JP2004263082A - Coated film and antireflection film using the same - Google Patents

Coated film and antireflection film using the same Download PDF

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Publication number
JP2004263082A
JP2004263082A JP2003055203A JP2003055203A JP2004263082A JP 2004263082 A JP2004263082 A JP 2004263082A JP 2003055203 A JP2003055203 A JP 2003055203A JP 2003055203 A JP2003055203 A JP 2003055203A JP 2004263082 A JP2004263082 A JP 2004263082A
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film
coating
refractive index
resin
organic solvent
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Shinya Yamaguchi
信也 山口
Michimasa Moriya
三千正 森屋
Nobuo Nakanishi
伸夫 中西
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Nippon Paper Industries Co Ltd
Jujo Paper Co Ltd
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Nippon Paper Industries Co Ltd
Jujo Paper Co Ltd
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Priority to JP2003055203A priority Critical patent/JP2004263082A/en
Priority to TW093105517A priority patent/TWI251678B/en
Priority to KR1020040014169A priority patent/KR20040081300A/en
Publication of JP2004263082A publication Critical patent/JP2004263082A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08Cellulose derivatives
    • C08L1/10Esters of organic acids, i.e. acylates
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00Coating compositions based on unspecified macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20Diluents or solvents
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041Lenses
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00Characterised by the use of unspecified polymers
    • C08J2300/12Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00Characterised by the use of unspecified polymers
    • C08J2300/24Thermosetting resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08Cellulose derivatives
    • C08J2301/10Esters of organic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/16Applications used for films

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • General Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Optics & Photonics (AREA)
  • Medicinal Chemistry (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Paints Or Removers (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coated film that can be prevented from suffering from color unevenness caused by interference and has high transmittance and to provide an antireflection film using the coated film. <P>SOLUTION: The coated film is formed by coating a coating material comprising an organic solvent and a resin composition as the main components on at least one surface of a transparent resin film substrate to form a transparent coating layer thereon wherein the coating material is capable of dissolving or swelling the surface of the resin film substrate. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【0001】
【発明の属する技術分野】
本発明は、透明な塗工フィルム及びこれを用いた反射防止フィルムに関し、特に液晶ディスプレイ、プラズマディスプレイ等の表面保護フィルムとして好適な塗工フィルム及びこれを用いた反射防止フィルムに関する。
【0002】
【従来技術】
各種の光学レンズ、計器のカバー、窓ガラス、あるいは液晶ディスプレイ、プラズマディスプレイ等の各種表示体の表面保護や反射防止を目的として、塗工したハードコート層を有する塗工フィルムが利用されている。ところが、この塗工フィルムでは、ハードコート層表面の反射光、及びハードコート層とフィルム基材との界面の反射光が互いに干渉して干渉色を生じ、さらにハードコート層の塗工厚みにムラがあると干渉色にも「色ムラ」と呼ばれる模様が生じて視認性を低下させる問題がある。
そこで、色ムラを改善するため、ハードコート層と基材との屈折率の差を低減させる技術が報告されている(例えば、特許文献1〜3参照)。
【0003】
【特許文献1】
特開平07−56002号公報
【特許文献2】
特開平07−151902号公報
【特許文献3】
特開平08−179123号公報
【0004】
【発明が解決しようとする課題】
しかしながら、上記特許文献1に記載された技術の場合、ハードコート層とプラスチック基板の屈折率を厚み方向にほぼ連続的に変化させることで色ムラは解消するものの、ハードコート層をCVD法によって形成するため、生産性、コストの点で問題がある。
【0005】
又、特許文献2に記載された技術の場合、ハードコート層となる塗膜と基材フィルムとの屈折率の差を小さくするべく、塗膜へ金属酸化物超微粒子を添加している。そのため、この微粒子が光を散乱してヘイズ(曇り)が生じたり、全光線透過率が低下するので、ヘイズ度が低く、高い透過鮮映性が要求されるフィルムが得られない。
【0006】
一方、特許文献3に記載された技術は、フィルム基材の屈折率に近い屈折率を持つ塗膜を形成させるものである。しかし、液晶ディスプレイ、プラズマディスプレイ等に使用される塗工フィルムでは、フィルム基材として光学異方性が無いセルロースエステルフィルムが用いられることが多いが、これと屈折率が近い塗料の選択が難しいため、使用できるフィルム基材に制限がある。
【0007】
また、色ムラの原因となる厚みムラを解消するため、従来は塗工ヘッドの精度向上、塗料のレベリング性、塗工時のフィルムテンション調整等の操作を行っていた。しかし、塗工ヘッドの精度向上には限界があり、又、塗料のレベリング性やフィルムテンションを調整しても、キャスト法で製造された平面性が悪い(表面の凹凸が大きい)フィルム、例えばトリアセチルセルロースフィルム等のセルロースエステルフィルムを用いた場合は厚みムラの解消が難しい。
【0008】
このように従来の技術では、基材フィルムに屈折率を近づけるために塗膜へ微粒子を添加するため、ヘイズ度が高くなって透過鮮映性が低下したり、あるいは使用できるフィルム基材やハードコート層に制限があった。
従って本発明の目的は、種々のフィルム基材やハードコート層を用いても干渉による色ムラを防止できるとともに、透過率が高い塗工フィルム及びこれを用いた反射防止フィルムを提供することにある。
【0009】
【課題を解決するための手段】
本発明者等は、上記課題を解決するために種々検討した結果、フィルム基体にハードコート層となる塗膜を塗布する際、フィルム基体の表面を溶解(膨潤)させることにより、ハードコート層とフィルム基体の界面を一体化させ、干渉による色ムラを防止できることを見出した。そして、このようにすると、ハードコート層へ微粒子を添加する必要がないので、ヘイズ度が低く高い透過鮮映性を有する塗工フィルムを得られることも判明した。
従って、本発明の上記の目的は、透明な樹脂フィルム基体の少なくとも片面に、有機溶媒と樹脂組成物とを主成分とする塗料を塗工して透明な塗工層を形成させてなる塗工フィルムであって、前記塗料が前記樹脂フィルム基体の表面を溶解又は膨潤可能であることを特徴とする塗工フィルムによって達成された。
特に、JIS−K7105に従って測定したヘイズ度が0.1〜3%である場合に、高い透過鮮映性が得られる。
又、前記樹脂組成物が熱硬化型樹脂組成物または紫外線硬化型樹脂組成物である場合や、前記樹脂フィルム基体がセルロースエステルフィルムであり、かつ前記有機溶媒が分子量100以下のケトン系有機溶剤または/及びエステル系有機溶剤である場合に、色ムラを有効に防止できる。
さらに、前記塗工層の屈折率と前記樹脂フィルム基体の屈折率との差が0.013以上である場合にも、色ムラを有効に防止できる。
本発明の上記の目的は、前記塗工フィルムの塗工層の上に、さらに低屈折率層を設け、前記低屈折率層の屈折率は前記塗工層の屈折率より低く、かつその差が0.01以上である反射防止フィルムによっても達成された。
【0010】
【発明の実施の形態】
以下、本発明を具体的に説明する。本発明の塗工フィルムは、透明な樹脂フィルム基体の少なくとも片面に、後述する塗料を塗工して透明な塗工層を形成させたことを特徴としている。そして、前記塗料が樹脂フィルム基体の表面を溶解又は膨潤させ、塗工層と樹脂フィルム基体の界面を一体化させて不明瞭とするため、色ムラを有効に防止するものと考えられる。
【0011】
本発明で用いる樹脂フィルム基体は、透明であればどのような樹脂フィルムを用いても良いが、例えば、トリアセチルセルロースフィルム、ジアセチルセルロースフィルム、アセテートブチレートセルロースフィルム、ポリエーテルサルホンフィルム、ポリアクリル系樹脂フィルム、ポリウレタン系樹脂フィルム、ポリエステルフィルム、ポリカーボネートフィルム、ポリスルホンフィルム、ポリエーテルフィルム、トリメチルペンテンフィルム、ポリエーテルケトンフィルム、(メタ)アクリロニトリルフィルム等が使用できる。特に、トリアセチルセルロースフィルム、及び一軸延伸ポリエステルが透明性に優れ、光学的に異方性が無い点で好適に用いられる。フィルムの厚みは、通常は8〜1000μm程度のものが好適に用いられる。
【0012】
上記塗料は、有機溶媒と樹脂組成物を主成分とし、樹脂フィルム基体の表面を溶解又は膨潤可能であることが必要である。ここで溶解又は膨潤可能とは、樹脂フィルム基体に塗料を塗布することによって樹脂フィルム基体の表面の成分が塗料中に溶出する状態を示し、X線分析や赤外線分析などにより塗工層を分析すると樹脂フィルム表面より溶出した成分を検出することができる。
【0013】
そして、塗料を塗工して得られる塗工層と樹脂フィルム基体の断面を電子顕微鏡などで観察すると、樹脂フィルム基体を溶解しない塗料を用いた場合には上記界面が明瞭に確認できるが、本発明の場合は界面が不明瞭となったり、消失する。これにより、上記界面で塗工層と樹脂フィルム基体が一体化し、界面での両者の屈折率差が急峻でなく連続的に変化し、干渉による色ムラを防止できるものと考えられる。そのため、本発明においては、従来のように塗工層と樹脂フィルム基体の屈折率差が小さい材料を選択したり、塗工層に微粒子を添加する必要がなく、種々のフィルム基体を選択できるとともに、ヘイズ度が低く高い透過鮮映性を有する塗工フィルムが得られる。
【0014】
特に、上記したトリアセチルセルロースフィルム等のセルロースエステルフィルムは、キャスト法で製造され平面性が悪い(表面の凹凸が大きい)ので、その上に形成する塗工層の厚みムラが生じ易く、それに起因して色ムラも発生し易くなるが、厚みムラ自体を解消することは技術的に難しい。しかし、本発明では、上述のように塗工層と樹脂フィルム基体の界面での両者の屈折率差を急峻でなく連続的に変化させるので、厚みムラを解消させずとも色ムラを防止できる。
【0015】
塗料に用いる有機溶媒は、特に制限はなく、例えば、ケトン系有機溶剤、エステル系有機溶剤、芳香族類、アルコール類、セロソルブ類など公知の溶剤を用いることができる。そして、樹脂フィルム基体がトリアセチルセルロースフィルム等のセルロースエステルフィルムである場合は、ケトン系有機溶剤または/及びエステル系有機溶剤、特に分子量100以下のケトン系有機溶剤または/及びエステル系有機溶剤を用いることが好ましい。上記溶剤の分子量が100以下であるとセルロースエステルフィルム表面を溶解する効果が大きい。分子量が100未満であるケトン類としてアセトン、メチルエチルケトン、メチル−n−プロピルケトン、ジエチルケトン、シクロヘキサノンなどが挙げられる。分子量が100未満であるエステル類としては酢酸メチル、酢酸エチル、プロピオン酸メチルなどが挙げられ、なかでも好ましい有機溶剤はシクロヘキサノンと酢酸エチルである。
【0016】
又、樹脂フィルム基体が上記セルロースエステルフィルムの場合、分子量100以下のケトン系有機溶剤または/及びエステル系有機溶剤が有機溶媒全体の50重量%以上(より好ましくは、60重量%以上)であることが好ましい。50重量%未満であると、樹脂フィルム基体の溶解や膨潤が不充分となり、干渉による色ムラ防止効果が得られにくいからである。但し、上記ケトン系有機溶剤やエステル系有機溶剤の割合が高すぎると、樹脂フィルム基体を過度に溶解したり膨潤するために樹脂フィルム基体が曇ったり、樹脂フィルム基体表面から溶出する物質が過度に塗膜に混入し、塗工層のハード性(硬さ)が低下するおそれがある。ここで、塗工層のハード性とは、塗工層の硬さをいい、ハード性が良好であるとは、スチールウールなど硬い物で擦っても塗工層表面に傷が入りにくい状態を示す。
【0017】
従って、通常は、上記ケトン系有機溶剤やエステル系有機溶剤の割合を80重量%以下とすることが好ましいが、塗料中の有機溶媒の割合を樹脂組成物に比べて少なくし、塗料の固形分濃度を高くするなどの方法により、フィルム基体に対する塗料の溶解の程度を調整すれば、有機溶媒中における上記ケトン系有機溶剤やエステル系有機溶剤の割合を80重量%以上としても差し支えない。
【0018】
塗料における有機溶媒の割合は、35〜60重量%とするのが好ましい。溶媒濃度が35重量%未満であると、樹脂フィルム基体の溶解や膨潤が不充分となり、干渉による色ムラ防止効果が得られにくい。一方、溶媒濃度が60重量%を超えると、樹脂フィルム基体を過度に溶解したり膨潤するために樹脂フィルム基体が曇ったり、樹脂フィルム基体表面から溶出する物質が過度に塗膜に混入し、塗工層のハード性(硬さ)が低下するおそれがある。
【0019】
塗料に用いる樹脂組成物は、透明であればよく、熱可塑性樹脂、熱硬化型樹脂、電離放射線硬化型樹脂などを単独又は混合して使用できる。特に、塗工層にハード性を付与するためには、硬化型樹脂を用いることが好ましく、硬化に熱を必要としない電離放射線硬化型樹脂組成物がより好ましい。ここで、電離放射線硬化型樹脂組成物は電子線や紫外線等を照射することによって硬化し、上記有機溶媒との溶解性が良好であれば、硬化後の屈折率に関係なくどのようなものも使用できる。
【0020】
電離放射線硬化型樹脂組成物としては、ウレタンアクリレート系樹脂、ポリエステルアクリレート系樹脂、及びエポキシアクリレート系樹脂等の中から適宜選択することが可能であり、特に、分子内に2個以上の(メタ)アクリロイル基を有する紫外線硬化可能な多官能アクリレ−トからなるものが好ましい。上記多官能アクリレ−トの具体例としては、(メタ)ネオペンチルグリコ−ルジアクリレ−ト、(メタ)1、6ヘキサンジオ−ルジアクリレ−ト、(メタ)トリメチロ−ルプロパントリアクリレ−ト、(メタ)ジトリメチロ−ルプロパンテトラアクリレ−ト、(メタ)ペンタエリスリト−ルテトラアクリレ−ト、(メタ)ペンタエリスリト−ルトリアクリレ−ト、(メタ)ジペンタエリスリト−ルヘキサアクリレ−ト等のポリオ−ルポリアクリレ−ト、ビスフェノ−ルAジグリシジルエ−テルのジアクリレ−ト、ネオペンチルグリコ−ルジグリシジルエ−テルのジアクリレ−ト、(メタ)1、6ヘキサンジオ−ルジグリシジルエ−テルのジアクリレ−トなどのエポキシ(メタ)アクリレ−ト、多価アルコ−ルと多価カルボン酸および/またはその無水物とアクリル酸とをエステル化することによって得ることが出来るポリエステル(メタ)アクリレ−ト、多価アルコ−ル、多価イソシアネ−ト及び水酸基含有アクリレ−トを反応させることによって得られるウレタンアクリレ−ト、ポリシロキサンポリアクリレ−ト等を挙げることができる。
【0021】
前記の紫外線硬化可能な多官能アクリレ−トは単独又は2種以上を混合して用いてもよく、塗料に用いる樹脂組成物をすべて重合性アクリレ−トとしてもよいが、樹脂組成物のうち重合性アクリレ−トの割合を95〜50重量%とするのが好ましい。尚、多官能アクリレ−トの他、2−ヒドロキシ(メタ)アクリレ−ト、2−ヒドロキシプロピル(メタ)アクリレ−ト、グリシジル(メタ)アクリレ−ト等の単官能アクリレ−トを、樹脂組成物全体の10重量%以下の量となるよう添加することもできる。
【0022】
また、塗工層の硬度を調整する目的で、塗料に重合性オリゴマ−を添加することができる。このような重合性オリゴマ−としては、末端メタクリレ−トポリメチルメタクリレ−ト、末端スチリルポリメタクリレ−ト、末端メタクリレ−トポリスチレン、末端メタクリレ−トポリエチレングリコ−ル、末端メタクリレ−トアクリロニトリル−スチレン共重合体、末端メタクリレ−トスチレン−メチルメタクリレ−ト共重合体などのマクロモノマ−を挙げることができる。重合性オリゴマ−の含有割合は、樹脂組成物全体の5〜50重量%とするのが好ましい。
【0023】
さらに、塗工層の圧着防止などの目的で、塗料に微粒子を添加してもよい。但し、微粒子を添加しすぎると後述するヘイズ度が高くなり、色ムラは目立たなくなるが、透過率や透過鮮映度が低下するため、ヘイズ度が高くならないよう微粒子の添加量を制限するのが好ましい。なお、圧着とは、塗工フィルムを巻き取りロール状にした際に、塗工層と基材フィルムのり面とが密着する現象をいい、圧着が部分的に生じたロールが巻きゆるみ、巻き締りしたり、あるいは保管温度によって膨張、収縮すると、ロールをほどいた時にフィルムに変形が生じる。
【0024】
微粒子は、塗料に分散させることが出来るものであれば特に限定されず、例えば有機又は無機の顔料を用いることができる。具体的には、シリカ、アルミナ、ジルコニア等の無機顔料の他、アクリル樹脂、ポリスチレン樹脂、ポリ塩化ビニル樹脂、ポリカーボネート樹脂、PMMA樹脂、シリコン樹脂、ポリウレタン樹脂等のポリマービーズが挙げられる。
【0025】
さらに、本発明の効果を損なわない範囲で、塗料に消泡剤、レベリング剤、揺変剤、増粘剤、粒子分散剤、帯電防止剤、酸化防止剤、紫外線吸収剤、光安定剤、重合禁止剤を含有することができる。塗料中の固形分濃度が低く、塗布した液膜が乾燥中に大きな厚みムラを生じて色ムラが懸念される場合は、レベリング剤、揺変剤、増粘剤を添加すればよい。
【0026】
以上のようにして調整された塗料は、マイクログラビアコーター、グラビアコーター、マイヤーバーコーター、ダイコーター等の塗工装置を用いて塗工することができる。塗工量は、乾燥後の塗工層が約2〜12g/mになるように調整すればよい。塗工後の塗料は、乾燥させたり、硬化型樹脂の場合は硬化処理することにより、塗工層を形成することができる。
【0027】
このようにして、塗工フィルムを製造することができる。好ましくは、塗工フィルムのヘイズ度をJIS−K7105に従って測定した値が0.1〜3%であるのがよい。ヘイズ度が3%を超えると塗工フィルムの透過率が低下し、透過鮮映性の高い塗工フィルムが得られないからである。ヘイズ度の下限を0.1%未満としたのは、樹脂フィルム基体のヘイズ度が約0.1%であり、これ以下とするのは実用上困難だからである。より好ましくはヘイズ度を0.1〜1%とする。
【0028】
又、本発明の塗工フィルムにおいては、塗工層の屈折率と樹脂フィルム基体の屈折率との差が0.013以上であっても、色ムラを有効に防止できるという特徴がある。つまり、従来はハードコート層と基材との屈折率の差を低減させ、干渉を生じ難くすることで色ムラを抑制していた。この場合、前記特許文献2によれば、両者の屈折率の差が0.003以上あると色ムラが生じるとされている。しかし、本発明はこれと全く異なる原理である、樹脂フィルム基体表面を溶解させて塗工層と樹脂フィルム基体の界面を不明瞭にさせる手法により色ムラを抑制している。又、本発明者らの検討では、両者の屈折率の差が0.013以上あると色ムラが生じることがわかった。従って、本発明では、塗工層と樹脂フィルム基体の屈折率差を調整する必要がなく、両者の屈折率差が0.013以上であっても構わない。そのため、フィルム基体や塗工層の選択の自由度が大きくなる。
【0029】
さらに、本発明の塗工フィルムの塗工層の上に低屈折率層を設けることにより反射防止フィルムとしてもよい。この場合、反射防止能を付与させるため、低屈折率層の屈折率を塗工層の屈折率よりも低くし、かつその差を0.01以上とする。又、塗工層の上に高屈折率層を設け、該高屈折率層の表面に低屈折率層を設けてもよいが、この場合も、低屈折率層の屈折率を高屈折率層の屈折率よりも低くし、かつその差を0.01以上とする。低屈折率層を形成する材料としては、有機ケイ素化合物、フッ素化合物、ホウ素化合物等を用いることができる。又、高屈折率を形成する材料としては、チタン酸化物(二酸化チタンやアルコキシチタン)や、高屈折率を有する金属酸化物微粒子を樹脂と混合したものを用いることができる。
【0030】
【実施例】
以下、本発明を実施例及び比較例によって更に詳述するが、本発明はこれらによって限定されるものではない。又、特に断らない限り、以下に記載する「部」及び「%」は、それぞれ「重量部」及び「重量%」を表す。
【0031】
1.塗料の調整
表1に示す樹脂組成物、有機溶媒、及び他の添加剤を用い、各実施例及び比較例毎に組成の異なる塗料を調整した。樹脂組成物はUV硬化型樹脂H601(ペンタエリスリトール系モノマー主成分、三洋化成株式会社製の商品名)を用い、上記有機溶媒の他、レベリング剤BYK−300(ビックケミー社製の商品名)対液0.05部を配合した。なお、比較例8、9の場合は、塗料にそれぞれ粒子径1.6、1.5μmのシリカ微粒子を配合した。樹脂組成物、有機溶媒、微粒子の配合割合は表1に示すとおりである。なお、表中のIPAはイソプロピルアルコールである。
【0032】
2.塗工フィルムの作成
表1に示すフィルム基体の一方の面に、上記塗料をマイヤーバーを用いて塗工した。塗工後、60℃のドライヤーで塗料中の希釈溶剤を蒸発させた後、UV光を照射して樹脂を硬化させて塗工層を形成し、塗工フィルムを作成した。塗工層の厚みは6μmであった。なお、表1において、TACは、厚さ80μmのトリアセチルセルロースフィルム(FT−80UZ:富士写真フィルム株式会社製の商品名)であり、ACは、厚さ125μmのアクリルフィルム(テクノロイS001:住友化学工業株式会社製の商品名)であり、PEは、厚さ75μmのポリエステルフィルム(A−4300:東洋紡績株式会社製の商品名)である。
なお、比較例9のみは次のようにして塗工した。まず、上記TACの一方の面に、各成分を表1の「/」の上側添字の配合割合とした塗料をマイヤーバーにて塗工し、各実施例と同様にして塗工フィルムを作成した。このときの塗工層の厚みは3μmで、その表面粗さRaは0.35μmであった。この塗工層の表面に、さらに各成分を表1の「/」の下側添字の配合割合とした塗料をマイヤーバーにて塗工し、各実施例と同様にして塗工フィルムを作成した。この第2の塗工層の厚みは3μmであり、2つの塗工層の合計厚みが6μmの塗工フィルムとした。
又、実施例1の塗工フィルムの塗工層上に、アルコキシシリケート100部(L1001:日産化学株式会社製)、エタノール300部(関東化学製、特級)を配合して固形分濃度1%に調整した塗料をマイヤーバーで塗工し、送風乾燥機で60℃、1分の条件で乾燥させることにより、膜厚110nmの低屈折率層を形成し、反射防止フィルムを得た。これを実施例16とする。得られた反射防止フィルムの平均正反射率(波長400〜700nm)は3.0%以下であり、低屈折率層を設けない実施例1の塗工フィルムの平均正反射率が5.6%であることから、この反射防止フィルムが充分な反射防止効果を有することがわかった。なお、反射率は分光光度計(日立製作所製のU−3310)で測定した。
【0033】
【表1】

Figure 2004263082
【0034】
3.評価
(1)界面の状態
各塗工フィルムの断面写真を走査型電子顕微鏡で撮影し、塗工層と樹脂フィルム基体との界面が明瞭に観察できたものを(フィルム基体が)「溶解せず」、界面が不明瞭なものを「溶解」と評価した。
(2)色ムラ
塗工フィルムの非塗工面側をスチールウールで擦り、その表面を黒色のスプレー塗料で着色してよく乾燥させた。この塗工フィルムを暗室で3波長タイプの蛍光灯下で塗工面側から目視観察したときの、色ムラの度合を評価した。
○:色ムラなし
△:わずかに色ムラあり
×:色ムラが目立つ
××:色ムラが顕著に目立つ
(3)対擦傷性
塗工フィルムの塗工層表面に、400gの荷重をかけた#0000のスチールウールを置き、スチールウールを動かして塗工層表面を擦り、発生した傷の程度を目視判定した。
○:擦傷なし
△:わずかに擦傷あり
×:擦傷が目立つ
(4)ヘイズ度
塗工フィルムのヘイズ度をJIS−K7105に従って測定した。
【0035】
得られた結果を表2に示す。なお、表2において、ケトン−エステルの割合とは、塗料に用いる有機溶媒全体に対する、分子量100以下のケトン類及び/またはエステル類の配合割合をいう。又、有機溶媒の割合とは、塗料(有機溶媒、樹脂組成物、及び他の添加剤)における有機溶媒の配合割合をいう。
【0036】
【表2】
Figure 2004263082
【0037】
表2から明らかなように、本発明の実施例1〜15では、色ムラ防止効果、対擦傷性に優れ、又,ヘイズ度が1%以下であり透過鮮映性に優れることが実証された。なお、実施例14では有機溶媒の割合が65重量%と多いため、対擦傷性が低下したが、本発明の目的とする色ムラ防止や、ヘイズ度の低減を達成することができた。そして、各実施例では、いずれも界面の樹脂フィルム基体が溶解していた。
【0038】
一方、比較例1、2の場合、有機溶媒としてシクロヘキサノンの代わりにそれぞれメチルイソブチルケトン、酢酸イソプロピルを用いたため、界面の樹脂フィルム基体が溶解せず、色ムラ防止効果が得られなかった。
【0039】
比較例3〜5の場合、有機溶媒中のシクロヘキサノン(ケトン−エステル)の割合が40〜0重量%と低いため、界面の樹脂フィルム基体が溶解せず、色ムラ防止効果が得られなかった。特に、ケトン−エステルが配合されていない比較例5の場合に色ムラ防止効果が最も劣化した。
【0040】
比較例6の場合、有機溶媒の割合が30重量%と低いため、界面の樹脂フィルム基体が溶解せず、色ムラ防止効果が得られなかった。
【0041】
比較例7の場合、樹脂フィルム基体としてアクリルフィルムを用いたが、塗料の有機溶媒の選択が不適であったため、界面の樹脂フィルム基体が溶解せず、色ムラ防止効果が得られなかった。
【0042】
比較例8,9の場合、塗工層に微粒子を添加したため、色ムラ防止効果は良好となったものの、ヘイズ度が3%を超えてしまい、フィルムの透過率や透過鮮映度が低下した。
【0043】
なお、本発明の各実施例では、ケトン−エステルの割合がいずれも50〜100重量%に範囲にあり、又、実施例14を除き、有機溶媒の割合がいずれも35〜60重量%に範囲にあった。これらのことから、ケトン−エステルの割合を50〜100重量%とし、又、有機溶媒の割合を35〜60重量%とするのが好ましいことが明らかである。
【0044】
【発明の効果】
本発明においては、塗工層となる塗料が樹脂フィルム基体の表面を溶解又は膨潤させるので、干渉による色ムラを防止できるとともに透過率や透過鮮映度が高い塗工フィルムが得られる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a transparent coating film and an antireflection film using the same, and more particularly, to a coating film suitable as a surface protection film for a liquid crystal display, a plasma display and the like, and an antireflection film using the same.
[0002]
[Prior art]
2. Description of the Related Art Coated films having a coated hard coat layer are used for the purpose of protecting the surface of various optical lenses, instrument covers, window glasses, and various display bodies such as liquid crystal displays and plasma displays and preventing reflection. However, in this coated film, the reflected light on the surface of the hard coat layer and the reflected light on the interface between the hard coat layer and the film substrate interfere with each other to generate an interference color, and further, the coating thickness of the hard coat layer becomes uneven. If there is, there is a problem that a pattern called "color unevenness" occurs in the interference color, and the visibility is reduced.
Then, in order to improve color unevenness, a technique for reducing the difference in the refractive index between the hard coat layer and the substrate has been reported (for example, see Patent Documents 1 to 3).
[0003]
[Patent Document 1]
Japanese Patent Application Laid-Open No. 07-56002 [Patent Document 2]
JP 07-151902 A [Patent Document 3]
JP 08-179123 A
[Problems to be solved by the invention]
However, in the case of the technique described in Patent Document 1, although the color unevenness is eliminated by changing the refractive indexes of the hard coat layer and the plastic substrate almost continuously in the thickness direction, the hard coat layer is formed by the CVD method. Therefore, there is a problem in terms of productivity and cost.
[0005]
Further, in the case of the technique described in Patent Document 2, ultrafine metal oxide particles are added to the coating film in order to reduce the difference in refractive index between the coating film serving as the hard coat layer and the base film. For this reason, the fine particles scatter light to cause haze (cloudiness) or decrease the total light transmittance, so that a film having a low haze degree and requiring high transmission clearness cannot be obtained.
[0006]
On the other hand, the technique described in Patent Document 3 is to form a coating film having a refractive index close to the refractive index of a film substrate. However, in a coating film used for a liquid crystal display, a plasma display, or the like, a cellulose ester film having no optical anisotropy is often used as a film substrate, but it is difficult to select a paint having a refractive index close to this. In addition, there is a limitation on the film substrate that can be used.
[0007]
Further, in order to eliminate thickness unevenness which causes color unevenness, conventionally, operations such as improvement in accuracy of a coating head, leveling property of a coating material, and adjustment of a film tension at the time of coating have been performed. However, there is a limit to improving the accuracy of the coating head, and even if the leveling property of the paint and the film tension are adjusted, a film produced by the casting method with poor flatness (large surface irregularities), for example, When a cellulose ester film such as an acetyl cellulose film is used, it is difficult to eliminate thickness unevenness.
[0008]
As described above, in the conventional technology, fine particles are added to the coating film to bring the refractive index closer to the base film, so that the haze degree is increased and transmission clearness is reduced, or the film base or hard film which can be used is used. There were restrictions on the coat layer.
Therefore, an object of the present invention is to provide a coating film having high transmittance and an antireflection film using the same, which can prevent color unevenness due to interference even when using various film substrates and hard coat layers. .
[0009]
[Means for Solving the Problems]
The present inventors have conducted various studies to solve the above problems, and as a result, when applying a coating film to be a hard coat layer on a film substrate, the surface of the film substrate is dissolved (swelled) to form a hard coat layer. They have found that the interface of the film substrate can be integrated to prevent color unevenness due to interference. Then, it was also found that in this case, it was not necessary to add fine particles to the hard coat layer, so that a coated film having a low haze degree and having high transmissive clarity could be obtained.
Accordingly, an object of the present invention is to provide a transparent resin film substrate having at least one surface coated with a coating mainly composed of an organic solvent and a resin composition to form a transparent coating layer. This is achieved by a coating film, wherein the coating material is capable of dissolving or swelling the surface of the resin film substrate.
In particular, when the haze degree measured in accordance with JIS-K7105 is 0.1 to 3%, high transmission clearness is obtained.
Further, when the resin composition is a thermosetting resin composition or an ultraviolet-curable resin composition, or when the resin film substrate is a cellulose ester film, and the organic solvent is a ketone-based organic solvent having a molecular weight of 100 or less or And / or when it is an ester organic solvent, color unevenness can be effectively prevented.
Furthermore, even when the difference between the refractive index of the coating layer and the refractive index of the resin film substrate is 0.013 or more, color unevenness can be effectively prevented.
The object of the present invention is to further provide a low refractive index layer on the coating layer of the coating film, the refractive index of the low refractive index layer is lower than the refractive index of the coating layer, and the difference Was also achieved by an antireflection film having a value of 0.01 or more.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described specifically. The coating film of the present invention is characterized in that a transparent coating film is formed on at least one surface of a transparent resin film substrate by applying a coating material described later. The paint dissolves or swells the surface of the resin film substrate, and unifies the interface between the coating layer and the resin film substrate, thereby making it difficult to effectively prevent color unevenness.
[0011]
As the resin film substrate used in the present invention, any resin film may be used as long as it is transparent, for example, triacetyl cellulose film, diacetyl cellulose film, acetate butyrate cellulose film, polyether sulfone film, polyacryl Resin films, polyurethane resin films, polyester films, polycarbonate films, polysulfone films, polyether films, trimethylpentene films, polyetherketone films, (meth) acrylonitrile films, and the like can be used. In particular, a triacetyl cellulose film and a uniaxially stretched polyester are preferably used because they are excellent in transparency and have no optical anisotropy. Usually, a film having a thickness of about 8 to 1000 μm is suitably used.
[0012]
It is necessary that the paint has an organic solvent and a resin composition as main components, and is capable of dissolving or swelling the surface of the resin film substrate. Here, dissolvable or swellable means that the components on the surface of the resin film substrate are eluted into the paint by applying the paint to the resin film substrate, and when the coating layer is analyzed by X-ray analysis or infrared analysis, etc. Components eluted from the resin film surface can be detected.
[0013]
When the cross section of the coating layer obtained by applying the coating material and the resin film substrate is observed with an electron microscope or the like, the above interface can be clearly confirmed when a coating material that does not dissolve the resin film substrate is used. In the case of the invention, the interface becomes unclear or disappears. Thereby, it is considered that the coating layer and the resin film substrate are integrated at the above-mentioned interface, the difference in refractive index between the two at the interface is not steep, but changes continuously, and color unevenness due to interference can be prevented. Therefore, in the present invention, there is no need to select a material having a small refractive index difference between the coating layer and the resin film substrate as in the related art, and it is not necessary to add fine particles to the coating layer, and various film substrates can be selected. Thus, a coated film having a low haze degree and high transmissive clarity can be obtained.
[0014]
In particular, cellulose ester films such as the above-mentioned triacetylcellulose films are manufactured by a casting method and have poor flatness (large irregularities on the surface), so that a coating layer formed thereon tends to have uneven thickness, which is caused by Color unevenness easily occurs, but it is technically difficult to eliminate the thickness unevenness itself. However, in the present invention, as described above, the refractive index difference at the interface between the coating layer and the resin film substrate is changed not steeply but continuously, so that color unevenness can be prevented without eliminating thickness unevenness.
[0015]
The organic solvent used for the coating material is not particularly limited, and for example, a known solvent such as a ketone organic solvent, an ester organic solvent, aromatics, alcohols, and cellosolves can be used. When the resin film substrate is a cellulose ester film such as a triacetyl cellulose film, use a ketone-based organic solvent or / and an ester-based organic solvent, particularly a ketone-based organic solvent or / and an ester-based organic solvent having a molecular weight of 100 or less. Is preferred. When the molecular weight of the solvent is 100 or less, the effect of dissolving the surface of the cellulose ester film is large. Examples of ketones having a molecular weight of less than 100 include acetone, methyl ethyl ketone, methyl-n-propyl ketone, diethyl ketone, and cyclohexanone. Esters having a molecular weight of less than 100 include methyl acetate, ethyl acetate, methyl propionate and the like, and among them, preferred organic solvents are cyclohexanone and ethyl acetate.
[0016]
When the resin film substrate is the above-mentioned cellulose ester film, the content of the ketone organic solvent and / or the ester organic solvent having a molecular weight of 100 or less is 50% by weight or more (more preferably 60% by weight or more) of the whole organic solvent. Is preferred. If the content is less than 50% by weight, the dissolution or swelling of the resin film substrate becomes insufficient, and it is difficult to obtain the effect of preventing color unevenness due to interference. However, if the proportion of the ketone-based organic solvent or ester-based organic solvent is too high, the resin film substrate becomes cloudy due to excessive dissolution or swelling of the resin film substrate, and substances eluted from the surface of the resin film substrate become excessive. There is a possibility that the hardness (hardness) of the coating layer is reduced by being mixed into the coating film. Here, the hardness of the coating layer refers to the hardness of the coating layer, and the term “good hardness” means that the surface of the coating layer is hardly damaged even when rubbed with a hard material such as steel wool. Show.
[0017]
Therefore, it is usually preferable that the proportion of the ketone-based organic solvent or ester-based organic solvent be 80% by weight or less, but the proportion of the organic solvent in the paint is reduced as compared with the resin composition, and the solid content of the paint is reduced. If the degree of dissolution of the paint in the film substrate is adjusted by, for example, increasing the concentration, the proportion of the ketone-based organic solvent or ester-based organic solvent in the organic solvent may be set to 80% by weight or more.
[0018]
The proportion of the organic solvent in the paint is preferably from 35 to 60% by weight. If the solvent concentration is less than 35% by weight, dissolution and swelling of the resin film substrate become insufficient, and it is difficult to obtain the effect of preventing color unevenness due to interference. On the other hand, if the solvent concentration exceeds 60% by weight, the resin film substrate is excessively dissolved or swelled, so that the resin film substrate becomes cloudy or substances eluted from the surface of the resin film substrate are excessively mixed into the coating film. Hardness (hardness) of the working layer may be reduced.
[0019]
The resin composition used for the coating material only needs to be transparent, and a thermoplastic resin, a thermosetting resin, an ionizing radiation-curable resin, or the like can be used alone or in combination. In particular, in order to impart hardness to the coating layer, a curable resin is preferably used, and an ionizing radiation-curable resin composition that does not require heat for curing is more preferable. Here, the ionizing radiation-curable resin composition is cured by irradiating an electron beam, ultraviolet light, or the like, as long as it has good solubility with the organic solvent, regardless of the refractive index after curing. Can be used.
[0020]
The ionizing radiation-curable resin composition can be appropriately selected from urethane acrylate-based resins, polyester acrylate-based resins, epoxy acrylate-based resins, and the like. It is preferable to use an ultraviolet-curable polyfunctional acrylate having an acryloyl group. Specific examples of the above polyfunctional acrylates include (meth) neopentylglycol diacrylate, (meth) 1,6 hexanediol diacrylate, (meth) trimethylolpropane triacrylate, (meth) ) Polyol polyacrylates such as ditrimethylolpropane tetraacrylate, (meth) pentaerythritol tetraacrylate, (meth) pentaerythritol triacrylate, (meth) dipentaerythritol hexaacrylate and the like. Epoxy, such as diacrylate of bisphenol A diglycidyl ether, diacrylate of neopentyl glycol diglycidyl ether, and diacrylate of (meth) 1,6 hexanediol diglycidyl ether ) Acrylates, polyalcohols and polycarboxylic acids and / or Urethane obtained by reacting polyester (meth) acrylate, polyhydric alcohol, polyvalent isocyanate and hydroxyl group-containing acrylate, which can be obtained by esterifying the anhydride of the above with acrylic acid. Acrylate and polysiloxane polyacrylate can be exemplified.
[0021]
The above-mentioned UV-curable polyfunctional acrylates may be used alone or as a mixture of two or more kinds, and the resin composition used for the coating may be all polymerizable acrylate. It is preferable that the proportion of the acrylate is 95 to 50% by weight. In addition to the polyfunctional acrylate, a monofunctional acrylate such as 2-hydroxy (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, etc. is used as a resin composition. It can also be added so as to be 10% by weight or less of the whole.
[0022]
For the purpose of adjusting the hardness of the coating layer, a polymerizable oligomer can be added to the paint. Examples of such a polymerizable oligomer include terminal methacrylate polymethyl methacrylate, terminal styryl polymethacrylate, terminal methacrylate polystyrene, terminal methacrylate polyethylene glycol, and terminal methacrylate acrylonitrile. Macromonomers such as styrene copolymer and terminal methacrylate styrene-methyl methacrylate copolymer can be mentioned. The content ratio of the polymerizable oligomer is preferably 5 to 50% by weight of the whole resin composition.
[0023]
Further, fine particles may be added to the paint for the purpose of preventing pressure-bonding of the coating layer. However, if the fine particles are added too much, the haze degree described later becomes high, and the color unevenness becomes inconspicuous, but the transmittance and the transmission sharpness decrease, so that the addition amount of the fine particles is limited so that the haze degree does not increase. preferable. In addition, pressure bonding refers to a phenomenon in which when a coating film is formed into a take-up roll, the coating layer and the surface of the base film are in close contact with each other. If the roll is unwound or expanded or contracted due to storage temperature, the film will be deformed when the roll is unwound.
[0024]
The fine particles are not particularly limited as long as they can be dispersed in the coating material. For example, organic or inorganic pigments can be used. Specifically, polymer beads such as an acrylic resin, a polystyrene resin, a polyvinyl chloride resin, a polycarbonate resin, a PMMA resin, a silicon resin, and a polyurethane resin, in addition to inorganic pigments such as silica, alumina, and zirconia, are mentioned.
[0025]
Furthermore, as long as the effects of the present invention are not impaired, antifoaming agents, leveling agents, thixotropic agents, thickeners, particle dispersants, antistatic agents, antioxidants, ultraviolet absorbers, light stabilizers, polymerization Inhibitors can be included. When the solid content concentration in the paint is low and the applied liquid film causes large thickness unevenness during drying and color unevenness is concerned, a leveling agent, a thixotropic agent, and a thickener may be added.
[0026]
The paint prepared as described above can be applied using a coating device such as a microgravure coater, a gravure coater, a Meyer bar coater, and a die coater. The coating amount may be adjusted so that the coating layer after drying is about 2 to 12 g / m 2 . The coating material after coating can be dried or, in the case of a curable resin, cured to form a coating layer.
[0027]
Thus, a coated film can be manufactured. Preferably, the value of the haze of the coated film measured according to JIS-K7105 is 0.1 to 3%. If the haze degree exceeds 3%, the transmittance of the coated film is reduced, and a coated film having high transmission clearness cannot be obtained. The reason why the lower limit of the haze degree is less than 0.1% is that the haze degree of the resin film substrate is about 0.1%, and it is practically difficult to reduce the haze degree to less than 0.1%. More preferably, the haze is set to 0.1 to 1%.
[0028]
Further, the coating film of the present invention has a feature that color unevenness can be effectively prevented even if the difference between the refractive index of the coating layer and the refractive index of the resin film substrate is 0.013 or more. That is, in the related art, the difference in the refractive index between the hard coat layer and the substrate is reduced, and interference is less likely to occur, thereby suppressing color unevenness. In this case, according to Patent Document 2, if the difference between the two refractive indexes is 0.003 or more, color unevenness occurs. However, in the present invention, color unevenness is suppressed by a technique that completely dissolves the surface of the resin film substrate to make the interface between the coating layer and the resin film substrate unclear, which is a completely different principle. In addition, the present inventors have found that when the difference between the two refractive indexes is 0.013 or more, color unevenness occurs. Therefore, in the present invention, it is not necessary to adjust the difference in the refractive index between the coating layer and the resin film substrate, and the difference between the two may be 0.013 or more. Therefore, the degree of freedom in selecting a film substrate and a coating layer is increased.
[0029]
Further, an antireflection film may be provided by providing a low refractive index layer on the coating layer of the coating film of the present invention. In this case, the refractive index of the low refractive index layer is made lower than the refractive index of the coating layer, and the difference is made 0.01 or more, in order to impart antireflection ability. Further, a high refractive index layer may be provided on the coating layer, and a low refractive index layer may be provided on the surface of the high refractive index layer. In this case, the refractive index of the low refractive index layer is also changed to the high refractive index layer. And the difference is 0.01 or more. As a material for forming the low refractive index layer, an organic silicon compound, a fluorine compound, a boron compound, or the like can be used. As a material for forming a high refractive index, titanium oxide (titanium dioxide or alkoxytitanium) or a material obtained by mixing metal oxide fine particles having a high refractive index with a resin can be used.
[0030]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" and "%" described below represent "parts by weight" and "% by weight", respectively.
[0031]
1. Preparation of Paints Using the resin compositions, organic solvents, and other additives shown in Table 1, paints having different compositions were prepared for each Example and Comparative Example. The resin composition is a UV-curable resin H601 (pentaerythritol-based monomer main component, trade name, manufactured by Sanyo Chemical Co., Ltd.). In addition to the above-mentioned organic solvent, a leveling agent BYK-300 (trade name, manufactured by BYK Chemie) 0.05 part was blended. In addition, in the case of Comparative Examples 8 and 9, silica fine particles having a particle diameter of 1.6 and 1.5 μm, respectively, were added to the paint. The mixing ratio of the resin composition, the organic solvent, and the fine particles is as shown in Table 1. IPA in the table is isopropyl alcohol.
[0032]
2. Preparation of Coated Film One of the surfaces of the film substrate shown in Table 1 was coated with the above coating material using a Meyer bar. After the coating, the diluting solvent in the coating was evaporated using a dryer at 60 ° C., and then the resin was cured by irradiating UV light to form a coating layer, thereby forming a coating film. The thickness of the coating layer was 6 μm. In Table 1, TAC is an 80 μm thick triacetyl cellulose film (FT-80UZ: trade name, manufactured by Fuji Photo Film Co., Ltd.), and AC is an 125 μm thick acrylic film (Technoloy S001: Sumitomo Chemical Co., Ltd.) PE is a 75 μm thick polyester film (A-4300: trade name, manufactured by Toyobo Co., Ltd.).
In addition, only the comparative example 9 was applied as follows. First, on one surface of the TAC, a coating material in which each component was mixed in the upper suffix of “/” in Table 1 was applied with a Meyer bar, and a coating film was prepared in the same manner as in each example. . At this time, the thickness of the coating layer was 3 μm, and the surface roughness Ra was 0.35 μm. On the surface of this coating layer, a coating material in which each component was added with a lower suffix of "/" in Table 1 was applied by a Meyer bar, and a coating film was prepared in the same manner as in each example. . The thickness of this second coating layer was 3 μm, and the total thickness of the two coating layers was 6 μm.
Further, 100 parts of alkoxysilicate (L1001: manufactured by Nissan Chemical Co., Ltd.) and 300 parts of ethanol (manufactured by Kanto Chemical Co., Ltd., special grade) were blended on the coating layer of the coating film of Example 1 to obtain a solid content concentration of 1%. The prepared coating material was applied with a Meyer bar, and dried at 60 ° C. for 1 minute using a blow dryer to form a low refractive index layer having a thickness of 110 nm, thereby obtaining an antireflection film. This is Example 16. The average regular reflectance (wavelength 400 to 700 nm) of the obtained antireflection film is 3.0% or less, and the average regular reflectance of the coating film of Example 1 having no low refractive index layer is 5.6%. Therefore, it was found that this antireflection film had a sufficient antireflection effect. The reflectance was measured with a spectrophotometer (U-3310 manufactured by Hitachi, Ltd.).
[0033]
[Table 1]
Figure 2004263082
[0034]
3. Evaluation (1) State of the Interface A cross-sectional photograph of each coating film was taken with a scanning electron microscope, and the one in which the interface between the coating layer and the resin film substrate could be clearly observed (the film substrate did not dissolve) ”And those with an unclear interface were evaluated as“ dissolved ”.
(2) The non-coated side of the color unevenness coated film was rubbed with steel wool, and the surface was colored with black spray paint and dried well. The degree of color unevenness when this coating film was visually observed from the coating surface side under a three-wavelength type fluorescent lamp in a dark room was evaluated.
:: No color unevenness Δ: Slight color unevenness X: Color unevenness is noticeable XX: Color unevenness is noticeable (3) A load of 400 g was applied to the surface of the coating layer of the scratch-resistant coating film. 0000 steel wool was placed, and the surface of the coating layer was rubbed by moving the steel wool, and the degree of scratches generated was visually determined.
:: no scratches △: slight scratches X: scratches are noticeable (4) Haze degree The haze degree of the coated film was measured according to JIS-K7105.
[0035]
Table 2 shows the obtained results. In Table 2, the ratio of ketone-ester refers to the mixing ratio of ketones and / or esters having a molecular weight of 100 or less with respect to the whole organic solvent used for the coating material. Further, the ratio of the organic solvent refers to the blending ratio of the organic solvent in the paint (organic solvent, resin composition, and other additives).
[0036]
[Table 2]
Figure 2004263082
[0037]
As is evident from Table 2, in Examples 1 to 15 of the present invention, it was demonstrated that the color unevenness preventing effect and the abrasion resistance were excellent, and the haze was 1% or less and the transmission clearness was excellent. . In Example 14, since the ratio of the organic solvent was as large as 65% by weight, the abrasion resistance was reduced. However, the prevention of color unevenness and the reduction in haze, which were the objects of the present invention, could be achieved. In each of the examples, the resin film substrate at the interface was dissolved.
[0038]
On the other hand, in Comparative Examples 1 and 2, since methyl isobutyl ketone and isopropyl acetate were used instead of cyclohexanone as the organic solvent, the resin film substrate at the interface did not dissolve and the effect of preventing color unevenness was not obtained.
[0039]
In Comparative Examples 3 to 5, since the ratio of cyclohexanone (ketone-ester) in the organic solvent was as low as 40 to 0% by weight, the resin film substrate at the interface was not dissolved, and the effect of preventing color unevenness was not obtained. In particular, in the case of Comparative Example 5 in which no ketone-ester was compounded, the effect of preventing color unevenness was most deteriorated.
[0040]
In the case of Comparative Example 6, since the proportion of the organic solvent was as low as 30% by weight, the resin film substrate at the interface was not dissolved, and the effect of preventing color unevenness was not obtained.
[0041]
In the case of Comparative Example 7, an acrylic film was used as the resin film substrate. However, since the selection of the organic solvent for the coating material was inappropriate, the resin film substrate at the interface did not dissolve and the effect of preventing color unevenness was not obtained.
[0042]
In the case of Comparative Examples 8 and 9, fine particles were added to the coating layer, so that the effect of preventing color nonuniformity was good, but the haze exceeded 3%, and the transmittance and transmission clearness of the film were reduced. .
[0043]
In each of the examples of the present invention, the ketone-ester ratio was in the range of 50 to 100% by weight, and except for Example 14, the ratio of the organic solvent was in the range of 35 to 60% by weight. Was in From these facts, it is clear that it is preferable to set the ratio of the ketone-ester to 50 to 100% by weight and the ratio of the organic solvent to 35 to 60% by weight.
[0044]
【The invention's effect】
In the present invention, since the coating material serving as the coating layer dissolves or swells the surface of the resin film substrate, it is possible to prevent color unevenness due to interference and obtain a coated film having high transmittance and high transmission sharpness.

Claims (6)

透明な樹脂フィルム基体の少なくとも片面に、有機溶媒と樹脂組成物とを主成分とする塗料を塗工して透明な塗工層を形成させてなる塗工フィルムであって、前記塗料が前記樹脂フィルム基体の表面を溶解又は膨潤可能であることを特徴とする塗工フィルム。At least one surface of a transparent resin film substrate, a coating film formed by applying a coating mainly composed of an organic solvent and a resin composition to form a transparent coating layer, wherein the coating is the resin A coated film capable of dissolving or swelling the surface of a film substrate. JIS−K7105に従って測定したヘイズ度が0.1〜3%である請求項1に記載された塗工フィルム。The coated film according to claim 1, wherein the haze degree measured according to JIS-K7105 is 0.1 to 3%. 前記樹脂組成物が熱硬化型樹脂組成物または紫外線硬化型樹脂組成物である請求項1または2に記載された塗工フィルム。The coated film according to claim 1, wherein the resin composition is a thermosetting resin composition or an ultraviolet curable resin composition. 前記樹脂フィルム基体がセルロースエステルフィルムであり、かつ前記有機溶媒が分子量100以下のケトン系有機溶剤または/及びエステル系有機溶剤である請求項1〜3のいずれかに記載された塗工フィルム。The coating film according to any one of claims 1 to 3, wherein the resin film substrate is a cellulose ester film, and the organic solvent is a ketone-based organic solvent and / or an ester-based organic solvent having a molecular weight of 100 or less. 前記塗工層の屈折率と前記樹脂フィルム基体の屈折率との差が0.013以上である請求項1〜4のいずれかに記載された塗工フィルム。The coating film according to any one of claims 1 to 4, wherein a difference between a refractive index of the coating layer and a refractive index of the resin film substrate is 0.013 or more. 請求項1〜5のいずれかに記載された塗工フィルムの塗工層の上に、さらに低屈折率層を設けた反射防止フィルムであって、前記低屈折率層の屈折率は前記塗工層の屈折率より低く、かつその差が0.01以上である反射防止フィルム。An antireflection film further comprising a low refractive index layer provided on the coating layer of the coating film according to claim 1, wherein the low refractive index layer has a refractive index of the coating. An antireflection film having a refractive index lower than that of the layers and a difference of 0.01 or more.
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