CA1083288A - Self sealing vehicle tire and butyl rubber sealant composition - Google Patents
Self sealing vehicle tire and butyl rubber sealant compositionInfo
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- CA1083288A CA1083288A CA241,978A CA241978A CA1083288A CA 1083288 A CA1083288 A CA 1083288A CA 241978 A CA241978 A CA 241978A CA 1083288 A CA1083288 A CA 1083288A
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Abstract
Abstract of the Disclosure A vehicle tire is disclosed having an internal circumferential layer of self-sealing composition on an internal surface, particularly behind the tire tread. The sealant layer is initially made up of the combination of specific quantities of high molecular weight curable butyl rubber, a low molecular weight curable butyl rubber, a liquid polybutylene tackifier, carbon black, suitable curing agents for the butyl rubber components, and optionally a partially hydrogenated block copolymer of styrene and a conjugated diene. When cured, this sealant layer effectively heals most punctures one-quarter inch in diameter or less in a vehicle tire at temperatures over the range of about -20° F.
to 270° F. without significant loss of air.
to 270° F. without significant loss of air.
Description
1~ 3.~
This inv~ntion relates to tubeless rubber tires constructed so as to be self-sealing with respect to small puncture holes. In one embodiment, this invention relates to a tire sealant composition for use on an internal surface of an automotive rubber tire whlch is capable of self-sealing puncture holes in the tread region when the tire is in use and at a temperature in the range of about -20F. to 270F. In another embodiment, the com-position may be used as a sealant for bicycle tires, in which case it must be capable of operating in a temperature range of approximately 30F. to 125F.
Considerable effort has been expended to develop a rubber tire for automotive applications which is capable of self-healing puncture wounds while in operation. United States patents 2,756,801, 2,765,018 and 2,782,829 disclose different approaches to this problem. The development~jof an effective self-healing tire is very difficult because the operating tire may experience temperatures over a very wide range. Tires on vehicles standing outside in the wintertime may experience temperatures of -20F or lower.
On the other hand, the tires of a vehicle traveling for prolonged periods in summer weather at highway speeds may reach temperatures of 220F. or higher. To be effective, the sealant portion of such a tire must be sufficiently tacky to stick to a puncturing object, or to itself if the puncturing object is removed, and have sufficie~t strength to seal the hole at any temperature in this broad range. Furthermore, the sealant must resist oxidative or thermal degradation when subjected to the air, which may become quite hot, filling the tire. None of the prior art ,; compositions and approaches directed to self-sealing tires, that we are aware of, are effective under all of these con-ditions. Furthermore, in our experience, no currently r ~?
3~8 available sealants effectively perform as a self-healing composition in vehicle tires under all t~e conditions that a tire can be expected to encounter.
Accordingly, it is an object of the present inven-tion to provide a vehicle tire construction incorporating an inner circumferential layer of sealant composition that is effective to seal puncture holes up to about one-quarter inch or so in diameter when the tire is at a temperature in the range of below zero Fahrenheit to about 270F. The multicomponent composition of the sealant layer has the ability to immediately heal a newly formed puncture hole at a temperature in this wide range and sufficient strength to prevent significant loss of air pressure.
It is another object of the present invention to provide a tire sealant composition suitable upon curing for use in a conventional rubber tire. The composition is a specific combination of several ingredients which cooperate to provide the ~elf-healing properties and the strength properties required for this demanding application.
In accordance with one embodiment of our invention, these and other objects and advantages are accomplished by provid~ng a circumferential layer of ~ured sealant composi-tion on an internal surface of a vehicle tire, particularly in the region behind the tread stock. The sealant layer is formed by initially mixing specific quantities of a relatively high molecular weight curable isobutylene-i- isoprene copolymer, a relatively low molecular weight cur-able isobutylene-isoprene copolymer, a liquid polybutylene tackifier, a partially hydrogenated block copolymer of a mono-vinyl arene and a conjugated diene, carbon black and a crosslinker and initiator to cure the butyl rubber compo-nents. For example, a sealant may be prepared by initially mixing 15 parts by weight of curable ~! -2-isobutylene-based copolymer having an average molecular weight in the range of about 100,000 to 300,000; 10 parts by weight of a curable isobutylene-based copolymer hav-ing an average molecular weight in the range of about 10,000 to 30,000; 65 parts by weight of a liquid polybuty-lene having an average molecular weight of about 500 to 5,000; 10 parts by weight carbon black; and 5 parts by weight of a partially hydrogenated block copolymer of the A-B-A configuration wherein prior to hydrogenation each-A is a polystyrene block and each B is-substant-ially~ a poly-isoprene block, the total molecular weight of the block copolymer being about 100,000 and the polyisoprene making up about two-thirds by weight of the block copolymer.
A suitable solvent, such as toluene, for the polymeric components may be employed to assist in the mix-ing and handling of the composition. A small amount of a crosslinking agent, such as para-quinone dioxime, and a crosslinking initiator, such as benzoyl peroxide, are em-- ployed to cure the two isobutylene copolymer components.
Where it is desired to apply a sealant layer of the subject composition to a preformed tire, a toluene dispersion of the uncured composition may be sprayed onto - the inside surface of the tire. For example, about 200 grams (on a solvent-free basis) of the above composition containing crosslinkers is air sprayed into a steel belted JR-78-15 tire preheated to 125F. The composition gels in about two to five minutes. The tire is then allowed to set at ambient temperature for one-half hour to allow for : evaporation of excees toluene and then placed in an oven at 125F. for an additional one-half hour to preheat the tire for spraying of the second coat of sealant. Thi~
procedure is repeated after the second coat. Upon comple-tion of the application of the third coat, the tire is again allowed to stand at room temperature for one-half '`'' 1083~88 hour and then placed in an oven at 125F. for sixteen hours for finai curing.
The thus formed sealant layer remains in its place in the tire despite normal usage thereof. Furthermore, it has the ability to fill and seal a puncture hole formed in the tire even at high speed and high temperature tire operation.
It is a principal object to provide a sealant compos7tion comprising a Partially cross-linked matrix, said matrix comprising 10 to 15 parts by weight of a high average molecular weight butyl rubber having an average molecular weight in the range of about 100,000 to 300,000, 6 to 10 parts by weight of a low average molecular weight butyl rubber having an average mole-10 cular weight in the range of about 10,000 to 30,000, and 5 to 17 parts of carbon black, in admixture with 60 to 65 parts by weight of a liquid polybutylene based tackifier.
Other advantages of our invention will become more apparent from a detailed description thereof which follows. Reference ~iill be made to the drawings, in which:
FIGURE 1 is a perspective view of a tire broken away to show the cross-sectional structure thereof and to display one embodiment of the invention in which the sealant layer is located on the innermost surface of the tire behind the tread; and FIGURE 2 is a perspective view of a tire broken away to show the cross-sectional structure of the tire and depicting another embodiment of the invention in which the subject sealing layer is located behind the tread and between an air impervious film conventionally employed in the tire and the carcass portion of the tire.
In FIGURE 1 is depiected a tubeless tire 10 which comprises the tread portion 12, carcass 14, and side walls 16. In tubeless tires it is generally desirable to employ a barrier layer or lining 18 which is imper-meable to air. The air impermeable lining 18 extends typically over the entire i-nner surface of the tire from one bead portion to the other bead 30 portion. In accordance with one embod7ment of our invention a sealing layer 20 is placed on the inside of the tire against the air barrier layer 18.
The sealant layer 20 is arranged and constructed to lie principally behind the tread of the tire because it is contemplated that the sealing ~ayer wilI serve principalIy to seal la~32&~
punctures coming through the tread portion of the tire.
FIGURE 2 depicts a tubeless tire 10 having parts similar to those depicted in FIGURE 1 (and identified by like numerals), except that in this embodiment of our in-vention the sealing layer 20 is located between the carcass 14 of the tire and the air impermeable barrier layer 20.
In general, it is preferred that our sealant layer be formed and cured at the time the tire is being manufactured. Production economies can be realized, in=
cluding the fact that the subject sealant layer can be cured at the higher temperatures (about 3504F.) employed in curing the other tire rubber compositions. When this is done it is possible to locate the sealant layer either betweèn the carcass 14 of the tire l~ and the air imperm- ~ -eable barrier layer 18 as shown in FIGURE 2, or inside the air imperme~ble layer 18 as shown in FIGURE 1. However, if the sealant layer is applied after the tire is manufac-tured, of course, it is only possible to place such layer inside the air impermeable barrier as shown in ~IGURE 1.
Our sealant layer 20 is a tacky, carbon-filled rubber material formed by curing a compound mixture of a high molecular weight and a low molecular weight butyl - rubber. In~orporated with these rubber materials prior to curing is a tackifier and, optionally, a thermoplastic elastomer bLock copolymer, preferably of poly~tyrene and polyisoprene, which significantly contributes to the high temperature strength and sealing capability of our sealing layer.
A better appreciation of our invention will be i 30 gained through specific examples which illustrate how the sealing composition is compounded, cured, applied and`
evaluated.
Example 1 The screening of a number of commercial sealants ~
.
.~ .
~Q83Z8~!3 had indicated that a curable butyl rubber sealant would be compatible with the rubber tires and might afford a good starting place for a self-sealing tire composition.
~owever, the butyl rubber-based sealant by itself did not have sufficient strength at high temperatures nor sufficient tack to serve as a tire sealant composition.
A commercially available sealant composition was obtained having the following compositions.
Ingredients Parts by Weight High molecular weight, curable butyl rubber 60 Low molecular weight, curable butyl rubber 40 HAF carbon black 50 SRF carbon black 25 MT Carbon black 25 Tung oil 5 Toluene 483.5 Para-quinone dioxime 2.5 .~ . ' .
The high molecular weight butyl rubber was a copolymer of 96% isobutylene and 4% isoprene. The average molecular weight of the polymer was in the range of 100,000 to 300,000. The low molecular weight butyl rubber was like-wise a copolymer of 96~ isobutylene and 4% isoprene. How-ever, the molecular weight of this butyl rubber was in the range of 10,000 to 30,000. These two butyl rubber compon-ents are curable because of the residual unsaturation pro-vided by the small isoprene content. The carbon black filler contributes strength to the sealant. The tung oil component is a processing additive. Toluene i9 a solvent for the uncured butyl rubber components. The para-quinone dioxime is a crosslinking agent which has to be oxidized to para-dinitroso benzene with a suitable oxidant, such as '; -6-'1083'~f~
lcad dioxide or benzoyl peroxide, to initiate curing.
In making up the subject sealant, 35 parts by weight of the above com~ercial composition (on a solvent-free basis) was mixed with 60 parts by weight of a liquid polybutylene-ba~ed tackifi~r and 5 parts by weight of a partially hydrogenated block copolymer of styrene and isoprene, and the para-quinone dioxime was added. In this case an additiona~ 1.5 parts of para-quinone dioxime per 100 parts of butyl rubber constituents were added. This made a total of 4 parts of the dioxime per 100 parts curable rubber. The additional dioxime crosslinker wa~
employed to increase the crosslink density of the cured -ru~ber and provide greater strength. These constituents were all dissolved or suspended in the toluene solvent.
The liquid tackifier was actually a copolymer of 98% butylene and 2% isobutylene. It had an average molecular weight in the range of 500 to 5,000. It was a commercial product available under the trade name "Indopol ~ H-300" .
The block copolymer employed was of the A-B-A
type wherein the A blocks were formed of polystyrene, the B blocks were polymeric segments of isoprene and some higher carbon chain length conjugated dienes. The block copolymer employed in the sealant of this example had an avérage molecular weight of about 100,000 and was made up of about 68% by weight polyisoprene. The block copolymer had been hydrogenated so that the polyisoprene segments were almost completely saturated. However, the polystyrene segments were not hydrogenated to any significant extent. The specific material used in this example was obtained under the trade designation "Kraton G-6500". ~lock copolymèrs of this type are described in United States patent 3,595,942.
New Uniroyal JR-78-15 steel belted radial tires * l~ k ~ ' .
3~3 were obtained to evaluate the subject sealant composition.
It was noted that the tires had residual mold release agent on their internal surfaces. To remove the mold re-lease agent, the tires were first mounted on a rotator and then one-half gallon of a soap solution containing a 50 milliliter cup of Amway SA-8 soap powder was added to a tire. A steel rotary brush on a flexible cable was then used to brush the tire with the soap solution while the tire was rotating. The tire was then thoroughly rinsed out with tap water. The rinse water was then removed, followed by a vacuuming step to remove the remaining water.
The tire was then dried at ambient prior to coating.
A tire was then preheated to 125F. A ~uantity of the subject sealant composition prepared as described above was provided. Ten parts of benzoyl peroxide per 100 parts of total curable butyl rubber constituents present were added to the mixture and thoroughly mixed therewith.
The sealant composition dispersed in toluene was then sprayed onto the inner surface of a cleaned and preheated tire employing commercial air paint spray equipment. A
pressure feed was employed and the sealant was sprayed using 50 psig compressed air. However, an airless spray system could also be used. The tire was rotated as the sealant was sprayed onto the internal surface and directed to the region behind the tread, as indicated at 20 in FIGURE 1.
Two hundred grams (on a solvent-free basis) of the sub-ject sealant composition were applied. Some of the solvent evaporated during spraying and the applied composition gelled in the tire in about five minutes. The tire was then left at ambient temperature for a minimum of one-half hour to evaporate excess solVent and cure the sealant layer. One-half hour prior to the second coating the tire was placed in an oven at 125F.
lQ~33~3~
The tire was remove~ from the oven and, while still warm, a second 200 gram layer (on a solvent-free basi~) of sealant composition i~entical to that described was applied. Much of the toluene solvent evaporated upon spraying and the second layer was observed to quickly gel.
The tire was set asi~e for one-half hour to allow much of the toluene to evaporate and returned to the oven for an additional one-half hour. The tire was then removed from the oven and a third 200 gram coating ~solvent-free basi~) was applied. The tire was returned to the oven as before and the third sealant layer cured at 125F. overnight.
The tire was then mounted on a wheei and inflated with air to 30 psig. The wheel was rotated and the tire was punctured with 0.200 and 0.250 inch diameter spikes at temperatures of -20F., ambient, and 270F., and the spikes were removed. After puncturing at each temperature, each puncture was squirted with a commercial soapy leak detector called "Snoop" to observe if any leakage took place. In each instance the tire sealed itself without any significant leakage of air.
~ , ' ' .
A second sealant composition was prepared. It was made up by mixing together 14.25 parts by weight of a curable high molecular weight butyl rubber having an average molecular weight in the range of 100,000 to 300,000, 9~5 parts by weight of a curable butyl rubber having a molecular weight in the range of 10,000 to 30,000, 62 parts by weight of the polybutylene liquid tackifier, 9.5 parts by weight of an industrial carbon black, a furnace black with a surface area of 235 sq. meters/gm and a pH of 9.0, 4.75 parts by partially hydrogenated block copolymer of polystyrene and polyisoprene, and 2.5 parts by weight para-quinone dioxime _g_ :1~83~A8 per 100 parts total curable butyl rubber constituent~.
This mixture was dissolved in and suspended in 90 part~
by weight of toluene. Just prior to usage, 10 parts by weight of benzoyl peroxide per 100 parts of butyl rubber components were dissolved in 60 parts of toluene and added to the curable rubber composition.
A number of Uniroyal JR-78-15 tires were cleaned with a soap-sodium metasilicate cleaning solution as des-cribed in Example 1. The tires were preheated to 125F.
and each coated with three 20D gram layers (solvent-free basis) of the subject composition. Each layer was observed to gel within a period of minutes. After the application of the third layer the tire was then set aside for one hour to allow for st of the toluene to evaporate at ambient and then placed in the oven at 125F., wherein solvent was evaporated and the sealing composition was cured over a sixtesn hour period. The tires were then mounted on wheels and tested with nail punctures through the tread at temperatures from -20F., ambient, and 270F.
as described in Example 1. In each instance the sealant healed the puncture hole without significant loss of air.
It has been noted that the healing occurs in the following manner. The sealant adheres to the nail when the nail is in the tire, and this sealant adhering to the nail i8 pulled into the puncture hold if the nail is removed. Air pressure helps to force sealant to the nail and also into the puncture hole. When a tire has been punctured and ; self-healed in accordance with the subject invention and then removed from its wheel and examined from the inside, it is usually very different to locate the puncture. The sealant is drawn or forced into the hole to very effectively ; heal it.
It has been found that the subject sealant composition must be formulated to contain certain specific ., ~
iQ~
constituents witllin narrow and definite composition ranges. In the automobile tire embodiment, the diffi-culty lies in providing a composition which has the ability to both re-heal any cut in the sealant caused by a puncture and seal a puncture hole at a temperature anywhere in the range from a~out -20F. to 270F. Once the hole has been filled (which must occur very rapidly), it is then necessary for the sealant to have sufficient strength to maintain air under pressures up to 30 to 40 psig and higher while the tire is continually being flexed and stressed as it is in normal vehicie use. While the automobile tire sealant has been tested and found effective at temperatures up to 270F.
it is usually felt automotive tires in normal usage will not experience temperatures above about 220F.
The automobile sealant embodiment is made up according to the following specification. Two curable butyl rubber components -- one a relatively high molecular weight constituent and the other a relatively high molecular weight constituent -- are employed in combination. Ten to fifteen parts of an isobutylene-based copolymer (preferably about 96% isobutylene - 4% isoprene) having an average molecular weight in the range of about 100,000 to 300,000 is employed in combination with 6 to 10 parts of a copolymer of 96% isobutylene and 4% isoprene, having an average molecular weight in the range of about 10,000 to 30,000. Mixed with the curable butyl rubber constitu-ents are 60 to 65 parts by weight of a liquid polybutylene (e.g., 98% butylene - 2% isobutylene) tackifier having an average molecular weight in the range of 500 to S,000.
This liquid saturated C4 polymer represents a major part of the total composition. It possesses excellent thermal stability, stickiness and flowability over the wide temp-erature range in which the subject sealant must serve.
33~8~
An optional polymeric constituent of the subject sealant composition is a thermoplastic, elastomeric, hydro-genated block copolymer having the general configuration A-(B-A)l 5. Four to ten parts of this hydrogenated block copolymer are employed in combination with the other con-stituents. If more than about 10% of the block copolymer is employed in the subject sealant (solvent-free and curing agent-free basis) the composition will not adequately self-heal. If the block copolymer content is less than 4% (on the same basis) the sealant does not have adequate strength temperatures above about 220F. Compositions which include no block copolymers whatsoever are neverthe-less useful as bic~cle tire sealants, since operating temperatures within a bicycle tire will normally not range above 125F.
Prior to hydrogenation each A (of the A-(B-A)1_5 - block copolymer) is a thermoplastic monovinyl arene polymer block and each B is a conjugated diene polymer block. In accordance with our invention the monovinyl arene i8 preferably styrene, but may also be alpha methyl styrene, ring alkylated styrenes and the like as well as mixtures thereof. Furthermore, in accordance with our invention the B block(s) may be prepared from conjugated dienes having from 4 to 10 carbon atoms, but preferably 4, 5 or more carbon atoms per monomer molecule, including specifically isoprene. The elastomeric polymerized conjugated diene component of the block copolymer typically makes up in total about two-thirds or more of the block copolymer with the thermoplastic polymer constituent making up the end groups and the balance of the copolymer. In accordance ! with our invention the average molecular weight of this block copolymer is suitably in the range of about 60,000 to 400,000 and preferably in the range of about 70,000 to 150,000. The composition is partially hydrogenated so that ~ I , lQ~3~
the conjugated diene block segment(s) are substantially fully saturated. ~lowever, the polystyrene segm~nts are not appreciably hydrogenated. Copolymers which are not hydrogenated in this fashion are not suitably resistant to oxidation and degradation at the high temperature end of the operating environment of the tire, particularly considering that there is considerable oxygen in the tire.
Carbon black filler in the amount of 5 to 17 parts by weight is also incorporated into the composition.
A furnace black having a high surface area and a basic pH
- is preferred.
A solvent, such as toluene, for the polymeric components may be employed in the preparation and applica-tion of the sealant composition.
Also incorporated in the composition is a suit-able crosslinker for the butyl rubber constituents. The preferred corsslinker for the butyl rubber constituents is para-quinone dioxime. However, other well known bu~yl rub-ber curing agents may be employed. At the time the curing is to take place it is also necessary to incorporate an oxidative initiator, such as benzoyl peroxide, to convert para-quinone dioxime to its crosslinking form, para-dinitroso benzene. Para-quinone dioxime and benzoyl perox-ide are preferred for use in combination in the practice of our invention because they promote rapid gel times.
The embodiments of the invention described in the specific examples involved spraying the subject sealing composition into tires that had already been manufactured.
In another embodiment, particularly suitable for applica-tions to bicycle tires, the sealant composition is formed ; and cured in the form of sheets and applied to the inside of the tire, as desired, employing a suitable adhesive.
However, in many instances it will be preferred to form and cure the sealant layer at the same time the tire is ~eing manufactl~red, One practice would be to first lay up the butyl rubber-based inner liner. An uncured seal-ing layer of the subject composition would then be placed on the inner liner member. Then the uncured carcass por-1:ion of the tire, including its layers of reinforcing belting and the like, would be formed after the sealing layer had been laid up. Subsequently, the treat stock would be laid on the uncured carcass. The whole tire would then be cured at normal curing temperatures of the orde~
of 350F., at which temperature the curing of the subject sealing composition would be greatly accelerated and comparable in time to the curing of the other portions of the tire. When the butyl rubber portion of the subject sealant layer is cured at this high temperat`ure, some modifications may be required in the type and amount of crosslinker and initiator employed as compared with the above examples.
Prior to the discovery of the subject composition a number of other known sealant and elastomeric materials were tested and evaluated as self-healing tire sealants.
For example, other butyl rubber-containing compositions were tried but failed to be self-sealing over the wide temperature ranges involved. Also, ethylene-~inyl acetate copolymers were tested and found lacking. Urethane rubbers were also evaluated and it was found that they would not satisfactorily seal puncture holes over the wide temperature ranges involved. We have also found, as indicated above, that even when employing the specific constituents described as elements fo the subject composition, a wide variation in their compositional ranges cannot be toierated and still obtain the benefits of the subject invention.
While our invention has been described in terms ~' l0~32a~
of a few specific embodiments thereof, it will be appreci-ated that other fonns could be adapted by one skilled in the art and, accordingly, our invention is to be considered limited only by the scope of the following claims.
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This inv~ntion relates to tubeless rubber tires constructed so as to be self-sealing with respect to small puncture holes. In one embodiment, this invention relates to a tire sealant composition for use on an internal surface of an automotive rubber tire whlch is capable of self-sealing puncture holes in the tread region when the tire is in use and at a temperature in the range of about -20F. to 270F. In another embodiment, the com-position may be used as a sealant for bicycle tires, in which case it must be capable of operating in a temperature range of approximately 30F. to 125F.
Considerable effort has been expended to develop a rubber tire for automotive applications which is capable of self-healing puncture wounds while in operation. United States patents 2,756,801, 2,765,018 and 2,782,829 disclose different approaches to this problem. The development~jof an effective self-healing tire is very difficult because the operating tire may experience temperatures over a very wide range. Tires on vehicles standing outside in the wintertime may experience temperatures of -20F or lower.
On the other hand, the tires of a vehicle traveling for prolonged periods in summer weather at highway speeds may reach temperatures of 220F. or higher. To be effective, the sealant portion of such a tire must be sufficiently tacky to stick to a puncturing object, or to itself if the puncturing object is removed, and have sufficie~t strength to seal the hole at any temperature in this broad range. Furthermore, the sealant must resist oxidative or thermal degradation when subjected to the air, which may become quite hot, filling the tire. None of the prior art ,; compositions and approaches directed to self-sealing tires, that we are aware of, are effective under all of these con-ditions. Furthermore, in our experience, no currently r ~?
3~8 available sealants effectively perform as a self-healing composition in vehicle tires under all t~e conditions that a tire can be expected to encounter.
Accordingly, it is an object of the present inven-tion to provide a vehicle tire construction incorporating an inner circumferential layer of sealant composition that is effective to seal puncture holes up to about one-quarter inch or so in diameter when the tire is at a temperature in the range of below zero Fahrenheit to about 270F. The multicomponent composition of the sealant layer has the ability to immediately heal a newly formed puncture hole at a temperature in this wide range and sufficient strength to prevent significant loss of air pressure.
It is another object of the present invention to provide a tire sealant composition suitable upon curing for use in a conventional rubber tire. The composition is a specific combination of several ingredients which cooperate to provide the ~elf-healing properties and the strength properties required for this demanding application.
In accordance with one embodiment of our invention, these and other objects and advantages are accomplished by provid~ng a circumferential layer of ~ured sealant composi-tion on an internal surface of a vehicle tire, particularly in the region behind the tread stock. The sealant layer is formed by initially mixing specific quantities of a relatively high molecular weight curable isobutylene-i- isoprene copolymer, a relatively low molecular weight cur-able isobutylene-isoprene copolymer, a liquid polybutylene tackifier, a partially hydrogenated block copolymer of a mono-vinyl arene and a conjugated diene, carbon black and a crosslinker and initiator to cure the butyl rubber compo-nents. For example, a sealant may be prepared by initially mixing 15 parts by weight of curable ~! -2-isobutylene-based copolymer having an average molecular weight in the range of about 100,000 to 300,000; 10 parts by weight of a curable isobutylene-based copolymer hav-ing an average molecular weight in the range of about 10,000 to 30,000; 65 parts by weight of a liquid polybuty-lene having an average molecular weight of about 500 to 5,000; 10 parts by weight carbon black; and 5 parts by weight of a partially hydrogenated block copolymer of the A-B-A configuration wherein prior to hydrogenation each-A is a polystyrene block and each B is-substant-ially~ a poly-isoprene block, the total molecular weight of the block copolymer being about 100,000 and the polyisoprene making up about two-thirds by weight of the block copolymer.
A suitable solvent, such as toluene, for the polymeric components may be employed to assist in the mix-ing and handling of the composition. A small amount of a crosslinking agent, such as para-quinone dioxime, and a crosslinking initiator, such as benzoyl peroxide, are em-- ployed to cure the two isobutylene copolymer components.
Where it is desired to apply a sealant layer of the subject composition to a preformed tire, a toluene dispersion of the uncured composition may be sprayed onto - the inside surface of the tire. For example, about 200 grams (on a solvent-free basis) of the above composition containing crosslinkers is air sprayed into a steel belted JR-78-15 tire preheated to 125F. The composition gels in about two to five minutes. The tire is then allowed to set at ambient temperature for one-half hour to allow for : evaporation of excees toluene and then placed in an oven at 125F. for an additional one-half hour to preheat the tire for spraying of the second coat of sealant. Thi~
procedure is repeated after the second coat. Upon comple-tion of the application of the third coat, the tire is again allowed to stand at room temperature for one-half '`'' 1083~88 hour and then placed in an oven at 125F. for sixteen hours for finai curing.
The thus formed sealant layer remains in its place in the tire despite normal usage thereof. Furthermore, it has the ability to fill and seal a puncture hole formed in the tire even at high speed and high temperature tire operation.
It is a principal object to provide a sealant compos7tion comprising a Partially cross-linked matrix, said matrix comprising 10 to 15 parts by weight of a high average molecular weight butyl rubber having an average molecular weight in the range of about 100,000 to 300,000, 6 to 10 parts by weight of a low average molecular weight butyl rubber having an average mole-10 cular weight in the range of about 10,000 to 30,000, and 5 to 17 parts of carbon black, in admixture with 60 to 65 parts by weight of a liquid polybutylene based tackifier.
Other advantages of our invention will become more apparent from a detailed description thereof which follows. Reference ~iill be made to the drawings, in which:
FIGURE 1 is a perspective view of a tire broken away to show the cross-sectional structure thereof and to display one embodiment of the invention in which the sealant layer is located on the innermost surface of the tire behind the tread; and FIGURE 2 is a perspective view of a tire broken away to show the cross-sectional structure of the tire and depicting another embodiment of the invention in which the subject sealing layer is located behind the tread and between an air impervious film conventionally employed in the tire and the carcass portion of the tire.
In FIGURE 1 is depiected a tubeless tire 10 which comprises the tread portion 12, carcass 14, and side walls 16. In tubeless tires it is generally desirable to employ a barrier layer or lining 18 which is imper-meable to air. The air impermeable lining 18 extends typically over the entire i-nner surface of the tire from one bead portion to the other bead 30 portion. In accordance with one embod7ment of our invention a sealing layer 20 is placed on the inside of the tire against the air barrier layer 18.
The sealant layer 20 is arranged and constructed to lie principally behind the tread of the tire because it is contemplated that the sealing ~ayer wilI serve principalIy to seal la~32&~
punctures coming through the tread portion of the tire.
FIGURE 2 depicts a tubeless tire 10 having parts similar to those depicted in FIGURE 1 (and identified by like numerals), except that in this embodiment of our in-vention the sealing layer 20 is located between the carcass 14 of the tire and the air impermeable barrier layer 20.
In general, it is preferred that our sealant layer be formed and cured at the time the tire is being manufactured. Production economies can be realized, in=
cluding the fact that the subject sealant layer can be cured at the higher temperatures (about 3504F.) employed in curing the other tire rubber compositions. When this is done it is possible to locate the sealant layer either betweèn the carcass 14 of the tire l~ and the air imperm- ~ -eable barrier layer 18 as shown in FIGURE 2, or inside the air imperme~ble layer 18 as shown in FIGURE 1. However, if the sealant layer is applied after the tire is manufac-tured, of course, it is only possible to place such layer inside the air impermeable barrier as shown in ~IGURE 1.
Our sealant layer 20 is a tacky, carbon-filled rubber material formed by curing a compound mixture of a high molecular weight and a low molecular weight butyl - rubber. In~orporated with these rubber materials prior to curing is a tackifier and, optionally, a thermoplastic elastomer bLock copolymer, preferably of poly~tyrene and polyisoprene, which significantly contributes to the high temperature strength and sealing capability of our sealing layer.
A better appreciation of our invention will be i 30 gained through specific examples which illustrate how the sealing composition is compounded, cured, applied and`
evaluated.
Example 1 The screening of a number of commercial sealants ~
.
.~ .
~Q83Z8~!3 had indicated that a curable butyl rubber sealant would be compatible with the rubber tires and might afford a good starting place for a self-sealing tire composition.
~owever, the butyl rubber-based sealant by itself did not have sufficient strength at high temperatures nor sufficient tack to serve as a tire sealant composition.
A commercially available sealant composition was obtained having the following compositions.
Ingredients Parts by Weight High molecular weight, curable butyl rubber 60 Low molecular weight, curable butyl rubber 40 HAF carbon black 50 SRF carbon black 25 MT Carbon black 25 Tung oil 5 Toluene 483.5 Para-quinone dioxime 2.5 .~ . ' .
The high molecular weight butyl rubber was a copolymer of 96% isobutylene and 4% isoprene. The average molecular weight of the polymer was in the range of 100,000 to 300,000. The low molecular weight butyl rubber was like-wise a copolymer of 96~ isobutylene and 4% isoprene. How-ever, the molecular weight of this butyl rubber was in the range of 10,000 to 30,000. These two butyl rubber compon-ents are curable because of the residual unsaturation pro-vided by the small isoprene content. The carbon black filler contributes strength to the sealant. The tung oil component is a processing additive. Toluene i9 a solvent for the uncured butyl rubber components. The para-quinone dioxime is a crosslinking agent which has to be oxidized to para-dinitroso benzene with a suitable oxidant, such as '; -6-'1083'~f~
lcad dioxide or benzoyl peroxide, to initiate curing.
In making up the subject sealant, 35 parts by weight of the above com~ercial composition (on a solvent-free basis) was mixed with 60 parts by weight of a liquid polybutylene-ba~ed tackifi~r and 5 parts by weight of a partially hydrogenated block copolymer of styrene and isoprene, and the para-quinone dioxime was added. In this case an additiona~ 1.5 parts of para-quinone dioxime per 100 parts of butyl rubber constituents were added. This made a total of 4 parts of the dioxime per 100 parts curable rubber. The additional dioxime crosslinker wa~
employed to increase the crosslink density of the cured -ru~ber and provide greater strength. These constituents were all dissolved or suspended in the toluene solvent.
The liquid tackifier was actually a copolymer of 98% butylene and 2% isobutylene. It had an average molecular weight in the range of 500 to 5,000. It was a commercial product available under the trade name "Indopol ~ H-300" .
The block copolymer employed was of the A-B-A
type wherein the A blocks were formed of polystyrene, the B blocks were polymeric segments of isoprene and some higher carbon chain length conjugated dienes. The block copolymer employed in the sealant of this example had an avérage molecular weight of about 100,000 and was made up of about 68% by weight polyisoprene. The block copolymer had been hydrogenated so that the polyisoprene segments were almost completely saturated. However, the polystyrene segments were not hydrogenated to any significant extent. The specific material used in this example was obtained under the trade designation "Kraton G-6500". ~lock copolymèrs of this type are described in United States patent 3,595,942.
New Uniroyal JR-78-15 steel belted radial tires * l~ k ~ ' .
3~3 were obtained to evaluate the subject sealant composition.
It was noted that the tires had residual mold release agent on their internal surfaces. To remove the mold re-lease agent, the tires were first mounted on a rotator and then one-half gallon of a soap solution containing a 50 milliliter cup of Amway SA-8 soap powder was added to a tire. A steel rotary brush on a flexible cable was then used to brush the tire with the soap solution while the tire was rotating. The tire was then thoroughly rinsed out with tap water. The rinse water was then removed, followed by a vacuuming step to remove the remaining water.
The tire was then dried at ambient prior to coating.
A tire was then preheated to 125F. A ~uantity of the subject sealant composition prepared as described above was provided. Ten parts of benzoyl peroxide per 100 parts of total curable butyl rubber constituents present were added to the mixture and thoroughly mixed therewith.
The sealant composition dispersed in toluene was then sprayed onto the inner surface of a cleaned and preheated tire employing commercial air paint spray equipment. A
pressure feed was employed and the sealant was sprayed using 50 psig compressed air. However, an airless spray system could also be used. The tire was rotated as the sealant was sprayed onto the internal surface and directed to the region behind the tread, as indicated at 20 in FIGURE 1.
Two hundred grams (on a solvent-free basis) of the sub-ject sealant composition were applied. Some of the solvent evaporated during spraying and the applied composition gelled in the tire in about five minutes. The tire was then left at ambient temperature for a minimum of one-half hour to evaporate excess solVent and cure the sealant layer. One-half hour prior to the second coating the tire was placed in an oven at 125F.
lQ~33~3~
The tire was remove~ from the oven and, while still warm, a second 200 gram layer (on a solvent-free basi~) of sealant composition i~entical to that described was applied. Much of the toluene solvent evaporated upon spraying and the second layer was observed to quickly gel.
The tire was set asi~e for one-half hour to allow much of the toluene to evaporate and returned to the oven for an additional one-half hour. The tire was then removed from the oven and a third 200 gram coating ~solvent-free basi~) was applied. The tire was returned to the oven as before and the third sealant layer cured at 125F. overnight.
The tire was then mounted on a wheei and inflated with air to 30 psig. The wheel was rotated and the tire was punctured with 0.200 and 0.250 inch diameter spikes at temperatures of -20F., ambient, and 270F., and the spikes were removed. After puncturing at each temperature, each puncture was squirted with a commercial soapy leak detector called "Snoop" to observe if any leakage took place. In each instance the tire sealed itself without any significant leakage of air.
~ , ' ' .
A second sealant composition was prepared. It was made up by mixing together 14.25 parts by weight of a curable high molecular weight butyl rubber having an average molecular weight in the range of 100,000 to 300,000, 9~5 parts by weight of a curable butyl rubber having a molecular weight in the range of 10,000 to 30,000, 62 parts by weight of the polybutylene liquid tackifier, 9.5 parts by weight of an industrial carbon black, a furnace black with a surface area of 235 sq. meters/gm and a pH of 9.0, 4.75 parts by partially hydrogenated block copolymer of polystyrene and polyisoprene, and 2.5 parts by weight para-quinone dioxime _g_ :1~83~A8 per 100 parts total curable butyl rubber constituent~.
This mixture was dissolved in and suspended in 90 part~
by weight of toluene. Just prior to usage, 10 parts by weight of benzoyl peroxide per 100 parts of butyl rubber components were dissolved in 60 parts of toluene and added to the curable rubber composition.
A number of Uniroyal JR-78-15 tires were cleaned with a soap-sodium metasilicate cleaning solution as des-cribed in Example 1. The tires were preheated to 125F.
and each coated with three 20D gram layers (solvent-free basis) of the subject composition. Each layer was observed to gel within a period of minutes. After the application of the third layer the tire was then set aside for one hour to allow for st of the toluene to evaporate at ambient and then placed in the oven at 125F., wherein solvent was evaporated and the sealing composition was cured over a sixtesn hour period. The tires were then mounted on wheels and tested with nail punctures through the tread at temperatures from -20F., ambient, and 270F.
as described in Example 1. In each instance the sealant healed the puncture hole without significant loss of air.
It has been noted that the healing occurs in the following manner. The sealant adheres to the nail when the nail is in the tire, and this sealant adhering to the nail i8 pulled into the puncture hold if the nail is removed. Air pressure helps to force sealant to the nail and also into the puncture hole. When a tire has been punctured and ; self-healed in accordance with the subject invention and then removed from its wheel and examined from the inside, it is usually very different to locate the puncture. The sealant is drawn or forced into the hole to very effectively ; heal it.
It has been found that the subject sealant composition must be formulated to contain certain specific ., ~
iQ~
constituents witllin narrow and definite composition ranges. In the automobile tire embodiment, the diffi-culty lies in providing a composition which has the ability to both re-heal any cut in the sealant caused by a puncture and seal a puncture hole at a temperature anywhere in the range from a~out -20F. to 270F. Once the hole has been filled (which must occur very rapidly), it is then necessary for the sealant to have sufficient strength to maintain air under pressures up to 30 to 40 psig and higher while the tire is continually being flexed and stressed as it is in normal vehicie use. While the automobile tire sealant has been tested and found effective at temperatures up to 270F.
it is usually felt automotive tires in normal usage will not experience temperatures above about 220F.
The automobile sealant embodiment is made up according to the following specification. Two curable butyl rubber components -- one a relatively high molecular weight constituent and the other a relatively high molecular weight constituent -- are employed in combination. Ten to fifteen parts of an isobutylene-based copolymer (preferably about 96% isobutylene - 4% isoprene) having an average molecular weight in the range of about 100,000 to 300,000 is employed in combination with 6 to 10 parts of a copolymer of 96% isobutylene and 4% isoprene, having an average molecular weight in the range of about 10,000 to 30,000. Mixed with the curable butyl rubber constitu-ents are 60 to 65 parts by weight of a liquid polybutylene (e.g., 98% butylene - 2% isobutylene) tackifier having an average molecular weight in the range of 500 to S,000.
This liquid saturated C4 polymer represents a major part of the total composition. It possesses excellent thermal stability, stickiness and flowability over the wide temp-erature range in which the subject sealant must serve.
33~8~
An optional polymeric constituent of the subject sealant composition is a thermoplastic, elastomeric, hydro-genated block copolymer having the general configuration A-(B-A)l 5. Four to ten parts of this hydrogenated block copolymer are employed in combination with the other con-stituents. If more than about 10% of the block copolymer is employed in the subject sealant (solvent-free and curing agent-free basis) the composition will not adequately self-heal. If the block copolymer content is less than 4% (on the same basis) the sealant does not have adequate strength temperatures above about 220F. Compositions which include no block copolymers whatsoever are neverthe-less useful as bic~cle tire sealants, since operating temperatures within a bicycle tire will normally not range above 125F.
Prior to hydrogenation each A (of the A-(B-A)1_5 - block copolymer) is a thermoplastic monovinyl arene polymer block and each B is a conjugated diene polymer block. In accordance with our invention the monovinyl arene i8 preferably styrene, but may also be alpha methyl styrene, ring alkylated styrenes and the like as well as mixtures thereof. Furthermore, in accordance with our invention the B block(s) may be prepared from conjugated dienes having from 4 to 10 carbon atoms, but preferably 4, 5 or more carbon atoms per monomer molecule, including specifically isoprene. The elastomeric polymerized conjugated diene component of the block copolymer typically makes up in total about two-thirds or more of the block copolymer with the thermoplastic polymer constituent making up the end groups and the balance of the copolymer. In accordance ! with our invention the average molecular weight of this block copolymer is suitably in the range of about 60,000 to 400,000 and preferably in the range of about 70,000 to 150,000. The composition is partially hydrogenated so that ~ I , lQ~3~
the conjugated diene block segment(s) are substantially fully saturated. ~lowever, the polystyrene segm~nts are not appreciably hydrogenated. Copolymers which are not hydrogenated in this fashion are not suitably resistant to oxidation and degradation at the high temperature end of the operating environment of the tire, particularly considering that there is considerable oxygen in the tire.
Carbon black filler in the amount of 5 to 17 parts by weight is also incorporated into the composition.
A furnace black having a high surface area and a basic pH
- is preferred.
A solvent, such as toluene, for the polymeric components may be employed in the preparation and applica-tion of the sealant composition.
Also incorporated in the composition is a suit-able crosslinker for the butyl rubber constituents. The preferred corsslinker for the butyl rubber constituents is para-quinone dioxime. However, other well known bu~yl rub-ber curing agents may be employed. At the time the curing is to take place it is also necessary to incorporate an oxidative initiator, such as benzoyl peroxide, to convert para-quinone dioxime to its crosslinking form, para-dinitroso benzene. Para-quinone dioxime and benzoyl perox-ide are preferred for use in combination in the practice of our invention because they promote rapid gel times.
The embodiments of the invention described in the specific examples involved spraying the subject sealing composition into tires that had already been manufactured.
In another embodiment, particularly suitable for applica-tions to bicycle tires, the sealant composition is formed ; and cured in the form of sheets and applied to the inside of the tire, as desired, employing a suitable adhesive.
However, in many instances it will be preferred to form and cure the sealant layer at the same time the tire is ~eing manufactl~red, One practice would be to first lay up the butyl rubber-based inner liner. An uncured seal-ing layer of the subject composition would then be placed on the inner liner member. Then the uncured carcass por-1:ion of the tire, including its layers of reinforcing belting and the like, would be formed after the sealing layer had been laid up. Subsequently, the treat stock would be laid on the uncured carcass. The whole tire would then be cured at normal curing temperatures of the orde~
of 350F., at which temperature the curing of the subject sealing composition would be greatly accelerated and comparable in time to the curing of the other portions of the tire. When the butyl rubber portion of the subject sealant layer is cured at this high temperat`ure, some modifications may be required in the type and amount of crosslinker and initiator employed as compared with the above examples.
Prior to the discovery of the subject composition a number of other known sealant and elastomeric materials were tested and evaluated as self-healing tire sealants.
For example, other butyl rubber-containing compositions were tried but failed to be self-sealing over the wide temperature ranges involved. Also, ethylene-~inyl acetate copolymers were tested and found lacking. Urethane rubbers were also evaluated and it was found that they would not satisfactorily seal puncture holes over the wide temperature ranges involved. We have also found, as indicated above, that even when employing the specific constituents described as elements fo the subject composition, a wide variation in their compositional ranges cannot be toierated and still obtain the benefits of the subject invention.
While our invention has been described in terms ~' l0~32a~
of a few specific embodiments thereof, it will be appreci-ated that other fonns could be adapted by one skilled in the art and, accordingly, our invention is to be considered limited only by the scope of the following claims.
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Claims (13)
1. A sealant composition comprising a partially cross-linked matrix, said matrix comprising 12 to 15 parts by weight of a high average molecular weight butyl rubber having an average molecular weight in the range of about 100,000 to 300,000, 6 to 8 parts by weight of a low average molecuar weight butyl rubber having an average molecular weight in the range of about 10,000 to 30,000, and 5 to 17 parts of carbon black, in admixture with 60 to 65 parts by weight of a liquid polybutylene based tackifier.
2. The sealant composition of claim 1, wherein the high and low molecular weight bityl rubbers are comprised of about 96%
isobutylene and about 4% isoprene by weight.
isobutylene and about 4% isoprene by weight.
3. The sealant composition of claim 1, including 4 to 10 parts by weight of a partially hydrogenated block copolymer in admix-ture with the matrix, said block copolymer having the general config-uration A-(B-A)1-5 wherein each A is monovinyl arene polymer block and each B is a substantially fully hydrogenated conjugated diene polymer block.
4. The sealant composition of claim 1, wherein the tackifier has an average molecular weight in the range of 500 to 5000.
5. A sealant composition comprising a reaction product of (1) 12 to 15 parts by weight of a high average molecular weight butyl rubber having an average molecular weight in the range of about 100,000 to 300,000, (2) 6 to 8 parts by weight of a low average molecular weight butyl rubber having an average molecular weight in the range of about 10,000 to 30,000, (3) 5 to 17 parts by weight of a carbon black reinforcer, (4) 60 to 65 parts by weight of a liquid polybuty-lene based tackifier; and (5) small but suitable amounts of cross-linking agents suitable for crosslinking butyl rubbers.
6. The sealant composition of claim 5, wherein the cross-linking agents are p-quinone dioxime and benzoyl peroxide.
7. The sealant composition of claim 5, including 4 to 10 parts by weight of a partially hydrogenated block copolymer in admixture with the reaction product, said block copolymer having the general configuration A-(B-A)1-5 wherein each A is a monovinyl arene polymer block and each B is substantially fully hydrogenated conjugated diene polymer block.
8. In a method of making a self sealing tire, the improve-ment which comprises the steps of a) compounding a sealant composition comprised of (1) 12 to 15 parts by weight of a high average molecular weight butyl rubber having an average molecular weight in the range of about 100,000 to 300,000, (2) 6 to 8 parts by weight of a low average molecular weight butyl rubber having an average molecular weight in the range of about 10,000 to 30,000, (3) 5 to 17 parts by weight of a carbon black reinforcer, (4) 60 to 65 parts by weight of a liquid polybutylene based tackifier; and (5) small but suitable amounts of crosslinking agents suitable for crosslinking butyl rubbers; and b) applying said sealant composition to the inner sur-face of the tire.
9. The method of claim 9, wherein the sealant composition is applied to the inner surface of the tire and cured in situ.
10. The method of claim 9, wherein the sealant composition is cured before application to the inner surface of the tire.
11. A self-healing tire comprising an annular envelope having a carcass portion and sidewall portions, and a layer of sealant material applied to at least said carcass portion made up of a parti-ally cross-linked matrix comprising 12 to 15 parts by weight of a high average molecular weight butyl rubber having an average molecular weight in the range of about 100,000 to 300,000, 6 to 8 parts by weight of a low average molecular butyl rubber having an average molecular weight in the range of about 10,000 to 30,000, and 5 to 17 parts of carbon black, in admixture with 60 to 65 parts by weight of a liquid polybutylene based tackifier.
12. The tire of claim 11, wherein the high and low molecular weight butyl rubbers are comprised of about 96% isobutylene and about 4% isoprene by weight.
13. The tire of claim 11, including 4 to 10 parts by weight of a partially hydrogenated block copolymer in admixture with the matrix, said block copolymer having the general configura-tion A-(B-A)1-5 wherein each A is a monovinyl arene polymer block and each B is a substantially fully hydrogenated conjugated diene polymer block.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA241,978A CA1083288A (en) | 1975-12-17 | 1975-12-17 | Self sealing vehicle tire and butyl rubber sealant composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA241,978A CA1083288A (en) | 1975-12-17 | 1975-12-17 | Self sealing vehicle tire and butyl rubber sealant composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1083288A true CA1083288A (en) | 1980-08-05 |
Family
ID=4104766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA241,978A Expired CA1083288A (en) | 1975-12-17 | 1975-12-17 | Self sealing vehicle tire and butyl rubber sealant composition |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1083288A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4895610A (en) * | 1983-08-15 | 1990-01-23 | The Goodyear Tire & Rubber Company | Self-sealing pneumatic tire and method of manufacturing the same |
| US5295525A (en) * | 1992-06-22 | 1994-03-22 | Michelin Recherche Et Technique S.A. | Puncture sealant formulation |
| EP2065221A1 (en) * | 2007-11-30 | 2009-06-03 | Continental Aktiengesellschaft | Rubber composition and tire |
| CN105838289A (en) * | 2016-03-30 | 2016-08-10 | 广西柳州科来迪机械有限公司 | Prick-resistant explosion-proof polymer synthetic high-viscoelasticity rubber for tyre and preparation method thereof |
| CN112940648A (en) * | 2021-03-09 | 2021-06-11 | 蓉驿时代科技有限公司 | Anti-puncture self-healing cross-linked colloid and preparation method thereof |
| CN113185934A (en) * | 2021-05-10 | 2021-07-30 | 四川远星橡胶有限责任公司 | Self-repairing adhesive composition and preparation method and use method thereof |
-
1975
- 1975-12-17 CA CA241,978A patent/CA1083288A/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4895610A (en) * | 1983-08-15 | 1990-01-23 | The Goodyear Tire & Rubber Company | Self-sealing pneumatic tire and method of manufacturing the same |
| US5295525A (en) * | 1992-06-22 | 1994-03-22 | Michelin Recherche Et Technique S.A. | Puncture sealant formulation |
| EP2065221A1 (en) * | 2007-11-30 | 2009-06-03 | Continental Aktiengesellschaft | Rubber composition and tire |
| CN105838289A (en) * | 2016-03-30 | 2016-08-10 | 广西柳州科来迪机械有限公司 | Prick-resistant explosion-proof polymer synthetic high-viscoelasticity rubber for tyre and preparation method thereof |
| CN105838289B (en) * | 2016-03-30 | 2018-05-25 | 广西柳州轮道科技有限公司 | A kind of tire high viscoplasticity sizing material of pricking-proof explosion-proof Polymer Synthesizing and preparation method thereof |
| CN112940648A (en) * | 2021-03-09 | 2021-06-11 | 蓉驿时代科技有限公司 | Anti-puncture self-healing cross-linked colloid and preparation method thereof |
| CN113185934A (en) * | 2021-05-10 | 2021-07-30 | 四川远星橡胶有限责任公司 | Self-repairing adhesive composition and preparation method and use method thereof |
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