CH625678A5 - Fungicide - Google Patents

Description

The invention relates to fungicidal compositions and their use in building protection and paint.

Technical products such as paints, plasters, fillers and sealants, plastic coatings, putties, adhesives and the like. can be infected by fungi. Biodegradable components of the technical materials serve as nutrients, and especially in the vicinity of food and luxury goods companies, dust from the products produced. Fungus infestation leads to discoloration and damage, the removal of which causes considerable economic losses. In areas of the food industry, fungal coatings can be a dangerous source of infection. For hygienic reasons, fungal infestation should therefore be avoided as far as possible. Building protection and sealing materials are therefore becoming more and more fungicidal.

It is known that both benzimidazole compounds and chloroacetamide, N-hydroxymethyl-chloroacetamide and other formaldehyde depot compounds have a microbicidal action. Benzimidazole compounds are widely used, e.g. for combating fungi in agriculture and against discoloring fungi in wood preservation. Chloroacetamide and formaldehyde depot substances have long been used for preservation, e.g. of paints and cooling lubricants.

Surprisingly, it has now been found that mixtures of a) 20 to 80% of at least one benzimidazole compound of the formulas I and II

(Xh?

/ C-N-C-OR1

H

II

or the corresponding salts with a (C12- to Ci8) -alkan-2o sulfonic acid, or with dodecylbenzenesulfonic acid and in which Rt is a (Q- to C4) -alkyl group and R2 is a (Q- to C18) -alkyl group, and b) 80 to 20% of at least one amine compound from the group chloroacetamide, N-hydroxymethylchloroacetamide, N-25 hydroxymethylethanolamine and addition or condensation product of formaldehyde and melamine, in particular with 3-6 moles of formaldehyde per mole of formaldehyde per mole of melamine or from formaldehyde and primary hydroxyalkylamines, which contain 2-6 carbon atoms in the alkyl radical, have a fungicidal activity even at concentrations which are considerably lower than the substances on their own. This increase in activity is achieved both by mixtures of benzimidazole compounds and chloroacetamide and by mixtures of benzimidazole compounds and formaldehyde depot-35 substances.

The agents according to the invention can be used particularly in the field of building protection to avoid fungal attack. They are fixed in the materials and are not leached from them or only under extreme conditions. There will be no adverse changes to the finished products, e.g. Discolouration, impairment of viscosity or delays in drying. The agents do not pollute the environment as they are free from harmful heavy metals and toxic polychlorinated compounds. They are also biodegradable. The mixtures according to the invention act against various types of fungi, such as e.g. Alternaria consortiale, Aspergillus niger and Pénicillium funiculosum, but also against Aureobasidium pullulans and Chaetomium globosum. Other microbicides, e.g. those with predominantly bactericidal activity can also be used.

Possible application amounts are 0.3-5% by weight of the agent containing the fungicidal mixture, based on the amount of the building protection agent or paint to be treated.

The fungicidal activity of the agents according to the invention was tested in the growth inhibition test using known methods. A mushroom culture medium consisting of 3% malt extract, 3% agar agar and 94% water was used. Graduated amounts of the test mixtures were added to each 20 ml of culture medium 6o and filled under sterile conditions in standard petri dishes with a diameter of 9 cm. Inoculation was carried out with spore suspensions of inclined tube cultures. Each Petri dish was mixed with approximately 100,000 germs from the respective test organism. Be-65 was incubated for 2 weeks at an optimal growth temperature of 28 ° C and 75% relative humidity.

Tables 1 and 2 show the minimum inhibitory concentrations (MIC values) based on the weight of the nutrient

3rd

625 678

the listed. At these concentrations, fungal growth is completely inhibited. At the next lower concentration there was still a clear inhibitory effect, but as a rule the test mushrooms grew in area within a week. In Table 1, the inhibitory concentrations determined are 5

concentrations of the individual components used in the mixtures according to the invention. Table 2 shows the values of examples of the mixtures according to the invention.

Abbreviations in the following tables:

A.c .: Alternaria consortiale

A. n .: Aspergillus niger

A. p .: Aureobasidium pullulans

C. g .: Chaetomium globosum

P. f .: Pénicillium funiculosum.

Table 1

Fungicidal action of components of the mixtures according to the invention, substance MIC values in%

A. c.

At.

A. p.

C. g.

P.f.

A)

2-methoxycarbonylamino benzimidazole

1

0.0005

0.00005

0.00005

0.00005

B)

2-methoxycarbonylamino-benzimidazole

4'-dodecyl benzenesulfonate

0.02

0.0005

0.0001

0.00005

0.0001

C)

2-methoxycarbonylamino-benzimidazole

dodecyl sulfonate

0.05

0.0005

0.0002

0.00005

0.0002

D)

l-methoxycarbonyl-3-dodecyl-s-

hexahydro-triazino-benzimidazole

0.1

0.001

0.0001

0.0001

0.0002

E)

l-methoxycarbonyl-3-octadecyl-s-

hexahydro-triazino-benzimidazole

0.2

0.0002

0.00005

0.00002

0.0005

1)

Chloroacetamide

0.1

0.2

0.05

0.05

0.1

2)

N-hydroxymethylchloroacetamide

0.1

0.05

0.05

0.05

0.1

3)

N-hydroxymethylethanolamine

0.1

0.5

0.2

0.2

0.2

4)

Tris-hydroxymethyl-melamine

0.2

0.2

0.1

0.05

0.05

5)

Hexahydroxymethyl melamine

0.2

0.2

0.2

0.05

0.1

Table 2

Fungicidal activity of mixtures according to the invention

substance

MIC values in% A. c.

At.

A. p.

c. G.

P.f.

40% A)

60% 1)

0.02

0.0002

0.0001

0.00005

0.0001

20% A)

80% 1)

0.02

0.0005

0.0001

0.0002

0.0001

40% A)

60% 2)

0.01

0.0005

0.00005

0.0001

0.00005

40% A)

60% 4)

0.05

0.0002

0.00005

0.00002

0.00005

60% A)

40% 5)

0.05

0.0002

0.00005

0.00002

0.00005

50% B)

50% 1)

0.02

0.0002

0.0001

0.00005

0.0001

60% C)

40% 1)

0.02

0.0002

0.00005

0.00005

0.0001

60% D)

40% 2)

0.05

0.0005

0.0001

0.00005

0.0001

30% E)

70% 3)

0.05

0.0002

0.00005

0.0001

50% A)

25% 1)

25% 2)

0.02

0.0002

-

0.00005

50% A)

25% 2)

25% 4)

0.02

0.0002

0.00005

0.01) 002

0.00002

50% B)

25% 2)

25% 3)

-

0.0002

0.0001

0.00002

0.0001

625 678

To determine the increase in activity, these MIC values were evaluated in accordance with the formulas given in DE-OS 1 950 677.

Then the increase in effectiveness is calculated as follows:

^ r _ 200 (calculated H - found H)

H calculated

H = minimum inhibitory concentration in%

H calculated is determined using the following equation:

H calculated = or

H calculated =

100 • Ha • H2 MrH2 + M2-H,

100 • Hj • H2 • H3

5 Mj-Ha-Hs + Mj-Hj + Ms-Hj-H ;;

Mi, M2, M3 =% contents of the components in the mixture H ,, H2, H3 = minimum inhibitory concentrations (in%) of the components.

The values obtained for the increase in activity in% io are shown in Table 3.

Table 3

Effectiveness in the mixtures according to the invention

Mixture% increase in effectiveness

A. c. A. n. S. p. C. g. P. f.

40% A) + 60% 1)

174

168

40

120

40

20% A) + 80% 1)

167

160

120

40

120

40% A) + 60% 2)

187

119

160

40

120

40% A) + 60% 4)

174

120

120

168

120

60% A) + 40% 5)

166

152

80

152

80

50% B) + 50% 1)

80

160

100

98

100

60% C) + 40% 1)

136

152

170

133

140

60% D) + 40% 2)

100

139

80

140

140

30% E) + 70% 3)

115

140

140

-

188

50% A) + 25% 1) + 25% 2)

178

160

-

-

100

50% A) + 25% 2) + 25% 4)

183

160

160

160

160

50% B) + 25% 2) + 25% 3)

-

160

100

160

100

In addition to determining the MIC values, the fungicidal effect was tested in a practical “filter test”. For this purpose, graduated amounts of 0.1-1% of the mixtures according to the invention were incorporated into various emulsion paints which had not been treated to be fungus-resistant, into cleaning material and into a commercially available casein-bound filler. The materials were then evenly applied on one side to circular paper filters with a diameter of 5.5 cm. After drying for several days and subsequent sterilization by UV exposure, the test specimens were placed with the uncoated side on nutrient media in petri dishes inoculated with a spore suspension of the respective test fungus. These Petri dishes were incubated for 2-4 weeks at 28 ° C and 75% relative humidity. After the end of the test, fungicide-free patterns were completely covered with fungi.

Test specimens with only 0.1% fungicide usually had a light growth of less than 10% of the total area, in a few cases the coatings were significantly overgrown up to 30%. Test specimens with 0.3% and more of the mixtures according to the invention were free from fungal growth, and in part there were growth-free zones of inhibition of several millimeters in width around the samples in the culture media. The following examples were tested in the filter test described. The results compared to fungicide-free materials are summarized in Table 4.

example 1

Dispersion paint, made from 30% water, 13% polyvinyl propionate acrylic ester dispersion, 9% titanium dioxide, 34% chalk, 10% other fillers and small amounts of hydroxypropylmethyl cellulose, defoamers, wetting agents and the like were mixed with 0.5 wt .% of a mixture of 6 parts of chloroacetamide (1) and 4 parts of 2-methoxycarbonylaminobenz-imidazole (A) fungicidal.

Example 2

Dispersion paint from Example 1 was treated with 0.1% by weight of a mixture of 6 parts of chloroacetamide (1) and 4 parts of 2-methoxycarbonylamino-benzimidazole (A) fungicide.

Example 3

Commercially available emulsion paint, containing styrene-acrylate dispersion, titanium dioxide, calcium carbonate and small amounts of carboxymethyl cellulose, was mixed with 0.3% by weight of a 45 mixture of 4 parts of N-hydroxymethyl-chloroacetamide (2) and 6 parts of 2-methoxycarbonylamino benzimidazole (A) fungicidal.

Example 4

Commercially available emulsion paint from Example 3 was fungicidal with 50 0.3% by weight of a mixture of 7 parts of N-hydroxymethylethanolamine (3) and 3 parts of l-methoxycarbonyl-3-octadecyl-s-hexahydrotriazino-benzimidazole (E) equipped.

55 Example 5

Coarse spray plaster, containing 13% styrene-acrylate dispersion, 5% titanium dioxide, 46% ground dolomite, 27% gravel with a grain size of 1.2 to 1.8 mm and small amounts of defoamer and wetting agent, was mixed with 1.0 wt. -% of a mixture of 8 parts of chloroacetamide (1) and 2 parts of 2-meth-oxycarbonylamino-benzimidazole (A) antifungal.

Example 6

65 spray plaster from Example 5 was treated with 0.3% by weight of a mixture of 5 parts of chloroacetamide (1) and 5 parts of 2-methoxycarbonylamino-benzimidazole-4'-dodecyl-benzenesulfonate (B) fungicidal.

35

5

625 678

Example 7

Commercial casein-bound filler was antifungal with 0.5% by weight of a mixture of 6 parts of chloroacetamide (1) and 4 parts of 2-methoxycarbonylamino-benzimidazole (A). s

Example 8

Commercial casein-bound filler was treated with 0.3% by weight of a mixture of 6 parts of chloroacetamide (1) and 4 parts of 2-methoxycarbonylamino-benzimidazole (A) fungicide.

Table 4

example

Test organism A. c.

At.

A. p.

C. g.

P.

1

2nd

1

1

1

1

2nd

5

3rd

4th

3rd

2nd

fungicide-free color

6

6

6

6

5

from example 1

3rd

3rd

2nd

1

1

2nd

4th

3rd

2nd

2nd

1

2nd

fungicide-free color

6

6

6

5

6

from example 3

5

1

1

1

1

1

6

3rd

2nd

1

1

3rd

fungicide-free spray plaster

6

6

6

6

6

from example 5

7

2nd

1

2nd

1

1

8th

3rd

2nd

2nd

2nd

1

fungicide-free filler

6

6

5

5

6

from Example 7 evaluation:

1: Samples not overgrown, inhibition zone larger than 3 mm 2: Samples not overgrown, inhibition zone less than 3 mm 3: Samples not overgrown, no inhibition zone 4: Samples up to 10% overgrown 5: Samples up to 30% overgrown 6: Area growth of over 30% of the sample area.

s

Claims (3)

625 678 2. Fungicidal composition according to claim 1, characterized in that it contains as component b) an addition or condensation product of 3 to 6 moles of formaldehyde per mole of melamine. 2nd PATENT CLAIMS 1. Fungicidal composition, characterized by the content of a mixture of a) 20 to 80% of at least one benzimidazole compound of the formulas I and II 0 C-N-C-OR- H (I) and or the corresponding salts with a (C12 to C18) alkane sulfonic acid or with dodecylbenzenesulfonic acid, and in which Ri denotes a (Cf to C4) alkyl group and R2 denotes a (Cj to Ci8) alkyl group; and b) 80 to 20% of at least one amine compound from the group chloroacetamide, N-hydroxymethylchloroacetamide, N-hydroxymethylethanolamine and addition or condensation product of formaldehyde and melamine or of formaldehyde and primary hydroxyalkylamines which contain 2 to 6 carbon atoms in the alkyl radical. 3. Use of fungicidal compositions according to claim 1 in building protection and paint in amounts of 0.3 to 5.0 wt .-%.