WO2014042047A1

WO2014042047A1 - Tire inner liner sheet and tire

Info

Publication number: WO2014042047A1
Application number: PCT/JP2013/073766
Authority: WO
Inventors: 和彦丸山
Original assignee: 住友ベークライト株式会社
Priority date: 2012-09-12
Filing date: 2013-09-04
Publication date: 2014-03-20
Also published as: TW201420361A; CN104619520B; KR20150054776A; JP2014054915A; JP6163721B2; TWI618637B; CN104619520A

Abstract

Provided is a tire inner liner sheet having improved adhesion at high temperatures between layers in the tire inner liner sheet of multilayer configuration having at least two layers comprising a gas barrier layer and an adhesive layer. The tire inner liner sheet of such description has a gas barrier layer and an adhesive layer, the gas barrier layer and the adhesive layer being interlayer-crosslinked by a crosslinking reaction, wherein the interlayer crosslinking is formed by a crosslinking reaction between a substance (A) having an epoxy group and a substance (B) having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an anhydrous carboxyl group, and an amino group.

Description

Tire inner liner seat and tire

The present invention relates to a tire inner liner sheet and a tire.
This application claims priority based on Japanese Patent Application No. 2012-200820 filed in Japan on September 12, 2012, the contents of which are incorporated herein by reference.

In response to social demands for energy conservation in recent years, weight reduction has been achieved by making tires thinner. Among tire members, there is a tire inner liner that is arranged inside the tire radial direction and has the function of preventing air leakage from the inside to the outside of the pneumatic tire, but the tire inner liner also improves gas barrier properties. In order to reduce weight, it has come to be done.

In order to reduce the weight of a tire, it has been proposed to use a thermoplastic resin, which has better gas barrier properties than butyl rubber and can reduce the thickness of the tire inner liner layer, for the tire inner liner. For example, it is disclosed that a nylon sheet layer is used in place of a conventional butyl rubber for a tire inner liner (see, for example, Patent Document 1).

Further, it is disclosed that an ethylene-vinyl alcohol copolymer layer is used as a tire inner liner instead of a conventional butyl rubber (for example, see Patent Document 2).

In addition, an SIBS layer containing a styrene-isobutylene-styrene triblock copolymer is used as an air permeation resistant (gas barrier) layer, and styrene-isoprene-- is used as an adhesive layer for adhering the air permeation resistant layer and carcass or insulation. A polymer sheet for a tire inner liner using an SIS layer containing a styrene triblock copolymer and / or an SIB layer containing a styrene-isobutylene diblock copolymer has been disclosed (for example, Patent Document 3).

JP-A-9-165469 JP 2009-220793 A JP 2012-31362 A

A tire inner liner sheet having a multi-layer structure having a gas barrier layer and an adhesive layer usually has an advantage that the adhesion between the inner liner and the carcass or the insulation is stable even at a high temperature and a pneumatic tire having excellent performance can be provided. . On the other hand, however, a problem has been found in that the adhesive strength between layers is insufficient at high temperatures and there is a tendency to delaminate.

Therefore, the present invention provides a tire inner liner sheet having improved adhesion at high temperatures between layers in a tire inner liner sheet having a gas barrier layer and an adhesive layer, and a pneumatic tire using the same.

The present invention also relates to a tire inner liner sheet having a gas barrier layer and an adhesive layer, wherein the gas barrier layer and the adhesive layer are subjected to interlayer crosslinking by a crosslinking reaction.

Furthermore, this invention relates to a tire provided with the sheet | seat for tire inner liners concerning this indication.

ADVANTAGE OF THE INVENTION According to this invention, the tire inner liner sheet | seat with which the adhesive force at the time of the high temperature in the layer in the tire inner liner sheet | seat of the structure which has two or more layers of a gas barrier layer and an adhesion layer improved, and pneumatic using the same Tires can be provided.

It is a typical sectional view showing half of the pneumatic tire in one embodiment of the present invention. It is a typical sectional view showing the sheet for inner liners in one embodiment of the present invention. It is a typical sectional view showing the sheet for inner liners in one embodiment of the present invention.

[tire]
In the present invention, the “tire” means a pneumatic tire unless otherwise specified. The structure of one embodiment of the “pneumatic tire” in the present invention that is not limited will be described with reference to FIG. FIG. 1 is a schematic cross-sectional view showing a half of a pneumatic tire according to an embodiment which is not limited.

The pneumatic tire 1 is not limited to these, but can be used for passenger cars, trucks / buses, heavy machinery and the like. The pneumatic tire 1 has a tread portion 2, a sidewall portion 3, and a bead portion 4. Further, a bead core 5 is embedded in the bead portion 4. Further, a carcass 6 provided from one bead portion 4 to the other bead portion, folded back at both ends to lock the bead core 5, and a belt layer 7 made of two plies arranged outside the crown portion of the carcass 6 are arranged. Has been. An inner liner 9 extending from one bead portion 4 to the other bead portion 4 is disposed on the inner side in the tire radial direction of the carcass 6. The belt layer 7 has two plies made of steel cord or aramid fiber cord arranged so that the plies intersect each other so that the cord is usually at an angle of 5 to 30 ° with respect to the tire circumferential direction. Is done. In the carcass, organic fiber cords such as polyester, nylon, and aramid are arranged at approximately 90 ° in the tire circumferential direction, and a bead extending in the sidewall direction from the upper end of the bead core 5 is located in a region surrounded by the carcass and the folded portion. An apex 8 is arranged. An insulation may be disposed between the inner liner 9 and the carcass 6.

The tire according to the present invention includes a tire provided with a sheet for an inner liner according to the present invention described later. One non-limiting embodiment of the tire according to the present invention uses the innerliner sheet according to the present invention as the innerliner 9 of FIG.

[Tire inner liner seat]
The tire inner liner sheet according to the present invention has two or more layers including a gas barrier layer and an adhesive layer, and the gas barrier layer and the adhesive layer are cross-linked by a cross-linking reaction. The cross-linking of the interlayer cross-linking is a non-vulcanized cross-linking that does not include a vulcanized cross-link in one aspect that is not limited, and includes a vulcanized cross-link and a non-vulcanized cross-link in another aspect.

The structure of one or more embodiments of the “sheet for tire inner liner” in the present invention that is not limited will be described with reference to FIGS. 2 and 3 are cross-sectional views of an example of a tire inner liner sheet according to an embodiment of the present invention that is not limited. The tire inner liner sheet 20 shown in FIG. 2 includes an adhesive layer 22 that adheres to carcass rubber or insulation, and a gas barrier layer 21 that contacts the adhesive layer 22. The gas barrier layer 21 and the adhesive layer 22 are cross-linked by a cross-linking reaction. The tire inner liner sheet 30 shown in FIG. 3 includes two adhesive layers (32 and 33) that adhere to carcass rubber or insulation, and a gas barrier layer 31 in contact therewith. The gas barrier layer 31 and the adhesive layer 32 are interlayer-crosslinked by a crosslinking reaction. The adhesive layer 32 and the adhesive layer 33 may or may not be cross-linked between layers.

[Interlayer cross-linking]
In one embodiment, the interlayer crosslinking in the tire inner liner sheet according to the present invention includes, in one embodiment, a substance having an epoxy group (A) (hereinafter also referred to as “crosslinking agent (A)”), a hydroxyl group, a carboxyl group, and an anhydrous carboxyl group. And a substance (B) having at least one group selected from the group consisting of amino groups (hereinafter also referred to as “crosslinking agent (B)”).

These combinations of cross-linking agents can be applied to a method for producing a tire inner liner sheet that includes laminating a resin used for an adhesive layer and a resin used for a gas barrier layer by coextrusion with a T-die extruder. In one non-limiting embodiment, the cross-linking reaction is performed by laminating the resin used for the adhesive layer containing the cross-linking agent (A) and the resin used for the gas barrier layer containing the cross-linking agent (B) by coextrusion with a T-die extruder. Perform interlaminar cross-linking. Alternatively, in one non-limiting embodiment, the resin used for the adhesive layer containing the crosslinking agent (B) and the resin used for the gas barrier layer containing the crosslinking agent (A) are laminated by coextrusion with a T-die extruder. A reaction is performed to form an interlayer bridge. And by this interlayer bridge | crosslinking, melt fluidization of the contact bonding layer at high temperature can be suppressed, and generation | occurrence | production of peeling with the gas barrier layer and contact bonding layer in a tire can be suppressed. Moreover, the said interlayer bridge | crosslinking can suppress generation | occurrence | production of peeling with a contact bonding layer and carcass rubber | gum or insulation in one or some embodiment. However, the method for forming the interlayer cross-linking and / or the method for producing the tire inner liner sheet according to the present invention is not limited to these.

In the present invention, the “gas barrier layer containing a crosslinking agent (A)” is a gas barrier layer formed from a resin used for a gas barrier layer containing a crosslinking agent (A), and has a functional group (epoxy) of the crosslinking agent (A). All or part of the group) includes a gas barrier layer in a state in which the interlayer crosslink is formed.
Similarly, the “adhesive layer containing the cross-linking agent (B)” is an adhesive layer formed from a resin used for the adhesive layer containing the cross-linking agent (B), and includes all or functional groups of the cross-linking agent (B). A part includes an adhesive layer in a state of forming the interlayer crosslink.

Therefore, the tire inner liner sheet according to the present invention has, in one or more embodiments, a gas barrier layer and an adhesive layer, and the gas barrier layer and the adhesive layer are cross-linked by a cross-linking reaction, The gas barrier layer contains a crosslinking agent (A), and the adhesive layer is a tire inner liner sheet containing a crosslinking agent (B). Further, in one or more embodiments, the tire inner liner sheet according to the present invention has a gas barrier layer and an adhesive layer, and the gas barrier layer and the adhesive layer are cross-linked by a cross-linking reaction. The gas barrier layer contains a crosslinking agent (B), and the adhesive layer is a tire inner liner sheet containing a crosslinking agent (A).

[Substance with Epoxy Group (A) / Crosslinking Agent (A)]
In the present invention, as the crosslinking agent (A), a known or later developed crosslinking agent having an epoxy group can be used. When the gas barrier layer contains a crosslinking agent (A), the crosslinking agent (A) is preferably compatible with the resin used for the gas barrier layer. Moreover, when an adhesive layer contains a crosslinking agent (A), it is preferable that a crosslinking agent (A) has compatibility with resin used for an adhesion layer.
In one or more non-limiting embodiments, the crosslinking agent (A) is an ethylene / glycidyl methacrylate copolymer, an ethylene / glycidyl methacrylate / vinyl acetate copolymer, an ethylene / glycidyl methacrylate / methyl acrylate copolymer, or a combination thereof. One type of cross-linking agent may be used, or two or more types may be used in combination.

[Substance (B) / Crosslinking agent (B) having at least one group selected from the group consisting of hydroxyl group, carboxyl group, anhydrous carboxyl group, and amino group]
In the present invention, as the crosslinking agent (B), a known or later developed crosslinking agent having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an anhydrous carboxyl group, and an amino group can be used. . When the gas barrier layer contains a crosslinking agent (B), the crosslinking agent (B) is preferably compatible with the resin used for the gas barrier layer. Moreover, when an adhesive layer contains a crosslinking agent (B), it is preferable that a crosslinking agent (B) has compatibility with resin used for an adhesion layer. In one or more non-limiting embodiments, the crosslinking agent (B) is a phenol resin, maleic anhydride modified EPDM (ethylene-propylene-diene rubber), maleic anhydride modified ethylene octene rubber, maleic anhydride modified PE (polyethylene), Maleic anhydride-modified PP (polypropylene), partially saponified ethylene / vinyl acetate copolymer, maleic anhydride-modified SEBS (fully hydrogenated styrenic elastomer), or a combination thereof. One type of cross-linking agent may be used, or two or more types may be used in combination.

[Gas barrier layer]
As the gas barrier layer, a polymer sheet having gas barrier properties can be used. In one or a plurality of embodiments, from the viewpoint of reducing the weight of the tire, an SIBS layer containing a styrene-isobutylene-styrene triblock copolymer (Japanese Patent Laid-Open No. 31362), a SIB layer containing a styrene-isobutylene diblock copolymer, a layer containing an isobutylene-paramethylstyrene copolymer rubber or a brominated product or a chlorinated product thereof, a layer containing a butyl rubber or a brominated product or a chlorinated product thereof, EVOH ( A layer containing an ethylene-vinyl alcohol copolymer) (see JP2009-220793), a layer containing PVOH (polyvinyl alcohol), a layer containing an ethylene-cycloolefin copolymer, a layer containing a polyethylene terephthalate resin, a poly Contains vinylidene chloride resin Layer, a layer containing a polychlorotrifluoroethylene resin, such as a layer comprising polyethylene naphthalate resin.

In one or a plurality of embodiments, the content of the crosslinking agent (A) or (B) in the gas barrier layer is preferably 5% by mass or more based on the entire gas barrier layer from the viewpoint of maintaining gas barrier properties and forming a crosslink. Preferably it is 7 mass% or more, More preferably, it is 9 mass% or more.
Moreover, from the same viewpoint, 20 mass% or less is preferable, More preferably, it is 17 mass% or less, More preferably, it is 15 mass% or less.

Content of polymer having gas barrier property in gas barrier layer, and styrene-isobutylene-styrene triblock copolymer, styrene-isobutylene diblock copolymer, isobutylene-paramethylstyrene copolymer rubber or brominated product thereof in gas barrier layer or Chlorinated product, butyl rubber or brominated product or chlorinated product thereof, EVOH, PVOH, ethylene-cycloolefin copolymer, polyethylene terephthalate resin, polyvinylidene chloride resin, polychlorotrifluoroethylene resin, polyethylene naphthalate resin, or combinations thereof In one or more embodiments, the content is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably from the viewpoint of maintaining gas barrier properties. Is at least 80 mass%. Further, from the viewpoint of maintaining gas barrier properties and forming a crosslink, it is preferably 97% by mass or less, more preferably 95% by mass or less, and still more preferably 91% by mass or less.

In one or a plurality of embodiments, the thickness of the gas barrier layer is preferably 10 μm or more, more preferably 200 μm or more, and further preferably 250 μm or more from the viewpoint of maintaining gas barrier properties. Moreover, from a viewpoint of weight reduction of a tire, 600 micrometers or less are preferable, More preferably, it is 500 micrometers or less, More preferably, it is 450 micrometers or less.

[Adhesive layer]
As the adhesive layer, a polymer sheet capable of providing adhesion with carcass rubber or insulation can be used. In one or a plurality of embodiments, from the viewpoint of weight reduction of the tire, an SIS layer containing a styrene-isoprene-styrene triblock copolymer. SI layer containing styrene-isoprene diblock copolymer, layer containing polybutadiene, layer containing ethylene propylene diene rubber, layer containing isobutylene-paramethylstyrene copolymer rubber or bromide or chlorinated product thereof, butyl rubber and bromine thereof Examples thereof include a layer containing fluoride or chlorinated product, a layer containing butadiene rubber, a layer containing chloroprene rubber, a layer containing acrylonitrile butadiene rubber, and the like.

In one or a plurality of embodiments, the content of the crosslinking agent (A) or (B) in the adhesive layer is preferably 10% by mass or more, more preferably 15% by mass with respect to the entire adhesive layer, from the viewpoint of crosslinking. As mentioned above, More preferably, it is 20 mass% or more. Moreover, from a viewpoint of weight reduction of a tire, 60 mass% or less is preferable, More preferably, it is 55 mass% or less, More preferably, it is 50 mass% or less.

Content of polymer capable of providing adhesion with carcass rubber or insulation in the adhesive layer, and styrene-isoprene-styrene triblock copolymer, styrene-isoprene block copolymer, polybutadiene, ethylene propylene diene rubber in the adhesive layer, The content of isobutylene-paramethylstyrene copolymer rubber or a brominated product or chlorinated product thereof, butyl rubber and a brominated product or chlorinated product thereof, or a combination thereof is, in one or more embodiments, the adhesiveness to carcass rubber or insulation. From the viewpoint of maintenance, the content is preferably 40% by mass or more, more preferably 45% by mass or more, and still more preferably 50% by mass or more with respect to the entire adhesive layer. Moreover, from a viewpoint of bridge | crosslinking formation, 90 mass% or less is preferable, More preferably, it is 85 mass% or less, More preferably, it is 80 mass% or less.

In one or a plurality of embodiments, the thickness of the adhesive layer is preferably 10 μm or more, more preferably 50 μm or more from the viewpoint of maintaining adhesion with carcass rubber or insulation. Moreover, from a viewpoint of weight reduction of a tire, 300 micrometers or less are preferable, More preferably, it is 200 micrometers or less. The adhesive layer may be laminated in two or more layers as shown in FIG.

The tire inner liner sheet according to the present invention may have two or more gas barrier layers and two or more adhesive layers, and other resins within a range not impairing basic performance. The other resin layer may have a crosslinking agent (A) or a crosslinking agent (B). In this case, the crosslinking agent (A) and the crosslinking agent (B) not only between the gas barrier layer and the adhesive layer, but also between the gas barrier layer and the other resin layer, the adhesive layer and the other resin layer, and the interlayer between the other resin layers. ) May be cross-linked by interlayer cross-linking reaction. For example, in the tire inner liner sheet 30 shown in FIG. 3, when the adhesive layer 32 includes a crosslinking agent (A), the adhesive layer 33 includes the crosslinking agent (B), whereby the adhesive layer 32 and the adhesive layer 33 are crosslinked. Interlayer crosslinking can be performed by a crosslinking reaction of the agent (A) and the crosslinking agent (B).

[Method for producing tire inner liner sheet]
A non-limiting embodiment of the method for producing a tire inner liner sheet according to the present invention includes a resin used for an adhesive layer containing a crosslinking agent (A) (or (B)) and a crosslinking agent (B) (or (A )) And the resin used for the gas barrier layer can be produced by laminating the adhesive layer and the gas barrier layer by coextrusion with a T-die extruder, and cooling them to room temperature on a cooling roll. The cross-linking reaction between the cross-linking agent (A) and the cross-linking agent (B) can be performed by coextrusion and lamination at a temperature at which the cross-linking reaction occurs. Alternatively, the adhesive layer and the gas barrier layer can be formed and then bonded together at a temperature at which a crosslinking reaction occurs.

The crosslinking reaction temperature of the crosslinking agent can be appropriately selected depending on the combination of crosslinking agents to be used. In one or a plurality of non-limiting embodiments, from the viewpoint of causing a crosslinking reaction, 190 ° C. or higher, 200 ° C. or higher, 210 ° C. or higher, or 220 ° C. or higher may be mentioned, and from the viewpoint of thermal stability of the material used for the sheet To 300 ° C. or less.

In the tire inner liner sheet according to the present invention, it is preferable that an average adhesive force between the gas barrier layer and the adhesive layer at 100 ° C. is 0.2 N / mm or more.

[Tire manufacturing method]
In one embodiment, the tire manufacturing method according to the present invention includes the following steps.
Preparing a green tire using the innerliner sheet according to the present invention as an innerliner;
The raw tire is mounted on a mold and vulcanized while being pressurized with a bladder to obtain a vulcanized tire;
The vulcanized tire is cooled at 50 to 120 ° C. for 10 to 300 seconds.

(Process for preparing raw tires)
The tire inner liner sheet according to the present invention is disposed in an inner liner portion of a green tire. When the tire inner liner sheet 20 of FIG. 2 is disposed, the adhesive layer 22 is disposed facing the outer side in the tire radial direction so that the adhesive layer 22 is adhered to the inner surface of the tire inside the carcass rubber 6. With this arrangement, excellent air permeation resistance and durability can be obtained. Further, even when the insulation is disposed between the inner liner 9 and the carcass 6, the adhesive layer 22 is disposed toward the outer side in the tire radial direction so as to contact the insulation. Adhesive strength with insulation can be increased.

In the tire of the present invention, any gas capable of exhibiting its function can be used as the gas for maintaining the tire internal pressure, and examples thereof include air, nitrogen, and helium.

The tire according to the present invention includes the tire inner liner sheet according to the present invention, so that peeling between the adhesive layer and the gas barrier layer is suppressed when the vehicle is running, and the tire has excellent durability.

The present invention further relates to one or a plurality of embodiments below.

<1> A tire inner liner sheet, comprising a gas barrier layer and an adhesive layer, wherein the gas barrier layer and the adhesive layer are interlayer-crosslinked by a crosslinking reaction.
<2> The interlayer crosslinking includes an epoxy group-containing substance (A) and a substance (B) having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an anhydrous carboxyl group, and an amino group. <1> The tire inner liner sheet according to <1>, which is formed by a crosslinking reaction.
<3> The gas barrier layer contains a substance (A) having an epoxy group, and the adhesive layer contains at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an anhydrous carboxyl group, and an amino group. The sheet for a tire inner liner according to <1> or <2>, which contains the substance (B) to be included.
<4> The substance (A) having an epoxy group is selected from the group consisting of ethylene / glycidyl methacrylate copolymer, ethylene / glycidyl methacrylate / vinyl acetate copolymer, ethylene / glycidyl methacrylate / methyl acrylate copolymer, and combinations thereof. The tire inner liner sheet according to <2> or <3>, which is a copolymer.
<5> The substance (B) having at least one group selected from the group consisting of hydroxyl group, carboxyl group, anhydrous carboxyl group, and amino group is a phenol resin, maleic anhydride-modified EPDM (ethylene-propylene-diene rubber) ), Maleic anhydride modified ethylene octene rubber, maleic anhydride modified PE (polyethylene), maleic anhydride modified PP (polypropylene), partially saponified ethylene / vinyl acetate copolymer, maleic anhydride modified SEBS (fully hydrogenated styrene elastomer) ) And a group consisting of a combination thereof, the tire inner liner sheet according to any one of <2> to <4>.
<6> The gas barrier layer is a SIBS layer containing a styrene-isobutylene-styrene triblock copolymer, a SIB layer containing a styrene-isobutylene diblock copolymer, an isobutylene-paramethylstyrene copolymer rubber, a brominated product thereof, or chlorine A layer selected from the group consisting of a layer containing a fluoride, a layer containing butyl rubber or a brominated or chlorinated product thereof, a layer containing EVOH (ethylene-vinyl alcohol copolymer), and a layer containing PVOH (polyvinyl alcohol). The tire inner liner sheet according to any one of <1> to <5>.
<7> The adhesive layer includes an SIS layer containing a styrene-isoprene-styrene triblock copolymer, an SI layer containing a styrene-isoprene diblock copolymer, a layer containing polybutadiene, a layer containing ethylene propylene diene rubber, isobutylene A layer containing paramethylstyrene copolymer rubber or its brominated or chlorinated layer, a layer containing butyl rubber and its brominated or chlorinated product, a layer containing butadiene rubber, a layer containing chloroprene rubber, and a layer containing acrylonitrile butadiene rubber The tire inner liner sheet according to any one of <1> to <6>, which is a layer selected from the group consisting of:
<8> A tire provided with the tire inner liner sheet according to any one of <1> to <7>.

Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to the following examples.

After mixing each resin according to the formulation shown in Table 1, co-extrusion is performed using a T-die extruder (screw diameter: φ40 mm, L / D: 28), and the adhesive layer 22 having a thickness of 200 μm and the gas barrier layer having a thickness of 400 μm. A sheet of 21 having a total thickness of 600 μm was prepared.

(Example 1)
As the adhesive layer 22, a styrene-isoprene-styrene copolymer (manufactured by Nippon Zeon Co., Ltd., product number: QUINTAC 3620), maleic anhydride modified EPDM (manufactured by DuPont, product number: Husabond N416, cross-linking agent (B)), And a phenol resin (manufactured by Sumitomo Bakelite Co., Ltd., product number: PR-19900, cross-linking agent (B)) were mixed according to the formulation shown in Table 1, and then charged into an extruder (cylinder temperature: 240 ° C.). Further, as the gas barrier layer 21, a styrene-isobutylene-styrene copolymer (manufactured by Kaneka Co., Ltd., Shibster 102T) and an ethylene / glycidyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., product number: Bondfast E, cross-linking agent (A)). Were mixed according to the formulation shown in Table 1, and then charged into an extruder (cylinder temperature: 180 ° C.). The adhesive layer 22 and the gas barrier layer 21 were obtained by laminating with a T die (die temperature: 240 ° C.) and then cooling and solidifying with a cooling roll (temperature: 25 ° C.).

(Comparative Example 1: No cross-linking agent (A))
As the adhesive layer 22, a styrene-isoprene-styrene copolymer (manufactured by ZEON Corporation, product number: QUINTAC 3620), maleic anhydride-modified EPDM (manufactured by DuPont, cross-linking agent (B)), and phenol resin (Sumitomo Bakelite Co., Ltd., product number: PR-19900, crosslinker (B)) was mixed according to the formulation shown in Table 1, and then charged into an extruder (cylinder temperature: 240 ° C.). As the gas barrier layer 21, a styrene-isobutylene-styrene copolymer (manufactured by Kaneka Corporation, Shibster 102T) was put into an extruder (cylinder temperature: 180 ° C.). The adhesive layer 22 and the gas barrier layer 21 were obtained by laminating with a T die (die temperature: 240 ° C.) and then cooling and solidifying with a cooling roll (temperature: 25 ° C.).

(Comparative Example 2: No crosslinking agent (B))
As the adhesive layer 22, a styrene-isoprene-styrene copolymer (manufactured by Zeon Corporation, product number: QUINTAC 3620) was put into an extruder (cylinder temperature: 240 ° C.). Further, as the gas barrier layer 21, a styrene-isobutylene-styrene copolymer (manufactured by Kaneka Corporation, Shibster 102T) and an ethylene / glycidyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd.) were mixed according to the formulation shown in Table 1, It put into the extruder (cylinder temperature: 180 degreeC). The adhesive layer 22 and the gas barrier layer 21 were obtained by laminating with a T die (die temperature: 240 ° C.) and then cooling and solidifying with a cooling roll (temperature: 25 ° C.).

[Evaluation of peel strength]
The peeling force was measured on the tire inner liner sheets of Example 1 and Comparative Examples 1 and 2 under the following conditions. The results are shown in Table 1 below.
(Peeling force evaluation method)
The gas barrier layer 21 and the adhesive layer 22 were each formed as a sheet having a thickness of 1 mm using a T-die extruder. A PTFE sheet having a length of about 1 cm is inserted into a part between the two gas barrier layers 21 and the two adhesive layers 22 so as to form a turning opening, and the two gas barrier layers 21 and the adhesive layer 22 are inserted. The two outer sides were sandwiched between metal meshes and bonded to each other so that the thickness of the two-layer sheet was 0.34 mm under the conditions of 240 ° C., 5 minutes, and 5 MPa, to obtain a sample for evaluating adhesive strength. After holding at 100 ° C. for 1 minute, the peel strength was measured by a T-type tensile peel test (500 mm / min) to obtain an average interlayer adhesion.

As shown in Table 1, in the tire inner liner sheet of Example 1 in which the adhesive layer and the gas barrier layer were cross-linked, the adhesive strength between the adhesive layer and the gas barrier layer at 100 ° C. was improved as compared with Comparative Examples 1 and 2. .

The present invention improves the adhesive force at high temperatures between layers in a tire inner liner sheet having a gas barrier layer and an adhesive layer, and can be applied to a tire inner liner sheet and a pneumatic tire using the same.

DESCRIPTION OF SYMBOLS 1 Pneumatic tire 2 Tread part 3 Side wall part 4 Bead part 5 Bead core 6 Carcass 7 Belt layer 8 Bead apex 9

Inner liner

20, 30 Tire

inner liner sheet

21, 31 Gas barrier layers 22, 32, 33 Adhesive layer

Claims

A tire inner liner sheet having a gas barrier layer and an adhesive layer, wherein the gas barrier layer and the adhesive layer are interlayer-crosslinked by a crosslinking reaction.
The interlayer crosslinking is performed by a crosslinking reaction between a substance (A) having an epoxy group and a substance (B) having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an anhydrous carboxyl group, and an amino group. The tire inner liner sheet according to claim 1, wherein the tire inner liner sheet is formed.
The gas barrier layer contains a substance (A) having an epoxy group, and the adhesive layer has a substance having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an anhydrous carboxyl group, and an amino group ( The sheet | seat for tire inner liners of Claim 1 or 2 containing B).
The substance (A) having an epoxy group is a copolymer selected from the group consisting of ethylene / glycidyl methacrylate copolymer, ethylene / glycidyl methacrylate / vinyl acetate copolymer, ethylene / glycidyl methacrylate / methyl acrylate copolymer, and combinations thereof. The seat for a tire inner liner according to claim 2 or 3.
A substance (B) having at least one group selected from the group consisting of the hydroxyl group, carboxyl group, anhydrous carboxyl group, and amino group is a phenol resin, maleic anhydride-modified EPDM (ethylene-propylene-diene rubber), anhydrous Maleic acid modified ethylene octene rubber, maleic anhydride modified PE (polyethylene), maleic anhydride modified PP (polypropylene), partially saponified ethylene / vinyl acetate copolymer, maleic anhydride modified SEBS (fully hydrogenated styrenic elastomer), and The tire inner liner sheet according to any one of claims 2 to 4, which is selected from the group consisting of these combinations.
The gas barrier layer includes a SIBS layer containing a styrene-isobutylene-styrene triblock copolymer, a SIB layer containing a styrene-isobutylene diblock copolymer, an isobutylene-paramethylstyrene copolymer rubber, or a brominated or chlorinated product thereof. A layer selected from the group consisting of a layer, a layer containing butyl rubber or a brominated or chlorinated product thereof, a layer containing EVOH (ethylene-vinyl alcohol copolymer), and a layer containing PVOH (polyvinyl alcohol). Item 6. The tire inner liner sheet according to any one of Items 1 to 5.
The adhesive layer is a SIS layer containing a styrene-isoprene-styrene triblock copolymer, an SI layer containing a styrene-isoprene diblock copolymer, a layer containing polybutadiene, a layer containing ethylene propylene diene rubber, isobutylene-paramethyl A group consisting of a layer containing a styrene copolymer rubber or a brominated or chlorinated product thereof, a layer containing a butyl rubber and a brominated or chlorinated product thereof, a layer containing a butadiene rubber, a layer containing a chloroprene rubber, and a layer containing an acrylonitrile butadiene rubber The tire inner liner sheet according to any one of claims 1 to 6, wherein the tire inner liner sheet is a layer selected from:
A tire comprising the tire inner liner sheet according to any one of claims 1 to 7.