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
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
  • C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
• • 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
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
  • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • 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
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • 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]
  • Y10T428/31511—Of epoxy ether
  • Y10T428/31525—Next to glass or quartz
• • 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
  • Y10T428/31529—Next to metal
• • 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]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31609—Particulate metal or metal compound-containing
  • Y10T428/31612—As silicone, silane or siloxane
• • 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]
  • Y10T428/31652—Of asbestos
  • Y10T428/31663—As siloxane, silicone or silane

Definitions

• the present invention relates to solventless siloxane epoxy compositions, and more particularly to solventless siloxane epoxy compositions that are thermally curable or curable by electron beam radiation.
• High performance metal, plastic, wood, and glass coatings are used in both indoor and outdoor applications, such as in building products, appliances, transports, etc. Due to increasingly more stringent emission rules and increasing energy costs associated with coating conversion and pollution controls, it is preferable that such coatings contain 100% solids and no volatile organic compounds (zero VOC's). Unfortunately, however, most of the non-polluting coating systems currently being used last only about 30 years.
• Thermal curing is also often unsuitable because of the impractical long oven length needed for the curing oven.
• a long oven is required because the thermal curing rate, i.e., conversion rate of the coating, for converting low viscosity monomers and oligomers to solid polymers is very slow.
• conversion to the solid state which provides tack-free, dry coatings can be completed quickly by simply evaporating the solvent from the solid resin solution.
• the present state-of-the-art thermal systems employ this technique.
• Most thermal curing coating chemistries are based on solution, emulsion, or dispersion of solid resins or very high viscosity resins (high molecular weight thermoplastic or thermostat resins), which involve very little or no curing (solidification).
• Electron beam (E-beam or E.B.) curable coatings which contain 100% solids and zero VOC, can be used for pigmented coatings, unlike U.V. curable coatings.
• current E-beam coatings suffer from the same performance limitations as do U.V. curable coatings, when compared with thermal systems. This is largely because the same resin and curing chemistries (acrylates) are employed in existing E-beam curable coatings as in the U.V. materials. Additional costs incurred with radiation (both UN. & E-beam) curable acrylate coatings include those associated with the use of nitrogen blanketing.
• E-beam irradiation is the most preferable for high speed coating lines when compared with thermal curing or UN. curing.
• Alternate available cationic curing (UN. & E.B.) epoxy chemistry coating compositions do not require nitrogen blanketing, but the cure rates of currently available epoxies are very slow when compared with acrylates.
• a soft, tacky surface is left outside the area irradiated by the beam, which is unacceptable in a high speed, low dose line.
• OEM Original Equipment Manufacture
• radiation curable (U.V. & E.B.) coatings have not been a good alternate technology for providing zero VOC, pollution-free coatings for coil coatings.
• current filled and pigmented coatings typically include the use of an environmentally unfavorable chromate filler in order to pass corrosion testing.
• the viscosities of the monomers and oligomers should be low enough to formulate a highly filled and/or pigmented coating (up to 65% by weight) without the use of any solvents, and the coating should also be able to meet the application viscosity (less than 3000 cps) of a high speed reverse roll coating system, i.e. greater than 400 FPM.
• the coatings should meet industry standards for each of the application areas in terms of adhesion, flexibility, gloss, weathering, corrosion, etc.
• the coating chemistry should be suitable for high speed, low dose E-beam cure lines and alternatively, for thermal curing, such that the materials can be immediately rolled into coils without any coating lift up problem, with or without nitrogen blanketing.
• the present invention meets the aforementioned needs and avoids the problems associated with available metal, plastic, wood, or glass coatings.
• the invention is predicated on the unexpected discovery of a new cationically curable resin chemistry based on novel siloxane epoxy resins. These novel resins can be cured by heat or by E- beam radiation and can be cured in air without the need for nitrogen blanketing. This is advantageous because the cost of maintaining an inert atmosphere can contribute substantially to the overall cost of curing by radiation.
• the compositions can be immediately rolled into coils without any coating lift up problem.
• the coatings of the present invention are solventless and therefore, contain zero VOC's, making them desirable for use in industry because they do not present any health hazards before polymeric conversion.
• the unique resins of the present invention are surprisingly superior to currently available coatings because they contain 100% solids, can be cured by high speed, low dose, E-beam radiation or thermally, and can be used as metal, plastic, wood, or glass coatings for both indoor and outdoor applications.
• Other advantages of the present compositions over currently available resins include excellent and improved cured film properties, such as exhibiting good adhesion, flexibility (tough without being brittle), weatherability, and unexpectedly good corrosion resistance even in the absence of a chromium-containing filler.
• the coating compositions may be clear or may contain fillers and/or pigments. Accordingly, in one aspect, the present invention is a clear coating composition comprising from about 90 to about 100 parts by weight of a base resin; from 0 to about 2 parts of an adhesion promoter and from about 3 to about 8 parts by weight of a cationic polymerization initiator.
• the base resin comprises: (A) from about 30 to about 50 parts by weight of a cycloaliphatic epoxy functional siloxane monomer having structure (IA)
• m is an integer having a value from 5 to 50; (C) from about 20 to about 50 parts by weight of at least one non-silicon- containing epoxy resin selected from the group consisting of (i) epoxidized vegetable oils, (ii) epoxidized vegetable oil esters, and (iii) 3,4-epoxycyclohexyl 3',4'-epoxycyclohexane carboxylate having structure (IIA) (IIA) (D) from 0 to about 30 parts by weight of one or more flexibilizers selected from the group of (i) epoxides based on a diglycidyl ether of bisphenol A having structure (I IB)
• the cationic polymerization initiator comprises at least one diaryliodonium salt, wherein each diaryliodonium salt is present in a corresponding separate catalyst solution comprising from about 40 to about 80 wt. % of a carrier medium and from about 20 to about 60 wt. % of the diaryliodonium salt or salts.
• Each diaryliodonium salt has structure (III)
• R is methyl or hydrogen; y is 0 or an integer from 1 to 25; and A " is a non- nucleophilic anion selected from the group consisting of [BF ] “ , [PF 6 ] “ , [AsF 6 ] ⁇ [SbF 6 ] ⁇ , [B(C 6 F 5 ) 4 ] ⁇ and [Ga(C 6 F 5 ) 4 ] ⁇
• the present invention is a coating composition
• a coating composition comprising from about 35 to about 62 parts by weight of the aforementioned base resin; from about 32 to about 65 parts by weight of one or more components selected from the group consisting of fillers, pigments, diluents, tougheners, flow control agents, and antifoaming agents; from 0 to about 1 part of an adhesion promoter and from about 2 to about 5 parts by weight of a cationic polymerization initiator, as previously described.
• Formulations containing fillers and/or pigments, as well as any of the other aforementioned components, are useful as primers or topcoats.
• the invention is a method for manufacturing a coated article.
• the first step of the method involves applying either the aforementioned clear coating composition or the coating composition containing fillers, pigments, diluents, tougheners, flow control agents, and/or antifoaming agents, as previously described, to an article made of wood, glass, plastic, or metal.
• the composition deposited on the article may be exposed to E-beam radiation or to thermal energy.
• the radiation generally ranges from about 3 to about 12 Mrad.
• thermal curing is employed, the article and composition are heated to a first maximum substrate temperature ranging from about 150 °C to about 260° C. Polymerization occurs to > 90% during the exposure to E-beam radiation or heating to the first maximum substrate temperature.
• the coated article may be heated to a second maximum substrate temperature ranging from about 80 °C to about 125° C.
• the invention is a coated article manufactured by the previously described method. Description of the Preferred Embodiments
• the present siloxane epoxy coating compositions include a base resin, an adhesion promoter and a cationic polymerization initiator.
• the filled/pigmented coatings additionally include fillers, pigments, diluents, tougheners, flow control agents, and/or antifoaming agents.
• these epoxy resin coatings can be cured by E-beam radiation or thermally to give the desired processing parameters and excellent cured film properties described herein in terms of adhesion, flexibility, weatherability, corrosion resistance, etc.
• the mere combination of these ingredients or similar ingredients followed by thermal heating or E-beam radiation does not guarantee a cured coating having excellent cured film properties. Instead, it is the amount of each specific component taken together as a whole that provides the unexpectedly superior cured coatings of the present invention.
• the base resin includes a cycloaliphatic epoxy functional siloxane monomer having structure (IA), an optional cycloaliphatic epoxy functional siloxane oligomer having structure (IB), one or more non-silicon containing epoxy resins, and optional flexibilizers.
• the clear, unfilled coating compositions contain from about 90 to about 100 parts by weight of the base resin relative to the total weight of the formulation, and the total weight of the pigmented and/or filled compositions contain from about 35 to about 62 parts by weight of the base resin.
• Cycloaliphatic epoxy functional siloxane monomer having structure (IA) has the chemical name l,l,3,3-tetramethyl-l ,3-bis[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl] disiloxane and has a molecular weight of 376 g/mole.
• Siloxane (IA) is commercially available from Polyset Company Inc., Mechanicville, New York as PC 1000.
• cycloaliphatic epoxy functional siloxane (IA) is incorporated into the base resin in amounts ranging from about 30 to about 50 parts by weight of the total base resin, and siloxane (IB), in amounts ranging from 0 to 30 parts by weight.
• non-silicon-containing epoxy resins include epoxidized vegetable oils and epoxidized vegetable oil esters, such as VIKOFLEX® 9010, which is a methyl epoxy linseedate available from Atofina Chemicals. Inc.
• EECH 3,4-epoxycyclohexyl 3',4'- epoxycyclohexane carboxylate
• EECH has structure (IIA) and is commercially available from Union Carbide as ERL 4221. Of these, epoxidized vegetable oil esters are generally preferred.
• the base resin may include up to about 30 parts by weight of one or more flexibilizers, which provide flexibility to the compositions.
• Suitable flexibilizers include epoxides having structure (TIB) above, which are based on a diglycidyl ether of bisphenol A. Examples include ARALDITE® 6084 and ARALDITE® 6097, which are available from Ciba Geigy in solid form. VIKOLOX® 14, which is a C-14 epoxidized alpha olefin available from Elf Atochem, is another suitable flexibilizer. Polyol flexibilizers, such as caprolactan triol, which is available from Solvay Interox, Inc. as CAPA® 4101 (previously sold as CAPA® 316) are also suitable.
• CAPA® 4101 has the chemical name 2-oxepanone and is a polymer of 2-2-bis(hydroxymethyl)-l, 3- propanediol having the chemical formula (C 6 H ⁇ 0 O 2 C 5 H ] 2 0 ).
• Additional useful flexibilizers include thermoplastic acrylic resins, such as DEGALAN® 64/12 and DEGALAN® P24, which are available from Rohm, limonene oxides, such as limonene dioxide available from Elf Atochem; elastiomers; and phenoxy resins. Allyl ethers are also useful flexibilizers, and examples include vinyl ethers and propenyl ethers available from ISP, BASF, etc. Other suitable flexibilizers would be obvious to those of skill, and the invention is not limited to the flexibilizers described herein.
• One preferred base resin for use in the present clear formulations contains from about 35 to about 40 parts by weight of the siloxane monomer having structure (IA), from 0 to about 15 parts by weight of the siloxane oligomer having structure (IB), but more preferably 10 parts, from about 28 to about 40 parts by weight of the non-silicon- containing epoxy resin(s), and from about 9 to about 17 parts by weight of the epoxide based on a diglycidyl ether of bisphenol A having structure (I IB).
• a preferred base resin contains from about 40 to about 45 parts by weight of the siloxane monomer having structure (IA), from about 5 to about 15 parts by weight of the siloxane oligomer having structure (IB), but more preferably 10 parts, from about 32 to about 40 parts by weight of the non-silicon-containing epoxy resin(s), and from about 5 to about 10 parts by weight of the epoxide based on a diglycidyl ether of bisphenol A having structure (1IB).
• the non-silicon-containing epoxy resin in these compositions is an epoxidized vegetable oil, such as VIKOFLEX® 9010.
• the present compositions may optionally include an adhesion promoter.
• an adhesion promoter In clear formulations, up to about 2 parts by weight of the adhesion promoter may be added for improved adhesion to metal. However, in filled and/or pigmented compositions, up to about 1 part by weight is sufficient to provide good adhesion to the cured films.
• adhesion promoters include, but are not limited to, epoxy alkoxysilanes, such as 2-(3,4-epoxycyclohexyl)-ethyl trimethoxysilane and 3- glycidyloxypropyltrimethoxysilane, both of which are available from Witco Corporation as A 186 and Al 87, respectively.
• the filled and pigmented coating formulations also contain from about 32 to about 65 parts by weight of fillers, pigments, diluents, tougheners, flow control agents, and/or antifoaming agents.
• ingredients include, but are not limited to, titanium dioxide pigments; such as Ti0 2 2160, TiO 2 2310, Ti0 2 2020, and the like available from Kronos, Inc.; talc (magnesium silicate hydroxide), such as Nytal 300, which is available from R.T.Vanderbilt; ceramic microspheres, such as ZeospheresTM microspheres, available from 3M as G-400 and G-200; antifoaming agents (foam suppressants), such as BYK® 501 available from BYK Chemie USA, Inc.; wetting agents, such as Silwet ® L-7604 available from OSI Specialities; grinding agents, such as BYK® 307, available from BYK Chemie USA, Inc.; and hydrophobic fumed silica, such as
• One unexpected and surprising advantage of the present pigmented/filled compositions over currently available primer and topcoat resins is that excellent corrosion resistance is exhibited even in the absence of a chromate or phosphate additive.
• current commercial coatings must include such anticorrosion ingredients, such as zinc chromate, strontium chromate, zinc phosphate, or strontium phosphate to pass corrosion testing. Because the use of these materials is an important environmental concern, elimination thereof in the compositions described herein makes the present coatings far more desirable than any coatings previously available.
• a cationic polymerization initiator is also included in the present coatings prior to curing, both thermally and by E-beam irradiation.
• the clear formulations contain from about 3 to about 8 parts by weight of the cationic polymerization initiator solution based on the total weight of the composition, and the filled/pigmented coatings include for curing from about 2 to about 5 parts by weight of the cationic polymerization initiator solution.
• the cationic polymerization initiator contains one or more diaryliodonium salts, each having the following formula (III):
• R is methyl or hydrogen
• y is 0 or an integer from 1 to 25.
• the methyl substituent may be located at any position of the aryl ring, i.e., at the 2, 3, or 4-carbon relative to the carbon attached to the iodine atom, which is identified as the 1 -carbon.
• the 2-, 3-, and 4-carbon positions are also known as ortho-, meta-, and para-, as anyone of ordinary skill would know.
• a “ is a non-nucleophilic anion, commonly [BF 4 ]-, [PF 6 ] “ , [AsF 6 ] ⁇ [SbF 6 ] ⁇ [B(C 6 F 5 ) 4 ] “ , or [Ga(C 6 F 5 ) 4 ] ⁇
• a negatively charged moiety is conventionally indicated herein by a minus sign, either in a circle or without the circle. Each symbol is used interchangeably, and may be positioned as a superscript relative to the moiety. Similarly, a positively charged moiety is denoted by a plus symbol, with or without the circle.
• Each selected diaryliodonium salt is separately dissolved in a carrier medium, which may be a monomer, to form a respective catalyst solution containing from about 20 to about 60 wt. % of the selected diaryliodonium salt and from about 40 to about 80 wt. % of the selected carrier medium.
• exemplary carriers include monomers such as 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate (EECH)(structure (IIA)) and bis(3,4-epoxycyclohexyl) adipate.
• EECH 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate
• bis(3,4-epoxycyclohexyl) adipate is not limited to these carriers, and other suitable carrier mediums would be obvious to one of ordinary skill.
• Bis(3,4-epoxycyclohexyl) adipate which is available
• One catalyst solution embodiment contains about 40 wt. % of the diaryliodonium salt and about 60 wt. % 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate (EECH) or bis(3,4-epoxycyclohexyl) adipate, but more preferably, EECH.
• diaryliodonium salts for use in polymerizing the present compositions are: [4-(2-hydroxy-l-tetradecyloxy)-phenyl] phenyliodonium hexafluorophosphate having structure (IIIA); [4-(2-hydroxy-l -tetradecyloxy)-phenyl] 4- methylphenyliodonium hexafluorophosphate having structure (IIIB); [4-(2-hydroxy-l- tetradecyloxy)-phenyI] phenyliodonium hexafluoroantimonate having structure (II IC); amd [4-(2-hydroxy-l -tetradecyloxy)-phenyl] 4-methylphenyliodonium hexafluoroantimonate having structure (HID): ⁇ - ⁇ CH3 ⁇ (IIIB)
• the fluorophosphate and fluoroantimonate diaryliodonium salt catalysts having structures (IIIA), (IIIB), (IIIC), and (HID) are commercially available from Polyset Company, respectively, as PC-2508, PCX-2519, PC-2506, and PCX-2509.
• the most preferred fluorophosphate diaryliodonium salt is that of structure (IIIA)
• the most preferred fluoroantimonate diaryliodonium salt is that of structure (IIIC)
• the polymerization initiator includes at least one diaryliodonium salt in a catalyst solution, but most preferably one or more of the aforementioned fluorophosphate or fluoroantimonate diaryliodonium salts in solution.
• the amount and identity of the cationic polymerization initiator is dependent upon whether the formulation is to be cured thermally or by E-beam radiation.
• an all phosphate iodonium catalyst solution may be suitable in some applications to provide satisfactory adhesion and performance after cure.
• An all antimonate iodonium catalyst may provide films that are very dry after E-beam irradiation, but in some cases such films may have inadequate adhesion and may exhibit some brittleness.
• an all antimonate iodonium catalyst solution provides a satisfactory cure and results in films that are dry, but not brittle, and not tacky. With either type of curing, however, it is often preferable to use a blend of phosphate/antimonate iodonium catalyst solutions to provide dry films with good adhesion.
• the identity and amount of catalyst can be adjusted depending on the type of curing to be done, as well as on the application and substrate.
• the cationic polymerization initiator preferably contains up to about 8 parts by weight of the fluorinated iodonium phosphate catalyst solution alone, up to about 4 parts by weight of the fluorinated iodonium antimonate catalyst solution alone, or a blend of the phosphate/antimonate solutions, such that the final formulation contains a total cationic polymerization initiator ranging from about 3 to about 8 parts by weight of the total composition.
• an exemplary cationic polymerization initiator for use in E-beam or thermal curing contains a 50 /50 (wt.
• each fluorophosphate and fluorantimonate iodonium salt catalyst solution i.e., equal parts by weight of each catalyst solution.
• the amount of each catalyst solution ranges from about 2 to about 4 parts by weight (e.g., 2 parts of the fluorantimonate iodonium salt catalyst solution and 2 parts of the fluorophosphate iodonium salt catalyst solution).
• another suitable blend contains about 3 parts by weight of the iodonium phosphate catalyst solution and about 1 part of the iodonium antimonate catalyst solution.
• Another suitable blend for E- beam curing contains about 4 parts by weight of the iodonium phosphate catalyst solution and about 2 parts by weight of the iodonium antimonate catalyst solution.
• an all iodonium phophate catalyst solution generally ranging from about 4 to about 8 parts by weight of the final formulation is suitable for E-beam curing.
• another initiator includes from about 2 to about 4 parts by weight of the iodonium antimonate catalyst solution without any iodonium phosphate catalyst.
• each catalyst is preferably present in a 40/60 (wt.
• the cationic polymerization initiator preferably contains up to about 4.4 parts by weight of the fluorinated phosphate iodonium catalyst solution alone, up to about 4 parts by weight of the fluorinated antimonate iodonium catalyst solution alone, or a blend of the phosphate/antimonate catalyst solutions, such that the final formulation contains a total cationic polymerization initiator ranging from about 2 to about 5 parts by weight of the total composition.
• a 50 /50 (wt. %) blend of each fluorophosphate and fluoroantimonate iodonium salt catalyst solution is suitable when curing by either heat or E-beam radiation.
• each catalyst solution ranges from about 1 to about 2.5 parts by weight (e.g., 1 part of the fluorantimonate iodonium salt catalyst solution and 1 part of the fluorophosphate iodonium salt catalyst solution).
• a suitable blend contains about 3 parts of the iodonium phosphate catalyst solution and about 1 part of the iodonium antimonate catalyst solution.
• Another suitable polymerization initiator for E-beam curing contains from about 2 to about 4 parts by weight of the iodonium phosphate catalyst solution and no iodonium antimonate catalyst solution.
• a preferred cationic polymerization initiator includes from about 2 to about 4 parts by weight of the iodonium antimonate catalyst solution alone without any iodonium phosphate catalyst.
• each catalyst is preferably present in a 40/60 (wt. %) solution of the iodonium salt in EECH, bis(3,4-epoxycyclohexyl) adipate, or other suitable carrier medium, but most preferably EECH.
• the catalyst solutions and blends included in both the filled/pigmented and unfilled, clear formulations may be adjusted according to the type of curing desired.
• an antimonate iodonium catalyst solution may be used alone, or some of it may be replaced with a phosphate iodonium catalyst solution.
• a phosphate iodonium catalyst solution For E-beam curing, most preferably, some or all of the antimonate iodonium catalyst solution may be replaced with the phosphate iodonium catalyst solution. Exemplary embodiments are found in, but not limited to, the formulations provided in the examples provided herein.
• the film may be slightly soft after curing.
• the composition may then be baked in air at a temperature for a time sufficient to obtain a film with desirable properties.
• postbake refers to such a drying step.
• a typical postbake which raises the substrate temperature to about 80 °C-125 °C for a period ranging from about 15 minutes to about an hour, is therefore often preferred for improving cured film properties.
• an improvement in adhesion is observed regardless of the type and source of the substrate (Al or steel, cleaned or not cleaned, treated or not treated, etc.).
• the present invention also includes a method for manufacturing a coated article, as well as the coated article manufactured by the method.
• the term "article” includes a wood, glass, plastic, or metal substrate.
• Applications include decorative, insulating, or protective coatings on such materials.
• a filled/pigmented or unfilled, clear formulation, as described herein is first deposited onto the article by conventional techniques known in the art, such as spray or roll coating.
• the composition applied to the article is cured by being exposed to E-beam radiation ranging from about 3 to about 12 Mrad.
• the composition on the article may be thermally cured by heating the article to a temperature ranging from about 150 °C to about 260 °C.
• This temperature corresponds to the maximum temperature of the substrate in the curing oven (or on the hotplate).
• the term “peak metal temperature' or “PMT” is often used in connection with this maximum substrate temperature.
• the composition is polymerized to > 90%.
• the coated article may be subjected to a postbake step to improve the properties of the coating.
• Flashing Regular hardware store roof flashing
• AL 36 Q-Panel of aluminum with a chromate pretreatment
• R 36-1 Q-Panel of steel with Bondrite 1000 iron phosphate P60 chrome and deionized water rinse
• Chrome Aluminum panel, 5000 series, with a chrome conversion coating
• Non-Chrome Aluminum panel, 5000 series, with a non-chrome conversion coating
• Galv. Galvanized steel panel
• Treated Galv . Galvanized steel panel with a phosphate pretreatment
• Galvalume Galvalume coated steel panel with no pretreatment
• HDGT hot dipped Galvanized treated steel panel with Bondrite
• Base resin (III) having the following composition was prepared:
• Base resin (IV) having the following composition was prepared:
• Base resin (V) having the following composition was prepared: Primer formulations containing Base Resin (V) and the following other components were prepared and tested:
• Base resin (VI) having the following composition was prepared:
• the formulations provide the desirable processing parameters and film properties described herein.
• EXAMPLE 20 E-Beam Cure with and without Postbake Top Coat Formulation
• Topcoat formulations containing Base Resin (TV) from Example 16 and the following other components were prepared and tested:
• Base resin (VII) having the following composition was prepared:
• Base resin (VIII) having the following composition was prepared:
• Base resin (IX) having the following composition was prepared:
• Base resin (X) having the following composition was prepared:
• Base resin (XI) having the following composition was prepared:
• Base resin (XII) having the following composition was prepared:
• ASTM test D 1654 was performed to determine the amount of creep of corrosion from a scribed line through a coating on the panel.
• maximum is the measurement in mils of the area of the scribe with the most creep;
• Mean is the average of all measured areas in mils.
• ASTM test D 714 was performed to determine the amount and type, if any, of coating blistering. A rating of 1 indicates the largest blisters, and 8 is the smallest in size. Distribution (distrib.) is the frequency of blisters on the panel.
• ASTM test D 610 was performed to determine the amount and type, if any, of surface rust on the panels.
• a frequency (freq.) of 0 means that > 50% of the surface is rusted, and 10 indicates that ⁇ 0.01% of surface is rusted.
• "Type” is the description of the type of surface rust found on the panels: "S” is spot; “P” is pinpoint; and "H” is hybrid.
• ASTM test D 3359 was performed to determine the adhesion of the coating to the substrate by tape pull.
• Table I ASTM Test B117-Salt Fog Weathering Test
• UV/condensation cycle alternated between exposure to 4 hours of UV light at 60 °C (using UVA lamps set to 0.72 W(m 2 nm)) and exposure to 4 hours of condensation at 50 °C using a UV/Condensation cabinet from Q-Panel Test Equipment as Model No. QUV/se.
• Each fog/dry cycle alternated between exposure to 1 hour fog at ambient temperature and exposure to 1 hour dry at 35 °C.
• the fog solution used was 0.05% by weight sodium chloride and 0.35% by weight ammonium sulfate in deionized water, and the Fog/Dry cabinet was Q-Panel Test Equipment Model No. Q-Fog-CCT600.

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=34193557

Family Applications (1)

Country Status (6)

Cited By (2)

Families Citing this family (23)

Citations (3)

Family Cites Families (8)

• 2003
  • 2003-08-07 US US10/636,101 patent/US6962948B2/en not_active Expired - Lifetime
• 2004
  • 2004-08-05 WO PCT/US2004/025176 patent/WO2005017057A1/en active IP Right Grant
  • 2004-08-05 DE DE200460003395 patent/DE602004003395T2/de not_active Expired - Fee Related
  • 2004-08-05 EP EP20040780077 patent/EP1651731B1/en active Active
  • 2004-08-05 AT AT04780077T patent/ATE346124T1/de not_active IP Right Cessation
  • 2004-08-05 AU AU2004264507A patent/AU2004264507A1/en not_active Abandoned
• 2005
  • 2005-03-15 US US11/079,971 patent/US7285579B2/en active Active

Patent Citations (3)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events