`Koch et al.
`
`(54)
`
`(75)
`
`(73)
`
`21
`22)
`(51)
`(52)
`
`58
`
`(56)
`
`ROOM TEMPERATURE CURABLE TRE
`PATCH
`Inventors: Russell W. Koch, Hartville; William
`W. Barbin, Massillon, both of Ohio
`Assignee: The Firestone Tire & Rubber
`Company, Akron, Ohio
`Appl. No.: 477,452
`Filed:
`Mar. 21, 1983
`Int, Cl. .............................................. B60C 21/00
`U.S. C. .................................... 152/370; 152/367;
`152/371; 156/95; 156/97; 264/36; 427/140;
`428/63
`Field of Search ................ 156/97, 95, 307.3, 315;
`427/140; 152/367, 371, 370; 428/63; 264/36
`References Cited
`U.S. PATENT DOCUMENTS
`3,644,256 2/1972 Broisman .............................. 269/29
`3,718,587 2/1973 Bhakuni ........
`... 252/8.6
`3,755,261 8/1973 VanGulick
`... 260/77.5
`3,779,794 12/1973 DeSantis ............................... 117/72
`3,834,934 9/1974 Broisman.
`117/76 T
`3,888,831 6/1975 Kogon ................................ 260/77.5
`3,966,530 6/1976 Cutts et al. .......................... 156/308
`3,991,255 1 1/1976 Blaskiewicz et al.
`... 428/425
`4,085,283 4/1978 Den Otter et al. ...
`... 260/248
`4,125,522 11/1978 Becker .................................. 528/61
`4,136,219 1/1979 Odam et al...
`427/385 B
`4,143,454 3/1979 Utsunomiya .......................... 29/460
`4,158,378 6/1979 Pearson et al. ...
`152/353 R.
`4,240,852 12/1980 Gomberg .............................. 156/96
`
`11)
`45
`
`4,434,832
`Mar. 6, 1984
`
`
`
`4,300,970 1 1/1981 Honda et al. ................... 156/244.11
`4,311,181 1/1982 Hausch .......
`52/353 R.
`4,327,138 4/1982 Hausch .................................. 428/36
`4,352,704 10/1982 Williams .............................. 156/125
`FOREIGN PATENT DOCUMENTS
`1352645 5/1971 United Kingdom .
`OTHER PUBLICATIONS
`"Room Temperature Vulcanizing Adhesive Based on
`Ethylene-Propylene-Diene Terpolymer,” Cantor, Uni
`royal, Paper No. 18, 10/10/73, Hughson Chemical Di
`vision, Lord Corporation, Products TS-2682-71.
`Primary Examiner-George F. Lesmes
`Assistant Examiner-P. R. Schwartz
`Attorney, Agent, or Firm-Daniel N. Hall
`(57)
`ABSTRACT
`The repair of a reinforced elastomer article having a
`hollow therein relates to utilizing an amine curable
`polymer or prepolymer and a cured elastomer patch.
`The hollow in the elastomer, which can extend either
`partially or completely through the article, is filled with
`a gum rubber which is thereafter cured by conventional
`means, such as with spotters. The area beneath the now
`filled hollow is coated with a treating agent, followed
`by the amine curable polymer or prepolymer and a
`cured patch. The polymer is then cured at room tem
`perature. One area of use is in the repair of tires.
`
`19 Claims, 2 Drawing Figures
`
`
`
`peasa
`N A
`ZAC FA
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`US. Patent Mar. 6, 1984
`U.S. Patent Mar. 6, 1984
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`Sheet 1 of 2
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`4,434,832
`4,434,832
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`FIG.|
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`Sheet 2 of 2
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`4,434,832
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`1.
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`ROOM TEMPERATURE CURABLE TRE PATCH
`
`O
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`15
`
`TECHNICAL FIELD
`The present invention relates to a composition and
`method for repairing reinforced elastomer articles hav
`ing a hollow therein, such as for example a puncture in
`a tire. More specifically, the present invention relates to
`the utilization of a patch in association with the elasto
`mer article and an amine curable polymer or prepoly
`mer which is curable at ambient temperatures and
`which acts as an adhesive agent.
`BACKGROUND ART
`Heretofore, reinforced rubber articles such as tires
`having a cut or opening therein have been repaired with
`a patch. Generally the opening is first filled with an
`uncured gum rubber which is thereafter cured by such
`means as portable heating units or spotters. If required,
`a patch is applied to the inner surface of the tire or other
`article. Usually such a patch is needed if the reinforcing
`materials in the article, primarily cords or belts have
`been partially or completely severed, providing a weak
`ened area prone to subsequent failure. In providing a
`25
`patch reinforced to the same degree as the amount of
`lost reinforcement, the repaired article is, at least in
`theory, as strong as before the injury.
`Prior art patches fall into two classes, the chemical
`cure patches which are high in cost and provide only
`poor adhesion to the substrate and uncured patches
`which require the use of heat for proper cure and adhe
`sion. Unlike the method of heat application for the gum
`rubber filler, a rather sophisticated process must be used
`35
`to cure this latter type of patch, to wit, a tire mold or
`similar device. Thus when a patch is required, on the
`spot or in situ repair is exceedingly cumbersome at best
`and in most cases impossible, requiring the article to be
`returned to the shop.
`40
`The present invention utilizes a cured rubber patch
`secured to the elastomer substrate through an adhesive
`system which is curable at ambient temperatures. There
`is therefore no need for the use of a tire mold to effect
`repair and the article can easily and quickly be treated in
`45
`the field, saving both time and expense. The adhesive
`system utilizes an amine curable polyurethane or other
`prepolymer and a treating agent.
`Considering the prior art, U.S. Pat. Nos. 3,755,261 to
`VanGulick; 3,888,831 to Kogan; 3,834,934 to Broisman;
`3,644,256 also to Broisman; and 3,718,587 to Bhakuni
`relate to amine curable curing agents, amine curable
`polymers, or R.F.L. type adhesives. However, these
`patents lack any suggestion of applicants' treating agent
`or repair of an elastomer article.
`55
`U.S. Pat. No. 3,779,794 to DeSantis relates to a mois
`ture-curable polyurethane sealant primer system,
`whereas U.S. Pat. No. 4,085,283 to DenOtter relates to
`flame retardants utilized in cyanuric acid derivatives.
`Hughson Chemical Division, Lord Corporation, Prod
`60
`uct No. PS-2682-71 relates to a surface primer for elas
`tomeric substances utilizing a proprietary compound
`thought to be mono- or dichloroisocyanuric acid. An
`article entitled "Room Temperature Vulcanizing Adhe
`sive Based on Ethylene-Propylene-Diene Terpolymer,"
`65
`Cantor, Uniroyal, Paper No. 18, presented to the Divi
`sion of Rubber Chemistry of the American Chemical
`Society, Denver, Colo., Oct. 10, 1973 relates to various
`
`4,434,832
`2
`oxidants which effect ambient temperature cures of
`E.P.D.M.
`U.S. Pat. No. 4,136,219 to Oldam relates to a polyure
`thane paint which is applied to vulcanized rubbers.
`British Pat. No. 1,352,645 relates to a polyurethane
`paint which is applied to vulcanized rubbers.
`U.S. Pat. No. 4,125,522 to Becker relates to a poly
`urethane adhesive, whereas U.S. Pat. No. 3,966,530 to
`Cutts relates to triazoline diones which are utilized in
`lieu of chlorinated or halogenated donors for treating
`elastomeric surfaces to improve adhesion.
`U.S. Pat. No. 4,143,454 to Utsonomiya relates to a
`method of attaching connecting parts of an offshore
`structure wherein a liquid rubber is applied over a treat
`ing solution which may contain a halogen molecule. As
`such, this reference lacks applicant's treating agent as
`well as repair of an elastomeric article having a patch
`thereon.
`U.S. Pat. No. 4,158,378 to Pearson relates to a cured
`rubber tire having a specific polyurethane therein and
`to a chlorine water treatment. Hence, Pearson also fails
`to teach or suggest applicant's recited treating agent as
`well as the patched article.
`British Pat. No. 1,352,645 relates to N- halogen sul
`fonamide treating agents which halogenize surfaces of
`synthetic and/or natural rubbers.
`U.S. Pat. No. 3,991,255 to Blaskjiewicz relates to the
`adhesion of a polyurethane to an EPDM surface utiliz
`ing various adhesives, however, Blaskjiewicz does not
`use his treating agent to form a treating layer and uti
`lizes elevated temperatures.
`U.S. Pat. No. 4,300,970 to Honda does not disclose
`amine curable resins or an ambient temperature cure.
`U.S. Pat. No. 4,240,852 to Gomberg relates only to
`the use of a cyanoacrylate adhesive.
`U.S. Pat. No. 4,352,704 to Williams relates to apply
`ing tire tread to a tire. This patent lacks any suggestion
`of applicant's treating agent or the repair of a tire aper
`ture.
`U.S. Pat. No. 4,327,138 to Hausch fails to disclose a
`cured rubber patch in repairing a rubber article.
`One prior art method of repairing a tire article relates
`to the utilization of a proprietary compound thought to
`be a mixture of rubber and accelerators which is applied
`to the aperture and then cured. In general, a very poor
`adhesion results and heat is required.
`DISCLOSURE OF THE INVENTION
`It is therefore an aspect of the present invention to
`provide a repaired reinforced elastomer article having a
`hollow therein utilizing a cured rubber patch and an
`amine curable polymer or prepolymer.
`It is another aspect of the present invention to pro
`vide a repaired reinforced elastomer article, as above, in
`which the hollow extends into or through the rein
`forced material and the repair is made at ambient tem
`peratures.
`It is a still further aspect of the present invention to
`provide a repaired elastomer article, as above, in which
`a layer of a treating agent is positioned on the inner
`surface of said article and on the cured rubber patch.
`It is yet a further aspect of the present invention to
`provide a repaired reinforced elastomer article, as
`above, wherein said repaired elastomer article is a tire,
`a conveyor belt or the like.
`It is still another aspect of the invention to provide a
`repaired elastomer article, as above, wherein said cured
`rubber patch is located juxtaposition to said hollow.
`
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`4.
`It is yet another aspect of the present invention to
`above and vinyl substituted aromatic compounds hav
`provide a repaired reinforced elastomer article, as
`ing from 8 to 15 carbon atoms. Examples of such vinyl
`above, wherein said patch has one or more cords
`substituted aromatic compounds include styrene, alpha
`therein.
`methylstyrene, and the like. An example of a specific
`It is still another aspect of the present invention to
`copolymer is styrene-butadiene rubber. Naturally, other
`provide a repaired reinforced elastomer article, as
`types of rubber compounds can be utilized such as the
`above, wherein said amine curable polymer or prepoly
`so called butyl rubbers, neoprene, that is polychloro
`mer is a urethane polymer or prepolymer, and wherein
`prene, and the like.
`said treating agent is trichloroisocyanuric acid (tri
`The preparation of such above noted various elasto
`chloro-s-triazinetrione).
`mers is well known to the art and the article in need of
`These and other aspects of the present invention,
`repair is often in the form of a tire, especially an off the
`which will become more apparent from the following
`road tire, a conveyor belt, or similar article. Regardless
`description, are achieved by: a repaired elastomer arti
`however of the type or nature of the article, it is desir
`cle, comprising: the elastomer article, said article hav
`able to clean the surface of the hollow prior to repair.
`ing a hollow therein; a cured gum rubber disposed
`15
`Cleaning can take place as through a physical treatment
`within said hollow; a treating agent applied to the inner
`of the area to be repaired, for example, as through buff
`surface of said article immediately surrounding said
`ing or skiving, that is, cutting or as removing a portion
`filled aperture, said treating agent selected from the
`of the surface. Another method involves the use of any
`group consisting of: N-halohydantoins, N-haloamides,
`conventional organic solvent to remove dirt and resi
`N-haloimides, and combinations thereof; an amine cur
`20
`due. Typical solvents include acetone and ethyl acetate.
`able polymer or prepolymer applied over the treated
`The next step in utilizing the invention is the packing
`surface of said article; and a patch positioned over said.
`of a quantity of uncured gum rubber 22 into the hollow
`polymer or prepolymer; wherein said polymer of pre
`12, most preferably from the outer surface defined as
`polymer is cured in situ at room temperature; and
`that surface of the substrate opposite where a patch 20
`wherein said elastomer article is cured and unsaturated.
`25
`is later positioned. The gum rubber is then cured in
`placed using conventional means such as a pair of
`BRIEF DESCRIPTION OF THE DRAWINGS
`heated plates, otherwise known as spotters, one applied
`FIG. 1 relates to a cross-sectional view showing the
`to the outer surface 24 and one to the inner surface of
`repair of a reinforced elastomeric article having a hol
`the substrate.
`low extending completely therethrough, according to
`30
`The types of gum rubber which can be used are well
`the present invention.
`known in the art, being generally composed of com
`FIG. 2 is a cross-sectional view showing the repair of
`pounds of natural rubber or rubber blends and typically
`a similar reinforced elastomeric article wherein the
`having other compounding ingredients such as sulfur,
`hollow extends only partially therethrough.
`carbon black, accelerators, and the like. A variety of all
`BEST MODE FOR CARRYING OUT THE
`purpose repair gums, readily available commercially,
`INVENTION
`can be used. Alternatively, one skilled in the art can
`readily devise a suitable gum rubber recipe without
`The instant invention is useful in repairing reinforced
`undue experimentation.
`elastomer articles wherein damage has been manifested
`Once the gum rubber has been cured in place, the
`as a chunk-out, leaving a hollow area in the article. The
`40
`innerside is buffed around the now filled aperture and a
`injury may extend completely through the article or
`treating agent 16 applied both to the substrate and the
`only through a portion thereof, but reinforcement, that
`cured gum rubber surfaces, which should of course be
`is cords, belts, or the like, contained in the article will
`have been partially or completely severed thereby pro
`first cleaned as outlined above. An amine curable poly
`mer 18 is then applied to the inner surface after having
`viding a weakened area.
`45
`been first allowed to thicken or partially "set up', re
`The invention can be seen with reference to the fig
`sulting in an increase in viscosity to several thousand
`ures. As is readily apparent, the salient features in each
`centipoise. This results in a toothpaste-like consistency
`are identical except that the hollow low 120 in FIG. 2
`helping hold the polymer in place while the patch is
`does not extend completely through the substrate. For
`applied.
`the sake of simplicity, all references to FIG. 1 shall have
`50
`The patch, after being buffed and having received a
`equal reference to FIG. 2, except for the dimensions of
`coating of treating agent 16, is then applied to the poly
`the hollow, as above. Referring then to FIG. 1, the
`mer surface. It is thereafter temporarily taped into place
`article is generally indicated by the number 10, compris
`ing a substrate 13 having embedded therein a plurality
`and held by some form of applied pressure, such as, in
`the case of a tire, a curing tube or a plurality of sand
`of reinforcement cords or belts 14, and a hollow 12.
`bags. The repair is allowed to set in this position for
`The substrate 13 can be any conventional elastomer
`approximately 24 hours. The end result is a repaired
`or rubber known to those skilled in the art and having
`unsaturated groups therein. For example, it can be made
`article having much better strength and durability than
`from conjugated dienes having from 4 to 12 carbon
`one repaired according to heretofore known methods.
`atoms such as butadiene, isoprene or the like. It can also
`In the embodiment of FIG. 2, the hollow 120 in the
`be made from natural rubber, that is, from a substance
`article 100 is in the form of a cavity wherein some cords
`which is obtained from various trees and plants which
`140 of the reinforced article have been damaged, sev
`grow in the tropics or desert portions of the world.
`ered, or the like. Usually at least 25 percent of the cords
`Such natural rubber generally has in excess of 90 and
`have been broken or damaged and the article is repaired
`usually in excess of 95% of cis 1,4-polyisoprene content.
`utilizing a patch. Either the cavity can be filled or the
`65
`The substrate may also be various elastomeric copoly
`patch applied first. In repair of cavity 120, the surface is
`mers such as those made from monomers of conjugated
`first cleaned. The cavity is then filled with a gum rubber
`dienes having from 4 to 12 carbon atoms as set forth
`220, generally to the level of the substrate 130. Natu
`
`60
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`rally, in this operation, the cavity is located in the upper
`polymers which can be cured with the amine curing
`most vertical position of the article.
`agent include the compounds set forth in U.S. Pat. No.
`The area to be patched is prepared as before by clean
`3,755,261 which is hereby fully incorporated by refer
`ing and even buffing, in which, in either embodiment,
`ence. Briefly, such compounds includes the various
`the tie-gum layer or the cord ply layer can be exposed.
`epoxy resins such as those disclosed in the Encyclopedia
`Treating layer 160 is applied to the patch area of sub
`of Polymer Science and Technology, Interscience Publish
`strate 130 as well as to one side of the patch 200. The
`ers, New York (1967), vol. 6, pages 212-221; halogen
`containing hydrocarbon polymers such as chloroprene
`amine curable polymer or prepolymer 180 is then ap
`plied to the treated side of the patch, with the patch in
`polymers, chlorinated butyl rubber and chlorinated
`turn being applied to the treated portion of substrate
`polyethylene and polypropylene; chlorosulfonated pol
`130. The ends of the patch can be taped to the substrate
`ymers such as those described in U.S. Pat. No.
`or held in place with a curing tube located inside the
`2,723,257; polymers containing acid halide groups such
`tire. The number of cords in the patch is as previously
`as COCl and haloformate groups such as OCOCl; poly
`mers containing anhydride groups which on reaction
`set forth. That is, if less than 25 percent of the cords are
`damaged, the use of the patch having cords therein is
`with diamines yield amide-acid linkages, and organo
`optional in that a solid rubber patch provides adequate
`polysiloxanes as described in U.S. Pat. No. 2,938,010.
`reinforcement. When approximately 25 to 50 percent of
`The urethane prepolymers or polymers, that is, those
`the cords are damaged, severed or the like, the strength
`which contain isocyanate groups, are generally formed
`of the cords in the patch is at least equal to the strength
`by first reacting a polyether polyol or a polyester polyol
`of such cords before being damaged. When approxi
`with a molar excess of a diisocyanate to form a prepoly
`mately 50 percent or more of the cords are damaged,
`mer having terminal isocyanate groups. The polymer is
`the strength of the cords and the patch is equal to the
`then cured to increase its molecular weight from less
`strength of the total number of cords in the substrate
`than about 3000 upwards to over 10,000. Examples of
`before any injury thereto. The repair is then cured at
`such polymers are set forth in U.S. Pat. Nos. 2,618,516;
`ambient temperature.
`2,777,831; 2,843,568; 2,866,774; 2,900,368; 2,929,800;
`25
`Suitable treating agents include the various N
`2,948,691; 2,948,707; and 3,114,735 all of which are
`hereby fully incorporated by reference. Typical specific
`halohydantoins, the various N-haloamides, the various
`examples of such polyurethanes include Adiprene
`N-haloimides and combinations thereof. Examples of
`various desirable N-halohydantoins include 1,3-
`L-367 which is a polytetramethylene ether glycol con
`dichloro-5,5-dimethyl halohydantoin; 1,3-dibromo-5,5-
`taining approximately 6.4% isocyanate end groups by
`30
`dimethyl hydantoin; 1,3-dichloro-5-methyl-5-isobutyl
`weight manufactured by DuPont; Adiprene L-42, a
`hydantoin; and 1,3-dichloro-5-methyl-5-hexyl hydan
`polytetramethylene ether glycol containing approxi
`mately 2.8% isocyanate end groups by weight, also
`toin. Examples of N-haloamides include N-bromoaceta
`mide and tetrachloroglycoluril. Examples of N-haloi
`manufactured by DuPont; and Cyanaprene A-7, a
`polyester-based coating polymer with approximately
`mides include N-bromosuccinimide and the various
`35
`chloro substituted s-triazinetriones, commonly known
`2.4% isocyanate end groups, manufactured by Ameri
`as mono-, di-, and trichlorocyanuric acids. A preferred
`can Cyanamid. Blends of these polyurethanes can also
`treating composition for use in the practice of the inven
`be utilized. Moreover, it has been found, particularly
`tion are the various mono-, di-, or trichloroisocyanuric
`with repair or application of the amine curable polymer
`to the patch area, that is the area between patch 20 and
`acids or combinations thereof. Trichloro-s-triazinetr
`ione (trichloroisocyanuric acid) is especially preferred.
`cured substrate 13, better adhesion is often obtained by
`The treating agents usually exist in solid form. They
`utilizing two different types of urethane. For example, a
`urethane containing a high amount by weight of isocya
`are readily soluble in solvents such as acetone and the
`like and thus can be applied in liquid form. Application
`nate end groups, such as Adiprene L-367 can be blended
`of the treating agent generally occurs at ambient tem
`with urethane containing a low amount by weight of
`45
`peratures. Application can occur through any conven
`isocyanate such as Adiprene L-42. The relative amount
`tional manner as through brushing, spraying, or the like.
`of one urethane to the other can range from about 1 to
`The amount applied is such that the rubber substrate
`about 99% and desirably from about 30 to about 70%
`by weight.
`surface is coated. Preferably, two or more coats of the
`treating agent or adhesive compound are used to insure
`To the amine curable prepolymer or polymer com
`pound is added a conventional amine curing agent,
`that all the cured rubber substrate surface has been
`known to those skilled in the art. Generally, any con
`coated.
`A typical amount of the treating agent in the suitable
`ventional or known amine curing agent can be used and
`solvent, for example ethyl acetate or acetone is gener
`therefore only a few specific examples will be given.
`ally from 0.1 to about 10% by weight based upon the
`Thus, the curing agent can be MOCA, that is, 4,4'-
`55
`total weight of said treating agent and solvent, and
`methylene bis(2-chloroaniline) or desirably, a complex
`preferably from about 0.5% to about 5%. Of course
`of 4-4'-methylene dianiline and a salt, or a complex of
`higher or lower concentrations can be utilized. This
`racemic 2,3-di-(4-aminophenyl) butane and a salt as set
`solvent system has been found to dry within a matter of
`forth in U.S. Pat. No. 3,755,261 to VanGulick which is
`hereby fully incorporated by reference. The methods
`minutes so that the amine curable polymer or prepoly
`60
`mer can be bonded thereto. It is thought that the adhe
`for preparing the complexes are also set forth therein. A
`sive treating system adds halogen groups, for example,
`preferred salt utilized with the 4,4'-methylene dianiline
`chlorine to the cured rubber which activates the cured
`compound is sodium chloride or lithium chloride. Due
`rubber surface, allowing the amine curable polymer or
`generally to availability and cost, the complexes or salts
`polymer system to adhere strongly to the cured rubber
`derived from 4,4'-methylene dianiline are highly pre
`65
`ferred. Another class of amine curing agents which can
`surface.
`Of the various amine curable polymers or prepoly
`be utilized are the various Versamides, that is, the con
`mers, the urethanes are preferred. Other prepolymers or
`densation products of polyamines and dibasic acids
`
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`from a conjugated diene having from 4 to 12 carbon
`obtained when certain unsaturated fatty acids are poly
`atoms, copolymers made from conjugated dienes hav
`merized, and are manufactured by The Henkel Chemi
`cal Company.
`ing from 4 to 12 carbon atoms with vinyl substituted
`The equivalent weight of the curing agent utilized
`aromatics having from 8 to 15 carbon atoms, for exam
`with regard to the curable prepolymer or polymer,
`ple styrene-butadiene rubber, and the like. In essence,
`including the amine curing agent, generally ranges from
`the patch can be made from the same type of rubber as
`about 85% to 15% with from about 95 to 105% being
`the substrate. Often, the patch will have a cushioned
`preferred. Often to facilitate processing, the curing
`layer thereon to alleviate stresses formed between the
`agent and especially an amine curing agent, such as the
`tire carcass and the patch.
`complex of 4,4'-methylene dianiline and a salt is utilized
`Because the patch must provide structural reinforce
`with a plasticizer such as dioctylphthalate (DOP) on a
`ment to the repaired article, it generally utilizes cords in
`50% weight basis or tetraethylene glycol bis (2-ethyl
`the same manner as the article. Although the number of
`hexanoate) manufactured by Union Carbide Corpora
`cords can range from a small number to a very large
`tion on a 50% weight basis under the trade name Flexol
`number, as above, they generally equal in strength the
`4GO. The amount of plasticizer can range from about
`cords damaged in the substrate. Such a provision pro
`20% to about 60 weight percent.
`vides an adequate reinforcement for the article. The
`The curing agent is blended with the prepolymer or
`cords can be made of polyester, nylon, steel, rayon, or
`polymers in various mixers such as dough mixers, high
`the like with nylon being preferred. It has been found
`speed impellers, paddle-type mixers, and the like. Small
`that according to the present invention, large hollows
`batches can be mixed by stirring with a spatula. Usually
`can be repaired up to approximately 8 inches in diame
`20
`the prepolymer or polymer is a liquid. If not, when
`te.
`mixed with the polar solvent, a liquid mixture results.
`In preparing the amine curable polymer system, gen
`However, even if a solid curing agent is used, when
`erally the amine curable polymer or prepolymer is
`added to the prepolymer or the polymer, and to a sol
`mixed with the polar solvent and thereafter the curing
`vent system, a liquid system results even though the
`agent. During cure, an effective and strong bond is
`curing agent (e.g., amine) can be in the form of a disper
`formed between the prepolymer or polymer system and
`sion. Thus, although the system may contain solids
`the treated elastomer substrate. Since the present inven
`therein, the solids exist in the form of a dispersion so
`tion relates to an ambient temperature cure, repair of
`that a liquid system is produced.
`large and cumbersome articles such as off the road tires,
`The curing agent and the amine curable polymers or
`conveyor belts, and the like can be made in situ. In other
`prepolymers form the curable polymer system which is
`words, the repair can be made at the job site. The only
`mixed with a polar solvent so that a liquid system is
`accessory which may be required is some means for
`obtained which cures at ambient or room temperature,
`holding the patch in place while the polymer cures. As
`that is, the prevailing temperature is from about 10
`above, this can be an inflatable bladder or one or more
`degrees C. to about 50 degrees C. Often the ambient
`sandbags. Since the cure is ambient, no steam chambers
`temperature will range from about 15 degrees C. to
`or other vulcanizing tire repair equipment is required
`about 35 degrees C. or 40 degrees C. The polar solvents
`other than that necessary to cure the gum rubber. This
`which can be utilized, especially with the amine curing
`of course also results in an energy savings.
`agent and the amine polymers or prepolymers are, for
`It is to be understood that various conventional addi
`example, set forth in U.S. Pat. No. 3,888,831 to Kogan
`40
`tives in typical amounts can be added to the amine
`which is hereby fully incorporated by reference. Such
`curing agent and prepolymer system such as colorants,
`solvents include those having dipole moments in excess
`softeners, fillers, antioxidants, plasticizers, and the like.
`of 0.4 Debye in which there are no more than a total of
`The invention will be better understood by reference
`8 methyl, methylene or tertiary carbon radicals per
`to the following representative examples:
`polar group.
`45
`Generally, the amount of solvent utilized per 100
`EXAMPLE
`parts by weight of the curable prepolymer or polymer
`Sidewall Section Repair
`ranges from about 2 to about 40, desirably from about 2
`An 11.00 R 24.5 steel radial truck tire containing two
`to about 20 and preferably from about 5 to about 15
`injuries in the sidewall was repaired as follows: injury
`parts by weight. Specific examples of preferred solvents
`include dimethylformamide, tetrahydrofuran, cyclo
`number 1 was inches wide by 4 inches long after
`buffing with a tungsten-carbide tip tool. The buffed area
`hexanone, ethyl acetate, nitromethane, nitroethane,
`nitroproprane, methyl ethyl ketone, and acetone. Ace
`was cleaned with a rubber solvent. The innerliner was
`then marked with an outline of the patch and likewise
`tone and methyl ethyl ketone are highly preferred. The
`buffed with the tungsten-carbide tool. Only the inner
`amount of curing agent based upon said polymer or
`55
`prepolymer ranges from about 0.85 to about 1.15 equiv
`liner was buffed. The buffed areas were cleaned again
`with a rubber solvent and allowed to dry thoroughly. A
`alents.
`Considering patch 20, it can generally be of any de
`coat of Firestone's Sup-R-Tac rubber cement was ap
`plied to the buffed areas. It also was allowed to dry
`sired size so long as it is greater in surface area than the
`thoroughly. An uncured patch was stitched into place
`hollow it seals. Typically, the surface area of the patch
`60
`is at least twice as great as the hollow. Generally, an
`(Rocson 5314-6, Rocson, Inc., Copley, Ohio). Uncured
`all-purpose gum rubber (Roscon regular cure AP repair
`appropriate patch size will be known to one skilled in
`the art of patch construction and/or patch application.
`gum) was then stitched into the external injury. The
`The patch is made of rubber and is generally fully
`repair was cured in a Vulcan split-rim mold.
`cured. Although cured natural rubber or a composition
`Injury number 2 was inch wide by 3i inches long
`after buffing with a tungsten-carbide tip tool. The cut
`containing at least 80% by weight of natural rubber is
`often preferred, any conventional type of cured rubber
`was cleaned thoroughly with a rubber solvent and al
`compound can be utilized. Thus, the patch can be made
`lowed to dry. A cover patch was cemented and stitched
`
`35
`
`50
`
`65
`
`MacNeil Exhibit 2058
`Yita v. MacNeil IP, IPR2020-01139
`Page 7
`
`
`
`Adiprene L 42
`Adiprene L 367
`Flexol 4GO
`Acetone
`Caytur 21
`
`150 grim.
`150 grim.
`30 grim.
`30 grm.
`
`72 grm. )
`
`A-side
`
`B-side
`
`2 grim.
`Black MB
`"15 parts of carbon black in Dioctyl phthalate base.
`
`10
`
`20
`
`25
`
`30
`
`45
`
`4,434,832
`10
`to the innerliner in order to hold the gum rubber in the
`cloth. After the surfaces had dried, several coats of a 3
`percent trichloro-s-triazinetrione in ethylacetate were
`external injury. The cover patch, made from the all
`purpose gum rubber, was about
`inch larger in all
`applied to the innerliner area and the patch. The primer
`directions than the injury and about inch thick. One
`was allowed to dry thoroughly. A standard 50/50 kit
`coat of Firestone's Sup-R-Tac rubber cement was ap
`described in example 1 was mixed thoroughly and al
`plied to the injured area and allowed to dry. Uncured
`lowed to thicken nearly to a non-pourable stage. The
`all-purpose gum rubber (Roscon regular cure AP repair
`material was then applied to the patch and innerliner
`gum) was stitched into t