DK159183B - PROCEDURE FOR COMBATING MICRO-ORGANISMS AND ANTIMICROBIAL AGENT - Google Patents

Description

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DK 159183 B

The present invention relates to a method for controlling microorganisms in or on organic or inorganic substrates or for protecting them against microorganism attacks, as well as antimicrobially active agents for carrying out the process.

DE-Publication No. 2,812,261 discloses a method for controlling microorganisms on various substrates by means of water-soluble phthalocyanine compounds, e.g. aluminum phthalocyanine compounds, especially 10 sulfonated aluminum phthalocyanine, as well as an agent containing this compound as an active substance.

SUMMARY OF THE INVENTION It is an object of the invention to provide a method for controlling microorganisms on various substrates and a corresponding means for carrying out this method which is more efficient, economical and more favorable than those known from the aforementioned DE Publication No. 2,812,261. agents. Surprisingly, it has been found that the use of sulfonated zinc and aluminum phthalocyanines, further substituted by neutral, non-water-solubilizing groups, significantly increases the efficiency of the known process.

The method of the invention for controlling microorganisms in or on organic or inorganic substrates or for protecting them against microorganism attack by treating the substrates to be liberated or protected against microorganisms with water-soluble zinc or aluminum phthalocyanines in the presence of water and under irradiation with light is peculiar in that as water-soluble zinc or aluminum phthalocyanines, sulfonated zinc or aluminum phthalocyanines are used which are further substituted by neutral, non-water-soluble groups, e.g. with halogen atoms or pseudohalogenes or mixtures of such phthalocyanine compounds.

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Particularly suitable zinc or aluminum phthalocyanines for use in the process of the invention are those of formula (MePC) x (1) ^ (SO-Y) 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 1 and 4, R means fluorine, chlorine, bromine, iodine or cyano, and x is any number between 0.1 and 8, present in the molecule. substituents R may be the same or different.

Particularly preferred among the compounds of formula (1) are those of formula R *, (MePC) X (2) "(so3Y ') v, wherein MePC means the zinc or aluminum phthalocyanine ring system, Y' means hydrogen, an alkali metal or ammonium ion, ν 'is any number between 1.3 and 4, R' means chlorine or bromine, and x 'is any number between 0.5 and 8.

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

In particular, among the compounds of formula (2) for use in the process of the invention are those wherein Y 'is hydrogen, sodium or potassium, v * is any number between 2 and 4, especially between 3 and 4, R "means chlorine or bromine, preferably chlorine, and x 'means any number between 0.8 and 2, for example those wherein Y' means hydrogen, sodium or potassium, ν 'is any number between 3 and 4, R' is bromine and x 'is a will-

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3 small numbers between Q, 5 and 1.5.

In the process of the invention, it is particularly preferred to use said aluminum phthalocyanine compounds, especially those of formula 5 (AlPC * (3) ^ (so3Y ") v" wherein AlPC 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.

The compounds of formulas (1) and (2) as well as the preferred compounds derived therefrom are novel compounds.

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 + / R 1 HN - R 1 R 3 wherein R 2 1-4 carbon atoms, at least one of the 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. As

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4 examples of such heterocyclic compounds can be mentioned 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 required in the molecule also depends on the number of substituents present. In all cases, so many sulfo groups must be present to ensure that a sufficient water solubility. A minimum solubility of 0.01 g / l may be difficult, but usually a solubility of 0.1-20 g / l is appropriate.

To exert their antimicrobial action, the zinc and aluminum phthalocyanine compounds useful in the process of the invention require the presence of oxygen and water as well as irradiation with light. It is therefore used in aqueous solutions or on moist substrates, and as the source of oxygen, the dissolved oxygen or the oxygen of the air serves. The presence of reducing agents Destroys or diminishes the effect of the substances.

The irradiation can be done 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, the radiation can, for example, 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 time than at higher intensity. Usually, depending on the field of application, it is possible to use lighting times of from a few minutes up to a few hours.

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

Already at very low concentrations of effective compound, e.g. at 0.001 ppm, good antimicrobial effects can be obtained. 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 the fact that an excess of 15 would result in 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 zinc and aluminum phthalocyanine compounds used in the process of the invention have a very broad spectrum effect against microorganisms. Thus, in the method of the invention, Gram-positive and Gram-negative bacteria can be combated primarily or various substrates can be protected from attack by these bacteria. There is also an excellent effect against fungi and yeast fungi.

The process according to the invention can furthermore add effect-enhancing compounds, i.a. 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 composition of the invention, 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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6

Due to the aforementioned broad spectrum action against microorganisms, the method of the invention or the present invention can be used in a variety of areas, 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 method of the invention. For this purpose, the laundry can be treated with aqueous solutions 10 of 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 conventional detergents, 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 it is either irradiated with a suitable artificial light source or simply 25 is exposed to the sunlight.

The antimicrobial active compounds can be added directly to the disinfection or washing fleet. However, they can also be incorporated into soaps or washing powders 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 amino glycerates, fatty alcohols, etc., so-called "builders" e.g. alkali metal poly and polymethaphosphates,

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7 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 microbial 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 process 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 method according to the invention and the agent according to the invention is the disinfection of hospital laundry, medical supplies 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 as well as floor 25 and wall surfaces can be treated with aqueous solutions containing the sulfonated zinc and 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

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8 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 method and means of the invention can also be used for bathing and disinfecting swimming pools.

To this end, the water in the swimming pool is suitably added to one or more of the phthalocyanine compounds useful in the process of the invention, preferably in an amount of between 0.001 and 50, especially between 0.01 and 10 ppm.

15 Lighting is done simply by means of the sunlight. Optionally, additional lighting can be made using 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 process according to the invention can be used for the decontamination of wastewater from clarifiers. For this purpose, e.g. 0.001-100, in particular 0.01-10 ppm, of one or more of the phthalocyanine compounds used in the wastewater used in the process of the invention. The irradiation is conveniently done by means of the sunlight, and further irradiation can be carried out with artificial light sources.

The above uses are only examples of the very broad scope of the process of the invention.

The invention also relates to antimicrobially effective agents for carrying out the process of the invention.

These agents are characterized in that they contain one or more sulfonated zinc and / or aluminum phthalates.

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9 cyanines that may be additional. substituted with neutral, non-water-solubilizing groups. Preferably, these agents contain phthalocyanine compounds of formulas (1) and (2) and their particularly preferred compounds, e.g. compounds of formula (3). In addition, said agents may also, according to the field of application, contain conventional formulation ingredients.

Preferred agents of this type contain one or more of the zinc or / and aluminum phthalocyanine compounds defined above, one or more inorganic salts, e.g. NaCl, KCl, NaBr, KBr, K2 SO4, Na2 SO4, K2CO3, Na2CO3, NaHCC> 3 and others, especially NaCl or / and Na2 SO4, and optionally water. Such an agent may consist, for example, of 50-80% of a compound of formula (1), especially of formula (2) or (3), 10-30% of NaCl 15 and / or Na2SC> 4, e.g. 5-15% NaCl and 5-15% Na2 SO4, and 0-30% water. These agents may also be in the form of aqueous solutions, e.g. in the form of a 5-50%, e.g. 5-20% solution.

As previously stated, the subject antimicrobial agents contain one or more sulfonated zinc or / and aluminum phthalocyanines which are further substituted by neutral, non-water-solubilizing groups, especially those of formulas (1) and (2) and those thereof. included particularly preferred compounds, e.g. those of formula (3), as well as optionally conventional formulation ingredients.

Preferred agents of this type contain one or more of the above defined aluminum phthalocyanine compounds, one or more inorganic salts such as NaCl, KCl, NaBr, KBr, K2 SO4, Na2 SO4, K2CO3, Na2CO3, NaHCO Na2 SO4 and optionally water. An agent of this type, for example, consists of ca. 50-80% of a compound of formula (1), especially of formula (2) or (3), 1-30% of NaCl and / or Na2SC> 4, e.g. 5-15% NaCl and 5-15% Na2 SO4, and 0-30% water.

This agent may also be in the form of an aqueous solution.

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10, e.g. in the form of a 5-50%, e.g. 5-20% solution.

The present detergents having antimicrobial effect contain, in addition to the active zinc or / and aluminum phthalocyanine, common detergent ingredients / e.g. one or more 5 organic detergents and basic builder substances.

The disclosed antimicrobially effective detergents contain e.g. the known mixtures of detergents, e.g. soap in the form of cuts or powders, synthetics, soluble salts of sulphonic acid halves of higher fatty alcohols, higher and / or multiple alkyl substituted aryl sulphonic acids, sulphocarboxylic acid esters with moderate to higher alcohols, fatty acid acylaminoalkyl oleoacrylate or amino amino acid glycerides, for example, builders "may be used alkali metal salts of carboxymethyl cellulose and other" soil redistribution inhibitors ", furthermore alkali metal silicates, alkali metal carbonates, alkali metal borates, alkali metal perborates, alkali metal percarbonates, nitrilotriacetic acid, ethylenediaminic acid, ethylenediaminic acid, ethylenediaminic acid

Further, for example, the detergents may contain, for example, antistatic agents, skin protection agents that supply the skin with fat, such as lanolin, enzymes, antimicrobials, perfumes, and optical clarifiers.

The present antimicrobially active detergents contain the sulfonated zinc or aluminum phthalocyanine compounds in an amount of preferably 0.0005 to 1.5, especially 0.005 to 1% by weight, based on the total weight of the detergent.

The present antimicrobially active detergents contain, for example, 0.005-1% by weight of the above-mentioned sulfonated zinc or / and aluminum phthalocyanine compounds, 10-50% by weight of anionic, nonionic, semipolar, ampholytic or / and amphionic surfactant, 0-80 % of a basic filler salt and optionally additional conventional detergent

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11 constituents, e.g. those listed above.

For example, as surfactants in the present compositions, water-soluble alkylbenzene sulfonates, alkyl sulfonates, ethoxylated alkyl ether sulfates, paraffin sulfonates, α-olefin sulfonates, alpha sulfocarboxylic acids, salts and esters thereof, alkyl glyceryl ether sulfonates, fatty sulfonates or fatty sulfates, ethoxy-ether sulfates, 2-acyloxyalkanesulfonates, β-alkyloxy-alkanesulfonates, soaps, ethoxylated fatty alcohols, alkylphenols, polypropoxy glycols, polypropoxyethylenediamines, amine oxides, phosphine oxides, sulfoxides, aliphatic secondary and tertiary amines, aliphatic ammonium and tertiary amines, sulfonium compounds or mixtures of these compounds.

As examples of basic filler salts which may be present in the present compositions in an amount of 10-60% by weight, Mention is made of water-soluble alkali metal carbonates, borates, phosphates, polyphosphates, hydrogen carbonates and silicates, water-soluble aminopolycarboxylates, phytates, polyphosphonates and carboxylates, and water-insoluble aluminum silicates.

The sulfonated zinc and aluminum phthalocyanine compounds used in the present process and in the present compositions can be prepared using 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, phthalodinitrile 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 substituents can also be introduced into the already built up phthalo-

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12 cyanine ring system, e.g. by chlorination, bromination or iodination (R = Cl, Br, J). The sulfonic acid groups can be introduced before (cf., for example, U.S. Patent No. 2,647,126) or later. If the structure of the phthalocyanine ring system is carried out from phthalic anhydride or phthalodinitrile in the presence of chlorides, e.g. AlCl3 or ZnCl2, phthalocyanines are formed which are already chlorinated, especially with a chlorine content of 0.5-1.5 moles of chlorine per liter. 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 both cases, the free sulfonic acid groups can then be transferred into 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 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 or aluminum salt or alcoholate.

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

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13 after the introduction of the halogen atoms.

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

Thomas "Phthalocyanine" (1963, pages 104 et seq.). Halogenated phthalocyanines or phthalocyanines containing other inert substituents can be prepared by mixing condensation of unsubstituted or similarly substituted phthalic acids or phthalic acid derivatives using conventional methods known from the phthalocyanine chemistry. 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 (Examples 1-5) and the process of the invention, parts and percentages are 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 appear in the preparation in part as sodium salts. Therefore, as is common from the dye chemistry, the group -SO3H also includes the sodium salts thereof. The x ^ ax values of the absorption spectrum used to characterize the phthalocyanine compounds are determined in a mixture of ethanol 25 and water (1: 1) at pH 7.

Example 1.

a) Place in an autoclave 128 g of phthalic acid dinitrile, 40 g of AlClg 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 400 ml of water containing 100 g of trisodium phosphate with stirring. Then the mixture is evaporated to dryness on a rotary evaporator, the crude product is stirred with 750 ml of water and then added

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14 60 g of 50% sodium hydroxide solution are heated to 75 ° C and 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 90-5 ° C), then filtered hot and washed. In this way, an aluminum phthalocyanine containing 1 mole of bound chlorine is prepared. moth.

b) 60 parts of the monochloro-aluminum-phthalocyanine prepared according to (a) are added to 260 volumes of 10 parts 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 1/2 hour 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 parts 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-r60 ° C. The saponification can be accelerated by the addition of catalytic amounts of pyridine.

After saponification, the slightly basic solution 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 (AlPC) Cl (SO 2 H) -. with a λ value of 674 nm. ό «5 - *" "4 max

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15

Example 2.

a) 118 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 molyhdate 15 parts of aluminum chloride and 200 parts by volume of trichlorobenzene (isomer mixture) are stirred thoroughly in a stirring flask. The mixture is heated to 195-205 ° C over 3 hours, after which the stirring is continued at this temperature for 16 hours. After cooling, add 500 parts by volume of isopropanol and stir for a short time, then suction filter the suspension. Wash the residue with 500 parts by volume of isopropanol. The residue is taken up in 800 parts by weight dilute sodium hydroxide solution and stir for 2 hours at 80-90 ° C. and washed with warm water. This is repeated in dilute hydrochloric acid, whereupon the formed pigment 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 according to (a) are transferred to (20.7) using the procedure of Example 1b) in the corresponding sulfo group-containing compounds. In this way,

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16 repeating compounds: (211) (AlPC) Cl (SO, Η),, λ = 674 nm 3 3-4 max (212) (A1PC) Cl2 (SO3H) 3_4 (213) (A1PC) C14 (SO3H) 3_4 5 (214) (AlPC) Br (SO, H), λ = 675 nm 3 3-4 max (215) (AlPC) Br, (SO, H) _ - = 677 nm 4 3 3-4 max (216) (AlPC) J (SO, Η),, λ, = 678 nm

o «3 4 ITlcLX

(217) (AlPC) 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 carried out by extraction 15 with hot dilute sodium hydroxide solution, hot water, hot 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 raonobromo-aluminum phthalocyanine 20 prepared according to a) is reacted analogously to the process described in Example Ib) with chlorosulfonic acid, and the monobromo-aluminum-phthalocyanine sulfochloride formed is transferred into 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 (AlPC) Br (SO, H) ,. (λ = 675 nm).

By analogy to the methods described in Example 1b) or Example 3b, however, instead of monochloro-aluminum phthalocyanine or monobromo-aluminum phthalocyanine, similar amounts of monofluoro, monoiod or monocyano-aluminum phthalocyanine are used, products of similar composition, namely A1 ( ) F (SO3H) 3_4, (AlPC) J (SO3H) 3_4 (Amax = 67.8 nm) and (AlPC) CN (SO3H) 3_4. The fluorine, iodine or cyanosubstituted aluminum phthalocyanines can be prepared

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17 analogously 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 1 hour 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 initially used monochloro-zinc phthalocyanine 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 ZnC 2

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Similarly, zinc phthalocyanine sulfonic acids of formula (ZnPC) F (SO3H) 3_4, (ZnPC) Br (SO3H) 3_4 / (ZnPC) J (SO3H) 3_4 and (ZnPC) CN (SO3H) 3_4 are prepared.

Example 5

5 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 200 parts by volume of isopropanol and suction filtered, after which the residue is washed with 200 parts by volume acetone. The residue is stirred in 800 parts by volume of dilute sodium hydroxide solution for 2 hours at 80-90 ° C, then 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.

Analogous 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: 25 (502) Tetrachlorzinc phthalocyanine (503) Monobromed Zinc Phthalocyanin (504) Tetrabrom Zinc Phthalocyanine (505) Monoiod Zinc Phthalocyanin (506) Diode Zinc Phthalocyanin

B) The halogenated phthalocyanine pigments (501) to (506) prepared according to (a) are transferred analogously to the process described in Example 4 in the corresponding sulfogroup-containing compounds. In this way, the following compounds are prepared:

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19 (511) (ZnPC) Cl (SO3H) 3_4 = 670 ran (512) (ZnPC) Cl4 (SO3H) 3_4 = 672 ran (513) (ZnPC) Br (SOoH) ^, λ = 669 ran (514) (ZnPC ) Br4 (SO3H) 3_4 5 (515) (ZnPC) J (SO3H) 3_4.

(516) (ZnPC) J2 (SO3H) 3_4

Example 6

Test for Effect against Bacteria and Fungi Method 10 An aqueous solution containing (AlPC) Br (SO3H) 3_4 or (AlPC) J (SOgH) 3_4 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 amount 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. Then, lighting is done with an incandescent or infrared lamp (infrared "Weiss" lamp,

Philips IR., 250 W, type 13372 E / 06), which is at a distance of 20 cm above the suspension surface, for 20 5, 10, 20, 30 and 60 minutes respectively. The seed count is then determined in the usual way by parallel counts. The germ in question

- N

reduction is calculated in tier potentials by the formula x = -log1Q, where Nq is the initial germination number and N is the number of surviving germs (average value of 5-10 parallel counts).

By comparison, the effect of (AlPC) (SC> 3H) 3__4 is determined in exactly the same way.

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

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20

Table I.

Exposure time in minutes ppm 5 10 ....... 2.0 ....... 30. 60 0.01 for low effect 0.1 0.5 5 (A1PC) (SO3H) 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 (SO 3 H) 3_4 0.1 1.6 2.4 3.2 3.7 4.5 1.0 3.3 4.0 > 4.6> 4.6> 4.6 10 0.01 1.0 1.8 2.7> 4.6> 4.6 (AlPC) J (SO3H) 3_4 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 (AlPC) Br (SO3H) 3_4 and (AlPC) 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 (AlPC) (SO 3 H) 3_4.

Similarly good results are obtained with compounds 20 (A1PC) F (SO3H) 3_4, (A1PC) C1 (SO3H) 3_4, (AlPC) CN (SO3H) 3_4, (AlPC) Cl2 (SO3H) 3_4, (AlPC) Cl4 (SC H) 3_4, (AlPC) Br (SC ^ H) 3_4, (AlPC) Br4 (SO3H) 3_4, (AlPC) J (SO3H) 3_4, (AlPC) J2 (SO3H) 3_4, (ZnPC) Cl (SO3H) 3_4 , (ZnPC) Br (SO3H) 3_4, (ZnPC) J (SO3H) 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 Eschericia 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 effect of the corresponding pure zinc or aluminum phthalocyanine sulfonic acid (without additional halogen or pseudohalo 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 15 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, but no microbicide compound is present. 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 (AlPC) Br (SO3H) 3_4 on Strept is tested. faecalis var. zymogenes 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 seeded with a Staphylococcus aureus ATCC 6538 seed suspension, whereby approx. 10 germs 30 are evenly distributed on the surface of a tile. Then the surface is sprayed with an aqueous solution containing 1 ppm off

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The compound of formula (AlPC) Cl (SO 2 H) 3_4, (AlPC) Br (SO 2 H) 3_4 or (AlPC) J (SOgH) 3_4. Then the surface is illuminated with a light bulb (250 W, distance 20 cm) for 30 and 45 minutes respectively.

When the lighting is complete, sampling is done at 5 knock-offs in Rodac bowls. After 30 minutes, in the case of treatment with (AlPC) Cl (SO 3 H) 3_4, 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 -10 states any germ growth.

Using the others of Example 6. as test compounds indicated by halogenated or CN-substituted phthalo-cyanine 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 the test compounds.

Example 9

Waste water decontamination from a clarifier 20 A sludge sample is taken from a laboratory clarifier and the sample is filtered through a paper filter. For the filtrate containing approx. 10 g / ml, a phthalocyanine compound of formula (AlPC) C1 (SC> 3H) 3_4, (AlPC) Br (SO3H) 3_4 or (AlPC) J (SC> 3H) 3_4 is added until the concentration of the filtrate 25 is 1 ppm. Then the filtrate is illuminated with standard light 380-2730 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 illumination time (from 1 to several hours) the number of the other germs present in the filtrate also decreases clearly.

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Example 1Q.

Swimming pool descent In open air, swimming pools are set up, each containing 5000 liters of water. To the water in a basin, compound 5 of formula (AlPC) Cl (SO 3 H) is added 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 number of germs is determined and b) the number of coliform germs.

10 Results In pools that do not contain monochloroaluminum phthalocyanine sulfonic acid, the coliform germs are propagated to 2-3 x 101 germ / 100 ml. In the basins containing the active substance, no coliform germs are observed until the 15th day of testing.

For a further experiment, a seed suspension containing Staphylococcus aureus ATCC 6538 and Eschericia coli ATCC 11229 is added at an amount of 50 germ per gram. 100 ml basin content for the water on the sixteenth day of the experiment. 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 consisting of autochthonous (derived from the swimming pool) seedling flora remains constant during the experiment.

Claims (12)

2nd DK 159183B 1. A method for controlling microorganisms in or on organic or inorganic substrates or for protecting them against attack by microorganisms by treating the substrates to be liberated or protected against microorganisms with water-soluble zinc or aluminum phthalocyanines in the presence of water and under irradiation with light, characterized in that, as water-soluble zinc or aluminum phthalocyanines, 10 are used sulfonated zinc or aluminum phthalocyanines, which are further substituted with neutral, non-water-solubilizing groups, e.g. with halogen atoms or pseudohalogens, or mixtures of such phthalocyanines. Process according to claim 1, characterized in that, as zinc or aluminum phthalocyanines, those of formula R (MePC) 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 is any number between 1 and 4, R is fluorine, chlorine, bromine, iodine or cyano, and x is any number between 0.1 and 8, present in the molecule groups R are the same or different.1 A process according to claim 2, characterized in that, as zinc or aluminum phthalocyanines, those of the formula R ', (MePC)' 'X (2)' '(soy, the zinc or aluminum phthalocyanine ring system, preferably the aluminum phthalocyanine ring system, Y '30 represents hydrogen, an alkali metal or ammonium ion, ν' is any number between 1.3 and 4f, preferably between 3 and 4, R 'means chlorine, bromine or iodine, and x 'is any number between 0.5 to 8, preferably between 0.8 and 4. Process according to claims 2-3, characterized in that a phthalocyanine of formula (1) or (2) is used, wherein MePC means the aluminum phthalocyanine ring system, preferably one of the formula (Aipac '' 01'1 ''). wherein "AlPC means the aluminum phthalocyanine ring system, x" is any number between 0.8 and 1.5, v "is any number between 3 and 4, and Y" means hydrogen or sodium. Process according to claim 1, characterized in that the substrates are treated in or with an aqueous bath containing one or more of the sulfonated zinc or aluminum phthalocyanine compounds defined in claims 2-4, or incorporating these compounds. in the substrates, if they consist of water or contain such, and irradiate the substrates with an artificial light source, preferably an incandescent or infrared lamp, either in the treatment bath or outside thereof, or irradiate the substrate with sunlight, either directly in the treatment bath or in the aqueous substrate or after removal from the bath in a moist state. Method according to Claim 5 for desiccating laundry, characterized in that the laundry is washed under infrared and / or visible light irradiation in a washing float containing, in addition to usual detergent components, 0.001 to 100 ppm of one or more of the claims 2-4 defined phthalocyanine derivatives and optionally an inorganic salt. A method according to claim 1 for surface germination, e.g. of floors, walls, furniture, etc., characterized in that said surfaces are applied to an aqueous solution containing one or more of the phthalocyanine compounds defined in claims 1-4, to which the still moist surfaces are exposed to sunlight and possibly another 5 are illuminated with an artificial light source that emits infrared and / or visible light. Process according to Claim 1 for bathing water in swimming pools, characterized in that 0.001-50, preferably 0.01-10 ppm of one or more of the phthalocyanine derivatives defined in claims 1-4, is added, the water in addition to Radiation with sunlight can also be irradiated with an artificial light source. Process according to claim 1 for the decontamination of sewage from clarification plants, characterized in that 0.001-100, preferably 0.01-10 ppm of one or more of the phthalocyanine derivatives defined in claims 1-4 are added, with sunlight can also be irradiated with an artificial light source. -. 10. Antimicrobial agent known to contain one or more of the sulfonated zinc or / and aluminum phthalocyanine compounds defined in claims 1-4. An agent according to claim 10, characterized in that, in addition to one or more of the sulfonated zinc or / and aluminum phthalocyanine compounds defined in claims 2-4, it contains one or more inorganic salts, e.g. NaCl or Na2 SO4, and optionally water. An agent according to claim 10, characterized in that it contains one or more of the sulfonated zinc or / and aluminum phthalocyanine compounds defined in claims 2-4 and optionally ordinary detergent ingredients.