WO2000059305A1

WO2000059305A1 - Microbicidal composition

Info

Publication number: WO2000059305A1
Application number: PCT/EP2000/002823
Authority: WO
Inventors: Wolfgang Lindner
Original assignee: Troy Chemie Gmbh
Priority date: 1999-04-01
Filing date: 2000-03-30
Publication date: 2000-10-12
Also published as: AU4396700A; DE10080787D2

Abstract

The invention relates to a microbicidal composition which comprises at least one active ingredient selected from groups a) to d): a) 2-methoxycarbonyl aminobenzimidazole or thiabendazole; b) octylisothiazolin-3-one or 3-iodopropinoxy-N-butyl carbamate; c) 2-mercaptopyridine-N-oxide-zinc salt; and d) an N-aryl-N', N'-dimethyl urea derivative or a chlorine-free triazine derivative from the class of 2-methylmercapto-dialkylamino-sym-triazines. The invention also relates to coatings containing the above compound.

Description

Microbiocidal composition

The present invention relates to a special microbiocidal composition, its production and use for coating, inter alia, mineral substrates as well as wood and textiles. The composition contains at least one active ingredient from four groups of different synergistic fungicides and algicides. It is particularly suitable for long-term avoidance of graying and discoloration of coatings, e.g. Facade painting.

Exterior wall and roof coatings that are exposed to the weather and light quickly change color due to dust and vegetation, e.g. Mold, yeast, algae and lichens. The growth with fungi can also affect the coating in its physical properties, e.g. Change adhesive strength, elasticity etc. The changes described are the result of a complex surface process in which physical and microbiological effects interact. One observes, for example, that microorganisms, fungi and algae prefer to settle and grow on soiled facade coatings, or that coatings colonized by algae and fungi quickly turn gray mechanically due to dust build-up.

In particular, coating materials with organic film formers on mineral substrates, textile finishes and wood coatings, but also plastic materials are to be mentioned, which pass through relatively quickly Overgrown algae and mushrooms. As a result, some of these areas become unsightly green to black in just a few months.

Furthermore, the full thermal protection systems with synthetic resin plasters attached to facades today to save energy have a strong tendency to attack algae and fungi due to their physical properties. After just a few weeks in the weather, the brightness decreased and the color changed.

Therefore, the tendency to soiling has been reduced by modifying the coating materials. For example, the binders can be chosen so that the stickiness after film formation is very low. The tendency to discolouration can also be favorably influenced by the choice of fillers and pigments as well as the theological additives. Particular attention has been paid to the adjustment of the water balance within such coating compositions. A quick drying after wetting prevents dust adherence as well as fungus and algae growth. Replacing reinforcement fibers made of cellulose with those made of synthetic materials such as nylon or polyester can also make the coating more stable.

It has also been recognized that the addition of microbiocidal substances to coating materials can delay discoloration and graying. Such substances are said to be easy to handle in a coating-producing factory, typically a paint factory. Furthermore, they are said to have little or no effect on the physical properties of the coating compositions. Especially in today's low-solvent dispersion coatings, fungicidal and algicidal active ingredients in the form of aqueous dispersions are therefore used as additives in order to avoid the introduction of solvents. To prevent discoloration due to microbial influence, modern facade coating compositions now have combined fungicides and algicides, such as a combination of 2-methoxycarbonylaminobenzimidazole (BCM), 2-thiocyanatomethylthiobenzothiazole (TCMTB) and 2-methylthio-4-cyclopropylamino-6-tertiarybutyl , 3,5-triazine, which are described in DE OS 42 42 389. The commercial product MERGAL S 90 PASTE from Troy Chemie consists of 2-methoxycarbonylaminobenzimidazole (BCM), 2-n-octylisothiazolin-3-one (OITZ) and 2-methylthio-4-cyclopropylamino-6-tertiarybutylamino-l, 3,5- triazine (Mctt).

JP-A 110 35 409 describes algicidal and fungicidal compositions comprising triazine and benzimidazole derivatives. These compositions can be used, for example, for circulating water systems, emulsion paints, solvent paints or plastic products made of PVP.

DE-A 197 05 085 describes exterior paints with a mixture consisting of a pyrithione derivative and an algicidally active triazine and optionally a benzimidazole or thiophene derivative, that is to say a combination of two or three classes of compounds having a microbiocidal action, for preventing fouling, in particular by fungi Alternaria genus.

In practice, however, it has been found that coating materials mixed with the additives known from the prior art often do not achieve the desired long-term effectiveness at low use concentrations. For example, on a full thermal insulation facade equipped with 0.1% diuron, significant discoloration due to massive algae growth was observed after only 2 years.

The addition of zinc pyrithione in combination with 2-methoxycarbonylaminobenzimidazole and an algicidal triazine derivative according to DE-A 197 05 085 cannot prevent short-term growth by Alternaria on exposed coatings. This effect cannot be discovered with the "filter test according to the VdL guideline" as a quick test, but it is noticeable on the weathering conditions or in moisture chamber tests.

To date, no solvent-free coating additives that are suitable for comprehensive protection against algae and fungi are known in the prior art.

There is a need for coating materials that allow an extended service life of the coating produced with it, in particular on mineral substrates, but at the same time can be produced economically and do not have a detrimental effect on the environment.

The object of the invention was therefore to provide a microbiocidal composition, in particular for use in coating compositions such as emulsion paints, synthetic resin plasters, silicone resin paints, silicone resin plasters, mineral paints and plasters, pigmented wood coatings based on alkyd resin, which have improved resistance to graying and discoloration due to physico-chemical and exhibit biological processes and thereby get an extended service life. By extending the service life, renovation times are postponed and thus a significant reduction in the effort to maintain the building in terms of environmental protection is achieved.

It has now surprisingly been found that compositions, formulations and coatings according to the invention which, in addition to the customary auxiliaries, e.g. Fillers, binders from the range of acrylates or styrene-acrylates or silicone resins, titanium dioxide pigments, conventional additives to improve the physical properties, contain a combination of at least four active substances from four different classes of substances, which are described below, and protect or discolour them against discolouration and graying. are protected. In addition, the combination according to the invention of the at least four active substances from different substance classes can be provided in a formulation which can be used as an additive in coating materials and does not require any organic solvents and is itself solvent-free.

The present invention thus relates to a microbiocidal composition comprising in each case at least one active ingredient selected from groups a), b), c) and d):

a) 2-methoxycarbonylaminobenzimidazole or thiabendazole, b) octylisothiazolin-3-one or 3-iodopropynoxy-N-butylcarbamate, c) 2-mercaptopyridine-N-oxide zinc salt (ZPT), and d) an N-aryl-N ', N'-dialkylurea derivative or a chlorine-free triazine derivative from the series of 2-methylmercapto-dialkylamino-symmetriazines. Chlorine-free triazine derivatives are those of the formula I.

GCHU

R2 - NH ^' N! L NH -R l

(I),

where Rl and R2 represent alkyl groups, and

N'.N'-dialkylurea derivatives of the formula π

in which

Rl, R2 alkyl groups, preferably methyl,

R5 H, chlorine, bromine, fluorine or alkyl,

R3, R4 represent H, chlorine, bromine, alkyl, trifluoromethyl or O-alyl, where aryl can be substituted, to call.

The above-mentioned active substances of group d) include in particular the following triazine derivatives with favorable physical properties, i.e. properties favorable for preservation, e.g. low water solubility and low vapor pressure:

Ametryn, Desmetryn, Dimethametryn, Dipropetryn, Methoprotryn, Prometryn, Terbutryn and 2-Methylthio-4-cyclopropylamino-6-tertiarybutylamino-l, 3,5-triazine (Mctt), or a mixture of two or more thereof, especially Mctt and / or Terbutryn.

Particularly preferred as N ', N'-dialkylurea derivatives of the formula II as active ingredients d) are the following compounds with favorable physical properties:

Chlorbromuron, chlorotoluron, diuron, difenoxuron, fluometuron, isoproturon, neburon, or a mixture of two or more thereof, in particular diuron and / or isoproturon.

In particular, the following combinations of active ingredients a) to d) are used according to the invention:

BCM, octylisothiazolinone, ZPT and Mctt;

BCM, octylisothiazolinone, ZPT and Terbutryn.

The compositions according to the invention preferably contain the active ingredients a) to d) in the following proportions by weight: a) 1 - 20% by weight, more preferably 3 - 12% by weight, b) 0.5 - 5% by weight, more preferably 1 - 3% by weight, c) 1 - 15% by weight %, more preferably 3 - 10% by weight, d) 1 - 30% by weight, more preferably 4 - 15% by weight,

each based on the total amount of the composition.

Furthermore, the present invention also relates to a microbicidal formulation, preferably a coating composition, with a content of the composition according to the invention of 0.001 to 2% by weight, preferably 0.01 to 1% by weight, in each case based on the total amount of the microbicidal agents Formulation.

The formulation according to the invention can be prepared using conventional methods known to those skilled in the art. It is no different from the production of conventional formulations. The composition according to the invention is added during production as an additional additive.

In addition to the composition according to the invention, the formulation comprises fillers, inert components, solvents and auxiliaries. The facade and roof coating materials consist of

Water, a synthetic resin dispersion and / or a silicone resin as a binder, titanium dioxide of the rutile type as a pigment, commercially available fillers such as calcium carbonate, chalk, Polyacrylate-based dispersants,

Cellulose-based thickeners, xanthan gums, layered silicates, commercially available defoamers, pH regulators, e.g. Ammonia, aliphatic amines, sodium hydroxide solution, potassium hydroxide solution.

The coating compositions can be formulated in a manner known per se. The ingredients are mixed, solid active ingredients being finely ground in water in the presence of the formulation auxiliaries to form a premix and then stirred into the liquid active ingredients. In addition to water, other solvents can be included.

The choice of solvent is not critical. Aromatic petrol, xylene, trimethylbenzene are particularly suitable for non-polar systems; Ketones such as Acetone, cyclohexanone, isophorone, methyl isobutyl ketone; Ethers and glycol ethers such as e.g. Diisopropyl ether, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, esters such as ethyl acetate, butyl acetate; Glycols, their mono- and diethers or their mono- or diesters.

Other additives can be included, such as defoamers, dispersants, emulsifiers, dyes, pigments, film-forming aids, thickeners, rheology modifiers, plasticizers, etc.

Other known antimicrobial substances can also be used in the formulations or coating compositions according to the invention. For example, the following additional fungicides and bactericides may be mentioned: quaternary ammonium salts (quats), such as e.g. Didecyldimethylammonium chloride,

Thiocyanate compounds such as 2-thiocyanatomethylthiobenzothiazole, Carbamates such as iodopropynyl butyl carbamate,

Isothiazolinone derivatives which are different from the substances according to b), e.g. 5-chloro-2-methylisothiazolinone / 2-methylisothiazolinone

Triazole fungicides, e.g. Tebuconazole, propiconazole

Imidazole fungicides, e.g. Prochloraz, Imazalil

Aldehydes, e.g. Formaldehyde or its depot compounds

Nitriles, e.g. Tetrachlorophthalonitrile inorganic oxides such as e.g. Zinc oxide.

Furthermore, the present invention also relates to the use of the formulation according to the invention for the microbicidal finishing of coating compositions, in particular paints, paints or plasters, in particular facade coating compositions, roof tile coating compositions, emulsion paints, synthetic resin plasters, silicone resin paints, silicone resin plasters, mineral paints, mineral plasters and pigmented wood paints based on alkyd resins.

Furthermore, the composition or formulation according to the invention can also be used advantageously in sealants and other technical coatings.

We have now surprisingly found that the coating compositions produced in this way are considerably more stable and more permanent against discoloration and graying than those known hitherto. It has also been found that the coatings are also effectively protected against microorganisms which have been isolated from conventional, fungicidal and algicidal facade coatings.

That is to say, coatings which have the composition according to the invention or are provided with specified active compound mixtures are not covered with vegetation even in regions and resist the discoloration in which finishing with the microbicides customary today is ineffective.

The coatings according to the invention are notable in particular for their high resistance to growth due to a broad spectrum of

Algae such as green algae e.g. of the following types:

Chlamydomonas, Chlorella, Chlorococcum, Microspora, Platymonas, Pleurococcus, Scenedesmus, Stichococcus, Trentepohlia and Ulothrix;

Blue-green algae (Cyanophyta), such as:

Anabaena, Anacystis, Chroococcus, Gleocapsa, Mycrocystis, Nostoc, Oscillatoria, Scytonema and Spirulina;

Yellow-green algae, e.g. Tribonema; Bacteria such as Escherichia coli;

Yeasts such as Rhodotorula spec; and

Mushrooms, such as:

Altemaria altemata, Aspergillus niger, Aureobasidium pullulans, Penicillium funiculosum, Trichoderma viride. In very general terms, the present invention relates to the use of the composition or formulation described above to avoid the graying and discoloration of coatings, in particular exterior paints.

In addition, the composition or formulation according to the invention represents a significant advance over the prior art because it can be easily prepared in user-friendly, solvent-free formulations, is stable in the coating compositions, does not cause discoloration and is therefore easy to use as an additive. The compositions or formulations according to the invention also allow a reduction in the economic outlay, in particular to the extent that the concentrations of the individual active compounds are lower than in the previously known “two or three combinations”. The renovation cycles of the facades provided with the coating agents used according to the invention are also extended This makes a significant contribution to protecting the environment and reducing energy consumption, and coatings on full thermal insulation systems (ETICS) according to the invention are particularly advantageous.

The present inventions will now be explained using a few examples.

example 1

Preparation of an emulsion paint (Table 1) Table 1

Comparison with products from DE 197 05 085 AI (Table 2)

Table 2

The color was produced in a Netzsch dissolver in a manner known from the prior art. For this purpose, water was initially introduced and then the thickeners and other components were introduced and dispersed in the order given in Table 1.

In Examples 2 and 3 below, Sample 1 each represents a formulation without microbicidal active ingredients. Samples 2 and 3 are formulations according to the invention, all other formulations are comparative samples.

Example 2

Growth test against fungi, special Altemaria altemata in a laboratory test (VdL method 06). Preparation and pretreatment of the samples as described in Example 3.

Soak the test specimens for 72 and 144 hours to simulate weathering.

The results of the tests using an emulsion paint from Example 1 are shown in Table 3:

Table 3

An + Pf = Aspergillus niger and Penicillium funiculosum

Ms = Mucor spec.

Aa96820 = Altemaria altemata (wild site strain - 96820)

Example 3

Growth test against algae in the laboratory test (VdL method 05).

The color samples thus obtained were each coated at 300 g / m ² on round filter papers (No. 597 from Schleicher & Schüll, diameter 5.5 cm) and then dried at a temperature of 30 ° C. for 72 hours.

To simulate leaching by rainwater, the test specimens coated with paint were watered with tap water for 72 and 144 hours. The leaching water was changed every 24 hours.

The growth resistance against algae was tested on solid Bold algae nutrient media. After double-sided sterilization under UV light, the dry test specimens were placed on the culture media in petri dishes. In each case 5 ml of a well-grown algae culture in Bold nutrient solution was inoculated onto the surface to be tested under sterile conditions, so that the color surface was pale green. After a incubation period of 14 days at a temperature of 29 ° C, the degree of fouling with algae on the paint coats was assessed visually on a scale from 0 to 4:

0 paint not overgrown

OH paint not overgrown; Formation of an inhibition zone

1 coat lightly overgrown, under 10% of the surface

2 coats overgrown, 10 to 30% of the surface

3 coats overgrown, 30 to 60% of the surface 4 coats overgrown, over 60% of the surface

The results are shown in Table 4:

Table 4

Chf + Stb Chlorella fusca and Stichococcus bacillaris Example 4

Synthetic resin plaster: fouling test against algae in a laboratory test (VdL method 05)

Table 5

The dispersion plaster was prepared analogously to the preparation according to Example 1. In Examples 4 to 7, the respective sample 1 corresponds to a formulation according to the invention and the other samples correspond to comparison samples.

Mctt was always used as triazine in the sample according to the invention and in comparison samples 2 and 4, while comparison samples 3 and 5 contained terbutryn as triazine.

The results of Example 4 are shown in Table 6:

Table 6

Example 5

Synthetic resin plasters: fouling test against fungi, especially Altemaria altemata in a laboratory test (VdL method 06).

The results of the review are shown in Table 7:

Table 7

Example 6

Fouling test against algae in a wet chamber test (ITECH method)

According to the test method developed by Prof. Boulon at ITECH, Lyon, the test specimens were exposed on calcium silicate carriers in a warm, humid climate, irrigated and exposed to extremely high algae concentrations. A flora of bacteria, fungi and algae developed in the chamber. Algae solutions from Chlorella fusca, Stichococcus bacillaris, Trentepholia odorata were inoculated.

The test duration was 6 weeks. The results are shown in Table 8:

Table 8

Example 7

Testing the discoloration-stabilizing effect in outdoor weathering.

The synthetic resin plasters from Example 6 were weathered on a weathering stand in Seelze with a 45 ° inclination to the north. To check the color changes, Lab values were measured before the start of the test and during weathering. Table 9 shows the results:

Table 9

Claims

claims

1. Microbicidal composition comprising in each case at least one active ingredient, selected from groups a), b), c) and d):

a) 2-methoxycarbonylaminobenzimidazole or thiabendazole, b) octylisothiazolin-3-one or 3-iodopropynoxy-N-butylcarbamate, c) 2-mercaptopyridine-N-oxide zinc salt, and d) an N-aryl-N ', N'- dialkylurea derivative or a chlorine-free triazine derivative from the series of 2-methylmercapto-dialkylamino-sym-triazines.

Composition according to approach 1 with the following proportions by weight of active ingredients a) to d):

a) 1 - 20% by weight,

b) 0.5-5% by weight,

c) 1-15% by weight,

d) 1-30% by weight, based in each case on the total amount of the composition and at least 30% by weight of conventional auxiliaries.

3. Composition according to claim 2, with the following proportions by weight of the active ingredients a) to d):

a) 3 - 12% by weight

b) 1-3% by weight

c) 3 - 10% by weight

d) 4 - 15 wt .-%, each based on the total amount of the composition.

4. Microbicidal formulation, the content of the composition according to any one of claims 1 to 3 of 0.001 to 2 wt .-%, preferably

0.01 to 1 wt .-%, based on the total amount of the microbiocidal formulation, and conventional auxiliaries.

5. Use of the microbiocidal formulation according to spoke 4 for the microbiocidal finishing of coating agents.

6. Use according to claim 5, wherein the coating agent is a facade coating agent, roof tile coating agent, emulsion paint, synthetic resin plaster, silicone resin paint, silicone resin plaster, mineral paint, mineral plaster, or a pigmented wood paint

Alkyd resin base.

7. Use of the microbiocidal composition or formulation according to one of claims 1 to 4 to avoid graying and discoloration of coatings. A method of making a formulation as claimed in Claim 4, which comprises:

Mixing of the components, solid active ingredients being finely ground in water in the presence of the formulation auxiliaries, and the liquid active ingredients are then stirred in.