JP2007224166A - Anti-aging sticking material and method for preventing aging of vulcanized rubber - Google Patents
Anti-aging sticking material and method for preventing aging of vulcanized rubber Download PDFInfo
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Abstract
Description
本発明は、老化防止用貼付材および架橋ゴムの老化防止方法に関する。 The present invention relates to an anti-aging patch and a method for preventing the aging of a crosslinked rubber.
タイヤ、ホース、防舷材等の屋外で使用されるゴム製品には、紫外線、オゾン、熱等による劣化を防ぐことを目的として老化防止剤が添加されている。
しかし、上記ゴム製品が長期間屋外で使用される場合、この老化防止剤は経時的に消費されて減少するため、架橋ゴムの劣化が生じて要求特性が発揮できなくなる問題がある。
Anti-aging agents are added to rubber products used outdoors such as tires, hoses, and fenders for the purpose of preventing deterioration due to ultraviolet rays, ozone, heat, and the like.
However, when the rubber product is used outdoors for a long period of time, this anti-aging agent is consumed and decreased over time, so that there is a problem that the required properties cannot be exhibited due to deterioration of the crosslinked rubber.
このような問題に対して、従来より、塗料・溶剤タイプの老化防止用組成物を架橋ゴムの表面に塗布して、塗膜を形成し、ゴム製品の劣化を防止する方法が提案されている。
上記塗料・溶剤タイプの老化防止用組成物としては、例えば、「硬化性ポリウレタンおよびまたは硬化性シリコンからなる塗料組成物において、芳香族アミン誘導体、フェノール誘導体、キノリン誘導体、ジチオカルバミン酸塩類およびイミダゾール類から選ばれる１種または２種以上の老化防止剤を上記塗料組成物に対し、０．１重量％〜１０重量％含むことを特徴とするゴム材料老化防止用塗料組成物」等が挙げられる（特許文献１参照。）。
For such problems, conventionally, a method for preventing deterioration of rubber products by applying a paint / solvent type anti-aging composition to the surface of a crosslinked rubber to form a coating film has been proposed. .
Examples of the paint / solvent type anti-aging composition include, for example, “in a paint composition comprising a curable polyurethane and / or curable silicon, from an aromatic amine derivative, a phenol derivative, a quinoline derivative, a dithiocarbamate salt, and an imidazole. Examples include a rubber material anti-aging coating composition characterized by containing one or more selected anti-aging agents in an amount of 0.1 wt% to 10 wt% with respect to the coating composition (patents). Reference 1).
しかしながら、従来の塗料・溶剤タイプの老化防止用組成物は、下記のような問題を有する。
（Ａ）垂直面等に用いた場合にタレを発生する。
（Ｂ）溶剤を含有するため、ゴム製品の表面を傷めたり、変色させるおそれがある。
（Ｃ）環境汚染を引き起こすおそれがある。
（Ｄ）密閉された空間での使用に適さない。
（Ｅ）屋外で使用する場合、風雨の影響により均一な塗膜を形成できない。
（Ｆ）形成される塗膜は、膜厚が比較的薄いので効果の持続性が短い。
However, conventional paint / solvent type anti-aging compositions have the following problems.
(A) Sagging occurs when used on a vertical surface.
(B) Since it contains a solvent, the surface of the rubber product may be damaged or discolored.
(C) There is a risk of causing environmental pollution.
(D) Not suitable for use in a sealed space.
(E) When used outdoors, a uniform coating film cannot be formed due to the influence of wind and rain.
(F) Since the coating film to be formed is relatively thin, the effect persistence is short.
そこで、本発明は、下記（ａ）〜（ｇ）の効果を有する老化防止用貼付材を提供することを目的とする。
（ａ）架橋ゴムに老化防止剤を移行することができ、架橋ゴムの耐老化性を復活できる。
（ｂ）水平面以外（垂直面等）にも使用できる。
（ｃ）ゴム製品の表面を傷めたり、変色させることがない。
（ｄ）環境汚染の問題がない。
（ｅ）密閉された空間でも使用できる。
（ｆ）屋外で使用する場合、風雨の影響がほとんどない。
（ｇ）ゴム製品の状態に応じて、適切な老化防止性を付与できる。
Therefore, an object of the present invention is to provide an anti-aging patch having the following effects (a) to (g).
(A) An anti-aging agent can be transferred to the crosslinked rubber, and the aging resistance of the crosslinked rubber can be restored.
(B) It can be used for other than horizontal surfaces (vertical surfaces, etc.).
(C) The surface of the rubber product is not damaged or discolored.
(D) There is no problem of environmental pollution.
(E) It can be used in a sealed space.
(F) When used outdoors, there is almost no influence of wind and rain.
(G) Appropriate anti-aging properties can be imparted depending on the state of the rubber product.
また、本発明は、上記（ａ）〜（ｇ）の効果を有する架橋ゴムの老化防止方法を提供することを目的とする。 Another object of the present invention is to provide a method for preventing aging of crosslinked rubber having the effects (a) to (g).
本発明者は、ゴム、熱可塑性エラストマーおよび樹脂からなる群から選択される少なくとも１種のポリマー成分１００質量部と、老化防止剤５〜５０質量部とを含有すると、上記（ａ）〜（ｇ）の効果を有する老化防止用貼付材となることを見出した。
また、本発明者は、ゴム、熱可塑性エラストマーおよび樹脂からなる群から選択される少なくとも１種のポリマー成分と、老化防止剤とを含有する老化防止用貼付材を架橋ゴムに貼付し、上記老化防止剤を上記架橋ゴムに移行させることにより、上記（ａ）〜（ｇ）の効果を有し、架橋ゴムの老化を防止できることを見出した。
本発明者は、これらの知見に基づき、本発明を完成させた。
When this inventor contains 100 mass parts of at least 1 sort (s) of polymer components selected from the group which consists of rubber | gum, a thermoplastic elastomer, and resin, and 5-50 mass parts of anti-aging agents, said (a)-(g It has been found that it becomes an anti-aging patch having the effect of).
In addition, the present inventor affixed an anti-aging patch containing at least one polymer component selected from the group consisting of rubber, thermoplastic elastomer and resin, and an anti-aging agent to the crosslinked rubber, and It has been found that by transferring the inhibitor to the crosslinked rubber, the effects of the above (a) to (g) can be obtained and aging of the crosslinked rubber can be prevented.
The present inventor has completed the present invention based on these findings.
即ち、本発明は、下記（１）〜（１０）を提供する。
（１）ゴム、熱可塑性エラストマーおよび樹脂からなる群から選択される少なくとも１種のポリマー成分１００質量部と、老化防止剤５〜５０質量部とを含有する老化防止用貼付材。
（２）前記ポリマー成分が、可撓性および粘着性を有する上記（１）に記載の老化防止用貼付材。
（３）前記老化防止剤が、フェノール誘導体、芳香族アミン誘導体、アミン−ケトン縮合物、ベンズイミダゾール誘導体、ジチオカルバミン酸誘導体およびチオウレア誘導体からなる群から選択される少なくとも１種である上記（１）または（２）に記載の老化防止用貼付材。
（４）更に、オイルを前記ポリマー成分１００質量部に対して３０質量部以下含有する上記（１）〜（３）のいずれかに記載の老化防止用貼付材。
（５）更に、カーボンブラックを含有する上記（１）〜（４）のいずれかに記載の老化防止用貼付材。
（６）シート状である上記（１）〜（５）のいずれかに記載の老化防止用貼付材。
（７）前記シート状老化防止用貼付材の片面または両面に、バックアップ材を有する上記（６）に記載の老化防止用貼付材。
（８）ゴム、熱可塑性エラストマーおよび樹脂からなる群から選択される少なくとも１種のポリマー成分と、老化防止剤とを含有する老化防止用貼付材を架橋ゴムに貼付し、前記老化防止剤を前記架橋ゴムに移行させて、前記架橋ゴムの老化を防止する、架橋ゴムの老化防止方法。
（９）前記老化防止剤を前記架橋ゴムに移行させた後、前記老化防止用貼付材を前記架橋ゴムから剥離する上記（８）に記載の架橋ゴムの老化防止方法。
（１０）前記老化防止用貼付材が、上記（１）〜（７）のいずれかに記載の老化防止用貼付材である、上記（８）または（９）に記載の架橋ゴムの老化防止方法。
That is, the present invention provides the following (1) to (10).
(1) An anti-aging patch comprising 100 parts by mass of at least one polymer component selected from the group consisting of rubber, thermoplastic elastomer and resin, and 5 to 50 parts by mass of an anti-aging agent.
(2) The anti-aging patch according to (1), wherein the polymer component has flexibility and adhesiveness.
(3) The above (1) or wherein the anti-aging agent is at least one selected from the group consisting of phenol derivatives, aromatic amine derivatives, amine-ketone condensates, benzimidazole derivatives, dithiocarbamic acid derivatives and thiourea derivatives. The patch for aging prevention according to (2).
(4) The patch for anti-aging according to any one of (1) to (3), further comprising 30 parts by mass or less of oil with respect to 100 parts by mass of the polymer component.
(5) The anti-aging patch according to any one of (1) to (4), further containing carbon black.
(6) The anti-aging patch according to any one of (1) to (5), which is in the form of a sheet.
(7) The anti-aging patch according to (6), wherein a backup material is provided on one or both sides of the sheet-like anti-aging patch.
(8) An anti-aging patch containing at least one polymer component selected from the group consisting of rubber, thermoplastic elastomer and resin, and an anti-aging agent is applied to the crosslinked rubber, and the anti-aging agent is A method for preventing aging of a crosslinked rubber, wherein the aging of the crosslinked rubber is prevented by transferring to the crosslinked rubber.
(9) The anti-aging method for cross-linked rubber according to (8), wherein the anti-aging patch is peeled from the cross-linked rubber after the anti-aging agent has been transferred to the cross-linked rubber.
(10) The anti-aging method for crosslinked rubber according to (8) or (9), wherein the anti-aging patch is the anti-aging patch according to any one of (1) to (7). .
本発明の老化防止用貼付材および本発明の架橋ゴムの老化防止方法は、下記の効果を有する。
（ａ）架橋ゴムに老化防止剤を移行することができ、架橋ゴムの耐老化性を復活できる。
（ｂ）水平面以外（垂直面等）にも使用できる。
（ｃ）ゴム製品の表面を傷めたり、変色させることがない。
（ｄ）溶剤を含有しないので、環境汚染の問題がない。
（ｅ）溶剤を含有しないので、密閉された空間でも使用できる。
（ｆ）屋外で使用する場合、風雨の影響がほとんどない。
（ｇ）厚さの調整や貼り換え等により、製品の状態に応じて、適切な老化防止性を付与できる。
The anti-aging patch of the present invention and the anti-aging method for crosslinked rubber of the present invention have the following effects.
(A) An anti-aging agent can be transferred to the crosslinked rubber, and the aging resistance of the crosslinked rubber can be restored.
(B) It can be used for other than horizontal surfaces (vertical surfaces, etc.).
(C) The surface of the rubber product is not damaged or discolored.
(D) Since no solvent is contained, there is no problem of environmental pollution.
(E) Since it does not contain a solvent, it can be used even in a sealed space.
(F) When used outdoors, there is almost no influence of wind and rain.
(G) Appropriate anti-aging properties can be imparted according to the state of the product by adjusting the thickness or reattaching.
以下、本発明をより詳細に説明する。
本発明の老化防止用貼付材（以下、単に「貼付材」ともいう。）は、ゴム、熱可塑性エラストマーおよび樹脂からなる群から選択される少なくとも１種のポリマー成分１００質量部と、老化防止剤５〜５０質量部とを含有する。
Hereinafter, the present invention will be described in more detail.
The anti-aging patch of the present invention (hereinafter also simply referred to as “patch”) includes at least one polymer component selected from the group consisting of rubber, thermoplastic elastomer and resin, and an anti-aging agent. 5 to 50 parts by mass.
上記ポリマー成分としては、ゴム、熱可塑性エラストマーおよび樹脂からなる群から選択される少なくとも１種であれば特に限定されないが、可撓性および粘着性を有するものが好ましく、ガラス転移点が室温（２５℃）以下であることがより好ましい。 The polymer component is not particularly limited as long as it is at least one selected from the group consisting of rubber, thermoplastic elastomer and resin, but is preferably flexible and adhesive, and has a glass transition point of room temperature (25 It is more preferred that the temperature
上記ゴムは、架橋ゴム、未架橋ゴムのいずれであってもよいが、一般的に、可撓性および粘着性に優れる点から、未架橋ゴムが好ましい。
未架橋ゴムとしては、具体的には、例えば、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、１，２−ブタジエンゴム、スチレン−ブタジエンゴム（ＳＢＲ）、アクリロニトリル−ブタジエンゴム（ＮＢＲ）、クロロプレンゴム、ブチルゴム（ＩＩＲ）、エチレン−プロピレン−ジエンゴム（ＥＰＤＭ）等のジエン系ゴムおよびこれらの水素添加物；エチレン−プロピレンゴム（ＥＰＭ）、エチレン−ブテンゴム（ＥＢＭ）、クロロスルホン化ポリエチレン、アクリルゴム、フッ素ゴム、ポリエチレンゴム、ポリプロピレンゴム等のオレフィン系ゴム；エピクロロヒドリンゴム；シリコーンゴム；およびウレタンゴム等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。
これらの中でも、粘着性が高く、加工性と物性が良好であるという点から、天然ゴム、イソプレンゴムが好ましい。
The rubber may be either a crosslinked rubber or an uncrosslinked rubber, but is generally preferably an uncrosslinked rubber from the viewpoint of excellent flexibility and adhesiveness.
Specific examples of the uncrosslinked rubber include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), and acrylonitrile-butadiene rubber. (NBR), diene rubbers such as chloroprene rubber, butyl rubber (IIR), ethylene-propylene-diene rubber (EPDM) and hydrogenated products thereof; ethylene-propylene rubber (EPM), ethylene-butene rubber (EBM), chlorosulfonated Examples include olefinic rubbers such as polyethylene, acrylic rubber, fluororubber, polyethylene rubber, and polypropylene rubber; epichlorohydrin rubber; silicone rubber; and urethane rubber. These may be used alone or in combination of two or more.
Among these, natural rubber and isoprene rubber are preferred from the viewpoints of high adhesiveness and good processability and physical properties.
架橋ゴムとしては、例えば、上記未架橋ゴムを加硫したもの等が挙げられる。中でも、天然ゴムが好ましい。 Examples of the crosslinked rubber include those obtained by vulcanizing the uncrosslinked rubber. Of these, natural rubber is preferable.
上記熱可塑性エラストマーとしては、具体的には、例えば、水添されていてもよいポリスチレン系エラストマー性ポリマー（ＳＢＳ、ＳＩＳ、ＳＥＢＳ等）、ポリオレフィン系エラストマー性ポリマー、ポリ塩化ビニル系エラストマー性ポリマー、ポリウレタン系エラストマー性ポリマー、ポリエステル系エラストマー性ポリマー、ポリアミド系エラストマー性ポリマー等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。 Specific examples of the thermoplastic elastomer include, for example, an optionally hydrogenated polystyrene elastomeric polymer (SBS, SIS, SEBS, etc.), a polyolefin elastomeric polymer, a polyvinyl chloride elastomeric polymer, and a polyurethane. Based elastomeric polymer, polyester based elastomeric polymer, polyamide based elastomeric polymer, and the like. These may be used alone or in combination of two or more.
上記樹脂としては、具体的には、例えば、（メタ）アクリル樹脂（エステル、ビニル系共重合体を含む）、ＡＢＳ樹脂、エチレン酢酸ビニル共重合体（ＥＶＡ）、ポリ塩化ビニル、ポリウレタン、ポリエステル、ポリオレフィン、ポリビニルアルコール、シリコーン樹脂等が挙げられる。これらは、単独で用いてもよく、２種以上を併用してもよい。 Specific examples of the resin include (meth) acrylic resins (including esters and vinyl copolymers), ABS resins, ethylene vinyl acetate copolymers (EVA), polyvinyl chloride, polyurethane, polyester, Examples include polyolefin, polyvinyl alcohol, and silicone resin. These may be used alone or in combination of two or more.
上記ポリマー成分の分子量は、特に限定されず、貼付材に要求される柔軟性等に応じて適宜設定することができる。 The molecular weight of the polymer component is not particularly limited, and can be appropriately set according to the flexibility required for the patch.
本発明に用いられる老化防止剤としては、特に限定されず、従来公知のゴム組成物に用いられる老化防止剤を使用できる。具体的には、例えば、フェノール誘導体、芳香族アミン誘導体、アミン−ケトン縮合物、ベンズイミダゾール誘導体、ジチオカルバミン酸誘導体、チオウレア誘導体等が好適に挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。 The anti-aging agent used in the present invention is not particularly limited, and anti-aging agents used in conventionally known rubber compositions can be used. Specific examples include phenol derivatives, aromatic amine derivatives, amine-ketone condensates, benzimidazole derivatives, dithiocarbamic acid derivatives, thiourea derivatives, and the like. These may be used alone or in combination of two or more.
上記フェノール誘導体としては、具体的には、例えば、スチレン化フェノール、２，６−ジ−ｔｅｒｔ−ブチルフェノール、２，６−ジ−ｔｅｒｔ−ブチルクレゾール、４，４′−ブチリデン−ビス（３−メチル−６−ｔｅｒｔ−ブチルフェノール）、４，４′−メチレン−ビス（２，６−ジ−ｔｅｒｔ−ブチルフェノール）、４，４′−チオ−ビス（６−ｔｅｒｔ−ブチル−ｍ−クレゾール）等が挙げられる。 Specific examples of the phenol derivative include styrenated phenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butylcresol, 4,4′-butylidene-bis (3-methyl). -6-tert-butylphenol), 4,4'-methylene-bis (2,6-di-tert-butylphenol), 4,4'-thio-bis (6-tert-butyl-m-cresol) and the like. It is done.
上記芳香族アミン誘導体としては、具体的には、例えば、４，４′−ビス（α，α−ジメチルベンジル）ジフェニルアミン、オクチル化ジフェニルアミン、Ｎ，Ｎ′−ジフェニル−ｐ−フェニレンジアミン、Ｎ，Ｎ′−ジ−２−ナフチル−ｐ−フェニレンジアミン、Ｎ−（１，３−ジメチルブチル）−Ｎ′−フェニル−ｐ−フェニレンジアミン等が挙げられる。 Specific examples of the aromatic amine derivative include 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, octylated diphenylamine, N, N′-diphenyl-p-phenylenediamine, and N, N. Examples include '-di-2-naphthyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, and the like.
上記アミン−ケトン縮合物としては、具体的には、例えば、２，２，４−トリメチル−１，２−ジヒドロキノリン重合体、６−エトキシ−１，２−ジヒドロ−２，２，４−トリメチルキノリン、ジフェニルアミンとアセトンの反応物等が挙げられる。 Specific examples of the amine-ketone condensate include 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-1,2-dihydro-2,2,4-trimethyl. Examples include quinoline, a reaction product of diphenylamine and acetone.
上記ベンズイミダゾール誘導体としては、具体的には、例えば、２−メルカプトベンズイミダゾール、２−メルカプトメチルベンズイミダゾール、２−メルカプトベンズイミダゾールの亜鉛塩等が挙げられる。 Specific examples of the benzimidazole derivative include 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptobenzimidazole, and the like.
上記ジチオカルバミン酸誘導体としては、具体的には、例えば、ジエチルジチオカルバミン酸ニッケル、ジブチルジチオカルバミン酸ニッケル等が挙げられる。 Specific examples of the dithiocarbamic acid derivative include nickel diethyldithiocarbamate and nickel dibutyldithiocarbamate.
上記チオウレア誘導体としては、具体的には、例えば、１，３−ビス（ジメチルアミノプロピル）−２−チオ尿素、トリブチルチオ尿素等が挙げられる。 Specific examples of the thiourea derivative include 1,3-bis (dimethylaminopropyl) -2-thiourea and tributylthiourea.
老化防止剤の含有量は、上記ポリマー成分１００質量部に対して、５〜５０質量部である。本発明の貼付材における老化防止剤の含有量は、通常のゴム製品における老化防止剤の含有量よりもかなり高く設定されているので、本発明の貼付材を架橋ゴムに密着させた場合、貼付材と架橋ゴムとの間に老化防止剤の濃度差が生じる。老化防止剤は低含有量の領域に移行する性質があるため、老化防止剤の含有量が上記の範囲であると、本発明の老化防止用貼付材から架橋ゴムへの老化防止剤の移行を容易に達成でき、ゴム製品自身の耐老化性を復活することができる。
老化防止剤の移行が速く、かつ、移行量が多く、長期間の耐老化性を付与できる点から、老化防止剤の含有量は、上記ポリマー成分１００質量部に対して、５〜３０質量部が好ましく、１０〜３０質量部がより好ましい。
Content of anti-aging agent is 5-50 mass parts with respect to 100 mass parts of said polymer components. The content of the anti-aging agent in the patch of the present invention is set to be considerably higher than the content of the anti-aging agent in ordinary rubber products. There is a difference in the concentration of the anti-aging agent between the material and the crosslinked rubber. Since the anti-aging agent has a property of shifting to a low content region, if the anti-aging content is in the above range, the anti-aging agent is transferred from the anti-aging patch of the present invention to the crosslinked rubber. It can be easily achieved and the aging resistance of the rubber product itself can be restored.
The content of the anti-aging agent is 5 to 30 parts by mass with respect to 100 parts by mass of the polymer component from the point that the migration of the anti-aging agent is fast, the amount of migration is large and long-term aging resistance can be imparted Is preferable, and 10-30 mass parts is more preferable.
本発明の老化防止用貼付材は、更に、オイルを上記ポリマー成分１００質量部に対して３０質量部以下含有するのが好ましい。オイルを含有すると、老化防止用貼付材の可撓性が向上し、更に、老化防止剤の架橋ゴムへの移行が容易になる。
オイルの種類は、特に限定されず、従来公知のゴム製品に軟化剤として用いられるオイル等を用いることができる。具体的には、例えば、石油系オイル、植物油系オイル、合成系オイル等が挙げられる。これらは、単独で用いてもよく、２種以上を併用してもよい。
The anti-aging patch of the present invention preferably further contains 30 parts by mass or less of oil with respect to 100 parts by mass of the polymer component. When oil is contained, the flexibility of the anti-aging patch is improved, and the transition of the anti-aging agent to a crosslinked rubber is facilitated.
The kind of oil is not particularly limited, and an oil used as a softening agent in conventionally known rubber products can be used. Specific examples include petroleum oils, vegetable oils, and synthetic oils. These may be used alone or in combination of two or more.
石油系オイルとしては、具体的には、例えば、パラフィン系、ナフテン系、アロマ系等が挙げられる。 Specific examples of petroleum-based oils include paraffinic, naphthenic, and aroma based oils.
上記オイルの含有量は、老化防止用貼付材の可撓性と老化防止剤の架橋ゴムへの移行のし易さの点から、上記ポリマー成分１００質量部に対して、３０質量部以下であり、５〜２０質量部が好ましく、５〜１５質量部がより好ましい。 The content of the oil is 30 parts by mass or less with respect to 100 parts by mass of the polymer component from the viewpoint of flexibility of the anti-aging patch and ease of migration of the anti-aging agent to a crosslinked rubber. 5 to 20 parts by mass is preferable, and 5 to 15 parts by mass is more preferable.
本発明の老化防止用貼付材は、更に、カーボンブラックを含有するのが好ましい。カーボンブラックは、着色剤、増量剤としての機能を有する。また、カーボンブラックは、老化防止剤等の分散性を向上できるので、老化防止剤等の配合量を多くできる。 The anti-aging patch of the present invention preferably further contains carbon black. Carbon black functions as a colorant and a bulking agent. Moreover, since carbon black can improve dispersibility, such as anti-aging agent, the compounding quantity of anti-aging agent etc. can be increased.
カーボンブラックの含有量は、上記ポリマー１００質量部に対して、３〜２０質量部が好ましく、３〜１０質量部がより好ましい。 3-20 mass parts is preferable with respect to 100 mass parts of said polymers, and, as for content of carbon black, 3-10 mass parts is more preferable.
本発明の老化防止用貼付材は、更に、粘着付与剤を含有するのが好ましい態様の１つである。粘着付与剤としては、具体的には、例えば、芳香族系炭化水素樹脂、飽和または不飽和脂肪族系炭化水素樹脂、テルペン樹脂、フェノール変性または芳香族変性テルペン樹脂等が挙げられる。 It is one of the preferred embodiments that the antiaging patch of the present invention further contains a tackifier. Specific examples of the tackifier include aromatic hydrocarbon resins, saturated or unsaturated aliphatic hydrocarbon resins, terpene resins, phenol-modified or aromatic-modified terpene resins, and the like.
本発明の老化防止用貼付材は、必要に応じて、本発明の目的を損わない範囲で、充填剤、顔料（染料）、可塑剤、難燃剤、分散剤、脱水剤、帯電防止剤等の各種添加剤等を含有することができる。 The anti-aging patch of the present invention may be a filler, a pigment (dye), a plasticizer, a flame retardant, a dispersant, a dehydrating agent, an antistatic agent, etc. Various additives and the like.
本発明の老化防止用貼付材は、液状でなく、架橋ゴムに貼付できるものであれば形状は特に限定されない。例えば、シート状（フィルム状を含む）、ペースト状、ペレット状等が挙げられる。これらの中でも、シート状が好ましい。 The shape of the anti-aging patch of the present invention is not particularly limited as long as it is not liquid and can be stuck to a crosslinked rubber. For example, a sheet form (including a film form), a paste form, a pellet form, and the like can be given. Among these, a sheet shape is preferable.
本発明の老化防止用貼付材の大きさおよび厚さは、特に限定されず、適宜選択することができる。本発明の老化防止用貼付材の厚さは、０．５〜１０ｍｍが好ましく、１〜６ｍｍがより好ましい。 The size and thickness of the anti-aging patch of the present invention are not particularly limited and can be appropriately selected. The thickness of the anti-aging patch of the present invention is preferably 0.5 to 10 mm, and more preferably 1 to 6 mm.
上記シート状老化防止用貼付材の片面または両面に、バックアップ材を有するのが好ましい態様の１つである。架橋ゴムに接触させる面の反対側の面にバックアップ材を有することにより、バックアップ材を有する面への老化防止剤の析出を抑制でき、架橋ゴムへの老化防止剤の移行を効率的に行うことが可能となる。また、貼付材の片面にバックアップ材を設けることにより、手に貼付材が張り付かないので貼付し易さ（作業性）を向上でき、更に、貼付材を補強できる。
バックアップ材を貼付材の両面に有する場合は、使用前の老化防止剤の表面への析出を抑制できる。この場合、片面のバックアップ材を剥がして使用することができる。
It is one of the preferred embodiments that a backup material is provided on one side or both sides of the sheet-like anti-aging patch. By having a backup material on the surface opposite to the surface in contact with the crosslinked rubber, it is possible to suppress the precipitation of the antioxidant on the surface having the backup material, and to efficiently transfer the antioxidant to the crosslinked rubber. Is possible. Further, by providing a backup material on one side of the adhesive material, the adhesive material does not stick to the hand, so that the ease of application (operability) can be improved and the adhesive material can be further reinforced.
In the case where the backup material is provided on both surfaces of the adhesive material, it is possible to suppress the precipitation of the anti-aging agent before use on the surface. In this case, the backup material on one side can be peeled off and used.
バックアップ材としては、具体的には、例えば、プラスチックフィルム、布、紙、繊維等が挙げられる。 Specifically as a backup material, a plastic film, cloth, paper, a fiber, etc. are mentioned, for example.
本発明の貼付材は、貼付材自体が粘着性を有していることが好ましいが、粘着性を補うために貼付材表面の一部または全部に、両面テープ、接着剤等の粘着部材を使用してもよい。 In the patch of the present invention, the patch itself preferably has adhesiveness, but in order to supplement the adhesiveness, an adhesive member such as a double-sided tape or adhesive is used on a part or all of the surface of the patch. May be.
本発明の貼付材の製造方法は、特に限定されず、例えば、上記の各成分（バックアップ材を除く。）を、バンバリーミキサー等のかくはん機を用いて十分に混練した後、所定の形状に成形する方法を用いることができる。必要に応じて、混練する際に加熱してもよい。必要に応じて、所定の形状にした後、バックアップ材を接着させてもよい。 The method for producing the patch of the present invention is not particularly limited. For example, the above components (excluding the backup material) are sufficiently kneaded using a stirrer such as a Banbury mixer, and then molded into a predetermined shape. Can be used. You may heat as needed, when kneading | mixing. If necessary, the back-up material may be bonded after the predetermined shape is obtained.
上述したように、本発明の老化防止用貼付材は、架橋ゴムに老化防止剤を移行することができ、架橋ゴムの耐老化性を復活できる。また、液ダレを生じず、水平面以外（垂直面等）にも使用できる。また、溶剤を使用しないので、ゴム製品の表面を傷めたり、変色させることがない。また、溶剤を含有しないので、環境汚染の問題がなく、密閉された空間でも使用できる。また、屋外で使用する場合、風雨の影響がほとんどない。また、貼付材の厚さや老化防止剤の含有量を調整したり、貼り換えを行うことにより、製品の状態に応じて、適切な老化防止性を付与できる。 As described above, the anti-aging patch of the present invention can transfer the anti-aging agent to the crosslinked rubber, and can restore the aging resistance of the crosslinked rubber. Moreover, it does not cause dripping and can be used for other than horizontal surfaces (vertical surfaces, etc.) In addition, since no solvent is used, the surface of the rubber product is not damaged or discolored. Moreover, since it does not contain a solvent, there is no problem of environmental pollution and it can be used in a sealed space. When used outdoors, there is almost no influence from wind and rain. Moreover, appropriate anti-aging properties can be imparted according to the state of the product by adjusting the thickness of the patch and the content of the anti-aging agent, or by performing re-sticking.
以下、本発明の架橋ゴムの老化防止方法（以下、本発明の老化防止方法という。）について詳細に説明する。
本発明の老化防止方法は、ゴム、熱可塑性エラストマーおよび樹脂からなる群から選択される少なくとも１種のポリマー成分と、老化防止剤とを含有する老化防止用貼付材を架橋ゴムに貼付し、上記老化防止剤を上記架橋ゴムに移行させて、上記架橋ゴムの老化を防止する、架橋ゴムの老化防止方法である。
Hereinafter, the anti-aging method of the crosslinked rubber of the present invention (hereinafter referred to as the anti-aging method of the present invention) will be described in detail.
The anti-aging method of the present invention comprises applying an anti-aging patch containing at least one polymer component selected from the group consisting of rubber, thermoplastic elastomer and resin, and an anti-aging agent to the crosslinked rubber, A method for preventing aging of a crosslinked rubber, wherein the aging inhibitor is transferred to the crosslinked rubber to prevent aging of the crosslinked rubber.
本発明の老化防止方法に用いられるポリマー成分（ゴム、熱可塑性エラストマー、樹脂）、老化防止剤は、上述した本発明の老化防止用貼付材に用いられるものと同様である。
本発明の老化防止方法に用いられる老化防止用貼付材としては、上述した本発明の老化防止用貼付材が好ましい。
The polymer component (rubber, thermoplastic elastomer, resin) and anti-aging agent used in the anti-aging method of the present invention are the same as those used for the anti-aging patch of the present invention described above.
As the anti-aging patch used in the anti-aging method of the present invention, the anti-aging patch of the present invention described above is preferable.
本発明の老化防止方法において、老化防止の対象となる架橋ゴムとしては、例えば、硫黄により架橋（加硫）されたジエン系ゴム、過酸化物により架橋されたジエン系ゴムおよび非ジエン系ゴム等が挙げられる。 In the aging prevention method of the present invention, examples of the crosslinked rubber to be subjected to aging prevention include, for example, diene rubber crosslinked (vulcanized) with sulfur, diene rubber crosslinked with peroxide, and non-diene rubber. Is mentioned.
上記貼付材は、架橋ゴム表面の老化を防止したい箇所またはその付近に貼付する。例えば、架橋ゴム表面に老化現象による亀裂が生じている場合において、その部分の老化の進行を抑制するため、または、耐老化性を復活させるために、当該亀裂部分を覆うようにシート状の貼付材を貼付すればよい。また、当該亀裂内部にペースト状の貼付材を充填して密着させることもできる。 The affixing material is affixed at or near the location where it is desired to prevent aging of the crosslinked rubber surface. For example, in the case where a crack due to an aging phenomenon has occurred on the surface of the crosslinked rubber, in order to suppress the progress of aging of the part or to restore the aging resistance, a sheet-like sticking is applied so as to cover the cracked part. What is necessary is just to stick material. Moreover, the paste-like patch can be filled into the crack and brought into close contact therewith.
本発明の老化防止方法において、上記老化防止用貼付材を架橋ゴムに貼付する方法としては、例えば、シート状の上記老化防止用貼付材を膨張および収縮が可能な装置の外面または内面に貼付し、その後上記装置を膨張させて、上記老化防止用貼付材を架橋ゴムに密着させて貼付する方法が好ましい態様の１つである。
上記膨張および収縮が可能な装置としては、例えば、バルーン、空気式防舷材等が挙げられる。バルーン、空気式防舷材は、内部圧力を増減することにより膨張、収縮することができ、簡便であるので好ましい。この方法によれば、直接手が届かない部位、例えば、ホースの内面等への貼付材の貼付を容易に行なうことができる。
In the anti-aging method of the present invention, as the method for applying the anti-aging patch to the crosslinked rubber, for example, the sheet-like anti-aging patch is applied to the outer surface or the inner surface of an apparatus capable of expanding and contracting. Then, one of the preferred embodiments is a method in which the device is then expanded so that the anti-aging patch is adhered to the crosslinked rubber for pasting.
Examples of the device capable of expanding and contracting include balloons and pneumatic fenders. Balloons and pneumatic fenders are preferred because they can be expanded and contracted by increasing or decreasing the internal pressure, and are simple. According to this method, it is possible to easily apply the adhesive material to a part that cannot be directly reached, such as the inner surface of the hose.
また、上記装置がチューブ状またはドーナツ状である場合、装置の内面に上記貼付材を貼付し、この装置を膨張させて、架橋ゴムに貼付材を密着させて貼付することができる。この方法は、例えば、筒型防舷材等の棒状のゴム製品に好適に使用できる。 Moreover, when the said apparatus is a tube shape or a donut shape, the said adhesive material can be affixed on the inner surface of an apparatus, this apparatus can be expanded, and an adhesive material can be stuck and adhere | attached on crosslinked rubber. This method can be suitably used for, for example, a rod-shaped rubber product such as a cylindrical fender.
上記貼付材を架橋ゴムに貼付すると、貼付材から架橋ゴムに老化防止剤が移行し始める。また、上記貼付材は、架橋ゴムに貼付されている間は、紫外線、オゾン等を遮断して、製品に直接作用させることがなく、延命効果が得られる。 When the patch is stuck to the crosslinked rubber, the anti-aging agent starts to migrate from the patch to the crosslinked rubber. Further, while the patch is stuck to the cross-linked rubber, ultraviolet rays, ozone and the like are blocked and the product does not directly act on the product, and a life extension effect is obtained.
上記老化防止用貼付材は、架橋ゴムに貼付したままでもよいが、老化防止剤が架橋ゴムに移行した後、前記架橋ゴムから剥離するのが外観を損なわないという点から好ましい使用方法の１つである。
老化防止剤の移行速度は貼付材と架橋ゴム表面との間の老化防止剤の濃度差や、周辺の温度等により影響を受けるので、貼付時間は使用状況に応じて適宜設定すればよい。通常、５０℃で１週間貼付した場合には老化防止剤の移行は十分達成できると考えられる。
The anti-aging patch may remain attached to the crosslinked rubber. However, after the anti-aging agent has migrated to the crosslinked rubber, it is one of the preferred methods of use since it does not impair the appearance when peeled off from the crosslinked rubber. It is.
Since the migration rate of the anti-aging agent is affected by the difference in the concentration of the anti-aging agent between the patch and the surface of the crosslinked rubber, the ambient temperature, and the like, the pasting time may be appropriately set according to the use situation. Usually, when applied at 50 ° C. for 1 week, it is considered that the migration of the anti-aging agent can be sufficiently achieved.
上述したように、本発明の老化防止方法は、架橋ゴムに老化防止剤を移行することができ、架橋ゴムの耐老化性を復活できる。また、液ダレを生じず、水平面以外（垂直面等）にも使用できる。また、溶剤を使用しないので、ゴム製品の表面を傷めたり、変色させることがない。また、溶剤を含有しないので、環境汚染の問題がなく、密閉された空間でも使用できる。また、屋外で使用する場合、風雨の影響がほとんどない。また、貼付材の厚さや老化防止剤の含有量を調整したり、貼り換えを行うことにより、製品の状態に応じて、適切な老化防止性を付与できる。 As described above, the anti-aging method of the present invention can transfer an anti-aging agent to the crosslinked rubber, and can restore the aging resistance of the crosslinked rubber. Moreover, it does not cause dripping and can be used for other than horizontal surfaces (vertical surfaces, etc.) In addition, since no solvent is used, the surface of the rubber product is not damaged or discolored. Moreover, since it does not contain a solvent, there is no problem of environmental pollution and it can be used in a sealed space. When used outdoors, there is almost no influence from wind and rain. Moreover, appropriate anti-aging properties can be imparted according to the state of the product by adjusting the thickness of the patch and the content of the anti-aging agent, or by performing re-sticking.
本発明の老化防止用貼付材および老化防止方法は、架橋ゴム製品に対して特に制限なく使用できる。応用例としては、タイヤを段積みして保管する際に、各タイヤ間にシート状の本発明の老化防止用貼付材を挟んでタイヤ表面の老化を防止することができる。 The anti-aging patch and the anti-aging method of the present invention can be used without particular limitation for crosslinked rubber products. As an application example, when the tires are stacked and stored, the tire surface anti-aging can be prevented by sandwiching the sheet-like anti-aging patch of the present invention between the tires.
以下、実施例を示して、本発明を具体的に説明する。ただし、本発明はこれらに限定されるものではない。
＜老化防止剤の移行実験＞
１．サンプルの作成
（実施例１）
未架橋の天然ゴム１００質量部と、老化防止剤（Ｎ−（１，３−ジメチルブチル）−Ｎ′−フェニル−ｐ−フェニレンジアミン、フレキシス社製）５質量部と、オイル（アロマオイル、昭和石油社製）３質量部と、カーボンブラック（ＨＴＣ＃１００、新日化カーボン社製）５質量部とをバンバリーミキサーに投入し、十分に混練した後、厚さ４ｍｍのシート状に成形して、老化防止用貼付材を得た。
Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
<Migration experiment of anti-aging agent>
1. Sample preparation (Example 1)
100 parts by mass of uncrosslinked natural rubber, 5 parts by mass of an antioxidant (N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, manufactured by Flexis), and oil (aroma oil, Showa (Petroleum) 3 parts by mass and carbon black (HTC # 100, made by Nisshin Carbon Co., Ltd.) 5 parts by mass are put into a Banbury mixer, kneaded sufficiently, and then molded into a 4 mm thick sheet. Thus, an anti-aging patch was obtained.
（実施例２）
老化防止剤の配合量を１０質量部に変更した以外は、実施例１と同様にシート状の老化防止用貼付材を得た。
(Example 2)
A sheet-like antiaging patch was obtained in the same manner as in Example 1 except that the blending amount of the antiaging agent was changed to 10 parts by mass.
（比較例１）
メチルエチルケトンと、老化防止剤（Ｎ−（１，３−ジメチルブチル）−Ｎ′−フェニル−ｐ−フェニレンジアミン、フレキシス社製）とを質量比７／３で混合して、老化防止用組成物を得た。
(Comparative Example 1)
Methyl ethyl ketone and an anti-aging agent (N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, manufactured by Flexis Co., Ltd.) are mixed at a mass ratio of 7/3 to obtain an anti-aging composition. Obtained.
（比較例２）
従来の溶剤タイプの老化防止用組成物（ＳＵＰＥＲ Ａｎｔｉ Ｃｒａｃｋ、横浜ゴム社製）と、老化防止剤（Ｎ−（１，３−ジメチルブチル）−Ｎ′−フェニル−ｐ−フェニレンジアミン、フレキシス社製）とを質量比９／１で混合して、老化防止用組成物を得た。
(Comparative Example 2)
Conventional solvent type anti-aging composition (SUPER Anti Crack, manufactured by Yokohama Rubber Co., Ltd.) and anti-aging agent (N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, manufactured by Flexis Co., Ltd.) ) At a mass ratio of 9/1 to obtain an anti-aging composition.
（比較例３）
実施例２のシート状老化防止用貼付材に、変性ゴム揮発油（日石三菱社製）を質量比（貼付材／揮発油）１／９となるように加えて十分に混合し、揮発油に貼付材を溶解させて、老化防止用組成物を得た。
(Comparative Example 3)
To the sheet-like anti-aging patch of Example 2, a modified rubber volatile oil (manufactured by Mitsubishi Oil Corporation) was added so as to have a mass ratio (patent / volatile oil) of 1/9, and mixed well, and the volatile oil The patch was dissolved in to obtain an anti-aging composition.
得られた実施例１〜２の老化防止用貼付材および比較例１〜３の老化防止用組成物について、下記の方法により、架橋ゴム（加硫ゴム）への老化防止剤の移行量を測定した。 With respect to the obtained anti-aging patch materials of Examples 1 and 2 and anti-aging compositions of Comparative Examples 1 to 3, the amount of anti-aging agent transferred to a crosslinked rubber (vulcanized rubber) was measured by the following method. did.
２．移行実験
防舷材用天然ゴムで作成したシート（以下、防舷材用ゴムシートという。）（１５０×１００×２ｍｍ）をアセトン抽出し、防舷材用ゴムシートに含まれる配合剤を抜いた。
次に、配合剤を抜いた防舷材用ゴムシートの表面に、実施例１〜２については各老化防止用貼付材を貼付け、比較例１〜３については各老化防止用組成物を刷毛で１回塗りして厚さ０．２ｍｍの膜を形成した。次に、オーブン内で５０℃で１週間加温した。
その後、老化防止用貼付材または老化防止用組成物を加硫ゴムシートから剥離して、加硫ゴムシートの表面（貼付面または塗布面）から０．５ｍｍずつ２層スライスして、表面側から第１層、第２層の試料とした。
上記で得られた第１層、第２層の試料を、アセトン１００ｍｌでソックスレー抽出器（ＪＩＳ Ｋ６２２９に準拠）を用いて４８時間抽出して、試料全体に占める移行した老化防止剤およびオイルの含有量の割合（アセトン抽出量）を求めた。
また、試料中に移行した老化防止剤をガスクロマトグラフィーで定量して、試料全体に占める老化防止剤の含有量の割合（老化防止剤移行量）を求めた。
結果を第１表に示す。
2. Transition experiment A sheet made of natural rubber for fenders (hereinafter referred to as a rubber sheet for fenders) (150 × 100 × 2 mm) was extracted with acetone, and the compounding agent contained in the rubber sheet for fenders was removed. .
Next, on the surface of the rubber sheet for anti-mold material from which the compounding agent was removed, each anti-aging patch was applied for Examples 1-2, and each anti-aging composition was brushed for Comparative Examples 1-3. The film was applied once to form a film having a thickness of 0.2 mm. Next, it was heated in an oven at 50 ° C. for 1 week.
Thereafter, the anti-aging patch or anti-aging composition is peeled off from the vulcanized rubber sheet and sliced into two layers of 0.5 mm each from the surface (applied surface or coated surface) of the vulcanized rubber sheet. Samples of the first layer and the second layer were used.
Samples of the first layer and the second layer obtained above are extracted with 100 ml of acetone using a Soxhlet extractor (conforming to JIS K6229) for 48 hours, and the transferred anti-aging agent and oil content in the entire sample are contained. The proportion of the amount (acetone extraction amount) was determined.
Further, the anti-aging agent transferred into the sample was quantified by gas chromatography, and the proportion of the content of the anti-aging agent in the entire sample (anti-aging agent transfer amount) was determined.
The results are shown in Table 1.
第１表に示す結果から明らかなように、実施例１〜２の老化防止用貼付材は、比較例１〜３の老化防止用組成物に比べて、老化防止剤の移行量がはるかに多かった。 As is apparent from the results shown in Table 1, the anti-aging patch materials of Examples 1 and 2 have a much larger migration amount of the anti-aging agent than the anti-aging compositions of Comparative Examples 1 to 3. It was.
＜耐老化性の評価＞
１．サンプルの作成
（比較例４）
防舷材用ゴムシート（１５０×１００×２ｍｍ）をダンベル状試験片（ＪＩＳダンベル３号）に打ち抜きサンプル１とした。
（比較例５）
アセトン抽出して配合剤を抜いた防舷材用ゴムシート（１５０×１００×２ｍｍ）をダンベル状試験片（ＪＩＳダンベル３号）に打ち抜きサンプル２とした。
（実施例３）
アセトン抽出して配合剤を抜いた防舷材用ゴムシート（１５０×１００×２ｍｍ）の表面に、実施例１の老化防止用貼付材を貼付け、ギアオーブン内で５０℃で１週間加温した。その後、老化防止用貼付材をゴムシートから剥離してダンベル状試験片（ＪＩＳダンベル３号）に打ち抜きサンプル３とした。
<Evaluation of aging resistance>
1. Sample preparation (Comparative Example 4)
A rubber sheet for fenders (150 × 100 × 2 mm) was punched out into a dumbbell-shaped test piece (JIS dumbbell No. 3) and used as sample 1.
(Comparative Example 5)
A rubber sheet for a fender (150 × 100 × 2 mm) from which a compounding agent was extracted by extraction with acetone was punched into a dumbbell-shaped test piece (JIS dumbbell No. 3), and used as sample 2.
(Example 3)
The anti-aging patch of Example 1 was applied to the surface of the rubber sheet for anti-mold material (150 × 100 × 2 mm) extracted with acetone and the compounding agent was removed, and heated at 50 ° C. for 1 week in a gear oven. . Thereafter, the anti-aging patch was peeled from the rubber sheet and punched into a dumbbell-shaped test piece (JIS dumbbell No. 3) to obtain a sample 3.
２．引張試験
上記サンプル１〜３について、ＪＩＳ Ｋ６２５１−２００４に準じて、破断強度（ＴB）〔ＭＰａ〕および破断伸び（ＥB）〔％〕を測定した。
また、上記サンプル１〜３を８０℃のギアオーブンに入れ、１２０時間および２４０時間老化させたものについて、同様に破断強度（ＴB）〔ＭＰａ〕および破断伸び（ＥB）〔％〕を測定した。
得られた結果から、破断強度保持率［１００×老化後ＴB／老化前ＴB （％）］および破断伸び保持率［１００×老化後ＥB／老化前ＥB （％）］を求めた。
結果を第２表に示す。
2. Tensile Test With respect to Samples 1 to 3, the breaking strength (T B ) [MPa] and the breaking elongation (E B ) [%] were measured according to JIS K6251-2004.
The samples 1 to 3 were placed in a gear oven at 80 ° C. and aged for 120 hours and 240 hours. Similarly, the breaking strength (T B ) [MPa] and elongation at break (E B ) [%] were measured. did.
From the results obtained, was determined breaking strength retention rate [after 100 × aging T B / aging before T B (%)] and elongation at break retention [100 × after aging E B / aging before E B (%)] .
The results are shown in Table 2.
第２表に示す結果から明らかなように、アセトン抽出により老化防止剤を抜いたサンプル２（比較例５）は、老化後の破断強度が大きく低下して保持率が低かった。
一方、アセトン抽出により老化防止剤を抜いたもの（サンプル２に相当）に本発明の老化防止用貼付材を貼り付けて老化防止剤を移行させたサンプル３（実施例３）は、比較例５に比べて老化後の破断強度および破断伸びの低下が少なく、耐老化性を復活できることが分かった。また、比較例４に比べて破断強度保持率および破断伸び保持率は同等またはそれ以上であったことから、本発明の老化防止用貼付材を使用することにより、耐老化性が失われた製品を初期の耐老化性レベル以上にすることが可能であり、防舷材等の製品の状態に応じて適切な耐老化性を付与し得ることが明らかとなった。
As is clear from the results shown in Table 2, Sample 2 (Comparative Example 5) from which the anti-aging agent was removed by extraction with acetone had a significantly reduced rupture strength after aging and a low retention rate.
On the other hand, Sample 3 (Example 3) in which the anti-aging agent of the present invention was applied to the sample from which the anti-aging agent was removed by extraction with acetone (corresponding to Sample 2) was transferred to Comparative Example 5 It was found that the aging resistance was revived with less decrease in breaking strength and breaking elongation after aging. Further, since the breaking strength retention rate and the breaking elongation retention rate were equal to or higher than those of Comparative Example 4, a product in which aging resistance was lost by using the anti-aging patch of the present invention. It has been clarified that the aging resistance can be made higher than the initial aging resistance level and appropriate aging resistance can be imparted depending on the state of the product such as the fender.
Claims (10)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009025044A1 (en) * | 2007-08-22 | 2009-02-26 | The Yokohama Rubber Co., Ltd. | Adhesive sheet material for aging prevention and method of preventing crosslinked rubber from aging |
| JP2018070813A (en) * | 2016-11-01 | 2018-05-10 | 住友ゴム工業株式会社 | Rubber composition for fenders |
| WO2020250996A1 (en) | 2019-06-13 | 2020-12-17 | 株式会社ブリヂストン | Antiaging-agent-supplying composition, antiaging-agent-supplying material, and method for supplying antiaging agent |
| CN112708214A (en) * | 2020-12-11 | 2021-04-27 | 厦门正新橡胶工业有限公司 | Anti-aging agent rubber patch, preparation method thereof and method for preparing tire by using anti-aging agent rubber patch |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009025044A1 (en) * | 2007-08-22 | 2009-02-26 | The Yokohama Rubber Co., Ltd. | Adhesive sheet material for aging prevention and method of preventing crosslinked rubber from aging |
| KR101174683B1 (en) | 2007-08-22 | 2012-08-16 | 요코하마 고무 가부시키가이샤 | Adhesive sheet material for aging prevention and method of preventing crosslinked rubber from aging |
| JP2018070813A (en) * | 2016-11-01 | 2018-05-10 | 住友ゴム工業株式会社 | Rubber composition for fenders |
| WO2020250996A1 (en) | 2019-06-13 | 2020-12-17 | 株式会社ブリヂストン | Antiaging-agent-supplying composition, antiaging-agent-supplying material, and method for supplying antiaging agent |
| CN113950512A (en) * | 2019-06-13 | 2022-01-18 | 株式会社普利司通 | Composition for supplying antioxidant, antioxidant supplying material, and method for supplying antioxidant |
| EP3985084A4 (en) * | 2019-06-13 | 2024-01-03 | Bridgestone Corp | Antiaging-agent-supplying composition, antiaging-agent-supplying material, and method for supplying antiaging agent |
| JP7464598B2 (en) | 2019-06-13 | 2024-04-09 | 株式会社ブリヂストン | Composition for supplying antioxidant, antioxidant supply material, and antioxidant supply method |
| CN112708214A (en) * | 2020-12-11 | 2021-04-27 | 厦门正新橡胶工业有限公司 | Anti-aging agent rubber patch, preparation method thereof and method for preparing tire by using anti-aging agent rubber patch |
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