SE440994B - Procedure for moulding a boat bottom against a mould surface - Google Patents

Abstract

Procedure for moulding a boat bottom against a mould surface, as characterized by that fact that one applies an anti-fouling boat bottom paint and mould release-agent on the shaping surface, effectively a composition containing fluorine hydrocarbon polymer and an anti-fouling agent, after which one forms a boat bottom of a plastic material on the mould surface with this coating as well as removing the moulded boat bottom from the mould surface with the outer coating of the anti-fouling boat bottom paint

Description

8001826-0 The transfer layer is applied in a desired thickness on the mold surface.

A common minimum thickness is 1 .mu.m, preferably 5 .mu.m or even 10 or 20; 1m, based on dry material if the transfer layer is applied as a composition containing volatile constituents. The maximum thickness can often be made high, for example up to 1 mm, up to 0.5 mm or in some cases up to 0, 1 or 0.05 mm or less, e.g. up to 0.025 mm.

These values are usually also suitable for release agents according to the above-mentioned Swedish patent application.

The layer applied on top of the transfer material can in the manufacture of boats of e.g. hardened and reinforced polyester plastic, consists of so-called gel-coat, usually gel-coat containing e.g. styrene-type components, such as styrene monomer.

The layer applied to the transfer layer may also contain components particularly suitable for improving the adhesion of the transfer layer, in the case of the antifouling agent according to the above-mentioned Swedish patent application e.g. halogenated hydrocarbons, such as halogenated hydrocarbons having up to 6 or 8 carbon atoms, preferably the halogenated hydrocarbons mentioned in this patent application and in particular those included in the antifouling composition. Good bonding can also be obtained with curable monomers, such as styrene monomer in the gel coat layer.

The invention is thus particularly valuable in applying an antifouling layer to the underwater part of a boat hull, this layer simultaneously acting as a release agent.

This layer can be applied e.g. by brushing, rolling, spraying, etc. A suitable method is to apply the antifouling agent according to the above-mentioned patent application by rolling with 1, 2 or 3 layers. 8001826-0 A composition effective as a ship bottom paint with antifouling properties, which can be used according to the invention, is stated in the Swedish patent publication 7613245-5.

This coating composition can be applied directly to a forming surface and act as a release agent while the composition is transferred with the desired layer thickness to the material applied as subsequent layers, e.g. a gelcoat layer for a boat bottom. The coating composition described below comprises a combination of fluorocarbon polymer, which may optionally contain unsubstituted hydrogen atoms and / or as a substituent other halogens, preferably chlorine or bromine. An additional release layer can also be applied closest to the mold surface, preferably of the same kind of composition as stated in the above-mentioned patent publication but with a lower content of antifouling compound, possibly completely without such a compound.

The coating composition under the memory includes a combination of fluorocarbon polymers and so-called "Antifouling agent" or "antifouling agent" means agents which, when introduced into a coating, prevent or counteract adhesion to and growth on the coating of organisms living in water, such as bacterial or diatom sludge, algae, snails, mussels, tube worms, shipworms , moss, teredos, limnoria, martesia, sphaeroma, oysters, bryozoans, etc. According to the invention, this agent is incorporated into the coating in an amount sufficient to prevent or counteract the adhesion and growth of these and other organisms in aqueous environments, such as lakes, Watercourses and seawater As a fluorocarbon polymer, a variety of fluorine-containing polymers can be used, for example, polytetrafluoroethylene, tetrafluoroethylene-perfluoropropane, polyvinylidene fluoride and ethylene-tetrafluoroethylene copolymers, and similar materials containing fluorine bonded to a carbon chain.

The fluoropolymers may be in the form of fine particles, for example with a particle size of less than 20 microns and often with a 1-micron. , _ mfg¿T? T «.; Äš: É" 'fn - Us. In 8Û0l826-0 4 particle size less than l0, um or l5, um. Often the majority of particles or the whole amount of particles have a grain size exceeding about 0, l, um or A normal grain size is about S / zm in average value 7 ~ _ For polytetrafluoroethylene, the density is suitably 2.14 - 2.20, in particular about 2.16. The melting point (crystal) is suitably about 280 - 33000, in particular about 30000. The average molecular weight can vary within wide limits, eg 1000 to 20,000 or 2000 to 5000, preferably about 3700. The softening point (ASTM E-28-58 ~ T) can vary eg between ^ 240 and 25 ° C, eg about 26 ° C.

Fluorocarbon polymers are most commonly marketed as dispersions in a suitable dispersant, for example chlorinated or fluorinated hydrocarbons, for example fluorinated hydrocarbons marketed under the trademark "FREON". An example is trichlorotrifluoroethane.

* In some cases it is also suitable that the solvent or dispersant has a certain dissolving effect on the fluorocarbon polymer, e.g. dissolves up to 25%, or 1 - 15%, preferably about 10%. Even lower degrees of solution, e.g. 0.1 - 1% can give some effect.

This dissolving effect may be partial so that the polymer swells only or forms a type of colloid.

The antifouling component of compositions of the invention may be selected from a variety of substances which have been found to be suitable for counteracting the overgrowth of coatings in water.

Such substances are described in a variety of publications and, by way of example, reference may be made to U.S. Pat. Nos. 3,787,217, 3,854,960 and 3,912,519. What is stated in these patents is intended to form part of the present description. Examples which may be mentioned in particular are copper metal in powder form as well as copper oxide, e.g. Cu20, as well as copper salts, arsenic salts, mercury compounds and chlorinated hydrocarbons, e.g. hexachlorocyclohexane, and also tin compounds, in particular triorganotin compounds, e.g. tributyl and triphenyltin compounds and tributyltin oxide. Along with these, such agents as colloidal silica gel, e.g. the 1 type produced by flame hydrolysis of silicon compounds. Åf) ¿% åš Å fi šfx 8001826-0 The amount of antifouling agents may vary within viísíräs limits. Calculated on the weight of the finished coating, the campus can contain up to 90 - 95% antifouling agents, preferably up to 50% and in particular up to 25%. Even lower levels, for example up to 5 or 10%, are suitable for certain types. The lowest effective limit also varies depending on the type of agent and can e.g. be between 5 and 10%. Lower levels, for example down to 1% or 0.1%, are also applicable.

The amount of fluorocarbon polymer also varies within wide limits depending on the amount of antifouling agent and other constituents, e.g. binder. Based on the weight of the finished coating, the fluorocarbon polymer weight can be up to 90-95, preferably up to 50% and in many cases up to 25%. Even levels up to 5 - 10% are useful. The lower content limit also varies depending on the other components and on the requirements. A lower limit between 10 and 25% is often desirable, but also lower levels are useful, for example down to 5% and also down to 1%.

In addition to fluorocarbon polymer and antifouling agents, the coating composition may also contain e.g. additional binders and pigments and similar excipients. LämPli9 fi bi ep åemed fi ï are, for example, epoxy resins and other adhesives of the thermoplastic or curable type, which are useful together with fluorocarbon polymers.

A variety of such materials are described in the literature, for example in Swedish patent specification 219,806, and what is stated in this patent specification is intended to form part of the present description.

Examples which may be mentioned are such curable and non-curable plastics as phenolic resins, urea-formaldehyde plastics, alkyd plastics, epoxy plastics, polyurethane plastics and alkylsilicon plastics, silicones.

It is also possible to apply compositions according to the invention to a surface which has first been provided with some form of priming treatment or primer of a per se well-known type, preferably with a release agent effect or low adhesion to the transfer material, such as fluorocarbon polymer, silicone resin and the like.

A variety of such primers or primer compositions are known in the art. 8001826-0 In addition to the ingredients indicated, the compositions used suitably also contain solvents which are removed after application of the composition to a vta by evaporation or dissolution. Examples of solvents are halogenated hydrocarbons, such as alkane and alkene hydrocarbons, for example chlorinated and / or fluorinated hydrocarbons, e.g. of the type methylene chloride, trichloroethane, trichloroethene and "FREON hydrocarbons", e.g. hydrocarbons having 1, 2, 3 or 4 carbon atoms in the chain which have a substantial proportion of the hydrogen atoms substituted by fluorine and optionally chlorine, preferably at least half or all of the hydrogen atoms substituted by fluorine and optionally chlorine, in particular trifluorotrichlorethylene. Solvent type aromatic hydrocarbons can also be used. Furthermore, solvent mixtures containing the indicated types of solvents can be used, such as trichlorotrifluoroethylene (eg 50%) + one or more of toluene, n-heptane and preferably trichloroethane.

The amount of solvent dispersant, calculated on the total weight, is often up to 95%, preferably up to 75% or 50%, in some cases up to 25%, but preferably at least 10%, in particular at least 20% and in particular at least 40%. . Other polar or non-polar liquids can also be used as solvents or dispersants for the paint compositions, e.g. hydrocarbons; alcohols, ketones, having 2 to 8 carbon atoms, and also water, the constituents of the composition being dispersed separately in water or mixed into a dispersion or solution in a water-soluble or insoluble liquid, which is dispersed in water.

The thickness of the coating applied to the molded article can be varied. Usually a coating thickness of less than 50 microns, preferably less than 25 microns, is used, e.g. below 10 or below 5 pm. A common lower thickness limit is 1-5 microns and a preferred thickness range is 5-15 microns. The amount of antifouling agents, e.g. copper powder or copper oxide, can vary in this case e.g. up to 50 g / m2, preferably up to 25 lg / m 2, e.g. up to 10 or 15 g / m2. A suitable lower limit is often between 1 and 5 g / m2 but also lower levels, e.g. 0.1 g / m2, are useful. A content of about 25-75%, preferably about 50% of the binder weight, is often suitable, e.g. for copper powder and the like. The coating applied to the mold surface is adjusted so that the desired thickness is obtained on the molded object. 8001826-0 As an example of a suitable pigment with special properties can also be mentioned pigments of layered lattice structure, e.g. molybdenum »disulfide, MoS2 or graphite. A suitable content of this substance is: robbery 0.1% up to 5 or 10%. MoS2 gives a special effect with polyfluorocarbon and also contributes to reduced friction and increased speed. Graphite can also be used as a replacement for or together with MoS2.

The compositions used can be distributed in various ways, such as single-component compositions but also as multi-component compositions. A suitable type is a bicomponent composition 1 which comprises a liquid component containing fluorocarbon polymer dispersed in solvents and optionally a binder, and a pigment component containing antifouling agents and optionally additional additives and optionally dispersant fi Preferably the pigment moiety is solid and powdered and mixed with . Suitable are, for example, a liquid component containing as main constituents one of a fluorocarbon polymer, e.g. of the "Teflon" type (polytetrafluoroethylene), e.g. with a fluorocarbon polymer content of about 20 - 80% and the remainder liquid dispersant, e.g. of the "FREON" type, and about 80% additional solvent, e.g. trichlorethylene or the like (e.g., "CHLOROTHENE NOW", sold by Dow Chemical Co.). The liquid component may additionally contain binders of other types, such as those mentioned above.

The pigment part may consist, for example, of copper powder in an amount of SO-90% and molybdenum disulfide in an amount of 10-50%, for example about 70% copper powder and 25% molybdenum disulfide. The weight ratio of liquid component to pigment component can be about 25 - 200 g of pigment per 800 - 975 g of the liquid component, the total weight being 1000 g. A suitable amount is about 875 g of liquid component and about 125 g of pigment with the foregoing stated composition of liquid, fluorocarbon polymer-containing component and pigment component.

A common size of the copper powder is about 300 to 30 mesh, e.g. 50% "fine" and 50% "superfine". Preferably, flake particles with a thickness / diameter ratio of 1/10 to 1/100, preferably 1/20 to 1/50, are used, preferably at least 50% and in particular at least 80% of the particles having a size of less than 10 μm in diameter. - -_ ---------- fl š_ ~ ¿~ _-äš = ~ ==: rílll 'f *' '8001826-0 The coatings can be applied in different ways, e.g. with brush, rollers, spraying, immersion, spraying. The deposits can also be melted on the substrate by heating the polytetrafluoroethylene, e.g. above 280 ° C, such as 300 - 31500, below 1 - 20, e.g. 5 - 10 minutes, or flame spray, e.g. plasma spray. The compositions used can be applied to different substrates, e.g. steel, zinc, aluminum, stainless steel, plastic, concrete, stone, (silicate) glass, porcelain, artificial stone, brick, wood, with or without color coatings, lacquer varnish, phosphate coatings, chromate coatings. The compositions may also contain corrosive ingredients, such as phosphoric acid and other acidic ingredients, which attack a substrate and improve adhesion. These ingredients may be of the Wash primer type and also include, for example, zinc chromate or other chromates and polyvinyl butyral and similar ingredients known from Wash primer. Other useful constituents, for example in compositions containing water as dispersing or emulsifying agents, are thermoplastic constituents, polyacrylates comprising copolymers of acrylic monomers with other unsaturated monomers, polyvinyl acetate, polystyrene, vinyl chloride-vinyl polymer isyl, styrene-amyl polymer chloride, butadiene copolymers, chlorine rubber, rosin resinate, linear polyesters such as polyethylene terephthalate, polybutylene terephthalate and the like.

As further examples of pigments and fillers may be mentioned anti-corrosion additives, such as lead monoxide, zinc chromate, zinc metal powder, aluminum metal powder, aluminum bronze powder and the like.

As further examples of antifouling agents, in particular active against balanides, e.g. barnacles, mussels, tube worms and the like, mixtures of Cu20 and Hg0 can be mentioned.

As further examples of fluorocarbon polymers may be mentioned polytrifluorochloroethylene, polyfluoroethylenepropylene, polyvinyl fluoride, polyvinylidene fluoride, fluorochubics, such as products obtained by vulcanization of polychlorotrifluoroethylene and / or vinylidene fluoride-hexafluoropropylene copolymers or polyfuncuric copolymers or polyfunucleoxylene copolymers m; The silicones (organosilicon compounds) useful according to the invention may be of the oil or resin type and curable or non-curable, linear or crosslinked. Silicones are described in detail e.g. in the book W. Noll: "Chemie und Technologie der Silicone", 2nd edition, Verlag Chemie, Weinheim, BRP, 1968 (the disclosure of which is included by reference), and in "Chemie und Technologie der Kunststoffe", Volume II , Akademische Verlagsgesellschaft Gees: & Portig KG, Leipzig, 1963, p. 789-858 (the disclosure of which is included by reference). Also suitable silanes, preferably those which can form silicone polymers or siloxanes (polysiloxane: may be included in compositions according to the invention.

The molecular weight of the organosilicon compounds used can vary within wide limits, e.g. medium and 100,000, e.g. 100 - 10,000.

The amount of organosilicon compound (including polymers) can vary based on the weight of the solid material from nothing up to 5%, preferably from 0.01%, in particular 0.1% and in particular 0.3% up to 3%, in particular up to 1%. .

The organosilicon compounds may also completely or partially replace the Asa fluorocyclic (hydrogen) polymers in compositions according to the invention. The organosilicon compounds used for this purpose may form. made by the ilans listed above. silincne -a. silox- anerna resp. linear or crosslinked polymers thereof.

Additional fluorocarbon polymers useful in the invention with or without hydrogen, chlorine, nitrogen or other atoms or groups in the recurring groups or otherwise incorporated into the molecule are set forth in the book Fluoropolymers, Leo A. Wall, Wiley-In fi ere, ience (High Polymers). Vol. XXV, Library of Congress Catalog Card Number: 74-l6šO23) (the disclosure of which is included by reference).

Examples of "antifouling" substances may also be mentioned: Organic and inorganic compounds of one or more elements belonging to the periodic table group 2a (Be, Mg, Ca, Sr, Ba), 3b (Sc, Y, La, Ce, Th ), 4b (Ti, Zr, Hf), 5b (V, Nb, Ta, U), 6b (Cr, Mo, W), 8001826-0 10 7b (Mn, Tc, Re), 8 (Fe, Ni, Co), lb (Cu, Ag, Au), 2b (Zn, Cd, Hg), 3a (B, Al, Ga, In, T1), 5a (P, As, Sb, Bi), 6a (S, Se , Te), 7a (F, Cl, Br, J), as well as other lanthamides, and also these elements in elemental form.

Examples are organic and inorganic heavy metal compounds.

Zn oxide, Zn thiocarbamate, Zn carbonate, Zn metal, Pb metal, acetate, phenyl lead compounds, phenol and phenyl compounds, e.g. phenyl-metal compounds, e.g. phenyl heavy metal compounds, phenylurea compounds, e.g. according to Swedish patent 7106810-0 (included by reference), triazine derivatives, e.g. combined with tin and / or zinc compounds, triphenylarsazine chloride, quinoxaline derivatives, chlorinated hydrocarbons, e.g. DDT, pentachlorophenol, tri-n-butyl fluoride, naphthenates, e.g. Cu-, Zn-, Fe-naphthenate, formaldehyde, paraformaldehyde.

Further examples are found in U.S. Patents 3,676,388, 3,266,913, 3,885,039, 3,100,718, 3,100,719, 3,794,501 and Swedish Patent Publications 334,613, 140,806, 213,824, 353,343, 381,275, 7206111-2, 370,082 (all included by reference).

Further N-dimethyl-N'-phenyl- (N'-fluorodichloromethylthio) -sulfamide.

Examples which may be mentioned are: cuprous, d., Coupling powder, carbon dioxide, cuprous oxide-hydroxyl (tax. 3: 1 markurol chloride), organic dental compounds including rifenyltin chloride, tritanyltan bromide, tri-p-cresyltin chloride, tranyl chloride, trichloride. tri- (p-chlorothenyltin) 41:10:11, tri- (m-chlorothenyltin) -chloride, nibutyltyltan fl-orid., dibutyloctyltennbrinide, tricyclohoacyltan chloride, triethyltennstearnt, tributyltannatannyl, tristuride _i :: Ifen;, 'ltcnnhyàruxid, trifanyltenntiácyanat, tritenyltenntriklor- acetst, tributyltennacatat, fi ributyítsnndecanat, tributyltannf naopenxann fi, trioktylüennqecanat, tributyltennozid, trioctyl tin oxide, triíanyltenniluorid, tributyltennoleat, tripropyltann- neodacanat, tributyltennlnurat, .tribut7štennektsnoat, tribut7l ~ tennšimetylknrbanat, tributyltunnrasinat, tributyltannkromat ,,. __: «~“ - v-- ~~~~ "" - ~~ - * "'me? F * ~" "" "°“ ï “? 4a (C, Si, Ge, Sn,? LÉ, n; .ef (Au 8001826-0 ll nmyldietyltsnndecanate, tributyltenn aftenat, tributyltenn- isooctylmarkaptoacatate, bis ~ (tri-butyltenn) -oxulat, bla- (tri-butyltenn) - malonate, bin- (tributyltann) -aaipate, bis- (tribut'ltannJ- -carbonate, organic lead compounds, eg triphenyl-lead acetate, tri-Ionyl-lead-torut, trirenyl-blyneodacannate, triphenyl-lead oleate, tri-phenyl-lead chloride , triphanyl-lead laurate, triethyl-lead-elastomer, triethyl-lead-acetate, triethyl-lead-at-arate, trinethyl-hlyl-stearate, triphonyl-lead-bromide, triphenyl-lead-fluoride, organic compounds such as 10,10'-oxybiaphenoxazine (SAf546), 1,2,5-trichlor -4,6-dinitrobenzene.

U hexachloroylene, dichlorodifangyl-tricyclate (DBT), ienolmercuric acetate, tetrachlorophthalonitrile, bis- (propylsulfonyl) -ethylene, etc. The antifouling agents are preferably insoluble in water. Fillers can be incorporated into the coating composition or into the coating, e.g. particles that improve the abrasion resistance or strength of the coating. Organic or inorganic material can be used, e.g. molten or sintered water-resistant materials, such as glass, ceramics, metals, etc. Particles may have a regular shape, e.g. spherical shape, such as glass spheres, or irregular shape, e.g. flake form, fiber form, form obtained by crushing, etc. The filler may also contain the antifouling agent and / or the carbon-fluoropolymer incorporated in or bound to the surface of the filler particles. The filler can also have a pigment effect or consist of pigment.

When using balls of glass or synthetic resin, e.g. of vinyl type, acrylic type or elastomer type, such as rubber, a diameter of about 1 - 100 μm, preferably 5 - 50 μm or 5 - 30 μm is suitable.

The balls can be incorporated to improve the frictional properties of the coating in water.

Example A coating composition having the following composition is prepared 100 grams of polytetrafluoroethylene, average molecular weight about 5006 100 grams of copper powder 30-300 mesh 30 grams of molybdenum disulfide whereby the polytetrafluoroethylene was dispersed in 770 grams of a mixture of 200 grams of trifluorotrichloroethane and 570 grams ,: icon QUAL: 8001826-0 12 A good long-term effect against vegetation in seawater was obtained with the coating thicknesses 5, 10, 25, 50 and 10, um in a dried state on the surface of molds for forming the bottom part of a boat by brushing, rolling or spraying one, two, three or more layers in succession until the desired thickness is obtained.

After drying to non-stick resp. to complete dryness, gelcoat was applied mainly containing styrene monomer as a curable resin component and any pigment, e.g. copper powder, e.g. in an amount of at least 1%, at least 5%, at least 10% of the gelcoat volume, preferably at most 50%, after which the remainder of the boat bottom was built up on the bottom form part as part of a boat hull. In other experiments, a ship bottom paint containing Cu 2 O was applied as a replacement for all or half of the copper powder. Furthermore, an addition of about 10% glass beads with a mean diameter of 5 and 5%, respectively, was used. 30; ¿m, calculated on the solids content of the composition. fl .UI w

Claims (7)

15 8001826-0 PATENT REQUIREMENTS 1. A method of forming a boat bottom against a mold surface, characterized in that a composition containing anti-fouling boat bottom paint and release agent containing fluorocarbon polymer and an antifouling substance is applied to the forming surface, after which the mold surface is coated with this layer. forms a boat bottom of plastic material and from the mold surface removes the shaped boat bottom with the outer layer of the antifouling boat bottom paint. 2. A method according to claim 1, characterized in that the composition acting as an antifouling boat bottom paint contains fluorocarbon polymers, calculated on the weight of dry composition or excluding solvent and dispersant of up to 95%, preferably up to 75% and in particular up to 50% or up to 25%, but at least 1%, preferably at least 5% and in particular at least 10% fluorocarbon polymer, and a content of antifouling agents of up to 95%, preferably up to 75%, in particular up to to 50% or up to 25%, but at least 0.1 3: preferably at least 1% and in particular at least 5 or at least 10 3. 3. A method according to claim 1 or 2, characterized in that tin compounds are used as antifouling agents, e.g. organotin compounds, arsenic compounds, mercury compounds, copper compounds, e.g. Cu20, copper metal, chlorinated hydrocarbons or mixtures of these substances. Method according to one of the preceding claims, characterized in that a layer of plastic material, preferably gelcoat or the like with a high content of curable component, in particular at least 50%, is preferably applied to the layer of anti-fouling boat primer paint on the mold surface. at least 75% and in particular 'Che 8001826-0 14 at least 90%, calculated on the volume, in particular styrene-based gel coat and then on this coating of plastic material builds up the rest of the boat bottom. Process according to one of the preceding claims, characterized in that the composition acting as an antifouling anti-fouling boat primer contains dispersing and / or solvents containing halogenated hydrocarbons, in particular fluorine and / or chlorohydrocarbons containing 1 4 carbon atoms in the chain, such as trifluorotrichloroethane, trichlorethylene, trichloroethane, methylene chloride, aromatic hydrocarbons such as toluene, polar solvents such as C1-C4-alkanols, water, acetone, in an amount of, by weight, up to 95 %, preferably up to 75% or 50%, in some cases up to 25%, preferably at least 10%, in particular at least 20% and in particular at least 40%. 6. '. Process according to any one of the preceding claims, characterized in that the fluorocarbon polymer consists of polytetrafluoroethylene, polytetrafluoroethylene-perfluoropropylene, polyvinylidene fluoride or ethylene-tetrafluoroethylene copolymer or mixtures thereof. 7. A method according to any one of the preceding claims, characterized in that a boat bottom of reinforced plastic, in particular polyester resin and preferably with glass fiber reinforcement or carbon fiber reinforcement, is formed on the mold surface. u »