JP2002015631A - Coating solution for photosensitive transparent electro- conductive film formation, patternized transparent electro-conductive film and manufacturing method of transparent electro-conductive film - Google Patents
Coating solution for photosensitive transparent electro- conductive film formation, patternized transparent electro-conductive film and manufacturing method of transparent electro-conductive filmInfo
- Publication number
- JP2002015631A JP2002015631A JP2000195685A JP2000195685A JP2002015631A JP 2002015631 A JP2002015631 A JP 2002015631A JP 2000195685 A JP2000195685 A JP 2000195685A JP 2000195685 A JP2000195685 A JP 2000195685A JP 2002015631 A JP2002015631 A JP 2002015631A
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- Prior art keywords
- conductive film
- tin
- transparent conductive
- forming
- photosensitive
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、基板上にパターン
化された透明導電膜を形成可能な感光性透明導電膜形成
用塗布液、パターン化された透明導電膜、および該透明
導電膜の製造方法に関する。さらに詳しくは、透明導電
膜形成材料として錫（Ｓｎ）系化合物のキレート錯体を
含有する感光性透明導電膜形成用塗布液、該塗布液を用
いて形成された優れた透明性と高い導電性、化学的安定
性を兼ね備え、しかもパターン加工性に優れたパターン
化された酸化錫系透明導電膜、および該透明導電膜の製
造方法に関するものである。The present invention relates to a photosensitive transparent conductive film forming coating solution capable of forming a patterned transparent conductive film on a substrate, a patterned transparent conductive film, and the production of the transparent conductive film. About the method. More specifically, a coating solution for forming a photosensitive transparent conductive film containing a chelate complex of a tin (Sn) -based compound as a material for forming a transparent conductive film, excellent transparency and high conductivity formed using the coating solution, The present invention relates to a patterned tin oxide-based transparent conductive film having both chemical stability and excellent pattern processability, and a method for producing the transparent conductive film.
【０００２】[0002]
【従来の技術】従来、ＬＣＤ、ＥＬ、ＰＤＰなどのディ
スプレイの透明電極やタッチパネルの透明電極などに使
用されるパターン化された透明導電膜の形成材料とし
て、錫ドープ酸化インジウム（以下、「ＩＴＯ」とい
う）材料が知られている。このＩＴＯ材料からなるパタ
ーン化された透明導電膜は、各種のＩＴＯ材料から真空
蒸着法、スパッタリング法、ＣＶＤ法により均一膜を形
成した後、フォトレジストによりレジストパターンを形
成し、さらに酸エッチングすることにより形成されてい
る。しかしながら、上記のパターン化されたＩＴＯの成
膜法は原料となるインジウム（Ｉｎ）源が高価であるこ
と、真空蒸着法、スパッタリング法、ＣＶＤ法などは、
使用する装置が高価で複雑であり、コストと量産性に問
題があること、また、フォトエッチング法は工程が煩雑
で、エッチング廃液の処理が厄介である。2. Description of the Related Art Conventionally, tin-doped indium oxide (hereinafter referred to as "ITO") has been used as a material for forming a patterned transparent conductive film used for transparent electrodes of displays such as LCDs, ELs, and PDPs, and transparent electrodes of touch panels. Materials) are known. The patterned transparent conductive film made of this ITO material is formed by forming a uniform film from various ITO materials by a vacuum deposition method, a sputtering method, and a CVD method, then forming a resist pattern with a photoresist, and further performing acid etching. Is formed. However, the above-mentioned patterned ITO film forming method requires an expensive indium (In) source as a raw material, and a vacuum evaporation method, a sputtering method, a CVD method, etc.
The equipment to be used is expensive and complicated, and there are problems in cost and mass productivity. In addition, the photoetching method requires complicated steps, and the treatment of the etching waste liquid is troublesome.
【０００３】また、上記ディスプレイの透明電極に用い
られる場合、一般に電流保証のため、さらにその膜上に
バスラインと呼ばれるＣｒ／Ｃｕ／ＣｒやＡｇの金属電
極配線が形成され、これも多くが均一膜のフォトエッチ
ング法で作製される。この際、透明電極には耐エッチン
グ薬品性が要求されるが、ＩＴＯの場合は充分ではな
い。When used for the transparent electrode of the above display, generally, a metal electrode wiring of a Cr / Cu / Cr or Ag called a bus line is formed on the film in order to guarantee a current, and many of them are uniform. It is produced by a photo-etching method of a film. At this time, the etching resistance of the transparent electrode is required, but the case of ITO is not sufficient.
【０００４】ＩＴＯとは対照的に、より安価な導電膜の
形成材料としてアンチモンドープ酸化錫（以下、「ＡＴ
Ｏ」という）がある。このＡＴＯはＩＴＯと比較し、若
干比抵抗が高いものの、化学的安定性（耐酸性、耐エッ
チング薬品性）や透明性が高く、ＩＴＯ同様種々の用途
の導電膜として使用されている。しかしＡＴＯは耐酸性
が強いため、ＡＴＯからなるパターン化された透明導電
膜はＩＴＯのような均一膜のフォトエッチング法で作製
することは困難で下記のようなリフトオフ法により専ら
作製される。リフトオフ法によるＡＴＯのパターン成膜
は、感光性レジストにより予めネガパターンを形成した
加熱基板上に、例えば二塩化ジメチル錫および三塩化ア
ンチモンの水溶液を吹き付け熱分解して成膜する方法
（ＣＶＤ法）である。しかしながら、この方法も約５０
０℃に基板を加熱することからＡＴＯの成膜中にレジス
トパターンが熱により損傷し、繊細なパターンが形成で
きないこと、反応排ガスの処理が厄介であるという問題
がある。[0004] In contrast to ITO, antimony-doped tin oxide (hereinafter referred to as "AT
O ”). Although this ATO has a slightly higher specific resistance than ITO, it has high chemical stability (acid resistance and etching chemical resistance) and transparency, and is used as a conductive film for various applications like ITO. However, since ATO has a strong acid resistance, it is difficult to produce a patterned transparent conductive film made of ATO by a photo-etching method of a uniform film such as ITO, and is produced exclusively by a lift-off method as described below. The ATO pattern film formation by the lift-off method is performed by spraying an aqueous solution of, for example, dimethyltin dichloride and antimony trichloride on a heated substrate on which a negative pattern has been formed in advance by using a photosensitive resist and thermally decomposing the film (CVD method). It is. However, this method also requires about 50
Since the substrate is heated to 0 ° C., there is a problem that the resist pattern is damaged by heat during the formation of the ATO and a delicate pattern cannot be formed, and that the treatment of the reaction exhaust gas is troublesome.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、上記
従来の技術が有する問題点を解決することにあり、より
具体的には、安価で安定性に優れた感光性透明導電膜形
成用塗布液；該感光性透明導電膜形成用塗布液を用いて
形成された透明性、導電性および塗膜の機械的強度、化
学的安定性に優れ、しかもパターン加工性に優れたパタ
ーン化された透明導電膜；ならびに成膜時の作業性がよ
く、非常に簡易な工程で微細にパターン化された透明導
電膜を作製することができる前記透明導電膜の製造方法
を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and more specifically, to form a photosensitive transparent conductive film which is inexpensive and excellent in stability. Coating liquid; patterned with excellent transparency, conductivity, mechanical strength and chemical stability of the coating film formed using the coating liquid for forming a photosensitive transparent conductive film, and excellent pattern processability. It is an object of the present invention to provide a method for producing a transparent conductive film, which is capable of producing a finely patterned transparent conductive film in a very simple process with good workability during film formation.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、鋭意検討
した結果、透明導電膜形成材料として特定の酸化錫系化
合物を使用することにより、上記の課題を解決すること
ができることを見出し、本発明を完成するに至った。す
なわち、本発明は、錫（Ｓｎ）化合物に有機配位子が配
位したキレート錯体と、紫外線硬化型または紫外線崩壊
型の感光性樹脂と、溶剤とを少なくとも含有することを
特徴とする感光性透明導電膜形成用塗布液（以下、「第
１の感光性透明導電膜形成用塗布液」ということがあ
る。）を提供する。Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above problems can be solved by using a specific tin oxide-based compound as a transparent conductive film forming material. The present invention has been completed. That is, the present invention provides a photosensitive composition comprising at least a chelate complex in which an organic ligand is coordinated with a tin (Sn) compound, a UV-curable or UV-degradable photosensitive resin, and a solvent. Provided is a coating liquid for forming a transparent conductive film (hereinafter, also referred to as a “first photosensitive transparent conductive film-forming coating liquid”).
【０００７】また、本発明は、錫（Ｓｎ）化合物とアン
チモン（Ｓｂ）化合物とにそれぞれ有機配位子が配位し
たキレート錯体と、紫外線硬化型または紫外線崩壊型の
感光性樹脂と、溶剤とを少なくとも含有することを特徴
とする感光性透明導電膜形成用塗布液（以下、「第２の
感光性透明導電膜形成用塗布液」ということがある。）
を提供する。Further, the present invention provides a chelate complex in which an organic ligand is coordinated to a tin (Sn) compound and an antimony (Sb) compound, an ultraviolet curable or ultraviolet decay type photosensitive resin, and a solvent. A coating liquid for forming a photosensitive transparent conductive film (hereinafter, may be referred to as a "second photosensitive transparent conductive film-forming coating liquid").
I will provide a.
【０００８】さらに、本発明は、前記第１の感光性透明
導電膜形成用塗布液または第２の感光性透明導電膜形成
用塗布液を、基板上に塗布、乾燥し、該乾燥膜を露光、
現像してパターン化し、焼成して得られた酸化錫を主成
分とすることを特徴とするパターン化された透明導電膜
を提供する。Further, the present invention provides a method for applying the first photosensitive transparent conductive film-forming coating solution or the second photosensitive transparent conductive film-forming coating solution on a substrate, followed by drying. ,
A patterned transparent conductive film is provided, which mainly comprises tin oxide obtained by developing, patterning, and firing.
【０００９】さらに、本発明は、前記前記第１の感光性
透明導電膜形成用塗布液または第２の感光性透明導電膜
形成用塗布液を、基板上に塗布、乾燥し、該乾燥膜上に
フォトマスクを設置し、紫外線を照射して露光した後、
現像してパターン化し、４００℃以上の温度で焼成する
ことを特徴とするパターン化された透明導電膜の製造方
法を提供する。Further, the present invention provides a method for applying the first photosensitive transparent conductive film forming coating solution or the second photosensitive transparent conductive film forming coating solution on a substrate, followed by drying. After installing a photomask and irradiating with ultraviolet light,
A method for producing a patterned transparent conductive film, characterized by developing and patterning and baking at a temperature of 400 ° C. or higher.
【００１０】[0010]
【発明の実施の形態】以下、実施の形態を挙げ、本発明
を詳細に説明する。なお、この実施の形態は発明の趣旨
をよりよく理解させるためのものであり、特に限定がな
い限り、本発明の内容を制限するものではない。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to embodiments. This embodiment is for better understanding of the gist of the invention, and does not limit the contents of the invention unless otherwise limited.
【００１１】「第１の感光性透明導電膜形成用塗布液」
第１の感光性透明導電膜形成用塗布液は、錫（Ｓｎ）
化合物に有機配位子が配位したキレート錯体と、紫外
線硬化型または紫外線崩壊型の感光性樹脂と、前記キ
レート錯体と前記感光性樹脂を溶解する溶剤とを少なく
とも含有している。ここに、前記の錫（Ｓｎ）化合物
は、有機配位子が配位してキレート錯体を形成し得るも
のであれば、特に限定されるものではない。錫化合物の
中でも、例えば、酢酸錫（II）、ぎ酸錫（II）、蓚酸錫
（II）、２−エチルヘキサン酸錫（II）、テトラメチル
錫（IV）、トリブチル酢酸錫（IV）、テトラｎ−プロポ
キシ錫（IV）などは、有機配位子との反応性がよく、か
つ得られるキレート錯体の溶解性が良好であるので好ま
しい。錫化合物は所望により２種以上を組合せ用いるこ
とができる。"First photosensitive transparent conductive film forming coating solution"
The coating liquid for forming the first photosensitive transparent conductive film is tin (Sn).
The compound contains at least a chelate complex in which an organic ligand is coordinated with a compound, a UV-curable or UV-degradable photosensitive resin, and a solvent that dissolves the chelate complex and the photosensitive resin. Here, the tin (Sn) compound is not particularly limited as long as the organic ligand can coordinate to form a chelate complex. Among the tin compounds, for example, tin (II) acetate, tin (II) formate, tin (II) oxalate, tin (II) 2-ethylhexanoate, tetramethyl tin (IV), tin (IV) tributyl acetate, Tetra n-propoxy tin (IV) and the like are preferable because they have good reactivity with the organic ligand and good solubility of the obtained chelate complex. If desired, two or more tin compounds can be used in combination.
【００１２】前記の有機配位子としては、β−ジケト
ン、アミノアルコール、多価アルコールが好適に使用で
きる。β−ジケトンの具体例としては、アセチルアセト
ン、アセト酢酸エチル、アセト酢酸メチルなどが挙げら
れ、アミルアルコールの具体例としては、ジエタノール
アミン、２−アミノエタノール、トリエタノールアミン
などが挙げられ、また、多価アルコールの具体例として
はエチレングリコール、プロピレングリコール、ジエチ
レングリコールなどが挙げられる。これらの有機配位子
の中でも、塗布液の安定性および錯体の熱分解性の点か
らアセチルアセトンが特に好ましい。有機配位子も所望
により２種以上を組合せ用いることができる。As the above-mentioned organic ligand, β-diketone, amino alcohol and polyhydric alcohol can be suitably used. Specific examples of β-diketone include acetylacetone, ethyl acetoacetate, and methyl acetoacetate. Specific examples of amyl alcohol include diethanolamine, 2-aminoethanol, and triethanolamine. Specific examples of the alcohol include ethylene glycol, propylene glycol, diethylene glycol and the like. Among these organic ligands, acetylacetone is particularly preferred from the viewpoint of the stability of the coating solution and the thermal decomposability of the complex. Two or more organic ligands can be used in combination, if desired.
【００１３】第１の感光性透明導電膜形成用塗布液中の
錫（Ｓｎ）の含有量は、塗布液重量に基づき酸化物（Ｓ
ｎＯ2）換算の合量で１〜２０重量％が好ましい。１重
量％未満では得られる透明導電膜の膜厚が薄くなり過
ぎ、透明導電膜のマトリックスが充分に形成されず、均
質性および導電性が低下する虞がある。また、２０重量
％を超えると塗布液中での溶解性が悪くなり、成膜時に
均一な膜を得ることが困難となり、また、得られる透明
導電膜の膜が厚くなり過ぎ、クラックが発生して緻密な
膜が得られない。The content of tin (Sn) in the coating liquid for forming the first photosensitive transparent conductive film is determined based on the weight of the oxide (Sn) based on the weight of the coating liquid.
The total amount is preferably 1 to 20% by weight in terms of nO 2 ). If the amount is less than 1% by weight, the thickness of the obtained transparent conductive film becomes too thin, the matrix of the transparent conductive film is not sufficiently formed, and the homogeneity and conductivity may be reduced. On the other hand, if the content exceeds 20% by weight, the solubility in the coating solution becomes poor, and it becomes difficult to obtain a uniform film at the time of film formation, and the obtained transparent conductive film becomes too thick, and cracks occur. And a dense film cannot be obtained.
【００１４】前記の感光性樹脂は、特に限定されること
はなく、一般に透明導電膜の形成に用いられる紫外線硬
化型のネガ型感光性樹脂、および紫外線崩壊型のポジ型
感光性樹脂を使用することができる。紫外線硬化型のネ
ガ型感光性樹脂の具体例としては、光重合性アクリル系
樹脂などが挙げられ、また、紫外線崩壊型のポジ型感光
性樹脂の具体例としてはノボラック系樹脂などが挙げら
れる。The above-mentioned photosensitive resin is not particularly limited, and a UV-curable negative photosensitive resin and a UV-degradable positive photosensitive resin generally used for forming a transparent conductive film are used. be able to. Specific examples of the UV-curable negative photosensitive resin include a photopolymerizable acrylic resin, and specific examples of the UV-degradable positive photosensitive resin include a novolak resin.
【００１５】前記の感光性樹脂の含有量は、特に制限さ
れるものではないが、塗布液重量に基づき、通常１〜２
０重量％、好ましくは５〜１５重量％である。含有量が
これより少ないと紫外線による膜の硬化あるいは崩壊が
十分行われず良好なパターンが得られない虞がある。ま
た、これよりも多いと焼成後の膜が多孔質となり緻密な
膜が得られず強度、密着性などが不良となる虞がある。
また、第１の感光性透明導電膜形成用塗布液には、感度
を向上させるため適宜重合開始剤、増感剤などを添加す
ることができる。Although the content of the photosensitive resin is not particularly limited, it is usually 1 to 2 based on the weight of the coating solution.
0% by weight, preferably 5 to 15% by weight. If the content is less than this, curing or disintegration of the film by ultraviolet rays may not be sufficiently performed, and a good pattern may not be obtained. On the other hand, if the amount is larger than this, the film after sintering becomes porous, and a dense film cannot be obtained, which may result in poor strength and adhesion.
Further, a polymerization initiator, a sensitizer, and the like can be appropriately added to the first photosensitive transparent conductive film forming coating solution in order to improve sensitivity.
【００１６】前記の溶剤としては、前記キレート錯体お
よび前記の感光性樹脂を溶解できるものであれば特に限
定されないが、塗工性を考慮して、１−プロパノール、
２−プロパノール、ベンジルアルコールなどのアルコー
ル類、アセチルアセトン、メチルイソブチルケトン、ジ
イソブチルケトンなどのケトン類、酢酸３−メトキシブ
チル、酢酸イソブチル、エチレングリコールモノアセタ
ートなどのエステル類、プロピレングリコールモノメチ
ルエーテル、プロピレングリコールモノエチルエーテ
ル、ジエチレングリコールモノメチルエーテルなどのグ
リコールエーテル類などの中沸点または高沸点有機溶媒
を用いることが好ましい。使用される溶剤の中には、ア
セチルアセトンのように、錫化合物に配位してキレート
錯体を形成し得るものも含まれる。溶剤は単独でまたは
２種以上を組合せて用いることができる。The solvent is not particularly limited as long as it can dissolve the chelate complex and the photosensitive resin, but in consideration of coatability, 1-propanol,
Alcohols such as 2-propanol and benzyl alcohol; ketones such as acetylacetone, methyl isobutyl ketone and diisobutyl ketone; esters such as 3-methoxybutyl acetate, isobutyl acetate and ethylene glycol monoacetate; propylene glycol monomethyl ether; propylene glycol It is preferable to use a medium- or high-boiling organic solvent such as glycol ethers such as monoethyl ether and diethylene glycol monomethyl ether. Some of the solvents used include those capable of coordinating with a tin compound to form a chelate complex, such as acetylacetone. The solvents can be used alone or in combination of two or more.
【００１７】第１の透明導電膜形成用塗布液は、例え
ば、次のようにして作製することができる。先ず、錫
（Ｓｎ）化合物と、前記の有機配位子と、前記の溶剤と
を混合し、これらを例えば沸点下で１〜５時間還流して
反応させ、前記の錫（Ｓｎ）化合物に有機配位子が配位
したキレート錯体を調製する。有機配位子の添加量は、
錫（Ｓｎ）原子１モルに対して０.２〜６モルが好まし
く、さらに、前記の有機配位子が前記の溶剤を兼ねる場
合は、有機配位子の添加量は大過剰であってよい。有機
配位子の添加量が０.２モルより少ないと完全なキレー
ト錯体が合成されず、未反応物が残留する。また、合成
は溶液の沸点下で行うのが好ましく、常温で合成すると
キレート化が不十分となる。The first transparent conductive film forming coating solution can be prepared, for example, as follows. First, a tin (Sn) compound, the above-mentioned organic ligand, and the above-mentioned solvent are mixed, and the mixture is refluxed, for example, at a boiling point for 1 to 5 hours to be reacted. A chelate complex having a ligand coordinated is prepared. The amount of organic ligand added is
The amount is preferably 0.2 to 6 mol with respect to 1 mol of tin (Sn) atom, and when the organic ligand also serves as the solvent, the amount of the organic ligand added may be large excess. . If the amount of the organic ligand is less than 0.2 mol, a complete chelate complex is not synthesized, and unreacted substances remain. Further, the synthesis is preferably performed at the boiling point of the solution, and when the synthesis is performed at normal temperature, chelation becomes insufficient.
【００１８】次いで、得られたキレート錯体を含む溶液
を冷却した後、この溶液に前記の感光性樹脂、および必
要に応じて前記の溶剤を添加、混合して透明導電膜形成
用塗布液を得る。このようにして得られた第１の感光性
透明導電膜形成用塗布液は安定性に優れ、９０日間放置
しても分離、沈降することはない。また、前記のキレー
ト錯体の化学構造は必ずしも明確ではないが、錫（Ｓ
ｎ）化合物として酢酸錫（II）を、有機配位子としてア
セチルアセトン（ＡＣＡＣと略記）を用いた場合、下記
式（１）で表わされる化学構造を有するものと推定され
る。 Ｓｎ（ＣＨ3ＣＯＯ）x（ＡＣＡＣ）2-x （１） ただし、０.２≦ｘ≦２.０である。Next, after cooling the obtained solution containing the chelate complex, the above-mentioned photosensitive resin and, if necessary, the above-mentioned solvent are added to this solution and mixed to obtain a coating solution for forming a transparent conductive film. . The coating liquid for forming the first photosensitive transparent conductive film thus obtained has excellent stability, and does not separate or settle even after being left for 90 days. Although the chemical structure of the chelate complex is not always clear, tin (S
n) When tin (II) acetate is used as the compound and acetylacetone (abbreviated as ACAC) is used as the organic ligand, it is assumed that the compound has a chemical structure represented by the following formula (1). Sn (CH 3 COO) x (ACAC) 2-x (1) where 0.2 ≦ x ≦ 2.0.
【００１９】「第２の感光性透明導電膜形成用塗布液」
第２の感光性透明導電膜形成用塗布液は、錫（Ｓｎ）
化合物とアンチモン（Ｓｂ）化合物とにそれぞれ有機配
位子が配位したキレート錯体と、紫外線硬化型または
紫外線崩壊型の感光性樹脂と、前記キレート錯体と前
記感光性樹脂を溶解する溶剤とを少なくとも含有してい
る。そして、この第２の感光性透明導電膜形成用塗布液
は、アンチモン（Ｓｂ）を含有しているので、第１の感
光性透明導電膜形成用塗布液よりも、導電性に優れた透
明導電膜を形成することができる。"Coating solution for forming second photosensitive transparent conductive film"
The coating liquid for forming the second photosensitive transparent conductive film is tin (Sn).
At least a chelate complex in which an organic ligand is coordinated to a compound and an antimony (Sb) compound, a UV-curable or UV-degradable photosensitive resin, and a solvent that dissolves the chelate complex and the photosensitive resin. Contains. Since the second photosensitive transparent conductive film forming coating solution contains antimony (Sb), a transparent conductive film having better conductivity than the first photosensitive transparent conductive film forming coating solution is used. A film can be formed.
【００２０】前記の錫（Ｓｎ）化合物については第１の
感光性透明導電膜形成用塗布液に準ずればよく、また、
アンチモン（Ｓｂ）源となる前記のアンチモン化合物と
しては、トリフェニルアンチモン、塩化アンチモンなど
が溶解性に優れ、キレート錯体が効率よく得られるので
好ましい。The tin (Sn) compound may be the same as the coating liquid for forming the first photosensitive transparent conductive film.
As the above-mentioned antimony compound serving as an antimony (Sb) source, triphenylantimony, antimony chloride and the like are preferable because they have excellent solubility and a chelate complex can be obtained efficiently.
【００２１】また、錫（Ｓｎ）とアンチモン（Ｓｂ）の
含有量は、塗布液重量に基づき酸化物（ＳｎＯ2、Ｓｂ2
Ｏ3）換算の合量で１〜２０重量％が好ましい。１重量
％以下では得られる透明導電膜の膜厚が薄くなり過ぎ、
透明導電膜のマトリックスが充分に形成されず、均質性
及び導電性が低下する虞がある。また、２０重量％を超
えると塗布液中での溶解性が悪くなり成膜時に均一な膜
を得ることができなくなる。また、得られる透明導電膜
の膜が厚くなり過ぎ、クラックが発生して緻密な膜が得
られない。The contents of tin (Sn) and antimony (Sb) are determined based on the weight of the coating solution based on the oxide (SnO 2 , Sb 2).
The total amount is preferably 1 to 20% by weight in terms of O 3 ). If it is less than 1% by weight, the thickness of the obtained transparent conductive film becomes too thin,
There is a possibility that the matrix of the transparent conductive film is not sufficiently formed, and the homogeneity and the conductivity are reduced. On the other hand, when the content exceeds 20% by weight, the solubility in the coating solution is deteriorated, so that a uniform film cannot be obtained at the time of film formation. Further, the obtained transparent conductive film becomes too thick, and cracks occur, so that a dense film cannot be obtained.
【００２２】アンチモン（Ｓｂ）の含有量は、塗布液重
量に基づき、酸化物（Ｓｂ2Ｏ3）に換算してＳｎＯ2１
００重量部に対して、３５重量部以下であることが好ま
しく、より好ましくは３０重量部以下である。アンチモ
ン（Ｓｂ）の配合比を変えることにより、得られる透明
導電膜の比抵抗値は６桁程度変化し、焼成温度、膜厚な
どによっても異なるが、アンチモン（Ｓｂ）の含有量の
増加と共に得られる透明導電膜の比抵抗値は低下し、錫
（Ｓｎ）とアンチモン（Ｓｂ）の比が、ＳｎＯ2とＳｂ2
Ｏ3に換算した重量比で約１００／６以下で膜の表面抵
抗値は数ｋΩ／□と透明電極として十分高い導電性を示
す。従って、透明導電膜に高い導電性を望むときはアン
チモン（Ｓｂ）の含有量はＳｂ2Ｏ3としてＳｎＯ2１０
０重量部に対して約６重量部以上であることが好まし
い。しかしながら、アンチモン（Ｓｂ）の量を、Ｓｂ2
Ｏ3としてＳｎＯ2１００重量部に対して３５重量部を超
える程度に増加しても、比抵抗はもはや低下せず、むし
ろ、アンチモン（Ｓｂ）源であるアンチモン化合物の塗
布液中での溶解性が不良となり、好ましくない。The antimony content of (Sb), based on the coating solution weight, oxide (Sb 2 O 3) in terms of SnO 2 1
The amount is preferably 35 parts by weight or less, more preferably 30 parts by weight or less, based on 00 parts by weight. By changing the compounding ratio of antimony (Sb), the specific resistance value of the obtained transparent conductive film changes by about six digits, and varies depending on the firing temperature, the film thickness, etc., but increases with the content of antimony (Sb). The specific resistance value of the resulting transparent conductive film decreases, and the ratio of tin (Sn) to antimony (Sb) changes to SnO 2 and Sb 2.
When the weight ratio in terms of O 3 is about 100/6 or less, the surface resistance of the film is several kΩ / □, which is sufficiently high as a transparent electrode. Therefore, when high conductivity is desired for the transparent conductive film, the content of antimony (Sb) is changed to SnO 2 10 as Sb 2 O 3.
It is preferably at least about 6 parts by weight per 0 parts by weight. However, the amount of antimony (Sb), Sb 2
Even if O 3 is increased to a level exceeding 35 parts by weight with respect to 100 parts by weight of SnO 2 , the specific resistance no longer decreases, but rather the solubility of the antimony compound as the antimony (Sb) source in the coating solution. Is not good and is not preferable.
【００２３】その他、前記の感光性樹脂、その塗布液中
の含有量、および溶剤については、第１の感光性透明導
電膜形成用塗布液に準ずればよい。また、第２の感光性
透明導電膜形成用塗布液にも、感度を向上させるため適
宜重合開始剤、増感剤などを添加することができる。In addition, the above photosensitive resin, its content in the coating solution, and the solvent may be the same as those of the first photosensitive transparent conductive film forming coating solution. Further, a polymerization initiator, a sensitizer and the like can be appropriately added to the coating liquid for forming the second photosensitive transparent conductive film in order to improve the sensitivity.
【００２４】この第２の透明導電膜形成用塗布液は、例
えば、次のようにして作製することができる。先ず、前
記の錫（Ｓｎ）化合物と、前記のアンチモン（Ｓｂ）化
合物と、前記の有機配位子と、前記の溶剤とを混合し、
これらを、例えば沸点下で１〜５時間還流して反応さ
せ、前記の錫（Ｓｎ）化合物およびアンチモン（Ｓｂ）
化合物にそれぞれ有機配位子が配位したキレート錯体を
調製する。有機配位子の添加量は、錫（Ｓｎ）原子とア
ンチモン（Ｓｂ）原子の合計１モルに対して０.２〜６
モルが好ましく、さらに、前記の有機配位子が前記の溶
剤を兼ねる場合は、有機配位子の添加量は大過剰であっ
てよい。有機配位子の添加量が０.２モルより少ないと
完全なキレート錯体が合成されず、未反応物が残留す
る。また、合成は溶液の沸点下で行うのが好ましく、常
温で合成するとキレート化が不十分となる。The coating liquid for forming the second transparent conductive film can be prepared, for example, as follows. First, the tin (Sn) compound, the antimony (Sb) compound, the organic ligand, and the solvent are mixed,
These are reacted under reflux, for example, at a boiling point for 1 to 5 hours, and the above-mentioned tin (Sn) compound and antimony (Sb)
A chelate complex in which an organic ligand is coordinated to each compound is prepared. The amount of the organic ligand added is 0.2 to 6 with respect to 1 mol of the total of tin (Sn) atoms and antimony (Sb) atoms.
Mole is preferable, and when the organic ligand also serves as the solvent, the amount of the organic ligand added may be a large excess. If the amount of the organic ligand is less than 0.2 mol, a complete chelate complex is not synthesized, and unreacted substances remain. Further, the synthesis is preferably performed at the boiling point of the solution, and when the synthesis is performed at normal temperature, chelation becomes insufficient.
【００２５】次いで、得られたキレート錯体を含む溶液
を冷却した後、この溶液に前記の感光性樹脂、および必
要に応じて前記の溶剤を添加、混合して透明導電膜形成
用塗布液を得る。このようにして得られた第２の感光性
透明導電膜形成用塗布液は安定性に優れ、９０日間放置
しても分離、沈降することはない。また、前記のキレー
ト錯体の化学構造は必ずしも明確ではないが、錫（Ｓ
ｎ）化合物として酢酸錫（II）を、アンチモン（Ｓｂ）
化合物としてトリフェニルアンチモンを、有機配位子と
してアセチルアセトン（ＡＣＡＣと略記）を用いた場
合、下記式（２）で表わされる化学構造を有するものと
推定される。 ｛Ｓｎ（ＣＨ3ＣＯＯ）x（ＡＣＡＣ）2-x・Ｓｂ（Ｃ6Ｈ5）y（ＡＣＡＣ）3-y｝ （２） ただし、０.２≦ｘ≦２.０、０.０≦ｙ≦３.０である。Next, after cooling the obtained solution containing the chelate complex, the above-mentioned photosensitive resin and, if necessary, the above-mentioned solvent are added to the solution and mixed to obtain a coating solution for forming a transparent conductive film. . The coating liquid for forming the second photosensitive transparent conductive film thus obtained has excellent stability, and does not separate or settle even after being left for 90 days. Although the chemical structure of the chelate complex is not always clear, tin (S
n) Tin (II) acetate as a compound, antimony (Sb)
When triphenylantimony is used as the compound and acetylacetone (abbreviated as ACAC) is used as the organic ligand, it is presumed to have a chemical structure represented by the following formula (2). {Sn (CH 3 COO) x (ACAC) 2-x · Sb (C 6 H 5 ) y (ACAC) 3-yた だ し (2) where 0.2 ≦ x ≦ 2.0, 0.0 ≦ y ≦ 3.0.
【００２６】「パターン化された透明導電膜およびその
製造方法」パターン化された透明導電膜は、前記の第１
または第２の感光性透明電極形成用塗布液を基板上に塗
布、乾燥した後、露光、現像してパターン化し、焼成す
ることによって作製される。透明導電膜形成用塗布液を
塗布するには、公知の方法が採用でき、例えばスピンコ
ート法、ロールコート法、ディップコート法などが採用
できる。塗布液の塗布量は、形成される焼成透明導電膜
の膜厚が２０ｎｍ〜５００ｎｍ、好ましくは４０ｎｍ〜
３００ｎｍとなるように適宜調整して塗布する。透明導
電膜の膜厚がこれより薄いと膜としてのネットワークが
十分形成されず、表明抵抗値が高くまた安定しない。逆
に厚いと膜にクラックが発生し易くなり緻密な膜が形成
できなくなる。"Patterned Transparent Conductive Film and Method for Producing the Same"
Alternatively, it is prepared by applying a second photosensitive transparent electrode forming coating solution on a substrate, drying the applied solution, exposing and developing it, patterning it, and baking it. For applying the coating liquid for forming a transparent conductive film, a known method can be employed, for example, a spin coating method, a roll coating method, a dip coating method, or the like. The coating amount of the coating solution is such that the thickness of the formed fired transparent conductive film is 20 nm to 500 nm, preferably 40 nm to 500 nm.
The coating is appropriately adjusted so as to have a thickness of 300 nm. If the thickness of the transparent conductive film is smaller than this, a network as a film is not sufficiently formed, and the assertion resistance value is high and unstable. Conversely, if the film is thick, cracks tend to occur in the film, and a dense film cannot be formed.
【００２７】塗布膜は、乾燥した後、露光、現像してパ
ターン化される。すなわち、塗布膜上に所定のパターン
を有するフォトマスクを設置して紫外線を照射して露光
し、次いで、テトラメチルアンモニウムハイドロキサイ
ト、ジエタノールアミンなどの有機アルカリ、または炭
酸ナトリウム、水酸化ナトリウム、水酸化カリウムなど
の無機アルカリの水溶液で現像してパターン化する。次
いで、パターン形成膜を４００℃以上の温度で３０分〜
２時間焼成することにより、透明導電膜が形成される。
焼成時の雰囲気は特に制限されず、通常大気中で行う。
上記の方法によれば、透明性、導電性および塗膜の機械
的強度、化学的安定性に優れ、しかもパターン加工性に
優れたパターン化された酸化錫系（第１の感光性透明導
電膜を使用した場合）、またはＡＴＯ系（第２の感光性
透明導電膜を使用した場合）の透明導電膜を、非常に簡
易な工程および低コストで作製することができる。After the coating film is dried, it is exposed and developed to be patterned. That is, a photomask having a predetermined pattern is set on the coating film and exposed to ultraviolet light, and then exposed to light. Then, an organic alkali such as tetramethylammonium hydroxide and diethanolamine, or sodium carbonate, sodium hydroxide, and hydroxide are used. The pattern is formed by developing with an aqueous solution of an inorganic alkali such as potassium. Next, the pattern forming film is heated at a temperature of 400 ° C. or more for 30 minutes or more.
By firing for 2 hours, a transparent conductive film is formed.
The atmosphere during firing is not particularly limited, and is usually performed in the air.
According to the above method, a patterned tin oxide-based (first photosensitive transparent conductive film) having excellent transparency, conductivity, mechanical strength and chemical stability of a coating film, and excellent pattern processability. ) Or an ATO-based (when the second photosensitive transparent conductive film is used) transparent conductive film can be manufactured with a very simple process and at low cost.
【００２８】実施例 以下、実施例及び比較例を掲げ、本発明を更に具体的に
説明する。実施例1 酢酸錫（キシダ化学社製）、３９.７ｇと、トリフェニ
ルアンチモン（関東化学社製）、６.４ｇをアセチルア
セトン（関東化学社製）６０.３ｇと混合した後、沸点
下で４時間還流して反応させ、アセチルアセトンが配位
したキレート錯体を得た。この時のＳｂ添加量はＳｂ2
Ｏ3換算でＳｎＯ2１００重量部に対して１０重量部であ
った。次に得られたキレート錯体を室温まで冷却後、ネ
ガ型感光性樹脂（富士フィルムオーリン社製；ＣＳＰ−
Ｓ００４）、１１５.１ｇと希釈溶剤となるアセチルア
セトン（関東化学社製）、７９.７ｇを添加し、室温で
１時間よく攪拌混合することで感光性導電膜形成用塗布
液を得た。塗布液中の錫（Ｓｎ）とアンチモン（Ｓｂ）
の含有量は酸化物（ＳｎＯ2、Ｓｂ2Ｏ3）換算の合量と
して塗布液重量に基づき９重量％であり、また、感光性
樹脂含有量は塗布液重量に基づき１２重量％であった。
なお、このようにして得られた感光性透明導電膜形成用
塗布液を、９０日間放置したところ、分離、沈降は生じ
なかった。EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples. Example 1 39.7 g of tin acetate (manufactured by Kishida Chemical Co., Ltd.) and 6.4 g of triphenylantimony (manufactured by Kanto Chemical Co., Ltd.) were mixed with 60.3 g of acetylacetone (manufactured by Kanto Chemical Co., Ltd.). The reaction was carried out by refluxing for hours to obtain a chelate complex coordinated with acetylacetone. At this time, the amount of Sb added was Sb 2
It was 10 parts by weight based on 100 parts by weight of SnO 2 in terms of O 3 . Next, after cooling the obtained chelate complex to room temperature, a negative photosensitive resin (manufactured by Fuji Film Ohlin Co .; CSP-
S004), 115.1 g, acetylacetone (manufactured by Kanto Chemical Co., Ltd.) as a diluting solvent, and 79.7 g, were added, and the mixture was thoroughly stirred and mixed at room temperature for 1 hour to obtain a coating solution for forming a photosensitive conductive film. Tin (Sn) and antimony (Sb) in coating solution
Was 9% by weight based on the weight of the coating solution in terms of oxide (SnO 2 , Sb 2 O 3 ), and the photosensitive resin content was 12% by weight based on the weight of the coating solution. .
When the coating liquid for forming a photosensitive transparent conductive film thus obtained was allowed to stand for 90 days, no separation or sedimentation occurred.
【００２９】得られた塗布液を無アルカリガラス（コー
ニング＃１７３７）基板上にスピンコーターで塗布した
後、オーブン中１３５℃で５分間乾燥を行った。その後
所定のパターン加工精度評価用のフォトマスク（線幅：
２、３、４、５、……、１５μｍ、線間：２、３、４、
５、……、１５μｍ）を設置して、紫外線露光を行っ
た。用いた紫外線露光機の露光強度は２ｍＷ／ｃｍ
2（ｉ線）で、照射した露光量は５００ｍＪ／ｃｍ2であ
った。次いで、３２℃に保持したテトラメチルアンモニ
ウムハイドロキサイト水溶液の浴で５分間パドル現像を
行い、所定のパターンを得た。この基板を大気中５８０
℃で１時間焼成することでパターン形成されたＡＴＯ系
透明導電薄膜が得られた。得られたパターン膜の膜厚を
触針式膜厚測定装置（ＤＥＫＴＡＫ３０３）、表面抵抗
及び比抵抗値を四端子法抵抗測定装置（三菱化学（株）
製ロレスタＡＰ）、波長５５０ｎｍの光透過率を分光光
度計（日本分光（株）製Ｖ−５７０）、ヘーズ値をヘー
ズメータ（東京電色（株）製 Haze Meter Model ＴＣ
−Ｈ３ＤＰＫ）、膜強度を消しゴム試験法、パターン加
工精度を光学顕微鏡観察法により、それぞれ評価した。
その結果を表１に示した。The obtained coating solution was applied on an alkali-free glass (Corning # 1737) substrate by a spin coater, and then dried in an oven at 135 ° C. for 5 minutes. After that, a photomask (line width:
2, 3, 4, 5,..., 15 μm, between lines: 2, 3, 4,
,..., 15 μm) and exposed to ultraviolet light. The exposure intensity of the used UV exposure machine was 2 mW / cm
At 2 (i-line), the exposure dose was 500 mJ / cm 2 . Subsequently, paddle development was performed for 5 minutes in a bath of an aqueous solution of tetramethylammonium hydroxide maintained at 32 ° C. to obtain a predetermined pattern. This substrate is placed in air at 580
By firing at 1 ° C. for 1 hour, a patterned ATO-based transparent conductive thin film was obtained. The thickness of the obtained pattern film is measured by a stylus-type film thickness measuring device (DEKTAK303), and the surface resistance and the specific resistance are measured by a four-terminal method resistance measuring device (Mitsubishi Chemical Corporation)
Loresta AP), light transmittance at a wavelength of 550 nm was measured with a spectrophotometer (V-570 manufactured by JASCO Corporation), and haze value was measured with a haze meter (Haze Meter Model TC manufactured by Tokyo Denshoku Co., Ltd.)
-H3DPK), a rubber strength eraser test method, and a pattern processing accuracy were evaluated by an optical microscope observation method.
The results are shown in Table 1.
【００３０】実施例２ トリフェニルアンチモンを添加しなかった他は実施例１
に準じて透明導電膜形成用塗布液を得た。この感光性透
明導電膜形成用塗布液を、９０日間放置したところ、分
離、沈降は生じなかった。この透明導電膜形成用塗布液
を用いた他は実施例１に準じてパターン形成された酸化
錫系透明導電膜を得た。このパターン形成された透明導
電膜の特性を実施例１に準じて評価した。その結果を表
１に示した。 Example 2 Example 1 except that triphenylantimony was not added.
A coating liquid for forming a transparent conductive film was obtained in accordance with When the coating liquid for forming a photosensitive transparent conductive film was allowed to stand for 90 days, no separation or sedimentation occurred. A tin oxide-based transparent conductive film patterned in the same manner as in Example 1 except that this coating liquid for forming a transparent conductive film was used was obtained. The characteristics of the patterned transparent conductive film were evaluated in accordance with Example 1. The results are shown in Table 1.
【００３１】実施例３ トリフェニルアンチモンの使用量を１５.７ｇとした他
は実施例１に準じて透明導電膜形成用塗布液を得た。こ
の感光性透明導電膜形成用塗布液を、９０日間放置して
ところ、分離、沈降は生じなかった。なお、Ｓｂ添加量
はＳｂ2Ｏ3換算でＳｎＯ2１００重量部に対して２６重
量部であり、塗布液中のＳｂとＳｎとの合量は（Ｓｂ2
Ｏ3＋ＳｎＯ2）換算で１０重量％であった。この透明導
電膜形成用塗布液を用いた他は実施例１に準じてパター
ン形成されたＡＴＯ系透明導電膜を得た。このパターン
形成された透明導電膜の特性を実施例１に準じて評価し
た。その結果を表１に示した。 Example 3 A coating solution for forming a transparent conductive film was obtained in the same manner as in Example 1 except that the amount of triphenylantimony used was 15.7 g. When the coating liquid for forming a photosensitive transparent conductive film was left for 90 days, no separation or sedimentation occurred. The amount of Sb added was 26 parts by weight based on 100 parts by weight of SnO 2 in terms of Sb 2 O 3, and the total amount of Sb and Sn in the coating solution was (Sb 2
O 3 + SnO 2 ) was 10% by weight. An ATO-based transparent conductive film having a pattern formed in accordance with Example 1 was obtained except that the coating liquid for forming a transparent conductive film was used. The characteristics of the patterned transparent conductive film were evaluated in accordance with Example 1. The results are shown in Table 1.
【００３２】実施例４ ネガ型感光性樹脂（ＣＳＰ−Ｓ００４）の使用量を３
２.３ｇ、希釈溶剤であるアセチルアセトンの使用量を
３１.４ｇとした他は実施例１に準じて透明導電膜形成
用塗布液を得た。この感光性透明導電膜形成用塗布液
を、９０日間放置してところ、分離、沈降は生じなかっ
た。なお、感光性樹脂含有量は５.９重量％であり、
（Ｓｂ2Ｏ3＋ＳｎＯ2）量は１７重量％であった。この
透明導電膜形成用塗布液を用いた他は実施例１に準じて
パターン形成されたＡＴＯ系透明導電膜を得た。このパ
ターン形成された透明導電膜の特性を実施例１に準じて
評価した。その結果を表１に示した。 Example 4 The amount of the negative photosensitive resin (CSP-S004) was changed to 3
A coating solution for forming a transparent conductive film was obtained in the same manner as in Example 1, except that 2.3 g of acetylacetone as a diluting solvent was used and 31.4 g of acetylacetone was used. When the coating liquid for forming a photosensitive transparent conductive film was left for 90 days, no separation or sedimentation occurred. The photosensitive resin content was 5.9% by weight,
The (Sb 2 O 3 + SnO 2 ) amount was 17% by weight. An ATO-based transparent conductive film having a pattern formed in accordance with Example 1 was obtained except that the coating liquid for forming a transparent conductive film was used. The characteristics of the patterned transparent conductive film were evaluated in accordance with Example 1. The results are shown in Table 1.
【００３３】実施例５ 焼成温度を５００℃とした他は実施例１に準じてパター
ン形成されたＡＴＯ系透明導電膜を得た。このパターン
形成された透明導電膜の特性を実施例１に準じて評価し
た。その結果を表１に示した。 Example 5 An ATO-based transparent conductive film patterned in the same manner as in Example 1 except that the sintering temperature was set to 500 ° C. was obtained. The characteristics of the patterned transparent conductive film were evaluated in accordance with Example 1. The results are shown in Table 1.
【００３４】実施例６ 焼成温度を４００℃とした他は実施例１に準じてパター
ン形成されたＡＴＯ系透明導電膜を得た。このパターン
形成された透明導電膜の特性を実施例１に準じて評価し
た。その結果を表１に示した。 Example 6 An ATO-based transparent conductive film having a pattern formed in the same manner as in Example 1 except that the sintering temperature was 400 ° C. was obtained. The characteristics of the patterned transparent conductive film were evaluated in accordance with Example 1. The results are shown in Table 1.
【００３５】比較例１ 無アルカリガラス基板（コーニング＃１７３７）上に感
光性レジスト樹脂（ＣＳＰ−００３Ａ；富士フィルムオ
ーリン社製）をロールコータを用いて塗布し、１３５℃
のホットプレート上で５分間乾燥した。その後、実施例
１で用いたフォトマスクと反対のパターン（ネガパター
ン）を有するパターン加工精度評価用のフォトマスク
（線幅：１０、２０、３０、４０、５０、６０、……、
１００μm、線間：１０、２０、３０、４０、５０、６
０、……、１００μm）を設置して２００ｍＪ／ｃｍ2の
露光量で露光した後、３０℃のアルカリ現像液（ＣＤ−
２０００；富士フィルムオーリン社製の５０％水溶液）
で５分間パドル現像しパターン膜（膜厚；５μm）を得
た。このネガパターン膜付き基板をＣＶＤ装置内のフォ
ットプレート上に設置し、５００℃に加熱した。COMPARATIVE EXAMPLE 1 A photosensitive resist resin (CSP-003A; manufactured by Fuji Film Ohlin Co.) was applied on an alkali-free glass substrate (Corning # 1737) using a roll coater.
For 5 minutes on a hot plate. Thereafter, a photomask (line width: 10, 20, 30, 40, 50, 60,...) For pattern processing accuracy evaluation having a pattern (negative pattern) opposite to the photomask used in Example 1 is used.
100 μm, between lines: 10, 20, 30, 40, 50, 6
0,..., 100 μm) and exposure at an exposure of 200 mJ / cm 2 , followed by 30 ° C. alkaline developer (CD-
2000; 50% aqueous solution manufactured by Fuji Film Ohlin)
For 5 minutes to obtain a pattern film (film thickness: 5 μm). The substrate with the negative pattern film was set on a photoplate in a CVD apparatus and heated to 500 ° C.
【００３６】一方、二塩化ジメチル錫：１４５．８重量
部、三塩化アンチモン：１２．５２重量部を精製水：２
００重量部に溶解させ、さらに塩酸：５重量部を添加し
て錫、アンチモン含有水溶液を作製した。この水溶液中
のＳｂ量は、Ｓｂ2Ｏ3換算でＳｎＯ2に対して８重量％
でり、ＳｂとＳｎとの合量はＳｂ2Ｏ3、ＳｎＯ2換算で
３０重量％であった。このようにして得られた水溶液を
定量ポンプを用いて２００℃以上に加熱したポットに滴
下して気化した混合ガスを得、この混合ガスを空気をキ
ャリアーガスとしてＣＶＤチャンバに導入し、ＣＶＤノ
ズルから加熱された前記ガラス基板に吹き付け、下記の
反応式に従って、ＡＴＯ膜を全面、すなわちパターンの
スペース部分と熱で変質した感光性レジスト膜上の全て
の面状に形成した。 （ＣＨ3）2ＳｎＣｌ2 → Ｓｎ＋２ＣＨ3Ｃｌ↑ ＳｂＣｌ3 → Ｓｂ＋３／２Ｃｌ2 Ｓｎ＋Ｓｂ＋Ｏ2（空気） → ＳｎＯ2（ＳｂがＳｎＯ
2結晶中に固溶したＡＴＯ膜）On the other hand, 145.8 parts by weight of dimethyltin dichloride and 12.52 parts by weight of antimony trichloride were added to 2 parts of purified water:
The solution was dissolved in 00 parts by weight, and 5 parts by weight of hydrochloric acid was further added to prepare an aqueous solution containing tin and antimony. The amount of Sb in this aqueous solution was 8% by weight based on SnO 2 in terms of Sb 2 O 3.
The total amount of Sb and Sn was 30% by weight in terms of Sb 2 O 3 and SnO 2 . The aqueous solution obtained in this manner was dropped into a pot heated to 200 ° C. or higher using a metering pump to obtain a gaseous mixed gas, and the mixed gas was introduced into a CVD chamber using air as a carrier gas, and was then introduced from a CVD nozzle. The ATO film was sprayed on the heated glass substrate, and an ATO film was formed on the entire surface, that is, on the entire surface of the pattern resist and the photosensitive resist film which was altered by heat according to the following reaction formula. (CH 3 ) 2 SnCl 2 → Sn + 2CH 3 Cl ↑ SbCl 3 → Sb + 3 / 2Cl 2 Sn + Sb + O 2 (air) → SnO 2 (Sb is SnO
( ATO film dissolved in 2 crystals)
【００３７】感光性レジスト膜は基板の加熱により、パ
ターンエッジ部が特に変質、変形および一部欠損してお
り、レジスト膜剥離後のＡＴＯ膜は設計どおりの微細な
パターン膜ではなかった。このパターン形成された透明
導電膜の特性を実施例１に準じて評価した。その結果を
表１に示した。The pattern edge of the photosensitive resist film was particularly deteriorated, deformed and partially missing due to the heating of the substrate, and the ATO film after peeling off the resist film was not a fine pattern film as designed. The characteristics of the patterned transparent conductive film were evaluated in accordance with Example 1. The results are shown in Table 1.
【００３８】[0038]
【表１】 [Table 1]
【００３９】[0039]
【発明の効果】本発明の感光性透明電極形成用塗布液
は、錫（Ｓｎ）化合物、または錫（Ｓｎ）化合物とアン
チモン（Ｓｂ）化合物のそれぞれに有機配位子が配位し
たキレート錯体を含有するので、安価で安定性に優れて
いる。また、この感光性透明電極形成用塗布液を基板上
に塗布、乾燥し、該乾燥膜を露光、現像してパターン化
し、さらに焼成して得られる、酸化錫系化合物からなる
透明導電膜は透明性、機械的および化学的安定性に優
れ、またドープするアンチモン量を変えることにより広
範囲の導電性を有する膜が得られ、ディスプレイなどの
透明電極材料や帯電防止材料として適している。さら
に、パターン化された透明導電膜の製造方法は、成膜時
の作業性が良く、非常に簡易な工程で微細なパターン化
された透明導電膜を作製することができる。The coating liquid for forming a photosensitive transparent electrode of the present invention comprises a tin (Sn) compound or a chelate complex in which an organic ligand is coordinated to each of a tin (Sn) compound and an antimony (Sb) compound. Since it contains, it is inexpensive and has excellent stability. The transparent conductive film made of a tin oxide-based compound, which is obtained by applying the coating liquid for forming a photosensitive transparent electrode on a substrate, drying the exposed film, exposing the developed film to a pattern, and further baking, is transparent. By changing the amount of doped antimony, a film having a wide range of conductivity can be obtained, and is suitable as a transparent electrode material for displays and antistatic materials by changing the amount of antimony to be doped. Further, the method for producing a patterned transparent conductive film has good workability at the time of film formation, and can produce a finely patterned transparent conductive film in a very simple process.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｇ０２Ｆ 1/1343 Ｇ０２Ｆ 1/1343 ５Ｇ３０７ Ｇ０３Ｆ 7/004 ５０１ Ｇ０３Ｆ 7/004 ５０１ ５Ｇ３２３ 7/40 ５０１ 7/40 ５０１ Ｈ０１Ｂ 1/20 Ｈ０１Ｂ 1/20 Ａ 5/14 5/14 Ａ Ｆターム(参考） 2H025 AA00 AB17 AC01 AD01 AD03 CC03 CC09 FA03 FA17 FA29 2H092 HA03 MA10 MA14 NA11 NA27 NA29 2H096 AA27 BA01 BA09 BA20 EA02 GA08 4J038 JC38 JC41 KA06 KA12 NA01 NA20 PA17 PA19 PB09 5G301 DA22 DA42 DD02 5G307 FA01 FB01 FC03 5G323 BA04 BB01 BC01 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) G02F 1/1343 G02F 1/1343 5G307 G03F 7/004 501 G03F 7/004 501 5G323 7/40 501 7/40 501 H01B 1/20 H01B 1/20 A 5/14 5/14 A F term (reference) 2H025 AA00 AB17 AC01 AD01 AD03 CC03 CC09 FA03 FA17 FA29 2H092 HA03 MA10 MA14 NA11 NA27 NA29 2H096 AA27 BA01 BA09 BA20 EA02 GA08 4J038 JC38 JC38 KA06 KA12 NA01 NA20 PA17 PA19 PB09 5G301 DA22 DA42 DD02 5G307 FA01 FB01 FC03 5G323 BA04 BB01 BC01
Claims (12)
たキレート錯体と、紫外線硬化型または紫外線崩壊型の
感光性樹脂と、溶剤とを少なくとも含有することを特徴
とする感光性透明導電膜形成用塗布液。1. A photosensitive transparent material comprising at least a chelate complex in which an organic ligand is coordinated with a tin (Sn) compound, a UV-curable or UV-degradable photosensitive resin, and a solvent. Coating solution for conductive film formation.
I）、ぎ酸錫（II）、蓚酸錫（II）、２−エチルヘキサ
ン酸錫（II）、テトラメチル錫（IV）、トリブチル酢酸
錫（IV）、テトラｎ−プロポキシ錫（IV）からなる群か
ら選ばれた少なくとも１種である請求項１記載の感光性
透明導電膜形成用塗布液。2. The method according to claim 1, wherein the tin (Sn) compound is tin acetate (I).
I), tin (II) formate, tin (II) oxalate, tin (II) 2-ethylhexanoate, tetramethyl tin (IV), tin (IV) tributyl acetate, and tetra-n-propoxy tin (IV) The coating liquid for forming a photosensitive transparent conductive film according to claim 1, which is at least one member selected from the group.
ミノアルコール、多価アルコールからなる群から選ばれ
た少なくとも１種である請求項１または請求項２記載の
感光性透明導電膜形成用塗布液。3. The formation of the photosensitive transparent conductive film according to claim 1, wherein the organic ligand is at least one selected from the group consisting of β-diketone, amino alcohol, and polyhydric alcohol. Coating solution.
量に基づき酸化物（ＳｎＯ2）換算で１〜２０重量％で
ある請求項１記載の感光性透明導電膜形成用塗布液。4. The coating liquid for forming a photosensitive transparent conductive film according to claim 1, wherein the content of tin (Sn) is 1 to 20% by weight in terms of oxide (SnO 2 ) based on the weight of the coating liquid. .
化合物とにそれぞれ有機配位子が配位したキレート錯体
と、紫外線硬化型または紫外線崩壊型の感光性樹脂と、
溶剤とを少なくとも含有することを特徴とする感光性透
明導電膜形成用塗布液。5. A tin (Sn) compound and antimony (Sb)
A chelate complex in which an organic ligand is coordinated with the compound, and a UV-curable or UV-degradable photosensitive resin,
A coating liquid for forming a photosensitive transparent conductive film, comprising at least a solvent.
I）、ぎ酸錫（II）、蓚酸錫（II）、２−エチルヘキサ
ン酸錫（II）、テトラメチル錫（IV）、トリブチル酢酸
錫（IV）、テトラｎ−プロポキシ錫（IV）からなる群か
ら選ばれた少なくとも１種である請求項５記載の感光性
透明導電膜形成用塗布液。6. The tin (Sn) compound is a tin acetate (I)
I), tin (II) formate, tin (II) oxalate, tin (II) 2-ethylhexanoate, tetramethyl tin (IV), tin (IV) tributyl acetate, and tetra-n-propoxy tin (IV) The coating liquid for forming a photosensitive transparent conductive film according to claim 5, which is at least one member selected from the group.
リフェニルアンチモン、塩化アンチモンからなる群から
選ばれた少なくとも１種である請求項５または請求項６
記載の感光性透明導電膜形成用塗布液。7. The antimony (Sb) compound is at least one selected from the group consisting of triphenylantimony and antimony chloride.
The coating liquid for forming a photosensitive transparent conductive film according to the above.
ミノアルコール、多価アルコールからなる群から選ばれ
た少なくとも１種である請求項５〜請求項７のいずれか
に記載の感光性透明導電膜形成用塗布液。8. The photosensitive material according to claim 5, wherein said organic ligand is at least one selected from the group consisting of β-diketones, amino alcohols, and polyhydric alcohols. A coating liquid for forming a transparent conductive film.
の含有量は、塗布液重量に基づき酸化物（ＳｎＯ2、Ｓ
ｂ2Ｏ3）換算の合量で１〜２０重量％である請求項５〜
請求項８のいずれかに記載の感光性透明導電膜形成用塗
布液。9. The tin (Sn) and antimony (Sb)
The content of oxide (SnO 2 , S
b 2 O 3) according to claim 5 which is 1 to 20% by weight in total of terms
A coating liquid for forming a photosensitive transparent conductive film according to claim 8.
は、酸化物（Ｓｂ2Ｏ3）に換算してＳｎＯ2１００重量
部に対して、３５重量部以下である請求項５〜請求項９
のいずれかに記載の感光性透明導電膜形成用塗布液。10. The content of the antimony (Sb) is 35 parts by weight or less based on 100 parts by weight of SnO 2 in terms of oxide (Sb 2 O 3 ).
The coating liquid for forming a photosensitive transparent conductive film according to any one of the above.
載の感光性透明導電膜形成用塗布液を基板上に塗布、乾
燥し、該乾燥膜を露光、現像してパターン化し、焼成し
て得られた酸化錫を主成分とすることを特徴とするパタ
ーン化された透明導電膜。11. A coating liquid for forming a photosensitive transparent conductive film according to claim 1, applied to a substrate, dried, and the dried film is exposed, developed, patterned and fired. A patterned transparent conductive film comprising tin oxide obtained as a main component.
載の感光性透明導電膜形成用塗布液を基板上に塗布、乾
燥し、該乾燥膜上にフォトマスクを設置し、紫外線を照
射して露光した後、現像してパターン化し、４００℃以
上の温度で焼成することを特徴とするパターン化された
透明導電膜の製造方法。12. A coating liquid for forming a photosensitive transparent conductive film according to any one of claims 1 to 10, which is applied to a substrate and dried, a photomask is provided on the dried film, and ultraviolet light is applied. And then exposing, developing, patterning, and firing at a temperature of 400 ° C. or higher.
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| CN1299330C (en) * | 2004-12-21 | 2007-02-07 | 中国科学院上海光学精密机械研究所 | Sulfide semiconductor mask for photoetching |
| JP2007526489A (en) * | 2003-06-05 | 2007-09-13 | イーストマン コダック カンパニー | UV curable conductive material in display |
| US8426107B2 (en) | 2008-05-14 | 2013-04-23 | Tokyo Ohka Kogyo Co., Ltd. | Positive-type photosensitive composition |
| JPWO2013099658A1 (en) * | 2011-12-28 | 2015-05-07 | 大日本印刷株式会社 | Optical laminate and image display device |
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| US7119218B2 (en) | 2003-03-31 | 2006-10-10 | Nof Corporation | Low melting point tin salt of carboxylic acid and method for producing the same |
| JP2007526489A (en) * | 2003-06-05 | 2007-09-13 | イーストマン コダック カンパニー | UV curable conductive material in display |
| CN1299330C (en) * | 2004-12-21 | 2007-02-07 | 中国科学院上海光学精密机械研究所 | Sulfide semiconductor mask for photoetching |
| US8426107B2 (en) | 2008-05-14 | 2013-04-23 | Tokyo Ohka Kogyo Co., Ltd. | Positive-type photosensitive composition |
| JP5238023B2 (en) * | 2008-05-14 | 2013-07-17 | 東京応化工業株式会社 | Positive photosensitive composition |
| JPWO2013099658A1 (en) * | 2011-12-28 | 2015-05-07 | 大日本印刷株式会社 | Optical laminate and image display device |
| US11169303B2 (en) | 2011-12-28 | 2021-11-09 | Dai Nippon Printing Co., Ltd. | Optical layered body and image display device |
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| US11535523B2 (en) | 2018-02-14 | 2022-12-27 | Mitsubishi Materials Corporation | Method for producing metal oxide dispersion liquid and method for producing infrared-radiation-shielding film |
| WO2019181833A1 (en) * | 2018-03-22 | 2019-09-26 | 三菱マテリアル株式会社 | Metal oxide microparticles, method for producing same, dispersion for forming infrared-shielding film, method for producing same, method for forming infrared-shielding film, and base material having infrared-shielding film |
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