CN104602911A

CN104602911A - Construction comprising tie layer

Info

Publication number: CN104602911A
Application number: CN201280075602.2A
Authority: CN
Inventors: J·K·M·科恩; M·B·罗德格斯; P·C·香农; A·H·邹; 原祐一; 柴田宽和; 添田善弘
Original assignee: Yokohama Rubber Co Ltd; Exxon Chemical Patents Inc
Current assignee: Yokohama Rubber Co Ltd; ExxonMobil Chemical Patents Inc
Priority date: 2012-09-06
Filing date: 2012-09-06
Publication date: 2015-05-06
Also published as: EP2892722A1; JP6238990B2; JP2015533687A; RU2610511C2; IN2015DN02472A; CA2883887C; CA2883887A1; WO2014039043A1; RU2015112290A

Abstract

A layered structure suitable for use in a pneumatic tire as an innerliner is prepared by directly bonding a fluid permeation prevention film and an adhesive tie layer together. Prior to bonding the two layers, the fluid permeation prevention layer is treated to remove any residual plasticizers or oils on the surface of the film. The tie layer comprises a mixture of 100 weight % of at least one halogenated isobutylene containing elastomer and about 1 to about 20 parts per hundred (phr) of at least one tackifier. The fluid permeation prevention film comprises an elastomeric component dispersed in a vulcanized or partially vulcanized state, as a discontinuous phase, in a matrix of the thermoplastic resin component. The two layers of the layered structure may be separately extruded and then adhered to each other or adhered to each other during a calendering operation wherein the adhesive tie layer composition is coated onto the treated film.

Description

Comprise the structure of tack coat

The cross reference of related application

This application claims the PCT application PCT/US2005/38705 submitted on October 27th, 2005, and the rights and interests of U.S. Patent application 12/091,608 submitted on October 26th, 2006, these two sections of documents are by reference to being incorporated herein.

Technical field

The present invention relates to and can be used for sandwich construction, such as tire construction, the composition of the tire tack coat particularly between liner and carcass.Especially, the present invention relates to the elastomer using halogenation containing isobutene, optionally at the elastomer had containing homodiene or rubber, such as, in the blend of natural rubber (NR) and styrene butadiene ribber (SBR), halogenation is used to contain the elastomeric rubber composition of isobutene.

Background technology

In order to prevent tyre cord from piercing through, namely enhancing tyre cord penetrates the situation of inner liner, and causes gas leakage and tyre failure, and conventional means adds cushion between the casing ply containing textile or all-steel cord and inner liner.This cushion has been called adhesive glue, tack coat, damping blend or liner backing layer, and generally includes the blend of natural rubber (NR) and SBR styrene butadiene rubbers (SBR).For the present invention, this tyre assembly is called " tack coat ".Usually, the composition of tack coat is similar to the composition of casing ply blend to provide the structure viscosity of necessity to maintain uncured or under " rubber " state coherent tire construction, to solidify adhesiveness and gratifying dynamic property during tire applications.But NR and SBR is highly permeable rubber.Therefore, will thicker cross section be required in case reduce air through this layer permeability and therefore maintain tire pressure.In order to by using thin, height impermeability liner to realize tire gross weight and reduce, the means reducing tack coat tranverse sectional thickness must be found.

U.S. Patent number 5,738,158 disclose a kind of pneumatic tire with air permeation prevention layer or inner liner, described air permeation prevention layer or inner liner are made up of the film of the resin combination comprising at least 20wt% thermoplastic polyester elastomer, described thermoplastic polyester elastomer is made up of the block copolymer of polybutylene terephthalate (PBT) and polyoxyalkylene imidodicarbonic diamide diacid, and the weight ratio of wherein polybutylene terephthalate (PBT)/polyoxyalkylene imidodicarbonic diamide diacid is 85/15 or lower.Resin combination may further include the rubber grain of dispersion, wherein said rubber grain dynamic vulcanization.Resin combination is used to be developed further by each inventor of common assignee as the design of inner liner; see such as; U.S. Patent number 6; 079; 465, described Patent request protection comprises the pneumatic tire of this kind of liner and discloses the application of various thermoplastic resin for described composition.Described patent also discloses exists tack coat with another layer with the bonding promoting inner liner in general structure or bonding strength.The further exploitation of this technology sticks to U.S. Patent number 6,062 to improve inner liner in described structure, is described, wherein controls melt viscosity and the solubility parameter of thermoplastic resin component and elastomeric component according to specific mathematical formula in 283.

Disclosed application U.S.2002/0066512 discloses the pneumatic tire comprising casing ply and inner liner, described casing ply comprises the cord flaggy being defined in the penetralia reinforcing cord layer extended between bead part, the cord along tire inner surface that described inner liner is arranged in described casing ply flaggy is inner, cover the substantially whole inner surface of tire, wherein said inner liner is made up of the airtight rubber of the halogenated butyl rubber and/or halogenated isobutylene-p-methylstyrene copolymer that comprise at least 10wt% at its rubber base-material, and the thickness that the cord that described inner liner plays casing ply flaggy from tire inner surface calculates is 0.2-0.7mm.It can be double-deck that described publication also discloses " inner liner " that defined by the rubber layer between tire inner surface and penetralia tyre cord or plies cords, comprises the internal layer of airtight rubber compounding thing and is not the skin of air-locked rubber based on diene.

Or, outer can have identical airtight rubber compounding thing or similar airtight rubber compounding thing, and described blend is described as comprising halogenated butyl rubber and/or halogenated isobutylene-p-methylstyrene copolymer and diene rubber and carbon black (see paragraph 28-34) further in described publication.

Other bibliography valuable comprises: WO 2004/081107, WO 2004/081106, WO 2004/081108, WO 2004/081116, WO 2004/081099, JP 2000238188, EP 01 424 219, U.S. Patent number 6,759,136 and U.S. Patent number 6,079,465.

Summary of the invention

The invention provides by using at least one height impermeability based on the elastomeric solution of isobutene in tack coat; Especially preferred impermeability elastomer is brominated isobutylene-isoprene copolymer (BIIR), that is, brombutyl copolymer.The present invention can be used for the tire adopting Thermoplastic elastomer tire liner composition, described liner composition based on engineering resin, the vulcanized blend of such as polyamide and BIMS (such as, using dynamic vulcanization preparation).Described tack coat and dynamic vulcanization alloy-layer directly adhere to, and can not damage the improvement realized by liner permeability characteristics and without the need to using additional adhesive means to be fixed together by described two layers.

An aspect of disclosure invention is the method forming layer structure, and wherein fluid impervious permeable membrane and adhesive tie layer are directly bonded together.Before by described two layers bonding, process fluid permeation prevention layer is to remove any residual plasticizer on described film surface or oil.Two of a layered structure layer can be extruded individually, then be adhering to each other or be adhering to each other during calendering operation, wherein adhesives layer composition is coated on described treated film.

Disclosure invention any in, at least one halogenation that described tack coat comprises 100wt% is containing the mixture of the elastomer of isobutene and at least one tackifier of about 20 parts of about 1-/100 parts (phr).

Disclosure invention any in, fluid impervious permeable membrane comprises and is dispersed in the elastomeric component in thermoplastic resin component's matrix using sulfuration or partial vulcanization state as discontinuous phase.

The present invention also can be used for that wherein air or liquid retaining layer be combined with another layer other apply, especially when other layer comprises enhancing fiber or cord, such as, require the flexible pipe and other container that keep gas or fluid.

Accompanying drawing is sketched

Fig. 1 is that process DVA film is to remove the schematic diagram of the multi-region baking oven of residual plasticizer;

Fig. 2 is the exemplary calendaring system applying adhesives glue-line; With

Fig. 3 is the simplification viewgraph of cross-section of the tire of the display position of various layer in the tire comprising tack coat.

Detailed Description Of The Invention

The present invention relates to for the rubber composition compared with impermeability tack coat between liner and casing ply to reduce tire weight maintaining airtyred heat resistance, durability and flexible demand simultaneously.The invention still further relates to the durability reducing there is improvement and realize the permeability with the tack coat of the excellent adhesion of casing ply and liner simultaneously.

Polymer can be used to refer to homopolymers, copolymer, interpretation, terpolymer, etc.Similarly, copolymer can refer to comprise at least two kinds of monomers, optionally has the polymer of other monomer.When claiming polymer to comprise monomer, described monomer is present in polymer with the derivative form of the polymerized form of monomer or monomer.But for ease of reference, phrase " comprises described (accordingly) monomer " to be waited as writing a Chinese character in simplified form.Similarly, when catalytic component is described as the neutral stable form comprising described component, it will be understood by those skilled in the art that: the activity form of described component is to produce the form of polymer with monomer reaction.

Isoalkene refers to any olefinic monomers on same carbon with two replacements.Polyene refers to any monomer with two or more double bonds.In a preferred embodiment, polyene anyly comprises two double bonds, and the preferably monomer of two conjugate double bonds, such as conjugated diene is as isoprene.

" elastomer " used herein refers to and defines consistent any polymer or the composition of polymer with ASTM D1566-06.Described term can use interchangeably with term " rubber ".

The present invention relates to and there is one comprise thermoplastic engineering resin's (also referred to as " engineering resin " or " thermoplastic resin ") as continuous phase and sulfuration (or partial vulcanization) the elastomer layer structure as the layer of decentralized photo.This kind of composition is such as called prepared by the technology of dynamic vulcanization by using, and the composition of gained is called dynamic vulcanization alloy (DVA); The details of this kind of composition and method of making the same is described herein.At it in airtyred context, DVA layer serves as tire flap.Generally speaking, this layer will be called air permeation prevention layer or barrier layer, because this layer is the layer with minimum permeability.

Adjacent with air permeation prevention layer is adhesive tie layer, so name be because it DVA liner and the adjacent layer in structure tire bonds-usual, described adjacent layer will be the radial inner surface of casing ply and the radial penetralia coating rubber of casing ply.Tack coat is preferably vulcanisable compound, and usually containing at least one reinforcer and non-essential additive such as processing aid etc., and for the present invention, tack coat comprises the elastomer of halogenation containing isobutene.

According to the present invention, by preparation and/or the process of air permeation prevention layer, adhesive tie layer directly can bond with air permeation prevention layer, and does not require to use intermediary adhesive layer between the two layers.

Fluid permeation prevention layer

Fluid permeation prevention layer is that sheet material or form membrane exist for use in tire construction usually, but also can exist by the tubular layer form in hose construction.Described sheet material or film can be extruded as blowing sheet material or tubular layer or casting film-forming.Cambial either method can obtain having the layer of thickness as required or variable thickness to reach more heavy thickness with it by zones of different corresponding for the various flexure region of the goods be used for wherein.

Fluid permeation prevention layer is formed by DVA as noted, and described DVA has the elastomer being dispersed in sulfuration in thermoplastic engineering resin's continuous phase or partial vulcanization as discrete particle.

Elastomer

The elastomer that can be used for DVA of the present invention is any C ₄-C ₇the elastomer that olefinic monomer is derivative.A kind of such elastomer used in the present invention is usually by making the mixture reaction preparation of monomer, and described mixture at least has (1) C ₄-C ₇olefinic monomer and (2) at least one polyene, monomer component.Described alkene accounts for the 70-99.5wt% of total monomer mixture in one embodiment by weight, in another embodiment, accounts for 85-99.5wt%.Alkene is C ₄-C ₇compound, its limiting examples is compound such as isobutene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 2-methyl-2-butene, 1-butylene, 2-butylene, hexene and 4-methyl-1-pentene.The preferred alkene of the present invention is C ₄-C ₇isoalkene or C ₄-C ₇isomonoolefin.Useful monomer is isobutene, obtains the polymer based on isobutene.In one embodiment, polyene component, with 30-0.5wt%, in another embodiment, is present in monomer mixture with 15-0.5wt%.In still another embodiment, the 8-0.5wt% of monomer mixture is polyene.Polyene is C ₄-C ₁₄polyene is as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, laurene, 6,6-dimethyl-fulvene, hexadiene, cyclopentadiene and pentadiene.Used in the present invention is that isobutene and 0.5-8wt% isoprene by making 92-99.5wt% reacts, or makes 99.5wt%-95wt% isobutene and 0.5wt%-5.0wt% isoprene react the elastomer obtained; This isobutylene-isoprene copolymer (IIR) is commonly referred to butyl rubber/elastomer.

Halogenated rubber is used to be useful in the present invention.Halogenated rubber is normally defined the rubber containing at least about 0.1 % by mole of halogen, and based on total mole of monomer and comonomer, this kind of halogen is selected from bromine, chlorine and iodine.Halogenated rubber used in the present invention comprises the elastomer (halogenated copolymers also referred to as based on isobutene) of halogenation containing isobutene.These elastomers can be described as C ₄-C ₇the random copolymer of the unit that the unit that isomonoolefin derives such as isobutene derives and other polymerizable unit of at least one.In one embodiment of the invention, halogenation is butyl-type rubber or branched butyl type rubber containing the elastomer of isobutene, particularly these elastomeric bromination patterns.Preferred halogenation used in the present invention comprises halogenated butyl rubber, such as brombutyl and chlorinated scoline based on the homopolymers of isobutene or copolymer.

Halogenated butyl rubber is by making the halogenation of above-mentioned butyl rubber product.Halogenation is undertaken by any mode, and the present invention does not limit by Halogenation process at this.The halogenation method of polymer such as butyl polymer is disclosed in U.S. Patent number 3,099, and 644,4,513,116 and 5,681, in 901.In conventional method, in hexane diluent, at 4-60 DEG C, use bromine (Br ₂) or chlorine (Cl ₂) as halogenating agent by halogenating butyl rubber.Halogenated butyl rubber has the Mooney viscosity (ML 1+8,125 DEG C) of about 27-about 51 usually.The normally about 0.1-10wt% of content of halogen, based on the weight of halogenated butyl rubber; Such as, about 0.5-5wt%; Or, the about 2.5wt% of about 0.8-; Such as, the about 2wt% of about 1-.Halogenation used in the present invention is Bromobutyl 2222 (ExxonMobil ChemicalCompany) containing the elastomeric Commercial embodiments of isobutene.The normally about 27-37 of its Mooney viscosity (ML l+8, at 125 DEG C, ASTMD1646-04, revision), and its bromine content is about 1.8-2.2wt%, relative to halogenated elastomer.In addition, Bromobutyl 2222 by manufacturer provide curing characteristics as follows: MH is about 28-40dNm, ML is about 7-18dNm (ASTM D2084-92A).Halogenation used in the present invention is Bromobutyl2255 (ExxonMobil Chemical Company) containing another Commercial embodiments elastomeric of isobutene.Its Mooney viscosity is about 41-51 (ML1+8, at 125 DEG C, ASTM D1646-04), and its bromine content is about 1.8-2.2wt%.In addition, its curing characteristics disclosed in manufacturer is as follows: MH is 34-48dNm, ML is 11-21dNm (ASTM D2084-92A).

Halogenation is halogenation, branching or " star-branched " butyl rubber containing another useful embodiment elastomeric of isobutene.In one embodiment, star-branched butyl rubber (" SBB ") is the composition comprising butyl rubber and polydiene or block copolymer.For the present invention, the method forming SBB is unrestricted.Polydiene, block copolymer or branching agent (hereinafter " polydiene ") normally cationoid reaction, and exist in the polymerization process of butyl or halogenated butyl rubber, or can be blended to form SBB with butyl rubber.Branching agent or polydiene can be any suitable branching agents, and the present invention is not limited to for the preparation polydiene of SBB or the type of branching agent.

In one embodiment, SBB is the composition of the copolymer of butyl as above or halogenated butyl rubber and following material: polydiene and be selected from styrene, polybutadiene, polyisoprene, poly-pentadiene, natural rubber, SBR styrene butadiene rubbers, ethylene-propylendiene rubber (EPDM), ethylene-propylene rubber (EPM), the partially hydrogenated polydiene of s-B-S and SIS.Based on total monomer content wt%, polydiene can by being usually greater than 0.3wt%; Or, the about 3wt% of about 0.3-; Or approximately 0.4-2.7wt% exists.

Preferably, branching used herein or " star-branched " butyl rubber are halogenations.In one embodiment, halogenated starbranched butyl rubber (" HSBB ") comprises the butyl rubber of halogenation or non-halogenation, and the polydiene of halogenation or non-halogenation or block copolymer.The present invention does not limit by the formation method of HSBB.Polydiene/block copolymer, or branching agent (hereinafter " polydiene ") normally cationoid reaction, and exist in the polymerization process of butyl or halogenated butyl rubber, or can with butyl or halogenated butyl rubber blended to form HSBB.Branching agent or polydiene can be any suitable branching agents, and the present invention is not limited to the type of the polydiene for preparing HSBB.

The Commercial embodiments of HSBB used in the present invention is Bromobutyl6222 (ExxonMobil Chemical Company), there is the Mooney viscosity (ML1+8 of about 27-37, at 125 DEG C, ASTM D1646-04 modified version), and the bromine content of about 2.2-2.6wt%.In addition, the curing characteristics of its Bromobutyl 6222 disclosed in manufacturer is as follows: MH is 24-38dNm, ML is 6-16dNm (ASTM D2084-92A).

Other elastomer used in the present invention is isoalkene-styrenic polymer.Useful isoolefin monomer is C ₄-C ₇isoalkene is isobutene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 2-methyl-2-butene and 4-methyl-1-pentene such as.Useful styrene monomer in isoolefin copolymers comprises styrene, ring-alkylated styrenes, alkoxystyrene, indenes and indene derivative and their combination.Ring-alkylated styrenes can be o-, m-or to alkyl-replacement styrene.In one embodiment, ring-alkylated styrenes is containing at least 80wt%, more preferably at least 90wt% para-isomer to ring-alkylated styrenes.Polymer can also comprise C ₄-C ₁₄the unit that polyene derives is as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, laurene, 6,6-dimethyl-fulvene, hexadiene, cyclopentadiene and pentadiene.Described polymer can also comprise functionalized interpolymer, and at least some alkyl substituent be wherein present on styrenic monomer units contains halogen, or other functional group further described below.These interpretations are referred to herein as " isoolefin copolymers containing halomethylstyrene " or referred to as " isoolefin copolymers ".

This type of isoolefin polymer can be characterized by the interpretation comprising the following monomeric unit along the random interval of polymer chain:

Wherein R and R ¹hydrogen independently, low alkyl group, preferred C ₁-C ₇alkyl and uncle or secondary alkyl halide, X is that functional group is as halogen.Desirable halogen is chlorine, bromine or their combination, preferred bromine.Preferably, R and R ¹each hydrogen naturally.Described-CRR ¹h and-CRR ¹x group can on styrene ring at ortho position, a position, or contraposition is substituted, and is preferably substituted in contraposition.In one embodiment, be present in that contraposition in described interpretation structure replaces cinnamic at the most 60 % by mole can be functionalized structure (2) above, in another embodiment, 0.1-5 % by mole.In still another embodiment, the amount of functionalized structure (2) is 0.4-1mol%.Functional group X can be halogen or by other group as carboxylic acid; Carboxylic salts; Carboxyl ester, acid amides and acid imide; Hydroxyl; Alcohol root; Phenol root; Mercaptan root; Thioether; Xanthan acid group; Cyanogen root; Cyanate radical; Amino some other functional groups nucleophilic displacement of fluorine of benzylic halogen introduced with their mixture.These functionalized isomonoolefin's copolymers, their preparation method, functionizing method and curing at U.S. Patent number 5,162, to have carried out more specifically open in 445.

The copolymer of the present invention usefully isobutene and p-methylstyrene, it contains 0.5-20 % by mole of p-methylstyrene, wherein contain bromine or chlorine atom up to the methyl substituents that the benzyl rings of 60 % by mole exists, preferred bromine atoms (p-bromometllylstyrene), and the pattern of acid or ester functional, wherein halogen atom is replaced by maleic anhydride or acrylic or methacrylic acid functional group.These interpretations are called " halogenation gathers (isobutylene-co-p-methylstyrene) " or " bromination gathers (isobutylene-co-p-methylstyrene) ".It should be understood that, the use of term " halogenation " or " bromination " is not limited to the halogenation method of copolymer, is only the description to comprising unit that isobutene derives, unit that p-methylstyrene derives and the copolymer to the unit that halomethylstyrene derives.

These functionalized polymerics preferably have and substantially form distribution uniformly that at least 95wt% polymer is had is following to alkylstyrene content: described to alkylstyrene content within described polymer average is to 10% of alkylstyrene content.The feature of preferred polymer is also: be less than 5, be more preferably less than the Narrow Molecular Weight Distribution (Mw/Mn) of 2.5, by the preferred viscosity average molecular weigh of gel permeation chromatography about 200,000 to about 2,000, in the scope of 000 and preferred number-average molecular weight in the scope of about 25,000 to about 750,000.

Poly-(isobutylene-co-p-methylstyrene) polymer of preferred halogenation is the brominated polymer of the general bromomethyl containing the about 5wt% of about 0.1-.In still another embodiment, the amount of bromomethyl is the about 2.5wt% of about 0.2-.Represent in another way, preferred copolymer contains the about 2.5 % by mole of bromines of about 0.05-, based on the weight of polymer, and more preferably about about 1.25 % by mole of bromines of 0.1-, and be substantially free of ring halogen or halogen in the polymer backbone.In one embodiment of the invention, interpretation is C ₄-C ₇the unit that the unit that isomonoolefin derives, p-methylstyrene derive and the copolymer to the unit that halomethylstyrene derives, be wherein present in interpretation, based on described interpretation to halomethylstyrene unit by the about 1mol% of about 0.4-.In another embodiment, be to bromometllylstyrene to halomethylstyrene.Mooney viscosity (1+8,125 DEG C, ASTM D1646-04, modified version) is about 60 mooney units of about 30-.

The elastomer that the elastomer that can be used for air permeation prevention layer and the halogenation that can be used for tack coat contain isobutene can be identical or different elastomer.In a preferred embodiment, being present in elastomer in air permeation prevention layer and being present in the halogenation in tack coat containing the elastomer of isobutene is identical elastomer.In a preferred embodiment, being present in elastomer in air permeation prevention layer and being present in the halogenation in tack coat containing the elastomer of isobutene is different elastomers.Preferably, the elastomer be present in air permeation prevention layer is the brominated copolymer of isobutene and p-methylstyrene and the elastomer containing isobutene be present in tack coat is brombutyl.

Thermoplastic engineering resin

For the present invention, thermoplastic engineering resin's (also referred to as " thermoplastic resin " or " thermoplastic ") be defined as be have higher than 500MPa Young's modulus and be preferably less than 60 × 10 ^-12cccm/cm ²seccmHg (at 30 DEG C), is preferably less than 25 × 10 ^-12cccm/cm ²any thermoplastic polymer of the air permeability coefficient of seccmHg (at 30 DEG C), copolymer or their mixture, include but not limited to, one or more in following material:

A) polyamide: nylon 6 (N6), nylon66 fiber (N66), nylon 46 (N46), nylon 11 (N1l), nylon 12 (N12), NYLON610 (N610), nylon 612 (N612), nylon 6/66 copolymer (N6/66), nylon 6/66/610 (N6/66/610), nylon MXD 6 (MXD6), nylon 6T (N6T), nylon 6/6T copolymer, nylon66 fiber/PP copolymer, nylon66 fiber/PPS copolymer;

B) mylar: polybutylene terephthalate (PBT) (PBT), PETG (PET), polyethylene glycol isophthalate (PEI), PET/PEI copolymer, polyacrylate (PAR), PBN (PBN), liquid crystal polyester, polyoxyalkylene imidodicarbonic diamide diacid/poly-butyrate terephthalic acid (TPA) ester copolymer and other aromatic polyester;

C) polynitrile resins: polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitritrile-styrene resin (AS), methacrylonitrile-styrene copolymer, methacrylonitrile-styrene-butadiene copolymer;

D) polymethacrylate resin: polymethyl methacrylate, polyethyl acrylate;

E) polyvinyl resin: such as, vinyl acetate (EVA), polyvinyl alcohol (PVA), vinyl alcohol/ethylene copolymer (EVOH), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), polyvinyl/polyethylene fork base co-polymer, polyvinylidene chloride/methacrylate copolymer;

F) celluosic resin: cellulose acetate, cellulose acetate-butyrate;

G) fluororesin: polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorostyrene PVF (PCTFE), tetrafluoroethylene/ethylene copolymer (ETFE);

H) polyimide resin: aromatic polyimide;

I) polysulfones;

J) polyacetals;

K) polylactone (polyactone);

L) polyphenylene oxide and polyphenylene sulfide;

M) phenylethylene-maleic anhydride;

N) aromatic polyketone; With

O) a) to mixture any and all in n) (comprise a) and n)) and at the mixture (comprise a) and n)) a) to the engineering resin of any illustrative or example in each in n).

For purposes of the invention, the definition of engineering resin does not comprise the polymer of the alkene with any degree of crystallinity, such as polyethylene and polypropylene.

Preferred engineering resin comprises polyamide and its mixture; Particularly preferred resin comprises nylon 6, nylon66 fiber, nylon 6/66 copolymer, nylon 11 and nylon 12 and their blend.

Additional component

Generally speaking, make elastomer polymer, such as, be used for preparing those crosslinked or sulfurations of tire.Crosslinked or sulfuration is completed by adding curing agent and/or promoter; The whole mixture of mentioned reagent is commonly referred to solidification " system ".As everyone knows, the physical property of vulcanizate compounds, performance characteristic are directly relevant with type to the number (crosslink density) of the crosslinking points formed during vulcanization reaction with durability.Curing agent comprises those components of promotion as mentioned above or the solidification of influence elastane body, and generally includes the conventional reagent in metal, promoter, sulphur, peroxide and other this area, and as mentioned above.Crosslinking agent or curing agent comprise at least one in such as sulphur, zinc oxide and aliphatic acid and composition thereof.Also the curing system comprising peroxide can be used.Usually, polymer composition can be cross-linked as follows: add the curing agent of such as sulphur, metal oxide (that is, zinc oxide, ZnO), organo-metallic compound, radical initiator etc. and heat described composition or mixture.When use is called the method for " dynamic vulcanization ", improve described method so that substantially side by side make at least one in composition curable component mix and sulfuration, or crosslinked, described composition comprise at least one can vulcanized rubber, elastomer or polymer and at least one use can the not vulcanizable elastomer of vulcanizing agent of curable component or polymer at least one.(such as, see, U.S. Patent number 6,079,465 and the bibliography wherein quoted).Specifically, following material is the Common Curing Agents that can play a role in the present invention: ZnO, CaO, MgO, Al ₂o ₃, CrO ₃, FeO, Fe ₂o ₃and NiO.These metal oxides can be combined with corresponding metal stearate complex (such as, the stearate of Zn, Ca, Mg and Al), or are combined with stearic acid and sulfur-containing compound or alkyl peroxide compound.Usually in curing agent, add the promoter being used for elastic composition sulfuration.Utilize or do not utilize the usual solidification " system " be called in the art for elastomer (one or more) of the curing agent (one or more) of at least one promoter.Because in order to useful effect, especially when using the elastomeric mixture of high diene rubbers and more hypoergia, usually use more than a kind of curing agent, so use curing system.

With regard to deposit the dynamic vulcanization of height of formation impenetrability layer in case at engineering resin with regard to, anyly the conventional curative system of saturated halogen polymer sulfuration can be can be used for sulfuration at least C ₄-C ₇the halogenation of elastomers copolymer of isomonoolefin and p-ring-alkylated styrenes, unless worked as selected thermoplastic engineering resin's (one or more) so that peroxide when will cause these resin self-crosslinkings, get rid of peroxide firming agent especially outside practice of the present invention, because described engineering resin is by self sulfuration or crosslinked, thus cause the non-thermal plasticity composition of undue solidification.To the curing system that halogenation of elastomers copolymer component of the present invention is suitable comprise zinc oxide and zinc stearate or stearic acid and, optionally, the combination of one or more following promoter or vulcanizing agent: Permalux (two-o-tolyl guanidinesalts of two catechol borates); HVA-2 (m-penylene two maleimide); Zisnet (2,4,6-tri-thiol-5-triazine); ZDEDC (zinc diethyl dithiocarbamate) and comprising, for the present invention, other dithiocar-bamate; TetroneA (two pentamethylene thiuram hexasulfide); Vultac 5 (alkylated phenol disulphide); SP1045 (resinox); SP1056 (alkylphenol-formaldehyde resin of bromination); DPPD (diphenyl-phenylene-diamine); Salicylic acid; Septichen; Wood rosin; Rosin acid; With TMTDS (tetramethylthiuram disulfide), use in combination with sulphur.

Dynamic vulcanization, making the halogen-containing copolymer of elastomer of fluid (gas or liquid, preferred air) impermeable layer at least part of, carries out under the condition of preferred complete cure.

With regard to the polymer that relates to herein and/or elastomer, term " solidification (cured) ", " sulfuration (vulcanized) ", or " being cross-linked " refers to and comprises formation such as, the bonding during chain extension or form chemical reaction crosslinked between polymer or elastomeric polymer chain and reach such degree: the elasticity physical efficiency experiencing described process is provided the functional of when tire used necessity by described curing reaction.For the present invention, when will be considered as " solidification ", " sulfuration " or " being cross-linked " containing elastomer compositions, completing completely of above-mentioned curing reaction will not be needed.Such as, for the present invention, if show satisfactory when the tire comprising tack coat is during manufacture and afterwards by the test of necessary product specification and on vehicle, then described tire fully solidification.In addition, even if may produce extra hardening time extra crosslinked, as long as tire can be used, then described composition be satisfactory, fully or substantially solidify, sulfuration or crosslinked.Known instrument and standard technique is used to carry out limited experiment, those of ordinary skill in the art can easily determine to select the suitable or optimum curing time for required by the elastomer (one or more) of binding layer composition and polymer (one or more), and the consumption of crosslinking agent (one or more) and promoter (one or more) and type and will be used for the solidification temperature of manufacture tire.

Here useful promoter comprises amine, guanidine, thiocarbamide, thiazole, thiuram, sulfenamide, sulfenimide, thiocarbamate, xanthate etc.Can by adding the acceleration that a certain amount of promoter reaches solidification process in composition.The mechanism of the sulfuration of the acceleration of natural rubber comprises the interaction of curing agent, promoter, complexity between activator and polymer.Ideally, connected together by two polymer chains and improving in the formation of effective crosslinking points of the overall strength of polymeric matrix, all available curing agent are consumed.Much promoter is as known in the art and comprises, but be not limited to following: stearic acid, diphenylguanidine (DPG), tetramethylthiuram disulfide (TMTD), 4, 4'-dithio morpholine (DTDM), tetrabutylthiuram disulfide (TBTD), 2, 2'-benzothiazole disulfide (MBTS), hexa-methylene-1, the two sodothiol dihydrate of 6-, 2-(morpholinothio) benzothiazole (MBS or MOR), the composition of 90%MOR and 10%MBTS (MOR90), the N-tert-butyl group-2-[4-morpholinodithio sulfenamide (TBBS) and N-oxygen diethylidene thiocarbamoyl-N-oxygen diethylidene sulfonamide (OTOS), 2 ethyl hexanoic acid zinc (ZEH), N, N'-diethyl thiourea.The curing agent that can use together with one or more crosslinkable polymers, promoter and curing system are well known in the art.

In one embodiment of the invention, at least one curing agent is usually with the about 15phr of about 0.1phr-; Or exist with the about 10phr of about 0.5phr-.

Composition described herein can have one or more filler components, such as calcium carbonate, clay, mica, silica and silicate, talcum, titanium dioxide, starch and other organic filler such as wood powder, and carbon black.The filler material be applicable to comprises carbon black such as channel black, furnace black, thermals, acetylene black, dim etc.It is most preferred for strengthening grade carbon black.Filler can also comprise other to be strengthened or non-reinforcing material such as silica, clay, calcium carbonate, talcum, titanium dioxide etc.Filler is generally by accounting for the about 50wt% of the about 20-of total composition, and more preferably approximately the level of 25-40wt% is present in composition (preferred liner).In one embodiment, filler is carbon black or modified carbon black.Preferred filler is half enhancing grade carbon black, and usually by about 10-150 part/100 part rubber, more preferably approximately the level of the about 120phr of 30-uses, by weight (phr).The grade of carbon black useful here comprises N110-N990, as described in RUBBERTECHNOLOGY 59-85 (1995).More desirably, can be used for the grade of the carbon black of such as tire tread, N229, N351, N339, N220, N234 and N110 of such as providing in ASTM (D3037, D1510 and D3765) are useful at this.Embodiment such as N330, N351, N550, N650, N660 and N762 of carbon black useful in such as sidewall are particularly useful at this.Can be used for such as, the embodiment of the carbon black of liner or interior pipe, such as N550, N650, N660, N762, N990 and Regal 85 (Cabot Corporation, Alpharetta, GA) etc. are particularly useful equally at this.

Due to the difference of thermoplastic resin in DVA and elastomeric dissolubility aspect, bulking agent can be adopted.This type of bulking agent is thought following and is acted on: improve, especially reduce the surface tension between the rubber of composition and thermoplastic component.The bulking agent be applicable to comprises olefinically unsaturated nitriles-conjugation based on the high saturation copolymer rubber (HNBR) of diene, epoxy natural rubber (ENR), ACM and their mixture, and there is the mutually isostructural copolymer of thermoplastic resin or elastomer polymer, or have can react with described thermoplastic resin or elastomer epoxy radicals, carbonyl, halogen group, amido, maleinization base, the copolymer of the structure of the copolymer of azoles quinoline base or hydroxyl.

Normally about about 10 weight portions of 0.5-of amount of bulking agent; Preferably approximately about 8 weight portions of 3-, based on the elastomer that 100 weight portions are total.

Minimize in mixing and/or the viscosity differences between processing period chien shih elastomer and thermoplastic resin component and strengthen Homogeneous phase mixing and intimate blend form, the blend mechanicalness that this has improved significantly and the permeability of expectation.But, the result of the flow activation intrinsic as elastomer polymer and shear shinning characteristic, the viscosity number under the temperature of the rising that elastomer polymer during mixing runs into and shear rate reduces and reduces much remarkable than the viscosity with elastomer blended thermoplastic component.This viscosity differences reduced between material is expected to obtain the DVA with acceptable elastomer dispersion size.

Be used for that the component of the viscosity increase-volume between elastomer and thermoplastic component is comprised low molecular polyamides before this, have and be about 10, the maleic anhydride grafted polymer of the molecular weight of 000 or larger, methacrylate copolymer, tertiary amine and secondary diamine.Example comprises ethylene-ethyl acrylate copolymer (the solid rubber shape material that can obtain from Mitsui-DuPont as the AR-201 of melt flow rate (MFR) with the 7g/10min measured according to JIS K6710) and the butyl benzyl sulfonamide (BBSA) of maleic anhydride graft." effectively " that these compounds can be used for increasing thermoplastic in elastomer/thermoplasticity blend measures.The amount of additive is selected to contrast to obtain the viscosity expected, and can not the characteristic of negative effect DVA.If exist too many, then impermeability may reduce and may must remove during aft-loaded airfoil excessive.If the bulking agent that Shortcomings is enough, then elastomer may can not phase inversion to become the decentralized photo in thermoplastic resin matrix.

The amount of the plasticizer existed in DVA is in the scope of the maximum from the minimum of about 2phr, 5phr or 10phr to 15phr, 20phr, 25phr, 30phr or 35phr.

The preparation of DVA

Term " dynamic vulcanization " is used for representing following vulcanization process in this article: wherein under the condition of the temperature of high shear and rising, mix engineering resin and rubber in the presence of a curing agent.As a result, described rubber, as fine grained, such as, is cross-linked with microgel simultaneously and is dispersed in the engineering resin of formation successive substrates; " dynamic vulcanization alloy " or DVA is called in composition this area of gained.Dynamic vulcanization is implemented as follows: equipment as roller mill, at the temperature being equal to or greater than rubber curing temperature, each composition is mixed in mixer, continuous mixer, kneader or mixing extruder (such as double screw extruder).The specific characteristic of the composition of dynamical cure is: even if there is the fact that rubber is solidification, still can by conventional thermoplastic material's process technology as extruded, injection moulding, compression moulding etc. is by composition processing and reprocessing.Waste material and/or flash (flashing) can also be collected and reprocess.

At least in part, under the condition of the preferred fully halogen-containing copolymer of vulcanized elastomer, carry out Technology of Dynamic Vulcanized.In order to complete this point, at the temperature being enough to make resin softening or, more generally, at the temperature of fusing point being greater than crystallization or semi-crystalline resins by thermoplastic engineering resin, elastomer copolymer together with other mixed with polymers non-essential.Preferably, premixed curing system in elastomeric component.Heating and plasticate usually and enough complete sulfuration at about 0.5-in about 10 minutes under curing temperature.Cure time can be reduced by improving curing temperature.The scope be applicable to of curing temperature is normally from the fusing point of about thermoplastic resin to about 300 DEG C; Such as, temperature can be that the fusing point of about matrix resin is to about 275 DEG C.Preferably, at the temperature of high about 10 DEG C-about 50 DEG C of the melt temperature than matrix resin, sulfuration is carried out.

Preferred continuation mixed process is until complete the sulfuration or crosslinked of desired level.If allow to continue sulfuration after stopping mixing, then described composition can may not be reprocessed as thermoplastic.But, dynamic vulcanization can be carried out by stages.Such as, sulfuration can be started in double screw extruder and use underwater pelletizer to form pellet by DVA material, thus by sulfuration quencher before sulfuration completes.Sulfidation can complete after a while under dynamic vulcanization conditions.Those skilled in the art are by the length of the appropriate amount of the curing agent that understands required by the sulfuration carrying out rubber, type and incorporation time.When necessity or when wishing to set up suitable concentration and condition, the curing agent of variable quantity (it can comprise one or more curing agent and/or promoter) can be used only to make the vulcanization of rubber, to determine best curing system to be used and to reach completely crued proper settings condition substantially.

Although preferably before enforcement dynamic vulcanization process, all components should be present in mixture, this is not necessary condition.Such as, all fillers added before the dynamic vulcanization stage are when deployed unnecessary with oil.Can adding portion or all filler and oil after the sulfiding is completed.If add them after hardening, some composition, such as stabilizing agent and processing aid more effectively act on.

Adhesive tie layer

Tack coat usually used as by use extrude or calender line formed sheet material or film exist.Tack coat or can be extruded or roll on the DVA layer formed with DVA coextrusion.

Adhesives layer composition comprises the mixture of following material: the halogenation of (1) 100wt% contains the elastomer of isobutene; (2) at least one filler of about about 50wt% of 20-; (3) at least one processing oil of about about 30wt% of 0-; (4) at least approximately about 15 parts/100 parts rubber (phr) of 0.1-for described elastomeric curing system; (5) at least one tackifier of about 10 parts/100 parts of 0.1-.In a preferred embodiment, halogenation is isobutene and C containing the elastomer of isobutene ₄-C ₁₄the halogen-containing random copolymer of polyene.In each case, halogen is selected from chlorine, bromine and their mixture.Useful elastomer can be selected from chlorinated scoline, brombutyl, chlorinated star branched butyl rubber, brominated star branched butyl rubber and their mixture.The halogenation of 100wt% is selected in described tack coat, to provide hypotonicity as the unique elastomer in tack coat containing the elastomer of isobutene.

The filler that can be used for tack coat comprises at least one filler be selected from following material: carbon black, clay, stripping clay, intercalation clay, dispersed clay, calcium carbonate, mica, silica, silicate, talcum, titanium dioxide, wood powder and their mixture.Preferably, described filler is selected from carbon black, peels off clay, intercalation clay and dispersed clay and their mixture.The normally about about 50wt% of 20-of amount of described at least one filler; The preferably approximately about 40wt% of 25-; Based on the gross weight of described binding layer composition.

Tack coat optionally comprises RUBBER PROCESS OIL or plasticizer oil.Term as used herein " processing oil " refers to processing oil and the synthesis plasticizer of petroleum derivation.This type of oil is mainly used to the processing of preparation (such as, mixing, calendering etc.) the period composition improving described layer.Generally speaking, processing oil can be selected from paraffinic oils, aromatic naphtha, naphthenic oil and Polybutene oil.Polybutene processing oil has about 8 carbon atoms of about 3-, more preferably approximately low-molecular-weight (lower than 15, the 000Mn) homopolymers of unit that derives of the alkene of about 6 carbon atoms of 4-or copolymer.In another embodiment, Polybutene oil is C ₄the homopolymers of raffinate or copolymer.Preferred polybutene processing oil normally has certain molecular weight, preferably approximately the synthetic fluid polybutene of the molecular weight of the about 2700Mn of 420Mn-.Molecular weight distribution-Mw/Mn-(" MWD ") normally about 1.8-about 3, the preferably approximately 2-about 2.8 of preferred Polybutene oil.The preferred density (g/ml) of useful polybutene processing oil is about 0.85-about 0.91.The bromine number (CG/G) of preferred Polybutene oil is for 450Mn processing oil about 40, extremely for about 8 of 2700Mn processing oil.

RUBBER PROCESS OIL also has ASTM title, and this depends on whether they fall into the classification of alkane, cycloalkanes or aromatic hydrocarbon matter processing oil.The type of the processing oil used will be usual and certain class elastomeric component conbined usage, and which class oil of identification should be used for specific application with specific rubber by common rubber chemistry worker.

The plasticizer oil be applicable to comprises oil or the Polybutene oil of aliphatic acid ester or hydrocarbon plasticizer oil such as alkane or cycloalkanes oil.

In still another embodiment, cycloalkanes, aliphatic series, alkane and other aromatic oil do not exist in the composition substantially.So-called " substantially not existing " refers to that cycloalkanes, aliphatic series, alkane and other aromatic oil can exist, and if any, is not more than 1phr in the composition.In still another embodiment, cycloalkanes, aliphatic series, alkane and other aromatic naphtha exist by being less than 2phr.

The normally about about 30wt% of 0-of amount of RUBBER PROCESS OIL or plasticizer oil; The preferably approximately about 20wt% of 0-; More preferably about about 10wt% of 0-, based on the gross weight of binding layer composition.Preferably, processing oil is cycloalkanes or polybutene type of oil.

Use the curing system comprising at least one curing agent and at least one promoter that described adhesive tie layer is solidified or sulfuration, described at least one curing agent and at least one promoter can be used for comprising the elastomer compositions of halogenation containing isobutene.Curing system for described adhesive tie layer comprises all above-mentioned curing agent for can be used for DVA described above and promoter.DVA and the curing system in tack coat can be identical or can not be identical; But when layer is adjacent to each other during formation and follow-up article configurations and urethane cure because cure system component should be compatible to the transfer of the interlayer of adjacent layer from a layer.Usually, curing system exists by the amount of at least about about 15 parts/100 parts rubber (phr) of 0.1-, but those skilled in the art are by known, large degree is depended on the concrete component of selected curing system by the unrestricted and amount used of the specified quantitative of curing system.

Other non-essential useful additive usually adds by the level being less than about 10phr and can be selected from pigment, antioxidant, antiozonant, processing aid, compound bulking agent etc. and their mixture.These non-essential additives can be comprised to realize specific advantage in the composition according to the meaning of compounder, such as, use the tackifier contact improved during Tyre structure adhere to or use antioxidant to improve the thermal ageing properties of hardening composition.

In a preferred embodiment, at least one tackifier are included in binding layer composition.For the present invention, tackifier comprise the material being called rosin or rosin derivative and the various derivatives being called the tackifier for the composition containing elastomer or polymer, such as acetylene-phenolic compound.The tackifier be particularly useful comprise the condensation product of butylphenol and acetylene, such as acetylene-p-t-butyl phenol that " Koresin " (BASF) is purchased, with as " MR1085A " (Mobile Rosin Oil Company, Mobile, Ala.) rosin tackifier be purchased, the i.e. blend of toll oil rosin and aliphatic acid.Some tackifier are appointed as and are especially can be used for giving particular polymers or elastomer viscosity, but may determine their also blends used in the present invention.

Viscosity generally refer to when use compared with short residence time and described blend when only using the pressure of some moderate amount that uncured rubber compounding thing is contacted adhere to it from it or adhere to ability on other blend (" Rubber Technology:Compounding and Testing forPerformance; " J.S.Dick, Ed., 42,2001).The time of staying and pressure are determined by the possibility that excess pressure and the time of staying destroy by for the equipment of described object and the sheet material of uncured composition usually.Viscosity also may affect by the dissolubility of various rubber components in each other and in overall composition.In some cases, the component of composition may be diffused into the surface of calendering or extrusion sheet or film and disturb viscosity, such as, if it is inorganic particle (being once called " frosting ").On the other hand, this kind of diffusion may improve viscosity, such as, if diffusivity component is the component of self display viscosity.It is the performance being difficult to measure that those skilled in the art should understand viscosity, and those skilled in the art may need the performance determination composition by evaluating composition in the shop test preparing final products or environment whether to reach enough levels of adhesion sometimes.Under existing conditions, that will generally include actual Tyre structure and determine whether tack coat shows enough Tyre structure viscosity so that uncured tire construction will combine during the initial stage inflation during the Tyre structure stage and between curing time until structure reaches enough solidification levels, and therefore the solidification each other of various tire layer adheres to; Comprise tack coat and those layers with its abutting contact, comprise, such as, the adhesion of casing ply and inner liner.There is not the standard test procedure measuring rubber compounding thing viscosity, but widely used instrument introduced " Tel-Tak Tackmeter " by Monsanto in 1969.Another test apparatus is the PICMA tack meter manufactured by Toyo SeikiSeisakusho (Japan).

In a preferred embodiment in accordance with this invention, at least one tackifier are pressed the about 20phr of about 1phr-; The preferably approximately about 18phr of 2phr-; More preferably about about 16phr of 3phr-; Such as, the concentration of the about 14phr of about 4phr-is added in binding layer composition.Or at least one tackifier are usually by about 15phr or less; Preferably approximately 12phr or less; More preferably about 10phr or less; Be more preferably about 9phr or less; Most preferably about 8phr or less; Such as, the about 10phr of about 1phr-; The about 9phr of about 1phr-; The about 9phr of about 2phr-; The about 8phr of about 2phr-; The level of the about 7phr of about 2phr-etc. uses, and comprises containing about 1,2,3,4,5,6,7,8,9 and 10phr value in the individual values of each and scope.Similarly, use the mixture of tackifier, such as, during two kinds of tackifier of identical or different chemical type, each in described tackifier can exist by equivalent or inequality, and the total amount of the tackifier used preferably retrains by the total amount just enumerated above.

Can individually and in combination, use the preparation adhesives layer compositions such as mixing apparatus such as Banbury blender, roller mill blender, extruder blender elastomer, filler, processing oil and other additive to be mixed and cure system component to be disperseed.Usually, at the temperature raised and high shear by the composition mixing except cure system component except to realize the gratifying dispersion in all inelastic body components to elastomer with elastomer in each other.After this kind of blend step, use, such as, rubber grinding machine or use the lower temperature of mixing extruder or banbury, will lower temperature is not cooled to containing the composition (being sometimes referred to as masterbatch) of cure system component and cure system component is distributed in described masterbatch compared with low sheraing section.The temperature of mixed curing agent is less than about 120 DEG C usually, is preferably less than about 100 DEG C.

Can use such as, adhesives layer composition is formed the layer being suitable for final use application by extruder or calender.When facilitating or having the used time, extrude the dual or multiple equipment extruded that can comprise and use and allow fluid (preferred air) impermeable layer and adhesive tie layer.Or, adhesive tie layer can be prepared as follows: compounding rubber composition is rolled into the sheet material with desired thickness, and is cut into by described sheet material and have suitable width and length to be used for the strip of liner application in specific dimensions or type tire.

In the present invention, tack coat prepares to be used for Tyre structure and has usually about 5mm or lower; Preferably approximately 2.5mm or lower; More preferably about 1.0mm or lower, about 0.9mm or lower, or about 0.8mm or lower; Even more preferably about about 2.0mm of 0.2-; The most preferably approximately about 1.5mm of 0.2-or the approximately about 0.8mm of 0.2mm-; The such as thickness of about about 0.9mm of 0.3-.Thickness for the tack coat of hose construction can be identical or different, and this depends on the application that described flexible pipe will be applied to.Such as, do not strengthen, low-pressure hose can have the performance requirement different from high pressure, reinforced hose, similarly, for the flexible pipe designed for liquid can be different from the flexible pipe for gas.The adjustment of thickness within the skill of product designer, engineer or chemist, if necessary, based on limited experiment.

Laminar composition/laminar structure

Mix DVA with realize expect composition and form after, it is typical for allowing material pass comminutor to form DVA pellet.Then by these pellet delivery film extruders with preparation extrude/blown film or supply blender to prepare casting films.According to the present invention, DVA is self is extrudate or curtain coating thing; Namely not by sheet material and the coextrusion of adhesive rete to produce the extra adhesion between DVA and adhesive tie layer.

After DVA film is formed, process described film to remove any residual plasticizer or oil; In the present invention, " residual plasticizer or oil " is defined as in an extruder between mixing period or during the preparation of film, is not grafted to the plasticizer or oil that are present on film surface in DVA and due to the thin of film.The removing carrying out the plasticizer/oil remained, to obtain the film being substantially free of any plasticizer/oil be present on film surface, wherein " is substantially free of " plasticizer being defined as and film being less than 0.1wt%.

Be exposed to hanker making plasticizer from least one surperficial flash distillation of film, evaporation, distillation and/or oxidation from a kind of method of DVA film removing plasticizer/oil.This can carry out as follows: more than plasticizer/oil flash, do not keep certain time of staying higher than heating film at the temperature of 15 or 10 or 5 or 1 DEG C, the heat treated film that the level of plasticizer in the DVA film of the initial preparation of level of plasticizer ratio then described DVA film cooling had with formation is little.Desirably, described film is exposed in oxygen during heating steps.In any embodiment of the present invention, to send continuously or continuous print gas flow heats simultaneously substantially in continuous elastic body length blowing up.Gas can be air, nitrogen/oxygen mixture, or is wherein mixed with other gas of oxidant.

Fig. 1 shows process DVA film to remove the method for residual plasticizer.Allow DVA film 10 through multi-region baking oven 12.DVA film 10 is made to launch from roller 14 and recoil on roller 16.Multi-region baking oven 12 citing illustrates to have four districts; But the number of actual zone used in the present invention can change from 2-10 district.By adopting the district in baking oven 12, the temperature of DVA material little by little can be improved or reduces with the plasticizer/oil realizing remaining immediately or delay remove, and provide the cooling gradually of any expectation of DVA film.In any embodiment of the present invention, plasticizer/oil flash is carried out in district N-2, and wherein N is the sum in district in baking oven 12 and district calculates by the order left that enters into from film 10.

The citing of recoil roller 16 is shown as and is close to the outlet of baking oven 12; But, it will be apparent for a person skilled in the art that if the film 18 of treated minimizing plasticizer does not reach the temperature of enough coolings to allow the recoil of film 10, then can adopt additional batching and clad roller, and the cooling way of other routine.

Or, replace the film 18 reducing plasticizer to recoil on roller 16, film 18 can be delivered to calendering operation so that the applying of adhesives sizing material layer.Apply the exemplary calendaring system display of adhesives sizing material layer in fig. 2; Because calendering applies to know, those skilled in the art will understand various calendaring system can be used for the present invention and the present invention does not limit by shown system.Allow DVA film 18 by one group of stack 20.When DVA film 18 is through the several gap produced by adjacent roller, it passes through for 22 times on the one group of material of the pencil shape containing adhesives layer composition ridge.Roller is the adjacent expectation thickness to acquire adhesive tie layer.

By the roller heating in calendering pipe group (calender bank) 20 to make DVA film 18 warm and to guarantee that the adhesives layer composition in pencil shape material ridge 22 has enough temperature to allow elastic composition flowing and level and smooth coating DVA film.The temperature and pressure of the roller in pipe group (bank) 20 enough should cause the degree bondd between DVA film 18 and described adhesives composition.The temperature of roller can change to 150 DEG C from 50 DEG C, preferably changes to 85 DEG C from 65 DEG C.Temperature should keep the curing temperature being less than binding layer composition to prevent any solidification of adhesive tie layer composition.

Described film leaves calendering pipe group 20 as the film 24 (this also can be called DVA laminate) that tack coat is coated with.In order to easy winding, due to the adhesion properties of adhesives composition, to prevent DVA laminate 24 at roller winding subsequently and memory period and himself to adhere on the film 24 that non-essential process film 26 can be put on coating.Before use DVA laminate 24, if remove from DVA laminate 24 the process film existed.

The present composition and the layer structure using such composition to be formed may be used for tire applications; Tire curing air bag; Casing air, such as wave absorber, barrier film; With flexible pipe application, comprise gas and fluid transporting hose.

Fig. 3 is half viewgraph of cross-section of the representative configuration example showing the impermeable or inner liner of airtyred air along the meridian direction of tire 28.At least one casing ply 30 is crossed between left and right bead core 32 (it should be pointed out that because only comprise 1/2nd of symmetrical cross-sections view for the sake of simplicity, so do not show second bead core).On tire inner surface, the inner side of casing ply 30 provides inner liner 34.What insert between inner liner 34 and casing ply 30 is adhesive tie layer 36.Adhesive tie layer 36 promotes that the adhesion of DVA air permeation prevention layer and tire inner surface and air keep quality.The surface that the surface contacted with inner liner 34 of tack coat 36 is relative directly contacts with interior casing ply 30, or more particularly, adhesive tie layer 36 directly contacts with the interior coating blend of radial direction of interior casing ply 30.

Pneumatic tire is also by the outer surface comprising tyre surface, the strap configurations formed by multiple layers and side wall member, with possible middle casing ply composition, described possible middle casing ply comprises the many laminations (ply) containing the tire enhancing fiber (such as, artificial silk, polyester, nylon or metallic fiber) embedded in rubber matrix.Tyre surface, belt and casing ply, and the change of tire size (that is, overall diameter and Sidewall Height) admissiblely not to limit by the present invention.Use above-mentioned layer usually to be formed on drum at tire and construct tire.After described drum constructs uncured tire, it is removed and puts into mold heat.Described mould contains can inflation tire air bag, and it is positioned at the inner periphery of uncured tire.After closing molding, for described airbag aeration and it is by forcing it to make tire against the inner surface of closing molding in early days at solidification process.Heat in described air bag and mould makes the temperature of tire be elevated to curing temperature.Curing temperature normally about 100 DEG C-about 250 DEG C; Preferably approximately 150 DEG C-about 200 DEG C.Hardening time can be about one minute to a few hours; Preferably approximately 5-30 minute.Hardening time and temperature depend on many variablees well known in the art, comprise the composition of tire components, comprise the curing system in each layer, whole tire size and thickness etc.Curing parameter can various known laboratory test methods auxiliary under determine, comprise test procedure and stress-strain testing, adherence test, the bending test etc. of description in ASTM D2084-01 (sulfuration of standard method of test-uses vibration disk solidification instrument of rubber performance).The sulfuration of green tire causes all components or the layer of tyre assembly, i.e. liner, casing ply and tread and side wall layer completely or substantially sulfuration completely or crosslinked.Except the desirable strength characteristic reaching every one deck and general structure, sulfuration also improves the adhesion between these components, thus from independently, multiple layer obtain solidify, one tire.

As discussed in detail above, inner liner shows advantageously low permeance property and preferably comprises the composition of dynamic vulcanization, and described composition comprises engineering resin, especially polyamide, and halogenated isobutylene-p-methylstyrene copolymer.In addition, due to tack coat based on can sulfuration halogenated isobutylene elastomer uniqueness composition result, especially its low air penetration performance and produce the ability that the high sulfuration of the liner surface that contacts with it adheres to, and allow to use thin tack coat compared with mainly containing the composition of high diene rubbers.The general structure based on this type of liner and tack coat of gained allows Tyre structure to have (and comprising other structure of air or liquid retaining layer and tack coat) weight of reduction.Usually, the weight saving of about 2%-about 16% can be realized; Or, the weight saving of about 4%-about 13%.Such improvement is especially significant in application examples is as pneumatic tire.

Following examples illustrating as embodiment of the present invention of request protection is provided.But, be to be understood that the details that the invention is not restricted to provide in embodiment.In addition, the any number range enumerated in description or claim, such as represent particular characteristic group, measurement unit, condition, physical state or percentile number range to be intended to literally go up specially be hereby incorporated by, or will belong to any numerical value of these scopes, any subgroup being included in the numerical value in cited any scope is specially hereby incorporated by.Such as, whenever openly having lower limit R _lwith upper limit R _unumber range time, particularly discloses any numerical value R belonging to described scope.Particularly, the following amount R in scope is particularly disclosed: R=R _l+ k (R _u-R _l), wherein k is the variable with 1% increment of 1%-100%, and such as k is 1%, 2%, 3%, 4%, 5%...50%, 51%, 52%....95%, 96%, 97%, 98%, 99% or 100%.In addition, as calculated above, any number range represented by any two R values is also disclosed especially.

Embodiment

Composition and sample is prepared according to following examples.The consumption of the often kind of component used is based on the rubber (phr) existed in part described composition of part/100.The component of commercially available product for adopting in the composition of embodiment below:

Table 1

Cure system component

Elastomer additives component

Engineering resin component

The test method being used for evaluating following sample provides in table 2.

Table 2

Preparation has the DVA of the thermoplastic elastomer (TPE) of the composition provided in table 3.Elastomeric component and vulcanizing system are loaded the first kneader, mixes about 3.5 minutes, at about 90 DEG C, pour out to prepare the elastomeric component of the promotion with vulcanizing system.Then by rubber comminutor by described mixture pelleting.Next, the elastomer of granulation and resin Composition are added twin screw mixing extruders and dynamic vulcanization and prepare composition for thermoplastic elastomer.According to the program described in EP 0 969 039, the part being " preparation of composition for thermoplastic elastomer " with particular reference to title prepares DVA.Sulfuration in double screw extruder is carried out at 230 DEG C.After DVA preparation and granulation, then DVA is delivered to film blow molding operation, wherein DVA extrudes as extrusion film.According to the present invention, DVA film not with adhesive coating coextrusion; DVA film is not containing adhesive.

Table 3

Component	Amount, phr
		BIMS	100
ZnO	0.15
		St-acid	0.60
ZnSt	0.30
		N6/66	66.53
Plasticizer	23.4
		Bulking agent	10
Stabilizing agent	0.5

After DVA film is as film coextrusion, the plasticizer remained via above-mentioned heating operation removing does not contain the DVA film of residual plasticizer/oil on the surface of the film with preparation.

As above for the compounding described preparation adhesives layer composition of conventional elastomers and exemplary casing ply blend.Composition provides in following table 4.All components amount in table 4 is part/100 part rubber (phr).

Table 4

Blend	T1	T2	T3	T4	Casing ply
						BIIR	100.00	100.00	100.00	100.00	--
NR					70
						SBR					30
N660	60.00	60.00	--	--	60
						N351	--	--	40.00	40.00	--
Flectol	--	--	--	--	1
						Processing oil	8.00	8.00	--	--	10
Struktol 40MS	7.00	--	4.00	4.00	--
						St-acid	1.00	2.00	2.00	2.00	2
ZnO	1.00	3.00	3.00	3.00	3
						MBTS	1.25	1.50	1.50	1.50	--

Table 4 continues

When directly boning with DVA film, the excellent adhesion of all adhesive tie layer displays to treated DVA layer.In peel adhesion test, along with the amount of tackifier in adhesive tie layer increases, in fact bonding between adhesive tie layer and DVA film reduces, but the bonding between adhesive tie layer and lamination blend is roughly the same for all adhesive compositions.With other DVA laminar construction, such as disclosed in U.S. Patent application 2008/314492, those are compared, if above-mentioned data display process DVA is to remove residual plasticizer/oil, then in the adhesive glue bed of material, multiple tackifier are adopted to be unnecessary, even still like this when there is no film adhesive layer.

Therefore, according to the present invention, in order to realize, to the excellent adhesion of the laminate containing DVA, not requiring to use film adhesive layer between DVA film and the adhesive glue bed of material.The plasticizer residual from the removing of DVA film and/or oil allow that adhesive tie layer more easily bonds with DVA film, and therefore improve the adhesiveness of DVA film in goods.More particularly, due to the adhesiveness improved, the tire containing the treated DVA film of described bonding will have the durability of improvement.

Claims

1. the manufacture method of laminar structure, comprises the following steps:

(A) the adhesives composition comprising the mixture of following material is formed:

(1) at least one halogenation of 100wt% contains the elastomer of isobutene;

(2) at least one filler of about about 50wt% of 20-;

(3) at least one processing oil of about about 30wt% of 0-;

(4) at least one tackifier of about about 20 parts of 1-/100 parts (phr); With

(5) approximately about 15 parts/100 parts rubber (phr) of 0.1-for described elastomeric curing system;

(B) the fluid permeation prevention composition comprising following component is formed:

(1) based on the gross weight of described polymer composition, at least at least one of 10wt% has thermoplastic engineering resin's component of the Young's modulus higher than 500MPa, wherein said thermoplastic engineering resin's component is selected from polyamide, mylar, polynitrile resins, polymethacrylate resin, polyvinyl resin, celluosic resin, fluororesin and imide resin

(2) based on the gross weight of described polymer composition, at least at least one of 10wt% has not higher than the elastomeric component of the Young's modulus of 500MPa, wherein said elastomeric component be selected from diene rubber, halogen-containing rubber, silicone rubber, containing sulphur rubber and fluorubber, and

(3) plasticizer of 2-30 part/100 part rubber, based on component (2),

Wherein described thermoplastic engineering resin, described elastomer and described plasticizer are mixed to be dispersed in as discontinuous phase in the successive substrates of described thermoplastic engineering resin by described elastomer under dynamic vulcanization conditions;

(C) film of described fluid permeation prevention composition is formed;

(D) process described fluid impervious permeable membrane and form treated film with the plasticizer remained from the surface removing of described film or oil; With

(E) surface of described treated film is directly applied to form described laminar structure with described adhesives composition.

2. the process of claim 1 wherein described adhesives composition calendering or be expressed on the surface of described treated film.

3. the method for claim 1 or 2, wherein step (E) carry out under conditions of heat and pressure with by described treated film together with described adhesives composition bond.

4. the method any one of claim 1-3, the component (1) of wherein said adhesives composition is (i) C ₄-C ₇isomonoolefin and the halogen-containing random copolymer to ring-alkylated styrenes, the described about 20wt% of about 0.5-ring-alkylated styrenes being accounted for described copolymer, or (ii) C ₄-C ₁₂isomonoolefin and C ₄-C ₁₄the halogen-containing random copolymer of polyene; In each case, described halogen is selected from chlorine, bromine and their mixture.

5. the method any one of claim 1-4, the described at least one elastomeric component of wherein said fluid permeation prevention composition is selected from C ₄-C ₇isomonoolefin and halide, brominated isobutylene-p-methylstyrene copolymer, hydrogenated nitrile-butadiene rubber, acrylonitrile-butadiene rubber, chlorosulfonated polyethylene, haloflex, epichlorohydrin rubber, chlorinated scoline and brombutyl to alkylstyrene copolymers.

6. the method any one of claim 1-5, wherein said at least one tackifier comprise condensation product and their the ingredients of a mixture that at least one is selected from rosin, rosin derivative, tert-butyl phenol and acetylene.

7. the method any one of claim 1-6, wherein said at least one tackifier comprise the mixture of the composition at least two kinds of condensation products and their mixture being selected from rosin, rosin derivative, tert-butyl phenol and acetylene.

8. two immediately adjacent layers can sulfuration laminar composition, the ground floor in wherein said two layers comprises fluid permeation prevention layer, and the second layer in described two layers comprises the mixture of following material:

(1) at least one halogenation of 100wt% contains the elastomer of isobutene;

(2) at least one filler of about about 50wt% of 20-;

(3) at least one processing oil of about about 30wt% of 0-;

(4) at least one tackifier of about about 20 parts/100 parts of 1-; With

(5) approximately 0.2-about 15 parts/100 parts of rubber for described elastomeric curing system;

Wherein said fluid permeation prevention layer comprises the polymer composition of the Young's modulus with 1-500MPa, and described polymer composition comprises:

(A) based on the gross weight of described polymer composition, at least at least one of 10wt% has thermoplastic engineering resin's component of the Young's modulus higher than 500MPa, wherein said thermoplastic engineering resin's component is selected from polyamide, mylar, polynitrile resins, polymethacrylate resin, polyvinyl resin, celluosic resin, fluororesin and imide resin

(B) based on the gross weight of described polymer composition, at least at least one of 10wt% has not higher than the elastomeric component of the Young's modulus of 500MPa, wherein said elastomeric component be selected from diene rubber, halogen-containing rubber, silicone rubber, containing sulphur rubber and fluorubber, and

The plasticizer of 2-30 part/100 part rubber, based on component (B), and

The total amount of the wherein said component of o (A) and described component (B) is at least 30wt%, based on the gross weight of described polymer composition, wherein said elastomeric component (B) is dispersed in the matrix of described thermoplastic resin component (A) using sulfuration or partial vulcanization state as discontinuous phase in described polymer composition, and

O wherein treated described fluid permeation prevention layer removes residual plasticizer with the surface from described layer.

9. the composition of claim 8, wherein said component (1) is (i) C ₄-C ₇isomonoolefin and the halogen-containing random copolymer to ring-alkylated styrenes, the described about 20wt% of about 0.5-ring-alkylated styrenes being accounted for described copolymer, or (ii) C ₄-C ₁₂isomonoolefin and C ₄-C ₁₄the halogen-containing random copolymer of polyene; In each case, described halogen is selected from chlorine, bromine and their mixture.

10. the composition of claim 8 or 9, wherein said at least one elastomeric component B is selected from C ₄-C ₇isomonoolefin and halide, brominated isobutylene-p-methylstyrene copolymer, hydrogenated nitrile-butadiene rubber, acrylonitrile-butadiene rubber, chlorosulfonated polyethylene, haloflex, epichlorohydrin rubber, chlorinated scoline and brombutyl to alkylstyrene copolymers.

Composition any one of 11. claim 8-10, wherein said at least one tackifier comprise condensation product and their the ingredients of a mixture that at least one is selected from rosin, rosin derivative, tert-butyl phenol and acetylene.

Composition any one of 12. claim 8-11, wherein said at least one tackifier comprise the mixture of the composition at least two kinds of condensation products and their mixture being selected from rosin, rosin derivative, tert-butyl phenol and acetylene.

Composition any one of 13. claim 8-12, wherein said fluid permeation prevention layer has 25 × 10 ^-12cccm/cm ²seccmHg (at 30 DEG C) or lower air permeability coefficient, the described at least one thermoplastic engineering resin of described polymer composition has 25 × 10 ^-12cccm/cm ²the described at least one elastomer of seccmHg (at 30 DEG C) or lower air permeability coefficient and described polymer composition has higher than 25 × 10 ^-12cccm/cm ²seccmHg (at 30 DEG C) or lower air permeability coefficient.

The composition being suitable for tire any one of 14. claim 8-13, the wherein said layer comprising at least one engineering resin is inner liner.

15. pneumatic tires, comprising:

I () comprises and has about 25 × 10 ^-12cccm/cm ²the air permeation prevention layer of the polymer composition of the Young's modulus of seccmHg (at 30 DEG C) or lower air permeability coefficient and the about 500MPa of about 1-, the described layer of described polymer composition comprises:

(A) based on the gross weight of described polymer composition, at least at least one of 10wt% has about 25 × 10 ^-12cccm/cm ²the thermoplastic resin component of seccmHg (at 30 DEG C) or lower air permeability coefficient and the Young's modulus higher than 500MPa, described resin Composition is selected from polyamide, mylar, polynitrile resins, polymethacrylate resin, polyvinyl resin, celluosic resin, fluororesin and imide resin

(B) based on the gross weight of described polymer composition, at least at least one of 10wt% has higher than about 25 × 10 ^-12cccm/cm ²the air permeability coefficient of sec cmHg (at 30 DEG C) and not higher than the elastomeric component of the Young's modulus of 500MPa, described elastomeric component be selected from diene rubber, halogen-containing rubber, silicone rubber, containing sulphur rubber and fluorubber, and

(C) plasticizer of 2-30 part/100 part rubber, based on component (B), and

Total amount (A)+(B) of wherein said component (A) and described component (B) is at least about 30wt%, based on the gross weight of described polymer composition, wherein said elastomeric component (B) is dispersed in using sulfided state as discontinuous phase in the matrix of thermoplastic resin component (A) in described polymer composition; With

Wherein said air permeation prevention layer is substantially free of residual plasticizer; With

(ii) directly contact the adhesive tie layer of described air permeation prevention layer, described tack coat comprises the mixture of following material:

(1) at least one halogenation of 100wt% contains the elastomer of isobutene;

(2) at least one filler of about about 50wt% of 20-;

(3) at least one processing oil of about about 30wt% of 0-;

(4) at least one tackifier of about about 20 parts of 1-/100 parts (phr); With

(5) approximately about 15 parts/100 parts rubber (phr) of 0.1-for described elastomeric curing system.

The pneumatic tire of 16. claims 15, wherein said component (i) (A) is at least one polyamide, and described component (i) (B) is C ₄-C ₇isomonoolefin and to the brominated random elastomeric copolymer of at least one of ring-alkylated styrenes, and described tack coat component (1) is (i) C ₄-C ₇isomonoolefin and the brominated random copolymer to ring-alkylated styrenes.

The pneumatic tire of 17. claims 15 or 16, wherein said at least one tackifier comprise condensation product and their the ingredients of a mixture that at least one is selected from rosin, rosin derivative, tert-butyl phenol and acetylene.