JPH08258504A - Pneumatic tire and manufacture thereof - Google Patents
Pneumatic tire and manufacture thereofInfo
- Publication number
- JPH08258504A JPH08258504A JP7051307A JP5130795A JPH08258504A JP H08258504 A JPH08258504 A JP H08258504A JP 7051307 A JP7051307 A JP 7051307A JP 5130795 A JP5130795 A JP 5130795A JP H08258504 A JPH08258504 A JP H08258504A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- tire
- pneumatic tire
- rubber
- air permeation
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229920001971 elastomer Polymers 0.000 claims abstract description 40
- 239000005060 rubber Substances 0.000 claims abstract description 39
- 229920001577 copolymer Polymers 0.000 claims abstract description 22
- 239000000853 adhesive Substances 0.000 claims abstract description 16
- 230000001070 adhesive effect Effects 0.000 claims abstract description 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010409 thin film Substances 0.000 claims abstract description 5
- 230000003449 preventive effect Effects 0.000 claims description 33
- 238000004073 vulcanization Methods 0.000 claims description 18
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 10
- 230000035699 permeability Effects 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- QLUXVUVEVXYICG-UHFFFAOYSA-N 1,1-dichloroethene;prop-2-enenitrile Chemical compound C=CC#N.ClC(Cl)=C QLUXVUVEVXYICG-UHFFFAOYSA-N 0.000 claims description 2
- 230000002140 halogenating effect Effects 0.000 claims 2
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract 2
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 78
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 230000026030 halogenation Effects 0.000 description 8
- 238000005658 halogenation reaction Methods 0.000 description 8
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 229920005549 butyl rubber Polymers 0.000 description 5
- 229920005555 halobutyl Polymers 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 229920003002 synthetic resin Polymers 0.000 description 5
- 239000000057 synthetic resin Substances 0.000 description 5
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229950009390 symclosene Drugs 0.000 description 4
- 230000037303 wrinkles Effects 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000010734 process oil Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920001986 Vinylidene chloride-vinyl chloride copolymer Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 239000004823 Reactive adhesive Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- -1 bromobutyl Chemical group 0.000 description 1
- 229920005557 bromobutyl Polymers 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- YZIPEAHOHOYNCE-UHFFFAOYSA-N chloroethene;1,1-dichloroethene;prop-2-enenitrile Chemical compound ClC=C.C=CC#N.ClC(Cl)=C YZIPEAHOHOYNCE-UHFFFAOYSA-N 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Tyre Moulding (AREA)
- Paints Or Removers (AREA)
- Tires In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、タイヤ内の空気圧保持
性を損なうことなく、タイヤの軽量化を図ると共に、ゴ
ム層との接着性に優れかつ耐久性、耐水性、耐熱性など
に優れた空気透過防止層を有する空気入りタイヤ及びそ
の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention aims to reduce the weight of a tire without impairing the air pressure retaining property in the tire, and also has excellent adhesiveness with a rubber layer and excellent durability, water resistance, heat resistance and the like. The present invention relates to a pneumatic tire having an air permeation preventive layer and a method for manufacturing the same.
【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
イナー層などの空気透過防止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１
mm（１０００μｍ）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 air permeation preventive layer such as an inner liner layer made of rubber having a low gas permeability such as halogenated butyl rubber is provided on the inner surface of a pneumatic tire in order to keep the tire air pressure constant. There is. 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, in addition to the thickness of the inner liner layer of halogenated butyl rubber, the thickness of tie rubber is added to make the total layer 1
The thickness exceeds mm (1000 μm), which is 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など
の空気透過防止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・se
c ・mmHg］が３０℃で１．０×１０-12 以下、７０℃で
５．０×１０-12 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以下の厚さに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 air permeation preventive layer such as an inner liner layer of a pneumatic tire in place of low gas permeable rubber such as butyl rubber. For example, in Japanese Patent Publication No. 47-31761, there is an air permeability coefficient [cm 3 (standard state) / cm · se on the inner surface of a vulcanized tire.
c · mmHg] is 1.0 × 10 −12 or less at 30 ° C. and 5.0 × 10 −12 or less at 70 ° C., a solution or dispersion liquid of a synthetic resin such as polyvinylidene chloride, a saturated polyester resin or a polyamide resin. Application to a thickness of 0.1 mm or less is disclosed.
【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熱性、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 the inner liner layer is inferior in heat resistance and moisture resistance (or water resistance).
【０００６】ところで、塩化ビニリデン系樹脂を空気入
りタイヤの空気透過防止層とした提案はいくつかなされ
ている。例えば、先に述べたように、特公昭４７−３１
７６１号公報には、塩化ビニリデン系樹脂などの合成樹
脂の溶液を塗布したチューブレスタイヤが提案され塩化
ビニリデン−アクリルエステル共重合体が開示されてお
り、また特開平５−２７８４０９号公報には、タイヤ内
周面に、塩化ビニリデン−塩化ビニル共重合体からなる
薄膜、または溶液を塗布し加硫することでインナーライ
ナー層を構成することが提案されている。しかしなが
ら、塩化ビニリデン−アクリルエステル共重合体はＴｇ
が４０℃以下で、長期の耐熱性に劣り、８０℃程度の温
度での長期使用に向かない。塩化ビニリデン−塩化ビニ
ル共重合体は塩素の含有量が多く、熱時に劣化しやす
い。また多くのものは加工性を良くするために１０％以
下の可塑剤を含んでいるが、この可塑剤が移行してフィ
ルムが硬化するなどして物性が低下するので実用的でな
いという問題がある。By the way, some proposals have been made to use vinylidene chloride resin as an air permeation preventive layer for pneumatic tires. For example, as described above, Japanese Patent Publication No.
Japanese Patent No. 761 discloses a tubeless tire coated with a solution of a synthetic resin such as vinylidene chloride resin, and discloses a vinylidene chloride-acrylic ester copolymer, and JP-A-5-278409 discloses a tire. It has been proposed to form an inner liner layer by coating a thin film of a vinylidene chloride-vinyl chloride copolymer or a solution on the inner peripheral surface and vulcanizing. However, the vinylidene chloride-acrylic ester copolymer has a Tg
Is less than 40 ° C, the long-term heat resistance is poor, and it is not suitable for long-term use at a temperature of about 80 ° C. The vinylidene chloride-vinyl chloride copolymer has a high chlorine content and is easily deteriorated when heated. Many of them also contain 10% or less of a plasticizer to improve processability, but this plasticizer migrates and the film hardens and the physical properties deteriorate, which is not practical. .
【０００７】[0007]
【発明が解決しようとする課題】本発明の目的は、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、ゴム層との接着性並びに耐水性や耐熱
性に優れた空気透過防止層を用いた空気入りタイヤ及び
その製造方法を提供することにある。DISCLOSURE OF THE INVENTION An object of the present invention is to enable weight reduction of a tire without impairing the air pressure retention of the tire, and to have excellent adhesiveness with a rubber layer and water resistance and heat resistance. A pneumatic tire using an air permeation preventive layer and a method for manufacturing the pneumatic tire.
【０００８】[0008]
【課題を解決するための手段】本発明に従えば、アクリ
ロニトリル５〜５０モル％を共重合してなる塩化ビニリ
デン−アクリロニトリル共重合体の薄膜で空気透過防止
層を構成してなる空気入りタイヤが提供される。According to the present invention, there is provided a pneumatic tire having an air permeation preventive layer formed of a thin film of vinylidene chloride-acrylonitrile copolymer obtained by copolymerizing 5 to 50 mol% of acrylonitrile. Provided.
【０００９】本発明に従えば、更に、未加硫ゴムからな
るグリーンタイヤのカーカス層の表面又は該カーカス層
の表面に設けた、例えば低気体透過性ゴムからなる空気
透過防止層などのゴム層の表面をハロゲン化処理した面
に、又はハロゲン化処理に代えて（又はハロゲン化処理
に加えて）、該表面に接着剤を塗布した面に、前記塩化
ビニリデン共重合体の溶液を散布又は塗布して、次いで
該グリーンタイヤを加硫せしめて空気透過防止層を構成
することからなる空気入りタイヤの製造方法が提供され
る。According to the present invention, a rubber layer such as an air permeation preventive layer made of, for example, a low gas permeable rubber is further provided on the surface of the carcass layer of the green tire made of unvulcanized rubber or on the surface of the carcass layer. The surface of the vinylidene chloride copolymer is sprayed or applied onto the surface of which the surface is treated with halogen, or in place of the halogenation (or in addition to the halogenation), on the surface of which the adhesive is applied. Then, a method for manufacturing a pneumatic tire is provided, which comprises vulcanizing the green tire to form an air permeation preventive layer.
【００１０】本発明に従えば、更にまた、加硫後のタイ
ヤのカーカス層の表面又は該カーカス層の表面に設け
た、例えば低気体透過性ゴムからなる空気透過防止層な
どのゴム層の表面をハロゲン化処理した面に、又はハロ
ゲン化処理に代えて（又はハロゲン化処理に加えて）、
該表面に接着剤を塗布した面に、前記塩化ビニリデン共
重合体の溶液を散布又は塗布して、前記塩化ビニリデン
共重合体で空気透過防止層を構成することからなる空気
入りタイヤの製造方法が提供される。According to the present invention, the surface of the carcass layer of the tire after vulcanization or the surface of a rubber layer provided on the surface of the carcass layer, such as an air permeation preventive layer made of rubber having low gas permeability. On the surface that has been subjected to the halogenation treatment, or instead of the halogenation treatment (or in addition to the halogenation treatment),
A method for producing a pneumatic tire, comprising spraying or coating a solution of the vinylidene chloride copolymer on the surface coated with an adhesive, and forming an air permeation preventive layer with the vinylidene chloride copolymer. Provided.
【００１１】以下、本発明を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ればその配置は問題では
ない。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 arrangement is not a problem as long as 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.
【００１２】図１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
１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。図１に
おいて４はサイドウォールを示す。FIG. 1 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. 1, 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. In FIG. 1, 4 indicates a sidewall.
【００１３】本発明において空気透過防止層を構成する
塩化ビニリデン共重合体は、前述の如く、必須成分とし
て、塩化ビニリデンとアクリロニトリルを含む共重合体
でアクリロニトリルの含量は全共重合体当り５〜５０モ
ル％、好ましくは１０〜３５モル％である。このアクリ
ロニトリルの含有量が少な過ぎる場合には汎用溶剤への
溶解性に乏しく、多過ぎるとヤング率が高くなり、実用
的でなくなるばかりでなく、実際の共重合体の合成上、
多量のアクリロニトリルを含有させることも難しくなる
ので好ましくない。塩化ビニリデン−アクリロニトリル
共重合体は更に５〜１５モル％の塩化ビニルを含む塩化
ビニリデン−アクリロニトリル−塩化ビニル３元共重合
体を用いてもよい。In the present invention, the vinylidene chloride copolymer constituting the air permeation preventive layer is a copolymer containing vinylidene chloride and acrylonitrile as an essential component as described above, and the content of acrylonitrile is 5 to 50 mol per the total copolymer. %, Preferably 10 to 35 mol%. When the content of this acrylonitrile is too small, it has poor solubility in a general-purpose solvent, and when it is too large, the Young's modulus becomes high, and not only becomes impractical, but on the actual synthesis of the copolymer,
It is also not preferable because it becomes difficult to contain a large amount of acrylonitrile. As the vinylidene chloride-acrylonitrile copolymer, a vinylidene chloride-acrylonitrile-vinyl chloride terpolymer containing 5 to 15 mol% of vinyl chloride may be used.
【００１４】これらの塩化ビニリデン共重合体は、例え
ばキシレン、トルエン、メチルエチルケトン、テトラヒ
ドロフランなどの溶剤、酢酸エチル、酢酸ブチルなどの
エステル系溶剤又はそれらの混合溶剤などの溶媒に可溶
である。These vinylidene chloride copolymers are soluble in, for example, solvents such as xylene, toluene, methyl ethyl ketone and tetrahydrofuran, ester solvents such as ethyl acetate and butyl acetate, and mixed solvents thereof.
【００１５】本発明に従って空気透過防止層を構成する
には、前記塩化ビニリデン−アクリロニトリル共重合体
樹脂を前記したような適当な溶剤中で混合しておいて、
塗布すればよい。溶液中の塩化ビニリデン共重合体の濃
度には塗布などに支障がない限り特に限定はないが、好
ましくは３〜５０重量％、更に好ましくは５〜３０重量
％程度である。この濃度が少な過ぎると付着樹脂量が少
なくて実用的でなく、逆に多過ぎると溶液粘度が高く作
業が困難となる。本発明に従った塩化ビニリデン−アク
リロニトリル共重合体は硬化後厚さ１０〜５０μｍで、
空気透過係数が、２５×１０-12 cc・cm／cm2 ・sec ・
cmHg以下、伸び（加硫後）１０％以上、（加硫前）１１
０％以上で、弾性率が１〜５００MPa の性能を発現す
る。このような塩化ビニリデン共重合体としては、例え
ば、ダウケミカル（株）サランＦ−３１０（アクリロニ
トリル含有量３０ mol％）が利用可能であり、この場
合、５５０％及び２MPa である。To form the air permeation preventive layer according to the present invention, the vinylidene chloride-acrylonitrile copolymer resin is mixed in a suitable solvent as described above,
It may be applied. The concentration of the vinylidene chloride copolymer in the solution is not particularly limited as long as it does not hinder coating and the like, but it is preferably 3 to 50% by weight, more preferably 5 to 30% by weight. If this concentration is too low, the amount of adhered resin is too small to be practical, and if it is too high, the solution viscosity becomes high and the work becomes difficult. The vinylidene chloride-acrylonitrile copolymer according to the present invention has a thickness of 10 to 50 μm after curing,
Air permeability coefficient is 25 × 10 -12 cc · cm / cm 2 · sec
cmHg or less, elongation (after vulcanization) 10% or more, (before vulcanization) 11
When it is 0% or more, the elastic modulus of 1 to 500 MPa is exhibited. As such a vinylidene chloride copolymer, for example, Saran F-310 (Acrylonitrile content 30 mol%) of Dow Chemical Co., Ltd. can be used, and in this case, it is 550% and 2 MPa.
【００１６】本発明に係る空気入りタイヤの第一の製造
方法について、図１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について説明す
ると、未加硫ゴムからなるグリーンタイヤのカーカス層
内面に、ハロゲン処理を施した後又は接着剤を塗布した
後、前記塩化ビニリデン−アクリロニトリル共重合体を
溶液状又は分散液状で散布又は塗布し、次いで、このグ
リーンタイヤを常法に従って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、これに順じて行うことができる。The first method for manufacturing a pneumatic tire according to the present invention will be described with reference to FIG. 1 in which the inner liner layer 3 is arranged inside the carcass layer 2. The green layer is made of unvulcanized rubber. The inner surface of the carcass layer of the tire, after subjected to a halogen treatment or after applying an adhesive, sprayed or applied the vinylidene chloride-acrylonitrile copolymer in a solution or dispersion liquid, then, this green tire according to a conventional method By vulcanizing, a desired lightweight pneumatic tire can be manufactured. When the air permeation preventive layer is provided on the outer peripheral surface of the carcass layer, it can be performed in accordance with this.
【００１７】一方、加硫後のタイヤのカーカス層の表面
又は該カーカス層の表面に設けたゴム層の表面に本発明
に従って空気透過防止層を配置する場合には、常法に従
って加硫した加硫後のカーカス層の表面をハロゲン処理
するか又は接着剤を塗布した後、前記本発明に係る液状
組成物を散布又は塗布し、必要に応じて加熱することに
より早く薄膜を形成せしめることによって所望の空気透
過防止層を有する軽量化空気入りタイヤを製造すること
ができる。On the other hand, when the air permeation preventive layer is arranged according to the present invention on the surface of the carcass layer of the tire after vulcanization or the surface of the rubber layer provided on the surface of the carcass layer, vulcanization according to a conventional method is carried out. After treating the surface of the carcass layer after vulcanization with halogen or applying an adhesive, the liquid composition according to the present invention is sprayed or applied, and if necessary, it is possible to form a thin film quickly by heating to obtain the desired composition. It is possible to manufacture a lightweight pneumatic tire having the air permeation preventive layer.
【００１８】本発明に係る空気入りタイヤの製造方法に
おいてカーカス層の表面に施すハロゲン化処理は従来か
ら一般的に行われている方法によることができ、例えば
一般的なゴムの塩素化処理用溶液、臭素溶液、ヨウ素溶
液などを使用することができる。塩素化処理用溶液には
トリクロロイソシアヌール酸／ＭＥＫ（メチルエチルケ
トン）の９５／５の溶液が例示できる。ここでトリクロ
ロイソシアヌール酸とＭＥＫの混合比は用途に合わせて
変更できることはもちろんである。また、ＭＥＫの代わ
りに酢酸エチルを用いることもできる。In the method for producing a pneumatic tire according to the present invention, the halogenation treatment applied to the surface of the carcass layer can be carried out by a method generally used in the past, for example, a general rubber chlorination treatment solution. , Bromine solution, iodine solution and the like can be used. An example of the chlorination solution is a trichloroisocyanuric acid / MEK (methyl ethyl ketone) 95/5 solution. It goes without saying that the mixing ratio of trichloroisocyanuric acid and MEK can be changed according to the application. Further, ethyl acetate can be used instead of MEK.
【００１９】本発明に係る空気入りタイヤの製造方法に
おいてカーカス層の表面に塗布する接着剤としては、加
熱時の熱で、加硫中にカーカス層のゴム及び空気透過防
止層の樹脂との接着反応が生じる様な反応性の接着剤で
あればよく、具体的にはフェノール系接着剤、塩化ゴム
系接着剤、イソシアネート系接着剤等が挙げられる。The adhesive applied to the surface of the carcass layer in the method of manufacturing a pneumatic tire according to the present invention is heat at the time of heating and adheres to the rubber of the carcass layer and the resin of the air permeation preventive layer during vulcanization. Any reactive adhesive that causes a reaction may be used, and specific examples thereof include a phenol-based adhesive, a chlorinated rubber-based adhesive, and an isocyanate-based adhesive.
【００２０】このような接着剤の好ましい例としては、
フェノール系（例えばロード社製ケムロック ２３４
Ｂ）、塩化ゴム系（例えばロード社製ケムロック ２０
５）、イソシアネート系（例えばロード社製ケムロック
４０２）などを用いることができる。接着剤の使用量
は従前通りで特に限定はない。Preferred examples of such an adhesive include:
Phenolic type (for example, Chemlock 234 manufactured by Road Co.)
B), a chlorinated rubber type (for example, Chemlock 20 manufactured by Lord Co.)
5), an isocyanate type (for example, Chemloc 402 manufactured by Lord Co., Ltd.) and the like can be used. The amount of the adhesive used is the same as before and is not particularly limited.
【００２１】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.
【００２２】本発明に係る空気透過防止層は、軟化点が
８０℃以上、好ましくは１００℃以上で、空気透過係数
が２５×１０-12 cc・cm／cm2 ・sec ・cmHg以下、好ま
しくは０．０５×１０-12 〜１０×１０-12 cc・cm／cm
2 ・sec ・cmHgである。空気透過係数を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 has a softening point of 80 ° C. or higher, preferably 100 ° C. or higher, and an air permeation coefficient of 25 × 10 −12 cc · cm / cm 2 · sec · cmHg or lower, preferably 0.05 x 10 -12 to 10 x 10 -12 cc · cm / cm
2 · sec · cmHg. Air permeability coefficient is 25 × 10 -12
The thickness of the air permeation preventive layer is 1 / th of the thickness of the conventional air permeation preventive layer when cc / cm / cm 2 · sec / cmHg or less.
It can be 2 or less.
【００２３】一方、ヤング率が１〜５００MPa 、好まし
くは１０〜３００MPa 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. If the Young's modulus is less than 1 MPa, it is not preferable because handling becomes difficult due to wrinkles during tire molding, and if it exceeds 500 MPa, tire deformation during running cannot be followed, which is not preferable.
【００２４】[0024]
【実施例】実施例１〜５及び比較例１〜３ 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。EXAMPLES Examples 1 to 5 and Comparative Examples 1 to 3 Hereinafter, the present invention will be described in more detail with reference to Examples, but it goes without saying that the present invention is not limited to the following Examples.
【００２５】なお実施例１〜３、５及び比較例１〜３は
タイヤ加硫後に塩化ビニリデン系樹脂組成物を塗布した
例で、タイヤ加硫機にて１８５℃、１５分、圧力２．３
MPaの条件で常法にて加硫したタイヤの内面をハロゲン
化処理（トリクロロイソシアヌール酸の３．３％の酢酸
エチル溶液を刷毛にて塗布し、２時間乾燥）又は接着剤
塗布（ロード社製ケムロック２０５を刷毛にて塗布し、
２時間乾燥）した後、トルエン３５重量％及びメチルエ
チルケトン６５重量％の混合溶媒に塩化ビニリデン樹脂
を２０重量％の割合で溶解させた溶液をスプレーにて塗
布し、８０℃の温風を２分間当てて乾燥させて、空気透
過防止層を形成した。また、実施例４は、タイヤ加硫前
に塩化ビニリデン系樹脂組成物を塗布した例で、常法に
て成型した未加硫ゴムからなるグリーンタイヤの内面を
上記と同様にハロゲン化処理した後、上記と同様に調整
した溶液を、スプレーにて塗布し、上記と同様に乾燥
し、タイヤ加硫機にて同様の加硫条件で加硫成型した。
さらには、標準例のタイヤは、インナーライナー層とし
て、以下の配合表のブチルゴム組成物を用いた。 ブチルゴム配合（単位：重量部） ───────────────────────── Ｂｒ−ＩＩＲ*1 １００ カーボンブラック（ＧＰＦ）*2 ６０ ステアリン酸 １ 石油系炭化水素樹脂*3 １０ パラフィン系プロセス油*4 １０ ３号ＺｎＯ ３ 促進剤（ＤＭ） １ 硫黄 ０．６ ───────────────────────── ＊１…Ｂｒ−ＩＩＲ：エクソンブロモブチル２２４４、
エクソン化学 ＊２…ＧＰＦ：シーストＶ、東海カーボン ＊３…エスコレッツ１１０２、エッソ化学 ＊４…パラフィン系プロセス油：マシン油２２、昭和シ
ェル石油Examples 1 to 3 and 5 and Comparative Examples 1 to 3 are examples in which the vinylidene chloride resin composition is applied after the tire is vulcanized, and the tire vulcanizer is used at 185 ° C. for 15 minutes at a pressure of 2.3.
The inner surface of the tire vulcanized by a conventional method under MPa condition was halogenated (3.3% ethyl acetate solution of trichloroisocyanuric acid was applied with a brush and dried for 2 hours) or adhesive (Road Co.) Apply Chemlock 205 made with a brush,
After drying for 2 hours), a solution prepared by dissolving 20% by weight of vinylidene chloride resin in a mixed solvent of 35% by weight of toluene and 65% by weight of methyl ethyl ketone is applied by spraying, and warm air at 80 ° C. is applied for 2 minutes. And dried to form an air permeation preventive layer. In addition, Example 4 is an example in which a vinylidene chloride resin composition was applied before tire vulcanization, and after the inner surface of a green tire made of unvulcanized rubber molded by a conventional method was halogenated in the same manner as above. A solution prepared in the same manner as above was applied by spraying, dried in the same manner as above, and vulcanization molded under the same vulcanization conditions using a tire vulcanizer.
Furthermore, in the tire of the standard example, the butyl rubber composition of the following formulation table was used as the inner liner layer. Butyl rubber compound (unit: parts by weight) ───────────────────────── Br-IIR * 1 100 Carbon black (GPF) * 2 60 Stearic acid 1 Petroleum hydrocarbon resin * 3 10 Paraffinic process oil * 4 No. 10 3 ZnO 3 accelerator (DM) 1 Sulfur 0.6 ───────────────────── ──── * 1: Br-IIR: exon bromobutyl 2244,
Exxon Chemical * 2 ... GPF: Seast V, Tokai Carbon * 3 ... Escorets 1102, Esso Chemical * 4 ... Paraffin-based process oil: Machine oil 22, Showa Shell Sekiyu
【００２６】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。The evaluation methods used in the following examples are as follows.
【００２７】溶解性 メチルエチルケトン：トルエンの比が６３：３５（重量
比）からなる混合溶媒１０ccに塩化ビニリデン系樹脂を
２０重量％となる量加え、攪拌して、３０分〜６０分の
うちに溶解する場合を○、溶解しない場合を×とした。 Solubility Methyl ethyl ketone: toluene was added in an amount of 20% by weight of vinylidene chloride resin to 10 cc of a mixed solvent having a ratio of 63:35 (weight ratio), and the mixture was stirred and dissolved in 30 to 60 minutes. When it was done, it was marked with ◯, and when it was not dissolved, it was marked with x.
【００２８】空気透過防止層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 ： フィルムサンプル（Ｉ）（メチルエチル
ケトン／トルエン＝６５／３５（重量比）の混合溶媒
に、塩化ビニリデン系樹脂を２０重量％で溶解し、ドク
ターナイフを用いて、ガラス上にのばし、常温で乾燥
し、さらに真空乾燥して、作成した厚さ約１００μｍの
シート）を用いた。 試験気体 ： 空気（Ｎ2 ：Ｏ2 ＝８：２） 試験温度 ： ３０℃The method for measuring the air permeation coefficient of the air permeation preventive layer was in accordance with JIS K7126 "Method for testing gas permeation rate of plastic films and sheets (method A)". Test piece: Vinylidene chloride resin was dissolved in a mixed solvent of film sample (I) (methylethylketone / toluene = 65/35 (weight ratio) at 20% by weight, and the solution was spread on glass using a doctor knife at room temperature. A sheet having a thickness of about 100 μm was used after drying and further vacuum drying. Test gas: Air (N 2 : O 2 = 8: 2) Test temperature: 30 ° C
【００２９】空気透過防止層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 ： 上で作成したフィルムサンプル（Ｉ）
を、溶液の流れ方向（ドクターナイフで引いた方向）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 method for measuring the Young's modulus of the air permeation preventive layer was based on JIS K6251 "Tensile test method for vulcanized rubber". Test piece: Film sample (I) prepared above
Was punched with a JIS No. 3 dumbbell in parallel with the flow direction of the solution (direction pulled by a doctor knife). Draw a tangent to the curve of the initial strain region of the obtained stress-strain curve,
Young's modulus was calculated from the slope of the tangent line.
【００３０】空気透過防止層の軟化点の測定方法 空気透過防止係数の測定で作成したのと同様の方法で、
厚さ約１mmのシートを用意し、５mm厚さに重ねてＴＭＡ
にて、荷重５ｇ、昇温速度１０℃／min で、圧縮法によ
り測定し、変曲点を軟化点とした。 Method for measuring the softening point of the air permeation preventive layer By the same method as the method for measuring the air permeation preventive coefficient,
Prepare a sheet with a thickness of about 1 mm and stack it to a thickness of 5 mm to TMA
Was measured by the compression method at a load of 5 g and a temperature rising rate of 10 ° C./min, and the inflection point was defined as the softening point.
【００３１】長期耐水性・耐吸湿性試験法 １６５ＳＲ１３ スチールラジアルタイヤ（リム １３
×４1/2 −Ｊ）を用いて、空気圧２００kPa 、荷重５．
５kN及び室温３８℃でφ１７０７mmドラム上で速度８０
km／ｈで走行する。１００００km走行後にタイヤ内面を
目視検査し、インナーライナー層にクラック、目視でき
るしわ、ライナー層の剥離・浮き上がりがあるものを不
合格、ないものを合格と判定する。なお、試験走行の直
前に、タイヤは相対湿度９８％及び室温７０℃で１０日
間放置する。 Long-term water resistance / moisture absorption resistance test method 165SR13 Steel radial tire (rim 13
× 4 1/2 -J), air pressure 200 kPa, load 5.
5kN and room temperature 38 ℃, speed 80 on φ1707mm drum
Drive at km / h. After running 10,000 km, the inner surface of the tire is visually inspected, and cracks in the inner liner layer, visible wrinkles, and peeling / lifting of the liner layer are rejected. Immediately before the test run, the tire is left for 10 days at a relative humidity of 98% and a room temperature of 70 ° C.
【００３２】長期耐久性試験法 １６５ＳＲ１３ スチールラジアルタイヤ（リム １３
×４1/2 −Ｊ）を用い、空気圧２００kPa で１５００cc
クラス乗用車に於いて、４名乗用時相当の荷重（６５kg
／人）を与え実路上を２万km走行する。走行後に、タイ
ヤをリムから外し、タイヤ内面のライナー層を目視観測
し、ライナー層にクラック、目視できるしわ、ライナー
層の剥離・浮き上がりがあるものを不合格、ないものを
合格と判定する。本試験は、ライナー層の強度劣化、接
着劣化等を実車にて総合的に評価することを目的とす
る。 Long-term durability test method 165SR13 Steel radial tire (rim 13
× 41 / 2-J), 1500cc at air pressure of 200kPa
In a passenger car in a class, a load equivalent to that of four passengers (65 kg
/ Person) and drive 20,000 km on the actual road. After running, the tire is removed from the rim, and the liner layer on the inner surface of the tire is visually observed. If the liner layer has cracks, visible wrinkles, or peeling / lifting of the liner layer, it is rejected. The purpose of this test is to comprehensively evaluate the strength deterioration and adhesion deterioration of the liner layer in an actual vehicle.
【００３３】長期耐熱性試験法 １６５ＳＲ１３ スチールラジアルタイヤ（リム １３
×４1/2 −Ｊ）を用い、空気圧２５０kPa 、荷重２．５
kN及び室温４５℃でφ１７０７mmドラム上で、速度１４
０km／ｈにて走行する。２５０００km走行後に、タイヤ
をリムから外し、タイヤ内面のライナー層を目視観測
し、ライナー層にクラック、目視できるしわ、ライナー
層の剥離・浮き上がりがあるものを不合格、ないものを
合格と判定する。なお、試験走行の直前に、タイヤは室
温８０℃以下で１４日間放置する。本試験は、ライナー
層の熱劣化による耐久性を室内ドラム上で再現評価する
ことを目的とする。 Long-term heat resistance test method 165SR13 Steel radial tire (rim 13
X41 / 2-J), air pressure 250kPa, load 2.5
kN and room temperature 45 ° C on φ1707mm drum, speed 14
Drive at 0 km / h. After running 25,000 km, the tire was removed from the rim, the liner layer on the inner surface of the tire was visually observed, and cracks in the liner layer, visible wrinkles, and peeling / lifting of the liner layer were rejected. Immediately before the test run, the tire is left at room temperature of 80 ° C. or lower for 14 days. The purpose of this test is to reproduce and evaluate the durability of the liner layer due to thermal deterioration on an indoor drum.
【００３４】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).
【００３５】タイヤカーカス用ゴム配合 ────────────────────── 品 名 重量部 ────────────────────── 天然ゴム ８０．０ ＳＢＲ１５０２ ２０．０ ＦＥＦカーボンブラック ５０．０ ステアリン酸 ２．０ 亜鉛華 ３．０ 硫 黄 ３．０ 加硫促進剤（ＮＳ） １．０ アロマオイル ２．０ ────────────────────── Rubber compound for tire carcass ────────────────────── Product name Weight part ───────────────── ────── Natural rubber 80.0 SBR1502 20.0 FEF carbon black 50.0 Stearic acid 2.0 Zinc white 3.0 Sulfur yellow 3.0 Vulcanization accelerator (NS) 1.0 Aroma oil 2. 0 ──────────────────────
【００３６】ハロゲン化処理方法 タイヤ加硫前のグリーンタイヤ、もしくは加硫後のタイ
ヤ内面全面を、トリクロロイソシアヌール酸の３．３％
酢酸エチル溶液を塗布し常温で３時間以上放置しハロゲ
ン化処理した。 Halogenation Treatment Method The green tire before vulcanization or the entire inner surface of the tire after vulcanization was treated with 3.3% trichloroisocyanuric acid.
An ethyl acetate solution was applied and left at room temperature for 3 hours or more for halogenation.
【００３７】加硫後のタイヤ内面をハロゲン化処理した
場合の実施例１〜３、未加硫のグリーンタイヤの内面を
ハロゲン化処理した場合の実施例４及び接着剤（ロード
社製ケムロック ２０５）で加硫後のタイヤ内面を処理
した場合の実施例５で得られた結果をそれぞれ以下の表
Ｉに示す。Examples 1 to 3 when the inner surface of the tire after vulcanization was halogenated, Example 4 when the inner surface of an unvulcanized green tire was halogenated, and an adhesive (Chemlock 205 manufactured by Lord Co.) The results obtained in Example 5 when the inner surface of the tire after vulcanization was treated with are shown in Table I below.
【００３８】[0038]
【表１】 [Table 1]
【００３９】[0039]
【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たまま、タイヤ
の軽量化を図ると共に、ゴム層との接着性に優れかつ耐
水性（耐湿性）や耐熱性に優れた空気透過防止層を有す
る空気入りタイヤを得ることができる。As described above, according to the present invention,
While maintaining good air pressure retention in the tire, we aim to reduce the weight of the tire and have an air permeation prevention layer that has excellent adhesion to the rubber layer and excellent water resistance (moisture resistance) and heat resistance. You can get tires.
【図面の簡単な説明】[Brief description of drawings]
【図１】本発明の空気入りタイヤの構造を示す子午線方
向半断面図である。FIG. 1 is a meridional direction half sectional view showing a structure of a 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
Claims (7)
合してなる塩化ビニリデン−アクリロニトリル共重合体
の薄膜で空気透過防止層を構成してなる空気入りタイ
ヤ。1. A pneumatic tire having an air permeation preventive layer formed of a thin film of vinylidene chloride-acrylonitrile copolymer obtained by copolymerizing 5 to 50 mol% of acrylonitrile.
空気透過係数が２５×１０-12 cc・cm／cm2 ・sec ・cm
Hg以下及びヤング率が１〜５００MPa である請求項１に
記載の空気入りタイヤ。2. The softening point of the air permeation preventive layer is 80 ° C. or higher,
Air permeability coefficient is 25 × 10 -12 cc ・ cm / cm 2・ sec ・ cm
The pneumatic tire according to claim 1, wherein the pneumatic tire has a Hg of not more than 1 and a Young's modulus of 1 to 500 MPa.
該カーカス層の表面に設けたゴム層の表面をハロゲン化
処理した後、請求項１に記載の塩化ビニリデン−アクリ
ロニトリル共重合体の溶液を散布又は塗布して空気透過
防止層を形成せしめる空気入りタイヤの製造方法。3. The vinylidene chloride-acrylonitrile copolymer solution according to claim 1, after halogenating the surface of the carcass layer of the tire after vulcanization or the surface of the rubber layer provided on the surface of the carcass layer. A method for producing a pneumatic tire, comprising spraying or applying to form an air permeation preventive layer.
該カーカス層の表面に設けたゴム層の表面に接着剤を散
布又は塗布した後、請求項１に記載の塩化ビニリデン−
アクリロニトリル共重合体の溶液を散布又は塗布して空
気透過防止層を形成せしめることからなる空気入りタイ
ヤの製造方法。4. The vinylidene chloride according to claim 1, after the adhesive is sprinkled or applied on the surface of the carcass layer of the tire after vulcanization or the surface of the rubber layer provided on the surface of the carcass layer.
A method for producing a pneumatic tire, which comprises spraying or applying a solution of an acrylonitrile copolymer to form an air permeation preventive layer.
ーカス層の表面又は該カーカス層の表面に設けたゴム層
の表面をハロゲン化処理した後、請求項１に記載の塩化
ビニリデン−アクリロニトリル共重合体の溶液を散布又
は塗布して加硫せしめ、空気透過防止層を形成せしめる
ことからなる空気入りタイヤの製造方法。5. The vinylidene chloride-acrylonitrile copolymerization according to claim 1, after halogenating the surface of a carcass layer of a green tire made of unvulcanized rubber or the surface of a rubber layer provided on the surface of the carcass layer. A method for producing a pneumatic tire, which comprises spraying or applying a coalescent solution and vulcanizing to form an air permeation preventive layer.
ーカス層の表面又は該カーカス層の表面に設けたゴム層
の表面に接着剤を散布又は塗布した後、請求項１に記載
の塩化ビニリデン−アクリロニトリル共重合体の溶液を
散布又は塗布して加硫せしめ、空気透過防止層を形成せ
しめることからなる空気入りタイヤの製造方法。6. The vinylidene chloride according to claim 1, after the adhesive is sprayed or applied to the surface of the carcass layer of the green tire made of unvulcanized rubber or the surface of the rubber layer provided on the surface of the carcass layer. A method for producing a pneumatic tire, which comprises spraying or applying a solution of an acrylonitrile copolymer and vulcanizing it to form an air permeation preventive layer.
イソシアネート系のいずれかである請求項４又は６に記
載の空気入りタイヤの製造方法。7. The method for producing a pneumatic tire according to claim 4, wherein the adhesive is phenolic, chlorinated rubber or isocyanate.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7051307A JPH08258504A (en) | 1995-01-27 | 1995-03-10 | Pneumatic tire and manufacture thereof |
| EP06006118A EP1669411B1 (en) | 1995-01-27 | 1996-01-25 | Pneumatic tire and process for production thereof |
| EP99114274A EP0952010B1 (en) | 1995-01-27 | 1996-01-25 | Pneumatic tire and process for production thereof |
| EP96101044A EP0723883B1 (en) | 1995-01-27 | 1996-01-25 | Pneumatic tire and process for production thereof |
| US08/591,295 US6024816A (en) | 1995-01-27 | 1996-01-25 | Pneumatic tire and process for production thereof |
| DE69637882T DE69637882D1 (en) | 1995-01-27 | 1996-01-25 | Pneumatic tires and process for its manufacture |
| DE69637877T DE69637877D1 (en) | 1995-01-27 | 1996-01-25 | Pneumatic tires and method of manufacture |
| EP08007365A EP1964890A1 (en) | 1995-01-27 | 1996-01-25 | Pneumatic tire and process for production thereof |
| DE69613494T DE69613494T2 (en) | 1995-01-27 | 1996-01-25 | Pneumatic tires and manufacturing method |
| US09/197,463 US6179941B1 (en) | 1995-01-27 | 1998-11-23 | Pneumatic tire and process for production thereof |
| US09/447,560 US6244317B1 (en) | 1995-01-27 | 1999-11-23 | Pneumatic tire and process for production thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7-11752 | 1995-01-27 | ||
| JP1175295 | 1995-01-27 | ||
| JP7051307A JPH08258504A (en) | 1995-01-27 | 1995-03-10 | Pneumatic tire and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08258504A true JPH08258504A (en) | 1996-10-08 |
Family
ID=26347270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7051307A Pending JPH08258504A (en) | 1995-01-27 | 1995-03-10 | Pneumatic tire and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08258504A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002219904A (en) * | 2001-01-25 | 2002-08-06 | Yokohama Rubber Co Ltd:The | Pneumatic tire |
-
1995
- 1995-03-10 JP JP7051307A patent/JPH08258504A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002219904A (en) * | 2001-01-25 | 2002-08-06 | Yokohama Rubber Co Ltd:The | Pneumatic tire |
| JP4507411B2 (en) * | 2001-01-25 | 2010-07-21 | 横浜ゴム株式会社 | Pneumatic tire |
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