WO1998000017A1

WO1998000017A1 - Piperidine and morpholine derivatives for protecting materials against infestation by algae

Info

Publication number: WO1998000017A1
Application number: PCT/EP1996/002856
Authority: WO
Inventors: Reinhardt Grade; Adalbert Braig
Original assignee: Ciba Specialty Chemicals Holding Inc.
Priority date: 1996-06-29
Filing date: 1996-06-29
Publication date: 1998-01-08
Also published as: AU6515596A

Abstract

Compounds having the formula (I), in which R1 stands for C1-C12 alkyl, C3-C12-cycloalkyl substituted or not by C1-C4 alkyl, phenyl or C7-C9 phenylalkyl; R2 stands for hydrogen or C1-C8 alkyl; R3, R4, R5 and R6 represent independently from each other hydrogen or C1-C8 alkyl, and X stands for oxygen or -CH2-, as well as their acid addition salts, are remarkably suitable for protecting technical materials such as wood, plastics, paints, lacquers, in particular antifouling lacquers, sealing compounds and adhesives, against infestation by algae.

Description

Piperidine and morphoiin derivatives for protecting materials from algal attack

The present invention relates to material compositions which are protected against algae attack and contain a technical material and a piperidine or morpholine derivative, the use thereof for technical material protection, and a method for protecting these materials from attack by algae.

The use of piperidine and morpholine derivatives, in particular fenpropidine and fenpropimorph, as fungicides in agriculture and horticulture is known and is described, for example, in DE-A-2 752 096, US-A-4 202 894, EP-A-0 235 082, US-A-4 753 954, EP-A-0 484 279, US-A-5 407 934, WO-A-95/07614 or EP-A-0452 267.

EP-A-0 003 749 and US-A-4 242 119 describe the use of certain triazines as seawater algicides.

None of the publications mentioned above suggests that piperidine or morpholine derivatives can be used in moist or wet environments in technical material protection in order to protect materials in moist or wet environments against algae attack.

It has now surprisingly been found that certain piperidine or morpholine derivatives have an excellent effect in this regard and thus protect in compositions with industrial materials from attack by algae.

The present invention therefore relates to material compositions which are protected against algae attack and which contain a) an industrial material, and b) at least one compound of the formula I.

wherein

Ri CrCι ₂ alkyl, unsubstituted or substituted by dC ₄ alkyl C ₃ -Cι ₂ cycloalkyl; Phenyl or C ₇ -C ₉ phenylalkyl means R _{2 is} hydrogen or -CC ₈ alkyl,

R ₃ , R, Rs and R _{6 are} independently hydrogen or -CC ₈ alkyl, and X is oxygen or -CH ₂ -, and the acid addition salts of these compounds.

Alkyl having up to 12 carbon atoms means a branched or unbranched radical, such as, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1, 3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1, 1, 3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1, 1, 3-trimethylhexyl, 1, 1, 3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylunecyl, dodecyl or 1, 1, 3,3,5, 5-hexamethylhexyl, A preferred meaning of Ri is for example, Cι-Cιo-alkyl, in particular Ci-Cβ-alkyl, for example, Cι-C alkyl _β. A particularly preferred meaning of Ri is, for example, -C ₄ alkyl, especially tert-butyl. A preferred meaning of R _2, R _3, R, R ₅ and R ₆ Cι-C alkyl _β, in particular, for example, Cι-C-Ce-alkyl d ₄ alkyl. A particularly preferred meaning of R ₂ , R ₃ , R ₄ , R ₅ and R ₆ is C1-C3-alkyl, in particular methyl.

Unsubstituted or substituted by C ₁ -C ₄ alkyl C ₃ -C ₂ cycloalkyl, which preferably contains 1 to 3, in particular 1 or 2 branched or unbranched C 1 -C ₄ alkyl group radicals, means, for example, cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl , Dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl or cyclodocecyl. Preferred is, for example, C ₃ -C ₈ cycloalkyl, in particular C ₅ -C ₇ cycloalkyl, for example cyclohexyl. C ₇ -C phenylalkyl means, for example, benzyl, α-methylbenzyl or α, α-dimethylbenzyl. Benzyl is preferred.

Of interest are algae-protected material compositions containing as

Component (b) at least one compound of formula I, wherein

R 1 -C ₈ alkyl, unsubstituted or substituted by C ₁ -C ₄ alkyl C ₃ -C ₈ cycloalkyl;

Means phenyl or benzyl,

R _{2 represents} hydrogen or -CC ₄ alkyl,

R ₃ and R ₄ independently of one another denote hydrogen or dC ₄ alkyl,

R ₅ and R _{6 represent} hydrogen, and

X means oxygen or -CH ₂ -.

Material compositions which are protected against algae attack and contain as component (b) at least one compound of the formula I in which R 1 is tert-butyl.

Preference is also given to material compositions which are protected against algae attack and contain, as component (b), at least one compound of the formula I in which R _{2 is} methyl.

Preference is likewise given to material compositions which are protected against algae attack and contain, as component (b), at least one compound of the formula I, in which if X is oxygen; R ₃ and R _{4 are} methyl, R ₅ and R _{6 are} hydrogen; and when X is -CH ₂ -; R ₃ , R, R ₅ and R _{6 represent} hydrogen.

Of particular interest are material compositions which are protected against algae attack and contain as component (b) at least one compound of the formula I in which

Ri means tert-butyl,

R _{2 represents} methyl; and when X represents oxygen;

R ₃ and R _{4 are} methyl,

R ₅ and R _{6 represent} hydrogen; and when X is -CH ₂ -;

R ₃ , R, R5 and R _{6 represent} hydrogen, and correspond to the formulas A and B.

(A) Fenpropimo h

UH ₃ H ₃ C - C (') CH; (B) fenpropidine

Material compositions containing component (b) containing 1- [3- (4-tert-butylphenyl) -2-methylpropyl] piperidine (fenpropidine, compound of the formula B) are very particularly preferred.

The compounds of formula I, wherein R _{2 is} different from hydrogen, contain a chiral center. From EP-A-0 452 267 it is known that, for example, the (S) enantiomer of fenpropidine (compound of the formula C)

(C) (S) -Fenpropidin

has a fungicidal activity which is a multiple of that of the racemic (R, S) - fenpropidine and exceeds the activity of the enantiomeric (R) -fenpropidine by a factor of approx. 7-23.

Of particular interest are therefore also material compositions which are protected against algae attack and contain as component (b) at least one compound of the formula I '

wherein

R _T C ₁ -C ₂ alkyl, unsubstituted or substituted by C ₁ -C ₄ alkyl C ₃ -C ₁₂ cycloalkyl;

Is phenyl or C ₇ -C ₉ phenylalkyl,

R _{2 represents} hydrogen or -CC ₈ alkyl,

R3, R, ₅ and R _{6 are} independently hydrogen or C -C _β alkyl, and

X means oxygen or -CH ₂ -, and the acid addition salts of these compounds.

The preferences of the general symbols R _{1 (} R ₂ , R ₃ , R ₄₎ R ₅ , R ₆ and X and the acid addition salts in the chiral compound of the formula I 'correspond to those in the racing compound of the formula I.

Material compositions which are protected against algae attack and contain as component (b) at least one compound of the formula I in which the chirality center of the compound of the formula I has an R configuration (configuration assignment according to the Cahn-Ingold-Prelog nomenclature) are very particularly preferred.

Acid addition salts of the compounds of formula I or mean, for example, salts of the compounds of formula I or I 'with inorganic or organic acids.

Suitable inorganic acids mean, for example, hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acid or sulfamic acid.

Suitable organic acids mean, for example, monofunctional and polyfunctional carboxylic acids, hydroxycarboxylic acids or ketocarboxylic acids, in particular β-ketocarboxylic acids, such as, for example, formic acid, acetic acid, propionic acid, heptanoic acid, lauric acid, stearic acid, maleic acid, fumaric acid, malonic acid, succinic acid, adipic acid, sebacic acid Tartaric acid, citric acid, benzoic acid, 4-methylbenzoic acid, o-toluic acid, o-nitrobenzoic acid, 4-nitrobenzoic acid, o-chlorobenzoic acid, 4-chlorobenzoic acid, 3-benzoylpropionic acid, 3- (4-methylbenzoyl) propionic acid, 3- ( 4-hydroxyphenyl) propionic acid, 3- (3,5-di-tert-butyl-3-hydroxy-ρhenyl) propionic acid, 4- (4-methylphenyl) butyric acid, 3- (4-methylphenylthio) propionic acid, 3- ( 4-methylphenoxy) propionic acid, 2- (4-methylphenylamino) propionic acid, phenylacetic acid, salicylic acid, phthalic acid, isophthalic acid, terephthalic acid, 3-nitro-isophthalic acid, sorbic acid, 2-mercaptobenzothiazoiylsuccinic acid prgacor 252) , Naphthenic acid, 3-hydroxynaphthalene-2-carboxylic acid, mandelic acid or lactic acid; and sulfonic acids such as sulfamic acid or 1,5-naphthalene disulfonic acid.

The compounds of the formula I and / or their acid addition salts are known and their preparation is described, for example, in DE-A-2 752 096, US-A-4 202 894, EP-A-0 235 082, US-A-4 753 954, EP -A-0 484 279, US-A-5 407 934 or EP-A-0452 267.

The enantiomerically pure compounds of the formula I 'are prepared in analogy to the instructions for the preparation of (S) -fenpropidine disclosed in EP-A-0 452 267.

The compounds of the formula I [component (b)] are suitable for protecting industrial materials against attack by algae.

Examples of technical materials are wood, cellulose, paper, plastics, paints, varnishes, greases, waxes, textiles, leather, glasses, rubber, sealants or adhesives.

In compositions with wood, the excellent action of the compounds of the formula I against the algae growth of the wood is used in particular. The wood to be protected is expediently treated with a formulation (for example wood protection glaze) which contains the compound of the formula I. In this way e.g. Building materials made of wood, but also buildings or ships that are made entirely or partially of wood, are protected against algae attack.

A particular advantage of the compound of the formula A (fenpropimorph) and the compound of the formula B (fenpropidine) within the compounds of the formula I is that below a concentration of 70 μg / day there is no permanent impairment for algae and other lower plant forms in natural soil waters, streams, rivers or canals are to be expected. They are therefore unusually advantageous for all material applications in which the material is in contact with water for a long time or permanently. The skilled worker is also familiar with formulation auxiliaries and additives which largely prevent their diffusion from the material.

Examples of plastics are:

1. Polymers of mono- and diolefins, for example polypropylene, polyisobutylene, poly-butene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene and polymers of cycloolefins such as e.g. of cyclopentene or norbomen; also polyethylene (which may optionally be cross-linked), e.g. High density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene ( LLDPE), branched low density polyethylene (VLDPE).

Polyolefins, i.e. Polymers of monoolefins, as mentioned by way of example in the preceding paragraph, in particular polyethylene and polypropylene, can be produced by various processes, in particular by the following methods:

a) radical (usually at high pressure and temperature).

b) by means of a catalyst, the catalyst usually containing one or more metals from Group IVb, Vb, Vlb or VIII. These metals usually have one or more ligands such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls, which can be either π- or σ-coordinated. These metal complexes may be free or fixed to carriers, ^'such as on activated magnesium chloride, titanium (lll) chloride, alumina or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalysts as such can be active in the polymerization, or further activators can be used, such as, for example, metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, the metals being elements from groups la, Ha and / or purple. The activators can be modified, for example, with further ester, ether, amine or silyl ether groups. These catalyst systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), e.g. Mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (e.g. PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (e.g. LDPE / HDPE).

3. Copolymers of mono- and diolefins with one another or with other vinyl monomers, such as e.g. Ethylene-propylene copolymers, linear low-density polyethylene (LLDPE) and mixtures thereof with low-density polyethylene (LDPE), propylene-butene-1 copolymers, propylene-isobutylene copolymers, ethylene-butene-1 copolymers, ethylene-hexene Copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers Copolymers and their copolymers with carbon monoxide, or ethylene-acrylic acid copolymers and their salts (ionomers), and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene norbornene; furthermore mixtures of such copolymers with one another and with polymers mentioned under 1), e.g. Polypropylene ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers, LDPE / ethylene-acrylic acid copolymers, LLDPE / ethylene-vinyl acetate copolymers, LLDPE / ethylene-acrylic acid copolymers and alternating or randomly constructed polyalkylene / carbon monoxide Copolymers and their mixtures with other polymers such as Polyamides.

4. Hydrocarbon resins (eg C ₅ -C ₉ ) including hydrogenated modifications thereof (eg tackifier resins) and mixtures of polyalkylenes and starch.

5. Polystyrene, poly- (p-methylstyrene), poly- (α-methylstyrene).

6. copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, such as, for example, styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and - methacrylate, styrene-maleic anhydride, styrene-acrylonitrile methyl acrylate; Mixtures of high impact strength from styrene copolymers and another polymer, such as, for example, a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; and block copolymers of styrene, such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene-propylene-styrene.

7. Graft copolymers of styrene or α-methylstyrene, e.g. Styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; Styrene, acrylonitrile and methyl methacrylate on polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; Styrene and maleimide on polybutadiene, styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile on polyalkylacrylates or polyalkyimethacrylates, styrene and acrylonitrile on acrylate-butadiene mixtures, copolymers with the copolymers mentioned under 6), such as, for example are known as so-called ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as e.g. Polychloroprene, chlorinated rubber, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or chlorosulphonated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, in particular polymers of halogen-containing vinyl compounds, such as e.g. Polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; and their copolymers, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.

9. Polymers which are derived from α, β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, impact-modified polymethyl methacrylates, polyacrylamides and polyacrylonitriles with butyl acrylate.

10. Copolymers of the monomers mentioned under 9) with one another or with other unsaturated monomers, such as, for example, acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkylacrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate butadiene -Terpolymers. 11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate, polyvinyl butyral, polyallyl phthalate, potyallyl melamine; and their copolymers with olefins mentioned in point 1.

12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or their copolymers with bisglycidyl ether.

13. Polyacetals, such as polyoxymethylene, and also such polyoxymethylenes, the comonomers, e.g. Ethylene oxide included; Polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides and their mixtures with styrene polymers or polyamides.

15. Polyurethanes derived from polyethers, polyesters and polybutadienes with terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other hand, and their precursors.

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6 , 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene, diamine and adipic acid; Polyamides made from hexamethylenediamine and iso- and / or terephthalic acid and optionally an elastomer as a modifier, e.g. Poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene-isophthalamide. Block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomeric or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Furthermore, polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (“RIM polyamide systems”).

17. Polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides, polyhydantoin and polybenzimidazoles. 18. Polyesters which are derived from dicarboxylic acids and dialcohols and / or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1, 4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates, and also block polyether esters which differ from polyethers Derive hydroxyl end groups; furthermore polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand and phenols, urea or melamine on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins, which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, and also vinyl compounds as crosslinking agents, as well as their halogen-containing, flame-retardant modifications.

24. Crosslinkable acrylic resins derived from substituted acrylic esters, e.g. of epoxy acrylates, urethane acrylates or polyester acrylates.

25. alkyd resins, polyester resins and acrylate resins which are crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins which are derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for example products of bisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, which are crosslinked by means of conventional hard materials such as anhydrides or amines with or without accelerators . 27. Natural polymers, such as cellutose, natural rubber, gelatin, and their polymer-homologously chemically modified derivatives, such as cellulose acetates, propionates and butyrates, or the cellulose ethers, such as methyl cellulose; as well as rosins and derivatives.

28. Mixtures (polyblends) of the aforementioned polymers, such as e.g. PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylates, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA PPO, PBT / PC / ABS or PBT / PET / PC.

Particularly preferred plastics are, for example, halogen-containing polymers (item 8 of the list) (chlorine-containing polymers), polyamides (item 16 of the list) or polyurethane foams (item 15 of the list).

The plastics with anti-algae treatment (containing the compounds of formula I) are suitable, for example, for the production of soft PVC films, ship hulls or house facade plasters.

Particularly preferred industrial materials are wood, chlorine-containing polymers, in particular polyvinyl chloride; Dispersion paints, sealants or antifouling varnishes that often come into contact with an environment that is optimal for algae growth, such as sea or fresh water.

Also of interest are material compositions protected against algae attack, wherein the material composition protected against algae attack is a coating composition, in particular a paint, and component (a) is an organic film-forming binder.

Paints are, for example, varnishes, paints or varnishes. These always contain an organic film-forming binder along with other optional components.

Preferred organic film-forming binders are all customary film formers for solvent-containing and solvent-free coating compositions. Examples of such film image ner are epoxy resins, polyurethane resins, aminoplast resins or mixtures of such resins; a basic aqueous dispersion or a solution of an acidic resin.

Of particular interest are organic film-forming binders for aqueous coating compositions such as Alkyl resins; Acrylic resins; 2-component epoxy resins; Polyurethane resins; Polyester resins, which are usually saturated; water-dilutable phenolic resins or derived dispersions; water-thinnable urea resins, resins based on vinyl / acrylic copolymers; Hybrid systems based on e.g. Epoxy acrylates.

More specifically, the alkyd resins can be water-thinnable alkyd resin systems, which can be used in air-drying or in the form of stoving systems, optionally in combination with water-thinnable melamine resins; it can also be an oxidative drying, air drying or stoving system, which can be used in combination with aqueous dispersions based on acrylic resins or their copolymers, with vinyl acetate, etc.

The acrylic resins can be pure acrylic resins, epoxyacrylate hybrid systems, acrylic acid or acrylic acid ester copolymers, combinations with vinyl resins or copolymers with vinyl monomers such as vinyl acetate, styrene or butadiene. These systems can be air drying systems or stoving systems.

Water-thinnable epoxy resins in combination with suitable polyamine crosslinkers have excellent mechanical and chemical resistance. When using liquid epoxy resins, there is no need to add organic solvents to aqueous systems. The use of solid resins or solid resin dispersions usually requires the addition of minor amounts of solvent to improve film formation.

Preferred epoxy resins are those based on aromatic polyols, in particular based on bisphenols. The epoxy resins are used in combination with crosslinkers. The latter can be, in particular, amino- or hydroxy-functional compounds, an acid, an acid anhydride or a Lewis acid. Examples of these are polyamines, polyaminoamides, polymers based on polysulfides, polyphenols, boron fluorides and their complex compounds, polycarboxylic acids, 1, 2-dicarboxylic anhydrides or pyromellitic dianhydride.

Polyurethane resins are derived from polyethers, polyesters and polybutadienes with terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other.

Suitable polyvinyl resins are, for example, polyvinyl butyral, polyvinyl acetate or their copolymers.

Suitable phenolic resins are synthetic resins, in the structure of which phenols are the main component, that is, above all, phenolic, cresol, xylenol and resorcinol-formaldehyde resins, alkylphenolic resins and condensation products from phenols with acetaldehyde, furfural, acrolein or other aldehydes. Modified phenolic resins are also of interest.

The coating compositions can additionally contain one or more components from the group of pigments, dyes, fillers, flow control agents, dispersants, thixotropic agents, adhesion promoters, antioxidants, light stabilizers or curing catalysts. They can also contain other known corrosion protection agents, for example corrosion protection pigments, such as phosphate- or borate-containing pigments or metal oxide pigments, or organic or inorganic corrosion inhibitors, e.g. Salts of nitroisophthalic acid, phosphoric esters, technical amines or substituted benzotriazoles.

The pigments are, for example, titanium dioxide, iron oxide, aluminum bronze or phthalocyanine blue.

Examples of fillers are talc, aluminum oxide, aluminum silicate, barite, mica or silicon dioxide. The compounds of formula I can also be applied to a carrier. Powdery fillers or pigments are particularly suitable for this.

Flow control agents and thixotropic agents are based, for example, on modified bentonites. Haftungsvett> esser are based, for example, on modified silanes.

The addition of basic fillers or pigments is also advantageous.

Examples of such basic fillers and pigments are calcium or magnesium carbonate, zinc oxide, zinc carbonate, zinc phosphate, magnesium oxide, aluminum oxide, aluminum phosphate or mixtures thereof. Examples of basic organic pigments are those based on aminoanthraquinone.

The compounds of the formula I can be added to the paint during its production, for example during the pigment distribution by grinding, or the compounds of the formula I are dissolved in a solvent and then stirred into the coating composition.

In the production of the organic film-forming binder by polymerization or polycondensation of monomers, the compounds of the formula I can be added to the monomers either in solid form or in solution before the polymerization.

If paints (paint formulations) are protected, these are preferably emulsion paints and antifouling paints.

Of particular interest are the material compositions according to the invention which are protected against algae attack, in which component (a) is an antiflouling lacquer.

Common raw materials for antifouling paints are the paint raw materials known as binders and known to the person skilled in the art, such as natural and synthetic resins; homo- and copolymeric products with the monomers such as vinyl chloride, vinylidene chloride, styrene, vinyl toluene, vinyl esters, vinyl alcohols, acrylic acid and methacrylic acid and their esters; Polyester and polyamide resins; chlorine rubber; natural and synthetic rubber, optionally chlorinated or cyclized; then also reaction resins such as epoxy resins, polyurethane resins, unsaturated polyesters, which can optionally be converted into film-forming higher molecular weight products by adding hardeners. The binders can be liquid or in dissolved form. In the case of dissolved binders, including thermoplastics, a protective film can also be formed by evaporating the solvent. Solid coating agents can be applied to objects, for example, in the powder coating process. Other common raw materials are, for example, tar, modifiers, dyes, inorganic or organic pigments, fillers and hardeners.

In addition to components (a) and (b), the algicidal compositions according to the invention can contain further additives.

If component (a) is an industrial material, the other additives are, for example, pigments, dyes, fillers, antioxidants, light stabilizers or biocides.

The amount of compounds of the formula I [component (b)] which is added to the industrial materials largely depends on the particular type of application and can therefore vary within wide limits. Component (b) is preferably added to the material to be protected from algae attack in an amount of 0.01 to 40%, in particular 0.1 to 20%, e.g. 0.1 to 10%, based on the weight of component (a), added.

The present invention also relates to a method for protecting industrial materials from attack by algae, which is characterized in that at least one compound of the formula I is incorporated into or applied to it.

Preferred is a method for protecting technical materials from infestation with algae, in which the technical materials are wood, cellulose, paper, plastics, paints, varnishes, fats, waxes, textiles, leather, glasses, rubber, sealants or adhesives.

A preferred embodiment of the present invention is also the use of the compounds of the formula I, in particular fenpropidine, as an algae-preventing additive in industrial materials. In summary, some important areas of application for the compounds of the formula I are again mentioned. As already mentioned, the latter are suitable, for example, as additives to building materials, preferably to mortars, plasters (interior plaster, exterior plaster or screed) or to mixtures containing hydraulic binders such as concrete, as an additive to paints, suitably to paints and varnishes, preferably to emulsion paints, as an active medium in anti-fouling or anti-fouling paints, so-called anti-fouling paints, for algae-preventing finishing of surface coatings in general and of wood, plastics, polymer materials, paper, leather and textiles, for the surface treatment of or for incorporation into building materials and components made of polymer material .

A preferred area of application is that in protective paints, in particular in antifouling paints, which, in addition to the usual base and additives, e.g. 0.01 to 40 wt .-%, preferably 0.1 to 20 wt .-%, based on the total mixture, contain at least one of the compound of formula I.

Finally, the compounds of the formula I can also be used in elastomeric coatings and also in silicone-elastomers and fluorine-containing polymers.

In practice, active ingredients are often used in combination with other biocides. The compounds of the formula I can also be combined with other biocides. Their simultaneous fungicidal action, which is particularly pronounced in fenpropimorph (compound of the formula A) and fenpropidine (compound of the formula B), is of great advantage. With antifouling paints, combinations of products often prove to be advantageous. Thus, the compounds of the formula I can be used in combination with Cu ₂ O, CuSCN, zinc oxide, triorganotin compounds, such as, for example, tributyltin fluoride or triphenyltin chloride, metallic copper or triazines, or in general with those compounds which are known to those skilled in the art to be effective against animal or plant growth , be combined.

Another form of use of the compounds of the formula I is incorporation into plastics or natural or synthetic rubbers, or application to surfaces of moldings made from these plastics, such as, for example, polyvinyl chlorides and their copolymers and copolymers, polyalkylenes, polyacrylates, polystyrenes, polyurethanes, polyisocyanates, polyesters or epoxy resins. The use of the compounds of the formula I is particularly expedient in plastics or polymer materials which are used as building materials and are, for example, exposed to the weather or used in the area of moist or wet areas. For example, roofing materials or claddings made of polyvinyl chloride, butyl rubber, chlorinated polyethylene, polyisobutylene, chloroprene, chloroisoprene, EPDM, PVC copolymers with vinyl acetate or ethyl vinyl acetate, polyacrylonitrile styrene, optionally in a mixture with fibrous fillers or optionally also in a blend with bitumen, or foamed Polyvinyl chlorides or polystyrenes, as insulation materials against heat and cold, are mentioned.

For application, the compounds of the formula I can be present in the following workup forms, the percentages by weight in brackets representing advantageous amounts of active ingredient:

Solid processing forms: dusts and spreading agents (up to 10%), granules, coating granules, impregnation granules and homogeneous granules, pellets (grains) (1 to 80%).

Liquid processing forms: a) Active ingredient concentrates dissolved or dispersible in water: wettable powders and pastes (25 to 90% in retail packs, 0.01 to 15% in ready-to-use solutions), emulsion and solution concentrates (10 to 50% in Commercial packaging; 0.01 to 15% in ready-to-use solution); b) Organic solutions (0.1 to 20%) and aerosols:

The compounds of the formula I can also be used together with other biocidal active substances in the processing forms mentioned above.

Bed games for such other biocides are:

a) Organo-sulfur compounds, for example methylene dithiocyanate (MBT), isothiazolones or 3,5-dimethyl-tetrahydro-1, 3,5-2H-thiodiazin-2-thione (DMTT). b) Chlorinated phenols, such as sodium pentachlorophenolate. Such compounds are characterized by a very broad spectrum of activity.

c) copper salts, such as copper sulfate and copper nitrate as additional algicides.

d) triazines such as 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine, in particular as algicides.

e) triorganotin compounds such as bis-tributyltin oxide (TBTO), in particular as fungicides and algicides.

f) wood biocides

1. Salt mixtures based on silicon fluorides, hydrogen fluorides, inorganic boron compounds, chromates, fluorides, arsenic (oxide, arsenates), copper salts (sulfate, naphthenate), tin or zinc salts.

2. Tar oil preparations

3. Organic active ingredients, such as pentachlorophenol, phenol, DDT, dieldrin, lindane, gammexan, chlorinated naphthalenes, dichlorofluoride, tributyltin compounds, pyrethroids, 3-iodo-2-propenyl-N-butylcarbamate, furmecyclox.

Such formulations can of course also contain other substances and auxiliaries which are usually used in such preparations. These include, for example, anionic, cationic or nonionic surface-active substances, electrolytes, complexing agents, solubilizers and colorants and fragrances. These additives serve, for example, to improve the wetting capacity, the curing stability, to adjust the viscosity and to increase the low-temperature stability of the solutions.

When used in emulsion paints and plasters, the compounds of the formula I can, for example, also be combined with other fungicides. Such combinations can bring technical advantages. In many cases, the combination with other algicides is also advantageous. The following examples further illustrate the invention. Parts or percentages are by weight.

Example 1: Determination of the minimum inhibitory concentration (MIC) for algae

The organisms against which fenpropidin is tested are grown in the Erlenmeyer in the nutrient medium under sterile conditions in a shaker at 24 ± 2 ° C under light (16 hours light-8 hours dark change). Tests are carried out against 6 representative algae:

1.) Unicellular algae widespread in water such as Chlorella vulgaris, Chlamidomonas reinhardtii and Selenastrum capricomutum.

2.) Algae and zoenobia-forming genera, such as Scenedesmus subspicatus, found in the various biotypes.

3.) The simple, thread-forming algae that usually appear in fast-flowing water in the colder seasons, such as Klebsormidium subtilissimum.

4.) The generally widespread, unbranched thread-forming algae, such as Tribonema aequale, appearing especially in spring at low temperature or in autumn, even in mild winters in water.

The nutrient medium is composed as follows: 1.0 g sodium nitrate (NaNO ₃ ), 0.05 g ammonium chloride (NH ₄ CI) 0.058 g calcium chloride (CaCl ₂ ), 0.5 g magnesium sulfate (MgSO ₄ x 7 H ₂ O) , 0.25 g of potassium dihydrogen phosphate (K ₂ HPO ₄ ) and 0.0024 g of iron trichloride (FeCI ₃ ) are dissolved in 1 liter of distilled water. To improve the growth of the various algae, soil extract is added to the nutrient medium. The nutrient medium mixed with the test substance (racemic fenpropidine, 0.001; 0.003; 0.01; 0.03; 0.10; 0.30; 1, 0 and 3.0 mg / l) is mixed with the respective algae suspension (9 Days old pre-cultures) inoculated so that a dilution of 1/50 to 1/625 is achieved. The effectiveness is indicated via the minimum inhibitory concentration (MIC in mg / l), which indicates the test substance concentration at which the growth of the algae is still prevented. After 11 days of incubation with shaking, the algae growth is evaluated. The results are summarized in Table 1: Table 1: minimum

Final dilution

Algae strain inhibitory concentration Algae strain culture

(mg / l)

Chlorella vulgaris 1: 625 0.30

Chlamidomonas reinhardtii 1: 625 0.01

Selenastrum capricomutum 1: 250 1, 00

Scenedesmus subspicatus 1: 125 0.01

Klebsormidium subtilissimum 1:50 0.10

Tribonema aequale 1: 500 0.03

Example 2: Use of the compounds of the formula I for protection against algae attack in anti-fouling lacquers.

To test the effectiveness against fouling on objects submerged in the sea, a compound of the formula I, in particular fenpropidine, is incorporated in antifouling paints. For this purpose, an antifouling paint based on PVC copolymer / rosin (1.2: 1 parts by weight) is produced, as is known to the person skilled in the art. The paint is spread on test panels. After drying (10 days at room temperature) the samples are hung in the Mediterranean (La Spezia / Italy). As a comparison, the corresponding colors are designed, but without the addition of a compound of the formula I. The effectiveness is given on a rating scale from 0 (= completely covered) to 10 (= completely covered). The results show that antifouling paints which contain a compound of the formula I are protected against attack by algae.

Claims

claims

1. Material composition protected against algae attack comprising a) a technical material, and b) at least one compound of the formula I.

wherein

R 1 -C ₂ alkyl, unsubstituted or substituted by CrC alkyl C ₃ -C ₁₂ cycloalkyl; Phenyl or C ₇ -C ₉ phenylalkyl means R _{2 is} hydrogen or -CC ₈ alkyl,

R3, R, Rs and R _{6 are} independently hydrogen or -CC ₈ alkyl, and X is oxygen or -CH ₂ -, and the acid addition salts of these compounds.

2. Composition according to claim 1, wherein

R 1 -C ₈ -alkyl, unsubstituted or substituted by dC -alkyl C ₃ -C ₈ cycloalkyl;

Means phenyl or benzyl,

R _{2 represents} hydrogen or -CC ₄ alkyl,

R ₃ and R ₄ independently of one another denote hydrogen or -CC alkyl,

R ₅ and R _{6 represent} hydrogen, and

X means oxygen or -CH ₂ -.

3. A composition according to claim 1, wherein R _{T is} tert-butyl.

4. The composition according to claim 1, wherein R _{2 is} methyl.

5. The composition according to claim 1, wherein when X represents oxygen;

R ₃ and R are methyl,

R ₅ and R _{6 represent} hydrogen; and when X is -CH ₂ -;

R ₃ , R, Rs and R _{6 represent} hydrogen.

6. The composition according to claim 1, wherein R 1 is tert-butyl,

R _{2 represents} methyl; and when X represents oxygen;

R ₃ and R _{4 are} methyl,

R ₅ and R _{6 represent} hydrogen; and when X is -CH ₂ -;

R ₃ , R, Rs and R _{6 represent} hydrogen.

7. The composition according to claim 1, wherein the compound of formula I 1 - [3- (4-tert-Butylphenyl) -2-methylpropyl] piperidine (fenpropidine) means.

8. The composition according to claim 1, wherein component (a) means wood, cellulose, paper, plastics, paints, lacquers, fats, waxes, textiles, leather, glasses, rubber, sealants or adhesives.

9. The composition according to claim 1, wherein component (a) is wood, chlorine-containing polymer, emulsion paints, sealants or antifouling lacquers.

10. The composition according to claim 1, wherein component (a) is polyvinyl chloride.

11. The composition according to claim 1, wherein the composition is a coating composition and component (a) is an organic film-forming binder.

12. The composition according to claim 1, wherein component (a) is an antifouling lacquer.

13. The composition according to claim 1, comprising, in addition to components (a) and (b), further additives.

14. Composition according to claim 13, containing as further additives pigments, dyes, fillers, antioxidants, light stabilizers or biocides.

15. The composition according to claim 1, wherein component (b) is present in an amount of 0.01 to 40% based on the weight of component (a).

16. A method for protecting technical materials against infestation of algae, characterized in that at least one compound of the formula I defined in claim 1 is incorporated into or applied to it.

17. The method according to claim 16, wherein the technical materials are wood, pulp, paper, plastics, paints, varnishes, fats, waxes, textiles, leather, glasses, rubber, sealants or adhesives.

18. Use of the compounds of formula I defined in claim 1 as algae-preventing additives in industrial materials.

19. Use according to claim 18, wherein the compound of formula I is fenpropidine.