Classifications

• • 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
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
  • C09D5/1662—Synthetic film-forming substance
• • 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
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
  • C09D5/1662—Synthetic film-forming substance
  • C09D5/1668—Vinyl-type polymers
• • 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
  • C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
  • C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
  • C09D139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
• • 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
  • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
• • 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
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers

Definitions

• This invention relates to marine anti-fouling (AF) paints generally used as topcoat paints for ships' hull, particularly to marine anti-fouling paints that polish at a predetermined rate and to a polymeric composition for a marine anti-fouling paint that hydrolyses at a predetermined rate in the presence of sea water.
• AF marine anti-fouling
• a topcoat paint comprising anti-fouling agents controls the extent of marine fouling.
• the anti-fouling agents are biocides that are freed from the paint surface at a rate such that their concentration is lethal to marine organisms.
• TBT tributyltin
• EP-A-51930 is a milestone patent disclosing such TBT copolymers.
• the "self-polishing" action leads to decrease in hull roughness during service.
• TBT systems have dominated the antifouling market for the last 20 years.
• tributyltin (TBT) had been shown to leach into the water (it is indeed a potent marine biocide which gives an enhanced anti-fouling effect), harming sea life, possibly entering the food chain, and causing deformations in oysters and sex changes in whelks.
• a marine paint comprising a film-forming polymer, prepared by polymerisation of monomer units A of at least one triorganotin salt of an olefinically unsaturated carboxylic acid and at least one comonomer B selected from the group comprising vinylpyrrolidone, vinylpiperidone and vinylcaprolactam, the balance being at least one C1-C4 alkylmethacrylate and/or styrene comonomer C.
• - EP-B-289 481 and EP-B-526 441 discloses marine paint compositions based on rosin or its copper or zinc derivatives and a copolymer of alkyl methacrylates and/or styrene with comonomers which are cyclic tertiary amides or imides having an alkenyl group.
• - EP-A-342 276 relates to the preparation of metal (preferably zinc or copper) containing resin composition which is characterised by having hydrolysable metal ester bonding at the end portion of pendant chain.
• GB 2 311 070 also describes a composition comprising a resin having at least one metal carboxylate.
• EP-B-0131 626 describes antifouling paints based on film-forming water insoluble, seawater erodible, polymeric binders containing trialkylsilyl (meth)acrylates;
• EP-A-755 733 discloses antifouling coating compositions based on such a trialkylsilyl esters containing copolymer and a chlorinated paraffin.
• An object of the present invention is to provide such improved self-polishing and anti-fouling paint compositions for use as topcoat paints for ships' hull.
• Another object of the invention is to provide improved polymeric binders for a marine anti-fouling paint that hydrolyses at a predetermined rate in the presence of seawater.
• a yet further object of the present invention is to provide an anti-fouling marine paint composition with a high solids content.
• the present invention provides a marine paint comprising essentially:
• a first polymer comprising from 20 to 70 wt% of monomer units A of at least one hydrolysable either tin or silicium ester of an olefinically unsaturated carboxylic acid or salt of copper, zinc, calcium of an olefinically unsaturated carboxylic acid, the balance of the monomer units being monomer units C selected from the group consisting of the esters of ethylenically unsaturated carboxylic acids with C1-C18 alcohols, styrene, alpha-methyl styrene, vinyl toluenes, and mixtures thereof.
• R' is a n-alkylidene radical having 2 to 8 carbon atoms
• - R" is selected from the group consisting of alkyl, cycloalkyl, aryl, alkylaryl and arylalkyl radicals having a maximum of 18 carbon atoms, - R'" is H or CH3, - R"" is a n-alkylidene radical having from 1 to 8 carbon atoms,
• - R"'" is H or R"
• the balance of the monomer units being monomer units C selected from the group consisting of the esters of ethylenically unsaturated carboxylic acids with C1-C18 alcohols, styrene, alpha-methyl styrene, vinyl toluenes, and mixtures thereof.
• At least one antifoulant At least one antifoulant.
• the relative ratio of the first polymer comprising monomer units A to the second polymer comprising monomer units B is from 95:5 to 10:90.
• the two polymeric binders are sufficiently compatible to produce a stable paint composition but sufficiently incompatible to give such structure to the paint that it can be applied in desired layer thicknesses. There will thus be less need to add thixotropic agents in order to obtain a suitable structure. It is known in the art that the solids content of a paint composition decreases when the amount of thixotropic agent increases; the paint compositions of the present invention will thus keep a high solids content.
• the groups R can be different but are preferably the same.
• the first polymer comprises from 20 to 70 wt% of monomer units A, preferably from 30 to 65 wt%, and more preferably from 50 to 60 wt%, the balance being monomer units C.
• the first polymer comprising monomer units A is a metal containing resin composition that can be obtained as described in EP-A- 342276 by reacting a mixture of
• an acid group containing base resin comprising essentially monomer units C and olefinically unsaturated carboxylic acids monomer units corresponding to monomer unit A;
• the metals are selected from the zinc, copper or calcium.
• the acid group containing base resin has an acid value of from 25 to 350 mg KOH/g, the low boiling organic basic acid has a boiling point of from 100 to 240 °C and the high boiling organic monobasic acid has a boiling point that is at least 20 °C higher than the boiling point of said low boiling organic basic acid.
• the first polymer comprising monomer units A has a number average molecular weight of from 1000 to 50000, and contains from 20 to 65 wt% of structural units derived from trialkylsilyl ester of polyme sable unsaturated carboxylic acid, as described in EP-A-775733.
• R' is a n-alkylidene radical having 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms, more preferably 3 carbon atoms.
• the most preferred monomer unit B is N-vinyl pyrrolidone.
• R"' is CH3; examples of such monomers are described in Polymer 39(17), 4165-9, 1998.
• N-vinyl lactams are being used, more preferably N-vinylpyrrolidone
• the second polymer comprises from 5 to 40 wt% of monomer units B, preferably from 10 to 30 wt% and more preferably from 15 to 30 wt%.
• Monomer units C are preferably selected from the group consisting of the esters of ethylenically unsaturated carboxylic acids with C1-C18 alcohols, styrene, alpha- methyl styrene, vinyl toluenes, and mixtures thereof.
• the ethylenically unsaturated carboxylic acid is more preferably selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, and mixtures thereof, most preferably selected from the group consisting of acrylic acid, methacrylic acid, and mixtures thereof.
• the alcohol may be an aliphatic or a cycloaliphatic alcohol, and it may be linear or branched; it is more preferably selected from C1-C10 alcohols, more preferably from C1-C4 alcohols, most preferably from C1-C2 alcohols.
• Typical examples of monomer units of the ester type are stearyl (meth)acrylate, isobornyl (meth)acrylate, lauryl methacrylate, n- butyl (meth)acrylate, isobutyl (meth)acrylate, ethyl (meth)acrylate and methyl (meth)acrylate.
• the polymer can be prepared by addition polymerisation of the appropriate monomers in the appropriate proportions at polymerisation conditions using a free radical catalyst such as e.g. benzoyl peroxide, tert-butyl peroxy 2-ethyl hexanoate (TBPEH), t-butyl peroxybenzoate (TBP), or azobisisobutyronitrile.
• a free radical catalyst such as e.g. benzoyl peroxide, tert-butyl peroxy 2-ethyl hexanoate (TBPEH), t-butyl peroxybenzoate (TBP), or azobisisobutyronitrile.
• TPEH tert-butyl peroxy 2-ethyl hexanoate
• TBP t-butyl peroxybenzoate
• azobisisobutyronitrile azobisisobutyronitrile
• Polymerisation is preferably carried out at a temperature in the range of 70-140°C although higher temperatures may be used providing that the solvent and the catalyst are adapted thereto. Within this range the use of higher temperatures produces polymers of lower molecular weight. Polymerisation may be carried out by heating all the polymer ingredients in the solvent or preferably by gradually adding the monomers and catalyst to the heated solvent. The latter procedure produces polymers of lower molecular weight.
• the ratio of the two polymers used to prepare the paint composition can vary over a broad range of values depending upon the desired properties of the composition.
• the relative ratio of the first polymer comprising monomer units A to the second polymer comprising monomer units B is from 95:5 to 10:90, preferably from 80:20 to 40:60.
• the antifoulant used as the other essential component in the coating composition of the present invention may be any of conventionally known antifoulants.
• the known antifoulants are roughly divided into inorganic compounds, metal-containing organic compounds, and metal-free organic compounds.
• the inorganic compounds include copper compounds (e.g. copper sulfate, copper powder, cuprous thiocyanate, copper carbonate, copper chloride, and the traditionally preferred cuprous oxide), zinc sulfate, zinc oxide, nickel sulfate, and copper nickel alloys.
• copper compounds e.g. copper sulfate, copper powder, cuprous thiocyanate, copper carbonate, copper chloride, and the traditionally preferred cuprous oxide
• zinc sulfate zinc oxide
• nickel sulfate nickel alloys.
• Examples of the metal-containing organic compounds include organo-copper compounds, organo-nickel compounds, and organo-zinc compounds. Also usable are manganese ethylene bis dithiocarbamate (maneb), propineb, and the like.
• Examples of the organo-copper compounds include copper nonylphenol- sulphonate, copper bis(ethylenediamine) bis(dodecylbenzenesulphonate), copper acetate, copper naphtenate, copper pyrithione and copper bis(pentachlorophenolate).
• Examples of the organo-nickel compounds include nickel acetate and nickel dimethyldithiocarbamate.
• organo-zinc compounds examples include zinc acetate, zinc carbamate, bis(dimethylcarbamoyl) zinc ethylene-bis(dithiocarbamate), zinc dimethyldithiocarbamate, zinc pyrithione, and zinc ethylene-bis(dithiocarbamate).
• mixed metal-containing organic compound one can cite (polymeric) manganese ethylene bis dithiocarbamate complexed with zinc salt (mancozeb).
• metal-free organic compounds examples include N- trihalomethylthiophthalimides, trihalomethylthiosulphamides, dithiocarbamic acids, N-arylmaleimides, 3-(substituted amino)-1 ,3 thiazolidine-2,4-diones, dithiocyano compounds, triazine compounds, oxathiazines and others.
• N-trihalomethylthiophthalimides examples include N- trichloromethylthiophthalimide and N-fluorodichloromethylthiophthalimide.
• dithiocarbamic acids include bis(dimethylthiocarbamoyl) disulphide, ammonium N-methyldithiocarbamate and ammonium ethylene- bis(dithiocarbamate).
• trihalomethylthiosulphamides examples include N-(dichlorofluoromethylthio)- N',N'-dimethyl-N-phenylsulphamide and N-(dichlorofluoromethylthio)-N',N'- dimethyl-N-(4-methylphenyl)sulphamide.
• N-arylmaleimides examples include N-(2,4,6-trichlorophenyl)maleimide, N-4 tolylmaleimide, N-3 chlorophenylmaleimide, N-(4-n-butylphenyl)maleimide, N- (anilinophenyl)maleimide, and N-(2,3-xylyl)maleimide.
• 3-(substituted amino)-1 ,3-thiazolidine-2,4-diones examples include 2- (thiocyanomethylthio)-benzothiazole, 3-benzylideneamino-1 , 3-thiazolidine-2,4- dione, 3-(4-methylbenzylideneamino)-1 ,3-thiazolidine-2,4-dione, 3-(2- hydroxybenzylideneamino)-1 ,3-thiazolidine-2,4-dione,3-(4- dimethylaminobenzylideamino)-1 ,3-thiazolidine-2,4-dione, and 3-(2,4- dichlorobenzylideneamino)-1 ,3-thiazolidine-2,4-dione.
• dithiocyano compounds examples include dithiocyanomethane, dithiocyanoethane, and 2,5-dithiocyanothiophene.
• triazine compounds examples include 2-methylthio-4-butylamino-6- cyclopropylamino-s-triazine.
• oxathiazines examples include 1 ,4,2-oxathiazines and their mono- and di-oxides such as disclosed in PCT patent WO 98/05719: mono- and di-oxides of 1 ,4,2- oxathiazines with a substituent in the 3 position representing (a) phenyl; phenyl substituted with 1 to 3 substituents independently selected from hydroxyl, halo, C1- 12 alkyl, C5-6 cycloalkyl, trihalomethyl, phenyl, C1-C5 alkoxy, C1-5 alkylthio, tetrahydropyranyloxy, phenoxy, C1-4 alkylcarbonyl, phenylcarbonyl, C1-4 alkylsulfinyl, carboxy or its alkali metal salt, C1-4 alkoxycarbonyl, C1-4 alkylaminocarbonyl, phenylaminocarbonyl, tolyiaminocarbonyl, morph
• metal-free organic compounds include 2,4,5,6- tetrachloroisophthalonitrile, N,N-dimethyl-dichlorophenylurea, 4,5-dichloro-2-n- octyl-4-isothiazoline-3-one, N,N-dimethyl-N'-phenyl-(N-fluorodichloromethylthio)- sulfamide, tetramethylthiuramdisulphide, 3-iodo-2-propinylbutyl carbamate, 2- (methoxycarbonylamino)benzimidazole, 2,3,5,6-tetrachloro-4- (methylsulphonyl)pyridine, diiodomethyl-p-tolyl sulphone, phenyl(bispyridine)bismuth dichloride, 2-(4-thiazolyl)benzimidazole, dihydroabietyl amine, N-methylol formamide and pyridine triphenyl
• the use as antifoulant of the oxathiazines disclosed in WO-A-9505739 has the added advantage (disclosed in EP-A-823462) of increasing the self-polishing properties of the paint.
• the paint formulation should preferably include at least an effective amount of at least one barnaclecide, such as cuprous oxide or thiocyanate.
• a preferred barnaclecide is disclosed in EP-A- 831134.
• EP-A-831134 discloses the use of from 0.5 to 9.9 wt%, based on the total weight of the dry mass of the composition, of at least one 2-trihalogenomethyl-3- halogeno-4-cyano pyrrole derivative substituted in position 5 and optionally in position 1 , the halogens in positions 2 and 3 being independently selected from the group consisting of fluorine, chlorine and bromine, the substituent in position 5 being selected from the group consisting of C1-8 alkyl, C1-8 monohalogenoalkyl, C5-6 cycloalkyl, C5-6 monohalogenocycloalkyl, benzyl, phenyl, mono- and di- halogenobenzyl, mono- and di-halogenophenyl, mono- and di-C1-4-alkyl benzyl, mono- and di-C1-4- alkyl phenyl, monohalogeno mono-C1-4-alkyl benzyl and monohalogeno mono-C1-4- alkyl
• One or more antifoulants selected from such antifoulants are employed in the present invention.
• the antifoulants are used in such an amount that the proportion thereof in the solids contents of the coating composition is usually from 0.1 to 90% by weight, preferably 0.1 to 80% by weight, and more preferably from 1 to 60% by weight. Too small antifoulant amounts do not produce an antifouling effect, while too large antifoulant amounts result in the formation of a coating film which is apt to develop defects such as cracking and peeling and thus becomes less effective in anti-fouling property.
• the paint further contains pigment(s), solvent(s) and additive(s).
• the paint composition contains one or more pigments (or fillers).
• the paint composition can contain one or more pigments which are "active" pigments, i.e. sparingly soluble in seawater. These pigments have a sea water solubility such that the pigment particles do not survive at the paint surface. These pigments have the effect of inducing the overall smoothing which the relatively- moving sea water exerts on the paint film, minimizing localized erosion and preferentially removing excrescencies formed during the application of the paint. Sparingly soluble pigments have long been used in self-polishing anti-fouling paints.
• Typical examples are cuprous thiocyanate, cuprous oxide, zinc oxide, cupric acetate meta-arsenate, zinc chromate, zinc dimethyl dithiocarbamate, zinc ethylene bis(dithiocarbamate) and zinc diethyl dithiocarbamate.
• the preferred sparingly soluble pigments are zinc oxide, cuprous oxide and cuprous thiocyanate. Mixtures of sparingly soluble pigments can be used, e.g.
• zinc oxide which is most effective at inducing the gradual dissolution of the paint, can be mixed with cuprous oxide, cuprous thiocyanate, zinc dimethyl or diethyl dithiocarbamate, or zinc ethylene bis-(dithiocarbamate) which are more effective marine biocides; the most preferred is a mixture of zinc oxide with cuprous oxide or thiocyanate.
• the paint composition can contain one or more pigments that are highly insoluble in seawater, such as titanium dioxide, talc or ferric oxide. Such highly insoluble pigments can be used at up to 40 percent by weight of the total pigment component of the paint. Highly insoluble pigments have the effect of retarding the erosion of the paint.
• the paint composition can contain one or more pigments or dyes that impart a color to the paint, e.g. titanium dioxide, cuprous oxide or iron oxide.
• the proportion of pigment to polymer is generally such as to give a pigment volume concentration of at least 25 percent, preferably at least 35 percent, in the dry paint film.
• the upper limit of pigment concentration is the critical pigment volume concentration. Paints having pigment volume concentrations of up to about 50 percent, for example, have been found very effective.
• organic solvent examples include aromatic hydrocarbons such as xylene and toluene; aliphatic hydrocarbons such as hexane and heptane, esters such as ethyl acetate and butyl acetate; amides such as N-methylpyrrolidone and N,N- dimethylformamide; alcohols such as isopropyl alcohol and butyl alcohol; ethers such as dioxane, THF and diethyl ether; and ketones such as methyl ethyl ketone, methyl isobutyl ketone and methyl isoamyl ketone.
• the solvent may be used alone or in combination thereof.
• Solvents are used to obtain the desired viscosity at the expected operating temperature for the application on the ship hull, preferably in the range of 10-50 dPa.s, more preferably of 20-40 dPa.s, most preferably of about 25 dPa.s.
• the nature of the solvents is also adapted to the expected operating temperature for the application on the ship hull, taking into account the desired drying time.
• Additive ingredients may optionally be incorporated into the coating composition of the present invention thus prepared.
• the additive ingredients are dehumidifiers, and additives ordinarily employed in coating compositions as stabilizers and anti-foaming agents.
• the solids content of binder solutions was determined by weighing before and after heating a sample for 1 hour at 120°C [standard test methods ISO 3233/ASTM 2697/DIN 53219].
• the molecular weight distribution was determined by gel permeation chromatography (GPC) with tetrahydrofuran (THF) as solvent and polystyrene as reference.
• GPC gel permeation chromatography
• THF tetrahydrofuran
• d polydispersity
• the thixotropic factor is determined by measuring the viscosity with a rotation viscosimeter (Haake VT 181 ) at a low and a high speed. It is defined as the ratio of the viscosity at 5.66 rpm to the viscosity at 181 rpm. [standard methods DIN 53018, 53019, 53214]. The thixotropic factor was measured at standard conditions with paints that all had been thinned down to a viscosity between 11 and 13 dPa.s
• the minimum duration of the test was 8 months.
• Two layers of the self-polishing paint to be tested were applied, to give a total dry film thickness between 200 and 300 ⁇ m.
• the tests were carried out in constantly refreshed natural seawater, at a constant temperature of 20 °C.
• the discs were rotated at 1000 rpm, corresponding to about 34 km/hr (18 knots/hr) at 9 cm from the centre.
• the total dry film thickness was determined at 7-week intervals, after allowing the paint to dry during one day. It was measured at a number of fixed points, each located at 9 cm from the centre of the discs.
• the stability of a paint composition was tested as follows: 250 I of the paint compositions were stored in a can at 40 °C during 6 months. The paint composition is acceptable if the following is observed:
• Polymer PA1 is a 53/47 (w/w) copolymer of tributyltin methacrylate (TBTMA) and methyl methacrylate (MMA).
• TTMA tributyltin methacrylate
• MMA methyl methacrylate
• Acid group containing base resins were prepared following the procedure described in reference examples 1 to 4 of EP-A-0,342,276_: ⁇ Reference resin R1.
• Polymer PA2 was prepared following the procedure described in example 18 of EP-A-0,342,276.
• the resinous varnish obtained in reference resin R1 was treated with copper acetate and naphtenic acid.
• the copper acrylate varnish so obtained had a solids content of 43.9 wt% and a Brookfield viscosity of 34 dPa.s.
• Polymer PA3 was prepared similarly from reference resin R2; the copper acrylate varnish so obtained had a solids content of 47.4% and a Brookfield viscosity of 11 dPa.s
• Polymer PA4 was prepared following the procedure described in Examples S-1 to S-6 of EP-A-0,775,733 with 57 wt% of tributylsilylmethacrylate (TBSiMA) and 43 wt% of MMA.
• Polymer PB1 was obtained by polymerising 65 g of methylacrylate (MA), 25 g of vinylpyrrolidone (VP) and 10 g of butylacrylate (BA) in 100 g of xylene, using TBPEH as initiator. Properties of Polymers PB1 to PB3 are given in Table A.
• Comparative examples CP1 and CP2 have been prepared according to methods known in the art and disclosed for example in European Patent n° EP B-0,218,573 where monomers A and B are incorporated in the same polymer .
• Polymer CP1 has the same monomer composition (and a similar Mw) as the 5:4 mixture of polymers PA1 and PB2 (see Tables A and G )
• Polymer CP2 has the same monomer composition (and a similar Mw) as the 5:4 mixture of polymers PA1 and PB1 (see Tables A and G )
• the synthesis of polymers having the same monomer composition as a mixture of polymer PA2 (or PA3) with any of polymers PB was not possible; the reaction with the copper derivative destroyed the lactam ring.
• the first polymer PA1 , the second polymer PB1 and dioctyl phthalate (DOP) were mixed respectively in solids volume ratio of 5:4:1.
• Pigments were added to the composition in an amount of 21 vol%, essentially under the form of Cu 2 0, that also acted as an antifoulant.
• Anti-settling agents (Bentonite) and stabilisers (Molecular sieve) were also added to the paint composition.
• the first polymer PA2 and the second polymer PB2 were mixed respectively in the volume ratio of 3:1.
• Example 14 The first polymer PA4 and the second polymer PB2 were mixed respectively in the volume ratio of 1 : 1.
• the quantities, components and ratios are summarised in Table E.
• SeanineTM 4,5-dichloro-2-n-octyl-4isothiazoline-3-one (30w% solution)
• No thixotropic agent has been added to any of examples 1 to 8 and C1 to C5.
• Comparative examples C6 to C11 contain only one polymer with both monomeric units A and B.
• various amounts of ThixatrolTM ST were used in order to increase the thixotropy to an acceptable level, respectively 0, 1 and 2 vol

Landscapes

• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Paints Or Removers (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Priority Applications (14)

Applications Claiming Priority (2)

Publications (1)

Family

ID=8171098

Family Applications (1)

Country Status (17)

Cited By (2)

Families Citing this family (9)

Citations (1)

Family Cites Families (3)

• 2000
  • 2000-02-25 EP EP00200666A patent/EP1127925A1/en not_active Withdrawn
• 2001
  • 2001-02-22 DK DK01919349T patent/DK1263898T3/da active
  • 2001-02-22 JP JP2001562634A patent/JP2003524056A/ja active Pending
  • 2001-02-22 AU AU4647901A patent/AU4647901A/xx active Pending
  • 2001-02-22 CN CNA2004100789095A patent/CN1618905A/zh active Pending
  • 2001-02-22 AU AU2001246479A patent/AU2001246479C1/en not_active Ceased
  • 2001-02-22 WO PCT/EP2001/002172 patent/WO2001062858A1/en not_active Ceased
  • 2001-02-22 KR KR1020027011136A patent/KR20020097186A/ko not_active Withdrawn
  • 2001-02-22 PL PL01357645A patent/PL357645A1/xx unknown
  • 2001-02-22 AT AT01919349T patent/ATE277132T1/de not_active IP Right Cessation
  • 2001-02-22 BR BR0108661-8A patent/BR0108661A/pt not_active IP Right Cessation
  • 2001-02-22 DE DE60105775T patent/DE60105775T2/de not_active Expired - Fee Related
  • 2001-02-22 CN CNB018064191A patent/CN1174056C/zh not_active Expired - Fee Related
  • 2001-02-22 ES ES01919349T patent/ES2228839T3/es not_active Expired - Lifetime
  • 2001-02-22 CA CA002400833A patent/CA2400833A1/en not_active Abandoned
  • 2001-02-22 HK HK02109448.7A patent/HK1047763B/en not_active IP Right Cessation
  • 2001-02-22 EP EP01919349A patent/EP1263898B1/en not_active Expired - Lifetime
  • 2001-02-22 PT PT01919349T patent/PT1263898E/pt unknown
• 2002
  • 2002-08-14 ZA ZA200206510A patent/ZA200206510B/en unknown
  • 2002-08-23 NO NO20024028A patent/NO20024028L/no not_active Application Discontinuation

Patent Citations (1)

Also Published As

Similar Documents

Legal Events