JP2016180122A - Surface treatment solution for rubber article, method for surface modification of rubber article, and method for producing rubber article - Google Patents
Surface treatment solution for rubber article, method for surface modification of rubber article, and method for producing rubber article Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
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- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0607—Rubber or rubber derivatives
- C09K2200/0612—Butadiene-acrylonitrile rubber
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Abstract
Description
本発明は、ゴム製品用表面処理液、ゴム製品の表面改質方法、及びゴム製品の製造方法に関する。 The present invention relates to a surface treatment solution for rubber products, a surface modification method for rubber products, and a method for producing rubber products.
一般に、ゴム製品は、ベース成分であるゴム材料(原料ゴム)に架橋剤等の種々の添加剤を配合したゴム組成物を混練し、混練されたゴム組成物(混練工程を経たゴム組成物)をシート状やチューブ状などの所望の形状に予備成形し(予備成形工程)、得られた未加硫のゴム成形体をさらに加硫成形し(加硫成形工程)、成形を終えたゴム成形体から不要な部分を除去して成形体の仕上げを行い(仕上げ工程)、その後、洗浄、乾燥等を行い、検査工程、包装工程等を経て最終製品とされる。 Generally, a rubber product is obtained by kneading a rubber composition in which various additives such as a crosslinking agent are blended with a rubber material (raw rubber) as a base component, and kneaded the rubber composition (rubber composition after the kneading process). Is molded into a desired shape such as a sheet or tube (preliminary molding process), and the resulting unvulcanized rubber molded body is further vulcanized (vulcanized molding process). Unnecessary parts are removed from the body to finish the molded body (finishing process), and thereafter, washing, drying, etc. are performed, and the final product is obtained through an inspection process, a packaging process and the like.
かかるゴム製品の製造工程中、加硫成形工程を経たゴム成形体が付着しやすいと、その後のゴム成形体(製品)の検査工程や包装工程でのゴム成形体(製品)の取り扱い性が低下するため、加硫成形工程を経たゴム成形体(すなわち、加硫ゴム成形体)が付着しにくいこと(すなわち、防着性を有すること)が好ましい。例えば、特許文献1には、加硫ゴムの粘着(付着)を防止できる粘着防止剤として、低分子量ポリエチレングリコールおよび必要に応じたマイクロクリスタンワックスを、それらの合計量に対して10〜30重量%の脂肪酸アマイド、20〜40重量%の非イオン界面活性剤、80〜120重量%の長鎖脂肪酸塩により水中油型に乳化した粘着防止剤が提案されている。しかし、この粘着防止剤は、充分な付着防止効果を発揮させるためには、高濃度で使用することが必要であり、それ故、加硫ゴムに該粘着防止剤を付すと、加硫ゴムの物理的性質を低下させてしまうという問題点がある。 If a rubber molded product that has undergone a vulcanization molding process tends to adhere during the manufacturing process of such a rubber product, the handleability of the rubber molded product (product) in the subsequent inspection process and packaging process of the rubber molded product (product) will be reduced. Therefore, it is preferable that the rubber molded body (that is, the vulcanized rubber molded body) that has undergone the vulcanization molding process is less likely to adhere (that is, has adhesion resistance). For example, in Patent Document 1, low molecular weight polyethylene glycol and optionally microcristan wax as an anti-tacking agent capable of preventing adhesion (adhesion) of vulcanized rubber is 10 to 30% by weight based on the total amount thereof. An anti-adhesive agent emulsified in an oil-in-water type with 20 to 40% by weight of a nonionic surfactant and 80 to 120% by weight of a long-chain fatty acid salt has been proposed. However, this anti-blocking agent needs to be used at a high concentration in order to exert a sufficient anti-adhesion effect. Therefore, if the anti-blocking agent is added to vulcanized rubber, There is a problem of deteriorating physical properties.
一方、従来からトリクロロイソシアヌル酸やジクロロイソシアヌル酸等のイソシアヌル酸のハロゲン化物を使用してゴムや樹脂の表面処理を行うことが知られている。例えば、特許文献2、3には、イソシアヌル酸のハロゲン化物によってゴム表面の摩擦係数低減と耐オゾン性の改良が図られることが開示されている。また、特許文献3にはトリクロロイソシアヌル酸を水に溶解させた処理液はトリクロロイソシアヌル酸を有機溶媒に溶解させた処理液に比べてゴムに発生するシワを防止できる点で有利であることが謳われている。 On the other hand, it is conventionally known that surface treatment of rubber or resin is performed using a halide of isocyanuric acid such as trichloroisocyanuric acid or dichloroisocyanuric acid. For example, Patent Documents 2 and 3 disclose that isocyanuric acid halides reduce the friction coefficient of the rubber surface and improve ozone resistance. Patent Document 3 discloses that a treatment liquid in which trichloroisocyanuric acid is dissolved in water is advantageous in that wrinkles generated in rubber can be prevented as compared with a treatment liquid in which trichloroisocyanuric acid is dissolved in an organic solvent. It has been broken.
電車などのドアの開閉駆動に用いられる空気圧シリンダ、電磁弁、または、スプール弁などにおける摺動部分、すなわち、回転や往復運動する部材(ピストン、スプール等)とこれに対面する部材(シリンダ、スリーブ等)間には、その摺動性を損なうことなく、これらの間に流れる流体を密封するために、パッキンなどのシールが装着される。このような摺動部分に適用される、所謂、摺動部用シールにおいては、運動部の摺動性を損なうことなく、運動部を作動させる作動液体または作動気体を密封することが必要となるため、表面の摩擦係数が小さいことが要求される。この種のシールとしては、例えば、コスト、耐油性等の観点から、ニトリルゴム(NBR)が多く使用されているが、ニトリルゴムは摩擦係数が高い。このため、ニトリルゴムからなるシールの表面を、上記の先行技術文献(特許文献2、3)に開示されている、トリクロロイソシアヌル酸を酢酸エチルに溶解させた処理液で処理をしたところ、処理液がシールの内部まで浸透して、シールの内部まで処理されてしまい、その結果、シールを伸張するとシールの表面に亀裂が発生し、シール性能が低下してしまうことが分かった。また、溶媒に有機溶媒を用いる場合、有機溶媒は揮発し易いため処理液の濃度が変わりやすく、環境への負荷も大きいという欠点があり、そこで、トリクロロイソシアヌル酸を水に溶解させた処理液を検討したが、トリクロロイソシアヌル酸を水に溶解させた処理液では、トリクロロイソシアヌル酸を高濃度に溶解させることができないため、処理による摩擦係数低減効果が十分でないことが分かった。一方、工業的に大量生産された、主成分がゴムからなるシールは、装置や機器に実際に装着する作業を行うまでは一括して保管されるために、保管されている間にシール同士が付着し、装置や機器に装着する前に付着したシール同士を分離する作業が必要になる。このため、シールが装着される装置や機器の製造効率を低下させる原因になっている。 Sliding parts of pneumatic cylinders, solenoid valves, spool valves, etc. used to open and close doors in trains, that is, members that rotate or reciprocate (pistons, spools, etc.) and members that face them (cylinders, sleeves) Etc.) in order to seal the fluid flowing between them without impairing the slidability, a seal such as packing is attached. In a so-called sliding portion seal applied to such a sliding portion, it is necessary to seal the working liquid or working gas that operates the moving portion without impairing the sliding property of the moving portion. Therefore, it is required that the surface friction coefficient is small. As this type of seal, for example, nitrile rubber (NBR) is often used from the viewpoint of cost, oil resistance, etc., but nitrile rubber has a high coefficient of friction. For this reason, when the surface of the seal made of nitrile rubber is treated with a treatment liquid disclosed in the above prior art documents (Patent Documents 2 and 3) in which trichloroisocyanuric acid is dissolved in ethyl acetate, the treatment liquid is obtained. As a result, it was found that when the seal was stretched, cracks occurred on the surface of the seal and the sealing performance deteriorated. In addition, when an organic solvent is used as a solvent, the concentration of the treatment liquid is easily changed because the organic solvent is easily volatilized, and there is a disadvantage that the burden on the environment is large. Although it examined, in the process liquid which dissolved the trichloroisocyanuric acid in water, since the trichloroisocyanuric acid cannot be dissolved in high concentration, it turned out that the friction coefficient reduction effect by a process is not enough. On the other hand, seals made of rubber, the main component of which are industrially mass-produced, are stored in a lump until they are actually installed on the device or equipment. It is necessary to work to separate the stickers that have adhered and adhered to each other before being attached to an apparatus or device. For this reason, it is the cause of reducing the manufacturing efficiency of the apparatus and apparatus with which a seal | sticker is mounted | worn.
本発明は、上記の事情に鑑みて成されたものであり、その解決しようとする課題は、ゴム製品(特にゴムシール)に対して、伸張性を低下させることなく、表面に低摩擦性を付与でき、しかも、保管時のゴム製品同士の付着防止効果も付与できる、ゴム製品用表面処理液および該表面処理液を使用したゴム製品の表面改質方法を提供することにある。 The present invention has been made in view of the above circumstances, and the problem to be solved is to impart low friction to the surface of rubber products (particularly rubber seals) without reducing extensibility. Another object of the present invention is to provide a surface treatment solution for rubber products and a method for modifying the surface of rubber products using the surface treatment solution, which can also provide an adhesion preventing effect between rubber products during storage.
また、ゴム組成物から加硫ゴム成形体からなるゴム製品を製造する際、ゴム成形体の物理的性質の低下をまねくことなく、ゴム成形体同士の付着防止を図ることができ、所望のゴム製品を効率良く製造できる、ゴム製品の製造方法を提供することにある。 In addition, when producing a rubber product comprising a vulcanized rubber molded body from a rubber composition, it is possible to prevent adhesion between the rubber molded bodies without causing deterioration in physical properties of the rubber molded body. An object of the present invention is to provide a method for producing a rubber product that can efficiently produce the product.
また、ゴム組成物から加硫ゴム成形体からなるゴム製品を製造する際、ゴム成形体の物理的性質の低下をまねくことなく、ゴム成形体同士の付着防止を図ることができ、しかも、低摩擦性が付与されたゴム製品を効率よく製造できる、ゴム製品の製造方法を提供することにある。 In addition, when producing a rubber product composed of a vulcanized rubber molded body from a rubber composition, it is possible to prevent adhesion between the rubber molded bodies without lowering the physical properties of the rubber molded body. An object of the present invention is to provide a method for producing a rubber product, which can efficiently produce a rubber product imparted with friction.
本発明者等は、上記の課題を解決するために鋭意研究をした結果、ジクロロイソシアヌル酸塩は水系溶媒に高濃度に溶解させることができ、しかも、その溶液はゴム製品(特にゴムシール)の内部に浸透しにくく、ゴム製品(特にゴムシール)の表面に低摩擦性と防着性を付与し得ることを知見した。 As a result of diligent research to solve the above problems, the inventors of the present invention can dissolve dichloroisocyanurate in an aqueous solvent at a high concentration, and the solution is contained in rubber products (particularly rubber seals). It has been found that it is difficult to penetrate into the surface of the rubber product and can impart low friction and adhesion to the surface of rubber products (especially rubber seals).
また、ジクロロイソシアヌル酸塩を水系溶媒に溶解させた溶液は、ゴム製品の製造過程でのゴム成形体(加硫ゴム成形体)の内部に浸透しにくく、該溶液で表面処理されたゴム成形体の物理的性質は、該溶液で表面処理される前のゴム成形体(加硫ゴム成形体)の物理的性質に対して変化し難いこと、さらに、該溶液にてゴム成形体(加硫ゴム成形体)を表面処理すれば、ゴム成形体に優れた防着性と低摩擦性を付与できることを知見した。 In addition, a solution obtained by dissolving dichloroisocyanurate in an aqueous solvent does not easily penetrate into a rubber molded body (vulcanized rubber molded body) in the production process of a rubber product, and the rubber molded body surface-treated with the solution. The physical properties of the rubber are hardly changed with respect to the physical properties of the rubber molded body (vulcanized rubber molded body) before being surface-treated with the solution. It has been found that if the molded body) is surface-treated, the rubber molded body can be provided with excellent adhesion and low friction.
また、ジクロロイソシアヌル酸塩を水系溶媒に溶解させた溶液は必ずしも加熱してゴム成形体の表面に付さなくても、常温付近の溶液をそのままゴム成形体に付着させた後、加熱することで、表面処理反応が進行し得ることを知見した。 In addition, a solution in which dichloroisocyanurate is dissolved in an aqueous solvent is not necessarily heated and attached to the surface of the rubber molded body. It was found that the surface treatment reaction can proceed.
本発明は、かかる知見に基づいて完成したものであり、その特徴は以下の通りである。
[1] ジクロロイソシアヌル酸塩が水系溶媒に溶解した溶液からなる、ゴム製品用表面処理液。
[2] ジクロロイソシアヌル酸塩が、ジクロロイソシアヌル酸アルカリ金属塩である、上記[1]記載の表面処理液。
[3] ジクロロイソシアヌル酸塩が、ジクロロイソシアヌル酸ナトリウムである、上記[1]記載の表面処理液。
[4] 溶液中のジクロロイソシアヌル酸塩の濃度が2〜20重量%である、上記[1]〜[3]のいずれか1つに記載の表面処理液。
[5] 50〜70℃に加温された溶液である、上記[1]〜[4]のいずれか1つに記載の表面処理液。
[6] ゴム製品がゴムシールである、上記[1]〜[5]のいずれか1つに記載の表面処理液。
[7] ゴムシールがニトリルゴム(NBR)を含む、上記[6]記載の表面処理液。
[8] ゴムシールが摺動部用ゴムシールである、上記[6]記載の表面処理液。
[9] 上記[1]〜[5]のいずれか1つに記載の表面処理液を、ゴム製品の表面に付すことを特徴とする、ゴム製品の表面改質方法。
[10] 表面処理液を50〜70℃に加温して、ゴム製品の表面に付す、上記[9]記載の方法。
[11] 表面処理液中にゴム製品を浸漬することを含む、上記[9]または[10]記載の方法。
[12] 浸漬時間が1〜30分である、上記[11]記載の方法。
[13] ゴム製品がゴムシールである、上記[9]〜[12]のいずれか1つに記載の方法。
[14] ゴム組成物から加硫ゴム成形体を作製するゴム成形体作製工程後に、ジクロロイソシアヌル酸塩が水系溶媒に溶解した溶液からなる20〜70℃の処理液を用いて該加硫ゴム成形体の表面処理を行う表面処理工程(I)を有することを特徴とする、ゴム製品の製造方法。
[15] ゴム成形体作製工程後に、該ゴム成形体作製工程を経て得られた加硫ゴム成形体から不要部分を取り除く仕上げ工程及び該仕上げ工程を経た加硫ゴム成形体の外観検査を行う検査工程を含むか、或いは、該仕上げ工程及び該検査工程に加えて、該検査工程を経た加硫ゴム成形体を包装する、包装工程をさらに含み、
表面処理工程(I)が、(i)ゴム成形体作製工程後、仕上げ工程前の期間、及び/又は、(ii)仕上げ工程後、検査工程前の期間にて、実施される、上記[14]記載のゴム製品の製造方法。
[16] 検査工程前に、洗浄工程および乾燥工程をさらに有し、仕上げ工程後、検査工程前に、表面処理工程(I)を有する場合は、該表面処理工程(I)後に、該洗浄工程および乾燥工程が行われる、上記[15]記載の方法。
[17] 処理液をゴム成形体表面に付す表面処理工程(I)が、処理液にゴム成形体を浸漬する工程である、上記[14]〜[16]のいずれか1つに記載の方法。
[18] 浸漬時間が、10秒〜30分である、上記[14]〜[17]のいずれか1つに記載の方法。
[19] 表面処理工程(I)に代えて、
ジクロロイソシアヌル酸塩が水系溶媒に溶解した溶液からなる40℃以下の処理液を加硫ゴム成形体の表面に付す第1工程と、加硫ゴム成形体の表面に付着した処理液の加熱および洗浄を行う第2工程とを含む表面処理工程(II)を有することを特徴する、上記[14]記載のゴム製品の製造方法。
[20] 第1工程が、温度が40℃以下の処理液中に加硫ゴム成形体を浸漬する工程である、上記[19]記載の方法。
[21] 浸漬時間が、1秒〜10分である、上記[20]記載の方法。
[22] 第2工程における処理液の加熱温度が40℃を超え、100℃以下である、上記[19]〜[21]のいずれか1つもに記載の方法。
[23] 第2工程が、第1工程を経て、表面に処理液が付着した加硫ゴム成形体を、温度が40℃を超え、100℃以下の温水に浸漬する工程である、上記[19]〜[21]のいずれか1つに記載の方法。
[24] 浸漬時間が、1〜10分である、上記[23]記載の方法。
[25] ゴム成形体作製工程後に、該ゴム成形体作製工程を経て得られた加硫ゴム成形体から不要部分を取り除く仕上げ工程及び該仕上げ工程を経た加硫ゴム成形体の外観検査を行う検査工程を含むか、或いは、該仕上げ工程及び該検査工程に加えて、該検査工程を経た加硫ゴム成形体を包装する、包装工程をさらに含み、
表面処理工程(II)が、(i)ゴム成形体作製工程後、仕上げ工程前の期間、及び/又は、(ii)仕上げ工程後、検査工程前の期間にて、実施される、上記[19]〜[22]ののいずれか1つに記載の方法。
[26] ゴム成形体作製工程後に、該ゴム成形体作製工程を経て得られた加硫ゴム成形体から不要部分を取り除く仕上げ工程及び該仕上げ工程を経た加硫ゴム成形体の外観検査を行う検査工程を含むか、或いは、該仕上げ工程及び該検査工程に加えて、該検査工程を経た加硫ゴム成形体を包装する、包装工程をさらに含み、
表面処理工程(II)が、(i)ゴム成形体作製工程後、仕上げ工程前の期間、及び/又は、(ii)仕上げ工程後、検査工程前の期間にて、実施される、上記[23]又は[24]記載の方法。
[27] 検査工程前に、洗浄工程および乾燥工程をさらに有し、仕上げ工程後、検査工程前に、表面処理工程(II)を有する場合は、該洗浄工程を、温度が40℃を超え、100℃以下の温水に加硫ゴム成形体を浸漬する工程にして、表面処理工程(II)の第2工程に充当させてなる、上記[26]に記載の方法。
[28] ゴム組成物が、ニトリルゴム(NBR)、水素化ニトリルゴム(H−NBR)、イソプレンゴム(IR)、ブタジエンゴム(BR)、スチレン−ブタジエンゴム(SBR)、クロロプレンゴム(CR)、ブチルゴム(IIR)、天然ゴム(NR)、およびエチレン−プロピレン−ジエンゴム(EPDM)からなる群から選択される1種以上のゴムに添加剤が配合されたものである、上記[14]〜[27]のいずれか1つに記載の方法。
[29] ゴム組成物が、ニ卜リルゴムに添加剤が配合されたニ卜リルゴム組成物である、上記[14]〜[27]のいずれか1つに記載の方法。
[30]
ゴム製品がゴムシールである、上記[14]〜[29]のいずれか1つに記載の方法。
The present invention has been completed based on such findings, and the features thereof are as follows.
[1] A surface treatment solution for rubber products, comprising a solution in which dichloroisocyanurate is dissolved in an aqueous solvent.
[2] The surface treatment liquid according to the above [1], wherein the dichloroisocyanurate is an alkali metal dichloroisocyanurate.
[3] The surface treatment liquid according to the above [1], wherein the dichloroisocyanurate is sodium dichloroisocyanurate.
[4] The surface treatment liquid according to any one of [1] to [3] above, wherein the concentration of dichloroisocyanurate in the solution is 2 to 20% by weight.
[5] The surface treatment liquid according to any one of [1] to [4] above, which is a solution heated to 50 to 70 ° C.
[6] The surface treatment liquid according to any one of the above [1] to [5], wherein the rubber product is a rubber seal.
[7] The surface treatment liquid according to [6] above, wherein the rubber seal contains nitrile rubber (NBR).
[8] The surface treatment liquid according to the above [6], wherein the rubber seal is a sliding portion rubber seal.
[9] A method for modifying a surface of a rubber product, comprising applying the surface treatment liquid according to any one of [1] to [5] to the surface of the rubber product.
[10] The method according to [9] above, wherein the surface treatment liquid is heated to 50 to 70 ° C. and applied to the surface of the rubber product.
[11] The method according to [9] or [10] above, comprising immersing a rubber product in the surface treatment liquid.
[12] The method according to [11] above, wherein the immersion time is 1 to 30 minutes.
[13] The method according to any one of [9] to [12] above, wherein the rubber product is a rubber seal.
[14] After the rubber molded body manufacturing step for manufacturing a vulcanized rubber molded body from the rubber composition, the vulcanized rubber molded body is processed using a treatment liquid at 20 to 70 ° C. composed of a solution in which dichloroisocyanurate is dissolved in an aqueous solvent. A method for producing a rubber product, comprising a surface treatment step (I) for performing surface treatment of a body.
[15] After the rubber molded body manufacturing process, a finishing process for removing unnecessary portions from the vulcanized rubber molded body obtained through the rubber molded body manufacturing process, and an inspection for inspecting the appearance of the vulcanized rubber molded body after the finishing process Including a process, or in addition to the finishing process and the inspection process, further including a packaging process of packaging the vulcanized rubber molded body that has undergone the inspection process,
[14] The surface treatment step (I) is performed in (i) a period after the rubber molded body preparation step and before the finishing step, and / or (ii) after the finishing step and before the inspection step. ] The manufacturing method of the rubber product of description.
[16] In the case of further having a cleaning process and a drying process before the inspection process, and having a surface treatment process (I) after the finishing process and before the inspection process, the cleaning process is performed after the surface treatment process (I). And the method according to [15] above, wherein a drying step is performed.
[17] The method according to any one of [14] to [16] above, wherein the surface treatment step (I) of applying the treatment liquid to the surface of the rubber molded body is a step of immersing the rubber molded body in the treatment liquid. .
[18] The method according to any one of [14] to [17] above, wherein the immersion time is 10 seconds to 30 minutes.
[19] Instead of the surface treatment step (I),
A first step of applying a treatment liquid of 40 ° C. or less comprising a solution of dichloroisocyanurate in an aqueous solvent to the surface of the vulcanized rubber molded body, and heating and washing of the treatment liquid adhered to the surface of the vulcanized rubber molded body The method for producing a rubber product according to [14] above, further comprising a surface treatment step (II) including a second step of performing the step.
[20] The method according to [19] above, wherein the first step is a step of immersing the vulcanized rubber molded article in a treatment liquid having a temperature of 40 ° C. or lower.
[21] The method according to [20] above, wherein the immersion time is 1 second to 10 minutes.
[22] The method according to any one of [19] to [21] above, wherein the heating temperature of the treatment liquid in the second step exceeds 40 ° C and is 100 ° C or less.
[23] The above-mentioned [19], wherein the second step is a step of immersing the vulcanized rubber molded body having the treatment liquid attached to the surface through the first step in warm water having a temperature of more than 40 ° C and not more than 100 ° C. ] The method as described in any one of [21].
[24] The method according to [23] above, wherein the immersion time is 1 to 10 minutes.
[25] After the rubber molded body manufacturing process, a finishing process for removing unnecessary portions from the vulcanized rubber molded body obtained through the rubber molded body manufacturing process and an inspection for inspecting the appearance of the vulcanized rubber molded body after the finishing process Including a process, or in addition to the finishing process and the inspection process, further including a packaging process of packaging the vulcanized rubber molded body that has undergone the inspection process,
[19] The surface treatment step (II) is carried out in (i) after the rubber molded body preparation step and before the finishing step and / or (ii) after the finishing step and before the inspection step [19 ] The method as described in any one of [22].
[26] After the rubber molded body manufacturing process, a finishing process for removing unnecessary portions from the vulcanized rubber molded body obtained through the rubber molded body manufacturing process, and an inspection for inspecting the appearance of the vulcanized rubber molded body after the finishing process Including a process, or in addition to the finishing process and the inspection process, further including a packaging process of packaging the vulcanized rubber molded body that has undergone the inspection process,
[23] The surface treatment step (II) is performed in (i) a period after the rubber molded body preparation step and before the finishing step, and / or (ii) after the finishing step and before the inspection step [23 ] Or the method according to [24].
[27] Before the inspection step, further having a cleaning step and a drying step, and after the finishing step and before the inspection step, and having the surface treatment step (II), the temperature of the cleaning step exceeds 40 ° C. The method according to [26] above, wherein the vulcanized rubber molded article is immersed in warm water of 100 ° C. or lower and applied to the second step of the surface treatment step (II).
[28] The rubber composition is nitrile rubber (NBR), hydrogenated nitrile rubber (H-NBR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), [14] to [27], wherein an additive is blended with one or more rubbers selected from the group consisting of butyl rubber (IIR), natural rubber (NR), and ethylene-propylene-diene rubber (EPDM). ] The method as described in any one of.
[29] The method according to any one of the above [14] to [27], wherein the rubber composition is a knuryl rubber composition in which an additive is blended with a knuryl rubber.
[30]
The method according to any one of [14] to [29] above, wherein the rubber product is a rubber seal.
本発明のゴム製品用表面処理液は、ゴムシール等のゴム製品に対して、ゴム製品の伸張性を低下させることなく、低摩擦性および防着性を効果的に付与することができる。特にニトリルゴム(NBR)のような表面の摩擦係数が高いゴムを含むゴム製品であっても、ゴム製品の伸張性を低下させることなく、低摩擦性を付与できる。このため、例えば、ニトリルゴム(NBR)を含むゴムシールを該処理液で表面処理することで、ニトリルゴム(NBR)が有する優れた耐油性及び機械的特性を活かしつつ、運動部の摺動性を維持し得る摺動部用シールを実現できる。また、本発明のゴム製品用表面処理液にて処理されたゴム製品は優れた防着性を示すため、保管時のゴム製品同士の付着を防止でき、ゴム製品が装着される装置や機器の製造現場において付着したゴム製品同士を分離する作業が不要になるため、装置や機器の製造効率向上に繋がる。 The surface treatment liquid for rubber products of the present invention can effectively impart low friction and adhesion to rubber products such as rubber seals without reducing the extensibility of the rubber products. In particular, even a rubber product including a rubber having a high surface friction coefficient such as nitrile rubber (NBR) can be imparted with low friction without reducing the extensibility of the rubber product. For this reason, for example, by applying a surface treatment to a rubber seal containing nitrile rubber (NBR) with the treatment liquid, the slidability of the moving part is improved while utilizing the excellent oil resistance and mechanical properties of nitrile rubber (NBR). A seal for the sliding portion that can be maintained can be realized. In addition, since rubber products treated with the surface treatment liquid for rubber products of the present invention exhibit excellent adhesion, adhesion between the rubber products during storage can be prevented, and the devices and equipment to which the rubber products are mounted can be prevented. Since it is not necessary to separate the rubber products adhering to each other at the manufacturing site, the manufacturing efficiency of the apparatus and equipment is improved.
また、本発明のゴム製品用表面処理液は、溶媒が水系溶媒からなる溶液であることから、室温以上に加温して使用することができ、加温してゴム製品の表面に付すことにより、処理効果をより高めることができる。 Moreover, since the surface treatment liquid for rubber products of the present invention is a solution composed of an aqueous solvent, it can be used after being heated to room temperature or higher, and is heated and applied to the surface of the rubber product. The processing effect can be further enhanced.
また、本発明のゴム製品の製造方法(表面処理工程(I)を有する態様又は表面処理工程(II)を有する態様)によれば、ゴム組成物から加硫ゴム成形体からなるゴム製品を製造する際、作業環境を悪化させることなく、ゴム成形体同士の付着防止を図ることができ、所期の物理的性質(物理的特性)を備えたゴム製品を効率良く製造することができる。また、ゴム成形体同士の付着防止に加えて、ゴム成形体に低摩擦性を付与することができるため、例えば、金属に対する摩擦係数が高いニトリルゴムをベース成分とするニトリルゴム組成物から金属に対して低摩擦性を示すゴム製品(加硫ゴム成形体)を得ることが可能である。 Further, according to the method for producing a rubber product of the present invention (an embodiment having the surface treatment step (I) or an embodiment having the surface treatment step (II)), a rubber product comprising a vulcanized rubber molded body is produced from the rubber composition. In doing so, it is possible to prevent adhesion between the rubber molded bodies without deteriorating the working environment, and it is possible to efficiently produce a rubber product having the desired physical properties (physical characteristics). Further, in addition to preventing adhesion between rubber molded bodies, it is possible to impart low friction to the rubber molded bodies. For example, from a nitrile rubber composition containing a nitrile rubber having a high coefficient of friction against metal to a metal. On the other hand, it is possible to obtain a rubber product (vulcanized rubber molding) exhibiting low friction.
また、本発明のゴム製品の製造方法(表面処理工程(I)を有する態様又は表面処理工程(II)を有する態様)によれば、ゴム製品が析出(ブルーム、ブリード等)を生じやすい成分を含むゴム組成物から製造されるものである場合に、加硫成形工程直後の、析出が生じていないゴム成形体(加硫ゴム成形体)が、ジクロロイソシアヌル酸塩が水系溶媒に溶解した溶液にて表面処理がなされることで、その後の析出、すなわち、仕上げ工程、検査工程および包装工程や、包装工程後の保管や輸送中におけるゴム製品からの析出(ブルーム、ブリード等)が生じることを防止でき、より信頼性の高いゴム製品を製造することができる。 In addition, according to the rubber product manufacturing method of the present invention (an embodiment having the surface treatment step (I) or an embodiment having the surface treatment step (II)), the rubber product is susceptible to precipitation (bloom, bleed, etc.). In the case where the rubber molded body containing the dichloroisocyanurate is dissolved in an aqueous solvent, the rubber molded body (vulcanized rubber molded body) in which no precipitation occurs immediately after the vulcanization molding step is produced. The surface treatment prevents the subsequent precipitation, that is, the precipitation (bloom, bleed, etc.) from the rubber product during the finishing process, inspection process and packaging process, and during storage and transportation after the packaging process. And a more reliable rubber product can be manufactured.
また、本発明のゴム製品の製造方法(表面処理工程(II)を有する態様)によれば、常温付近の処理液を使用するため、処理液の劣化を抑制でき、表面処理を繰り返し行う場合に、処理液を補充するだけでよく、劣化した処理液の廃棄の問題がない。このため、処理液に伴うコストを削減でき、また、処理液の廃棄がないので、環境汚染の懸念もない。 In addition, according to the rubber product manufacturing method of the present invention (a mode having the surface treatment step (II)), since the treatment liquid near room temperature is used, deterioration of the treatment liquid can be suppressed, and the surface treatment is repeatedly performed. It is only necessary to replenish the treatment liquid, and there is no problem of discarding the deteriorated treatment liquid. For this reason, costs associated with the processing liquid can be reduced, and there is no concern about environmental pollution because the processing liquid is not discarded.
なお、本明細書中の「常温」とは、JIS Z 8703に規定の20℃±15℃(5〜35℃)のことであり、「常温付近」とは、1〜40℃を指す。 In addition, “normal temperature” in this specification means 20 ° C. ± 15 ° C. (5-35 ° C.) defined in JIS Z 8703, and “near normal temperature” means 1-40 ° C.
以下、本発明をその好適な実施形態に即して説明する。 Hereinafter, the present invention will be described with reference to preferred embodiments thereof.
[表面処理液および表面改質方法]
本発明のゴム製品用表面処理液(以下、単に「表面処理液」または「処理液」とも略称する。)は、ジクロロイソシアヌル酸塩が水系溶媒に溶解した溶液からなる。なお、処理対象のゴム製品の典型例としては、ゴムシール(特に摺動部用ゴムシール)が挙げられる。
[Surface treatment liquid and surface modification method]
The surface treatment liquid for rubber products of the present invention (hereinafter simply referred to as “surface treatment liquid” or “treatment liquid”) consists of a solution in which dichloroisocyanurate is dissolved in an aqueous solvent. A typical example of the rubber product to be treated includes a rubber seal (particularly, a rubber seal for a sliding portion).
本発明における、「水系溶媒」とは、典型的には水であるが、水に水溶性有機溶媒が溶解した水溶液も「水系溶媒」として使用することができる。このような水溶性有機溶媒としては、例えば、メタノール、エタノール等の低級アルコール類;アセトン、メチルエチルケトン等の低級ケトン類;酢酸などの低級カルボン酸類;エチレングリコール、プロピレングリコール、ジエチレングリコール等のグリコール類;アセトアルデヒド等のアルデヒド類等が挙げられる。水溶性有機溶媒は水へのジクロロイソシアヌル酸塩の溶解度を著しく低下させない範囲で使用され、通常、水に対して30重量%以下の範囲内で使用することができる。 In the present invention, the “aqueous solvent” is typically water, but an aqueous solution in which a water-soluble organic solvent is dissolved in water can also be used as the “aqueous solvent”. Examples of such water-soluble organic solvents include lower alcohols such as methanol and ethanol; lower ketones such as acetone and methyl ethyl ketone; lower carboxylic acids such as acetic acid; glycols such as ethylene glycol, propylene glycol and diethylene glycol; acetaldehyde And aldehydes. The water-soluble organic solvent is used within a range that does not significantly reduce the solubility of dichloroisocyanurate in water, and can usually be used within a range of 30% by weight or less based on water.
また、本発明における、「ジクロロイソシアヌル酸塩」とは、水系溶媒に溶解し得る塩であれば、特に制限なく使用できるが、低摩擦性付与効果の観点から、ナトリウム塩、カリウム塩等のアルカリ金属塩が好ましく、ナトリウム塩が特に好ましい。なお、ジクロロイソシアヌル酸ナトリウムやジクロロイソシアヌル酸カリウムは、通常の無水物の他に結晶水を有する水和物も用いることができる。本発明において、ジクロロイソシアヌル酸塩は1種または2種以上を使用できる。 In the present invention, the “dichloroisocyanurate” can be used without particular limitation as long as it is a salt that can be dissolved in an aqueous solvent. However, from the viewpoint of the effect of imparting low friction, alkali such as sodium salt and potassium salt can be used. Metal salts are preferred and sodium salts are particularly preferred. In addition, the sodium dichloroisocyanurate and potassium dichloroisocyanurate can also use the hydrate which has crystal water other than a normal anhydride. In the present invention, one or more dichloroisocyanurates can be used.
本発明の表面処理液(すなわち、ジクロロイソシアヌル酸塩が水系溶媒に溶解した溶液)中のジクロロイソシアヌル酸塩の含有量は、処理液全体当たり2〜15重量%が好ましく、より好ましくは2〜10重量%であり、特に好ましくは、5〜10重量%である。15重量%より多いと、当該処理液によるゴム製品の表面処理中に発生する気泡量が多くなり、表面処理による反応が阻害されて、所期の効果が得られ難くなる。また、2重量%未満ではゴム製品の表面に十分な低摩擦性を付与することが困難な傾向となる。 The content of dichloroisocyanurate in the surface treatment liquid of the present invention (that is, a solution in which dichloroisocyanurate is dissolved in an aqueous solvent) is preferably 2 to 15% by weight, more preferably 2 to 10%, based on the entire treatment liquid. % By weight, particularly preferably 5 to 10% by weight. When the amount is more than 15% by weight, the amount of bubbles generated during the surface treatment of the rubber product with the treatment liquid increases, the reaction due to the surface treatment is inhibited, and the desired effect is hardly obtained. If it is less than 2% by weight, it tends to be difficult to impart sufficient low friction to the surface of the rubber product.
本発明のゴム製品の表面改質方法は、本発明の表面処理液をゴム製品の表面に付す(接触させる)ことによってなされる。本発明の表面処理液は、溶媒が水系溶媒からなる溶液であることから、室温保存が可能であり、また、加熱して室温以上の温度にしても、溶媒が蒸発しにくい。また、本発明の表面処理液を50〜70℃程度まで加熱し、50〜70℃の温度を維持した状態、すなわち、本発明の表面処理液を50〜70℃に加温した状態でゴム製品の表面に付すと一層高い処理効果(表面改質効果)を得ることができる。表面処理液を70℃を超える温度に加温すると、ゴム製品の表面処理中に発生する気泡量が多くなって、処理効果が却って低下する傾向になり、また、部分的にゴム製品の内部まで処理液が浸透して、均一処理が困難となってしまう場合がある。また、水溶液の蒸発が顕著になり、処理液の寿命の点でも好ましくない。 The surface modification method for a rubber product of the present invention is performed by applying (contacting) the surface treatment liquid of the present invention to the surface of the rubber product. Since the surface treatment liquid of the present invention is a solution composed of an aqueous solvent, it can be stored at room temperature, and the solvent hardly evaporates even when heated to room temperature or higher. Further, the rubber product in a state where the surface treatment liquid of the present invention is heated to about 50 to 70 ° C. and maintained at a temperature of 50 to 70 ° C., that is, the surface treatment liquid of the present invention is heated to 50 to 70 ° C. A higher treatment effect (surface modification effect) can be obtained by attaching to the surface. When the surface treatment liquid is heated to a temperature exceeding 70 ° C., the amount of bubbles generated during the surface treatment of the rubber product increases, and the treatment effect tends to decrease. The treatment liquid may permeate and make uniform treatment difficult. Further, the evaporation of the aqueous solution becomes remarkable, which is not preferable from the viewpoint of the life of the treatment liquid.
本発明の表面処理液をゴム製品の表面に付す(接触させる)方法は特に限定されないが、ゴム製品を処理液中に浸漬する処理、ゴム製品に処理液をスプレー塗布する処理、はけ塗り等が挙げられるが、作業が簡易で、短時間で効果が得られるという観点から、浸漬処理が好ましい。浸漬時間は1〜15分程度が好ましく、より好ましくは1〜10分程度である。15分を超えると、ゴム製品の表面に微細なクラック(走査型電子顕微鏡(SEM)による1000倍での観察によって確認されるクラック)を生じ、ゴム製品の性能が低下する傾向となる。1分未満では、十分に高い低摩擦性付与効果および/または十分に高い防着性付与効果が得られにくくなる。本発明の表面処理液をゴムシール表面に付した後は、通常、水またはアルコール等の有機溶媒に数秒程度ゴムシールを浸すことでゴムシール表面の処理液を洗浄し、その後取り出して室温で自然乾燥させる。なお、処理液および洗浄液の温度が高温であると、ゴムシールが高温状態で取り出されることになり、乾燥時の乾燥時間の短縮にもつながる。従って、上述の50〜70℃に加温した処理液は、表面改質の処理効率の観点からも好ましい。 The method of applying (contacting) the surface treatment liquid of the present invention to the surface of the rubber product is not particularly limited, but the treatment of immersing the rubber product in the treatment liquid, the treatment of spraying the treatment liquid onto the rubber product, brushing, etc. However, the dipping treatment is preferable from the viewpoint that the operation is simple and the effect can be obtained in a short time. The immersion time is preferably about 1 to 15 minutes, more preferably about 1 to 10 minutes. If it exceeds 15 minutes, fine cracks (cracks confirmed by observation with a scanning electron microscope (SEM) at 1000 times) are generated on the surface of the rubber product, and the performance of the rubber product tends to be lowered. If it is less than 1 minute, it will become difficult to obtain a sufficiently high low-friction imparting effect and / or a sufficiently high adhesion-preventing effect. After the surface treatment liquid of the present invention is applied to the rubber seal surface, the treatment liquid on the rubber seal surface is usually washed by immersing the rubber seal in water or an organic solvent such as alcohol for several seconds, and then taken out and naturally dried at room temperature. When the temperature of the treatment liquid and the cleaning liquid is high, the rubber seal is taken out at a high temperature, which leads to shortening of the drying time during drying. Therefore, the above-mentioned treatment liquid heated to 50 to 70 ° C. is preferable also from the viewpoint of the treatment efficiency of surface modification.
[ゴム製品の製造方法]
本発明のゴム製品の製造方法(以下、「本発明方法」とも略称する)は、ゴム組成物から加硫ゴム成形体を作製するゴム成形体作製工程後に、ジクロロイソシアヌル酸塩が水系溶媒に溶解した溶液からなる処理液をゴム成形体表面に付す表面処理工程を有することを主たる特徴とする。
[Production method of rubber products]
The method for producing a rubber product of the present invention (hereinafter also abbreviated as “the method of the present invention”) is a method in which a dichloroisocyanurate is dissolved in an aqueous solvent after a rubber molded body preparation step for preparing a vulcanized rubber molded body from a rubber composition. The main feature is that it has a surface treatment step of attaching the treatment liquid comprising the solution to the surface of the rubber molded body.
従来からのゴム製品の製造方法と同様に、本発明方法における、ゴム組成物から加硫ゴム成形体を作製するゴム成形体作製工程は、混練されたゴム組成物を予備成形し、さらに加硫成形する態様(すなわち、混練されたゴム組成物を予備成形する予備成形工程と、予備成形工程を経て得られたゴム成形体を加硫成形する加硫成形工程とからなる態様)か、或いは、混練されたゴム組成物を射出成形して加硫ゴム成形体を得る態様からなる。 Similar to conventional rubber product manufacturing methods, the rubber molded body preparation step for preparing a vulcanized rubber molded body from the rubber composition in the method of the present invention involves pre-molding the kneaded rubber composition and further vulcanizing the rubber composition. A mode of molding (that is, a mode comprising a preforming step of preforming a kneaded rubber composition and a vulcanization molding step of vulcanizing a rubber molded body obtained through the preforming step), or The kneaded rubber composition is injection molded to obtain a vulcanized rubber molded body.
また、ゴム成形体作製工程後は、基本的に、ゴム成形体作製工程で得られた加硫ゴム成形体の不要部分を取り除く仕上げ工程、仕上げ工程を経た加硫ゴム成形体の外観検査を行う検査工程を含む。また、仕上げ工程で生じたゴム屑等の除去、ゴム製品の美観、表面性状の安定化等のために、仕上げ工程を経た加硫ゴム成形体を洗浄、乾燥してから(すなわち、洗浄工程および乾燥工程を行ってから)、検査工程を行うことがあり、また、多くの場合、検査工程を経て良品とされた加硫ゴム成形体(ゴム製品)は、保管や、出荷後の製品の流通過程での製品保護等のために、包装材に計数の上(すなわち、所定数を計数してから包装材に)包装される(すなわち、包装工程を有する)ことがある。 In addition, after the rubber molded body manufacturing process, basically, the appearance inspection of the vulcanized rubber molded body that has undergone the finishing process and finishing process to remove unnecessary portions of the vulcanized rubber molded body obtained in the rubber molded body manufacturing process is performed. Includes inspection process. In addition, the vulcanized rubber molded product that has undergone the finishing process is washed and dried in order to remove rubber scraps generated in the finishing process, to improve the appearance of the rubber product, to stabilize the surface properties, etc. After performing the drying process), the inspection process may be performed. In many cases, the vulcanized rubber molded product (rubber product) that has been made a good product through the inspection process is stored and distributed after shipment. In order to protect the product in the process, the packaging material may be counted (that is, after a predetermined number is counted) and then packaged (that is, having a packaging process).
本明細書中、「未加硫」、「加硫成形」および「加硫ゴム」等における「加硫」とは、硫黄、或いは、硫黄と加硫促進剤を使用してゴムのポリマー分子を化学的に結合して三次元化すること、或いは、該三次元化された状態を意味するだけでなく、有機過酸化物等の硫黄以外の架橋剤を使用してゴムのポリマー分子を化学的に結合して三次元化すること、或いは、該三次元化された状態を意味する。 In the present specification, “vulcanization” in “unvulcanized”, “vulcanized molding”, “vulcanized rubber” and the like refers to the polymer molecule of rubber using sulfur or sulfur and a vulcanization accelerator. Not only does it chemically combine to make it three-dimensional, but it means not only the three-dimensional state, but also uses a cross-linking agent other than sulfur, such as an organic peroxide, to chemically modify the rubber polymer molecules. To be three-dimensionally combined with or the three-dimensional state.
以下、本発明方法におけるゴム組成物および各工程を詳しく説明する。
ゴム組成物は、ベース成分であるゴム材料に、架橋剤、架橋促進剤、スコーチ防止剤、老化防止剤、充填剤、可塑剤、架橋助剤、加工助剤、プロセス油、難燃剤等の種々の添加剤が配合された組成物であり、これらの添加剤はゴム材料とともに混練機に投入される。
Hereinafter, the rubber composition and each step in the method of the present invention will be described in detail.
The rubber composition includes various rubber materials such as a crosslinking agent, a crosslinking accelerator, a scorch inhibitor, an anti-aging agent, a filler, a plasticizer, a crosslinking aid, a processing aid, a process oil, and a flame retardant. These additives are added to a kneader together with the rubber material.
ゴム材料は、特に限定されず、例えば、ニトリルゴム(NBR)、水素化ニトリルゴム(H−NBR)、イソプレンゴム(IR)、ブタジエンゴム(BR)、スチレン−ブタジエンゴム(SBR)、クロロプレンゴム(CR)、ブチルゴム(IIR)、天然ゴム(NR)、エチレン-プロピレン-ジエンゴム(EPDM)等が挙げられる。ゴム材料は1種又は2種以上を使用できる。 The rubber material is not particularly limited. For example, nitrile rubber (NBR), hydrogenated nitrile rubber (H-NBR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), chloroprene rubber ( CR), butyl rubber (IIR), natural rubber (NR), ethylene-propylene-diene rubber (EPDM) and the like. One or more rubber materials can be used.
架橋剤は、ゴムのポリマー分子を化学的に結合して三次元化するために添加する材料であり、硫黄または有機過酸化物等が好適に使用される。有機過酸化物としては、例えば、ジt−ブチルパーオキサイド、ジクミルパーオキサイド、t−ブチルクミルパーオキサイド、1,1−ジ(t−ブチルパーオキシ)−3,3,5−トリメチルシクロヘキサン、2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)ヘキサン、2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)へキシン−3,1,3−ジ(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(ベンゾイルパーオキシ)ヘキサン、t−ブチルパーオキシベンゾエート、t−ブチルパーオキシイソプロピルカーボネート、n−ブチル−4,4−ジ(t−ブチルパーオキシ)バレレート等が例示される。架橋剤は1種又は2種以上を使用できる。 The cross-linking agent is a material added to chemically bond rubber polymer molecules into a three-dimensional structure, and sulfur or organic peroxide is preferably used. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,1,3-di (t -Butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, n-butyl-4,4-di Examples thereof include (t-butylperoxy) valerate. One or more crosslinking agents can be used.
架橋促進剤としては、例えば、チウラム系加硫促進剤、スルフェンアミド系加硫促進剤、チアゾール系加硫促進剤、ジチオカルバミン酸塩系加硫促進剤等が例示される。スコーチ防止剤としては、例えば、N−シクロヘキシルチオフタルイミド、N−ニトロジフェニルアミン、無水フタル酸、N−フェニル−N−(トリクロロメチルチオ)ベンゼンスルホンアミド等が例示される。老化防止剤としては、例えば、アミン系老化防止剤、フェノール系老化防止剤、イミダゾール系老化防止剤等が例示される。充填剤としては、例えば、カーボンブラック、炭酸カルシウム、シリカ、硫酸バリウム、酸化チタン、水酸化マグネシウム、水酸化アルミニウム、タルク、クレー、グラファイ卜、珪酸カルシウム等が例示される。可塑剤としては、例えば、フタル酸ジオクチル(DOP)等のフタル酸系可塑剤、ジオクチルアジペート等のアジピン酸系可塑剤、セバシン酸ジオクチル等のセバシン酸系可塑剤、トリ−(2−エチルヘキシル)トリメリテート等のトリメリット酸系可塑剤、ポリエーテルやポリエステル等の重合型可塑剤等が例示される。架橋助剤としては、例えば、トリアリルシアヌレー卜、トリアリルイソシアヌレート、N,N’−m−フェニレンビスマレイミド、トリメチロールプロパントリメタクリレート、トリアリルトリメリテート、1,2ーポリブタジエンなどの多官能性化合物が例示される。加工助剤としては、例えば、ステアリン酸、パルミチン酸、パラフィンワックス等が例示される。プロセス油としては、例えば、アロマティック系プロセスオイル、ナフテン系プロセスオイル、パラフィン系プロセスオイル等が例示される。また、難燃剤としては、例えば、水酸化アルミニウム、水酸化マグネシウム等の水和金属酸化物、デカブロモジフェニルエタン等の臭素系化合物等が例示される。これら架橋剤以外の各添加剤も架橋剤と同様に1種又は2種以上を使用できる。 Examples of the crosslinking accelerator include thiuram vulcanization accelerators, sulfenamide vulcanization accelerators, thiazole vulcanization accelerators, dithiocarbamate vulcanization accelerators, and the like. Examples of the scorch inhibitor include N-cyclohexylthiophthalimide, N-nitrodiphenylamine, phthalic anhydride, N-phenyl-N- (trichloromethylthio) benzenesulfonamide, and the like. Examples of the anti-aging agent include amine-based anti-aging agents, phenol-based anti-aging agents, and imidazole-based anti-aging agents. Examples of the filler include carbon black, calcium carbonate, silica, barium sulfate, titanium oxide, magnesium hydroxide, aluminum hydroxide, talc, clay, graphite, calcium silicate, and the like. Examples of the plasticizer include phthalic acid plasticizers such as dioctyl phthalate (DOP), adipic acid plasticizers such as dioctyl adipate, sebacic acid plasticizers such as dioctyl sebacate, and tri- (2-ethylhexyl) trimellitate. Examples thereof include trimellitic acid plasticizers such as polyethers, and polymerization plasticizers such as polyethers and polyesters. Examples of the crosslinking aid include triallyl cyanurate, triallyl isocyanurate, N, N′-m-phenylenebismaleimide, trimethylolpropane trimethacrylate, triallyl trimellitate, 1,2-polybutadiene and the like. Multifunctional compounds are exemplified. Examples of processing aids include stearic acid, palmitic acid, paraffin wax, and the like. Examples of the process oil include aromatic process oil, naphthene process oil, paraffin process oil, and the like. Examples of the flame retardant include hydrated metal oxides such as aluminum hydroxide and magnesium hydroxide, and bromine compounds such as decabromodiphenylethane. Each additive other than these crosslinking agents can be used alone or in combination of two or more as in the case of the crosslinking agent.
ゴム組成物における各種添加剤の配合量は、製造すべきゴム製品の用途、要求特性等に応じて常法に従って適宜調整される。例えば、ゴム材料にニトリルゴムを使用してシール材を製造する場合、ゴム組成物の典型的な組成としては、以下の組成が例示される。 The compounding amount of various additives in the rubber composition is appropriately adjusted according to a conventional method according to the use of rubber products to be manufactured, required characteristics, and the like. For example, when manufacturing a sealing material using nitrile rubber as a rubber material, the following composition is illustrated as a typical composition of a rubber composition.
(組成例1)
ニトリルゴム:100重量部
架橋剤(典型的には硫黄):0.1〜3重量部
充填剤(典型的にはカーボンブラック):20〜150重量部
架橋促進剤:2〜6.5重量部
加工助剤:0.1〜5重量部
可塑剤:3〜20重量部
老化防止剤:0.5〜5重量部
酸化亜鉛:3〜7重量部
(Composition Example 1)
Nitrile rubber: 100 parts by weight Crosslinking agent (typically sulfur): 0.1 to 3 parts by weight Filler (typically carbon black): 20 to 150 parts by weight Crosslinking accelerator: 2 to 6.5 parts by weight Processing aid: 0.1-5 parts by weight Plasticizer: 3-20 parts by weight Anti-aging agent: 0.5-5 parts by weight Zinc oxide: 3-7 parts by weight
また、ゴム材料にEPDMを使用してシール材を製造する場合、ゴム組成物の典型的な組成としては、以下の組成が例示される。 Moreover, when manufacturing a sealing material using EPDM for a rubber material, the following compositions are illustrated as a typical composition of a rubber composition.
(組成例2)
EPDM:100重量部
酸化亜鉛:3〜7重量部
ステアリン酸:0.3〜1.5重量部
カーボンブラック:50〜120重量部
ナフテン系オイル:30〜80重量部
加硫促進剤:0.7〜2.4重量部
硫黄:0.1〜3重量部
(Composition Example 2)
EPDM: 100 parts by weight Zinc oxide: 3-7 parts by weight Stearic acid: 0.3-1.5 parts by weight Carbon black: 50-120 parts by weight Naphthenic oil: 30-80 parts by weight Vulcanization accelerator: 0.7 -2.4 parts by weight Sulfur: 0.1-3 parts by weight
ゴム組成物の混練は、公知の混練機(例えば、オープンロール、インターミックス、ニーダー、バンバリーミキサ等)や二軸混練押出機などを用いて行われる。混練温度、混練条件等は製造すべきゴム製品の用途、要求特性等に応じて常法に従って適宜設定される。 The rubber composition is kneaded using a known kneader (for example, an open roll, an intermix, a kneader, a Banbury mixer, etc.), a twin-screw kneading extruder, or the like. The kneading temperature, kneading conditions, and the like are appropriately set according to conventional methods according to the use, required characteristics, etc. of the rubber product to be manufactured.
予備成形工程では、混練されたゴム組成物を、製造すべきゴム製品(加硫ゴム成形体)に近い形状または成形しやすい形状に予備成形する。予備成形には、従来からのゴム製品の製造時における予備成形工程において広く使用されているような例えば、押出機、オープンロール、プレフォマなどの装置が好ましく用いられる。予備成形して得られる未加硫ゴムの成形体の形状および大きさは製造すべきゴム製品(加硫ゴム成形体)の形状および大きさを考慮して適宜選択される。なお、射出成形によって加硫ゴム成形体を得る場合は、あらかじめ混練時にリボン形状に仕上げておくことにより、予備成形工程は不要であり、混練工程後、予備成形工程を経ることなく、加硫成形工程が行われる。 In the preforming step, the kneaded rubber composition is preformed into a shape close to a rubber product to be manufactured (vulcanized rubber molded body) or a shape that is easy to mold. For the pre-molding, devices such as an extruder, an open roll, and a pre-former that are widely used in a pre-molding process in manufacturing a conventional rubber product are preferably used. The shape and size of the unvulcanized rubber molded body obtained by preforming are appropriately selected in consideration of the shape and size of the rubber product (vulcanized rubber molded body) to be manufactured. In addition, when obtaining a vulcanized rubber molded body by injection molding, a preforming process is unnecessary by finishing in a ribbon shape at the time of kneading in advance. After the kneading process, the vulcanization molding is performed without passing through the preforming process. A process is performed.
加硫成形工程では、例えば、射出成形機、圧縮成形機、加熱プレス成形機などを用いて、所定の温度で加熱成形して、加硫ゴム成形体を得る。加熱温度および加熱時間はゴム材料、製造すべきゴム製品の形状などに応じて適宜設定されるが、一般的には、130〜200℃、1分〜120分の範囲内で選択される。具体的には、例えば、ゴム組成物がニトリルゴム組成物の場合、好適な温度条件としては、約150〜200℃で約2〜30分間程度加熱する態様が挙げられる。 In the vulcanization molding step, for example, using an injection molding machine, a compression molding machine, a hot press molding machine, or the like, heat molding is performed at a predetermined temperature to obtain a vulcanized rubber molded body. The heating temperature and heating time are appropriately set according to the rubber material, the shape of the rubber product to be manufactured, etc., but are generally selected within the range of 130 to 200 ° C. and 1 to 120 minutes. Specifically, for example, when the rubber composition is a nitrile rubber composition, suitable temperature conditions include a mode of heating at about 150 to 200 ° C. for about 2 to 30 minutes.
加硫成形工程を経て得られた加硫ゴム成形体は通常バリなどの不要部分が生じており、このため、バリなどの不要部分を取り除くための仕上げ工程が行われる。仕上げ工程は、通常、打ち抜き機、手毟り等を使用して、装置乃至人の手によって行われる。 The vulcanized rubber molded body obtained through the vulcanization molding process usually has unnecessary parts such as burrs, and therefore, a finishing process for removing unnecessary parts such as burrs is performed. The finishing process is usually performed by an apparatus or a human hand using a punching machine, a hand-knot, or the like.
仕上げ工程後に行われる洗浄工程では、通常、洗浄液として水道水または工業用のイオン交換水などをゴム成形体表面に吹き付けたり、流しかけたりするか、或いは、水道水または工業用のイオン交換水などが充填された洗浄槽にゴム成形体を浸漬する。洗浄工程により、仕上げ工程を経た加硫ゴム成形体は梱包作業へ移る。なお、ゴム成形体表面への不純物の付着などを抑制する観点から洗浄液としてはイオン交換水を使うことが好適であり、イオン交換水としては、例えば、25℃での導電率が、5〜25MΩ・cm、好ましくは、10〜20MΩ・cmのものを使用するのが好ましい。洗浄液の温度は、常温若しくは常温よりも高い温度であればよく、後の乾燥工程のことを考慮すると、常温よりも20〜80℃以内の範囲で高い温度であることが好ましい。また、洗浄槽は、2つ以上、好ましくは3つ以上(8つ以下)設けてもよく、複数の洗浄槽にて、ゴム成形体の移し替えを行うことで、洗浄効果が向上する。 In the cleaning process performed after the finishing process, tap water or industrial ion exchange water is usually sprayed or poured on the surface of the rubber molded body as a cleaning liquid, or tap water or industrial ion exchange water is used. The rubber molded body is dipped in a cleaning tank filled with. By the washing process, the vulcanized rubber molded body that has undergone the finishing process is transferred to a packing operation. In addition, it is suitable to use ion-exchange water as the cleaning liquid from the viewpoint of suppressing the adhesion of impurities to the rubber molded body surface. As the ion-exchange water, for example, the conductivity at 25 ° C. is 5 to 25 MΩ. · Cm, preferably 10 to 20 MΩ · cm is preferably used. The temperature of the cleaning liquid may be normal temperature or higher than normal temperature, and considering the subsequent drying step, it is preferable that the temperature is higher in the range of 20 to 80 ° C. than normal temperature. Also, two or more, preferably three or more (eight or less) cleaning tanks may be provided, and the cleaning effect is improved by transferring the rubber molding in a plurality of cleaning tanks.
乾燥工程は、洗浄工程を経たゴム成形体を乾燥する工程であり、通常、ゴム成形体を大気中で自然乾燥させる。なお、乾燥を促進するために、例えば、50〜100℃程度の熱風を吹き付けて乾燥を行ってもよい。 The drying step is a step of drying the rubber molded body that has undergone the cleaning process, and usually the rubber molded body is naturally dried in the air. In addition, in order to accelerate | stimulate drying, you may dry by blowing a hot air of about 50-100 degreeC, for example.
検査工程は、最終のゴム製品とするために、ゴム成形体の外観を目視、拡大鏡、画像解析装置等にて検査し、ゴム成形体の表面の傷の有無を検査する工程である。かかる検査工程にて良品と不良品とが選別される。 The inspection step is a step of inspecting the appearance of the rubber molded body by visual inspection, a magnifying glass, an image analysis device, or the like to make a final rubber product, and inspecting the surface of the rubber molded body for scratches. In this inspection process, good products and defective products are selected.
包装工程は、ゴム製品の保管や出荷後のゴム製品の輸送過程での保護等のために、検査工程を経たゴム成形体を包装材にて包装する工程である。かかる包装工程では、複数個のゴム成形体が無作為に包装袋に入れて梱包される。なお、ここでいう、「梱包」は輸送を目的とした「工業包装」の意味である。 The packaging process is a process in which a rubber molded body that has undergone the inspection process is packaged with a packaging material in order to store the rubber product or protect the rubber product in the transportation process after shipment. In such a packaging process, a plurality of rubber moldings are randomly packed in a packaging bag. Here, “packaging” means “industrial packaging” for the purpose of transportation.
本発明方法では、上述の通り、ゴム組成物から加硫ゴム成形体を作製するゴム成形体作製工程後に、ジクロロイソシアヌル酸塩が水系溶媒に溶解した溶液からなる処理液(以下、「本発明の処理液」ともいう)を用いて加硫ゴム成形体の表面処理を行う表面処理工程が行われる。ここで、「ジクロロイソシアヌル酸塩が水系溶媒に溶解した溶液からなる処理液」は、前述のゴム製品用表面処理液と同じものである。かかる処理液は、ゴム成形体の内部に浸透しにくく、ゴム成形体の表面のみに作用し、ゴム成形体の物理的性質の低下をまねくことなく、ゴム成形体の表面に防着性を付与する。 In the method of the present invention, as described above, after the rubber molded body preparation step for preparing a vulcanized rubber molded body from the rubber composition, a treatment liquid (hereinafter referred to as “the present invention”) comprising a solution in which dichloroisocyanurate is dissolved in an aqueous solvent. A surface treatment step of performing a surface treatment of the vulcanized rubber molded body using a "treatment liquid") is performed. Here, the “treatment liquid comprising a solution in which dichloroisocyanurate is dissolved in an aqueous solvent” is the same as the aforementioned surface treatment liquid for rubber products. Such a treatment liquid hardly penetrates into the inside of the rubber molded body, acts only on the surface of the rubber molded body, and gives adhesion to the surface of the rubber molded body without deteriorating the physical properties of the rubber molded body. To do.
なお、処理液中のジクロロイソシアヌル酸塩の含有量は、処理液全体当たり2〜20重量%が好ましく、より好ましくは2〜15重量%であり、特に好ましくは2〜10重量%である。20重量%より多いと、当該処理液によるゴム成形体の表面処理中に発生する気泡量が多くなり、表面処理による反応が阻害されて、所期の効果が得られ難くなる。また、2重量%未満ではゴム成形体表面に十分な低摩擦性を付与することが困難な傾向となる。 In addition, the content of dichloroisocyanurate in the treatment liquid is preferably 2 to 20% by weight, more preferably 2 to 15% by weight, and particularly preferably 2 to 10% by weight based on the whole treatment liquid. When the amount is more than 20% by weight, the amount of bubbles generated during the surface treatment of the rubber molded body with the treatment liquid increases, the reaction by the surface treatment is inhibited, and the desired effect is hardly obtained. If it is less than 2% by weight, it tends to be difficult to impart sufficient low friction to the surface of the rubber molded body.
本発明方法は、表面処理工程が、20〜70℃の処理液にて加硫ゴム成形体の表面処理を行う工程(表面処理工程(I))からなる第1の態様の方法と、表面処理工程が、40℃以下の処理液を加硫ゴム成形体の表面に付す第1工程と、加硫ゴム成形体の表面に付着した処理液の加熱および洗浄を行う第2工程とを含む工程(表面処理工程(II))からなる第2の態様の方法を含む。 The method of the present invention is the method of the first aspect, wherein the surface treatment step comprises a step (surface treatment step (I)) of subjecting the vulcanized rubber molded body to a surface treatment with a treatment liquid at 20 to 70 ° C. The process includes a first process in which a treatment liquid of 40 ° C. or less is applied to the surface of the vulcanized rubber molded body, and a second process in which the treatment liquid adhered to the surface of the vulcanized rubber molded body is heated and washed ( The method of the 2nd aspect which consists of surface treatment process (II)) is included.
第1の態様
表面処理工程(I)は、(i)ゴム成形体作製工程後、仕上げ工程前の期間、及び/又は、(ii)仕上げ工程後、検査工程前の期間にて、実施される。なお、表面処理工程(I)が、(ii)仕上げ工程後、検査工程前の期間に実施される場合は、通常、洗浄工程および乾燥工程は、表面処理工程(I)後、検査工程前に行われる。表面処理工程(I)では、後述のとおり、処理液をゴム成形体の表面に付した後、通常、水やアルコールによる洗浄と乾燥を行うが、かかる工程順とすることで、表面処理工程(I)での洗浄と乾燥を省略することができる。
The first aspect surface treatment step (I) is performed in (i) a period after the rubber molded body preparation step and before the finishing step, and / or (ii) after the finishing step and before the inspection step. . In addition, when surface treatment process (I) is implemented in the period before (ii) finishing process and before an inspection process, a washing process and a drying process are usually after surface treatment process (I) and before an inspection process. Done. In the surface treatment step (I), as described later, after the treatment liquid is applied to the surface of the rubber molded body, it is usually washed and dried with water or alcohol, but the surface treatment step ( Cleaning and drying in I) can be omitted.
処理液を20〜70℃に加熱し、20〜70℃の温度を維持した状態(処理液を20〜70℃に加温した状態)でゴム成形体の表面に付すことで、より高い処理効果(防着性付与効果)を得ることができる。処理液を70℃を超える温度に加温すると、ゴム成形体の表面処理中に発生する気泡量が多くなって、処理効果が却って低下する。また、部分的にゴム成形体の内部まで処理液が浸透して、均一処理が困難な傾向となる。処理液が20℃より低い温度であると、表面処理が進行せず、生産効率が低下する。50℃以上70℃以下の範囲に加温した処理液が特に好ましい。 A higher treatment effect is achieved by heating the treatment liquid to 20 to 70 ° C and maintaining the temperature of 20 to 70 ° C (the treatment liquid is heated to 20 to 70 ° C) on the surface of the rubber molded body. (Adhesiveness imparting effect) can be obtained. When the treatment liquid is heated to a temperature exceeding 70 ° C., the amount of bubbles generated during the surface treatment of the rubber molded body increases, and the treatment effect decreases. Further, the treatment liquid partially penetrates into the rubber molded body, and uniform treatment tends to be difficult. When the treatment liquid is at a temperature lower than 20 ° C., the surface treatment does not proceed and the production efficiency is lowered. A treatment liquid heated in a range of 50 ° C. or higher and 70 ° C. or lower is particularly preferable.
ゴム成形体の表面に、処理液を付す(接触させる)方法は特に限定されないが、ゴム成形体を処理液中に浸漬する方法、ゴム成形体に処理液をスプレー塗布する方法、ゴム成形体に処理液をはけ塗りする方法、ゴム成形体に処理液をかけ流す方法等が挙げられるが、作業が簡易で、短時間で効果が得られ、しかも、多数個のゴム成形体を一括して均一に処理ができるという観点から、浸漬処理が好ましい。 The method of attaching (contacting) the treatment liquid to the surface of the rubber molded body is not particularly limited, but the method of immersing the rubber molded body in the treatment liquid, the method of spray-coating the treatment liquid on the rubber molded body, the rubber molded body Examples include a method of brushing the treatment liquid, a method of pouring the treatment liquid over the rubber molded body, etc., but the work is simple, an effect can be obtained in a short time, and a large number of rubber molded bodies can be collected at once. The immersion treatment is preferable from the viewpoint that the treatment can be performed uniformly.
浸漬時間は10秒〜30分程度が好ましく、より好ましくは30秒〜15分程度である。30分を超えると、製品内部への処理液の浸透の影響が生じ、引張により表面に亀裂が発生する傾向となる。10秒未満では、十分に高い防着性付与効果が得られにくくなる傾向となる。処理液をゴム成形体表面に付した後は、通常、水またはアルコール等の有機溶媒に数秒程度ゴム成形体を浸すことでゴム成形体表面の処理液を洗浄し、その後取り出して室温で自然乾燥させる。 The immersion time is preferably about 10 seconds to 30 minutes, more preferably about 30 seconds to 15 minutes. When it exceeds 30 minutes, the influence of the penetration of the treatment liquid into the product occurs, and the surface tends to crack by tension. If it is less than 10 seconds, it tends to be difficult to obtain a sufficiently high adhesion-imparting effect. After the treatment liquid has been applied to the surface of the rubber molded body, the rubber molded body surface is usually washed by immersing the rubber molded body in water or an organic solvent such as alcohol for several seconds, and then removed and air-dried at room temperature. Let
第2の態様
表面処理工程(II)は、(i)ゴム成形体作製工程後、仕上げ工程前の期間、及び/又は、(ii)仕上げ工程後、検査工程前の期間にて、実施される。なお、表面処理工程(II)が、(ii)仕上げ工程後、検査工程前の期間に実施される場合、通常、洗浄工程および乾燥工程は、表面処理工程(II)後、検査工程前に行われる。なお、この場合、洗浄工程を、温度が40℃を超え、100℃以下の温水に加硫ゴム成形体を浸漬する工程にすることで、該洗浄工程を、後記にて詳述する、表面処理工程(II)の第2工程に充当させることができるので、ゴム製品の製造工程を簡略化できる、利点がある。
The second aspect surface treatment step (II) is performed in (i) a period after the rubber molded body production step and before the finishing step, and / or (ii) after the finishing step and before the inspection step. . When the surface treatment process (II) is performed in the period after the finishing process (ii) and before the inspection process, the cleaning process and the drying process are usually performed after the surface treatment process (II) and before the inspection process. Is called. In this case, the cleaning step is a step of immersing the vulcanized rubber molded body in warm water having a temperature exceeding 40 ° C. and not higher than 100 ° C., and the cleaning step will be described in detail later. Since the second step of the step (II) can be applied, there is an advantage that the manufacturing process of the rubber product can be simplified.
表面処理工程(II)は、温度が40℃以下の処理液を加硫ゴム成形体の表面に付す第1工程と、第1工程を経て加硫ゴム成形体の表面に付着した処理液の加熱および洗浄を行う第2工程とを含む。 The surface treatment step (II) includes a first step of applying a treatment liquid having a temperature of 40 ° C. or less to the surface of the vulcanized rubber molded body, and heating of the treatment liquid attached to the surface of the vulcanized rubber molded body through the first step. And a second step of performing cleaning.
第1工程
この工程は、加硫ゴム成形体の表面に処理液を付着させる工程である。
ゴム成形体の表面に温度が40℃以下の処理液を付す(接触させる)方法は特に限定されないが、ゴム成形体を処理液中に浸漬する方法、ゴム成形体に処理液をスプレー塗布する方法、ゴム成形体に処理液をはけ塗りする方法、ゴム成形体に処理液をかけ流す方法等が挙げられるが、作業が簡易で、短時間で効果が得られ、しかも、多数個のゴム成形体を一括して均一に処理ができるという観点から、浸漬処理が好ましい。なお、処理液の温度は、1℃以上、40℃以下が好ましく、より好ましくは20℃以上、40℃以下であり、特に好ましくは、20℃以上、30℃以下である。1℃未満であると、ジクロロシアヌル酸塩の水系溶媒への溶解性が低下する傾向および処理液の凝固が生じる虞がある。
1st process This process is a process of making a process liquid adhere to the surface of a vulcanized rubber molding.
The method of attaching (contacting) the treatment liquid having a temperature of 40 ° C. or less to the surface of the rubber molded body is not particularly limited, but the method of immersing the rubber molded body in the treatment liquid or the method of spray-coating the treatment liquid on the rubber molded body There are a method of brushing the treatment liquid on the rubber molded body, a method of pouring the treatment liquid on the rubber molded body, etc., but the work is simple, the effect can be obtained in a short time, and many rubber moldings Immersion treatment is preferred from the viewpoint that the body can be uniformly treated at once. In addition, the temperature of the treatment liquid is preferably 1 ° C. or higher and 40 ° C. or lower, more preferably 20 ° C. or higher and 40 ° C. or lower, and particularly preferably 20 ° C. or higher and 30 ° C. or lower. If it is lower than 1 ° C., the solubility of dichlorocyanurate in an aqueous solvent tends to decrease and the coagulation of the treatment liquid may occur.
浸漬処理の場合、浸漬時間は、1秒〜10分程度が好ましく、より好ましくは5分〜10分程度である、10分を超えると、表面処理がそれ以上に進行し難く、また、1秒未満では、表面に処理液が十分に付着せず、十分な効果が得られにくくなる傾向となる。 In the case of the immersion treatment, the immersion time is preferably about 1 second to 10 minutes, more preferably about 5 minutes to 10 minutes. If it exceeds 10 minutes, the surface treatment hardly proceeds further, and 1 second. If it is less than 1, the treatment liquid does not adhere sufficiently to the surface, and it tends to be difficult to obtain a sufficient effect.
第2工程
この工程は、表面処理を実効させる工程であり、加硫ゴム成形体の表面に付着した処理液の加熱および洗浄を行う。なお、処理液の加熱温度は、40℃を超え、100℃以下が好適である。
該第2工程は具体的には以下の態様が挙げられる。
(A)表面に処理液が付着した加硫ゴム成形体を、温度が40℃を超え、100℃以下の温水に浸漬する態様。
(B)表面に処理液が付着した加硫ゴム成形体を、40℃を超え、100℃以下の温度に設定されたオーブンの中に入れて(通過させて)加熱した後、加硫ゴム成形体を温水にて洗浄する態様。
Second Step This step is a step for effecting the surface treatment, and heating and washing of the treatment liquid adhering to the surface of the vulcanized rubber molded body is performed. In addition, the heating temperature of a process liquid exceeds 40 degreeC and 100 degrees C or less is suitable.
Specific examples of the second step include the following aspects.
(A) A mode in which a vulcanized rubber molded body having a treatment liquid attached to the surface is immersed in warm water having a temperature exceeding 40 ° C and not more than 100 ° C.
(B) The vulcanized rubber molded body with the treatment liquid adhering to the surface is placed in an oven set to a temperature exceeding 40 ° C. and not higher than 100 ° C. (heating) and then heated, and then vulcanized rubber molding is performed. A mode in which the body is washed with warm water.
(A)の態様の場合、表面に処理液が付着した加硫ゴム成形体を、温度が40℃を超え、100℃以下の温水に浸漬することで、温水中で温水によって加硫ゴム成形体の表面に付着した処理液が加熱されて加硫ゴム成形体との反応が進行し、浸漬を継続することで、処理液が加硫ゴム成形体表面から洗い流される。温水の温度が40℃以下であると、処理液と加硫ゴム成形体との反応が十分に進行せず、十分な表面処理効果が得られない。また、温水の温度が100℃を超えると、温水の蒸発が激しくなり、実用性がなくなる。なお、処理液と加硫ゴム成形体との反応を十分に進行させるために、温水の温度は50℃〜70℃が好ましい。 In the case of the embodiment (A), the vulcanized rubber molded product with the treatment liquid adhering to the surface is immersed in warm water having a temperature exceeding 40 ° C. and not higher than 100 ° C., so that the vulcanized rubber molded product is heated with warm water in warm water. The treatment liquid adhering to the surface is heated to react with the vulcanized rubber molded body, and the treatment liquid is washed away from the surface of the vulcanized rubber molded body by continuing the immersion. When the temperature of the hot water is 40 ° C. or lower, the reaction between the treatment liquid and the vulcanized rubber molded article does not proceed sufficiently, and a sufficient surface treatment effect cannot be obtained. On the other hand, when the temperature of the hot water exceeds 100 ° C., the evaporation of the hot water becomes intense and the practicality is lost. In addition, in order to fully advance reaction with a process liquid and a vulcanized rubber molded object, the temperature of warm water has preferable 50 to 70 degreeC.
浸漬時間は、1秒〜10分程度が好ましく、より好ましくは2分〜8分程度、特に好ましくは5〜7分程度である。1秒未満であると、表面処理効果が得難くなる傾向にあり、10分を超えると、それ以上の効果が得難くなる傾向となる。 The immersion time is preferably about 1 second to 10 minutes, more preferably about 2 minutes to 8 minutes, and particularly preferably about 5 to 7 minutes. If it is less than 1 second, the surface treatment effect tends to be difficult to obtain, and if it exceeds 10 minutes, it is difficult to obtain a further effect.
ここで、温水は、例えば、水道水、工業用のイオン交換水等を加熱したものであり、特に限定されないが、不純物による悪影響を受けにくいため、工業用のイオン交換水が好ましい。 Here, the hot water is, for example, heated tap water, industrial ion-exchanged water, and the like, and is not particularly limited, but industrial ion-exchanged water is preferable because it is not easily affected by impurities.
(B)の態様の場合、表面に処理液が付着した加硫ゴム成形体を、40℃を超え、100℃以下の温度に設定されたオーブン中に入れることで、加硫ゴム成形体の表面に付着した処理液が加熱されて加硫ゴム成形体との反応が進行する。オーブン中の温度は、50℃〜70℃が好ましい。また、オーブン中での加熱時間は、特に限定されないが、1秒〜30分程度が好ましく、10秒〜10分程度がより好ましい。 In the case of the mode (B), the surface of the vulcanized rubber molded body is obtained by placing the vulcanized rubber molded body with the treatment liquid attached to the surface in an oven set to a temperature of 40 ° C. or higher and 100 ° C. or lower. The treatment liquid adhering to is heated and the reaction with the vulcanized rubber molded body proceeds. As for the temperature in oven, 50 to 70 degreeC is preferable. The heating time in the oven is not particularly limited, but is preferably about 1 second to 30 minutes, and more preferably about 10 seconds to 10 minutes.
オーブン中での加熱後に行われる温水による洗浄では、温水をゴム成形体表面に吹き付けたり、流しかけたりするか、或いは、温水にゴム成形体を浸漬する。温水の温度は特に限定はされないが、40℃を超え、100℃以下が好ましく、50℃〜70℃がより好ましい。温水に浸漬する場合、浸漬時間は、1秒〜3分程度が好ましく、30秒〜1分が特に好ましい。 In the washing with warm water performed after heating in the oven, warm water is sprayed or poured on the surface of the rubber molded body, or the rubber molded body is immersed in warm water. Although the temperature of warm water is not specifically limited, it exceeds 40 degreeC, 100 degrees C or less is preferable, and 50 to 70 degreeC is more preferable. When immersed in warm water, the immersion time is preferably about 1 second to 3 minutes, particularly preferably 30 seconds to 1 minute.
表面処理工程(II)において、第2工程の後は、加硫ゴム成形体を室温(1〜30℃)で自然乾燥させる。 In the surface treatment step (II), after the second step, the vulcanized rubber molded body is naturally dried at room temperature (1 to 30 ° C.).
本発明の処理液は、加硫成形された加硫ゴム成形体に対して優れた防着性付与効果を示し、また、加硫ゴム成形体の表面に低摩擦性を付与する効果も有する。従って、(i)ゴム成形体作製工程後(すなわち、加硫成形工程後)、仕上げ工程前の期間、及び/または、(ii)仕上げ工程後、検査工程前の期間に、表面処理工程が行われることで、加硫ゴム成形体の表面に防着性が付与されるため、検査工程および包装工程等でのゴム製品(加硫ゴム成形体)同士の付着が防止され、検査工程および包装工程等におけるゴム製品(加硫ゴム成形体)の取り扱い性が向上し、その結果、ゴム製品の製造効率を向上させることができる。 The treatment liquid of the present invention exhibits an excellent anti-adhesive property imparting effect to a vulcanized rubber molded product, and also has an effect of imparting low friction to the surface of the vulcanized rubber molded product. Therefore, (i) the surface treatment process is performed after the rubber molding production process (that is, after the vulcanization molding process) and before the finishing process, and / or (ii) after the finishing process and before the inspection process. As a result, adhesion of rubber products (vulcanized rubber moldings) in the inspection process and the packaging process is prevented, and the inspection process and the packaging process. As a result, the handleability of rubber products (vulcanized rubber moldings) can be improved, and as a result, the production efficiency of rubber products can be improved.
また、特にゴム製品が析出(ブルーム、ブリード等)が生じやすい成分を含むゴム組成物から製造されるゴム製品である場合、ゴム成形体作製工程(すなわち、加硫成形工程)直後の析出が生じていない加硫ゴム成形体に対して表面処理工程が行われることで、その後の析出、すなわち、仕上げ工程、検査工程および包装工程等や、包装工程後の保管や輸送中における析出を抑制できる効果がある。従って、ゴム成形体からの添加剤成分の析出(ブルーム、ブリード等)が生じやすい配合組成のゴム組成物からゴム製品を製造する際に、本発明方法は有益である。ゴム成形体からの添加剤成分の析出(ブルーム、ブリード等)が生じやすい配合組成のゴム組成物の例としては、例えば、以下のゴム組成物Aが挙げられる。 In particular, when the rubber product is a rubber product manufactured from a rubber composition containing a component that is likely to cause precipitation (bloom, bleed, etc.), precipitation occurs immediately after the rubber molded body preparation step (ie, vulcanization molding step). The effect of suppressing the subsequent precipitation, that is, the finishing process, the inspection process, the packaging process, and the like during storage and transportation after the packaging process by performing the surface treatment process on the vulcanized rubber molded body that has not been There is. Therefore, the method of the present invention is useful in producing a rubber product from a rubber composition having a compounding composition in which additive components (bloom, bleed, etc.) are likely to precipitate from the rubber molded body. As an example of a rubber composition having a compounding composition in which precipitation (bloom, bleed, etc.) of the additive component from the rubber molded body is likely to occur, for example, the following rubber composition A is exemplified.
(ゴム組成物A)
NBR:100重量部
酸化亜鉛:1〜10重量部
ステアリン酸:1〜10重量部
充填剤(カーボン;SRFカーボン):20〜120重量部
可塑剤(DOP):1〜40重量部
架橋剤(硫黄):1〜10重量部
加硫促進剤:1〜10重量部
(Rubber composition A)
NBR: 100 parts by weight Zinc oxide: 1 to 10 parts by weight Stearic acid: 1 to 10 parts by weight Filler (carbon; SRF carbon): 20 to 120 parts by weight Plasticizer (DOP): 1 to 40 parts by weight Crosslinking agent (sulfur) ): 1 to 10 parts by weight Vulcanization accelerator: 1 to 10 parts by weight
また、処理液はゴム成形体の物理的性質の低下をまねくことなく、ゴム成形体表面に低摩擦性を付与するため、特にニトリルゴム(NBR)のような金属面に対する摩擦係数が高いゴムをベース成分とするゴム組成物からシール材(ゴムシール)を製造する態様では、シール材(ゴムシール)の伸張性を低下させることなく、金属面に対して優れた低摩擦性を有するシール材(ゴムシール)を効率良く製造することができる。従って、本発明方法は、特に摺動部用シール材(ゴムシール)の製造方法として好適である。 In addition, since the treatment liquid imparts low friction to the surface of the rubber molded body without deteriorating the physical properties of the rubber molded body, a rubber having a high friction coefficient against a metal surface such as nitrile rubber (NBR) is used. In an embodiment in which a sealing material (rubber seal) is produced from a rubber composition as a base component, a sealing material (rubber seal) having excellent low friction against a metal surface without reducing the extensibility of the sealing material (rubber seal). Can be manufactured efficiently. Therefore, the method of the present invention is particularly suitable as a method for producing a sliding part sealing material (rubber seal).
なお、本発明方法は、各種産業分野における種々のゴム製品の製造に適用でき、例えば、自動車用ウエザーストリップ;自動車用ホース(例えばブレーキホース、ラジエターホース、ヒーターホース、エアークリーナーホース等);送水用ホース;ガス用ホース;建材のシール材(例えば、ガスケット、エアータイト、目地材、戸当たり部等);自動車用シールのシール材(例えば、Oリング、RL(ラジアルリップ)、シールリング等);建設機械・油圧機器用シールのシール材(例えば、Oリング、キャップシール用Oリング、Uパッキン、回転軸シール、ウエアリング、Dリング、RLシール等);空気圧機器用シールのシール材(例えば、ピストン用パッキン、ロッド用パッキン、Xリング等);真空・半導体装置用シールのシール材;産業機器用シールのシール材(キャップシール用リング等)等のゴム製品の製造に有用である。 The method of the present invention can be applied to the production of various rubber products in various industrial fields. For example, automotive weather strips; automotive hoses (for example, brake hoses, radiator hoses, heater hoses, air cleaner hoses, etc.); Hose; gas hose; sealing material for building materials (for example, gasket, air tight, joint material, door stopper, etc.); sealing material for automotive seal (for example, O-ring, RL (radial lip), seal ring, etc.); Seals for construction machinery and hydraulic equipment seals (for example, O-rings, O-rings for cap seals, U-packings, rotary shaft seals, wear rings, D-rings, RL seals, etc.); (Piston packing, rod packing, X ring, etc.); Vacuum / semiconductor device seal ; Industrial instrument seal of the sealing member (cap seal ring and the like) are useful in the manufacture of rubber products, such as.
以下、実施例及び比較例を示して本発明をより具体的に説明するが、本発明は以下の実施例によって何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited at all by the following examples.
実施例1〜3
(処理液の調製)
ジクロロイソシアヌル酸ナトリウムを溶解量(濃度)が、2重量%、5重量%、10重量%である水溶液からなる3種の処理液を調製した。
Examples 1-3
(Preparation of treatment solution)
Three types of treatment liquids were prepared which consisted of aqueous solutions having a dissolution amount (concentration) of sodium dichloroisocyanurate of 2% by weight, 5% by weight and 10% by weight.
(試料)
ゴム成分がNBRからなるシート状に加硫成形した成形体を50mm(縦)×20mm(横)×2mm(厚さ)に加工し、作製した。
(sample)
A molded body obtained by vulcanizing and molding the rubber component into a sheet made of NBR was processed to a size of 50 mm (length) × 20 mm (width) × 2 mm (thickness).
(処理方法)
処理方法1:25℃に加温した処理液中に上記の試験片を所定時間(1分、5分、10分)浸漬後、洗浄、乾燥処理して、表面改質を行った。
(Processing method)
Treatment method 1: The test piece was immersed in a treatment solution heated to 25 ° C. for a predetermined time (1 minute, 5 minutes, 10 minutes), then washed and dried to perform surface modification.
処理方法2:60℃に加温した処理液中に上記の試験片を所定時間(1分、5分、10分)浸漬後、洗浄、乾燥処理して、表面改質を行った。 Treatment method 2: The test piece was immersed in a treatment solution heated to 60 ° C. for a predetermined time (1 minute, 5 minutes, 10 minutes), then washed and dried to perform surface modification.
比較例1
酢酸エチル(EA)にトリクロロイソシアヌル酸を溶解させたトリクロロイソシアヌル酸の溶解量(濃度)が2重量%の処理液を調製した以外は、実施例と同様にして表面改質を行った。
Comparative Example 1
Surface modification was carried out in the same manner as in Example except that a treatment liquid having a dissolution amount (concentration) of trichloroisocyanuric acid in which trichloroisocyanuric acid was dissolved in ethyl acetate (EA) was 2% by weight was prepared.
以上の実施例1〜4、比較例1のゴム部材(試料)に対して下記の評価試験を実施した。 The following evaluation tests were performed on the rubber members (samples) of Examples 1 to 4 and Comparative Example 1 described above.
[評価試験]
(1)摩擦試験(静摩擦係数及び動摩擦係数の測定)
JIS−K7125を参考にHEIDON社製の表面性測定器を用いた。水平な試験テーブル上で試験片(任意サイズ)にボール圧子(SUS304)を接点に100gの荷重をかけ、75mm/minで試験片を水平に動かした際のボール圧子と試験片間の摩擦係数を測定した。
[Evaluation test]
(1) Friction test (measurement of static friction coefficient and dynamic friction coefficient)
A surface property measuring instrument manufactured by HEIDON was used with reference to JIS-K7125. Apply the ball indenter (SUS304) to the test piece (arbitrary size) on the horizontal test table and apply a load of 100g to the contact point. It was measured.
(2)防着性試験
試験片の処理表面同士を接触させて上からlkg程度の荷重を5分程度かけ、荷重を取り除いた際に、試験片同士が付着しており、多少の振動を与えたり振ったりしても全く分離しない場合を不可(×)、付着はしているが、軽く振動を与えたり振ったりすれば分離する場合を可(△)、付着していない場合を良好(○)とした。
(2) Anti-adhesion test When the treated surfaces of the test pieces are brought into contact with each other, a load of about 1 kg is applied for about 5 minutes from the top, and when the load is removed, the test pieces adhere to each other and give some vibration. If it does not separate at all even if it shakes or shakes, it is impossible (×), but it adheres, but if it is lightly shaken or shaken, it can be separated (△), and it does not adhere (○ ).
(3)伸張性試験
試験片を100%〜150%程度伸張させ、その表面を目視で観察して亀裂が認められるものを不可(×)、目視では亀裂は全く認められないが、その表面をマイクロスコープ(200倍)で観察した場合に認められるものを可(△)、200倍でも亀裂が認められないものを良好(○)とした。
(3) Stretchability test The test piece is stretched by about 100% to 150%, and the surface is visually observed to make cracks impossible (×). What was observed when observed with a microscope (200 times) was acceptable (Δ), and what was not observed even at 200 times was judged good (◯).
下記表1〜3が試験結果である。 The following Tables 1-3 are test results.
実施例4
ゴム材料であるニトリルゴム100重量部、架橋剤としての硫黄0.5重量部、充填剤としてのカーボンブラック60重量部、架橋促進剤(TT:テトラメチルチウラムジサルファイド)1.5重量部、加工助剤(ステアリン酸)1重量部、可塑剤(DOP)5重量部をバンバリーミキサーに投入し、その後シート状に加硫成形した成形体から、50mm(縦)×20mm(横)×2mm(厚さ)の試験片を作製した。この試験片をジクロロイソシアヌル酸ナトリウムの溶解量(濃度)が2重量%の水溶液からなる25℃の処理液に10分間浸漬した。浸漬後、槽から取り出し、60℃のイオン交換水中に60秒浸漬(洗浄)後、取り出し、自然乾燥させ、乾燥後、前記の評価試験を行った。
Example 4
100 parts by weight of nitrile rubber as a rubber material, 0.5 parts by weight of sulfur as a crosslinking agent, 60 parts by weight of carbon black as a filler, 1.5 parts by weight of a crosslinking accelerator (TT: tetramethylthiuram disulfide), processing 1 part by weight of auxiliary agent (stearic acid) and 5 parts by weight of plasticizer (DOP) were put into a Banbury mixer, and then vulcanized and formed into a sheet shape, 50 mm (length) x 20 mm (width) x 2 mm (thickness) A) test piece was prepared. This test piece was immersed for 10 minutes in a treatment liquid at 25 ° C. composed of an aqueous solution having a dissolution amount (concentration) of sodium dichloroisocyanurate of 2% by weight. After immersion, the sample was taken out from the tank, immersed (washed) in 60 ° C. ion-exchanged water for 60 seconds, taken out, dried naturally, and dried, and then subjected to the evaluation test.
実施例5
処理液の温度を60℃にして、60℃の処理液に5分間浸漬した以外は、実施例4と同じとした。
Example 5
The temperature of the treatment liquid was set to 60 ° C., and the same as Example 4 except that the treatment liquid was immersed in the treatment liquid at 60 ° C. for 5 minutes.
実施例6
ジクロロイソシアヌル酸ナトリウムの溶解量(濃度)が10重量%の水溶液からなる60℃の処理液に5分間浸漬した以外は、実施例4と同じとした。
Example 6
The same procedure as in Example 4 was performed except that the solution (concentration) of sodium dichloroisocyanurate was immersed in a treatment solution at 60 ° C. composed of an aqueous solution of 10% by weight for 5 minutes.
比較例2
処理液を、酢酸エチル(EA)にトリクロロイソシアヌル酸を溶解させたトリクロロイソシアヌル酸の溶解量(濃度)が2重量%の処理液に変更した以外は、実施例4と同様にした。
Comparative Example 2
The processing solution was the same as Example 4 except that the amount (concentration) of trichloroisocyanuric acid obtained by dissolving trichloroisocyanuric acid in ethyl acetate (EA) was changed to 2% by weight.
比較例3
表面処理を行わない以外は、実施例4と同じ試料片を使った。
Comparative Example 3
The same specimen as in Example 4 was used except that the surface treatment was not performed.
下記表4に実施例4〜6および比較例2、3の試験結果を示す。 Table 4 below shows the test results of Examples 4 to 6 and Comparative Examples 2 and 3.
上記の表4の結果から、ジクロロイソシアヌル酸塩が水系溶媒に溶解した溶液からなる処理液であれば、加硫ゴム成形体に対して、伸張性を低下させることなく、低摩擦性および防着性を付与できることが分かる。従って、加硫ゴム成形体を作製するゴム成形体作製工程後に、ジクロロイソシアヌル酸塩が水系溶媒に溶解した溶液からなる処理液で加硫ゴム成形体の表面を処理することで、ゴム成形体同士の付着防止を図ることができ、所期の物理的性質(物理的特性)を備えたゴム製品を効率良く製造できることが明らかになった。 From the results of Table 4 above, if the treatment liquid is a solution in which dichloroisocyanurate is dissolved in an aqueous solvent, the low rub resistance and adhesion can be prevented without reducing the extensibility of the vulcanized rubber molded article. It can be seen that sex can be imparted. Therefore, after the rubber molded body production step for producing the vulcanized rubber molded body, the surface of the vulcanized rubber molded body is treated with a treatment liquid composed of a solution in which dichloroisocyanurate is dissolved in an aqueous solvent. It has been clarified that the rubber product having the desired physical properties (physical properties) can be efficiently produced.
実施例7
ゴム材料であるニトリルゴム100重量部、架橋剤としての硫黄0.5重量部、充填剤としてのカーボンブラック60重量部、架橋促進剤(TT:テトラメチルチウラムジサルファイド)1.5重量部、加工助剤(ステアリン酸)1重量部、可塑剤(DOP)5重量部をバンバリーミキサーに投入し、その後シート状に加硫成形した成形体から、50mm(縦)×20mm(横)×2mm(厚さ)の試験片を作製した。この試験片をジクロロイソシアヌル酸ナトリウムの溶解量(濃度)が2重量%の水溶液からなる25℃の処理液を収容した洗浄槽の処理液に10分間浸漬した。浸漬後、試験片を槽から取り出し、60℃のイオン交換水中に60秒浸漬(洗浄)後、取り出し、自然乾燥させ、乾燥後、前記の評価試験を行った。
Example 7
100 parts by weight of nitrile rubber as a rubber material, 0.5 parts by weight of sulfur as a crosslinking agent, 60 parts by weight of carbon black as a filler, 1.5 parts by weight of a crosslinking accelerator (TT: tetramethylthiuram disulfide), processing 1 part by weight of auxiliary agent (stearic acid) and 5 parts by weight of plasticizer (DOP) were put into a Banbury mixer, and then vulcanized and formed into a sheet shape, 50 mm (length) x 20 mm (width) x 2 mm (thickness) A) test piece was prepared. This test piece was immersed for 10 minutes in the treatment liquid of the washing tank which accommodated the 25 degreeC treatment liquid which consists of aqueous solution whose dissolution amount (concentration) of sodium dichloroisocyanurate is 2 weight%. After the immersion, the test piece was taken out from the tank, immersed in 60 ° C. ion exchange water for 60 seconds (washed), taken out, naturally dried, and dried, and then the evaluation test was performed.
実施例8
処理液の温度を30℃にし、30℃の処理液に試験片を5分間浸漬し、処理液の槽から取り出し、試験片を75℃のイオン交換水中に2分間浸漬させた以外は、実施例7と同じとした。
Example 8
Example except that the temperature of the treatment liquid was set to 30 ° C., the test piece was immersed in the treatment liquid at 30 ° C. for 5 minutes, taken out from the bath of the treatment liquid, and the test piece was immersed in ion exchange water at 75 ° C. for 2 minutes. Same as 7.
実施例9
ジクロロイソシアヌル酸ナトリウムの溶解量(濃度)が10重量%の水溶液からなる35℃の処理液に試験片を1分間浸漬し、処理液の槽から取り出し、試験片を65℃のイオン交換水中に8分間浸漬させた以外は、実施例7と同じとした。
Example 9
The test piece is immersed in a treatment liquid at 35 ° C. made of an aqueous solution having a dissolution amount (concentration) of sodium dichloroisocyanurate of 10% by weight for 1 minute, taken out from the tank of the treatment liquid, and the test piece is placed in ion exchange water at 65 ° C. for 8 minutes. The same as Example 7 except that it was immersed for a minute.
比較例4
処理液を、酢酸エチル(EA)にトリクロロイソシアヌル酸を溶解させたトリクロロイソシアヌル酸の溶解量(濃度)が2重量%の処理液に変更した以外は、実施例7と同様にした。
Comparative Example 4
The treatment solution was the same as that of Example 7 except that the treatment amount of the trichloroisocyanuric acid in which trichloroisocyanuric acid was dissolved in ethyl acetate (EA) was changed to 2% by weight.
比較例5
表面処理を行わない以外は、実施例7と同じ試料片を使った。
Comparative Example 5
The same specimen as in Example 7 was used except that the surface treatment was not performed.
下記表5に実施例7〜9および比較例4、5の試験結果を示す。
上記の表4、5の結果から、ジクロロイソシアヌル酸塩が水系溶媒に溶解した溶液からなる処理液により、加硫ゴム成形体であるゴムシールに対して、伸張性を低下させることなく、低摩擦性および防着性を付与できることが分かる。従って、加硫ゴム成形体を作製するゴム成形体作製工程後に、かかる処理液で加硫ゴム成形体の表面を処理する工程を行うことで、ゴム成形体同士の付着防止を図ることができ、所期の物理的性質(物理的特性)を備えたゴム製品を効率良く製造できることが明らかになった。 From the results of Tables 4 and 5 above, the treatment liquid composed of a solution in which dichloroisocyanurate is dissolved in an aqueous solvent is used to reduce the friction property without reducing the extensibility of the rubber seal as a vulcanized rubber molded body. It can also be seen that adhesion can be imparted. Therefore, after the rubber molded body production step for producing the vulcanized rubber molded body, by performing the process of treating the surface of the vulcanized rubber molded body with such a treatment liquid, it is possible to prevent adhesion between the rubber molded bodies, It became clear that rubber products with the desired physical properties (physical properties) can be produced efficiently.
本出願は日本で出願された特願2014−066908、特願2014−220218及び特願2015−003218を基礎としており、その内容は本明細書に全て包含される。 This application is based on patent application Nos. 2014-066908, 2014-220218, and 2015-003218 filed in Japan, the contents of which are incorporated in full herein.
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Citations (6)
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JPS5663432A (en) * | 1979-10-31 | 1981-05-30 | Zeon Kosan Kk | Treatment for surface of vulcanized rubber |
JPS60108438A (en) * | 1983-11-17 | 1985-06-13 | Toyoda Gosei Co Ltd | Method for treating surface of vulcanized rubber |
JPH09507690A (en) * | 1994-01-25 | 1997-08-05 | コモンウェルス・サイエンティフィック・アンド・インダストリアル・リサーチ・オーガナイゼーション | Surface treatment of rubber and rubber-based materials |
JP2007256709A (en) * | 2006-03-24 | 2007-10-04 | Tokai Rubber Ind Ltd | Roll for electrophotographic equipment and its manufacturing method |
JP2013132312A (en) * | 2011-12-26 | 2013-07-08 | Bridgestone Sports Co Ltd | Method of manufacturing golf ball, and golf ball |
JP2014090957A (en) * | 2012-11-06 | 2014-05-19 | Bridgestone Sports Co Ltd | Method for manufacturing golf ball and golf ball |
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- 2015-03-27 JP JP2016510521A patent/JP6495244B2/en active Active
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS5663432A (en) * | 1979-10-31 | 1981-05-30 | Zeon Kosan Kk | Treatment for surface of vulcanized rubber |
JPS60108438A (en) * | 1983-11-17 | 1985-06-13 | Toyoda Gosei Co Ltd | Method for treating surface of vulcanized rubber |
JPH09507690A (en) * | 1994-01-25 | 1997-08-05 | コモンウェルス・サイエンティフィック・アンド・インダストリアル・リサーチ・オーガナイゼーション | Surface treatment of rubber and rubber-based materials |
JP2007256709A (en) * | 2006-03-24 | 2007-10-04 | Tokai Rubber Ind Ltd | Roll for electrophotographic equipment and its manufacturing method |
JP2013132312A (en) * | 2011-12-26 | 2013-07-08 | Bridgestone Sports Co Ltd | Method of manufacturing golf ball, and golf ball |
JP2014090957A (en) * | 2012-11-06 | 2014-05-19 | Bridgestone Sports Co Ltd | Method for manufacturing golf ball and golf ball |
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