TWI478992B - Low temperature application coating composition comprising polyurea and a phosphorus-containing polyol and footwear comprising polyurea - Google Patents

Description

Low-temperature application coating composition comprising polyurea and phosphorus-containing polyalcohol and footwear containing polyurea

The present invention is directed to a coating composition comprising polyurea and a footwear comprising polyurea.

This invention was made with government support under Contract No. 200-2007-20426 awarded by the Centers for Disease Control and Prevention. The U.S. Government may have certain rights in the invention.

This patent application claims the US Provisional Patent entitled "LOW TEMPERATURE APPLICATION COATING COMPOSITION POLYUREA AND A PHOSPHORUS-CONTAINING POLYOL", which was applied for on September 24, 2008. The right of U.S. Provisional Patent Application Serial No. 61/046,515, the entire disclosure of which is incorporated herein by reference.

Coating compositions are used in a variety of industries. Such industries may include, but are not limited to, land vehicles such as automobiles, trucks, sport utility vehicles, motorcycles; ships such as boats, boats and submarines; aircraft such as aircraft and helicopters; industry, such as commercial equipment and Structures (including walls and roofs); buildings, such as construction vehicles and structures (including walls and roofs); military, such as military vehicles (eg, tanks and highly mobile multi-purpose wheeled vehicles (humvee)) and military structures (including walls) And roofs, such as ammunition boxes and battery enclosures; and similar industries.

In these industries, coatings serve a variety of purposes, such as protecting various components from corrosion, abrasion, impact, chemicals, ultraviolet light, flames and heat, and other environmental exposures, thereby imparting impact and explosion to the components deposited by the coating. Alleviation. Therefore, much effort has been expended to develop coating compositions with improved properties.

Coatings are often used in the footwear industry. Footwear is usually divided into two parts, the upper and the sole. The upper is a portion of the footwear that is designed to comfortably enclose the foot, while the sole is a portion of the footwear that is designed to provide traction, protection, cushioning, and/or durability.

The upper typically contains many different components, which are often made of different materials. Such materials include, for example, natural leather, synthetic leather, vinyl, and fabrics such as nylon; other textiles may also be used. Many upper components (especially "toe caps") are subject to wear and/or wear even during normal use of the shoe.

Similarly, soles often include different components made of different materials. The midsole is usually made of a foam such as an ethylene-vinyl acetate (EVA) foam, or a foam of a polyurethane such as TPU. These materials are elastically compressed under the applied load, such as the force generated by the feet and legs during physical activity. Many shoes, particularly athletic shoes, include a cushioning device or bladder that is in another shoe assembly, such as a midsole, outsole, and the like. The balloon can be an expandable insert made of a compression resistant polymeric material to provide additional cushioning for the footwear wearer. Such bladders may be filled with, for example, pulp, water, or other fluids such as air or nitrogen. The outsole is often made of synthetic rubber and/or natural rubber such as a rubber composition filled with cerium oxide. The outsole is subject to wear and/or wear even during normal use of the shoe.

Accordingly, there is a need for improved resistance and/or durability of the shoe assembly to wear, wear and other damage.

The present invention is directed to a coating composition comprising polyurea formed from a reaction mixture comprising: (a) a first component comprising an isocyanate, the first component being Having a temperature of 7 ° C a viscosity of 2000 centipoise (cPs); and (b) a second component comprising an amine, the second component being Having a temperature of 7 ° C 1700 cPs viscosity. The invention is also directed to a method of coating a substrate with the coating.

The invention is further directed to footwear comprising an assembly that is at least partially coated with a composition comprising polyurea.

As used herein, unless expressly stated otherwise, all numbers such as the <RTI ID=0.0> </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; Any range of values recited herein is intended to include all subranges that are included. The plural includes the singular and the singular encompasses the plural. "include" and similar terms are open ended, that is, they mean "including but not limited to". For example, although in this context (including the scope of the patent application), there is a "one" polyurea, a "poly" ester, an "is" isocyanate, an "one" amine, a "one" polyalcohol, a "one" polythiol, The invention is described in terms of "a" prepolymer, "a" catalyst, and the like, but a mixture of all such materials can be used. Also, as used herein, the term "polymer" means both a prepolymer, an oligomer, and both a homopolymer and a copolymer; the prefix "poly" refers to two or more. .

As used herein, the term "curing" refers to a coating that at least partially crosslinks any crosslinkable component of the composition. In some embodiments, the crosslink density (ie, the degree of crosslinking) of the crosslinkable component is from 5% to 100% of complete crosslinking, such as from 35% to 85%, or in some cases 50% to 85% range. Those skilled in the art will appreciate that the presence of crosslinks and the degree of crosslinking (i.e., crosslink density) can be determined by a variety of methods, such as dynamic mechanical thermal analysis using a Polymer Laboratories MK III DMTA analyzer under nitrogen ( DMTA).

The viscous measurements used herein were measured using a PHYSICA MCR 301 rheometer (available from Antone Paar GmbH, Austria) with a 50 mm/1[deg.] cone. The sample to be measured was loaded onto a conical disk at 23.89 ° C and the viscosity measurement was performed at a constant shear rate of 1000 s ^-1 at a suitable temperature.

As used herein, the coating composition has been tested for tensile strength and/or elongation % according to ASTM D638-08 standards after it has been applied to a substrate and cured.

References herein to any one or more monomers generally refer to monomers that are polymerizable with another polymerizable compound, such as another monomer or polymer. Unless otherwise indicated, it will be appreciated that once the monomer components react with each other to form a compound, the compound will comprise residues of the monomer component.

Coating composition

The present invention is directed to a coating composition comprising polyurea formed from a reaction mixture comprising the following components: a first component (sometimes referred to herein as an "isocyanate component") comprising an isocyanate; Two components (sometimes referred to herein as "amine components"), which comprise an amine. The first group is in Having a temperature of 7 ° C Viscosity of 2000 cPs, and the second component is Having a temperature of 7 ° C 1700 cPs viscosity. In certain embodiments, the coating composition can further comprise a polyurethane.

In some embodiments, the coating composition exhibits % elongation after application to the substrate and after curing 10. For example, in some embodiments, the elongation % can be 100, such as 200. In some embodiments, the coating composition exhibits maximum tensile strength after application to the substrate and after curing 5 MPa, such as 10 MPa.

Isocyanate component

As noted above, in Viscosity of the first component at a temperature of 7 ° C (such as in the range of 7 ° C to 13 ° C) 2000 centipoise (cP). In some embodiments, the viscosity 1800, or 1500. In some embodiments, the viscosity of the first component ranges from 1100 centipoise to 1600 centipoise at a temperature in the range of from 13 °C to 10 °C.

As used herein, the term "isocyanate" includes unblocked isocyanate compounds capable of forming a covalent bond with a reactive group such as a hydroxyl, thiol or amine functional group. Thus, isocyanate may be referred to as "free isocyanate" as would be understood by those skilled in the art. In certain embodiments, the isocyanate of the present invention may be monofunctional (containing one isocyanate functional group (NCO)), or the isocyanate used in the present invention may be polyfunctional (containing two or more isocyanate functional groups) (NCO)). The isocyanate can also be blocked. Any combination of isocyanate and/or isocyanate functional prepolymers can be used in accordance with the invention.

The isocyanates suitable for use in the present invention are numerous and widely variable. The isocyanates can include such isocyanates as are known in the art. Non-limiting examples of suitable isocyanates can include monomeric isocyanates and/or polymeric isocyanates. The isocyanate can be selected from monomers, prepolymers, oligomers, or blends thereof. In one embodiment, the isocyanate can be a C ₂ -C ₂₀ straight chain, a branched chain, a cyclic, an aromatic, an aliphatic, or a combination thereof.

Isocyanates suitable for use in the present invention may include, but are not limited to, isophorone diisocyanate (IPDI), which is 3,3,5-trimethyl-5-isocyanate-methyl-cyclohexyl isocyanate. a hydrogenated substance such as cyclohexyl diisocyanate, 4,4'-methylene dicyclohexyl diisocyanate (H ₁₂ MDI); a mixed aryl alkyl diisocyanate such as diisocyanate Tetramethylxyl ester, OCN-C(CH ₃ ) ₂ -C ₆ H ₄ C(CH ₃ ) ₂ -NCO; polymethylene isocyanate, such as 1,4-butane diisocyanate, diiso 1,5-pentane dicarboxylate, 1,6-hexane diisocyanate (HMDI), 1,7-heptane diisocyanate, 2,2,4-trimethyl diisocyanate Hexanediester and 2,4,4-trimethylhexyl diisocyanate, 1,10-decane diisocyanate, and 2-methyl-1,5-pentane diisocyanate ; and mixtures thereof.

Non-limiting examples of the aromatic isocyanate used in the present invention may include, but are not limited to, diphenyl phenyl isocyanate; toluene diisocyanate (TDI); xylyl diisocyanate; 1, 5 -naphthalene diisocyanate; 2,4-diisocyanatochlorophenyl phenyl ester; diisocyanate diisocyanate; diisocyanate diisocyanate; toluidine diisocyanate; alkylated phenyl diisocyanate a methylene interrupted aromatic diisocyanate such as methylene diphenyl diisocyanate; an alkylated analog comprising a 4,4'-isomer (MDI), such as 3,3'-dimethyl Base-4,4'-diphenylmethane diisocyanate; polymerized methylene diphenyl diisocyanate; and mixtures thereof.

In certain embodiments, isocyanate monomers can be used. It is believed that the use of isocyanate monomers (i.e., monomers containing no residues from the preparation of the prepolymer) can reduce the viscosity of the polyurea composition, thereby improving its fluidity, and can provide a polyurea coating to the prior coating. Improved adhesion of the coating and/or uncoated substrate. In an alternative embodiment of the invention, at least 1% by weight or at least 2% by weight, or at least 4% by weight of the isocyanate component comprises at least one isocyanate monomer.

In certain embodiments of the invention, the isocyanate may comprise an oligomeric isocyanate such as, but not limited to, a dimer such as a uretdione ring of 1,6-hexane diisocyanate; a terpolymer, Biuret and isocyanurate such as 1,6-hexane diisocyanate, and isocyanurate of isophorone diisocyanate, urethane and polymerized oligomer. Modified isocyanates can also be used including, but not limited to, carbodiimides and ureton-imines, and mixtures thereof. Suitable materials include, without limitation, those materials available from Bayer Corporation (Pittsburgh, PA) under the name DESMODUR, and include DESMODUR N 3200, DESMODUR N 3300, DESMODUR N 3400, DESMODUR XP 2410, and DESMODUR XP 2580.

In some embodiments, the isocyanate component comprises an isocyanate functional prepolymer formed from a reaction mixture comprising an isocyanate and another material. Any isocyanate known in the art, such as any of the materials described above, can be used to form the prepolymer. As used herein, "isocyanate functional prepolymer" refers to the reaction product of an isocyanate with a polyamine and/or other isocyanate-reactive groups, such as a polyalcohol; the isocyanate-functional prepolymer has at least one isocyanate functional group. (NCO).

In certain embodiments of the invention, the isocyanate functional prepolymer comprises an isocyanate pre-reacted with a material comprising a flame retardant material, such as a phosphorus containing polyol. Suitable isocyanate functional prepolymers comprising a flame retardant material are disclosed in paragraphs [0017] to [0023] of U.S. Patent Application Serial No. 12/122,980, the disclosure of which is incorporated herein by reference. As described in this excerpt, in certain embodiments, the phosphorus-containing polyol itself may be the reaction product of a phosphorus-containing polyol (sometimes referred to as an "initial" phosphorus-containing polyol) with another compound.

However, in some embodiments, the polyol used to form the prepolymer is not a phosphorus containing polyol. Suitable phosphorus-free polyols include polytetrahydrofuran materials such as those sold under the trade name TERATHANE (e.g., TERATHANE 250, TERATHANE 650, TERETHANE 1000, available from Invista Corporation).

The polyurea coating composition which exhibits improved fire resistance and/or heat resistance may comprise any phosphorus-containing isocyanate prepolymer. As used herein, the terms "flame retardant", "refractory", "heat-resistant", "heat-resistant" and the like mean the ability to withstand flames or heat without ignition. As used herein, the terms "modified fire resistance" and "modified heat resistance" mean any degree of improved fire resistance or heat resistance, respectively, which is the same as a coating composition having a flame retardant material, such as a coating composition. A coating composition having a flame retardant material is demonstrated in comparison.

In certain embodiments, the isocyanate component comprises an isocyanate (non-prepolymer isocyanate) and an isocyanate functional prepolymer. The non-prepolymer isocyanate may be the same or different than the isocyanate used to form the isocyanate functional prepolymer. If a combination of isocyanates is used, the isocyanates should be substantially compatible, for example, the isocyanate functional prepolymers can be substantially compatible with the non-prepolymer isocyanates. As used herein, "substantially compatible" means the ability of a material to form a substantially homogeneous blend with other materials and will remain substantially homogeneous over time. The reaction of the isocyanate with an organic material, such as in the formation of an isocyanate functional prepolymer, helps to make the isocyanate compatible.

Amine component

The amine component contains a suitable amine. in Viscosity of the second component at a temperature of 7 ° C (such as in the range of 7 ° C to 13 ° C) 1700 centipoise, such as 1500 centipoise or 1000 centipoise. The amine component herein may be referred to as a "curing agent" as it will react or cure with an isocyanate to form a polyurea. In certain embodiments, the ratio of isocyanate group equivalents to amine equivalents is greater than 1, and the isocyanate component and the amine component can be applied to the substrate in a 1:1 volume mixing ratio.

Suitable polyamines are numerous and can vary widely. Such polyamines can include such polyamines as 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 the polyamines listed herein. Amine-terminated polyureas can also be used. Amines containing a tertiary amine functional group can be used, with the proviso that the amine further comprises at least two primary amine groups and/or secondary amine groups. In certain embodiments in which the isocyanate functional prepolymer comprises a polyamine, the ratio of isocyanate (NCO) equivalents to amine (NH) equivalents can be greater than one.

In certain embodiments, the amine can include, for example: a monoamine; or a polyamine having at least two functional groups, such as a diamine, a triamine, or a higher functional amine; and mixtures thereof. In other embodiments, the amine can be aromatic or aliphatic (such as a cycloaliphatic), or a mixture thereof. Non-limiting examples of suitable monoamines can include aliphatic polyamines such as, but not limited to, ethylamine, isomeric propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, and benzylamine. Suitable first-order polyamines include, but are not limited to, ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,3-diaminopentane (DYTEK EP, Invista) 1,6-Diaminohexane, 2-methyl-1,5-pentanediamine (DYTEK A, Invista), 2,5-diamino-2,5-dimethylhexane, 2, 2,4-Trimethyl-1,6-diamino-hexane and/or 2,4,4-trimethyl-1,6-diamino-hexane, 1,11-diamino-10 Mono-, 1,12-diaminododecane, 1,3-cyclohexanediamine and/or 1,4-cyclohexanediamine, 1-amino-3,3,5-trimethyl-5 - aminomethyl-cyclohexane, 2,4-hexahydrotoluenediamine and / or 2,6-hexahydrotoluenediamine, 2,4'-diaminodicyclohexylmethane, 4,4'- Diaminodicyclohexylmethane (PACM-20, Air Products) and 3,3'-dialkyl-4,4'-diaminodicyclohexylmethane (such as 3,3'-dimethyl-4) , 4'-diaminodicyclohexylmethane (DIMETHYL DICYKAN or LAROMIN C260, BASF; ANCAMINE 2049, Air Products) and 3,3'-diethyl-4,4'-diaminodicyclohexylmethane), 2,4-Diaminotoluene and/or 2,6-diaminotoluene, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6-di Amine, 3,5-dimethylthio-2,4-toluene , 3,5-dimethylthio-2,4-toluenediamine, 2,4'-diaminodiphenylmethane and/or 4,4'-diaminodiphenylmethane, di-extension Trisamine, bishexamethylenetriamine, or a combination thereof. Polyalkylene oxide amines are also suitable. The polyalkylene oxide amines comprise two or more primary or secondary amine groups attached to a backbone derived from, for example, propylene oxide, ethylene oxide, butylene oxide or mixtures thereof. Examples of such amines include those obtained in the name of JEFFAMINE, such as (not limited to) JEFFAMINE D-230, D-400, D-2000, HK-511, ED-600, ED-900, ED-2003, T-403, T-3000, T-5000, SD-231, SD-401, SD-2001, and ST-404 (Huntsman Corporation). The amines have an approximate molecular weight in the range of from 200 to 7500.

Secondary cycloaliphatic diamines are also useful in the present invention. Suitable cycloaliphatic diamines include, without limitation, JEFFLINK 754 (Huntsman Corporation); CLEARLINK 1000 (Dorf-Ketal Chemicals, LLC); and aspartate functional amines, such as those obtained in the name of DESMOPHEN, Such as DESMOPHEN NH1220, DESMOPHEN NH 1420 and DESMOPHEN NH 1520 (Bayer Materials Science LLC). Other suitable secondary amines useful in the present invention include reaction products of materials such as those described herein containing a primary amine functional group with acrylonitrile. For example, the secondary amine can be the reaction product of 4,4'-diaminodicyclohexylmethane with acrylonitrile. Alternatively, the secondary amine can be the reaction product of isophoronediamine and acrylonitrile, such as POLYCLEAR 136 (available from BASF/Hansen Group LLC).

Other amines useful in the present invention include adducts of primary polyamines with monoepoxides or polyepoxides, such as the reaction product of isophoronediamine with CARDURA E-10P.

The polyurea composition of the present invention may also comprise one or more amines, such as in U.S. Patent Application Serial Nos. 11/611,979, 11/611,984, 11/611,988, 11/611,982, and 11/611,986. The amines described in the above are incorporated herein by reference.

Other ingredients

In certain embodiments, the coating composition can include one or more other ingredients in the first component (isocyanate) and/or the second component (amine). Similarly, the coating can comprise one or more other components mixed with the first component and the second component prior to use. Other ingredients may include, for example, flame retardant materials and or in lieu of an isocyanate functional prepolymer comprising a flame retardant material as described herein. Other flame retardant materials may be added to the isocyanate and/or amine components of the present invention.

Any flame retardant material known in the art can be used as the other flame retardant material of the present invention. Such flame retardants may include, for example, those flame retardants described in paragraphs [0035] and [0038] of U.S. Patent Application Serial No. 12/122,980, the disclosure of which is incorporated herein by reference. Into this article. Other suitable flame retardant materials include, but are not limited to, U.S. Patent No. 6,015,510 (line 4, column 31 to line 5, line 41, which is incorporated herein by reference) and No. 5,998,503 ( Row 4, column 31 to row 5, column 41, the extracts are incorporated herein by reference) flame retardant polymers; halogenated phosphates or halogen-free phosphates; powdered dioxide Bismuth or smog-like cerium oxide; layered ceric acid salt; aluminum hydroxide; brominated flame retardant; ginseng (2-chloropropyl) phosphate; ginseng (2,3-dibromopropyl) phosphate; (1,3-Dichloropropyl) phosphate; diammonium phosphate; various halogenated aromatic compounds; cerium oxide; aluminum trihydrate; polyvinyl chloride and the like; and mixtures thereof. In certain embodiments, the flame retardant material is ginseng (2-chloropropyl) phosphate obtained from Supresta under the name FYROL PCF. When the flame retardant is a low viscosity liquid, it can also reduce the viscosity of the isocyanate and/or amine component, thereby enhancing sprayability. In certain embodiments, the flame retardant material may include a monobasic phosphonate and/or a dibasic phosphonate, such as in the two publications of U.S. Patent Publication Nos. 2005/0004277 A1 and 2005/0004278 A1 [0025 The same as those described in paragraph [0070], which are incorporated herein by reference.

In some embodiments, an antioxidant, a hindered amine light stabilizing compound, or a combination thereof can be used as the flame retardant of the present invention. Suitable antioxidants for use in the present invention include phenol-based antioxidants and/or phosphorus-based antioxidants. Suitable examples of such antioxidants are disclosed in Table 1 of U.S. Patent Publication No. 2007/0203269, which is hereby incorporated by reference in its entirety herein in its entirety in its entirety in its entirety in its entirety. Suitable hindered amine light stabilizing compounds useful in the present invention include polymeric hindered amine light stabilizing compounds, monomer hindered amine light stabilizing compounds, or combinations thereof. Suitable polymeric hindered amine light stabilizing compounds include TINUVIN 266, CHIMASORB 199FL, CHIMASORB 944 FDL, TINUVIN 622 (all of which are available from Ciba), CYASORB UV3529, CYASORB UV 3346 (both available from Cytec Industries), A hindered amine light stabilizing functional group polymer, or a combination thereof. Suitable monomer hindered amine light stabilizing compounds useful in the present invention include CYASORB UV3853 (available from Cytec).

The amount of flame retardant material used can vary widely depending on the needs of the user. In certain embodiments, the flame retardant in other flame retardant materials and isocyanate functional prepolymers may comprise up to 35% by weight, based on the total weight of the reactants in the coating composition.

The coatings used in accordance with the present invention may further comprise any other resin and/or additive that will impart the desired properties to the coating. For example, in certain embodiments, the polyurea coating can comprise a resin and/or additive that imparts other flexibility to the coating. In certain embodiments, the resin can be a polyurethane resin. Flexible polyurethane resins are known in the art and are described, for example, in U.S. Patent Application Serial Nos. 11/155,154, 11/021,325, 11/020,921, 12/056,306, and The relevant portions of these applications are incorporated herein by reference. The polyurethane itself may be added to the composition comprising the polyurea, or the polyurethane may be formed in situ in the polyurea composition. It will be appreciated that the polyurethane can be formed by reacting a hydroxy functional component with an isocyanate which is largely reacted in the same manner as the amine and isocyanate components described herein. Thus, the hydroxy functional component can be mixed with or in addition to the amine component to form a hydroxy functional component for in situ formation of the polyurethane.

Other compositions comprising polyureas suitable for use in the present invention include U.S. Patent Application Serial Nos. 11/211,188, 11/460,439, 11/591,312, 11/611,979, 11/611,982, and 11 Their compositions are described in the specification of the entire disclosure of which is incorporated herein by reference.

The polyurea coating composition of the present invention may optionally include standard materials in the art such as, but not limited to, fillers, glass fibers, stabilizers, thickeners, tackifiers, catalysts, colorants, antioxidants, ultraviolet rays. Absorbents, hindered amine light stabilizers, rheology modifiers, flow additives, antistatic agents, and other performance or property modifiers well known in surface coating technology, and mixtures thereof. Suitable rheology modifiers include solid and/or liquid rheology modifiers which may be organic based and/or inorganic based polymers such as bentonite, aerosolized cerium oxide, BYK 411 (available from Chemie). ; or a combination thereof. The filler may comprise clay and/or ceria, and the tackifier may comprise an amine functional material, an amine decane, and the like; examples of fillers and tackifiers are further described in U.S. Publication No. 2006/0046068 and the U.S. Application No. 11/591,312, which is incorporated herein in its entirety by reference. In alternative embodiments, the materials may be combined with an isocyanate component, an amine component, or both. In another embodiment, at least one of these materials is added to the amine followed by reaction with the isocyanate. In certain embodiments, the coating may further comprise a small amount of solvent, and in certain embodiments, the coating may be substantially solvent free. "Substantially solvent free" means that the coating may contain a small amount of solvent, such as 5%, 2%, 1% or less.

In another embodiment, the coating compositions of the present invention may include a colorant. As used herein, the term "colorant" means any substance that imparts color and/or other opacity and/or other visual effects 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 may be used in the coating of the present invention.

Examples of colorants include pigments, dyes, and tints, such as those used in the paint industry and/or those listed by the Dry Color Manufacturers Association (DCMA), as well as special effect compositions. . Colorants can include, for example, finely powdered solid powders that are insoluble but wettable under the conditions of use. The colorant can be organic or inorganic and can be agglomerates or non-agglomerates. The colorant can be incorporated into the coating by grinding or simple mixing. The colorant can be incorporated into the coating by grinding using a grinding vehicle such as an acrylic grinding media, and those skilled in the art will be familiar with the use of the milling media.

Examples of pigment and/or pigment compositions include, but are not limited to, carbazole dioxazine crude pigments; azo, monoazo, disazo, naphthol AS, salt (lake), benzimidazolone, Condensation, metal complex, isoindolinone, isoporphyrin and polycyclic phthalocyanine, quinacridone, hydrazine, perinone, diketopyrrolopyrazole, thioindigo , indanthrone, pyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine, triaryl , quinacridone pigment; diketopyrrolopyrrole ("DPPBO red"), titanium dioxide, carbon black, carbon fiber, graphite, other conductive pigments and / or fillers, and mixtures thereof. The terms "pigment" and "colored filler" are used interchangeably.

Examples of dyes include, but are not limited to, solvent-based and/or water-based dyes such as acid dyes, azo dyes, basic dyes, direct dyes, disperse dyes, reactive dyes, solvent dyes, sulfur dyes, mordant dyes, for example : bismuth vanadate, ruthenium, osmium, aluminum, quinacridone, thiazole, thiazine, azo, indigo, nitro, nitroso, oxazine, phthalocyanine, quinoline, guanidine and triphenylmethane.

Examples of coloring agents include, but are not limited to, pigments dispersed in water-based or water-miscible carriers, such as AQUA-CHEM 896, available from Degussa, Inc., Accurate Dispersions, available from Eastman Chemical, Inc. Department of CHARISMA COLORANTS and MAXITONER INDUSTRIAL COLORANTS.

As noted above, the colorant can be in the form of a dispersion including, but not limited to, a dispersion of nanoparticles. The nanoparticle dispersion can include one or more highly dispersed nanoparticle colorants and/or colorant particles that produce the desired visible color and/or opacity and/or visual effect. The nanoparticle dispersion can include a colorant such as a pigment or dye 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 co-milling an organic or inorganic pigment starting material with a grinding media having a particle size of less than 0.5 mm. Examples of nanoparticle dispersions and methods for their manufacture are found in U.S. Patent No. 6,875,800 B2, the disclosure of which is incorporated herein by reference. The nanoparticle dispersion can also be produced by crystallization, precipitation, gas phase condensation, and chemical abrasion (i.e., partial dissolution). To minimize the re-agglomeration of the nanoparticles within the coating, a resin coated nanoparticle dispersion can be used. As used herein, "resin-coated nanoparticle dispersion" means a continuous phase in which discrete "composite particles" are dispersed, and the "composite particles" comprise nanoparticles and nanoparticles on the nanoparticles. coating. Examples of the resin-coated nanoparticle dispersions and their methods of manufacture are described in U.S. Patent Application Serial No. 10/876,031, filed on Jun. U.S. Patent Application Serial No. 60/482,167, filed on Jan. 24, which is hereby incorporated by reference.

Examples of special effect compositions that can be used in the coatings of the present invention include the production of one or more appearance effects (such as, reflective, pearlescent, metallic luster, phosphorescent, fluorescent, photochromic, photosensitive, thermochromic, angiochromic (goniochromism) and/or color change pigments and/or compositions. Other special effect compositions can provide other perceptible properties such as light reflectivity, opacity or texture. In a non-limiting embodiment, the special effect composition can produce a color shift such that when the coating is viewed at different angles, the color of the coating changes. An example of a color effect composition is found in U.S. Patent No. 6,894,086, the disclosure of which is incorporated herein by reference. Other color effect compositions may include transparent coated mica and/or synthetic mica, coated ceria, coated alumina, transparent liquid crystal pigments, liquid crystal coatings and/or due to refractive index differences within the material rather than due to material surface and Any composition that causes a difference in refractive index between the air to cause interference.

In certain embodiments, the photosensitive composition and/or photochromic composition (which reversibly changes its color when exposed to one or more light sources) can be used in the coatings of the present invention. The photochromic and/or photosensitive composition can be activated by exposure to radiation of a specified wavelength. When the composition is excited, the molecular structure changes and the altered structure exhibits a novel color that is different from the original color of the composition. When the radiation exposure is removed, the photochromic and/or photosensitive composition can return to a dormant state wherein the composition returns to the original color. In a non-limiting embodiment, the photochromic and/or photosensitive composition can be colorless in a non-excited state and exhibit color in an excited state. A full color change can occur from a few milliseconds to a few minutes, such as 20 seconds to 60 seconds. Examples of photochromic and/or photosensitive compositions include photochromic dyes.

In one embodiment, the photosensitive composition and/or photochromic composition can be associated with and/or at least partially associated with the polymeric material of the polymer and/or polymerizable component (such as by covalent bonding) ). Photosensitivity associated with and/or at least partially associated with a polymer and/or polymerizable component in accordance with non-limiting embodiments of the present invention as compared to some coatings in which the photosensitive composition can migrate out of the coating and crystallize in the matrix The composition and/or photochromic composition migrates out of the coating with minimal. Examples of photosensitive compositions and/or photochromic compositions and methods of making the same are found in U.S. Patent Application Serial No. 10/892,919, the disclosure of which is incorporated herein by reference.

In general, the colorant can be present in the coating composition in any amount sufficient to provide the desired properties, visual and color effects. The colorant may comprise from 1% to 65% by weight of the composition of the invention, such as from 3% to 40% or from 5% to 35% by weight, wherein the weight % is based on the total weight of the composition.

In another embodiment, the coating composition of the present invention when applied to a substrate has a color that matches the color of the associated substrate. As used herein, the terms "match" and like terms, when referring to color matching, mean that the color of the coating composition of the present invention generally corresponds to the desired color or the color of the associated substrate. This match can be visually observed or confirmed using a spectroscopic device. For example, when the matrix of the polyurea coating composition is a footwear component, such as a polymeric bladder or upper assembly, the color of the coating substantially matches the color of the other footwear component. For example, a toe coated in accordance with the present invention can be matched to the remaining components of the upper, the midsole, and/or the outsole. This match can be visually observed or confirmed using a spectroscopic device.

Coating system

The coating of the present invention can be part of a multilayer coating composite comprising a plurality of coatings applied thereto (such as a pretreatment layer, an electrocoat, a primer, a primer, and/or Or a transparent coating) substrate. At least one of the undercoat layer and the clear coat layer may contain a colorant, and/or the clear coat layer may contain a tackifier. The addition of a tackifier to the clear coat improves the adhesion between the clear coat and the coating composition applied thereto, but the inventors do not wish to be bound by any mechanism. In this embodiment, the coating composition of the present invention may be a reaction product of an isocyanate with an amine and a coloring agent additive. The coating composition of the present invention containing a colorant can be applied to at least a portion of the article or structure. The color of the coated article or structure can match the color of the associated substrate. "Related matrix" may refer to a substrate in an article or structure that is not coated with the coating composition of the present invention; the substrate that is joined, attached, or adhered to the article or structure but not coated with the coating composition of the present invention may also be a "related matrix." "."

Accordingly, the present invention is further directed to a method of coating a substrate comprising coating any of the coating compositions described herein onto at least a portion of the substrate. The coating compositions of the present invention can be formulated and coated using a variety of techniques known in the art. In an embodiment, conventional spray techniques can be used. In this embodiment, the isocyanate may be combined with the amine such that the ratio of the isocyanate group equivalent to the amine equivalent is greater than 1, and the isocyanate and the amine may be applied to the substrate in a volume ratio of 1:1; the reaction mixture may be Coating onto an uncoated or coated substrate to form a first coating on the uncoated substrate or to form a subsequent coating on the coated substrate. In determining the ratio of isocyanate group equivalents to reactive amine group equivalents, all amine reactive groups, i.e., amine groups from any one or more of the amines used in the coating, are contemplated. Those skilled in the art will appreciate that in calculating the ratio of isocyanate equivalents to amine component equivalents, the count of all reactive amine groups can include hydroxyl groups and/or thiol groups. Those skilled in the art will also recognize that other mixing volumes or weight ratios can be used while maintaining a net ratio of the sum of the isocyanate functional groups to the amine, hydroxyl, and/or thiol groups greater than one.

It will be appreciated that the compositions of the present invention are two component ("2K") compositions. Thus, the isocyanate component and the amine component remain separated until just prior to coating. It will be appreciated that the composition may be cured under ambient conditions, but hot air or heat curing may be applied to the coating composition to accelerate the curing of the coating composition or to enhance coating properties such as adhesion. Other components containing other ingredients may be used according to the needs of the user.

In one embodiment, a sprayable coating composition can be prepared using a two component mixing device. In this embodiment, the isocyanate and amine are added to the high pressure impingement mixing device. The isocyanate was added to the "A side" and the amine was added to the "B side". The A side stream and the B side stream collide with each other and are immediately sprayed onto at least a portion of the uncoated or coated substrate. The isocyanate is reacted with an amine to produce a coating composition that cures upon application to an uncoated or coated substrate. The A side and / or the B side can also be heated before coating to reach Temperature of 70 ° C (such as 60 ° C). Heating can help to better match the viscosity between the two components and thus achieve better mixing, but it is not a necessary condition for the curing reaction to occur. In fact, the benefit achieved by the present invention is that the viscosity is reduced and thus the "sprayability" is better without the need to heat one or both of the components. This benefit is particularly beneficial when heating and/or pressurization is not desired, such as when coating walls in caves, mines, and other enclosed structures. Therefore, The A side and/or the B side are coated at a temperature of 23 ° C (such as 7 ° C to 14 ° C).

In some embodiments, a coating apparatus "static mixing tube" applicator known in the art can be used in the present invention. In this device, the isocyanate and the amine are each stored in separate chambers. When pressure was applied, the components were introduced into the mixing tube in a volume ratio of 1:1. Component mixing is affected by turbulent flow patterns within the tube or by the path of the corkscrew. The outlet end of the tube can have an atomizing capability suitable for spraying the reaction mixture. Alternatively, the fluid reaction mixture can be applied to the matrix in the form of beads. Static mixing tube applicators are available from Plas-Pak Industries Inc. or Cammda Corporation.

The volume mixing ratio of the isocyanate to the amine may be a ratio at which the reaction mixture of the obtained isocyanate and the amine may be applied to the substrate in a volume ratio of 1:1. As used herein, "volume mixing ratio 1:1" means that the volume mixing ratio of each component varies by up to 20% or up to 10% or up to 5%.

The equivalent ratio of isocyanate groups to amine groups can be selected to control the cure rate of the coating compositions of the present invention. In certain embodiments, it has been found that when the equivalent ratio of isocyanate groups to amine groups (also referred to as reaction index) is greater than 1, such as from 1.01:1 to 1.10:1, or from 1.03:1 to 1.10:1, or 1.05 Curing and adhesion advantages are obtained when 1 to 1.08:1, or 1.01:1 to 1.4:1, or 1.01:1 to 1.5:1, or 1.3:1 or greater than 1.3:1. For example, the use of such ratios can be obtained on clear coatings having lower surface functionality after curing, such as clear coatings containing urethane melamine, hydroxy melamine, 2K urethane and decane. Good adhesion. The term "volume ratio 1:1" means that the volume ratio of the components varies by up to 20% or up to 10% or up to 5%.

In a non-limiting embodiment, commercially available mixing devices can be used, such as those described in paragraphs [0037] and [0038] of U.S. Patent Publication No. 2007/0160851, the disclosure of which is incorporated herein by reference. This is incorporated herein by reference.

The coating compositions of the present invention can be applied to a variety of substrates. Non-limiting examples of suitable substrates can include, but are not limited to, metal, natural and/or synthetic stone, ceramic, glass, brick, cement, concrete, cinder brick, wood, and composites and laminates thereof; wallboard, Drywall, sheetrock, cement board, plastic, paper, PVC; roofing materials such as shingles, roofing composites and laminates, and roof drywall; polystyrene foam, Plastic composites, acrylic composites, impact composites, asphalt, fiberglass, earth, gravel and the like. Metals may include, but are not limited to, aluminum, cold rolled steel, electrogalvanized steel, hot dip galvanized steel, titanium, and alloys; plastics may include, but are not limited to, TPO, SMC, TPU, polypropylene, polycarbonate, polyethylene And polyamine (nylon). The substrate may be a primed metal and/or plastic; that is, an organic or inorganic layer is applied thereto. Furthermore, the coating compositions of the present invention may be applied to the substrates to impart one or more of a variety of properties such as, but not limited to, corrosion resistance, abrasion resistance, impact resistance, fire resistance. And/or heat resistance, chemical resistance, ultraviolet light resistance, structural integrity, impact relaxation, explosion mitigation, sound absorbing, decorative and the like. As used herein, "shock mitigation" refers to the action of reducing or reducing bullets or other types of gun ammunition. As used herein, "explosion mitigation" refers to reducing or mitigating the secondary effects of an explosion. In a non-limiting example, the coating composition of the present invention can be applied to at least a portion of a building structure or article, such as, but not limited to, a vehicle. "Carriers" include, but are not limited to, civil, commercial and military land, water and airborne vehicles such as automobiles, trucks, boats, boats, submarines, aircraft, helicopters, highly mobile multi-purpose wheeled vehicles and tanks. The article can be a building structure. "Building structure" includes, but is not limited to, at least a portion of structures (including residential, commercial, and military structures) such as roofs, floors, support beams, walls, and the like. The "building structure" also includes mining-related structures (including structures with limited caliber). Typical mine structures include trunk lines, auxiliary trunk lines, mining roadway entrances, production mining areas, vents, and other active work areas associated with underground mining. Thus, the compositions of the present invention can also be used to coat mine supports, beams, seals, stops, mine walls, exposed formations, and the like, and can be further sealed separately or in combination with other layers. / or strengthen the mine structure. As used herein, the term "matrix" may refer to an outer or inner surface of at least a portion of an article, or the article itself. In an embodiment, the base body is a truck compartment.

In certain embodiments, the substrate can comprise a footwear component and the article is a footwear or shoe. Accordingly, the present invention is further directed to footwear comprising polyurea. More specifically, one or more components of the footwear may comprise a polyurea coating, and/or a polyurea used to form the material of the assembly itself. The polyurea can be the polyurea described above or any other polyurea known in the art.

As used herein, the terms "shoes" and "shoes" include track and field shoes and sports shoes, men's and women's dress shoes, men's and women's casual shoes, children's shoes, sandals, flip flops, boots, work boots. Outdoor footwear, orthopedic shoes, slippers and the like. The term "shoe assembly" includes any component of a shoe, including an outsole, a midsole, a polymeric bladder, an upper material, and an insole. It should be understood that these components are made from many different materials or substrates. In certain embodiments, a footwear assembly coated in accordance with the present invention forms a full upper or a partial upper. A particularly suitable shoe face coated in accordance with the present invention is divided into a toe. "Lace" is understood to mean the front end portion of a shoe that is typically subjected to relatively high levels of wear and/or wear. It has been surprisingly found that coating this portion of the shoe with a composition comprising polyurea results in improved wear resistance and/or abrasion resistance.

In another embodiment, the coated assembly comprises a polymeric balloon. The polymer bladder can be filled, for example, with pulp, water, or other fluids such as gases including air, nitrogen, and the like. Such airbags are known in the footwear industry and are described, for example, in U.S. Patent Nos. 6,944,973, 6,119,371, 5,713,141, 5,952,065, 5,353,459, 4,506,460, and 4,219,945. The relevant portions of the patents are hereby incorporated by reference. It has been surprisingly found that coating a polymeric balloon with a composition comprising polyurea provides the balloon with improved puncture resistance, for example, against sharp objects such as thorns, rocks, metal objects, glass articles, etc.; The object can pierce the footwear airbag.

In certain embodiments, the polymeric balloon is contained within a midsole, and the midsole is a midsole that is at least partially coated with a composition comprising polyurea. For example, a polyurea composition can be applied to the underside of a balloon containing a nitrogen-filled polymer to protect the balloon from puncture failure. In other embodiments, the polymeric balloon is contained within the outsole.

The polyurea-containing coating used to coat footwear and/or footwear components in accordance with the present invention can be any polyurea coating known in the art. It will be appreciated that the polyurea is typically formed by reacting an amine component with an isocyanate component. Any amine and/or isocyanate known in the art may be used, including any of the amines and/or isocyanates described above, and/or any of those described in US Publication No. 2006/046068 A1, 2007/0160851 A1. No. 2007/0160853 A1 and No. 2008/0160318 A1, and U.S. Patent Application Nos. 11/460,439, 11/591,312, 11/611,982, 12/122,980, 12/122,972 And their amines and/or isocyanates in U.S. Patent Application Serial No. 12/122,983, the entire disclosure of which is incorporated herein by reference. In certain embodiments, the polyurea is formed from a reaction mixture comprising: a first component comprising an isocyanate, the first component being Having a temperature of 7 ° C a viscosity of 2000 centipoise; and a second component comprising an amine, Having a temperature of 7 ° C Viscosity of 1700 centipoise. Any other ingredients as described above may also be used in one or both of these components.

In one embodiment, the coating composition of the present invention can be applied to a carrier film or used as a double-sided coating application to create an engraved surface, the carrier film and the double-coated application described in U.S. Patent Application Serial No. 11/460,439, paragraphs [0041] to [0046] and paragraphs [0047] through [0049] are incorporated herein by reference. In some embodiments, the carrier film can have a thickness of up to 1 inch. In certain embodiments, the flexural modulus of the carrier film can be as measured according to ASTM-412. 1500 mPA, such as 1400 mPa.

In certain embodiments, the coating compositions of the present invention can be applied to a bare (eg, untreated, uncoated) substrate, a pretreated substrate, and/or a coated substrate having at least one other coating. . In one embodiment, the coating compositions of the present invention can be applied to a multilayer coating composite. The first coating applied to the substrate can be selected from various coating compositions known in the art for surface coating substrates. Non-limiting examples can include, but are not limited to, electroplatable film forming compositions, primer compositions, pigmented or unpigmented single coating compositions, pigmented or unpigmented basecoat compositions, transparent faces Paint compositions, industrial coating compositions, and the like. In another non-limiting embodiment, the coating composition of the present invention can be applied to a substrate comprising a pretreatment and a coating such as, but not limited to, an electrocoat, a primer, a primer, a clearcoat, and Combined) on a multilayer coating composite. In other embodiments, the coatings of the present invention can be used with any of the coatings described above and/or another polyurea coating and/or polyurea/polyurethane coating. The coating may comprise the same or different polyurea or polyurea/polyurethane coating compositions. For example, the first layer can be a polyurea composition comprising an aliphatic and/or aromatic amine component and/or an aliphatic and/or aromatic isocyanate; and the second layer can comprise the same or different aliphatic And/or a combination of an aromatic amine component and/or an aliphatic and/or aromatic isocyanate. In another embodiment, the outermost coating may comprise a coating composition that provides the desired durability. The desired durability may depend on the use of the coating composition of the present invention and/or its coatable substrate. In one embodiment, a combination of aliphatic and/or aromatic amines and/or isocyanates may be selected to provide the outermost composition with considerable durability. For example, when tested using the Weatherometer (Atlas Material Testing Solutions) according to the SAE J1960 method, the outermost coating may have a durability of 1000 kJ to 6000 kJ or 800 hours to 4000 hours. In this embodiment, the first layer may be a polyurea composition comprising an isocyanate and an amine, wherein at least one of the amine and/or polyisocyanate may be aromatic; and the second layer may comprise an aliphatic amine and a fat A polyurea composition of a family isocyanate. In some embodiments, a flame retardant coating composition, such as a water-based latex flame retardant coating composition, can be applied to the cured polyurea coating composition disclosed herein. For example, in certain embodiments, SPEEDHIDE 42-7 (available from PPG Industries, Inc.) can be applied to a polyurea coating composition. In other embodiments, Chemical Agent Resistant Coating (CARC) known in the art can be applied to at least a portion of the polyurea to enhance its fire resistance.

The footwear component that is at least partially coated in accordance with the present invention may be uncoated or may have been pre-coated with another coating or other coating. It may be desirable to select a polyurea coating that will be compatible with previous coatings. In certain embodiments, it may be desirable to add a tackifier to the polymeric coating whether the component is coated or not. In other embodiments, it may be desirable to apply the tackifier directly to the footwear component prior to application of the polyurea coating. In other embodiments, it may be desirable to wipe the footwear assembly with a solvent prior to application of the polyurea coating; suitable solvents include those solvents that are not deleterious to the coated substrate, such as acetone, MEK, isopropanol, and the like. . In other embodiments, particularly when the footwear component comprises a foam, it may be desirable to immerse the component in a powder prior to application of the polyurea coating, as described in U.S. Patent Application Serial No. 11/448,627, the disclosure of which application This is incorporated herein by reference in its entirety.

In other embodiments, the invention is directed to footwear comprising a component comprising polyurea. In such embodiments, rather than having a polyurea coating on the assembly (or in addition to having a polyurea coating on the assembly), the polyurea actually forms part of the material that makes up the assembly. A typical shoe assembly that is within this embodiment is an outsole, but the invention is not limited thereto.

Any of the compositions described above comprising polyureas can be used to form a footwear component. Typically, the composition comprising the polyurea will further comprise a particulate filler. The particulate filler can be any organic or inorganic filler such as a filler used to form, for example, rubber products such as typical outsole, tires, and the like. In this technique, these fillers are sometimes referred to as "reinforcing fillers". A typical reinforcing filler is cerium oxide. Any suitable hydrophilic or hydrophobic cerium oxide, such as highly dispersed precipitated cerium oxide, may be used as understood by those skilled in the art to refer to cerium oxide having the basic ability to disintegrate and disperse in the matrix. Ceria is widely available, such as from PPG Industries, Inc. Another suitable reinforcing filler includes carbon black. Other fillers include, for example, metal oxides and metal carbides (including alumina and boron carbide), clay (natural and synthetic), mica (natural and synthetic), glass fiber, inorganic metal powder, talc, calcium sulfate, strontium. Calcium acid, organic fibers, polymer fibers and polymer particles.

The filler can be in any form such as a powder, microbeads, granules, spheres, particles or fibers. The size of the filler can range, for example, from 0.01 microns to 1000 microns. Particulate fillers can be used to affect the physical and/or mechanical properties of the polyurea, such as viscosity, modulus, tangent angle, and the like. Footwear comprising components made using the polyurea described herein and one or more particulate fillers may also have reduced hysteresis, improved traction, and the like. Particulate fillers can also be used to improve the durability and/or wear resistance of footwear components.

When the polyurea composition used to form the footwear component of the present invention comprises an inorganic filler, it may further comprise a coupling agent. A coupling agent is understood to be an agent having a portion that reacts with the surface of the inorganic filler and a portion that binds to the polyurea or the component forming the polyurea. The coupling agent may comprise, for example, an organodecane or may comprise a bifunctional ceria coupling agent. Couplers are widely available, and those skilled in the art can determine the appropriate coupler depending on the type of filler used. Suitable coupling agents are described, for example, in U.S. Patent No. 7,211,611, the disclosure of which is incorporated herein by reference.

The composition comprising the polyurea can be formulated in any manner. After compounding, a shoe assembly (such as an outsole) can be formed from the polyurea composition by a number of methods. The method includes, for example, spraying to another shoe component (such as a midsole); casting a polyurea formulation sheet and post-processing the sheet into a desired shape and form; casting the polyurea formulation into a mold; The urea formulation is sprayed into the mold or shot out to form the assembly. The use of any of the polyurea compositions described herein (especially with one or more fillers) in the manufacture of shoe components provides ease of manufacture as compared to conventional methods of making natural rubber and/or synthetic rubber. In addition, a shoe assembly (such as an outsole) made as described herein will generally provide good traction to the user, especially under wet conditions such as rain or snow. The assembly will also typically exhibit enhanced wear resistance and/or wear resistance as compared to a typical natural and/or synthetic rubber outsole. Finally, the puncture resistance of the assembly is enhanced compared to existing footwear components. When the component is a polymer balloon coated with a polyurea composition itself or a polymer balloon coated with a polyurea composition itself, it is contained in a polyurea coated component or contained in polyurea. This is especially true when the components are inside.

The abrasion resistance observed in the footwear assembly of the present invention is particularly critical in the sole and other portions of the outsole, but in footwear (especially tennis shoes where the toe is often towed during exercise, such as during use) ) The toe of the toe is also particularly critical. It is often the case that the wearer can wear the toe cap so that the aesthetics are even damaged and eventually cause the toe to wear through the hole.

The coating of the invention or the coating used according to the invention may be applied to a thickness of from 20 mils to 1000 mils, or from 40 mils to 150 mils, or from 60 mils to 100 mils (1524 micrometers - 2540 microns), or on a dry film in the range of 500 mils to 750 mils. It should be understood that these coatings are relatively "thick". The coating compositions of the present invention may also be applied in relatively thin layers, such as from 0.1 mils to less than 15 mils, such as from 0.1 mils to 10 mils, from 0.5 mils to 3 mils, or from 1 mil to 2 mils. . Any endpoints within these ranges may also be combined. The layers can be used alone or in conjunction with other coatings, such as any coating known in the art or described herein. When coated with a sufficient thickness (eg, 10 mils to 1000 mils, such as 100 mils to 200 mils or 125 mils +/- 10 mils), the polyurea layer of the present invention can provide an explosion and/or Impact mitigation. When coated at a sufficient thickness (e.g., from 0.5 mils to 100 mils), the composition provides abrasion resistance, puncture resistance, and the like to the footwear. It will be appreciated that the thickness of the composition required to provide an appropriate degree of puncture resistance can be greater than the thickness of the composition required to provide an appropriate degree of abrasion resistance. The appropriate thickness can be determined according to the needs of the user.

Having described the specific embodiments of the present invention in detail, it is understood that various modifications and alternatives can The scope of the present invention is to be construed as being limited by the scope of the appended claims.

Example 1

The modified polyphosphoric acid diol was prepared from the following ingredients:

The above ingredients are fed into a suitable reactor equipped with a heating mantle, a reflux condenser, an overhead stirrer, a thermocouple and a N ₂ inlet. A nitrogen blanket was applied to the reactor and the mixture was heated to 140 °C over 2 hours in increments of 10 °C. The reaction mixture was maintained at this temperature and sampled for epoxy equivalent weight approximately every 4 hours. After 13.25 hours, the epoxy equivalent weight was determined to be infinite (no titration endpoint) and the reaction was judged complete. The obtained resin was a transparent viscous fluid, and its measured solid content (110 ° C, 1 hr) was 88.4%. According to the Gardner-Holt scale, the viscosity was Z2, the acid value was 2.7 mg KOH/g, and the hydroxyl value was obtained. 82.2 mg KOH/g; and Mw was 1126, Mn was 553, Mz was 1866, and the peak molecular weight was 620 as determined by gel permeation chromatography (relative to polystyrene standards).

Example 2

A substantially compatible isocyanate component comprising a phosphorus-containing isocyanate functional prepolymer is prepared from the following ingredients as described below.

A total of 7537 grams of DESMODUR XP2580 was placed in a suitable reaction vessel equipped with a stirrer, temperature probe, condenser, and nitrogen inlet tube and blanketed with nitrogen. A total of 338 grams of the resin from Example A and 875 grams of FYROL PCF were then added and mixed for 15 minutes at ambient temperature. Next, 0.14 grams of dibutyltin dilaurate was added and the mixture was slowly heated to 50 °C, then heated to 80 °C and finally heated to 100 °C. The contents of the reactor were cooled, and the isocyanate equivalent weight of the resin was measured and the equivalent isocyanate equivalent weight of the resin was determined to be 253 g/e. A total of 307 grams of XP2580 was then added to the contents of the flask, thoroughly mixed and the contents of the reactor were decanted. The final material was a clear, compatible resin having a measured solids content of 99% and an isocyanate equivalent weight of 250 grams per equivalent.

Example 3

A slurry of the amine component is prepared from the following ingredients as described below:

The ingredients were combined and fed into a Premier Mill HM 1.5 VSD Series SuperMill (SPX Corporation) with a 8 mm addition of 1.0 mm Mill Mates Plus TZP grinding media (Zircoa, Inc.) at a grinding speed of 2400 rpm Grinding. When the particle size was 7.5 Hegman after the introduction to the grind meter, it was judged that the grinding was completed.

Example 4

The amine component is prepared from the following ingredients as described below: Then add the ingredients listed in the above table together under ambient conditions.

The invention and comparative examples

The polyurea coating composition of the present invention (Example 4 and Example 2 in Table 1 below) was prepared by combining the isocyanate functional "A" side component and the amine functional "B" side component in the following manner: A polyurea coating composition was prepared by mixing each A side component having a volume ratio of 1:1 with each B side component in a static mixing tube applicator apparatus available from Plas-Pak Industries, Inc. The coating composition was sprayed onto a 6" x 18" plate of calcium citrate fiber reinforced high pressure treated building sheet containing natural source fibers at a film thickness of 70 mils to 90 mils (according to the name of Tunnel Board Z from Taylored) Industries, Indianola, PA). The tack time of the coating was determined by periodically touching the panel with a gloved hand and was judged to be non-tacky when the glove no longer adhered to the coating. In all cases, the coating was tack-free for <2 minutes. A comparative example (examples BDL1724S and CAT128 in Table 1 below) was also applied in the manner described above with the exception that the "A" and "B" side components were heated to 60 °C prior to spraying. In these examples, the isocyanate "A" side component was CAT-128 (available from PPG Industries, Inc.) and the amine functional "B" side component was BDL-1742S (available from PPG Industries, Inc.).

The viscosity measurement results of the present invention and comparative examples were measured using a PHYSICA MCR 301 rheometer (available from Antone Paar GmbH, Austria) having a 50 mm/1° conical disk. The sample to be measured was loaded onto a conical disk at 23.89 ° C, and the viscosity measurement was obtained at a constant shear rate of 1000 s ^-1 at an appropriate temperature.

As can be seen from Table 1, the isocyanate component of the present invention (Example 2) has a significantly lower viscosity, whereby the isocyanate component of the present invention can be sprayed onto the substrate without heating the components prior to spraying.

Example 5

The amine component is prepared from the following ingredients as described below:

Then add the ingredients listed in the above table together under ambient conditions.

Example 6 and Example 7

The polyurea coating composition of the present invention (Example 6 and Example 7 in Table 2) was prepared by combining the isocyanate functional "A" side component with the amine functional "B" side component in the following manner: A polyurea coating composition was prepared by mixing each A side component having a volume ratio of 1:1 with each B side component in a static mixing tube applicator apparatus obtained from Plas-Pak Industries, Inc. A coating composition of about 20 mils was sprayed onto the TPU foam substrate under ambient conditions. After aging for 24 hours under ambient conditions, Examples 6 and 7 were excellent in crosshatch adhesion (according to ASTM D3359-08) to the TPU foam matrix.

Claims (19)

A coating composition comprising polyurea formed from a reaction mixture comprising: (a) a first component comprising an isocyanate, the first component being Having a temperature of 7 ° C a viscosity of 2000 centipoise, wherein the isocyanate comprises an isocyanate functional prepolymer formed from a reaction mixture comprising an isocyanate and a substance comprising a phosphorus containing polyol; and (b) comprising an amine Two components, wherein the second component is Having a temperature of 7 ° C Viscosity of 1700 centipoise. The coating composition of claim 1, wherein the second component is Having a temperature of 7 ° C Viscosity of 1000 centipoise. The coating composition of claim 1 wherein the phosphorus-containing polyol is the reaction product of the initial phosphorus-containing polyol and the epoxy-functional compound. The coating composition of claim 3, wherein the epoxy functional compound comprises glycidyl neodecanoate. The coating composition of claim 3, wherein the phosphorus-containing polyol is a reaction product of a phosphoric acid-containing, epoxy-functional compound and, optionally, a phosphorus-containing polyol. A method of coating a substrate comprising applying a coating composition according to claim 1 to at least a portion of the substrate. A substrate that is at least partially coated with a coating composition as claimed in claim 1. The substrate of claim 7, wherein the substrate comprises footwear. A footwear comprising an assembly that is at least partially coated with a coating composition of claim 1. The footwear of claim 9, wherein the component comprises an upper component. The footwear of claim 10, wherein the upper assembly comprises a toe assembly. The footwear of claim 9, wherein the component comprises a polymeric balloon. The footwear of claim 9, wherein the composition comprising the polyurea further comprises a tackifier. The footwear of claim 9, wherein the composition comprising the polyurea further comprises a polyurethane. A footwear comprising an assembly comprising the coating composition of claim 1. The footwear of claim 15 wherein the component comprises a midsole. The footwear of claim 15 wherein the component comprises an outsole. The footwear of claim 15 wherein the component further comprises a reinforcing filler. The footwear of claim 18, wherein the filler is an inorganic filler.