JP4631221B2 - Method for producing functional film - Google Patents

Description

【０１０５】
実施例１〜８及び比較例１〜２の測定結果を表１に示す。実施例１〜８の導電性フィルムはいずれも、電気抵抗値が低く、圧縮層の強度も強く、圧縮層と支持体フィルムとの密着性にも優れていた。
実施例１〜６から、プレス圧が高いほど導電性がより良好となり、圧縮層強度が強く、圧縮層と支持体フィルムとの密着性も強固となリ、セロハンテープの粘着剤が導電面に残ってしまうほどであった。
樹脂を含む導電層よりも樹脂を含まない導電層の方が、より優れた導電性が得られた。また、実施例１〜８の導電性フィルムはいずれも、可視光透過率の点においても透明性にも優れていた。
【０１０６】
これに対して、比較例１のものは、圧縮工程を行っていないので、実施例１〜６のものに比べ、電気抵抗値が高い。
比較例２のものは、従来のように圧縮しなくても塗膜が形成できるようにバインダー樹脂を多量に用いた。バインダー樹脂を多量に用いたので塗膜の強度は十分であったが、電気抵抗値が高かった。
【０１０７】
［実施例９：ＩＴＯ／ＴｉＯ₂ 多層機能性層の形成］
この実施例は、まず、ＩＴＯ圧縮層を支持体上に転写形成し、次に、ＩＴＯ圧縮層上にＴｉＯ₂ 圧縮層を転写形成した例である。本発明の製造方法における多層圧縮層の形成を説明するための図４及び図５を参照して説明する。
【０１０８】
１．第１圧縮層の形成
実施例２と同様にして、支持体(1) 上に第１圧縮層としてＩＴＯ微粒子圧縮層(4I)を形成した。圧縮圧力：３４７Ｎ／ｍｍ² 。
【０１０９】
２．第２圧縮層の形成
（転写支持体）
実施例１で用いたのと同じＰＥＴベースフィルム(2a)上にシリコーンハードコート層(2b)が形成された転写支持体(2) を用いた。
【０１１０】
（転写前駆フィルムの作成）
一次粒径が３０〜７０ｎｍのＴｉＯ₂ 微粒子１００重量部にエタノール９００重量部を加え、メディアをジルコニアビーズとして分散機にて分散した。得られた塗液を転写支持体(2) のハードコート層(2b)上に、バーコーターを用いて塗布し、５０℃の温風を送って乾燥し、ＴｉＯ₂ 微粒子含有層(P4II)を形成した。このようにして、転写前駆フィルム(5) を得た。ＴｉＯ₂ 微粒子含有層(P4II)の厚みは０．７μｍであった。
【０１１１】
（第２層圧縮層の形成）
図４に示すように、ＩＴＯ圧縮層(4I)が形成された支持体(1) と、ＴｉＯ₂ 微粒子含有層(P4II)が形成された転写前駆フィルム(5) とを、ＩＴＯ圧縮層(4I)とＴｉＯ₂ 微粒子含有層(P4II)とが接するように重ね合わせ、ロールプレス機を用いて挟み圧縮した。圧縮圧力：３４７Ｎ／ｍｍ² 。圧縮後に、転写支持体(2) を支持体(1) 上のＴｉＯ₂ 微粒子の圧縮層(4II) から剥離した。このようにして、図５に示す層構成の支持体(1) 上にＩＴＯ微粒子の圧縮層(4I)及びＴｉＯ₂ 微粒子の圧縮層(4II) が形成されたＩＴＯ／ＴｉＯ₂ フィルムを得た。ＩＴＯ微粒子圧縮層(4I)の厚みは１．０μｍであり、ＴｉＯ₂ 微粒子圧縮層(4II) の厚みは０．５μｍであった。剥離は容易に行われ、ＴｉＯ₂ 微粒子圧縮層(4II) 面が完全に露出していた。
【０１１２】
（９０度ピール試験）
上記９０度ピール試験の結果、セロハンテープを剥がすのに６Ｎ／１２ｍｍの力を要した。ピール試験後の圧縮層(4II) 表面を調べたところ、セロハンテープの粘着剤が付着し、ＩＴＯ圧縮層(4I)とＴｉＯ₂ 圧縮層(4II) との間の剥がれもなかった。剥がしたセロハンテープの粘着面を調べたところ、粘着性があった。
従って、圧縮層(4I)(4II) の強度は６Ｎ／１２ｍｍ以上であった。
得られたＩＴＯ／ＴｉＯ₂ 多層機能性フィルムは、太陽電池として利用できる。
【０１１３】
［実施例１０：転写用機能性フィルムの作成］
この実施例は、本発明の方法により得られた圧縮されたＩＴＯフィルムを用いて、転写用ＩＴＯフィルムを作成し、転写用ＩＴＯフィルムのＩＴＯ圧縮層をポリカーボネート基板上に転写した例である。図６〜図８を参照して説明する。
【０１１４】
１．圧縮層の形成
（支持体）
７５μｍ厚のＰＥＴフィルムＨＳＬ（帝人デュポンフィルム製）(1) 上に、シリコーンハードコート液ＫＰ−８５４（信越化学工業（株）製）を塗布、乾燥し、２μｍ厚の未硬化のシリコーンハードコート層(H) を形成した。
【０１１５】
（転写前駆フィルムの作成）
実施例１で用いたのと同じＰＥＴベースフィルム(2a)上にシリコーンハードコート層(2b)が形成された転写支持体(2) を用いた。実施例１と同様にして、この転写支持体(2) のハードコート層(2b)上に、ＩＴＯ微粒子含有層(P4)を形成し、転写前駆フィルム(5) を得た。
【０１１６】
（圧縮層の形成）
シリコーンハードコート層(H) が形成された支持体(1) と、ＩＴＯ微粒子含有層(P4)が形成された転写前駆フィルム(5) とを、シリコーンハードコート層(H) とＩＴＯ微粒子含有層(P4)とが接するように重ね合わせ、ロールプレス機を用いて挟み圧縮した。圧縮圧力：３４７Ｎ／ｍｍ² 。圧縮後に、転写支持体(2) を支持体(1) 上のＩＴＯ微粒子の圧縮層(4) から剥離した。このようにして、図６に示す層構成の支持体(1) 上にシリコーンハードコート層(H) 及びＩＴＯ微粒子の圧縮層(4) が形成されたＩＴＯフィルムを得た。剥離は容易に行われ、ＩＴＯ微粒子圧縮層(4) 面が完全に露出していた。
次に、ＩＴＯフィルムを、１００℃の雰囲気下に１時間おいて、未硬化シリコーンハードコート層(H) を硬化させた。ＩＴＯ微粒子圧縮層(4) の厚みは１．０μｍであった。
【０１１７】
２．転写用機能性フィルムの作成
（接着剤層の形成）
アクリル樹脂１ＢＲ−３０５（固形分：３９．５％、大成化工（株）製）１００重量部に、紫外線硬化型樹脂ＳＤ−３１８（大日本インキ化学工業（株）製）９２重量部、メチルエチルケトン１３７重量部を加えて、接着剤層用塗布液とした。前記塗布液を、シリコーン剥離ＰＥＴフィルムＳ３１４(R) 上に塗布、乾燥して、１０μｍ厚の接着剤層(7) を形成した。
【０１１８】
上記１で得られたＩＴＯフィルムのＩＴＯ圧縮層(4) と、シリコーン剥離ＰＥＴフィルムＳ３１４(R) の接着剤層(7) とが接するように、両フィルムをラミネートした。このようにして、図７に示す層構成の転写用ＩＴＯフィルムを作成した。
【０１１９】
３．ポリカーボネート板への機能性層の付与
得られた転写用ＩＴＯフィルムのシリコーン剥離ＰＥＴフィルムＳ３１４(R) を剥がして、接着剤層(7) を露出させ、接着剤層(7) が２ｍｍ厚みのポリカーボネート板(6) に接するようにラミネーターにて貼り付けた。紫外線を照射して、接着剤層(7) を硬化させた。その後、支持体ＰＥＴフィルム(1) を剥がした。ポリカーボネート板(6) 上にＩＴＯ圧縮層(4) が形成され、ＩＴＯ圧縮層(4) 上には硬化したシリコーンハードコート層(H) が存在した。このようにして、図８に示すように、ポリカーボネート板(6) 上に、接着剤層(7) を介して、ＩＴＯ圧縮層(4) が付与された。
【０１２０】
実施例１〜８では、無機微粒子としてＩＴＯ微粒子をそれぞれ用いて、無機機能性フィルムを作製した例を示した。実施例９では、無機微粒子としてＩＴＯ微粒子及びＴｉＯ₂ 微粒子を用いて、ＩＴＯ／ＴｉＯ₂ 多層機能性フィルムを作製した例を示した。上記実施例と同様にして、ＷＯ₃ 微粒子、Ａｌ₂ Ｏ₃ 微粒子等の種々の性質を有する無機微粒子を用いて、種々の無機機能性層を作製することができる。
【０１２１】
実施例１０に示したように、本発明の方法により得られた機能性フィルムを用いて、転写用機能性フィルムを作成し、転写用機能性フィルムの機能性微粒子圧縮層を種々の基板上に転写することができる。板材のように可撓性に乏しい物体に均一厚みの機能性層を付与する場合に利点がある。
【０１２２】
前述の実施例はあらゆる点で単なる例示にすぎず、限定的に解釈してはならない。さらに、請求の範囲の均等範囲に属する変更は、すべて本発明の範囲内のものである。
【０１２３】
【発明の効果】
本発明によれば、機能性微粒子を含む塗料を転写支持体に塗布、乾燥して転写前駆フィルムを作成し、機能性層を形成すべき支持体と前記転写前駆フィルムとを重ね合わせて圧縮するという簡便な操作で機能性フィルムが得られる。本発明による機能性層は、十分な機械的強度を有すると共に、従来の塗布法におけるバインダー樹脂による弊害が解消され、その結果、目的とする機能がより向上する。
【０１２４】
本発明によれば、導電性塗料を転写支持体に塗布、乾燥して転写前駆フィルムを作成し、導電層を形成すべき支持体と前記転写前駆フィルムとを重ね合わせて圧縮するという簡便な操作で透明導電性フィルムが得られる。本発明による透明導電層は、導電性に優れ、透明性にも優れる。さらに、十分な機械的強度を有し、導電層と支持体との密着性も強固であり、長期間使用することが可能である。
【０１２５】
また、本発明の方法によれば、導電性フィルムの大面積化にも対応でき、装置が簡便で生産性が高く、低コストで透明導電膜を始め各種の機能性フィルムを製造できる。
【図面の簡単な説明】
【図１】 本発明の製造方法における圧縮層の形成を説明するための図である。
【図２】 実施例における９０度ピール試験を説明するための図である。
【図３】 本発明の製造方法で得られる機能性フィルムの一例を示す断面図である。
【図４】 本発明の製造方法における多層圧縮層の形成を説明するための図である。
【図５】 本発明の製造方法で得られる多層機能性層を有する機能性フィルムの一例を示す断面図である。
【図６】 本発明の製造方法で得られる機能性フィルムの一例を示す断面図である。
【図７】 本発明の製造方法で得られる機能性フィルムを用いて作成される転写用機能性フィルムの一例を示す断面図である。
【図８】 転写用機能性フィルムの機能性層が付与された物体の一例を示す断面図である。
【符号の説明】
(R1)(R2)：プレスロール
(G1)(G2)：ガイドローラ
(1) ：支持体
(2) ：転写支持体
(2a)：転写支持体ベース
(2b)：ハードコート層
(P4)：機能性微粒子含有層
(4) ：機能性微粒子圧縮層
(5) ：転写前駆フィルム
(6) ：対象物体
(7) ：接着剤層
(H) ：ハードコート層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a functional film having at least a functional layer comprising a compressed layer of functional fine particles on a support. In the present invention, the functional film includes both a functional film and a functional sheet. Moreover, what a support body is a metal is also contained in the functional film of this invention.
[0002]
The functional layer is a layer having a function, and the function means a function performed through a physical and / or chemical phenomenon. Functional layers include conductive layer, ultraviolet shielding layer, infrared shielding layer, magnetic layer, ferromagnetic layer, dielectric layer, ferroelectric layer, electrochromic layer, electroluminescence layer, insulating layer, light absorption layer, light selection Layers having various functions such as an absorption layer, a reflection layer, an antireflection layer, a catalyst layer, and a photocatalyst layer are included.
[0003]
In particular, the present invention relates to a method for producing a transparent conductive film having a transparent conductive layer. The transparent conductive layer can be used as a transparent electrode such as an electroluminescence panel electrode, an electrochromic element electrode, a liquid crystal electrode, a transparent surface heating element, and a touch panel, and can also be used as a transparent electromagnetic wave shielding layer.
[0004]
[Prior art]
Conventionally, functional layers made of various functional materials have been used for physical vapor deposition (PVD) methods such as vacuum deposition, laser ablation, sputtering, ion plating, and chemicals such as thermal CVD, photo CVD, and plasma CVD. Manufactured by chemical vapor deposition (CVD). These generally require a large-scale apparatus, and some are not suitable for forming a large-area film.
[0005]
It is also known to form a film by coating using a sol-gel method. The sol-gel method is suitable for forming a film having a large area, but in many cases, it is necessary to sinter the inorganic material at a high temperature after coating.
[0006]
For example, the transparent conductive layer is as follows. Currently, the transparent conductive layer is mainly produced by a sputtering method. There are various types of sputtering methods. For example, an inert gas ion generated by direct current or high frequency discharge in vacuum is accelerated and collided with the target surface, and atoms constituting the target are knocked out from the surface and deposited on the substrate surface. This is a method of forming a film.
The sputtering method is excellent in that a conductive layer having a low surface electrical resistance can be formed even if the surface has a relatively large area. However, there is a drawback that the apparatus is large and the film forming speed is slow. If the area of the conductive layer is further increased in the future, the apparatus will further increase. This causes a problem that technically the control accuracy must be increased, and a problem that the manufacturing cost increases from another viewpoint. Further, in order to compensate for the slow deposition rate, the number of targets is increased to increase the speed, but this is also a factor that increases the size of the apparatus.
[0007]
Attempts have also been made to produce a transparent conductive layer by a coating method. In the conventional coating method, a conductive paint in which conductive fine particles are dispersed in a binder solution is applied on a substrate, dried and cured, and a conductive layer is formed. The coating method has an advantage that a conductive layer having a large area can be easily formed, the apparatus is simple, the productivity is high, and the conductive layer can be manufactured at a lower cost than the sputtering method. In the coating method, when conductive fine particles come into contact with each other, an electric path is formed and conductivity is expressed. However, the conductive layer produced by the conventional coating method has a drawback that contact is insufficient, and the resulting conductive layer has a high electric resistance value (inferior in conductivity), and its application is limited.
[0008]
As a method for producing a transparent conductive layer by a conventional coating method, for example, in JP-A-9-109259, a coating composed of conductive powder and a binder resin is applied on a transfer plastic film and dried to form a conductive layer. First step, pressurizing the surface of the conductive layer to a smooth surface (5 to 100 kg / cm²), A second process of heating (70 to 180 ° C.), and a third process of laminating this conductive layer on a plastic film or sheet and thermocompression bonding is disclosed.
In this method, a large amount of binder resin is used (in the case of inorganic conductive powder, 100 to 500 parts by weight of conductive powder with respect to 100 parts by weight of binder, and in the case of organic conductive powder, binder 100 is used. Therefore, a transparent conductive layer having a low electric resistance value cannot be obtained.
[0009]
For example, JP-A-8-199096 discloses a coating material for forming a conductive layer which is made of tin-doped indium oxide (ITO) powder, a solvent, a coupling agent, a metal organic acid salt or an inorganic acid salt and does not contain a binder. The method of apply | coating to a board and baking at the temperature of 300 degreeC or more is disclosed. In this method, since no binder is used, the electric resistance value of the conductive layer is lowered. However, since it is necessary to perform a baking process at a temperature of 300 ° C. or higher, it is difficult to form a conductive layer on a support such as a resin film. That is, the resin film melts, carbonizes, or burns at a high temperature. Depending on the type of resin film, for example, a polyethylene terephthalate (PET) film may have a limit of 130 ° C.
[0010]
Japanese Patent No. 2999464 discloses a transparent conductive film comprising a paste obtained by dispersing ultrafine powder of ITO in a solvent together with a resin on a resin film, drying, and then rolling with a steel roll. A manufacturing method is disclosed.
[0011]
In JP-A-7-235220, a dispersion containing conductive fine particles such as ITO and containing no binder is applied on a glass substrate and dried slowly, and an overcoat made of silica sol is formed on the obtained ITO film. A method of applying a liquid and then performing drying or baking following drying is disclosed. According to this publication, the overcoat coating film made of silica sol is dried and cured and contracted, and the ITO fine particles in the ITO film are firmly brought into contact with each other by the curing and shrinkage stress at that time. If the contact between the ITO fine particles is insufficient, the electrical resistance of the conductive film is high. In order to obtain a large curing shrinkage stress, it is necessary to dry the overcoat coating film at a high temperature of 150 to 180 ° C. However, when the support is a resin film, the resin film is deformed by such a high temperature.
According to the publication, the overcoat made of silica sol also contributes to the bonding between the conductive film and the glass substrate. That is, the strength of the conductive film can be obtained by the overcoat made of silica sol. However, unless the overcoat solution is applied and cured and contracted, the electric resistance of the conductive film is high and the strength of the film is low. Furthermore, in order to improve the optical characteristics of the conductive film and reduce the surface resistance, it is necessary to dry slowly after applying the dispersion liquid of the conductive fine particles on the glass substrate. An overcoat film made of silica sol has a drawback that cracks occur when the film thickness is large.
[0012]
[Problems to be solved by the invention]
Against such a background, various functions are manifested while taking advantage of the coating method that it is easy to form a functional layer with a large area, the equipment is simple, the productivity is high, and the functional layer can be produced at low cost. It is desired to develop a method for obtaining a functional layer that can be obtained.
[0013]
Especially for the conductive layer, it is easy to form a conductive layer with a large area, the device is simple, the productivity is high, and the transparency of the electrical resistance value is low while taking advantage of the coating method that the conductive layer can be manufactured at a low cost. Development of a method for obtaining a conductive layer is desired.
[0014]
Then, the objective of this invention is providing the manufacturing method of the functional film which has a functional layer which can express the various functions by the apply | coating method.
[0015]
In particular, an object of the present invention is to provide a method for producing a transparent conductive film having a transparent conductive layer having a low electrical resistance value by a coating method. Furthermore, a method for producing a transparent conductive film that can form a conductive layer without requiring a high-temperature heating operation, and that can provide a uniform and uniform conductive layer, and a transparent conductive film that can cope with an increase in the area of the conductive layer. It is in providing the manufacturing method of.
[0016]
[Means for Solving the Problems]
Conventionally, in a coating method, a functional layer cannot be formed unless a large amount of binder resin is used, or if a binder resin is not used, a functional layer can be obtained unless the functional substance is sintered at a high temperature. It was considered impossible.
As for the conductive layer, the conductive layer cannot be formed unless a large amount of the binder resin is used, or if the binder resin is not used, the conductive layer cannot be obtained unless the conductive material is sintered at a high temperature. It was thought.
[0017]
However, as a result of intensive studies, the inventor has surprisingly been able to express various functions without compression using a large amount of binder resin and without firing at a high temperature and having mechanical strength by compression. We found that a functional layer was obtained. The present inventor has found that a transparent conductive layer having a low electrical resistance value can be obtained when a conductive material is used.
[0018]
That is, the present inventor applies a liquid in which functional fine particles are dispersed to a support and dries to form a functional fine particle-containing layer, and then compresses the functional fine particle-containing layer to compress the functional fine particles. It reached | attained the manufacturing method of the functional film which has a functional layer which consists of a compression layer of functional fine particles on a support body including forming a layer.
[0019]
As a result of further investigation, the present inventor first formed a functional fine particle-containing layer on a transfer support, and then transferred the functional fine particle-containing layer onto the support when the functional fine particle-containing layer was compressed. It has been found that a functional film having a functional layer composed of a compressed layer of functional fine particles can be obtained.
[0020]
  That is, the present invention applies a liquid in which functional fine particles are dispersed onto a transfer support and is dried to produce a transfer precursor film in which a functional fine particle-containing layer is formed on the transfer support.
  The support on which the functional layer is to be formed and the transfer precursor film are overlapped so that the support and the functional fine particle-containing layer are in contact with each other, and the functional fine particle-containing layer is formed.44 N / mm ² With the above compression forceCompression to form a compressed layer of functional fine particles on the support,
  It is a method for producing a functional film having at least a functional layer comprising a compressed layer of functional fine particles on a support, comprising peeling the transfer support from the compressed layer of functional fine particles.
[0021]
The present invention is the above-described method for producing a functional film, wherein the surface on which the functional layer of the support is to be formed is softer than the surface on which the functional fine particle-containing layer of the transfer support is to be formed.
[0022]
BookThe invention is the method for producing a functional film, wherein the functional fine particle-containing layer is compressed at a temperature at which the support and the transfer support are not deformed.
  This invention is a manufacturing method of the said functional film which compresses the said functional fine particle content layer using a roll press machine.
[0023]
The present invention is the method for producing a functional film, wherein the transfer support has a hard coat layer on the surface on which the functional fine particle-containing layer is to be formed.
The present invention is the method for producing the functional film, wherein the support is a resin film.
[0024]
The present invention is the method for producing the functional film, wherein the functional fine particles are selected from inorganic fine particles.
In the present invention, the functional layer includes a conductive layer, an ultraviolet shielding layer, an infrared shielding layer, a magnetic layer, a ferromagnetic layer, a dielectric layer, a ferroelectric layer, an electrochromic layer, an electroluminescence layer, an insulating layer, and a light absorption layer. The method for producing a functional film, wherein the functional film is selected from the group consisting of a light selective absorption layer, a reflection layer, an antireflection layer, a catalyst layer, and a photocatalyst layer.
[0025]
When the functional layer is a conductive layer, conductive fine particles are used as the functional fine particles. The present invention is a method for producing a conductive film, wherein a conductive layer is formed using conductive fine particles as the functional fine particles in the method for producing a functional film.
[0026]
In the present invention, the conductive fine particles include tin oxide, indium oxide, zinc oxide, cadmium oxide, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), tin-doped indium oxide (ITO), and aluminum-doped zinc oxide. The method for producing the conductive film described above, using conductive inorganic fine particles selected from the group consisting of (AZO).
[0027]
In the present invention, the dispersion of the functional fine particles may contain a small amount of resin, but particularly preferably does not contain a resin. When the dispersion of functional fine particles contains a resin, the content of the resin is preferably less than 25 when expressed in volume and the volume of the functional fine particles is 100. In particular, in the production of a conductive film, it is preferable that the functional fine particle dispersion does not contain a resin from the viewpoint of obtaining a conductive layer having a low electric resistance value.
[0028]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the functional layer is not particularly limited, and is not limited to a conductive layer, an ultraviolet shielding layer, an infrared shielding layer, a magnetic layer, a ferromagnetic layer, a dielectric layer, a ferroelectric layer, an electrochromic layer, or electroluminescence. A layer having various functions such as a layer, an insulating layer, a light absorption layer, a light selective absorption layer, a reflection layer, an antireflection layer, a catalyst layer, and a photocatalyst layer is included. Therefore, in the present invention, functional fine particles that should constitute the target layer are used. The functional fine particles are not particularly limited, and mainly inorganic fine particles having a cohesive force are used. In any functional film production, a functional coating film having sufficient mechanical strength can be obtained by applying the method of the present invention, and a binder in a conventional coating method using a large amount of binder resin. The harmful effects caused by the resin can be eliminated. As a result, the intended function is further improved.
[0029]
For example, in the production of a transparent conductive layer, tin oxide, indium oxide, zinc oxide, cadmium oxide, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), tin-doped indium oxide (ITO), aluminum-doped zinc oxide Conductive inorganic fine particles such as (AZO) are used. ITO is preferable in that it provides better conductivity. Or what coated inorganic material, such as ATO and ITO, on the surface of fine particles which have transparency, such as barium sulfate, can also be used. The particle diameter of these fine particles varies depending on the degree of scattering required depending on the application of the conductive film, and cannot be generally described depending on the shape of the particles, but is generally 10 μm or less, preferably 1.0 μm or less, 5 nm to 100 nm is more preferable.
[0030]
Alternatively, organic conductive fine particles may be used. Examples of the organic conductive fine particles include those in which a metal material is coated on the surface of resin fine particles.
[0031]
By applying this production method, excellent conductivity can be obtained. In the present invention, the transparent means that visible light is transmitted. Regarding the degree of light scattering, the required level varies depending on the use of the conductive layer. In the present invention, those having scattering, which is generally referred to as translucent, are also included.
[0032]
In the production of a ferromagnetic layer, γ-Fe₂O_Three, Fe_ThreeO_FourMainly composed of iron oxide magnetic powders such as Co-FeOx and Ba ferrite and ferromagnetic metal elements such as α-Fe, Fe-Co, Fe-Ni, Fe-Co-Ni, Co, and Co-Ni Ferromagnetic alloy powder or the like is used. By applying this production method, the saturation magnetic flux density of the magnetic coating film is improved.
[0033]
In the production of dielectric layers and ferroelectric layers, magnesium titanate, barium titanate, strontium titanate, lead titanate, lead zirconate titanate (PZT), lead zirconate, lanthanum added Dielectric or ferroelectric fine particles such as lead zirconate titanate (PLZT), magnesium silicate, and lead-containing perovskite compounds are used. Application of this manufacturing method can improve dielectric properties or ferroelectric properties.
[0034]
In the production of metal oxide layers that exhibit various functions, iron oxide (Fe₂O_Three), Silicon oxide (SiO₂), Aluminum oxide (Al₂O_Three), Titanium dioxide (TiO₂), Titanium oxide (TiO), zinc oxide (ZnO), zirconium oxide (ZrO)₂), Tungsten oxide (WO_Three) And other metal oxide fine particles are used. By applying this manufacturing method, the filling degree of the metal oxide in the film is increased, so that each function is improved. For example, SiO on which a catalyst is supported₂, Al₂O_ThreeWhen is used, a porous catalyst layer having practical strength can be obtained. TiO₂When is used, the photocatalytic function can be improved. In addition, WO_ThreeWhen is used, an improvement in the coloring effect in the electrochromic display element can be obtained.
[0035]
In the production of the electroluminescence layer, zinc sulfide (ZnS) fine particles are used. By applying this production method, an inexpensive electroluminescence layer can be produced by a coating method.
[0036]
In the present invention, a liquid in which functional fine particles selected from the above-mentioned various functional fine particles are dispersed is used as a functional coating depending on the purpose.
[0037]
The liquid in which functional fine particles such as conductive fine particles are dispersed is not particularly limited, and various known liquids can be used. For example, as liquid, saturated hydrocarbons such as hexane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, propanol and butanol, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, diisobutyl ketone, etc. Ketones, esters such as ethyl acetate and butyl acetate, ethers such as tetrahydrofuran, dioxane and diethyl ether, amides such as N, N-dimethylformamide, N-methylpyrrolidone (NMP) and N, N-dimethylacetamide And halogenated hydrocarbons such as ethylene chloride and chlorobenzene. Among these, polar liquids are preferable, and those having an affinity for water, such as alcohols such as methanol and ethanol, and amides such as NMP, have good dispersibility without using a dispersant. It is preferable. These liquids can be used singly or as a mixture of two or more. Moreover, a dispersing agent can also be used according to the kind of liquid.
[0038]
Water can also be used as the liquid. When water is used, the transfer support needs to be hydrophilic. Since the resin film is usually hydrophobic, it easily repels water and it is difficult to obtain a uniform film. When the transfer support is a resin film, it is necessary to mix alcohol with water or to make the surface of the transfer support hydrophilic.
[0039]
The amount of the liquid to be used is not particularly limited, and the fine particle dispersion may have a viscosity suitable for a coating method described later. For example, the amount of the liquid is about 100 to 100,000 parts by weight with respect to 100 parts by weight of the fine particles. It is preferable to select appropriately according to the kind of the fine particles and the liquid. In general, the smaller the particle size of the fine particles, the larger the specific surface area and the higher the viscosity. When using fine particles having a large specific surface area, the amount of liquid may be increased to lower the solid content concentration. Even when the coating film thickness is thin, it is preferable to use a coating solution having a low solid content by increasing the amount of the liquid.
[0040]
The dispersion of the fine particles in the liquid may be performed by a known dispersion method. For example, it is dispersed by a sand grinder mill method. In dispersing, it is also preferable to use media such as zirconia beads in order to loosen the aggregation of the fine particles. Also, care should be taken not to mix impurities such as dust during dispersion.
[0041]
The fine particle dispersion preferably contains no resin. That is, it is preferable that the resin amount = 0. If the dispersion of fine particles does not contain a resin, the functional fine particle-containing layer (before compression) formed by coating on the transfer support does not contain a resin.
[0042]
In the conductive layer, if no resin is used, the contact between the conductive fine particles is not hindered by the resin. Therefore, the conductivity between the conductive fine particles is ensured, and the electric resistance value of the obtained conductive layer is low. A resin can be included as long as it does not impair the conductivity, but the amount is very small compared to the amount used as a binder resin in the prior art. For example, the upper limit of the content of the resin in the dispersion is represented by the volume before dispersion, and the volume of the conductive fine particles is 100, and the volume is less than 25. In the prior art, since strong compression is not performed, a large amount of binder must be used to obtain the mechanical strength of the coating film. When an amount of resin that plays a role as a binder is used, contact between the conductive fine particles is inhibited by the binder, electron transfer between the fine particles is inhibited, and conductivity is lowered.
[0043]
On the other hand, the resin has an effect of improving the haze of the conductive layer. However, from the viewpoint of conductivity, the resin is preferably used in a volume range of less than 25 when the volume of the conductive fine particles is represented as 100 and expressed as a volume before dispersion, and a volume of less than 20 It is more preferable to use within the range. Moreover, although the effect of improving haze is reduced, it is most preferable not to use a resin from the viewpoint of conductivity.
[0044]
WO_ThreeFine particles and TiO₂Even in a functional layer using fine particles and other functional fine particles, if the resin is not used, the contact between the fine particles is not hindered by the resin, so that each function can be improved. It is possible to include a resin as long as the contact between the fine particles is not hindered and does not impair each function, but the amount is, for example, about 80 or less when the volume of each fine particle is 100. Volume.
[0045]
Al₂O_ThreeIn a catalyst layer using fine particles or the like, the surface of fine particles having a catalytic function is not covered by the resin unless a resin is used. For this reason, the function as a catalyst is improved. In the catalyst layer, the more voids inside the layer, the more active points as a catalyst. Therefore, it is preferable not to use a resin as much as possible from this viewpoint.
[0046]
Thus, it is preferable not to use a resin in the functional layer at the time of compression (that is, in the dispersion liquid of the functional fine particles), and even if used, a small amount is preferable. The amount of the resin to be used may be appropriately determined because it can be changed to some extent according to the purpose of the functional layer.
[0047]
Various additives may be blended in the fine particle dispersion within a range satisfying performance required for each function such as conductivity and catalytic action. For example, additives such as ultraviolet absorbers, surfactants, and dispersants.
[0048]
In the present invention, a dispersion of functional fine particles such as conductive fine particles is applied onto a transfer support and dried to form a functional fine particle-containing layer such as a conductive fine particle-containing layer on the transfer support.
[0049]
The transfer support is not particularly limited, and various materials such as a resin film, metal, cloth, and paper can be used. However, it is preferable to use a flexible material that does not crack during compression in the subsequent process and that can be easily peeled off after compression. The shape of the transfer support can be a film, foil, mesh, woven fabric, or the like.
[0050]
As the transfer support, a flexible resin film that does not break even when the compression force in the compression step is increased is suitable. The resin film is lightweight, easy to handle, and easy to peel after compression. In the present invention, a resin film can be used as a transfer support since there is no pressurization step at high temperature and no firing step.
Examples of the resin film include polyester films such as polyethylene terephthalate (PET), polyolefin films such as polyethylene and polypropylene, polycarbonate films, acrylic films, norbornene films (manufactured by JSR Corporation, Arton, etc.), and the like.
[0051]
In the present invention, the transfer support may have a hard coat layer on the surface on which the functional fine particle-containing layer is to be formed. When the functional fine particle-containing layer is formed on the hard coat layer of the transfer support, the functional fine particles are not embedded in the hard coat layer in the subsequent compression step, so that the adhesion of the functional fine particles to the transfer support is improved. It is not strong, and the adhesion of the functional fine particles to the support becomes stronger, and as a result, the transfer of the functional fine particle layer from the transfer support to the support becomes easy.
[0052]
The hard coat layer can be formed by applying a solution obtained by dissolving a hard coat agent in a solvent as necessary, applying the solution on the transfer support base, drying it, and curing it.
The hard coat agent is not particularly limited, and various known hard coat agents can be used. For example, silicone-based, acrylic-based, melamine-based thermosetting hard coat agents can be used. Among these, the silicone-based hard coat agent is excellent in that high hardness can be obtained.
[0053]
Further, an ultraviolet curable hard coat agent such as an unsaturated polyester resin-based or acrylic-based radical polymerizable hard coat agent or an epoxy-based or vinyl ether-based cationic polymerizable hard coat agent may be used. The ultraviolet curable hard coat agent is preferable from the viewpoint of productivity such as curing reactivity. Among these, in view of curing reactivity and surface hardness, an acrylic radical polymerizable hard coating agent is desirable.
[0054]
The hard coat agent may be applied by a known method such as a roll coater such as a gravure cylinder, reverse, or Mayer bar, or a slit die coater.
After application, it is dried in an appropriate temperature range and then cured. In the case of a thermosetting hard coat agent, appropriate heat is applied. For example, in the case of a silicone type hard coat agent, it is cured by heating to about 60 to 120 ° C. for 1 minute to 48 hours. In the case of an ultraviolet curable hard coat agent, it is cured by irradiating with ultraviolet rays. For ultraviolet irradiation, a xenon lamp, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, etc.²It is good to irradiate to some extent. The thickness of the hard coat layer is, for example, about 0.5 to 20 μm, preferably about 2 to 5 μm.
[0055]
The application of the functional fine particle dispersion onto the transfer support is not particularly limited and can be performed by a known method. For example, a high-viscosity dispersion liquid of 1000 cps or more can be applied by a coating method such as a blade method or a knife method. The low viscosity dispersion of less than 500 cps can be applied by a coating method such as a bar coating method, a kiss coating method, or a squeeze method, or the dispersion can be attached to the support by spraying or spraying. It is. Furthermore, a coating method such as a reverse roll method, a direct roll method, an extrusion nozzle method, a curtain method, a gravure roll method, or a dip method can be used regardless of the viscosity of the dispersion.
[0056]
The drying temperature depends on the type of liquid used for dispersion, but is preferably about 10 to 150 ° C. If it is less than 10 ° C, condensation of moisture in the air tends to occur, and if it exceeds 150 ° C, the resin film support is deformed. Also, care should be taken so that impurities do not adhere to the surface of the fine particles during drying.
[0057]
The thickness of the functional fine particle-containing layer after coating and drying depends on the compression conditions in the next step and the use of each functional layer such as a conductive layer finally obtained after compression and transfer onto the support. The thickness may be about 0.1 to 10 μm.
[0058]
Thus, when functional fine particles such as conductive fine particles are dispersed in a liquid, applied, and dried, a uniform film can be easily formed. When the fine particle dispersion is applied and dried, the fine particles form a film even if no binder is present in the dispersion. The reason for forming a film without the presence of a binder is not necessarily clear, but when the liquid is reduced after drying, fine particles gather together due to capillary force. Furthermore, the fact that it is a fine particle has a large specific surface area and a strong cohesive force, so it is thought that it may become a film. However, the strength of the film at this stage is weak. Further, the conductive layer has a high electric resistance value, and the electric resistance value varies greatly.
[0059]
As described above, the functional fine particle-containing layer is formed on the transfer support to obtain a transfer precursor film.
[0060]
Next, while the functional fine particle-containing layer of the transfer precursor film is compressed, it is transferred onto the support on which the functional layer is to be formed.
The support on which the functional layer is to be formed is not particularly limited, and various types such as a resin film, metal, cloth, and paper can be used. However, those that do not crack during compression are preferred. The shape of the support can be a film, foil, mesh, woven fabric, or the like.
[0061]
The surface on which the functional layer of the support is to be formed is preferably softer than the surface on which the functional fine particle-containing layer of the transfer support is to be formed. During the compression step, the adhesion of the functional fine particles to the support is stronger than the adhesion of the functional fine particles to the transfer support, and as a result, the functional fine particle layer from the transfer support to the support. Is easy to transfer.
[0062]
As the support, a flexible resin film that does not break even when the compression force in the compression step is increased is suitable. The resin film is lightweight and easy to handle. In the present invention, a resin film can be used as a support since there is no pressurization step at high temperature and no firing step. Examples of the resin film are the same as those mentioned for the transfer support. Further, if necessary, the support surface may be subjected to corona discharge treatment or easy adhesion treatment.
[0063]
In the present invention, the support may have a resin layer on the surface on which the functional layer is to be formed. The resin layer is required to have such a softness that a part of the functional fine particles is embedded in the resin layer during the compression step so that the compressed layer of the functional fine particles is formed on the resin layer with good adhesion. It is done. Accordingly, the resin layer is preferably softer than, for example, pencil hardness 2H. The degree of softness required for the resin layer depends on the hardness of the transfer support surface (hardness of the hard coat layer, if formed), the type and particle size of functional fine particles, and the compression pressure. Change.
[0064]
A soft resin can be used for the resin layer of the support. Examples of such a resin include those that can obtain a relatively low hardness from acrylic resin, urethane resin, vinyl chloride resin, silicone resin, and the like. Use. The resin layer may contain fine particles such as silica for adjusting the hardness of the resin layer, and a filler for coloring and ultraviolet absorption, as long as the adhesion is not adversely affected. After compression, the soft resin layer may be cured with heat, ultraviolet light, or the like. For example, since the hard coat agent is also soft before curing, it can be used for this resin layer. And it can also be set as a hard-coat layer by giving a hardening process after compression.
[0065]
In the present invention, since it is not necessary to apply the dispersion liquid of the functional fine particles directly to the surface on which the functional layer is to be formed, for example, even if the resin layer is soluble in the dispersion liquid, There is an advantage that the compression layer can be formed on the resin layer without dissolving the resin layer.
[0066]
The support on which the functional layer is to be formed and the transfer precursor film are overlapped so that the support and the functional fine particle-containing layer of the transfer precursor film are in contact with each other, and the functional fine particle-containing layer such as the conductive fine particle-containing layer is compressed. Then, a compressed layer of functional fine particles such as conductive fine particles is formed on the support.
[0067]
By compressing, the strength of the film is improved. That is, by compressing, the contact points between functional fine particles such as conductive fine particles increase and the contact surface increases. For this reason, the coating film strength increases. Since the fine particles originally have a property of easily agglomerating, they become a strong film by being compressed.
[0068]
In the conductive layer, the coating strength increases and the electrical resistance decreases. In the catalyst layer, the strength of the coating film is increased and a porous film is formed because no resin is used or the amount of resin is small. Therefore, a higher catalytic function can be obtained. Also in other functional layers, it is possible to form a high-strength film in which fine particles are connected to each other, and since no resin is used or the amount of resin is small, the filling amount of fine particles in a unit volume increases. Therefore, higher functions can be obtained.
[0069]
  By compressing, the film strength is improved and the functional fine particle-containing layer is transferred from the transfer support side to the support side.
  Compression is 44 N / mm²With the above compression forceYeah.44 N / mm²If the pressure is less than 1, the functional fine particle-containing layer such as the conductive fine particle-containing layer cannot be sufficiently compressed, and it is difficult to obtain a functional layer such as a conductive layer having excellent functionality such as conductivity. 138 N / mm²The above compressive force is more preferable, 183 N / mm²The compression force of is more preferable. The higher the compression force, the better the coating strength and the better the adhesion with the support. In the conductive layer, a layer having higher conductivity is obtained, the strength of the conductive layer is improved, and the adhesion between the conductive layer and the support is strengthened. The higher the compression force, the higher the pressure resistance of the device, so generally 1000 N / mm²The compression force up to is appropriate.
[0070]
Further, it is preferable that the compression is performed at a temperature at which the support and the transfer support are not deformed. For example, when the support and / or the transfer support is a resin film, the temperature is equal to or lower than the glass transition temperature (secondary transition temperature) of the resin. When the support is made of metal, the temperature range is such that the metal does not melt.
[0071]
The compression is not particularly limited and can be performed by a sheet press, a roll press, or the like, but is preferably performed using a roll press machine. Roll press is a method in which a film to be compressed is sandwiched between rolls and compressed, and the roll is rotated. A roll press is uniformly high pressure, and is more suitable for productivity than a sheet press.
[0072]
The roll temperature of the roll press machine is preferably room temperature (an environment in which humans can easily work) from the viewpoint of productivity. In the compressed atmosphere (hot press) in which the heated atmosphere or the roll is heated, there is a problem that the resin film stretches when the compression pressure is increased. When the compression pressure is weakened so that the resin film of the support does not stretch under heating, the mechanical strength of the coating film decreases. In the conductive layer, the mechanical strength of the coating film decreases and the electrical resistance increases. It is also preferable to adjust the temperature so that the roll temperature does not rise due to heat generation when continuously compressed by a roll press.
[0073]
When there is a reason for wanting to minimize moisture adhesion on the surface of fine particles, a heated atmosphere may be used to reduce the relative humidity of the atmosphere, but the temperature range is within the range where the film does not easily stretch. It is. Generally, it is a temperature range below the glass transition temperature (secondary transition temperature). In consideration of fluctuations in humidity, the temperature may be a little higher than the required temperature.
If the support is made of metal, it is possible to create a heated atmosphere up to a temperature range in which the metal does not melt.
[0074]
The glass transition temperature of the resin film is obtained by measuring dynamic viscoelasticity, and indicates a temperature at which the dynamic loss of main dispersion reaches a peak. For example, when looking at a PET film, its glass transition temperature is around 110 ° C.
[0075]
The roll of the roll press machine is preferably a metal roll because a strong pressure is applied. Further, the roll surface may be treated with hard chrome, a ceramic sprayed film, a film obtained by ion plating such as TiN, or a hard film such as DLC (diamond-like carbon).
[0076]
Following compression, the transfer support is peeled from the compressed layer of functional particulates.
In this way, a compressed layer of functional fine particles such as conductive fine particles is formed on the support. The thickness of the functional fine particle compression layer such as conductive fine particles may be about 0.05 to 10 μm, preferably 0.1 to 5 μm, more preferably 0.1 to 3 μm, although it depends on the application. Most preferred is 1-2 μm.
[0077]
Further, in order to obtain a thick compressed layer of about 10 μm, a series of operations of applying a dispersion of fine particles, drying, and compressing may be repeated when the transfer precursor film is formed.
Furthermore, in the present invention, it is of course possible to form each functional layer such as a conductive layer on both sides of the support.
[0078]
Each functional layer such as a transparent conductive layer thus obtained exhibits excellent functionality such as conductivity and catalytic action, and does not use a binder resin or a small amount of resin that does not function as a binder. Despite the use of the film, it has a practically sufficient film strength and excellent adhesion to the support.
[0079]
In the method for producing a functional film of the present invention, it is also possible to obtain a functional fine particle compressed layer composed of at least two layers of different functional fine particle compressed layers.
The multilayer structure is formed by repeating a series of operations of applying and drying a dispersion of the corresponding functional fine particles when forming the transfer precursor film, forming a multilayer functional fine particle-containing layer, and then performing compression. can get.
It is also preferable to prepare a plurality of transfer precursor films having a single functional fine particle-containing layer, and sequentially compress the functional fine particle-containing layer and transfer it onto a support.
[0080]
Depending on the purpose and application of the multilayer functional layer, a multilayer structure may be formed by combining a plurality of functional layers having different functions. By combining a plurality of functional layers, for example, multilayer functional layers for solar cells, electroluminescent elements, electrochromic elements and the like can be obtained.
[0081]
Specifically, for solar cells, a multilayer structure including a transparent conductive layer, a transparent insulator layer, a chalcopallite structure semiconductor layer composed of Group I, Group III, and Group IV, and a metal electrode is sequentially exemplified.
For the distributed direct current operation electroluminescent element, a multilayer structure of a transparent conductive layer, an EL light emitting layer, and a back electrode is exemplified in order.
Examples of the transmissive electrochromic device include a multilayer structure of a transparent conductive layer, a first color developing layer, a dielectric layer, a second color developing layer, and a transparent conductive layer in this order.
In addition to these, various multilayer structures according to various applications are conceivable.
[0082]
In the case of a multilayer structure, not all of the layers constituting the multilayer functional layer need necessarily be compressed layers. For example, in the case of a solar cell, the transparent conductive layer, the transparent insulator layer, and the semiconductor layer may be formed by compression, and the metal electrode may be formed by vapor deposition.
[0083]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
[0084]
FIG. 1 is a diagram for explaining formation of a compressed layer in the production method of the present invention.
In FIG. 1, a functional fine particle-containing layer (P4) is formed on a transfer support (2) having a hard coat layer (2b) formed on a base film (2a), and a transfer precursor film (5) and Has been. Between the pair of upper and lower press rolls (R1) and (R2) of the roll press machine, the support (1) and the transfer precursor film (5) and the surface on which the functional layer of the support (1) is to be formed and the film The layers are compressed so as to overlap with the functional fine particle-containing layer (P4) of (5). The functional fine particle-containing layer (P4) is compressed into a compressed layer (4). After that, when both (1) and (5) pass through the guide rollers (G1) and (G2) where appropriate, the transfer support (2) and the compression layer (4) are peeled off, and the support (1) is removed. Thus, the compression layer (4) is transferred and formed.
[0085]
  Example 18These are examples in which ITO fine particles are used as conductive fine particles in order to obtain a transparent conductive film for use in an electroluminescence panel electrode.
[0086]
(Preparation of transfer precursor film)
300 parts by weight of ethanol was added to 100 parts by weight of ITO fine particles (manufactured by Dowa Mining Co., Ltd.) having a primary particle size of 10 to 30 nm, and the media was dispersed as zirconia beads with a disperser. The obtained coating solution is applied onto the hard coat layer (2b) of the transfer support (2) using a bar coater, dried by sending hot air of 50 ° C. to form an ITO fine particle-containing layer (P4). did. In this way, a transfer precursor film (5) was obtained. The thickness of the ITO fine particle-containing layer (P4) was 1.7 μm.
[0087]
(Support)
A 75 μm thick PET film HSL (manufactured by Teijin DuPont Films) was used as the support (1).
[0088]
(Formation of compressed layer)
The support (1) and the transfer precursor film (5) were overlapped so that the support (1) and the ITO fine particle-containing layer (P4) were in contact, and sandwiched and compressed using a roll press machine.
[0089]
Prior to compression, first, a preliminary experiment for confirming the compression pressure was performed.
Room temperature (23 ° C.) without rotating the roll and heating the roll using a roll press machine having a pair of metal rolls having a diameter of 140 mm (the roll surface is hard chrome plated) Then, the support (1) and the transfer precursor film (5) were sandwiched and compressed. At this time, the pressure per unit length in the film width direction was 1000 N / mm. Next, when the pressure was released and the length in the film longitudinal direction of the portion compressed and transferred to the support was examined, it was 2 mm. From this result, 500 N / mm per unit area²It will be compressed with the pressure of.
[0090]
Next, the same support (1) and transfer precursor film (5) as those used in the preliminary experiment were sandwiched between metal rolls and compressed under the above conditions, and the roll was rotated and compressed at a feed rate of 5 m / min. . After compression, the transfer support (2) was peeled from the ITO fine particle compression layer (4) on the support (1). Thus, an ITO film (FIG. 3) in which a compressed layer (4) of ITO fine particles was formed on the support (1) was obtained. The thickness of the ITO fine particle compressed layer (4) was 1.0 μm. Peeling was easily performed, and the surface of the ITO fine particle compressed layer (4) was completely exposed.
[0091]
(Electrical resistance)
The film on which the ITO fine particle compressed layer (4) was formed was cut into a size of 50 mm × 50 mm. When the electrical resistance was measured by applying a tester to two points at the diagonal corners, it was 3 kΩ.
[0092]
(90 degree peel test)
In order to evaluate the adhesion of the ITO fine particle compressed layer (4) to the support film (1) and the strength of the compressed layer (4), a 90 degree peel test was conducted. This will be described with reference to FIG.
A double-sided tape (12) was applied to the surface of the support film (1) opposite to the surface on which the compression layer (4) was formed in the film on which the compression layer (4) was formed. This was cut out to a size of 25 mm × 100 mm. This test sample was attached to a stainless steel plate (13). Cellophane adhesive tape (width 12 mm, manufactured by Nitto Denko, No. 29) (14) was applied to both ends (25 mm side) of the sample so that the test sample was not peeled off. (FIG. 2 (a)).
[0093]
A cellophane adhesive tape (width 12 mm, manufactured by Nitto Denko, No. 29) (15) was applied to the compressed layer (4) surface of the test sample so as to be parallel to the long side of the sample. The sticking length of the cellophane tape (15) and the sample was 50 mm. The end on which the cellophane tape (15) was not attached was attached to the tension meter (16), and the cellophane tape (15) was set so that the angle formed by the application surface of the cellophane tape (15) and the non-application surface (15a) was 90 degrees. The cellophane tape (15) was pulled off at a speed of 100 mm / min. At this time, the speed at which the tape (15) is peeled off and the stainless steel plate (13) to which the test sample is attached move at the same speed, and the non-sticking surface (15a) of the cellophane tape (15) and the test sample surface are always 90%. It was to be a degree. The force (F) required for peeling with a tensiometer (16) was measured. (FIG. 2 (b)).
[0094]
After the test, the surface of the peeled compressed layer (4) and the cellophane tape were examined. When there is an adhesive on both surfaces, the compressed layer (4) was not destroyed, but the adhesive layer of the cellophane tape was destroyed, that is, the force required to peel off the adhesive strength ( F) value, and the strength of the compressed layer (4) is more than the value (F).
[0095]
In this test, since the upper limit of the strength of the adhesive is 6N / 12mm, what is indicated as 6N / 12mm in Table 1 is the case where there is an adhesive on both surfaces as described above, It represents that the strength of the compressed layer (4) is 6 N / 12 mm or more. If the value is smaller than this, there is no adhesive on the surface of the compressed layer (4), and part of the compressed layer is adhered to the surface of the cellophane tape, and at that value, the compressed layer (4) is broken. Represents. A value of 3N / 12 mm or more is a practical level.
[0096]
As a result of the 90-degree peel test, in Example 1, a force of 6 N / 12 mm was required to peel off the cellophane tape. When the surface of the compressed layer (4) after the peel test was examined, the cellophane tape adhesive was adhered. When the adhesive surface of the peeled cellophane tape was examined, it was found to be sticky. Therefore, the strength of the compressed layer (4) was 6 N / 12 mm or more.
[0097]
[Examples 2 to 6]
In Example 1, a compressed ITO film was obtained in the same manner as in Example 1 except that the compression pressure was changed to the values shown in Table 1 and compressed. The electrical resistance was measured and a 90 degree peel test was performed.
[0098]
[Comparative Example 1]
For comparison, a physical property test was performed on the transfer precursor film (5) on which the ITO fine particle-containing layer (P4) of Example 1 was formed. The electric resistance of the ITO fine particle-containing layer (P4) not subjected to compression treatment was 340 kΩ.
[0099]
[Example 7]
In Example 2, a compressed ITO film was obtained in the same manner as in Example 2 except that the feeding speed during compression was changed to 2.5 m / min. The electrical resistance was measured and a 90 degree peel test was performed.
[0100]
[Comparative Example 2]
100 parts by weight of PVDF was dissolved in 900 parts by weight of NMP to obtain a resin solution. 1000 parts by weight of the resin solution and 900 parts by weight of NMP were added to 100 parts by weight of ITO fine particles (manufactured by Dowa Mining Co., Ltd.) having a primary particle size of 10 to 30 nm, and the media was dispersed as zirconia beads with a disperser.
The obtained coating solution was applied onto a 50 μm thick PET film using a bar coater and dried (100 ° C., 3 minutes) to obtain an ITO film. The thickness of the ITO coating film was 1.0 μm. The electrical resistance was measured and a 90-degree peel test was performed (the volume of PVDF was 383 when the volume of ITO fine particles was 100).
The result of the 90 degree peel test was 3.4 N / 12 mm. This is because PVDF oozes out on the surface of the coating film due to the large amount of resin, and the adhesion of the cellophane tape to the coating film surface was low, and the coating film was not destroyed. Accordingly, the coating film strength was 3.4 N / 12 mm or more.
[0101]
[Example 8]
(Support)
A 50 μm-thick PET film HPE (manufactured by Teijin DuPont Films) (1) is coated with a silicone hard coat liquid KP-854 (manufactured by Shin-Etsu Chemical Co., Ltd.), dried and uncured with a thickness of 2 μm. A silicone hard coat layer (H) was formed.
[0102]
(Preparation of transfer precursor film)
A transfer support (2) in which a silicone hard coat layer (2b) was formed on the same PET base film (2a) as used in Example 1 was used. In the same manner as in Example 1, an ITO fine particle-containing layer (P4) was formed on the hard coat layer (2b) of the transfer support (2) to obtain a transfer precursor film (5).
[0103]
(Formation of compressed layer)
The support (1) on which the silicone hard coat layer (H) is formed and the transfer precursor film (5) on which the ITO fine particle-containing layer (P4) is formed, the silicone hard coat layer (H) and the ITO fine particle-containing layer. (P4) was placed in contact with each other, and sandwiched and compressed using a roll press. Compression pressure: 347 N / mm². After compression, the transfer support (2) was peeled from the ITO fine particle compression layer (4) on the support (1). Thus, an ITO film in which the silicone hard coat layer (H) and the compressed layer (4) of ITO fine particles were formed on the support (1) having the layer structure shown in FIG. 6 was obtained. Peeling was easily performed, and the surface of the ITO fine particle compressed layer (4) was completely exposed.
Next, the uncured silicone hard coat layer (H) was cured by placing the ITO film in an atmosphere at 100 ° C. for 1 hour. The thickness of the ITO fine particle compressed layer (4) was 1.0 μm. The electrical resistance was measured and a 90 degree peel test was performed.
[0104]
[Table 1]

[0105]
Table 1 shows the measurement results of Examples 1 to 8 and Comparative Examples 1 and 2. Each of the conductive films of Examples 1 to 8 had a low electrical resistance value, a strong compression layer, and excellent adhesion between the compression layer and the support film.
From Examples 1 to 6, the higher the press pressure, the better the conductivity, the stronger the compression layer, the stronger the adhesion between the compression layer and the support film, and the adhesive of the cellophane tape on the conductive surface. It remained so much.
Better conductivity was obtained in the conductive layer containing no resin than in the conductive layer containing resin. Moreover, all of the conductive films of Examples 1 to 8 were excellent in transparency in terms of visible light transmittance.
[0106]
On the other hand, since the thing of the comparative example 1 has not performed the compression process, compared with the thing of Examples 1-6, an electrical resistance value is high.
In Comparative Example 2, a large amount of binder resin was used so that a coating film could be formed without compression as in the prior art. Since a large amount of binder resin was used, the strength of the coating film was sufficient, but the electrical resistance value was high.
[0107]
[Example 9: ITO / TiO₂Formation of multilayer functional layer]
In this embodiment, an ITO compressed layer is first transferred and formed on a support, and then a TiO layer is formed on the ITO compressed layer.₂This is an example in which a compression layer is transferred and formed. This will be described with reference to FIGS. 4 and 5 for explaining the formation of the multilayer compressed layer in the production method of the present invention.
[0108]
1. Formation of the first compression layer
In the same manner as in Example 2, an ITO fine particle compressed layer (4I) was formed as a first compressed layer on the support (1). Compression pressure: 347 N / mm².
[0109]
2. Formation of the second compression layer
(Transfer support)
A transfer support (2) in which a silicone hard coat layer (2b) was formed on the same PET base film (2a) as used in Example 1 was used.
[0110]
(Preparation of transfer precursor film)
TiO with primary particle size of 30-70 nm₂900 parts by weight of ethanol was added to 100 parts by weight of fine particles, and the media was dispersed as zirconia beads with a disperser. The obtained coating solution is applied onto the hard coat layer (2b) of the transfer support (2) using a bar coater, dried by sending hot air of 50 ° C., and TiO 2.₂A fine particle-containing layer (P4II) was formed. In this way, a transfer precursor film (5) was obtained. TiO₂The thickness of the fine particle-containing layer (P4II) was 0.7 μm.
[0111]
(Formation of second layer compression layer)
As shown in FIG. 4, the support (1) on which the ITO compression layer (4I) is formed, and TiO₂The transfer precursor film (5) on which the fine particle-containing layer (P4II) is formed, and the ITO compressed layer (4I) and TiO₂The layers were stacked so as to be in contact with the fine particle-containing layer (P4II), and sandwiched and compressed using a roll press. Compression pressure: 347 N / mm². After compression, the transfer support (2) is replaced with TiO on the support (1).₂Peeled from the compressed layer (4II) of fine particles. In this way, the ITO fine particle compression layer (4I) and TiO on the support (1) having the layer structure shown in FIG.₂ITO / TiO with fine particle compression layer (4II)₂A film was obtained. The thickness of the ITO fine particle compressed layer (4I) is 1.0 μm, and TiO₂The thickness of the fine particle compressed layer (4II) was 0.5 μm. Peeling is easy and TiO₂The surface of the fine particle compressed layer (4II) was completely exposed.
[0112]
(90 degree peel test)
As a result of the 90-degree peel test, a force of 6 N / 12 mm was required to peel off the cellophane tape. When the surface of the compressed layer (4II) after the peel test was examined, the adhesive of the cellophane tape adhered and the ITO compressed layer (4I) and TiO₂There was no peeling between the compressed layer (4II). When the adhesive surface of the peeled cellophane tape was examined, it was found to be sticky.
Therefore, the strength of the compressed layers (4I) (4II) was 6 N / 12 mm or more.
Obtained ITO / TiO₂The multilayer functional film can be used as a solar cell.
[0113]
[Example 10: Creation of functional film for transfer]
In this example, a transfer ITO film was prepared using the compressed ITO film obtained by the method of the present invention, and the ITO compression layer of the transfer ITO film was transferred onto a polycarbonate substrate. This will be described with reference to FIGS.
[0114]
1. Formation of compressed layer
(Support)
A 75 μm thick PET film HSL (manufactured by Teijin DuPont Films) (1) A silicone hard coat solution KP-854 (manufactured by Shin-Etsu Chemical Co., Ltd.) is applied and dried, and a 2 μm thick uncured silicone hard coat layer (H) was formed.
[0115]
(Preparation of transfer precursor film)
A transfer support (2) in which a silicone hard coat layer (2b) was formed on the same PET base film (2a) as used in Example 1 was used. In the same manner as in Example 1, an ITO fine particle-containing layer (P4) was formed on the hard coat layer (2b) of the transfer support (2) to obtain a transfer precursor film (5).
[0116]
(Formation of compressed layer)
The support (1) on which the silicone hard coat layer (H) is formed and the transfer precursor film (5) on which the ITO fine particle-containing layer (P4) is formed, the silicone hard coat layer (H) and the ITO fine particle-containing layer. (P4) was placed in contact with each other, and sandwiched and compressed using a roll press. Compression pressure: 347 N / mm². After compression, the transfer support (2) was peeled from the ITO fine particle compression layer (4) on the support (1). Thus, an ITO film in which the silicone hard coat layer (H) and the compressed layer (4) of ITO fine particles were formed on the support (1) having the layer structure shown in FIG. 6 was obtained. Peeling was easily performed, and the surface of the ITO fine particle compressed layer (4) was completely exposed.
Next, the uncured silicone hard coat layer (H) was cured by placing the ITO film in an atmosphere of 100 ° C. for 1 hour. The thickness of the ITO fine particle compressed layer (4) was 1.0 μm.
[0117]
2. Creation of functional film for transfer
(Formation of adhesive layer)
100 parts by weight of acrylic resin 1BR-305 (solid content: 39.5%, manufactured by Taisei Kako Co., Ltd.), 92 parts by weight of UV curable resin SD-318 (manufactured by Dainippon Ink and Chemicals), methyl ethyl ketone 137 Part by weight was added to obtain an adhesive layer coating solution. The coating solution was applied onto a silicone-exfoliated PET film S314 (R) and dried to form an adhesive layer (7) having a thickness of 10 μm.
[0118]
Both films were laminated so that the ITO compressed layer (4) of the ITO film obtained in 1 and the adhesive layer (7) of the silicone-exfoliated PET film S314 (R) were in contact with each other. In this way, a transfer ITO film having a layer structure shown in FIG. 7 was prepared.
[0119]
3. Addition of functional layer to polycarbonate plate
The resulting transfer ITO film is peeled off from the silicone release PET film S314 (R) to expose the adhesive layer (7), and the laminator so that the adhesive layer (7) is in contact with the 2 mm thick polycarbonate plate (6). Pasted with. The adhesive layer (7) was cured by irradiating with ultraviolet rays. Thereafter, the support PET film (1) was peeled off. An ITO compressed layer (4) was formed on the polycarbonate plate (6), and a cured silicone hard coat layer (H) was present on the ITO compressed layer (4). In this way, as shown in FIG. 8, the ITO compression layer (4) was applied on the polycarbonate plate (6) via the adhesive layer (7).
[0120]
  Example 18In the above, an example in which an inorganic functional film was produced using ITO fine particles as inorganic fine particles was shown. Example9Then, ITO fine particles and TiO as inorganic fine particles₂Using fine particles, ITO / TiO₂The example which produced the multilayer functional film was shown. In the same manner as in the above example, WO_ThreeFine particles, Al₂O_ThreeVarious inorganic functional layers can be produced using inorganic fine particles having various properties such as fine particles.
[0121]
  Example10As shown in the above, a functional film for transfer is prepared using the functional film obtained by the method of the present invention, and the functional fine particle compressed layer of the functional film for transfer is transferred onto various substrates. Can do. This is advantageous when a functional layer having a uniform thickness is applied to an object having poor flexibility such as a plate material.
[0122]
The foregoing embodiments are merely illustrative in all respects and should not be construed as limiting. Furthermore, all modifications belonging to the equivalent scope of the claims are within the scope of the present invention.
[0123]
【The invention's effect】
According to the present invention, a coating containing functional fine particles is applied to a transfer support and dried to form a transfer precursor film, and the support on which the functional layer is to be formed and the transfer precursor film are overlaid and compressed. A functional film can be obtained by a simple operation. The functional layer according to the present invention has sufficient mechanical strength and eliminates the harmful effects caused by the binder resin in the conventional coating method. As a result, the intended function is further improved.
[0124]
According to the present invention, a conductive operation is applied to a transfer support and dried to form a transfer precursor film, and the support on which the conductive layer is to be formed and the transfer precursor film are overlaid and compressed. A transparent conductive film can be obtained. The transparent conductive layer according to the present invention is excellent in conductivity and excellent in transparency. Furthermore, it has sufficient mechanical strength, and the adhesiveness between the conductive layer and the support is strong, and can be used for a long time.
[0125]
Further, according to the method of the present invention, it is possible to cope with an increase in the area of the conductive film, the apparatus is simple, the productivity is high, and various functional films including a transparent conductive film can be produced at low cost.
[Brief description of the drawings]
FIG. 1 is a view for explaining formation of a compressed layer in the production method of the present invention.
FIG. 2 is a view for explaining a 90-degree peel test in Examples.
FIG. 3 is a cross-sectional view showing an example of a functional film obtained by the production method of the present invention.
FIG. 4 is a view for explaining the formation of a multilayer compressed layer in the production method of the present invention.
FIG. 5 is a cross-sectional view showing an example of a functional film having a multilayer functional layer obtained by the production method of the present invention.
FIG. 6 is a cross-sectional view showing an example of a functional film obtained by the production method of the present invention.
FIG. 7 is a cross-sectional view showing an example of a functional film for transfer produced using a functional film obtained by the production method of the present invention.
FIG. 8 is a cross-sectional view showing an example of an object provided with a functional layer of a functional film for transfer.
[Explanation of symbols]
(R1) (R2): Press roll
(G1) (G2): Guide roller
(1): Support
(2): Transfer support
(2a): Transfer support base
(2b): Hard coat layer
(P4): Functional fine particle-containing layer
(4): Functional fine particle compression layer
(5): Transfer precursor film
(6): Target object
(7): Adhesive layer
(H): Hard coat layer

Claims (10)

The liquid in which the functional fine particles are dispersed is applied on the transfer support and dried to create a transfer precursor film in which the functional fine particle-containing layer is formed on the transfer support.
The support on which the functional layer is to be formed and the transfer precursor film are overlapped so that the support and the functional fine particle-containing layer are in contact with each other, and the functional fine particle-containing layer is compressed with a compressive force of 44 N / mm ² or more. A functional layer comprising a compressed layer of functional fine particles on a support, comprising compression, forming a compressed layer of functional fine particles on the support, and then peeling the transfer support from the compressed layer of functional fine particles. A method for producing a functional film having at least   The method for producing a functional film according to claim 1, wherein the surface of the support on which the functional layer is to be formed is softer than the surface on which the functional fine particle-containing layer of the transfer support is to be formed. Compressed at a temperature at which the functional fine particle-containing layer and the support and the transfer support is not deformed, method for producing a functional film according to claim 1 or 2. The manufacturing method of the functional film of any one of Claims 1-3 which compresses the said functional fine particle content layer using a roll press machine. The said transfer support body is a manufacturing method of the functional film of any one of Claims 1-4 which has a hard-coat layer in the surface in which a functional fine particle content layer should be formed. The method for producing a functional film according to any one of claims 1 to 5 , wherein the support is a resin film. The method for producing a functional film according to any one of claims 1 to 6 , wherein the functional fine particles are selected from inorganic fine particles. Functional layer is conductive layer, ultraviolet shielding layer, infrared shielding layer, magnetic layer, ferromagnetic layer, dielectric layer, ferroelectric layer, electrochromic layer, electroluminescence layer, insulating layer, light absorption layer, light selective absorption layer, the reflective layer, anti-reflection layer is selected from the group consisting of a catalyst layer and photocatalyst layer, method for producing a functional film according to any one of claims 1-7. Using conductive fine particles as the functional fine particles, to form a conductive layer, method for producing a functional film according to any one of claims 1-8. Examples of the conductive fine particles include tin oxide, indium oxide, zinc oxide, cadmium oxide, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), tin-doped indium oxide (ITO), and aluminum-doped zinc oxide (AZO). The method for producing a functional film according to claim 9 , wherein conductive inorganic fine particles selected from the group consisting of:

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