Patent GB-1102430-A (GB)
Title: Antifouling compositions and methods using metal salts of substituted benzimidazoles
IPC: C09D5/16
Filed: 1965-12-21
Abstract: Resinous anti-foulant coatings comprise compounds of formula <FORM:1102430/C3/1> where R is thiazolyl and R5 is hydrogen, phenyl, phenylthio, phenoxy, heterocyclic, C1- 5 alkyl, C1- 5 alkylthio, C1- 5 alkoxy, halo or halophenyl, together with vinyl resins e.g. vinyl acetate-vinyl chloride copolymer, polyvinyl chloride, polyvinyl acetate, polyvinyl butyral, or phenolic resins e.g. phenol-formaldehyde resin. Pigments, solvents, plasticizers, and driers may also be present, many of which are specified. In the examples (1) a vinyl chloride (86 weight per cent)-vinyl acetate (14 weight per cent) copolymer (average molecular weight of 10,000) is mixed with gum rosin, tricresyl phosphate, titanium dioxide, magnesium-calcium silicate, mercuric 2-(41-thiazolyl)-benzimidazole, methyl isobutyl ketone, and xylene; (2) phenol-formaldehyde and coumarone-indene resins are mixed with linseed oil, tung oil, zinc naphthenate, mica, diatomaceous silica naphtha, and zinc 2 - (41 - thiazolyl) - 5 - phenyl-benzimidazole; (5) coumarone-indene resin is mixed with gum rosin, coal tar, aluminium stearate, chlorinated rubber, mineral spirits, naphtha, Indian red, mercuric 2-(21-thiazolyl)-5 - (41 - fluorophenyl) - benzimidazole; and (6) the copolymer of (1) is mixed with gum rosin, mercuric 2-(21-thiazolyl) benzimidazole, methyl isobutyl ketone, tricresyl phosphate and aluminium stearate.ALSO:Paint compositions comprise complexes of lead, mercuric or zinc cations with compounds of formula <FORM:1102430/C4-C5/1> where R is thiazolyl, and R5 is hydrogen, phenyl, phenoxy, phenylthio, heterocyclic, C1-5 alkyl, C1-5 thio, C1-5 alkoxy, halo, or halophenyl together with a paint vehicle e.g. shellac or coal tar (pitch).  Other constituents may include driers, e.g. zinc naphthenate or manganese linoleate, toxic pigments e.g. cuprous chloride or oxide, cupric carbonate, mercuric oxide, or tributyl tin, non-toxic pigments e.g. diatomaceous silica, magnesium silicate, mica, Venetian red, Indian red, Barytes, precipitated chalk, zinc oxide, magnesium oxide, metallic zinc, or iron oxide, solvents e.g. methyl isobutyl ketone, naphtha, or xylene, and plasticizers e.g. abietates, chlorinated diphenyl, chlorinated rubber, tricresyl phosphate, dehydrated castor oil, coumaroneindene resin, paraffin wax, tall oils, linseed, tung and bodied fish oils. In Example 1, the formulation contains a vinyl copolymer & gum rosin, Example 2, synthetic resins, linseed oil and tung oil, Example 3, gum rosin and linseed oil, Example 4, gum rosin and paraffin wax, Example 5, gum rosin and coal tar, and Example 6, gum rosin and a vinyl copolymer, together with the anti-fouling compound of the invention and other ingredients of those above specified.ALSO:Complexes of a lead, mercuric or zinc cation with a compound of formula <FORM:1102430/C2/1> where R is thiazolyl and R5 is hydrogen phenyl, heterocyclic, phenoxy, phenylthio, C1- 5 alkyl, C1- 5 alkylthio, C1- 5 alkoxy, halo, or halophenyl are prepared by intimately contacting a heterocycle of the above formula with a lead, mercuric or zinc salt, optionally in the presence of solvents or dispersing media.  The process may also be carried out by mixing an aqueous solution of the metal salt, e.g. sulphate, nitrate or halide, with a hydrohalide of the above benzimidazoles.  The complexes are useful as paints or resin coatings for ships to prevent fouling by animals and plants. Suitable solvents and dispersing media are dimethylsulphoxide, formamide, dimethylformamide, xylene, toluene, hexane, heptane, water, methanol, ethanol and isopropanol.  In the examples, mercuric-, plumbic- and zinc-2-(41 - thiazolyl - benzimidazole, mercuric - 2 - (21-thiazolyl) - benzimidazole, and mercuric - 2 - (41 - thiazolyl) - 5 - (41 - fluorophenyl) - benzimidazole are prepared from the corresponding benzimidazole and metal chloride.ALSO:A marine anti-foulant composition used for coating under-water surfaces, e.g. ships, comprises a compound of formula:-  <FORM:1102430/B1-B2/1> where R is thiazolyl and R5 is hydrogen, phenyl, phenoxy, phenylthio, heterocyclic, C1-5 alkyl, C1-5 alkoxy, C1-5 alkylthio, halo, or halophenyl, together with a resin coating vehicle.  Such coatings include coal tar, shellac, vinyl resins, e.g. vinylchloride-vinyl acetate copolymer, polyvinyl chloride, polyvinyl acetate and polyvinyl butyral, phenol-formaldehyde resin, and coumarone-idene resin.  Other specified ingredients include driers, pigments, plasticizers and solvents.  A test describes the treatment of a porous carbon block with an aqueous dispersion of the benzimidazoles specified below, to achieve impregnation with substantially all the dispersed complexes by air evacuation and immersion.  The complexes used are mercuric, zinc and plumbic 2-(4\sv-thiazolyl)-benzimidazoles. Exs. 1-6 list suitable anti-foulant formulations including certain of the resins, the benzimidazoles, and the other additives.