WO2004098289A1

WO2004098289A1 - Synergistic antimicrobial composition with terbutryn

Info

Publication number: WO2004098289A1
Application number: PCT/EP2003/004769
Authority: WO
Inventors: Amaro Izquierdo Ramis; Joan Seguer Bonaventura
Original assignee: Laboratorios Miret S.A.
Priority date: 2003-05-07
Filing date: 2003-05-07
Publication date: 2004-11-18
Also published as: EP1622451A1; BR0318286A; MXPA05011916A; AU2003236629A1

Abstract

Compositions comprising a first component selected from terbutryn and cybutryn and at least one second component selected from chlorothalonil, 2-octyl-2H-isothiazol-3-one and 4,5-dichloro-2-octyl-2H-isothiazol-3-one. These compositions show a synergistic antimicrobial activity.

Description

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-l,3,5-triazine-2,4- diylamine (hereafter terbutryn) and 2-methyltlιio-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 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 = Qbiodde-i/QBiociDE-i + 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 _bi_oci_de-i : rninimum inhibition concentration of biocide-1 in the mixture of biocide 1 and biocide-2 Q BI_OCIDE-I: Minimum inhibition concentration of biocide-1 as single biocide without biocide-2, Q _bi_oci_de-₂ : minimum inhibition concentration of biocide-2 in the mixture of biocide-1 and biocide-2 Q BI_OCIDE-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-pyridine thiol 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.

i 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.

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.

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.

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 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 terbutryn 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.

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.

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.

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.

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.

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.

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.

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.

A GICIDE

Example 10.

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.

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.

For that purpose aqueous dispersions with different concentrations were prepared of terbutryn and NOIT and the effect of these preparations were investigated against Chlorella vulgaris. Table 11.

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

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.

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- butylammo-6-cycloproρylamino-s-triazine (cybutrin) .

Claims

1. Antimicrobial composition comprising a first component selected from terbutryn and cybutryn and at least one second component 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).

2. The composition of claim 1, the first component being terbutryn.

3. The composition of claim 1 or 2, the second component being chlorothalonil.

4. The antimicrobial composition according to any of claims 1 to 3, further comprising as a third component 3-iodo-2-propinyl butylcarbamate (IPBC) or zinc-2-pyridine thiol 1 -oxide.

5. A microbiocidal composition according to any of claims 1 to 3 wherein the weight ratio of first component to the second component is from 100:1 to 1 : 100.

6. The microbiocidal composition according to claim 4 wherein the weight ratio of the first composition to the third component is from 100:1 to 1: 100.

7. Composition according to any of claims 1 to 3, wherein the ratio of terbutryn to other biocides is 20:1 to 1:20, preferably from 1:1 to 1: 1.

8. Composition according to claim 4, wherein the ratio of terbutryn to other biocides is 20:1 to 1:20, preferably from 1:1 to 1: 1.

9. The use of the antimicrobial compositions according to any of the previous claims for inhibiting the growth of bacteria fungi and algae in aqueous paints and coatings, preserving wood and cutting fluids, and controlling slime-producing fungi in pulp and paper mill.