JP4956877B2

JP4956877B2 - Decorative FRP molded product manufacturing method, decorative FRP molded product with shaped sheet, and decorated FRP molded product

Info

Publication number: JP4956877B2
Application number: JP2001292934A
Authority: JP
Inventors: 和宏須賀
Original assignee: Dai Nippon Printing Co Ltd
Current assignee: Dai Nippon Printing Co Ltd
Priority date: 2001-09-26
Filing date: 2001-09-26
Publication date: 2012-06-20
Anticipated expiration: 2021-09-26
Also published as: JP2003094472A

Description

【０００１】
【発明の属する技術分野】
本発明は、建築物、浴室等の床材に好適な、加飾ＦＲＰ（繊維強化プラスチック）成形品の製造方法に関する。特に、滑り防止性があり、転倒を防止すべき部分に好適な加飾ＦＲＰ成形品が得られる製造方法に関する。
【０００２】
【従来の技術】
ＦＲＰ成形品の成形時に、樹脂表面側に化粧シートを挿入して接着積層することで、表面加飾した加飾ＦＲＰ成形品が得られ（特開平７−３１４５９７号公報等参照）、また、成形型面に凹凸を設けておき、成形時にエンボスすることで、表面に凹凸を設けた成形品も得られる（特開平８−１１８３８４号公報等参照）。表面凹凸により、岩肌状や桝目状等の意匠感を付与して高級感ある成形品にできる。
【０００３】
【発明が解決しようとする課題】
しかしながら、上記の如き岩肌状や桝目状等の凹凸は、滑り防止という観点からは、穏やかな凹凸である為に、床表面に単なる水が在る場合では滑り難くなり、ある程度の効果はあるが、それが洗剤や石鹸が溶けた水の場合は滑り易い。また、この様な穏やかな凹凸では、体重が軽く、脚力に劣る幼児や高齢者にとっては、摩擦力も少なく滑り易いといった問題があった。したがって、特に浴室の床用途では、実用上の滑り防止効果は得られていなかった。
また、ＦＲＰ成形樹脂の内部離型剤が徐々にブリードアウトし、この点でも成形品表面が滑り易くなるという問題もあった。また、成形型の型面の広い領域に凹凸を設けるには、型加工代が高価となるという問題もあった。
【０００４】
すなわち、本発明の課題は、浴室床材等で、その表面上に石鹸水がある場合でも滑り防止効果が得られ、且つコスト高にならない、加飾ＦＲＰ成形品を製造する方法を提供することである。
【０００５】
【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、本発明の加飾ＦＲＰ成形品の製造方法では、一対の成形型の間に、ＦＲＰ未硬化物、絵柄層を有する加飾繊維質シートを挿入して積層し、更に、表面に凹部の間口が２０μｍ〜１ｍｍ、深さが５〜２００μｍの溝状の凹部である微細凹凸を有する賦形シートの微細凹凸面に熱硬化性樹脂の未硬化物或いは硬化物の層による透明な塗工層を形成したものを、該塗工層が前記加飾繊維質シート側と対面する様にして積層し、次いで、一対の成形型を閉じ、加熱加圧し、前記ＦＲＰ未硬化物、及び塗工層の熱硬化性樹脂の硬化を完了させ、次いで、一対の成形型を開くと共に、賦形シートを剥離除去する、事により、表面に微細凹凸を有する熱硬化性樹脂の硬化物よりなる透明な表面保護層兼滑防止層の裏面に、絵柄層、及びＦＲＰ層を積層してなる加飾ＦＲＰ成形品を得る方法とした。
【０００６】
この様な方法とすることで、賦形シートから、成形後は成形品表面を成す表面保護層兼滑防止層に微細凹凸が賦形されることにより、浴室等で石鹸水がある場合でも、滑り防止効果が得られる。該滑り防止効果は、微細凹凸により石鹸水を押し流す部分が存在し、且つ微細凹凸が足裏の接触部分に食い込むことにより、発現すると考えられる。しかも、本発明では、微細凹凸の賦形には賦形フィルムを使うので、成形型型面に微細凹凸を設けて、それから直接賦形する場合に比べて、コスト高にならず安価に賦形できる。その上、成形型に傷が付いても、傷が微小である限りに於いては、成形品表面に傷は賦形されず、且つ成形品表面に賦形される微細凹凸形状も不変である。その為、成形型を交換する頻度も少なくて済む。また、表面保護層兼滑防止層によって、ＦＲＰ成形樹脂の内部離型剤が徐々にブリードアウトするのも低減でき、離型剤ブリードアウトで滑り易くなるのも抑えることが出来る。
また、請求項２は、請求項１に記載の加飾ＦＲＰ成形品の製造方法において、前記賦形シートの微細凹凸が、成形版胴法により形成されたものである。さらに、請求項３は、請求項１または請求項２に記載の加飾ＦＲＰ成形品の製造方法において、前記賦形シートの微細凹凸が、電離放射線硬化性樹脂組成物の硬化物である。さらに、請求項４は、請求項１〜３のいずれかに記載の加飾ＦＲＰ成形品の製造方法において、前記塗工層が、充填剤を含有するものである。
また、請求項５に記載の発明は、表面に凹部の間口が２０μｍ〜１ｍｍ、深さが５〜２００μｍの溝状の凹部である微細凹凸を有する賦形シートの微細凹凸側に、表面に微細凹凸を有する熱硬化性樹脂の硬化物よりなる透明な表面保護層兼滑防止層を有し、該表面保護層兼滑防止層の裏面に、絵柄層を有する加飾繊維質シート、及びＦＲＰ層を積層してなる賦形シート付き加飾ＦＲＰ成形品である。さらに、請求項６は、請求項５に記載の賦形シート付き加飾ＦＲＰ成形品において、前記賦形シートの微細凹凸が、電離放射線硬化性樹脂組成物の硬化物である。さらに、請求項７は、請求項５または６に記載の賦形シート付き加飾ＦＲＰ成形品において、前記表面保護層兼滑防止層が、充填剤を含有するものである。
また、請求項８に記載の発明は、表面に凹部の間口が２０μｍ〜１ｍｍ、深さが５〜２００μｍの溝状の凹部である微細凹凸を有する熱硬化性樹脂の硬化物よりなる透明な表面保護層兼滑防止層を有し、該表面保護層兼滑防止層の裏面に、絵柄層を有する加飾繊維質シート、及びＦＲＰ層を積層してなる加飾ＦＲＰ成形品である。さらみ、請求項９は、請求項８に記載の加飾ＦＲＰ成形品において、前記表面保護層兼滑防止層が、充填剤を含有するものである。
【０００７】
【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。
【０００８】
〔概要〕
本発明による製造方法では、図１の説明図で各材料を積層する状況を概念的に示す如く、それぞれ油圧シリンダ８１のラム８２等により開閉動作する一対の成形型Ｍａ及びＭｂの間に、先ず、ＦＲＰ未硬化物５、絵柄層を有する加飾繊維質シート４を挿入して積層し、更に、表面に微細凹凸２Ａを有する賦形シートＳの該微細凹凸面に熱硬化性樹脂の未硬化物或いは硬化物の層による透明な塗工層３Ａを形成したものを、該塗工層３Ａが前記加飾繊維質シート４側と対面する様にして積層する。
【０００９】
図２は、加熱加圧前に於ける積層状態の各層を拡大した断面図であり、例示した賦形シートＳは、基材シート１１上に微細凹凸２Ａを表面に有する微細凹凸賦形層１２を積層した構成である。そして、賦形シートＳの微細凹凸２Ａ上に、繊維質シート４１に絵柄層４２が印刷等で形成された構成の加飾繊維質シート４が、同図の場合は該絵柄層４２側を賦形シートＳ側を向けて積層され、さらにこの加飾繊維質シート４の上に、ＦＲＰ未硬化物５が積層された状態である。
【００１０】
そして、一対の成形型Ｍａ及びＭｂを閉じて加熱加圧し、ＦＲＰ未硬化物５、塗工層３Ａの熱硬化性樹脂の硬化を完了させた後、一対の成形型Ｍａ及びＭｂを開き、賦形シートＳは剥離除去する。
【００１１】
以上の結果、例えば図６の断面図で例示の如き、加飾ＦＲＰ成形品Ｄが得られる。加飾ＦＲＰ成形品Ｄに於いては、前記塗工層３Ａは、前記微細凹凸２Ａとは逆凹凸形状の微細凹凸２が賦形された熱硬化性樹脂の硬化物よりなる透明な表面保護層兼滑防止層３となって成形品表面を成し、またその下側には、絵柄層４２、ＦＲＰ層６（加飾繊維質シートの繊維質シート４１に熱硬化性樹脂が含浸硬化した層と、ＦＲＰ未硬化物５が硬化した層）が積層された構成等とする。
【００１２】
〔賦形シート〕
図３の断面図で、本発明で使用する賦形シートＳの一例を示す。該賦形シートＳは、基材シート１１上に微細凹凸賦形層１２を設けた構成である。微細凹凸賦形層１２の表面には、成形品表面に設けるべき微細凹凸２（図６及び図７参照）とは逆凹凸形状の微細凹凸２Ａを設けてある。
【００１３】
上記基材シート１１としては、特に限定は無く、樹脂シート、紙、金属箔等が使用できるが、通常は、樹脂シートが用いられる。樹脂シートの場合の基材シートの厚みは、通常２０〜３００μｍ程度であるが、耐熱性、取り扱い易さ等の点で、好ましくは５０〜２００μｍ程度である。
基材シートに樹脂シートを用いる場合、該樹脂としては、例えば、熱可塑性ポリエステル樹脂、ポリカーボネート樹脂、アクリル樹脂、ポリアミド樹脂（ナイロン）、トリアセチルセルロース樹脂等が使用できる。なお、上記熱可塑性ポリエステル樹脂としては、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、エチレン−テレフタレート−イソフタレート共重合体、ポリエチレンナフタレート、ポリエステル系熱可塑性エラストマー等が使用できる。なお、ポリエステル系熱可塑性エラストマーは、ハードセグメントに高結晶性で高融点の芳香族ポリエステル、ソフトセグメントにはガラス転移温度が−７０℃以下の非晶性ポリエーテルを使用した、ブロックポリマーである。前記高結晶性で高融点の芳香族ポリエステルには、例えばポリブチレンテレフタレートが使用され、上記非晶性ポリエーテルには、例えばポリテトラメチレンエーテルグリコールが使用される。耐熱性、コストの点では、二軸延伸ポリエチレンテレフタレートが最適である。なお、樹脂シートは、必要に応じ適宜、染料や顔料等の着色剤で着色しても良い。
【００１４】
賦形シートＳ上の微細凹凸２Ａは、最終的に成形品表面に設ける微細凹凸２とは逆凹凸関係の凹凸であるが、この様な賦形シートＳ上の微細凹凸２Ａとしては、滑り防止効果の点で、凹部の間口（幅）２０μｍ〜１ｍｍ、深さ５〜２００μｍ程度の溝状の凹部多数からなる凹凸形状とするのが、滑り防止効果の点で良い。賦形シート上の微細凹凸２Ａに於ける溝状の凹部は、賦形後の成形品上の微細凹凸２では、凸条部となる。また、微細凹凸賦形層１２の厚みは、微細凹凸の深さを実現できるものとすれば良く、従って、５〜３００μｍ程度である。
図４に、賦形後の成形品表面上の微細凹凸２として、その数例の平面視形状を示す。符号２１は凸部、符号２２は凹部を示す。図４(Ａ)は格子状、図４(Ｂ)は斜格子状、図４(Ｃ)は三角格子状、図４(Ｄ)は六角格子状、図４(Ｅ)は平行直線状である。
【００１５】
上記の如き微細凹凸２Ａを有する賦形シートＳの作製方法は、特に限定されるものではないが、微細な凹凸を再現性良く形成でき、且つ生産性も良い点で、これから述べる「成形版胴法」が最適である。但し、この他の方法として、樹脂フィルムの熱プレスによるエンボス加工で作製する事も可能ではあるが、微細性に関しては、「成形版胴法」の方が好ましい。
【００１６】
「成形版胴法」は、特開昭５７−８７３１８号公報、特公昭５７−２２７５５号公報、特公昭６３−５００６６号公報、特開平７−３２４７６号公報等に開示されるものであって、成形版胴（賦形版、ロール凹版等とも呼称される）の凹凸形状を忠実に電離放射性硬化性樹脂の硬化物に賦形する方法である。基本的には、以下の工程からなる（図５参照）。
【００１７】
（１）表面に目的とする微細凹凸２Ａの凹凸形状と同形状且つ逆凹凸の凹凸形状（微細凹凸２と同形状）９１を形成した円筒形状の成形版胴９２を用意し、これを軸芯の回りに回転させる。
（２）連続帯状の基材シート１１を、該成形版胴９２の周速度と同速度で供給する。
（３）該基材シート１１と該成形版胴９２とを、その間に電離放射線硬化性樹脂の未硬化液状組成物９４を介して重ね合わせて密着させ、該液状組成物が該成形版胴の少なくとも凹部を完全に充填する様にする。
（４）その状態のままで電離放射線照射器９５から電離放射線９６を照射して、該液状組成物を架橋、硬化させる。
（５）而る後に、基材シート１１を、それに接着し且つ成形版胴上の凹凸形状９１が賦形された電離放射線硬化性樹脂の硬化物からなり表面に微細凹凸２Ａを有する微細凹凸賦形層１２と共に、成形版胴９２から剥離除去する。この結果、微細凹凸２Ａを有する微細凹凸賦形層１２が基材シート１１に接着した構成で賦形シートＳが得られる。
【００１８】
以上の方法に於いて、成形版胴９２としては、公知の凹版、グラビア版、エンボス版と基本的には、同様の材料、同様の構造、同様の製法によるものを用いれば良い。成形版胴の材料としては、通常は鉄、銅等の金属が用いられる。但し、成形版胴内部から紫外線或いは可視光線を照射する場合には、硝子、石英等の透明な材料を用いる。
成形版胴の軸芯の回りの回転駆動は、通常の輸転式グラビア印刷機、輪転式エンボス機等と同様な機構、方法を用いれば良い。基材シートの成形版胴への密着の為には、ゴム、金属等の押圧ローラ９７で圧着する。又基材シートの成形版胴からの剥離にもゴム、金属等の剥離ローラ９８で押さえて剥離する。基材シートは連続帯状のものを用いる。此の様な基材シートは巻出ロール（供給ロール）から巻き出して、微細凹凸２Ａの形成後は巻取りロール（排紙ロール）で巻き取る。
【００１９】
基材シートと成形版胴とを、その間に電離放射線硬化性樹脂の未硬化液状組成物を介して重ね合わせて密着させる態様としては、次の（１）〜（３）がある。（１）先ず基材シート上に未硬化液状組成物を塗布し、次いで該塗布面が成形版胴表面に向くようにして、該基材シートを該成形版胴に重ね合わせる。（２）図５の如く先ず成形版胴９２上に液状組成物９４をＴダイ型樹脂液供給手段９３等を用いて塗布し、次いで該成形版胴上の塗布面に基材シート１１を重ね合わせる。（３）先ず成形版胴上と基材シート上との各々に液状組成物を塗布し、次いで該基材シートと該成形版胴とを各々の塗布面が対向する様にして重ね合わせる。
【００２０】
成形版胴と基材シート間にある未硬化液状組成物への電離放射線の照射の態様としては、次の（Ａ）と（Ｂ）がある。（Ａ）図５の如く電離放射線に対して透明な基材シートを選び（例えば紫外線に対してポリエチレンテレフタレートシート、電子線に対しては薄葉紙を選択）、基材シート側から照射する。（Ｂ）電離放射線に対して透明な成形版胴を選び（例えば、紫外線に対して石英の成形版胴を選択）、成形版胴の内部から照射する。
【００２１】
基材シートの材料は、（１）ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等の熱可塑性樹脂ポリエステル樹脂、ポリエチレン、ポリプロピレン、ポリメチルペンテン、オレフィン系熱可塑性樹脂エラストマー等のポリオレフィン樹脂、ポリ塩化ビニル、ポリカーボネート、ポリスチレン、ＡＢＳ樹脂、アクリル樹脂等の樹脂シート、（２）薄葉紙、上質紙、クラフト紙、和紙等の紙、（３）硝子、ビニロン、ポリエステル、セルロース等の繊維からなる不織布、或いは織布、（４）アルミニウム、鉄、銅等の金属箔等がある。なお、上記（２）〜（４）は、透明な成形版胴内からの紫外線照射、又は電子線等の高透過性放射線の場合のみ可能である。
【００２２】
電離放射線硬化性樹脂としては、分子中に（メタ）アクリロイル基、（メタ）アクリロイルオキシ基等の重合性不飽和結合、又は、エポキシ基等のカチオン重合性官能基を有するプレポリマー、モノマー、又はポリマーを、１種のみ又は２種以上適宜混合した組成物を用いる。或いは、ポリエンとポリチオールとの組み合わせによるポリエン／チオール系のプレポリマーからなる組成物も用いることができる。組成物は、未硬化時に液状のものを用いる。
【００２３】
前記分子中に重合性不飽和結合を有するプレポリマーの例としては、不飽和ジカルボン酸と多価アルコールの縮合物等の不飽和ポリエステル類、ポリエステル（メタ）アクリレート、ウレタン（メタ）アクリレート、エポキシ（メタ）アクリレート、メラミン（メタ）アクリレート、シリコーン（メタ）アクリレート等の（メタ）アクリレート類がある〔尚、本明細書では（メタ）アクリレートとは、アクリレート又はメタクリレートの意味で用いる。以下同様〕。前記分子中に重合性不飽和結合を有するモノマーの例としては、スチレン、α−メチルスチレン等のスチレン系モノマー、（メタ）アクリル酸メチル、（メタ）アクリル酸−２−エチルヘキシル、（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸ブトキシエチル等の単官能（メタ）アクリル酸エステル類、エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等の多官能（メタ）アクリル酸エステル類、（メタ）アクリル酸−２−（Ｎ，Ｎ−ジエチルアミノ）エチル、（メタ）アクリル酸−２−（Ｎ，Ｎ−ジメチルアミノ）エチル、（メタ）アクリル酸−２−（Ｎ，Ｎ−ジベンジルアミノ）エチル等の不飽和酸の置換アミノアルコールエステル類、（メタ）アクリルアミド等の不飽和カルボン酸アミド等がある。
【００２４】
また、分子中にカチオン重合性官能基を有するプレポリマーとしては、ビスフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂、脂肪族型エポキシ樹脂等、脂肪環型エポキシ樹脂等のエポキシ樹脂、脂肪族系ビニルエーテル、芳香族系ビニルエーテル、ウレタン系ビニルエーテル、エステル系ビニルエーテル等のビニルエーテル系樹脂、環状エーテル系樹脂、スピロ系化合物等のプレポリマー等がある。
【００２５】
また、ポリエン／チオール系のプレポリマーとしては、分子中に２個以上のメルカプト基を有するポリチオール化合物、例えば、トリメチロールプロパントリチオグリコレート、トリメチロールプロパントリチオプロピレート、ペンタエリスリトールテトラチオグリコール等がある。一方、ポリエンとしては、ジオールとジイソシアネートによるポリウレタンの両端にアリルアルコールを付加したもの等がある。
【００２６】
電離放射線硬化性樹脂としては、以上の化合物を必要に応じ１種もしくは２種以上混合して用いるが、樹脂組成物に通常の塗工適性を付与するために、前記プレポリマー又はオリゴマーを５質量％以上、前記モノマー及び／又はポリチオールを９５質量％以下とすることが好ましい。
また、硬化物の可撓性、表面硬度、剥離性等の物性を調節する為に前記電離放射線硬化性樹脂に対して、以下の様な電離放射線非硬化性樹脂を１〜７０質量％程度混合して用いることができる。電離放射線非硬化性樹脂としてはウレタン系樹脂、セルロース系樹脂、ポリエステル系樹脂、アクリル系樹脂、ブチラール樹脂、ポリ塩化ビニル、ポリ酢酸ビニル等の熱可塑性樹脂を用いることができる。また、剥離性を向上させる為に、シリコーン樹脂、ワックス等の滑剤を添加することができる。
【００２７】
特に紫外線で硬化させる場合には前記電離放射線硬化性樹脂組成物に光重合開始剤を添加する。分子中にラジカル重合性不飽和結合を有する化合物に対しては、アセトフェノン類、ベンゾフェノン類、ミヒラーベンゾイルベンゾエート、α−アミロキシムエステル、テトラメチルメウラムモノサルファイド、チオキサントン類等がある。
分子中にカチオン重合性官能基を有する化合物に対しては、芳香族ジアゾニウム塩、芳香族スルホニウム塩、芳香族ヨードニウム塩、メタロセン化合物、ベンゾインスルホン酸エステル、ジアリルヨードシル塩等がある。又、必要に応じて更に、光増感剤としてｎ−ブチルアミン、トリエチルアミン、トリ−ｎ−ブチルホスフィン等を混合して用いることもできる。
【００２８】
以上の電離放射線硬化性樹脂組成物の未硬化液状組成物を成形版胴、或いは基材シートに塗工するには公知の各種方法、例えば、ロールコート、カーテンフローコート、Ｔダイコート等の方法を用る。特に成形版胴に塗工の場合はインキパン中の液状組成物に、回転する成形版胴を浸漬させる（所謂ドブ浸け）も可能である。
【００２９】
尚、ここで電離放射線としては、電磁波又は荷電粒子線のうち分子を重合、架橋し得るエネルギーを有するものを意味し、紫外線、可視光線、Ｘ線、電子線、α線等があるが、通常紫外線、又は電子線が用いられる。紫外線源としては、超高圧水銀灯、高圧水銀灯、低圧水銀灯、カーボンアーク灯、ブラックライトランプ、メタルハライドランプ等の光源が使用される。電子線源としては、コッククロフトワルトン型、バンデグラフト型、共振変圧器型、絶縁コア変圧器型、或いは、直線型、ダイナミトロン型、高周波型等の各種電子線加速器を用い、１００〜１０００ｋｅＶ、好ましくは、１００〜３００ｋｅＶのエネルギーをもつ電子を照射するものが使用される。
【００３０】
〔塗工層〕
上述の如き賦形シートは、ＦＲＰ未硬化物等と重ねる前に、その微細凹凸２Ａの面に、熱硬化性樹脂の未硬化物或いは硬化物の層による透明な塗工層３Ａを塗工形成しておく（図１参照）。この塗工層３Ａは、成形後は、成形品表面の透明な表面保護層となると共に、微細凹凸担持層（滑防止層）ともなる。また、成形品に於いて、下側の絵柄層が透視できる様に塗工層は透明（無着色又は着色）とする。なお、塗工層を硬化物とする場合は、半硬化又は完全硬化させる。但し、半硬化、或いは未硬化の場合は、流動性が無く固体であることが、作業性の点で好ましい。
【００３１】
上記熱硬化性樹脂としては、例えば、ジアリルフタレート（ＤＡＰ）樹脂、不飽和ポリエステル樹脂、エポキシ変性ポリエステル樹脂、エポキシ樹脂、メラミン樹脂、ウレタン樹脂等が使用できる。
【００３２】
上記熱硬化性樹脂は、適宜、硬化剤、反応性希釈剤、充填剤、その他添加剤等を添加して使用する。例えば、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、ナフテン酸コバルト等の硬化反応触媒、スチレン単量体等の反応性希釈剤等を添加する。また、充填剤としては、例えば、コロイダルシリカ等のシリカ、炭酸カルシウム、クレー、タルク等の粉末を添加する。充填剤添加により、未硬化或いは半硬化状態での流動性、粘着性を低減できる。
【００３３】
また、その他添加剤は、例えば、着色剤、減摩剤、光安定剤、抗菌剤、防カビ剤等である。減摩剤としては、例えば、アルミナ（α−アルミナ等）、アルミノシリケート等の粉末を添加する。特に、塗工層は、成形後は表面保護層兼滑防止層として成形品表面を成し、また、浴室床材等の水周り用途を考えると、抗菌剤や防カビ剤の添加は好ましい。抗菌剤としては、例えば、銀イオンをイオン交換可能に担持したゼオライト粉末等、防カビ剤としては、例えば、１０，１０−オキシビスフェノキシアルシン等を添加すれば良い。
【００３４】
なお、塗工層を賦形シートの微細凹凸上に塗工形成するには、ロールコート等の公知の塗工法によれば良い。その際、塗工適性調整の為に、必要に応じ適宜、揮発性溶剤を添加した樹脂を使用し、塗布後、該溶剤は乾燥させる。塗工層の厚さは、賦形する微細凹凸の深さに応じたものとすれば良く、５〜３００μｍ程度である。
【００３５】
〔加飾繊維質シート〕
加飾繊維質シート４は、繊維質シート４１に印刷等によって絵柄層４２を形成したシートである。繊維質シート４１が未含浸のものは、その中に成形時の熱圧によってＦＲＰ未硬化物５の樹脂が含浸する。そして成形後は、該樹脂含浸した繊維質シート４１は、ＦＲＰ未硬化物５の硬化物と共に、ＦＲＰ層６となる（図６参照）。
【００３６】
使用時まで絵柄層４２を担持しておく事になる繊維質シート４１は、成形後は、成形品の寸法安定性にも寄与する。また、成形時に、絵柄層４２を賦形シートＳ側にして積層すれば、絵柄層の絵柄の歪み、流れ、或いは亀裂も生じ難くなる。
【００３７】
上記繊維質シート４１としては、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。なかでも、コスト、物性、密着性、含浸性能、緩い凹凸への形状追従性等を考慮すると、厚さ０．２ｍｍ以下の合成樹脂繊維の不織布が好ましい。例えば、ポリエステル樹脂繊維の不織布が好適である。
なお、繊維質シートは、樹脂未含浸でも良いのだが、樹脂含浸しておいても良い。該樹脂には、例えば前述塗工層で列記した様な熱硬化性樹脂が使用できる。
【００３８】
なお、絵柄層４２は、印刷等の公知の形成法で繊維質シート４１に対して形成される。例えば、印刷は、グラビア印刷、シルクスクリーン印刷、オフセット印刷、インキジェットプリント等で行う。絵柄は、用途によるが、例えば、石目模様、砂目模様、梨地模様、タイル貼調模様、煉瓦積調模様、木目模様、布目模様、皮絞模様、文字、幾何学模様、全面ベタ、或いはこれら二種以上の組合せ等を用いる。なお、絵柄層形成用のインキは、例えば、アクリル樹脂、塩化ビニル−酢酸ビニル共重合体、ポリエステル樹脂、セルロース系樹脂、ウレタン樹脂等の単体又はこれらを含む混合物がバインダー樹脂として用いられ、チタン白、亜鉛華、カーボンブラック、鉄黒、弁柄、朱、黄鉛、チタンイエロー、コバルトブルー、群青等の無機顔料、アニリンブラック、キナクリドンレッド、イソインドリノンイエロー、フタロシアニンブルー等の有機顔料、アルミニウム箔粉、真鍮箔粉、二酸化チタン被覆雲母箔粉等の光輝性顔料、蛍光顔料、或いはその他染料等が着色剤として用いられる。
【００３９】
〔ＦＲＰ未硬化物〕
ＦＲＰ未硬化物５としては、ＦＲＰ成形材料として従来公知のもので良く、本発明の場合では、なかでも、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は既にシート状に成形されている為、平板状乃至は平板近似の成形品の成形に好適である。なお、ＦＲＰ未硬化物は、加熱により硬化させる。
ＦＲＰ未硬化物の樹脂としては、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、ウレタン樹脂等の所謂熱硬化性樹脂も使用できる。また、ＦＲＰの強化材としての繊維は、ガラス繊維が代表的だが、炭素繊維、チタン酸カリウム繊維等の無機繊維、或いはポリエステル繊維、ナイロン繊維、ビニロン繊維等の合成樹脂繊維等も使用される。
また、ＦＲＰ未硬化物には、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したものを用いる。
【００４０】
ＦＰＲ未硬化物５は、他材料と積層した状態で成形型やプレス機等による加熱加圧によって、樹脂含浸し硬化した繊維質シート４１と共にＦＲＰ層６を構成する。加熱加圧条件は、ＦＰＲ未硬化物や塗工層に使用する樹脂等に応じた条件となる。
【００４１】
〔加熱加圧〕
加熱加圧により、積層した上述各材料を接着し強固に一体化すると同時に、成形品表面には、賦形シート上の微細凹凸２Ａとは逆凹凸形状の微細凹凸２が賦形され、図６の断面図で例示の如き、所望の加飾ＦＲＰ成形品Ｄが得られる。
加熱加圧の条件は、ＦＰＲ未硬化物や塗工層等に使用する樹脂等に応じた条件となる。例えば、加熱温度１００〜１７０℃、加圧圧力５〜２０ＭＰａ、加熱加圧時間１〜８０ｍｉｎ程度である。なお、成形型には、適度に公知の離型剤を吹き付けておいて成形すると、脱型性が良い。
【００４２】
ところで、成形型の型面には、図１の成形型Ｍｂで例示の如く凹凸を設けておいても良い。該凹凸は、本発明で言うところの微細凹凸２及び２Ａよりも、大きな（緩やかな）大柄凹凸である。該大柄凹凸は、例えば、岩肌状、桝目状、煉瓦積状等である。型面上の大柄凹凸は、賦形シートを介して成形品表面に賦形される。成形時には、賦形シートは大柄凹凸の凹凸形状に追従させることができるので、賦形シートが邪魔になることはない。賦形シートでは表現し難い様な高低差が大きく緩やかな山谷のある凹凸は、この大柄凹凸として成形型の型面から賦形するのが好適である。
上記の如き大柄凹凸によって、図７の断面図で例示する加飾ＦＲＰ成形品Ｄの如く、その表面に、上記の如き大柄凹凸７に重なって微細凹凸２を有する成形品が得られる。そして、加飾ＦＲＰ成形品Ｄは、大柄凹凸によって、より高意匠なものとなる。
【００４３】
〔用途〕
なお、本発明による加飾ＦＲＰ成形品の用途は、特に限定されるものではないが、好適には、その表面に水が存在する場合での滑防止性能を活かせる用途に用いられる。例えば、建築物、浴室等の床材である。また、自動車、電車、航空機、船舶等の床材も好適である。なお、加飾ＦＲＰ成形品の全体形状は、平板状の他、立体形状でも良い。
【００４４】
【実施例】
以下、実施例及び比較例により本発明を更に詳述する。
【００４５】
〔実施例１〕
先ず、図３の如き賦形シートＳとして、基材シート１１とする厚さ１００μｍの二軸延伸ポリエチレンテレフタレートシート上に、図５で示す様な成形版胴法によって、紫外線で硬化する電離放射線硬化性樹脂〔３官能ウレタンアクリレートプレポリマー、ＤＰＨＡ（ジペンタエリスリトールヘキサアクリレート）、及びベンゾフェノン系光重合開始剤による未硬化液状組成物〕の硬化物としての微細凹凸賦形層１２を積層して賦形シートを作製した。微細凹凸賦形層１２に形成した微細凹凸２Ａの凹凸形状は、多数の直線溝状で、凹部の開口幅５０μｍ、凸部の幅５０μｍ、凹部の深さ２０μｍとした。
【００４６】
次に上記賦形シートＳの微細凹凸２Ａの面上に、熱硬化性樹脂としてコロイダルシリカを１０質量％添加したジアリルフタレート（ＤＡＰ）樹脂からなる塗液を、ロールコートにより塗布し加熱乾燥して、半硬化状態の熱硬化性樹脂からなる厚さ５０μｍの透明な塗工層３Ａを形成した。
【００４７】
一方、加飾繊維質シート４としては、坪量１００ｇ／ｍ²のポリエステル製不織布からなる繊維質シート４１の片面に、ポリエステルポリオール１００質量部とヘキサメチレンジイソシアネート８質量部とからなるバインダー樹脂に着色剤を添加したグラビアインキを、グラビア印刷して、花崗岩調の絵柄層４２を設けたものを用意した。
【００４８】
そして、図１の説明図の様にして、成形品表面側に対応する成形型Ｍｂ（図面下側）には型面に岩肌調の大柄凹凸７を設けたものを用い、該成形型Ｍｂ側の下側から順に、（塗工層３Ａを上向きの）塗工層３Ａ付きの賦形シートＳ、（絵柄層４２は下向きの）加飾繊維質シート４、ＳＭＣからなるＦＲＰ未硬化物５を重ねて、一対の成形型Ｍａ及びＭｂ間に挿入した。なお、上記ＳＭＣとしては、不飽和ポリエステル樹脂に硝子繊維を補強繊維として用いたものを使用した。
【００４９】
そして、１５０℃に加熱された成形型Ｍａ及びＭｂを閉じて、７Ｐａ（約７０ｋｇｆ／ｃｍ²）の圧力で１０分間、加熱加圧した後、成形型を開いて、成形品表面から賦形シートＳのみを剥離して、図７の如き構成の加飾ＦＲＰ成形品Ｄを得た。
【００５０】
得られた加飾ＦＲＰ成形品Ｄは、表面の大柄凹凸７により一見通常の岩肌調のものであるが、表面を拡大して観察すると、図４（Ｅ）の平面視形状の様で、凸部２１及び凹部２２の幅が５０μｍ、深さ２０μｍの、万線状の微細凹凸２が形成されていた。
【００５１】
〔比較例１〕
実施例１に於いて、賦形シートの代わりに、その基材シートに直接塗工層を形成したものを用いた他は、実施例１と同様にして成形後、成形品表面から基材シートを剥離して、大柄凹凸のみ賦形された加飾ＦＲＰ成形品を得た。
【００５２】
〔評価結果〕
実施例１及び比較例１による各加飾ＦＲＰ成形品について、その表面を水で濡らした場合と、石鹸水で濡らした場合の両方について、滑り防止効果を評価した。評価は、成形品表面を水或いは石鹸水で濡らした後、その表面を手のひらで往復して擦り、滑り具合を確認した。
その結果、微細凹凸を有する実施例１の加飾ＦＲＰ成形品は、水、石鹸水、どちらの場合でも、滑りにくく、滑り防止効果は良好であった。一方、微細凹凸がなく大柄凹凸のみの比較例１の加飾ＦＲＰ成形品は、石鹸水はもちろん、水でも滑り易く、滑り防止効果は無かった。
【００５３】
【発明の効果】
本発明によれば、成形品表面に賦形された微細凹凸により、浴室等で表面に石鹸水がある場合でも、石鹸水の流れが押し分けられ微細凹凸が足に食い込む為か、滑り防止効果が得られる。しかも、微細凹凸の賦形には賦形フィルムを使うので、成形型型面に微細凹凸を設けて、それから賦形する場合に比べて、コスト高にならず安価に賦形できる。また、表面保護層兼滑防止層によって、ＦＲＰ成形樹脂の内部離型剤が徐々にブリードアウトするのも低減でき、離型剤ブリードアウトで滑り易くなるのも抑えることが出来る。
【図面の簡単な説明】
【図１】本発明にて一対の成形型内に、各材料を積層する状況を概念的に説明図。
【図２】成形型内の各材料の積層状態を示す部分拡大断面図。
【図３】本発明で使用する賦形シートの一例を示す断面図。
【図４】本発明で賦形される微細凹凸の平面視形状の数例を示すを平面図。
【図５】賦形シートの作製法の一例（成形版胴法）を概念的に示す説明図。
【図６】本発明で得られる加飾ＦＲＰ成形品の一例を示す断面図。
【図７】本発明で得られる加飾ＦＲＰ成形品の別の一例を示す断面図。
【符号の説明】
１１基材シート
１２微細凹凸賦形層
２（賦形後の）微細凹凸
２Ａ（賦形シート上の）微細凹凸
２１（賦形後の）微細凹凸の凸部
２２（賦形後の）微細凹凸の凹部
３表面保護層兼滑防止層
３Ａ塗工層
４加飾繊維質シート
４１繊維質シート
４２絵柄層
５ＦＲＰ未硬化物
６ＦＲＰ層
７大柄凹凸
８１油圧シリンダ
８２ラム
９１凹凸形状
９２成形版胴
９３Ｔダイ型樹脂液供給手段
９４未硬化樹脂液
９５電離放射線照射器
９６電離放射線
９７押圧ローラ
９８剥離ローラ
Ｄ加飾ＦＲＰ成形品
Ｍａ成形型
Ｍｂ成形型
Ｓ賦形シート[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a decorated FRP (fiber reinforced plastic) molded article suitable for flooring materials such as buildings and bathrooms. In particular, the present invention relates to a method for producing a decorative FRP molded article that has anti-slip properties and is suitable for a portion that should be prevented from falling.
[0002]
[Prior art]
At the time of molding of the FRP molded product, a decorative FRP molded product with a surface decoration is obtained by inserting a decorative sheet on the resin surface side and laminating and laminating (see JP-A-7-314597, etc.). By providing unevenness on the mold surface and embossing at the time of molding, a molded product having unevenness on the surface can also be obtained (see JP-A-8-118384, etc.). Due to the surface irregularities, it is possible to give a sense of design such as a rock surface or a grid shape to a high-quality molded product.
[0003]
[Problems to be solved by the invention]
However, the unevenness such as the rock surface and the mesh shape as described above is a gentle unevenness from the viewpoint of slip prevention, and therefore it is difficult to slip when there is mere water on the floor surface, and there is a certain effect. If it is water with detergent or soap dissolved, it is slippery. In addition, such a gentle unevenness has a problem that an infant or an elderly person who is light in weight and inferior in leg strength has little frictional force and is easy to slide. Therefore, practically, an anti-slip effect has not been obtained particularly in bathroom floor applications.
Further, the internal release agent of the FRP molding resin gradually bleeds out, and there is also a problem that the surface of the molded product becomes slippery in this respect. In addition, in order to provide unevenness in a wide area of the mold surface of the mold, there is a problem that the mold processing cost is expensive.
[0004]
That is, an object of the present invention is to provide a method for producing a decorative FRP molded product that is effective in preventing slipping even when there is soapy water on the surface of a bathroom flooring or the like and that does not increase the cost. It is.
[0005]
[Means for Solving the Problems]
  Therefore, in order to solve the above problems, in the method for producing a decorated FRP molded product of the present invention, a decorative fiber sheet having an FRP uncured product and a pattern layer is inserted and laminated between a pair of molds. And on the surfaceIt is a groove-shaped recess having a recess opening of 20 μm to 1 mm and a depth of 5 to 200 μm.What formed the transparent coating layer by the layer of the uncured or hardened material of thermosetting resin on the fine uneven surface of the shaping sheet which has fine unevenness, the coating layer is the above-mentioned decorative fiber sheet side and Laminate so as to face each other, then close the pair of molds, heat and press to complete the curing of the FRP uncured product and the thermosetting resin of the coating layer, and then open the pair of molds At the same time, the patterning sheet and the FRP layer are laminated on the back surface of the transparent surface protective layer and anti-slip layer made of a cured thermosetting resin having fine irregularities on the surface by peeling and removing the shaped sheet. It was set as the method of obtaining the decorative FRP molded product which becomes.
[0006]
  By such a method, from the shaped sheet, after molding, by forming fine irregularities in the surface protective layer and anti-slip layer forming the surface of the molded product, even when there is soapy water in the bathroom, A slip prevention effect is obtained. The anti-slip effect is considered to be manifested by the presence of a portion where soap water is washed away by the fine unevenness and the fine unevenness biting into the contact portion of the sole. Moreover, in the present invention, since a shaping film is used for shaping the fine irregularities, the shaping is performed at a low cost without increasing the cost as compared with the case of forming the fine irregularities on the mold surface and then shaping directly. it can. In addition, even if the mold is scratched, as long as the scratch is minute, the surface of the molded product is not scratched, and the fine uneven shape formed on the surface of the molded product is unchanged. . For this reason, the frequency of exchanging the mold is small. Further, the surface protective layer and anti-slip layer can reduce the bleed-out of the internal release agent of the FRP molding resin gradually, and can also prevent the release agent bleed-out from becoming slippery.
  Further, according to claim 2, in the method for producing a decorated FRP molded product according to claim 1, fine irregularities of the shaped sheet are formed by a molding plate cylinder method. Furthermore, Claim 3 is the hardened | cured material of the ionizing radiation-curable resin composition in the manufacturing method of the decorating FRP molded product of Claim 1 or Claim 2, and the fine unevenness | corrugation of the said shaping sheet. Furthermore, Claim 4 is a manufacturing method of the decorated FRP molded product according to any one of Claims 1 to 3, wherein the coating layer contains a filler.
  In addition, the invention according to claim 5 is characterized in that the surface of the shaped sheet having fine irregularities which are groove-shaped concave portions having a concave opening of 20 μm to 1 mm and a depth of 5 to 200 μm on the surface is fine on the surface. A decorative fiber sheet having a transparent surface protection layer and anti-slip layer made of a cured product of a thermosetting resin having irregularities, and having a pattern layer on the back surface of the surface protection layer and anti-slip layer, and an FRP layer Is a decorative FRP molded product with a shaping sheet. Furthermore, claim 6 is a decorated FRP molded product with a shaped sheet according to claim 5, wherein the fine irregularities of the shaped sheet are a cured product of an ionizing radiation curable resin composition. Furthermore, Claim 7 is a decorative FRP molded product with a shaped sheet according to Claim 5 or 6, wherein the surface protective layer and anti-slip layer contains a filler.
  The invention according to claim 8 is a transparent surface made of a cured product of a thermosetting resin having fine irregularities which are groove-shaped recesses having a recess opening of 20 μm to 1 mm and a depth of 5 to 200 μm on the surface. A decorative FRP molded article having a protective layer and anti-slip layer, and a decorative fiber sheet having an image layer and an FRP layer laminated on the back surface of the surface protective layer and anti-slip layer. In addition, according to claim 9, in the decorative FRP molded article according to claim 8, the surface protective layer and anti-slip layer contains a filler.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[0008]
〔Overview〕
In the manufacturing method according to the present invention, as shown conceptually in the explanatory diagram of FIG. 1, firstly, a pair of molds Ma and Mb that are opened and closed by the ram 82 of the hydraulic cylinder 81 and the like are firstly shown. , FRP uncured material 5 and decorative fibrous sheet 4 having a pattern layer are inserted and laminated, and the thermosetting resin is uncured on the fine uneven surface of the shaped sheet S having fine unevenness 2A on the surface. A layer in which a transparent coating layer 3A is formed by a layer of a product or a cured product is laminated so that the coating layer 3A faces the decorative fiber sheet 4 side.
[0009]
FIG. 2 is an enlarged cross-sectional view of each layer in a laminated state before heating and pressing, and the illustrated shaped sheet S has a fine uneven shaped layer 12 having fine unevenness 2A on the surface of the base sheet 11. It is the structure which laminated | stacked. The decorative fibrous sheet 4 having a structure in which the pattern layer 42 is formed on the fibrous sheet 41 by printing or the like on the fine irregularities 2A of the shaped sheet S is applied to the pattern layer 42 side in the case of FIG. In this state, the FRP uncured material 5 is laminated on the decorative fiber sheet 4.
[0010]
Then, the pair of molds Ma and Mb are closed and heated and pressurized to complete the curing of the thermosetting resin of the FRP uncured product 5 and the coating layer 3A, and then the pair of molds Ma and Mb are opened and applied. The shaped sheet S is peeled and removed.
[0011]
As a result, a decorated FRP molded product D as illustrated in the cross-sectional view of FIG. 6 is obtained. In the decorative FRP molded product D, the coating layer 3A is a transparent surface protective layer made of a cured product of a thermosetting resin in which fine unevenness 2 having a shape opposite to the fine unevenness 2A is formed. The anti-slip layer 3 forms the surface of the molded product, and on the lower side thereof, the pattern layer 42 and the FRP layer 6 (the layer in which the thermosetting resin is impregnated and cured on the fibrous sheet 41 of the decorative fibrous sheet) And a layer in which the FRP uncured product 5 is cured).
[0012]
[Shaping sheet]
In sectional drawing of FIG. 3, an example of the shaping sheet S used by this invention is shown. The shaped sheet S has a configuration in which a fine uneven shaped layer 12 is provided on a substrate sheet 11. On the surface of the fine concavo-convex shaping layer 12, fine concavo-convex 2A having a reverse concavo-convex shape opposite to the fine concavo-convex 2 (see FIGS. 6 and 7) to be provided on the surface of the molded product is provided.
[0013]
There is no limitation in particular as the said base material sheet 11, Although a resin sheet, paper, metal foil, etc. can be used, a resin sheet is used normally. The thickness of the base sheet in the case of a resin sheet is usually about 20 to 300 μm, but preferably about 50 to 200 μm in terms of heat resistance, ease of handling, and the like.
When a resin sheet is used for the base sheet, for example, a thermoplastic polyester resin, a polycarbonate resin, an acrylic resin, a polyamide resin (nylon), a triacetyl cellulose resin, or the like can be used. Examples of the thermoplastic polyester resin include polyethylene terephthalate, polybutylene terephthalate, ethylene-terephthalate-isophthalate copolymer, polyethylene naphthalate, polyester-based thermoplastic elastomer, and the like. The polyester-based thermoplastic elastomer is a block polymer using a hard crystalline aromatic polyester having a high crystallinity and a high melting point, and an amorphous polyether having a glass transition temperature of −70 ° C. or lower for the soft segment. For example, polybutylene terephthalate is used for the highly crystalline aromatic polyester having a high melting point, and for example, polytetramethylene ether glycol is used for the amorphous polyether. Biaxially stretched polyethylene terephthalate is optimal in terms of heat resistance and cost. The resin sheet may be appropriately colored with a colorant such as a dye or a pigment as necessary.
[0014]
The fine irregularities 2A on the shaped sheet S are irregularities having a reverse irregularity relationship with the fine irregularities 2 that are finally provided on the surface of the molded product. From the standpoint of the effect, it is sufficient for the anti-slip effect to have a concave-convex shape composed of a large number of groove-like concave portions having a frontage (width) of the concave portion of 20 μm to 1 mm and a depth of about 5 to 200 μm. The groove-like recesses in the fine irregularities 2A on the shaped sheet become ridges in the fine irregularities 2 on the molded product after shaping. Moreover, the thickness of the fine uneven | corrugated shaped layer 12 should just be able to implement | achieve the depth of a fine unevenness | corrugation, Therefore, it is about 5-300 micrometers.
In FIG. 4, the planar view shape of the example is shown as the fine unevenness | corrugation 2 on the molded article surface after shaping. Reference numeral 21 denotes a convex portion, and reference numeral 22 denotes a concave portion. 4A is a lattice shape, FIG. 4B is an oblique lattice shape, FIG. 4C is a triangular lattice shape, FIG. 4D is a hexagonal lattice shape, and FIG. 4E is a parallel straight line shape. .
[0015]
The method for producing the shaped sheet S having the fine irregularities 2A as described above is not particularly limited, but the “molding plate cylinder” to be described below is preferable because fine irregularities can be formed with good reproducibility and productivity. The “method” is optimal. However, as another method, it is possible to produce the resin film by embossing by hot pressing, but regarding the fineness, the “molding plate cylinder method” is preferable.
[0016]
"Forming plate cylinder method" is disclosed in JP-A-57-87318, JP-B-57-22755, JP-B-63-50066, JP-A-7-32476, etc. This is a method of faithfully shaping the irregular shape of a molding plate cylinder (also called a shaping plate, roll intaglio etc.) into a cured product of an ionizing radiation curable resin. Basically, it consists of the following steps (see FIG. 5).
[0017]
(1) A cylindrical forming plate cylinder 92 having a concave-convex shape (same shape as the fine concave-convex 2) 91 having the same shape as the concave-convex shape of the desired fine concave-convex 2A on the surface and the same shape as the concave-convex shape is prepared Rotate around.
(2) The continuous belt-like substrate sheet 11 is supplied at the same speed as the peripheral speed of the molding plate cylinder 92.
(3) The base sheet 11 and the molding plate cylinder 92 are overlapped and adhered through an uncured liquid composition 94 of an ionizing radiation curable resin therebetween, and the liquid composition is attached to the molding plate cylinder. At least the recess is completely filled.
(4) In this state, ionizing radiation 96 is irradiated from the ionizing radiation irradiator 95 to crosslink and cure the liquid composition.
(5) After that, the substrate sheet 11 is adhered to it and made of a cured product of an ionizing radiation curable resin in which the uneven shape 91 on the molding plate cylinder is formed. The mold layer 12 is peeled off together with the forming layer 12. As a result, the shaped sheet S is obtained with a configuration in which the fine unevenness shaping layer 12 having the fine unevenness 2A is adhered to the base sheet 11.
[0018]
In the above method, as the forming plate cylinder 92, a known intaglio plate, gravure plate, and emboss plate may be basically used with the same material, the same structure, and the same manufacturing method. As the material of the forming plate cylinder, metals such as iron and copper are usually used. However, when irradiating ultraviolet rays or visible rays from the inside of the molding plate cylinder, a transparent material such as glass or quartz is used.
The rotation drive around the axis of the molding plate cylinder may be performed using the same mechanism and method as those of a normal rotary gravure printing machine, rotary embossing machine, and the like. In order for the base sheet to adhere to the molding plate cylinder, it is pressure-bonded by a pressure roller 97 such as rubber or metal. Also, the base sheet is peeled off from the molding plate cylinder by pressing with a peeling roller 98 of rubber, metal or the like. The base sheet is a continuous strip. Such a base sheet is unwound from an unwinding roll (supply roll), and is wound up by a winding roll (discharge roll) after the formation of the fine irregularities 2A.
[0019]
The following (1) to (3) are the modes in which the base sheet and the molding plate cylinder are overlapped and adhered through an uncured liquid composition of an ionizing radiation curable resin therebetween. (1) First, an uncured liquid composition is applied onto a base sheet, and then the base sheet is overlaid on the forming plate cylinder so that the coated surface faces the surface of the forming plate cylinder. (2) First, as shown in FIG. 5, the liquid composition 94 is applied onto the molding plate cylinder 92 by using a T-die type resin liquid supply means 93 or the like, and then the base sheet 11 is overlaid on the coating surface on the molding plate cylinder. Match. (3) First, the liquid composition is applied to each of the mold plate cylinder and the base sheet, and then the base sheet and the mold cylinder are overlapped so that the respective application surfaces face each other.
[0020]
Examples of irradiation with ionizing radiation to the uncured liquid composition between the molding plate cylinder and the base sheet include the following (A) and (B). (A) As shown in FIG. 5, a substrate sheet transparent to ionizing radiation is selected (for example, a polyethylene terephthalate sheet is selected for ultraviolet rays, and a thin paper is selected for electron beams), and irradiation is performed from the substrate sheet side. (B) A molding plate cylinder transparent to ionizing radiation is selected (for example, a quartz molding plate cylinder is selected for ultraviolet rays), and irradiation is performed from the inside of the molding plate cylinder.
[0021]
The material of the base sheet is (1) thermoplastic resin polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyolefin resin such as polyethylene, polypropylene, polymethylpentene, olefin thermoplastic elastomer, polyvinyl chloride , Resin sheets such as polycarbonate, polystyrene, ABS resin, acrylic resin, (2) thin paper, fine paper, kraft paper, Japanese paper, etc., (3) non-woven fabric or woven made of glass, vinylon, polyester, cellulose, etc. There are cloth, (4) metal foil such as aluminum, iron and copper. In addition, said (2)-(4) is possible only in the case of ultraviolet rays from the inside of a transparent molding plate cylinder, or highly transmissive radiations, such as an electron beam.
[0022]
As an ionizing radiation curable resin, a prepolymer, a monomer having a polymerizable unsaturated bond such as a (meth) acryloyl group, a (meth) acryloyloxy group, or a cationic polymerizable functional group such as an epoxy group in the molecule, or A composition in which only one kind or two or more kinds of polymers are appropriately mixed is used. Alternatively, a composition composed of a polyene / thiol prepolymer based on a combination of polyene and polythiol can also be used. The composition is liquid when uncured.
[0023]
Examples of the prepolymer having a polymerizable unsaturated bond in the molecule include unsaturated polyesters such as a condensation product of unsaturated dicarboxylic acid and polyhydric alcohol, polyester (meth) acrylate, urethane (meth) acrylate, epoxy ( There are (meth) acrylates such as (meth) acrylate, melamine (meth) acrylate, and silicone (meth) acrylate [In the present specification, (meth) acrylate is used in the meaning of acrylate or methacrylate. The same applies below). Examples of the monomer having a polymerizable unsaturated bond in the molecule include styrene monomers such as styrene and α-methylstyrene, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and (meth) acrylic. Monofunctional (meth) acrylic acid esters such as methoxyethyl acid, butoxyethyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate , Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Crylate esters, (meth) acrylic acid-2- (N, N-diethylamino) ethyl, (meth) acrylic acid-2- (N, N-dimethylamino) ethyl, (meth) acrylic acid-2- (N , N-dibenzylamino) ethyl and other unsaturated amino alcohol esters of unsaturated acids, and unsaturated carboxylic acid amides such as (meth) acrylamide.
[0024]
Examples of the prepolymer having a cationically polymerizable functional group in the molecule include bisphenol-type epoxy resins, novolac-type epoxy resins, aliphatic-type epoxy resins, alicyclic epoxy resins and other epoxy resins, aliphatic vinyl ethers, aromatic There are vinyl ether resins such as group vinyl ethers, urethane vinyl ethers and ester vinyl ethers, prepolymers such as cyclic ether resins and spiro compounds.
[0025]
The polyene / thiol-based prepolymer includes polythiol compounds having two or more mercapto groups in the molecule, such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, pentaerythritol tetrathioglycol, etc. There is. On the other hand, examples of the polyene include those obtained by adding allyl alcohol to both ends of polyurethane by diol and diisocyanate.
[0026]
As the ionizing radiation curable resin, one or two or more of the above compounds may be mixed and used as necessary. In order to impart ordinary coating suitability to the resin composition, 5 mass of the prepolymer or oligomer is used. It is preferable to make the monomer and / or polythiol 95% by mass or more.
In addition, in order to adjust the physical properties such as flexibility, surface hardness, peelability, etc. of the cured product, the following ionizing radiation non-curable resin is mixed with about 1 to 70% by mass with respect to the ionizing radiation curable resin. Can be used. As the ionizing radiation non-curable resin, thermoplastic resins such as urethane resin, cellulose resin, polyester resin, acrylic resin, butyral resin, polyvinyl chloride, and polyvinyl acetate can be used. In order to improve the peelability, a lubricant such as silicone resin and wax can be added.
[0027]
In particular, when curing with ultraviolet rays, a photopolymerization initiator is added to the ionizing radiation curable resin composition. Examples of the compound having a radically polymerizable unsaturated bond in the molecule include acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, tetramethylmeurum monosulfide, thioxanthones and the like.
Examples of the compound having a cationically polymerizable functional group in the molecule include aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene compounds, benzoin sulfonic acid esters, diallyl iodosyl salts and the like. Further, if necessary, n-butylamine, triethylamine, tri-n-butylphosphine and the like can be mixed and used as a photosensitizer.
[0028]
In order to apply the uncured liquid composition of the ionizing radiation curable resin composition to the molding plate cylinder or the base sheet, various known methods such as roll coating, curtain flow coating, and T-die coating are used. Use. In particular, in the case of coating on a forming plate cylinder, it is possible to immerse the rotating forming plate cylinder in a liquid composition in an ink pan (so-called soaking).
[0029]
Here, the ionizing radiation means an electromagnetic wave or charged particle beam having energy capable of polymerizing and crosslinking molecules, and includes ultraviolet rays, visible rays, X-rays, electron beams, α rays, etc. Ultraviolet rays or electron beams are used. As the ultraviolet ray source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light lamp, a metal halide lamp is used. As the electron beam source, various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, a high frequency type, etc. are used, preferably 100 to 1000 keV, preferably That irradiates electrons having energy of 100 to 300 keV is used.
[0030]
[Coating layer]
The above-mentioned shaped sheet is formed by applying a transparent coating layer 3A of a thermosetting resin uncured product or a cured product layer on the surface of the fine irregularities 2A before being overlapped with an FRP uncured product or the like. (See FIG. 1). After forming, the coating layer 3A becomes a transparent surface protective layer on the surface of the molded product, and also serves as a fine uneven support layer (anti-slip layer). In the molded product, the coating layer is transparent (no coloring or coloring) so that the lower pattern layer can be seen through. When the coating layer is a cured product, it is semi-cured or completely cured. However, in the case of semi-cured or uncured, it is preferable from the viewpoint of workability that it is solid without fluidity.
[0031]
Examples of the thermosetting resin include diallyl phthalate (DAP) resin, unsaturated polyester resin, epoxy-modified polyester resin, epoxy resin, melamine resin, and urethane resin.
[0032]
The thermosetting resin is used by appropriately adding a curing agent, a reactive diluent, a filler, other additives, and the like. For example, when an unsaturated polyester resin is used as a thermosetting resin, a thermal polymerization initiator such as benzoyl peroxide or methyl ethyl ketone peroxide, a curing reaction catalyst such as cobalt naphthenate, a reactive diluent such as styrene monomer, etc. Add. Moreover, as a filler, powders, such as silica, such as colloidal silica, calcium carbonate, clay, and talc, are added, for example. By adding a filler, fluidity and tackiness in an uncured or semi-cured state can be reduced.
[0033]
Other additives include, for example, a colorant, a lubricant, a light stabilizer, an antibacterial agent, and an antifungal agent. As the lubricant, for example, powders such as alumina (α-alumina, etc.), aluminosilicate, etc. are added. In particular, the coating layer forms the surface of the molded product as a surface protective layer and anti-slip layer after molding, and addition of an antibacterial agent and an antifungal agent is preferable in consideration of the use around water such as bathroom flooring. As the antibacterial agent, for example, zeolite powder carrying silver ions so that ion exchange is possible, and as the antifungal agent, for example, 10,10-oxybisphenoxyarsine may be added.
[0034]
In addition, what is necessary is just to use well-known coating methods, such as a roll coat, in order to apply and form a coating layer on the fine unevenness | corrugation of a shaping sheet. At that time, in order to adjust the coating suitability, a resin to which a volatile solvent is added is used as necessary, and the solvent is dried after coating. The thickness of a coating layer should just be according to the depth of the fine unevenness | corrugation to shape, and is about 5-300 micrometers.
[0035]
[Decorated fiber sheet]
The decorative fiber sheet 4 is a sheet in which a pattern layer 42 is formed on a fiber sheet 41 by printing or the like. If the fibrous sheet 41 is not impregnated, the resin of the FRP uncured product 5 is impregnated therein by the hot pressure during molding. After molding, the resin-impregnated fibrous sheet 41 becomes the FRP layer 6 together with the cured product of the FRP uncured product 5 (see FIG. 6).
[0036]
The fiber sheet 41 that holds the pattern layer 42 until use contributes to the dimensional stability of the molded product after molding. Further, when the pattern layer 42 is laminated on the shaping sheet S side at the time of molding, distortion, flow, or cracking of the pattern of the pattern layer is less likely to occur.
[0037]
As the material of the fibrous sheet 41, synthetic resin fibers made of acrylic, nylon, polyester, polypropylene, rayon, acetate, vinylon, polyvinyl chloride, etc., natural organic fibers such as cellulose, pulp, wool, etc. Inorganic fiber made of glass, asbestos, potassium titanate, alumina, silica, carbon or the like is 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. Among these, in view of cost, physical properties, adhesion, impregnation performance, shape followability to loose irregularities, etc., a synthetic resin fiber nonwoven fabric having a thickness of 0.2 mm or less is preferable. For example, a nonwoven fabric of polyester resin fibers is suitable.
The fibrous sheet may be not impregnated with resin, but may be impregnated with resin. As the resin, for example, thermosetting resins as listed in the coating layer can be used.
[0038]
The pattern layer 42 is formed on the fibrous sheet 41 by a known forming method such as printing. For example, the printing is performed by gravure printing, silk screen printing, offset printing, ink jet printing, or the like. The pattern depends on the application, for example, stone pattern, sand pattern, pear texture, tiled pattern, brick pattern, wood pattern, fabric pattern, skinned pattern, letters, geometric pattern, full face pattern, or A combination of two or more of these is used. The ink for forming the pattern layer includes, for example, a simple substance such as acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester resin, cellulose resin, urethane resin, or a mixture containing these as a binder resin. , Zinc white, carbon black, iron black, dial, inorganic pigments such as vermilion, yellow lead, titanium yellow, cobalt blue, ultramarine blue, organic pigments such as aniline black, quinacridone red, isoindolinone yellow, phthalocyanine blue, aluminum foil Bright pigments such as powder, brass foil powder, titanium dioxide-coated mica foil powder, fluorescent pigments, or other dyes are used as colorants.
[0039]
[FRP uncured product]
The FRP uncured product 5 may be a conventionally known FRP molding material. In the present invention, SMC (sheet molding compound), BMC (bulk molding compound), etc. are typically used. . In particular, since SMC is already formed into a sheet shape, it is suitable for forming a flat plate shape or a molded product approximate to a flat plate shape. The FRP uncured product is cured by heating.
Typical examples of the FRP uncured resin are unsaturated polyester resins, but other resins such as (curable) acrylic resins, epoxy resins, diallyl phthalate resins, melamine resins, urethane resins, and so-called thermosetting resins. Can also be used. The fiber as the reinforcing material of FRP is typically glass fiber, but inorganic fiber such as carbon fiber and potassium titanate fiber, or synthetic resin fiber such as polyester fiber, nylon fiber, and vinylon fiber are also used.
In addition, for FRP uncured products, fillers such as silica, alumina, and calcium carbonate, colorants such as pigments and dyes, curing catalysts, thickeners, stabilizers, plasticizers, lubricants, hardeners, and the like are appropriately added as necessary. A material to which a flame retardant, a thermoplastic resin or the like is added is used.
[0040]
The FPR uncured product 5 constitutes the FRP layer 6 together with the fiber sheet 41 that has been impregnated with the resin and cured by heating and pressing with a mold, a press, or the like while being laminated with another material. The heating and pressing conditions are conditions according to the FPR uncured product and the resin used for the coating layer.
[0041]
[Heating and pressing]
By heating and pressing, the above-mentioned laminated materials are bonded and firmly integrated, and at the same time, the surface of the molded product is formed with fine unevenness 2 opposite to the fine unevenness 2A on the shaped sheet. The desired decorative FRP molded product D is obtained as illustrated in the sectional view of FIG.
The conditions for heating and pressing are conditions according to the resin used for the uncured FPR, the coating layer, and the like. For example, the heating temperature is 100 to 170 ° C., the pressing pressure is 5 to 20 MPa, and the heating and pressing time is about 1 to 80 minutes. It should be noted that when the mold is molded by appropriately spraying a known release agent, the mold release property is good.
[0042]
Incidentally, the mold surface of the mold may be provided with irregularities as illustrated in the mold Mb of FIG. The irregularities are larger (gradual) larger irregularities than the fine irregularities 2 and 2A referred to in the present invention. The large pattern unevenness is, for example, a rock surface shape, a grid shape, a brick shape, or the like. Large irregularities on the mold surface are shaped on the surface of the molded product through the shaped sheet. At the time of molding, the shaped sheet can follow the uneven shape of the large pattern, so that the shaped sheet does not get in the way. It is preferable to form the unevenness with a large and uneven mountain valley, which is difficult to express with the shaped sheet, from the mold surface as this large unevenness.
By the large pattern unevenness as described above, a molded product having the fine unevenness 2 is obtained on the surface so as to overlap the large pattern unevenness 7 as in the decorated FRP molded product D illustrated in the cross-sectional view of FIG. And the decoration FRP molded product D becomes a higher design thing by large pattern unevenness | corrugation.
[0043]
[Use]
In addition, the use of the decorative FRP molded product according to the present invention is not particularly limited, but preferably, the decorative FRP molded product is used for an application that can make use of anti-slip performance when water is present on the surface thereof. For example, flooring materials for buildings and bathrooms. In addition, floor materials such as automobiles, trains, airplanes, and ships are also suitable. The overall shape of the decorative FRP molded product may be a three-dimensional shape in addition to a flat plate shape.
[0044]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
[0045]
[Example 1]
First, as a shaped sheet S as shown in FIG. 3, ionizing radiation curing which is cured with ultraviolet rays on a biaxially stretched polyethylene terephthalate sheet having a thickness of 100 μm as a base sheet 11 by a forming plate cylinder method as shown in FIG. 5. A fine uneven surface forming layer 12 as a cured product of a functional resin [trifunctional urethane acrylate prepolymer, DPHA (dipentaerythritol hexaacrylate) and an uncured liquid composition with a benzophenone photopolymerization initiator] A sheet was produced. The uneven shape of the fine unevenness 2A formed on the fine unevenness shaping layer 12 was a large number of linear grooves, with the opening width of the recesses being 50 μm, the width of the protrusions being 50 μm, and the depth of the recesses being 20 μm.
[0046]
Next, a coating liquid made of diallyl phthalate (DAP) resin added with 10% by mass of colloidal silica as a thermosetting resin is applied on the surface of the fine irregularities 2A of the shaped sheet S by roll coating and dried by heating. Then, a transparent coating layer 3A having a thickness of 50 μm made of a semi-cured thermosetting resin was formed.
[0047]
On the other hand, the decorated fiber sheet 4 has a basis weight of 100 g / m.²A gravure ink in which a colorant is added to a binder resin composed of 100 parts by weight of polyester polyol and 8 parts by weight of hexamethylene diisocyanate is printed on one side of a fibrous sheet 41 made of polyester non-woven fabric. What provided the layer 42 was prepared.
[0048]
As shown in the explanatory diagram of FIG. 1, the mold Mb (lower side of the drawing) corresponding to the molded article surface side is provided with large irregularities 7 having a rock surface tone on the mold surface. In order from the lower side, the shaped sheet S with the coating layer 3A (with the coating layer 3A facing upward), the decorative fibrous sheet 4 (with the pattern layer 42 facing downward), and the uncured FRP 5 made of SMC It was overlapped and inserted between the pair of molds Ma and Mb. In addition, as said SMC, what used the glass fiber as a reinforcing fiber for unsaturated polyester resin was used.
[0049]
Then, the molds Ma and Mb heated to 150 ° C. are closed to 7 Pa (about 70 kgf / cm²) At a pressure of 10) for 10 minutes, and then the mold was opened, and only the shaped sheet S was peeled from the surface of the molded article to obtain a decorated FRP molded article D having the configuration shown in FIG.
[0050]
The obtained decorative FRP molded product D looks like a normal rock surface due to the large irregularities 7 on the surface. However, when the surface is enlarged and observed, it looks like a plan view shape in FIG. The line-shaped fine unevenness | corrugation 2 with the width | variety of the part 21 and the recessed part 22 of 50 micrometers and the depth of 20 micrometers was formed.
[0051]
[Comparative Example 1]
In Example 1, instead of the shaped sheet, the substrate sheet was formed from the surface of the molded article after molding in the same manner as in Example 1 except that the substrate sheet was directly formed with a coating layer. The decorative FRP molded product in which only the large irregularities were shaped was obtained.
[0052]
〔Evaluation results〕
About each decorative FRP molded product by Example 1 and Comparative Example 1, the anti-slip effect was evaluated both when the surface was wet with water and when it was wet with soapy water. In the evaluation, the surface of the molded product was wetted with water or soapy water, and then the surface was rubbed back and forth with the palm of the hand to confirm the sliding condition.
As a result, the decorated FRP molded product of Example 1 having fine irregularities was not slippery in either case of water or soapy water, and the slip prevention effect was good. On the other hand, the decorated FRP molded product of Comparative Example 1 having no fine irregularities and only large irregularities was easily slippery with water as well as soapy water and had no anti-slip effect.
[0053]
【The invention's effect】
According to the present invention, due to the fine unevenness formed on the surface of the molded product, even if there is soapy water on the surface in a bathroom or the like, the flow of soapy water is pushed apart and the fine unevenness bites into the foot, or it has an anti-slip effect. can get. And since a shaping | molding film is used for the shaping | molding of a fine unevenness | corrugation, compared with the case where a fine unevenness | corrugation is provided in a shaping | molding die surface and it shape | molds from it, it can shape at low cost. Further, the surface protective layer and anti-slip layer can reduce the bleed-out of the internal release agent of the FRP molding resin gradually, and can also prevent the release agent bleed-out from becoming slippery.
[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a conceptual illustration of a situation where materials are stacked in a pair of molds in the present invention.
FIG. 2 is a partially enlarged cross-sectional view showing a stacked state of each material in a mold.
FIG. 3 is a cross-sectional view showing an example of a shaped sheet used in the present invention.
FIG. 4 is a plan view showing several examples of a planar view shape of fine irregularities formed by the present invention.
FIG. 5 is an explanatory diagram conceptually showing an example of a method for producing a shaped sheet (molding plate cylinder method).
FIG. 6 is a cross-sectional view showing an example of a decorated FRP molded product obtained in the present invention.
FIG. 7 is a cross-sectional view showing another example of a decorated FRP molded product obtained in the present invention.
[Explanation of symbols]
11 Substrate sheet
12 Fine irregularities shaping layer
2 Fine irregularities (after shaping)
2A Fine irregularities (on the shaped sheet)
21 Convex part of fine irregularities (after shaping)
22 Recesses with fine irregularities (after shaping)
3 Surface protective layer and anti-slip layer
3A coating layer
4 decorative fiber sheet
41 Fiber sheet
42 picture layer
5 FRP uncured material
6 FRP layer
7 Large irregularities
81 Hydraulic cylinder
82 Lamb
91 Uneven shape
92 Molding cylinder
93 T-die type resin liquid supply means
94 Uncured resin liquid
95 Ionizing radiation irradiator
96 Ionizing radiation
97 Pressing roller
98 Peeling roller
D Decorative FRP molded product
Ma mold
Mb mold
S shaping sheet

Claims

Between the pair of molds, an FRP uncured product, a decorative fibrous sheet having a pattern layer is inserted and laminated,
Further, a layer of an uncured or cured product of a thermosetting resin on a fine uneven surface of a shaped sheet having fine unevenness which is a groove-shaped recess having a recess opening of 20 μm to 1 mm and a depth of 5 to 200 μm on the surface. Laminated with the coating layer formed so that the coating layer faces the decorative fiber sheet side,
Next, the pair of molds are closed and heated and pressurized to complete the curing of the FRP uncured product and the thermosetting resin of the coating layer,
Next, the pair of molds are opened and the shaped sheet is peeled and removed.
By this, a decorative FRP molded product obtained by laminating a pattern layer and an FRP layer on the back surface of a transparent surface protective layer and anti-slip layer made of a cured thermosetting resin having fine irregularities on the surface is obtained. A method for producing a decorated FRP molded product.

The manufacturing method of the decorating FRP molded product of Claim 1 with which the fine unevenness | corrugation of the said shaping sheet was formed by the molding plate cylinder method.

The method for producing a decorated FRP molded article according to claim 1 or 2, wherein the fine irregularities of the shaped sheet are a cured product of an ionizing radiation curable resin composition.

The method for producing a decorated FRP molded product according to claim 1, wherein the coating layer contains a filler.

From a cured product of a thermosetting resin having fine irregularities on the surface, on the fine irregularities side of the shaped sheet having fine irregularities, which are groove-shaped concave portions having a recess of 20 μm to 1 mm and a depth of 5 to 200 μm on the surface. A decorative sheet with a shaping sheet comprising a transparent surface protective layer and anti-slip layer, and a decorative fiber sheet having a pattern layer on the back surface of the surface protective layer and anti-slip layer, and an FRP layer. FRP molded product.

The decorated FRP molded product with a shaped sheet according to claim 5, wherein the fine irregularities of the shaped sheet are a cured product of an ionizing radiation curable resin composition.

The decorative FRP molded article with a shaping sheet according to claim 5 or 6, wherein the surface protective layer and anti-slip layer contains a filler.

The surface has a transparent surface protection layer and anti-slip layer made of a cured product of a thermosetting resin having fine irregularities which are groove-shaped concave portions having a concave opening of 20 μm to 1 mm and a depth of 5 to 200 μm, A decorative FRP molded article obtained by laminating a decorative fiber sheet having a pattern layer and an FRP layer on the back surface of the surface protective layer and anti-slip layer.

The decorated FRP molded product according to claim 8, wherein the surface protective layer and anti-slip layer contains a filler.