JP2006215175A - Reflective polarizing film - Google Patents
Reflective polarizing film Download PDFInfo
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- JP2006215175A JP2006215175A JP2005026383A JP2005026383A JP2006215175A JP 2006215175 A JP2006215175 A JP 2006215175A JP 2005026383 A JP2005026383 A JP 2005026383A JP 2005026383 A JP2005026383 A JP 2005026383A JP 2006215175 A JP2006215175 A JP 2006215175A
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Abstract
Description
本発明は、液晶表示装置の部材として用いる反射性偏光フォルムに関する。 The present invention relates to a reflective polarizing form used as a member of a liquid crystal display device.
偏光フィルムは従来から液晶表示装置の部材として用いられてきた。吸収性偏光フィルム（これはしばしばＴＡＣ／吸収性偏光フィルム／ＴＡＣの積層体として用いられる。なお、トリアセテートをＴＡＣと略記する。）を液晶セルの両面に配置した積層体とし、この積層体と光源の間に反射性偏光フィルムを配置することで液晶表示の輝度向上が図られてきた。 Conventionally, a polarizing film has been used as a member of a liquid crystal display device. An absorptive polarizing film (which is often used as a laminate of TAC / absorptive polarizing film / TAC. Triacetate is abbreviated as TAC.) Is a laminate in which both sides of a liquid crystal cell are arranged. The brightness of liquid crystal displays has been improved by disposing a reflective polarizing film between them.
液晶表示装置の輝度をさらに向上するためには、液晶セルの両面に配置されていた吸収性偏光フィルムのうち光源側に配置されているもの、すなわちＴＡＣ／吸収性偏光フィルム／ＴＡＣの積層体を、反射性偏光フィルムおよび吸収性偏光フィルムの積層体、すなわち反射性偏光フィルム／吸収性偏光フィルム／ＴＡＣの積層体で置き換えることが有効である。この場合、反射性偏光フィルムには、吸収性偏光フィルムとの十分な接着性が求められる。 In order to further improve the luminance of the liquid crystal display device, an absorptive polarizing film disposed on both sides of the liquid crystal cell is disposed on the light source side, that is, a laminate of TAC / absorptive polarizing film / TAC. It is effective to replace with a laminate of a reflective polarizing film and an absorptive polarizing film, that is, a laminate of a reflective polarizing film / absorbing polarizing film / TAC. In this case, the reflective polarizing film is required to have sufficient adhesiveness with the absorbent polarizing film.
本発明は、輝度の高い液晶表示が可能である反射性偏光フィルム／吸収性偏光フィルム／ＴＡＣの積層体の形態で液晶表示装置の部材として用いるときに吸収性偏光フィルムとの接着性の良好な易接着反射性偏光フィルムを提供することを課題とする。 The present invention has good adhesion to an absorptive polarizing film when used as a member of a liquid crystal display device in the form of a laminate of a reflective polarizing film / absorbing polarizing film / TAC capable of high-brightness liquid crystal display. It is an object to provide an easily adhesive reflective polarizing film.
すなわち本発明は、正の応力光学係数を有する熱可塑性樹脂からなる厚み０．０５〜０．５μｍの第１の層と熱可塑性樹脂からなる厚み０．０５〜０．５μｍの第２の層とを交互に合計５０１層以上含んでなる１軸多層積層延伸フィルム、およびこのうえに設けられた易接着層からなり、易接着層はガラス転移点２０〜９０℃のコポリエステル５５〜８５重量％およびケン化度８０〜９０ｍｏｌ％のポリビニルアルコール１５〜４５重量％からなることを特徴とする反射性偏光フィルムである。 That is, the present invention provides a first layer having a thickness of 0.05 to 0.5 μm made of a thermoplastic resin having a positive stress optical coefficient and a second layer having a thickness of 0.05 to 0.5 μm made of a thermoplastic resin. A uniaxial multilayer laminated stretched film comprising 501 layers or more alternately, and an easy adhesion layer provided thereon, the easy adhesion layer comprising 55 to 85% by weight of a copolyester having a glass transition point of 20 to 90 ° C. and A reflective polarizing film comprising 15 to 45% by weight of polyvinyl alcohol having a saponification degree of 80 to 90 mol%.
本発明によれば、輝度の高い液晶表示が可能であり、液晶表示装置の部材として用いるときに吸収性偏光フィルムとの接着性の良好な易接着反射性偏光フィルムを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, a liquid crystal display with high brightness | luminance is possible, and when using as a member of a liquid crystal display device, an easily-adhesive reflective polarizing film with favorable adhesiveness with an absorptive polarizing film can be provided.
以下、本発明を詳細に説明する。
［１軸延伸多層積層フィルム］
本発明において、第１の層を構成する樹脂は、正の応力複屈折（応力光学係数と同義である）を有する熱可塑性樹脂であることが必要である。正の応力複屈折を有する熱可塑性樹脂としては、ポリエチレンナフタレート（PEN）およびその異性体（例えば、2,6-、1,4-、1,5-、2,7-、および2,3-PEN）、ポリアルキレンテレフタレート（例えば、ポリエチレンテレフタレート ポリブチレンテレフタレート、およびポリ-1,4-シクロヘキサンジメチレンテレフタレート）、ポリイミド（例えば、ポリアクリル酸イミド）、ポリエーテルイミド、ポリアルキレンポリマー（例えば、ポリエチレン、ポリプロピレン、ポリブチレン、ポリイソブチレン、およびポリ（4-メチル）ペンテン）、フッ素化ポリマー（例えば、ペルフルオロアルコキシ樹脂、ポリテトラフルオロエチレン、フッ素化エチレン−プロピレンコポリマー、ポリフッ化ビニリデン、およびポリクロロトリフルオロエチレン）、塩素化ポリマー（例えば、ポリ塩化ビニリデンおよびポリ塩化ビニル）、ポリスルホン、ポリエーテルスルホン、ポリアクリロニトリル、ポリアミド、シリコーン樹脂、エポキシ樹脂、ポリ酢酸ビニル、ポリエーテルアミド、アイオノマー樹脂、エラストマー（例えば、ポリブタジエン、ポリイソプレン、およびネオプレン）、ならびにポリウレタンなどがある。
Hereinafter, the present invention will be described in detail.
[Uniaxially stretched multilayer laminated film]
In the present invention, the resin constituting the first layer needs to be a thermoplastic resin having positive stress birefringence (synonymous with the stress optical coefficient). Thermoplastic resins with positive stress birefringence include polyethylene naphthalate (PEN) and its isomers (eg 2,6-, 1,4-, 1,5-, 2,7-, and 2,3 -PEN), polyalkylene terephthalate (eg, polyethylene terephthalate, polybutylene terephthalate, and poly-1,4-cyclohexanedimethylene terephthalate), polyimide (eg, polyacrylimide), polyetherimide, polyalkylene polymer (eg, polyethylene) , Polypropylene, polybutylene, polyisobutylene, and poly (4-methyl) pentene), fluorinated polymers (eg, perfluoroalkoxy resins, polytetrafluoroethylene, fluorinated ethylene-propylene copolymers, polyvinylidene fluoride, and polychlorotrifluoroethylene) ), Chlorinated poly (Eg, polyvinylidene chloride and polyvinyl chloride), polysulfone, polyethersulfone, polyacrylonitrile, polyamide, silicone resin, epoxy resin, polyvinyl acetate, polyetheramide, ionomer resin, elastomer (eg, polybutadiene, polyisoprene, And neoprene), and polyurethane.
その中でも、応力複屈折の大きいポリエチレンナフタレート（PEN）およびその異性体（例えば、2,6-、1,4-、1,5-、2,7-、および2,3-PEN）や、ポリアルキレンテレフタレート（例えば、ポリエチレンテレフタレート ポリブチレンテレフタレート、およびポリ-1,4-シクロヘキサンジメチレンテレフタレート）などが好ましい。とりわけポリエチレンナフタレート（PEN）およびその異性体（例えば、2,6-、1,4-、1,5-、2,7-、および2,3-PEN）が好適である。 Among them, polyethylene naphthalate (PEN) with high stress birefringence and its isomers (for example, 2,6-, 1,4-, 1,5-, 2,7-, and 2,3-PEN), Polyalkylene terephthalate (for example, polyethylene terephthalate, polybutylene terephthalate, and poly-1,4-cyclohexanedimethylene terephthalate) is preferable. Particularly preferred is polyethylene naphthalate (PEN) and its isomers (eg, 2,6-, 1,4-, 1,5-, 2,7-, and 2,3-PEN).
第２の層を構成する樹脂は、熱可塑性樹脂であればよい。例えば上記に挙げた熱可塑性樹脂に加え、アタクチックポリスチレン、ポリカーボネート、ポリメタクリレート（例えば、ポリイソブチルメタクリレート、ポリプロピルメタクリレート、ポリエチルメタクリレート、およびポリメチルメタクリレート）、ポリアクリレート（例えば、ポリブチルアクリレートおよびポリメチルアクリレート）、シンジオタクチックポリスチレン（sPS）、シンジオタクチックポリ-α-メチルスチレン、シンジオタクチックポリジクロロスチレン、これらの任意のポリスチレンから成るコポリマーおよびブレンド、セルロース誘導体（例えば、エチルセルロース、酢酸セルロース、プロピオン酸セルロース、酢酸酪酸セルロース、およびニトロセルロース）などが挙げられる。 The resin constituting the second layer may be a thermoplastic resin. For example, in addition to the thermoplastic resins listed above, atactic polystyrene, polycarbonate, polymethacrylate (eg, polyisobutyl methacrylate, polypropyl methacrylate, polyethyl methacrylate, and polymethyl methacrylate), polyacrylate (eg, polybutyl acrylate and polymethacrylate) Methyl acrylate), syndiotactic polystyrene (sPS), syndiotactic poly-α-methylstyrene, syndiotactic polydichlorostyrene, copolymers and blends of any of these polystyrenes, cellulose derivatives (eg, ethyl cellulose, cellulose acetate, Cellulose propionate, cellulose acetate butyrate, and nitrocellulose).
特に第２の層として、正の応力複屈折（応力光学係数と同義である）を有する熱可塑性樹脂を使用する場合には、第１の層を構成する熱可塑性樹脂の融点よりも１５〜６０℃低いことが好ましい。その中でも、層間密着性の観点から第１の層にとりわけ好適なポリエチレンナフタレート（PEN）およびその異性体（例えば、2,6-、1,4-、1,5-、2,7-、および2,3-PEN）の融点よりも１５〜６０℃低いPENのコポリマー（例えば、2,6-、1,4-、1,5-、2,7-、および／または2,3-ナフタレンジカルボン酸もしくはそれらのエステルと、(a)テレフタル酸もしくはそのエスデル、(b)イソフタル酸もしくはそのエステル、(c)フタル酸もしくはそのエステル、(d)アルカングリコール、(e)シクロアルカングリコール（例えば、シクロヘキサンジメタノールジオール）、(f)アルカンジカルボン酸、および／または(g)シクロアルカンジカルボン酸（例えば、シクロヘキサンジカルボン酸）とのコポリマー）、ポリアルキレンテレフタレートのコポリマー（例えば、テレフタル酸もしくはそのエステルと、(a)ナフタレンジカルボン酸もしくはそのエステル、(b)イソフタル酸もしくはそのエステル、(c)フタル酸もしくはそのエステル、(d)アルカングリコール、(e)シクロアルカングリコール（例えば、シクロヘキサンジメタノールジオール）、(f)アルカンジカルボン酸、および／または(g)シクロアルカンジカルボン酸（例えば、シクロヘキサンジカルボン酸）とのコポリマー）、スチレンコポリマー（例えば、スチレン−ブタジエンコポリマーおよびスチレン−アクリロニトリルコポリマー）、ならびに4,4’−二安息香酸とエチレングリコールとのコポリマーなど、のコポリマーなどが挙げられる。 In particular, when a thermoplastic resin having positive stress birefringence (synonymous with the stress optical coefficient) is used as the second layer, the melting point of the thermoplastic resin constituting the first layer is 15-60. A lower temperature is preferred. Among them, polyethylene naphthalate (PEN) particularly suitable for the first layer from the viewpoint of interlayer adhesion and isomers thereof (for example, 2,6-, 1,4-, 1,5-, 2,7-, And copolymers of PEN (eg, 2,6-, 1,4-, 1,5-, 2,7-, and / or 2,3-naphthalene that are 15-60 ° C. below the melting point of 2,3-PEN) A dicarboxylic acid or ester thereof and (a) terephthalic acid or esdel thereof, (b) isophthalic acid or ester thereof, (c) phthalic acid or ester thereof, (d) alkane glycol, (e) cycloalkane glycol (for example, Cyclohexanedimethanoldiol), (f) alkanedicarboxylic acids, and / or (g) copolymers with cycloalkanedicarboxylic acids (eg cyclohexanedicarboxylic acid)), copolymers of polyalkylene terephthalates (eg terephthalic acid Or (a) naphthalene dicarboxylic acid or its ester, (b) isophthalic acid or its ester, (c) phthalic acid or its ester, (d) alkane glycol, (e) cycloalkane glycol (for example, cyclohexane) Dimethanoldiol), (f) alkanedicarboxylic acid, and / or (g) copolymer with cycloalkanedicarboxylic acid (eg, cyclohexanedicarboxylic acid)), styrene copolymer (eg, styrene-butadiene copolymer and styrene-acrylonitrile copolymer), And copolymers of 4,4′-dibenzoic acid and ethylene glycol.
第１の層は、ポリエチレン−２，６−ナフタレンジカルボキシレートからなることが好ましい。第２の層は、イソフタル酸成分またはテレフタル酸成分を１．５〜２０モル％共重合した共重合ポリエチレン−２，６−ナフタレンジカルボキシレートであることが好ましい。 The first layer is preferably made of polyethylene-2,6-naphthalenedicarboxylate. The second layer is preferably a copolymerized polyethylene-2,6-naphthalenedicarboxylate obtained by copolymerizing an isophthalic acid component or a terephthalic acid component in an amount of 1.5 to 20 mol%.
以下、さらに本発明における１軸延伸多層積層フィルムの好適な例について詳述する。
本発明のもっとも好適な例において、第１の層を構成する樹脂は、主たる繰返し単位がエチレン−２，６−ナフタレンジカルボキシレート成分からなるポリエステルである。好ましくは、後述の第２の層を構成するポリエステルよりも融点を高度に維持できることから、ホモポリエチレン−２，６−ナフタレンジカルボキシレートまたは繰返し単位の９５モル％以上がエチレン−２，６−ナフタレンジカルボキシレート成分からなる共重合ポリエチレン−２，６−ナフタレンジカルボキシレートである。エチレン−２，６−ナフタレンジカルボキシレート成分のモル数が繰返し単位の９５モル％未満だと、融点が低下し、後述の第２の層を構成するポリエステルとの融点差が得られがたく、結果として、多層延伸フィルムに十分な屈折率差を付与しがたい。これらの中でも、融点を高度に維持できることから、ホモポリエチレン−２，６−ナフタレンジカルボキシレートが好ましい。エチレン−２，６−ナフタレンジカルボキシレート成分以外の共重合成分としては、イソフタル酸、２，７−ナフタレンジカルボン酸のような他の芳香族カルボン酸；アジピン酸、アゼライン酸、セバシン酸、デカンジカルボン酸等の如き脂肪族ジカルボン酸；シクロヘキサンジカルボン酸の如き脂環族ジカルボン酸等の酸成分や、ブタンジオール、ヘキサンジオール等の如き脂肪族ジオール；シクロヘキサンジメタノールの如き脂環族ジオール等、グリコール成分を好ましく挙げることができる。
Hereinafter, the suitable example of the uniaxially stretched multilayer laminated film in this invention is explained in full detail.
In the most preferred example of the present invention, the resin constituting the first layer is a polyester whose main repeating unit is an ethylene-2,6-naphthalenedicarboxylate component. Preferably, since the melting point can be maintained higher than that of the polyester constituting the second layer described later, 95% by mole or more of homopolyethylene-2,6-naphthalenedicarboxylate or repeating units is ethylene-2,6-naphthalene. It is a copolymerized polyethylene-2,6-naphthalenedicarboxylate composed of a dicarboxylate component. When the number of moles of the ethylene-2,6-naphthalenedicarboxylate component is less than 95 mol% of the repeating unit, the melting point is lowered, and it is difficult to obtain a difference in melting point from the polyester constituting the second layer described later. As a result, it is difficult to give a sufficient refractive index difference to the multilayer stretched film. Among these, homopolyethylene-2,6-naphthalenedicarboxylate is preferable because the melting point can be maintained at a high level. Examples of copolymer components other than the ethylene-2,6-naphthalenedicarboxylate component include other aromatic carboxylic acids such as isophthalic acid and 2,7-naphthalenedicarboxylic acid; adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid Aliphatic dicarboxylic acids such as acids; Acid components such as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; Aliphatic diols such as butanediol and hexanediol; Glycol components such as alicyclic diols such as cyclohexanedimethanol Can be preferably mentioned.
ところで、第１の層を構成する樹脂の融点は、２６０〜２７０℃の範囲であることが、後述の第２の層を構成する樹脂との融点差を比較的大きくできることから必要である。第１の層を構成する樹脂の融点が下限よりも低いと、第２の層を構成する樹脂との融点差が小さくなり、結果として、得られる多層延伸フィルムに十分な屈折率差を付与することが困難になる。なお、共重合していないポリエチレン−２，６−ナフタレンジカルボキシレートの融点は、通常２６７℃近傍である。 By the way, it is necessary for the melting point of the resin constituting the first layer to be in the range of 260 to 270 ° C. because the melting point difference from the resin constituting the second layer described later can be relatively large. When the melting point of the resin constituting the first layer is lower than the lower limit, the melting point difference from the resin constituting the second layer is reduced, and as a result, a sufficient refractive index difference is imparted to the resulting multilayer stretched film. It becomes difficult. The melting point of uncopolymerized polyethylene-2,6-naphthalenedicarboxylate is usually around 267 ° C.
本発明の好適な例において、第２の層を構成する樹脂は、融点が２１０〜２５５℃である主たる繰返し単位がエチレン−２，６−ナフタレンジカルボキシレート成分からなるポリエステルである。特に２軸延伸における製膜性の観点から、結晶性ポリエステルであることが必要である。また、前述の第１の層を構成するポリエステルよりも融点を低くできることから、好ましくは繰返し単位の７５〜９７モル％がエチレン−２，６−ナフタレンジカルボキシレート成分からなり、３〜２５モル％がそれ以外の共重合成分からなる共重合ポリエチレン−２，６−ナフタレンジカルボキシレートである。エチレン−２，６−ナフタレンジカルボキシレート成分のモル数が繰返し単位の７５モル％未満であるか共重合成分のモル数が２５モル％を超えると、実質的にポリマーが非晶性を示し、２軸延伸での製膜性が低下し、かつ前述の第１の層を構成するポリエステルとの組成が大きく異なり、層間の密着性が低下しやすい。他方、エチレン−２，６−ナフタレンジカルボキシレート成分のモル数が繰返し単位の９７モル％を超えるか共重合成分のモル数が３モル％未満だと、前述の第１の層を構成するポリエステルとの融点差が小さくなり、結果として、多層延伸フィルムに十分な反射率を付与することが困難となる。エチレン−２，６−ナフタレンジカルボキシレート成分以外の共重合成分としては、イソフタル酸、２，７−ナフタレンジカルボン酸のような他の芳香族カルボン酸；アジピン酸、アゼライン酸、セバシン酸、デカンジカルボン酸等の如き脂肪族ジカルボン酸；シクロヘキサンジカルボン酸の如き脂環族ジカルボン酸等の酸成分や、ブタンジオール、ヘキサンジオール等の如き脂肪族ジオール；シクロヘキサンジメタノールの如き脂環族ジオール等、グリコール成分を好ましく挙げることができる。これらの中でも、比較的、延伸性を維持しながら融点を低下させやすいことからテレフタル酸またはイソフタル酸が好ましい。 In a preferred example of the present invention, the resin constituting the second layer is a polyester whose main repeating unit having a melting point of 210 to 255 ° C. is composed of an ethylene-2,6-naphthalenedicarboxylate component. In particular, from the viewpoint of film forming property in biaxial stretching, it is necessary to be a crystalline polyester. Further, since the melting point can be made lower than that of the polyester constituting the first layer, preferably 75 to 97 mol% of the repeating unit is composed of an ethylene-2,6-naphthalenedicarboxylate component, and 3 to 25 mol%. Is a copolymerized polyethylene-2,6-naphthalenedicarboxylate composed of other copolymer components. When the number of moles of the ethylene-2,6-naphthalenedicarboxylate component is less than 75 mole% of the repeating unit or the number of moles of the copolymer component exceeds 25 mole%, the polymer is substantially amorphous, The film-forming property by biaxial stretching is lowered, and the composition with the polyester constituting the first layer is greatly different, and the adhesion between the layers tends to be lowered. On the other hand, when the number of moles of the ethylene-2,6-naphthalenedicarboxylate component exceeds 97 mol% of the repeating unit or the number of moles of the copolymer component is less than 3 mol%, the polyester constituting the first layer described above As a result, it becomes difficult to give sufficient reflectivity to the multilayer stretched film. Examples of copolymer components other than the ethylene-2,6-naphthalenedicarboxylate component include other aromatic carboxylic acids such as isophthalic acid and 2,7-naphthalenedicarboxylic acid; adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid Aliphatic dicarboxylic acids such as acids; acid components such as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aliphatic diols such as butanediol and hexanediol; glycol components such as alicyclic diols such as cyclohexanedimethanol Can be preferably mentioned. Among these, terephthalic acid or isophthalic acid is preferable because it is relatively easy to lower the melting point while maintaining stretchability.
ところで、第２の層を構成する樹脂の融点は、２１０〜２５５℃の範囲であることが、前述の第１の層を構成する樹脂との融点差を比較的大きくできることから好ましい。第２の層を構成する樹脂の融点が上限よりも高いと、第１の層を構成する樹脂との融点差が小さくなり、結果として、得られる多層延伸フィルムに十分な屈折率差を付与することが困難になる。一方、第２の層を構成する樹脂の融点が下限よりも低くするには、第１の層を構成する樹脂との組成が大きく変更することになり、得られる１軸延伸多層積層フィルムに十分な層間の密着性を付与することが困難になる。なお、第２の層を構成する樹脂の融点は、フィルムにする前の段階から低い必要はなく、延伸処理後に低くなっていれば良い。例えば、ホモポリエチレン−２，６−ナフタレンジカルボキシレートとそれ以外の他のポリエステルとを用意し、これらを溶融混練時にエステル交換させたものであってもよい。 Incidentally, the melting point of the resin constituting the second layer is preferably in the range of 210 to 255 ° C., since the difference in melting point from the resin constituting the first layer can be relatively large. When the melting point of the resin constituting the second layer is higher than the upper limit, the melting point difference from the resin constituting the first layer is reduced, and as a result, a sufficient refractive index difference is imparted to the resulting multilayer stretched film. It becomes difficult. On the other hand, in order for the melting point of the resin constituting the second layer to be lower than the lower limit, the composition with the resin constituting the first layer is greatly changed, which is sufficient for the obtained uniaxially stretched multilayer laminated film. It becomes difficult to provide adhesion between layers. Note that the melting point of the resin constituting the second layer does not need to be low from the stage before forming the film, and may be low after the stretching treatment. For example, homopolyethylene-2,6-naphthalene dicarboxylate and other polyesters other than that may be prepared, and these may be transesterified during melt kneading.
第１の層および第２の層は、層間の光干渉によって選択的に光を反射するために、それぞれ１層の厚みが０．０５〜０．５μｍである。多層光学フィルムの反射特性は、層数、屈折率差、層の厚みで決定する。本発明における１軸延伸多層積層フィルムが示す反射波長帯は、可視光域から近赤外線領域であることから、上記層厚の範囲とすることが必要である。層厚みが０．５μｍを越えると反射帯域が赤外線領域になり反射偏光フィルムとして有用性が得られない。他方０．０５μｍ未満であると反射光は、反射帯域が紫外線領域になり、実質的に性能が得られなくなる。 Each of the first layer and the second layer has a thickness of 0.05 to 0.5 μm in order to selectively reflect light by optical interference between the layers. The reflection characteristics of the multilayer optical film are determined by the number of layers, refractive index difference, and layer thickness. Since the reflection wavelength band shown by the uniaxially stretched multilayer laminated film in the present invention is from the visible light region to the near infrared region, it is necessary to set the layer thickness within the above range. When the layer thickness exceeds 0.5 μm, the reflection band becomes an infrared region, and usefulness as a reflective polarizing film cannot be obtained. On the other hand, if the thickness is less than 0.05 μm, the reflected light has a reflection band in the ultraviolet region, and substantially no performance can be obtained.
本発明における１軸延伸多層積層フィルムでは、積層数は、少なくとも５０１層必要である。層数が５０１層未満であると、波長４００〜８００ｎｍにわたり、上記の目的とする光学特性を満足するすることができない。積層数の上限は、生産性およびフィルムのハンドリング性など観点から、高々２００１層であることが好ましい。 In the uniaxially stretched multilayer laminated film in the present invention, the number of laminated layers needs to be at least 501 layers. If the number of layers is less than 501 layers, the above-described optical characteristics cannot be satisfied over a wavelength range of 400 to 800 nm. The upper limit of the number of layers is preferably at most 2001 layers from the viewpoint of productivity and film handling.
この１軸延伸多層積層フィルムでは、第１の層の平均厚みに対する第２の層の平均厚みの比率は、好ましくは０．５〜５．０、さらに好ましくは１．０〜４．０、特に好ましくは１．５〜３．５である。第１の層と第２の層の厚み比を変化させることにより層間の密着性を維持したまま、また使用する樹脂を変更することなく、１軸延伸多層積層フィルムの機械特性を調整することができる。第１の層の平均厚みに対する第２の層の平均厚みの比率が０．５未満であると１軸延伸多層積層フィルムの延伸方向に裂け易くなる。他方、第１の層の平均厚みに対する第２の層の平均厚みの比率が５．０を超えると熱処理による配向緩和の差異に１軸延伸多層積層フィルムの厚みの変動が大きくなる。 In this uniaxially stretched multilayer laminated film, the ratio of the average thickness of the second layer to the average thickness of the first layer is preferably 0.5 to 5.0, more preferably 1.0 to 4.0, particularly Preferably it is 1.5-3.5. By changing the thickness ratio between the first layer and the second layer, the mechanical properties of the uniaxially stretched multilayer laminated film can be adjusted while maintaining the adhesion between the layers and without changing the resin used. it can. When the ratio of the average thickness of the second layer to the average thickness of the first layer is less than 0.5, the uniaxially stretched multilayer laminated film is easily torn in the stretching direction. On the other hand, when the ratio of the average thickness of the second layer to the average thickness of the first layer exceeds 5.0, the variation in the thickness of the uniaxially stretched multilayer laminate film increases due to the difference in orientation relaxation due to heat treatment.
本発明における１軸延伸多層積層フィルムでは、第１の層および第２の層それぞれの最大厚みと最小厚みの比率は、好ましくは１．５〜５．０、さらに好ましくは２．０〜４．０、特に好ましくは２．５〜３．５である。第１の層および第２の層は、段階的に変化してもよく、連続的に変化してもよい。このように積層された第１の層および第２の層のそれぞれが変化することで、より広い波長域の光を反射することができる。第１の層および第２の層それぞれの最大厚みと最小厚みの比率が１．５未満であると、４００〜８００ｎｍの波長域に渡り前述の目的となる反射特性をカバーできない。他方、第１の層および第２の層それぞれの最大厚みと最小厚みの比率が５．０を超えると反射帯域が広がりすぎ、反射率が低下するために、前述の目的となる反射特性が得られない。また、このとき、積層構造として、段階的または、連続的に変化する多層構造の表層または、内部に０．５ｕｍ以上の層が１層以上存在してもよい。 In the uniaxially stretched multilayer laminated film of the present invention, the ratio between the maximum thickness and the minimum thickness of each of the first layer and the second layer is preferably 1.5 to 5.0, more preferably 2.0 to 4. 0, particularly preferably 2.5 to 3.5. The first layer and the second layer may change stepwise or may change continuously. By changing each of the first layer and the second layer laminated in this manner, light in a wider wavelength range can be reflected. When the ratio between the maximum thickness and the minimum thickness of each of the first layer and the second layer is less than 1.5, the above-described reflection characteristics cannot be covered over the wavelength range of 400 to 800 nm. On the other hand, if the ratio between the maximum thickness and the minimum thickness of each of the first layer and the second layer exceeds 5.0, the reflection band becomes too wide and the reflectance is lowered, so that the above-described reflection characteristics can be obtained. I can't. At this time, as a laminated structure, one or more layers of 0.5 μm or more may exist in the surface layer of a multilayer structure that changes stepwise or continuously.
本発明における１軸延伸多層積層フィルムは、１軸延伸フィルムの延伸方向とフィルム面内方向を基準とする平面に対して平行な偏光成分について、波長４００〜８００ｎｍの平均反射率が９０％以上、好ましくは９５％以上、さらに好ましくは９８％以上であり、同平面に対して垂直な偏光成分について、波長４００〜８００ｎｍの平均反射率が好ましくは１５％以下、さらに好ましくは１０％以下、さらに好ましくは５％以下、特に好ましくは１％以下である。１軸延伸フィルムの延伸方向とフィルム面内方向を基準とする平面に対して平行な偏光成分について、波長４００〜８００ｎｍの平均反射率が９０％未満であると反射偏光フィルムとしての偏光反射性能が不十分であり、液晶ディスプレイなどの輝度向上フィルムのとして十分な性能を発現しない。また、同平面に対して垂直な偏光成分について、波長４００〜８００ｎｍの平均反射率が１５％を超えると反射偏光フィルムとしての偏光透過率が低下するため、液晶ディスプレイなどの輝度向上フィルムのとして性能が劣る。 The uniaxially stretched multilayer laminated film in the present invention has an average reflectance of a wavelength of 400 to 800 nm of 90% or more with respect to a polarization component parallel to a plane based on the stretching direction of the uniaxially stretched film and the film in-plane direction. Preferably, it is 95% or more, more preferably 98% or more, and with respect to a polarized light component perpendicular to the same plane, the average reflectance at a wavelength of 400 to 800 nm is preferably 15% or less, more preferably 10% or less, more preferably Is 5% or less, particularly preferably 1% or less. About the polarization component parallel to the plane based on the stretching direction of the uniaxially stretched film and the in-plane direction of the film, if the average reflectance at a wavelength of 400 to 800 nm is less than 90%, the polarization reflection performance as a reflective polarizing film is It is insufficient, and does not exhibit sufficient performance as a brightness enhancement film such as a liquid crystal display. In addition, with respect to a polarized light component perpendicular to the same plane, if the average reflectance at a wavelength of 400 to 800 nm exceeds 15%, the polarized light transmittance as a reflective polarizing film decreases, so that it can be used as a brightness enhancement film for liquid crystal displays and the like. Is inferior.
この１軸延伸多層積層フィルムでは、１軸延伸フィルムの延伸方向とフィルム面内方向を基準とする平面に対して平行な偏光成分について、波長４００〜８００ｎｍの各波長における最大反射率と最小反射率の差が１０％以内であり、かつ、同平面に対して垂直な偏光成分について、波長４００〜８００ｎｍの各波長における最大反射率と最小反射率の差が１０％以内であることが好ましい。上記偏光成分の最大反射率と最小反射率の差が１０％を超えると、反射または透過する光の色相のずれが生じるために液晶ディスプレイなどに使用に問題が生じることがある。 In this uniaxially stretched multilayer laminated film, the maximum reflectance and the minimum reflectance at each wavelength of 400 to 800 nm with respect to the polarization component parallel to the plane based on the stretching direction of the uniaxially stretched film and the film in-plane direction. The difference between the maximum reflectance and the minimum reflectance at each wavelength of 400 to 800 nm is preferably within 10% for a polarized light component perpendicular to the same plane and within 10%. If the difference between the maximum reflectance and the minimum reflectance of the polarization component exceeds 10%, the hue of the reflected or transmitted light may be shifted, which may cause a problem in use for a liquid crystal display or the like.
図１に、本発明における１軸延伸多層積層フィルムの反射率曲線の一例を示す。Ｐ偏光とは、フィルムの延伸方向とフィルム面と垂直方向を含む面内に平行な偏光成分であり、Ｓ偏光とは、フィルムの延伸方向とフィルム面と垂直方向を含む面内に垂直な変更成分を示す。 In FIG. 1, an example of the reflectance curve of the uniaxial stretching multilayer laminated film in this invention is shown. P-polarized light is a polarized light component that is parallel to a plane that includes a film stretching direction and a direction perpendicular to the film surface, and S-polarized light is a change that is perpendicular to the film stretching direction and a plane that includes a direction perpendicular to the film surface. Ingredients are shown.
本発明における１軸延伸多層積層フィルムでは、第１の層および第２の層それぞれの最大厚みと最小厚みの比率が１．５〜５．０であることが好ましい。第１の層および第２の層は、段階的に変化してもよく、連続的に変化してもよい。このように積層された第１の層および第２の層のそれぞれが変化することで、より広い波長域の光を反射することができる。また、積層体の表層や中間層に０．５μｍ以上の厚膜層が存在してもよい。 In the uniaxially stretched multilayer laminated film of the present invention, the ratio of the maximum thickness and the minimum thickness of each of the first layer and the second layer is preferably 1.5 to 5.0. The first layer and the second layer may change stepwise or may change continuously. By changing each of the first layer and the second layer laminated in this manner, light in a wider wavelength range can be reflected. Further, a thick film layer of 0.5 μm or more may be present on the surface layer or intermediate layer of the laminate.
本発明における１軸延伸多層積層フィルムにおける、多層構造を積層する方法は特に限定されないが、例えば、第１の層用ポリエステルを２５１層、第２の層用ポリエステルを２５０層に分岐させた第１の層と第２の層が交互に積層され、その流路が連続的に１〜３倍までに変化する多層フィードブロック装置を使用する方法や、多層フィードブロック装置により、２０１層の均一な層を積層しておき、その積層された流動体をさらに１．０：１．３：２．０の比で積層された面に垂直に３分岐したのち再び積層して６０１層にするといった方法もある。また、両者を組み合わせた方法を用いることもできる。 The method for laminating the multilayer structure in the uniaxially stretched multilayer laminated film of the present invention is not particularly limited. For example, the first layer polyester is divided into 251 layers and the second layer polyester is branched into 250 layers. The layer and the second layer are alternately stacked, and a method using a multi-layer feed block device in which the flow path continuously changes by 1 to 3 times, or a multi-layer feed block device, 201 uniform layers In another method, the laminated fluid is further branched into three perpendicularly to the laminated surface at a ratio of 1.0: 1.3: 2.0, and then laminated again to form a 601 layer. is there. Moreover, the method which combined both can also be used.
本発明における１軸延伸多層積層フィルムは、上述の第１の層および第２の層を、交互に少なくとも合計５０１層積層したものである。なお、本発明における１軸延伸多層積層フィルムは、前述のとおり、目的とする反射偏光フィルムとしての光学特性を満足するために１軸方向に延伸されている。このとき、延伸方向は、縦方向であっても、横方向であってもよい。また、光学特性を満足される範囲で多段延伸を付与してもよい。また、延伸方法としては、棒状ヒータによる加熱延伸、ロール加熱延伸、テンター延伸など公知の延伸方法を用いることができるが、ロールとの接触によるキズの低減や延伸速度などの観点から、テンター延伸が好ましい。 The uniaxially stretched multilayer laminated film in the present invention is obtained by alternately laminating at least a total of 501 layers of the first layer and the second layer described above. In addition, as described above, the uniaxially stretched multilayer laminated film in the present invention is stretched in the uniaxial direction in order to satisfy the optical properties as the target reflective polarizing film. At this time, the stretching direction may be the longitudinal direction or the lateral direction. Moreover, you may provide multistage extending | stretching in the range by which an optical characteristic is satisfied. In addition, as a stretching method, a known stretching method such as heat stretching with a rod heater, roll heating stretching, and tenter stretching can be used, but from the viewpoint of reduction of scratches due to contact with the roll and stretching speed, tenter stretching is performed. preferable.
特に、本発明における１軸延伸多層積層フィルムは、層間の密着性及び延伸加工の製膜性を確保する観点から、第１の層、第２の層ともに、正の応力光係数を示す結晶性樹脂を使用し、かつ第２の層の樹脂は、延伸後には、少なくとも部分的に溶融されて配向が緩和されていることが好ましい。このようにして得られた１軸延伸多層積層フィルムは、ＤＳＣ（示差走査熱量計）で測定される融点が２つ以上存在し、かつそれらの融点か５℃以上異なることが好ましい。ここで、測定される融点は、高融点側が高屈折率を示す第１の層であり、低融点側は、低屈折率を示す第２の層であることは容易に想像がつくであろう。また、さらに好ましくは、延伸後に第２の層は少なくとも部分的に溶融されているために、ＤＳＣで測定される結晶化ピークが１５０℃〜２２０℃の範囲に存在することが好ましい。結晶化ピークが１５０℃以下であると、フィルムの延伸時に一方の層が急激に結晶化するために製膜時の製膜性が低下したり、膜質の均質性が低下しやすく、結果として、色相の斑などが発生することがある。一方で結晶化ピークが２２０℃以上であると、熱固定処理で第二の層を融解するときに、結晶化が同時に起こり、十分な屈折率差を発現させ難くなる。 In particular, the uniaxially stretched multilayer laminated film according to the present invention has a crystallinity exhibiting a positive stress light coefficient in both the first layer and the second layer from the viewpoint of ensuring adhesion between layers and film forming property of stretching. The resin is used, and the second layer resin is preferably at least partially melted and relaxed in orientation after stretching. The uniaxially stretched multilayer laminated film thus obtained preferably has two or more melting points measured by DSC (differential scanning calorimeter), and the melting points thereof are preferably different by 5 ° C. or more. Here, it can be easily imagined that the measured melting point is the first layer exhibiting a high refractive index on the high melting point side, and the second layer exhibiting the low refractive index on the low melting point side. . More preferably, since the second layer is at least partially melted after stretching, the crystallization peak measured by DSC is preferably in the range of 150 ° C to 220 ° C. When the crystallization peak is 150 ° C. or lower, one of the layers rapidly crystallizes when the film is stretched, so that the film-forming property at the time of film formation is reduced, or the uniformity of the film quality is likely to be reduced. Spots of hue may occur. On the other hand, when the crystallization peak is 220 ° C. or higher, when the second layer is melted by heat setting, crystallization occurs at the same time, and it becomes difficult to express a sufficient refractive index difference.
このように、本発明における１軸延伸多層積層フィルムは、ともに結晶性を示す第一の層の樹脂と第二の層の樹脂を延伸することによって、均質な膜質のフィルムが得られ、かつ延伸工程の後に第二の層を融解することで、層間密着性を向上させることと同時に反射性能を向上させることができる。従って、本発明における１軸延伸多層積層フィルムでは、ＤＳＣによる結晶ピークが１５０℃〜２２０℃に存在し、融点差が５℃以上異なる２つ以上の融解ピークが観測される１軸延伸多層積層フィルムが好ましい。 As described above, the uniaxially stretched multilayer laminated film in the present invention is obtained by stretching the resin of the first layer and the resin of the second layer, both of which exhibit crystallinity, and a film having a uniform film quality is obtained and stretched. By melting the second layer after the process, the interlayer adhesion can be improved and simultaneously the reflection performance can be improved. Therefore, in the uniaxially stretched multilayer laminate film of the present invention, a uniaxially stretched multilayer laminate film in which a crystal peak by DSC exists at 150 ° C. to 220 ° C., and two or more melting peaks different in melting point difference by 5 ° C. or more are observed Is preferred.
また、本発明における１軸延伸多層積層フィルムは、延伸処理された方向の破断強度は、それぞれ１００ＭＰａ以上であることが好ましい。破断強度が１００ＭＰａ未満だと、多層延伸フィルムの加工時における取り扱い性が低下したり、製品にしたときの耐久性が低下したりする。また、破断強度が１００ＭＰａ以上であると、フィルムの腰が強くなり、巻取り性が向上するという利点もある。好ましい破断強度は、縦方向が１５０ＭＰａ以上、特に２００ＭＰａ以上で、横方向が１５０ＭＰａ以上、特に２００ＭＰａ以上である。また、縦方向と横方向の強度比は、３以下であることが耐引裂き性を十分に具備できることから好ましい。特に縦方向と横方向の強度比が２以下であると、さらに耐引裂き性を向上できることから好ましい。破断強度の上限は、特に限定はされないが、延伸工程の安定性を維持する観点から、高々５００ＭＰａであることが好ましい。 The uniaxially stretched multilayer laminated film in the present invention preferably has a breaking strength in the stretched direction of 100 MPa or more. When the breaking strength is less than 100 MPa, the handleability during processing of the multilayer stretched film is lowered, and the durability when it is made into a product is lowered. Further, when the breaking strength is 100 MPa or more, there is an advantage that the stiffness of the film becomes strong and the winding property is improved. The preferred breaking strength is 150 MPa or more in the longitudinal direction, particularly 200 MPa or more, and 150 MPa or more, particularly 200 MPa or more in the transverse direction. In addition, the strength ratio in the longitudinal direction and the transverse direction is preferably 3 or less because tear resistance can be sufficiently obtained. In particular, the strength ratio in the longitudinal direction and the transverse direction is preferably 2 or less because tear resistance can be further improved. The upper limit of the breaking strength is not particularly limited, but is preferably at most 500 MPa from the viewpoint of maintaining the stability of the stretching process.
また、本発明における１軸延伸多層積層フィルムは、ポリエチレン−２，６−ナフタレンジカルボキシレートを主成分とすることから、特に熱寸法安定性が高いことが特徴であり、とりわけ加工プロセスにおいて、１６０℃以上の高温を必要とする場合にも十分に対応することができる。本フィルムの延伸処理された方向（製膜方向および幅方向のいずれか）の１５０℃で３０分間処理したときの熱収縮率が、好ましくは５．０％以下、さらに好ましくは１．５％以下、とくに好ましくは１．０％以下である。また、本発明における１軸延伸多層積層フィルムの２００℃で１０分間処理したときの製膜方向および幅方向のいずれかの熱収縮率は、好ましくは３．０％以下、さらに好ましくは２．０％以下、特に好ましくは１．５％以下である。 In addition, the uniaxially stretched multilayer laminated film in the present invention is characterized by particularly high thermal dimensional stability since it mainly comprises polyethylene-2,6-naphthalenedicarboxylate. Even when a high temperature of ℃ or higher is required, it can sufficiently cope. The heat shrinkage rate when treated for 30 minutes at 150 ° C. in the direction in which the film is stretched (either in the film forming direction or in the width direction) is preferably 5.0% or less, more preferably 1.5% or less. Especially preferably, it is 1.0% or less. In addition, the heat shrinkage rate in either the film forming direction or the width direction when the uniaxially stretched multilayer laminated film in the present invention is treated at 200 ° C. for 10 minutes is preferably 3.0% or less, more preferably 2.0. % Or less, particularly preferably 1.5% or less.
また、本発明における１軸延伸多層積層フィルムは、第１の層および第２の層を構成する樹脂が、ともに結晶性樹脂であることが好ましい。第１の層および第２の層を構成する樹脂がともに結晶性樹脂であると、延伸などの処理が不均一になりがたく、結果としてフィルムの厚み斑を小さくすることができる。厚み斑の範囲は、下記式で示される厚み変動率が、好ましくは１０％未満、さらに好ましくは５％未満、特に好ましくは３．０％未満である。フィルム厚みの変動幅が１０％以上になると、光学特性のずれが大きくなり色相ずれなどから目的とする光学特性が得られない。
厚み変動率（％）＝（Ｔｍａｘ−Ｔｍｉｎ）／（ＴＡｖｅ）
ここで、上記式中のＴｍａｘは最大厚み、Ｔｍｉｎは最小厚み、およびＴＡｖｅは庭訓厚みである。
In the uniaxially stretched multilayer laminated film of the present invention, it is preferable that the resins constituting the first layer and the second layer are both crystalline resins. If both the resin constituting the first layer and the second layer are crystalline resins, the treatment such as stretching is unlikely to be uneven, and as a result, the thickness unevenness of the film can be reduced. The range of thickness spots is such that the thickness fluctuation rate represented by the following formula is preferably less than 10%, more preferably less than 5%, and particularly preferably less than 3.0%. When the fluctuation width of the film thickness is 10% or more, the optical characteristic shift becomes large, and the target optical characteristic cannot be obtained due to hue shift or the like.
Thickness variation rate (%) = (T max −T min ) / (T Ave )
Here, T max in the above formula is the maximum thickness, T min is the minimum thickness, and T Ave is the garden thickness.
本発明の１軸延伸多層積層フィルムは、フィルムの巻取り性を向上させるため、第１の層または第２の層の少なくとも一方に不活性粒子を１軸延伸多層積層フィルムの重量を基準として、好ましくは０．００１重量％〜０．５重量％、さらに好ましくは０．００５〜０．２重量％含有する。不活性粒子の平均粒径は、好ましくは０．０１μｍ〜２μｍ、さらに好ましくは０．０５〜１μｍ、特に好ましくは０．１〜０．３μｍである。平均粒径が下限よりも小さいか、含有量が下限よりも少ないと、１軸延伸多層積層フィルムの巻取り性を向上させる効果が不十分になりやすく、他方、不活性粒子の含有量が上限を超えるか、平均粒径が上限を超えると、粒子による多層延伸フィルムの光学特性の悪化が顕著になり好ましくない。 In order to improve the rollability of the film, the uniaxially stretched multilayer laminate film of the present invention is based on the weight of the uniaxially stretched multilayer laminate film with inert particles in at least one of the first layer and the second layer. The content is preferably 0.001 to 0.5% by weight, more preferably 0.005 to 0.2% by weight. The average particle diameter of the inert particles is preferably 0.01 μm to 2 μm, more preferably 0.05 to 1 μm, and particularly preferably 0.1 to 0.3 μm. If the average particle size is smaller than the lower limit or the content is less than the lower limit, the effect of improving the winding property of the uniaxially stretched multilayer laminated film tends to be insufficient, while the content of inert particles is the upper limit. If the average particle size exceeds the upper limit, the deterioration of the optical properties of the multilayer stretched film due to the particles becomes remarkable, which is not preferable.
つぎに、本発明における１軸延伸多層積層フィルム製造方法の最も好ましい例について、詳述する。
本発明における１軸延伸多層積層フィルムは、融点が２６０〜２７０℃のエチレン−２，６−ナフタレンジカルボキシレート成分を主たる繰返し単位とするポリエステル（第１の層用）と、該第１の層を構成するポリエステルよりも、延伸処理後の融点が少なくとも１０℃以上低い、エチレン−２，６−ナフタレンジカルボキシレート成分を主たる繰返し単位とするポリエステル（第２の層用）とを、溶融状態で交互に少なくとも５０１層以上重ね合わせた状態で、押出し、多層未延伸フィルム（シート状物とする工程）とする。このとき、積層された５０１層以上の積層物は、その層厚が段階的または、連続的に１．５倍〜５．０倍の範囲で変化するように積層される。
Next, the most preferable example of the method for producing a uniaxially stretched multilayer laminated film in the present invention will be described in detail.
The uniaxially stretched multilayer laminated film according to the present invention includes a polyester (for the first layer) having an ethylene-2,6-naphthalenedicarboxylate component having a melting point of 260 to 270 ° C. as a main repeating unit, and the first layer. A polyester (for the second layer) having an ethylene-2,6-naphthalenedicarboxylate component as a main repeating unit, the melting point after stretching being lower by at least 10 ° C. than the polyester constituting In a state where at least 501 layers are alternately stacked, extrusion is performed to obtain a multilayer unstretched film (a step of forming a sheet-like material). At this time, the laminated body of 501 or more laminated | stacked is laminated | stacked so that the layer thickness may change in the range of 1.5 times-5.0 times in steps or continuously.
なお、第１の層および第２の層を構成するポリエステルは、前述の第１の層および第２の層で説明したのと、同様である。第１の層用ポリエステルの融点が２６０℃未満だと、第２の層用ポリエステルとの融点差が十分につかず、結果として、得られる多層延伸フィルムの層間に十分な屈折率差が付与できない。一方、ホモポリエチレン−２，６−ナフタレンジカルボキシレートの融点が２６７℃近傍であることから、第１の層用ポリエステルの融点の上限は高々２７０℃程度である。また、第２の層用ポリエステルの融点が、第１の層用ポリエステルよりも１５℃以上低くないときは、第２の層用ポリエステルとの融点差が十分につかず、結果として、得られる多層延伸フィルムの層間に十分な屈折率差が付与できない。第１の層用ポリエステルの融点と第２の層用ポリエステルの融点差の上限は、両者の密着性を維持する観点から、高々５０℃であることが好ましい。 The polyester constituting the first layer and the second layer is the same as that described for the first layer and the second layer. If the melting point of the first layer polyester is less than 260 ° C., the melting point difference from the second layer polyester is not sufficient, and as a result, a sufficient refractive index difference cannot be imparted between the layers of the resulting multilayer stretched film. On the other hand, since the melting point of homopolyethylene-2,6-naphthalenedicarboxylate is around 267 ° C., the upper limit of the melting point of the first layer polyester is about 270 ° C. at most. In addition, when the melting point of the second layer polyester is not lower by 15 ° C. or more than the first layer polyester, the difference in melting point from the second layer polyester is not sufficient, and as a result, the resulting multilayer stretch A sufficient refractive index difference cannot be imparted between the layers of the film. The upper limit of the melting point difference between the first layer polyester and the second layer polyester is preferably at most 50 ° C. from the viewpoint of maintaining the adhesion between the two layers.
このようにして得られた多層未延伸フィルムは、製膜方向、またはそれに直交する幅方向のいずれか１軸方向（フィルム面に沿った方向）に延伸される。延伸温度は、第１の層のポリエステルのガラス転移点の温度（Ｔｇ）〜Ｔｇ＋５０℃の範囲が好ましい。このときの面積倍率は２〜１０倍であることが好ましい。延伸倍率が大きい程、第１の層および第２の層における個々の層における面方向のバラツキが、延伸による薄層化により小さくなる、すなわち、多層延伸フィルムの光干渉が面方向に均一になるので好ましい。このときの延伸方法は、棒状ヒータによる加熱延伸、ロール加熱延伸、テンター延伸など公知の延伸方法を用いることができるが、ロールとの接触によるキズの低減や延伸速度などの観点から、テンター延伸が好ましい。 The multilayer unstretched film thus obtained is stretched in any one axial direction (direction along the film surface) in the film forming direction or in the width direction perpendicular thereto. The stretching temperature is preferably in the range of the glass transition temperature (Tg) to Tg + 50 ° C. of the polyester of the first layer. In this case, the area magnification is preferably 2 to 10 times. The larger the draw ratio is, the smaller the variation in the plane direction of the individual layers in the first layer and the second layer is due to the thinning by stretching, that is, the optical interference of the multilayer stretched film becomes uniform in the plane direction. Therefore, it is preferable. As the stretching method at this time, known stretching methods such as heat stretching with a rod heater, roll heating stretching, and tenter stretching can be used. From the viewpoints of reducing scratches due to contact with the roll and stretching speed, tenter stretching is performed. preferable.
本発明の最大の特徴は、このようにして延伸された多層フィルムを、第２の層用ポリエステルの融点よりも１０℃低い温度から、第１の層用ポリエステルの融点よりも１５℃低い温度の範囲で熱処理して、第２の層内の分子鎖の配向を緩和させ、第２の層の屈折率を低下させることにある。熱処理の温度が、第２の層用ポリエステルの融点よりも１０℃を超えて低いと、第２の層内の分子鎖の配向を緩和させて屈折率を低下させる効果が不十分となり、得られる１軸延伸多層積層フィルムに十分な屈折率差を付与できない。一方、熱処理の温度が、第１の層用ポリエステルの融点よりも１０℃以上低い温度でないと、第１の層内の分子鎖の配向も緩和されて屈折率が低下し、得られる1軸延伸多層積層フィルムに十分な屈折率差を付与できない。好ましい熱処理の温度は、第２の層用ポリエステルの融点よりも６℃低い温度から、第１の層用ポリエステルの融点よりも１６℃低い温度、さらには第２の層用ポリエステルの融点よりも２℃低い温度から、第１の層用ポリエステルの融点よりも１８℃低い温度である。なお、熱処理の時間は、１〜６０秒が好ましい。 The most important feature of the present invention is that the multilayer film thus stretched is heated from a temperature 10 ° C. lower than the melting point of the second layer polyester to 15 ° C. lower than the melting point of the first layer polyester. Heat treatment in a range is to relax the orientation of molecular chains in the second layer and lower the refractive index of the second layer. When the temperature of the heat treatment is lower than the melting point of the polyester for the second layer by more than 10 ° C., the effect of reducing the refractive index by relaxing the molecular chain orientation in the second layer is obtained and obtained. A sufficient refractive index difference cannot be imparted to the uniaxially stretched multilayer laminated film. On the other hand, if the temperature of the heat treatment is not lower than the melting point of the polyester for the first layer by 10 ° C. or more, the orientation of the molecular chain in the first layer is relaxed, the refractive index is lowered, and the resulting uniaxial stretching A sufficient refractive index difference cannot be imparted to the multilayer laminated film. A preferable heat treatment temperature is 6 ° C. lower than the melting point of the second layer polyester, 16 ° C. lower than the melting point of the first layer polyester, and 2 more than the melting point of the second layer polyester. The temperature is lower by 18 ° C. than the melting point of the first layer polyester. The heat treatment time is preferably 1 to 60 seconds.
また、この熱処理の温度や時間を変化させることにより、樹脂の組成を変化させることなく、第２の層の屈折率を調整することができる、すなわち樹脂の組成を変化させることなく、１軸延伸多層積層フィルムの反射特性を変化させることができる。 Also, by changing the temperature and time of this heat treatment, the refractive index of the second layer can be adjusted without changing the resin composition, that is, uniaxial stretching without changing the resin composition. The reflection characteristics of the multilayer laminated film can be changed.
［易接着層］
易接着層は、ガラス転移点２０〜９０℃のコポリエステル５５〜８５重量％およびケン化度８０〜９０ｍｏｌ％のポリビニルアルコール１５〜４５重量％からなる。コポリエステルが５５重量％未満では１軸延伸多層積層フィルムとの接着性が不足し、８５重量％を超えると吸収性偏光フィルムとの接着性が低下する。ポリビニルアルコールが、１５重量％未満ではインク受像層との接着性が不足し、４５重量％を超えると耐ブロッキング性が低下する。
[Easily adhesive layer]
The easy-adhesion layer is composed of 55 to 85% by weight of copolyester having a glass transition point of 20 to 90 ° C. and 15 to 45% by weight of polyvinyl alcohol having a saponification degree of 80 to 90 mol%. If the copolyester is less than 55% by weight, the adhesion to the uniaxially stretched multilayer laminate film is insufficient, and if it exceeds 85% by weight, the adhesion to the absorbent polarizing film is lowered. If the polyvinyl alcohol is less than 15% by weight, the adhesion to the ink image-receiving layer is insufficient, and if it exceeds 45% by weight, the blocking resistance is lowered.
コポリエステルのガラス転移点（以下Ｔｇと略記することがある）は２０〜９０℃、好ましくは２５〜８０℃である。Ｔｇが２０℃未満であるとフイルムがブロッキングしやすく、９０℃を超えるとフイルムの削れ性や接着性が低下する。 The glass transition point (hereinafter sometimes abbreviated as Tg) of the copolyester is 20 to 90 ° C., preferably 25 to 80 ° C. If the Tg is less than 20 ° C, the film is likely to block, and if it exceeds 90 ° C, the shaving properties and adhesiveness of the film are deteriorated.
易接着層のコポリエステルは、親水性を付与するために、スルホン酸塩基を有するジカルボン酸成分が、コポリエステルを構成する全カルボン酸成分１００モル％あたり好ましくは１〜１６モル％、さらに好ましくは１．５〜１４モル％含有する。スルホン酸塩基を有するジカルボン酸成分が１モル％未満ではコポリエステルの親水性が不足して好ましくなく、１６モル％を超えると塗膜の耐湿性が低下するので好ましくない。 In order to impart hydrophilicity to the copolyester of the easy-adhesion layer, the dicarboxylic acid component having a sulfonate group is preferably 1 to 16 mol%, more preferably 100 mol% of all carboxylic acid components constituting the copolyester. It contains 1.5-14 mol%. If the dicarboxylic acid component having a sulfonate group is less than 1 mol%, the hydrophilicity of the copolyester is insufficient, and if it exceeds 16 mol%, the moisture resistance of the coating film decreases, which is not preferable.
コポリエステルとしては、テレフタル酸、イソフタル酸、２，６―ナフタリンジカルボン酸、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、フェニルインダンジカルボン酸、アジピン酸、セバシン酸、５―スルホイソフタル酸、トリメリット酸、ジメチロールプロピオン酸等のカルボン酸成分及び５―Ｎａスルホイソフタル酸、５―Ｋスルホイソフタル酸、５―Ｋスルホテレフタル酸等のスルホン酸塩基を有するジカルボン酸成分と、エチレングリコール、ジエチレングリコール、ネオペンチレングコール、１，４―ブタンジオール、１，６―ヘキサンジオール、１，４―シクロヘキサンジメタノール、グリセリン、トリメチロールプロパン、ビスフェノール―Ａのアルキレンオキシド付加物等のヒドロキシ化合物成分とから構成されるポリエステルを用いることができる。 Copolyesters include terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, hexahydroterephthalic acid, 4,4'-diphenyldicarboxylic acid, phenylindanedicarboxylic acid, adipic acid, sebacic acid, 5-sulfoisophthalic acid, Dicarboxylic acid components having carboxylic acid components such as trimellitic acid and dimethylolpropionic acid and sulfonate groups such as 5-Na sulfoisophthalic acid, 5-K sulfoisophthalic acid, and 5-K sulfoterephthalic acid, and ethylene glycol and diethylene glycol Hydroxy compounds such as neopentylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, glycerin, trimethylolpropane, and bisphenol-A alkylene oxide adduct Can be used et constituted polyester.
ポリビニルアルコールには、ケン化度が８０〜９０ｍｏｌ％のものを用いる。ケン化度が８０ｍｏｌ％未満であると易接着層の耐湿性が低下し、９０ｍｏｌ％を超えると吸収性偏光フィルムとの接着性が低下する。 Polyvinyl alcohol having a saponification degree of 80 to 90 mol% is used. When the degree of saponification is less than 80 mol%, the moisture resistance of the easy-adhesion layer decreases, and when it exceeds 90 mol%, the adhesion with the absorbent polarizing film decreases.
易接着層は、フィルムの滑り性を付与する目的で、ポリエステル樹脂とポリビニルアルコールとの合計１００重量部あたり、平均粒径２０〜８０nmの微粒子を３〜２５重量部含有することが好ましい。この場合に、微粒子の含有量が３重量％未満ではフイルムの滑性、すなわち搬送性が不足して好ましくなく、２５重量％を超えると削れ性が低下するので好ましくない。 The easy-adhesion layer preferably contains 3 to 25 parts by weight of fine particles having an average particle diameter of 20 to 80 nm per 100 parts by weight in total of the polyester resin and polyvinyl alcohol for the purpose of imparting slipperiness of the film. In this case, if the content of the fine particles is less than 3% by weight, the slipperiness of the film, that is, the transportability is insufficient, which is not preferable.
易接着層は、ポリエステル樹脂とポリビニルアルコールとの合計１００重量部あたり、下記式（Ｉ）で表わされる架橋剤を５〜２０重量部をさらに含有することが好ましい。 The easy adhesion layer preferably further contains 5 to 20 parts by weight of a crosslinking agent represented by the following formula (I) per 100 parts by weight of the total of the polyester resin and polyvinyl alcohol.
この化合物を用いることにより、塗膜とＰＶＡ層との接着性が極めて強固なものとなる。架橋剤が５重量％未満では吸収性偏光フィルムと接着する際に接着性が不足して好ましくなく、２０重量％を超えると耐ブロッキング性の低下、ポリエステルフィルムとの接着性が低下するため好ましくない。 By using this compound, the adhesiveness between the coating film and the PVA layer becomes extremely strong. When the crosslinking agent is less than 5% by weight, the adhesiveness is insufficient when adhering to the absorptive polarizing film, and when it exceeds 20% by weight, the blocking resistance is deteriorated, and the adhesion to the polyester film is deteriorated. .
本発明においては、接着性とフィルムの巻き取り性を確保する観点から、易接着層は、好ましくはコポリエステル、ポリビニルアルコール、微粒子および架橋剤からなる。 In the present invention, from the viewpoint of securing adhesiveness and film winding property, the easy-adhesion layer is preferably composed of copolyester, polyvinyl alcohol, fine particles, and a crosslinking agent.
易接着層の好適な例において、コポリエステルおよびポリビニルアルコールの合計１００重量に対して、微粒子３〜３５重量部および架橋剤５〜２０重量部を配合した塗剤を用いる。 In a preferred example of the easy-adhesion layer, a coating agent containing 3 to 35 parts by weight of fine particles and 5 to 20 parts by weight of a crosslinking agent is used with respect to a total of 100 weights of copolyester and polyvinyl alcohol.
易接着層の表面エネルギーは、好ましくは５０〜６５ｄｙｎｅ／ｃｍ、さらに好ましくは５２〜６０ｄｙｎｅ／ｃｍである。表面エネルギーが５０ｄｙｎｅ／ｃｍ未満であると、親水性である吸収性偏光フィルムとの接着性が不良となり好ましくなく、６５ｄｙｎｅ／ｃｍを超えると基体である反射性偏光フィルムとの密着性が不足したり、塗膜の耐湿性が不足することがあるため好ましくない。 The surface energy of the easy adhesion layer is preferably 50 to 65 dyne / cm, and more preferably 52 to 60 dyne / cm. If the surface energy is less than 50 dyne / cm, the adhesiveness with the hydrophilic absorbing polarizing film becomes unfavorable, and if it exceeds 65 dyne / cm, the adhesion with the reflective polarizing film as the substrate is insufficient. This is not preferable because the moisture resistance of the coating film may be insufficient.
易接着層の表面エネルギーは、上述の易接着層の成分からなる塗膜を、例えば０．０２〜１μｍの厚さで積層することにより得ることができる。 The surface energy of the easy-adhesion layer can be obtained by laminating a coating film composed of the components of the above-mentioned easy-adhesion layer, for example, with a thickness of 0.02 to 1 μm.
易接着層の表面中心線平均粗さ（Ｒａ）は、１０ｎｍ〜２５０ｎｍの範囲にあることが、フィルムの耐ブロッキング性や搬送性が良好となるため好ましい。 The surface center line average roughness (Ra) of the easy-adhesion layer is preferably in the range of 10 nm to 250 nm because the blocking resistance and transportability of the film are improved.
易接着層は、易接着層を構成する組成物を、好ましくは水溶液、水分散液または乳化液として、一軸積層延伸フィルムのうえに塗布することにより製造することができる。塗布方法としては、公知の任意の塗布法が適用できる。例えばロールコート法、グラビアコート法、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、含浸法及びカーテンコート法などを単独または組み合わせて用いることができる。塗布量は、走行しているフイルム１ｍ２あたり好ましくは０．５〜２０ｇ、さらに好ましくは１〜１０ｇである。 The easy-adhesion layer can be produced by applying the composition constituting the easy-adhesion layer, preferably as an aqueous solution, aqueous dispersion or emulsion, onto a uniaxial laminated stretched film. As the coating method, any known coating method can be applied. For example, a roll coating method, a gravure coating method, a roll brush method, a spray coating method, an air knife coating method, an impregnation method, and a curtain coating method can be used alone or in combination. The coating amount is preferably 0.5 to 20 g, more preferably 1 to 10 g, per 1 m 2 of the running film.
実施例をもって、本発明をさらに説明する。なお、実施例中の物性や特性は、下記の方法にて測定または評価した。
（１）コポリエステルの融点
コポリエステル試料を１０ｍｇサンプリングし、ＤＳＣ（ＴＡインスツルメンツ社製、商品名：ＤＳＣ２９２０）を用い、２０℃／ｍｉｎ．の昇温速度で、融点を測定した。
The invention is further described by way of examples. In addition, the physical property and characteristic in an Example were measured or evaluated by the following method.
(1) Melting point of copolyester 10 mg of a copolyester sample was sampled and used at 20 ° C./min. Using DSC (trade name: DSC2920, manufactured by TA Instruments). The melting point was measured at a temperature elevation rate of.
（２）各層の厚み
サンプルを三角形に切り出し、包埋カプセルに固定後、エポキシ樹脂にて包埋する。そして、包埋されたサンプルをミクロトーム（ＵＬＴＲＡＣＵＴ−Ｓ、製造元：ライヘルト社）で製膜方向と厚み方向に沿って切断し、厚さ５０ｎｍの薄膜切片にした。得られた薄膜切片を、透過型電子顕微鏡（製造元：日本電子（株）、商品名：ＪＥＭ２０１０）を用いて、加速電圧１００ｋＶにて観察・撮影し、写真から各層の厚みを測定した。表１中に示した層厚の定義を下記の示す。
層厚比：第一の層のうち０．０５〜０．５にある範囲の層の平均厚み
(2) Thickness of each layer A sample is cut into triangles, fixed to an embedded capsule, and then embedded in an epoxy resin. And the embedded sample was cut | disconnected along the film forming direction and the thickness direction with the microtome (ULTRACUT-S, manufacturer: Reichert), and it was set as the thin-film section | slice of thickness 50nm. The obtained thin film slices were observed and photographed at an accelerating voltage of 100 kV using a transmission electron microscope (manufacturer: JEOL Ltd., trade name: JEM2010), and the thickness of each layer was measured from the photograph. The definition of the layer thickness shown in Table 1 is shown below.
Layer thickness ratio: Average thickness of layers in the range of 0.05 to 0.5 in the first layer
（３）反射率、反射波長
分光光度計（島津製作所製、ＭＰＣ−３１００）を用い、光源側に偏光フィルタを装着し、各波長でのアルミ蒸着したミラーとの相対鏡面反射率を波長４００ｎｍから８００ｎｍの範囲で測定した。このとき、偏光フィルタの透過軸をフィルムの延伸方向と合わせるように配置した場合の測定値をＰ偏光とし、偏光フィルタの透過軸をフィルムの延伸方向と直交するように配置した場合の測定値をＳ偏光とした。それぞれの偏光成分について、４００−８００ｎｍの範囲での反射率の平均値を平均反射率とし、測定された反射率の中で最大のものを、最大反射率とし、最小のものを最小反射率とした。表１中の最大反射率差は下記の式で表される。
最大反射率差（％）＝最大反射率（％）−最小反射率（％）
(3) Reflectance and reflection wavelength Using a spectrophotometer (manufactured by Shimadzu Corp., MPC-3100), a polarizing filter is attached to the light source side, and the relative specular reflectance with the aluminum-deposited mirror at each wavelength is measured from a wavelength of 400 nm. Measurements were made in the range of 800 nm. At this time, the measurement value when the transmission axis of the polarizing filter is aligned with the stretching direction of the film is P-polarized light, and the measurement value when the transmission axis of the polarizing filter is orthogonal to the stretching direction of the film is S-polarized light was used. For each polarization component, the average value of the reflectance in the range of 400-800 nm is the average reflectance, the largest of the measured reflectances is the maximum reflectance, and the smallest is the minimum reflectance. did. The maximum reflectance difference in Table 1 is expressed by the following formula.
Maximum reflectance difference (%) = Maximum reflectance (%)-Minimum reflectance (%)
（４）ヘーズ値
日本電色工業社製のヘーズ測定器（ＮＤＨ―２０）を使用してフィルムのヘーズ値を測定した。尚、フィルムのヘーズを下記の基準で評価した。
◎： ヘーズ値≦０．５％ ……フィルムのヘーズ極めて良好
○：０．５％＜ヘーズ値≦１．０％ ……フィルムのヘーズ良好
×：１．０％＜ヘーズ値 ……フィルムのヘーズ不良
(4) Haze value The haze value of the film was measured using a haze measuring device (NDH-20) manufactured by Nippon Denshoku Industries Co., Ltd. The film haze was evaluated according to the following criteria.
◎: Haze value ≦ 0.5% …… Extremely good haze of film ○: 0.5% <Haze value ≦ 1.0% …… Good haze of film ×: 1.0% <Haze value …… Haze of film Bad
（５）中心線平均表面粗さ（Ｒａ）
ＪＩＳ Ｂ０６０１に準じ、（株）小坂研究所製の高精度表面粗さ計 ＳＥ―３ＦＡＴを使用して、針の半径２μｍ、荷重３０ｍｇで拡大倍率２０万倍、カットオフ０．０８ｍｍの条件下にチャートを描かせ、表面粗さ曲線からその中心線方向に測定長さＬの部分を抜き取り、この抜き取り部分の中心線をＸ軸、縦倍率の方向とＹ軸として、粗さ曲線をＹ＝ｆ（ｘ）で表わした時、次の式で与えられた値をｎｍ単位で表わした。また、この測定は、基準長を１．２５ｍｍとして４個測定し、平均値で表わした。
(5) Centerline average surface roughness (Ra)
In accordance with JIS B0601, using a high-precision surface roughness meter SE-3FAT manufactured by Kosaka Laboratory Co., Ltd. A chart is drawn, and a portion of the measurement length L is extracted from the surface roughness curve in the center line direction. The center line of this extraction portion is the X axis, the direction of the vertical magnification and the Y axis, and the roughness curve is Y = f When represented by (x), the value given by the following equation was expressed in nm. In this measurement, four pieces were measured with a reference length of 1.25 mm and expressed as an average value.
（６）摩擦係数（μｓ）
ＡＳＴＭ Ｄ１８９４―６３に準じ、東洋テスター社製のスリッパリー測定器を使用し、塗膜形成面とポリエチレンテレフタレートフィルム（塗膜非形成面）との静摩擦係数（μｓ）を測定した。但し、スレッド板はガラス板とし、荷重は１ｋｇとした。尚、フィルムの滑り性を下記の基準で評価した。
◎： 摩擦係数（μｓ）≦０．５ ……滑り性極めて良好
○：０．５＜摩擦係数（μｓ）≦０．８ ……滑り性良好
×：０．８＜摩擦係数（μｓ） ……滑り性不良
(6) Friction coefficient (μs)
In accordance with ASTM D1894-63, a slippery measuring device manufactured by Toyo Tester was used to measure the static friction coefficient (μs) between the coating film forming surface and the polyethylene terephthalate film (coating film non-forming surface). However, the thread plate was a glass plate and the load was 1 kg. The slipping property of the film was evaluated according to the following criteria.
◎: Friction coefficient (μs) ≦ 0.5 …… Excellent sliding property ○: 0.5 <Friction coefficient (μs) ≦ 0.8 …… Good sliding property ×: 0.8 <Friction coefficient (μs) …… Poor slipperiness
（７）耐ブロッキング性
２枚のフィルムを、塗膜形成面と非形成面が接するように重ね合せ、これに、６０℃、８０％ＲＨの雰囲気下で１７時間にわたって０．６ｋｇ／ｃｍ2の圧力をかけ、その後、剥離して、その剥離力により耐ブロッキング性を下記の基準で評価した。
◎： 剥離力＜９８ｍＮ／５ｃｍ ……耐ブロッキング性極めて良好
○：９８ｍＮ／５ｃｍ≦剥離力＜１４７ｍＮ／５ｃｍ ……耐ブロッキング性良好
△：１４７ｍＮ／５ｃｍ≦剥離力＜１９６ｍＮ／５ｃｍ ……耐ブロッキング性やや良好
×：１９６ｍＮ／５ｃｍ≦剥離力 ……耐ブロッキング性不良
(7) Blocking resistance Two films were laminated so that the coating-formed surface and the non-forming surface were in contact with each other, and the pressure was 0.6 kg / cm 2 over 17 hours in an atmosphere of 60 ° C. and 80% RH. And then peeled off, and the blocking resistance was evaluated according to the following criteria based on the peeling force.
◎: Peeling force <98 mN / 5 cm …… Excellent blocking resistance ◯: 98 mN / 5 cm ≦ Peeling force <147 mN / 5 cm …… Good blocking resistance Δ: 147 mN / 5 cm ≦ Peeling force <196 mN / 5 cm ...... Blocking resistance Slightly good ×: 196 mN / 5 cm ≦ peeling force ...... Poor blocking resistance
（８）表面エネルギー
Ｗ．Ａ．Ｚｉｓｍａｎ：“Ｃｏｎｔａｃｔ Ａｕｇｌｅ， Ｗｅｔｔａｂｉｌｉｔｙ ａｎｄ Ａｄｈｅｓｉｏｎ”，Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，（１９６４）に従い、測定した臨界表面張力γｃをもって、表面エネルギーとした。
(8) Surface energy A. Zisman: “Contact Augle, Wetability and Adhesion”, Am. Chem. Soc. , (1964), the measured critical surface tension γc was used as the surface energy.
（９）耐湿性
前記ブロッキング性の評価において、処理条件を６０℃×７０％ＲＨ×１７時間としたほかは同様の方法で剥離強度（ｇ／５０ｍｍ）を測定した。測定結果より下記の通り評価した。
剥離強度≦１０ｇ／５０ｍｍ …耐湿性良好
１０ｇ／５０ｍｍ＜剥離強度≦３０ｇ／５０ｍｍ …耐湿性やや良好
３０ｇ／５０ｍｍ≦剥離強度 …耐湿性不良
(9) Moisture resistance In the evaluation of the blocking property, the peel strength (g / 50 mm) was measured by the same method except that the processing conditions were 60 ° C. × 70% RH × 17 hours. From the measurement results, the evaluation was as follows.
Peel strength ≦ 10 g / 50 mm ... Good moisture resistance 10 g / 50 mm <Peel strength ≤ 30 g / 50 mm ... Slightly good moisture resistance 30 g / 50 mm ≤ Peel strength ... Poor moisture resistance
（１０）水分散性
塗布剤を水で希釈して０．２重量％の水分散体とし、石英製セルを用いて、日立製作所製 ダブルビーム分光光度計（２２８Ａ型機）にて光線透過率を測定した。測定結果より下記の通り評価した。
光線透過率≧５０％ ……水分散性良好
５０％＞光線透過率≧３０％ ……水分散性やや良好
３０％＞光線透過率 ……水分散性不良
(10) Water dispersibility The coating agent is diluted with water to give a 0.2% by weight water dispersion, and the light transmittance is measured with a double beam spectrophotometer (228A model) manufactured by Hitachi using a quartz cell. Was measured. From the measurement results, the evaluation was as follows.
Light transmittance ≧ 50% …… Good water dispersibility 50%> Light transmittance ≧ 30% …… Water dispersibility slightly good 30%> Light transmittance …… Poor water dispersibility
（１１）接着性
湿度９０％、温度８０℃、１時間と、温度−２０℃、１時間のヒートサイクルテストを２００サイクル繰り返したときの、外観評価を次のとおり評価した。
○：外観に変化無し
×：サンプルに白化現象または、フィルム同士の剥がれが見られる。
(11) Adhesiveness Appearance evaluation was evaluated as follows when a heat cycle test of humidity 90%,
○: No change in appearance ×: Whitening phenomenon or peeling between films is observed in the sample.
（１２）長期耐久性
サンプルフィルムを湿度９５％、温度６５℃環境中に１０００時間放置し、平面状に放置した際のサンプルフィルム処理前後の偏光度変化から、下記に従って評価した。
○： 処理後の偏光度が処理前の９５％以上
×： 処理後の偏光度が処理前の９５％未満
(12) Long-term durability The sample film was evaluated in accordance with the following from the change in the degree of polarization before and after the sample film treatment when the sample film was left in an environment of 95% humidity and a temperature of 65 ° C. for 1000 hours and left in a flat shape.
○: The degree of polarization after treatment is 95% or more before treatment. ×: The degree of polarization after treatment is less than 95% before treatment.
［実施例１］
固有粘度（オルトクロロフェノール、３５℃）０．６２のポリエチレン−２，６−ナフタレンジカルボキシレート（ＰＥＮ）に真球状シリカ粒子（平均粒径：０．３μｍ、長径と短径の比：１．０２、粒径の平均偏差：０．１）を０．１５ｗｔ％添加したものを第１の層用ポリエステルとし、第２の層用ポリエステルとして固有粘度（オルトクロロフェノール、３５℃）０．６２のテレフタル酸１０ｍｏｌ％共重合ポリエチレン−２，６−ナフタレンジカルボキシレート（ＴＡ１０ＰＥＮ）を準備した。そして、第１の層用ポリエステルおよび第２の層用ポリエステルを、それぞれ１７０℃で５時間乾燥後、押出し機に供給し、３００℃まで加熱して溶融状態とし、第１の層用ポリエステルを３０１層、第２の層用ポリエステルを３００層に分岐させた後、第１の層と第２の層が交互に積層され、かつ層厚が最大／最小で３倍まで、連続的に変化するような多層フィードブロック装置を使用して、その積層状態を保持したままダイへと導き、キャスティングドラム上にキャストして第１の層と第２の層の各層の厚みが１．０：２．０になるように調整し、第１の層と第２の層が交互に積層された総数６０１層の未延伸多層積層フィルムを作成した。
[Example 1]
Polyethylene-2,6-naphthalenedicarboxylate (PEN) having an intrinsic viscosity (orthochlorophenol, 35 ° C.) of 0.62 and true spherical silica particles (average particle size: 0.3 μm, ratio of major axis to minor axis: 1. 02, 0.15 wt% of the average particle size deviation is 0.15 wt% polyester, and the second layer polyester is intrinsic viscosity (orthochlorophenol, 35 ° C.) 0.62 A 10 mol% terephthalic acid copolymerized polyethylene-2,6-naphthalenedicarboxylate (TA10PEN) was prepared. Then, the first layer polyester and the second layer polyester are each dried at 170 ° C. for 5 hours, then supplied to an extruder, heated to 300 ° C. to be in a molten state, and the first layer polyester is 301 After the polyester for the second layer and the second layer are branched into 300 layers, the first layer and the second layer are alternately laminated, and the layer thickness continuously changes up to 3 times at maximum / minimum. Using a multi-layer feed block apparatus, the laminated state is led to a die and cast on a casting drum so that the thickness of each of the first layer and the second layer is 1.0: 2.0. Thus, a total of 601 unstretched multilayer laminated films in which the first layer and the second layer were alternately laminated were prepared.
次に該多層未延伸フイルムの片面にコポリエステルとして、酸成分がテレフタル酸［６０モル％］、イソフタル酸［３６モル％］および５―Ｎａスルホイソフタル酸［４モル％］、グリコール成分がエチレングリコール［６０モル％］およびネオペンチルグリコール［４０モル％］よりなる共重合ポリエステル（Ｔｇ＝３０℃、以下、単に［Ｅ］という）５１重量％、ケン化度８６〜８９モル％のポリビニルアルコール２０重量％、平均粒径４０ｎｍの架橋アクリル樹脂粒子１０重量％、下記式（II）で示される化合物（Ｓ）１０重量％並びにポリオキシエチレンラウリルエーテル９重量％からなる組成の、固形分濃度４重量％の水性液をロールコーターにて塗布した。 Next, as a copolyester on one side of the multilayer unstretched film, the acid component is terephthalic acid [60 mol%], isophthalic acid [36 mol%] and 5-Na sulfoisophthalic acid [4 mol%], and the glycol component is ethylene glycol. Copolymer polyester comprising [60 mol%] and neopentyl glycol [40 mol%] (Tg = 30 ° C., hereinafter simply referred to as [E]) 51 wt%, polyvinyl alcohol having a saponification degree of 86 to 89 mol%, 20 wt% %, A composition comprising 10% by weight of crosslinked acrylic resin particles having an average particle size of 40 nm, 10% by weight of the compound (S) represented by the following formula (II) and 9% by weight of polyoxyethylene lauryl ether, and a solid content concentration of 4% by weight. Was applied with a roll coater.
該多層未延伸フイルムを乾燥しつつ、１３５℃の温度で機械方向に５．２倍に延伸し、２４５℃で３秒間熱固定処理を行った。得られたフィルムの厚みは、５５μｍであった。 While the multilayer unstretched film was dried, the multilayer unstretched film was stretched 5.2 times in the machine direction at a temperature of 135 ° C., and heat-set at 245 ° C. for 3 seconds. The thickness of the obtained film was 55 μm.
フィルムの製造条件を表１にまとめて示す。表１において、ＰＥＮはポリエチレンナフタレンジカルボキシレートを意味し、ＴＡ１０ＰＥＮはテレフタル酸を１０モル％共重合したポリエチレンナフタレンジカルボキシレートを意味する。 The production conditions for the film are summarized in Table 1. In Table 1, PEN means polyethylene naphthalene dicarboxylate and TA10PEN means polyethylene naphthalene dicarboxylate copolymerized with 10 mol% of terephthalic acid.
得られた１軸延伸多層積層フィルムの特性を表２に示す。 Table 2 shows the properties of the obtained uniaxially stretched multilayer laminated film.
次いで、吸収偏光フィルムとしてヨウ素を含有させたＰＶＡフィルム（厚み３０μｍ）を準備し、ＰＶＡ系接着剤により、ヨウ素を含有させたＰＶＡフィルムの片面と１軸延伸多層積層フィルムの水性液をコートした面をそれぞれの偏光軸があうように接着した。ついで、ヨウ素を含有させたＰＶＡフィルムの他方の面に透明保護フィルムとしてＴＡＣフィルム（厚み１００μｍ）を貼り合わせることによって、全体厚み１９０μｍの反射吸収性偏光フィルムつき吸収吸収性偏光フィルムを作製したところ、良好な接着性を示した。
Next, a PVA film (thickness 30 μm) containing iodine is prepared as an absorbing polarizing film, and one side of the PVA film containing iodine and an aqueous liquid of a uniaxially stretched multilayer laminated film are coated with a PVA adhesive. Were bonded so that their respective polarization axes were matched. Next, an absorptive absorptive polarizing film with a reflective absorptive polarizing film having a total thickness of 190 μm was prepared by laminating a TAC film (
［比較例１］
水性液を塗布しない以外は、実施例１と同様にして得た１軸延伸多層積層フィルムの特性を表２に示す。
[Comparative Example 1]
Table 2 shows the properties of the uniaxially stretched multilayer laminated film obtained in the same manner as in Example 1 except that the aqueous liquid was not applied.
［実施例２〜９、比較例２〜５］
水性液の組成を表３に示すように変更する以外は、実施例１と同様にして得た１軸延伸多層積層フィルムの特性を表２に示す。
[Examples 2 to 9, Comparative Examples 2 to 5]
Table 2 shows the properties of the uniaxially stretched multilayer laminated film obtained in the same manner as in Example 1 except that the composition of the aqueous liquid is changed as shown in Table 3.
表１において、コポリエステルの種類は表３に示すとおりである。また、また、表３においてポリビニルアルコールの種類Ｐ、ＱおよびＲは、下記の化合物であることを示す。
Ｐ：ケン化度８６〜８９ｍｏｌ％のポリビニルアルコール
Ｑ：ケン化度７４〜７８ｍｏｌ％のポリビニルアルコール
Ｒ：ケン化度９２〜９５ｍｏｌ％のポリビニルアルコール
In Table 1, the types of copolyesters are as shown in Table 3. Moreover, in Table 3, the types P, Q, and R of polyvinyl alcohol indicate the following compounds.
P: polyvinyl alcohol having a saponification degree of 86 to 89 mol% Q: polyvinyl alcohol having a saponification degree of 74 to 78 mol% R: polyvinyl alcohol having a saponification degree of 92 to 95 mol%
表３において微粒子の種類ＭおよびＮは、下記の化合物であることを示す。
Ｍ：平均粒径 ４０ｎｍの架橋アクリル粒子
Ｎ：平均粒径 ８０ｎｍのコロイダルシリカ粒子
In Table 3, the types M and N of the fine particles indicate the following compounds.
M: Cross-linked acrylic particle having an average particle diameter of 40 nm N: Colloidal silica particle having an average particle diameter of 80 nm
表３において架橋剤の種類ＳおよびＴは下記式（ＩＩ）および式（ＩＩＩ）の化合物であることを示す。 In Table 3, the types S and T of the crosslinking agent indicate compounds of the following formulas (II) and (III).
本発明の反射性偏光フィルムは、液晶表示装置に偏光板として用いることができる。 The reflective polarizing film of the present invention can be used as a polarizing plate in a liquid crystal display device.
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| PCT/JP2005/016165 WO2006025548A1 (en) | 2004-08-30 | 2005-08-29 | Optical film laminate |
| US11/661,279 US20070264447A1 (en) | 2004-08-30 | 2005-08-29 | Optical Film Laminated Body |
| TW94129773A TWI382932B (en) | 2004-08-30 | 2005-08-30 | Optical film laminates |
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