US20110078851A1 - Surface composition and method of application - Google Patents

Surface composition and method of application Download PDF

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Publication number
US20110078851A1
US20110078851A1 US12/996,726 US99672609A US2011078851A1 US 20110078851 A1 US20110078851 A1 US 20110078851A1 US 99672609 A US99672609 A US 99672609A US 2011078851 A1 US2011078851 A1 US 2011078851A1
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United States
Prior art keywords
surface composition
clear
composition according
barrier layer
pool
Prior art date
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Abandoned
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US12/996,726
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English (en)
Inventor
Lew Beale
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hydrawall Pty Ltd
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Hydrawall Pty Ltd
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Filing date
Publication date
Priority claimed from AU2009900767A external-priority patent/AU2009900767A0/en
Application filed by Hydrawall Pty Ltd filed Critical Hydrawall Pty Ltd
Assigned to HYDRAWALL PTY LTD reassignment HYDRAWALL PTY LTD ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BEALE, LEW
Publication of US20110078851A1 publication Critical patent/US20110078851A1/en
Abandoned legal-status Critical Current

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    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—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 carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/02—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • 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
    • C09D135/00—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 carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/02—Homopolymers or copolymers of esters
    • 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
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04H—BUILDINGS OR LIKE STRUCTURES FOR PARTICULAR PURPOSES; SWIMMING OR SPLASH BATHS OR POOLS; MASTS; FENCING; TENTS OR CANOPIES, IN GENERAL
    • E04H4/00—Swimming or splash baths or pools
    • E04H4/0018—Easily movable or transportable swimming pools
    • E04H2004/0068—Easily movable or transportable swimming pools made of plastic shells or plastic elements including at least parts of walls and floors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/31797—Next to addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

Definitions

  • the present invention relates to a surface composition for use in protecting surfaces subjected to extended periods of submersion from degradation and fading, such as protecting a surface layer finish of swimming pools and spa pools.
  • the present invention also relates to a method of application of a surface composition and to products manufactured therefrom.
  • swimming pools and spa pools can be installed for private or public use and for a variety of different uses, such as competition, exercise, recreation, relaxation or therapy. Construction methods for pools can vary, though the in-ground version is most popular if the pool is to remain as a permanent fixture.
  • the main types of in-ground pools are concrete, fibreglass reinforced plastic (FRP) and vinyl-lined pools.
  • Fibreglass pools are typically the most popular for private installations, such as those installed at a private residence. Fibreglass pools are made from fibreglass reinforced plastic which has been moulded into a basin shape, which is the final shape of the pool. The shape and configuration of the pool is dependent on that of the mould. Typically, any one pool manufacturer will have a set selection of moulds that a consumer can select their pool design from.
  • Selection of the shape and size of the fibreglass pool is one important decision that the consumer must make when selecting their pool.
  • the other most important decision is selection of the pool surface finish, which dictates the appearance the pool will have when filled with water.
  • Selection of surface finish can include selection of colour, sparkle or shimmer, the combination of which can match the appearance of the pool to its surroundings as well as give the appearance of colour depth and brilliance as well as capture marble or granite effects.
  • the surface is totally immersed in water and remains as such interminably. That is, the water is never completely discharged and remains within the pool structure at all times. This inevitably creates a two-fold problem.
  • the first is that the water itself, which is typically of a temperature between 12 to 41° C., is a harsh solvent capable of dissolving any water soluble material (WSM) and hydrolysing any of the water soluble components used in manufacture of the pool.
  • WSM water soluble material
  • the second problem is that the water must be sanitised in order to kill algae and pathogens such as bacteria and protozoa, since without sanitisation; the pathogens will otherwise thrive in the water, creating a perfect place for micro-organisms to transfer from one person to the next.
  • Pool filter systems can assist in keeping the water clean; however, to properly take care of water pathogens, it is necessary to introduce a disinfecting agent into the water.
  • the most popular pool disinfectant is chlorine, which can be introduced in various forms, such as calcium hypochlorite or sodium hypochlorite. Chlorine is also produced by the electrolysis of salt, commonly called “salt water chlorinators”. When these compounds are added to water, the chlorine component reacts to form various chemicals, including hypochlorous acid, which acts to kill the pathogens.
  • Salt water chlorinators When these compounds are added to water, the chlorine component reacts to form various chemicals, including hypochlorous acid, which acts to kill the pathogens.
  • Alternative sanitizers such as bromide, ozone or hydrogen peroxide carry out essentially the same disinfecting function.
  • hypochlorous acid is not a particularly stable compound, it is usually necessary to add further chemicals to the pool water, including stabilising agents such as cyanuric acid.
  • pH level of the pool water is desirably maintained at generally neutral levels (a pH between 7 and 7.8), since water that is either too acidic or too alkaline will cause undesirable chemical reactions.
  • Further chemicals are typically added to the pool water to maintain the pH, such as sodium carbonate or sodium bicarbonate to raise the pH and sodium bisulfate or liquid acids such as hydrochloric or sulphuric acid.
  • a surface composition for reducing degradation and fading of surfaces subjected to extended periods of submersion in an aqueous liquid comprising at least one clear barrier layer and at least one under layer, wherein the clear barrier layer is in use, disposed atop the under layer and in contact with the aqueous liquid whereby the clear barrier layer protects the structure and appearance of the under layer.
  • the surface composition is particularly useful in applications where the surface is subjected to extended periods of submersion in liquids containing hydrolysing or oxidising agents, exposure to ultra violet radiation, or combinations thereof, whereby the clear barrier layer provides structural protection against degradation from chemical attack and from fading due to UV exposure.
  • the under layer is a decorative layer, containing one or more decorative or ornamental agents provided to impart a desired visual or aesthetic appearance.
  • the decorative or ornamental agents can include, but are not limited to, pigments, particles and chips.
  • the surface composition finds particular application in the creation of a surface finish to swimming pools and spa pools; particularly fibre reinforced plastic (FRP) pools.
  • FRP fibre reinforced plastic
  • the surface composition provides strong interlaminar bonding between the barrier layer and the under layer.
  • the surface composition of the invention advantageously minimises delamination and prevents osmotic blistering.
  • the composition comprises one or more UV inhibitors, absorbers and/or stabilisers.
  • the clear barrier layer comprises one or more UV inhibitors, absorbers and/or stabilisers.
  • the clear barrier layer is a clear polyester gelcoat.
  • the clear polyester gelcoat comprises one or more phthalate containing polyesters, vinyl containing polyesters or methyl methacrylate containing polyesters. More preferably, the clear polyester gelcoat comprises a phthalate containing polyester particularly a phthalate containing polyester derived from an isophthalic neopentyl glycol (iso-NPG).
  • the iso-NPG is advantageously combined with additives, including promoters and UV inhibitors/absorbers, which are added prior to application of the iso-NPG to a pool mould.
  • the barrier layer comprises a triazine based UV absorber. Additionally or alternatively the barrier layer comprises a hindered amine light stabiliser.
  • the barrier layer comprises one or more metal promoters preferably one or more metal promoters selected from the group consisting of zinc octoate, potassium octoate or cobalt octoate. Particularly preferred promoters are a mixture of zinc octoate and potassium octoate.
  • the under layer comprises one or more polyesters, vinyl esters or terephthalate based resins.
  • the under layer comprises one or more epoxy vinyl esters, brominated epoxy vinyl esters, novolac epoxy vinyl ester resins or elastomer modified vinyl ester resins.
  • a particularly preferred under layer is an epoxy vinyl ester resin comprising a bisphenol-A epoxy vinyl ester resin.
  • the under layer comprises one or more metal promoters.
  • the under layer is provided with decorative additives such as pigments, which can include organic or inorganic pigments and optionally, other decorative elements, such as small chips or particles, so as to impart a granite, marble, crystalline or quartz appearance.
  • decorative additives such as pigments, which can include organic or inorganic pigments and optionally, other decorative elements, such as small chips or particles, so as to impart a granite, marble, crystalline or quartz appearance.
  • a method of manufacturing a pool surface composition comprising application of a clear gelcoat liquid to a pool mould, permitting the gelcoat to cure and subsequently applying a coloured or decorative vinyl ester layer to the cured gelcoat.
  • a swimming pool or spa pool having a surface composition comprised of at least one clear barrier layer and at least one under layer wherein the clear barrier is in use, disposed atop the under layer and in contact with liquid in the pool, whereby the clear barrier layer protects the under layer from degradation.
  • FIG. 1 is a simplified diagram of layers of a surface composition according to the present invention.
  • FIG. 2 is a photograph comparing effect of submersion and chemical exposure on a panel of FRP of known surface composition and of a surface composition of the present invention.
  • FIGS. 3 to 14 are photographs of a series of test panels comparing weathering resistance.
  • the surface composition of the present invention finds particular application in the creation of a surface finish or layer in FRP swimming pools and pool spas, in which the surface is submersed within and in direct contact with water, particularly water containing hydrolysing and/or oxidising agents, such as from pool sanitising chemicals, for prolonged periods of time.
  • the surface composition has the primary object of not only maintaining structural integrity of the FRP product whilst immersed in water, but also of protecting decorative elements such as pigmentation, from damage or fading caused by prolonged exposure to water, chemicals and UV radiation.
  • the surface composition includes a clear barrier gelcoat surface layer which is in use, in direct contact with the water and any chemicals that the water may contain.
  • the purpose of the clear barrier layer is to protect the second gelcoat layer, this second, or decorative layer containing decorative components or additives, such as pigmentation and chips or particles, from degradation by the water, chemicals and UV light. That is, the clear barrier layer, applied to a pool or spa pool mould prior to application of the second, decorative or coloured gelcoat layer, has the purpose of protecting the decorative qualities within the second layer, the maintenance of which is essential in preserving the cosmetic or aesthetic qualities of the pool.
  • composition of the present invention has solved these issues by utilisation of specific components and additives in each of the clear barrier layer and the coloured, decorative layer located underneath.
  • the clear barrier layer of the surface composition of the present invention is provided as a clear polyester gelcoat such as a clear isophthalic neopentyl glycol (iso-NPG).
  • a clear polyester gelcoat such as a clear isophthalic neopentyl glycol (iso-NPG).
  • iso-NPG is a high quality, high molecular weight iso-NPG.
  • a non-limiting example of a suitable iso-NPG is the commercially available Cray Valley (Cray Valley Korea Co. Ltd) formulated gelcoat, Polycor GPLY 9107-011, which is an unsaturated polyester resin in styrene monomer.
  • clear barrier layer Whilst this is a preferred composition for the clear barrier layer, it is envisaged that a selection of other suitable products can also be used, such as, but not limited to, clear orthophthalic NPG based gelcoat, clear orthophthalic gelcoat, clear vinyl ester gelcoat or clear methyl methacrylate modified gelcoat.
  • additives are added to the unpromoted iso-NPG to impart the qualities needed to protect the second, decorative layer.
  • the additives include specific promoters and UV inhibitors and/or UV absorbers.
  • promoters are one of the chief factors in the success of the application of the clear barrier gelcoat layer and its inclusion in the present surface composition. It is usual in the art of FRP pool manufacture, that the promoter of choice is cobalt based, namely cobalt octoate, which is purple in colour. The addition of this component alone is sufficient to alter the colour of the resin, making it less than clear.
  • mixed metal promoters are added to the iso-NPG.
  • Preferred metal promoters are zinc octoate (6%) and potassium octoate (12%), which, on being added to the iso-NPG, do not alter the colour. Further, even on catalysation and curing, they do not alter the clarity of the gelcoat.
  • iso-NPG iso-NPG's, whilst having physical qualities that are ideal for the present application, being known to be more hydrolytically stable than other resins such as orthophthalic resins, are more difficult to apply and more difficult to process. For at least this reason, iso-NPGs have been considered as unsuitable for purposes of providing a clear barrier gelcoat or indeed, even for general widespread application in creation of FRP pools. High molecular weight iso-NPG's are more reactive and are prone to shrinkage from the mould if applied too thickly, or are over catalysed or promoted, or sprayed in less than ideal conditions.
  • the selection of the mixed metal promoters such as zinc octoate and potassium octoate have overcome curing problems and permitted the creation of a clear layer having a strong positive cure.
  • the clear barrier gelcoat advantageously has qualities that will protect the coloured gelcoat layer from UV fading
  • at least one UV inhibitor and/or absorber or a light stabiliser is also added to the iso-NPG.
  • two UV absorbers are added, known commercially under the trade marks TinuvinTM and ChimasorbTM, each produced by CibaTM Specialty Chemicals Inc.
  • Preferred blends are TinuvinTM 384-2 and ChimasorbTM 119FL.
  • Particularly preferred blends are TinuvinTM 400 and TinuvinTM 123.
  • thixotropic agents are added to the iso-NPG as required, such as thixotropic agents. Selection of thixotropic agent is not of itself critical for the present surface composition to work, only to make the uncured components appropriately sprayable, which is necessary for the method of application of iso-NPG in creation of FRP pools known to the art. However, the thixotropic agent should be hydrophobic, so as to repel moisture. Elimination of moisture is necessary to maintain the clarity of the clear barrier gelcoat, since moisture will cause the gelcoat to become misty and detract from the aesthetic qualities.
  • the combination of specific components as described above advantageously provides a clear barrier gelcoat that can be sprayed onto the pool mould prior to the application of the second coloured gelcoat.
  • the combination of components is clear prior to application and remains clear after application and curing.
  • the successful creation of the clear barrier gelcoat cannot be successful in the intended application as a pool surface composition unless it also facilitates application of the second coloured gelcoat without wrinkling of the clear coat. It is also necessary that a strong interlaminar bond between the first and second gelcoats be created so as to eliminate possibility of delamination between the adjacent gelcoat layers.
  • the composition of the second coloured gelcoat is critical.
  • the second colour gelcoat is comprised essentially of a vinyl ester resin.
  • Vinyl ester resins have properties which advantageously lend themselves to the present application, in that they are extremely strong, have great hydrolytic stability, offer excellent tensile and flexural strengths and have a high heat distortion temperature and are therefore able to resist osmotic blistering. In addition, they have excellent adhesive and bonding characteristics and are very chemically resistant.
  • vinyl esters have never been used as a carrier for decorative agents such as pigment and texturising agents in pool surface compositions or in any application where the surface is exposed to water for prolonged periods. Vinyl esters are known to degrade when subjected to constant water submersion and continuous UV radiation. As such, any gelcoat made from a vinyl ester and applied to a pool surface will change colour on manufacture, on application and particularly after aging and exposure to water and UV light.
  • vinyl esters have been thought to be inherently unsuitable for application in pool surfaces due to the fact that when used as a gelcoat, they characteristically cure softer than a polyester resin. That is, using a Barber Coleman impresser to test for Barcol hardness, a vinyl ester resin can test at about 25% lower than the hardness of an iso-NPG or ortho-NPG based gelcoat. As such, despite having many positive attributes, vinyl ester gelcoats are generally unable to withstand the rigors of pool usage, particularly from abrasion from cleaning products, cleaning methods and automatic pool cleaners.
  • the vinyl ester resin selected for the present invention is one that is formulated to be clear and importantly, not show the distinguishing brown tones of conventional vinyl ester resins.
  • Standard vinyl ester resins are brown and thus do not provide a good base for application of the available variety of different pigmentations. Since one of the objectives of the present invention is to permit the use of not only standard colours in pools, but an expanded array of colours as well as culturing and texturizing of colours with the addition of small chips or particles, it is desirable that the vinyl ester selected can remain as clear as possible, even after application and curing.
  • a non-limiting example of a vinyl ester that has been found to be suitable for application in the present invention is bisphenol-A epoxy vinyl ester resin, such as Cray Valley Epovia KayakTM KRF-1001MV, which is a clear transparent liquid resin.
  • Any suitable vinyl ester can be utilised, as long as it is able to provide excellent cure of the vinyl ester gelcoat and can enable the coexistence of the highly water and chemical resistant vinyl ester resin behind the clear barrier gelcoat.
  • composition for the clear barrier gelcoat it is envisaged that other products may also be suitable for use in the coloured gelcoat layer.
  • Possible non-limiting examples are a selection of polyester, vinyl ester or terephthalate based resins or gelcoats that can incorporate pigments and/or texturising components, including any bisphenol-A epoxy vinyl ester resin, brominated epoxy vinyl ester resin, novolac epoxy vinyl ester resin or elastomer modified vinyl ester resin.
  • the selection of additives added to the vinyl ester is significant for imparting desired qualities to the overall surface composition.
  • mixed metal promoters such as zinc octoate and potassium octoate.
  • suitable additives include Shen Catalyst PC-6, dimethyl aniline, EFKA-2020 defoaming agent and styrene monomers. In applications where the final colour of the coloured layer is relatively dark, it may be appropriate to add cobalt octoate (6% and 8%).
  • a suitable thixotropic agent is also added to enable sprayability.
  • the present invention also includes a method of manufacture of a surface composition and manufacture of a FRP product, such as a swimming pool or spa pool.
  • the method essentially comprises the application of a clear polyester gelcoat liquid, in this case, the clear high molecular weight iso-NPG, to the surface of a mould.
  • the iso-NPG containing additives as described above, is sprayed evenly onto the mould in a manner known to the art, achieving a minimal wet thickness of 0.65 mm.
  • the cured gelcoat preferably achieves a minimum Barcol hardness of 35 within 24 hours of application.
  • the clear barrier layer is able to provide the durability and abrasion resistance to withstand normal daily use of a swimming pool, including the use of automatic pool cleaners and in the case especially of spa pools, to water temperatures of up to 41° C.
  • the vinyl ester in this case, bisphenol-A epoxy vinyl ester resin, with additives as described above, is sprayed onto the gelcoated mould to give the product its coloured and optionally, textured appearance.
  • the vinyl ester is then also permitted to cure as required.
  • further structural and chemical and/or corrosion barrier layers are added as required and as dictated by the specific intended use of the product.
  • further layers may comprise a further vinyl ester corrosion barrier to improve impact resistance and thermal insulation, an isophthalic corrosion and structural layer, fibreglass lamination and also further reinforcing layers.
  • the cured finished product is released from the mould, trimmed and transported to its place of service.
  • the creation of a product, such as a swimming pool, with the surface composition of the present invention confers quality and resilience of product that has not yet been achieved in the art.
  • the present surface composition provides a clear barrier layer or gelcoat that will not discolour or fail under the harmful effects of UV radiation, such as is experienced when the pool is situated outdoors and therefore exposed to long periods of sunlight, or the combination of water and chemicals.
  • this clear barrier layer provides such an increased degree of protection that the second coloured or decorative layer disposed beneath can last for even longer periods of time than previously possible without fade or discolouration of pigmentation.
  • the degree of protection conferred by the clear barrier layer is such that a wider range of pigments can be employed in the coloured layer. That is, organic pigments, which would otherwise be destroyed or compromised upon exposure particularly to UV and oxidising agents, can be included in the coloured gelcoat layer.
  • FRP fibreglass reinforced plastic
  • a series of square panels, measuring approximately 200 mm ⁇ 200 mm were cut from two variations of FRP with a known surface composition (control panels) and also from two variations of FRP having the surface composition of an embodiment of the present invention applied thereon.
  • the variations are as recited in Table 1 below:
  • Each panel was placed in a separate tank of water and a trichlorisocyanurate swimming pool disinfection tablet was placed in direct contact with the surface of each panel, with both panel and tablet being fully submerged in the water.
  • the tablet was placed directly on each panel to simulate the effect of many years degradation and bleaching of a pool surface by water and disinfectant.
  • the tablet in each tank was weighed down to prevent migration of the tablet across the surface of the panel due to the release of gases and surface interactions.
  • each tank was emptied daily and replaced with clean fresh tap water to ensure that the chlorine residual in the test water was not excessively high and did not contribute to early fading of the panels.
  • each panel was washed, photographed and inspected for signs of colour or surface degradation. After replacement of the water and panel in each tank, the same tablet was replaced in exactly the same location upon the panel surface. Each panel was checked after two hours to ensure that the tablet had not moved from its position.
  • Panels PBC and PD were removed from the testing program after two days of exposure since panel PD (without the inventive surface composition) had faded and deteriorated beyond repair.
  • panel PAC was removed, cleaned and finely sanded by mild, gentle rubbing of the surface (600 grit wet and dry). This action, which was almost effortless, caused immediate removal of the discolouration. The panel was then polished and returned to the testing process.
  • a further PAC panel was subjected to the testing process without any intermediate polishing or cleaning.
  • panel PC was examined, where it was established that the surface was significantly degraded, showing extreme pitting and oxidation of the surface in contact with the tablet.
  • the degree of damage caused to the surface was such that it was irreparable and irreversible.
  • panel PAC showed little change to the surface, other than slight staining from the chlorine (green colour of free available chlorine) and extremely slight surface pitting. No degradation of the actual pigmentation in the panel itself was observed. After mild abrasion with 600 grit wet and dry, the surface pitting and the majority of chlorine discolouration was removed.
  • Panels PAC and PBC as described in Example 1 were subjected to water resistance tests in accordance with “AS/NZS 1838-1994 swimming pools—premoulded fibre-reinforced plastics—design and fabrication” Standards. This Standard requires that the panels are able to pass 30 days at 80° C. in accordance with the prescribed Degradation Rating (Table E1 from the Standard). Both panels were subjected to the required conditions and passed the test with exceptional results. There was no degradation of the surface and no osmotic blistering. After 75 days there was still no osmotic blistering visible and negligible internal surface degradation.
  • the surface composition of the present invention advantageously enables the manufacture of FRP swimming pools and spa pools that are essentially completely fade resistant, exceeding current industry standards, and which comply with AS/NZS 1838-1994 with regard to blister resistance, chemical resistance and hydrolytic stability.
  • Each panel was exposed to 4 hours of condensation at 50° C. followed by 8 hours of UV-A exposure at 60° C. This pattern was repeated for the duration of a 2000 hour test.
  • Each panel was given a different identification letter being panels G, H, I, J, K, L, M, N, O, P, Q and R.
  • Each panel was intrinsically different. Ten panels were manufactured using a surface composition according to an embodiment of the present invention and two panels were made from what may be considered to be industry best practice.
  • a liquid hydroxyphenyl-triazine (HPT) UV absorber A liquid hydroxyphenyl-triazine (HPT) UV absorber.
  • a liquid UV absorber of the hydroxyphenyl-benzotriazole class is hydroxyphenyl-benzotriazole class.
  • a liquid HALS stabilizer based on hindered aminoether functionality.
  • the panels were set up and tested according to ASTM G 154-06 and evaluated after 500 hours, 1000 hours, 1500 hours and 2000 hours.
  • Table 3 summarises the colour, coatings, additives and results of tests on the twelve panels.
  • Panel H contained 1.5% additives in comparison to Panel G with 1%. As there were not any derogatory effects on Panel H after 2000 hours it was concluded that Panel H would in all probability out perform Panel G under the conditions of ASTM G154-06 for periods longer than 2000 hours.
  • inventive composition offers the following major improvements and benefits over standard coatings particularly when combined with the advantageous characteristics of TINUVINTM 400 and TINUVINTM 123 absorbers and stabilizers.
  • the surface composition of the present invention finds particular application in the manufacture of swimming pools and pool spas, it is equally applicable and useful for any product, particularly FRP product, which spends any significant period of time submerged in water and/or subjected to UV radiation.

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  • Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Mathematical Physics (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Polymerisation Methods In General (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
US12/996,726 2009-02-23 2009-12-23 Surface composition and method of application Abandoned US20110078851A1 (en)

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