JP2012248424A - Conductive laminate and method for producing the same - Google Patents
Conductive laminate and method for producing the same Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000002245 particle Substances 0.000 claims abstract description 121
- 238000000034 method Methods 0.000 claims abstract description 59
- 239000000758 substrate Substances 0.000 claims abstract description 42
- 239000004020 conductor Substances 0.000 claims abstract description 29
- 239000006185 dispersion Substances 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 229920000307 polymer substrate Polymers 0.000 claims description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims description 15
- 150000004706 metal oxides Chemical class 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 12
- 230000009477 glass transition Effects 0.000 claims description 11
- 229910003437 indium oxide Inorganic materials 0.000 claims description 11
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000010304 firing Methods 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 229910052752 metalloid Inorganic materials 0.000 claims description 7
- 150000002738 metalloids Chemical class 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000012530 fluid Substances 0.000 abstract 2
- 238000000576 coating method Methods 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 12
- 238000005245 sintering Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000011521 glass Substances 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 150000002472 indium compounds Chemical class 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GRPQBOKWXNIQMF-UHFFFAOYSA-N indium(3+) oxygen(2-) tin(4+) Chemical compound [Sn+4].[O-2].[In+3] GRPQBOKWXNIQMF-UHFFFAOYSA-N 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011135 tin Substances 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
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、導電性積層体及びその製造方法に関する。特に本発明は、フラットパネルディスプレイ、タッチパネル、太陽電池等のための透明導電性積層体、及びその製造方法に関する。 The present invention relates to a conductive laminate and a method for producing the same. Especially this invention relates to the transparent conductive laminated body for flat panel displays, a touch panel, a solar cell, etc., and its manufacturing method.
電子産業においては、基材及びこの基材上に堆積している導電性膜を有する導電性積層体が、プリント基板、半導体デバイス等の多くの用途で用いられている。 In the electronic industry, a conductive laminate having a base material and a conductive film deposited on the base material is used in many applications such as printed circuit boards and semiconductor devices.
また、導電性積層体のなかでも透明導電性積層体は、透明電極を必要とする多くの用途で使用されており、例えばフラットパネルディスプレイ（例えば液晶ディスプレイ及びプラズマディスプレイ）、タッチパネル、太陽電池等のための透明電極として使用されている。このような透明導電性積層体の透明導電性膜を形成するための具体的な材料としては、透明導電性金属酸化物、特に酸化インジウム−スズ（ＩＴＯ）が用いられている。 In addition, among conductive laminates, transparent conductive laminates are used in many applications that require transparent electrodes, such as flat panel displays (for example, liquid crystal displays and plasma displays), touch panels, solar cells, and the like. It is used as a transparent electrode. As a specific material for forming such a transparent conductive film of the transparent conductive laminate, a transparent conductive metal oxide, particularly indium tin oxide (ITO) is used.
このような導電性積層体の製造方法としては、（１）真空蒸着法、スパッタリング法等の物理的蒸着法（ＰＶＤ法）；（２）原料を反応させて堆積させる化学的蒸着法（ＣＶＤ法）；（３）スプレー法、スピンコート法、ディップコート法及びスクリーン印刷法等の塗布法が知られている。これらのうちのＰＶＤ法及びＣＶＤ法（上記（１）及び（２））は、導電性、及び随意に透明性が良好な導電性積層体を得るために好ましいので、一般に使用されている。しかしながらこれらの方法では、大がかりな装置が必要であり、真空工程を用いるためコストが高い傾向がある。したがって、真空工程を用いない塗布法（上記（３））によって導電性積層体を提供することが検討されている（特許文献１〜３）。
As a method for producing such a conductive laminate, (1) physical vapor deposition (PVD method) such as vacuum vapor deposition or sputtering; (2) chemical vapor deposition (CVD method) in which raw materials are reacted and deposited (3) Coating methods such as spraying, spin coating, dip coating, and screen printing are known. Among these, the PVD method and the CVD method (above (1) and (2)) are generally used because they are preferable for obtaining a conductive laminate having good conductivity and optionally transparency. However, these methods require a large-scale apparatus, and tend to be expensive because a vacuum process is used. Therefore, it has been studied to provide a conductive laminate by a coating method that does not use a vacuum process (above (3)) (
塗布法によって透明導電性積層体を形成するための方法としては、可溶性のスズ及び／又はインジウム化合物を含有している溶液を用いる方法；特定のＩＴＯ粒子を含有する溶液を用いる方法（特許文献１及び２）；ＩＴＯ粒子の層を形成し、この層上にオーバーコートを提供する方法（特許文献３）；ＩＴＯ粒子と可溶性のスズ及び／又はインジウム化合物を含有している溶液を用いる方法（特許文献４〜６等）が知られている。 As a method for forming a transparent conductive laminate by a coating method, a method using a solution containing soluble tin and / or an indium compound; a method using a solution containing specific ITO particles (Patent Document 1) And 2); a method of forming a layer of ITO particles and providing an overcoat on this layer (Patent Document 3); a method of using a solution containing ITO particles and a soluble tin and / or indium compound (Patent Document 3) Documents 4 to 6) are known.
また、塗布法によって透明導電性積層体を形成するための方法としては、ＩＴＯ粒子の層を形成し、その後でフラッシュランプ、レーザー光等を用いてＩＴＯ粒子の焼結を行うことによって、高温でのＩＴＯ粒子の焼結を行わずに、透明導電性積層体を得ることも知られている（特許文献７〜１１等）。 Further, as a method for forming a transparent conductive laminate by a coating method, a layer of ITO particles is formed, and then the ITO particles are sintered using a flash lamp, laser light, etc., at a high temperature. It is also known to obtain a transparent conductive laminate without sintering the ITO particles (Patent Documents 7 to 11 etc.).
本発明では、導電性、及び随意に透明性に関して好ましい特性を有する導電性積層体を、高温での処理を行わずに得ることを可能にする方法を提供する。また、本発明では、このような方法によって製造できる新規な導電性積層体を提供する。 The present invention provides a method that makes it possible to obtain a conductive laminate having favorable properties with respect to conductivity, and optionally transparency, without treatment at high temperatures. Moreover, in this invention, the novel electroconductive laminated body which can be manufactured by such a method is provided.
本件発明者等は、導電性粒子の層を、第１の光源を用いて焼成させ、そしてその後で第２の光源を用いて焼結させることによって、好ましい導電性、及び随意に透明性を有する導電性積層体を、高温での処理を行わずに提供できることを見出して、下記の本発明に想到した。ここで、第１の光源は、境界波長以下の波長のエネルギーの割合が第２の光源よりも少なく、且つ境界波長は、２５０〜４５０ｎｍの範囲の波長から選択される。 The inventors have preferred conductivity, and optionally transparency, by firing the layer of conductive particles using a first light source and then sintering using a second light source. The inventors have found that a conductive laminate can be provided without performing treatment at a high temperature, and have arrived at the present invention described below. Here, the first light source has a lower energy ratio than the second light source, and the boundary wavelength is selected from wavelengths in the range of 250 to 450 nm.
〈１〉（ａ）金属、半金属、金属酸化物、半金属酸化物、及びこれらの組み合わせからなる群より選択される導電性材料の粒子が分散している分散液の層を、基材上に提供すること、
（ｂ）上記分散液の層を乾燥及び焼成して、上記基材上に導電性粒子層を形成すること、
（ｃ）上記導電性粒子層に、第１の光源を用いて照射すること、及び
（ｄ）工程（ｃ）の後で、上記導電性粒子層に、第２の光源を用いて照射すること、
を含み、
上記第１の光源は、境界波長以下の波長のエネルギーの割合が上記第２の光源よりも少なく、且つ
上記境界波長が、２５０ｎｍ〜４５０ｎｍの範囲の波長から選択される、
基材及びこの基材上に堆積している導電性膜を有する導電性積層体を製造する方法。
〈２〉上記基材が透明基材であり、且つ上記導電性膜が透明導電性層である、上記〈１〉項に記載の方法。
〈３〉工程（ｂ）において、上記乾燥及び焼成を３００℃以下の温度で行う、上記〈１〉又は〈２〉項に記載の方法。
〈４〉上記境界波長が、２５０ｎｍ、３００ｎｍ、３５０ｎｍ、４００ｎｍ、又は４５０ｎｍである、上記〈１〉〜〈３〉項のいずれか一項に記載の方法。
〈５〉上記第１の光源は、境界波長以下の波長のエネルギーの割合が２０％以下であり、且つ上記第２の光源は、境界波長以下の波長のエネルギーの割合が２０％超である、上記〈１〉〜〈４〉項のいずれか一項に記載の方法。
〈６〉上記導電性材料の粒子の平均粒子径が１〜１００ｎｍである、上記〈１〉〜〈５〉項のいずれか一項に記載の方法。
〈７〉上記第１の導電性金属酸化物が、酸化インジウム、ドープされた酸化インジウム、酸化亜鉛、ドープされた酸化亜鉛、及びそれらの組み合わせからなる群より選択される材料である、上記〈１〉〜〈６〉項のいずれか一項に記載の方法。
〈８〉上記第１の導電性金属酸化物が、金属原子数に基づいて５０％以上の酸化インジウムを含有している、上記〈１〉〜〈７〉項のいずれか一項に記載の方法。
〈９〉工程（ａ）において、上記導電性材料の粒子が液体媒体中に分散している分散液を提供し、そしてこの分散液を上記基材に塗布することによって、上記分散液層を上記基材上に提供する、上記〈１〉〜〈８〉項のいずれか一項に記載の方法。
〈１０〉工程（ａ）で用いられる上記分散液が、乾燥及び焼成したときに導電性金属酸化物となる金属化合物を更に含有している、上記〈１〉〜〈９〉項のいずれか一項に記載の方法。
〈１１〉ポリマー基材、及びこのポリマー基材上に堆積している導電性膜を有し、
上記ポリマー基材のガラス転移温度が、３００℃以下であり、
上記導電性膜が、互いに結合している導電性材料の粒子を含み、且つ
導電性膜の表面抵抗値が、５００Ω／□以下である、
導電性積層体。
〈１２〉上記ポリマー基材が透明基材であり、且つ上記導電性膜が透明導電性層である、上記〈１１〉項に記載の導電性積層体。
〈１３〉上記導電性材料の粒子の平均粒子径が１〜１００ｎｍである、上記〈１１〉又は〈１２〉項に記載の導電性積層体。
〈１４〉上記ポリマー基材に面している表面側と比較して、上記ポリマー基材と反対側の表面側において、上記導電性膜中の上記導電性材料の粒子の結合の程度が大きい、上記〈１１〉〜〈１３〉項のいずれか一項に記載の導電性積層体。
〈１５〉上記第１の導電性金属酸化物が、金属原子数に基づいて５０％以上の酸化インジウムを含有している、上記〈１１〉〜〈１４〉項のいずれか一項に記載の導電性積層体。
<1> (a) A layer of a dispersion in which particles of a conductive material selected from the group consisting of metals, metalloids, metal oxides, metalloid oxides, and combinations thereof are dispersed on the substrate To provide,
(B) drying and firing the layer of the dispersion to form a conductive particle layer on the substrate;
(C) irradiating the conductive particle layer with a first light source; and (d) irradiating the conductive particle layer with a second light source after step (c). ,
Including
The first light source has a lower energy ratio than the second light source, and the boundary wavelength is selected from wavelengths in the range of 250 nm to 450 nm.
A method for producing a conductive laminate having a substrate and a conductive film deposited on the substrate.
<2> The method according to <1>, wherein the substrate is a transparent substrate, and the conductive film is a transparent conductive layer.
<3> The method according to <1> or <2>, wherein in the step (b), the drying and baking are performed at a temperature of 300 ° C. or lower.
<4> The method according to any one of <1> to <3>, wherein the boundary wavelength is 250 nm, 300 nm, 350 nm, 400 nm, or 450 nm.
<5> The first light source has a ratio of energy of a wavelength equal to or less than a boundary wavelength, and the second light source has a ratio of energy of a wavelength equal to or less than the boundary wavelength to more than 20%. The method according to any one of <1> to <4> above.
<6> The method according to any one of <1> to <5> above, wherein the conductive material particles have an average particle diameter of 1 to 100 nm.
<7> The above <1>, wherein the first conductive metal oxide is a material selected from the group consisting of indium oxide, doped indium oxide, zinc oxide, doped zinc oxide, and combinations thereof. The method according to any one of <1> to <6>.
<8> The method according to any one of <1> to <7>, wherein the first conductive metal oxide contains 50% or more of indium oxide based on the number of metal atoms. .
<9> In the step (a), a dispersion liquid in which the particles of the conductive material are dispersed in a liquid medium is provided, and the dispersion liquid layer is applied to the substrate by applying the dispersion liquid to the substrate. The method according to any one of <1> to <8> above, which is provided on a substrate.
<10> Any one of <1> to <9> above, wherein the dispersion used in step (a) further contains a metal compound that becomes a conductive metal oxide when dried and fired. The method according to item.
<11> having a polymer substrate and a conductive film deposited on the polymer substrate;
The glass transition temperature of the polymer substrate is 300 ° C. or lower,
The conductive film includes particles of conductive material bonded to each other, and the surface resistance value of the conductive film is 500Ω / □ or less,
Conductive laminate.
<12> The conductive laminate according to <11>, wherein the polymer base material is a transparent base material, and the conductive film is a transparent conductive layer.
<13> The conductive laminate according to <11> or <12>, wherein the conductive material particles have an average particle diameter of 1 to 100 nm.
<14> The degree of bonding of the particles of the conductive material in the conductive film is large on the surface side opposite to the polymer base, compared to the surface side facing the polymer base. The conductive laminate according to any one of <11> to <13> above.
<15> The conductive material according to any one of <11> to <14>, wherein the first conductive metal oxide contains 50% or more of indium oxide based on the number of metal atoms. Laminate.
本発明の方法によれば、好ましい導電性、及び随意に透明性を有する導電性積層体を、高温での処理を行わずに得ることができる。すなわち、この本発明によれば、高温での処理を行うことが困難な基材上においてさえも、小さい抵抗値を有する導電性膜を提供することができる。また、本発明の導電性積層体によれば、ガラス転移温度が低い基材を用いているにもかかわらず、小さい抵抗値を有することができる。 According to the method of the present invention, a conductive laminate having preferable conductivity and optionally transparency can be obtained without performing treatment at a high temperature. That is, according to the present invention, it is possible to provide a conductive film having a small resistance value even on a substrate that is difficult to be processed at a high temperature. Moreover, according to the electroconductive laminated body of this invention, although a base material with a low glass transition temperature is used, it can have a small resistance value.
《導電性積層体を製造する本発明の方法》
導電性積層体を製造する本発明の方法を、図１を用いて概念的に説明する。この方法では、基材、及びこの基材上に堆積している導電性膜を有する導電性積層体を製造する。本発明の方法では、比較的高い温度での焼結を行わない場合であっても、好ましい表面抵抗、及び随意に好ましい透明性、ヘーズ値等を有する導電性積層体を製造することができる。この方法では特に、透明導電性積層体、すなわち基材が透明基材であり且つ導電性膜が透明導電性層である導電性積層体を製造することができる。
<< Method of the Present Invention for Producing Conductive Laminate >>
The method of the present invention for producing a conductive laminate will be conceptually described with reference to FIG. In this method, a conductive laminate having a base material and a conductive film deposited on the base material is manufactured. In the method of the present invention, even when sintering is not performed at a relatively high temperature, it is possible to produce a conductive laminate having a preferable surface resistance and optionally a preferable transparency, haze value, and the like. In particular, this method can produce a transparent conductive laminate, that is, a conductive laminate in which the substrate is a transparent substrate and the conductive film is a transparent conductive layer.
〈（ａ）分散液層の形成工程〉
図１（ａ）で示すように、導電性積層体を製造する本発明の方法では始めに、導電性材料の粒子１が液体媒体２中に分散している分散液の層１０を、基材３上に提供する。
<(A) Step of forming dispersion layer>
As shown in FIG. 1A, in the method of the present invention for producing a conductive laminate, first, a
ここで、この分散液の層１０の形成のためには例えば、導電性材料の粒子１が液体媒体２中に分散している分散液を提供し、そしてこの分散液を基材３に塗布することができる。この場合、分散液を基材３に塗布するためには、スピンコーティング、ディップコーティング、噴霧、インクジェット、マイヤーバー、マイクログラビア、スロットダイ等の任意の塗布法を用いることができる。
Here, for the formation of the
導電性材料の粒子としては、金属、半金属、金属酸化物、半金属酸化物、及びこれらの組み合わせからなる群より選択される任意の導電性材料の粒子を用いることができる。具体的な導電性粒子としては、金、銀、銅、パラジウム、錫、白金、タングステン、ニッケル、タンタル、インジウム、亜鉛、チタン、クロム、鉄、シリコン、ゲルマニウム、アンチモン、テルル及びコバルト、並びにこれらの組み合わせ及び酸化物からなる群より選択される材料を含む粒子を挙げることができる。 As the particles of the conductive material, particles of any conductive material selected from the group consisting of metals, metalloids, metal oxides, metalloid oxides, and combinations thereof can be used. Specific conductive particles include gold, silver, copper, palladium, tin, platinum, tungsten, nickel, tantalum, indium, zinc, titanium, chromium, iron, silicon, germanium, antimony, tellurium and cobalt, and these Mention may be made of particles comprising a material selected from the group consisting of combinations and oxides.
本発明の方法において、透明導電性積層体、すなわち基材が透明基材であり且つ導電性膜が透明導電性層である導電性積層体を製造する場合、本発明において使用する導電性材料の粒子としては、最終的な導電性層としたときに透明性が高い導電性材料の粒子を用いることが好ましい。 In the method of the present invention, when producing a transparent conductive laminate, that is, a conductive laminate in which the substrate is a transparent substrate and the conductive film is a transparent conductive layer, the conductive material used in the present invention As the particles, it is preferable to use particles of a conductive material having high transparency when the final conductive layer is formed.
この場合、導電性材料の粒子としては、透明導電性金属酸化物又は半金属酸化物、特にインジウム、ドープされた酸化インジウム、酸化亜鉛、ドープされた酸化亜鉛、及びそれらの組み合わせからなる群より選択される材料の粒子を用いることができる。ここで、酸化インジウムのドープは例えば、スズ、亜鉛、ゲルマニウム、モリブデン、フッ素、チタン、ジルコニウム、ハフニウム、ニオブ、タンタル、タングステン、テルル、及びそれらの組み合わせからなる群より選択される元素によって行うことができる。また、酸化亜鉛のドープは例えば、インジウム、アルミニウム、ガリウム、ホウ素、インジウム、イットリウム、スカンジウム、フッ素、バナジウム、ケイ素、ゲルマニウム、チタン、ジルコニウム、ハフニウム、及びそれらの組み合わせからなる群より選択される元素によって行うことができる。 In this case, the conductive material particles are selected from the group consisting of transparent conductive metal oxides or metalloid oxides, particularly indium, doped indium oxide, zinc oxide, doped zinc oxide, and combinations thereof. Particles of the material to be used can be used. Here, indium oxide is doped with an element selected from the group consisting of tin, zinc, germanium, molybdenum, fluorine, titanium, zirconium, hafnium, niobium, tantalum, tungsten, tellurium, and combinations thereof, for example. it can. In addition, the doping of zinc oxide is, for example, by an element selected from the group consisting of indium, aluminum, gallium, boron, indium, yttrium, scandium, fluorine, vanadium, silicon, germanium, titanium, zirconium, hafnium, and combinations thereof. It can be carried out.
より具体的には、導電性材料の粒子としては、金属原子数に基づいて５０％以上、６０％以上、７０％以上、８０％以上、９０％以上、又は９５％以上の酸化インジウム、及び随意に残部の酸化スズ、酸化亜鉛等の他の金属酸化物を含有する導電性金属酸化物の粒子を用いることができる。すなわち例えば、本発明において使用する導電性材料の粒子は、酸化インジウム−スズ（ＩＴＯ）、酸化インジウム−亜鉛（ＩＺＯ）等の粒子であってよい。 More specifically, the conductive material particles include 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more of indium oxide based on the number of metal atoms, and optionally In addition, conductive metal oxide particles containing other metal oxide such as tin oxide and zinc oxide can be used. That is, for example, the particles of the conductive material used in the present invention may be particles of indium oxide-tin (ITO), indium oxide-zinc (IZO), or the like.
このような導電性材料の粒子の平均粒子径は、１ｎｍ以上、５ｎｍ以上、又は１０ｎｍ以上であって、５０ｎｍ以下、８０ｎｍ以下、１００ｎｍ以下、又は２００ｎｍ以下であってよい。ここで、平均粒子径が１００ｎｍ以下であることは光学的に透明な透明導電性膜を得るために好ましい。 The average particle size of such conductive material particles may be 1 nm or more, 5 nm or more, or 10 nm or more, and may be 50 nm or less, 80 nm or less, 100 nm or less, or 200 nm or less. Here, the average particle diameter is preferably 100 nm or less in order to obtain an optically transparent transparent conductive film.
工程（ａ）で用いられる分散液は、乾燥及び焼成したときに、上記のような導電性材料となる金属化合物、例えば金属塩化物を更に含有していてもよい。このような金属化合物としては例えば、金属塩化物、金属硝酸塩、金属酢酸塩、特に塩化インジウム、塩化スズ、及び塩化亜鉛を挙げることができる。 The dispersion used in the step (a) may further contain a metal compound, for example, a metal chloride, which becomes a conductive material as described above when dried and fired. Examples of such metal compounds include metal chlorides, metal nitrates, metal acetates, particularly indium chloride, tin chloride, and zinc chloride.
〈基材〉
本発明の方法において用いることができる基材としては、乾燥及び焼成工程における加熱に耐えることができる任意の基材、特に透明基材を用いることができる。ここで、この基材は、ポリマーのような有機材料であっても、ガラスなどのような無機材料であってもよい。
<Base material>
As the substrate that can be used in the method of the present invention, any substrate that can withstand the heating in the drying and firing steps, particularly a transparent substrate, can be used. Here, the substrate may be an organic material such as a polymer or an inorganic material such as glass.
また、この基材、特に透明基材としては、３００℃以下、２５０℃以下、２００℃以下、１５０℃以下、又は１００℃以下のガラス転移温度を有する基材、特にポリマー基材、すなわち高温での加熱を行うことができない基材を用いることができる。このようなポリマー基材としては、ポリアクリレート（ガラス転移温度：約１１０℃）、非晶質ポリオレフィン（ガラス転移温度：約１４０℃）、ポリカーボネート（ガラス転移温度：約１５０℃）、ポリエーテルサルホン（ガラス転移温度：約２３０℃）、ポリアミドイミド（ガラス転移温度：約２７５℃）を挙げることができる。 Moreover, as this base material, especially a transparent base material, the base material which has a glass transition temperature of 300 degrees C or less, 250 degrees C or less, 200 degrees C or less, 150 degrees C or less, or 100 degrees C or less, especially a polymer base material, ie, high temperature A base material that cannot be heated can be used. As such a polymer substrate, polyacrylate (glass transition temperature: about 110 ° C.), amorphous polyolefin (glass transition temperature: about 140 ° C.), polycarbonate (glass transition temperature: about 150 ° C.), polyethersulfone (Glass transition temperature: about 230 ° C.) and polyamideimide (glass transition temperature: about 275 ° C.).
〈（ｂ）乾燥及び焼成工程〉
本発明の方法は、基材上の分散液層を乾燥及び焼成して、図１（ｂ）で示すように、導電性粒子層２０を形成する乾燥及び焼成工程を含む。この乾燥及び焼成は、導電性粒子層２０中の液体成分の少なくとも一部、例えば液体成分の実質的な部分を除去するのに充分な程度まで行う。具体的には、例えばこの乾燥及び焼成は、３００℃以下、２５０℃以下、２００℃以下、１５０℃以下、１００℃以下、又は８０℃以下の温度で行う。また、この乾燥及び焼成工程を比較的低い温度で行うことは、比較的耐熱性が低い材料、例えばポリマーのような有機材料を透明基材として用いる場合に好ましい。
<(B) Drying and firing step>
The method of the present invention includes a drying and firing step in which the dispersion layer on the substrate is dried and fired to form the
この乾燥及び焼成は例えば１分以上、１０分以上、又は１時間以上であって、５時間以下、又は１０時間以下にわたって行うことができる。 This drying and baking can be performed for, for example, 1 minute or more, 10 minutes or more, or 1 hour or more, and 5 hours or less or 10 hours or less.
〈（ｃ）及び（ｄ）第１及び第２の光源の照射〉
本発明の方法は、導電性粒子層に、第１の光源を用いて照射することを含む。また、本発明の方法は、第１の光源を用いた照射の後で、導電性粒子層に、第２の光源を用いて照射することを含む。ここで、第１の光源は、境界波長以下の波長のエネルギーの割合が、第２の光源よりも少ない。
<(C) and (d) Irradiation of first and second light sources>
The method of the present invention includes irradiating the conductive particle layer with a first light source. In addition, the method of the present invention includes irradiating the conductive particle layer with the second light source after the irradiation with the first light source. Here, the first light source has a lower energy ratio than the second light source.
本発明の方法では、初めに第１の光源、すなわち短波長の光の割合が少なく且つ長波長の光の割合が多い光源を用いて、導電性粒子層を照射する。これによれば、長波長の光は導電性粒子層を透過し易いので、図１（ｃ）で示すように、導電性粒子層３０全体にわたって導電性粒子が焼成される。
In the method of the present invention, first, the conductive particle layer is irradiated using the first light source, that is, the light source having a small proportion of short wavelength light and a large proportion of long wavelength light. According to this, since long wavelength light is easy to permeate | transmit an electroconductive particle layer, as shown in FIG.1 (c), electroconductive particle is baked over the
また、本発明の方法では、第１の光源を用いた照射の後で、第２の光源、すなわち短波長の光の割合が大きく且つ長波長の光の割合が小さい光源を用いて、導電性粒子層を照射する。これによれば、短波長の光源では個々の光子が大きいエネルギーを有しているので、光子のエネルギーを受け取った部分の焼結が進行し易い。また、短波長の光源は比較的導電性粒子層を透過しにくいので、図１（ｄ）で示すように、導電性粒子層４０の表面部分の導電性粒子の焼結が特に促進される。したがって例えば、本発明の方法では、得られる導電性膜の厚さが１００ｎｍ以下、１５０ｎｍ以下、３００ｎｍ以下、５００ｎｍ以下又は１０００ｎｍ以であり、それによって短波長の光源によって焼結される割合が多くなるようにすることができる。
In the method of the present invention, after irradiation using the first light source, the second light source, that is, a light source having a large proportion of short-wavelength light and a small proportion of long-wavelength light, Irradiate the particle layer. According to this, since individual photons have large energy in a short wavelength light source, sintering of the portion that receives the photon energy is likely to proceed. In addition, since the light source having a short wavelength is relatively difficult to transmit through the conductive particle layer, the sintering of the conductive particles on the surface portion of the
すなわち、本発明の方法では、第１の光源を用いた照射によって、導電性粒子層の全体にわたって導電性粒子を焼成させるとともに、第２の光源を用いた照射によって、導電性粒子層、特に導電性粒子層の表面側を更に焼結させる。 That is, in the method of the present invention, the conductive particles are baked over the entire conductive particle layer by irradiation using the first light source, and the conductive particle layer, particularly conductive, is irradiated by irradiation using the second light source. The surface side of the conductive particle layer is further sintered.
これに対して、長波長の光源を用いて導電性粒子層を照射するのみだと、個々の光子のエネルギーが小さいことによって、導電性粒子の焼結が充分に進行しない場合がある。また、短波長の光源を用いて導電性粒子層を照射するのみだと、導電性粒子層が事前に充分に焼成されていない場合、例えば熱による焼成を比較的低温で行った場合には、光子のエネルギーを受け取った部分で導電性粒子層が破損することがある。これは、短波長の光源では、個々の光子が大きいエネルギーを有していることによる。 On the other hand, if the conductive particle layer is only irradiated using a long wavelength light source, the sintering of the conductive particles may not sufficiently proceed due to the small energy of individual photons. In addition, if only the conductive particle layer is irradiated using a short wavelength light source, if the conductive particle layer is not sufficiently fired in advance, for example, when firing by heat at a relatively low temperature, The conductive particle layer may be damaged at the portion that receives the photon energy. This is due to the fact that each photon has a large energy in a short wavelength light source.
ここで、第１の光源と第２の光源とを区別するための境界波長は、２５０〜４５０ｎｍの範囲の波長から選択され、例えば２５０ｎｍ、３００ｎｍ、３５０ｎｍ、４００ｎｍ、又は４５０ｎｍであってよい。この境界波長は、導電性粒子層の厚さ、導電性粒子層の光透過性等に依存している。より具体的には例えば、導電性粒子層の厚さが比較的厚い場合、及び／又は導電性粒子の透過性が低い場合には、一般に比較的大きい波長を境界波長として選択して、第１の光源による照射が、膜厚全体に達し、それによって導電性粒子が膜厚全体において焼結されるようにすることができる。 Here, the boundary wavelength for distinguishing between the first light source and the second light source is selected from wavelengths in the range of 250 to 450 nm, and may be, for example, 250 nm, 300 nm, 350 nm, 400 nm, or 450 nm. This boundary wavelength depends on the thickness of the conductive particle layer, the light transmittance of the conductive particle layer, and the like. More specifically, for example, when the thickness of the conductive particle layer is relatively thick and / or when the conductivity of the conductive particles is low, the first wavelength is generally selected as the boundary wavelength. Irradiation by the light source can reach the entire film thickness, whereby the conductive particles can be sintered throughout the film thickness.
〈第１の光源〉
第１の光源としては、例えばキセノンランプ、水銀ランプを挙げることができる。
<First light source>
Examples of the first light source include a xenon lamp and a mercury lamp.
第１の光源は例えば、第１の光源は例えば、照射の単位面積当たりのエネルギーが、０．１〜５０．０Ｊ／ｃｍ２であってよい。また更に、第１の光源は、境界波長以下の波長のエネルギーの割合が２０％以下、１０％以下、又は５％以下であってよい。 For example, the first light source may be, for example, an energy per unit area of irradiation of 0.1 to 50.0 J / cm 2 . Still further, in the first light source, the ratio of energy of wavelengths below the boundary wavelength may be 20% or less, 10% or less, or 5% or less.
また、第１の光源による照射は複数回に分けて行うことができ、個々の照射の光照射時間は例えば、０．１ｍ秒〜１０分であってよい。 Moreover, the irradiation with the first light source can be performed in a plurality of times, and the light irradiation time of each irradiation may be, for example, 0.1 milliseconds to 10 minutes.
第１の光源による照射の程度は、導電性粒子層の厚さ、導電性粒子層の光透過性等に依存しており、第２の光源による照射の際に導電性粒子層が劣化しない程度まで、導電性粒子層を焼成させることが好ましい。 The degree of irradiation with the first light source depends on the thickness of the conductive particle layer, the light transmittance of the conductive particle layer, etc., and the degree to which the conductive particle layer does not deteriorate upon irradiation with the second light source It is preferable to fire the conductive particle layer.
〈第２の光源〉
第２の光源、すなわち比較的短波長の光源としては、エキシマレーザー又はエキシマランプ、例えばＫｒＦレーザー（中心波長：２４８ｎｍ）、ＡｒＦレーザー（中心波長：１９３ｎｍ）、Ａｒ２エキシマランプ（中心波長：１２６ｎｍ）、Ｋｒ２エキシマランプ（中心波長：１４６ｎｍ）、Ｘｅ２エキシマランプ（中心波長：１７２ｎｍ）、ＫｒＣｌエキシマランプ（中心波長：２２２ｎｍ）、ＸｅＣｌエキシマランプ（中心波長：３０８ｎｍ）等を挙げることができる。
<Second light source>
As the second light source, that is, a light source having a relatively short wavelength, an excimer laser or an excimer lamp, for example, KrF laser (center wavelength: 248 nm), ArF laser (center wavelength: 193 nm), Ar 2 excimer lamp (center wavelength: 126 nm) Kr 2 excimer lamp (center wavelength: 146 nm), Xe 2 excimer lamp (center wavelength: 172 nm), KrCl excimer lamp (center wavelength: 222 nm), XeCl excimer lamp (center wavelength: 308 nm), and the like.
第２の光源は例えば、第２の光源は例えば、照射の単位面積当たりのエネルギーが、１０〜１０００ｍＪ／ｃｍ２であってよい。また更に、第２の光源は、境界波長以下の波長のエネルギーの割合が２０％超、３０％超、４０％超、５０％超、６０％超、７０％超、８０％超、又は９０％超であってよい。 For example, the second light source may be, for example, an energy per unit area of irradiation of 10 to 1000 mJ / cm 2 . Still further, in the second light source, the ratio of energy of wavelengths below the boundary wavelength is over 20%, over 30%, over 40%, over 50%, over 60%, over 70%, over 80%, or 90%. It can be super.
また、第２の光源による照射は複数回に分けて行うことができ、個々の照射の光照射時間は例えば、１ｎ秒〜１０００ｎ秒であってよい。 Further, the irradiation with the second light source can be performed in a plurality of times, and the light irradiation time of each irradiation may be, for example, 1 nsec to 1000 nsec.
《本発明の導電性積層体》
本発明の導電性積層体は、ポリマー基材、及びこのポリマー基材上に堆積している導電性膜を有し、ポリマー基材のガラス転移温度が、３００℃以下であり、導電性膜が、互いに結合している導電性材料の粒子を含み、且つ導電性膜の表面抵抗値が、５００Ω／□以下である。本発明の導電性積層体は特に、基材が透明基材であり且つ導電性膜が透明導電性層である透明導電性積層体である。
<< Conductive Laminate of the Present Invention >>
The conductive laminate of the present invention has a polymer substrate and a conductive film deposited on the polymer substrate, the glass transition temperature of the polymer substrate is 300 ° C. or lower, and the conductive film is , Including particles of conductive material bonded to each other, and the surface resistance value of the conductive film is 500Ω / □ or less. The conductive laminate of the present invention is particularly a transparent conductive laminate in which the substrate is a transparent substrate and the conductive film is a transparent conductive layer.
本発明の導電性積層体は、ガラス転移温度が低いポリマー基材を用いているにもかかわらず、小さい表面抵抗値を有することができる。このような本発明の導電性積層体は、導電性積層体を製造する本発明の方法を用いて製造することができる。なお、使用可能なポリマー基材に関しては、本発明の方法に関する記載を参照することができる。 The conductive laminate of the present invention can have a small surface resistance value despite using a polymer substrate having a low glass transition temperature. Such a conductive laminate of the present invention can be produced using the method of the present invention for producing a conductive laminate. In addition, regarding the polymer base material which can be used, the description regarding the method of this invention can be referred.
〈膜厚〉
本発明の導電性積層体の導電性膜の膜厚は、意図する用途に応じて決定することができる。また、本発明の導電性積層体の導電性膜の膜厚は、意図する用途に応じて決定することができ、例えば意図する用途で所望とされる表面抵抗値、光透過率、ヘーズ値、強度、及び／又は密着性に応じて決定することができる。具体的には例えば、この導電性膜の膜厚は、１０ｎｍ以上、３０ｎｍ以上であって、１００ｎｍ以下、１５０ｎｍ以下、３００ｎｍ以下、５００ｎｍ以下又は１０００ｎｍ以下であってよい。
<Film thickness>
The film thickness of the conductive film of the conductive laminate of the present invention can be determined according to the intended use. Moreover, the film thickness of the conductive film of the conductive laminate of the present invention can be determined according to the intended use, for example, the surface resistance value, the light transmittance, the haze value, which are desired for the intended use, It can be determined according to strength and / or adhesion. Specifically, for example, the thickness of the conductive film may be 10 nm or more and 30 nm or more, and may be 100 nm or less, 150 nm or less, 300 nm or less, 500 nm or less, or 1000 nm or less.
〈表面抵抗値〉
本発明の導電性積層体は例えば、５００Ω／□以下、４００Ω／□以下、３００Ω／□以下、又は２５０Ω／□以下の表面抵抗値を有することができる。
<Surface resistance value>
The conductive laminate of the present invention can have a surface resistance value of, for example, 500Ω / □ or less, 400Ω / □ or less, 300Ω / □ or less, or 250Ω / □ or less.
〈全光透過率〉
本発明の透明導電性積層体の透明導電性膜は例えば、８０．０％以上、８５．０％以上、８８．０％以上、９０．０％以上、又は９１．０％以上の全光透過率を有することができる。
<Total light transmittance>
The transparent conductive film of the transparent conductive laminate of the present invention has a total light transmission of, for example, 80.0% or more, 85.0% or more, 88.0% or more, 90.0% or more, or 91.0% or more. Can have a rate.
〈ヘーズ値〉
本発明の透明導電性積層体の透明導電性膜は例えば、１０．０％以下、５．０％以下、３．０％以下、又は１．０％以下のヘーズ値を有することができる。
<Haze value>
The transparent conductive film of the transparent conductive laminate of the present invention can have, for example, a haze value of 10.0% or less, 5.0% or less, 3.0% or less, or 1.0% or less.
上記記載のように、本発明の方法で用いられる第２の光源から照射される短波長の光源は、比較的導電性粒子層を透過しにくい。したがって、本発明の導電性積層体の製造方法によって本発明の導電性積層体を製造する場合、ポリマー基材に面している表面側と比較して、ポリマー基材と反対側の表面側において、導電性膜中の導電性材料の粒子の結合の程度が大きい。具体的には例えば、本発明の導電性積層体は、導電性膜の表面から深さ方向に１００ｎｍ以下、５０ｎｍ以下、３０ｎｍ以下の部分のみが実質的に焼結されたものであってよい。 As described above, the short wavelength light source irradiated from the second light source used in the method of the present invention is relatively difficult to transmit through the conductive particle layer. Accordingly, when the conductive laminate of the present invention is manufactured by the method of manufacturing the conductive laminate of the present invention, the surface side opposite to the polymer substrate is compared with the surface side facing the polymer substrate. The degree of bonding of the conductive material particles in the conductive film is large. Specifically, for example, the conductive laminate of the present invention may be one in which only portions of 100 nm or less, 50 nm or less, and 30 nm or less are substantially sintered in the depth direction from the surface of the conductive film.
〈その他〉
なお、導電性材料、基材等に関しては、上記の導電性積層体を製造する本発明の方法に関する上記の記載を参照することができる。
<Others>
In addition, regarding conductive material, a base material, etc., said description regarding the method of this invention which manufactures said electroconductive laminated body can be referred.
〈実施例１：第１の光源による照射１回実施後、第２の光源による照射１回実施〉
以下で示すようにして、本発明の透明導電性積層体を得た。
Example 1: After one irradiation with the first light source, one irradiation with the second light source>
The transparent conductive laminate of the present invention was obtained as shown below.
（ＩＴＯ粒子層の形成）
平均１次粒子径が２０ｎｍのＩＴＯ粒子を含有する粒子分散液（ＣＩＮＫナノテック株式会社製、１０ｗｔ％、水分散液、界面活性剤添加なし）を、スピンコート法を用いてガラス基板に塗布して、ＩＴＯ粒子が分散している分散液の層をガラス基板上に形成した。その後、吸着型ホットプレートを用いて、分散液の層を５０℃で３分にわたって予備乾燥し、その後、酸素濃度１％以下の窒素雰囲気において２５０℃で４時間にわたって焼成をおこなって、ＩＴＯ粒子層を作成した。
(Formation of ITO particle layer)
A particle dispersion containing ITO particles having an average primary particle diameter of 20 nm (CINK Nanotech Co., Ltd., 10 wt%, aqueous dispersion, no surfactant added) was applied to a glass substrate using a spin coating method. A layer of dispersion in which ITO particles are dispersed was formed on a glass substrate. Thereafter, the dispersion layer is preliminarily dried at 50 ° C. for 3 minutes using an adsorption type hot plate, and then baked at 250 ° C. for 4 hours in a nitrogen atmosphere having an oxygen concentration of 1% or less to obtain an ITO particle layer. It was created.
２５０℃での焼成後のＩＴＯ粒子層の表面抵抗値（４探針法：三菱化学社製 ロレスタ）は、９，５００Ωであった。 The surface resistance value (4-probe method: Loresta, manufactured by Mitsubishi Chemical Corporation) of the ITO particle layer after firing at 250 ° C. was 9,500Ω.
（第１の光源による照射）
２５０℃での焼成後のＩＴＯ粒子層を、キセノンランプ（波長分布を図２に示す（製品カタログから抜粋）、照射エネルギー１０Ｊ／ｃｍ２・ｓ、３５０ｎｍ（境界波長）以下の波長のエネルギーの割合が１０％以下）を、第１の光源として用いて、１．０ミリ秒間にわたって照射した（１０ｍＪ／ｃｍ２）。
(Irradiation by the first light source)
The ITO particle layer after firing at 250 ° C. is a xenon lamp (wavelength distribution shown in FIG. 2 (extracted from the product catalog), irradiation energy 10 J / cm 2 · s, ratio of energy of wavelengths below 350 nm (boundary wavelength) Was used as the first light source and irradiated for 1.0 millisecond (10 mJ / cm 2 ).
この照射後の表面抵抗値は、５，５００Ωであった。ＡＦＭ（ＳＩＩ社製）を用いて塗膜表面を観察したが、ＩＴＯ粒子の焼結は確認されなかった。 The surface resistance value after this irradiation was 5,500Ω. The surface of the coating film was observed using AFM (manufactured by SII), but sintering of the ITO particles was not confirmed.
（第２の光源による照射）
ＡｒＦエキシマレーザー装置（ビーム社製、中心波長１９３ｎｍ、３５０ｎｍ（境界波長）以下の波長のエネルギーの割合が約１００％）を第２の光源として用いて、１００Ｊ／ｃｍ２照射した。この装置では、実質的に全てのエネルギーが約１９３ｎｍの波長の光として出力されている。
(Irradiation by the second light source)
An ArF excimer laser device (manufactured by Beam Co., Ltd., center wavelength 193 nm, energy ratio of wavelength of 350 nm (boundary wavelength) or less) was used as the second light source, and irradiation was performed at 100 J / cm 2 . In this apparatus, substantially all energy is output as light having a wavelength of about 193 nm.
この照射後の表面抵抗値は、２９０Ωであった。大幅な表面抵抗値の低下が観察された。ただし、導電性膜は若干白化していた。ＡＦＭでＩＴＯ粒子塗膜の表面を観察するとＩＴＯ粒子が焼結していることが確認された。 The surface resistance value after this irradiation was 290Ω. A significant reduction in surface resistance was observed. However, the conductive film was slightly whitened. When the surface of the ITO particle coating film was observed with AFM, it was confirmed that the ITO particles were sintered.
〈実施例２：第１の光源による照射２回実施後、第２の光源による照射１回実施〉
（ＩＴＯ粒子層の形成、及び第１の光源による照射）
実施例１と同様にして、ＩＴＯ粒子層を形成し、そして第１の光源による照射を行った。
<Embodiment 2: After irradiation twice with the first light source, once irradiation with the second light source>
(Formation of ITO particle layer and irradiation by first light source)
In the same manner as in Example 1, an ITO particle layer was formed, and irradiation with a first light source was performed.
この照射後の表面抵抗値は、５，５００Ωであった。ＡＦＭ（ＳＩＩ社製）を用いて塗膜表面を観察したが、ＩＴＯ粒子の焼結は確認されなかった。 The surface resistance value after this irradiation was 5,500Ω. The surface of the coating film was observed using AFM (manufactured by SII), but sintering of the ITO particles was not confirmed.
その後、第１の光源による照射を同一の条件で再度行った。 Thereafter, irradiation with the first light source was performed again under the same conditions.
この照射後の表面抵抗値は、３，５００Ωであった。ＡＦＭ（ＳＩＩ社製）を用いて塗膜表面を観察したが、ＩＴＯ粒子の焼結は確認されなかった。 The surface resistance value after this irradiation was 3,500Ω. The surface of the coating film was observed using AFM (manufactured by SII), but sintering of the ITO particles was not confirmed.
（第２の光源による照射）
実施例１と同様にして、第２の光源による照射を行った。
(Irradiation by the second light source)
In the same manner as in Example 1, irradiation with the second light source was performed.
この照射後の表面抵抗値は、２２０Ωであった。実施例１と同様にしてＡＦＭを用いてＩＴＯ粒子塗膜の表面を観察するとＩＴＯ粒子が焼結していることが確認された。また、導電性膜の白化はほとんど観察されなかった。 The surface resistance value after this irradiation was 220Ω. When the surface of the ITO particle coating film was observed using AFM in the same manner as in Example 1, it was confirmed that the ITO particles were sintered. Further, almost no whitening of the conductive film was observed.
〈実施例３：第１の光源による照射１回実施後、第２の光源による照射３回実施〉
（ＩＴＯ粒子層の形成、及び第１の光源による照射）
実施例１と同様にして、ＩＴＯ粒子層を形成し、そして第１の光源による照射を行った。
<Embodiment 3: After the first irradiation with the first light source, the irradiation with the second light source is performed three times>
(Formation of ITO particle layer and irradiation by first light source)
In the same manner as in Example 1, an ITO particle layer was formed, and irradiation with a first light source was performed.
この照射後の表面抵抗値は、５，５００Ωであった。ＡＦＭ（ＳＩＩ社製）を用いて塗膜表面を観察したが、ＩＴＯ粒子の焼結は確認されなかった。 The surface resistance value after this irradiation was 5,500Ω. The surface of the coating film was observed using AFM (manufactured by SII), but sintering of the ITO particles was not confirmed.
（第２の光源による照射）
その後、実施例１と同一の条件で第２の光源による照射を３回繰り返し行った。
(Irradiation by the second light source)
Thereafter, irradiation with the second light source was repeated three times under the same conditions as in Example 1.
１回目の照射後の表面抵抗値は、２８０Ωであった。２回目の照射後の表面抵抗値は、１９０Ωであり、塗膜表面が金属反射を示すようになり、塗膜の白化は観察されなかった。３回目の照射後の表面抵抗値は、１８０Ωであった。実施例１と同様にしてＡＦＭを用いてＩＴＯ粒子塗膜の表面を観察するとＩＴＯ粒子が焼結していることが確認された。 The surface resistance value after the first irradiation was 280Ω. The surface resistance value after the second irradiation was 190Ω, the surface of the coating film showed metal reflection, and no whitening of the coating film was observed. The surface resistance value after the third irradiation was 180Ω. When the surface of the ITO particle coating film was observed using AFM in the same manner as in Example 1, it was confirmed that the ITO particles were sintered.
〈実施例４：第１の光源による照射２回実施後、第２の光源による照射３回実施〉
（ＩＴＯ粒子層の形成、及び第１の光源による照射）
実施例１と同様にしてＩＴＯ粒子層を形成し、そして実施例２と同様にして第１の光源による照射を２回行った。
<Example 4: Irradiation with the first light source is performed twice and then irradiation with the second light source is performed three times>
(Formation of ITO particle layer and irradiation by first light source)
An ITO particle layer was formed in the same manner as in Example 1, and irradiation with the first light source was performed twice in the same manner as in Example 2.
この照射後の表面抵抗値は、３，３００Ωであった。ＡＦＭ（ＳＩＩ社製）を用いてと膜表面を観察したが、ＩＴＯ粒子の焼結は確認されなかった。 The surface resistance value after this irradiation was 3,300Ω. The film surface was observed using AFM (manufactured by SII), but sintering of ITO particles was not confirmed.
（第２の光源による照射）
その後、実施例３と同一の条件で第２の光源による照射を３回繰り返し行った。
(Irradiation by the second light source)
Thereafter, irradiation with the second light source was repeated three times under the same conditions as in Example 3.
１回目の照射後の表面抵抗値は、２３０Ωであった。２回目の照射後の表面抵抗値は、１６０Ωであり、塗膜表面が金属反射を示すようになり、塗膜の白化は観察されなかった。３回目の照射後の表面抵抗値は、１５５Ωであった。実施例１と同様にしてＡＦＭを用いてＩＴＯ粒子塗膜の表面を観察するとＩＴＯ粒子が焼結していることが確認された。 The surface resistance value after the first irradiation was 230Ω. The surface resistance value after the second irradiation was 160Ω, the coating film surface showed metal reflection, and no whitening of the coating film was observed. The surface resistance value after the third irradiation was 155Ω. When the surface of the ITO particle coating film was observed using AFM in the same manner as in Example 1, it was confirmed that the ITO particles were sintered.
実施例１〜４の結果から、粒子が焼結しない範囲で第１の光源で複数回照射すること、第２の光源で複数回照射して粒子を焼結させること、又はこれらの両方を実施することによって、安定し再現性良く、導電性の高い導電膜を形成することが可能であることが確認された。 From the results of Examples 1 to 4, the first light source is irradiated a plurality of times within the range where the particles are not sintered, the second light source is irradiated a plurality of times to sinter the particles, or both. By doing this, it was confirmed that it is possible to form a conductive film that is stable, has good reproducibility, and high conductivity.
〈比較例１：第１の光源による照射を行なわずに第２の光源による照射１回実施〉
（ＩＴＯ粒子層の形成）
実施例１と同様にして、ＩＴＯ粒子層を形成した。
<Comparative Example 1: Implementing once irradiation with the second light source without performing irradiation with the first light source>
(Formation of ITO particle layer)
In the same manner as in Example 1, an ITO particle layer was formed.
（第２の光源による照射）
第１の光源による照射を行わずに、形成されたＩＴＯ粒子層に、実施例１と同様の条件で第２の光源による照射を行った。
(Irradiation by the second light source)
Without performing irradiation with the first light source, the formed ITO particle layer was irradiated with the second light source under the same conditions as in Example 1.
第２の光源による照射後のＩＴＯ粒子層はガラス基板から完全に剥がれ、導電性を確認することができなかった。 The ITO particle layer after irradiation with the second light source was completely peeled off from the glass substrate, and the conductivity could not be confirmed.
〈比較例２〉
（ＩＴＯ粒子層の形成、及び第２の光源による照射）
比較例１と同様にして、ＩＴＯ粒子層を形成し、そして第２の光源による照射を行った。ただしここでは、ＩＴＯ粒子層の焼成を、２５０℃ではなく、４００℃で行った。
<Comparative example 2>
(Formation of ITO particle layer and irradiation by second light source)
In the same manner as in Comparative Example 1, an ITO particle layer was formed, and irradiation with a second light source was performed. Here, however, the ITO particle layer was baked at 400 ° C. instead of 250 ° C.
２５０℃焼成を行った比較例１の場合とは異なり、第２の光源による照射後でも、ＩＴＯ粒子層はガラス基板から剥がれていなかった。この照射後の表面抵抗値は、７８０Ωであった。 Unlike the case of Comparative Example 1 in which baking was performed at 250 ° C., the ITO particle layer was not peeled off from the glass substrate even after irradiation with the second light source. The surface resistance value after this irradiation was 780Ω.
１ 導電性材料の粒子
２ 導電性材料の粒子が分散している分散液
３ 基材
１０ 分散液層
２０、３０、４０ 導電性粒子層
DESCRIPTION OF
Claims (15)
（ｂ）前記分散液の層を乾燥及び焼成して、前記基材上に導電性粒子層を形成すること、
（ｃ）前記導電性粒子層に、第１の光源を用いて照射すること、及び
（ｄ）工程（ｃ）の後で、前記導電性粒子層に、第２の光源を用いて照射すること、
を含み、
前記第１の光源は、境界波長以下の波長のエネルギーの割合が前記第２の光源よりも少なく、且つ
前記境界波長が、２５０ｎｍ〜４５０ｎｍの範囲の波長から選択される、
基材及びこの基材上に堆積している導電性膜を有する導電性積層体を製造する方法。 (A) providing on the substrate a layer of a dispersion in which particles of a conductive material selected from the group consisting of metals, metalloids, metal oxides, metalloid oxides, and combinations thereof are dispersed; thing,
(B) drying and firing the layer of the dispersion to form a conductive particle layer on the substrate;
(C) irradiating the conductive particle layer with a first light source; and (d) irradiating the conductive particle layer with a second light source after step (c). ,
Including
The first light source has a ratio of energy of a wavelength equal to or less than a boundary wavelength less than that of the second light source, and the boundary wavelength is selected from wavelengths in a range of 250 nm to 450 nm.
A method for producing a conductive laminate having a substrate and a conductive film deposited on the substrate.
前記ポリマー基材のガラス転移温度が、３００℃以下であり、
前記導電性膜が、互いに結合している導電性材料の粒子を含み、且つ
導電性膜の表面抵抗値が、５００Ω／□以下である、
導電性積層体。 Having a polymer substrate and a conductive film deposited on the polymer substrate;
The glass transition temperature of the polymer substrate is 300 ° C. or less,
The conductive film includes particles of conductive material bonded to each other, and the surface resistance value of the conductive film is 500Ω / □ or less,
Conductive laminate.
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