JP6720874B2 - How to use a tire vulcanization bladder - Google Patents
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- JP6720874B2 JP6720874B2 JP2016562664A JP2016562664A JP6720874B2 JP 6720874 B2 JP6720874 B2 JP 6720874B2 JP 2016562664 A JP2016562664 A JP 2016562664A JP 2016562664 A JP2016562664 A JP 2016562664A JP 6720874 B2 JP6720874 B2 JP 6720874B2
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- 238000004073 vulcanization Methods 0.000 title claims description 32
- 229920005549 butyl rubber Polymers 0.000 claims description 39
- 229920001971 elastomer Polymers 0.000 claims description 38
- 239000005060 rubber Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000005011 phenolic resin Substances 0.000 claims description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- 230000002093 peripheral effect Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000013329 compounding Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 241000079947 Lanx Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
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- 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
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/02—Moulds or cores; Details thereof or accessories therefor with incorporated heating or cooling means
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L11/00—Compositions of homopolymers or copolymers of chloroprene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、加硫ブラダーの製造に用いるゴム組成物およびそれを用いたタイヤ加硫ブラダーに関する。 The present invention relates to a rubber composition used for producing a vulcanization bladder and a tire vulcanization bladder using the rubber composition.
一般に空気入りタイヤは、未加硫タイヤを加硫金型に装入し、その未加硫タイヤの内腔にゴム袋状の加硫ブラダーを挿入し、該加硫ブラダー内にスチーム等の加熱加圧媒体を圧入して膨張させ、未加硫タイヤの外面を加硫金型の内面に押圧しながら加硫を行なう工程を経て製造される。
加硫ブラダーを繰り返し使用すると、コンパウンドの熱老化やタイヤから移行してくる硫黄によりゴム同士が架橋して硬くなり、クラックを生じさせ、ブラダーライフ（ブラダーの使用寿命）が終了する。
そこでブラダーライフを延長させるために、当業界では様々な試みがなされている。
例えば下記特許文献１には、複数層からなるタイヤ製造用ブラダーであって、シリコーンゴム組成物を含む最外層と、ブチルゴム組成物を含むブチルゴム層と、を有し、前記最外層と前記ブチルゴム層との間に、シリコーンゴム組成物と樹脂化合物とを含む中間層を有するタイヤ製造用ブラダーが開示されている。
しかし、前記のような従来技術では多層構成であるためにその製造に手間がかかるとともに所望のブラダーライフを得るには至らなかった。Generally, for pneumatic tires, an unvulcanized tire is loaded into a vulcanizing mold, a rubber bag-shaped vulcanizing bladder is inserted into the inner cavity of the unvulcanizing tire, and heating of steam or the like is performed in the vulcanizing bladder. It is manufactured through a process in which a pressurizing medium is press-fitted and expanded to press the outer surface of the unvulcanized tire against the inner surface of the vulcanizing mold to perform vulcanization.
When the vulcanization bladder is repeatedly used, the rubber is crosslinked and hardened due to heat aging of the compound and sulfur migrating from the tire, causing cracks and ending the bladder life (use life of the bladder).
Therefore, various attempts have been made in the art to extend the bladder life.
For example, in Patent Document 1 below, a bladder for tire production comprising a plurality of layers, having an outermost layer containing a silicone rubber composition and a butyl rubber layer containing a butyl rubber composition, the outermost layer and the butyl rubber layer A bladder for tire production having an intermediate layer containing a silicone rubber composition and a resin compound between the two is disclosed.
However, in the above-mentioned conventional technology, since it has a multi-layered structure, it takes time and effort to manufacture it, and it has not been possible to obtain a desired bladder life.
したがって本発明の目的は、従来技術よりも簡単な方法で、タイヤ加硫ブラダーに求められる物性を損なうことなく、ブラダーライフを大幅に延長することのできる、タイヤ加硫ブラダー用ゴム組成物およびそれを用いたタイヤ加硫ブラダーを提供することにある。 Therefore, the object of the present invention is a rubber composition for a tire vulcanizing bladder, which can greatly extend the bladder life without impairing the physical properties required for a tire vulcanizing bladder, by a method simpler than the prior art. It is to provide a tire vulcanizing bladder using.
本発明者らは鋭意研究を重ねた結果、特定の不飽和度を有するブチルゴムを特定量で配合することにより、上記課題を解決できることを見出し、本発明を完成することができた。 As a result of intensive studies, the present inventors have found that the above problem can be solved by compounding a butyl rubber having a specific degree of unsaturation in a specific amount, and have completed the present invention.
すなわち本発明は以下の通りである。
１．ブチルゴムを９２質量部以上含むゴム成分１００質量部に対し、前記ブチルゴムが、０．６〜１．１％の不飽和度を有するブチルゴム（１）３０〜１００質量％および１．５〜２．０％の不飽和度を有するブチルゴム（２）０〜７０質量％から構成されることを特徴とするタイヤ加硫ブラダー用ゴム組成物。
２．前記ブチルゴム（１）の不飽和度が、０．６〜１．０％であることを特徴とする前記１に記載のタイヤ加硫ブラダー用ゴム組成物。
３．前記ゴム成分が、ブチルゴム９２〜９７質量部およびクロロプレンゴム３〜８質量部からなることを特徴とする前記１に記載のタイヤ加硫ブラダー用ゴム組成物。
４．前記ゴム成分１００質量部に対し、窒素吸着比表面積（Ｎ２ＳＡ）が７０〜１２０ｍ２／ｇのカーボンブラックを２０〜８０質量部およびフェノール系樹脂を１〜１５質量部配合することを特徴とする前記１に記載のタイヤ加硫ブラダー用ゴム組成物。
５．前記１〜４のいずれかに記載のタイヤ加硫ブラダー用ゴム組成物を用いて成形したタイヤ加硫ブラダー。
６．前記タイヤ加硫ブラダーの複合伸び率が１５〜５０％となるように、前記タイヤ加硫ブラダーを用いてタイヤ成形が行われることを特徴とする前記４に記載のタイヤ加硫ブラダーを使用する方法。
７．前記タイヤ加硫ブラダーの複合伸び率が３０〜４０％となるように、前記タイヤ加硫ブラダーを用いてタイヤ成形が行われることを特徴とする前記６に記載のタイヤ加硫ブラダーを使用する方法。That is, the present invention is as follows.
1. With respect to 100 parts by mass of a rubber component containing 92 parts by mass or more of butyl rubber, the butyl rubber has a degree of unsaturation of 0.6 to 1.1% Butyl rubber (1) 30 to 100% by mass and 1.5 to 2.0. % Of butyl rubber (2) having a degree of unsaturation of 0 to 70% by mass, and a rubber composition for a tire vulcanizing bladder.
2. The rubber composition for a tire vulcanization bladder according to the above 1, wherein the butyl rubber (1) has an unsaturation degree of 0.6 to 1.0%.
3. 2. The rubber composition for a tire vulcanizing bladder according to 1 above, wherein the rubber component is composed of 92 to 97 parts by mass of butyl rubber and 3 to 8 parts by mass of chloroprene rubber.
4. 20 to 80 parts by mass of carbon black having a nitrogen adsorption specific surface area (N 2 SA) of 70 to 120 m 2 /g and 1 to 15 parts by mass of a phenolic resin are blended with 100 parts by mass of the rubber component. The rubber composition for a tire vulcanizing bladder according to 1 above.
5. A tire vulcanization bladder molded using the rubber composition for a tire vulcanization bladder according to any one of 1 to 4 above.
6. The method for using the tire vulcanization bladder according to the above 4, wherein tire molding is performed using the tire vulcanization bladder so that the composite elongation of the tire vulcanization bladder is 15 to 50%. ..
7. The method for using the tire vulcanization bladder according to the above 6, wherein tire molding is performed using the tire vulcanization bladder so that the composite elongation of the tire vulcanization bladder is 30 to 40%. ..
本発明によれば、特定の不飽和度を有するブチルゴムを特定量で配合したので、従来技術よりも簡単な方法で、タイヤ加硫ブラダーに求められる物性を損なうことなく、ブラダーライフを大幅に延長することのできる、タイヤ加硫ブラダー用ゴム組成物およびそれを用いたタイヤ加硫ブラダーを提供することができる。
本発明で使用するブチルゴム（１）は、０．６〜１．１％という低い不飽和度を有している。このように分子中の二重結合量が少ないことから、タイヤから移行してくる硫黄によりゴム同士が架橋する現象が抑制される。また、低い不飽和度を有するブチルゴム（１）は、これよりも高い不飽和度を有するブチルゴムに比べ、良好な破断伸びを有する。したがって、熱老化によるゴムの硬化をも抑制することができる。According to the present invention, since butyl rubber having a specific degree of unsaturation is compounded in a specific amount, the bladder life can be greatly extended by a method simpler than the conventional technique without impairing the physical properties required for a tire vulcanization bladder. It is possible to provide a rubber composition for a tire vulcanization bladder and a tire vulcanization bladder using the same.
The butyl rubber (1) used in the present invention has a low degree of unsaturation of 0.6 to 1.1%. Since the amount of double bonds in the molecule is small in this way, the phenomenon that rubbers are cross-linked by sulfur transferred from the tire is suppressed. Further, the butyl rubber (1) having a low degree of unsaturation has a good elongation at break as compared with the butyl rubber having a higher degree of unsaturation. Therefore, the curing of rubber due to heat aging can also be suppressed.
以下、本発明をさらに詳細に説明する。
（ゴム成分）
本発明の加硫ブラダー用ゴム組成物は、ゴム成分全体を１００質量部としたときに、ブチルゴム(IIR)を９２質量部以上含む。そしてこのブチルゴムは、０．６〜１．１％の不飽和度を有するブチルゴム（１）３０〜１００質量％および１．５〜２．０％の不飽和度を有するブチルゴム（２）０〜７０質量％から構成される。
前記ブチルゴム（１）の配合量は、本発明の効果が向上するという観点から、40〜80質量％が好ましく、50〜60質量％がさらに好ましい。
また前記ブチルゴム（２）が配合される場合、その配合量は、ブチルゴム全体に対し、３０〜７０質量％が好ましい。Hereinafter, the present invention will be described in more detail.
(Rubber component)
The rubber composition for a vulcanized bladder of the present invention contains 92 parts by mass or more of butyl rubber (IIR) when the total amount of the rubber component is 100 parts by mass. This butyl rubber is a butyl rubber (1) having a degree of unsaturation of 0.6 to 1.1%, 30 to 100% by mass, and a butyl rubber (2) having a degree of unsaturation of 1.5 to 2.0%. Composed of mass%.
From the viewpoint of improving the effect of the present invention, the compounding amount of the butyl rubber (1) is preferably 40 to 80% by mass, more preferably 50 to 60% by mass.
Moreover, when the said butyl rubber (2) is mix|blended, 30-70 mass% of the compounding quantity is preferable with respect to the whole butyl rubber.
ここで本発明でいう不飽和度は、１Ｈ−ＮＭＲを用いて求めることができる。
本発明の効果が向上するという観点から、ブチルゴム（１）の不飽和度は、0.6〜1.0％が好ましい。また、ブチルゴム（２）の不飽和度は、1.6〜1.8％が好ましい。Here, the degree of unsaturation in the present invention can be determined by using 1 H-NMR.
From the viewpoint of improving the effect of the present invention, the unsaturation degree of the butyl rubber (1) is preferably 0.6 to 1.0%. The butyl rubber (2) preferably has a degree of unsaturation of 1.6 to 1.8%.
また本発明におけるゴム成分は、前記のブチルゴム以外に、他のゴム成分を配合することもできる。
とくに本発明においては、クロロプレンゴム（ＣＲ）を配合するのが好ましく、その配合量は、ゴム成分全体を１００質量部としたときに、ブチルゴム９２〜９７質量部およびクロロプレンゴム３〜８質量部からなることが好ましい。Further, the rubber component in the present invention may be blended with other rubber components in addition to the above butyl rubber.
Particularly in the present invention, it is preferable to blend chloroprene rubber (CR), and the blending amount is from 92 to 97 parts by mass of butyl rubber and 3 to 8 parts by mass of chloroprene rubber when the total rubber component is 100 parts by mass. It is preferable that
（カーボンブラック）
本発明では、熱伝導性をさらに高めるために、カーボンブラックを配合することができる。カーボンブラックの窒素吸着比表面積（Ｎ２ＳＡ）は、７０〜１２０ｍ２／ｇであることが本発明の効果の観点から好ましい。
カーボンブラックの配合量は、ゴム成分１００質量部に対し、例えば２０〜８０質量部であり、好ましくは40〜70質量部である。
なお窒素吸着比表面積（Ｎ２ＳＡ）は、ＪＩＳ Ｋ６２１７−２に準拠して求めるものとする。(Carbon black)
In the present invention, carbon black can be blended in order to further enhance the thermal conductivity. The nitrogen adsorption specific surface area (N 2 SA) of carbon black is preferably 70 to 120 m 2 /g from the viewpoint of the effect of the present invention.
The blending amount of carbon black is, for example, 20 to 80 parts by mass, preferably 40 to 70 parts by mass, relative to 100 parts by mass of the rubber component.
The nitrogen adsorption specific surface area (N 2 SA) is determined according to JIS K6217-2.
（フェノール系樹脂）
本発明では、不飽和度の低いブチルゴム（１）を配合することから、架橋剤としてフェノール系樹脂を配合するのが好ましい。
フェノール系樹脂としては、ノボラック型フェノール樹脂、ノボラック型クレゾール樹脂、ノボラック型レゾルシン樹脂等が挙げられる。
フェノール系樹脂の配合量は、ゴム成分１００質量部に対し、例えば１〜１５質量部であり、好ましくは5〜10質量部である。(Phenolic resin)
In the present invention, since butyl rubber (1) having a low degree of unsaturation is blended, it is preferable to blend a phenolic resin as a crosslinking agent.
Examples of the phenolic resin include novolac type phenol resin, novolac type cresol resin, and novolac type resorcin resin.
The compounding amount of the phenolic resin is, for example, 1 to 15 parts by mass, and preferably 5 to 10 parts by mass with respect to 100 parts by mass of the rubber component.
本発明に係る加硫ブラダー用ゴム組成物には、前記した成分に加えて、加硫又は架橋剤、加硫又は架橋促進剤、老化防止剤、可塑剤などのゴム組成物に一般的に配合されている各種添加剤を配合することができ、かかる添加剤は一般的な方法で混練して組成物とすることができる。これらの添加剤の配合量も、本発明の目的に反しない限り、従来の一般的な配合量とすることができる。また本発明の加硫ブラダー用ゴム組成物は従来のタイヤ加硫ブラダーの製造方法に従ってタイヤ加硫ブラダーを製造することができる。 In the rubber composition for vulcanized bladder according to the present invention, in addition to the above-mentioned components, a vulcanization or cross-linking agent, a vulcanization or cross-linking accelerator, an antioxidant, a plasticizer, etc. are generally added to the rubber composition. Various known additives can be blended, and such additives can be kneaded into a composition by a general method. The amounts of these additives to be added can also be conventional general amounts, unless the object of the present invention is violated. The rubber composition for a vulcanization bladder of the present invention can be used to manufacture a tire vulcanization bladder according to a conventional method for manufacturing a tire vulcanization bladder.
なお本発明のタイヤ加硫ブラダーは、下記の式１により算出される複合伸び率が１５〜５０％となるように、タイヤ成形を行うことが好ましい。
式１： 複合伸び率＝縦方向伸び率＊周方向伸び率
縦方向伸び率＝タイヤペリフェリ／ブラダーペリフェリ
周方向伸び率＝（タイヤ外径−ブラダー外径）／ブラダー外径
複合伸び率が上記範囲にあることにより、不飽和度の低いブチルゴム（１）の配合により生じる経時によるモジュラス低下を抑制することができる。これにより、経時によるタイヤ加硫ブラダー表面のシワ発生を防止でき、好ましい。
さらに好ましい前記複合伸び率は、30〜40％である。The tire vulcanization bladder of the present invention is preferably subjected to tire molding so that the composite elongation calculated by the following formula 1 becomes 15 to 50%.
Formula 1: Composite elongation=longitudinal elongation*circumferential elongation Percentage longitudinal elongation=tire peripheral/bladder peripheral peripheral elongation=(tire outer diameter-bladder outer diameter)/bladder outer diameter Within the above range, it is possible to suppress the decrease in modulus over time due to the incorporation of the butyl rubber (1) having a low degree of unsaturation. This is preferable because wrinkles on the surface of the tire vulcanization bladder can be prevented from occurring over time.
The more preferable composite elongation percentage is 30 to 40%.
以下、本発明を実施例および比較例によりさらに説明するが、本発明は下記例に制限されるものではない。 Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited to the following examples.
実施例１〜８および比較例１〜５
サンプルの調製
表１に示す配合（質量部）において、９０リットルの密閉式バンバリーミキサーで５分間混練し、１８０℃でミキサー外に放出させて室温冷却した後、さらにオープンロールにて混練し、ゴム組成物を得た。次に得られたゴム組成物を所定の金型中で１９０℃、２０分間プレス加硫し、タイヤ加硫ブラダーを得た。得られたタイヤ加硫ブラダーについて、以下の試験を行った。なお、タイヤ加硫ブラダーは、タイヤサイズ１９５／６５Ｒ１５の空気入りタイヤの製造する際に、前記の式１に基づいて求めた複合伸び率が１５％（実施例１）、５０％（実施例２）または３０％（その他の実施例および比較例）となるサイズに調整した。Examples 1-8 and Comparative Examples 1-5
Sample Preparation In the formulation (parts by mass) shown in Table 1, knead with a 90 liter closed Banbury mixer for 5 minutes, discharge at 180° C. outside the mixer and cool to room temperature, and then knead with an open roll to give a rubber. A composition was obtained. Next, the obtained rubber composition was press-vulcanized in a predetermined mold at 190° C. for 20 minutes to obtain a tire vulcanization bladder. The following tests were conducted on the obtained tire vulcanization bladder. The tire vulcanization bladder has a composite elongation rate of 15% (Example 1) and 50% (Example 2) obtained in accordance with Equation 1 above when manufacturing a pneumatic tire having a tire size of 195/65R15. ) Or 30% (other examples and comparative examples).
ブラダー使用回数：タイヤサイズ１９５／６５Ｒ１５の空気入りタイヤを製造し、ブラダーの表面荒れが発生するまでのタイヤ加硫本数を調べた。結果は比較例１の値を１００として指数表示した。この指数が高いほどブラダーライフが延長されていることを示す。
破断伸び：ＪＩＳ Ｋ６２５１に準拠して引張試験にて評価した。結果は比較例１の値を１００として指数表示した。この指数が高いほど破断伸びが高いことを示す。
結果を併せて表１に示す。Number of times of use of bladder: A pneumatic tire having a tire size of 195/65R15 was manufactured, and the number of vulcanized tires until the surface roughness of the bladder occurred was examined. The result was shown as an index with the value of Comparative Example 1 as 100. The higher this index is, the longer the bladder life is.
Elongation at break: Evaluated by a tensile test according to JIS K6251. The result was shown as an index with the value of Comparative Example 1 as 100. The higher this index, the higher the elongation at break.
The results are also shown in Table 1.
＊１：ブチルゴム（１）（ランクセスラバー社製ＢＵＴＹＬ１００シリーズ。０．６％または１．１％の不飽和度を有する。）
＊２：ブチルゴム（２）（ランクセスラバー社製ＢＵＴＹＬ３０１シリーズ。１．５％または２．０％の不飽和度を有する。）
＊３：クロロプレンゴム（昭和電工（株）製ショウプレンＷ）
＊４：カーボンブラック（キャボットジャパン（株）製ショウブラックＮ２２０、Ｎ２ＳＡ＝１１１ｍ２／ｇ）
＊５：オイル（昭和シェル石油（株）製エキストラクト４号Ｓ）
＊６：酸化亜鉛（正同化学工業（株）製酸化亜鉛３種）
＊７：フェノール系樹脂（日立化成（株）製ヒタノール）*1: Butyl rubber (1) (BUTYL100 series manufactured by LANX Thess Rubber, which has a degree of unsaturation of 0.6% or 1.1%.)
*2: Butyl rubber (2) (BUTYL301 series manufactured by LANX Thess Rubber, which has an unsaturation degree of 1.5% or 2.0%.)
*3: Chloroprene rubber (Showpren W manufactured by Showa Denko KK)
*4: Carbon black (Show Black N220, N 2 SA=111 m 2 /g manufactured by Cabot Japan Ltd.)
*5: Oil (Extract No. 4S manufactured by Showa Shell Sekiyu KK)
*6: Zinc oxide (3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd.)
*7: Phenolic resin (Hitaanol manufactured by Hitachi Chemical Co., Ltd.)
前記の表１から明らかなように、実施例１〜８で調製されたゴム組成物は、特定の不飽和度を有するブチルゴム（１）を特定量で配合したので、従来の代表的な比較例１に比べて、破断伸びを悪化させることなく、ブラダーライフが顕著に改善されている。
これに対し、比較例２〜５は、ブチルゴム（１）の配合量が本発明で規定する下限未満であるので、ブラダーライフの改善効果が僅かな範囲に留まっていることが判明した。As is clear from Table 1 above, the rubber compositions prepared in Examples 1 to 8 contained butyl rubber (1) having a specific degree of unsaturation in a specific amount. Compared with No. 1, the bladder life was remarkably improved without deteriorating the elongation at break.
On the other hand, in Comparative Examples 2 to 5, since the compounding amount of butyl rubber (1) was less than the lower limit specified in the present invention, it was found that the effect of improving the bladder life remained within a slight range.
Claims (5)
前記タイヤ加硫ブラダーの、下記式１で定義される複合伸び率が１５〜５０％となるように、前記タイヤ加硫ブラダーを用いてタイヤ成形が行われることを特徴とするタイヤ加硫ブラダーの使用方法。
式１：複合伸び率＝縦方向伸び率＊周方向伸び率
縦方向伸び率＝タイヤペリフェリ／ブラダーペリフェリ
周方向伸び率＝（タイヤ外径−ブラダー外径）／ブラダー外径
タイヤ加硫ブラダー用ゴム組成物： ブチルゴムを含むゴム成分を含有し、前記ブチルゴムは、前記ゴム成分全体を１００質量部としたときに９２質量部以上を占め、前記ブチルゴムが、０．６〜１．１％の不飽和度を有するブチルゴム（１）３０〜１００質量％および１．５〜２．０％の不飽和度を有するブチルゴム（２）０〜７０質量％から構成される。 A method of using a tire vulcanizing bladder molded using the rubber composition for a tire vulcanizing bladder,
A tire vulcanization bladder, in which tire molding is performed using the tire vulcanization bladder so that a composite elongation rate defined by the following formula 1 of the tire vulcanization bladder is 15 to 50%. how to use.
Formula 1: Composite elongation rate = longitudinal elongation rate * circumferential elongation rate
Longitudinal elongation = tire peripheral/bladder peripheral
Circumferential elongation rate = (tire outer diameter-bladder outer diameter)/bladder outer diameter
Rubber composition for tire vulcanization bladder: Contains a rubber component including butyl rubber, the butyl rubber occupies 92 parts by mass or more when the total amount of the rubber component is 100 parts by mass, and the butyl rubber has a content of 0.6 to 1 Butyl rubber (1) having a degree of unsaturation of 1% and 30 to 100% by mass and butyl rubber (2) having a degree of unsaturation of 1.5 to 2.0% and 0 to 70% by mass .
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| JP2014245656 | 2014-12-04 | ||
| JP2014245656 | 2014-12-04 | ||
| PCT/JP2015/083943 WO2016088817A1 (en) | 2014-12-04 | 2015-12-03 | Rubber composition for tire-vulcanizing bladder, and tire-vulcanizing bladder produced using same |
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| CN109385015A (en) * | 2018-11-01 | 2019-02-26 | 永橡胶有限公司 | A kind of preparation method improving tire curing bladder production security |
| CN114025949B (en) * | 2019-07-18 | 2023-07-21 | 横滨橡胶株式会社 | Air bag for vulcanizing tyre |
| CN112175307A (en) * | 2020-09-30 | 2021-01-05 | 永一橡胶有限公司 | Preparation method of high-ductility tire curing bladder |
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| JPS61185548A (en) * | 1985-02-13 | 1986-08-19 | Yokohama Rubber Co Ltd:The | Rubber composition for vulcanized bladder |
| JPS6268838A (en) * | 1985-09-19 | 1987-03-28 | Yokohama Rubber Co Ltd:The | Rubber composition for vulcanized bladder |
| JPH1086156A (en) * | 1996-08-29 | 1998-04-07 | Continental Ag | Bladder consisting of rubber for vulcanizing tire or air spring |
| JP3741800B2 (en) * | 1996-10-25 | 2006-02-01 | 株式会社ブリヂストン | Rubber composition for bladder for vulcanization |
| JP5232081B2 (en) * | 2009-06-11 | 2013-07-10 | 住友ゴム工業株式会社 | Rubber composition for bladder and bladder |
| JP5221623B2 (en) * | 2010-10-27 | 2013-06-26 | 住友ゴム工業株式会社 | Rubber composition for bladder and bladder |
| JP6114081B2 (en) * | 2013-03-22 | 2017-04-12 | 横浜ゴム株式会社 | Rubber composition for vulcanization bladder and vulcanization bladder for tire using the same |
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