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
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
  • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • 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
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
  • C09D163/10—Epoxy resins modified by unsaturated compounds
• • 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
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
• • 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

Definitions

• This invention relates to coating compositions for marine structures, to such structures and to methods of making them.
• G.B.967,921 which covers the addition of oxalic acid
• hydroxy polycarboxyiic acids such as tartaric acid
• G.B.1,526,597 which covers the addition of benzotriazole to the resin to get a good bond between copper foil and glass-reinforced polyester in the manufacture of copper clad laminates for electrical purposes.
• polyester and similarly curable resins are stable in the presence of 20—80% by weight of copper or copper alloy powder if they have an acid value below about 10 mg KOH/g, preferably not greater than 5,
• compositions cure with a tack-free air surface.
• a tack-free surface is extremely surprising in view of the expected inhibiting effect of copper and in view of the fact that acid values of the order of 20-30 are much more normal. It is furthermore remarkable that when such normal resins are mixed with coppe powder (which is suggested in US Patent 3219505), they prove to be unstable and lumpy once the peroxide is added to the system after storage.
• the similarly curable resins usable in the invention are those cured by a free—radical-initiated cross-linking mechanism such as vinyl esters and urethane acrylates.
• the compositions according to this invention can be used as fouling-resistant coatings on structures for use in marine environments e.g. boats, buoys, platforms, pontoons, etc. Abrasion of the surface to expose copper particles is not necessary when high levels of copper are used although it is preferable to do so when lower levels of copper powder or copper alloy (below around 30% by weight) are employed.
• the resins are most commonly unsaturated polyester resins which are manufactured by the combination of an ⁇ , ⁇ — unsaturated dicarboxvlic acid or anhydride, with or without the addition of a saturated dicarboxylic acid or anhydride and one or more glycols.
• the resultant condensate is dissolved in an. unsaturated vinyl compound so that the liquid resin is 100% reactive and can be converted to a rigid crosslinked structure at room temperature by the addition of an organic peroxide in the presence of a promoter.
• vinyl type monomers — styrene, vinyl toluene, chlorostyrene, bromo styrene, methyl meth acryiate, ethyiene glycoi dimethacrylate.
• resins that can be used are the so-called vinyl esters and urethane acrylates. Both of these have low acid values and are dissolved in vinyl type monomers such as styrene.
• the former are made by the reaction of acrylic or methacrylic acid with p ⁇ lyepoxides whilst the latter are the reaction products of di- or poly hydroxy compounds (which may be polymeric), di- or poly isocyanates and hydroxy alkyl acrylates or methacryiates.
• the copper or copper alloy powder used in this invention can be of any suitable particle size and shape but the preferred material is a copper or copper alloy powder which passes 100, and better still, 300 mesh (British Standard) and is irregular in shape.
• thixotropic agents such as fumed silicas sold under the trade marks Aerosil ® and
• Cab-O-Sil ® and the materials may be coloured by the use of suitable pigments and dyestuffs.
• Preferred amounts of particulate copper or alloy are in the range 20 to 80% by weight of the total composition, more particularly 30-75% by weight. Any slight segregation and settling of the powder in the gelcoat once applied, tending to increase the concentration of the metal towards the lower face of the gel, will not be objectionable.
• the invention is not limited to gel coats; use of the compositions as flow coats (a finishing coat on an exposed face of the substrate) on GRP and other substrates such as steel or cement also show excellent properties. There is no reason why the compositions described should be limited to marine structures as they could equally be used for decorative purposes e.g. gel coats on cladding panels.
• a gelcoat was prepared using the following formulation:- CRYSTIC® 390 (a polyester resin 270 p.b.w. based on isophthalic acid, maleic anhydride, propyiene and diethylene giycols, of acid number approximately 17 to 20)
• a gelcoat was prepared as in Example 1 except that the CRYST ⁇ C ® 390 was replaced by CRYSTZC® D3402, an isophthalic acid-based resin similar to CRYSTIC ® 390 except that it has an acid value below 10 mgKOH/g as against 17-20 mgKCH/g for CRYSTIC®390. This material was storage stable for several weeks and did not exhibit lumpiness when peroxide catalysts such as those mentioned in Example 1 were added.
• a laminate was made by coating a mould with the composition of Example 2 and after gelation three layers of 450 g/m glass mat were laid up on it using CRYSTIC ® 196 resin without added copper but catalysed in the same manner. The laminate was exposed to marine fouling without abrasion and showed no substantial signs of fouling after 2 years immersion.
• a gelcoat was prepared as below:-
• Laminates showed no evidence of marina fouling after 3 months immersion during thesummer whereas a con-trol having no copper showed pronounced fouling
• a Gelcoat was made as below, with approx. 30% Cu in place of the approx. 70% Cu of Ex. 1-3
• a very low acid value polyester resin was made by condensing propylene glycoi and isophthalic acid at 210 C to an acid value of 30- 3mg KOH/g. Maleic anhydride was then added and the reaction continued to an acid value of 30 ⁇ 3mg KOH/g. The resin was cooled to 180°C and sufficient Cardura E10 (aglycidyl ester of versatic acid) added to react with the remaining carboxyl groups in the resin. When the acid value was below 5 the resin was cooled and blended with styrene monomer containing toluhydroquinone as inhibitor. The final resin solution had a viscosity of 7.9 poise at 25 C, a solids content of 66.4% and an acid value of 1 mg/KOH/g. This was converted to a gelcoat as below:-
• a gelcoat was made from a urethane acrylate resin based on a caprolactone diol, isophorone di-iso-cyanate and hydroxy ethyl acrylate. This was dissolved in styrene to give a 70 per cent solids solution with an acid value below 1 mg KOH/g.
• the gelcoat formulation was:
• This composition was stable for at least three months showing no discolouration and no formation of lumps when catalysed with MEKP after that storage. Similar results are obtained if the copper powder content is decreased to approx. 50 and approx. 60% of the total composition in place of the approx. 70% of the formulation given.
• a gelcoat was made from a vinyl ester resin as follows:-
• the gelcoat composition of Example 3 was used as a coating.
• a conventional cured GRP laminate was solvent wiped and lightly abraded and a 0.4 mm thick layer of the catalysed gelcoat of Example 3 appliad. After curing . its surface was not tacky, the applied layer had good adhesion and no deterioration was noticeable after several weeks ' immersion in sea water.
• British Standard Meshes are referred to above; 3ritish Standard mesh 100 has a nominal aperture of 0.152 mm and British Standard Mesh 300 a nominal aperture of 0.053 mm: heavy metal particles of a size lying between or (within reason) outside this range may be used in the present invention.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Paints Or Removers (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Medicines Containing Material From Animals Or Micro-Organisms (AREA)
• Application Of Or Painting With Fluid Materials (AREA)

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• 1981
  • 1981-08-06 DE DE8181303598T patent/DE3161133D1/de not_active Expired
  • 1981-08-06 WO PCT/GB1981/000157 patent/WO1982000653A1/en not_active Ceased
  • 1981-08-06 AT AT81303598T patent/ATE4908T1/de not_active IP Right Cessation
  • 1981-08-06 JP JP56502605A patent/JPH0150266B2/ja not_active Expired
  • 1981-08-06 GB GB8208102A patent/GB2095691A/en not_active Withdrawn
  • 1981-08-06 EP EP81303598A patent/EP0046354B1/en not_active Expired
  • 1981-08-06 IE IE1795/81A patent/IE51759B1/en not_active IP Right Cessation
  • 1981-08-06 US US06/375,135 patent/US4410642A/en not_active Expired - Lifetime
  • 1981-08-06 BR BR8108744A patent/BR8108744A/pt not_active IP Right Cessation
  • 1981-08-12 NZ NZ198016A patent/NZ198016A/xx unknown
  • 1981-08-13 IN IN908/CAL/81A patent/IN154169B/en unknown
  • 1981-08-13 PT PT73518A patent/PT73518B/pt not_active IP Right Cessation
  • 1981-08-14 ZA ZA815614A patent/ZA815614B/xx unknown
  • 1981-08-14 ES ES504752A patent/ES8304601A1/es not_active Expired
  • 1981-08-14 CA CA000383947A patent/CA1184686A/en not_active Expired
• 1982
  • 1982-04-06 DK DK157982A patent/DK163521C/da not_active IP Right Cessation
  • 1982-04-14 FI FI821313A patent/FI72336C/fi not_active IP Right Cessation

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