JP2003096253A - Rubber composition stable for chlorine-based sterilized water - Google Patents
Rubber composition stable for chlorine-based sterilized waterInfo
- Publication number
- JP2003096253A JP2003096253A JP2001286666A JP2001286666A JP2003096253A JP 2003096253 A JP2003096253 A JP 2003096253A JP 2001286666 A JP2001286666 A JP 2001286666A JP 2001286666 A JP2001286666 A JP 2001286666A JP 2003096253 A JP2003096253 A JP 2003096253A
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- Japan
- Prior art keywords
- rubber
- main chain
- double bond
- chlorine
- synthetic resin
- 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.)
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Abstract
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【発明の属する技術分野】本発明は塩素（Ｃｌ２）、次
亜塩素酸（ＨＣｌＯ）、次亜塩素酸イオン（ＣｌＯ−）
等の塩素系物質を含む水に対して安定なゴム組成物に関
し、特に塩素系殺菌剤を含む上水道水と接する機器に用
いられる耐塩素ゴム組成物に関する。TECHNICAL FIELD The present invention relates to chlorine (Cl 2 ), hypochlorous acid (HClO), and hypochlorite ion (ClO − ).
TECHNICAL FIELD The present invention relates to a rubber composition containing chlorine-based substances such as, for example, stable against water, and more particularly to a chlorine-resistant rubber composition used in equipment in contact with tap water containing a chlorine-based bactericide.
【０００２】[0002]
【従来の技術】我国の水道水の殺菌はＣｌ２（塩素）又
はＮａＣｌＯ（次亜塩素酸ナトリウム）に依る塩素系殺
菌法が主体である。そして、この上水道中の残留有効塩
素濃度は、一般的に０．５〜１．０ＰＰＭの範囲である
が１．５ＰＰＭ程度と濃度の高い地域も見られる。近
年、水源となる河川、湖等の汚染が進み殺菌に使用する
塩素系殺菌剤の投入量が増す傾向にある。一方、我国の
生活水準の向上に伴い、各種給湯機器、食器洗浄機器、
ソーラーシステム等が普及し、各所でこれらの機器類が
利用されている。更に高層住宅等に使用されている減圧
弁機器、揚水機器の普及、これに伴い各所の配水管を接
続する接続機器等の使用が増大している。2. Description of the Related Art The main sterilization of tap water in Japan is a chlorine-based sterilization method using Cl 2 (chlorine) or NaClO (sodium hypochlorite). The residual effective chlorine concentration in the water supply is generally in the range of 0.5 to 1.0 PPM, but some regions have a high concentration of about 1.5 PPM. In recent years, the pollution of rivers, lakes, etc., which are water sources, has advanced, and the amount of chlorine-based germicide used for sterilization tends to increase. On the other hand, with the improvement of living standard in Japan, various hot water supply equipment, dishwashing equipment,
Solar systems and the like have become widespread, and these devices are being used in various places. In addition, pressure reducing valve equipment and pumping equipment used in high-rise houses are becoming widespread, and along with this, the use of connecting equipment for connecting water pipes at various places is increasing.
【０００３】これらの機器には多くのゴム製品が内蔵さ
れており、当初それらのゴム部品はＮＢＲ、ＥＰＭ、Ｅ
ＰＤＭ、Ｈ−ＮＢＲ等のゴム材質で作成され、充分な実
用耐久性を有すると推測されため多方面に於いて使用さ
れてきた。ところが、これらのゴム製品が上水道水に残
存する塩素系殺菌剤におかされて漏水が発生したり、あ
るいは侵されたゴム製品がちぎれて水中に浮遊し水道水
を汚染するという問題が発生し、関連業界でその対策に
苦慮しているのが現状である。Many rubber products are built in these devices, and initially, those rubber parts were NBR, EPM, E.
It is made of a rubber material such as PDM or H-NBR, and has been used in various fields because it is assumed to have sufficient practical durability. However, there is a problem that these rubber products are put into a chlorine-based bactericidal agent remaining in tap water to cause water leakage, or the affected rubber products are torn and float in water to contaminate tap water, The current situation is that the related industry is having difficulty in taking measures.
【０００４】このような問題を解決するため、エチレン
−プロピレン−ジエン・ターポリマーと、フェノールホ
ルムアルデヒド樹脂及びフタル酸系プレポリマーからな
る耐塩素水性ゴム（特開平９−２４９７７８）や、エチ
レン−プロピレンゴムと水素化アクリロニトリル・ブタ
ジエンゴムとをブレンドした耐塩素水性ゴム（特開平９
−１５７４６４）や、さらにエチレン−プロピレンゴム
と水素化アクリロニトリル・ブタジエンゴムとにジフェ
ニルアミンとメルカプトベンズイミダゾールを添加した
耐塩素水性ゴム（特開平１０−６０１９８）や、エチレ
ンプロピレン系ゴムにフッ素樹脂系微粉体を配合した耐
塩素水性ゴム（特開平５−２３０３００）が提案されて
いる。In order to solve such a problem, a chlorine-resistant water resistant rubber (Japanese Patent Application Laid-Open No. 9-249778) comprising an ethylene-propylene-diene terpolymer, a phenol formaldehyde resin and a phthalic acid prepolymer, and an ethylene-propylene rubber. Chlorine-resistant water-based rubber blended with hydrogenated acrylonitrile-butadiene rubber (Patent Document 1)
-1574664), or a chlorine-resistant water-based rubber obtained by adding diphenylamine and mercaptobenzimidazole to ethylene-propylene rubber and hydrogenated acrylonitrile-butadiene rubber (JP-A-10-60198), and ethylene propylene rubber, and fluororesin fine powder. A chlorine-resistant water-based rubber (JP-A-5-230300) has been proposed.
【０００５】この他にもゴム部材中にハイドロタルサイ
トを添加した耐水性ゴム（特開平６−２０００８０）
や、エチレン−プロピレン−エチリデンノルボーネン共
重合ゴムを使用したバタフライ弁用のラバーシート（特
開平５−４４８５７）や、オレフィン共重合体ポリマー
に有機不飽和シランとラジカル発生剤とシラノール重合
触媒及び酸化防止剤からなる給水給湯器用のゴムホース
（特開２０００−８５３５４）が提案されている。さら
には、エチレンプロピレンゴムとブチルゴムとからなる
ブレンドゴムにシリカ系充填剤を耐塩素水性ゴム組成物
が提案されている。（特開平４−３５３５４３）In addition to this, a water resistant rubber having hydrotalcite added to a rubber member (Japanese Patent Laid-Open No. 6-201280)
Or a rubber sheet for a butterfly valve using ethylene-propylene-ethylidene norbornene copolymer rubber (JP-A-5-44857), an olefin copolymer polymer with an organic unsaturated silane, a radical generator, a silanol polymerization catalyst and oxidation. A rubber hose (for example, Japanese Patent Laid-Open No. 2000-85354) for a water heater and water heater, which includes an inhibitor, has been proposed. Further, a chlorine-resistant water-based rubber composition in which a silica type filler is added to a blend rubber composed of ethylene propylene rubber and butyl rubber has been proposed. (JP-A-4-353543)
【０００６】[0006]
【発明が解決しようとする課題】ところが、上述した従
来の耐塩素性ゴムは現実には充分な耐塩素性を有するま
でには至っていない。そのため、近年では耐薬品性など
耐候性に優れるフッ素系ゴムを使用する例が増えてきた
が、このフッ素系ゴムはコストが高いうえ、耐薬品性以
外のゴムの物性に劣る場合がある。この様な実情に鑑
み、本発明は塩素系殺菌剤を含む水に対する耐久性を有
し、詳しくは、冷水、温水、熱水と長期間接触もしくは
浸漬された状態にあっても、塩素系殺菌剤による劣化を
受けることが極めて少なく、フッ素系ゴムに匹敵する耐
久性を有し、かつ物性の優れたコストの安い耐塩素性の
高いゴム組成物を提供することにある。However, the above-mentioned conventional chlorine-resistant rubber has not yet reached sufficient chlorine resistance in reality. Therefore, in recent years, an example of using a fluorine-based rubber having excellent weather resistance such as chemical resistance has increased, but this fluorine-based rubber is high in cost and may have inferior physical properties of the rubber other than the chemical resistance. In view of such circumstances, the present invention has durability against water containing a chlorine-based bactericide, and in particular, cold water, hot water, even in a state of being in contact with or immersed in hot water for a long time, chlorine-based sterilization It is an object of the present invention to provide a rubber composition that is extremely resistant to deterioration by a chemical agent, has durability comparable to that of a fluorine-based rubber, has excellent physical properties, and has low cost and high chlorine resistance.
【０００７】[0007]
【課題を解決するための手段】本発明者は、塩素系殺菌
水がゴムを劣化させる機構について鋭意検討を続けた結
果、（ａ）主鎖に２重結合を実質的に有しない飽和系合
成ゴムと、（ｂ）主鎖に２重結合を有するゴム素材及び
／又は主鎖に２重結合を有する合成樹脂と、（ｃ）充填
剤と、（ｄ）加硫剤、及び（ｅ）加硫促進剤とを主成分
とし、前記（ｂ）主鎖に２重結合を有するゴム素材及び
／又は主鎖に２重結合を有する合成樹脂の不飽和度が５
％以上であるゴム組成物とすることで前記課題を解決す
るに至った。The inventors of the present invention have conducted extensive studies on the mechanism by which chlorine-based sterilizing water deteriorates rubber, and as a result, (a) a saturated system synthesis having substantially no double bond in the main chain. Rubber, (b) a rubber material having a double bond in the main chain and / or a synthetic resin having a double bond in the main chain, (c) a filler, (d) a vulcanizing agent, and (e) The degree of unsaturation of the rubber material (b) having a double bond in the main chain and / or the synthetic resin having a double bond in the main chain, which has a sulfur accelerator as a main component, is 5
The above problem has been solved by using a rubber composition having a content of at least%.
【０００８】次に本発明の各要素について詳述する。本
発明を構成する（ａ）主鎖に２重結合を実質的に有しな
い飽和系合成ゴムは、加硫後のゴムの伸びや引っ張り強
度など加硫ゴムとしての基本的な物性を担うものであ
り、水道水等に含まれる塩素により劣化しないよう出来
る限り不飽和基を含まないゴム素材とすることが有効で
ある。具体的には、エチレン−プロピレン−ジエンゴム
（ＥＰＤＭ）、エチレン−プロピレンゴム（ＥＰＭ）、
水素化ニトリルブタジエンゴム（Ｈ−ＮＢＲ）、クロロ
スルホン化ポリエチレン（ＣＳＭ）、塩素化ポリエチレ
ン（ＣＰＥ）、エピクロルヒドリンゴム（ＣＨＲ、ＣＨ
Ｃ）、及びアクリルゴム（ＡＣＭ、ＡＮＭ）などが好ま
しく用いられるが、これらのゴム素材以外にも実質的に
不飽和基を有さないか、有していても極少量であれば使
用可能である。Next, each element of the present invention will be described in detail. The saturated synthetic rubber (a) which does not substantially have a double bond in the main chain constituting the present invention is responsible for basic physical properties as a vulcanized rubber such as elongation and tensile strength of the rubber after vulcanization. Therefore, it is effective to use a rubber material containing no unsaturated groups as much as possible so as not to be deteriorated by chlorine contained in tap water. Specifically, ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM),
Hydrogenated nitrile butadiene rubber (H-NBR), chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CPE), epichlorohydrin rubber (CHR, CH
C) and acrylic rubbers (ACM, ANM) and the like are preferably used, but other than these rubber materials, there is substantially no unsaturated group, or even if it has an extremely small amount, it can be used. is there.
【０００９】特に、塩素を含む上水道がまわりに使用さ
れる機器（給湯器など）など、水温が大きく変化する機
器に組み込まれるゴム製品においては、エチレン−プロ
ピレン−ジエンゴム（ＥＰＤＭ）、エチレン−プロピレ
ンゴム（ＥＰＭ）、及び水素化ニトリルブタジエンゴム
（水素化ＮＢＲ）がより好ましい。これらのゴム素材は
１種単独でも２種以上をブレンドして使用することも可
能である。Particularly, in a rubber product incorporated in a device whose water temperature greatly changes, such as a device around which a tap water containing chlorine is used (such as a water heater), ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM) and hydrogenated nitrile butadiene rubber (hydrogenated NBR) are more preferable. These rubber materials may be used alone or in a blend of two or more.
【００１０】本発明では（ｂ）主鎖に２重結合を有する
ゴム素材及び／又は主鎖に２重結合を有する合成樹脂
が、加硫後のゴム製品における耐塩素性を向上させてい
るものと思われる。その詳細な機構は不明であるが、加
硫後のゴム製品中に含まれる（ｂ）成分中の２重結合が
優先的に塩素と結合し、塩素置換された部位が近接する
水素と脱塩酸反応を繰り返すことにより、分子中に多く
の塩素を取り込むことが出来るようになるのではないと
考えられる。このため、前述の（ａ）飽和系ゴムに対す
る塩素のアタックが減少して高分子鎖の切断が起こりに
くくなるため、ゴムの劣化が進行せず耐塩素性が著しく
向上するものと思われる。In the present invention, (b) a rubber material having a double bond in the main chain and / or a synthetic resin having a double bond in the main chain improves chlorine resistance in a rubber product after vulcanization. I think that the. Although the detailed mechanism is unknown, the double bond in the component (b) contained in the rubber product after vulcanization preferentially bonds with chlorine, and hydrogen and dehydrochlorination where chlorine-substituted sites are close to each other. It is considered that it is not possible to incorporate a large amount of chlorine in the molecule by repeating the reaction. For this reason, it is considered that the chlorine attack on the above-mentioned (a) saturated rubber is reduced and the polymer chain is less likely to be broken, so that the deterioration of the rubber does not proceed and the chlorine resistance is significantly improved.
【００１１】上述の（ｂ）主鎖に２重結合を有するゴム
素材及び／又は主鎖に２重結合を有する合成樹脂として
は、分子内に不飽和結合を有するゴム素材や樹脂であれ
ば使用可能であるが、不飽和度が５％以上であることが
適当である。ここで用いる不飽和度をスチレンゴム（Ｓ
ＢＲ スチレンーブタジエン共重合ゴム）を例にとって
説明する。一般的にスチレンゴムは、（−ＣＨ２−ＣＨ
＝ＣＨ−ＣＨ２−）ｘの２重結合を有するブタジエンセ
グメントと、（−ＣＨ−ＣＨ（Ｐｈ）−）ｙのスチレン
セグメントとを所定の割合で共重合して作られるが、こ
こでいう不飽和度５％とは、ｘ／ｘ＋ｙ≧５％と表すこ
とができ、言い換えれば共重合体中にブタジエンセグメ
ントを５％以上含むスチレンゴムとすることができる。
なお、スチレンセグメント中にもベンゼン環（Ｐｈ）に
２重結合を有しているが、この場合は主鎖ではなく側鎖
であるため、本発明には該当しない。また、（−ＣＨ２
−Ｃ（ＣＨ３）＝ＣＨ−ＣＨ２−）ｎで示されるイソプ
レンゴムや、（−ＣＨ２−ＣＨ＝ＣＨ−ＣＨ２−）ｎで
示されるブタジエンゴムでは、不飽和度は１００％近い
ものとなる。本発明では、（ｂ）成分の添加量との兼ね
合いもあるが、少なくとも不飽和度を５％以上有するこ
とが必要であり、それ以下であると有効な耐塩素性が得
られない場合がある。また、フッ素系ゴムに匹敵する耐
塩素性を実現するには不飽和度を３０％以上とすること
が好ましい。As the rubber material (b) having a double bond in the main chain and / or the synthetic resin having a double bond in the main chain, any rubber material or resin having an unsaturated bond in the molecule can be used. Although possible, it is suitable that the degree of unsaturation is 5% or more. The degree of unsaturation used here is styrene rubber (S
BR styrene-butadiene copolymer rubber) will be described as an example. Generally styrene rubber, (- CH 2 -CH
= CH-CH 2 - and butadiene segments with) double bonds x, (- CH-CH ( Ph) -) but the y styrene segments are made by copolymerizing at a predetermined ratio, here not The degree of saturation of 5% can be expressed as x / x + y ≧ 5%, in other words, it can be a styrene rubber containing 5% or more of a butadiene segment in the copolymer.
Although the styrene segment also has a double bond in the benzene ring (Ph), this case does not correspond to the present invention because it is a side chain rather than a main chain. In addition, (-CH 2
-C (CH 3) = CH- CH 2 -) or isoprene rubber represented by n, (- CH 2 -CH = CH-CH 2 -) in the butadiene rubber represented by n, those unsaturation nearly 100% Becomes In the present invention, there is a balance with the amount of the component (b) added, but it is necessary to have at least an unsaturation degree of 5% or more, and if it is less than that, effective chlorine resistance may not be obtained. . Further, in order to realize chlorine resistance comparable to that of fluororubber, the degree of unsaturation is preferably 30% or more.
【００１２】前述の主鎖に２重結合を有する重合体のセ
グメント単位としては、−ＣＨ２−Ｃ（Ｒ）＝ＣＨ−Ｃ
Ｈ２−（Ｒはメチル基、又は塩素）で表されるイソプレ
ン構造やクロロプレン構造、あるいはこれらの誘導体
や、−ＣＨ２−ＣＨ＝ＣＨ−ＣＨ２−で表されるブタジ
エン構造あるいはこれらの誘導体が上げられる。本発明
に用いられる主鎖に２重結合を有するゴム素材の具体例
としては、天然ゴム（ＮＲ）、イソプレンゴム（Ｉ
Ｒ）、スチレンゴム（ＳＢＲ）、ブタジエンゴム（Ｂ
Ｒ）、ニトリルゴム（ＮＢＲ）及びクロロプレンゴム
（ＣＲ）などが上げられる。なお、主鎖に２重結合を持
たないイソブチレンセグメントと主鎖に２重結合を有す
るイソプレンセグメントを共重合して得られるブチルゴ
ム（ＩＩＲ）は、その市販品の多くがイソプレンセグメ
ントの含有量が数％以下（不飽和度５％未満）であるた
め、本発明には適さない場合が多い。As the segment unit of the above-mentioned polymer having a double bond in the main chain, —CH 2 —C (R) ═CH—C
H 2 - (R is methyl, or chlorine) isoprene structure or chloroprene structure represented by or or derivatives thereof,, -CH 2 -CH = CH- CH 2 - butadiene structure or a derivative thereof represented by the Can be raised. Specific examples of the rubber material having a double bond in the main chain used in the present invention include natural rubber (NR) and isoprene rubber (I).
R), styrene rubber (SBR), butadiene rubber (B
R), nitrile rubber (NBR) and chloroprene rubber (CR). In addition, butyl rubber (IIR) obtained by copolymerizing an isobutylene segment having no double bond in the main chain and an isoprene segment having a double bond in the main chain has many isoprene segment contents of many commercially available products. % Or less (unsaturation degree less than 5%), it is often not suitable for the present invention.
【００１３】また、主鎖に２重結合を有する合成樹脂と
しては、スチレン−ブタジエン−スチレンブロックコポ
リマー（ＳＢＳ）、スチレン−イソプレン−スチレンブ
ロックコポリマー（ＳＩＳ）、ポリメチルメタアクリレ
ート（ＰＭＭＡ）、ポリ酢酸ビニル（ＰＶＡｃ）、アク
リロニトリル−ブタジエン−スチレン共重合体（ＡＢ
Ｓ）、不飽和ポリエステル（無水マレイン酸−無水フタ
ル酸−プロピレンゴリコール共重合体）などが挙げられ
る。As the synthetic resin having a double bond in the main chain, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), polymethylmethacrylate (PMMA), polyacetic acid. Vinyl (PVAc), acrylonitrile-butadiene-styrene copolymer (AB
S), unsaturated polyester (maleic anhydride-phthalic anhydride-propylene glycol copolymer) and the like.
【００１４】これらの（ｂ）主鎖に２重結合を有するゴ
ム素材及び／又は主鎖に２重結合を有する合成樹脂の配
合量は、（ａ）主鎖に２重結合を実質的に有しない飽和
系合成ゴム１００重量部に対し、５〜５０重量部、好ま
しくは１０〜３５重量部である。（ｂ）成分の配合量が
５重量部未満であると有効な耐塩素性が得られず、また
５０重量部を越えると加硫後のゴム物性が低下する。The amount of the rubber material (b) having a double bond in the main chain and / or the synthetic resin having a double bond in the main chain is (a) substantially having a double bond in the main chain. 5 to 50 parts by weight, preferably 10 to 35 parts by weight, relative to 100 parts by weight of the saturated synthetic rubber. If the compounding amount of the component (b) is less than 5 parts by weight, effective chlorine resistance cannot be obtained, and if it exceeds 50 parts by weight, the rubber physical properties after vulcanization deteriorate.
【００１５】本発明に使用できる（ｃ）充填剤として
は、従来から公知の充填剤が使用可能である。具体的に
はカーボンブラックや、珪酸、珪酸塩、炭酸カルシウ
ム、炭酸マグネシウム、クレー、タルク、ベントナイ
ト、セリサイト、マイカ、アスベスト、珪酸カルシウ
ム、アルミナ水和物、硫酸バリウムなどの無機系充填剤
や、ポリエチレン樹脂、ポリプロピレン樹脂、スチレン
樹脂、クマロン−インデン樹脂、メラミン樹脂、フェノ
ール樹脂及びコルク粉末などの有機系充填剤が挙げられ
る。また、充填剤の配合量は、（ａ）主鎖に２重結合を
実質的に有しない飽和系合成ゴム１００重量部に対し
て、０．１〜２００重量部であるが、充填剤の種類によ
っては前記範囲外であっても配合可能な場合がある。こ
れらの充填剤はその目的に合わせて任意に種類、配合量
を決定すればよい。As the filler (c) usable in the present invention, conventionally known fillers can be used. Specifically, carbon black, and inorganic fillers such as silicic acid, silicates, calcium carbonate, magnesium carbonate, clay, talc, bentonite, sericite, mica, asbestos, calcium silicate, alumina hydrate, and barium sulfate, Examples of the organic filler include polyethylene resin, polypropylene resin, styrene resin, coumarone-indene resin, melamine resin, phenol resin and cork powder. The amount of the filler compounded is 0.1 to 200 parts by weight with respect to 100 parts by weight of the saturated synthetic rubber (a) having substantially no double bond in the main chain. Depending on the case, it may be possible to mix even outside the above range. The type and blending amount of these fillers may be arbitrarily determined according to the purpose.
【００１６】本発明に使用できる（ｄ）加硫剤（架橋
剤）及び（ｅ）加硫促進剤としては、従来から公知のも
のが使用可能である。加硫剤としては、例えば硫黄、粉
末硫黄、硫黄華、沈降硫黄、コロイド硫黄、塩化硫黄な
どの硫黄系化合物、セレン、テルル、酸化亜鉛、酸化マ
グネシウム、一酸化鉛などの無機化合物、モルホリンジ
スルフィド、アルキルフェノールジスルフィド、チウラ
ムジスルフィドなどの有機硫黄化合物、ジチオカルバミ
ン酸塩、オキシム類、ジニトロソ化合物、ポリアミン、
有機過酸化物などの有機系加硫剤が挙げられる。また、
加硫促進剤としては、例えば酸化亜鉛、酸化マグネシウ
ムなどの金属酸化物、水酸化カルシウムなどの金属水酸
化物、ステアリン酸、オレイン酸、ラウリン酸などの脂
肪酸、ステアリン酸亜鉛などの脂肪酸誘導体、ジエタノ
ールアミン、トリエタノールアミン、ジシクロヘキシル
アミンなどのアミン類、また、チアゾール系、スルフィ
ンアミド系、チウラム系、ジチオ酸塩系など各種有機化
合物が挙げられる。これらの加硫剤や加硫促進剤は２種
以上を混合して使用することもでき、また、必要に応じ
て従来公知の加硫助剤を併用してもよい。前記加硫剤や
加硫促進剤の添加量は従来から公知の添加量の範囲で差
し支えなく、ゴム素材や他の配合物の種類によって適宜
に決定される。As the (d) vulcanizing agent (crosslinking agent) and (e) vulcanization accelerator which can be used in the present invention, those conventionally known can be used. The vulcanizing agent, for example, sulfur, powdered sulfur, sulfur flower, precipitated sulfur, colloidal sulfur, sulfur compounds such as sulfur chloride, selenium, tellurium, zinc oxide, magnesium oxide, lead monoxide and other inorganic compounds, morpholine disulfide, Organic sulfur compounds such as alkylphenol disulfide and thiuram disulfide, dithiocarbamates, oximes, dinitroso compounds, polyamines,
Examples include organic vulcanizing agents such as organic peroxides. Also,
Examples of the vulcanization accelerator include metal oxides such as zinc oxide and magnesium oxide, metal hydroxides such as calcium hydroxide, fatty acids such as stearic acid, oleic acid and lauric acid, fatty acid derivatives such as zinc stearate and diethanolamine. Amines such as triethanolamine, dicyclohexylamine, and various organic compounds such as thiazole-based, sulfinamide-based, thiuram-based, and dithioate-based compounds. Two or more kinds of these vulcanizing agents and vulcanization accelerators may be mixed and used, and if necessary, a conventionally known vulcanization aid may be used in combination. The addition amount of the vulcanizing agent or vulcanization accelerator may be within the range of the conventionally known addition amount, and is appropriately determined depending on the type of the rubber material and other compound.
【００１７】この他にも加硫後のゴム製品の使用目的に
応じて様々な添加剤が使用可能である。例えば耐塩素性
をより高める目的で、ステアリン酸カルシウム、ステア
リン酸亜鉛、ステアリン酸錫、ジオクチル錫メルカプト
系、ジオクチル錫マレート系、モノオクチル錫メルカプ
ト系、ジブチル錫メルカプト系、ジブチル錫マレート
系、ジブチル錫ラウレート系の各化合物やハイドロタル
サイト類、エポキシ化大豆油、エポキシ亜麻仁油、エポ
キシ化木綿油等のエポキシ化植物油を添加してもよい。In addition to these, various additives can be used depending on the intended use of the rubber product after vulcanization. For example, for the purpose of further increasing chlorine resistance, calcium stearate, zinc stearate, tin stearate, dioctyltin mercapto, dioctyltin malate, monooctyltin mercapto, dibutyltin mercapto, dibutyltin malate, dibutyltin laurate. You may add each compound of a system, hydrotalcites, epoxidized soybean oil, epoxy flaxseed oil, epoxidized vegetable oil, such as epoxidized cotton oil.
【００１８】本発明にはさらに、通常のゴム組成物に添
加される公知の加硫助剤、加工助剤、老化防止剤、補強
剤、軟化剤、着色剤、充填剤等を添加しても良い。Further, known vulcanization aids, processing aids, antioxidants, reinforcing agents, softeners, coloring agents, fillers and the like which are added to ordinary rubber compositions may be added to the present invention. good.
【００１９】本発明のゴム組成物は、通常前述した各成
分を混練りし所望の形状に成形した後、加硫を施すこと
によって製品化される。具体的な成形加硫方法として
は、従来から公知の射出成形、加圧（プレス）成形、押
し出し成形、カレンダー成形などの方法が利用でき、例
えば加圧成形を行う場合は１３０〜１８０℃で、５０〜
３００ｋｇｆ／ｃｍ２に加圧し、２〜３０分加硫させる
ことにより成形できる。その他の方法においても条件を
適宜選択することで容易に成形可能である。また、必要
に応じて２次加硫を行ってもよい。The rubber composition of the present invention is usually made into a product by kneading the above-mentioned components and molding them into a desired shape, followed by vulcanization. As a concrete molding vulcanization method, conventionally known methods such as injection molding, pressure (press) molding, extrusion molding and calender molding can be used. For example, in the case of performing pressure molding, at 130 to 180 ° C., 50-
It can be molded by applying a pressure of 300 kgf / cm 2 and vulcanizing for 2 to 30 minutes. In other methods, molding can be easily performed by appropriately selecting the conditions. Moreover, you may perform secondary vulcanization | cure as needed.
【００２０】[0020]
【発明の実施の形態】以下実施例に基づき本発明を詳述
する。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail based on the following examples.
【実施例１〜４０、比較例１〜１２】表１〜６に示され
る配合割合で各成分を混練りし、均一な状態の加硫ゴム
組成物を得た。次にこの加硫ゴム組成物を任意の条件
（温度：１６０〜１７５℃ 時間：７〜１０分程度 加
圧：１８０ｋｇｆ／ｃｍ２ この成形加硫条件はゴム素
材や架橋剤の種類、添加量などに任意に設定される。）
で加硫させ、ｔ２（厚み２ｍｍ）、２５０□（２５０ｍ
ｍ×２５０ｍｍ）のゴムシートを得た。このゴムシート
から３５ｍｍ×３５ｍｍの試料を採取し、塩素濃度２０
０ｐｐｍの７０℃温水に浸漬し、表１〜８中に示すとお
り所定時間経過後の試料片の変化状態を目視及び指触に
よりゴムの劣化と浸漬液の状態を評価した。その結果を
表１〜６に示す。なお、比較例１０のフッ素系ゴム以外
は、一次加硫のみで二次加硫は行っていない。Examples 1 to 40, Comparative Examples 1 to 12 The components were kneaded at the compounding ratios shown in Tables 1 to 6 to obtain vulcanized rubber compositions in a uniform state. Next, this vulcanized rubber composition is subjected to arbitrary conditions (temperature: 160 to 175 ° C., time: about 7 to 10 minutes, pressure: 180 kgf / cm 2). Is set arbitrarily.)
Vulcanized at t2 (thickness 2 mm), 250 □ (250 m
A rubber sheet of m × 250 mm) was obtained. A 35 mm x 35 mm sample was taken from this rubber sheet, and the chlorine concentration was 20
The specimen was immersed in 0 ppm hot water at 70 ° C., and as shown in Tables 1 to 8, the deterioration state of the rubber and the state of the immersion liquid were evaluated visually and by touch with the finger for the change state of the sample piece after a predetermined time. The results are shown in Tables 1-6. It should be noted that, except for the fluorine-based rubber of Comparative Example 10, only secondary vulcanization was performed without primary vulcanization.
【００２１】なお、各表中の試験結果の評価は以下に準
ずる。
＜ゴム劣化試験＞
Ａ：全く又は殆ど劣化していない
Ｂ：やや劣化
Ｃ：かなり劣化、実用上支障有り
Ｄ：劣化大、ゴム崩壊
＜浸漬液の状態＞
Ａ：変化なし
Ｂ：やや汚染、小ゴムカス浮遊
Ｃ：かなり汚染、ゴムカス浮遊大
Ｄ：汚染大、黒水状となる。The evaluation of the test results in each table is based on the following. <Rubber deterioration test> A: No or almost no deterioration B: Some deterioration C: Significant deterioration, trouble in practical use D: Large deterioration, rubber collapse <Immersion liquid state> A: No change B: Some pollution, small Rubber debris floating C: considerably contaminated, rubber debris floating large D: contaminated, black water.
【００２２】[0022]
【表１】 [Table 1]
【００２３】[0023]
【表２】 [Table 2]
【００２４】[0024]
【表３】 [Table 3]
【００２５】[0025]
【表４】 [Table 4]
【００２６】[0026]
【表５】 [Table 5]
【００２７】[0027]
【表６】 [Table 6]
【００２８】[0028]
【表７】 [Table 7]
【００２９】前記各表の成分記号等は以下を意味する。
（ａ）主鎖に２重結合を実質的に有しない飽和系合成ゴ
ム
・エスプレン５２４：住友化学工業社製 エチレンプロ
ピレンゴム（ＥＰＤＭ）
・ゼットポール１０２０：日本ゼオン社製 水素化ニト
リルブタジエンゴム（Ｈ−ＮＢＲ）
（ｂ）主鎖に２重結合を有するゴム素材及び／又は主鎖
に２重結合を有する合成樹脂
・ＩＲ２２００：日本ゼオン社製 ポリイソプレンゴム
（ＩＲ）
・ニッポール１０４１：日本ゼオン社製 ニトリルブタ
ジエンゴム（ＮＢＲ）
その他のゴム
・バイトン Ｅ６０Ｃ：デュポン・ダウ・エラストマー
社製 フッ素ゴムで、加硫剤は系中に既に含有されてい
る。
・ブチル３６５：日本ブチル社製 不飽和３％のブチル
ゴム（ＩＩＲ）
（ｄ）加硫剤及び（ｅ）加硫促進剤
加硫系１（硫黄系）
・ノクセラーＣＺ：大内新興化学社製 加硫促進剤
・ノクセラーＴＲＡ：大内新興化学社製 加硫促進剤
・ノクセラーＭ：大内新興化学社製 加硫促進剤
・ノクセラーＴＴ：大内新興化学社製 加硫促進剤
・アクチングＳＬ：吉富製薬社製 加硫促進剤
加硫系２（パーオキサイド系）
・ＴＭＰＴ：トリメチロールプロパントリアクリレート
・パーヘキサ２５Ｂ：日本油脂社製 有機過酸化物
・ペロキシモンＦ４０：日本油脂社製 有機過酸化物
（ｃ）充填剤
ＦＥＦカーボン：旭カーボン社製
その他
ノクラツクＣＤ：大内新興化学社製 老化防止剤
ノクラックＭＢ：大内新興化学社製 老化防止剤
ＴＰ−９５：三洋貿易社製 可塑剤The component symbols and the like in the above tables mean the following. (A) Saturated synthetic rubber which does not substantially have a double bond in the main chain-Esprene 524: Ethylene propylene rubber (EPDM) manufactured by Sumitomo Chemical Co., Ltd.-Zetpol 1020: Hydrogenated nitrile butadiene rubber manufactured by Zeon Corporation (H) -NBR) (b) A rubber material having a double bond in the main chain and / or a synthetic resin having a double bond in the main chain-IR2200: manufactured by ZEON Corporation Polyisoprene rubber (IR) -Nippole 1041: manufactured by ZEON CORPORATION Nitrile Butadiene Rubber (NBR) Other Rubber Viton E60C: Fluorine rubber manufactured by DuPont Dow Elastomers, in which the vulcanizing agent is already contained in the system. -Butyl 365: Nippon Butyl Co., Ltd. Unsaturated 3% butyl rubber (IIR) (d) Vulcanizing agent and (e) Vulcanization accelerator Vulcanizing system 1 (Sulfur type) -Noccer CZ: Ouchi Shinko Chemical Co., Ltd. Vulcanization accelerator / NOXCELLER TRA: Ouchi Shinko Chemical Co., Ltd. Vulcanization accelerator / NOXCELLER M: Ouchi Shinko Chemical Co., Ltd. Vulcanization accelerator / NOXCELLER TT: Ouchi Shinko Chemical Co., Ltd. Vulcanization accelerator / Acting SL: Yoshitomi Pharmaceutical Co., Ltd. Vulcanization accelerator Vulcanization system 2 (peroxide system) -TMPT: trimethylolpropane triacrylate-Perhexa 25B: NOF Corporation's organic peroxide-PEROXIMONE F40: NOF Corporation's organic peroxide (c ) Filler FEF Carbon: Asahi Carbon Co., Ltd. Others Nocrack CD: Ouchi Shinko Chemical Co., Ltd. Antioxidant Nocrac MB: Ouchi Shinko Chemical Co., Ltd. Antiaging Agent TP-95: Sanyo Trading Co., Ltd. Plastic
【００３０】表１〜６によれば、（ａ）主鎖に２重結合
を実質的に有しない飽和系合成ゴム１００重量部に対し
て、（ｂ）主鎖に２重結合を有するゴム素材及び／又は
主鎖に２重結合を有する合成樹脂をゴム組成物を５重量
部以上配合すると５００時間程度までは充填剤のカーボ
ン紛の脱落が起こらず、また、１０重量部以上配合する
と１０００時間を超えてもカーボン紛の脱落がないもの
がある。According to Tables 1 to 6, (a) 100 parts by weight of a saturated synthetic rubber having substantially no double bond in the main chain, and (b) a rubber material having a double bond in the main chain. And / or the synthetic resin having a double bond in the main chain is mixed with the rubber composition in an amount of 5 parts by weight or more, the carbon powder of the filler does not fall off for up to about 500 hours, and if 10 parts by weight or more is added, it is 1000 hours. Some carbon powder does not fall off even if it exceeds.
【００３１】また、表１の比較例３〜６から、主鎖に２
重結合を有するゴム素材単体では、全く耐塩素性を有し
ていないことが分かる。さらに、表７によれば、本発明
のゴム組成物は、１０００時間を超える塩素含有水への
浸漬後でもフッ素系ゴムと同等もしくはそれ以上のゴム
物性を有しており、十分な耐久性を有していることが分
かる。In addition, from Comparative Examples 3 to 6 in Table 1, 2 was added to the main chain.
It can be seen that the rubber material alone having a heavy bond does not have chlorine resistance at all. Further, according to Table 7, the rubber composition of the present invention has rubber properties equivalent to or higher than that of the fluorine-based rubber even after immersion in chlorine-containing water for more than 1000 hours, and has sufficient durability. You know that you have.
【００３２】[0032]
【発明の効果】（ａ）主鎖に２重結合を実質的に有しな
い飽和系合成ゴムと、（ｂ）不飽和度が５％以上の主鎖
に２重結合を有するゴム素材及び／又は主鎖に２重結合
を有する合成樹脂と、（ｃ）充填剤と、（ｄ）加硫剤、
及び（ｅ）加硫促進剤とを配合した組成物は、水道水な
ど塩素を含む水に対して十分な耐塩素性を有している。
この耐塩素性は主に（ｂ）主鎖に２重結合を有するゴム
素材及び／又は主鎖に２重結合を有する合成樹脂の配合
量に依存し、特に（ａ）主鎖に２重結合を実質的に有し
ない飽和系合成ゴム１００重量部に対して１０重量部以
上添加した系では、フッ素系ゴムに匹敵する耐塩素性を
有する。EFFECTS OF THE INVENTION (a) A saturated synthetic rubber having substantially no double bonds in the main chain, and (b) a rubber material having a double bond in the main chain having an unsaturation degree of 5% or more and / or A synthetic resin having a double bond in the main chain, (c) a filler, (d) a vulcanizing agent,
The composition containing (e) the vulcanization accelerator has sufficient chlorine resistance against water containing chlorine such as tap water.
This chlorine resistance mainly depends on the compounding amount of (b) a rubber material having a double bond in the main chain and / or a synthetic resin having a double bond in the main chain, and particularly (a) a double bond in the main chain. In a system in which 10 parts by weight or more is added to 100 parts by weight of a saturated synthetic rubber which does not substantially contain chlorine, chlorine resistance comparable to that of a fluorine-based rubber is obtained.
【００３３】また、１０００時間を超えてカーボン紛の
脱落を起こさなかったゴムは、一般的なゴム物性におい
てもフッ素系ゴムに匹敵もしくはそれを凌ぐ十分な耐久
性を有している。このため、（ａ）〜（ｅ）の各成分を
任意に選択配合して目的に応じた製品を製造することが
容易で、コストの安いゴム製品が得られる。Further, the rubber which did not cause the carbon powder to fall off for more than 1000 hours has a durability which is equal to or more than that of the fluororubber in general rubber physical properties. Therefore, it is possible to easily produce a product according to the purpose by arbitrarily blending the components (a) to (e) and obtain a low cost rubber product.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｌ 11/00 Ｃ０８Ｌ 11/00 Ｆターム(参考） 4J002 AC012 AC032 AC062 AC071 AC072 AC082 AC092 AH003 BB033 BB123 BB151 BB241 BB271 BC033 BG041 BK003 CC033 CC183 CH041 DA036 DA047 DA117 DE077 DE078 DE088 DE107 DE108 DE146 DE157 DE236 DG017 DG046 DJ006 DJ026 DJ036 DJ046 DJ056 EF058 EG048 EK007 EN007 EN038 EN048 ES007 ES017 EV047 EV147 EV168 EV288 EV328 FD013 FD016 FD147 FD158 GB00 GC00─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C08L 11/00 C08L 11/00 F term (reference) 4J002 AC012 AC032 AC062 AC071 AC072 AC082 AC092 AH003 BB033 BB123 BB151 BB241 BB271 BC033 BG041 BK003 CC033 CC183 CH041 DA036 DA047 DA117 DE077 DE078 DE088 DE107 DE108 DE146 DE157 DE236 DG017 DG046 DJ006 DJ026 DJ036 DJ046 DJ056 EF058 EG048 GC EK007 EN007 EN038 EN048 ES007 ES017 EV047 EV016FD03 EV038 EV017 EV038 EV0
Claims (7)
い飽和系合成ゴムと、（ｂ）主鎖に２重結合を有するゴ
ム素材及び／又は主鎖に２重結合を有する合成樹脂と、
（ｃ）充填剤と、（ｄ）加硫剤、及び（ｅ）加硫促進剤
とを主成分とし、前記（ｂ）主鎖に２重結合を有するゴ
ム素材及び／又は主鎖に２重結合を有する合成樹脂の不
飽和度が５％以上であることを特徴とする塩素系殺菌水
に安定なゴム組成物。1. A saturated synthetic rubber having substantially no double bonds in its main chain, and (b) a rubber material having double bonds in its main chain and / or having double bonds in its main chain. Synthetic resin,
A rubber material having (c) a filler, (d) a vulcanizing agent, and (e) a vulcanization accelerator as main components, and having (b) a double bond in the main chain and / or double in the main chain. A rubber composition stable to chlorine-based sterilizing water, wherein the synthetic resin having a bond has an unsaturation degree of 5% or more.
しない飽和系合成ゴムが、エチレン−プロピレン−ジエ
ンゴム（ＥＰＤＭ）、エチレン−プロピレンゴム（ＥＰ
Ｍ）、水素化ニトリルブタジエンゴム（水素化ＮＢ
Ｒ）、クロロスルホン化ポリエチレン（ＣＳＭ）、塩素
化ポリエチレン（ＣＰＥ）、エピクロルヒドリンゴム
（ＣＨＲ、ＣＨＣ）、及びアクリルゴム（ＡＣＭ、ＡＮ
Ｍ）から選択される１種以上である請求項１に記載の塩
素系殺菌水に安定なゴム組成物。2. The saturated synthetic rubber having substantially no double bond in the main chain (a) is ethylene-propylene-diene rubber (EPDM) or ethylene-propylene rubber (EP).
M), hydrogenated nitrile butadiene rubber (hydrogenated NB
R), chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CPE), epichlorohydrin rubber (CHR, CHC), and acrylic rubber (ACM, AN)
The rubber composition stable to chlorine-based sterilizing water according to claim 1, which is one or more selected from M).
しない飽和系合成ゴムが、エチレン−プロピレン−ジエ
ンゴム（ＥＰＤＭ）、エチレン−プロピレンゴム（ＥＰ
Ｍ）、及び水素化ニトリルブタジエンゴム（水素化ＮＢ
Ｒ）から選択される１種以上である請求項２に記載の塩
素系殺菌水に安定なゴム組成物。3. The saturated synthetic rubber (a) having substantially no double bond in the main chain is ethylene-propylene-diene rubber (EPDM) or ethylene-propylene rubber (EP).
M), and hydrogenated nitrile butadiene rubber (hydrogenated NB
The rubber composition stable to chlorine-based sterilizing water according to claim 2, which is one or more selected from R).
素材及び／又は主鎖に２重結合を有する合成樹脂の不飽
和度が３０％以上である請求項１に記載の塩素系殺菌水
に安定なゴム組成物。4. The chlorine-based material according to claim 1, wherein (b) the rubber material having a double bond in the main chain and / or the synthetic resin having a double bond in the main chain has an unsaturation degree of 30% or more. A rubber composition that is stable to sterilizing water.
素材及び／又は主鎖に２重結合を有する合成樹脂の添加
量が、（ａ）主鎖に２重結合を実質的に有しない飽和系
合成ゴム１００重量部に対して５〜５０重量部である請
求項１に記載の塩素系殺菌水に安定なゴム組成物。5. The addition amount of the rubber material (b) having a double bond in the main chain and / or the synthetic resin having a double bond in the main chain is substantially the same as (a) the double bond in the main chain. The rubber composition stable to chlorine-based sterilizing water according to claim 1, which is contained in an amount of 5 to 50 parts by weight based on 100 parts by weight of the saturated synthetic rubber which is not contained.
素材及び／又は主鎖に２重結合を有する合成樹脂が、分
子内に下記式（１）で示されるセグメントを有する重合
体である請求項１に記載の塩素系殺菌水に安定なゴム組
成物。 （ただし、ＲはＨ、ＣＨ３又はＣｌ）6. A polymer in which the rubber material (b) having a double bond in the main chain and / or the synthetic resin having a double bond in the main chain has a segment represented by the following formula (1) in the molecule. The rubber composition stable to chlorine-based sterilizing water according to claim 1. (However, R is H, CH 3 or Cl)
素材及び／又は主鎖に２重結合を有する合成樹脂が、天
然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、スチレンゴ
ム（ＳＢＲ）、ブタジエンゴム（ＢＲ）、ニトリルゴム
（ＮＢＲ）、及びクロロプレンゴム（ＣＲ）から選択さ
れる１種以上である請求項１記載の塩素系殺菌水に安定
なゴム組成物。7. The rubber material (b) having a double bond in the main chain and / or the synthetic resin having a double bond in the main chain are natural rubber (NR), isoprene rubber (IR), styrene rubber (SBR). ), A butadiene rubber (BR), a nitrile rubber (NBR), and a chloroprene rubber (CR), the rubber composition stable to chlorine-based sterilizing water according to claim 1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001286666A JP2003096253A (en) | 2001-09-20 | 2001-09-20 | Rubber composition stable for chlorine-based sterilized water |
| PCT/JP2002/003776 WO2002085978A1 (en) | 2001-04-19 | 2002-04-16 | Rubber compositions stable to water sterilized with chlorine and molded rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001286666A JP2003096253A (en) | 2001-09-20 | 2001-09-20 | Rubber composition stable for chlorine-based sterilized water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003096253A true JP2003096253A (en) | 2003-04-03 |
| JP2003096253A5 JP2003096253A5 (en) | 2011-02-24 |
Family
ID=19109602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001286666A Pending JP2003096253A (en) | 2001-04-19 | 2001-09-20 | Rubber composition stable for chlorine-based sterilized water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003096253A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004137369A (en) * | 2002-10-17 | 2004-05-13 | Three Bond Co Ltd | Rubber composition |
| JP2009191216A (en) * | 2008-02-18 | 2009-08-27 | Morisei Kako:Kk | Rubber prevented from whitening by tap water |
| WO2010050494A1 (en) * | 2008-10-29 | 2010-05-06 | ダイソー株式会社 | Semi-conductive rubber composition and vulcanizate thereof |
| JP2017122140A (en) * | 2016-01-05 | 2017-07-13 | 三菱電線工業株式会社 | Rubber composition and rubber seal prepared therewith |
| JP7167376B1 (en) | 2022-07-04 | 2022-11-08 | 株式会社小野ダスキン | Rubber composition and mat |
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| JP2004137369A (en) * | 2002-10-17 | 2004-05-13 | Three Bond Co Ltd | Rubber composition |
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| JP2017122140A (en) * | 2016-01-05 | 2017-07-13 | 三菱電線工業株式会社 | Rubber composition and rubber seal prepared therewith |
| JP7167376B1 (en) | 2022-07-04 | 2022-11-08 | 株式会社小野ダスキン | Rubber composition and mat |
| JP2024006701A (en) * | 2022-07-04 | 2024-01-17 | 株式会社小野ダスキン | Rubber composition and mat |
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