AT304729B

Hydrophilic polymer coating for underwater structures

Abstract

This record has no abstract on file.

AT304729B, drawing sheet 1 — Sheet 1 of 4

Term

Term ended

Expired 5 March 1990, 36.6 years ago.

5 claims: 2 independent, 3 dependent

1
CLAIMS:5 1. Use of a water-insoluble, in water at least 20% swellable hydrophilic Acrylic resin and optionally an antifouling additive and / or pigments and / or solvents existing mixture or a mixture of a convertible to an acrylic resin mixture of appropriate 17 No. 3 04720 and monomers, if appropriate, of the specified type for the production of coatings on hulls or hulls or on components flown around by aqueous media.
4
4th Use of a mixture according to one of claims 1, 2 or 3, which contains a copolymer of acrylate or methacrylate and from 0.05 to 20% by weight of a crosslinking agent or in addition to the mixture of monomers for the copolymer, a crosslinking agent in the for the purpose specified in claim 1,

Independent claims2

285 paragraphs in 15 sections, as filed

claimed

<td>©</td><td>Start of patent duration: Longest possible duration:</td><td>15, May 1972</td>

<td>©</td><td>Issued on:</td><td>January 25, 1973</td>

<td>©</td><td>Inventor:</td><td></td>

CM

O

CO

DT-AS

209 685 1 234 897 1 234 898

DT-AS

FR-PS

251 890 1 324 705

No. 3 04724

It is an object of the invention to reduce the hydrodynamic resistance of hulls or hulls, but also the hydrodynamic resistance of stationary, but flowed around by aqueous media components. This is possible within the scope of the invention by using a hydrophilic acrylic resin which is water-insoluble, at least 20% swellable in water and optionally an antifouling additive and / or pigments and / or solvents or a mixture of a mixture of correspondingly convertible to such an acrylic resin Monomers and, where appropriate, additives of the specified type for the production of coatings on hulls or Hulls or components flowed around by aqueous media. The achievable in the inventive use of water-insoluble in water at least 20% swellable resins reduction in hydrodynamic resistance of hulls or Hulls or components flowed around by aqueous media are presumably due to the fact that, during the swelling of the coating, the coating softens so much, that they can align with the assumption of optimum hydrodynamic form of the body flowed around by the aqueous medium practically parallel to the flow strands of the aqueous medium and also hydrodynamically attenuates the swollen in the swollen state coating and thus reduces the turbulence of the flow.

In foul-inhibiting additives possibly contained in the mixtures to be used according to the invention, the lifetime of the coatings increases while, in mixtures to be used in accordance with the invention, any solvents present facilitate the production of the coating.

Acrylic polymers of the type to be used according to the invention are described inter alia in German Auslegeschriften 1209685, 1234897 and 1234898, but are recommended there for the production of baking finishes.

In the present invention, watercraft of all kinds, such as sailboats, yachts, rowing boats, water skis, cargo and passenger ships but also fixed assets, such as shipyards, bridge pier, Landungsstege, etc., regardless of whether these watercraft or construction parts made of wood, metal , Plastic, fiberglass, concrete or other materials are to be equipped with underwater coatings. In addition to reducing hydrodynamic drag, mixtures containing antifouling additives will protect marine vessels or structural members against marine organisms or clams such as Cirripedia, Baianus balanoides, Lepas fascicularis, algae, mucus, drillworms, oysters, brozoen, or marine animals, such as Tunicata or Urochordata, scored.

It is essential that the hydrophilic acrylic resins be insoluble in water, otherwise they can not be applied in a durable form to the submerged surface. The hydrophilic acrylic resins are said to absorb at least 20% of their weight in water, but preferably not more than about 120% by weight of water. It has been found that linear polymers, which are usually alcohol soluble, are particularly advantageously usable, although crosslinked polymers can also be used, provided that they are in a processable state.

For the preparation of the acrylate resin or the mixture of monomers as the hydrophilic monomer which can be converted to such an acrylate resin, preference is given to using a hydroxyalkyl acrylate or methacrylate having a lower alkyl radical or a hydroxyalkoxyalkyl acrylate or methacrylate having a lower alkyl radical, for example 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoacrylate , Diethylene glycol monoacrylate, diethylene glycol monomethacrylate, 2-hydroxypropyl acrylate or methacrylate, 3-hydroxypropyl acrylate or methacrylate, dipropylene glycol monoacrylate or methacrylate used. Particularly preferred are hydroxyalkyl acrylates and methacrylates, in particular 2-hydroxyethyl methacrylate.

Acrylamide or methacrylamides, such as N-propylacrylamide, M-isopropylacrylamide, N-isopropylmethacrylamide, N-propylmethacrylamide, N-butylacrylamide, N-methylacrylamide and N-methylmethacrylamide, diacetone acrylamide, can also be used as the monomer. N- (2-hydroxyethyl) acrylamide and N- (2-hydroxyethyl) methacrylamide.

Similarly, it is also possible to use copolymers of these monomers with one another or with other copolymerizable monomers. When the hydrophilic monomer gives a polymer which is water-soluble, such as polyacrylamide, it is necessary to use a water-insoluble copolymerizable monomer in water so that the resulting copolymer swells only in the water and does not dissolve in the water. The copolymerizable monomer may be used in amounts of from 0.05 to 50% by weight. Preferably, the comonomers are methyl acrylate, ethyl acrylate, isopropyl acrylate, propyl acrylate, butyl acrylate, sec. Butyl acrylate, pentyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, sec, butyl methacrylate, pentyl methacrylate, lower alkoxyethyl acrylates and methacrylates such as methoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl acrylate and ethoxyethyl methacrylate, triethylene glycol acrylate and methacrylate, and glycol monoacrylate or methacrylate.

It is also possible to use unsaturated amines, such as p-aminostyrene, o-aminostyrene, 2-amino-4-vinyltoluene, alkylaminoalkyl acrylates and methacrylates, for example diethylaminoethyl acrylate or methacrylate, dimethylaminoethyl acrylate or methacrylate, tert. Butylaminoethyl acrylate or methacrylate, piperidine ethyl acrylate or methacrylate, morpholine ethyl acrylate or methacrylate, 2-vinylpyridine, 5-. inylpy3

No. 3,047,289, 4-vinylpyridine, 2-ethyl-5-vinylpyridine, dimethylaminopropyl acrylate or methacrylate, dipropylaminoethyl acrylate or methacrylate, di-n-butylaminoethyl acrylate or methacrylate, di-sec-butylaminoethyl acrylate or -methacrylate, Dimethylaminoäthylvinyläther, Diäthylaminoäthylvinylsulfid, Diäthylaminoäthylvinyläther, Aminoäthylvinyläther, Aminoäthylvinylsulfid, Monomethylaminoäthylvinylsulfid, Monomethylaminoäthylvinyläther, Ν- (γ -Monomethylamino) propylacrylamide, N- (ß-monomethylamino) ethylacrylamide or -methacrylamide, 10-aminodecylvinylether, 8-aminooctylvinylether, 5-aminopentylvinylether, 3-aminopropylvinylether, 4-aminobutylvinylether, 2-aminobutylvinylether, monoethylaminoethylmethacrylate, N- (3,5, 5-trimethylhexyl) aminoethylvinylether, N-Cyclohexylaminoäthylvinyläther, 2- ( 1, 1,3,3-tetramethylbutylamino) -ethyl methacrylate, N-tert. Butylaminoäthylvinyläther, N-Methylaminoäthylvinyläther, N-2-Äthylhexylaminoäthylvinyläther, N-tert. Butylaminoäthylvinyläther, N-tert. Octylaminoäthylvinyläther, 2-Pyrrolidonathylacrylat or methacrylate, 3- (dimethylaminoethyl) - 2-hydroxypropyl acrylate or methacrylate, 2Aminoäthylacrylat or methacrylate. Preferred amino compounds are Alkylaminoäthylacrylate and methacrylates and in particular tert. Butylaminoäthylmethacrylat.

Although linear polymers, u.zw. Both homopolymers, such as copolymers are preferred, when hydrophilic resins are used only to prevent friction in watercraft, and crosslinked Hydromischpolymerisate can be used. Such crosslinked copolymers are particularly preferably used if you want to incorporate rot-inhibiting substances in order to achieve a long-lasting adhesion of the underwater coating on the base material.

Preferably, the crosslinking agent is present in amounts of from 0.1 to 2.5, and more preferably in amounts of not more than 2.0% by weight, although also amounts of from 0.05 to 15 or even to 20% by weight of crosslinking agent can be used. Of course, care must be taken that not so much crosslinking agent is used that the product can no longer absorb at least 20% by weight of water.

Typical examples of crosslinking agents are, inter alia, ethylene glycol diacrylate or dimethacrylate, 1,2- or 1,3- or 1,4-butylene dimethacrylate, propylene glycol diacrylate or dimethacrylate, diethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, divinylbenzene, divinyltoluene, diallyl tartrate, allyl pyruvate, allyl maleate, divinyl tartrate, triallylmelamine, N, N'-methylene-bis-acrylamide, glycerol trimethacrylate , Diallylmaleinate, divinyl ether, diallylmonoethylene glycol citrate, ethylene glycol vinylallyl citrate, allyl vinyl maleate, diallyl itaconate, Ethylene glycol diesters of itaconic acid, divinylsulfone, hexahydro-1,3,5-triacryltriazine, triallyl phosphite, diallyl esters of benzenephonic acid, polyesters of maleic anhydride with triethylene glycol, polyallyl glucose such as triallyl glucose, polyallylsucrose such as pentaallylsucrose, sucrose diacrylate, glucose dimethacrylate, pentaerythritol tetraacrylate, sorbitol dimethacrylate, diallyl aconitrate, Divinyl citraconate, diallyl fumarate.

Further, to the mixture, ethylenically unsaturated acids or their salts such as acrylic acid, cinnamic acid, crotonic acid, methacrylic acid, itaconic acid, aconitic acid, maleic acid, fumaric acid, mesaconic acid and citraconic acid may be added. Furthermore, as already mentioned, partial esters may be used, such as mono-2-hydroxypropyl itaconate, mono-2-hydroxyethyl itaconate, mono-2-hydroxyethyl citraconate, mono-2-hydroxypropylaconitate, mono-2-hydroxyethyl maleate, mono-2-hydroxypropyl fumarate, monomethyl itaconate, Monoethyl titaconate, mono-itaconic acid ester of monomethyl ether of diethylene glycol and mono-maleic acid ester of monomethyl ether of diethylene glycol.

The polymers can be prepared as syrup-shaped casting compositions, as aqueous dispersions, by aqueous suspension polymerization or as solutions in organic solvents, such as ethyl alcohol, methyl alcohol, propyl alcohol, isopropyl alcohol, formamide, dimethyl sulfoxide or other appropriate solvents.

The polymerization can be carried out at temperatures between 20 to 150 ° C and usually between 35 or 40 to 90 ° C and can be terminated after application of the underwater coating. The polymerization can be carried out with a free-radical catalyst in amounts of from 0.05 to 1% by weight of the polymerisable monomers. Typical catalysts are tert. Butyl peroctoate, benzoyl peroxide, isopropyl percarbonate, 2,4-dichlorobenzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide and dicumyl peroxide. For catalyzation, it is also possible to use jets, for example UV rays or y-rays.

For example, it is possible to use polymers which are prepared in accordance with Examples A to H.

Unless otherwise stated below, all quantities and proportions are by weight.

Example A: 1000 g of a silicone oil, namely polydimethylsiloxane, 100 g of 2-hydroxyethyl methacrylate and 0.33 g of isopropyl percarbonate were added to a flask equipped with a stirrer and heating mantle. The contents of the flask were stirred vigorously at 100 ° C under nitrogen. After 15 minutes, the slurry was filtered off to isolate the polymer. The polymeric powder was reslurried in 300 ml of xylene, filtered and dried. It was obtained in 98% yield, an alcohol-soluble powder having a particle size of 2 to 5μ.

Example B: The procedure was analogous to Example A, but now xylene instead of silicone oil

No. 3,047,229 and 300 g of 2-hydroxyethyl methacrylate, the amount of isopropyl percarbonate being increased to 0.99 g. A polymer was obtained in spheres in a yield of 85%.

Example C: The procedure was analogous to Example A, wherein the 2-hydroxyethyl methacrylate was replaced by 100 g of 3-hydroxypropyl methacrylate, whereby a thermoplastic, solvent-soluble hydrophilic finely divided polymer was obtained.

Example D: 800 g of ethylene glycol monomethyl ether, 180 g of 2-hydroxyethyl methacrylate, 20 g of acrylic acid and 2 g of tert. Butyl peroctoate was placed in a flask. The solution was heated and stirred under CO atmosphere for 6 hours. The product obtained was thermoplastic and solvent-soluble and could be cured to a crosslinked, solvent-insoluble polymer by further heating, especially with the addition of further catalyst.

Example E: A pouring syrup of 100 parts of 2-hydroxyethyl acrylate, 0.2 parts of ethylene glycol dimethacrylate and 0.4 parts of tert. Butyl peroctoate produced.

Example F: 10 kg of 2-hydroxyethyl methacrylate, 150 g of ethylene glycol dimethacrylate and 4.0 g of tert-butyl peroctoate were heated at 95 ° C. for 50 minutes with stirring to obtain a syrup having a viscosity of 420 cP at 30 ° C. This syrup was tert with 20 g Äthylenglykoldimethacry lat and 20 g. Butyl peroctoate added and stirred until homogeneous.

Corresponding results were also obtained when the ethylene glycol dimethacrylate was replaced by divinylbenzene.

Example G: 75 l of ethanol, 1 kg of t-butylaminoethyl methacrylate, 1.5 kg of N-isopropylacylamide and 22.5 kg of hydroxyethyl methacrylate containing 0.3% of ethylene glycol dimethacrylate were added together with 100 g of tert-butyl peroctoate to a reaction vessel and heated to 85 ° C. for 7 h to achieve up to 90% polymerization.

The hydrophilic polymers according to the invention can be used to obtain antifouling coatings conventional inorganic or organic additives such as cuprous oxide, copper powder, mercury oxide or mixtures of copper oxide and mercury oxide in a ratio of 3: 1, organic tin compounds, such as triphenyltin chloride, triphenyltin bromide, tri-p-cresyltin chloride, triethyltin chloride, tributyltin chloride, phenyldiäthylzinnfluorid, tri- (chlorphenylzinn) chloride, tri- (m-chlorophenylzinn) chloride, dibutyltethyltin bromide, dibutyloctyltin bromide, tricyclohexyltin chloride, triethyltin stearate, tributyltin stearate, Triethyltin fluoride, tributyltin fluoride, diphenylethyltin chloride, diphenylethyltin fluoride, triphenyltin hydroxide, triphenyltin thiocyanate, Triphenylzinntrichloracetat, tributyltin acetate, tributyl tin neodecanoate, tributyltin neopentanoate, trioctyltin neodecanoate, Tributylzinnoxyd, Trioctylzinnoxyd, Triphenylzinnfluorid, Tributylzinnoleat, Tripropylzinn neodecanoate, tributyltin, Tributylzinnoctanoat, Tributylzinndimethylcarbamat, Tributylzinnresinat, Tributylzinnchromat, Amyldiäthylzinn neodecanoate, tributyltin naphthenate, Tributylzinnisooctylmercaptoacetat, bis- (tributyltin) - oxalate, bis (tributyltin) malonate, Bis (tributyltin) adipate, bis (tributyltin) carbonate, organic lead compounds, such as triphenyl lead acetate, triphenylbearearate, triphenylbleine dodecanoate, triphenyl leadioleate, triphenylbleach chloride, triphenyl lead laurate, triethyl leadioleate, triethyl lead acetate, triethyl bisulphearate, trimethylbultrearate, triphenylboron bromide, triphenyl lead fluoride, organic compounds such as 10, 10'-oxybisphenoxazine, 1,2,3-trichloro-4,6-dinitrobenzene, hexachlorophene, dichlorodiphenyltrichloroethane (DDT), Phenol mercuric acetate, tetrachloroisophthalonitrile, bis (n-propylsulfonyl) ethylene and the like. contain.

The amount of fäulnishemmendem substance varies for the coating composition in question, depending on the active ingredient used and the nature of the expected infestation. In general, the antifouling agents are used in amounts of from 2 to 50% by weight, based on the resin, although amounts of 0.1% can be used.

Furthermore, conventional pigments and fillers, such as titanium dioxide, red lead, activated carbon, red iron oxide, talc, aluminum silicate, Fullererde, volcanic dust, zinc oxide, calcium carbonate u. Like. Be used.

The underwater coating mixtures according to the invention can be applied from a solution of organic solvents or from aqueous dispersions. Suitable solvents include lower aliphatic alcohols such as methanol, ethanol, propanol and isopropanol or mixtures thereof with higher boiling alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, Äthylenglykolmonoäthyläther, diacetone alcohol, n-butanol, sec. Butanol, isobutanol and mixtures of these solvents with water.

The coating compositions of the invention generally have good adhesion to underwater surfaces protected by corrosion resistant coatings, such as epoxy resin or vinyl resin based paints, on previously applied antifouling coatings, and on polyester / fiberglass layers. Typical paints are described, for example, in U.S. Pat. Nos. 2,970,923 and 3,214,279 and No. 3,236,793, respectively.

The layer thickness of the applied coating depends on the composition in question and on the manner of application. The layer may be 0.0025 to 6.35 mm and more. In general, coatings range from 0.075 to 0.125 mm. The coating compounds can be applied to the hull

No. 304729 or applied to the posts in the water in the usual way, for example, by brushing, dipping, spraying or rolling.

The coatings applied to hulls are generally brought into the water shortly after drying. When these coatings are prepared from linear, alcohol-soluble polymers, they remain alcohol soluble. However, as already mentioned, it is possible to use cured or crosslinked coatings which have better mechanical resistance. Here, one can use the above-mentioned peroxide catalysts alone or as part of a two-component system which is mixed in the coating composition immediately before application.

Optionally, the coating can also be cured by incorporating a free-radical exciter and heating the coated surface after drying.

A two-component catalyst system for carrying out the curing at room temperature, for example 20 ° C, consists of the abovementioned peroxides together with amine accelerators, such as N, N-dimethylaminoethyl acetate, N, N-dimethylaniline, N, N-dimethylaminoethanol, Ν, Ν- dimethyltoluidine. The accelerator may be present in amounts from 0.05 to 1% by weight of the peroxide, for example as a mixture of 89% benzoyl peroxide with 11% dimethylaniline.

In the following the invention will be explained in more detail with reference to drawings; show it:

1 shows a watercraft with a coating according to the invention and FIG. 2 shows a cross section along the line 2-2 according to FIG.

In the drawings, the boat -2- is in the water and has a coating -6- of hydroxyethyl methacrylate polymers below the waterline-8-. Optionally, the entire boat can also be coated with the polymer. The layer thickness of the coating -6- is drawn considerably larger for reasons of clarity.

Example 1: 50 parts of 2-hydroxyethyl methacrylate and 30 parts of TiO2 were finely ground in a ball mill and then tert with 50 parts of 2-hydroxyethyl methacrylate together with 0.2 parts of ethylene glycol dimethacrylate, 0.1 part of cobalt naphthenate or another metallic siccativ or catalyst and with 0.4 parts. Butyl peroctoate added. The resulting viscous mass was brushed onto a wooden hull and cured at 20 to 235 ° C. The resulting protective coating prevented the approach of marine animals and algae and gives better corrosion resistance. In addition, the frictional resistance to water is reduced.

Example 2: The procedure was analogous to Example 1, wherein the coating composition was poured onto a boat hull made of steel and cured at 100 ° C in the absence of cobalt naphthenate. The frictional resistance to a non-coated hull was significantly lower.

Example 3: The procedure was analogous to Example 1, but now an isomeric mixture of hydroxyisopropyl methacrylate was used instead of hydroxyethyl methacrylate.

Example 4: A glass-lined reaction vessel was tert with 400 kg of ethanol, 200 kg of hydroxyethyl methacrylate and 250 g. Butyl peroctoate fed. The reactor was purged with nitrogen for about one hour and heated to 80 ° C. It was then heated to 80 ° C for 7 h, whereby a 90% conversion of hydroxyethyl methacrylate was achieved. The resulting solution, containing 18% by weight of the polymer, was used to make a coating for sailboats and motorboats, with hulls made of wood, metal and fiberglass, ie a fiberglass impregnated with polyester.

Example 5: Example 4 was repeated, now using 10 kg of methyl methacrylate and 90 kg of hydroxyethyl methacrylate as the monomer. After 7 hours, a conversion of 95% was achieved. The resulting solution was used to prepare a marine vehicle coating composition according to Example 4.

Example 6: Work was carried out according to Example 4, now using 40 kg of methyl methacrylate and 60 kg of hydroxyethyl methacrylate as the monomer. A 90% conversion was achieved after 6 hours. The resulting solution was used to prepare a coating composition for watercraft analogous to Example 4.

Example 7: An approximately 7 m fiberglass boat with an outboard engine of 100 hp was driven at two different speeds between two buoys about 1.6 miles away. The average speeds between the two buoys were determined in both directions at low speed and higher speed. Then the boat was pulled ashore, washed and dried. Subsequently, a polymeric solution according to Example 4 was applied with a roller in a wall thickness of 0.020 to 0.025 mm. The boat was put back on the water again and again the speed determined at low speed and medium speed between the two buoys. Hereby, the following results were obtained:

No. 3 047 2 9

<td>driving speed</td><td>Speed in knots before coating</td><td>Speed in knots after coating</td>

<td>medium ride</td><td>17.2</td><td>19.8</td>

These values show that at a speed of about 10 knots, a reduction in resistance of 13% was achieved, while at a higher speed a reduction of 15% was achieved.

Example 8: The viscosity of water was measured at 23 ° C in a Brookfield RVT synchroelekrisc: viscometer with spindle # 1 at 100 rpm. Hiebei a value of 11, lcP was achieved. The spindle was removed, dried and coated with a solution according to Example 4 by dipping the spindle in the mixture and allowing it to dry after draining. The layer thickness was about 0, 012 mm. The re-measured viscosity was 10.7 cP, and the peripheral speed of the No. 1 spindle was about 0.013 mm / h. At this speed, a friction reduction of about 4% was observed.

Example 9: A 2 m polyester / fiberglass boat was pulled with a rope with intermediate spring scale with a capacity of 10 kg at a speed of 25 knots. On the spring scale, an average power of 8 kg set. After the washed and dried boat body had been coated with a polymer solution according to Example 4 by brush application with a layer thickness of 0.037 mm, in the same towing test at a speed of 2 5 knots only a force of 6.5 kg was read on the spring balance, which corresponds to an 18% reduction in frictional resistance.

Example 10: In a compulsory mixer, 200 g of triphenyl lead acetate and 50 g of titanium dioxide were dispersed in 8 kg of the polymer solution according to Example 4; this dispersion was 2 kg sec. Butyl alcohol added. A No. 1 spindle of a Brookfield viscometer was coated by immersion in the dispersion having a caliper thickness of about 0.015 mm. In water, the viscosity was determined according to Example 3 at 10.5 cP. After removal of the coating, a value of 11.0 cP was achieved.

The coating composition of Example 10 was used in wooden hulled sailboats and polyester / fiberglass hulls to provide an antifouling coating that reduces frictional drag.

Example 11: Example 4 was repeated, using 40 kg of hydroxypropyl acrylate and 80 kg of hydroxyethyl methacrylate as the monomer. After 7 h, a conversion of 85% was achieved. The procedure of Example 8 was repeated with this solution, with similar results. The solution according to Example 11 was also applied to the metal bottom of a motor boat to obtain a friction reducing coating.

Example 12: The procedure was analogous to Example 11, but instead of hydroxypropyl acrylate 20 kg of acrylamide were used and similar results could be achieved.

Example 13 To 500 g of a coating dispersion according to Example 10 were added 2 g of ethylene dimethacrylate (ethylene glycol dimethacrylate), 1 g of benzoyl peroxide and 0.4 g of N, N-dimethylaniline. The coating was immediately applied to a polyester / fiberglass boat body. After drying and standing for 2 h at 24 ° C, the coating in alcohol showed only a swelling, but no dissolution. The resulting coating was more swollen in water than that of Example 10. It also acted as a decay-preventing coating to reduce frictional forces.

Several tests have been carried out to determine the antifouling with hydrophilic polymers according to the invention. After 6 months of test on polyester resin plates, the best results were achieved with triphenyl lead acetate as an antifouling agent. The results were also better than blends containing the antifouling additives concerned, but no hydrophilic polymers.

Most antifouling compounds for overseas ships are based on the addition of copper (I) oxide pigment, which is relatively inert. Much of the copper (I) oxide is not exploited since it is encapsulated in the resin and is only available if the resin itself is destroyed. Another disadvantage of copper (I) oxide is that it favors galvanic corrosion. Further, it is unsuitable for decorative paints because it is relatively dark in color.

Generally, antifouling paints are expected to have 2 1/2 years of effectiveness, although copper (I) oxide coatings are only effective for 12 to 18 months. This is especially true in tankers and large freighters, since even small deposits on the hull increase the frictional resistance and significantly reduce the economy, which is particularly noticeable in tankers. In addition, the periodic removal of lugs on the hull increases inefficiency.

Although numerous organometallic and organic pesticides have been developed in recent years, which have a large spectrum of activity and a good activity against marine organisms. A wirt7

However, the use of these products in antifouling ship coatings was difficult, particularly because of the encapsulation of these substances. Although the new additives are all much more effective than copper (I) oxide, they can only be used in much smaller concentrations than copper (I) oxide due to their relatively high cost. At these relatively low concentrations, however, there is no permanent contact between the toxic-acting particles in the paint, so that these agents can not be used as economically as copper (I) oxide, which in turn is partially inactivated by the encapsulation , Although a modification of the paints by the addition of inert fillers or pigments or water-soluble resins improves the utilization of the toxic activity, but reduces the physical nature of the coatings to uselessness. So far, compromises have been made by using mixtures of organometallic antifoulants together with cuprous oxide to combine mechanical strength and pesticidal activity. However, such blends eliminate the major advantages of organic and organometallic antifouling agents, namely, prevention of galvanic corrosion due to the cuprous oxide and decorative appearance of the paint.

However, the use of the hydrophilic water-insoluble polymers according to the invention surprisingly reduces the problem of encapsulation of the active antifouling agents in a per se impermeable resin system due to the water swellability of the hydrophilic layer.

In other acrylic resins and in other resin systems, solid organic and organometallic antifouling agents do not exhibit significant activity unless their concentration in the coating exceeds a threshold of about 25% by weight of the resin. In the case of the coating compositions according to the invention, the activity starts at much lower concentrations, which shows that the hydrophilic resin does not encapsulate the active particles completely or impermeably.

Example 14: Several series of experiments were carried out to determine if various toxic or antifouling substances have efficacy against marine organisms when incorporated in an unmodified layer of hydroxyethyl methacrylate homopolymer. Ethanol solutions of hydroxyethyl methacrylate homopolymers containing from 2 to 32% of the active ingredients were applied to test panels and tested in seawater in Miami Beach. Hiebei three chemically different compounds, namely hexachlorophene, tetrachloroisophthalonitrile and triphenyl lead acetate (TPLA) were used. These solutions, which contained 14% hydroxyethyl methacrylate homopolymer, were applied by brushes to test strips consisting of glass fiber reinforced polyester that had been cleaned with a sandblast blower. The details of the composition are given in the following Table 1.

The test strips were examined every 30 days. After the first period, all three compositions showed some activity against marine organisms. The resin itself was inactive, as evidenced by a control strip that was quickly coated with deposits. The test strips with hexachlorophene showed good protection, except for a plate containing 2% active ingredients as the lowest limit. Coatings with tetrachloroisophthalonite exhibited moderate and those with triphenyl lead acetate (TPLA) excellent activity. The layers were completely free of slime or mud and showed no deposits or rot. In all cases, the physical nature of the coatings was unchanged. This is surprising because organic lead compounds have not heretofore been effective in protecting paints, although they exhibit broad spectrum activity in seawater when leaching from porous blocks.

After 5 months immersion, the test strips were removed with the hexachlorophene and tetrachloroisophthalonitrile-containing paints, as they showed a strong coating. The coatings with TPLA were still excellent. After 6 months of testing two test strips with the highest concentration of active substances, namely 16 to 32%, still showed 100% effectiveness, while the layer with 8% triphenyl lead acetate (TPLA) showed a 92%, that with 4% TPLA had an 84% and the 2% TPLA offset layer had only 36% potency. The complete results are shown in Table 2.

\ r.304729

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Nr.304729

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Nr.304729

EXAMPLE 15 Further experiments were carried out with triphenyl lead acetate (TPLA) at four different concentrations of 2 to 16% by weight in hydroxyethyl methacrylate homopolymer and also in two copolymers of once 90% hydroxyethyl methacrylate (Hema) and 10% methyl methacrylate and 60% hydroxyethyl methacrylate ( Hema) and 40% methyl methacrylate. The copolymers have a lower seawater permeability than hydroxyethyl methacrylate homopolymer. These coatings were applied both with brushes and with squeegees, u.zw. on 20 x 25 cm sheets of aluminum alloy. After 1 month, it was found that the paints based on hydroxyethyl methacrylate homopolymer were better than those based on the copolymers. Pigmentation of hydroxyethyl methacrylate homopolymer (HMP) did not change the efficacy.

There were prepared 12 different paint compositions containing all 153 g of the invention to be used acrylate, 240 g of iron oxide and 614 g of ethanol per 1 paint composition.

The mixtures Nos. 1 to 4 each contained hydroxyethyl methacrylate homopolymer (HMP), the mixtures Nos. 5 to 8 in each case the copolymer of 90% hydroxyethyl methacrylate (Hema) and 10% methyl methacrylate and the paints Nos. 9 to 12 the copolymer of 60% Hydroxyethyl methacrylate (Hema) and 40%

Methyl methacrylate.

The paint compositions Nos. 1, 5 and 9 each contained 11 g of triphenyl lead acetate (TPLA) corresponding to 2%, the paint compositions Nos. 2, 6 and 10 each 4%, the paint compositions Nos. 3, 7 and 11 each 8% and the paint compositions Nos. 4, 8 and 12 each 16% Triphenylbleiacetat.

The mixtures containing 2, 4, 8 or 16% in each case still contained 130, 115, 85 and 20 30% talcum per 1 coating mass. All mixtures contained 39.6% pigments and 24.5% by volume non-volatile

Ingredients.

The following Table 3 shows the results after 1 month immersion time.

Table 3

<td>polymer</td><td>% TPLA</td><td>Color no.</td><td>experimental sheet</td><td>behavior by appearance</td><td>1 month Efficacy in%</td>

Nr.304729

Table 3 (continued)

<td>polymer</td><td>% TPLA</td><td>Color no.</td><td>experimental sheet</td><td>Behavior by appearance</td><td>1 month Efficacy in%</td>

<td>60/40</td><td>2</td><td>9</td><td>9-1 / c</td><td>Blow, peeling</td><td>25</td>

<td>60/40</td><td></td><td></td><td>9-2 / c</td><td>Blow, peeling</td><td>35</td>

<td>60/40</td><td>4</td><td>10</td><td>10-1 / c</td><td>Blow, peeling</td><td>70</td>

<td>60/40</td><td></td><td></td><td>10-2 / c</td><td>not manufactured</td><td></td>

<td>60/40</td><td>8th</td><td>11</td><td>11-1 / c</td><td>Blow, Peeling, corrosion appearance</td><td>85</td>

<td>60/40</td><td></td><td></td><td>11-2 / c</td><td>Blow, Peeling, corrosion appearance</td><td>25</td>

<td>60/40</td><td>16</td><td>12</td><td>12-1 / c</td><td>not manufactured</td><td></td>

<td>60/40</td><td></td><td></td><td>12-2 / c</td><td>not manufactured</td><td></td>

<td>60/40</td><td></td><td></td><td>12-2 / b</td><td>peeling</td><td>75</td>

For the test panels b means that the mass was applied with brushes or the letter c that the paint was poured.

Example 16: In another series of experiments aluminum sheets were coated with HMP solutions containing the following antifouling substances:

No. 304729

<td>test sheet</td><td>antifouling substance</td>

<td>A</td><td>Bis (tri-n-butyltin) oxide TBTO</td>

<td>B</td><td>Triphenyltin chloride TPTCI</td>

<td>C</td><td>Tributyltin fluoride TBTF</td>

<td>e</td><td>Triphenylblue chloride TPLC</td>

<td>F</td><td>Triphenyl lead laurate TPLL</td>

<td>G</td><td>1,2,3-trichloro-6 "-dinitrobenzene TCDN</td>

<td>H</td><td>saturated solution of TCDN in TBTO PBTO fzirka 20.5 ^ - TCDN)</td>

<td>I</td><td>10, 10'-Oxybisphenoxarsine OPO</td>

<td>1</td><td>Mercury (I) - chloride, powdered g</td>

<td>K</td><td>Copper (I) oxide, quality AA</td>

The composition of the various paint compositions is shown in Table 4 below, while the results after one month of immersion are shown in Table 5. The experiments were again carried out in seawater near Miami. Test panels K4 and K16, with cast and brushed coatings containing copper oxide on aluminum, were believed to have exhibited galvanic corrosion; however, as copper fl) oxide was important for comparative purposes, additional K6 and K16 paints were applied to glass fiber reinforced polyester strips. These test strips with K4 were achieved by brush application while K16 was cast, u.zw. only because the last-mentioned test strips were sufficiently flat to apply the coating exactly.

Some of the compositions showed excellent results, u.zw. not only because of the protective effect, but also because of the considerable pigment content.

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<td rowspan="9">Composition of paints based on HMP with 4 and 16% of different antifouling substances in g each 1</td><td>E / sixteen</td><td>CO.-Η 1 | ο ο T IO 00 T CO vH T-ι cq co</td><td>1118</td>

<td>Color no.</td><td>> 'S i_) £ $ S £ & § 1 j <8 i <QMCQCl, © .3d £ lm Ü3 E-1 Egg E-1 E-1 W E- ·: <J</td><td>A total of</td>

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Table 5

<td colspan="5">Behavior in the immersion test</td>

<td>Active ingredient</td><td>Color no.</td><td>Sheet metal no.</td><td>nature</td><td>Behavior in %</td>

<td></td><td>E / sixteen</td><td>E16.1 / c</td><td>soft</td><td>98</td>

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Table 5 (continued)

<td>Active ingredient</td><td>Color No,</td><td>Sheet metal no.</td><td>nature</td><td>Behavior in %</td>

<td>Mercury (I) -</td><td>J / 4</td><td>J4. 1 / c</td><td>Good</td><td>100</td>

<td>chloride</td><td></td><td>J4.1 / b</td><td>Good</td><td>95</td>

<td>Copper (I) oxide</td><td>K / 4</td><td>K4.1 / c</td><td>Korrosionser-</td><td>95</td>