JP2009242618A - Foamed sheet of rubber-based resin with closed cell and its manufacturing method - Google Patents
Foamed sheet of rubber-based resin with closed cell and its manufacturing method Download PDFInfo
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本発明は、ゴム系樹脂独立気泡発泡シートに関し、詳しくは、アイオノマー変性されたゴム系樹脂を含み、電気、エレクトロニクス、車輌などの分野で各種シール材として好適に用いることができるゴム系樹脂独立気泡発泡シート及びその製造方法に関する。 The present invention relates to a rubber-based resin closed cell foam sheet, and more specifically, a rubber-based resin closed cell that includes an ionomer-modified rubber resin and can be suitably used as various sealing materials in the fields of electricity, electronics, vehicles, and the like. The present invention relates to a foam sheet and a method for producing the same.
現在、建築、土木、電気、エレクトロニクス、車輌等の各種分野におけるシール材として、発泡体が広く使用されている。このようなシール材に供される発泡体としては、例えば、ポリエチレン系樹脂、ポリプロピレン系樹脂等からなる熱可塑性樹脂発泡体や、合成ゴム又は天然ゴムからなるゴム発泡体等が挙げられる。 Currently, foam is widely used as a sealing material in various fields such as architecture, civil engineering, electricity, electronics, and vehicles. Examples of the foam used for such a sealing material include a thermoplastic resin foam made of polyethylene resin, polypropylene resin, etc., a rubber foam made of synthetic rubber or natural rubber, and the like.
シール材の中でも、パッキン・ガスケット材は、車両、弱電などの各種構造物の間隙を埋めるために使用され、衝撃に対するクッションとしての働きを持ちつつ、構造物内部への塵の侵入を防止する為に用いられる。 Among seal materials, packing / gasket materials are used to fill gaps in various structures such as vehicles and light electrical power, and serve as cushions against impacts while preventing dust from entering the structure. Used for.
この種の発泡体からなるパッキン・ガスケット材は、耐衝撃性及び防塵性が要求される周縁部に圧縮した状態で設置され、その圧縮柔軟性及び反発応力により界面との隙間を塞ぎ、塵の侵入を防止している。この場合、シール材の圧縮柔軟性が低いと、発泡体が圧縮状態から形状回復しようとする反発力により、被シール部材が変形したり、被シール部材の変形により被シール部分の隙間が拡大したりするといった問題があり、その結果、シール性能が劣り、防塵できないといった問題点があった。 Packing and gasket materials made of this type of foam are installed in a compressed state at the periphery where impact resistance and dust resistance are required. The compression flexibility and repulsive stress close the gap between the interface and dust. Prevents intrusion. In this case, if the compression flexibility of the sealing material is low, the sealed member is deformed due to the repulsive force of the foam to recover its shape from the compressed state, or the gap of the sealed portion is enlarged due to the deformation of the sealed member. As a result, there is a problem that the sealing performance is inferior and the dust cannot be prevented.
そこで、加圧等の手段によって発泡体中の気泡を破泡させることにより連続気泡化させ、発泡体の圧縮柔軟性を向上させることが行われている。しかし、気泡を連続気泡化すると、発泡体の圧縮柔軟性は著しく向上するものの、止水性が低下してしまうという新たな問題が発生してしまう。即ち、連続気泡構造を有する発泡体からなるシール材を用いると、被シール部分の隙間よりも非常に厚いシール材を必要とするにもかかわらず、初期シール性が不充分である等、完全な止水性が期待できなかった。 Therefore, it has been practiced to open the bubbles by breaking the bubbles in the foam by means such as pressurization to improve the compression flexibility of the foam. However, when the bubbles are made into continuous cells, the compression flexibility of the foam is remarkably improved, but a new problem that the waterstop performance is lowered occurs. That is, when a sealing material made of a foam having an open cell structure is used, a sealing material that is much thicker than the gap of the sealed portion is required, but the initial sealing property is insufficient. The water stopping property could not be expected.
一般に、ゴム発泡体などは、優れたクッション性を有し、クッション材、パット材などの用途に有用である。発泡構造体における独立気泡と連続気泡とを比較すると、前者は、気泡間が立体格子状に隔壁で仕切られた構造であるのに対して、後者は、互いに隣接する気泡間を連通させる貫通孔が隔壁に形成された構造であり、後者の方が力学的に変形させやすい。しかしながら、連続気泡は、止水作用があまり期待できないのに対し、独立気泡は、気泡間の隔壁のために止水作用が期待できる。 In general, a rubber foam or the like has excellent cushioning properties and is useful for applications such as cushion materials and pad materials. Comparing the closed cells and the open cells in the foam structure, the former is a structure in which the bubbles are partitioned by a partition in a three-dimensional grid, whereas the latter is a through-hole that communicates between adjacent bubbles. Is a structure formed in the partition wall, and the latter is more easily mechanically deformed. However, open cells cannot be expected to have a water-stopping effect, whereas closed cells can be expected to have a water-stopping effect because of the partition walls between the bubbles.
独立気泡と連続気泡との両気泡を有する発泡構造体は、連続気泡に基づく易変形性による複雑な間隙への充填作業の容易性と、独立気泡に基づく止水性とをともに期待できるため、複雑な間隙に充填して使用する定型の止水シ―ル材として適していると考察され、例えば、独立気泡と連続気泡との両気泡を有する発泡構造体で気泡皮膜を吸水膨潤性とし、しかも長さ１ｃｍ当たりの気泡数を８個以上としたことを特徴とする定型シ−ル材などが提案されている（特許文献１）。 A foam structure with both closed and open cells can be expected to have both ease of filling a complex gap due to easy deformation based on open cells and water-stop properties based on closed cells. It is considered to be suitable as a fixed water sealing material that is used by filling a small gap.For example, a foam structure having both closed and open cells is made to have a water-swellable foam film, A fixed seal material characterized in that the number of bubbles per 1 cm length is 8 or more has been proposed (Patent Document 1).
しかしながら、独立気泡と連続気泡との両気泡を有する発泡構造体を、止水シ―ル材として使用する場合、時間の経過により、発泡構造体としての反発応力が緩和され、これに伴って、発泡構造体と被シール部材（止水対象となる構造部材）界面との接触面圧が低下し、この界面沿いに水漏れが発生して、止水シ―ル材として有効に機能しなくなるという問題があった。 However, when a foam structure having both closed cells and open cells is used as a water sealing material, the repulsive stress as the foam structure is relieved with the passage of time. The contact surface pressure between the foam structure and the member to be sealed (structural member to be water-stopped) decreases, and water leaks along this interface, making it unable to function effectively as a water-proof seal material. There was a problem.
従って、止水性能のために独立気泡発泡体からなり、長時間使用しても、発泡体としての反発応力が緩和されず、界面密着性に優れた高性能の発泡体が強く要望されていた。 Therefore, it consists of closed-cell foam for water-stopping performance, and even if it is used for a long time, the repulsive stress as a foam is not relieved, and a high-performance foam excellent in interfacial adhesion has been strongly demanded. .
本発明は、例えば、防塵シール材として用いた場合にあっても長時間に亘って被シール部材との界面に間隙が生じない高性能のシール性能を発揮し得るゴム系樹脂独立気泡発泡シート及びその製造方法を提供する。 The present invention is, for example, a rubber-based resin closed cell foam sheet capable of exhibiting high-performance sealing performance that does not cause a gap at the interface with a member to be sealed for a long time even when used as a dustproof sealing material, and A manufacturing method thereof is provided.
本発明のゴム系樹脂独立気泡発泡シートは、ゴム系樹脂及び繊維を含有するゴム系樹脂独立気泡発泡シートであって、ＪＩＳ Ｋ７２２２に準拠して測定された見掛け密度が１００〜２００ｋｇ／ｍ3で、ＪＩＳ Ｋ６２６２に準拠して８０℃、２４時間の条件下にて測定された圧縮永久歪みが５０％以下で、ＪＩＳ Ｋ６７６７に準拠して測定された５０％圧縮応力が２００ｋＰａ以下であることを特徴とする。 The rubber-based resin closed-cell foamed sheet of the present invention is a rubber-based resin closed-cell foamed sheet containing a rubber-based resin and fibers, and has an apparent density of 100 to 200 kg / m 3 measured in accordance with JIS K7222. The compression set measured under conditions of 80 ° C. and 24 hours according to JIS K6262 is 50% or less, and the 50% compression stress measured according to JIS K6767 is 200 kPa or less. And
ゴム系樹脂としては、室温でゴム弾性（rubber elasticity）を有するものであれば、特に限定されず、例えば、クロロプレンゴム（ＣＲ）、イソプレンゴム（ＩＲ）、ブチルゴム（ＩＩＲ）、ニトリルゴム（ニトリル−ブタジエンゴム）（ＮＢＲ）、天然ゴム、スチレン−ブタジエン共重合体ゴム（ＳＢＲ）、ブタジエンゴム（ＢＲ）、ウレタンゴム、フッ素ゴム、アクリルゴム、エチレン−プロピレン共重合体ゴム、エチレン−プロピレン−ジエン共重合体ゴム、ウレタンゴム、シリコーンゴムなどが挙げられ、ゴム系樹脂シートのクッション性や耐久性に優れていることから、ニトリル−ブタジエンゴム（ＮＢＲ）、スチレン−ブタジエン共重合体ゴム（ＳＢＲ）、ブチルゴム（ＩＩＲ）、クロロプレンゴム（ＣＲ）が好ましく、ニトリル−ブタジエンゴム（ＮＢＲ）がより好ましい。なお、ニトリル−ブタジエンゴム（ＮＢＲ）は、ニトリルゴムとも、アクリロニトリル−ブタジエン共重合体ゴムともいい、又、スチレン−ブタジエン共重合体ゴム（ＳＢＲ）は、スチロールゴムともいい、ブタジエンとスチレンの共重合体ゴムである。 The rubber-based resin is not particularly limited as long as it has rubber elasticity at room temperature. For example, chloroprene rubber (CR), isoprene rubber (IR), butyl rubber (IIR), nitrile rubber (nitrile- Butadiene rubber (NBR), natural rubber, styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), urethane rubber, fluorine rubber, acrylic rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer Polymer rubber, urethane rubber, silicone rubber, etc. are mentioned, and since the cushioning property and durability of the rubber-based resin sheet are excellent, nitrile-butadiene rubber (NBR), styrene-butadiene copolymer rubber (SBR), Butyl rubber (IIR) and chloroprene rubber (CR) are preferred, and nitrile- Tajiengomu (NBR) is more preferable. Nitrile-butadiene rubber (NBR) is also called nitrile rubber or acrylonitrile-butadiene copolymer rubber, and styrene-butadiene copolymer rubber (SBR) is also called styrene rubber. It is a united rubber.
本発明のゴム系樹脂独立気泡発泡シートには繊維が含有されている。このように繊維を含有させることによって、ゴム系樹脂独立気泡発泡シートに剛性及び高い圧縮回復性を付与している。 The rubber-based resin closed-cell foamed sheet of the present invention contains fibers. By containing fibers in this way, rigidity and high compression recovery are imparted to the rubber-based resin closed cell foam sheet.
上記繊維としては、ポリエチレン繊維、ポリプロピレン繊維、ポリエチレンテレフタレート繊維、ポリブチレンテレフタレート繊維、ポリエチレンナフタレート繊維、ポリブチレンナフタレート繊維などが挙げられ、ポリエチレンテレフタレート繊維、ポリブチレンテレフタレート繊維、ポリエチレンナフタレート繊維、ポリブチレンナフタレート繊維が好ましく、ポリエチレンナフタレート繊維がより好ましい。なお、繊維は単独で用いられても二種以上が併用されてもよい。 Examples of the fiber include polyethylene fiber, polypropylene fiber, polyethylene terephthalate fiber, polybutylene terephthalate fiber, polyethylene naphthalate fiber, polybutylene naphthalate fiber, and the like. Polyethylene terephthalate fiber, polybutylene terephthalate fiber, polyethylene naphthalate fiber, poly Butylene naphthalate fibers are preferred, and polyethylene naphthalate fibers are more preferred. In addition, a fiber may be used independently or 2 or more types may be used together.
上記繊維の製造方法としては、特に限定されず、フラッシュ紡糸法、スパンボンド紡糸法、メルトブロー紡糸法、エレクトロスピニング法などの公知の紡糸方法が挙げられる。繊維はモノフィラメントであることが好ましい。又、繊維のアスペクト比（繊維長／繊維径）は、１００以下が好ましい。 The method for producing the fiber is not particularly limited, and examples thereof include known spinning methods such as a flash spinning method, a spunbond spinning method, a melt blow spinning method, and an electrospinning method. The fibers are preferably monofilaments. The aspect ratio (fiber length / fiber diameter) of the fiber is preferably 100 or less.
繊維を上述したアスペクト比とするために繊維を切断する必要があるが、繊維を切断するにあたっては、従来公知の装置を用いることができ、例えば、ミルミキサーを用いて切断する方法が挙げられる。 Although it is necessary to cut | disconnect a fiber in order to make a fiber into the aspect-ratio mentioned above, in cut | disconnecting a fiber, a conventionally well-known apparatus can be used, For example, the method of cut | disconnecting using a mill mixer is mentioned.
ゴム系樹脂独立気泡発泡シート中における繊維の含有量は、少ないと、ゴム系樹脂独立気泡発泡シートに剛性及び優れた圧縮回復性を付与することができないことがあるので、ゴム系樹脂１００重量部に対して１〜５０重量部が好ましい。 If the content of fibers in the rubber-based resin closed-cell foamed sheet is small, the rubber-based resin closed-cell foamed sheet may not be imparted with rigidity and excellent compression recovery properties. The amount is preferably 1 to 50 parts by weight.
ゴム系樹脂独立気泡発泡シートには、粘度、ゲル分率、強度などの調節などを行うために添加剤が添加されていてもよい。このような添加剤としては、例えば、加硫促進剤、加硫遅延剤、軟化剤（可塑剤）、充填剤、老化防止剤、酸化防止剤、顔料、着色剤、防カビ剤、発泡助剤、安定剤、紫外線吸収剤、顔料、難燃剤、帯電防止剤などが挙げられる。 Additives may be added to the rubber-based resin closed-cell foamed sheet in order to adjust viscosity, gel fraction, strength, and the like. Examples of such additives include vulcanization accelerators, vulcanization retarders, softeners (plasticizers), fillers, anti-aging agents, antioxidants, pigments, colorants, anti-mold agents, and foaming aids. , Stabilizers, ultraviolet absorbers, pigments, flame retardants, antistatic agents and the like.
上記加硫促進剤としては、例えば、アルデヒドアンモニア類やアルデヒドアミン類、グアニジン類やチアゾール類、スルフェンアミド類やチューラム類、ジチオカルバミン酸類やキサントゲン酸類、チオウレア類などが挙げられる。 Examples of the vulcanization accelerator include aldehyde ammonias, aldehyde amines, guanidines, thiazoles, sulfenamides, turums, dithiocarbamic acids, xanthogenic acids, thioureas, and the like.
又、上記加硫遅延剤としては、例えば、無水フタル酸、安息香酸、サリチル酸などの有機酸、Ｎ−ニトロソ−ジフェニルアミン、Ｎ−ニトロソ−フェニル−β−ナフチルアミンなどの加硫遅延剤、ポリ（メタ）アクリル酸アルキルエステルなどのアクリル系樹脂、ポリ塩化ビニルなどが挙げられる。 Examples of the vulcanization retarder include organic acids such as phthalic anhydride, benzoic acid and salicylic acid, vulcanization retarders such as N-nitroso-diphenylamine and N-nitroso-phenyl-β-naphthylamine, and poly (meta ) Acrylic resin such as alkyl acrylate, polyvinyl chloride and the like.
上記軟化剤としては、例えば、塩素化パラフィンなどのパラフィン類やワックス類、アマニ油などの乾性油類や動植物油類、石油系オイル類や各種の低分量ポリマー類、フタル酸エステル類やリン酸エステル類、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挙げられる。 Examples of the softening agent include paraffins and waxes such as chlorinated paraffin, drying oils such as linseed oil, animal and vegetable oils, petroleum oils, various low-volume polymers, phthalates and phosphoric acid. Examples thereof include esters, stearic acid and esters thereof, alkylsulfonic acid esters and tackifiers.
更に、上記充填剤としては、例えば、タルク、炭酸カルシウム、ベントナイト、カーボンブラック、フュームドシリカ、アルミニウムシリケート、アセチレンブラック、アルミニウム粉などが挙げられる。 Furthermore, examples of the filler include talc, calcium carbonate, bentonite, carbon black, fumed silica, aluminum silicate, acetylene black, and aluminum powder.
ゴム系樹脂独立気泡発泡シートのゲル分率は、低いと、ゴム系樹脂独立気泡発泡シートの圧縮永久歪みが低下し、高いと、ゴム系樹脂独立気泡発泡シートの圧縮柔軟性が低下するので、８５〜９５重量％が好ましく、９０〜９５重量％がより好ましい。 If the gel fraction of the rubber-based resin closed cell foam sheet is low, the compression set of the rubber-based resin closed cell foam sheet decreases, and if it is high, the compression flexibility of the rubber resin closed cell foam sheet decreases. 85 to 95% by weight is preferable, and 90 to 95% by weight is more preferable.
なお、ゴム系樹脂独立気泡発泡シートのゲル分率は、下記の要領で測定されたものをいう。ゴム系樹脂独立気泡発泡シートをＡｇ秤量し、これを１２０℃のキシレン中に２４時間浸漬して不溶解分を２００メッシュの金網で濾過し、金網上の残渣を真空乾燥して乾燥残渣の重量を測定し（Ｂｇ）、下記式により算出した。
ゲル分率（重量％）＝（Ｂ／Ａ）×１００
In addition, the gel fraction of a rubber-type resin closed cell foam sheet says what was measured in the following way. The rubber-based resin closed-cell foamed sheet is weighed, and immersed in xylene at 120 ° C. for 24 hours, the insoluble matter is filtered through a 200-mesh wire mesh, and the residue on the wire mesh is vacuum-dried to dry the weight of the residue. (Bg) was calculated according to the following formula.
Gel fraction (% by weight) = (B / A) × 100
ゴム系樹脂独立気泡発泡シートの独立気泡率は、小さいと、ゴム系樹脂独立気泡発泡シートのシール性能止が低下することがあるので、８０〜１００％が好ましく、８５〜１００％がより好ましい。 When the closed cell ratio of the rubber-based resin closed cell foamed sheet is small, the sealing performance of the rubber-based resin closed cell foamed sheet may be deteriorated, so 80 to 100% is preferable, and 85 to 100% is more preferable.
ここで、ゴム系樹脂独立気泡発泡シートの独立気泡率は、下記の要領で測定されたものをいう。先ず、ゴム系樹脂独立気泡発泡シートから一辺が５ｃｍの平面正方形状で且つ一定厚みの試験片を切り出す。そして、試験片の厚みを測定して試験片の見掛け体積Ｖ1を算出すると共に、試験片の重量Ｗ1を測定する。 Here, the closed cell ratio of the rubber-based resin closed cell foam sheet is measured in the following manner. First, a test piece having a flat square shape with a side of 5 cm and a constant thickness is cut out from the rubber-based resin closed cell foam sheet. Then, the thickness of the test piece is measured to calculate the apparent volume V 1 of the test piece, and the weight W 1 of the test piece is measured.
次に、気泡の占める見掛け体積Ｖ2を下記式に基づいて算出する。なお、試験片を構成している樹脂の密度は１ｇ／ｃｍ3とする。
気泡の占める見掛け体積Ｖ2＝Ｖ1−Ｗ1
Next, the apparent volume V 2 occupied by the bubbles is calculated based on the following formula. The density of the resin constituting the test piece is 1 g / cm 3 .
Apparent volume occupied by bubbles V 2 = V 1 −W 1
続いて、試験片を２３℃の蒸留水中に水面から１００ｍｍの深さに沈めて、試験片に１５ｋＰａの圧力を３分間に亘って加える。しかる後、試験片を水中から取り出して試験片の表面に付着した水分を除去して試験片の重量Ｗ2を測定し、下記式に基づいて連続気泡率Ｆ1及び独立気泡率Ｆ2を算出する。
連続気泡率Ｆ1（％）＝１００×（Ｗ2−Ｗ1）／Ｖ2
独立気泡率Ｆ2（％）＝１００−Ｆ1
Subsequently, the test piece is submerged in distilled water at 23 ° C. to a depth of 100 mm from the water surface, and a pressure of 15 kPa is applied to the test piece over 3 minutes. After that, the test piece is taken out of the water, the water adhering to the surface of the test piece is removed, the weight W 2 of the test piece is measured, and the open cell rate F 1 and the closed cell rate F 2 are calculated based on the following formulas. To do.
Open cell ratio F 1 (%) = 100 × (W 2 −W 1 ) / V 2
Closed cell ratio F 2 (%) = 100−F 1
ゴム系樹脂独立気泡発泡シートの発泡倍率は、低いと、小さいと、ゴム系樹脂独立気泡発泡シートが脆くなって強度が保てなくなり、長期間に亘ってシール性能を維持することができない一方、大きいと、ゴム系樹脂独立気泡発泡シートが硬くなって圧縮柔軟性が低下し或いは圧縮時の反発力が大きくなり、被シール部材が変形し、被シール部材の変形により被シール部分の隙間が拡大してシール性が低下するので、５〜１５倍が好ましい。 While the expansion ratio of the rubber-based resin closed cell foam sheet is low and small, the rubber-based resin closed cell foam sheet becomes brittle and cannot maintain strength, while the sealing performance cannot be maintained over a long period of time. If it is large, the rubber-based resin closed cell foam sheet becomes hard and the compression flexibility decreases or the repulsive force at the time of compression increases, the sealed member is deformed, and the gap of the sealed portion is expanded by the deformation of the sealed member. And since sealing performance falls, 5 to 15 times is preferable.
そして、ゴム系樹脂独立気泡発泡シートのＪＩＳ Ｋ７２２２に準拠した見掛け密度は、小さいと、ゴム系樹脂独立気泡発泡シートが脆くなって強度が保てなくなり、長期間に亘ってシール性能を維持することができない一方、大きいと、ゴム系樹脂独立気泡発泡シートが硬くなって圧縮柔軟性が低下し或いは圧縮時の反発力が大きくなり、被シール部材が変形し、被シール部材の変形により被シール部分の隙間が拡大してシール性が低下するので、１００〜２００ｋｇ／ｍ3に限定される。 If the apparent density in accordance with JIS K7222 of the rubber-based resin closed cell foamed sheet is small, the rubber-based resin closed cell foamed sheet becomes brittle and the strength cannot be maintained, and the sealing performance is maintained for a long period of time. On the other hand, if it is large, the rubber-based resin closed cell foam sheet becomes hard and the compression flexibility is lowered or the repulsive force at the time of compression is increased. The gap is enlarged and the sealing performance is lowered, so that it is limited to 100 to 200 kg / m 3 .
又、ゴム系樹脂独立気泡発泡シートのＪＩＳ Ｋ６２６２に準拠して８０℃、２４時間の条件下にて測定された圧縮永久歪みは、高いと、ゴム系樹脂独立気泡発泡シートの形状回復性が低下し、ゴム系樹脂独立気泡発泡シートを防塵シール材として用いた際に長期防塵性が定価するので、５０％以下に限定され、４０％以下が好ましい。 In addition, when the compression set measured under conditions of 80 ° C. and 24 hours in accordance with JIS K6262 of the rubber-based resin closed cell foam sheet is high, the shape recoverability of the rubber-based resin closed cell foam sheet is lowered. However, when the rubber-based resin closed cell foam sheet is used as a dust-proof sealing material, long-term dust resistance is fixed, so it is limited to 50% or less, and preferably 40% or less.
更に、ゴム系樹脂独立気泡発泡シートにおけるＪＩＳ Ｋ６７６７に準拠して測定された５０％圧縮応力は、高いと、ゴム系樹脂独立気泡発泡シートの柔軟性が低下し、ゴム系樹脂独立気泡発泡シートをシール材として用いた際にシール部分に割れや浮きが生じるので、２００ｋＰａ以下に限定され、ゴム系樹脂独立気泡発泡シートを防塵シール材として用いる場合には１０〜２００ｋＰａが好ましい。 Furthermore, if the 50% compression stress measured in accordance with JIS K6767 in the rubber-based resin closed cell foam sheet is high, the flexibility of the rubber-based resin closed cell foam sheet is reduced, and the rubber-based resin closed cell foam sheet is reduced. When used as a sealing material, cracks and floats occur in the sealing portion, so the pressure is limited to 200 kPa or less, and 10 to 200 kPa is preferable when a rubber-based resin closed cell foam sheet is used as a dustproof sealing material.
次に、ゴム系樹脂独立気泡発泡シートの製造方法を説明する。ゴム系樹脂独立気泡発泡シートの製造方法としては、公知の方法を採用することができ、例えば、ゴム系樹脂、繊維、架橋剤及び熱分解型発泡剤に、必要に応じて充填剤等が添加されてなる発泡性原料組成物を必要に応じてバンバリーミキサーや加圧ニーダなどの混練り機で混練した後、カレンダー、押出機、コンベアベルトキャスティングなどにより連続的に混練して発泡性樹脂シートを製造し、この未架橋の発泡性樹脂シートを加熱して架橋しつつ或いは架橋後に発泡させてゴム系樹脂独立気泡発泡シートを製造する方法、ゴム系樹脂、繊維及び熱分解型発泡剤に、必要に応じて充填剤等が添加されてなる発泡性原料組成物を必要に応じてバンバリーミキサーや加圧ニーダなどの混練り機で混練した後、カレンダー、押出機、コンベアベルトキャスティングなどにより連続的に混練して発泡性樹脂シートを製造し、この発泡性樹脂シートに電離性放射線を照射して発泡性樹脂シートを架橋した後、発泡性樹脂シートを加熱して発泡させてゴム系樹脂独立気泡発泡シートを製造する方法などが挙げられる。 Next, the manufacturing method of a rubber-type resin closed cell foam sheet is demonstrated. As a method for producing a rubber-based resin closed-cell foamed sheet, a known method can be adopted. For example, a filler or the like is added to a rubber-based resin, a fiber, a crosslinking agent, and a pyrolytic foaming agent as necessary. The foamable raw material composition is kneaded by a kneader such as a Banbury mixer or a pressure kneader as necessary, and then continuously kneaded by a calendar, an extruder, a conveyor belt casting or the like to obtain a foamable resin sheet. Necessary for the manufacturing method of rubber-based resin closed-cell foamed sheet by heating and crosslinking this uncrosslinked foamable resin sheet by heating or after crosslinking, rubber-based resin, fiber and pyrolytic foaming agent If necessary, the foamable raw material composition to which a filler or the like is added is kneaded with a kneader such as a Banbury mixer or a pressure kneader, and then a calender, an extruder, or a conveyor bed. A foamable resin sheet is manufactured by kneading continuously by casting, etc., and the foamable resin sheet is irradiated with ionizing radiation to crosslink the foamable resin sheet, and then the foamable resin sheet is heated and foamed. And a method of producing a rubber-based resin closed cell foam sheet.
上記架橋剤としては、例えば、有機過酸化物、硫黄、硫黄化合物等が挙げられ、有機過酸化物が好ましい。電離性放射線としては、例えば、光、γ線、電子線などが挙げられる。上記有機過酸化物としては、例えば、ジイソプロピルベンゼンヒドロパーオキサイド、２,４−ジクロロベンゾイルパーオキサイド、ベンゾイルパーオキサイド、ｔ−ブチルパーベンゾエート、クミルハイドロパーオキサイド、ｔ−ブチルハイドロパーオキサイド、１,１−ジ（ｔ−ブチルパーオキシ）−３,３,５−トリメチルヘキサン、ｎ−ブチル−４,４−ジ（ｔ−ブチルパーオキシ）バレレート、α,α'−ビス（ｔ−ブチルパーオキシイソプロピル）ベンゼン、２,５−ジメチル−２,５−ジ（ｔ−ブチルパーオキシ）ヘキシン−３、ｔ−ブチルパーオキシクメンなどが挙げられ、上記硫黄化合物としては、例えば、テトラメ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、ジメチルジチオカルバミン酸亜鉛、２−メルカプトベンゾチアゾール、ジベンゾチアジルジスルフィド、Ｎ−シクロヘキシル−２−ベンゾチアゾールスルフェンアミド、Ｎ−ｔ−ブチル−２−ベンゾチアゾールスルフェンアミド、一塩化硫黄、二塩化硫黄などが挙げられる。 As said crosslinking agent, an organic peroxide, sulfur, a sulfur compound etc. are mentioned, for example, An organic peroxide is preferable. Examples of ionizing radiation include light, γ-rays, and electron beams. Examples of the organic peroxide include diisopropylbenzene hydroperoxide, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, t-butyl perbenzoate, cumyl hydroperoxide, t-butyl hydroperoxide, 1, 1-di (t-butylperoxy) -3,3,5-trimethylhexane, n-butyl-4,4-di (t-butylperoxy) valerate, α, α′-bis (t-butylperoxy) Isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, t-butylperoxycumene and the like. Examples of the sulfur compound include tetramethylthiuram disulfide, Tetramethylthiuram monosulfide, zinc dimethyldithiocarbamate, 2-mercapto Examples include benzothiazole, dibenzothiazyl disulfide, N-cyclohexyl-2-benzothiazole sulfenamide, Nt-butyl-2-benzothiazole sulfenamide, sulfur monochloride, sulfur dichloride and the like.
又、発泡性原料組成物中における架橋剤の含有量は、少ないと、発泡性原料組成物のゲル分率（架橋度）が発泡に適したものとならずに破泡してしまい、ゴム系樹脂独立気泡発泡シートを得ることできないことがある一方、多いと、発泡性原料組成物のゲル分率（架橋度）が上がりすぎて、発泡性原料組成物が発泡しないことがあるので、ゴム系樹脂１００重量部に対して０．０５〜１０重量部が好ましく、０．１〜７重量部がより好ましい。 Further, if the content of the crosslinking agent in the foamable raw material composition is small, the gel fraction (crosslinking degree) of the foamable raw material composition does not become suitable for foaming and bubbles are broken. While it may not be possible to obtain a resin closed-cell foamed sheet, if too much, the gel fraction (crosslinking degree) of the foamable raw material composition will increase too much, and the foamable raw material composition may not foam. 0.05-10 weight part is preferable with respect to 100 weight part of resin, and 0.1-7 weight part is more preferable.
上記熱分解型発泡剤とは加熱により分解して発泡ガスを発生させるものをいい、このような熱分解型発泡剤としては、特に限定されず、例えば、アゾジカルボンアミド、ベンゼンスルホニルヒドラジド、ジニトロソペンタメチレンテトラミン、トルエンスルホニルヒドラジド、４,４−オキシビス（ベンゼンスルホニルヒドラジド）等が挙げられる。これらの熱分解型発泡剤は単独で用いられてもよく２種以上が併用されてもよい。 The pyrolytic foaming agent refers to those that decompose by heating to generate foaming gas. Such pyrolytic foaming agent is not particularly limited, and examples thereof include azodicarbonamide, benzenesulfonylhydrazide, and dinitroso. Examples include pentamethylenetetramine, toluenesulfonyl hydrazide, 4,4-oxybis (benzenesulfonyl hydrazide), and the like. These thermal decomposition type foaming agents may be used independently and 2 or more types may be used together.
発泡性原料組成物中における熱分解型発泡剤の含有量は、少ないと、ゴム系樹脂発泡シートの発泡倍率が上がらずに見掛け密度が高くなってしまい、ゴム系樹脂発泡シートの反発力が高くなることがある一方、多いと、ゴム系樹脂発泡シートの見掛け密度が低くなり、圧縮永久歪みが大きくなり、ゴム系樹脂独立気泡発泡シートの形状回復性が低下して、長期間に亘ってシール性能を維持することができないことがあるので、ゴム系樹脂１００重量部に対して１〜１０重量部が好ましい。 If the content of the thermally decomposable foaming agent in the foamable raw material composition is small, the foaming ratio of the rubber-based resin foamed sheet does not increase and the apparent density increases, and the repulsive force of the rubber-based resin foamed sheet is high. On the other hand, if it is large, the apparent density of the rubber-based resin foam sheet will be low, the compression set will be large, the shape recoverability of the rubber-based resin closed cell foam sheet will be reduced, and it will seal for a long time Since performance may not be maintained, 1 to 10 parts by weight is preferable with respect to 100 parts by weight of the rubber-based resin.
又、電離性放射線の照射量としては、ゴム系樹脂の特性によって適宜、調整すればよく、０．５〜１０Ｍｒａｄが好ましく、０．７〜５．０Ｍｒａｄがより好ましい。 Moreover, what is necessary is just to adjust suitably according to the characteristic of rubber-type resin as an irradiation amount of ionizing radiation, 0.5-10 Mrad is preferable and 0.7-5.0 Mrad is more preferable.
このようにして得られたゴム系樹脂独立気泡発泡シートは、電気、エレクトロニクス、車輌などの分野において各種シール材として好適に用いることができる。特に、防塵対象となる構造部材との間に隙間が生じず、長期間に亘って優れた防塵性を発揮するので、パッキング材やガスケット材として好適に用いることができる。 The rubber-based resin closed cell foam sheet thus obtained can be suitably used as various sealing materials in the fields of electricity, electronics, vehicles and the like. In particular, since no gap is generated between the structural member to be dust-proof and excellent dust-proof properties are exhibited over a long period of time, it can be suitably used as a packing material or a gasket material.
本発明のシール材は、ゴム系樹脂及び繊維を含有するゴム系樹脂独立気泡発泡シートであって、ＪＩＳ Ｋ７２２２に準拠して測定された見掛け密度が１００〜２００ｋｇ／ｍ3で、ＪＩＳ Ｋ６２６２に準拠して８０℃、２４時間の条件下にて測定された圧縮永久歪みが５０％以下で、ＪＩＳ Ｋ６７６７に準拠して測定された５０％圧縮応力が２００ｋＰａ以下であることを特徴とし、低反発でありながら優れたシール性能を長期間に亘って維持する。 The sealing material of the present invention is a rubber-based resin closed-cell foamed sheet containing a rubber-based resin and fibers, and has an apparent density measured according to JIS K7222 of 100 to 200 kg / m 3 , according to JIS K6262. The compression set measured under conditions of 80 ° C. and 24 hours is 50% or less, and the 50% compression stress measured in accordance with JIS K6767 is 200 kPa or less. Maintain excellent sealing performance over a long period of time.
そして、上記ゴム系樹脂独立気泡発泡シートにおいて、繊維がモノフィラメントであり、繊維長が５００μｍ以下で且つ繊維のアスペクト比が１００以下である場合には、ゴム系樹脂独立気泡発泡シートの発泡倍率を高く維持しつつ、低反発でありながら優れたシール性能を長期間に亘って維持することができる。 In the rubber-based resin closed cell foam sheet, when the fiber is a monofilament, the fiber length is 500 μm or less, and the fiber aspect ratio is 100 or less, the expansion ratio of the rubber-based resin closed cell foam sheet is increased. While maintaining, excellent sealing performance can be maintained over a long period of time while being low repulsion.
（実施例１）
ニトリル−ブタジエンゴム（ＮＢＲ、密度：０．９６ｇ／ｃｍ3）１００重量部、アゾジカルボンアミド（大塚化学社製 商品名「ＡＣ―ｋ３」）５重量部、ポリエチレンナフタレート（ＰＥＮ）のモノフィラメント（繊維長：２００μｍ、アスペクト比：１００）３０重量部を押出機に供給して溶融混練し押出して発泡性樹脂シートを得た。なお、ポリエチレンナフタレートのモノフィラメントは、ポリエチレンナフタレート（重量平均分子量：２００００）を１，１，１，３，３，３−ヘキサフルオロ−２−プロパノールに溶解させてエレクトロスピニング法によって２０ｋＶにて紡糸して得られたものである。
Example 1
Nitrile-butadiene rubber (NBR, density: 0.96 g / cm 3 ) 100 parts by weight, azodicarbonamide (trade name “AC-k3” manufactured by Otsuka Chemical Co., Ltd.) 5 parts by weight, polyethylene naphthalate (PEN) monofilament (fiber) (Length: 200 μm, aspect ratio: 100) 30 parts by weight were supplied to an extruder, melt-kneaded and extruded to obtain a foamable resin sheet. Polyethylene naphthalate monofilament is obtained by dissolving polyethylene naphthalate (weight average molecular weight: 20000) in 1,1,1,3,3,3-hexafluoro-2-propanol and spinning at 20 kV by electrospinning. It was obtained.
得られた発泡性樹脂シートに加速電圧５００ｋｅＶにて０．８Ｍｒａｄの電子線を照射して発泡性樹脂シートを架橋した。次に、発泡性樹脂シートを発泡炉に供給して２３０℃に加熱することによってアゾジカルボンアミドを分解発泡させて見掛け密度が１６２ｋｇ／ｍ3、厚さが２．５ｍｍのゴム系樹脂独立気泡発泡シートを得た。 The obtained foamable resin sheet was irradiated with 0.8 Mrad electron beam at an acceleration voltage of 500 keV to crosslink the foamable resin sheet. Next, the foamable resin sheet is supplied to a foaming furnace and heated to 230 ° C. to decompose and foam the azodicarbonamide so that the apparent density is 162 kg / m 3 and the thickness is 2.5 mm. A sheet was obtained.
（実施例２）
ポリエチレンナフタレートのモノフィラメントとして、繊維長が５００μｍで且つアスペクト比が１００であるポリエチレンナフタレートのモノフィラメントを用いたこと以外は実施例１と同様にして見掛け密度が１７６ｋｇ／ｍ3、厚さが２．５ｍｍのゴム系樹脂独立気泡発泡シートを得た。
(Example 2)
The apparent density is 176 kg / m 3 and the thickness is 2. as in Example 1, except that a polyethylene naphthalate monofilament having a fiber length of 500 μm and an aspect ratio of 100 is used as the polyethylene naphthalate monofilament. A 5 mm rubber resin closed cell foam sheet was obtained.
（実施例３）
ポリエチレンナフタレートのモノフィラメントとして、繊維長が５００μｍで且つアスペクト比が５０であるポリエチレンナフタレートのモノフィラメントを用いたこと以外は実施例１と同様にして見掛け密度が１１４ｋｇ／ｍ3、厚さが２．５ｍｍのゴム系樹脂独立気泡発泡シートを得た。
(Example 3)
The apparent density is 114 kg / m 3 and the thickness is 2. as in Example 1, except that a polyethylene naphthalate monofilament having a fiber length of 500 μm and an aspect ratio of 50 is used as the polyethylene naphthalate monofilament. A 5 mm rubber resin closed cell foam sheet was obtained.
（比較例１）
ポリエチレンナフタレートのモノフィラメントを用いなかったこと以外は実施例１と同様にして見掛け密度が１８２ｋｇ／ｍ3、厚さが２．５ｍｍのゴム系樹脂独立気泡発泡シートを得た。
(Comparative Example 1)
A rubber-based resin closed cell foamed sheet having an apparent density of 182 kg / m 3 and a thickness of 2.5 mm was obtained in the same manner as in Example 1 except that polyethylene naphthalate monofilament was not used.
（比較例２）
ポリエチレンナフタレートのモノフィラメントとして、繊維長が１０００μｍで且つアスペクト比が１００であるポリエチレンナフタレートのモノフィラメントを用いたこと以外は実施例１と同様にして見掛け密度が１６７ｋｇ／ｍ3、厚さが２．５ｍｍのゴム系樹脂独立気泡発泡シートを得た。
(Comparative Example 2)
The apparent density is 167 kg / m 3 and the thickness is 2. as in Example 1, except that a polyethylene naphthalate monofilament having a fiber length of 1000 μm and an aspect ratio of 100 is used as the polyethylene naphthalate monofilament. A 5 mm rubber resin closed cell foam sheet was obtained.
（比較例３）
ポリエチレンナフタレートのモノフィラメントとして、繊維長が５００μｍで且つアスペクト比が２００であるポリエチレンナフタレートのモノフィラメントを用いたこと以外は実施例１と同様にして見掛け密度が１７５ｋｇ／ｍ3、厚さが２．５ｍｍのゴム系樹脂独立気泡発泡シートを得た。
(Comparative Example 3)
The apparent density was 175 kg / m 3 and the thickness was 2. as in Example 1, except that a polyethylene naphthalate monofilament having a fiber length of 500 μm and an aspect ratio of 200 was used as the polyethylene naphthalate monofilament. A 5 mm rubber resin closed cell foam sheet was obtained.
得られたゴム系樹脂独立気泡発泡シートについて、８０℃、２４時間の条件下におけるＪＩＳ Ｋ６２６２に準拠した圧縮永久歪み、ＪＩＳ Ｋ６７６７に準拠した５０％圧縮応力及びゲル分率を上述の要領で測定し、更に、発泡倍率を測定し、その結果を表１に示した。 About the obtained rubber-based resin closed cell foam sheet, the compression set according to JIS K6262 under the conditions of 80 ° C. and 24 hours, the 50% compressive stress and the gel fraction according to JIS K6767 were measured as described above. Further, the expansion ratio was measured, and the results are shown in Table 1.
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| JP2013072052A (en) * | 2011-09-29 | 2013-04-22 | Sanwa Kako Co Ltd | Chloroprene rubber open-cell foam and method for producing the same |
| WO2020009239A1 (en) * | 2018-07-06 | 2020-01-09 | 株式会社ブリヂストン | Polyurethane foam for seat pads, automobile seat pad, and production method for polyurethane foam for seat pads |
| WO2020009240A1 (en) * | 2018-07-06 | 2020-01-09 | 株式会社ブリヂストン | Flexible polyurethane foam, automobile seat pad, and production method for flexible polyurethane foam |
| JP2020012095A (en) * | 2018-07-06 | 2020-01-23 | 株式会社ブリヂストン | Polyurethane foam for seat pad, automobile seat pad, and method for producing polyurethane foam for seat pad |
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| JP2013072052A (en) * | 2011-09-29 | 2013-04-22 | Sanwa Kako Co Ltd | Chloroprene rubber open-cell foam and method for producing the same |
| WO2020009239A1 (en) * | 2018-07-06 | 2020-01-09 | 株式会社ブリヂストン | Polyurethane foam for seat pads, automobile seat pad, and production method for polyurethane foam for seat pads |
| WO2020009240A1 (en) * | 2018-07-06 | 2020-01-09 | 株式会社ブリヂストン | Flexible polyurethane foam, automobile seat pad, and production method for flexible polyurethane foam |
| JP2020012095A (en) * | 2018-07-06 | 2020-01-23 | 株式会社ブリヂストン | Polyurethane foam for seat pad, automobile seat pad, and method for producing polyurethane foam for seat pad |
| CN112384569A (en) * | 2018-07-06 | 2021-02-19 | 株式会社普利司通 | Soft polyurethane foam, automobile seat cushion, and process for producing soft polyurethane foam |
| JPWO2020009240A1 (en) * | 2018-07-06 | 2021-07-08 | 株式会社ブリヂストン | Manufacturing method of flexible polyurethane foam, automobile seat pad, and flexible polyurethane foam |
| CN112384569B (en) * | 2018-07-06 | 2023-04-11 | 株式会社普利司通 | Soft polyurethane foam, automobile seat cushion, and process for producing soft polyurethane foam |
| JP7284595B2 (en) | 2018-07-06 | 2023-05-31 | 株式会社アーケム | Polyurethane foam for seat pad, seat pad for automobile, and method for producing polyurethane foam for seat pad |
| JP7323894B2 (en) | 2018-07-06 | 2023-08-09 | 株式会社ブリヂストン | Flexible polyurethane foam, automotive seat pad, and method for producing flexible polyurethane foam |
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