JPS6160101B2 - - Google Patents
Info
- Publication number
- JPS6160101B2 JPS6160101B2 JP3771777A JP3771777A JPS6160101B2 JP S6160101 B2 JPS6160101 B2 JP S6160101B2 JP 3771777 A JP3771777 A JP 3771777A JP 3771777 A JP3771777 A JP 3771777A JP S6160101 B2 JPS6160101 B2 JP S6160101B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- rubber
- sealant
- parts
- divalent metal
- 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.)
- Expired
Links
- 239000000565 sealant Substances 0.000 claims description 59
- 239000000203 mixture Substances 0.000 claims description 43
- 229920001971 elastomer Polymers 0.000 claims description 38
- 239000005060 rubber Substances 0.000 claims description 38
- 229910044991 metal oxide Inorganic materials 0.000 claims description 27
- 150000004706 metal oxides Chemical class 0.000 claims description 27
- 229920001083 polybutene Polymers 0.000 claims description 11
- 229920002367 Polyisobutene Polymers 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 description 15
- 238000004132 cross linking Methods 0.000 description 7
- 230000002265 prevention Effects 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 235000014692 zinc oxide Nutrition 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 230000009969 flowable effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 229920005556 chlorobutyl Polymers 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920005557 bromobutyl Polymers 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- LULCPJWUGUVEFU-UHFFFAOYSA-N Phthiocol Natural products C1=CC=C2C(=O)C(C)=C(O)C(=O)C2=C1 LULCPJWUGUVEFU-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C19/00—Tyre parts or constructions not otherwise provided for
- B60C19/12—Puncture preventing arrangements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
- B29C73/16—Auto-repairing or self-sealing arrangements or agents
- B29C73/163—Sealing compositions or agents, e.g. combined with propellant agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
- B29C73/16—Auto-repairing or self-sealing arrangements or agents
- B29C73/18—Auto-repairing or self-sealing arrangements or agents the article material itself being self-sealing, e.g. by compression
- B29C73/20—Auto-repairing or self-sealing arrangements or agents the article material itself being self-sealing, e.g. by compression the article material only consisting in part of a deformable sealing material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D30/00—Producing pneumatic or solid tyres or parts thereof
- B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
- B29D30/0681—Parts of pneumatic tyres; accessories, auxiliary operations
- B29D30/0685—Incorporating auto-repairing or self-sealing arrangements or agents on or into tyres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D30/00—Producing pneumatic or solid tyres or parts thereof
- B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
- B29D30/0681—Parts of pneumatic tyres; accessories, auxiliary operations
- B29D30/0685—Incorporating auto-repairing or self-sealing arrangements or agents on or into tyres
- B29D2030/0686—Incorporating sealants on or into tyres not otherwise provided for; auxiliary operations therefore, e.g. preparation of the tyre
- B29D2030/069—Incorporating sealants on or into tyres not otherwise provided for; auxiliary operations therefore, e.g. preparation of the tyre through the use of a cylindrical support, e.g. a drum
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は釘などによるタイヤのパンクを防止す
る極めて高シール性の粘着シーラント組成物層を
備えた空気入りタイヤに関するものである。
最近の人命尊重、安全重視の風潮の中で一般の
乗用車タイヤも積極的な改善がなされ、より安全
なタイヤの開発がすすめられている。その一つ
が、チユーブレスタイヤの接地部内面にシーラン
ト層を設けたいわゆる自己シール性タイヤであ
る。この自己シール性タイヤは、ある程度までの
大きさの釘であれば釘が貫通したままの状態で、
長期間、長距離走行しても内圧は低下せず、また
その釘を抜いた場合、あるいは釘が走行中に抜け
た場合にも、釘穴を自動的にシールするため内圧
が低下しないというすぐれた性質を有し、特殊リ
ムを必要としないという利点も兼ね備えている。
しかし、シーラントに釘等への付着性、粘着性を
賦与するためにシーラントの粘度を低くおさえて
いるために、走行によるタイヤの温度上昇と、遠
心力とによりシーラントが流動し、タイヤのバラ
ンス不良をひき起し、車の操縦安定性や乗心地を
損なうという欠点を有している。また、タイヤの
踏面肩部内面のシーラントが中央部へ流動して、
踏面肩部のシール性能を失なうという欠点もあ
る。
本発明者らは以上のような欠点を改良し、より
安全性の高いタイヤを提供するために種々検討し
た結果、非流動性のシーラント層を備えた空気入
りタイヤを完成した。即ち本発明者らはハロゲン
化ゴムやカルボキシル変性スチレン・ブタジエン
共重合体等が二価の金属酸化物により架橋する特
性に着眼し、ハロゲン化ゴムやカルボキシル変性
スチレン・ブタジエン共重合体等の二価の金属酸
化物で架橋し得るゴムを含む炭化水素系ゴムと、
ポリブテンまたはポリイソブチレン系軟化剤と、
二価の金属酸化物とから成るシーラント組成物を
空気入りタイヤに応用して本発明を完成した。
本発明の空気入りタイヤは、二価の金属酸化物
で架橋し得るゴムの群から選ばれる１種もしくは
２種以上のゴムを少なくとも10重量部以上含む炭
化水素系ゴム100重量部と、ポリブテンまたはポ
リイソブチレン系軟化剤から選ばれる１種もしく
は２種の軟化剤60〜200未満重量部と、上記二価
の金属酸化物で架橋し得るゴムの架橋剤として二
価の金属酸化物の群から選ばれる１種もしくは２
種以上の、二価の金属酸化物0.1〜175重量部とを
含む配合組成物から成る非流動性パンク防止用シ
ーラント組成物層をタイヤ本体内面に備えたこと
を特徴とする。
本発明のタイヤに用いられるシーラント組成物
に使用する炭化水素系ゴムは天然ゴム、ポリイソ
プレンゴム、ポリブタジエンゴム、スチレン・ブ
タジエン共重合体等のジエン系ゴム、ブチルゴ
ム、ポリイソブチレン、エチレン・プロピレン共
重合体、エチレン・プロピレン・非共役ジエン共
重合体等である。二価の金属酸化物で架橋し得る
ゴムとしては、塩素化ブチルゴム、臭素化ブチル
ゴム、クロロプレンゴム、塩素化ポリエチレン、
クロルスルフオン化ポリエチレン、エピクロルヒ
ドリンゴム、ジブロモポリブタジエン等のハロゲ
ン化ゴムや、カルボキシル変性スチレンブタジエ
ン共重合体、無水マレイン酸変性ポリイソプレン
ゴム、末端にカルボキシル基を有する液状のポリ
ブタジエンやスチレンブタジエン共重合体、チオ
コール等があるが、塩素化ブチルゴムや臭素化ブ
チルゴムが好ましい。これらの二価の金属酸化物
で架橋し得るゴムは１種のみを用いても、また２
種以上をブレンドしてもよいが、少なくとも10重
量部以上、好ましくは25重量部以上含まねばなら
ない。二価の金属酸化物で架橋し得るゴムの量が
10重量部より少ない場合は、二価の金属酸化物に
よる架橋が不十分であるため、この組成物から成
るシーラント組成物層を備えたタイヤは、走行に
より、シーラントが流動する結果となる。
次に、ポリブテンは市販されているものは平均
分子量が3000以下の粘稠な液体であるが、これを
加えることにより当該シーラント組成物を軟化
し、本発明によるタイヤのパンクシール効果が向
上する。低分子量のポリプテンを当該シーラント
組成物に配合すると、第１図に示すポリブテンが
シーラント組成物層２に隣接するインナーライナ
ー３、更にはカーカス４へ移行して、これらのシ
ーラント層の物性を低下させることがあるため、
ポリブテンの平均分子量は800以上であることが
好ましい。
また、ポリイソブチレン系軟化剤は市販のもの
はStaudinger粘度平均分子量で約20000以下の粘
稠な流動体のもので、これを加えることにより、
当該シーラント組成物を軟化し、また、本発明に
よるタイヤのパンクシール効果が向上する。当該
シーラント組成物に加えるポリブテンまたはポリ
イソブチレン系軟化剤の量は60〜200未満重量
部、好ましくは80〜200未満重量部である。ポリ
ブテンまたはポリイソブチレン系軟化剤量が60重
量部未満の場合は粘着性、釘等への付着性に乏し
く、200重量部より多い場合には、シーラント組
成物の粘度が非常に低く、また軟化剤の混入時に
二価の金属酸化物で架橋し得るゴムとの混練が著
しく困難になる等の如く加工上不利であり、ま
た、このような低粘度のシーラント組成物層はタ
イヤ内面に備えたタイヤは走行によりシーラント
が流動する結果となる。なおポリブテンまたはポ
リイソブチレン系軟化剤は単独で用いても併用し
てもよい。
次に二価の金属酸化物としては、一般にゴム用
の無機加硫剤として用いられる亜鉛華、リサー
ジ、マグネシアや、酸化カドミニウム、酸化ニツ
ケル、酸化第一スズ、酸化カルシウム等を用い、
２種類以上を併用しても良い。加える二価の金属
酸化物の量は0.1重量部から175重量部、好ましく
は0.1重量部から125重量部である。二価の金属酸
化物量が0.1重量部より少ない場合は、架橋密度
が低すぎるため、非流動性シーラントは形成され
ない。また二価の金属酸化物量が175重量部より
多い場合には、シーラント組成物層の粘度が非常
に高くなり、粘着性や釘等への付着性等のパンク
防止用シーラントとしての性能が損なわれる。
当然シーラント組成物にはハロゲン化ゴムを含
むゴム、ポリブテンまたはポリイソブチレン系軟
化剤、二価の金属酸化物の他に必要に応じて、ス
テアリン酸等の脂肪等、無機充填剤等を加えても
よい。
脂肪酸は10重量部以下、好ましくは５重量部以
下に用いる。脂肪酸を添加することにより、ニー
ダー等で加工する際の加工性が改良されるが、添
加量が10重量部より多い場合には、離型剤として
の性質が顕著になり釘等への付着性が低下しパン
クシール性能が損なわれる。脂肪酸を添加するこ
とにより、ハロゲン化ゴムの二価の金属酸化物に
よる架橋が促進されるため、二価の金属酸化物の
添加量が少ない場合や、炭化水素系ゴム中におけ
るハロゲン化ゴムの含量が低い場合に脂肪酸を併
用することが好ましい。無機充填剤は60重量部以
下を加えてもよいが、これより多い場合にはパン
ク防止用シーラントとしての性能が低下する。用
いる無機充填剤は、カーボンブラツク、シリカ、
炭酸カルシウム等一般ゴム用に用いられるもので
あれば何でもよく、二種類以上を併用しても差支
えがない。
本発明の非流動性パンク防止用粘着シーラント
組成物層を備えた空気入りタイヤの製造は例えば
以下のようにして行なうことができる。
上述のシーラント組成物はニーダー等により練
ることができ、押出機により任意の形状のシート
に押出すことが可能である。また金型を作成し、
100℃程度の温度で短時間プレスすることにより
シート化することも可能である。
生タイヤ成型に際しては、第２図に示す成型機
５上にカバーゴム６を貼り、その上に当該シーラ
ント組成物シート７を貼り、更にその上にカバー
ゴム８を貼り、以後は通常のチユーブレスタイヤ
の成型法に従つて成型する。前記カバーゴム６、
シート７及びカバーゴム８は予め貼り合せたサン
ドイツチ構造のものを作つておくこともでき、ま
た場合によつては外側のカバーゴム８は省いても
よい。このようにして得られた生タイヤの加硫は
通常の方法で行なうことができるが、加硫時間は
若干長くする必要がある。タイヤ加硫中にタイヤ
本体はイオウ等により加硫するが、当該シーラン
ト組成物は、含まれる二価の金属酸化物により架
橋し、粘着性および釘等への付着性と非流動性と
を兼ね備えたパンク防止用シーラント組成物層２
を形成する。
また、本発明のタイヤの製造は次の方法でも行
なうことができる。上述のシーラント組成物を金
型によるプレス加熱で、ハロゲン化ゴムと二価の
金属酸化物との架橋反応と、シート化とを同時に
行ない、得られたシートを加硫済みのタイヤの内
面に貼り付ける。この際、適当な接着剤を用いて
もよい。シーラント組成物層の厚さは、パンクシ
ール性能に大きな影響を及ぼすが、タイヤ性能、
生産性とを考慮すれば１〜４mmであることが好ま
しい。
本発明に関する実施例は、以下に詳細に説明す
る。
実施例 １
パンク防止用シーラントとして有効な配合ゴム
組成物を得るために、軟化剤の変量テストを行な
つた。即ち、表１に示すシーラント組成物を小型
ニーダーで練り、釘への付着性および室温におけ
る流動性をしらべた。軟化剤量（ポリブテンと流
動性ポリイソブチレンの合計量）が50重量部以下
では、シーラント組成物の釘への付着性は乏し
く、60重量部以上では良好であつた。しかし軟化
剤量が200を越えると、釘への付着性は大である
が、非常に流動性が大きく、取扱いが困難であつ
た。なお、釘への付着性は次のようにしてしらべ
た。
The present invention relates to a pneumatic tire equipped with an adhesive sealant composition layer having extremely high sealing properties to prevent the tire from being punctured by nails or the like. With the recent trend of respecting human life and emphasizing safety, general passenger car tires are being actively improved, and safer tires are being developed. One of these is a so-called self-sealing tire, in which a sealant layer is provided on the inner surface of the ground-contacting part of a tubeless tire. This self-sealing tire allows nails of up to a certain size to penetrate,
The internal pressure does not drop even if the car is driven for a long time and over long distances, and even if the nail is pulled out or the nail falls out while driving, the nail hole is automatically sealed, so the internal pressure does not drop. It also has the advantage of not requiring a special rim.
However, because the viscosity of the sealant is kept low in order to give it adhesion and stickiness to nails, etc., the increase in temperature of the tire during driving and centrifugal force causes the sealant to flow, resulting in poor tire balance. This has the disadvantage of causing problems in the handling stability and ride comfort of the vehicle. In addition, the sealant on the inner surface of the tire's tread shoulder flows toward the center,
Another disadvantage is that the sealing performance of the tread shoulder is lost. The present inventors conducted various studies to improve the above-mentioned drawbacks and provide a safer tire, and as a result, they completed a pneumatic tire equipped with a non-flowable sealant layer. That is, the present inventors focused on the property that halogenated rubber and carboxyl-modified styrene-butadiene copolymers, etc. are crosslinked by divalent metal oxides. a hydrocarbon rubber containing a rubber that can be crosslinked with a metal oxide;
A polybutene or polyisobutylene softener,
The present invention was completed by applying a sealant composition comprising a divalent metal oxide to a pneumatic tire. The pneumatic tire of the present invention comprises 100 parts by weight of a hydrocarbon rubber containing at least 10 parts by weight of one or more rubbers selected from the group of rubbers that can be crosslinked with divalent metal oxides, and polybutene or 60 to less than 200 parts by weight of one or two softeners selected from polyisobutylene-based softeners, and a crosslinking agent for rubber that can be crosslinked with the divalent metal oxides selected from the group of divalent metal oxides. type 1 or 2
The present invention is characterized in that the inner surface of the tire body is provided with a non-flowable puncture-preventing sealant composition layer made of a compounded composition containing 0.1 to 175 parts by weight of divalent metal oxides of at least 100% of divalent metal oxides. The hydrocarbon rubber used in the sealant composition used in the tire of the present invention is natural rubber, polyisoprene rubber, polybutadiene rubber, diene rubber such as styrene-butadiene copolymer, butyl rubber, polyisobutylene, ethylene-propylene copolymer. ethylene/propylene/non-conjugated diene copolymers, etc. Rubbers that can be crosslinked with divalent metal oxides include chlorinated butyl rubber, brominated butyl rubber, chloroprene rubber, chlorinated polyethylene,
Halogenated rubbers such as chlorosulfonated polyethylene, epichlorohydrin rubber, and dibromopolybutadiene, carboxyl-modified styrene-butadiene copolymers, maleic anhydride-modified polyisoprene rubbers, liquid polybutadiene and styrene-butadiene copolymers with carboxyl groups at the ends, Examples include thiocol, but chlorinated butyl rubber and brominated butyl rubber are preferred. Rubbers that can be crosslinked with these divalent metal oxides can be crosslinked even if only one type is used or two types can be crosslinked.
Although more than one species may be blended, the content must be at least 10 parts by weight, preferably 25 parts by weight or more. The amount of rubber that can be crosslinked with divalent metal oxides is
If it is less than 10 parts by weight, the crosslinking by the divalent metal oxide will be insufficient, resulting in the sealant flowing in a tire equipped with a sealant composition layer made of this composition when running. Next, commercially available polybutene is a viscous liquid with an average molecular weight of 3000 or less, and adding it softens the sealant composition and improves the puncture sealing effect of the tire according to the present invention. When low molecular weight polyptene is blended into the sealant composition, the polybutene shown in FIG. 1 migrates to the inner liner 3 adjacent to the sealant composition layer 2 and further to the carcass 4, reducing the physical properties of these sealant layers. Because of this,
The average molecular weight of the polybutene is preferably 800 or more. In addition, commercially available polyisobutylene softeners are viscous fluids with a Staudinger viscosity average molecular weight of approximately 20,000 or less, and by adding this,
The sealant composition is softened and the puncture sealing effect of the tire according to the present invention is improved. The amount of polybutene or polyisobutylene softener added to the sealant composition is from 60 to less than 200 parts by weight, preferably from 80 to less than 200 parts by weight. If the amount of the polybutene or polyisobutylene softener is less than 60 parts by weight, the adhesiveness and adhesion to nails, etc. will be poor, and if it is more than 200 parts by weight, the viscosity of the sealant composition will be very low, and the softener When a sealant composition layer of this type is mixed in, it becomes extremely difficult to knead with rubber that can be crosslinked with a divalent metal oxide, which is disadvantageous in terms of processing. This results in the sealant flowing due to driving. Note that the polybutene or polyisobutylene softeners may be used alone or in combination. Next, as divalent metal oxides, zinc white, litharge, magnesia, which are generally used as inorganic vulcanizing agents for rubber, cadmium oxide, nickel oxide, stannous oxide, calcium oxide, etc. are used.
Two or more types may be used together. The amount of divalent metal oxide added is from 0.1 parts by weight to 175 parts by weight, preferably from 0.1 parts by weight to 125 parts by weight. If the amount of divalent metal oxide is less than 0.1 parts by weight, the crosslinking density is too low and no non-flowable sealant is formed. In addition, if the amount of divalent metal oxide is more than 175 parts by weight, the viscosity of the sealant composition layer becomes extremely high, and its performance as a puncture prevention sealant such as stickiness and adhesion to nails etc. is impaired. . Of course, in addition to rubber including halogenated rubber, polybutene or polyisobutylene softeners, and divalent metal oxides, fats such as stearic acid, inorganic fillers, etc. may also be added to the sealant composition as necessary. good. The fatty acid is used in an amount of 10 parts by weight or less, preferably 5 parts by weight or less. Addition of fatty acids improves processability when processing with a kneader, etc., but if the amount added is more than 10 parts by weight, its properties as a mold release agent become significant and the adhesion to nails etc. decreases and puncture sealing performance is impaired. Adding fatty acids promotes crosslinking of halogenated rubber with divalent metal oxides, so when the amount of divalent metal oxides added is small, or when the content of halogenated rubber in hydrocarbon rubber is It is preferable to use fatty acids in combination when the The inorganic filler may be added in an amount of 60 parts by weight or less, but if the amount is more than 60 parts by weight, the performance as a puncture prevention sealant will deteriorate. The inorganic fillers used are carbon black, silica,
Any material used for general rubber such as calcium carbonate may be used, and there is no problem even if two or more kinds are used in combination. A pneumatic tire equipped with the non-flowable puncture-preventing pressure-sensitive adhesive sealant composition layer of the present invention can be produced, for example, as follows. The above-mentioned sealant composition can be kneaded using a kneader or the like, and extruded into a sheet of any shape using an extruder. We also created a mold,
It is also possible to form a sheet by pressing at a temperature of about 100°C for a short time. When molding a green tire, a cover rubber 6 is pasted on the molding machine 5 shown in FIG. Mold according to the tire molding method. the cover rubber 6;
The sheet 7 and cover rubber 8 may be bonded together in advance to form a sandwich structure, or the outer cover rubber 8 may be omitted in some cases. The green tire thus obtained can be vulcanized by a conventional method, but the vulcanization time needs to be slightly longer. During tire vulcanization, the tire body is vulcanized by sulfur, etc., and the sealant composition is crosslinked by the divalent metal oxide contained therein, and has both adhesiveness and adhesion to nails, etc., and non-flowability. Puncture prevention sealant composition layer 2
form. Further, the tire of the present invention can also be manufactured by the following method. The above-mentioned sealant composition is press-heated with a mold to simultaneously perform a crosslinking reaction between the halogenated rubber and the divalent metal oxide and to form a sheet, and the resulting sheet is applied to the inner surface of a vulcanized tire. wear. At this time, a suitable adhesive may be used. The thickness of the sealant composition layer has a large effect on puncture sealing performance, but it also affects tire performance,
In consideration of productivity, the thickness is preferably 1 to 4 mm. Embodiments of the invention are described in detail below. Example 1 A softener variation test was conducted to obtain a compounded rubber composition effective as a puncture protection sealant. That is, the sealant compositions shown in Table 1 were kneaded in a small kneader, and their adhesion to nails and fluidity at room temperature were examined. When the amount of softener (total amount of polybutene and fluid polyisobutylene) was less than 50 parts by weight, the sealant composition had poor adhesion to nails, and when it was more than 60 parts by weight, it was good. However, when the amount of softener exceeds 200%, the adhesion to nails is high, but the fluidity is very high and handling is difficult. The adhesion to nails was determined as follows.
【表】【table】
【表】
小型ニーダーで練つたシーラント組成物を金型
に入れて100℃、10分間プレスして厚さ３mmのシ
ートに成型し、これに直径３mmの釘をさし込み、
引抜いたときのシーラント組成物の付着量を目視
により判定した。
実施例 ２
非流動性シーラントを得るために亜鉛華の変量
テストを行なつた。表２に示すシーラント組成物
を小型ニーダーで練り、得られたシーラント組成
物からJIS １号型ダンベル状試験片を作製し、最
大応力を測成した。また東洋精機製作所製タツク
ネステスターにより粘着荷重を測定し、更に、シ
ーラント組成物のキシレンへの溶解性をもしらべ
た。[Table] The sealant composition kneaded in a small kneader was put into a mold and pressed at 100℃ for 10 minutes to form a sheet with a thickness of 3 mm, into which a nail with a diameter of 3 mm was inserted.
The amount of sealant composition adhered to the sample when it was pulled out was visually determined. Example 2 A variable test of zinc white was conducted to obtain a non-flowing sealant. The sealant composition shown in Table 2 was kneaded in a small kneader, and a JIS No. 1 dumbbell-shaped test piece was prepared from the obtained sealant composition, and the maximum stress was measured. In addition, the adhesive load was measured using a toughness tester manufactured by Toyo Seiki Seisakusho, and the solubility of the sealant composition in xylene was also examined.
【表】
上表から明らかなように、亜鉛華を0.1重量部
加えても塩素化ブチルゴムの架橋がおこり、非流
動性パンク防止用シーラントとしての性能を備え
ている。しかし、亜鉛華量が175重量部を越えて
200重量部近くになると、配合ゴム組成物の強度
が極端に高くなりパンク防止用シーラントとして
の性能は失なわれた。
実施例 ３
各種の金属酸化物を用いて、非流動性シーラン
トを形成するか否かをしらべた。表３に示すシー
ラント組成物を小型ニーダーで練り、得られたシ
ーラント組成物を175℃で20分プレス加熱したも
のについてキシレンへの溶解性をしらべた。これ
らの結果は表３に示した。亜鉛華、酸化カルシウ
ム、マグネシア、リサージは架橋がおこるが、酸
化チタンでは架橋がおこらず、非流動性シーラン
トを得られない。[Table] As is clear from the above table, crosslinking of chlorinated butyl rubber occurs even when 0.1 part by weight of zinc white is added, and it has the performance as a non-flowing puncture prevention sealant. However, if the amount of zinc exceeds 175 parts by weight,
When the amount was close to 200 parts by weight, the strength of the compounded rubber composition became extremely high and its performance as a puncture prevention sealant was lost. Example 3 Various metal oxides were used to determine whether they would form a non-flowing sealant. The sealant compositions shown in Table 3 were kneaded in a small kneader, and the resulting sealant compositions were press-heated at 175° C. for 20 minutes and their solubility in xylene was examined. These results are shown in Table 3. Zinc white, calcium oxide, magnesia, and litharge cause crosslinking, but titanium oxide does not cause crosslinking, making it impossible to obtain a non-flowing sealant.
【表】【table】
【表】
表４に示すシーラント組成物を小型ニーダーで
練り、得られたシーラント組成物を175℃で20分
間プレス加熱したもののキシレン溶解性を調べ
た。表４の結果は全ゴム中のハロゲン化ゴム量が
25％以上であればキシレン不溶で亜鉛華により架
橋をしていることを示している。
実施例 ５
各種のパンク防止用粘着シーラント組成物層を
備えたタイヤを作り、そのパンクシール性能と、
シーラント組成物層の走行による流動性とをしら
べた。静的パンクシール性能は次のようにしてし
らべた。即ち、所定内圧（1.7Kg／cm2）を充填し
たタイヤに直径3.1mmおよび4.1mmの鉄釘をトレツ
ド中央部の溝に内部まで貫通するように打込み、
５分放置後釘を引抜き、24時間後の内圧を測定し
た。動的パンクシール性能は次の方法でしらべ
た。所定内圧（1.7Kg／cm2）を充填したタイヤに
直径3.1mmの鉄釘をトレツド中央部の溝、および
トレツド肩部の溝にそれぞれ２本ずつ、内部まで
貫通するように打込みドラム走行試験機で80Km／
hrの速度で1500Km連続走行させた。それからトレ
ツド中央部の釘を抜き24時間物の内圧を測定し
て、更にトレツド肩部の釘を抜き、24時間後の内
圧を測定して、空気もれの有無を確認した。ま
た、テスト終了後、シーラント組成物層の流動状
態を観察した。これらの結果を表５にまとめた。[Table] The sealant composition shown in Table 4 was kneaded in a small kneader, and the resulting sealant composition was press-heated at 175° C. for 20 minutes, and the solubility in xylene was examined. The results in Table 4 show that the amount of halogenated rubber in the total rubber is
If it is 25% or more, it indicates that it is insoluble in xylene and is crosslinked by zinc white. Example 5 Tires equipped with various puncture prevention adhesive sealant composition layers were made, and their puncture sealing performance and
The fluidity of the sealant composition layer during running was examined. Static puncture seal performance was examined as follows. That is, iron nails with diameters of 3.1 mm and 4.1 mm were driven into a tire filled with a predetermined internal pressure (1.7 kg/cm 2 ) into a groove in the center of the tread so that they penetrated into the tire.
After leaving it for 5 minutes, the nail was pulled out and the internal pressure was measured 24 hours later. Dynamic puncture sealing performance was investigated using the following method. Two iron nails with a diameter of 3.1 mm are inserted into the groove of the center of the tread and the groove of the shoulder of the tread so that they penetrate inside the tire filled with the specified internal pressure (1.7 Kg/cm 2 ). 80km/
I ran it continuously for 1500km at a speed of hr. Then, the nail at the center of the tread was removed and the internal pressure was measured for 24 hours.The nail at the shoulder of the tread was also removed and the internal pressure was measured 24 hours later to check for air leaks. Furthermore, after the test was completed, the flow state of the sealant composition layer was observed. These results are summarized in Table 5.
【表】
Ａ〜Ｅおよび比較例１〜４のすべてのタイヤは
静的パンクシール性能においては差がみられな
い。動的パンクシール性能と、シーラントの流動
に関しては、本発明に基づくタイヤＡ〜Ｅと比較
例とでは大きな差が見られる。
すなわち、本発明に基づくＡ〜Ｅのタイヤは、
シーラントの走行による流動がなく、トレツド中
央部、肩部のいずれもパンクシール効果を有して
いるのに対して、本発明の構成要素を欠いた比較
例１、２および市販のシールタイヤである比較例
３、４はシーラントの流動が大きくトレツド肩部
のパンクシール性能が失われている。
これらの結果から本発明によるタイヤは走行に
よるシーラントの流動がなく、すぐれたパンクシ
ール性能を有するものであることが明らかであ
る。[Table] There is no difference in static puncture sealing performance between all tires A to E and Comparative Examples 1 to 4. Regarding dynamic puncture sealing performance and sealant flow, there are large differences between tires A to E based on the present invention and the comparative example. That is, tires A to E based on the present invention are:
The sealant does not flow due to running and has a puncture sealing effect in both the center and shoulder areas of the tread, whereas Comparative Examples 1 and 2 and commercially available sealed tires lack the constituent elements of the present invention. In Comparative Examples 3 and 4, the flow of the sealant was large and the puncture sealing performance at the tread shoulder was lost. From these results, it is clear that the tire according to the present invention has excellent puncture sealing performance without any flow of sealant due to running.
第１図は本発明による空気入りタイヤの断面図
で、第２図はタイヤ成型方法の概略図である。
１……カバーゴム、２……シーラント組成物
層、３……インナーライナー、４……カーカス、
５……成型機、６……カバーゴム、７……シーラ
ント組成物シート、８……カバーゴム。
FIG. 1 is a sectional view of a pneumatic tire according to the present invention, and FIG. 2 is a schematic diagram of a tire molding method. 1... Cover rubber, 2... Sealant composition layer, 3... Inner liner, 4... Carcass,
5... Molding machine, 6... Cover rubber, 7... Sealant composition sheet, 8... Cover rubber.
Claims (1)
選ばれる１種もしくは２種以上のゴムを少なくと
も10重量部以上含む炭化水素系ゴム100重量部
と、ポリブテンまたはポリイソブチレン系軟化剤
から選ばれる１種もしくは２種の軟化剤60〜200
未満重量部と、上記二価の金属酸化物で架橋し得
るゴムの架橋剤として二価の金属酸化物の群から
選ばれる１種もしくは２種以上の二価の金属酸化
物0.1〜175重量部とを含む配合組成物から成る非
流動性パンク防止用シーラント組成物層をタイヤ
本体内面に備えたことを特徴とする非流動性パン
ク防止用シーラント組成物層を備えた空気入りタ
イヤ。1 100 parts by weight of a hydrocarbon rubber containing at least 10 parts by weight of one or more rubbers selected from the group of rubbers that can be crosslinked with divalent metal oxides, and a softener selected from polybutene or polyisobutylene. One or two types of softener 60 to 200
and 0.1 to 175 parts by weight of one or more divalent metal oxides selected from the group of divalent metal oxides as a crosslinking agent for rubber that can be crosslinked with the divalent metal oxides. 1. A pneumatic tire equipped with a non-flowing puncture-preventing sealant composition layer comprising a non-flowing puncture-preventing sealant composition layer on the inner surface of the tire body, the layer comprising a blended composition comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3771777A JPS53124803A (en) | 1977-04-01 | 1977-04-01 | Pneumatic tire with layer of punctureepreventing nonnfluidic sealant compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3771777A JPS53124803A (en) | 1977-04-01 | 1977-04-01 | Pneumatic tire with layer of punctureepreventing nonnfluidic sealant compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS53124803A JPS53124803A (en) | 1978-10-31 |
| JPS6160101B2 true JPS6160101B2 (en) | 1986-12-19 |
Family
ID=12505257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3771777A Granted JPS53124803A (en) | 1977-04-01 | 1977-04-01 | Pneumatic tire with layer of punctureepreventing nonnfluidic sealant compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS53124803A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0425605Y2 (en) * | 1987-03-26 | 1992-06-19 |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57195760A (en) * | 1981-05-29 | 1982-12-01 | Toyo Tire & Rubber Co Ltd | Heat-resistant rubber composition |
| US4665963A (en) * | 1983-06-01 | 1987-05-19 | Polysar Limited | Pneumatic tire inner liner having puncture sealing characteristics |
| GB2236534B (en) * | 1989-09-29 | 1993-02-03 | Day Jiann Jinn | A tyre |
| JP3961042B2 (en) * | 1995-03-15 | 2007-08-15 | 藤倉ゴム工業株式会社 | Cable sealant |
| JP3917314B2 (en) * | 1999-02-01 | 2007-05-23 | 住友ゴム工業株式会社 | Pneumatic tire and method for manufacturing pneumatic tire |
| JP4167340B2 (en) * | 1999-03-08 | 2008-10-15 | 住友ゴム工業株式会社 | Pneumatic tire and method for manufacturing pneumatic tire |
| JP4409814B2 (en) * | 2001-09-26 | 2010-02-03 | 横浜ゴム株式会社 | Pneumatic tire having an adhesive sealant layer and method for producing the same |
| JP3593526B2 (en) * | 2002-05-31 | 2004-11-24 | 須賀工業株式会社 | Rubber composition and molded product thereof |
| JP3747212B2 (en) * | 2004-06-21 | 2006-02-22 | 須賀工業株式会社 | Molded product of rubber composition |
| FR3002490B1 (en) * | 2013-02-25 | 2015-03-27 | Michelin & Cie | SELF-SWITCHING PNEUMATIC HAVING ADDITIONAL FLANK FRAME |
| WO2017179576A1 (en) * | 2016-04-14 | 2017-10-19 | 住友ゴム工業株式会社 | Rubber composition for pneumatic tires |
| JP6583456B2 (en) * | 2018-03-20 | 2019-10-02 | 横浜ゴム株式会社 | SEALANT MATERIAL COMPOSITION AND PNEUMATIC TIRE |
-
1977
- 1977-04-01 JP JP3771777A patent/JPS53124803A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0425605Y2 (en) * | 1987-03-26 | 1992-06-19 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS53124803A (en) | 1978-10-31 |
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