JP4788070B2

JP4788070B2 - Manufacturing method of fiber reinforced thermosetting resin decorative board

Info

Publication number: JP4788070B2
Application number: JP2001190643A
Authority: JP
Inventors: 一弘高橋
Original assignee: Dai Nippon Printing Co Ltd
Current assignee: Dai Nippon Printing Co Ltd
Priority date: 2001-06-25
Filing date: 2001-06-25
Publication date: 2011-10-05
Anticipated expiration: 2021-06-25
Also published as: JP2003001657A

Description

【０００１】
【発明の属する技術分野】
本発明は、建築物の床材や壁材、浴室、洗面台等の各種用途で、ＦＲＰ（繊維強化プラスチック）成形品等として使用され得る、繊維強化熱硬化性樹脂化粧板を製造する方法に関する。
【０００２】
【従来の技術】
従来、繊維強化熱硬化性樹脂化粧板を製造する方法としては、例えば、模様付き不織布、印刷紙等の加飾シートに、熱硬化性樹脂を含浸させた未硬化シートに、ガラス繊維等の補強繊維（強化繊維）を含む熱硬化性樹脂未硬化基材層を重ねて、加熱加圧し熱硬化させて積層する方法（特開昭４８−１２８７６号公報等参照）が知られている。また、未硬化基材層には、シート状のＳＭＣ（シートモールディングコンパウンド）や、塊状のＢＭＣ（バルクモールディングコンパウンド）を用いれば、作業性等がより向上する。
【０００３】
この場合、補強繊維によって強度が増すが、該繊維によって表面凹凸が出来、平滑性が低下する。そこで、特に表面凹凸が目立ち易い鏡面性が要求される場合には、ポリエチレンテレフタレート等から成る熱可塑性樹脂シートの裏面に装飾層を印刷した印刷シートの裏面に、不織布を裏打ちした化粧シートを用いて、該化粧シートの裏面側にＳＭＣ等の未硬化基材層を重ね、加熱加圧して硬化させて積層する方法（特開平８−１１８３８４号公報等参照）等も開示されている。
【０００４】
【発明が解決しようとする課題】
しかしながら、化粧板表面が熱可塑性樹脂シートとなる様な構成では、鏡面性は良いが、熱硬化性樹脂で表面を構成する場合に比べて、表面の耐熱性が劣った。また、未硬化基材層にＳＭＣやＢＭＣを用いれば、作業性は良いが、その反面、補強繊維として短繊維が使用される関係で、長繊維が使われる織布等による繊維強化に比べて、機械的強度が劣ることがあった。
【０００５】
すなわち、本発明の課題は、鏡面性、表面耐熱性、及び機械的強度を良くできる、繊維強化熱硬化性樹脂化粧板の製造方法を提供することである。また、生産性も良好な繊維強化熱硬化性樹脂化粧板の製造方法を提供することである。
【０００６】
【課題を解決するための手段】
そこで、上記課題を解決すべく、本発明の繊維強化熱硬化性樹脂化粧板の製造方法では、補強繊維と熱硬化性樹脂の未硬化物とから成る未硬化基材層と、補強繊維を含ま無い熱硬化性樹脂の未硬化物から成る未硬化表面層とを、間に繊維質シートを挟んで積層した状態で、鏡面板をその鏡面が上記未硬化表面層に当接する様にして加熱加圧して、前記未硬化基材層及び上記未硬化表面層中の熱硬化性樹脂を硬化させて、次いで、加熱加圧を停止した後、未硬化表面層が硬化して成る表面層上から鏡面板を剥離除去する方法とした。
【０００７】
この様な製造方法とすることで、化粧板表面を形成する表面層（未硬化表面層の硬化物）中には、補強繊維が含まれていない為に、鏡面性を良くでき、且つ該表面層は熱硬化性樹脂の硬化物から成る為に、表面耐熱性も良くできる。しかも、繊維質シートが中間層として介在している為に、基材層（未硬化基材層の硬化物）中の補強繊維がたとえ短繊維であっても、機械的強度を良く出来る。従って、鏡面性、表面耐熱性、及び機械的強度が得られる製造方法となる。
【０００８】
また、本発明の繊維強化熱硬化性樹脂化粧板の製造方法は、上記方法に於いて、押出し機により補強繊維を含む樹脂組成物を押出して未硬化基材層をベルト上に形成し、更に該未硬化基材層上に繊維質シートを積層し、更に該繊維質シート上に、押出し機により補強繊維を含ま無い樹脂組成物を押出して未硬化表面層を積層し、次いで、、未硬化表面層側に加圧ベルトとして鏡面板とする鏡面加圧ベルトを用い、上下から加圧ベルトで挟んでベルトプレス方式にて加熱加圧を行う様にした。
【０００９】
この様な方法とすることで、積層及び加熱加圧操作を、バッチ式の間欠処理では無く、連続処理で円滑に行えるので、生産性が良くなる。
【００１０】
【発明の実施の形態】
以下、図面を参照しながら本発明の実施の形態を説明する。
【００１１】
〔要旨〕
先ず、図１は本発明による繊維強化熱硬化性樹脂化粧板の製造方法を、その一形態（枚葉熱プレス機による加熱加圧方式）で概念的に説明する概念図である。同図に示す形態では、先ず、図１（Ａ）の如く、下型２１１内に、補強繊維１１と熱硬化性樹脂の未硬化物１２Ａとから成る板状或いはシート状の未硬化基材層１０Ａを積層する。次いで、図１（Ｂ）の如く、未硬化樹脂基材層１０Ａの上に繊維質シート２１を載せ、次いで、図１（Ｃ）の如く、更に該繊維質シート２１の上に、補強繊維を含まない熱硬化性樹脂の未硬化物からなる未硬化表面層３０Ａを載せ、該未硬化表面層３０Ａの上に鏡面板４３をその鏡面が未硬化表面層３０Ａに接する向きにして載せる。
【００１２】
そして、図１（Ｄ）の如く、未硬化基材層１０Ａと繊維質シート２１と未硬化表面層３０Ａとがこの順に重なり、未硬化表面層３０Ａに鏡面板４３が当接する様にして重ねた状態の積層物を、下型２１１と上型２１２とを閉じて、加熱加圧する。加熱加圧のうち加圧は、枚葉熱プレス機２００が備える上下一対の駆動装置２２０によって、ラム２２１を油圧シリンダ２２２で上下に進退駆動させて、下型２１１及び上型２１２からなる型２１０を閉じて、積層物を加圧する。一方、加熱は、下型２１１及び上型２１２内には、電熱或いは加熱流体等によるヒータが埋設されており、これによって積層物を加圧と同時に加熱する。
【００１３】
繊維質シート２１の繊維間の空隙には、加熱加圧により、未硬化の熱硬化性樹脂１２が、下側からは未硬化基材層１０Ａから、上側からは未硬化表面層３０Ａから浸出して、空隙を有する繊維質シートは、熱硬化性樹脂で含浸された状態の繊維質シート２１となって、これが中間層２０となる。
【００１４】
そして、（繊維質シート２１中に浸出した熱硬化性樹脂も含めて）未硬化基材層１０Ａと未硬化表面層３０Ａ中の熱硬化性樹脂が硬化した後、型２１０を型開きして、加熱加圧（加熱と加圧とを同時に行う操作）を停止させる。そして、鏡面板４３を、未硬化表面層３０Ａが硬化して出来た表面層３０から剥離除去する。
【００１５】
そして、各層が積層一体化した積層体を型内から取出せば、図１（Ｅ）の如く、下から順に、未硬化基材層１０Ａが硬化して出来た基材層１０と、繊維質シート２１内に未硬化基材層１０Ａや未硬化表面層３０Ａ内の熱硬化性樹脂が侵出して出来た、繊維質シート２１を熱硬化性樹脂硬化物１２中に含む中間層２０と、未硬化表面層３０Ａが硬化して出来た表面が鏡面の表面層３０とが、積層した構成の繊維強化熱硬化性樹脂化粧板１００が得られる。すなわち、補強繊維１１を熱硬化性樹脂の硬化物１２中に含む基材層１０と、繊維質シート２１を熱硬化性樹脂の硬化物１２中に含む中間層２０と、補強繊維は含まず熱硬化性樹脂の硬化物からなり表面が鏡面の表面層３０とが、順次積層した構成の繊維強化熱硬化性樹脂化粧板１００が得られる。
【００１６】
次に、用いる各材料について説明する。
【００１７】
〔未硬化基材層〕
先ず、未硬化基材層１０Ａは、補強繊維１１と未硬化の熱硬化性樹脂１２Ａとから成り、該熱硬化性樹脂が硬化後は、硬化した熱硬化性樹脂の硬化物１２中に補強繊維１１を有する基材層１０となる。未硬化基材層１０Ａとしては、ＳＭＣ（シートモールディングコンパウンド）やＢＭＣ（バルクモールディングコンパウンド）等が代表的には使用される。特にＳＭＣは、その樹脂組成物が既にシート状に成形されている為、平板状の化粧板をバッチ式処理で製造するのに好適である。また、塊状に樹脂組成物を供給する場合は、ベルト上に供給すれば、連続生産に好適である。シート状の場合は一旦有形物としたものであるが、塊状の場合は、押出し機により押出して供給し積層することができる。
【００１８】
上記補強繊維１１としては、硝子繊維が代表的であるが、この他に、炭素繊維、石英繊維等の様な無機繊維、ポリエステル繊維、ナイロン繊維、アラミド繊維、ビニロン繊維等の合成樹脂繊維等も使用される。なお、補強繊維は、連続繊維でも良いが、通常それをカットした短繊維が用いられる。
【００１９】
また、上記熱硬化性樹脂としては、不飽和ポリエステル樹脂が代表的であるが、その他の樹脂、例えば、（硬化性）アクリル樹脂、エポキシ樹脂、ジアリルフタレート樹脂、メラミン樹脂、ウレタン樹脂等の熱硬化性樹脂も使用できる。
なお、本発明に於ける未硬化とは、全く硬化が進行していない状態の他に、硬化が一部進行しているが完全硬化前の状態でも良い。未硬化表面層の場合も同様である。
【００２０】
なお、未硬化基材層１０Ａ中には、必要に応じて適宜、シリカ、アルミナ、炭酸カルシウム等の充填剤、顔料や染料等の着色剤、硬化触媒、増粘剤、安定剤、可塑剤、滑剤、難燃剤、熱可塑性樹脂等を添加する。例えば上記硬化触媒としては、不飽和ポリエステル樹脂を熱硬化性樹脂として用いる場合では、ベンゾイルパーオキサイド、メチルエチルケトンパーオキサイド等の熱重合開始剤を添加する。
【００２１】
〔繊維質シート〕
繊維質シート２１により、基材層１０による機械的強度を補強し、また、加飾シートを、繊維質シートと未硬化表面層間に介在させて加飾する場合には、加熱加圧時に熱硬化性樹脂の未硬化物が流動しても、該加飾シートの絵柄が流れたり、歪んだりするのを防止する。なお、繊維質シートは、加熱加圧時に、未硬化基材層や未硬化表面層中に存在する、未硬化の熱硬化性樹脂の一部が該繊維質シート中に進入し、硬化した熱硬化性樹脂と繊維質シートとによる中間層となる。
【００２２】
繊維質シートは、その材料としては、アクリル、ナイロン、ポリエステル、ポリプロピレン、レーヨン、アセテート、ビニロン、ポリ塩化ビニル等からなる合成樹脂繊維や、セルロース、パルプ、羊毛等の天然有機物繊維、或いは、ガラス、石綿、チタン酸カリウム、アルミナ、シリカ、炭素等からなる無機質繊維等を使用する。また、繊維の集合形態としては、織布、不織布、或いは編布が用いられる。セルロースからなる不織布が紙であり、紙としては、上質紙、クラフト紙、和紙等が挙げられる。
なお、繊維質シートには、その繊維間に、ポリエステル樹脂、エポキシ樹脂、（硬化性）アクリル樹脂、ウレタン樹脂等による熱硬化性樹脂を含浸した含浸シートを繊維質シートとして用いても良い。この場合、使用時には、熱硬化性樹脂は未硬化のものを使用するのが、密着性の点から好ましい。
【００２３】
なお、未硬化基材層中の補強繊維と、繊維質シートの繊維との関係は、表１の如く構成する形態は、成形性の点で好ましい形態の一つである。すなわち、繊維質シート２１は、織布で繊維長が化粧板全域に及ぶ長さのものとし、未硬化基材層（基材層）の補強繊維１１は、繊維長が１〜１０ｍｍ程度の短繊維で、短繊維が散布された様に分布し、織り或いは編み等の交絡構造が無いものとする。この様に構成する場合は、曲げ変形した場合の応力（引張又は圧縮）が最大化する、化粧板の表面及び裏面は、繊維がまったく無いか（未硬化表面層）、或いは繊維が有っても交絡構造を持たない（未硬化基材層）為、曲げ変形に十分追従して、凹凸の化粧板を製造するに必要な成形性が良好となるからである。
また、成形時の曲げ変形時の応力（引張又は圧縮）が集中し難い積層体の中間部分に、変形し難く、強度も高い、長繊維で且つ交絡構造を有する織布を位置させることによって、化粧板の強度を向上し得る。なお、この様な層内の位置に周期的交絡構造を持つ織布を持ってきたが為に、新たに生じる問題は、交絡構造が非周期的な不織布の場合よりも、繊維質シート２１の繊維形状が化粧板表面に浮き出すことである。但し、この場合は、本発明に於いては、未硬化表面層は補強繊維無添加とし、且つ最表面を鏡面板に当接させて加熱加圧することで解決される。
【００２４】
【表１】

【００２５】
〔未硬化表面層〕
未硬化表面層３０Ａは、補強繊維を含ま無い熱硬化性樹脂の未硬化物から成る層であり、該未硬化物が硬化後は、熱硬化性樹脂の硬化物からなる表面層３０となる。表面層となるこの未硬化表面層中には、補強繊維を含有させないことで、補強繊維添加による表面凹凸発生による鏡面性低下を防ぐ。
未硬化表面層３０Ａとしては、代表的には、ＳＭＣ（シートモールディングコンパウンド）やＢＭＣ（バルクモールディングコンパウンド）として使用される樹脂組成物に対して、補強繊維は添加していない繊維未含有の樹脂組成物を使用することができる。ＳＭＣ或いはＢＭＣは、通常、補強繊維が添加された樹脂組成物を指すが、未硬化表面層として使用する樹脂組成物には、鏡面性を良くする為に、補強繊維は添加しない。但し、繊維以外の其の他の添加物（例えば充填剤等）は含んでいても良い。
【００２６】
また、未硬化表面層に使用する熱硬化性樹脂としては、前述未硬化基材層と同様に、不飽和ポリエステル樹脂が代表的であるが、その他の樹脂、例えば、（硬化性）アクリル樹脂、エポキシ樹脂、ジアリルフタレート樹脂、メラミン樹脂、ウレタン樹脂等の熱硬化性樹脂も使用できる。
【００２７】
なお、未硬化表面層１０Ａ中には、必要に応じて適宜、シリカ、アルミナ、炭酸カルシウム等の充填剤、顔料や染料等の着色剤、硬化触媒、増粘剤、安定剤、可塑剤、滑剤、減磨剤、難燃剤、熱可塑性樹脂等を添加する。例えば上記硬化触媒としては、不飽和ポリエステル樹脂を熱硬化性樹脂として用いる場合では、ベンゾイルパーオキサイド、メチルエチルケトンパーオキサイド等の熱重合開始剤を添加する。また、減磨剤は、未硬化表面層は最終的に化粧板表面を構成するので、特に用途が床材等では添加は効果的であり、アルミナ（α−アルミナ等）、シリカ、アリミノシリケート、雲母等の粉末が使用できる。
【００２８】
未硬化表面層は、それに用いる樹脂組成物を、シート状或いは（シート形状で）塊状で、未硬化基材層上に積層した繊維シート上に供給し積層する。シート状の場合は一旦有形物としたものであるが、塊状の場合は、押出し機により押出して供給し積層することができる。
【００２９】
なお、未硬化表面層を含め各層の厚みは、用途によるが、加熱加圧後の厚みとなる、表面層、中間層、基材層に於いて、通常１０〜１０００μｍ程度である。
【００３０】
〔加飾〕
本発明による製造方法では、未硬化基材層、繊維質シート、及び未硬化表面層の３層のみを積層し積層一体化しても良いが、必要に応じ更に、繊維強化熱硬化性樹脂化粧板に加飾処理を施す。加飾の代表的態様としては、（１）層自体の着色、（２）層中の繊維自体の染色（着色）、（３）別途装飾層の付与、等がある。
【００３１】
（１）層自体の着色は、例えば、表面層、中間層、基材層の何れか１層以上を着色する。着色するには、加飾すべき層の樹脂中に着色剤を添加すれば良い。着色剤としては、公知の顔料、染料等であり、例えば、弁柄、クロムバーミリオン、黄鉛、チタン黄色、群青、コバルトブルー、アンチモン白、チタン白、墨（カーボンブラック）、鉄黒等の無機顔料、イソインドリノンイエロー、ベンジジンイエロー、キナクリドンレッド、ポリアゾレッド、フタロシアニンブルー、インダスレンブルー等の有機顔料（乃至は染料）、アルミニウム、錫、真鍮等の鱗片状薄片からなる金属顔料、二酸化チタン被覆雲母、塩基性炭酸鉛等の鱗片状薄片からなる真珠光沢顔料（パール顔料）等である。
【００３２】
（２）加飾すべき層中の繊維自体の染色（着色）は、有機繊維の場合は公知の染料を用いる。また、ガラス繊維の場合はガラス中に公知の遷移金属（銅、コバルト、鉄、プラセオジウム等）系のガラス着色用顔料を添加して、紡績してガラス繊維とする。
【００３３】
（３）別途、装飾層の付与は、絵柄インキ層や、金属薄膜層等を装飾層として付与すれば良い。これら装飾層は、基材層、中間層（繊維質シート）、表面層等の各層に、直接絵柄印刷、金属蒸着等により形成することも可能ではあるが、繊維質シートや、未硬化の熱硬化性樹脂による層（未硬化基材層、未硬化表面層）に印刷や蒸着を施すことは一般には困難であり、生産効率も良く無い。よって、好ましくは、以下の（Ａ）や（Ｂ）の方法によると良い。
なお、装飾層は、意匠表現上、化粧板に於いて表面層の外表面に来る位置でも良いが、表面層に接して設ける場合はその内面側にするのが、表面層が装飾層に対する保護層となる点で好ましい。また、装飾層の絵柄は、例えば木目、石目、布目、砂目、タイル貼模様、煉瓦積模様、皮絞模様、幾何学模様、文字、記号、全面ベタ等である。
【００３４】
（Ａ）転写印刷法により、繊維質シート、或いは、未硬化基材層、未硬化表面層上に、絵柄インキ層を形成する。一例を挙げれば、特公平３−４７１８３号公報に記載の如き方法が挙げられる。すなわち、表面層に転写する場合の一例を説明すれば、未硬化表面層とする塊状の樹脂組成物を型上に供給した後、該塊状の樹脂組成物上に、転写シートをローラにより押し付けて樹脂組成物を延伸して未硬化表面層とすると同時に、該未硬化表面層上に転写シートを重ね、而る後、転写シートのベースシートを剥離することで、転写シートの転写層を未硬化表面層に転写する。
【００３５】
（Ｂ）予め印刷を施した加飾シートを、未硬化表面層と繊維質シートとの間に挟む。加飾シートは、基材シートに、上記の如き絵柄インキ層、金属薄膜層、或いは基材シート自体の着色等の１種又は２種以上の装飾処理を施したものを用いる。なお、基材シートとしては、前記の如き繊維質シートと同様の物、或いは、アクリル樹脂、ポリエステル樹脂、ポリスチレン、ＡＢＳ樹脂等の樹脂からなる、厚さ２０〜２００μｍ程度のシート等を用いる。
【００３６】
〔加熱加圧〕
なお、未硬化基材層、繊維質シート、及び未硬化表面層、更に必要に応じ適宜な位置に加飾シート等を積層し、これら各層を積層一体化する為の加熱加圧条件は、未硬化基材層や未硬化表面層に使用する熱硬化性樹脂等に応じた条件となる。例えば、不飽和ポリエステル樹脂を使用する場合、通常、１２０〜１６０℃、１〜１０ＭＰａ、加熱加圧時間５〜２０ｍｉｎ程度である。
【００３７】
また、加熱加圧する為の熱圧の加え方は、特に制限は無い。図１で説明した加熱加圧方式は枚葉熱プレス機によるバッチ式であり、間欠処理工程となる。一方、これから図２を参照して説明する加熱加圧方式はベルト挟持式熱プレス機によるベルトプレス方式であり、連続処理工程となる。
【００３８】
図２で概念的に示すベルト挟持式熱プレス機３００は、一対のエンドレスの加圧ベルト、すなわち、加圧ベルト３１０と鏡面Ｍを有する鏡面加圧ベルト３１０Ｍによって、加熱加圧する。これら加圧ベルト３１０及び３１０Ｍは、それぞれ一対の駆動ローラ３２０で同一速度で図面矢印方向に駆動され、それぞれ多数のガイドローラ３３０でガイドされて積層材料１００Ａを、搬送する。また、そして、各加圧ベルト３１０及び３１０Ｍの内側には、それぞれ加熱加圧装置３４０が配置され、加圧ベルト３１０或いは３１０Ｍの裏側から、積層材料１００Ａを加圧ベルト３１０及び３１０Ｍを通して加熱加圧する様になっている。加熱加圧装置３４０は、金属盤中に加熱水蒸気、加熱油を流通させたり、或いは、誘導加熱等により加熱する。また、加圧は、流体圧による。また、一対の加圧ベルトのうち、未硬化表面層に当接させる側の加圧ベルトには、該層に当接する面が鏡面の鏡面加圧ベルト３１０Ｍが用いられる。鏡面加圧ベルト３１０Ｍは、炭素鋼、ステンレス鋼等の金属からなり、必要に応じて表面にクロムめっき等を施すしたものが使われる。該鏡面加圧ベルトの鏡面とする側の表面は、所望の鏡面が得られる様な鏡面（表面粗さ）とする。表面粗さ（ＪＩＳＢ０６０１規定）は、中心線平均粗さ（Ｒａ）で１μｍ以下、より好ましくは０．１μｍとするのが良い。
【００３９】
そして、同図では積層すべき積層材料１００Ａは、加圧ベルト３１０とは別の搬送ベルト３５０上に準備される。積層材料の準備は、予め別品として用意した各層を、手作業で搬送ベルト上で重ね合せる等しても良いが、図示はしいが、例えば次の様にして準備すれば、量産性が良い。なお、積層材料を載置する側の加圧ベルト３１０の長さを長くして、同図搬送ベルトを兼用させて、該搬送ベルトを省略しても良いことは、もちろんである。
【００４０】
すなわち、先ず、押出し機により未硬化基材層とする補強繊維を含む樹脂組成物を押出して、搬送ベルト上に未硬化基材層を形成する。押出しはＴダイ等により層状に押出せば良い。なお、未硬化基材層は、間欠押出しで枚葉のシート状に形成する以外に、連続的に押出して連続帯状のシート状（ウェブ状）に形成しても良い。そして、ベルト上に形成された未硬化基材層の上に、更に枚葉シート状の繊維質シートを載置し積層する。そして、該繊維質シートの上に、押出し機により未硬化表面層とする補強繊維を含ま無い樹脂組成物を押出して、繊維シート上に未硬化表面層を載置し積層すれば、これらが積層された積層材料１００Ａが得られる。また、必要に応じ加飾シートも使用する場合は、例えば、繊維質シート積層後に加飾シートを重ねて、その後で未硬化表面層を重ねれば良い。
なお、積層材料を構成する各層を、全て連続帯状で重ねて、その後で、所望の長さに切断して、枚葉の積層材料１００Ａとしても良い。
【００４１】
そして、搬送ベルト上に準備された積層材料１００Ａは、加圧ベルト３１０上に渡されて、次いで、未硬化表面層側は鏡面加圧ベルト３１０Ｍを適用して加熱加圧されて、熱硬化性樹脂を硬化させると共に各層を積層一体化し、その結果、所望の繊維強化熱硬化性樹脂化粧板１００が得られる。
【００４２】
〔その他〕
未硬化基材層、繊維質シート、及び未硬化表面層の積み上げ順序は、上述した順序の他に、逆順でも良い。
図３で概念的に示す枚葉熱プレス機による製造方法では、図１で例示の順とは逆順の方法であり、未硬化表面層３０Ａから順に型上に積層して行く方法である。この方法によれば、表面層の直下に装飾層を容易に積層できる。すなわち、図３に例示する場合で言えば、先ず、図３（Ａ）の如く、鏡面Ｍを有する下型兼鏡面板４１Ｍ内に、補強繊維を含まない熱硬化性樹脂の未硬化物からなる未硬化表面層３０Ａを載せ、次いで、図３（Ｂ）の如く、該未硬化表面層３０Ａの上に加飾シート５０を載せてから、図３（Ｃ）の如く、該加飾シートの上に繊維質シート２１として、該繊維質シート２１に熱硬化性樹脂の未硬化物１２Ａが含浸されてなる未硬化中間層２０Ａを積層する。そして、この後、図３（Ｄ）の如く、補強繊維１１と熱硬化性樹脂の未硬化物１２Ａとから成る未硬化基材層１０Ａを積層する。そして、図３（Ｅ）の如く、下型兼鏡面板４１Ｍと上型４２とから成る型４０を閉じて、加熱加圧する。
【００４３】
そして、熱硬化性樹脂が硬化して各層が積層一体化した積層体を、型内から取出せば、図３（Ｆ）の如く、裏側（図面下方）から順に、未硬化基材層１０Ａが硬化して出来た、補強繊維１１を熱硬化性樹脂硬化物１２中に含む基材層１０、繊維質シート２１を熱硬化性樹脂の硬化物１２中に含む中間層２０、加飾シート５０、未硬化表面層３０Ａが硬化して出来た表面鏡面の表面層３０が、この順に積層一体化した構成の繊維強化熱硬化性樹脂化粧板１００が得られる。
【００４４】
〔繊維強化熱硬化性樹脂化粧板の用途〕
本発明で得られ繊維強化熱硬化性樹脂化粧板の用途は特に限定されないが、例えば化粧パネルや化粧部材等として各種用途に用いられる。好適には、その表面の鏡面性、表面耐熱性等の表面物性を活かせる用途に用いられる。例えば、建築物の床材や壁材、浴室の床材や壁材、洗面化粧台等の住設機器、手摺、扉等の建具、家具、家電製品のキャビネット、自動車、電車、航空機、船舶等の乗物内装材、容器等の各種分野に用いる事ができる。なお、繊維強化熱硬化性樹脂化粧板の形状は、立体形状の他、平板状でも良い。
【００４５】
【実施例】
次に実施例により本発明を更に詳述する。
【００４６】
〔実施例１〕
エンドレス加圧ベルト上に、先ず、樹脂組成物として下記表２で示す組成のペーストＢを、Ｔダイにて押出して未硬化基材層１０Ａを積層した。次いで、該未硬化基材層１０Ａの上に、繊維質シート２１としてガラス繊維の織布を積層し、更にその上に、樹脂組成物として下記表２で示す組成のペーストＡを、Ｔダイにて押出して未硬化表面層３０Ａを積層して、積層材料１００Ａとした。
【００４７】
【表２】

【００４８】
次いで、該積層材料１００Ａを、図２で示した様なベルト挟持式熱プレス機３００にて、温度１５０℃、圧力８Ｐａ（８０ｋｇｆ／ｃｍ²）で５分間、加熱加圧して、各層を積層一体化すると共に熱硬化性樹脂は硬化させて、平板状で図１（Ｅ）の様な繊維強化熱硬化性樹脂化粧板１００を作製した。
【００４９】
〔比較例１〕
実施例１に於いて、エンドレス加圧ベルト上に、ペーストＢをＴダイにて押出して未硬化基材層１０Ａを積層した後、繊維質シート２１及び未硬化表面層３０Ａの積層は省略したものを、そのまま、実施例１と同様して、ベルト挟持式熱プレス機３００にて加熱加圧して、未硬化基材層１０Ａが硬化した基材層１０のみの単層から成る繊維強化熱硬化性樹脂化粧板を作製した。
【００５０】
〔比較例２〕
実施例１に於いて、エンドレス加圧ベルト上に、ペーストＢをＴダイにて押出して未硬化基材層１０Ａを積層後、その上に繊維質シート２１を積層した後、繊維質シートの上に、ペーストＡの代わりにペーストＢをＴダイにて押出して、未硬化表面層として未硬化基材層１０Ａを積層した積層物を、実施例１と同様して、ベルト挟持式熱プレス機３００にて加熱加圧して、各層を積層一体化すると共に熱硬化性樹脂は硬化させて、繊維強化熱硬化性樹脂化粧板を作製した。
【００５１】
〔性能比較〕
実施例及び比較例の繊維強化熱硬化性樹脂化粧板は、その表面が、実施例１のみ鏡面が得られ鏡面性が良好であったが、各比較例では補強繊維の影響で表面に凹凸が出来、鏡面性に劣った。
なお、各化粧板は、いずれも表面耐熱性は良好ではあったが、機械的強度は、各比較例に比べて実施例の方が良かった。
【００５２】
【発明の効果】
（１）本発明によれば、鏡面性、表面耐熱性、及び機械的強度が良い繊維強化熱硬化性樹脂化粧板が得られる。
（２）また、加熱加圧をベルトプレス方式で行えば、枚葉熱プレス機の様にバッチ式の間欠処理では無く、連続処理が可能となる為に、円滑に製造でき生産性が良くなる。
【図面の簡単な説明】
【図１】本発明による繊維強化熱硬化性樹脂化粧板の製造方法を、その一形態で概念的に説明する概念図。
【図２】本発明による製造方法を、加熱加圧方式に於ける別の一形態（ベルトプレス方式）で概念的に説明する概念図。
【図３】本発明の製造方法を、別の一形態で概念的に説明する概念図。
【符号の説明】
１０基材層
１０Ａ未硬化基材層
１１補強繊維
１２熱硬化性樹脂の硬化物
１２Ａ熱硬化性樹脂の未硬化物
２０中間層
２０Ａ未硬化中間層
２１繊維質シート
３０表面層
３０Ａ未硬化表面層
４０型
４１Ｍ下型兼鏡面板
４２上型
４３鏡面板
５０加飾シート
１００繊維強化熱硬化性樹脂化粧板
１００Ａ積層材料
２００枚葉熱プレス機
２１０型
２１１下型
２１２上型
２２０駆動装置
２２１ラム
２２２油圧シリンダ
３００ベルト挟持式熱プレス機
３１０加圧ベルト
３１０Ｍ鏡面加圧ベルト
３２０駆動ローラ
３３０ガイドローラ
３４０加熱加圧装置
３５０搬送ローラ[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a fiber reinforced thermosetting resin decorative board that can be used as an FRP (fiber reinforced plastic) molded article or the like in various uses such as flooring and wall materials of buildings, bathrooms, and washstands. .
[0002]
[Prior art]
Conventionally, as a method for producing a fiber-reinforced thermosetting resin decorative board, for example, a decorative sheet such as a patterned nonwoven fabric or printing paper, a non-cured sheet impregnated with a thermosetting resin, and reinforcement of glass fiber or the like A method is known in which a thermosetting resin uncured base material layer containing fibers (reinforced fibers) is stacked and laminated by heating and pressurizing and thermosetting (see Japanese Patent Application Laid-Open No. 48-12876, etc.). Moreover, if a sheet-like SMC (sheet molding compound) or a massive BMC (bulk molding compound) is used for the uncured base material layer, workability and the like are further improved.
[0003]
In this case, the strength is increased by the reinforcing fiber, but the surface is uneven by the fiber, and the smoothness is lowered. Therefore, in particular, when specularity with which surface irregularities are conspicuous is required, a decorative sheet with a nonwoven fabric lined on the back surface of a printed sheet in which a decorative layer is printed on the back surface of a thermoplastic resin sheet made of polyethylene terephthalate or the like is used. Also disclosed is a method of laminating an uncured base material layer such as SMC on the back side of the decorative sheet and curing it by heating and pressurization (see JP-A-8-118384, etc.).
[0004]
[Problems to be solved by the invention]
However, in the configuration in which the decorative plate surface is a thermoplastic resin sheet, the mirror surface property is good, but the heat resistance of the surface is inferior compared to the case where the surface is made of a thermosetting resin. In addition, if SMC or BMC is used for the uncured base material layer, workability is good, but on the other hand, short fibers are used as the reinforcing fibers, so compared to fiber reinforcement with woven fabrics etc. in which long fibers are used. The mechanical strength may be inferior.
[0005]
That is, the subject of this invention is providing the manufacturing method of a fiber reinforced thermosetting resin decorative board which can improve specularity, surface heat resistance, and mechanical strength. Moreover, it is providing the manufacturing method of a fiber reinforced thermosetting resin decorative board with favorable productivity.
[0006]
[Means for Solving the Problems]
Therefore, in order to solve the above problems, the method for producing a fiber-reinforced thermosetting resin decorative board of the present invention includes an uncured base layer composed of a reinforcing fiber and an uncured material of a thermosetting resin, and a reinforcing fiber. In the state where the uncured surface layer made of uncured thermosetting resin is laminated with a fibrous sheet in between, the mirror surface plate is heated so that the mirror surface is in contact with the uncured surface layer. The thermosetting resin in the uncured base layer and the uncured surface layer is cured, and then the heating and pressurization is stopped, and then the uncured surface layer is cured and the mirror is applied from above the surface layer. The face plate was peeled and removed.
[0007]
By using such a production method, the surface layer (cured product of the uncured surface layer) that forms the decorative board surface does not contain reinforcing fibers, so that the specularity can be improved and the surface is improved. Since the layer is made of a cured product of a thermosetting resin, the surface heat resistance can be improved. Moreover, since the fibrous sheet is interposed as an intermediate layer, the mechanical strength can be improved even if the reinforcing fibers in the base material layer (cured product of the uncured base material layer) are short fibers. Therefore, it becomes a manufacturing method which can obtain specularity, surface heat resistance, and mechanical strength.
[0008]
Further, the method for producing a fiber-reinforced thermosetting resin decorative board of the present invention is the method described above, wherein a resin composition containing reinforcing fibers is extruded by an extruder to form an uncured base material layer on the belt, A fibrous sheet is laminated on the uncured substrate layer, and a resin composition not containing reinforcing fibers is extruded onto the fibrous sheet by an extruder to laminate an uncured surface layer, and then uncured. A mirror pressure belt, which is a mirror plate, is used as a pressure belt on the surface layer side, and is heated and pressed by a belt press method by sandwiching the pressure belt from above and below.
[0009]
By setting it as such a method, since lamination | stacking and a heating-pressing operation can be smoothly performed not by a batch type intermittent process but by a continuous process, productivity improves.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[0011]
[Summary]
First, FIG. 1 is a conceptual diagram for conceptually explaining a method for producing a fiber-reinforced thermosetting resin decorative plate according to the present invention in one form thereof (heating and pressing method using a single-wafer heat press). In the form shown in the figure, first, as shown in FIG. 1 (A), a plate-shaped or sheet-shaped uncured base material layer composed of reinforcing fibers 11 and an uncured material 12A of a thermosetting resin in a lower mold 211. 10A is laminated. Next, as shown in FIG. 1 (B), a fibrous sheet 21 is placed on the uncured resin base material layer 10A. Then, as shown in FIG. 1 (C), reinforcing fibers are further placed on the fibrous sheet 21. An uncured surface layer 30A made of an uncured thermosetting resin not included is placed, and a mirror plate 43 is placed on the uncured surface layer 30A so that the mirror surface is in contact with the uncured surface layer 30A.
[0012]
Then, as shown in FIG. 1D, the uncured base material layer 10A, the fibrous sheet 21, and the uncured surface layer 30A are overlapped in this order, and the mirror plate 43 is overlapped with the uncured surface layer 30A. The laminated body in the state is heated and pressurized with the lower mold 211 and the upper mold 212 closed. Of the heating and pressurization, pressurization is performed by driving a ram 221 up and down with a hydraulic cylinder 222 by a pair of upper and lower drive devices 220 provided in the single-wafer heat press machine 200 to form a mold 210 including a lower mold 211 and an upper mold 212. Is closed and the laminate is pressurized. On the other hand, in the lower mold 211 and the upper mold 212, a heater is embedded in the lower mold 211 and the upper mold 212, thereby heating the laminate simultaneously with pressurization.
[0013]
In the space between the fibers of the fibrous sheet 21, uncured thermosetting resin 12 is leached from the uncured base layer 10A from the lower side and from the uncured surface layer 30A from the upper side by heating and pressing. The fibrous sheet having voids becomes the fibrous sheet 21 impregnated with the thermosetting resin, which becomes the intermediate layer 20.
[0014]
And after the thermosetting resin in the uncured base material layer 10A and the uncured surface layer 30A is cured (including the thermosetting resin leached in the fibrous sheet 21), the mold 210 is opened, Stop the heating and pressurization (operation to perform heating and pressurization simultaneously). Then, the mirror plate 43 is peeled off from the surface layer 30 formed by curing the uncured surface layer 30A.
[0015]
And if the laminated body which each layer laminated | stacked and integrated is taken out from a type | mold, as shown in FIG.1 (E), the base material layer 10 which the uncured base material layer 10A hardened | cured in order from the bottom, and a fibrous sheet The intermediate layer 20 containing the fibrous sheet 21 in the thermosetting resin cured product 12 formed by the thermosetting resin in the uncured base material layer 10A and the uncured surface layer 30A leaching in A fiber reinforced thermosetting resin decorative board 100 having a structure in which the surface layer 30 having a mirror-finished surface layer formed by curing the surface layer 30A is obtained. That is, the base material layer 10 including the reinforcing fiber 11 in the cured product 12 of the thermosetting resin, the intermediate layer 20 including the fibrous sheet 21 in the cured product 12 of the thermosetting resin, and the heat without including the reinforcing fiber. A fiber-reinforced thermosetting resin decorative board 100 having a configuration in which a surface layer 30 made of a cured product of a curable resin and having a mirror surface is sequentially laminated is obtained.
[0016]
Next, each material used will be described.
[0017]
[Uncured substrate layer]
First, the uncured substrate layer 10A is composed of reinforcing fibers 11 and an uncured thermosetting resin 12A. After the thermosetting resin is cured, the reinforcing fibers are contained in the cured product 12 of the cured thermosetting resin. The base material layer 10 having 11 is obtained. As the uncured base material layer 10A, SMC (sheet molding compound), BMC (bulk molding compound), or the like is typically used. In particular, since the resin composition of SMC is already formed into a sheet shape, it is suitable for manufacturing a flat decorative plate by batch processing. Moreover, when supplying a resin composition in a lump form, if it supplies on a belt, it is suitable for continuous production. In the case of a sheet form, it is once made into a tangible material, but in the case of a lump form, it can be extruded and supplied by an extruder and laminated.
[0018]
The reinforcing fiber 11 is typically a glass fiber, but in addition to this, inorganic fibers such as carbon fiber and quartz fiber, synthetic resin fibers such as polyester fiber, nylon fiber, aramid fiber, vinylon fiber, etc. used. The reinforcing fiber may be a continuous fiber, but a short fiber obtained by cutting it is usually used.
[0019]
The above thermosetting resin is typically an unsaturated polyester resin, but other resins such as (curing) acrylic resin, epoxy resin, diallyl phthalate resin, melamine resin, urethane resin, etc. Can also be used.
In the present invention, the term “uncured” refers to a state in which the curing has partially progressed in addition to the state in which the curing has not progressed at all. The same applies to an uncured surface layer.
[0020]
In the uncured base material layer 10A, a filler such as silica, alumina and calcium carbonate, a colorant such as a pigment and a dye, a curing catalyst, a thickener, a stabilizer, a plasticizer, Add lubricant, flame retardant, thermoplastic resin, etc. For example, as the curing catalyst, when an unsaturated polyester resin is used as the thermosetting resin, a thermal polymerization initiator such as benzoyl peroxide or methyl ethyl ketone peroxide is added.
[0021]
[Fibrous sheet]
When the fiber sheet 21 reinforces the mechanical strength of the base material layer 10 and decorates the decorative sheet by interposing it between the fiber sheet and the uncured surface layer, it is thermally cured during heating and pressurization. Even if the uncured product of the functional resin flows, the decorative sheet is prevented from flowing or distorted. In addition, the fibrous sheet is a heat that has been cured when a part of the uncured thermosetting resin that is present in the uncured base material layer or the uncured surface layer enters the fibrous sheet during heating and pressurization. It becomes an intermediate | middle layer by curable resin and a fibrous sheet.
[0022]
The fiber sheet is made of synthetic resin fibers made of acrylic, nylon, polyester, polypropylene, rayon, acetate, vinylon, polyvinyl chloride, etc., natural organic fibers such as cellulose, pulp, wool, or glass, Inorganic fibers made of asbestos, potassium titanate, alumina, silica, carbon, etc. are used. In addition, a woven fabric, a non-woven fabric, or a knitted fabric is used as an aggregate form of the fibers. Nonwoven fabric made of cellulose is paper, and examples of paper include high-quality paper, craft paper, and Japanese paper.
For the fibrous sheet, an impregnated sheet impregnated with a thermosetting resin such as a polyester resin, an epoxy resin, a (curable) acrylic resin, or a urethane resin between the fibers may be used as the fibrous sheet. In this case, at the time of use, it is preferable from the point of adhesiveness to use an uncured thermosetting resin.
[0023]
In addition, as for the relationship between the reinforcing fiber in the uncured base material layer and the fiber of the fibrous sheet, the form as shown in Table 1 is one of the preferred forms in terms of moldability. That is, the fibrous sheet 21 is a woven fabric having a fiber length that extends over the entire decorative plate, and the reinforcing fiber 11 of the uncured base material layer (base material layer) has a short fiber length of about 1 to 10 mm. It is assumed that the fibers are distributed as if the short fibers were dispersed and have no entanglement structure such as weaving or knitting. When configured in this way, the stress (tensile or compression) when bending deformation is maximized, the front and back surfaces of the decorative board have no fibers (uncured surface layer) or have fibers. This is because, since it does not have an entangled structure (uncured base material layer), the moldability required to produce an uneven decorative board sufficiently follows bending deformation.
Further, by positioning a woven fabric having an entangled structure with long fibers, which is difficult to be deformed and has high strength, in an intermediate portion of the laminate in which stress (tensile or compression) during bending deformation at the time of molding is difficult to concentrate. The strength of the decorative board can be improved. In addition, since the woven fabric having the periodically entangled structure is brought to the position in such a layer, the newly generated problem is that the fibrous sheet 21 has a more entangled structure than the non-periodic nonwoven fabric. The fiber shape is raised on the surface of the decorative board. However, in this case, in the present invention, the uncured surface layer can be solved by adding no reinforcing fiber and heating and pressing the outermost surface in contact with the mirror plate.
[0024]
[Table 1]

[0025]
[Uncured surface layer]
The uncured surface layer 30A is a layer made of an uncured material of a thermosetting resin that does not contain reinforcing fibers, and after the uncured material is cured, it becomes the surface layer 30 made of a cured material of the thermosetting resin. The uncured surface layer that becomes the surface layer does not contain reinforcing fibers, thereby preventing a decrease in specularity due to surface irregularities caused by the addition of reinforcing fibers.
As the uncured surface layer 30A, a fiber-free resin composition in which reinforcing fibers are not added to a resin composition used as SMC (sheet molding compound) or BMC (bulk molding compound) is typically used. Things can be used. SMC or BMC usually refers to a resin composition to which reinforcing fibers are added. However, reinforcing fibers are not added to the resin composition used as the uncured surface layer in order to improve the specularity. However, other additives (for example, fillers) other than fibers may be included.
[0026]
In addition, as the thermosetting resin used for the uncured surface layer, an unsaturated polyester resin is representative, like the uncured base material layer, but other resins such as a (curable) acrylic resin, Thermosetting resins such as epoxy resins, diallyl phthalate resins, melamine resins and urethane resins can also be used.
[0027]
In the uncured surface layer 10A, fillers such as silica, alumina and calcium carbonate, colorants such as pigments and dyes, curing catalysts, thickeners, stabilizers, plasticizers and lubricants are appropriately added as necessary. Add abrasives, flame retardants, thermoplastics, etc. For example, as the curing catalyst, when an unsaturated polyester resin is used as the thermosetting resin, a thermal polymerization initiator such as benzoyl peroxide or methyl ethyl ketone peroxide is added. In addition, since the uncured surface layer finally constitutes the decorative board surface, the anti-friction agent is particularly effective when used for flooring or the like, such as alumina (α-alumina, etc.), silica, ariminosilicate, Powders such as mica can be used.
[0028]
The uncured surface layer supplies and laminates the resin composition used therefor on a fiber sheet laminated in a sheet form (in the form of a sheet) and laminated on the uncured base material layer. In the case of a sheet form, it is once made into a tangible material, but in the case of a lump form, it can be extruded and supplied by an extruder and laminated.
[0029]
In addition, although the thickness of each layer including a non-hardened surface layer is based on a use, it is about 10-1000 micrometers normally in the surface layer, intermediate | middle layer, and base material layer used as the thickness after heating-pressing.
[0030]
〔Decorative〕
In the production method according to the present invention, only three layers of an uncured base material layer, a fiber sheet, and an uncured surface layer may be laminated and integrated, but if necessary, a fiber reinforced thermosetting resin decorative board Is decorated with. As typical aspects of the decoration, there are (1) coloring of the layer itself, (2) dyeing (coloring) of the fiber itself in the layer, (3) provision of a separate decoration layer, and the like.
[0031]
(1) For coloring the layer itself, for example, one or more of the surface layer, the intermediate layer, and the base material layer are colored. In order to color, a colorant may be added to the resin of the layer to be decorated. Examples of the colorant include known pigments, dyes, and the like, such as petals, chrome vermilion, yellow lead, titanium yellow, ultramarine blue, cobalt blue, antimony white, titanium white, black ink (carbon black), and iron black. Inorganic pigments, isoindolinone yellow, benzidine yellow, quinacridone red, polyazo red, phthalocyanine blue, indanthrene blue and other organic pigments (or dyes), aluminum, tin, brass and other metallic flakes, titanium dioxide coating Pearlescent pigments (pearl pigments) composed of flakes such as mica and basic lead carbonate.
[0032]
(2) For the dyeing (coloring) of the fibers themselves in the layer to be decorated, a known dye is used in the case of organic fibers. In the case of glass fiber, a known transition metal (copper, cobalt, iron, praseodymium, etc.) glass coloring pigment is added to the glass and spun into glass fiber.
[0033]
(3) Separately, the decorative layer may be applied by providing a pattern ink layer, a metal thin film layer, or the like as the decorative layer. These decorative layers can be formed directly on each layer such as a base material layer, an intermediate layer (fibrous sheet), and a surface layer by pattern printing, metal vapor deposition, or the like. It is generally difficult to print or vapor-deposit a layer (uncured substrate layer, uncured surface layer) made of a curable resin, and the production efficiency is not good. Therefore, it is preferable to use the following methods (A) and (B).
The decorative layer may be positioned on the outer surface of the surface layer on the decorative board in terms of design, but if it is provided in contact with the surface layer, the surface layer is on the inner surface side to protect the decorative layer. It is preferable at the point which becomes a layer. In addition, the decorative layer picture is, for example, wood grain, stone grain, cloth grain, sand grain, tiled pattern, brickwork pattern, skin-drawn pattern, geometric pattern, character, symbol, full face, and the like.
[0034]
(A) A pattern ink layer is formed on a fibrous sheet, an uncured base material layer, or an uncured surface layer by a transfer printing method. If an example is given, the method as described in Japanese Patent Publication No. 3-47183 will be mentioned. That is, an example of the case of transferring to the surface layer will be described. After supplying the block-shaped resin composition to be an uncured surface layer onto the mold, the transfer sheet is pressed onto the block-shaped resin composition with a roller. The resin composition is stretched to form an uncured surface layer, and at the same time, the transfer sheet is stacked on the uncured surface layer, and then the transfer sheet base sheet is peeled off to uncur the transfer sheet transfer layer. Transfer to the surface layer.
[0035]
(B) A pre-printed decorative sheet is sandwiched between the uncured surface layer and the fibrous sheet. As the decorative sheet, a base sheet that has been subjected to one or more decorative treatments such as coloring of the pattern ink layer, the metal thin film layer, or the base sheet itself is used. In addition, as a base material sheet, the sheet | seat etc. about 20-200 micrometers thick which consist of the thing similar to the above fiber sheets or resin, such as an acrylic resin, a polyester resin, a polystyrene, an ABS resin, are used.
[0036]
[Heating and pressing]
The uncured substrate layer, the fibrous sheet, the uncured surface layer, and a decorative sheet or the like are laminated at appropriate positions as necessary, and the heating and pressing conditions for laminating and integrating these layers are as follows. It becomes the conditions according to the thermosetting resin etc. which are used for a hardening base material layer or an uncured surface layer. For example, when an unsaturated polyester resin is used, it is usually 120 to 160 ° C., 1 to 10 MPa, and the heating and pressing time is about 5 to 20 minutes.
[0037]
Moreover, there is no restriction | limiting in particular how to apply the heat pressure for heating and pressurizing. The heating and pressing method described in FIG. 1 is a batch method using a single-wafer heat press and is an intermittent processing step. On the other hand, the heating and pressurizing method to be described with reference to FIG. 2 is a belt pressing method using a belt-clamping hot press machine, which is a continuous processing step.
[0038]
The belt-clamping hot press 300 conceptually shown in FIG. 2 is heated and pressurized by a pair of endless pressure belts, that is, a mirror surface pressure belt 310M having a pressure belt 310 and a mirror surface M. The

pressure belts

310 and 310M are each driven in the direction indicated by the arrow at the same speed by a pair of drive rollers 320, and are each guided by a number of guide rollers 330 to convey the laminated material 100A. Further, heating and pressurizing devices 340 are disposed inside the

respective pressure belts

310 and 310M, and the laminated material 100A is heated and pressed through the

pressure belts

310 and 310M from the back side of the

pressure belt

310 or 310M. It is like. The heating and pressurizing device 340 circulates heated steam and heated oil in the metal plate, or heats by induction heating or the like. Further, pressurization is based on fluid pressure. Further, of the pair of pressure belts, a mirror surface pressure belt 310 </ b> M whose surface abutting against the layer is a mirror surface is used as the pressure belt on the side to be in contact with the uncured surface layer. The mirror pressure belt 310M is made of a metal such as carbon steel or stainless steel, and the surface of which is plated with chromium or the like as required. The surface of the mirror pressure belt that is the mirror surface is a mirror surface (surface roughness) that provides a desired mirror surface. The surface roughness (JIS B0601 standard) is 1 μm or less, more preferably 0.1 μm in terms of centerline average roughness (Ra).
[0039]
In the drawing, the laminated material 100A to be laminated is prepared on a transport belt 350 different from the pressure belt 310. For the preparation of the laminated material, each layer prepared in advance as a separate product may be manually overlapped on the conveyor belt, but it is not illustrated, but for example, if it is prepared as follows, mass productivity is good. . Of course, the length of the pressure belt 310 on the side where the laminated material is placed may be increased so that the conveyor belt is also used, and the conveyor belt may be omitted.
[0040]
That is, first, a resin composition containing a reinforcing fiber to be an uncured base material layer is extruded by an extruder to form an uncured base material layer on the transport belt. Extrusion may be performed in a layer form by a T die or the like. The uncured base material layer may be continuously extruded to be formed into a continuous belt-like sheet (web shape) in addition to being formed into a sheet-like sheet by intermittent extrusion. Then, a sheet-like fibrous sheet is further placed and laminated on the uncured base material layer formed on the belt. And if the resin composition which does not contain the reinforcement fiber made into an uncured surface layer by an extruder is extruded on the fibrous sheet, and the uncured surface layer is placed on the fiber sheet and laminated, these are laminated. The laminated material 100A thus obtained is obtained. Moreover, when using a decorating sheet as needed, what is necessary is just to pile up a decorating sheet after a fiber sheet lamination | stacking, and to pile up an unhardened surface layer after that, for example.
Note that all the layers constituting the laminated material may be stacked in a continuous band shape, and then cut into a desired length to form a single-layer laminated material 100A.
[0041]
Then, the laminated material 100A prepared on the conveyor belt is transferred onto the pressure belt 310, and then the uncured surface layer side is heated and pressurized by applying the mirror surface pressure belt 310M to be thermosetting. The resin is cured and the layers are laminated and integrated. As a result, a desired fiber-reinforced thermosetting resin decorative board 100 is obtained.
[0042]
[Others]
The order of stacking the uncured base material layer, the fibrous sheet, and the uncured surface layer may be reversed in addition to the order described above.
In the manufacturing method using the single-wafer heat press conceptually shown in FIG. 3, the order is the reverse of the order illustrated in FIG. 1, and is a method in which the uncured surface layer 30A is laminated on the mold in order. According to this method, the decoration layer can be easily laminated immediately below the surface layer. That is, in the case illustrated in FIG. 3, first, as shown in FIG. 3A, the lower mold / mirror plate 41 </ b> M having the mirror surface M is made of an uncured material of a thermosetting resin that does not include reinforcing fibers. The uncured surface layer 30A is placed, and then the decorative sheet 50 is placed on the uncured surface layer 30A as shown in FIG. 3B, and then the decorative sheet 50 is placed on the decorative sheet as shown in FIG. Further, as the fibrous sheet 21, an uncured intermediate layer 20A formed by impregnating the fibrous sheet 21 with an uncured material 12A of a thermosetting resin is laminated. Thereafter, as shown in FIG. 3D, an uncured base material layer 10A composed of reinforcing fibers 11 and an uncured material 12A of a thermosetting resin is laminated. Then, as shown in FIG. 3E, the mold 40 composed of the lower mold / mirror plate 41M and the upper mold 42 is closed and heated and pressurized.
[0043]
And if the laminated body which the thermosetting resin hardened | cured and each layer laminated | stacked and integrated is taken out from a type | mold, uncured base material layer 10A will harden | cure sequentially from the back side (downward drawing) like FIG.3 (F). The base material layer 10 including the reinforcing fiber 11 in the thermosetting resin cured product 12, the intermediate layer 20 including the fibrous sheet 21 in the thermosetting resin cured product 12, the decorative sheet 50, and the like. A fiber-reinforced thermosetting resin decorative board 100 having a configuration in which the surface mirror surface 30 having a cured surface layer 30A is laminated and integrated in this order is obtained.
[0044]
[Use of fiber-reinforced thermosetting resin decorative board]
Although the use of the fiber reinforced thermosetting resin decorative board obtained in the present invention is not particularly limited, it can be used for various applications such as a decorative panel and a decorative member. Preferably, it is used for applications in which surface physical properties such as specularity and surface heat resistance of the surface can be utilized. For example, building flooring and wall materials, bathroom flooring and wall materials, bathroom equipment such as bathroom vanities, handrails, doors and other fittings, furniture, home appliance cabinets, automobiles, trains, aircraft, ships, etc. It can be used in various fields such as vehicle interior materials and containers. In addition, the shape of the fiber-reinforced thermosetting resin decorative plate may be a flat shape as well as a three-dimensional shape.
[0045]
【Example】
Next, the present invention will be described in further detail with reference to examples.
[0046]
[Example 1]
On the endless pressure belt, first, paste B having the composition shown in Table 2 below was extruded as a resin composition with a T-die to laminate an uncured base material layer 10A. Next, a glass fiber woven fabric is laminated as the fibrous sheet 21 on the uncured substrate layer 10A, and a paste A having the composition shown in Table 2 below as a resin composition is further formed on the T-die. Then, the uncured surface layer 30A was laminated to obtain a laminated material 100A.
[0047]
[Table 2]

[0048]
Next, the laminated material 100A is heated at a temperature of 150 ° C. and a pressure of 8 Pa (80 kgf / cm) in a belt-clamping hot press 300 as shown in FIG. ² ) For 5 minutes, the layers were laminated and integrated, and the thermosetting resin was cured, so that a fiber-reinforced thermosetting resin decorative board 100 as shown in FIG.
[0049]
[Comparative Example 1]
In Example 1, the paste B was extruded by a T-die on the endless pressure belt to laminate the uncured substrate layer 10A, and then the lamination of the fibrous sheet 21 and the uncured surface layer 30A was omitted. As in Example 1, the fiber-reinforced thermosetting property consisting of a single layer of only the base material layer 10 in which the uncured base material layer 10A is cured by heating and pressing with a belt-clamping hot press 300. A resin decorative board was produced.
[0050]
[Comparative Example 2]
In Example 1, after paste B is extruded by a T-die on the endless pressure belt and the uncured base material layer 10A is laminated, the fibrous sheet 21 is laminated thereon, and then the fibrous sheet 21 In addition, a paste obtained by extruding paste B instead of paste A with a T-die and laminating an uncured substrate layer 10A as an uncured surface layer is a belt-clamping hot press 300 as in Example 1. The layers were integrated with each other by heating and pressing, and the thermosetting resin was cured to produce a fiber-reinforced thermosetting resin decorative board.
[0051]
[Performance comparison]
The fiber-reinforced thermosetting resin decorative plates of the examples and comparative examples had a mirror surface that had a good mirror surface only in Example 1, but in each comparative example, the surface was uneven due to the influence of reinforcing fibers. Made and inferior in specularity.
Each decorative board had good surface heat resistance, but the mechanical strength of the example was better than that of each comparative example.
[0052]
【The invention's effect】
(1) According to the present invention, a fiber-reinforced thermosetting resin decorative board having good specularity, surface heat resistance, and mechanical strength can be obtained.
(2) Also, if heating and pressurization is performed by a belt press system, continuous processing is possible instead of batch-type intermittent processing like a single-wafer heat press, so that it can be manufactured smoothly and productivity is improved. .
[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a conceptual diagram conceptually illustrating, in one form, a method for producing a fiber-reinforced thermosetting resin decorative board according to the present invention.
FIG. 2 is a conceptual diagram for conceptually explaining the manufacturing method according to the present invention in another form (belt press system) in the heating and pressurizing system.
FIG. 3 is a conceptual diagram conceptually illustrating the manufacturing method of the present invention in another form.
[Explanation of symbols]
10 Base material layer
10A Uncured substrate layer
11 Reinforcing fiber
12 Cured product of thermosetting resin
12A Uncured product of thermosetting resin
20 middle class
20A Uncured intermediate layer
21 Fiber sheet
30 Surface layer
30A Uncured surface layer
40 type
41M Lower and mirror plate
42 Upper mold
43 Mirror plate
50 Decorative sheet
100 Fiber reinforced thermosetting resin decorative board
100A laminated material
200 sheet heat press machine
210 type
211 Lower mold
212 Upper mold
220 Drive device
221 Lamb
222 Hydraulic cylinder
300 Belt-clamping heat press machine
310 Pressure belt
310M Mirror surface pressure belt
320 Driving roller
330 Guide roller
340 Heating and pressurizing device
350 Transport roller

Claims

A fibrous sheet is sandwiched between an uncured substrate layer composed of reinforcing fibers and an uncured material of a thermosetting resin, and an uncured surface layer composed of an uncured material of a thermosetting resin that does not contain reinforcing fibers. In such a state that the mirror plate is heated and pressed so that the mirror surface is in contact with the uncured surface layer, the thermosetting resin in the uncured substrate layer and the uncured surface layer is cured. Then, after stopping the heating and pressurization, the mirror plate is peeled and removed from the surface layer formed by curing the uncured surface layer.

A resin composition containing reinforcing fibers is extruded by an extruder to form an uncured substrate layer on the belt, and a fiber sheet is further laminated on the uncured substrate layer, and further extruded onto the fiber sheet. A resin composition not containing reinforcing fibers is extruded by a machine to laminate an uncured surface layer, and then a pressure belt is used from above and below using a mirror surface pressure belt as a pressure plate on the uncured surface layer side as a pressure belt. The method for producing a fiber-reinforced thermosetting resin decorative board according to claim 1, wherein heating and pressurization is performed by a belt press method.