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
  • 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
• • 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
  • C08G59/40—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 curing agents used
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4085—Curing agents not provided for by the groups C08G59/42 - C08G59/66 silicon containing 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/10—Metal compounds
  • C08K3/105—Compounds containing metals of Groups 1 to 3 or of Groups 11 to 13 of the Periodic Table
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing 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
  • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
  • C08K5/57—Organo-tin compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
  • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
  • C08K2003/321—Phosphates
• • 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
  • C08K5/54—Silicon-containing compounds
  • C08K5/544—Silicon-containing compounds containing nitrogen

Definitions

• the present disclosure is directed to epoxy resin based compositions useful for protective coatings and the like and, more specifically, to epoxy- polysiloxane polymer compositions having improved properties of flexibility, weatherability, and reduced shrinkage along with corrosion resistance, compressive strength and chemical resistance at least comparable to conventional epoxy polysiloxane coating formulations.
• Epoxy coating materials are well known and have gained commercial acceptance as protective and decorative coatings for steel, aluminum, galvanizing, wood and concrete in maintenance, marine, construction, architectural, aircraft, automotive, flooring, and product finishing markets.
• the basic raw materials used to prepare these coatings generally comprise as essential components (a) an epoxy resin, (b) a hardener, and (c) pigment, aggregate, or other components.
• the epoxide resins are those having more than one 1,2-epoxy group per molecule and may be saturated or unsaturated, aliphatic, cycloaliphatic, or heterocyclic.
• the epoxy resins generally contain glycidyl ester or glycidyl ether groups and have a weight per epoxide of 100 to 5,000.
• the hardener is typically chosen from the general classes of aliphatic amines or aliphatic amine adducts, polyamides, polyamidoamines, cycloaliphatic amines, aromatic amines, Mannich bases, ketimines, and carboxylic derivatives.
• Pigments and aggregates include, for example, titanium dioxide and other inorganic and organic color pigments, silica, barium sulfate, magnesium silicate, calcium silicate, fumed silica, garnet, feldspar, carbon black and the like.
• Epoxy based protective coatings represent one of the most widely used methods of corrosion control. They may be used to provide long term protection of steel, concrete, aluminum, and other structures under a broad range of corrosive conditions, extending from atmospheric exposure to full immersion in strongly corrosive solutions. For over 20 years, these coatings have been formulated from either a solid or liquid epoxy resin cured with an aliphatic polyamine or polyamide resin, e.g., Shell Epon 1001, or Epon 828 epoxy resins cured with diethylene triamine (DETA) or Versamid 100 series polyamides. In typical two package coating systems, the epoxy resin component is usually the vehicle for pigment grinding and dispersion of other aggregates and various additives.
• Epoxy based protective coatings posses many properties which make them desirable as coating materials. They are readily available and are easily applied by a variety of methods including spraying, rolling and brushing. They adhere well to steel, concrete and other substrates, have low moisture vapor transmission rates, act as barriers to water, chloride and sulfate ion ingress, provide excellent corrosion protection under a variety of atmospheric exposure conditions and have good resistance to many chemicals and solvents.
• Epoxy based materials may also be formulated as surfacers or flooring materials primarily for application over concrete.
• one commercially successful epoxy based flooring material utilizes liquid bisphenol A epoxy resin and a modified aliphatic polyamine combined with graded silica sand aggregate.
• epoxy based coating and flooring materials may not display good resistance to weathering in sunlight. While such coatings may maintain their chemical and corrosion resistance, exposure to the ultraviolet (UV) light component of sunlight may result in a surface degradation phenomenon known as chalking which changes both the color and gloss retention of the original coating. Where color and gloss retention is desired or required, epoxy protective coatings are typically top- coated with a more weatherable coating, such as an alkyd, vinyl or aliphatic polyurethane coating. The end result is a two or sometimes three coat system which provides the desired corrosion resistance and weatherability, but which is also labor intensive and expensive to apply.
• UV ultraviolet
• epoxy based coating and flooring materials require resistance to mechanical abuse.
• coated materials may be subjected to impact or flexing which may result in cracking or other imperfections in the epoxy coating. Subsequent exposure to weathering or chemicals may result in contact with chemicals and the underlying surface materials, potentially resulting in oxidation of the underlying material, degradation of the epoxy coating from the underside, and/or release of the epoxy coating from the surface.
• epoxy based coating and flooring materials have gained wide commercial acceptance, the need nevertheless remains for epoxy based materials with improved chemical and corrosion resistance, resistance to mechanical abuse (such as flexing or impact), and improved color or gloss retention.
• Epoxy coatings and flooring materials with improved color and gloss retention are needed wherever they may be exposed to sunlight.
• An epoxy coating which doesn't chalk and does not require a weatherable topcoat is desirable.
• Coating and flooring materials with improved chemical, corrosion, impact, flex, and abrasion resistance are needed for both primary and secondary chemical containment structures, for protecting steel and concrete in chemical, power generation, railcar, sewage and waste water treatment, automotive, and paper and pulp processing industries.
• the present disclosure provides for new epoxy based coating and flooring compositions displaying one or more of improved chemical resistance, resistance to weathering, corrosion resistance, resistance to mechanical abuse, flexibility, high tensile and compressive strength, and excellent resistance impact and abrasion.
• the present disclosure provides new epoxy-polysiloxane polymer coating compositions.
• the present disclosure provides an epoxy-polysiloxane polymer coating composition comprising water, a polysiloxane having the formula:
• a non-aromatic epoxide resin having more than one 1 ,2-epoxide group per molecule with an epoxide equivalent weight of 100 to 5,000; and a cure system comprising a blend comprising at least one trialkoxy functional aminosilane and at least one amino functional polysiloxane resin, where the blend has an alkoxy content of 10% by weight to 25% by weight.
• each Ri is a hydroxy group or an alkyl, aryl, or alkoxy group having up to six carbon atoms
• each R 2 is independently hydrogen or an alkyl or aryl group having up to six carbon atoms
• n is selected so that the molecular weight for the polysiloxane is 400 to 10,000.
• the present disclosure provides an epoxy- polysiloxane polymer coating composition
• an epoxy- polysiloxane polymer coating composition comprising water, from 20% to 80% by weight of a polysiloxane having the formula:
• a non-aromatic epoxide resin having more than one 1 ,2-epoxide group per molecule with an epoxide equivalent weight of 100 to 5,000; up to 15% by weight of a cure accelerator comprising a tin catalyst in the form of an octanoate, a dodecanoate, or a naphthanate; up to 15% by weight of a flexible epoxy resin based on the glycidyl ether of castor oil having an epoxide equivalent weight of 200 to 1,000; and from 5% to 40% by weight of a cure system comprising a blend of at least one trialkoxy functional aminosilane and at least one amino functional polysiloxane resin, where the blend has an average alkoxy functionality value of 2.2 to 2.8 and is added in an amount sufficient to provide an amine equivalent to epoxide equivalent of 0.7: 1.0 to 1.3: 1.0 in the coating composition.
• each Ri is a hydroxy group or an alkyl, aryl, or alkoxy group having up to six carbon atoms
• each R 2 is a hydrogen or an alkyl or aryl group having up to six carbon atoms
• n is selected so that the molecular weight for the polysiloxane to 10,000.
• the amino functional polysiloxane resin has a general formula
• R 5 is a difunctional organic radical selected from an aryl, an alkyl, a dialkylaryl, an alkoxyalkyl, an alkylaminoalkyl, or a cycloalkyl radical, each 5 is independently an alkyl, hydroxyalkyl, alkoxyalkyl, or hydroxyalkoxyalkyl group containing less than six carbon atoms, each R 8 is a difunctional organic radical independently selected from an aryl, alkyl, dialkylaryl, alkoxyalkyl, alkylaminoalkyl, or cycloalkyl radical, each R is independently an aryl, phenyl, (Ci-C 4 )alkyl, (Ci-C 4 )alkoxy, or
• m is selected so that the blend has an amine equivalent weight of 112 to 250 g/NH.
• the present disclosure provides for a coated substrate, wherein the substrate comprises at least one surface coated with an epoxy- polysiloxane polymer coating composition as described herein.
• the present disclosure provides a method for protecting a surface of a substrate from the undesired effects of one or more of chemicals, corrosion, and weather by coating the surface with a coating composition prepared by the method comprising preparing a resin composition, adding a cure system to the resin component to form a fully cured epoxy-modified polysiloxane coating composition, where the blend has an average alkoxy functionality value of 2.2 to 2.8, and applying the coating composition to the surface of a substrate to be protected before the composition becomes fully cured.
• the resin composition comprises water, a polysiloxane having the formula:
• each Ri is a hydroxy group or an alkyl, aryl, or alkoxy group having up to six carbon atoms
• each R 2 is a hydrogen or an alkyl or aryl group having up to six carbon atoms
• n is selected so that the molecular weight for the polysiloxane is 400 to 10,000.
• the cure system comprises a blend of at least one trialkoxy functional aminosilane and at least one amino functional polysiloxane resin; and optionally a cure accelerator comprising at least one metal catalyst.
• compositions according to the various embodiments of the present disclosure display improved properties, such as, but not limited to, resistance to chemicals, resistance to corrosion or oxidation, and/or improved weatherability for the surface coated with the coating composition, compared to surfaces coated with conventional epoxy-modified polysiloxane coating compositions.
• any numerical range recited herein is intended to include all sub-ranges subsumed therein.
• a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
• the present disclosure provides for an epoxy-polysiloxane polymer coating composition suitable for coating surfaces and providing improved chemical, corrosion, and/or weather resistance.
• the epoxy- polysiloxane polymer coating may comprise water, a resin component comprising a polysiloxane and a non-aromatic epoxide resin, and a cure system, wherein the combined composition reacts to form a cross-linked epoxy-polysiloxane polymer structure.
• the coating composition may further comprise a flexible epoxy rein based on a glycidyl ether of castor oil.
• the coating composition may optionally comprise a cure accelerator comprising at least one metal catalyst.
• the resin may comprise a blend of a polysiloxane, an epoxide resin, and optionally a organooxysilane.
• a polysiloxane used to make up the resin component
• various embodiments of the polysiloxanes include, but are not limited to, those having Formula I:
• each Ri may be selected from the group consisting of the hydroxy group and alkyl, aryl, and alkoxy groups having up to six carbon atoms.
• Each R 2 may be selected from the group consisting of hydrogen and alkyl and aryl groups having up to six carbon atoms.
• n may be an integer selected so that the molecular weight of the polysiloxane is in the range of 400 to 10,000 Daltons.
• the Ri and R 2 may comprise groups having less than six carbon atoms, for example, to facilitate rapid hydrolysis of the polysiloxane, which reaction may be driven by the volatility of the alcohol analog product of the hydrolysis.
• Ri and R 2 groups having greater than six carbon atoms may impair the hydrolysis of the polysiloxane due to the relatively low volatility of each alcohol analog.
• Methoxy, ethoxy and silanol functional polysiloxanes having n selected such that the molecular weights are 400 to 2000 may be used in specific embodiments for formulating coating compositions of the present disclosure.
• suitable methoxy functional polysiloxanes may include: DC-3074 and DC-3037 commercially available from Dow Corning Corp., Midland, MI; GE SRI 91 and SY-550 commercially available from Wacker located in Adrian, MI.
• Silanol functional polysiloxanes include, but are not limited to, Dow Coming's DC840, Z6018, Q 1-2530 and 6-2230 intermediates.
• the coating composition may comprise from 20% to 80% by weight of the polysiloxane. In other embodiments, the coating composition may comprise 15% to 65% by weight of the polysiloxane. In one embodiment, the coating composition may comprise approximately 31% by weight of the polysiloxane.
• Suitable epoxy resins useful in forming coating embodiments of this disclosure may include non-aromatic epoxy resins that contain more than one and in certain embodiments, two 1,2-epoxy groups per molecule.
• epoxide resin and “epoxy resin” are used interchangeably.
• the epoxide resins may be liquid rather than solid and may have an epoxide equivalent weight of 100 to 5,000, in other embodiments ranging of 100 to 2,000, and still other embodiments of 100 to 500, and have a reactivity of about two.
• the epoxide resins may be non-aromatic hydrogenated cyclohexane dimethanol and diglycidyl ethers of hydrogenated
• Bisphenol A-type epoxide resin such as Eponex 1510, and Eponex 1513
• non-aromatic epoxy resin may include EP-4080E (cycloaliphatic epoxy resin) commercially available from Adeka, Japan; DER 732 and DER 736.
• the epoxy resin may be EP-4080E.
• Such non-aromatic hydrogenated epoxide resins may be desired for their limited reactivity of about two, which promote formation of a linear epoxy polymer and prohibits formation of a cross-linked epoxy polymer. Without intending to be limited to a specific interpretation, it is believed that the resulting linear epoxy polymer formed by adding the hardener to the epoxide resin may be at least partially responsible for the enhanced weatherability of this composition.
• the coating composition may comprise from 20% to 80% by weight of the epoxide resin, and in other embodiment from 15% to 45% by weight of epoxide resin. According to one embodiment, the coating composition may comprise about 26% by weight of the non-aromatic epoxide resin.
• the various embodiments of the coating compositions comprise a cure system.
• the cure system may comprise a blend of one or more alkoxy functional aminosilanes.
• the cure system may comprise a blend of at least one trialkoxy functional aminosilane and at least one amino functional polysiloxane resin, where the blend has an alkoxy content of 10% by weight to 25% by weight.
• the blend comprising alkoxy functional aminosilanes or the blend comprising at least one trialkoxy functional aminosilane and at least one aminofunctional polysiloxane resin may have an average alkoxy functionality value ranging from 2.0 to 2.8.
• the blend of alkoxy functional aminosilanes or the blend comprising at least one trialkoxy functional aminosilane and at least one aminofunctional polysiloxane resin may have an average alkoxy functionality value ranging from 2.2 to 2.8.
• the cure system may comprise from 5% to 40% by weight of the coating composition, and in other embodiment from 10% to 30% by weight of the coating composition. According to one embodiment, the cure system may comprise about 14% by weight of the coating composition. In certain embodiments, the cure system is added in an amount sufficient to provide an amine equivalent to epoxide equivalent ratio of 0.7: 1.0 to 1.3 : 1.0 in the coating composition, and in other embodiments a ratio of 0.95 : 1.00 to 1.05 : 1.00.
• the blend of alkoxy functional aminosilanes may comprise at least one dialkoxy functional aminosilanes, wherein the blend has an average alkoxy functionality value of about 2.0.
• the at least one dialkoxy functional aminosilane may have a structure:
• R5 may be a difunctional organic radical independently selected from the group consisting of aryl, alkyl, dialkylaryl, alkoxyalkyl, alkylaminoalkyl, and cycloalkyl radicals, each alkyl, aryl, cycloalkyl, and alkoxy group containing up to 6 carbon atoms
• each R 6 and R 7 may be independently selected from alkyl, hydroxyalkyl, alkoxyalkyl or hydroxyalkoxyalkyl groups wherein each alkyl, aryl, cycloalkyl, and alkoxy group in the Re and R 7 groups contain up to 6 carbon atoms.
• each R 6 and R 7 group may be independently chosen from (Ci-Ce)alkyl groups and each R 5 is independently chosen from (Ci-Ce)alkyl groups and (C ⁇ - C 6 )alkylamino(Ci-C 6 )alkyl groups.
• suitable dialkoxy functional aminosilanes may include aminopropylmethyldimethoxysilane,
• aminopropylethyldimethoxysilane aminopropylethyldimethoxysilane, aminopropylethyldiethoxysilane, ⁇ - ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminoisobutyl- methyldimethoxysilane, and aminoneohexylmethyl dimethoxysilane.
• suitable commercially available dialkoxy functional aminosilanes include
• DYNASYLAN® 1505 aminopropylmethyldimethoxysilane having an amine equivalent weight of 81.57, commercially available from Evonik Degussa Corp., USA
• SILQUEST® A-2639 aminohexylmethyldimethoxysilane having an amine equivalent weight of 102.7, commercially available from Crompton OSi Specialties, South Charleston, WV
• SILQUEST® A-2120 N-beta-(aminoethyl)- gamma-aminopropyl methyldimethoxysilane
• the cure system may comprise a blend of at least one dialkoxy functional aminosilane and at least one trialkoxy functional aminosilane.
• the cure system blend may have an average alkoxy functionality value ranging from 2.2 to 2.8, and in certain
• Suitable dialkoxy functional aminosilanes for use in various embodiments described herein may have a structure:
• R5 may be a difunctional organic radical independently selected from the group consisting of aryl, alkyl, dialkylaryl, alkoxyalkyl,
• alkylaminoalkyl, and cycloalkyl radicals each alkyl, aryl, cycloalkyl, and alkoxy group containing up to 6 carbon atoms
• each R 6 and R 7 may be independently selected from alkyl, hydroxyalkyl, alkoxyalkyl or hydroxyalkoxyalkyl groups wherein each alkyl, aryl, cycloalkyl, and alkoxy group in the 5 and R 7 groups contains up to 6 carbon atoms.
• each R 6 and R 7 group may be independently chosen from (Ci-Ce)alkyl groups and each R 5 is independently chosen from (Ci-Ce)alkyl groups and (Ci-C 6 )alkylamino(Ci-C 6 )alkyl groups.
• Suitable dialkoxy functional aminosilanes are described herein.
• Suitable trialkoxy functional aminosilanes may include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltripropoxysilane, aminoneohexyltrimethoxysilane, ⁇ - ⁇ -(aminoethyl)-y- aminopropytrimethoxysilane, N- -(aminoethyl)-y-aminopropyltriethoxysilane, N- phenylaminopropyl trimethoxysilane, trimethoxysilylpropyl di ethylene triamine, 3-(3- aminophenoxy)propyl trimethoxysilane, aminoethyl aminomethyl phenyl trimethoxysilane, 2-aminoethyl-3 -aminopropyl-tris-2-ethylhexoxysilane, N- aminohexyl aminopropyl trimethoxysilane, and trisamino
• Suitable commercially available dialkoxy functional aminosilanes include SILQUEST® A-l 100 (aminopropyltrimethoxysilane having an amine equivalent weight of 89.7), SILQUEST® A-l 110 (aminopropyltriethoxysilane having an amine equivalent weight of 111), SILQUEST® A-l 120 (N-beta-(aminoethyl)- gamma-aminopropytrimethoxysilane), and SILQUEST® A-1637, commercially available from Crompton OSi Specialties, South Charleston, WV.
• Other suitable trialkoxy functional aminosilanes include those set forth in U.S. Patent No. 7,459,515 at column 10, lines 38-65, incorporated herein by this reference.
• the aminosilanes are mixed together in a ratio to provide the desired average alkoxy functionality value.
• the at least one dialkoxy functional aminosilane will have an average alkoxy functionality value of 2.0 and the at least one trialkoxy functional aminosilane will have an average alkoxy functionality value of 3.0 and the blend of the alkoxy aminosilanes will have an average alkoxy functionality value ranging from 2.2 to 2.8.
• the blend may comprise from 20% to 80% by weight of the dialkoxy functional aminosilane and from 80% to 20% by weight of the trialkoxy functional aminosilane, based on the total weight of aminosilane in the blend.
• the blend may comprise from 27% to 73% by weight of the dialkoxy functional aminosilane and from 72% to 28% by weight of the trialkoxy functional aminosilane, based on the total weight of aminosilane in the blend.
• the cure system may comprise at least one trialkoxy functional aminosilane and at least one amino functional polysiloxane resin.
• the at least one trialkoxy functional aminosilane may have a structure as set forth herein.
• the amino functional polysiloxane resin may have a general structure According to the structure of the amino functional polysiloxane resin, each Rg may be a difunctional organic radical independently selected from the group consisting of aryl, alkyl, dialkylaryl, alkoxyalkyl, alkylaminoalkyl, and cycloalkyl radicals, each R may independently selected from the group consisting of aryl, phenyl, (Ci-C 4 )alkyl, (Ci-C 4 )alkoxy, and -OSi(R ) 2 RgNH 2 .
• the polysiloxane may have a structure where m is selected so that the blend has an amine equivalent weight ranging from 112 to 250.
• the cure system will have an alkoxy content (wt% alkoxy) of 10% and 25% by weight.
• the cure system blend may have an average alkoxy functionality ranging from 2.2 to 2.8 and in certain embodiments from 2.26 to 2.78.
• R 9 may be selected from a phenyl, methyl, methoxy, -OSi(R 9 ) 2 RgNH 2 group and mixtures of any thereof.
• the amino functional polysiloxane resin may comprise a methyl, phenyl, and -OSi(R 9 ) 2 RgNH 2 group substitution at R 9 .
• the amino functional polysiloxane resin may be SILRES® HP2000 an amino functional methyl phenyl silicone resin, having an amine equivalent weight of 230-255 grams/NH, commercially available from Wacker Chemical Corporation, Adrian, Michigan.
• the amino functional polysiloxane resin may be DOW CORNING® 3055 Resin, a flexible amino-functional phenyl methyl silicone resin (CAS No.
• the cure system comprising at least one trialkoxy functional aminosilane and the amino functional polysiloxane resin may comprise from 15% to 85% by weight of the trialkoxy functional aminosilane and from 85% to 15% of the amino functional polysiloxane resin.
• the cure system may comprise from 70%> to 85% of the trialkoxy functional aminosilane and from 15% to 30% of the amino functional polysiloxane resin.
• the at least one amino functional polysiloxane resin may have a structure where each R 9 may independently comprise (Ci-C 4 )alkyl groups, phenyl groups, (Ci-C4)alkoxy groups, and -OSi(R 9 ) 2 R 8 NH 2 .
• the at least one amino functional polysiloxane resin may have a structure where R includes greater than 70% of phenyl group substitution, less than 30% (Ci-C4)alkyl group substitution and less than 2.0% (Ci-C4)alkoxy group substitution and in specific embodiments, less than 0.5%> of (Ci-C4)alkoxy group substitution.
• the at least one amino functional polysiloxane resin may have a structure where each R 9 may independently comprise (Ci-C 4 )alkyl groups, phenyl groups, (Ci-C4)alkoxy groups, and -OSi(R 9 ) 2 R 8 NH 2 .
• the at least one amino functional polysiloxane resin may have
• polysiloxane resin may be an amino functional phenyl methyl polysiloxane resin, such as, but not limited to SILRES® HP2000 or DOW CORNING® 3055.
• the late least one amino functional polysiloxane resin may have an amine equivalent weight of 230 to 280 g/NH, and in other embodiments from 240 to 280 g/NH, and even 250 to 270 g/NH.
• the cure system may further comprise a cure accelerator.
• the cure accelerator may be a metal catalyst in the form of an
• organometallic catalyst comprising the one or more metal.
• Cure accelerators comprising at least one organometallic catalyst may be useful for the purpose of further accelerating the curing rate of the coating composition into a protective film coating over a broad temperature range.
• the organometallic catalyst cure accelerator may provide accelerated cure rates at the ambient temperature.
• Suitable cure accelerator may include at least one metal catalyst comprising a metal selected from zinc, manganese, zirconium, titanium, cobalt, iron, lead, bismuth, or tin and having the formula
• R 12 where "Me” is the metal, Rio and Rn may be independently selected from acyl groups, alkyl groups, aryl groups, or alkoxy groups, wherein the acyl, alkyl, aryl and alkoxy groups may each have up to twelve carbon atoms.
• R12 and R13 may be selected from those groups set forth for R 10 and Rn or from inorganic atoms such as halogens, sulfur or oxygen.
• the Rio, R11, R12 and R13 groups may be selected from butyl, acetates, laurates, octanoates, neodecanoates or naphthanates.
• the cure accelerator may be an organometallic tin catalyst or titanium catalyst, such as, for example, dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin diacetyldiacetonate, dioctyltindilaurate, dioctyltindiacetate, or
• the cure system may comprise up to 10% by weight of the cure accelerator, and in other embodiments from 0.02% to 7% by weight of the cure accelerator, based on the total weight of the cure system.
• the proportion of the cure system to resin component may vary over a wide range.
• the coating compositions, according to one embodiment described herein, may comprise from 20% to 80% by weight of the polysiloxane, from 20% to 80% by weight of the non-aromatic epoxy resin, and from 5% to 40% by weight of the cure system.
• the coating compositions of the present disclosure may further comprise a flexible epoxy resin, such as a flexible resin based on the glycidyl ether of castor oil, CAS No. 74398-71-3.
• a flexible epoxy resin such as a flexible resin based on the glycidyl ether of castor oil, CAS No. 74398-71-3.
• the flexible epoxy resin may be a glycidyl ether of castor oil having an epoxide equivalent of 200 to 1,000.
• Suitable glycidyl ethers of castor oil include, but are not limited to, HeloxyTM 505, a castor oil polyglycidyl ether having an epoxide equivalent of 200 to 500, commercially available from Momentive Specialty Chemicals, Columbus, OH, as well as other commercially available castor oil polyglycidyl ethers under CAS No. 74398-71-3.
• Suitable flexible epoxy resins may include Erisys GE-22 diglycidylether of cyclohexanedimethanol, Erisys GE-36 diglycidylether of polyoxypropyleneglycol, Erisys GE-60 sorbitol glycidyl ether (the Erisys line of diglycidyl ethers are commercially available from CVC Specialty Chemicals, Moorestown, NJ) and CoatOSil* 2810 di-epoxy functional
• the flexible epoxy resin may be included in the coating composition where the coating composition comprises up to 15% by weight of the flexible epoxy resin. In other embodiments, the coating composition may comprise from 2% to 15% by weight of the flexible epoxy resin, or even from 5% to 15% by weight of the flexible epoxy resin.
• the coating composition may optionally comprise one or more organooxysilane.
• the organooxysilane may have the general formula: 0 R 11
• Rio may be selected from alkyl or cycloalkyl groups containing up to six carbon atoms or aryl groups containing up to ten carbon atoms.
• Rn is independently selected from alkyl, hydroxyalkyl, alkoxyalkyl, or hydroxyalkyoxyalkyl groups containing up to six carbon atoms.
• Rn may comprise groups having up to six carbon atoms, for example, to facilitate rapid hydrolysis of the organooxysilane, which reaction may be driven by the evaporation of the alcohol analog product of the hydrolysis. Without intending to be limited, it is believed that Rn groups having greater than six carbon atoms may impair the hydrolysis of the organooxysilane due to the relatively low volatility of each alcohol analog.
• the silane may be a trialkoxysilane, such as Union Carbide's A-163 (methyl trimethoxysilane), A-162, and A-137 and Dow Coming's Z6070 and Z6124.
• the coating composition may comprise from 1% to 10% by weight of the organooxysilane. In one embodiment the coating composition may optionally comprise 0.1% to 10% percent by weight organooxysilane or even from 0.7% to 5% by weight organooxysilane.
• the coating compositions may comprise one or more other components, including but not limited to, including mono- and di-epoxides, corrosion inhibitors, moisture scavengers, pigments, aggregates, rheological modifiers, plasticizers, antifoam agents, adhesion promoters, suspending agents, thixotropic agents, catalysts, pigment wetting agents, bituminous and asphaltic extenders, antisettling agents, diluents, UV light stabilizers, air release agents, dispersing aids, solvents, surfactants, or mixtures of any thereof.
• components including but not limited to, including mono- and di-epoxides, corrosion inhibitors, moisture scavengers, pigments, aggregates, rheological modifiers, plasticizers, antifoam agents, adhesion promoters, suspending agents, thixotropic agents, catalysts, pigment wetting agents, bituminous and asphaltic extenders, antisettling agents, diluents, UV light stabilizers, air release agents
• the epoxy polysiloxane coating composition may comprise up to 10% by weight of such components.
• the coating composition may additionally comprise one or more corrosion inhibitors.
• suitable corrosion inhibitors include, but are not limited to, zinc phosphate based corrosion inhibitors, for example, micronized HALOX® SZP-391, HALOX® 430 calcium phosphate, HALOX® ZP zinc phosphate, HALOX® SW-111 strontium phosphosilicate, HALOX® 720 mixed metal phosphor-carbonate, and HALOX® 550 and 650 proprietary organic corrosion inhibitors commercially available from Halox, Hammond, IN.
• Other suitable corrosion inhibitors may include HEUCOPHOS® ZPA zinc aluminum phosphate and HEUCOPHOS® ZMP zinc molybdenum phosphate, commercially available from Heucotech Ltd, Fairless Hills, PA.
• Corrosion inhibitors may be included into the coating composition in amounts of 1% to 7% by weight.
• Various embodiments of the coating composition may additionally comprise one or more light stabilizers, such as liquid hindered amine light stabilizers ("HALS”) or UV light stabilizers.
• HALS liquid hindered amine light stabilizers
• UV light stabilizers include, for example, TINUVIN® HALS compounds such as
• UV light stabilizers include, for example, CYASORB® light stabilizers, such as CYASORB® UV-1164L (2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4- isooctyloxyphenyl)-l,3,5-triazine), commercially available from Cytec Industries, Woodland Park, NJ and TINUVIN® 1130 and TINUVIN® 328 commercially available from BASF, Ludwigshafen, Germany.
• the one or more light stabilizer may be included into the coating composition in amounts of 0.25% to 4.0% by weight.
• compositions may be selected from organic or inorganic color pigments and may include, for example, titanium dioxide, carbon black, lampblack, zinc oxide, natural and synthetic red, yellow, brown and black iron oxides, toluidine and benzidine yellow, phthalocyanine blue and green, and carbazole violet, and extender pigments including ground and crystalline silica, barium sulfate, magnesium silicate, calcium silicate, mica, micaceous iron oxide, calcium carbonate, zinc powder, aluminum and aluminum silicate, gypsum, feldspar and the like.
• the amount of pigment that may be used to form the composition is understood to vary, depending on the particular composition application, and can be zero when a clear composition is desired.
• the epoxy polysiloxane composition may comprise up to 50 percent by weight fine particle size pigment and/or aggregate. In some embodiments, using greater than 50 percent by weight fine particle size pigment and/or aggregate ingredient may produce a composition that can be too viscous for application. In certain compositions where it is desirable to have more than 50% pigment or aggregate in the final composition, such as a zinc rich primer which contains up to 90% zinc in the dry film or flooring composition which may contain up to 80% pigment/aggregate, the pigment or aggregate may be packaged separately as a third component. Depending on the particular end use, certain embodiments of the coating compositions may comprise from 20% to 35% by weight fine particle size aggregate and/or pigment.
• the pigment and/or aggregate ingredient may typically be added to the epoxy resin portion of the resin component, for example, by dispersing with a Cowles mixer to at least 3 Hegman fineness of grind, or alternatively may be ball milled or sand milled to the same fineness of grind before addition of the polysiloxane ingredient.
• selection of a fine particle size pigment or aggregate and dispersion or milling to 3 Hegman grind allows for the atomization of mixed resin and cure components with conventional air, air-assisted airless, airless and electrostatic spray equipment, and may provide a smooth, uniform surface appearance after application.
• epoxy-polysiloxane compositions of this disclosure may be formulated for application with conventional air, airless, air- assisted airless and electrostatic spray equipment, brush, or roller.
• compositions may be used as protective coatings for steel, galvanizing, aluminum, concrete and other substrates at dry film thicknesses in the range of from 25 micrometers to two millimeters.
• pigment or aggregate ingredients useful in forming the composition of the present disclosure may be selected from a fine particle size material, for example but not limited to, having at least 90 weight % greater than 325 mesh U.S. sieve size.
• the present coating composition may comprise water and the water may be present in an amount sufficient to bring about both the hydrolysis of the polysiloxane and the subsequent condensation of the silanols.
• Non-limiting sources of water may include atmospheric humidity and adsorbed moisture on the pigment or aggregate material. Additional water may be added, for example, to accelerate cure depending on ambient conditions, such as the use of the coating and flooring composition in arid environments.
• embodiments of the epoxy-polysiloxane composition may comprise up to a stoichiometric amount of water to facilitate hydrolysis.
• Compositions that are prepared without added water may not contain the amount of moisture needed for the hydrolysis and condensation reactions, and may therefore produce a composition product having an insufficient degree of ultraviolet, corrosion and chemical resistance.
• Compositions that are prepared using greater than about two percent by weight water tend to hydrolyze and polymerize to form an undesirable gel before application.
• the epoxy-polysiloxane composition may be prepared using approximately 1% by weight water.
• water may be added to the epoxy-polysiloxane resin.
• Other sources of water may include trace amounts present in the epoxide resin, cure system, thinning solvent, or other ingredients. Regardless of its source, the total amount of water used should be the stoichiometric amount needed to facilitate the hydrolysis reaction. Water exceeding the stoichiometric amount may be undesirable since excess water may act to reduce the surface gloss of the finally-cured composition product.
• the present disclosure provides for an epoxy-polysiloxane polymer coating composition
• an epoxy-polysiloxane polymer coating composition comprising water, from 20% to 80% by weight of a polysiloxane having the general formula I
• R ls R 2 and n are as described herein, from 20%> to 80%> by weight of a non- aromatic epoxide resin having more than one 1 ,2-epoxide group per molecule and with an epoxide equivalent weight of from 100 to 5,000, up to 15% by weight of a cure accelerator comprising a tin organometallic catalyst in the form of an octanoates, a dodecanoate, or a naphthanate, up to 15% by weight of a flexible epoxy resin based on the glycidyl ether of castor oil having an epoxide equivalent weight of 200 to 1,000, and from 5% to 40% by weight of a cure system comprising a blend of at least one trialkoxy functional aminosilane and at least one amino functional polysiloxane resin, wherein the blend has an average alkoxy functionality value ranging from 2.0 to 2.8, and is added in an amount sufficient to provide an amine equivalent to epoxide equivalent ratio of from 0.7: 1.0 to
• each R5, R 6 , and R 7 are independently as described herein and the amino functional polysiloxane resin may have the structure where each Rg is a difunctional organic radical selected from the structures described herein and each R 9 is independently selected from aryl, phenyl, (Ci-C4)alkyl, (C ⁇ - C 4 )alkoxy, and -OSi(R9) 2 RgNH 2 , where m is selected so that the blend has an amine equivalent weight of 1 12 to 250 g/NH.
• the at least one amino functional polysiloxane resin may be an amino functional phenyl methyl polysiloxane resin, as described herein.
• Epoxy-polysiloxane compositions according to various embodiments of the present disclosure are generally low in viscosity and can be spray applied without the addition of a solvent.
• organic solvents may be added to improve atomization and application with electrostatic spray equipment or to improve flow, leveling and/or appearance when applied by brush, roller, or standard air and airless spray equipment.
• Exemplary solvents useful for this purpose include, but are not limited to, esters, ethers, alcohols, ketones, glycols and the like.
• the amount of solvent added to compositions of the present disclosure may be limited by government regulation under the Clean Air Act to approximately 420 grams solvent per liter of the composition.
• Certain embodiment of the epoxy-polysiloxane compositions of the present disclosure may be supplied as a two-package system, for example, in moisture proof containers.
• the first package may contain the epoxy resin, polysiloxane resin, any pigment and/or aggregate ingredient, additives and/or solvent if desired.
• the second package may contain the cure system, comprising one or more of the dialkoxy aminosilanes, trialkoxy aminosilanes, amino functional polysiloxanes, and/or optionally catalysts or accelerating agents.
• Certain embodiments of the coating compositions of the present disclosure may be supplied as 3 -package systems where the pigment and/or aggregate are supplied in a separate package e.g. for a
• Epoxy-polysiloxane compositions according to the present disclosure can be applied and fully cure at ambient temperature conditions in the range of from - 6° C to 50° C. At temperatures below -18° C cure may be slowed. However, the coating compositions of various embodiments of the present disclosure may be applied under bake or cure temperatures up to 40° C to 120° C.
• the embodiments of the epoxy-polysiloxane coating compositions described herein are cured by: (1) the reaction of the epoxy resin with the cure system to form epoxy polymer chains; (2) the hydrolytic polycondensation of the polysiloxane ingredient to produce alcohol and polysiloxane polymer; and (3) the copolymerization of the epoxy polymer chains with the polysiloxane polymer to form a fully-cured epoxy-polysiloxane polymer composition.
• the epoxy-polysiloxane coating composition may exist as a uniformly dispersed arrangement of linear epoxy chain fragments that are cross-linked with a continuous polysiloxane polymer chain, thereby forming a non-interpenetrating polymer network (IPN) chemical structure that has substantial advantages over conventional epoxy systems.
• IPN non-interpenetrating polymer network
• the proportion of curing composition to resin component may vary over a wide range.
• the epoxy resin may be cured with sufficient cure system where amine hydrogens react with the epoxide group of the epoxy resin to form epoxy chain polymers and to react with the polysiloxane to form polysiloxane polymers, where the epoxy chain polymers and polysiloxane polymers may copolymerize to form the cured cross-linked epoxy polysiloxane polymer composition.
• the epoxy resin component may be cured with sufficient cure system to provide from 0.7 to 1.3 amine equivalent weight per 1.0 epoxide equivalent weight. In other embodiments, the epoxy resin component may be cured with sufficient cure system to provide from 0.95 to 1.05 amine equivalent weight per 1.0 epoxide equivalent weight.
• the silane moiety of the cure system condenses with the polysiloxane ingredient, and the epoxy resin undergoes chain extension with by reaction with the amino groups pendent from the polysiloxane to form a fully-cured epoxy-polysiloxane polymer composition.
• the epoxy resin functions as a cross-linking enhancer that adds to the cross-link density of the composition without diminishing the beneficial features of the polysiloxane.
• the chemical and physical properties of the epoxy- polysiloxane composition of the present disclosure may be affected by judicious choice of epoxy resin, polysiloxane, cure system and other optional components, such as pigment or aggregate components.
• Various embodiments of the epoxy- polysiloxane coating composition that can be prepared by combining the components as described herein displays improved resistance to caustic, is weatherable, corrosion resistance, flexibility, allows infinite recoatability, provides abrasion resistance better than conventional epoxy-polysiloxane coating compositions.
• Epoxy-polysiloxane coating compositions of the present disclosure may exhibit an unexpected and surprising improvement in chemical corrosion and weathering resistance as well as high tensile and compressive strength, flexibility, and excellent impact and abrasion resistance.
• Certain embodiments of the present disclosure may also include a coated substrate comprising a substrate having at least one surface coated with a coating composition according to an embodiment described herein.
• Coating compositions of the present disclosure may be applied to a desired substrate surface to protect it from weathering, impact, and exposure to corrosion and/or chemical(s).
• Illustrative substrates that may be treated using the coating compositions described herein include, but are not limited to, wood, plastic, concrete, vitreous surfaces, and metallic surfaces.
• Coating compositions according to the embodiments described herein may find use as a top coating disposed either directly onto the substrate surface itself or disposed onto one or more prior or other underlying coating, e.g., an inorganic or organic primer coating, disposed on the substrate surface to achieve a desired purpose.
• Embodiments of the present disclosure provide a method for protecting a surface of a substrate from the undesired effects of one or more of chemical(s), corrosion, and weather by coating at least one surface of the substrate, such as a substrate as described herein, with a coating composition prepared by a method comprising forming a resin component, adding a cure system to the resin component to form a fully cured epoxy-modified polysiloxane coating composition, and applying the coating composition to the at least one surface of the substrate to be protected before the coating composition becomes fully cured.
• the resin component may be formed by combining water, a polysiloxane having formula I, and a non-aromatic epoxide resin having more than one 1 ,2-epoxide group per molecule with an epoxide equivalent weight in the range of from 100 to 5,000.
• the cure system may be as described herein and in one embodiment may comprise a blend of at least one trialkoxy functional aminosilane and at least one amino functional polysiloxane resin and optionally a cure accelerator comprising at least one metal catalyst, where the blend has an average alkoxy functionality value ranging from 2.2 to 2.8.
• the blend of the cure system may have an amine equivalent weight ranging from 112 to 250 g/NH.
• the resin component may further include a flexible epoxy resin based on a glycidyl ether of castor oil having an epoxide equivalent weight in the range of 200 to 1,000.
• Coating compositions of the various embodiments described herein can be applied to a surface to be treated by conventional techniques such as spraying or brushing or the like, and are usually applied in films of from 50 to 250 micrometers in thickness, or in some embodiments up to 1.5 millimeters in thickness. If necessary, multiple layers of the coating composition may be applied to the surface to be protected. For example, for use with a wooden substrate, such as in the furniture industry, the coating may be applied with a dry film thickness of 75 to 125 micrometers to provide a desired degree of protection to the underlying surface. On other surface structures, coatings of appropriate thickness may be applied to provide the desired level of protection.
• the coating composition once applied to the at least one surface of the substrate may be allowed to cure at ambient temperature until fully cured or, alternatively, may be cured at an elevated temperature, from ambient temperature up to 150°C - 200° C, for example, by placing the coated substrate in a drying or curing oven.
• the substrate may be removed from the oven after complete curing of the coating composition or after partial curing of the coating composition, after which the coating composition may continue to cure on the substrate at ambient temperature until complete cure is attained.
• exemplary epoxy siloxane coating systems according to the present disclosure are formulated and tested for weatherability, durability, corrosion resistance and chemical resistance and compared with comparative coating systems.
• the resin component for the formulation were prepared as follows.
• a cycloaliphatic epoxy resin (Adeka EP-4080E, 256.3 g, commercially available from Adeka Corporation, Tokyo, Japan) was weight into a 1 liter stainless steel mixing vessel and placed under a Hockmeyer mixer fitted with a Cowles blade.
• Surfactant (RHODAFAC® RE 610, 4.2 g, commercially available from Solvay, Rhodia Group, New Brunswick, NJ) and defoamer (Foamtrol, 4.4 g, commercially available from Munzing NA, Bloomfield, NJ) were added to the mixing vessel while mixing at low speed followed by addition of a thixotrope (CRAYVALLAC® extra, 16.3 g, commercially available from Palmer Holland Inc.
• CRAYVALLAC® extra 16.3 g, commercially available from Palmer Holland Inc.
• HALOX® SZP-391 JM 55.5 g, commercially available from Halox, Hammond, IN
• silicone resin DC-3074, 384.8 g, commercially available from Dow Corning, Midland, MI
• the resin component for the formulation were prepared as follows.
• a cycloaliphatic epoxy resin (Adeka EP-4080E, 570.3 g, commercially available from Adeka Corporation, Tokyo, Japan) was weight into a 1 liter stainless steel mixing vessel and placed under a Hockmeyer mixer fitted with a Cowles blade.
• Surfactant RHODAFAC® RE 610, 4.2 g, commercially available from Solvay, Rhodia Group, New Brunswick, NJ
• defoamer Foamtrol, 4.4 g, commercially available from Munzing NA, Bloomfield, NJ
• CRAYVALLAC® extra 16.3 g, commercially available from Palmer Holland Inc. North Olmsted, OH.
• the batch was then dispersed at high speed while bringing the temperature of the mixture to 71°C (160°F). These conditions were held for 30 minutes.
• the batch was then cooled to 49°C (120°F) while stirring at slow speed.
• Titanium dioxide (TIOXIDE® TR60, 401.8 g, commercially available from Huntsman, The Woodlands, TX) at a rate that is sufficient to avoid agglomeration.
• TX Titanium dioxide
• the batch was mixed at high speed for 20 minutes until a 6 Hegman grind was obtained.
• the remaining components including a corrosion inhibitor (HALOX® SZP-391 JM, 55.5 g, commercially available from Halox, Hammond, IN); silicone resin (DC-3074, 113.0 g, commercially available from Dow Corning, Midland, MI); a flexible epoxy resin (HELOXYTM 505, 70.0 g, commercially available from Momentive Specialty
• the resin component for the formulation were prepared as follows.
• a cycloaliphatic epoxy resin (Adeka EP-4080E, 355.4 g, commercially available from Adeka Corporation, Tokyo, Japan) was weight into a 1 liter stainless steel mixing vessel and placed under a Hockmeyer mixer fitted with a Cowles blade.
• Surfactant (RHODAFAC® RE610, 5.0 g, commercially available from Solvay, Rhodia Group, New Brunswick, NJ) and defoamer (Foamtrol, 5.3 g, commercially available from Munzing NA, Bloomfield, NJ) were added to the mixing vessel while mixing at low speed followed by addition of a thixotrope (DISPARLON® 6500, 7.7 g, commercially available from King Industries, Norwalk, CT). The batch was then dispersed at high speed while bringing the temperature of the mixture to 71°C (160°F). These conditions were held for 30 minutes. The batch was then cooled to 49°C (120°F) while stirring at slow speed.
• a thixotrope (DISPARLON® 6500, 7.7 g, commercially available from King Industries, Norwalk, CT).
• Titanium dioxide (TIOXIDE® TR60, 401.4 g, commercially available from Huntsman, The Woodlands, TX) at a rate that is sufficient to avoid agglomeration. After addition of the Ti0 2 , the batch was mixed at high speed for 20 minutes until a 6 Hegman grind was obtained.
• the remaining components including a silicone resin (DC-3074, 402.6 g, commercially available from Dow Corning, Midland, MI); a HALS light stabilizer (TINUVIN® 292, 22.9 g, commercially available from BASF, Ludwigshafen, Germany); and silicone additives DC-57 (4.1 g, commercially available from Dow Corning, Midland, MI) and BYK- 36 IN (11.0 g, commercially available from BYK, Wallingford, CT) were then added to the mixture and the batch was mixed until uniform and then poured into a 1 quart can for storage as comparative Resin Component C.
• the components and weights are presented in Table 1.
• cure systems 1, 2, 3 4, 5, and 6 according to embodiments of the present disclosure were prepared, along with comparative cure systems 7 and 8.
• the components and amounts for each cure system is presented in Table 2.
• the components were weighted into a 1 pint container, sealed and placed on a shaker for 5 minutes to provide cure systems 1, 2, 3, 4, 5, and 6 and comparative cure systems 7 and 8.
• Cure system 1 was prepared by combining a dialkoxy functional aminosilane (DYNASYLAN® 1505, 93.2 g, commercially available from Evonik Degussa Corp, USA) with a metal catalyst cure accelerator (T-l, dibutyltin diacetate, 6.8 g, commercially available from Air Products, AUentown, PA).
• the resulting cure system had an average alkoxy functionality of 2.0, an average alkoxy weight % of 34.7% and an average amine equivalent weight of 87.6 g/NH.
• Cure system 2 was prepared by combining a dialkoxy functional aminosilane (DYNASYLAN® 1505, 25.0 g, commercially available from Evonik Degussa Corp, USA) and a trialkoxy functional aminosilane (SILQUEST® Al 110, 68.2 g, commercially available from Crompton OSi Specialties, South Charleston, WV) with a metal catalyst cure accelerator (T-l, dibutyltin diacetate, 6.8 g, commercially available from Air Products, Allentown, PA).
• T-l dibutyltin diacetate, 6.8 g, commercially available from Air Products, Allentown, PA.
• the resulting cure system had an average alkoxy functionality of 2.73, an average alkoxy weight % of 44.6% and an average amine equivalent weight of 94.3 g/NH.
• Cure system 3 was prepared by combining a dialkoxy functional aminosilane (DYNASYLAN® 1505, 67.3 g, commercially available from Evonik Degussa Corp, USA) and a trialkoxy functional aminosilane (SILQUEST® Al 110, 25.9 g, commercially available from Crompton OSi Specialties, South Charleston, WV) with a metal catalyst cure accelerator (T-l, dibutyltin diacetate, 6.8 g, commercially available from Air Products, Allentown, PA).
• T-l dibutyltin diacetate, 6.8 g, commercially available from Air Products, Allentown, PA.
• the resulting cure system had an average alkoxy functionality of 2.28, an average alkoxy weight % of 41.6% and an average amine equivalent weight of 90.0 g/NH.
• Cure system 4 was prepared by combining a trialkoxy functional aminosilane (SILQUEST® Al 110, 23.2 g, commercially available from Crompton OSi Specialties, South Charleston, WV) and an amino functional polysiloxane resin (SILRES® HP-2000, 70.0 g, commercially available from Wacker Chemical Corporation, Adrian, MI) with a metal catalyst cure accelerator (T-l, dibutyltin diacetate, 6.8 g, commercially available from Air Products, Allentown, PA).
• the resulting cure system had an average alkoxy functionality of 2.8, an average alkoxy weight % of 16.9% and an average amine equivalent weight of 183.8 g/NH.
• Cure system 5 was prepared by combining a trialkoxy functional aminosilane (SILQUEST® Al 110, 73.2 g, commercially available from Crompton OSi Specialties, South Charleston, WV) and an amino functional polysiloxane resin (DOW CORNING® 3055 Resin, 20.0 g, commercially available from Dow Corning Corporation, Midland, MI) with a metal catalyst cure accelerator (T-l, dibutyltin diacetate, 6.8 g, commercially available from Air Products, Allentown, PA).
• the resulting cure system had an average alkoxy functionality of 2.78, an average alkoxy weight % of 37.8% and an average amine equivalent weight of 112.2 g/NH.
• Cure system 6 was prepared by combining a trialkoxy functional aminosilane (SILQUEST® Al 110, 24.0 g, commercially available from Crompton OSi Specialties, South Charleston, WV) and an amino functional polysiloxane resin (DOW CORNING® 3055 Resin, 69.2 g, commercially available from Dow Corning Corporation, Midland, MI) with a metal catalyst cure accelerator (T-l, dibutyltin diacetate, 6.8 g, commercially available from Air Products, Allentown, PA).
• the resulting cure system had an average alkoxy functionality of 2.26, an average alkoxy weight % of 12.3% and an average amine equivalent weight of 169.8 g/NH.
• Comparative cure system 7 was prepared by combining an amino functional polysiloxane resin (DOW CORNING® 3055 Resin, 96.0 g, commercially available from Dow Corning Corporation, Midland, MI) with a metal catalyst cure accelerator (T-l, dibutyltin diacetate, 4.0 g, commercially available from Air Products, Allentown, PA).
• the resulting cure system had an average alkoxy functionality of less than 0.1, an average alkoxy weight % of less than 0.1% and an average amine equivalent weight of 255.8 g/NH.
• Comparative cure system 8 was prepared by combining a trialkoxy functional aminosilane (SILQUEST® Al 100, 93.2 g, commercially available from Crompton OSi Specialties, South Charleston, WV) with a metal catalyst cure accelerator (T-1, dibutyltin diacetate, 6.8 g, commercially available from Air Products, Allentown, PA).
• SILQUEST® Al 100 93.2 g
• metal catalyst cure accelerator T-1, dibutyltin diacetate, 6.8 g, commercially available from Air Products, Allentown, PA.
• the resulting cure system had an average alkoxy functionality of 3.0, an average alkoxy weight % of 50.1% and an average amine equivalent weight of 109.8 g/NH.
• Coating formulations according to certain embodiments of the present invention were prepared using a resin component (Examples 1 and 2 and comparative resin in Example 3) and cure system (Example 4).
• a resin component Examples 1 and 2 and comparative resin in Example 3
• cure system Example 4
• Resin A 100 g was combined with Cure System 7 (26.6 g).
• the coating formulations are mixed with a stoichiometric ratio of amine equivalents to epoxy equivalents as follows: 0.96: 1.00, 0.96:1.00, 0.96: 1.00, 1.00: 1.00 1.03: 1.00, 1.00: 1.00, 1.00: 1.00, and 1.00: 1.00 for coating formulations 1, 2, 3, 4, 5, 6, 7, and 8, respectively.
• the resin component and the cure system were weighed into a container and stirred with a metal spatula until well mixed to provide a coating composition.
• the resulting coating composition was sprayed onto steel panels using a DEVILBISS® spray gun and the coating allowed to cure to hardness (ASTM
• the panels coated with the compositions of the coating formulations were tested for percent elongation (conical mandrel, ASTM D522).
• the epoxy siloxane formulations (6 mils) were applied over 3 mils of a zinc rich epoxy primer and tested for resistance to salt spray/fog (ASTM Bl 17) over 5000 hours.
• the panels were analyzed after 5000 hours for face blister (ASTM D714), face rusting (ASTM D1654), and scribe creepage (ASTM D1654).
• epoxy siloxane coating compositions made according to the present disclosure display improved flexibility as measured by conical mandrel elongation, particularly after aging, than the comparative prior art composition. Weatherability and corrosion resistance tests showed that the epoxy siloxane coatings displayed improved properties over the comparative prior art composition.

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• Wood Science & Technology (AREA)
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• Paints Or Removers (AREA)
• Aftertreatments Of Artificial And Natural Stones (AREA)
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