JP4586306B2 - Prepreg of diallyl phthalate prepolymer for laminates - Google Patents
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Description
【０００１】
【産業上の利用分野】
本発明はジアリルフタレートプレポリマーを使用した積層板用プリプレグに関し、特に住宅、車両、船舶、航空機等の内装用あるいは家具調度類に使用される化粧板用として好適なジアリルフタレートプレポリマーを使用したプリプレグ及び該プリプレグ積層板基材に熱圧積層した化粧板に関するものである。
【０００２】
【従来の技術】
特開平１１−１４０２０３号、特開平１１−１４０７７７号等に例示されているが、ジアリルフタレート樹脂硬化物の透明性の良好さ、高い表面硬度と光沢の良さ、耐熱性と耐薬品性、寸法安定性などの優秀な性質を利用して、これまで住宅、車両、船舶、航空機等の屋内用内装材化粧板としてテーブル、こたつの天板、システムキッチンなどに広く利用されてきた。このジアリルフタレート樹脂製化粧板はジアリルフタレートプレポリマー、ジアリルフタレートモノマー、不飽和ポリエステル、硬化剤、離型剤、重合調整剤、充填剤、紫外線吸収剤、その他添加剤からなるプリプレグと基板であるパーティクルボードやベニヤ板、厚紙やアルミ等の金属板などをプレス等で加熱加圧して張り合わせて製造されている。
【０００３】
ジアリルフタレートプレポリマーのプリプレグの製造方法は、基材として植物繊維、ガラス繊維やポリエステル等の合成繊維からなる不織布や織布などのシート状基材を用い、ジアリルフタレートプレポリマーとその他の配合剤を有機溶剤に溶解して作成した樹脂液を含浸した後、溶媒を加熱除去するというものである。この方法は現在でも広く実施されている。
【０００４】
【発明が解決しようとする課題】
近年環境問題による省資源、省エネルギーが要求されるようになり、多くの溶媒とエネルギーを使用するプリプレグ製造方法の改善が求められている。その対策として溶剤を使用することなくプリプレグを製造する方法がいろいろ検討されているが、まだジアリルフタレートプレポリマーを使用したプリプレグには無溶剤で安価に製造する適当な方法がなかった。
【０００５】
ジアリルフタレート樹脂の市販品のポリスチレン換算重量平均分子量は約３万から５万であり、フェノール樹脂や不飽和ポリエステル樹脂、エポキシ樹脂のそれに比較して高く、たとえジアリルフタレート樹脂以外の樹脂で溶媒を使用することなくプリプレグ基材中に樹脂を含浸できる方法（例えば特開平１１−２２６９５０号）があっても、同じ方法、同じ工程ではプリプレグ基材隅々までジアリルフタレートプレポリマー組成物を含浸できず、ボイドが発生して商品価値の低いものしかできなかった。
【０００６】
本発明者は、従来製造が困難であった溶剤を使用することなしでプリプレグ、あるいは積層板を得ようとして研究した結果、ジアリルフタレートプレポリマーを溶解し反応できる液体成分に硬化触媒を混合したものをプリプレグ基材に塗布後、ジアリルフタレートプレポリマーを散布することで、基材へのプレポリマー組成物の含浸性が従来の溶剤を使用したものと同等になるとの知見を得、さらに研究を重ねて本発明を完成した。
【０００７】
【課題を解決するための手段及び作用】
本発明は上記課題を解決したもので、ジアリルフタレートプレポリマーを溶解することができ且つ硬化触媒によりジアリルフタレートプレポリマーと反応して硬化する液体成分に、硬化触媒を溶解したものをシート状繊維基材の片面あるいは両面に、シート状繊維基材の重量の５〜５０％に相当する量を塗布した後、該塗布両面に粉末状硬化触媒を分散させたジアリルフタレートプレポリマーの微粉末を散布したことを特徴とする積層板用ジアリルフタレートプレポリマーのプリプレグである。
【０００８】
本発明に用いられるジアリルフタレートプレポリマーとは、ジアリルオルソフタレートプレポリマー、ジアリルイソフタレートプレポリマー、ジアリルテレフタレートプレポリマーの単独あるいはそれらの共重合体又はそれらの混合物で、粒径が１０００μｍ以下、好ましくは７００μｍ以下で平均粒子径がメジアン径で５０μｍ以下のものを示す。
【０００９】
本発明においては上記ジアリルフタレートプレポリマーはジアリルフタレートプレポリマー単独でなくてもよく、上記ジアリルフタレートプレポリマー１００〜５０重量％と、粒径が７００μｍ以下で平均粒子径がメジアン径５０μｍ以下であれば融点５０℃以上の不飽和ポリエステル０〜５０重量％との混合物であってもよい。
【００１０】
不飽和ポリエステルとしては、不飽和酸としてマレイン酸、フマル酸、イタコン酸を単独あるいは混合して使用し、飽和酸として芳香族系多塩基酸のイソフタル酸、テレフタル酸、トリメリット酸、ピロメリット酸を単独あるいは混合して使用したもので、これら不飽和酸と飽和酸の混合物とエチレングリコール、プロピレングリコール、ジエチレングリコール等の多価アルコールとの反応生成物で、融点が５０℃以上の物をさす。
【００１１】
不飽和ポリエステルを加える理由としては、ジアリルフタレートプレポリマーと液体成分との組み合わせよりも更に流動性が必要な場合、例えばシート状繊維基材の厚みが大きい時などに流動性向上の目的で加える。しかし、５０重量％を超えるとジアリルフタレート樹脂の特徴である熱変形温度が高いなどの耐熱性や耐水性が低下するので好ましくない。
【００１２】
本発明に用いられるジアリルフタレートプレポリマーを溶解することが可能で硬化触媒によりジアリルフタレートプレポリマーと反応する液体成分とは、分子内に少なくともアリル基、アクリル基、チオール基を単独あるいは２種類以上を１〜６個まで含む２３℃での粘度が６０００ｍＰａ・ｓ以下の物質をいい、かつ２３℃でジアリルフタレートプレポリマーを３０重量％以上溶解可能なものをいう。ここでいうアリル基は、メタリル基であってよく、またアクリル基はメタアクリル基であってもよい。これらを単独あるいは混合して使用することができる。液体成分としてアリルベンゾエート、ジアリルオルソフタレートモノマー、ジアリルイソフタレートモノマー、ジアリルテレフタレートモノマー、トリアリルイソシアネート、トリアリルシアネート、トリメチロールプロパントリアクリレート、ジペンタエリスリトールヘキサアクリレート、ペンタエリスリトールテトラキスチオグリコレートなどを例示することができる。
【００１３】
本発明に用いられる硬化触媒は、ベンゾイルパーオキサイド、ターシャリーブチルパーベンゾエイト、メチルエチルケトンパーオキサイド、ジクミルパーオキサイド等、従来からジアリルフタレート系樹脂プリプレグや成形材料で使用されてきた過酸化物系硬化剤をあげることができる。
【００１４】
シート状繊維基材としては、植物繊維、ガラス繊維やポリエステル等の合成繊維からなる不織布や織布、紙、ダンボール、金属繊維やカーボン繊維からなる織布やマット類等があげられ、これらの基材の原料は単独または混合して使用してもよい。
【００１５】
本発明のプリプレグは、化粧板の基板である合板、パーティクルボード、中密度繊維板（ＭＤＦ基板）、その他無機質板、金属板基板、厚紙、ダンボール紙などに１枚、あるいは複数枚とって積層し熱圧成形して化粧積層板となる。成形は、温度１３０〜２００℃、圧力０．１〜３ＭＰａ、時間２０秒〜２分で実施する。
【００１６】
次に本発明の実施の態様について述べる。まず、ジアリルフタレートプレポリマーを溶解することが可能で硬化触媒によりジアリルフタレート系樹脂と反応する液体成分に硬化触媒として該液体成分に可溶な有機過酸化物を０．１から１０重量％混合溶解したものをつくる。前記液体成分にアクリル基やチオール基を含むときは、重合抑制剤としてヒドロキノンやヒドロキノンモノメチルエーテル、ターシャリーブチルカテコールなどを１０００ｐｐｍ以下の量で添加できる。またこの液には、各種シランカップリング剤や離型剤、充填剤、紫外線吸収剤、色素や顔料等の着色剤など必要に応じて添加できる。
【００１７】
プリプレグ基材であるシート状繊維基材をポリエステル製フィルムを敷いた平らな台の上に広げ、前記液体成分配合物を均一に散布または付着させる。その方法としてはスプレーによる吹き付け、各種コーターによる塗布など特に限定されない。通常片面だけの散布ないし付着でよいがシート状繊維基材が厚ければ両面に散布または付着させる。
【００１８】
この付着量は、シート状繊維基材の性質、性状、重量（単位面積当たり）により異なるが、通常、シート状繊維基材の重量の５〜５０重量％とする。この量が少ないときは後にジアリルフタレートプレポリマーをこの上から散布してプリプレグとし、その後さらに基板と共に加熱加圧したときジアリルフタレートプレポリマーの流動が少なくなり、プリプレグ基材を十分ジアリルフタレートプレポリマーが含浸することなく、樹脂が抜け落ちた欠陥部分ができやすく外観上好ましくない。また、この量が多すぎてもジアリルフタレートプレポリマーをこの上から散布しプリプレグとした時、タックが残り後の工程での取り扱いが困難になる。
【００１９】
次にこの上からジアリルフタレートプレポリマー（固体状の不飽和ポリエステルを５０重量％以下含んでいてもよい）をシート状繊維基材の両面に散布する。この時ジアリルフタレートプレポリマーの硬化触媒として、有機過酸化物が平均粒径１０μｍ以下の炭酸カルシウム等の充填剤に分散されたものを樹脂に対して０．１〜１０重量％配合することも必須とする。このほか、各種充填剤、離型剤、紫外線吸収剤、色素や顔料等の着色剤など必要に応じて、ジアリルフタレートプレポリマー量の２０重量％まで添加できる。その際には散布前にあらかじめそれらの材料を各種ブレンダーやミキサーで撹拌混合しておく。
【００２０】
この散布量は、シート状繊維基材の性質、性状、重量（単位面積当たり）により異なるが、通常、シート状繊維基材の重量の５０〜３００％とする。この量の２０〜８０重量％をシート状繊維基材の片面に、残り８０〜２０重量％をもう一方の片面に散布する。この量が少ないときは基板との成形後充分な艶が得られなくて化粧性が悪いものに仕上がる。また、散布量が多すぎても艶はある程度以上には上がらずコスト増になる。
【００２１】
散布方法としては、シート状繊維基材上面から振りかける方法、各種コーターによる塗布方法、静電塗装、スプレーによる吹き付け法等、樹脂粉末が良好に散布付着できる方法であれば特に限定されない。この時、シート状繊維基材は特に加熱加温する必要はないが、樹脂を散布後、粘着感がなくなるまでには散布した液体成分の量によって変るが、室温で１〜２時間程度放置すれば液体成分はジアリルフタレートプレポリマーを溶解吸収し粘着感はなくなる。こうして粘着感がなくなる頃にはシート状繊維基材とポリエステルフィルムの間の粘着もわずかとなり、ポリエステルフィルムからはぎとることができるようになる。このようになってからポリエステルフィルムからはぎとって裏返し、残りのジアリルフタレートプレポリマーを散布すればよい。
【００２２】
一方、工程の時間短縮のためにプレポリマーを散布した後のシート状繊維基材を加熱することができる。５０〜１３０℃のオーブン中に５〜６０分加熱して取り出すことによりタックはほぼなくなる。その後、シート状繊維基材を裏返して残りのプレポリマー組成物を散布すること、あるいは散布後さらに同様に加熱することでプリプレグができる。
【００２３】
この結果、まずジアリルフタレートプレポリマーを溶解することが可能な液体成分によってプリプレグ基材が隅々まで濡れた状態になり、次にジアリルフタレートプレポリマーを散布することで付着したジアリルフタレートプレポリマーが液体成分に溶解され、プリプレグ基材にしみこんでいく。更に熱圧プレス時には、液体成分を包含したジアリルフタレートプレポリマーの粘度がそれ単独の時に比べ格段に低下し短い成形時間の間でもプリプレグ基材の隅々まで含浸することができ、プリプレグ全面を樹脂で覆うことができて樹脂の抜け落ちのない、表面が平滑で、艶の良好な化粧積層板が得られる。
【００２４】
一方、液体成分からみれば、ジアリルフタレートプレポリマーに吸着されることになって、液体で濡れた表面が見た目に乾いた状態になってそれ以降の積層板基材との重ね合わせや、熱圧プレス工程での取り扱いが溶媒を使用したときのプリプレグと同じ状況で操作可能になるのである。
【００２５】
【実施例、比較例】
次に本発明の実施例を比較例と共に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。実施例、比較例で示される部及び％はすべて重量部及び重量％である。
【００２６】
実施例１
ジアリルオルソフタレートモノマー（ダイソー（株）製、２３℃粘度注１ １２ｍＰａ・ｓ）にジクミルパーオキサイド（日本油脂（株）製、パークミルＤ、フレーク状、純品）を３％撹拌溶解させたものを８０ｇ／ｍ２のパターン印刷紙に家庭用スプレーを使って２０ｇ／ｍ２の割合で散布した。この上にジアリルオルソフタレートプレポリマー（ダイソー（株）製、メジアン径注２ ３２μｍ）１００部にジクミルパーオキサイド（日本油脂（株）製、パークミルＤ−４０、粉体状、４０％品）５部及びステアリン酸亜鉛（堺化学（株）製）１部をポリ袋中で３分間振り混ぜたものを８０ｇ／ｍ２の半分の４０ｇ／ｍ２の割合で目開き７０１μｍのフルイを使用して均一に散布した。１３０℃のオーブンで５分間加熱し、冷えた後裏返し、残りのジアリルオルソフタレートプレポリマー組成物を４０ｇ／ｍ２の割合で同様に散布し、１３０℃のオーブンで５分間加熱しプリプレグをえた。
【００２７】
このプリプレグを用い１５ｍｍ厚のパーティクルボードに１４０℃、１．５ＭＰａの圧力で２分間熱圧積層した。
注１ ２３℃粘度はデジタル粘度計ＤＶＭ−Ｅ型（東京計器）で測定した。以下同じ。
注２ メジアン径はマイクロトラックＨＲＡ粒度分析計（日機装）で測定した。
以下同じ。
【００２８】
実施例２
ジアリルイソフタレートモノマー（ダイソー（株）製、２３℃粘度１８ｍＰａ・ｓ）に純品のジクミルパーオキサイド３％、ヒドロキノン（和光純薬（株）製）０．０１％を溶解しシリカ粉（塩野義製薬（株）製）２％添加したもの、９０ｇ／ｍ２のガラス不織布、ジアリルイソフタレートプレポリマー（ダイソー（株）製、メジアン径２５μｍ）及びジアリルイソフタレートプレポリマー組成物の散布量を９０ｇ／ｍ２とした以外は実施例１と同様にしてプリプレグを作った。このプリプレグを用い温度を１５０℃とした以外は実施例１と同様にしてパーティクルボードに積層した。
【００２９】
実施例３
ジアリルテレフタレートモノマー（ダイソー（株）製、２３℃粘度１４ｍＰａ・ｓ）に純品のジクミルパーオキサイド３％及びカーボン（東海カーボン（株）製、シースト３）０．５％を加え、家庭用ジューサーミキサー（ＪＭ３６１三菱電機、ミキサー部パーツはＪＥ−１６２を使用）で３分間撹拌混合したこと以外は実施例２と同様にしてプリプレグを作った。このプリプレグを用い実施例２と同様にしてパーティクルボードに積層した。
【００３０】
実施例４
ジアリルオルソフタレートモノマー９０部とトリアリルイソシアネート（日本化成（株）製、２３℃粘度１０５ｍＰａ・ｓ） １０部を混合し、これに純品のジクミルパーオキサイド３％、ヒドロキノン０．０１％を溶解しメタクリルシラン（東芝シリコーン（株）製）１％を加えたもの、及びジアリルオルソフタレートプレポリマー５０部と市販品をハンマーミルで粉砕後目開き７０１μｍフルイでパスしたテレフタル酸系不飽和ポリエステル（日本ユピカ（株）製、ユピカ８５２４、酸価１８、１５０℃粘度９．３Ｐａ・ｓ、軟化点９６℃、メジアン径４６μｍ）５０部の混合物に４０％品のジクミルパーオキサイド５％、ステアリン酸亜鉛１％、酸化チタン（石原産業（株）製）１％を添加したものを使用した他は実施例１と同様にしてプリプレグを作った。このプリプレグを用い１５ｍｍ厚のＭＤＦ基板に実施例２と同一条件で積層した。
【００３１】
実施例５
ジアリルイソフタレートモノマー９０部とトリメチロールプロパントリアクリレート（共栄社化学（株）製）１０部を混合し、これに純品のジクミルパーオキサイド３％、ヒドロキノン０．０５％を加えたものにメタクリルシラン１％を添加したこと、ジアリルオルソフタレートプレポリマー５０部と実施例４と同一のテレフタル酸系不飽和ポリエステル５０部との混合物に４０％品のジクミルパーオキサイド５％、ステアリン酸亜鉛１％、シリカ粉１％を添加したこと、シート状繊維基材として１４０ｇ／ｍ２のクラフト紙を用いたこと及び液体成分の塗布量として３５ｇ／ｍ２にしたこと以外は実施例１と同様にしてプリプレグを作った。このプリプレグを用いて厚み４ｍｍのダンボール紙に１５０℃、０．８ＭＰａの圧、２分間の条件で積層した。
【００３２】
比較例１
液体成分を全く散布しないで、実施例１と同様にしてプリプレグを作り、同様のパーティクルボードに実施例１と同一条件で積層した。
【００３３】
比較例２
液体成分の散布量を６０ｇ／ｍ２とした以外は実施例１と同様にしてプリプレグを作り、同様にパーティクルボードに実施例１と同一条件で積層した。
【００３４】
実施例、比較例でえられた積層化粧板の評価結果を表１に示す。評価方法は次の通りである。
作業性 プリプレグを作成する時や積層板に重ねてプレスする際のプリプレグのべたつき、プリプレグからの樹脂の飛散、剥落がどうか観察した。
離型性 積層板のプレス成形時、プレスが終了して開圧した時に熱板から外れる時間を測定した。
外観 積層板のプレス成形後、プリプレグを積層した表面に、樹脂の欠落部分や艶落ち部分等の外観異常がないか観察した。
硬化性 積層板のプレス成形し室温まで冷えた後、プリプレグを積層した表面に、クロロホルムを充分に染み込ませた綿棒を置きガラスシャーレで蓋をして、１５分経過後その部分をふき取ってから外観が変化していないか観察した。
【００３５】
【表１】
注４ べたつきひどく、ポリエステル製フィルムから離れにくくなり作業が困難となった。
注５ 上記注３の欠陥部分以外でも、艶のないところがある。
注６ 樹脂の流動が良すぎて、プリプレグ基材の上に載っている量が少なく、全体に艶が悪い。
【００３６】
【発明の効果】
本発明によれば、ジアリルフタレートプレポリマーを使用したプリプレグ及び積層板を有機溶剤を使用しないで作ることができる。またこのようにして作ったプリプレグ及び積層板は、従来のように有機溶媒を使用して作ったものと何ら遜色ないものができる。[0001]
[Industrial application fields]
TECHNICAL FIELD The present invention relates to a prepreg for a laminate using a diallyl phthalate prepolymer, and in particular, a prepreg using a diallyl phthalate prepolymer suitable for interior decoration of a house, a vehicle, a ship, an aircraft, etc., or a decorative board used for furniture furniture. Further, the present invention relates to a decorative board that is hot-pressure laminated on the prepreg laminated board substrate.
[0002]
[Prior art]
Illustrated in JP-A-11-140203, JP-A-11-140777, etc., but good transparency, high surface hardness and glossiness of cured diallyl phthalate resin, heat resistance and chemical resistance, dimensional stability By utilizing the excellent properties such as the property, it has been widely used as a decorative plate for indoor interiors of houses, vehicles, ships, aircraft, etc., for tables, kotatsu top plates, system kitchens and the like. This diallyl phthalate resin decorative board is made of diallyl phthalate prepolymer, diallyl phthalate monomer, unsaturated polyester, curing agent, mold release agent, polymerization regulator, filler, UV absorber, and other additives. It is manufactured by laminating a board, a plywood board, a metal board such as cardboard or aluminum, etc. by heating and pressing with a press or the like.
[0003]
The prepreg of diallyl phthalate prepolymer uses a sheet-like substrate such as a nonwoven fabric or a woven fabric made of synthetic fibers such as plant fibers, glass fibers, and polyesters as a substrate, and diallyl phthalate prepolymer and other compounding agents. After impregnating a resin solution prepared by dissolving in an organic solvent, the solvent is removed by heating. This method is still widely practiced today.
[0004]
[Problems to be solved by the invention]
In recent years, resource saving and energy saving due to environmental problems have been demanded, and improvement of a prepreg manufacturing method using many solvents and energy has been demanded. As a countermeasure, various methods for producing a prepreg without using a solvent have been studied. However, a prepreg using a diallyl phthalate prepolymer still has no suitable method for producing it at low cost without using a solvent.
[0005]
Commercially available diallyl phthalate resin has a polystyrene equivalent weight average molecular weight of about 30,000 to 50,000, which is higher than that of phenolic resin, unsaturated polyester resin, and epoxy resin, and uses solvents for resins other than diallyl phthalate resin. Even if there is a method (for example, JP-A-11-226950) that can impregnate the resin in the prepreg base material without carrying out, the same method, the same process, cannot impregnate the diallyl phthalate prepolymer composition to every corner of the prepreg base material, Only voids with low product value were produced.
[0006]
As a result of studying to obtain a prepreg or a laminate without using a solvent that has been difficult to produce in the past, the present inventors have mixed a curing catalyst with a liquid component that can dissolve and react with a diallyl phthalate prepolymer. After applying to the prepreg base material, by spreading the diallyl phthalate prepolymer, the knowledge that the prepolymer composition impregnation into the base material is equivalent to that using a conventional solvent was obtained, and further research was repeated. The present invention has been completed.
[0007]
[Means and Actions for Solving the Problems]
The present invention solves the above-mentioned problems, and a sheet-like fiber base is prepared by dissolving a curing catalyst in a liquid component capable of dissolving a diallyl phthalate prepolymer and reacting with the diallyl phthalate prepolymer by a curing catalyst. After applying an amount corresponding to 5 to 50% of the weight of the sheet-like fiber base material on one side or both sides of the material, a fine powder of diallyl phthalate prepolymer in which a powdered curing catalyst was dispersed was spread on both sides of the coating. A prepreg of diallyl phthalate prepolymer for laminates, characterized in that.
[0008]
The diallyl phthalate prepolymer used in the present invention is a diallyl orthophthalate prepolymer, diallyl isophthalate prepolymer, diallyl terephthalate prepolymer alone or a copolymer thereof, or a mixture thereof, preferably having a particle size of 1000 μm or less, preferably The average particle diameter is 700 μm or less and the median diameter is 50 μm or less.
[0009]
In the present invention, the diallyl phthalate prepolymer may not be the diallyl phthalate prepolymer alone, as long as the diallyl phthalate prepolymer is 100 to 50% by weight, the particle size is 700 μm or less, and the average particle size is 50 μm or less. It may be a mixture of 0 to 50% by weight of unsaturated polyester having a melting point of 50 ° C. or higher.
[0010]
As unsaturated polyester, maleic acid, fumaric acid and itaconic acid are used alone or in combination as unsaturated acids, and aromatic polybasic acids such as isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid are used as saturated acids. Is a reaction product of a mixture of an unsaturated acid and a saturated acid and a polyhydric alcohol such as ethylene glycol, propylene glycol, diethylene glycol, etc., and has a melting point of 50 ° C. or higher.
[0011]
The reason for adding the unsaturated polyester is to improve the fluidity when the fluidity is further required than the combination of the diallyl phthalate prepolymer and the liquid component, for example, when the thickness of the sheet-like fiber substrate is large. However, if it exceeds 50% by weight, the heat resistance and water resistance, such as the high heat distortion temperature characteristic of diallyl phthalate resin, are lowered, which is not preferable.
[0012]
The liquid component capable of dissolving the diallyl phthalate prepolymer used in the present invention and reacting with the diallyl phthalate prepolymer by the curing catalyst is at least an allyl group, an acryl group, and a thiol group in the molecule, or two or more types. It refers to a substance having a viscosity of 6000 mPa · s or less at 23 ° C. including 1 to 6 and capable of dissolving 30% by weight or more of diallyl phthalate prepolymer at 23 ° C. The allyl group here may be a methallyl group, and the acryl group may be a methacryl group. These can be used alone or in combination. Examples of liquid components include allyl benzoate, diallyl orthophthalate monomer, diallyl isophthalate monomer, diallyl terephthalate monomer, triallyl isocyanate, triallyl cyanate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetrakisthioglycolate, etc. be able to.
[0013]
Curing catalysts used in the present invention are peroxide-based curings conventionally used in diallyl phthalate resin prepregs and molding materials such as benzoyl peroxide, tertiary butyl perbenzoate, methyl ethyl ketone peroxide, and dicumyl peroxide. You can give the agent.
[0014]
Examples of the sheet-like fiber base material include non-woven fabrics and woven fabrics made of synthetic fibers such as vegetable fibers, glass fibers and polyesters, papers, cardboard, woven fabrics and mats made of metal fibers and carbon fibers, and the like. You may use the raw material of a material individually or in mixture.
[0015]
The prepreg of the present invention is laminated on a decorative board substrate such as plywood, particle board, medium density fiber board (MDF board), other inorganic board, metal board board, cardboard, cardboard, etc. Hot pressed to form a decorative laminate. Molding is performed at a temperature of 130 to 200 ° C., a pressure of 0.1 to 3 MPa, and a time of 20 seconds to 2 minutes.
[0016]
Next, embodiments of the present invention will be described. First, it is possible to dissolve diallyl phthalate prepolymer and mix 0.1 to 10% by weight of organic peroxide soluble in the liquid component as a curing catalyst in the liquid component that reacts with the diallyl phthalate resin by the curing catalyst. Make what you did. When the liquid component contains an acrylic group or a thiol group, hydroquinone, hydroquinone monomethyl ether, tertiary butyl catechol, or the like can be added in an amount of 1000 ppm or less as a polymerization inhibitor. In addition, various silane coupling agents, mold release agents, fillers, ultraviolet absorbers, coloring agents such as dyes and pigments, and the like can be added to this liquid as necessary.
[0017]
A sheet-like fiber base material, which is a prepreg base material, is spread on a flat table on which a polyester film is laid, and the liquid component composition is uniformly dispersed or adhered. The method is not particularly limited, such as spraying by spraying or coating by various coaters. Usually, it may be spread or adhered on only one side, but if the sheet-like fiber substrate is thick, it is spread or adhered on both sides.
[0018]
This adhesion amount varies depending on the properties, properties, and weight (per unit area) of the sheet-like fiber substrate, but is usually 5 to 50% by weight of the weight of the sheet-like fiber substrate. When this amount is small, diallyl phthalate prepolymer is sprinkled from above to make a prepreg, and then when heated and pressed together with the substrate, the flow of diallyl phthalate prepolymer is reduced, and the prepreg base material is sufficiently filled with diallyl phthalate prepolymer. Without impregnation, a defective part from which the resin has fallen off is easily formed, which is not preferable in appearance. Even if this amount is too large, when diallyl phthalate prepolymer is sprayed from above to form a prepreg, it becomes difficult to handle in the process after the tack remains.
[0019]
Next, diallyl phthalate prepolymer (which may contain 50% by weight or less of solid unsaturated polyester) is sprayed on both sides of the sheet-like fiber base material. At this time, as a curing catalyst for the diallyl phthalate prepolymer, it is also essential to blend 0.1 to 10% by weight of a resin in which an organic peroxide is dispersed in a filler such as calcium carbonate having an average particle size of 10 μm or less. And In addition, various fillers, mold release agents, ultraviolet absorbers, coloring agents such as dyes and pigments can be added up to 20% by weight of the diallyl phthalate prepolymer amount as necessary. In that case, those materials are mixed and stirred in advance by various blenders and mixers before spraying.
[0020]
The amount of application varies depending on the properties, properties, and weight (per unit area) of the sheet-like fiber substrate, but is usually 50 to 300% of the weight of the sheet-like fiber substrate. 20 to 80% by weight of this amount is sprayed on one side of the sheet-like fiber substrate, and the remaining 80 to 20% by weight is sprayed on the other side. When this amount is small, a sufficient gloss cannot be obtained after molding with the substrate, resulting in poor cosmetic properties. Moreover, even if there is too much application | coating amount, gloss does not go up to a certain extent, but it becomes a cost increase.
[0021]
The spraying method is not particularly limited as long as the resin powder can be sprayed and adhered satisfactorily, such as a method of sprinkling from the upper surface of the sheet-like fiber substrate, a coating method using various coaters, an electrostatic coating method, or a spraying method using spray. At this time, it is not necessary to heat and heat the sheet-like fiber base material. However, after the resin is sprayed, it varies depending on the amount of the liquid component sprayed until the feeling of stickiness disappears, but it can be left at room temperature for about 1-2 hours. In this case, the liquid component dissolves and absorbs the diallyl phthalate prepolymer and does not feel sticky. By this time, when the feeling of adhesion disappears, the adhesion between the sheet-like fiber base material and the polyester film becomes slight and can be peeled off from the polyester film. After that, the polyester film is peeled off and turned over, and the remaining diallyl phthalate prepolymer is sprayed.
[0022]
On the other hand, the sheet-like fiber base material after spraying the prepolymer can be heated to shorten the process time. By removing it by heating it in an oven at 50 to 130 ° C. for 5 to 60 minutes, tack is almost eliminated. Thereafter, the sheet-like fiber base material is turned over and the remaining prepolymer composition is sprayed, or after spraying, the prepreg can be heated in the same manner.
[0023]
As a result, first, the prepreg base material is wetted to every corner by the liquid component capable of dissolving the diallyl phthalate prepolymer, and then the diallyl phthalate prepolymer adhered by spraying the diallyl phthalate prepolymer is liquid. It is dissolved in the ingredients and penetrates into the prepreg base material. Furthermore, during hot pressing, the viscosity of the diallyl phthalate prepolymer containing the liquid component is markedly reduced compared to when it is alone, so that it can be impregnated throughout the prepreg substrate even during a short molding time. Thus, a decorative laminate having a smooth surface and good gloss can be obtained.
[0024]
On the other hand, when viewed from the liquid component, it is adsorbed by the diallyl phthalate prepolymer, and the surface wetted by the liquid becomes visually dry, and it is superposed on the subsequent laminate substrate or hot pressure. The handling in the pressing process becomes possible in the same situation as the prepreg when a solvent is used.
[0025]
[Examples and comparative examples]
Next, examples of the present invention will be described in detail together with comparative examples, but the present invention is not limited to these examples. All parts and percentages shown in the examples and comparative examples are parts by weight and percentages by weight.
[0026]
Example 1
Diallyl orthophthalate monomer (manufactured by Daiso Co., Ltd., 23 ° C. viscosity Note 1 12 mPa · s) obtained by stirring and dissolving 3% of dicumyl peroxide (Nippon Yushi Co., Ltd., Park Mill D, flakes, pure product) I was sprayed at a rate of 20g / m 2 by using a household spray pattern printing paper of 80g / m 2. On top of this, 100 parts of diallyl orthophthalate prepolymer (Daiso Co., Ltd., median diameter Note 2 32 μm) and dicumyl peroxide (Nippon Yushi Co., Ltd., Park Mill D-40, powder, 40% product) 5 use sieve having an opening of 701μm in parts and proportions of zinc stearate (Sakai chemical Co., Ltd.) 1 part half those shaken for 3 minutes in a plastic bag of 80 g / m 2 to 40 g / m 2 Evenly sprayed. The mixture was heated in an oven at 130 ° C. for 5 minutes, cooled, turned over, and the remaining diallyl orthophthalate prepolymer composition was sprayed in the same manner at a rate of 40 g / m 2 , and heated in an oven at 130 ° C. for 5 minutes to obtain a prepreg.
[0027]
Using this prepreg, hot pressure lamination was performed on a particle board having a thickness of 15 mm at 140 ° C. and a pressure of 1.5 MPa for 2 minutes.
Note 1 The 23 ° C. viscosity was measured with a digital viscometer DVM-E type (Tokyo Keiki). same as below.
Note 2: The median diameter was measured with a Microtrac HRA particle size analyzer (Nikkiso).
same as below.
[0028]
Example 2
Silica powder (Shiono) by dissolving 3% pure dicumyl peroxide and 0.01% hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.) in diallyl isophthalate monomer (manufactured by Daiso Co., Ltd., 23 ° C., viscosity 18 mPa · s) 90 g / m 2 glass nonwoven fabric, diallyl isophthalate prepolymer (Daiso Co., median diameter 25 μm) and diallyl isophthalate prepolymer composition spraying amount of 90 g A prepreg was prepared in the same manner as in Example 1 except that the ratio was / m 2 . The prepreg was laminated on the particle board in the same manner as in Example 1 except that the temperature was 150 ° C.
[0029]
Example 3
Diallyl terephthalate monomer (manufactured by Daiso Co., Ltd., 23 ° C. viscosity 14 mPa · s) is added with pure dicumyl peroxide 3% and carbon (Tokai Carbon Co., Ltd., Seast 3) 0.5%. A prepreg was made in the same manner as in Example 2 except that the mixture was stirred and mixed for 3 minutes with a mixer (JM361 Mitsubishi Electric, mixer part using JE-162). Using this prepreg, it was laminated on a particle board in the same manner as in Example 2.
[0030]
Example 4
90 parts of diallyl orthophthalate monomer and 10 parts of triallyl isocyanate (manufactured by Nippon Kasei Co., Ltd., 23 ° C., viscosity 105 mPa · s) are mixed, and 3% pure dicumyl peroxide and 0.01% hydroquinone are dissolved in this. Terephthalic acid-based unsaturated polyester obtained by adding 1% methacrylic silane (manufactured by Toshiba Silicone Co., Ltd.) and 50 parts of diallyl orthophthalate prepolymer and a commercially available product after pulverizing with a hammer mill and passing through a 701 μm sieve Yupica 8524, Iupica 8524, acid number 18, 150 ° C. viscosity 9.3 Pa · s, softening point 96 ° C., median diameter 46 μm) 50 parts mixture of 40% dicumyl peroxide 5%, zinc stearate Example 1 was used except that 1% and titanium oxide (Ishihara Sangyo Co., Ltd.) 1% were added. I made a prepreg. Using this prepreg, a 15 mm thick MDF substrate was laminated under the same conditions as in Example 2.
[0031]
Example 5
90 parts by weight of diallyl isophthalate monomer and 10 parts of trimethylolpropane triacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) are mixed with methacrylic silane to which 3% pure dicumyl peroxide and 0.05% hydroquinone are added. 1% was added, 50% of diallyl orthophthalate prepolymer and 50 parts of the same terephthalic acid-based unsaturated polyester as in Example 4, 40% dicumyl peroxide 5%, zinc stearate 1%, Pre-preg in the same manner as in Example 1 except that 1% of silica powder was added, 140 g / m 2 of kraft paper was used as the sheet-like fiber base material, and the coating amount of the liquid component was 35 g / m 2. made. Using this prepreg, it was laminated on corrugated cardboard having a thickness of 4 mm under the conditions of 150 ° C., 0.8 MPa pressure and 2 minutes.
[0032]
Comparative Example 1
A prepreg was prepared in the same manner as in Example 1 without spraying any liquid component, and was laminated on the same particle board under the same conditions as in Example 1.
[0033]
Comparative Example 2
A prepreg was prepared in the same manner as in Example 1 except that the amount of liquid component applied was 60 g / m 2 , and was similarly laminated on the particle board under the same conditions as in Example 1.
[0034]
Table 1 shows the evaluation results of the laminated decorative boards obtained in the examples and comparative examples. The evaluation method is as follows.
Workability It was observed whether the prepreg was sticky when the prepreg was created or when it was stacked and pressed, and the resin was scattered or peeled off from the prepreg.
Releasability At the time of press molding of the laminate, the time required to release from the hot plate when the press was completed and the pressure was released was measured.
Appearance After press-molding the laminate, the surface on which the prepreg was laminated was observed for appearance abnormalities such as missing portions of resin and glossy portions.
Hardening After pressing the laminated board and cooling to room temperature, place a cotton swab soaked in chloroform on the surface where the prepreg was laminated, cover it with a glass petri dish, and wipe it off after 15 minutes. Was observed for changes.
[0035]
[Table 1]
Note 4 It was very sticky and difficult to separate from the polyester film, making it difficult to work.
Note 5 There are some areas other than the defects in Note 3 above that are not glossy.
Note 6 The flow of the resin is too good, the amount on the prepreg base material is small, and the overall gloss is poor.
[0036]
【The invention's effect】
According to the present invention, a prepreg and a laminate using a diallyl phthalate prepolymer can be produced without using an organic solvent. In addition, the prepreg and laminate produced in this way can be the same as those produced using an organic solvent as in the prior art.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001185625A JP4586306B2 (en) | 2001-05-16 | 2001-05-16 | Prepreg of diallyl phthalate prepolymer for laminates |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001185625A JP4586306B2 (en) | 2001-05-16 | 2001-05-16 | Prepreg of diallyl phthalate prepolymer for laminates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002338711A JP2002338711A (en) | 2002-11-27 |
| JP4586306B2 true JP4586306B2 (en) | 2010-11-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2001185625A Expired - Fee Related JP4586306B2 (en) | 2001-05-16 | 2001-05-16 | Prepreg of diallyl phthalate prepolymer for laminates |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5099400B2 (en) * | 2005-12-06 | 2012-12-19 | ダイソー株式会社 | Decorative plate with excellent surface smoothness |
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|---|---|---|---|---|
| JPS5379962A (en) * | 1976-12-23 | 1978-07-14 | Osaka Soda Co Ltd | Production of decorative plate |
| JPS5569612A (en) * | 1978-11-16 | 1980-05-26 | Toray Ind Inc | Resin composition for fiber-reinforcement |
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| JPH11140203A (en) * | 1997-11-13 | 1999-05-25 | Daiso Co Ltd | Diallyl phthalate-based resin impregnated paper cloth for short time molding |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002338711A (en) | 2002-11-27 |
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