JP2001110238A - Low reflectance transparent conductive laminated film - Google Patents
Low reflectance transparent conductive laminated filmInfo
- Publication number
- JP2001110238A JP2001110238A JP2000162439A JP2000162439A JP2001110238A JP 2001110238 A JP2001110238 A JP 2001110238A JP 2000162439 A JP2000162439 A JP 2000162439A JP 2000162439 A JP2000162439 A JP 2000162439A JP 2001110238 A JP2001110238 A JP 2001110238A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- transparent conductive
- conductive layer
- film
- low
- 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.)
- Pending
Links
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000013532 laser treatment Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 230000037387 scars Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Laminated Bodies (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、優れた帯電防止効
果、電磁波遮蔽効果及び機械強度特性を有する透明導電
性フイルムに関する。さらには、反射防止効果、及び防
汚性に優れた反射防止用透明導電性フイルムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent conductive film having excellent antistatic effect, electromagnetic wave shielding effect and mechanical strength characteristics. Further, the present invention relates to an antireflection transparent conductive film having an excellent antireflection effect and antifouling property.
【０００２】[0002]
【従来の技術】近年電子機器分野において、透明性のあ
る帯電防止や電磁波シールド材料が種々の装置で必要に
なっている。ＴＶやコンピュータディスプレイとして用
いられている陰極線管やプラズマディスプレーは、フェ
ースパネル面に発生する静電気により埃が付着して視認
性が低下する他、電磁波を輻射して周囲に悪影響を及ぼ
すなどの問題点を有している。 また陰極線管のフラッ
ト化等により、反射防止機能が必要となっている。また
フェースパネル面は手が触れたり、汚れを落とすことに
より、擦り傷が発生しやすい問題があった。2. Description of the Related Art In recent years, in the field of electronic equipment, transparent antistatic and electromagnetic wave shielding materials have been required for various devices. Cathode ray tubes and plasma displays used as TVs and computer displays have the problem that dust adheres to the face panel surface due to static electricity, which reduces visibility, and radiates electromagnetic waves to adversely affect the surroundings. have. Further, the flattening of the cathode ray tube or the like requires an antireflection function. In addition, the face panel surface has a problem that scratches are easily generated by touching or removing dirt.
【０００３】帯電防止、電磁波遮蔽および反射防止を目
的として、銀等の金属あるいはＩＴＯ等の導電性金属酸
化物を蒸着・スパッタ等で導電性層をフェースパネル面
に直接形成させる方法が提案されているが、膜形成には
真空処理や高温処理が必要であり、製造費が高価になっ
たり、生産性に問題があった。For the purpose of preventing static electricity, shielding electromagnetic waves and preventing reflection, a method has been proposed in which a conductive layer is formed directly on the face panel surface by vapor deposition or sputtering of a metal such as silver or a conductive metal oxide such as ITO. However, vacuum processing and high-temperature processing are required for film formation, which increases the manufacturing cost and raises productivity problems.
【０００４】また、ゾル−ゲル法による塗布方式の導電
性薄膜の形成法も提案されているが（羽生等，Ｎａｔｉ
ｏｎａｌ Ｔｅｃｎｉｃａｌ Ｒｅｐｏｒｔ ４０，Ｎ
ｏ．１，（１９９４）９０）、高温処理が必要であり，
透明基材であるプラスチックフイルム上やハードコート
上への積層は基材の変質が起こることにより，基材とし
て使用できる素材が限定されてしまう問題があった。A method of forming a conductive thin film by a coating method by a sol-gel method has also been proposed (Hani et al., Nati.
onal Technical Report 40, N
o. 1, (1994) 90), high temperature treatment is required,
Lamination on a plastic film or a hard coat, which is a transparent base material, has a problem in that the quality of the base material changes and the materials that can be used as the base material are limited.
【０００５】導電性酸化物微粒子やコロイドを分散させ
た透明導電性塗料も提案されているが（特開平６−３４
４４８９号公報、特開平７−２６８２５１号公報等）、
得られた透明導電性層の導電性が低い問題があった。[0005] A transparent conductive paint in which conductive oxide fine particles and colloids are dispersed has also been proposed (JP-A-6-34).
4489, JP-A-7-268251, etc.),
There was a problem that the conductivity of the obtained transparent conductive layer was low.
【０００６】さらに、導電性をあげるため、金属微粒子
からなる透明導電膜が提案されるようになってきた（例
えば、特開平９−５５１７５号公報）。透明導電膜上に
テトラエトキシシラン等の反射防止塗料を塗布すること
により低反射透明導電膜を形成する方法が提案されてい
る（例えば、特開平１０−１４２４０１号公報）。透明
基材の上に金属微粒子を塗布しただけでは機械強度が弱
いという問題や、テトラエトキシシラン等の反射防止塗
料は長時間の高温熱処理が必要であり、ゾル−ゲル法に
よる反射防止層の積層は透明基材の使用が限られてしま
う問題が生じてしまい，上記低反射透明導電膜の形成方
法ではガラスフェースパネルに直接塗布することしかで
きないという問題があった．そこで，設備投資が大き
く，高温処理が必要なフェースパネル前面に直接塗膜を
形成させる方法に対し，基材に薄膜を形成したものを張
り付ける方法も提案されている（瀧等，Ｎａｔｉｏｎａ
ｌ Ｔｅｃｈｎｉｃａｌ Ｒｅｐｏｒｔ，４２，Ｎｏ．
３（１９９６）２６４−２６８）。Further, in order to increase conductivity, a transparent conductive film made of metal fine particles has been proposed (for example, Japanese Patent Application Laid-Open No. 9-55175). A method of forming a low-reflection transparent conductive film by applying an antireflection paint such as tetraethoxysilane on the transparent conductive film has been proposed (for example, Japanese Patent Application Laid-Open No. H10-142401). The problem that mechanical strength is weak just by coating metal fine particles on a transparent base material, and anti-reflective coatings such as tetraethoxysilane require long-term high-temperature heat treatment, and the anti-reflection layer is laminated by a sol-gel method. However, there is a problem that the use of the transparent base material is limited, and the above method of forming the low-reflection transparent conductive film can only be applied directly to the glass face panel. Therefore, a method in which a thin film is formed on a substrate is applied to a method in which a coating film is formed directly on the front surface of a face panel which requires a high temperature treatment and requires a high temperature treatment (Taki et al., Natia).
l Technical Report, 42, No.
3 (1996) 264-268).
【０００７】これらの薄膜の形成方法は，ＩＴＯ等の導
電性金属酸化物を蒸着・スパッタ等で導電性層を形成さ
せる方法であり、膜形成には真空処理が必要であり、製
造費が高価になったり、生産性に問題があった。The method of forming these thin films is a method of forming a conductive layer by depositing or sputtering a conductive metal oxide such as ITO, and requires vacuum treatment for film formation, which is expensive in manufacturing cost. Or there was a problem with productivity.
【０００８】例えば、特開平１０−３８６８号公報に記
載されているように、電磁波遮蔽のための導電性層には
アースすることが必要であるが、これらの導電層用保護
層を形成した場合には、導電性はその保護層表面からと
ることが困難となり、導電性層になんらかのターミナル
を設けたり、導電性層を何らかの方法で露出させアース
させる必要があった。そのために、導電性層に導電性テ
ープを取り付けた後、低屈折率層を形成させたり、表面
の保護膜を剥離させたり、あるいは保護膜を貫通させた
り、超音波溶接したりして、導電層をアースすることが
必要であった。したがって、これらの加工工程において
導電層に傷が付き耐候性悪化を発生したり、保護膜やそ
の他の機能層の損傷を伴ったりして、商品価値を損なう
ことが多々見られた。さらに、コスト的にも大きな負荷
を与え生産性に劣るという欠点を有するものであった。For example, as described in Japanese Patent Application Laid-Open No. 10-3868, a conductive layer for shielding electromagnetic waves needs to be grounded, but when a protective layer for these conductive layers is formed, In this case, it is difficult to obtain conductivity from the surface of the protective layer, and it has been necessary to provide some terminals in the conductive layer or to expose the conductive layer by some method and to ground. Therefore, after attaching the conductive tape to the conductive layer, the low refractive index layer is formed, the protective film on the surface is peeled off, or the protective film is penetrated, or ultrasonic welding is performed. It was necessary to ground the layer. Therefore, in these processing steps, the conductive layer is often scratched and deteriorated in weather resistance, and the protective film and other functional layers are often damaged, thereby impairing the commercial value. Further, it has a drawback that it imposes a heavy load on cost and is inferior in productivity.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、上記の課題
を解決するためになされたものであって、帯電防止性、
電磁波遮蔽性、反射防止性、機械特性、防汚性に加えて
生産性にも優れたフェースパネルに貼り付けることの可
能な低反射導電性積層フイルムを提供することであり、
さらには導電性フィルム表面から直接アース可能な生産
性に優れた透明導電性フイルムを提供することにある。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and has an antistatic property,
It is an object of the present invention to provide a low-reflection conductive laminated film that can be attached to a face panel that is excellent in productivity in addition to electromagnetic wave shielding properties, antireflection properties, mechanical properties, and antifouling properties.
Another object of the present invention is to provide a transparent conductive film excellent in productivity which can be directly grounded from the surface of the conductive film.
【００１０】[0010]
【課題を解決するための手段】上記の課題は、透明基材
上にハードコート層と，少なくとも１種の金属または金
属酸化物からなる微粒子を有する透明導電層と、該透明
導電層の外層に形成され、少なくとも１層の防汚性を有
する透明導電層保護層とを含むことを特徴とする低反射
透明導電性積層フイルムにより解決された。The above object is achieved by providing a hard coat layer on a transparent substrate, a transparent conductive layer having fine particles of at least one kind of metal or metal oxide, and an outer layer of the transparent conductive layer. This problem has been solved by a low-reflection transparent conductive laminated film characterized in that it comprises at least one transparent conductive layer protective layer having antifouling properties.
【００１１】本発明の低反射透明導電フイルムを、ＴＶ
やコンピュータディスプレイとして用いられている陰極
線管やプラズマディスプレーの表面に直接ラミネートす
ることにより、ＰＶＤ法やＣＶＤ法を用いる従来の導電
性被膜の形成技術やフェースパネル等に直接導電性皮膜
等を塗布する方法に比べ、設備も工程も格段に簡易化す
ることができる。さらに、フイルムの導電層保護層表面
から直接アースを取ることができ、生産工程も簡略化で
きる。The low-reflection transparent conductive film of the present invention is a TV
Laminating directly on the surface of a cathode ray tube or plasma display used as a computer display, or a conventional conductive film forming technique using a PVD method or a CVD method, or directly applying a conductive film to a face panel, etc. Compared with the method, the equipment and the process can be significantly simplified. Further, the ground can be taken directly from the surface of the conductive layer protective layer of the film, and the production process can be simplified.
【００１２】以下、本発明の態様について説明するが本
発明はこれらに限定されるものではない。 （１）透明基材上にハードコート層と、少なくとも１種
の金属からなる微粒子を有する透明導電層と、該透明導
電層の外層に形成され、該透明導電層の屈折率と異なる
屈折率を有する少なくとも１層の防汚性を有する導電層
保護層とを含むことを特徴とする低反射透明導電性積層
フイルム。 （２）透明基材上に、少なくとも１層の透明導電層と透
明導電層に隣接する導電層用保護層を有する透明導電性
フイルムにおいて、該導電層用保護層が誘電体力率が
０．０１（５０Ｈｚ）以上の樹脂を含有する層であるこ
とを特徴とする透明導電性フイルム。 （３）透明基材上にハードコート層と、少なくとも1層
の１種以上の金属あるいは金属酸化物からなる導電性微
粒子を有する透明導電層と、該透明導電層の外側に形成
された導電層保護層を有する透明導電性フィルムにおい
て、該導電層保護層が該透明導電層の屈折率と異なる屈
折率を有する少なくとも1層からなる防汚性を有する層
からなり、さらに誘電体力率が０．０１（５０Ｈｚ）以
上の樹脂を含有する層であることを特徴とする低反射透
明導電性フィルム。 （４）少なくとも1層の１種以上の金属あるいは金属酸
化物からなる導電性微粒子を有する透明導電層の表面抵
抗が１０ＫΩ／□（９０Ｖ印加電圧）以下であることを
特徴とする（３）に記載の低反射透明導電性フイルム。 （５）少なくとも1層の１種以上の金属あるいは金属酸
化物からなる導電性微粒子を有する透明導電層におい
て、導電性金属粒子の粒子サイズが１〜２００ｎｍであ
ることを特徴とする（３）または（４）に記載の低反射
透明導電性フイルム。 （６）該導電性微粒子が金、銀もしくは銅を主体とする
金属または金属酸化物であることを特徴とする（３）か
ら（５）のいずれかに記載の低反射透明導電性フイル
ム。 （７）該金属からなる微粒子が、銀あるいは銀を主体と
する合金の微粒子であることを特徴とする（３）から
（６）のいずれかに記載の低反射透明導電性積層フイル
ム。 （８）該防汚性を有する導電層保護層の屈折率が、１．
３０以上１．７０以下であることを特徴とする（３）か
ら（７）のいずれかに記載の低反射透明導電性積層フイ
ルム。 （９）導電層用保護層の厚さが、１０〜５００ｎｍであ
ることを特徴とする（３）から（８）のいずれかに記載
の低反射透明導電性積層フイルム。 （１０）該防汚性を有する導電層保護層が、少なくとも
１層の反射防止層と、防汚性を有する最外層からなるこ
とを特徴とする（３）から（９）のいずれかに記載の低
反射透明導電性積層フイルム。 （１１）該防汚性を有する最外層がフッ素を含む化合物
を含有することを特徴とする（３）から（１０）のいず
れかにに記載の低反射透明導電性積層フイルム。 （１２）該導電層用保護層からの表面抵抗が２ＫΩ／□
（９０Ｖ印加電圧）以下であることを特徴とする（３）
から（１１）のいずれかに記載の低反射透明導電性フイ
ルム。 （１３）該透明基材がハードコート層を有するプラスチ
ックフイルムであることを特徴とする（３）から（１
２）のいずれかに記載の低反射透明導電性フイルム。 （１４）（３）から（１３）のいずれかに記載の導電層
保護層付き導電性フイルムの表面から直接アースをとる
ことを特徴とする透明導電性フイルムの接地方法。Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto. (1) a hard coat layer on a transparent substrate, a transparent conductive layer having fine particles of at least one kind of metal, and a refractive index different from the refractive index of the transparent conductive layer formed on an outer layer of the transparent conductive layer. A low-reflection transparent conductive laminated film comprising at least one conductive layer protective layer having an antifouling property. (2) A transparent conductive film having on a transparent substrate at least one transparent conductive layer and a protective layer for a conductive layer adjacent to the transparent conductive layer, wherein the protective layer for the conductive layer has a dielectric power factor of 0.01. A transparent conductive film, which is a layer containing a resin of (50 Hz) or higher. (3) a hard coat layer on a transparent substrate, a transparent conductive layer having at least one layer of conductive fine particles of one or more metals or metal oxides, and a conductive layer formed outside the transparent conductive layer In the transparent conductive film having a protective layer, the conductive layer protective layer is composed of at least one antifouling layer having a refractive index different from that of the transparent conductive layer, and further has a dielectric power factor of 0.1. A low-reflection transparent conductive film, which is a layer containing a resin of 01 (50 Hz) or higher. (4) The transparent conductive layer having at least one layer of conductive fine particles made of one or more metals or metal oxides has a surface resistance of 10 KΩ / □ (90 V applied voltage) or less. The low-reflection transparent conductive film according to the above. (5) In the transparent conductive layer having at least one layer of conductive fine particles made of one or more metals or metal oxides, the conductive metal particles have a particle size of 1 to 200 nm (3) or The low-reflection transparent conductive film according to (4). (6) The low-reflection transparent conductive film according to any one of (3) to (5), wherein the conductive fine particles are a metal or a metal oxide mainly composed of gold, silver or copper. (7) The low-reflection transparent conductive laminated film according to any one of (3) to (6), wherein the fine particles made of the metal are fine particles of silver or an alloy mainly containing silver. (8) The conductive layer protective layer having antifouling property has a refractive index of 1.
The low-reflection transparent conductive laminated film according to any one of (3) to (7), wherein the thickness is 30 or more and 1.70 or less. (9) The low-reflection transparent conductive laminated film according to any one of (3) to (8), wherein the thickness of the conductive layer protective layer is 10 to 500 nm. (10) The conductive layer protective layer having antifouling property comprises at least one antireflection layer and an outermost layer having antifouling property, according to any one of (3) to (9). Low reflective transparent conductive laminated film. (11) The low-reflection transparent conductive laminated film according to any one of (3) to (10), wherein the outermost layer having antifouling properties contains a compound containing fluorine. (12) The surface resistance from the conductive layer protective layer is 2 KΩ / □
(90V applied voltage) or less (3)
The low-reflection transparent conductive film according to any one of (1) to (11). (13) The transparent substrate is a plastic film having a hard coat layer, wherein (3) to (1)
The low-reflection transparent conductive film according to any one of 2). (14) A method for grounding a transparent conductive film, wherein the ground is directly taken from the surface of the conductive film with a conductive layer protective layer according to any one of (3) to (13).
【００１３】[0013]
【発明の実施の形態】次に本発明の構成を例にとり説明
する。図１に、本発明の好ましい一実施形態である低反
射透明導電性積層フイルムを示す。基材ベースの側から
ハードコート層、導電性微粒子からなる透明導電層と、
その外層に導電層保護層が形成され、最外層の防汚層か
ら構成されている。導電層保護層が防汚機能を兼ねてい
てもよく、その場合は防汚層を省略することができる。Next, the configuration of the present invention will be described as an example. FIG. 1 shows a low-reflection transparent conductive laminated film according to a preferred embodiment of the present invention. A hard coat layer from the side of the base material base, a transparent conductive layer made of conductive fine particles,
A conductive layer protective layer is formed on the outer layer, and is constituted by the outermost antifouling layer. The conductive layer protective layer may also have an antifouling function, in which case the antifouling layer can be omitted.
【００１４】本発明の積層フイルムは、ハードコート層
を設けたことによりフイルムの傷付を防止し、金属微粒
子または金属酸化物微粒子からなる透明導電層が積層さ
れているので導電性であり、帯電が防止されると共に、
陰極線管等から輻射される電磁波を効果的に遮断するこ
とができ、さらに透明導電層の屈折率と異なる屈折率を
有する導電層保護層により外部からの反射光を低下させ
ることができ、誘電体力率が０．０１（５０Ｈｚ）以上
の樹脂を含有する導電層保護層によりフイルム表面から
直接アースをとることができる。防汚性のある導電層保
護層あるいは最外層に設けた防汚層により、フイルムの
汚れを防止することができる。The laminated film of the present invention is provided with a hard coat layer to prevent the film from being damaged, and is electrically conductive because a transparent conductive layer composed of fine metal particles or fine metal oxide particles is laminated. Is prevented,
Electromagnetic waves radiated from a cathode ray tube or the like can be effectively blocked, and furthermore, a reflected light from the outside can be reduced by a conductive layer protective layer having a refractive index different from that of the transparent conductive layer. The ground can be taken directly from the film surface by the conductive layer protective layer containing a resin having a rate of 0.01 (50 Hz) or more. The conductive layer protective layer having antifouling property or the antifouling layer provided on the outermost layer can prevent the film from being stained.
【００１５】本発明に用いられる基材は、フイルム状の
プラスチックフイルムであり、ポリエチレンテレフタレ
ート、ポリエチレンナフタレート、ポリエチレンテレフ
タレートとポリエチレンナフタレート共重合物あるいは
混合物等のポリエステル、ポリカーボネート、ノルボル
ネン系樹脂（環状オレフィン共重合体）、トリアセチル
セルロース、ジアセチルセルロース等のセルロース樹
脂、ポリアリレート、ポリメタクリル酸メチルエステル
等のフイルムが好ましい。これらのフイルムの厚みは２
０〜５００μｍが好ましく、薄すぎると膜強度が弱く、
厚いとスティフネスが大きく貼り付けが困難になり、１
００〜２００μｍがより好ましい。The substrate used in the present invention is a plastic film in the form of a film, such as polyester such as polyethylene terephthalate, polyethylene naphthalate, or a copolymer or mixture of polyethylene terephthalate and polyethylene naphthalate, polycarbonate, norbornene-based resin (cyclic olefin resin). Copolymers), cellulose resins such as triacetyl cellulose and diacetyl cellulose, and films such as polyarylate and polymethyl methacrylate are preferred. The thickness of these films is 2
0 to 500 μm is preferable, and if too thin, the film strength is weak,
If it is thick, stiffness becomes large and it becomes difficult to attach it.
00 to 200 μm is more preferable.
【００１６】本発明の基材は、いずれも疎水性の表面を
有するためその表面を各種処理することが好ましい。例
えば、薬品処理、機械的処理、コロナ放電処理、火焔処
理、紫外線処理、高周波処理、グロー放電処理、活性プ
ラズマ処理、レーザー処理、混酸処理、オゾン酸化処
理、などの表面活性化処理をしてその上に構成層を付与
し接着力を得る方法が挙げられる。また、一旦前述のこ
れらの表面処理をした後、あるいは表面処理なしで、下
塗層を設けその上に構成層を付与する方法も好ましい。
下塗層の構成としても種々の工夫が行なわれており、第
１層として支持体によく接着する層を設け、その上に第
２層として構成層とよく接着する親水性の樹脂層を塗布
する所謂重層法と、疎水性基と親水性基との両方を含有
する樹脂層を一層のみ塗布する単層法とがある。Since the base material of the present invention has a hydrophobic surface, it is preferable to subject the surface to various treatments. For example, surface activation treatment such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc. There is a method in which a constituent layer is provided thereon to obtain an adhesive force. Further, a method in which an undercoat layer is provided and a constituent layer is provided thereon after the above-mentioned surface treatment is performed once or without the surface treatment is also preferable.
Various contrivances have been made for the structure of the undercoat layer. A layer that adheres well to the support is provided as the first layer, and a hydrophilic resin layer that adheres well to the constituent layer is applied thereon as the second layer. There is a so-called multi-layer method and a single-layer method in which only one resin layer containing both a hydrophobic group and a hydrophilic group is applied.
【００１７】表面処理の中でも好ましいのは、紫外線照
射処理、火焔処理、コロナ処理、グロー処理である。紫
外線照射処理については、特公昭４３−２６０３号、特
公昭４３−２６０４号、特公昭４５−３８２８号記載の
処理方法などによって行われるのが好ましく、高圧水銀
灯で紫外線の波長が１８０〜３２０ｎｍの間であるもの
が好ましい。次にコロナ放電処理について記すと、、従
来公知のいずれの方法、例えば特公昭４８−５０４３
号、同４７−５１９０５号、特開昭４７−２８０６７
号、同４９−８３７６７号、同５１−４１７７０号、同
５１−１３１５７６号等に開示された方法により達成す
ることができる。放電周波数は５０Ｈｚ〜５０００ＫＨ
ｚ、好ましくは５ＫＨｚ〜数１００ＫＨｚが適当であり
特に好ましくは１０ＫＨｚ〜３０ＫＨｚである。又、火
焔処理としては天然ガス、液化プロパンガスなどを利用
でき空気との混合比が重要である。好ましいガス／空気
の混合比は容積比で、プロパンでは１／１４〜１／２
２、より好ましくは１／１６〜１／１９である。天然ガ
スでは１／６〜１／１０、より好ましくは１／７〜１／
９である。火焔処理量は、１〜５０Ｋｃａｌ／ｍ2、よ
り好ましくは３〜２０Ｋｃａｌ／ｍ2である。また効果
的な表面処理であるグロー放電処理は、従来知られてい
るいずれの方法、例えば特公昭３５−７５７８号、同３
６−１０３３６号、同４５−２２００４号、同４５−２
２００５号、同４５−２４０４０号、同４６−４３４８
０号、米国特許３，０５７，７９２号、同３，０５７，
７９５号、同３，１７９，４８２号、同３，２８８，６
３８号、同３，３０９，２９９号、同３，４２４，７３
５号、同３，４６２，３３５号、同３，４７５，３０７
号、同３，７６１，２９９号、英国特許９９７，０９３
号、特開昭５３−１２９２６２号等を用いることができ
る。Preferred among the surface treatments are ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment. The ultraviolet irradiation treatment is preferably carried out by the treatment method described in JP-B-43-2603, JP-B-43-2604, or JP-B-45-3828. Is preferred. Next, the corona discharge treatment will be described by any of the conventionally known methods, for example, Japanese Patent Publication No. 48-5043.
No. 47-51905, JP-A-47-28067.
, 49-83767, 51-41770, 51-131576, and the like. Discharge frequency is 50Hz-5000KH
z, preferably 5 KHz to several 100 KHz, and particularly preferably 10 KHz to 30 KHz. In addition, natural gas, liquefied propane gas and the like can be used for the flame treatment, and the mixing ratio with air is important. A preferable gas / air mixing ratio is a volume ratio, and propane is 1/14 to 1/2.
2, more preferably 1/16 to 1/19. For natural gas, 1/6 to 1/10, more preferably 1/7 to 1 /
9 The flame treatment amount is 1 to 50 Kcal / m 2 , more preferably 3 to 20 Kcal / m 2 . The glow discharge treatment, which is an effective surface treatment, can be performed by any of the conventionally known methods, for example, Japanese Patent Publication No. 35-7578 and No. 3
Nos. 6-10336, 45-22004 and 45-2
No. 2005, No. 45-24040, No. 46-4348
0, U.S. Pat. Nos. 3,057,792 and 3,057,
No. 795, No. 3,179,482, No. 3,288,6
Nos. 38, 3,309,299, 3,424,73
No. 5, 3,462,335, 3,475,307
No. 3,761,299, British Patent 997,093
And JP-A-53-129262 can be used.
【００１８】次に、下塗法について述べると、例えば塩
化ビニル、塩化ビニリデン、スチレン、ブタジエン、メ
タクリル酸（エステル）、アクリル酸（エステル）、イ
タコン酸（エステル）、無水マレイン酸などの中かち選
ばれたモノマーからなる重合体、ポリエチレンイミン、
エポキシ樹脂、グラフト化ゼラチン、ニトロセルロー
ス、など数多くのポリマーを挙げることができる。また
本発明では親水性下塗ポリマーも利用でき水溶性ポリマ
ー、セルロースエステル、ラテックスポリマー、水溶性
ポリエステルなどが例示される。水溶性ポリマーとして
は、ゼラチン、ゼラチン誘導体、カゼイン、寒天、アル
ギン酸ソーダ、でんぷん、ポリビニールアルコール、ポ
リアクリル酸共重合体、無水マレイン酸共重合体などで
あり、セルロースエステルとしてはカルボキシメチルセ
ルロース、ヒドロキシエチルセルロースなどである。ラ
テックスポリマーとしては塩化ビニル含有共重合体、塩
化ビニリデン含有共重合体、アクリル酸エステル含有共
重合体、酢酸ビニル含有共重合体、ブタジエン含有共重
合体などである。下塗り層の硬化剤も有効に利用でき例
えばクロム塩（クロム明ばんなど）、アルデヒド類（ホ
ルムアルデヒド、グルタールアルデなど）、イソシアネ
ート類、活性ハロゲン化合物（２，４−ジクロロ−６−
ヒドロキシ−Ｓ−トリアジンなど）、エピクロルヒドリ
ン樹脂などを挙げることができる。本発明に係わる下塗
液は、一般によく知られた塗布方法、例えばディップコ
ート法、エアーナイフコート法、カーテンコート法、ロ
ーラーコート法、ワイヤーバーコート法、グラビアコー
ト法、或いは米国特許第２，６８１，２９４号明細書に
記載のホッパーを使用するエクストルージョンコート法
により塗布することができる。Next, the undercoating method will be described. For example, the undercoating method is selected from vinyl chloride, vinylidene chloride, styrene, butadiene, methacrylic acid (ester), acrylic acid (ester), itaconic acid (ester), maleic anhydride and the like. Polymer consisting of a monomer, polyethyleneimine,
Numerous polymers such as epoxy resins, grafted gelatin, nitrocellulose and the like can be mentioned. In the present invention, a hydrophilic undercoat polymer can also be used, and examples thereof include water-soluble polymers, cellulose esters, latex polymers, and water-soluble polyesters. Examples of the water-soluble polymer include gelatin, a gelatin derivative, casein, agar, sodium alginate, starch, polyvinyl alcohol, a polyacrylic acid copolymer, and a maleic anhydride copolymer. And so on. Latex polymers include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylate-containing copolymers, vinyl acetate-containing copolymers, butadiene-containing copolymers, and the like. A curing agent for the undercoat layer can also be used effectively, for example, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutar alde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-).
Hydroxy-S-triazine) and epichlorohydrin resin. The undercoating liquid according to the present invention can be prepared by applying a well-known coating method such as dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, or US Pat. No. 2,681. , 294, can be applied by an extrusion coating method using a hopper.
【００１９】本発明に用いるハードコート層には公知の
硬化性樹脂を用いることができ、熱硬化樹脂、活性エネ
ルギー線硬化型樹脂等の公知のものをあげることができ
る。熱硬化性樹脂としてはメラミン樹脂、ウレタン樹
脂、エポキシ樹脂等のプレポリマーの架橋反応を利用す
るものを挙げることができる。また活性エネルギー線硬
化型樹脂の例としては多官能モノマーが挙げられ、たと
えば多官能アクリレートまたはメタクリレート（例えば
ペンタエリスリトールテトラ（メタ）アクリレートやジ
ペンタエリスリトールヘキサ（メタ）アクリレート、ト
リメチロールプロパントリ（メタ）アクリレート等）に
代表される活性エネルギー線硬化性化合物が挙げられ
る。活性エネルギー線としては、紫外線、電子線、ガン
マ線等が上げられるが、紫外線が好ましい。紫外線照射
による硬化の場合は、これらの硬化性化合物中には必要
に応じて重合開始剤を添加することが好ましい。活性エ
ネルギー線硬化性樹脂の例としては、ペンタエリスリト
ールテトラ（メタ）アクリレートやジペンタエリスリト
ールヘキサ（メタ）アクリレート等の活性エネルギー線
硬化性化合物が好ましい。Known hardening resins can be used for the hard coat layer used in the present invention, and known ones such as thermosetting resins and active energy ray-curable resins can be used. Examples of the thermosetting resin include those utilizing a crosslinking reaction of a prepolymer such as a melamine resin, a urethane resin, and an epoxy resin. Examples of the active energy ray-curable resin include polyfunctional monomers, for example, polyfunctional acrylates or methacrylates (for example, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropanetri (meth) acrylate). Active energy ray-curable compounds represented by acrylates, etc.). Examples of the active energy ray include an ultraviolet ray, an electron beam, a gamma ray and the like, and an ultraviolet ray is preferable. In the case of curing by ultraviolet irradiation, it is preferable to add a polymerization initiator to these curable compounds as needed. As an example of the active energy ray-curable resin, an active energy ray-curable compound such as pentaerythritol tetra (meth) acrylate or dipentaerythritol hexa (meth) acrylate is preferable.
【００２０】また、ハードコート層中には硬度をアップ
させるため、充填剤として、シリカ、アルミナ、ジルコ
ニア、チタニア等の金属酸化物の微粒子やコロイダル粒
子を添加することできる。これらの粒子の硬さは硬い方
が好ましく、モース硬度６以上のものがより好ましい。
これらの微粒子の粒子サイズは１〜１００ｎｍが好まし
い。１００ｎｍを越えるとヘイズが出やすくなり、１ｎ
ｍ以下では分散が難しく充填剤の効果が得難くなる。微
粒子の添加量は硬化性樹脂の５体積％以上、５０体積％
以下が好ましく、２０体積％以上、４５体積％以下がよ
り好ましい。５０％以上では膜が脆く、５体積％未満で
は添加した効果が得られない。これらの金属酸化物微粒
子は分散及び樹脂との相互作用を大きくするため、表面
修飾処理を行うことが好ましい。表面修飾の例として
は、（メタ）アクリル基含有のシランカップリング剤、
カルボン酸、リン酸等の極性基を含有する(メタ)アクリ
ル酸誘導体等を挙げることができる。In order to increase the hardness in the hard coat layer, fine particles of metal oxides such as silica, alumina, zirconia and titania and colloidal particles can be added as a filler. The hardness of these particles is preferably higher, and those having a Mohs hardness of 6 or more are more preferable.
The particle size of these fine particles is preferably from 1 to 100 nm. If it exceeds 100 nm, haze is likely to appear and 1n
If it is less than m, dispersion is difficult and the effect of the filler is difficult to obtain. The addition amount of the fine particles is 5% by volume or more and 50% by volume of the curable resin.
Or less, more preferably 20% by volume or more and 45% by volume or less. If it is 50% or more, the film is brittle, and if it is less than 5% by volume, the added effect cannot be obtained. These metal oxide fine particles are preferably subjected to a surface modification treatment in order to increase the dispersion and the interaction with the resin. Examples of surface modification include (meth) acrylic group-containing silane coupling agents,
(Meth) acrylic acid derivatives containing a polar group such as carboxylic acid and phosphoric acid can be exemplified.
【００２１】ハードコートの層厚は２〜３０μｍが好ま
しく、４〜１０μｍが特に好ましい。さらに必要に応じ
て、アニオン界面活性剤、カチオン界面活性剤を添加し
たり、コロナ処理、グロー処理等の表面処理を行い、表
面の親水性、密着性を向上させることができる。The layer thickness of the hard coat is preferably from 2 to 30 μm, particularly preferably from 4 to 10 μm. Further, if necessary, an anionic surfactant or a cationic surfactant may be added, or a surface treatment such as a corona treatment or a glow treatment may be performed to improve the hydrophilicity and adhesion of the surface.
【００２２】本発明の導電層は、少なくとも１種以上の
導電性金属あるいは導電性金属酸化物を含有する層であ
り、その導電層の抵抗が１０ＫΩ／□（９０Ｖ印加電
圧）以下、好ましくは１０〜１０００Ω／□、さらに好
ましくは１０Ω〜７００Ω／□であることを特徴とす
る。これらの層の作成に当たっては、金属又は金属酸化
物を蒸着、スパッタやメッキ等により作成する方法と、
金属粒子又は金属酸化物粒子等の導電性微粒子を塗布
し、導電層を形成する方法があるが、導電性微粒子の塗
布により導電性層を形成する方法が生産性向上の点で好
ましい。導電性金属微粒子としては、金、銀、銅、アル
ミニウム、鉄、ニッケル、パラジウム、プラチナあるい
はこれらの合金などである。また導電性金属酸化物微粒
子としては、酸化インジウム、酸化スズ、酸化アンチモ
ン、酸化亜鉛、酸化アルミニウム、酸化珪素、酸化鉄あ
るいはこれらの複合酸化物である。これらの中でも、本
発明では金属微粒子が好ましく、特に銀が好ましい。さ
らに耐候性の観点から銀とパラジウムの合金が好ましい
く、パラジウムの含有量としては５〜３０質量％が好ま
しい。パラジウムが少ないと耐候性が悪く、パラジウム
が多くなると導電性が低下する。The conductive layer of the present invention is a layer containing at least one or more conductive metals or conductive metal oxides, and the resistance of the conductive layer is 10 KΩ / □ (90 V applied voltage) or less, preferably 10 KΩ / □ (90 V applied voltage). To 1000 Ω / □, more preferably 10 Ω to 700 Ω / □. In creating these layers, a method of depositing a metal or metal oxide by vapor deposition, sputtering, plating, or the like,
There is a method of forming a conductive layer by applying conductive fine particles such as metal particles or metal oxide particles, and a method of forming a conductive layer by applying conductive fine particles is preferable from the viewpoint of improving productivity. Examples of the conductive metal fine particles include gold, silver, copper, aluminum, iron, nickel, palladium, platinum, and alloys thereof. Examples of the conductive metal oxide fine particles include indium oxide, tin oxide, antimony oxide, zinc oxide, aluminum oxide, silicon oxide, iron oxide, and composite oxides thereof. Among these, metal fine particles are preferable in the present invention, and silver is particularly preferable. Further, from the viewpoint of weather resistance, an alloy of silver and palladium is preferable, and the content of palladium is preferably 5 to 30% by mass. If the amount of palladium is small, the weather resistance is poor, and if the amount of palladium is large, the conductivity decreases.
【００２３】金属粒子または金属酸化物粒子の作成方法
としては、通常の低真空蒸発法による微粒子の作製方法
や金属塩の水溶液を還元する金属コロイド作製方法が挙
げられる。これらの金属粒子の平均粒径は１〜２００ｎ
ｍが好ましい。２００ｎｍを越える場合には、金属粒子
による光の吸収が大きくなり、このために粒子層の光透
過率が低下すると同時にヘーズが大きくなる。また、こ
れら金属微粒子の平均粒径が１ｎｍ未満の場合には微粒
子の分散が困難になること、微粒子層の表面抵抗が急激
に大きくなるため、本発明の目的を達成しうる程度の低
抵抗値を有する被膜を得ることができない。透明導電層
は実質的に金属微粒子のみからなることが好ましく、バ
インダー等の非導電性のものを含有しないことが導電性
の観点から好ましい。Examples of the method for producing metal particles or metal oxide particles include a method for producing fine particles by a usual low vacuum evaporation method and a method for producing a metal colloid for reducing an aqueous solution of a metal salt. The average particle size of these metal particles is 1 to 200 n.
m is preferred. If it exceeds 200 nm, the absorption of light by the metal particles becomes large, so that the light transmittance of the particle layer decreases and the haze increases. When the average particle size of these metal fine particles is less than 1 nm, dispersion of the fine particles becomes difficult, and the surface resistance of the fine particle layer increases rapidly, so that a low resistance value that can achieve the object of the present invention is obtained. Cannot be obtained. The transparent conductive layer is preferably substantially composed of only metal fine particles, and preferably does not contain a nonconductive material such as a binder from the viewpoint of conductivity.
【００２４】金属微粒子または金属酸化物粒子を含む透
明導電層は、水を主体とする溶剤に分散した塗料をハー
ドコート上に塗布して作製する。これらの水と混合する
溶剤としてはエチルアルコール、ｎ−プロピルアルコー
ル、ｉ−プロピルアルコール、１−ブチルアルコール、
２−ブチルアルコール、ｔ−ブチルアルコール、メチル
セルソルブ、ブチルセルソルブ等のアルコールが好まし
い。The transparent conductive layer containing metal fine particles or metal oxide particles is prepared by applying a coating material dispersed in a solvent mainly composed of water on a hard coat. As a solvent to be mixed with these waters, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, 1-butyl alcohol,
Alcohols such as 2-butyl alcohol, t-butyl alcohol, methyl cellosolve and butyl cellosolve are preferred.
【００２５】金属微粒子または金属酸化物粒子の塗布量
としては、５０〜１５０ｍｇ／ｍ2が好ましく、塗布量
が少ないと導電性が取れず、塗布量が多いと透過性が劣
る。The coating amount of the metal fine particles or metal oxide particles is preferably from 50 to 150 mg / m 2. If the coating amount is small, the conductivity cannot be obtained, and if the coating amount is large, the transmittance is poor.
【００２６】透明導電層の表面抵抗率は，ＴＣＯ（スエ
ーデン中央労働者協議会）ガイドラインをクリアーする
ため１０００Ω／□以下が必要であり、透過性は５０％
以上が好ましい。本発明の透明導電性フィルムは、その
透明性において表示機器を鑑賞する際に、暗くても使用
に耐えられる限り特に限定されないが、好ましくは可視
光の透過率で５０％以上が好ましく、５５％以上が更に
好ましく、６０％以上が特に好ましい。The surface resistivity of the transparent conductive layer must be 1000 Ω / □ or less in order to meet the TCO (Swedish Central Workers' Council) guidelines, and the transmittance is 50%.
The above is preferred. The transparent conductive film of the present invention is not particularly limited in terms of its transparency as long as it can withstand use even when it is dark when viewing a display device, but preferably has a visible light transmittance of 50% or more, preferably 55%. The above is more preferred, and the proportion is particularly preferably 60% or more.
【００２７】次に本発明の導電層用保護層について詳細
に記載する。本発明の導電層保護層に用いる素材として
はその誘電体力率が０．０１（周波数５０Ｈｚ）以上の
樹脂が好ましい。ここで、誘電体力率とは電気絶縁体の
特性項目であり、その値が大きい程絶縁破壊されやす
く、本発明では好ましい導電層用保護層の樹脂として用
いられる。この値については、化学便覧基礎編II、１１
７７頁〜１１７９頁（昭和５０年６月２０日、丸善株式
会社発行）に記載されている。本発明の誘電体力率が
０．０１以上を有する樹脂としては特に限定されない
が、例えばポリイソプレン（誘電体力率（以下同様）約
０．０３以上）、クロロスルホン化ポリエチレン（約
０．０３以上）、多硫化ゴム（約０．１）、フッ素ゴム
（約０．０３）、カゼイン（約０．０６）、フェノール
樹脂（約０．０５以上）、多硫化エポキシ樹脂（０．０
１以上）、尿素樹脂（約０．０３以上）、メラミン樹脂
（約０．０３）、ナイロン６（０．０１以上）、ナイロ
ン６６（０．０１以上）、ポリメタクリル酸メチル（約
０．０５）、アクリル酸エチル・エチレン共重合体
（０．０１以上）、ポリ塩化ビニル（０．０１以上）、
ポリ塩化ビニリデン（約０．０３以上）、ポリフッ化ビ
ニリデン（約０．０５）、（モノ−、ジ−、トリ−）ア
セチルセルロース（約０．０２）、ニトロセルロース
（約０．１）、などを挙げることができる。Next, the protective layer for a conductive layer of the present invention will be described in detail. As a material used for the conductive layer protective layer of the present invention, a resin having a dielectric power factor of 0.01 (frequency 50 Hz) or more is preferable. Here, the dielectric power factor is a characteristic item of the electrical insulator, and the larger the value, the more easily the dielectric breakdown occurs. In the present invention, the dielectric power factor is used as a preferable resin for the conductive layer protective layer. For this value, see the Chemical Handbook Basics II, 11
77 to 1179 (June 20, 1975, published by Maruzen Co., Ltd.). The resin having a dielectric power factor of 0.01 or more in the present invention is not particularly limited. For example, polyisoprene (dielectric power factor (the same applies hereinafter) of about 0.03 or more), chlorosulfonated polyethylene (about 0.03 or more) , Polysulfide rubber (about 0.1), fluorine rubber (about 0.03), casein (about 0.06), phenol resin (about 0.05 or more), polysulfide epoxy resin (0.0
1 or more), urea resin (about 0.03 or more), melamine resin (about 0.03), nylon 6 (0.01 or more), nylon 66 (0.01 or more), polymethyl methacrylate (about 0.05 ), Ethyl acrylate / ethylene copolymer (0.01 or more), polyvinyl chloride (0.01 or more),
Polyvinylidene chloride (about 0.03 or more), polyvinylidene fluoride (about 0.05), (mono-, di-, tri-) acetylcellulose (about 0.02), nitrocellulose (about 0.1), etc. Can be mentioned.
【００２８】これらの中でも好ましく用いられる樹脂と
しては、フッ素ゴム、フェノール樹脂、尿素樹脂、メラ
ミン樹脂、ナイロン６、ナイロン６６、ポリメタクリル
酸メチル、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリ
フッ化ビニリデン、ポリビニルホルマール、（モノ−、
ジ−、トリ−）アセチルセルロース、ニトロセルロー
ス、更に活性エネルギー線（紫外線、電子線、ガンマ線
など）硬化樹脂などをあげることができる。その中でも
本発明では、ポリオールの多官能ビニル誘導体（メタ
（アクリレート）ポリエステルなど）から作成された活
性エネルギー線で重合された樹脂が、表面硬度、機械強
度の具備ができることから、好ましい。好ましいものと
しては、トリメチロールプロパントリ（メタ）アクリレ
ート、ペンタエリスリトールテトラ（メタ）アクリレー
トやジペンタエリスリトールヘキサ（メタ）アクリレー
ト等が挙げられる。これらの活性エネルギー線硬化樹脂
には必要に応じて重合開始剤を添加することが好まし
い。Among these resins, preferred resins include fluoro rubber, phenol resin, urea resin, melamine resin, nylon 6, nylon 66, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, and polyvinyl formal. , (Mono,
Examples thereof include di-, tri-) acetylcellulose, nitrocellulose, and resins curable with active energy rays (ultraviolet rays, electron rays, gamma rays, etc.). Among them, in the present invention, a resin polymerized with an active energy ray formed from a polyfunctional vinyl derivative of a polyol (such as a meta (acrylate) polyester) is preferable because it can have surface hardness and mechanical strength. Preferred examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate. It is preferable to add a polymerization initiator to these active energy ray-curable resins as needed.
【００２９】本発明の導電層用保護層の膜厚は、保護層
表面から導電性が取れればその厚さは限定されないが、
好ましくは１０〜２０００ｎｍであり、より好ましくは
２０〜１０００ｎｍであり、さらには２０〜５００ｎｍ
であり、さらには１０〜５００ｎｍであり、特に３０〜
３００ｎｍである。導電層用保護層の上からの表面抵抗
は１０ＫΩ／□以下（９０Ｖ印加電圧）であることが好
ましいく、より好ましくは５ＫΩ／□以下であり、さら
には２ＫΩ以下であり、１ＫΩ／□以下であることが特
に好ましい（好ましくは１０Ω／□以上）。特に導電層
保護層膜厚が３００ｎｍの場合は、印加電圧が１０Ｖで
も１ｋΩ以下の表面抵抗を得ることができる。本発明の
保護膜を形成した後の表面抵抗は形成前の表面抵抗に対
して０．５〜１．５の比で有ることが好ましい。保護膜
を形成することにより導電層の金属、金属粒子、金属酸
化物あるいは金属酸化物粒子の固定がしっかりでき、表
面抵抗が低下するため保護膜塗設前後の抵抗率の変化が
小さくなる。保護膜の厚みが厚くなると本来絶縁性の化
合物であるため、表面抵抗は大きくなり皮膜塗設前後の
抵抗の比は大きくなってしまう。本発明の導電層用保護
膜は、屈折率を制御することにより、反射防止層として
の機能も発揮することが可能である。The thickness of the protective layer for a conductive layer of the present invention is not limited as long as conductivity is obtained from the surface of the protective layer.
It is preferably from 10 to 2000 nm, more preferably from 20 to 1000 nm, furthermore from 20 to 500 nm.
And more preferably from 10 to 500 nm, especially from 30 to 500 nm.
300 nm. The surface resistance from above the conductive layer protective layer is preferably 10 KΩ / □ or less (applied voltage of 90 V), more preferably 5 KΩ / □ or less, further 2 KΩ or less, and 1 KΩ / □ or less. It is particularly preferred (preferably 10 Ω / □ or more). In particular, when the thickness of the conductive layer protective layer is 300 nm, a surface resistance of 1 kΩ or less can be obtained even when the applied voltage is 10 V. The surface resistance after forming the protective film of the present invention is preferably 0.5 to 1.5 with respect to the surface resistance before forming. By forming the protective film, the metal, metal particles, metal oxide or metal oxide particles of the conductive layer can be firmly fixed, and the surface resistance is reduced, so that the change in resistivity before and after the application of the protective film is reduced. When the thickness of the protective film increases, the surface resistance increases because the compound is originally an insulating compound, and the ratio of resistance before and after coating the film increases. The protective film for a conductive layer of the present invention can also function as an anti-reflection layer by controlling the refractive index.
【００３０】導電層用保護層は、必要に応じて金属酸化
物を添加することも可能である。具体的には、シリカ、
アルミナ、ジルコニア、チタニア等の酸化物を挙げるこ
とができる。こられの酸化物は、膜強度を上げるため、
屈折率を変化させるために添加される。また、保護膜の
更に外側にオーバーコート層を設けることも可能であ
る。オーバーコート層を生成する具体例としては、公知
のフッ素を含有する低表面エネルギーの化合物が好まし
く、具体的にはフッ化炭化水素基を含有するシリコン化
合物、フッ化炭化水素基含有ポリマーが挙げられる。こ
れらの化合物は、オーバーコート層に設けるだけでな
く、保護膜中に添加することもできる。特に、添加後表
面近傍に配向し表面改質できる添加物が好ましい。The protective layer for a conductive layer may be added with a metal oxide as needed. Specifically, silica,
Oxides such as alumina, zirconia, and titania can be given. These oxides increase the film strength,
It is added to change the refractive index. Further, an overcoat layer can be provided further outside the protective film. As a specific example of forming the overcoat layer, a known fluorine-containing low surface energy compound is preferable, and specific examples thereof include a fluorocarbon-containing silicon compound and a fluorocarbon-containing polymer. . These compounds can be added not only to the overcoat layer but also to the protective film. In particular, additives that can be oriented near the surface after addition and that can modify the surface are preferred.
【００３１】本発明の透明導電層の屈折率と異なる屈折
率を有する少なくとも１層の透明性導電層保護層は、屈
折率が１．７０以下の層である。導電層保護層の最外層
が防汚機能を有する形態であってもよく、この時の導電
層保護層の屈折率は、１．３０以上、１．７０以下であ
ることが好ましい。より好ましくは、１．３５以上、
１．６０以下である。屈折率が１．７０を超えると反射
率が大きくなり反射防止の効果が小さくなる。また１．
３０未満になると、透明導電層との界面での反射が大き
くなる。At least one transparent conductive layer protective layer having a refractive index different from that of the transparent conductive layer of the present invention is a layer having a refractive index of 1.70 or less. The outermost layer of the conductive layer protective layer may have an antifouling function, and the refractive index of the conductive layer protective layer at this time is preferably 1.30 or more and 1.70 or less. More preferably, 1.35 or more,
1.60 or less. If the refractive index exceeds 1.70, the reflectance increases and the antireflection effect decreases. Also 1.
If it is less than 30, reflection at the interface with the transparent conductive layer will increase.
【００３２】屈折率が１．３０以上、１．７０以下の範
囲の物質としては、例えばポリエステル樹脂、アクリル
樹脂、エポキシ樹脂、メラミン樹脂、ポリウレタン樹
脂、ポリビニルブチラール樹脂、紫外線硬化樹脂などの
有機系合成樹脂（更に具体的には、ポリマーハンドブッ
ク（四版）、VI−５７１から（１９９９）、ＪＯＨＮＷ
ＩＬＥＹ ＆ ＳＯＮ、ＩＮＣ．に記載）、ケイ素など
の金属アルコキシドの加水分解物、またはシリコーンモ
ノマー、シリコーンオリゴマーなどの有機・無機系化合
物等を挙げることができる。特に好ましくは、ペンタエ
リスリトールテトラ（メタ）アクリレートやジペンタエ
リスリトールヘキサ（メタ）アクリレート等の活性エネ
ルギー線硬化性樹脂あるいはこれらに微粒子のシリカや
アルミナ等を添加したものが表面硬度も上げることで好
ましい。Examples of the substance having a refractive index of 1.30 or more and 1.70 or less include organic synthetic resins such as polyester resin, acrylic resin, epoxy resin, melamine resin, polyurethane resin, polyvinyl butyral resin, and ultraviolet curing resin. Resins (more specifically, Polymer Handbook (4th edition), VI-571 to (1999), JOHNW
ILEY & SON, INC. ), Hydrolysates of metal alkoxides such as silicon, and organic / inorganic compounds such as silicone monomers and silicone oligomers. Particularly preferably, active energy ray-curable resins such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate, or those obtained by adding fine particles of silica or alumina to these resins are preferable in terms of increasing the surface hardness.
【００３３】導電層保護層厚は反射防止の観点からは、
５０〜１５０ｎｍが好ましく、反射率低下に効果がある
厚みに設定することが好ましい。 導電層保護層の屈折
率と厚み（ｎｍ）の積が、１００〜２００の範囲に入る
ことが好ましい。The thickness of the conductive layer protective layer is, from the viewpoint of antireflection,
The thickness is preferably 50 to 150 nm, and is preferably set to a thickness that is effective in reducing the reflectance. The product of the refractive index and the thickness (nm) of the conductive layer protective layer preferably falls within the range of 100 to 200.
【００３４】透明導電性層の屈折率と異なる導電層保護
層の防汚性を向上させるために、フッ素および／または
ケイ素を含有する化合物を含有させることができる。こ
れらの化合物としては、公知のフッ素化合物やケイ素化
合物、あるいはフッ素とケイ素含有部を有するブロック
を有する化合物が挙げられ、さらに樹脂あるいは金属酸
化物等と相溶性の良いセグメントとフッ素あるいはケイ
素を含有するセグメントとを有する化合物が好ましく、
透明導電性層の屈折率の異なる透明導電層保護層への添
加することで、表面にフッ素あるいはケイ素が偏在させ
ることができる。In order to improve the antifouling property of the conductive protective layer different from the refractive index of the transparent conductive layer, a compound containing fluorine and / or silicon can be contained. Examples of these compounds include known fluorine compounds and silicon compounds, or compounds having a block having a fluorine and silicon-containing portion, and further contain a segment having good compatibility with a resin or a metal oxide and fluorine or silicon. And a compound having a segment,
Fluorine or silicon can be unevenly distributed on the surface by adding the transparent conductive layer to the transparent conductive layer protective layer having a different refractive index.
【００３５】これらの具体的な化合物としては、フッ素
あるいはケイ素を含有するモノマーと他の親水性あるい
は親油性のモノマーとのブロック共重合体、あるいはグ
ラフト共重合体があげられる。フッ素含有モノマーとし
てはヘキサフルオロイソプロピルアクリレート、ヘプタ
デカフルオロデシルアクリレート、パーフルオロアルキ
ルスルホンアミドエチルアクリレート、パーフルオロア
ルキルアミドエチルアクリレート等に代表されるパーフ
ルオロアルキル基含有（メタ）アクリル酸エステルがあ
げられる。ケイ素含有モノマーとしてはポリジメチルシ
ロキサンと（メタ）アクリル酸等の反応によるシロキサ
ン基を有するモノマーがあげられる。親水性あるいは親
油性のモノマーとしては、メチルアクリレート等の（メ
タ）アクリル酸エステル、末端に水酸基含有ポリエステ
ルと（メタ）アクリル酸のエステル、ヒドロキシエチル
（メタ）アクリレート、ポリエチレングリコールの（メ
タ）アクリル酸エステル等があげられる。市販の化合物
としては、パーフルオロアルキル鎖のミクロドメイン構
造を有するアクリル系オリゴマーのデフェンサＭＣＦ−
３００、３１２、３２３等、パーフルオロアルキル基・
親油性基含有オリゴマーのメガファックＦ−１７０，Ｆ
−１７３，Ｆ−１７５等、パーフルオロアルキル基・親
水性基含有オリゴマーのメガファックＦ−１７１等（大
日本インキ化学(株)製）や、表面移行性に優れたセグメ
ントと樹脂に相溶するセグメントよりなるビニルモノマ
ーのブロックポリマーであるフッ化アルキル系のモディ
パーＦ−２００、２２０、６００、８２０等、シリコン
系のモディパーＦＳ−７００、７１０等（日本油脂(株)
製）があげられる。Specific examples of these compounds include a block copolymer or a graft copolymer of a monomer containing fluorine or silicon and another hydrophilic or lipophilic monomer. Examples of the fluorine-containing monomer include perfluoroalkyl group-containing (meth) acrylates represented by hexafluoroisopropyl acrylate, heptadecafluorodecyl acrylate, perfluoroalkylsulfonamidoethyl acrylate, perfluoroalkylamidoethyl acrylate, and the like. Examples of the silicon-containing monomer include a monomer having a siloxane group resulting from a reaction between polydimethylsiloxane and (meth) acrylic acid. Examples of hydrophilic or lipophilic monomers include (meth) acrylic acid esters such as methyl acrylate, esters of hydroxyl group-containing polyester and (meth) acrylic acid at the terminal, hydroxyethyl (meth) acrylate, and (meth) acrylic acid of polyethylene glycol. Esters and the like. Commercially available compounds include acrylic oligomer defencer MCF- having a microdomain structure of a perfluoroalkyl chain.
300, 312, 323, etc., perfluoroalkyl group
Lipophilic group-containing oligomer Megafac F-170, F
-173, F-175 etc., compatible with perfluoroalkyl group / hydrophilic group-containing oligomers such as Megafac F-171 (manufactured by Dainippon Ink & Chemicals, Inc.) and segments with excellent surface migration properties and resins Alkyl fluoride-based Modiper F-200, 220, 600, 820, etc., which are block copolymers of vinyl monomers composed of segments, Silicon-based Modiper FS-700, 710, etc. (Nippon Oil & Fats Co., Ltd.)
Made).
【００３６】透明導電性層の屈折率と異なる透明導電層
保護層へのこれらの化合物の添加は、表面への偏在によ
り、例えば接触角が９０゜以上、好ましくは１００゜以
上になる量であればよく、具体的な添加量は、導電層保
護層の１〜５０質量％、更に好ましくは５〜３０質量％
が好ましい。量が少ないと表面の防汚性が劣り、５０質
量％以上では膜強度が低下し、耐傷性が劣る。The addition of these compounds to the protective layer of the transparent conductive layer having a refractive index different from that of the transparent conductive layer may be, for example, in an amount such that the contact angle is 90 ° or more, preferably 100 ° or more due to uneven distribution on the surface. The specific addition amount may be 1 to 50% by mass, more preferably 5 to 30% by mass of the conductive layer protective layer.
Is preferred. If the amount is small, the antifouling property of the surface is poor, and if it is 50% by mass or more, the film strength is reduced and the scratch resistance is poor.
【００３７】最外層の防汚層に用いる化合物は、屈折率
が１．３０以上、１．５０以下の化合物が好ましく、フ
ッ素原子を含有した低表面エネルギー性の化合物が好ま
しく、具体的には、特開昭５７−３４５２６号、特開平
２−１９８０１号、特開平３−１７９０１号公報等に記
載のフッ化炭化水素基を含有するシリコン化合物、フッ
化炭化水素基含有ポリマー等が挙げられる。The compound used for the outermost antifouling layer is preferably a compound having a refractive index of 1.30 or more and 1.50 or less, and is preferably a compound having a low surface energy containing a fluorine atom. Examples of the compound include a fluorocarbon group-containing silicon compound and a fluorohydrocarbon group-containing polymer described in JP-A-57-34526, JP-A-2-19801, and JP-A-3-17901.
【００３８】本発明の積層フイルムの作製は、透明基材
フイルム上に各層の塗料をディッピング法、スピナー
法、スプレー法、ロールコーター法、ブレード法、ワイ
ヤーバー法等の公知の薄膜塗布方法で各層を順次形成、
乾燥して作製することができる。各薄膜の作成方法とし
てはワイヤーバーによる方法が好ましい。The laminated film of the present invention is prepared by coating the coating material of each layer on a transparent base film by a known thin film coating method such as dipping, spinner, spraying, roll coater, blade, or wire bar. Sequentially formed,
It can be made by drying. As a method for forming each thin film, a method using a wire bar is preferable.
【００３９】[0039]
【実施例】以下、実施例によって本発明を更に具体的に
説明する。 （１）塗料の調製： ハードコート層塗布液の調整： （シリカ微粒子の表面処理）平均粒径が１５ｎｍのシリ
カ微粒子の４０質量％メタノール分散液２００ｇを、撹
拌装置、温度計および還流冷却管を装着した５００ｍｌ
のガラス製三口フラスコに入れた。ここに２Ｎ塩酸０．
２ｇを加え、窒素気流下で６０℃に昇温した後、３−メ
タクリロイルオキシプロピルトリメトキシシラン１０ｇ
を添加し、４時間撹拌を続け、シリカ微粒子を表面処理
した。 （ハードコート層用塗布液の調製）表面処理したシリカ
微粒子の４３質量％メタノール分散液１１６ｇに、メタ
ノール９７ｇ、イソプロパノール１６３ｇおよび酢酸ブ
チル１６３ｇを加えた。混合液に、ジペンタエリスリト
ールペンタアクリレートとジペンタエリスリトールヘキ
サアクリレートの混合物（ＤＰＨＡ、日本化薬（株）
製）２００ｇを加えて溶解した。得られた溶液に、光重
合開始剤（イルガキュア１８４、チバガイギー社製）
７．５ｇを加えて溶解した。混合物を３０分間撹拌した
後、孔径１μｍのポリプロピレン製フィルターで濾過し
てハードコート層用塗布液を調製した。The present invention will be described more specifically with reference to the following examples. (1) Preparation of Paint: Preparation of Coating Solution for Hard Coat Layer: (Surface Treatment of Silica Fine Particles) 200 g of 40% by mass methanol dispersion of silica fine particles having an average particle diameter of 15 nm was placed in a stirrer, a thermometer and a reflux condenser. 500ml attached
In a three-necked glass flask. Here, 2N hydrochloric acid was added.
After adding 2 g and heating to 60 ° C. under a nitrogen stream, 10 g of 3-methacryloyloxypropyltrimethoxysilane was added.
Was added and stirring was continued for 4 hours to surface-treat the silica fine particles. (Preparation of Coating Solution for Hard Coat Layer) 97 g of methanol, 163 g of isopropanol and 163 g of butyl acetate were added to 116 g of a 43% by mass methanol dispersion of surface-treated silica fine particles. A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.)
200 g) and dissolved. A photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy) is added to the obtained solution.
7.5 g was added and dissolved. After stirring the mixture for 30 minutes, the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a hard coat layer.
【００４０】銀コロイド塗布液の調製： （銀コロイド分散液の調整）３０質量％硫酸鉄（II）Ｆ
ｅＳＯ4・７Ｈ2Ｏ、４０質量％のクエン酸を調製、混合
し、２０℃に保持、攪拌しながらこれに１０質量％の硝
酸銀と硝酸パラジウム（モル比９／１に混合したもの）
溶液を２００ｍｌ／ｍｉｎの速度で添加混合し、その後
生成した遠心分離により水洗を繰り返し、最終的に３質
量％になるように純水を加え、銀パラジウムコロイド分
散液を調製した。得られた本発明の導電性粒子である銀
コロイド粒子の粒径は、ＴＥＭで約９〜１２ｎｍであっ
た。融合結合高周波プラズマ（ＩＣＰ）による測定の結
果、銀とパラジウムの比は９／１の仕込み比と同一であ
った。 （銀コロイド塗布液の調整）前記銀コロイド分散液１０
０ｇにｉ−プロピルアルコールを加え、超音波分散し孔
径１μｍのポリプロピレン製フィルターで濾過して塗布
液を調整した。Preparation of silver colloid coating liquid: (Preparation of silver colloid dispersion liquid) 30% by mass of iron (II) sulfate F
eSO 4 .7H 2 O, 40% by mass of citric acid were prepared and mixed, kept at 20 ° C., and stirred with 10% by mass of silver nitrate and palladium nitrate (mixed at a molar ratio of 9/1).
The solution was added and mixed at a rate of 200 ml / min, and thereafter, washing with water was repeated by centrifugation, and pure water was finally added to a concentration of 3% by mass to prepare a silver-palladium colloidal dispersion. The particle size of the obtained silver colloid particles, which are the conductive particles of the present invention, was about 9 to 12 nm by TEM. As a result of measurement by fusion bonding high frequency plasma (ICP), the ratio of silver to palladium was the same as the charging ratio of 9/1. (Preparation of Silver Colloid Coating Solution) The above silver colloid dispersion 10
To 0 g, i-propyl alcohol was added, ultrasonically dispersed, and filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution.
【００４１】導電層保護層用塗布液の調整 ジペンタエリスリトールペンタアクリレートとジペンタ
エリスリトールヘキサアクリレートの混合物（ＤＰＨ
Ａ、日本化薬（株）製）２ｇと光重合開始剤（イルガキ
ュア９０７、チバガイギー社製）８０ｍｇおよび光増感
剤（カヤキュアーＥＴＸ、日本化薬（株）製）３０ｍｇ
をメチルイソブチルケトン／２−ブタノール／メタノー
ルの混合溶液（２／２／１質量比）溶解した。溶解濃度
は所定の厚みになるように調整し、混合物を３０分間撹
拌した後、孔径１μｍのポリプロピレン製フィルターで
濾過して導電層保護層用塗布液を調製した．Preparation of Coating Solution for Conductive Layer Protective Layer A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPH
A, 2 g of Nippon Kayaku Co., Ltd., 80 mg of photopolymerization initiator (Irgacure 907, Ciba-Geigy) and 30 mg of photosensitizer (Kayacure ETX, Nippon Kayaku Co., Ltd.)
Was dissolved in a mixed solution of methyl isobutyl ketone / 2-butanol / methanol (2/2/1 mass ratio). The dissolution concentration was adjusted to a predetermined thickness, the mixture was stirred for 30 minutes, and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a conductive layer protective layer.
【００４２】防汚層用塗布液の調製 熱架橋性含フッ素ポリマー（ＪＮ−７２１４、ＪＳＲ
（株）製）にイソプロピルアルコールを加えて、０．０
６質量％の粗分散液を調製した。粗分散液を、更に超音
波分散し、防汚層用塗布液を調製した。Preparation of Coating Solution for Antifouling Layer Thermally crosslinkable fluorine-containing polymer (JN-7214, JSR
Isopropyl alcohol)
A 6% by mass crude dispersion was prepared. The coarse dispersion was further ultrasonically dispersed to prepare a coating solution for an antifouling layer.
【００４３】防汚性を有する導電層保護層用の塗布液
(a)の調整 反応性フッ素ポリマー（ＪＳＲ（株）製ＪＮ−７２１９
屈折率１．４０）の１０質量％メチルイソブチルケト
ン溶液を、ｔ−ブチルアルコールとメチルイソブチルケ
トンの等質量混合溶媒で希釈し、反応性フッ素ポリマー
の２質量％溶液を調整した。Coating solution for conductive layer protective layer having antifouling property
Preparation of (a) Reactive fluoropolymer (JN-7219 manufactured by JSR Corporation)
A 10% by mass methyl isobutyl ketone solution having a refractive index of 1.40) was diluted with an equal mass mixed solvent of t-butyl alcohol and methyl isobutyl ketone to prepare a 2% by mass solution of a reactive fluoropolymer.
【００４４】防汚性を有する導電層保護層用の塗布液
(b)の調整 の導電層保護層用塗布液と同様に、ジペンタエリスリ
トールペンタアクリレートとジペンタエリスリトールヘ
キサアクリレートの混合物（ＤＰＨＡ、日本化薬（株）
製）２ｇと光重合開始剤（イルガキュア９０７、チバガ
イギー社製）８０ｍｇおよび光増感剤（カヤキュアーＥ
ＴＸ、日本化薬（株）製）３０ｍｇに加えて、パーフル
オロアルキル基含有アクリル酸エステル０．４ｇ（メガ
ファックＦ−５３１Ａ、大日本インキ化学工業（株）
製）をメチルイソブチルケトン／２−ブタノール／メタ
ノールの混合溶液（２／２／１質量比）溶解した。溶解
濃度は所定の厚みになるように調整し、混合物を３０分
間撹拌した後、孔径１μｍのポリプロピレン製フィルタ
ーで濾過して導電層保護層用塗布液を調製した。Coating solution for conductive layer protective layer having antifouling property
In the same manner as in (b), the mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.)
2g), 80 mg of a photopolymerization initiator (Irgacure 907, Ciba Geigy) and a photosensitizer (Kayacure E)
TX, Nippon Kayaku Co., Ltd.) 30 mg, and a perfluoroalkyl group-containing acrylate 0.4 g (MegaFac F-531A, Dainippon Ink and Chemicals, Inc.)
Was dissolved in a mixed solution of methyl isobutyl ketone / 2-butanol / methanol (2/2/1 mass ratio). The dissolution concentration was adjusted to a predetermined thickness, the mixture was stirred for 30 minutes, and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a conductive layer protective layer.
【００４５】実施例１ 低反射導電性積層フイルムの作製：１７５μｍのポリエ
チレンテレフタレートフイルムにワイヤーバーを用いて
ハードコート塗布液を層厚８μｍになるように塗布・
乾燥し、紫外線照射しハードコート層を作製した。コロ
ナ処理を施した後、上記銀コロイド塗布液をワイヤー
バーで塗布量が７０ｍｇ／ｍ2になるように塗布し、４
０℃で乾燥した。この導電層塗布面に、ポンプで送液し
た純水をスプレーでかけ、エアーナイフで過剰の水を除
去した後、１２０℃５分乾燥した。次いで、導電層保護
層用塗布液を膜厚９０ｎｍになるように塗布・乾燥
し、紫外線照射した。さらに、防汚層用塗布液を同様
に＃３のワイヤーバーで塗布し１２０℃で乾燥・熱処理
を行った。尚、導電層保護層の屈折率は１．５２、防汚
層の厚みは３ｎｍで屈折率は１．４２５であった。Example 1 Preparation of a low-reflection conductive laminated film: A hard coat coating solution was applied to a 175 μm polyethylene terephthalate film using a wire bar so as to have a layer thickness of 8 μm.
It was dried and irradiated with ultraviolet rays to form a hard coat layer. After the corona treatment, the above silver colloid coating solution was coated with a wire bar so that the coating amount was 70 mg / m 2 ,
Dried at 0 ° C. Pure water sent by a pump was sprayed on the conductive layer application surface, excess water was removed with an air knife, and then dried at 120 ° C. for 5 minutes. Next, a coating liquid for a conductive layer protective layer was applied and dried so as to have a thickness of 90 nm, and irradiated with ultraviolet rays. Further, the coating solution for the antifouling layer was similarly applied with a # 3 wire bar, and dried and heat-treated at 120 ° C. Incidentally, the refractive index of the conductive layer protective layer was 1.52, the thickness of the antifouling layer was 3 nm, and the refractive index was 1.425.
【００４６】比較例１〜３ 実施例と同様に、ハードコートを積層しない積層フイル
ム（比較例１）、導電層保護層の無い積層フイルム（比
較例２）、防汚層の無い積層フイルム（比較例３）をそ
れぞれ作製した。作製した積層フイルムの特性を測定し
た結果を表１に示す。Comparative Examples 1 to 3 As in the examples, a laminated film without a hard coat (Comparative Example 1), a laminated film without a conductive layer protective layer (Comparative Example 2), and a laminated film without an antifouling layer (Comparative Example) Example 3) was produced. Table 1 shows the results of measuring the characteristics of the produced laminated film.
【００４７】[0047]
【表１】 [Table 1]
【００４８】実施例２ 実施例１と同様に、ポリエチレンテレフタレートフィル
ムにハードコート層、銀コロイド層を設け、その後上記
の塗布液をワイヤーバーで乾燥膜厚が９６ｎｍとなる
ように塗布し、１２０℃で乾燥・熱硬化処理を施した。Example 2 In the same manner as in Example 1, a hard coat layer and a silver colloid layer were provided on a polyethylene terephthalate film, and then the above coating solution was applied using a wire bar to a dry film thickness of 96 nm. For drying and heat curing.
【００４９】実施例３ 実施例１と同様に、上記、の導電層保護層用塗布
液、防汚層塗布液の変わりにの塗布液だけを塗布し、
実施例１と同様紫外線照射を行った。Example 3 In the same manner as in Example 1, only the coating liquid for the conductive layer protective layer and the antifouling layer coating liquid described above was applied.
Ultraviolet irradiation was performed in the same manner as in Example 1.
【００５０】比較例４および５ 実施例２と同様にして、ハードコートを積層しない積層
フィルム（比較例４）、導電層保護層のない積層フィル
ム（比較例５）をそれぞれ作成した。Comparative Examples 4 and 5 In the same manner as in Example 2, a laminated film having no hard coat (Comparative Example 4) and a laminated film having no conductive layer protective layer (Comparative Example 5) were produced.
【００５１】実施例２、３、比較例４、５を実施例１と
同様の測定を行い表２の結果を得た。In Examples 2 and 3, and Comparative Examples 4 and 5, the same measurements as in Example 1 were performed, and the results shown in Table 2 were obtained.
【００５２】[0052]
【表２】 [Table 2]
【００５３】実施例４から１１、比較例６および７ 実施例１と同様に、の導電性保護層の膜厚を変化させ
る試料、及び表３に記載の樹脂を用いて、同様の操作で
透明導電性フイルムを作製した。Examples 4 to 11, Comparative Examples 6 and 7 In the same manner as in Example 1, using the sample in which the film thickness of the conductive protective layer was changed and the resin shown in Table 3, the transparent operation was performed in the same manner. A conductive film was produced.
【００５４】[0054]
【表３】 [Table 3]
【００５５】表１において、各々の測定は実施例及び比
較例の試料を用い、以下に示す方法で行った。 （１）表面抵抗率 フイルムを温度２５℃、相対湿度６０％の条件で２時間
調湿後、４端子法表面抵抗率計（三菱化学(株)製「ロレ
スタＦＰ」）による測定値。 （２）透過率 島津製作所(株)製分光光度計（ＵＶ−２４００ＰＣ）を
用いた、４００〜８００ｎｍの波長の平均透過率。 （３）平均反射率 分光光度計（日本分光(株)製）を用いた、４５０〜６５
０ｎｍの波長領域における入射光５゜における正反射の
平均反射率。 （４）鉛筆硬度 フイルムを温度２５℃、相対湿度６０％の条件で２時間
調湿後、ＪＩＳ−Ｓ−６００６が規定する試験用鉛筆を
用いて、ＪＩＳ−Ｋ−５４００が規定する鉛筆硬度評価
方法による硬度。 （５）防汚性 フイルム表面に指紋を付着させ、東レ(株)製トレシーを
用いてふき取った状態の評価（○は指紋が完全にふき取
れた状態、×は指紋の一部がふき取れずに残った状
態）。 （６）耐傷性 ２００ｇ／ｃｍ2の荷重で、＃００００のスチールウー
ルでフイルム表面を６０往復擦った後の傷の状態（Ａ：
傷は認められなった。Ｂ：傷が少し認められた。Ｃ：傷
が相当認められた。Ｄ：傷が著しく認められた。）。In Table 1, each measurement was performed using the samples of Examples and Comparative Examples according to the following method. (1) Surface Resistivity After a film was conditioned for 2 hours at a temperature of 25 ° C. and a relative humidity of 60%, a value measured by a four-terminal method surface resistivity meter (“Loresta FP” manufactured by Mitsubishi Chemical Corporation). (2) Transmittance Average transmittance at a wavelength of 400 to 800 nm using a spectrophotometer (UV-2400PC) manufactured by Shimadzu Corporation. (3) Average reflectance 450-65 using a spectrophotometer (manufactured by JASCO Corporation)
Average reflectance of specular reflection of incident light 5 ° in a wavelength region of 0 nm. (4) Pencil hardness After conditioning the film at a temperature of 25 ° C. and a relative humidity of 60% for 2 hours, using a test pencil specified by JIS-S-6006, a pencil hardness evaluation specified by JIS-K-5400. Hardness by way. (5) Antifouling property Evaluation of the state where a fingerprint was adhered to the film surface and wiped off using Toray's Toraysee (○ indicates that the fingerprint was completely wiped off, and × indicates that the fingerprint was partially wiped off. Left in the state). (6) Scratch resistance Scratch state after rubbing the film surface 60 times with # 0000 steel wool under a load of 200 g / cm 2 (A:
No scars were found. B: Some scratches were observed. C: Scratches were considerably recognized. D: Scratches were remarkably observed. ).
【００５６】実施例１のフイルム（１０×１０ｃｍ2）
の対角表面に銅箔を導電性テープで貼りつけ、フイルム
から引き出した銅箔間の抵抗をテスターで測定したとこ
ろ、抵抗は９００Ωを示し、優れた導電性を有すること
を確認した。比較例７のフイルムで同様の測定を行った
が、抵抗は１０ＭΩ以上であった。The film of Example 1 (10 × 10 cm 2 )
The copper foil was stuck on the diagonal surface of the film with a conductive tape, and the resistance between the copper foils pulled out from the film was measured with a tester. The resistance was 900Ω, confirming that the film had excellent conductivity. The same measurement was performed on the film of Comparative Example 7, but the resistance was 10 MΩ or more.
【００５７】[0057]
【発明の効果】本発明の低反射透明導電性積層フイルム
は、ハードコート層、透明導電性層、防汚性を有する保
護層からなる簡単な層構成により、優れた機械特性帯電
防止性および電磁波遮蔽性に優れていると共に、表面反
射が防止された機能を有しているフイルムである。さら
に、表面抵抗が小さく、且つ導電層保護層の誘電力率が
大きいため、、表面から直接アースすることができる。
従って、陰極線管やプラズマディスプレー等の表面に積
層し、簡単な方法でアースがとれることにより、電磁波
遮蔽、反射防止、表面の汚れ防止機能を付加できる低反
射透明導電性積層フイルムを供与することができる。The low-reflection transparent conductive laminated film of the present invention has excellent mechanical properties, antistatic properties and electromagnetic waves due to a simple layer structure comprising a hard coat layer, a transparent conductive layer, and a protective layer having antifouling properties. This film has excellent shielding properties and a function of preventing surface reflection. Furthermore, since the surface resistance is small and the dielectric power factor of the conductive layer protective layer is large, it can be directly grounded from the surface.
Therefore, it is possible to provide a low-reflection transparent conductive laminated film that can be laminated on the surface of a cathode ray tube, a plasma display, or the like and provided with a function of shielding electromagnetic waves, preventing reflection, and preventing surface contamination by being grounded in a simple manner. it can.
【図１】本発明の低反射透明導電性積層フイルムの構成
の模式図である。FIG. 1 is a schematic view of a configuration of a low-reflection transparent conductive laminated film of the present invention.
１ 透明基材 ２ ハードコート層 ３ 透明導電層 ４ 導電層保護層 ５ 防汚層 DESCRIPTION OF SYMBOLS 1 Transparent base material 2 Hard coat layer 3 Transparent conductive layer 4 Conductive layer protective layer 5 Antifouling layer
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｇ０２Ｂ 1/10 Ｇ０２Ｂ 1/10 Ａ Ｈ０５Ｋ 9/00 Ｚ (72)発明者 畑山 剣一郎 神奈川県南足柄市中沼210番地 富士写真 フイルム株式会社内 (72)発明者 本 隆裕 神奈川県南足柄市中沼210番地 富士写真 フイルム株式会社内 Ｆターム(参考） 2K009 AA02 AA15 BB11 BB24 CC03 CC09 CC14 CC26 CC42 CC47 DD03 DD05 DD17 EE03 EE05 4F100 AA20 AB01C AB17C AB24C AB25C AB31C AH05D AK01A AK17 AK25 AK42 AT00A BA04 BA07 BA10D CC00B DE01C EH46 EJ08 EJ54 EJ55 GB41 JD06 JG01 JG01C JG03 JG04C JG05D JK12B JL06D JN01 JN01A JN01C JN06D JN18D YY00C YY00D 5E321 BB23 BB32 BB44 GG01 GG05 GH01 5G307 FA02 FB01 FB02 FC08 FC10──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) G02B 1/10 G02B 1/10 A H05K 9/00 Z (72) Inventor Kenichiro Hatayama Nakanuma, Minamiashigara-shi, Kanagawa 210 Fuji Photo Film Co., Ltd. (72) The inventor Takahiro Moto 210 Nakanuma, Minamiashigara, Kanagawa Prefecture F Photo Film Co., Ltd. F-term (reference) 2K009 AA02 AA15 BB11 BB24 CC03 CC09 CC14 CC26 CC42 CC47 DD03 DD05 DD17 EE03 EE05 4F100 AA20 AB01C AB17C AB24C AB25C AB31C AH05D AK01A AK17 AK25 AK42 AT00A BA04 BA07 BA10D CC00B DE01C EH46 EJ08 EJ54 EJ55 GB41 JD06 JG01 JG01C JG03 JG04C JG05D JK12B JL06D JN01 JN01A JN01C JN06D JN18D YY00C YY00D 5E321 BB23 BB32 BB44 GG01 GG05 GH01 5G307 FA02 FB01 FB02 FC08 FC10
Claims (14)
とも１種の金属からなる微粒子を有する透明導電層と、
該透明導電層の外層に形成され、該透明導電層の屈折率
と異なる屈折率を有する少なくとも１層の防汚性を有す
る導電層保護層とを含むことを特徴とする低反射透明導
電性積層フイルム。1. A hard coat layer on a transparent substrate, a transparent conductive layer having fine particles of at least one metal,
A low-reflection transparent conductive laminate, comprising: at least one conductive layer protective layer having an antifouling property having a refractive index different from the refractive index of the transparent conductive layer, formed on an outer layer of the transparent conductive layer. Film.
電層と透明導電層に隣接する導電層用保護層を有する透
明導電性フイルムにおいて、該導電層保護層の誘電体力
率が０．０１（５０Ｈｚ）以上の樹脂を含有する層であ
ることを特徴とする透明導電性フイルム。2. A transparent conductive film having on a transparent substrate at least one transparent conductive layer and a protective layer for a conductive layer adjacent to the transparent conductive layer, wherein the conductive layer protective layer has a dielectric power factor of 0. A transparent conductive film, which is a layer containing a resin of 01 (50 Hz) or higher.
とも1層の１種の金属あるいは金属酸化物からなる導電
性微粒子を有する透明導電層と、該透明導電層の外側に
形成された導電層保護層を有する透明導電性フィルムに
おいて、該導電層保護層が該透明導電層の屈折率と異な
る屈折率を有する少なくとも1層からなる防汚性を有す
る層からなり、さらに誘電体力率が０．０１（５０Ｈ
ｚ）以上の樹脂を含有する層であることを特徴とする低
反射透明導電性フィルム。3. A hard coat layer on a transparent substrate, a transparent conductive layer having at least one conductive fine particle made of one kind of metal or metal oxide, and a conductive layer formed outside the transparent conductive layer. In a transparent conductive film having a layer protective layer, the conductive layer protective layer is composed of at least one antifouling layer having a refractive index different from the refractive index of the transparent conductive layer, and further has a dielectric power factor of 0. .01 (50H
z) A low-reflection transparent conductive film, which is a layer containing the above resin.
属酸化物からなる導電性微粒子を有する透明導電層の表
面抵抗が１０ＫΩ／□（９０Ｖ印加電圧）以下であるこ
とを特徴とする請求項３に記載の低反射透明導電性フイ
ルム。4. The transparent conductive layer having at least one layer of conductive fine particles made of one kind of metal or metal oxide has a surface resistance of 10 KΩ / □ (applied voltage of 90 V) or less. 4. The low-reflection transparent conductive film according to item 1.
属酸化物からなる導電性微粒子を有する透明導電層にお
いて、導電性金属粒子の粒子サイズが１〜２００ｎｍで
あることを特徴とする請求項３または４に記載の低反射
透明導電性フイルム。5. The transparent conductive layer having at least one layer of conductive fine particles made of one kind of metal or metal oxide, wherein the particle size of the conductive metal particles is 1 to 200 nm. Or the low-reflection transparent conductive film according to 4.
体とする金属または金属酸化物であることを特徴とする
請求項３から５のいずれかに記載の低反射透明導電性フ
イルム。6. The low-reflection transparent conductive film according to claim 3, wherein the conductive fine particles are a metal or a metal oxide mainly composed of gold, silver or copper.
を主体とする合金の微粒子であることを特徴とする請求
項３から６のいずれかに記載の低反射透明導電性積層フ
イルム。7. The low-reflection transparent conductive laminated film according to claim 3, wherein the fine particles made of a metal are fine particles of silver or an alloy mainly containing silver.
が、１．３０以上１．７０以下であることを特徴とする
請求項３から７のいずれかに記載の低反射透明導電性積
層フイルム。8. The low-reflection transparent conductive material according to claim 3, wherein the refractive index of the conductive layer protective layer having antifouling property is 1.30 or more and 1.70 or less. Laminated film.
ｎｍであることを特徴とする請求項３から８のいずれか
に記載の低反射透明導電性積層フイルム。9. The protective layer for a conductive layer has a thickness of 10 to 500.
The low-reflection transparent conductive laminated film according to any one of claims 3 to 8, wherein
なくとも１層の反射防止層と、防汚性を有する最外層か
らなることを特徴とする請求項３から９のいずれかに記
載の低反射透明導電性積層フイルム。10. The conductive layer protective layer having an antifouling property comprises at least one antireflection layer and an outermost layer having an antifouling property. Low reflective transparent conductive laminated film.
む化合物を含有することを特徴とする請求項３から１０
のいずれかにに記載の低反射透明導電性積層フイルム。11. The method according to claim 3, wherein the outermost layer having antifouling properties contains a compound containing fluorine.
The low-reflection transparent conductive laminated film according to any one of the above.
ＫΩ／□（９０Ｖ印加電圧）以下であることを特徴とす
る請求項３から１１のいずれかに記載の低反射透明導電
性フイルム。12. The surface resistance from the protective layer for a conductive layer is 2
The low-reflection transparent conductive film according to any one of claims 3 to 11, wherein the film has a value of KΩ / □ (applied voltage of 90 V) or less.
プラスチックフイルムであることを特徴とする請求項３
から１２のいずれかに記載の低反射透明導電性フイル
ム。13. The method according to claim 3, wherein the transparent substrate is a plastic film having a hard coat layer.
13. The low-reflection transparent conductive film according to any one of items 1 to 12.
導電層保護層付き導電性フイルムの表面から直接アース
をとることを特徴とする低反射透明導電性フイルムの接
地方法。14. A method for grounding a low-reflection transparent conductive film, wherein the ground is directly taken from the surface of the conductive film with a conductive layer protective layer according to claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000162439A JP2001110238A (en) | 1999-06-02 | 2000-05-31 | Low reflectance transparent conductive laminated film |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11-155462 | 1999-06-02 | ||
| JP15546299 | 1999-06-02 | ||
| JP21884799 | 1999-08-02 | ||
| JP11-218847 | 1999-08-02 | ||
| JP2000162439A JP2001110238A (en) | 1999-06-02 | 2000-05-31 | Low reflectance transparent conductive laminated film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001110238A true JP2001110238A (en) | 2001-04-20 |
Family
ID=27320837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000162439A Pending JP2001110238A (en) | 1999-06-02 | 2000-05-31 | Low reflectance transparent conductive laminated film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001110238A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002329598A (en) * | 2001-05-01 | 2002-11-15 | Toyo Metallizing Co Ltd | Antistatic hard coat film |
| JP2002341107A (en) * | 2001-05-15 | 2002-11-27 | Toppan Printing Co Ltd | Conductive anti-reflection film |
| JP2003075604A (en) * | 2001-09-03 | 2003-03-12 | Nitto Denko Corp | Anti-reflection anti-glare film, method of manufacturing the same, optical element, and image display device |
| JP2005324435A (en) * | 2004-05-14 | 2005-11-24 | Teijin Dupont Films Japan Ltd | Transparent conductive laminated film and photoactive electrode for photochemical battery |
| JP2006079731A (en) * | 2004-09-09 | 2006-03-23 | Fuji Photo Film Co Ltd | Optical information recording medium |
| JP2011060617A (en) * | 2009-09-11 | 2011-03-24 | Toppan Printing Co Ltd | Transparent conductive laminate, method of manufacturing the same, and capacitance touch panel |
| JP2011082558A (en) * | 2002-08-17 | 2011-04-21 | Three M Innovative Properties Co | Durable emi shielding film |
| JP2013083871A (en) * | 2011-10-12 | 2013-05-09 | Tamron Co Ltd | Antireflection film and manufacturing method of antireflection film |
| CN112005132A (en) * | 2018-03-29 | 2020-11-27 | 东洋纺株式会社 | Antifouling film with protective film and method for producing the same |
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2000
- 2000-05-31 JP JP2000162439A patent/JP2001110238A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002329598A (en) * | 2001-05-01 | 2002-11-15 | Toyo Metallizing Co Ltd | Antistatic hard coat film |
| JP2002341107A (en) * | 2001-05-15 | 2002-11-27 | Toppan Printing Co Ltd | Conductive anti-reflection film |
| JP2003075604A (en) * | 2001-09-03 | 2003-03-12 | Nitto Denko Corp | Anti-reflection anti-glare film, method of manufacturing the same, optical element, and image display device |
| JP2011082558A (en) * | 2002-08-17 | 2011-04-21 | Three M Innovative Properties Co | Durable emi shielding film |
| JP2005324435A (en) * | 2004-05-14 | 2005-11-24 | Teijin Dupont Films Japan Ltd | Transparent conductive laminated film and photoactive electrode for photochemical battery |
| JP2006079731A (en) * | 2004-09-09 | 2006-03-23 | Fuji Photo Film Co Ltd | Optical information recording medium |
| JP2011060617A (en) * | 2009-09-11 | 2011-03-24 | Toppan Printing Co Ltd | Transparent conductive laminate, method of manufacturing the same, and capacitance touch panel |
| JP2013083871A (en) * | 2011-10-12 | 2013-05-09 | Tamron Co Ltd | Antireflection film and manufacturing method of antireflection film |
| CN112005132A (en) * | 2018-03-29 | 2020-11-27 | 东洋纺株式会社 | Antifouling film with protective film and method for producing the same |
| WO2021060139A1 (en) * | 2019-09-25 | 2021-04-01 | 日東電工株式会社 | Transparent electroconductive film and method for producing same |
| JP2021049708A (en) * | 2019-09-25 | 2021-04-01 | 日東電工株式会社 | Transparent electroconductive film and method for producing the same |
| CN114467150A (en) * | 2019-09-25 | 2022-05-10 | 日东电工株式会社 | Transparent conductive film and method for producing same |
| JP7341821B2 (en) | 2019-09-25 | 2023-09-11 | 日東電工株式会社 | Transparent conductive film and its manufacturing method |
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