TWI592761B - Method for forming conductive pattern and conductive pattern substrate - Google Patents

以下，對本發明的較佳的實施方式進行詳細地說明。另外，本說明書中所謂「(甲基)丙烯酸酯」，是指「丙烯酸酯」及「甲基丙烯酸酯」。同樣，所謂「(甲基)丙烯酸基」，是指「丙烯酸基」及「甲基丙烯酸基」，所謂「(甲基)丙烯醯基」，是指「丙烯醯基」及「甲基丙烯醯基」。 Hereinafter, preferred embodiments of the present invention will be described in detail. In addition, in this specification, "(meth)acrylate" means "acrylate" and "methacrylate". Similarly, the term "(meth)acrylic group" means "acrylic group" and "methacrylic acid group", and the term "(meth)acryloyl group" means "acryloyl group" and "methacryloyl group". base".

本實施方式的導電圖案的形成方法包括：準備依序具備支撐膜、含有導電性纖維的導電層、以及含有感光性樹脂的感光性樹脂層的感光性導電膜，並以導電層密接於基材上的方式層壓導電層及感光性樹脂層的層壓步驟；以及藉由將上述基材上的感光性樹脂層進行曝光及顯影而形成導電圖案的圖案化步驟。 The method for forming a conductive pattern according to the present embodiment includes preparing a photosensitive conductive film including a support film, a conductive layer containing conductive fibers, and a photosensitive resin layer containing a photosensitive resin, and bonding the conductive layer to the substrate a lamination step of laminating a conductive layer and a photosensitive resin layer; and a patterning step of forming a conductive pattern by exposing and developing the photosensitive resin layer on the substrate.

本說明書中，導電層與感光性樹脂層的邊界不需要一定得明確。導電層只要在感光層的面方向可獲得導電性即可，亦可為在導電層中混合感光性樹脂層的形態。例如，可在導電層中含 浸構成感光性樹脂層的組成物、或構成感光性樹脂層的組成物可存在於導電層的表面。 In the present specification, the boundary between the conductive layer and the photosensitive resin layer need not necessarily be specified. The conductive layer may have conductivity in the surface direction of the photosensitive layer, and may be a form in which a photosensitive resin layer is mixed in the conductive layer. For example, it can be included in the conductive layer The composition immersed in the photosensitive resin layer or the composition constituting the photosensitive resin layer may be present on the surface of the conductive layer.

圖1是表示感光性導電膜的一例的示意剖面圖。圖1所示的感光性導電膜10具備：第一膜(支撐膜)1、設置於第一膜1上的感光層4、以及設置於感光層4上的第二膜(覆蓋膜)5。感光層4具備：設置於支撐膜1上的含有導電性纖維的導電層2、以及設置於導電層2上的感光性樹脂層3。 FIG. 1 is a schematic cross-sectional view showing an example of a photosensitive conductive film. The photosensitive conductive film 10 shown in FIG. 1 includes a first film (support film) 1, a photosensitive layer 4 provided on the first film 1, and a second film (cover film) 5 provided on the photosensitive layer 4. The photosensitive layer 4 includes a conductive layer 2 containing conductive fibers and a photosensitive resin layer 3 provided on the conductive layer 2 on the support film 1.

以下，分別對構成感光性導電膜10的支撐膜1、含有導電性纖維的導電層2、感光性樹脂層3及覆蓋膜5進行詳細地說明。 Hereinafter, the support film 1 constituting the photosensitive conductive film 10, the conductive layer 2 containing the conductive fibers, the photosensitive resin layer 3, and the cover film 5 will be described in detail.

作為支撐膜1，可列舉：聚對苯二甲酸乙二酯膜、聚乙烯膜、聚丙烯膜、聚碳酸酯膜等具有耐熱性及耐溶劑性的聚合物膜。這些中，就透明性、耐熱性等的觀點而言，較佳為聚對苯二甲酸乙二酯膜及聚丙烯膜。 Examples of the support film 1 include a polymer film having heat resistance and solvent resistance such as a polyethylene terephthalate film, a polyethylene film, a polypropylene film, or a polycarbonate film. Among these, from the viewpoints of transparency, heat resistance and the like, a polyethylene terephthalate film and a polypropylene film are preferable.

為了在之後容易自導電層2剝離，上述聚合物膜較佳為經脫模處理者。 In order to easily peel off from the conductive layer 2 afterwards, the above polymer film is preferably a mold release treatment.

本實施方式中，可使支撐膜1較覆蓋膜5更優先地進行剝離。因此，覆蓋膜5與感光性樹脂層3的黏接強度較佳為大於導電層2與支撐膜1的黏接強度。這些聚合物膜較佳為以較覆蓋膜5更容易被剝離的方式實施了厚度的調整、材質的選擇及表面處理者。在調整厚度時，支撐膜1的厚度與覆蓋膜5的厚度之比，較佳為1：1~1：10，更佳為1：1.5~1：5。進而佳為1：2~1： 5。 In the present embodiment, the support film 1 can be peeled off more preferentially than the cover film 5. Therefore, the adhesion strength between the cover film 5 and the photosensitive resin layer 3 is preferably larger than the adhesion strength between the conductive layer 2 and the support film 1. It is preferable that these polymer films are adjusted in thickness, material selection, and surface treatment so that the cover film 5 is more easily peeled off. When the thickness is adjusted, the ratio of the thickness of the support film 1 to the thickness of the cover film 5 is preferably 1:1 to 1:10, more preferably 1:1.5 to 1:5. And then the best is 1:2~1: 5.

支撐膜1的厚度較佳為5μm~100μm，更佳為10μm~50μm，特佳為15μm~25μm。藉由將支撐膜1的厚度設為5μm以上，而可獲得更充分的機械強度。例如在塗敷用以形成導電層2的導電性纖維分散液或用以形成感光性樹脂層3的感光性樹脂組成物的步驟中，難以產生支撐膜的破壞等，且操作性優異。藉由將支撐膜1的厚度設為100μm以下，而可使支撐膜1與導電層2的剝離強度變得適度，而容易剝離。 The thickness of the support film 1 is preferably from 5 μm to 100 μm, more preferably from 10 μm to 50 μm, particularly preferably from 15 μm to 25 μm. By setting the thickness of the support film 1 to 5 μm or more, more sufficient mechanical strength can be obtained. For example, in the step of applying the conductive fiber dispersion for forming the conductive layer 2 or the photosensitive resin composition for forming the photosensitive resin layer 3, it is difficult to cause breakage of the support film or the like, and the workability is excellent. By setting the thickness of the support film 1 to 100 μm or less, the peeling strength of the support film 1 and the conductive layer 2 can be made moderate, and peeling can be easily performed.

作為導電層2所含有的導電性纖維，可列舉：金、銀、鉑等金屬纖維，及碳奈米管(carbon nano-tube)等碳纖維等。這些可單獨使用1種或組合使用2種以上。就導電性的觀點而言，較佳為使用金纖維及/或銀纖維，就可容易地調整所形成的導電圖案的導電性的觀點而言，更佳為使用銀纖維。金纖維及銀纖維可單獨使用1種或組合使用2種以上。 Examples of the conductive fibers contained in the conductive layer 2 include metal fibers such as gold, silver, and platinum, and carbon fibers such as carbon nano-tubes. These may be used alone or in combination of two or more. From the viewpoint of conductivity, it is preferred to use silver fibers and/or silver fibers, and it is more preferable to use silver fibers from the viewpoint of easily adjusting the conductivity of the formed conductive patterns. The gold fiber and the silver fiber may be used alone or in combination of two or more.

上述金屬纖維例如可藉由利用NaBH₄等還原劑將金屬離子還原的方法、或多元醇法而製備。另外，上述碳奈米管可使用尤尼蒂姆(Unidym)公司的Hipco單層碳奈米管等市售品。 The metal fiber can be produced, for example, by a method of reducing a metal ion using a reducing agent such as NaBH ₄ or a polyol method. Further, as the carbon nanotube, a commercially available product such as a Hipco single-layer carbon nanotube of Unidym Co., Ltd. can be used.

導電性纖維的纖維徑較佳為1nm~50nm，更佳為2nm~20nm，特佳為3nm~10nm。另外，導電性纖維的纖維長較佳為1μm~100μm，更佳為2μm~50μm，特佳為3μm~10μm。纖維徑及纖維長可藉由掃描型電子顯微鏡進行測定。 The fiber diameter of the conductive fiber is preferably from 1 nm to 50 nm, more preferably from 2 nm to 20 nm, and particularly preferably from 3 nm to 10 nm. Further, the fiber length of the conductive fiber is preferably from 1 μm to 100 μm, more preferably from 2 μm to 50 μm, particularly preferably from 3 μm to 10 μm. The fiber diameter and fiber length can be measured by a scanning electron microscope.

導電層2的厚度根據使用本發明的感光性導電膜所形成的導電圖案或其用途、所要求的導電性等而不同，較佳為1μm以下，更佳為1nm~0.5μm，特佳為5nm~0.1μm。若導電層2的厚度為1μm以下，則450nm~650nm的波長區域中的透光率高，圖案形成性亦優異，特別適合於透明電極的製作。導電層2的厚度是指藉由掃描型電子顯微鏡照片所測定出的值。 The thickness of the conductive layer 2 varies depending on the conductive pattern formed by using the photosensitive conductive film of the present invention, the use thereof, the required conductivity, and the like, and is preferably 1 μm or less, more preferably 1 nm to 0.5 μm, and particularly preferably 5 nm. ~0.1μm. When the thickness of the conductive layer 2 is 1 μm or less, the light transmittance in the wavelength region of 450 nm to 650 nm is high, and the pattern formation property is also excellent, and it is particularly suitable for the production of a transparent electrode. The thickness of the conductive layer 2 refers to a value measured by a scanning electron micrograph.

導電層2較佳為具有導電性纖維彼此接觸而成的網狀結構。具有此種網狀結構的導電層2可形成於感光性樹脂層3的支撐膜側表面，但若在將支撐膜剝離時所露出的表面的面方向上可獲得導電性，則亦能以包含於感光性樹脂層3的支撐膜側表層的形態而被形成。 The conductive layer 2 is preferably a mesh structure in which conductive fibers are in contact with each other. The conductive layer 2 having such a mesh structure can be formed on the side of the support film side of the photosensitive resin layer 3, but can be contained if the conductivity is obtained in the surface direction of the surface exposed when the support film is peeled off. It is formed in the form of the surface layer of the support film side of the photosensitive resin layer 3.

含有導電性纖維的導電層2例如可藉由將添加有上述導電性纖維、與水及/或有機溶劑、與視需要的界面活性劑等分散穩定劑等的導電性纖維分散液塗敷於支撐膜1上後，進行乾燥而形成。另外，在乾燥後，可對所形成的導電層2進一步加壓。藉由對導電層進行加壓形成，導電性纖維間的接點增加，而可提高導電性。作為此時的線壓，較佳為0.6MPa~2.0MPa，更佳為1.0MPa~1.5MPa。導電層2中，導電性纖維亦可與界面活性劑、分散穩定劑等共存。 The conductive layer 2 containing the conductive fibers can be applied to the support by, for example, a conductive fiber dispersion containing the above-mentioned conductive fibers, a water and/or an organic solvent, and a dispersion stabilizer such as an optional surfactant. After the film 1 is dried, it is formed. Further, after drying, the formed conductive layer 2 can be further pressurized. By pressurizing the conductive layer, the contact between the conductive fibers is increased, and the conductivity can be improved. The linear pressure at this time is preferably 0.6 MPa to 2.0 MPa, and more preferably 1.0 MPa to 1.5 MPa. In the conductive layer 2, the conductive fibers may coexist with a surfactant, a dispersion stabilizer, or the like.

塗敷例如可藉由輥塗法、缺角輪塗佈(comma coat)法、凹版塗佈法、氣刀塗佈法、模塗法、棒塗法、及噴霧塗佈法等公 知的方法進行。另外，乾燥可藉由熱風對流式乾燥機等在30℃~150℃下進行1分鐘~30分鐘左右。 The coating can be carried out, for example, by a roll coating method, a comma coat method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, and a spray coating method. The method of knowing is carried out. Further, the drying may be carried out at 30 ° C to 150 ° C for 1 minute to 30 minutes by a hot air convection dryer or the like.

作為感光性樹脂層3，可列舉：由含有(A)黏合劑聚合物、(B)具有乙烯性不飽和鍵的光聚合性化合物及(C)光聚合起始劑的感光性樹脂組成物所形成者。 The photosensitive resin layer 3 is exemplified by a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. Former.

作為(A)黏合劑聚合物，可列舉：丙烯酸系樹脂、苯乙烯系樹脂、環氧系樹脂、醯胺系樹脂、醯胺環氧系樹脂、醇酸系樹脂、酚系樹脂等。這些可單獨使用或組合使用2種以上。(A)黏合劑聚合物可藉由使聚合性單體進行自由基聚合等而製造。 Examples of the (A) binder polymer include an acrylic resin, a styrene resin, an epoxy resin, a guanamine resin, a guanamine epoxy resin, an alkyd resin, and a phenol resin. These can be used individually or in combination of 2 or more types. (A) The binder polymer can be produced by radical polymerization or the like of a polymerizable monomer.

作為上述聚合性單體，可列舉：苯乙烯、乙烯基甲苯、α-甲基苯乙烯等在α-位或芳香族環上被取代的可聚合的苯乙烯衍生物；二丙酮丙烯醯胺等丙烯醯胺；丙烯腈；乙烯基正丁醚等乙烯基醇的醚類；(甲基)丙烯酸烷基酯、(甲基)丙烯酸芳基酯、(甲基)丙烯酸四氫糠基酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二乙基胺基乙酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、(甲基)丙烯酸、α-溴丙烯酸、α-氯丙烯酸、β-呋喃基丙烯酸、β-苯乙烯基丙烯酸、順丁烯二酸，順丁烯二酸酐，順丁烯二酸單甲酯、順丁烯二酸單乙酯、順丁烯二酸單異丙酯、順丁烯二酸環己酯等順丁烯二酸單酯，反丁烯二酸、肉桂酸、α-氰基肉桂酸、衣康酸，丁烯酸，丙炔酸等。 Examples of the polymerizable monomer include a polymerizable styrene derivative substituted with an α-position or an aromatic ring such as styrene, vinyltoluene or α-methylstyrene; diacetone acrylamide or the like. Ethylene amide; acrylonitrile; ethers of vinyl alcohols such as vinyl n-butyl ether; alkyl (meth)acrylate, aryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, Methyl) dimethylaminoethyl acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, (meth)acrylic acid, α-bromoacrylic acid, α-chloroacrylic acid, β-furylacrylic acid, β-styrylacrylic acid, butene Diacid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, cyclohexyl maleate, etc. Acid monoester, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like.

作為上述(甲基)丙烯酸烷基酯，可列舉：(甲基)丙烯酸 甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸二環戊酯等。 As the above alkyl (meth)acrylate, (meth)acrylic acid is exemplified. Methyl ester, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate , octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, (A) Base) lauryl acrylate, dicyclopentyl (meth) acrylate, and the like.

作為上述(甲基)丙烯酸芳基酯，可列舉(甲基)丙烯酸苄酯等。 The aryl (meth)acrylate may, for example, be benzyl (meth)acrylate.

作為上述聚合性單體，此外可列舉2官能的(甲基)丙烯酸酯等。具體可列舉：乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯。這些可單獨使用或組合使用2種以上。 Further, examples of the polymerizable monomer include a bifunctional (meth)acrylate. Specific examples thereof include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and dipropylene glycol. Di(meth)acrylate, tripropylene glycol di(meth)acrylate. These can be used individually or in combination of 2 or more types.

本實施方式中，(A)黏合劑聚合物較佳為含有源自(a)(甲基)丙烯酸、及(b)(甲基)丙烯酸烷基酯的結構單元的共聚物。 In the present embodiment, the (A) binder polymer is preferably a copolymer containing a structural unit derived from (a) (meth)acrylic acid and (b) alkyl (meth)acrylate.

就使鹼性顯影性更良好的觀點而言，(A)黏合劑聚合物較佳為具有羧基。作為用以獲得此種黏合劑聚合物的具有羧基的聚合性單體，可列舉如上所述的(甲基)丙烯酸等。 The (A) binder polymer preferably has a carboxyl group from the viewpoint of improving alkali developability. As the polymerizable monomer having a carboxyl group for obtaining such a binder polymer, (meth)acrylic acid or the like as described above can be mentioned.

(A)黏合劑聚合物所具有的羧基的比率是作為用以獲得黏合劑聚合物而使用的具有羧基的聚合性單體相對於全部聚合性單體的比例，較佳為10質量%~50質量%，更佳為12質量%~40質量%，特佳為15質量%~30質量%，極佳為15質量%~25質量 %。就鹼性顯影性優異的方面而言，上述比率較佳為10質量%以上，就耐鹼性優異的方面而言，較佳為50質量%以下。 (A) The ratio of the carboxyl group of the binder polymer is a ratio of the polymerizable monomer having a carboxyl group to the total of the polymerizable monomer used to obtain the binder polymer, and preferably 10% by mass to 50% % by mass, more preferably 12% by mass to 40% by mass, particularly preferably 15% by mass to 30% by mass, and excellently 15% by mass to 255% by mass %. The ratio is preferably 10% by mass or more in terms of excellent alkali developability, and is preferably 50% by mass or less from the viewpoint of excellent alkali resistance.

(A)黏合劑聚合物的重量平均分子量較佳為10000~200000，但就解像度的觀點而言，較佳為15000~150000，更佳為30000~150000，尤佳為30000~100000。另外，重量平均分子量的測定條件設為與本申請案說明書的實施例相同的測定條件。 The weight average molecular weight of the (A) binder polymer is preferably from 10,000 to 200,000, but from the viewpoint of resolution, it is preferably from 15,000 to 150,000, more preferably from 30,000 to 150,000, and particularly preferably from 30,000 to 100,000. In addition, the measurement conditions of the weight average molecular weight are the same measurement conditions as the Example of this specification.

作為(B)成分的光聚合性化合物，可使用具有乙烯性不飽和鍵的光聚合性化合物。 As the photopolymerizable compound of the component (B), a photopolymerizable compound having an ethylenically unsaturated bond can be used.

作為具有乙烯性不飽和鍵的光聚合性化合物，可列舉：一官能乙烯系單體、二官能乙烯系單體、具有至少3個可聚合的乙烯性不飽和鍵的多官能乙烯系單體等。 Examples of the photopolymerizable compound having an ethylenically unsaturated bond include a monofunctional vinyl monomer, a difunctional vinyl monomer, and a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated bonds. .

作為上述一官能乙烯系單體，例如可列舉：作為上述(A)成分的較佳例即共聚物的合成所用的單體而例示的(甲基)丙烯酸、(甲基)丙烯酸烷基酯及可與這些共聚合的單體。 Examples of the monofunctional vinyl monomer include (meth)acrylic acid and alkyl (meth)acrylate which are exemplified as monomers used for the synthesis of the copolymer which is a preferred example of the component (A). A monomer that can be copolymerized with these.

作為上述二官能乙烯系單體，可列舉：聚乙二醇二(甲基)丙烯酸酯(乙氧基的數量為2~14者)、三羥甲基丙烷二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯(伸丙基的數量為2~14者)；雙酚A聚氧乙烯二(甲基)丙烯酸酯(2,2-雙(4-(甲基)丙烯醯氧基聚乙氧基苯基)丙烷)、雙酚A二縮水甘油醚二(甲基)丙烯酸酯；多元酸(鄰苯二甲酸酐等)與具有羥基及乙烯性不飽和鍵的物質(丙烯酸β-羥基乙酯、甲基丙烯酸β-羥基乙酯等)的酯化物 等。作為上述雙酚A聚氧乙烯二甲基丙烯酸酯，可列舉：雙酚A二氧乙烯二丙烯酸酯、雙酚A二氧乙烯二甲基丙烯酸酯、雙酚A三氧乙烯二丙烯酸酯、雙酚A三氧乙烯二甲基丙烯酸酯、雙酚A五氧乙烯二丙烯酸酯、雙酚A五氧乙烯二甲基丙烯酸酯、雙酚A十氧乙烯二丙烯酸酯、雙酚A十氧乙烯二甲基丙烯酸酯等。 Examples of the difunctional vinyl monomer include polyethylene glycol di(meth)acrylate (the amount of the ethoxy group is 2 to 14), trimethylolpropane di(meth)acrylate, and poly Propylene glycol di(meth) acrylate (the number of propyl groups is 2 to 14); bisphenol A polyoxyethylene di(meth) acrylate (2,2-bis(4-(methyl) propylene oxime) Polyethoxyphenyl)propane), bisphenol A diglycidyl ether di(meth)acrylate; polybasic acid (phthalic anhydride, etc.) and a substance having a hydroxyl group and an ethylenically unsaturated bond (Acrylic acid β Esterified product of -hydroxyethyl ester, β-hydroxyethyl methacrylate, etc. Wait. Examples of the bisphenol A polyoxyethylene dimethacrylate include bisphenol A dioxyethylene diacrylate, bisphenol A dioxyethylene dimethacrylate, bisphenol A trioxyethylene diacrylate, and double Phenol A trioxyethylene dimethacrylate, bisphenol A pentaoxyethylene diacrylate, bisphenol A pentaoxyethylene dimethacrylate, bisphenol A decaoxyethylene diacrylate, bisphenol A decaoxyethylene two Methacrylate and the like.

作為上述具有至少3個可聚合的乙烯性不飽和鍵的多官能乙烯系單體，可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等多元醇與α,β-不飽和羧酸反應而得的化合物；三羥甲基丙烷三縮水甘油醚三丙烯酸酯等含有縮水甘油基的化合物與α,β-不飽和羧酸加成而得的化合物等。 Examples of the polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated bonds include trimethylolpropane tri(meth)acrylate and tetramethylol methane tri(meth)acrylate. a compound obtained by reacting a polyhydric alcohol such as tetramethylol methane tetra(meth)acrylate, dipentaerythritol penta (meth) acrylate or dipentaerythritol hexa(meth) acrylate with an α,β-unsaturated carboxylic acid a compound obtained by adding a glycidyl group-containing compound such as trimethylolpropane triglycidyl ether triacrylate to an α,β-unsaturated carboxylic acid.

作為(C)光聚合起始劑，可列舉：二苯甲酮、N,N,N',N'-四甲基-4,4'-二胺基二苯甲酮(米其勒酮)、N,N,N',N'-四乙基-4,4'-二胺基二苯甲酮、4-甲氧基-4'-二甲基胺基二苯甲酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮-1,2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基-丙酮-1等芳香族酮；2-乙基蒽醌、菲醌、2-第三丁基蒽醌、八甲基蒽醌、1,2-苯并蒽醌、2,3-苯并蒽醌、2-苯基蒽醌、2,3-二苯基蒽醌、1-氯蒽醌、2-甲基蒽醌、1,4-萘醌、9,10-菲醌、2-甲基-1,4-萘醌、2,3-二甲基蒽醌等醌類；安息香甲醚、安息香乙醚、安息香苯醚等安息香醚化合物；安息香、甲基安息香、乙基安息香等安 息香化合物；1,2-辛烷二酮,1-[4-(苯硫基)苯基-,2-(O-苯甲醯基肟)]、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)等肟酯化合物；2,4,6-三甲基苯甲醯基-二苯基-氧化膦等氧化膦化合物；苯偶醯二甲基縮酮等苯偶醯衍生物；2-(鄰氯苯基)-4,5-二苯基咪唑二聚物、2-(鄰氯苯基)-4,5-二(甲氧基苯基)咪唑二聚物、2-(鄰氟苯基)-4,5-二苯基咪唑二聚物、2-(鄰甲氧基苯基)-4,5-二苯基咪唑二聚物、2-(對甲氧基苯基)-4,5-二苯基咪唑二聚物等2,4,5-三芳基咪唑二聚物；9-苯基吖啶、1,7-雙(9,9'-吖啶基)庚烷等吖啶衍生物；N-苯基甘胺酸、N-苯基甘胺酸衍生物、香豆素系化合物、噁唑系化合物等。另外，2個2,4,5-三芳基咪唑的芳基的取代基可形成相同且對稱的化合物，亦可形成相異而非對稱的化合物。另外，亦可如二乙基噻噸酮與二甲基胺基苯甲酸的組合般，將噻噸酮系化合物與三級胺化合物組合。 As the (C) photopolymerization initiator, benzophenone, N, N, N', N'-tetramethyl-4,4'-diaminobenzophenone (michlerone) can be mentioned. ,N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl Benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholine Aromatic ketones such as ketone-acetone-1; 2-ethyl fluorene, phenanthrenequinone, 2-tert-butyl fluorene, octamethyl hydrazine, 1,2-benzopyrene, 2,3-benzo Bismuth, 2-phenylindole, 2,3-diphenylanthracene, 1-chloroindole, 2-methylindole, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl Anthraquinones such as 1,4-naphthoquinone and 2,3-dimethylhydrazine; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin, methyl benzoin, ethyl benzoin, etc. Aroma compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzylidenehydrazide)], ethyl ketone, 1-[9-ethyl An oxime ester compound such as -6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethenylhydrazine); 2,4,6-trimethylbenzene a phosphine oxide compound such as formazan-diphenyl-phosphine oxide; a benzoin derivative such as benzoin dimethyl ketal; and a 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer. , 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, etc. 2,4,5- Triaryl imidazole dimer; acridine derivative such as 9-phenyl acridine, 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine, N-phenylglycine An amine derivative, a coumarin compound, an oxazole compound, and the like. Further, the substituents of the aryl groups of the two 2,4,5-triarylimidazoles may form the same and symmetrical compounds, and may also form compounds which are different from each other in symmetry. Further, a thioxanthone-based compound may be combined with a tertiary amine compound as in the combination of diethylthioxanthone and dimethylaminobenzoic acid.

這些中，就所形成的感光性樹脂層的透明性、及製成薄膜時的圖案形成能力而言，較佳為肟酯化合物或氧化膦化合物。 Among these, an oxime ester compound or a phosphine oxide compound is preferable in terms of the transparency of the photosensitive resin layer to be formed and the pattern forming ability at the time of film formation.

相對於(A)黏合劑聚合物及(B)具有乙烯性不飽和鍵的光聚合性化合物的總量100質量份，上述(A)黏合劑聚合物的調配量較佳為40質量份~80質量份，更佳為50質量份~70質量份。藉由將該調配量設為40質量份以上，而塗膜性(塗敷性)優異，並可進一步抑制樹脂自感光性導電膜(感光性元件)的端部滲出的現象(亦稱為邊緣融合(edge fusion))。另外，藉由將該調 配量設為80質量份以下，而可提高感度，且可獲得充分的機械強度。 The amount of the (A) binder polymer is preferably 40 parts by mass to 80 parts by mass based on 100 parts by mass of the total of the (A) binder polymer and (B) the photopolymerizable compound having an ethylenically unsaturated bond. The mass part is more preferably 50 parts by mass to 70 parts by mass. When the amount is 40 parts by mass or more, the coating property (coating property) is excellent, and the phenomenon that the resin oozes from the end portion of the photosensitive conductive film (photosensitive element) can be further suppressed (also referred to as edge). Edge fusion). In addition, by adjusting the tone When the amount is set to 80 parts by mass or less, the sensitivity can be improved, and sufficient mechanical strength can be obtained.

相對於(A)黏合劑聚合物及(B)具有乙烯性不飽和鍵的光聚合性化合物的總量100質量份，上述(B)具有乙烯性不飽和鍵的光聚合性化合物的調配量較佳為20質量份~60質量份，更佳為30質量份~50質量份。藉由將該調配量設為20質量份以上，而可提高感度，並可獲得充分的機械強度。另外，藉由將該調配量設為60質量份以下，而塗膜性(塗敷性)優異，並可進一步抑制邊緣融合。 The amount of the photopolymerizable compound having the ethylenically unsaturated bond (B) is more than 100 parts by mass based on the total amount of the (A) binder polymer and (B) the photopolymerizable compound having an ethylenically unsaturated bond. Preferably, it is 20 parts by mass to 60 parts by mass, more preferably 30 parts by mass to 50 parts by mass. By setting the blending amount to 20 parts by mass or more, the sensitivity can be improved, and sufficient mechanical strength can be obtained. In addition, when the blending amount is 60 parts by mass or less, the coating property (coating property) is excellent, and edge fusion can be further suppressed.

相對於(A)黏合劑聚合物及(B)具有乙烯性不飽和鍵的光聚合性化合物的總量100質量份，上述(C)光聚合起始劑的調配量較佳為0.1質量份~20質量份，更佳為0.2質量份~10質量份。藉由將該調配量設為0.1質量份以上，而可提高感度。藉由將該調配量設為20質量份以下，而可更均勻地進行由曝光引起的感光性樹脂層的硬化。 The amount of the photopolymerization initiator (C) is preferably 0.1 part by mass based on 100 parts by mass of the total of the (A) binder polymer and (B) the photopolymerizable compound having an ethylenically unsaturated bond. 20 parts by mass, more preferably 0.2 parts by mass to 10 parts by mass. By setting the blending amount to 0.1 part by mass or more, the sensitivity can be improved. By setting the blending amount to 20 parts by mass or less, the curing of the photosensitive resin layer by exposure can be performed more uniformly.

本發明中的感光性樹脂組成物中，根據需要可添加：孔雀綠(malachite green)等染料、三溴甲基苯基碸、隱色結晶紫等光發色劑、熱發色防止劑、對甲苯磺醯胺等塑化劑、顏料、填充劑、消泡劑、阻燃劑、穩定劑、密接性賦予劑、勻平劑、剝離促進劑、抗氧化劑、香料、成像劑、熱交聯劑等。相對於(A)黏合劑聚合物及(B)光聚合性化合物的總量100質量份，這些添加劑 的添加量分別可含有0.01質量份~20質量份左右。這些可單獨使用或組合使用2種類以上。 In the photosensitive resin composition of the present invention, if necessary, a dye such as malachite green, a photochromic agent such as tribromomethylphenylphosphonium or leuco crystal violet, or a thermochromic preventing agent may be added. Plasticizers such as toluene sulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion imparting agents, leveling agents, peeling accelerators, antioxidants, perfumes, imaging agents, thermal crosslinking agents Wait. These additives are 100 parts by mass based on the total amount of the (A) binder polymer and (B) photopolymerizable compound The amount of addition may be from 0.01 part by mass to 20 parts by mass, respectively. These can be used individually or in combination of 2 or more types.

感光性樹脂層3可藉由在形成於支撐膜1上的導電層2上，視需要塗敷溶解於甲醇、乙醇、丙酮、甲基乙基酮、甲基溶纖劑、乙基溶纖劑、甲苯、N,N-二甲基甲醯胺、丙二醇單甲醚等溶劑或這些的混合溶劑且固體成分為10質量%~60質量%左右的感光性樹脂組成物的溶液後，進行乾燥而形成。但此時，為了防止後續步驟中的有機溶劑的擴散，乾燥後的感光性樹脂層中的殘存有機溶劑量較佳為2質量%以下。 The photosensitive resin layer 3 can be dissolved and dissolved on methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, and ethyl cellosolve as needed on the conductive layer 2 formed on the support film 1. a solvent such as toluene, N,N-dimethylformamide or propylene glycol monomethyl ether or a mixed solvent of these, and a solid content of a solution of a photosensitive resin composition of about 10% by mass to 60% by mass, followed by drying form. In this case, in order to prevent the diffusion of the organic solvent in the subsequent step, the amount of the residual organic solvent in the photosensitive resin layer after drying is preferably 2% by mass or less.

塗敷可藉由輥塗法、缺角輪塗佈法、凹版塗佈法、氣刀塗佈法、模塗法、棒塗法、噴霧塗佈法等公知的方法進行。塗敷後，用以除去有機溶劑等的乾燥，可藉由熱風對流式乾燥機等在70℃~150℃下進行5分鐘~30分鐘左右。 The coating can be carried out by a known method such as a roll coating method, a notch wheel coating method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, or a spray coating method. After the application, the drying for removing the organic solvent or the like can be carried out at 70 ° C to 150 ° C for 5 minutes to 30 minutes by a hot air convection dryer or the like.

感光性樹脂層3的厚度根據用途而不同，較佳為乾燥後的厚度為0.05μm~50μm，更佳為0.05μm~15μm，尤佳為0.1μm~10μm，特佳為0.1μm~8μm，極佳為0.1μm~5μm。藉由將該厚度設為0.05μm以上，而容易形成藉由塗敷所得的感光性樹脂層3。另外，藉由將該厚度設為50μm以下，而透光性良好，可獲得充分的感度，且可使轉印後的感光層的光硬化性優異。 The thickness of the photosensitive resin layer 3 varies depending on the application, and is preferably 0.05 μm to 50 μm after drying, more preferably 0.05 μm to 15 μm, still more preferably 0.1 μm to 10 μm, particularly preferably 0.1 μm to 8 μm. Good is 0.1μm~5μm. By setting the thickness to 0.05 μm or more, the photosensitive resin layer 3 obtained by coating is easily formed. In addition, by setting the thickness to 50 μm or less, the light transmittance is good, and sufficient sensitivity can be obtained, and the photosensitive layer after transfer can be excellent in photocurability.

作為覆蓋膜5，可列舉：作為可用作支撐膜1的聚合物膜而例示者。此時，支撐膜1較佳為以較覆蓋膜5更優先地被剝 離的方式，藉由支撐膜及覆蓋膜的膜厚控制、表面處理等而受到調整。 The cover film 5 is exemplified as a polymer film which can be used as the support film 1. At this time, the support film 1 is preferably peeled off more preferentially than the cover film 5. The manner of separation is adjusted by film thickness control of the support film and the cover film, surface treatment, and the like.

覆蓋膜5的厚度較佳為10μm~200μm，更佳為15μm~150μm，特佳為15μm~100μm。 The thickness of the cover film 5 is preferably from 10 μm to 200 μm, more preferably from 15 μm to 150 μm, particularly preferably from 15 μm to 100 μm.

就可使感度及解像度良好的觀點而言，覆蓋膜5的霧度值較佳為0.01%~5.0%，更佳為0.01%~3.0%，尤佳為0.01%~2.0%，特佳為0.01%~1.0%。另外，霧度值可依據JIS K 7105而測定，可藉由NDH-1001DP(日本電色工業股份有限公司製造、商品名)等市售的濁度計等而測定。 The haze value of the cover film 5 is preferably from 0.01% to 5.0%, more preferably from 0.01% to 3.0%, even more preferably from 0.01% to 2.0%, particularly preferably from the viewpoint of good sensitivity and resolution. %~1.0%. In addition, the haze value can be measured in accordance with JIS K 7105, and can be measured by a commercially available turbidity meter or the like such as NDH-1001DP (manufactured by Nippon Denshoku Industries Co., Ltd., trade name).

關於本實施方式的感光性導電膜，雖然記載了在支撐膜上依序塗佈、形成導電層、感光性樹脂層的製造方法，但感光性導電膜的製造方法並不限定於此。圖2是表示感光性導電膜的製造方法的一例的示意剖面圖。圖2所示的製造方法的特徵在於：在第一膜(支撐膜)1上形成導電層2，另外在第二膜(覆蓋膜)5上形成感光性樹脂層3。將如上述般進行而獲得的2片膜，以使導電層2與感光性樹脂層3積層的方式，藉由滾筒(roller)50進行層壓，藉此製造感光性導電膜。根據該製造方法，由於個別形成導電層與感光性樹脂層，因此與重複塗佈溶液的製造方法相比，各層內的結構(例如導電層的網狀結構)的控制變得更容易。較佳為將此時的形成有導電層的膜及/或形成有感光性樹脂層的膜加熱至60℃~130℃而進行層壓，壓接壓力較佳為設為0.2MPa~ 0.8MPa左右。 In the photosensitive conductive film of the present embodiment, a method of manufacturing a conductive layer and a photosensitive resin layer on the support film in this order is described. However, the method for producing the photosensitive conductive film is not limited thereto. 2 is a schematic cross-sectional view showing an example of a method of producing a photosensitive conductive film. The manufacturing method shown in FIG. 2 is characterized in that a conductive layer 2 is formed on the first film (support film) 1, and a photosensitive resin layer 3 is formed on the second film (cover film) 5. The two films obtained as described above were laminated by a roller 50 so that the conductive layer 2 and the photosensitive resin layer 3 were laminated, thereby producing a photosensitive conductive film. According to this manufacturing method, since the conductive layer and the photosensitive resin layer are separately formed, it is easier to control the structure (for example, the mesh structure of the conductive layer) in each layer than the method of manufacturing the repeated coating solution. Preferably, the film on which the conductive layer is formed and/or the film on which the photosensitive resin layer is formed are heated to 60 to 130 ° C for lamination, and the pressure of the pressure is preferably set to 0.2 MPa. About 0.8MPa.

本實施方式中，上述導電層2及上述感光性樹脂層3的積層體(感光層4)較佳為450nm~650nm的波長區域中的最小透光率為80%以上，更佳為85%以上。在感光層4滿足此種條件時，容易實現顯示面板等中的高亮度化。另外，將構成感光層4的上述導電層2及上述感光性樹脂層3這兩層的合計膜厚設為1μm~10μm時，450nm~650nm的波長區域中的最小透光率較佳為80%以上，更佳為85%以上。在導電層及感光性樹脂層滿足此種條件時，容易實現顯示面板等中的高亮度化。 In the present embodiment, the laminated body (photosensitive layer 4) of the conductive layer 2 and the photosensitive resin layer 3 preferably has a minimum light transmittance of 80% or more, more preferably 85% or more in a wavelength region of 450 nm to 650 nm. . When the photosensitive layer 4 satisfies such conditions, it is easy to achieve high luminance in a display panel or the like. When the total thickness of the two layers of the conductive layer 2 and the photosensitive resin layer 3 constituting the photosensitive layer 4 is 1 μm to 10 μm, the minimum light transmittance in the wavelength region of 450 nm to 650 nm is preferably 80%. More preferably, it is 85% or more. When the conductive layer and the photosensitive resin layer satisfy such conditions, it is easy to achieve high luminance in a display panel or the like.

感光性導電膜在支撐膜或覆蓋膜上、或兩膜上可進一步具有黏接層、氣體阻隔層等層。 The photosensitive conductive film may further have a layer such as an adhesive layer or a gas barrier layer on the support film or the cover film or on both films.

感光性導電膜例如可直接以平板狀的形態、或以捲繞在圓筒狀等的捲芯的卷(roll)狀的形態儲藏。 The photosensitive conductive film can be stored, for example, in a flat plate shape or in a roll shape wound around a cylindrical core.

作為捲芯，只要是先前所使用的捲芯，則並無特別限定，例如可列舉：聚乙烯樹脂、聚丙烯樹脂、聚苯乙烯樹脂、聚氯乙烯樹脂、ABS(Acrylonitrile Butadiene Styrene)樹脂(丙烯腈-丁二烯-苯乙烯共聚物)等塑膠。另外，就保護端面的觀點而言，較佳為在捲繞成卷狀的感光性導電膜的端面設置端面分隔件，此外，就耐邊緣融合的觀點而言，較佳為設置防濕端面分隔件。另外，在捆包感光性導電膜時，較佳為藉由包裹於透濕性小的黑色片材(black sheet)中而包裝。 The core is not particularly limited as long as it is a previously used core, and examples thereof include a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, and an ABS (Acrylonitrile Butadiene Styrene) resin (propylene). Plastics such as nitrile-butadiene-styrene copolymer. Further, from the viewpoint of protecting the end face, it is preferable to provide an end face spacer on the end surface of the photosensitive conductive film wound in a roll shape, and further, it is preferable to provide a moisture-proof end face separation from the viewpoint of edge fusion resistance. Pieces. Further, when the photosensitive conductive film is bundled, it is preferably packaged by being wrapped in a black sheet having a small moisture permeability.

〈導電圖案的形成方法〉 <Method of Forming Conductive Pattern>

圖3(a)~圖3(d)是用以說明本實施方式的導電圖案的形成方法的示意剖面圖。本實施方式的方法包括：將上述的感光性導電膜10的支撐膜1剝離，以導電層2與基材20密接的方式進行層壓的層壓步驟(圖3(a)及圖3(b))；藉由將基材上的感光層進行曝光及顯影而形成導電圖案的圖案化步驟(圖3(c)及圖3(d))。圖案化步驟包括：對具有覆蓋膜5的感光層4的規定部分照射光化射線的曝光步驟(圖3(c))，以及然後將覆蓋膜5剝離而對感光層4進行顯影的顯影步驟(圖3(d))。 3(a) to 3(d) are schematic cross-sectional views for explaining a method of forming a conductive pattern according to the embodiment. The method of the present embodiment includes a step of laminating the support film 1 of the photosensitive conductive film 10 described above and laminating the conductive layer 2 in close contact with the substrate 20 (Fig. 3(a) and Fig. 3(b) The patterning step of forming a conductive pattern by exposing and developing the photosensitive layer on the substrate (Fig. 3(c) and Fig. 3(d)). The patterning step includes an exposure step of irradiating a prescribed portion of the photosensitive layer 4 having the cover film 5 with an actinic ray (Fig. 3(c)), and then a developing step of peeling off the cover film 5 to develop the photosensitive layer 4 ( Figure 3 (d)).

作為基材20，可使用玻璃基板、聚碳酸酯等塑膠基板等基板。基材20的厚度可根據使用目的而適當選擇，亦可使用膜狀基材。作為膜狀基材，例如可列舉：聚對苯二甲酸乙二酯膜、聚碳酸酯膜、環烯烴聚合物膜。作為基材20，可使用已藉由ITO等而形成了透明電極等的基板。基材20較佳為450nm~650nm的波長區域中的最小透光率為80%以上者。在基材20滿足此種條件時，容易實現顯示面板等中的高亮度化。 As the substrate 20, a substrate such as a glass substrate or a plastic substrate such as polycarbonate can be used. The thickness of the substrate 20 can be appropriately selected depending on the purpose of use, and a film-form substrate can also be used. Examples of the film-form substrate include a polyethylene terephthalate film, a polycarbonate film, and a cycloolefin polymer film. As the substrate 20, a substrate on which a transparent electrode or the like has been formed by ITO or the like can be used. The substrate 20 preferably has a minimum light transmittance of 80% or more in a wavelength region of 450 nm to 650 nm. When the substrate 20 satisfies such conditions, it is easy to achieve high luminance in a display panel or the like.

層壓步驟例如藉由以下方法進行：將感光性導電膜10的支撐膜1除去後，一邊加熱一邊將導電層2側壓接於玻璃基板等基材20而進行積層。另外，就密接性及追隨性的觀點而言，該作業較佳為在減壓下進行積層。感光性導電膜10的積層較佳為將導電層2以及感光性樹脂層3及/或基材20加熱至70℃~130℃， 這些條件並無特別限制。另外，若如上述般將導電層2及感光性樹脂層3加熱至70℃~130℃，則無須預先對基材20進行預熱處理，為了進一步提高積層性，亦可進行基材20的預熱處理。 The lamination step is carried out, for example, by removing the support film 1 of the photosensitive conductive film 10, and then laminating the conductive layer 2 side to the substrate 20 such as a glass substrate while heating, and laminating. Further, from the viewpoint of adhesion and followability, it is preferable to carry out the lamination under reduced pressure. The laminate of the photosensitive conductive film 10 is preferably such that the conductive layer 2 and the photosensitive resin layer 3 and/or the substrate 20 are heated to 70 ° C to 130 ° C. These conditions are not particularly limited. Further, when the conductive layer 2 and the photosensitive resin layer 3 are heated to 70° C. to 130° C. as described above, it is not necessary to preheat the substrate 20 in advance, and in order to further improve the buildup property, the substrate 20 may be preliminarily prepared. Heat treatment.

在上述感光性導電膜10的積層中，壓接壓力較佳為0.1MPa~1.0MPa左右(1kgf/cm²~10kgf/cm²左右)，更佳為0.2MPa~0.8MPa。 In the laminate of the photosensitive conductive film 10, the pressure of the pressure is preferably about 0.1 MPa to 1.0 MPa (about 1 kgf/cm ² to 10 kgf/cm ² ), more preferably 0.2 MPa to 0.8 MPa.

在曝光步驟中，藉由照射光化射線而將感光性樹脂層硬化，藉由該硬化物而將導電層固定，藉此在基材上形成導電圖案。作為曝光步驟中的曝光方法，可列舉：通過被稱為原圖(artwork)的負型或正型遮罩圖案而圖像狀地照射光化射線L的方法(遮罩曝光法)。作為光化射線的光源，可使用公知的光源、例如碳弧燈、水銀蒸氣電弧燈、超高壓水銀燈、高壓水銀燈、氙燈等有效地放射紫外線、可見光等者。另外，可使用Ar離子雷射、半導體雷射等有效地放射紫外線、可見光等者。而且，亦可使用照片用散光(flood)燈泡、太陽燈等有效地放射可見光者。另外，亦可採用藉由使用雷射曝光法等的直接成像法(direct imaging method)而圖像狀地照射光化射線的方法。 In the exposure step, the photosensitive resin layer is cured by irradiating the actinic ray, and the conductive layer is fixed by the cured product, thereby forming a conductive pattern on the substrate. The exposure method in the exposure step includes a method of irradiating the actinic ray L in an image form by a negative or positive mask pattern called an artwork (mask exposure method). As the light source of the actinic ray, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp or the like can be used to efficiently emit ultraviolet rays, visible light or the like. Further, it is possible to effectively emit ultraviolet rays, visible light, or the like using an Ar ion laser or a semiconductor laser. Moreover, it is also possible to use a photo with a flood light bulb, a sun light, or the like to effectively emit visible light. Further, a method of irradiating the actinic rays imagewise by using a direct imaging method such as a laser exposure method may be employed.

此時的光化射線L的曝光量根據所使用的裝置、感光性樹脂組成物的組成等而不同，較佳為5mJ/cm²~1000mJ/cm²，更佳為10mJ/cm²~200mJ/cm²。就光硬化性優異的方面而言，較佳為10mJ/cm²以上，就解像性的方面而言，較佳為200mJ/cm²以 下。藉由將曝光量設為1000mJ/cm²以下，而可抑制感光層的變色。 The exposure amount of the actinic ray L at this time varies depending on the apparatus to be used, the composition of the photosensitive resin composition, and the like, and is preferably ⁵ mJ/cm ² to 1000 mJ/cm ² , more preferably 10 mJ/cm ² to 200 mJ/ Cm ² . In terms of excellent photocurability, it is preferably 10 mJ/cm ² or more, and in terms of resolution, it is preferably 200 mJ/cm ² or less. By setting the exposure amount to 1000 mJ/cm ² or less, discoloration of the photosensitive layer can be suppressed.

在感光性樹脂層上的覆蓋膜5對光化射線L為透明時，可通過覆蓋膜5照射光化射線L，在覆蓋膜5為遮光性時，在將覆蓋膜5除去後對感光性樹脂層照射光化射線。 When the cover film 5 on the photosensitive resin layer is transparent to the actinic ray L, the actinic ray can be irradiated by the cover film 5, and when the cover film 5 is light-shielding, the cover film 5 is removed and the photosensitive resin is removed. The layer illuminates the actinic ray.

另外，如上所述般，本發明所用的感光性導電膜只要以使支撐膜比覆蓋膜先剝離的方式，藉由支撐膜1及覆蓋膜5的膜厚、材質等的選擇、表面處理等，調節兩膜的黏接強度即可。 In addition, as described above, the photosensitive conductive film used in the present invention is selected such that the thickness and material of the support film 1 and the cover film 5 are selected, surface treatment, etc., so that the support film is peeled off from the cover film. Adjust the bonding strength of the two films.

另外，在基材20對光化射線L為透明時，可自基材側通過基材照射光化射線，但就解像度的方面而言，較佳為自感光性樹脂層側對感光性樹脂層照射光化射線。 In addition, when the base material 20 is transparent to the actinic ray L, the actinic ray may be irradiated from the substrate side through the substrate, but in terms of resolution, the photosensitive resin layer is preferably applied from the photosensitive resin layer side. Irradiating actinic rays.

根據本實施方式的導電圖案的形成方法，藉由將另外製作的感光性導電膜10層壓於基材20而設置感光層4，可更簡便地在基材20上形成感光層4，並可實現生產性的提高。另外，根據本發明的導電圖案的形成方法，可在玻璃基板、塑膠基板等基材上容易地形成透明的導電圖案。 According to the method of forming a conductive pattern of the present embodiment, by providing the photosensitive layer 4 by laminating the separately prepared photosensitive conductive film 10 on the substrate 20, the photosensitive layer 4 can be formed on the substrate 20 more easily, and Achieve productivity improvement. Further, according to the method for forming a conductive pattern of the present invention, a transparent conductive pattern can be easily formed on a substrate such as a glass substrate or a plastic substrate.

在顯影步驟(形成導電圖案的步驟)中，將感光層的未曝光部(曝光部以外的部分)除去。具體而言，在感光層上存在透明的覆蓋膜5時，首先將覆蓋膜5除去，然後藉由濕式顯影將感光層的未曝光部除去。藉此，在具有規定圖案的樹脂硬化層3b下殘留含有導電性纖維的導電層2，並形成導電圖案2a。如此，如圖3(d)所示般，可獲得具有導電圖案的導電圖案基板40。 In the developing step (step of forming a conductive pattern), the unexposed portion (portion other than the exposed portion) of the photosensitive layer is removed. Specifically, when the transparent cover film 5 is present on the photosensitive layer, the cover film 5 is first removed, and then the unexposed portion of the photosensitive layer is removed by wet development. Thereby, the conductive layer 2 containing the conductive fibers remains under the resin-hardened layer 3b having a predetermined pattern, and the conductive pattern 2a is formed. Thus, as shown in FIG. 3(d), the conductive pattern substrate 40 having the conductive pattern can be obtained.

濕式顯影是使用鹼性水溶液、水系顯影液、有機溶劑系顯影液等與感光性樹脂對應的顯影液，藉由噴霧、揺動浸漬、刷洗、刮擦(scrapping)等公知的方法而進行。 The wet development is carried out by a known method such as spraying, immersion immersion, brushing, or scraping, using a developing solution corresponding to a photosensitive resin such as an alkaline aqueous solution, an aqueous developing solution, or an organic solvent developing solution.

作為顯影液，可使用鹼性水溶液等安全、且穩定、操作性良好者。作為上述鹼性水溶液的鹼，可使用：鋰、鈉、鉀等鹼金屬的氫氧化物(氫氧化鹼)；鋰、鈉、鉀、銨等的碳酸鹽或重碳酸鹽(碳酸鹼)；鋰、鈉、鉀、銨等的硼酸鹽或聚硼酸鹽；磷酸鉀、磷酸鈉等鹼金屬磷酸鹽；焦磷酸鈉、焦磷酸鉀等鹼金屬焦磷酸鹽等。 As the developer, an alkaline aqueous solution or the like can be used, which is safe, stable, and excellent in workability. As the base of the alkaline aqueous solution, a hydroxide of an alkali metal such as lithium, sodium or potassium (aluminum hydroxide); a carbonate of a lithium, sodium, potassium or ammonium carbonate or a bicarbonate (carbonate); lithium can be used. , borate or polyborate such as sodium, potassium or ammonium; alkali metal phosphate such as potassium phosphate or sodium phosphate; alkali metal pyrophosphate such as sodium pyrophosphate or potassium pyrophosphate.

作為顯影所用的鹼性水溶液，較佳為0.1質量%~5質量%碳酸鈉水溶液、0.1質量%~5質量%碳酸鉀水溶液、0.1質量%~5質量%氫氧化鈉水溶液、0.1質量%~5質量%四硼酸鈉水溶液等。另外，顯影所用的鹼性水溶液的pH值較佳為設為9~11的範圍，其溫度依據感光性樹脂層的顯影性而被調節。另外，鹼性水溶液中亦可混入表面活性劑、消泡劑、用以促進顯影的少量有機溶劑等。 The alkaline aqueous solution used for development is preferably 0.1% by mass to 5% by mass of sodium carbonate aqueous solution, 0.1% by mass to 5% by mass of potassium carbonate aqueous solution, 0.1% by mass to 5% by mass of sodium hydroxide aqueous solution, and 0.1% by mass to 55%. A mass% sodium tetraborate aqueous solution or the like. Further, the pH of the alkaline aqueous solution used for development is preferably in the range of 9 to 11, and the temperature thereof is adjusted depending on the developability of the photosensitive resin layer. Further, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution.

另外，可使用包含水或鹼性水溶液與1種以上有機溶劑的水系顯影液。此處，作為鹼性水溶液所含的鹼，除了上述鹼以外，可列舉：硼砂、偏矽酸鈉、氫氧化四甲基銨、乙醇胺、乙二胺、二乙三胺、2-胺基-2-羥基甲基-1、3-丙二醇、1,3-二胺基丙醇-2、嗎福啉(morpholine)等。 Further, an aqueous developing solution containing water or an aqueous alkaline solution and one or more organic solvents can be used. Here, examples of the base contained in the alkaline aqueous solution include borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, and 2-amino group. 2-hydroxymethyl-1, 3-propanediol, 1,3-diaminopropanol-2, morpholine, and the like.

作為有機溶劑，例如可列舉：甲基乙基酮、丙酮、乙酸乙酯、具有碳數為1~4的烷氧基的烷氧基乙醇、乙醇、異丙醇、丁醇、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚。這些可單獨使用1種或組合使用2種以上。 Examples of the organic solvent include methyl ethyl ketone, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, and diethylene glycol. Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether. These may be used alone or in combination of two or more.

水系顯影液較佳為將有機溶劑的濃度設為2質量%~90質量%，其溫度可依據顯影性進行調整。而且，水系顯影液的pH值較佳為在感光性樹脂層可充分顯影的範圍內儘可能減小，較佳為設為pH值為8~12，更佳為設為pH值為9~10。另外，水系顯影液中亦可添加少量界面活性劑、消泡劑等。 The aqueous developing solution preferably has a concentration of the organic solvent of 2% by mass to 90% by mass, and the temperature thereof can be adjusted depending on the developability. Further, the pH of the aqueous developing solution is preferably as small as possible within a range in which the photosensitive resin layer can be sufficiently developed, and preferably has a pH of 8 to 12, more preferably a pH of 9 to 10. . Further, a small amount of a surfactant, an antifoaming agent, or the like may be added to the aqueous developing solution.

作為有機溶劑系顯影液，例如可列舉：1,1,1-三氯乙烷、N-甲基吡咯烷酮、N,N-二甲基甲醯胺、環己酮、甲基異丁基酮、γ-丁內酯等。這些有機溶劑為了防止起火，較佳為在1質量%~20質量%的範圍內添加水。以上顯影液可根據需要而併用2種以上。 Examples of the organic solvent-based developing solution include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, and methyl isobutyl ketone. Γ-butyrolactone and the like. In order to prevent ignition, these organic solvents preferably add water in a range of 1% by mass to 20% by mass. The above developer may be used in combination of two or more kinds as needed.

作為顯影的方式，可列舉：浸漬方式、攪拌(paddle)方式、高壓噴霧方式、噴霧方式、刷洗、刮擦等。這些中，就解像度提高的觀點而言，較佳為使用高壓噴霧方式。 Examples of the development method include a immersion method, a paddle method, a high pressure spray method, a spray method, a brushing, and a scratch. Among these, from the viewpoint of improving the resolution, it is preferred to use a high pressure spray method.

本實施方式的導電圖案的形成方法中，在顯影後根據需要，可藉由進行60℃~250℃左右的加熱或0.2J/cm²~10J/cm²左右的曝光而將導電圖案進一步硬化。 The method of forming a conductive pattern according to the present embodiment, after development if necessary, can be exposed by heating for about ² to about 60 ℃ ~ 250 ℃ or 0.2J / cm ² ~ 10J / cm and the conductive pattern is further cured.

如此，根據本實施方式的導電圖案的形成方法，可不形成如ITO等無機膜般的蝕刻抗蝕劑(etching resist)，而在玻璃基 板、塑膠基板等基板上容易形成透明的導電圖案。 As described above, according to the method of forming the conductive pattern of the present embodiment, an etching resist such as an inorganic film such as ITO can be formed without forming an etching resist. A transparent conductive pattern is easily formed on a substrate such as a board or a plastic substrate.

本發明的導電圖案基板可藉由上述導電圖案的形成方法而得。就可有效地用作透明電極等的觀點而言，導電圖案的表面電阻率較佳為2000Ω/□以下，更佳為1000Ω/□以下，特佳為500Ω/□以下。表面電阻率例如可藉由導電性纖維分散液的濃度、塗敷量等進行調整。 The conductive pattern substrate of the present invention can be obtained by the above-described method of forming a conductive pattern. The surface resistivity of the conductive pattern is preferably 2000 Ω/□ or less, more preferably 1000 Ω/□ or less, and particularly preferably 500 Ω/□ or less from the viewpoint of being effectively used as a transparent electrode or the like. The surface resistivity can be adjusted, for example, by the concentration of the conductive fiber dispersion, the amount of coating, and the like.

本發明的導電圖案基板較佳為450nm~650nm的波長區域中的最小透光率為80%以上，更佳為85%以上。在導電圖案基板40滿足此種條件時，顯示面板等中的視認性提高。 The conductive pattern substrate of the present invention preferably has a minimum light transmittance of 80% or more, more preferably 85% or more in a wavelength region of 450 nm to 650 nm. When the conductive pattern substrate 40 satisfies such conditions, the visibility in the display panel or the like is improved.

本發明的導電圖案的形成方法例如可較佳地用於形成靜電電容式觸控面板的透明電極。圖4是表示透明電極(X位置座標)103及透明電極(Y位置座標)104存在於同一平面上的靜電電容式觸控面板的一例的平面圖，圖5是其一部分缺口立體圖。圖6是沿著圖5中的Ⅵ-Ⅵ線的部分剖面圖。上述靜電電容式觸控面板在透明基板101上具有：檢測靜電電容變化而作為X位置座標的透明電極103、以及作為Y位置座標的透明電極104。這些作為X位置座標、Y位置座標的各透明電極103、透明電極104具有用以與控制觸控面板的電信號的驅動元件電路(未圖示)的控制電路連接的引出配線105a及引出配線(lead wiring)105b。 The method of forming the conductive pattern of the present invention can be preferably used, for example, to form a transparent electrode of a capacitive touch panel. 4 is a plan view showing an example of a capacitive touch panel in which a transparent electrode (X position coordinate) 103 and a transparent electrode (Y position coordinate) 104 are present on the same plane, and FIG. 5 is a partially broken perspective view thereof. Figure 6 is a partial cross-sectional view taken along line VI-VI of Figure 5 . The capacitive touch panel has a transparent electrode 103 as a X position coordinate and a transparent electrode 104 as a Y position coordinate on the transparent substrate 101. Each of the transparent electrodes 103 and the transparent electrodes 104, which are the X-position coordinates and the Y-position coordinates, has a lead-out wiring 105a and a lead-out wiring for connecting to a control circuit of a driving element circuit (not shown) that controls an electrical signal of the touch panel ( Lead wiring) 105b.

在透明電極(X位置座標)103與透明電極(Y位置座標)104交叉的部分設置絕緣膜106。上述絕緣膜選自具有電絕緣 特性、透明性、耐顯影性的材料。作為此種材料，可列舉：薄膜且透明的感光性膜等。 An insulating film 106 is provided at a portion where the transparent electrode (X position coordinate) 103 and the transparent electrode (Y position coordinate) 104 intersect. The above insulating film is selected from the group consisting of electrical insulation A material with properties, transparency, and developability. As such a material, a film and a transparent photosensitive film etc. are mentioned.

對藉由本發明的導電圖案的形成方法的靜電電容式觸控面板的製造方法進行說明。首先，在透明基板101上形成透明電極(X位置座標)103。具體而言，以導電層與透明基板101接觸的方式層壓感光性導電膜(層壓步驟)。對經轉印的感光層(導電層及感光性樹脂層)，以成所期望的形狀的方式經由遮光遮罩而圖案狀地照射光化射線(曝光步驟)。然後，除去遮光遮罩、接著將支撐膜剝離、並進行顯影，藉此將感光層的未曝光部除去，而形成導電圖案(顯影步驟)。藉由該導電圖案形成檢測X位置座標的透明電極103。 A method of manufacturing a capacitive touch panel by the method of forming a conductive pattern of the present invention will be described. First, a transparent electrode (X position coordinate) 103 is formed on the transparent substrate 101. Specifically, a photosensitive conductive film is laminated in such a manner that the conductive layer is in contact with the transparent substrate 101 (laminating step). The transferred photosensitive layer (the conductive layer and the photosensitive resin layer) is irradiated with actinic rays in a pattern through a light-shielding mask so as to have a desired shape (exposure step). Then, the light-shielding mask is removed, and then the support film is peeled off and developed, whereby the unexposed portion of the photosensitive layer is removed to form a conductive pattern (developing step). The transparent electrode 103 for detecting the X position coordinate is formed by the conductive pattern.

接著，形成透明電極(Y位置座標)104。在藉由上述步驟形成的透明電極103的一部分(例如欲使透明電極103與透明電極104交叉的部分)上設置絕緣膜106，在透明基板101上進一步層壓新的感光性導電膜，藉由上述同樣的操作，形成檢測Y位置座標的透明電極104。藉由本發明的導電圖案的形成方法，形成透明電極，藉此可在同一平面上形成透明電極(X位置座標)103及透明電極(Y位置座標)104。另外，由於在透明基板101側形成有導電圖案，因此在形成引出配線105a及引出配線105b時，容易實現所形成的導電圖案與引出配線的導通。 Next, a transparent electrode (Y position coordinate) 104 is formed. An insulating film 106 is disposed on a portion of the transparent electrode 103 formed by the above steps (for example, a portion where the transparent electrode 103 and the transparent electrode 104 are to be crossed), and a new photosensitive conductive film is further laminated on the transparent substrate 101. The same operation as described above forms the transparent electrode 104 for detecting the Y position coordinate. According to the method of forming a conductive pattern of the present invention, a transparent electrode is formed, whereby a transparent electrode (X position coordinate) 103 and a transparent electrode (Y position coordinate) 104 can be formed on the same plane. Further, since the conductive pattern is formed on the transparent substrate 101 side, when the lead wiring 105a and the lead wiring 105b are formed, it is easy to achieve conduction between the formed conductive pattern and the lead wiring.

接著，在透明基板101的表面形成用以與外部電路連接 的引出配線105a及引出配線105b。引出配線例如可使用含有薄片(flake)狀的銀等的導電膏材料，使用網版印刷法而形成。 Next, a surface of the transparent substrate 101 is formed to be connected to an external circuit. The lead wiring 105a and the lead wiring 105b. The lead wiring can be formed, for example, by a screen printing method using a conductive paste material containing silver or the like in the form of flakes.

另外，在上述靜電電容式觸控面板的製造方法中，其中之一的透明電極(例如透明電極(X位置座標)103)及引出配線105a、引出配線105b，可藉由使用透明導電材料的公知的方法，預先形成於透明基板101上。該情況下，亦可在同一平面內形成透明電極(X位置座標)103及透明電極(Y位置座標)104，且可獲得黏接性、解像性更優異的導電圖案。另外，藉由利用上述步驟進行圖案化，而可形成經橋接的透明電極(Y位置座標)104的導電圖案。 Further, in the method of manufacturing the capacitive touch panel, one of the transparent electrodes (for example, the transparent electrode (X position coordinate) 103), the lead wiring 105a, and the lead wiring 105b can be known by using a transparent conductive material. The method is previously formed on the transparent substrate 101. In this case, a transparent electrode (X position coordinate) 103 and a transparent electrode (Y position coordinate) 104 can be formed in the same plane, and a conductive pattern having more excellent adhesion and resolution can be obtained. Further, by patterning by the above steps, a conductive pattern of the bridged transparent electrode (Y-position coordinate) 104 can be formed.

另外，藉由本發明的導電圖案的形成方法的靜電電容式觸控面板的製造方法，並不限定於上述方法。例如，亦可使用如下基板：藉由利用透明導電材料的公知的方法，在透明基板101上預先形成透明電極(X位置座標)103、以及成為其後檢測Y位置座標的透明電極104的透明電極的一部分。圖7(a)、圖7(b)是用以說明同一平面上存在透明電極的靜電電容式觸控面板的製造方法的一例的圖，圖7(a)是表示具備透明電極的基板的一部分缺口立體圖，圖7(b)是表示所得的靜電電容式觸控面板的一部分缺口立體圖。圖8(a)~圖8(c)是用以說明同一平面上存在透明電極的靜電電容式觸控面板的製造方法的一例的圖。 Moreover, the method of manufacturing the capacitive touch panel by the method of forming a conductive pattern of the present invention is not limited to the above method. For example, a substrate in which a transparent electrode (X position coordinate) 103 and a transparent electrode which is a transparent electrode 104 for detecting a Y position coordinate are formed in advance on the transparent substrate 101 by a known method using a transparent conductive material a part of. 7(a) and 7(b) are views showing an example of a method of manufacturing a capacitive touch panel in which a transparent electrode is present on the same plane, and FIG. 7(a) shows a part of a substrate including a transparent electrode. FIG. 7(b) is a partially cutaway perspective view showing the obtained capacitive touch panel. 8(a) to 8(c) are diagrams for explaining an example of a method of manufacturing a capacitive touch panel in which a transparent electrode is present on the same plane.

首先，準備如圖7(a)及圖8(a)所示的預先形成有 透明電極(X位置座標)103、與透明電極的一部分104a的基板，在透明電極103的一部分(被透明電極的一部分104a夾著的部分)設置絕緣膜106(圖8(b))。然後，在上述基板上層壓感光性導電膜，藉由與上述曝光步驟及顯影步驟相同的方法，形成導電圖案。可藉由該導電圖案而形成透明電極的橋接部104b(圖8(c))。藉由該透明電極的橋接部104b，而可將預先形成的透明電極的一部分104a彼此導通，從而形成透明電極(Y位置座標)104。 First, prepare as shown in Fig. 7(a) and Fig. 8(a) in advance. The transparent electrode (X position coordinate) 103 and the substrate of the portion 104a of the transparent electrode are provided with an insulating film 106 (a portion sandwiched by a portion 104a of the transparent electrode) of the transparent electrode 103 (Fig. 8(b)). Then, a photosensitive conductive film is laminated on the substrate, and a conductive pattern is formed by the same method as the above-described exposure step and development step. The bridge portion 104b of the transparent electrode can be formed by the conductive pattern (Fig. 8(c)). A portion 104a of the transparent electrode formed in advance can be electrically connected to each other by the bridge portion 104b of the transparent electrode, thereby forming a transparent electrode (Y position coordinate) 104.

預先形成的透明電極例如可藉由使用ITO等的公知的方法而形成。 The previously formed transparent electrode can be formed, for example, by a known method using ITO or the like.

另外，引出配線105a、引出配線105b除了透明導電材料外，可藉由使用Cu、Ag等金屬等的公知的方法而形成。在本發明的導電圖案的形成方法中，可使用預先形成有引出配線105a、引出配線105b的基板。在使用此種基板時，根據本發明的導電圖案形成方法，可實現與引出配線直接導通，且可在與透明電極(X位置座標)絕緣的狀態下，形成透明電極(Y位置座標)，並可更簡便地製造導電圖案基板。 In addition to the transparent conductive material, the lead wiring 105a and the lead wiring 105b can be formed by a known method using a metal such as Cu or Ag. In the method of forming a conductive pattern of the present invention, a substrate on which the lead wiring 105a and the lead wiring 105b are formed in advance can be used. When such a substrate is used, according to the conductive pattern forming method of the present invention, direct conduction with the lead wiring can be realized, and a transparent electrode (Y position coordinate) can be formed in a state of being insulated from the transparent electrode (X position coordinate), and The conductive pattern substrate can be manufactured more easily.

實施例 Example

以下，基於實施例對本發明進行具體地說明，但本發明並不限定於此。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

〈導電性纖維分散液(銀纖維分散液)的製備〉 <Preparation of Conductive Fiber Dispersion (Silver Fiber Dispersion)

[藉由多元醇法的銀纖維的製備] [Preparation of Silver Fiber by Polyol Method]

在2000mL的3口燒瓶中，加入乙二醇500mL，在氮氣環境下，一邊藉由磁力攪拌器攪拌一邊藉由油浴加熱至160℃。於其中滴加另外準備的將2mg的PtCl₂溶解於50mL的乙二醇中而得的溶液。4分鐘~5分鐘後，分別自滴液漏斗歷時1分鐘滴加：將5g的AgNO₃溶解於乙二醇300mL中而得的溶液、以及將重量平均分子量為4萬的聚乙烯吡咯烷酮(和光純藥工業股份有限公司製造)5g溶解於乙二醇150mL中而得的溶液，然後在160℃下攪拌60分鐘。 In a 2000 mL three-necked flask, 500 mL of ethylene glycol was added, and the mixture was heated to 160 ° C in an oil bath while stirring under a nitrogen atmosphere with a magnetic stirrer. A separately prepared solution obtained by dissolving 2 mg of PtCl ₂ in 50 mL of ethylene glycol was added dropwise thereto. After 4 minutes to 5 minutes, the solution was added dropwise from the dropping funnel for 1 minute: a solution obtained by dissolving 5 g of AgNO ₃ in 300 mL of ethylene glycol, and a polyvinylpyrrolidone having a weight average molecular weight of 40,000 (and pure light) 5 g of a solution obtained by dissolving in 150 mL of ethylene glycol was stirred at 160 ° C for 60 minutes.

放置上述反應溶液直至成為30℃以下後，藉由丙酮稀釋至10倍，藉由離心分離機以2000轉進行20分鐘離心分離，並將上清液傾析。在沈澱物中添加丙酮並攪拌後，藉由與上述相同的條件進行離心分離，並將丙酮傾析。然後，使用蒸餾水以相同的方式進行2次離心分離，而獲得銀纖維。藉由光學顯微鏡觀察所得的銀纖維，結果纖維徑(直徑)為約5nm、纖維長為約5μm。 The reaction solution was allowed to stand at 30 ° C or lower, diluted with acetone to 10 times, centrifuged at 2000 rpm for 20 minutes by a centrifugal separator, and the supernatant was decanted. After acetone was added to the precipitate and stirred, the mixture was centrifuged under the same conditions as above, and acetone was decanted. Then, centrifugal separation was carried out twice in the same manner using distilled water to obtain silver fibers. The obtained silver fiber was observed by an optical microscope, and as a result, the fiber diameter (diameter) was about 5 nm, and the fiber length was about 5 μm.

[銀纖維分散液的製備] [Preparation of Silver Fiber Dispersion]

在純水中，以成為0.2質量%的濃度的方式分散上述所得的銀纖維，及以成為0.1質量%的濃度的方式分散十二烷基-五乙二醇，而獲得導電性纖維分散液1。 The silver fiber obtained above was dispersed in a concentration of 0.2% by mass in pure water, and dodecyl-pentaethylene glycol was dispersed so as to have a concentration of 0.1% by mass to obtain a conductive fiber dispersion 1 .

〈感光性樹脂組成物的溶液的製備〉 <Preparation of Solution of Photosensitive Resin Composition>

[丙烯酸系樹脂的合成] [Synthesis of Acrylic Resin]

在具備攪拌機、回流冷卻器、溫度計、滴液漏斗及氮氣導入 管的燒瓶中，添加甲基溶纖劑與甲苯的混合液(甲基溶纖劑/甲苯=3/2(質量比)、以下稱為「溶液s」)400g，一邊吹入氮氣一邊攪拌，加熱至80℃。另一方面，準備將作為單體的甲基丙烯酸100g、甲基丙烯酸甲酯250g、丙烯酸乙酯100g及苯乙烯50g、與作為起始劑的偶氮雙異丁腈0.8g混合而得的溶液(以下稱為「溶液a」)。接著，在加熱至80℃的溶液s中，歷時4小時滴加溶液a後，一邊在80℃攪拌一邊保溫2小時。接著，在燒瓶內歷時10分鐘滴加在100g的溶液s中溶解有偶氮雙異丁腈1.2g而得的溶液。接著，一邊攪拌滴加後的溶液，一邊在80℃下保溫3小時後，歷時30分鐘加熱至90℃。在90℃下保溫2小時後，進行冷卻而獲得黏合劑聚合物溶液。在該黏合劑聚合物溶液中，添加丙酮並以不揮發成分(固體成分)為50質量%的方式製備，而獲得作為(A)成分的黏合劑聚合物溶液。所得的黏合劑聚合物的重量平均分子量以藉由凝膠滲透層析法(Gel Permeation Chromatography，GPC)的標準聚苯乙烯換算計為80000。將其設為丙烯酸系聚合物A。另外，測定重量平均分子量的GPC的測定條件如下述所述。 With mixer, reflux cooler, thermometer, dropping funnel and nitrogen introduction In a flask of the tube, 400 g of a mixture of methyl cellosolve and toluene (methyl cellosolve/toluene = 3/2 (mass ratio), hereinafter referred to as "solution s") was added, and the mixture was stirred while blowing nitrogen gas. Heat to 80 ° C. On the other hand, a solution obtained by mixing 100 g of methacrylic acid as a monomer, 250 g of methyl methacrylate, 100 g of ethyl acrylate, and 50 g of styrene, and 0.8 g of azobisisobutyronitrile as a starter was prepared. (hereinafter referred to as "solution a"). Next, the solution a was added dropwise to the solution s heated to 80 ° C for 4 hours, and then kept at 80 ° C for 2 hours while stirring. Next, a solution obtained by dissolving 1.2 g of azobisisobutyronitrile in 100 g of the solution s was added dropwise to the flask over 10 minutes. Next, while stirring the dropwise addition solution, the mixture was kept at 80 ° C for 3 hours, and then heated to 90 ° C for 30 minutes. After holding at 90 ° C for 2 hours, cooling was carried out to obtain a binder polymer solution. To the binder polymer solution, acetone was added and prepared in a nonvolatile content (solid content) of 50% by mass to obtain a binder polymer solution as the component (A). The weight average molecular weight of the obtained binder polymer was 80,000 in terms of standard polystyrene by Gel Permeation Chromatography (GPC). This was made into the acrylic polymer A. Further, the measurement conditions of GPC for measuring the weight average molecular weight are as follows.

[GPC測定條件] [GPC measurement conditions]

機種：日立L6000(日立製作所股份有限公司製造) Model: Hitachi L6000 (manufactured by Hitachi, Ltd.)

檢測：L3300RI(日立製作所股份有限公司製造) Testing: L3300RI (manufactured by Hitachi, Ltd.)

管柱：Gelpack GL-R440+GL-R450+GL-R400M(日立化成股份有限公司製造) Pipe column: Gelpack GL-R440+GL-R450+GL-R400M (manufactured by Hitachi Chemical Co., Ltd.)

管柱規格：直徑10.7mm×300mm Column specifications: diameter 10.7mm × 300mm

溶劑：四氫呋喃(tetrahydrofuran，THF) Solvent: tetrahydrofuran (THF)

試樣濃度：採集NV(不揮發成分濃度)50質量%的樹脂溶液120mg、並溶解於5mL的THF中 Sample concentration: 120 mg of a resin solution having a NV (nonvolatile content concentration) of 50% by mass was collected and dissolved in 5 mL of THF.

注入量：200μL Injection volume: 200μL

壓力：4.9MPa Pressure: 4.9MPa

流量：2.05mL/min Flow rate: 2.05mL/min

[感光性樹脂組成物的溶液的製備] [Preparation of Solution of Photosensitive Resin Composition]

將表1所示的材料以同表所示的調配量(單位：質量份)進行調配，而製備感光性樹脂組成物的溶液。 The materials shown in Table 1 were formulated in the same amount as the one shown in the same table (unit: parts by mass) to prepare a solution of the photosensitive resin composition.

〈感光性導電膜的製作〉 <Production of Photosensitive Conductive Film>

(實施例1) (Example 1)

在作為支撐膜的厚度為16μm的聚對苯二甲酸乙二酯膜(PET膜、帝人股份有限公司製造、商品名：G2-16)上，以25g/m²均勻地塗佈上述導電性纖維分散液1，藉由100℃的熱風對流式乾燥機乾燥10分鐘，在室溫(25℃)下以1MPa的線壓進行加壓，藉此在支撐膜上形成含有導電性纖維的導電層。另外，藉由掃描型電子顯微鏡照片進行了測定，結果導電層的乾燥後的膜厚為約0.1μm。 The above-mentioned conductive fiber was uniformly coated at 25 g/m ² on a polyethylene terephthalate film (PET film, manufactured by Teijin Co., Ltd., trade name: G2-16) having a thickness of 16 μm as a support film. The dispersion 1 was dried by a hot air convection dryer at 100 ° C for 10 minutes, and pressurized at a room pressure (25 ° C) at a line pressure of 1 MPa to form a conductive layer containing conductive fibers on the support film. Further, as a result of measurement by a scanning electron microscope photograph, the film thickness after drying of the conductive layer was about 0.1 μm.

接著，將上述感光性樹脂組成物的溶液均勻地塗佈於另外準備的厚度為50μm的聚對苯二甲酸乙二酯膜(PET膜、帝人股份有限公司製造、商品名：G2-50)上，藉由100℃的熱風對流式乾燥機乾燥10分鐘，而形成感光性樹脂層。另外，藉由掃描型 電子顯微鏡照片進行了測定，結果感光性樹脂層的乾燥後的膜厚為5μm。 Then, the solution of the photosensitive resin composition was uniformly applied to a polyethylene terephthalate film (PET film, manufactured by Teijin Co., Ltd., trade name: G2-50) having a thickness of 50 μm prepared separately. The photosensitive resin layer was formed by drying with a hot air convection dryer at 100 ° C for 10 minutes. In addition, by scanning type The electron micrograph was measured, and as a result, the film thickness after drying of the photosensitive resin layer was 5 μm.

將以如上方式所得的形成有導電層的PET膜與形成有感光性樹脂層的PET膜，以導電層與感光性樹脂層相對的方式配置，在120℃、0.4MPa的條件下層壓，藉此製作目標感光性導電膜。 The PET film having the conductive layer obtained as described above and the PET film on which the photosensitive resin layer was formed were disposed such that the conductive layer and the photosensitive resin layer faced each other, and laminated at 120 ° C and 0.4 MPa. A target photosensitive conductive film is produced.

〈表面電阻率及透光率的測定〉 <Measurement of surface resistivity and light transmittance>

將厚度為1mm的聚碳酸酯基板加溫至80℃，在其表面上，一邊將在實施例1中所得的感光性導電膜的支撐膜(厚度為16μm的PET膜)剝離，一邊使導電層與聚碳酸酯基板對向，並且在120℃、0.4MPa的條件下層壓。層壓後，將基板冷卻並在基板的溫度為23℃的時，自覆蓋膜(厚度為50μm的PET膜)側，使用具有超高壓水銀燈的曝光機(歐克(OAK)製作所股份有限公司製造、商品名：EXM-1201)，以1000mJ/cm²的曝光量對感光層(導電層及感光性樹脂層)進行光照射。在曝光後，在室溫(25℃)下放置15分鐘，接著將作為覆蓋膜的PET膜剝離，藉此在聚碳酸酯基板上形成含有銀纖維的導電膜，而獲得導電膜基板。對所得的導電膜基板，進行表面電阻率及450nm~650nm的波長區域中的最小透光率的評價。使用下述測定裝置測定出的導電膜的表面電阻率為100Ω/□，450nm~650nm的波長區域中的最小透光率(包括基板)為90%。 The polycarbonate substrate having a thickness of 1 mm was heated to 80° C., and the support film (the PET film having a thickness of 16 μm) obtained in Example 1 was peeled off while the conductive layer was formed. It was opposed to the polycarbonate substrate and laminated at 120 ° C and 0.4 MPa. After lamination, the substrate was cooled and, when the temperature of the substrate was 23 ° C, from the side of the cover film (PET film having a thickness of 50 μm), an exposure machine having an ultrahigh pressure mercury lamp (manufactured by OAK Co., Ltd.) was used. In the product name: EXM-1201), the photosensitive layer (the conductive layer and the photosensitive resin layer) was irradiated with light at an exposure amount of 1000 mJ/cm ² . After the exposure, it was allowed to stand at room temperature (25 ° C) for 15 minutes, and then the PET film as a cover film was peeled off, whereby a conductive film containing silver fibers was formed on the polycarbonate substrate to obtain a conductive film substrate. The obtained conductive film substrate was evaluated for surface resistivity and minimum light transmittance in a wavelength region of 450 nm to 650 nm. The surface resistivity of the conductive film measured by the following measuring apparatus was 100 Ω/□, and the minimum light transmittance (including the substrate) in the wavelength region of 450 nm to 650 nm was 90%.

[表面電阻率的測定] [Measurement of surface resistivity]

使用非接觸型表面電阻計(奈普森(Napson)股份有限公司製造、EC-80P)進行測定。 The measurement was performed using a non-contact type surface resistance meter (manufactured by Napson Co., Ltd., EC-80P).

[透光率的測定] [Measurement of light transmittance]

使用分光光度計(日立高新技術(Hitachi High-Technologies)股份有限公司製造、商品名「U-3310」)，測定450nm~650nm的波長區域中的最小透光率。 The minimum light transmittance in a wavelength region of 450 nm to 650 nm was measured using a spectrophotometer (manufactured by Hitachi High-Technologies Co., Ltd., trade name "U-3310").

〈導電圖案的形成〉 <Formation of Conductive Patterns>

將厚度為1mm的聚碳酸酯基板加溫至80℃，在其表面上，一邊將支撐膜剝離，一邊使導電層與聚碳酸酯基板對向，並在120℃、0.4MPa的條件下層壓了實施例1中所得的感光性導電膜。層壓後，將基板冷卻並在基板的溫度為23℃的時，在作為覆蓋膜的PET膜面上，密接具有線寬/間隙寬為200μm/200μm且長度為100mm的配線圖案的光罩。接著，使用具有超高壓水銀燈的曝光機(歐克製作所股份有限公司製造、商品名：EXM-1201)，以30mJ/cm²的曝光量對感光層(導電層及感光性樹脂層)進行光照射。 The polycarbonate substrate having a thickness of 1 mm was heated to 80 ° C, and the support film was peeled off while the conductive layer was opposed to the polycarbonate substrate, and laminated at 120 ° C and 0.4 MPa. The photosensitive conductive film obtained in Example 1. After lamination, the substrate was cooled, and when the temperature of the substrate was 23 ° C, a mask having a wiring pattern having a line width/gap width of 200 μm/200 μm and a length of 100 mm was adhered to the PET film surface as a cover film. Next, the photosensitive layer (conductive layer and photosensitive resin layer) was irradiated with an exposure amount of 30 mJ/cm ² using an exposure machine (manufactured by Oak Industries, Inc., trade name: EXM-1201) having an ultrahigh pressure mercury lamp. .

曝光後，在室溫(25℃)下放置15分鐘，接著將作為覆蓋膜的PET膜剝離，在30℃下噴霧1質量%的碳酸鈉水溶液30秒而進行了顯影。顯影後，在聚碳酸酯基板上形成線寬/間隙寬為約200μm/200μm的含有銀纖維的導電圖案。並確認到各個導電圖案被良好地形成著。 After the exposure, the film was allowed to stand at room temperature (25 ° C) for 15 minutes, and then the PET film as a cover film was peeled off, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C for 30 seconds to develop. After development, a conductive pattern containing silver fibers having a line width/gap width of about 200 μm/200 μm was formed on the polycarbonate substrate. It was confirmed that the respective conductive patterns were well formed.

[產業上之可利用性] [Industrial availability]

根據本發明的導電圖案的形成方法，能以充分的解像度形成與基材的黏接性充分、且表面電阻率充分小的導電圖案。此外，可將設置於基板表面的連接端子等與導電圖案簡便地連接。 According to the method for forming a conductive pattern of the present invention, a conductive pattern having sufficient adhesion to a substrate and having a sufficiently small surface resistivity can be formed with sufficient resolution. Further, the connection terminals and the like provided on the surface of the substrate can be easily connected to the conductive pattern.