SYNERGISTIC ANTIMICROBIAL COMPOSITION WITH TERBUTRYN 1. Field of the invention This invention concerns microbiocidal synergistic compositions, which comprise a first component selected from N2-tert-butyl-N4-ethyl-6-methylthio-1, 3,5-triazine-2, 4- diylamine (hereafter terbutryn) and 2-methylthio-4-t-butylamino-6-cyclopropylamino-s- triazine (hereafter cybutrin) in combination with other biocides, which are intended to provide more effectiveness for paints, coatings, concrete, wood, textiles as well as other formulations that may be attacked by fungi and/or algae.

2. Description Terbutryn has been mixed with various biocides combination form for various applications.

EP-A-0741 971 discloses terbutryn with 3-iodo-2-propinyl butylcarbamate (IPBC) synergistic combinations. it is the intention of the present invention to provide novel combinations of biocides on the basis of terbutryn or cybutryn with improved properties, in particular displaying a synergistic effect, so that it will be possible to achieve the same final effects with a reduced total amount of biocide.

The interaction of the two components of the biocides mixture is calculated according to the method described by Kull et al. (Kull F. C., Eisman P. C., Sylwestrowicz H. D. and <BR> <BR> Mayer R. L. , Applied Microbiology 1961,6 : 538-541). According to this method, the so- called synergy index is calculated according to the following formula: Synergy index SI = Qbiacide-l/QBIOCIDE-l + Q biocide-2/QBIOCIDE-2 The elements used for the calculation of the synergy index according to the above formula have the following meaning :- Q biocide-1 : minimum inhibition concentration of biocide-1 in the mixture of biocide 1 and biocide-2 Q BIOCIDE-1 Minimum inhibition concentration of biocide-1 as single biocide without biocide-2, Q biocide-2 : minimum inhibition concentration of biocide-2 in the mixture of biocide-1 and biocide-2 Q BIOCIDE-2 : minimum inhibition concentration of biocide-2 as single biocide without biocide-1.

All these symbols indicate a particular concentration leading to a particular end point, in this case the complete inhibition of all growth of microorganisms, so that the selected end point is in fact the minimal inhibitory concentration (mic).

The method of Kull et al. for the calculation of the synergy index allows a very quick evaluation of the type of interaction displayed by the two components of the biocidal mixture. When the synergy index displays a value of more than 1, then there is an antagonism between the two components. When the synergy index is 1, then there is an addition of the effects of the two components. When the synergy index displays a value of less than 1, then there is a synergism between the two components.

The invention is now explained by a number of examples. In these examples terbutryn, (CAS Number: 886-50-0) and chlorothalonil (CAS Number: 1897-45-6), and/or 2-octyl- 2H-isothiazol-3-one (NOIT) (CAS Number : 26530-20-1), and/or 4,5-dichloro-2-octyl- 2H-isothiazol-3-one (DCOIT) (CAS Number: 64359-81-5), alone and in a number of different combinations have been tested against a number of antimicrobial preparations.

Effects of the invention This invention yields antimicrobial compositions comprising as the active ingredient a first component selected from terbutryn and cybutryn, the preferred one being terbutryn.

The antimicrobial composition comprises at least one second component, which is selected from the group consisting of chlorothalonil, 2-octyl-2H-isothiazol-3-one (NOIT) and 4, 5-dichloro-2-octyl-2H- isothiazol-3-one (DCOIT). Accordingly the compositions of the invention comprise a combination of terburtyn or cybutryn with chlorothalonil alone, but also a combination of terburtyn or cybutryn with chlorothalonil and NOIT, a further combination of terburtyn or cybutryn with chlorothalonil and DCOIT and a combination of terburtyn or cybutryn with chlorothalonil, NOIT and DCOIT.

Each of these combination displays excellent properties, the most preferred combination is terbutryn with chlorothalonil.

It is possible to add a further component from a third group of compounds consisting of (a) 3-iodo-2-propinyl butylcarbamate (IPBC) and (b) Zinc-2-pyridinethiol 1-oxide.

The compositions of the invention produce a synergistic effect, are highly safe and highly effective, and have a broad antimicrobial spectrum.

Important applications of the synergistic antimicrobial compositions of the present invention include, but are not limited: inhibition of the growth of bacteria fungi and algae in aqueous paints and coatings, preservation of wood and cutting fluids, and control of slime-producing fungi in pulp and paper mill; protection of paint films, especially exterior paints, from attack by fungi and algae which occurs during weathering of the paint film.

FUNGICIDES Example 1.

In this example the synergism of the combinations of terbutryn and chlorothalonil has been investigated.

For that purpose aqueous dispersions with different concentrations were prepared of terbutryn and chlorothalonil and the effect of these preparations were investigated against Aspergillus niger.

Table 1. Terbutryn/Chlor o-thalonil Qter QTER Qter/QTER Qc QC Qc/QC SI % 100/0 4096 4096 1 80/20 512 4096 0,125 1 1 1,0 1,125 60/40 64 4096 0,016 1 1 1 1,016 50/50 32 4096 7, 8 x 10-3 0,5 1 0,5 0,5 40/60 8 4096 2, 0 x 10-3 0,5 1 0,5 0,5 20/80 4 4096 9, 8x 10-4 0,5 1 0,5 0,5 0/100 1 1 1 Ter: Terbutryn C: chlorothalonil It is evident from the data in the table, that the most optimal combination of the two components terbutryn and chlorothalonil is found at a concentration of 50% (w/w) of terbutryn and 50% (w/w) chlorothalonil, 40% (w/w) of terbutryn and 60% (w/w) chlorothalonil, and 20% (w/w) of terbutryn and 80% (w/w) chlorothalonil.

Example 2.

In this example the synergism of combinations of terbutryn and chlorothalonil has been investigated.

For that purpose aqueous dispersions with different concentrations were prepared of terbutryn and chlorothalonil and the effect of these preparations were investigated against Penicillium caseicolum.

Table 2. ter/ terbutryn/chlorothalonil Qter QTER QTER Q QC QC/QC SI 100/0 4096 4096 1 80/20 512 4096 0,125 1 1,0 1,0 1,125 60/40 64 4096 0, 016 1 1,0 1 1,016 50/50 32 4096 7, 8 x 10-3 0, 5 1,0 0,5 0,5 40/60 8 4096 2, 0 x 10-3 0, 5 1,0 0,5 0,5 20/80 4 4096 9, 8 x 10-4 0, 5 1, 0 0,5 0,5 0/100 1, 0 1,0 1 It is evident from the data in the table, that the most optimal combination of the two components terbutryn and chlorothalonil is found at a concentration of 50% (w/w) of terbutryn and 50% (w/w) chlorothalonil, 40% (w/w) of terbutryn and 60% (w/w) chlorothalonil, and 20% (w/w) of terbutryn and 80% (w/w) chlorothalonil.

Example 3.

In this example the influence of the synergism of combinations of terbutryn and chlorothalonil in the inventive composition has been investigated.

For that purpose aqueous dispersions with different-concentrations were prepared of terbutryn and chlorothalonil and the effect of these preparations were investigated against Aurobasidium pullulans.

Table 3. Terbutryn/Chlorothaloni Qter QWER QTÉR Qc QC Qc/QC SI I QTER QC/QC 100/0 4096 4096 1 80/20 512 4096 0, 125 2 2, 5 0, 8 0, 9125 60/40 64 4096 0, 0156 1, 5 2, 5 0, 6 0, 6156 50/50 32 4096 7, 8 x 10-3 1 2, 5 0, 4 0, 4 40/60 8 4096 2, 0x 10-3 1 2, 5 0, 4 0, 4 20/80 4 4096 9, 8 x 10'1 2,5 0, 4 0,4 0/100 2. 5 2, 5 1- It is evident from the data in the table, that the present combination displays a synergistic effect over the whole investigated range and that the most optimal combination of the two components terbutryn and chlorothalonil is found at a concentration of 50% (w/w) of terbutryn and 50% (w/w) chlorothalonil, 40% (w/w) of terbutryn and 60% (w/w) chlorotalonil, and 20% (w/w) of terbutryn and 80% (w/w) chlorothalonil.

Example 4.

In this example the influence of the synergism of combinations of terbutyn and 2-octyl- 2H-isothiazol-3-one (NOIT) in the inventive composition has been investigated.

For that purpose aqueous dispersions with different concentrations were prepared of terbutryn and NOIT and the effect of these preparations were investigated against Aspergillus niger.

Table 4. ter/ Terbutryn/NOIT Qter QrBR Q Qnoit QNOIT Q SI 100/0 4096 4096 1 80/20 512 4096 0, 125 2, 5 2, 5 1, 0 1, 125 60/40 64 4096 0, 016 2 2, 5 0, 8 0, 816 50/50 32-4096 7, 8 x 10-3 1, 5 2, 5 0, 6 0, 6 40/60 8 4096 2, 0 x 10-3 1 2, 5 0, 4 0, 4 20/80 4 4096 9, 8x 10-4 1 2, 5 0, 4 0, 4 0/100 2, 5 2, 5 1 It is evident from the data in the table, that the most optimal combination of the two components terbutryn and NOIT is found at a concentration of 50% (w/w) of terbutryn and 50% (w/w) NOIT, 40% (w/w) of terbutryn and 60% (w/w) NOIT, and 20% (w/w) of terbutryn and 80% (w/w) NOIT.

Example 5.

In this example the influence of the synergism of combinations of terbutryn and NOIT in the inventive composition has been investigated.

For that purpose aqueous dispersions with different concentrations were prepared of terbutryn and NOIT and the effect of these preparations were investigated against Penicillium caseicolum.

Table 5. Terbutryn/NOI Qter QTER ter/Qnoit QNOIT Qnoit/QNOI SI QTER T 100/0 4096 4096 1 80/20 512 4096 0, 125 2, 5 2, 5 1, 0 1, 125 60/40 64 4096 0, 0156 2 2, 5 0, 8 0, 815 6 50/50 32 4096 7, 8 x 10-1, 5 2, 5 0, 6 0, 6 40/60 8 4096 2, 0 x 10-1 2, 5 0, 4 0, 4 3 20/80 4 4096 9, 8 x 10-1 2, 5 0, 4 0, 4 4 0/100 1 4096 2, 4x l0~ 2, 5 2, 5 1 4 It is evident from the data in the table, that the most optimal combination of the two components terbutryn and 2-octyl-2H-isothiazol-3-one is found at a concentration of 50% (w/w) of terbutryn and 50% (w/w) NOIT, 40% (w/w) of terbutryn and 60% (w/w) NOIT, and 20% (w/w) of terbutryn and 80% (w/w) NOIT.

Example 6. In this example the influence of the synergism of combinations of terbutryn and 2-octyl- 2H-isothiazol-3-one in the inventive composition has been investigated.

For that purpose aqueous dispersions with different concentrations were prepared of terbutryn and NOIT and the effect of these preparations were investigated against Aurobasidium pullulans.

Table 6. tfr/ terbutrynfNOIT Qter QTER QTER Qnoit QNOIT Qnoit/QNOI SI QUER T 100/0 4096 4096 1 80/20 512 4096 0, 125 2, 5 2, 5 1, 0 1, 125 60/40 64 4096 0, 0156 2 2, 5 0, 8 0, 815 6 SO150 32 4096 7, 8 x lo-3 1X ; 2, 5-0, 6 0, 6 40/60 8 4096 2, 0 x 103 1 2, 5 0, 4 0, 4 20/80 4 4096 9, 8x 104 1 2, 5 0, 4 0, 4 0/100 2, 5 2, 5 1 It is evident from the data in the table, that the most optimal combination of the two components terbutryn and 2-octyl-2H-isothiazol-3-one is found at a concentration of 50% (w/w) of terbutryn and 50% (w/w) 2-octyl-2H-isothiazol-3-one, 40% (w/w) of terbutryn and 60% (w/w) 2-octyl-2H-isothiazol-3-one, and 20% (w/w) of terbutryn and . 80% (w/w) 2-octyl-2H-isothiazol-3-one.

Example 7.

In this example the influence of the synergism of combinations of terbutryn and DCOIT in the inventive composition has been investigated. For that purpose aqueous dispersions with different concentrations were prepared of terbutryn and DCOIT and the effect of these preparations were investigated against Aspergillus niger.

Table 7. Terbutryn/DCOIT Qter Q. I. ER ter/Qdcot QDCOI DROIT DCOIT 100/0 4096 4096 1 80/20 512 4096 0, 125 2, 5 2, 5 1, 0 1, 60/40 64 4096 0, 0156 2 2, 5 0, 8 0, 2 50/50 32 4096 7, 8 x 10-3 1, 5 2, 5 0, 6 ( 40/60 8 4096 2, 0 x 10-3 1 2, 5 0, 4 20/80 4 4096 9, 8x 104 1 2, 5 0, 4 0/100 2, 5 2, 5 1 It is evident from the data in the table, that the most optimal combination of the two components terbutryn and DCOIT is found at a concentration of 50% (w/w) of terbutryn and 50% (w/w) DCOIT, 40% (w/w) of terbutryn and 60% (w/w) DCOIT, and 20% (w/w) of terbutryn and 80% (w/w) DCOIT.

Example 8.

In this example the influence of the synergism of combinations of terbutryn and DCOIT in the inventive composition has been investigated.

For that purpose aqueous dispersions with different concentrations were prepared of terbutryn and DCOIT and the effect of these preparations were investigated against Penicillium caseicolum.

Table 8. Terbutr COIT ter ter/ Q QTER Q. I. ER Qdcoit QC DCOTI Qdcoit QC SI DOIT 100/0 4096 4096 1- 80/20 512 4096 0, 125 2, 5 2, 5 1, 0 1, 125 60/40 64 4096 0, 0156 2 2, 5 0, 8 0, 8156 50/50 32 4096 7, 8 x 10-3 1, 5 2, 5 0, 6 0, 6 40/60 8 4096 2, 0 x 10-3 1 2, 5 0, 4 0, 4 20/80 4 4096 9, 8 x 104 1 2, 5 0, 4 0, 4 0/100 2 2, 5 2, 5 1 It is evident from the data in the table, that the most optimal combination of the two components terbutryn and chlorothalonil is found at a concentration of 50% (w/w) of terbutryn and 50% (w/w) DCOIT, 40% (w/w) of terbutryn and 60% (w/w) DCOIT, and 20% (w/w) of terbutryn and 80% (w/w) DCOIT.

Example 9.

In this example the influence of the synergism of combinations of terbutryn and DCOIT in the inventive composition has been investigated.

For that purpose aqueous dispersions with different concentrations were prepared of terbutryn and DCOIT and the effect of these preparations were investigated against Aurobasidium Pullulans.

Table 9. Terbutryn/ter/Qao, t DCOIT QTER QC DCOTT 100/0 4096 4096 1 80/20 512 4096 0, 125 2, 5 2, 5 1, 0 1, 125 60/40 64 4096 0, 0156 2 2, 5 0, 8 0, 8156 50/50 32 4096 7, 8 x 10-3 1, 5 2, 5 0, 6 0, 6 40/60 8 4096 2, 0 x 10-3 1 2, 5 0, 4 0, 4 20/80 4 4096 9, 8 x 10'4 1 2, 5 0, 4 0, 4 0/100 2, 5 2, 5 1 It is evident from the data in the table, that the most optimal combination of the two components terbutyn and DCOIT is found at a concentration of 50% (w/w) of terbutyn and 50% (w/w) DCOIT, 40% (w/w) of terbutryn and 60% (w/w) DCOIT, and 20% (w/w) of terbutryn and 80% (w/w) DCOIT.

ALGICIDE Example 10.

In this example the influence of the synergism of combinations of terbutryn and chlorothalonil in the inventive composition has been investigated.

For that purpose aqueous dispersions with different concentrations were prepared of terbutryn and chlorothalonil and the effect of these preparations were investigated against Chlorella vulgaris.

Table 10. ter/ Terbutryn/chlorothalonil Qter QTER ter Qc QC si QTER Qc/QC 100/0 1 1 1 80/20 1 1 1 200 500 0, 4 1, 4 60/40 0, 5 1 0, 5 150 500 0, 2 0, 7 50/50 0, 5 1 0, 5 125 500 0, 25 0, 75 40/60 0, 5 1 0, 5 100 500 0, 2 0, 7 20/80 0, 5 1 0, 5 25 500 0, 05 0, 55 0/100---500 50 1- It is evident from the data in the table, that the most optimal algaecide combination of the two components terbutryn and chlorothalonil is found at a concentration of 20% (w/w) of terbutryn and 80% (w/w) chlorothalonil, 40% (w/w) of terbutryn and 60% (w/w), 50% (w/w) of terbutryn and 50% (w/w) chlorothalonil, 60% (w/w) of terbutryn and 40% (w/w) chlorothalonil.

Example 11.

In this example the influence of the synergism of combinations of terbutryn and NOIT in the inventive composition has been investigated.

For that purpose aqueous dispersions with different concentrations were prepared of terbutryn and NOIT and the effect of these preparations were investigated against Clzlorella vulgaris.

Table 11. tf-r/ terbutryn/NOIT Qter QTER ter Qnoit QNOIT Qnoit/QN SI OIT 100/0 1 1 1 80/20 1 1 1 175 750 0, 23 1, 23 60/40 0, 5 1 0, 5 150 750 0, 2 0, 7 50/50 0, 5 1 0, 5 100 750 0, 13 0, 63 40/60 0, 5 1 0, 5 75 750 0, 1 0, 6 20/80 0, 5 1 0, 5 20 750 0, 03 0, 53 0/100---750 750 1 It is evident from the data in the table, that the most optimal algaecide combination of the two components terbutryn and NOIT is found at a concentration of 20% (w/w) of terbutryn and 80% (w/w) NOIT, 40% (w/w) of terbutryn and 60% (w/w), 50% (w/w) of terbutryn and 50% (w/w) NOIT, 60% (w/w) of terbutryn and 40% (w/w) NOIT.

Example 12 In this example the influence of the synergism of combinations of terbutryn and DCOIT in the inventive composition has been investigated.

For that purpose aqueous dispersions with different concentrations were prepared of terbutryn and DCOIT and the effect of these preparations were investigated against Chlorella vulgaris.

Table 12. te terbutryn/DCOIT Qter QTER Q Qdcoit QDCOIT Qdcoit/Q si DOIT 100/0 1 1 1- 80/20 1 1 1 4 5 0, 8 1, 8 60/40 0, 5 1 0, 5 2 5 0, 4 0, 9 50/50 0, 5 1 0, 5 2 5 0, 4 0, 9 40/60 0, 5 1 0, 5 1 5 0, 2 0, 7 20/80 0, 5 1 0, 5 1 5 0, 2 0, 7 0/100 5 5 I It is evident from the data in the table, that the most optimal algaecide combination of the two components terbutryn and DCOIT is found at a concentration of 20% (w/w) of terbutryn and 80% (w/w) DCOIT, 40% (w/w) of terbutryn and 60% (w/w), 50% (w/w) of terbutryn and 50% (w/w) DCOIT, 60% (w/w) of terbutryn and 40% (w/w) DCOIT.

The same synergistic effect is observed when terbutryn is substituted by 2-methylthio-4-t- butylamino-6-cyclopropylamino-s-triazine (cybutrin).