JP4101194B2 - Foam molding - Google Patents
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- JP4101194B2 JP4101194B2 JP2004058616A JP2004058616A JP4101194B2 JP 4101194 B2 JP4101194 B2 JP 4101194B2 JP 2004058616 A JP2004058616 A JP 2004058616A JP 2004058616 A JP2004058616 A JP 2004058616A JP 4101194 B2 JP4101194 B2 JP 4101194B2
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Description
本発明は、発泡成形体に係り、特に、シール材として用いられる発泡成形体に関する。 The present invention relates to a foam molded body, and more particularly to a foam molded body used as a sealing material.
地中に埋設された下水道や排水路等の管路は、ヒューム管、陶管等が広く使用されている。これらの管路の内壁は、硫化水素やその他の腐食ガス及び付着物による侵食や劣化によって管厚が薄くなり強度が低下してしまう。また、地圧や地盤沈下等の影響により、管路継目部の隙間や管路自体のクラックが発生すると、地下水等の管路内への流入や管路内の水の地中への漏水が起こり、管路周辺の土砂が流出して管路外周面に空洞部が発生し、路面陥没などの原因となってしまう。 As pipes such as sewers and drainage channels buried in the ground, fume pipes, ceramic pipes, etc. are widely used. The inner walls of these pipes are reduced in thickness due to erosion and deterioration caused by hydrogen sulfide and other corrosive gases and deposits. In addition, if a crack in the pipe joint or the pipe itself occurs due to the influence of earth pressure or ground subsidence, the inflow of underground water or other water into the pipe or leakage of water in the pipe into the ground may occur. Occurring, earth and sand around the pipe flow out, and a hollow portion is generated on the outer peripheral surface of the pipe, which causes a road surface depression.
上記問題を解決するために管路を補修する手段として、嵌合体を管路の筒長方向に沿って筒状に組み立てた後、嵌合体と管路内面との空隙内に硬化性充填材を注入する手段が知られている（例えば特許文献１参照）。この手段では、嵌合体の嵌合部に合成ゴムや水膨張性ゴム等のシール材を介在させているが、このシール材は、嵌合部材に接着部材等で貼り付けて使用されているものであり、シール材の自重によって、シール材と接着部材との剥離や接着部材と嵌合部材との剥離が発生してシール材が落下してしまうという問題があった。また、シール材として合成ゴムを採用した際には、合成ゴム自体が経時的に劣化して弾性が低下し、嵌合部に隙間が発生してしまうという問題があった。 As a means for repairing the pipe line in order to solve the above problem, after assembling the fitting body into a cylindrical shape along the pipe length direction of the pipe line, a curable filler is placed in the gap between the fitting body and the pipe inner surface. Means for injecting is known (for example, see Patent Document 1). In this means, a sealing material such as synthetic rubber or water-expandable rubber is interposed in the fitting portion of the fitting body. This sealing material is used by being attached to the fitting member with an adhesive member or the like. In addition, due to the weight of the sealing material, there is a problem in that the sealing material falls due to peeling between the sealing material and the adhesive member and peeling between the adhesive member and the fitting member. Further, when synthetic rubber is employed as the sealing material, there has been a problem that the synthetic rubber itself deteriorates with time and the elasticity is lowered, and a gap is generated in the fitting portion.
管路の内面に新たな管路を新設せずに、管路の補修部に環状のゴムバンドを帯状の鋼製バンドで圧着させて漏水止めを行う方法も知られている（例えば特許文献２参照）。しかしながらこの方法では、漏水止めのためのゴムバンドを、鋼製バンドによって非常に強い圧力で圧着しなければならないこと、経時変化によってゴムバンドが劣化し再度漏水が発生してしまうという問題があった。
本発明の課題は、シール性を維持し作業性を向上させたシール材として用いることのできる発泡成形体を提供することにある。 The subject of this invention is providing the foaming molding which can be used as a sealing material which maintained the sealing performance and improved workability | operativity.
本発明者らは、鋭意検討を重ねた結果、特定組成物を含有させた組成物を加硫及び発泡処理した発泡成形体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させるに至った。 As a result of intensive studies, the present inventors have found that the above problems can be solved by a foamed molded article obtained by vulcanizing and foaming a composition containing a specific composition, and have completed the present invention.
すなわち本発明は、硫黄加硫可能なゴム成分：１００質量部、下記一般式（Ａ）で表されるスルホアルキル（メタ）アクリレート系単量体、下記一般式（Ｂ）で表される（メタ）アクリルアミド系単量体及び下記一般式（Ｃ）で表される（メタ）アクリル酸系単量体からなる共重合体の架橋物：１０〜１００質量部、加硫剤：０．１〜１０質量部、加硫促進剤：０．１〜１０質量部、加熱発泡剤：０．５〜５０質量部を含有する組成物を、加硫及び発泡処理したものであり、密度が０．２〜０．８ｇ／ｃｍ３、２３℃の精製水に７日間浸漬して吸水させたときの膨張倍率が１．２〜８倍であり、シール材として用いられることを特徴とする発泡成形体である。
（式中のＲ１は水素原子又はメチル基、Ｒ２は炭素数２〜４の直鎖状又は分岐鎖状アルキレン基、Ｘは水素原子、アルカリ金属、アルカリ土類金属及びアンモニウム基のうちのいずれか１種を示す）
（式中のＲ３、Ｒ４、Ｒ５はそれぞれ水素原子又はメチル基を示す）
（式中のＲ６は水素原子又はメチル基、Ｙは水素原子、アルカリ金属、アルカリ土類金属及びアンモニウム基のうちのいずれか１種を示す）
That is, the present invention is a sulfur vulcanizable rubber component: 100 parts by mass, a sulfoalkyl (meth) acrylate monomer represented by the following general formula (A), and represented by the following general formula (B) (meta ) Crosslinked product of copolymer consisting of acrylamide monomer and (meth) acrylic acid monomer represented by the following general formula (C): 10 to 100 parts by mass, vulcanizing agent: 0.1 to 10 A composition containing parts by mass, a vulcanization accelerator: 0.1 to 10 parts by mass, and a heating foaming agent: 0.5 to 50 parts by mass is vulcanized and foamed, and has a density of 0.2 to 0.8 g / cm 3 , a foamed molded article having an expansion ratio of 1.2 to 8 times when immersed in purified water at 23 ° C. for 7 days and used as a sealing material .
(R 1 in the formula is a hydrogen atom or a methyl group, R 2 is a linear or branched alkylene group having 2 to 4 carbon atoms, X is one of hydrogen atom, alkali metal, alkaline earth metal and ammonium groups Any one is shown)
(Wherein R 3 , R 4 and R 5 each represent a hydrogen atom or a methyl group)
(Wherein R 6 represents a hydrogen atom or a methyl group, Y represents any one of a hydrogen atom, an alkali metal, an alkaline earth metal and an ammonium group)
本発明の発泡成形体は、熱分解性発泡剤を組成物中で膨張させて軽量化を図ると共に、ゴム成分を加硫させて強度を保持したものであり、接着部材からの自重による剥離を防止できるという効果を有する。また、発泡成形体中に吸水性樹脂を配合したものであり、接触した水を吸水して膨張するため、水漏れに対するシール性を向上できるという効果を有する。 The foamed molded product of the present invention is a material which is made by expanding a thermally decomposable foaming agent in the composition to reduce the weight and vulcanizing the rubber component to maintain the strength. It has the effect that it can be prevented. Moreover, since the water-absorbent resin is blended in the foamed molded article and the contacted water is absorbed and expanded, it has an effect of improving the sealing performance against water leakage.
本発明の硫黄加硫可能なゴム成分は、後述する吸水性樹脂、加硫剤、加硫促進剤及び熱分解性発泡剤等をその内部に均一に分散保持させるものであり、例えば、天然ゴム、イソプレンゴム、スチレンブタジエンゴム、クロロプレンゴム等のジエン系ゴムの他にブチルゴム、エチレンプロピレンジエンゴム等の主鎖中に少量の二重結合を導入したものが挙げられる。本発明のゴム成分にあっては、これらの単体だけでなく、混練性、成形性等を改善するために２種以上を混合して使用してもよい。これらの中でも特に、クロロプレンゴム及び／又はエチレンプロピレンゴムを用いると混練性、成形性が改善される効果が高く好ましい。 The rubber component capable of sulfur vulcanization of the present invention is to uniformly disperse and hold a water-absorbing resin, a vulcanizing agent, a vulcanization accelerator, a thermally decomposable foaming agent and the like, which will be described later. In addition to diene rubbers such as isoprene rubber, styrene butadiene rubber and chloroprene rubber, there may be mentioned those in which a small amount of double bonds are introduced into the main chain such as butyl rubber and ethylene propylene diene rubber. In the rubber component of the present invention, not only these simple substances but also two or more kinds may be mixed and used in order to improve kneadability and moldability. Among these, use of chloroprene rubber and / or ethylene propylene rubber is preferable because the effect of improving kneadability and moldability is high.
本発明に用いる吸水性樹脂としては、一般式（化１）で表されるスルホアルキル（メタ）アクリレート系単量体、一般式（化２）で表される（メタ）アクリルアミド系単量体及び一般式（化３）で表される（メタ）アクリル酸系単量体からなる共重合体の架橋物である。
スルホアルキル（メタ）アクリレート系単量体の例としては、２−スルホエチルアクリレート、２−スルホエチルメタクリレート、２−スルホプロピルアクリレート、２−スルホブチルアクリレート、２−スルホブチルメタクリレートなどの不飽和スルホン酸や、それらのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩などが挙げられ、これらは単独でも２種以上を組み合わせてもよい。 Examples of sulfoalkyl (meth) acrylate monomers include unsaturated sulfonic acids such as 2-sulfoethyl acrylate, 2-sulfoethyl methacrylate, 2-sulfopropyl acrylate, 2-sulfobutyl acrylate, and 2-sulfobutyl methacrylate. And alkali metal salts, alkaline earth metal salts, and ammonium salts thereof. These may be used alone or in combination of two or more.
（メタ）アクリルアミド系単量体の例としては、アクリルアミド、メタクリルアミド、Ｎ−メチルアクリルアミド、Ｎ−メチルメタクリルアミド、Ｎ，Ｎ−ジメチルメタクリルアミドなどが挙げられ、これらは単独でも２種以上を組み合わせてもよい。 Examples of (meth) acrylamide monomers include acrylamide, methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, N, N-dimethyl methacrylamide, etc., and these may be used alone or in combination of two or more. May be.
（メタ）アクリル酸系単量体の例としては、アクリル酸、メタクリル酸、それらのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩などが挙げられ、これらは単独でも２種以上を組み合わせてもよい。 Examples of (meth) acrylic acid monomers include acrylic acid, methacrylic acid, alkali metal salts thereof, alkaline earth metal salts, ammonium salts, and the like. These may be used alone or in combination of two or more. Good.
本発明の吸水性樹脂の配合量は、ゴム成分１００質量部あたり１０〜１００質量部である。配合量が１０質量部未満では発泡成形体の水膨張倍率が不十分となり、１００質量部を超えると発泡成形体自体の強度が低下するため好ましくない。 The amount of the water-absorbent resin of the present invention is 10 to 100 parts by mass per 100 parts by mass of the rubber component. If the blending amount is less than 10 parts by mass, the water expansion ratio of the foamed molded product becomes insufficient, and if it exceeds 100 parts by mass, the strength of the foamed molded product itself decreases, which is not preferable.
本発明の加硫剤及び加硫促進剤は、ゴム成分の架橋度を向上させ、得られる発泡成形体自体の強度を向上させるものである。 The vulcanizing agent and vulcanization accelerator of the present invention improve the degree of crosslinking of the rubber component and improve the strength of the resulting foamed molded product itself.
加硫剤としては、硫黄、ポリスルフィド、塩化硫黄等の含硫黄化合物からなる硫黄系、ｐ−キノンジオキシム、ｐ−ｐ−ジベンゾイルキノンオキシム等のオキシム系、ｔ−ブチルハイドロパーオキサイド、アセチルアセトンパーオキサイド、クメンハイドロパーオキサイド等の有機過酸化物系がある。加硫剤は少なくとも硫黄系のものを含めれば、複数種のものを組み合わせて使用してもよい。これら加硫剤の使用量は、ゴム成分１００質量部あたり０．１〜１０質量部、特に０．５〜５質量部が好ましい。 Vulcanizing agents include sulfur-based compounds containing sulfur-containing compounds such as sulfur, polysulfide, and sulfur chloride, oxime-based compounds such as p-quinonedioxime and pp-dibenzoylquinoneoxime, t-butyl hydroperoxide, and acetylacetone peroxide. There are organic peroxides such as oxide and cumene hydroperoxide. As long as the vulcanizing agent includes at least a sulfur-based one, a plurality of types may be used in combination. The amount of these vulcanizing agents used is preferably 0.1 to 10 parts by mass, particularly 0.5 to 5 parts by mass per 100 parts by mass of the rubber component.
加硫処理の促進を目的に加硫促進剤が使用される。加硫促進剤としては、テトラメチルチウラムジスルフィド、テトラブチルチウラムジスルフィド、テトラメチルチウラムモノスルフィド、ジペンタメチレンチウラムテトラスルフィド等のチウラム系、２−メルカプトベンゾチアゾール、ジベンゾチアゾールジスルフィド等のチアゾール系、ジメチルジチオカルバミン酸亜鉛、ジエチルジチオカルバミン酸亜鉛等のジチオカルバミン酸塩系、ｎ−ブチルアルデヒドアニリン等のアルデヒドアミン系、Ｎ−シクロヘキシル−２−ベンゾチアジルスルフェンアミド等のスルフェンアミド系、ジオルソトリルグアニジン、ジオルソニトリルグアニジン等のグアニジン系、チオカルバニリド、ジエチルチオユリア、トリメチルチオユリア等のチオユリア系、亜鉛華などの化合物がある。加硫促進剤は、これらの単体だけでなく、２種以上のものを組み合わせて使用してもよい。これら加硫促進剤の使用量は、ゴム成分１００質量部あたり０．１〜１０質量部で、特に０．２〜５質量部が好ましい。 A vulcanization accelerator is used for the purpose of accelerating the vulcanization treatment. Vulcanization accelerators include thiurams such as tetramethylthiuram disulfide, tetrabutylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram tetrasulfide, thiazoles such as 2-mercaptobenzothiazole, dibenzothiazole disulfide, dimethyldithiocarbamine Dithiocarbamates such as zinc oxide, zinc diethyldithiocarbamate, aldehyde amines such as n-butyraldehydeaniline, sulfenamides such as N-cyclohexyl-2-benzothiazylsulfenamide, diorthotolylguanidine, di There are guanidine compounds such as orthonitrile guanidine, thiourea compounds such as thiocarbanilide, diethylthiourea and trimethylthiourea, and zinc white compounds. The vulcanization accelerator may be used in combination of not only these simple substances but also two or more kinds. The amount of these vulcanization accelerators used is 0.1 to 10 parts by mass, particularly 0.2 to 5 parts by mass, per 100 parts by mass of the rubber component.
加熱発泡剤としては、アゾジカルボンアミド、アゾビスイソブチロニトリル、アゾジアミノベンゼン、アゾシクロヘキシルニトリル等のアゾ系発泡剤、Ｎ，Ｎ’−ジニトロソペンタメチレンテトラミン、Ｎ，Ｎ’−ジメチルＮ，Ｎ’−ジニトロソテレフタルアミド等のニトロソ系発泡剤、ベンゼンスルフォニルヒドラジド、ｐ，ｐ’−オキシビス（ベンゼンスルフォニルヒドラジド）、トルエンスルフォニルヒドラジド、ジフェニルスルホン−３，３’−ジスルフォニルヒドラジド等のスルフォニルヒドラジド系発泡剤等の有機系発泡剤、重炭酸アンモニウム、炭酸アンモニウム、炭酸水素ナトリウム、亜硝酸アンモニウム、カルシウムアジド等の無機系発泡剤が使用できる。発泡剤の使用量は、目的とする発泡体の物性に応じて適宜調整すればよいが、ゴム成分１００質量％あたり０．５〜５０質量部、特に１〜２０質量部が好ましい。また、必要に応じて、これら発泡剤と併用して発泡助剤を使用してもよい。発泡助剤としては、サリチル酸、フタル酸、ステアリン酸、しゅう酸、尿酸またはその誘導体などがあげられる。 Examples of the heating foaming agent include azo foaming agents such as azodicarbonamide, azobisisobutyronitrile, azodiaminobenzene, azocyclohexylnitrile, N, N′-dinitrosopentamethylenetetramine, N, N′-dimethylN, Nitroso-based blowing agents such as N′-dinitrosotephthalamide, sulfonyl hydrazides such as benzenesulfonyl hydrazide, p, p′-oxybis (benzenesulfonyl hydrazide), toluenesulfonyl hydrazide, diphenylsulfone-3,3′-disulfonyl hydrazide Organic foaming agents such as foaming agents, and inorganic foaming agents such as ammonium bicarbonate, ammonium carbonate, sodium hydrogen carbonate, ammonium nitrite and calcium azide can be used. Although the usage-amount of a foaming agent should just adjust suitably according to the physical property of the target foam, 0.5-50 mass parts per 100 mass% of rubber components, especially 1-20 mass parts are preferable. Moreover, you may use a foaming adjuvant in combination with these foaming agents as needed. Examples of the foaming aid include salicylic acid, phthalic acid, stearic acid, oxalic acid, uric acid or derivatives thereof.
本発明の発泡成形体は、これらの成分を含有する組成物を混練し、所望する形状に成形し、加熱発泡剤の発泡開始温度以上で加熱して発泡処理と加硫処理を行うことによって得られるものである。なお、加硫処理と発泡処理は、別工程で行ってもよく同時に行ってもよい。 The foamed molded article of the present invention is obtained by kneading a composition containing these components, molding the composition into a desired shape, and heating and heating at a temperature equal to or higher than the foaming start temperature of the heating foaming agent to perform foaming and vulcanization. It is what Note that the vulcanization treatment and the foaming treatment may be performed in separate steps or simultaneously.
発泡成形体の密度は、良好な機械的強度及び柔軟性を得られる点で、０．２〜０．８ｇ／ｃｍ３であるものが好ましい。密度が０．２ｇ／ｃｍ３に満たない場合は、発泡体の圧縮、反発力が小さいため止水効果が十分に得られず設置初期の止水性が低下してしまい、０．８ｇ／ｃｍ３を超える場合は、シール材の柔軟性低下、重量増加となり施工性不良、シール材の剥がれ等の不具合が生じ好ましくない。 The density of the foamed molded product is preferably 0.2 to 0.8 g / cm 3 in that good mechanical strength and flexibility can be obtained. When the density is less than 0.2 g / cm 3 , the compression and repulsion force of the foam is small, so that the water stop effect cannot be sufficiently obtained and the water stop at the initial stage of installation is lowered, and 0.8 g / cm 3 If it exceeds 1, the flexibility of the sealing material will decrease and the weight will increase, causing problems such as poor workability and peeling of the sealing material.
発泡成形体の水膨張倍率は、次式（数１）により算出されるもので、２３℃の精製水に７日間浸漬させて吸水させた発泡成形体の膨張倍率を表したものであり、１．２〜８倍であるものが好ましい。水膨張倍率が１．２倍に満たない場合は、発泡成形体の膨張不足により施工箇所から漏水が発生しても塞ぎきれず、８倍を超える場合は、発泡成形体自体の強度が低下してしまうので好ましくない。
組成物を混練する装置としては、従来公知のミキサー、バンバリーミキサー、ニーダーミキサー、二本ロール等の混練装置があり、混練した組成物を成形する装置としては、従来公知のプレス成形、押し出し成形、カレンダー成形等の成形装置がある。一般には、組成物をゴム用押出し機で製品形状に押出し、次いで、加硫槽内に導入し、熱空気、流動床、マイクロ波等の手段によって加熱することにより加硫及び発泡を行うことが出来る。また、発泡成形体の形状は、シート状やテープ状など適宜用途に合わせて設計すれば良い。
As an apparatus for kneading the composition, there are kneading apparatuses such as conventionally known mixers, Banbury mixers, kneader mixers, two rolls, etc., and as apparatuses for molding the kneaded composition, conventionally known press molding, extrusion molding, There are molding devices such as calendar molding. In general, the composition is extruded into a product shape with a rubber extruder, then introduced into a vulcanizing tank, and vulcanized and foamed by heating by means of hot air, fluidized bed, microwave or the like. I can do it. Moreover, what is necessary is just to design the shape of a foaming molding according to a use suitably, such as a sheet form and a tape form.
なお、本発明の発泡成形体は、その効果を阻害しない範囲で、通常の加硫ゴムに使用される無機充填剤、可塑剤、軟化剤、老化防止剤、加工助剤、滑剤、粘着付与剤等を併用しても良いものである。無機充填剤としては、例えば、シリカ、珪藻土、アルミナ、酸化亜鉛、酸化チタン、酸化マグネシウム、酸化鉄、ホウ酸亜鉛、ホウ酸、炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛、炭酸バリウム、ハイドロタルサイト、水酸化アルミニウム、水酸化マグネシウム、硫酸カルシウム、硫酸バリウム、ケイ酸カルシウム、タルク、クレー、マイカ、ベントナイト、活性白土、セピオライト、ガラス繊維、ガラスビーズ、窒化アルミニウム、窒化ホウ素、カーボンブラック、グラファイト、炭素繊維等があり、これらは単体だけでなく２種以上を混合して使用しても良い。また、無機充填剤の粒径は、ゴム成分への分散性の観点から、１〜５０μｍが好ましい。カーボンブラックは、補強剤として機能し、得られる発泡成形体の圧縮歪低減に有効である。成形性の調整に有効な可塑剤や軟化剤の例としては、パラフィン系やナフテン系等のプロセスオイル、流動パラフィン、その他のパラフィン類、ワックス類、シリコーンオイルや液状ポリブテン等の合成高分子系軟化剤、フタル酸系やアジピン酸系、セバシン酸系やリン酸系等のエステル系可塑剤類、ステアリン酸やそのエステル類、アルキルスルホン酸エステル類や粘着付与剤などがあげられる。 The foamed molded article of the present invention is an inorganic filler, plasticizer, softening agent, anti-aging agent, processing aid, lubricant, and tackifier used in ordinary vulcanized rubber as long as the effect is not impaired. Etc. may be used in combination. Examples of the inorganic filler include silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, magnesium oxide, iron oxide, zinc borate, boric acid, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, hydrotalcite, water Aluminum oxide, magnesium hydroxide, calcium sulfate, barium sulfate, calcium silicate, talc, clay, mica, bentonite, activated clay, sepiolite, glass fiber, glass beads, aluminum nitride, boron nitride, carbon black, graphite, carbon fiber, etc. These may be used alone or in combination of two or more. The particle size of the inorganic filler is preferably 1 to 50 μm from the viewpoint of dispersibility in the rubber component. Carbon black functions as a reinforcing agent and is effective in reducing the compression strain of the resulting foamed molded article. Examples of plasticizers and softeners that are effective in adjusting formability include paraffinic and naphthenic process oils, liquid paraffin, other paraffins, waxes, synthetic polymer softening such as silicone oil and liquid polybutene. Agents, ester plasticizers such as phthalic acid, adipic acid, sebacic acid and phosphoric acid, stearic acid and its esters, alkylsulfonic acid esters and tackifiers.
本発明の発泡成形体は、施工箇所の形状によって種々の形状を選定できるが一般にテープ状が好適である。発泡成形体は施工箇所に市販の両面テープや接着剤で貼り付けてもよく、釘打、ビス止め等によって結合されてもよい。 The foamed molded article of the present invention can be selected from various shapes depending on the shape of the construction site, but generally a tape shape is suitable. The foamed molded product may be affixed to the construction site with a commercially available double-sided tape or adhesive, or may be bonded by nailing, screwing, or the like.
管路の補修として本発明の発泡成形体が好適に用いられる例として、次のものが挙げられる。すなわち、特許文献１に記載されているように、管路内に搬入可能な補強部材を用いて管路内面に中空骨組み状の補強体を組立て、その補強体の内側に複数の嵌合部材を取り付けて内面部材を嵌合させ、これら嵌合体を管路の筒長方向に沿って筒状に組み立てた後、嵌合体と管路内面との空隙内に硬化性充填材を注入することによって補修する方法において、本発明の発泡成形体を嵌合部材へ貼り付けて、嵌合体の漏水を防止する方法である。また、特許文献２に記載されているように、管路の漏水部分に内面から環状ゴムバンドを帯状の鋼製バンドで圧着装着する際に、ゴムバンドと管路内面との間に本発明の発泡成形体を介在させる方法に用いてもよい。 The following is mentioned as an example in which the foaming molding of the present invention is used suitably as repair of a pipe line. That is, as described in Patent Document 1, a hollow frame-shaped reinforcing body is assembled on the inner surface of the pipe using a reinforcing member that can be carried into the pipe, and a plurality of fitting members are provided inside the reinforcing body. After fitting and fitting the inner surface members and assembling these fitting bodies into a cylindrical shape along the tube length direction of the pipe line, repairing is performed by injecting a curable filler into the gap between the fitting body and the pipe inner face. In this method, the foamed molded product of the present invention is attached to the fitting member to prevent water leakage of the fitted product. Further, as described in Patent Document 2, when the annular rubber band is pressure-bonded to the water leakage portion of the pipe from the inner surface with a band-shaped steel band, the gap between the rubber band and the inner face of the pipe is You may use for the method of interposing a foaming molding.
ここで、内面部材及び嵌合部材は下水道管用ポリエチレン樹脂をはじめとするオレフィン系熱可塑性樹脂、不飽和ポリエステル樹脂、繊維強化樹脂やステンレス等の金属が使用できる。また中空骨組み状の補強体は鋼材等からなる高剛性材料が用いられる。硬化性充填材としては、例えばセメントミルク、モルタル、コンクリート等のセメント系材料、あるいはエポキシ樹脂等の熱硬化性樹脂等が用いることができ、要求性能やコスト等によって選択される。環状ゴムバンドは必要な強度、耐久性、弾性を有する合成ゴムであり、クロロプレンゴム、スチレンブタジエンゴム、イソプレンゴム、アクリロニトリル−ブタジエンゴム、エチレン−プロピレン−ジエンゴム等が使用できる。 Here, the inner surface member and the fitting member can be made of metal such as olefin-based thermoplastic resin such as polyethylene resin for sewer pipes, unsaturated polyester resin, fiber reinforced resin, and stainless steel. The hollow frame-shaped reinforcing body is made of a highly rigid material made of steel or the like. As the curable filler, for example, a cement-based material such as cement milk, mortar, concrete, or a thermosetting resin such as an epoxy resin can be used, and is selected according to required performance, cost, and the like. The cyclic rubber band is a synthetic rubber having necessary strength, durability, and elasticity, and chloroprene rubber, styrene butadiene rubber, isoprene rubber, acrylonitrile-butadiene rubber, ethylene-propylene-diene rubber, and the like can be used.
以下、本発明を実施例により具体的に説明するが、これらの実施例は本発明を限定するものでない。なお、以下の説明における部及び％は質量基準に基づく。 Hereinafter, the present invention will be specifically described by way of examples. However, these examples do not limit the present invention. In addition, the part and% in the following description are based on a mass reference | standard.
「実施例１」
本実施例において使用した材料は、それぞれ以下に示したものである。
（１）ゴム成分：クロロプレンゴム（電気化学化学工業(株)製、「ＥＳ−７０」)、エチレン−プロピレン−ジエンゴム（ＤＳＭジャパン(株)製、「ケルタン６６４０Ｂ」）
（２）吸水性樹脂：スルホエチルアクリレート−アクリルアミド−アクリル酸共重合体ナトリウム塩の架橋物（（株）日本触媒製「アクアリックＣＳ−６Ｓ」）
（３）加硫剤：粉末硫黄（細井化学工業（株）製）
（４）加硫促進剤：Ｎ−シクロヘキシル−２−ベンゾチアジルスルフェンアミド（大内新興（株）製、「ノクセラーＣＺ」）、テトラメチルチウラムジスルフィド（大内新興（株）製、「ノクセラーＴＴ」）、酸化亜鉛（堺化学（株）製、「亜鉛華３号」）
（５）加熱発泡剤：アゾジカルボンアミド（白石カルシウム（株）製、「セロゲンＡＺ」）、ｐ，ｐ’−オキシビス（ベンゼンスルフォニルヒドラジド））（白石カルシウム（株）製、「セロゲンＯＴ−１」、尿素化合物（永和化成（株）製、「セルペースト１０１Ｗ」）
（６）無機充填剤：ホワイトカーボン（日本シリカ（株）製、「ニップシールＶＮ３」）
（７）可塑剤：ジ−ｎ−オクチルフタレート（大八化学（株）製、「Ｎ−ＤＯＰ」）
（８）老化防止剤：４，４’−（α，α−ジメチルベンジル）ジフェニルアミン（大内新興（株）製、「ノクラックＣＤ」）
（９）カーボンブラック：旭カーボン（株）製、「＃６０」
（１０）軟化剤：プロセスオイル（日本サン石油（株）製、「サンパー１５０」）
（１１）粘着剤：ポリブテン（アモコ社製、「Ｈ３００」）
"Example 1"
The materials used in this example are as shown below.
(1) Rubber component: Chloroprene rubber (manufactured by Electrochemical Chemical Co., Ltd., “ES-70”), ethylene-propylene-diene rubber (manufactured by DSM Japan Co., Ltd., “Keltan 6640B”)
(2) Water-absorbing resin: crosslinked product of sulfoethyl acrylate-acrylamide-acrylic acid copolymer sodium salt (“AQUALIC CS-6S” manufactured by Nippon Shokubai Co., Ltd.)
(3) Vulcanizing agent: Powdered sulfur (made by Hosoi Chemical Co., Ltd.)
(4) Vulcanization accelerator: N-cyclohexyl-2-benzothiazylsulfenamide (manufactured by Ouchi Shinsei Co., Ltd., “Noxeller CZ”), tetramethylthiuram disulfide (manufactured by Ouchi Shinsei Co., Ltd., “Noxeller”) TT "), zinc oxide (manufactured by Sakai Chemical Co., Ltd.," Zinc Hana 3 ")
(5) Heating foaming agent: azodicarbonamide (manufactured by Shiroishi Calcium Co., Ltd., “Serogen AZ”), p, p′-oxybis (benzenesulfonylhydrazide)) (manufactured by Shiroishi Calcium Co., Ltd., “Serogen OT-1”) Urea compound (manufactured by Eiwa Kasei Co., Ltd., “Cell Paste 101W”)
(6) Inorganic filler: White carbon (Nippon Silica Co., Ltd., “Nip seal VN3”)
(7) Plasticizer: Di-n-octyl phthalate (“N-DOP” manufactured by Daihachi Chemical Co., Ltd.)
(8) Anti-aging agent: 4,4 ′-(α, α-dimethylbenzyl) diphenylamine (manufactured by Ouchi Shinsei Co., Ltd., “NOCRACK CD”)
(9) Carbon black: “# 60” manufactured by Asahi Carbon Co., Ltd.
(10) Softener: Process oil (manufactured by Nippon Sun Oil Co., Ltd., “Thumper 150”)
(11) Adhesive: Polybutene (Amoco, “H300”)
「発泡成形体」
表１の配合Ａに示した成分を、容量３リットルのニーダーミキサーを用いて１２０℃で２分間混練した。次いで、得られた混練物を二本ロールで練りながら、表１の配合Ｂに示した成分を添加して５分間混練し、幅２０ｍｍ、厚み１０ｍｍの口金を取り付けたゴム用押出機にて帯状に押出成形し、次いで、熱風加硫槽を用いて２１０℃で２分間加熱して加硫処理及び発泡処理を行い、発泡成形体を得た。
"Foamed molded product"
The ingredients shown in Formulation A in Table 1 were kneaded for 2 minutes at 120 ° C. using a kneader mixer with a capacity of 3 liters. Next, while kneading the obtained kneaded material with two rolls, the components shown in Formulation B in Table 1 were added and kneaded for 5 minutes, and a belt-shaped extruder was attached to a rubber extruder equipped with a die having a width of 20 mm and a thickness of 10 mm. Then, vulcanization treatment and foaming treatment were performed by heating at 210 ° C. for 2 minutes using a hot air vulcanizing tank to obtain a foamed molded product.
本実施例にあっては、以下に記載した各特性を評価し、表１にまとめた。各特性の測定方法を以下に示す。
密度：ＪＩＳ Ｋ ６２６８に準じて電子比重計（Ｍｉｒａｇｅ Ｔｒａｄｉｎｇ社製：ＥＷ１２０ＳＧ）で測定した。
水膨張倍率：長さ５０ｍｍ×巾２０ｍｍ×厚さ３ｍｍに切断した試料の質量を測定した後、２３℃の精製水に７日間浸漬させて吸水させ、資料表面の水分をろ紙でふき取って質量を測定し、次式（数２）により水膨張倍率を求めた。
止水圧：図１に示したように、発泡成形体（１）を、外径５０ｃｍ鋼製の止水圧試験機（２）に接着セットして初期圧縮率０％でボルト（３）にて締結し止水圧試験機（２）内に水を満たし、７日間吸水養生させた後水圧をかけて漏水が発生する直前の水圧を測定した。
In this example, each characteristic described below was evaluated and summarized in Table 1. The measuring method of each characteristic is shown below.
Density: Measured with an electronic hydrometer (Mirage Trading, Inc .: EW120SG) according to JIS K 6268.
Water expansion ratio: After measuring the mass of a sample cut to a length of 50 mm × width of 20 mm × thickness of 3 mm, the sample was immersed in purified water at 23 ° C. for 7 days to absorb water, and the moisture on the surface of the material was wiped off with a filter paper. The water expansion ratio was determined by the following equation (Equation 2).
Water stop pressure: As shown in FIG. 1, the foamed molded body (1) is bonded and set to a water stop pressure tester (2) made of steel with an outer diameter of 50 cm and fastened with a bolt (3) at an initial compression rate of 0%. The water stop pressure tester (2) was filled with water, and was allowed to absorb water for 7 days, and then water pressure was applied to measure the water pressure immediately before the occurrence of water leakage.
「実施例２〜４」及び「比較例１〜２」
実施例２〜４及び比較例１〜２においては、実施例１のゴム組成物の配合を、それぞれ表１に記載した材料および配合量に変更し、実施例１と同様の方法で成形体を得、その各特性を評価したものである。各特性の評価結果を、表１にまとめた。
"Examples 2-4" and "Comparative Examples 1-2"
In Examples 2 to 4 and Comparative Examples 1 and 2, the compounding of the rubber composition of Example 1 was changed to the materials and compounding amounts described in Table 1, respectively, and the molded product was obtained in the same manner as in Example 1. Obtained and evaluated for each characteristic. The evaluation results of each characteristic are summarized in Table 1.
１ 発泡成形体
２ 止水圧試験機
３ ボルト
４ 入水口
５ 排水口
６ 水圧計
DESCRIPTION OF SYMBOLS 1 Foam molding 2 Water stop pressure tester 3 Bolt 4 Water inlet 5 Water outlet 6 Water pressure gauge
Claims (3)
密度が０．２〜０．８ｇ／ｃｍ３、２３℃の精製水に７日間浸漬して吸水させたときの膨張倍率が１．２〜８倍であり、
シール材として用いられることを特徴とする発泡成形体。
（式中のＲ１は水素原子又はメチル基、Ｒ２は炭素数２〜４の直鎖状又は分岐鎖状アルキレン基、Ｘは水素原子、アルカリ金属、アルカリ土類金属及びアンモニウム基のうちのいずれか１種を示す）
（式中のＲ３、Ｒ４、Ｒ５はそれぞれ水素原子又はメチル基を示す）
（式中のＲ６は水素原子又はメチル基、Ｙは水素原子、アルカリ金属、アルカリ土類金属及びアンモニウム基のうちのいずれか１種を示す） Rubber component capable of sulfur vulcanization: 100 parts by mass, sulfoalkyl (meth) acrylate monomer represented by the following general formula (A), (meth) acrylamide single monomer represented by the following general formula (B) And a crosslinked product of a copolymer composed of a (meth) acrylic acid monomer represented by the following general formula (C): 10 to 100 parts by mass, vulcanizing agent: 0.1 to 10 parts by mass, vulcanization Accelerator: 0.1 to 10 parts by mass, heating foaming agent: a composition containing 0.5 to 50 parts by mass, vulcanized and foamed,
The expansion ratio is 1.2 to 8 times when the density is 0.2 to 0.8 g / cm 3 and immersed in purified water of 23 ° C. for 7 days to absorb water,
A foamed molded article characterized by being used as a sealing material.
(R 1 in the formula is a hydrogen atom or a methyl group, R 2 is a linear or branched alkylene group having 2 to 4 carbon atoms, X is one of hydrogen atom, alkali metal, alkaline earth metal and ammonium groups Any one is shown)
(Wherein R 3 , R 4 and R 5 each represent a hydrogen atom or a methyl group)
(Wherein R 6 represents a hydrogen atom or a methyl group, Y represents any one of a hydrogen atom, an alkali metal, an alkaline earth metal and an ammonium group)
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