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JP5174303B2 - the film - Google Patents

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Publication number
JP5174303B2
JP5174303B2 JP2001274510A JP2001274510A JP5174303B2 JP 5174303 B2 JP5174303 B2 JP 5174303B2 JP 2001274510 A JP2001274510 A JP 2001274510A JP 2001274510 A JP2001274510 A JP 2001274510A JP 5174303 B2 JP5174303 B2 JP 5174303B2
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film
solvent
resistant layer
film according
coating
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JP2003080639A (en
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真人 藤田
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Mitsubishi Plastics Inc
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Mitsubishi Plastics Inc
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Priority to JP2001274510A priority Critical patent/JP5174303B2/en
Priority to KR1020020054251A priority patent/KR100936512B1/en
Publication of JP2003080639A publication Critical patent/JP2003080639A/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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/08Heat treatment
    • 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
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12Chemical modification
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/17Amines; Quaternary ammonium compounds
    • C08K5/19Quaternary ammonium compounds
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3025Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • 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
    • C08J2367/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Laminated Bodies (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Adhesive Tapes (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Description

【0001】
【発明の属する技術分野】
本発明は、偏光板、位相差板または視野角拡大フィルムの表面保護フィルムに好適なフィルムに関するもので、透明で、摩擦や剥離した際の帯電が少なく、帯電防止性および耐溶剤性が改良された基材フィルムに関するものである。
【0002】
【従来の技術】
偏光板(または位相差板等)やそれに準じた積層体等の光学部品の表面には、表面保護の目的でポリエチレン、ポリプロピレン等の透明な保護フィルムが積層されている。液晶ディスプレイ等の組込みが完了した後に、これらの保護フィルムが剥離によって除去される場合が多いが、この剥離時に静電気が発生して周囲のゴミが巻き込まれるという問題がある。
特に、近年、高精細化に対応したTFT方式による液晶ディスプレイでは、保護フィルムを剥離した際の剥離帯電によりTFT素子を破壊する問題がある。
一方、従来保護フィルムとして用いられているポリエチレン、ポリプロピレン等のフィルムは、透明性が劣っており、ディスプレイが組み込まれた後に、製品の欠陥検査を行う時に、その保護フィルムの透明性が劣るために欠陥検査を精度良く行うことが困難である。
【0003】
保護フィルムの透明性を増加させるために、透明性の高いポリエチレンテレフタレートフィルムを基材とした積層フィルムを用いることが考えられるが、その場合でも、例えば、その保護フィルムを偏光板に貼り合せて裁断した際、裁断面から微粘着層の粘着剤がはみ出し、偏光板を重ね合わしたときに保護フィルム表面に付着してしまうことがある。保護フィルムの表面に付着した粘着剤は製品の検品の障害になるだけでなく、べた付きのため製品出荷の支障となる。
そこで現在は、粘着剤が付着した場合、エタノールやメタノール・酢酸エチルなどの有機溶剤で表面を拭い取る作業が通常行われている。しかし、この作業により、保護フィルムの表面層の耐久性が不十分であれば、拭き取り作業による表面の白化または表面固有抵抗の劣化により、保護フィルムとして十分な性能を発現できなくなる。
また、粘着剤が付着しないように保護フィルムの表面の高い離型性を付与することも考えられるが、離型性が高すぎると、後工程において不都合が生じる。具体的には、偏光板(または位相差板等)をガラス基板等に貼着した後、偏光板(または位相差板等)上の保護フィルムにセロハン粘着テープを押しつけてからその粘着テープを持ち上げることにより、役目を果たした保護フィルムを剥離除去する作業において、保護フィルム表面の離型性のためにセロハン粘着テープが保護フィルムから剥がれる等して作業効率が悪くなる。
【0004】
【発明が解決しようとする課題】
本発明の目的は、かかる従来技術の問題を解消し、透明であって、各種ディスプレイの表面保護フィルムに用いた際に剥離帯電が少なく、かつ偏光板などに用いた際、表面の汚れだけを容易に除去できる効果を併せ持ち、また製品の欠陥検査時に障害とならないず、後工程の保護フィルム剥離作業においても作業効率の高いフィルムを提供することにある。
【0005】
【課題を解決するための手段】
本発明者は、上記課題に鑑み鋭意検討した結果、特定の構成からフィルムによれば、上記課題が容易に解決できることを見いだし、本発明を完成するに至った。すなわち、本発明の要旨は、基材フィルムの片面に微粘着層を有し、もう一方の面に、当該基材フィルムの配向結晶化が完了する前に帯電防止剤、水性樹脂、および架橋剤を含有する塗布液を塗布することにより形成された帯電防止性の耐溶剤層を有するフィルムであり、暗室で蛍光灯下での目視検査による当該フィルムの1平方メートル当たりのキズの個数が1個未満であり、フィルムのヘーズが10%以下であることを特徴とするフィルムに存する。
【0006】
【発明の実施の形態】
以下、本発明を具体的に説明する。
本発明における基材フィルムは、高い透明性を有するフィルムであることが好ましく、例えば、ポリエステルフィルム、ポリカーボネートフィルム、トリアセチルセルロースフィルム、ポリプロピレンフィルム、ポリエチレンフィルムなどを例として挙げることができる。これらの中でも、生産性、加工性において優れるポリエステルフィルムが好ましい。ポリエステルフィルムとしては、一軸配向フィルム、二軸配向フィルムのどちらも用いることができるが、二軸配向フィルムを用いることが好ましい。
ポリエステルフィルムを構成するポリエステルとしては、ジカルボン酸成分とグリコール成分とを重縮合して得られる線状ポリエステルであることが好ましい。
【0007】
ポリエステルを構成するジカルボン酸成分としては、テレルタル酸、イソフタル酸、2,6−ナフタレンジカルボン酸、ヘキサヒドロテレフタル酸、4.4´−ジフェニルジカルボン酸、アジピン酸、セバシン酸、ドデカンジカルボン酸等を例示しうる。特にフィルムの機械的性質の点からテレフタル酸、イソフタル酸、2,6−ナフタレンジカルボン酸が好ましい。
ポリエステルを構成するグリコール成分としては、エチレングリコール、ジエチレングリコール、プロピレングリコール、1,3−プロパンジオール、1,4−ブタンジオール、ネオペンチルグリコール、1,6−へキサンジオール、シクロヘキサンジメタノール、ポリエチレングリコール等を例示しうる。特にフィルムの剛直性の点からエチレングリコールが好ましい。
【0008】
上記のポリエステルは、第3成分として上記ジカルボン酸成分あるいはグリコール成分を共重合したコポリエステルであってもよく、三官能以上の多価カルボン酸成分あるいはポリオール成分を含んでもよく、得られるポリエステルが実質的に線状となる範囲(例えば5モル%以下)で少量共重合したポリエステルであってもよい。
本発明で用いるポリエステルとしては、ポリエチレンテレフタレートまたはポリエチレン−2,6−ナフタレートが特に好ましい。
かかるポリエステルは常法により作ることができ、ポリエステルの固有粘度(オルトクロロフェノール中、35℃)が、0.45以上であるとフィルムの剛性が大きい等の機械的特性が良好となるため好ましい。上記ポリエステルには、酸化ケイ素、酸化アルミニウム、酸化マグネシウム、炭酸カルシウム、カオリン、タルク、酸化チタン、硫酸バリウム等のような無機微粒子、架橋シリコーン樹脂、架橋ポリスチレン樹脂、架橋アクリル樹脂、尿素樹脂、メラミン樹脂等のような耐熱性ポリマーからなる有機微粒子を含有させることができる。これらの中でも、酸化ケイ素が好ましい。
【0009】
このほかに、テレフタル酸とイソフタル酸等の共重合ポリエステル、安定剤、酸化防止剤、紫外線吸収剤、蛍光増白剤等を必要に応じてポリエステル中に含有することもできる。
本発明で用いるポリエステルフィルムは、透明性の高いことが好ましく、特に高透明二軸延伸フィルムであることが好ましい。
本発明で用いるポリエステルフィルムは、公知の方法で製造することができる。例えば、二軸延伸ポリエステルフィルムは、ポリエステルレジンを乾燥後、押出し機にて溶融し、ダイ(例えばT−ダイ等)から回転冷却ドラム上に押出し、急冷して未延伸フィルムを製造し、次いで当該未延伸フィルムを縦方向および横方向に延伸し、必要に応じて熱固定することによって製造することができる。ポリエステルフィルムの厚さは通常5〜250μmの範囲であり、10〜100μm、さらには20〜50μmの範囲が好ましい。
【0010】
本発明のフィルムは、フィルム基材の片方の面に帯電防止性の耐溶剤層を有し、もう一方の表面に微粘着層を有する構成である。
本発明で言う微粘着層とは、例えば、当該層をステンレス板(SUS304)に貼合せ、23℃で6時間以上経時後に300mm/分の速度で180度の角度で剥離するときの剥離力が、2〜60g/25mmであるものを指し、微粘着層を構成する粘着剤としては、アクリル系、ゴム系またはウレタン系の粘着剤を用いることができ、特に、微粘着層の耐久性の点でアクリル系粘着剤が好ましい。
微粘着層は、剥離フィルムなどを貼り合せた後、再剥離する際、相手側に粘着剤の移行がないことが好ましい。
また、粘着剤のタイプとしては、熱硬化タイプ、UV硬化タイプ、EB硬化タイプ、ホットメルトタイプが挙げられ、さらに、耐久性や粘着剤の移行を抑えるために、イソシアネート系やエポキシ系の架橋剤を適宜使用できる。
【0011】
微粘着層の塗布方式および塗布条件などの塗布方法は、後述の帯電防止剤および汚れ防止剤を含む層の塗布方法と同じ方法に加え、ドクターブレードコート法などで実施することができる。
微粘着層表面には、必要に応じて離形剤で処理した剥離(離形)フィルムを貼り合せることができる。
本発明において、微粘着層の厚みは、3〜100μm、さらには5〜50μmであるのが好ましい。厚みが3μm未満であると十分な微接着効果が得られないことがあり、他方100μmを超える層は、過剰品質であり不経済であるうえ、保護フィルムの透明性を損なう場合がある。
【0012】
本発明において、帯電防止性と言うのは、表面の固有抵抗が、1×1013Ω/□以下、好ましくは1×107〜1×1011Ω/□、さらに好ましくは1×107〜1×1010Ω/□の範囲であることを指し、当該表面を有機溶剤(エタノールが好ましい)で処理した後の表面固有抵抗が、1×1013Ω/□以下、さらには1×107〜1×1011Ω/□、特に1×107〜1×1010Ω/□の範囲であることが好ましい。表面固有抵抗の値が1×1013Ω/□を超えると、剥離帯電を制御することが困難となる。
また、本発明における耐溶剤層とは、溶剤拭き処理後の表面固有抵抗の範囲が本発明の1×1013Ω/□以下を満足し、溶剤拭き処理後のセロハン粘着テープに対する剥離力が本発明の範囲の100g/24mm以上であることを満足し、かつ、溶剤拭き処理後のフィルムのヘーズが1〜10%、全光線透過率が80%以上であるものを意味する。
【0013】
帯電防止性を有する耐溶剤層を構成する成分としては、帯電防止樹脂や導電性樹脂等任意の帯電防止能を持つ高分子等から適宜選択することができる。
この帯電防止剤としては、例えば、第4級アンモニウム塩、ピリジニウム塩、第1〜3級アミノ基等のカチオン性官能基を有するカチオン性帯電防止剤、スルホン酸塩基、硫酸エステル塩基、リン酸エステル塩基、ホスホン酸塩基等のアニオン性官能基を有するアニオン系帯電防止剤、アミノ酸系、アミノ硫酸エステル系等の両性帯電防止剤、ポリオール系、ポリグリセリン系、ポリエチレングリコール系等のノニオン性官能基を有するの帯電防止剤等の各種高分子型帯電防止剤が挙げられ、また、第3級アミノ基や第4級アンモニウム基を有し、電離放射線により重合可能なモノマーやオリゴノマー、例えば、N,N−ジアルキルアミノアルキル(メタ)アクリレートモノマー、それらの第4級化合物等の重合性帯電防止剤、さらにポリアニリン、ポリピロール、ポリチオフェンなどの導電性ポリマー等も使用できる。これらの中でも、第4級アンモニウム塩型カチオン性官能基を有する高分子型帯電防止剤が好ましい。
【0014】
本発明においては、帯電防止剤として高分子帯電防止剤と同時に、低分子量の帯電防止剤、またはスズ、アンチモン系フィラー、酸化インジウム系等の導電性フィラーも併用することができる。
本発明においては、耐溶剤層のポリエステルフィルムへの密着性等の向上のために、バインダーとしてポリエステル類、ポリウレタン類、アクリル樹脂類、ポリビニル樹脂類、ポリオレフィン類などの熱可塑性樹脂および/または熱硬化性アクリル樹脂、メラミン樹脂、エポキシ樹脂などの熱硬化性樹脂などを含有させてもよい。
本発明において、耐溶剤層の耐溶剤性をより改良するために、架橋剤として、メチロール化あるいはアルコキシメチル化したメラミン系化合物、尿素系化合物、エポキシ系化合物、イソシアネート系化合物、カルボジイミド化合物、オキサゾリン系化合物、シランカップリング剤系化合物から選ばれた少なくとも1種類を含有することが特に好ましい。
【0015】
上述の層を構成する、帯電防止剤,バインダー、架橋剤の量比は、その選択される化合物よって最適値が異なるため特に規定するものではないが、下記の層特性を満足する量比であることが好ましい。
耐溶剤層中の帯電防止剤の含有量は、通常5重量%以上、好ましくは10〜90%の範囲であり、帯電防止剤がイオン性官能基を有する化合物の重合体である場合は、15〜90重量%、さらには20〜90重量%の範囲とすることが好ましい。帯電防止剤の比率が少なすぎると、十分な表面固有抵抗を達成することが難しくなり、また帯電防止剤の比率が多くなりすぎると、耐溶剤性の点で十分な効果を得られない場合がある。
【0016】
さらに本発明のフィルムにおいて、耐溶剤層表面のセロテープ剥離荷重は、100g/24mm以上、さらには200g/24mm以上、特に400〜600g/24mmの範囲であることが好ましく、耐溶剤層表面を有機溶剤(エタノールが好ましい)で処理した後のセロテープ剥離加重は、通常100g/24mm以上であり、200g/24mm以上、さらには400g/24mm以上、特に400〜600g/24mmの範囲であることが好ましい。セロテープ剥離荷重が、100g/24mm未満では、保護フィルムを剥がす工程で、保護フィルムからセロテープが剥がれやすくなり、作業効率が悪くなる傾向がある。また、600g/24mmより大きくなると、帯電防止層の表面の異物、微粘着糊の糊移り等をを有機溶剤で拭いてとる作業の効率が悪くなる傾向がある。
【0017】
さらに本発明のフィルムのヘーズは、通常10%以下であり、1〜8%、さらには1〜6%、特に2〜5%の範囲が好ましく、耐溶剤層表面を有機溶剤(エタノールが好ましい)で処理した後の基材フィルムのヘーズについても、上記範囲にあることが好ましい。基材フィルムのヘーズが、10%を超えると、偏光板などの保護フィルムとして用いた場合、透明性が悪いために製品の欠陥検査工程で十分な精度がでないことがある。また、ヘーズが低すぎると、基材表面にキズが入りやすくなり、製品の欠陥検査工程での障害となる場合がある。
本発明のフィルムのフィルムを保護フィルムとして用いる場合、欠陥検査工程での障害を防ぐために、本発明のフィルムの表面には、蛍光灯下、目視で確認できるようなキズがないことが好ましい。
本発明において、耐溶剤層の厚みは、通常0.001〜0.5μm、好ましくは0.01〜0.2μm、さらに好ましくは0.01〜0.1μm、特に好ましくは0.02〜0.07μmの範囲である。厚みが0.001μm未満であると、十分な帯電防止効果やその耐溶剤性の効果が得られなくなることがあり、他方0.5μmを超えると、もはや過剰品質であり、経済的メリットがなくなってしまう。
【0018】
本発明のフィルムを構成する耐溶剤層は、水性塗液(水を媒体とする水溶性樹脂または水分散性樹脂)を塗布して形成することが好ましいが、少量の有機溶剤を含有した水性塗液を塗布して形成することも可能である。この有機溶剤としては、エタノール、イソプロパノール、エチレングリコール、グリセリン等のアルコール類、エチルセロソルブ、t−ブチルセロソルブ、プロピレングリコールモノメチルエーテル、テトラヒドロフラン等のエーテル類、アセトン、メチルエチルケトン等のケトン類、酢酸エチル等のエステル類、ジメチルエタノールアミン等のアミン類等を例示することができる。これらは単独、もしくは複数を組み合わせて用いることができる。水性塗液に、必要に応じてこれらの有機溶剤を適宜選択し、含有させることで、塗液の安定性、塗布性あるいは塗膜特性を助けることができる。
【0019】
本発明において、用いる塗液の固形分濃度は特に制約はないが、通常30重量%以下であり、0.2〜20重量%、さらには0.5〜15重量%、特に1〜10重量%の範囲が好ましい。塗液の固形分濃度が薄くなると、塗布はじきが生じやすくなる等の塗布面状の均一性に問題が生じやすくなる。また、塗液の固形分濃度が30重量%を超えると、塗布液の粘度が高くなる傾向にあり、このため塗布外観が悪化することがある。
本発明において、耐溶剤層は、基材フィルムの少なくとも一方の面に設ければよいが、微粘着層と反対の面のみに設ける方が、経済的メリットがある。
【0020】
基材フィルムとしてポリエステルフィルム等の延伸フィルムを用いる場合、公知の方法で延伸されて結晶配向が完了したポリエステルフィルム、あるいはポリエステルを熱溶融してそのままフィルム状とした未延伸フィルム、未延伸フィルムを縦方向または横方向のいずれか一方に配向させた一軸延伸フィルム、縦方向および横方向の2方向に低倍率延伸配向させたもの(最終的に縦方向および横方向に再延伸させて配向結晶化を完了させる前の二軸延伸フィルム)等の結晶配向が完了する前のポリエステルフィルムへ塗布する例、および配向結晶化が終了した後のフィルムに塗布する例が挙げられる。配向結晶化を完了する前に塗布層を形成する方法が好ましい。塗布層が形成された後に、熱固定による例えば200℃以上の高温処理が施されることにより、該塗布層の帯電防止性、その耐溶剤性が向上する。また、別工程での塗布処理によるフィルムのロールとの接触が無くなるためフィルム表面のキズの抑制にも有効となる。
【0021】
基材フィルムへの塗液の塗布方法としては、公知の任意の塗布方法が適用できる。例えばロールコート法、グラビアコート法、マイクログラビアコート法、リバースコート法、バーコート法、ロールブラッシュ法、スプレーコート法、エアーナイフコート法、含浸法およびカーテンコート法、ダイコート法などを単独または組み合わせて適用するとよい。
【0022】
【実施例】
以下、本発明を実施例によりさらに詳細に説明するが、本発明は、その要旨を越えない限り、以下の実施例に限定されるものではない。なお、本発明における各種の物性および特性の測定方法、定義は下記のとおりである。また、実施例および比較例中、「部」および「%」とあるのは、各「重量部」および「重量%」を意味する。
【0023】
(1)表面固有抵抗値
日本ヒューレット・パッカード社製高抵抗測定器:HP4339Bおよび測定電極:HP16008Bを使用し、23℃,50%RHの測定雰囲気で十分調湿後、印可電圧100Vで1分後の基材フィルムの帯電防止層の表面固有抵抗値を測定した。
表面固有抵抗は、以下の基準で評価した。
○:1×1011以下
△:1×1011を超え1×1013まで
×:1×1013を超える
【0024】
(2)セロテープ剥離荷重
粘着テープ(ニチバン製セロテープ)を基材フィルムの耐溶剤層表面に貼り付け、23℃,50%RHの測定雰囲気下で30分調湿後、300mm/分の速度で180度の角度で粘着テープを剥離するときの剥離荷重をインテスコ社製引張試験機で測定した。
セロテープ剥離加重は、以下の基準で評価した。
◎:400〜600g/24mm
○-1:200以上400g/24mm未満
○-2:600g/24mmを超える
△:100g/24mm以上200g/24mm未満
×:100g/24mm未満
【0025】
(3)透明性
日本電色工業社製分球式濁度計:NDH−300Aを用い、JIS−K6714に準じてフィルムヘーズと全光線透過率を測定した。
ヘーズは以下の基準で評価した。
○:6%以下
△:6%を超え10%まで
×:10%を超える
全光線透過率は以下の基準で評価した。
○:80%以上
×:80%未満
【0026】
(4)フィルム表面検査
基材フィルムを暗室で約5平方メートルの基材フィルムを蛍光灯下で目視検査し、キズの個数を数え、1平方メートル当たりに換算して求めた。
○:1個未満
×:1個以上
【0027】
(5)溶剤処理
太平理化工業社ラビングテスター専用治具(5cm×7cm,500g)にシート状コットン(旭化成社製ベンコット)を巻き付け、そこにエタノールを2ml染みこませて、耐溶剤層表面を5往復(15cm長の範囲)拭いてサンプルを調整した。
【0028】
(6)セロテープ剥離試験
表面保護フィルムの微粘着層面をガラス板に貼着後、帯電防止層面にセロハン粘着テープ(ニチバン製セロテープ,24mm巾)を用いて剥離除去試験を行った。剥離除去試験の結果は、以下の基準で評価した。
○:剥離ミスなく、表面保護フィルムを連続で除去できる
△:100回の試験中、少なくとも1回剥離ミスがある
×:連続して剥離ミスが発生する
【0029】
(7)微粘着糊拭き取り試験
表面保護フィルムの耐溶剤層表面に、微粘着層面をこすりつけた後、微粘着層をエタノールを染みこませたシート状コットンで拭き取った。微粘着層拭き取り試験の結果は、以下の基準で評価した。
○:耐溶剤層表面の外観変化なく、容易に拭き取れた
△:耐溶剤層表面の外観変化はないが、拭き取りに時間を要した
×:耐溶剤層表面の外観が変化した
【0030】
本発明で用いた塗布剤成分は以下のとおりである。
[帯電防止層成分]
帯電防止剤(A1):ポリジアリルジメチルアンモニウムクロライド(平均分子量:約30000)
水性樹脂(B1):水性アクリル樹脂(日本カーバイド工業社製、ニカゾールA−08)
水性樹脂(B2):部分ケン化型ポリビニルアルコール(ケン化度:約88モル%)
水性樹脂(B3):酸化ポリエチレン水分散体(ジョンソンポリマー社製、ジョンワックス 26)
架橋剤(C1):メトキシメチロールメラミン(大日本インキ社製、ベッカミン J101)
【0031】
実施例1
極限粘度0.65dl/gのポリエチレンテレフタレート(平均粒径約2.4μmのシリカ粒子を0.05%含有)のペレットを180℃で熱風乾燥結晶化後、押出し機に供給し、280〜300℃の温度でTダイからシート状に溶融押し出しし、静電密着法を併用し、20℃に温度調整した鏡面冷却ドラム上にキャスト・急冷し、厚さ約720μmの未延伸フィルムを得た。次にこのフィルムを85℃で長手方向に3.7倍延伸し、一軸延伸フィルムを得た。このフィルムに耐溶剤層として、4級アンモニウム塩型カチオン性高分子帯電防止剤:A1、アクリル樹脂:B1、メラミン系化合物:C1を、40/30/30(固形分換算重量比)の比率で混合し、イオン交換水で固形分濃度3重量%に希釈し調製し調整した塗布液をポリエステルフィルムの片面に、バーコーターを用いて約5μm(wet厚)塗布した。次に110〜150℃のゾーンで横方向に3.9倍延伸し、230℃で熱処理して、結晶配向の完了した厚さ50μmの二軸延伸ポリエステルフィルムを得た。この横方向の延伸処理以降の熱処理で塗膜を乾燥させ帯電防止層を設けたフィルムを得た。この方法によって得られたポリエステルフィルムのヘーズは4%、全光線透過率は、89%であった。
次に、この耐溶剤層と反対の面に、微粘着層としてアクリル系粘着剤(帝国化学株式会社製、SG−800)100部(固形分重量部)に対し、イソシアネート硬化剤(日本ポリウレタン株式会社製、コロネートHL)10部(固形分重量部)を加えた塗工液を、バーコーターを用いて塗布し、100℃、2分間塗膜を乾燥・硬化させ、厚み20μmの微粘着層を設け、表面保護フィルムを作成した。この表面保護フィルムの特性を下記表4に示す。
【0032】
実施例2〜4
耐溶剤層を構成する成分を下記表1に記載の組成に変更する以外は実施例1と同じ方法で基材フィルムを作成した。この基材フィルムの耐溶剤層の構成を表1に示し、そのフィルム特性を下記表2および表3に示し、このフィルムを用いた表面保護フィルムの特性を表4に示す。
【0033】
比較例1
耐溶剤層を設けない以外は実施例1と同じ方法で基材フィルムを作成した。その後、基材フィルム表面に通常条件でコロナ処理し、実施例1記載の塗布液をバーコーターで塗布し、150℃、1分間塗膜を乾燥・硬化させ、耐溶剤層を設けた基材フィルムを作成した。この基材フィルムの耐溶剤層の構成を表1に示し、そのフィルム特性を表2に示し、このフィルムを用いた表面保護フィルムの特性を表4に示す。
【0034】
比較例
耐溶剤層を設けない以外は実施例1と同じ方法で基材フィルムを作成した。この基材フィルムの耐溶剤層の構成を表1に示し、そのフィルム特性を表2に示し、このフィルムを用いた表面保護フィルムの特性を表4に示す。
【0035】
比較例3〜5
耐溶剤層を構成する成分を表1に記載の組成に変更する以外は実施例1と同じ方法で基材フィルムを作成した。この基材フィルムの帯電防止層の構成を表1に示し、そのフィルム特性を表2および表3に示し、このフィルムを用いた表面保護フィルムの特性を表4に示す。
【0036】
【表1】

Figure 0005174303
【0037】
【表2】
Figure 0005174303
【0038】
【表3】
Figure 0005174303
【0039】
【表4】
Figure 0005174303
【0040】
【発明の効果】
本発明のフィルムは、透明であって、各種ディスプレイの表面保護フィルムに用いた際に剥離帯電が少なく、かつ偏光板などに用いた際、表面の汚れだけを容易に除去できる効果を併せ持ち、また製品の欠陥検査時に障害とならないず、後工程の保護フィルム剥離作業においても作業効率の高いフィルムを提供することができ、その工業的価値は高い。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a film suitable for a surface protective film of a polarizing plate, a retardation plate or a viewing angle widening film, is transparent, has little charge when rubbed or peeled, and has improved antistatic properties and solvent resistance. The present invention relates to a base film.
[0002]
[Prior art]
A transparent protective film such as polyethylene or polypropylene is laminated on the surface of a polarizing plate (or a retardation plate or the like) or an optical component such as a laminate according to the polarizing plate for the purpose of surface protection. In many cases, these protective films are removed by peeling after the liquid crystal display or the like is assembled, but there is a problem in that static electricity is generated at the time of peeling and surrounding dust is caught.
In particular, in recent years, a TFT-type liquid crystal display corresponding to high definition has a problem of destroying the TFT element due to peeling charging when the protective film is peeled off.
On the other hand, polyethylene, polypropylene, and other films conventionally used as protective films are inferior in transparency, and when a product is inspected for defects after the display is incorporated, the transparency of the protective film is inferior. It is difficult to accurately perform defect inspection.
[0003]
In order to increase the transparency of the protective film, it is conceivable to use a laminated film based on a highly transparent polyethylene terephthalate film. Even in that case, for example, the protective film is bonded to a polarizing plate and cut. When doing so, the adhesive of the slightly adhesive layer may protrude from the cut surface and adhere to the surface of the protective film when the polarizing plates are overlaid. The pressure-sensitive adhesive adhering to the surface of the protective film not only obstructs the inspection of the product, but also makes it difficult to ship the product due to stickiness.
Therefore, at present, when an adhesive is attached, an operation of wiping the surface with an organic solvent such as ethanol, methanol or ethyl acetate is usually performed. However, if the durability of the surface layer of the protective film is insufficient due to this operation, sufficient performance as a protective film cannot be exhibited due to whitening of the surface or deterioration of the surface resistivity due to the wiping operation.
In addition, it is conceivable to impart a high releasability on the surface of the protective film so that the pressure-sensitive adhesive does not adhere. However, if the releasability is too high, inconvenience occurs in the subsequent process. Specifically, after attaching a polarizing plate (or retardation plate, etc.) to a glass substrate, etc., the cellophane adhesive tape is pressed against a protective film on the polarizing plate (or retardation plate, etc.) and then the adhesive tape is lifted. Thus, in the operation of peeling off and removing the protective film that has played a role, the cellophane adhesive tape is peeled off from the protective film due to the releasability of the surface of the protective film, resulting in poor work efficiency.
[0004]
[Problems to be solved by the invention]
The object of the present invention is to solve such problems of the prior art, and is transparent, has little peeling charge when used in a surface protective film for various displays, and only removes dirt on the surface when used for a polarizing plate. Another object of the present invention is to provide a film that has an effect that can be easily removed and that does not become an obstacle when inspecting a defect of a product and that has a high work efficiency even in a protective film peeling operation in a subsequent process.
[0005]
[Means for Solving the Problems]
As a result of intensive studies in view of the above problems, the present inventor has found that the above problems can be easily solved according to a film from a specific configuration, and has completed the present invention. That is, the gist of the present invention is that a base film has a slightly adhesive layer on one side, and an antistatic agent, an aqueous resin, and a cross-linking agent are formed on the other side before orientation crystallization of the base film is completed. a film having a coating solution solvent layer of the formed antistatic by applying a containing, per square number of scratches per meter is less than one of the film by visual inspection under a fluorescent lamp in a dark room And the film has a haze of 10% or less.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be specifically described.
The substrate film in the present invention is preferably a film having high transparency, and examples thereof include a polyester film, a polycarbonate film, a triacetyl cellulose film, a polypropylene film, and a polyethylene film. Among these, a polyester film excellent in productivity and workability is preferable. As the polyester film, either a uniaxially oriented film or a biaxially oriented film can be used, but a biaxially oriented film is preferably used.
The polyester constituting the polyester film is preferably a linear polyester obtained by polycondensation of a dicarboxylic acid component and a glycol component.
[0007]
Examples of dicarboxylic acid components constituting the polyester include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, 4.4'-diphenyldicarboxylic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, etc. Yes. In particular, terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are preferable from the viewpoint of mechanical properties of the film.
Examples of the glycol component constituting the polyester include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexanedimethanol, polyethylene glycol, etc. Can be illustrated. In particular, ethylene glycol is preferable from the viewpoint of the rigidity of the film.
[0008]
The polyester may be a copolyester obtained by copolymerizing the dicarboxylic acid component or glycol component as the third component, and may contain a trifunctional or higher polyvalent carboxylic acid component or polyol component. It may be a polyester copolymerized in a small amount within a linear range (for example, 5 mol% or less).
As the polyester used in the present invention, polyethylene terephthalate or polyethylene-2,6-naphthalate is particularly preferable.
Such a polyester can be produced by a conventional method, and an intrinsic viscosity of the polyester (in orthochlorophenol, 35 ° C.) of 0.45 or more is preferable because mechanical properties such as high film rigidity are improved. Examples of the polyester include inorganic fine particles such as silicon oxide, aluminum oxide, magnesium oxide, calcium carbonate, kaolin, talc, titanium oxide, and barium sulfate, a crosslinked silicone resin, a crosslinked polystyrene resin, a crosslinked acrylic resin, a urea resin, and a melamine resin. Organic fine particles made of a heat-resistant polymer such as can be contained. Among these, silicon oxide is preferable.
[0009]
In addition, copolymerized polyesters such as terephthalic acid and isophthalic acid, stabilizers, antioxidants, ultraviolet absorbers, fluorescent brighteners, and the like can be contained in the polyester as necessary.
The polyester film used in the present invention preferably has high transparency, and is particularly preferably a highly transparent biaxially stretched film.
The polyester film used in the present invention can be produced by a known method. For example, a biaxially stretched polyester film is obtained by drying a polyester resin, melting it with an extruder, extruding it from a die (such as a T-die) onto a rotating cooling drum, and quenching to produce an unstretched film. It can manufacture by extending | stretching an unstretched film to the vertical direction and a horizontal direction, and heat-setting as needed. The thickness of the polyester film is usually in the range of 5 to 250 μm, preferably 10 to 100 μm, and more preferably 20 to 50 μm.
[0010]
The film of the present invention has a structure in which an antistatic solvent-resistant layer is provided on one surface of a film substrate and a slightly adhesive layer is provided on the other surface.
The slight adhesion layer referred to in the present invention is, for example, a peeling force when the layer is bonded to a stainless steel plate (SUS304) and peeled at an angle of 180 degrees at a speed of 300 mm / min after 6 hours or more at 23 ° C. The pressure-sensitive adhesive constituting the fine-adhesive layer can be an acrylic, rubber-based or urethane-based adhesive, and particularly the durability of the fine-adhesive layer. An acrylic adhesive is preferred.
When the fine adhesive layer is peeled off again after bonding a release film or the like, it is preferable that the adhesive does not migrate to the other side.
In addition, examples of the adhesive type include thermosetting type, UV curing type, EB curing type, and hot melt type. Furthermore, in order to suppress the durability and transfer of the adhesive, an isocyanate or epoxy crosslinking agent is used. Can be used as appropriate.
[0011]
Application methods such as the application method and application conditions of the slightly adhesive layer can be carried out by the doctor blade coating method in addition to the same method as the application method of the layer containing the antistatic agent and antifouling agent described later.
If necessary, a release (release) film treated with a release agent can be bonded to the surface of the slightly adhesive layer.
In the present invention, the thickness of the slightly adhesive layer is preferably 3 to 100 μm, more preferably 5 to 50 μm. If the thickness is less than 3 μm, a sufficient fine adhesion effect may not be obtained. On the other hand, a layer exceeding 100 μm is excessive in quality and uneconomical, and may impair the transparency of the protective film.
[0012]
In the present invention, the antistatic property means that the surface resistivity is 1 × 10 13 Ω / □ or less, preferably 1 × 10 7 to 1 × 10 11 Ω / □, and more preferably 1 × 10 7 to 1 × 10 10 Ω / □ indicates that the surface has a specific resistance after treatment with an organic solvent (preferably ethanol) of 1 × 10 13 Ω / □ or less, and further 1 × 10 7 It is preferable to be in the range of ˜1 × 10 11 Ω / □, particularly 1 × 10 7 to 1 × 10 10 Ω / □. If the value of the surface resistivity exceeds 1 × 10 13 Ω / □, it becomes difficult to control the peeling charge.
In addition, the solvent resistant layer in the present invention means that the range of the surface resistivity after the solvent wiping treatment satisfies 1 × 10 13 Ω / □ or less of the present invention, and the peel strength against the cellophane adhesive tape after the solvent wiping treatment is It means that 100 g / 24 mm or more of the range of the invention is satisfied, the haze of the film after the solvent wiping treatment is 1 to 10%, and the total light transmittance is 80% or more.
[0013]
The component constituting the solvent-resistant layer having antistatic properties can be appropriately selected from polymers having any antistatic ability such as antistatic resins and conductive resins.
Examples of the antistatic agent include a cationic antistatic agent having a cationic functional group such as a quaternary ammonium salt, a pyridinium salt, and a primary to tertiary amino group, a sulfonate group, a sulfate ester base, and a phosphate ester. Anionic antistatic agents having anionic functional groups such as bases and phosphonic acid groups, amphoteric antistatic agents such as amino acids and aminosulfate esters, nonionic functional groups such as polyols, polyglycerols, and polyethylene glycols Various antistatic agents such as antistatic agents, and monomers and oligomers having tertiary amino groups and quaternary ammonium groups that can be polymerized by ionizing radiation, such as N, N Polymerizable antistatic agents such as dialkylaminoalkyl (meth) acrylate monomers, quaternary compounds thereof, and poly Phosphorus, polypyrrole, conductive polymers such as polythiophene can be used. Among these, a polymer type antistatic agent having a quaternary ammonium salt type cationic functional group is preferable.
[0014]
In the present invention, a low molecular weight antistatic agent or a conductive filler such as tin, antimony filler, indium oxide or the like can be used in combination with the polymer antistatic agent as the antistatic agent.
In the present invention, a thermoplastic resin such as polyesters, polyurethanes, acrylic resins, polyvinyl resins, polyolefins and / or thermosetting as a binder for improving the adhesion of the solvent resistant layer to the polyester film. A thermosetting resin such as an acrylic resin, a melamine resin, or an epoxy resin may be included.
In the present invention, in order to further improve the solvent resistance of the solvent-resistant layer, as a crosslinking agent, methylolated or alkoxymethylated melamine compound, urea compound, epoxy compound, isocyanate compound, carbodiimide compound, oxazoline type It is particularly preferable to contain at least one selected from a compound and a silane coupling agent compound.
[0015]
The amount ratio of the antistatic agent, binder and cross-linking agent constituting the above-mentioned layer is not particularly specified because the optimum value varies depending on the selected compound, but is the amount ratio satisfying the following layer characteristics. It is preferable.
The content of the antistatic agent in the solvent-resistant layer is usually 5% by weight or more, preferably in the range of 10 to 90%. When the antistatic agent is a polymer of a compound having an ionic functional group, 15 It is preferable to be in the range of -90% by weight, more preferably 20-90% by weight. If the ratio of the antistatic agent is too small, it is difficult to achieve sufficient surface resistivity, and if the ratio of the antistatic agent is too large, a sufficient effect may not be obtained in terms of solvent resistance. is there.
[0016]
Furthermore, in the film of the present invention, the cello tape peeling load on the surface of the solvent resistant layer is preferably 100 g / 24 mm or more, more preferably 200 g / 24 mm or more, particularly preferably in the range of 400 to 600 g / 24 mm. The cello tape peeling load after treatment with (ethanol is preferred) is usually 100 g / 24 mm or more, preferably 200 g / 24 mm or more, more preferably 400 g / 24 mm or more, and particularly preferably in the range of 400 to 600 g / 24 mm. When the cello tape peeling load is less than 100 g / 24 mm, the cello tape is easily peeled off from the protective film in the step of peeling off the protective film, and the working efficiency tends to be deteriorated. On the other hand, if it is larger than 600 g / 24 mm, the efficiency of the work of wiping off foreign matters on the surface of the antistatic layer, the transfer of fine adhesive paste, etc. with an organic solvent tends to be deteriorated.
[0017]
Further, the haze of the film of the present invention is usually 10% or less, preferably 1 to 8%, more preferably 1 to 6%, particularly preferably 2 to 5%, and the surface of the solvent-resistant layer is an organic solvent (ethanol is preferred). The haze of the base film after being treated with is preferably within the above range. When the haze of the substrate film exceeds 10%, when used as a protective film such as a polarizing plate, the transparency may be poor and the accuracy of the product defect inspection process may not be sufficient. On the other hand, if the haze is too low, the surface of the substrate is likely to be scratched, which may be an obstacle in the product defect inspection process.
When the film of the film of the present invention is used as a protective film, it is preferable that the surface of the film of the present invention is free from scratches that can be visually confirmed under a fluorescent lamp in order to prevent failure in the defect inspection process.
In the present invention, the thickness of the solvent-resistant layer is usually 0.001 to 0.5 μm, preferably 0.01 to 0.2 μm, more preferably 0.01 to 0.1 μm, and particularly preferably 0.02 to 0.00. The range is 07 μm. If the thickness is less than 0.001 μm, sufficient antistatic effect and solvent resistance effect may not be obtained. On the other hand, if the thickness exceeds 0.5 μm, the quality is no longer excessive and there is no economic merit. End up.
[0018]
The solvent-resistant layer constituting the film of the present invention is preferably formed by applying an aqueous coating liquid (water-soluble resin or water-dispersible resin using water as a medium), but an aqueous coating containing a small amount of an organic solvent. It is also possible to form by applying a liquid. Examples of the organic solvent include alcohols such as ethanol, isopropanol, ethylene glycol, and glycerin, ethers such as ethyl cellosolve, t-butyl cellosolve, propylene glycol monomethyl ether, and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate. And amines such as dimethylethanolamine. These can be used alone or in combination. By appropriately selecting and containing these organic solvents in the aqueous coating liquid as necessary, stability of the coating liquid, applicability, or coating film characteristics can be assisted.
[0019]
In the present invention, the solid content concentration of the coating liquid to be used is not particularly limited, but is usually 30% by weight or less, 0.2 to 20% by weight, further 0.5 to 15% by weight, particularly 1 to 10% by weight. The range of is preferable. When the solid content concentration of the coating liquid is reduced, problems such as application repelling uniformity, such as easy application repelling, are likely to occur. On the other hand, when the solid content concentration of the coating liquid exceeds 30% by weight, the viscosity of the coating liquid tends to be high, and the coating appearance may be deteriorated.
In the present invention, the solvent-resistant layer may be provided on at least one surface of the base film, but it is economically advantageous to provide it only on the surface opposite to the slightly adhesive layer.
[0020]
When using a stretched film such as a polyester film as a base film, a polyester film that has been stretched by a known method and crystal orientation has been completed, or an unstretched film that has been made into a film by heat-melting the polyester, Uniaxially stretched film oriented in either the horizontal or horizontal direction, and stretched and oriented at low magnification in two directions, the machine direction and the transverse direction (finally oriented and crystallized by redrawing in the machine direction and the transverse direction) Examples of application to a polyester film before completion of crystal orientation such as a biaxially stretched film before completion) and examples of application to a film after completion of orientation crystallization are given. A method of forming a coating layer before completing the orientation crystallization is preferable. After the coating layer is formed, a high temperature treatment of, for example, 200 ° C. or more by heat setting is performed, whereby the antistatic property and the solvent resistance of the coating layer are improved. Moreover, since the contact with the roll of the film by the application | coating process at another process is lose | eliminated, it becomes effective also in suppression of the crack of a film surface.
[0021]
As a method for applying the coating solution to the base film, any known coating method can be applied. For example, roll coating method, gravure coating method, micro gravure coating method, reverse coating method, bar coating method, roll brush method, spray coating method, air knife coating method, impregnation method and curtain coating method, die coating method, etc. alone or in combination It is good to apply.
[0022]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded. In addition, the measurement methods and definitions of various physical properties and characteristics in the present invention are as follows. In Examples and Comparative Examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.
[0023]
(1) Surface resistivity value Using a high resistance measuring instrument made by Hewlett-Packard Japan: HP4339B and measuring electrode: HP16008B, after sufficient humidity adjustment in a measurement atmosphere of 23 ° C. and 50% RH, after 1 minute at an applied voltage of 100V The surface specific resistance value of the antistatic layer of the base film was measured.
The surface resistivity was evaluated according to the following criteria.
○: 1 × 10 11 or less △: 1 × 10 11 × to 1 × 10 13 exceed: 1 × more than 10 13 [0024]
(2) Cello tape peeling load Adhesive tape (Nichiban cello tape) was applied to the surface of the solvent-resistant layer of the base film, and after conditioning for 30 minutes in a measurement atmosphere of 23 ° C. and 50% RH, 180 mm at a rate of 300 mm / min. The peeling load when peeling the adhesive tape at an angle of degree was measured with an Intesco tensile tester.
The cello tape peeling load was evaluated according to the following criteria.
A: 400 to 600 g / 24 mm
○ -1: 200 or more and less than 400 g / 24 mm ○ -2: More than 600 g / 24 mm Δ: 100 g / 24 mm or more and less than 200 g / 24 mm x: Less than 100 g / 24 mm
(3) Transparency Nippon Denshoku Kogyo Co., Ltd. spheroid turbidimeter: NDH-300A was used to measure film haze and total light transmittance according to JIS-K6714.
Haze was evaluated according to the following criteria.
○: 6% or less Δ: Over 6% to 10% x: Total light transmittance exceeding 10% was evaluated according to the following criteria.
○: 80% or more ×: less than 80%
(4) Film surface inspection The substrate film of about 5 square meters was visually inspected under a fluorescent lamp in a dark room, and the number of scratches was counted and converted per square meter.
○: Less than 1 x: 1 or more 【0027】
(5) Solvent treatment Taihei Rika Kogyo Co., Ltd. Rubbing tester dedicated jig (5cm x 7cm, 500g) is wrapped with sheet-like cotton (Bencot manufactured by Asahi Kasei Co., Ltd.), and 2ml of ethanol is infiltrated there, so that the surface of the solvent-resistant layer is 5 A sample was prepared by wiping back and forth (15 cm long).
[0028]
(6) Cellophane peeling test After the surface of the surface protective film was adhered to the glass plate, a peeling removal test was conducted using a cellophane adhesive tape (Nichiban cello tape, 24 mm width) on the surface of the antistatic layer. The results of the peel removal test were evaluated according to the following criteria.
○: The surface protective film can be removed continuously without peeling mistakes. Δ: At least one peeling mistake occurs during 100 tests. ×: Continuous peeling mistakes occur.
(7) Fine-adhesive glue wiping test After the fine-adhesive layer surface was rubbed against the surface of the solvent-resistant layer of the surface protective film, the fine-adhesive layer was wiped with a sheet-like cotton soaked with ethanol. The result of the slightly adhesive layer wiping test was evaluated according to the following criteria.
○: Easily wiped without change in the appearance of the solvent-resistant layer Δ: No change in the appearance of the surface of the solvent-resistant layer, but time-consuming wiping ×: Change in the appearance of the surface of the solvent-resistant layer
The coating agent components used in the present invention are as follows.
[Antistatic layer component]
Antistatic agent (A1): polydiallyldimethylammonium chloride (average molecular weight: about 30000)
Aqueous resin (B1): Aqueous acrylic resin (Nicarbazole A-08, manufactured by Nippon Carbide Industries, Ltd.)
Aqueous resin (B2): partially saponified polyvinyl alcohol (degree of saponification: about 88 mol%)
Aqueous resin (B3): Oxidized polyethylene aqueous dispersion (John Wax 26, manufactured by Johnson Polymer Co., Ltd.)
Crosslinking agent (C1): Methoxymethylol melamine (Dainippon Ink Co., Ltd., Becamine J101)
[0031]
Example 1
Pellets of polyethylene terephthalate having an intrinsic viscosity of 0.65 dl / g (containing 0.05% silica particles having an average particle size of about 2.4 μm) are dried by hot air crystallization at 180 ° C. and then supplied to an extruder at 280 to 300 ° C. The film was melt-extruded from a T die into a sheet shape at a temperature of 1, and cast and quenched on a mirror-cooled drum whose temperature was adjusted to 20 ° C. in combination with an electrostatic adhesion method to obtain an unstretched film having a thickness of about 720 μm. Next, this film was stretched 3.7 times in the longitudinal direction at 85 ° C. to obtain a uniaxially stretched film. As a solvent-resistant layer on this film, a quaternary ammonium salt type cationic polymer antistatic agent: A1, acrylic resin: B1, and melamine compound: C1 in a ratio of 40/30/30 (weight ratio in terms of solid content). A coating solution prepared by mixing, diluting with ion-exchanged water to a solid content concentration of 3% by weight, and applying the coating solution was applied to one side of a polyester film with a bar coater by about 5 μm (wet thickness). Next, the film was stretched 3.9 times in the transverse direction in a zone of 110 to 150 ° C. and heat treated at 230 ° C. to obtain a biaxially stretched polyester film having a thickness of 50 μm and having completed crystal orientation. The coating film was dried by heat treatment after the transverse stretching treatment to obtain a film provided with an antistatic layer. The haze of the polyester film obtained by this method was 4%, and the total light transmittance was 89%.
Next, on the surface opposite to the solvent-resistant layer, an isocyanate curing agent (Nippon Polyurethane Co., Ltd.) was added to 100 parts (solid weight part) of an acrylic adhesive (Teikoku Chemical Co., Ltd., SG-800) as a slightly adhesive layer. A coating solution to which 10 parts (solid part by weight, manufactured by Coronate HL) was added was applied using a bar coater, and the coating film was dried and cured at 100 ° C. for 2 minutes to form a slightly adhesive layer having a thickness of 20 μm. A surface protective film was prepared. The characteristics of this surface protective film are shown in Table 4 below.
[0032]
Examples 2-4
A base film was prepared in the same manner as in Example 1 except that the components constituting the solvent-resistant layer were changed to the compositions shown in Table 1 below. The constitution of the solvent resistant layer of this base film is shown in Table 1, the film characteristics are shown in Table 2 and Table 3 below, and the characteristics of the surface protection film using this film are shown in Table 4.
[0033]
Comparative Example 1
A base film was prepared in the same manner as in Example 1 except that the solvent resistant layer was not provided. Thereafter, the substrate film surface was subjected to corona treatment under normal conditions, the coating liquid described in Example 1 was applied with a bar coater, the coating film was dried and cured at 150 ° C. for 1 minute, and a solvent-resistant layer was provided. It was created. The structure of the solvent resistant layer of this base film is shown in Table 1, the film characteristics are shown in Table 2, and the characteristics of the surface protection film using this film are shown in Table 4.
[0034]
Comparative Example 2
A base film was prepared in the same manner as in Example 1 except that the solvent resistant layer was not provided. The structure of the solvent resistant layer of this base film is shown in Table 1, the film characteristics are shown in Table 2, and the characteristics of the surface protection film using this film are shown in Table 4.
[0035]
Comparative Examples 3-5
A base film was prepared in the same manner as in Example 1 except that the components constituting the solvent-resistant layer were changed to the compositions shown in Table 1. The structure of the antistatic layer of this base film is shown in Table 1, the film characteristics are shown in Table 2 and Table 3, and the characteristics of the surface protection film using this film are shown in Table 4.
[0036]
[Table 1]
Figure 0005174303
[0037]
[Table 2]
Figure 0005174303
[0038]
[Table 3]
Figure 0005174303
[0039]
[Table 4]
Figure 0005174303
[0040]
【Effect of the invention】
The film of the present invention is transparent, has little peeling charge when used for a surface protective film of various displays, and has an effect of easily removing only surface dirt when used for a polarizing plate, etc. A film with high work efficiency can be provided even in a protective film peeling operation in the subsequent process without causing any obstacles during product defect inspection, and its industrial value is high.

Claims (8)

基材フィルムの片面に微粘着層を有し、もう一方の面に、当該基材フィルムの配向結晶化が完了する前に帯電防止剤、水性樹脂、および架橋剤を含有する塗布液を塗布することにより形成された帯電防止性の耐溶剤層を有するフィルムであり、暗室で蛍光灯下での目視検査による当該フィルムの1平方メートル当たりのキズの個数が1個未満であり、フィルムのヘーズが10%以下であることを特徴とするフィルム。  A base film has a slightly adhesive layer on one side, and on the other side, a coating solution containing an antistatic agent, an aqueous resin, and a crosslinking agent is applied before orientation crystallization of the base film is completed. The film has an antistatic solvent-resistant layer formed by the above method, and the number of scratches per square meter of the film is less than 1 by visual inspection under a fluorescent lamp in a dark room, and the film has a haze of 10 % Or less. 耐溶剤層が塗布により形成され、塗布後少なくとも一方向に延伸され、熱処理されていることを特徴とする請求項1記載のフィルム。  The film according to claim 1, wherein the solvent-resistant layer is formed by coating, stretched in at least one direction after coating, and heat-treated. 耐溶剤層表面をエタノールで処理した後の表面固有抵抗が1×1013以下であることを特徴とする請求項1または2記載のフィルム。The film according to claim 1 or 2, wherein the surface resistivity after treatment of the solvent-resistant layer surface with ethanol is 1 x 10 13 or less. 耐溶剤層表面をエタノールで処理した後のセロハン粘着テープに対する剥離力が100g/24mm以上であることを特徴とする請求項1〜3の何れかに記載のフィルム。  The film according to any one of claims 1 to 3, wherein the peel strength of the cellophane adhesive tape after the solvent-resistant layer surface is treated with ethanol is 100 g / 24 mm or more. 耐溶剤層表面をエタノールで処理した後のフィルムのヘーズが1〜10%、全光線透過率が80%以上であることを特徴とする請求項1〜4の何れかに記載のフィルム。  The film according to any one of claims 1 to 4, wherein the haze of the film after the surface of the solvent-resistant layer is treated with ethanol is 1 to 10%, and the total light transmittance is 80% or more. フィルムを蛍光灯下で観察した際に目視確認できる表面キズがないことを特徴とする請求項1〜5の何れかに記載のフィルム。  6. The film according to claim 1, wherein there is no surface scratch that can be visually confirmed when the film is observed under a fluorescent lamp. 耐溶剤層が、イオン性官能基を有する化合物の重合体を含むことを特徴とする請求項1〜6の何れかに記載のフィルム。  The film according to claim 1, wherein the solvent-resistant layer contains a polymer of a compound having an ionic functional group. 偏光板、位相差板および視野角拡大フィルムから選ばれる少なくとも1つの積層体の表面保護用として用いられることを特徴とする請求項1〜7の何れかに記載のフィルム。The film according to any one of claims 1 to 7, wherein the film is used for surface protection of at least one laminate selected from a polarizing plate, a retardation plate and a viewing angle widening film.
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