CN101428530A - Innerliner for tire and tire using the same - Google Patents
Innerliner for tire and tire using the same Download PDFInfo
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- CN101428530A CN101428530A CNA2008101752382A CN200810175238A CN101428530A CN 101428530 A CN101428530 A CN 101428530A CN A2008101752382 A CNA2008101752382 A CN A2008101752382A CN 200810175238 A CN200810175238 A CN 200810175238A CN 101428530 A CN101428530 A CN 101428530A
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Abstract
The present invention provides an inner liner for tyer and the tyer with the same. The inner liner for tyer can joint the adjacent rubber component without adhesive and has the advantages of excellent economy, excellent low temperature resistance, and high selecting freedom of material between resin layer and adjacent rubber component. The inner linear for tyre according to the invention is formed through laminating the composition containing elastomer component on the resin layer and irradiating the energy beam necessary for partially generating crosslinking between the resin layer and the elastomer component. Thus the energy beam is electron ray preferably. The absolute value of the difference between the SP value of resin of resin layer and the SP value of elastomer component is less than 9. The layer formed by the composition comprising elastomer component and the adjacent rubber component are co-crosslinked through vulcanizing.
Description
Technical field
The present invention relates to a kind of inner liner for tire, it can not use cement to engage in abutting connection with rubber components, and economy and low temperature resistance are good, selects the degree of freedom height in abutting connection with the material of rubber components and the resin bed that constitutes inside liner.
Background technology
Before,, be equipped on as the air barrier layer in the inside liner of tire inner surface, use a kind of rubber composition for keeping the interior pressure of tire, its with butyl rubber or halogenated butyl rubber etc. as main material.But these are with the rubber composition of butyl-like rubber as main material, because the air barrier is lower, when this rubber composition was used for inside liner, the thickness of inside liner must make about 1mm.Therefore, the weight that inside liner accounts for tire is about 5%, becomes obstacle to improve aspect the motor vehicle fuel expense in the weight that reduces tire.In order to overcome these problems, a kind of inner liner for pneumatic tire is disclosed, it also possesses the low resin bed of gas-premeable except rubber components such as described butyl rubber, improve the air barrier and reduce weight (with reference to Japanese kokai publication hei 6-40207 communique) thereby take into account.
In the manufacturing of this inner liner for pneumatic tire, for with resin bed with engage in abutting connection with rubber components, use indirect cement or the contour polar rubber of epoxy styrene butadiene styrene rubber (with reference to No. 2007/0031661 specification sheets of U.S. Patent Application Publication).But the price of this indirect cement or high polar rubber is very high, and the glass transition temperature of the poly-mer in cooperating is higher, when using as tyre element, breaks the low temperature resistance deficiency in the travelling in the winter time sometimes.
Patent documentation 1: Japanese kokai publication hei 6-40207 communique
Patent documentation 2: No. 2007/0031661 specification sheets of U.S. Patent Application Publication
Summary of the invention
The problem that invention will solve
In order to address these problems, also developed a kind of method, this method by under adjacency rubber and resin bed fit-state to its irradiation electron ray, thereby engage in abutting connection with importing co-crosslinking between rubber and this resin bed at this.
But in this method, bond strength depends on employed resin bed and changes in abutting connection with the material of rubber components, and therefore, in order to keep described bond strength, various Material Selection are restricted.
Other aspects, a kind of method is disclosed in TOHKEMY 2007-276235 communique, this method fits in the rubber composition parts by the laminated resin body with thermoplastic elastomer, after the tire that formed by the stacked body of this resin-rubber carried out the electron ray irradiation with parts, crosslinked by sulfuration again to import.But,,,, have the relatively poor situation of anti-deterioration of rubber layer so form uneven eyed structure sometimes owing in rubber layer, import carbon-carbon bond and sulfur-crosslinked by electron ray irradiation and sulfuration according to this method.In addition, do not have knitting layer, the viscosity deficiency between rubber and the film is so there is situation about peeling off when tire building.
Therefore, the object of the present invention is to provide a kind of inner liner for tire, it does not use high price cement such as indirect cement or high polar rubber and can engage in abutting connection with rubber components, and economy and low temperature resistance are good, and resin bed and select the degree of freedom height in abutting connection with the material of rubber components.
The method of dealing with problems
The inventor etc. have carried out in-depth study in order to reach above-mentioned purpose, found that, a kind of inner liner for tire can be provided, it is by the stacked composite that contains the elastic body composition on resin bed, then to its irradiation energy ray, can with good strength with engage in abutting connection with rubber components, economy and low temperature resistance are good, and resin bed and select the degree of freedom height, and finished the present invention in abutting connection with the material of rubber components.
That is, inner liner for tire of the present invention, it is by the stacked composite that contains the elastic body composition on resin bed, and irradiation makes, and the partly crosslinked required energy-ray of generation forms between this resin bed and this elastic body composition.
In inner liner for tire of the present invention, described energy-ray is preferably electron ray.
In addition, in the suitable example of inner liner for tire of the present invention, the absolute value of difference that constitutes the SP value of the SP value of resin of described resin bed and described elastic body composition is in 9.
In other suitable examples of inner liner for tire of the present invention, by the described composite that contains the elastic body composition form the layer by the sulfuration with carry out co-crosslinking in abutting connection with rubber components.
In other suitable examples of inner liner for tire of the present invention, described elastic body composition is a diene elastomers.
In other suitable examples of inner liner for tire of the present invention, described elastic body composition is that weight average molecular weight is 1000～150000 composition.
In other suitable examples of inner liner for tire of the present invention, described elastic body composition is that weight average molecular weight is 150000～3000000 composition.
In other suitable examples of inner liner for tire of the present invention, described elastic body composition is that weight average molecular weight is that 1000～150000 composition and weight average molecular weight are 150000～3000000 mixture of ingredients.
In other suitable examples of inner liner for tire of the present invention, described composite comprises viscosity and gives composition.
In other suitable examples of inner liner for tire of the present invention, described resin bed contains the protective cover that is formed by thermoplastic elastomer.
In other suitable examples of inner liner for tire of the present invention, described thermoplastic elastomer is thermoplastic carbamate's class elastic body.
In other suitable examples of inner liner for tire of the present invention, the described composite that contains the elastic body composition comprises carbon black.
In other suitable examples of inner liner for tire of the present invention, the described composite that contains the elastic body composition comprises crosslinking agent, crosslinking accelerator and crosslinked promotion auxiliary agent.
In other suitable examples of inner liner for tire of the present invention, described resin bed contains that oxygen permeability coefficient is 9.0 * 10 under 20 ℃, 65%RH
-12Cm
3Cm/cm
2The barrier layer that seccmHg is following.
In other suitable examples of inner liner for tire of the present invention, described barrier layer comprise ethylene-vinyl alcohol copolymer, modified ethylene vinyl alcohol copolymer and polyamide any.
In addition, the fetus face that tire of the present invention has pair of bead portion, pair of sidewall portion and connects two sidewall portions, also has between above-mentioned pair of bead the bracing ply of tire radial outside that extends, strengthens the carcass of its each one and be disposed at the crown part of described carcass with ring-type, it is characterized in that the tire inner surface in described carcass inboard has arbitrary described inner liner for tire.
The manufacture method of inner liner for tire of the present invention is characterized in that, the stacked composite that contains the elastic body composition on described resin bed then, makes the partly crosslinked required energy-ray of generation between this resin bed and this elastic body composition to its irradiation.
In the suitable example of the manufacture method of inner liner for tire of the present invention, described energy-ray is an electron ray.
In other suitable examples of the manufacture method of inner liner for tire of the present invention, the absolute value of difference that constitutes the SP value of the SP value of resin of described resin bed and described elastic body composition is in 9.
In other suitable examples of the manufacture method of inner liner for tire of the present invention, the layer that forms by the described composite that contains the elastic body composition by sulfuration with carry out co-crosslinking in abutting connection with rubber components.
In other suitable examples of the manufacture method of inner liner for tire of the present invention, described elastic body composition is a diene elastomers.
In other suitable examples of the manufacture method of inner liner for tire of the present invention, described elastic body composition is that weight average molecular weight is 1000～150000 composition.
In other suitable examples of the manufacture method of inner liner for tire of the present invention, described elastic body composition is that weight average molecular weight is 150000～3000000 composition.
In other suitable examples of the manufacture method of inner liner for tire of the present invention, described elastic body composition is that weight average molecular weight is that 1000～150000 composition and weight average molecular weight are 150000～3000000 mixture of ingredients.
In other suitable examples of the manufacture method of inner liner for tire of the present invention, described composite comprises viscosity and gives composition.
In other suitable examples of the manufacture method of inner liner for tire of the present invention, described resin bed contains the protective cover that is formed by thermoplastic elastomer.
In other suitable examples of the manufacture method of inner liner for tire of the present invention, described thermoplastic elastomer is thermoplastic carbamate's class elastic body.
In other suitable examples of the manufacture method of inner liner for tire of the present invention, the described composite that contains the elastic body composition comprises carbon black.
In other suitable examples of the manufacture method of inner liner for tire of the present invention, the described composite that contains the elastic body composition comprises crosslinking agent, crosslinking accelerator and crosslinked promotion auxiliary agent.
In other suitable examples of the manufacture method of inner liner for tire of the present invention, described resin bed contains that oxygen permeability coefficient is 9.0 * 10 under 20 ℃, 65%RH
-12Cm
3Cm/cm
2The barrier layer that seccmHg is following.
In other suitable examples of the manufacture method of inner liner for tire of the present invention, described barrier layer comprise ethylene-vinyl alcohol copolymer, modified ethylene vinyl alcohol copolymer and polyamide any.
In addition, in the manufacture method of tire of the present invention, the fetus face that described tire has pair of bead portion, pair of sidewall portion and connects two sidewall portions, also possesses between above-mentioned pair of bead the bracing ply of tire radial outside that extends, strengthens the carcass of its each one and be disposed at the crown part of described carcass with ring-type, it is characterized in that the tire inner surface in described carcass inboard has the inner liner for tire of making by the manufacture method of inner liner for tire of the present invention.
The invention effect
According to the present invention, a kind of inner liner for tire is provided, it can not use high price cements such as indirect cement or high polar rubber to engage in abutting connection with rubber components and form, and economy and low temperature resistance are good, and resin bed and in abutting connection with the Material Selection degree of freedom height of rubber components.
Description of drawings
Fig. 1 is the partial cross section figure of an embodiment of tire of the present invention.
Nomenclature:
1 bead part
2 sidewall portions
3 fetus faces
4 carcasses
5 bracing plys
6 inside liners
7 bead cores
8 bracing ply enhancement Layers
The specific embodiment
The manufacture method of inner liner for tire of the present invention is characterized in that, the stacked composite that contains the elastic body composition on resin bed, and irradiation makes the partial cross-linked required energy-ray of generation between this resin bed and this elastic body composition.Like this, by irradiation energy ray behind stacked described composite on the described resin bed, described resin bed engages with described elastic body composition co-crosslinking.That is to say, the elastic body composition carry out crosslinked in, described elastic body composition carries out co-crosslinking with the resin that constitutes resin bed, thereby resin bed is engaged securely with the composite that contains the elastic body composition.Here, for described resin bed and described elastic body composition co-crosslinking, the radiation dose that shines described energy-ray is preferably 1kGy～600kGy.At this, if described radiation dose is not enough 1kGy, then described co-crosslinking is insufficient, there are situation about peeling off in described resin bed and described composite, if surpass 600kGy, the deterioration of then described resin bed and described elastic body composition is easy to generate, in addition, in elastic body, carry out crosslinked, during sulfuration described elastic body composition with can't co-vulcanization in abutting connection with rubber.
Described energy-ray is meant: make strand dissociate with the electromagnetic wave that produces free radical etc.And, be not particularly limited as described energy-ray, for example can enumerate electron ray, gamma line, ultraviolet ray and far-infrared rays etc.In addition, in the present invention, when utilizing ultraviolet irradiation, need to add reagent, in addition, when utilizing the irradiation of gamma line, need isotope in order to promote to solidify, not easy.On the other hand, in the present invention, when utilizing the electron ray irradiation, might not need to add reagent or isotope, but and momentary switch, very easy.In addition, electron ray also has the radiation dose rate advantage bigger than gamma line.Therefore, as described energy-ray preferred electron ray.
As mentioned above, in the technical scheme of in aforementioned TOHKEMY 2007-276235 communique, putting down in writing, in abutting connection with rubber and the resin bed that contains the elastic body composition at the irradiation electron ray and when vulcanizing then, because at adjacency rubber, resin bed with contain and import carbon-carbon bond and sulfur-crosslinked between the composite of elastic body composition, so form uneven eyed structure sometimes, and the anti-deterioration of rubber layer is relatively poor.On the other hand, in the present invention, owing at adjacency rubber and contain and only import sulfur-crosslinkedly between the composite of elastic body composition, compare with the technical scheme of putting down in writing in the TOHKEMY 2007-276235 communique, eyed structure is more even, and the anti-deterioration of rubber layer is higher.
In addition, as the layer that constitutes described resin bed, can enumerate and contain thermoplastic carbamate's class elastic body, polystyrene-poly (ethylene/butylene) block-polystyrene copolymer, nylon 6, nylon 6,6, polybutadiene, maleic anhydride modified polyethylene, maleic anhydride modified poly-butadiene, ethylene-vinyl alcohol copolymer (EVOH), modification EVOH, polyethylene, polypropylene, polyethylene terephthalate (PET), vinylidene chloride, polybutylene terephthalate (PBT), vinyl acetate resinoid etc., because the air barrier is good and the inflation pressure retention of tire is increased substantially, therefore, the layer that preferably contains modification EVOH.
As described elastic body composition, can enumerate elastic body that polyisoprene (for example natural rubber), styrene-butadiene-copolymer, styrene isoprene butadidenne 2 membered copolymers, styrene butadiene acrylonitrile copolymer, ethylene-propylene-diene terpolymer, polyisobutene, isobutylene isoprene copolymer, poly-butadiene, butyl rubber etc. have the diene skeleton, olefin polymer, EXXPRO and be the material of main chain backbone with halogenated butyl etc.Here, because it is good with the co-crosslinking of foreign peoples or similar rubber in the vulcanizing system of sulphur, and be the electron ray cross-linking type, pretend and be the preferred diene elastomers of aforementioned elastic body composition, the preferred polyisoprene of the main chain backbone of aforementioned elastic body composition, styrene-butadiene-copolymer, poly-butadiene.In addition, aforementioned diene elastomers can be periodic copolymer, for example can enumerate SBS, SIS (SIS) etc.In addition, but aforementioned elastic body composition partial hydrogenation.
As described elastic body composition, preferably weight average molecular weight is 1000～150000 composition, and being more preferably is 3000～120000 composition, further 3500～100000 composition preferably.In addition, described elastic body composition preferably weight average molecular weight be 150000～3000000 composition.In addition, described elastic body composition preferably weight average molecular weight be that 1000～150000 composition and weight average molecular weight are 150000～3000000 mixture of ingredients.Here, the weight average molecular weight less than 1000 of described elastic body composition then has the inadequate situation of collapse strength of foregoing, surpasses at 3000000 o'clock, and the viscosity of foregoing is insufficient.In addition, weight average molecular weight is that 1000～150000 composition has viscosity and gives function, and weight average molecular weight is that 150000～3000000 composition has the function that improves collapse strength.In addition, as described composition, can use the material of the backbone structure identical with the above-mentioned material of enumerating as the elastic body composition.
In addition, described composite is fit to comprise viscosity and gives composition.Give composition as this viscosity, be preferably as the known material of adhesive agent, be not particularly limited, for example can enumerate gum resin, toll oil rosin, wood rosin, Foral, disproportionated rosin, newtrex, ester gum, Foral pentaerythritol ester of natural materials or derivatives thereof etc., and petroleum resin of synthetic resin, coumarone indeneresin, styrene resin, phenol resin, Xylene resin etc.
The radiation dose of described electron ray is preferably the scope of 5～600kGy, more preferably the scope of 10～500kGy.During the radiation dose of electron ray is not enough 5kGy, be difficult to carry out crosslinked, and when surpassing 600kGy, the deterioration of the shaped object of then described composite and described resin is easy to generate.
Here, the described form that contains the composite of elastic body composition is not particularly limited, film like or aqueously all can.When said composition is under the situation of liquid composition, preferably on resin bed after this constituent of coating, carry out the electron ray irradiation after being dried when containing solvent again.In addition, when this aqueous composite contains solvent,, be not particularly limited, can be fit to enumerate organic solvents such as toluene as long as elastic body is dispersed or dissolved.In addition, the absolute value of difference that constitutes the SP value of the SP value of resin of described resin bed and described elastic body composition is preferably in 9, more preferably in 8, more preferably in 6, is preferably in 4.37 especially.Like this, if the difference of resin and elastomeric SP value is less,, thereby can improve the connectivity between resin and the composite then because the elastomeric compatibility on resin increases, can import more mutual actions such as co-crosslinking.In addition, owing to can select elastic body according to employed resin and in abutting connection with the material of rubber layer, so each Material Selection degree of freedom height.
In inner liner for tire of the present invention and manufacture method thereof, preferred described contain the composite of elastic body composition with in abutting connection with the rubber components co-crosslinking.The described composite that contains the elastic body composition engages with adjacency rubber layer physical property owing to having stickness, imports co-crosslinking by sulfuration between them, thereby makes joint more strong.
In inner liner for tire of the present invention and manufacture method thereof, described resin bed preferably contains the layer that thermoplastic elastomer (TPE) forms.And,, be suitably for thermoplastic carbamate's class elastic body as this thermoplastic elastomer.Contain the layer that forms by thermoplastic elastomer by described resin bed, can make the barrier layer part thin layerization of resin bed, and also can suppress the generation or the stretching, extension of the be full of cracks of this barrier layer.The reaction that described thermoplastic carbamate's class elastic body can pass through polyalcohol, isocyanate compound and short chain diatomic alcohol obtains.Polyalcohol and short chain diatomic alcohol by with the addition reaction of isocyanate compound, form straight chain shape polyurethane.Here, polyalcohol forms soft in thermoplastic carbamate's class elastic body, and isocyanate compound and short chain diatomic alcohol form hard part.And the kind by changing raw material, use level, polymerizing condition etc. can change the elastomeric character of thermoplastic carbamate's class in wide scope.
In addition, in inner liner for tire of the present invention and manufacture method thereof, the described composite that contains the elastic body composition preferably comprises carbon black.Comprise carbon black by the described composite that contains the elastic body composition, increased intensity, and increased the engaging force between film-elastic body.
In inner liner for tire of the present invention and manufacture method thereof, the described composite that contains the elastic body composition preferably comprises crosslinking agent, crosslinking accelerator and crosslinked promotion auxiliary agent.The composite that contains the elastic body composition can improve the cross-linking efficiency when vulcanizing by comprising crosslinking agent, crosslinking accelerator and crosslinked promotion auxiliary agent.Here, as described crosslinking agent,, generally cooperate sulphur in order to adjust crosslinking rate and modulus of elasticity.In addition, as described crosslinking accelerator, can enumerate diphenylguanidine (DPG), tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), 2-mercaptobenzothiazole zinc salt (ZnBDC), 2-mercaptobenzothiazole (MBT), two sulfo-2-[4-morpholinodithios (MBTS), N cyclohexyl 2 benzothiazole sulfenamide (CBS) and N tert butyl benzothiazole 2 sulfenamide (BBS) etc.In addition, can enumerate zinc white (zinc oxide) etc. as described crosslinked promotion auxiliary agent.
In inner liner for tire of the present invention and manufacture method thereof, described resin bed contains preferably that oxygen permeability coefficient is 9.0 * 10 under 20 ℃, 65%RH
-12Cm
3Cm/cm
2The barrier layer that seccmHg is following, more preferably the oxygen permeability coefficient of this barrier layer is 1.0 * 10
-12Cm
3Cm/cm
2Below the seccmHg, more preferably 5.0 * 10
-13Cm
3Cm/cm
2Below the seccmHg.Here, oxygen permeability coefficient uses as the typical value of the gas-premeable of expression resin bed.If oxygen permeability coefficient surpasses 9.0 * 10 under 20 ℃, 65%RH
-12Cm
3Cm/cm
2SeccmHg then when using as inside liner, for the inflation pressure retention (air barrier) that improves tire, has to thicken described resin bed, can not reduce the weight of tire fully.
As described barrier layer, expectation has can be by the structure of energy-ray irradiation with described elastic body composition co-crosslinking.Here, when described barrier layer can not be with elastic body composition co-crosslinking, when for example described barrier layer is inorganic overlay film of evaporation (aluminium oxide etc.) or inorganic filler, can be under energy-ray can with the inorganic overlay film of configuration on the elastic body of elastic body composition co-crosslinking or the TPE, elastic body composition and TPE adjacency is implemented.In addition, when barrier layer can pass through energy-ray " crosslinked ", can make barrier layer and TPE adjacency.Reason is, barrier layer since by energy-ray with elastic body composition co-crosslinking and barrier property slightly reduces, but by with the TPE adjacency, can prevent such barrier property reduction.As energy-ray irradiation down can with the described barrier layer of elastomer layer co-crosslinking, be suitably for the layer that contains at least a formation in ethylene-vinyl alcohol copolymer, modified ethylene vinyl alcohol copolymer and the polyamide.These poly-mers are also applicable to the high material of the barrier properties for gases of packaging material for food degree, and it is fit in order to satisfy the desired performance of inner liner for tire.In addition,, be preferably the material with soft chain segment of energy-ray cross-linking type, can enumerate styrene ethylene butylene styrene periodic copolymer (SEBS), thermoplastic polyurethane (TPU), polyethylene (PE) etc. as TPE.
Tire of the present invention, expectation has above-mentioned inner liner for tire and adopts above-mentioned inner liner for tire to make.Below, with reference to accompanying drawing tire of the present invention is elaborated.Fig. 1 is the partial cross section figure of an embodiment of tire of the present invention.The fetus face 3 that tire shown in Figure 1 has pair of bead portion 1 and pair of sidewall portion 2 and connects two sidewall portions 2, also possess between above-mentioned pair of bead 1 and extend and strengthen its each one 1 with ring-type, 2,3 carcass 4 and by the bracing ply (belt) 5 that 2 bracing plys of the tire radial outside of the crown part that is disposed at this carcass 4 form has also disposed inside liner 6 on the tire inner surface of these external these carcass 4 inboards.
In the tire of illustrated example, body and being formed from the radially outside laterally revers turn part that curls in the inboard of tire width direction on every side that carcass 4 is extended by ring-type between the pair of bead core 7 that is embedded in respectively in the above-mentioned bead part 1 at each bead core 7, but in tire of the present invention, the number of plies and the structure of carcass 4 are not limited by this example.
In addition, though in the tire of illustrated example, bracing ply 5 is formed by 2 bracing ply, and in tire of the present invention, the sheet number that constitutes the bracing ply of bracing ply 5 is not limited.Here, bracing ply is formed by the rubberised layer of the cord that extends with respect to the tire equator face tilt usually, and 2 bracing plys are stacked in the mode that the clamping equatorial plane reciprocally intersects by the cord that constitutes this bracing ply, thus formation bracing ply 5.In addition, the tire of illustrated example has at the tire radial outside of above-mentioned bracing ply 5 to cover the bracing ply enhancement Layer 8 that bracing ply 5 integral body are configured, but tire of the present invention have or not bracing ply enhancement Layer 8 can, also can possess the bracing ply enhancement Layer of other structure.Here, bracing ply enhancement Layer 8 is formed by the rubberised layer with respect to the cord of the substantially parallel arrangement of tire circumferential direction usually.
The inner liner for tire of the application of the invention can provide tire and manufacture method thereof, and the economy and the low temperature resistance of this tire are good, and the relatively simple for structure and lightweight of inside liner, thus combustion to take efficient also good.In addition, though but gases such as filling air, nitrogen, helium in the tire of the present invention are considered many fillings of cost air.
Inner liner for tire of the present invention is seen as the resin with viscosity from another point of view.Therefore, inner liner for tire of the present invention can suitably be selected aforementioned resin and foregoing etc., also can use the resin with viscosity in as other purposes of needs.
Embodiment
Below, by embodiment the present invention is described more specifically, but the present invention is not subjected to any qualification of these embodiment, in the scope that does not change its aim, can suitably change.
The method for making of resin bed 1
In the compressive reaction groove, (190 ℃ of ethylene-vinyl alcohol copolymers that add 44 moles of % of ethylene contents, the saponification degree 99.9% of 2 mass parts, MFR:5.5g/10 under the 2160g loading minute) and 8 mass parts N-N-methyl-2-2-pyrrolidone N-s, under 120 ℃, added thermal agitation 2 hours, ethylene-vinyl alcohol copolymer is dissolved fully.After wherein adding 0.4 mass parts epoxypropane, 160 ℃ of heating 4 hours.Heating makes it to separate out in the distilled water of 100 mass parts, and fully washs N-N-methyl-2-2-pyrrolidone N-and unreacted epoxypropane with a large amount of distilled waters after finishing, and obtains modified ethylene vinyl alcohol copolymer.In addition, with comminutor the modified ethylene vinyl alcohol copolymer of gained being refined as particle diameter is about 2mm, fully washs with a large amount of distilled waters then.After dry 8 hours, the use double screw extrusion machine is 200 ℃ of fusions and carry out granulationization in a vacuum for particle after at room temperature will washing.Use this granulation, and adopt the film-forming machine that constitutes by 40mmf extruder (PLABORco., the PLABOR GT-40-A that Ltd makes) and T die head,, obtain the single-layer resin layer 1 of thick 20 μ m with following extrusion condition film forming.
Form: single screw extrusion machine (non-belt type)
L/D：24
Bore: 40mmf
Screw rod: one pole light-duty (single full-light type), surfaces nitrided steel
Screw rod rotation number: 40rpm
Mould: 550mm width rack type die
Lip interval: 0.3mm
Cylinder body, die head temperature is set: C1/C2/C3/ joint/die head=180/200/210/210/210 (℃)
The method for making of resin bed 2
Remove and replace 44 moles of % of ethylene contents, (190 ℃ of the ethylene-vinyl alcohol copolymers of saponification degree 99.9%, MFR:5.5g/10 under the 2160g loading minute), (190 ℃ of the ethylene-vinyl alcohol copolymers of ethylene contents 32 moles of %, saponification degree 99.9% have been used, MFR:7.0g/10 under the 2160g loading minute) outside, resin bed 2 made in the same manner with above-mentioned resin bed 1.
The method for making of resin bed 3
Use double screw extrusion machine; the granulation 80 quality % that the method for making of described resin bed 1 is obtained, mix, obtain resin combination with granulation 20 quality % by the granulation acquisition of the synthetic back of known method synthesis of maleic anhydride modification hydrogenation styrene-ethylene-butadiene-styrene block copolymer.Use this resin combination and thermoplastic polyurethanes (TPU) (KURAMIRON 3190 that (strain) KRARAY makes), adopt 2 kinds of 3 layers of co-extrusion devices, with following co-extrusion modling condition, make resin bed 3 (thermoplastic urethane layers/resin combination layer/thermoplastic urethane layers, thick 20/20/20 (μ m)).
The extrusion temperature of each resin: C1/C2/C3/ die head=170/170/200/200 ℃
The extruder specification of each resin:
Thermoplastic polyurethane: the smart machine work in 25mm φ extruder P25-18AC[Osaka Co., Ltd. makes]
Resin combination (D) or modification EVOH (B): the smart machine manufacturing of 20mm φ extruder LABO machine ME type CO-EXT[Toyo Co., Ltd.]
T die head specification: 2 kinds of 3 layers of usefulness of 500mm width [PLABOR co., Ltd makes]
The temperature of chill roll: 50 ℃
Rate of delivery: 4m/ minute
Modulator approach in abutting connection with rubber 1
Make with the prescription composition of record in the following table 1 in abutting connection with rubber 1.
Table 1
| Mass parts | |
| Butyl rubber * 1 | 100 |
| N-550 (carbon black) | 50 |
| Stearic acid * 2 | 2 |
| Zinc white * 3 | 3 |
| Vulcanization accelerator * 4 | 1 |
| Sulphur | 0.5 |
*1 Exxon Mobile CHEMICAL (system), Exxon BROMO BUTYL222
*2 new Japanese physics and chemistry (system) 50S
*3 HAKISUITECH (strain) make, 2 kinds of zinc white, pulverulent product
*The emerging chemical frbre industry of 4 imperial palaces (strain) is made, NOCCELER DM
Method of adjustment in abutting connection with rubber 2
Make with the prescription composition of record in the following table 2 in abutting connection with rubber 2.
Table 2
| Mass parts | |
| NR*1 | 50 |
| SBR*2 | 68.75 |
| GPF N-660 (carbon black) * 3 | 43 |
| Processing oil * 4 | 8 |
| Ageing resistant * 5 | 1.5 |
| Stearic acid * 6 | 1.5 |
| Zinc white * 7 | 4 |
| Vulcanization accelerator * 8 | 0.5 |
| Vulcanization accelerator * 9 | 1 |
| Sulphur | 2.66 |
*1 RSS3 number
*2 JSR (system), SBR 1712 (18.75 mass parts oiling aromatic naphtha (aromatic oil))
*3 rising sun CARBON (system), 50S
*4 SUN OIL COMPANY companies (system), Sundex 790
*The emerging chemical frbre industry of 5 imperial palaces (strain) is made, Nocrac 224-S, 2,2,4-trimethyl-1,2-EEDQ poly-mer
*6 new Japanese physics and chemistry (system), 50S
*7 HAKISUITECH (system), 2 kinds of zinc white, pulverulent product
*8 Kawaguchi's chemical frbre industrys (system), Accel M, 2-mercaptobenzothiazole
*9 Kawaguchi's chemical frbre industrys (system), Accel CZ, N cyclohexyl 2 benzothiazole sulfenamide
The method of adhesive test
About the sample of adhesive test mensuration usefulness, be benchmark with JIS Z0237, the adhesive test of popping one's head in is measured viscosity.Measured value with comparative example 1 is 100, with other measured value exponentiate.
The test method of the associativity between elastic body-resin bed
Following components A is immersed in the toluene, and the sample of the but not stripping of composition layer swelling (elastic body is not gone out by the toluene extracting) on the components A is evaluated as well, and the sample of the composition layer stripping on the components A (elastic body is gone out by the toluene extracting) is evaluated as bad.
The evaluation method of inflation pressure retention
Inflation pressure retention for the tire of above-mentioned making, under air is pressed 140kPa, be equivalent to increase the weight of 6kN on the going barrel of speed of 80km/h and exert pressure, is implemented travelling of 10000km.Use the tire do not travel and travel under these conditions after tire, estimate inflation pressure retention under the following conditions.Inflation pressure retention for will test make after tire is loaded onto the steel ring of 6JJ * 15 in pressure be to measure its interior pressure after 3 months by 240kPa, estimate with following formula:
Inflation pressure retention=((240-b)/(240-a)) * 100
[in the formula, a is the test interior pressure of tire after 3 months, and b is the interior pressure behind 3 months of not traveling tire (using the air tyre of common elastometric lining layer) of following comparative example 1 record].And other measured values are carried out exponentiate with the value of comparative example 1 as 100.
The evaluation method of the back outward appearance of travelling
The back outward appearance of travelling be evaluated as the visual observations tire inner surface, estimate inside liner and have or not and peel off.
Embodiment 1
On the resin bed 1 of the long 20cm * wide 10cm that makes by said method, coating solution, this solution is with IR2200 (JSR manufacturing, polyisoprene, the weight average molecular weight: 140000) be dissolved in solution that 500ml toluene obtain, and make it abundant drying of 40g as foregoing.Then, use day electron beam irradiation device of new HIGHT VOLTAGE (strain) manufacturing " to produce and use Curetron EBC200-100 ", carry out electron ray irradiation (accelerated voltage 200kV), obtain components A with radiation dose shown in the table.Use this components A, test according to the associativity that said method carries out between adhesive test and elastic body-resin bed.Peeling off drag is: the coated face of the foregoing of components A with make according to said method overlaps in abutting connection with rubber 1 after, vulcanize the formation complex, this complex is that benchmark carries out T type peel test with JIS K6854 then, mensuration is peeled off drag.Measured value is carried out exponential representation with the drag of peeling off of comparative example 1 as 100.In addition, set components A as inside liner,, obtain automobile tyre (195/65R15) by under common conditions of vulcanization, vulcanizing in the gamut of tire curing inside face not.Use this automobile tyre, outward appearance after travelling by said method mensuration inflation pressure retention and observation.The result is shown in the table 3.Here, the mol wt of elastic body composition is the weight average molecular weight (Mw) of the polystyrene conversion using gel permeation chromatograph (GPC) and try to achieve.
Embodiment 2
Embodiment 2 mixes and uses outside 40g IR2200 and the 10gLIR30 (KURARAY system, polyisoprene) except replacing 40g IR2200, carries out according to the method for embodiment 1.The result is shown in the table 3.
Embodiment 5
Embodiment 5 is except replacing IR2200, mix to use the zinc oxide that 40g IR2200 and 17.2g carbon black, 1.0g sulphur (crosslinking agent), 0.2g make as the HAKISUITECH of crosslinking accelerator as the Accel CZ of the Accel M of Kawaguchi's chemical frbre industry manufacturing of crosslinking accelerator, the chemical frbre industry manufacturing of 0.4g Kawaguchi and 1.6g and take to carry out according to the method for embodiment 1 outside the electron ray exposure of 25kGy.The result is shown in the table 3.
Embodiment 7
Embodiment 7 is except replacing in abutting connection with rubber 1, use by said method make outside rubber 2, carry out according to the method for embodiment 1.The result is shown in the table 4.
29000) and use in abutting connection with rubber 2 and replace carrying out according to the method for embodiment 5 embodiment 8 is except also mix using 10g Liq IR (liquid polyisoprene, weight average molecular weight: in abutting connection with rubber 1.The result is shown in the table 4.
Embodiment 9
Embodiment 9 replaces carrying out according to the method for embodiment 5 in abutting connection with rubber 1 except also mixing to use 10g acetylene phenol resin and use in abutting connection with rubber 2.The result is shown in the table 4.
Embodiment 10
Embodiment 10 replaces carrying out according to the method for embodiment 1 polyisoprene except using SBR (#1500, weight average molecular weight 440000).The result is shown in the table 4.
Embodiment 11
Embodiment 11 replaces carrying out according to the method for embodiment 9 resin bed 1 except using resin bed 3.The result is shown in the table 4.
Embodiment 12
Embodiment 12 replaces carrying out according to the method for embodiment 1 IR2200 except using Liq IR.The result is shown in the table 4.
Comparative example 1
Comparative example 1 carries out according to the method for embodiment 1 except being coated with outside the foregoing (that is, only resin bed 1 has shone electron ray) after to resin bed 1 irradiation electron ray.The result is shown in the table 4.
Comparative example 2
Comparative example 2 except the resin bed 2 that adopts Metalock R30M (Japan's chemical research manufacturing) and will make according to said method with engage in abutting connection with rubber 1, carry out according to the method for comparative example 1.The result is shown in the table 4.
Shown in table 3 and table 4, with respect to comparative example, embodiment has good viscosity, peels off drag, the associativity between elastic body.And, use the tire of the inside liner manufacturing of embodiment to compare with the tire of the inside liner manufacturing of using comparative example, inflation pressure retention is good, and also not having in appearance after travelling peeled off, and is good.
Claims (32)
1. inner liner for tire, partly crosslinked required energy-ray of generation forms between described resin bed and described elastic body composition by making in stacked composite that contains the elastic body composition and irradiation on the resin bed for it.
2. inner liner for tire according to claim 1 is characterized in that, described energy-ray is an electron ray.
3. inner liner for tire according to claim 1 is characterized in that, the absolute value of difference that constitutes the SP value of the SP value of resin of described resin bed and described elastic body composition is in 9.
4. inner liner for tire according to claim 1 is characterized in that, by the described composite that contains the elastic body composition form the layer by the sulfuration with carry out co-crosslinking in abutting connection with rubber components.
5. inner liner for tire according to claim 1 is characterized in that, described elastic body composition is a diene elastomers.
6. inner liner for tire according to claim 1 is characterized in that, described elastic body composition is that weight average molecular weight is 1000～150000 composition.
7. inner liner for tire according to claim 1 is characterized in that, described elastic body composition is that weight average molecular weight is 150000～3000000 composition.
8. inner liner for tire according to claim 1 is characterized in that, described elastic body composition is that weight average molecular weight is that 1000～150000 composition and weight average molecular weight are 150000～3000000 mixture of ingredients.
9. inner liner for tire according to claim 1 is characterized in that, described composite comprises viscosity and gives composition.
10. inner liner for tire according to claim 1 is characterized in that described resin bed contains the protective cover that is formed by thermoplastic elastomer.
11. inner liner for tire according to claim 10 is characterized in that, described thermoplastic elastomer is thermoplastic carbamate's class elastic body.
12. inner liner for tire according to claim 1 is characterized in that, the described composite that contains the elastic body composition comprises carbon black.
13. inner liner for tire according to claim 1 is characterized in that, the described composite that contains the elastic body composition comprises crosslinking agent, crosslinking accelerator and crosslinked promotion auxiliary agent.
14. inner liner for tire according to claim 1 is characterized in that, described resin bed contains that oxygen permeability coefficient is 9.0 * 10 under 20 ℃, 65%RH
-12Cm
3Cm/cm
2The barrier layer that seccmHg is following.
15. inner liner for tire according to claim 14 is characterized in that, described barrier layer comprise ethylene-vinyl alcohol copolymer, modified ethylene vinyl alcohol copolymer and polyamide any.
16. tire, the fetus face that described tire has pair of bead portion and pair of sidewall portion and connects two sidewall portions, also has between described pair of bead the bracing ply of tire radial outside that extends and strengthen the carcass of its each one and be disposed at the crown part of described carcass with ring-type, it is characterized in that
Tire inner surface in described carcass inboard has each described inner liner for tire in the claim 1～15.
17. the manufacture method of each described inner liner for tire in the claim 1～15, it is characterized in that, the stacked composite that contains the elastic body composition on described resin bed, then, its irradiation is made the partly crosslinked required energy-ray of generation between described resin bed and described elastic body composition.
18. the manufacture method of inner liner for tire according to claim 17 is characterized in that, described energy-ray is an electron ray.
19. the manufacture method of inner liner for tire according to claim 17 is characterized in that, the absolute value of difference that constitutes the SP value of the SP value of resin of described resin bed and described elastic body composition is in 9.
20. the manufacture method of inner liner for tire according to claim 17 is characterized in that, by the described composite that contains the elastic body composition form the layer by the sulfuration with carry out co-crosslinking in abutting connection with rubber components.
21. the manufacture method of inner liner for tire according to claim 17 is characterized in that, described elastic body composition is a diene elastomers.
22. the manufacture method of inner liner for tire according to claim 17 is characterized in that, described elastic body composition is that weight average molecular weight is 1000～150000 composition.
23. the manufacture method of inner liner for tire according to claim 17 is characterized in that, described elastic body composition is that weight average molecular weight is 150000～3000000 composition.
24. the manufacture method of inner liner for tire according to claim 17 is characterized in that, described elastic body composition is that weight average molecular weight is that 1000～150000 composition and weight average molecular weight are 150000～3000000 mixture of ingredients.
25. the manufacture method of inner liner for tire according to claim 17 is characterized in that, described composite comprises viscosity and gives composition.
26. the manufacture method of inner liner for tire according to claim 17 is characterized in that, described resin bed contains the protective cover that is formed by thermoplastic elastomer.
27. the manufacture method of inner liner for tire according to claim 26 is characterized in that, described thermoplastic elastomer is thermoplastic carbamate's class elastic body.
28. the manufacture method of inner liner for tire according to claim 17 is characterized in that, the described composite that contains the elastic body composition comprises carbon black.
29. the manufacture method of inner liner for tire according to claim 17 is characterized in that, the described composite that contains the elastic body composition comprises crosslinking agent, crosslinking accelerator and crosslinked promotion auxiliary agent.
30. the manufacture method of inner liner for tire according to claim 17 is characterized in that, described resin bed contains that oxygen permeability coefficient is 9.0 * 10 under 20 ℃, 65%RH
-12Cm
3Cm/cm
2The barrier layer that seccmHg is following.
31. the manufacture method of inner liner for tire according to claim 30 is characterized in that, described barrier layer comprise ethylene-vinyl alcohol copolymer, modified ethylene vinyl alcohol copolymer and polyamide any.
32. the manufacture method of a tire, the fetus face that described tire has pair of bead portion and pair of sidewall portion and connects two sidewall portions, also possesses between described pair of bead the bracing ply of tire radial outside that extends and strengthen the carcass of its each one and be disposed at the crown part of described carcass with ring-type, it is characterized in that
Tire inner surface in described carcass inboard has the inner liner for tire of making by the manufacture method of each described inner liner for tire in the claim 17～31.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007288906 | 2007-11-06 | ||
| JP2007288906 | 2007-11-06 | ||
| JP2007-288906 | 2007-11-06 | ||
| JP2008281361 | 2008-10-31 | ||
| JP2008281361A JP5461822B2 (en) | 2007-11-06 | 2008-10-31 | tire |
| JP2008-281361 | 2008-10-31 |
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| Publication Number | Publication Date |
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| CN101428530A true CN101428530A (en) | 2009-05-13 |
| CN101428530B CN101428530B (en) | 2012-05-30 |
Family
ID=40644258
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101752382A Active CN101428530B (en) | 2007-11-06 | 2008-11-06 | Innerliner for tire and tire using the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5461822B2 (en) |
| CN (1) | CN101428530B (en) |
Cited By (4)
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| CN103732396A (en) * | 2011-05-31 | 2014-04-16 | 株式会社普利司通 | Multi-layered structure, inner liner for pneumatic tire, and pneumatic tire |
| CN103732397A (en) * | 2011-05-31 | 2014-04-16 | 株式会社普利司通 | Multi-layer structure, inner liner for pneumatic tire, and pneumatic tire |
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| CN105899594A (en) * | 2013-11-21 | 2016-08-24 | 阿利桑那化学公司 | Additives for rubber compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012002750A2 (en) * | 2010-06-30 | 2012-01-05 | 코오롱인더스트리 주식회사 | Film for tire inner liner, and preparation method thereof |
| JP5652050B2 (en) | 2010-08-19 | 2015-01-14 | 横浜ゴム株式会社 | Method for producing thermoplastic resin composition |
| US9724968B2 (en) | 2011-05-31 | 2017-08-08 | Bridgestone Corporation | Multilayer structure, inner liner for pneumatic tire, and pneumatic tire |
| JP6208927B2 (en) * | 2011-05-31 | 2017-10-04 | 株式会社ブリヂストン | Multilayer structure, inner liner for pneumatic tire, and pneumatic tire |
| JP6138429B2 (en) * | 2011-05-31 | 2017-05-31 | 株式会社ブリヂストン | Multilayer structure, inner liner for tire and pneumatic tire |
| US9399374B2 (en) | 2011-06-30 | 2016-07-26 | Kolon Industries, Inc. | Film for a tire inner liner and preparation method therefor |
| WO2013002602A2 (en) * | 2011-06-30 | 2013-01-03 | 코오롱인더스트리 주식회사 | Film for an inner liner of a tire and method for manufacturing same |
| JP5885988B2 (en) * | 2011-10-12 | 2016-03-16 | 株式会社ブリヂストン | Method for producing crosslinked film |
| JP6163721B2 (en) * | 2012-09-12 | 2017-07-19 | 住友ベークライト株式会社 | Tire inner liner seat and tire |
| JP2016055715A (en) * | 2014-09-08 | 2016-04-21 | 住友ベークライト株式会社 | Sheet for tire inner liner, and tire |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1036571A (en) * | 1996-07-23 | 1998-02-10 | Yokohama Rubber Co Ltd:The | Functional thermoplastic elastomer composition and its production |
| JPH1025375A (en) * | 1996-07-12 | 1998-01-27 | Yokohama Rubber Co Ltd:The | Thermoplastic elastomer composition and pneumatic tire and hose using the same |
| US6034164A (en) * | 1997-02-21 | 2000-03-07 | Exxon Research And Engineering Co. | Nanocomposite materials formed from inorganic layered materials dispersed in a polymer matrix |
| WO2006071311A1 (en) * | 2004-12-29 | 2006-07-06 | Exxonmobile Chemical Patents Inc. | Select elastomeric blends and their use in articles |
| JP2007276235A (en) * | 2006-04-05 | 2007-10-25 | Bridgestone Corp | Method for producing tire |
| JP4976730B2 (en) * | 2006-04-06 | 2012-07-18 | 株式会社ブリヂストン | Tire member laminate and tire using the tire member laminate |
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2008
- 2008-10-31 JP JP2008281361A patent/JP5461822B2/en active Active
- 2008-11-06 CN CN2008101752382A patent/CN101428530B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103732396A (en) * | 2011-05-31 | 2014-04-16 | 株式会社普利司通 | Multi-layered structure, inner liner for pneumatic tire, and pneumatic tire |
| CN103732397A (en) * | 2011-05-31 | 2014-04-16 | 株式会社普利司通 | Multi-layer structure, inner liner for pneumatic tire, and pneumatic tire |
| CN103732396B (en) * | 2011-05-31 | 2016-01-20 | 株式会社普利司通 | Multilayer structure making, pneumatic tire inner liner and pneumatic tire |
| CN104284922A (en) * | 2012-05-08 | 2015-01-14 | 株式会社普利司通 | Rubber sheet, pneumatic tire using same, and method for producing rubber sheet |
| CN104284922B (en) * | 2012-05-08 | 2018-04-03 | 株式会社普利司通 | Sheet rubber, using its pneumatic tire and sheet rubber production method |
| CN105899594A (en) * | 2013-11-21 | 2016-08-24 | 阿利桑那化学公司 | Additives for rubber compositions |
| CN105899594B (en) * | 2013-11-21 | 2020-03-13 | 阿利桑那化学公司 | Additive for rubber composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5461822B2 (en) | 2014-04-02 |
| CN101428530B (en) | 2012-05-30 |
| JP2009132379A (en) | 2009-06-18 |
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