CN106626992B - Pneumatic tire and its manufacturing method with sealant layer - Google Patents
Pneumatic tire and its manufacturing method with sealant layer Download PDFInfo
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- CN106626992B CN106626992B CN201710010780.1A CN201710010780A CN106626992B CN 106626992 B CN106626992 B CN 106626992B CN 201710010780 A CN201710010780 A CN 201710010780A CN 106626992 B CN106626992 B CN 106626992B
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- sealant
- tire
- peroxide
- butyl
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C19/00—Tyre parts or constructions not otherwise provided for
- B60C19/12—Puncture preventing arrangements
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of tire with built-in sealant includes: carcass, carcass includes one or more layers casing ply, the tyre surface of outer circumference, with radial internal layer, a pair of bead is extended radially inwardly to the sidewall of respective bead by the axially outer edge of tread portion, sealant, sealant includes the catabolite for ionizing butyl polymer sealant precursor composition, and sealant is inwardly arranged from the layer on the inside of carcass, and self-styled performance can be provided for tire.
Description
Background technique
The present invention relates to the tires with inner sealing oxidant layer, in particular to by sealant precursor layer shape
At containing ionization butyl polymer sealant layer tire.
Tyre puncture is the intrinsic problem of inflated rubber tire.Sealant is developed and as stratification due to the above reasons,
Tire bring is influenced with reducing to pierce through on the inside of the tyre surface and casing ply of tire.Further, puncture is likely to occur in any
At a temperature of.At a lower temperature, the single layer sealant effectiveness of low viscosity is good；But at relatively high temperatures, due to the sealing
The viscosity of agent is lower, and then will lead to it and trickle from tire in use and come out.Exhausting for tire sealant causes to take turns
Tire loses the self-styled ability of perforation.Similarly, there is highly viscous single layer sealant to have good sealing effect at high temperature, but
It is that at low temperature, sealant is possibly close to solid-state, and then can not flow to tyre puncture position and be blocked.
Tire with built-in sealant layer is known in the art.Typically, the sealant of these tires passes through in tire
In sulfidation, degradation reaction is occurred by the sealant precursor layer based on butyl rubber and is obtained.Such as U.S. Patent number
4895610,6962181,7073550,7674344 and 8293049；And 2005/0113502 He of US publication number
2005/021568, contents of the above patents is both incorporated herein by reference.The color of sealant layer can be black or other face
Color；And sealant layer may include staple fiber, such as polyester or polyurethane fiber；Also it may include other kinds of filler aggregation
Body is to assist to realize that blocking hole for nailing pierces through.
Summary of the invention
The present invention relates to a kind of containing the built-in anti-tire for piercing through sealant, which includes carcass, carcass
Including one or more layers casing ply, the tyre surface of outer circumference and the layer of radially inner side, a pair of bead is outside by the axis of tread portion
Edge extends radially inwardly to sidewall and the sealant of respective bead, and sealant is by the precursor of the butyl polymer containing ionization by peroxide
Compound catalysis thermal degradation is formed, and sealant is inwardly arranged from the layer of the above-mentioned inside of carcass, provides self-styled performance for tire
's.
First aspect present invention provides a kind of with the built-in anti-tire for piercing through sealant, comprising:
Carcass, carcass include one or more layers casing ply, the tyre surface of outer circumference and the layer of radially inner side,
A pair of bead,
The sidewall of respective bead is extended radially inwardly to by the axially outer edge of tread portion,
Sealant, the sealant include the catabolite for ionizing butyl polymer sealant precursor composition, the sealing
Agent is inwardly arranged from the layer on the inside of the carcass, and
The sealant can provide self-styled performance for tire.
In one embodiment, the tire of any one of present invention, further comprises the covering above the sealant
Layer, the coating is innermost layer.
The described in any item tires of the present invention, wherein the 100% of the coating stretch surely modulus 0.5MPa extremely
Between 0.25MPa.
In one embodiment, the tire of any one of present invention, wherein before the ionization butyl polymer sealant
Body composition includes, based on the content of polymer therein,
The ionization butyl polymer composition of 100 parts by weight, it includes 20 weight % to the ionization fourth of 100 weight %
Based polyalcohol, the number-average molecular weight of the ionization butyl polymer composition is between 200000 to 500000, Mooney viscosity
Range between 40 to 58,
The filling oil of about 5 to 35 parts by weight,
The calcium carbonate of about 100 parts by weight,
The silica of about 50 parts by weight, and
The peroxide degradation catalyst of about 1 to 16 parts by weight, every 100 parts by weight of rubber (phr).
In one embodiment, the tire of any one of present invention, wherein the sealant layer is by using peroxide
It generates, self-accelerating decomposition temperature (SADT) range of the peroxide is between 50 to 140 DEG C.
Second aspect of the present invention provides a kind of tire manufacturing method, this method comprises:
Manufacture tire base；
Sealant precursor containing ionization butyl polymer composition and one or more peroxide is added supreme
It states in tire base, which includes, and based on 100 parts by weight of rubber (phr), ionizes butyl polymer
5 to 100 parts by weight；
Vulcanize the tire base；
Wherein, degradation occurs for the sealant precursor layer containing ionization butyl polymer instead in wheel blank sulfidation
It answers, forms sealant layer.
In one embodiment, the method for any one of present invention, the ionization butyl polymer composition is from described
Carcass is inside and is arranged outward from the inner liner, wherein the ionization butyl polymer composition includes:
The ionization butyl polymer of 100 parts by weight, ionize the number-average molecular weight of butyl polymer 200000 to
Between 500000,125 DEG C of Mooney viscosity ML (1+8) value ranges between 25 to 65,
The filling oil of about 5 to 35 parts by weight,
The calcium carbonate of about 100 parts by weight,
The silica of about 50 parts by weight,
The peroxide degradation catalyst of about 1 to 16 parts by weight.
In one embodiment, the method for any one of present invention, peroxide are selected from: 4,4- bis- (t-butyl peroxies
Base) n-butyl pentanoate；2,5-bis(t-butylperoxy)-2,5-dimethylhexane；1,1- di-t-butyl peroxy -3,3,5- three
Hexahydrotoluene；2,5- dimethyl -2,5- di-t-butyl peroxy -3- hexin；P- chlorobenzyl peroxide；2,4- benzyl dichloride
Base peroxide；2,2- bis- (t-butylperoxy) butane；Di-tert-butyl peroxide；Benzyl peroxide；Peroxidating two is different
Propyl benzene；- 2,5 bis(t-butylperoxy)s of 2,5- dimethyl-hexane.
In one embodiment, the method for any one of present invention, the number-average molecular weight for ionizing butyl polymer exist
Between 300000 to 400000.
In one embodiment, the method for any one of present invention, peroxide is dicumyl peroxide and dual-tert-butyl
The mixture of cumyl peroxide.
In one embodiment, the method for any one of present invention, tire is within the temperature range of 132 DEG C to 166 DEG C
It is formed and is vulcanized.
In one embodiment, the method for any one of present invention, sealant precursor composition further include peroxide
Compound activator.
In one embodiment, the tire of any one of present invention, the 100% of sealant precursor stretch the model of modulus M100 surely
It is trapped among between 400-900psi, preferably between 450-700psi.
In one embodiment, the present invention any one of method, peroxide activator be it is poly- [[6- (1,1,3,3 ,-
Tetramethyl butyl) amino] -1,3,5- triazine -2,4- replace] [(2,2,6,6,-tetramethyl -4- piperidines)-imido] -1,6- oneself two
Alcohol [(2,2,6,6,-tetramethyl -4- piperidines)-imido]].
In one embodiment, the method for any one of present invention, peroxide activator are selected from one kind of following substance
It is or a variety of: poly- [[6- (1,1,3,3,-tetramethyl butyl) amino]-s- triazine -2,4- substitution] [(2,2,6,6,-tetramethyl -4-
Piperidines)-imido] hexamethylene [(2,2,6,6,-tetramethyl -4- piperidines)-imido]], amine oxide two (adds hydrogen ox ester alkyl)；The last of the ten Heavenly stems two
Acid esters two (adds hydrogen ox ester alkyl).
Third aspect present invention provides a kind of tire of method manufactures described in any item according to the present invention.
Fourth aspect present invention provides a kind of tire of method manufactures described in any item according to the present invention.
Detailed description of the invention
For technical staff related to the present invention, it is described below and refers to attached drawing by reading, the present invention is above-mentioned
And other feature and advantage will be obvious.Attached drawing includes:
Fig. 1: being the sectional view for implementing tire of the invention；With
Fig. 2: being the enlarged section at the position 2-2 along tire in Fig. 1.
Specific embodiment
The present invention relates to a kind of tire containing sealant layer, which is passed through in tire vulcanization process by precursor
The composition of the butyl polymer containing ionization is formed by peroxide catalyzed thermal degradation.I.e. the tire, which has, is arranged in inside tires
Thermal degradation ionization butyl polymer sealant layer, which forms from precursor layer.The tire includes carcass,
Carcass includes one or more layers casing ply, the tyre surface of outer circumference and radially inner most inner liner (liner layer), a pair of of tire
Circle, the sidewall of respective bead, sealant layer and coating, sealant layer are extended radially inwardly to by the axially outer edge of tread portion
And coating is arranged on the above-mentioned most interior layer of carcass, wherein sealant is in tire vulcanization process by being based on ion
Thermal degradation is formed the composition of change butyl polymer in the presence of a peroxide, and then the ionization fourth of the thermal degradation inside formation
Based polyalcohol sealant layer.Sealant layer is inwardly arranged from the layer of the above-mentioned inside of carcass, provides self-styled performance for tire.
Term " sealant precursor " used herein above means that the composition itself is not sealant, but it is being taken turns
Sealant is transformed by thermal degradation in the vulcanisation step of tire preparation." precursor layer " refers to the layer of sealant precursor.Precursor layer
The ionization butyl rubber that can be 100% is being also possible to ionize butyl rubber and other rubber mix and can be converted into
The mixture of sealant, the mixture of the butyl rubber and butyl rubber of such as ionization, the mixture also exist in tyre vulcanization
Degradation forms the runny tacky sealant of low molecular weight under high temperature." degradation " used herein above refers to rubber molecular chain
Fracture so that the rubber content of low molecular weight rises.
In the present invention, sealant precursor layer is assembled into the unvulcanized tire (one by commonly using tyre forming process production
As be known as tire base) in.After unvulcanized tire building containing sealant precursor layer, which cures by standard method.It is close
Envelope agent precursor layer is assembled into tire, inwardly and from liner layer (can be inner liner) is arranged outward from carcass.It can replace
Generation, sealant precursor layer also can be set in the inside of tyre airtight layer (liner layer), in this case, while need one
Slice width degree coating more broader than sealant precursor layer.The effect of coating is the low molecular weight for preventing from being formed by sealant precursor
Tacky sealant pollutes curing bag.
The physical property of sealant precursor layer includes that sealant precursor layer will have sufficiently high viscosity, so that it is not
It is easy to operate in the molding standard step of vulcanized tyre and tire vulcanization process.That is, sealant precursor layer has enough
Green strength (modulus) keeps its shape in tire building process, and enough viscosity guarantees itself and adjacent layer in tire building
Bonding and enough intensity keep its shape when applying high pressure during high temperature vulcanized.
Since sealant precursor layer passes through vulcanizing treatment with tire together, by ionizing the thermal degradation of butyl polymer,
Sealant layer is formed in situ.In fact, in polymer composition layer ionization butyl polymer degradation form low viscosity,
Easily flowing cohesive material, the material have self-styled performance of perforating.That is, during tire is high temperature vulcanized, sealing
Agent precursor layer is transformed to anti-puncture sealant layer.The degradation of sealant precursor layer can be by one or more as catalyst
The presence of peroxide and realize.
Most rubber composition, for example, those are based on natural rubber, butadiene rubber, the rubber of butadiene-styrene rubber etc.
Composition when heating under the conditions of existing for the peroxide, can usually be hardened due to crosslinking reaction.However, being based on
The composition of butyl rubber, when heating jointly with peroxide, which reacts mainly due to thermal degradation (stopping of chain) occurs
And soften.Butyl rubber forms brombutyl by bromination reaction.Different from butyl rubber, brombutyl is in peroxide
It occur frequently that cross-linking reaction causes the content of hard rubber to rise under the conditions of compound is existing.Ionization butyl can pass through bromination fourth
Base occurs following chemical reaction and obtains:
During the experiment it was unexpectedly observed that different from brominated butyl, the composition based on ionization butyl is in peroxidating
Softer material can be degraded under the conditions of object is existing.Therefore, composition and suitable peroxide containing ionization butyl
It is used as sealant precursor after composition compounding, which can degrade when tire is high temperature vulcanized and be formed runny
Tire seal agent material.
It ionizes butyl rubber and derives from halogenated butyl rubber.And halogenated butyl rubber derives from butyl rubber.Butyl rubber
Glue is obtained by isobutene and a small amount of isoprene copolymer.Generally, butyl rubber contains the isoamyl of 0.5mol%~4mol%
The isobutene units of diene and 99.5mol%~96mol%.It can be applied to the butyl in the polymer composition of tire of the present invention
The range of the number-average molecular weight of rubber is about 200000~600000, and preferably 300000~500000；And Mooney viscosity ML (1+8)
The range of/125 DEG C of values is 25~65.Butyl rubber is converted into brombutyl, further by reacting brominated butyl
Bromo functional groups are transformed into the limidazolium functional group of ionization in rubber, and then form and show the reversible of physical crosslinking performance
Ionic associate.
At least one ionization butyl polymer can obtain commercialized product, commodity from Lang Sheng (Lanxess) company
Entitled X_ButylTMI4565P, Mooney viscosity ML (1+8)/125 DEG C 56 ± 4MU of value, ion concentration are 0.4 ± 0.1 mole of %,
Total reactable bromine content is that the content of 0.5 ± 0.2 mole of % and 1,4- isoprene is 0.5 ± 0.2 mole of %.
Composition based on 100 parts by weight (parts by weight/100 parts by weight of rubber) ionization butyl polymer can be used as sealing
Agent precursor uses.Ionization butyl polymer can also be applied in combination with other in the elastomer of tyre vulcanization temperature degradation.One
The example of a this polymer is butyl rubber.That is the ionization butyl polymer and 0 to 95 weight of 100 to 5 parts by weight (phr)
The combination for measuring the butyl rubber of part (phr) can be used for obtaining tire sealant composition.
In the present invention, the polymer composition layer for being mounted to inside tires preferably has following component distribution, weight
Measure part/100 parts by weight of rubber
The ionization butyl polymer of 100 parts by weight, such as: the X_Butyl of Lanxess Corporation's productionTMI4565P；
The silica of about 10 to 100 parts by weight, such as: the filler of Sidistrar 320 or other models；
The adhesive of about 1 to 15 parts by weight, such as: the Wingtack 85 of Dao Daer (Total) company production；
The calcium carbonate of about 20-200 parts by weight, such as: the Hubercarb Q3 of Huber company production；
The oil of about 5 to 35 parts by weight, and
The suitable peroxide of about 1 to 16 parts by weight.
It is any (about 150 DEG C) catalysis to be based on ionizing the precursor composition of butyl (rubber) at a temperature of tyre vulcanization
Or mixtures thereof the peroxide that thermal degradation (chain termination) reaction occurs can use.Preferably, using only in high temperature, that is, existing
More than about 100 DEG C (212 °F), just decompose peroxide compositions.This peroxide such as, has identical or different free radical
The peroxidized t-butyl perbenzoate and/or dialkyl peroxide of group, such as dialkyl phenyl organic peroxide and/or alkyl
Peracid ester.Preferred peroxide degradation catalyst includes two peroxy radicals.In general, two peroxy radicals meetings
It reacts with the tertiary butyl groups on ionization butyl polymer molecule.The main positions of two peroxide groups connection can
To be aliphatic, alicyclic or aromatic free radical.Some peroxide degradation catalyst candidates, comprising: 2,5- is bis-
(t-butylperoxy) -2,5- dimethylhexane；1,1- di-tert-butyl peroxide -3,3,5- trimethyl-cyclohexane；2,5- diformazan
Base -2,5- bis(t-butylperoxy) -3- hexin；P- chlorobenzyl peroxide；2,4- dichloro benzyl peroxide；2,2- is bis-
(t-butylperoxy) butane；Di-tert-butyl peroxide；Benzyl peroxide；2,5- bis(t-butylperoxy) -2,5- two
Methyl hexane；Cumyl peroxide；2,5- dimethyl -2,5- two (t-butylperoxy) hexane.These peroxide degradations
Catalyst can be added in polymeric compositions in the form of pure component, can also load to mine that is inert, can flowing freely
It is added on material carrier.The example of some inert carriers is calcium carbonate and silica.It wherein include 35 to 60 parts by weight
The carrier of active component (peroxide) be proved to be effectively.For example, load has 40 weight percent peroxidating diisopropyls
The inert carrier of benzene is applied to available extraordinary experiment in polymer composition layer as peroxide degradation catalyst
As a result.
Although reaction mechanism be not it is fully aware of, the application of activator within the scope of the invention, such as based on 2,
The application of the hindered amine of 2,6,6- tetraalkyl piperidines, activator can activate organic peroxide, in a sense, can be reduced
The dosage of organic peroxide, and then the more efficiently degradation ionization butyl polymer in sealant layer forming process.These
Activator is known in the art, for example, the United States Patent (USP) No 7 of D ' Sidocky et al., the content disclosed in 674,344 pass through
Reference is integrated in the present invention.
One representative 2 based on hindered amine, the example of the hindered amine of 2,6,6- tetraalkyl piperidines are, for example, pressing 50/
Poly- [[6- (1,1,3,3,-tetramethyl butyl) amino]-s- triazine -2,4- substitution] [(2,2,6,6, the-tetramethyl -4- of 50 mixing
Piperidines)-imido] hexamethylene [(2,2,6,6,-tetramethyl -4- piperidines)-imido]] (also referred to as PTP) and amine oxide two (add hydrogen ox
Ester alkyl) (by BASF withFS410FF title sale).
The example of another peroxide activator is, by PTP, amine oxide two (adding hydrogen ox ester alkyl) and sebacate
Two (adding hydrogen ox ester alkyl) (by BASF withFS811 title sale) formed mixture.
The example of another peroxide activator is, poly- [[6- (1,1,3,3,-tetramethyl butyl) amino] -1,3,
5- triazine -2,4- replaces] [(2,2,6,6,-tetramethyl -4- piperidines)-imido] -1,6-HD [(2,2,6,6,-tetramethyl -
4- piperidines)-imido]], by BASF with944FDL, title sale.
In fact, typically the composition containing above-mentioned PTP is the composition containing above-mentioned PTP, it is also possible to also contain
The composition of sebacate two (adding hydrogen ox ester alkyl) is also possible to optionally also contain amine oxide two (adding hydrogen ox ester alkyl)
Composition.In fact, using the above-mentioned hindered amine for being based on 2,2,6,6- tetraalkyl piperidines, especially above-mentioned PTP, or comprising
The amine composition that is obstructed based on 2,2,6,6- tetraalkyl piperidines of (including) above-mentioned PTP, for the ionization in sealant precursor
Organic peroxide is activated in the degradation process of butyl polymer, is considered being important herein.Its object is to as far as possible
Ground reduces concentration of the sealant precursor based on the organic peroxide in ionization butyl polymer composition, excessive unreacted
The built-in sealant layer that can remain in of peroxide in, and in turn, come into contact with the phase in tire with built-in sealant layer
Adjacent rubber composition.
Each composition of sealant layer can be kneaded by any convenient rubber mixing equipment, such as mixing in banbo
Machine.There is rubber composition used in sealant layer enough viscosity and raw rubber bonding force to ensure itself and unvulcanized tire (tire
Base) bonding, avoid sealant layer that delamination occurs when producing under standard, tire building technical conditions for a long time, and
It avoids using complicated, expensive molding equipment.
Sealant precursor strip based on ionization butyl polymer can extend to another from the side shoulder region of tire
Side.That is, the sealant precursor strip can cover the crown position of entire tire.According to different tire specification, sealing
The thickness of agent precursor layer can be adjusted.In general, the thickness of polymer composition layer can be in 0.1cm (0.04 English
It is very little) it is adjusted between 0.635cm (0.25 inch) range.The thickness of preferred polymers composition layer is at 0.2cm (0.08 inch)
To between 0.4cm (0.16 inch) range.For car tyre, the optimum thickness of polymer composition layer is 0.25cm
(0.1 inch).
Inflation of the invention is that can carry out them in the conventional tyre vulcanization period after vulcanized tyre (tire base) assembles
Vulcanization.Tyre vulcanization can be carried out in very wide sulfurizing temperature range.However, currently preferred tyre vulcanization temperature range
At 132 DEG C (270 °F) between 166 DEG C (330 DEG C).More there is the tyre vulcanization temperature range of choosing at 143 DEG C (290 °F) to 154
Between DEG C (310 DEG C).For the duration of curing cycle of the invention, preferred time range was at 10 to 14 minutes, more
It is 12 minutes for the preferred time.
The tire building program that can apply standard of the invention.It, can after completing tire base (unvulcanized tire) molding
With selective use layer protecting film on the sealant coating of the innermost layer of tire.The width of protective film is than sealant
Layer slightly wide (about wide 2 inch in every side).Just in case innermost layer sealant coating is ruptured or is torn in the mold, the protective film energy
So that curing bag is protected from pollution and keeps cleaning.Such protective film is known in the art.For example, Coveris high
The trade name of energy packaging company productionC917, with a thickness of 2 millimeters of non-stretched nylon-6s, 6 films.It protects
The overlap length for holding about 1 inch of film end removes the protective film after facilitating vulcanization.This structure in Majumdar, Logan and
It is had been described in the United States Patent (USP) No 7,332,047 of Lukich, which is incorporated herein by reference herein.It protects
Cuticula can also use on tire assembly drum as first layer.For convenience's sake, it is preferable that protective film both sides, which are posted, to be had
The thermoplastic film of pressure sensitive adhesive.The film of this structure in the United States Patent (USP) No 7,419,557 of Majumdar and Page
It is described, which is incorporated herein by reference herein.Although membrane material be not it is crucial, compared to nylon-
6,6 films, it is preferable to use dynamic vulcanization alloy (Dynamically Vulcanized Alloy, DVA) in tire building process
Film, because there is DVA lower stretch modulus can extend under lesser power in tire building.This material
The use of material has been described in 776,851, is hereby incorporated by reference herein in the United States Patent (USP) No8 of Majumdar.
Other United States Patent (USP)s No8,021,730 and 8,158,721 is also hereby incorporated by reference herein.In encapsulant composition
In added organic peroxide activator to accelerate to degrade, this method D ' Sidocky United States Patent (USP) No7,674,
To be described in 344, it is hereby incorporated by reference herein.
The present invention is compound by inner liner (liner layer) and sealant precursor layer.Inner liner (liner layer) includes: brominated butyl
Rubber, carbon black, naphthenic oil, stearic acid, phenolic resin tackifier, aromatic hydrocarbon resins mixture (
40MS resin is manufactured by Struktol company, the U.S.), magnesia, zinc oxide, sulphur, 2,2 '-disulfide group bisbenzothiazoles are (logical
Often with title MBTS sale).Sealant precursor includes: be added in the first nonproductive (NP) compounding procedure: ionization butyl is poly-
Object is closed, paraffin oil, silica, clay, titanium dioxide, mica, Masterbatch be (Akrochem company, the U.S.E2295 green master batch andThe orange master batch of E6615), and/or be based on
Processing aid (the processing aid of Struktol company, U.S. production of mixing-in fat acid derivativeHPS11).?
Finished composition (PR) process is added: organic peroxide, such as (t-butylperoxy) n-butyl pentanoate of 4,4- bis- (such as Akzonobel
Company's production17-40B-GR)。
Preferably, tire of the present invention is prepared in the following order:
1. the sealant coating with formula shown in table 1 is kneaded and is calendered to a thickness of 1 millimeter, width with it is airtight
Layer (liner layer) is suitable or is slightly wider than sealant precursor layer.
2. the sealant precursor with formula shown in table 2 is kneaded and is calendered to a thickness of 3 millimeters, width is wider than tyre surface
It spends about 15 millimeters small.
3. the sealant coating of above-mentioned #1 is applied on tire assembly drum.
4. next, by the sealant precursor applications of above-mentioned #2 on tire assembly drum
5. next, inner liner (liner layer) is applied on tire assembly drum by typical tire moulding process, then will remain
Remaining layer is discharged by normal tyre forming process.
Embodiment
By the compounding raw materials in mixer, the sealant precursor composition based on ionization butyl polymer is obtained.It will
Other raw materials other than organic peroxide are mixed in the first (nonproductive) compounding procedure, are then kneaded in second (production)
Organic peroxide is added process.Composition of raw materials is as shown in table 2 below.Raw material components are right by every 100 parts by weight of rubber (phr)
The parts by weight meter answered.
Table 1
Table 2
Sealant precursor applications be can be used as into after product compositions are processed in tire building process.Embodiment 1 passes through vibration
The data for swinging disk rheometer (ODR) test are as shown in table 2.Before precursor composition degradation, initial moment is
16.95dN·m；(this process simulation tire vulcanization process), precursor composition after 30 minutes under the conditions of 150 DEG C of temperature
It is converted into sealant by thermal degradation reaction, final torque is 5.07dNm.The variation of this torque is mainly due to having
Chain caused by machine peroxide catalyzed is broken (degradation) reaction.If mainly crosslinking reaction in sulfidation, that sizing material is most
Whole torque value should be able to get higher (degree of cross linking increase), as brombutyl.Unvulcanized sealant precursor layer film
Tensile strength (also become green strength) as shown in table 2.In table 2, M100, M200 and M300 respectively correspond sizing material and exist
Corresponding modulus value when 100%, 200% and 300% elongation strain occurs.
Other carries out refining glue acquisition by mixer based on the sealant precursor composition of ionization butyl polymer.
Other than organic peroxide, other all raw materials are all mixed in the first (nonproductive) process, then in second (production) work
Organic peroxide is added in sequence.Each raw material is as shown in table 3 below.Raw material presses the corresponding parts by weight table of every 100 parts by weight of rubber (phr)
Show.
Table 3
Annotation
1Vul-Cup 40KE is a containing 40%, a '-dual-tert-butyl cumyl peroxide
2Di-Cup 40KE is the cumyl peroxide containing 40%
The initial moment of all compositions may each be about 22.60dNm, then due to these compositions are sent out in ODR equipment
Heat (150 DEG C, 30 minutes) formation sealant materials of degradation, their torque value are decreased to less than 4.52dNm.With contain base
It is compared in the composition (embodiment 2) of 100% butyl rubber, the material containing ionization butyl polymer (implemented by embodiment 3
Example 4 and embodiment 5) there is significant higher green strength.As shown in table 3, close based on 100 parts by weight (phr) butyl rubber
Agent is sealed, tensile strength is 33psi (embodiment 2)；By by the butyl rubber of 20 parts by weight (phr) with 20 parts by weight (phr)
Ionization butyl polymer replace after, tensile strength is increased to 171psi (embodiment 3).It therefore, it is expected to, only need
Butyl rubber is substituted with the ionization butyl polymer of a small amount of (such as 5 parts by weight (phr)), it is strong significantly to improve stretching
Degree.It therefore, include the sealant precursor for ionizing butyl rubber, even if the content of ionization butyl rubber is very low, compared to
Based on the sealant precursor of 100 parts by weight (phr) butyl rubber content, also relatively it is easier to operate to.
For convenience of explanation, some internal materials of tire are omitted in attached drawing, such as belt and casing ply, but these
Component is still to be present in actual tire construction.
Fig. 1 is shown as the sectional view of vulcanized tyre 10 of the invention.The size and each layer of actual tire of each layer component of the figure
Thickness and width it is all disproportionate, because of the sequence of each layer component of this figure main presentation rather than actual size.In fact, width
Can be wide to entire tire is covered, it can also the narrow slice to along central tire.Fig. 2 is shown as the section of each layer of tire in Fig. 1
Schematic diagram.It is similar to the dimension scale of each layer of Fig. 1, the practical actual thickness of each layer and wide of the size of each layer of Fig. 2 tire and tire
It spends disproportionate, mainly shows each layer of tire sequence herein rather than practical actual size.As shown, sealant precursor layer exists
Formd in tire vulcanization process sealant layer 102, sealant coating or inner liner (liner layer) with it is identical just as shape
Formula shows (104).Although showing the both ends that sealant coating 104 extends to sidewall 106 in figure, sealant coating is practical
It can be arranged by form known in the art.After the vulcanization of tire base, sealant precursor layer is converted to sealant layer 102.Fig. 1 is also shown
Show that sealant layer is placed between inner liner (liner layer) 104 and carcass transition zone 108 in the present invention.Carcass transition zone 108 is located at
Between the innermost layer and sealant layer 102 of carcass 116, sealant layer is formed after tyre vulcanization by sealant precursor layer.
The application of carcass transition zone is known in the art, and can use as needed when sealant layer is arranged.Other of tire are each
Part-structure is also demonstrated in Figure 1, such as tyre surface 114, carcass 116 and unexpansive tyre bead 118.
The 100% of coating stretches modulus in 0.5MPa between 2.5MPa surely.Sealant layer is by using peroxidating produce
Raw, self-accelerating decomposition temperature (ASDT) range of peroxide is between 50-140 DEG C.The 100% of sealant precursor stretches modulus surely
(M100) within the scope of 400-900psi, preferably in the range of 450-700psi.
Above-described embodiment is the description and explanation to the principle of the invention, and it not is to contain the present invention that these, which are illustrated and described,
Full content or the present invention is confined in these specific forms.Principle according to the present invention can be in the above-described embodiments
Many improve and variation can be done.The above embodiments are primarily to preferably explain that the principle of the present invention is applied with it, is made
It those skilled in the art's principle through the invention and is preferably utilized by being suitably modified, and according to special-purpose
This patent.
Claims (18)
1. a kind of with the built-in anti-tire for piercing through sealant, comprising:
Carcass, carcass include one or more layers casing ply, the tyre surface of outer circumference and the layer of radially inner side,
A pair of bead,
The sidewall of respective bead is extended inwardly to by the axially outer edge diameter of tread portion,
Sealant, the sealant include ionize butyl polymer sealant precursor composition catabolite, the sealant from
Layer on the inside of the carcass is inwardly arranged, and
The sealant can provide self-styled performance for tire；
The sealant is formed by the precursor of the butyl polymer containing ionization by peroxide catalyzed thermal degradation.
2. tire described in claim 1, further comprises the coating above the sealant, the coating is most
Internal layer.
3. tire as stated in claim 2, wherein the 100% of the coating stretch surely modulus 0.5MPa to 0.25MPa it
Between.
4. tire described in claim 1, wherein the ionization butyl polymer sealant precursor composition includes being based on
The content of polymer therein,
The ionization butyl polymer composition of 100 parts by weight, it is poly- that it includes the ionization butyl of 20 weight % to 100 weight %
Object is closed, the number-average molecular weight of the ionization butyl polymer composition is between 200000 to 500000, the model of Mooney viscosity
It is trapped among between 40 to 58,
The filling oil of 5 to 35 parts by weight,
The calcium carbonate of 100 parts by weight,
The silica of 50 parts by weight, and
The peroxide degradation catalyst of 1 to 16 parts by weight, every 100 parts by weight of rubber (phr).
5. tire described in claim 1, wherein the sealant layer is generated by using peroxide, the peroxide
Self-accelerating decomposition temperature (SADT) range is between 50 to 140 DEG C.
6. tire according to claim 4, the 100% of sealant precursor stretches the range of modulus M100 in 400-900psi surely
Between.
7. tire according to claim 4, the 100% of sealant precursor stretches the range of modulus M100 in 450-700psi surely
Between.
8. a kind of tire manufacturing method, this method comprises:
Manufacture tire base；
Sealant precursor containing ionization butyl polymer composition and one or more peroxide is added to above-mentioned tire
In base, which includes, based on 100 parts by weight of rubber (phr), ionization butyl polymer 5 to
100 parts by weight；
Vulcanize the tire base；
Wherein, in wheel blank sulfidation degradation reaction, shape occur for the sealant precursor layer containing ionization butyl polymer
At sealant layer.
9. according to the method described in claim 8, the ionization butyl polymer composition is from carcass inwardly and from wheel
Tire inner liner is arranged outward, wherein the ionization butyl polymer composition includes:
The ionization butyl polymer of 100 parts by weight ionizes the number-average molecular weight of butyl polymer 200000 to 500000
Between, 125 DEG C of Mooney viscosity ML (1+8) value ranges between 25 to 65,
The filling oil of 5 to 35 parts by weight,
The calcium carbonate of 100 parts by weight,
The silica of 50 parts by weight,
The peroxide degradation catalyst of 1 to 16 parts by weight.
10. according to the method described in claim 8, peroxide is selected from: 4,4- bis- (t-butylperoxy) n-butyl pentanoates；2,
5- bis(t-butylperoxy)-2,5-dimethylhexane；1,1 di tert butylperoxy 3,3,5 trimethylcyclohexane；2,5-
Dimethyl -2,5- di-t-butyl peroxy -3- hexin；P- chlorobenzyl peroxide；2,4- dichloro benzyl peroxide；2,2-
Two (t-butylperoxy) butane；Di-tert-butyl peroxide；Benzyl peroxide；Cumyl peroxide；2,5- dimethyl-
2,5 bis(t-butylperoxy)s-hexane.
11. according to the method described in claim 8, ionization butyl polymer number-average molecular weight 300000 to 400000 it
Between.
12. according to the method described in claim 8, peroxide is dicumyl peroxide and dual-tert-butyl cumyl peroxide
Mixture.
13. according to the method described in claim 8, tire is to carry out molding and sulphur within the temperature range of 132 DEG C to 166 DEG C
Change.
14. according to the method described in claim 8, sealant precursor composition further includes peroxide activator.
15. according to the method for claim 14, peroxide activator is poly- [[6- (1,1,3,3 ,-tetramethyl butyl) ammonia
Base] -1,3,5- triazine -2,4- substitution] [(2,2,6,6,-tetramethyl -4- piperidines)-imido] -1,6-HD [(2,2,6,6, -
Tetramethyl -4- piperidines)-imido]].
16. according to the method for claim 14, peroxide activator is selected from the one or more of following substance: poly- [[6-
(1,1,3,3,-tetramethyl butyl) amino]-s- triazine -2,4- substitution] [(2,2,6,6,-tetramethyl -4- piperidines)-imido] ring
Hexane [(2,2,6,6,-tetramethyl -4- piperidines)-imido]], amine oxide two (adds hydrogen ox ester alkyl)；Sebacate two (adds hydrogen ox
Ester alkyl).
17. a kind of tire of method according to claim 11 manufacture.
18. a kind of tire of method according to claim 11 manufacture.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/991,575 US10589478B2 (en) | 2014-12-16 | 2016-01-08 | Pneumatic tire having sealant layer |
| US14/991,575 | 2016-01-08 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022229914A1 (en) * | 2021-04-30 | 2022-11-03 | Pirelli Tyre S.P.A. | Self-sealing tyre for vehicle wheels |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT201900001153A1 (en) * | 2019-01-25 | 2020-07-25 | Bridgestone Europe Nv Sa | METHOD AND APPLICATION SYSTEM FOR APPLYING A SEALANT AGENT ON THE INTERNAL SURFACE OF A TIRE |
| CN110254136B (en) * | 2019-05-10 | 2023-10-10 | 浙江美亿佳新科技有限公司 | Puncture-proof electric motor car tire and production method thereof |
| JP2021046488A (en) * | 2019-09-18 | 2021-03-25 | 横浜ゴム株式会社 | Sealant material composition |
| CN114867812B (en) * | 2019-12-17 | 2024-04-02 | 横滨橡胶株式会社 | Sealant material composition |
| US20220410516A1 (en) * | 2021-06-24 | 2022-12-29 | The Goodyear Tire & Rubber Company | Self sealing tire |
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