JP2006167919A - Laminate, its manufacturing method and tire using the laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate suitably usable as an inner liner or the like, constituted by bonding and integrating a resin film layer and a rubbery elastomer layer through an adhesive layer, good in workability in its manufacturing process and having excellent anti-peeling force, and a tire using the same. <P>SOLUTION: The laminate is manufactured by bonding the resin film layer (A) and the rubbery elastomer layer (B) through the adhesive layer (C). The adhesive composition which constitutes the adhesive layer (C) contains 0.1 pt.mass or above of a thiuram type and/or substituted dithiocarbamate type vulcanization accelerator (b), 0.1 pt.mass or above of a silane coupling agent (c) and 0.1 pt.mass or above of at least one of poly-p-dinitrobenzene and 1,4-phenylenedimaleimide (d) as a crosslinking agent and a crosslinking aid with respect to 100 pts.mass of a rubber component (a). Its manufacturing method and the tire using the laminate are also disclosed. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a laminate, a method for manufacturing the same, and a tire using the same. More specifically, the present invention is a laminate in which a resin film layer and a rubber-like elastic body layer are joined and integrated via an adhesive layer, and the workability in the manufacturing process is good, and the peel resistance is In particular, the present invention relates to a laminate that is suitably used as an inner liner of a pneumatic tire, a method for efficiently producing the laminate, and a tire that uses the laminate.

Conventionally, an inner liner layer mainly composed of a low-gas-permeable butyl rubber such as butyl rubber or halogenated butyl rubber has been provided on the inner surface of a pneumatic tire in order to prevent air leakage and keep the tire air pressure constant. Yes. However, if the content of these butyl rubbers is increased, the strength of the unvulcanized rubber will decrease, and it will easily cause rubber breakage and sheet holes. Sometimes the inner cord tends to be exposed.
Therefore, the blending amount of the butyl rubber is naturally limited, and when using a rubber composition blended with the butyl rubber, the thickness of the inner liner layer needs to be around 1 mm from the viewpoint of air barrier properties. . Therefore, the weight of the inner liner layer in the tire is about 5%, which has been an obstacle for reducing the weight of the tire and improving the fuel efficiency of the automobile.
Therefore, in accordance with social demands for energy saving in recent years, a method for reducing the thickness of the inner liner layer has been proposed for the purpose of reducing the weight of automobile tires. For example, a method of using a nylon film layer or a vinylidene chloride layer as an inner liner layer instead of a conventional butyl rubber is disclosed (for example, see Patent Document 1 and Patent Document 2). In addition, it is disclosed that a film of a composition comprising a blend of a thermoplastic resin such as a polyamide-based resin or a polyester-based resin and an elastomer is used for the inner liner layer (see, for example, Patent Document 3).

However, the methods using these films, although the weight of the tire can be reduced to a certain extent, since the matrix agent is a crystalline resin material, it is particularly resistant to cracking and bending when used at a low temperature of 5 ° C. or lower. There is a drawback that the fatigue property is inferior to that of a normally used butyl rubber compounded composition layer, and tire production is also complicated.
On the other hand, an ethylene-vinyl alcohol copolymer (hereinafter sometimes abbreviated as EVOH) is known to have excellent gas barrier properties. EVOH has an air permeability of 1/100 or less that of an inner liner rubber composition containing a butyl rubber, so that it can significantly improve the internal pressure retention even at a thickness of 50 μm or less, and the tire weight. Can be reduced.
Therefore, it can be said that it is effective to use EVOH for the tire inner liner in order to improve the air permeability of the pneumatic tire. For example, a pneumatic tire having a tire inner liner made of EVOH is disclosed (see, for example, Patent Document 4).

However, when this EVOH is used as a tire inner liner, the internal pressure retention effect is large, but the elastic modulus is significantly higher than that of rubber used in ordinary tires. Sometimes occurred.
For this reason, when using an inner liner made of EVOH, the internal pressure retention before use of the tire is greatly improved, but the internal pressure retention of the tire after use subjected to bending deformation at the time of tire rolling is higher than that before use. There was a problem that it may decrease.
In order to solve this problem, for example, a resin comprising 60 to 99% by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 20 to 70 mol%, a saponification degree of 85% or more, and 1 to 40% by weight of a hydrophobic plasticizer. A tire inner liner using a composition is disclosed (for example, see Patent Document 5), but the bending resistance is not always satisfactory.
Accordingly, there has been a demand for the development of an inner liner that has a high degree of bending resistance and can be made thinner while maintaining gas barrier properties.
As such an inner liner, for example, a laminated body in which a rubber-like elastic film or sheet having excellent bending resistance and a resin film having good gas barrier properties are joined and integrated can be considered. In this case, it is required that workability in the manufacturing process of the laminate is good and that the peel resistance is excellent.

Japanese Patent Laid-Open No. 7-40702 JP-A-7-81306 JP-A-10-26407 JP-A-6-40207 JP 2002-52904 A

  Under such circumstances, the present invention can be suitably used as an inner liner that can be made thinner, and the resin film layer and the rubber-like elastic layer are joined and integrated via an adhesive layer. And it aims at providing the laminated body which is excellent in workability | operativity in the manufacturing process, and is excellent in peeling resistance, and a tire using the same.

（Ｒ¹及びＲ²はそれぞれ炭素数１〜４の炭化水素基、Ｒ³は炭素数１〜１５の二価の炭化水素基、ｐは０〜２の整数、Ｒ⁴は下記一般式（II）で表される二価の官能基である。）

（Ｒ⁵〜Ｒ⁷は直鎖状又は分岐を有する炭素数１〜２０の二価の脂肪族もしくは脂環式炭化水素基、二価の芳香族基又は硫黄及び酸素以外のヘテロ元素を含む二価の有機基であって、Ｒ⁵〜Ｒ⁷はそれぞれ同一でも異なってもよく、ｘはそれぞれ平均値として１以上４未満の数である。）
（４） （ｃ）成分におけるシランカップリング剤が、下記平均組成式（III）で表されるシランカップリング剤である上記（１）の積層体、

（ｎは１〜３の整数、ｍは１〜９の整数、ｙは１以上の整数で分布を有する。）
（５） （ｃ）成分におけるシランカップリング剤が、下記組成式（ＩＶ）の硫黄含有シランカップリング剤である上記（１）の積層体、

（Ｒ⁸及びＲ⁹はそれぞれ炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基、Ｒ¹⁰は炭素数１〜１５の二価の炭化水素基、ｐは０〜２の整数である。）
（６） 接着剤組成物において、（ａ）ゴム成分１００質量部当り、５０質量％以上のブチル系ゴムを含む上記（１）〜（５）の積層体、
（７） ブチル系ゴム系ゴムが、ブチルゴム及び／又はハロゲン化ブチルゴムである上記（６）の積層体、
（８） 接着剤組成物において、（ａ）ゴム成分が、ハロゲン化ブチルゴム７０質量部％以上と、天然ゴム及び／又はイソプレンゴム５質量％以上を含む上記（１）〜（７）の積層体、
（９） 接着剤組成物において、（ａ）ゴム成分１００質量部に対して、（ｆ）充填剤を２〜５０質量部含む上記（１）〜（８）の積層体、
（１０） （ｆ）充填剤がカーボンブラック、湿式法によるシリカ、水酸化アルミニウム、酸化アルミニウム、酸化マグネシウムの中から選ばれる少なくとも一種である上記（８）の積層体、
（１１） （ｂ）加硫促進剤が、置換ジチオカルバミン酸塩系加硫促進剤である上記（１）〜（１０）の積層体、
（１２） 置換ジチオカルバミン酸塩系加硫促進剤が、ジベンジルジチオカルバミン酸亜鉛である上記（１１）の積層体、
（１３） （Ａ）樹脂フイルム層の厚さが２００μｍ以下であり、（Ｂ）ゴム状弾性体層の厚さが２００μｍ以上である上記（１）〜（１２）の積層体、
（１４） （Ａ）樹脂フイルム層が、熱可塑性ウレタン系エラストマー層を含む上記（１）〜（１３）の積層体、
（１５） （Ａ）樹脂フイルム層が、変性エチレン−ビニルアルコール共重合体層を含む上記（１）〜（１４）の積層体、
（１６） （Ａ）樹脂フイルム層が、熱可塑性ウレタン系エラストマー層を含むと共に、変性エチレン‐ビニルアルコール共重合体層を一層以上含む多層フイルムからなる層である上記（１４）、（１５）の積層体、
（１７） （Ｂ）ゴム状弾性体層を構成するゴム状弾性体が、ブチル系ゴム５０質量％以上を含むゴム成分を含有する上記（１）〜（１６）の積層体、
（１８） ブチル系ゴムが、ブチルゴム及び／又はハロゲン化ブチルゴムである（１７）の積層体、
（１９） 有機溶媒を含む接着剤組成物からなる塗工液を、樹脂フイルム表面に塗工、乾燥したのち、その上にゴム状弾性体フイルム又はシートを貼合し、加熱・加硫処理をすることを特徴とする、（１）〜（１８）の製造方法、
（２０） 有機溶媒を含む接着剤組成物からなる塗工液を、ゴム状弾性体フイルム又はシート表面に塗工、乾燥したのち、その上に樹脂フイルムを貼合し、加熱・加硫処理をする、上記（１）〜（１８）の積層体の製造方法、
（２１） 有機溶媒として、ヒルデブランド（Hildebrand）溶解性パラメーターδ値が１４〜２０ＭＰａ^1/2の範囲にあるものを用いる上記（１９）、（２０）の積層体の製造方法、
（２２） 加熱・加硫温度が１２０℃以上である上記（１９）〜（２１）の積層体の製造方法、及び
（２３） 上記（１）〜（１８）の積層体を用いたことを特徴とするタイヤ、
を提供するものである。 As a result of intensive studies to achieve the above object, the present inventors have obtained an adhesive layer in which a resin film layer and a rubber-like elastic body layer are formed using an adhesive composition having a specific composition. It has been found that the object can be achieved by a laminate that is joined and integrated through the laminated body. The present invention has been completed based on such findings.
That is, the present invention
(1) A laminate in which (A) a resin film layer and (B) a rubber-like elastic body layer are joined together via (C) an adhesive layer, and the adhesive constituting the (C) adhesive layer The agent composition comprises (b) a thiuram-based and / or substituted dithiocarbamate-based vulcanization accelerator at least 0.1 part by mass per 100 parts by mass of the rubber component, and (c) a silane coupling agent at 0.1 mass. And (d) a laminate comprising 0.1 part by mass or more of at least one of poly-p-dinitrosobenzene and 1,4-phenylene dimaleimide as a crosslinking agent and a crosslinking aid,
(2) The laminate according to (1), wherein the adhesive composition further contains (e) 10% by mass or more of chlorosulfonated polyethylene as a rubber component,
(3) The laminate of (1) above, wherein the silane coupling agent in component (c) is a sulfur-containing silane coupling agent represented by the following average composition formula (I):

(R ¹ and R ² are each a hydrocarbon group having 1 to 4 carbon atoms, R ³ is a divalent hydrocarbon group having 1 to 15 carbon atoms, p is an integer of 0 to 2, and R ⁴ is a general formula (II ) Is a divalent functional group represented by

(R ^{5 to} R ⁷ are linear or branched divalent aliphatic or alicyclic hydrocarbon groups having 1 to 20 carbon atoms, divalent aromatic groups, or heteroelements other than sulfur and oxygen. And each of R ^{5 to} R ⁷ may be the same or different, and x is an average value of 1 or more and less than 4.)
(4) The laminate of (1) above, wherein the silane coupling agent in component (c) is a silane coupling agent represented by the following average composition formula (III):

(N is an integer of 1 to 3, m is an integer of 1 to 9, and y is an integer of 1 or more and has a distribution.)
(5) The laminate of (1) above, wherein the silane coupling agent in component (c) is a sulfur-containing silane coupling agent of the following composition formula (IV):

(R ⁸ and R ⁹ are each an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, R ¹⁰ is a divalent hydrocarbon group having 1 to 15 carbon atoms, and p is an integer of 0 to 2. is there.)
(6) In the adhesive composition, (a) the laminate of (1) to (5) above containing 50% by mass or more of butyl rubber per 100 parts by mass of the rubber component,
(7) The laminate according to (6), wherein the butyl rubber rubber is butyl rubber and / or halogenated butyl rubber,
(8) The adhesive composition, wherein (a) the rubber component contains 70 parts by mass or more of halogenated butyl rubber and 5% by mass or more of natural rubber and / or isoprene rubber, ,
(9) In the adhesive composition, (a) the laminate of the above (1) to (8) containing 2 to 50 parts by mass of the filler with respect to 100 parts by mass of the rubber component,
(10) (f) The laminate according to (8), wherein the filler is at least one selected from carbon black, silica by a wet method, aluminum hydroxide, aluminum oxide, and magnesium oxide,
(11) (b) The laminate of (1) to (10) above, wherein the vulcanization accelerator is a substituted dithiocarbamate vulcanization accelerator,
(12) The laminate of (11) above, wherein the substituted dithiocarbamate vulcanization accelerator is zinc dibenzyldithiocarbamate,
(13) (A) The laminate of (1) to (12) above, wherein the resin film layer has a thickness of 200 μm or less, and (B) the rubbery elastic layer has a thickness of 200 μm or more,
(14) (A) The laminate of the above (1) to (13), wherein the resin film layer includes a thermoplastic urethane-based elastomer layer,
(15) (A) The laminate of (1) to (14) above, wherein the resin film layer includes a modified ethylene-vinyl alcohol copolymer layer,
(16) (A) The above-mentioned (14), (15), wherein the resin film layer is a layer comprising a multilayer film including a thermoplastic urethane elastomer layer and at least one modified ethylene-vinyl alcohol copolymer layer. Laminate,
(17) (B) Laminated body of said (1)-(16) in which the rubber-like elastic body which comprises a rubber-like elastic body layer contains the rubber component containing 50 mass% or more of butyl-type rubbers,
(18) The laminate of (17), wherein the butyl rubber is butyl rubber and / or halogenated butyl rubber,
(19) A coating solution comprising an adhesive composition containing an organic solvent is applied to the resin film surface and dried, and then a rubber-like elastic film or sheet is bonded thereon, followed by heating and vulcanization treatment. The manufacturing method of (1)-(18) characterized by performing,
(20) A coating solution comprising an adhesive composition containing an organic solvent is applied to a rubber-like elastic film or sheet surface, dried, and then a resin film is bonded thereon, followed by heating and vulcanization treatment. A method for producing the laminate of (1) to (18) above,
(21) The method for producing a laminate according to (19) and (20) above, wherein an organic solvent having a Hildebrand solubility parameter δ value in the range of 14 to 20 MPa ^1/2 is used.
(22) The method for producing a laminate of (19) to (21) above, wherein the heating / vulcanizing temperature is 120 ° C. or higher, and (23) the laminate of (1) to (18) above is used. Tire,
Is to provide.

  According to the present invention, the resin film layer and the rubber-like elastic body layer, which can be suitably used as an inner liner capable of reducing the thickness, are joined and integrated through the adhesive layer, and the production thereof In addition to good workability in the process, it is possible to provide a laminate having excellent peel resistance and a tire using the laminate.

The laminate of the present invention has a structure in which (A) a resin film layer and (B) a rubber-like elastic body layer are joined and integrated via (C) an adhesive layer.
The resin film constituting the layer (A) in the laminate of the present invention is not particularly limited as long as it has good gas barrier properties and appropriate mechanical strength, and various resin films can be used. it can. Examples of such a resin film material include polyamide resins, polyvinylidene chloride resins, polyester resins, ethylene-vinyl alcohol copolymer resins, and thermoplastic urethane elastomers. These may be used individually by 1 type, and may be used in combination of 2 or more types. Moreover, the resin film produced using these materials may be a single layer film or a multilayer film having two or more layers.
Among the above materials, thermoplastic urethane elastomers are excellent in water resistance and adhesiveness to rubber, and are preferably used in the outer layer portion particularly in multilayer films. The ethylene-vinyl alcohol copolymer resin is a preferable material because it has a very low air permeation amount and excellent gas barrier properties.

The thermoplastic urethane-based elastomer (hereinafter sometimes abbreviated as TPU) is an elastomer having a urethane group (—NH—COO—) in the molecule, and includes (1) a polyol (long chain diol), (2 It is produced by a three-component intermolecular reaction of a) diisocyanate and (3) a short-chain diol. The polyol and the short chain diol undergo an addition reaction with an isocyanate to produce a linear polyurethane. Among these, the polyol becomes a flexible portion (soft segment) of the elastomer, and the diisocyanate and the short-chain diol become a hard portion (hard segment). The properties of TPU depend on the properties of raw materials, polymerization conditions, and blending ratio, and among these, the type of polyol greatly affects the properties of TPU. Many of the basic properties are determined by the type of long chain diol, but the hardness is adjusted by the proportion of hard segments.
The types are (i) caprolactone type (polylactone ester polyol obtained by ring-opening caprolactone), (b) adipic acid type (= adipate type) <adipic acid ester polyol of adipic acid and glycol>, (ha ) PTMG (polytetramethylene glycol) type (= ether type) <polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran>.

As the ethylene-vinyl alcohol copolymer resin, a modified ethylene-vinyl alcohol copolymer obtained by reacting an ethylene compound with an ethylene-vinyl alcohol copolymer is particularly preferable. By modifying in this way, the elastic modulus of the unmodified ethylene-vinyl alcohol copolymer can be greatly reduced, and the breakability during bending and the degree of occurrence of cracks can be improved.
In the ethylene-vinyl alcohol copolymer used for this modification treatment, the ethylene unit content is preferably 25 to 50 mol%. From the viewpoint of obtaining good flex resistance and fatigue resistance, the ethylene unit content is more preferably 30 mol% or more, and even more preferably 35 mol% or more. From the viewpoint of gas barrier properties, the ethylene unit content is more preferably 48 mol% or less, and even more preferably 45 mol% or less. When the ethylene unit content is less than 25 mol%, flex resistance and fatigue resistance may be deteriorated, and melt moldability may be deteriorated. Moreover, when it exceeds 50 mol%, there exists a possibility that gas barrier property may be insufficient.
The saponification degree of the ethylene-vinyl alcohol copolymer used for the modification treatment is preferably 90 mol% or more, more preferably 95 mol% or more, further preferably 98 mol% or more, and optimally 99 mol%. More than mol%. If the degree of saponification is less than 90 mol%, the gas barrier properties and the thermal stability during production of the laminate may be insufficient.

The preferred melt flow rate (MFR) (under 190 ° C. and 21.18 N load) of the ethylene-vinyl alcohol copolymer (A) used in the modification treatment is 0.1 to 30 g / 10 min, more preferably 0.3 to 25 g / 10 min. However, when the melting point of the ethylene-vinyl alcohol copolymer is around 190 ° C. or exceeds 190 ° C., it is measured under a load of 21.18 N at a plurality of temperatures equal to or higher than the melting point. The logarithm of MFR is plotted on the vertical axis and expressed as a value extrapolated to 190 ° C.
In the modification treatment, the epoxy compound is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight, further preferably 5 to 5 parts by weight with respect to 100 parts by weight of the unmodified ethylene-vinyl alcohol copolymer. It can be carried out by reacting 35 parts by mass. In this case, it is advantageous to carry out the reaction in a solution using a suitable solvent.

  In the modification treatment method by solution reaction, a modified ethylene-vinyl alcohol copolymer is obtained by reacting an epoxy compound with an ethylene-vinyl alcohol copolymer solution in the presence of an acid catalyst or an alkali catalyst. The reaction solvent is preferably a polar aprotic solvent which is a good solvent for an ethylene-vinyl alcohol copolymer such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide and N-methylpyrrolidone. Reaction catalysts include acid catalysts such as p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, sulfuric acid and boron trifluoride, and alkali catalysts such as sodium hydroxide, potassium hydroxide, lithium hydroxide and sodium methoxide. Is mentioned. Of these, it is preferable to use an acid catalyst. As a catalyst amount, about 0.0001-10 mass parts is suitable with respect to 100 mass parts of ethylene-vinyl alcohol copolymers. The modified ethylene-vinyl alcohol copolymer can also be produced by dissolving an ethylene-vinyl alcohol copolymer and an epoxy compound in a reaction solvent and performing a heat treatment.

The epoxy compound used for the modification treatment is not particularly limited, but is preferably a monovalent epoxy compound. When the epoxy compound is divalent or higher, a cross-linking reaction with the ethylene-vinyl alcohol copolymer may occur, and the quality of the laminate may be deteriorated due to the generation of gels and blisters. From the viewpoint of ease of production of the modified ethylene-vinyl alcohol copolymer, gas barrier properties, flex resistance, and fatigue resistance, preferred monovalent epoxy compounds include glycidol and epoxy propane.
The melt flow rate (MFR) (under 190 ° C. and 21.18 N load) of the modified ethylene-vinyl alcohol copolymer used in the present invention is not particularly limited, but it has good gas barrier properties, flex resistance and fatigue resistance. From the viewpoint of obtaining, it is preferably 0.1 to 30 g / 10 minutes, more preferably 0.3 to 25 g / 10 minutes, and further preferably 0.5 to 20 g / 10 minutes. However, when the melting point of the modified EVOH is around 190 ° C or exceeds 190 ° C, it is measured at a plurality of temperatures above the melting point under a load of 21.18N. Plotted on the axis and expressed as a value extrapolated to 190 ° C.

The oxygen permeation amount at 20 ° C. and 65 RH% of the film layer made of this modified ethylene-vinyl alcohol copolymer is preferably 3 × 10 ⁻¹⁵ cm ³ · cm ² · sec · Pa or less. ^{× 10 -16 cm 3 · cm /} cm 2 · more preferably sec · Pa or less, and more preferably not more than ^{3 × 10 -16 cm 3 · cm} / cm 2 · sec · Pa.
In the laminate of the present invention, the molding method of the resin film constituting the layer (A) is not particularly limited, and in the case of a single layer film, a conventionally known method such as a solution casting method, a melt extrusion method, a calendar method, etc. is adopted. Among these methods, a melt extrusion method such as a T-die method or inflation is preferable. In the case of a multilayer film, a laminating method by coextrusion is preferably used.
The thickness of the (A) resin film layer in the laminate of the present invention is preferably 200 μm or less from the viewpoint of reducing the gauge when the laminate is used as an inner liner. Moreover, when too thin, there exists a possibility that the effect which joined the (A) layer to the (B) layer may not fully be exhibited.
Therefore, the lower limit of the thickness of the layer (A) is about 1 μm, a more preferable thickness is 10 to 150 μm, and a further preferable thickness is 20 to 100 μm.
In the laminate of the present invention, (A) the resin film layer preferably includes a thermoplastic urethane-based elastomer layer, and particularly includes a thermoplastic urethane-based elastomer layer and further includes the modified ethylene-vinyl alcohol copolymer layer. A layer composed of the above-mentioned multilayer film is preferable.

As a specific example of such a multilayer film, there can be mentioned a multilayer film having a three-layer structure in which thermoplastic urethane elastomer films are laminated on both sides of a modified ethylene-vinyl alcohol copolymer film.
In order to improve the adhesiveness with the adhesive layer provided on the (A) layer, the resin film constituting the layer (A) is formed on at least the surface of the adhesive layer by an oxidation method or an unevenness method, if desired. Surface treatment can be applied. Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone, ultraviolet irradiation treatment, and the like. Examples include solvent processing methods. These surface treatment methods are appropriately selected depending on the type of the base film, but generally, the corona discharge treatment method is preferably used from the viewpoints of effects and operability.

In the laminate of the present invention, as the rubber-like elastic body constituting the layer (B), those containing a rubber component containing 50% by mass or more of butyl rubber are preferably used. Examples of the butyl rubber include butyl rubber and / or halogenated butyl rubber. Among the butyl rubbers, the vulcanization speed is fast, heat resistance, adhesiveness, and compatibility with other unsaturated rubbers. Halogenated butyl rubber is preferred from the standpoint of superiority.
Examples of the halogenated butyl rubber include chlorinated butyl rubber, brominated butyl rubber, and modified rubber thereof. For example, there is “Enjay Butyl HT10-66” (trademark, manufactured by Enjay Chemical Co., Ltd.) as a chlorinated butyl rubber, and “bromobutyl 2255” (trademark, manufactured by Exxon Corp.) as a brominated butyl rubber. Further, a chlorinated or brominated modified copolymer of a copolymer of isomonoolefin and paramethylstyrene can be used as the modified rubber, and is available as, for example, “Expro 50” (trademark, manufactured by Exxon). .
A preferable content of the butyl rubber in the rubber component in the rubber-like elastic body is 70 to 100% by mass from the viewpoint of air permeation resistance, and 0 to 50% by mass, preferably 0 in the rubber component. Diene rubber and epichlorohydrin rubber can be contained at a ratio of ˜30 mass%.

Examples of the diene rubber include natural rubber (NR), isoprene rubber (IR), cis 1,4-polybutadiene (BR), syndiotactic-1,2-polybutadiene (1, 2BR), and styrene butadiene rubber (SBR). , Acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR) and the like.
On the other hand, epichlorohydrin rubber includes epichlorohydrin homopolymer rubber, copolymer rubber of epichlorohydrin ethylene oxide, copolymer rubber of epichlorohydrene and allyl glycidyl ether, epichlorohydrin and There are terpolymer rubbers of ethylene oxide and allyl glycidyl ether, and any of them can be used in the present invention.
In the present invention, the diene rubber and epichlorohydrin rubber may be used singly or in combination of two or more.

In order to improve the air permeation resistance, the low temperature crack resistance, the bending fatigue resistance and the like, the rubber-like elastic body can contain an inorganic filler in addition to the rubber component. In particular, the inorganic filler for improving the air permeation resistance is preferably a layered or plate-like one. Examples of such a filler include kaolin, clay, mica, feldspar, silica, and an aqueous alumina composite.
The content of the inorganic filler is usually about 10 to 180 parts by mass, preferably 20 to 120 parts by mass per 100 parts by mass of the rubber component.
Further, for the purpose of improving the strength of the unvulcanized rubber, 0 to 50 parts by mass, preferably 10 to 50 parts by mass of carbon black can be further contained per 100 parts by mass of the rubber component. The type of the carbon black is not particularly limited, and any one of those conventionally used as reinforcing fillers for rubber can be appropriately selected and used. For example, SRF, GPF, FEF, HAF, ISAF , SAF and the like.
In the present invention, the total content of the inorganic filler and carbon black is from the balance surface such as air permeation resistance, bending fatigue resistance, low temperature crack resistance and workability, per 100 parts by mass of the rubber component, A range of 30 to 200 parts by mass is preferable, and a range of 50 to 140 parts by mass is particularly preferable.

For the purpose of improving the dispersibility of the inorganic filler and carbon black in the rubber component and improving the desired physical properties, the rubber-like elastic body further contains 0 to 5 parts by weight of the dispersion improver per 100 parts by weight of the rubber component. It can be included. Examples of the dispersion improver include a silane coupling agent, dimethyl stearylamine, and triethaneramine.
These may be used individually by 1 type and may be used in combination of 2 or more types.
Further, in the rubbery elastic body, when the carbon black is blended, naphthenic or paraffinic oil is contained in an amount of 1 part by mass or more, particularly 3 to 20 parts by mass per 100 parts by mass of the rubber component. It is preferable to make it. Here, naphthenic oil preferably has% C _N by ring analysis of 30 or more, paraffinic oil% C _P 60 or more ones are preferable.

The rubbery elastic body can contain organic short fibers as desired. By including this organic short fiber, when the laminate of the present invention is used as an inner liner, it is possible to suppress the inner surface cord exposure that occurs when the inner liner is thinned to produce a tire. The organic short fibers preferably have an average diameter of 1 to 100 μm and an average length of about 0.1 to 0.5 mm. This organic short fiber may be blended as FRR (complex of short fiber and unvulcanized rubber).
The content of such organic short fibers is preferably 0.3 to 15 parts by mass per 100 parts by mass of the rubber component. The material of the organic short fiber is not particularly limited, and examples thereof include polyamides such as nylon 6, nylon 66, syndiotactic-1,2-polybutadiene, isotactic polypropylene, polyethylene and the like. Polyamide is preferred.

Further, in order to increase the modulus of the organic fiber-blended rubber, a rubber-fiber adhesion improver such as hexamethylenetetramine or resorcin can be further blended.
In the rubbery elastic body, various chemicals usually used in the rubber industry, such as a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, and a scorch, are used in addition to the above-mentioned compounding agents, as long as the object of the present invention is not impaired. Vulcanization accelerators such as an inhibitor, zinc white and stearic acid can be blended.
In the laminate of the present invention, the rubber-like elastic body constituting the layer (B) is obtained by extruding a rubber composition containing the above-described components into a film or sheet form at an unvulcanized stage by a conventional method. Can be obtained.
The thickness of the rubber-like elastic body layer (B) in the laminate of the present invention is usually 200 μm or more. Considering a reduction in gauge when used as an inner liner, it is appropriately determined depending on the tire size, but the upper limit is about 1500 μm. The preferred thickness is 200 to 1200 μm, and particularly preferably 300 to 800 μm.

  (B) When the laminate of the present invention provided with a rubber-like elastic layer is applied to an inner liner of a tire, the above-mentioned (A) resin film layer is used with a thin gauge of 200 μm or less, so that the bending resistance, Fatigue resistance is improved, and breakage and cracks are less likely to occur due to bending deformation during rolling of the tire. Even if it breaks, the (A) resin film layer has a very good adhesion with the (B) rubber-like elastic layer via the adhesive layer (C), which will be described in detail later, and is difficult to peel off, and cracks Because it is difficult to extend, large breaks and cracks do not occur. Even when it occurs, (B) the rubber elastic layer compensates for the gas barrier properties of the breakage and cracks generated in the (A) resin film layer, so that good internal pressure can be maintained even after use of the tire.

The adhesive composition constituting the adhesive layer (C) in the laminate of the present invention includes (a) 100 parts by mass of the rubber component, and (b) a thiuram-based and / or substituted dithiocarbamate-based vulcanization accelerator. 0.1 part by mass or more, (c) 0.1 part by mass or more of a silane coupling agent, and (d) at least one of poly-p-dinitrosobenzene and 1,4-phenylene dimaleimide as a crosslinking agent and a crosslinking aid. In which the composition contains 0.1 part by mass or more.
The rubber component (a) in the adhesive composition is not particularly limited as long as it forms the adhesive composition, but is preferably a halogenated butyl rubber and / or a diene rubber. The halogenated butyl rubber and the diene rubber are as exemplified in the description of the rubber-like elastic body constituting the layer (B). Of the diene rubbers, natural rubber (NR) and isoprene rubber (IR) are preferable.
These halogenated butyl rubbers and diene rubbers may be used singly or in combination of two or more. However, from the viewpoint of peeling resistance, particularly 70% by mass or more of halogenated butyl rubber, natural rubber and It is preferable that it contains 5% by mass or more of isoprene rubber.

In the adhesive composition, it is preferable that (a) 10% by mass or more of (e) chlorosulfonated polyethylene is included as a rubber component, if desired. The chlorosulfonated polyethylene (hereinafter sometimes abbreviated as CSM) is a synthetic rubber having a saturated structure that does not contain double bonds and is produced by chlorinating and chlorosulfonated polystyrene using chlorine and sulfurous acid gas. Excellent stability such as weather resistance, ozone resistance and heat resistance. CSM is commercially available from DuPont under the trade name “Hypalon”. From the viewpoints of improving the peel resistance of the adhesive layer, heat resistance, etc., those containing 10 to 40% by mass of CSM are preferable.
In addition, (a) the rubber component may contain diene rubber or butyl rubber in a proportion of 0 to 50% by mass, preferably 0 to 30% by mass. The diene rubber is as exemplified in the description of the rubber-like elastic body constituting the layer (B).
In the present invention, from the viewpoint of peeling resistance, it is particularly preferable to contain 70% by mass or more of halogenated butyl rubber, 10% by mass or more of chlorosulfonated polyethylene and 5% by mass or more of natural rubber and / or isoprene rubber.

この組成式において、Ｒ¹及びＲ²はそれぞれ炭素数１〜４の炭化水素基であって、例えば、メチル基，エチル基，ｎ−プロピル基，イソプロピル基，ｎ−ブチル基，イソブチル基，ｔ−ブチル基，ビニル基，アリル基，イソプロペニル基等が挙げられる。尚、Ｒ¹とＲ²は同一でも異なってもよい。また、Ｒ³は炭素数１〜１５の２価の炭化水素基であって、例えば、メチレン基，エチレン基，プロピレン基，ｎ−ブチレン基，イソブチレン基，へキシレン基，デシレン基，フェニレン基，メチルフェニルエチレン基等が挙げられる。ｐは０〜２の整数を示す。
組成式（Ｉ）のＲ⁴は下記一般式（II）に記載される二価の官能基である。

ここでＲ⁵〜Ｒ⁷は直鎖状又は分岐を有する炭素数１〜２０の脂肪族もしくは脂環式２価の炭化水素基、２価の芳香族基又は硫黄及び酸素以外のヘテロ元素を含む２価の有機基であり、例えばメチレン基，エチレン基，プロピレン基，ｎ−ブチレン基，イソブチレン基，へキシレン基，デシレン基，シクロへキシレン基、フェニレン基，フェニルメチレン基、メチルフェニルエチレン基等及びこれらに硫黄及び酸素以外のヘテロ元素である窒素，リン等が導入された基などが挙げられる。尚、上記Ｒ⁵〜Ｒ⁷はそれぞれ同一でも異なってもよい。
また、Ｒ⁴は硫黄原子を含むことを必須とし、ｘは平均値として１以上４未満である。ｘはそれぞれ平均値として１．５以上４未満であることが好ましく、さらには１．５以上３以下であることが最も好ましい。 The silane coupling agent of component (c) in the adhesive composition is (A) ensuring the workability (tack) for attaching the resin film layer and (B) rubber-like elastic layer, and peeling after heating and vulcanization adhesion Used to improve drag.
(C) As a silane coupling agent which is a component, the silane coupling agent containing sulfur is used preferably. The following three types of silane coupling agents containing sulfur are suitable. The first silane coupling agent A has an organooxysilyl group at both ends of the molecule, and sulfide or polysulfide at the center of the molecule. It is a compound represented by average composition formula (I) which has these.

In this composition formula, R ¹ and R ² are each a hydrocarbon group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, t -A butyl group, a vinyl group, an allyl group, an isopropenyl group, etc. are mentioned. R ¹ and R ² may be the same or different. R ³ is a divalent hydrocarbon group having 1 to 15 carbon atoms, such as methylene group, ethylene group, propylene group, n-butylene group, isobutylene group, hexylene group, decylene group, phenylene group, Examples thereof include a methylphenylethylene group. p shows the integer of 0-2.
R ^{4 in the} composition formula (I) is a divalent functional group described in the following general formula (II).

Here, R ^{5 to} R ⁷ contain a linear or branched aliphatic or alicyclic divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent aromatic group, or a hetero element other than sulfur and oxygen. Divalent organic group such as methylene group, ethylene group, propylene group, n-butylene group, isobutylene group, hexylene group, decylene group, cyclohexylene group, phenylene group, phenylmethylene group, methylphenylethylene group, etc. And groups in which nitrogen, phosphorus, etc., which are hetero elements other than sulfur and oxygen, are introduced. The R ^{5 to} R ⁷ may be the same or different.
R ⁴ must contain a sulfur atom, and x is 1 or more and less than 4 as an average value. Each x is preferably an average value of 1.5 or more and less than 4, more preferably 1.5 or more and 3 or less.

ポリサルファイド部Ｓｙは、ｙが１以上、例えばＳ1 〜Ｓ9 のような異なる硫黄原子数の分布を有している。また全ポリスルフィドシラン成分量に対してｙが３のトリスルフィドシラン含有量が２５％以上、好ましくは３０％以上であり、かつｙが５以上のポリスルフィドシラン含有量が５０％以下、好ましくは４０％以下である。トリスルフィドシランが２５％未満、あるいはｙが５以上のポリスルフィドシランが５０％を越えると混練り中のゲル化による加工性が低下して好ましくない。
また、式中、ｎは１〜３の整数、ｍは１〜９の整数を示し、好ましくは２〜５の整数を示す。
さらに、ポリサルファイド部Ｓｙのｙの平均数は、２〜３の範囲にあることが望ましい。ｙの平均数が２未満では抗破壊性および弾性率が低下しやすく、またｙの平均数が３を越えると混練り中のゲル化による加工性の低下が起こり易くなるので、上記の範囲にあることが望ましい。 The second silane coupling agent B used in the adhesive composition is a compound represented by the following average composition formula (III):

In the polysulfide part Sy, y is 1 or more, for example, a distribution of different numbers of sulfur atoms such as S1 to S9. Further, the content of trisulfide silane having y of 3 with respect to the total amount of polysulfide silane components is 25% or more, preferably 30% or more, and the content of polysulfide silane with y being 5 or more is 50% or less, preferably 40%. It is as follows. If the trisulfide silane is less than 25%, or if the polysulfide silane having y of 5 or more exceeds 50%, the processability due to gelation during kneading is unfavorable.
Moreover, in formula, n shows the integer of 1-3, m shows the integer of 1-9, Preferably the integer of 2-5 is shown.
Furthermore, the average number of y in the polysulfide part Sy is preferably in the range of 2-3. If the average number of y is less than 2, the anti-destructive property and the elastic modulus are likely to be reduced, and if the average number of y is more than 3, the workability is likely to be reduced due to gelation during kneading. It is desirable to be.

As the silane coupling agent, for example, the alkoxy group of the bis (trialkoxysilylalkyl) polysulfide having the average composition formula (III) is, for example, methoxy group, ethoxy group, propoxy group; the alkyl group is, for example, methyl group, ethyl group, n-propyl Examples thereof include a group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group; a compound in which polysulfide group -Sy- is a group having the distribution of sulfur atoms.
Although the manufacturing method of the silane coupling agent of average composition formula (III) is not particularly limited, it can be manufactured as follows based on, for example, the method described in JP-A-7-228588. Anhydrous sodium sulfide and sulfur are reacted in a polar solvent in an inert gas atmosphere at an appropriate molar ratio, for example, in the range of 1: 1 to 1: 3 to obtain sodium polysulfide, which is then converted to halogenoalkoxysilane. Is added and reacted in an inert gas atmosphere.

Ｒ⁸及びＲ⁹はそれぞれ炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基、Ｒ¹⁰は炭素数１〜１５の二価の炭化水素基、ｐは０〜２の整数である。硫黄成分はメルカプト基として含まれる。 The third sulfur-containing silane coupling agent C used in the adhesive composition is a compound represented by the following composition formula (IV).

R ⁸ and R ⁹ are each an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, R ¹⁰ is a divalent hydrocarbon group having 1 to 15 carbon atoms, and p is an integer of 0 to 2. . The sulfur component is included as a mercapto group.

  Although the said sulfur containing silane coupling agent used for the said adhesive composition is mix | blended 0.1 mass part or more with respect to 100 mass parts of (a) rubber components, the sticking workability | operativity which is the objective of this invention The upper limit of the silane coupling agent blended from the viewpoint of the effect of improving the peel resistance is preferably 30 parts by mass, and more preferably 20 parts by mass or less.

In the adhesive composition, a filler can be included as the component (f). As this filler, an inorganic filler and / or carbon black can be used. Examples of the inorganic filler include silica by a wet method (hereinafter referred to as wet silica), aluminum hydroxide, aluminum oxide, and magnesium oxide. These may be used individually by 1 type, and may be used in combination of 2 or more types.
On the other hand, about carbon black, it is as having illustrated in description of the rubber-like elastic body which comprises the above-mentioned (B) layer.
In the adhesive composition, the content of the filler as the component (f) is preferably 2 to 2 per 100 parts by mass of the rubber component as the component (a) in terms of tackiness and peeling resistance. It is selected in the range of 50 parts by mass, more preferably 5 to 35 parts by mass. In particular, from the viewpoint of tackiness, it is preferable to contain 5 parts by mass or more of an inorganic filler together with carbon black.

In the adhesive composition, as the component (b), a laminate obtained by containing 0.1 part by mass or more of a thiuram-based and / or substituted dithiocarbamate-based vulcanization accelerator per 100 parts by mass of the rubber component Can exhibit a desired peel resistance. Although there is no restriction | limiting in particular about the upper limit of content of the said vulcanization accelerator, Usually, it is about 5 mass parts. The preferable content of the vulcanization accelerator is in the range of 0.3 to 3 parts by mass.
Examples of the thiuram vulcanization accelerator include tetramethylthiuram monosulfide, tetramethylthiuram disulfide, activated tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram monosulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide, Examples include dipentamethylene thiuram hexasulfide, tetrabenzyl thiuram disulfide, and tetrakis (2-ethylhexyl) thiuram disulfide.

On the other hand, as the substituted dithiocarbamate vulcanization accelerator, for example, sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium di-n-butyldithiocarbamate, potassium dimethyldithiocarbamate, lead ethylphenyldithiocarbamate, zinc dimethyldithiocarbamate, Zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc dibenzyldithiocarbamate, zinc N-pentamethylenedithiocarbamate, zinc ethylphenyldithiocarbamate, tellurium diethyldithiocarbamate, copper dimethyldithiocarbamate, pentamethylenedithiocarbamate piperidine, etc. Is mentioned.
In the present invention, at least one selected from the thiuram vulcanization accelerator and the substituted dithiocarbamate vulcanization accelerator is used. Among these, the substituted dithiocarbamate vulcanization accelerator is used. Particularly preferred is zinc dibenzyldithiocarbamate.

In the adhesive composition, in order to improve the peel resistance after heat treatment, (d) at least one of poly-p-dinitrosobenzene and 1,4-phenylene dimaleimide is used as a crosslinking agent and a crosslinking aid. It is necessary to blend.
Poly-p-dinitrosobenzene is an effective cross-linking agent for rubbers with few double bonds such as halogenated butyl rubber. Unvulcanized compound by adding poly-p-dinitrosobenzene and heat treatment It can prevent cold flow of products, improve extrusion properties, physical properties of vulcanizates, and adjust plasticity.
In addition, vulcanization using 1,4-phenylene dimaleimide produces a carbon-carbon covalent bond and improves heat resistance and aging resistance. In particular, it is an effective crosslinking agent for chlorosulfonated polyethylene rubber.
The compounding amount of the component (d) with respect to the adhesive composition is preferably 0.2 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the rubber component of the adhesive composition. Part by mass.

In the adhesive composition, a vulcanization accelerator other than the vulcanization accelerator of the component (b) can be used in combination. Examples of the vulcanization accelerator that can be used in combination include at least one selected from guanidine, thiazole, sulfenamide, thiourea, xanthate, and the like.
In the adhesive composition part, a tackifying resin, a vulcanizing agent, stearic acid, zinc oxide, an anti-aging agent and the like can be contained as desired within a range that does not impair the object of the present invention.
As the tackifying resins, for example coumarone - indene resins; beta-pinene resins, terpene resins such as α- pinene resin; phenol - terpene resins; C ₅ petroleum resins, petroleum hydrocarbons such as C ₉ petroleum resin Resins; phenolic resins obtained by reaction of alkylphenol and formaldehyde; xylene resins; rosin resins; dicyclopentadiene resins; styrene resins.

Next, the manufacturing method of the laminated body of this invention is demonstrated.
First, each component which comprises the said adhesive composition is added to an organic solvent, and it melt | dissolves or disperses and prepares the coating liquid which consists of an adhesive composition containing an organic solvent.
At this time, as the organic solvent, (a) an organic solvent having a Hildebrand solubility parameter δ value of 14 to 20 MPa ^1/2 which is a good solvent for the rubber component is used. Examples of such an organic solvent include toluene, xylene, n-hexane, cyclohexane, methyl ethyl ketone, and chloroform. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.
The solid content concentration of the coating solution thus prepared is appropriately selected in consideration of coating properties and handleability, but is usually in the range of 5 to 50% by mass, preferably 10 to 30% by mass. is there.
Next, after coating and drying the coating liquid on the surface of the resin film constituting the layer (A), the rubber-like elastic film or sheet constituting the layer (B) is bonded thereon, The laminate of the present invention is obtained by heating and vulcanization treatment.

Alternatively, after coating and drying the coating liquid on the surface of the rubbery elastic film or sheet constituting the layer (B), the resin film constituting the layer (A) is bonded thereon. The laminate of the present invention is obtained by heating and vulcanizing.
Of these two methods, the former method is usually used.
In the above method, when the resin film constituting the layer (A) has a modified ethylene-vinyl alcohol copolymer layer, the resin film and the rubber-like elastic film or sheet are pasted via the adhesive composition layer. Before combining, the modified ethylene-vinyl alcohol copolymer layer is preferably crosslinked by irradiating the resin film with energy rays in advance. If this cross-linking operation is not performed, the modified ethylene-vinyl alcohol copolymer layer is remarkably deformed in the subsequent heating and vulcanization step, and a uniform layer cannot be maintained, and the resulting laminate is predetermined. There is a risk that the function of.
Examples of the energy rays include ionizing radiation such as ultraviolet rays, electron beams, X-rays, α rays, and γ rays, and electron beams are preferable.
As for the electron beam irradiation method, a method of introducing a resin film into an electron beam irradiation apparatus and irradiating the electron beam can be mentioned. Although it does not specifically limit regarding the dose of an electron beam, Preferably it exists in the range of 10-60 Mrad. When the electron dose to irradiate is lower than 10 Mrad, it becomes difficult to crosslink. On the other hand, when the electron dose to be irradiated exceeds 60 Mrad, the deterioration of the resin film easily proceeds. More preferably, the electron dose range is 20 to 50 Mrad.

The heating / vulcanizing treatment is usually performed at a temperature of 120 ° C. or higher, preferably 125 to 200 ° C., more preferably 130 to 180 ° C. In addition, when the laminated body of this invention is used as an inner liner of a pneumatic tire, the said heating and vulcanization process is normally performed at the time of tire vulcanization.
The laminate of the present invention has characteristics such as good tackiness, good workability and excellent peel resistance by using an adhesive composition having a specific composition. It is suitably used as an inner liner that can be made thinner.
The present invention also provides a tire using the laminate.
FIG. 1 is a partial cross-sectional view showing an example of a pneumatic tire using the laminate of the present invention as an inner liner layer. The tire is wound around a bead gore 1 so that a cord direction is directed in a radial direction. A carcass layer 2 including a carcass ply, an inner liner layer 3 made of the laminate of the present invention disposed on the inner side in the tire radial direction of the carcass layer, and an outer side in the tire radial direction of the crown portion of the carcass layer. The belt portion includes two belt layers 4, a tread portion 5 disposed on the upper portion of the belt portion, and sidewall portions 6 disposed on the left and right sides of the tread portion.
FIG. 2 is a cross-sectional detail view of an example of the inner liner layer made of the laminate of the present invention in the pneumatic tire. The inner liner layer (laminated layer of the present invention) 3 is made of unmodified ethylene-vinyl alcohol. A resin film layer 13 in which thermoplastic urethane elastomer layers 12a and 12b are laminated on both surfaces of the polymer layer 11 and a rubber-like elastic body layer 15 are joined and integrated through an adhesive layer 14. It has the structure which becomes. The rubber-like elastic body layer 15 is bonded to the carcass layer 2 in FIG. 1 on the surface opposite to the adhesive layer 14.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Production Example 1 Production of Modified Ethylene-Vinyl Alcohol Copolymer An ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol% and a saponification degree of 99.9 mol% (MFR: 5.5 g / 10 min) was placed in a pressure reaction vessel. (190 ° C, under 21.18N load)) 2 parts by weight and 8 parts by weight of N-methyl-2-pyrrolidone were charged, and the ethylene-vinyl alcohol copolymer was completely obtained by heating and stirring at 120 ° C for 2 hours. Dissolved. To this was added 0.4 part by mass of epoxypropane as an epoxy compound, and then heated at 160 ° C. for 4 hours. After the heating, it was precipitated in 100 parts by mass of distilled water, and N-methyl-2-pyrrolidone and unreacted epoxypropane were sufficiently washed with a large amount of distilled water to obtain a modified ethylene-vinyl alcohol copolymer. Further, the resulting modified ethylene-vinyl alcohol copolymer was fined to a particle size of about 2 mm with a pulverizer, and then sufficiently washed with a large amount of distilled water again. The washed particles were vacuum-dried at room temperature for 8 hours, and then melted at 200 ° C. using a twin-screw extruder and pelletized.

Production Example 2 Production of 3-layer film Using the modified EVOH obtained in Production Example 1 and thermoplastic polyurethane (Kuraray Co., Ltd., Kuramylon 3190) as an elastomer, using a two-kind three-layer coextrusion apparatus, A three-layer film (thermoplastic polyurethane layer / modified EVOH layer / thermoplastic polyurethane layer) was produced under the following coextrusion molding conditions. The thickness of each layer is 20 μm for both the modified EVOH layer and the thermoplastic polyurethane layer.
The coextrusion molding conditions are as follows.
Layer structure:
Thermoplastic polyurethane / modified EVOH / thermoplastic polyurethane (thickness 20/20/20, unit is μm)
Extrusion temperature of each resin:
C1 / C2 / C3 / die = 170/170/220/220 ° C.
Extruder specifications for each resin:
Thermoplastic polyurethane:
25mmφ extruder P25-18AC (manufactured by Osaka Seiki Co., Ltd.)
Modified EVOH:
20mmφ Extruder Lab Machine ME Type CO-EXT (Toyo Seiki Co., Ltd.)
T-die specification:
500mm width for 2 types and 3 layers (Plastic Engineering Laboratory Co., Ltd.)
Cooling roll temperature: 50 ° C
Pickup speed: 4m / min

Production Example 3 Production of Unvulcanized Rubber-like Elastic Sheet A rubber composition having the following composition was prepared to produce an unvulcanized rubber-like elastic sheet having a thickness of 500 μm.
Rubber composition (compounding unit: parts by mass)
Br-IIR (Bromobutyl 2244, manufactured by JSR Corporation): 100
GPF carbon black (Asahi Carbon Co., Ltd. # 55): 60
SUNPAR2280 (Nihon Sun Oil Co., Ltd.): 7
Stearic acid (Asahi Denka Kogyo Co., Ltd.): 1
Noxeller DM (Ouchi Shinsei Chemical Co., Ltd.): 1.3
Zinc oxide (manufactured by Hakusui Chemical Co., Ltd.): 3
Sulfur (manufactured by Karuizawa Refinery): 0.5

Production Example 4 Synthesis of Silane Coupling Agent of Average Composition Formula (I) 80 g of ethanol and anhydrous sodium sulfide in a 0.5 liter separable flask equipped with a nitrogen gas inlet tube, a thermometer, a Dimroth condenser and a dropping funnel 10.92 g (0.14 mol) and 4.48 g (0.14 mol) of sulfur were charged, and the temperature was raised to 80 ° C. While stirring this solution, 49.91 g (0.14 mol) of a compound represented by an average composition formula (CH ₃ CH ₂ O) ₃ Si— (CH ₂ ) ₃ —S— (CH ₂ ) ₆ —Cl and 1 , 6-dichlorohexane 10.85 g (0.07 mol) was slowly added dropwise. After completion of dropping, stirring was continued at 80 ° C. for 10 hours. After completion of the stirring, the mixture was cooled and the produced salt was filtered off. Then, ethanol as a solvent was distilled under reduced pressure to obtain 55.1 g of a brown transparent solution. As a result of IR analysis, ¹ H-NMR analysis and supercritical chromatography analysis of this product, average composition formula (CH ₃ CH ₂ O) ₃ Si— (CH ₂ ) ₃ —S— (CH ₂ ) ₆ —S ₂ - and _{(CH 2) 6 -S- (CH} 2) 3 -Si (OCH 2 CH 3) was confirmed to be the compound represented by the _{3 - (CH 2) 6 -S} 2. That is, in the average composition formula (I), R ¹ is an ethyl group, R ³ is an n-propyl group, and R ⁴ is (CH ₂ ) ₆ —S ₂ — (CH ₂ ) ₆ —S ₂ — (CH ₂ ) _6. (R ⁴ corresponds to the general formula (II), R ⁵ , R ⁶ and R ⁷ are (CH ₂ ) ₆ , x is an average value of 1.5), p = 0 and m = 1. . The purity of this product by GPC analysis was 85.5%.

Examples 1-11
The rubber component, filler, stearic acid, zinc white, vulcanization accelerator, and sulfur among the types and amounts of the components shown in Table 1 are kneaded according to a conventional method in advance. The remaining components shown in Table 1 were added to 1000 parts by mass of toluene (δ value: 18.2 MPa ^1/2 ) as an organic solvent, and dissolved or dispersed to prepare each adhesive coating solution.
Using the electron beam irradiation apparatus “Curetron EBC200-100 for production” manufactured by Nissin High Voltage Co., Ltd., the three-layer film obtained in Production Example 2 was irradiated with an electron beam under the conditions of an acceleration voltage of 200 kV and an irradiation energy of 30 Mrad. After the cross-linking treatment, each adhesive coating liquid was applied to one side and dried, and then the unvulcanized rubber-like elastic sheet obtained in Production Example 3 was bonded thereon.
Next, this was heated and vulcanized at 160 ° C. for 15 minutes to produce each laminate shown in FIG.

Comparative Example 1
A laminate was produced in the same manner as in Examples 1 to 10, except that METALOC R-46 manufactured by Toyo Chemical Laboratory was used as the adhesive.
Comparative Example 2
A laminate was prepared in the same manner as in Examples 1 to 11 except that 100 parts by mass of polyisoprene as a rubber component and only zinc dibenzyldithiocarbamate as an accelerator were used as the adhesive.
Comparative Example 3
A laminate was prepared in the same manner as in Examples 1 to 11 except that 100 parts by mass of brominated butyl rubber as a rubber component and only zinc dibenzyldithiocarbamate as an accelerator were used as the adhesive.
Comparative Example 4
A laminate was produced in the same manner as in Examples 1 to 11 except that 100 parts by mass of brominated butyl rubber as a rubber component and only tetrakis (2-ethylhexyl) thiuram disulfide as an accelerator were used as an adhesive.
Comparative Example 5
A laminate was prepared in the same manner as in Examples 1 to 11 except that 100 parts by mass of brominated butyl rubber as a rubber component and only tetrabenzyl thiuram disulfide as an accelerator were used as an adhesive.
For the adhesive coating solution prepared in Examples 1 to 11, the commercially available adhesive used in Comparative Example 1, and the adhesive coating solution of Comparative Examples 2 to 5, a probe tack test was performed in accordance with JIS Z0237. The tack was measured, and the index was displayed with the tack of Comparative Example 1 as 100.
Moreover, about the laminated body produced in Examples 1-11 and Comparative Examples 1-5, based on JISK6854, a T-type peeling test is performed, a peeling resistance is measured, and the peeling display of the comparative example 1 is set to 100 as an index display. did.
These results are shown in Table 1.

(note)
* Br-IIR: Bromobutyl rubber, manufactured by JSR, "Bromobutyl 2244"
* IR: Isoprene synthetic rubber, manufactured by JSR, "IR2200"
* Chlorosulfonated polyethylene: DuPont, Dow Elastomers LLC, “Hypalon”
* Silane coupling agent A: manufactured in Production Example 4. R ¹ is an ethyl group, R ³ is a propylene group, R ^{5 to} R ⁷ are hexylene groups, p = 0, x = average 1.5 * Silane coupling agent B: Degussa, “Si75”
* Silane coupling agent C: 3-mercaptopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., “KBE803”
* Carbon black: “Asahi # 80” manufactured by Asahi Carbon Co., Ltd.
* Wet silica: "AQ" manufactured by Tosoh Silica
* Magnesium oxide: “Starmag L”, manufactured by Kamishima Chemical Industries
* ZTC, zinc dibenzyldithiocarbamate, manufactured by Ouchi Shinsei Chemical Co., Ltd., “Noxera-ZTC”
* TOT: Tetrakis (2-ethylhexyl) thiuram disulfide, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., “Noxera-TOT-N”
* TBzTD: Tetrabenzylthiuram disulfide, manufactured by Sanshin Chemical Industry Co., Ltd., “Suncellor TBzTD”
* Accelerator DM: Dibenzothiazyl disulfide, manufactured by Ouchi Shinsei Chemical Co., Ltd., “Noxeller DM”
* Accelerator D: Diphenylguanidine, manufactured by Ouchi Shinsei Chemical Co., Ltd., “Noxeller D”
* C ₅ resin: Nippon Zeon Co., Ltd., "Clayton A100"
* Stearic acid: “Stearic acid 50S” manufactured by Shin-Nihon Riken
* Zinc flower: manufactured by Hakusui Tech Co., Ltd., zinc oxide, powder product * Sulfur: manufactured by Tsurumi Chemical Co., Ltd.

  The laminated body of the present invention is a laminated body in which a resin film layer and a rubber-like elastic body layer are joined and integrated via an adhesive layer. It is excellent and is suitably used as an inner liner of a pneumatic tire.

It is a fragmentary sectional view showing an example of the tire of the present invention. It is a cross-sectional detail drawing which shows an example of a structure of the laminated body of this invention.

Explanation of sign

1: Beat core 2: Carcass layer 3: Inner liner layer (laminated body layer of the present invention)
4: Belt part 5: Tread part 6: Side wall part 7: Bead filler 11: Modified ethylene-vinyl alcohol copolymer layer 12a, 12b: Thermoplastic urethane-based elastomer layer 13: Resin film layer 14: Adhesive layer 15: Rubber elastic layer

Claims (23)

  (A) A resin film layer and (B) a rubber-like elastic body layer are laminated bodies joined via (C) an adhesive layer, and the adhesive composition constituting the (C) adhesive layer (A) per 100 parts by mass of the rubber component, (b) 0.1 part by mass or more of a thiuram-based and / or substituted dithiocarbamate-based vulcanization accelerator, (c) 0.1 part by mass or more of a silane coupling agent and (D) A laminate comprising 0.1 part by mass or more of at least one of poly-p-dinitrosobenzene and 1,4-phenylene dimaleimide as a crosslinking agent and a crosslinking aid.   The laminate according to claim 1, wherein the adhesive composition further comprises (e) 10% by mass or more of chlorosulfonated polyethylene as a rubber component. The laminate according to claim 1, wherein the silane coupling agent in component (c) is a sulfur-containing silane coupling agent represented by the following average composition formula (I).

(R ¹ and R ² are each a hydrocarbon group having 1 to 4 carbon atoms, R ³ is a divalent hydrocarbon group having 1 to 15 carbon atoms, p is an integer of 0 to 2, and R ⁴ is a general formula (II ) Is a divalent functional group represented by

(R ^{5 to} R ⁷ are linear or branched divalent aliphatic or alicyclic hydrocarbon groups having 1 to 20 carbon atoms, divalent aromatic groups, or heteroelements other than sulfur and oxygen. And each of R ^{5 to} R ⁷ may be the same or different, and x is an average value of 1 or more and less than 4.) The laminate according to claim 1, wherein the silane coupling agent in component (c) is a silane coupling agent represented by the following average composition formula (III).

(N is an integer of 1 to 3, m is an integer of 1 to 9, and y is an integer of 1 or more and has a distribution.) The laminate according to claim 1, wherein the silane coupling agent in component (c) is a sulfur-containing silane coupling agent of the following composition formula (IV).

(R ⁸ and R ⁹ are each an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, R ¹⁰ is a divalent hydrocarbon group having 1 to 15 carbon atoms, and p is an integer of 0 to 2. is there.)   The laminate according to any one of claims 1 to 5, wherein the adhesive composition comprises (a) 50% by mass or more of butyl rubber per 100 parts by mass of the rubber component.   The laminate according to claim 6, wherein the butyl rubber rubber is butyl rubber and / or halogenated butyl rubber.   The laminate according to any one of claims 1 to 7, wherein in the adhesive composition, (a) the rubber component contains 70 parts by mass or more of halogenated butyl rubber and 5% by mass or more of natural rubber and / or isoprene rubber.   The adhesive composition according to any one of claims 1 to 8, comprising 2 to 50 parts by mass of a filler (f) with respect to 100 parts by mass of the rubber component (a).   (F) The laminate according to claim 9, wherein the filler is at least one selected from carbon black, silica by a wet method, aluminum hydroxide, aluminum oxide, and magnesium oxide.   (B) The vulcanization accelerator is a substituted dithiocarbamate vulcanization accelerator, The laminate according to any one of claims 1 to 10.   The laminate according to claim 11, wherein the substituted dithiocarbamate vulcanization accelerator is zinc dibenzyldithiocarbamate.   The thickness of (A) resin film layer is 200 micrometers or less, The thickness of (B) rubber-like elastic-body layer is 200 micrometers or more, The laminated body in any one of Claims 1-12.   (A) The laminated body in any one of Claims 1-13 in which a resin film layer contains a thermoplastic urethane type elastomer layer.   (A) The laminated body in any one of Claims 1-14 in which the resin film layer contains the layer which is a modified ethylene-vinyl alcohol copolymer.   The laminate according to claim 14 or 15, wherein (A) the resin film layer is a layer composed of a multilayer film including a thermoplastic urethane elastomer layer and at least one modified ethylene-vinyl alcohol copolymer layer.   (B) The laminated body according to any one of claims 1 to 16, wherein the rubber-like elastic body constituting the rubber-like elastic body layer contains a rubber component containing 50% by mass or more of butyl rubber.   The laminate according to claim 17, wherein the butyl rubber is butyl rubber and / or halogenated butyl rubber.   Applying and drying a coating liquid composed of an adhesive composition containing an organic solvent on the surface of a resin film, and then sticking a rubber-like elastic film or sheet thereon, followed by heating and vulcanization treatment The manufacturing method of the laminated body in any one of Claims 1-18 characterized by the above-mentioned.   Applying and drying a coating liquid consisting of an adhesive composition containing an organic solvent on a rubber-like elastic film or sheet surface, then bonding a resin film on it, and heating / vulcanizing it. The manufacturing method of the laminated body in any one of Claims 1-18 characterized by the above-mentioned. The method for producing a laminate according to claim 19 or 20, wherein an organic solvent having a Hildebrand solubility parameter δ value in the range of 14 to 20 MPa ^1/2 is used.   The method for producing a laminate according to any one of claims 19 to 21, wherein the heating / vulcanizing temperature is 120 ° C or higher. A tire using the laminate according to any one of claims 1 to 18.

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