JP2005239973A - Fluorinated fullerene-containing rubber composition and molded product therefrom - Google Patents
Fluorinated fullerene-containing rubber composition and molded product therefrom Download PDFInfo
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Abstract
Description
本発明は、離型性に適したゴム組成物に関し、特に自動成形やライン生産の合理化に適した離型性フッ素化フラーレンゴム組成物及びそれを用いた成形体に関する。 The present invention relates to a rubber composition suitable for releasability, and particularly to a releasable fluorinated fullerene rubber composition suitable for automatic molding and rationalization of line production and a molded body using the same.
離型性に優れたシリコーンゴム成形物を反転母型として、複製品を製造することは公知のことであり、このようにして作られたエポキシ樹脂、ウレタン樹脂などの注型樹脂成形品は自動車部品、電気電子部品、プラモデル、工芸品などとして実用的に供給されている。最近、このようにして得られた注型樹脂成形品の難燃性や耐熱性等の特性が重要視されるようになってきており、このためにエポキシ樹脂やウレタン樹脂などには、種々の添加剤が配合されるようになっている。その結果、従来のシリコーンゴム母型では離型耐久性が損なわれ、１つの母型から作成できる複製品の個数が著しく少なくなってきた。 It is well known to produce a replica using a silicone rubber molding with excellent releasability as an inversion matrix, and cast resin moldings such as epoxy resins and urethane resins made in this way are automobiles. It is practically supplied as parts, electrical and electronic parts, plastic models, and crafts. Recently, the properties such as flame retardancy and heat resistance of cast resin moldings obtained in this way have come to be regarded as important. For this reason, epoxy resins and urethane resins have various properties. Additives are added. As a result, the mold release durability is impaired in the conventional silicone rubber matrix, and the number of replicas that can be made from one matrix is remarkably reduced.
注型樹脂に対するシリコーンゴム母型の離型耐久性を向上するための技術としては、特許文献１に、離型耐久性を向上させるために型取り用オルガノポリシロキサン組成物が提案されている。しかし、この技術においては、１００回程度のウレタン型取り回数が得られたとされているが、まだ十分に満足できるものではなかった。 As a technique for improving the mold release durability of the silicone rubber matrix for the casting resin, Patent Document 1 proposes an organopolysiloxane composition for mold making in order to improve the mold release durability. However, in this technique, it is said that the number of times of urethane mold taking about 100 times was obtained, but it was not yet satisfactory.
特に、導電性樹脂などを充填し転写ができる凹部を有する母型（例えば半導体製造装置）、剥離させるなどで転写ができる凸部を有する母型（例えばスタンプ）においては、限界があり満足できるものではなかった。 In particular, there are limitations on the mother mold (for example, a semiconductor manufacturing apparatus) having a concave portion that can be filled with conductive resin and transferred, and the mother mold (for example, a stamp) having a convex portion that can be transferred by peeling, etc. It wasn't.
一方、一般的に、各種ゴムは、金型等の金属に付着しやすく、成形時の金型からの離型性が悪い。そこで、（１）ワックス等の加工助剤をゴム内に配合したり、（２）様々な離型剤を成形型に塗布したり、（３）フッ素系ガスを成形型に吹き付けたりなどをして成形されている。 On the other hand, in general, various rubbers are likely to adhere to a metal such as a mold, and the releasability from the mold during molding is poor. Therefore, (1) compounding processing aids such as wax in the rubber, (2) applying various mold release agents to the mold, (3) spraying fluorine gas on the mold, etc. Are molded.
しかし、（１）加工助剤の配合量を多くすればゴムの物性を悪化させたり、加工助剤が金型に付着して熱劣化を起し不良品を発生させたりする問題と、（２）離型剤を金型に塗布すれば、一工程増えて製造コストが高くなる問題と、（３）フッ素ガスを吹き付ける方法では、フッ素系ガスをそのまま大気中に放出するわけには行かず、その処理装置を必要とする問題とがある。 However, (1) If the amount of the processing aid is increased, the physical properties of the rubber are deteriorated, or the processing aid adheres to the mold and causes thermal deterioration to generate defective products. ) If the mold release agent is applied to the mold, the production cost increases by one step. (3) The method of spraying fluorine gas does not release the fluorine-based gas into the atmosphere as it is. There is a problem that requires the processing device.
特に、フッ素系ゴムの成形体は、耐熱性、対油性、耐薬品性等に優れ、自動車部品、石油掘削製品、工業用材料を中心に高い信頼性を要求される分野で好適に用いられているが、他のゴム成形物と比較して高価であること、ゴム成形時の金型からの離型性が劣ること、母型として用いた場合の樹脂成形体に対する離型性に劣るため使用される分野は限定されてきた。 In particular, the molded products of fluoro-based rubber are excellent in heat resistance, oil resistance, chemical resistance, etc., and are suitably used in fields that require high reliability, especially in automotive parts, oil drilling products, and industrial materials. However, it is expensive compared to other rubber moldings, inferior in releasability from the mold during rubber molding, and inferior in releasability to resin molding when used as a mother mold Fields that have been limited have been limited.
フッ素ゴムの優れた特性を保持しながら離型性を向上させる技術としては、特許文献２、フッ素オイルを配合する方法が提案されている。
コストを低下する手段としては、アクリルゴム、水添ＮＢＲ、エビクロルドリン等とのブレンドした組成物が検討されている。特許文献３、特許文献４には、アクリルゴムとブレンドして得たフッ素ゴム組成物が提案されているが、フッ素ゴム組成物の成形時の金型からの離型性およびフッ素ゴム母型からの樹脂成形体の離型性は必ずしも十分でなかった。
As a technique for improving the releasability while maintaining the excellent characteristics of fluororubber, Patent Document 2 and a method of blending fluoro oil have been proposed.
As a means for reducing the cost, a composition blended with acrylic rubber, hydrogenated NBR, shrimp chlordrin and the like has been studied. Patent Document 3 and Patent Document 4 propose a fluororubber composition obtained by blending with acrylic rubber. From the mold release property of the fluororubber composition and the fluororubber matrix. The releasability of this resin molding was not always sufficient.
本発明は、ゴムを成形する場合の金型からの離型性と、母型として用いる場合の成形材料との離型耐久性が従来よりもはるかに高く、且つ転写性の良いゴム組成物の提供を目的とする。 The present invention relates to a rubber composition having a mold release property from a mold when molding rubber and a mold release durability from a molding material when used as a mother mold, which is much higher than conventional and has good transferability. For the purpose of provision.
本発明の第一は、フッ素化フラーレンをゴム内に配合してなることを特徴とするゴム組成物に関するものである。
フッ素化フラーレンは、液状のゴム組成物内に配合しても良い。
また、ゴムの加硫、成形において必要な２価金属酸化物、２価金属水酸化物、カーボンブラック、各種フィラー、顔料、硬化剤、硬化遅延剤などを含有しても良いし、適当な離型性及び／又は硬度にさせるために主ゴムと異なるゴムの配合、オイルの配合などの割合を調整しても良い。
The first of the present invention relates to a rubber composition comprising fluorinated fullerene blended in rubber.
The fluorinated fullerene may be blended in the liquid rubber composition.
It may also contain divalent metal oxides, divalent metal hydroxides, carbon black, various fillers, pigments, curing agents, curing retarders, etc. necessary for rubber vulcanization and molding. In order to achieve moldability and / or hardness, the proportion of the rubber different from the main rubber, the proportion of oil, etc. may be adjusted.
本発明の第二は、上記ゴム組成物を硬化、成形してなる成形体に関するものである。
特に、フッ素化フラーレンを、離型性などに優れているシリコーン系ゴムとの配合又は各種特性に優れているフッ素系ゴムとの配合をすることで得られるフッ素化フラーレン含有ゴム組成物を用いて硬化、成形してなる成形体に関するものである。
The second of the present invention relates to a molded product obtained by curing and molding the rubber composition.
In particular, by using a fluorinated fullerene-containing rubber composition obtained by blending fluorinated fullerene with a silicone rubber excellent in releasability or the like or a fluorine rubber excellent in various properties. The present invention relates to a molded product obtained by curing and molding.
本発明の請求項１によれば、フッ素化フラーレンを配合したゴム組成物であり、ゴムを成形する場合、母型（例えば金型、樹脂型）からの離型性が従来ゴムよりもはるかに優れたゴム組成物を提供することが可能となる。 According to claim 1 of the present invention, it is a rubber composition containing a fluorinated fullerene, and when molding rubber, the releasability from the mother mold (for example, mold, resin mold) is much higher than that of conventional rubber. It is possible to provide an excellent rubber composition.
本発明の請求項２によれば、フッ素化フラーレンの配合割合を変えたゴム組成物であり、ゴムの種類及び用途、成形方法に応じ、配合割合を変えることで適当な離型性及び特性（例えば成形性）を有するゴム組成物を提供することが可能となる。 According to claim 2 of the present invention, it is a rubber composition in which the blending ratio of the fluorinated fullerene is changed. By changing the blending ratio according to the type and application of the rubber and the molding method, appropriate release properties and characteristics ( For example, it is possible to provide a rubber composition having moldability.
本発明の請求項３によれば、液状のゴム組成物であり、離型性に優れ、微細な形状を形成するゴム組成物を提供することが可能となる。 According to claim 3 of the present invention, it is possible to provide a rubber composition which is a liquid rubber composition, has excellent releasability and forms a fine shape.
本発明の請求項４によれば、液状のシリコーン系ゴム組成物であり、離型性に優れ、微細な形状を形成でき、弾力性、耐熱性などを有するゴム組成物を提供することが可能となる。 According to claim 4 of the present invention, it is possible to provide a rubber composition which is a liquid silicone rubber composition, has excellent releasability, can form a fine shape, has elasticity, heat resistance and the like. It becomes.
本発明の請求項５によれば、液状のフッ素系ゴム組成物であり、離型性に優れ、微細な形状を形成でき、耐油性、耐炎性、耐引き裂き性などを有するゴム組成物を提供することが可能となる。 According to claim 5 of the present invention, there is provided a rubber composition which is a liquid fluorine-based rubber composition, has excellent releasability, can form a fine shape, and has oil resistance, flame resistance, tear resistance and the like. It becomes possible to do.
本発明の請求項６によれば、真空容器を用いたプラズマ法で生成したフッ素化フラーレンを配合したゴム組成物であり、大気中に有害フッ素ガスの放出を防止することができる製法で生成したものを用いて、離型性の優れたゴム組成物を提供することが可能となる。 According to claim 6 of the present invention, it is a rubber composition containing a fluorinated fullerene produced by a plasma method using a vacuum vessel, and produced by a production method capable of preventing the release of harmful fluorine gas into the atmosphere. It becomes possible to provide a rubber composition having excellent mold release properties.
本発明の請求項７によれば、フラーレンはＣ６０であり、離型性に優れ、ゴムへの分散性に優れたゴム組成物を提供することが可能となる。 According to claim 7 of the present invention, the fullerene is C 60, excellent releasability, it is possible to provide an excellent rubber composition dispersibility in rubber.
本発明の請求項８によれば、フラーレンはＣ７０であり、Ｃ６０でよりも少ない配合割合でも、離型性に優れたゴム組成物を提供することができ、コスト低減をすることが可能となる。 According to claim 8 of the present invention, the fullerene is C 70, even with a small proportion than in C 60, it is possible to provide an excellent rubber composition in releasability, it can be a cost reduction It becomes.
本発明の請求項９によれば、前記ゴム組成物のいずれかを用いて硬化した成形体であり、離型耐久性に優れ、且つ転写性に優れたゴム製成形体を提供することが可能となる。 According to the ninth aspect of the present invention, it is possible to provide a rubber molded body which is a molded body cured using any of the rubber compositions, which has excellent mold release durability and excellent transferability. It becomes.
本発明の請求項１０によれば、前記ゴム組成物のいずれかを用いて硬化したゴム製母型であり、樹脂等を成形する場合、該樹脂等との離型耐久性に優れたゴム組成物を提供することが可能となる。すなわち、樹脂成形（例えば真空注型成形）における離型耐久性（例えば繰り返し成形する場合の成形樹脂に対する離型維持性）に優れた成形体（例えば型取り用ゴム製母型）を提供することが可能となる。 According to the tenth aspect of the present invention, the rubber composition is cured with any of the rubber compositions, and when molding a resin or the like, the rubber composition having excellent mold release durability with the resin or the like. Things can be provided. That is, to provide a molded body (for example, a mold made of rubber for molding) having excellent mold release durability (for example, mold release maintaining ability for molded resin in the case of repeated molding) in resin molding (for example, vacuum casting). Is possible.
本発明の請求項１１によれば、前記ゴム組成物のいずれかを用いて硬化した成形体が、凹及び／又は凸部を形成した転写ができる転写用母型であり、離型耐久性に優れた転写用成形体を提供することが可能となる。特に、液状のゴム組成物である請求項３〜５のいずれかを用いれば、離型耐久性に優れ、微細な形状を形成した転写用母型を提供することが可能となる。すなわち、例えば半導体などのnｍレベルの微細パターン形成やガラス基板を用いる蛍光表示装置の微細パターン形成などに有用である。 According to the eleventh aspect of the present invention, the molded body cured by using any of the rubber compositions is a transfer mother mold capable of transferring a concave and / or convex portion, and is excellent in mold release durability. It becomes possible to provide an excellent molded article for transfer. In particular, if any one of claims 3 to 5 which is a liquid rubber composition is used, it is possible to provide a transfer master having excellent mold release durability and a fine shape. That is, for example, it is useful for forming a fine pattern of an nm level such as a semiconductor or a fine pattern of a fluorescent display device using a glass substrate.
本発明の請求項１２によれば、前記ゴム組成物のいずれかを用いて硬化した板状の成形体であり、離型耐久性に優れ、摩擦係数（摩擦抵抗）の少ない板（プレート）を提供することができる。 According to the twelfth aspect of the present invention, there is provided a plate-like molded body cured by using any of the rubber compositions, a plate (plate) having excellent release durability and a low friction coefficient (friction resistance). Can be provided.
本発明の請求項１３によれば、前記ゴム組成物のいずれかを用いて硬化したシート又はフィルムである成形体であり、離型耐久性に優れ、摩擦係数（摩擦抵抗）の少ないシート又はフィルムを提供することができる。 According to the thirteenth aspect of the present invention, there is provided a molded body that is a sheet or a film cured using any of the rubber compositions, and is a sheet or film that has excellent release durability and a low coefficient of friction (friction resistance). Can be provided.
本発明の請求項１４によれば、前記成形体のいずれかを用いた積層体又は積層板であり、離型耐久性に優れ、摩擦係数（摩擦抵抗）の少ない積層体又は積層板を提供することができ、安価なゴム成形体と積層することにより、コストを低減することが可能となる。 According to the fourteenth aspect of the present invention, there is provided a laminate or a laminate using any one of the above molded products, which is excellent in mold release durability and has a low coefficient of friction (friction resistance). The cost can be reduced by laminating with an inexpensive rubber molded body.
上記、離型性に優れたゴム組成物及びそれを用いた離型耐久性及び転写性に優れた成形体を提供することは、半導体製造ライン用材、燃料電池用材、自動車用材、航空機用材、成形部品材料、押出部品材料、ダイヤフラム材料、バルブ材料、継手材料、Ｏリング材料などに有用である。 Providing a rubber composition having excellent releasability and a molded article having excellent mold release durability and transferability using the rubber composition, semiconductor production line material, fuel cell material, automobile material, aircraft material, molding It is useful for part materials, extruded part materials, diaphragm materials, valve materials, joint materials, O-ring materials and the like.
本発明者は、フッ素化フラーレン生成プロセスの発見を達成し、このフッ素化フラーレンの有効活用を考えた。
フッ素化フラーレンとは、フッ素とフラーレンの化合物ＣｎＦｍ（ｎ＝５０〜１００、ｎ＞ｍ）であり、個体である。また、電子吸引性の強いフッ素のため、良い電子受容体であり、サッカーボール状のＣ６０とフッ素原子との化合物において、カゴの形を保ったままでは最大４６個のフッ素原子がつくことが知られている。
本発明のゴム組成物は、請求項１に記載したように、フッ素化フラーレンを配合することで、金属との離型性に富み、ゴムを成形する場合、金型からの離型性に優れている。
なお、ゴムの加硫、成形において必要な２価金属酸化物、２価金属水酸化物、カーボンブラック、各種フィラー、顔料、硬化剤、硬化遅延剤などを含有しても良いし、適当な離型性及び／又は硬度にさせるために主ゴムと異なるゴムの配合、オイルの配合などの割合を調整しても良い。
The present inventor achieved the discovery of a fluorinated fullerene production process and considered effective utilization of the fluorinated fullerene.
The fluorinated fullerene is a compound of fluorine and fullerene CnFm (n = 50 to 100, n> m) and is an individual. It is also known to be a good electron acceptor due to its strong electron withdrawing fluorine, and it is known that a soccerball-like compound of C60 and fluorine atoms will have a maximum of 46 fluorine atoms if the cage shape is maintained. It has been.
As described in claim 1, the rubber composition of the present invention is rich in releasability from metal by compounding fluorinated fullerene, and is excellent in releasability from a mold when rubber is molded. ing.
The rubber may contain divalent metal oxides, divalent metal hydroxides, carbon black, various fillers, pigments, curing agents, curing retarders, etc., which are necessary for rubber vulcanization and molding. In order to achieve moldability and / or hardness, the proportion of the rubber different from the main rubber, the proportion of oil, etc. may be adjusted.
本発明はゴム組成物のフッ素化フラーレンの配合量においては、請求項２に記載したように、フッ素化フラーレンの配合量は、ゴム成分１００重量部に対して０．１〜２００重量部が好ましい。
０．１重量部以下では、離型性改良効果が発現しない場合がある。また、安価な他の離型剤を配合した方がコスト低減になる場合がある。
離型性の優れているシリコーンゴムなどは、該ゴム以外のゴムに比べて、少ない重量部で良い。０．１重量部以上とすることで離型耐久性がより一層向上する。ただ、２００重量部を超えると、ゴムの特性が用途に適合しない場合、例えば硬くなり過ぎる場合、又は、射出成形や押出成形において金属への離型性が良くなり過ぎてせん断力による混練が不足する場合がある。
In the blending amount of the fluorinated fullerene of the rubber composition of the present invention, as described in claim 2, the blending amount of the fluorinated fullerene is preferably 0.1 to 200 parts by weight with respect to 100 parts by weight of the rubber component. .
If the amount is 0.1 parts by weight or less, the effect of improving releasability may not appear. In addition, the cost may be reduced by adding another inexpensive release agent.
Silicone rubber or the like having excellent releasability may be less in weight parts than other rubbers. When the content is 0.1 parts by weight or more, the mold release durability is further improved. However, if it exceeds 200 parts by weight, if the rubber properties are not suitable for the application, for example, it becomes too hard, or the mold release property to the metal becomes too good in injection molding or extrusion molding, and kneading due to shearing force is insufficient. There is a case.
かかる観点から、配合するゴムの特性及び用途、成形方法に応じ、配合する割合を適当な量にする必要がある。一般的には、５〜１００重量部がより好ましく、特に、機械的特性の安定性から１０〜６０重量部がさらに好ましい。
本発明のゴム組成物は、請求項３に記載したように、液状の組成物にしたものが好ましい。すなわち、真空及び圧送によるＬＩＭ真空注型成形（例えば１液真空注型成形、２液混合真空注型成形）による微細な形状を形成でき、また、微細な形状モデルを正確に反転複写することもできる。
主ゴム成分としては、例えば、天然ゴム及びＥＰＤＭ・ＳＢＲ・ＮＢＲ・ＣＲなどの合成ゴムであっても良い。しかし、請求項４に記載したように、離型性・弾力性・耐熱性などに優れている液状のシリコーン系ゴムがより好ましい。
また、請求項５に記載したように、耐熱性、耐久性などに優れている液状のフッ素系ゴムもより好ましい。
From this point of view, it is necessary to adjust the blending ratio to an appropriate amount according to the characteristics and application of the blended rubber and the molding method. In general, the amount is more preferably 5 to 100 parts by weight, and particularly preferably 10 to 60 parts by weight in view of the stability of mechanical properties.
As described in claim 3, the rubber composition of the present invention is preferably a liquid composition. In other words, a fine shape can be formed by vacuum and pressure LIM vacuum casting (for example, one-component vacuum casting, two-component mixed vacuum casting), and a minute shape model can be accurately inverted and copied. it can.
As the main rubber component, for example, natural rubber and synthetic rubber such as EPDM, SBR, NBR, and CR may be used. However, as described in claim 4, a liquid silicone rubber that is excellent in releasability, elasticity, heat resistance and the like is more preferable.
Further, as described in claim 5, a liquid fluorine-based rubber that is excellent in heat resistance, durability and the like is more preferable.
本発明のフッ素化フラーレンは、請求項６に記載したように、プラズマ法で生成されたフラーレンが好ましい。前記生成方法は、大気中への有害窒素ガスの放出を防止することが可能である。なお、空フラーレン（内部に元素を内包しないフラーレン）でもよいが、内部に元素を内包した内包フラーレンでもよい。
フラーレンとしては、請求項７に記載したように、Ｃｎ（ｎ＝５０〜１００）おいて、Ｃ６０が最も好ましい。Ｃ６０は対称性が良好であるためゴムへの分散性がよく、又、高次フラーレンと比べ、安定性がある。ただ、請求項８に記載したように、高次フラーレン、例えばＣ70は、フッ素原子量が多くなるので離型性向上には有効であるため用いても良い。
本発明のゴム組成物およびそれを用いた請求項９に記載の成形体は、従来のゴム組成物及びそれを用いた成形体よりもはるかに優れた離型性・離型耐久性を有している。
As described in claim 6, the fluorinated fullerene of the present invention is preferably a fullerene produced by a plasma method. The generation method can prevent the release of harmful nitrogen gas into the atmosphere. In addition, although empty fullerene (fullerene which does not include an element inside) may be sufficient, the inclusion fullerene which included the element inside may be sufficient.
As the fullerene, as described in claim 7, C 60 is most preferable in C n (n = 50 to 100). C 60 has good symmetry, so it has good dispersibility in rubber and is more stable than higher fullerenes. However, as described in claim 8, higher fullerenes, for example C 70 may be used because it is effective for a fluorine atom amount releasability improved because increases.
The rubber composition according to the present invention and the molded article according to claim 9 using the rubber composition have a far superior release property and release durability than the conventional rubber composition and the molded article using the rubber composition. ing.
ゴム組成物としては用途に応じて選定する。例えば反発弾性を要求される用途では、シリコーン系ゴムを用いることが好ましい。天然ゴムを用いても良い。
用途としては、例えば、各種ゴム製母型があげられる。請求項１０に記載の型取り用母型、請求項１１に記載の転写用母型（例えば転写用スタンプ等）に好適に用いることができる。フッ素原子を含むため、金属及び各種樹脂との離型性に優れ、離型耐久性も優れた各種ゴム製母型に用いることができる。また、補強性フィラーとして機械的特性など（例えば引張強さ、硬度、耐磨耗性、耐候性、耐炎性など）を調整した各種ゴム製母型に用いることができる。
The rubber composition is selected according to the application. For example, it is preferable to use silicone rubber in applications that require impact resilience. Natural rubber may be used.
Examples of uses include various rubber mother dies. The mold can be suitably used for a mold for molding according to claim 10 and a mold for transfer according to claim 11 (for example, a stamp for transfer). Since it contains a fluorine atom, it can be used for various rubber mother dies that are excellent in releasability from metals and various resins and also excellent in releasability. Moreover, it can be used for various rubber molds in which mechanical properties and the like (for example, tensile strength, hardness, abrasion resistance, weather resistance, flame resistance, etc.) are adjusted as reinforcing fillers.
ゴム組成物へのフッ素化フラーレンの配合において、試作品（モデル）製作用型取り母型であれば、コスト削減のために配合重量部を少なくし、離型耐久性を低下させても良い。プリンター用ロールなどを製造する型取り用母型の場合は、離型耐久性を重視すれば良い。
また、軟らかい樹脂（例えば導電性樹脂）の特定パターン形成（例えば特定パターンの転写）のために転写用母型の場合も離型耐久性を重視すれば良い。特に、電子工業部品の微細なパターン形成（例えば半導体などのnｍレベルの微細パターン形成やガラス基板を用いる蛍光表示装置の微細パターン形成）に好適に用いることができる。
In the blending of the fluorinated fullerene into the rubber composition, if it is a prototype (model) production type mold base, the blending weight part may be reduced to reduce the cost and the mold release durability may be lowered. In the case of a mold master for producing printer rolls, emphasis is placed on mold release durability.
Further, in the case of a transfer mother die for forming a specific pattern (for example, transfer of a specific pattern) of a soft resin (for example, conductive resin), it is only necessary to place importance on release durability. In particular, it can be suitably used for forming fine patterns of electronic industrial parts (for example, forming fine patterns of nm level such as semiconductors and forming fine patterns of fluorescent display devices using glass substrates).
母型を製作する方法は、例えば２液混合用液状ゴム組成物を用いて真空注型法で製作する場合、ゴムを計量し真空脱泡した後、２液を混合し、前記混合物を反転複写用のマスターモデルをセットした型枠内へ２液を混合したゴム組成物を注入し、真空脱泡して硬化させた後、型を開きマスターモデルを取り外す。又は、２つのタンクを設け、圧送により２液を射出し、混合させながら反転複写用のマスターモデルをセットした金型内へ真空注型し、真空脱泡して硬化させ、型を開きマスターモデルを取り外す。
なお、液状のゴム組成物としては、シリコーン系ゴムが好ましい。また、フッ素系ゴムも好ましい。
For example, in the case of manufacturing by a vacuum casting method using a liquid rubber composition for two-component mixing, the rubber is weighed and vacuum defoamed, then the two components are mixed, and the mixture is inverted and copied. A rubber composition in which two liquids are mixed is poured into a mold in which a master model is set, and after vacuum defoaming and curing, the mold is opened and the master model is removed. Alternatively, two tanks are provided, two liquids are injected by pressure feeding, mixed and vacuum cast into a mold set with a master model for reverse copying, vacuum defoamed and cured, the mold is opened, and the master model is opened Remove.
The liquid rubber composition is preferably a silicone rubber. Fluorine rubber is also preferable.
液状のゴム組成物以外を用いてゴム製母型を製作する場合、例えばロール混練又は押出機にて作成した板状のゴム組成物を、射出成形又はプレス成形にてゴム製母型を製作しても良い。ただ、微細な形状を形成するのは、困難な場合がある。
なお、本発明の成形体は、請求項１２に記載したように、板状のゴム成形体は、摺動用部材に用いることができる。例えば、請求項１５に記載したように、自動車のワイパー用ゴム材にも用いることができる。
When producing a rubber mold using a material other than the liquid rubber composition, for example, a rubber mold is produced by injection molding or press molding of a plate-shaped rubber composition prepared by roll kneading or an extruder. May be. However, it may be difficult to form a fine shape.
In addition, as for the molded object of this invention, as described in Claim 12, the plate-shaped rubber molded object can be used for the member for sliding. For example, as described in claim 15, it can also be used for rubber materials for automobile wipers.
製作方法としては、前記と同様、真空注型法、射出成形法、プレス法などがある。
また、請求項１３に記載したように、シート又はフィルムは、金属や樹脂等との離型性を向上させるためのコーティング材に用いることができる。例えば、射出成形法の場合、金型内にシート又はフィルムを装填しながら、射出成形を行うことで成形品の表面にコーティングができる。
そして、請求項１４に記載したように、本願請求項１０〜１３の成形体の少なくとも１項を用いた積層体または積層板にすることで、離型耐久性に優れ、摩擦係数の少ない成形体を得ることもできる。
As the manufacturing method, there are a vacuum casting method, an injection molding method, a pressing method and the like as described above.
In addition, as described in claim 13, the sheet or film can be used as a coating material for improving releasability from metals, resins, and the like. For example, in the case of an injection molding method, the surface of a molded product can be coated by performing injection molding while loading a sheet or film in a mold.
And, as described in claim 14, by forming a laminate or laminate using at least one of the molded products of claims 10 to 13 of the present application, a molded product having excellent mold release durability and a low friction coefficient. You can also get
本例では、市販のウレタン注型用シリコーンゴムと、フッ素化フラーレンと、硬化遅延剤とを組成物として、フッ素化フラーレンの配合量を変化させ、その組成物で凹部を有する母型を成形した。市販のウレタン樹脂を母型の凹状部に充填し、常温（２３℃）で硬化させ、ウレタン成形体が母型に接着するまでの型取り回数（離型耐久性）を測定した。
ブランク ４８回
１重量部 １０２回
３重量部 ４３２回
５重量部 ８９６回
１０重量部 １１０３回
なお、約２０回までの離型性については、特に差異は認められずブランク成形体でも離型性は良好であった。
In this example, a commercially available silicone rubber for urethane casting, a fluorinated fullerene, and a curing retarder were used as a composition, and the blending amount of the fluorinated fullerene was changed, and a matrix having recesses was molded with the composition. . A commercially available urethane resin was filled in the concave portion of the mother mold and cured at room temperature (23 ° C.), and the number of times of mold removal (mold release durability) until the urethane molded body adhered to the mother mold was measured.
Blank 48 times 1 part by weight 102 times 3 parts by weight 432 times 5 parts by weight 896 times 10 parts by weight 1103 times There is no particular difference in the releasability up to about 20 times. It was good.
本例では、シリコーンゴム１００重量部に対し、フッ素化フラーレンを５重量部配合し、フッ素化フラーレンゴム組成物を作成した。一方、フッ素化フラーレンを配合していないゴム組成物（比較例）も作成した。前記ゴム組成物を用いて、真空注型法にて凹部を設けた平板状のシリコーンゴム母型を作成した。前記母型に、エポキシ樹脂を充填させ、転写を繰り返し行い、転写性の比較評価を行った。他の点は実施例１と同様とした。
本例では、フッ素化フラーレンを配合したものは、離型耐久性において、配合していないものよりも良好であり、約１０〜５０倍の離型耐久性があった。
In this example, 5 parts by weight of fluorinated fullerene was blended with 100 parts by weight of silicone rubber to prepare a fluorinated fullerene rubber composition. On the other hand, a rubber composition (comparative example) containing no fluorinated fullerene was also prepared. Using the rubber composition, a flat silicone rubber mold having recesses was formed by vacuum casting. The matrix was filled with an epoxy resin, transfer was repeated, and transferability was evaluated for comparison. The other points were the same as in Example 1.
In this example, the compound containing fluorinated fullerene was better in mold release durability than the one not compounded, and had a mold release durability of about 10 to 50 times.
本例では、フッ素ゴム１００重量部に対して、フッ素化フラーレン１００重量部を配合したゴム組成物を作成した。一方、フッ素ゴム１００重量部に対して、カーボンブラック１００重量部を配合したゴム組成物（比較例）を作成した。その他の点では、実施例２と同様とした。
本例では、フッ素化フラーレンを配合したものは、離型耐久性において、カーボンブラックを配合したものよりも良好であり、約５０〜１００倍の離型耐久性があった。
In this example, a rubber composition was prepared by blending 100 parts by weight of fluorinated fullerene with 100 parts by weight of fluororubber. On the other hand, a rubber composition (comparative example) in which 100 parts by weight of carbon black was blended with 100 parts by weight of fluororubber was prepared. The other points were the same as in Example 2.
In this example, the compound containing fluorinated fullerene was better in mold release durability than the compound containing carbon black, and had a mold release durability of about 50 to 100 times.
本例では、フッ素ゴム１００重量部に対して、フッ素化フラーレン５０重量部配合した組成物を作成した。一方、フッ素ゴム１００重量部に対して、カーボンブラック５０重量部を配合した組成物（比較例）を作成した。前記ゴム組成物を用い、Ｏリングの金型にて成形し、離型性を比較した。金型からの離型性は、カーボンブラックを配合した組成物は非常に困難であったが、フッ素化フラーレンを配合した組成物は非常に良好であった。 In this example, a composition was prepared by blending 50 parts by weight of fluorinated fullerene with 100 parts by weight of fluororubber. On the other hand, a composition (comparative example) was prepared by blending 50 parts by weight of carbon black with respect to 100 parts by weight of fluororubber. Using the rubber composition, it was molded with an O-ring mold and the releasability was compared. The mold releasability from the mold was very difficult for the composition containing carbon black, but the composition containing fluorinated fullerene was very good.
本例では、天然ゴム１００重量部に対して、フッ素化フラーレン５０重量部を配合した組成物を用いて成形した板と、カーボンブラック５０重量部を配合した組成物を用いて成形した板（比較例）を用いて、耐摩耗性を比較した。
金属円板を回転させ、それへ成形体を接触させ、磨耗量を測定することから耐磨耗性を評価した。
本例では、カーボンブラックを配合したものよりも、フッ素化フラーレンを配合したものの方が、非常に良好であり、前者に対し後者は約３０％磨耗量が少なかった。
このことは、フッ素化フラーレンを配合した組成物の成形体は、カーボンブラックを配合した成形体よりも、金属に対する摩擦係数が少ないことを意味している。すなわち、フッ素化フラーレンを配合した組成物の成形体は、カーボンブラックを配合した成形体よりも、摺動性を要求される用途には有効である。例えば金属性管軸を摺動させる部分に用いるＯリングにおいて、フッ素化フラーレンを配合した組成物の成形体は、カーボンブラックを配合した成形体よりも、長期摺動性維持に有効である。
In this example, a plate formed by using a composition in which 50 parts by weight of fluorinated fullerene is blended with 100 parts by weight of natural rubber, and a plate formed by using a composition in which 50 parts by weight of carbon black are blended (comparison) Example) was used to compare the wear resistance.
The wear resistance was evaluated by rotating the metal disk, bringing the compact into contact therewith, and measuring the amount of wear.
In this example, the compound containing the fluorinated fullerene was much better than the compound containing carbon black, and the latter had about 30% less wear than the former.
This means that the molded product of the composition blended with the fluorinated fullerene has a smaller coefficient of friction against the metal than the molded product blended with carbon black. That is, a molded product of a composition blended with fluorinated fullerene is more effective for applications requiring slidability than a molded product blended with carbon black. For example, in an O-ring used for a portion on which a metallic tube shaft is slid, a molded product of a composition containing fluorinated fullerene is more effective in maintaining long-term slidability than a molded product containing carbon black.
Claims (15)
The molded body according to any one of claims 12 to 14, wherein the molded body is a rubber plate for an automobile wiper.
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| JP2016079358A (en) * | 2014-10-22 | 2016-05-16 | 昭和電工株式会社 | Fluorine-containing elastomer composition, molded article hereof and device incorporating molded article |
| WO2016104604A1 (en) * | 2014-12-26 | 2016-06-30 | 昭和電工株式会社 | Fluorine-containing elastomer composition, molded article, seal material, and device |
| CN109054395A (en) * | 2018-06-27 | 2018-12-21 | 华南理工大学 | A kind of high temperature resistant halogen-free flame-retardant silicon rubber and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005325198A (en) * | 2004-05-13 | 2005-11-24 | Ideal Star Inc | Fluorinated fullerene-containing resin composition and molded product using the same |
| JP2016079358A (en) * | 2014-10-22 | 2016-05-16 | 昭和電工株式会社 | Fluorine-containing elastomer composition, molded article hereof and device incorporating molded article |
| WO2016104604A1 (en) * | 2014-12-26 | 2016-06-30 | 昭和電工株式会社 | Fluorine-containing elastomer composition, molded article, seal material, and device |
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