BIOCIDE AGENTS

Abstract

The present invention relates to biocidal agents with excellent fungicidal and algicidal action, consisting at least of an algicide, propiconazole and an iodopropargyl compound, where preferably at least one of the active ingredients is bound, preferably microencapsulated.

Claims

1. A biocidal agent comprising biocidally active ingredients, wherein the active ingredients comprise; A) at least one algicide selected from the group of the triazine algicides, urea algicides and uracil algicides; B) propiconazole; and C) at least one iodopropargyl compound.

2. The biocidal agent as claimed in claim 1, wherein at least one of the active ingredients is bound, preferably microencapsulated.

3. The biocidal agent as claimed in claim 1, wherein the at least one algicide is selected from the group consisting of terbutryn, cybutryn, propazin, terbuton, diuron, benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and terbacil.

4. The biocidal agent as claimed in claim 1, wherein the algicide is diuron.

5. The biocidal agent as claimed in claim 1, wherein the at least one iodopropargyl compound is selected from the group consisting of 3-iodo-2-propynyl propylcarbamate, 3-iodo-2-propynyl butylcarbamate (IPBC), 3-iodo-2-propynyl m-chlorophenylcarbamate, 3-iodo-2-propynyl phenylcarbamate, 3-iodo-2-propynyl 2,4,5-trichlorophenyl ether, 3-iodo-2-propynyl-4-chlorophenylformal (IPCF), di(3-iodo-2-propynyl)hexyl dicarbamate, 3-iodo-2-propynyloxyethanol ethylcarbamate, 3-iodo-2-propynyloxyethanol phenylcarbamate, 3-iodo-2-propynyl thioxothioethylcarbamate, 3-iodo-2-propynylcarbamic acid ester (IPC), N-iodopropargyloxycarbonylalanine, N-iodopropargyloxycarbonylalanine ethyl ester, 3-(3-iodopropargyl)benzoxazol-2-one, 3-(3-iodopropargyl)-6-chlorobenzoxazol-2-one, 3-iodo-2-propynyl alcohol, 4-chlorphenyl-3-iodopropargyformal, 3-bromo-2,3-diiodo-2-propenyl ethylcarbamate, 3-iodo-2-propynyl n-hexylcarbamate, and 3-iodo-2-propynyl cyclohexylcarbamate.

6. The biocidal agent as claimed in claim 1, wherein the at least one iodopropargyl compound is 3-iodo-2-propynyl butylcarbamate.

7. The biocidal agent as claimed in claim 1, wherein the weight ratio of propiconazole to the sum of iodopropargyl compound(s) is 1:100 to 100:1, preferably 1:20 to 20:1 and particularly preferably 1:9 to 9:1.

8. The biocidal agent as claimed in claim 1, wherein the weight ratio of algicide(s) to the sum of propiconazole and the sum of iodopropargyl compound(s) Is 1:100 to 100:1, preferably 1:20 to 20:1 and particularly preferably 1:9 to 9:1.

9. The biocidal agent as claimed in claim 1, wherein the agent comprises 0.5 to 80% by weight, preferably 1 to 70% by weight, in particular 1 to 60% by weight of the active ingredients.

10. The biocidal agent as claimed in claim 2, at least one of the active ingredients is microencapsulated in microcapsules.

11. The biocidal agent as claimed in claim 10, wherein the microcapsules have a volume-averaged particle size of 0.3 to 100 μm.

12. The biocidal agent as claimed in claim 10, wherein the microcapsules comprise a melamine formaldehyde polymer as encapsulation material.

13. (canceled)

14. A method of protecting technical materials against attack and/or destruction by microorganisms, the method comprising incorporating biocidal agents as claimed in claim 1 into or onto the technical material to act on the microorganisms or their habitat.

15. A technical material obtained by treating a technical material with a biocidal agent as claimed in claim 1.

16. The technical material as claimed in claim 15, wherein the technical material is selected from adhesives, sizes, paper, cardboard, leather, wood, woodbase materials, wood/plastic composites, paints, coating compositions, plasters, cooling lubricants and heat transfer liquids.

17. The biocidal agent as claimed in claim 1, wherein: the at least one algicide is selected from the group consisting of terbutryn, cybutryn, propazin, terbuton, diuron, benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and terbacil; the iodopropargyl compounds are selected from the group consisting of 3-iodo-2-propynyl propylcarbamate, 3-iodo-2-propynyl butylcarbamate (IPBC), 3-iodo-2-propynyl m-chlorophenylcarbamate, 3-iodo-2-propynyl phenylcarbamate, 3-iodo-2-propynyl 2,4,5-trichlorophenyl ether, 3-iodo-2-propynyl-4-chlorophenylformal (IPCF), di(3-iodo-2-propynyl)hexyl dicarbamate, 3-iodo-2-propynyloxyethanol ethylcarbamate, 3-iodo-2-propynyloxyethanol phenylcarbamate, 3-iodo-2-propynyl thioxothioethylcarbamate, 3-iodo-2-propynylcarbamic acid ester (IPC), N-iodopropargyloxycarbonylalanine, N-iodopropargyloxycarbonylalanine ethyl ester, 3-(3-iodopropargyl)benzoxazol-2-one, 3-(3-iodopropargyl)-6-chlorobenzoxazol-2-one, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargylformal, 3-bromo-2,3-diiodo-2-propenyl ethylcarbamate, 3-iodo-2-propynyl n-hexylcarbamate, and 3-iodo-2-propynyl cyclohexylcarbamate; the weight ratio of algicide(s) to the sum of propiconazole and the sum of iodopropargyl compound(s) is 1:100 to 100:1; the weight ratio of algicide(s) to the sum of propiconazole and the sum of iodopropargyl compound(s) is 1:100 to 100:1; the agent comprises 0.5 to 80% by weight, preferably 1 to 70% by weight, in particular 1 to 60% by weight of active ingredients of the components A), B) and C); and at least one of the active ingredients is microencapsulated in microcapsules.

18. The biocidal agent as claimed in claim 17, wherein: the agent comprises 1 to 60% by weight of active ingredients A), B) and C); the weight ratio of propiconazole to the sum of iodopropargyl compound(s) is 1:20 to 20:1; the weight ratio of algicide(s) to the sum of propiconazole and the sum of iodopropargyl compound(s) is 1:20 to 20:1; and the at least one algaecide is the active ingredient microencapsulated in the capsules.

19. The biocidal agent as claimed in claim 18, wherein: the at least one algicide is diuron; the iodopropargyl compound is 3-iodo-2-propynyl butylcarbamate; the weight ratio of propiconazole to 3-iodo-2-propynyl butylcarbamate is 1:9 to 9:1; the weight ratio of diuron to the sum of weights of propiconazole and 3-iodo-2-propynyl butylcarbamate is 1:9 to 9:1; the microcapsules have a volume-averaged particle size of 0.3 to 100 μm; and the microcapsules comprise a melamine formaldehyde polymer as encapsulation material.

Description

EXAMPLES

Materials

[0105] Gum Arabic solution (4% by weight)

[0106] Coadis™ BR3 (50% by weight in H2O) (dispersion reagent; aqueous polyacrylate salt solution from Coatex)

[0107] SILOFOAM®SRE (silicone antifoam emulsion antifoam from Wacker)

[0108] Maprenal®/water solution (1:1) (Maprenal® MF 921 w/85WA melamine-formaldehyde binder from INEOS Melamines)

[0109] Preventol® D7 (pack preservative with about 1.5% by weight chloromethylisothiazolinone/methylisothiazolinone 3:1)

[0110] Preventol® BIT 20D (pack preservative with about 20% by weight benzisothiazolinone)

[0111] Urea

[0112] Preventol® A 6 (Diuron)

[0113] Preventol® MP 100 (IPBC)

[0114] Preventol® A 12 (Propiconazole)

[0115] Sipernat® 50 S (precipitated silica; Evonik)

[0116] Preventol® A 14-D (suspension comprising 20% Diuron, 10% BCM, 3% OIT)

[0117] Preventol® MP 400 (suspension comprising 40% IPBC; manufacturer Lanxess)

[0118] Soprophor® S25 (emulsifier based on tris-sterylphenyl ether ethoxylates)

[0119] Preventol® BM 25 (pack preservative comprising 2.4% by weight benzisothiazolinone and 4.9% by weight methylisothiazolinone)

[0120] Rhodopol-G® (thickener based on xanthan gum from Solvay Rhodia)

[0121] Pluronic F127: Ethylene oxide-propylene oxide block copolymer

[0122] Oparyl MT 820: Sodium didisobutylnaphthalenesulfonate

Example 1 (Production of Propiconazole on Sipernat 50 S)

[0123] 463 g of propiconazole (content 97.1% by weight) were charged to a pot and heated to 60° C. With paddle-blade stirring, 300 g of Sipernat 50 S were slowly added thereto. The initially doughy mass became readily stirrable and free-flowing after a short time. Finally, 3.75 g of Aerosil 200 were also added and the mixture was stirred further.

[0124] This gave a white, free-flowing powder. To monitor the homogeneity, samples were taken at three different points and analyzed as to the active ingredient content using HPLC:

[0125] In this connection, contents of 58.7% by weight, 58.7% by weight and 59.5% by weight of propiconazole were ascertained.

Example 2 (Production of Encapsulated Diuron)

[0126] A 1000 ml stainless steel beaker was charged at room temperature with 33.79 g of gum Arabic solution, 6.75 g of Coadis® BR3 solution and 451.5 g of water together with 2.7 g of defoamer Silfoam® SRE. By adding citric acid solution (50% by weight), the pH was adjusted to 2.99. Then, 135 g of diuron were added with stirring and the mixture was thoroughly mixed for 30 minutes using a stirring rod (Ultra-Turrax). The crude mixture was transferred to a 1000 ml flat-flange pot and heated to the deposition temperature of 60° C. At this temperature, 135.5 g of a Maprenal®/water solution (1:1) were added dropwise to the diuron suspension over a period of 3 hours. When the addition was complete, the mixture was heated to 80° C. and stirred for 4 hours. Then, the mixture was cooled to room temperature and further stirred for 12 hours. The pH was then adjusted to pH 8 by adding sodium hydroxide solution (50% by weight). Then, the 2.26 g of Soprophor® S25, 0.75 g of Preventol® D7, 0.72 g of Preventol® BIT 20D, 1.2 g of Rhodopol-G® and 37.65 g of urea were added and the mixture was stirred to homogeneity. Content: 16.5% by weight of diuron.

Example 3 (Production of Encapsulated IPBC)

[0127] In a 1 L stainless steel pot, at room temperature, 3.76 g of Coadis BR, 37.5 g of 4% strength by weight gum Arabic solution and 3.03 g of antifoam Wacker SRE were processed in 637.22 g of water with stirring to give a slightly cloudy solution.

[0128] Then, by adding 8.85 g of a 50% strength by weight solution of citric acid in water, the pH was reduced from pH=7.70 to pH=2.96.

[0129] The solution obtained in this way was transferred to a 1000 ml flat-flange pot with impeller stirrer and Ultraturrax. With stirring using an impeller stirrer, 150.09 g of IPBC were added at approx. 400-420 rpm.

[0130] Then, the mixture was heated to 70° C., during which above 60° C. and from the onset of melting of the IPBC, the Ultra-Turrax was switched on (15600 rpm) and, after reaching 70° C., the mixture was emulsified for at least 30 min.

[0131] Then, 150 g of a 50% strength by weight solution of Marprenal MF 921w/85WA in water was metered in over the course of 3 h. The Ultra-Turrax initially continued to run. After 10% of the melamine-formaldehyde polymer had been metered in, the Ultra-Turrax was switched off and the reaction mixture was stirred further only by means of impeller stirrer at an unchanged stirring speed.

[0132] Following the complete metered addition of the melamine-formaldehyde polymer, the reaction mixture was after-stirred for a further 4 h at 70° C., then let down and removed by suction with membrane pump vacuum. The moist filtercake was then washed with 67 g, 27 g and 7 g of hot (80° C.) water. This gave 312.50 g of the white, moist product.

Example 4

[0133] At room temperature, 75.57 g of Preventol MP 400, 30 g and 104 g of water were stirred. To this was added, with stirring, 25 g of propiconazole on Sipernat 50 S (see Example 1) and stirring was continued for 30 minutes until the suspension was homogeneous. Then, 269.46 g of the capsule suspension from Example 2 were added and the mixture was homogenized with slow stirring. To this was added, with further stirring, 0.5 g of Preventol D 7, 0.5 g of Preventol BIT 20 D, 20.0 g of a 3% strength aqueous solution of Rhodopol G in water (xanthan gum solution) and a further 6 g of water. The homogeneous white suspension comprised 9.0% by weight of diuron, 6.1% by weight of IPBC and 3.0% by weight of propiconazole. The viscosity (rotary viscometer RC 20/Rheotec) was 370.3 mPas at 30 l/s.

Example 5

Propiconazole Emulsion

[0134] At RT, 61.66 g of propiconazole and 21.43 g of methyl oleate were mixed together with stirring. To this were added 10 g of Soprophor S 25, 1.5 g of Pluronic F 127 and 2.5 g of Oparyl MT 820 and the mixture was stirred for 30 minutes. Then, 322.3 g of water were added and the mixture was emulsified on the dissolver (10000 rpm). Finally, a further 0.5 g of Preventol D 7. 0.5 g of Preventol BIT 20 D, 39.8 g of a 3% strength solution of Rhodopol G in water and a further 39.8 g of water were added with stirring. The white emulsion comprised 12.7% by weight of propiconazole (HPLC).

[0135] Preparation of the Suspoemulsion

[0136] At room temperature, 90 g of Preventol MP 400-D and 26.2 g of water are stirred with 150 g of the propiconazole emulsion according to this example. Then, with further stirring, 327.27 g of the capsule suspension according to Example 2, 0.6 g of Preventol D 7, 0.6 g of Preventol BIT 20 D, 2.83 g of 3% strength aqueous solution of Rhodopol G and 3.67 g of further water were added.

[0137] This gave a white suspoemulsion with the following active ingredient contents (HPLC):

8.9% by weight of diuron
6.0% by weight of IPBC
3.2% by weight of IPBC
Viscosity: 237 mPas at 30 l/s.

Example 6

[0138] 10 g of Pluronic F 127 and 10 g of Soprophor S 25 were firstly dissolved in 95.6 g of water and then, with stirring, 62.76 g of the encapsulated IPBC from Example 3 were added. With further stirring, a further 272.73 g of the encapsulated diuron from Example 2 were added and the mixture was after-stirred for 30 min. Then, a further 1.0 g of Preventol BM 25, 15.05 g of 3% strength Rhodopol G solution and a further 8.35 g of water were added with stirring.

[0139] This gave a white, homogeneous suspension with a viscosity of 541 mPas at 30 I/s (rotary viscometer/Rheotec). Active ingredient contents (HPLC):

8.9% by weight of diuron
6.3% by weight of IPBC
3.0% by weight of propiconazole.

Example 7: Investigation of the Fungicidal and Algicidal Efficacy

[0140] To assess the fungicidal and algicidal efficacy, two exterior emulsion paints were equipped with the biocidal agents according to Example 4, a homogeneous white suspension comprising 9.0% by weight of diuron, 6.1% by weight of IPBC and 3.0% by weight of propiconazole in the stated amounts.

[0141] The exterior emulsion paints used were:

Paint No. 1:

[0142]

TABLE-US-00001 Tronox Titanium RKB2 35.0 Titanium dioxide EWO powder 20.0 BaSO.sub.4 Micro Mica 15.0 Magnesium aluminum silicate Talc AT1 5.0 Magnesium silicate Chalk BLP2 25.0 Calcite (CaCO.sub.3) Tylose MH 2000 P2, 2% 20.0 Methylhydroxyethylcellulose H.sub.2O 5.0 Distilled water Calgon N, 10% 2.5 Polyphosphate Pigment distributor A, 10% 2.5 Polyacrylic acid salt Mowilith DM 2H (binder) 80.0 Polyvinyl acetate Sum 210.0 Solids fraction 140.0 66.7%

Paint No. 2:

[0143]

TABLE-US-00002 Tronox Titanium RKB2 40.0 Titanium dioxide Talco 1N 15.0 Magnesium silicate Durcal 5 45.0 Calcite (CaCO.sub.3) Walsroder MC 3000 S 2% 30.0 Methylcellulose H2O 6.5 Distilled water Calgon N 10% 3.0 Polyphosphate Pigment distributor A 10% 1.0 Polyacrylic acid salt Agitan 281 (1:1 in Texanol) 1.0 Antifoam White spirit 5.0 Mixture of aliphatic hydro- carbons Butyl diglycol acetate 1.5 Acronal 290 D (binder) 71.0 Polyacrylic acid ester Sum 219.0 Solids fraction 135.5 61.9%

[0144] To simulate aging, the samples, after drying, were soaked for 24 h in running tap water at a flow rate of 6 Uh (+/−1 L) (24 h washing). One set of the unsoaked samples was subjected to UV irradiation for 4 weeks and visually assessed after 1, 2 and 4 weeks. All samples were subjected to an agar diffusion test (AD test). The following test organisms were used: Ascomycetes and Deuteromycetes (Alternaria alternata, Aspergillus flavus, Aspergillus niger, Aspergillus ustus, Aureobasidium pulhdans, Cladosporium herbaru, Paecilomyces variotii, Paecilomyces variotii, Penicillium citrinum and Stachybotrys chartarum) and Algae (known facade destroyers: Phiormidiumn tergestinum, Chlorella vulgaris, Phormidium spec., Desmodesmus commuis).

[0145] Evaluation of the AD Test

[0146] The evaluation of the mold test takes place after incubation for 3 weeks at 29° C.+/−1° C.

[0147] Passed: [Good/Moderate]

)* Inhibition of algae growth
0 (0- . . . ) Surface of the specimen growth-free, but zone of inhibition around the specimen [in mm]
0 Surface of the specimen growth-free
1)# Corner growth, marginal growth on the specimen
1 Surface of the specimen covered with up to 10% growth
2 Surface of the specimen covered with 10-30% growth

[0148] Not Passed: [Inadequate]

3 Surface of the specimen covered with 30-50% growth
4 Surface of the specimen covered with 50-100% growth

TABLE-US-00003 TABLE 1 Results of the AD test against mold and algae in exterior emulsion paint based on PVAc (Paint No. 1) Mold Algae Finish [% by weight] OB 24 h washing OB 24 h washing Unpreserved (0.00) 4 4 4 4 0.50 1 3 0)* 0)* 0.75 1.sup.# 2 0)* 0)* 1.00 0 (0-20) 1 0)* 0)* 1.25 0 (0-20) 1 0)* 0)* 1.50 0 (0-20) 1.sup.# 0)* 0)* 1.75 0)* 1.sup.# 0)* 0)* 2.00 0)* 0 (0-20) 0)* 0)*

TABLE-US-00004 TABLE 2 Results of the AD test against mold and algae in exterior emulsion paint based on STA (Paint No. 2) Mold Algae Finish OB 24 h washing OB 24 h washing Unpreserved (0.00) 4 4 4 4 0.50 1 3 1 1 0.75 1.sup.# 1 0)* 1 1.00 0 1 0)* 1 1.25 0 (0-20) 1.sup.# 0)* 1 1.50 0)* 0 (0-20) 0)* 0)*