CN101636283B - Tire innerliner - Google Patents
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- CN101636283B CN101636283B CN200780048892.0A CN200780048892A CN101636283B CN 101636283 B CN101636283 B CN 101636283B CN 200780048892 A CN200780048892 A CN 200780048892A CN 101636283 B CN101636283 B CN 101636283B
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Abstract
A method of preparing a green tire innerliner, the method comprising mixing one or more vulcanizable rubbery polymers, less than 0.75 parts by weight zinc oxide, less than 0.75 parts by weight magnesium oxide, and less than 0.75 parts by weight sulfur, per 100 parts by weight rubber, to form a vulcanizable mixture and extruding the mixture to form a green tire innerliner.
Description
The application requires the rights and interests of the U.S. Provisional Patent Application sequence number 60/877,765 of submitting on December 29th, 2006 and the U.S. Provisional Patent Application sequence number 60/967,215 of submitting on August 31st, 2007, and it is incorporated herein with for referencial use.
Technical field
One or more embodiment of the present invention relates to the tire formulation for inside liner.
Background technology
Airtyred inside face can comprise elastic composition, and it is designed to prevent or postpone breathing freely from tire inner air chamber.This elastic composition is commonly referred to inside liner.Relatively airproof rubber such as butyl rubber and halogenated butyl rubber are typically used as the main rubber components in the inside liner.
Inside liner can comprise the sheet material by the elastomeric relative thin of compounding additive and vulcanizing system preparation.In the time of on tire being formed at tire assembly drum (building drum), the elastic body prescription can be laminated to the inside face of not tire curing tire carcass layer.The final sulfuration of composite structure produces the tire with the sulfuration inside liner that is attached to carcass.
The needed character of inside liner comprises good anti-permeability to air (resistance to airpermeation), flexible resistance and to the adhesiveness of tire carcass.Low-permeable is generally by realizing with high-tg polymer such as butyl rubber or halogenated butyl rubber.High-tg polymer can with other elastic bodys such as SBR or natural rubber blend.Flexible resistance and pulling strengrth will be somewhat dependent upon modulus.
Natural rubber and butyl rubber can be by vulcanizing with sulfur vulcanization system.Halogenated butyl rubber can be by vulcanizing with Metal-oxide vulcanization system and sulfur vulcanization system.
The typical amount for the blend of halogenated butyl rubber or halogenated butyl rubber and natural rubber of reporting in the document is 3 to 5 parts of (based on each hundred parts of rubber (phr)) zinc oxide and 0.5 to 1 part of sulphur phr.
Therefore, expect a kind of method for the preparation of the tire flap layer formula, described tire flap layer formula has the good combination that comprises permeability to air, flexible resistance, pulling strengrth percentage elongation and adhering character.Specifically expectation is vulcanisable compound, and it comprises one or more rubber-like polymers and causes the inside liner prescription to have the vulcanizing system of these character best of breeds.
Summary of the invention
One or more embodiment of the present invention provides the method for preparing the green tire inside liner, but the method comprises one or more polysulphide rubbers shaped polymers, the zinc oxide that is lower than 0.75 weight portion, the sulphur (based on per 100 parts by weight of rubber) that is lower than the magnesium oxide of 0.75 weight portion and is lower than 0.75 weight portion are mixed, but to form cured blend and this compound is extruded to form the green tire inside liner.
Other embodiments provide the method for preparing the green tire inside liner, the method comprises that the rubber that will comprise halogenated rubber mixes with comprising one or more vulcanizing systems that are selected from the vulcanizator in the group that is comprised of sulphur, magnesium oxide and zinc oxide, but to form cured blend, wherein the crosslinkable on vulcanizing system and the halogenated rubber is at least 0.1: 1 to 1.8: 1 to the mol ratio of the molal quantity of (crosslinkablepair); And this compound extruded to form the green tire inside liner.
Other embodiments provide the tire that comprises inside liner, and wherein inside liner comprises the rubber composition of at least part of sulfuration, and wherein rubber composition is characterised in that swelling (swollen) polymer volume mark (V
r) be lower than 0.15.
Description of drawings
Fig. 1 is half cross sectional drawing of tire according to one or more embodiments of the present invention.
The specific embodiment
In one or more embodiments, the invention provides the method for the preparation of the tire that comprises inside liner.Other embodiments relate to the inside liner prescription and use the tire of these inside liner prescription preparations.
Example according to tire of the present invention is shown among Fig. 1.Tire 10 comprises fetus face 12, bracing ply section (belt package) 14, sidewall section 16, tire shoulder section 18, inside liner carcass plies 20, cavity 22 and bead part 30, and described bead part 30 comprises bead core 31.Carcass 32 extends between tire figure section 30.Bead core 31 helps to keep bead part 30 against vehicle rim 35.Air-inflation tyre can be such as U.S. Patent number 5,866, and that discusses in 171,5,876,527,5,931,211 and 5,971,046 makes, and these documents are incorporated herein with for referencial use.
In one or more embodiments, inside liner can be by conventional calendering or mixing technology preparation, and to form the not sulfuration compounding rubber strip of proper width, it is sometimes referred to as insulation rubber.This insulation rubber can be tire the first member that is applied to tire assembly drum, makes up other members of tire on it or around it.In other embodiments, before inside liner being positioned on this drum, itself and other tyre assembly can be formed assembly set.When vulcanized tyre, inside liner can become the part of the integrated co-vulcanization of tire.Tire liner and preparation method thereof is that this area knack technical personnel is known.
In one or more embodiments, vulcanizable inside liner composite can be shaped to layer or sheet.Known such as those skilled in the art, this layer can be produced by mill, flattening mill, bull extruder or other suitable equipment via press or with rubber composition.In one or more embodiments, this layer can be by flattening mill production.Then, this unvulcanized layer or sheet can consist of the inside face of the half finished rubber tire construction that can be described as carcass.
Enforcement of the present invention needn't be considered inside liner thickness.In one embodiment, the thickness that inside liner of the present invention has a uncured rubber about 0.02 to about 0.5cm scope, in other embodiments about 0.03 to about 0.45cm scope, in other embodiments about 0.04 to about 0.4cm scope, in other embodiments about 0.05 to about 0.2cm scope, in other embodiments, about 0.08 to about 0.2cm scope.
In one or more embodiments, in tyre vulcanization operating period, under hot pressing condition, can with not sulfuric horizon and tire carcass and with other tyre assembly co-vulcanization.In one or more embodiments, the sulfuration that contains the tire of inside liner of the present invention can be carried out to about 200 ℃ temperature at about 100 ℃.In one embodiment, sulfuration is carried out under about 110 ℃ of temperature to about 180 ℃ of scopes.Can use any vulcanization process known in the art, be included in heating in press or the mould, heat or in salt bath, heat with superheated steam or hot salt.In one embodiment, heating realizes in press or mould.Those skilled in the art can easily select conditions of vulcanization, to realize the suitable sulfuration of various tyre assemblies.
In one or more embodiments, the inside liner of sulfuration is by becoming the integrated part of tire with the tire co-vulcanization.In one or more embodiments, inside liner is vulcanized to adjacent tyre assembly (for example carcass), and adhered thereto thus, until the gained layered product passes through the degree about the industrial standard that adheres to, for example can be by the definite standard of blow point analysis (blow point analysis).
In one or more embodiments, the inside liner of sulfuration has about 0.02 thickness to about 0.35cm scope.In another embodiment, the inside liner of sulfuration has about 0.04 thickness to about 0.15cm scope.
In one or more embodiments, the air-inflation tyre with integrated inside liner can consist of with the oblique of passenger tyre, truck tyre or other types or the form of pneumatic radial tire.
In one or more embodiments, comprise rubber components and vulcanizing system for the preparation of the vulcanizable inside liner composite of above-mentioned green tire inside liner.Vulcanizable inside liner composite can also comprise that other are generally used for preparing the component in the vulcanizable inside liner compositions field.
Vulcanizing system can comprise a large amount of vulcanizers, and it includes but not limited to sulphur compounds, metallic oxide or peroxide vulcanizing system.Vulcanizator can be used singly or in combination.The sulphur compounds comprises conventional for the manufacture of those cmpds in the tire field.These cmpds also can be described as sulphur or sulfur crosslinking agent.In one or more embodiments, sulphur comprises free sulphur and those cmpds as the sulphur compound donator as known in the art (for example, thiuram such as thiuram-disulfide) that also can be described as elemental sulfur.
Vulcanizator is described in Kirk-Othmer, Encyclopedia of ChemicalTechnology, 365-468, (the 3rd edition, 1982), particularly VulcanizationAgents and Auxiliary Materials, 390-402, A.Y.Coran, Vulcanization in Encyclopedia of Polymer Science andEngineering, (the 2nd edition, 1989), Frederick R.Erich, Science andTechnology of Rubber, Chapter 7, Academic Press (1978), RobertF.Ohm, The Vanderbilt Rubber Handbook, pp.92-122 (the 13rd edition, 1990), Krishna C.Baranwal﹠amp; Howard L.Stephens, BasicElastomer Technology, Chapter 9, (the 1st edition, 2001), and and MauriceMorton, Rubber Technology, Chapter 10, and (the 2nd edition, 1981) is incorporated herein it with for referencial use.
In one or more embodiments, vulcanizing system comprises sulfur crosslinking agent, zinc oxide and/or magnesium oxide.
In one embodiment, vulcanisable compound comprises zinc oxide, its amount is to about 0.8 weight portion (pbw) zinc oxide based on per 100 parts by weight of rubber (phr) about 0, about 0.1 to about 0.75pbw zinc oxide p hr in other embodiments, about 0.2 to about 0.5pbw zinc oxide p hr in other embodiments, and about 0.25 to about 0.38pbw zinc oxide p hr in other embodiments.
In certain embodiments, vulcanisable compound comprises the zinc oxide p hr less than about 0.75pbw, in other embodiments less than the zinc oxide p hr of about 0.5pbw, in other embodiments less than the zinc oxide p hr of about 0.38pbw, in other embodiments less than the zinc oxide p hr of 0.3pbw, in other embodiments less than the zinc oxide p hr of 0.2pbw, in other embodiments less than the zinc oxide p hr of 0.15pbw, in other embodiments less than the zinc oxide p hr of 0.10pbw, in other embodiments less than the zinc oxide p hr of 0.05pbw.In one embodiment, vulcanisable compound does not contain zinc oxide.
In one embodiment, vulcanisable compound comprises magnesium oxide, its amount is for about 0 to about 0.8pbw magnesium oxide phr, be about 0.1 to about 0.75pbw magnesium oxide phr in other embodiments, being about 0.2 to about 0.5pbw magnesium oxide phr in another embodiment, is about 0.25 to about 0.38pbw magnesium oxide phr in another embodiment.
In certain embodiments, vulcanisable compound comprises the magnesium oxide phr less than about 0.75pbw, in other embodiments less than the magnesium oxide phr of about 0.5pbw, in other embodiments less than the magnesium oxide phr of about 0.38pbw, in other embodiments less than the magnesium oxide phr of 0.3pbw, in other embodiments less than the magnesium oxide phr of 0.2pbw, in other embodiments less than the magnesium oxide phr of 0.15pbw, in other embodiments less than the magnesium oxide phr of 0.10pbw, in other embodiments less than the magnesium oxide phr of 0.05pbw.In one embodiment, vulcanisable compound does not contain magnesium oxide.
In one embodiment, vulcanisable compound comprises about 0 to about 0.6pbw sulphur phr, about 0.05 to about 0.55pbw sulphur phr in another embodiment, and about 0.08 to about 0.25pbw sulphur phr in another embodiment, and about 0.1 to about 0.13pbw sulphur phr in another embodiment.
In these or other embodiment, vulcanisable compound comprises the sulphur phr less than about 0.75pbw, in other embodiments less than the sulphur phr of 0.6pbw, in other embodiments less than the sulphur phr of 0.55pbw, in other embodiments less than the sulphur phr of about 0.45pbw, in other embodiments less than the sulphur phr of about 0.40pbw, in other embodiments less than the sulphur phr of about 0.35pbw, in other embodiments less than the sulphur phr of about 0.25pbw, in other embodiments less than the sulphur phr of about 0.13pbw, in other embodiments less than the sulphur phr of about 0.10pbw, in other embodiments less than the sulphur phr of about 0.07pbw, in other embodiments less than the sulphur phr of about 0.05pbw.In one embodiment, vulcanisable compound does not contain sulphur.
In one or more embodiments, mention the total cure agent addition that to vulcanize in the inside liner composite.This total cure agent addition refers to sulfur crosslinking agent and comprises the total amount of zinc oxide and magnesian metal oxide cross-linked agent.In one or more embodiments, the total cure agent addition in the inside liner vulcanisable compound of the present invention is about 0.05 to about 1.5phr.In these or other embodiment, total cure agent addition in the inside liner vulcanisable compound is less than 1.8pbw vulcanizator phr, in other embodiments less than 1.5pbw vulcanizator phr, in other embodiments less than 1.3pbw vulcanizator phr, in other embodiments less than 1.2pbw vulcanizator phr, in other embodiments less than 1.1pbw vulcanizator phr, in other embodiments less than 1.0pbw vulcanizator phr, in other embodiments less than 0.9pbw vulcanizator phr, in other embodiments less than 0.8pbw vulcanizator phr.
In one or more embodiments, the amount of zinc oxide can be calculated based on vulcanizing the Number of Halogen Atoms that exists in the inside liner composite.In one or more embodiments, can vulcanize the Number of Halogen Atoms that the Number of Halogen Atoms that exists in the inside liner composite represents to be connected to halogenated rubber.More specifically, in one embodiment, the zinc oxide molecular number of existence approximates greatly half that can vulcanize the Number of Halogen Atoms that exists in the inside liner composite.The zinc oxide weight that those skilled in the art can will add based on the known information calculations that comprises mol wt and avogadros constant.
In one or more embodiments, the amount of sulfur crosslinking agent can be calculated based on the double key number that can vulcanize in the inside liner composite.More specifically, the sulfur crosslinking agent molecular number of existence approximates greatly half that can vulcanize the double key number that exists in the inside liner composite.Double key number can be determined by means known in the art.The sulfur crosslinking agent weight that those skilled in the art can will add based on the known information calculations that comprises mol wt and avogadros constant.
In one or more embodiments, mention the stoichiometry equivalent of vulcanizator.The amount of this vulcanizator is can come the required theoretical crosslinking agent of complete cross-linked rubber with crosslink sites by consuming all.Because cross bond (crosslink) forms between two crosslink sites, so a molecule of crosslinking agent and the reaction of a pair of crosslink sites form cross bond.In other words, the ratio of vulcanizator molecule and a pair of crosslink sites is that to consume in theory all crosslink sites needed.
In one or more embodiments, but be halogenated butyl rubber for the preparation of the polysulphide rubbers of inside liner composite, it comprises halogen atom and two keys at each crosslink sites place.Therefore, crosslink sites can react with metallic oxide or sulfur vulcanization agent.But comprise at polysulphide rubbers in the situation of natural rubber that crosslink sites comprises two keys, it can react with the sulfur vulcanization agent.Therefore, but include only at polysulphide rubbers in the situation of halogenated butyl rubber, the stoichiometry equivalent of vulcanizator will be based on metallic oxide and sulphur.But comprise at polysulphide rubbers in the situation of halogenated butyl rubber and natural rubber that the stoichiometry equivalent of sulphur can distribute between natural rubber and halogenated butyl rubber.
Because the rubber for the preparation of tire flap layer composition of the present invention comprises unsaturated rubber and/or halogenated rubber, two keys that those skilled in the art will understand in the unsaturated rubber are crosslink sites of sulfur vulcanization agent, and this sulfur vulcanization agent can form the sulfur-bearing cross bond between a pair of pair of key.Equally, the halogen atom of halogen atom or halogenated rubber is metallic oxide such as zinc oxide or magnesian crosslink sites, when the cracking halogen atom, forms directly crosslinked between two crosslink sites.
In one or more embodiments, but comprise at polysulphide rubbers in the situation of natural rubber and halogenated butyl rubber, will be less than the vulcanizator of the stoichiometry equivalent of 100 % by weight for the preparation of vulcanisable compound of the present invention.That is, based on 1/2 of sulfuration site sum in the rubber that whenever will vulcanize, use the vulcanizator less than 1 molecule.In one or more embodiments, less than 90%, in other embodiments less than 80%, in other embodiments less than 70%, in other embodiments less than 60%, in other embodiments less than 50%, in other embodiments less than 40%, in other embodiments less than 30%, in other embodiments less than 20%, in other embodiments less than the vulcanizator of 10% stoichiometry equivalent for the preparation of the inside liner composite that vulcanizes of the present invention.
In one or more embodiments, but comprise at polysulphide rubbers in the situation of halogenated butyl rubber, will be less than the vulcanizator of the stoichiometry equivalent of 180 % by weight for the preparation of vulcanisable compound of the present invention.That is, based on 1/2 of sulfuration site sum in the rubber that whenever will vulcanize, use the vulcanizator less than 1.8 molecules.In one or more embodiments less than 180%, in other embodiments less than 170%, in other embodiments less than 160%, in other embodiments less than 150%, in other embodiments less than 140%, in other embodiments less than 130%, in other embodiments less than 120%, in other embodiments less than 110%, in other embodiments less than the vulcanizator of 100% stoichiometry equivalent for the preparation of the inside liner composite that vulcanizes of the present invention.
In one or more embodiments, advantageously find: the aggregate level of the vulcanizator that uses in can vulcanizing the inside liner composite (for example sulphur, MgO and ZnO) can be determined with reference to the Number of Halogen Atoms in halogenation (for example halobutyl) rubber components.The technology that should be used for determine the vulcanizator aggregate level can be used for rubber components wherein comprise 100 % by weight halogenated rubbers or wherein rubber components comprise those vulcanisable compounds of the blend of halogenated rubber and non-halogenated rubber.Comprise at rubber components in the situation of blend, find: the vulcanizator level can be except with reference to considering that the distribution of vulcanizator between halogenated rubber and non-halogenated rubber determine that the distribution between this halogenated rubber and the non-halogenated rubber is determined with weight basis based on the relative weight percentum of halogenated rubber and non-halogenated rubber the situation of non-halogenated rubber.In a plurality of embodiments, this technology is used for comprising the vulcanisable compound of rubber components, this rubber components comprises at least 50 % by weight, at least 60 % by weight in other embodiments, at least 70 % by weight in other embodiments, at least 80 % by weight in other embodiments, at least 90 % by weight halogenated rubbers (for example halogenated butyl rubber) in other embodiments are based on the total weight of rubber components.
According to these embodiments, with the common consistent mode of above-mentioned those embodiments, determine the mol ratio between the right molal quantity of the molal quantity of vulcanizator and the crosslinkable on the halogenated rubber.The right molal quantity of crosslinkable that also can be described as potential cross bond (potential crosslink) comprises based on every potential mole cross bond or crosslinkable being two moles of crosslink sites.As mentioned above, the crosslink sites in the halogenated rubber comprises two keys and halogen atom.Because each site has dual degree of functionality, so can form cross bond with sulphur or metallic oxide.Because the double key number in the halogenated rubber equals Number of Halogen Atoms (at least for complete halogenated rubber), so the crosslink sites sum can be determined from the halogen atom sum is simple.Certainly, the halogen atom sum can be determined based on the weight stoichiometry ground of halogen.Because two crosslink sites form crosslinkable to or potential cross bond, so crosslinkable to or the molal quantity of cross bond be 1/2 of halogen atom sum.Surprisingly, these calculating have confirmed it is useful, even make for example vulcanizator distribution of multiple hypotheses: only have a sulphur atom to participate in each cross bond, with only have a cross bond to form (even these sites have dual degree of functionality and can form in theory two cross bonds) at every loci place, and other apparent hypothesis for those skilled in the art.
Therefore, in these embodiments, the vulcanizator total amount (is sulphur, the molal quantity of MgO and ZnO) with the crosslinkable of halogenated rubber to or the mol ratio of the molal quantity of potential cross bond can be up to 1.8: 1, in other embodiments up to 1.7: 1, in other embodiments up to 1.6: 1, in other embodiments up to 1.5: 1, in other embodiments up to 1.4: 1, in other embodiments up to 1.3: 1, in other embodiments up to 1.2: 1, in other embodiments up to 1.1: 1, in other embodiments up to 1.0: 1, in other embodiments up to 0.9: 1, in other embodiments up to 0.8: 1, in other embodiments up to 0.7: 1.In these or other embodiment, the mol ratio of the molal quantity that the cross bond of vulcanizator total amount and halogen polymer is right can be at least 0.05: 1, in other embodiments at least 0.1: 1, in other embodiments at least 0.2: 1, in other embodiments at least 0.3: 1, in other embodiments at least 0.4: 1, in other embodiments at least 0.5: 1.
In these or other embodiment, total crosslinking agent of use (for example sulphur, zinc oxide and magnesium oxide) amount can be the amount that is enough to reach the sulfuration level, the concrete swollen polymer volume fraction (V of the inside liner composite of the available sulfuration of this sulfuration level
r) characterize.Understand V such as those skilled in the art
rWith sulphurous water straight connect relevant, to such an extent as to V for example
rAlong with the sulphurous water pancake is low and reduce.In one or more embodiments, comprise the maximum V that will reach sulfuration inside liner sample for the preparation of the vulcanizator total amount of inside liner composite of the present invention
rSulfuration dosage or lower, described maximum V
rBe lower than 0.15, be lower than in other embodiments 0.14, be lower than in other embodiments 0.13, be lower than in other embodiments 0.12, be lower than in other embodiments 0.11, be lower than in other embodiments 0.10, be lower than in other embodiments 0.9, be lower than in other embodiments 0.8, be lower than in other embodiments 0.7, be lower than in other embodiments 0.6, be lower than in other embodiments 0.5.
In one or more embodiments, polymer volume mark (V
r) can determine in the following manner: the polysulphide rubbers sample is placed solvent, make thus swell rubber, then after the specified time amount, measure the weight of swollen rubber.Weigh behind the swollen rubber, this sample drying is also weighed again to remove solvent.An available concrete grammar comprises rubber sample is placed two ounces wide-mouth bottle and about 1-1.5g that weighs.Before sample is placed wide-mouth bottle, measure example weight in 0.0001g.Cyclohexane is added wide-mouth bottle, until wide-mouth bottle whole about 66%.Then wide-mouth bottle is sealed.After 24 hours, remove the cyclohexane that is absorbed by rubber, and replace with fresh cyclohexane.This sample was soaked 48 hours in the cyclohexane of replacing at least again.After altogether more than 72 hours, cyclohexane is poured out from wide-mouth bottle, simultaneously sample is remained in the wide-mouth bottle.Then this wide-mouth bottle is resealed, simultaneously sample is transferred to balance, sample is taken out from wide-mouth bottle, blot gently with paper handkerchief on its surface, this sample is positioned in the weighing pan of uncovered (teared), and this swelling sample of weighing is extremely near 0.0001g.After weighing, sample is placed the aluminium dish, and dry 1-2 hour of air.Then sample is placed the vacuum furnace under 50 ℃, to realize about constant weight more than 24 hours.Then weigh sample and be recorded as dry weight.
In the situation of these measurements, V
rCan be based on following calculating.At first, the weight fraction of the interior solubility thing of concrete sample calculates from rubber compounding (that is, based on the composition in the discussion rubber compounding).Soluble material in the prescription comprises oil and hydrocarbon resin.Those skilled in the art can recognize other soluble materials in the various prescriptions.From this weight fraction, get rid of the amount of potential soluble polymer.Then, theory of computation dry sample weight, its initial sample weight that equals before the swelling multiply by (weight fraction of 1-solubility thing).Then, the excessive solubility thing weight that adopts as soluble polymer deducts actual sample weight by the theoretical dry sample weight after swelling and calculates.As the amount of soluble polymer after the swelling of total blend mark based on excessive solubility thing weight divided by swelling before initial sample weight determine.The initial polymer weight fraction of blend calculates divided by the umber of total blend based on per 100 rubber with the initial umber of Polymers in per 100 rubber.Then, insoluble polymer weight fraction (before the swelling) can deduct in the blend soluble polymer weight fraction by initial polymer weight fraction from blend and determines in the blend.It should be understood that after the swelling that polymer weight equals insoluble polymer weight in the swelling blend in the dry blend.This value can be determined by initial sample weight being multiply by in the blend insoluble polymer weight fraction.It will also be appreciated that polymer volume in the dry blend equals the polymer volume in the swelling blend.For the sample that contains a kind of poly-mer, it equals in the dry blend polymer weight divided by density polymer.For two kinds of blend polymers, polymer volume in the dry blend equals: the weight fraction of the first poly-mer is divided by the density of the first poly-mer in the front initial sample of swelling, add before the swelling in the initial sample weight fraction of the second poly-mer divided by the density of the second poly-mer, and this summation be multiply by polymer weight in the dry sample.The density of for example, getting brombutyl (BIIR) is that the density of 0.93g/ml and natural rubber is 0.92g/ml.Weight of solvent in the swollen polymer can be determined by deducting dry sample weight from the swelling example weight.Solvent volume in the swelling sample can be by determining weight of solvent that wherein getting cyclohexane density is 0.774g/ml divided by solvent density.Finally, V
rThat polymer volume adds solvent volume sum in the swelling sample divided by polymer volume in the dry sample in the dry sample.As known in the art, the aviation value of test of many times can be for increasing measuring accuracy.Surpass for the blend of two kinds of poly-mers for containing, the rubber volume with two kinds of poly-mers add with the item number that provides " which " poly-mer and the ratio of himself density with calculate.
In one or more embodiments, the rubber components that can vulcanize the inside liner composite can comprise the poly-mer of one kind of multiple crosslinkables or sulfuration; These poly-mers can be described as rubber-like polymer or elastic body.In one or more embodiments, rubber-like polymer is selected based on its hypotonicity to gas, good damping property, good resistance to effect of heat, good chemical resistance, good ozone resistants and good inoxidizability.In one or more embodiments, can vulcanize the inside liner composite and can comprise the isobutylene type elastic body.These elastic bodys can use separately or use with other elastic body combinations.Other elastic bodys can comprise natural and synthetic elastomer.
The isobutylene type elastic body comprises polyisobutene homopolymer, isobutylene/isoprene copolymer and halide derivative thereof.The isobutylene type elastic body further comprises halogenated isobutylene-p-methylstyrene copolymer.Isobutylene type elastic body and halide derivative thereof are called " butyl rubber " and " halogenated butyl rubber " sometimes.
The butyl rubber that is obtained commercially comprises poly-(metering system-co-2-methyl isophthalic acid, 3-butadidenne) and poly-(isobutylene-co-isoprene).
In one or more embodiments, butyl rubber is by preparing butylene and isoprene copolymer.The relative quantity of these monomers will determine the molar percentage degree of unsaturation of gained copolymer.In other words, the isoprene molar percentage in the copolymerization will be corresponding to the molar percentage degree of unsaturation in the copolymer.In one or more embodiments, the isobutylene type elastic body can have the molar percentage degree of unsaturation and be lower than approximately 3, is lower than in other embodiments approximately 2.5, is lower than in other embodiments about 2.
Halogenated butyl rubber can comprise neoprene based rubber (CIIR), brombutyl rubber (BIIR) or its compound.In one or more embodiments, halogenated butyl rubber can comprise about 0.5 halogen atom to about 5 percentage by weights, about 0.7 halogen atom to about 4 percentage by weights in other embodiments, about 1 halogen atom to about 3 percentage by weights in other embodiments is based on the total weight of halogenated butyl rubber.
In one or more embodiments, the rubber components of vulcanisable compound comprises about 60 to about 100 percentage by weights, or about 80 halogenated butyl rubbers to about 100 percentage by weights in other embodiments.In other embodiments, in rubber components, use about 80 to about 100phr halogenated butyl rubber.In one or more embodiments, at least 80 % by weight of vulcanisable compound, at least 90 % by weight in other embodiments, at least 95 % by weight in other embodiments, the rubber components of at least 99 % by weight comprises halogenated rubber (for example halogenated butyl rubber) in other embodiments.
In one or more embodiments, vulcanisable compound further comprises natural rubber.In one embodiment, natural rubber exists with about 0 amount to about 60 percentage by weights (wt.%) of prescription rubber components total amount, about 0 of about rubber components total amount to about 40 percentage by weights in other embodiments, and 0 of about rubber components total amount to about 20 percentage by weights in other embodiments.In another embodiment, about 5 of prescription rubber components total amount to about 50 percentage by weights (wt.%) be natural rubber.
In one or more embodiments, the vulcanisable compound that uses among the present invention comprises halogenated butyl rubber and natural rubber.In one or more embodiments, the weight ratio of halogenated butyl rubber and natural rubber can be at least 1: 1, in other embodiments at least 2: 1, in other embodiments at least 4: 1, in other embodiments at least 7: 1, in other embodiments at least 8: 1, in other embodiments at least 8.5: 1, in other embodiments at least 9.0: 1.In these or other embodiment, the weight ratio of halogenation-butyl rubber and natural rubber can be lower than 9.8: 1, is lower than in other embodiments 9.5: 1, is lower than in other embodiments 9.0: 1.
In one or more embodiments, but vulcanizate compositions comprises processing returns (process returns), and it is included in the interior glue of scrapping by the acquisition of various sources of manufacturing equipment.In one embodiment, the processing returns can account for vulcanisable compound total rubber component about 0 to about 50 (or in other embodiments about 5 to about 25) percentage by weight (wt.%).
In one or more embodiments, can vulcanize the inside liner composite and can comprise that synthetic polymer is such as but not limited to synthetic polyisoprenes, poly-butadiene, polyisobutene-co-isoprene, poly-chloroprene rubber, poly-(ethene-co-propylene), poly-(styrene-co-butadidenne), poly-(styrene-co-isoprene) and poly-(styrene-co-isoprene-co-butadidenne), poly-(isoprene-co-butadidenne), poly-(ethene-co-propylene-co-diene), thiokol, acrylic rubber, poly-urethane rubber, silaatic and epichlorohydrin rubber.In one or more embodiments, these synthetic polymers can use as rubber separately, to form the rubber components of vulcanisable compound.In other embodiments, they can use with isobutylene type rubber, to form the rubber components of vulcanisable compound.In other embodiments, synthetic polymer can be used in combination with isobutylene type poly-mer and natural rubber, to form the rubber components of vulcanisable compound.
Spendable other compositions comprise accelerator, oil, wax, scorch retarder, processing aid, zinc oxide, tackifier, enhancing resin, aliphatic acid such as stearic acid, peptizer, atiozonant and one kind of multiple extra rubber.
Spendable filler comprises inorganic filler and organic filler.Organic filler can comprise carbon black and starch.Inorganic filler can comprise clay of silicon dioxide, aluminium hydroxide, magnesium hydroxide, clay (aluminosilicate of hydration), chemical functionalization and composition thereof.In specific embodiments, filler comprises non-enhancing or coarse black.As known in the art, these carbon black fillers can be that generally being classified as than the N 300 by AS TM D-1765 is more those of coarse grain (for example N550) of carbon black.In one or more embodiments, can vulcanize the inside liner composite and comprise filler total amount level about 30 to about 100pbw, about 50 to about 80pbw in other embodiments, and about 55 to about 75pbw phr in other embodiments.
The present composition can be by using the preparation of normal compound technology.In one or more embodiments, rubber composition can comprise that the initial masterbatch of rubber components and filler prepares by formation.This initial masterbatch can about 25 ℃ to about 125 ℃ initial temperature, about 135 ℃ mixing to about 180 ℃ dump temperature.In order to prevent prevulcanization (also becoming incipient scorch), this initial masterbatch can not comprise vulcanizator.In case the processing initial masterbatch can be introduced vulcanizator and be blended at low temperatures initial masterbatch in final mix stage, it does not preferably cause curing process.Randomly, extra mix stage is sometimes referred to as again refining, and it can adopt between masterbatch mix stage and final mix stage.The stage of refining can add various compositions again at this.Rubber compounding technology and use therein additive are disclosed in Stephens, The Compounding andVulcanization of Rubber, in Rubber Technology (the 2nd edition, 1973).
In one or more embodiments, tire liner prepared according to the methods of the invention has the good combination that comprises permeability to air, flexible resistance, pulling strengrth and adhering character.
In one or more embodiments, when comparing with the oxygen permeability of tire liner by using the preparation of a large amount vulcanizator more, the oxygen permeability of tire liner prepared in accordance with the present invention is identical or slightly increase.
In one or more embodiments, the adhesiveness of tire liner prepared in accordance with the present invention unexpectedly can be compared with the adhesiveness of the inside liner of the excessive vulcanizator preparation of the use implemented in the prior art.In specific embodiments, when comparing with the adhesiveness of tire liner by using the preparation of a large amount vulcanizator more, the adhesiveness of tire liner prepared in accordance with the present invention increases.
In one or more embodiments, when with when using as comparing fatigue life of the tire liner of the vulcanizator preparation of the disclosed more a large amount of prior art, increase fatigue life of tire liner prepared in accordance with the present invention.Unexpectedly, in the situation that adhesiveness is not had technical deleterious effect, obtain the fatigue life of increase.
Experiment
Sample 1-10
To also can be described as the various rubber composition preparations of inside liner prescription, sulfuration, and for the test of thinking in the important characteristic of inside liner.Each prescription comprises 100 weight portions (pbw) rubber, 60pbw carbon black, 8pbw processing oil, 2pbw stearic acid, 7pbw hydrocarbon resin, 4pbw phenol resin and 1.25pbw vulcanization accelerator phr.Sulphur, zinc oxide and magnesian level are as changing described in the following table.In addition, this table shows the rubber type that uses.The rubber that uses comprise have about 2 % by weight halogenated rubbers (BIIR), natural rubber (NR) and/or synthetic poly-(styrene-co-butadidenne) (SBR).One-tenth component described in the table is reported with weight portion.
Each prescription uses that normally used conventional two stage mixing technologies prepare in the field of preparation tyre assembly rubber compounding in laboratory scale inner mixing roll.Generally speaking, zinc oxide, sulphur and vulcanization accelerator are introduced into prescription and mixing in the second mix stage, it carries out being lower than otherwise can causing under the temperature of temperature of harmful initiation sulfuration.
Then will fill a prescription in two roller mills compressing tablet to thickness about 0.075 inch or as be used for the required thickness of concrete mould of concrete test.For some test, sheet material vulcanized 55 minutes under 300 °F in hydraulic compressor.Depend on test specification, cut (dye-cut) for intended shape with specimen is dried.In the situation of adhesiveness test, in case consist of sample, sulfuration just comes into force.
The prescription details of using among the table 1 sampling 1-10, and the test result of carrying out.
Monsanto is used in endurance failure test (f2f)
TM" Fatigue to Failure " tester carries out, and promotes test thereby this tester has No. 24 cams of 100 circulations of per minute running to change specimen.About 3 inches long of specimen, about 0.5 inch wide at its widest width place, and about 0.06 inch.This sample is generally dumb-bell shape or dog bone shape, has about 1.13 inches long and about 0.13 inch wide of center test area.Sample edge (along 0.5 inch edge) comprises having the rib that is generally ring shaped cross-section that extends along the edge, thereby helps to guarantee that sample can fully be supported in test equipment.This test is passed through Mylar
TMRectangular sheet (0.5 inch * 1 inch) is bonded on the sample both sides and promotes in the position of test equipment clamping near the sample of rib.In other words, four Mylar of every sample application
TM, two in the top side, and two in the bottom side.Mylar
TMThe stickup of sheet effectively reduces by 1.13 inches test area to about 0.5 inch long.
Oxygen permeability (O
2Perm) by using Mocon
TMOxtran 2/61 test machine utilization and the similar method of ASTM D-3985 are carried out.Generally speaking, polysulphide rubbers sample (about 0.03 inch) is used to form the baffle plate between two gas zone or chamber.The first Room that is under 65 ℃ comprises the zero gas (zero-grade air) of blowing over rubber sample one side with 125ml/min.Being in equally another chamber under 65 ℃ comprises with 35ml/min and blows over the nitrogen of rubber sample and the compound of hydrogen (2%).Be positioned at this indoor exhaust gas oxygensensor that comprises nitrogen/hydrogen blend and detect the oxygen level that penetrated rubber sample.Detected oxygen amount is reported as the volume of per unit length time per unit, as is expressed as cm
3/ cmsec, it equals cm
2/ sec.
The adhesiveness test is undertaken by about one inch wide * about four inches long specimen of structure.Specimen is five layers of sample, it comprise with by the adjacent supporting layer of sample prescription test layer in blocks (it is hot rolling (calendared) fabric), this supporting layer and mesh fabric are adjacent, the rubber sheet that is produced by rubber compounding of moulding is adjacent after this mesh fabric and the carcass ply layer formula, this rubber sheet be adjacent with the supporting layer of direct adjacent with the sample rubber compounding similar hot rolling fabric of supporting layer.This laminate structure that comprises two-layer rubber (i.e. not sulfuration) rubber was vulcanized 55 minutes under 300 °F in hydraulic compressor.The layer of representative sample inside liner pulls open with the rate of extension of 50.8mm/ per minute with the layer that represents casingply.The power that these layers are pulled open (produce separate in mesh layer) is with the energy record of per unit face area, and it is lbin/per square inch, equal pound/per inch.Test is carried out under 25 ℃ and 100 ℃.
Table 1 also provides the mol ratio of vulcanizator total amount (zinc oxide, sulphur and magnesium oxide do not comprise accelerator) with the molar weight in the interior sulfuration of BIIR site.As discussing in this specification sheets, comprise at rubber components in the situation of multiple rubber, suppose that the amount of the vulcanizator that is allocated in BIIR equals the weight ratio of BIIR and other rubber components (for example natural rubber and buna-S).For example, for the sample that comprises 60%BIIR and 40% natural rubber, 60 % by weight vulcanizators are allocated in BIIR.
Table 1 also provides the crosslink density of polysulphide rubbers sample, based on using the polymer volume mark (V that said method is determined in the literary composition
r).For unaged sample, at room temperature, be similar to ASTM D-412 and determine 100% modulus.
Sample 11-16
Use and six other samples described in the above-mentioned similar method preparation table 2 of method for sample 1-10.The zinc oxide level of these samples remains on 0.38pbw phr.Test is used and is carried out for the consistent method of the method for sample 1-10 with above-mentioned equally.
Sample 17-21
Use and other 5 samples described in the above-mentioned similar method preparation table 3 of method for sample 1-10.The zinc oxide level of these samples remains on 0.75pbw phr.Test is used and is carried out for the consistent method of the method for sample 1-10 with above-mentioned equally.
Sample 22-33
Use and other 12 samples described in the above-mentioned similar method preparation table 4 of method for sample 1-10.The zinc oxide level of these samples remains on 1.5pbw phr, and the magnesium oxide level remains on 0.111pbw phr.Test is used and is carried out for the consistent method of the method for sample 1-10 with above-mentioned equally.
Sample 34-36
Use and other 3 samples described in the above-mentioned similar method preparation table 5 of method for sample 1-10.The zinc oxide level of these samples remains on 1.5pbw phr, and simultaneous oxidation magnesium changes.Test is used and is carried out for the consistent method of the method for sample 1-10 with above-mentioned equally.
For those skilled in the art, it all will be apparent not departing from the various improvement of the scope of the invention and spirit and changing.The present invention never is limited to the illustrative embodiment described in the literary composition.
Claims (16)
1. method for the preparation of the green tire inside liner, the method comprises:
But with one or more polysulphide rubbers shaped polymers, be lower than 0.75 part by weight of zinc oxide, be lower than 0.75 weight portion magnesium oxide and be lower than 0.75 weight portion sulphur and mix, based on per 100 parts by weight of rubber, but to form cured blend; With
This compound is extruded to form the green tire inside liner.
2. method according to claim 1, but wherein said polysulphide rubbers shaped polymer comprises butyl rubber, halogenated butyl rubber or its compound.
3. method according to claim 2, but wherein said polysulphide rubbers shaped polymer comprises the halogenated butyl rubber that contains 1 to 3 percentage by weight halogen, based on the total weight of halogenated butyl rubber.
4. method according to claim 1, but wherein said polysulphide rubbers shaped polymer comprises the halogenated butyl rubber of 60 to 100 percentage by weights and the natural rubber of 0 to 40 percentage by weight, but based on the total weight of polysulphide rubbers shaped polymer.
5. method according to claim 1, wherein said compound comprises the sulphur that is lower than 0.55 weight portion, based on per 100 parts by weight of rubber.
6. method according to claim 1, wherein said compound comprises the magnesium oxide that is lower than 0.5 weight portion, based on per 100 parts by weight of rubber.
7. method according to claim 1, it further comprises by utilizing the green tire inside liner to make up the step of green tire.
8. method according to claim 1, wherein said sulphur, zinc oxide and magnesian total weight are less than 1.2 weight portions, based on per 100 parts by weight of rubber.
9. method according to claim 1, wherein said sulphur, zinc oxide and magnesian total weight are less than 1.8 weight portions, based on per 100 parts by weight of rubber.
10. method according to claim 7, it further comprises the step of vulcanizing described green tire.
11. method according to claim 1, but wherein said polysulphide rubbers shaped polymer comprise halogenated rubber and wherein vulcanizing system comprise that one or more are selected from the vulcanizator in the group that is comprised of sulphur, magnesium oxide and zinc oxide, wherein sulphur adds that magnesium oxide adds that the mol ratio of the molal quantity that the total amount of zinc oxide and the crosslinkable on the described halogenated rubber are right is 0.05: 1 to 1.8: 1; With described compound is extruded to form the green tire inside liner.
12. method according to claim 11, the mol ratio of the molal quantity that the crosslinkable on wherein said vulcanizing system and the halogenated rubber is right are 0.1: 1 to 1.5: 1.
13. method according to claim 11, the mol ratio of the molal quantity that the crosslinkable on wherein said vulcanizing system and the halogenated rubber is right are 0.2: 1 to 1.0: 1.
14. method according to claim 11, the mol ratio of the molal quantity that the crosslinkable on wherein said vulcanizing system and the halogenated rubber is right are 0.3: 1 to 0.9: 1.
15. method according to claim 7, wherein said green tire inside liner comprises the rubber composition of at least part of sulfuration, and wherein said rubber composition is characterised in that swollen polymer volume fraction V
rBe lower than 0.15.
16. method according to claim 15, wherein said rubber composition are characterised in that swollen polymer volume fraction V
rBe lower than 0.13.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US87776506P | 2006-12-29 | 2006-12-29 | |
| US60/877,765 | 2006-12-29 | ||
| US96721507P | 2007-08-31 | 2007-08-31 | |
| US60/967,215 | 2007-08-31 | ||
| PCT/US2007/026390 WO2008082592A2 (en) | 2006-12-29 | 2007-12-28 | Tire innerliner |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310054867.0A Division CN103121379B (en) | 2006-12-29 | 2007-12-28 | Tire innerliner |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101636283A CN101636283A (en) | 2010-01-27 |
| CN101636283B true CN101636283B (en) | 2013-03-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200780048892.0A Expired - Fee Related CN101636283B (en) | 2006-12-29 | 2007-12-28 | Tire innerliner |
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| CN (1) | CN101636283B (en) |
| ES (1) | ES2355772T3 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103303066B (en) * | 2013-07-12 | 2015-11-18 | 江苏通用科技股份有限公司 | Bevelled edge type liner layer structure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1500678A1 (en) * | 2002-04-18 | 2005-01-26 | Bridgestone Corporation | Rubber composition for inner liner and tire |
| EP1543998A1 (en) * | 2003-12-17 | 2005-06-22 | The Goodyear Tire & Rubber Company | Tire with innerliner for prevention of vapor permeation |
| CN1715318A (en) * | 2004-06-28 | 2006-01-04 | 固特异轮胎和橡胶公司 | Pneumatic tire having an innerliner comprised butyl rubber and dispersion of pre-cured diene-based rubber |
-
2007
- 2007-12-28 CN CN200780048892.0A patent/CN101636283B/en not_active Expired - Fee Related
- 2007-12-28 ES ES07868068T patent/ES2355772T3/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1500678A1 (en) * | 2002-04-18 | 2005-01-26 | Bridgestone Corporation | Rubber composition for inner liner and tire |
| EP1543998A1 (en) * | 2003-12-17 | 2005-06-22 | The Goodyear Tire & Rubber Company | Tire with innerliner for prevention of vapor permeation |
| CN1715318A (en) * | 2004-06-28 | 2006-01-04 | 固特异轮胎和橡胶公司 | Pneumatic tire having an innerliner comprised butyl rubber and dispersion of pre-cured diene-based rubber |
Non-Patent Citations (1)
| Title |
|---|
| JP特开平9-132005A 1997.05.20 |
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| ES2355772T3 (en) | 2011-03-30 |
| CN101636283A (en) | 2010-01-27 |
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