JP2018181436A - Manufacturing method of electric conductive film and electric conductive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electric conductive film and a manufacturing method thereof.SOLUTION: An electric conductive film is made by forming many fine lines having hydrophilic group on a surface of a clear film, giving nanoparticles of coated copper, silver or gold on the many fine lines, and giving heat treatment.SELECTED DRAWING: None

Description

The present invention relates to a method of manufacturing a conductive film and a conductive film. More specifically, a plurality of fine lines having hydrophilic groups are formed on the surface of the transparent film, and then the surface-coated metal nanoparticles are applied onto the many fine lines, and then heat treatment is performed. The present invention relates to a method for producing a conductive film.

Heretofore, many types of conductive films have been proposed, and some of them have been put to practical use. A typical example is an ITO film in which a film of indium tin oxide (ITO: Indium Tin Oxide) is formed on the surface of a transparent film by a sputtering method or the like. This ITO film has excellent characteristics of transparency and conductivity, and is used in a wide range of fields, such as touch panels for smartphones and mobile phones. Due to the fact that ITO film is manufactured by PVD (Physical Vapor Deposition) method using a vacuum device and the size of the electrical resistance of ITO film, its application is not suitable for large screen use, and it is only small. It is limited to smartphones, which are screens, and touch panels for mobile phones.

On the other hand, the demand for touch panels is relatively large for large screens, so the development of large-sized conductive films compatible with these is being promoted. One of the methods of obtaining a large sized conductive film is a method of forming a large number of fine lines of a conductive metal on the surface of a transparent film. This method uses, for example, an ink (dope) containing a fine powder of a conductive metal (specifically, Cu, Ag, Au, etc.) on the surface of a transparent film, and is finely processed by a printing method such as gravure offset printing. This is a method of forming a wire, or a method of forming a fine line of a conductive metal by photolithography and etching of a metal film (specifically, Cu or the like) formed on the entire surface of a transparent film.
The fine lines of the conductive metal formed by these processing methods have a narrow width of one line of several μm, and usually about 5 μm. Further, among the above methods, the printing method such as the gravure offset printing method has a problem that the line width spreads as the number of processed sheets increases, and the processing tolerance is about ± 2 μm in the photolithography and the etching processing method. There is a risk of It is required that fine wires of conductive metal do not generate broken parts in the manufacturing process and that they do not break or break during use. Current printing methods such as gravure offset printing, photolithography, and etching methods are methods of forming fine lines of conductive metal without breaking, fine lines of conductive metal that do not break or break in practical use There have been technical limitations as an industrial method of forming a film on a large screen.
According to Japanese Patent Application Laid-Open No. 2008-101501, when forming a large number of conductive metal wires as a method not to lose the conductive characteristics as a whole even if disconnection or breakage of the conductive metal wires occurs in part, adjacent 2 Methods and conductive metal wire films have been proposed to form a reticulated pattern such that ~ 6, preferably 3-5, form a set of conductive lines.
This film is intended to thin the conductive metal wire to a certain extent, and to compensate for the conductive loss by the reticulation pattern even if partial breakage or breakage occurs.

Therefore, as a means for forming a fine line of a conductive metal on the surface of a transparent film, the present inventors have researched methods other than printing such as gravure offset printing, photolithography and etching. As one of the methods, we focused on the electroless plating method. The method of metal plating on a plastic surface by electroless plating is a method known per se. This method is often intended to form a film on a plastic surface by metal plating, and is not intended to form metal fine lines in a precisely designed pattern.
The inventors of the present invention have found that the surface of the transparent film is usually hydrophobic, and a pattern of hydrophilic fine lines can be formed on this surface, and if the catalyst can be deposited on the hydrophilic fine lines, the fine lines are formed. The following findings were obtained as a result of repeated research based on the presumption that it is possible to apply a fine line of conductive metal.
(I) When a surface of a transparent film having a hydrophobic surface is irradiated with ultraviolet light of a constant wavelength through a photomask, a pattern of many fine lines having a hydrophilic group is formed (ii) formation The catalyst can be easily applied onto the fine lines (iii) A fine line pattern of many conductive metals can be formed on the transparent film if electroless plating is performed on the fine line pattern to which the catalyst is applied. And (iv) the thus-formed conductive film has a fine line pattern of a conductive metal with a high precision and minimal breakage or breakage even if the fine line is thin.

Based on the above findings, the inventor of the present invention has made it clear that “(1) the surface of a transparent film having a hydrophobic surface is
When irradiated with sky ultraviolet light, a large number of fine particles having hydrophilic groups on the surface of the transparent film
A step of obtaining an ultraviolet light irradiation film in which a ray is formed (ultraviolet light irradiation step),
(2) A step of applying a catalyst on many fine lines of the obtained ultraviolet light irradiated film
(Catalyst application step) and
(3) Next, conductive metal plating process is performed on a large number of fine lines to which the obtained catalyst is applied.
Conductive film characterized in that it comprises a process (plating process) for applying
Manufacturing method. "
Proposed as a heading (Japanese Patent Application No. 2016-015837).
The inventor has conducted research on further improvement in the above-described previously proposed method. As a result, in the catalyst application step in the above method, "surface-coated metal nanoparticles" are used instead of "catalyst" and then heat treatment is applied to form on the surface of the transparent film, metal nanoparticles. The present invention has been found out that a large number of fine lines on which a conductive metal film is laminated are formed.
Thus, according to the present invention, the following method for producing a conductive film and the conductive film are provided.
1. (1) True to the surface of a transparent film having a hydrophobic surface through a photomask
When irradiated with sky ultraviolet light, a large number of fine particles having hydrophilic groups on the surface of the transparent film
A step of obtaining an ultraviolet light irradiation film in which a ray is formed (ultraviolet light irradiation step),
(2) Gold coated on many fine lines of the obtained ultraviolet light irradiated film
Process of applying a metal nanoparticle (metal nanoparticle application process) and
(3) Subsequently, a large number of fine particles to which the obtained surface-coated metal nanoparticles are applied
Conduction characterized by comprising a step of subjecting a thin line to a heat treatment (heat treatment step)
Film manufacturing method.
2. Said vacuum ultraviolet light has a wavelength of 150 to 200 nm;
How to make a film.
3. The transparent film is made of polyethylene terephthalate (PET), polyethylene
(PEN), polycarbonate (PC), polymethyl methacrylate
(PMMA), polycycloolefin (PCO) or polyparaxy
A film formed of rylene (PPX) or the above-mentioned 1 which is a composite film
The manufacturing method of the electroconductive film as described.
4. The fine line is made of the conductive film according to the above 1 having a width of 1 to 50 μm.
How to make.
5. The plurality of fine lines are separated by a gap (the distance between the centers of two adjacent fine lines)
The method for producing a conductive film according to 1 above, wherein the thickness is 5 to 3000 μm.
6. The metal nanoparticles are formed of copper (Cu), silver (Ag), or gold (Au)
The manufacturing method of the electroconductive film of said 1 which is an expanded nanoparticle.
7. The metal nanoparticles have an alkylamine or alkylamine and an oil on the surface.
The conductive according to 1 above, which is a metal nanoparticle coated with a film containing fatty acid
How to make a film.
8. The metal nanoparticles may have an average particle size of 3 nm to 30 nm.
Method of producing a conductive film.
9. A transparent film having a hydrophobic surface, having hydrophilic groups on the surface
A large number of fine lines are formed and formed on the fine lines from metal nanoparticles
An electroconductive film characterized in that the electroconductive metal film is laminated.

According to the present invention, there is provided a conductive film having a pattern of fine lines of a large number of conductive metal films formed of metal nanoparticles. The fine line of the conductive metal film in this conductive film is obtained by applying the metal nanoparticles coated on the surface to the surface of the fine line of the ultraviolet light irradiated film and further heat treatment, so the fine line of the conductive metal film is fine. The wire is precise and there are very few breaks and breakages. Therefore, it can be advantageously used as a conductive film. For example, it can be effectively used as a material for large-screen touch panels, EL lights, electromagnetic wave shield films, and heating elements by utilizing its characteristics.

JP, 2013-54708, A (patent 5734799)

As a transparent film which is a base film of the conductive film of the present invention, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polymethyl methacrylate (PMMA), polycycloolefin (PCO) or A film formed of polyparaxylylene (PPX) can be suitably used. Of these, films made of PET, PEN, PCO or PC are particularly preferred. These transparent films may be uniaxially or biaxially stretched, and the thickness thereof is 25 to 300 μm, preferably 38 to 250.
μm is advantageous.
The transparent film described above usually exhibits hydrophobicity on its surface, but the transparent film described above may be coated with a layer having hydrophobicity to improve its properties. It may be a laminate of the above-mentioned transparent film and another transparent substrate. In the present invention, to be hydrophobic with respect to the surface of the transparent film means that the characteristic value of the wetting tension of the surface is 40 mN / m or less, preferably 37 mN / m or less. This "mN / m" unit may be expressed as "dyn / cm".

According to the method of the present invention, vacuum ultraviolet light is irradiated to the surface of a transparent film having a hydrophobic surface through a photomask to form a large number of fine lines having a hydrophilic group on the surface. At this time, in the photomask, the width of the fine line having the formed hydrophilic group is 1 to
The width of the UV irradiation should be designed to be 50 μm, preferably 1 to 40 μm, particularly preferably 1 to 30 μm.
The wavelength of vacuum ultraviolet light may be in the range of 150 to 200 nm. In addition, the photomask has a gap between many fine lines (a distance between the center lines of adjacent fine lines) of 5 to
It is desirable to be designed to be 3000 μm, preferably 10 to 2500 μm.
It is important that vacuum ultraviolet light irradiation is such that the proportion of hydrophilic groups in the formed fine line is sufficiently hydrophilic. Here, to be hydrophilic means that the characteristic value of the wetting tension is 50.
It is desirable that mN / m or more, preferably 55 mN / m to 65 mN / m.
The rate of irradiation of vacuum ultraviolet light for forming hydrophilic fine lines also changes its preferable value depending on the rate of hydrophobicity of the surface of the transparent film before irradiation. That is, the characteristic value of the hydrophilic wetting tension of the fine line of the film after irradiation is 10mN / m or more, preferably 15mN / m or more, with respect to the value of the characteristic of the wetting tension of the hydrophobic film before irradiation. It is advantageous to irradiate vacuum ultraviolet light, as it occurs.

In the present invention, metal nanoparticles are applied to a transparent film on which hydrophilic fine lines are formed, and then heat treatment is performed. The metal nanoparticle application and heat treatment are methods of applying and heating metal nanoparticles on the surface of fine lines by the following method.
The metal nanoparticles used to apply the metal nanoparticles on the many fine lines of the ultraviolet light irradiated film are nanoparticles formed of copper (Cu), silver (Ag), or gold (Au), Preferred are copper or silver nanoparticles, and most preferred are copper nanoparticles. The metal nanoparticles suitably have an average particle size of 3 nm to 30 nm, and more preferably have an average particle size of 5 nm to 25 nm. Since metal nanoparticles tend to aggregate by themselves, those coated on the surface are used to prevent aggregation. At that time, as a coating material, (a) primary or secondary alcohol having 3 to 6 carbon atoms, or a derivative of these alcohols, (b) polyvinyl pyrrolidone, (c) alkylamine, (d) alkyl as a coating material Mixtures of amines and fatty acids and the like are used. Of these, alkylamines or mixtures of alkylamines and fatty acids are preferred.
The metal nanoparticles coated with the surface are applied onto a large number of fine lines of an ultraviolet light irradiated film (metal nanoparticle application step) and then heated by a heat treatment step, the coating material used for the coating is Degraded or removed.

Thus, a transparent film is obtained in which a large number of fine lines are formed by laminating conductive metal films formed of metal nanoparticles having a line width of 1 to 50 μm. The fine lines formed on the film have a width of 1 to 50 μm, preferably 1 to 30 μm, but according to the present invention they are formed from extremely thin metal nanoparticles having a width of 1 to 10 μm, in particular 1 to 5 μm. The fine lines of the resulting conductive metal film are characterized in that a conductive film formed by patterning in a large number can be obtained precisely and without breakage or breakage.
The fine lines of the conductive metal film formed of a large number of metal nanoparticles may be linear, may be corrugated, or may be a combination of linear and corrugated. The gap distance may be 5 to 3000 μm, preferably 10 to 2500 μm.
As described above, the conductive film of the present invention is a film in which fine lines of a conductive metal film formed of a large number of metal nanoparticles are formed in a linear and substantially parallel pattern on a film surface. is there. However, when actually used as a conductive film, a large number of fine lines of a conductive metal film formed of (a) metal nanoparticles may be used as independent conductive lines. Also, (b) adjacent 2 to 6, preferably 3 to 5 may be used as a set of conductive lines, and (c) adjacent 2 to 6, preferably 3 to 5 one. The fine lines of the conductive metal film formed of adjacent metal nanoparticles in one set of conductive lines may form a reticulated pattern.

実施例１〜３の試験用フィルム面は、真空紫外光照射後、ぬれ張力が増加し、水接
触角が低下した。これは、真空紫外光照射により親水性基が導入され、ぬれ張力が増
加したことを示唆する。
一方、比較例１の試験用フィルム面は、真空紫外光照射前と照射後で、ぬれ張力、
水接触角ともに、ほとんど変化しなかった。

実施例４および比較例２
［銅ナノ粒子付与液］
銅ナノ粒子付与液を以下の手順で調整した。
酢酸銅（５．４６ｇ）をエチレングリコール（６０ｍＬ）に溶解させ、酢酸銅溶液を
調整した。また、１−アミノ−２−プロパノール（２３．２ｍＬ）をエチレングリコ
ール（６０ｍＬ）に溶解させ、１−アミノ−２−プロパノールの溶液を調整した。上
記酢酸銅溶液に、上記１−アミノ−２−プロパノールの溶液を加えると、錯形成に伴
い溶液は濃い青色に変化した。
以下のこれを「原料溶液」とする。
原料溶液を攪拌しながら空気雰囲気下で２５℃において、銅モル換算で約１５倍量
のヒドラジン（１４．５８ｍＬ）を添加した。ヒドラジンの添加直後に、原料溶液か
ら大量の気泡が発生して、瞬時に赤みのある黒色へと変化した。次いで、空気雰囲気
下で24時間放置し、銅ナノ粒子分散液を調整した。
Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡ）５０ｍＬを別途用意した。ＤＭＡに対し
て銅ナノ粒子分散液２５ｍＬを液滴が見える程度にゆっくりと滴下して混合溶液を
調整した。当該混合溶液を、数分間大気中に放置して、空気にさらしたところ、懸濁
した。懸濁した混合溶液の遠心分離を行い、銅ナノ粒子を沈殿させた。溶液から上澄
みを除去し、銅ナノ粒子沈殿物を採取して、１４ｍＬのＤＭＡを添加した。次いで、
ボルテックスミキサーを用いて銅ナノ粒子沈殿物をＤＭＡ中に分散させて洗浄を行
った。銅ナノ粒子のＤＭＡ分散液の遠心分離を行い、銅ナノ粒子を沈殿させた。上澄
みを除去し、残った銅ナノ粒子沈殿物に対して、２０ｍＬのトルエンを添加して、ボ
ルテックスミキサーを用いて分散させて洗浄を行った。銅ナノ粒子のトルエン分散液
の遠心分離を行い、銅ナノ粒子を沈殿させた。上澄みを除去し残った銅ナノ粒子沈殿
物に対して、２０ｍＬのヘキサンを添加して、ボルテックスミキサーを用いて分散さ
せて洗浄を行った。銅ナノ粒子のヘキサン分散液の遠心分離を行い、銅ナノ粒子を沈
殿させた。上澄みを除去して銅ナノ粒子を分離し、洗浄を完了した。
銅ナノ粒子に対して、プロピレングリコールとグリセロールとの１：１（体積比）
の混合溶媒を、銅の含有量が４０重量％になるように添加した。混合溶媒添加後、上
層に浮上したヘキサンを除去した。ボルテックスミキサーを用いて銅ナノ粒子を分散
させ、銅ナノ粒子に残留していたヘキサンを分離除去した。次いで、減圧乾燥を３分
間行い、分散液中のヘキサンを全て除去した。以上の操作により、銅ナノ粒子付与液
を得た。
［試験用フィルム］
東洋包材株式会社製ハードコートフィルム「ＳＨ−６１８８−Ｈ２５Ａ／ＳＰ２」
の未処理面に、KISCO株式会社にて、ポリパラキシリレン樹脂コーティングを行っ
た。ポリパラキシリレン樹脂コーティング面を実施例４の試験用フィルム面として用
いた。
東レ株式会社製ポリプロピレンフィルム「トレファンＢＯ ＃５０−２５００Ｈ」
の片面を比較例２の試験用フィルム面として用いた。
［紫外光照射、銅ナノ粒子付与、加熱処理］
実施例４および比較例２の試験用フィルム面に真空紫外光（１５０−２００ｎｍ）
を、フォトマスク（クロムマスク、基板：信越石英株式会社製ＳＵＰＲＡＳＩＬ−
Ｆ３１０、厚さ２．３ｍｍ）越しに、5分間照射した。
次に銅ナノ粒子付与液を用いて、バーコーターにより実施例４および比較例２の試
験用フィルム面に塗布した。
実施例４の試験用フィルム面は、いずれも真空紫外光の透過部のみ銅ナノ粒子が付
与されており、真空紫外光の遮蔽部には銅ナノ粒子が付与されていないことが確認さ
れた。
一方、比較例２の試験用フィルム面は、真空紫外光の透過部、遮蔽部にかかわらず
銅ナノ粒子が付与されなかった。
次に、実施例４の銅ナノ粒子を付与した試験用フィルムを、窒素の流量１ｍＬ／
ｍｉｎの条件下で、８５℃で１時間３０分乾燥させた。次いで、窒素の流量１ｍＬ／
ｍｉｎの条件下で、１５０℃で１５分間加熱処理し、銅ナノ粒子を焼結させて、銅膜
を形成した。銅膜の線幅は約５μm、銅膜の厚さは約０．１μmであった。

実施例５〜７及び比較例３
［銀ナノ粒子付与液］
銀ナノ粒子付与液を以下の手順で調整した。
ｎ−オクチルアミン４．３２ｇ、ｎ−ドデシルアミン１．２４８ｇを混合し、この混
合液にシュウ酸銀６．０８ｇを加え、１０分間攪拌し、シュウ酸イオン・アルキルア
ミン・銀錯化合物を調整した。これを１００℃で６０分間加熱攪拌すると、青色光沢
を呈する懸濁液へと変化した。これにメタノール１０ｍＬを加え、遠心分離により得
られた沈殿物を自然乾燥すると、青色光沢の銀ナノ粒子４．５０ｇが得られた。
銀ナノ粒子を、銀の含有量が４０重量％になるように、ｎ−ブタノールとｎ−オク
タンの混合溶媒に分散させ、銀ナノ粒子付与液を得た。
［試験用フィルム］
帝人株式会社製「ピュアエース Ｃ１１０−１００」の片面を実施例５の試験用フ
ィルム面として用いた。
グンゼ株式会社製「Ｆ１フィルム Ｆ１−ＩＳＯ−１００−Ｔ−０」の片面を実施
例６の試験用フィルム面として用いた。
東洋包材株式会社製ハードコートフィルム「ＳＨ−６１８８−Ｈ２５Ａ／ＳＰ２」
の未処理面に、KISCO株式会社にて、ポリパラキシリレン樹脂コーティングを行っ
た。ポリパラキシリレン樹脂コーティング面を実施例７の試験用フィルム面として用
いた。
東レ株式会社製ポリプロピレンフィルム「トレファンＢＯ ＃５０−２５００Ｈ」
の片面を比較例３の試験用フィルム面として用いた。
［紫外光照射、銀ナノ粒子付与、加熱処理］
実施例５〜７および比較例３の試験用フィルム面に真空紫外光（１５０−２００
ｎｍ）を、フォトマスク（クロムマスク、基板：信越石英株式会社製ＳＵＰＲＡＳＩ
Ｌ−Ｆ３１０、厚さ２．３ｍｍ）越しに、5分間照射した。
次に銀ナノ粒子付与液を用いて、スピンコートにより実施例５〜７よび比較例３の
試験用フィルム面に塗布した。
実施例５〜７の試験用フィルム面は、いずれも真空紫外光の透過部のみ銀ナノ粒子
が付与されており、真空紫外光の遮蔽部には銀ナノ粒子が付与されていないことが確
認された。
一方、比較例３の試験用フィルム面は、真空紫外光の透過部、遮蔽部にかかわらず
銀ナノ粒子が付与されなかった。
次いで、実施例５〜７の銀ナノ粒子を付与した試験用フィルムを１２０℃で４０分
間加熱処理し、銀ナノ粒子を焼結させて、銀膜を形成した。銀膜の線幅は約５μm、
銀膜の厚さは約０．１μmであった。


The conductive film of the present invention is excellent in transparency, and the aperture ratio is in the range of 85 to 99%, preferably 87 to 99%. Here, the aperture ratio is defined as 100% of the total area of the effective region (film) including the portion where fine lines of the conductive metal film formed of metal nanoparticles are formed and the portion where the fine line is not formed. It refers to the ratio of the area excluding the total area occupied by the fine lines of the conductive metal film formed of nanoparticles.
According to the present invention, it is possible to easily form fine lines of a conductive metal film formed of a large number of metal nanoparticles on a large size film suitable for a large screen. That is, it becomes possible to provide a large sized conductive film without any problem.
The present invention can be used for small to large, preferably large-sized touch panels, EL lights, electromagnetic wave shielding films, or heating elements using conductive films.
The present invention will be described in detail by way of the following examples.


Examples 1 to 3 and Comparative Example 1
[Test film]
One side of “Pure Ace C110-100” manufactured by Teijin Limited was used as a test film surface of Example 1.
One side of “F1 film F1-ISO-100-T-0” manufactured by Gunze Co., Ltd. was used as the test film side of Example 2.
Toyo Coat Co., Ltd. hard coat film "SH-6188-H25A / SP2"
On the untreated side of the above, polyparaxylylene resin coating was applied at KISCO Co., Ltd. The polyparaxylylene resin coated surface was used as the test film surface of Example 3.
Toray Industries, Inc. polypropylene film "Torrefan BO # 50-2500H"
The one side of was used as the test film side of Comparative Example 1.
[Evaluation of irradiation effect of vacuum ultraviolet light]
Vacuum ultraviolet light (150-200 nm) was made of synthetic quartz glass (SU
The test film surface was irradiated for 5 minutes through PRASIL-F310 (thickness 2.3 mm).
The contact angle of water on the vacuum ultraviolet light irradiated portion of the test film surface was measured.
Further, the wet tension of the vacuum ultraviolet light irradiated portion of the film surface for test was measured using the mixture for the wet tension test.
The evaluation results of the irradiation effect of vacuum ultraviolet light of Examples 1 to 3 and Comparative Example 1 are shown in the following table.

The test film surfaces of Examples 1 to 3 had increased wetting tension and decreased contact angle with water after irradiation with vacuum ultraviolet light. This suggests that the hydrophilic group was introduced by vacuum ultraviolet light irradiation and the wetting tension was increased.
On the other hand, the test film surface of Comparative Example 1 had a wetting tension, before and after vacuum ultraviolet light irradiation.
There was almost no change in the water contact angle.

Example 4 and Comparative Example 2
[Copper nanoparticle application liquid]
The copper nanoparticle application liquid was adjusted in the following procedure.
Copper acetate (5.46 g) was dissolved in ethylene glycol (60 mL) to prepare a copper acetate solution. Further, 1-amino-2-propanol (23.2 mL) was dissolved in ethylene glycol (60 mL) to prepare a solution of 1-amino-2-propanol. When the above solution of 1-amino-2-propanol was added to the above copper acetate solution, the solution turned deep blue as the complex formation.
The following is referred to as a "raw material solution".
About 15 volumes of hydrazine (14.58 mL) in terms of molar copper was added at 25 ° C. under air atmosphere while stirring the raw material solution. Immediately after the addition of hydrazine, a large amount of air bubbles were generated from the raw material solution, and the color instantly turned to reddish black. Then, it was left to stand in an air atmosphere for 24 hours to prepare a copper nanoparticle dispersion.
50 mL of N, N-dimethylacetamide (DMA) was separately prepared. A mixed solution was prepared by slowly dropping 25 mL of a copper nanoparticle dispersion solution to DMA so that the droplets could be seen. The mixed solution was left in the air for several minutes, exposed to air, and suspended. The suspended mixed solution was centrifuged to precipitate copper nanoparticles. The supernatant was removed from the solution, the copper nanoparticle precipitate was collected, and 14 mL of DMA was added. Then
The copper nanoparticle precipitate was dispersed in DMA and washed using a vortex mixer. Centrifugation of copper nanoparticles in DMA dispersion was carried out to precipitate copper nanoparticles. The supernatant was removed, and 20 mL of toluene was added to the remaining copper nanoparticle precipitate, dispersed using a vortex mixer, and washed. The toluene dispersion of copper nanoparticles was centrifuged to precipitate copper nanoparticles. The supernatant was removed and the remaining copper nanoparticle precipitate was washed by adding 20 mL of hexane and dispersing using a vortex mixer. The hexane dispersion of copper nanoparticles was centrifuged to precipitate copper nanoparticles. The supernatant was removed to separate the copper nanoparticles and the washing was completed.
1: 1 (volume ratio) of propylene glycol and glycerol to copper nanoparticles
Mixed solvent was added such that the copper content was 40% by weight. After the mixed solvent was added, the hexane floated on the upper layer was removed. The copper nanoparticles were dispersed using a vortex mixer to separate and remove hexane remaining in the copper nanoparticles. Then, drying under reduced pressure was performed for 3 minutes to remove all hexane in the dispersion. A copper nanoparticle-imparted solution was obtained by the above operation.
[Test film]
Toyo Coat Co., Ltd. hard coat film "SH-6188-H25A / SP2"
On the untreated side of the above, polyparaxylylene resin coating was applied at KISCO Co., Ltd. The polyparaxylylene resin coated surface was used as the test film surface of Example 4.
Toray Industries, Inc. polypropylene film "Torrefan BO # 50-2500H"
The one side of was used as the test film side of Comparative Example 2.
[UV light irradiation, copper nanoparticle application, heat treatment]
Vacuum ultraviolet light (150-200 nm) on the test film surface of Example 4 and Comparative Example 2
The photomask (chrome mask, substrate: SUPRASIL-Shin-Etsu Quartz Co., Ltd.
It irradiated for 5 minutes over F310 and thickness 2.3mm.
Next, it was applied to the test film surface of Example 4 and Comparative Example 2 by a bar coater using a copper nanoparticle application liquid.
In all of the test film surfaces in Example 4, it was confirmed that copper nanoparticles were applied only to the vacuum ultraviolet light transmitting portion, and no copper nanoparticles were applied to the vacuum ultraviolet light shielding portion. The
On the other hand, no copper nanoparticles were applied to the test film surface of Comparative Example 2 regardless of the vacuum ultraviolet light transmitting part and the shielding part.
Next, the test film provided with the copper nanoparticles of Example 4 was subjected to a nitrogen flow of 1 mL /
It was dried at 85 ° C. for 1 hour and 30 minutes under the conditions of min. Then, the nitrogen flow rate 1 mL /
Heat treatment was performed at 150 ° C. for 15 minutes under min conditions to sinter the copper nanoparticles to form a copper film. The line width of the copper film was about 5 μm, and the thickness of the copper film was about 0.1 μm.

Examples 5 to 7 and Comparative Example 3
[Silver nanoparticle application liquid]
The silver nanoparticle application liquid was adjusted in the following procedure.
4.32 g of n-octylamine and 1.248 g of n-dodecylamine are mixed, and 6.08 g of silver oxalate is added to the mixed solution, and the mixture is stirred for 10 minutes to prepare an oxalate-alkylamine-silver complex compound. did. When this was heated and stirred at 100 ° C. for 60 minutes, it turned into a suspension exhibiting a blue gloss. To this, 10 mL of methanol was added, and the precipitate obtained by centrifugation was naturally dried to obtain 4.50 g of blue glossy silver nanoparticles.
Silver nanoparticles were dispersed in a mixed solvent of n-butanol and n-octan so that the content of silver was 40% by weight, to obtain a silver nanoparticle-carrying liquid.
[Test film]
One side of “Pure Ace C110-100” manufactured by Teijin Limited was used as a test film surface of Example 5.
One side of “F1 film F1-ISO-100-T-0” manufactured by Gunze Co., Ltd. was used as a test film surface of Example 6.
Toyo Coat Co., Ltd. hard coat film "SH-6188-H25A / SP2"
On the untreated side of the above, polyparaxylylene resin coating was applied at KISCO Co., Ltd. The polyparaxylylene resin coated surface was used as the test film surface of Example 7.
Toray Industries, Inc. polypropylene film "Torrefan BO # 50-2500H"
The one side of was used as the test film side of Comparative Example 3.
[UV light irradiation, addition of silver nanoparticles, heat treatment]
Vacuum ultraviolet light (150-200) was applied to the test film surfaces of Examples 5 to 7 and Comparative Example 3
nm), photomask (chrome mask, substrate: SUPRASI manufactured by Shin-Etsu Quartz Co., Ltd.)
It irradiated for 5 minutes through L-F310 (2.3 mm in thickness).
Next, it apply | coated to the film surface for a test of Examples 5-7 and the comparative example 3 by spin coating using silver nanoparticle application | coating liquid.
It was confirmed that silver nanoparticles were applied only to the transmitting part of vacuum ultraviolet light in each of the test film surfaces in Examples 5 to 7, and that silver nanoparticles were not applied to the shielding part of vacuum ultraviolet light. It was done.
On the other hand, silver nanoparticles were not applied to the test film surface of Comparative Example 3 regardless of the vacuum ultraviolet light transmitting part and the shielding part.
Subsequently, the film for a test provided with the silver nanoparticle of Examples 5-7 was heat-processed at 120 degreeC for 40 minutes, the silver nanoparticle was sintered, and the silver film was formed. The line width of the silver film is about 5 μm,
The thickness of the silver film was about 0.1 μm.

Claims (9)

(1) Vacuum ultraviolet through a photomask on the surface of a transparent film having a hydrophobic surface
When irradiated with light, many fine lines having hydrophilic groups are formed on the surface of the transparent film
Obtaining an irradiated ultraviolet light irradiation film (ultraviolet light irradiation process),
(2) Surface-coated metal nano on many fine lines of the obtained ultraviolet light irradiated film
Step of applying particles (step of applying metal nanoparticles) and (3) subsequently to the obtained surface-coated metal nanoparticles are applied to a large number of fine lines
A conductive film characterized by comprising a step of applying a heat treatment (heat treatment step)
Manufacturing method.
The method for producing a conductive film according to claim 1, wherein the vacuum ultraviolet light has a wavelength of 150 to 200 nm.
The transparent film is made of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC) or polymethyl methacrylate (P).
The method for producing a conductive film according to claim 1, which is a film formed of MMA), polycycloolefin (PCO) or polyparaxylylene (PPX), or a composite film.
The conductive film according to claim 1, wherein the fine line has a width of 1 to 50 μm.
Production method.
The plurality of fine lines have a gap distance (a distance between the centers of two adjacent fine lines) of 5
The method for producing a conductive film according to claim 1, which is 3000 μm.
The method for producing a conductive film according to claim 1, wherein the metal nanoparticles are nano particles formed of copper (Cu), silver (Ag), or gold (Au).
The method for producing a conductive film according to claim 1, wherein the metal nanoparticles are metal nanoparticles whose surface is coated with an alkylamine or a film containing an alkylamine and a fatty acid.
The method for producing a conductive film according to claim 1, wherein the metal nanoparticles have an average particle size of 3 nm to 30 nm.
A transparent film having a hydrophobic surface, on the surface of which a large number of fine lines having hydrophilic groups are formed, and on the fine lines, a conductive metal film formed of metal nanoparticles is laminated. A conductive film characterized by