JP2017007123A - 成形体 - Google Patents
成形体 Download PDFInfo
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- JP2017007123A JP2017007123A JP2015122342A JP2015122342A JP2017007123A JP 2017007123 A JP2017007123 A JP 2017007123A JP 2015122342 A JP2015122342 A JP 2015122342A JP 2015122342 A JP2015122342 A JP 2015122342A JP 2017007123 A JP2017007123 A JP 2017007123A
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Images
Classifications
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Abstract
Description
本発明の成形体(以下、単に「本発明」と称する場合がある)は、ハードコート層、基材層、熱可塑性樹脂層を少なくとも含み、成形体が曲面形状を有し、成形体の最表面が該ハードコート層である。本発明の成形体の好ましい態様の1例(ハードコート層/基材層/熱可塑性樹脂層)を図1に示す。本発明の成形体は、ハードコート層、基材層、熱可塑性樹脂層以外の層、例えば粘着剤層、アンカー層、低反射層、防汚層、撥水層、撥油層、防曇層、保護フィルム層、印刷層、導電層、電磁波シールド層、紫外線吸収層、赤外線吸収層、ブルーライトカット層等を有していてもよい。上記曲面形状は、成形体の全体若しくは一部に平面ではない部分(曲面部)を有していればよく、曲面は最表面のハードコート層に向かって、凸形状に湾曲しても凹形状に湾曲してもよいが、凸形状に湾曲していることが好ましい。本発明の成形体は、後述の成形体の製造方法により作製できる。なお、上記ハードコート層は、上記基材層の表面において、一部のみに形成されていてもよいし、全面に形成されていてもよい。
本発明において上記ハードコート層は、後述する硬化性組成物の硬化物で形成されている。上記ハードコート層は、上記硬化性組成物(ハードコート層形成用硬化性組成物)により形成されたハードコート層(硬化性組成物の硬化物層)である。なお、上記ハードコート層は、後述する成形体の製造方法((A)ハードコート層形成工程)により、硬化性組成物から作製することができる。
本発明において上記硬化性組成物は、カチオン硬化性シリコーン樹脂、レベリング剤を少なくとも含む。硬化性組成物は、上記以外にカチオン硬化性シリコーン樹脂以外のエポキシ化合物(以下、単に「エポキシ化合物」と称する場合がある)や硬化触媒等を含んでいてもよい。本発明において硬化性組成物の最も好ましい態様としては、カチオン硬化性シリコーン樹脂、エポキシ化合物、レベリング剤、硬化触媒を含むものを挙げることができる。特に本発明における硬化性組成物は、以下の特有のカチオン硬化性シリコーン樹脂を用いていることを特徴とする。
上記カチオン硬化性シリコーン樹脂は、単量体を構成する単位としてシルセスキオキサン単位を含み、全単量体単位のうちエポキシ基を有する単量体単位の割合が、50モル%以上であり、且つ数平均分子量が、1000〜3000である。なお、上記数平均分子量は、GPC(ゲルパーミエーションクロマトグラフィー)による標準ポリスチレン換算の値である。
測定装置:商品名「JNM−ECA500NMR」(日本電子(株)製)
溶媒:重クロロホルム
積算回数:1800回
測定温度:25℃
測定装置:商品名「FT−720」((株)堀場製作所製)
測定方法:透過法
分解能:4cm-1
測定波数域:400〜4000cm-1
積算回数:16回
測定装置:商品名「LC−20AD」((株)島津製作所製)
カラム:Shodex KF−801×2本、KF−802、及びKF−803(昭和電工(株)製)
測定温度:40℃
溶離液:THF、試料濃度0.1〜0.2重量%
流量:1mL/分
検出器:UV−VIS検出器(商品名「SPD−20A」、(株)島津製作所製)
分子量:標準ポリスチレン換算
上記カチオン硬化性シリコーン樹脂は、公知乃至慣用のポリオルガノシロキサンの製造方法により製造することができ、例えば、1種又は2種以上の加水分解性シラン化合物を加水分解及び縮合させる方法により製造できる。但し、上記加水分解性シラン化合物としては、上述の式(1)で表される構成単位を形成するための加水分解性三官能シラン化合物(下記式(a)で表される化合物)を必須の加水分解性シラン化合物として使用する必要がある。
硬化性組成物は、上記カチオン硬化性シリコーン樹脂以外のエポキシ化合物を含んでいてもよい。上記カチオン硬化性シリコーン樹脂に加えて、エポキシ化合物を含むことにより、高い表面硬度を有し、可とう性及び加工性に優れた硬化物を形成できる。
上記硬化性組成物は、表面平滑性の向上ため、レベリング剤を含む。レベリング剤としては、表面張力低下能を有していればよく、慣用のレベリング剤を使用することができる。レベリング剤としては、表面張力低下能に優れる点から、シリコーン系レベリング剤、フッ素系レベリング剤が好ましく、特にシリコーン系レベリング剤が好ましい。本発明では、カチオン硬化性シリコーン樹脂とレベリング剤とを組合せることにより、表面平滑性を向上でき、透明性や光沢(外観)、滑り性等を向上できる。さらに、特定のレベリング剤を特定量用いることにより、表面硬度や耐擦傷性をより向上させることができる。
上記硬化性組成物は、さらに、硬化触媒を含むことが好ましい。なかでも、よりタックフリーとなるまでの硬化時間が短縮できる点で、硬化触媒として光カチオン重合開始剤を含むことが特に好ましい。
上記硬化性組成物は、さらに、その他任意の成分として、沈降シリカ、湿式シリカ、ヒュームドシリカ、焼成シリカ、酸化チタン、アルミナ、ガラス、石英、アルミノケイ酸、酸化鉄、酸化亜鉛、炭酸カルシウム、カーボンブラック、炭化ケイ素、窒化ケイ素、窒化ホウ素等の無機質充填剤、これらの充填剤をオルガノハロシラン、オルガノアルコキシシラン、オルガノシラザン等の有機ケイ素化合物により処理した無機質充填剤;シリコーン樹脂、エポキシ樹脂、フッ素樹脂等の有機樹脂微粉末;銀、銅等の導電性金属粉末等の充填剤、硬化助剤、溶剤(有機溶剤等)、安定化剤(酸化防止剤、紫外線吸収剤、耐光安定剤、熱安定化剤、重金属不活性化剤等)、難燃剤(リン系難燃剤、ハロゲン系難燃剤、無機系難燃剤等)、難燃助剤、補強材(他の充填剤等)、核剤、カップリング剤(シランカップリング剤等)、滑剤、ワックス、可塑剤、離型剤、耐衝撃改良剤、色相改良剤、透明化剤、レオロジー調整剤(流動性改良剤等)、加工性改良剤、着色剤(染料、顔料等)、帯電防止剤、分散剤、表面改質剤(スリップ剤等)、艶消し剤、消泡剤、抑泡剤、脱泡剤、抗菌剤、防腐剤、粘度調整剤、増粘剤、光増感剤、発泡剤等の慣用の添加剤を含んでいてもよい。これらの添加剤は1種を単独で、又は2種以上を組み合わせて使用できる。
上記硬化性組成物は、特に限定されないが、上記の各成分を室温で又は必要に応じて加熱しながら攪拌・混合することにより調製することができる。なお、硬化性組成物は、各成分があらかじめ混合されたものをそのまま使用する1液系の組成物として使用することもできるし、例えば、別々に保管しておいた2以上の成分を使用前に所定の割合で混合して使用する多液系(例えば、2液系)の組成物として使用することもできる。
上記硬化性組成物におけるカチオン硬化性化合物の重合反応を進行させることにより、該硬化性組成物を硬化させることができ、硬化物を得ることができる。硬化の方法は、周知の方法より適宜選択でき、例えば、活性エネルギー線の照射、及び/又は、加熱する方法を挙げることができる。上記活性エネルギー線としては、例えば、赤外線、可視光線、紫外線、X線、電子線、α線、β線、γ線等のいずれを使用することもできる。なかでも、取り扱い性に優れる点で、紫外線が好ましい。
本発明の成形体における基材層に用いる基材としては、例えば、プラスチック基材、金属基材、セラミックス基材、半導体基材、ガラス基材、紙基材、木基材(木製基材)、表面が塗装表面である基材等の公知乃至慣用の基材を用いることができる。なかでも、プラスチック基材(プラスチック材料により構成された基材)が好ましい。
本発明の成形体における上記熱可塑性樹脂層を構成する熱可塑性樹脂としては、例えば、オレフィン系樹脂、ビニル系重合体(付加重合系樹脂)、ポリエステル系樹脂、ポリアミド系樹脂、ポリカーボネート系樹脂、ポリウレタン系樹脂、ポリフェニレンオキシド系樹脂、ポリフェニレンスルフィド系樹脂、ポリスルホン系樹脂、セルロース誘導体、ポリイミド系樹脂等を挙げることができる。これらの熱可塑性樹脂のうち、成形性、機械的特性などの点から、オレフィン系樹脂、ビニル系重合体(スチレン系樹脂、(メタ)アクリル系樹脂、ポリアクリロニトリル系樹脂、塩化ビニル系樹脂、ビニルアルコール系樹脂等)、ポリエステル系樹脂が好ましい。これらの熱可塑性樹脂は、単独で又は二種以上組み合わせて使用することができる。上記熱可塑性樹脂層の好ましい態様としては、シート状の熱可塑性樹脂シート、上記熱可塑性樹脂を射出成形等で成形した熱可塑性樹脂の成形物の態様を挙げることができる。
本発明の成形体は、特に制限されないが、以下の(A)〜(C)の工程を含む方法により製造することができる。本発明の成形体は、以下の(A)〜(C)以外の工程(例えば、アンカー層や粘着剤層を設ける工程)を含む製造方法にて製造してもよい。なかでも本発明の成形体では、後述する(A)(B)(C)の順で製造する方法(一体成形)、又は(A)(C)(B)の順で製造する方法(後貼り)が好ましい。
(A)基材層上にハードコート層を形成する(ハードコート層形成工程)
(B)基材層と熱可塑性樹脂層を貼り合せる(貼合工程)
(C)成形体を所望の曲面形状に成形する(成形工程)
上記ハードコート層形成工程は、基材層上にハードコート層を形成させ、基材付きハードコートフィルムを作製する工程である。ハードコート層の形成は、公知乃至慣用のハードコートフィルムの製造方法に準じて製造することができ、その製造方法は特に限定されないが、上記基材の少なくとも一方の表面に上記硬化性組成物(ハードコート層形成用硬化性組成物)を塗布し、必要に応じて溶剤を乾燥によって除去した後、硬化性組成物(硬化性組成物層)を硬化させることにより製造できる。硬化性組成物を硬化させる際の条件は、特に限定されず、上述の硬化物を形成する際の条件から適宜選択可能である。なお、基材付きハードコートフィルムは、基材付きハードコートシートであってもよい。
上記貼合工程は、図2に示すように基材付きハードコートフィルム(基材側)と熱可塑性樹脂層を貼り合せる工程であり、公知乃至慣用の貼合方法にて行うことができる。貼合方法は特に限定されないが、容易に貼り合わせることができ、生産性が良い点から、基材と熱可塑性樹脂層の一方又は両方を加熱し、圧力をかけてヒートプレスする方法が好ましい。上記ヒートプレスは、枚葉方式で行っても、ロールトゥロール方式で行ってもよい。加熱する温度は、基材や熱可塑性樹脂の融点以上の温度であればよいが、例えば100〜500℃であり、好ましくは150〜300℃である。圧力は、例えば0.1〜100Paであり、好ましくは1〜50Paである。上記貼合工程では、上記ヒートプレス以外にも、粘着剤を用いる方法等を挙げることができる。粘着剤としては、アクリル系粘着剤、シリコン系粘着剤等の公知乃至慣用の粘着剤を用いることができる。
上記成形工程は、所望の曲面形状に成形する工程であり、公知乃至慣用の成形方法にてすることができ、その方法は特に限定されないが、真空成形、射出成形等の型を用いた成形方法を挙げることができる。なかでも容易に成形できる点から、真空成形が好ましい。
(カチオン硬化性シリコーン樹脂の調製)
温度計、攪拌装置、還流冷却器、及び窒素導入管を取り付けた300ミリリットルのフラスコ(反応容器)に、窒素気流下で2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン(以下、「EMS」と称する)161.5ミリモル(39.79g)、フェニルトリメトキシシラン(以下、「PMS」と称する)9ミリモル(1.69g)、及びアセトン165.9gを仕込み、50℃に昇温した。このようにして得られた混合物に、5%炭酸カリウム水溶液4.70g(炭酸カリウムとして1.7ミリモル)を5分で滴下した後、水1700ミリモル(30.60g)を20分かけて滴下した。なお、滴下の間、著しい温度上昇は起こらなかった。その後、50℃のまま、重縮合反応を窒素気流下で4時間行った。
重縮合反応後の反応溶液中の生成物を分析したところ、数平均分子量は1911であり、分子量分散度は1.47であった。上記生成物の29Si−NMRスペクトルから算出されるT2体とT3体のモル比[T3体/T2体]は10.3であった。生成物のFT−IRスペクトルを上述の方法で測定したところ、1100cm-1付近に一つの固有吸収ピークを有することが確認された。
その後、反応溶液を冷却し、下層液が中性になるまで水洗を行い、上層液を分取した後、1mmHg、40℃の条件で上層液から溶媒を留去し、無色透明の液状の生成物(エポキシ基を有するシルセスキオキサン単位を含むカチオン硬化性シリコーン樹脂;硬化性樹脂A)を得た。上記生成物のTd5は370℃であった。
得られた硬化性樹脂A5.0重量部、硬化触媒0.1重量部、レベリング剤0.05重量部の混合溶液を作製し、これをハードコート液(硬化性組成物)として使用した。
得られた基材付きハードコートフィルムの基材層側に熱可塑性樹脂層として熱可塑性樹脂(PMMA)シート(商品名「アクリプレン」、三菱レイヨン(株)社製、厚み200μm)を温度110℃、2.5kg/cm2の条件でヒートプレスして、基材付きハードコートフィルムと熱可塑性樹脂シートを一体化させた。その後、真空成形機(浅野研究所製、真空圧空成機「FK−0431−10」)内にて、一体化したシート(250mm×250mm)が150℃になるまで予熱し、真空成形用の金型として、凸型の曲面形状を有するアルミ製金型を使用し、予熱されたシートをハードコート層が上になるように金型上に移動させ、金型内で吸引して曲面形状の成形体を得た。
実施例2〜5については、表1に示すように、硬化性樹脂の配合量を変更し、エポキシ化合物を0.5重量部添加して混合物(組成物)を調製する以外は実施例1と同様にして基材付きハードコートフィルムを作製し、成形体を作製した。なお、実施例2〜5で得られた組成物におけるポリオルガノシルセスキオキサンのFT−IRスペクトルを上述の方法で測定したところ、いずれも1100cm-1付近に一つの固有吸収ピークを有することが確認された。なお、ハードコート層の厚みは、表1に示すとおりである。
(カチオン硬化性シリコーン樹脂の調製)
温度計、攪拌装置、還流冷却器、及び窒素導入管を取り付けた300ミリリットルのフラスコ(反応容器)に、窒素気流下でEMS161.5ミリモル(39.79g)、PMS9ミリモル(1.69g)、及びアセトン165.9gを仕込み、50℃に昇温した。このようにして得られた混合物に、5%炭酸カリウム水溶液4.70g(炭酸カリウムとして1.7ミリモル)を5分で滴下した後、水1700ミリモル(30.60g)を20分かけて滴下した。なお、滴下の間、著しい温度上昇は起こらなかった。その後、50℃のまま、重縮合反応を窒素気流下で4時間行った。
重縮合反応後の反応溶液中の生成物を分析したところ、数平均分子量は1799であり、分子量分散度は1.57であった。上記生成物の29Si−NMRスペクトルから算出されるT2体とT3体のモル比[T3体/T2体]は10.1であった。生成物のFT−IRスペクトルを上述の方法で測定したところ、1100cm-1付近に一つの固有吸収ピークを有することが確認された。
その後、反応溶液を冷却し、下層液が中性になるまで水洗を行い、上層液を分取した後、1mmHg、40℃の条件で上層液から溶媒を留去し、無色透明の液状の生成物(エポキシ基を有するシルセスキオキサン単位を含むカチオン硬化性シリコーン樹脂;硬化性樹脂B)を得た。上記生成物のTd5は370℃であった。
得られた硬化性樹脂B4.5重量部、エポキシ化合物0.5重量部、硬化触媒0.05重量部、レベリング剤0.05重量部の混合溶液を作製し、これをハードコート液(硬化性組成物)として使用した。得られたハードコート液から、実施例1と同様にして基材付きハードコートフィルムを作製し、成形体を作製した。
ハードコート液(硬化性組成物)の組成及びハードコート層の厚みを表1に示すように変更したこと以外は実施例6と同様にして、ハードコート液を作製し、成形体を作製した。
比較例1〜4については、表1に示す硬化性樹脂を使用し、レベリング剤を使用せずに、混合物(組成物)を調製したこと以外は実施例1と同様にしてハードコートフィルムを作製し、成形体を作製した。
上記で得た成形体におけるハードコート層表面の鉛筆硬度(表面硬度)を、JIS K5600−5−4に準じて評価した。この評価結果を表1に示す。なお、評価は3回行い最も硬いものを評価結果とした。
上記で得たハードコートフィルムの曲げ(耐屈曲性)を、円筒形マンドレルを使用してJIS K5600−5−1に準じて評価した。この評価結果を表1に示す。
(硬化性樹脂)
PETIA:ペンタエリスリトールトリアクリレートとペンタエリスリトールテトラアクリレートの混合物、商品名「PETIA」(ダイセル・オルネクス(株)製)
IRR214K:トリシクロデカンジメタノールジアクリレート、商品名「IRR214K」(ダイセル・オルネクス(株)製)
TA−100:アクリルシリコーン樹脂、商品名「SQ TA−100」(東亜合成(株)製)
SI−20:アクリルシリコーン樹脂、商品名「SQ SI−20」(東亜合成(株)製)
(エポキシ化合物)
セロキサイド2021P:3,4−エポキシシクロヘキシルメチル(3,4−エポキシ)シクロヘキサンカルボキシレート、商品名「セロキサイド2021P」((株)ダイセル製)
エポキシ化合物A:ビス(3,4−エポキシシクロヘキシルメチル)エーテル
EHPE3150:2,2−ビス(ヒドロキシメチル)−1−ブタノールの1,2−エポキシ−4−(2−オキシラニル)シクロヘキサン付加物、商品名「EHPE3150」((株)ダイセル製)
エポキシ化合物B:2,2−ビス(3,4−エポキシシクロヘキシルメチル)プロパン
(溶剤)
MEK:メチルエチルケトン
(硬化触媒)
WPI−124:商品名「WPI−124」、(和光純薬工業(株)製、光酸発生剤の50%溶液)
硬化触媒A:[4−(4−ビフェニルチオ)フェニル]−4−ビフェニルフェニルスルホニウム トリス(ペンタフルオロエチル)トリフルオロホスフェートのプロピレングリコールメチルエーテルアセテート50%溶液
イルガキュア 184:光重合開始剤、商品名「IRGACURE 184」(BASFジャパン(株)製)
(レベリング剤)
サーフロン S−243:フッ素化合物のエチレンオキサイド付加物、商品名「サーフロン S−243」(AGCセイミケミカル(株)製)
2 ハードコート層
3 基材層
4 熱可塑性樹脂層
5 基材付きハードコートフィルム
Claims (15)
- ハードコート層、基材層、熱可塑性樹脂層を少なくとも含む曲面形状を有する成形体であって、成形体の最表面が前記ハードコート層であり、前記ハードコート層が、硬化性組成物の硬化物で形成され、前記硬化性組成物が、カチオン硬化性シリコーン樹脂、レベリング剤を少なくとも含み、前記カチオン硬化性シリコーン樹脂が、シルセスキオキサン単位を含み、全単量体単位のうちエポキシ基を有する単量体単位の割合が50モル%以上であり、且つ1000〜3000の数平均分子量を有する成形体。
- シロキサン構成単位の全量(100モル%)に対する、前記式(1)で表される構成単位及び前記式(2)で表される構成単位の合計の割合(総量)が、55〜100モル%である請求項3に記載の成形体。
- 前記カチオン硬化性シリコーン樹脂の分子量分散度(重量平均分子量/数平均分子量)が、1.0〜3.0である請求項1〜4の何れか1項に記載の成形体。
- 前記レベリング剤が、シリコーン系レベリング剤及び/又はフッ素系レベリング剤であり、かつエポキシ基に対する反応性基及び/又は加水分解縮合性基を有する請求項1〜6の何れか1項に記載の成形体。
- 前記レベリング剤の割合が、前記カチオン硬化性シリコーン樹脂100重量部に対して、0.01〜10重量部である請求項1〜7の何れか1項に記載の成形体。
- 前記レベリング剤が、ヒドロキシル基を有するシリコーン系レベリング剤であり、且つレベリング剤の割合が、前記カチオン硬化性シリコーン樹脂100重量部に対して、0.01〜5重量部である請求項1〜8の何れか1項に記載の成形体。
- さらに、硬化触媒を含む請求項1〜9の何れか1項に記載の成形体。
- 前記硬化触媒が、光カチオン重合開始剤である請求項10に記載の成形体。
- 前記硬化触媒が、熱カチオン重合開始剤である請求項10に記載の成形体。
- 前記硬化性組成物が、ハードコート層形成用硬化性組成物である請求項1〜12のいずれか1項に記載の成形体。
- 前記ハードコート層の厚さが、0.1〜200μmである請求項1〜13のいずれか1項に記載の成形体。
- ロールトゥロール方式で製造された請求項1〜14の何れか1項に記載の成形体。
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JP2018189800A (ja) * | 2017-05-02 | 2018-11-29 | 株式会社ダイセル | 曲面ディスプレイ用ハードコートフィルム、ハードコートフィルム付き透明基板及びディスプレイ装置 |
WO2019054424A1 (ja) * | 2017-09-12 | 2019-03-21 | 株式会社ダイセル | プラスチックレンズ |
WO2019054425A1 (ja) * | 2017-09-12 | 2019-03-21 | 株式会社ダイセル | プラスチックレンズ |
KR20210013087A (ko) * | 2018-05-18 | 2021-02-03 | 주식회사 다이셀 | 적층 필름 및 폴더블 디바이스 |
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JP6626950B2 (ja) * | 2018-01-29 | 2019-12-25 | 住友化学株式会社 | 光学積層体 |
KR20220031925A (ko) * | 2019-09-27 | 2022-03-14 | 후지필름 가부시키가이샤 | 하드 코트층 형성용 조성물, 하드 코트 필름, 하드 코트 필름의 제조 방법, 및 하드 코트 필름을 포함하는 물품 |
CN112760034A (zh) * | 2020-12-28 | 2021-05-07 | 浙江伟星光学有限公司 | 一种增加树脂镜片表面硬度的加硬液 |
US11938670B2 (en) * | 2021-09-01 | 2024-03-26 | GM Global Technology Operations LLC | Powder coated vacuum formed articles |
IT202200011891A1 (it) * | 2022-06-06 | 2023-12-06 | Sicis Int Srl | Lastra multistrato laminata |
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WO2016203958A1 (ja) | 2016-12-22 |
US20180362803A1 (en) | 2018-12-20 |
KR20180019116A (ko) | 2018-02-23 |
JP6619954B2 (ja) | 2019-12-11 |
CN111093963B (zh) | 2022-02-25 |
CN111093963A (zh) | 2020-05-01 |
TW201708447A (zh) | 2017-03-01 |
TWI701303B (zh) | 2020-08-11 |
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