Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
  • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
  • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4202—Two or more polyesters of different physical or chemical nature
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
  • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/06—Polyurethanes from polyesters
• • C—CHEMISTRY; METALLURGY
  • C14—SKINS; HIDES; PELTS; LEATHER
  • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
  • C14C11/00—Surface finishing of leather
  • C14C11/003—Surface finishing of leather using macromolecular compounds
  • C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen

Definitions

• the present invention relates generally to solvent-based flexible polymer coatings, and more specifically to coatings having a first polyester polyol having low functionality, a second polyester polyol having a functionality higher than the first polyester polyol, and an isocyanate.
• the present invention further relates to flexible substrates coated with these coatings.
• Two-component (“2K”) polyurethane coatings can be effective in protecting substrates from moisture, abrasion, corrosion, ultraviolet radiation and/or object impact.
• Polyurethane coatings are typically durable and have high tensile strength, and good chemical and solvent resistance.
• a polyurethane coating that can conform to a flexible substrate without cracking as the substrate is flexed is desired. .
• the present invention provides coating compositions comprising a first component comprising a first polyester polyol having a first functionality and a second polyester polyol having a second functionality, wherein the second functionality is greater than the first functionality, and a second component comprising an isocyanate, wherein the NCO:OH ratio of the coating is 1 :1 or greater.
• the present invention also provides flexible substrates coated with one or more of the coatings described above.
• the present invention is directed to a 2K solvent-based polymer coating composition.
• the first component comprises a first polyester polyol having a first functionality and a second polyester polypi having a second functionality, wherein the second functionality is greater than the first functionality.
• “Functionality” refers to the number of hydroxyl groups per molecule of the polyol.
• Polyol refers to polyol a ⁇ d/or polyol composition.
• the second component comprises an isocyanate.
• the NCO:OH ratio of the coating composition is 1 :1 or greater.
• NCO:OH ratio refers to the ratio of isocyanate groups to hydroxyl groups in the coating composition. It will be appreciated that the two components, when combined, produce a polyurethane coating.
• the difference between the hydroxyl numbers of the first polyester polyol and the second polyester polyol is at least 10. In another embodiment, the difference between the hydroxyl numbers of the first polyester polyol and the second polyester polyol is at least 20.
• the first polyester polyol of the first component has a low functionality. As used herein, the term "low functionality" and like terms mean that the polyester polyol has a hydroxyl number of less than 65, such as less than 60. A suitable low functionality polyester polyol has a hydroxyl number of from 40 to 60. In one embodiment, the first polyester polyol has a hydroxyl number of from 54 to 58.
• the low functionality of the first polyester polyol results in increased flexibility and a lower tendency to form crosslinks when reacted with an isocyanate in a coating.
• Any polyester polyol having a low functionality can be used in the present invention.
• the first polyester polyol can be the reaction product of a carboxylic acid and polyalcohol; such a product is commercially available as DESMOPHEN 1625A from Bayer Corporation.
• the second polyester polyol of the first component has a medium functionality.
• the term "medium functionality" and . like terms mean that the polyester polyol has a hydroxyl number of from 90 to 125.
• the second polyester polyol has a hydroxyl number of from 104 to 118.
• the medium functionality of the second polyester polyol typically increases the crosslink density of the coating, resulting in increased coating hardness and improved chemical resistance.
• Any polyester polyol having medium functionality can be used in the present invention.
• the second polyester polyol can be the reaction product of a polyol, an aromatic dicarboxylic acid and/or anhydride, and/or an aliphatic dicarboxylic acid and/or anhydride.
• the second polyester polyol can be the reaction product of isophthalic acid, phthalic anhydride, adipic acid, trimethylol propane, and 1 ,6 hexanediol; such a product is commercially available as DESMOPHEN 670 A-80 from Bayer Corporation.
• either one or both of the polyester polyols specifically exclude neopentyl glycol. .
• the first and second polyester polyols can be combined together to form a polyester polyol blend in the first component.
• the ratio of the first polyester polyol to the second polyester polyol in the polyester polyol blend is from 5:1 to 8:1 :
• the ratio of the first polyester polyol to the second polyester polyol in the polyester polyol blend is from 6.5:1 to 7.5:1.
• the amount of the first polyester polyol and the amount of the second polyester polyol in the blend can be selected to optimize certain features of each polyol. For example, an increased amount of the first polyester polyol results in increased flexibility, while an increased amount of the second polyester polyol results in increased hardness and chemical resistance.
• the first polyester polyol, the second polyester polyol and an acrylic polyol can be combined to produce a first component.
• An acrylic polyol can be added to the polyester polyol blend in the first component in order to further increase the strength of the coating.
• the acrylic polyol is a styrenated acrylic polyol.
• acrylic polyols examples include copolymers of methyl (meth)acrylate with hydroxy functional (meth)acrylate monomers, copolymers of isobornyl (meth)acrylate, ethyl (meth)acrylate copolymers, hydroxyl-ethyl (meth)acrylate, and hydroxyl-propyl methacrylate.
• the acrylic polyols can have functionality or be substantially nonfunctional.
• acrylic polyols used in the present invention can have a hydroxyl number of at least.50.
• acrylic polyols, such as styrenated acrylic polyols can be added to the first component in an amount up to 40 weight percent. - . ' . ⁇ ' '.
• the acrylic polyols can be provided in any amount desired to provide sufficient strength to the coating.
• the acrylic polyols will typically crosslink with isocyanate in the final coating, thereby increasing the crosslink density and hardness of the coating. Since increased amounts of acrylic polyol may increase the strength of the coating, but decrease the amount of flexibility, the desired amount of acrylic polyol must be determined based upon the needs of the user.
• the second component of the two-component coating comprises an isocyanate.
• isocyanate and like terms include isocyanate, polyisocyanates, and cyclic trir ⁇ ers of polyisocyanates.
• Suitable isocyanates include isophorone diisocyanate, 1 ,3- or 1 ,4-cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, tetraalkylxyene diisocyanates such as m- tetramethyl xylene diisocyanate, p-phenylene diisocyanate, polymethylene polyphenyl isocyanate, diphenylmethylene diisocyanate, 2,6-toluene diisocyanate, diahisdine diisocyanate, bitolylene diisocyanate, naphthalene-1 ,4-diisocyanate, bis(4-isocyanato phenyl)methane, 4,4'-diphenylpropane diisocyanate, hexamethylene diisocyanate, and, where appropriate, trimers thereof, such as an isocyanate trimer of hexamethylene diiso
• the amount of polyester polyol blend, and acrylic polyol if used, in the first component and the amount of isocyanate in the second component can be selected such that the ratio of isocyanate groups to hydroxy! groups, i.e. NCO:OH, will produce a coating composition having an NCO:OH ratio of 1 :1 or greater.
• NCO:OH ratio of 1 :1 or greater.
• "Greater than 1 :1", “1 :1 or greater”, and like terms mean that the NCO component will be higher than the OH component.
• the NCO:OH ratio is greater than 1 :1.
• the NCO:OH ratio is at least 1.2:1 , such as greater than 1.2:1.
• the NCO:OH ratio is at least 1.4:1 , such as greater than 1.4:1. In certain embodiments, the NCO:OH ratio is 1.7:1 or greater, such as 2:1 or greater. In general, the NCO:OH ratio can be 3:1 or lower, such as 2.5:1 or lower. It is surprising that the coatings of certain embodiments of the present invention, such as those having an NCO:OH ratio of . greater than 1.2:1 , exhibit improved flexibility. Conventional teachings indicate that coatings having higher NCO:OH ratios exhibit increased rigidity. In traditional polyurethane compositions, excess isocyanate groups (NCO groups) typically form side reactions with available amines, water and/or alcohols, and become rigid.
• NCO groups excess isocyanate groups
• a coating having a relatively high NCO:OH ratio as compared to traditional coatings has improved flexibility. It is further surprising that coatings according to certain embodiments of the present invention wherein the NCO:OH ratio is 1.2:1 or greater, such as 1.4:1 or greater, may have a Young's modulus and/or tensile strength typical for coatings having a lower NCO:OH ratio.
• Various additives can be added to the coating in accordance with the present invention. Typically, these additives are added to the first component, but could be added to either or both components based upon the needs of the user.
• suitable additives include solvents such as acetates, alcohols, ketones, glycols, ethers, aliphatics, cycloaliphatics and aromatics.
• solvents such as acetates, alcohols, ketones, glycols, ethers, aliphatics, cycloaliphatics and aromatics.
• acetates include ethyl acetate, butyl acetate, and glycol acetate.
• ketones include methyl ethyl ketone and methyl-N-amyl ketone.
• aromatics are toluene, naphthalene and xylene.
• one or more solvents are added to each of the first component and the second component.
• Suitable solvent blends can include, for example, one or more acetates, propanol and its derivatives, one or more ketones, one or more alcohols and/or one or more aromatics.
• Other suitable additives include texture-enhancing additives such as silica or a paraffin wax to improve the surface feel of the coating and to enhance stain resistance.
• Other suitable additives can include those standard in the art, including but not limited to plasticizers, leveling agents, adhesion promoters, colorants, rheology modifiers, ultra-violet (UV) absorbers, and hindered amine light . stabilizers (HALS).
• the coatings of the present invention can also include a colorant.
• a colorant means any substance that imparts color and/or other opacity and/or other visual effect to the composition.
• the colorant can be added to the coating in any suitable form, such as discrete particles, dispersions, solutions and/or flakes. A single colorant or a mixture of two or more colorants can be used in the coatings of the present invention.
• Example colorants include pigments, dyes and tints, such as those ' used in the paint industry and/or listed in the Dry Color Manufacturers Association (DCMA), as well as special effect compositions.
• a colorant may include, for example, a finely divided solid powder that is insoluble but wettable under the conditions of use.
• a colorant can be organic or inorganic and can be agglomerated or non-agglomerated. Colorants can be incorporated into the coatings by use of a grind vehicle, such as an acrylic grind vehicle, the use of which will be familiar to one skilled in the art.
• Example pigments and/or pigment compositions include, but are not limited to, carbazole dioxazine crude pigment, azo, monoazo, disazo, naphthol AS, salt-type (lakes), benzimidazolone, condensation, metal complex, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigments, diketo pyrrolo pyrrole red (“DPPBO red”), titanium dioxide, carbon black and mixtures thereof.
• DPPBO red diketo pyrrolo pyrrole red
• Example dyes include, but are not limited to, those that are solvent and/or aqueous based such as pthalo green or blue, iron oxide, bismuth vanadate, anthraquinone, perylene, aluminum and quinacridone.
• Example tints include, but are. not limited to,, pigments dispersed in water-based or water miscible carriers such as AQUA-CHEM 896 commercially available from Degussa, Inc., CHARISMA COLORANTS arid MAXiTONER INDUSTRIAL COLORANTS commercially available from Accurate Dispersions, division of Eastman Chemical, Inc.
• the colorant can be in the form of a dispersion including, but not limited to, a nanoparticle dispersion.
• Nanoparticle dispersions can include one or more highly dispersed nanoparticle colorants and/or colorant particles that produce a desired visible color and/or opacity and/or visual effect.
• Nanoparticle dispersions can include colorants such as pigments or dyes having a particle size of less than 150 nm, such as less than 70 nm, or less than 30 nm..
• Nanoparticles can be produced by. milling stock organic or inorganic pigments with grinding media having a particle size of less than 0.5 mm.
• Example nanoparticle ! dispersions and methods for making them are identified in U.S. Patent No.
• Nanoparticle dispersions can also be produced by crystallization/ precipitation, gas phase condensation, and chemical attrition (i.e., partial dissolution).
• a dispersion of resin-coated nanoparticles can be used.
• a "dispersion of resin-coated nanoparticles" refers to a continuous phase in which is dispersed discreet "composite microparticles” that comprise a nanoparticle and a resin coating on the nanoparticle.
• Example dispersions of resin-coated nanoparticles and methods for making them are identified in U.S. Application No.
• Example special effect compositions that may be used in the coating of the present invention include pigments and/or compositions that produce one or more appearance effects such as reflectance, pearlescence, metallic sheen, phosphorescence, fluorescence, photochromism, photosensitivity, thermochromism, goniochromism and/or color-change. Additional special effect compositions can provide other perceptible properties, such as opacity or texture.
• special effect compositions can produce a color shift, such that the color of the coating changes when the coating is viewed at different angles.
• Example color effect compositions are identified in U.S. Application Publication No. 2003/0125416, incorporated herein by reference.
• Additional color effect compositions can include transparent coated mica and/or synthetic mica, coated silica, coated alumina, a transparent liquid crystal pigment, a liquid crystal coating, and/or any composition wherein interference results from a refractive index differential within the, material and not because of the refractive index differential between the surface of the material and the air.
• a photosensitive composition and/or photochromic composition which reversibly alters its color when exposed to one or more light sources, can be used in the coating of the present invention.
• Photochromic and/or photosensitive compositions can be activated by exposure to radiation of a specified wavelength. When the composition becomes excited, the- molecular structure is changed and the altered structure exhibits a new color that is different from the original color of the composition. When the exposure to radiation is removed, the photochromic and/or photosensitive composition can return to a state of rest, in which the original color of the composition returns.
• the photochromic and/or photosensitive composition can be coloriess in a non-excited state and exhibit a color in an excited state. Full color- change can appear within milliseconds to several minutes, such as from 20 seconds to 60 seconds.
• Example photochromic and/or photosensitive compositions include photochromic dyes:
• the photosensitive composition and/or photochromic composition can be associated with and/or at least partially bound to, such as by covalent bonding, a polymer and/or polymeric materials of a polymerizable component.
• the photosensitive composition and/or photochromic composition associated with and/or at least partially bound to a polymer and/or polymerizable component in accordance with a non-limiting embodiment of the present invention have minimal migration out of the coating.
• Example photosensitive compositions and/or photochromic compositions and methods for making them are identified in U.S. Application Serial No. 10/892,919 filed July 16, 2004, incorporated herein by reference. .
• the colorant can be present in the coating composition in any amount sufficient to impart the desired visual and/or color effect.
• the colorant may comprise from 1 to 65 weight percent of the present compositions, such as from 3 to 40 weight percent or 5 to 35 weight percent, with weight percent based on the total weight of the compositions.
• the coating compositions according to the present invention are suitable for producing any type of coating, and are particularly suitable as topcoats on substrates.
• the coating of the present invention can be used as a single application coating or monocoat.
• the coating can be used as one or more of a multiple application coating in which each coat may contain the same or different additives.
• the coatings of the present invention can be used alone or in combination with other coatings.
• the present invention is also directed to a coated flexible substrate having a coating deposited on at least a portion of the substrate.
• the coating can be any of the coatings described above.
• the coating compositions obtained by mixing the two components has a limited potlife and can be applied to flexible substrates in any known manner such as brushing, spraying, rolling, roll coating, slot coating and/or dipping.
• the curing of these coatings can comprise a flash at ambient or elevated temperatures followed by a thermal bake in order to obtain optimum properties.
• the coatings of the present invention are typically deposited on the flexible substrate to a thickness of from 0.1 to 3 mils. In one embodiment, the coating is deposited to a thickness of from 0.5 to 1.0 mils.
• the term “flexible substrate” refers to a substrate that can undergo mechanical stresses, such as bending or stretching and the like, without significant irreversible change.
• the flexible substrates are compressible substrates.
• “Compressible substrate” and like terms refer to a substrate capable of undergoing a compressive deformation and returning to substantially the same shape once the compressive deformation has ⁇ ceased.
• the term “compressive deformation” and like terms mean a mechanical stress that reduces the volume at least temporarily of a substrate in at least one direction.
• flexible substrates includes non-rigid substrates, such as thermoplastic urethane (TPU), synthetic leather, natural leather, finished natural leather, finished synthetic leather, foam, polymeric bladders filled with air, liquid, and/or plasma, urethane elastomers, synthetic textiles and natural textiles.
• TPU thermoplastic urethane
• Fraam can be a polymeric or natural material comprising open cell foam and/or closed cell foam.
• Open cell foam means that the foam comprises a plurality of . interconnected air chambers;
• closed cell foam means that the foam comprises discrete closed pores.
• Example foams include but are not limited to polystyrene foams, polyvinyl acetate and/or copolymers; polyvinyl chloride and/or copolymers; poly(meth)acryNmide foams, polyvinylchlpride foams, polyurethane foams, and pblyolefinic foams and polyolefin blends.
• Polyolefinic foams include but are not limited to polypropylene foams, polyethylene foams and ethylene vinyl acetate (“EVA”) foams.
• EVA foam can include flat sheets or slabs or molded EVA foams, such as shoe midsoles. Different types of EVA foam can have different types of surface porosity.
• Molded EVA can comprise a dense surface or "skin", whereas flat sheets or slabs can exhibit a porous surface.
• "Textiles” can include fabric, mesh, netting, cord, and the like, and comprises, for example, canvas, nylon, cotton, polyester, and the like. These lists are not meant to be exhaustive.
• the flexible coatings of the present invention have a wide variety of applications.
• the flexible substrate can be part of sporting equipment or apparel, such as athletic shoes, balls, bags, clothing and the like; an automotive interior component; a motorcycle component; household furnishings and decorations and the like. Surprisingly, when the coatings described herein were applied to rigid substrates and subjected to cure, the coating remained tacky and was readily marred.
• Coatings of the present invention exhibit flexibility such that they are suitable for application onto flexible substrates.
• the present coatings do not readily crack when the substrates are manually flexed.
• Another benefit of the coatings of the present invention is that the coatings do not crack or peel when restrained in a flexed position for an extended period of time, such as up to three months.
• the coatings described herein have an elongation to break of at least 50 percent, such as at least 100 percent.
• the coating has an NCO:OH ratio of 1.4:1 and an elongation to break of greater than 100 percent.
• a flexible substrate coated with a coating of the present invention has an elongation to break of at least 197 percent.
• the term "elongation to break” means the percent strain in the tensile mode at the point at which specimen failure is observed. Higher elongation to break indicates more elongation of the specimen. Elongation to break can be determined, for example, using an lnstron Mini 44 Unit equipped with a 5ON load cell.
• CAB-531-1 and CAB-551-0.01 - cellulose acetate butyrate which are commercially available from Eastman Chemical.
• BAYSILONE OL17 - flow control additive which is commercially available from Bayer Corporation.
• Solvents resins/additive solutions - toluene, n-butyl acetate, naphthalene, methyl ether propylene glycol acetate and mineral spirits. • . • .
• polyester polyol (a) and polyester polyol (b) were mixed at constant low speed using a rotary stirrer at ambient temperature. Subsequently, N-butyl acetate, 10% tin catalyst solution (90%-methyl amyl ketone) and polysiloxane additive were added with agitation to the resin solution.
• UV absorber/stabilizer solution and 2.6 g of the final solvent blend generally consisting of 11 to 12% methyl ethyl ketone, 70 to 75% glycol ketone and .17 to 18% toluene were added to produce a final clearcoat composition.
• the blend was stirred for 20 minutes at medium speed to assure full incorporation of components before continuing with the procedure.
• the aluminum tint includes 0.169 g Silberline STAR-BRITE 1150 vacuum-metallized aluminum having 1.28% pigment dispersed in 22.59% binder, cellulose acetate butyrate and non-functional methacrylate resin having 76.13% solvent ethyl / N-butyl acetate solvent blend.
• the sample was agitated for 20 minutes to complete the incorporation of the pigments into the resin system.
• Additions of 0.219 g tin catalyst solution (90% - methyl N-amyl ketone) and 0.133 g UV absorber solution (80%-N-butyl acetate/100 aromatic solvent) were added to Component A under agitation.
• Example 3 which contained functional and non-functional acrylic polyolSj the acrylic polyol resin was mixed with the non-functional acrylic resin using a rotary stirrer at an ambient temperature at low speed. 6:41 g of various solvents consisting of ethyl acetate(13.2%), methyl N-amyl ketone (23.85%), glycol acetate (29.9%) and 100 aromatic solvent (33.07%) were added to the resin solution. Next, 0.43 g UV stabilizers/absorbers, 0.01 g 10% tin solution and 0.065 g of silicone additives were added. The blend was stirred for 20 minutes at medium speed to assure full agitation of the components, which were then stirred to the remainder of Component A.
• various solvents consisting of ethyl acetate(13.2%), methyl N-amyl ketone (23.85%), glycol acetate (29.9%) and 100 aromatic solvent (33.07%) were added to the resin solution.
• the two-component polyurethane compositions were prepared by the .following procedure: Component A (including the solvent reducer) was mixed with Component B isocyanate blend (including the solvent reducer shown in Table 1 ) in appropriate amounts to give the indicated NCO:OH ratio for 2 minutes to assure complete incorporation.
• the blended viscosity of the final coatings were measured at 15-25 seconds using #2 viscosity Zahn cup.
• the coatings were applied over a flexible substrate via a conventional Binks Model #7 gun at either an atomization pressure of 60-70 psi and low fluid flow, or an atomized pressure of 50-60 psi and medium fluid flow (Example 3). The coating was sprayed to cover the substrate to approximately 0.6 mils of film build thickness.
• Example 4 and Example 3 are shown in Tables 2 to 4 over a variety of flexible substrates. Both Examples 3 and 4 passed initial/final adhesion testing, 10-day humidity testing and flexibility testing over each type of flexible substrate: EVA foam, thermoplastic polyurethane laminated, finished natural leather, vinyl. (PVA) and thermoplastic polyurethane. According to the standard test method ASTM D3359 test method B, all five coated substrates demonstrated a 5 classification on a scale of 0 to 5, indicating excellent adhesion onto the surface.
• B refers to the test method B of ASTM Standard D3359- lattice pattern cut through coating . to substrate, pressure-sensitive tape applied and quickly removed. . • ' , •
• Adhesion ASTM D3359 [0042] As shown in Table 4, a flexibility, bend test was performed on both samples over the five substrates. After a seven day post-cure, the substrate was manually bent to 180°. There were no indications of cracking or stripping of the coating from any substrate.
• Example 4 obtained exc-ept ⁇ onal film properties over thermoplastic polyurethane plastic.
• Table 5 contains detailed performance information on this flexible coating in Example 4 over thermoplastic urethahe (TPU).
• TPU thermoplastic urethahe
• ASTM test method required for the pencil hardness test, final results displayed between HB-F hardness categories on a scale of 6HB-6H.
• a 2-minute spot exposure test was performed using three solvents - methyl ethyl ketone, ethanol and methanol.
• the chrome coating showed no signs of color or gloss variation.
• Another standard spot exposure test for 24 hours involved different common liquids such as olive oil, lemon juice, motor oil, hand cream, cola and coffee. All liquids passed observing no visible change in coating appearance.
• the taber abrasion test using Norman abrasion tester performed up to 75 cycles without complete coating loss to substrate.
• the standard alcohol resistance test passed at 50 double rubs of ethanol with no change in color or gloss.
• One significant physical test performed over the chrome coating was the flexibility test done over a three-month period.
• the coated TPU substrate was manually folded to 180° and restrained with a clip for a period of three months. At the conclusion of the three-month period, there were rio signs of cracking or change of coating color/gloss over the period of time.
• Another test demonstrating flexibility involved impact resistance based on the standard test method in ASTM D2794-93. The failure end point was observed using 1.45 inch- pounds producing slight cracking at the center contact point.
• Example 3 The coating of Example 3 was prepared having three different
• NCO:OH ratio as high as 5:1 , exhibit a tensile strength, Young's modulus and toughness that are typical for coatings having a significantly lower NCO:OH ratio, such as less than 1.7:1. . .
• Examples 1-4 were coated over standard synthetic leather as ' described above, and further tested as shown in Table 7.
• o Cure time is measured as time necessary at 22 0 C to gel - gel means that the coating is not pourable. . . .
• o Bond Strength is an industry standard test and is a measure of the force necessary to rip the paint from the substrate, and is measured in. PLI (pounds per linear inch).
• o Bally Flex also an industry standard test, measures crack resistance using a Bally

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