JP4995878B2 - Transparent conductive film forming dispersion, transparent conductive film forming photocurable composition, and transparent conductive film - Google Patents
Transparent conductive film forming dispersion, transparent conductive film forming photocurable composition, and transparent conductive film Download PDFInfo
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Description
本発明は、保存安定性に優れた透明導電膜形成用分散液、透明導電膜形成用光硬化性組成物及び該組成物から得られる透明導電膜に関し、より詳しくは、プラスチック、金属、木材、紙、ガラス、スレート等の各種基材の表面に透明性に優れ、且つ、帯電防止機能を有する透明導電膜を形成し得る光硬化性組成物、該組成物から得られる透明性に優れ、且つ、帯電防止機能を有する透明導電膜、及び、そのような光硬化性組成物の調製に用いられる保存安定性に優れた透明導電膜形成用分散液に関する。 The present invention for forming transparent conductive film dispersion having excellent storage stability, relates to a transparent conductive film obtained from the transparent conductive film forming photocurable composition and the composition, and more particularly, plastic, metal, wood, A photocurable composition that is excellent in transparency on the surface of various substrates such as paper, glass, and slate and that can form a transparent conductive film having an antistatic function, excellent in transparency obtained from the composition, and The present invention also relates to a transparent conductive film having an antistatic function, and a dispersion for forming a transparent conductive film excellent in storage stability used for the preparation of such a photocurable composition.
近年、各種基材の表面の傷付き（擦傷）防止や汚染防止のための保護コーティング材や、印刷インクのバインダー材として、優れた塗工性を有し、且つ、各種基材の表面に硬度、耐擦傷性、耐摩耗性、低カール性、密着性、透明性、耐薬品性、塗膜面の外観等に優れた透明導電膜を形成し得る硬化性組成物が要求されている。 In recent years, it has excellent coating properties as a protective coating material for preventing scratches (abrasion) on surfaces of various substrates and preventing contamination, and a binder material for printing inks, and the surface of various substrates has hardness. There is a demand for a curable composition capable of forming a transparent conductive film excellent in scratch resistance, abrasion resistance, low curling properties, adhesion, transparency, chemical resistance, coating film appearance, and the like.
また、フラットパネルディスプレイ、タッチパネル、プラスチック光学部品等への用途においては、上記要求に加えて、透明性に優れ、且つ、帯電防止機能を有する透明導電膜等の透明導電膜を形成し得る硬化性組成物が要求されている。 Moreover, in applications to flat panel displays, touch panels, plastic optical components, etc., in addition to the above requirements, curability that can form a transparent conductive film such as a transparent conductive film that is excellent in transparency and has an antistatic function. There is a need for a composition.
更に、液晶ディスプレイ、陰極管表示装置等の画像表示装置及び光学製品においては反射防止膜（透明導電膜）が使用されている。この反射防止膜には、高い透明性及び低い反射率の特性に加え、耐擦傷性及び埃やゴミ等の異物の付着を防止する機能が要求されている。そのため、反射防止膜の高屈折率層には、高い透明性及び高い屈折率特性に加え、優れた耐擦傷性及び帯電防止特性が求められている。 Further, liquid crystal display, an antireflection film (transparent conductive film) is used in an image display device and optical products such as cathode ray tube display. In addition to the characteristics of high transparency and low reflectance, the antireflection film is required to have a scratch resistance and a function of preventing adhesion of foreign matters such as dust and dirt. Therefore, the high refractive index layer of the antireflection film is required to have excellent scratch resistance and antistatic properties in addition to high transparency and high refractive index properties.
そして、このような透明導電膜に帯電防止機能を付与する手段としては、硬化性組成物中に界面活性剤、導電性ポリマー、又は主として金属酸化物からなる導電性微粒子等を添加する方法が知られており、特に永久帯電防止効果を有する膜を作製するという目的を考慮した場合には、導電性微粒子を添加する方法が一般的となっている。そのような導電性微粒子を添加する方法としては、樹脂溶液又は溶剤中にキレート剤を配合し、その配合物中に無機酸化物を分散させる方法がある（例えば、特許文献１及び２参照）。 As a means for imparting an antistatic function to such a transparent conductive film, a method of adding a surfactant, a conductive polymer, or conductive fine particles mainly composed of a metal oxide to the curable composition is known. In particular, in consideration of the purpose of producing a film having a permanent antistatic effect, a method of adding conductive fine particles is common. As a method for adding such conductive fine particles, there is a method in which a chelating agent is blended in a resin solution or a solvent, and an inorganic oxide is dispersed in the blend (for example, see Patent Documents 1 and 2).
上記の用途に用いられる透明導電膜形成用分散液及びその硬化性組成物については、導電性微粒子の粒子径が小さく、且つ、分散液が保存安定性に優れていることが求められている。上記の特許文献１及び２に記載されているキレート剤は金属とキレートを形成するので、分散処理過程で使用される金属製機器や塗布機材を腐食させるという問題がある。 About the dispersion liquid for transparent conductive film formation used for said use, and its curable composition, it is calculated | required that the particle diameter of electroconductive fine particles is small and the dispersion liquid is excellent in storage stability. Since the chelating agents described in Patent Documents 1 and 2 form chelates with metals, there is a problem of corroding metal equipment and coating equipment used in the dispersion treatment process.
本発明は、上記の問題に鑑みてなされたものであり、（１）基材の表面に透明性に優れていると共に帯電防止機能を有する透明導電膜を形成することができ、分散処理過程で使用される金属製機器や塗布機材を腐食させることのない透明導電膜形成用光硬化性組成物、（２）該透明導電膜形成用光硬化性組成物から得られる透明導電膜等の各種の透明導電膜、（３）該透明導電膜形成用光硬化性組成物から得られる透明導電膜を有するディスプレイ、及び（４）そのような透明導電膜形成用光硬化性組成物の調製に用いられる保存安定性に優れた透明導電膜形成用分散液を提供することを目的とする。 The present invention has been made in view of the above-mentioned problems. (1) A transparent conductive film having excellent antistatic function and excellent transparency can be formed on the surface of a substrate. metal equipment and does not cause corrosion of the coating equipment for forming transparent conductive film photocurable composition used, (2) the transparent conductive film of the transparent conductive film or the like obtained from forming photocurable composition various a transparent conductive film, used for the preparation of (3) a display having a transparent conductive film obtained from the transparent conductive film forming photocurable composition, and (4) such a transparent conductive film forming photocurable composition It aims at providing the dispersion liquid for transparent conductive film formation excellent in storage stability.
本発明者らは、上記の諸目的を達成するために鋭意検討した結果、分散媒中に特定の導電性微粒子及び特定の金属錯体を特定の割合で分散させることにより保存安定性に優れた透明導電膜形成用分散液が得られることを見出し、また、そのような透明導電膜形成用分散液を用いることにより分散処理過程で金属製機器や塗布機材を腐食させることのない透明導電膜形成用光硬化性組成物が得られることを見出し、本発明を完成した。 As a result of diligent investigations to achieve the above-mentioned objects, the present inventors have found that transparent particles having excellent storage stability can be obtained by dispersing specific conductive fine particles and specific metal complexes at a specific ratio in a dispersion medium. It is found that a dispersion for forming a conductive film is obtained, and for forming a transparent conductive film that does not corrode metal equipment and coating equipment during the dispersion process by using such a dispersion for forming a transparent conductive film. It discovered that a photocurable composition was obtained and completed this invention.
即ち、本発明の透明導電膜形成用分散液は、導電性微粒子１００質量部当り、アルコキシドを含まず、かつ、透明導電膜形成後に該透明導電膜を形成する成分として残存する金属錯体（以下、「膜形成成分の金属錯体」と称する場合がある。）を２〜４５質量部の割合で含むと共に、分散媒を４０〜１０００質量部の割合で含み、硬化性組成物を構成してこの硬化性組成物により屈折率１．４５〜１．９０、光透過率７５%以上、ヘイズ２．０%以下及び表面抵抗値１×１０ 9 Ω／□以下の透明導電膜を形成するための分散液であり、
前記導電性微粒子がＩＴＯ、ＡＴＯ、酸化錫、酸化亜鉛、酸化インジウム、アンチモン酸亜鉛及び五酸化アンチモンよりなる群から選ばれる１種類のみの金属酸化物であって、前記金属錯体がジルコニウム、チタン、アルミニウム、亜鉛、インジウム及び錫からなる群から選ばれる金属とβ-ジケトンからなる群から選ばれる配位子とからなること（但し、前記導電性微粒子以外の屈折率１．５５以上の無機微粒子を含む場合、及び分散媒としてエチレングリコールを含む場合を除く。）を特徴とする。
That is, the dispersion for forming a transparent conductive film of the present invention contains a metal complex (hereinafter referred to as “component”) that does not contain alkoxide and remains as a component that forms the transparent conductive film after forming the transparent conductive film, per 100 parts by weight of the conductive fine particles. This may be referred to as a “metal complex of a film-forming component.”) In a ratio of 2 to 45 parts by mass and a dispersion medium in a ratio of 40 to 1000 parts by mass to constitute a curable composition and this curing Dispersion for forming a transparent conductive film having a refractive index of 1.45 to 1.90, a light transmittance of 75% or more, a haze of 2.0% or less, and a surface resistance value of 1 × 10 9 Ω / □ or less by a conductive composition And
The conductive fine particles are only one kind of metal oxide selected from the group consisting of ITO, ATO, tin oxide, zinc oxide, indium oxide, zinc antimonate and antimony pentoxide, and the metal complex is zirconium, titanium, It consists of a metal selected from the group consisting of aluminum, zinc, indium and tin and a ligand selected from the group consisting of β-diketone (however, inorganic fine particles having a refractive index of 1.55 or more other than the conductive fine particles) And the case of containing ethylene glycol as a dispersion medium).
そして、本発明の透明導電膜形成用光硬化性組成物は、上記の透明導電膜形成用分散液に加えて、活性エネルギー線硬化性化合物を１０〜１０００質量部の割合で含むと共に、光重合開始剤をこの活性エネルギー線硬化性化合物１００質量部当り０．１〜２０質量部の割合で含むことを特徴とする。 And the photocurable composition for transparent conductive film formation of this invention contains an active energy ray-curable compound in the ratio of 10-1000 mass parts in addition to said dispersion liquid for transparent conductive film formation, and photopolymerization. An initiator is contained at a ratio of 0.1 to 20 parts by mass per 100 parts by mass of the active energy ray-curable compound .
更に、本発明の透明導電膜は、上記の透明導電膜形成用光硬化性組成物を基材上に塗布又は印刷し、硬化させて得られるものであることを特徴とし、好ましくは、屈折率が１．４５〜１．９０であり、光透過率が７５%以上であり、ヘイズが２．０%以下であり、且つ表面抵抗値が１×１０ 9 Ω／□以下であることを特徴とする。 Furthermore, the transparent conductive film of the present invention is characterized by being obtained by applying or printing the above-mentioned photocurable composition for forming a transparent conductive film on a substrate and curing it, preferably having a refractive index. 1.45 to 1.90, the light transmittance is 75% or more, the haze is 2.0% or less, and the surface resistance value is 1 × 10 9 Ω / □ or less. To do.
本発明により、（１）分散液の保存安定性に優れた透明導電膜形成用分散液が提供され、（２）基材の表面に透明性に優れ、且つ、帯電防止機能を有する透明導電膜を形成することができ、分散処理過程で使用される金属製機器や塗布機材を腐食させることのない透明導電膜形成用光硬化性組成物が提供され、更に（３）該組成物から得られる透明性に優れ、且つ、帯電防止機能を有する透明導電膜が提供される。 The present invention, (1) excellent storage stability for forming transparent conductive film dispersion of the dispersion is provided, (2) excellent in transparency on the surface of the substrate, and a transparent conductive film having an antistatic function And a photocurable composition for forming a transparent conductive film that does not corrode metal equipment and coating equipment used in the dispersion treatment process, and (3) is obtained from the composition. A transparent conductive film having excellent transparency and an antistatic function is provided.
以下に本発明の実施の形態を具体的に説明する。
本発明の透明導電膜形成用分散液は、導電性微粒子、膜形成成分の金属錯体及び分散媒を含有している。本発明で用いる導電性微粒子の形状については特に限定されない。導電性微粒子の導電性としては体積抵抗率として１０7Ω・cm以下、好ましくは１０3Ω・cm以下である。また、導電性微粒子の大きさについては、一次粒子径で、通常、１〜５００nm、好ましくは１０〜１００nmのものを使用することができる。
Embodiments of the present invention will be specifically described below.
The dispersion for forming a transparent conductive film of the present invention contains conductive fine particles, a metal complex of a film forming component, and a dispersion medium. The shape of the conductive fine particles used in the present invention is not particularly limited. The conductive fine particles have a volume resistivity of 10 7 Ω · cm or less, preferably 10 3 Ω · cm or less. As for the size of the conductive fine particles, those having a primary particle diameter of usually 1 to 500 nm, preferably 10 to 100 nm can be used.
本発明で用いる導電性微粒子の種類については、ＩＴＯ、ＡＴＯ、酸化錫、酸化亜鉛、酸化インジウム、アンチモン酸亜鉛、及び五酸化アンチモンよりなる群から選ばれる１種類のみの金属酸化物が用いられる。酸化錫についてはリンなどの元素をドープしたものを用いることもできる。酸化亜鉛についてはガリウムやアルミニウムをドープしたものを用いることもできる。 About the kind of electroconductive fine particles used by this invention, only 1 type of metal oxide chosen from the group which consists of ITO, ATO, a tin oxide, a zinc oxide, an indium oxide, a zinc antimonate, and an antimony pentoxide is used . As the tin oxide, one doped with an element such as phosphorus can also be used. It can also Mochiiruko the doped with gallium or aluminum for zinc oxide.
本発明の透明導電膜形成用分散液おいては、上記の導電性微粒子に加えて、分散媒中に膜形成成分の金属錯体が配合される。この金属錯体は、分散液において分散剤として機能するので、分散液の保存安定性に優れた透明導電膜形成用分散液を得ることができる。また、金属錯体は分散過程で使用される金属製機器や塗布機材を腐食することは殆どない。 In the transparent conductive film forming dispersion of the present invention, in addition to the conductive fine particles, a metal complex as a film forming component is blended in the dispersion medium. Since this metal complex functions as a dispersant in the dispersion, a dispersion for forming a transparent conductive film having excellent storage stability of the dispersion can be obtained. Further, the metal complex hardly corrodes metal equipment and coating equipment used in the dispersion process.
本発明で用いる膜形成成分の金属錯体としては、透明導電膜形成用分散液の色味が少ない点で、ジルコニウム、チタン、アルミニウム、亜鉛、インジウム及び錫からなる群から選ばれる金属と、β-ジケトンからなる群から選ばれる配位子、好ましくはピバロイルトリフルオルアセトン、アセチルアセトン、トリフルオルアセチルアセトン及びヘキサフルオルアセチルアセトンからなる群から選ばれる配位子、より好ましくはアルコキシドを含まない金属錯体を挙げることができる。アルコキシドを含む金属錯体を用いた場合には、アルコキシドが溶剤に含まれる水分又は空気中の水分と経時的に反応し、透明導電膜形成用分散液及び透明導電膜形成用光硬化性組成物の保存安定性及び膜特性が低下する傾向がある。 The metal complexes of film forming component used in the present invention, in view color of the transparent conductive film forming dispersion is small, a metal selected zirconium, titanium, aluminum, zinc, from the group consisting of indium and tin, beta- A ligand selected from the group consisting of diketones, preferably a ligand selected from the group consisting of pivaloyltrifluoroacetone, acetylacetone, trifluoroacetylacetone and hexafluoroacetylacetone, more preferably a metal complex containing no alkoxide. Can be mentioned. When a metal complex containing an alkoxide is used, the alkoxide reacts with moisture contained in the solvent or moisture in the air over time, and the transparent conductive film forming dispersion and the transparent conductive film forming photocurable composition Storage stability and membrane properties tend to decrease .
なお、分散液の保存安定性をより向上させる目的で、分散助剤として更に他の分散剤を添加してもよい。そのような分散助剤の種類は、特に限定されないが、そのような分散助剤として、好ましくは、ポリオキシエチレンアルキル構造を有するリン酸エステル系ノニオン型分散剤を挙げることができる。 For the purpose of further improving the storage stability of the dispersion, another dispersant may be added as a dispersion aid. The kind of the dispersion aid is not particularly limited, but as such a dispersion aid, a phosphate ester nonionic dispersant having a polyoxyethylene alkyl structure is preferable.
本発明で用いる分散媒としては、水、メタノール、エタノール、イソプロパノール、ノルマルブタノール、2-ブタノール、オクタノール等のアルコール類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、4-ヒドロキシ-4-メチル-2-ペンタノン等のケトン類；酢酸エチル、酢酸ブチル、乳酸エチル、γ-ブチロラクトン、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等のエステル類；エチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル等のエーテル類；ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素類；ジメチルホルムアミド、N,N-ジメチルアセトアセトアミド、N-メチルピロリドン等のアミド類等を挙げることができる。それらの中でも、エタノール、イソプロパノール、ノルマルブタノール、2-ブタノール、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、4-ヒドロキシ-4-メチル-2-ペンタノン、酢酸エチル、酢酸ブチル、トルエン、キシレン、エチルベンゼンが好ましく、メチルエチルケトン、ブタノール、キシレン、エチルベンゼン、トルエンがより好ましい。本発明においては、分散媒として一種単独で用いることも、二種以上を併用することもできる。 Examples of the dispersion medium used in the present invention include alcohols such as water, methanol, ethanol, isopropanol, normal butanol, 2-butanol, and octanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2- Ketones such as pentanone; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; benzene , Aromatic hydrocarbons such as toluene, xylene, ethylbenzene; amides such as dimethylformamide, N, N-dimethylacetoacetamide, N-methylpyrrolidone, etc. Can be mentioned. Among them, ethanol, isopropanol, normal butanol, 2-butanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, ethyl acetate, butyl acetate, toluene, xylene, and ethylbenzene are preferable, and methyl ethyl ketone Butanol, xylene, ethylbenzene, and toluene are more preferable. In the present invention, the dispersion medium may be used alone or in combination of two or more.
本発明の透明導電膜形成用分散液においては、各成分の配合割合は透明導電膜形成用分散液の用途に応じて適宜設定できるが、導電性微粒子１００質量部当り、膜形成成分の金属錯体の含有量は好ましくは２〜４５質量部、より好ましくは５〜２０質量部であり、分散媒の含有量は好ましくは４０〜１０００質量部、より好ましくは６０〜６００質量部である。金属錯体の量が上記の下限値より少ない場合には導電性微粒子の分散不良となり、上記の上限値より多い場合には金属錯体が分散媒中に溶解せず、沈殿が生じることがある。また、分散媒の量が上記の下限値より少ない場合には金属錯体の溶解、導電性微粒子の分散が不十分となり、上記の上限値より多い場合には透明導電膜形成用分散液の濃度が薄すぎて実用的でなくなる。 In the dispersion for forming a transparent conductive film of the present invention, the mixing ratio of each component can be appropriately set according to the use of the dispersion for forming a transparent conductive film, but the metal complex of the film forming component per 100 parts by mass of the conductive fine particles. The content of is preferably 2 to 45 parts by mass, more preferably 5 to 20 parts by mass, and the content of the dispersion medium is preferably 40 to 1000 parts by mass, more preferably 60 to 600 parts by mass. When the amount of the metal complex is less than the above lower limit value, the conductive fine particles are poorly dispersed. When the amount is more than the above upper limit value, the metal complex does not dissolve in the dispersion medium and precipitation may occur. In addition, when the amount of the dispersion medium is less than the above lower limit value, the dissolution of the metal complex and the dispersion of the conductive fine particles are insufficient, and when the amount is more than the above upper limit value, the concentration of the dispersion liquid for forming the transparent conductive film is It is too thin to be practical.
本発明の透明導電膜形成用分散液は、導電性微粒子、金属錯体及び分散媒を任意の順序で添加し、充分に混合することにより得られる。普通には、金属錯体を溶解した分散媒中に導電性微粒子を分散させて製造する。分散操作を行う前にはプレ分散操作を行うとなおよい。プレ分散操作は、金属錯体を溶解した分散媒中に、ディスパー等で撹拌しながら、導電性微粒子を徐々に加えていき、これら導電性微粒子の塊が目視で確認されなくなるまでよく撹拌すればよい。 The dispersion for forming a transparent conductive film of the present invention can be obtained by adding conductive fine particles, a metal complex and a dispersion medium in an arbitrary order and mixing them sufficiently. Usually, it is produced by dispersing conductive fine particles in a dispersion medium in which a metal complex is dissolved. It is even better to perform a pre-dispersion operation before performing the dispersion operation. In the pre-dispersion operation, the conductive fine particles are gradually added to the dispersion medium in which the metal complex is dissolved while stirring with a disper or the like, and the conductive fine particles may be stirred well until a lump of the conductive fine particles is not visually confirmed. .
導電性微粒子の分散操作は、ペイントシェーカー、ボールミル、サンドミル、セントリミル等を用いて行うことができる。分散操作の際に、ガラスビーズ、ジルコニアビーズ等の分散ビーズを用いることが好ましい。ビーズ径は、特に限定されないが、通常０．０５〜１mm程度であり、好ましくは０．０５〜０．６５mmである。 The dispersion operation of the conductive fine particles can be performed using a paint shaker, a ball mill, a sand mill, a sentry mill or the like. In the dispersion operation, it is preferable to use dispersed beads such as glass beads and zirconia beads. The bead diameter is not particularly limited, but is usually about 0.05 to 1 mm, preferably 0.05 to 0.65 mm .
本発明の透明導電膜形成用分散液においては、導電性微粒子の粒子径は、メジアン径で、好ましくは１２０nm以下、さらに好ましくは８０nm以下である。メジアン径がそれ以上であると、透明導電膜形成用光硬化性組成物から得られる透明導電膜のヘイズが高くなる傾向がある。 In the dispersion for forming a transparent conductive film of the present invention, the particle diameter of the conductive fine particles is a median diameter, preferably 120 nm or less, more preferably 80 nm or less. There exists a tendency for the haze of the transparent conductive film obtained from the photocurable composition for transparent conductive film formation to become it that a median diameter is more than that.
本発明の透明導電膜形成用分散液は、導電性微粒子が長期にわたり安定に分散しており、また、金属を腐食させるアセチルアセトン等が含有されていないため、金属製の容器に保管が可能である。 The dispersion for forming a transparent conductive film according to the present invention has a stable dispersion of conductive fine particles over a long period of time, and does not contain acetylacetone or the like that corrodes metal, so that it can be stored in a metal container. .
本発明の透明導電膜形成用分散液は、保護膜形成用組成物、反射防止膜形成用組成物、接着剤、シーリング材、バインダー材等に含ませて用いることができ、特に帯電防止機能を有する反射防止膜を形成する組成物に好適に用いることができる。 The dispersion for forming a transparent conductive film of the present invention can be used by being included in a composition for forming a protective film, a composition for forming an antireflection film, an adhesive, a sealing material, a binder material, etc., and particularly has an antistatic function. It can use suitably for the composition which forms the anti-reflective film which has.
本発明の透明導電膜形成用光硬化性組成物は、導電性微粒子、金属錯体、活性エネルギー線硬化性化合物、光重合開始剤及び分散媒を含有しており、導電性微粒子、金属錯体及び分散媒は上記した通りである。 The photocurable composition for forming a transparent conductive film of the present invention contains conductive fine particles, a metal complex, an active energy ray-curable compound, a photopolymerization initiator and a dispersion medium, and the conductive fine particles, the metal complex and the dispersion. The medium is as described above.
本発明で用いる活性エネルギー線硬化性化合物としては、ラジカル重合性モノマー、ラジカル重合性オリゴマー等を挙げることができる。
ラジカル重合性モノマーの具体例としては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、イソプロピル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ブチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、メトキシポリエチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート、ポリエチレングリコールポリプロピレングリコールモノ(メタ)アクリレート、ポリエチレングリコールポリテトラメチレングリコールモノ(メタ)アクリレート、グリシジル(メタ)アクリレート等の単官能(メタ)アクリレート；エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、アリルジ(メタ)アクリレート、ビスフェノールＡジ(メタ)アクリレート、エチレンオキサイド変性ビスフェノールＡジ(メタ)アクリレート、ポリエチレンオキサイド変性ビスフェノールＡジ(メタ)アクリレート、エチレンオキサイド変性ビスフェノールＳジ(メタ)アクリレート、ビスフェノールＳジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、1,3-ブチレングリコールジ(メタ)アクリレート等の二官能(メタ)アクリレート；トリメチロールプロパントリ(メタ)アクリレート、グリセロールトリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、エチレン変性トリメチロールプロパントリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート等の三官能以上の(メタ)アクリレート；スチレン、ビニルトルエン、酢酸ビニル、N-ビニルピロリドン、アクリロニトリル、アリルアルコール等のラジカル重合性モノマーを挙げることができる。
Examples of the active energy ray-curable compound used in the present invention include radical polymerizable monomers and radical polymerizable oligomers.
Specific examples of the radical polymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofluorine Furyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene Monofunctional (meth) acrylates such as glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol polytetramethylene glycol mono (meth) acrylate, and glycidyl (meth) acrylate Relate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, allyl di (meth) acrylate, bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, polyethylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol S di (meth) acrylate, bisphenol S di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate Bifunctional (meth) acrylates such as rate; trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene modified trimethylolpropane tri (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and other trifunctional or more (meth) acrylates; styrene, vinyl toluene, vinyl acetate, N-vinyl pyrrolidone, acrylonitrile, allyl alcohol, etc. Mention may be made of radically polymerizable monomers.
また、ラジカル重合性オリゴマーの具体例としては、ポリエステル(メタ)アクリレート、ポリウレタン(メタ)アクリレート、エポキシ(メタ)アクリレート、ポリエーテル(メタ)アクリレート、オリゴ(メタ)アクリレート、アルキド(メタ)アクリレート、ポリオール(メタ)アクリレート、シリコーン(メタ)アクリレートなどの(メタ)アクリロイル基を少なくとも１個有するプレポリマーを挙げることができる。特に好ましいラジカル重合性オリゴマーは、ポリエステル、エポキシ、ポリウレタンの各(メタ)アクリレートである。本発明において活性エネルギー線硬化性化合物は一種単独で用いることも、二種以上を併用することもできる。 Specific examples of the radical polymerizable oligomer include polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, oligo (meth) acrylate, alkyd (meth) acrylate, polyol Examples thereof include prepolymers having at least one (meth) acryloyl group such as (meth) acrylate and silicone (meth) acrylate. Particularly preferred radical polymerizable oligomers are (meth) acrylates of polyester, epoxy, and polyurethane. In this invention, an active energy ray hardening compound can be used individually by 1 type, or can also use 2 or more types together.
本発明の透明導電膜形成用光硬化性組成物においては、光重合開始剤（光増感剤）を含有するので、少量の活性エネルギー線の照射で透明導電膜形成用光硬化性組成物を硬化させることができる。 Since the photocurable composition for forming a transparent conductive film of the present invention contains a photopolymerization initiator (photosensitizer), the photocurable composition for forming a transparent conductive film is formed by irradiation with a small amount of active energy rays. It can be cured.
本発明で用いる光重合開始剤（光増感剤）としては、例えば、1-ヒドロキシシクロヘキシルフェニルケトン、ベンゾフェノン、ベンジルジメチルケトン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、p-クロロベンゾフェノン、4-ベンゾイル-4-メチルジフェニルサルファイド、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタノン-1、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノプロパノン-1を挙げることができる。光重合開始剤は一種単独で用いることも、二種以上を併用することもできる。 Examples of the photopolymerization initiator (photosensitizer) used in the present invention include 1-hydroxycyclohexyl phenyl ketone, benzophenone, benzyl dimethyl ketone, benzoin methyl ether, benzoin ethyl ether, p-chlorobenzophenone, 4-benzoyl-4 2-methyldiphenyl sulfide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 Can be mentioned. A photoinitiator can be used individually by 1 type, or can also use 2 or more types together.
本発明の透明導電膜形成用光硬化性組成物においては、各成分の配合割合は透明導電膜形成用光硬化性組成物の用途に応じて適宜設定できるが、導電性微粒子１００質量部当り、金属錯体の含有量は好ましくは２〜４５質量部、より好ましくは５〜２０質量部であり、分散媒の含有量は好ましくは４０〜１０００質量部、より好ましくは６０〜６００質量部であり、活性エネルギー線硬化性化合物の含有量は好ましくは１０〜１０００質量部、より好ましくは２５〜１５０質量部であり、且つ活性エネルギー線硬化性化合物１００質量部当り光重合開始剤の含有量は好ましくは０．１〜２０質量部、より好ましくは１〜１５質量部である。 In the photocurable composition for forming a transparent conductive film of the present invention, the blending ratio of each component can be appropriately set according to the use of the photocurable composition for forming a transparent conductive film, but per 100 parts by mass of the conductive fine particles, The content of the metal complex is preferably 2-45 parts by mass, more preferably 5-20 parts by mass, and the content of the dispersion medium is preferably 40-1000 parts by mass, more preferably 60-600 parts by mass, The content of the active energy ray curable compound is preferably 10 to 1000 parts by mass, more preferably 25 to 150 parts by mass, and the content of the photopolymerization initiator per 100 parts by mass of the active energy ray curable compound is preferably It is 0.1-20 mass parts, More preferably, it is 1-15 mass parts.
ここで、金属錯体の量が上記の下限値より少ない場合には導電性微粒子の分散不良となる傾向があり、上記の上限値より多い場合には金属錯体が分散媒中に溶解せず、沈殿が生じることがある。分散媒の量が上記の下限値より少ない場合には金属錯体の溶解、導電性微粒子の分散が不十分となる傾向があり、上記の上限値より多い場合には透明導電膜形成用分散液の濃度が薄すぎて導電性微粒子の添加効果が不十分となる傾向がある。活性エネルギー線硬化性化合物の量が上記の下限値より少ない場合には透明導電膜の屈折率が高くなるが透明性が低下する傾向があり、上記の上限値より多い場合には透明導電膜の屈折率が所望程度には高くならない。また、光重合開始剤の量が上記の下限値より少ない場合には光硬化性組成物の硬化速度が低下する傾向があり、上記の上限値よりも多くてもそれに見合った効果が得られない。 Here, when the amount of the metal complex is less than the above lower limit value, the conductive fine particles tend to be poorly dispersed, and when the amount is more than the above upper limit value, the metal complex does not dissolve in the dispersion medium and precipitates. May occur. Dissolution of the metal complex in the case the amount of dispersion medium is lower than the lower limit, there is a tendency that dispersibility becomes insufficient conductive particles, if more than the upper limit of the above transparent conductive film forming dispersion The concentration is too thin and the effect of adding conductive fine particles tends to be insufficient. Tend to the amount of the active energy ray-curable compound is a high refractive index of the transparent conductive film when less than the lower limit of the reduced transparency, if more than the upper limit of the above transparent conductive film The refractive index is not as high as desired. In addition, when the amount of the photopolymerization initiator is less than the above lower limit value, the curing rate of the photocurable composition tends to decrease, and even if the amount exceeds the above upper limit value, an effect commensurate with it cannot be obtained. .
更に、本発明の透明導電膜形成用光硬化性組成物には、その目的を損なわない範囲内で、上記以外の慣用の各種添加剤を配合してもよい。このような添加剤として、重合禁止剤、硬化触媒、酸化防止剤、レベリング剤、カップリング剤等を挙げることができる。 Furthermore, you may mix | blend various conventional additives other than the above in the range which does not impair the objective to the photocurable composition for transparent conductive film formation of this invention. Examples of such additives include a polymerization inhibitor, a curing catalyst, an antioxidant, a leveling agent, and a coupling agent.
本発明の透明導電膜形成用光硬化性組成物は、プラスチック（ポリカーボネート、ポリメチルメタクリレート、ポリスチレン、ポリエステル、ポリオレフィン、エポキシ樹脂、メラミン樹脂、トリアセチルセルロース樹脂、ポリエチレンテレフタレート、ＡＢＳ樹脂、ＡＳ樹脂、ノルボルネン系樹脂等）、金属、木材、紙、ガラス、スレート等の各種基材の表面に塗布又は印刷し、硬化させて膜を形成することができ、例えば、プラスチック光学部品、タッチパネル、フィルム型液晶素子、プラスチック容器、建築内装材としての床材、壁材、人工大理石等の傷付き（擦傷）防止や汚染防止のための保護コーティング材；フィルム型液晶素子、タッチパネル、プラスチック光学部品等の反射防止膜；各種基材の接着剤、シーリング材；印刷インクのバインダー材等に用いられ、特に帯電防止機能を有する反射防止膜を形成する組成物に好適に用いることができる。また、高屈折率微粒子が配合された透明導電膜形成用光硬化性組成物の場合には、特に高屈折率の透明導電膜の形成に好適に用いることができる。 The photocurable composition for forming a transparent conductive film of the present invention is a plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetylcellulose resin, polyethylene terephthalate, ABS resin, AS resin, norbornene. Resin, etc.), metal, wood, paper, glass, slate, etc., can be applied or printed on the surface of the substrate and cured to form a film. For example, plastic optical components, touch panels, film type liquid crystal elements Protective coating materials for preventing scratches (scratches) and preventing contamination of plastic containers, flooring materials for building interiors, wall materials, artificial marble, etc .; antireflection films for film-type liquid crystal elements, touch panels, plastic optical components, etc. ; Adhesives and sealing materials for various substrates; Used binder materials such click, can be suitably used particularly composition for forming an antireflection film having an antistatic function. Moreover, in the case of the photocurable composition for transparent conductive film formation mix | blended with the high refractive index microparticles | fine-particles, it can use suitably for formation of the transparent conductive film of especially high refractive index.
基材への透明導電膜形成用光硬化性組成物の塗布又は印刷は、常法に従って、例えば、ロールコート、スピンコート、スクリーン印刷などの手法で行うことができる。必要により加熱して分散媒（溶媒）を蒸発させ、塗膜を乾燥させ、次いで、活性エネルギー線（紫外線又は電子線）を照射する。活性エネルギー線源としては、低圧水銀灯、高圧水銀灯、メタルハライドランプ、キセノンランプ、エキシマレーザー、色素レーザーなどの紫外線源、ならびに電子線加速装置を使用することができる。活性エネルギー線の照射量は、紫外線の場合には５０〜３０００mJ/cm2、電子線の場合には０．２〜１０００μC/cm2の範囲内が適当である。この活性エネルギー線の照射により、上記活性エネルギー線硬化性化合物が重合し、導電性微粒子が樹脂で結合された膜が形成される。この膜の膜厚は一般的に０．1〜１０．０μmの範囲内であることが好ましい。 Application | coating or printing of the photocurable composition for transparent conductive film formation to a base material can be performed by methods, such as roll coating, spin coating, and screen printing, according to a conventional method. If necessary, the dispersion medium (solvent) is evaporated by heating, the coating film is dried, and then irradiated with active energy rays (ultraviolet rays or electron beams). As the active energy ray source, an ultraviolet ray source such as a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, an excimer laser, or a dye laser, and an electron beam accelerator can be used. The irradiation amount of the active energy ray is suitably within the range of 50 to 3000 mJ / cm 2 in the case of ultraviolet rays and 0.2 to 1000 μC / cm 2 in the case of electron beams. By irradiation with this active energy ray, the active energy ray-curable compound is polymerized to form a film in which conductive fine particles are bonded with a resin. In general, the thickness of this film is preferably in the range of 0.1 to 10.0 μm.
本発明の透明導電膜形成用分散液で調製した透明導電膜形成用光硬化性組成物を硬化させて得られる本発明の透明導電膜は、導電性微粒子が透明導電膜内で均一に分散していて、屈折率の制御が可能で、透明性が高く、ヘイズが低く、具体的には屈折率が１．４５〜１．９０であり、光透過率が７５%以上であり、ヘイズが２．０%以下であり、且つ表面抵抗値が１×１０ 9 Ω／□以下である。 The transparent conductive film of the present invention obtained by curing a photocurable composition for forming a transparent conductive film prepared with the dispersion for forming a transparent conductive film of the present invention has conductive fine particles uniformly dispersed in the transparent conductive film. The refractive index can be controlled, the transparency is high, the haze is low, specifically, the refractive index is 1.45 to 1.90, the light transmittance is 75% or more, and the haze is 2 0.0% or less and the surface resistance value is 1 × 10 9 Ω / □ or less .
以下に、実施例及び比較例により本発明を具体的に説明する。なお、実施例及び比較例において「部」は全て「質量部」である。 The present invention will be specifically described below with reference to examples and comparative examples. In Examples and Comparative Examples, “parts” are all “parts by mass”.
〔実施例１〜５及び比較例１〜２〕
実施例１〜５及び比較例１〜２で使用した成分は以下の通りである。
[Examples 1-5 and Comparative Examples 1-2]
The components used in Examples 1 to 5 and Comparative Examples 1 and 2 are as follows.
＜導電性微粒子＞
ＡＴＯ（屈折率２．０、体積抵抗率１０Ω・cm、一次粒子径０．０５μm）
ＩＴＯ（屈折率２．０、体積抵抗率０．０２Ω・cm、一次粒子径０．０４μm）
酸化錫（屈折率２．０、体積抵抗率１００Ω・cm、一次粒子径０．０６μm）
酸化亜鉛（屈折率１．９５、体積抵抗率１００Ω・cm、一次粒子径０．０６μm）
<Conductive fine particles>
ATO (refractive index 2.0, volume resistivity 10Ω · cm, primary particle diameter 0.05μm)
ITO (refractive index 2.0, volume resistivity 0.02Ω · cm, primary particle diameter 0.04μm)
Tin oxide (refractive index 2.0, volume resistivity 100Ω · cm, primary particle size 0.06μm)
Zinc oxide (refractive index 1.95, volume resistivity 100Ω · cm, primary particle size 0.06μm)
＜無機微粒子＞
酸化アルミニウム（屈折率１．７６、一次粒子径０．０４μm）
<Inorganic fine particles>
Aluminum oxide (refractive index 1.76, primary particle size 0.04 μm)
＜金属錯体＞
ジルコニウムアセチルアセトナート〔Zr(C5H7O2)4〕
チタンアセチルアセトナート〔Ti(C5H7O2)4〕
亜鉛アセチルアセトナート〔Zn(C5H7O2)2〕
ジブチル-錫ビスアセチルアセトナート〔(C4H9)2Sn(C5H7O2)2〕
<Metal complex>
Zirconium acetylacetonate (Zr (C 5 H 7 O 2 ) 4 )
Titanium acetylacetonate (Ti (C 5 H 7 O 2 ) 4 )
Zinc acetylacetonate (Zn (C 5 H 7 O 2 ) 2 )
Dibutyl-tin bisacetylacetonate ((C 4 H 9 ) 2 Sn (C 5 H 7 O 2 ) 2 )
＜分散助剤＞
ビックケミージャパン（株）製、BYK-142
<Dispersing aid>
BYK-142, manufactured by Big Chemie Japan
＜活性エネルギー線硬化性化合物＞
日本化薬（株）製、KAYARAD DPHA
<Active energy ray-curable compound>
Nippon Kayaku Co., Ltd., KAYARAD DPHA
＜光重合開始剤＞
チバ・スペシャリティ・ケミカルズ（株）製、IRGACURE 184
<Photopolymerization initiator>
IRGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd.
＜キレート剤＞
ダイセル化学工業（株）製、アセチルアセトン
<Chelating agent>
Daicel Chemical Industries, Ltd., Acetylacetone
〔実施例１〕
酸化錫１００部に対し、２０部のジルコニウムアセチルアセトナート、２５０部のメチルエチルケトン及び４００部のガラスビーズとなる量で全成分を容器に入れ、ペイントシェーカーで３時間練合した。練合後、ガラスビーズを取り除いて分散液を得た。この分散液に４３部のDPHA、２部のIRGACURE 184及び６５部のメチルエチルケトンを加えて光硬化性組成物を得た。バーコーターを用いてこの光硬化性組成物を膜厚１００μmのＰＥＴフィルム（東洋紡（株）製 A4100）上に塗布し、有機溶媒を蒸発させた後、空気下で高圧水銀灯を用いて３００mJ/cm2の光を照射し、厚み３μmの透明導電膜を作製した。膜の作製は光硬化性組成物直後及び６ヵ月後に行った。
[Example 1]
All components were put into a container in an amount of 20 parts of zirconium acetylacetonate, 250 parts of methyl ethyl ketone and 400 parts of glass beads with respect to 100 parts of tin oxide, and kneaded with a paint shaker for 3 hours. After kneading, the glass beads were removed to obtain a dispersion. 43 parts of DPHA, 2 parts of IRGACURE 184 and 65 parts of methyl ethyl ketone were added to this dispersion to obtain a photocurable composition. This photocurable composition was applied onto a 100 μm-thick PET film (A4100 manufactured by Toyobo Co., Ltd.) using a bar coater, the organic solvent was evaporated, and then 300 mJ / cm using a high-pressure mercury lamp under air. A transparent conductive film having a thickness of 3 μm was produced by irradiating the light of No. 2 . The film was prepared immediately after and 6 months after the photocurable composition.
〔実施例２〕
ＡＴＯ１００部に対し、１０部のチタンアセチルアセトナート、１０部のBYK-142、２５０部の2-ブタノール及び４００部のガラスビーズとなる量で全成分を容器に入れ、ペイントシェーカーで３時間練合した。練合後、ガラスビーズを取り除いて分散液を得た。この分散液に４３部のDPHA、２部のIRGACURE 184及び６５部の2-ブタノールを加えて光硬化性組成物を得た。その後、実施例１と同様の方法により、厚み３μmの透明導電膜を作製した。
[Example 2]
Add 100 parts of ATO to 10 parts of titanium acetylacetonate, 10 parts of BYK-142, 250 parts of 2-butanol and 400 parts of glass beads in a container and knead for 3 hours in a paint shaker. did. After kneading, the glass beads were removed to obtain a dispersion. 43 parts DPHA, 2 parts IRGACURE 184 and 65 parts 2-butanol were added to this dispersion to obtain a photocurable composition. Thereafter, a transparent conductive film having a thickness of 3 μm was produced in the same manner as in Example 1.
〔実施例３〕
ＡＴＯ１００部に対し、１０部のジブチル-錫ビスアセチルアセトナート、２５０部の2-ブタノール及び４００部のガラスビーズとなる量で全成分を容器に入れ、ペイントシェーカーで３時間練合した。練合後、ガラスビーズを取り除いて分散液を得た。この分散液に４３部のDPHA、２部のIRGACURE 184及び６５部の2-ブタノールを加えて光硬化性組成物を得た。その後、実施例１と同様の方法により、厚み３μmの透明導電膜を作製した。
Example 3
All components were placed in a container in an amount of 10 parts dibutyl-tin bisacetylacetonate, 250 parts 2-butanol and 400 parts glass beads to 100 parts of ATO, and kneaded for 3 hours with a paint shaker. After kneading, the glass beads were removed to obtain a dispersion. 43 parts DPHA, 2 parts IRGACURE 184 and 65 parts 2-butanol were added to this dispersion to obtain a photocurable composition. Thereafter, a transparent conductive film having a thickness of 3 μm was produced in the same manner as in Example 1.
〔参考例４〕
ＡＴＯ５０部に対し５０部のＩＴＯ、１０部のジブチル-錫ビスアセチルアセトナート、２５０部の2-ブタノール及び４００部のガラスビーズとなる量で全成分を容器に入れ、ペイントシェーカーで３時間練合した。練合後、ガラスビーズを取り除いて分散液を得た。この分散液に４３部のDPHA、２部のIRGACURE 184及び６５部の2-ブタノールを加えて光硬化性組成物を得た。その後、実施例１と同様の方法により、厚み３μmの透明導電膜を作製した。
[ Reference Example 4 ]
Put all components in a container in an amount of 50 parts ITO, 10 parts dibutyl-tin bisacetylacetonate, 250 parts 2-butanol and 400 parts glass beads for 50 parts of ATO, and knead in a paint shaker for 3 hours. did. After kneading, the glass beads were removed to obtain a dispersion. 43 parts DPHA, 2 parts IRGACURE 184 and 65 parts 2-butanol were added to this dispersion to obtain a photocurable composition. Thereafter, a transparent conductive film having a thickness of 3 μm was produced in the same manner as in Example 1.
〔参考例５〕
ＩＴＯ６０部に対し、４０部の酸化アルミニウム、２５部のジブチル-錫ビスアセチルアセトナート、２５０部の2-ブタノール及び４００部のガラスビーズとなる量で全成分を容器に入れ、ペイントシェーカーで３時間練合した。練合後、ガラスビーズを取り除いて分散液を得た。この分散液に６７部のDPHA、６．７部のIRGACURE 184及び１７０部の2-ブタノールを加えて光硬化性組成物を得た。その後、実施例１と同様の方法により、厚み３μmの透明導電膜を作製した。
[ Reference Example 5 ]
Put all the ingredients in a container in an amount of 40 parts of aluminum oxide, 25 parts of dibutyl-tin bisacetylacetonate, 250 parts of 2-butanol and 400 parts of glass beads for 60 parts of ITO and paint shaker for 3 hours Kneaded. After kneading, the glass beads were removed to obtain a dispersion. 67 parts of DPHA, 6.7 parts of IRGACURE 184 and 170 parts of 2-butanol were added to this dispersion to obtain a photocurable composition. Thereafter, a transparent conductive film having a thickness of 3 μm was produced in the same manner as in Example 1.
〔比較例１〕
酸化錫１００部に対し、２０部のBYK-142、２５０部の2-ブタノール及び４００部のガラスビーズとなる量で全成分を容器に入れ、ペイントシェーカーで３時間練合した。練合中に分散液が増粘した。
[Comparative Example 1]
All components were put into a container in an amount of 20 parts of BYK-142, 250 parts of 2-butanol and 400 parts of glass beads with respect to 100 parts of tin oxide, and kneaded with a paint shaker for 3 hours. The dispersion thickened during kneading.
〔比較例２〕
２０部のチタンアセチルアセトナートの代わりに２０部のアセチルアセトンを添加した以外は実施例２と同様の処理により、厚み３μmの透明導電膜を作製した。
[Comparative Example 2]
A transparent conductive film having a thickness of 3 μm was produced in the same manner as in Example 2 except that 20 parts of acetylacetone was added instead of 20 parts of titanium acetylacetonate.
＜評価方法＞
（１）無機微粒子のメジアン径
実施例及び比較例で作製した分散液及び光硬化組成物に分散している無機微粒子のメジアン径を、日機装（株）製 Microtrac粒度分布計を用いて、作製直後、３ヶ月後（４０℃保管）、６ヶ月後（４０℃保管）に、以下の条件で測定した。
<Evaluation method>
(1) Median diameter of inorganic fine particles The median diameter of inorganic fine particles dispersed in the dispersions and photocured compositions prepared in Examples and Comparative Examples was measured immediately using a Microtrac particle size distribution meter manufactured by Nikkiso Co., Ltd. After 3 months (40 ° C storage) and 6 months (40 ° C storage), the measurement was performed under the following conditions.
（２）透明導電膜の透過率、ヘイズ
実施例及び比較例で得た透明導電膜について、透過率及びヘイズを日本電色工業（株）製NDH 5000で測定した。測定値は基材を含んだ値である。
(2) Transmittance and Haze of Transparent Conductive Film About the transparent conductive film obtained in Examples and Comparative Examples, the transmittance and haze were measured with NDH 5000 manufactured by Nippon Denshoku Industries Co., Ltd. The measured value is a value including the base material.
（３）表面抵抗値
実施例及び比較例で得た透明導電膜について、三菱化学株式会社製のハイレスタIP MCP-HT260で測定した。
(3) Surface resistance value About the transparent conductive film obtained by the Example and the comparative example, it measured by Hiresta IP MCP-HT260 by Mitsubishi Chemical Corporation.
（４）屈折率
実施例及び比較例で得た透明導電膜について、（株）アタゴ製アッべ屈折計DRM4（20℃）で測定した。
(4) Refractive index About the transparent conductive film obtained by the Example and the comparative example, it measured by Abago KK Abbe refractometer DRM4 (20 degreeC).
（５）金属製容器の腐食
実施例及び比較例で作製した分散液をステンレス容器（SUS304；Fe-Cr-Ni系ステンレス鋼製）に入れ、１ヶ月間静置した後のステンレス容器の腐食の状態を目視にて評価した。
(5) Corrosion of metal containers Corrosion of stainless steel containers after placing the dispersions prepared in Examples and Comparative Examples in stainless steel containers (SUS304; made of Fe-Cr-Ni stainless steel) for 1 month The state was evaluated visually.
上記の各々の測定の結果、評価の結果を各々の組成物の組成と共に第１表に示す。
第１表に示すデータから明らかなように、金属錯体を含有した場合（実施例１〜５）では、分散助剤の有無に関わらず、優れた保存安定性を有する分散液が得られ、金属製容器に保管した場合でも金属製容器に腐食は確認されなかった。さらに、実施例１〜５で得られた分散液を用いた光硬化性組成物を塗布して得られた透明導電膜は屈折率が１．４５〜１．９０、透過率が７５%以上、ヘイズ２．０%以下、表面抵抗値が１０12Ω／□以下という、帯電防止機能、高透明性を有し且つ導電性に優れていた。金属錯体を添加しなかった場合（比較例１）には、分散が困難で均一な分散液を得ることができなかった。また、アセチルアセトンを添加して分散させた分散液（比較例２）を金属製容器に保存した場合に、容器の腐食が顕著に認められた。 As is apparent from the data shown in Table 1, when a metal complex was contained (Examples 1 to 5), a dispersion having excellent storage stability was obtained regardless of the presence or absence of a dispersion aid. No corrosion was observed on the metal container even when stored in the container. Furthermore, the transparent conductive film obtained by applying the photocurable composition using the dispersion obtained in Examples 1 to 5 has a refractive index of 1.45 to 1.90, a transmittance of 75% or more, The haze was 2.0% or less, the surface resistance value was 10 12 Ω / □ or less, the antistatic function, high transparency, and excellent conductivity. When the metal complex was not added (Comparative Example 1), it was difficult to disperse and a uniform dispersion could not be obtained. Moreover, when the dispersion liquid (Comparative Example 2) in which acetylacetone was added and dispersed was stored in a metal container, the corrosion of the container was noticeable.
Claims (7)
前記導電性微粒子がＩＴＯ、ＡＴＯ、酸化錫、酸化亜鉛、酸化インジウム、アンチモン酸亜鉛及び五酸化アンチモンよりなる群から選ばれる１種類のみの金属酸化物であって、前記金属錯体がジルコニウム、チタン、アルミニウム、亜鉛、インジウム及び錫からなる群から選ばれる金属とβ-ジケトンからなる群から選ばれる配位子とからなること（但し、前記導電性微粒子以外の屈折率１．５５以上の無機微粒子を含む場合、及び分散媒としてエチレングリコールを含む場合を除く。）を特徴とする透明導電膜形成用分散液。 It contains 2 to 45 parts by weight of a metal complex that does not contain alkoxide and remains as a component that forms the transparent conductive film after forming the transparent conductive film, per 100 parts by weight of the conductive fine particles. The curable composition is formed by including 1000 parts by mass and the refractive index is 1.45 to 1.90, the light transmittance is 75% or more, the haze is 2.0% or less, and the surface resistance is 1. It is a dispersion for forming a transparent conductive film of × 10 9 Ω / □ or less ,
The conductive fine particles are only one kind of metal oxide selected from the group consisting of ITO, ATO, tin oxide, zinc oxide, indium oxide, zinc antimonate and antimony pentoxide, and the metal complex is zirconium, titanium, It consists of a metal selected from the group consisting of aluminum, zinc, indium and tin and a ligand selected from the group consisting of β-diketone (however, inorganic fine particles having a refractive index of 1.55 or more other than the conductive fine particles) A transparent conductive film-forming dispersion liquid, characterized in that it contains and excludes ethylene glycol as a dispersion medium.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009217991A JP4995878B2 (en) | 2009-09-18 | 2009-09-18 | Transparent conductive film forming dispersion, transparent conductive film forming photocurable composition, and transparent conductive film |
| PCT/JP2010/065919 WO2011034079A1 (en) | 2009-09-18 | 2010-09-15 | Electrically conductive microparticle dispersion, photocurable composition containing electrically conductive microparticles, and cured film containing electrically conductive microparticles |
| KR1020127009864A KR101752221B1 (en) | 2009-09-18 | 2010-09-15 | Electrically conductive microparticle dispersion, photocurable composition containing electrically conductive microparticles, and cured film containing electrically conductive microparticles |
| CN201080036039.9A CN102473475B (en) | 2009-09-18 | 2010-09-15 | Electrically conductive microparticle dispersion, photocurable composition containing electrically conductive microparticles, and article |
| TW099131643A TWI529225B (en) | 2009-09-18 | 2010-09-17 | A conductive fine particle dispersion liquid, a photohardenable composition containing conductive microparticles, and a hardening film containing conductive microparticles |
Applications Claiming Priority (1)
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| JP5908287B2 (en) * | 2012-01-24 | 2016-04-26 | 日立マクセル株式会社 | Composition for forming transparent conductive film and transparent conductive film |
| CN103360854A (en) | 2012-03-28 | 2013-10-23 | 厦门纳诺泰克科技有限公司 | High-transparency low-radiation energy-saving combined material for glass and preparation method thereof |
| FR2993999B1 (en) * | 2012-07-27 | 2014-09-12 | Nanomade Concept | METHOD FOR MANUFACTURING A TRANSPARENT TOUCH SURFACE AND TOUCH SURFACE OBTAINED BY SUCH A METHOD |
| JP5858197B2 (en) * | 2013-10-16 | 2016-02-10 | 日立化成株式会社 | Laminated body including conductive fiber, photosensitive conductive film, method for manufacturing conductive pattern, conductive pattern substrate, and touch panel |
| US9587132B2 (en) * | 2014-03-20 | 2017-03-07 | E I Du Pont De Nemours And Company | Thermoformable polymer thick film transparent conductor and its use in capacitive switch circuits |
| CN105223775B (en) * | 2014-07-04 | 2020-03-13 | 富士胶片株式会社 | Curable composition, method for producing cured film, touch panel, and display device |
| JP6141902B2 (en) * | 2014-07-04 | 2017-06-07 | 富士フイルム株式会社 | Curable composition, method for producing cured film, cured film, touch panel, and display device |
| US10508203B2 (en) * | 2014-09-26 | 2019-12-17 | The Boeing Company | Compositions and coatings with non-chrome corrosion inhibitor particles |
| JP6436487B2 (en) * | 2014-12-29 | 2018-12-12 | 小林 博 | Manufacturing method for manufacturing transparent conductive film |
| JP6825115B2 (en) * | 2017-09-05 | 2021-02-03 | 富士フイルム株式会社 | Curable composition, cured product, and lens unit |
| CN113861729B (en) * | 2021-10-14 | 2022-12-09 | 新纶新能源材料(常州)有限公司 | High-corrosion-resistance environment-friendly coating and preparation method thereof |
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| JP2001139847A (en) * | 1999-11-12 | 2001-05-22 | Dainippon Toryo Co Ltd | Active energy ray-curable coating composition |
| WO2005025787A1 (en) * | 2003-09-12 | 2005-03-24 | National Institute Of Advanced Industrial Science And Technology | Metal nano particle liquid dispersion capable of being sprayed in fine particle form and being applied in laminated state |
| JP5309440B2 (en) * | 2005-11-15 | 2013-10-09 | 三菱マテリアル株式会社 | Composition for forming electrode of solar cell, method for forming the electrode, and method for producing solar cell using the electrode obtained by the forming method |
| JP4620634B2 (en) * | 2006-06-06 | 2011-01-26 | 株式会社パワーシステム | Electrode member for non-aqueous electronic parts |
| JP2008010236A (en) * | 2006-06-28 | 2008-01-17 | Kyocera Corp | Transparent conductive film and forming method therefor, photoelectric transfer device, and photovoltaic generator device |
| JP4817254B2 (en) * | 2006-12-01 | 2011-11-16 | 大日本塗料株式会社 | Zirconium oxide particle dispersion, photocurable composition containing zirconium oxide particles, and cured film |
| JP2009135098A (en) * | 2007-10-31 | 2009-06-18 | Sumitomo Metal Mining Co Ltd | Coating liquid for translucent conductive film formation, and translucent conductive film |
| JP5020130B2 (en) * | 2008-03-13 | 2012-09-05 | 日立マクセル株式会社 | Transparent conductive film forming ink and transparent conductive film |
| JP5077950B2 (en) * | 2008-03-19 | 2012-11-21 | 大日本塗料株式会社 | Dispersion, transparent conductive film forming composition, transparent conductive film and display |
| JP5598892B2 (en) * | 2008-04-21 | 2014-10-01 | 大日本塗料株式会社 | Laminated transparent film |
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| KR101752221B1 (en) | 2017-06-29 |
| WO2011034079A1 (en) | 2011-03-24 |
| JP2011065966A (en) | 2011-03-31 |
| CN102473475B (en) | 2014-04-16 |
| TWI529225B (en) | 2016-04-11 |
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| KR20120087921A (en) | 2012-08-07 |
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