EP2111421A2

EP2111421A2 - Polyurethaneurea system

Info

Publication number: EP2111421A2
Application number: EP07874557A
Authority: EP
Inventors: Philippe Laubry
Original assignee: Michelin Recherche et Technique SA Switzerland; Michelin Recherche et Technique SA France; Societe de Technologie Michelin SAS
Current assignee: Compagnie Generale des Etablissements Michelin SCA; Michelin Recherche et Technique SA France
Priority date: 2006-10-30
Filing date: 2007-10-30
Publication date: 2009-10-28
Also published as: CN101528798A; JP2010508417A; WO2008149180A3; WO2008149180A2; JP5442443B2; CN101528798B

Abstract

A polyurethaneurea system that includes in some embodiments Parts A and B reaction components for a polyurethaneurea, wherein an exemplary embodiment provides a Part A that comprises between 55 and 75 wt.% of an oligomeric polyol, between 3 and 7 wt.% of an aromatic diamine chain extender, and between 0.1 and 1.5 % of a reactivity catalyst; Part B includes between 1 and 15 wt.% of a short aromatic diisocyanate and between 5 and 35 wt.% of an aromatic diisocyanate prepolymer that is the reaction product of a short aromatic diisocyanate and a diol. The polyurethaneurea system may further comprise an elastomer-surface activator comprising a second short aromatic diisocyanate and a second aromatic diisocyanate prepolymer, wherein at least one of the second diisocyanates may be the same as at least one of the diisocyanates of Part B.

Description

POLYURETHANEUREA SYSTEM

BACKGROUND OF THE INVENTION Field, of the. Invention

[0001] This invention relates generally to polyurethaneurea systems and more particularly, to polyurethaneurea systems useful for bonding and filling elastomers, especially elastomers comprising cross-linked rubber.

Description of the Related Art

[0002] Various adhesive products, including polyurethane adhesive products, are commercially available to use as sealants or to patch polymeric elastomeric materials such as, for example, natural rubber, synthetic rubber, plasticized polyvinyl chloride, polychloroprene and the like.

[0003] Polyurethanes are typically synthesized from a polyisocyanate, a polyglycols and a chain extender. The chain extender is typically selected from a low molecular weight diol, diamine, aminoalcohol or water. When the chain extender is a diol, the polyurethane that is formed consists entirely of urethane linkages. However, if, for example, the chain extender is water, aminoalcohol or a diamine, both urethane and urea linkages are present and the resulting composition is called a polyurethaneurea or PUU. Therefore, a polyurethane type composition having both urethane and urea linkages may be called a polyurethaneurea.

SUMMARY OF THE INVENTION

[0004] Particular embodiments of the present invention include a polyurethaneurea system that is useful for bonding and/or repairing an elastomer. The system includes reaction components that react to form a polyurethaneurea, the reaction components including a Part A and a Part B. These Parts may comprise mixtures as follows, with the mass fraction of each of the reaction components based upon the total mass of the part A and part B reaction components: Part A is a mixture comprising between about 55 and about 75 wt.% of an oligomeric polyol (a primary polyol in some embodiments) having an average molecular weight greater than about 1000, between about 3 and about 7 wt.% of an aromatic diamine chain extender, and between about 0.1 and about 1.5 % of a reactivity catalyst; Part B is a mixture comprising between about 1 and about 15 wt.% of a short aromatic diisocyanate and between about 5 and about 35 wt.% of an aromatic diisocyanate prepolymer that is the reaction product of a short aromatic diisocyanate and a diol. Particular embodiments of the polyurethaneurea system provide that a ratio of isocyanate functionalities to a total of the amine and hydroxyl functionalities in the mixture of part A and part B is between about 0.8 and about 2. Alternatively, particular embodiments provide that the ratio is between about about 1 and about 1.07.

[0005] The polyurethaneurea system may further comprise an elastomer-surface activator comprising a second short aromatic diisocyanate and a second aromatic diisocyanate prepolymer, wherein at least one of the second diisocyanates may be the same as at least one of the diisocyanates of Part B.

[0006] Particular embodiments of the present invention further provide a process, comprising reacting the reaction components of the polyurethaneurea system described above. The method may further include applying the polyurethaneurea to a face of a cross-linked rubber article and bonding the face of the cross-linked rubber article to a substrate. Particular embodiments of the process may further include applying an elastomer-surface activator to the face of the cross-linked rubber article, wherein the elastomer-surface activator comprises a second short aromatic diisocyanate and a second aromatic diisocyanate prepolymer. Optionally, the process may include priming the face of the cross-linked rubber article with a solution of trichloroisocyanuric acid in a solvent.

[0007] Particular embodiments of the present invention further include articles comprising a component bonded to the article with the polyurethaneurea system described above.

[0008] Particular embodiments of the present invention provide a method for retreading a tire, including applying the elastomer-surface activator to a bonding surface of a tread band, applying the polyurethaneurea material to the bonding surface of the tread band, and placing the bonding surface of the tread band having the polyurethaneurea material thereon onto an outer bonding surface of a tire carcass.

[0009] Particular embodiments of the present invention further provide a method of repairing an elastomeric article, comprising coating a damaged surface of the elastomeric article with the elastomer-surface activator, wherein the damaged surface is an exposed surface of a hole, gash, gouge, split, cut or tear in the article; and filling the hole, gash, gouge, split, cut or tear in the article with the polyurethaneurea described above. [0010] The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular description of a preferred embodiment of the invention, as illustrated in the accompanying drawing wherein like reference numbers represent like parts of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

[0011] FIG. 1 is a graph plotting elongation and modulus of different rubber compositions and an exemplary polyurethaneurea material in accordance with the present invention.

[0012] FIG. 2 is a graph plotting strain and true stress of different rubber compositions and an exemplary polyurethaneurea material in accordance with the present invention.

[0013] FIG. 3 is a graph plotting elongation and hysteresis of different rubber compositions and an exemplary polyurethaneurea material in accordance with the present invention.

[0014] FIG. 4 is a graph plotting break stress and break strain of several different rubber compositions bonded with exemplary polyurethaneurea systems in accordance with the present invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0015] The present invention includes a polyurethaneurea system, methods of its making and methods of its use. The polyurethaneurea system is useful as an adhesive and/or as a repair material for various articles, including elastomeric articles and including elastomeric articles that comprise a cross-linked (cured) rubber compound. The polyurethaneurea system is useful as a repair material to fill holes, gashes, gouges, splits, cuts, tears and/or other damage resulting in a loss of the original material, including elastomeric material, that is to be repaired. The present invention further includes articles having the polyurethaneurea as an adhesive and/or repair material.

[0016] The polyurethaneurea system of particular embodiments provides a polyurethaneurea product resulting from the reaction of Part A and Part B reaction components. Part A may comprise a mixture of reaction components including an oligomeric polyol and an aromatic diamine chain extender while Part B may comprise a mixture of reaction components including a short aromatic diisocyanate and an aromatic diisocyanate prepolymer, the prepolymer being the reaction product of a short aromatic diisocyanate with a diol. Advantageously, particular embodiments include no solvent and/or no fillers in the Part A and Part B mixtures.

[0017] The mixture of the Part A and Part B reaction components may be characterized in some embodiments as having a ratio of isocyanate functionalities to a total of the amine and hydroxyl functionalities in the mixture of between about 0.9 and about 2. Other embodiments have such a ratio of between about 1 and about 1.7 while other embodiments have a ratio of between about 1 and about 1.07 or between about 1 and about 1.03.

[0018] The Part A mixture used to form the polyurethaneurea system of particular embodiments includes an oligomeric polyol and an aromatic diamine chain extender. The oligomeric polyol reacts to form the urethane linkages in the polyurethaneurea composition. Particular embodiments include an oligomeric polyol having an average molecular weight greater than about 1000 or between about 1000 and 4000 while other embodiments include a polyol having an average molecular weight of between about 1500 and 4000 or between about 2000 and about 4000. All molecular weights are expressed throughout as weight average molecular weights unless otherwise indicated.

[0019] The oligomeric polyol reaction component of particular embodiments may be characterized as having no oligomeric polyol having a molecular weight of less than about 1000 or alternatively, less than about 900 or less than about 800. Alternatively, in particular embodiments, the oligomeric polyol may include no more than about 5 wt.% or alternatively no more than about 10 wt.%, 15 wt.% or about 25 wt.% of oligomeric polyol having a molecular weight of less than about 1000, less than about 900 or less than about 800 respectively.

[0020] The oligomeric polyol reaction component of particular embodiments may further be characterized as being predominately a primary oligomeric polyol. For example, some embodiments may include an oligomeric polyol as being 100 wt.% primary oligomeric polyol or alternatively at least 95 wt.% primary oligomeric polyol or at least 75 wt.% primary oligomeric polyol. Particular embodiments include an oligomeric polyol reaction component having an OH functionality of about 2.

[0021] Non-limiting examples of suitable primary oligomeric polyols include polyether polyols, amine-terminated polyols, polyester polyols, polyester ether polyols, polycyclic polyols and polycarbonate polyols. Polyether polyols include polytetramethylene ether glycol (PTMEG). Amine-terminated polyols are based on polyether glycols that have had the terminal hydroxyl groups replaced by primary or secondary amino functionalities. The polyester polyol may include, for example, polyethylene adipates, polyethyleneglycol adipates, polycaprolactone diols, and polycaprolactone-polyadipate copolymer diols.

[0022] For those embodiments that do not include only a primary oligomeric polyol, then secondary polyols, for example, may be included in as a reaction component in particular embodiments. Such secondary oligomeric polyol may include, for example, polybutylene oxide glycol (PBO), polypropylene oxide glycol (PPO) and castor oil.

[0023] Optionally, the oligomeric polyol reaction component may include mixtures of oligomeric polyol selected from those described above and/or from others as known to those having ordinary skill in the art.

[0024] Particular embodiments include an amount of the oligomeric polyol reaction component (expressed as the wt.% of the total mass of the reactant components of Part A and Part B) as being between about 50 wt.% and about 80 wt. % of the total mass or alternatively between about 55 wt.% and about 75 wt. % or between about 60 wt.% and about 72 wt. %.

[0025] Another reaction component that may be included in the Part A mixture is an aromatic diamine chain extender. The aromatic diamine chain extender reacts to form the urea linkages in the polyurethaneurea reaction product. The aromatic diamine chain extender may be, for example, a primary and/or a secondary aromatic diamine. Particular embodiments include only primary aromatic diamine or the aromatic diamine reaction component may include, for example, at least 75 wt.% or at least 95 wt.% primary aromatic diamine.

[0026] Non-limiting examples of the aromatic diamine chain extender reaction component include 2,4 and 2,6 isomers of DETDA (diethyltoluenediamine), methylenebis(N,N-dibutyldianiline), EPDA (isophoronediamine), or 3,5-dimethylthio-2,4- toluenediamine, 3,5-dimethylthio-2,6-toluenediamine isomers or mixtures thereof. Other examples include methylene dianiline (MDA), 4,4'-methylene-bis-3-(chloro-2,6- diethylbenzenamine) (MCDEA); 4,4'-methylene-bis-(2-ethyl-6-methylaniline) (MMEA); 4,4'-bis-(2,6-diethylaniline) (MDEA); 4,4'-methylene-bis-(2-isopropyl-6-methylaniline) (MMPA); 4,4'-bis(sec-butylamino) diphenylmethane ; phenyl-enediamine; methylene- bis-orthochloroaniline (MBOCA); 4,4'-methylene-bis-(2-methyl-aniline) (MMA); 4,4'- methylene-bis-(2-chloro-6-ethylaniline) (MCEA); l,2-bis(2-amino-phenylthio) ethane; N,N'-di-alkyl-p-phenylenediamine; 4,4'-methylene-bis(2,6-diisopropylaniline) (MDIPA); dimethylthiotol-uenediamine (DMTDA) or mixtures thereof.

[0027] Optionally, the aromatic diamine chain extender reaction component may include mixtures of aromatic diamine chain extender selected from those described above and/or from others as known to those having ordinary skill in the art.

[0028] Particular embodiments include an amount of the aromatic diamine chain extender reaction component (expressed as the wt.% of the total mass of the reactant components of Part A and Part B) as being between about 0 wt.% and about 10 wt. % of the total mass or alternatively between about 5 wt.% and about 7 wt. % or between about 3.5 wt.% and about 5 wt. %.

[0029] The Part B mixture used to form the polyurethaneurea system of particular embodiments includes a short aromatic diisocyanate and a prepolymer. The prepolymer may be formed of a short aromatic diisocyanate and a diol. A short aromatic diisocyanate is typically a non-polymerized component.

[0030] The short aromatic diisocyanate reaction component included in particular embodiments may be characterized as being a low-viscosity liquid at room temperature for ease of handling; e.g., a short aromatic diisocyanate having a viscosity of between about 20 and about 30 cps at 25 ⁰C. The short aromatic diisocyanate reaction component typically has a molecular weight that is less than about 500 with particular embodiments having a molecular weight of between 160 and 500 or alternatively between 160 and 300. In particular embodiments, the short aromatic diisocyanate reaction component may have a isocyanate functionality of 2 or alternatively, between about 1.8 and 2.2 or between about 1.9 and about 2.1.

[0031] Non-limiting examples of suitable short aromatic diisocyanates include, for example, phenylene diisocyanate, p- and m-phenylene diisocyanates; toluene diisocyanates, xylene diisocyanates, 2, 4 and/or 2,6 toluene diisocyanates (TDI), 1,5- naphthalene diisocyanate; carbodimide modified methylene diisocyanate, 4, 4'-diphenyl- methane diisocyanate (MDI) and, if appropriate, its higher homologues (polymeric MDI), modified MDI compounds, naphthalene diisocyanates (NDI), isomer mixtures of individual aromatic diisocyanates or combinations thereof. An example of a modified MDI compound that is useful as a short aromatic diisocyanate is a polycarbodiimide- modified diphenylmethane diisocyanate such as is available from the Dow Chemical Company as ISONATE 143L.

[0032] Particular embodiments include an amount of the short aromatic diisocyanates reaction component (expressed as the wt.% of the total mass of the reactant components of Part A and Part B) as being between about 0 wt.% and about 25 wt. % of the total mass or alternatively between about 1 wt.% and about 15 wt. % or between about 1 wt.% and about 13 wt. %.

[0033] The aromatic diisocyanate prepolymer reaction component of the Part B mixture of the polyurethaneurea system may in particular embodiments be characterized as the reaction product between a short aromatic diisocyanate as described above and a diol. The aromatic diisocyanate prepolymer may further be characterized as having an isocyanate functionality of 2 or alternatively, between about 1.8 and 2.2 or between about 1.9 and about 2.1.

[0034] In particular embodiments, the diol reacted to form the aromatic diisocyanate prepolymer is a primary diol. In particular embodiments, the diol used to form the prepolymer may be 100 wt.% a primary diol, may be greater than about 95 wt.% a primary diol, may be greater than about 75 wt.% a primary diol or may be greater than about 50 wt.% a primary dio!. Particular embodiments include a diol having a molecular weight of between about 250 and about 3000 or alternatively, between about 400 and about 2000.

[0035] Typically, suitable prepolymers may have a molecular weight that is greater than 500 or that is between about 500 and about 4000. Other embodiments include prepolymers having a molecular weight that is between about 800 and about 3000 or alternatively, between about 850 and about 1500.

[0036] A useful prepolymer as a reaction component for particular embodiments may be the reaction product of a short aromatic diisocyanate and a polyether or polyester- based primary diol. An example of a useful polyether-based aromatic diisocyanate prepolymer is a polyether-based diphenylmethane diisocyanate terminated prepolymer such as is available from Chemtura as VIBRATHANE B836. This prepolymer is the reaction product of a polyether with diphenylmethane diisocyanate (MDI).

[0037] Particular embodiments include an amount of the aromatic diisocyanate prepolymer reaction component (expressed as the wt.% of the total mass of the reactant components of Part A and Part B) as being between about 0 wt.% and about 50 wt. % of the total mass or alternatively between about 5 wt.% and about 45 wt. % or between about 10 wt.% and about 35 wt. %.

[0038] The pot life, or the time limit for use of the polyurethaneurea adhesive/repair material before it becomes too viscous to spread, may be between about 1.5 and about 4 minutes at 40 ⁰C after the reaction components (Part A and Part B) have been mixed together. Particular embodiments of the polyurethaneurea system may therefore include, as a reaction component, a reactivity catalyst that is useful to adjust the pot life, as known to those having ordinary skill in the art. An exemplary reactivity catalyst is alicyclic (cyclo-aliphatic) tertiary amine such as triethylenediamine.

[0039] The reactivity catalyst may be typically added to the reaction components at between about 0.1 and about 1.5 wt.% of the total reaction components (Part A and Part B). In other embodiments, the reactivity catalyst may be added to the reaction components at between about 0 and about 15 wt.%, between about 0.05 and about 9 wt.% or between about .4 and about 1 wt.%.

[0040] It was found that in particular embodiments, the omission of the catalyst provided a polyurethaneurea material that was much more rigid and quite opaque when compared to the material of other embodiments that resulted when the catalyst was added. Particular embodiments that include the reactivity catalyst advantageously provide a polyurethaneurea material that is typically similar in physical properties, e.g., rigidity, elongation at break and hysteresis, to the rubber elastomeric materials being bonded and/or repaired.

[0041] Protectorants may also be added to the reaction components to provide protection against environmental hazards. Such protectorants may include, for example, antioxidants, UV absorbers, light stabilizers and combinations thereof. Reactive polymeric colorants may also be added as reaction components to provide coloration to the polyurethaneurea material. For example, if repairing a tire, black colorant may be used so that the repair material matches the color of the tire.

[0042] Particular embodiments of the polyurethaneurea system may further include an elastomer-surface activator used to coat the surface of a material being bonded or repaired prior to the application of the Part A and Part B mixtures. The material being bonded and/or repaired by the polyurethaneurea system of particular embodiments may be an elastomeric material and/or a cross-linked rubber material. The use of the elastomer- surface activator provides, in particular embodiments, an improved bonding of the polyurethaneurea formed from the Part A and Part B mixtures to the surfaces being bonded or repaired.

[0043] The elastomer-surface activator of particular embodiments may comprise a short aromatic diisocyanate (as described above) and a prepolymer. The prepolymer may, for example, be the reaction product between a short aromatic diisocyanate and a diol as disclosed above. For particular embodiments, the short aromatic diisocyanate of the elastomer-surface activator may be the same as the short aromatic diisocyanate selected as a reaction component of the Part B mixture or the short aromatic diisocyanate of the elastomer-surface activator may be different than the short aromatic diisocyanate selected as a reaction component of the Part B mixture. Particular embodiments include an elastomer-surface activator comprising only the short aromatic diisocyanate and the prepolymer without a solvent while other embodiments include a solvent.

[0044] For those embodiments that include a solvent in the elastomer-surface activator, the solvent content is typically between about 35 and about 65 wt.% based upon the total mass of the elastomer-surface activator. Suitable solvents include, for example, toluene, ethyl acetate, methyl ethyl ketone (MEK) or mixtures thereof. Particular embodiments of the elastomer-surface activator comprise an amount of the short aromatic diisocyanate of between about 0 and about 90 wt.%, or alternatively between about 0 and about 80 wt.% or between about 5 and about 80 wt.% based upon the total mass of the diisocyanate in the elastomer-surface activator, the remainder being the prepolymer. Particular embodiments include, for example, an about 50:50 wt.% mix of the short aromatic diisocyanate to the aromatic diisocyanate prepolymer or alternatively, an about 5:95 wt.% ratio of the short aromatic diisocyanate to the aromatic diisocyanate prepolymer in the activator.

[0045] Particular embodiments of the present invention also include methods for making the polyurethaneurea adhesive/repair material. A particular embodiment includes reacting the Part A mixture with the Part B mixture. In one embodiment, the following amounts (expressed as weight percent of the total mass of reactant components) are reacted:

Part A a) between about 55 and about 75 % of the oligomeric polyol having an average molecular weight greater than 1000; b) between about 3 and about 7 % of an aromatic diamine chain extender; and c) between 0.1 and 1.5 % of the reactivity catalyst. Part B: d) between about 1 and about 15 % of the short aromatic diisocyanate; e) between about 5 and about 35 % of the prepolymer.

[0046] It may be noted that the rigidity of the polyurethaneurea material may be adjusted by changing the ratio of the aromatic diamine chain extender to the polyol in the Part A mixture. By increasing the amount of the aromatic amine, the rigidity typically increases in the resulting polyurethaneurea material.

[0047] Optionally, between about 0 and about 5 wt.% of protectorants and/or colorants may be added to the reactant mixture. Particular embodiments may include between about 0.5 and about 2 wt.% of these materials. Typically these materials may be added to the Part A mixture of reactant components. In particular embodiments, some or all of these components may be added to the Part b mixture of reactant components.

[0048] Particular embodiments of the method for making the polyurethaneurea composition include dispensing the two-part reaction mix through an adhesive dispenser and further, through a dispenser that may have a static mixer. The static mixer, which is typically disposable, ensures that the Part A and Part B mixtures are well mixed during the dispensing step. The adhesive dispenser may be manually, pneumatically or electrically operated. The adhesive dispenser may be used as an alternative to manually proportioning and mixing the Part A and Part B mixtures.

[0049] Such dispensers and their use are well known by those having ordinary skill in the art and are available, for example, from ConProTec, Inc., having an office in New Hampshire, under the trade name MIXPAC Systems. The cartridge volume ratio of the adhesive dispenser must be compatible with the adhesive formulation. For example, the MIXPAC systems are available in models that provide mixed adhesive in mix ratios of the two part systems of 1 :1, 2: 1, 4:1 or 10:1.

[0050] Bonding and/or repairing elastomer surfaces using particular embodiments of the polyurethaneurea system may include treating the surfaces to be bonded and/or repaired with the elastomer-surface activator. In particular embodiments of the method, at least one of the surfaces to be bonded and/or repaired include an elastomeric surface, some of which may include an elastomer comprising a cross-linked rubber composition. Optionally, but not required, the elastomer surfaces may be cleaned and treated with a primer to improve the adhesiveness and wetability of the surfaces to be bonded and/or repaired prior to applying the elastomer-surface activator and/or the polyurethaneurea reaction components. Treatment with such a primer typically removes the contamination layers or layers of poor adhesion. An exemplary primer is, for example, a solution of trichloroisocyanuric acid (TIC) in a solvent, for example 2-6% TIC in ethyl acetate.

[0051] If the primer is used, the primer may be brushed onto the elastomer surfaces and left on the surfaces for about 15 minutes. Then the surfaces may be rinsed with a solvent, such as with ethyl acetate, to remove any excess TIC. These steps may be repeated until the surface is clean and ready for the elastomer-surface activator and/or the polyurethaneurea reaction components.

[0052] The elastomer-surface activator may be applied to the surfaces to be bonded and/or repaired using a brush, spatula, sprayer or other means known to those having ordinary skill in the art. One or more layers of the elastomer-surface activator may be applied to obtain the desired thickness. Particular embodiments include applying a thickness of the elastomer-surface activator of up to about 0.5 mm or alternatively, between about 0.05 and about 0.25 mm. The adhesion of the polyurethaneurea material is typically improved with the use of the elastomer-surface activator prior to application of the two-part polyurethaneurea reaction components.

[0053] Particular embodiments of repairing an article and/or bonding surfaces with the polyurethaneurea system may be advantageously carried out at ambient temperatures, i.e., between about 20 ⁰C and about 40 ⁰C. If opposing faces are being bonded together, a pressure of, for example, between about 0.03 bar and about 5 bar, may be applied to the bonding pieces, wherein the duration of exertion is typically proportionately longer at lower pressures.

[0054] A maturation time for the polyurethaneurea system used in the present invention may be used when bonding and/or repairing materials. This maturation time may typically be about 48 hours at ambient temperature or a few hours at a temperature of between 60 ⁰C and 100 ⁰C. Advantageously, the polyurethaneurea system formed primarily of primary diols as discussed above maintains its bonded/repaired state even when subjected to temperatures of at least 130 ⁰C, which is a typical curing temperature during a tire retreading process using a cushion gum material to attach the tread to the tire carcass. [0055] Advantageously, particular embodiments of the polyurethaneurea system provides a material that possesses rigidity and hysteresis characteristics that are quite compatible with the rigidity and hysteresis of various cross-linked rubber elastomers used in tires. This characteristic of the polyurethaneurea material makes it very useful as an adhesive and/or repair material for tires.

[0056] Particular embodiments of the present invention include articles having bonded faces and/or repairs using the polyurethaneurea system disclosed herein. For example, an article according to particular embodiments of the invention comprises parts that are bonded together at opposing faces by the disclosed polyurethaneurea system, wherein at least one of the opposing faces comprises a cross-linked rubber composition. After mixing the polyurethaneurea reaction components, the polyurethaneurea reaction components are typically applied to the opposing faces of the parts, for example by using a spray gun, a brush or a two-part adhesive gun. In particular embodiments, the elastomer- surface activator is applied to both surfaces of the faces prior to the application of the mixed polyurethaneurea reaction components.

[0057] A particular embodiment of the present invention includes a tire having an elastomer patch bonded thereto by the polyurethaneurea system disclosed herein. The elastomer patch may comprise radio frequency identification (RFID) technology and the patch may be bonded to the inner or outer surface of the tire.

[0058] Other embodiments include bonding articles to a surface of another article, such as a tire. Such articles that may be bonded to a surface of another article such as a tire include, for example, letters made of an elastomer material or made of metal or fabric. Other articles may include an electronic component or device that may be bonded directly to the surface of the other article, such as a tire, without mounting or enclosing the electronic component or device in a patch. Non-limiting examples of such devices may include, for example, an RFID chip, a surface acoustic wave (SAW) sensor, a pressure and/or temperature sensor. Such devices may be mounted on an inside surface of a tire or on an outside surface of a tire. Such embodiments may include any or all of the following steps: cleaning the surface of the article, such as a tire; applying (as described above) a primer (such as a solution of TIC in a solvent) to the surface; applying (as described above) the elastomer-surface activator to the surface; placing the electronic component or device on the surface of the tire; applying the mixed Part A and Part B reaction components directly over at least a portion of the electronic component, or device thereby bonding the electronic component or device directly to the surface. As noted before, in embodiments that include bonding an article to a tire surface, the article (such as an electronic device or component) may be bonded to the outer or inner surface of the tire.

[0059] Optionally, a component such as, for example, an RFID device or a SAW sensor may be applied using a transfer film as known to those having ordinary skill in the art. A transfer film may be a flexible plastic sheet. The device may be placed on the transfer film and then covered at least partially with the polyurethaneurea components (Part A and Part B mixtures). The film with the tag may then be placed at the desired location, e.g., the surface of a tire, with the film facing outward. The film may then be peeled off leaving the component bonded to the surface.

[0060] A tire or other article comprising an elastomer surface may be repaired by filling a hole, cut, gash, gouge or other opening in the article with the polyurethaneurea system disclosed herein. Passenger tires, truck tires, motorcycle tires, off-road tires and other types of tires may be repaired or patched using the polyurethaneurea system of the present invention. The material is especially useful for repairing a gash, hole or gouge in the sidewall of a tire. In particular embodiments, the articles are repaired by applying the elastomer surface activator and then the Part A and Part B mixture.

[0061] Particular embodiments of the present invention therefore include tires or other articles having elastomeric surfaces to be bonded and/or repaired with the polyurethaneurea system. In the case of a tire having a cut, crack, hole or gouge, the area to be repaired is typically prepared by removing loose surface material and cleaning the surface within and around the damaged area. Preparation may include buffing the surface inside the gouge, cut or crack via any conventional apparatus or treatment.

[0062] If cords in the tire have been damaged, the damaged cords may be removed and a reinforced patch applied to the inner surface of the tire as known to those having ordinary skill in the art. Such cords may be made of polyester, nylon, steel, rayon and the like. The reinforced patch may be bonded to the inner surface of the tire using the polyurethaneurea system disclosed herein. Likewise, if the damage results in a hole through the sidewall, a patch may similarly be applied to the inner surface of the tire as part of the repair.

[0063] The interior faces of the gouge, crack and/or hole may then optionally be coated with the elastomer-surface activator as described above. The damaged area is then filled with the polyurethaneurea material by mixing the Part A and Part B materials and applying the mixture in the crack or gouge. The material is then allowed to cure at ambient temperature, i.e., between about 20 ⁰C and 40 ⁰C. The material can be placed in an autoclave if other repairs to the tire require curing under heat and pressure as known to those having ordinary skill in the art.

[0064] Since the curing of the polyurethaneurea material occurs at ambient temperature, the polyurethaneurea system of the present invention is particularly useful for in situ repair of large items, such as off-the-road tires, conveyor belts and the like. The polyurethaneurea system can be used on the job site with no special autoclaves, steam chambers or vulcanizable tire repair equipment needed.

[0065] Particular embodiments of the present invention further include bonding a tread band to a tire carcass, wherein the tire carcass is new or used. Bonding a tread band to a used tire carcass is known as retreading a tire. Embodiments of the present invention further include a tire having a tread bonded thereto with the polyurethaneurea system of the present invention.

[0066] A retread process of the present invention includes removing the old tread from a tire carcass, treating the tire carcass with the elastomer-surface activator or treating the tread band with the elastomer-surface activator or treating both with the elastomer- surface activator. The method further includes applying the mixed polyurethaneurea reactants to the exposed faces of the tread band or the tire carcass or both, and then placing the tread band over the surface of the tire carcass.

[0067] Particular embodiments of the present invention include bonding or repairing articles having elastomeric faces, especially those having at least one face comprising a cross-linked rubber composition. Particular embodiments have at least one face comprising a cross-linked rubber composition comprising predominately at least one diene elastomer.

[0068] The term "diene elastomer" means an elastomer derived at least in part (i.e., a homopolymer or a copolymer) from diene monomers (monomers bearing two conjugated or unconjugated carbon-carbon double bonds), in particular: any homopolymer obtained by polymerization of a conjugated diene monomer containing from 4 to 12 carbon atoms; any copolymer obtained by copolymerization of one or more dienes, conjugated together or with one or more vinyl aromatic compounds containing from 8 to 20 carbon atoms; a ternary copolymer obtained by copolymerization of ethylene or of an alpha-olefin containing 3 to 6 carbon atoms with an unconjugated diene monomer containing from 6 to 12 carbon atoms, such as the elastomers obtained from ethylene or from propylene with an unconjugated diene monomer of the above-mentioned type, in particular, 1,4-hexadiene, ethyl idenenorbomene or dicyclopentadiene; or a copolymer of isobutene and of isoprene (butyl rubber or HR), and also the halogen, in particular chloro or bromo, versions of this type of copolymer.

[0069] Particularly preferred diene elastomers are chosen from the group consisting of polybutadienes (BR), polyisoprenes (IR) or natural rubber (NR), styrene- butadiene copolymers (SBR), terpolymers of ethylene, of propylene and of a diene (EPDM), butyl rubber and chloroprene.

[0070] In a further embodiment of the invention, one of the faces of the parts to be bonded together by the polyurethaneurea system adhesive to obtain the above- mentioned article comprises a cross-linked rubber composition, while the other face comprises a ferrous metal or an iron-based metal alloy, such as steel.

[0071] According to a still further embodiment of the invention, one of the faces comprises a cross-linked rubber composition, while the other face comprises a synthetic fabric, such as a fabric of bi-elastic knit type to form membranes of configuration containing fibers sold under the registered trademark "LYCRA".

[0072] According to a still further aspect of the invention, one of the faces comprises a cross-linked rubber composition, while the other face comprises a rigid plastic, such as a thermosetting polyurethane (for example, application of decoration to tire covers).

[0073] The invention is further illustrated by the following examples, which are to be regarded only as illustrations and not delimitative of the invention in any way.

Example 1

[0074] Batches of the polyurethaneurea system were prepared using the reactant components shown in Table 1. The two-part adhesive/repair materials were prepared by mixing the Part A components with the Part B components. These polyurethaneurea materials were then used to bond two pieces of elastomer together by filling a gap between the two pieces of elastomer with the polyurethaneurea system. The resulting bonding strengths were then measured. Table 1 - Pol iirethaneurea Reactant Com onents

[0075] ETHACURE 300 is a short-chained aromatic diamine chain extender available from Albemarle Corporation. This product is predominately the aromatic diamine 3,5-dimethylthio-2,4- (and 2,6) toluenediamine (DMTDA). TERATHANE 2900 is a oligomeric polyol available from DuPont. This product is a polytetramethylene ether glycol (PTMEG) having an average molecular weight of 2900. REACTINT BLACK X95AB is a polyol bound colorant available from Milliken Chemical. TINUVIN B75 is a protectorant system available from Ciba Specialty Chemicals. ISONATE 143L is a polycarbodiimide-based aromatic diisocyanate available from Dow Chemical. This modified MDI product is a polycarbodiimide-modified diphenylmethane diisocyanate. VIBRATHANE B836 is a polyether-based aromatic diisocyanate available from Chemtura. This product is an MDI-terminated polyether (PTMEG backbone) diisocyanate. DABCO 33-LV is the reactivity catalyst triethylenediamine available from Air Products.

[0076] The Part A materials were mixed together and the Part B materials were mixed together and each were then loaded into the cartridges of a two-part adhesive dispenser gun. The cartridges were inserted into the two-part cartridge-based adhesive dispenser gun. The ratio that the gun dispenser delivered Part A and Part B to the static mixer was 4:1; i.e., the dispenser delivered 4 times as much volume of Part A as of Part B, for Al and A2 and 2:1 for A3. The Part A and Part B reaction components were mixed by the adhesive dispenser through the attached disposable static mixer.

[0077] Elastomer-surface activator was also prepared. The elastomer surface activator was prepared by mixing the diisocyanates in the quantities shown in Table 1 with a solvent. The weight percent of each of the diisocyanates shown in Table 1 is based upon the total mass of the diisocyanates. The diisocyanates were mixed in a solvent to form the elastomer-surface activator that was made up of 50 wt.% (based on the total weight of the solution) of ethyl acetate or toluene as the solvent and 50 wt.% of the diisocyanates.

Example 2

[0078] Three different rubber elastomer materials were prepared using methods well known to those have ordinary skill in the art. The three materials were a sidewall type (SW) rubber composition comprising natural rubber and cis-polybutadiene rubber, an inner liner type (IL) rubber comprising butyl rubber and a tread type (T) rubber comprising natural rubber. These materials further comprised vulcanizing agents, etc. as known to those having ordinary skill in the art.

[0079] Each composition was calendered to a thickness of 2.5 mm and cut into 15x15 cm squares. These squares were cured in a 15x15 cm mold. A strip approximately 1.25 cm was cut from each cured square so that each of the remaining parts of the squares were separated by about 1.25 cm. The volume between the two parts, which was created by cutting out the strip, was then filled with the polyurethaneurea material prepared in Example 1. Some of the surfaces were treated with the elastomer-surface activator prepared in Example 1. It should be noted that the Part A components were heated to 40 ⁰C to improve their flow characteristics. After heating to 40 ⁰C, the material will cool to room temperature but maintain good flow characteristics for several hours (4-8) thereafter.

[0080] After the polyurethaneurea material filled the gap between the two halves, the samples were cured in the mold. The mold top exerted a pressure of about 1.5 bar on the samples as they were curing. The curing occurred in the mold utilizing the following procedure: after the top was set in place, the mold was heated over a 20 minute period to bring the temperature up from room temperature to 130 ⁰C; the temperature was held at 130 ⁰C for 100 minutes. After cooling, the squares were removed and each cut into six strips to form 6 samples for testing. Example 3

[0081] The test specimens prepared in Example 2 were tested to determine their elongation at break property. The elongation property was measured as elongation at break (%), as measured at 23 ⁰C in accordance with ASTM Standard D412 on ASTM C test pieces. Both the elongation at break % and the break strain (MPa) were recorded. The results are shown in Table 2 for test specimens comprising the sidewall rubber (SW) composition, in Table 3 for test specimens comprising the inner liner (IL) composition and in Table 4 for test specimens comprising the tread (T) composition.

[0082] Test specimen No. 1 shown in each of the three tables below was a rubber witness test. The test results for the rubber witness test provided the elongation at break physical property of the rubber composition itself without being bonded with the polyurethaneurea system of the present invention.

[0083] As shown in Tables 2, 3 and 4, some of the bonded surfaces of the test specimens were primed using a solution of trichloroisocyanuric acid (TIC) in a solvent. The tables indicate which of the specimens were primed, the solvent used and the number of times the solution was applied. For example, test specimen No. 3 shown in Table 2 was primed with three coatings (brush) of a TIC 5 wt.% in ethyl acetate solution. The sample was allowed to dry for 30 minutes at room temperature after being primed and was washed with ethyl acetate after drying.

[0084] Likewise, the tables indicate which test specimens were treated with the elastomer-surface activator comprising the components shown in Table 1 of Example 1. The solution of the elastomer-surface activator is also provided in the tables as well as for how long the specimens were allowed to dry before the PUU formulation was added to the surfaces.

Table 4 - Test Results for Tread Rubber (T) Com osition

[0085] The test results shown in Tables 2-5 are plotted in FIG. 4. The selected zones circles in FIG. 4 define an optimal adhesion condition for each of the different rubber compositions.

Example 4

[0086] Samples of the A2 material were prepared and allowed to cure into sheets. ASTM C test pieces of each of the rubber compositions (T, SW, IL) that were prepared in Example 2 as well as of the A2 material were prepared. [0087] The moduli of elongation were then measured on the test pieces at 10%, 50%, 100%, 200% and 300% at a temperature of 26 ⁰C in accordance with ASTM D412 (1998) on the ASTM C test pieces. These are true secant moduli in MPa, that is to say the secant moduli calculated reduced to the real cross-section of the test piece at the given elongation. Hysteresis was also determined on each of the test pieces. The test procedures were run on an INSTRON, Model 5500R test machine.

[0088] The results of these tests are shown in FIGS 1-3. As may be seen from these figures, the A2 polyurethaneurea material matches well the rigidity and elasticity measurements of the different rubber compositions. FIGS. 1 and 2 illustrate that the A2 material is more rigid at low deformation. FIG. 3 illustrates the low hysteresis of the material at low deformation. Although not clearly shown in FIG. 2, it has been shown that at high deformation, e.g., above 300 % strain, the A2 material is softer than the T and SW material.

[0089] The terms "comprising," "including," and "having," as used in the claims and specification herein, shall be considered as indicating an open group that may include other elements not specified. The term "consisting essentially of," as used in the claims and specification herein, shall be considered as indicating a partially open group that may include other elements not specified, so long as those other elements do not materially alter the basic and novel characteristics of the claimed invention. The terms "a," "an," and the singular forms of words shall be taken to include the plural form of the same words, such that the terms mean that one or more of something is provided. The terms "at least one" and "one or more" are used interchangeably. The term "one" or "single" shall be used to indicate that one and only one of something is intended. Similarly, other specific integer values, such as "two," are used when a specific number of things is intended. The terms "optionally," "may," and similar terms are used to indicate that an item, condition or step being referred to is an optional (not required) feature of the invention. Ranges that are expressed as being between two points, such as between x and y, include x and y in the range.

[0090] It should be understood from the foregoing description that various modifications and changes may be made in the preferred embodiments of the present invention without departing from its true spirit. The foregoing description is provided for the purpose of illustration only and should not be construed in a limiting sense. Only the language of the following claims should limit the scope of this invention.

Claims

CLAIMSWhat is claimed is:

1. A polyurethaneurea system, wherein reaction components react to form polyurethaneurea, the reaction components comprising: part A, wherein part A is a mixture comprising: between about 55 and about 75 wt.% of an oligomeric polyol having an average molecular weight greater than about 1000; between about 3 and about 7 wt.% of an aromatic diamine chain extender; and between about 0.1 and about 1.5 wt.% of a reactivity catalyst; and part B, wherein part B is a mixture comprising: between about 1 and about 15 wt.% of a short aromatic diisocyanate; and between about 5 and about 35 wt.% of an aromatic diisocyanate prepolymer that is the reaction product of a short aromatic diisocyanate and a diol, wherein the mass fraction of each of the reaction components is based upon the total mass of the part A and part B reaction components.

2. The polyurethaneurea system of claim 1, wherein the oligomeric polyol comprises greater than 50 wt.% primary oligomeric polyol.

3. The polyurethaneurea system of claim 1, wherein the oligomeric polyol comprises greater than about 95 wt.% primary oligomeric polyol.

4. The polyurethaneurea system of claim 1, further comprising: an elastomer-surface activator comprising a second short aromatic diisocyanate and a second aromatic diisocyanate prepolymer.

5. The polyurethaneurea system of claim 4, wherein at least one of the second diisocyanates of claim 2 is the same as at least one of the diisocyanates of claim 1.

6. The polyurethaneurea system of claim 4, wherein the elastomer-surface activator further comprises a solvent.

7. The polyurethaneurea system of claim 4, wherein the elastomer-surface activator includes between 0 and 90 wt.% of the short aromatic diisocyanate, wherein the mass fraction is based upon the total mass of the diisocyanates in the elastomer-surface activator.

8. The polyurethaneurea system of claim 7, wherein the elastomer-surface activator includes between 5 and 80 wt.% of the short aromatic diisocyanate.

9. The polyurethaneurea system of claim 1, further comprising up to 2 wt.% protectorants selected from antioxidants, UV absorbers, light stabilizers or combinations thereof.

10. The polyurethaneurea system of claim 1, further comprising reactive polymeric colorants.

11. The polyurethaneurea system of claim 1, wherein the short aromatic diisocyanate is a polycarbodiimide-modified diphenylmethane diisocyanate.

12. The polyurethaneurea system of claim 1, wherein the short aromatic diisocyanate is selected from 2, 4 and/or 2,6 toluene diisocyanate (TDI), 4, 4'-diphenyl-methane diisocyanate (MDI), polymeric MDI, modified MDI compounds, naphthalene diisocyanate (NDI) or combinations thereof.

13. The polyurethaneurea system of claim 1, wherein the aromatic diisocyanate prepolymer is an MDI-terminated polyether diisocyanate.

14. The polyurethaneurea system of claim 1, wherein the aromatic diisocyanate prepolymer is the reaction product of the diol that is selected from a polyether-based diol, a polyester-based diol or combinations thereof.

15. The polyurethaneurea system of claim 1, wherein the oligomeric polyol is a polytetramethyleneglycol having an average molecular weight between about 1500 and about 4000.

16. The polyurethaneurea system of claim 1 , wherein the aromatic diamine chain extender is a mixture of 2,4 and 2,6 isomers of dimethylthiotoluenediamine.

17. The polyurethaneurea system of claim 1, wherein a ratio of isocyanate functionalities to a total of the amine and hydroxyl functionalities in a mixture of part A and part B is between 0.8 and 2.

18. The polyurethaneurea system of claim 17, wherein the ratio of isocyanate functionalities to the total of the amine and hydroxyl functionalities in the mixture of part A and part B is between 1.0 and 1.07.

19. A process, comprising: reacting the following reaction components in mass fraction relative to the total mass of reactants to form a polyurethane urea repair material: part A, wherein part A is a mixture comprising: between 55 and 75 wt.% of an oligomeric polyol having an average molecular weight greater than 1000; and between 3 and 7 wt.% of an aromatic diamine chain extender; and between 0.1 and 1.5 % of a reactivity catalyst; and part B, wherein part B is a mixture comprising: between 1 and 15 wt.% of a short aromatic diisocyanate; and between 5 and 35 wt.% of an aromatic diisocyanate prepolymer that is the reaction product of a short aromatic diisocyanate and a diol.

20. The process of claim 19, further comprising: applying the polyurethaneurea to a face of a cross-linked rubber article; and bonding the face of the cross-linked rubber article to a substrate.

21. The process of claim 19, further comprising: applying an elastomer-surface activator to the face of the cross-linked rubber article, wherein the elastomer-surface activator comprises a second short aromatic diisocyanate and a second aromatic diisocyanate prepolymer.

22. The process of claim 21 , further comprising: priming the face of the cross-linked rubber article with a solution of trichloroisocyanuric acid in a solvent.

23. The process of claim 19, wherein the substrate is a face of a cross-linked rubber article.

24. An article, comprising: a component bonded to the article with the polyurethaneurea system of claim 4.

25. The article of claim 24, wherein bonded faces between the component and the article are of cross-linked rubber composition.

26. The article of claim 25, wherein the article is a tire.

27. The article of claim 26, wherein the component is a tread band.

28. The article of claim 26, wherein the component is a patch.

29. The article of claim 26, wherein at least one of the bonded faces between the component and the article are of cross-linked rubber composition.

30. The article of claim 29, wherein a face of the component comprises a synthetic fabric, a thermosetting polymer, a ferrous metal, an iron-based metal alloy or combinations thereof.

31. The article of claim 29, wherein a face of the article comprises a synthetic fabric, a thermosetting polymer, a ferrous metal, an iron-based metal alloy or combinations thereof.

32. The article of claim 26, wherein the component is an electronic device.

33. The article of claim 32, wherein the component comprises an RFID chip.

34. The article of claim 32, wherein the article comprises a SAW sensor.

35. A method for retreading a tire, comprising: applying the elastomer-surface activator of claim 2 to a bonding surface of a tread band; applying the polyurethaneurea material of claim 1 to the bonding surface of the tread band; placing the bonding surface of the tread band having the polyurethaneurea material thereon onto an outer bonding surface of a tire carcass.

36. The method of claim 35, further comprising: applying the elastomer-surface activator of claim 2 to the outer bonding surface of the tire carcass; applying the polyurethaneurea material of claim 1 to the outer bonding surface of the tire carcass.

37. A method of repairing an elastomeric article, comprising: coating a damaged surface of the elastomeric article with the elastomer-surface activator of claim 2, wherein the damaged surface is an exposed surface of a hole, gash, gouge, split, cut or tear in the article; filling the hole, gash, gouge, split, cut or tear in the article with the polyurethaneurea of claim 1.

38. The method of claim 37, wherein the article is a tire.

39. The method of claim 37, wherein the hole, gash, gouge, split, cut or tear is in a sidewall of the tire.

40. The method of claim 37, wherein the hole, gash, gouge, split, cut or tear is in an interior surface of the tire.

41. An article repaired by the method of claim 37.

42. The article of claim 41, wherein the article is a tire.