JP2018206651A - Method for producing conductive material and conductive material precursor - Google Patents
Method for producing conductive material and conductive material precursor Download PDFInfo
- Publication number
- JP2018206651A JP2018206651A JP2017111999A JP2017111999A JP2018206651A JP 2018206651 A JP2018206651 A JP 2018206651A JP 2017111999 A JP2017111999 A JP 2017111999A JP 2017111999 A JP2017111999 A JP 2017111999A JP 2018206651 A JP2018206651 A JP 2018206651A
- Authority
- JP
- Japan
- Prior art keywords
- conductive material
- silver halide
- layer
- material precursor
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004020 conductor Substances 0.000 title claims abstract description 145
- 239000002243 precursor Substances 0.000 title claims abstract description 85
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 229910052709 silver Inorganic materials 0.000 claims abstract description 151
- 239000004332 silver Substances 0.000 claims abstract description 151
- -1 silver halide Chemical class 0.000 claims abstract description 109
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- 239000000470 constituent Substances 0.000 claims abstract description 14
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- 238000002360 preparation method Methods 0.000 description 17
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Landscapes
- Conductive Materials (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
Description
本発明は、タッチパネル、電磁波シールド材、アンテナ回路、電子回路等の用途に用いることができる導電材料を製造することが可能な導電材料の製造方法、および導電材料前駆体に関する。 The present invention relates to a method for producing a conductive material capable of producing a conductive material that can be used for applications such as a touch panel, an electromagnetic shielding material, an antenna circuit, and an electronic circuit, and a conductive material precursor.
スマートフォン、パーソナル・デジタル・アシスタント（ＰＤＡ）、ノートＰＣ、タブレットＰＣ、ＯＡ機器、医療機器、あるいはカーナビゲーションシステム等の電子機器においては、これらのディスプレイに入力手段としてタッチパネルセンサーが広く用いられている。 In electronic devices such as smartphones, personal digital assistants (PDAs), notebook PCs, tablet PCs, OA devices, medical devices, and car navigation systems, touch panel sensors are widely used as input means for these displays.
タッチパネルセンサーには、位置検出の方法により光学方式、超音波方式、抵抗膜方式、表面型静電容量方式、投影型静電容量方式等があり、上記したディスプレイ用途においては抵抗膜方式と投影型静電容量方式が好適に利用されている。抵抗膜方式のタッチパネルセンサーは、透明支持体上に光透過性導電層を有する導電材料を２枚利用し、これら導電材料をドットスペーサーを介して対向配置した構造を有しており、タッチパネルセンサーの１点に力を加えることにより光透過性導電層同士が接触し、各光透過性導電層に印加された電圧をもう一方の光透過性導電層を通して測定することで、力の加えられた位置の検出を行うものである。一方、投影型静電容量方式のタッチパネルセンサーは、２層の光透過性導電層を有する導電材料を１枚、または１層の光透過性導電層を有する導電材料を２枚利用し、指等を接近させた際の光透過性導電層間の静電容量変化を検出し、指を接近させた位置の検出を行うものである。後者は可動部分がないため耐久性に優れる他、多点同時検出ができることから、スマートフォンやタブレットＰＣ等で、とりわけ広く利用されている。 Touch panel sensors include optical methods, ultrasonic methods, resistive film methods, surface capacitive methods, projection capacitive methods, etc., depending on the position detection method. A capacitance method is preferably used. The resistive film type touch panel sensor has a structure in which two conductive materials having a light-transmitting conductive layer on a transparent support are used and these conductive materials are arranged to face each other via a dot spacer. By applying a force to one point, the light-transmitting conductive layers are brought into contact with each other, and the voltage applied to each light-transmitting conductive layer is measured through the other light-transmitting conductive layer, so that the position where the force is applied Is detected. On the other hand, a projected capacitive touch panel sensor uses one conductive material having two light-transmitting conductive layers or two conductive materials having one light-transmitting conductive layer, such as a finger. The capacitance change between the light-transmitting conductive layers when the two are brought close to each other is detected, and the position where the finger is brought close is detected. The latter has excellent durability because it has no moving parts, and can detect multiple points at the same time. Therefore, the latter is widely used particularly in smartphones and tablet PCs.
上記光透過性導電層を有する導電材料には、透明支持体上に酸化スズ（ＳｎＯ２）、酸化インジウムスズ（ＩＴＯ）や酸化亜鉛（ＺｎＯ）等からなる導電膜を真空蒸着法、スパッタリング法、イオンプレーティング法等のドライプロセスによって設けたものがよく知られている。 For the conductive material having the light transmissive conductive layer, a conductive film made of tin oxide (SnO 2 ), indium tin oxide (ITO), zinc oxide (ZnO), or the like is formed on a transparent support by vacuum deposition, sputtering, Those provided by a dry process such as an ion plating method are well known.
また、上記ドライプロセス以外にも、導電性高分子、カーボンナノチューブ、例えば金属ナノワイヤ等の金属微粒子のネットワーク構造を使用したウェットプロセスにより形成された光透過性導電層を有する導電材料も提案されている。 In addition to the dry process, a conductive material having a light-transmitting conductive layer formed by a wet process using a network structure of conductive fine particles, carbon nanotubes, and metal fine particles such as metal nanowires has also been proposed. .
現在、光透過性導電層として主流なのはＩＴＯ導電膜である。しかしながらＩＴＯ導電膜は屈折率が大きく、光の表面反射が大きいため、全光線透過率が低下する問題や、可撓性が低いため、ＩＴＯ導電膜が屈曲した際に亀裂が生じて電気抵抗値が高くなる問題があった。また、使用するインジウムの枯渇の懸念、生産コスト高も問題点として挙げられ、上述のウェットプロセスにより形成された光透過性導電層を有する導電材料が代替材料として検討されている。 At present, the ITO conductive film is mainly used as the light transmissive conductive layer. However, since the ITO conductive film has a large refractive index and a large surface reflection of light, there is a problem that the total light transmittance is reduced, and since the flexibility is low, a crack occurs when the ITO conductive film is bent, resulting in an electric resistance value. There was a problem that increased. In addition, there are concerns about depletion of indium used and high production costs, and a conductive material having a light-transmitting conductive layer formed by the above-described wet process is being investigated as an alternative material.
また、近年では銀塩感光材料を導電材料前駆体として用い、金属銀細線からなる網目状金属銀細線パターンを形成し光透過性導電層とする方法も提案されている。例えば直接現像方式を用いて支持体上に網目状金属銀細線パターンを形成する方法が国際公開第２００１／５１２７６号パンフレット（特許文献１）、特開２００４−２２１５６４号公報（特許文献２）に開示され、例えば硬化現像方式を用いて支持体上に網目状金属銀細線パターンを形成する方法が特開２００７−５９２７０号公報（特許文献３）に開示される。また特開２００３−７７３５０号公報（特許文献４）や特開２００５−２５０１６９号公報（特許文献５）等では、支持体上に物理現像核層とハロゲン化銀乳剤層を少なくともこの順に有する導電材料前駆体に、可溶性銀塩形成剤および還元剤をアルカリ液中で作用させ、支持体上に網目状金属銀細線パターンを形成する銀塩拡散転写法が開示されている。特に銀塩拡散転写法によれば金属の中で最も導電性の高い銀からなる細線を、再現性良く容易に形成できるため、高透過率、高導電性を両立した導電材料を形成可能である。さらに、この方法で得られた光透過性導電層はＩＴＯ導電膜よりも可撓性が高く折り曲げに強いという利点があり、可撓性を有する支持体上へ形成するのに適している。 In recent years, a method has been proposed in which a silver salt light-sensitive material is used as a conductive material precursor to form a mesh-like metal silver fine wire pattern made of metal silver fine wires to form a light transmissive conductive layer. For example, methods for forming a reticulated metallic silver fine wire pattern on a support using a direct development method are disclosed in International Publication No. 2001/51276 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2004-221564 (Patent Document 2). For example, Japanese Unexamined Patent Publication No. 2007-59270 (Patent Document 3) discloses a method of forming a reticulated metallic silver fine wire pattern on a support using a curing development method. In JP-A-2003-77350 (Patent Document 4), JP-A-2005-250169 (Patent Document 5), etc., a conductive material having a physical development nucleus layer and a silver halide emulsion layer at least in this order on a support. A silver salt diffusion transfer method is disclosed in which a soluble silver salt forming agent and a reducing agent are allowed to act on a precursor in an alkaline solution to form a reticulated metallic silver fine wire pattern on a support. In particular, according to the silver salt diffusion transfer method, a thin wire made of silver having the highest conductivity among metals can be easily formed with good reproducibility, so that a conductive material having both high transmittance and high conductivity can be formed. . Furthermore, the light-transmitting conductive layer obtained by this method has the advantage that it is more flexible and stronger than bending than the ITO conductive film, and is suitable for being formed on a flexible support.
しかしながら、上記した方法で得られた光透過性導電層は、金属銀細線部分が光を透過しないため、網目状金属銀細線パターンが視認されやすいという問題が存在する。これを改善するには金属銀細線の一層の細線化が必要であるが、単純に細線化した場合には金属銀細線の抵抗値が上昇するため、タッチパネルセンサーの感度が低下する。つまり、より高い導電性を有する導電材料が求められていた。 However, the light-transmitting conductive layer obtained by the above-described method has a problem that the mesh-like metal silver fine wire pattern is easily visible because the metal silver fine wire portion does not transmit light. In order to improve this, it is necessary to further thin the metal silver thin wire. However, when the wire is simply thinned, the resistance value of the metal silver thin wire increases, so the sensitivity of the touch panel sensor decreases. That is, a conductive material having higher conductivity has been demanded.
一方、導電性に優れた導電材料の製造方法として、特開２００８−２５１４１７号公報（特許文献６）には、支持体上に銀塩を含有する銀塩含有層を有する感光材料を露光し、現像することによって得られる透明導電膜の製造方法において、分子量が２０００のポリエチレングリコールを含有する現像液で現像処理する具体例が記載されているが、更なる改善が求められていた。 On the other hand, as a method for producing a conductive material having excellent conductivity, JP 2008-251417 A (Patent Document 6) exposes a photosensitive material having a silver salt-containing layer containing a silver salt on a support, In the method for producing a transparent conductive film obtained by development, a specific example of developing with a developer containing polyethylene glycol having a molecular weight of 2000 is described, but further improvement has been demanded.
本発明の課題は、高い導電性を有する導電材料を製造することが可能な導電材料の製造方法、および導電材料前駆体を提供することにある。 An object of the present invention is to provide a method for producing a conductive material capable of producing a conductive material having high conductivity, and a conductive material precursor.
本発明の上記課題は、以下の発明によって達成される。
（１）支持体上にハロゲン化銀粒子を含有するハロゲン化銀乳剤層を少なくとも有する導電材料前駆体を像様に露光し、その後、現像する導電材料の製造方法において、平均分子量が３０００以上のポリエチレングリコールおよび／またはその誘導体の存在下で現像することを特徴とする導電材料の製造方法。
The above object of the present invention is achieved by the following invention.
(1) In a method for producing a conductive material in which a conductive material precursor having at least a silver halide emulsion layer containing silver halide grains on a support is imagewise exposed and then developed, the average molecular weight is 3000 or more. A method for producing a conductive material, wherein development is performed in the presence of polyethylene glycol and / or a derivative thereof.
（２）支持体上にハロゲン化銀粒子を含有するハロゲン化銀乳剤層を少なくとも有する導電材料前駆体であって、該導電材料前駆体が有する構成層の少なくとも一層が、平均分子量が３０００以上のポリエチレングリコールおよび／またはその誘導体を含有することを特徴とする導電材料前駆体。 (2) A conductive material precursor having at least a silver halide emulsion layer containing silver halide grains on a support, wherein at least one of the constituent layers of the conductive material precursor has an average molecular weight of 3000 or more. A conductive material precursor comprising polyethylene glycol and / or a derivative thereof.
本発明により、高い導電性を有する導電材料を製造することが可能な導電材料の製造方法、および導電材料前駆体を提供することができる。 According to the present invention, it is possible to provide a conductive material manufacturing method and a conductive material precursor capable of manufacturing a conductive material having high conductivity.
以下、本発明について説明する。本発明の導電材料の製造方法では、支持体上にハロゲン化銀乳剤層を少なくとも有する導電材料前駆体を像様に露光した後、平均分子量が３０００以上のポリエチレングリコールおよび／またはその誘導体の存在下で現像することを特徴とする。 The present invention will be described below. In the method for producing a conductive material of the present invention, a conductive material precursor having at least a silver halide emulsion layer on a support is imagewise exposed, and then in the presence of polyethylene glycol having an average molecular weight of 3000 or more and / or a derivative thereof. It develops by.
本発明においてポリエチレングリコールおよび／またはその誘導体の存在下で現像するとは、導電材料前駆体が露光された後の現像時に、その反応系内にポリエチレングリコールおよび／またはその誘導体が存在していることを意味する。よってポリエチレングリコールおよび／またはその誘導体は導電材料前駆体が含有していてもよく、現像液が含有していてもよく、導電材料前駆体と現像液の両方が含有していてもよい。中でも、導電材料前駆体がポリエチレングリコールおよび／またはその誘導体を含有することが、高い導電性を有する導電材料を得ることができるため特に好ましい。 In the present invention, development in the presence of polyethylene glycol and / or a derivative thereof means that polyethylene glycol and / or a derivative thereof are present in the reaction system at the time of development after the conductive material precursor is exposed. means. Therefore, the polyethylene glycol and / or derivative thereof may be contained in the conductive material precursor, may be contained in the developer, or may be contained in both the conductive material precursor and the developer. Among them, it is particularly preferable that the conductive material precursor contains polyethylene glycol and / or a derivative thereof because a conductive material having high conductivity can be obtained.
＜ポリエチレングリコールおよび／またはその誘導体＞
本発明に用いるポリエチレングリコールおよび／またはその誘導体は、平均分子量が３０００以上であることが必要であり、より好ましくは６０００以上である。ポリエチレングリコールおよび／またはその誘導体の平均分子量の上限は特に限定されないが、１００万以下であることが溶解性の観点から好ましい。平均分子量が３０００未満のポリエチレングリコールおよび／またはその誘導体を用いた場合、高い導電性を有する導電材料を得ることはできない。本発明に用いるポリエチレングリコール誘導体としては、ポリエチレングリコールが有する１つ以上のヒドロキシ基をエーテル化、エステル化、アルコキシ化したものを例示できる。具体的には、ポリエチレングリコールモノメチルエーテル、ポリエチレングリコールジメチルエーテル、ポリエチレングリコールモノエチルエーテル、ポリエチレングリコールジエチルエーテル、ポリエチレングリコールモノステアリルエーテル、ポリエチレングリコールジステアリルエーテル、ポリエチレングリコール（モノメチル・モノエチル）エーテル、ポリエチレングリコール（モノパルミチル・モノステアリル）エーテル、ポリエチレングリコール（モノパルミチル・モノヘプタデシル）エーテル、ポリエチレングリコールモノ酢酸エステル、ポリエチレングリコールジ酢酸エステル、ポリエチレングリコールモノステアリン酸エステル、ポリエチレングリコールジステアリン酸エステル、ポリエチレングリコール（モノステアリン酸・モノパルミチン酸）エステル、モノメトキシポリエチレングリコールステアリン酸エステル等が挙げられ、これらを２種類以上併用してもよい。なお本発明における平均分子量は、特に断りがない限り数平均分子量を言い、数平均分子量とは、分子の大きさの重み付けを考慮しない方法で算出した平均分子量であり、ポリエチレングリコールおよび／またはその誘導体の平均分子量はゲルパーミエーションクロマトグラフを用いて、ポリエチレングリコールによる校正曲線と対比させて算出して求めることができる。
<Polyethylene glycol and / or its derivative>
The polyethylene glycol and / or derivative thereof used in the present invention needs to have an average molecular weight of 3000 or more, more preferably 6000 or more. The upper limit of the average molecular weight of polyethylene glycol and / or its derivative is not particularly limited, but is preferably 1,000,000 or less from the viewpoint of solubility. When polyethylene glycol having an average molecular weight of less than 3000 and / or a derivative thereof is used, a conductive material having high conductivity cannot be obtained. Examples of the polyethylene glycol derivative used in the present invention include those obtained by etherification, esterification, or alkoxylation of one or more hydroxy groups of polyethylene glycol. Specifically, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol diethyl ether, polyethylene glycol monostearyl ether, polyethylene glycol distearyl ether, polyethylene glycol (monomethyl monoethyl) ether, polyethylene glycol (monopalmityl) Monostearyl) ether, polyethylene glycol (monopalmityl monoheptadecyl) ether, polyethylene glycol monoacetate, polyethylene glycol diacetate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol (monosteary Acid monopalmitate) ester, monomethoxy polyethylene glycol monostearate, and the like, may be used in combination two or more of these. The average molecular weight in the present invention means the number average molecular weight unless otherwise specified, and the number average molecular weight is an average molecular weight calculated by a method that does not consider weighting of the molecular size, and is polyethylene glycol and / or a derivative thereof. The average molecular weight can be calculated and compared with a calibration curve using polyethylene glycol using a gel permeation chromatograph.
導電材料前駆体がポリエチレングリコールおよび／またはその誘導体を含有する場合、後述する導電材料前駆体が有するハロゲン化銀乳剤層、物理現像核層、中間層や保護層等のその他の構成層のいずれの層がポリエチレングリコールおよび／またはその誘導体を含有していてもよく、２つ以上の層が含有していてもよい。中でも保護層がポリエチレングリコールおよび／またはその誘導体を含有することが高い導電性を有する導電材料が得られるため特に好ましい。ポリエチレングリコールおよび／またはその誘導体の含有量は特に限定されないが、１ｍｇ／ｍ２〜０．５ｇ／ｍ２であることが好ましく、より好ましくは５ｍｇ／ｍ２〜０．１ｇ／ｍ２である。 When the conductive material precursor contains polyethylene glycol and / or a derivative thereof, any of other constituent layers such as a silver halide emulsion layer, a physical development nucleus layer, an intermediate layer and a protective layer, which the conductive material precursor described later has The layer may contain polyethylene glycol and / or a derivative thereof, and two or more layers may contain it. Among them, it is particularly preferable that the protective layer contains polyethylene glycol and / or a derivative thereof because a conductive material having high conductivity can be obtained. The content of polyethylene glycol and / or a derivative thereof is not particularly limited, but is preferably 1 mg / m 2 to 0.5 g / m 2 , more preferably 5 mg / m 2 to 0.1 g / m 2 .
現像液がポリエチレングリコールおよび／またはその誘導体を含有する場合、その含有量は０．１〜１０ｇ／Ｌであることが高い導電性を有する導電材料が得られるため好ましく、より好ましくは０．２５〜５ｇ／Ｌである。 When the developer contains polyethylene glycol and / or a derivative thereof, the content is preferably 0.1 to 10 g / L because a conductive material having high conductivity is obtained, and more preferably 0.25 to 0.25. 5 g / L.
導電材料前駆体にポリエチレングリコールおよび／またはその誘導体を含有させる方法は特に限定されず、導電材料前駆体の製造時に各構成層に含有させてもよく、製造後の導電材料前駆体を、水や公知の有機溶剤にポリエチレングリコールおよび／またはその誘導体を溶解させた溶液に接触させて含有させてもよい。 The method of incorporating polyethylene glycol and / or a derivative thereof into the conductive material precursor is not particularly limited, and may be included in each constituent layer at the time of producing the conductive material precursor. You may make it contact and contain the solution which melt | dissolved polyethyleneglycol and / or its derivative (s) in the well-known organic solvent.
＜導電材料前駆体＞
本発明の導電材料の製造方法にて用いる導電材料前駆体について説明する。本発明の導電材料前駆体は、支持体上にハロゲン化銀粒子を含有するハロゲン化銀乳剤層を少なくとも有する。
<Precursor of conductive material>
The conductive material precursor used in the method for producing a conductive material of the present invention will be described. The conductive material precursor of the present invention has at least a silver halide emulsion layer containing silver halide grains on a support.
＜支持体＞
導電材料前駆体が有する支持体の材質は特に限定されないが、本発明の導電材料をタッチパネルセンサー等の光透過性が必要な用途に利用する場合、導電材料の透明性の観点から、支持体は光透過性を有することが特に好ましい。光透過性を有する支持体としては、ポリエチレン、ポリプロピレン等のポリオレフィン系樹脂、ポリ塩化ビニル、塩化ビニル共重合体等の塩化ビニル系樹脂、エポキシ樹脂、ポリアリレート、ポリサルフォン、ポリエーテルサルフォン、ポリイミド、フッ素樹脂、フェノキシ樹脂、トリアセチルセルロース、ポリエチレンテレフタレート、ポリイミド、ポリフェニレンスルファイド、ポリエチレンナフタレート、ポリカーボネート、アクリル樹脂、セロファン、ナイロン、ポリスチレン系樹脂、ＡＢＳ樹脂等の各種樹脂フィルム、石英ガラス、無アルカリガラス等のガラス等が例示できる。導電材料の透明性の観点から、支持体の全光線透過率は６０％以上が好ましく、特に好ましくは７０％以上であり、同様の観点から支持体のヘイズは０〜３％が好ましく、特に好ましくは０〜２％である。支持体の厚さは１０〜３００μｍであることが取り扱い性や透明性の観点から好ましい。支持体はその表面の少なくとも一方の面に、易接着層、ハードコート層、反射防止層、防眩層等の公知の層を有していてもよい。
<Support>
The material of the support that the conductive material precursor has is not particularly limited, but when the conductive material of the present invention is used for applications that require light transmission such as a touch panel sensor, from the viewpoint of the transparency of the conductive material, the support is It is particularly preferable to have light transmittance. As a light-transmitting support, polyolefin resins such as polyethylene and polypropylene, vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers, epoxy resins, polyarylate, polysulfone, polyethersulfone, polyimide, Fluorine resin, phenoxy resin, triacetyl cellulose, polyethylene terephthalate, polyimide, polyphenylene sulfide, polyethylene naphthalate, polycarbonate, acrylic resin, cellophane, nylon, polystyrene resin, ABS resin and other various resin films, quartz glass, alkali-free glass Examples thereof include glass. From the viewpoint of the transparency of the conductive material, the total light transmittance of the support is preferably 60% or more, particularly preferably 70% or more. From the same viewpoint, the haze of the support is preferably 0 to 3%, particularly preferably. Is 0 to 2%. The thickness of the support is preferably 10 to 300 μm from the viewpoint of handleability and transparency. The support may have a known layer such as an easy-adhesion layer, a hard coat layer, an antireflection layer, or an antiglare layer on at least one surface thereof.
＜ハロゲン化銀乳剤層＞
導電材料前駆体が有するハロゲン化銀乳剤層は、ハロゲン化銀粒子が均一に分散された（乳化された）ハロゲン化銀乳剤を含有する層であることを意味し、したがってハロゲン化銀乳剤層はハロゲン化銀粒子を含有する。ハロゲン化銀乳剤に関する銀塩写真フィルムや印画紙、印刷製版用フィルム、フォトマスク用エマルジョンマスク等で用いられる技術はそのまま用いることができる。
<Silver halide emulsion layer>
The silver halide emulsion layer contained in the conductive material precursor means that the silver halide grains are a layer containing a silver halide emulsion in which silver halide grains are uniformly dispersed (emulsified). Contains silver halide grains. Techniques used for silver halide photographic film, photographic paper, printing plate making film, emulsion mask for photomask, etc. relating to silver halide emulsions can be used as they are.
ハロゲン化銀乳剤層が含有するハロゲン化銀粒子は、塩化銀、臭化銀、ヨウ化銀およびフッ化銀のいずれであってもよく、これらの組み合わせでもよい。ハロゲン化銀粒子の形成には、順混合、逆混合、同時混合等の当業界では周知の方法が用いられる。中でも同時混合法の１種で、粒子形成される液相中のｐＡｇを一定に保ついわゆるコントロールドダブルジェット法を用いることが、粒径の揃ったハロゲン化銀粒子が得られる点において好ましい。本発明において、導電材料の金属銀細線の導電性の観点やハロゲン化銀粒子の分散安定性の観点から、好ましいハロゲン化銀粒子の平均粒径は０．２５μｍ以下、特に好ましくは０．０５〜０．２μｍである。ハロゲン化銀乳剤層が含有するハロゲン化銀粒子は、８０ｍｏｌ％以上が塩化銀であることが導電材料の金属銀細線の導電性の観点から好ましく、特に好ましくは９０ｍｏｌ％以上である。 The silver halide grains contained in the silver halide emulsion layer may be any of silver chloride, silver bromide, silver iodide and silver fluoride, or a combination thereof. For the formation of silver halide grains, methods well known in the art such as forward mixing, reverse mixing and simultaneous mixing are used. Among them, it is preferable to use a so-called controlled double jet method in which a pAg in a liquid phase in which grains are formed is kept constant as one type of simultaneous mixing method, from the viewpoint of obtaining silver halide grains having a uniform particle diameter. In the present invention, from the viewpoint of the conductivity of the metal silver fine wire of the conductive material and the viewpoint of the dispersion stability of the silver halide grains, the preferred average grain diameter of the silver halide grains is 0.25 μm or less, particularly preferably 0.05 to 0.2 μm. The silver halide grains contained in the silver halide emulsion layer are preferably 80 mol% or more of silver chloride from the viewpoint of the conductivity of the metal silver fine wire of the conductive material, and particularly preferably 90 mol% or more.
ハロゲン化銀粒子の形状は特に限定されず、例えば、球状、立方体状、平板状（六角平板状、三角形平板状、四角形平板状など）、八面体状、十四面体状など様々な形状であることができる。 The shape of the silver halide grains is not particularly limited. For example, the shape can be various shapes such as a spherical shape, a cubic shape, a flat plate shape (hexagon flat plate shape, a triangular flat plate shape, a quadrangular flat plate shape, etc.), an octahedron shape, and a tetrahedron shape. Can be.
ハロゲン化銀粒子は、その形成あるいは物理熟成の過程において必要に応じて亜硫酸塩、鉛塩、タリウム塩、あるいはロジウム塩もしくはその錯塩、イリジウム塩もしくはその錯塩などVIII族金属元素の塩もしくはその錯塩を共存させてもよい。また、種々の化学増感剤によって増感することができ、イオウ増感法、セレン増感法、貴金属増感法など当業界で一般的な方法を、単独、あるいは組み合わせて用いることができる。 In the process of formation or physical ripening of silver halide grains, sulfites, lead salts, thallium salts, rhodium salts or complex salts thereof, iridium salts or complex salts thereof, and the like, or salts of group VIII metal elements or complex salts thereof are used. You may coexist. Further, it can be sensitized by various chemical sensitizers, and methods commonly used in the art such as sulfur sensitization method, selenium sensitization method and noble metal sensitization method can be used alone or in combination.
ハロゲン化銀粒子は、必要に応じて分光増感することもできる。また、ハロゲン化銀粒子は必ずしもネガ感光性でなくてもよく、必要に応じてポジ感光性を持つハロゲン化銀粒子としてもよい。これにより、ネガ型をポジ型に、ポジ型をネガ型に変換することができる。ポジ感光性を持つハロゲン化銀粒子に関しては、特開平８−１７１２１０号公報、同平８−２０２０４１号公報に記載されている方法によって作製することができる。 The silver halide grains can be spectrally sensitized as necessary. Further, the silver halide grains are not necessarily negative photosensitive, and may be silver halide grains having positive photosensitivity as required. Thereby, a negative type can be converted into a positive type, and a positive type can be converted into a negative type. The silver halide grains having positive photosensitivity can be prepared by the method described in JP-A-8-171210 and JP-A-8-202041.
ハロゲン化銀乳剤層はハロゲン化銀粒子の保護コロイドとしてバインダーを含有することが好ましい。バインダーとしては水溶性高分子化合物、非水溶性高分子化合物が例示できる。 The silver halide emulsion layer preferably contains a binder as a protective colloid for silver halide grains. Examples of the binder include water-soluble polymer compounds and water-insoluble polymer compounds.
水溶性高分子化合物は限定されず、公知のものを使用できる。具体的にはゼラチン、カゼイン、アルブミンなどのタンパク質、澱粉、デキストリン等の多糖類、セルロースおよびその誘導体（例えばカルボキシルメチルセルロース、ヒドロキシルプロピルセルロース、メチルセルロースなど）、アルギン酸、カラギーナン、グアーガム、キサンタンガム、フコイダン、キトサン、ヒアルロン酸、ポリエチレンオキサイド、ポリビニルアルコール、ポリビニルピロリドン、ポリビニルメチルエーテル、ポリアクリルアミド、ポリエチレンイミン、ポリアリルアミン、ポリビニルアミン、ポリリジン、ポリアクリル酸やこれらのグラフト重合ポリマー等が例示できる。またコハク化ゼラチンなど公知の方法で修飾した化合物を用いることもできる。 A water-soluble high molecular compound is not limited, A well-known thing can be used. Specifically, proteins such as gelatin, casein and albumin, polysaccharides such as starch and dextrin, cellulose and derivatives thereof (eg, carboxymethylcellulose, hydroxylpropylcellulose, methylcellulose, etc.), alginic acid, carrageenan, guar gum, xanthan gum, fucoidan, chitosan, Examples include hyaluronic acid, polyethylene oxide, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, polyacrylamide, polyethyleneimine, polyallylamine, polyvinylamine, polylysine, polyacrylic acid, and graft polymerization polymers thereof. A compound modified by a known method such as succinylated gelatin can also be used.
非水溶性高分子化合物としては公知の単独重合体や共重合体が例示できる。単独重合体としては酢酸ビニル、塩化ビニル、スチレン、メチルアクリレート、ブチルアクリレート、メタクリロニトリル、ブタジエン、イソプレンなどがあり、共重合体としてはエチレン・ブタジエン、スチレン・ブタジエン、スチレン・ｐ−メトオキシスチレン、スチレン・酢酸ビニル、酢酸ビニル・塩化ビニル、酢酸ビニル・マレイン酸ジエチル、メチルメタクリレート・アクリロニトリル、メチルメタクリレート・ブタジエン、メチルメタクリレート・スチレン、メチルメタクリレート・酢酸ビニル、メチルメタクリレート・塩化ビニリデン、メチルアクリレート・アクリロニトリル、メチルアクリレート・ブタジエン、メチルアクリレート・スチレン、メチルアクリレート・酢酸ビニル、アクリル酸・ブチルアクリレート、メチルアクリレート・塩化ビニル、ブチルアクリレート・スチレン等が例示できる。上記非水溶性高分子化合物としては、水に分散させたエマルションを使用することが好ましい。非水溶性高分子化合物のエマルションの平均粒径は０．０１〜１．０μｍであることが好ましく、特に好ましくは０．０５〜０．８μｍである。 Examples of the water-insoluble polymer compound include known homopolymers and copolymers. Homopolymers include vinyl acetate, vinyl chloride, styrene, methyl acrylate, butyl acrylate, methacrylonitrile, butadiene, and isoprene. Copolymers include ethylene / butadiene, styrene / butadiene, and styrene / p-methoxystyrene. , Styrene / vinyl acetate, vinyl acetate / vinyl chloride, vinyl acetate / diethyl maleate, methyl methacrylate / acrylonitrile, methyl methacrylate / butadiene, methyl methacrylate / styrene, methyl methacrylate / vinyl acetate, methyl methacrylate / vinylidene chloride, methyl acrylate / acrylonitrile , Methyl acrylate / butadiene, methyl acrylate / styrene, methyl acrylate / vinyl acetate, acrylic acid / butyl acrylate, methyl Acrylate-vinyl chloride, butyl acrylate-styrene and the like. As the water-insoluble polymer compound, it is preferable to use an emulsion dispersed in water. The average particle size of the emulsion of the water-insoluble polymer compound is preferably 0.01 to 1.0 μm, particularly preferably 0.05 to 0.8 μm.
上記した中でも、分散安定性が優れたハロゲン化銀粒子が得られることから、ハロゲン化銀乳剤層は水溶性高分子化合物を含有することが好ましく、ゼラチンを含有することが特に好ましい。 Among the above, since silver halide grains having excellent dispersion stability can be obtained, the silver halide emulsion layer preferably contains a water-soluble polymer compound, and particularly preferably contains gelatin.
導電材料前駆体が有するハロゲン化銀乳剤層の銀／バインダー質量比は１．３以上であることが導電材料の金属銀細線の導電性の観点から好ましく、同じ観点からハロゲン化銀粒子の含有量は銀換算で２ｇ／ｍ２以上であることが好ましい。さらに好ましくは銀／バインダー質量比が１．７〜３．５、ハロゲン化銀粒子の含有量は銀換算で２．５〜４．０ｇ／ｍ２である。銀／バインダー質量比は高すぎるとハロゲン化銀粒子の保護コロイドとしてのバインダーの割合が不足するため、ハロゲン化銀粒子の分散安定性が不足する場合がある。またハロゲン化銀粒子の含有量を増やしすぎることは、長い現像時間が必要となったり、支持体に近い側のハロゲン化銀粒子の感光性が低下したりする場合がある。 The silver / binder mass ratio of the silver halide emulsion layer of the conductive material precursor is preferably 1.3 or more from the viewpoint of the conductivity of the metal silver fine wire of the conductive material, and from the same viewpoint, the content of silver halide grains Is preferably 2 g / m 2 or more in terms of silver. More preferably, the silver / binder mass ratio is 1.7 to 3.5, and the content of silver halide grains is 2.5 to 4.0 g / m 2 in terms of silver. If the silver / binder mass ratio is too high, the ratio of the binder as a protective colloid for the silver halide grains is insufficient, so that the dispersion stability of the silver halide grains may be insufficient. If the content of the silver halide grains is excessively increased, a long development time may be required, or the photosensitivity of the silver halide grains on the side close to the support may be lowered.
ハロゲン化銀乳剤層は、現像主薬を含有してもよい。現像主薬としては、写真現像の分野で公知の現像主薬を用いることができ、後述する現像液が含有していてもよい現像主薬が例示できる。現像主薬は２種以上含有していてもよい。 The silver halide emulsion layer may contain a developing agent. As the developing agent, a developing agent known in the field of photographic development can be used, and a developing agent that may be contained in a developer described later can be exemplified. Two or more developing agents may be contained.
ハロゲン化銀乳剤層は、バインダーを架橋する目的で後述する物理現像核層が含有していてもよい架橋剤を含有できるが、銀塩拡散転写法により金属銀細線を形成する場合、現像後に不要になったハロゲン化銀乳剤層を水洗除去するため、架橋剤はこれを妨げない範囲で用いることが好ましい。また、ハロゲン化銀乳剤層は公知の写真用添加剤を含有してもよい。具体的にはＲｅｓｅａｒｃｈ Ｄｉｓｃｌｏｓｕｒｅ Ｉｔｅｍ １７６４３（１９７８年１２月）および１８７１６（１９７９年１１月）、３０８１１９（１９８９年１２月）に記載、あるいは引用された文献に記載されている添加剤を例示できる。その他、有機溶剤、界面活性剤、消泡剤、増粘剤等の各種の公知の添加剤を含有してもよい。 The silver halide emulsion layer can contain a cross-linking agent that may be contained in the physical development nucleus layer described later for the purpose of cross-linking the binder, but is unnecessary after development when forming a metal silver fine wire by the silver salt diffusion transfer method. In order to remove the silver halide emulsion layer formed by washing with water, it is preferable to use a crosslinking agent in a range that does not hinder this. The silver halide emulsion layer may contain a known photographic additive. Specific examples include additives described in Research Disclosure Item 17643 (December 1978) and 18716 (November 1979) and 308119 (December 1989) or cited. In addition, you may contain various well-known additives, such as an organic solvent, surfactant, an antifoamer, and a thickener.
＜物理現像核層＞
本発明の導電材料の製造方法において、銀塩拡散転写法により金属銀細線を形成することが、導電性の高い金属銀細線を得る観点から最も好ましく、この場合、導電材料前駆体は支持体上に物理現像核を少なくとも含有する物理現像核層を有することが特に好ましい。物理現像核層は、支持体上に直接有していてもよく、易接着層等の支持体が有する他の層上に有していてもよい。物理現像核としては、重金属あるいはその硫化物からなる微粒子（粒子サイズは１〜数十ｎｍ程度）が用いられる。例えば、金、銀等の金属コロイド、パラジウム、亜鉛等の水溶性塩と硫化物を混合した金属硫化物等が挙げられる。導電材料上の金属銀細線と物理現像核層との接着性の観点から、物理現像核層における物理現像核の含有量は、固形分で０．０１〜１０ｍｇ／ｍ２が好ましい。
<Physical development nucleus layer>
In the method for producing a conductive material of the present invention, it is most preferable to form a metal silver fine wire by a silver salt diffusion transfer method from the viewpoint of obtaining a metal silver fine wire having high conductivity. In this case, the conductive material precursor is on the support. It is particularly preferable to have a physical development nucleus layer containing at least physical development nuclei. The physical development nucleus layer may be directly provided on the support, or may be provided on another layer of the support such as an easy adhesion layer. As the physical development nuclei, fine particles (having a particle size of about 1 to several tens of nm) made of heavy metals or sulfides thereof are used. Examples thereof include metal colloids such as gold and silver, metal sulfides obtained by mixing water-soluble salts such as palladium and zinc and sulfides, and the like. From the viewpoint of adhesion between the metal silver fine wire on the conductive material and the physical development nucleus layer, the physical development nucleus content in the physical development nucleus layer is preferably 0.01 to 10 mg / m 2 in terms of solid content.
物理現像核層は上記した物理現像核以外にハロゲン化銀乳剤層が含有するバインダーとして例示した水溶性高分子化合物や、非水溶性高分子化合物を含有することが好ましく、水溶性高分子化合物を含有することがより好ましく、中でもポリエチレンイミン、ポリアリルアミン等のアミノ基を有する水溶性高分子化合物を含有することが特に好ましい。物理現像核層が含有する水溶性高分子化合物や非水溶性高分子化合物の含有量は、物理現像核に対して１０〜１００００質量％が好ましい。 The physical development nucleus layer preferably contains a water-soluble polymer compound exemplified as a binder contained in the silver halide emulsion layer in addition to the above-described physical development nucleus or a water-insoluble polymer compound. It is more preferable to contain, and it is particularly preferable to contain a water-soluble polymer compound having an amino group such as polyethyleneimine or polyallylamine. The content of the water-soluble polymer compound or water-insoluble polymer compound contained in the physical development nucleus layer is preferably 10 to 10,000% by mass with respect to the physical development nucleus.
物理現像核層が水溶性高分子化合物を含有する場合、該水溶性高分子化合物を架橋するために架橋剤を含有することが好ましい。架橋剤は特に限定されず、公知の架橋剤を用いることができる。具体的にはテトライソプロピルチタネート、チタンアセチルアセトネート、チタンラクテート、ノルマルブチルジルコネート、ジルコニウムモノアセチルアセトネート、アルミニウムトリスアセチルアセトネート等の有機金属化合物、ホルムアルデヒド、グリオキサール、グルタルアルデヒド、３−メチルグルタルアルデヒド、サクシンアルデヒド、アジポアルデヒド等のアルデヒド類、尿素やエチレン尿素等のＮ−メチロール化合物、ムコクロル酸、２，３−ジヒドロキシ−１，４−ジオキサン等のアルデヒド等価体、２，４−ジクロロ−６−ヒドロキシ−ｓ−トリアジン塩や、２，４−ジヒドロキシ−６−クロロ−トリアジン塩等の活性ハロゲンを有する化合物、ジビニルスルホン、ジビニルケトンやＮ，Ｎ，Ｎ−トリアクリロイルヘキサヒドロトリアジン、活性な三員環であるエチレンイミノ基を２つ以上有する化合物、ソルビトールポリグリシジルエーテルやポリグリセロールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル等のエポキシ基を分子中に２個以上有する化合物、硫酸カリウムアルミニウム（ミョウバン）、その他「高分子の化学反応」（大河原 信 著、１９７２、化学同人社）の２．６．７章、５．２章、９．３章等に記載の架橋剤等が例示できる。中でもグリオキサール、グルタルアルデヒド、３−メチルグルタルアルデヒド、サクシンアルデヒド、アジポアルデヒド等のジアルデヒド類やエポキシ基を分子中に２個以上有する化合物が好ましい。架橋剤は、物理現像核層に含まれる水溶性高分子化合物に対して０．１〜８０質量％を物理現像核層に含有させることが好ましい。 When the physical development nucleus layer contains a water-soluble polymer compound, it is preferable to contain a crosslinking agent in order to crosslink the water-soluble polymer compound. A crosslinking agent is not specifically limited, A well-known crosslinking agent can be used. Specifically, organometallic compounds such as tetraisopropyl titanate, titanium acetylacetonate, titanium lactate, normal butyl zirconate, zirconium monoacetylacetonate, aluminum trisacetylacetonate, formaldehyde, glyoxal, glutaraldehyde, 3-methylglutaraldehyde Aldehydes such as succinaldehyde and adipaldehyde, N-methylol compounds such as urea and ethyleneurea, aldehyde equivalents such as mucochloric acid and 2,3-dihydroxy-1,4-dioxane, 2,4-dichloro-6 Compounds having active halogen such as -hydroxy-s-triazine salt and 2,4-dihydroxy-6-chloro-triazine salt, divinyl sulfone, divinyl ketone and N, N, N-triacryloylhexyl Hydrotriazine, compounds having two or more active three-membered ethyleneimino groups, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol 2.6.7 chapters of compounds having two or more epoxy groups in the molecule, such as diglycidyl ether, potassium aluminum sulfate (alum), and other “chemical reactions of polymers” (Shin Okawara, 1972, Kagaku Dojinsha) Examples include the crosslinking agents described in Chapters 5.2 and 9.3. Of these, dialdehydes such as glyoxal, glutaraldehyde, 3-methylglutaraldehyde, succinaldehyde, adipaldehyde and compounds having two or more epoxy groups in the molecule are preferable. The crosslinking agent preferably contains 0.1 to 80% by mass in the physical development nucleus layer with respect to the water-soluble polymer compound contained in the physical development nucleus layer.
物理現像核層は、上記した物質以外にも有機溶剤、界面活性剤、消泡剤、増粘剤等の各種の公知の添加剤を含有してもよい。 The physical development nucleus layer may contain various known additives such as an organic solvent, a surfactant, an antifoaming agent, and a thickener in addition to the above-described substances.
＜その他の構成層＞
導電材料前駆体は、必要に応じて、裏塗り層、中間層、保護層等の非感光性層を有することができる。特に銀塩拡散転写法により金属銀細線を形成する場合、導電材料前駆体は中間層、保護層を有することが好ましい。中間層は現像後に不要になったハロゲン化銀乳剤層の水洗除去を促進する目的で、物理現像核層とハロゲン化銀乳剤層の間に有することが好ましい。保護層はハロゲン化銀乳剤層を傷付きから保護し、現像処理中にハロゲン化銀乳剤層の銀が系外に拡散するのを抑制し、物理現像核上への銀の析出効率を高める目的から、ハロゲン化銀乳剤層の上に有することが好ましい。これらの非感光性層は、主に水溶性高分子化合物からなる層であり、ハロゲン化銀乳剤層が含有するバインダーとして例示した水溶性高分子化合物を用いることができる。非感光性層の水溶性高分子化合物量としては、各々の用途によって異なるが、０．００１〜１０ｇ／ｍ２の範囲が好ましい。これら非感光性層は、水溶性高分子化合物を架橋する目的で、物理現像核層が含有していてもよい架橋剤を含有できるが、銀塩拡散転写法により金属銀細線を形成する場合、現像後に不要になった各構成層を水洗除去するため、これを妨げない範囲で用いることが好ましい。
<Other constituent layers>
The conductive material precursor can have a non-photosensitive layer such as a backing layer, an intermediate layer, and a protective layer, if necessary. In particular, when a metal silver fine wire is formed by a silver salt diffusion transfer method, the conductive material precursor preferably has an intermediate layer and a protective layer. The intermediate layer is preferably provided between the physical development nucleus layer and the silver halide emulsion layer for the purpose of accelerating the washing and removal of the silver halide emulsion layer that is no longer necessary after development. The protective layer protects the silver halide emulsion layer from scratches, suppresses the silver halide emulsion layer from diffusing out of the system during development processing, and increases the efficiency of silver deposition on the physical development nuclei. From the above, it is preferable to have it on the silver halide emulsion layer. These non-photosensitive layers are layers mainly composed of a water-soluble polymer compound, and the water-soluble polymer compounds exemplified as the binder contained in the silver halide emulsion layer can be used. The amount of the water-soluble polymer compound in the non-photosensitive layer varies depending on each application, but is preferably in the range of 0.001 to 10 g / m 2 . These non-photosensitive layers can contain a cross-linking agent that the physical development nucleus layer may contain for the purpose of cross-linking water-soluble polymer compounds, but when forming a metal silver fine wire by silver salt diffusion transfer method, Since each constituent layer that has become unnecessary after development is removed by washing with water, it is preferably used in a range that does not hinder this.
上記した各構成層中には、ハロゲン化銀乳剤の感光波長域に吸収極大を有する非増感性染料または顔料を、画質向上のためのハレーション、あるいはイラジエーション防止剤として用いることが好ましい。ハレーション防止剤は、上記裏塗り層あるいは、物理現像核層、中間層等のハロゲン化銀乳剤層と支持体の間に設けられる層に用いることが好ましく、これら２つ以上の層に分けて用いてもよい。イラジエーション防止剤としては、ハロゲン化銀乳剤層に用いることが好ましい。これら非増感性染料または顔料の添加量は、目的の効果が得られるのであれば特に限定されないが、０．０１〜１ｇ／ｍ２の範囲が好ましい。また上記した各構成層は、必要に応じて公知の写真用添加剤、界面活性剤、マット剤、滑剤、後述する現像液が含有していてもよい現像主薬等を含有できる。 In each of the above-described constituent layers, it is preferable to use a non-sensitizing dye or pigment having an absorption maximum in the photosensitive wavelength region of the silver halide emulsion as a halation for preventing image quality improvement or an irradiation prevention agent. The antihalation agent is preferably used in the above-mentioned backing layer or a layer provided between the silver halide emulsion layer such as the physical development nucleus layer and the intermediate layer and the support, and is used separately in these two or more layers. May be. The irradiation inhibitor is preferably used in a silver halide emulsion layer. The addition amount of these non-sensitizing dyes or pigments is not particularly limited as long as the desired effect can be obtained, but a range of 0.01 to 1 g / m 2 is preferable. Each of the constituent layers described above can contain a known photographic additive, surfactant, matting agent, lubricant, a developing agent that may be contained in a developer described later, and the like, if necessary.
＜導電材料前駆体の製造方法＞
上記したハロゲン化銀乳剤層、物理現像核層、中間層や保護層等の、各構成層を支持体上に設ける方法は特に限定されないが、均一な厚みの各構成層を生産性よく設ける観点から、塗布により設けることが特に好ましい。塗布方法としてはディップコーティング、スライドコーティング、カーテンコーティング、バーコーティング、エアーナイフコーティング、ロールコーティング、グラビアコーティング、スプレーコーティング等が例示できるがこれらに限定されず、公知の塗布方法を用いることができる。
<Method for producing conductive material precursor>
The method of providing each constituent layer on the support, such as the above-described silver halide emulsion layer, physical development nucleus layer, intermediate layer and protective layer, is not particularly limited, but the viewpoint of providing each constituent layer with a uniform thickness with high productivity Therefore, it is particularly preferable to provide by coating. Examples of the application method include dip coating, slide coating, curtain coating, bar coating, air knife coating, roll coating, gravure coating, spray coating, and the like, but are not limited thereto, and known application methods can be used.
＜露光工程＞
本発明の導電材料の製造方法は、支持体上に所望する幾何学形状の金属銀細線を有する金属銀細線パターンを形成することを目的とし、導電材料前駆体を現像する工程の前に、像様に露光する工程を有する。像様に露光する方法としては、所望する金属銀細線パターンに応じた幾何学形状を有する透過原稿を用意し、導電材料前駆体のハロゲン化銀乳剤層を有する側の面に密着させて露光する方法、あるいは各種レーザー光（例えば４００〜４３０ｎｍに発振波長を有する青色半導体レーザーから発振されるレーザー光）を導電材料前駆体のハロゲン化銀乳剤層を有する側の面に照射し、所望する金属銀細線パターンに応じた幾何学形状に走査露光する方法等が例示できる。
<Exposure process>
The method for producing a conductive material of the present invention aims to form a metal silver fine wire pattern having a metal silver fine wire having a desired geometric shape on a support, and an image is formed before the step of developing the conductive material precursor. A step of exposing in the same manner. As an image-wise exposure method, a transparent original having a geometric shape corresponding to a desired metal silver fine line pattern is prepared, and is exposed by being brought into close contact with the surface of the conductive material precursor having the silver halide emulsion layer. Method or various kinds of laser light (for example, laser light oscillated from a blue semiconductor laser having an oscillation wavelength of 400 to 430 nm) is irradiated on the surface having the silver halide emulsion layer of the conductive material precursor, and the desired metallic silver A method of scanning exposure to a geometric shape corresponding to the fine line pattern can be exemplified.
＜現像工程＞
本発明の導電材料の製造方法は、導電材料前駆体を像様に露光した後に、現像液に接触させる現像工程を有する。本発明において銀塩拡散転写法により金属銀細線を形成する場合、現像液に接触させることでハロゲン化銀乳剤層のハロゲン化銀粒子が溶解・拡散し、物理現像核上で還元され金属銀細線パターンが形成される。この場合、導電材料前駆体にネガ型のハロゲン化銀粒子を用いた場合、露光により光を照射されなかったハロゲン化銀乳剤層に対応する部分が金属銀細線となり、ポジ型のハロゲン化銀粒子を用いた場合、露光により光を照射されたハロゲン化銀乳剤層に対応する部分が金属銀細線となる。
<Development process>
The method for producing a conductive material of the present invention includes a developing step in which a conductive material precursor is imagewise exposed and then brought into contact with a developer. In the present invention, when forming a metal silver fine wire by the silver salt diffusion transfer method, the silver halide grains in the silver halide emulsion layer are dissolved and diffused by contact with a developer, and reduced on the physical development nucleus to be reduced. A pattern is formed. In this case, when negative type silver halide grains are used as the conductive material precursor, the portion corresponding to the silver halide emulsion layer not irradiated with light by exposure becomes a metal silver fine wire, and positive type silver halide grains Is used, the portion corresponding to the silver halide emulsion layer irradiated with light by exposure becomes a fine metal silver wire.
＜現像液＞
前述の導電材料前駆体が有する各構成層が現像主薬を含有する場合、上記した現像液は必ずしも現像主薬を含有する必要はなく、現像可能となる潜像核を有するハロゲン化銀粒子の還元を可能とするためのアルカリ性剤を含有する。アルカリ性剤として、例えば水酸化カリウム、水酸化ナトリウム、水酸化リチウム、第３リン酸ナトリウム、あるいは各種アミン化合物が挙げられる。現像液のｐＨは１０以上が好ましくさらに１１〜１４の範囲が好ましい。
<Developer>
When each constituent layer of the conductive material precursor described above contains a developing agent, the developer described above does not necessarily need to contain a developing agent, and silver halide grains having latent image nuclei that can be developed can be reduced. Contains an alkaline agent to make it possible. Examples of the alkaline agent include potassium hydroxide, sodium hydroxide, lithium hydroxide, tribasic sodium phosphate, and various amine compounds. The pH of the developer is preferably 10 or more, and more preferably in the range of 11-14.
前述の導電材料前駆体が有する各構成層が、現像可能となる潜像核を有するハロゲン化銀粒子の還元を可能とする量の現像主薬を含有しない場合、上記した現像液は現像主薬を含有する。現像液が含有する現像主薬としては、例えば、ハイドロキノン、カテコール、ピロガロール、メチルハイドロキノン、クロロハイドロキノン等のポリヒドロキシベンゼン類、１−フェニル−４，４−ジメチル−３−ピラゾリドン、１−フェニル−３−ピラゾリドン、１−ｐ−トリル−３−ピラゾリドン、１−フェニル−４−メチル−３−ピラゾリドン、１−フェニル−４−メチル−４−ヒドロキシメチル−３−ピラゾリドン、１−ｐ−クロロフェニル−３−ピラゾリドン等の３−ピラゾリドン類、パラメチルアミノフェノール、パラアミノフェノール、パラヒドロキシフェニルグリシン、パラフェニレンジアミン、アスコルビン酸等が挙げられ、これらを２種類以上併用してもよい。導電材料の金属銀細線の導電性の観点から、現像液中の現像主薬の含有量は１〜１００ｇ／Ｌであることが好ましい。 When each of the constituent layers of the conductive material precursor described above does not contain an amount of developing agent that enables the reduction of silver halide grains having latent image nuclei that can be developed, the developer described above contains the developing agent. To do. As the developing agent contained in the developer, for example, polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, chlorohydroquinone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-3- Pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-p-chlorophenyl-3-pyrazolidone Such as 3-pyrazolidones, paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, paraphenylenediamine, ascorbic acid and the like, and two or more of these may be used in combination. From the viewpoint of the conductivity of the metallic silver fine wire of the conductive material, the content of the developing agent in the developer is preferably 1 to 100 g / L.
現像液はその他に、亜硫酸ナトリウムや亜硫酸カリウム等の保恒剤や、ｐＨを好ましい範囲に保つために炭酸塩やリン酸塩等のｐＨ緩衝剤を含有することが好ましい。さらに臭化物イオン、ベンズイミダゾール、ベンゾトリアゾール、１−フェニル−５−メルカプトテトラゾール等、現像核を持たないハロゲン化銀粒子が還元されないように加えられるカブリ防止剤を含有していてもよい。 In addition, the developer preferably contains a preservative such as sodium sulfite or potassium sulfite and a pH buffer such as carbonate or phosphate in order to keep the pH within a preferable range. Further, it may contain an antifoggant added such that bromide ions, benzimidazole, benzotriazole, 1-phenyl-5-mercaptotetrazole and the like are added so that silver halide grains having no development nucleus are not reduced.
銀塩拡散転写法により金属銀細線を形成する場合、現像液は拡散転写現像を行うために可溶性銀錯塩形成剤を含有することが特に好ましい。可溶性銀錯塩形成剤としては、具体的にはチオ硫酸アンモニウムやチオ硫酸ナトリウムのようなチオ硫酸塩、チオシアン酸ナトリウムやチオシアン酸アンモニウムのようなチオシアン酸塩、亜硫酸ナトリウムや亜硫酸水素カリウムのような亜硫酸塩、１，１０−ジチア−１８−クラウン−６、２，２′−チオジエタノールなどのチオエーテル類、オキサゾリドン類、２−メルカプト安息香酸およびその誘導体、ウラシルのような環状イミド類、アルカノールアミン、ジアミン、特開平９−１７１２５７号公報に記載のメソイオン性化合物、５，５−ジアルキルヒダントイン類、アルキルスルホン類、他に「Ｔｈｅ Ｔｈｅｏｒｙ ｏｆ ｔｈｅ ｐｈｏｔｏｇｒａｐｈｉｃ Ｐｒｏｃｅｓｓ（４ｔｈ ｅｄｉｔｉｏｎ，ｐ４７４〜４７５）」、Ｔ．Ｈ．Ｊａｍｅｓ著に記載されている化合物が挙げられる。これらの可溶性銀錯塩形成剤の中で特にアルカノールアミンが好ましい。アルカノールアミンとしては、例えばＮ−（２−アミノエチル）エタノールアミン、ジエタノールアミン、Ｎ−メチルエタノールアミン、トリエタノールアミン、Ｎ−エチルジエタノールアミン、ジイソプロパノールアミン、エタノールアミン、４−アミノブタノール、Ｎ，Ｎ−ジメチルエタノールアミン、３−アミノプロパノール、２−アミノ−２−メチル−１−プロパノール等が挙げられる。これらの可溶性銀錯塩形成剤は単独で、または複数組み合わせて使用することができる。導電材料の金属銀細線の導電性の観点から、現像液中の可溶性銀錯塩形成剤量の含有量としては０．１〜４０ｇ／Ｌが好ましく、より好ましくは１〜２０ｇ／Ｌである。 In the case of forming a metal silver fine wire by the silver salt diffusion transfer method, it is particularly preferable that the developer contains a soluble silver complex salt forming agent in order to perform diffusion transfer development. Specific examples of soluble silver complex forming agents include thiosulfates such as ammonium thiosulfate and sodium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, and sulfites such as sodium sulfite and potassium hydrogen sulfite. Thioethers such as 1,10-dithia-18-crown-6,2,2'-thiodiethanol, oxazolidones, 2-mercaptobenzoic acid and its derivatives, cyclic imides such as uracil, alkanolamines, diamines, JP-A-9-171257, mesoionic compounds, 5,5-dialkylhydantoins, alkyl sulfones, and other "The Theory of the Photographic Process (4th edition, p474-475)", TH. Examples include compounds described in James. Of these soluble silver complex salt forming agents, alkanolamines are particularly preferred. Examples of the alkanolamine include N- (2-aminoethyl) ethanolamine, diethanolamine, N-methylethanolamine, triethanolamine, N-ethyldiethanolamine, diisopropanolamine, ethanolamine, 4-aminobutanol, N, N- Examples include dimethylethanolamine, 3-aminopropanol, and 2-amino-2-methyl-1-propanol. These soluble silver complex salt forming agents can be used alone or in combination. From the viewpoint of the conductivity of the metallic silver fine wire of the conductive material, the content of the soluble silver complex salt forming agent in the developer is preferably 0.1 to 40 g / L, more preferably 1 to 20 g / L.
＜現像条件＞
導電材料前駆体に接触させる現像液の温度は特に限定されないが、現像速度の観点、およびハロゲン化銀乳剤層が現像液中に溶出するのを防止する観点から１５℃〜３０℃が好ましく、１８℃〜２７℃が特に好ましい。現像時間は生産効率を考慮して１２０秒以下が好ましい。
<Development conditions>
The temperature of the developer to be brought into contact with the conductive material precursor is not particularly limited, but is preferably 15 ° C. to 30 ° C. from the viewpoint of development speed and from the viewpoint of preventing the silver halide emulsion layer from eluting into the developer. C. to 27.degree. C. is particularly preferred. The development time is preferably 120 seconds or less in consideration of production efficiency.
像様に露光した後の導電材料前駆体に現像液を接触させる方式としては、浸漬方式や塗布方式を例示できる。浸漬方式は、例えば、タンクに大量に貯流された現像液中に、露光済みの導電材料前駆体を浸漬しながら搬送するものであり、塗布方式は、例えば導電材料前駆体上に現像液を１ｍ２あたり４０〜１２０ｍＬ程度塗布するものである。 Examples of the method for bringing the developer into contact with the conductive material precursor after imagewise exposure include an immersion method and a coating method. In the immersion method, for example, the exposed conductive material precursor is transported while being immersed in a large amount of developer stored in a tank. In the coating method, for example, the developer is applied on the conductive material precursor. About 40 to 120 mL is applied per 1 m 2 .
本発明の導電材料の製造方法において、銀塩拡散転写法ではなく、特開２００４−２２１５６４号公報等に示された直接現像方式を用いて金属銀細線を形成する場合、現像液に接触後、酢酸やクエン酸等の酸を含有する停止液に接触させて現像を停止させる工程や、チオ硫酸塩やチオシアン酸塩等のハロゲン化銀溶剤を含有する定着液に接触させ、未露光のハロゲン化銀乳剤層中のハロゲン化銀粒子を溶解除去する定着工程を有していてもよい。 In the method for producing a conductive material of the present invention, when a metal silver fine wire is formed using a direct development method disclosed in JP-A-2004-221564, etc., instead of the silver salt diffusion transfer method, after contact with the developer, Unexposure halogenation by contacting a stop solution containing acid such as acetic acid or citric acid to stop development or contact with a fixer containing a silver halide solvent such as thiosulfate or thiocyanate A fixing step of dissolving and removing silver halide grains in the silver emulsion layer may be provided.
＜水洗工程＞
上記方法に従い導電材料前駆体を現像した後、あるいは上述した定着工程の後に、水洗することが好ましい。特に銀塩拡散転写法により金属銀細線を形成する場合、現像後の導電材料前駆体を水洗することで、現像後に不要となったハロゲン化銀乳剤層等の各構成層を除去し、金属銀細線を支持体上に露出させることができる。水洗は水単体で行ってもよく、炭酸塩やリン酸塩等のｐＨ緩衝剤を含有する水で行ってもよく、腐敗を防止する目的で防腐剤を含有する水で行ってもよい。
<Washing process>
It is preferable to wash with water after developing the conductive material precursor according to the above method or after the fixing step described above. In particular, when forming a metal silver fine wire by the silver salt diffusion transfer method, each constituent layer such as a silver halide emulsion layer that has become unnecessary after development is removed by washing the conductive material precursor after development with water. Fine wires can be exposed on the support. Washing with water may be carried out with water alone, with water containing a pH buffer such as carbonate or phosphate, or with water containing a preservative for the purpose of preventing spoilage.
水洗方法としては、スクラビングローラ等を用いて温水シャワーを噴射しながら除去する方法や温水をノズル等でジェット噴射しながら水の勢いで除去する方法がある。また、シャワーやスリットを複数個設けて、除去の効率を高めることもできる。また、ハロゲン化銀乳剤層を除去する際には、水洗除去の代わりに、剥離紙等に転写剥離する方法を用いてもよい。剥離紙等で転写剥離する方法としては、ハロゲン化銀乳剤層上の余分な現像液を予めローラ等で絞り取っておき、ハロゲン化銀乳剤層等と剥離紙を密着させてハロゲン化銀乳剤層等をプラスチック樹脂フィルムから剥離紙に転写させて剥離する方法である。剥離紙としては吸水性のある紙や不織布、あるいは紙の上にシリカのような微粒子顔料とポリビニルアルコールのようなバインダーとで吸水性の空隙層を設けたものが用いられる。 As a water washing method, there are a method of removing hot water shower while spraying using a scrubbing roller or the like, and a method of removing hot water by jetting with a nozzle or the like with the force of water. Also, a plurality of showers and slits can be provided to increase the removal efficiency. Further, when removing the silver halide emulsion layer, a method of transferring and peeling to a release paper or the like may be used instead of washing with water. As a method of transferring and peeling with release paper, etc., excess developer on the silver halide emulsion layer is squeezed out beforehand with a roller, etc., and the silver halide emulsion layer and the release paper are brought into close contact with each other to remove the silver halide emulsion layer etc. This is a method of transferring from a plastic resin film to release paper and peeling. As the release paper, water-absorbing paper or non-woven fabric, or paper having a water-absorbing void layer formed of fine pigment such as silica and binder such as polyvinyl alcohol on the paper is used.
＜現像後の後処理＞
導電材料前駆体を現像し得られた金属銀細線の表面に対し、公知の金属表面処理を施してもよい。例えば特開２００８−３４３６６号公報に記載されているような還元性物質、水溶性リンオキソ酸化合物、水溶性ハロゲン化合物を作用させてもよく、特開２０１３−１９６７７９号公報に記載されているような分子内に２つ以上のメルカプト基を有するトリアジンもしくはその誘導体を作用させてもよく、特開２０１１−２０９６２６号公報に記載されているように硫化反応による黒化処理を施してもよい。あるいは特開２００７−１２４０４号公報に記載されているようにタンパク質分解酵素等の酵素を含有する処理液で処理し、残存するゼラチン等の除去を促進してもよい。
<Post-processing after development>
A known metal surface treatment may be applied to the surface of the metal silver fine wire obtained by developing the conductive material precursor. For example, a reducing substance, a water-soluble phosphorus oxo acid compound, or a water-soluble halogen compound as described in JP 2008-34366 A may be allowed to act, as described in JP 2013-19679 A A triazine having two or more mercapto groups in the molecule or a derivative thereof may be allowed to act, and as described in JP 2011-209626 A, blackening treatment by a sulfurization reaction may be performed. Alternatively, as described in JP-A-2007-12404, treatment with a treatment solution containing an enzyme such as a proteolytic enzyme may be performed to promote the removal of remaining gelatin or the like.
＜導電材料＞
本発明の導電材料の製造方法により得られた導電材料の、支持体上の金属銀細線の線幅は特に限定されないが、１〜５００μｍであることが導電材料の信頼性の観点から好ましい。
<Conductive material>
The line width of the metal silver fine wire on the support of the conductive material obtained by the method for producing a conductive material of the present invention is not particularly limited, but is preferably 1 to 500 μm from the viewpoint of the reliability of the conductive material.
本発明の導電材料の製造方法により得られた導電材料をタッチパネルセンサーに利用する場合、導電材料は金属銀細線からなる網目状金属銀細線パターンを有することが好ましい。網目状金属銀細線パターンは複数の単位格子を網目状に配置した幾何学形状を有することがセンサーの感度、視認性（センサーの形状が見えにくい）等の観点から好ましい。単位格子の形状としては、例えば正三角形、二等辺三角形、直角三角形等の三角形、正方形、長方形、菱形、平行四辺形、台形等の四角形、六角形、八角形、十二角形、二十角形等のｎ角形、星形等を組み合わせた形状が挙げられ、またこれらの形状の単独の繰り返し、あるいは２種類以上の複数の形状の組み合わせが挙げられる。中でも単位格子の形状としては正方形もしくは菱形が好ましい。またボロノイ図形やドロネー図形、ペンローズタイル図形等に代表される不規則幾何学形状も好ましい網目状金属銀細線パターンの形状の一つである。 When using the conductive material obtained by the manufacturing method of the conductive material of this invention for a touch panel sensor, it is preferable that a conductive material has a mesh-like metal silver fine wire pattern which consists of a metal silver fine wire. The mesh-like metallic silver thin wire pattern preferably has a geometric shape in which a plurality of unit cells are arranged in a mesh shape from the viewpoint of sensor sensitivity, visibility (the sensor shape is difficult to see), and the like. Examples of unit cell shapes include triangles such as regular triangles, isosceles triangles, right triangles, squares, rectangles, rhombuses, parallelograms, trapezoids, etc., hexagons, octagons, dodecagons, decagons, etc. The shape which combined n square, star shape, etc. of these is mentioned, The repetition of these shapes independently, or the combination of two or more types of multiple shapes is mentioned. Among them, the shape of the unit cell is preferably a square or a rhombus. Irregular geometric shapes represented by Voronoi figures, Delaunay figures, Penrose tile figures, etc. are also one of the preferred mesh-like metallic silver thin line patterns.
本発明の導電材料の製造方法により得られた導電材料をタッチパネルセンサーに利用する場合、本発明の導電材料の製造方法により得られた導電材料の金属銀細線を有する側の面、あるいはもう一方の側の面には、前述の導電材料や、化学強化ガラス、ソーダガラス、石英ガラス、無アルカリガラス等のガラス、ポリエチレンテレフタレート等の各種樹脂からなるフィルム、および上記したガラスやフィルムの少なくとも一方の面にハードコート層、反射防止層、防眩層、偏光層、ＩＴＯ等からなる導電膜等の公知の機能層を有する材料を、接着層を介して有することができる。接着層は特に限定されず、特開平９−２５１１５９号公報や特開２０１１−７４３０８号公報等に例示されているような透明性の高いアクリル系粘着剤を使用した光学用粘着テープや、特開２００９−４８２１４号公報、特開２０１０−２５７２０８号公報等に例示されているような透明性の高い硬化型樹脂等、公知のものを使用できる。光学用粘着テープ、透明性の高い硬化型樹脂はともに市販されており、前者では住友スリーエム（株）製高透明性接着剤転写テープ（８１７１ＣＬ／８１７２ＣＬ／８１４６−１／８１４６−２／８１４６−３／８１４６−４等）、日東電工（株）製光学用透明粘着シート（ＬＵＣＩＡＣＳ（登録商標） ＣＳ９６２２Ｔ／ＣＳ９８６２ＵＡ等）、積水化学工業（株）製高透明両面テープ５４００Ｘシリーズ（５４０５Ｘ−７５／５４０７Ｘ−７５等）等が例示でき、後者ではデクセリアルズ（株）製光学弾性樹脂ＳＶＲ（登録商標）シリーズ（ＳＶＲ１１５０、ＳＶＲ１３２０等）、協立化学産業（株）製ＷＯＲＬＤ ＲＯＣＫ（登録商標）シリーズ（ＨＲＪ（登録商標）−４６、ＨＲＪ−２０３等）、ヘンケルジャパン（株）製紫外線硬化型光学透明接着剤Ｌｏｃｔｉｔｅ（登録商標） ＬＯＣＡシリーズ（Ｌｏｃｔｉｔｅ３１９２、３１９３、３１９５、５１９２等）を例示でき、いずれも好ましく用いることができる。 When the conductive material obtained by the method for producing a conductive material of the present invention is used for a touch panel sensor, the surface of the conductive material obtained by the method for producing a conductive material of the present invention on the side having a metal silver fine wire, or the other side On the side surface, the above-mentioned conductive material, chemically tempered glass, soda glass, quartz glass, alkali-free glass and other films, films made of various resins such as polyethylene terephthalate, and at least one of the above-described glasses and films In addition, a material having a known functional layer such as a hard coat layer, an antireflection layer, an antiglare layer, a polarizing layer, a conductive film made of ITO, or the like can be provided via an adhesive layer. The adhesive layer is not particularly limited, and an optical pressure-sensitive adhesive tape using a highly transparent acrylic pressure-sensitive adhesive as exemplified in JP-A-9-251159 and JP-A-2011-74308, Known materials such as highly transparent curable resins as exemplified in JP-A No. 2009-48214 and JP-A No. 2010-257208 can be used. Both optical pressure-sensitive adhesive tapes and highly transparent curable resins are commercially available. The former is a highly transparent adhesive transfer tape (8171CL / 8172CL / 8146-1 / 8146-2 / 8146-3) manufactured by Sumitomo 3M Limited. / 8146-4 etc.), Nitto Denko Co., Ltd. optical transparent adhesive sheet (LUCIACS (registered trademark) CS9622T / CS9862UA etc.), Sekisui Chemical Co., Ltd. highly transparent double-sided tape 5400X series (5405X-75 / 5407X-) In the latter case, the optical elastic resin SVR (registered trademark) series (SVR1150, SVR1320, etc.) manufactured by Dexerials Co., Ltd., and the WARLD ROCK (registered trademark) series (HRJ (registered trademark) manufactured by Kyoritsu Chemical Industry Co., Ltd.) Trademark) -46, HRJ-203, etc.), UV curing manufactured by Henkel Japan K.K. Type optical transparent adhesive Loctite (registered trademark) LOCA series (Loctite 3192, 3193, 3195, 5192 etc.) can be exemplified, and any of them can be preferably used.
以下、本発明に関し実施例を用いて詳細に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to a following example, unless the summary is exceeded.
＜導電材料前駆体１の作製＞
支持体として、厚み１００μｍのポリエチレンテレフタレートフィルムを用いた。なお、支持体の全光線透過率は９２％、ヘイズは０．８％であった。
<Preparation of Conductive Material Precursor 1>
A polyethylene terephthalate film having a thickness of 100 μm was used as the support. The support had a total light transmittance of 92% and a haze of 0.8%.
次に下記組成の物理現像核層塗液を支持体上に塗布、乾燥して物理現像核層を設けた。 Next, a physical development nucleus layer coating solution having the following composition was coated on a support and dried to provide a physical development nucleus layer.
＜硫化パラジウムゾルの調製＞
Ａ液 塩化パラジウム ５ｇ
塩酸 ４０ｍＬ
蒸留水 １０００ｍＬ
Ｂ液 硫化ソーダ ８．６ｇ
蒸留水 １０００ｍＬ
Ａ液とＢ液を撹拌しながら混合し、３０分後にイオン交換樹脂の充填されたカラムに通し硫化パラジウムゾルを得た。
<Preparation of palladium sulfide sol>
Liquid A Palladium chloride 5g
Hydrochloric acid 40mL
Distilled water 1000mL
B liquid sodium sulfide 8.6g
Distilled water 1000mL
Liquid A and liquid B were mixed with stirring, and 30 minutes later, the solution was passed through a column filled with an ion exchange resin to obtain palladium sulfide sol.
＜物理現像核層塗液／１ｍ２あたり＞
前記硫化パラジウムゾル（固形分として） ０．５ｍｇ
２質量％グリオキサール水溶液 ０．２ｍＬ
界面活性剤（Ｓ−１） ４ｍｇ
デナコール（登録商標）ＥＸ−８３０ ２５ｍｇ
（ナガセケムテックス（株）製ポリエチレングリコールジグリシジルエーテル、平均分子量５２６）
１０質量％エポミン（登録商標）ＳＰ−２００水溶液 ０．１ｇ
（（株）日本触媒製ポリエチレンイミン；平均分子量１００００）
<Physical development nucleus layer coating solution / per 1 m 2 >
The palladium sulfide sol (as solid content) 0.5mg
2% by mass aqueous glyoxal solution 0.2mL
Surfactant (S-1) 4mg
Denacol (registered trademark) EX-830 25mg
(Negase ChemteX Co., Ltd. polyethylene glycol diglycidyl ether, average molecular weight 526)
10% by mass of Epomin (registered trademark) SP-200 aqueous solution 0.1 g
(Nippon Shokubai Polyethyleneimine; average molecular weight 10,000)
続いて、支持体に近い方から順に下記組成の中間層１、ハロゲン化銀乳剤層１、および保護層１を上記物理現像核層の上に塗布、乾燥して、導電材料前駆体１を得た。ハロゲン化銀乳剤層１が含有するハロゲン化銀乳剤は、コントロールドダブルジェット法で製造した。このハロゲン化銀乳剤が含有するハロゲン化銀粒子は、塩化銀９５ｍｏｌ％と臭化銀５ｍｏｌ％で、平均粒径が０．１５μｍになるように調製した。このようにして得られたハロゲン化銀粒子を定法に従いチオ硫酸ナトリウムと塩化金酸を用い、金イオウ増感を施した。こうして得られたハロゲン化銀乳剤は、銀１ｇあたり０．５ｇのゼラチンを保護コロイド（バインダー）として含有する。 Subsequently, the intermediate layer 1, the silver halide emulsion layer 1, and the protective layer 1 having the following composition are coated on the physical development nucleus layer in order from the side closer to the support and dried to obtain a conductive material precursor 1. It was. The silver halide emulsion contained in the silver halide emulsion layer 1 was produced by the controlled double jet method. The silver halide grains contained in this silver halide emulsion were prepared so that the average particle diameter was 0.15 μm with 95 mol% of silver chloride and 5 mol% of silver bromide. The silver halide grains thus obtained were subjected to gold sulfur sensitization using sodium thiosulfate and chloroauric acid according to a conventional method. The silver halide emulsion thus obtained contains 0.5 g of gelatin as a protective colloid (binder) per 1 g of silver.
＜中間層１組成／１ｍ２あたり＞
ゼラチン ０．５ｇ
界面活性剤（Ｓ−１） ５ｍｇ
染料１ ５ｍｇ
<Intermediate layer 1 composition / 1 m 2 >
Gelatin 0.5g
Surfactant (S-1) 5mg
Dye 1 5mg
＜ハロゲン化銀乳剤層１組成／１ｍ２あたり＞
ハロゲン化銀乳剤 ３．０ｇ銀相当
１−フェニル−５−メルカプトテトラゾール ３ｍｇ
界面活性剤（Ｓ−１） ２０ｍｇ
<Silver halide emulsion layer 1 composition / m 2 >
Silver halide emulsion 3.0g Silver equivalent 1-Phenyl-5-mercaptotetrazole 3mg
Surfactant (S-1) 20mg
＜保護層１組成／１ｍ２あたり＞
ゼラチン １ｇ
不定形シリカマット剤（平均粒径３．５μｍ） １０ｍｇ
界面活性剤（Ｓ−１） １０ｍｇ
<1 composition of protective layer / 1 m 2 >
1g of gelatin
Amorphous silica matting agent (average particle size 3.5μm) 10mg
Surfactant (S-1) 10mg
＜導電材料前駆体２の作製＞
保護層１に平均分子量が３１００のポリエチレングリコールを２０ｍｇ／ｍ２含有させた以外は導電材料前駆体１と同様にして、導電材料前駆体２を得た。
<Preparation of Conductive Material Precursor 2>
A conductive material precursor 2 was obtained in the same manner as the conductive material precursor 1 except that the protective layer 1 contained 20 mg / m 2 of polyethylene glycol having an average molecular weight of 3100.
＜導電材料前駆体３の作製＞
保護層１に平均分子量が８８００のポリエチレングリコールを２０ｍｇ／ｍ２含有させた以外は導電材料前駆体１と同様にして、導電材料前駆体３を得た。
<Preparation of Conductive Material Precursor 3>
A conductive material precursor 3 was obtained in the same manner as the conductive material precursor 1 except that the protective layer 1 contained 20 mg / m 2 of polyethylene glycol having an average molecular weight of 8800.
＜導電材料前駆体４の作製＞
保護層１に平均分子量が１１０００のポリエチレングリコールを２０ｍｇ／ｍ２含有させた以外は導電材料前駆体１と同様にして、導電材料前駆体４を得た。
<Preparation of Conductive Material Precursor 4>
A conductive material precursor 4 was obtained in the same manner as the conductive material precursor 1 except that the protective layer 1 contained 20 mg / m 2 of polyethylene glycol having an average molecular weight of 11000.
＜導電材料前駆体５の作製＞
保護層１に平均分子量が２００００のポリエチレングリコールを２０ｍｇ／ｍ２含有させた以外は導電材料前駆体１と同様にして、導電材料前駆体５を得た。
<Preparation of Conductive Material Precursor 5>
A conductive material precursor 5 was obtained in the same manner as the conductive material precursor 1 except that the protective layer 1 contained 20 mg / m 2 of polyethylene glycol having an average molecular weight of 20000.
＜導電材料前駆体６の作製＞
保護層１に平均分子量が４０００のポリエチレングリコールモノメチルエーテルを２０ｍｇ／ｍ２含有させた以外は導電材料前駆体１と同様にして、導電材料前駆体６を得た。
<Preparation of Conductive Material Precursor 6>
A conductive material precursor 6 was obtained in the same manner as the conductive material precursor 1 except that the protective layer 1 contained 20 mg / m 2 of polyethylene glycol monomethyl ether having an average molecular weight of 4000.
＜導電材料前駆体７の作製＞
ハロゲン化銀乳剤層１に平均分子量が８８００のポリエチレングリコールを２０ｍｇ／ｍ２含有させた以外は導電材料前駆体１と同様にして、導電材料前駆体７を得た。
<Preparation of Conductive Material Precursor 7>
A conductive material precursor 7 was obtained in the same manner as the conductive material precursor 1 except that the silver halide emulsion layer 1 contained 20 mg / m 2 of polyethylene glycol having an average molecular weight of 8800.
＜導電材料前駆体８の作製＞
中間層１に平均分子量が８８００のポリエチレングリコールを２０ｍｇ／ｍ２含有させた以外は導電材料前駆体１と同様にして、導電材料前駆体８を得た。
<Preparation of Conductive Material Precursor 8>
A conductive material precursor 8 was obtained in the same manner as the conductive material precursor 1 except that the intermediate layer 1 contained 20 mg / m 2 of polyethylene glycol having an average molecular weight of 8800.
＜導電材料前駆体９の作製＞
保護層１およびハロゲン化銀乳剤層１の両方に平均分子量が８８００のポリエチレングリコールをそれぞれ１０ｍｇ／ｍ２含有させた以外は導電材料前駆体１と同様にして、導電材料前駆体９を得た。
<Preparation of Conductive Material Precursor 9>
A conductive material precursor 9 was obtained in the same manner as the conductive material precursor 1 except that both the protective layer 1 and the silver halide emulsion layer 1 each contained 10 mg / m 2 of polyethylene glycol having an average molecular weight of 8800.
＜導電材料前駆体１０の作製＞
保護層１に平均分子量が１０００のポリエチレングリコールを２０ｍｇ／ｍ２含有させた以外は導電材料前駆体１と同様にして、導電材料前駆体１０を得た。
<Preparation of Conductive Material Precursor 10>
A conductive material precursor 10 was obtained in the same manner as the conductive material precursor 1 except that the protective layer 1 contained 20 mg / m 2 of polyethylene glycol having an average molecular weight of 1000.
＜導電材料前駆体１１の作製＞
保護層１に平均分子量が２０００のポリエチレングリコールを２０ｍｇ／ｍ２含有させた以外は導電材料前駆体１と同様にして、導電材料前駆体１１を得た。
<Preparation of Conductive Material Precursor 11>
A conductive material precursor 11 was obtained in the same manner as the conductive material precursor 1 except that the protective layer 1 contained 20 mg / m 2 of polyethylene glycol having an average molecular weight of 2000.
＜現像液１の作製＞
水酸化カリウム ２５ｇ
ハイドロキノン １８ｇ
１−フェニル−３−ピラゾリドン ２ｇ
亜硫酸カリウム ８０ｇ
Ｎ−メチルエタノールアミン １５ｇ
臭化カリウム １．２ｇ
全量を水で１０００ｍＬ、ｐＨ＝１２．２に調整した。
<Preparation of Developer 1>
Potassium hydroxide 25g
Hydroquinone 18g
1-phenyl-3-pyrazolidone 2g
Potassium sulfite 80g
N-methylethanolamine 15g
Potassium bromide 1.2g
The total amount was adjusted to 1000 mL with water and pH = 12.2.
＜現像液２の作製＞
平均分子量が３１００のポリエチレングリコールを１．０ｇ／Ｌ追加した以外は現像液１と同様にして、現像液２を得た。
<Preparation of Developer 2>
Developer 2 was obtained in the same manner as Developer 1, except that 1.0 g / L of polyethylene glycol having an average molecular weight of 3100 was added.
＜現像液３の作製＞
平均分子量が８８００のポリエチレングリコールを１．０ｇ／Ｌ追加した以外は現像液１と同様にして、現像液３を得た。
<Preparation of Developer 3>
Developer 3 was obtained in the same manner as Developer 1, except that 1.0 g / L of polyethylene glycol having an average molecular weight of 8800 was added.
＜現像液４の作製＞
平均分子量が２０００のポリエチレングリコールを１．０ｇ／Ｌ追加した以外は現像液１と同様にして、現像液４を得た。
<Preparation of Developer 4>
Developer 4 was obtained in the same manner as Developer 1, except that 1.0 g / L of polyethylene glycol having an average molecular weight of 2000 was added.
＜導電材料１〜１４の作製＞
上記した導電材料前駆体１〜１１それぞれについて、線幅５．０μｍ、一辺の長さが３００μｍの正方形を単位格子とする網目状パターンからなるポジ型透過原稿を密着し、水銀灯を光源とする密着プリンターで４００ｎｍ以下の光をカットする樹脂フィルターを介して露光した。その後、露光済みの導電材料前駆体１〜１１と上記した現像液１〜４を、後述する表１の組み合わせにて現像し（露光済みの導電材料前駆体を２０℃の現像液中に９０秒間浸漬し）、続いてハロゲン化銀乳剤層、中間層、および保護層を４０℃の温水で水洗除去し、乾燥処理することで、網目状金属銀細線パターンを有する導電材料１〜１４を得た。導電材料１〜１４の網目状金属銀細線パターンを構成する金属銀細線の線幅を顕微鏡で観察したところ、いずれも５．０μｍであった。
<Preparation of conductive materials 1-14>
For each of the conductive material precursors 1 to 11 described above, a positive-type transparent original composed of a mesh pattern having a unit grid of a square having a line width of 5.0 μm and a side length of 300 μm is adhered, and a mercury lamp is used as a light source It exposed through the resin filter which cuts the light below 400 nm with a printer. Thereafter, the exposed conductive material precursors 1 to 11 and the developers 1 to 4 described above are developed with the combinations shown in Table 1 described later (the exposed conductive material precursor is placed in a developer at 20 ° C. for 90 seconds. Then, the silver halide emulsion layer, the intermediate layer, and the protective layer were washed away with warm water at 40 ° C. and dried to obtain conductive materials 1 to 14 having a mesh-like metallic silver fine wire pattern. . When the line width of the metal silver fine wire which comprises the mesh-like metal silver fine wire pattern of the electrically-conductive materials 1-14 was observed with the microscope, all were 5.0 micrometers.
＜導電性評価＞
導電材料１〜１４の網目状金属銀細線パターンの表面抵抗率を、（株）三菱ケミカルアナリテック製、ロレスタ（登録商標）−ＧＰ／ＥＳＰプローブを用いて、ＪＩＳ Ｋ ７１９４に従い測定した。導電材料１が有する網目状金属銀細線パターンの表面抵抗率を基準とし、導電材料２〜１４が有する網目状金属銀細線パターンの表面抵抗率が、導電材料１の表面抵抗率の９５〜１０５％の場合は「×」、８５〜９５％の場合は「△」、７５〜８５％の場合は「〇」、７５％以下の場合は「◎」として導電性の評価を実施した。この結果を表１に示す。
<Electrical conductivity evaluation>
The surface resistivity of the mesh metal silver fine wire patterns of the conductive materials 1 to 14 was measured according to JIS K 7194 using a Loresta (registered trademark) -GP / ESP probe manufactured by Mitsubishi Chemical Analytech. Based on the surface resistivity of the mesh-like metallic silver fine wire pattern that the conductive material 1 has, the surface resistivity of the mesh-like metallic silver fine wire pattern that the conductive material 2 to 14 has is 95 to 105% of the surface resistivity of the conductive material 1. The electrical conductivity was evaluated as “×” in the case of “、”, “Δ” in the case of 85 to 95%, “◯” in the case of 75 to 85%, and “◎” in the case of 75% or less. The results are shown in Table 1.
表１の結果から本発明の有効性が判る。 The effectiveness of the present invention can be seen from the results in Table 1.
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