JP5172597B2 - Inner liner for pneumatic tires - Google Patents
Inner liner for pneumatic tires Download PDFInfo
- Publication number
- JP5172597B2 JP5172597B2 JP2008270828A JP2008270828A JP5172597B2 JP 5172597 B2 JP5172597 B2 JP 5172597B2 JP 2008270828 A JP2008270828 A JP 2008270828A JP 2008270828 A JP2008270828 A JP 2008270828A JP 5172597 B2 JP5172597 B2 JP 5172597B2
- Authority
- JP
- Japan
- Prior art keywords
- styrene
- block copolymer
- inner liner
- block
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 229920001400 block copolymer Polymers 0.000 claims description 42
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- 229920006132 styrene block copolymer Polymers 0.000 claims description 15
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Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、加硫工程を必要とせず、空気バリア性、柔軟性、靱性とカーカスへの接着性に優れた空気入りタイヤ用インナーライナーに関する。 The present invention relates to an inner liner for a pneumatic tire that does not require a vulcanization step and has excellent air barrier properties, flexibility, toughness, and adhesion to a carcass.
従来、耐気体透過性材料としてブチルゴムは種々の分野で利用されている。例えば、薬栓やタイヤインナーライナー用材料として使用されている。しかし、タイヤインナーライナー用材料として使用する場合には、加硫操作を必要とするため操作性に劣るという問題点があった。 Conventionally, butyl rubber has been used in various fields as a gas-permeable material. For example, it is used as a material for medicine plugs and tire inner liners. However, when used as a material for a tire inner liner, there is a problem that the operability is poor because a vulcanization operation is required.
特許文献１には芳香族ビニル化合物とイソブチレンとのブロック共重合体とカーボンブラックとを含有するタイヤインナーライナー用ゴム組成物が開示されている。これは加硫工程を必要とせず、ガスバリアには優れているものの未だカーカス層を構成するゴムとの接着は不十分であった。
本発明は、上記の課題に鑑みてなされたものであって、空気入りタイヤのインナーライナー層として加硫操作を必要とせず、空気バリア性、柔軟性、靱性とカーカスへの接着性のバランスに優れたインナーライナーを提供することにある。 The present invention has been made in view of the above problems, and does not require a vulcanization operation as an inner liner layer of a pneumatic tire, and balances air barrier properties, flexibility, toughness, and adhesion to a carcass. It is to provide an excellent inner liner.
本発明者らは、鋭意検討した結果、本発明を完成するに至った。すなわち本発明は、芳香族ビニル系化合物を主体とする重合体ブロック（ａ）およびイソブチレンを主体とする重合体ブロック（ｂ）からなるブロック共重合体（Ａ）を含む層と、芳香族ビニル化合物を主体とする重合体ブロックと共役ジエンを主体とする重合体ブロックとからなるブロック共重合体、またはその水素添加物（Ｂ）を含む層とを積層したことを特徴とする空気入りタイヤ用インナーライナーに関する。 As a result of intensive studies, the present inventors have completed the present invention. That is, the present invention relates to a layer comprising a block copolymer (A) comprising a polymer block (a) mainly comprising an aromatic vinyl compound and a polymer block (b) mainly comprising isobutylene, and an aromatic vinyl compound. An inner layer for a pneumatic tire, characterized by laminating a block copolymer comprising a polymer block mainly comprising a conjugated diene and a block containing a hydrogenated product (B) thereof. Regarding the liner.
好ましい実施態様としては、ブロック共重合体（Ａ）の重量平均分子量が３０，０００〜１５０，０００であり、かつ芳香族ビニル系化合物を主体とする重合体ブロック（ａ）を１０〜４０重量％含むことを特徴とする空気入りタイヤ用インナーライナーに関する。 As a preferred embodiment, the block copolymer (A) has a weight average molecular weight of 30,000 to 150,000, and 10 to 40% by weight of the polymer block (a) mainly composed of an aromatic vinyl compound. It is related with the inner liner for pneumatic tires characterized by including.
好ましい実施態様としては、ブロック共重合体（Ａ）の芳香族ビニル系化合物がスチレンであり、かつブロック共重合体（Ａ）の重量平均分子量／数平均分子量が１．３以下であることを特徴とする空気入りタイヤ用インナーライナーに関する。 In a preferred embodiment, the aromatic vinyl-based compound of the block copolymer (A) is styrene, and the weight average molecular weight / number average molecular weight of the block copolymer (A) is 1.3 or less. The present invention relates to an inner liner for a pneumatic tire.
好ましい実施態様としては、芳香族ビニル化合物を主体とする重合体ブロックと共役ジエンを主体とする重合体ブロックとからなるブロック共重合体、またはその水素添加物（Ｂ）が、スチレン−ブタジエンブロック共重合体、スチレンーブタジエンースチレンブロック共重合体、スチレン−イソプレンブロック共重合体、スチレン−イソプレン−スチレンブロック共重合体、スチレン−エチレン・プロピレン−スチレンブロック共重合体、スチレン−エチレン・ブチレン−スチレンブロック共重合体、スチレン−エチレン・エチレン・プロピレン−スチレンブロック共重合体からなる群より選ばれる少なくとも１種であることを特徴とする空気入りタイヤ用インナーライナーに関する。 As a preferred embodiment, a block copolymer composed of a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene, or a hydrogenated product (B) thereof, comprises a styrene-butadiene block copolymer. Polymer, styrene-butadiene-styrene block copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene / propylene-styrene block copolymer, styrene-ethylene / butylene-styrene The present invention relates to an inner liner for a pneumatic tire, which is at least one selected from the group consisting of a block copolymer and a styrene-ethylene / ethylene / propylene / styrene block copolymer.
好ましい実施態様としては、ブロック共重合体（Ａ）を含む層がブロック共重合体（Ａ）１００重量部に対してさらにエチレン−ビニルアルコール共重合体（Ｃ）を１〜５００重量部を含有することを特徴とする空気入りタイヤ用インナーライナーに関する。 As a preferred embodiment, the layer containing the block copolymer (A) further contains 1 to 500 parts by weight of the ethylene-vinyl alcohol copolymer (C) with respect to 100 parts by weight of the block copolymer (A). The present invention relates to an inner liner for a pneumatic tire.
さらに本発明は、多層押出によって成形されたことを特徴とする上記記載の空気入りタイヤ用インナーライナーに関する。 Furthermore, the present invention relates to the above inner liner for a pneumatic tire, which is formed by multilayer extrusion.
本発明の空気入りタイヤ用インナーライナーは加硫工程を必要とせず、空気バリア性、柔軟性、靱性とカーカスへの接着性のバランスに優れたインナーライナーに優れており、タイヤの組み立て容易化、あるいはガス圧の保持力の向上に好適である。 The inner liner for a pneumatic tire of the present invention does not require a vulcanization step, and is excellent in an inner liner excellent in the balance of air barrier properties, flexibility, toughness and adhesion to a carcass, facilitating tire assembly, Or it is suitable for the improvement of the holding | maintenance force of gas pressure.
本発明の空気入りタイヤ用インナーライナーは芳香族ビニル系化合物を主体とする重合体ブロック（ａ）およびイソブチレンを主体とする重合体ブロック（ｂ）からなるブロック共重合体（Ａ）を含む層と芳香族ビニル化合物を主体とする重合体ブロックと共役ジエンを主体とする重合体ブロックとからなるブロック共重合体、またはその水素添加物（Ｂ）を含む層とを積層したものである。 The inner liner for a pneumatic tire of the present invention comprises a layer containing a block copolymer (A) comprising a polymer block (a) mainly composed of an aromatic vinyl compound and a polymer block (b) mainly composed of isobutylene. A block copolymer composed of a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene, or a layer containing a hydrogenated product (B) thereof is laminated.
本発明のブロック共重合体（Ａ）とは芳香族ビニル系化合物を主体とする重合体ブロック（ａ）およびイソブチレンを主体とする重合体ブロック（ｂ）からなるブロック共重合体である。 The block copolymer (A) of the present invention is a block copolymer comprising a polymer block (a) mainly composed of an aromatic vinyl compound and a polymer block (b) mainly composed of isobutylene.
芳香族ビニル系化合物としては、スチレン、ｏ−、ｍ−又はｐ−メチルスチレン、α−メチルスチレン、β−メチルスチレン、２，６−ジメチルスチレン、２，４−ジメチルスチレン、α−メチル−ｏ−メチルスチレン、α−メチル−ｍ−メチルスチレン、α−メチル−ｐ−メチルスチレン、β−メチル−ｏ−メチルスチレン、β−メチル−ｍ−メチルスチレン、β−メチル−ｐ−メチルスチレン、２，４，６−トリメチルスチレン、α−メチル−２，６−ジメチルスチレン、α−メチル−２，４−ジメチルスチレン、β−メチル−２，６−ジメチルスチレン、β−メチル−２，４−ジメチルスチレン、ｏ−、ｍ−又はｐ−クロロスチレン、２，６−ジクロロスチレン、２，４−ジクロロスチレン、α−クロロ−ｏ−クロロスチレン、α−クロロ−ｍ−クロロスチレン、α−クロロ−ｐ−クロロスチレン、β−クロロ−ｏ−クロロスチレン、β−クロロ−ｍ−クロロスチレン、β−クロロ−ｐ−クロロスチレン、２，４，６−トリクロロスチレン、α−クロロ−２，６−ジクロロスチレン、α−クロロ−２，４−ジクロロスチレン、β−クロロ−２，６−ジクロロスチレン、β−クロロ−２，４−ジクロロスチレン、ｏ−、ｍ−又はｐ−ｔ−ブチルスチレン、ｏ−、ｍ−又はｐ−メトキシスチレン、ｏ−、ｍ−又はｐ−クロロメチルスチレン、ｏ−、ｍ−又はｐ−ブロモメチルスチレン、シリル基で置換されたスチレン誘導体、インデン、ビニルナフタレン等が挙げられる。これらの中でも、工業的な入手性やガラス転移温度の点から、スチレン、α−メチルスチレン、および、これらの混合物が好ましく、特にスチレンが好ましい。 Aromatic vinyl compounds include styrene, o-, m- or p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o. -Methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene, 2 , 4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2,4-dimethyl Styrene, o-, m- or p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-chlorostyrene, α-chloro-m- Chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α- Chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, o-, m- or p- t-butylstyrene, o-, m- or p-methoxystyrene, o-, m- or p-chloromethylstyrene, o-, m- or p-bromomethylstyrene, styrene derivatives substituted with silyl groups, indene And vinyl naphthalene. Among these, styrene, α-methylstyrene, and a mixture thereof are preferable from the viewpoint of industrial availability and glass transition temperature, and styrene is particularly preferable.
イソブチレンを主成分とする重合体ブロック（ｂ）は、イソブチレンに由来するユニットが６０重量％以上、好ましくは８０重量％以上から構成される重合体ブロックである。 The polymer block (b) mainly composed of isobutylene is a polymer block composed of 60% by weight or more, preferably 80% by weight or more of units derived from isobutylene.
いずれの重合体ブロックも、共重合成分として、相互の単量体を使用することができるほか、その他のカチオン重合可能な単量体成分を使用することができる。このような単量体成分としては、脂肪族オレフィン類、ジエン類、ビニルエーテル類、シラン類、ビニルカルバゾール、β−ピネン、アセナフチレン等の単量体が例示できる。これらはそれぞれ単独で又は２種以上を組み合わせて使用することができる。 Any of the polymer blocks can use mutual monomers as copolymerization components, and other monomer components capable of cationic polymerization. Examples of such a monomer component include monomers such as aliphatic olefins, dienes, vinyl ethers, silanes, vinyl carbazole, β-pinene, and acenaphthylene. These can be used alone or in combination of two or more.
脂肪族オレフィン系単量体としては、エチレン、プロピレン、１−ブテン、２−メチル−１−ブテン、３−メチル−１−ブテン、ペンテン、ヘキセン、シクロヘキセン、４−メチル−１−ペンテン、ビニルシクロヘキサン、オクテン、ノルボルネン等が挙げられる。 Aliphatic olefin monomers include ethylene, propylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, hexene, cyclohexene, 4-methyl-1-pentene, vinylcyclohexane Octene, norbornene and the like.
ジエン系単量体としては、ブタジエン、イソプレン、ヘキサジエン、シクロペンタジエン、シクロヘキサジエン、ジシクロペンタジエン、ジビニルベンゼン、エチリデンノルボルネン等が挙げられる。 Examples of the diene monomer include butadiene, isoprene, hexadiene, cyclopentadiene, cyclohexadiene, dicyclopentadiene, divinylbenzene, and ethylidene norbornene.
ビニルエーテル系単量体としては、メチルビニルエーテル、エチルビニルエーテル、（ｎ−、イソ）プロピルビニルエーテル、（ｎ−、ｓｅｃ−、ｔｅｒｔ−、イソ）ブチルビニルエーテル、メチルプロペニルエーテル、エチルプロペニルエーテル等が挙げられる。 Examples of the vinyl ether monomer include methyl vinyl ether, ethyl vinyl ether, (n-, iso) propyl vinyl ether, (n-, sec-, tert-, iso) butyl vinyl ether, methyl propenyl ether, ethyl propenyl ether and the like.
シラン化合物としては、ビニルトリクロロシラン、ビニルメチルジクロロシラン、ビニルジメチルクロロシラン、ビニルジメチルメトキシシラン、ビニルトリメチルシラン、ジビニルジクロロシラン、ジビニルジメトキシシラン、ジビニルジメチルシラン、１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン、トリビニルメチルシラン、γ−メタクリロイルオキシプロピルトリメトキシシラン、γ−メタクリロイルオキシプロピルメチルジメトキシシラン等が挙げられる。 Examples of the silane compound include vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3. , 3-tetramethyldisiloxane, trivinylmethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and the like.
本発明の（Ａ）成分は、芳香族ビニル系ブロックとイソブチレン系ブロックから構成されている限り、その構造には特に制限はなく、例えば、直鎖状、分岐状、星状等の構造を有するブロック共重合体、ジブロック共重合体、トリブロック共重合体、マルチブロック共重合体等のいずれも選択可能である。好ましい構造としては、物性バランス及び成形加工性の点から、芳香族ビニル系重合体ブロック−イソブチレン系重合体ブロック−芳香族ビニル系重合体ブロックで構成されるトリブロック共重合体が挙げられる。これらは所望の物性・成形加工性を得る為に、それぞれ単独で又は２種以上を組み合わせて使用することができる。 The component (A) of the present invention is not particularly limited as long as it is composed of an aromatic vinyl block and an isobutylene block, and has, for example, a linear, branched, or star structure. Any of a block copolymer, a diblock copolymer, a triblock copolymer, a multiblock copolymer, and the like can be selected. A preferable structure includes a triblock copolymer composed of an aromatic vinyl polymer block, an isobutylene polymer block, and an aromatic vinyl polymer block from the viewpoint of physical property balance and molding processability. These may be used alone or in combination of two or more in order to obtain desired physical properties and moldability.
芳香族ビニル系重合体ブロックとイソブチレン系重合体ブロックの割合に関しては、特に制限はないが、柔軟性およびゴム弾性の点から、（Ａ）成分における芳香族ビニル系重合体ブロックの含有量が１０〜４０重量％であることが好ましく、１０〜３５重量％であることがさらに好ましい。 The ratio of the aromatic vinyl polymer block to the isobutylene polymer block is not particularly limited, but the content of the aromatic vinyl polymer block in the component (A) is 10 from the viewpoint of flexibility and rubber elasticity. It is preferably ˜40% by weight, more preferably 10 to 35% by weight.
また（Ａ）成分の分子量にも特に制限はないが、流動性、成形加工性、ゴム弾性等の面から、ＧＰＣ測定による重量平均分子量で３０，０００〜３００，０００であることが好ましく、３０，０００〜１５０，０００であることが特に好ましい。重量平均分子量が３０，０００よりも低い場合には機械的な物性が十分に発現されない傾向があり、一方３００，０００を超える場合には流動性、加工性が悪化する傾向がある。 The molecular weight of the component (A) is not particularly limited, but is preferably 30,000 to 300,000 in terms of weight average molecular weight by GPC measurement from the viewpoint of fluidity, molding processability, rubber elasticity, and the like. 1 to 150,000 is particularly preferable. When the weight average molecular weight is lower than 30,000, mechanical properties tend not to be sufficiently exhibited, whereas when it exceeds 300,000, fluidity and workability tend to deteriorate.
本発明の（Ａ）成分としては、ブロック共重合体（Ａ）の重量平均分子量が３０，０００〜１５０，０００であり、かつ芳香族ビニル系化合物を主体とする重合体ブロック（ａ）を１０〜４０重量％含むことがこのましい。さらには、ブロック共重合体（Ａ）の芳香族ビニル系化合物がスチレンであり、かつブロック共重合体（Ａ）の重量平均分子量／数平均分子量が１．３以下であることが好ましい。 As the component (A) of the present invention, the block copolymer (A) has a weight average molecular weight of 30,000 to 150,000 and 10 polymer blocks (a) mainly composed of an aromatic vinyl compound. It is preferable to contain ~ 40% by weight. Furthermore, it is preferable that the aromatic vinyl-based compound of the block copolymer (A) is styrene, and the weight average molecular weight / number average molecular weight of the block copolymer (A) is 1.3 or less.
（Ａ）成分の製造方法については特に制限はないが、例えば、下記一般式（Ｉ）で表される化合物の存在下に、単量体成分を重合させることにより得られる。
（ＣＲ1Ｒ2Ｘ）ｎＲ3 （Ｉ）
［式中Ｘはハロゲン原子、炭素数１〜６のアルコキシ基またはアシロキシ基から選ばれる置換基、Ｒ1、Ｒ2はそれぞれ水素原子または炭素数１〜６の１価炭化水素基でＲ1、Ｒ2は同一であっても異なっていても良く、Ｒ3は一価若しくは多価芳香族炭化水素基または一価若しくは多価脂肪族炭化水素基であり、ｎは１〜６の自然数を示す。］
Although there is no restriction | limiting in particular about the manufacturing method of (A) component, For example, it can obtain by polymerizing a monomer component in presence of the compound represented by the following general formula (I).
(CR 1 R 2 X) nR 3 (I)
[Wherein X is a halogen atom, a substituent selected from an alkoxy group having 1 to 6 carbon atoms or an acyloxy group, R 1 and R 2 are each a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R 1 , R 2 may be the same or different, R 3 is a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic hydrocarbon group, and n represents a natural number of 1 to 6. . ]
上記一般式（Ｉ）で表わされる化合物は開始剤となるものでルイス酸等の存在下炭素陽イオンを生成し、カチオン重合の開始点になると考えられる。本発明で用いられる一般式（Ｉ）の化合物の例としては、次のような化合物等が挙げられる。 The compound represented by the above general formula (I) serves as an initiator, and is considered to generate a carbon cation in the presence of a Lewis acid or the like and serve as a starting point for cationic polymerization. The following compounds etc. are mentioned as an example of the compound of general formula (I) used by this invention.
（１−クロル−１−メチルエチル）ベンゼン［Ｃ6Ｈ5Ｃ（ＣＨ3）2Ｃｌ］、１，４−ビス（１−クロル−１−メチルエチル）ベンゼン［１，４−Ｃｌ（ＣＨ3）2ＣＣ6Ｈ4Ｃ（ＣＨ3）2Ｃｌ］、１，３−ビス（１−クロル−１−メチルエチル）ベンゼン［１，３−Ｃｌ（ＣＨ3）2ＣＣ6Ｈ4Ｃ（ＣＨ3）2Ｃｌ］、１，３，５−トリス（１−クロル−１−メチルエチル）ベンゼン［１，３，５−（ＣｌＣ（ＣＨ3）2）3Ｃ6Ｈ3］、１，３−ビス（１−クロル−１−メチルエチル）−５−（ｔｅｒｔ−ブチル）ベンゼン［１，３−（Ｃ（ＣＨ3）2Ｃｌ）2-５−（Ｃ（ＣＨ3）3）Ｃ6Ｈ3］ (1-Chloro-1-methylethyl) benzene [C 6 H 5 C (CH 3 ) 2 Cl], 1,4-bis (1-chloro-1-methylethyl) benzene [1,4-Cl (CH 3 ) 2 CC 6 H 4 C (CH 3 ) 2 Cl], 1,3-bis (1-chloro-1-methylethyl) benzene [1,3-Cl (CH 3 ) 2 CC 6 H 4 C (CH 3 ) 2 Cl], 1,3,5-tris (1-chloro-1-methylethyl) benzene [1,3,5- (ClC (CH 3 ) 2 ) 3 C 6 H 3 ], 1,3-bis (1-Chloro-1-methylethyl) -5- (tert-butyl) benzene [1,3- (C (CH 3 ) 2 Cl) 2 -5- (C (CH 3 ) 3 ) C 6 H 3 ]
これらの中でも特に好ましいのはビス（１−クロル−１−メチルエチル）ベンゼン［Ｃ6Ｈ4（Ｃ（ＣＨ3）2Ｃｌ）2］、トリス（１−クロル−１−メチルエチル）ベンゼン［（ＣｌＣ（ＣＨ3）2）3Ｃ6Ｈ3］である。［なおビス（１−クロル−１−メチルエチル）ベンゼンは、ビス（α−クロロイソプロピル）ベンゼン、ビス（２−クロロ−２−プロピル）ベンゼンあるいはジクミルクロライドとも呼ばれ、トリス（１−クロル−１−メチルエチル）ベンゼンは、トリス（α−クロロイソプロピル）ベンゼン、トリス（２−クロロ−２−プロピル）ベンゼンあるいはトリクミルクロライドとも呼ばれる］。 Of these, bis (1-chloro-1-methylethyl) benzene [C 6 H 4 (C (CH 3 ) 2 Cl) 2 ], tris (1-chloro-1-methylethyl) benzene [( ClC (CH 3 ) 2 ) 3 C 6 H 3 ]. [Bis (1-chloro-1-methylethyl) benzene is also called bis (α-chloroisopropyl) benzene, bis (2-chloro-2-propyl) benzene or dicumyl chloride, and tris (1-chloro- 1-methylethyl) benzene is also referred to as tris (α-chloroisopropyl) benzene, tris (2-chloro-2-propyl) benzene, or tricumyl chloride.
（Ａ）成分を製造する際には、さらにルイス酸触媒を共存させることもできる。このようなルイス酸としてはカチオン重合に使用できるものであれば良く、ＴｉＣｌ4、ＴｉＢｒ4、ＢＣｌ3、ＢＦ3、ＢＦ3・ＯＥｔ2、ＳｎＣｌ4、ＳｂＣｌ5、ＳｂＦ5、ＷＣｌ6、ＴａＣｌ5、ＶＣｌ5、ＦｅＣｌ3、ＺｎＢｒ2、ＡｌＣｌ3、ＡｌＢｒ3等の金属ハロゲン化物；Ｅｔ2ＡｌＣｌ、ＥｔＡｌＣｌ2等の有機金属ハロゲン化物を好適に使用することができる。中でも触媒としての能力、工業的な入手の容易さを考えた場合、ＴｉＣｌ4、ＢＣｌ3、ＳｎＣｌ4が好ましい。ルイス酸の使用量は、特に限定されないが、使用する単量体の重合特性あるいは重合濃度等を鑑みて設定することができる。通常は一般式（Ｉ）で表される化合物に対して０．１〜１００モル当量使用することができ、好ましくは１〜５０モル当量の範囲である。 When the component (A) is produced, a Lewis acid catalyst can be present together. Such Lewis acid may be any one that can be used for cationic polymerization. TiCl 4 , TiBr 4 , BCl 3 , BF 3 , BF 3 .OEt 2 , SnCl 4 , SbCl 5 , SbF 5 , WCl 6 , TaCl 5 , VCl 5 , FeCl 3 , ZnBr 2 , AlCl 3 , AlBr 3, etc .; metal halides such as Et 2 AlCl, EtAlCl 2, etc. can be preferably used. Of these, TiCl 4 , BCl 3 , and SnCl 4 are preferable in view of the ability as a catalyst and industrial availability. The amount of Lewis acid used is not particularly limited, but can be set in view of the polymerization characteristics or polymerization concentration of the monomer used. Usually, it is 0.1-100 mol equivalent with respect to the compound represented with general formula (I), Preferably it is the range of 1-50 mol equivalent.
（Ａ）成分の製造に際しては、さらに必要に応じて電子供与体成分を共存させることもできる。この電子供与体成分は、カチオン重合に際して、成長炭素カチオンを安定化させる効果があるものと考えられており、電子供与体の添加によって、分子量分布の狭い、構造が制御された重合体を生成することができる。使用可能な電子供与体成分としては特に限定されないが、例えば、ピリジン類、アミン類、アミド類、スルホキシド類、エステル類、または金属原子に結合した酸素原子を有する金属化合物等を挙げることができる。 In the production of the component (A), an electron donor component can be allowed to coexist if necessary. This electron donor component is believed to have the effect of stabilizing the growth carbon cation during cationic polymerization, and the addition of an electron donor produces a polymer with a narrow molecular weight distribution and a controlled structure. be able to. The electron donor component that can be used is not particularly limited, and examples thereof include pyridines, amines, amides, sulfoxides, esters, and metal compounds having an oxygen atom bonded to a metal atom.
（Ａ）成分の重合は必要に応じて有機溶媒中で行うことができ、有機溶媒としてはカチオン重合を本質的に阻害しなければ、特に制約なく使用することができる。具体的には、塩化メチル、ジクロロメタン、クロロホルム、塩化エチル、ジクロロエタン、ｎ−プロピルクロライド、ｎ−ブチルクロライド、クロロベンゼン等のハロゲン化炭化水素；ベンゼン、トルエン、キシレン、エチルベンゼン、プロピルベンゼン、ブチルベンゼン等のアルキルベンゼン類；エタン、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン等の直鎖式脂肪族炭化水素類；２−メチルプロパン、２−メチルブタン、２，３，３−トリメチルペンタン、２，２，５−トリメチルヘキサン等の分岐式脂肪族炭化水素類；シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン等の環式脂肪族炭化水素類；石油留分を水添精製したパラフィン油等を挙げることができる。 The polymerization of the component (A) can be carried out in an organic solvent as necessary, and the organic solvent can be used without particular limitation as long as it does not substantially inhibit cationic polymerization. Specifically, halogenated hydrocarbons such as methyl chloride, dichloromethane, chloroform, ethyl chloride, dichloroethane, n-propyl chloride, n-butyl chloride, chlorobenzene; benzene, toluene, xylene, ethylbenzene, propylbenzene, butylbenzene, etc. Alkylbenzenes; linear aliphatic hydrocarbons such as ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane; 2-methylpropane, 2-methylbutane, 2,3,3-trimethylpentane, 2 Branched aliphatic hydrocarbons such as 1,2,5-trimethylhexane; cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane and ethylcyclohexane; paraffin oil obtained by hydrorefining petroleum fractions, etc. .
これらの溶媒は、（Ａ）成分を構成する単量体の重合特性及び生成する重合体の溶解性等のバランスを考慮して、それぞれ単独で又は２種以上を組み合わせて使用することができる。 These solvents can be used alone or in combination of two or more in consideration of the balance of the polymerization characteristics of the monomer constituting the component (A) and the solubility of the polymer produced.
上記溶媒の使用量は、得られる重合体溶液の粘度や除熱の容易さを考慮して、重合体の濃度が１〜５０ｗｔ％、好ましくは５〜３５ｗｔ％となるように決定される。 The amount of the solvent used is determined so that the concentration of the polymer is 1 to 50 wt%, preferably 5 to 35 wt%, in consideration of the viscosity of the resulting polymer solution and the ease of heat removal.
実際の重合を行うに当たっては、各成分を冷却下例えば−１００℃以上０℃未満の温度で混合する。エネルギーコストと重合の安定性を釣り合わせるために、特に好ましい温度範囲は−３０℃〜−８０℃である。 In carrying out the actual polymerization, each component is mixed at a temperature of, for example, −100 ° C. or more and less than 0 ° C. under cooling. In order to balance the energy cost and the stability of polymerization, a particularly preferred temperature range is −30 ° C. to −80 ° C.
芳香族ビニル化合物を主体とする重合体ブロックと、共役ジエンを主体とする重合体ブロックとからなるブロック共重合体またはその水素添加物（Ｂ）としては、芳香族ビニル化合物を主体とする重合体ブロック（ｃ）と、共役ジエン重合体ブロック（ｄ）とからなるブロック共重合体である。例えば、（ｃ）−（ｄ）、（ｃ）−（ｄ）−（ｃ）、（ｄ）−（ｃ）−（ｄ）−（ｃ）、（ｃ）−（ｄ）−（ｃ）−（ｄ）−（ｃ）等の構造を有するビニル芳香族化合物−共役ジエンブロック共重合体又はその水添ブロック共重合体を挙げることができる。これらは混合して使用しても良い。上記（水添）ブロック共重合体（以下、（水添）ブロック共重合体とは、ブロック共重合体、及び／又は、水添ブロック共重合体を意味する。）は、芳香族ビニル化合物を５〜６０重量％、好ましくは、２０〜５０重量％含む。芳香族ビニル化合物を主体とする重合体ブロック（ｃ）は好ましくは、芳香族ビニル化合物のみから成るか、または芳香族ビニル化合物５０重量％以上、好ましくは７０重量％以上と任意成分、例えば（水素添加された）共役ジエン（以下、（水素添加された）共役ジエンとは、共役ジエン、及び／又は、水素添加された共役ジエンを意味する）との共重合体ブロックである。（水素添加された）共役ジエンを主体とする重合体ブロック（ｄ）は好ましくは、（水素添加された）共役ジエンのみから成るか、または（水素添加された）共役ジエン５０重量％以上、好ましくは７０重量％以上と任意成分、例えば芳香族ビニル化合物との共重合体ブロックである。 A block copolymer comprising a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene, or a hydrogenated product (B) thereof, is a polymer mainly composed of an aromatic vinyl compound. A block copolymer comprising a block (c) and a conjugated diene polymer block (d). For example, (c)-(d), (c)-(d)-(c), (d)-(c)-(d)-(c), (c)-(d)-(c)- Examples thereof include a vinyl aromatic compound-conjugated diene block copolymer having a structure such as (d)-(c) or a hydrogenated block copolymer thereof. You may mix and use these. The (hydrogenated) block copolymer (hereinafter, (hydrogenated) block copolymer means a block copolymer and / or a hydrogenated block copolymer) is an aromatic vinyl compound. 5 to 60% by weight, preferably 20 to 50% by weight. The polymer block (c) mainly composed of an aromatic vinyl compound is preferably composed only of an aromatic vinyl compound or an optional component such as (hydrogen) of 50% by weight or more, preferably 70% by weight or more of an aromatic vinyl compound. An added) conjugated diene (hereinafter referred to as (hydrogenated) conjugated diene means a conjugated diene and / or a hydrogenated conjugated diene). The polymer block (d) mainly composed of (hydrogenated) conjugated dienes is preferably composed only of (hydrogenated) conjugated dienes or more than 50% by weight of (hydrogenated) conjugated dienes, preferably Is a copolymer block of 70% by weight or more and an optional component such as an aromatic vinyl compound.
上記（水添）ブロック共重合体の溶液粘度（５％トルエン溶液、７７°Ｆ、ＡＳＴＭ Ｄ−２１９６）の範囲は、５〜５００ｃｐｓ、好ましくは２０〜３００ｃｐｓである。 The solution viscosity (5% toluene solution, 77 ° F., ASTM D-2196) of the above (hydrogenated) block copolymer is in the range of 5 to 500 cps, preferably 20 to 300 cps.
上記（水添）ブロック共重合体の数平均分子量は、好ましくは５，０００〜１，５００，０００、より好ましくは、１０，０００〜５５０，０００、更に好ましくは９０，０００〜４００，０００の範囲であり、分子量分布は１０以下である。ブロック共重合体の分子構造は、直鎖状、分岐状、放射状あるいはこれらの任意の組合せのいずれであってもよい。 The number average molecular weight of the (hydrogenated) block copolymer is preferably 5,000 to 1,500,000, more preferably 10,000 to 550,000, still more preferably 90,000 to 400,000. The molecular weight distribution is 10 or less. The molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof.
また、これらの芳香族ビニル化合物を主体とする重合体ブロック（ｃ）、共役ジエンを主体とする重合体ブロック（ｄ）において、分子鎖中の共役ジエン化合物又は芳香族ビニル化合物由来の単位の分布がランダム、テーパード（分子鎖に沿ってモノマー成分が増加又は減少するもの）、一部ブロック状又はこれらの任意の組合せでなっていてもよい。芳香族ビニル化合物を主体とする重合体ブロック（ｃ）又は共役ジエンを主体とする重合体ブロック（ｄ）がそれぞれ２個以上ある場合には、各重合体ブロックはそれぞれが同一構造であっても異なる構造であってもよい。 Further, in the polymer block (c) mainly composed of these aromatic vinyl compounds and the polymer block (d) mainly composed of conjugated dienes, the distribution of units derived from the conjugated diene compounds or aromatic vinyl compounds in the molecular chain. May be random, tapered (in which the monomer component increases or decreases along the molecular chain), partially in a block form, or any combination thereof. When there are two or more polymer blocks (c) mainly composed of aromatic vinyl compounds or polymer blocks (d) mainly composed of conjugated dienes, each polymer block may have the same structure. Different structures may be used.
（水添）ブロック共重合体を構成する芳香族ビニル化合物としては、例えば、スチレン、α−メチルスチレン、ビニルトルエン、ｐ−第３ブチルスチレン等のうちから１種又は２種以上を選択でき、なかでもスチレンが好ましい。また共役ジエンとしては、例えば、ブタジエン、イソプレン、１，３−ペンタジエン、２，３−ジメチル−１，３−ブタジエン等のうちから１種又は２種以上が選ばれ、なかでもブタジエン、イソプレン及びこれらの組合せが好ましい。 As the aromatic vinyl compound constituting the (hydrogenated) block copolymer, for example, one or more types can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, and the like. Of these, styrene is preferable. Further, as the conjugated diene, for example, one or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc., among which butadiene, isoprene, and these The combination of is preferable.
水添ブロック共重合体における共役ジエンを主体とする重合体ブロック（ｄ）において、そのミクロ構造は、任意であり、例えば、ブロックＢがブタジエン単独で構成される場合、ポリブタジエンブロックにおいては、１，２−ミクロ構造が好ましくは２０〜５０重量％、特に好ましくは２５〜４５重量％である。その水添率は任意であるが好ましくは５０％以上、より好ましくは５５％以上、更に好ましくは６０％以上である。また、１，２−結合を選択的に水素添加したものであっても良い。ブロックＢがイソプレンとブタジエンの混合物で構成される場合、１，２−ミクロ構造が好ましくは５０％未満、より好ましくは２５％未満、より更に好ましくは１５％未満である。ブロック（ｄ）がイソプレン単独で構成される場合。ポリイソプレンブロックにおいてはイソプレンの好ましくは７０〜１００重量％が１，４−ミクロ構造を有し、かつイソプレンに由来する脂肪族二重結合の好ましくは少なくとも９０％が水素添加されたものが好ましい。 In the polymer block (d) mainly composed of conjugated diene in the hydrogenated block copolymer, the microstructure thereof is arbitrary. For example, when the block B is composed of butadiene alone, The 2-microstructure is preferably 20-50% by weight, particularly preferably 25-45% by weight. The hydrogenation rate is arbitrary, but is preferably 50% or more, more preferably 55% or more, and further preferably 60% or more. Alternatively, the 1,2-bond may be selectively hydrogenated. When block B is composed of a mixture of isoprene and butadiene, the 1,2-microstructure is preferably less than 50%, more preferably less than 25%, and even more preferably less than 15%. The block (d) is composed of isoprene alone. In the polyisoprene block, preferably 70 to 100% by weight of isoprene has a 1,4-microstructure, and preferably at least 90% of the aliphatic double bonds derived from isoprene are hydrogenated.
用途により、水素添加したブロック共重合体を使用する場合には、好ましくは上記水添物を用途に合わせて適宜使用することができる。 When a hydrogenated block copolymer is used depending on the application, the hydrogenated product can be suitably used according to the application.
芳香族ビニル化合物を主体とする重合体ブロックと、共役ジエンを主体とする重合体ブロックとからなるブロック共重合体またはその水素添加物（Ｂ）の具体例としては、スチレン−ブタジエンブロック共重合体、スチレン−ブタジエン−スチレンブロック共重合体（ＳＢＳ）、スチレン−イソプレンブロック共重合体、スチレン−イソプレン−スチレンブロック共重合体（ＳＩＳ）、スチレン−イソプレン・ブタジエン−スチレンブロック共重合体（ＳＩＢＳ）、スチレン−エチレン・ブテン−スチレンブロック共重合体（ＳＥＢＳ）、スチレン−エチレン・プロピレン−スチレンブロック共重合体（ＳＥＰＳ）、スチレン−エチレン・エチレン・プロピレン−スチレンブロック共重合体（ＳＥＥＰＳ）、スチレン−ブタジエン・ブチレン−スチレンブロック共重合体（部分水素添加スチレン−ブタジエン−スチレンブロック共重合体、ＳＢＢＳ）、スチレン−エチレン・ブチレン−スチレンブロック共重合体等を挙げることができる。そのなかでも成分（Ａ）との親和性の理由により、スチレン−ブタジエンブロック共重合体、スチレンーブタジエンースチレンブロック共重合体、スチレン−イソプレンブロック共重合体、スチレン−イソプレン−スチレンブロック共重合体、スチレン−エチレン・プロピレン−スチレンブロック共重合体、スチレン−エチレン・ブチレン−スチレンブロック共重合体、スチレン−エチレン・エチレン・プロピレン−スチレンブロック共重合体からなる群より選ばれる少なくとも１種が好ましい。 Specific examples of a block copolymer comprising a polymer block mainly comprising an aromatic vinyl compound and a polymer block mainly comprising a conjugated diene or a hydrogenated product thereof (B) include a styrene-butadiene block copolymer Styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer (SIS), styrene-isoprene-butadiene-styrene block copolymer (SIBS), Styrene-ethylene-butene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene・ Butylene Styrene block copolymer (partially hydrogenated styrene - butadiene - styrene block copolymer, SBBS), a styrene - ethylene butylene - or styrene block copolymers. Among them, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer due to the affinity with component (A). At least one selected from the group consisting of a styrene-ethylene / propylene / styrene block copolymer, a styrene / ethylene / butylene / styrene block copolymer, and a styrene / ethylene / ethylene / propylene / styrene block copolymer is preferable.
本発明の（Ｂ）成分は複数種選択して配合しても良い。 Multiple (B) components of the present invention may be selected and blended.
本発明のインナーライナーにはガスバリア性の向上の観点からさらに成分（Ａ）に対してエチレン−ビニルアルコール共重合体（Ｃ）を含有しても良い。エチレン−ビニルアルコール共重合体（Ｃ）は、エチレン含有量は２０〜７０モル％であることが好ましい。エチレン含有量が２０モル％を下回ると柔軟性に劣り耐屈曲性に劣る恐れがある上熱成形性に劣る恐れがある。また、７０モル％を上回るとガスバリア性が不足する恐れがある。成分（Ｃ）の配合量は成分（Ａ）１００重量部に対して好ましくは１〜４００重量部、さらに好ましくは１０〜４００重量部含有することが好ましい。成分（Ｃ）の配合量が４００重量部を超えると柔軟性が失われ長期での屈曲疲労特性に劣る可能性がある。 The inner liner of the present invention may further contain an ethylene-vinyl alcohol copolymer (C) with respect to the component (A) from the viewpoint of improving gas barrier properties. The ethylene-vinyl alcohol copolymer (C) preferably has an ethylene content of 20 to 70 mol%. If the ethylene content is less than 20 mol%, the flexibility may be inferior and the flex resistance may be inferior, and the thermoformability may be inferior. Moreover, when it exceeds 70 mol%, there exists a possibility that gas barrier property may be insufficient. The amount of component (C) is preferably 1 to 400 parts by weight, more preferably 10 to 400 parts by weight, based on 100 parts by weight of component (A). When the compounding amount of the component (C) exceeds 400 parts by weight, the flexibility is lost and the bending fatigue characteristics in the long term may be inferior.
本発明のインナーライナー用組成物にはカーカスゴムへの密着性の点から、さらに粘着付与剤を含有していても良い。粘着付与剤には天然のロジン、テルペン、合成のクマロンインデン樹脂、石油樹脂、アルキルフェノール樹脂などが挙げられる。粘着付与剤の配合量は成分（Ａ）と（Ｂ）との合計１００重量部に対して好ましくは１〜８０重量部である。 The composition for an inner liner of the present invention may further contain a tackifier from the viewpoint of adhesion to carcass rubber. Examples of the tackifier include natural rosin, terpene, synthetic coumarone indene resin, petroleum resin, and alkylphenol resin. The blending amount of the tackifier is preferably 1 to 80 parts by weight with respect to 100 parts by weight of the total of components (A) and (B).
本発明のインナーライナーを構成する層にはさらに目的に応じて充填剤、老化防止剤、軟化剤、加工助剤を添加しても良い。例えば充填剤には、カーボンブラック、湿式シリカ、乾式シリカ、炭酸カルシウム、カオリン、タルク、クレー等が挙げられ、老化防止剤には酸化防止剤、紫外線吸収剤、光安定剤が挙げられ、軟化剤にはパラフィン系オイル、ナフテン系オイル、アロマ系オイル、ナタネ油、ジオクチルフタレート、ジオクチルアジペートなどが挙げられ、加工助剤には高級脂肪酸、脂肪酸エステル、脂肪酸金属塩、脂肪酸アミド、パラフィンワックス、脂肪アルコール、フッ素・シリコーン系樹脂、高分子量ポリエチレンが挙げられる。 A filler, an antioxidant, a softening agent, and a processing aid may be further added to the layer constituting the inner liner of the present invention according to the purpose. For example, fillers include carbon black, wet silica, dry silica, calcium carbonate, kaolin, talc, clay, etc. Antiaging agents include antioxidants, ultraviolet absorbers, light stabilizers, softeners Include paraffinic oil, naphthenic oil, aroma oil, rapeseed oil, dioctyl phthalate, dioctyl adipate, etc., and processing aids include higher fatty acids, fatty acid esters, fatty acid metal salts, fatty acid amides, paraffin wax, fatty alcohols , Fluorine / silicone resin, and high molecular weight polyethylene.
本発明のライナー層を構成する樹脂組成物を得るには公知の混合方法を用いることができ、混合には公知の溶融混練の方法が適用できる。例えば配合される成分を加熱混練機、例えば、一軸押出機、二軸押出機、ロール、バンバリーミキサー、ブラベンダー、ニーダー、高剪断型ミキサー等を用いて溶融混練することで製造することができる。溶融混練の温度は、１００〜２４０℃が好ましい。１００℃よりも低い温度では（Ａ）〜（Ｃ）成分の溶融が不十分となり、混練が不均一となる傾向がある。２４０℃よりも高い温度では、（Ａ）〜（Ｃ）成分の熱分解、熱架橋が起こる傾向がある。得られた組成物を次に押出成形、カレンダー成形といった熱可塑性樹脂、熱可塑性エラストマーをフィルム化する通常の方法によってフィルム化すれば良い。特に共押出設備を用いて二層フィルムを得るのが層間の接着性、生産性の面で好ましい。 A known mixing method can be used to obtain the resin composition constituting the liner layer of the present invention, and a known melt-kneading method can be applied to the mixing. For example, it can manufacture by melt-kneading the component mix | blended using a heat kneading machine, for example, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, a Brabender, a kneader, a high shear mixer, etc. The temperature for melt kneading is preferably 100 to 240 ° C. If the temperature is lower than 100 ° C., the components (A) to (C) are not sufficiently melted and kneading tends to be non-uniform. At temperatures higher than 240 ° C., thermal decomposition and thermal crosslinking of components (A) to (C) tend to occur. What is necessary is just to film-form the obtained composition by the normal method of film-forming thermoplastic resin and thermoplastic elastomer, such as extrusion molding and calendar molding. In particular, it is preferable to obtain a two-layer film using a coextrusion facility in terms of adhesion between layers and productivity.
本発明のインナーライナーの厚みは合計２０μｍ〜１５００μｍの範囲に有ることが好ましい。厚みが２０μｍを下回るとインナーライナーの耐屈曲性が低下しタイヤ転動時の屈曲変形による破断や亀裂が生じる恐れがある。一方厚みが１５００μｍを超えるとタイヤ重量低減のメリットが少なくなる。 The thickness of the inner liner of the present invention is preferably in the range of 20 μm to 1500 μm in total. When the thickness is less than 20 μm, the bending resistance of the inner liner is lowered, and there is a risk of breakage or cracking due to bending deformation at the time of tire rolling. On the other hand, when the thickness exceeds 1500 μm, the merit of reducing the tire weight is reduced.
以下、実施例にて本発明をさらに詳しく説明するが、これらの実施例によって本発明は何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.
尚、実施例に先立ち各種測定法、評価法、実施例について説明する。 Prior to the examples, various measurement methods, evaluation methods, and examples will be described.
（引張弾性率）
ＪＩＳ Ｋ ６２５１に準拠し、試験片としてシートをダンベルで７号型に打抜いたものを用意し、これを測定に使用した。引張速度は１００ｍｍ／分とした。弾性率は歪みが０．５％〜５％の応力を基に算出した。
(Tensile modulus)
In accordance with JIS K 6251, a test piece obtained by punching a sheet into No. 7 with a dumbbell was prepared and used for measurement. The tensile speed was 100 mm / min. The elastic modulus was calculated based on the stress having a strain of 0.5% to 5%.
（引張強度）
ＪＩＳ Ｋ ６２５１に準拠し、試験片としてシートをダンベルで７号型に打抜いたものを用意し、これを測定に使用した。引張速度は１００ｍｍ／分とした。
(Tensile strength)
In accordance with JIS K 6251, a test piece obtained by punching a sheet into No. 7 with a dumbbell was prepared and used for measurement. The tensile speed was 100 mm / min.
（引張伸び）
ＪＩＳ Ｋ ６２５１に準拠し、試験片としてシートをダンベルで７号型に打抜いたものを用意し、これを測定に使用した。引張速度は１００ｍｍ／分とした。
(Tensile elongation)
In accordance with JIS K 6251, a test piece obtained by punching a sheet into No. 7 with a dumbbell was prepared and used for measurement. The tensile speed was 100 mm / min.
（ガスバリア性）
ガスバリア性は気体透過性を評価し、酸素の透過度を評価した。酸素の透過度は、得られたシートから１００ｍｍ×１００ｍｍの試験片を切り出し、ＪＩＳＫ７１２６に準拠して、２３℃、０％ＲＨ、１ａｔｍの差圧法にて測定した。
(Gas barrier properties)
For gas barrier properties, gas permeability was evaluated, and oxygen permeability was evaluated. The oxygen permeability was measured by cutting out a 100 mm × 100 mm test piece from the obtained sheet and measuring it at 23 ° C., 0% RH, 1 atm in accordance with JISK7126.
（接着性）
イソプレンゴムとの接着性を評価した。イソプレンゴムの２ｍｍ厚未加硫シートと貼り合わせ、１５０℃、５０ＭＰａで４０分加熱加圧加硫を行った後、幅２ｃｍ×６ｃｍに切り出した後、１８０°剥離試験を行い応力を測定した。試験速度は２００ｍｍ／ｍｉｎで行い、剥離開始後３ｃｍ〜５ｃｍの応力の平均値を採用した。
(Adhesiveness)
The adhesion with isoprene rubber was evaluated. After laminating with a 2 mm thick unvulcanized sheet of isoprene rubber and performing heat and pressure vulcanization at 150 ° C. and 50 MPa for 40 minutes, the sheet was cut into a width of 2 cm × 6 cm, and then subjected to a 180 ° peel test to measure stress. The test speed was 200 mm / min, and an average value of stress of 3 cm to 5 cm was adopted after the start of peeling.
（実施例等記載成分の内容）
成分（Ａ）：スチレン−イソブチレン−スチレンブロック共重合体（株式会社カネカ社製 商品名「ＳＩＢＳＴＡＲ１０２Ｔ」）重量平均分子量１１２，０００ スチレン含量１２ｗｔ％。
成分（Ｂ）−１：スチレン−イソプレン−スチレンブロック共重合体（クレイトンポリマージャパン社製 商品名「クレイトンＤ１１６１ＪＰ」）
成分（Ｂ）−２：スチレン−ブタジエン−スチレンブロック共重合体（クレイトンポリマージャパン社製 商品名「クレイトンＤＫＸ４０５ＣＰ」）
成分（Ｃ）：エチレン含量４４ｍｏｌ％エチレン−ビニルアルコール系共重合体（株式会社クラレ社製 商品名「ＥＶＡＬ Ｅ１０５Ａ」）
粘着付与樹脂：脂環族飽和炭化水素樹脂（荒川化学社製「アルコンＰ−７０」）。
(Contents of description components such as Examples)
Component (A): Styrene-isobutylene-styrene block copolymer (trade name “SIBSTAR102T” manufactured by Kaneka Corporation) Weight average molecular weight 112,000 Styrene content 12 wt%.
Component (B) -1: Styrene-isoprene-styrene block copolymer (trade name “Clayton D1161JP” manufactured by Kraton Polymer Japan Co., Ltd.)
Component (B) -2: Styrene-butadiene-styrene block copolymer (trade name “Clayton DKX405CP” manufactured by Kraton Polymer Japan Co., Ltd.)
Component (C): ethylene content 44 mol% ethylene-vinyl alcohol copolymer (trade name “EVAL E105A” manufactured by Kuraray Co., Ltd.)
Tackifying resin: alicyclic saturated hydrocarbon resin ("Arcon P-70" manufactured by Arakawa Chemical Co., Ltd.).
（製造例１）イソプレンゴムシートの作製
イソプレンゴム（株式会社ＪＳＲ社製 商品名「ＩＲ２２００」）を４００ｇ、カーボンブラック（旭カーボン旭♯５０）２００ｇを４０℃に設定した１Ｌニーダー（株式会社モリヤマ社製）に投入し５０ｒｐｍで５分間混練した後、硫黄６ｇ、N-ｔｅｒｔ-ブチル-２-ベンゾチアゾリルスルフェンアミド８ｇ、酸化亜鉛８ｇ、ステアリン酸８ｇを投入し２分間混練した後排出し、８０℃で加熱プレス（神藤金属社製）にて２ｍｍ厚のシート状に成形した。
(Production Example 1) Production of isoprene rubber sheet 1 L kneader (Molyama Co., Ltd.) in which 400 g of isoprene rubber (trade name “IR2200” manufactured by JSR Corporation) and 200 g of carbon black (Asahi Carbon Asahi # 50) were set at 40 ° C. And then kneaded for 5 minutes at 50 rpm, charged with 6 g of sulfur, 8 g of N-tert-butyl-2-benzothiazolylsulfenamide, 8 g of zinc oxide and 8 g of stearic acid, kneaded for 2 minutes and discharged. The sheet was formed into a sheet having a thickness of 2 mm at 80 ° C. with a heating press (manufactured by Shinto Metal Co., Ltd.).
（実施例１）
成分（Ａ）、成分（Ｂ）−１をそれぞれＴダイ（ダイリップ径２０００μｍ、幅２００ｍｍ）が取り付けられた多層単軸押出機（東洋精機社製、多層押出機、スクリュー径１５ｍｍφ、フィードブロック方式）の異なるホッパーに投入しダイヘッド温度２００℃で成分（Ａ）を回転数４０ｒｐｍ、成分（Ｂ）を１０ｒｐｍで共押出を行い５００μｍ厚の多層フィルムを得た。得たフィルムの引張試験、ガスバリア性、接着性の測定を行い表１のような結果を得た。
Example 1
Ingredient (A) and Ingredient (B) -1 are each a multi-layer single-screw extruder equipped with a T-die (die lip diameter 2000 μm, width 200 mm) (manufactured by Toyo Seiki Co., Ltd., multilayer extruder, screw diameter 15 mmφ, feed block method) And a co-extruded component (A) at a rotational speed of 40 rpm and a component (B) at 10 rpm at a die head temperature of 200 ° C. to obtain a multilayer film having a thickness of 500 μm. The obtained film was subjected to tensile tests, gas barrier properties, and adhesion measurements, and the results shown in Table 1 were obtained.
（実施例２）
成分（Ｂ）−１を成分（Ｂ）−２に変更した以外は実施例１と同様に多層フィルムを得て、得たフィルムの引張試験、ガスバリア性、接着性の測定を行った。
(Example 2)
A multilayer film was obtained in the same manner as in Example 1 except that the component (B) -1 was changed to the component (B) -2, and the tensile test, gas barrier property, and adhesiveness of the obtained film were measured.
（実施例３）
成分（Ａ）と成分（Ｃ）を表１の割合で配合し、２軸押出機を用いて１７０℃で混練しペレットを得た。得られたペレットと成分（Ｂ）−１をそれぞれＴダイ（ダイリップ径２０００μｍ、幅２００ｍｍ）が取り付けられた多層単軸押出機（東洋精機社製、多層押出機、スクリュー径１５ｍｍφ、フィードブロック方式）の異なるホッパーに投入しダイヘッド温度２００℃で成分（Ａ）を含む樹脂を回転数４０ｒｐｍ、成分（Ｂ）−１を１０ｒｐｍで共押出を行い５００μｍ厚の多層フィルムを得た。得たフィルムの引張試験、ガスバリア性、接着性の測定を行い表１のような結果を得た。
(Example 3)
Component (A) and component (C) were blended in the proportions shown in Table 1 and kneaded at 170 ° C. using a twin-screw extruder to obtain pellets. Multi-layer single-screw extruder (multilayer extruder manufactured by Toyo Seiki Co., Ltd., screw diameter 15 mmφ, feed block system) to which the obtained pellets and component (B) -1 were each attached with a T-die (die lip diameter 2000 μm, width 200 mm) The resin containing the component (A) was coextruded at a rotational speed of 40 rpm and the component (B) -1 was coextruded at 10 rpm at a die head temperature of 200 ° C. to obtain a multilayer film having a thickness of 500 μm. The obtained film was subjected to tensile tests, gas barrier properties, and adhesion measurements, and the results shown in Table 1 were obtained.
（実施例４）
成分（Ａ）、成分（Ｃ）と粘着付与樹脂を表１の割合で配合し、２軸押出機を用いて１７０℃で混練しペレットを得た以外は実施例７と同様にフィルムを得て、得たフィルムの引張試験、ガスバリア性、接着性の測定を行った。
Example 4
A film was obtained in the same manner as in Example 7 except that the component (A), the component (C) and the tackifier resin were blended in the ratios shown in Table 1 and kneaded at 170 ° C. using a twin-screw extruder to obtain pellets. The film was subjected to tensile tests, gas barrier properties, and adhesion measurements.
（実施例５）
成分（Ａ）と成分（Ｃ）を表１の割合で配合し、２軸押出機を用いて１７０℃で混練しペレットを得た。また、成分（Ｂ）−１と粘着付与樹脂を表１の割合で配合し、２軸押出機を用いて１７０℃で混練しペレットを得た。これらのペレットはそれぞれＴダイ（ダイリップ径２０００μｍ、幅２００ｍｍ）を取り付けた多層単軸押出機（東洋精機社製、多層押出機、スクリュー径１５ｍｍφ、フィードブロック方式）の異なるホッパーに投入されダイヘッド温度２００℃で成分（Ａ）を含む樹脂を回転数４０ｒｐｍ、成分（Ｂ）を含む樹脂を１０ｒｐｍで共押出を行い５００μｍ厚の多層フィルムを得た。得たフィルムの引張試験、ガスバリア性、接着性の測定を行い表１のような結果を得た。
(Example 5)
Component (A) and component (C) were blended in the proportions shown in Table 1 and kneaded at 170 ° C. using a twin-screw extruder to obtain pellets. Moreover, component (B) -1 and tackifying resin were mix | blended in the ratio of Table 1, and it knead | mixed at 170 degreeC using the twin-screw extruder, and obtained the pellet. Each of these pellets was put into different hoppers of a multi-layer single-screw extruder (manufactured by Toyo Seiki Co., Ltd., multi-layer extruder, screw diameter 15 mmφ, feed block method) equipped with a T die (die lip diameter 2000 μm, width 200 mm). The resin containing the component (A) was coextruded at 40 ° C. and the resin containing the component (B) was coextruded at 10 rpm to obtain a 500 μm thick multilayer film. The obtained film was subjected to tensile tests, gas barrier properties, and adhesion measurements, and the results shown in Table 1 were obtained.
（比較例１）
成分（Ａ）をＴダイ（ダイリップ径２０００μｍ、幅２００ｍｍ）を取り付けた単軸押出機（東洋精機社製、スクリュー径１５ｍｍφ）のホッパーに投入しダイヘッド温度２００℃で４００μｍ厚のフィルムを得た。得られたフィルムの引張試験、ガスバリア性、接着性の測定を行い表１の結果を得た。
(Comparative Example 1)
The component (A) was put into a hopper of a single screw extruder (manufactured by Toyo Seiki Co., Ltd., screw diameter 15 mmφ) equipped with a T die (die lip diameter 2000 μm, width 200 mm) to obtain a film having a die head temperature of 200 ° C. and a thickness of 400 μm. The obtained film was subjected to tensile tests, gas barrier properties, and adhesion measurements, and the results shown in Table 1 were obtained.
（比較例２）
成分（Ａ）と成分（Ｃ）を表１の割合で配合し、２軸押出機を用いて１７０℃で混練しペレットを得た。得られたペレットから比較例１と同様にフィルムを得て、得られたフィルムの引張試験、ガスバリア性、接着性の測定を行い表１の結果を得た。
(Comparative Example 2)
Component (A) and component (C) were blended in the proportions shown in Table 1 and kneaded at 170 ° C. using a twin-screw extruder to obtain pellets. A film was obtained from the obtained pellets in the same manner as in Comparative Example 1, and the tensile test, gas barrier property and adhesiveness of the obtained film were measured, and the results shown in Table 1 were obtained.
（比較例３）
成分（Ａ）、成分（Ｃ）と粘着付与樹脂を表１の割合で配合し、２軸押出機を用いて１７０℃で混練しペレットを得た以外は比較例２と同様にフィルムを得て、得たフィルムの引張試験、ガスバリア性、接着性の測定を行った。
(Comparative Example 3)
A film was obtained in the same manner as in Comparative Example 2 except that the component (A), the component (C) and the tackifying resin were blended in the ratios shown in Table 1 and kneaded at 170 ° C. using a twin screw extruder to obtain pellets. The film was subjected to tensile tests, gas barrier properties, and adhesion measurements.
（比較例４）
ブチルゴム（株式会社ＪＳＲ社製 商品名「ブチル２６８」）を４００ｇ、カーボンブラック（旭カーボン旭♯５０）１２０ｇを４０℃に設定した１Ｌニーダー（株式会社モリヤマ社製）に投入し５０ｒｐｍで５分間混練した後、硫黄８ｇ、N-ｔｅｒｔ-ブチル-２-ベンゾチアゾリルスルフェンアミド８ｇ、酸化亜鉛１２ｇ、ステアリン酸８ｇ、プロセスオイル（株式会社出光興産社製 商品名「ＰＷ３８０」）８０ｇを投入し２分間混練した後排出し、８０℃で加熱プレス（神藤金属にて１０００μｍ厚のシート状に成形した。一部はシートを１５０℃２０分間加熱プレスした後、引張試験、ガスバリア性の測定を行った。残りのシートを用いて比較例１と同様にして接着性の評価を行った。
(Comparative Example 4)
400 g of butyl rubber (trade name “butyl 268” manufactured by JSR Corporation) and 120 g of carbon black (Asahi Carbon Asahi # 50) are charged into a 1 L kneader (manufactured by Moriyama Co., Ltd.) set at 40 ° C. and kneaded at 50 rpm for 5 minutes. Then, 8 g of sulfur, 8 g of N-tert-butyl-2-benzothiazolylsulfenamide, 12 g of zinc oxide, 8 g of stearic acid, and 80 g of process oil (trade name “PW380” manufactured by Idemitsu Kosan Co., Ltd.) After kneading for a minute, the product was discharged and heated at 80 ° C. (formed into a sheet having a thickness of 1000 μm by Shinto Metal. Part of the sheet was heated and pressed at 150 ° C. for 20 minutes, and then a tensile test and gas barrier properties were measured. Using the remaining sheets, the adhesion was evaluated in the same manner as in Comparative Example 1.
成分（Ｂ）からなる層を備える本発明の実施例１〜５は、成分（Ｂ）からなる層を備えない比較例１〜３よりも高い接着強度を示した。また、実施例１〜５は従来のインナーライナーに用いられてきた加硫工程を必須とするブチルゴム配合である比較例４に比べて高い接着強度を示した。実施例１〜５は、従来のゴム専用の加工機を必要とせず、容易に通常の熱可塑性樹脂を扱える押出機で実施することが可能である。 Examples 1 to 5 of the present invention including a layer composed of the component (B) showed higher adhesive strength than Comparative Examples 1 to 3 not including the layer composed of the component (B). Moreover, Examples 1-5 showed high adhesive strength compared with the comparative example 4 which is a butyl rubber compounding which requires the vulcanization process used for the conventional inner liner. Examples 1 to 5 do not require a conventional rubber-dedicated processing machine, and can be easily implemented with an extruder that can handle a normal thermoplastic resin.
これらの事から本発明のインナーライナーはカーカスゴムへの接着とインナーライナーの生産性に優れていることが分かる。 From these facts, it can be seen that the inner liner of the present invention is excellent in adhesion to carcass rubber and productivity of the inner liner.
Claims (6)
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| FR2939076B1 (en) * | 2008-12-03 | 2011-10-21 | Michelin Soc Tech | AIR-LAYERED MULTILAYER LAMINATE FOR PNEUMATIC OBJECT |
| JP5330350B2 (en) | 2010-07-07 | 2013-10-30 | 住友ゴム工業株式会社 | Polymer sheet for inner liner and pneumatic tire using the same |
| WO2012026177A1 (en) * | 2010-08-25 | 2012-03-01 | 住友ゴム工業株式会社 | Pneumatic tire and process for production thereof, and tire curing bladder |
| JP5106600B2 (en) * | 2010-08-25 | 2012-12-26 | 住友ゴム工業株式会社 | Tire vulcanizing bladder and pneumatic tire manufactured using the same |
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| JP5913796B2 (en) * | 2010-08-25 | 2016-04-27 | 住友ゴム工業株式会社 | Pneumatic tire using polymer laminate for inner liner |
| JP5632684B2 (en) * | 2010-09-03 | 2014-11-26 | 住友ゴム工業株式会社 | Pneumatic tire and manufacturing method thereof |
| JP5632686B2 (en) * | 2010-09-07 | 2014-11-26 | 住友ゴム工業株式会社 | Pneumatic tire |
| JP5592217B2 (en) * | 2010-09-30 | 2014-09-17 | 住友ゴム工業株式会社 | Truck and bus tires |
| JP5620783B2 (en) * | 2010-10-19 | 2014-11-05 | 株式会社カネカ | Composition for inner liner for pneumatic tire and inner liner for pneumatic tire |
| JP5670699B2 (en) * | 2010-10-26 | 2015-02-18 | 住友ゴム工業株式会社 | Pneumatic tire |
| JP5138758B2 (en) * | 2010-11-02 | 2013-02-06 | 住友ゴム工業株式会社 | Pneumatic tire |
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| JP4944239B1 (en) * | 2010-11-17 | 2012-05-30 | 住友ゴム工業株式会社 | Pneumatic tire manufacturing method |
| JP5225431B2 (en) | 2010-12-06 | 2013-07-03 | 住友ゴム工業株式会社 | Strip, method for producing the same, and method for producing a pneumatic tire |
| JP5758618B2 (en) * | 2010-12-14 | 2015-08-05 | 住友ゴム工業株式会社 | Pneumatic tire and manufacturing method thereof |
| JP5048881B1 (en) * | 2011-05-13 | 2012-10-17 | 住友ゴム工業株式会社 | Pneumatic tire |
| BR112013029031A2 (en) * | 2011-05-13 | 2017-01-10 | Sumitomo Rubber Ind | pneumatic |
| JP5469155B2 (en) * | 2011-11-22 | 2014-04-09 | 住友ゴム工業株式会社 | Pneumatic tire manufacturing method |
| EP3351372B1 (en) | 2011-10-04 | 2019-06-05 | Sumitomo Rubber Industries, Ltd. | Method for manufacturing pneumatic tires |
| KR20140088154A (en) * | 2011-11-09 | 2014-07-09 | 스미토모 고무 고교 가부시키가이샤 | Pneumatic tire |
| JP5592420B2 (en) * | 2012-02-15 | 2014-09-17 | 住友ゴム工業株式会社 | Truck or bus tire |
| JP5497829B2 (en) * | 2012-04-19 | 2014-05-21 | 住友ゴム工業株式会社 | Pneumatic tire |
| DE102013214168A1 (en) * | 2012-08-15 | 2014-02-20 | Sumitomo Rubber Industries, Ltd. | tire |
| US20170361653A1 (en) * | 2014-12-31 | 2017-12-21 | Xavier Saintigny | Tire component |
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| EP1987962B1 (en) * | 2006-02-23 | 2011-07-13 | The Yokohama Rubber Co., Ltd. | Multilayer body and pneumatic tire using same |
| US20090288749A1 (en) * | 2006-04-04 | 2009-11-26 | The Yokohama Rubber Co., Ltd. | Pneumatic tire having light shielding layer on surface |
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