DK159396B - SULPHONATED ZINC AND ALUMINUM PHTHALOCYAN COMPOUNDS AND THEIR PREPARATION - Google Patents

Description

in

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The present invention relates to novel sulfonated zinc and aluminum phthalocyanine compounds and to processes for their preparation.

From the specification to US Patent Nos. 3,927,967, 4,033,718 and 4,094,806, DE Publication No. 2,222,829 and 2,627,449, and descriptions to European Patent Application Nos. 3149, 3371 and 3861, it is known to employ photosensitizing compounds, e.g. water-soluble, especially sulfonated phthalocyanine derivatives and corresponding detergents for bleaching fabrics. Further, from the disclosure of U.S. Patent No. 4,166,718, a method of bleaching textiles is known by water-soluble aluminum phthalocyanine compounds, e.g. by means of sulfonated aluminum phtha-locyanin compounds, and a corresponding detergent.

DE-publication specification 2,812,261 also discloses a method for controlling microorganisms on various substrates by means of water-soluble phthalocyanine compounds, e.g. aluminum phthalocyanine compounds, especially sulfonated aluminum phthalocyanine, and an agent containing this compound as an active substance.

It is an object of the invention to provide photosensitizing compounds for use in bleaching textiles and for controlling microorganisms on various substrates and for corresponding agents for carrying out these methods which are more effective, economical and more favorable than the known agents. Surprisingly, it has been found that sulfonated zinc and aluminum phthalocyanines, which are further substituted by neutral, non-water-solubilizing groups, significantly increase the effectiveness of the known methods.

The sulfonated zinc or aluminum phthalocyanines of the invention correspond to the formula

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2 x Rx (MePC) (1) (303γ) ν wherein MePC means the zinc or aluminum phthalocyanine ring system, Y means hydrogen / an alkali metal, ammonium or amine salt, v means any number between 0.1 and 4, R 5 fluorine, chlorine, bromine, iodine or cyano and x means any number between 0.1 and 8, the substituents R present in the molecule being the same or different.

Particularly preferred among the compounds of formula (1) are those of formula

O I

(MePcrX '(2) ^ <so3ymv, wherein MePC means the zinc or aluminum phthalocyanine ring system, Y' represents hydrogen, an alkali metal or ammonium ion, ν 'is any number between 1.3 and 4, R' means chlorine, bromine or iodine, and x 'is any number between 0.5 and 8.

In formula (2), ν 'is preferably any number between 2 and 4, between 3 and 4, and x1 is preferably any number between 0.8 and 4. As is often the case in the phthalocyanine chemistry, the individual consists of products of mixtures, since in the manufacture, e.g. sulfonation and halogenation, not formed in a single compound.

In particular, among the compounds of formula (2) are mentioned in which Y 'is hydrogen, sodium or potassium, ν' is any number between 2 and 4, especially between 3 and 4, R 'is chlorine or bromine, preferably chlorine, and x 'means any number between 0.8 and 2, for example those wherein Y' is hydrogen, sodium or potassium, ν 'is any number between 3 and 4, R' is bromine and x "is any number between 0.5 and 1.5.

It is particularly preferred to use the said aluminum phthalocyanine compounds, especially those of the formula

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3 / C1'x "(A1Pc £ L (3)

(S03Y ") vB

wherein A1PC means the aluminum phthalocyanine ring system, x "means any number between 0.8 and 1.5, v" means any number between 3 and 4, and Y "means hydrogen or sodium.

As is known from the phthalocyanine chemistry, the third valence of the aluminum in the aluminum phthalocyanine ring system is saturated with an additional ligand, e.g. an anion. This anion may be identical to the anion in the aluminum compound which has been used to prepare the complex. It has no bearing on the effect of the compound in question. Examples of such anions include halide, sulfate, nitrate, acetate and hydroxyl ions.

"Amine salt ions" Y includes a substituted ammonium ion of the formula + yR1 m - r2 e3 wherein R 1, R 2 and R 2 each represent hydrogen, or optionally with halogen, hydroxy, phenyl or cyano substituted alkyl, preferably with 1- 4 carbon atoms, at least one of the 20 R substituents being different from hydrogen. In addition, two R groups may together with the nitrogen atom form a saturated 5 or 6 membered heterocyclic group, optionally further containing an oxygen or nitrogen atom as a ring link. Examples of such heterocyclic compounds include piperidine, piperazine, morpholine, pyrrolidine, imidazolidine, etc.

The index v indicates the degree of sulfonation, which of course is not necessarily an integer. Preferred sulfonation rates are between 1.3 and 4, especially between 2 and 4. The number of sulfo groups needed in the molecule also depends on the number

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4 of the substituents present R. In all cases, so many sulfo groups must be present that sufficient water solubility is ensured. A minimum solubility of 0/01 g / l may be sufficient, but usually a solubility of 0.1-20 g / l is appropriate.

The bleaching of the fabrics with the subject sulfonated zinc or aluminum phthalocyanine is preferably carried out in neutral or basic pH range.

The present zinc or aluminum phthalocyanines are advantageously used in amounts of 0.01 to 100, especially 0.01 to 50 mg / L of treatment bath, the amount used being able to vary with the degree of sulfonation and the substituent R.

The compounds of the invention are preferably used in combined washing and bleaching processes, in which case the aqueous bath also contains an organic detergent such as soap or synthetic detergent (see below), and optionally other detergent additives such as dirt suspending agents, e.g. sodium carboxymethyl cellulose, and optical brighteners. Therefore, the sulfonated zinc or aluminum phthalocyanine may either already be incorporated into the corresponding detergent or it may later be added to the washing float. However, the process can also be carried out as a pure bleaching process without detergent additives.

In this case, it is advantageous for the treatment bath 25 to contain an electrolyte, e.g. sodium chloride, sodium sulfate or sodium tripolyphosphate, to ensure absorption of the aluminum phthalocyanine dye. The amount of electrolyte can be from approx. 0.5 to 20 g / l.

The bleaching process is conveniently carried out at temperatures in the range of from approx. 20 to approx. 100, especially from approx. 20 to approx. 85 ° C, for a period of from 15 minutes up to 5 hours, preferably from 15 minutes to 60 minutes.

The bleaching process requires the presence of oxygen and

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5 radiation with light. As an oxygen source, the dissolved oxygen present in the air is sufficient.

The irradiation can be done with an artificial light source that emits light in e.g. the visible and / or the infrared region, e.g. an incandescent lamp or an infrared lamp whereby the bleach or wash bath can be directly irradiated, e.g. by means of a light source inside the container in which the float is located, e.g. a lamp in a washing machine, or by means of a light source outside the container. However, irradiation can only be carried out after removing the fabrics from the treatment bath. In this case, however, the fabrics must be moist or must later be moisturized again. However, as a light source, sunlight can also be particularly advantageous, as the fabrics are exposed to sunlight either during a treatment in the soaking bath 15 or after the treatment in the wash or bleach bath.

In order to exert their antimicrobial effect, the present zinc and aluminum phthalocyanine compounds require the presence of oxygen and water as well as irradiation with light.

20 Therefore, you work in aqueous solutions or on moist. substrates, and as the source of oxygen, the oxygen dissolved in the water or the oxygen of the air serves. The presence of reducing agents destroys or diminishes the effect of the substances.

The irradiation can be carried out with an artificial light source which, for example, gives light in the infrared and / or visible area or sunlight can be used. For example, good effect is achieved with light in the range of approx. 300 to approx. 2500 nm. Thus, for example, the irradiation can be done with a conventional incandescent lamp. Lighting intensity may vary within wide limits. It depends on the concentration of the active compound, the nature of the substrate or other substances present which affect the light output. As a second parameter, the illumination time can be varied, ie. at low light intensity, illumination must be carried out for a longer period of time than at greater intensity. Usually is

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6 it is possible, depending on the field of application, to use lighting times of from a few minutes up to a few hours.

When the process is carried out in an aqueous bath, e.g. germination of textiles, the irradiation with light can be carried out directly in the treatment bath with an artificial light source placed inside or outside of it, or the substrates can be illuminated at an later stage in an artificial light source or exposed to the sunlight. .

Already at very low concentrations of active compound, e.g. at 0.001 ppm, good antimicrobial effects can be achieved. Depending on the area of application and the phthalocyanine derivative used, a concentration of between 0.05 and 100 is preferred, preferably between 0.01 and 50 ppm. Since the active compounds are dyes, the upper concentration limit is determined by an undesired staining of the substrates. The upper concentration limit is thus limited by the average color strength of the medium used, but the upper limit can be at 1000 ppm and above.

The present zinc and aluminum phthalocyanine compounds have a very broad spectrum effect against microorganisms. Thus, primarily, gram-positive and gram-negative bacteria can be combated, or various substrates can be protected from attack by these bacteria. There is also an excellent effect against fungi and yeast fungi.

Furthermore, the compounds of the invention can be used in conjunction with effect-enhancing compounds, e.g. electrolytes, e.g. inorganic salts such as sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium acetate, ammonium acetate, alkali metal phosphates, alkali metal tripolyphosphates, especially sodium chloride and sodium sulfate. These salts can be added to the agents or they can be added directly by the application process such that they are present in the treatment solution at a concentration of preferably from 0.1 to 10%.

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Due to the aforementioned broad spectrum action against microorganisms, the compounds of the invention can be used in a variety of fields, examples of which are given below.

5 An important application is the germination of fabrics of synthetic or natural fabrics. Thus, household or industrial laundry disinfection can be performed using the compounds of the invention. For this purpose, the laundry can be treated with aqueous solutions of 10 water-soluble phthalocyanine derivatives under irradiation with light in the manner described above. In the treatment fleet, the phthalocyanine dye may advantageously be present at a concentration of 0.01 to 50 mg / l. The germination can advantageously also be carried out together with the washing process. For this purpose, the laundry is treated with a washing float containing common washing active substances, one or more water-soluble zinc or aluminum phthalocyanine derivatives and optionally inorganic salts and / or other antimicrobially active compounds. The washing process can be performed manually, e.g. in a tub or it can be carried in a washing machine. The necessary irradiation may be carried out during the washing process by suitable light sources, or the wet laundry may be added at a later date, e.g. during drying, either irradiated with a suitable artificial light source or simply exposed to the sunlight.

The compounds of the invention can be added directly to the disinfection or washing float. However, they can also be incorporated into soaps or detergents containing the known mixtures of detergents, such as e.g. soap 30 in the form of cuts or powders, synthetic substances, soluble salts of sulfonic acid halves of higher fatty alcohols, higher and / or several times alkyl-substituted arylsulfonic acids, sulfocarboxylic acid esters with moderate to higher alcohols, fatty acid acylaminoalkyl or amino acid glycerates, etc., so-called "builders", e.g. alkali metal poly and polymethaphosphates,

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8 alkali metal pyrophosphates, alkali metal salts of carboxymethyl cellulose and other so-called "soil redistribution inhibitors"; lanolin / enzymes, perfumes and dyes, optical brighteners, other inorganic salts and / or other antimicrobial active compounds.

It is important that the washing floats or detergent contain no reducing agents, as this would mean that the oxygen needed for the antimicrobial action of the phthalocyanins would then not be available.

The compounds of the invention can also be used for anti-microbial impregnation of textiles, since the zinc and aluminum phthalocyanine derivatives are well retained by the fibers, thereby ensuring a long-lasting effect.

Another area of application of the compounds of the invention is disinfection of hospital laundry, medical utensils and equipment as well as of floors, walls and furniture (surface disinfection) in general and in particular in hospitals. Disinfection of hospital laundry can be done in the manner described above for ordinary laundry. The other articles and floor and wall surfaces can be treated with 25 aqueous solutions containing the sulfonated zinc or aluminum phthalocyanine compounds, under or with subsequent irradiation with suitable light sources. The disinfectant solutions may additionally contain detergent, other antimicrobially active compounds and / or inorganic salts.

For example, for surface disinfection, an aqueous solution of the subject phthalocyanine compounds may be applied to the respective surfaces, e.g. by spraying, which solution preferably contains from ca. 0.001 to approx. 50 ppm 9 DK 1593968 active substance. The solution may also contain other common additives, e.g. wetting, dispersing or emulsifying agents, detergents and optionally inorganic salts. The surface is simply exposed to the sunlight after application of the solution or, if necessary, it can be further irradiated with an artificial light source, e.g. an incandescent lamp. It is recommended to keep the surface moist during irradiation.

Advantageously, the compounds of the invention can also be used for bathing and disinfecting swimming pools. For this purpose, the water in the swimming pool is suitably added to one or more of the subject phthalocyanine compounds, preferably in an amount of between 0.001 and 50, especially between 0.01 and 10 ppm. The lighting is done simply by means of the sunlight. Optionally, additional lighting can be made using 15 built-in lamps. Using the described method, the water in swimming pools can be kept free of bothersome germs and maintain an excellent water quality.

Furthermore, the compounds of the invention can be used for the decomposition of wastewater from clarification plants. For this purpose, e.g. 0.001-100, especially 0.01-10 ppm, of one or more of the subject phthalocyanine compounds for the wastewater. The radiation is expediently done with the help of sunlight, and additional radiation can be made with artificial light sources.

The above-mentioned uses are only examples of the very broad scope of the compounds of the invention.

The sulfonated zinc and aluminum phthalocyanine compounds of the invention can be prepared using methods of the phthalocyanine chemistry known per se. The non-water-solubilizing substituents, e.g. for example, the substituents R in formulas (1) and (2) may already be present in the starting materials used to build the phthalocyanine ring backbone, e.g. phthalic anhydride, phthalo-

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10 dinitrile or phthalodiimide. After the construction of the correspondingly substituted, possibly already metallized, phthalocyanine, the sulfonic acid groups can be introduced if these do not already exist in the starting materials. Many 5 substituents can also be introduced into the already constructed phthalocyanine ring system, e.g. by chlorination, bromination or iodination (R = Cl, Br, J). The sulfonic acid groups may be introduced before (cf., for example, U.S. Patent No. 2,647,126) or later. If the structure of the phthalocyanine ring system 10 is carried out from phthalic anhydride or phthalodinitrile in the presence of chlorides, e.g. AlCl 3 or ZnCl 2 mole of aluminum phthalo-cyanine. In such products, the sulfonic acid groups can also be introduced at a later date. For the preparation of differently substituted phthalocyanine compounds, the above methods can be suitably combined. All of the methods are well known and extensively described in the phthalocyanine chemistry.

The introduction of the sulfonic acid groups can be carried out, for example, by sulfonation, e.g. using oleum. Alternatively, similarly unsulfonated phthalocyanines can also be reacted with chlorosulfonic acid to the corresponding phthalocyanine sulfochlorides which are then hydrolyzed to the sulfonic acids.

In either case, the free sulfonic acid groups can then be transferred to salts thereof.

All reactions with the built-up phthalocyanine ring system can already be carried out with the zinc or aluminum complex.

However, it is also possible to introduce the substituents into the metal-free phthalocyanine skeleton and then to metallize it using methods known per se, cf. eg. U.S. Patent No. 4,166,780, e.g. by reacting the metal-free phthalocyanine compounds with a zinc cell aluminum salt or alcoholate. 1 5 For the introduction of halogen atoms, diazotization can also be carried out

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11 of zinc or aluminum phthalocyanine substituted with amino groups, after which the diazonium group or groups are exchanged with halogen (Sandmeyer reaction). The introduction of the sulfo groups in this case can also be done before or after the introduction of the halogen atoms.

The structure of the phthalocyanine ring backbone from phthalic acid derivatives, thereby forming chlorinated phthalocyanines, is described in Ullmann's "Encyclopaedia der technischen Chemie", 4th edition, volume 18, page 508 et seq., And by F.H. Moser and A.L.

10 Thomas "Phthalocyanine" (1963), page 104 et seq. Halogenated phthalocyanines or phthalocyanins containing other inert substituents can be prepared by blending condensation of unsubstituted or similarly substituted phthalic acids or phthalic acid derivatives using conventional methods of phthalocyanine. In the following embodiments 1a, 2a, 3a and 5a, the implementation of such methods is illustrated. In the following examples which illustrate the preparation of the active substances according to the invention, 20 are parts and percentages by weight, unless otherwise stated. In all examples, the A1PC means the aluminum phthalocyanine ring system and the ZnPC zinc phthalocyanine ring system. Furthermore, the phthalocyanine sulfonic acids are produced in part as sodium salts. Therefore, as is generally the case with the dye chemistry, the group -SO3H also includes the sodium salts thereof. The values of λ ^^ values from the absorption spectrum used to characterize the phthalocyanine compounds are determined in a mixture of ethanol and water (1: 1) at pH 7.

Example 1 ♦ a) Into an autoclave are placed 128 g of phthalic acid dinitrile, 40 g of AlCl 2 and 650 g of 1,2-dichlorobenzene. After rinsing with nitrogen, the reaction mass is heated for 26 hours to ca. 170 ° C. After cooling and deaeration, the suspension is poured into the stirring

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12 400 ml of water containing 100 g of trisodium phosphate. Then the mixture is evaporated to dryness on a rotary evaporator, the crude product is stirred with 750 ml of water, then 60 g of 50% sodium hydroxide solution is added, heated to 75 ° C, after which the mixture is kept at this temperature for 2 hours. The crude product is then filtered off, stirred in 500 ml of water containing 80 g of 32% hydrochloric acid (2 hours at 90-95 ° C), then filtered hot and washed. In this way, an aluminum phthalocyanine containing 1 mole of bound chlorine 10 moth.

b) 60 parts of the monochloro-aluminomphthalocyanine prepared according to (a) are added to 260 volumes of chlorosulfonic acid under good stirring. With the aid of external cooling, the temperature is maintained at 20-25 ° C. The reaction mixture is first stirred for 15 1/2 hours at room temperature, after which the temperature is raised to 110-115 ° C over one hour. After 1/2 hour, the reaction temperature is raised to 130-135 ° C over 1 hour, after which the reaction mixture is left at this temperature for 4 hours.

The reaction mixture is then cooled to 70-75 ° C, and 125 volumes of thionyl chloride are added over 45 minutes. Stirring is continued for 1 hour at 85-90 ° C, after which the reaction mass is cooled to room temperature and then poured into a mixture of ice and water. The cold sulfochloride suspension is suction filtered and washed acid-free with ice water.

The moist sulfochloride paste is suspended in 1200 parts of water. The sulfochloride groups are converted to sulfo groups by the addition of sodium hydroxide at 50-60 ° C. The saponification can be accelerated by the addition of catalytic amounts of pyridine.

After saponification, the slightly basic solution 30 is evaporated to dryness. In this way 105 parts of a water-soluble blue powder are obtained. Analysis of the product shows that it contains 1 mole of organically bound chlorine and approx. 3.5 moles of sulfonic acid groups per moles of aluminum phthalocyanine corresponding to the formula (A1PC) Cl (SO-H) _. with a λ value of 674 nm. ό max

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0.13

Example 2.

a) 118 parts of urea, 20 parts of 4-chlorophthaic acid, 44.4 parts of phthalic anhydride, 27 parts of xylenesulfonic acid (isomer mixture), 1 part of ammonium molybdate, 15 parts of aluminum chloride and 200 parts of 5 trichlorobenzene (isomeric mixture) are stirred thoroughly in a stirring flask. over 3 hours is heated to 195-205 ° C and stirring is continued at this temperature for 16 hours. After cooling, 500 volumes of isopropanol are added and stirred for a short time, after which the suspension is suction filtered. The residue is washed with 500 volumes of isopropanol. The residue is taken up in 800 parts of dilute sodium hydroxide solution, then stirred for 2 hours at 80-90 ° C, suction filtered and washed with warm water. This is repeated in dilute hydrochloric acid, whereupon the pigment formed is washed acid-free in hot water and dried. There are approx. 50 parts of monochloraluminum phthalocyanine (201) in the form of a blue powder.

Proceed in the same manner as described above, however, replacing 4-chlorophthalic acid with similar amounts of dichlorophthalic acid or anhydride, tetrachlorophthalic acid or anhydride, 4-bromophthalic acid or anhydride, tetrabromophthalic acid or anhydride, 4-iodophthalic acid or -anhydride or di-iodophthalic acid or anhydride to give the following halogenated phthalocyanines (pigments): (202) Dichloraluminum phthalocyanine (203)

b) The halogenated phthalocyanine pigments (201) prepared in (a) (207) are transferred using the procedure of Example 1b) into the corresponding sulfogroup-containing compounds. In this way, the following compounds are prepared:

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14 (211) (A1PC) C1 (SO3H) 3_4 Xmax = 674 nm (212) (A1PC) C12 (SO3H) 3_4 (213) (A1PC) C14 (SO3H) 3_4 (214) (AlPC) Br (SOOH) _. λ 675 nm '3 3-4 max 5 (215) (AlPC) Br4 (SO3H) 3_4 Xmax = 677 nm (216) (A1PC) J (SO-, H). . X = 678 nm

O v 4 illdA

(217) (A1PC) J2 (SO3H) 3_4

Example 3

a) In a sulfonation flask, 44.4 parts of phthalic anhydride, 22.7 parts of 4-bromophthalic anhydride, 74 parts of urea and 17 parts of aluminum chloride are heated to 215-220 ° C and the mixture is stirred for 2 hours at this temperature. After cooling, the solidified mass is comminuted. The purification is done by extraction with hot dilute sodium hydroxide solution, hot water, hot 15 dilute hydrochloric acid and again with hot water. After drying, 16.5 parts of monobromous aluminum phthalocyanine are obtained in the form of a blue powder.

b) The monobromous aluminum phthalocyanine prepared according to (a) is reacted analogously to the procedure described in Example 1b) with chlorosulfonic acid and the monobromous aluminum phthalocyanine sulfochloride formed is transferred to the corresponding sulfonic acid by basic hydrolysis. In this way, a product is obtained which contains by analysis 1 mole of organically bound bromine and approx.

3.5 moles of sulfonic acid groups per mole of aluminum phthalocyan and, therefore, corresponds to the formula (A1PC) Br (SO..H) _. (X = 675 nm).

3 3-4 max

By analogy to the procedures described in Example 1b) or Example 3b, however, instead of monochloro-aluminum phthalocyanine or monobromo-aluminum phthalocyanine, similar amounts of monofluoro, monoiodine or monocyano-aluminum phthalocyanine are used, products of similar composition, namely A1 ( ) F (SO 3 H) 3_4, (AlPC) J (SC> 3H) 3_4 (Xmax = 678 nm) and (AlPC) CN (SO-jH) 3_4. The fluorine, iodine or cyanosubstituted aluminum phthalocyanines can be produced ✓

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15 by analogy to Example 3a) in known manner by mixing synthesis from the corresponding substituted phthalic acid compounds and unsubstituted phthalic acid compounds.

Example 4

5 60 parts of monochloro-zinc phthalocyanine are added to 260 volumes of chlorosulfonic acid with good stirring. During the addition, the temperature is maintained at 20-25 ° C by external cooling. The reaction mixture is first stirred for 1/2 hour at room temperature, then the temperature is increased to 110-115 ° C over 1 hour.

After 1/2 hour, the reaction temperature is raised to 130-135 ° C over 1 hour and the reaction mixture is left at this temperature for 4 hours. Then, the reaction mixture is cooled to 70-75 ° C and 125 volumes of thionyl chloride are added over 45 minutes. The reaction mixture is stirred for an additional 15 hours at 85-90 ° C, after which the reaction mass is cooled to room temperature and poured into a mixture of ice and water. The cold sulfochloride suspension is suction filtered and washed acid-free with ice water.

The moist sulfochloride paste is suspended in 1200 parts of water 20 and hydrolyzed at 50-60 ° C by the addition of sodium hydroxide to the sodium salt of monochlorinated zinc phthalocyanine sulfonic acid.

The slightly alkaline solution is evaporated to dryness. In this way, a water-soluble blue powder is obtained. This product corresponds to the formula (ZnPC) Cl (SO H) (λ = 670 nm).

The monochlorinated zinc phthalocyanine used as the starting product is prepared using the known urea process by mixing synthesis of 1 equivalent of 4-chlorophthalic anhydride with 3 equivalents of phthalic anhydride with the addition of anhydrous ZnCl 2

Similarly, zinc phthalocyanine sulfonic acids are prepared with the formulas (ZnPC) F (SO 2 H) 3_4, (ZnPC) Br (SO-3H) 3_4, (ZnPC) J (SO3H) 3_4 and (ZnPC) CN (SO3H) 3_4.

Example 5

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a) In a stirrer, a uniform mixture of 150 parts of urea, 20 parts of 4-chlorophthalic acid, 44.4 parts of phthalic anhydride, 27 parts of xylenesulfonic acid (isomer mixture), 1 part of ammonium molybdate and 20 parts of zinc chloride is heated slowly to 150 ° C. .

After 2 hours, the temperature is raised to 180-190 ° C and the mixture is stirred for a further 12 hours. The cooled mass is comminuted, stirred with 20 parts by volume of isopropanol and suction filtered, after which the residue is washed with 200 parts by volume of acetone.

The residue is stirred in 800 volumes of dilute sodium hydroxide solution for 2 hours at 80-90 ° C, then suction filtered and washed with warm water. The residue is then stirred in dilute hydrochloric acid for 2 hours at 80-90 ° C, then suction filtered, washed acid-free with water and dried.

In this way, 34 parts of monochlorinated zinc phthalocyanine (501) are obtained in the form of a blue powder.

By analogy to the procedure described above, however, substituting 4-chlorophthalic acid with similar amounts of tetrachloro, 4-bromo, tetrabromo, 4-iodo or diiophthalic acid, the following halogenated phthalocyanines (pigments) are prepared: (502) Tetrachlorzinc phthalocyanine ( 503) Monobromed Zinc Phthalocyanin (504) Tetrabrom Zinc Phthalocyanin (505) Monoiod Zinc Phthalocyanin (506) Diode Zinc Phthalocyanin.

b) The halogenated phthalocyanine pigments (501) to (506) prepared in accordance with (a) are transferred analogously to the corresponding sulfo group-containing compounds described in Example 4. In this way, the following compounds are prepared: (511) (ZnPC) Cl (SO-H) -. λ = 670 nm 3 3-4 max (512) (ZnPC) Cl4 (SO3H) 3_4 Amax = 672 nm (513) (ZnPC) Br (SO-H) 0. λ = 669 nm 3 3-4 max 35 (514) δNPC) Br4 (SO3H) 3_4 (515) (ZnPC) J (SO3H) 3_4 (516) (ZnPC) J2 (SO3H) 3_4

Example 6

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Testing of Effect against Bacteria and Fungi Procedure

An aqueous solution containing (A1PC) Br (SO ^ H) or 5 (A1PC) J (SO ^ H) at a concentration of 0.01, 0.1 and 1.0 ppm respectively is added to a seed suspension of Staphylococcus aureus ATCC 6538 with a defined seed rate per ml.

This test suspension is contained in a beaker under a water-cooled glass plate to avoid heating as a result of the subsequent illumination. Lighting is then performed with an incandescent lamp or an infrared lamp (infrared lamp "Weiss", Philips IR, 250 W, type 13372 E / 06) located at a distance of 20 cm above the suspension surface, in 15, 10, 20 respectively. , 30 and 60 minutes. The seed count is then determined in the usual way by parallel counts. The corresponding germ-n reduction is calculated in tier potentials by the formula x = -log ^ -, where Nq is the initial germination number and N is the number of surviving germs (average value of 5-10 parallel counts).

In comparison, the effect of (A1PC) (SO3H) 3_4 is determined in exactly the same way.

The obtained germ reductions x are given in Table I below.

Table I.

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Exposure time in minutes ppm 5 10 20 30 60 0.01 for low effect 0.1 0.5 5 (A1PC) (SO 3 H) 3_4 0.1 0.2 0.9 1.2 2.0 1.0 0.9 1, 6 2.3 2.7 3.4 0.01 0.7 1.5 2.0 2.9 (AlPC) Br (SO3H) 3_4 0.1 1.6 2.4 3.2 3.7 4, 1.0 1.0 3.3 4.0> 4.6> 4.6> 4.6 0.01 0.01 1.0 1.8 2.7> 4.6> 4.6 (A1PC) J (SO 0.1 2.3 3.6> 4.6> 4.6> 4.6 1.0 4.1> 4.6> 4.6> 4.6> 4.6

The results set forth in Table I show that with the compounds (A1PC) Br (SO3H) 3_4 and (A1PC) J (SO3H) 3_4, excellent anti-bacterial action is obtained, even at very short illumination times. These values are substantially better than those obtained with the corresponding non-halogenated compound of formula (A1PC) (SO3H) 3_4.

Similarly good results are obtained with compounds 20 (aipc) f (so3h) 3_4, (aipc) ci <so3h) 3_4, (aipc) cn (so3h) 3_4, (A1PC) C12 (SO3H) 3_4, (A1PC) C14 (SO3H) 3_4, (AlPC) Br (SO3H) 3_4, (AlPC) Br4 (SO3H) 3_4, (A1PC) J (SC> 3H) 3_4, (A1PC) J2 (SO-jH) 3_4, (ZnPC) Cl (SO3H) 3_4 , (ZnPC) Br (SO3H) 3_4, (ZnPC) J (SC> 3H) 3_4, (ZnPC) Cl4 (SO3H) 3-4, (ZnPC) Br4 (SO3H) 3_4 and (ZnPC) J2 (SO3H) 3 < _4.

The test procedure described above is repeated, using the following bacteria and fungi instead of Staphylococcus aureus ATCC 6538 as test germs:

Streptomyces faecalis var. zymogenes NCTC 5957 Escherichia coli NCTC 8196 30 Pseudomonas aeruginosa ATCC 15442

Proteus vulgaris ATCC 6896 Aspergillus niger ATCC 6275

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Candida albicans ATCC 10259 Trichophyton mentagrophytes ATCC 9533.

The above-mentioned zinc and aluminum phthalocyanine sulfonic acids having a halogen atom or cyano group in the molecule also have excellent effects on these test germs. The action of each of these compounds is substantially better than the action of the corresponding pure zinc or aluminum phthalocyanine sulfonic acid (without additional halogen or pseudo-halogen in the molecule).

Example 7.

Testing of disinfection effect on textiles

A piece of woven cotton fabric is stretched onto a metal frame and seeded with a test suspension described in Example 6 (containing (AlPC) Br (SO 2 H) and a test germ line). The metal frame, which is connected to a motor, is then rotated and illuminated with an infrared lamp. A glass plate is placed between the lamp and the fabric piece which is cooled with liquid water to avoid heating the fabric piece. Under the same experimental conditions, a piece of fabric is treated in parallel, on which, however, no microbicide compound is applied. After 1 hour of illumination, quantitative determination of the germ numbers is made and the germ reduction induced by the phthalocyanine in question is calculated. The effect of (A1PC) Br (SO 1 H) on Strept.faecalis var was tested. zymogenes 25 NCTC 5957. Approximately the same germ reduction is found as in Example 6.

Example 8.

surface Disinfection

Enamelled tiles of size 4 x 4 cm are inoculated with a Staphy-20 lococcus aureus ATCC 6538 seed suspension, whereby approx. 10 ^ germ is evenly distributed on the surface of a tile. Then, the surface is sprayed with an aqueous solution containing 1 ppm of the compound of formula (AlPC) Cl (SO 2 H), (A1PC) Br (SO 3 H)

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20 or (AlPC) J (SO 2 H). Then the surface is illuminated with a light bulb (250 W, distance 20 cm) for 30 and 45 minutes respectively.

Once the lighting is complete, sampling is done by knocking in Rodac bowls. After 30 minutes, in the case of treatment with (AlPC) Cl (SO 3 H), only one colony can be detected, whereas in the case of the other two test compounds and at an exposure time of 45 minutes for all three test compounds, no evidence can be found at all. any germ growth.

Using the others of Example 6 listed as test compounds, halogenated or CN-substituted phthalocyanine sulfonic acids in the above-described surface disinfection test, similarly good results are obtained. After an exposure time of 45 minutes, no germ growth on the surface can be detected in treatment with all 15 test compounds.

Example 9

Depletion of wastewater from a treatment plant

A sludge sample is taken from a laboratory clarifier, 20 and the sample is filtered through a paper filter. For the filtrate containing approx. 10 ° g / ml, a phthalocyanine compound of formula (AlPC) Cl (SO 2 H), (AlPC) Br (SO 3 H) 34 or (AlPC) J (SO 3 H) is added until the concentration of the filtrate is 1 ppm. Then the filtrate is illuminated with standard light 380-225730 nm, 300 mW / cm. At different times, the seed count in the filtrate is determined. After 45 minutes, there are no longer staphylococci. After longer exposure time (from 1 to several hours), the number of other germs present in the filtrate also decreases clearly.

Example 10.

Descent of swimming pools In the open air swimming pools, each containing 5000 liters of water, are set up. To the water in a basin is added the compound

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21 of the formula (AlPC) Cl (SO 2 H) at a concentration of 0.5 ppm.

At intervals of 1-5 days, water samples are taken and quantitative determination of the germ numbers is made. In the microbiological test, a) the total germ number and b) the number 5 of coliform germs is determined.

Results In basins that do not contain monochloroaluminum phthalocyanine sulfonic acid, the coliform germs are propagated to 2-3 x 101 germ / 100 ml. In basins containing the active substance, no coliform germs are found until the sixteenth day of testing.

For a further experiment, a seed suspension containing Staphylococcus aureus ATCC 6538 and Escherichia coli ATCC 11229 is added at an amount of 50 germ per gram. 100 ml basin content for the water on 15th of the 16th trial day. A measurement immediately after the seed addition shows a uniform distribution in the basin. After 24 hours, no coliform germ content and staphylococci in the basin containing the active substance (100 ml of water) are detected. The total seed count of 20 autochthon (originating from the swimming pool) seedling flora remains constant during the experiment.

Example 11.

A 1g cotton fabric soaked in red tea is treated at 55 ° C under illumination with a 200W 25 incandescent lamp for 1 hour with stirring with 200ml of an aqueous washing float containing 0.75 ppm (A1PC ) Cl (SC> 3H) (prepared according to Example 1 or 2) and 1 g of detergent having the following composition:

Sodium dodecylbenzenesulfonate 16% Sodium tripolyphosphate 43%

Sodium silicate 4%

Magnesium silicate 2%

Fatty alcohol sulfate 4%

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22

Sodium Carboxymethyl Cellulose 1%

Sodium salt of ethylene diamine tetraacetic acid 0.5% Sodium sulfate 29.5%

Then visual evaluation of the fabric is performed, whereby it turns out that its brightness is far above the brightness of the soiled fabric. However, the piece of fabric treated as above is also clearly lighter than a piece of fabric treated under similar conditions, however 0.75 ppm of pure (A1PC) (SO 2 H) 3_4 (without nucleated chlorine) is used as photobleach.

Measurements of the brightness value of the fabric pieces with an Elrepho photometer from the company Zeiss confirm the visual assessment.

To the results obtained with (A1PC) Cl (SO ^ H) correspondingly good results are obtained when instead of the latter compound (A1PC) F (SO3H) 3_4, (AlPC) Br (SO3H) 3_4, (A1PC) J (SO3H) 3_4, (A1PC) CN (SO3H) 3_4, (AlPC) Br4 (SO3H) 3_4, (A1PC) C12 (SO3H) 3_4, (A1PC) C14 (SO3H) 3_4, (ZnPC) Cl4 (SO3H) 3_4, {ZnPC) Br4 (SO3H) 3_4, (ZnPC) Cl (SO3H) 3_4, (ZnPC) F (SO3H) 3_4, (ZnPC) Br (SO3H) 3_4 or (ZnPC) J (SO3H) 3_4.

The soiling of the cotton fabric with tea is done as follows: 1 g of tea ("Fine Ceylon Fannings Tea") is boiled for one hour in 600 ml of demineralized water and filtered. The filtered tea leaves are taken up in 400 ml of demineralized water and then boiled for approx. 60 minutes. The two filtrates are combined and the volume is adjusted to 1000 ml with demineralized water. In this tea, 45 g of cotton fabric (bleached and leached) is treated under constant motion at 100 ° C for 2 1/2 hours, after which the "dyeing process" is continued in a cooling bath for an additional 16 hours. Then 5 g of sodium chloride is added to the tea float and the treatment is continued for 2 1/2 hours at 100 ° C. Then, cooling is done and the

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23 the cotton fabric is rinsed twice at 60 ° C and dried at 100 ° C. Then, the soiled substance is washed with a raft containing 5 g / l of detergent of the above composition at 90 ° C for 20 minutes in a ration ratio of 1:20, 5 then rinsed hot and cold and dried at 100 ° C for 1 hour. a dryer.

The lamp used is a "Luxram" incandescent lamp 220/230 V, 200 W E 27, matted. The lamp is placed about 10 cm above the wash raft. The measured illuminance is 19000 lux.

Example 12.

• cf. 10 samples weighing 1 g of a brown dyed cotton fabric are added to a washing float containing 4 g / l of a detergent of the composition specified in Example 11 and a certain amount (by weight, calculated on weight of substance (fat) (AlPC) Cl (SO-jH) 3_4, (AlPC) Br (SO3H) 3_4, (AlPC) J (SO3H) 3_4 and for comparison purposes (AlPC) (S © 3H) 7_4. The weight amounts are shown in the following Table 2. During constant movement of the samples to be bleached, these are washed at 50 ° C for 60 minutes at a beautiful ratio of 1: 100 and 20 under illumination with an infrared lamp. The samples are then rinsed and dried, and the bleaching rate of the dried samples is measured using a Zeiss Elrepho ^ photometer (standard light type D 65, 2 degree normal viewer, measuring 35 mm 0) in the form of brightness values, expressed as a percentage, calculated compared to the absolute white according to CIE Recommendation of 1.1.1969. The measured values are listed in Table II below and are average values.

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Table II.

24

Test compound Amount in wash- Brightness value of the float (%) in% (A1PC) C1 (SO3H) 3_4 0.0035 80.20 (AlPC) Br (SO3H) 3_4 0.002 81.67 5 (A1PC) J (SO3H) 3_4 0.0023 81.05 (A1PC) (SO3H) 3_4 0.004 80.20 --- --- 56.5 (= test sample is unbleached)

The results in Table II show that the halogen-containing aluminum-phthalocyanine sulfonic acid derivatives, when used in small amounts, give the same high or even higher bleach rate than the non-halogenated aluminum phthalocyanine sulfonic acid (A1PC) (SO3H) 3_4 · used for comparison.

Using similar zinc phthalocyanine derivatives 15 similar results are obtained.

^)

The dyeing of the cotton samples is carried out as follows: 150 mg of the commercially available brown dye of the formula

OH. OH O

x— / / ν '.—. || .-.

<ζ ^> - Ν = Ν ^ | ^ Ν = Ν- <ζ ν, -Ο-ΝΗ- ^ ^ -Ν = Ν- | —C-CH3 SO-jH X Ν

3 Τ Ηθ 'V

OH I

Η 20 is dissolved in 2000 ml of water containing 1 g of soda at a temperature of 50 ° C. In this color float, 100 g of cotton fabric (bleached, leached) is stained with constant movement, heating the bath to 90 ° C over 30 minutes. At 90 ° C, the staining is done for 90 minutes, during which time 25 g of Glauber salt is added in four equal portions at 15 minute intervals.

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When the dyeing is complete, rinse cold twice, then make a dressing in a bath containing 0.75 g / l crystalline copper sulfate and 1 ml / l glacial acetic acid, at 60 ° C and a nice ratio of 1:20 for 20 minutes. Then two 5 times cold rinsing of the staining is done, then dried in a hot air oven at 100 ° C.

The lamp used is a "Philips" infrared lamp (white), 220/230 V, 250 W with reflector, type 13372 E / 06. The lamp is placed approx. 15 cm above the raft.

Example 13.

10 g of a brown dye cotton sample according to Example 12 is placed in 200 ml of water containing 0.75 mg of (AlPC) Br (SO 3 H) 3 4, (A1PC) J (SO 3 H) 3_4 or (AlPC) Cl (SO3H) 3_4 and 0.2 g sodium tripolyphosphate. The barrel is heated under constant motion to 75 ° C and maintained for 90 minutes at this temperature, then 4 g Glauber's salt is added in four equal portions at 10 minute intervals. Then, briefly rinse the fabric sample, which is then dried in a circulating air dryer at 100 ° C. All 20 of the operations described above are carried out under extensive light exclusion.

For comparison, a similar sample is treated, using the same amount of a non-halogenated aluminum phthalocyanine sulfonic acid (AlPC) (SO3H) 3_4 instead of 0.75 mg of the above halogenated phthalocyanine sulfonic acids.

The stained fabric samples are then moistened with a buffer solution of pH 10 (composition: 0.03 mol / 1 disodium tetraborate and 0.042 mol / 1 sodium hydroxide) and illuminated at room temperature under an overhead projector (portable Projector Model 088/88 BH from company 3M with a lamp of type 78-8454 / 3480 from General Electric, 240 V, 480 W), the pieces of fabric being placed under a glass plate in a

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26 distance of 30 cm from the lamp (measured illuminance: 46000 lux). For control purposes, a brown colored piece of fabric which is not treated with an aluminum phthalocyanine is similarly illuminated.

5 To determine the brown dye decomposed by the illumination and the amount of the phthalo-cyanine compounds remaining on the sample, the samples are color-metrically evaluated against adjusting stains. It turns out that with (A1PC) Cl (SO ^ H) 3.4 / (AlPC) Br (SO ^ H) and (A1PC) J (SO ^ H) at different illumination times more brown dye is decomposed than with non- halo-generated aluminum phthalocyanine sulfonic acid.

When using the corresponding zinc compounds prepared according to Examples 4 or 5 instead of the aluminum compounds or the aluminum compounds of formula 15 (aipc) ci2 (so3h) 3_4, (aipc) ci4 (so3h) 3_4, (aipc) f (so3h) 3_4f (AlPC ) Br4 (SO3H) 3_4 or (A1PC) J2 (SO3H) 3_4, similar results are obtained.

Example 14.

Ten samples of 1 g of a woven cotton-dyed cotton fabric according to Example 12 are added to a washing float containing 4 g / l of a detergent having the composition of Example 11 and 0.005 or 0.01% by weight, calculated on the weight of the substance * (ZnPC) Cl (SC> 3H) 3_4, (ZnPC) Br (SO3H) 3_4, (ZnPC) Cl4 (SO3H) 3_4, and for comparison purposes (ZnPC) (SO3H) 3__4.

25 During constant movement of the samples to be bleached, these are washed at 50 ° C for 60 and 120 minutes, respectively, at a beautiful ratio of 1: 100 and ”under illumination with an infrared lamp (see Example 12). The samples are then rinsed and dried to measure the bleaching of the dried samples using an Eliss 30 rephc @ photometer from the firm of Zeiss (standard light type D 65, 2 degree normal viewer, measuring 35 mm 0) in the form of brightness values (Y), expressed in percent, calculated on the absolute white according to CIE Recommendation of 1.1.1969. The values obtained are listed in the following table, and are average values.

27

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Table III.

Test compound Amount in wash Brightness values Y in% nice (in wt%, after calculated on tissue 60 minutes 120 minutes weight) (ZnPC) (SO 3 H) 3_4 0.005 74.2 75.6 __0.01__76.4__79.0_ ( ZnPC) Cl (SO3H) 3_4 0.005 80.6 82.1 __0.01__83.0 ___ 85.3 (ZnPC) Cl4 (SO3H) 3_4 0.005 79.6 82.3 __0.01__82.1__85.3_ (ZnPC) Br (SO3H ) 3_4 0.005 80.6 83.9 __0.01__81.5 84.7_ 50.3 (= Test sample is unbleached)

The results in Table 3 show that the halogen-containing zinc phthalocyanine sulfonic acids give significantly higher brightness values than the non-halogenated zinc phthalocyanine sulfonic acid used for comparison. In other words, the halogen-containing compounds can be used at substantially lower amounts than the non-halogenated product to obtain the same or better brightness value.

Example 15

The washing process described in Example 14 is repeated, however, (a) the amount of test compound used is 0.015% by weight, based on the weight of the cotton fabric, b) the finished 20 floats are illuminated for 30 minutes prior to the introduction of the cotton fabric, and c) the illumination time after the addition of the fabric (= bleaching time) is only 60 minutes.

The measurement of the bleaching rate of the fabric is carried out in the same way as described in Example 14. In Table IV below, the values obtained are listed. The individual values are an average value of 10 single measurements.

$

Table IV.

28

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Test compound Brightness value (Y) (ZnPC) (SO3H) 3_4 70.6 (ZnPC) Cl (SO3H) 3_4 79.4 5 (ZnPC) Cl4 (SO3H) 3_4 78.2 (ZnPC) Br (SO3H) 3_4 77.8 51 , 1

The results in Table 4 show that when the float is exposed to illumination before the actual washing process, with the halogenated phthalocyanine sulfonic acids, surprisingly significantly greater brightness values are obtained than with the corresponding non-halo-generated compound. This circumstance has practical significance, e.g. when a housewife prepares the washing raft and leaves it to light, e.g. in the open, without immediately starting the washing process. In this case, the halogenated phthalocyanine compounds give significantly better bleaching effect.

Similarly good results are also obtained with the other phthalocyanine compounds mentioned in Examples 1-5.

Example 16.

Fabric samples weighing 5 g soiled with red wine (EMPA test sample No. 114, from Eidgenossischen Materialpruf-und Versuchsanstalt, CH-9001 St. Gallen, Unterstrasse 11) are washed at a good ratio of 1:50 at 50 ° C for 30 minutes 25 in a float containing 5 g / l of a detergent having the composition of Example 11 and 0.005% by weight, based on the weight of the test piece, (AlPC) (SO3H) 3_4 or (AlPC) Br4 (SO3H) 3_4 . In comparison, a substance sample is washed in a raft that does not contain phthalocyanine compound.

After washing, briefly rinse the specimens, which are then laid for 2 hours in the midday sun and moistened several times. Then, the degree of bleaching of the drug samples is determined

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29 (brightness) in the same manner as in Example 14. The resulting brightness values (Y) are given in Table V below.

Table V.

Washing process Brightness values (Y) 5 1) without phthalocyanine compound 66.2 2) with 0.005% (AlPC) (SO-jH) 3_4 79.8 3) with 0.005% (AlPC) Br4 (SO3H) 3_4 83.4

Test sample without sink 43.6

The results in Table 5 show again that the halogenated phtha-10 locyanine sulfonic acids give a significantly better bleaching effect (stain removal effect) than the corresponding non-halogenated compound.

Claims (7)

Zinc or aluminum phthalocyanine compounds, characterized in that they have the general formula -Rx (MePC) (1). "(SOQY) 3 v 5 wherein MePC means the zinc or aluminum phthalocyanine ring system, Y means hydrogen, an alkali metal, ammonium or amine salt, v means any number between 0.1 and 4, R means fluorine, chlorine, bromine, iodine or cyano, and x is any number between 0.1 and 8, the substituents R present in the molecule being the same or different. Phthalocyanine compounds according to claim 1, characterized in that they have the general formula. (MePC) "~ (SO3Y ') vI (2) wherein MePC means the zinc or aluminum phthalocyanine ring system, especially the aluminum phthalocyanine ring system, Y' means hydrogen, an alkali metal or ammonium ion, ν 'means any number between 1.3 and 4 , especially between 3 and 4, R 'means chlorine, bromine or iodine, and x' represents any number between 0.5 and 8, especially between 0.8 and 4, especially such compounds wherein Y 'represents hydrogen, sodium or potassium, ν 'means a number between 2 and 4, preferably between 3 and 4, R1 represents chlorine or bromine, especially chlorine, and x' means any number between 0.8 and 2. Phthalocyanine compounds according to claim 1 or 2, characterized in that MePC means the aluminum phthalocyanine ring system, in particular compounds of the formula (AlPCjT ^ xso3Y ")" wherein A1PC means the aluminum phthalocyanine ring system, x "denotes any number between 0/8 and 1.5, v "means any number between 3 and 4 / and Y" means hydrogen or sodium. A process for the preparation of phthalocyanine compounds of general formula R (MePCj ^ X (1) (SO_Y) 3 v) wherein MePC means the zinc or aluminum phthalocyanine ring system / Y means hydrogen, an alkali metal, ammonium or amine salt, v is any number between 0.1 and 10 4, R is fluorine, chlorine, bromine, iodine or cyano, and x is any number between 0.1 and 8, the substituents R present in the molecule being the same or different characterized by sulfonating a phthalocyanine of formula 15 (MePC -) - Rx especially with oleum, whereupon the resulting sulfonic acid is optionally converted into a salt thereof. Process according to claim 4, characterized in that a phthalocyanine of formula 20 (MePC -) - R X is reacted with chlorosulfonic acid and hydrolyzed the sulfochloride formed. A process for the preparation of phthalocyanine compounds of formula R "(MePCiT x (2) (so3Y) v , v is any number between Q, 1 and 4, R "means chlorine, bromine or iodine, and x means any number between 0.1 and 8, characterized by chlorinating, brominating or iodinating a sulfonated phthalocyanine having the formula (MePC ·) - (- SO 3 Y) v wherein MePC, Y and v have the meanings given above. A process for preparing phthalocyanine compounds of the general formula R 10 (MePexT x (1) (so3Y) v wherein MePC means the zinc or aluminum phthalocyanine ring system, Y means hydrogen, an alkali metal, ammonium or amine salt, v means any numbers between 0.1 and 4, R is fluorine, chlorine, bromine, iodine or cyano, and x is any number between 0.1 and 8, the substituents R present in the molecule being the same or different, characterized by reacting a phthalocyanine of the formula (Ρ0ζ ^ Χ <SO3Y) v 20 wherein PC means the metal-free phthalocyanine ring system and R, x, Y and v have the meanings given above, with a zinc cell aluminum salt or alcoholate.