WO2019216893A1 - Compositions durcissables et leur utilisation en tant que revêtements et composants pour articles chaussants - Google Patents

Compositions durcissables et leur utilisation en tant que revêtements et composants pour articles chaussants Download PDF

Info

Publication number
WO2019216893A1
WO2019216893A1 PCT/US2018/031855 US2018031855W WO2019216893A1 WO 2019216893 A1 WO2019216893 A1 WO 2019216893A1 US 2018031855 W US2018031855 W US 2018031855W WO 2019216893 A1 WO2019216893 A1 WO 2019216893A1
Authority
WO
WIPO (PCT)
Prior art keywords
curable composition
isocyanate
weight
polyamine
abrasion resistant
Prior art date
Application number
PCT/US2018/031855
Other languages
English (en)
Inventor
Benjamin Kabagambe
Ronald J. KRALIC
Cynthia Kutchko
Edward R. Millero, Jr.
Katie M. CUMPSTON
Susan F. Donaldson
Jonathan P. BREON
Christina A. Winters
Hongying Zhou
Original Assignee
Ppg Industries Ohio, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ppg Industries Ohio, Inc. filed Critical Ppg Industries Ohio, Inc.
Priority to PCT/US2018/031855 priority Critical patent/WO2019216893A1/fr
Priority to US16/266,894 priority patent/US20190168495A1/en
Publication of WO2019216893A1 publication Critical patent/WO2019216893A1/fr

Links

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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3237—Polyamines aromatic
    • C08G18/324—Polyamines aromatic containing only one aromatic ring
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3821—Carboxylic acids; Esters thereof with monohydroxyl 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
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy 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
    • 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
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino 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
    • 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
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate 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
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2410/00—Soles
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium

Definitions

  • polyisocyanates used to prepare the isocyanate-functional prepolymer are often aliphatic.
  • suitable polyisocyanates include isophorone diisocyanate (IPDI), which is 3,3,5-trimethyl-5-isocyanato-methyl-cyclohexyl isocyanate; hydrogenated materials such as cyclohexylene diisocyanate, 4,4'- methylenedicyclohexyl diisocyanate (H12MDI); polymethylene isocyanates such as IPDI), which is 3,3,5-trimethyl-5-isocyanato-methyl-cyclohexyl isocyanate; hydrogenated materials such as cyclohexylene diisocyanate, 4,4'- methylenedicyclohexyl diisocyanate (H12MDI); polymethylene isocyanates such as
  • the polyisocyanate is reacted with (i) a polyamine having primary and/or secondary amino groups, and/or (ii) a polyol.
  • the polyamines and polyols may be any of those known in the art, such as acrylic, polyester, polycarbonate, polybutadiene and/or polyether.
  • Polyethers are used most often. Suitable polyethers include polyoxyalkyleneamines having two or more primary and/or secondary amino groups attached to a backbone, derived, for example, from propylene oxide, ethylene oxide, butylene oxide or a mixture thereof.
  • amines examples include those available under the designation JEFFAMINE, such as JEFFAMINE D-230, D-400, D-2000, HK- 51 1 , ED-600, ED-900, ED-2003, T-403, T-3000, T-5000, SD-231 , SD-401 , SD-2001 , and ST-404 (from Huntsman Corporation).
  • JEFFAMINE such as JEFFAMINE D-230, D-400, D-2000, HK- 51 1 , ED-600, ED-900, ED-2003, T-403, T-3000, T-5000, SD-231 , SD-401 , SD-2001 , and ST-404 (from Huntsman Corporation).
  • JEFFAMINE such as JEFFAMINE D-230, D-400, D-2000, HK- 51 1 , ED-600, ED-900, ED-2003, T-403, T-3000, T-5000, SD-231 , SD-401 , SD-2001 , and
  • substituent R1 is hydrogen or lower alkyl containing from 1 to 5 carbon atoms including mixed substituents, and n is typically from 2 to 6 and m is from 8 to 100 or higher. Included are poly(oxytetramethylene) glycols, poly(oxytetraethylene) glycols, poly(oxy-1 ,2-propylene) glycols, and poly(oxy-1 ,2-butylene) glycols.
  • the isocyanate-functional prepolymer typically has a weight average molecular weight of 1 ,300 to 20,000, often 1 ,400 to 15,000, or 4,000 to 15,000, or 5,000 to 10,000.
  • the isocyanate-functional prepolymer usually has an isocyanate equivalent weight greater than 300, often 400 to 1 ,000.
  • the curable composition of the present invention further comprises (b) a curing agent that in turn comprises a mixture of polyamines. At least one polyamine in the mixture has an amine equivalent weight of 125 to 250. Such polyamines provide hardness to the curable composition.
  • Suitable polyamines can include those that are known in the art. Non-limiting examples of suitable polyamines can include but are not limited to primary and secondary amines, and mixtures thereof, such as any of those disclosed herein. Amine terminated polyureas may also be used. Amines comprising tertiary amine functionality can be used provided that the amine further comprises at least two primary and/or secondary amino groups.
  • At least one polyamine in the mixture having an amine equivalent weight of 125 to 250 may be a non-cyclic polyamine which comprises secondary amino groups. It has been found that including such a non-cyclic polyamine in the curable composition of the present invention significantly improves abrasion resistance of a coating layer or component made from the curable composition, even if no inorganic particles as described below are included in the curable composition as abrasion resistant additive.
  • the term“non-cyclic polyamine” refers to a molecule comprising more than one amino group per molecule, the amino groups being linked by one or more linear or branched aliphatic organic moieties, which molecule does not comprise a cyclic moiety.
  • Suitable non-cyclic polyamines having an amine equivalent weight of 125 to 250 which comprise secondary amino groups include aspartic ester functional amines, such as that available under the name DESMOPHEN NH 1220 (Covestro LLC).
  • the curing agent often comprises about 8 percent by weight DESMOPFIEN NH 1220, a non-cyclic amine with an amine equivalent weight of about 234, about 8 percent by weight CLEARLINK 1000, a cycloaliphatic amine with an amine equivalent weight of about 161 , and about 84 percent by weight JEFFAMINE T-5000, a trifunctional aliphatic amine that has an amine equivalent weight of about 1902.
  • the curable composition of the present invention further comprises (c) an abrasion resistant additive.
  • the abrasion resistant additive comprises organic particles. Often the particles are chemically inert, untreated and uncoated particles. By“chemically inert” is meant that the particles do not chemically react with any other component in the curable composition.
  • the organic particles demonstrate a volume average particle size of at least 5 microns, such as 5 to 7.5 microns or 9.75 to 60 microns.
  • the abrasion resistant additive may further comprise inorganic particles.
  • the inorganic particles typically demonstrate a volume average particle size of at least 90 microns, often at least 95 microns.
  • Suitable inorganic particles include, inter alia, untreated alumina, such as those available in the MICROGRIT line of products from Micro Abrasives Corporation. Combinations of each type of particle are also possible.
  • an aminosilane for use as an adhesion promoter is y-aminopropyltriethoxysilane (commercially available as SILQUEST A1 100 from Momentive Performance Chemicals). SILQUEST A1 1 10 and A LINK 35 from Momentive Performance Chemicals may also be used.
  • Metal-containing adhesion promoters may include metal chelate complexes such as an aluminum chelate complex (e.g. K-Kat 5218 available from King Industries) or tin-containing compositions such as stannous octoate and organotin compounds such as dibutyltin dilaurate and dibutyltin diacetate.
  • Other adhesion promoters may include salts such as chlorine phosphate, butadiene resins such as an epoxidized, hydroxyl terminated polybutadiene resin (e.g. POLY bd® 605E available from Atofina Chemicals, Inc.), polyester polyols (e.g.
  • Suitable organic titanate adhesion promoters include tetra n-butyl titanate, tetra isopropyl titanate, butyl isopropyl titanate, and titanium acetyl acetonate.
  • Suitable organic zirconate adhesion promoters include those capable of reacting with hydroxy group thus promoting cross- linking, which are commercially available from Dorfketal Chemicals(i) Pvt.
  • the curable composition of the present invention may comprise the reaction product of an epoxy resin and a polythiol.
  • Suitable epoxy resins include, for instance, one or more polyepoxides such as polyglycidyl ethers of bisphenol A, polycaprolactone modified bisphenol A epoxy resins, and bisphenol F diepoxides.
  • the epoxy resin may also comprise an epoxy-dimer adduct.
  • Suitable polythiols include, for instance, poly(mercaptopropionates), such as those available under the designation THIOCURE from Bruno Bock Chemische Fabrik GmbH & Co. KG.
  • polyurethane can be formed by reacting a hydroxyl functional component with an isocyanate, much in the same manner as the amine and isocyanate components described herein react.
  • a hydroxyl functional component can be mixed with, or used in addition to, the amine component for in situ polyurethane formation.
  • the curable compositions of the present invention may optionally include materials standard in the art such as fiberglass, stabilizers, thickeners, catalysts, colorants, antioxidants, UV absorbers, hindered amine light stabilizers, rheology modifiers, flow additives, anti-static agents and other performance or property modifiers that are well known in the art of surface coatings, and mixtures thereof.
  • Suitable rheology modifiers include solid and/or liquid rheology modifiers, which can be organic and/or inorganic based polymers, such as bentonite clay, fumed silica, BYK 41 1 (available from Chemie), or combinations thereof.
  • the curable composition of the present invention may 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 composition 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 compositions of the present invention. It is noted that particulate colorants are different from the particles present in the abrasion resistant additive (c). It has been found that particulate colorants do not impart sufficient abrasion resistance to the curable compositions to be considered suitable, as shown in the examples below.
  • 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 compositions by grinding or simple mixing. Colorants can be incorporated by grinding into the composition 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, carbon fiber, graphite, other conductive pigments and/or fillers and mixtures thereof.
  • DPPBO red diketo pyrrolo pyrrole red
  • the colorant can be in the form of a dispersion including 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 and/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. 6,875,800 B2.
  • 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. 10/876,031 filed June 24, 2004, and U.S. Provisional Application No. 60/482,167 filed June 24, 2003.
  • 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 composition 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 colorless 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 have minimal migration out of the composition.
  • the curable compositions of the present invention when applied to a substrate for example as a coating, may possess color that matches the color of an associated substrate.
  • the term “matches” and like terms when referring to color matching means that the color of the coating composition of the present invention substantially corresponds to a desired color or the color of an associated substrate. This can be visually observed, or confirmed using spectroscopy equipment.
  • the substrate for the curable composition is a footwear component, such as a polymeric bladder or upper component
  • the color of the curable composition may substantially match that of another footwear component.
  • a toe coated with a curable composition of the present invention can be color matched to the rest of the shoe upper, the midsole and/or the outsole. This match can be visually observed, or confirmed using spectroscopy equipment.
  • the composition can be cured at ambient conditions, although heated air or a heat cure can be applied to the composition in order to accelerate curing of the composition or to enhance properties such as adhesion.
  • ambient conditions is meant without the application of heat or other energy; for example, when a curable composition undergoes a thermosetting reaction without baking in an oven, use of forced air, irradiation, or the like to prompt the reaction, the reaction is said to occur under ambient conditions.
  • ambient temperature ranges from 60 to 90 °F (15.6 to 32.2 °C), such as a typical room temperature, 72°F (22.2°C).
  • the composition may be exposed to actinic radiation or to an elevated temperature for a time sufficient to at least partially cure the curable film-forming composition.
  • compositions may be applied to the substrate by one or more of a number of methods including 3D-printing, spraying, dipping/immersion, brushing, extrusion, dispensing, or flow coating.
  • the substrate comprises flooring, they are most often applied by spraying.
  • Conventional spray techniques and equipment for air spraying and electrostatic spraying and either manual or automatic methods can be used as described below.
  • the coating layer typically has a dry film thickness of 1 -25 mils (25.4-635 microns), often 5-80 mils (127-2032 microns). Curing conditions may be as described above.
  • the curable composition When the curable composition is spray applied to a substrate, the composition may be prepared using a two-component mixing device.
  • isocyanate and amine are added to a high pressure impingement mixing device.
  • the isocyanate is added to the“A-side” and amine is added to the“B-side”.
  • the A- and B- side streams are impinged upon each other and immediately sprayed onto at least a portion of an uncoated or coated substrate.
  • the isocyanate and the amine react to produce a coating composition that is cured upon application to the uncoated or coated substrate.
  • the A- and/or B-side can also be heated prior to application, such as to a temperature of ⁇ 70°C, such as 60°C. Heating may promote a better viscosity match between the two components and thus better mixing, but is not necessary for the curing reaction to occur.
  • the A- and/or B-side may be applied at a temperature ⁇ 23°C, such as from 7°C to 14°C.
  • A“static mix tube” applicator which is an application device known in the art, may be used with the present invention.
  • the isocyanate and amine are each stored in a separate chamber.
  • each of the components is brought into a mixing tube in a 1 : 1 ratio by volume. Mixing of the components is effected by way of a torturous or cork screw pathway within the tube.
  • the exit end of the tube may have atomization capability useful in spray application of the reaction mixture.
  • the fluid reaction mixture may be applied to a substrate as a bead.
  • a static mix tube applicator is commercially available from Plas- Pak Industries Inc. or Cammda Corporation.
  • the ratio of equivalents of isocyanate groups to amine groups may be selected to control the rate of cure of the coating composition of the present invention. It has been found that cure and adhesion advantages may result when the ratio of the equivalents of isocyanate groups to amine groups (also known as the reaction index) is greater than one, such as from 1 .01 to 1 .10: 1 , or from 1 .03 to 1 .10: 1 , or from 1 .05 to 1 .08: 1 or from 1 .01 to 1.4 to 1 or from 1 .01 to 1 .5, or 1 .3 or greater to 1 .
  • the term“1 : 1 volume ratio” means that the volume ratio varies by up to 20% for each component, or up to 10% or up to 5%.
  • diols used to make the isocyanate-functional prepolymers can be aromatic or aliphatic diols, such as, polycarbonate, polyether glycols, polyesters, polycaprolactones, polybutadienes, polyamides, siloxane diols, alkyd diols and acrylic diols.
  • the dry film thickness of the outsole varies depending on the relative amounts of each type of particle. For example, when the weight ratio of organic particles to inorganic particles is less than 10:40, the dry film thickness of the outsole is typically 508 to 25,400 microns. When the weight ratio of organic particles to inorganic particles is at least 40: 10, the dry film thickness of the outsole is typically 25.4 to 254 microns.
  • a curable composition comprising:
  • an isocyanate-functional prepolymer wherein the isocyanate-functional prepolymer comprises (i) a reaction product of a polyisocyanate and a polyamine having primary and/or secondary amino groups; and/or (ii) a reaction product of a polyisocyanate and a polyol;
  • composition according to aspect 10 wherein the organic particles of the abrasion resistant additive demonstrate a volume average particle size of 5 to 7.5 microns. 12. The composition according to any of the preceding aspects, wherein the abrasion resistant additive (c) further comprises inorganic particles, which comprise untreated alumina, or wherein the abrasion resistant additive (c) does not comprise inorganic particles having a volume average particle size of at least 90 microns.
  • the substrate comprises wood, metal, glass, fabric, leather, a composite, or a polymeric material.
  • the final material had a measured isocyanate equivalent weight of 505.8 as measured by ASTM D2572 “Standard Test Method for Isocyanate Groups in Urethane Materials or Prepolymers” and a weight average Molecular Weight (Mw) of ⁇ 5,300 as measured by Gel Permeation Chromatography versus a polystyrene standard.
  • An isocyanate-functional prepolymer was prepared from the following ingredients as described below:
  • a total of 450 grams of isophorone diisocyanate was placed in a suitable reaction vessel equipped with a stirrer, temperature probe, a condenser and a nitrogen inlet tube and blanketed with nitrogen gas.
  • room temperature (23°C) 1 ,668 grams of JEFFAMINE D2000 and was added over 25 minutes, during which time the temperature increased to about 62°C.
  • 0.43 grams of dibutyltin dilaurate was added and the mixture held for 30 minutes after which the mixture was heated to 70°C. The mixture was held at 70°C for 1 hour, during which time the isocyanate equivalent weight reached about 1 ,000 grams per equivalent.
  • An isocyanate-functional prepolymer was prepared from the following ingredients as described below:
  • the temperature was reduced to 80°C and 353.0g of Desmodur XP2580 and 1059.3g of Tolonate HDT LV2 were added and the temperature further reduced to 60°C. After 1 hour, the material had a measured isocyanate equivalent weight of about 259 grams per equivalent.
  • 780.7grams of methyl amyl ketone was added and the final mixture has an isocyanate equivalent weight of about 341 grams per equivalent as measured by ASTM D2572 “Standard Test Method for Isocyanate Groups in Urethane Materials or Prepolymers” and the polymer had a weight average Molecular Weight (Mw) of ⁇ 1 ,400 as measured by Gel Permeation Chromatography versus a polystyrene standard.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des compositions durcissables comprenant : (a) un prépolymère à fonction isocyanate ; (b) un agent de durcissement comprenant un mélange de polyamines, au moins une polyamine présentant un poids équivalent d'amine variant de 125 à 250 ; et (c) un additif résistant à l'abrasion comprenant des particules organiques. Le prépolymère à fonction isocyanate est (i) un produit réactionnel d'un polyisocyanate et d'une polyamine comportant des groupes amine primaire et/ou secondaire ; et/ou (ii) un produit réactionnel d'un polyisocyanate et d'un polyol. Lors de l'application de la composition sur un substrat sous la forme d'un revêtement et après durcissement pour former un substrat revêtu, le substrat revêtu présente une perte de revêtement inférieure à 0,33 cm3 après avoir été soumis à 1 000 cycles d'un essai d'abrasion TABER utilisant des bandes de papier de verre S-42 et deux poids de 1 000 grammes. L'invention concerne également des substrats revêtus et des composants pour articles chaussants préparés à partir des compositions.
PCT/US2018/031855 2016-11-09 2018-05-09 Compositions durcissables et leur utilisation en tant que revêtements et composants pour articles chaussants WO2019216893A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US2018/031855 WO2019216893A1 (fr) 2018-05-09 2018-05-09 Compositions durcissables et leur utilisation en tant que revêtements et composants pour articles chaussants
US16/266,894 US20190168495A1 (en) 2016-11-09 2019-02-04 Rubber replacement articles and their use as footwear components

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2018/031855 WO2019216893A1 (fr) 2018-05-09 2018-05-09 Compositions durcissables et leur utilisation en tant que revêtements et composants pour articles chaussants

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US15/346,853 Continuation-In-Part US10240064B2 (en) 2016-11-09 2016-11-09 Curable compositions and their use as coatings and footwear components

Publications (1)

Publication Number Publication Date
WO2019216893A1 true WO2019216893A1 (fr) 2019-11-14

Family

ID=62245498

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2018/031855 WO2019216893A1 (fr) 2016-11-09 2018-05-09 Compositions durcissables et leur utilisation en tant que revêtements et composants pour articles chaussants

Country Status (1)

Country Link
WO (1) WO2019216893A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023012000A1 (fr) * 2021-08-02 2023-02-09 Basf Se Composition de résine à double durcissement comprenant un composé contenant des uretdiones et son utilisation en impression 3d

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2092104A (en) 1933-08-26 1937-09-07 Maytag Co Clutch mechanism
US2132504A (en) 1938-02-17 1938-10-11 Morgan Smith S Co Hydraulic machine
US4219945A (en) 1978-06-26 1980-09-02 Robert C. Bogert Footwear
US4506460A (en) 1982-06-18 1985-03-26 Rudy Marion F Spring moderator for articles of footwear
US5353459A (en) 1993-09-01 1994-10-11 Nike, Inc. Method for inflating a bladder
US5630408A (en) 1993-05-28 1997-05-20 Ranco Incorporated Of Delaware Gas/air ratio control apparatus for a temperature control loop for gas appliances
US5630608A (en) 1994-01-28 1997-05-20 Atomic Austria Gmbh Ski brake
US5674567A (en) * 1994-04-26 1997-10-07 Gencorp Inc. Low VOC, primerless, polyurethane compositions
US5713141A (en) 1994-08-31 1998-02-03 Nike, Inc. Cushioning device with improved flexible barrier membrane
US6119371A (en) 1998-01-09 2000-09-19 Nike, Inc. Resilient bladder for use in footwear
US6875800B2 (en) 2001-06-18 2005-04-05 Ppg Industries Ohio, Inc. Use of nanoparticulate organic pigments in paints and coatings
US6894086B2 (en) 2001-12-27 2005-05-17 Ppg Industries Ohio, Inc. Color effect compositions
US6944973B2 (en) 2001-09-17 2005-09-20 Nike, Inc. Protective cage for footwear bladder
US20070160851A1 (en) 2005-08-25 2007-07-12 Barancyk Steven V Polyurea coating comprising an amine/(meth)acrylate oligomeric reaction product
US20100076143A1 (en) * 2008-04-21 2010-03-25 Ppg Industries Ohio, Inc. Low temperature application coating composition comprising polyurea and a phosphorus-containing polyol and footwear comprising polyurea
CN108003767A (zh) * 2017-12-20 2018-05-08 长沙盾甲新材料科技有限公司 一种复合耐磨剂及耐磨型聚脲弹性体涂料

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2092104A (en) 1933-08-26 1937-09-07 Maytag Co Clutch mechanism
US2132504A (en) 1938-02-17 1938-10-11 Morgan Smith S Co Hydraulic machine
US4219945A (en) 1978-06-26 1980-09-02 Robert C. Bogert Footwear
US4219945B1 (en) 1978-06-26 1993-10-19 Robert C. Bogert Footwear
US4506460A (en) 1982-06-18 1985-03-26 Rudy Marion F Spring moderator for articles of footwear
US5630408A (en) 1993-05-28 1997-05-20 Ranco Incorporated Of Delaware Gas/air ratio control apparatus for a temperature control loop for gas appliances
US5353459A (en) 1993-09-01 1994-10-11 Nike, Inc. Method for inflating a bladder
US5630608A (en) 1994-01-28 1997-05-20 Atomic Austria Gmbh Ski brake
US5674567A (en) * 1994-04-26 1997-10-07 Gencorp Inc. Low VOC, primerless, polyurethane compositions
US5713141A (en) 1994-08-31 1998-02-03 Nike, Inc. Cushioning device with improved flexible barrier membrane
US5952065A (en) 1994-08-31 1999-09-14 Nike, Inc. Cushioning device with improved flexible barrier membrane
US6119371A (en) 1998-01-09 2000-09-19 Nike, Inc. Resilient bladder for use in footwear
US6875800B2 (en) 2001-06-18 2005-04-05 Ppg Industries Ohio, Inc. Use of nanoparticulate organic pigments in paints and coatings
US6944973B2 (en) 2001-09-17 2005-09-20 Nike, Inc. Protective cage for footwear bladder
US6894086B2 (en) 2001-12-27 2005-05-17 Ppg Industries Ohio, Inc. Color effect compositions
US20070160851A1 (en) 2005-08-25 2007-07-12 Barancyk Steven V Polyurea coating comprising an amine/(meth)acrylate oligomeric reaction product
US20100076143A1 (en) * 2008-04-21 2010-03-25 Ppg Industries Ohio, Inc. Low temperature application coating composition comprising polyurea and a phosphorus-containing polyol and footwear comprising polyurea
CN108003767A (zh) * 2017-12-20 2018-05-08 长沙盾甲新材料科技有限公司 一种复合耐磨剂及耐磨型聚脲弹性体涂料

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 201839, Derwent World Patents Index; AN 2018-37503H, XP002787671 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023012000A1 (fr) * 2021-08-02 2023-02-09 Basf Se Composition de résine à double durcissement comprenant un composé contenant des uretdiones et son utilisation en impression 3d

Similar Documents

Publication Publication Date Title
US10240064B2 (en) Curable compositions and their use as coatings and footwear components
US8822594B2 (en) Low temperature application coating composition comprising polyurea and a phosphorus-containing polyol and footwear comprising polyurea
US7968197B2 (en) Polyurea coating comprising an amine/(meth)acrylate oligomeric reaction product
US7968198B2 (en) Polyurea coating comprising a polyamine/mono(meth)acrylate reaction product
US7968212B2 (en) Triamine/aspartate curative and coatings comprising the same
US7972701B2 (en) Substrates coated with a polyurea comprising a (meth)acrylated amine reaction product
US11286400B2 (en) Curable compositions containing reactive functional compounds and polysiloxane resins, articles of manufacture and coated articles prepared therefrom, and a method of mitigating dirt build-up on a substrate
US20190168495A1 (en) Rubber replacement articles and their use as footwear components
WO2019216893A1 (fr) Compositions durcissables et leur utilisation en tant que revêtements et composants pour articles chaussants
CN113366045B (zh) 橡胶替代制品和其作为鞋类组件的用途

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18727576

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18727576

Country of ref document: EP

Kind code of ref document: A1