JPWO2016140157A1 - Tire inner liner seat and tire - Google Patents

Abstract

The tire inner liner sheet of the present invention has an air barrier layer and a water vapor barrier layer laminated on the air barrier layer, and the air barrier layer comprises a polyester resin, a polyamide resin, a polynitrile resin, a polyvinyl resin, 1 or more types of resins selected from the group consisting of polyfluorinated resins and polyolefin resins are included, and the water vapor barrier layer includes one or more types of resins selected from the group consisting of polyamide resins, polyfluorinated resins and polyolefin resins. .

Description

  The present invention relates to a tire inner liner sheet and a tire.

  In recent years, the demand for lower fuel consumption of vehicles has been increasing. In connection with this, in addition to weight reduction by reducing the thickness of the tire, there is a tendency to realize a hard-to-deform tire that can reduce rolling resistance, that is, to improve shape stability. This tendency is the same for the inner liner which is a member for maintaining the air pressure of the tire and is one of the components forming the tire, and in particular, from the viewpoint of thinning and improvement of gas barrier properties. Various studies have been made.

  For example, the following technologies are focused on reducing the thickness of the inner liner and improving the gas barrier property.

  Patent Document 1 describes a technique in which a thermoplastic resin that is superior in gas barrier properties and has a thinner tire inner liner layer than a butyl rubber is used for the tire inner liner.

  Patent Document 2 describes a technique related to a tire inner liner formed using an ethylene-vinyl alcohol copolymer instead of a conventional butyl rubber.

  Patent Document 3 discloses a tire inner liner having a gas barrier layer containing a styrene-isobutylene-styrene copolymer, and an adhesive layer containing a styrene-isoprene-styrene copolymer and adhering carcass or insulation. Techniques relating to polymer sheets are described.

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

  However, in recent years, the technical level required for various characteristics of tire inner liners has been increasing. Therefore, a sheet used for forming a conventional tire inner liner (hereinafter, referred to as a tire inner liner sheet) is required to be further improved in terms of thinning and improvement of gas barrier properties.

  In view of such circumstances, an object of the present invention is to provide a tire inner liner sheet with improved gas barrier properties while maintaining conventional required characteristics, and a tire using the same.

According to the present invention, an air barrier layer;
A water vapor barrier layer laminated to the air barrier layer;
Have
The air barrier layer includes one or more resins selected from the group consisting of polyester resins, polyamide resins, polynitrile resins, polyvinyl resins, polyfluorinated resins, and polyolefin resins,
Provided is a tire inner liner sheet in which the water vapor barrier layer includes one or more resins selected from the group consisting of polyamide resins, polyfluorinated resins, and polyolefin resins.

  Furthermore, according to this invention, the tire containing the said sheet | seat for tire inner liners is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the sheet | seat for tire inner liners which improved the gas barrier property, maintaining the required required characteristic, and a tire using the same can be provided.

<Seat for tire inner liner>
A tire inner liner sheet according to the present embodiment (hereinafter referred to as the present sheet) includes an air barrier layer and a water vapor barrier layer laminated on the air barrier layer. And the air barrier layer in this sheet contains at least one resin selected from the group consisting of polyester resin, polyamide resin, polynitrile resin, polyvinyl resin, polyfluorinated resin and polyolefin resin, and the water vapor barrier layer is made of polyamide resin And one or more resins selected from the group consisting of polyfluorinated resins and polyolefin resins. By doing so, it is possible to realize a tire inner liner sheet useful for improving the gas barrier property of the tire while maintaining the conventional required characteristics.

  Since this sheet has a water vapor barrier layer as described above, it is possible to exhibit high gas barrier properties even under high humidity conditions. Moreover, when this sheet | seat is used as a tire inner liner, it can prevent not only the air | air from the inside of a tire but air also invading from the tire exterior. In other words, according to the present sheet, the state immediately after manufacturing the tire can be maintained for a long time. Therefore, when this sheet is used as a tire inner liner, it is possible to realize a tire excellent in shape stability with reduced rolling resistance and less deformation as compared with the case where a conventional sheet is used.

  The thickness of the sheet is preferably 0.05 mm or more and 1.5 mm or less, more preferably 0.05 mm or more and 1.2 mm or less, and most preferably 0.05 mm or more and 1.0 mm or less. By doing so, it is possible to realize an inner liner that is excellent in gas barrier properties and thinned as compared with a conventional sheet.

The gas barrier property of the air barrier layer in this sheet is such that the value of the oxygen permeability coefficient in terms of a thickness of 20 μm at 25 ° C. and 65% RH of the air barrier layer is preferably 1 cc / m ² · day · atm or more 5 × 10 ³ cc / m ² · day · atm or less, more preferably 1 cc / m ² · day · atm or more and 3 × 10 ³ cc / m ² · day · atm or less, more preferably 1 cc / m ² It is not less than day · atm and not more than 1 × 10 ³ cc / m ² · day · atm. In this way, when this sheet is used as a tire inner liner, it is possible to realize a tire capable of exhibiting shape stability with reduced rolling resistance and less deformation, regardless of the weight of the vehicle body. In other words, when the value of the oxygen permeation coefficient is within the above numerical range, it is possible to realize a tire having excellent shape stability that is not easily affected by stress applied during tire travel.

The gas barrier property of the water vapor barrier layer in this sheet is such that the water vapor permeability in terms of a thickness of 20 μm at 40 ° C. and 90% RH of the water vapor barrier layer is 1 g / m ² · day to 150 g / m ² · day. Is preferably 1 g / m ² · day or more and 120 g / m ² · day or less. By doing so, it is possible to realize an inner liner that is even better in terms of gas barrier properties under high humidity conditions.

  The peel strength at the adhesive interface between the air barrier layer and the water vapor barrier layer in this sheet is preferably 1.0 N / mm or more and 10.0 N / mm or less, and more preferably 1.5 N / mm or more and 10.0 N. / Mm or less, and most preferably 2.0 N / mm or more and 10.0 N / mm or less. By doing so, it is possible to realize an inner liner that can maintain a good adhesion state even when the tire generates heat during traveling.

  The sheet may have a plurality of air barrier layers. For example, the sheet can have a first air barrier layer and a second air barrier layer. In this case, the first air barrier layer, the water vapor barrier layer, and the second air barrier layer are preferably laminated in this order. Moreover, this sheet | seat may have a some water vapor | steam barrier layer. For example, the sheet can have a first water vapor barrier layer and a second water vapor barrier layer. In this case, the first water vapor barrier layer, the air barrier layer, and the second water vapor barrier layer are preferably laminated in this order. By doing so, it is possible to realize an inner liner having a high gas barrier property as compared with a conventional sheet. Specifically, when this sheet has the multilayer structure described above, the innermost barrier layer of the tire can reduce the possibility of deterioration of the tire due to the influence (moisture, etc.) from the external environment. It becomes. In addition, when the air barrier layer and the water vapor barrier layer are not laminated so that their surfaces are bonded to each other, between the air barrier layer and the water vapor barrier layer, from the viewpoint of improving the durability of the tire, An adhesive layer may be interposed.

  As described above, the material forming the air barrier layer in this sheet is a material containing at least one resin selected from the group consisting of polyester resins, polyamide resins, polynitrile resins, polyvinyl resins, polyfluorinated resins, and polyolefin resins. More specifically, it is as follows. Specific examples of the polyester resin include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, a copolymer of polybutylene terephthalate and polycarbonate, a copolymer of polybutylene terephthalate and polycaprolactone, and polybutylene terephthalate. Examples thereof include a copolymer of polyglycol and a copolymer of polybutylene naphthalate and polyglycol. Specific examples of the polyamide resin include nylon 6, nylon 11, nylon 12, nylon 6,6, nylon 6,10, nylon 10,10, nylon 6,12, a copolymer of nylon 6 and nylon 6,6, Nylon 6, nylon 6, 6 and nylon 12 copolymer, nylon 6 and nylon 12 copolymer, nylon 12 and polyether copolymer, aromatic nylon and the like. Examples of the polynitrile resin include polyacrylonitrile. Specific examples of the polyvinyl resin include polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene and vinyl alcohol copolymer, and the like. Specific examples of the polyvinyl fluoride resin include polyvinyl fluoride, polyvinylidene fluoride, vinylidene fluoride and chlorotrifluoroethylene copolymer, vinylidene fluoride and hexafluoropropylene copolymer, polychlorotrifluoroethylene, ethylene and chloro Examples thereof include a copolymer of trifluoroethylene, a copolymer of tetrafluoroethylene, difluoroethylene, and hexafluoropropylene. Specific examples of the polyolefin resin include polyethylene and polypropylene. These may be used alone or in combination, and further, those obtained by copolymerization of monomers constituting these resins may be used. Among them, nylon 6, nylon 6,6, nylon 6 and nylon 6,6 copolymer, nylon 6 and nylon from the viewpoint of exhibiting high gas barrier properties even under high humidity conditions and having high cut elongation. 12 copolymer, nylon 6 and nylon 6,6 and nylon 12 copolymer, polyvinyl fluoride, polyvinylidene fluoride, vinylidene fluoride and chlorotrifluoroethylene copolymer, vinylidene fluoride and hexafluoropropylene copolymer The coalescence is preferred.

  Further, the material forming the air barrier layer in the present sheet may contain additives such as fillers, antistatic agents, antiblocking agents, plasticizers, and elastomers as long as the object of the present invention is not impaired. Good.

  As described above, the material forming the water vapor barrier layer in this sheet is a material containing one or more selected from the group consisting of a polyfluorinated resin, a polyamide resin, or a polyolefin resin. More specifically, Street. Specific examples of the polyvinyl fluoride resin include polyvinyl fluoride, polyvinylidene fluoride, vinylidene fluoride and chlorotrifluoroethylene copolymer, vinylidene fluoride and hexafluoropropylene copolymer, polychlorotrifluoroethylene, ethylene and chloro Examples thereof include a copolymer of trifluoroethylene, a copolymer of tetrafluoroethylene, difluoroethylene, and hexafluoropropylene. Specific examples of the polyamide resin include nylon 6, nylon 11, nylon 12, nylon 6,6, nylon 6,10, nylon 10,10, nylon 6,12, a copolymer of nylon 6 and nylon 6,6, Nylon 6, nylon 6, 6 and nylon 12 copolymer, nylon 12 and polyether copolymer, aromatic nylon and the like. Specific examples of the polyolefin resin include polyethylene, polypropylene, polycycloolefin, ethylene and cycloolefin copolymer, and these may be modified polyolefin. These may be used alone or in combination, and further, those obtained by copolymerization of monomers constituting these resins may be used. Among these, polyethylene, polypropylene, polychlorotrifluoroethylene, and nylon 12 are preferable from the viewpoint of realizing an inner liner that exhibits high gas barrier properties even under high humidity conditions.

  In addition, the material forming the water vapor barrier layer in the present sheet contains additives such as fillers, antistatic agents, antiblocking agents, plasticizers, elastomers, and rubbers as long as the object of the present invention is not impaired. May be.

  The cut elongation of the air barrier layer in this sheet is preferably 80% or more and 1500% or less, more preferably 110% or more and 1500% or less, and most preferably 150% or more and 1500% or less. By doing so, since the tire inner liner sheet can follow the expansion of the member in the tire manufacturing process, the inner pressure retaining property of the tire is maintained without causing a defect in the tire inner liner sheet. be able to. The cutting elongation can be measured according to JIS K6251-2010.

  In this sheet, the cut elongation of the water vapor barrier layer is preferably 80% or more and 1500% or less, more preferably 110% or more and 1500% or less, and most preferably 150% or more and 1500% or less. . By doing so, since the tire inner liner sheet can follow the expansion of the member in the tire manufacturing process, the inner pressure retaining property of the tire is maintained without causing a defect in the tire inner liner sheet. be able to. The cutting elongation can be measured according to JIS K6251-2010.

  The thickness of the air barrier layer is preferably 0.01 mm or more and 0.75 mm or less, more preferably 0.01 mm or more and 0.6 mm or less, and most preferably 0.01 mm or more and 0.5 mm or less. is there. By doing so, it is possible to realize an inner liner that is excellent in gas barrier properties and thinned as compared with a conventional sheet.

  The thickness of the water vapor barrier layer is preferably 0.04 mm or more and 0.75 mm or less, more preferably 0.05 mm or more and 0.75 mm or less, and most preferably 0.1 mm or more and 0.75 mm or less. is there. By doing so, it is possible to realize an inner liner that is excellent in gas barrier properties and thinned as compared with a conventional sheet.

  Moreover, when the water vapor | steam barrier layer in this sheet | seat is formed with the material containing polyolefin resin, it is preferable that this polyolefin resin is modified polyolefin resin. In other words, the water vapor barrier layer in this sheet is preferably a modified polyolefin layer formed of a material containing a modified polyolefin resin. By doing so, it becomes possible to impart a function as an adhesive layer to the water vapor barrier layer. Therefore, when a modified polyolefin layer is used as the water vapor barrier layer in this sheet, it is possible to maintain a good adhesion state even when the tire generates heat during running, and the inner layer has excellent gas barrier properties under high humidity conditions. A liner can be realized. When the sheet has a plurality of water vapor barrier layers, the water vapor barrier layer may have only the modified polyolefin layer, but the modified polyolefin layer and a resin other than the modified polyolefin resin may be used. It is good also as a structure with which the water vapor | steam barrier layer formed with the material to contain coexisted.

  As the modified polyolefin resin, maleic anhydride-modified polyolefin resin is preferable. Furthermore, the maleic anhydride-modified polyolefin resin is preferably a maleic anhydride-modified polyethylene resin or a maleic anhydride-modified polypropylene resin. By doing so, it is possible to realize an inner liner capable of maintaining a better adhesion state even when heat is generated during running of the tire.

  Moreover, the material which forms the modified polyolefin layer in this sheet | seat may contain additives, such as a filler, a plasticizer, an elastomer, and rubber, if it is a range which does not impair the objective of this invention.

  When this sheet has a plurality of water vapor barrier layers including a modified polyolefin layer, the layer structure is determined by a material containing a resin other than the first air barrier layer, the first modified polyolefin layer, and the modified polyolefin resin. The formed water vapor barrier layer, the second modified polyolefin layer, and the second air barrier layer are laminated in this order to form a multilayer structure of five or more layers, or a first layer formed of a material containing a resin other than the modified polyolefin resin. The first water vapor barrier layer, the first modified polyolefin layer, the air barrier layer, the second modified polyolefin layer, and the second water vapor barrier layer formed of a material containing a resin other than the modified polyolefin resin are laminated in this order. It is preferable to have a multilayer structure of 5 layers or more. In this way, even when the tires generate heat during running, it is possible to maintain an excellent adhesion state, and it is possible to realize an inner liner superior in gas barrier properties under high humidity conditions compared to conventional sheets. Become. In addition, this sheet | seat may be provided with the structure of 5 layers or more, The layer structure can be suitably selected according to a use environment.

  This sheet can be produced using a known method such as a co-extrusion method, an extrusion lamination method, a dry lamination method, or an inflation method. Each layer may be manufactured separately and then bonded by a laminator or the like, or may be formed by an air-cooled or water-cooled coextrusion inflation method or a coextrusion T-die method. Among them, a method of laminating materials for forming each layer by co-extrusion with a T-die extruder, and cooling this to room temperature with a cooling roll is particularly preferable in terms of excellent thickness control of each layer. Further, the air barrier layer and the water vapor barrier layer may be directly bonded, or may be bonded via a modified polyolefin layer.

<Tire>
The tire according to the present embodiment refers to a pneumatic tire. Here, with reference to FIG. 1, the structure of the tire which concerns on this embodiment is demonstrated. The tire according to the present embodiment can be used for passenger cars, trucks, buses, heavy machinery and the like. Moreover, since the tire according to the present embodiment includes the above-described tire inner liner sheet, the tire has excellent shape stability with reduced rolling resistance and less deformation as compared with a conventional tire. Moreover, according to the tire which concerns on this embodiment, it is also possible to reduce in weight compared with the conventional tire.

  Specifically, the tire according to the present embodiment includes a tread portion that is in direct contact with a road surface during traveling, a sidewall portion that forms a side surface of the tire and protects a carcass described later, and a rim that includes the tire on a wheel. And a beat portion for fixing both ends of the carcass. In the tire according to this embodiment, from the inside to the outside, the inner liner formed by the tire inner liner sheet according to this embodiment described above and the carcass forming the tire framework are in this order. Is arranged in. In the tire, an insulation may be interposed between the inner liner and the carcass. In the tire according to the present embodiment, a belt layer is disposed between the tread portion and the carcass in order to reinforce the tread portion. Specifically, the belt layer is disposed outside the crown portion of the carcass and plays a role of increasing the rigidity of the tread portion. Furthermore, a beat core is arranged at the beat portion of the tire so that the end portion of the carcass is folded back and the carcass is pulled and fixed to the rim during traveling.

Next, a method for manufacturing a tire according to the present embodiment will be described.
The method for manufacturing a tire according to the present embodiment includes a step of preparing a raw tire using an inner liner sheet as an inner liner, and the raw tire is mounted on a mold and vulcanized while being pressurized by a bladder. A step of obtaining a tire, and a step of cooling the vulcanized tire at 50 to 120 ° C. for 10 to 300 seconds.

  In the step of preparing the green tire described above, the tire inner liner sheet is disposed on the inner liner portion of the green tire. The tire inner liner sheet used at this time is preferably one in which corona discharge treatment or plasma surface treatment has been performed on the surface in advance from the viewpoint of strengthening the adhesion with an adjacent member (carcass ply). . Moreover, as a method of arranging the tire inner liner sheet in the inner liner portion in the step of preparing the raw tire described above, for example, the carcass ply is placed via an adhesive so that the carcass ply faces the outer edge side of the tire. Examples thereof include a method of bringing the sheet into close contact with the ply and a method of pressing the sheet against the carcass ply. Here, specific examples of the adhesive include an epoxy resin adhesive, an acrylic resin adhesive, a vulcanized adhesive, and a silicone adhesive.

  In the tire according to the present embodiment, any gas that can exhibit its function can be used as the gas that maintains the tire internal pressure. Specific examples of such gas include air, nitrogen, helium and the like.

  As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these. In the following description, a water vapor barrier layer formed of a material containing a modified polyolefin resin is referred to as a modified polyolefin layer, and a water vapor barrier layer formed of a material containing a resin other than the modified polyolefin resin is referred to as a water vapor barrier layer. Examples will now be described.

<Example 1>
Polyester resin (manufactured by Teijin Ltd., TRN-8580FC) is used as a material for forming an air barrier layer, and maleic anhydride-modified polyolefin resin (manufactured by Mitsui Chemicals, Admer (registered trademark) SF731) is used as a material for forming a modified polyolefin layer. Was used. The above-mentioned various materials are put into a T-die extruder (screw diameter: φ50 mm, L / D: 28, manufactured by SunNT, SNT50-36V type extruder), and cooled and solidified using a cooling roll. A multilayer sheet having a three-layer structure in which an air barrier layer / modified polyolefin layer / air barrier layer were laminated in this order was formed by a coextrusion T-die method, whereby an inner liner sheet of Example 1 was obtained. The thickness of the obtained sheet | seat for inner liners was 120 micrometers. The thickness of each layer was 10 μm for the air barrier layer and 100 μm for the modified polyolefin layer.

<Example 2>
Nylon 6 (manufactured by Ube Industries, UBE nylon (registered trademark) 1022B) is used as a material for forming an air barrier layer, and maleic anhydride-modified polypropylene resin (manufactured by Mitsui Chemicals, Admer ( Polypropylene (Sumitomo Chemical Co., Ltd., FS2011DG2) was used as a material for forming the water vapor barrier layer. The above-mentioned various materials are put into a T-die extruder (screw diameter: φ50 mm, L / D: 28, manufactured by SunNT, SNT50-36V type extruder), and cooled and solidified using a cooling roll. Using a coextrusion T-die method, a multilayer sheet having a five-layer structure in which an air barrier layer / modified polyolefin layer / water vapor barrier layer / modified polyolefin layer / air barrier layer are laminated in this order is formed. A sheet was obtained. The thickness of the obtained sheet | seat for inner liners was 120 micrometers. The thickness of each layer was 10 μm for the air barrier layer, 10 μm for the modified polyolefin layer, and 80 μm for the water vapor barrier layer.

<Example 3>
Maleic anhydride-modified polyethylene resin (manufactured by Mitsui Chemicals, Admer (registered trademark) NF308) is used as the material for forming the modified polyolefin layer, and linear short-chain branched polyethylene (Prime Polymer Co., Ltd.) is used as the material for forming the water vapor barrier layer. A sheet for an inner liner was produced in the same manner as in Example 2 except that Neozex 3510F) was used.

<Example 4>
A multilayer having a three-layer structure in which an air barrier layer / modified polyolefin layer / air barrier layer are laminated in this order using the material forming the air barrier layer of Example 2 and the material forming the modified polyolefin layer of Example 2 An inner liner sheet was prepared in the same manner as in Example 1 except that the sheet was formed into a film. In addition, the thickness of the obtained sheet | seat for inner liners was 120 micrometers. The thickness of each layer was 10 μm for the air barrier layer and 100 μm for the modified polyolefin layer.

<Example 5>
A multilayer having a three-layer structure in which the air barrier layer / modified polyolefin layer / air barrier layer are laminated in this order using the material forming the air barrier layer of Example 3 and the material forming the modified polyolefin layer of Example 3 An inner liner sheet was prepared in the same manner as in Example 1 except that the sheet was formed into a film. In addition, the thickness of the obtained sheet | seat for inner liners was 120 micrometers. The thickness of each layer was 10 μm for the air barrier layer and 100 μm for the modified polyolefin layer.

<Example 6>
A multilayer having a three-layer structure in which the material for forming the air barrier layer of Example 2 and the material for forming the modified polyolefin layer of Example 2 are laminated in the order of modified polyolefin layer / air barrier layer / modified polyolefin layer. An inner liner sheet was prepared in the same manner as in Example 1 except that the sheet was formed into a film. In addition, the thickness of the obtained sheet | seat for inner liners was 120 micrometers. The thickness of each layer was 20 μm for the air barrier layer and 50 μm for the modified polyolefin layer.

<Example 7>
A multilayer having a three-layer structure in which the material for forming the air barrier layer of Example 3 and the material for forming the modified polyolefin layer of Example 3 are laminated in the order of modified polyolefin layer / air barrier layer / modified polyolefin layer. An inner liner sheet was prepared in the same manner as in Example 1 except that the sheet was formed into a film. In addition, the thickness of the obtained sheet | seat for inner liners was 120 micrometers. The thickness of each layer was 20 μm for the air barrier layer and 50 μm for the modified polyolefin layer.

<Example 8>
For the inner liner in the same manner as in Example 2 except that a copolymer of nylon 6 and nylon 12 (manufactured by Ube Industries, UBE nylon (registered trademark) 7024B) was used as a material for forming the air barrier layer. A sheet was produced.

<Example 9>
An inner liner sheet was produced in the same manner as in Example 7 except that polyvinylidene chloride resin (SOLVAY, IXAN (registered trademark) PVS 815) was used as a material for forming the air barrier layer.

<Example 10>
An inner liner sheet was produced in the same manner as in Example 7 except that polyvinylidene fluoride resin (manufactured by ARKEMA, Kynar (registered trademark) 740) was used as a material for forming the air barrier layer.

<Comparative Example 1>
Nylon 6 (manufactured by Ube Industries, UBE nylon (registered trademark) 1022B) is transferred to a T-die extruder (screw diameter: φ50 mm, L / D: 28, manufactured by SunNT, SNT50-36V type extruder). A sheet for an inner liner made of a single air barrier layer having a thickness of 150 μm was prepared by a T-die extrusion method that was charged, cooled and solidified using a cooling roll.

<Comparative example 2>
An inner liner sheet was prepared in the same manner as in Comparative Example 1 except that a single-layer sheet composed of an air barrier layer was prepared using a polyester resin (manufactured by Teijin Limited, TRN-8580FC).

<Comparative Example 3>
A sheet for an inner liner was prepared in the same manner as in Comparative Example 1 except that a single-layer sheet composed of a modified polyolefin layer was produced using a maleic anhydride-modified polyolefin resin (manufactured by Mitsui Chemicals, Admer (registered trademark) SF731). Produced.

<Comparative example 4>
The inner layer was made in the same manner as in Comparative Example 1 except that a single-layer sheet consisting of an air barrier layer was produced using a copolymer of nylon 6 and nylon 12 (UBE Nylon (registered trademark) 7024B, manufactured by Ube Industries). A liner sheet was prepared.

<Comparative Example 5>
An inner liner sheet was produced in the same manner as in Comparative Example 1 except that a single layer sheet composed of a water vapor barrier layer was produced using polypropylene (FS2011DG2 manufactured by Sumitomo Chemical Co., Ltd.).

<Comparative Example 6>
A sheet for an inner liner was produced in the same manner as in Comparative Example 1 except that a single-layer sheet composed of a water vapor barrier layer was produced using linear short-chain branched polyethylene (manufactured by Prime Polymer Co., Neozex 3510F).

<Comparative Example 7>
A sheet for an inner liner was prepared in the same manner as in Comparative Example 1 except that a single-layer sheet composed of a modified polyolefin layer was produced using a maleic anhydride-modified polypropylene resin (manufactured by Mitsui Chemicals, Admer (registered trademark) QB510). Produced.

<Comparative Example 8>
A sheet for an inner liner was prepared in the same manner as in Comparative Example 1 except that a single-layer sheet composed of a modified polyolefin layer was prepared using a maleic anhydride-modified polyethylene resin (manufactured by Mitsui Chemicals, Admer (registered trademark) NF308). Produced.

  Using the inner liner sheets obtained in the examples and comparative examples as inner liners, 195 / 65R15 size tires were produced in accordance with ordinary methods. In any of the sheets, an adhesive was applied on the surface subjected to corona discharge treatment (discharge current: 6 A, treatment speed: 10 m / min) to a film thickness of 60 μm, and then dried to adhere to the carcass ply.

  The following evaluation was performed using the sheet | seat for inner liners obtained by the Example and the comparative example. The results are shown in Table 1.

<Evaluation method>
-Oxygen permeability coefficient in terms of 20 μm thickness of air barrier layer: The oxygen permeability coefficient in terms of thickness of 20 μm of air barrier layer is a material that forms the air barrier layer contained in the inner liner sheet of each example and each comparative example A single-layer film having a thickness T of 150 μm obtained by the extrusion T-die method under the same conditions as in the above Examples and Comparative Examples except that a single-layer sheet is formed instead of a multilayer sheet. Using an oxygen permeability measuring device (Oxytran (registered trademark) OX-TRAN 2/21) manufactured by (MOCON), measurement was performed according to Appendix B in JIS K7126-2. The measurement conditions were set at 25 ° C. and 65% RH. The unit is cc / m ² · day · atm.

Water vapor permeability in terms of 20 μm thickness of water vapor barrier layer: The water vapor permeability in terms of 20 μm thickness of the water vapor barrier layer is a material that forms the water vapor barrier layer contained in the inner liner sheet of each example and each comparative example A single-layer film having a thickness T of 150 μm obtained by the extrusion T-die method under the same conditions as in the above Examples and Comparative Examples except that a single-layer sheet is formed instead of a multilayer sheet. Using a water vapor permeability measuring device (PERMATRAN-W 3/33) manufactured by (MOCON), measurement was performed in accordance with JIS K7126-2. The measurement conditions were set to 40 ° C. and 90% RH. The unit is g / m ² · day. When a modified polyolefin layer was included, the water vapor permeability was measured for both the water vapor barrier layer and the modified polyolefin layer.

Peel strength: T die extruder (screw diameter: φ50 mm, L / D: 28, SNT50-36V type) using the material forming the air barrier layer contained in the inner liner sheet of each example and each comparative example The sheet was formed as a 0.5 mm thick sheet (hereinafter referred to as an air barrier layer) using an extruder, manufactured by San NTT Co., Ltd. Moreover, using the material which forms the water vapor | steam barrier layer contained in the sheet | seat for inner liners of each Example, or a modified polyolefin layer, T-die extruder (screw diameter: φ50mm, L / D: 28, SNT50-36V type extrusion) And a sheet having a thickness of 0.5 mm (hereinafter referred to as a water vapor barrier layer or a modified polyolefin layer). The air barrier layer and the water vapor barrier layer or the modified polyolefin layer are overlapped, and a PTFE sheet having a length of about 1 cm is formed in a part between the air barrier layer and the water vapor barrier layer or the modified polyolefin layer so as to be a turning opening. Inserted and sandwiched between both outer sides with a metal mesh, and bonded so that the thickness of the two-layer sheet is 0.6 mm under the conditions of 260 ° C., 15 minutes, 5 MPa, 130 mm length × 25 mm width strip for peeling strength evaluation A sample was used. The peel strength between layers was measured by a T-type peel test at a tensile speed of 500 mm / min in accordance with JIS-K6854-3 under an atmosphere of 23 ° C. and 50% RH. The unit is N / mm. The evaluation results were as follows.
○: 1.0 N / mm or more and 10.0 N / mm or less ×: less than 1.0 N / mm

-Cutting elongation: The cutting elongation of the inner liner sheet was obtained by forming a single layer sheet instead of a multilayer sheet by using a material forming a layer included in the inner liner sheet of each example and each comparative example. Except for the point, with respect to a single layer film having a thickness of 150 μm obtained by the extrusion T-die method under the same conditions as in the above Examples and Comparative Examples, according to JIS K6251-2010 under the conditions of 23 ° C. and 50% RH. It was measured. The unit is%.

Adhesive strength with carcass rubber sheet at 23 ° C .: T-die extruder (screw diameter: φ50 mm, L / D: 28) formed from the material forming the outermost layer contained in the inner liner sheet of each example and comparative example , SNT50-36V type extruder, manufactured by San NTT Co., Ltd.). About the obtained sheet | seat, after apply | coating the adhesive agent so that it might become a film thickness of 60 micrometers on the surface which carried out the corona discharge process (discharge current: 6A, process speed: 10 m / min), it dried. Rubber sheet for carcass having an adhesive surface of 2 mm thickness obtained (70 parts by mass of natural rubber, 30 parts by mass of styrene butadiene rubber, 40 parts by mass of carbon black, 7 parts by mass of process oil, 2 parts by mass of stearic acid, zinc oxide 5 parts by mass, 3 parts by mass of sulfur, 1 part by mass of vulcanization accelerator), and a PTFE sheet is inserted with a length of about 1 cm so as to be partly turned, and both outer sides are made of metal mesh The sample was sandwiched and bonded so that the thickness of the two-layer sheet was 1.5 mm under the conditions of 170 ° C., 15 minutes, and 5 MPa, and a 130 mm long × 25 mm wide strip was used as a sample for adhesive strength evaluation. Next, after holding the sample so that the temperature of the prepared sample becomes 23 ° C., a tensile tester (Tensilon Universal Tester RTG-1310, manufactured by Orientec Co., Ltd.) was used, with a chuck interval of 30 mm and a tensile speed of 500 mm / min. Under the conditions, the S—S curve (stress-strain curve) at 23 ° C. and 50% RH was measured, and the value was divided by the width (25 mm) to measure the adhesive force, thereby obtaining the average adhesive force. When the material broke, the maximum load was taken as the adhesive strength. The evaluation results were as follows.
A: 8.0 N / mm or more B: 5.0 N / mm or more, less than 8.0 N / mm

Adhesive strength with the carcass rubber sheet at 80 ° C .: The material forming the outermost layer contained in the inner liner sheet of each example and comparative example is a T-die extruder (screw diameter: φ50 mm, L / D: 28 , SNT50-36V type extruder, manufactured by San NTT Co., Ltd.). About the obtained sheet | seat, after apply | coating the adhesive agent so that it might become a film thickness of 60 micrometers on the surface which carried out the corona discharge process (discharge current: 6A, process speed: 10 m / min), it dried. Rubber sheet for carcass having an adhesive surface of 2 mm thickness obtained (70 parts by mass of natural rubber, 30 parts by mass of styrene butadiene rubber, 40 parts by mass of carbon black, 7 parts by mass of process oil, 2 parts by mass of stearic acid, zinc oxide 5 parts by mass, 3 parts by mass of sulfur, 1 part by mass of vulcanization accelerator), and a PTFE sheet is inserted with a length of about 1 cm so as to be partly turned, and both outer sides are made of metal mesh The sample was sandwiched and bonded so that the thickness of the two-layer sheet was 1.5 mm under the conditions of 170 ° C., 15 minutes, and 5 MPa, and a 130 mm long × 25 mm wide strip was used as a sample for adhesive strength evaluation. Next, after holding the sample so that the temperature of the prepared sample is 23 ° C., holding the sample at 80 ° C. for 15 minutes, then using a tensile tester (Tensilon Universal Tester RTG-1310, manufactured by Orientec), Measure the S-S curve (stress-strain curve) at 80 ° C. and 50% RH under the conditions of a chuck interval of 30 mm and a tensile speed of 500 mm / min, and measure the adhesive force by dividing the value by the width (25 mm). It was set as the average adhesive strength. When the material broke, the maximum load was taken as the adhesive strength. The evaluation results were as follows.
A: 2.0 N / mm or more Δ: Less than 2.0 N / mm

-Workability at the time of tire production: Evaluation was performed according to the following criteria.
○: “No problem”, there is no particular problem at the time of tire production as usual.
X: “Film cutting”, one or more sheets were cut at the time of tire preparation. “Difficult to form”, when forming a tire, the tension of the sheet is too great to form. “Peeling before vulcanization”, the sheet was formed at the time of tire production, but the inner liner was peeled off from the carcass ply before vulcanization.

-Tire air leakage: After assembling the rim, each tire was adjusted to an internal pressure of 2.0 kg / cm ² , left at 25 ± 1 ° C. for 48 hours, and the internal pressure was adjusted again to 2.0 kg / cm ² . Further, the tire was allowed to stand at 25 ± 1 ° C. for 60 days, and the rate of decrease of the tire internal pressure during the 60 days was calculated from the following equation. The result was indexed with the tire of Comparative Example 1 as 100. The evaluation results were as follows. Larger values indicate better internal pressure retention and better.
Air leakage property = {(P1-P0) / P0} × 100
(In the formula, P0 represents the initial internal pressure, (2.0 kg / cm ² ), and P1 represents the tire internal pressure after being left for 60 days.)
A: 105 or more B: More than 100 and less than 105 x: 100 or less

・ Air leakage of tires in a high humidity environment: After assembling the rim, each tire is adjusted to an internal pressure of 2.0 kg / cm ² and left at 25 ± 1 ° C. for 48 hours, and the internal pressure is set to 2.0 kg / cm again. ² and then left for 60 days at 40 ± 1 ° C. and 90% RH. The rate of decrease of the tire internal pressure during this 60 days was calculated from the following equation, and the result was indexed with the tire of Comparative Example 1 as 100 did. The evaluation results were as follows. Larger values indicate better internal pressure retention and better.
Air leakage property = {(P1-P0) / P0} × 100
(In the formula, P0 represents the initial internal pressure, (2.0 kg / cm ² ), and P1 represents the tire internal pressure after being left for 60 days.)
A: 105 or more B: More than 100 and less than 105 x: 100 or less

-Water vapor barrier property of the entire inner liner sheet: Using the inner liner sheet of each example and comparative example, using a water vapor permeability measuring device (PERMATRAN-W 3/33) manufactured by MOCON , Measured according to JIS K7126-2. The measurement conditions were set to 40 ° C. and 90% RH. The unit is g / m ² · day. The evaluation results were as follows.
O: Water vapor permeability in terms of thickness 20 μm is 150 g / m ² · day or less.
X: Water vapor permeability in terms of thickness of 20 μm indicates a value greater than 150 g / m ² · day.

Tire appearance: The inside of the vulcanized tire was inspected, and the number of ridges per tire was measured by visual appearance. The evaluation results were as follows.
○: 0 × 1 or more

  Each of the inner liner sheets of each example was excellent in gas barrier properties while maintaining the conventional required characteristics. In addition, the tire using the inner liner sheet of each example was excellent in shape stability that was able to reduce rolling resistance and was difficult to deform.

  This application claims the priority on the basis of Japanese application Japanese Patent Application No. 2015-41069 for which it applied on March 3, 2015, and takes in those the indications of all here.

According to the present invention, an air barrier layer;
A water vapor barrier layer laminated to the air barrier layer;
Have
The air barrier layer includes one or more resins selected from the group consisting of polyester resins, polyamide resins, polynitrile resins, polyvinyl resins, polyfluorinated resins, and polyolefin resins,
The water vapor barrier layer includes a modified polyolefin layer,
The resin constituting the modified polyolefin layer is a maleic anhydride-modified polyolefin resin.
A tire inner liner sheet is provided.

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.
Hereinafter, examples of the reference form will be added.
1.
An air barrier layer;
A water vapor barrier layer laminated to the air barrier layer;
Have
The air barrier layer includes one or more resins selected from the group consisting of polyester resins, polyamide resins, polynitrile resins, polyvinyl resins, polyfluorinated resins, and polyolefin resins,
The tire inner liner sheet, wherein the water vapor barrier layer includes one or more resins selected from the group consisting of polyamide resins, polyfluorinated resins, and polyolefin resins.
2.
The air barrier layer has an oxygen permeability coefficient value in terms of a thickness of 20 μm at 25 ° C. and 65% RH of 1 cc / m ² · day · atm to 5 × 10 ³ cc / m ² · day · atm. 1. The sheet | seat for tire inner liners as described in.
3.
The water vapor permeability of the water vapor barrier layer in terms of a thickness of 20 μm at 40 ° C. and 90% RH is 1 g / m ² · day to 150 g / m ² · day. Or 2. The sheet | seat for tire inner liners as described in.
4).
1. The tire inner liner sheet has a thickness of 0.05 mm to 1.5 mm. To 3. The sheet | seat for tire inner liners as described in any one of these.
5.
Laminated so that the surfaces of the air barrier layer and the water vapor barrier layer are bonded to each other;
1. The peel strength at the adhesive interface between the air barrier layer and the water vapor barrier layer is 1.0 N / mm or more and 10.0 N / mm or less. To 4. The sheet | seat for tire inner liners as described in any one of these.
6).
The tire inner liner sheet includes the first air barrier layer and the second air barrier layer, and the first air barrier layer, the water vapor barrier layer, and the second air barrier layer are in this order. 1. has a multilayer structure formed by laminating To 5. The sheet | seat for tire inner liners as described in any one of these.
7).
The tire inner liner sheet includes the first water vapor barrier layer and the second water vapor barrier layer, and the first water vapor barrier layer, the air barrier layer, and the second water vapor barrier layer are in this order. 1. has a multilayer structure formed by laminating To 5. The sheet | seat for tire inner liners as described in any one of these.
8).
The water vapor barrier layer is a modified polyolefin layer containing a modified polyolefin resin as the polyolefin resin. To 7. The sheet | seat for tire inner liners as described in any one of these.
9.
7. the modified polyolefin resin is a maleic anhydride modified polyolefin resin; The sheet | seat for tire inner liners as described in.
10.
1. Thru 9. A tire comprising the tire inner liner sheet according to any one of the above.

Claims (10)

An air barrier layer;
A water vapor barrier layer laminated to the air barrier layer;
Have
The air barrier layer includes one or more resins selected from the group consisting of polyester resins, polyamide resins, polynitrile resins, polyvinyl resins, polyfluorinated resins, and polyolefin resins,
The tire inner liner sheet, wherein the water vapor barrier layer includes one or more resins selected from the group consisting of polyamide resins, polyfluorinated resins, and polyolefin resins. The air barrier layer has an oxygen permeability coefficient value in terms of a thickness of 20 μm at 25 ° C. and 65% RH of 1 cc / m ² · day · atm to 5 × 10 ³ cc / m ² · day · atm. The tire inner liner sheet according to claim 1. 3. The tire inner according to claim 1, wherein a water vapor permeability of the water vapor barrier layer in terms of a thickness of 20 μm at 40 ° C. and 90% RH is 1 g / m ² · day or more and 150 g / m ² · day or less. Liner sheet.   The tire inner liner sheet according to any one of claims 1 to 3, wherein the tire inner liner sheet has a thickness of 0.05 mm to 1.5 mm. Laminated so that the surfaces of the air barrier layer and the water vapor barrier layer are bonded to each other;
The tire inner liner according to any one of claims 1 to 4, wherein a peel strength at an adhesive interface between the air barrier layer and the water vapor barrier layer is 1.0 N / mm or more and 10.0 N / mm or less. Sheet.   The tire inner liner sheet includes the first air barrier layer and the second air barrier layer, and the first air barrier layer, the water vapor barrier layer, and the second air barrier layer are in this order. The sheet for a tire inner liner according to any one of claims 1 to 5, wherein the tire inner liner has a multilayer structure formed by laminating.   The tire inner liner sheet includes the first water vapor barrier layer and the second water vapor barrier layer, and the first water vapor barrier layer, the air barrier layer, and the second water vapor barrier layer are in this order. The sheet for a tire inner liner according to any one of claims 1 to 5, wherein the tire inner liner has a multilayer structure formed by laminating.   The tire inner liner sheet according to any one of claims 1 to 7, wherein the water vapor barrier layer is a modified polyolefin layer containing a modified polyolefin resin as the polyolefin resin.   The sheet for a tire inner liner according to claim 8, wherein the modified polyolefin resin is a maleic anhydride-modified polyolefin resin.   A tire comprising the tire inner liner sheet according to any one of claims 1 to 9.