JP2022519589A - Their use as rubber substitutes and footwear components - Google Patents

Abstract

A rubber substitute prepared from a curable composition is provided. The curable composition comprises an isocyanate-functional prepolymer, a curing agent comprising a mixture of polyamines in which at least one polyamine has an amine equivalent of 125-250, and organic particles exhibiting a volume average particle size of at least 5 microns. Includes abrasion resistant additives. The isocyanate-functional prepolymer is (i) a reaction product of a polyisocyanate with a polyamine having a primary amino group and / or a secondary amino group, and / or (ii) a reaction product of a polyisocyanate with a polyol.

Description

Cross-reference to related applications This application is a partial continuation of US Patent Application No. 15 / 346,853, filed November 9, 2016, entitled "CURABLE COMPOSITIONS AND THEIR USE AS COATINGS AND FOOTWEAR COMPANY". .. This application is also a partial continuation of PCT International Patent Application No. PCT / US2018 / 031855, filed May 9, 2018, entitled "CURABLE COMPOSITIONS AND THEIR USE AS COATINGS AND FOOTWEAR COMPANY". Both of the aforementioned patent applications are incorporated herein by reference in their entirety.

Fields of Invention The present invention is directed to rubber substitutes prepared from curable compositions.

Background Curable compositions are often used as coated and molded or extruded articles in a wide variety of industries. Such industries include land planes such as cars, trucks, sports utility vehicles and motorcycles; surface planes such as boats, ships and submarines; aircraft such as planes and helicopters, commercial equipment and structures including walls and roofs. Equipment; structures such as construction vehicles and structures including walls and roofs, military vehicles such as military vehicles, and military structures including walls and roofs, such as ammunition cases and battery housings, among others. Not limited.

The curable composition can also be used as a rubber substitute in footwear and other industries. Footwear such as shoes is generally divided into two parts, an upper and a sole. The upper is part of the footwear designed to comfortably surround the foot, and the sole, which typically includes an insole, optionally a midsole, and an outsole, is towed, protected, cushioned, and / or It is part of footwear designed to provide a durable wear surface.

The upper is typically composed of many different components and is often made of different materials. Such materials include, for example, fabrics such as natural leather, synthetic leather, vinyl, and nylon, and other fabrics may be used. Many upper components, especially the "toes", can experience wear and / or wear during normal use of the shoe.

Similarly, soles often contain different components made of different materials. The midsole is typically made of foam such as ethylene vinyl acetate (EVA) foam or polyurethane foam such as TPU foam. These materials elastically compress under applied loads such as the forces produced by the feet and legs during physical activity. Many shoes, especially athletic shoes, include a filled shock absorber or bladder within another shoe component, such as a midsole, outsole. The bladder can be an inflatable insert made of a resistant compressible polymeric material to provide additional cushioning to the wearer of the footwear. These bladder can be filled with, for example, gel, water, or other fluid such as air or nitrogen. Outsole is often made of synthetic rubber and / or natural rubber, such as a silica-filled rubber composition. The outsole may also experience wear and / or wear during normal use of the shoe.

Therefore, it is desired to improve the resistance and / or durability of the shoe component and other consumer articles against wear, abrasion and / or other damage.

Abstract of the Invention The present invention is a rubber substitute article, which is (a) an isocyanate functional prepolymer, and (i) a reaction product of a polyisocyanate and a polyamine having a primary amino group and / or a secondary amino group. And / or a curing agent comprising a mixture of an isocyanate functional prepolymer and (b) a polyamine comprising (ii) a reaction product of a polyisocyanate and a polyol, wherein at least one polyamine in the curing agent. , A rubber substitute article prepared from a curable composition comprising a curing agent having an amine equivalent of 125-250 and (c) an abrasion resistant additive containing organic particles. Organic particles exhibit a volume average particle size of at least 5 microns.

Detailed Description of the Invention When used herein, all numbers, such as those representing values, ranges, quantities, or percentages, are referred to as "unless the term explicitly appears." It can be read as if it were prefaced by the word "about". Any numerical range listed herein is intended to include all subranges contained therein. The plural includes the singular and vice versa. The terms "contains" and similar terms are open-ended, that is, they mean "contains, but is not limited to". For example, the present invention relates to "a" polyurea, "a" polyurethane, "a" isocyanate, "a" amine, "a" polyol, "a" polythiol, "a" prepolymer, "a" catalyst and the like. As described herein, including the claims, all mixtures of such can be used. Also, as used herein, the term "polymer" means both prepolymers, oligomers, and homopolymers and copolymers, and the prefix "poly" is more than two or two. Refers to many.

References herein to any monomer (s) generally refer to a monomer that can be polymerized with another monomer or another polymerizable compound, such as a polymer. Unless otherwise indicated, it should be understood that when the monomer components react with each other to form a compound, the compound contains residues of the monomer component.

The curable composition used to prepare the rubber substitutes of the present invention comprises (a) an isocyanate-functional prepolymer. The isocyanate-functional prepolymer comprises (i) a reaction product of a polyisocyanate with a polyamine having a primary amino group and / or a secondary amino group, and / or (ii) a reaction product of a polyisocyanate with a polyol. It is noted that when used in a list, the phrase "and / or" is meant to include each individual component in the list, and alternative embodiments that include any combination of components. sea bream. For example, the list "A, B, and / or C" is meant to include seven other embodiments comprising A, or B, or C, or A + B, or A + C, or B + C, or A + B + C. Also, as used herein, an "isocyanate-functional prepolymer" is a reaction product of a polyisocyanate with a polyamine and / or a polyol and, optionally, other isocyanate-reactive groups such as thiol. Pointing to, isocyanate-functional prepolymers have at least one free isocyanate functional group (NCO). A combination of isocyanate-functional prepolymers can be used according to the present invention. Reaction mixtures used to prepare isocyanate-functional prepolymers are usually essentially free of any phosphorus-containing polyols. Curable compositions are also usually essentially free of phosphorus-containing polyols or reaction products thereof. When used throughout the specification, including the claims, "essentially absent" means that the compound is intentionally absent in the composition, if the compound is present in the composition. , The compound is accidentally present in an amount of less than 0.1 weight percent, usually less than a trace amount.

As used herein, the terms "curable" and "curable" mean that any crosslinkable component of the composition is at least partially crosslinked or crosslinked via a chemical reaction. Also refers to a good composition. For example, the crosslink density (ie, degree of crosslink) of the crosslinkable component is 5% to 100% of the complete crosslink, eg, at least 5%, or at least 35%, or at least 50%, and at most 100%, or. At most 85% range. Those skilled in the art will appreciate that the presence and extent of cross-linking, i.e., the cross-linking density, can be determined by various methods such as dynamic mechanical thermal analysis (DMTA) using a Polymer Laboratories MK III DMTA analyzer performed under nitrogen. Will do.

As used herein, the term "isocyanate" includes unblocked isocyanate compounds capable of forming covalent bonds with reactive groups such as hydroxyl groups, thiol groups, or amine functional groups. Therefore, isocyanate can refer to "free isocyanate". Alternatively, the isocyanate can be blocked with any known blocking agent.

Suitable polyisocyanates for use in the preparation of isocyanate-functional prepolymers can include one or more of those known in the art. Non-limiting examples of suitable polyisocyanates include monomeric, dimeric, trimer, and / or oligomeric polyisocyanates. For example, isocyanates can be C2 _{- C20} linear, branched, cyclic, aromatic, aliphatic, or a combination thereof.

Isocyanates The polyisocyanates used to prepare functional prepolymers are often aliphatic. Examples of suitable polyisamethylenes are isofolone diisocyanate (IPDI), which is 3,3,5-trimethyl-5-isosyanato-methyl-cyclohexamethylene diisocyanate; cyclohexamethylene diisocyanate, 4,4'-methylene dicyclohexamdicyclohexamethylene diisocyanate (H ₁₂ MDI). Hydrogenation materials such as 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (HMDI), 1,7-heptamethylene diisocyanate, 2,2,4- and 2, Polymethylene isocyanates such as 4,4-trimethylene hexamethylene diisocyanate, 1,10-decamethylene diisocyanate, and 2-methyl-1,5-pentamethylene diisocyanate; and mixtures thereof.

Examples of aromatic polyisocyanates include phenylene diisocyanate, toluene diisocyanate (TDI), xylene diisocyanate, 1,5-naphthalene diisocyanate, chlorophenylene 2,4-diisocyanate, bitluene diisocyanate, dianisidine diisocyanate, trizine diisocyanate, and alkylated benzene. Methylene interrupted aromatic diisocyanides such as diisocyanates and methylene diphenyl diisocyanates, 4,4'-isomers (MDI) containing alkylation analogs such as 3,3'-dimethyl-4,4'-diphenylmethane diisocyanates, and polymeric methylene diphenyls. Diisocyanates; mixed aralkyl diisocyanates such as tetramethylxylyl diisocyanate, OCN-C (CH ₃ ) ₂ -C ₆ H ₄ C (CH ₃ ) ₂ -NCO; and mixtures thereof.

Polyisocyanates used to prepare isocyanate-functional prepolymers include dimer such as uretdione of 1,6-hexamethylene diisocyanate, trimer such as biuret and isocyanurate of 1,6-hexane diisocyanate, and Isophorone diisocyanate isocyanurates, as well as alophonates, can be included. Modified isocyanates containing carbodiimides and ureton-imines, as well as mixtures thereof, can also be used. Suitable materials include, but are not limited to, those available from Covestro LLC under the name DESMODUR N 3200, DESMODUR N 3300, DESMODUR N 3400, DESMODUR N 3900, and DESMODUR XP 2580. .. TOLONATE HDT LV2, available from Vencorex Chemicals, is also suitable. Isocyanate-functional acrylics can also be used.

Based on the total weight of the resin solids in the isocyanate-functional prepolymer (a), it is advantageous to use polyisocyanates in excess, often greater than 10 weight percent. Excess polyisocyanate functions as a plasticizer in the curable composition.

The polyisocyanate is reacted with (i) a polyamine having a primary and / or a secondary amino group, and / or (ii) a polyol. Polyamines and polyols can be any of those known in the art such as acrylics, polyesters, polycarbonates, polybutadienes, and / or polyethers. Polyether is most often used. Suitable polyethers include, for example, polyoxyalkylenes having two or more skeleton-bound primary and / or secondary amino groups derived from propylene oxide, ethylene oxide, butylene oxide, or mixtures thereof. Amine can be mentioned. Examples of such amines are JEFFAMINE D-230, D-400, D-2000, HK-511, ED-600, ED-900, ED-2003, T-403, T-3000, T-5000, SD- Includes those available under the name JEFFAMIN such as 231, SD-401, SD-2001, and ST-404 (from Huntsman Corporation). Such amines have an approximate number average molecular weight in the range of 200-7500. As used herein, the number or weight average molecular weight of polymers and oligomers is determined by gel permeation chromatography (GPC) using polystyrene standards.

または

式中、置換基Ｒ１は、混合置換基を含む１～５個の炭素原子を含有する水素または低級アルキルであり、ｎは、典型的には、２～６であり、ｍは、８～１００または１００を超える。ポリ（オキシテトラメチレン）グリコール、ポリ（オキシテトラエチレン）グリコール、ポリ（オキシ－１，２－プロピレン）グリコール、およびポリ（オキシ－１，２－ブチレン）グリコールが含まれる。 Suitable polyethers having a hydroxyl group include polyether polyols such as polyalkylene ether polyols, including those having the following structural formulas:

or

In the formula, the substituent R1 is a hydrogen or a lower alkyl containing 1 to 5 carbon atoms containing a mixed substituent, n is typically 2 to 6 and m is 8 to 100. Or more than 100. Includes poly (oxytetramethylene) glycols, poly (oxytetraethylene) glycols, poly (oxy-1,2-propylene) glycols, and poly (oxy-1,2-butylene) glycols.

Also, various polyols, such as polyether polyols formed from oxyalkylation of diols such as ethylene glycol, 1,6-hexanediol, bisphenol A, etc., or other polyols such as trimethylolpropane, pentaerythritol and the like. Higher polyols are also useful. Higher functional polyols that can be utilized as shown can be made, for example, by oxyalkylation of compounds such as sucrose or sorbitol. One commonly used oxyalkylation method is to react the polyol with an alkylene oxide, such as propylene oxide or ethylene oxide, in the presence of an acidic or basic catalyst. Specific polyether polyols include TERATHANE available from Invista Corporation (eg, TERATHANE 250, TERATHANE 650, TERATHANE 1000), and TERACOL, as well as Lyndell Chemical Co., Ltd. Some are sold under the name POLYMEG available from. Also useful for isocyanate-functional prepolymers are polyester polyols, butadiene diols, and triols, as well as saturated versions thereof, chlorinated olefin polyols, hydrazides, and polyamide polyols, and polyurethane polyols.

Isocyanate-functional prepolymers are typically 1,300 to 20,000, often 1,400 to 15,000, or 4,000 to 15,000, or 5,000 to 10,000. It has a weight average molecular weight. In addition, isocyanate-functional prepolymers typically have an isocyanate equivalent of greater than 300, often greater than 400-1,000.

The curable composition used to prepare the rubber substitutes of the present invention may further comprise a non-prepolymer isocyanate such as a monomeric polyisocyanate in combination with an isocyanate functional prepolymer. The non-prepolymer isocyanate can be the same as or different from the polyisocyanate used to form the isocyanate-functional prepolymer and may include one or more of those disclosed above. .. When using a combination of isocyanates, the isocyanates should be, for example, substantially compatible, and the isocyanate-functional prepolymers can be substantially compatible with non-prepolymer isocyanates. As used herein, "substantially compatible" is a material that forms a blend with another material that is substantially homogeneous over time and remains substantially homogeneous over time. Means ability. For example, the reaction of isocyanates with organic materials in the formation of isocyanate-functional prepolymers helps to adapt the isocyanates.

The curable composition used to prepare the rubber substitutes of the present invention further comprises (b) a curing agent comprising a mixture of polyamines. At least one polyamine in the mixture has an amine equivalent of 125-250. Such polyamines provide hardness to the curable composition. Suitable polyamines can include those known in the art. Non-limiting examples of suitable polyamines include, but are not limited to, primary and secondary amines, and mixtures thereof such as any of those disclosed herein. Amine-terminated polyureas can also be used. Amines containing a tertiary amine functional group can be used provided that the amine further comprises at least two primary and / or secondary amino groups.

The at least one polyamine in the mixture having an amine equivalent of 125-250 can be an acyclic polyamine containing a secondary amino group. Including such acyclic polyamines in the curable composition is made from the curable composition even if the inorganic particles as described below are not contained in the curable composition as an abrasion resistant additive. It has been found that the wear resistance of the coated coating layer or component is significantly improved. As used herein, the term "acyclic polyamine" refers to a molecule containing more than one amino group per molecule, where an amino group is more than one or one in which the molecule does not contain a cyclic moiety. It is linked by many straight or branched aliphatic organic moieties. Suitable acyclic polyamines with an amine equivalent of 125-250, including secondary amino groups, include asparagine ester functional amines, such as those available under the name DESMOPHEN NH 1220 (Covetro LLC).

Mixtures of polyamines can include, for example, polyamines having at least two functional groups, such as bifunctional, trifunctional, or higher functional amines, and combinations thereof. Polyamines can be aromatics such as alicyclics or aliphatics, or mixtures thereof. Suitable primary polyamines include ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,3-diaminopentane (DYTEK EP, Invista), 1,6-diaminohexane, 2-methyl-1,5. -Pentanediamine (DYTEKA, Invista), 2,5-diamino-2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11 -Diaminoundecane, 1,12-diaminododecane, 1,3- and / or 1,4-cyclohexanediamine, 1-amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane (isophoronediamine or IPDA), 2,4- and / or 2,6-hexahydrotoluenediamine, 2,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane (PACM-20, Air Products) and 3,3'-dialkyl-4 , 4'-diaminodicyclohexylmethane (3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (DIMETHYL DICYKAN or LAROMIN C260, BASF; ANCAMINE 2049, Air Products) and 3,3'-diethyl-4,4' -Diaminodicyclohexylmethane, etc.), 2,4- and / or 2,6-diaminotoluene, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6-diamine, 3,5 -Dimethylthio-2,4-toluenediamine, 3,5-dimethylthio-2,4-toluenediamine, 2,4'-and / or 4,4'-diaminodiphenylmethane, dipropylenetriamine, bishexamethylenetriamine, or theirs. The combination of.

Secondary alicyclic diamines can also be used in the present invention. Suitable alicyclic diamines include JEFFLINK 754 (Huntsman Corporation), CLEARLINK 1000 (Dorf-Ketal Chemicals, LLC), and asparagine ester functional amines such as DESMOPHEN NH 1420, and DESMOPHEN NH 1520 (Co Examples are those commercially available under the name DESMOPHEN. Other suitable secondary amines that can be used in the present invention include reaction products with acrylonitrile in materials containing primary amine functionality, such as those described herein. For example, the secondary amine can be the reaction product of 4,4'-diaminodicyclohexylmethane with acrylonitrile. Alternatively, the secondary amine can be a reaction product of isophorone diamine and acrylonitrile, such as POLYCLEAR 136 (available from BASF / Hansen Group LLC). Aliphatic secondary diamines often have up to 200, and more often up to 162 amine equivalents.

Other polyamines that can be used as the curing agent (b) in the present invention include Hexion, Inc. Examples include adducts of primary polyamines with mono or polyepoxides, such as the reaction product of isophorone diamine with CARDURA E-10P, available from.

Often, the curing agent (b) is a 5-50 weight percent aliphatic polyamine with an amine equivalent of 125-250 and a 50-95 weight percent aliphatic polyamine with an amine equivalent of 900-2500. ,including. For example, the curing agent comprises 20 weight percent CLEARLINK 1000 with an amine equivalent of about 161 and 80 weight percent JEFFAMINE T-5000, which is a trifunctional aliphatic amine with an amine equivalent of about 1902.

When an acyclic polyamine having an amine equivalent of 125-250 including a secondary amino group is contained in the curing agent (b), the curing agent (b) is often the total polyamine in the curable composition. Includes the acyclic polyamine in an amount of 1 to 20 weight percent, eg, 1.5 to 15 weight percent, or 2 to 12.5 weight percent, or 3 to 10 weight percent, based on weight. For example, the curing agent is often about 8 weight percent DESMOPHEN NH 1220, an acyclic amine with an amine equivalent of about 234, CLEARLINK 1000 at about 8 weight percent, an alicyclic amine with an amine equivalent of about 161. And contains about 84 weight percent of JEFFAMINE T-5000, which is a trifunctional aliphatic amine with an amine equivalent of about 1902.

The curing agent (b) may further contain an additional resin having a hydroxyl functional group. Examples include polyester polyols such as the polyether polyols disclosed above and polyether polyols. TERATHANE 650 is often used as an additional resin in the curing agent. Such resins, when used, may be present in an amount of 2-15 weight percent based on the total weight of solids in the curing agent.

The curable composition used to prepare the rubber substitutes of the present invention further comprises (c) a wear resistant additive. Abrasion resistant additives include 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. Organic particles exhibit a volume average particle size of at least 5 microns, such as 5-60 microns, or 5-30 microns, or 5-10 microns, or 5-7.5 microns, or 9.75-60 microns. The abrasion resistant additive may further contain inorganic particles. Inorganic particles typically exhibit a volume average particle size of at least 90 microns, often at least 95 microns. Particle sizes within these size ranges are available via laser diffraction according to ISO 13320: 2009 using a HELOS particle size analyzer available from Symboltec GmbH and using Fraunhofer Enhanced Assessment, unless otherwise indicated. Be measured. Alternatively, the curable composition may be less than 5 weight percent, eg, less than 4 weight percent, eg, less than 3 weight percent, eg, less than 2 weight percent, based on the total weight of solids in the curable composition. It may contain less than 1 weight percent, for example 0 weight percent, inorganic particles containing alumina and having a volume average particle size of 90 microns or at least 90 microns. Alternatively, the composition may essentially contain no inorganic particles.

Suitable organic particles include polyethylene, polypropylene, and saturated linear primary alcohols (with an average carbon chain length of C20 to C50). Examples of such saturated linear primary alcohols include Baker Hughes, Inc. Includes UNILIN alcohol available from. As PETROLITE such as PETROLITE 5000 T6, Baker Hughes, Inc. Polyethylene and polypropylene particulate copolymers with a volume average particle size of 5.0-7.5 microns available from are also available.

Suitable inorganic particles include, among other things, untreated alumina, eg, those commercially available on the MICROGRIT line of products from the Micro Abrasives Corporation. It is also possible to combine various particles.

Depending on the intended use when the inorganic particles are included in the wear resistant additive, the weight ratio of the organic particles to the inorganic particles in the wear resistant additive may be 1: 99 to 99: 1, for example 10 :. It can range from 90 to 90:10, 50:50, or less than 10:40. Abrasion resistant additives are typically at least 0.25 weight percent, or at least 0.5 weight percent, or at least 2 weight percent, and more, based on the total weight of solids in the curable composition. It is present in the curable composition in an amount of at most 20 weight percent, or at most 10 weight percent, or at most 9 weight percent, or at most 5 weight percent. Abrasion resistant additives are typically 0.5-8 weight percent, or 1-7 weight percent, or 1.5-6 weight percent, based on the total weight of solids in the curable composition. , Or in an amount of 2-5 weight percent, are present in the curable composition.

The curable composition used to prepare the rubber substitutes of the present invention may contain one or more additional constituents. Additional constituents may include, for example, amine functional materials, adhesion promoters such as aminosilanes, halogenated polyolefins (eg, chlorinated polyolefins), or organic titanates or zirconates. 1,5-diazabicyclo [4.3.0] nona-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-en, and / or 1,4-diazabicyclo [2.2.2 ] Octane-containing tertiary amines are exemplary amine functional materials suitable as adhesion promoters. An example of an aminosilane for use as an adhesion promoter is y-aminopropyltriethoxysilane (commercially available as SILQUEST A1100 from Momentive Performance Chemicals). SILQUEST A1110 and ALINK 35 from Momentive Performance Chemicals can also be used. Other suitable amine functional adhesion promoters include 1,3,4,6,7,8-hexahydro-2H-pyrimidin- (1,2-A) -pyrimidine, hydroxyethylpiperazine, N-aminoethylpiperidine. , Dimethylamine Ethyl Ether, Tetramethylimiminopropoylamine (Commercially available as POLYCAT® 15 from Air Products and Chemicals, Inc., blocked amines such as adducts of IPDI and dimethylamine, melamine itself. Examples thereof include melamine such as, or iminomelamine resin (eg, CYMEL (registered trademark) 220 or CYMEL (registered trademark) 303 available from Allnex). The metal-containing adhesion promoter is an aluminum chelate complex (eg, King Industries). It may contain a metal chelate complex such as K-Kat 5218) available from, or tin-containing compositions such as stannous octanoate and organic tin compounds such as dibutyltin dilaurate and dibutyltin diacetate, as other adhesion promoters. Is a salt such as chlorine phosphate, a butadiene resin such as an epoxidized hydroxyl-terminated polybutadiene resin (eg, POLY bd® 605E available from Atofina Chemicals, Inc.), a polyester polyol (eg, Solveay America, Inc.). CAPA® 3091, which is a polyester triol available from, and urethane acrylate compositions such as aromatic urethane acrylate oligomers (eg, CN999 available from Sartomer Company, Inc.) can be mentioned as suitable organics. Titanate adhesion promoters include tetra n-butyl titanate, tetraisopropyl titanate, butylisopropyl titanate, and titanium acetylacetonate. Suitable organic zirconate adhesion promoters include those capable of reacting with a hydroxy group. , This facilitates cross-linking, which are commercially available from Dorfketal Chemicals (I) Pvt. Ltd. such as Tizor 212, Tizor LA, Tizor 215, Tizor 223, Tizor 227, Tizor 282. In addition, the curable composition is made of an epoxy resin and polythiol. It may contain reaction products. Suitable epoxy resins include, for example, polyglycidyl ether of bisphenol A, polycaprolactone-modified bisphenol A epoxy resin, and one or more polyepoxy such as bisphenol F diepoxy. Epoxy resins may also contain epoxy dimer adducts. Suitable polythiols include, for example, Bruno Bock Chemische Fabrik GmbH & Co. Examples include poly (mercaptopropionate) such as those available from KG under the name THIOCURE.

The curable composition used to prepare the rubber substitute according to the invention may further comprise any additional resin and / or additive that imparts the desired properties to the composition. For example, the composition may further comprise a resin and / or an additive that imparts additional flexibility to the coating formed from the composition. Flexible polyurethane resins are known in the art and are, for example, incorporated herein by reference in appropriate parts of US Patent Application Nos. 11 / 155,154, 11 / 021,325. Nos. 11 / 020, 921, 12 / 056, 306, and 12 / 056, 304. The polyurethane itself can be added to the composition, or the polyurethane can be in situ formed in the curable composition. It will be appreciated that polyurethane can be formed by reacting the hydroxyl functional component with isocyanate in much the same way that the amine and isocyanate components described herein react. Thus, the hydroxyl functional component can be mixed with or used in addition to the amine component for in situ polyurethane formation.

The curable composition used to prepare the rubber substitute of the present invention is, if necessary, glass fiber, stabilizer, thickener, catalyst, colorant, antioxidant, UV absorber, hindered amine light. Includes standard materials in the art such as stabilizers, rheology modifiers, flow additives, antistatic agents, and other performance or property modifiers well known in the field of surface coatings, as well as mixtures thereof. obtain. Suitable rheology modifiers include solid and / or liquid rheology modifiers that can be organic and / or inorganic based polymers such as bentonite clay, fumed silica, BYK411 (available from Chemie), or a combination thereof. Is included.

The curable composition used to prepare the rubber substitutes of the present invention may contain colorants. 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 composition in any suitable form such as individual particles, dispersions, solutions, and / or flakes. A single colorant or a mixture of two or more colorants can be used in the rubber substitute article of the present invention. It should be noted that the particulate colorant is different from the particles present in the abrasion resistant additive (c). As shown in the following examples, particulate colorants have been found to not impart sufficient wear resistance to curable compositions that are considered suitable.

Examples of colorants include pigments, dyes and tints, such as those used in the paint industry and / or those described in the Dry Color Manufacturers Association (DCMA), as well as special effects compositions. The colorant may include, for example, a finely divided solid powder that is insoluble under conditions of use but moist. The colorant may be organic or inorganic and may be aggregated or non-aggregated. The colorant can be incorporated into the composition by grinding or simple mixing. The colorant can be incorporated into the composition by grinding using a grinding vehicle such as an acrylic grinding vehicle, the use of which will be well known to those of skill in the art.

Exemplary pigments and / or pigment compositions include carbazoledioxazine crude pigments, azo, monoazo, diazo, naphthol AS, salt type (lake), benzoimidazolone, condensates, metal complexes, isoindoline, isoindoline. And polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolopyrrole, thioindigo, anthraquinone, indanslon, anthrapyrimidine, flavanthrone, pyranthron, anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigment, diketopyrrolopyrrole Examples include, but are not limited to, red (“DPPBO Red”), titanium dioxide, black carbon, carbon fibers, graphite, other conductive pigments and / or fillers, and mixtures thereof. The terms "pigment" and "coloring filler" can be used interchangeably.

Exemplary dyes include acidic dyes, azo dyes, basic dyes, direct dyes, disperse dyes, reactive dyes, solvent dyes, sulfur dyes, medial dyes such as bismuth vanadate, anthraquinone, perylene, aluminum, quinacridone, etc. Examples include solvent-based and / or aqueous-based ones such as thiazole, thiazine, azo, indigoid, nitro, nitroso, oxadin, phthalocyanine, quinoline, stilben, and triphenylmethane.

As an exemplary tint, Degussa, Inc. AQUA-CHEM 896, Eastman Chemical, Inc., commercially available from. Examples thereof include pigments dispersed in water-based carriers or water-miscible carriers such as CHARISMA COLORANTS and MAXITONER INDUSTRIAL COLORANTS commercially available from the Accurate Dispersions department of.

As mentioned above, the colorant can be in the form of a dispersion comprising a nanoparticle dispersion. 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 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. The nanoparticles can be produced by the step of grinding the raw organic pigment and / or the inorganic pigment in a grinding medium having a particle size of less than 0.5 mm. Exemplary nanoparticle dispersions and methods of their preparation are specified in US Pat. No. 6,875,800B2. Nanoparticle dispersions can also be produced by crystallization, precipitation, gas phase condensation, and chemical friction (ie, partial dissolution). Resin-coated nanoparticles dispersions can be used to minimize reaggregation of nanoparticles in the coating. As used herein, "resin-coated nanoparticles dispersion" refers to a continuous phase in which inconspicuous "composite microparticles", including nanoparticles and a resin coating on the nanoparticles, are dispersed. .. Exemplary dispersions of resin-coated nanoparticles and methods for their preparation were filed US Patent Application No. 10 / 876,031 filed June 24, 2004 and June 24, 2003. It is specified in US Provisional Application No. 60 / 482,167.

Exemplary special effect compositions that may be used in the compositions used to prepare the rubber substitutes of the present invention include reflectance, pearly luster, metallic luster, phosphorescence, fluorescence, photochromism, photosensitivity, and the like. Pigments and / or compositions that produce one or more appearance effects such as thermochromism, goniochromism, and / or color change. Additional special effects compositions can provide other perceptible properties such as reflectivity, opacity, or texture. The special effects composition can generate a color shift such that the color of the coating changes when the coating is viewed at different angles. Exemplary color effect compositions are specified in US Pat. No. 6,894,086, which is incorporated herein by reference. Additional color effect compositions may include transparent coated mica and / or synthetic mica, coated silica, coated alumina, transparent liquid crystal pigments, liquid crystal coatings, and / or any composition. The interference arises from the difference in index of refraction within the material and not due to the difference in index of refraction between the surface of the material and the air.

Photosensitive and / or photochromic compositions that reversibly change their color when exposed to one or more light sources can be used in the compositions of the invention. Photochromic and / or photosensitive compositions can be activated by exposure to radiation of a specified wavelength. When the composition is excited, the molecular structure changes and the changed structure shows a new color that is different from the original color of the composition. When the exposure to radiation is removed, the photochromic composition and / or the photosensitive composition can return to a dormant state in which the original color of the composition returns. The photochromic and / or photosensitive composition is colorless in the non-excited state and can exhibit color in the excited state. Full color changes can appear within milliseconds to milliseconds, such as 20 to 60 seconds. Exemplary photochromic and / or photosensitive compositions include photochromic dyes.

The photosensitive composition and / or the photochromic composition can be associated with and / or at least partially attached to the polymeric material of the polymer and / or the polymerizable component, such as by covalent bonds. Photosensitive and / or photochromic compositions associated with and / or at least partially bound to polymers and / or polymerizable components have minimal migration from the composition.

In general, the colorant can be present in the curable composition in any amount sufficient to impart the desired properties, visual and / or color effects. The colorant may include 1-65 weight percent of the composition, such as 3-40 weight percent or 5-35 weight percent, based on the total weight of the composition.

The curable composition used to prepare the rubber substitutes of the present invention may have a color that matches the color of the associated substrate, for example when applied to the substrate as a coating. As used herein, when the terms "matching" and similar terms refer to color matching, the color of the coating composition of the invention substantially corresponds to the desired color or the color of the associated substrate. Means that. This can be observed visually or confirmed using a spectroscopic instrument. For example, if the substrate for the curable composition is a footwear component such as a polymeric bladder or upper component, the color of the curable composition substantially matches the color of another footwear component. obtain. For example, a toe coated with the rubber substitute of the present invention can match the color to the rest of the shoe's upper, midsole, and / or outsole. This match can be observed visually or confirmed using a spectroscopic instrument.

The curable composition is typically prepared as a multi-packaging system to prevent the components from curing prior to use. The term "multi-packaging system" means a composition in which various components are maintained separately until just prior to use, such as being applied to a substrate as a coating. The compositions of the present invention are usually prepared as two package (“2K”) compositions, the isocyanate functional prepolymer (a) is the first package and the curing agent (b) is the second package. Is. The rubber substitutes of the present invention are suitable for use as coatings, or they can be molded, cast, 3D printed, or otherwise molded into a manufactured article.

The composition can be cured under ambient conditions, but heated air or thermosetting may be applied to the composition to accelerate the curing of the composition or to enhance properties such as adhesion. can. The "ambient" condition means that no heat or other energy is applied, for example, the curable composition is subjected to a thermosetting reaction, the use of forced air, irradiation, etc. without baking in the oven. When prompted, the reaction is said to occur under ambient conditions. Generally, the ambient temperature is in the range of 60-90 ° F (15.6-32.2 ° C), such as a typical room temperature of 72 ° F (22.2 ° C). Alternatively, the composition may be exposed to chemical lines or elevated temperatures for a time sufficient to cure the curable membrane-forming composition at least partially. Typical chemical beam conditions are 1.5-2.0 mW / cm ² irradiation intensity and 315-400 nm (UVA). The composition can typically cure at ambient temperature for a period ranging from about 45 seconds to about 12 hours. For example, the composition can be cured at 72 ° F. (22.2 ° C.) over a period ranging from about 45 seconds to about 12 hours. When utilized in combination with ambient temperature and baking to achieve other desired properties such as better adhesion, the composition is typically left for a period of about 45 seconds to about 30 minutes, followed by. It can be adjusted (cured) for a period of about 20 minutes to about 12 hours at a temperature of up to about 140 ° F. (60 ° C.).

The rubber substitute article of the present invention is formed from a film-forming composition: A) a substrate having at least one coatable surface and B) a film-forming composition applied to and cured on at least one surface of the substrate. Can be used to form a coated substrate comprising a coating layer. The film-forming composition is prepared from the curable composition described above.

Non-limiting examples of suitable substrates are metals, natural and / or synthetic stones, ceramics, glass, bricks, cement, concrete, cinder blocks, wood and composites, and laminates thereof; wall materials, dry Walls, sheet locks, cement boards, plastics, paper, PVC, roofing materials such as singles, roofing composites and laminates, and roofing materials drywall, styrofoam®, plastic composites, acrylic composites, ballistics. Examples include composite materials, asphalt, fiberglass, soil and gravel. Examples of the metal include, but are not limited to, aluminum, cold-rolled steel, electrozinc-plated steel, heat-immersed zinc-plated steel, titanium, and alloys, and polymer materials include TPO, SMC, and TPU. , Polyamide, Polycarbonate, Polyethylene, and Polyamide (Nylon), but are not limited thereto. The substrate can be a primed metal and / or plastic, i.e. an organic or inorganic layer is applied to the substrate. Materials commonly used for fabrics such as ethylene vinyl acetate (EVA) foam or polyurethane (such as TPU) foam, leather, and footwear, including foam, are also suitable substrates.

The curable composition is applied to a bare (eg, untreated, uncoated) substrate, a pretreated substrate, and / or a coated substrate having at least one other coating. obtain. For example, the surface of the substrate may be plasma treated prior to application of the curable composition to enhance adhesion between the substrate surface and the coating layer. Alternatively, an adhesive layer or binding layer containing an adhesion promoter and / or a reaction product of the epoxy resin and polythiol may be placed between the substrate and the coating layer. Suitable adhesion promoters and reaction products include those already mentioned above. For example, the adhesion promoter in the adhesive layer may include organic titanates or organic zirconates. In another example, the reaction product of the epoxy resin and polythiol in the adhesive layer is, for example, as described in US Patent Application No. 62 / 560,998. In the epoxy thiol adhesive layer, the layer typically comprises two component compositions, the first component comprising an epoxy compound and the second component comprising a polythiol curing agent and a curing catalyst. The polythiol curing agent chemically reacts with the epoxy compound. Suitable epoxy resins include, for example, polyglycidyl ether of bisphenol A, polycaprolactone-modified bisphenol A epoxy resin, and one or more polyepoxy such as bisphenol F diepoxy. Epoxy resins may also contain epoxy dimer adducts. Suitable polythiols include, for example, Bruno Bock Chemische Fabrik GmbH & Co. Examples include poly (mercaptopropionate) such as those available from KG under the name THIOCURE.

In another example, the curable composition may be applied to a multi-layer coating composite. The first coating applied to the substrate can be selected from a variety of coating compositions known in the art for surface coated substrates. Non-limiting examples include electrodepositable film-forming compositions, primer compositions, pigmented or non-pigmented monocoat compositions, pigmented or non-pigmented basecoat compositions, transparent topcoat compositions, industrial coatings. The composition and the like may be mentioned.

The composition can be applied to the substrate by one or more of several methods including 3D printing, spraying, immersion / water immersion, brushing, extrusion, distribution, or flow coating. If the substrate contains flooring, they are most often applied by spraying. Conventional spraying techniques and equipment for air spraying and electrostatic spraying, as well as either manual or automatic methods, can be used as described below. The coating layer typically has a dry film thickness of 1 to 25 mils (25.4 to 635 microns), often 5 to 80 mils (127 to 2032 microns). The curing conditions may be as described above.

When the curable composition is sprayed onto the substrate, the composition can be prepared using a two-component mixing device. In this example, isocyanates and amines are added to the high pressure shock mixer. Isocyanate is added to the "A side" and amine is 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 reacts with the 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 to a temperature of ≦ 70 ° C, for example 60 ° C, prior to coating. Heating can promote better viscosity matching between the two components and thus better mixing, but is not necessary for the curing reaction to occur. The A side and / or the B side can be coated at a temperature of ≦ 23 ° C. such as 7 ° C. to 14 ° C.

A "static mixing tube" applicator, a coating device known in the art, can be used with the present invention. In this device, isocyanates and amines are stored in separate chambers. When pressure is applied, each of the components is brought into the mixing tube at a volume ratio of 1: 1. Mixing of ingredients is done via a meandering or corkscrew path in the tube. The outlet end of the tube may have a spraying capacity useful for spraying the reaction mixture. Alternatively, the fluid reaction mixture can be applied to the substrate as beads. The static mixing tube applicator is available from Plas-Pak Industries Inc. Alternatively, it is commercially available from Cammda Corporation.

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

It is believed that an equivalent ratio of isocyanate groups to amine groups may be selected to control the cure rate of the composition. The ratio of the equivalent of isocyanate groups to amine groups (also known as reaction index) is greater than 1, eg 1.01 to 1.10: 1, or 1.03 to 1.10: 1, or 1.05 to 1. If it is 08: 1, or 1.01 to 1.4 to 1, or 1.01 to 1.5, or 1.3 or more than 1.3 to 1, curing and bonding benefits can occur. I know. The term "1: 1 volume ratio" means that the volume ratio varies by up to 20%, or up to 10%, or up to 5% for each component.

Commercially available mixing devices, such as those described in paragraphs [0037] and [0038] of US Patent Publication No. 2007/0168051, can be used.

Further, the curable composition in the formation of the rubber substitute article of the present invention can be deposited or extruded by 3D printing. Suitable methods and equipment are described, for example, in US Patent Application No. 15 / 680,846. In 3D printing, a 3D object typically deposits at least two co-reactive components on a substrate and then at least a portion or layer of the underlying portion or layer until the article is completely formed. It is made by forming at least one part or cross-section layer of an object, optionally by depositing one or more additional parts or layers of the object over a portion. If the substrate is a supporting substrate for manufacturing purposes only, the finished product is removed from the substrate. Alternatively, the substrate can be part of a manufactured object of which the rubber substitute is a component. For example, the substrate can be the midsole of a shoe.

In the present invention, the isocyanate-functional prepolymer can be provided to the mixer as the first component by the first pump, and the curing agent can be provided to the mixer as the second component by the second pump, and is curable. A composition may be provided, which may then be deposited / extruded through a nozzle connected to the mixer. The abrasion resistant additive can be contained in the first component or the second component, or can be contained in the mixture formed in the mixer. In addition, if the additive manufacturing process does not include a heating line, the isocyanate-functional prepolymer must be liquid. Some of the diols used to make isocyanate-functional prepolymers are aromatic or aliphatic diols such as polycarbonates, polyether glycols, polyesters, polycaprolactones, polybutadienes, polyamides, siloxane diols, alkyd diols, and It can be an acrylic diol.

After applying the curable composition to the substrate as a coating and curing to form a coated substrate, the coated substrate is an S-42 sandpaper strip from Taber Industries and two 1, After being subjected to a 1,000 cycle TABER abrasion test using a weight of 000 grams, it exhibits a coating loss of less than 0.33 cm ³ . The TABER abrasion test is performed as described in the following examples.

The rubber substitutes of the present invention are automotive parts such as automotive parts and accessories including bumpers, fenders, hoods, doors, panels, trims, etc .; special floors and running tracks, for any application in which rubber is conventionally used. Exercise equipment, ball components (cores for basketball, baseball, golf balls, lacrosse balls, etc., surface coatings, etc.); Protective equipment for sports and other applications such as chest protectors and helmet components Can be used for grips and / or stick components such as bats for ice hockey, field hockey, lacrosse and the like.

The rubber substitutes of the present invention are particularly suitable for use as footwear and / or footwear components prepared from any of the curable compositions described above. The curable composition can be used as a coating on the footwear component or can be used to form the entire article of the footwear or the footwear component itself. As used herein, the terms "footwear" and "shoes" are athletic and sports shoes, men's and women's dress shoes, men's and women's casual shoes, children's shoes, sandals, thonged sandals, boots. , Work boots, outdoor footwear, orthopedic shoes, slippers, etc. The term "footwear component" includes any component of the shoe, including the outsole, midsole, polymeric bladder, upper material, and shoe liner. It will be recognized that these components are made from several different materials or substrates. In certain examples, footwear components coated according to the present invention form all or part of the shoe upper. A particularly suitable portion of the upper coated by the present invention is the toe. "Toe" will typically be understood as referring to the front of a shoe that experiences a relatively high level of wear and / or wear. Surprisingly, it has been found that coating this portion of the shoe with the rubber substitute composition of the present invention improves resistance to abrasion and / or abrasion.

The footwear component may also include a polymeric bladder coated with the curable composition described above. The polymeric bladder can be filled with, for example, plasma, water, or other fluid such as a gas containing air, nitrogen, and the like. Such bladder is known in the footwear industry, for example, U.S. Pat. Nos. 6,944,973, 6,119,371, 5,713,141, 5,952,065, U.S. Pat. It is described in the same No. 5,353,459, the same No. 4,506,460, and the same No. 4,219,945.

In certain embodiments of the invention, the polymeric bladder is a midsole contained within the midsole and at least partially coated with the rubber substitute of the invention. For example, the composition can be applied to the underside of a midsole containing a nitrogen-filled polymeric bladder to protect the bladder from puncture failure. In another embodiment, the polymeric bladder is contained within the outsole.

The footwear component can also be an outsole containing the curable composition described above. The outsole casts a sheet of curable composition and post-treats the sheet to the desired shape and form, casts the curable composition in the mold, sprays the curable composition into the mold, 3D. It can be formed by printing or injection molding of the components. The outsole can be preformed and then adhesively attached to the midsole. Adhesion between the midsole containing the curable composition and the outsole is a step of including an adhesion promoter in the curable composition and a step of treating the surface of the midsole before applying the curable composition ( Before applying the outsole to the midsole, and / or at least one of the midsole and / or the outsole, an adhesive layer containing the adhesion promoter and / or the reaction product of the epoxy resin and polythiol. It can be reinforced by the step of applying to one surface. It may be desirable to wipe the midsole with a solvent before applying the preformed outsole (or if the outsole is formed in situ, before applying the curable composition), as a suitable solvent. Is harmless to coated substrates such as acetone, MEK, isopropanol and the like. If the midsole contains foam, it may be desirable to immerse the ingredients in a powder prior to application of the outsole, as described in US Patent Application No. 11 / 448,627.

The dry film thickness of the footwear component is 20 to 1,000 mils (508 to 25,400 microns), or 40 to 150 mils (1,016 to 3,810 microns), or 60 to 100 mils (1,524 to 524 to). It can be in the range of 2,540 microns), or 500 to 750 millimills (12,700 to 19,050 microns). It will be understood that these layers are relatively "thick". The compositions of the invention are also 0.1 to less than 15 mils (2.54 to less than 381 microns), or 0.1 to 10 (2.54 to 254 microns), or 0.5 to 3 (12.7). It can also be applied as a thinner layer (~ 76.2 microns), or 1-2 mils (25.4-50.8 microns). Any of the endpoints within these ranges can be combined. Since the inorganic particles that can be used are much larger than the organic particles used for the abrasion resistant additive in the curable composition, the dry film thickness of the outsole will vary depending on the relative amount of each type of particle. do. For example, if the weight ratio of organic particles to inorganic particles is less than 10:40, the dry film thickness of the outsole is typically 508-25,400 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.

Footwear components such as outsoles prepared as described herein typically provide good traction to the user, especially in wet conditions such as rain or snow. This component also typically exhibits enhanced wear and / or abrasion resistance compared to a typical natural and / or synthetic rubber outsole.

The wear resistance observed in the footwear component according to the invention is particularly relevant to the tread and other parts of the shoe's outsole, but especially in shoes where the toes are often dragged during play, such as during service. Especially relevant to the toes of shoes used especially for tennis. In many cases, the wearer's wear on the toes can spoil the aesthetics, or the shoe itself, and ultimately puncture the toes. The footwear components of the present invention are typically 0.33 cm ³ after being subjected to a 1,000 cycle TABER abrasion test using an S-42 sandpaper strip and two 1,000 gram weights. Shows less than material loss.

It may be said that each of the above-mentioned features and examples, and combinations thereof, is included in the present invention. Accordingly, the invention is drawn to the following non-limiting aspects:
1. 1. It ’s a rubber substitute,
(A) Isocyanate-functional prepolymers, (i) reaction products of polyisocyanates with polyamines having primary and / or secondary amino groups, and / or (ii) reactions of polyisocyanates with polyols. Products, including isocyanate-functional prepolymers, and
(B) A curing agent containing a mixture of polyamines, wherein at least one polyamine in the curing agent has an amine equivalent of 125 to 250.
(C) A rubber comprising an abrasion resistant additive comprising organic particles, wherein the organic particles are prepared from a curable composition comprising an abrasion resistant additive having a volume average particle size of at least 5 microns. Alternative goods.
2. 2. The rubber substitute according to embodiment 1, wherein at least one polyamine in the curing agent having an amine equivalent of 125-250 is an acyclic polyamine containing a secondary amino group.
3. 3. The rubber substitute according to embodiment 1 or 2, wherein the abrasion resistant additive is present in the composition in an amount ranging from 0.25 to 9 weight percent based on the total solid content weight of the composition.
4. The rubber substitute according to any of the preceding embodiments, wherein the polyisocyanate used to prepare the isocyanate-functional prepolymer is an aliphatic.
5. The rubber substitute according to any of the preceding embodiments, wherein the isocyanate-functional prepolymer has an isocyanate equivalent of greater than 300.
6. Preliminary embodiments in which the curing agent comprises 5-50 weight percent aliphatic polyamines having an amine equivalent of 125-250 and 50-95 weight percent aliphatic polyamines having an amine equivalent of 900-2500. The rubber substitute article described in any of.
7. The rubber substitute according to any of the preceding embodiments, wherein the organic particles of the abrasion resistant additive comprises particles that are chemically inert, untreated, and uncoated.
8. The rubber substitute according to any of the preceding embodiments, wherein the organic particles include polyethylene, polypropylene, and / or a saturated linear primary alcohol (with an average carbon chain length of C ₂₀ to C ₅₀ ).
9. The rubber substitute according to any of the preceding embodiments, wherein the rubber substitute comprises a footwear component.
10. The rubber substitute according to aspect 9, wherein the footwear component exhibits a dry film thickness of 25.4 to 254 microns.
11. The rubber substitute according to aspect 9 or 10, further comprising an adhesive layer applied to at least one surface of the footwear component, wherein the adhesive layer comprises an adhesion promoter and / or a reaction product of an epoxy resin and polythiol. ..
12. The rubber substitute article according to any of aspects 9 to 11, wherein the adhesive layer comprises an adhesion promoter comprising organic titanate or zirconate.
13. The rubber substitute article 3Ds the article by forming at least one portion or cross-sectional layer of the article by depositing at least two co-reactive components on the substrate until the article is completely formed. Any of aspects 1-12, prepared by printing, wherein the first co-reactive component comprises an isocyanate-functional prepolymer (a) and the second co-reactive component comprises a curing agent (b). Rubber substitute article described in Crab.
14. A method for preparing a rubber substitute article according to any one of aspects 1 to 12 by 3D printing.
(A) A step of depositing at least two co-reactive components on a substrate to form a cross-sectional layer of an article.
(B) If necessary, a step of depositing an additional layer of co-reactive components over at least a portion of the pre-applied layer.
(C) A step of repeating step (b) until the article is completely formed, and
(D) The first co-reactive component comprises the isocyanate-functional prepolymer (a) and the second co-reactive component comprises, as required, a step of removing the article from the substrate. A method comprising a curing agent (b).

Example A
Isocyanate-functional prepolymers were prepared from the following constituents as described below:

A total of 1,000 grams of isophorone diisocyanate was placed in a suitable reaction vessel equipped with a stirrer, temperature probe, condenser, and nitrogen inlet tube and blanketed with nitrogen gas. The contents of the flask were heated to 40 ° C., then 2,217 grams of JEFFAMIN D2000 was added over 70 minutes, during which the temperature rose to about 56 ° C. After the supply was complete, 0.65 grams of dibutyltin dilaurate was added and the mixture was heated to 70 ° C. The mixture was kept at 70 ° C. for 2.5 hours, during which the isocyanate equivalents reached about 500 grams per equivalent. The final material was measured by ASTM D2572, "Standard Test Method for Isocyanate Groups in Urethane Materials or Prepolymers", 505.8 measured isocyanate equivalents, and by gel permeation chromatography. It had a weight average molecular weight (Mw) of about 5,300 relative to the polystyrene standard.

Example B
Isocyanate-functional prepolymers were prepared from the following constituents as described below:

A total of 450 grams of isophorone diisocyanate was placed in a suitable reaction vessel equipped with a stirrer, temperature probe, condenser, and nitrogen inlet tube and blanketed with nitrogen gas. At room temperature (23 ° C.), 1,668 grams of JEFFAMIN D2000 was added over 25 minutes, during which the temperature rose to about 62 ° C. After the supply was complete, 0.43 grams of dibutyltin dilaurate was added, the mixture was held for 30 minutes and then the mixture was heated to 70 ° C. The mixture was kept at 70 ° C. for 1 hour, during which the isocyanate equivalent reached about 1,000 grams per equivalent. The final material is a polystyrene standard as measured by ASTM D2572 "Standard Test Method for Isocyanate Groups in Urethane Materials or Prepolymers" with 1025 measured isocyanate equivalents and by gel permeation chromatography. It had a weight average molecular weight (Mw) of about 6,800.

Example C
Isocyanate-functional prepolymers were prepared from the following constituents as described below:

A total of 850 grams of isophorone diisocyanate was placed in a suitable reaction vessel equipped with a stirrer, temperature probe, condenser, and nitrogen inlet tube and blanketed with nitrogen gas. At room temperature (22 ° C.), 2,346 grams of JEFFAMIN D2000 was added over 70 minutes, during which the temperature rose to about 57 ° C. After the supply was complete, 0.64 grams of dibutyltin dilaurate was added, the mixture was held for 15 minutes and then the mixture was heated to 70 ° C. The mixture was kept at this temperature for 1.25 hours, during which the isocyanate equivalent reached about 650 grams per equivalent. The final material is the measured isocyanate equivalent of 653 as measured by ASTM D2572 "Standard Test Method for Isocyanate Groups in Urethane Materials or Prepolymers" and the polystyrene standard as measured by gel permeation chromatography. It had a weight average molecular weight (Mw) of about 5,300.

Example D
Isocyanate-functional prepolymers were prepared from the following constituents as described below:

A total of 760 grams of isophorone diisocyanate was placed in a suitable reaction vessel equipped with a stirrer, temperature probe, condenser, and nitrogen inlet tube and blanketed with nitrogen gas. At room temperature (22 ° C.), 1,356.4 grams of JEFFAMINE D2000 was added over 70 minutes, during which the temperature rose to about 56 ° C. After the supply was complete, 0.42 grams of dibutyltin dilaurate was added, the mixture was held for 15 minutes and then the mixture was heated to 70 ° C. The mixture was kept at this temperature for 2 hours, during which the isocyanate equivalent reached about 404 grams per equivalent. The final material is the measured isocyanate equivalent of 403 as measured by ASTM D2572, "Standard Test Method for Isocyanate Groups in Urethane Materials or Prepolymers", and the polystyrene standard as measured by gel permeation chromatography. It had a weight average molecular weight (Mw) of about 4,600.

Example E
Isocyanate-functional prepolymers were prepared from the following constituents as described below:

A total of 575 grams of isophorone diisocyanate was placed in a suitable reaction vessel equipped with a stirrer, temperature probe, condenser, and nitrogen inlet tube and blanketed with nitrogen gas. At room temperature (22 ° C.), 1,935.2 grams of JEFFAMINE D2000 was added over 60 minutes, during which the temperature rose to about 57 ° C. After the supply was complete, 0.51 grams of dibutyltin dilaurate was added, the mixture was held for 15 minutes and then the mixture was heated to 70 ° C. The mixture was kept at this temperature for 1.5 hours, during which the isocyanate equivalent reached about 865 grams per equivalent. Next, 215.7 g of Desmodur XP2580 and 182.7 g of Tolonate HDT LV2 were added and the materials were mixed. After 1 hour, the final material has a measured isocyanate equivalent of 599 as measured by ASTM D2572 "Standard Test Method for Isocyanate Groups in Urethane Materials or Prepolymers" and the polymer is gel permeation chromatographed. It had a weight average molecular weight (Mw) of about 5,400 relative to the polystyrene standard as measured by graphography.

Example F
Isocyanate-functional prepolymers were prepared from the following constituents as described below:

A total of 355 grams of isophorone diisocyanate was placed in a suitable reaction vessel equipped with a stirrer, temperature probe, condenser, and nitrogen inlet tube and blanketed with nitrogen gas. At room temperature (21 ° C.), 598.4 grams of Arcol Polyol PPG 725 was added over 30 minutes and no temperature increase was observed. After the supply was complete, 0.062 grams of dibutyltin dilaurate was added, the mixture was held for 10 minutes and then the mixture was slowly heated to 80 ° C. The temperature was raised to 100 ° C. and the mixture was kept at this temperature for 2 hours, during which the isocyanate equivalent reached about 585 grams per equivalent. The temperature was lowered to 80 ° C. and 353.0 g of Desmodur XP2580 and 1059.3 g of Tolonate HDT LV2 were added to further reduce the temperature to 60 ° C. After 1 hour, the material had a measured isocyanate equivalent of about 259 grams per equivalent. Next, 780.7 g of methylamylketone was added and the final mixture was about 341 grams per equivalent as measured by ASTM D2572 "Standard Test Method for Isocyanate Groups in Urethane Materials or Prepolymers". Having an isocyanate equivalent, the polymer had a weight average molecular weight (Mw) of about 1,400 relative to the polystyrene standard as measured by gel permeation chromatography.

Formulation Examples Examples 1 and 5 are control examples having the same composition (different batches) and do not contain the polishing components as used in the compositions of the present invention. Examples 2 to 4 are comparative examples, which contain inorganic particles as an abrasion resistant additive but do not contain organic particles. Examples 6 and 7 show compositions prepared according to the present invention. The curable composition was prepared from the following constituents:

"A" side: A total of 100 grams of isocyanate-functional prepolymer was used. In some cases, one or more prepolymers were mixed to achieve the desired properties. The contents were kept at 60 ° C. prior to application to achieve spray viscosity.

"B" side: The amine component was prepared from the components listed in the above Examples. In Example 1, all the constituents are mixed with zircoa beads and ground in a LAU mixer for 3 hours. In Examples 2-7, the prepaste is mixed using JEFFAMIN T5000 and TiO ₂ in the desired proportions and ground in LAU using Zircoa beads for 3 hours. The paste was filtered and used with the remaining resin components to bring the desired levels of TiO ₂ and JEFFAMINE T5000 levels. Alumina or PETROLITE 5000 T6 particles were then added and mixed using a cowl's blade.

The polyurea coating composition of the present invention was prepared by combining the isocyanate functional "A" side component and the amine functional "B" side component by the following method:

Place the free membrane of the polyurea coating composition into a double tubular syringe equipped with a static mixing tube and a pneumatic applicator gun (available from Plus-Pak Industries) to inject the ingredients on the A and B sides. It was produced by injecting onto a polyethylene sheet in a 1: 1 ratio and then immediately stretching with a Gardco adjustable micrometer membrane applicator at about 60-80 mils. The membrane was rested at 104 ° F for 1 day before testing the membrane properties (Young's modulus, elongation, and glass transition temperature).

Coefficients and elongation characteristics were measured using an INSTRON 4443 with a pulling rate of 50 mm / min at room temperature (23 ° C.). The glass transition temperature was measured using a TA Instruments 2980 DMA dynamic mechanical analyzer. DMA test parameters included tensile membrane mode, 20 μm amplitude, 1 Hz frequency, 40 cNm clamping force, and 3 ° C./min heating rate.

The hardness value is about 6 cm in diameter by charging the A side and B side into a double tubular syringe equipped with a static mixing tube and a pneumatic applicator gun, and injecting the components into a mold at a ratio of 1: 1. And determined by forming a round "pack" 0.2 cm thick. After resting at 104 ° F for 1 day, the pack was tested. The hardness of the polyurea pack was measured with a Shore D durometer (Pacific Transducer Corp. Model 212) under ambient conditions.

TABER abrasion test: The coating was applied to the primed panel by the stretching method, and a hole was made in the center and cut into 4 inch × 4 inch pieces. The panel was then weighed and mounted on a flat turntable platform (Taver Rotation Platform Abrasion Tester) that rotates on a vertical axis at a fixed speed. Two Taber polishing wheels were covered with sandpaper (Taber Industries S-42), applied at a specific pressure of two 1,000 gram weights and lowered onto the surface of the specimen. As the turntable rotated, the wheel was driven by the sample in the opposite direction around the horizontal axis. Two 500 cycle runs (72 rpm) were performed on each sample and the mass was recorded after 500 cycles of each set. Volume loss in cc units was calculated using the mass loss and density of the coating and plotted as shown in the table below for comparison.

As can be seen in Table 1 above, it was observed that the organic particles improved the abrasion resistance when not used in combination with the inorganic particles, that is, even with 0% inorganic particles and 0 to 10% organic particles.

Example G
Isocyanate functional polymers were prepared from the following constituents as described below:

A suitable reaction vessel equipped with a stirrer, temperature probe, condenser, and nitrogen inlet tube and blanketed with nitrogen gas contained a total of 600.2 grams of isophorone diisocyanate and 0.563 g of dibutyltin dilaurate. At room temperature (23 ° C.), 2,213.3 grams of Polymega 2000 was added over 75 minutes, during which the reaction exotherm reached about 60 ° C. After the supply was complete, the mixture was slowly heated to 70 ° C. The reaction was held at this temperature for 90 minutes, during which the isocyanate equivalent reached about 910 grams per equivalent. Next, 228.2 g of Desmodur XP2580 and 196.3 g of Tolonate HDT LV2 are added and the mixture is stirred for about 30 minutes, after which the material is ASTM D2572 "Standard for isocyanate groups in urethane materials or prepolymers". It has a measured isocyanate equivalent of about 622 grams per equivalent as measured by "Test Method" and the polymer has a molecular weight of about 7,960 relative to the polystyrene standard as measured by gel permeation chromatography. It had Mw).

Examples 8 (control) to 10 show the performance of the organic abrasion resistant component using the urethane functional prepolymer.

The data in Table 2 show that the curable composition of the present invention has a wear resistance of a secondary amino group even when a considerably small amount of the wear resistant additive is used and the wear resistant additive does not contain inorganic particles. It is shown that significant improvement can be achieved by including acyclic polyamines having an amine equivalent of 125 to 250, including the above, in the curing agent.

Although embodiments of the invention are described in detail, it will be appreciated by those skilled in the art that various modifications and alternatives to those details may be developed in the light of the overall teachings of the present disclosure. Let's do it. Accordingly, the particular configurations disclosed are meant to be illustrative only, but not limited to, the scope of the invention giving the entire scope of the appended claims and any and all equivalents thereof.

Claims (21)

It ’s a rubber substitute,
(A) Isocyanate-functional prepolymers, (i) reaction products of polyisocyanates with polyamines having primary and / or secondary amino groups, and / or (ii) reactions of polyisocyanates with polyols. Products, including isocyanate-functional prepolymers, and
(B) A curing agent containing a mixture of polyamines, wherein at least one polyamine in the curing agent has an amine equivalent of 125 to 250.
(C) A wear-resistant additive containing organic particles, wherein the organic particles have a volume average particle size of at least 5 microns.
A rubber substitute article prepared from a curable composition comprising. The rubber substitute article according to claim 1, wherein at least one polyamine in the curing agent having an amine equivalent of 125 to 250 is a non-cyclic polyamine containing a secondary amino group. The rubber substitute according to claim 1, wherein the wear resistant additive is present in the composition in an amount in the range of 0.25 to 9 weight percent based on the total solid content weight of the composition. The rubber substitute article according to claim 1, wherein the polyisocyanate used for preparing the isocyanate-functional prepolymer is an aliphatic. The rubber substitute according to claim 1, wherein the isocyanate-functional prepolymer has an isocyanate equivalent of more than 300. The curing agent comprises 5-50 weight percent aliphatic polyamines having an amine equivalent of 125-250 and 50-95 weight percent aliphatic polyamines having an amine equivalent of 900-2500. The rubber substitute article according to 1. The rubber substitute article according to claim 1, wherein the organic particles include particles that are chemically inert, untreated, and uncoated. The rubber substitute according to claim 1, wherein the organic particles contain polyethylene, polypropylene, and / or a saturated linear primary alcohol (with an average carbon chain length of C ₂₀ to C ₅₀ ). The rubber substitute article according to claim 1, wherein the rubber substitute article includes a footwear component. The rubber substitute article according to claim 9, wherein at least one polyamine in the curing agent having an amine equivalent of 125 to 250 is a non-cyclic polyamine containing a secondary amino group. The rubber substitute according to claim 9, wherein the wear resistant additive is present in the composition in an amount in the range of 0.25 to 9 weight percent based on the total solid content weight of the composition. The rubber substitute article according to claim 9, wherein the polyisocyanate used for preparing the isocyanate-functional prepolymer is an aliphatic. The rubber substitute according to claim 9, wherein the isocyanate-functional prepolymer has an isocyanate equivalent of greater than 300. The curing agent comprises 5-50 weight percent aliphatic polyamines having an amine equivalent of 125-250 and 50-95 weight percent aliphatic polyamines having an amine equivalent of 900-2500. The rubber substitute article according to 9. The rubber substitute article according to claim 9, wherein the organic particles include particles that are chemically inert, untreated, and uncoated. The rubber substitute according to claim 9, wherein the organic particles contain polyethylene, polypropylene, and / or a saturated linear primary alcohol (with an average carbon chain length of C ₂₀ to C ₅₀ ). The rubber substitute according to claim 9, wherein the footwear component exhibits a dry film thickness of 25.4 to 254 microns. The rubber substitute according to claim 9, further comprising an adhesive layer applied to the surface of at least one of the footwear components, wherein the adhesive layer comprises an adhesion promoter and / or a reaction product of an epoxy resin and polythiol. Goods. The rubber substitute article according to claim 18, wherein the adhesive layer contains an adhesion promoter containing organic titanate or zirconate. The rubber substitute article is said to form at least one portion or cross-sectional layer of the article by depositing at least two co-reactive components on a substrate until the article is completely formed. The article is prepared by 3D printing, wherein the first co-reactive component comprises the isocyanate-functional prepolymer (a) and the second co-reactive component comprises the curing agent (b). Item 1 The rubber substitute article. The method for preparing the rubber substitute article according to claim 1 by 3D printing.
(A) A step of depositing at least two co-reactive components on a substrate to form a cross-sectional layer of the article.
(B) If necessary, a step of depositing an additional layer of the co-reactive component over at least a portion of the pre-applied layer.
(C) A step of repeating step (b) until the article is completely formed, and
(D) The first co-reactive component comprises the isocyanate-functional prepolymer (a), comprising the step of removing the article from the substrate, if necessary, and the second co-reactivity. The method, wherein the component comprises the curing agent (b).