JPH08259741A - Polymer composition for tire and pneumatic tire made thereof - Google Patents
Polymer composition for tire and pneumatic tire made thereofInfo
- Publication number
- JPH08259741A JPH08259741A JP7150353A JP15035395A JPH08259741A JP H08259741 A JPH08259741 A JP H08259741A JP 7150353 A JP7150353 A JP 7150353A JP 15035395 A JP15035395 A JP 15035395A JP H08259741 A JPH08259741 A JP H08259741A
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- Prior art keywords
- tire
- weight
- component
- polymer composition
- rubber
- Prior art date
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐空気透過性と柔軟性
とのバランスに優れたタイヤ用ポリマー組成物に関し、
更に詳しくは空気入りタイヤのタイヤ内の空気圧保持性
を損なうことなく、インナーライナー層などの空気透過
防止層を薄くしてタイヤの軽量化を図ることが出来るタ
イヤ用ポリマー組成物及びそれを空気透過防止層に用い
た空気入りタイヤに関する。FIELD OF THE INVENTION The present invention relates to a tire polymer composition having an excellent balance between air permeation resistance and flexibility.
More specifically, a tire polymer composition capable of reducing the weight of a tire by thinning an air permeation preventive layer such as an inner liner layer without impairing the air pressure retention in the tire of a pneumatic tire and the air permeation thereof. The present invention relates to a pneumatic tire used for a prevention layer.
【０００２】[0002]
【従来の技術】燃料消費率の低減は自動車における大き
な技術的課題の一つであり、この対策の一環として空気
入りタイヤの軽量化に対する要求も益々強いものになっ
てきている。2. Description of the Related Art Reducing the fuel consumption rate is one of the major technical problems in automobiles, and as part of this measure, there is an increasing demand for weight reduction of pneumatic tires.
【０００３】ところで、空気入りタイヤの内面には、タ
イヤ空気圧を一定に保持するためにブチルゴム、ハロゲ
ン化ブチルゴムなどのような低気体透過性のゴムからな
るインナーライナー層が設けられている。しかしなが
ら、ハロゲン化ブチルゴムはヒステリシス損失が大きい
ため、タイヤの加硫後に、カーカスコード間の間隙にお
いて、カーカス層の内面ゴム及びインナーライナー層に
波打ちが生じた場合、カーカス層の変形とともにインナ
ーライナーゴム層が変形するので、転動抵抗が増加する
という問題がある。このため、一般に、インナーライナ
ー層（ハロゲン化ブチルゴム）とカーカス層の内面ゴム
との間にヒステリシス損失が小さいタイゴムと呼ばれる
ゴムシートを介して両者を接合している。従って、ハロ
ゲン化ブチルゴムのインナーライナー層の厚さに加え
て、タイゴムの厚さが加算され、層全体として１mm（１
０００μｍ）を超える厚さになり、結果的に製品タイヤ
の重量を増大させる原因の一つになっていた。By the way, an inner liner layer made of a rubber having a low gas permeability such as butyl rubber or halogenated butyl rubber is provided on the inner surface of the pneumatic tire in order to keep the tire air pressure constant. However, since halogenated butyl rubber has a large hysteresis loss, when the inner surface rubber and inner liner layer of the carcass layer are corrugated in the gap between the carcass cords after vulcanization of the tire, the inner liner rubber layer is deformed along with the deformation of the carcass layer. Since there is deformation, there is a problem that rolling resistance increases. Therefore, in general, the inner liner layer (halogenated butyl rubber) and the inner surface rubber of the carcass layer are joined together via a rubber sheet called tie rubber having a small hysteresis loss. Therefore, the thickness of the tie rubber is added to the thickness of the inner liner layer of halogenated butyl rubber, and the total layer thickness is 1 mm (1
The thickness was more than 000 μm), which was one of the causes of increasing the weight of the product tire as a result.
【０００４】空気入りタイヤのインナーライナー層とし
てブチルゴムなどの低気体透過性ゴムに代えて種々の材
料を用いる技術が提案されている。例えば、特公昭４７
−３１７６１号公報には加硫タイヤの内面に、空気透過
係数［cm3(標準状態）／cm・sec ・mmHg］が３０℃で１
０×１０-13 以下、７０℃で５０×１０-13 以下の、ポ
リ塩化ビニリデン、飽和ポリエステル樹脂、ポリアミド
樹脂などの合成樹脂の溶液又は分散液を０．１mm以下で
塗布することが開示されている。Techniques have been proposed in which various materials are used as an inner liner layer of a pneumatic tire in place of low gas permeability rubber such as butyl rubber. For example,
-31761 discloses that the inner surface of a vulcanized tire has an air permeability coefficient [cm 3 (standard state) / cm · sec · mmHg] of 1 at 30 ° C.
It is disclosed that a solution or dispersion of synthetic resin such as polyvinylidene chloride, saturated polyester resin, polyamide resin or the like having a concentration of 0 × 10 −13 or less and 50 × 10 −13 or less at 70 ° C. is applied in an amount of 0.1 mm or less. There is.
【０００５】しかしながら、この公報に開示の技術は、
加硫タイヤのカーカス内周面に、もしくはインナーライ
ナー内周面に、特定の空気透過係数を有する合成樹脂の
被覆層を設けて合成樹脂被覆層の厚さを０．１mm以下に
することが記載されているが、この公報に記載された空
気入りタイヤはゴムと合成樹脂との接着性に問題があ
り、またインナーライナー層が耐湿性（又は耐水性）に
劣るという欠点を有する。However, the technique disclosed in this publication is
It is stated that a synthetic resin coating layer having a specific air permeability coefficient is provided on the inner peripheral surface of the carcass of the vulcanized tire or on the inner peripheral surface of the inner liner so that the thickness of the synthetic resin coating layer is 0.1 mm or less. However, the pneumatic tire described in this publication has a problem in adhesiveness between rubber and synthetic resin, and has a drawback that the inner liner layer is inferior in moisture resistance (or water resistance).
【０００６】特開平５−３３０３０７号公報にはタイヤ
内面をハロゲン化処理（従来から知られている塩素化処
理用液、臭素溶液、ヨウ素溶液を使用）し、その上にメ
トキシメチル化ナイロン、共重合ナイロン、ポリウレタ
ンとポリ塩化ビニリデンのブレンド、ポリウレタンとポ
リフッ化ビニリデンのブレンドのポリマー皮膜（膜厚１
０〜２００μｍ）を形成することが開示されている。JP-A-5-330307 discloses that the inner surface of a tire is subjected to a halogenation treatment (using a conventionally known chlorination treatment liquid, a bromine solution and an iodine solution), and a methoxymethylated nylon, Polymer film of polymerized nylon, blend of polyurethane and polyvinylidene chloride, blend of polyurethane and polyvinylidene fluoride (film thickness 1
0-200 μm) is disclosed.
【０００７】更に特開平５−３１８６１８号公報には、
メトキシメチル化ナイロンの薄膜をインナーライナーと
する空気入りタイヤが開示されており、この技術によれ
ば、グリーンタイヤ内面にメトキシメチル化ナイロンの
溶液又はエマルジョンを散布又は塗布し、次いでタイヤ
を加硫するか、或いは加硫後タイヤ内面にメトキシメチ
ル化ナイロンの溶液又はエマルジョンを散布又は塗布す
ることによって空気入りタイヤを製造している。しかし
ながら、これらの公報に開示の技術においても薄膜の耐
水性に劣る欠点に加えて、膜厚の均一性を保持すること
が困難な欠点を有している。Further, in Japanese Patent Laid-Open No. 5-318618,
A pneumatic tire using a methoxymethylated nylon thin film as an inner liner is disclosed. According to this technique, a methoxymethylated nylon solution or emulsion is sprayed or applied on the inner surface of a green tire, and then the tire is vulcanized. Alternatively, a pneumatic tire is manufactured by spraying or applying a solution or emulsion of methoxymethylated nylon onto the inner surface of the tire after vulcanization. However, the techniques disclosed in these publications also have a drawback that it is difficult to maintain the uniformity of the film thickness in addition to the drawback that the thin film has poor water resistance.
【０００８】更に、特開平６−４０２０７号公報には、
ポリ塩化ビニリデンフィルムまたはエチレンビニルアル
コール共重合体フィルムから成る低空気透過層と、ポリ
オレフィン系フィルム、脂肪族ポリアミドフィルム、ま
たは、ポリウレタンフィルムから成る接着層を有した多
層フィルムをタイヤの空気透過防止層として使用してい
る例がある。しかしながら、この系では低空気透過層が
柔軟性に欠け、タイヤ走行時の材料の伸縮にフィルムが
追従できず、亀裂を発生することがあった。Further, in Japanese Patent Laid-Open No. 6-40207,
A low air permeability layer composed of a polyvinylidene chloride film or an ethylene vinyl alcohol copolymer film, and a polyolefin film, an aliphatic polyamide film, or a multilayer film having an adhesive layer composed of a polyurethane film as an air permeation preventive layer of a tire. There is an example in use. However, in this system, the low air permeable layer lacked flexibility, the film could not follow the expansion and contraction of the material during tire running, and cracks sometimes occurred.
【０００９】更に特開平５−５０８４３５号公報にはタ
イヤインナーライナー用組成物としてＣ4 〜Ｃ7 イソモ
ノオレフィンとｐ−アルキルスチレンのハロゲン含有コ
ポリマーにカーボンブラック、可塑剤油及び加硫剤を含
む組成物をタイヤインナーライナーに使用することが提
案されているが、かかるインナーライナーは空気透過係
数が不十分で更なるタイヤの軽量化には適当でない。Further, in JP-A-5-508435, a halogen-containing copolymer of C 4 -C 7 isomonoolefin and p-alkylstyrene is contained in a composition for a tire inner liner, carbon black, a plasticizer oil and a vulcanizing agent. Although it has been proposed to use the composition for a tire inner liner, such an inner liner has an insufficient air permeability coefficient and is not suitable for further weight reduction of a tire.
【００１０】[0010]
【発明が解決しようとする課題】前述の通り、ブチルゴ
ムに代わる、空気入りタイヤのインナーライナー層用の
種々の材料が提案されているが、未だ実用化されるには
至っていない。特に空気入りタイヤのインナーライナー
層として必要な耐空気透過性と柔軟性とのバランスに優
れた材料は未だ開発されるに至っていない。従って、本
発明の目的は、空気入りタイヤの空気圧保持性を損なう
ことなく、タイヤの軽量化を可能にし、かつ、ゴム層と
の接着性、空気入りタイヤの空気透過防止層用として最
適のタイヤ用ポリマー組成物及びそれを用いて空気透過
防止層を構成した空気入りタイヤを提供することにあ
る。As mentioned above, various materials for the inner liner layer of pneumatic tires have been proposed in place of butyl rubber, but they have not yet been put to practical use. In particular, a material having a good balance between air permeation resistance and flexibility, which is necessary for the inner liner layer of a pneumatic tire, has not yet been developed. Therefore, an object of the present invention is to enable the weight reduction of the tire without impairing the air pressure retaining property of the pneumatic tire, and the adhesiveness with the rubber layer, the optimum tire for the air permeation preventive layer of the pneumatic tire. To provide a polymer composition for use and a pneumatic tire having an air permeation preventive layer using the same.
【００１１】[0011]
【課題を解決するための手段】本発明に従えば、（Ａ）
空気透過係数が２５×１０-12 cc・cm／cm2 ・sec ・cm
Hg以下でヤング率が５００MPa 超の少なくとも一種の熱
可塑性樹脂を全ポリマー成分重量当り１０重量％以上並
びに（Ｂ）空気透過係数が２５×１０-12 cc・cm／cm2
・sec ・cmHg超でヤング率が５００MPa 以下の少なくと
も一種のエラストマー成分を全ポリマー成分重量当り１
０重量％以上で、成分（Ａ）及び成分（Ｂ）の合計量
（Ａ）＋（Ｂ）が全ポリマー成分重量当り３０重量％以
上となる量で含み、かつ空気透過係数が２５×１０-12
cc・cm／cm2 ・sec ・cmHg以下でヤング率が１〜５００
MPa のタイヤ用ポリマー組成物が提供される。According to the present invention, (A)
Air permeability coefficient is 25 × 10 -12 cc ・ cm / cm 2・ sec ・ cm
At least one thermoplastic resin having a Young's modulus of more than 500 MPa and Hg or less and 10% by weight or more based on the weight of all polymer components, and (B) an air permeability coefficient of 25 × 10 −12 cc · cm / cm 2
・ Sec ・ At least one elastomer component with Young's modulus of 500MPa or less and cmHg or more is 1 per weight of all polymer components.
The amount of the component (A) and the component (B) (A) + (B) is 30% by weight or more based on the total weight of the polymer components, and the air permeability coefficient is 25 × 10 −. 12
cc ・ cm / cm 2・ sec ・ cmHg or less, Young's modulus is 1 to 500
A MPa polymer composition for tires is provided.
【００１２】本発明に従えば、また、上記タイヤ用ポリ
マー組成物を空気透過防止層に用いた空気入りタイヤが
提供される。According to the present invention, there is also provided a pneumatic tire using the polymer composition for a tire as an air permeation preventive layer.
【００１３】本発明に従ったポリマー組成物に（Ａ）成
分として配合される熱可塑性樹脂は、空気透過係数が２
５×１０-12 cc・cm／cm2 ・sec ・cmHg以下、好ましく
は０．１×１０-12 〜１０×１０-12 cc・cm／cm2 ・se
c ・cmHgでヤング率が５００MPa 超、好ましくは５００
〜３０００MPa の任意の熱可塑性樹脂を用いることがで
き、その配合量は樹脂及びゴムを含むポリマー成分の合
計重量当り１０重量％以上、好ましくは２０〜８５重量
％である。The thermoplastic resin blended as the component (A) in the polymer composition according to the present invention has an air permeability coefficient of 2.
5 × 10 −12 cc · cm / cm 2 · sec · cmHg or less, preferably 0.1 × 10 −12 to 10 × 10 −12 cc · cm / cm 2 · se
c · cmHg, Young's modulus is more than 500MPa, preferably 500
Any thermoplastic resin of up to 3000 MPa can be used, and the compounding amount thereof is 10% by weight or more, preferably 20 to 85% by weight, based on the total weight of the polymer components including the resin and rubber.
【００１４】そのような熱可塑性樹脂としては、例えば
以下のような熱可塑性樹脂及びこれらの又はこれらを含
む任意の樹脂混合物を挙げることができる。Examples of such a thermoplastic resin include the following thermoplastic resins and any of these or any resin mixture containing them.
【００１５】ポリアミド系樹脂（例えばナイロン６（Ｎ
６）、ナイロン６６（Ｎ６６）、ナイロン４６（Ｎ４
６）、ナイロン１１（Ｎ１１）、ナイロン１２（Ｎ１
２）、ナイロン６１０（Ｎ６１０）、ナイロン６１２
（Ｎ６１２）、ナイロン６／６６共重合体（Ｎ６／６
６）、ナイロン６／６６／６１０共重合体（Ｎ６／６６
／６１０）、ナイロンＭＸＤ６（ＭＸＤ６）、ナイロン
６Ｔ、ナイロン６／６Ｔ共重合体、ナイロン６６／ＰＰ
共重合体、ナイロン６６／ＰＰＳ共重合体）、ポリエス
テル系樹脂（例えばポリブチレンテレフタレート（ＰＢ
Ｔ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリエ
チレンイソフタレート（ＰＥＩ）、ＰＥＴ／ＰＥＩ共重
合体、ポリアリレート（ＰＡＲ）、ポリブチレンナフタ
レート（ＰＢＮ）、液晶ポリエステル、ポリオキシアル
キレンジイミド酸／ポリブチレートテレフタレート共重
合体などの芳香族ポリエステル）、ポリニトリル系樹脂
（例えばポリアクリロニトリル（ＰＡＮ）、ポリメタク
リロニトリル、アクリロニトリル／スチレン共重合体
（ＡＳ）、メタクリロニトリル／スチレン共重合体、メ
タクリロニトリル／スチレン／ブタジエン共重合体）、
ポリメタクリレート系樹脂（例えばポリメタクリル酸メ
チル（ＰＭＭＡ）、ポリメタクリル酸エチル）、ポリビ
ニル系樹脂（例えば酢酸ビニル（ＥＶＡ）、ポリビニル
アルコール（ＰＶＡ）、ビニルアルコール／エチレン共
重合体（ＥＶＯＨ）、ポリ塩化ビニリデン（ＰＶＤ
Ｃ）、ポリ塩化ビニル（ＰＶＣ）、塩化ビニル／塩化ビ
ニリデン共重合体、塩化ビニリデン／メチルアクリレー
ト共重合体）、セルロース系樹脂（例えば酢酸セルロー
ス、酢酸酪酸セルロース）、フッ素系樹脂（例えばポリ
フッ化ビニリデン（ＰＶＤＦ）、ポリフッ化ビニル（Ｐ
ＶＦ）、ポリクロルフルオロエチレン（ＰＣＴＦＥ）、
テトラフロロエチレン／エチレン共重合体（ＥＴＦ
Ｅ））、イミド系樹脂（例えば芳香族ポリイミド（Ｐ
Ｉ））などを挙げることができる。Polyamide resin (for example, nylon 6 (N
6), nylon 66 (N66), nylon 46 (N4
6), nylon 11 (N11), nylon 12 (N1
2), nylon 610 (N610), nylon 612
(N612), nylon 6/66 copolymer (N6 / 6
6), nylon 6/66/610 copolymer (N6 / 66
/ 610), nylon MXD6 (MXD6), nylon 6T, nylon 6 / 6T copolymer, nylon 66 / PP
Copolymer, nylon 66 / PPS copolymer, polyester resin (eg polybutylene terephthalate (PB)
T), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, polyoxyalkylene diimidic acid / polybutyrate terephthalate Aromatic polyesters such as copolymers), polynitrile resins (for example, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, methacrylonitrile / styrene) / Butadiene copolymer),
Polymethacrylate resin (for example, polymethyl methacrylate (PMMA), polyethyl methacrylate), polyvinyl resin (for example, vinyl acetate (EVA), polyvinyl alcohol (PVA), vinyl alcohol / ethylene copolymer (EVOH), polychlorination Vinylidene (PVD
C), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer), cellulose resin (eg cellulose acetate, cellulose acetate butyrate), fluorine resin (eg polyvinylidene fluoride) (PVDF), polyvinyl fluoride (P
VF), polychlorofluoroethylene (PCTFE),
Tetrafluoroethylene / ethylene copolymer (ETF
E)), imide resin (for example, aromatic polyimide (P
I)) etc. can be mentioned.
【００１６】前述の如く、これらの熱可塑性樹脂は特定
の空気透過係数、ヤング率及び配合量としなければなら
ない。ヤング率５００MPa 以下の柔軟性を有し、かつ空
気透過係数が２５×１０-12 cc・cm／cm2 ・sec ・cmHg
以下である素材は、工業的にまだ開発されておらず、ま
た、空気透過係数が２５×１０-12 cc・cm／cm2 ・sec
・cmHgを超えると、タイヤ用ポリマー組成物としての耐
空気透過性が低下し、タイヤの空気透過防止層としての
機能を果たさなくなる。更に、これらの熱可塑性樹脂の
配合量が１０重量％未満の場合にも同様に耐空気透過性
が低下して、タイヤの空気透過防止層としては使用でき
ないこととなるので好ましくない。As described above, these thermoplastic resins must have a specific air permeability coefficient, Young's modulus and compounding amount. It has a Young's modulus of less than 500MPa and an air permeability coefficient of 25 × 10 -12 cc · cm / cm 2 · sec · cmHg.
The following materials have not yet been industrially developed and have an air permeability coefficient of 25 × 10 -12 cc · cm / cm 2 · sec.
-If it exceeds cmHg, the air permeation resistance of the polymer composition for tires decreases, and the tire does not function as an air permeation preventive layer. Further, when the blending amount of these thermoplastic resins is less than 10% by weight, the air permeation resistance is similarly reduced, and it cannot be used as an air permeation preventive layer of a tire, which is not preferable.
【００１７】本発明に従った樹脂組成物に（Ｂ）成分と
して配合されるエラストマー成分は、空気透過係数が２
５×１０-12 cc・cm／cm2 ・sec ・cmHgより大きく、ヤ
ング率が５００MPa 以下の任意のエラストマーもしくは
それらの任意のブレンド又はこれらにエラストマーの分
散性や耐熱性などの改善その他のために一般的にエラス
トマーに配合される補強剤、充填剤、架橋剤、軟化剤、
老化防止剤、加工助剤などの配合剤を必要量添加したエ
ラストマー組成物で、その配合量は空気透過防止層を構
成する樹脂及びエラストマー成分を含むポリマー成分の
合計量の全重量当り１０重量％以上、好ましくは１０〜
８５重量％である。The elastomer component blended as the component (B) in the resin composition according to the present invention has an air permeability coefficient of 2
For any elastomer having a Young's modulus of less than 500 MPa and larger than 5 × 10 −12 cc · cm / cm 2 · sec · cmHg, or any blend thereof, or improving the dispersibility and heat resistance of the elastomer. Reinforcing agents, fillers, cross-linking agents, softening agents, which are generally incorporated in elastomers,
An elastomer composition in which a necessary amount of a compounding agent such as an antiaging agent or a processing aid is added, and the compounding amount is 10% by weight based on the total weight of the total amount of the resin constituting the air permeation preventive layer and the polymer component including the elastomer component. Above, preferably 10
It is 85% by weight.
【００１８】そのようなエラストマー成分を構成するエ
ラストマーとしては、上記空気透過係数及びヤング率を
有するものであれば、特に限定されないが、例えば以下
のようなものを挙げることができる。The elastomer constituting such an elastomer component is not particularly limited as long as it has the above-mentioned air permeability coefficient and Young's modulus, but examples thereof include the following.
【００１９】ジエン系ゴム及びその水添物（例えばＮ
Ｒ、ＩＲ、エポキシ化天然ゴム、ＳＢＲ、ＢＲ（高シス
ＢＲ及び低シスＢＲ）、ＮＢＲ、水素化ＮＢＲ、水素化
ＳＢＲ）、オレフィン系ゴム（例えばエチレンプロピレ
ンゴム（ＥＰＤＭ、ＥＰＭ）、マレイン酸変性エチレン
プロピレンゴム（Ｍ−ＥＰＭ）、ＩＩＲ、イソブチレン
と芳香族ビニル又はジエン系モノマー共重合体、アクリ
ルゴム（ＡＣＭ）、アイオノマー）、含ハロゲンゴム
（例えば臭素化ブチルゴム（Ｂｒ−ＩＩＲ）、塩素化ブ
チルゴム（Ｃｌ−ＩＩＲ）、イソブチレンパラメチルス
チレン共重合体の臭素化物（Ｂｒ−ＩＰＭＳ）、クロロ
プレンゴム（ＣＲ）、ヒドリンゴム（ＣＨＲ，ＣＨ
Ｃ）、クロロスルホン化ポリエチレン（ＣＳＭ）、塩素
化ポリエチレン（ＣＭ）、マレイン酸変性塩素化ポリエ
チレン（Ｍ−ＣＭ））、シリコンゴム（例えばメチルビ
ニルシリコンゴム、ジメチルシリコンゴム、メチルフェ
ニルビニルシリコンゴム）、含イオウゴム（例えばポリ
スルフィドゴム）、フッ素ゴム（例えばビニリデンフル
オライド系ゴム、含フッ素ビニルエーテル系ゴム、テト
ラフルオロエチレン−プロピレン系ゴム、含フッ素シリ
コン系ゴム、含フッ素ホスファゼン系ゴム）、熱可塑性
エラストマー（例えばスチレン系エラストマー、ポリオ
レフィン系エラストマー、ポリエステル系エラストマ
ー、ポリウレタン系エラストマー、ポリアミド系エラス
トマー）などを挙げることができる。Diene rubbers and hydrogenated products thereof (for example, N
R, IR, epoxidized natural rubber, SBR, BR (high cis BR and low cis BR), NBR, hydrogenated NBR, hydrogenated SBR), olefin rubber (eg ethylene propylene rubber (EPDM, EPM), maleic acid modified) Ethylene propylene rubber (M-EPM), IIR, isobutylene and aromatic vinyl or diene monomer copolymer, acrylic rubber (ACM), ionomer), halogen-containing rubber (for example, brominated butyl rubber (Br-IIR), chlorinated butyl rubber) (Cl-IIR), bromide of isobutylene paramethylstyrene copolymer (Br-IPMS), chloroprene rubber (CR), hydrin rubber (CHR, CH
C), chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CM), maleic acid modified chlorinated polyethylene (M-CM)), silicone rubber (for example, methyl vinyl silicone rubber, dimethyl silicone rubber, methylphenyl vinyl silicone rubber). , Sulfur-containing rubber (for example, polysulfide rubber), fluororubber (for example, vinylidene fluoride rubber, fluorovinyl ether rubber, tetrafluoroethylene-propylene rubber, fluorosilicone rubber, fluorophosphazene rubber), thermoplastic elastomer ( Examples thereof include styrene elastomer, polyolefin elastomer, polyester elastomer, polyurethane elastomer, polyamide elastomer) and the like.
【００２０】なお、エラストマー成分として前記特開平
５−５０８４３５号公報に開示されているような、Ｃ4
〜Ｃ7 イソモノオレフィンとｐ−アルキルスチレンのハ
ロゲン（例えばＢｒ，Ｃｒ，Ｉ）含有共重合体ゴムであ
って、ｐ−アルキルスチレン含有量が全共重合体ゴムの
５．５〜２５重量％、好ましくは６．０〜２０重量％、
ハロゲン含有量が１．０重量％以上、好ましくは１．０
〜５．０重量％で、ムーニー粘度ＭＬ1+8 （１２５℃）
が３０以上、好ましくは３５〜７０の共重合体ゴムを用
いることができる。このゴムを使用する場合の（Ａ）成
分と（Ｂ）成分との重量比は（Ａ）／（Ｂ）＝１０／９
０〜９０／１０、好ましくは１５／８５〜８５／１５で
ある。As an elastomer component, C 4 as disclosed in JP-A-5-508435 is used.
To C 7 isomonoolefin and a halogen (eg Br, Cr, I) -containing copolymer rubber of p-alkylstyrene, wherein the p-alkylstyrene content is 5.5 to 25% by weight of the total copolymer rubber. , Preferably 6.0 to 20% by weight,
Halogen content is 1.0% by weight or more, preferably 1.0
~ 5.0% by weight, Mooney viscosity ML 1 + 8 (125 ℃)
Of 30 or more, preferably 35 to 70, can be used. When this rubber is used, the weight ratio of the component (A) and the component (B) is (A) / (B) = 10/9
It is 0 to 90/10, preferably 15/85 to 85/15.
【００２１】前記共重合体ゴムのｐ−アルキルスチレン
含有量が５．５重量％未満では得られたタイヤ用ポリマ
ー組成物の耐空気透過性が低下するので好ましくなく、
逆に２５重量％を超えると低温で脆化しやすくなるので
好ましくない。またハロゲン含有量が１．０重量％未満
では引張強さなどの機械的強度が低下するので好ましく
なく、ムーニー粘度が３０未満ではやはり、耐空気透過
性が低下するので好ましくない。更に（Ａ）成分／
（Ｂ）成分の配合比（重量基準）が１０／９０未満では
やはり耐空気透過性が低下するので好ましくなく、逆に
９０／１０を超えると柔軟性が低下するので好ましくな
い。If the p-alkylstyrene content of the above-mentioned copolymer rubber is less than 5.5% by weight, the air resistance of the obtained polymer composition for tires is lowered, which is not preferable.
On the contrary, if it exceeds 25% by weight, embrittlement easily occurs at low temperature, which is not preferable. Further, when the halogen content is less than 1.0% by weight, mechanical strength such as tensile strength is lowered, which is not preferable, and when the Mooney viscosity is less than 30, air permeation resistance is also lowered, which is not preferable. Further (A) component /
If the blending ratio (weight basis) of the component (B) is less than 10/90, the air permeation resistance is also lowered, which is not preferable, and conversely, if it exceeds 90/10, the flexibility is lowered, which is not preferable.
【００２２】なお、かかる共重合体ゴムのひとつとして
は、ＥＸＸＯＮ ＣＨＥＭ：よりＥＸＸＰＲＯとして市
販されており、例えば下記式で示される構造（Ａ）のイ
ソブチレンとｐ−メチルスチレンとの共重合体ゴムをＢ
ｒ2 で一部臭素化した下記構造（Ｂ）の共重合体ゴムで
ある。これは本願発明において好適に用いることができ
る。One of such copolymer rubbers is commercially available from EXXON CHEM: EXXPRO, and is, for example, a copolymer rubber of isobutylene and p-methylstyrene having the structure (A) represented by the following formula. B
It is a copolymer rubber of the following structure (B) partially brominated with r 2 . This can be preferably used in the present invention.
【００２３】[0023]
【化１】 Embedded image
【００２４】前記した特定の熱可塑性樹脂とエラストマ
ー成分との相溶性が異なる場合は、第３成分として適当
な相溶化剤を用いて両者を相溶化させるのが好ましい。
系に相溶化剤を混合することにより、熱可塑性樹脂とエ
ラストマー成分との界面張力が低下し、その結果、分散
層を形成しているゴム粒子径が微細になることから両成
分の特性はより有効に発現されることになる。そのよう
な相溶化剤としては一般的に熱可塑性樹脂及びエラスト
マー成分の両方又は片方の構造を有する共重合体、或い
は熱可塑性樹脂又はエラストマー成分と反応可能なエポ
キシ基、カルボニル基、ハロゲン基、アミノ基、オキサ
ゾリン基、水酸基等を有した共重合体の構造をとるもの
とすることができる。これらは混合される熱可塑性樹脂
とエラストマー成分の種類によって選定すれば良いが、
通常使用されるものにはスチレン／エチレン・ブチレン
ブロック共重合体（ＳＥＢＳ）及びそのマレイン酸変性
物、ＥＰＤＭ、ＥＰＤＭ／スチレン又はＥＰＤＭ／アク
リロニトリルグラフト共重合体及びそのマレイン酸変性
物、スチレン／マレイン酸共重合体、反応性フェノキシ
樹脂等を挙げることができる。かかる相溶化剤の配合量
には特に限定はないが、好ましくはポリマー成分（熱可
塑性樹脂とエラストマー成分の総和）１００重量部に対
して、０．５〜２０重量部が良い。When the compatibility between the specific thermoplastic resin and the elastomer component is different, it is preferable to use a suitable compatibilizing agent as the third component to make them compatible.
By mixing the compatibilizer into the system, the interfacial tension between the thermoplastic resin and the elastomer component is lowered, and as a result, the diameter of the rubber particles forming the dispersion layer becomes fine, so that the characteristics of both components are better. It will be effectively expressed. Such a compatibilizer is generally a copolymer having a structure of one or both of a thermoplastic resin and an elastomer component, or an epoxy group, a carbonyl group, a halogen group, an amino group capable of reacting with the thermoplastic resin or the elastomer component. It may have a structure of a copolymer having a group, an oxazoline group, a hydroxyl group and the like. These may be selected depending on the types of thermoplastic resin and elastomer component to be mixed,
Commonly used are styrene / ethylene / butylene block copolymer (SEBS) and its maleic acid modified product, EPDM, EPDM / styrene or EPDM / acrylonitrile graft copolymer and its maleic acid modified product, styrene / maleic acid. Examples thereof include copolymers and reactive phenoxy resins. The amount of the compatibilizer to be blended is not particularly limited, but is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the polymer component (the total amount of the thermoplastic resin and the elastomer component).
【００２５】特定の熱可塑性樹脂（Ａ）とエラストマー
成分（Ｂ）との組成比は、フィルムの厚さ、耐空気透過
性、柔軟性のバランスで適宜決めればよいが、好ましい
範囲は重量比で１０／９０〜９０／１０、更に好ましく
は２０／８０〜８５／１５である。The composition ratio of the specific thermoplastic resin (A) and the elastomer component (B) may be appropriately determined depending on the balance of film thickness, air permeation resistance and flexibility, but the preferred range is the weight ratio. 10/90 to 90/10, more preferably 20/80 to 85/15.
【００２６】本発明に係るポリマー組成物には、上記必
須成分（Ａ）及び（Ｂ）のポリマー成分に加えて第三成
分として、本発明のタイヤ用ポリマー組成物の必要特性
を損なわない範囲で前記した相溶化剤ポリマーなどの他
のポリマーを混合することができる。他ポリマーを混合
する目的は、熱可塑性樹脂とエラストマー成分との相溶
性を改良するため、材料のフィルム成形加工性を良くす
るため、耐熱性向上のため、コストダウンのため等があ
り、これに用いられる材料としては、例えばポリエチレ
ン（ＰＥ）、ポリプロピレン（ＰＰ）、ポリスチレン
（ＰＳ）、ＡＢＳ、ＳＢＳ、ポリカーボネート（ＰＣ）
等が挙げられる。この第三成分（Ｃ）のポリマーについ
ては、その空気透過係数、ヤング率は、ポリマー組成物
として所定の値をもつものであれば、特に限定はない。The polymer composition according to the present invention contains, as a third component in addition to the polymer components of the above-mentioned essential components (A) and (B), within a range that does not impair the required characteristics of the tire polymer composition of the present invention. Other polymers such as the compatibilizer polymers described above can be mixed. The purpose of mixing other polymers is to improve the compatibility between the thermoplastic resin and the elastomer component, to improve the film forming processability of the material, to improve the heat resistance, to reduce the cost, etc. Examples of materials used include polyethylene (PE), polypropylene (PP), polystyrene (PS), ABS, SBS, polycarbonate (PC).
Etc. The air permeability coefficient and Young's modulus of the polymer of the third component (C) are not particularly limited as long as they have predetermined values as a polymer composition.
【００２７】本発明に係るポリマー組成物は、前記した
通り、特定の空気透過係数及びヤング率を有するポリマ
ー成分（Ａ）及び（Ｂ）を必須の構成成分として含む
が、これを図示すれば図１のグラフ図に示す通りとな
り、図１において成分（Ａ）は領域Ｘに、成分（Ｂ）は
領域Ｙに、そして得られたポリマー組成物は領域Ｚに相
当する。As described above, the polymer composition according to the present invention contains the polymer components (A) and (B) having a specific air permeability coefficient and Young's modulus as essential constituents. 1, the component (A) corresponds to the region X, the component (B) corresponds to the region Y, and the obtained polymer composition corresponds to the region Z in FIG.
【００２８】本発明において、成分（Ａ）に属する熱可
塑性樹脂Ａ1 〜Ａn を決定し、（ここでｉ番目の熱可塑
性樹脂Ａi のヤング率をＡix、空気透過係数をＡiyとし
て、Ａi ＝（Ａix，Ａiy）と表す）これらの平均値Ａａ
ｖ（＝Σφｉ（Ａix，Ａiy）（ｉ＝１〜ｎ）、ここでφ
ｉはＡｉの重量分率）を求める。この点Ａａｖと空気透
過係数が２５×１０-12 cc・cm／cm2 ・sec ・cmHg、ヤ
ング率５００MPa の点Ｐとを直線で結び、直線ＡａｖＰ
を外挿してできた直線の下側と、空気透過係数２５×１
０-12 cc・cm／cm2 ・sec ・cmHg以上の領域Ｓに、Ｙ領
域に属する（Ｂ）成分、Ｂ1 〜Ｂn の平均値Ｂａｖ（＝
Σφｉ（Ｂix，Ｂiy）（ｉ＝１〜ｎ）、ここでφｉはＢ
ｉの重量分率、Ｂixはｉ番目のエラストマー成分のヤン
グ率、Ｂ iyはｉ番目のエラストマー成分の空気透過係
数）が入るようなエラストマーを選択し、（Ａ）成分、
（Ｂ）成分を適当配合で混合することにより目的の領域
Ｚに入るポリマー組成物を得ることができる。In the present invention, the heat resistance belonging to component (A)
Plastic resin A1~ An, (Where i is the thermoplastic
Resin AiYoung's modulus of Aix, The air permeability coefficient is Aiyage
Ai= (Aix, Aiy)) These average values Aa
v (= Σφi (Aix, Aiy) (I = 1 to n), where φ
i is the weight fraction of Ai). This point Aav and air permeability
Over coefficient 25 × 10-12cc / cm / cm2・ Sec ・ cmHg,
A straight line AavP
Below the straight line created by extrapolation, and the air permeability coefficient 25 x 1
0-12cc / cm / cm2・ Sec ・ In the area S of cmHg or more, Y area
(B) component belonging to range, B1~ BnAverage value Bav (=
Σφi (Bix, Biy) (I = 1 to n), where φi is B
i weight fraction, BixIs the yan of the i-th elastomer component
Rate, B iyIs the air permeation coefficient of the i-th elastomer component
Select an elastomer that contains
By mixing the component (B) in an appropriate composition, the target area
A polymer composition entering Z can be obtained.
【００２９】以下、本発明のタイヤ用ポリマー組成物を
用いて製造した空気透過防止層を有する空気入りタイヤ
について更に詳しく説明する。本発明に係る空気入りタ
イヤの空気透過防止層は、タイヤ内部の任意の位置、即
ちカーカス層の内側又は外側、或いはその他の位置に配
置することができる。要はタイヤ内部からの空気の透過
拡散を防止して、タイヤ内部の空気圧を長期間保持する
ことができるように配置することにより本発明の目的が
達成される。The pneumatic tire having an air permeation preventive layer produced by using the polymer composition for a tire of the present invention will be described in more detail below. The air permeation preventive layer of the pneumatic tire according to the present invention can be arranged at any position inside the tire, that is, inside or outside the carcass layer, or at any other position. In short, the object of the present invention is achieved by arranging the tire so that the air pressure inside the tire can be prevented and the air pressure inside the tire can be maintained for a long period of time.
【００３０】図２は空気入りタイヤの空気透過防止層の
配置の典型例を例示する子午線方向半断面図である。図
２において、左右一対のビードコア１，１間にカーカス
層２が装架され、このカーカス層２の内側のタイヤ内面
には、インナーライナー層３が設けられている。このイ
ンナーライナー層３は本発明では前記タイヤ用ポリマー
組成物から構成されている。図２において４はサイドウ
ォールを示す。FIG. 2 is a half-sectional view in the meridian direction illustrating a typical example of the arrangement of the air permeation preventive layer of a pneumatic tire. In FIG. 2, a carcass layer 2 is mounted between a pair of left and right bead cores 1, 1 and an inner liner layer 3 is provided on the inner surface of the tire inside the carcass layer 2. The inner liner layer 3 is composed of the tire polymer composition in the present invention. In FIG. 2, 4 indicates a sidewall.
【００３１】本発明において空気透過防止層を構成する
ポリマー組成物の製造方法は、予め熱可塑性樹脂とエラ
ストマー成分（ゴムの場合は未加硫物）とを２軸混練押
出機等で溶融混練し、連続相を形成する熱可塑性樹脂中
にエラストマー成分を分散させることによる。エラスト
マー成分を加硫する場合には、混練下で加硫剤を添加
し、エラストマー成分を動的加硫させても良い。また、
熱可塑性樹脂またはエラストマー成分への各種配合剤
（加硫剤を除く）は、上記混練中に添加しても良いが、
混練の前に予め混合しておくことが好ましい。熱可塑性
樹脂とエラストマー成分の混練に使用する混練機として
は、特に限定はなく、スクリュー押出機、ニーダ、バン
バリミキサー、２軸混練押出機等が挙げられる。中でも
熱可塑性樹脂とエラストマー成分の混練およびエラスト
マー成分の動的加硫には２軸混練押出機を使用するのが
好ましい。さらに、２種類以上の混練機を使用し、順次
混練してもよい。溶融混練の条件として、温度は熱可塑
性樹脂が溶融する温度以上であれば良い。また、混練時
の剪断速度は１０００〜７５００ Sec-1であるのが好ま
しい。混練全体の時間は３０秒から１０分、また加硫剤
を添加した場合には、添加後の加硫時間は１５秒から５
分であるのが好ましい。上記方法で作製されたポリマー
組成物は、次に押出し成形またはカレンダー成形によっ
てフィルム化される。フィルム化の方法は、通常の熱可
塑性樹脂または熱可塑性エラストマーをフィルム化する
方法によれば良い。In the present invention, the method for producing the polymer composition constituting the air permeation preventive layer is such that the thermoplastic resin and the elastomer component (unvulcanized product in the case of rubber) are melt-kneaded in advance with a twin-screw kneading extruder or the like. , By dispersing the elastomer component in the thermoplastic resin that forms the continuous phase. When vulcanizing the elastomer component, a vulcanizing agent may be added under kneading to dynamically vulcanize the elastomer component. Also,
Various compounding agents (excluding the vulcanizing agent) to the thermoplastic resin or the elastomer component may be added during the kneading,
It is preferable to mix them in advance before kneading. The kneading machine used for kneading the thermoplastic resin and the elastomer component is not particularly limited, and examples thereof include a screw extruder, a kneader, a Banbury mixer, and a twin-screw kneading extruder. Above all, it is preferable to use a twin-screw kneading extruder for the kneading of the thermoplastic resin and the elastomer component and the dynamic vulcanization of the elastomer component. Further, two or more kinds of kneaders may be used and kneading may be sequentially performed. As a condition for melt-kneading, the temperature may be equal to or higher than the temperature at which the thermoplastic resin melts. The shear rate during kneading is preferably 1000 to 7500 Sec -1 . The total kneading time is 30 seconds to 10 minutes, and if a vulcanizing agent is added, the vulcanization time after addition is 15 seconds to 5 minutes.
Minutes are preferred. The polymer composition produced by the above method is then formed into a film by extrusion or calendering. The method of forming a film may be based on a method of forming a film of a usual thermoplastic resin or thermoplastic elastomer.
【００３２】このようにして得られる薄膜は、熱可塑性
樹脂（Ａ）のマトリクス中にエラストマー成分（Ｂ）が
不連続相として分散した構造をとる。かかる状態の分散
構造をとることにより柔軟性と耐空気透過性のバランス
を付与することが可能でかつ、耐熱変形性改善、耐水性
向上等の効果を得ることが出来、かつ熱可塑の加工が可
能となるため通常の樹脂用成形機即ち押出し成形また
は、カレンダー成形によって、フィルム化することが可
能となる。フィルム化の方法は、通常の熱可塑性樹脂ま
たは、熱可塑性エラストマーをフィルム化する方法によ
れば良い。The thin film thus obtained has a structure in which the elastomer component (B) is dispersed as a discontinuous phase in the matrix of the thermoplastic resin (A). By adopting a dispersion structure in such a state, it is possible to give a balance between flexibility and air permeation resistance, and it is possible to obtain effects such as improved heat distortion resistance and improved water resistance, and thermoplastic processing. Since it becomes possible, it is possible to form a film by a usual resin molding machine, that is, extrusion molding or calender molding. The method of forming a film may be a method of forming an ordinary thermoplastic resin or thermoplastic elastomer into a film.
【００３３】本発明に係るポリマー組成物の薄膜から成
る空気透過防止層を有する空気入りタイヤの製造方法に
ついて、図２に示すように、インナーライナー層３をカ
ーカス層２の内側に配置する場合の一例を説明すると、
予め本発明のポリマー組成物を所定の幅と厚さの薄膜状
に押し出し、それをタイヤ成型用ドラム上に円筒に貼り
着ける。その上に未加硫ゴムからなるカーカス層、ベル
ト層、トレッド層等の通常のタイヤ製造に用いられる部
材を順次貼り重ね、ドラムを抜き去ってグリーンタイヤ
とする。次いで、このグリーンタイヤを常法に従って加
熱加硫することにより、所望の軽量化空気入りタイヤを
製造することができる。なお、カーカス層の外周面に空
気透過防止層を設ける場合にも、これに準じて行うこと
ができる。Regarding the method for producing a pneumatic tire having an air permeation preventive layer comprising a thin film of the polymer composition according to the present invention, as shown in FIG. 2, when the inner liner layer 3 is arranged inside the carcass layer 2, To explain one example,
The polymer composition of the present invention is extruded in advance into a thin film having a predetermined width and thickness, which can be adhered to a cylinder on a tire molding drum. Members such as a carcass layer made of unvulcanized rubber, a belt layer, and a tread layer, which are used in ordinary tire manufacturing, are successively laminated on top of this, and the drum is removed to obtain a green tire. Then, the desired lightweight pneumatic tire can be manufactured by subjecting this green tire to heat vulcanization according to a conventional method. It should be noted that when the air permeation preventive layer is provided on the outer peripheral surface of the carcass layer, the same process can be performed.
【００３４】本発明に従った空気透過防止層を接着せし
めるゴム層の材料には特に限定はなく、従来からタイヤ
用ゴム材料として一般に使用されている任意のゴム材料
とすることができる。そのようなゴムとしては、例え
ば、ＮＲ，ＩＲ，ＢＲ，ＳＢＲ等のジエン系ゴム、ハロ
ゲン化ブチルゴム、エチレン−プロピレン共重合ゴム、
スチレン系エラストマー等にカーボンブラック、プロセ
スオイル、加硫剤等の配合剤を添加したゴム組成物とす
ることができる。The material of the rubber layer to which the air permeation preventive layer according to the present invention is adhered is not particularly limited, and any rubber material conventionally used as a rubber material for tires can be used. Examples of such rubber include diene rubbers such as NR, IR, BR, SBR, halogenated butyl rubber, ethylene-propylene copolymer rubber,
A rubber composition can be obtained by adding a compounding agent such as carbon black, process oil and a vulcanizing agent to a styrene-based elastomer or the like.
【００３５】本発明に係る空気透過防止層は、空気透過
係数が２５×１０-12 cc・cm／cm2・sec ・cmHg以下、
好ましくは５×１０-12 cc・cm／cm2 ・sec ・cmHg以下
である。空気透過係数の下限は特にないが、事実上は
０．０５×１０-12 cc・cm／cm 2 ・sec ・cmHgである。
空気透過量を２５×１０-12 cc・cm／cm2 ・sec ・cmHg
以下にすることによって空気透過防止層の厚さを従来の
空気透過防止層の厚さの１／２以下にすることができ
る。The air permeation preventive layer according to the present invention is an air permeation preventive layer.
Coefficient is 25 × 10-12cc / cm / cm2・ Sec ・ cmHg or less,
Preferably 5 × 10-12cc / cm / cm2・ Sec ・ cmHg or less
Is. There is no particular lower limit for the air permeability coefficient, but in practice
0.05 x 10-12cc / cm / cm 2・ Sec ・ cmHg.
Air permeation rate is 25 × 10-12cc / cm / cm2・ Sec ・ cmHg
The thickness of the air permeation preventive layer is
Can be less than 1/2 the thickness of the air permeation preventive layer
It
【００３６】一方、ヤング率が１〜５００MPa 、好まし
くは１０〜３００MPa 、厚さが０．０２〜１．０mm、好
ましくは０．０５〜０．５mmである。ヤング率が１MPa
未満ではタイヤ成型時にシワがよる等によりハンドリン
グが困難になるので好ましくなく、逆に５００MPa 超で
は走行時のタイヤ変形に追従できないので好ましくな
い。On the other hand, the Young's modulus is 1 to 500 MPa, preferably 10 to 300 MPa, and the thickness is 0.02 to 1.0 mm, preferably 0.05 to 0.5 mm. Young's modulus is 1 MPa
When it is less than 500 MPa, it is not preferable because handling becomes difficult due to wrinkles during tire molding. On the contrary, when it exceeds 500 MPa, it is not preferable because the tire deformation during running cannot be followed.
【００３７】[0037]
【実施例】以下、実施例に従って本発明を更に具体的に
説明するが、本発明を以下の実施例に限定するものでな
いことは言うまでもない。以下の例において使用した評
価方法は以下の通りである。EXAMPLES The present invention will be described in more detail below with reference to Examples, but it goes without saying that the present invention is not limited to the following Examples. The evaluation methods used in the following examples are as follows.
【００３８】フィルムの空気透過係数測定法 ＪＩＳ Ｋ７１２６「プラスチックフィルム及びシート
の気体透過度試験方法（Ａ法）」に準じた。 試験片 ： 各例で作成したフィルムサンプルを用い
た。 試験気体 ： 空気（Ｎ2 ：Ｏ2 ＝８：２） 試験温度 ： ３０℃ Film air permeation coefficient measurement method: JIS K7126 "Plastic film and sheet gas permeation test method (method A)" was followed. Test piece: The film sample prepared in each example was used. Test gas: Air (N 2 : O 2 = 8: 2) Test temperature: 30 ° C
【００３９】フィルムのヤング率の測定法 ＪＩＳ Ｋ６２５１「加硫ゴムの引張試験方法」に準じ
た。 試験片 ： 各例で作成したフィルムサンプルをフィ
ルムの押出成型時の樹脂の押出方向に平行に、ＪＩＳ３
号ダンベルで打ち抜いた。得られた応力〜ひずみ曲線の
初期ひずみ領域の曲線に接線を引き、その接線の傾きよ
りヤング率を求めた。 The measuring method of Young's modulus of the film was based on JIS K6251 "Tensile test method of vulcanized rubber". Test piece: The film sample prepared in each example was placed in parallel with the resin extrusion direction at the time of extrusion molding of the film in accordance with JIS3.
I punched it out with a dumbbell. A tangent line was drawn on the curve of the initial strain region of the obtained stress-strain curve, and Young's modulus was obtained from the slope of the tangent line.
【００４０】タイヤ空気漏れ性能試験法 １６５ＳＲ１３ スチールラジアルタイヤ（リム １３
×４1/2 −Ｊ）を使用して、初期圧力２００kPa 、無負
荷条件にて室温２１℃で３ヶ月間放置して測定間隔４日
毎に圧力を測定した。測定圧力Ｐｔ、初期圧力Ｐｏ及び
経過日数ｔとして、関数： Ｐｔ／Ｐｏ＝ｅｘｐ（−αｔ） に回帰してα値を求める。得られたαを用い、ｔ＝３０
を下式に代入し、 β＝［１−ｅｘｐ（−αｔ）］×１００ β値を得る。このβ値を１ヶ月当りの圧力低下率（％／
月）とする。 Tire Air Leakage Performance Test Method 165SR13 Steel Radial Tire (Rim 13
The pressure was measured at an interval of 4 days with an initial pressure of 200 kPa and no load at room temperature of 21 ° C. for 3 months. As the measured pressure Pt, the initial pressure Po, and the elapsed days t, the α value is obtained by regressing the function: Pt / Po = exp (−αt). Using the obtained α, t = 30
Is substituted into the following formula to obtain β = [1−exp (−αt)] × 100 β value. This β value is the rate of pressure drop per month (% /
Month).
【００４１】以下に示す各実施例及び比較例で用いたポ
リマーの銘柄及び基本物性を表Ｉに掲げる。ここで、エ
ラストマー成分の中のゴムの基本物性に関しては原料単
味では形状が保持できず、測定が困難な材料もあるの
で、表IIの配合にて加硫したものの値を典型的な特性と
して示している。また、各配合剤の銘柄を表III に示
す。Table I shows the brands and basic physical properties of the polymers used in the following Examples and Comparative Examples. Here, regarding the basic physical properties of the rubber in the elastomer component, the shape cannot be maintained by the raw material alone, and there are some materials that are difficult to measure, so the values of those vulcanized with the formulation in Table II are used as typical characteristics. Shows. The brands of each compounding agent are shown in Table III.
【００４２】[0042]
【表１】 [Table 1]
【００４３】[0043]
【表２】 [Table 2]
【００４４】[0044]
【表３】 [Table 3]
【００４５】[0045]
【表４】 [Table 4]
【００４６】実施例１〜８ 表IV〜表XIに示す各種配合割合（重量部）で種々の熱可
塑性樹脂成分（Ａ）の１種または２種とエラストマー成
分（Ｂ）及び場合によっては、加硫剤、滑材等の他成分
とを２軸混練機にて混練、ペレット化し、次に押出機で
幅３５０mm、厚さ０．１mmのフィルムとした。得られた
フィルムの空気透過係数及びヤング率を測定し、結果を
それぞれ表IV〜表XIに示した。 Examples 1 to 8 One or two of various thermoplastic resin components (A) at various compounding ratios (parts by weight) shown in Tables IV to XI, an elastomer component (B) and, in some cases, additions. Other components such as a sulfurizing agent and a lubricant were kneaded and pelletized by a biaxial kneader, and then a film having a width of 350 mm and a thickness of 0.1 mm was formed by an extruder. The air permeability coefficient and Young's modulus of the obtained film were measured, and the results are shown in Tables IV to XI, respectively.
【００４７】[0047]
【表５】 [Table 5]
【００４８】[0048]
【表６】 [Table 6]
【００４９】[0049]
【表７】 [Table 7]
【００５０】[0050]
【表８】 [Table 8]
【００５１】[0051]
【表９】 [Table 9]
【００５２】[0052]
【表１０】 [Table 10]
【００５３】[0053]
【表１１】 [Table 11]
【００５４】[0054]
【表１２】 [Table 12]
【００５５】[0055]
【表１３】 [Table 13]
【００５６】[0056]
【表１４】 [Table 14]
【００５７】実施例９ 表XII に示す各種配合割合（重量部）で種々の熱可塑性
樹脂成分（Ａ）とエラストマー成分（Ｂ）及び第３成分
（ポリカーボネート）と、場合によっては加硫剤、滑材
等の他成分とを２軸混練機にて混練、ペレット化し、次
に押出機で幅３５０mm、厚さ０．２mmのフィルムとし
た。得られたフィルムの空気透過係数及びヤング率を測
定し、結果を表XII に示した。 Example 9 Various thermoplastic resin components (A), an elastomer component (B) and a third component (polycarbonate) at various compounding ratios (parts by weight) shown in Table XII, a vulcanizing agent and a lubricating agent as the case may be. The other ingredients and other components were kneaded by a biaxial kneader and pelletized, and then a film having a width of 350 mm and a thickness of 0.2 mm was formed by an extruder. The air permeability coefficient and Young's modulus of the obtained film were measured, and the results are shown in Table XII.
【００５８】[0058]
【表１５】 [Table 15]
【００５９】実施例１０〜１３及び比較例１ Ｂｒ−ＩＩＲ及びＢｒ−ＩＰＭＳに各種配合剤を混合
し、密閉式のバンバリーミキサー中で、マスターバッチ
Ａ，Ｂを作製した。マスターバッチの配合を表XIIIに示
す。 Examples 10 to 13 and Comparative Example 1 Br-IIR and Br-IPMS were mixed with various compounding agents to prepare master batches A and B in a closed Banbury mixer. The masterbatch formulation is shown in Table XIII.
【００６０】[0060]
【表１６】 [Table 16]
【００６１】これらのマスターバッチをゴム用ペレタイ
ザーを用いてペレット化し、表XIVに示す各種配合割合
（重量部）で２軸混練機にて樹脂材料及び架橋剤と混練
し、ペレット化し、次に押出機で幅３５０mm、厚さ０．
１mmのフィルムを作製した。得られたフィルムの空気透
過係数及びヤング率を測定した。さらに、これらのフィ
ルムをタイヤ成形用のドラムに巻き、その上にカーカ
ス、サイドベルト、トレッド等のタイヤ部材を積層さ
せ、インフレートさせて、グリーンタイヤとした。グリ
ーンタイヤは、加硫機で１８０℃、１０分間加硫させ、
タイヤサイズ１６５ＳＲ１３のタイヤに仕上げた。These master batches were pelletized using a pelletizer for rubber, kneaded with a resin material and a cross-linking agent at various compounding ratios (parts by weight) shown in Table XIV with a biaxial kneader, pelletized, and then extruded. Machine width 350mm, thickness 0.
A 1 mm film was made. The air permeability coefficient and Young's modulus of the obtained film were measured. Further, these films were wound on a tire forming drum, and a tire member such as a carcass, a side belt and a tread was laminated thereon and inflated to obtain a green tire. Green tires are vulcanized by a vulcanizer at 180 ° C for 10 minutes,
A tire having a tire size of 165SR13 was finished.
【００６２】一方比較例として、グリーンタイヤの内面
に厚さ約０．７mmのタイゴムを介して、未加硫のブチル
ゴムから成る約０．５mmのインナーライナー層を有する
グリーンタイヤを成形し、その後、加硫して、タイヤを
仕上げた（サイズ１６５ＳＲ１３）。インナーライナー
層の配合及び空気透過係数、ヤング率は実施例同様に表
XIV に示した。得られた空気入りタイヤのインナーライ
ナー層の重量測定及び空気漏れ試験を行った。結果を表
XIV に示す。On the other hand, as a comparative example, a green tire having an inner liner layer of about 0.5 mm made of unvulcanized butyl rubber was formed on the inner surface of the green tire through a tie rubber having a thickness of about 0.7 mm, and then, The tire was vulcanized and finished (size 165SR13). The composition, air permeability coefficient and Young's modulus of the inner liner layer are shown in the same manner as in the examples.
Shown in XIV. The weight measurement and air leakage test of the inner liner layer of the obtained pneumatic tire were performed. Table of results
Shown in XIV.
【００６３】[0063]
【表１７】 [Table 17]
【００６４】実施例１４ 表XVに示す８種類の臭素変性したポリイソブチレン−ｐ
−メチルスチレン共重合体ゴムを用いて前記実施例に示
したのと同様にして、熱可塑性樹脂成分としてＮ１１
（リルサンＢＥＳＮＯ ＴＬ）（表Ｉ参照）、Ｎ６／６
６（ウルトラミッドＣ３５）（表Ｉ参照）及びＥＶＯＨ
（エバールＥＰＥ１５３Ｂ）（表Ｉ参照）を用いて表XV
I 、表XVII及び表XVIII に示したポリマーの配合比で空
気透過係数及びヤング率を評価した。結果は表XVI 〜表
XVIII に示す。なお、変性ポリイソプレンゴムのゴム配
合は以下の通りとした。ゴム配合 ────────────────────── 変性ポリイソブチレンゴム １００重量部 ステアリン酸亜鉛 １重量部 ステアリン酸 ２重量部 亜鉛華３号 ０．５重量部 ────────────────────── Example 14 Eight kinds of brominated polyisobutylene-p shown in Table XV
-Methylstyrene copolymer rubber was used in the same manner as shown in the above-mentioned example to prepare N11 as a thermoplastic resin component.
(Rilsan BESNO TL) (see Table I), N6 / 6
6 (Ultramid C35) (see Table I) and EVOH
Table XV using (EVAL EPE153B) (see Table I)
The air permeability coefficient and Young's modulus were evaluated by the compounding ratios of the polymers shown in I, Table XVII and Table XVIII. Results are in Table XVI-Table
Shown in XVIII. The rubber composition of the modified polyisoprene rubber was as follows. Rubber compounding ────────────────────── Modified polyisobutylene rubber 100 parts by weight Zinc stearate 1 part by weight Stearic acid 2 parts by weight Zinc Hua No. 3 0.5 parts by weight Department ──────────────────────
【００６５】[0065]
【表１８】 [Table 18]
【００６６】[0066]
【表１９】 [Table 19]
【００６７】[0067]
【表２０】 [Table 20]
【００６８】[0068]
【表２１】 [Table 21]
【００６９】[0069]
【発明の効果】以上説明したように、本発明に従えば、
タイヤ内の空気圧保持性を良好に保持し、かつ柔軟性を
維持しつつ、タイヤの軽量化を図ることができる、空気
入りタイヤの空気透過防止層に適したタイヤ用ポリマー
組成物を得ることができる。As described above, according to the present invention,
It is possible to obtain a tire polymer composition suitable for an air permeation preventive layer of a pneumatic tire, which can maintain the air pressure retaining property in the tire favorably and can reduce the weight of the tire while maintaining the flexibility. it can.
【図１】本発明に係るポリマー成分（Ａ）及び（Ｂ）並
びに本発明のポリマー組成物の空気透過率とヤング率と
の関係を示すグラフ図である。FIG. 1 is a graph showing the relationship between air permeability and Young's modulus of polymer components (A) and (B) according to the present invention and the polymer composition of the present invention.
【図２】本発明の空気入りタイヤのインナーライナー部
の構造を示す子午線方向半断面図である。FIG. 2 is a meridional direction half cross-sectional view showing the structure of the inner liner portion of the pneumatic tire of the present invention.
１…ビードコア ２…カーカス層 ３…インナーライナー層 ４…サイドウォール 1 ... Bead core 2 ... Carcass layer 3 ... Inner liner layer 4 ... Sidewall
───────────────────────────────────────────────────── フロントページの続き (72)発明者 黒田 紀明 神奈川県平塚市追分２番１号 横浜ゴム株 式会社平塚製造所内 (72)発明者 井川 勝弘 神奈川県平塚市追分２番１号 横浜ゴム株 式会社平塚製造所内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Noriaki Kuroda No. 2 Oiwake, Hiratsuka-shi, Kanagawa Yokohama Rubber Co., Ltd. Hiratsuka Factory (72) Inventor Katsuhiro Ikawa No. 2 Oiwake, Hiratsuka-shi, Kanagawa Yokohama Rubber Co., Ltd. Ceremony Company Hiratsuka Factory
Claims (6)
・cm／cm2 ・sec ・cmHg以下でヤング率が５００MPa 超
の少なくとも一種の熱可塑性樹脂を全ポリマー成分重量
当り１０重量％以上並びに（Ｂ）空気透過係数が２５×
１０-12 cc・cm／cm2 ・sec ・cmHg超でヤング率が５０
０MPa 以下の少なくとも一種のエラストマー成分を全ポ
リマー成分重量当り１０重量％以上で、成分（Ａ）及び
成分（Ｂ）の合計量（Ａ）＋（Ｂ）が全ポリマー成分重
量当り３０重量％以上となる量で含み、かつ空気透過係
数が２５×１０-12 cc・cm／cm2 ・sec ・cmHg以下でヤ
ング率が１〜５００MPa のタイヤ用ポリマー組成物。1. (A) Air permeability coefficient is 25 × 10 -12 cc
・ Cm / cm 2・ sec ・ cmHg or less, and Young's modulus of more than 500 MPa, at least one kind of thermoplastic resin is 10% by weight or more based on the weight of all polymer components, and (B) the air permeability coefficient is 25 ×.
10 -12 cc ・ cm / cm 2・ sec ・ cmHg and Young's modulus is 50
At least one elastomer component of 0 MPa or less is 10% by weight or more based on the weight of all polymer components, and the total amount (A) + (B) of the components (A) and (B) is 30% by weight or more based on the weight of all polymer components. A polymer composition for a tire, which comprises the following amount and has an air permeability coefficient of 25 × 10 −12 cc · cm / cm 2 · sec · cmHg or less and a Young's modulus of 1 to 500 MPa.
ミド系樹脂、ポリエステル系樹脂、ポリニトリル系樹
脂、ポリメタクリレート系樹脂、ポリビニル系樹脂、セ
ルロース系樹脂、フッ素系樹脂及びイミド系樹脂の群か
ら選ばれた少なくとも一種の熱可塑性樹脂である請求項
１記載のタイヤ用ポリマー組成物。2. The thermoplastic resin as the component (A) is selected from the group consisting of polyamide resins, polyester resins, polynitrile resins, polymethacrylate resins, polyvinyl resins, cellulose resins, fluorine resins and imide resins. The polymer composition for tires according to claim 1, which is at least one kind of thermoplastic resin selected.
系ゴム及びその水添物、オレフィン系ゴム、含ハロゲン
系ゴム、シリコンゴム、含イオウゴム、フッ素ゴム並び
に熱可塑性エラストマーの群から選ばれた少なくとも一
種のエラストマーである請求項１又は２に記載のタイヤ
用ポリマー組成物。3. The component (B) elastomer is at least selected from the group consisting of diene rubbers and hydrogenated products thereof, olefin rubbers, halogen-containing rubbers, silicone rubbers, sulfur-containing rubbers, fluororubbers and thermoplastic elastomers. The tire polymer composition according to claim 1 or 2, which is a kind of elastomer.
不連続相を形成している請求項１〜３のいずれか１項に
記載のタイヤ用ポリマー組成物。4. The tire polymer composition according to claim 1, wherein the elastomer as the component (B) forms a discontinuous phase in the composition.
7 イソモノオレフィンとｐ−アルキルスチレンのハロゲ
ン含有共重合体ゴムであって、ｐ−アルキルスチレン含
有量が５．５〜２５重量％、ハロゲン含有量が１．０重
量％以上でムーニー粘度ＭＬ1+8 （１２５℃）が３０以
上の共重合体ゴムを含んでなるゴムを用い、熱可塑性成
分（Ａ）とエラストマー成分（Ｂ）との重量比（Ａ）／
（Ｂ）が１０／９０〜９０／１０である請求項１，２又
は４記載のタイヤ用ポリマー組成物。5. C 4 to C as the elastomer component (B)
7 A halogen-containing copolymer rubber of isomonoolefin and p-alkylstyrene, wherein the p-alkylstyrene content is 5.5 to 25% by weight, the halogen content is 1.0% by weight or more, and the Mooney viscosity ML 1 A rubber containing a copolymer rubber having a +8 (125 ° C.) of 30 or more is used, and the weight ratio (A) / of the thermoplastic component (A) and the elastomer component (B) /
(B) is 10 / 90-90 / 10, The polymer composition for tires of Claim 1, 2 or 4.
イヤ用ポリマー組成物の薄膜を空気透過防止層に用いた
空気入りタイヤ。6. A pneumatic tire using a thin film of the tire polymer composition according to claim 1 for an air permeation preventive layer.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15035395A JP3217239B2 (en) | 1995-01-23 | 1995-06-16 | Polymer composition for tire and pneumatic tire using the same |
| US08/589,450 US6079465A (en) | 1995-01-23 | 1996-01-22 | Polymer composition for tire and pneumatic tire using same |
| EP96100910A EP0722850B2 (en) | 1995-01-23 | 1996-01-23 | Polymer composition for tire and pneumatic tire using same |
| DE69602286T DE69602286T3 (en) | 1995-01-23 | 1996-01-23 | Polymer compositions and their use in pneumatic tires |
| US09/276,745 US6334919B1 (en) | 1995-01-23 | 1999-03-26 | Polymer composition for tire and pneumatic tire using same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7-8394 | 1995-01-23 | ||
| JP839495 | 1995-01-23 | ||
| JP15035395A JP3217239B2 (en) | 1995-01-23 | 1995-06-16 | Polymer composition for tire and pneumatic tire using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08259741A true JPH08259741A (en) | 1996-10-08 |
| JP3217239B2 JP3217239B2 (en) | 2001-10-09 |
Family
ID=26342908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15035395A Expired - Lifetime JP3217239B2 (en) | 1995-01-23 | 1995-06-16 | Polymer composition for tire and pneumatic tire using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3217239B2 (en) |
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