JP4284728B2 - Antireflection film, laminate including antireflection film, and method for producing antireflection film - Google Patents

Description

【００５７】
［一般式（５）中、Ｒ⁹、Ｒ¹⁰、Ｒ¹³〜Ｒ¹⁶は炭素数１〜６の一価の有機基であり、Ｒ¹¹およびＲ¹²は−ＣＮまたは−ＣＯＯＣＨ₃であり、ｐ、ｑ、ｓ、ｙ、ｔは１〜６の整数であり、ｚは１〜２０の整数である。］
【００５８】
また、一般式（５）で表される化合物として、具体的に下記式（６）で表される化合物がより好ましい。
【００５９】
【化２】

【００６０】
［式（６）中、ｙおよびｚは、一般式（５）おける内容と同様である。］
【００６１】
（５）フッ素含量
フッ素含有重合体中のフッ素含量は特に制限されるものではないが、例えば、３重量％以上の値、より好ましくは５〜６０重量％の範囲内の値とすることである。フッ素含有重合体中のフッ素含量が３重量％未満である場合には、反射防止効果が低下したり、幅広い範囲において屈折率の値を変化させることが困難となる場合があるためである。
なお、フッ素含有重合体中のフッ素含量は、アリザリンコンプレクソン法を用いて測定することができ、重合時におけるフッ素含有単量体の使用量（含有割合）や種類を調整することにより、容易に制御することができる。
【００６２】
（５）フッ素含有重合体の添加量
フッ素含有重合体の添加量は、特に制限されるものではないが、例えば、（Ａ）成分１００重量部に対して、０．５〜２５０重量部の範囲内の値とするのが好ましい。この理由は、フッ素含有重合体の添加量が０．５重量部未満となると、添加効果が発現しない場合があり、一方、２５０重量部を超えると保存安定性や塗装性が低下する場合があるためである。
したがって、確実に添加効果が得られ、またより保存安定性が優れている観点から、フッ素含有重合体の添加量を、（Ａ）成分１００重量部に対して、１〜２００重量部の範囲内の値とするのがより好ましく、３〜１５０重量部の範囲内の値とするのがさらに好ましい。
【００６３】
［第３の実施形態］
本発明の第３の実施形態は、加水分解性シラン化合物の加水分解物（Ａ成分）、光酸発生剤（Ｂ成分）、脱水剤（Ｃ成分）およびシリカ粒子（Ｅ成分）を含有する光硬化性組成物を基材上で光硬化してなる反射防止膜である。このようにシリカ粒子を添加（配合）することにより、得られる反射防止膜の硬化収縮を低減することができる。また、反射防止膜の機械的強度、例えば、ヤング率の値を高くして、耐擦傷性をより向上させることもできる。
以下、第３の実施形態に使用するシリカ粒子の詳細について説明するが、加水分解性シラン化合物の加水分解物（Ａ成分）、光酸発生剤（Ｂ成分）、脱水剤（Ｃ成分）等については、第１の実施形態と同様のものが使用できるため、ここでの説明は省略する。
【００６４】
（１）シリカ粒子の添加量
第３の実施形態に使用するシリカ粒子の添加量は、特に制限されるものではないが、例えば、（Ａ）成分１００重量部に対して、０．１〜１００重量部の範囲内の値とするのが好ましい。この理由は、シリカ粒子の添加量が０．１重量部未満となると、添加効果が発現しない場合があり、一方、１００重量部を超えると保存安定性や塗装性が低下する場合があるためである。
したがって、確実に添加効果が得られるとともに、保存安定性がより優れていることから、シリカ粒子の添加量を、（Ａ）成分１００重量部に対して、０．２〜８０重量部の範囲内の値とするのがより好ましく、０．５〜５０重量部の範囲内の値とするのがさらに好ましい。
【００６５】
（２）シリカ粒子の種類
第３の実施形態に使用するシリカ粒子は、シリカを主成分とする粒子であれば良く、シリカ以外の他の成分を含んでいても良い。そのようなシリカ以外の成分としてはアルカリ金属酸化物、アルカリ土類金属酸化物、及びＴｉ、Ｚｒ、Ａｌ、Ｂ、Ｓｎ、Ｐ等の酸化物を挙げることができる。
また、シリカ粒子の平均粒子径を、０.００１〜０．２μｍの範囲内の値とするのが好ましい。さらに、シリカ粒子を用いて透明な光硬化性組成物あるいは反射防止膜を形成することを目的とする場合には、より好ましくは０.００１〜０.０１μｍの範囲内の値とすることである。
【００６６】
また、使用するシリカ粒子の屈折率（温度２５℃、Ｎａ−Ｄ線、以下、同様）と、光硬化性組成物の屈折率との差を、０．０２（−）以下とするように、シリカ粒子を選択することが好ましい。屈折率差を、このような値とすることにより、反射防止膜の透明性をより高めることができる。
【００６７】
［第４の実施形態］
本発明の第４の実施形態は、加水分解性シラン化合物の加水分解物（Ａ成分）、光酸発生剤（Ｂ成分）、脱水剤（Ｃ成分）および反応性希釈剤（Ｆ成分）を含有する光硬化性組成物を基材上で光硬化してなる反射防止膜である。このように反応性希釈剤を添加（配合）することにより、基材に対する密着力を向上させたり、得られる反射防止膜の硬化収縮を低減したり、あるいは反射防止膜の機械的強度を制御することができる。さらに、ラジカル重合性の反応性希釈剤を用いた場合には、ラジカル発生剤を添加することにより、光硬化性組成物の光硬化性をよりきめ細かく調節することができる。また、カチオン重合性の反応性希釈剤を用いた場合には、光硬化性や機械的特性を調節することができる。
以下、第４の実施形態における反応性希釈剤（Ｆ成分）の詳細について説明するが、加水分解性シラン化合物の加水分解物（Ａ成分）、光酸発生剤（Ｂ成分）および脱水剤（Ｃ成分）等については、第１の実施形態と同様のものが使用できるため、ここでの説明は省略する。
【００６８】
▲１▼反応性希釈剤の配合量
第４の実施形態において、反応性希釈剤の配合量（添加量）は特に制限されるものではないが、例えば、（Ａ）成分１００重量部に対して、０．１〜８０重量部の範囲内の値とするのが好ましい。この理由は、反応性希釈剤の配合量が０．１重量部未満となると、添加効果が発現しない場合があり、一方、８０重量部を超えると、得られる反射防止膜の耐候性が低下する場合があるためである。したがって、反応性希釈剤の配合量を１〜５０重量部の範囲内の値とするのがより好ましく、２〜２０重量部の範囲内の値とするのがさらに好ましい。
【００６９】
▲２▼反応性希釈剤の種類
次に、第４の実施形態に使用する反応性希釈剤の種類について説明する。かかる反応性希釈剤としてカチオン重合性モノマーおよびエチレン性不飽和モノマーあるいはいずれか一方のモノマーを配合することが好ましい。
具体的に、カチオン重合性モノマーとしては、エポキシ化合物、オキセタン化合物、オキソラン化合物、環状アセタール化合物、環状ラクトン化合物、チイラン化合物、チエタン化合物、ビニルエーテル化合物、スピロオルソエステル化合物、環状エーテル化合物、環状チオエーテル化合物等を挙げることができる。
【００７０】
また、エチレン性不飽和モノマーはエチレン性不飽和結合（Ｃ＝Ｃ）を分子中に有する化合物であり、１分子中に１個のエチレン性不飽和結合を有する単官能モノマー、および１分子中に２個以上のエチレン性不飽和結合を有する多官能モノマーと定義することができる。
好ましいエチレン性不飽和モノマーとして、例えば、イソボルニル（メタ）アクリレート、ラウリル（メタ）アクリレート、ブトキシエチル（メタ）アクリレートポリエチレングリコールモノ（メタ）アクリレート、ボルニル（メタ）アクリレート、メチルトリエチレンジグリコール（メタ）アクリレートを挙げることができる。
【００７１】
［第５の実施形態］
本発明の第５の実施形態は、第１〜第４の実施形態で説明した反射防止膜を基材表面に有する積層体である。なお、積層体は少なくとも基材と、反射防止膜とを含んでいれば良く、種々の変形例が含まれる。以下、第５の実施形態の積層体を、図１〜図３を参照しつつ具体的に説明する。
図１は、基材上１２に直接形成された反射防止膜１０を含む積層体１４の断面図であり、図２は、基材１２と反射防止膜１０との間にハードコート層１６を介在させた積層体１８の断面図である。また、図３は、下側から、基材１２と、ハードコート層１６と、第１の高屈折率層２０と、第１の反射防止膜２２と、第２の高屈折率層２４と、第２の反射防止膜２６とを順次に形成して構成した多層構造の積層体２８の断面図である。
【００７２】
図１に示す積層体１４の場合、反射防止膜１０を直接基材１２上に形成することができるので、構成が単層とシンプルであり、しかも精度良く形成することができる。
また、図２に示す積層体１８のように、反射防止膜１０と基材１２との間に、ハードコート層１６を介在させると、反射防止膜１０の基材１２に対する密着力をより向上させることができ、また、ハードコート層１６の機械的特性に起因して積層体１８としての耐久性がより向上する。なお、ハードコート層１６は、例えば、ＳｉＯ₂、エポキシ系樹脂、アクリル系樹脂、メラミン系樹脂等の材料から構成するのが好ましく、さらには、その厚さを１〜５０μｍの範囲内の値とするのが好ましく、より好ましくは５〜１０μｍの範囲内の値とすることである。
【００７３】
また、図３に示す積層体２８のように、第１および第２の反射防止層２２、２６のほかに、比較的高い屈折率の値、例えば、１．５〜２．０（−）の範囲内の値を有する、厚さ５０〜２００ｎｍの第１および第２の高屈折率層２０、２４を、それぞれ第１および第２の反射防止層２２、２６と接して設けることも好ましい。このように本発明の反射防止層に接して高屈折率層２０、２４を設け、しかも複数層設けることにより、より優れた反射防止効果を得ることができる。
また、高屈折率層２０、２４を設ける場合、より優れた反射防止効果が得られることから、反射防止層２２、２６と、高屈折率層２０、２４との間の屈折率差を０．０５（−）以上の値とするのが好ましく、０．１〜０．５（−）の範囲内の値とするのがより好ましく、０．１５〜０．５（−）の範囲内の値とするのがさらに好ましい。
【００７４】
また、図２〜図３の積層体１８、２８に示すようにハードコート層１６や高屈折率層２０、２４、あるいはプライマー層（図示しない。）を設ける場合にも、その上に本発明の光硬化性組成物をコーティングした後に紫外線等を照射することにより、反射防止膜１０、２２、２６を容易に形成することができる。その場合、反射防止効果の一端を担う高屈折率層２０、２４を含めて本発明の反射防止膜（反射防止層）と称する場合がある。
【００７５】
また、図１〜図３に示す積層体１４、１８、２８における基材１２の種類は、光が透過する際に反射防止効果が所望されるものであれば特に制限されるものではないが、例えば、ガラス、ポリカーボネート系樹脂、ポリエステル系樹脂またはアクリル系樹脂等を挙げることができる。基材１２がガラスの場合には、具体的な積層体として、カメラのレンズ部やテレビ（ＣＲＴ、ＬＣＤ）の画面表示部あるいは窓ガラス等が挙げられる。また、ポリカーボネート系樹脂、ポリエステル系樹脂またはアクリル系樹脂からなる基材１２の場合には、液晶表示装置におけるカラーフィルター等が挙げられる。
【００７６】
［第６の実施形態］
本発明の第６の実施形態は、以下に示す第１の工程および第２の工程を含む反射防止膜（反射防止膜を基材表面に有する積層体）の製造方法に関する実施形態である。なお、第１の工程は、上述した第１〜５の実施形態のいずれか一つの光硬化性組成物を基材上で成形する工程（成形工程と称する場合がある。）であり、第２の工程は、露光機を用いて露光することにより、光硬化性組成物を光硬化させる工程（露光工程と称する場合がある。）である。
【００７７】
（１）第１の工程
光硬化性組成物の成形方法は特に制限されるものではないが、例えば、ディップコータやスピンコータ、あるいはバーコータを用いて、光硬化性組成物を塗布、形成することが好ましい。具体的に、スピンコータを用いた場合、スピンコータ内に、基材を固定した後、一例として、回転数１０００ｒｐｍの条件で、予め粘度調整した光硬化性組成物を回転塗布することが好ましい。
また、光硬化性組成物の成形後（光硬化前）の厚さは特に制限されるものではないが、例えば、５０〜１０００ｎｍの範囲内の値であることが好ましい。この理由は、成形後の厚さが５０ｎｍ未満では、光硬化性組成物を所定形状に保持することが困難となる場合があり、一方、１０００ｎｍを超えると、光干渉等が生じて、反射防止膜としたときに、反射防止効果が乏しくなる場合があるためである。
【００７８】
また、第１の工程において、光硬化性組成物の成形後に、１００〜１５０℃の温度で予備加熱（プリベイク）することが好ましい。このような条件で光硬化性組成物を予備加熱することにより、光硬化性組成物における揮発部分を有効に除去することができ、光硬化性組成物の成形品が型崩れすることがなくなる。また、加水分解性シラン化合物（Ａ成分）のシラノールの一部を反応させることができ、基材に対する密着力や現像時における耐薬品（現像剤）性を向上させることもできる。
ただし、過度に加熱して、現像特性が逆に低下しないように、１１０〜１４０℃の温度で加熱することがより好ましく、１１５〜１３０℃の温度で加熱することがより好ましい。
【００７９】
さらに、加熱時間については、加熱温度を考慮して定めるのが好ましいが、１００〜１５０℃の温度で予備加熱する場合、１〜２０分の加熱時間とするのが好ましい。この理由は、加熱時間が１分未満となると、シラノールの反応が不均一となる場合があり、一方、加熱時間が１０分を超えると、シラノールが過度に反応して、現像液を用いて精度良く現像することが困難となる場合があるためである。したがって、加熱時間を２〜１５分の範囲内の値とするのが好ましく、３〜１０分の範囲内の値とするのがさらに好ましい。
なお、加熱手段については特に制限されるものではなく、例えば、オーブンや赤外線ランプを用いることができる。
【００８０】
（２）第２の工程
また、第２の工程における光硬化方法は第１の実施形態で一部説明したとおりであるが、全面露光して光硬化させることはもちろんのこと、所定パターンを有するフォトマスク介して非収束光を光硬化性組成物にパターン露光したり、あるいは、多数の光ファイバーを束ねた導光部材を用い、フォトマスクのパターンに対応する光ファイバーからのみ光照射して、パターン露光することも好ましい。このようにパターン露光することにより、露光して硬化させた光硬化物部分と、露光せず未硬化の光硬化性組成物部分とを精度良く形成することができる。具体的に、マスクパターンのライン／スペース（比率５０／５０）が１０μｍ以上の範囲、より好ましくは３０μｍ以上の範囲、さらに好ましくは、５０μｍ以上の範囲において、光硬化させた後、現像により基材の露出部を再現性良く形成できることが確認されている。
したがって、未硬化の光硬化性組成物部分のみを、現像液を用いて容易にウエット現像（除去）することができ、基材の露出部、すなわち反射防止膜が設けられていない部分を短時間かつ容易に形成することができる。よって、このような基材の露出部を利用して、所望の部材を強固に接着固定等することができる。
【００８１】
さらに、第２の工程において、光硬化物である反射防止膜をさらに加熱することも好ましい。その場合、基材もしくは塗膜の分解開始温度以下である温度２５〜２００℃、５分〜７２時間の条件で加熱するのが好ましい。このように反射防止膜を加熱することにより、より耐熱性や耐候性に優れた反射防止膜（積層体）を得ることができる。
【００８２】
【実施例】
以下、本発明の実施例を説明するが、本発明の範囲はこれら実施例の記載に限定されるものではない。また、実施例中、各成分の配合量は特に記載のない限り重量部を意味している。
【００８３】
［実施例１］
（光硬化性組成物の調製）
撹拌機および蒸留装置を備えた容器内に、メチルトリメトキシシラン（ＭＴＭＳ、８０．０ｇ、０．５５８モル）と、電気伝導率が８×１０^-5Ｓ・ｃｍ^-1のイオン交換水（１６．０ｇ、０．８８９モル）とを収容した後、温度６０℃、６時間の条件で加熱撹拌することにより、メチルトリメトキシシランの加水分解を行った。次いで、容器内の温度を８０℃に昇温させた後、メチルイソブチルケトン（以下、ＭＩＢＫと略記）を滴下しながら、加水分解により副生したメタノールを蒸留除去した。そして、最終的に固形分を２２重量％に調整し、（Ａ）成分であるポリシロキサンを含有する溶液（以下、ポリシロキサン溶液１と称する。）を得た。得られたポリシロキサン溶液１について、ＧＰＣを用いてポリスチレン換算の重量平均分子量を測定したところ、１５００という値が得られた。
次いで、得られたポリシロキサン溶液１（固形分および溶剤の合計）１００重量部あたり、（Ｂ）成分の光酸発生剤として、ＳＩ−１００Ｌ（三新化学（株）製）を３重量部、（Ｃ）成分の脱水剤として、オルト蟻酸メチル（和光純薬工業（株）製）５重量部をそれぞれ添加して、光硬化性組成物Ａを得た。
【００８４】
（反射防止膜の形成および評価）
（１）光硬化性１
得られた光硬化性組成物Ａ（溶液）に、ＭＩＢＫとｎ−ブタノールとの等量混合溶媒を添加して、固形分濃度を３重量％に調整した。次いで、大気条件下に、ポリカーボネート板（厚さ１ｍｍ、帝人化成（株）製）上に、ディップコータを用いて塗膜を形成した。
次いで、室温（２５℃）、２分の条件で乾燥して、厚さ０．１μｍの塗膜を得た後、大気下、温度２５℃、露光量が１００ｍＪ／ｃｍ²（照射時間１秒）、２００ｍＪ／ｃｍ²（照射時間２秒）および３００ｍＪ／ｃｍ²（照射時間３秒）となるように、オーク製作所（株）製のコンベア式高圧水銀ランプ（２ｋＷ）を用いて紫外線を照射し、反射防止膜を形成した。また、窒素中、温度２５℃の条件で、同様に紫外線を照射して、反射防止膜を形成した。得られた反射防止膜につき、指触で表面タックを測定し、以下の基準で光硬化性を評価した。結果を表１に示す。さらに、
◎：１００ｍＪ／ｃｍ²露光後、反射防止膜の表面タックがない。
○：２００ｍＪ／ｃｍ²露光後、反射防止膜の表面タックがない。
△：３００ｍＪ／ｃｍ²露光後、反射防止膜の表面タックがない。
×：３００ｍＪ／ｃｍ²露光後、反射防止膜の表面タックがある。
【００８５】
（２）光硬化性２
得られた光硬化性組成物（溶液）を温度４０℃で１ヶ月間および３ヶ月間保管した後、目視で外観変化（粘度増加）を測定し、さらに上記（１）の光硬化性を測定して、以下の基準で長期保存後の光硬化性を評価した。得られた結果を表１に、保存安定性として示す。
◎：３ヶ月経過後も、外観変化や光硬化性の変化は観察されない。
○：１ヶ月経過後も、外観変化や光硬化性の変化は観察されない。
×：１ヶ月経過後に、外観変化あるいは光硬化性の低下が観察される。
【００８６】
（３）反射防止性
光硬化性組成物をポリカーボネート板上にディップコートした後、前記コンベア式高圧水銀ランプを用いて、大気中で露光量が２００ｍＪ／ｃｍ²となるように紫外線を照射して、厚さ０．１μｍの反射防止膜を含む積層体を形成した。得られた積層体（反射防止膜）の反射防止効果を分光反射率測定装置（大型試料室積分球付属装置１５０−０９０９０を組み込んだ自記分光光度計Ｕ−３４１０、日立製作所（株）製）により図４に示すように波長４００〜８００ｎｍの範囲で反射率を測定して評価した。すなわち、アルミの蒸着膜における反射率を基準（１００％）として、各波長における積層体（反射防止膜）の反射率を測定し、そのうち波長５５０ｎｍにおける光の反射率から以下の基準で反射防止効果を評価した。結果を表１に示す。
◎：反射率が１％以下の値である。
○：反射率が２％以下の値である。
△：反射率が３％以下の値である。
×：反射率が３％を超える値である。
【００８７】
（４）透明性
光硬化性組成物を石英板上にスピンコートした後、前記コンベア式高圧水銀ランプを用いて、大気中で露光量が２００ｍＪ／ｃｍ²となるように紫外線を照射し、厚さ１０μｍの透明性測定用の光硬化物（反射防止膜）を形成した。次いで、分光光度計を用いて、得られた光硬化物における波長５５０ｎｍの光透過率（Ｔ／％）を測定し、得られた光透過率から以下の基準で透明性を評価した。結果を表１に示す。
○：光透過率が９５％以上の値である。
△：光透過率が８０〜９５％未満の値である。
×：光透過率が８０％未満の値である。
【００８８】
（５）屈折率
光硬化性組成物をポリテトラフルオロエチレン製フィルム上にバーコータを用いて塗布した後、前記コンベア式高圧水銀ランプを用いて、大気中で露光量が２００ｍＪ／ｃｍ²となるように紫外線を照射し、厚さ２０μｍの屈折率測定用の光硬化物（反射防止膜）を形成した。得られた光硬化物におけるＮａ−Ｄ線の屈折率を、測定温度２５℃の条件で、アッベ屈折率計を用いて測定した。結果を表１に示す。
【００８９】
（６）耐候性
光硬化性組成物を石英板上にスピンコートした後、前記コンベア式高圧水銀ランプを用いて、大気中で露光量が２００ｍＪ／ｃｍ²となるように紫外線を照射し、厚さ２μｍの耐候性測定用の光硬化物（反射防止膜）を形成した。得られた光硬化物についてＪＩＳ Ｄ０２０５に準拠して（湿度５０％、温度６３℃、降雨１８分／１２０分照射の条件）、サンシャインカーボンアーク灯式耐光性試験機を用い、促進耐候試験を実施した。そして、促進耐候試験１０００時間後および２０００時間後における光硬化物の外観を目視で観察し、以下の基準で以て耐候性を評価した。また、同時に、ＪＩＳ Ｋ７１０３に準拠した黄変度を△ＹＩ値で以て測定し、同様に光硬化物の耐候性を評価した。結果を表１に示す。
○：外観変化（クラック等）が無く、また△ＹＩ値が０．１以下である。
△：外観変化（クラック等）がほとんど無く、また△ＹＩ値が２以下である。
×：外観変化（クラック等）が認められるか、△ＹＩ値が２を超えている。
【００９０】
（７）耐擦傷性
光硬化性組成物をポリカーボネート板上にディップコートした後、前記コンベア式高圧水銀ランプを用いて、大気中で露光量が２００ｍＪ／ｃｍ²となるように紫外線を照射し、厚さ０．１μｍの反射防止膜を含む積層体を形成した。得られた積層体における反射防止膜の表面を、ペーパー（キムワイプ、十条キンバリー（株）製）により、荷重１ｋｇ／ｃｍ²の条件で２５回こすり、傷の発生具合や剥離具合および鉛筆硬度試験から、以下の基準に照らして反射防止膜の耐擦傷性を評価した。結果を表１に示す。
◎：反射防止膜に傷の発生や剥離は観察されず、鉛筆硬度が２Ｈ以上である。
〇：反射防止膜に傷の発生や剥離は観察されず、鉛筆硬度が２Ｈ未満である。
△：反射防止膜の剥離は観察されないが、微細な傷の発生が観察される。
×：反射防止膜の一部が剥離したり、筋状の傷の発生が多数観察される。
【００９１】
（８）耐汚染性
光硬化性組成物をポリカーボネート板上にディップコートした後、前記コンベア式高圧水銀ランプを用いて、大気中で、露光量が２００ｍＪ／ｃｍ²となるように紫外線を照射し、厚さ０．１μｍの反射防止膜を含む積層体を形成した。得られた積層体における反射防止膜の耐汚染性を、汚染物質（指紋および黒マジック）を用いてスポット試験を行い、以下の基準で判断した。結果を表１に示す。◎：指紋および黒マジックについて、それぞれ乾布を用いて１回で拭き取ることができる。
○：指紋については乾布を用いて１０回未満で拭き取ることができ、黒マジックについては、エチルアルコールを用いて１０回未満で拭き取ることができる。
△：指紋については乾布を用いて１０回以上で拭き取ることができ、黒マジックについては、エチルアルコールを用いて１０回以上で拭き取ることができる。
×：指紋については乾布を用いて拭き取ることができず、黒マジックについては、エチルアルコールを用いて拭き取ることができない。
【００９２】
［実施例２］
実施例１におけるポリカーボネート板の替わりに、ポリエチレンテレフタレートフィルム（厚さ１８８μｍ、東洋紡（株）製）を基材として用いたほかは、実施例１と同様に光硬化性組成物Ａから反射防止膜を形成して、図５に示すように反射率等を測定し、評価した。得られた結果を表１に示す。ただし、透明性、屈折率および耐候性については、実施例１の繰り返し試験となるため、実施例２ではこれらの評価試験を省略し、表１には実施例１で得られた結果を示してある。
【００９３】
［実施例３］
（光硬化性樹脂組成物の調製）
（１）フッ素含有重合体の重合
内容積１．０リットルの電磁撹拌機を備えたステンレス製のオートクレーブを窒素ガスを用いて十分に置換した。次いで、このオートクレーブ内に、酢酸エチル（重合溶剤）３００ｇと、エチルビニルエーテル２４．０ｇと、ヒドロキシブチルビニルエーテル２５．８ｇと、ノニオン性反応性乳化剤ＮＥ−３０（旭電化工業（株）製）１０．０ｇと、ラジカル発生剤としてアゾ基含有ポリジメチルシロキサンＶＰＳ−１００１（和光純薬工業（株）製）１．０ｇと、過酸化ラウロイル０．５ｇとを収容した。そして、共重合成分等を十分に撹拌した後、ドライアイスおよびメタノールを用いて−５０℃まで冷却し、再度窒素ガスを用いて系内の酸素を除去した。
次いで、ヘキサフルオロプロピレン（ガス）９９．９ｇをオートクレーブ内に導入した後、オートクレーブ内の温度を７０℃に昇温した。なお、７０℃に達した時点での、オートクレーブ内の圧力は５．９ｋｇｆ／ｃｍ2であった。
【００９４】
次いで、オートクレーブ内の共重合成分等を撹拌しながら、温度を７０℃に保持したまま２０時間かけてラジカル重合反応を行った。そして、オートクレーブ内の圧力が２．５ｋｇｆ／ｃｍ²まで低下した時点で、オートクレーブを水冷して反応を停止させた。オートクレーブ内の温度が室温まで降下したのを確認した後、オートクレーブを開放し、未反応モノマーを系外に放出させるとともに、フッ素含有共重合体溶液（ポリマー溶液）を取り出した。
得られたフッ素含有共重合体溶液を、多量のメタノールに投入し、フッ素含有共重合体を析出させた。その後、多量のメタノールを用いてフッ素含有共重合体を洗浄し、さらに温度５０℃の真空乾燥を行い、水酸基を有するフッ素含有重合体の精製物を得た。得られた共重合体１について、以下のような評価項目をそれぞれ５回測定し平均した。
【００９５】
▲１▼重量平均分子量の測定
得られたフッ素含有共重合体の精製物を、濃度０．５重量％となるようにＴＨＦ（テトラヒドロフラン）に溶解させた。次いで、ＧＰＣ装置ＨＬＣ−８０２０（東ソー（株）製）を用いて、フッ素含有共重合体のＧＰＣカラムからの溶出時間を屈折率計（ＲＩ）で検出し、得られた溶出時間から、ポリスチレン換算分子量として、フッ素含有共重合体の重量平均分子量を算出した。その結果、得られたフッ素含有共重合体の重量平均分子量は、４２，０００であった。
【００９６】
▲２▼フッ素含量の測定
得られたフッ素含有共重合体のフッ素含量を、アリザリンコンプレクソン法に準拠して測定した。その結果、得られたフッ素含有共重合体のフッ素含量は、４６．１重量％であった。
【００９７】
（２）フッ素含有共重合体の変性
得られた水酸基を有するフッ素含有共重合体１００ｇと、γ−イソシアネートプロピルトリエトキシシラン２０ｇと、メチルイソブチルケトン５００ｇと、ジブチルスズジラウレート０．０１ｇとを撹拌機付きの反応容器内に収容した。次いで、撹拌しながら、窒素ガス雰囲気下、温度２０℃、１２時間の条件で、水酸基を有するフッ素含有共重合体とγ−イソシアネートプロピルトリエトキシシランとを反応させた。
【００９８】
次いで、得られた反応液の一部を取り出し、これに所定量のジブチルアミンを添加して、反応液中の未反応のγ−イソシアネートプロピルトリエトキシシランと反応させた。なお、反応しなかったジブチルアミン量を、０．１Ｎの塩酸を用いて滴定し、未反応のγ−イソシアネートプロピルトリエトキシシラン量を求めた。その結果、反応液中において、γ−イソシアネートプロピルトリエトキシシランは完全に消費されており、γ−イソシアネートプロピルトリエトキシシランと水酸基を有するフッ素含有共重合体とが十分に反応していることが確認された。また、反応溶液の一部をＮａＣｌ板上に塗布し、窒素雰囲気下で乾燥することにより塗膜を形成した。この塗膜について赤外線スペクトルを測定したところ、イソシアネート基に由来したピークは観察されず、一方で、イソシアネート基が反応した生成したウレタン基に由来する新たなピークが観察された。
したがって、以上の滴定および赤外線スペクトルの結果から、γ−イソシアネートプロピルトリエトキシシランとフッ素含有共重合体との反応は完結し、シラン変性されたフッ素含有共重合体が得られたことが確認された。
【００９９】
さらに、シラン変性されたフッ素含有共重合体を含むことが確認された反応液の一部を取り出し、これを多量のメタノール中に投入し、シラン変性されたフッ素含有共重合体を析出させた。その後、多量のメタノールを用いて、シラン変性されたフッ素含有共重合体を洗浄し、さらに温度５０℃の真空乾燥を行い、シラン変性されたフッ素含有重合体の精製物を得た。
【０１００】
（３）シラン化合物の縮合
実施例１と同様に、ＭＴＭＳ縮合物溶液である、固形分濃度が２２重量％のポリシロキサン溶液１を得た。
【０１０１】
（４）光硬化性樹脂組成物の調製
シラン変性されたフッ素含有重合体の精製物を、ＭＩＢＫに溶解させて、固形分濃度が２２重量％の共重合体溶液とした。この共重合体溶液３０ｇと、ポリシロキサン溶液１ ７０ｇと、光酸発生剤としてのＳＩ−１００Ｌ ０．６６ｇとを撹拌機付きの容器内に収容後、均一に混合撹拌して光硬化性樹脂組成物Ｂを得た。
【０１０２】
（反射防止膜の形成および評価）
得られた光硬化性樹脂組成物Ｂを用い、実施例１と同様に反射防止膜（評価用の光硬化物を含む。）を形成して評価した。結果を表１に示す。
【０１０３】
［実施例４］
（光硬化性組成物の調製）
撹拌機付の容器内に、メチルトリメトキシシラン（５３．２８ｇ、０．３９１８モル）と、メタノール分散コロイド状シリカ（１３３．２ｇ、シリカ含量３０重量％、日産化学（株）製メタノールシリカゾル）と電気伝導率が８×１０^-5Ｓ・ｃｍ^-1のイオン交換水（１１．２８ｇ、０．６２８モル）とを収容した後、温度６０℃、６時間の条件で加熱撹拌することにより加水分解を行った。次いで、ＭＩＢＫを滴下しながら、加水分解により副生したメタノールを蒸留除去した。そして、最終的に固形分を２２重量％に調整し、本発明の（Ａ）成分であるポリシロキサンおよび（Ｅ）成分であるシリカ粒子を含有するポリシロキサン溶液（以下、ポリシロキサン溶液２と称する。）を得た。得られたポリシロキサン溶液２について、ＧＰＣを用いてポリスチレン換算の重量平均分子量を測定したところ、１８００という値が得られた。
次いで、得られたポリシロキサン溶液２（固形分および溶剤）１００重量部あたり、（Ｂ）成分として、光酸発生剤ＳＩ−１００Ｌ（三新化学（株）製）を３重量部、（Ｃ）成分として、脱水剤であるオルト蟻酸メチル５重量部をそれぞれ添加して、光硬化性組成物Ｃを得た。
【０１０４】
（反射防止膜の形成および評価）
得られた光硬化性樹脂組成物Ｃを用い、実施例１と同様に反射防止膜（評価用の光硬化物を含む。）を形成して評価した。結果を表１に示す。
【０１０５】
［実施例５］
実施例１で調製した光硬化性組成物Ａに、反応性希釈剤ＫＲＭ−２１１０（旭電化（株）製）を５重量部添加して、光硬化性組成物Ｄとしたほかは、実施例１と同様に反射防止膜（評価用の光硬化物を含む。）を形成して評価した。結果を表１に示す。
【０１０６】
［実施例６］
（高屈折率膜の形成）
金属酸化物微粒子含有コート剤Ｎｏ．１３５２（住友大阪セメント（株）製）１００重量部と、シランカップリング剤ＴＥＳＯＸ（東亜合成（株）製）５重量部と、光ラジカル発生剤イルガキュア１８４（チバスペシャリティケミカルズ（株）製）３重量部とを混合後、さらにＭＩＢＫとｔ−ブチルアルコールとの等量混合溶液を添加して、固形分３重量％の高屈折率膜溶液を光硬化性組成物Ｅとして調製した。
得られた光硬化性組成物Ｅを、ディップコータを用いてポリカーボネート板に塗布した後、高圧水銀ランプを用いて、窒素中で、露光量が２００ｍＪ／ｃｍ²となるように紫外線を照射し、厚さが０．１μｍであり、屈折率の値が１．７（−）である高屈折率膜を形成した。
【０１０７】
（反射防止膜の形成および評価）
得られた高屈折率膜上に、実施例１で調製した光硬化性組成物Ａと同様の光硬化性組成物から反射防止膜（評価用の光硬化物を含む。）を形成して評価した。なお、透明性、屈折率および耐候性については、実施例１の繰り返し試験となるため、実施例６ではこれらの評価試験を省略し、表１には実施例１で得られた結果を示してある。
【０１０８】
［実施例７］
実施例６において、実施例１で調製した光硬化性組成物Ａを使用する代わりに、実施例３で調製した光硬化性組成物Ｂを用いたほかは、実施例６と同様に、高屈折率膜および反射防止膜を形成して評価した。結果を表１に示す。なお、透明性、屈折率および耐候性については、実施例３の繰り返し試験となるため、実施例６ではこれらの評価試験を省略し、表１には実施例３で得られた結果を示してある。
【０１０９】
［実施例８］
（ハードコート層の形成）
アクリルモノマーであるＤＰＨＡ４０重量部と、アロニックスＴＯ−７５６（東亜合成（株）製）６０重量部と、前述したイルガキュア１８４ ３重量部とを混合してハードコート層用の光硬化性組成物Ｆを調製した。得られた光硬化性組成物Ｆを、バーコータを用いてポリカーボネート板に塗布した後、高圧水銀ランプを用いて、窒素中で、露光量が５００ｍＪ／ｃｍ²となるように紫外線を照射し、厚さが５．０μｍであるハードコート層を形成した。
【０１１０】
（反射防止膜の形成および評価）
得られたハードコート層上に、実施例７と同様に、高屈折率膜および反射防止膜を形成して評価した。結果を表１に示す。
【０１１１】
［比較例３］
（光硬化性組成物の作製）
実施例１と同様にして、ポリシロキサン溶液１を作製した。次いで、得られたポリシロキサン溶液１ １００重量部あたり、光酸発生剤ＳＩ−１００Ｌ（三新化学（株）製）を３．０重量部添加して、光硬化性組成物Ｇを得た。すなわち、比較例３においては、実施例１と異なり脱水剤を添加せず、光硬化性組成物Ｇを調製した。
【０１１２】
（反射防止膜の形成および評価）
実施例１と同様に、光硬化性組成物Ｇから反射防止膜（評価用の光硬化物を含む。）を形成して評価した。それぞれの結果を表１に示す。実施例１における結果との比較から、比較例３においては脱水剤を添加していないため、光硬化性組成物Ｇにおける光硬化性や保存安定性が相対的に低下しているものの、その他の特性は同等であることが確認された。
【０１１３】
［比較例１および２］
（光硬化性組成物の調製）
フッ素系ポリマーＫＹＮＥＲ ＡＤＳ（エルフーアトム社製）８０重量部に対して、アクリルモノマーであるＤＰＨＡ（日本化薬（株）製）２０重量部と、光ラジカル発生剤イルガキュア１８４（チバスペシャリティケミカルズ（株）製）３重量部を添加し、さらに固形分濃度３重量％となるようにＭＩＢＫに溶解させて、光硬化性組成物Ｈを得た。
【０１１４】
（光硬化性組成物の評価）
実施例１（基材：ポリカ−ボネート板）および実施例２（基材：ＰＥＴフィルム）と同様に、得られた光硬化性組成物Ｈから基板の種類を変えて反射防止膜（評価用の光硬化物を含む。）を形成して評価した。それぞれの結果を表１に示す。なお、透明性、屈折率および耐候性については、比較例１と比較例２において繰り返し試験となるため、比較例２ではこれらの評価試験を省略し、表１には比較例１で得られた結果を示してある。
【０１１５】
【表１】

【０１１６】
【発明の効果】
本発明の反射防止膜あるいはその反射防止膜を含む積層体によれば、反射防止膜の形成材料として特定の加水分解性シラン化合物と、光酸発生剤とからなる光硬化性組成物を使用することから、酸素存在下においても光硬化反応により反射防止膜が形成可能であり、しかも得られた反射防止膜あるいは当該反射防止膜を含む積層体において、優れた反射防止効果や耐汚染性を得ることが可能となった。
【０１１７】
また、反射防止膜の形成材料として、特定の加水分解性シラン化合物と、光酸発生剤と、脱水剤とを組み合わせることにより保存安定性や光硬化性に優れた光硬化性組成物を得ることができ、したがって、酸素存在下においてもより速い光硬化反応により反射防止膜が形成可能であり、しかも得られた反射防止膜あるいは当該反射防止膜を含む積層体において、優れた反射防止効果や耐汚染性を得ることが可能となった。
【０１１８】
さらに、本発明の反射防止膜の製造方法によれば、反射防止膜の形成材料として特定の加水分解性シラン化合物と、光酸発生剤とからなる光硬化性組成物を使用して、基材上に反射防止膜を形成することから、優れた反射防止効果や耐汚染性を有する反射防止膜を、酸素存在下においても光硬化反応を利用として形成することが可能となった。その他、本発明の反射防止膜の製造方法によれば、パターン露光することにより、任意の箇所に反射防止膜を形成することが可能となった。
【図面の簡単な説明】
【図１】本発明の積層体の断面を示す図である（その１）。
【図２】本発明の積層体の断面を示す図である（その２）。
【図３】本発明の積層体の断面を示す図である（その３）。
【図４】実施例１の反射防止膜（大気中硬化）および使用した基板（ポリカーボネート板）における反射率測定チャートである。
【図５】実施例２の反射防止膜（大気中硬化）および使用した基板（ＰＥＴフィルム）における反射率測定チャートである。
【符号の説明】
１０、２２、２６ 反射防止膜
１２ 基材
１４、１８、２８ 積層体
１６ ハードコート層
２０、２２ 高屈折率層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an antireflection film obtained from a photocurable composition, a laminate including the antireflection film, and a method for producing the antireflection film. More specifically, an antireflection film that has an excellent antireflection effect, stain resistance, and the like and can be formed by a photocuring reaction even in the presence of oxygen, a laminate including the antireflection film, and the antireflection film It relates to a manufacturing method.
[0002]
[Prior art]
As a material for forming the antireflection film, for example, thermosetting polysiloxane compositions are known. JP-A-61-2477453, JP-A-6-25599, JP-A-7-331115, and JP-A-5-331115. 10-232301 and the like.
However, the antireflection film obtained from such a thermosetting polysiloxane composition needs to be heat-treated at a high temperature for a long time, resulting in a problem that productivity is low or the type of substrate to be applied is limited. It was observed. Moreover, since this thermosetting polysiloxane composition has poor storage stability, it is generally a two-component type in which the main agent and the curing agent are separated, and there is a problem that handling is complicated.
[0003]
Further, as a material for forming an antireflection film, a photocurable resin composition that is cured using light such as ultraviolet rays is also known, such as JP-A-1-197570, JP-A-6-136062, and JP-A-6-138620. No. 9-203861 and Japanese Patent Application Laid-Open No. 10-239502.
However, the main component in the photocurable resin composition is a fluorine-containing vinyl-based resin, and since radical polymerization is used for photocuring, active radicals are easily deactivated by oxygen in the atmosphere, often resulting in poor curing. Some cases have been seen. In particular, in a thin film application such as an antireflection film targeted by the present invention, there is a problem in that it is easily affected by oxygen in the atmosphere and the photocurable resin composition cannot be substantially photocured. In addition, the antireflection film made of a fluorine-containing vinyl resin has a problem of low hardness and poor scratch resistance, or poor weather resistance and stain resistance.
[0004]
[Problems to be solved by the invention]
As described above, as a conventional material for forming an antireflection film, a thermosetting polysiloxane composition has a long curing time and requires high-temperature heat treatment, so that applicable substrates are limited and further preserved. It had the problem of poor stability. On the other hand, the conventional photocurable composition comprising a fluorine-containing vinyl resin is susceptible to oxygen, and has a problem that it is inferior in scratch resistance, weather resistance or contamination resistance in the obtained antireflection film. Had.
[0005]
Therefore, the inventors of the present invention diligently studied, and as a material for forming the antireflection film, by using a photocurable composition that combines a specific hydrolyzable silane compound and a photoacid generator, It has been found that the above problems can be solved. That is, the present invention has an antireflection film having excellent antireflection effect and stain resistance, and can be formed by a photocuring reaction even in the presence of oxygen, a laminate including the antireflection film, and the antireflection film It aims at providing the manufacturing method of.
[0006]
[Means for Solving the Problems]
  The present invention provides a photocurable composition containing the following components (A) to (C):A method for producing an antireflection film, comprising a molding step and a step of photocuring the molded photocurable composition to form an antireflection filmAbout.
(A) At least one compound selected from the group consisting of a hydrolyzable silane compound represented by the general formula (1), a hydrolyzate thereof, and a condensate thereof
(R¹)_PSi (X)_4-P      (1)
[In general formula (1), R¹Is a non-hydrolyzable organic group having 1 to 12 carbon atoms, X is a hydrolyzable group, and p is an integer of 0 to 3. ]
(B) Photoacid generator
(C) Dehydrating agent
  With such an antireflection film, it can be formed without being affected by oxygen even in the atmosphere, and in the obtained antireflection film, an excellent antireflection effect and stain resistance, Excellent photocurability can be obtained.
[0007]
Moreover, when comprising the anti-reflective film of this invention, it is preferable to contain a fluorine-containing polymer as (D) component in the photocurable composition to be used.
By containing the fluorine-containing polymer in this way, the value of the refractive index of the obtained antireflection film can be lowered to increase the antireflection effect or to further improve the stain resistance.
[0008]
Moreover, when comprising the anti-reflective film of this invention, it is preferable to contain a silica particle as (E) component in the photocurable composition to be used.
By containing silica particles in this way, curing shrinkage of the obtained antireflection film can be reduced, or the mechanical strength of the antireflection film can be improved.
[0009]
Moreover, when comprising the anti-reflective film of this invention, it is preferable to contain a reactive diluent as (F) component in the photocurable composition to be used.
By including a reactive diluent in this way, the adhesion of the resulting antireflection film to the substrate can be improved, curing shrinkage can be reduced, or the mechanical strength of the antireflection film can be adjusted. .
[0010]
Another aspect of the present invention relates to a laminate including an antireflection film, which includes the above-described antireflection film on a substrate. For example, a laminated body including a base material made of glass, polycarbonate resin, polyester resin, or acrylic resin can be used, such as a camera lens unit, a television (CRT) screen display unit, or a color filter in a liquid crystal display device. In the field of application of a wide range of antireflection films, excellent antireflection effects and durability can be obtained.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the antireflection film of the present invention (first to fourth embodiments), embodiments of a laminate including the antireflection film (fifth embodiment), and embodiments of the method of manufacturing an antireflection film (first embodiment) Embodiment 6) will be specifically described with reference to the drawings as appropriate.
[0013]
[First Embodiment]
In the first embodiment of the present invention, a photocurable composition containing a hydrolyzate (component A) of a hydrolyzable silane compound, a photoacid generator (component B), and a dehydrating agent (component C) is used as a light source. It is an antireflection film obtained by curing.
With such an antireflection film, it can be formed quickly using a photocuring reaction without being affected by oxygen even in the atmosphere (air), and also has an excellent antireflection effect and contamination resistance. In addition, excellent storage stability and higher hardness (for example, 2H or more in pencil hardness) can be obtained by the action of the dehydrating agent.
[0014]
(1) Hydrolyzate in hydrolyzable silane compound
(1) Structure
The hydrolyzate used in the first embodiment is a compound obtained by hydrolyzing the hydrolyzable silane compound represented by the general formula (1).
(R¹)_PSi (X)_4-P    (1)
[In general formula (1), R¹Is a non-hydrolyzable organic group having 1 to 12 carbon atoms, X is a hydrolyzable group, and p is an integer of 0 to 3. ]
[0015]
Here, the hydrolyzable group represented by X is usually hydrolyzed by heating within the temperature range of room temperature (25 ° C.) to 100 ° C. in the presence of non-catalyst and excess water, thereby producing a silanol group. Or a group capable of forming a siloxane condensate. The subscript p in the general formula (1) is an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 1.
However, in the hydrolyzate of the hydrolyzable silane compound represented by the general formula (1), a partially unhydrolyzed hydrolyzable group may remain. In that case, the hydrolyzable silane compound and the hydrolyzate And become a mixture.
[0016]
The hydrolyzate of a hydrolyzable silane compound means not only a compound in which an alkoxy group is changed to a silanol group by a hydrolysis reaction but also a partial condensate in which some silanol groups are condensed with each other. .
Furthermore, the hydrolyzable silane compound does not necessarily need to be hydrolyzed at the time of blending the photocurable composition, and at least a part of the hydrolyzable group is hydrolyzed at the stage of light irradiation. good. That is, in the photocurable composition used in the first embodiment, when the hydrolyzable silane compound is used without being hydrolyzed in advance, water is added in advance to hydrolyze the hydrolyzable group. By generating silanol groups, the photocurable composition can be photocured to form an antireflection film.
[0017]
(2) Specific examples of hydrolyzable silane compounds
Next, a specific example of the hydrolyzable silane compound represented by the formula (1) (sometimes simply referred to as a silane compound) will be described.
First, as a silane compound having a non-polymerizable organic group, tetrachlorosilane, tetraaminosilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, trimethoxysilane, Examples include silane compounds substituted with four hydrolyzable groups such as triethoxysilane.
[0018]
Similarly, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, pentafluorophenyltrimethoxy Examples include silane compounds substituted with three hydrolyzable groups such as silane, phenyltrimethoxysilane, d3-methyltrimethoxysilane, nonafluorobutylethyltrimethoxysilane, and trifluoromethyltrimethoxysilane.
[0019]
Similarly, silane compounds substituted with two hydrolyzable groups such as dimethyldichlorosilane, dimethyldiaminosilane, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, and dibutyldimethoxysilane, and trimethylchlorosilane, hexa Mention may be made of silane compounds substituted with one hydrolyzable group such as methyldisilazane, trimethylsilane, tributylsilane, trimethylmethoxysilane, tributylethoxysilane.
[0020]
Further, as the silane compound having a polymerizable organic group, the non-hydrolyzable organic group R in the general formula (1) is used.¹Any of a silane compound having a polymerizable organic group and a silane compound having a polymerizable organic group in the hydrolyzable group X in the general formula (1) can be used.
[0021]
Here, in any polymerizable organic group, the carbon number of the organic group is preferably a value in the range of 1 to 12. Specifically, the non-hydrolyzed organic group R in the general formula (1)¹Examples of silane compounds containing a polymerizable organic group include (meth) acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, glycidyloxytrimethoxysilane, and 3- (3-methyl-3-oxetanemethoxy) propyltrimethoxysilane. And oxacyclohexyltrimethoxysilane.
[0022]
Examples of the silane compound containing a polymerizable organic group in the hydrolyzable group X in the general formula (1) include tetra (meth) acryloxysilane, tetrakis [2- (meth) acryloxyethoxy] silane, tetra Glycidyloxysilane, tetrakis (2-vinyloxyethoxy) silane, tetrakis (2-vinyloxybutoxy) silane, tetrakis (3-methyl-3-oxetanemethoxy) silane, methyltri (meth) acryloxysilane, methyl [2- (Meth) acryloxyethoxy] silane, methyl-triglycidyloxysilane, methyltris (3-methyl-3-oxetanemethoxy) silane. These can be used alone or in combination of two or more.
[0023]
(3) Hydrolyzate of hydrolyzable silane compound
Next, the molecular weight of the hydrolyzate of the hydrolyzable silane compound will be described. Such molecular weight can be measured as a weight average molecular weight in terms of polystyrene using gel permeation chromatography (hereinafter abbreviated as GPC) using tetrahydrofuran as a mobile phase.
And it is preferable to make the weight average molecular weight of a hydrolyzate into the value within the range of 500-10000 normally. When the value of the weight average molecular weight in the hydrolyzate is less than 500, the film formability of the coating film may be lowered. On the other hand, when it exceeds 10,000, the photocurability may be lowered. Therefore, it is more preferable to set the weight average molecular weight in the hydrolyzate to a value within the range of 1000 to 5000.
[0024]
(2) Photoacid generator
(1) Definition
The photoacid generator (component B) added to the photocurable composition is an acidic activity capable of photocuring (crosslinking) the hydrolyzable silane compound as component (A) by irradiating energy rays such as light. Defined as a compound capable of releasing a substance.
In addition, examples of the light energy rays irradiated to decompose the photoacid generator and generate cations include visible light, ultraviolet rays, infrared rays, X rays, α rays, β rays, γ rays, and the like. . However, it is preferable to use ultraviolet rays from the viewpoint of having a constant energy level, a high curing speed, a relatively low irradiation device, and a small size.
[0025]
Moreover, when forming the laminated body of 1st Embodiment, it is also preferable to use together the radical generator mentioned later with a photo-acid generator with a photocurable composition. The radical which is a neutral active substance does not promote the condensation reaction of the silanol group, but when the radically polymerizable functional group is contained in the component (A), the polymerization of the functional group may be promoted. it can. Therefore, the photocurable composition can be cured more efficiently.
[0026]
(2) Types of photoacid generator
Next, the kind of photo-acid generator used for 1st Embodiment is demonstrated. Such photoacid generators include onium salts having a structure represented by the general formula (2) (first group of compounds) and sulfonic acid derivatives having a structure represented by the general formula (3) (second group of compounds). Compound).
[0027]
[R² _aR^Three _bR^Four _cR^Five _dW]^{+ m} [MZ_{m + n}]^-m    (2)
[In General Formula (2), the cation is an onium ion, W is S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, or —N≡N, and R², R^Three, R^FourAnd R^FiveAre the same or different organic groups, a, b, c and d are each an integer of 0 to 3, and (a + b + c + d) is equal to the valence of W. M is a halide complex [MX_{m + n}], For example, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, and Co. Z is, for example, a halogen atom or an aryl group such as F, Cl, Br, etc., m is the net charge of the halide complex ion, and n is the valence of M. ]
[0028]
Q_S-[S (= O)₂-R⁶]_t    (3)
[In the general formula (3), Q is a monovalent or divalent organic group, R6 is a monovalent organic group having 1 to 12 carbon atoms, the subscript s is 0 or 1, and the subscript t is 1 or 2. . ]
[0029]
First, an onium salt that is a compound of the first group is a compound that can release an acidic active substance by receiving light. Among such compounds of the first group, more effective onium salts are aromatic onium salts, particularly preferably diaryliodonium salts represented by the following general formula (4).
[R⁷-Ar¹-I⁺-Ar²-R⁸] [Y^-] (4)
[In the general formula (4), R⁷And R⁸Are each a monovalent organic group, which may be the same or different, and R⁷And R⁸At least one of them has an alkyl group having 4 or more carbon atoms, Ar¹And Ar²Are each an aromatic group, which may be the same or different, Y^-Is a monovalent anion and is a group 3 or 5 fluoride anion of the periodic table or ClO_Four ^-, CF_Three-SO_Three ^-An anion selected from ]
[0030]
Examples of the sulfonic acid derivative represented by the general formula (3) as the second group of compounds include disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imidosulfonates, benzoin. Examples include sulfonates, sulfonates of 1-oxy-2-hydroxy-3-propyl alcohol, pyrogallol trisulfonates, and benzyl sulfonates.
Of the sulfonic acid derivatives represented by the general formula (3), imide sulfonates are more preferable, and among imide sulfonates, a trifluoromethyl sulfonate derivative is more preferable.
[0031]
(3) Amount of photoacid generator added
Next, the addition amount (content ratio) of the photo-acid generator used for a photocurable composition is demonstrated. The amount of the photoacid generator to be added is not particularly limited, but it is preferably a value within the range of 0.1 to 15 parts by weight with respect to 100 parts by weight of component (A). If the addition amount of the photoacid generator is less than 0.1 parts by weight, the photocurability may be lowered and a sufficient curing rate may not be obtained. On the other hand, if the addition amount of the photoacid generator exceeds 15 parts by weight, the weather resistance and heat resistance of the resulting cured product may be lowered.
Therefore, from the viewpoint of better balance between photocurability and the weather resistance of the resulting cured product, the addition amount of the photoacid generator is in the range of 1 to 10 parts by weight with respect to 100 parts by weight of component (A). It is more preferable to set the value within the range.
[0032]
(3) Dehydrating agent
(1) Definition
The dehydrating agent used in the photocurable composition is defined as a compound that converts to a substance other than water by a chemical reaction, or a compound that does not affect photocurability and storage stability by physical adsorption or inclusion. .
That is, by containing such a dehydrating agent, the conflicting characteristics of storage stability and photocurability can be improved without impairing the weather resistance and heat resistance of the photocurable composition. The reason for this is that the storage stability of the photocurable composition is improved because the dehydrating agent effectively absorbs water entering from the outside. On the other hand, in the condensation reaction, which is a photocurable reaction, It is considered that the photocurability of the photocurable composition is improved because the dehydrating agent effectively absorbs the sucrose sequentially.
[0033]
(2) Types of dehydrating agents
Next, the kind of dehydrating agent used for a photocurable composition is demonstrated. The type of the dehydrating agent is not particularly limited, but is at least one compound selected from the group consisting of carboxylic acid esters, acetals (including ketals), and carboxylic acid anhydrides as the organic compound. It is preferable. Further, it is also preferable to use ceramic powder having a dehydrating function as the inorganic compound. These dehydrating agents exhibit an excellent dehydrating effect, and can effectively exhibit the function of the dehydrating agent with a small amount of addition.
[0034]
The carboxylic acid ester as the dehydrating agent is selected from carboxylic acid ortho ester, carboxylic acid silyl ester, and the like.
Here, preferable examples of the carboxylic acid orthoester include methyl orthoformate, ethyl orthoformate, propyl orthoformate, butyl orthoformate, methyl orthoacetate, ethyl orthoacetate, propyl orthoacetate, butyl orthoacetate, methyl orthopropionate and orthopropion. Examples include ethyl acid. Of these carboxylic acid orthoesters, orthoformic acid esters are particularly preferred as the dehydrating agent in the present invention from the viewpoint of exhibiting a more excellent dehydrating effect and further improving storage stability and photocurability.
Preferred carboxylic acid silyl esters include trimethylsilyl acetate, tributylsilyl acetate, trimethylsilyl formate, trimethylsilyl oxalate and the like.
[0035]
Preferred acetals include, for example, acetone dimethyl acetal, acetone diethyl acetal, methyl ethyl ketone dimethyl acetal, methyl ethyl ketone dimethyl acetal, cyclohexanone dimethyl acetal, and cyclohexanone diethyl acetal. These acetals show an excellent dehydrating effect, and can further improve the storage stability and photocurability of the photocurable composition.
[0036]
Examples of preferable carboxylic acid anhydrides include formic anhydride, acetic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and acetic acid benzoic anhydride. In particular, acetic anhydride and succinic anhydride are preferable because they are particularly excellent in dehydrating effect.
[0037]
Examples of the ceramic powder having a preferable dehydrating function include silica gel particles, alumina particles, silica alumina particles, activated clay, and zeolite. These ceramic powders have a strong affinity for water and can exhibit an excellent dehydration effect.
[0038]
(3) Addition amount of dehydrating agent
Next, the addition amount of the dehydrating agent used in the photocurable composition will be described. The addition amount of the dehydrating agent is not particularly limited, but it is usually preferable to set the value within the range of 0.1 to 100 parts by weight with respect to 100 parts by weight of component (A). The reason for this is that when the addition amount of the dehydrating agent is less than 0.1 parts by weight, the effect of the addition is poor and the effect of improving the storage stability and photocurability may be low. When the addition amount exceeds 100 parts by weight, the effect of improving storage stability and photocurability may be saturated.
Therefore, more preferably, the addition amount of the dehydrating agent is set to a value within the range of 0.5 to 50 parts by weight with respect to 100 parts by weight of the component (A), and more preferably 1 to 10 parts by weight. The value is within the range of.
[0039]
(4) Additive
The photocurable composition includes radical photopolymerization initiators, photosensitizers, organic solvents, polymerization inhibitors, polymerization initiator assistants, leveling agents, and wettability improvements as long as the objects and effects of the present invention are not impaired. It is also preferable to further contain additives such as an agent, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupling agent, an inorganic filler, a pigment, and a dye.
[0040]
(5) Antireflection film
(1) Method of forming an antireflection film
When forming an anti-reflective film from a photocurable composition, it is preferable to take the method of coating. As such a coating method, a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, an ink jet method, or the like can be used. Among these, when the substrate is plate-shaped, it is particularly preferable to use the dipping method.
[0041]
Further, the means for photocuring the photocurable composition is not particularly limited. For example, light having a wavelength of 150 to 400 nm is used by using a light source such as a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, or an excimer lamp. Is preferably irradiated. It is also preferable to irradiate the photocurable composition with light while scanning laser light or convergent light obtained using a lens, mirror, or the like. Furthermore, using a mask having a light transmission part of a predetermined pattern, the composition is irradiated with non-converging light through this mask, or a light guide member formed by bundling a large number of optical fibers is used to guide the light. It is also preferable to irradiate light through an optical fiber corresponding to a predetermined pattern on the member.
[0042]
▲ 2 ▼ Thickness
The thickness of the antireflection film is not particularly limited. For example, in the case of a single layer, the thickness is preferably in the range of 50 to 1000 nm. The reason for this is that when the thickness is less than 50 nm, the antireflection effect and the adhesion to the substrate may be reduced. On the other hand, when the thickness exceeds 1000 nm, optical interference occurs and the antireflection effect is obtained. This is because it may decrease.
Therefore, when the antireflection film is a single layer, the thickness is more preferably set to a value in the range of 50 to 500 nm, and further preferably set to a value in the range of 60 to 200 nm.
[0043]
In the case where a plurality of antireflection films are provided to form a multilayer structure, the thickness is preferably set to a value obtained by multiplying the preferred thickness in the case of a single antireflection film by the number of layers. For example, when two antireflection films are provided, the total thickness is preferably set to a value in the range of 100 to 2000 nm.
[0044]
(3) Refractive index
Although the lower the refractive index value of the antireflection film, the better the antireflection effect is obtained, specifically, a value of 1.7 (−) or less is preferable, and more preferably 1.3 to 1.6 (− ) In the range of 1.3 to 1.5 (−), and more preferably in the range of 1.3 to 1.5 (−). The reason for this is that when the refractive index is less than 1.3 (−), the types of materials that can be used may be excessively limited, while when the refractive index exceeds 1.7 (−). This is because the antireflection effect may be significantly reduced.
[0045]
In the case where a plurality of antireflection films are provided, it is sufficient that at least one of the antireflection films has a refractive index value within the above-described range. It may have a refractive index value exceeding.
[0046]
[Second Embodiment]
The second embodiment of the present invention contains a hydrolyzate (A component) of a hydrolyzable silane compound, a photoacid generator (B component), a dehydrating agent (C component), and a fluorine-containing polymer (D component). It is an antireflection film formed by photocuring a photocurable composition. By adding (compounding) the fluorine-containing polymer as described above, the refractive index value of the obtained antireflection film can be reduced, and the contamination resistance can be improved. Therefore, it is possible to adjust the refractive index value very finely and to expand the application of the antireflection film.
Hereinafter, although the fluorine-containing polymer used for 2nd Embodiment is demonstrated in detail, the hydrolyzate (A component) of a hydrolysable silane compound, a photo-acid generator (B component), and a dehydrating agent (C component) Since the same thing as 1st Embodiment can be used also in 2nd Embodiment about this etc., description here is abbreviate | omitted.
[0047]
(1) Types of fluorine-containing polymers (fluorine-containing monomers)
The type of fluorine-containing polymer is not particularly limited as long as it is a polymer having a fluorine atom in the molecule. For example, fluoroolefins, perfluoroalkyl vinyl ether, perfluoroalkoxyalkyl vinyl ether, fluoroalkyl vinyl ether, Polymers obtained by polymerizing fluorine-containing monomers such as fluoroalkoxyalkyl vinyl ethers and fluorine-containing (meth) acrylic acid esters are preferred.
[0048]
More specifically, fluoroolefins such as trifluoroethylene, tetrafluoroethylene, pentafluoropropylene and hexafluoropropylene, fluoroalkyl vinyl ethers and fluoroalkoxyalkyl vinyl ethers are preferable, and hexafluoropropylene is particularly preferable.
[0049]
(2) Copolymerization component 1
In addition, when a fluorine-containing polymer is polymerized, a hydrolyzable silyl group-containing monomer, an epoxy group-containing monomer, an oxetane group-containing monomer, a hydroxyl group (hydroxy group) -containing monomer, and a carboxyl group-containing It is preferable to copolymerize at least one copolymer component 1 (reactive group-containing monomer) selected from the group consisting of monomers.
By copolymerizing such a reactive group-containing monomer, a hydrolyzable silyl group, epoxy group, oxetane group, hydroxyl group and carboxyl group can be easily introduced into the molecule as the functional group. Therefore, the compatibility between the fluorine-containing polymer and the hydrolyzable silane compound is improved, and furthermore, the fluorine-containing polymer can be reacted with the hydrolyzable silane compound.
[0050]
The amount of the copolymerizable component used is not particularly limited. For example, when the total amount of the copolymerizable component is 100 mol%, the amount used is in the range of 1 to 70 mol%. A value within the range is preferable. The reason is that if the amount used is less than 1 mol%, the effect of addition may be poor, while if it exceeds 70 mol%, the resulting fluorine-containing polymer may be easily gelled. Therefore, from the viewpoint of a better balance between the effect of addition and the prevention of gelation, it is more preferable to set the amount used within a range of 3 to 50 mol%.
[0051]
(3) Copolymerization component 2
In addition, when the fluorine-containing polymer is polymerized, a copolymer component other than those described above (copolymer component 2), for example, methyl vinyl ether, can be obtained from the viewpoint of further improving the yield and easily adjusting the fluorine content. Alkyl vinyl ethers such as vinyl acetate; carboxylic acid vinyl esters such as vinyl acetate; α-olefins such as ethylene and propylene; and (meth) acrylic acid esters such as methyl (meth) acrylate. In addition, these copolymerizable components may be used individually by 1 type, or may be used in combination of 2 or more type.
[0052]
Further, the amount of these copolymer components used is not particularly limited. For example, when the total amount of the copolymer components is 100 mol%, the amount used is in the range of 10 to 70 mol%. A value is preferred. The reason for this is that when the amount used is less than 10 mol%, the effect of addition may be poor. On the other hand, when the amount used exceeds 70 mol%, the amount of fluorine-containing monomer used is relatively reduced, and in a wide range, This is because it may be difficult to adjust the value of the refractive index, or the solubility in an organic solvent may be reduced.
[0053]
(4) Radical polymerization of fluorine-containing polymers
The fluorine-containing polymer described above can be obtained by radical polymerization of a fluorine-containing monomer or the like in the presence of a radical polymerization initiator (radical generator). More specifically, for example, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, and a solution polymerization method can be employed as the radical polymerization method. In addition, the polymerization operation in the radical polymerization method can be appropriately selected according to the purpose, such as batch system, semi-continuous system, and continuous system.
[0054]
Examples of the radical polymerization initiator include ketone peroxides; hydroperoxides; peroxyesters; azo compounds; persulfates; iodine-containing fluorine compounds. These radical polymerization initiators can be used alone or in combination of two or more.
From the viewpoint of adjusting the radical polymerization rate, it is also preferable to use an inorganic reducing agent such as sodium hydrogen sulfite and sodium pyrosulfite and an organic reducing agent such as cobalt naphthenate and dimethylaniline together with the radical polymerization initiator described above. .
[0055]
Moreover, it is also preferable to use the azo group containing polysiloxane compound represented by following General formula (5) as a preferable radical polymerization initiator. By using such a radical polymerization initiator, a radical polymerization reaction can be caused, and a siloxane bond can be easily introduced into the obtained fluoropolymer.
[0056]
[Chemical 1]

[0057]
[In general formula (5), R⁹, R^Ten, R¹³~ R¹⁶Is a monovalent organic group having 1 to 6 carbon atoms, R¹¹And R¹²Is -CN or -COOCH_ThreeP, q, s, y, and t are integers of 1 to 6, and z is an integer of 1 to 20. ]
[0058]
Moreover, as a compound represented by General formula (5), the compound specifically represented by following formula (6) is more preferable.
[0059]
[Chemical formula 2]

[0060]
[In formula (6), y and z are the same as the contents in general formula (5). ]
[0061]
(5) Fluorine content
The fluorine content in the fluorine-containing polymer is not particularly limited, but is, for example, a value of 3% by weight or more, more preferably 5-60% by weight. This is because when the fluorine content in the fluorine-containing polymer is less than 3% by weight, the antireflection effect may be lowered, or it may be difficult to change the refractive index value in a wide range.
The fluorine content in the fluorine-containing polymer can be measured using the alizarin complexone method, and can be easily adjusted by adjusting the amount (content ratio) and type of the fluorine-containing monomer during polymerization. Can be controlled.
[0062]
(5) Addition amount of fluorine-containing polymer
Although the addition amount of a fluorine-containing polymer is not specifically limited, For example, it is preferable to set it as the value within the range of 0.5-250 weight part with respect to 100 weight part of (A) component. The reason for this is that when the addition amount of the fluorine-containing polymer is less than 0.5 parts by weight, the addition effect may not be exhibited, whereas when it exceeds 250 parts by weight, the storage stability and paintability may be deteriorated. Because.
Therefore, the addition effect of the fluorine-containing polymer is within the range of 1 to 200 parts by weight with respect to 100 parts by weight of the component (A) from the viewpoint of surely obtaining the addition effect and more excellent storage stability. More preferably, the value is in the range of 3 to 150 parts by weight.
[0063]
[Third Embodiment]
The third embodiment of the present invention is a light containing a hydrolyzate (A component) of a hydrolyzable silane compound, a photoacid generator (B component), a dehydrating agent (C component), and silica particles (E component). It is an antireflection film formed by photocuring a curable composition on a substrate. Thus, by adding (compounding) silica particles, curing shrinkage of the obtained antireflection film can be reduced. Moreover, the mechanical strength of the antireflection film, for example, the value of Young's modulus can be increased to further improve the scratch resistance.
Hereinafter, although the detail of the silica particle used for 3rd Embodiment is demonstrated, about hydrolyzate (A component) of a hydrolysable silane compound, a photo-acid generator (B component), a dehydrating agent (C component), etc. Since the same thing as 1st Embodiment can be used, description here is abbreviate | omitted.
[0064]
(1) Addition amount of silica particles
The addition amount of the silica particles used in the third embodiment is not particularly limited. For example, a value in the range of 0.1 to 100 parts by weight with respect to 100 parts by weight of the component (A) It is preferable to do this. The reason for this is that when the addition amount of silica particles is less than 0.1 parts by weight, the effect of addition may not be exhibited, whereas when it exceeds 100 parts by weight, storage stability and paintability may be deteriorated. is there.
Therefore, since the addition effect is surely obtained and the storage stability is more excellent, the addition amount of the silica particles is within the range of 0.2 to 80 parts by weight with respect to 100 parts by weight of the component (A). More preferably, the value is within the range of 0.5 to 50 parts by weight.
[0065]
(2) Types of silica particles
The silica particles used in the third embodiment may be particles having silica as a main component, and may contain components other than silica. Examples of components other than silica include alkali metal oxides, alkaline earth metal oxides, and oxides such as Ti, Zr, Al, B, Sn, and P.
Moreover, it is preferable to make the average particle diameter of a silica particle into the value within the range of 0.001-0.2 micrometer. Furthermore, when the objective is to form a transparent photocurable composition or antireflection film using silica particles, the value is more preferably in the range of 0.001 to 0.01 μm. .
[0066]
Further, the difference between the refractive index of the silica particles to be used (temperature 25 ° C., Na-D line, hereinafter the same) and the refractive index of the photocurable composition is set to 0.02 (−) or less, It is preferred to select silica particles. By setting the difference in refractive index to such a value, the transparency of the antireflection film can be further increased.
[0067]
[Fourth Embodiment]
4th Embodiment of this invention contains the hydrolyzate (A component) of a hydrolysable silane compound, a photo-acid generator (B component), a dehydrating agent (C component), and a reactive diluent (F component). It is the antireflection film formed by photocuring the photocurable composition which carries out on a base material. By adding (mixing) the reactive diluent in this way, the adhesion to the substrate is improved, the curing shrinkage of the resulting antireflection film is reduced, or the mechanical strength of the antireflection film is controlled. be able to. Furthermore, when a radical polymerizable reactive diluent is used, the photocurability of the photocurable composition can be more finely adjusted by adding a radical generator. In addition, when a cationic polymerizable reactive diluent is used, the photocurability and mechanical properties can be adjusted.
Hereinafter, although the detail of the reactive diluent (F component) in 4th Embodiment is demonstrated, the hydrolyzate (A component) of a hydrolysable silane compound, a photo-acid generator (B component), and a dehydrating agent (C) About the component) etc., since the thing similar to 1st Embodiment can be used, description here is abbreviate | omitted.
[0068]
(1) Compounding amount of reactive diluent
In 4th Embodiment, although the compounding quantity (addition amount) of a reactive diluent is not restrict | limited in particular, For example, it is the range of 0.1-80 weight part with respect to 100 weight part of (A) component. A value within the range is preferable. The reason for this is that when the amount of the reactive diluent is less than 0.1 parts by weight, the effect of addition may not be manifested. On the other hand, when the amount exceeds 80 parts by weight, the weather resistance of the resulting antireflection film decreases. This is because there are cases. Therefore, the amount of the reactive diluent is more preferably in the range of 1 to 50 parts by weight, and still more preferably in the range of 2 to 20 parts by weight.
[0069]
(2) Types of reactive diluents
Next, the type of reactive diluent used in the fourth embodiment will be described. As such a reactive diluent, it is preferable to blend a cationically polymerizable monomer and / or an ethylenically unsaturated monomer.
Specific examples of the cationic polymerizable monomer include epoxy compounds, oxetane compounds, oxolane compounds, cyclic acetal compounds, cyclic lactone compounds, thiirane compounds, thietane compounds, vinyl ether compounds, spiro orthoester compounds, cyclic ether compounds, cyclic thioether compounds, and the like. Can be mentioned.
[0070]
The ethylenically unsaturated monomer is a compound having an ethylenically unsaturated bond (C = C) in the molecule, a monofunctional monomer having one ethylenically unsaturated bond in one molecule, and in one molecule It can be defined as a polyfunctional monomer having two or more ethylenically unsaturated bonds.
Preferred ethylenically unsaturated monomers include, for example, isobornyl (meth) acrylate, lauryl (meth) acrylate, butoxyethyl (meth) acrylate polyethylene glycol mono (meth) acrylate, bornyl (meth) acrylate, methyltriethylene diglycol (meth) Mention may be made of acrylates.
[0071]
[Fifth Embodiment]
The fifth embodiment of the present invention is a laminate having the antireflection film described in the first to fourth embodiments on the substrate surface. In addition, the laminated body should just contain the base material and the antireflection film at least, and various modifications are included. Hereinafter, the laminated body of 5th Embodiment is demonstrated concretely, referring FIGS. 1-3.
FIG. 1 is a cross-sectional view of a laminate 14 including an antireflection film 10 formed directly on a substrate 12, and FIG. 2 shows a hard coat layer 16 interposed between the substrate 12 and the antireflection film 10. It is sectional drawing of the made laminated body 18. FIG. Also, FIG. 3 shows, from the bottom, the base material 12, the hard coat layer 16, the first high refractive index layer 20, the first antireflection film 22, the second high refractive index layer 24, It is sectional drawing of the laminated body 28 of the multilayer structure comprised by forming the 2nd antireflection film 26 in order.
[0072]
In the case of the laminate 14 shown in FIG. 1, since the antireflection film 10 can be directly formed on the base material 12, the structure is simple as a single layer and can be formed with high accuracy.
Moreover, when the hard coat layer 16 is interposed between the antireflection film 10 and the base material 12 as in the laminate 18 shown in FIG. 2, the adhesion of the antireflection film 10 to the base material 12 is further improved. In addition, the durability of the laminate 18 is further improved due to the mechanical properties of the hard coat layer 16. The hard coat layer 16 is made of, for example, SiO.₂, Epoxy resin, acrylic resin, melamine resin, and the like are preferable. Further, the thickness is preferably set to a value in the range of 1 to 50 μm, more preferably 5 to 10 μm. The value is within the range.
[0073]
In addition to the first and second antireflection layers 22 and 26 as in the laminated body 28 shown in FIG. 3, a relatively high refractive index value, for example, 1.5 to 2.0 (−). It is also preferable to provide the first and second high refractive index layers 20 and 24 having a thickness within the range and having a thickness of 50 to 200 nm in contact with the first and second antireflection layers 22 and 26, respectively. In this way, by providing the high refractive index layers 20 and 24 in contact with the antireflection layer of the present invention and providing a plurality of layers, a more excellent antireflection effect can be obtained.
Further, when the high refractive index layers 20 and 24 are provided, a better antireflection effect can be obtained. Therefore, the refractive index difference between the antireflective layers 22 and 26 and the high refractive index layers 20 and 24 is set to 0. It is preferable to set it as the value of 05 (-) or more, It is more preferable to set it as the value within the range of 0.1-0.5 (-), The value within the range of 0.15-0.5 (-) More preferably.
[0074]
Further, when the hard coat layer 16, the high refractive index layers 20, 24, or the primer layer (not shown) is provided as shown in the laminates 18 and 28 in FIGS. The antireflection films 10, 22, and 26 can be easily formed by irradiating ultraviolet rays or the like after coating the photocurable composition. In that case, the high refractive index layers 20 and 24 that bear one end of the antireflection effect may be referred to as the antireflection film (antireflection layer) of the present invention.
[0075]
Moreover, the kind of the base material 12 in the laminates 14, 18, and 28 shown in FIGS. 1 to 3 is not particularly limited as long as an antireflection effect is desired when light is transmitted. For example, glass, polycarbonate resin, polyester resin or acrylic resin can be used. In the case where the substrate 12 is made of glass, examples of a specific laminate include a camera lens unit, a screen display unit of a television (CRT, LCD), a window glass, and the like. Moreover, in the case of the base material 12 which consists of a polycarbonate-type resin, a polyester-type resin, or an acrylic resin, the color filter etc. in a liquid crystal display device are mentioned.
[0076]
[Sixth Embodiment]
The sixth embodiment of the present invention is an embodiment relating to a method for producing an antireflection film (a laminate having an antireflection film on a substrate surface) including the following first step and second step. In addition, a 1st process is a process (it may be called a formation process) which shape | molds any one photocurable composition of the 1st-5th embodiment mentioned above on a base material, and is 2nd. This step is a step of photocuring the photocurable composition by exposure using an exposure machine (sometimes referred to as an exposure step).
[0077]
(1) First step
The molding method of the photocurable composition is not particularly limited, but it is preferable to apply and form the photocurable composition using, for example, a dip coater, a spin coater, or a bar coater. Specifically, when a spin coater is used, after fixing the substrate in the spin coater, as an example, it is preferable to spin-coat a photocurable composition whose viscosity has been adjusted in advance under the condition of a rotational speed of 1000 rpm.
Moreover, the thickness after shaping | molding (before photocuring) of a photocurable composition is not specifically limited, For example, it is preferable that it is a value within the range of 50-1000 nm. The reason is that if the thickness after molding is less than 50 nm, it may be difficult to keep the photocurable composition in a predetermined shape. This is because when the film is used, the antireflection effect may be poor.
[0078]
Moreover, in the first step, it is preferable to preheat (pre-bake) at a temperature of 100 to 150 ° C. after the molding of the photocurable composition. By preheating the photocurable composition under such conditions, the volatile portion in the photocurable composition can be effectively removed, and the molded product of the photocurable composition will not lose its shape. Moreover, a part of silanol of the hydrolyzable silane compound (component A) can be reacted, and the adhesion to the substrate and the chemical resistance (developer) during development can be improved.
However, it is more preferable to heat at a temperature of 110 to 140 ° C., and more preferable to heat at a temperature of 115 to 130 ° C. so that the development characteristics are not deteriorated by excessive heating.
[0079]
Furthermore, the heating time is preferably determined in consideration of the heating temperature, but when preheating is performed at a temperature of 100 to 150 ° C., the heating time is preferably 1 to 20 minutes. The reason for this is that when the heating time is less than 1 minute, the reaction of silanol may become non-uniform. On the other hand, when the heating time exceeds 10 minutes, the silanol reacts excessively and accuracy is increased using a developer. This is because it may be difficult to develop well. Therefore, the heating time is preferably set to a value within the range of 2 to 15 minutes, and more preferably set to a value within the range of 3 to 10 minutes.
The heating means is not particularly limited, and for example, an oven or an infrared lamp can be used.
[0080]
(2) Second step
In addition, the photocuring method in the second step is as described in part in the first embodiment, but not only the entire surface is exposed and photocured, but also non-converged light through a photomask having a predetermined pattern. It is also preferable to perform pattern exposure by exposing the photocurable composition to a pattern, or using a light guide member in which a large number of optical fibers are bundled and irradiating light only from the optical fiber corresponding to the photomask pattern. By performing pattern exposure in this way, a photocured product portion that has been exposed and cured and a photocurable composition portion that has not been exposed and has not been cured can be formed with high accuracy. Specifically, the mask pattern line / space (ratio 50/50) is in the range of 10 μm or more, more preferably in the range of 30 μm or more, and even more preferably in the range of 50 μm or more. It has been confirmed that the exposed portion can be formed with good reproducibility.
Therefore, only the uncured photocurable composition portion can be easily wet-developed (removed) using a developer, and the exposed portion of the base material, that is, the portion where the antireflection film is not provided, can be removed in a short time. And it can form easily. Therefore, it is possible to firmly bond and fix a desired member using such an exposed portion of the base material.
[0081]
Furthermore, in the second step, it is also preferable to further heat the antireflection film that is a photocured product. In that case, it is preferable to heat on the conditions of the temperature 25-200 degreeC which is below the decomposition | disassembly start temperature of a base material or a coating film, and 5 minutes-72 hours. By heating the antireflection film in this way, an antireflection film (laminate) having more excellent heat resistance and weather resistance can be obtained.
[0082]
【Example】
Examples of the present invention will be described below, but the scope of the present invention is not limited to the description of these examples. Moreover, unless otherwise indicated, the compounding quantity of each component in an Example means the weight part.
[0083]
[Example 1]
(Preparation of photocurable composition)
In a vessel equipped with a stirrer and distillation apparatus, methyltrimethoxysilane (MTMS, 80.0 g, 0.558 mol) and an electrical conductivity of 8 × 10^-FiveS · cm^-1Of ion-exchanged water (16.0 g, 0.889 mol), methyltrimethoxysilane was hydrolyzed by heating and stirring at a temperature of 60 ° C. for 6 hours. Subsequently, after raising the temperature in the container to 80 ° C., methanol by-produced by hydrolysis was distilled off while dropping methyl isobutyl ketone (hereinafter abbreviated as MIBK) dropwise. And finally, solid content was adjusted to 22 weight% and the solution (henceforth the polysiloxane solution 1) containing the polysiloxane which is (A) component was obtained. About the obtained polysiloxane solution 1, when the weight average molecular weight of polystyrene conversion was measured using GPC, the value of 1500 was obtained.
Next, 3 parts by weight of SI-100L (manufactured by Sanshin Chemical Co., Ltd.) as a photoacid generator of component (B) per 100 parts by weight of the resulting polysiloxane solution 1 (total of solids and solvent), As a dehydrating agent of component (C), 5 parts by weight of methyl orthoformate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to obtain a photocurable composition A.
[0084]
(Formation and evaluation of antireflection film)
(1) Photocurability 1
To the obtained photocurable composition A (solution), a mixed solvent of equal amounts of MIBK and n-butanol was added to adjust the solid content concentration to 3% by weight. Next, a coating film was formed using a dip coater on a polycarbonate plate (thickness 1 mm, manufactured by Teijin Chemicals Ltd.) under atmospheric conditions.
Next, after drying at room temperature (25 ° C.) for 2 minutes to obtain a coating film having a thickness of 0.1 μm, the temperature is 25 ° C. and the exposure amount is 100 mJ / cm in the air.²(Irradiation time 1 second), 200 mJ / cm²(Irradiation time 2 seconds) and 300 mJ / cm²(An irradiation time of 3 seconds) was irradiated with ultraviolet rays using a conveyor type high pressure mercury lamp (2 kW) manufactured by Oak Manufacturing Co., Ltd. to form an antireflection film. In addition, an antireflection film was formed by irradiating ultraviolet rays in the same manner at 25 ° C. in nitrogen. About the obtained anti-reflective film, surface tack was measured by finger touch and the photocurability was evaluated according to the following criteria. The results are shown in Table 1. further,
A: 100 mJ / cm²There is no surface tack of the antireflection film after exposure.
○: 200 mJ / cm²There is no surface tack of the antireflection film after exposure.
Δ: 300 mJ / cm²There is no surface tack of the antireflection film after exposure.
X: 300 mJ / cm²After the exposure, there is a surface tack of the antireflection film.
[0085]
(2) Photocurability 2
After the obtained photocurable composition (solution) was stored at a temperature of 40 ° C. for 1 month and 3 months, the appearance change (viscosity increase) was visually measured, and the photocurability of (1) above was further measured. Then, the photocurability after long-term storage was evaluated according to the following criteria. The obtained results are shown in Table 1 as storage stability.
A: No change in appearance or change in photocurability is observed even after 3 months.
○: Appearance change and photo-curing change are not observed after 1 month.
X: After one month, a change in appearance or a decrease in photocurability is observed.
[0086]
(3) Antireflection
After dip-coating the photocurable composition onto a polycarbonate plate, the exposure amount is 200 mJ / cm in the atmosphere using the conveyor type high-pressure mercury lamp.²The laminated body including the antireflection film having a thickness of 0.1 μm was formed by irradiating ultraviolet rays so that The antireflection effect of the obtained laminate (antireflection film) was measured with a spectral reflectance measuring device (a self-recording spectrophotometer U-3410 incorporating a large sample chamber integrating sphere attachment device 150-09090, manufactured by Hitachi, Ltd.). As shown in FIG. 4, the reflectance was measured and evaluated in the wavelength range of 400 to 800 nm. That is, the reflectance of the laminated body (antireflection film) at each wavelength is measured using the reflectance of the aluminum vapor deposition film as a reference (100%), and the antireflection effect is measured according to the following criteria from the reflectance of light at a wavelength of 550 nm. Evaluated. The results are shown in Table 1.
A: The reflectance is 1% or less.
A: The reflectance is 2% or less.
Δ: The reflectance is 3% or less.
X: Reflectance is a value exceeding 3%.
[0087]
(4) Transparency
After spin-coating the photocurable composition on a quartz plate, the exposure amount is 200 mJ / cm in the atmosphere using the conveyor type high-pressure mercury lamp.²Ultraviolet rays were irradiated so as to form a photocured material (antireflection film) for transparency measurement having a thickness of 10 μm. Subsequently, using the spectrophotometer, the light transmittance (T /%) of wavelength 550nm in the obtained photocured material was measured, and transparency was evaluated on the following reference | standard from the obtained light transmittance. The results are shown in Table 1.
A: The light transmittance is a value of 95% or more.
Δ: Light transmittance is a value of 80 to less than 95%.
X: Light transmittance is a value of less than 80%.
[0088]
(5) Refractive index
After the photocurable composition is applied onto a polytetrafluoroethylene film using a bar coater, the exposure amount is 200 mJ / cm in the atmosphere using the conveyor type high-pressure mercury lamp.²Ultraviolet rays were irradiated so that a photocured material (antireflection film) having a thickness of 20 μm for refractive index measurement was formed. The refractive index of Na-D line in the obtained photocured product was measured using an Abbe refractometer at a measurement temperature of 25 ° C. The results are shown in Table 1.
[0089]
(6) Weather resistance
After spin-coating the photocurable composition on a quartz plate, the exposure amount is 200 mJ / cm in the atmosphere using the conveyor type high-pressure mercury lamp.²Ultraviolet rays were irradiated so that a photocured material (antireflection film) having a thickness of 2 μm for weather resistance measurement was formed. The obtained photocured material is subjected to an accelerated weathering test using a sunshine carbon arc lamp type light resistance tester in accordance with JIS D0205 (conditions of humidity 50%, temperature 63 ° C., rainfall 18 minutes / 120 minutes irradiation). did. The appearance of the photocured product after 1000 hours and 2000 hours after the accelerated weathering test was visually observed, and the weather resistance was evaluated according to the following criteria. At the same time, the yellowing degree based on JIS K7103 was measured by the ΔYI value, and the weather resistance of the photocured product was similarly evaluated. The results are shown in Table 1.
○: No change in appearance (cracks, etc.), and ΔYI value is 0.1 or less.
Δ: Almost no change in appearance (cracks, etc.), and ΔYI value is 2 or less.
X: Appearance change (crack etc.) is recognized, or ΔYI value exceeds 2.
[0090]
(7) Scratch resistance
After dip-coating the photocurable composition onto a polycarbonate plate, the exposure amount is 200 mJ / cm in the atmosphere using the conveyor type high-pressure mercury lamp.²Then, an ultraviolet ray was irradiated so as to form a laminate including an antireflection film having a thickness of 0.1 μm. The surface of the antireflection film in the obtained laminate was loaded with 1 kg / cm of paper (Kimwipe, manufactured by Jujo Kimberley Co., Ltd.).²The scratch resistance of the antireflection film was evaluated in accordance with the following criteria from rubbing 25 times under the above conditions, the degree of occurrence of scratches, the degree of peeling, and the pencil hardness test. The results are shown in Table 1.
A: Scratches and peeling are not observed in the antireflection film, and the pencil hardness is 2H or more.
○: No scratches or peeling were observed in the antireflection film, and the pencil hardness was less than 2H.
Δ: Peeling of the antireflection film is not observed, but generation of fine scratches is observed.
X: A part of the antireflection film peels off, or many streak-like scratches are observed.
[0091]
(8) Pollution resistance
After dip-coating the photocurable composition on a polycarbonate plate, the exposure amount is 200 mJ / cm in the atmosphere using the conveyor type high-pressure mercury lamp.²Then, an ultraviolet ray was irradiated so as to form a laminate including an antireflection film having a thickness of 0.1 μm. The anti-reflection coating of the obtained laminate was subjected to a spot test using contaminants (fingerprints and black magic) and judged according to the following criteria. The results are shown in Table 1. (Double-circle): About a fingerprint and black magic, it can wipe off at once using a dry cloth, respectively.
○: Fingerprints can be wiped less than 10 times using a dry cloth, and black magic can be wiped less than 10 times using ethyl alcohol.
Δ: Fingerprints can be wiped 10 times or more using a dry cloth, and black magic can be wiped 10 times or more using ethyl alcohol.
X: The fingerprint cannot be wiped off using a dry cloth, and the black magic cannot be wiped off using ethyl alcohol.
[0092]
[Example 2]
Instead of the polycarbonate plate in Example 1, an antireflection film was formed from the photocurable composition A in the same manner as in Example 1 except that a polyethylene terephthalate film (thickness: 188 μm, manufactured by Toyobo Co., Ltd.) was used as a base material. After forming, the reflectance and the like were measured and evaluated as shown in FIG. The obtained results are shown in Table 1. However, since transparency, refractive index, and weather resistance are repeated tests of Example 1, these evaluation tests are omitted in Example 2, and Table 1 shows the results obtained in Example 1. is there.
[0093]
[Example 3]
(Preparation of photocurable resin composition)
(1) Polymerization of fluorine-containing polymer
A stainless steel autoclave equipped with an electromagnetic stirrer with an internal volume of 1.0 liter was sufficiently replaced with nitrogen gas. Next, in this autoclave, 300 g of ethyl acetate (polymerization solvent), 24.0 g of ethyl vinyl ether, 25.8 g of hydroxybutyl vinyl ether, and nonionic reactive emulsifier NE-30 (manufactured by Asahi Denka Kogyo Co., Ltd.) 10. 0 g, 1.0 g of azo group-containing polydimethylsiloxane VPS-1001 (manufactured by Wako Pure Chemical Industries, Ltd.) as a radical generator and 0.5 g of lauroyl peroxide were accommodated. And after fully stirring a copolymerization component etc., it cooled to -50 degreeC using dry ice and methanol, and removed oxygen in the system again using nitrogen gas.
Next, after 99.9 g of hexafluoropropylene (gas) was introduced into the autoclave, the temperature inside the autoclave was raised to 70 ° C. When the temperature reached 70 ° C., the pressure in the autoclave was 5.9 kgf / cm 2.
[0094]
Next, a radical polymerization reaction was carried out over 20 hours while maintaining the temperature at 70 ° C. while stirring the copolymer components in the autoclave. And the pressure in the autoclave is 2.5 kgf / cm²When the temperature dropped to 1, the autoclave was cooled with water to stop the reaction. After confirming that the temperature in the autoclave had dropped to room temperature, the autoclave was opened to release unreacted monomers out of the system, and a fluorine-containing copolymer solution (polymer solution) was taken out.
The obtained fluorine-containing copolymer solution was put into a large amount of methanol to precipitate a fluorine-containing copolymer. Thereafter, the fluorine-containing copolymer was washed with a large amount of methanol, and further vacuum dried at a temperature of 50 ° C. to obtain a purified product of the fluorine-containing polymer having a hydroxyl group. About the obtained copolymer 1, the following evaluation items were each measured 5 times and averaged.
[0095]
(1) Measurement of weight average molecular weight
The purified product of the obtained fluorine-containing copolymer was dissolved in THF (tetrahydrofuran) to a concentration of 0.5% by weight. Next, using a GPC apparatus HLC-8020 (manufactured by Tosoh Corporation), the elution time from the GPC column of the fluorine-containing copolymer was detected with a refractometer (RI), and from the resulting elution time, polystyrene conversion As the molecular weight, the weight average molecular weight of the fluorine-containing copolymer was calculated. As a result, the obtained fluorine-containing copolymer had a weight average molecular weight of 42,000.
[0096]
(2) Measurement of fluorine content
The fluorine content of the obtained fluorine-containing copolymer was measured based on the alizarin complexone method. As a result, the fluorine content of the obtained fluorine-containing copolymer was 46.1% by weight.
[0097]
(2) Modification of fluorine-containing copolymer
100 g of the obtained fluorine-containing copolymer having a hydroxyl group, 20 g of γ-isocyanatopropyltriethoxysilane, 500 g of methyl isobutyl ketone, and 0.01 g of dibutyltin dilaurate were placed in a reaction vessel equipped with a stirrer. Next, the fluorine-containing copolymer having a hydroxyl group was reacted with γ-isocyanatopropyltriethoxysilane under stirring under a nitrogen gas atmosphere at a temperature of 20 ° C. for 12 hours.
[0098]
Next, a part of the obtained reaction solution was taken out, a predetermined amount of dibutylamine was added thereto, and reacted with unreacted γ-isocyanatopropyltriethoxysilane in the reaction solution. The amount of unreacted dibutylamine was titrated with 0.1N hydrochloric acid to determine the amount of unreacted γ-isocyanatopropyltriethoxysilane. As a result, it was confirmed that γ-isocyanatopropyltriethoxysilane was completely consumed in the reaction solution, and γ-isocyanatopropyltriethoxysilane and the fluorine-containing copolymer having a hydroxyl group were sufficiently reacted. It was done. A part of the reaction solution was applied on a NaCl plate and dried in a nitrogen atmosphere to form a coating film. When the infrared spectrum of this coating film was measured, no peak derived from the isocyanate group was observed, while a new peak derived from the generated urethane group reacted with the isocyanate group was observed.
Therefore, from the results of the above titration and infrared spectrum, it was confirmed that the reaction between γ-isocyanatopropyltriethoxysilane and the fluorine-containing copolymer was completed, and a silane-modified fluorine-containing copolymer was obtained. .
[0099]
Further, a part of the reaction solution confirmed to contain a silane-modified fluorine-containing copolymer was taken out and poured into a large amount of methanol to precipitate a silane-modified fluorine-containing copolymer. Thereafter, the silane-modified fluorine-containing copolymer was washed with a large amount of methanol, and further vacuum dried at a temperature of 50 ° C. to obtain a purified product of the silane-modified fluorine-containing polymer.
[0100]
(3) Condensation of silane compounds
As in Example 1, a polysiloxane solution 1 having a solid content concentration of 22% by weight, which was an MTMS condensate solution, was obtained.
[0101]
(4) Preparation of photocurable resin composition
The purified product of the silane-modified fluorine-containing polymer was dissolved in MIBK to obtain a copolymer solution having a solid content concentration of 22% by weight. 30 g of this copolymer solution, 170 g of the polysiloxane solution 1, and 0.66 g of SI-100L as a photoacid generator were placed in a container equipped with a stirrer, and then mixed and stirred uniformly to form a photocurable resin composition. Product B was obtained.
[0102]
(Formation and evaluation of antireflection film)
Using the obtained photocurable resin composition B, an antireflection film (including a photocured material for evaluation) was formed and evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0103]
[Example 4]
(Preparation of photocurable composition)
In a vessel equipped with a stirrer, methyltrimethoxysilane (53.28 g, 0.3918 mol), methanol-dispersed colloidal silica (133.2 g, silica content 30 wt%, methanol silica sol manufactured by Nissan Chemical Co., Ltd.) Electrical conductivity is 8 × 10^-FiveS · cm^-1Of the ion-exchanged water (11.28 g, 0.628 mol) was subjected to hydrolysis by heating and stirring under conditions of a temperature of 60 ° C. for 6 hours. Next, while dropping MIBK, methanol by-produced by hydrolysis was distilled off. Finally, the solid content is adjusted to 22% by weight, and a polysiloxane solution (hereinafter referred to as polysiloxane solution 2) containing the polysiloxane as the component (A) and the silica particles as the component (E) of the present invention. .) About the obtained polysiloxane solution 2, when the weight average molecular weight of polystyrene conversion was measured using GPC, the value of 1800 was obtained.
Next, 3 parts by weight of photoacid generator SI-100L (manufactured by Sanshin Chemical Co., Ltd.) as component (B) per 100 parts by weight of the resulting polysiloxane solution 2 (solid content and solvent), (C) As a component, 5 parts by weight of methyl orthoformate as a dehydrating agent was added to obtain a photocurable composition C.
[0104]
(Formation and evaluation of antireflection film)
Using the obtained photocurable resin composition C, an antireflection film (including a photocured material for evaluation) was formed and evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0105]
[Example 5]
Except for adding 5 parts by weight of a reactive diluent KRM-2110 (manufactured by Asahi Denka Co., Ltd.) to the photocurable composition A prepared in Example 1, the photocurable composition D was used. 1 was evaluated by forming an antireflection film (including a photocured product for evaluation). The results are shown in Table 1.
[0106]
[Example 6]
(Formation of high refractive index film)
Metal oxide fine particle-containing coating agent No. 1352 (manufactured by Sumitomo Osaka Cement Co., Ltd.), 5 parts by weight of silane coupling agent TESOX (manufactured by Toagosei Co., Ltd.), and photoradical generator Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.) Then, an equivalent mixed solution of MIBK and t-butyl alcohol was further added to prepare a high refractive index film solution having a solid content of 3% by weight as a photocurable composition E.
After the obtained photocurable composition E was applied to a polycarbonate plate using a dip coater, the exposure amount was 200 mJ / cm in nitrogen using a high-pressure mercury lamp.²The film was irradiated with ultraviolet rays to form a high refractive index film having a thickness of 0.1 μm and a refractive index value of 1.7 (−).
[0107]
(Formation and evaluation of antireflection film)
On the obtained high refractive index film, an antireflection film (including a photocured material for evaluation) is formed from the photocurable composition similar to the photocurable composition A prepared in Example 1, and evaluated. did. In addition, since it becomes the repetition test of Example 1 about transparency, a refractive index, and a weather resistance, these evaluation tests are abbreviate | omitted in Example 6, and the result obtained in Example 1 is shown in Table 1 is there.
[0108]
[Example 7]
In Example 6, instead of using the photocurable composition A prepared in Example 1, high refractive index was obtained in the same manner as in Example 6 except that the photocurable composition B prepared in Example 3 was used. An evaluation film and an antireflection film were formed and evaluated. The results are shown in Table 1. In addition, since it becomes a repetition test of Example 3 about transparency, a refractive index, and a weather resistance, these evaluation tests are abbreviate | omitted in Example 6, and the result obtained in Example 3 is shown in Table 1 is there.
[0109]
[Example 8]
(Formation of hard coat layer)
A photocurable composition F for hard coat layer is prepared by mixing 40 parts by weight of DPHA which is an acrylic monomer, 60 parts by weight of Aronix TO-756 (manufactured by Toa Gosei Co., Ltd.) and 3 parts by weight of Irgacure 184 described above. Prepared. After the obtained photocurable composition F was applied to a polycarbonate plate using a bar coater, the exposure amount was 500 mJ / cm in nitrogen using a high-pressure mercury lamp.²Then, a hard coat layer having a thickness of 5.0 μm was formed.
[0110]
(Formation and evaluation of antireflection film)
On the obtained hard coat layer, in the same manner as in Example 7, a high refractive index film and an antireflection film were formed and evaluated. The results are shown in Table 1.
[0111]
[Comparative Example 3]
(Preparation of photocurable composition)
  A polysiloxane solution 1 was produced in the same manner as in Example 1. Next, 3.0 parts by weight of a photoacid generator SI-100L (manufactured by Sanshin Chemical Co., Ltd.) was added per 100 parts by weight of the obtained polysiloxane solution 1 to obtain a photocurable composition G. That is,Comparative Example 3Unlike Example 1, the photocurable composition G was prepared without adding a dehydrating agent.
[0112]
(Formation and evaluation of antireflection film)
  In the same manner as in Example 1, an antireflection film (including a photocured product for evaluation) was formed from the photocurable composition G and evaluated. The results are shown in Table 1. From comparison with the results in Example 1,Comparative Example 3Since no dehydrating agent was added, the photocurability and storage stability of the photocurable composition G were relatively lowered, but other characteristics were confirmed to be equivalent.
[0113]
[Comparative Examples 1 and 2]
(Preparation of photocurable composition)
Fluorine polymer KYNER ADS (manufactured by El Hoatom) 80 parts by weight DPHA (manufactured by Nippon Kayaku Co., Ltd.) 20 parts by weight and photo radical generator Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 3 parts by weight was added, and further dissolved in MIBK so that the solid content concentration was 3% by weight to obtain a photocurable composition H.
[0114]
(Evaluation of photocurable composition)
In the same manner as in Example 1 (base material: polycarbonate plate) and Example 2 (base material: PET film), an antireflection film (for evaluation) was obtained by changing the type of the substrate from the obtained photocurable composition H. It was evaluated by forming a photocured product. The results are shown in Table 1. In addition, about transparency, refractive index, and a weather resistance, since it becomes a repetition test in the comparative example 1 and the comparative example 2, in the comparative example 2, these evaluation tests were abbreviate | omitted and Table 1 obtained by the comparative example 1 Results are shown.
[0115]
[Table 1]

[0116]
【The invention's effect】
According to the antireflection film of the present invention or the laminate including the antireflection film, a photocurable composition comprising a specific hydrolyzable silane compound and a photoacid generator is used as a material for forming the antireflection film. Therefore, an antireflection film can be formed by a photocuring reaction even in the presence of oxygen, and in the obtained antireflection film or a laminate including the antireflection film, an excellent antireflection effect and stain resistance are obtained. It became possible.
[0117]
Moreover, as a material for forming an antireflection film, a photocurable composition having excellent storage stability and photocurability is obtained by combining a specific hydrolyzable silane compound, a photoacid generator, and a dehydrating agent. Therefore, an antireflection film can be formed by a faster photocuring reaction even in the presence of oxygen, and in the obtained antireflection film or a laminate including the antireflection film, an excellent antireflection effect and resistance It became possible to obtain contamination.
[0118]
Furthermore, according to the method for producing an antireflection film of the present invention, a photocurable composition comprising a specific hydrolyzable silane compound and a photoacid generator is used as a material for forming the antireflection film, Since the antireflection film is formed on the antireflection film, it is possible to form an antireflection film having an excellent antireflection effect and antifouling property using a photocuring reaction even in the presence of oxygen. In addition, according to the method for producing an antireflection film of the present invention, it is possible to form an antireflection film at an arbitrary position by pattern exposure.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a laminate according to the present invention (part 1).
FIG. 2 is a view showing a cross section of the laminate of the present invention (part 2).
FIG. 3 is a view showing a cross section of the laminate of the present invention (part 3).
4 is a reflectance measurement chart for an antireflection film (curing in the atmosphere) and a substrate (polycarbonate plate) used in Example 1. FIG.
5 is a reflectance measurement chart for an antireflection film (cured in the air) and a substrate (PET film) used in Example 2. FIG.
[Explanation of symbols]
10, 22, 26 Antireflection film
12 Base material
14, 18, 28 Laminate
16 Hard coat layer
20, 22 High refractive index layer

Claims (1)

Reflection characterized by including a step of molding a photocurable composition containing the following components (A) to (C) and a step of photocuring the molded photocurable composition to form an antireflection film. Manufacturing method of prevention film.
(A) At least one compound selected from the group consisting of a hydrolyzable silane compound represented by the general formula (1), a hydrolyzate thereof, and a condensate thereof (R ¹ ) _P Si (X) _4-P ( 1)
[In General Formula (1), R ¹ is a non-hydrolyzable organic group having 1 to 12 carbon atoms, X is a hydrolyzable group, and p is an integer of 0 to 3. ]
(B) Photoacid generator (C) Dehydrating agent

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