JP2010089974A - Carbon aggregate molded article and method of manufacturing carbon aggregate molded article - Google Patents
Carbon aggregate molded article and method of manufacturing carbon aggregate molded article Download PDFInfo
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この発明は、炊飯釜、鍋、トースター等の電磁誘導加熱が可能な電磁調理器具に使用するカーボン凝結体成形品に関する。さらに、カーボン凝結体成形品を得る無酸素状態下の焼成処理に供するカーボン粉粒と高炭素含有物質である結合材が主体のカーボン凝結体成形材料と射出成型などの金型を用いたカーボン凝結体成形品の製造方法に関する。 The present invention relates to a carbon aggregate molded product used for an electromagnetic cooking appliance capable of electromagnetic induction heating such as a rice cooker, a pan, a toaster or the like. In addition, carbon agglomerates using carbon aggregates mainly composed of carbon powder particles and high carbon-containing binders that are subjected to an oxygen-free firing process to obtain a carbon agglomerated molded article and a mold such as injection molding The present invention relates to a method for manufacturing a body molded product.
電磁加熱調理器であるコンロや炊飯器は、高周波磁場発生装置である誘導加熱コイルが発生する渦電流によって磁性体金属である鉄やステンレスなどが発熱する電磁誘導加熱を利用するもので、調理器による食品の速やかで均一な加熱が得られるという特徴を有する。当該電磁加熱調理器には、アルミニウムや銅などを積層したクラッド材を鍋状の成形品として用いていたが、クラッド材は鍋や釜などの形状加工が困難で、さらに表面をフッ素樹脂などの耐熱樹脂塗装面の各積層界面が剥離し易いなどの不具合もあった。 The stove or rice cooker, which is an electromagnetic heating cooker, uses electromagnetic induction heating in which iron or stainless steel, which is a magnetic metal, generates heat due to eddy current generated by an induction heating coil, which is a high-frequency magnetic field generator. It is characterized in that the food can be heated quickly and uniformly. The electromagnetic heating cooker used a clad material laminated with aluminum or copper as a pot-shaped molded product, but the clad material is difficult to shape, such as a pan or kettle, and the surface is made of fluorine resin or the like. There were also inconveniences such as easy peeling of each laminated interface on the heat-resistant resin coating surface.
そこで、鍋を誘導加熱したときに、鍋に渦電流が発生し易くすると共に、発生した熱が鍋全体に均一且つ速やかに伝達し易くし、また、この鍋の製造時に鍋が変形したりする欠点を解消するために、鍋の外底面部または外周面部に対向するように設けられ上記鍋を誘導加熱する誘導加熱コイルを備えると共に、この誘導加熱コイルを通電制御する制御手段を備えたものにおいて、鍋をカーボン純度が９９．９％以上の黒鉛から構成したことにより、誘導加熱時に鍋に渦電流が発生し易くなると共に、発生した熱が鍋全体に均一且つ速やかに伝達するようになる。しかも、上記鍋を製造する場合、クラッド材製の鍋とは異なり、製造時に鍋が傷付いたり、変形したりすることがなくなり、鍋の品質が向上する誘導加熱調理器が提案されている（例えば、特許文献１参照）。 Therefore, when the pan is induction heated, eddy currents are easily generated in the pan, and the generated heat is easily and evenly transmitted to the entire pan, and the pan is deformed when the pan is manufactured. In order to eliminate the disadvantages, an induction heating coil that is provided so as to be opposed to the outer bottom surface portion or the outer peripheral surface portion of the pan and induction-heats the pan, and that includes a control means that controls energization of the induction heating coil. Since the pan is made of graphite having a carbon purity of 99.9% or more, an eddy current is easily generated in the pan during induction heating, and the generated heat is uniformly and quickly transmitted to the entire pan. Moreover, in the case of manufacturing the above-described pan, an induction heating cooker has been proposed in which the pan is not damaged or deformed during manufacturing, unlike the clad-made pan, and the quality of the pan is improved ( For example, see Patent Document 1).
また、従来の電磁加熱調理器が急激に高温と成り、かつ急激に冷めて熱効率が悪いこと、並びに焼肉など焼物調理に不向きであることを解消し、炭火焼のような温和な熱で焼肉などの焼物調理をすることができ、かつスイッチを切っても長時間の保温性がある電磁加熱調理器を提供することを目的として、ケ−シング内の高周波磁場発生装置に接して炭素圧縮体から成る器物を配設した電磁加熱調理器、炭素圧縮成型器物から成る電磁加熱調理器が提案されている（例えば、特許文献２参照）。 In addition, the conventional electromagnetic heating cooker suddenly becomes high temperature, and suddenly cools and heat efficiency is poor, and it is not suitable for grilled meat cooking such as grilled meat, and grilled meat with mild heat such as charcoal grill For the purpose of providing an electromagnetic heating cooker that can cook pottery and can retain heat for a long time even when the switch is turned off, it comes in contact with the high-frequency magnetic field generator in the casing from the carbon compression body. There have been proposed an electromagnetic heating cooker including a container and an electromagnetic heating cooker including a carbon compression molded article (see, for example, Patent Document 2).
上述の特許文献１記載の誘導加熱調理器の製造方法は、コークスなどのカーボン粉粒にフェノールやピッチなどの高炭素含有物である結合材を主体とする混合物を成型し、これを無酸素雰囲気下の１０００〜３０００℃で加熱して得たカーボンの凝結体を得た後、任意の形状に切削加工したものである。しかし、カーボンの焼結体を切削加工して任意の形状に加工することは、切削の大半を占める容器の凹状を成す中空部分にある素材の廃棄が多く、且つ加工工数も大きい、という課題があった。
In the method of manufacturing an induction heating cooker described in
これらの課題を解決する手段として、カーボンの粉粒とフェノール樹脂の原料液やタールピッチなどの結合材との混合物を金型内に注入して加圧するなどして賦型した後、得られた成形品を焼成処理することによって鍋状に成形されたカーボンの凝結体を得る手段が提案されている（例えば、特許文献３参照）。
上記特許文献３の成形手段は、射出したカーボンなどの混合物である成型材料の金型への充填が、金型内にある空気を排出して未充填を回避し、射出時の加圧力を減衰させずに付加して均質で高い強度や伝熱特性などの確保を図るものである。しかし、単なるカーボン粉粒と結合材の混合物は、金型内での流動時に結合材が溶融してカーボン粉粒の搬送を可能とするため、電磁誘導加熱が可能な調理器具として使用する上で必要な強度や電気伝導、熱伝達に優れる凝結体を得るには、カーボン粉粒の混合比を高くすることが必須である。
The molding means of
しかし、カーボン粉粒の混合比が高い組成は、極めて高い粘度を呈する上に、カーボン粉粒の表面が十分に濡れないためにカーボン粉粒同志が凝集して流動性を喪失し易い、という課題がある。 However, a composition with a high mixing ratio of carbon particles exhibits an extremely high viscosity, and the surfaces of the carbon particles are not sufficiently wetted so that the carbon particles are likely to aggregate and easily lose fluidity. There is.
このような充填性に劣る原料を用いた場合に得られる成形品は、カーボン粉粒の細密充填に必要な圧力付加が不十分で、カーボン粉粒同士が接合できない部分もあるので、無酸素雰囲気で焼成処理したカーボン凝結体成形品は多くの気孔が残留し、曲げや引張りなどの各種強度や熱伝導率は本来の特性に比較して低くなるという課題があった。 The molded product obtained when using such a raw material with inferior filling properties has insufficient pressure applied for dense filling of carbon particles, and there are parts where the carbon particles cannot be joined together. The carbon coagulated product fired in the process had many pores, and there was a problem that various strengths such as bending and tension and thermal conductivity were lower than the original characteristics.
さらに、上述した各種強度の低下は、成形品表面を塗装した場合に塗膜の受ける引張り応力によって成形材料が凝集破壊を来して剥離し易くなって、見掛け上塗膜の密着性が悪いという課題を有する。 Furthermore, the above-mentioned reductions in various strengths indicate that when the surface of a molded article is coated, the molding material is subject to cohesive failure due to the tensile stress received by the coating film, and is easily peeled off, and apparently the adhesion of the coating film is poor. Has a problem.
つまり、電磁誘導加熱が可能な調理器具として好適な強度と電気特性や熱伝導率を備えるには、カーボン粉粒を高度に密接して含有させることが必要である上、成形時の流動性、得られた凝結体成形品の各種強度低下と塗膜密着性低下という課題を回避する必要がある。 In other words, in order to provide strength and electrical characteristics and thermal conductivity suitable as a cooking utensil capable of electromagnetic induction heating, it is necessary to contain carbon particles highly closely, and fluidity during molding, It is necessary to avoid the problems of various strength reductions and coating film adhesion reductions of the obtained aggregate molded product.
この発明は、上記のような課題を解決するためになされたもので、従来の混合物のように結合材が介在せずに欠陥部分を残留させることがなく、各種強度や熱伝導率に優れるカーボン凝結体成形品及びカーボン凝結体成形品の製造方法を提供することを目的とする。 The present invention has been made to solve the above-described problems, and does not leave a defective portion without a binder as in a conventional mixture, and is excellent in various strengths and thermal conductivity. It is an object of the present invention to provide a method for producing an aggregate molded article and a carbon aggregate molded article.
この発明に係るカーボン凝結体成形品は、カーボン粉粒と高炭素含有物とからなる成形材料に、シロキサンを含有する草木表皮又は種子殻の薫蒸炭と高炭素含有物とから成る改質材料を積層した状態で加熱加圧成形して得た成形品の炭化処理物であることを特徴とする。 The carbon agglomerate molded article according to the present invention is a reformed material comprising a siloxane-containing plant skin or seed shell fumigated charcoal and a high carbon content in a molding material comprising carbon particles and a high carbon content. It is characterized by being a carbonized product of a molded product obtained by heat and pressure molding in a state of being laminated.
この発明に係るカーボン凝結体成形品は、カーボン粉粒の混合比を高くしても、カーボン粉粒表面に未硬化のフェノール樹脂が被覆されているので、流動過程でカーボン粉粒同志が接触しても滑りやすくなって凝集し難いことから、高い流動性を呈することになる。しかも、粉粒間が低い圧力付加であっても、カーボン粉粒同士の接合に際して、結合材のフェノール樹脂未硬化物が前記カーボン粉粒同士を融着させることができるので、従来の混合物のように結合材が介在しない欠陥部分を残留させることがなく、各種強度や熱伝導率に優れるカーボン凝結体成形品が得られる。 In the carbon aggregate molded product according to the present invention, even if the mixing ratio of the carbon particles is increased, the carbon particle surfaces are coated with uncured phenol resin, so that the carbon particles are in contact with each other in the flow process. However, since it becomes slippery and hardly aggregates, it exhibits high fluidity. In addition, even when the pressure between the powder particles is low, the carbon resin particles can be fused together by the phenol resin uncured material of the binder when the carbon particles are bonded to each other. In this way, a carbon aggregate molded article excellent in various strengths and thermal conductivity can be obtained without leaving a defective portion in which no binder is present.
実施の形態１．
圧縮成形によって鍋状の種子殻燻蒸炭凝結体をカーボン粉粒凝結体に積層した成型品とその製造方法に関し、原料炭粉粒と結合材との混合物である成形材料を鍋状の金型に充填した後、加熱・加圧して得た成形品を無酸素の高温雰囲気下で焼成処理して得る電磁誘導加熱調理器具とその製造方法を、以下に詳述する。
In relation to a molded product in which a pan-like seed shell fumigated coal condensate is laminated on a carbon particle agglomerate by compression molding and a manufacturing method thereof, a molding material that is a mixture of raw material carbon powder particles and a binder is put into a pot-shaped mold. The electromagnetic induction heating cooking utensil obtained by baking the molded product obtained by heating and pressurizing after filling in an oxygen-free high temperature atmosphere and the manufacturing method thereof will be described in detail below.
まず、石油コークスを無酸素状態の高温（約３０００℃）で焼成して、電磁誘導加熱の効率に優れるグラファイト化した黒鉛の塊状物を０．２ｍｍ以下に粉砕したカーボン粉粒をエタノールと水の混合溶媒で希釈したフェノール溶液中の減圧下で混合する。そして、その表面を十分に濡らした後、さらにカーボン粉粒を均一分散させるように混合しながらホルムアルデヒドを添加しながら、重合を進行させる。流動性に好適な半硬化状態を確保するに至るまで、本実施の形態では７０℃以下で約１５０分間の撹拌を行った。 First, carbon coke obtained by firing petroleum coke at an oxygen-free high temperature (about 3000 ° C.) and pulverizing a graphitized graphite lump excellent in electromagnetic induction heating efficiency to 0.2 mm or less is used as ethanol and water. Mix under reduced pressure in a phenol solution diluted with a mixed solvent. Then, after the surface is sufficiently wetted, the polymerization is allowed to proceed while adding formaldehyde while mixing so as to uniformly disperse the carbon particles. In this embodiment, stirring was performed at 70 ° C. or lower for about 150 minutes until a semi-cured state suitable for fluidity was ensured.
重合の進行とともに、溶剤中に分散させたカーボン粉粒を核とする半硬化状態のフェノール樹脂が塗膜となって析出しながらエマルジョンを形成する。本実施の形態に用いる成形材料と成すには、これをロータリー乾燥機に移して冷却することにより、エタノールと水の混合溶媒中にあって、カーボン粉粒の表面に析出させた半硬化状態のフェノール樹脂を固化させる低温状態で溶媒を飛散させて乾燥させることによって、粒状微粉末とした。 As the polymerization proceeds, an emulsion is formed while a semi-cured phenol resin having carbon particles dispersed in a solvent as a core is deposited as a coating film. To form the molding material used in the present embodiment, it is transferred to a rotary dryer and cooled, so that it is in a mixed solvent of ethanol and water, and is in a semi-cured state deposited on the surface of carbon particles. The solvent was scattered and dried at a low temperature for solidifying the phenol resin to obtain a granular fine powder.
この時、得られた粒状微粉末にはカーボン粉粒を核とせず、フェノール樹脂のみで形成された球状粉粒も混入しており、これを比重分別により排除した。得られた成形材料は、合成した未硬化状態のフェノール樹脂がカーボンの粉粒の外周面に膜として保持した粒状を成し、粒子表面の樹脂保有率が約１８ｗｔ％を備えて成る成形材料を得た。粒子表面の樹脂保有率が約１８ｗｔ％を備えて成る成形材料が、カーボン粉粒と高炭素含有物とからなる成形材料である。 At this time, the obtained granular fine powder did not have carbon powder as a core, but also spherical powder formed only with a phenol resin, which was excluded by specific gravity fractionation. The obtained molding material is formed into a granular material in which the synthesized uncured phenol resin is held as a film on the outer peripheral surface of the carbon particles, and the resin content on the particle surface is about 18 wt%. Obtained. A molding material having a resin retention rate of about 18 wt% on the particle surface is a molding material composed of carbon powder and a high carbon content.
同様手段により、シロキサンを含有する草木表皮又は種子殻の薫蒸炭と高炭素含有物とから成る改質材料として成形材料の核として、籾殻を４８０℃の窒素雰囲気下で燻蒸することによって得たが３５μｍの籾殻の燻蒸炭を用いて、概略、０．０５〜０．３ｍｍの直径を有する粒状を成して、粒子表面の樹脂保有率が約２５ｗｔ％の改質材料を確保した。 By the same means, obtained by fumigating rice husks in a nitrogen atmosphere at 480 ° C. as the core of the molding material as a reforming material consisting of fumigated charcoal of vegetation epidermis or seed shell containing siloxane and high carbon content Using a fumigated charcoal of rice husk having a diameter of 35 μm, a granular material having a diameter of approximately 0.05 to 0.3 mm was roughly formed, and a modified material having a resin retention rate of about 25 wt% on the particle surface was secured.
次に、これら成形材料を用いて鍋状の成形品を得る圧縮成形の手段について詳述する。金型は硬化温度である約１６５℃に加熱しておき、壁面の肉厚に見合う任意の量の成形材料を均一な厚さに投入する。次いで、同様に壁面の肉厚に見合う任意の量の改質材料を積層するようにして投入後、圧縮成形を行った。本実施の形態では、改質材料を、約１００μｍの成形後の厚さとなるように、その粉粒を散布することによって達成した。 Next, a compression molding means for obtaining a pot-shaped molded product using these molding materials will be described in detail. The mold is heated to a curing temperature of about 165 ° C., and an arbitrary amount of molding material commensurate with the wall thickness is poured into a uniform thickness. Subsequently, similarly, an arbitrary amount of the modifying material corresponding to the wall thickness was laminated so as to be laminated, followed by compression molding. In the present embodiment, the modified material is achieved by spraying the powder particles so as to have a thickness after molding of about 100 μm.
このとき、上述工程で得たフェノール樹脂が硬化反応の初期段階に発生する副生成物である水蒸気などのガスの放散を促す目的で、硬化の進行に伴う流動粘度が過度に上昇しない時間、本実施の形態では、１０〜３０秒間、触圧程度の低圧で加圧して未硬化状態のフェノール樹脂を溶融させることが、成形品表面にガス溜まりなどの凹状の変形を有さずに賦型する上で有効であった。 At this time, the phenol resin obtained in the above process is a time during which the fluid viscosity accompanying the progress of curing does not increase excessively for the purpose of promoting the diffusion of gas such as water vapor, which is a by-product generated in the initial stage of the curing reaction. In the embodiment, the uncured phenol resin is melted by pressurizing at a low pressure such as a contact pressure for 10 to 30 seconds, so that the molded product surface is molded without having a concave deformation such as a gas reservoir. It was effective above.
低圧加圧完了後に引き続いて、一旦、金型を僅かに開放して、発生した水蒸気などのガスを放出した後、高圧状態、本実施の形態では、約１０ＭＰａで加圧して任意時間、本実施の形態では３００〜３６０秒間の放置にてフェノール樹脂を完全硬化させた後、金型から取り出した。 Following the completion of low-pressure pressurization, once the mold is slightly opened and the generated gas such as water vapor is released, then the high-pressure state, in this embodiment, pressurizing at about 10 MPa, this time, this implementation In this form, the phenol resin was completely cured by leaving for 300 to 360 seconds, and then taken out from the mold.
上述手段によって得られた成形材料は、製造を容易と成す塊状物を破砕して得たカーボン粉粒が備える鋭角な端面を未硬化状態のフェノール樹脂が隠蔽して平滑な面を形成して成るため、加圧時における金型内の空隙を埋めるように移動しやすい、つまり、流動性に優れるという特徴を有する。 The molding material obtained by the above-mentioned means is formed by forming a smooth surface by concealing the sharp end face of the carbon particles obtained by crushing the lump that is easy to manufacture, with the uncured phenolic resin concealing it. Therefore, it has the feature that it is easy to move so as to fill the void in the mold during pressurization, that is, it has excellent fluidity.
さらに、成形材料同士が接した部位にはカーボン粉粒を被覆したフェノール系樹脂未硬化物が存在するので、加熱・加圧成形時に粉粒同志が密接して融着するので、従来の単純な混合物のように結合材の存在し得ない部分が欠陥部分として残留することがないので、高い強度や熱伝導率などの優れた諸特性を確保することができる。 Furthermore, since there is an uncured phenolic resin coated with carbon particles at the site where the molding materials are in contact with each other, the powder particles are intimately fused at the time of heating and pressure molding, so the conventional simple Since a portion where the binder cannot exist such as a mixture does not remain as a defective portion, excellent characteristics such as high strength and thermal conductivity can be ensured.
得られた成形品は、無酸素雰囲気の約１２００℃でフェノール樹脂を炭化させて、鍋状を成すカーボン凝結体を得た。このとき、フェノールの分解生成物が当該成形品から放散せずに内部に滞留して膨張し、表面層の近傍で亀裂や局部的な膨れの発生防止を目的に、温度上昇を段階的に行うことが肝要である。 The obtained molded product was carbonized with phenol resin at about 1200 ° C. in an oxygen-free atmosphere to obtain a carbon aggregate in the form of a pan. At this time, the decomposition product of phenol stays inside and expands without being diffused from the molded product, and the temperature is increased stepwise in order to prevent the occurrence of cracks and local swelling near the surface layer. It is important.
つまり、フェノール樹脂の分解が活発になって急激な重量減少を来す３５０℃、５００℃、８００℃近傍は温度の緩い上昇または保持を行う。具体的には、３００℃迄を０．５℃／ｍｉｎで速く昇温後、３５０℃に１℃／ｈｒの緩い昇温で到達後、５時間の保持をした。また、４５０℃迄を５℃／ｈｒ、５００℃迄を１℃／ｈｒで到達後、５時間の保持をした。さらに、７５０℃迄を５℃／ｈｒ、８００℃迄を２℃／ｈｒで到達後、３時間の保持をした。その後、０．５℃／ｍｉｎで１２００℃に到達させて２時間の保持を行った。 That is, in the vicinity of 350 ° C., 500 ° C., and 800 ° C. where the decomposition of the phenol resin becomes active and causes a rapid weight loss, the temperature is slowly increased or maintained. Specifically, the temperature was rapidly increased up to 300 ° C. at 0.5 ° C./min, then reached 350 ° C. at a moderate temperature increase of 1 ° C./hr, and then held for 5 hours. Further, after reaching 450 ° C. at 5 ° C./hr and up to 500 ° C. at 1 ° C./hr, it was held for 5 hours. Further, after reaching 5 ° C./hr up to 750 ° C. and 2 ° C./hr up to 800 ° C., it was held for 3 hours. Then, it reached 1200 degreeC at 0.5 degreeC / min, and hold | maintained for 2 hours.
また、冷却については、０．５℃／ｍｉｎで室温近傍まで冷却した。 Moreover, about cooling, it cooled to room temperature vicinity at 0.5 degree-C / min.
これとは別に、比較例として、カーボン粉粒または籾殻炭と半硬化状態のフェノール樹脂とを押出機で混練後、１ｍｍ以下に粉砕した成形用原料とし、金型内にカーボン粉粒と半硬化状態のフェノール樹脂を混練した成形材料のみを金型に載置し、その上に前記カーボン粉粒単独の成形材料に籾殻炭と半硬化状態のフェノール樹脂の成形材料の同量を混合したものを積層して載置し、これを圧縮成形して凝結体成形品を確保した。この凝結体成形品は、無酸素雰囲気で焼成処理によってカーボン粉粒または籾殻炭単独またはカーボン粉粒または籾殻炭と籾殻炭との積層品である鍋状の凝結体成形品であり、本実施の形態との比較を行うための凝結体成形品Ａ（比較例１）とした。 Separately, as a comparative example, carbon powder or rice husk charcoal and a semi-cured phenol resin are kneaded with an extruder and used as a molding raw material that is pulverized to 1 mm or less. Only the molding material kneaded with the phenol resin in the state is placed on the mold, and then the same amount of the molding material of rice husk charcoal and the semi-cured phenol resin is mixed with the molding material of the carbon powder alone. Laminated and placed, and compression molded to secure a molded product. This aggregate molded product is a pan-shaped aggregate molded product which is a carbon granule or rice husk charcoal alone or a laminate of carbon granule or rice husk charcoal and rice husk charcoal by a firing treatment in an oxygen-free atmosphere. It was set as the aggregate molded article A (comparative example 1) for comparing with a form.
次に、上記手段にて作成した鍋状を成すカーボンの凝結体成形品に関し、成型時に成型用原料を配した底面と、流動過程にあって終点に近い側部内面上部の各部位における塗膜密着性について評価した。凝結体成形品が備える気孔内に含浸する塗料として、外面には耐摩耗性と耐熱性に優れるシリコーン樹脂を、内面には調理具材が密着するのを防止するフッ素樹脂を、各々、塗布した。塗料は凝結体表面にある多くの気孔に含浸し、これに伴ってアンカー効果によって塗膜が強固に固着する。 Next, regarding the carbon aggregate formed product in the form of a pan formed by the above means, the bottom surface on which the raw material for molding was arranged at the time of molding, and the coating film on each part of the upper part of the inner surface of the side part in the flow process and close to the end point The adhesion was evaluated. As the paint impregnated in the pores of the aggregate molded product, a silicone resin excellent in wear resistance and heat resistance was applied to the outer surface, and a fluorine resin was applied to the inner surface to prevent the cooking utensils from sticking to each other. . The coating impregnates many pores on the surface of the aggregate, and accompanying this, the coating is firmly fixed by the anchor effect.
塗膜の剥離強さ（塗膜密着性）を、塗料のみに１ｍｍ間隔で縦横、各々に１１本の切れ目を碁盤目状に入れた面上にテープを密着させ、これの引き剥し動作の繰り返し数１０回によって生じる升目部分の欠損箇所を確認し、欠損のない部分の升目の数で評価するテープ剥離試験を行った。このテープ剥離試験の検体は鍋の外面に相当するので、底面部分が「カーボン粉粒単独の鍋状の凝結体成形品」になる。 The peeling strength of the coating film (coating film adhesion) is determined by repeating the peeling operation of the tape only on the side of the grid cut in the form of a grid of eleven cuts at 1 mm intervals in the paint only. A tape peeling test was performed in which the missing portion of the mesh portion generated by several tens of times was confirmed and evaluated by the number of the meshes of the portion having no defect. Since the specimen of this tape peeling test corresponds to the outer surface of the pan, the bottom portion becomes a “pan-shaped aggregate formed product of carbon powder alone”.
上述したテープ剥離試験（塗膜密着性）の評価に加え、塗装面の外観評価の結果を図１に示す。図１は凝結体成形品Ｂ（実施の形態１）と凝結体成形品Ａ（比較例１）の塗膜密着性及び外観の評価結果を示す図である。 In addition to the evaluation of the tape peeling test (coating film adhesion) described above, the result of the appearance evaluation of the painted surface is shown in FIG. FIG. 1 is a diagram showing evaluation results of coating film adhesion and appearance of the aggregate molded product B (Embodiment 1) and the aggregate molded product A (Comparative Example 1).
図１に示すように、改質材料を成形材料に積層して成形した凝結体成形品Ｂ（実施の形態１）に対し、カーボン粉粒とフェノール樹脂の混練物である成形材料のみで成形した凝結体成形品Ａ（比較例１）の場合は、側面上部が光沢に劣る（曇り有り）ものの、内外面ともに平滑な塗膜面を備え、ほぼ同等の外観を呈した。 As shown in FIG. 1, the aggregated molded product B (Embodiment 1) formed by laminating the reforming material on the molding material was molded only with the molding material that is a kneaded product of carbon powder and phenol resin. In the case of the aggregated molded product A (Comparative Example 1), the upper part of the side surface was inferior in gloss (has fogging), but both the inner and outer surfaces had smooth coating surfaces and exhibited almost the same appearance.
反面、塗膜密着性は、凝結体成形品Ａ（比較例１）では成形材料を伴う塗膜欠落を確認、特に側面上部で顕著に多く見られた。即ち、凝結体成形品Ａ（比較例１）では、側面上部において、１００箇所の升目のうち、欠損のない部分の升目の数は１２であった。また、底面では、１００箇所の升目のうち、欠損のない部分の升目の数は２４であった。これに対して、凝結体成形品Ｂ（実施の形態１）では、何れの部分においても欠損を生じることが無く、有意に優れた塗膜密着性を示した。 On the other hand, coating film adhesion was confirmed to be remarkable in the upper part of the side surface, particularly in the aggregated molded product A (Comparative Example 1), confirming the absence of the coating film accompanying the molding material. That is, in the aggregated molded product A (Comparative Example 1), the number of cells having no defect among the 100 cells in the upper part of the side surface was 12. On the bottom surface, the number of cells having no defect among the 100 cells was 24. On the other hand, in the aggregated molded product B (Embodiment 1), there was no defect in any part, and the coating adhesion was significantly excellent.
また、成形品の内面部分にあり、開口部外縁部分と底部分における籾殻炭とフェノール樹脂から成る改質材料を積層した約１ｍｍの表層部分を採取し、表層部分を上位置（非応力負荷面）にした場合（１）と、表層部分を下位置（非応力負荷面）にした場合（２）の曲げ強度を各々測定し、その結果を図２に示す。図２は凝結体成形品Ｂ（実施の形態１）と凝結体成形品Ａ（比較例１）の曲げ強度の測定結果を示す図である。 In addition, a surface layer portion of about 1 mm in which the reformed material made of rice husk charcoal and phenolic resin is laminated on the outer edge portion and the bottom portion of the opening is sampled, and the surface layer portion is in the upper position (non-stressed load surface) ) And (2) when the surface layer portion is in the lower position (non-stressed load surface), the bending strength is measured, and the results are shown in FIG. FIG. 2 is a diagram showing the measurement results of the bending strength of the aggregate molded product B (Embodiment 1) and the aggregate molded product A (Comparative Example 1).
図２に示すように、凝結体成形品Ｂ（実施の形態１）は、カーボン粉粒または籾殻炭とフェノール樹脂を混練したのみの成形材料および改質材料で成形してカーボン粉粒同士の結合が不十分な欠陥部分を有した凝結体成形品Ａ（比較例１）に比較して、優位に高い曲げ強度を呈した。 As shown in FIG. 2, the aggregated molded product B (Embodiment 1) is formed of a molding material and a reforming material obtained by kneading carbon powder or rice husk charcoal and a phenol resin, and bonding the carbon particles together. Compared with the aggregated molded product A (Comparative Example 1) having an insufficient defect part, it exhibited a significantly higher bending strength.
以上に述べた結果から、カーボン粉粒および籾殻炭の表面にフェノール樹脂を配した本実施の形態による成形材料は、押出機で混練した比較例の成型用原料に比較して、底面と側面上部が均質であることから流動性に優れていることが確認できた。また、籾殻炭からなる表面層は高い強度を備え、なかでも本実施の形態による籾殻炭表面に半硬化状態のフェノール樹脂塗膜を形成した場合には、特に優れていることを確認した。 From the results described above, the molding material according to the present embodiment in which the phenol resin is arranged on the surface of the carbon particles and rice husk charcoal is compared with the molding material of the comparative example kneaded by the extruder, and the bottom surface and the upper side surface. Was confirmed to be excellent in fluidity. Further, it was confirmed that the surface layer made of rice husk charcoal has high strength, and in particular, when a semi-cured phenol resin coating film is formed on the surface of the rice husk charcoal according to the present embodiment, it was confirmed that the surface layer was particularly excellent.
以上のように、本実施の形態によるカーボン凝結体の成型用原料は高い流動性に基づいて得られた成型物の均質性と共に、実用上の必要とする特性に優れていることを確認した。 As described above, it was confirmed that the raw material for molding the carbon aggregate according to the present embodiment was excellent in the properties required for practical use as well as the homogeneity of the molded product obtained based on the high fluidity.
また、塗料を含浸させる表面層を成す改質材料において、結合材の含有量を多くして成形品の表面の平滑性を確保する場合には、そこに保持する気孔が少なくなることから、塗料の含浸が少なくなって塗膜の密着性が低下する傾向を呈するようになる。このため、改質材料には易分解性の繊維、例えば、強度低下を来さない程度の量であって、３０μｍ程度の太さを有するポリプロピレンの繊維（易分解性の繊維の一例）を混合することによって、塗料が含浸するための気孔を確保することができる。 Further, in the modified material forming the surface layer impregnated with the paint, when the content of the binder is increased to ensure the smoothness of the surface of the molded product, the pores retained therein are reduced. As a result, the adhesion of the coating film tends to decrease. For this reason, the modified material is mixed with easily degradable fibers, for example, polypropylene fibers (an example of easily degradable fibers) having a thickness of about 30 μm that does not cause a decrease in strength. By doing so, pores for impregnation of the paint can be secured.
この場合、繊維の材料には圧縮成形における成型温度で溶融する熱可塑性樹脂が好ましい。加熱・加圧状態で改質材料の粉粒の間隙にある繊維が流動を促すように作用するとともに、粉粒間の空隙に充填して不定形で連続して保持された後、高温の焼成処理過程で分解して、塗料の含浸に好適な気孔を形成するので、都合がよい。 In this case, the fiber material is preferably a thermoplastic resin that melts at the molding temperature in compression molding. In the heated / pressurized state, the fibers in the gaps between the particles of the modified material act to promote flow, and after filling the gaps between the granules and holding them in an irregular shape, firing at a high temperature It is convenient because it decomposes during the process to form pores suitable for impregnation of the paint.
なお、本実施の形態では、成形材料や改質材料の結合材にフェノール樹脂をはじめとする熱硬化性樹脂を用いたが、これに替えて、高温で流動性を呈するタールやピッチなどの炭素含有率の高い物質を用いることによって、高温焼成時における分解生成物を飛散した後の炭素が十分に残存して、収縮や結合力の不足が生じることもないので、代替が可能である。 In this embodiment, a thermosetting resin such as a phenol resin is used as a binder for a molding material or a reforming material. Instead, carbon such as tar or pitch that exhibits fluidity at high temperatures. By using a substance having a high content rate, carbon after the decomposition product at the time of high-temperature firing is sufficiently left behind, and shrinkage and lack of bonding strength do not occur.
実施の形態２．
圧縮成形によって種子殻燻蒸炭をカーボン粉粒に混合した成形材料を表面層に積層して得た鍋状の凝結体成型品とその製造方法を、以下に詳述する。 A pot-shaped aggregate molded product obtained by laminating a molding material obtained by mixing seed shell fumigation charcoal into carbon powder by compression molding on the surface layer and a manufacturing method thereof will be described in detail below.
まず、石油コークスを無酸素状態の高温（約３０００℃）で焼成してグラファイト化した黒鉛の塊状物を０．２ｍｍ以下に粉砕したカーボン粉粒物とアルコール（例えば、エタノール）と水とを混合した溶媒で希釈したフェノール溶液中の減圧下で混合し、その表面を十分に濡らした後、さらにカーボン粉粒を均一分散させるように混合しながらホルムアルデヒド（アルデヒド基を含む化合物の一例）を添加しながら、重合を進行させる。流動性に好適な半硬化状態を確保するに至るまで、本実施の形態では７０℃以下で約１５０分間の撹拌を行った。 First, carbon powder obtained by calcining petroleum coke at an oxygen-free high temperature (about 3000 ° C.) and graphitized to a mass of 0.2 mm or less, alcohol (for example, ethanol), and water are mixed. After mixing under reduced pressure in a phenol solution diluted with a solvent, and thoroughly wetting the surface, add formaldehyde (an example of a compound containing an aldehyde group) while mixing to further disperse the carbon particles. The polymerization is allowed to proceed. In this embodiment, stirring was performed at 70 ° C. or lower for about 150 minutes until a semi-cured state suitable for fluidity was ensured.
重合の進行とともに、溶剤中に分散するカーボン粉粒を核としながら半硬化状態のフェノール樹脂が塗膜を形成して析出し、エマルジョンを形成する。成形品の成形材料を成す成形材料とするには、これを冷却して半硬化状態のフェノール樹脂を固化させた状態で溶媒を飛散させて乾燥して粒状の微粉末を確保した後、フェノール樹脂のみの微粉末を比重分別により排除した。得られた成形材料は、カーボンの粉粒の外周面に膜として保持した粒状が備える未硬化状態のフェノール樹脂の保有率は約２１ｗｔ％であった。 As the polymerization proceeds, a semi-cured phenolic resin forms a coating and precipitates with the carbon particles dispersed in the solvent as the core, forming an emulsion. In order to obtain a molding material that forms a molding material of a molded product, the powder is cooled and the semi-cured phenol resin is solidified, and then the solvent is scattered and dried to secure a granular fine powder. Only fine powder was excluded by specific gravity fractionation. The obtained molding material had an uncured phenolic resin retention rate of about 21 wt% with the particles held as a film on the outer peripheral surface of the carbon particles.
成形材料の核に平均粒径が約３５μｍに粉砕した籾殻炭を用いて、表面に半硬化状態のフェノール樹脂を保有率が約２８ｗｔ％となるように調整した粒状の微粉末である改質材料を確保した。これに前述の成形材料の同量を加え、さらに熱可塑性樹脂であるポリアミドの繊維（易分解性の繊維の一例）を約３％混合して、鍋状成形品の表面層に用いた。籾殻炭は、草木又は種子殻の薫蒸炭の粉末の一例である。ポリアミド以外でも、ＰＢＴまたはポリプロピレンなどのオレフィン系樹脂でも同様の効果を奏する。 A reformed material which is a granular fine powder in which rice husk charcoal having an average particle size of about 35 μm is used as the core of the molding material, and the phenolic resin in a semi-cured state is adjusted to about 28 wt% on the surface. Secured. To this, the same amount of the above-mentioned molding material was added, and about 3% of a polyamide fiber (an example of an easily degradable fiber) as a thermoplastic resin was mixed and used for the surface layer of the pot-shaped molded product. Rice husk charcoal is an example of fumigated charcoal powder of vegetation or seed husk. In addition to polyamide, olefin-based resins such as PBT or polypropylene have the same effect.
次に、上述した成形材料などを用いて金型内での鍋状の成形品を得る手段について詳述する。硬化温度である約１６５℃に加熱した金型内に壁面肉厚の約４／５に見合う量の成形材料を均一な厚さになるように投入し、次いで、成形材料と改質材料の同量混合物を壁面肉厚の約１／５に見合う量を均一厚さになるように積層後、すぐに圧縮成形を行った。 Next, means for obtaining a pot-shaped molded product in the mold using the molding material described above will be described in detail. An amount of molding material corresponding to about 4/5 of the wall thickness is put into a mold heated to a curing temperature of about 165 ° C. so as to have a uniform thickness. After the amount mixture was laminated so that an amount corresponding to about 1/5 of the wall thickness was a uniform thickness, compression molding was performed immediately.
このとき、カーボン粉粒などを被覆したフェノール樹脂が、硬化過程に発生する副生成物である水蒸気などのガスの放散を促す反面、フェノール樹脂の過度な流出や流動不足に至らないよう、硬化反応の進行に伴う適正な流動粘度を確保するよう、１０〜３０秒間、触圧程度の低圧加圧後に金型を僅かに開放して発生した水蒸気などのガスを放出し、約１０Ｍｐａの高圧加圧して３００〜３６０秒間の保持をしてフェノール樹脂を硬化させた後、成形品を金型から取り出した。 At this time, the phenol resin coated with carbon particles, etc., promotes the release of gas such as water vapor, which is a by-product generated during the curing process. In order to ensure the proper fluid viscosity with the progress of the gas flow, the gas such as water vapor generated by slightly opening the mold after low pressure press for about 10 to 30 seconds is released, and high pressure press of about 10 Mpa is performed. The phenolic resin was cured by holding for 300 to 360 seconds, and then the molded product was taken out from the mold.
ここで用いた成形材料は、鋭角な破断面を備えたカーボン粉粒に半硬化状態のフェノール樹脂を被覆したことにより、表面が平滑な面を備えた粒状であるため、加熱・加圧時における金型内を、空隙を埋めながら好適な位置に流動するので、流動性に優れるという特徴を有する。 The molding material used here is a granule with a smooth surface by coating a semi-cured phenol resin on carbon particles with an acute fracture surface. Since it flows in a suitable position while filling the voids in the mold, it has a feature of excellent fluidity.
さらに、表面にフェノール樹脂未硬化物を備えた成形材料同士が接した部位で融着するので、従来の混合物のように結合材の存在しない部分が接して接合しない欠陥部分を生じないことから、高い強度や熱伝導率などの優れた諸特性を確保することができる。 Furthermore, since the molding material with the phenol resin uncured material on the surface is fused at the site where the materials are in contact with each other, it does not cause a defective portion that does not contact and join the portion where the binder does not exist like a conventional mixture, Excellent properties such as high strength and thermal conductivity can be ensured.
次に、上記成形品は無酸素雰囲気の約１２００℃でフェノール樹脂を炭化させて鍋状を成す凝結体成形品Ｃ（実施の形態２）を得た。このとき、フェノールの分解生成物が当該成形品から放散せずに内部に滞留して膨張し、鏡面層の近傍で亀裂や局部的な膨れ発生を防止するため、温度上昇を段階的に行うことが肝要である。 Next, the molded article was obtained by carbonizing a phenol resin at about 1200 ° C. in an oxygen-free atmosphere to obtain a condensate molded article C (Embodiment 2) having a pan shape. At this time, in order to prevent the decomposition product of phenol from staying inside the molded product without diffusing and expanding, and to prevent the occurrence of cracks and local swelling in the vicinity of the mirror surface layer, the temperature rise is performed in stages. Is essential.
つまり、フェノール樹脂の分解が活発になって急激な重量減少を来す３５０℃、５００℃、８００℃近傍は温度の緩い上昇または保持を行う。具体的には、３００℃迄を０．５℃／ｍｉｎで速く昇温後、３５０℃に１℃／ｈｒの緩い昇温で到達後、５時間の保持をした。また、４５０℃迄を５℃／ｈｒ、５００℃迄を１℃／ｈｒで到達後、５時間の保持をした。さらに、７５０℃迄を５℃／ｈｒ、８００℃迄を２℃／ｈｒで到達後、３時間の保持をした。その後、０．５℃／ｍｉｎで１２００℃に到達させて２時間の保持を行った。 That is, in the vicinity of 350 ° C., 500 ° C., and 800 ° C. where the decomposition of the phenol resin becomes active and causes a rapid weight loss, the temperature is slowly increased or maintained. Specifically, the temperature was rapidly increased up to 300 ° C. at 0.5 ° C./min, then reached 350 ° C. at a moderate temperature increase of 1 ° C./hr, and then held for 5 hours. Further, after reaching 450 ° C. at 5 ° C./hr and up to 500 ° C. at 1 ° C./hr, it was held for 5 hours. Further, after reaching 5 ° C./hr up to 750 ° C. and 2 ° C./hr up to 800 ° C., it was held for 3 hours. Then, it reached 1200 degreeC at 0.5 degreeC / min, and hold | maintained for 2 hours.
また、冷却については、０．５℃／ｍｉｎで室温近傍まで冷却した。 Moreover, about cooling, it cooled to room temperature vicinity at 0.5 degree-C / min.
これとは別に、成形材料と改質材料を混合せずに、籾殻炭に半硬化状態のフェノール樹脂が被覆した改質材料のみを表面層に配設した鍋状の凝結体成形品を作製し、これを比較試料である凝結体成形品Ｄ（比較例２）とした。 Separately from this, a pot-shaped condensate molded product in which only the modified material in which the husk charcoal is coated with a semi-cured phenolic resin is arranged on the surface layer is prepared without mixing the molding material and the modified material. This was designated as a condensed product D (Comparative Example 2) as a comparative sample.
次に、上記手段にて作製した凝結体成形品を比較したところ、凝結体成形品Ｃ（実施の形態２）に対して、比較試料の凝結体成形品Ｄ（比較例２）は、底面と側壁との境界部分で亀裂が発生した。これは、焼成処理段階における成形材料と改質材料の寸法変化率が大きく異なり、圧縮成形時に上型が直接、接する改質材料が内部にある成形材料に比較して流動性が劣るため、改質材料の多くが残留する成形品の底部と、多くが成形材料で構成される側壁部の界面で、強度低下を伴う焼成処理段階で生じる各材料の収縮率の差異に基づく応力に耐えられずに亀裂が発生したものである。 Next, when the aggregate molded product produced by the above means was compared, the aggregate molded product D (Comparative Example 2) of the comparative sample was compared with the bottom of the aggregate molded product C (Embodiment 2). Cracks occurred at the boundary with the side wall. This is because the ratio of dimensional change between the molding material and the reforming material in the firing process is greatly different, and the fluidity is inferior compared to the molding material in which the reforming material that is in direct contact with the upper mold during compression molding. It cannot withstand the stress due to the difference in the shrinkage rate of each material that occurs in the firing process stage with a decrease in strength at the interface between the bottom of the molded product where most of the quality material remains and the side wall that consists mostly of the molding material. Cracks occurred.
従って、凝結体成形品Ｃ（実施の形態２）は成形材料と改質材料の混合物で底面上層が構成されたので、寸法変化率の差異が縮小して発生する応力を抑制した。また、塗料を含浸して調理面を構成する改質材料にポリアミド繊維を混合したので、金型温度よりも低温で溶融して流動を促す効果を付与するので、底面部に改質材料の多くが滞留することなしに側壁部にまで到達したので、亀裂の発生が抑止できた。 Therefore, in the aggregate molded product C (Embodiment 2), the bottom surface upper layer is composed of the mixture of the molding material and the reforming material, and therefore the stress generated by reducing the difference in the dimensional change rate is suppressed. In addition, since polyamide fiber is mixed with the reforming material that impregnates the paint and constitutes the cooking surface, it gives the effect of promoting flow by melting at a temperature lower than the mold temperature. Since it reached the side wall without staying, the generation of cracks could be suppressed.
また、ポリアミドの繊維は、改質材料の粉粒同士が接する間隙と空隙を充填して不定形で連続して保持された後、高温の焼成処理過程で分解して気孔を形成するので、塗料の含浸に好適な気孔を形成するので、都合がよい。 Also, the polyamide fiber fills the gaps and voids where the particles of the modifying material are in contact with each other and is continuously held in an indeterminate shape, and then decomposes to form pores during the high-temperature firing treatment process. This is convenient because it forms pores suitable for impregnation of the resin.
なお、本実施の形態では、成形材料や改質材料の結合材にフェノール樹脂をはじめとする熱硬化性樹脂を用いたが、これに替えて、高温で流動性を呈するタールピッチなどの炭素含有率の高い物質を用いることによって、高温焼成時における分解生成物を飛散した後の炭素が十分に残存して、収縮や結合力の不足が生じることもないので、代替が可能である。 In this embodiment, a thermosetting resin such as a phenol resin is used as a binder for a molding material or a reforming material. Instead, a carbon-containing material such as tar pitch that exhibits fluidity at high temperatures is used. By using a substance having a high rate, the carbon after the decomposition products at the time of high-temperature firing are sufficiently left behind, so that shrinkage and lack of bonding force do not occur.
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| CN109044082A (en) * | 2018-09-29 | 2018-12-21 | 宁波百飞特厨具有限公司 | Frying pan |
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