CA1228807A - Mixtures having biocidal activity - Google Patents
Mixtures having biocidal activityInfo
- Publication number
- CA1228807A CA1228807A CA000438373A CA438373A CA1228807A CA 1228807 A CA1228807 A CA 1228807A CA 000438373 A CA000438373 A CA 000438373A CA 438373 A CA438373 A CA 438373A CA 1228807 A CA1228807 A CA 1228807A
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- Canada
- Prior art keywords
- compound
- alkyl
- formula
- iii
- mixture according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
- A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
- A01N55/04—Tin
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/34—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-halogen bonds; Phosphonium salts
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/50—Mixtures of different organic impregnating agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
Abstract
Mixtures having biocidal activity Abstract Compounds of the formula I and/or II and/or VI
(I), (II), (VI) in which R1, X, Y, L, M, r, t and n are as defined in the description can be rendered soluble in water by adding com-pounds of the formula III
(III) in which R2, R3 and Q are as defined in the description.
Mixtures of this type have a good biocidal activity and are particularly suitable for the preservation of materials and for water treatment.
(I), (II), (VI) in which R1, X, Y, L, M, r, t and n are as defined in the description can be rendered soluble in water by adding com-pounds of the formula III
(III) in which R2, R3 and Q are as defined in the description.
Mixtures of this type have a good biocidal activity and are particularly suitable for the preservation of materials and for water treatment.
Description
LZZ88~:)7 3-14133/CGM 277/+
Mixtures having biocidal activity The present invention relates to mixtures having biocidal activity and containing an organotin compound or a tin halide and a phosphonium halide, the use of these mix-lures as besides, and a process for solubilising organotin compounds in water.
It is known that triorganotin compounds, in portico-far organotin oxides, can be used as besides, and their importance has increased continually in recent years. For a long time it was only possible to use such substances as solutions in organic solvents. Their applicability was therefore limited for technological and ecological reasons.
There was therefore a need to be able to employ besides having a similar activity, but soluble in water. The use of organotin compounds together with ammonium salts in aqueous systems was suggested in British Patent Specification 1,467,420 as a means of increasing the volubility in water.
However, this method is not entirely satisfactory; in many cases only dispersions are formed, which makes it necessary to use organic solvents concomitantly, or there is hardly any increase in the sealability in water, or none, which is relevant, for example, to solubilising organotin fluorides.
In other cases, although the organotin compounds are disk solved at low concentrations, the solutions prove unstable.
The combination tetradecyltriphenylphosphonium chloride/TBT0 is suggested for use in industrial cooling water systems in a data sheet of the firm Carlisle The present invention relates to mixtures containing a) at least one organotin compound of the formula I and/or aye II and/or VI
L R3Sn ¦ X (I), R3Sn-Y-SnR3 (II), Sol My (Al), in which n is 1, 2 or 3, r and t independently of one another can assume values from O to 4, it being necessary for the total (rut) to be 4, L and M independently of one another are fluoride, chloride, bromide, iodide, cyanide, Senate or thiocyanate, X is the anion of an n-basic inorganic acid or an n-basic carboxylic acid or is -OH, Y is oxygen or sulfur and R1 is C1-C6-alkyl which is unsubstituted or subset-tuned by hydroxyl, cyan or halogen, C3~C7-cycloalkyl, phenol or 2-methyl-2-phenylpropyl, and b) at least one phosphonium compound of the formula III
~R3PR~l Q ( I I I ) in which R2 can be as defined for R1 and R3 is C1-C22-alkyd, C8-C22-alkyl which is substituted by hydroxyl or color-inn C8-CzO-alkylbenzyl or a group of the formula lo -Z-PR23 (IV) in which R2 is as defined above and Z is a linear or branched (CVH2v) group, v being a number from 2 to 22 and it being possible for this group to be interrupted once or several times by -O-, -S-, -OX-, -coo- -N(R)- in which R is hydrogen or C1-C4-alkyl and Q is a halide, the combinations III:I or IVY or III:II being present in the mixture in a molar ratio of at least no or at least 1:1 or at least 2:1, respectively; and R2 must not be phenol if the mixture consists of the phosphonium compound III in which R3 is C1-Cz2-alkyl and of the organotin compound of the formula II in which R1 is n-butyl and Y is oxygen.
Examples of R1 and R2 as C1-C6-alkyl and of R3 as C1-C2z-alkyl are linear or branched alkyd radicals, such as methyl, ethyl n-propyl, isopropyl, n-butyl, sec.-bottle, tert.-butyl, namely, isoamyl, n-hexyl, n-octyl, ~L2;~:8~
Mixtures having biocidal activity The present invention relates to mixtures having biocidal activity and containing an organotin compound or a tin halide and a phosphonium halide, the use of these mix-lures as besides, and a process for solubilising organotin compounds in water.
It is known that triorganotin compounds, in portico-far organotin oxides, can be used as besides, and their importance has increased continually in recent years. For a long time it was only possible to use such substances as solutions in organic solvents. Their applicability was therefore limited for technological and ecological reasons.
There was therefore a need to be able to employ besides having a similar activity, but soluble in water. The use of organotin compounds together with ammonium salts in aqueous systems was suggested in British Patent Specification 1,467,420 as a means of increasing the volubility in water.
However, this method is not entirely satisfactory; in many cases only dispersions are formed, which makes it necessary to use organic solvents concomitantly, or there is hardly any increase in the sealability in water, or none, which is relevant, for example, to solubilising organotin fluorides.
In other cases, although the organotin compounds are disk solved at low concentrations, the solutions prove unstable.
The combination tetradecyltriphenylphosphonium chloride/TBT0 is suggested for use in industrial cooling water systems in a data sheet of the firm Carlisle The present invention relates to mixtures containing a) at least one organotin compound of the formula I and/or aye II and/or VI
L R3Sn ¦ X (I), R3Sn-Y-SnR3 (II), Sol My (Al), in which n is 1, 2 or 3, r and t independently of one another can assume values from O to 4, it being necessary for the total (rut) to be 4, L and M independently of one another are fluoride, chloride, bromide, iodide, cyanide, Senate or thiocyanate, X is the anion of an n-basic inorganic acid or an n-basic carboxylic acid or is -OH, Y is oxygen or sulfur and R1 is C1-C6-alkyl which is unsubstituted or subset-tuned by hydroxyl, cyan or halogen, C3~C7-cycloalkyl, phenol or 2-methyl-2-phenylpropyl, and b) at least one phosphonium compound of the formula III
~R3PR~l Q ( I I I ) in which R2 can be as defined for R1 and R3 is C1-C22-alkyd, C8-C22-alkyl which is substituted by hydroxyl or color-inn C8-CzO-alkylbenzyl or a group of the formula lo -Z-PR23 (IV) in which R2 is as defined above and Z is a linear or branched (CVH2v) group, v being a number from 2 to 22 and it being possible for this group to be interrupted once or several times by -O-, -S-, -OX-, -coo- -N(R)- in which R is hydrogen or C1-C4-alkyl and Q is a halide, the combinations III:I or IVY or III:II being present in the mixture in a molar ratio of at least no or at least 1:1 or at least 2:1, respectively; and R2 must not be phenol if the mixture consists of the phosphonium compound III in which R3 is C1-Cz2-alkyl and of the organotin compound of the formula II in which R1 is n-butyl and Y is oxygen.
Examples of R1 and R2 as C1-C6-alkyl and of R3 as C1-C2z-alkyl are linear or branched alkyd radicals, such as methyl, ethyl n-propyl, isopropyl, n-butyl, sec.-bottle, tert.-butyl, namely, isoamyl, n-hexyl, n-octyl, ~L2;~:8~
2-ethylhexyl, decal, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl or docosyl. The invention also relates to mixtures of such alkyd groups as tetradecyl and hexadecyl. R3 is preferably C8-C18-alkYl, especially C12 Colloquial It is also preferable for R1 and R2 independently of one another to be C1-C6-alkyl, especially n-butyl.
Examples of R1, R2 and R3 as C1-C6-hydroxyalkyl are methylol, 2-hydroxyethyl, 4-hydroxylbutyl or 6-hydroxy-Huxley, preferably methylol~
As C3-C7-cycloalkyl, R1 and R2 are especially cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycle-hotly, preferably cyclohexyl.
Examples of R3 as substituted C8-C22-alkyl are 8-chlorooctyl, 4-chlorooctadecyl, 10-hydroxydecyl or 20-hydroxyeicosyl.
R3 us preferably C8-C20-alkylbenzyl and can be sub-stituted, for example, on the phenol ring by methyl, ethyl, Huxley, decal, dodecyl, sec.-butyl, tert.-butyl or isoamyl.
If R3 is a group of the formula IV, Z is, for example ethylene, 1,3-trimethylene, 1,4-tetramethylene, prOpylidene, -CH2CH2-0-CH2cH2-~ (C~20)4cH2cH2 ' -CH2CH2-NH-CH2CH2-~ -CH2CH2 N(CH3) CH2CH2 -CH2COOCH2cH2 Examples of R as C1-C4-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl or t.-butyl.
Examples of X as the anion of an inorganic acid are fluoride, chloride, bromide, iodide, cyanide, Senate, trio-Senate, nitrate, sulfate, phosphate thiophosphate or born ate. The preferred anions are fluoride and chloride.
As a carboxylate anion, X is the anion of an n-basic carboxylic acid, for example format, acetate, preappoint, acrylate, methacrylate, hexanoate, subacute, naphthenate, abietate or citrate.
n is preferably 1.
Y is preferably oxygen.
1~2~80~
Mixtures in which the compound of the formula I is tributyltin chloride or fluoride are particularly preferred.
Mixtures in which the compound of the formula II is d;-(tributyltin) oxide are also of interest.
R2 in the formula III is as defined for R1 in the formulae I and II, but, within the definitions given, R1 and R2 in a mixture according to the invention can be entirely different.
As a halide, Q is fluoride, chloride, bromide or iodide, preferably fluoride and especially chloride.
In order to syllables 1 mow of a compound of the formula I [Risk] X to an adequate extent it us advantageous if the mixture contains at least n mow of the compound of the formula III, whereas in the case of compounds of the formula VI at least 1 mow of the compound of the formula III
per mow of the compound VI is adequate.
As a rule, a twice molar amount of a compound of the formula III is sufficient to give excellent results with the compounds of the formula II. If desired, the compound III can, of course, also be employed in a large excess in the mixture, for instance on a molar ratio of 50:1. In order to obtain a good biocidal action, in practice mixtures of come pounds of the formula III and I or III and VI or III and II
are employed in a molar ratio of no to 20:1 or of 1:1 to 20:1 or of 2:1 to Z0:1, respectively, preferably no to 12:1 or 1:1 to 12:1 or 2:1 to 12:1, respectively.
Preferred mixtures contain at least one or~anotin compound of the formula I and/or II in which X is fluoride, chloride, bromide, iodide, cyanide, Senate, thiocyanate, nitrate, sulfate, phosphate, thiophosphate, borate, format, acetate, preappoint, acrylate, methacrylate~ hexanoate, naphthenate, subacute or hydroxide, R1 is C1-C6-alkyl, methylol, cyclohexyl, phenol or 2-methyl-2-phenylpropyl, and also contain at least one phosphonium compound of the formula III in which R2 can be as defined for R1 and R3 is ~X~:8~r' I
C8~Cz2-alkyl which is unsubstituted or substituted by hydroxyl or chlorine, or is C8-Czo-alkylbenzyl, and in which Q is fluoride, chloride, bromide or iodide; R2 must not be phenol if the mixture consists of the phosphonium compound III in which R3 is C8-C2z-alkyl and of the organotin compound II in which R1 is n-butyl and Y is oxygen.
Particular interest attaches to mixtures containing compounds of the formulae I and/or II and/or VI and III in which n is 1 and X and/or L and/or M are fluoride or color-ides Y is oxygen and R1 and R2 independently of one another are C1-C6-alkyl or phenol, and R3 is Cg-C18-alkyl or Cg-Czo~alkylbenzyl and Q is chloride or fluoride; in this case RZ must not be phenol if the mixture contains a come pound of the formula II on which R3 is C8-C18-alkyl, R1 is n-butyl and Y is oxygen.
Mixtures which are particularly preferred contain at least the compound tri-n-butyltetradecylphosphonium chloride and the compound di-(tri-n-butyltin) oxide.
Mixtures which are also preferred contain at least the compound tri-n-butyltetradecylphosphonium chloride and the compound tri-n-butyltin chloride.
Mixtures which are also of interest contain at least the compound tri-n-butyltetradecylphosphonium chloride and the compound tri-n-butyltin fluoride.
Mixtures which also deserve consideration contain at least the compound tri-n-butyltetradecylphosphonium color-ire and the compound triphenyltin hydroxide.
Preferred mixtures contain at least the compound tri-n-butyl-tetradecylphosphonium chloride and the compound triphenyltin acetate.
The following are examples of compounds of the for-mute I:
1. Tr;methyltin chloride 2. Tri-n-butyltin fluoride
Examples of R1, R2 and R3 as C1-C6-hydroxyalkyl are methylol, 2-hydroxyethyl, 4-hydroxylbutyl or 6-hydroxy-Huxley, preferably methylol~
As C3-C7-cycloalkyl, R1 and R2 are especially cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycle-hotly, preferably cyclohexyl.
Examples of R3 as substituted C8-C22-alkyl are 8-chlorooctyl, 4-chlorooctadecyl, 10-hydroxydecyl or 20-hydroxyeicosyl.
R3 us preferably C8-C20-alkylbenzyl and can be sub-stituted, for example, on the phenol ring by methyl, ethyl, Huxley, decal, dodecyl, sec.-butyl, tert.-butyl or isoamyl.
If R3 is a group of the formula IV, Z is, for example ethylene, 1,3-trimethylene, 1,4-tetramethylene, prOpylidene, -CH2CH2-0-CH2cH2-~ (C~20)4cH2cH2 ' -CH2CH2-NH-CH2CH2-~ -CH2CH2 N(CH3) CH2CH2 -CH2COOCH2cH2 Examples of R as C1-C4-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl or t.-butyl.
Examples of X as the anion of an inorganic acid are fluoride, chloride, bromide, iodide, cyanide, Senate, trio-Senate, nitrate, sulfate, phosphate thiophosphate or born ate. The preferred anions are fluoride and chloride.
As a carboxylate anion, X is the anion of an n-basic carboxylic acid, for example format, acetate, preappoint, acrylate, methacrylate, hexanoate, subacute, naphthenate, abietate or citrate.
n is preferably 1.
Y is preferably oxygen.
1~2~80~
Mixtures in which the compound of the formula I is tributyltin chloride or fluoride are particularly preferred.
Mixtures in which the compound of the formula II is d;-(tributyltin) oxide are also of interest.
R2 in the formula III is as defined for R1 in the formulae I and II, but, within the definitions given, R1 and R2 in a mixture according to the invention can be entirely different.
As a halide, Q is fluoride, chloride, bromide or iodide, preferably fluoride and especially chloride.
In order to syllables 1 mow of a compound of the formula I [Risk] X to an adequate extent it us advantageous if the mixture contains at least n mow of the compound of the formula III, whereas in the case of compounds of the formula VI at least 1 mow of the compound of the formula III
per mow of the compound VI is adequate.
As a rule, a twice molar amount of a compound of the formula III is sufficient to give excellent results with the compounds of the formula II. If desired, the compound III can, of course, also be employed in a large excess in the mixture, for instance on a molar ratio of 50:1. In order to obtain a good biocidal action, in practice mixtures of come pounds of the formula III and I or III and VI or III and II
are employed in a molar ratio of no to 20:1 or of 1:1 to 20:1 or of 2:1 to Z0:1, respectively, preferably no to 12:1 or 1:1 to 12:1 or 2:1 to 12:1, respectively.
Preferred mixtures contain at least one or~anotin compound of the formula I and/or II in which X is fluoride, chloride, bromide, iodide, cyanide, Senate, thiocyanate, nitrate, sulfate, phosphate, thiophosphate, borate, format, acetate, preappoint, acrylate, methacrylate~ hexanoate, naphthenate, subacute or hydroxide, R1 is C1-C6-alkyl, methylol, cyclohexyl, phenol or 2-methyl-2-phenylpropyl, and also contain at least one phosphonium compound of the formula III in which R2 can be as defined for R1 and R3 is ~X~:8~r' I
C8~Cz2-alkyl which is unsubstituted or substituted by hydroxyl or chlorine, or is C8-Czo-alkylbenzyl, and in which Q is fluoride, chloride, bromide or iodide; R2 must not be phenol if the mixture consists of the phosphonium compound III in which R3 is C8-C2z-alkyl and of the organotin compound II in which R1 is n-butyl and Y is oxygen.
Particular interest attaches to mixtures containing compounds of the formulae I and/or II and/or VI and III in which n is 1 and X and/or L and/or M are fluoride or color-ides Y is oxygen and R1 and R2 independently of one another are C1-C6-alkyl or phenol, and R3 is Cg-C18-alkyl or Cg-Czo~alkylbenzyl and Q is chloride or fluoride; in this case RZ must not be phenol if the mixture contains a come pound of the formula II on which R3 is C8-C18-alkyl, R1 is n-butyl and Y is oxygen.
Mixtures which are particularly preferred contain at least the compound tri-n-butyltetradecylphosphonium chloride and the compound di-(tri-n-butyltin) oxide.
Mixtures which are also preferred contain at least the compound tri-n-butyltetradecylphosphonium chloride and the compound tri-n-butyltin chloride.
Mixtures which are also of interest contain at least the compound tri-n-butyltetradecylphosphonium chloride and the compound tri-n-butyltin fluoride.
Mixtures which also deserve consideration contain at least the compound tri-n-butyltetradecylphosphonium color-ire and the compound triphenyltin hydroxide.
Preferred mixtures contain at least the compound tri-n-butyl-tetradecylphosphonium chloride and the compound triphenyltin acetate.
The following are examples of compounds of the for-mute I:
1. Tr;methyltin chloride 2. Tri-n-butyltin fluoride
3. Tri-n-butyltin chloride
4. Tri-n-butyltin acetate
5. Tri-n-butyltin acrylate
6, Tri-n-butylt;n methacrylate
7. Tris-tri-n-butytin phosphate
8. TricycLohexyltin chloride
9. Triphenyltin chloride
10. Triphenyltin fluoride ll.Di-n-butyl-propyltin chloride 1Z. Tri-n-butyltin naphthenate 13. Triphenyltin hydroxide 14. Tricyclohexyltin hydroxide 15. Tri-n-butyltin bonniest 16. Tri-n-butyltin cyanide 17. Tri-n-butyltin thiocyanate The following are examples of compounds of the for-mute II:
18. Di-(trimethyltin) oxide 19. Di-(tri-n-butyltin) oxide 20. Di-(tri-n~butyltin) sulfide 21. Di-(tr;cyclohexyl) oxide 22. D;-(tr;cyclohexyl) sulfide 23. Di-(triphenyltin) oxide 24, D;-(triphenyltin) sulfide 25. Di-(tri-n-propyltin) oxide 26, Di-(tricyclohexyltin) oxide The following are examples of compounds of the formula III:
27. Tri-n-butyl-n~dodecylphosphonium chloride 28. Tri-n-butyltetradecylphosphon;um chloride 29. Tri-n-butyl-n~decylphosphonium chloride 30. Tri-n-butyl-n tctradecylphosphonium bromide 31. Trimethylol-p~laurylbenzylphosphon;um chloride 32, Tri-n-butyl-~n-laurylphosphonium chloride 33. Tri-n-butyl-n-laurylphosphonium bromide 34. Tri-n-butyl-n-hexadecylphosphonium chloride 35. Tri-n-butyl-n~dodecylphosphonium bromide 36. Tri-n-butyl-p~laurylbenzylphosphonium chloride 37. Triphenyl-n-tetradecylphosphonium bromide 38. Triphenyl-n-octadecylphosphonium bromide ~22~380~
39. Triphenyl-n-dodecylphosphonium fluoride 40. Triphenyl-n-dodecylphosphonium chloride The following are examples of compounds of the for-mute VI:
41- Tin tetrachloride 42. Tin tetrafluoride 43. Tin tetrabromide 44. Tin tetraiocdide Good results are achieved with mixtures of the following compounds: (2+34), (2+27), (18+28), (2+29), (3+28), (19+28), (12+28), (2+37), (2+38), (28+41) and (2+30).
The tar, salts of the formula I, II and VI are common-Cole available products. The phosphon;um halides of the formula III are also commercial products or can be prepared by known methods from the corresponding phosph;nes and an organic halide.
The invention also relates to the use of a mixture Courtney at yeast one organot;n compound of the formula I
ardor II and/or VI and at least one phosphon;um halide of the formula III as a buzzed.
The mixtures according to the invention provide a broad spectrum of action for the control of animal and plant pests, leading to many different possible uses, for example as bactericide or disinfectants, against the formation of slime in paper manufacture and as fung;c;des, insecticides, acaricides, herbicides and alg;cides. In add ton the novel substances are excellently suitable for use as incus-trial antimicrobial agents for the protection of materials, for example for protecting wood, cellulose and paper, text-ties and leather, dyes, pants ant fouling paints and smiler coating substances, optical glass and other types of glass, cooling water, plastics, rubber and adhesives, drooling and cutting oils, petroleum, lubricants, waxes and fuels and other materiels In particular, the mixtures according to the oven ton can also be used for protecting biodegradable plastics and plastics compositeness, preferably for protecting ~L;22~
plasticized polyvinyl chloride or polyvinylidene chloride.
Depending on the purpose for which they are used, the compounds are employed in the concentration ranges known to those skilled in the art. The limits of the customary concentrations are given by the following values: whereas in cooling water concentrations as low as the Pam range are sufficient, in anti-fouling formulations concentrations of up to 40 X by weight are customary.
A preferred field of application is constituted by protective coating agents, particularly anti-fouling paints, which are based on organic materials and, besides the custom-cry primary materials and additives, contain 0.5 - 60 % by weight, preferably 3 - 40 % by weight and especially 8 - 25 X
by weight, based on the total mixture, of a compound of the formula I or mixtures thereof.
Customary primary materials for anti-fouling paints are the paint raw materials designated binders and known to those skilled in the art, such as natural and synthetic resins, homopolymeric and copolymeric products containing the monomers vinyl chloride, vinylidene chloride, styrenes vinyltoluene, vinyl esters, acrylic acids and methacrylic acid and esters thereof, and also chlorinated rubber, natural and synthetic rubber, if appropriate chlorinated or cyclised, and also reactive resins, such as epoxide resins, polyurethane resins and unsaturated polyesters which can, if desired, be converted into film-forming, higher-molecular products by the addition of curing agents.
The binders can be liquid or can be present in soul-lion. In the case of dissolved binders, including thcrmo~
plastics, a protective film can also be Formed by the vapor-anion of the solvent. Solid coating agents can, for example, be applied to articles by the powder coating process. Fur-then examples of customary primary materials are tar, mod-liens, dyes, inorganic or organic pigments, fillers and curing agents.
The use of the mixtures according to the invention as aqueous solutions or solutions containing water in the ~LX2~ 7 _ 9 _ protection of materials, in particular in disinfectants, in water treatment, in wood preservatives and in anti-fouling paints is, however, to be particularly emphasized.
The buzzed mixtures which can be used in accordance with the invention can also contain further active substances.
The following are examples of these:
a) Organosulfur compounds, for example ethylene dithiocyan~
ate (MET) or 3,5-dimethyltetrahydro-1,3,5-2H-thiadiazine-2-throne (DMTT). Substances of this type are employed in paper manufacture, particularly against the formation of slime.
b) Chlorinated phenols, such as sodium pentachlorophenate.
Compounds of this type are distinguished by a broad spectrum of action.
c) Copper salts, such as copper sulfate, in small quantities are effective algicides.
d) 2,2-Dibromo-3-nitrilopropionamide (DBNPA) as an algicide, fungicide and bactericide.
e) Chlorine and bromide are known, effective algicides and bactericide which are used particularly in water treatment.
f) Chlorine dioxide, chloroisocyanurates and hypochlorites are also customary besides in water treatment.
g) Known wood besides 91. Salt mixtures based on: silicofluorides, hydrogen fluorides, inorganic boron compounds, chromates, fluorides, arsenic (oxide or arsenates), a copper salt (sulfate or naphthenate), tin and zinc salts and mercury compounds.
9 . Tar oil preparations 93. Organic active compounds: pentachlorophenol, phenol, DOT, dieldrin, London or gammexane and chlorinated nap-thalenes.
h) Known disinfectants:
Phenol or phenol derivatives, formaldehyde and/or other aldehydes or derivatives, chlorine and organic or on-organic substances containing active chlorine, amphoteric surfactants.
i) In addition, it has proved particularly advantageous to use the mixtures according to the invention together with 2~380~
ammonium halides of the formula V:
[ R (R NO OR Q (V) on which Q us halogen and R4 and R5 independently of one another are hydrogen, C1-C6-alkyl, C1-C6-hydroxyalkyl or a polyglycol radical having a degree of polymerization of 2 to 25 and R6 us hydrogen, hydroxyl, C1-C6-alkyl, C1-C6-hydroxyalkyl, glycidyl, C1-C6-halogenoalkyl, phenol, bouncily, Cg-C22-alkylben7yl, monochlorobenzyl, d;chlorobenzyl, monon;trobenzyl, d;nitrobenzyl, trimethoxys;lylpropyl or in-ethoxysilylpropyl, and R7 is Cg-C2z-alkyl, a polyglycol radical having a degree of polymerization of 2-25, R8-phenoxy-ethoxyethyl, R8-C(O)NH-(CH2)m or R8-0-phenoxyethoxyethyl in which R8 is C1-C12-alkyl and m is 2 or 3, and R7 is also a group of the formula VII -Z-(R4)N(R5)R6 in which Z
us a linear or branched (CvHzv)group in which v is a number from 2 to 22 and R4, R5 and R6 are as defined above and, in addition, two of the radicals R4, R5, R6 and R7, together with the nitrogen atom to which they are attached, form a saturated or partially unsaturated heterocycl;c rung which is unsubstituted or substituted by one or two methyl or ethyl groups, or three of the radicals R4, R5, I and R7, together with the nitrogen atom to which they are attached, form an unsaturated heterocyclic ring which is us-substituted or substituted by one or two methyl, ethyl, hydroxyl or acutely groups.
Examples of R4, R5 and R6 as C1-C6-alkyl are linear or branched alkyd radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec~-butyl, namely, i50amyl or n-hexyl.
Examples of R4, R5 and R6 as C1-C6-hydroxy alkyd are methylol, 2-hydroxyethyl, 3-hydroxypropyl or 6-hydroxyhexyl.
Examples of R6 as C1-C6-halogenoalkyl, preferably C1-C2-halogenoalkyl are chloromethyl, 2-bromoethyl or 6-chlorohexyl. Halogen is preferably chlorine. Radicals such as 2-hydroxy-3-chloropropyl should also be mentioned.
~X2880~
R6 is substituted or unsubstituted bouncily, such as o-, m- or p-methylbenzyl, 2,3-, 2,4-, 3,4- or 2,5-dimethyl-bouncily, nonylbenzyl, laurylbenzyl, tetradecylbenzyl, o-, m-or p-chlorobenzyl, 2,3-, 3,4-, 3,5- or 2,5-dichlorobenzyl, o-, m- or p-nitrobenzyl or 2,3-, 3,4-, 3,5- or 2,5-d;nitro-bouncily.
As Cg-c22-alkyl~ R7 can be n-octyl, 2-ethyl-Huxley or branched or unbranched nonyl, decal, undecyl, do-decal, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl or docosyl.
Examples of R8 as C1-C12-alkyl are methyl, ethyl, n-propyl, n-butyl, sec.-butyl, n-hexyl, n~octyl, 2-ethyl-Huxley, 1,1,3,3-tetramethylbutyl or unbranched or branched nonyl, decal or dodecyl.
If two of the radicals R4, R5, R6 and R7, together with the nitrogen atom, form a saturated or partially saturated heterocylic ring which is unsubstituted or subset-tuned by one or two methyl or ethyl groups, this is, for example, pyrrolidine, piperidine, 2-methylpiperidine, piper-amine, Z,5-dimethylpiperazine or morpholine.
If three of the radicals R4, R5, R6 and R7, together with the nitrogen atom, form an unsaturated hotter-cyclic ring which is unsubstituted or substituted by one or two methyl or ethyl groups, this can be pardon, 4-methyl-pardon, quinoline, pyrimidine, thiazole, imidazole, ox-zone, 2-hydroxypyridine or 4-acetylpyridine.
Compounds of the formula V can be employed in a molar ratio of û:1 to 50:1, preferably up to 6:1, based on the compounds of the formula I or II or VI. Preferably, the molar ratio of the sum of the compounds of the formula III
to the compounds of the formula I is no to 12:1, to the compounds of the formula II is 2~1 to 12:1 and to the come pounds of the formula VI is 1:1 to 12:1.
In addition, further substances and assistants such as are customarily used concomitantly in such preparations can, of course, also be present in such formulations. En-apples of these are cat;onic or non ionic surface-active ~8~307 substances, electrolytes, completing agents, solubilisers and dyes and perfumes. These additives are used, for example, to improve the wetting power and the resistance to hardening, to adjust the viscosity and to increase the stability to cold conditions of the solutions.
The invention also relates to a process for soul-bilising compounds of the formula I and/or II and/or VI in water, wherein the aqueous medium contains at least one compound of the formula III, the molar ratio of the compounds of the formulae III:I and IVY being at least no and 1:1, respectively, and the ratio of the compounds of the formulae III to II being at least 2:1.
The precise mechanism of action of the solubilisation is not known, but it can result in an interaction between the compounds of the formulae III and I and/or II and/or VI, which can, for instance, be compared with a salvation effect.
It is particularly advantageous for the transport of aqueous systems containing besides if these systems con lain the besides dissolved in high concentrations. These systems are diluted by the final consumer to the concentra-lion desired for the particular application or, in many cases, are employed as such. The present invention also relates, therefore, to aqueous systems containing at least one organotin compound of the formulae I and/or II and/or VI
and at least one compound of the formula III, the molar ratio of the compounds of the formula III:I or IVY being at least no or 1:1, respectively, and the ratio of the come pounds of the formulae III:II being at least 2:1.
These solutions contain about 0~1 to US mow X of the compound of the formula I or of the formula VI, about 0.1 to 3 mow % of the compound of the formula II and about 0.1 to 6 mow % of the compound of the formula III.
The concentration us selected within these approx;-mate limits, depending on the end use. Thus in wood preserve anion, for example, high concentrations are of interest, whereas lower concentrations can also be selected for water treatment.
~.Z~38~7 The invention is illustrated in greater detail in the examples below.
Example 1: Di-(tributyltin) oxide (compound 19) is added at 30C to an 80% aqueous solution of tributyltetradecyl-phosphonium chloride (compound 28). This mixture is shaken continuously for 24 hours. A check is then made to see whether the whole quantity of tributyltin oxide has disk solved.
It is possible in this way to dissolve 8.4 mow % of the compound (19), whereas the final concentration of the compound (28) is 9.2 mow %. The same final concentration of (19) is obtained of a 40% aqueous solution of (28) is used initially.
Example ?: Using an experimental procedure analogous to that in Example 1, except that the compound (19) is replaced by (compound 3), 3.8 mow % of tributyltin chloride can be dissolved, the final concentration of the compound (28) being 15.3 mow %.
Example 3: Using an experimental procedure analogous to that in Example 1, except that the compound (19) is replaced by (compound 2), 2.9 mow of tributyltin fluoride can be dissolved, the final concentration of the compound (28) being 16.7 mow %. The same result is also obtained using a 40% solution of t28).
Examples 4-7: The following results are achieved (final concentrations) analogously to Example 1:
En- P compound Sun ~omppund ample _ _ _ _ __ ___ _ No. No. (I ) by (Lyle%) 78 139,2 l22 2 9 6 27 17,9 2 2,9 7 30 15,9 2 1'5~___ _ 122~3~307 Example 8: Test of activity in cooling circuits.
The cooling circuits, which are in the open natural solar radiation, entry of dust and effects of weathering), consist of:
a) a plastics vessel having a volume of 113 liters and an overflow, b) a pump (21 litres/minute at a head of 3 m) and c) a cooling tower equipped with boards of Oregon (swooped), Oregon (heart wood), oak, spruce, asbestos cement and PUKE.
The inflow of fresh water was adjusted to such a rate as to compensate for the loss through spray and evaporation, and the besides were diluted in a ratio of approximately 1:Z in 24 hours.
The cooling circuits are infested as the result of natural entry of dust and not by deliberate inoculation.
To prevent the formation of slime and the growth of algae, the cooling Crockett us treated with:
1. 50 ppm/week or 25 ppm/week of an aqueous formulation con-tanning 35 % of the compound 22 and 5 % of the compound 3 in H20, and 2. 21 Pam twice a week of a solution containing 45 % of the compound 28 and 5 % of the compound 19 in water.
The test was evaluated by observing the growth on the boards visually.
The circuit which had been treated at 50 ppm/week for the first three months and at 25 Pam for the next two months, and the circuit which had boon treated At 2]. porn Willis a week exhibited no sign at all of incipient slime Formation and growth of algae. A solution of the phosphon;um compound 28 employed on its own on these concentrations and at this ire-quench would not completely suppress the growth of algae for thus period of tome.
Example 9: Growth on wood Small blocks of spruce wood, 7 x 10 x 10 mm in size, 3L2~88Q~
were dried for 30 minutes in vacua. The blocks were then vacuum impregnated by keeping them in vacua for 30 minutes in 100 my of distilled water and buzzed and then subjecting them in the water to a pressure treatment (2 atmospheres gauge applied by compressed air) for 18 hours. The pieces of wood treated in this way were first subjected to leaching in running water and were then dried.
The dried pieces of wood were laid on potato-glucose ajar, and the wood and the surrounding ajar were inoculated with 0.1 ml of a spore suspension of a mixed culture of Aspergillus Niger Apergillus Phoenicia, Penicillium fun-culosum, Alternaria alternate, Cladosporum cladasporoidis, Aureobasidium pullulans and Cheetomium globusum (1~1+1 etc.).
After the wood had incubated for 4 weeks at 28C, growth was evaluated in accordance with the following rating:
1 = growth on the wood 2 = slight growth on the wood 3 = no growth on the wood 4 = no growth on the wood and inhibitory zone of 1 % of Growth after storage Growth after story compound compound in water for 1 week age in water for 4 weeks The excellent action of the formulations in preserve in wood even after storage in water, can be seen from the table.
18. Di-(trimethyltin) oxide 19. Di-(tri-n-butyltin) oxide 20. Di-(tri-n~butyltin) sulfide 21. Di-(tr;cyclohexyl) oxide 22. D;-(tr;cyclohexyl) sulfide 23. Di-(triphenyltin) oxide 24, D;-(triphenyltin) sulfide 25. Di-(tri-n-propyltin) oxide 26, Di-(tricyclohexyltin) oxide The following are examples of compounds of the formula III:
27. Tri-n-butyl-n~dodecylphosphonium chloride 28. Tri-n-butyltetradecylphosphon;um chloride 29. Tri-n-butyl-n~decylphosphonium chloride 30. Tri-n-butyl-n tctradecylphosphonium bromide 31. Trimethylol-p~laurylbenzylphosphon;um chloride 32, Tri-n-butyl-~n-laurylphosphonium chloride 33. Tri-n-butyl-n-laurylphosphonium bromide 34. Tri-n-butyl-n-hexadecylphosphonium chloride 35. Tri-n-butyl-n~dodecylphosphonium bromide 36. Tri-n-butyl-p~laurylbenzylphosphonium chloride 37. Triphenyl-n-tetradecylphosphonium bromide 38. Triphenyl-n-octadecylphosphonium bromide ~22~380~
39. Triphenyl-n-dodecylphosphonium fluoride 40. Triphenyl-n-dodecylphosphonium chloride The following are examples of compounds of the for-mute VI:
41- Tin tetrachloride 42. Tin tetrafluoride 43. Tin tetrabromide 44. Tin tetraiocdide Good results are achieved with mixtures of the following compounds: (2+34), (2+27), (18+28), (2+29), (3+28), (19+28), (12+28), (2+37), (2+38), (28+41) and (2+30).
The tar, salts of the formula I, II and VI are common-Cole available products. The phosphon;um halides of the formula III are also commercial products or can be prepared by known methods from the corresponding phosph;nes and an organic halide.
The invention also relates to the use of a mixture Courtney at yeast one organot;n compound of the formula I
ardor II and/or VI and at least one phosphon;um halide of the formula III as a buzzed.
The mixtures according to the invention provide a broad spectrum of action for the control of animal and plant pests, leading to many different possible uses, for example as bactericide or disinfectants, against the formation of slime in paper manufacture and as fung;c;des, insecticides, acaricides, herbicides and alg;cides. In add ton the novel substances are excellently suitable for use as incus-trial antimicrobial agents for the protection of materials, for example for protecting wood, cellulose and paper, text-ties and leather, dyes, pants ant fouling paints and smiler coating substances, optical glass and other types of glass, cooling water, plastics, rubber and adhesives, drooling and cutting oils, petroleum, lubricants, waxes and fuels and other materiels In particular, the mixtures according to the oven ton can also be used for protecting biodegradable plastics and plastics compositeness, preferably for protecting ~L;22~
plasticized polyvinyl chloride or polyvinylidene chloride.
Depending on the purpose for which they are used, the compounds are employed in the concentration ranges known to those skilled in the art. The limits of the customary concentrations are given by the following values: whereas in cooling water concentrations as low as the Pam range are sufficient, in anti-fouling formulations concentrations of up to 40 X by weight are customary.
A preferred field of application is constituted by protective coating agents, particularly anti-fouling paints, which are based on organic materials and, besides the custom-cry primary materials and additives, contain 0.5 - 60 % by weight, preferably 3 - 40 % by weight and especially 8 - 25 X
by weight, based on the total mixture, of a compound of the formula I or mixtures thereof.
Customary primary materials for anti-fouling paints are the paint raw materials designated binders and known to those skilled in the art, such as natural and synthetic resins, homopolymeric and copolymeric products containing the monomers vinyl chloride, vinylidene chloride, styrenes vinyltoluene, vinyl esters, acrylic acids and methacrylic acid and esters thereof, and also chlorinated rubber, natural and synthetic rubber, if appropriate chlorinated or cyclised, and also reactive resins, such as epoxide resins, polyurethane resins and unsaturated polyesters which can, if desired, be converted into film-forming, higher-molecular products by the addition of curing agents.
The binders can be liquid or can be present in soul-lion. In the case of dissolved binders, including thcrmo~
plastics, a protective film can also be Formed by the vapor-anion of the solvent. Solid coating agents can, for example, be applied to articles by the powder coating process. Fur-then examples of customary primary materials are tar, mod-liens, dyes, inorganic or organic pigments, fillers and curing agents.
The use of the mixtures according to the invention as aqueous solutions or solutions containing water in the ~LX2~ 7 _ 9 _ protection of materials, in particular in disinfectants, in water treatment, in wood preservatives and in anti-fouling paints is, however, to be particularly emphasized.
The buzzed mixtures which can be used in accordance with the invention can also contain further active substances.
The following are examples of these:
a) Organosulfur compounds, for example ethylene dithiocyan~
ate (MET) or 3,5-dimethyltetrahydro-1,3,5-2H-thiadiazine-2-throne (DMTT). Substances of this type are employed in paper manufacture, particularly against the formation of slime.
b) Chlorinated phenols, such as sodium pentachlorophenate.
Compounds of this type are distinguished by a broad spectrum of action.
c) Copper salts, such as copper sulfate, in small quantities are effective algicides.
d) 2,2-Dibromo-3-nitrilopropionamide (DBNPA) as an algicide, fungicide and bactericide.
e) Chlorine and bromide are known, effective algicides and bactericide which are used particularly in water treatment.
f) Chlorine dioxide, chloroisocyanurates and hypochlorites are also customary besides in water treatment.
g) Known wood besides 91. Salt mixtures based on: silicofluorides, hydrogen fluorides, inorganic boron compounds, chromates, fluorides, arsenic (oxide or arsenates), a copper salt (sulfate or naphthenate), tin and zinc salts and mercury compounds.
9 . Tar oil preparations 93. Organic active compounds: pentachlorophenol, phenol, DOT, dieldrin, London or gammexane and chlorinated nap-thalenes.
h) Known disinfectants:
Phenol or phenol derivatives, formaldehyde and/or other aldehydes or derivatives, chlorine and organic or on-organic substances containing active chlorine, amphoteric surfactants.
i) In addition, it has proved particularly advantageous to use the mixtures according to the invention together with 2~380~
ammonium halides of the formula V:
[ R (R NO OR Q (V) on which Q us halogen and R4 and R5 independently of one another are hydrogen, C1-C6-alkyl, C1-C6-hydroxyalkyl or a polyglycol radical having a degree of polymerization of 2 to 25 and R6 us hydrogen, hydroxyl, C1-C6-alkyl, C1-C6-hydroxyalkyl, glycidyl, C1-C6-halogenoalkyl, phenol, bouncily, Cg-C22-alkylben7yl, monochlorobenzyl, d;chlorobenzyl, monon;trobenzyl, d;nitrobenzyl, trimethoxys;lylpropyl or in-ethoxysilylpropyl, and R7 is Cg-C2z-alkyl, a polyglycol radical having a degree of polymerization of 2-25, R8-phenoxy-ethoxyethyl, R8-C(O)NH-(CH2)m or R8-0-phenoxyethoxyethyl in which R8 is C1-C12-alkyl and m is 2 or 3, and R7 is also a group of the formula VII -Z-(R4)N(R5)R6 in which Z
us a linear or branched (CvHzv)group in which v is a number from 2 to 22 and R4, R5 and R6 are as defined above and, in addition, two of the radicals R4, R5, R6 and R7, together with the nitrogen atom to which they are attached, form a saturated or partially unsaturated heterocycl;c rung which is unsubstituted or substituted by one or two methyl or ethyl groups, or three of the radicals R4, R5, I and R7, together with the nitrogen atom to which they are attached, form an unsaturated heterocyclic ring which is us-substituted or substituted by one or two methyl, ethyl, hydroxyl or acutely groups.
Examples of R4, R5 and R6 as C1-C6-alkyl are linear or branched alkyd radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec~-butyl, namely, i50amyl or n-hexyl.
Examples of R4, R5 and R6 as C1-C6-hydroxy alkyd are methylol, 2-hydroxyethyl, 3-hydroxypropyl or 6-hydroxyhexyl.
Examples of R6 as C1-C6-halogenoalkyl, preferably C1-C2-halogenoalkyl are chloromethyl, 2-bromoethyl or 6-chlorohexyl. Halogen is preferably chlorine. Radicals such as 2-hydroxy-3-chloropropyl should also be mentioned.
~X2880~
R6 is substituted or unsubstituted bouncily, such as o-, m- or p-methylbenzyl, 2,3-, 2,4-, 3,4- or 2,5-dimethyl-bouncily, nonylbenzyl, laurylbenzyl, tetradecylbenzyl, o-, m-or p-chlorobenzyl, 2,3-, 3,4-, 3,5- or 2,5-dichlorobenzyl, o-, m- or p-nitrobenzyl or 2,3-, 3,4-, 3,5- or 2,5-d;nitro-bouncily.
As Cg-c22-alkyl~ R7 can be n-octyl, 2-ethyl-Huxley or branched or unbranched nonyl, decal, undecyl, do-decal, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl or docosyl.
Examples of R8 as C1-C12-alkyl are methyl, ethyl, n-propyl, n-butyl, sec.-butyl, n-hexyl, n~octyl, 2-ethyl-Huxley, 1,1,3,3-tetramethylbutyl or unbranched or branched nonyl, decal or dodecyl.
If two of the radicals R4, R5, R6 and R7, together with the nitrogen atom, form a saturated or partially saturated heterocylic ring which is unsubstituted or subset-tuned by one or two methyl or ethyl groups, this is, for example, pyrrolidine, piperidine, 2-methylpiperidine, piper-amine, Z,5-dimethylpiperazine or morpholine.
If three of the radicals R4, R5, R6 and R7, together with the nitrogen atom, form an unsaturated hotter-cyclic ring which is unsubstituted or substituted by one or two methyl or ethyl groups, this can be pardon, 4-methyl-pardon, quinoline, pyrimidine, thiazole, imidazole, ox-zone, 2-hydroxypyridine or 4-acetylpyridine.
Compounds of the formula V can be employed in a molar ratio of û:1 to 50:1, preferably up to 6:1, based on the compounds of the formula I or II or VI. Preferably, the molar ratio of the sum of the compounds of the formula III
to the compounds of the formula I is no to 12:1, to the compounds of the formula II is 2~1 to 12:1 and to the come pounds of the formula VI is 1:1 to 12:1.
In addition, further substances and assistants such as are customarily used concomitantly in such preparations can, of course, also be present in such formulations. En-apples of these are cat;onic or non ionic surface-active ~8~307 substances, electrolytes, completing agents, solubilisers and dyes and perfumes. These additives are used, for example, to improve the wetting power and the resistance to hardening, to adjust the viscosity and to increase the stability to cold conditions of the solutions.
The invention also relates to a process for soul-bilising compounds of the formula I and/or II and/or VI in water, wherein the aqueous medium contains at least one compound of the formula III, the molar ratio of the compounds of the formulae III:I and IVY being at least no and 1:1, respectively, and the ratio of the compounds of the formulae III to II being at least 2:1.
The precise mechanism of action of the solubilisation is not known, but it can result in an interaction between the compounds of the formulae III and I and/or II and/or VI, which can, for instance, be compared with a salvation effect.
It is particularly advantageous for the transport of aqueous systems containing besides if these systems con lain the besides dissolved in high concentrations. These systems are diluted by the final consumer to the concentra-lion desired for the particular application or, in many cases, are employed as such. The present invention also relates, therefore, to aqueous systems containing at least one organotin compound of the formulae I and/or II and/or VI
and at least one compound of the formula III, the molar ratio of the compounds of the formula III:I or IVY being at least no or 1:1, respectively, and the ratio of the come pounds of the formulae III:II being at least 2:1.
These solutions contain about 0~1 to US mow X of the compound of the formula I or of the formula VI, about 0.1 to 3 mow % of the compound of the formula II and about 0.1 to 6 mow % of the compound of the formula III.
The concentration us selected within these approx;-mate limits, depending on the end use. Thus in wood preserve anion, for example, high concentrations are of interest, whereas lower concentrations can also be selected for water treatment.
~.Z~38~7 The invention is illustrated in greater detail in the examples below.
Example 1: Di-(tributyltin) oxide (compound 19) is added at 30C to an 80% aqueous solution of tributyltetradecyl-phosphonium chloride (compound 28). This mixture is shaken continuously for 24 hours. A check is then made to see whether the whole quantity of tributyltin oxide has disk solved.
It is possible in this way to dissolve 8.4 mow % of the compound (19), whereas the final concentration of the compound (28) is 9.2 mow %. The same final concentration of (19) is obtained of a 40% aqueous solution of (28) is used initially.
Example ?: Using an experimental procedure analogous to that in Example 1, except that the compound (19) is replaced by (compound 3), 3.8 mow % of tributyltin chloride can be dissolved, the final concentration of the compound (28) being 15.3 mow %.
Example 3: Using an experimental procedure analogous to that in Example 1, except that the compound (19) is replaced by (compound 2), 2.9 mow of tributyltin fluoride can be dissolved, the final concentration of the compound (28) being 16.7 mow %. The same result is also obtained using a 40% solution of t28).
Examples 4-7: The following results are achieved (final concentrations) analogously to Example 1:
En- P compound Sun ~omppund ample _ _ _ _ __ ___ _ No. No. (I ) by (Lyle%) 78 139,2 l22 2 9 6 27 17,9 2 2,9 7 30 15,9 2 1'5~___ _ 122~3~307 Example 8: Test of activity in cooling circuits.
The cooling circuits, which are in the open natural solar radiation, entry of dust and effects of weathering), consist of:
a) a plastics vessel having a volume of 113 liters and an overflow, b) a pump (21 litres/minute at a head of 3 m) and c) a cooling tower equipped with boards of Oregon (swooped), Oregon (heart wood), oak, spruce, asbestos cement and PUKE.
The inflow of fresh water was adjusted to such a rate as to compensate for the loss through spray and evaporation, and the besides were diluted in a ratio of approximately 1:Z in 24 hours.
The cooling circuits are infested as the result of natural entry of dust and not by deliberate inoculation.
To prevent the formation of slime and the growth of algae, the cooling Crockett us treated with:
1. 50 ppm/week or 25 ppm/week of an aqueous formulation con-tanning 35 % of the compound 22 and 5 % of the compound 3 in H20, and 2. 21 Pam twice a week of a solution containing 45 % of the compound 28 and 5 % of the compound 19 in water.
The test was evaluated by observing the growth on the boards visually.
The circuit which had been treated at 50 ppm/week for the first three months and at 25 Pam for the next two months, and the circuit which had boon treated At 2]. porn Willis a week exhibited no sign at all of incipient slime Formation and growth of algae. A solution of the phosphon;um compound 28 employed on its own on these concentrations and at this ire-quench would not completely suppress the growth of algae for thus period of tome.
Example 9: Growth on wood Small blocks of spruce wood, 7 x 10 x 10 mm in size, 3L2~88Q~
were dried for 30 minutes in vacua. The blocks were then vacuum impregnated by keeping them in vacua for 30 minutes in 100 my of distilled water and buzzed and then subjecting them in the water to a pressure treatment (2 atmospheres gauge applied by compressed air) for 18 hours. The pieces of wood treated in this way were first subjected to leaching in running water and were then dried.
The dried pieces of wood were laid on potato-glucose ajar, and the wood and the surrounding ajar were inoculated with 0.1 ml of a spore suspension of a mixed culture of Aspergillus Niger Apergillus Phoenicia, Penicillium fun-culosum, Alternaria alternate, Cladosporum cladasporoidis, Aureobasidium pullulans and Cheetomium globusum (1~1+1 etc.).
After the wood had incubated for 4 weeks at 28C, growth was evaluated in accordance with the following rating:
1 = growth on the wood 2 = slight growth on the wood 3 = no growth on the wood 4 = no growth on the wood and inhibitory zone of 1 % of Growth after storage Growth after story compound compound in water for 1 week age in water for 4 weeks The excellent action of the formulations in preserve in wood even after storage in water, can be seen from the table.
Claims (23)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A mixture containing a) at least one organotin compound of the formula I and/or II and/or VI
(I), R?Sn-Y-SnR? (II), SnLrMt (VI), in which n is 1, 2 or 3, r and t independently of one another can assume values from 0 to 4, it being necessary for the total (r + t) to be 4, L and M independently of one another are fluoride, chloride, bromide, iodide, cyanide, cyanate or thiocyanate, X is the anion of an n-basic inorganic acid or an n-basic carboxylic acid or is -OH, Y is oxygen or sulfur and R1 is C1-C6-alkyl which is unsubstituted or substituted by hydroxyl, cyano or halogen, C3-C7-cycloalkyl or 2-methyl-2-phenylpropyl, and, provided the organotin compound is of formula II, R1 additionally is phenyl, and b) at least one phosphonium compound of the formula III
(III), in which R2 can be as defined for R1 and R3 is C1-C22-alkyl, C8-C22-alkyl which is substituted by hydroxyl or chlorine, C8-C20-alkylbenzyl or a group of the formula IV-Z-PR? (IV), in which R2 is as defined above and Z is a linear or branched (CvH2v) group, v being a number from 2 to 22 and it being possible for this group to be interrupted once or several times by -O-, -S-, -OC(O)-, -C(O)-O- or -N(R)- in which R is hydrogen or C1-C4-alkyl and Q is a halide, the combinations III:I or III:VI or III:II
- 16a -being present in the mixture in a molar ratio of at least n:l or at least 1:1 or at least 2:1, respectively; and R2 must not be phenyl if the mixture consists of the phosphonium compound III in which R3 is C1-C22-alkyl and of the organotin compound of the formula II in which R1 is n-butyl and Y is oxygen.
(I), R?Sn-Y-SnR? (II), SnLrMt (VI), in which n is 1, 2 or 3, r and t independently of one another can assume values from 0 to 4, it being necessary for the total (r + t) to be 4, L and M independently of one another are fluoride, chloride, bromide, iodide, cyanide, cyanate or thiocyanate, X is the anion of an n-basic inorganic acid or an n-basic carboxylic acid or is -OH, Y is oxygen or sulfur and R1 is C1-C6-alkyl which is unsubstituted or substituted by hydroxyl, cyano or halogen, C3-C7-cycloalkyl or 2-methyl-2-phenylpropyl, and, provided the organotin compound is of formula II, R1 additionally is phenyl, and b) at least one phosphonium compound of the formula III
(III), in which R2 can be as defined for R1 and R3 is C1-C22-alkyl, C8-C22-alkyl which is substituted by hydroxyl or chlorine, C8-C20-alkylbenzyl or a group of the formula IV-Z-PR? (IV), in which R2 is as defined above and Z is a linear or branched (CvH2v) group, v being a number from 2 to 22 and it being possible for this group to be interrupted once or several times by -O-, -S-, -OC(O)-, -C(O)-O- or -N(R)- in which R is hydrogen or C1-C4-alkyl and Q is a halide, the combinations III:I or III:VI or III:II
- 16a -being present in the mixture in a molar ratio of at least n:l or at least 1:1 or at least 2:1, respectively; and R2 must not be phenyl if the mixture consists of the phosphonium compound III in which R3 is C1-C22-alkyl and of the organotin compound of the formula II in which R1 is n-butyl and Y is oxygen.
2. A mixture according to claim 1 containing at least one organotin compound of the formula I and/or II in which X is fluoride, chloride, bromide, iodide, cyanide, cyanate, thiocyanate, nitrate, sulfate, phosphate, thiophosphate, borate, formate, acetate, propionate, acrylate, methacrylate, hexanoate, naphthenate, sebacate or hydroxide, and R1 is C1-C6-alkyl, methylol, cyclohexyl, phenyl or 2-methyl-1-phenylpropyl, and also containing at least one phosphonium compound of the formula III in which R2 can be as defined for R1 and R3 is C8-C22-alkyl which is unsubstituted or substituted by hydroxyl or chlorine or is C8-C20-alkyl-benzyl.
3. A mixture according to claim 1 containing compounds of the formula I and/or II and/or VI and III in which n is 1 and X and/or L and/or M is fluoride or chloride, Y is oxygen and R1 and R2 independently of one another are C1-C6-alkyl or phenyl and R3 is C8-C18-alkyl or C8-C20-alkylbenzyl and Q is chloride or fluoride.
4. A mixture according to claim 1, wherein R3 in the formula III is C8-C18-alkyl.
5. A mixture according to claim 4, wherein R3 is C12-C16-alkyl.
6. A mixture according to claim 1, wherein X in the formula I is fluoride or chloride.
7. A mixture according to claim 1, wherein R1 and R2 in the formulae I, II and III independently of one another are C1-C6-alkyl
8. A mixture according to claim 7, wherein R1 and R2 are n-butyl.
9. A mixture according to claim 1, wherein R3 in the formula III is C8-C20-alkylbenzyl.
10. A mixture according to claim 1, wherein the compound of the formula II is tributyltin chloride or fluoride.
11. A mixture according to claim 1, wherein the compound of the formula II is di-(tributyltin) oxide.
12. A mixture according to claim 1 containing at least the compound tri-n-butyltetradecylphosphonium chloride and the compound di-(tri-n-butyltin) oxide.
13. A mixture according to claim 1 containing at least the compound tri-n-butyltetradecylphosphonium chloride and the compound tri-n-butyltin chloride.
14. A mixture according to claim 1 containing at least the compound tri-n-butyltetradecylphosphonium chloride and the compound tri-n-butyltin fluoride.
15. A mixture according to claim 1 containing at least the compound tri-n-butyltetradecylphosphonium chloride and the compound triphenyltin hydroxide.
16. A mixture according to claim 1 containing at least the compound tri-n-butyltetradecylphosphonium chloride and the compound triphenyltin acetate.
17. A mixture according to claim 1, containing, in addi-tion, at least ammonium halide of the formula V
(V) in which Q is halogen and R4 and R5 independently of one another are hydrogen, C1-C6-alkyl, C1-C6-hydroxyalkyl or a polyglycol radical having a degree of polymerisation of 2 to 25, and R6 is hydrogen, hydroxyl, C1-C6-alkyl, C1-C6-hydroxyalkyl, glycidyl, C1-C6-halogenoalkyl, phenyl, benzyl, C8-C22-alkylbenzyl, monochlorobenzyl, dichloro-benzyl, mononitrobenzyl, dinitrobenzyl, trimethoxysilylpropyl or triethoxysilylpropyl, and R7 is C8-C22-alkyl, a poly-glycol radical having a degree of polymerisation of 2-25, R8-phenoxyethoxyethyl, R8-C(O)NH-(CH2)m- or R8-O-phenoxyethoxyethyl in which R8 is C1-C12-alkyl and m is 2 or 3, and R7 is also a group of the formula VII
-Z-(R4)N(R5)R6 (VII) in which Z is as defined in claim 1 and R4, R5 and R6 are as defined above, and, in addition, two of the radicals R4, R5, R6 and R7, together with the nitrogen atom to which they are attached, form a satu-rated or partially unsaturated heterocyclic ring which is un-substituted or substituted by one or two methyl or ethyl groups, or three of the radicals R4, RS, R6 and R7, together with the nitrogen atom to which they are attached, form an unsaturated heterocyclic ring which is unsubstituted or substituted by one or two methyl, ethyl, hydroxyl or acetyl groups.
(V) in which Q is halogen and R4 and R5 independently of one another are hydrogen, C1-C6-alkyl, C1-C6-hydroxyalkyl or a polyglycol radical having a degree of polymerisation of 2 to 25, and R6 is hydrogen, hydroxyl, C1-C6-alkyl, C1-C6-hydroxyalkyl, glycidyl, C1-C6-halogenoalkyl, phenyl, benzyl, C8-C22-alkylbenzyl, monochlorobenzyl, dichloro-benzyl, mononitrobenzyl, dinitrobenzyl, trimethoxysilylpropyl or triethoxysilylpropyl, and R7 is C8-C22-alkyl, a poly-glycol radical having a degree of polymerisation of 2-25, R8-phenoxyethoxyethyl, R8-C(O)NH-(CH2)m- or R8-O-phenoxyethoxyethyl in which R8 is C1-C12-alkyl and m is 2 or 3, and R7 is also a group of the formula VII
-Z-(R4)N(R5)R6 (VII) in which Z is as defined in claim 1 and R4, R5 and R6 are as defined above, and, in addition, two of the radicals R4, R5, R6 and R7, together with the nitrogen atom to which they are attached, form a satu-rated or partially unsaturated heterocyclic ring which is un-substituted or substituted by one or two methyl or ethyl groups, or three of the radicals R4, RS, R6 and R7, together with the nitrogen atom to which they are attached, form an unsaturated heterocyclic ring which is unsubstituted or substituted by one or two methyl, ethyl, hydroxyl or acetyl groups.
18. A mixture according to claim 17, wherein two of the radicals R4, R5, R6 and R7, together with the nitrogen, form pyrrolidine, piperidine or morpholine, or three of the radicals R4, R5, R6 and R7, together with the nitrogen, form pyridine, quinoline, pyrimidine, thiazole or imidazole.
19. A mixture according to claim 1, wherein the molar ratio of the compounds of the formulae III:I is n:l to 20:1.
20. A mixture according to claim 1, wherein the molar ratio of the compounds of the formulae III:II is 2:1 to 20:1.
21. A mixture according to claim 1, wherein the molar ratio of the compounds of the formulae III:VI is 1:1 to 20:1.
22. An aqueous system containing at least one organotin compound of the formulae I and/or II and/or VI.
(I), R?Sn-Y-SnR? (II), SnLrMt (VI), in which n is 1, 2 or 3, r and t independently of one another can assume values from 0 to 4, it being necessary for the total (r + t) to be 4, L and M independently of one another are fluoride, chlor-ide, bromide, iodide, cyanide, cyanate or thiocyanate, X is the anion of an n-basic inorganic acid or an n-basic carboxylic acid or is -OH, Y is oxygen or sulfur and R1 is C1-C6-alkyl which is unsubstituted or substituted by hydroxyl, cyano or halogen, C3-C7-cycloalkyl, phenyl or 2-methyl-2-phenylpropyl, and, containing at least one phosphonium compound of the formula III
(III), in which R2 can be as defined for R1 and R3 is C1-C22-alkyl, C8-C22-alkyl which is substituted by hydroxyl or chlorine, C8-C20-alkylbenzyl or a group of the formula IV -Z-PR? (IV), in which R2 is as defined above and Z is a linear or branched (CvH2v) group, v being a number from 2 to 22 and it being possible for this group to be interrupted once or several times by -O-, -S-l -OC(O)-, -C(O)-O or -N(R)- in which R is hydrogen or C1-C4-alkyl and Q is a halide, the combinations III:I or III:VI or III:II being present in the mixture in a molar ratio of at least n:l or at least 1:1 or at least 2:1, respectively; and R2 must not be phenyl if the mixture consists of the phosphonium compound III in which R3 is C1-C22- alkyl and of the organotin compound of the formula II in which R1 is n-butyl and Y is oxygen.
(I), R?Sn-Y-SnR? (II), SnLrMt (VI), in which n is 1, 2 or 3, r and t independently of one another can assume values from 0 to 4, it being necessary for the total (r + t) to be 4, L and M independently of one another are fluoride, chlor-ide, bromide, iodide, cyanide, cyanate or thiocyanate, X is the anion of an n-basic inorganic acid or an n-basic carboxylic acid or is -OH, Y is oxygen or sulfur and R1 is C1-C6-alkyl which is unsubstituted or substituted by hydroxyl, cyano or halogen, C3-C7-cycloalkyl, phenyl or 2-methyl-2-phenylpropyl, and, containing at least one phosphonium compound of the formula III
(III), in which R2 can be as defined for R1 and R3 is C1-C22-alkyl, C8-C22-alkyl which is substituted by hydroxyl or chlorine, C8-C20-alkylbenzyl or a group of the formula IV -Z-PR? (IV), in which R2 is as defined above and Z is a linear or branched (CvH2v) group, v being a number from 2 to 22 and it being possible for this group to be interrupted once or several times by -O-, -S-l -OC(O)-, -C(O)-O or -N(R)- in which R is hydrogen or C1-C4-alkyl and Q is a halide, the combinations III:I or III:VI or III:II being present in the mixture in a molar ratio of at least n:l or at least 1:1 or at least 2:1, respectively; and R2 must not be phenyl if the mixture consists of the phosphonium compound III in which R3 is C1-C22- alkyl and of the organotin compound of the formula II in which R1 is n-butyl and Y is oxygen.
23. A system according to claim 22, containing about 0.1 to 1.5 mol % of the compound of the formula I or of the formula VI, and/or about 0.1 to 3 mol % of the compound of the formula II, and about 0.1 to 6 mol % of the compound of the formula III.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH587782 | 1982-10-06 | ||
| CH5877/82-1 | 1982-10-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1228807A true CA1228807A (en) | 1987-11-03 |
Family
ID=4300820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000438373A Expired CA1228807A (en) | 1982-10-06 | 1983-10-05 | Mixtures having biocidal activity |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0109354B1 (en) |
| JP (1) | JPS5988496A (en) |
| CA (1) | CA1228807A (en) |
| DE (1) | DE3367719D1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6310172B1 (en) | 1998-03-06 | 2001-10-30 | Bayer Aktiengesellschaft | Water-dispersible polyisocyanate preparations for producing repulpable paper |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2178959B (en) * | 1985-07-17 | 1989-07-26 | Grace W R & Co | Biocidal mixture |
| US4615807A (en) * | 1985-07-23 | 1986-10-07 | United States Environmental Resources, Corp. | Method for wastewater treatment |
| DE3628801A1 (en) * | 1986-08-25 | 1988-03-03 | Henkel Kgaa | ANTIMICROBIALLY EFFECTIVE MIXTURES |
| DE4112652A1 (en) * | 1991-04-18 | 1992-10-22 | Wolman Gmbh Dr | WOOD PRESERVATIVES |
| EP0544619A1 (en) * | 1991-11-27 | 1993-06-02 | Ciba-Geigy Ag | Protection of non-aqueous systems with biocides |
| ZA928476B (en) * | 1991-11-27 | 1993-05-06 | Fmc Corp Uk Ltd | Composition for protecting timber from fungal growth. |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1204226B (en) * | 1963-12-10 | 1965-11-04 | Boehringer Sohn Ingelheim | Process for the preparation of bisquaterner tin complex salts |
| NL126753C (en) * | 1963-12-18 | |||
| DE1802375A1 (en) * | 1968-10-10 | 1970-11-05 | C H Boehringer Sohm | Fungicidal mixtures |
| NO147264C (en) * | 1973-03-09 | 1983-03-09 | Albright & Wilson | PROCEDURE FOR TREATING CELLULOS MATERIALS |
-
1983
- 1983-10-03 DE DE8383810445T patent/DE3367719D1/en not_active Expired
- 1983-10-03 EP EP83810445A patent/EP0109354B1/en not_active Expired
- 1983-10-05 CA CA000438373A patent/CA1228807A/en not_active Expired
- 1983-10-06 JP JP18765383A patent/JPS5988496A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6310172B1 (en) | 1998-03-06 | 2001-10-30 | Bayer Aktiengesellschaft | Water-dispersible polyisocyanate preparations for producing repulpable paper |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5988496A (en) | 1984-05-22 |
| EP0109354B1 (en) | 1986-11-20 |
| DE3367719D1 (en) | 1987-01-08 |
| EP0109354A1 (en) | 1984-05-23 |
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