JP2006294532A - Conductive film - Google Patents
Conductive film Download PDFInfo
- Publication number
- JP2006294532A JP2006294532A JP2005116706A JP2005116706A JP2006294532A JP 2006294532 A JP2006294532 A JP 2006294532A JP 2005116706 A JP2005116706 A JP 2005116706A JP 2005116706 A JP2005116706 A JP 2005116706A JP 2006294532 A JP2006294532 A JP 2006294532A
- Authority
- JP
- Japan
- Prior art keywords
- refractive index
- conductive film
- film
- layer
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000004080 punching Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
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- 238000005809 transesterification reaction Methods 0.000 description 1
- YZVRVDPMGYFCGL-UHFFFAOYSA-N triacetyloxysilyl acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)OC(C)=O YZVRVDPMGYFCGL-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- QHUNJMXHQHHWQP-UHFFFAOYSA-N trimethylsilyl acetate Chemical compound CC(=O)O[Si](C)(C)C QHUNJMXHQHHWQP-UHFFFAOYSA-N 0.000 description 1
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Images
Landscapes
- Laminated Bodies (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
本発明は導電性フィルムに関するものである。さらに詳しくは、透明性に優れ、液晶ディスプレイ（ＬＣＤ）透明タッチパネル、有機エレクトロルミネッセンス素子、無機エレクトロルミネッセンスランプ等の透明電極や電磁波シールド材として好適に使用することができる透明導電性フィルムに関するものである。 The present invention relates to a conductive film. More specifically, the present invention relates to a transparent conductive film that is excellent in transparency and can be suitably used as a transparent electrode such as a liquid crystal display (LCD) transparent touch panel, an organic electroluminescence element, an inorganic electroluminescence lamp, or an electromagnetic shielding material. .
従来、液晶ディスプレイ、透明タッチパネル等の透明電極や電磁波シールド材として透明導電性フィルムが好適に用いられている。かかる透明導電性フィルムとしては、ポリエチレンテレフタレート（ＰＥＴ）、トリアセチルセルロース（ＴＡＣ）等の透明フィルム表面の少なくとも片面に、酸化インジウム（Ｉｎ２Ｏ３）、酸化錫（ＳｎＯ２）、Ｉｎ２Ｏ３とＳｎＯ２の混合焼結体（ＩＴＯ）等を、真空蒸着法、スパッタリング法、イオンプレーティング法等のドライプロセスによって設けたものがよく知られている。 Conventionally, a transparent conductive film is suitably used as a transparent electrode such as a liquid crystal display or a transparent touch panel or an electromagnetic shielding material. Examples of such transparent conductive films include indium oxide (In 2 O 3 ), tin oxide (SnO 2 ), In 2 O 3 on at least one surface of a transparent film surface such as polyethylene terephthalate (PET) or triacetyl cellulose (TAC). It is well known that a mixed sintered body (ITO) of SnO 2 and SnO 2 is provided by a dry process such as a vacuum deposition method, a sputtering method, or an ion plating method.
しかし、通常透明導電性フィルムは、ウェブ状での連続加工や打ち抜き加工があり、また、表面加工中も曲げられた状態で用いられたり、また保管されたりするため、上記ドライプロセスにより得られる透明導電性フィルムは、該加工工程や保管している間にクラックが発生して表面抵抗が増大したりすることがあった。 However, the transparent conductive film usually has continuous processing and punching processing in a web shape, and is used in a bent state during surface processing and is also stored. In the conductive film, cracks may occur during the processing step or storage, and the surface resistance may increase.
一方、透明基材フィルムの上に導電性高分子を塗布すること（ウエットプロセス）により形成される透明導電塗膜層は、膜自体に柔軟性があり、クラックなどの問題は生じがたい。また、導電性高分子を塗布することによって透明導電性フィルムを得る方法は、ドライプロセスとは異なって製造コストが比較的安く、またコーティングスピードも一般的に速いので生産性に優れるという利点もある。このような導電性高分子の塗布によって得られる透明導電性フィルムは、これまで一般的に用いられてきたポリチオフェン、ポリアニリン、ポリピロール等は、開発の初期段階では高い導電性が得られないために帯電防止用途などに使用が限定されていたり、導電塗膜層自体の色相が問題となったりしていた。しかし、最近では製法の改良などによりこれらの問題も改善されてきている。例えば、３，４−ジアルコキシチオフェンをポリアニオン存在下で酸化重合することによって得られるポリ（３，４−ジアルコキシチオフェン）とポリアニオンとからなる導電性高分子（特許文献１）は、近年の製法の改良（特許文献２および特許文献３）などにより、高い光線透過率を保ったまま低い表面抵抗を発現している。
On the other hand, the transparent conductive coating film layer formed by applying a conductive polymer on a transparent substrate film (wet process) has flexibility in the film itself, and problems such as cracks hardly occur. In addition, the method of obtaining a transparent conductive film by applying a conductive polymer has the advantage that the manufacturing cost is relatively low unlike the dry process, and the coating speed is generally high, so that the productivity is excellent. . Transparent conductive films obtained by applying such conductive polymers are charged with polythiophene, polyaniline, polypyrrole, etc., which have been generally used so far, because high conductivity cannot be obtained at the initial stage of development. The use was limited to the prevention use etc., or the hue of the conductive coating layer itself was problematic. However, these problems have recently been improved by improving the production method. For example, a conductive polymer (Patent Document 1) comprising a poly (3,4-dialkoxythiophene) obtained by oxidative polymerization of 3,4-dialkoxythiophene in the presence of a polyanion and a polyanion is a recent production method. (
しかしながら、これらの改良された透明導電性フィルムも、タッチパネルなどの用途分野では依然光線透過率が不十分であり、さらなる改善が求められている。従来フィルム等の光線透過率を上げるためには、屈折率が高い材料と低い材料とを組合わせ、光の干渉効果による反射防止を利用する方法が提案されているが、導電性高分子からなる透明導電塗膜層の屈折率は１．５前後であり、光学干渉によって十分な反射低減（透過上昇）を実現できるような低屈折率層や高屈折率層を湿式塗工によって得ることは困難であった。 However, these improved transparent conductive films still have insufficient light transmittance in application fields such as touch panels, and further improvements are required. Conventionally, in order to increase the light transmittance of a film or the like, a method has been proposed in which a material having a high refractive index and a material having a low refractive index are combined and antireflection by light interference effect is used. The refractive index of the transparent conductive coating layer is around 1.5, and it is difficult to obtain a low refractive index layer or a high refractive index layer that can realize sufficient reflection reduction (transmission increase) by optical interference by wet coating. Met.
本発明は、上記背景技術を鑑みなされたもので、その目的は、表面反射が抑制され、優れた透明性を呈する導電性フィルムを提供することにある。 This invention is made | formed in view of the said background art, The objective is to provide the electroconductive film which surface reflection is suppressed and which exhibits the outstanding transparency.
本発明者は、上記課題を達成するため鋭意検討した結果、透明導電塗膜層と基材フィルムとの間に特定の屈折率を有する低屈折率層を設けた場合、光線透過率が向上して透明性に優れた導電性フィルムが得られることを見出し、本発明に到達した。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have improved the light transmittance when a low refractive index layer having a specific refractive index is provided between the transparent conductive coating film layer and the base film. The inventors have found that a conductive film excellent in transparency can be obtained, and have reached the present invention.
かくして本発明によれば、「基材フィルムの少なくとも片面に、内部に空隙を有する見かけの屈折率が１．１０〜１．３５の低屈折率層および透明導電塗膜層がこの順に積層された導電性フィルムであって、その波長５５０ｎｍにおける表面反射率が４％以下で、かつ表面抵抗が１０〜５×１０５Ω／□であることを特徴とする導電性フィルム。」が提供される。 Thus, according to the present invention, "a low refractive index layer having an apparent refractive index of 1.10 to 1.35 and a transparent conductive coating layer having voids therein are laminated in this order on at least one side of the base film. A conductive film having a surface reflectance of 4% or less at a wavelength of 550 nm and a surface resistance of 10 to 5 × 10 5 Ω / □ is provided.
また好ましい態様として、該透明導電塗膜層が、下記一般式
で表される繰返し単位からなるポリカチオン状のポリチオフェンと、ポリアニオンとから構成される導電性高分子を含有すること、該透明導電塗膜層が、下記一般式
で表される繰返し単位からなるポリカチオン状のポリチオフェンとポリアニオンとから構成される導電性高分子と、テトラアルコキシシランおよびアルコキシ基以外の反応性の官能基を有するトリアルコキシシランからなる群より選ばれる少なくとも一種のシラン化合物との反応性生物を含有すること、該シラン化合物が、グリシドキシ基を有するトリアルコキシシランであること、該低屈折率層が平均粒径５〜２００ｎｍの有機／無機複合粒子からなること、該低屈折率層がフッ素原子と珪素原子とを含有していること、さらには、ポリエステル樹脂およびオキサゾリン基とポリアルキレンオキシド鎖とを有するアクリル樹脂を構成成分として含有するアンカーコート層が基材フィルムと低屈折率層の間に設けられていること、の少なくとも一つを具備する導電性フィルムが提供される。
As a preferred embodiment, the transparent conductive coating layer has the following general formula:
Containing a conductive polymer composed of a polycationic polythiophene composed of a repeating unit represented by the following formula: and a polyanion, the transparent conductive coating layer having the following general formula:
Selected from the group consisting of a conductive polymer composed of a polycationic polythiophene comprising a repeating unit represented by formula (II) and a polyanion, and a trialkoxysilane having a reactive functional group other than a tetraalkoxysilane and an alkoxy group. It contains a reactive organism with at least one silane compound, the silane compound is a trialkoxysilane having a glycidoxy group, and the organic / inorganic composite particle having an average particle diameter of 5 to 200 nm. The low refractive index layer contains a fluorine atom and a silicon atom, and further, an anchor coat layer containing a polyester resin and an acrylic resin having an oxazoline group and a polyalkylene oxide chain as a constituent component At least between the base film and the low refractive index layer Conductive films comprising one is provided.
本発明の導電性フィルムは、透明導電塗膜層と基材フィルムとの間に、内部に空隙を有する特定の低屈折率層が形成されているため、光の表面反射率を低減させることができ、優れた透明性と導電性とを兼備した導電性フィルムを生産性良く提供することができる。また、本発明の透明導電性フィルムは、表面反射率が抑制されているので、透明タッチパネル、液晶ディスプレイ（ＬＣＤ）、有機エレクトロルミネッセンス素子、無機エレクトロルミネッセンス素子等の透明電極や電磁波シールド材として好適に使用できる。 In the conductive film of the present invention, a specific low refractive index layer having voids is formed between the transparent conductive coating layer and the base film, so that the surface reflectance of light can be reduced. In addition, a conductive film having both excellent transparency and conductivity can be provided with high productivity. Moreover, since the surface reflectance is suppressed, the transparent conductive film of the present invention is suitable as a transparent electrode such as a transparent touch panel, a liquid crystal display (LCD), an organic electroluminescence element, an inorganic electroluminescence element, or an electromagnetic shielding material. Can be used.
本発明の導電性フィルムを、まず図面を用いて説明する。図１は、本発明の導電性フィルムの断面図、すなわち層構成の一例を示すものである。図１中、符号１は基材フィルム、符号２は低屈折率層、符号３は透明導電塗膜層を、符号４はハードコート層を示す。図１から分かるように、本発明の導電性フィルムは、基材フィルムの少なくとも片面に低屈折率層が積層され、該低屈折率層の上にさらに透明導電塗膜層が積層されたものである。このような構成を有するものであれば、例えばハードコート層等の他の機能層が、本発明の目的を損なわない限りにおいて形成されていてもよく、図１（ｂ）には透明導電塗膜層を形成した面とは反対側にハードコート層が設けられた例が示されている。
First, the conductive film of the present invention will be described with reference to the drawings. FIG. 1 shows a cross-sectional view of the conductive film of the present invention, that is, an example of a layer structure. In FIG. 1, reference numeral 1 is a base film,
このように本発明の導電性フィルムは、基材フィルムの少なくとも片面に、内部に空隙を有する見かけの屈折率が１．１０〜１．３５、好ましくは１．２０〜１．３５である低屈折率層および透明導電塗膜層がこの順で積層されている必要がある。この順序が逆になって、透明導電塗膜層の上に空隙を有する低屈折率層が積層されていると、十分な表面抵抗が確保できないだけでなく、反射率低減（透過率向上）の効果も得られなくなるので好ましくない。 As described above, the conductive film of the present invention has a low refractive index having an apparent refractive index of 1.10 to 1.35, preferably 1.20 to 1.35 having voids inside at least on one side of the base film. The rate layer and the transparent conductive coating layer need to be laminated in this order. If this order is reversed and a low refractive index layer having voids is laminated on the transparent conductive coating layer, not only a sufficient surface resistance cannot be secured, but also the reflectance is reduced (transmittance is improved). Since the effect cannot be obtained, it is not preferable.
また本発明の透明導電性フィルムは、その全光線透過率が７０％以上であることが好ましい。該全光線透過率が７０％未満であると、液晶ディスプレイ、透明タッチパネル等の透明電極や電磁波シールド材として用いたときに、十分な透明性が得がたい。特に好ましい全光線透過率は７５％以上、さらには８０％以上である。このような全光線透過率は、後述の基材フィルム、透明導電塗膜層の選定によって適宜調整できる。 The transparent conductive film of the present invention preferably has a total light transmittance of 70% or more. When the total light transmittance is less than 70%, it is difficult to obtain sufficient transparency when used as a transparent electrode such as a liquid crystal display or a transparent touch panel or an electromagnetic shielding material. Particularly preferred total light transmittance is 75% or more, and further 80% or more. Such a total light transmittance can be suitably adjusted with selection of the below-mentioned base film and transparent conductive coating layer.
さらに本発明の導電性フィルムは、その透明導電塗膜層の表面抵抗が１０〜１×１０５Ω／□の範囲にあることが好ましい。該表面抵抗が上限を超えると、液晶ディスプレイ、透明タッチパネル等の透明電極や電磁波シールド材として用いたときに電極として十分に機能しなかったり、十分な電磁波シールド特性が得られなくなる。一方、下限未満にすることは製造工程が不安定になりやすいので好ましくない。好ましい表面抵抗は１０〜５×１０４Ω／□、特に１０〜９×１０３Ω／□の範囲である。 Furthermore, the conductive film of the present invention preferably has a surface resistance of the transparent conductive coating layer in the range of 10 to 1 × 10 5 Ω / □. When the surface resistance exceeds the upper limit, when used as a transparent electrode such as a liquid crystal display or a transparent touch panel or as an electromagnetic shielding material, the surface resistance does not function sufficiently, or sufficient electromagnetic shielding characteristics cannot be obtained. On the other hand, making it less than the lower limit is not preferable because the manufacturing process tends to be unstable. The preferred surface resistance is in the range of 10-5 × 10 4 Ω / □, especially 10-9 × 10 3 Ω / □.
以下、本発明の導電性フィルムを形成する各層について、さらに詳述する。
本発明における低屈折率層は、内部に空隙を有していて見かけの屈折率が１．１０〜１．３５の範囲となるものであれば任意であり、例えば、無機化合物と有機化合物との複合粒子、好ましくはその平均粒径が５〜２００ｎｍの複合粒子からなるものをあげることができる。ここで該複合粒子としては、有機化合物または有機化合物と無機化合物の複合化合物中に無機微粒子が分散されている形態、有機化合物または有機化合物と無機化合物の複合化合物によって表面もしくは内部が改質された無機微粒子を含有している形態、一部無機成分によって変性された有機化合物が層を形成している形態、有機物質と無機物質が縮合等によって直接結合した複合化合物が層を形成している形態、およびそれらの組合わせによる形態などをあげることができる。これらの中でも有機化合物もしくは有機／無機複合化合物によって表面もしくは内部を改質された無機化合物微粒子が、有機化合物、無機化合物もしくはそれらの複合化合物からなるバインダー成分に分散されている組成物が望ましい。また分散された無機化合物微粒子は、分散後に自身が持つ官能基を介して表面もしくは内部を改質する有機化合物または有機化合物と無機化合物の複合化合物もしくはこれら粒子を層内で固定せしめる成分と化学結合を形成してもよい。重要なことは、塗膜形成された低屈折率層が内部に空隙を有し、見かけの屈折率が前記範囲となることである。例え層の内部に空隙が存在していても、見かけの屈折率が前記範囲外となる場合には、十分な反射防止効果（透過率上昇効果）を得ることができないので好ましくない。
Hereinafter, each layer forming the conductive film of the present invention will be described in more detail.
The low refractive index layer in the present invention is optional as long as it has voids inside and an apparent refractive index is in the range of 1.10 to 1.35. For example, an inorganic compound and an organic compound The composite particles, preferably those composed of composite particles having an average particle diameter of 5 to 200 nm can be mentioned. Here, as the composite particles, a form in which inorganic fine particles are dispersed in an organic compound or a composite compound of an organic compound and an inorganic compound, and the surface or the inside is modified by the organic compound or a composite compound of an organic compound and an inorganic compound. A form containing inorganic fine particles, a form in which an organic compound partially modified by an inorganic component forms a layer, a form in which a composite compound in which an organic substance and an inorganic substance are directly bonded by condensation or the like forms a layer , And combinations thereof, and the like. Among these, a composition in which inorganic compound fine particles whose surface or inside is modified by an organic compound or an organic / inorganic composite compound is dispersed in a binder component composed of the organic compound, the inorganic compound, or a composite compound thereof is desirable. In addition, the dispersed inorganic compound fine particles are chemically bonded to an organic compound that modifies the surface or the interior through a functional group possessed after dispersion, a composite compound of an organic compound and an inorganic compound, or a component that fixes these particles in the layer. May be formed. What is important is that the low refractive index layer on which the coating film is formed has voids inside, and the apparent refractive index falls within the above range. Even if there are voids inside the layer, if the apparent refractive index is outside the above range, a sufficient antireflection effect (transmittance increasing effect) cannot be obtained, which is not preferable.
また、本発明の低屈折率層にはフッ素原子を含まれていることが好ましい。フッ素原子を含有する形態は特に限定されないが、例えば無機微粒子を改質する有機化合物、有機／無機複合化合物に含有されるのが好ましい。フッ素原子を含有する化合物の主成分としては有機化合物、無機化合物のどちらかに限定されるものではないが、フッ素原子を有する単量体を含む単量体成分を重合して得られる重合体であることが好ましい。フッ素原子を含む単量体としては、例えばパーフルオロアルキル基を有する有機化合物、または構造の一部にパーフルオロアルキル基を含有する金属アルコキシド、もしくは構造の一部にパーフルオロアルキル基を持つ有機／無機複合体などがあげられる。パーフルオロアルキル基としてはパーフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基、パーフルオロブチル基、パーフルオロヘキシル基、パーフルオロオクチル基、パーフルオロデシル基、パーフルオロドデシル基、パーフルオロテトラデシル基が好適である。このような単量体は１種または２種以上を用いることができる。これらフッ素原子を含む化合物は低屈折率層に含有された有機／無機複合粒子中でもよいし、それら粒子を固定するバインダー成分に含有されていてもよい。 The low refractive index layer of the present invention preferably contains fluorine atoms. Although the form containing a fluorine atom is not particularly limited, for example, it is preferably contained in an organic compound or an organic / inorganic composite compound that modifies inorganic fine particles. The main component of a compound containing a fluorine atom is not limited to either an organic compound or an inorganic compound, but is a polymer obtained by polymerizing a monomer component containing a monomer having a fluorine atom. Preferably there is. Examples of the monomer containing a fluorine atom include an organic compound having a perfluoroalkyl group, a metal alkoxide having a perfluoroalkyl group in part of the structure, or an organic / peroxide having a perfluoroalkyl group in part of the structure. Examples include inorganic composites. Perfluoroalkyl groups include perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluorohexyl, perfluorooctyl, perfluorodecyl, perfluorododecyl, perfluorotetradecyl. A group is preferred. One or more of these monomers can be used. These compounds containing fluorine atoms may be contained in the organic / inorganic composite particles contained in the low refractive index layer, or may be contained in a binder component that fixes the particles.
さらに本発明の低屈折率層は、珪素原子を含有していることが好ましい。珪素を含有する形態も特に限定されないが、例えば無機微粒子を改質する有機化合物、有機／無機複合化合物に含有されるのが好ましい。また、モノマー／ポリマーどちらの形態でも構わない。例としては珪素主鎖ポリマー、シランカップリング剤、およびシランカップリング剤の部分加水分解物または加水分解物の縮合によって得られた珪素酸化物ポリマーなどがあげられる。 Further, the low refractive index layer of the present invention preferably contains silicon atoms. Although the form containing silicon is not particularly limited, for example, it is preferably contained in an organic compound or an organic / inorganic composite compound that modifies inorganic fine particles. Moreover, any form of a monomer / polymer may be used. Examples include a silicon main chain polymer, a silane coupling agent, and a silicon oxide polymer obtained by condensation of a partial hydrolyzate or hydrolyzate of the silane coupling agent.
該低屈折率層の膜厚は特には限定されないが、好ましくは０．００１〜１μｍ、さらに好ましくは０．００５〜０．７μｍ、最も好ましくは０．０１〜０．５μｍである。 The film thickness of the low refractive index layer is not particularly limited, but is preferably 0.001 to 1 μm, more preferably 0.005 to 0.7 μm, and most preferably 0.01 to 0.5 μm.
次に、本発明における透明導電塗膜層は、表面抵抗を下げられ、かつ透明性も具備するものであれば特に制限されないが、下記一般式
この導電性高分子（ａ）を構成するポリ（３，４−ジ置換チオフェン）のＲ１およびＲ２は相互に独立して水素または炭素数が１〜４のアルキル基を表すか、あるいは一緒になって任意に置換されてもよい炭素数が１〜１２のアルキレン基を表す。Ｒ１およびＲ２が一緒になって形成される、置換基を有してもよい炭素数が１〜１２のアルキレン基の代表例としては、１，２−アルキレン基（例えば、１，２−シクロヘキシレンおよび２，３−ブチレンなど）があげられる。また、Ｒ１およびＲ２が一緒になって形成される炭素数が１〜１２のアルキレン基の好適な例としては、メチレン、１，２−エチレンおよび１，３−プロピレン基があげられ、１，２−エチレン基が特に好適である。具体例としては、アルキル置換されていてもよいメチレン基、炭素数１〜１２のアルキル基もしくはフェニル基で置換されていてもよい１，２−エチレン基、１，３−プロピレン基が挙げられる。 R 1 and R 2 of the poly (3,4-disubstituted thiophene) constituting the conductive polymer (a) each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, or together Represents an alkylene group having 1 to 12 carbon atoms which may be optionally substituted. As a typical example of the alkylene group having 1 to 12 carbon atoms which may be substituted and formed by R 1 and R 2 together, a 1,2-alkylene group (for example, 1,2- Cyclohexylene and 2,3-butylene). Further, preferable examples of the alkylene group having 1 to 12 carbon atoms formed by R 1 and R 2 together include methylene, 1,2-ethylene and 1,3-propylene groups. The 2-ethylene group is particularly preferred. Specific examples include a methylene group which may be alkyl-substituted, a 1,2-ethylene group and a 1,3-propylene group which may be substituted with a C 1-12 alkyl group or a phenyl group.
一方導電性高分子（ａ）を構成するポリアニオンとしては、高分子状カルボン酸類（例えばポリアクリル酸、ポリメタクリル酸、ポリマレイン酸など）、高分子状スルホン酸（例えばポリスチレンスルホン酸、ポリビニルスルホン酸など）などがあげられる。これらの高分子状カルボン酸およびスルホン酸類は、ビニルカルボン酸およびビニルスルホン酸類と他の重合可能な低分子化合物、例えばアクリレート類およびスチレンなどとの共重合体であってもよい。これらポリアニオンの中でもポリスチレンスルホン酸およびその全べてもしくは一部が金属塩であるものが好ましく用いられる。 On the other hand, examples of the polyanion constituting the conductive polymer (a) include polymeric carboxylic acids (for example, polyacrylic acid, polymethacrylic acid, polymaleic acid, etc.), polymeric sulfonic acids (for example, polystyrene sulfonic acid, polyvinyl sulfonic acid, etc.). ) Etc. These polymeric carboxylic acids and sulfonic acids may be copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable low molecular compounds such as acrylates and styrene. Among these polyanions, those having polystyrene sulfonic acid and all or part of which are metal salts are preferably used.
本発明における透明導電塗膜層を形成するためのコーティング組成物は、上述の導電性高分子を主成分として水に分散させた分散液を用いるが、必要に応じてポリエステル、ポリアクリル、ポリウレタン、ポリ酢酸ビニル、ポリビニルブチラールなどの適当な有機高分子材料をバインダーとして添加することができる。 The coating composition for forming the transparent conductive coating layer in the present invention uses a dispersion in which the above-mentioned conductive polymer is dispersed in water as a main component, but if necessary, polyester, polyacryl, polyurethane, A suitable organic polymer material such as polyvinyl acetate or polyvinyl butyral can be added as a binder.
さらに必要に応じて、バインダーを溶解させる目的、もしくは基材フィルムへの濡れ性を改善する目的、固形分濃度を調整する目的などで、水と相溶性のある適当な溶媒を添加することができる。例えば、アルコール類（メタノール、エタノール、プロパノール、イソプロパノールなど）、アミド類（ホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、アセトアミド、Ｎ−メチルアセトアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルプロピオンアミド）などが好ましく用いられる。 Furthermore, if necessary, an appropriate solvent compatible with water can be added for the purpose of dissolving the binder, improving the wettability to the base film, or adjusting the solid content concentration. . For example, alcohols (methanol, ethanol, propanol, isopropanol, etc.), amides (formamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide) and the like are preferable. Used.
また得られる透明導電塗膜層の塗膜強度を向上させる目的で、さらにアルコキシシランまたはアシロキシシランを添加してもよい。これらのシラン化合物は、加水分解され、その後の縮合反応された反応生成物の形態で透明導電塗膜層中に存在する。これらのシラン化合物としては、例えばメチルトリアセトキシシラン、ジメチルジアセトキシシラン、トリメチルアセトキシシラン、テトラアセトキシシラン、テトラメトキシシラン、テトラエトキシシラン、テトライソプロポキシシラン、テトライソブトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、トリメチルエトキシシラン、フェニルトリエトキシシランなどがあげられる。なかでも、テトラメトキシシラン、テトラエトキシシラン、テトライソプロポキシシラン、テトライソブトキシシランなどのテトラアルコキシシランおよびγ−グリシドキシプロピルトリメトキシシラン、ビニルトリエトキシシランなどのアルコキシ基以外の反応性官能基を有するトリアルコキシシランが好ましく、特にグリシドキシ基を有するトリアルコキシシランが好ましい。 Further, for the purpose of improving the coating strength of the transparent conductive coating layer obtained, alkoxysilane or acyloxysilane may be further added. These silane compounds are present in the transparent conductive coating layer in the form of a reaction product obtained by hydrolysis and subsequent condensation reaction. Examples of these silane compounds include methyltriacetoxysilane, dimethyldiacetoxysilane, trimethylacetoxysilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetraisobutoxysilane, methyltriethoxysilane, dimethyl Examples thereof include diethoxysilane, trimethylethoxysilane, and phenyltriethoxysilane. Among them, reactive functional groups other than tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane and tetraisobutoxysilane, and alkoxy groups such as γ-glycidoxypropyltrimethoxysilane and vinyltriethoxysilane. A trialkoxysilane having a glycidoxy group is particularly preferable.
このようなシラン化合物の加水分解／縮合を効率よく進行させるためには触媒を併用することが好ましい。触媒としては酸性触媒または塩基性触媒のいずれをも用いることができる。酸性触媒としては、酢酸、塩酸、硝酸等の無機酸、酢酸、クエン酸、プロピオン酸、しゅう酸、ｐ−トルエンスルホン酸等の有機酸等が好適である。一方塩基性触媒としてはアンモニア、トリエチルアミン、トリプロピルアミン等の有機アミン化合物、ナトリウムメトキシド、カリウムメトキシド、カリウムエトキシド、水酸化ナトリウム、水酸化カリウム等のアルカリ金属化合物などが好適である。 In order to efficiently proceed such hydrolysis / condensation of the silane compound, it is preferable to use a catalyst in combination. As the catalyst, either an acidic catalyst or a basic catalyst can be used. As the acidic catalyst, inorganic acids such as acetic acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid, citric acid, propionic acid, oxalic acid and p-toluenesulfonic acid are suitable. On the other hand, as the basic catalyst, organic amine compounds such as ammonia, triethylamine and tripropylamine, and alkali metal compounds such as sodium methoxide, potassium methoxide, potassium ethoxide, sodium hydroxide and potassium hydroxide are suitable.
さらに、上記の透明導電塗膜層形成用のコーティング組成物には、基材フィルムに対する濡れ性を向上させる目的で、少量の界面活性剤を加えてもよい。好ましい界面活性剤としては、非イオン性界面活性剤（例えば、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンアルキルエーテル、ソルビタン脂肪酸エステルなど）、およびフッ素系界面活性剤（例えばフルオロアルキルカルボン酸塩、パーフルオロアルキルベンゼンスルホン酸塩、パーフルオロアルキル４級アンモニウム塩、パーフルオロアルキルポリオキシエチレンエタノールなど）があげられる。 Furthermore, you may add a small amount of surfactant to said coating composition for transparent conductive coating layer formation in order to improve the wettability with respect to a base film. Preferred surfactants include nonionic surfactants (eg, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, sorbitan fatty acid ester, etc.), and fluorosurfactants (eg, fluoroalkylcarboxylates, Fluoroalkylbenzene sulfonate, perfluoroalkyl quaternary ammonium salt, perfluoroalkyl polyoxyethylene ethanol, etc.).
透明導電塗膜層を形成する際の塗布方法としては、それ自体公知の方法を採用できる。例えばリップダイレクト法、コンマコーター法、スリットリバース法、ダイコーター法、グラビアロールコーター法、ブレードコーター法、スプレーコーター法、エアーナイフコート法、ディップコート法、バーコーター法などが好ましく挙げられる。熱硬化性樹脂をバインダーとして併用した場合には、透明導電塗膜層の塗設はそれぞれを形成する成分を含む塗液を基材フィルムに塗布し、加熱乾燥させて塗膜を形成させる。加熱条件としては８０〜１６０℃で１０〜１２０秒間、特に１００〜１５０℃で２０〜６０秒間が好ましい。ＵＶ硬化性樹脂またはＥＢ硬化性樹脂をバインダーとして併用した場合には、一般的には予備乾燥を行った後、紫外線照射または電子線照射を行なう。 As a coating method for forming the transparent conductive coating layer, a method known per se can be adopted. For example, the lip direct method, the comma coater method, the slit reverse method, the die coater method, the gravure roll coater method, the blade coater method, the spray coater method, the air knife coat method, the dip coat method, the bar coater method and the like are preferable. When a thermosetting resin is used in combination as a binder, the coating of the transparent conductive coating layer is performed by applying a coating liquid containing components for forming each to the base film and drying by heating to form a coating film. The heating condition is preferably 80 to 160 ° C. for 10 to 120 seconds, particularly preferably 100 to 150 ° C. for 20 to 60 seconds. When a UV curable resin or an EB curable resin is used in combination as a binder, generally, after preliminary drying, ultraviolet irradiation or electron beam irradiation is performed.
また、かかる透明導電塗膜層を形成するための塗液を後述するアンカーコート層上に塗布する際には、必要に応じて、さらに密着性・塗工性を向上させるための予備処理として、該アンカーコート層表面にコロナ放電処理、プラズマ放電処理などの物理的表面処理を施しても構わない。 In addition, when applying a coating liquid for forming such a transparent conductive coating layer on the anchor coat layer described later, as necessary, as a preliminary treatment for further improving the adhesion and coating properties, The anchor coat layer surface may be subjected to physical surface treatment such as corona discharge treatment or plasma discharge treatment.
なお、透明導電塗膜層の厚みは０．０１〜０．３０μｍの範囲、特に０．０２〜０．２５μｍの範囲であることが好ましい。該塗膜の厚さが薄すぎると十分な導電性が得られないことがあり、逆に厚すぎると、透過率が不足したり、ブロッキングを起こしたりすることがある。 The thickness of the transparent conductive coating layer is preferably in the range of 0.01 to 0.30 μm, particularly preferably in the range of 0.02 to 0.25 μm. If the thickness of the coating film is too thin, sufficient conductivity may not be obtained. Conversely, if it is too thick, the transmittance may be insufficient or blocking may occur.
次に本発明における基材フィルムは特に制限する必要はないが、（メタ）アクリル系樹脂、ポリスチレン、ポリ酢酸ビニル、ポリエチレンやポリプロピレンのようなポリオレフィン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリイミド、ポリアミド、ポリスルホン、ポリカーボネート、ポリエチレンテレフタラート（以下、ＰＥＴと称することがある。）、ポリエチレンナフタレート（以下、ＰＥＮと称することがある。）などのポリエステル（全酸成分を基準として２０モル％以下、好ましくは１０モル％以下の第３成分を共重合していてもよい）やアミノ基、エポキシ基、ヒドロキシル基、カルボニル基等の官能基で一部変性した樹脂、トリアセチルセルロース（ＴＡＣ）などからなるフィルムが好適である。これらの基材フィルムのうち、機械特性や透明性、生産コストの点からポリエステル（ＰＥＴ、ＰＥＮおよびそれらの共重合ポリエステル）フィルムが特に好ましい。基材フィルムの厚みも特に制限されないが、５００μｍ以下が好ましい。５００μｍより厚い場合には剛性が強すぎて、得られたフィルムをディスプレイなどに貼付ける際の取扱い性が低下しやすい。 Next, the base film in the present invention is not particularly limited, but (meth) acrylic resin, polystyrene, polyvinyl acetate, polyolefin such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, polyimide, polyamide, Polysulfone, polycarbonate, polyethylene terephthalate (hereinafter sometimes referred to as PET), polyester such as polyethylene naphthalate (hereinafter sometimes referred to as PEN) (20 mol% or less based on the total acid component, preferably 10% by mole or less of the third component may be copolymerized), a resin partially modified with a functional group such as an amino group, an epoxy group, a hydroxyl group, or a carbonyl group, a film made of triacetyl cellulose (TAC), etc. Is preferred. Of these substrate films, polyester (PET, PEN and their copolyester) films are particularly preferred from the viewpoints of mechanical properties, transparency, and production costs. The thickness of the base film is not particularly limited, but is preferably 500 μm or less. When it is thicker than 500 μm, the rigidity is too strong, and the handleability when the obtained film is attached to a display or the like tends to be lowered.
基材フィルムと前記低屈折率層との間の接着性を向上させるためにアンカーコート層を設けることが好ましい。アンカーコート層としては、透明性を備えるものであれば特に制限はされないが、ポリウレタン、ポリアクリレート、ポリエステル、ポリビニルピロリドン、ポリビニルアルコール、ポリビニルアルコール／ポリエチレン共重合体などの高分子バインダーを例示することができる。なかでも、接着性の観点からポリエステル樹脂およびオキサゾリン基とポリアルキレンオキシド鎖とを有するアクリル樹脂の両方を構成成分とする高分子バインダーが好ましい。 In order to improve the adhesion between the base film and the low refractive index layer, an anchor coat layer is preferably provided. The anchor coat layer is not particularly limited as long as it has transparency, but examples thereof include polymer binders such as polyurethane, polyacrylate, polyester, polyvinyl pyrrolidone, polyvinyl alcohol, and polyvinyl alcohol / polyethylene copolymer. it can. Among these, from the viewpoint of adhesiveness, a polymer binder having both a polyester resin and an acrylic resin having an oxazoline group and a polyalkylene oxide chain as constituent components is preferable.
ここで用いられるポリエステル樹脂としては、以下に示す多塩基酸とポリオールとからなるポリエステルを例示することができるが、特に水（多少の有機溶剤を含有していてもよい）に可溶性または分散性のポリエステルが好ましい。また、オキサゾリン基とポリアルキレンオキシド鎖とを有するアクリル樹脂も、水（多少の有機溶剤を含有していてもよい）に可溶性または分散性のアクリル樹脂が好ましい。 Examples of the polyester resin used herein include polyesters composed of the following polybasic acids and polyols, but are particularly soluble or dispersible in water (may contain some organic solvent). Polyester is preferred. The acrylic resin having an oxazoline group and a polyalkylene oxide chain is also preferably an acrylic resin that is soluble or dispersible in water (may contain some organic solvent).
かかるオキサゾリン基とポリアルキレンオキシ鎖とを有するアクリル樹脂は、例えば以下に示すオキサゾリン基を有するモノマーとポリアルキレンオキシド鎖を有するモノマーとを共重合成分として含むもので、他の共重合成分を含んでいても構わない。 Such an acrylic resin having an oxazoline group and a polyalkyleneoxy chain contains, for example, a monomer having the following oxazoline group and a monomer having a polyalkylene oxide chain as copolymerization components, and includes other copolymerization components. It does not matter.
まずオキサゾリン基を有するモノマーとしては、例えば２−ビニル−２−オキサゾリン、２−ビニル−４−メチル−２−オキサゾリン、２−ビニル−５−メチル−２−オキサゾリン、２−イソプロペニル−４−メチル−２−オキサゾリン、２−イソプロペニル−５−メチル−２−オキサゾリン等を挙げることができ、これらの１種または２種以上の混合物を使用することができる。これらの中で２−イソプロペニル−２−オキサゾリンが工業的に入手しやすく好適である。かかるオキサゾリン基を有するアクリル樹脂を用いることによりアンカーコート層の凝集力が向上し、透明導電塗膜層との密着性がより強固になる。さらにフィルム製膜工程内や透明導電塗膜層加工工程における金属ロールに対する耐擦傷性を基材フィルム表面に付与できる。なお、オキサゾリン基を含有するモノマーの含有量は、該アクリル樹脂中の含有量として２〜４０重量％、好ましくは３〜３５重量％、さらに好ましくは５〜３０重量％である。 First, examples of the monomer having an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-4-methyl. -2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline and the like, and one or a mixture of two or more of these can be used. Of these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially. By using an acrylic resin having such an oxazoline group, the cohesive force of the anchor coat layer is improved, and the adhesion with the transparent conductive coating layer is further strengthened. Furthermore, the abrasion resistance with respect to the metal roll in a film forming process or a transparent conductive coating-film layer processing process can be provided to the base film surface. In addition, content of the monomer containing an oxazoline group is 2 to 40 weight% as content in this acrylic resin, Preferably it is 3 to 35 weight%, More preferably, it is 5 to 30 weight%.
次にポリアルキレンオキシド鎖を有するモノマーとしては、アクリル酸、メタクリル酸のエステル部にポリアルキレンオキシドを付加させたものを挙げることができる。ポリアルキレンオキシド鎖はポリメチレンオキシド、ポリエチレンオキシド、ポリプロピレンオキシド、ポリブチレンオキシド等を挙げることができる。ポリアルキレンオキシド鎖の繰り返し単位は３〜１００であることが好ましい。かかるポリアルキレンオキシド鎖を有するアクリル樹脂を用いることによりアンカーコート層中のポリエステル樹脂とアクリル樹脂の相溶性がポリアクリレンオキシド鎖を含有しないアクリル樹脂と比較してよくなり、アンカーコート層の透明性を向上させることができる。ここでポリアルキレンオキシド鎖の繰返し単位が３より小さいとポリエステル樹脂とアクリル樹脂との相溶性が低下してアンカーコート層の透明性が悪くなり、逆に１００より大きいとアンカーコート層の耐湿熱性が下がり、高湿度、高温下での透明導電塗膜層との密着性が悪化する。なお、ポリアルキレンオキシド鎖を有するモノマーの含有量は、該アクリル樹脂中の含有量として３〜４０重量％、好ましくは４〜３５重量％、さらに好ましくは５〜３０重量％である。 Next, examples of the monomer having a polyalkylene oxide chain include those obtained by adding polyalkylene oxide to an ester part of acrylic acid or methacrylic acid. Examples of the polyalkylene oxide chain include polymethylene oxide, polyethylene oxide, polypropylene oxide, and polybutylene oxide. The repeating unit of the polyalkylene oxide chain is preferably 3 to 100. By using such an acrylic resin having a polyalkylene oxide chain, the compatibility of the polyester resin and the acrylic resin in the anchor coat layer is improved compared to an acrylic resin not containing a polyacrylene oxide chain, and the transparency of the anchor coat layer is improved. Can be improved. Here, when the repeating unit of the polyalkylene oxide chain is smaller than 3, the compatibility between the polyester resin and the acrylic resin is lowered and the transparency of the anchor coat layer is deteriorated. Decrease, adhesion with the transparent conductive coating layer at high humidity and high temperature deteriorates. In addition, content of the monomer which has a polyalkylene oxide chain is 3 to 40 weight% as content in this acrylic resin, Preferably it is 4 to 35 weight%, More preferably, it is 5 to 30 weight%.
アンカーコート層を形成するポリエステル樹脂のアンカーコート層中の含有割合は５〜９５重量％であることが好ましく、特に５０〜９０重量％であることが好ましい。アンカーコート層を形成するオキサゾリン基とポリアルキレンオキシド鎖とを有するアクリル樹脂のアンカーコート層中の含有割合は５〜９０重量％であることが好ましく、特に１０〜５０重量％であることが好ましい。ポリエステル樹脂が９５重量％を超える、もしくはオキサゾリン基とポリアルキレンオキシド鎖とを有するアクリル樹脂が５重量％未満になるとアンカーコート層の凝集力が低下し、透明導電塗膜層の密着性が不十分になる場合がある。 The content ratio of the polyester resin forming the anchor coat layer in the anchor coat layer is preferably 5 to 95% by weight, and particularly preferably 50 to 90% by weight. The content of the acrylic resin having an oxazoline group and a polyalkylene oxide chain forming the anchor coat layer in the anchor coat layer is preferably 5 to 90% by weight, and particularly preferably 10 to 50% by weight. When the polyester resin exceeds 95% by weight, or the acrylic resin having an oxazoline group and a polyalkylene oxide chain is less than 5% by weight, the cohesive force of the anchor coat layer is lowered and the adhesiveness of the transparent conductive coating layer is insufficient. It may become.
上記アンカーコート層中には脂肪族ワックスを０．５〜３０重量％含有させることが好ましく、特に１〜１０重量％含有させることが好ましい。この割合が０．５重量％より少ないとフィルム表面の滑性向上効果が認められなくなることがある。一方３０重量％を越えると基材フィルムへの密着や、透明導電塗膜層に対するアンカーコート性が不足する場合がある。 The anchor coat layer preferably contains 0.5 to 30% by weight of aliphatic wax, particularly preferably 1 to 10% by weight. When this ratio is less than 0.5% by weight, the effect of improving the smoothness of the film surface may not be recognized. On the other hand, when it exceeds 30% by weight, the adhesion to the base film and the anchor coat property to the transparent conductive coating layer may be insufficient.
さらに、上記アンカーコート層中には平均粒子径が０．００５〜０．５μｍの範囲にある微粒子を０．１〜２０重量％含有させることが好ましい。アンカーコート層中の微粒子の含有量が０．１重量％未満であると、フィルムの滑性が低下してロール状に巻き取ることが困難になることがあり。逆に２０重量％を超えるとアンカーコート層の透明性が低下して、ディスプレイ／タッチパネル等の用途によっては使用できなくなることがある。なお、アンカーコート層を形成する高分子バインダーと微粒子との屈折率差は、反射防止効果およびヘイズの観点から０．０２以下であることが好ましく、屈折率差がこれを超えて大きくなると得られる導電性フィルムの透明性が低下する場合がある。 Further, the anchor coat layer preferably contains 0.1 to 20% by weight of fine particles having an average particle diameter in the range of 0.005 to 0.5 μm. If the content of the fine particles in the anchor coat layer is less than 0.1% by weight, the slipperiness of the film may be lowered and it may be difficult to wind the film into a roll. On the other hand, if it exceeds 20% by weight, the transparency of the anchor coat layer is lowered, and it may be impossible to use depending on the application such as a display / touch panel. The difference in refractive index between the polymer binder forming the anchor coat layer and the fine particles is preferably 0.02 or less from the viewpoint of the antireflection effect and haze, and can be obtained when the refractive index difference exceeds this value. The transparency of the conductive film may decrease.
次に、該アンカーコート層を基材フィルム上に形成させるために、上記の成分を水溶液、水分散液または乳化液等の水性塗液の形態として使用することが好ましい。塗膜を形成するために、必要に応じて、前記成分以外に他の成分、例えば帯電防止剤、着色剤、界面活性剤、紫外線吸収剤等を添加することもできる。特に滑剤を添加することにより、耐ブロッキング性をさらに良好なものとすることができる。 Next, in order to form the anchor coat layer on the base film, the above components are preferably used in the form of an aqueous coating solution such as an aqueous solution, an aqueous dispersion or an emulsion. In order to form a coating film, in addition to the above components, other components such as an antistatic agent, a colorant, a surfactant, and an ultraviolet absorber can be added as necessary. In particular, the addition of a lubricant can further improve the blocking resistance.
アンカーコート層の塗工に用いる水性塗液の固形分濃度は通常２０重量％以下であるが特に１〜１０重量％であることが好ましい。この割合が１重量％未満であると、基材フィルムへの濡れ性が不足することがあり、一方２０重量％を超えると塗液の貯蔵安定性やアンカーコート層の外観が悪化することがある。 The solid content concentration of the aqueous coating liquid used for coating the anchor coat layer is usually 20% by weight or less, but preferably 1 to 10% by weight. If this ratio is less than 1% by weight, the wettability to the substrate film may be insufficient, while if it exceeds 20% by weight, the storage stability of the coating liquid and the appearance of the anchor coat layer may be deteriorated. .
アンカーコート層を基材フィルムに塗工するには、任意の段階で実施することができるが、ポリエステルフィルムを例に説明すると、その製造過程で実施するのが好ましく、特に配向結晶化が完了する前のポリエステルフィルムに塗布するのが好ましい。 The anchor coat layer can be applied to the base film at any stage. However, when the polyester film is described as an example, it is preferably performed during the production process, and the oriented crystallization is completed. It is preferably applied to the previous polyester film.
ここで配向結晶化が完了する前のポリエステルフィルムとは、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何れか一方に配向せしめた一軸配向フィルム、さらには縦方向および横方向の二方向に低倍率延伸配向せしめたもの（最終的に縦方向、また横方向に再延伸せしめて配向結晶化を完了せしめる前の二軸延伸フィルム）等を含むものである。なかでも未延伸フィルムまたは一方向に配向せしめた一軸延伸フィルムにアンカーコート層を形成するための水性塗液を塗布し、そのまま縦延伸および／または横延伸と熱固定とを施すのが好ましい。 Here, the polyester film before completion of oriented crystallization is an unstretched film, a uniaxially oriented film in which the unstretched film is oriented in either the longitudinal direction or the transverse direction, and further in two directions, the longitudinal direction and the transverse direction. And the like that have been stretched and oriented at a low magnification (biaxially stretched film before being finally re-stretched in the machine direction or transverse direction to complete orientation crystallization). In particular, it is preferable to apply an aqueous coating liquid for forming an anchor coat layer to an unstretched film or a uniaxially stretched film oriented in one direction, and to perform longitudinal stretching and / or lateral stretching and heat setting as it is.
アンカーコート層を形成するための水性塗液を基材フィルムに塗布する際には、塗布性を向上させるための予備処理として、フィルム表面にコロナ処理、火炎処理、プラズマ処理等の物理処理を施すか、あるいは組成物と共にこれと化学的に不活性な界面活性剤を併用することが好ましい。 When applying the aqueous coating liquid for forming the anchor coat layer to the base film, physical treatment such as corona treatment, flame treatment, plasma treatment, etc. is applied to the film surface as a preliminary treatment for improving the coatability. Alternatively, it is preferable to use a chemically inert surfactant together with the composition.
アンカーコート層を形成する際の塗布方法としては、それ自体公知の方法を採用すればよい。例えばリップダイレクト法、コンマコーター法、スリットリバース法、ダイコーター法、グラビアロールコーター法、ブレードコーター法、スプレーコーター法、エアーナイフコート法、ディップコート法、バーコーター法などを例示することができ、これらの方法を単独または組み合わせて用いることができる。なお、塗膜は必要に応じてフィルムの片面のみに形成してもよいし、両面に形成してもよい。 As a coating method for forming the anchor coat layer, a method known per se may be employed. For example, lip direct method, comma coater method, slit reverse method, die coater method, gravure roll coater method, blade coater method, spray coater method, air knife coat method, dip coat method, bar coater method, etc. These methods can be used alone or in combination. In addition, a coating film may be formed only in the single side | surface of a film as needed, and may be formed in both surfaces.
本発明の導電性フィルムは、上述のとおり基材フィルムの少なくとも片面に、内部に空隙を有する低屈折率層および透明導電塗膜層がこの順序で積層されているものであるが、透明導電塗膜層が形成される側と反対の面に、必要に応じてアンカーコート層、ハードコート層などの塗膜を設けることもできる。 As described above, the conductive film of the present invention has a low refractive index layer having a void inside and a transparent conductive coating layer laminated in this order on at least one surface of the base film. If necessary, a coating film such as an anchor coat layer or a hard coat layer can be provided on the surface opposite to the side on which the film layer is formed.
以下、実施例をあげて本発明をさらに具体的に説明する。なお、実施例中における各評価は下記の方法にしたがった。 Hereinafter, the present invention will be described more specifically with reference to examples. In addition, each evaluation in an Example followed the following method.
（１）反射率、膜厚および屈折率
反射率については、反射分光膜厚計（大塚電子製、商品名「ＦＥ−３０００」）を用いて試料導電性フィルムの透明導電塗膜層側の波長３００〜８００ｎｍにおける反射率を測定した。
低屈折率層、透明導電塗膜層、アンカーコート層の膜厚および屈折率は、それぞれの層を形成した後に反射率を測定し、その測定値について、代表的な屈折率の波長分散の近似式としてｎ−ｋ Ｃａｕｃｈｙの分散式を引用し、スペクトルの実測値とフィッティングさせることにより求めた。
〈反射率〉
◎：波長５５０ｎｍにおける反射率が３％以下
○：波長５５０ｎｍにおける反射率が３％超、４％以下
×：波長５５０ｎｍにおける反射率が４％超
(1) Reflectance, film thickness and refractive index For reflectance, the wavelength on the transparent conductive coating layer side of the sample conductive film using a reflection spectral film thickness meter (made by Otsuka Electronics, trade name “FE-3000”) The reflectance at 300 to 800 nm was measured.
The film thickness and refractive index of the low-refractive index layer, transparent conductive coating layer, and anchor coat layer are measured by measuring the reflectance after each layer is formed, and the measured values approximate the wavelength dispersion of typical refractive indexes. The nk Cauchy dispersion formula was cited as the formula, and it was obtained by fitting with the measured value of the spectrum.
<Reflectance>
◎: Reflectance at a wavelength of 550 nm is 3% or less ○: Reflectance at a wavelength of 550 nm is more than 3%, 4% or less ×: Reflectance at a wavelength of 550 nm is more than 4%
（２）ガラス転移温度
サンプル約１０ｍｇを測定用のアルミニウム製パンに封入して示差熱量計（デュポン社製 Ｖ４．ＯＢ２０００型ＤＳＣ）に装着し、２５℃から２０℃／分の速度で３００℃まで昇温させ、３００℃で５分間保持した後取り出し、直ちに氷の上に移して急冷する。このパンを再度示差熱量計に装着し、２５℃から２０℃／分の速度で３００℃まで昇温させてガラス転移温度（Ｔｇ：℃）を測定する。
(2) Glass transition temperature Approximately 10 mg of sample is sealed in an aluminum pan for measurement and attached to a differential calorimeter (DuPont V4.OB2000 DSC), and the temperature is increased from 25 ° C. to 300 ° C. at a rate of 20 ° C./min. The temperature is raised, held at 300 ° C. for 5 minutes, then taken out, immediately transferred onto ice and rapidly cooled. The pan is again attached to the differential calorimeter, and the glass transition temperature (Tg: ° C.) is measured by increasing the temperature from 25 ° C. to 300 ° C. at a rate of 20 ° C./min.
（３）固有粘度
固有粘度（〔η〕ｄｌ／ｇ）は２５℃のｏ−クロロフェノール溶液で測定する。
(3) Intrinsic viscosity Intrinsic viscosity ([η] dl / g) is measured with an o-chlorophenol solution at 25 ° C.
（４）全光線透過率
ＪＩＳ Ｋ７１５０にしたがい、スガ試験機（株）製のヘイズメーターＨＣＭ−２Ｂにて測定し、下記の基準で評価した。
＜全光線透過率＞
○：全光線透過率≧７０％ ・・・透明性良好
×：全光線透過率＜７０％ ・・・透明性不良
(4) Total light transmittance Measured with a haze meter HCM-2B manufactured by Suga Test Instruments Co., Ltd. according to JIS K7150, and evaluated according to the following criteria.
<Total light transmittance>
◯: Total light transmittance ≧ 70%. Excellent transparency X: Total light transmittance <70%.
（５）表面抵抗
三菱化学社製Ｌｏｒｅｓｔｅｒ ＭＣＰ−Ｔ６００を用いて、ＪＩＳ Ｋ７１９４に準拠して測定した。
測定は任意の箇所を５回測定し、それらの平均値とした。また評価は以下の基準で行った。
○：表面抵抗が１０〜１０４Ω／□の範囲にある
×：表面抵抗が１０〜１０４Ω／□の範囲にない
(5) Surface resistance It measured based on JISK7194 using Mitsubishi Chemical Corporation Lorester MCP-T600.
The measurement was performed five times at an arbitrary location, and the average value thereof was taken. Evaluation was performed according to the following criteria.
○: Surface resistance is in the range of 10 to 10 4 Ω / □ ×: Surface resistance is not in the range of 10 to 10 4 Ω / □
［実施例１］
＜アンカーコート層形成用塗液の調整＞
ポリエステル：酸成分が２，６−ナフタレンジカルボン酸６５モル％／イソフタル酸３０モル％／５−ナトリウムスルホイソフタル酸５モル％、グリコール成分がエチレングリコール９０モル％／ジエチレングリコール１０モル％で構成されている（Ｔｇ＝８０℃、平均分子量１３０００）。
[Example 1]
<Adjustment of anchor coat layer forming coating solution>
Polyester: The acid component is composed of 65 mol% of 2,6-naphthalenedicarboxylic acid / 30 mol% of isophthalic acid / 5 mol% of 5-sodium sulfoisophthalic acid, and the glycol component is composed of 90 mol% of ethylene glycol / 10 mol% of diethylene glycol. (Tg = 80 ° C., average molecular weight 13000).
なお、かかるポリエステルは特開平６−１１６４８７号公報の実施例１に記載の方法に準じて下記のとおり製造した。すなわち２,６−ナフタレンジカルボン酸ジメチル４４部、イソフタル酸ジメチル４部、エチレングリコール３４部、ジエチレングリコール２部を反応器に仕込み、これにテトラブトキシチタン０．０５部を添加して窒素雰囲気下で温度を２３０℃にコントロールして加熱し、生成するメタノールを留去させてエステル交換反応を行った。次いで反応系の温度を徐々に２５５℃までに上昇させ系内を１ｍｍＨｇの減圧にして重縮合反応を行い、ポリエステルを得た。
Such a polyester was produced as follows according to the method described in Example 1 of JP-A-6-116487. That is, 44 parts of
アクリル：メチルメタクリレート３０モル％／２−イソプロペニル−２−オキサゾリン３０モル％／ポリエチレンオキシド（ｎ＝１０）メタクリレート１０モル％／アクリルアミド３０モル％で構成されている（Ｔｇ＝５０℃）。 Acrylic: 30 mol% methyl methacrylate / 2 mol of 2-isopropenyl-2-oxazoline / polyethylene oxide (n = 10) 10 mol% methacrylate / 30 mol% acrylamide (Tg = 50 ° C.)
なお、かかるアクリルは特開昭６３−３７１６７号公報の製造例１〜３に記載の方法に準じて下記のとおり製造した。すなわち、四つ口フラスコに、界面活性剤としてラウリルスルホン酸ナトリウム３部およびイオン交換水１８１部を仕込んで窒素気流中で６０℃まで昇温させ、次いで重合開始剤として過硫酸アンモニウム０．５部、亜硝酸水素ナトリウム０．２部を添加し、さらにモノマー類であるメタクリル酸メチル２３．３部、２−イソプロペニル−２−オキサゾリン２２．６部、ポリエチレンオキシド（ｎ＝１０）メタクリレート４０．７部、アクリルアミド１３．３部の混合物を３時間にわたり、液温が６０〜７０℃になるように調整しながら滴下した。滴下終了後も同温度範囲に２時間保持しつつ攪拌下に反応を継続させ、次いで冷却して固形分が３５％のアクリル水分散体を得た。 The acrylic was produced as follows according to the method described in Production Examples 1 to 3 of JP-A-63-37167. That is, in a four-necked flask, 3 parts of sodium lauryl sulfonate and 181 parts of ion-exchanged water as surfactants were charged and heated to 60 ° C. in a nitrogen stream, and then 0.5 parts of ammonium persulfate as a polymerization initiator, 0.2 part of sodium hydrogen nitrite was added, and further 23.3 parts of methyl methacrylate as monomers, 22.6 parts of 2-isopropenyl-2-oxazoline, 40.7 parts of polyethylene oxide (n = 10) methacrylate A mixture of 13.3 parts of acrylamide was added dropwise over 3 hours while adjusting the liquid temperature to 60 to 70 ° C. After completion of dropping, the reaction was continued with stirring while maintaining the same temperature range for 2 hours, and then cooled to obtain an acrylic water dispersion having a solid content of 35%.
添加剤：シリカフィラー（平均粒径１００ｎｍ）（日産化学株式会社製：商品名スノーテックスＺＬ）
濡れ剤：ポリオキシエチレン（ｎ＝７）ラウリルエーテル（三洋化成株式会社製 商品名ナロアクティーＮ−７０）
Additive: Silica filler (average particle size 100 nm) (manufactured by Nissan Chemical Co., Ltd .: trade name Snowtex ZL)
Wetting agent: polyoxyethylene (n = 7) lauryl ether (trade name NAROACTY N-70, manufactured by Sanyo Chemical Co., Ltd.)
＜基材フィルムおよびアンカーコート層の形成＞
溶融ポリエチレンテレフタレート（〔η〕＝０．６２ｄｌ/ｇ、Ｔｇ＝７８℃）をダイより押し出し、常法により冷却ドラムで冷却して未延伸フィルムとし、次いで縦方向に３．４倍延伸した後、その両面に上述のポリエステル６０部、アクリル３０部、添加剤５部、濡れ剤５部からなる塗液をイオン交換水で濃度８％に調整し、ロールコーターで均一に塗布した。次いで塗工後にこのフィルムを横方向に１２５℃で３．６倍延伸し、２２０℃で幅方向に３％収縮させ熱固定を行い、アンカーコート層が形成された、厚さ１８８μｍの基材フィルムを得た。なお、塗膜の厚さはそれぞれ０．１０μｍであった。
<Formation of base film and anchor coat layer>
Molten polyethylene terephthalate ([η] = 0.62 dl / g, Tg = 78 ° C.) was extruded from a die, cooled with a cooling drum by a conventional method to form an unstretched film, and then stretched 3.4 times in the longitudinal direction. A coating solution comprising 60 parts of polyester, 30 parts of acrylic, 5 parts of additive, and 5 parts of a wetting agent was adjusted to a concentration of 8% with ion-exchanged water on both surfaces and uniformly applied with a roll coater. Next, after coating, the film was stretched 3.6 times in the transverse direction at 125 ° C., shrunk 3% in the width direction at 220 ° C. and heat-fixed, and a base film with a thickness of 188 μm was formed. Got. The thickness of each coating film was 0.10 μm.
〈低屈折率層の形成〉
四つ口フラスコ内でイオン交換水１７９ｇにクエン酸１ｇを溶解させた液に、ヘプタデカフルオロデシルメチルジメトキシシラン１０ｇをゆっくりと添加し、全量投入後１０分間の攪拌を行った。その溶液中に平均粒径６０ｎｍの中空シリカ粒ＩＰＡ分散ゾル（固形分２０％、触媒化成工業製）９５ｇを攪拌しながら少量づつ混合し、全量投入後液温を６０℃に保ち２時間攪拌を行うことで粒子の表面処理を行った。処理後、エバポレーターを用いて溶媒を除いた後、窒素雰囲気下１２０℃で２時間の乾燥を行い。表面処理中空シリカ粒子（Ｓ−１）を約２０ｇ得た。次にこのフラスコにメタノール９００ｇ、エタノール３００ｇイオン交換水５５０ｇ、２重量％の濃度のアンモニア水５０ｇを加えて１時間攪拌した後、さらにテトラメトキシシラン１６２ｇ、γ―メタクリロキシプロピルトリメトキシシラン１８ｇを加え、白濁した液が透明になるまで６時間の攪拌を行って加水分解反応を進行させてコーティング前駆液（Ａ）を作成した。
<Formation of low refractive index layer>
In a four-necked flask, 10 g of heptadecafluorodecylmethyldimethoxysilane was slowly added to a solution in which 1 g of citric acid was dissolved in 179 g of ion-exchanged water, and the whole was added and stirred for 10 minutes. In this solution, 95 g of hollow silica particle IPA dispersion sol (solid content 20%, manufactured by Catalytic Chemical Industry Co., Ltd.) 95 g with an average particle diameter of 60 nm was mixed little by little while stirring. The surface treatment of the particles was performed. After the treatment, the solvent was removed using an evaporator, followed by drying at 120 ° C. for 2 hours in a nitrogen atmosphere. About 20 g of surface-treated hollow silica particles (S-1) were obtained. Next, 900 g of methanol, 300 g of ethanol, 550 g of ion-exchanged water and 50 g of ammonia water having a concentration of 2% by weight were added to the flask and stirred for 1 hour, and then 162 g of tetramethoxysilane and 18 g of γ-methacryloxypropyltrimethoxysilane were added. Then, the coating precursor solution (A) was prepared by agitating for 6 hours until the cloudy solution became transparent to advance the hydrolysis reaction.
ｔ−ブチルメタクリレート３０ｇ、２-ヒドロキシエチルメタクリレート７０ｇ、ブチルアクリレート１００ｇを窒素雰囲気下１１０℃の温度に保った酢酸ブチル２００ｇに滴下ロートを用いて混合した溶液に２，２’−アゾビスイソブチロニトリル２ｇを添加し、液を２時間加熱することで共重合を行いコーティング前駆液（Ｂ）を得た。次にコーティング前駆液（Ａ）１８０ｇに酢酸エチル３２０ｇ、イソプロピルアルコール１６０ｇ、レベリング剤としてシリコーンオイルを０．１ｇ添加した溶液を３時間攪拌し、その溶液にコーティング前駆液（Ｂ）２０ｇを滴下ロートを用いて徐々に混合し、全量滴下後３時間攪拌を行い、固形分濃度２０％のコーティング主剤（Ｃ）を得た。コーティング主剤（Ｃ）５ｇ、ＭＩＢＫ６６．２ｇ、イソシアネート系硬化剤０．１２ｇを混合して１０分攪拌することで固形分濃度１．５％のコーティング液（Ｄ）を調整した。コーティング液（Ｄ）をマイヤーバーにて塗工し、１５０℃の温度下１分で乾燥・硬化反応させて低屈折率層を得た。マイヤーバーの番手にて膜厚が４５ｎｍになるように調整した。得られた低屈折率層を顕微鏡で観察すると空隙部が観察され、また、その屈折率は１．２６０であった。 2,2′-Azobisisobutyro was added to a solution obtained by mixing 30 g of t-butyl methacrylate and 70 g of 2-hydroxyethyl methacrylate and 100 g of butyl acrylate with 200 g of butyl acetate kept at a temperature of 110 ° C. using a dropping funnel. Nitrile (2 g) was added, and the liquid was heated for 2 hours for copolymerization to obtain a coating precursor liquid (B). Next, a solution obtained by adding 320 g of ethyl acetate, 160 g of isopropyl alcohol and 0.1 g of silicone oil as a leveling agent to 180 g of the coating precursor solution (A) is stirred for 3 hours, and 20 g of the coating precursor solution (B) is dropped into the solution. The mixture was gradually mixed and stirred for 3 hours after dropping the whole amount to obtain a coating main agent (C) having a solid content concentration of 20%. A coating liquid (D) having a solid content concentration of 1.5% was prepared by mixing 5 g of the coating main agent (C), 66.2 g of MIBK, and 0.12 g of an isocyanate curing agent and stirring for 10 minutes. The coating liquid (D) was applied with a Mayer bar and dried and cured at a temperature of 150 ° C. for 1 minute to obtain a low refractive index layer. The film thickness of the Meyer bar was adjusted to 45 nm. When the obtained low refractive index layer was observed with a microscope, voids were observed and the refractive index was 1.260.
＜透明導電塗膜層の形成＞
導電性ポリマー：ポリ（３，４−エチレンジオキシチオフェン）０．５重量％とポリスチレンスルホン酸（分子量Ｍｎ＝１５０，０００）０．８重量％を含んでなるポリマーの水分散体（ＢａｙｔｒｏｎＰ：バイエルＡＧ製）９７部に対して３部のジエチレングリコールを添加した塗液を、マイヤーバーを用いて上記のアンカーコート層を設けた基材フィルム上に塗工し、１３０℃で２分間の乾燥を行い、透明導電塗膜層を得た。得られた透明導電塗膜層の厚みは０．０１４μｍ、屈折率は１．５０であった。得られた評価結果を表１および表２に示す。
<Formation of transparent conductive coating layer>
Conductive polymer: aqueous dispersion of polymer (BaytronP: Bayer) comprising 0.5% by weight of poly (3,4-ethylenedioxythiophene) and 0.8% by weight of polystyrene sulfonic acid (molecular weight Mn = 150,000) (Manufactured by AG) 3 parts of diethylene glycol was added to 97 parts of the coating film on the base film provided with the anchor coat layer using a Mayer bar and dried at 130 ° C. for 2 minutes. A transparent conductive coating layer was obtained. The transparent conductive coating layer obtained had a thickness of 0.014 μm and a refractive index of 1.50. The obtained evaluation results are shown in Tables 1 and 2.
［実施例２および３］
低屈折率層および透明導電塗膜層の膜厚を表１記載のとおりに変更し、さらに実施例３においてはアンカーコート層を設けない以外は実施例１と同様に行った。得られた評価結果を表１および表２に示す。
[Examples 2 and 3]
The thicknesses of the low refractive index layer and the transparent conductive coating layer were changed as shown in Table 1, and in Example 3, the same procedure as in Example 1 was performed except that no anchor coat layer was provided. The obtained evaluation results are shown in Tables 1 and 2.
［実施例４］
基材フィルムを形成する材料として溶融ポリエチレン−２,６−ナフタレート（［η］＝０．６５ｄｌ／ｇ、Ｔｇ＝１２１℃）をダイより押出し、常法により冷却ドラムで冷却して未延伸フィルムとし、次いで縦方向に３．４倍延伸した後、その両面に実施例１で用いた塗液の濃度８．２％の水性塗液をロールコーターで均一に塗布した。次いで塗工後にこのフィルムを横方向に１２５℃で３．６倍延伸し、２２０℃で幅方向に３％収縮させ熱固定を行い、アンカーコート層が形成された、厚さ１８８μｍの基材フィルムを得た。なお、塗膜の厚さは０．１５μｍであった。次いで、低屈折率層および透明導電塗膜層の膜厚が表１記載のとおりになるようにする以外は実施例１と同様にして導電性フィルムを得た。得られた評価結果を表１および表２に示す。
[Example 4]
As a material for forming the base film, molten polyethylene-2,6-naphthalate ([η] = 0.65 dl / g, Tg = 121 ° C.) is extruded from a die and cooled by a cooling drum by a conventional method to form an unstretched film. Subsequently, the film was stretched 3.4 times in the longitudinal direction, and then an aqueous coating solution having a concentration of 8.2% of the coating solution used in Example 1 was uniformly applied on both sides thereof with a roll coater. Next, after coating, the film was stretched 3.6 times in the transverse direction at 125 ° C., shrunk 3% in the width direction at 220 ° C. and heat-fixed, and a base film with a thickness of 188 μm was formed. Got. The thickness of the coating film was 0.15 μm. Next, a conductive film was obtained in the same manner as in Example 1 except that the film thicknesses of the low refractive index layer and the transparent conductive coating layer were as shown in Table 1. The obtained evaluation results are shown in Tables 1 and 2.
［比較例１］
低屈折率層としてアクリル系ＨＣ（商品名 ＨＣ９００： 大日精化製）をマイヤーバーを用いて塗工した以外は実施例２と同様の操作を行った。得られた低屈折率層の膜厚は０．２５μｍ、屈折率は１．５１であった。評価結果を表１および表２に示す。
[Comparative Example 1]
The same operation as in Example 2 was performed except that acrylic-based HC (trade name HC900: manufactured by Dainichi Seika) was applied as a low refractive index layer using a Mayer bar. The resulting low refractive index layer had a thickness of 0.25 μm and a refractive index of 1.51. The evaluation results are shown in Tables 1 and 2.
［比較例２］
低屈折層を形成しなかった以外は実施例１と同様の操作を行った。評価結果を表１および表２に示す。
[Comparative Example 2]
The same operation as in Example 1 was performed except that the low refractive layer was not formed. The evaluation results are shown in Tables 1 and 2.
これらの表からわかるように、透明導電塗膜層の下に、層内に空隙部が形成された見かけの屈折率が特定範囲にある低屈折率層を設けることにより、表面反射を低減することができ、透明性の高い導電性フィルムが得られる。 As can be seen from these tables, surface reflection can be reduced by providing a low-refractive-index layer with an apparent refractive index in a specific range with voids formed in the layer under the transparent conductive coating layer. And a highly transparent conductive film can be obtained.
以上に説明した本発明の導電性フィルムは、優れた透明性および導電性を有しているので、透明タッチパネル、液晶ディスプレイ（ＬＣＤ）、有機エレクトロルミネッセンス素子、無機エレクトロルミネッセンス素子等の透明電極や電磁波シールド材として極めて有用である。 Since the conductive film of the present invention described above has excellent transparency and conductivity, transparent electrodes such as transparent touch panels, liquid crystal displays (LCDs), organic electroluminescence elements, inorganic electroluminescence elements, and electromagnetic waves It is extremely useful as a shielding material.
１ 基材フィルム
２ 低屈折率層
３ 透明導電塗膜層
４ ハードコート層
1
Claims (6)
で表される繰返し単位からなるポリカチオン状のポリチオフェンと、ポリアニオンとからなる導電性高分子を含有する請求項１に記載の導電性フィルム。 The transparent conductive coating layer has the following general formula
The conductive film according to claim 1, comprising a conductive polymer composed of a polycationic polythiophene comprising a repeating unit represented by formula (I) and a polyanion.
で表される繰返し単位からなるポリカチオン状のポリチオフェンと、ポリアニオンとから構成される導電性高分子と、テトラアルコキシシランおよびアルコキシ基以外の反応性の官能基を有するトリアルコキシシランからなる群より選ばれる少なくとも一種のシラン化合物との反応生成物を含有する請求項１記載の導電性フィルム。 The transparent conductive coating layer has the following general formula
Selected from the group consisting of a polycationic polythiophene composed of a repeating unit represented by the following formula: a conductive polymer composed of a polyanion, and a tetraalkoxysilane and a trialkoxysilane having a reactive functional group other than an alkoxy group. The conductive film according to claim 1, comprising a reaction product with at least one silane compound.
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| JP2000149661A (en) * | 1998-11-05 | 2000-05-30 | Samsung General Chem Co Ltd | Polythiophene-based conductive polymer solution composition having high conductivity and high transparency |
| JP2003216061A (en) * | 2001-10-25 | 2003-07-30 | Matsushita Electric Works Ltd | Composite thin film holding substrate, transparent conductive film holding substrate and vertical cavity surface-emitting body |
| JP2003157724A (en) * | 2001-11-21 | 2003-05-30 | Mitsubishi Polyester Film Copp | Conductive film |
| JP2003292655A (en) * | 2002-04-04 | 2003-10-15 | Teijin Dupont Films Japan Ltd | Antistatic laminated polyester film |
| JP2004345278A (en) * | 2003-05-23 | 2004-12-09 | Sony Corp | Transparent conductive base, resistive film type touch panel and display element |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008120443A1 (en) * | 2007-03-29 | 2008-10-09 | Nagase Chemtex Corporation | Conductive multilayer body |
| JP2009190267A (en) * | 2008-02-14 | 2009-08-27 | Fujifilm Corp | Conductive film forming substrate, conductive film, and manufacturing method of conductive film |
| JP2010192186A (en) * | 2009-02-17 | 2010-09-02 | Toray Ind Inc | Transparent conductive laminate |
| JP2011204402A (en) * | 2010-03-24 | 2011-10-13 | Toppan Printing Co Ltd | Transparent conductive layer laminated base material and touch panel using the same |
| JP2012187806A (en) * | 2011-03-10 | 2012-10-04 | Toppan Printing Co Ltd | Transparent conductive layer laminated base material |
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