JP4252278B2 - Method for producing heat-treated sheet molding material - Google Patents
Method for producing heat-treated sheet molding material Download PDFInfo
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- JP4252278B2 JP4252278B2 JP2002302595A JP2002302595A JP4252278B2 JP 4252278 B2 JP4252278 B2 JP 4252278B2 JP 2002302595 A JP2002302595 A JP 2002302595A JP 2002302595 A JP2002302595 A JP 2002302595A JP 4252278 B2 JP4252278 B2 JP 4252278B2
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- 239000012778 molding material Substances 0.000 title claims description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 28
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- 229910052751 metal Inorganic materials 0.000 claims description 18
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- 238000000465 moulding Methods 0.000 claims description 10
- 239000005995 Aluminium silicate Substances 0.000 claims description 8
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 description 21
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- 239000004412 Bulk moulding compound Substances 0.000 description 8
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- 239000004566 building material Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
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- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910000669 Chrome steel Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000737 Duralumin Inorganic materials 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
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- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 description 1
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Images
Landscapes
- Reinforced Plastic Materials (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、熱処理されたシート状成型材料の製造方法に関する。
【０００２】
【従来の技術】
従来、フェノール樹脂、無機フィラー、無機繊維を含有したシート状成型材料はフェノールＳＭＣ（シートモールディングコンパウンド）やフェノールＢＭＣ（バルクモールディングコンパウンド）と呼ばれ、それから成型される成型体は防火性に優れた材料として様々な用途に利用可能であることが知られている。とりわけ防火基準の厳しい建築分野においては家屋の外壁、屋根、床等の材料としての展開が可能である。これらの建築材料は一般にパネルの形状をしているものが多い。このため上記成型材料はシート状をしていることが好ましく、これをプレス成型で様々な形に加工するケースが多い。フェノール樹脂は熱硬化性樹脂であるため一定温度に加熱した金型にシート状成型材料を装てんし、一定時間、一定圧力で加圧した後に脱型して成型体を得る。このような方法は、例えば特開平３‐１４０３３２号公報に開示されている。
【０００３】
フェノールＳＭＣやフェノールＢＭＣをプレス成型によって成型する場合、もっとも困難なのはショートのない状態の製品を得ることである。ここでショートとは型内部の隅々まで成型材料が行き渡らず、製品の一部が欠けた状態となることを言う。一般に知られている不飽和ポリエステル樹脂系の成型材料に比べて、フェノール系の成型材料は型内での材料の流動性が小さく、このため複雑な形状をした型内では材料の行き渡らない部分が発生し、プレス工程での製品収率が悪化する傾向が見られる。ショートした部分を良く観察すると、その周辺部分の硬化物には成型材料中の樹脂分と一部の無機フィラーのみが流動し、無機繊維の含有量が著しく小さくなっていることがわかる。これは加熱状態で成型材料が型内を流動する際に、当初は均一に混合していた材料が分離を起こし、無機繊維は取り残され、流動しやすい樹脂分と無機フィラー分のみが流動した結果である。
【０００４】
このような状況は不飽和ポリエステル樹脂系の成型材料でも起こることが知られており、これを防止するための方法として成型材料を一定の温度で一定時間熱処理した後、加熱・加圧成型するということが行われる。このような方法は、例えば特開昭５５‐３７３０８号公報に開示されている。この方法によって成型材料中の樹脂成分は無機フィラー、無機繊維へ十分に含浸され、無機フィラー、無機繊維の表面と相互作用してより強固な界面を形成するようになる。この結果として高温下のプレスにおいても樹脂と無機フィラー、無機繊維が分離することなく、均一な組成で流動するようになる。この効果はフェノール系の成型材料についても同様である。
【０００５】
しかしながらフェノール系の成型材料は不飽和ポリエステル系の成型材料と比較して、このような熱処理において材料全体が均一に処理されにくいという欠点を有している。熱処理の効果は材料の硬度に現れてくるが、例えば建築材料用のパネルをプレス成型によって成型する際、１メートル四方の大きさのフェノールＳＭＣをオーブン中で熱処理すると、中央部分は熱処理が不十分でやわらかいままであり、周辺部分は熱処理が過剰となって硬くなりすぎる傾向が見られる。また処理に使用するオーブンの特性によっては材料の左右で硬度に差がみられることもある。このように材料の中で熱処理の度合いに差が出ると、成型の際のショートの発生率が高くなり好ましくない。処理の時間を長くすると処理効果は高くなるが、熱処理が過剰となると成型材料は硬くなりすぎて、成型時に全く流動しなくなってしまう。すなわち良好な成型を行うためには、材料全体を適度な時間で均一に熱処理することにより硬度のばらつきを最小限に抑える必要がある。またこの傾向は高い温度と短い時間で効率的に熱処理する場合、あるいは処理する成型材料の大きさが大きくなってくる場合に顕著となる。このため建築材料用途のように成型体が比較的大きく、さらに高い生産性を要求される成型材料を処理する場合にはこの問題が深刻になる。このような問題に対して特開平０４‐２１４３０６号公報には不飽和ポリエステル樹脂系の成型材料を高周波加熱によって均一に熱処理する方法が開示されているがフェノール系の成型材料においてはこの方法で均一な処理をすることは困難である。
【０００６】
【特許文献１】
特開平３−１４０３３２号公報
【特許文献２】
特開昭５５−３７３０８号公報
【特許文献３】
特開平４−２１４３０６号公報
【０００７】
【発明が解決しようとする課題】
本発明は、成型材料を均一に熱処理することのできる、熱処理されたシート状成型材料の製造方法を提供するものである。
【０００８】
【課題を解決するための手段】
本発明者は、前記、本発明課題を達成するために鋭意検討を重ねた結果、本発明を完成させるに至った。
すなわち、本発明は、下記の通りである。
１．少なくともフェノール樹脂、無機フィラー、無機繊維を含有したフェノール系のシート状成型材料を、オーブン中において、一定の温度雰囲気中で熱処理するに際して、該シート状成型材料をその両側から金属製のプレートにて挟み込み、該シート状成型材料の両面に該金属製のプレートを接触させた状態において、前記オーブン中に静置せしめて、かかる熱処理を行なうことを特徴とする熱処理されたフェノール系のシート状成型材料の製造方法。
２．前記無機フィラーが、カオリンクレーおよび／または水酸化アルミニウムを含むことを特徴とする前記１に記載の熱処理されたフェノール系のシート状成型材料の製造方法。
３．前記シート状成型材料の上面と下面に、それぞれキャリアフィルムが貼り付けられていることを特徴とする前記１又は２に記載の熱処理されたフェノール系のシート状成型材料の製造方法。
４．前記金属製のプレートが、予め処理温度に予熱されていることを特徴とする前記１乃至３の何れか一つに記載の熱処理されたフェノール系のシート状成型材料の製造方法。
５．前記金属製のプレートが、前記シート状成型材料よりも大きな寸法を有していることを特徴とする前記１乃至４の何れか一つに記載の熱処理されたフェノール系のシート状成型材料の製造方法。
【０００９】
【発明の実施の形態】
以下に、本発明について、その好ましい態様を中心に、詳細に説明する。
本発明は、少なくともフェノール樹脂、無機フィラー、無機繊維を含んだシート状成型材料に均一に熱履歴を加える方法に関する。
フェノール樹脂とは、レゾール系フェノール樹脂であっても、ノボラック系フェノール樹脂であっても良く、また、これらの樹脂に、必要に応じて重合度を高める目的で酸触媒や塩基触媒を添加して用いても良いが、常温で液状を示すレゾール系フェノール樹脂を無触媒で用いることが、成形加工が容易にできる点、生産性が上げられる点から好ましい。
【００１０】
フェノール樹脂のシート状成型材料中の含量としては、１〜６０質量パーセントであることが好ましく、１０〜４０質量パーセントであることがより好ましい。フェノール樹脂の含量をこの範囲とすることによって、良好な成形性と防火性が確保できる。なおフェノール樹脂は通常、フェノール樹脂中の樹脂成分に対して１〜４０質量パーセントの水分を含んでいる場合が多いが、この水分の質量もフェノール樹脂の質量とする。この水分の質量は特に限定されないが、樹脂と他の成分を混合する際に扱いやすい樹脂の性状を維持するため、レゾール樹脂中の含有量で１０〜３０質量パーセントの範囲とするのが好ましい。
【００１１】
無機フィラーとはカオリンクレー、水酸化アルミニウム、炭酸カルシウム、タルク、マイクロバルーン、硫化バリウム、無水ケイ酸、けい藻土、ガラスパウダー、マイカ、炭酸マグネシウム、三酸化アンチモン、ゾノトライト、トバモライト、ワラストナイト、けい砂等をいう。中でも得られる成型体の防火性を高めるためにカオリンクレイ、水酸化アルミニウムが好ましく用いられる。これらの無機フィラーは１種のみで用いることもできるし、２種以上の混合物として用いることもできる。無機フィラーとしてカオリンクレイと水酸化アルミニウムを含む場合、その混合比は質量比でカオリンクレイ：水酸化アルミニウム＝１：１０〜１０：１の範囲とすることが好ましく、１：６〜６：１の範囲とすることがより好ましい。無機フィラーの含量としてはシート状成型材料中の含量として１０〜７０質量パーセントであることが好ましく、２０〜６０質量パーセントであることがより好ましい。無機フィラーの含量をこの範囲とすることによって、相対的に樹脂の量が小さくなり、得られたパネルの防火性が低下するのを防止することが出来る。
【００１２】
無機繊維とはガラス繊維または鉱物繊維あるいはそれらの混合物をいう。特にガラス繊維は強度が大きく形状が均一なので好適である。本発明において、ガラス繊維はＥ−ガラス、Ｃ−ガラス、Ｔ−ガラス、ＡＲ−ガラス、Ｄ−ガラスなどガラスの種類は特に限定されないが、コスト面などから考えるとＥ−ガラスが好ましい。無機繊維の平均繊維径は得られるパネル強度を確保する点から３〜１００μｍが好ましく、６〜５０μｍであることがより好ましい。また無機繊維の平均繊維長は得られるパネル強度を確保する点および成形性の観点から０．０１〜５．０ｃｍが好ましく、０．１〜３．０ｃｍであることがより好ましい。
【００１３】
シート状成型材料とは、厚みに対して横幅と縦幅の大きい、加熱や酸硬化によって成型体に成型可能な材料をいう。厚みは０．１〜１００ｍｍが好ましく、１〜１０ｍｍがより好ましい。厚みをこの範囲とすることによって成型時のハンドリング性や成型性を良好に保つことができる。また横幅と縦幅は特に限定されないが、熱処理の際の作業性を考慮して、縦横の寸法をそれぞれ５０００ｍｍ以内、好ましくは２０００ｍｍ以内とするのが良い。またシート状成型材料の上面と下面にはシートのべたつきによる作業性の低下を防止するためキャリアフィルムが貼られていることが好ましい。このキャリアフィルムは素材がポリエチレン、ポリプロピレン、ポリアミド、ポリエステル、ポリ塩化ビニル、ポリ塩化ビニリデン等で厚みが１０〜１００μｍのものを使用するのが好ましい。キャリアフィルムの厚みをこの範囲とすることにより、シート状成型材料を十分に保護し、熱処理する際の処理効率を良好に保つことができる。またこのシート状成型材料にはフェノール樹脂に増粘性を付与したり、得られた成型体に難燃性、耐候性、離型性等を付与するために難燃剤、紫外線吸収剤、内部離型剤、増粘剤等の添加剤を加えることが好ましい。本発明において特に好ましい添加剤は増粘剤として水酸化カルシウム、内部離型剤としてステアリン酸亜鉛であり、シート状成型材料中に０．０１〜５質量パーセント含有されていることが好ましい。またＳＭＣシートを作製する際、樹脂ペーストの粘度が高すぎるときは粘度調整用の純水を必要量加えてもよい。
【００１４】
シート状成型材料を作製する方法については、本発明の場合特に限定されず、例えば「強化プラスチック成形材料」（平成元年、社団法人強化プラスチック協会編）ＳＭＣ編、ＢＭＣ編に記載されているような公知の方法を用いることができる。材料中に含まれる無機繊維の長さを一定以上に保ちたい場合にはＳＭＣ（シートモールディングコンパンド）法により材料を作製するのが好適であり、無機繊維の長さを短くしたい場合にはＢＭＣ（バルクモールディングコンパウンド）法により材料を作製するのが好適である。ここでＳＭＣ（シートモールディングコンパンド）法とは主に、成型材料を構成する原料のうち無機繊維以外の成分を混練してペースト状とし、このペーストをキャリアフィルム上にコーティングした後、このフィルム２枚の間に無機繊維を適当な長さに切断しながら挟みこみ２枚のフィルムを一体化して成型材料とする方法であり、例えば特開昭４８−９４７６４号公報、特開昭５４−３９４６９号公報に記載されている。またＢＭＣ（バルクモールディングコンパンド）法とは主に、無機繊維も含めた成形材料を構成する全ての原料を同時にニーダー等の混練機で混練し、混練後のコンパンドをシート状、棒状、塊状に加工して成形材料とする方法であり、例えば特願２０００−０２４３０９に記載されている。
【００１５】
本発明は上記のシート状成型材料を熱処理する場合、その両面（上面と下面）に金属製のプレートを接触させながら熱処理を行う。ここで金属製のプレートとは、銀、銅、金、アルミニウム、マグネシウム、タングステン、鉄等の単体金属や、ステンレス鋼、クロム鋼、ジュラルミン、真チュウ、鋳鉄等の合金で構成されたプレート（板）をいう。なおその材料となる金属については、その一部が酸化物等の化合物となっていても良い。
【００１６】
プレートの大きさは特に限定されない。厚みは０．１〜１００ｍｍが好ましく、１〜１０ｍｍがより好ましい。横と縦の寸法は処理するシート状成型材料の大きさに合わせて選択すれば良いが、熱処理の均一性を保持するため処理するシートの大きさに対して、縦横の幅がおよそ１０パーセント大きいプレートを選択することが好ましい。また本発明において熱処理とはシート状成型材料に一定時間、定温で熱履歴を加えることをいう。加圧・加熱して材料を完全に硬化させ成型体を得る工程とは異なる。熱処理の方法については上記のようにシート状成型材料の両面に金属製のプレートを接触させた状態で、オーブン中のような一定の温度雰囲気中で一定時間保持して行う。この時、金属製プレートがしっかり密着していない場合は固定金具を用いて固定しても良い。また金属製のプレートは予め処理温度に余熱しておくことが好ましい。また熱処理の温度については４０〜１００℃が本法の効果を発揮するのに好ましい温度範囲である。こうすることによってより均一な熱処理を行うことが可能となる。
以下、実施例により本発明を説明する。
【００１７】
【実施例１】
レゾール系フェノール樹脂（昭和高分子（株）製、商品名「ＢＲＬ−２４０」）１００質量部、純水１６質量部、増粘剤として水酸化カルシウム（関東化学（株）製 試薬特級）１質量部、内部離型剤としてステアリン酸亜鉛（関東化学（株）製 試薬一級）３質量部、水酸化アルミニウム（昭和電工（株）製、商品名「ハイジライトＨ３２」）８３質量部、カオリンクレイ（ＥＮＧＥＬＨＡＲＤ社製、商品名「ＡＳＰ-４００Ｐ」）８３質量部をハンドミキサー（芝浦製作所製、品名「ＢＭＶ-１５０Ａ」）で１０分間混合し樹脂ペーストとした。
この樹脂ペーストをＳＭＣ製造装置（月島機械（株）製）にセットした。厚み４０μｍポリプロピレン製フィルムをキャリアーフィルムとしてこの原料ペーストを１ｍｍ厚で塗布しながら装置の上下２か所から走らせた。この際、ガラス繊維ロービング（日東紡（株）製、商品名「ＲＳ２４０ＰＢ」）を平均繊維長２５ｍｍに切断しながら２枚のキャリアーフィルムへ挟み込むように添加した。このときの添加量は得られるシート状成型材料のガラス繊維の含量がおよそ２０質量パーセントとなるように調整した。得られたシート状成型材料の厚みはおよそ３ｍｍとなった。これを縦５００ｍｍ、横１０００ｍｍの大きさに裁断して熱処理を行った。このとき予め８０℃に予熱した、厚み５ｍｍ、縦６００ｍｍ、横１１００ｍｍの鋼板プレート（規格ＳＳ４１）２枚に、図１に示すように、シート状成型材料を挟み込み、８０℃のオーブン（高林理化株式会社製、型式「ＰＳＦＳ‐１５１０型」）中で４時間静置した。これを取り出し室温になるまで放置してから硬度計（高分子計器株式会社製、アスカーＣ型）で硬度を測定した。硬度は、図２に示すように、シート全面に対して５０箇所測定しその平均値、範囲、標準偏差で熱処理の均一性を評価した。図３および表１に結果を示した。硬度の値はシート全体に対してほぼ定値であり均一な熱処理が施されていることがわかる。
【００１８】
【実施例２】
用いる金属製プレートを厚み１０ｍｍのアルミ板（規格Ａ１１００）とする以外は、実施例１と同様にシート状成型材料を作製して熱処理を施し硬度を評価した。結果を図３および表１に示した。実施例１と同様、硬度の値はシート全体に対してほぼ定値であり均一な熱処理が施されていることがわかる。
【００１９】
【実施例３】
用いる金属製プレートを厚み１０ｍｍのステンレス鋼板（ＳＵＳ３０４）とする以外は、実施例１と同様にシート状成型材料を作製して熱処理を施し硬度を評価した。結果を図３および表１に示した。実施例１および２と同様、硬度の値はシート全体に対してほぼ定値であり均一な熱処理が施されていることがわかる。
【００２０】
【実施例４】
レゾール系フェノール樹脂（昭和高分子（株）製、商品名「ＢＲＬ−２４０」）１００質量部、純水１６質量部、増粘剤として水酸化カルシウム（関東化学（株）製 試薬特級）１質量部、内部離型剤としてステアリン酸亜鉛（関東化学（株）製 試薬一級）３質量部、水酸化アルミニウム（昭和電工（株）製、商品名「ハイジライトＨ３２」）８３質量部、カオリンクレイ（ＥＮＧＥＬＨＡＲＤ社製、商品名「ＡＳＰ-４００Ｐ」）８３質量部、ガラス繊維チョップドストランド（日東紡（株）製、商品名「ＲＳ２４０ＰＢ」を裁断、平均繊維長３ｍｍ）をオムニミキサー（千代田技研工業（株）製、商品名「ＯＭ−５」）で１０分間混合した。この混合物をち厚み４０μｍポリプロピレン製キャリアーフィルム２枚の間にはさみこんで、ハンドローラーを用いておよそ３ｍｍの厚みのシート状成型材料とした。これを実施例１と同様に処理して評価した結果を図３および表１に示した。実施例１〜３と同様、硬度の値はシート全体に対してほぼ定値であり均一な熱処理が施されていることがわかる。
【００２１】
【比較例１】
熱処理の際に鋼板プレートを用いず、シート状成型材料をそのままオーブンの中で静置する以外は実施例１と同様にシート状成型材料を作製し評価した。結果を図３および表１に示した。実施例と比較し、シート中央部の硬度が小さく、周辺部の硬度が大きくになりる傾向が見られる。
【００２２】
【表１】
【発明の効果】
本発明により、熱処理を均一におこなうことができ、硬度のばらつきの少ない、熱履歴を受けたシート状成型材料を製造することが出来る。
【図面の簡単な説明】
【図１】本発明において、シート状成型材料を熱処理する方法の例を示す断面図である。
【図２】本発明の実施例および比較例において、シート状成型材料の硬度を測定するときの測定点（黒点）の位置と番号を表した平面図である。
【図３】本発明の実施例と比較例において測定した硬度の測定値を示すグラフである。測定位置の番号は図２に示された番号に対応している。
【符号の説明】
１ 金属製プレート
２ キャリアフィルム
３ シート状成型材料[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a heat-treated sheet-shaped molding material.
[0002]
[Prior art]
Conventionally, a sheet-shaped molding material containing phenol resin, inorganic filler, and inorganic fiber is called phenol SMC (sheet molding compound) or phenol BMC (bulk molding compound), and the molded product molded therefrom is a material with excellent fire resistance. It is known that it can be used for various purposes. In particular, in the construction field with strict fire prevention standards, it can be developed as materials for the outer walls, roofs, floors, etc. of houses. Many of these building materials generally have a panel shape. For this reason, the molding material is preferably in the form of a sheet, and there are many cases where this is processed into various shapes by press molding. Since the phenolic resin is a thermosetting resin, a sheet-shaped molding material is loaded on a mold heated to a constant temperature, pressed at a certain pressure for a certain time, and then demolded to obtain a molded body. Such a method is disclosed in, for example, Japanese Patent Laid-Open No. 3-140332.
[0003]
When phenol SMC or phenol BMC is molded by press molding, the most difficult thing is to obtain a product without a short circuit. Here, short means that the molding material does not reach every corner of the mold, and a part of the product is missing. Compared to generally known unsaturated polyester resin molding materials, phenolic molding materials have less fluidity in the mold, so there are parts where the material does not spread in the complex shaped mold. The product yield in the press process tends to deteriorate. When the shorted part is observed well, it can be seen that only the resin content in the molding material and a part of the inorganic filler flow in the cured product in the peripheral part, and the content of the inorganic fiber is remarkably reduced. This is because when the molding material flows in the mold in the heated state, the material that was originally mixed uniformly is separated, the inorganic fibers are left behind, and only the resin component and the inorganic filler component that flow easily flow. It is.
[0004]
It is known that such a situation also occurs in unsaturated polyester resin-based molding materials, and as a method for preventing this, the molding material is heat-treated at a certain temperature for a certain time, and then heated and pressure-molded. Is done. Such a method is disclosed, for example, in JP-A-55-37308. By this method, the resin component in the molding material is sufficiently impregnated into the inorganic filler and the inorganic fiber, and interacts with the surface of the inorganic filler and the inorganic fiber to form a stronger interface. As a result, even in a press at a high temperature, the resin, the inorganic filler, and the inorganic fiber flow without separation and with a uniform composition. This effect is the same for phenolic molding materials.
[0005]
However, phenol-based molding materials have the disadvantage that the entire material is difficult to be uniformly treated by such heat treatment as compared with unsaturated polyester-based molding materials. The effect of heat treatment appears in the hardness of the material. For example, when a panel for building material is molded by press molding, if a phenol SMC with a size of 1 meter square is heat-treated in an oven, the heat treatment is insufficient in the center part. However, there is a tendency for the peripheral part to become too hard due to excessive heat treatment. Depending on the characteristics of the oven used for processing, there may be a difference in hardness between the right and left of the material. Thus, if there is a difference in the degree of heat treatment among the materials, the occurrence rate of short circuit during molding becomes high, which is not preferable. If the treatment time is lengthened, the treatment effect is enhanced, but if the heat treatment is excessive, the molding material becomes too hard and does not flow at all during molding. That is, in order to perform good molding, it is necessary to minimize the variation in hardness by uniformly heat-treating the entire material in an appropriate time. This tendency becomes prominent when the heat treatment is efficiently performed at a high temperature and in a short time, or when the size of the molding material to be processed increases. For this reason, this problem becomes serious when processing a molding material that requires a relatively large molded product and requires higher productivity, such as a building material application. To solve this problem, Japanese Patent Laid-Open No. 04-214306 discloses a method of uniformly heat-treating an unsaturated polyester resin-based molding material by high-frequency heating. It is difficult to perform a proper process.
[0006]
[Patent Document 1]
Japanese Patent Laid-Open No. 3-140332 [Patent Document 2]
JP 55-37308 A [Patent Document 3]
Japanese Patent Laid-Open No. 4-214306
[Problems to be solved by the invention]
The present invention provides a method for producing a heat-treated sheet-like molding material that can uniformly heat-treat the molding material.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above-described object of the present invention, the present inventor has completed the present invention.
That is, the present invention is as follows.
1. When a phenolic sheet-shaped molding material containing at least a phenol resin, an inorganic filler, and inorganic fibers is heat-treated in a constant temperature atmosphere in an oven, the sheet-shaped molding material is applied to a metal plate from both sides thereof. pinching, in a state in which both sides are brought into contact with the metal plate of the sheet-like molding material is allowed to stand in the oven, the sheet-like molding material of phenolic heat treated, characterized in that performing the heat treatment Manufacturing method.
2. Wherein the inorganic filler, the method for manufacturing a sheet-like molding material of the heat-treated phenol according to the 1, characterized in that it comprises a kaolin clay and / or aluminum hydroxide.
3. 3. The method for producing a heat-treated phenol-based sheet-shaped molding material according to 1 or 2, wherein carrier films are respectively attached to an upper surface and a lower surface of the sheet-shaped molding material.
4). 4. The method for producing a heat-treated phenolic sheet-shaped molding material according to any one of 1 to 3, wherein the metal plate is preheated to a treatment temperature in advance.
5. 5. The heat-treated phenol-based sheet-shaped molding material according to any one of 1 to 4, wherein the metal plate has a size larger than that of the sheet-shaped molding material. Method.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Below, this invention is demonstrated in detail focusing on the preferable aspect.
The present invention relates to a method for uniformly applying a thermal history to a sheet-shaped molding material containing at least a phenol resin, an inorganic filler, and inorganic fibers.
The phenol resin may be a resole phenol resin or a novolac phenol resin, and an acid catalyst or a base catalyst may be added to these resins for the purpose of increasing the degree of polymerization as required. Although it may be used, it is preferable to use a resol-type phenol resin which is liquid at room temperature without a catalyst from the viewpoint of easy molding and productivity.
[0010]
As content in the sheet-like molding material of a phenol resin, it is preferable that it is 1-60 mass percent, and it is more preferable that it is 10-40 mass percent. By making the content of the phenol resin within this range, good moldability and fire resistance can be ensured. In addition, although the phenol resin usually contains 1 to 40 mass percent of water with respect to the resin component in the phenol resin in many cases, the mass of this water is also the mass of the phenol resin. The mass of the moisture is not particularly limited, but is preferably in the range of 10 to 30 percent by mass in the resol resin in order to maintain easy-to-handle resin properties when the resin and other components are mixed.
[0011]
Inorganic fillers are kaolin clay, aluminum hydroxide, calcium carbonate, talc, microballoon, barium sulfide, silicic anhydride, diatomaceous earth, glass powder, mica, magnesium carbonate, antimony trioxide, zonotlite, tobermorite, wollastonite, This refers to sand. Of these, kaolin clay and aluminum hydroxide are preferably used in order to improve the fire resistance of the molded article obtained. These inorganic fillers can be used alone or as a mixture of two or more. When kaolin clay and aluminum hydroxide are included as the inorganic filler, the mixing ratio is preferably in the range of kaolin clay: aluminum hydroxide = 1: 10 to 10: 1 by mass ratio of 1: 6 to 6: 1. It is more preferable to set the range. The content of the inorganic filler is preferably 10 to 70 mass percent, more preferably 20 to 60 mass percent, as the content in the sheet-shaped molding material. By setting the content of the inorganic filler within this range, it is possible to prevent the amount of the resin from becoming relatively small and the fire resistance of the obtained panel from being lowered.
[0012]
Inorganic fibers refer to glass fibers, mineral fibers or mixtures thereof. In particular, glass fiber is suitable because of its high strength and uniform shape. In the present invention, the glass fiber is not particularly limited in the type of glass such as E-glass, C-glass, T-glass, AR-glass, and D-glass, but E-glass is preferable from the viewpoint of cost. The average fiber diameter of the inorganic fibers is preferably 3 to 100 μm, and more preferably 6 to 50 μm, from the viewpoint of securing the obtained panel strength. The average fiber length of the inorganic fibers is preferably 0.01 to 5.0 cm, more preferably 0.1 to 3.0 cm from the viewpoint of securing the obtained panel strength and moldability.
[0013]
The sheet-shaped molding material refers to a material that has a large width and length with respect to the thickness and can be molded into a molded body by heating or acid curing. The thickness is preferably 0.1 to 100 mm, and more preferably 1 to 10 mm. By making the thickness within this range, it is possible to maintain good handling properties and moldability during molding. The horizontal width and the vertical width are not particularly limited, but the vertical and horizontal dimensions are preferably within 5000 mm, preferably within 2000 mm, in consideration of workability during heat treatment. Moreover, it is preferable that a carrier film is affixed to the upper and lower surfaces of the sheet-shaped molding material in order to prevent deterioration of workability due to stickiness of the sheet. This carrier film is preferably made of polyethylene, polypropylene, polyamide, polyester, polyvinyl chloride, polyvinylidene chloride or the like having a thickness of 10 to 100 μm. By setting the thickness of the carrier film within this range, it is possible to sufficiently protect the sheet-shaped molding material and maintain good processing efficiency during heat treatment. In addition, this sheet-shaped molding material is provided with a flame retardant, an ultraviolet absorber, an internal mold release agent in order to impart thickening to the phenol resin, or to impart flame retardancy, weather resistance, releasability, etc. to the obtained molded product. It is preferable to add additives such as an agent and a thickener. Particularly preferred additives in the present invention are calcium hydroxide as a thickener and zinc stearate as an internal mold release agent, and it is preferably contained in the sheet-form molding material in an amount of 0.01 to 5 mass percent. Moreover, when producing the SMC sheet, if the viscosity of the resin paste is too high, a necessary amount of pure water for viscosity adjustment may be added.
[0014]
The method for producing the sheet-shaped molding material is not particularly limited in the case of the present invention. For example, as described in “Strengthened plastic molding material” (edited by the Japan Reinforced Plastics Association), SMC edition, BMC edition. Any known method can be used. In order to keep the length of the inorganic fiber contained in the material above a certain level, it is preferable to produce the material by the SMC (Sheet Molding Compound) method, and in order to shorten the length of the inorganic fiber, BMC ( It is preferable to produce the material by a bulk molding compound) method. Here, the SMC (sheet molding compound) method is mainly used to knead ingredients other than inorganic fibers among the raw materials constituting the molding material into a paste, coat this paste on a carrier film, In this method, the inorganic fiber is cut into an appropriate length between the two films and the two films are integrated to form a molding material. For example, Japanese Patent Laid-Open Nos. 48-94764 and 54-39469 are disclosed. It is described in. The BMC (Bulk Molding Compound) method is mainly used to knead all the raw materials composing the molding material including inorganic fibers with a kneader or other kneader at the same time, and process the compound after kneading into a sheet, rod, or block. For example, it is described in Japanese Patent Application No. 2000-024309.
[0015]
In the present invention, when the above-described sheet-shaped molding material is heat-treated, the heat-treatment is performed while contacting a metal plate on both surfaces (upper surface and lower surface). Here, the metal plate is a plate (plate) made of a single metal such as silver, copper, gold, aluminum, magnesium, tungsten, or iron, or an alloy such as stainless steel, chrome steel, duralumin, true chew, or cast iron. ). In addition, about the metal used as the material, the one part may become compounds, such as an oxide.
[0016]
The size of the plate is not particularly limited. The thickness is preferably 0.1 to 100 mm, and more preferably 1 to 10 mm. The horizontal and vertical dimensions may be selected in accordance with the size of the sheet-shaped molding material to be processed, but the vertical and horizontal width is approximately 10% larger than the size of the sheet to be processed in order to maintain the uniformity of the heat treatment. It is preferred to select a plate. In the present invention, the heat treatment means adding a heat history to the sheet-shaped molding material at a constant temperature for a certain time. This is different from the process of obtaining a molding by pressurizing and heating to completely cure the material. As for the heat treatment method, as described above, the metal plate is brought into contact with both surfaces of the sheet-shaped molding material, and the heat treatment is carried out by holding for a certain time in a constant temperature atmosphere such as in an oven. At this time, if the metal plate is not firmly attached, it may be fixed using a fixing bracket. The metal plate is preferably preheated to the processing temperature in advance. Moreover, about the temperature of heat processing, 40-100 degreeC is a preferable temperature range for exhibiting the effect of this method. By doing so, a more uniform heat treatment can be performed.
Hereinafter, the present invention will be described by way of examples.
[0017]
[Example 1]
100 parts by mass of resol phenol resin (trade name “BRL-240”, manufactured by Showa High Polymer Co., Ltd.), 16 parts by mass of pure water, 1 mass of calcium hydroxide as a thickener (reagent special grade, manufactured by Kanto Chemical Co., Ltd.) Part, 3 parts by weight of zinc stearate (reagent grade, manufactured by Kanto Chemical Co., Ltd.), 83 parts by weight of aluminum hydroxide (made by Showa Denko Co., Ltd., trade name “Hijilite H32”), kaolin clay ( 83 parts by mass of ENGELHARD (trade name “ASP-400P”) was mixed with a hand mixer (trade name “BMV-150A”, manufactured by Shibaura Seisakusho) for 10 minutes to obtain a resin paste.
This resin paste was set in an SMC manufacturing apparatus (manufactured by Tsukishima Kikai Co., Ltd.). A 40 μm thick polypropylene film was used as a carrier film, and this raw material paste was applied at a thickness of 1 mm, and was run from two places above and below the apparatus. At this time, glass fiber roving (manufactured by Nittobo Co., Ltd., trade name “RS240PB”) was added so as to be sandwiched between two carrier films while cutting to an average fiber length of 25 mm. The addition amount at this time was adjusted so that the glass fiber content of the obtained sheet-shaped molding material was about 20 mass percent. The thickness of the obtained sheet-shaped molding material was about 3 mm. This was cut into a size of 500 mm in length and 1000 mm in width and subjected to heat treatment. At this time, as shown in FIG. 1, a sheet-shaped molding material is sandwiched between two steel plate plates (standard SS41) having a thickness of 5 mm, a length of 600 mm, and a width of 1100 mm preheated to 80 ° C., and an oven at 80 ° C. (Takabayashi Rika Co., Ltd.). The product was allowed to stand for 4 hours in a company model “PSFS-1510”. This was taken out and allowed to stand at room temperature, and then the hardness was measured with a hardness meter (Asker C type, manufactured by Kobunshi Keiki Co., Ltd.). As shown in FIG. 2, the hardness was measured at 50 points on the entire sheet surface, and the uniformity of the heat treatment was evaluated based on the average value, range, and standard deviation. The results are shown in FIG. 3 and Table 1. It can be seen that the hardness value is almost constant for the entire sheet, and uniform heat treatment is performed.
[0018]
[Example 2]
Except that the metal plate to be used is an aluminum plate (standard A1100) having a thickness of 10 mm, a sheet-like molding material was prepared and heat-treated in the same manner as in Example 1 to evaluate the hardness. The results are shown in FIG. As in Example 1, the hardness value is almost constant for the entire sheet, and it can be seen that uniform heat treatment is performed.
[0019]
[Example 3]
Except that the metal plate to be used was a stainless steel plate (SUS304) having a thickness of 10 mm, a sheet-like molding material was prepared and heat-treated in the same manner as in Example 1 to evaluate the hardness. The results are shown in FIG. As in Examples 1 and 2, the hardness value is almost constant for the entire sheet, and it can be seen that uniform heat treatment is performed.
[0020]
[Example 4]
100 parts by mass of resol phenol resin (trade name “BRL-240”, manufactured by Showa High Polymer Co., Ltd.), 16 parts by mass of pure water, 1 mass of calcium hydroxide as a thickener (reagent special grade, manufactured by Kanto Chemical Co., Ltd.) Part, 3 parts by weight of zinc stearate (reagent grade, manufactured by Kanto Chemical Co., Ltd.), 83 parts by weight of aluminum hydroxide (made by Showa Denko Co., Ltd., trade name “Hijilite H32”), kaolin clay ( ENGELHARD, trade name “ASP-400P” 83 parts by mass, glass fiber chopped strand (manufactured by Nittobo Co., Ltd., trade name “RS240PB”,
[0021]
[Comparative Example 1]
A sheet-shaped molding material was prepared and evaluated in the same manner as in Example 1 except that the sheet-shaped molding material was left in the oven as it was without using a steel plate during the heat treatment. The results are shown in FIG. Compared with the examples, there is a tendency that the hardness of the central portion of the sheet is small and the hardness of the peripheral portion is large.
[0022]
[Table 1]
【The invention's effect】
According to the present invention, it is possible to produce a sheet-shaped molding material that can be uniformly subjected to heat treatment and that has undergone a thermal history with little variation in hardness.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing an example of a method for heat-treating a sheet-shaped molding material in the present invention.
FIG. 2 is a plan view showing positions and numbers of measurement points (black dots) when measuring the hardness of a sheet-shaped molding material in Examples and Comparative Examples of the present invention.
FIG. 3 is a graph showing measured values of hardness measured in Examples and Comparative Examples of the present invention. The number of the measurement position corresponds to the number shown in FIG.
[Explanation of symbols]
1
Claims (5)
該シート状成型材料をその両側から金属製のプレートにて挟み込み、該シート状成型材料の両面に該金属製のプレートを接触させた状態において、前記オーブン中に静置せしめて、かかる熱処理を行なうことを特徴とする熱処理されたフェノール系のシート状成型材料の製造方法。When a phenolic sheet-shaped molding material containing at least a phenol resin, an inorganic filler, and inorganic fibers is heat-treated in a constant temperature atmosphere in an oven,
The sheet-shaped molding material is sandwiched between metal plates from both sides, and the metal plate is brought into contact with both surfaces of the sheet-shaped molding material , and then left in the oven to perform the heat treatment . A method for producing a heat-treated phenolic sheet-shaped molding material, characterized in that:
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| JP2002302595A JP4252278B2 (en) | 2002-10-17 | 2002-10-17 | Method for producing heat-treated sheet molding material |
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| JP2002302595A JP4252278B2 (en) | 2002-10-17 | 2002-10-17 | Method for producing heat-treated sheet molding material |
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| JP4252278B2 true JP4252278B2 (en) | 2009-04-08 |
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| CN101812908B (en) * | 2010-04-02 | 2013-11-06 | 朱雄 | Fire-proof heat insulation composite decorative plate and manufacture process thereof |
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