TWI693160B - Production method of conductive film and conductive film - Google Patents

Production method of conductive film and conductive film Download PDF

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TWI693160B
TWI693160B TW105124155A TW105124155A TWI693160B TW I693160 B TWI693160 B TW I693160B TW 105124155 A TW105124155 A TW 105124155A TW 105124155 A TW105124155 A TW 105124155A TW I693160 B TWI693160 B TW I693160B
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resin
resin layer
group
conductive film
carboxyl group
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TW201718247A (en
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鳥羽正彦
內田博
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日商昭和電工股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form

Abstract

本發明之課題為提供與基板之密著性、環境耐性及耐擦傷性為高之導電薄膜之製造方法及導電薄膜。 An object of the present invention is to provide a method for manufacturing a conductive thin film with high adhesion to a substrate, environmental resistance, and scratch resistance, and a conductive thin film.

解決手段係使用含第1官能基之第1樹脂組成物於基板上形成第1樹脂層(S1)，將該第1樹脂層乾燥至導電材料不沉入層內部之程度後(S2)，於第1樹脂層上形成俯視具有開口部之導電圖型(S3、S4)，使用含可與上述第1樹脂層之第1官能基共硬化之第2官能基之第2樹脂組成物，以覆蓋導電圖型之至少一部分之方式形成第2樹脂層，使第1樹脂層與第2樹脂層共硬化(S5)。 The solution is to form the first resin layer (S1) on the substrate using the first resin composition containing the first functional group, and dry the first resin layer to the extent that the conductive material does not sink into the layer (S2), A conductive pattern (S3, S4) having an opening is formed on the first resin layer in plan view, and a second resin composition containing a second functional group co-hardenable with the first functional group of the first resin layer is used to cover The second resin layer is formed by at least a part of the conductive pattern, and the first resin layer and the second resin layer are co-hardened (S5).

Description

導電薄膜之製造方法及導電薄膜 Manufacturing method of conductive film and conductive film

本發明有關導電薄膜之製造方法及導電薄膜。 The invention relates to a method for manufacturing a conductive film and a conductive film.

導電薄膜係因應於對各種電子零件之用途而開發、生產多種類。例如透明導電薄膜使用於液晶顯示器(LCD)、電漿顯示器面板(PDP)、有機電致發光型顯示器、太陽電池(PV)及觸控面板(TP)之透明電極、抗靜電(ESD)薄膜以及電磁波遮蔽(EMI)薄膜等之各種領域。作為該等透明導電薄膜，以往雖使用利用ITO(氧化銦錫)者，但有銦之供給穩定性低，製造成本高，欠缺柔軟性，以及成膜時需要高溫之問題。因此，已活躍地進行取代ITO之透明導電薄膜之探討。該等中，含有金屬奈米線之透明導電薄膜係導電性、光學特性及柔軟性優異，可藉濕式製程成膜，製造成本低，成膜時不需要高溫，故適合作為代替ITO之透明導電薄膜。 The conductive film is developed and produced according to the application of various electronic parts. For example, transparent conductive films are used for transparent electrodes, antistatic (ESD) films and liquid crystal displays (LCD), plasma display panels (PDP), organic electroluminescent displays, solar cells (PV), and touch panels (TP). Various fields such as electromagnetic wave shielding (EMI) film. As such transparent conductive thin films, those using ITO (indium tin oxide) have been used in the past, but there are problems of low supply stability of indium, high manufacturing cost, lack of flexibility, and high temperature required during film formation. Therefore, the discussion of replacing the ITO transparent conductive film has been actively carried out. Among them, the transparent conductive film containing metal nanowires is excellent in conductivity, optical properties and flexibility, and can be formed by a wet process, the manufacturing cost is low, and the film does not require high temperature, so it is suitable as a transparent substitute for ITO Conductive film.

例如含有銀奈米線、具有高導電性、光學特 性、柔軟性之透明導電膜為已知(參考專利文獻1)。又，下述專利文獻2中，揭示於透明基材上具有含有金屬奈米線之透明導電層之透明導電薄膜之製造方法。 For example, it contains silver nanowires, has high electrical conductivity, optical characteristics The transparent conductive film of flexibility and flexibility is known (refer patent document 1). In addition, Patent Document 2 below discloses a method for manufacturing a transparent conductive film having a transparent conductive layer containing metal nanowires on a transparent substrate.

如此之透明導電薄膜中，導電層與基板之密著性必須為高。此外，尤其是含有金屬奈米線之透明導電薄膜，由於銀等之金屬之每質量之表面積大，容易與各種化合物反應，故有缺乏環境耐性之問題。因此，由步驟中使用之各種藥劑或洗淨液之影響或因長期保存遭受之空氣中之氧或水分之影響等，使奈米構造體腐蝕、容易使導電性降低。且，尤其於電子材料等之用途中，為了防止微粒子狀之雜質或碎屑或灰塵等於基板表面之附著或混入，較多情況係利用使用刷子等之物理洗淨步驟，但藉由該步驟亦有表面造成損傷之問題。 In such a transparent conductive film, the adhesion between the conductive layer and the substrate must be high. In addition, in particular, transparent conductive films containing metal nanowires have a problem of lack of environmental resistance due to the large surface area per mass of metals such as silver, which are easily reacted with various compounds. Therefore, due to the influence of various chemicals or cleaning solutions used in the step or the influence of oxygen or moisture in the air due to long-term storage, the nanostructure is corroded and the conductivity is easily reduced. Moreover, especially in the use of electronic materials, etc., in order to prevent the attachment or mixing of particulate-like impurities, debris, or dust equal to the surface of the substrate, a physical cleaning step using a brush or the like is often used, but this step also There is a problem of surface damage.

為了解決此，已進行多種嘗試於包含銀奈米線之透明導電薄膜之表面層合保護膜，而對該透明導電薄膜賦予環境耐性及耐擦傷性(參考專利文獻3~4)。 In order to solve this, various attempts have been made to laminate a protective film on the surface of a transparent conductive film containing silver nanowires, and to impart environmental resistance and scratch resistance to the transparent conductive film (refer to Patent Documents 3 to 4).

因此，對透明導電薄膜要求導電層與基板之密著性、環境耐性及耐擦傷性為高。 Therefore, the transparent conductive film is required to have high adhesion between the conductive layer and the substrate, environmental resistance, and scratch resistance.

〔先前技術文獻〕 [Previous Technical Literature] 〔專利文獻〕 [Patent Literature]

專利文獻1：日本特表2010-507199號公報 Patent Literature 1: Japanese Special Publication No. 2010-507199

專利文獻2：日本專利第5609008號公報 Patent Document 2: Japanese Patent No. 5609008

專利文獻3：日本特開2014-191894號公報 Patent Document 3: Japanese Patent Application Publication No. 2014-191894

專利文獻4：日本特開2013-200943號公報 Patent Document 4: Japanese Patent Application Publication No. 2013-200943

本發明之目的在於提供導電層與基板之密著性、環境耐性及耐擦傷性為高之導電薄膜之製造方法及導電薄膜。 An object of the present invention is to provide a method for manufacturing a conductive film and a conductive film having high adhesion between a conductive layer and a substrate, environmental resistance, and scratch resistance.

為了達成上述目的，本發明之一實施形態係導電薄膜之製造方法，其特徵為包含：使用含第1官能基之第1樹脂組成物於基板上形成第1樹脂層之步驟，於前述第1樹脂層上形成俯視具有開口部之導電圖型之步驟，使用含可與前述第1樹脂層之第1官能基共硬化之第2官能基之第2樹脂組成物，以覆蓋前述導電圖型之至少一部分之方式形成第2樹脂層之步驟，及使前述第1樹脂層與第2樹脂層共硬化之步驟。 In order to achieve the above object, one embodiment of the present invention is a method for manufacturing a conductive film, which is characterized by comprising: a step of forming a first resin layer on a substrate using a first resin composition containing a first functional group. The step of forming a conductive pattern with an opening on the resin layer in plan view, using a second resin composition containing a second functional group co-hardenable with the first functional group of the first resin layer to cover the conductive pattern The step of forming the second resin layer by at least a part of the steps, and the step of co-hardening the first resin layer and the second resin layer.

上述導電圖型較好於前述第1樹脂層之表面上黏性消失後而形成。 The conductive pattern is preferably formed after the viscosity on the surface of the first resin layer disappears.

又，上述第1官能基只要包含羧基、羥基、環氧基、(甲基)丙烯醯基、乙烯基、烯丙基等之具有後述步驟所致之反應性之部位即可，第1樹脂組成物較好包含含羧基之聚胺基甲酸酯、酚酚醛清漆型環氧樹脂、苯氧基樹脂、含羧基之聚胺基甲酸酯與以羧基基準未達當量之 環氧化合物之混合物、鄰苯二甲酸二烯丙酯樹脂之任一者。 In addition, the first functional group only needs to include a carboxyl group, a hydroxyl group, an epoxy group, a (meth)acryloyl group, a vinyl group, an allyl group, etc. that have reactivity due to the steps described below. The first resin composition The material preferably contains a carboxyl group-containing polycarbamate, a phenol novolak epoxy resin, a phenoxy resin, a carboxyl group-containing polycarbamate, and a carboxyl group-based equivalent of less than Either a mixture of epoxy compounds or diallyl phthalate resin.

又，上述第2樹脂組成物較好包含含羧基之聚胺基甲酸酯與環氧化合物之混合物、酚酚醛清漆型環氧樹脂、苯氧基樹脂、含羧基之聚胺基甲酸酯與以羧基基準為當量以上之環氧化合物之混合物、鄰苯二甲酸二烯丙酯樹脂與丙烯酸酯單體之混合物之任一者。 Further, the second resin composition preferably includes a mixture of a carboxyl group-containing polyurethane and an epoxy compound, a phenol novolac epoxy resin, a phenoxy resin, a carboxyl group-containing polyurethane and Either a mixture of an epoxy compound having an equivalent or more based on a carboxyl group, a mixture of diallyl phthalate resin and acrylate monomer.

又，上述基板、第1樹脂層、導電圖型及第2樹脂層較好各為透明。 In addition, the substrate, the first resin layer, the conductive pattern, and the second resin layer are preferably transparent.

且，本發明之其他實施形態係導電薄膜，其特徵係於基板上具有含第1官能基之第1樹脂層，於該第1樹脂層上具有俯視具有開口部之導電圖型，以覆蓋該導電圖型之至少一部分之方式形成含第2官能基之第2樹脂層，且於前述導電圖型開口部具有第1樹脂層之第1官能基與第2樹脂層之第2官能基之硬化反應部分。 Moreover, another embodiment of the present invention is a conductive film, which is characterized by having a first resin layer containing a first functional group on the substrate, and having a conductive pattern with an opening in a plan view on the first resin layer to cover the Forming a second resin layer containing a second functional group by at least a part of the conductive pattern, and having the first functional group of the first resin layer and the second functional group of the second resin layer in the opening of the conductive pattern The reaction part.

上述導電薄膜之全光線透過率較好為70%以上。 The total light transmittance of the conductive film is preferably 70% or more.

上述導電圖型亦可包含無序之具有交叉接觸部之金屬奈米線。 The above conductive pattern may also include disordered metal nanowires with cross-contacts.

上述導電圖型亦可包含規則或不規則地形成之金屬細線圖型。 The above conductive pattern may also include metal thin line patterns formed regularly or irregularly.

依據本發明，可提供與基板之密著性、環境 耐性、耐擦傷性及光學特性良好之導電薄膜。 According to the present invention, adhesion to the substrate and environment can be provided Conductive film with good resistance, scratch resistance and optical properties.

10‧‧‧基板 10‧‧‧ substrate

12‧‧‧第1樹脂層 12‧‧‧The first resin layer

14‧‧‧導電圖型 14‧‧‧Conductive pattern

16‧‧‧第2樹脂層 16‧‧‧The second resin layer

18‧‧‧金屬奈米線 18‧‧‧Metal Nanowire

19‧‧‧金屬細線 19‧‧‧Metal fine wire

20‧‧‧開口部 20‧‧‧Opening

圖1係實施形態之導電薄膜之製造方法之步驟圖。 FIG. 1 is a process diagram of the manufacturing method of the conductive thin film of the embodiment.

圖2係實施形態之導電薄膜部分放大之概念圖。 FIG. 2 is a conceptual diagram of an enlarged part of the conductive film of the embodiment.

圖3係顯示實施例1及比較例7之導電薄膜之環境耐性評價結果之圖。 FIG. 3 is a graph showing the environmental resistance evaluation results of the conductive films of Example 1 and Comparative Example 7. FIG.

以下說明用以實施本發明之形態(以下稱為實施形態)。 The following describes an embodiment for implementing the present invention (hereinafter referred to as an embodiment).

實施形態之導電薄膜之製造方法之特徵為包含：使用含第1官能基之第1樹脂組成物於基板上形成第1樹脂層之步驟，於第1樹脂層上形成俯視具有開口部之導電圖型之步驟，使用含可與上述第1樹脂層之第1官能基共硬化之第2官能基之第2樹脂組成物，以覆蓋導電圖型之至少一部分之方式形成第2樹脂層之步驟，及使第1樹脂層與第2樹脂層共硬化之步驟。 The method for manufacturing a conductive film of an embodiment is characterized by including the steps of forming a first resin layer on a substrate using a first resin composition containing a first functional group, and forming a conductive pattern having an opening in a plan view on the first resin layer The step of forming a second resin layer containing a second functional group co-hardenable with the first functional group of the first resin layer to form a second resin layer so as to cover at least a part of the conductive pattern, And the step of co-hardening the first resin layer and the second resin layer.

圖1中顯示本實施形態之導電薄膜之製造方法之步驟圖。圖1中，首先於基板10上形成第1樹脂層(底塗層)12(S1：第1樹脂層形成步驟)。此處，第1樹脂層12只要為與基板10之密著性優異之樹脂則可使用。 FIG. 1 shows a step diagram of the manufacturing method of the conductive film of this embodiment. In FIG. 1, first, a first resin layer (undercoat layer) 12 is formed on a substrate 10 (S1: first resin layer forming step). Here, the first resin layer 12 can be used as long as it has excellent adhesion to the substrate 10.

實施上述S1(第1樹脂層形成步驟)之方法並未限定，舉例為例如網版印刷、凹版印刷及該等之平版印刷、棒塗佈器、模具塗佈器、凹版塗佈器等之接觸印刷、噴墨印刷、噴霧塗佈、佈膠等之非接觸印刷。 The method of implementing the above S1 (first resin layer forming step) is not limited, and examples include contact such as screen printing, gravure printing, and lithography, bar coater, die coater, gravure coater, etc. Non-contact printing for printing, inkjet printing, spray coating, cloth glue, etc.

作為構成基板10之基材並未特別限制，但可使用玻璃基板或PET(聚對苯二甲酸乙二酯)薄膜、PEN(聚萘二甲酸乙二酯)薄膜等之樹脂薄膜等。 The base material constituting the substrate 10 is not particularly limited, but a resin film such as a glass substrate, PET (polyethylene terephthalate) film, PEN (polyethylene naphthalate) film, or the like can be used.

又，第1樹脂層12係藉由包含於基板10表面上形成後，可與後述之構成第2樹脂層之第2樹脂組成物所含之第2官能基共硬化之第1官能基的第1樹脂組成物所構成。 Further, the first resin layer 12 is formed by the first functional group contained on the surface of the substrate 10 and can be co-hardened with the second functional group contained in the second resin composition constituting the second resin layer described later. 1 Made of resin composition.

其次，上述第1樹脂層12係較好藉由於基板10之表面上形成層狀之第1樹脂組成物後常溫或以適宜溫度加熱，而硬化或乾燥至用以形成後述之導電圖型之導電材料不會沉入第1樹脂層12內部之程度(S2：第1樹脂組成物乾燥步驟)。硬化或乾燥程度可藉由JIS K 5701之利用平行板黏度計所致之試驗之結果為0mm，亦即成為無流動性之狀態而判定，但若使用於常溫形成固體之樹脂層之樹脂組成物則由於於後述之導電圖型形成步驟中，導電材料不會完全沉入第1樹脂層12內而較佳。第1樹脂層12之形成(S1)、硬化或乾燥(S2)後，於第1樹脂層12上形成俯視具有開口部之導電圖型14。「導電圖型」亦包含形成為全面鋪滿狀。後述之圖2(a)所示之俯視具有開口部之導電圖型14，可藉由例如於第1樹脂 層12上將金屬奈米線分散於分散介質之墨水(以下有時稱為「金屬奈米線墨水」)予以圖型印刷(S3：印刷步驟)，對該金屬奈米線墨水進行光照射或藉加熱進行燒成(S4：燒成步驟)而得。含有經燒成之金屬奈米線之導電圖型之表面成為較第1樹脂層12表面露出於上方之狀態。 Next, the first resin layer 12 is preferably hardened or dried to form a conductive pattern to be described later by forming a layered first resin composition on the surface of the substrate 10 after heating at room temperature or at an appropriate temperature. The degree to which the material does not sink into the first resin layer 12 (S2: first resin composition drying step). The degree of hardening or drying can be determined by the test result of the parallel plate viscometer of JIS K 5701 being 0mm, which means that it has no fluidity, but if it is used in a resin composition that forms a solid resin layer at room temperature Therefore, in the conductive pattern forming step described later, it is preferable that the conductive material does not completely sink into the first resin layer 12. After the first resin layer 12 is formed (S1), hardened or dried (S2), a conductive pattern 14 having an opening in plan view is formed on the first resin layer 12. "Conductive pattern" also includes the formation of full coverage. The conductive pattern 14 having an opening in a plan view shown in FIG. 2(a) described later can be obtained by, for example, the first resin The ink on which the metal nanowire is dispersed in the dispersion medium (hereinafter sometimes referred to as "metal nanowire ink") is pattern-printed on the layer 12 (S3: printing step), and the metal nanowire ink is irradiated with light or It is obtained by heating and firing (S4: firing step). The surface of the conductive pattern containing the fired metal nanowire is exposed above the surface of the first resin layer 12.

此處所謂「開口部」意指如圖2(a)、(b)所示，於金屬奈米線18或金屬細線19之間具有空隙，使後述之第2樹脂組成物可接觸於第1樹脂組成物般之厚度方向之貫通部。又，圖2(a)、(b)係部分放大導電圖型14之概念圖。 The "opening" here means that, as shown in FIGS. 2(a) and (b), there is a gap between the metal nanowire 18 or the metal thin wire 19, so that the second resin composition described later can contact the first The penetration part in the thickness direction like a resin composition. 2 (a), (b) is a partially enlarged conceptual view of the conductive pattern 14.

使用金屬奈米線墨水時，藉由印刷使金屬奈米線18於基板上無序地堆積為具有交叉接觸部，以該交叉接觸部使金屬奈米線18彼此電性連接(包含接觸之情況)藉此展現導電性(圖2(a))。又，該情況之開口部20因無序地堆積之金屬奈米線18而成為不規則形狀。使用金屬奈米線墨水印刷鋪滿膜時，亦可獲得具有於厚度方向貫通之開口部20之導電圖型。此處所謂「金屬奈米線」意指具有直徑為數十nm~數百nm，長度為數μm~數十μm之形狀者。 When using metal nanowire ink, the metal nanowires 18 are randomly deposited on the substrate by printing to have cross contact portions, and the metal nanowires 18 are electrically connected to each other by the cross contact portions (including the case of contact) ) Thereby exhibiting electrical conductivity (Figure 2(a)). In addition, the opening 20 in this case has an irregular shape due to the disorderly deposited metal nanowires 18. When the metal nanowire ink is used to print the covered film, a conductive pattern having an opening 20 penetrating in the thickness direction can also be obtained. The “metal nanowire” here means a shape having a diameter of several tens of nm to several hundreds of nm and a length of several μm to several tens of μm.

又，圖2(b)所示之例，係由金屬細線19形成規則形狀(矩形狀)之開口部20。金屬細線19可使用金屬箔或後述之金屬奈米粒子墨水而形成。又，圖2(b)之例，係金屬細線19排列為格子狀且具有交叉部， 但亦可形成為例如於一定方向平行排列且不具有交叉部。且，金屬細線19亦可不規則配置，將開口部20作成不規則形狀。 In the example shown in FIG. 2( b ), the opening 20 of a regular shape (rectangular shape) is formed by the thin metal wires 19. The metal thin wires 19 can be formed using metal foil or metal nanoparticle ink described later. Also, in the example of FIG. 2(b), the metal thin wires 19 are arranged in a lattice and have intersections, However, it may be formed, for example, to be arranged in parallel in a certain direction without intersecting portions. Furthermore, the thin metal wires 19 may be arranged irregularly, and the opening 20 may be formed in an irregular shape.

於上述S3(印刷步驟)實施之印刷方法並無限定，若為可圖型印刷金屬奈米線墨水之印刷方法則可採用任何者。舉例為例如網版印刷、凹版印刷及該等之平版印刷、棒塗佈器、模具塗佈器、凹版塗佈器等之接觸印刷、噴墨印刷、噴霧塗佈、佈膠等之非接觸印刷。進行上述接觸印刷時，藉由於基板10塗佈例如第1樹脂組成物形成第1樹脂層12後，較好成為指觸乾燥狀態(無觸黏性(tack free))，亦即表面無黏性(無觸黏性)之狀態。藉此，即使印刷裝置接觸於第1樹脂層12，亦可進行良好印刷。又，構成第1樹脂層12之第1樹脂組成物於與構成第2樹脂層16之第2樹脂組成物共硬化時，基於縮短硬化時間之目的，亦可混合硬化促進劑。第1樹脂組成物含有後述之環氧化合物時，期望預先混合硬化促進劑。 The printing method implemented in the above S3 (printing step) is not limited, and any printing method can be adopted as long as it can be a pattern printing metal nanowire ink. Examples are non-contact printing such as screen printing, gravure printing, and lithography, bar coater, die coater, gravure coater, etc., inkjet printing, spray coating, cloth glue, etc. . When performing the above-mentioned contact printing, after the substrate 10 is coated with, for example, the first resin composition to form the first resin layer 12, it is preferably in a dry state of finger touch (tack free), that is, the surface is not tacky (Non-tacky) state. Thereby, even if the printing device is in contact with the first resin layer 12, good printing can be performed. In addition, when the first resin composition constituting the first resin layer 12 is co-cured with the second resin composition constituting the second resin layer 16, a curing accelerator may be mixed for the purpose of shortening the curing time. When the first resin composition contains an epoxy compound described later, it is desirable to mix a hardening accelerator in advance.

另一方面，進行如噴墨方式之非接觸印刷時，第1樹脂層12並無必要成為指觸乾燥狀態，只要成為導電材料不會完全沉入第1樹脂層12內部之程度，亦即成為導電材料之表面露出於第1樹脂層12表面上之狀態即可。 On the other hand, when performing non-contact printing such as the inkjet method, the first resin layer 12 does not need to be in a dry state of touch, as long as the conductive material does not completely sink into the inside of the first resin layer 12, that is, it becomes The surface of the conductive material may be exposed on the surface of the first resin layer 12.

又，作為導電圖型14之印刷所使用之墨水不限定於上述金屬奈米線墨水，亦可使用例如金屬奈米粒子 墨水。但使用金屬奈米粒子墨水時，為了展現導電性，必須使導電粒子彼此成為緻密接觸之狀態，形成為鋪滿膜時，俯視時幾乎不存在開口部20。因此，為了形成具有開口部20之圖型，例如如圖2(b)所示，有必要形成具有開口部20之細線圖型(金屬細線19之圖型)。細線圖型可規則地形成亦可不規則地形成，亦可形成為如網格圖型般之具有交叉部。此處所謂「金屬奈米粒子」意指具有nm等級之粒徑之球狀、角狀、扁平「板」狀等，較好為具有球狀形狀者。 In addition, the ink used for the printing of the conductive pattern 14 is not limited to the above-mentioned metallic nanowire ink, and for example, metallic nanoparticles may also be used ink. However, when metal nanoparticle ink is used, in order to exhibit conductivity, the conductive particles must be brought into close contact with each other, and when it is formed to be covered with a film, the opening 20 hardly exists in a plan view. Therefore, in order to form the pattern having the opening 20, for example, as shown in FIG. 2(b), it is necessary to form the thin line pattern having the opening 20 (the pattern of the metal thin line 19). The thin line pattern may be formed regularly or irregularly, or may be formed to have intersections like a grid pattern. The term "metallic nanoparticles" as used herein means spherical, angular, flat "plate", etc. having a particle size of nm order, preferably those having a spherical shape.

印刷後之形成導電圖型14之基板若全光線透過率為80%以上，則由於確保用以使第1樹脂層12與後述之第2樹脂層16接觸之充分空隙故而較佳。 If the total light transmittance of the substrate on which the conductive pattern 14 is formed after printing is 80% or more, it is preferable to ensure sufficient space for contacting the first resin layer 12 and the second resin layer 16 described later.

其次，以被覆導電圖型之至少一部分之方式形成第2樹脂層(上覆層)16(S5：第2樹脂層形成步驟)。該步驟可藉由與前述S1(第1樹脂層形成步驟)同樣方法實施。所謂「至少一部分」包含全部。例如於作為用以取得與外部之導通之電極部而成為一部分維持露出之狀態時，該部分不被被覆。此種情況成為一部分被被覆。此處，第2樹脂層16係以含有可與構成上述第1樹脂層12之第1樹脂組成物所含之第1官能基共硬化之第2官能基之第2樹脂組成物構成。第2樹脂層形成步驟(S5)後，使第1樹脂層12與第2樹脂層16基於上述第1官能基及第2官能基而共硬化(S6：共硬化步驟(圖示省略))。亦即，使第1樹脂層12所含之第1官能基與 第2樹脂層16所含之第2官能基進行硬化反應。導電圖型14於厚度方向具有開口部20，於該開口部20埋入構成第2樹脂層16之第2樹脂組成物，於與第1樹脂層12之介面進行硬化反應。亦即，導電圖型14之開口部20中具有第1樹脂層12之第1官能基與第2樹脂層16之第2官能基之硬化反應部分。其結果，成為導電圖型14由第1樹脂層12與第2樹脂層16夾住並且於導電圖型14之開口部20中被保持，獲得與基板10具有良好密著性之導電圖型14。作為第1樹脂層12之第1官能基與第2樹脂層16之第2官能基之組合，舉例為例如羧基/環氧基、環氧基/羧基、羥基/羧基、(甲基)丙烯醯基/乙烯基、乙烯基/(甲基)丙烯醯基、烯丙基/(甲基)丙烯醯基等，但不限定於此。 Next, the second resin layer (overlying layer) 16 is formed so as to cover at least a part of the conductive pattern (S5: second resin layer forming step). This step can be implemented by the same method as the aforementioned S1 (first resin layer forming step). The so-called "at least a part" includes all. For example, when a part of the electrode part for obtaining conduction with the outside remains exposed, the part is not covered. This situation becomes part of the cover. Here, the second resin layer 16 is composed of a second resin composition containing a second functional group co-hardenable with the first functional group contained in the first resin composition constituting the first resin layer 12. After the second resin layer forming step (S5), the first resin layer 12 and the second resin layer 16 are co-hardened based on the first functional group and the second functional group (S6: co-hardening step (not shown)). That is, the first functional group contained in the first resin layer 12 and The second functional group contained in the second resin layer 16 undergoes a hardening reaction. The conductive pattern 14 has an opening 20 in the thickness direction. The second resin composition constituting the second resin layer 16 is buried in the opening 20 and undergoes a hardening reaction at the interface with the first resin layer 12. That is, the opening 20 of the conductive pattern 14 has a hardening reaction portion of the first functional group of the first resin layer 12 and the second functional group of the second resin layer 16. As a result, the conductive pattern 14 is sandwiched between the first resin layer 12 and the second resin layer 16 and held in the opening 20 of the conductive pattern 14 to obtain the conductive pattern 14 having good adhesion to the substrate 10 . The combination of the first functional group of the first resin layer 12 and the second functional group of the second resin layer 16 is exemplified by, for example, carboxyl/epoxy, epoxy/carboxy, hydroxy/carboxy, (meth)acrylonitrile Group/vinyl group, vinyl group/(meth)acryloyl group, allyl group/(meth)acryloyl group, etc., but not limited thereto.

作為構成上述第1樹脂層12之第1樹脂組成物與構成第2樹脂層16之第2樹脂組成物之組合，以(第1樹脂層：第2樹脂層)之順序舉例為(含羧基之聚胺基甲酸酯(第1官能基為羧基)：含羧基之聚胺基甲酸酯與環氧化合物之混合物(第2官能基為環氧基))、(酚酚酸清漆型環氧樹脂(第1官能基為環氧基)：酚酚醛清漆型環氧樹脂(第2官能基為環氧基))、(苯氧基樹脂(第1官能基為環氧基)：苯氧基樹脂(第2官能基為環氧基))、(含羧基之聚胺基甲酸酯(第1官能基為羧基)：苯氧基樹脂(第2官能基為環氧基))、(含羧基之聚胺基甲酸酯與以羧基基準未達當量之環氧化合物之 混合物(第1官能基為羧基)：含羧基之聚胺基甲酸酯與以羧基基準為當量以上之環氧化合物之混合物(第2官能基為環氧基))、(鄰苯二甲酸二烯丙酯樹脂(第1官能基為烯丙基)：鄰苯二甲酸二烯丙酯與丙烯酸酯單體之混合物(第2官能基為烯丙基及丙烯醯基))等。 As a combination of the first resin composition constituting the first resin layer 12 and the second resin composition constituting the second resin layer 16, the order of (first resin layer: second resin layer) is exemplified by (containing a carboxyl group) Polyurethane (the first functional group is a carboxyl group): a mixture of a carboxyl group-containing polyurethane and an epoxy compound (the second functional group is an epoxy group)), (phenolic novolac epoxy Resin (first functional group is epoxy group): phenol novolac epoxy resin (second functional group is epoxy group)), (phenoxy resin (first functional group is epoxy group): phenoxy group Resin (the second functional group is an epoxy group)), (polycarbamate containing a carboxyl group (the first functional group is a carboxyl group): phenoxy resin (the second functional group is an epoxy group)), (containing Carboxylic Polyurethanes and Epoxy Compounds Not Equivalent to Carboxyl Standards Mixture (the first functional group is a carboxyl group): a mixture of a urethane group containing a carboxyl group and an epoxy compound having an equivalent or more based on the carboxyl group (the second functional group is an epoxy group)), (diphthalic acid Allyl ester resin (the first functional group is an allyl group): a mixture of diallyl phthalate and acrylate monomers (the second functional group is an allyl group and acryl group), etc.

上述組合內，於第1樹脂組成物含有含羧基之聚胺基甲酸酯，第2樹脂組成物含有含羧基之聚胺基甲酸酯與環氧基化合物之組合時，藉由使第1樹脂層12與第2樹脂層16加熱，使第1樹脂層12與第2樹脂層16所含之含羧基之聚胺基甲酸酯之羧基(第1官能基)與環氧化合物之環氧基(第2官能基)鍵結而共硬化。第1樹脂組成物包含含羧基之聚胺基甲酸酯與以羧基基準未達當量之環氧化合物，第2樹脂組成物包含含羧基之聚胺基甲酸酯與以羧基基準為當量以上之環氧化合物之組合時，亦同樣共硬化。且，於酚酚醛清漆型環氧樹脂組成物彼此、苯氧基樹脂組成物彼此之組合時，藉由添加適宜之環氧樹脂用硬化劑並加熱而共硬化。該情況第1官能基及第2官能基均成為環氧基。且，於第1樹脂組成物包含含羧基之聚胺基甲酸酯，第2樹脂組成物包含苯氧基樹脂之組合時，藉由使第1樹脂層12與第2樹脂層16加熱，使羧基(第1官能基)與環氧基(第2官能基)鍵結而共硬化。再者，於第1樹脂組成物包含鄰苯二甲酸二烯丙酯(第1官能基為烯丙基)，第2樹脂組成物包含鄰苯二甲酸二烯丙酯與丙烯酸酯單體(第2官能基為烯丙基及丙烯醯基) 之組合時，藉由光照射進行加成聚合而共硬化。 In the above combination, when the first resin composition contains a carboxyl group-containing polyurethane and the second resin composition contains a carboxyl group-containing polyurethane and epoxy compound, the first The resin layer 12 and the second resin layer 16 are heated so that the carboxyl group (first functional group) of the carboxyl group-containing polyurethane contained in the first resin layer 12 and the second resin layer 16 and the epoxy of the epoxy compound The group (second functional group) is bonded and co-hardened. The first resin composition contains a carboxyl group-containing polycarbamate and an epoxy compound not equivalent in terms of carboxyl groups, and the second resin composition contains a carboxyl group-containing polycarbamate and an equivalent in carboxyl groups or more The epoxy compounds are also hardened together. In addition, when the phenol novolac-type epoxy resin composition and the phenoxy resin composition are combined, they are hardened by adding an appropriate epoxy resin hardener and heating. In this case, both the first functional group and the second functional group become epoxy groups. In addition, when the first resin composition includes a carboxyl group-containing polyurethane and the second resin composition includes a combination of phenoxy resins, the first resin layer 12 and the second resin layer 16 are heated so that The carboxyl group (first functional group) and the epoxy group (second functional group) are bonded and co-hardened. Furthermore, the first resin composition contains diallyl phthalate (the first functional group is allyl group), and the second resin composition contains diallyl phthalate and acrylate monomer (section (2 functional groups are allyl and acryl) In the combination, addition polymerization is carried out by light irradiation to co-harden.

此處，上述基板10、第1樹脂層12、導電圖型14及第2樹脂層16較好為透明。藉此，可應用於觸控面板等之透明元件。此處，所謂透明意指全光線透過率為80%以上。包含該等之構成之本發明的導電薄膜之全光線透過率較好為70%以上，更好為75%以上，又更好為80%以上。 Here, the substrate 10, the first resin layer 12, the conductive pattern 14 and the second resin layer 16 are preferably transparent. Therefore, it can be applied to transparent elements such as touch panels. Here, transparent means that the total light transmittance is 80% or more. The total light transmittance of the conductive film of the present invention including such a composition is preferably 70% or more, more preferably 75% or more, and still more preferably 80% or more.

實施例 Examples

以下具體說明本發明之實施例。又，以下之實施例係為了使容易理解本發明者，本發明並非限定於該等實施例。 The following specifically describes embodiments of the present invention. In addition, the following embodiments are for the purpose of making the present invention easy to understand, and the present invention is not limited to these embodiments.

本實施例中，樹脂之分子量及酸價以及導電圖型之全光線透過率及表面電阻如以下般測定。 In this example, the molecular weight and acid value of the resin as well as the total light transmittance and surface resistance of the conductive pattern were measured as follows.

<分子量> <molecular weight>

以凝膠滲透層析儀(以下記為GPC)測定之聚苯乙烯換算之值。 The value converted from polystyrene measured by a gel permeation chromatography (hereinafter referred to as GPC).

GPC之測定條件如下。 The measurement conditions of GPC are as follows.

裝置名：日本分光股份有限公司製HPLC單元HSS-2000 Device name: HPLC unit HSS-2000 manufactured by JASCO Corporation

管柱：Shodex管柱LF-804 Column: Shodex LF-804

移動相：四氫呋喃 Mobile phase: tetrahydrofuran

流速：1.0mL/min Flow rate: 1.0mL/min

檢測器：日本分光股份有限公司製RI-2031Plus Detector: RI-2031Plus manufactured by JASCO Corporation

溫度：40.0℃ Temperature: 40.0℃

試料量：試料環管100μl Sample volume: sample loop 100μl

試料濃度：調製為約0.1質量% Sample concentration: adjusted to about 0.1% by mass

<酸價> <acid value>

於100ml三角燒瓶中以精密天平精秤試料約0.2g，於其中添加乙醇/甲苯=1/2(質量比)之混合溶劑10ml並溶解。進而於該容器中添加1~3滴作為指示劑之酚酞乙醇溶液，充分攪拌試料直至均一。其以0.1N氫氧化鉀-乙醇溶液滴定，將指示劑之微紅色持續30秒時，設為中和終點。將由其結果使用下述計算式所得之值作為樹脂之酸價。 In a 100ml Erlenmeyer flask, use a precision balance to weigh about 0.2g of the sample, add 10ml of a mixed solvent of ethanol/toluene = 1/2 (mass ratio) and dissolve it. Furthermore, 1 to 3 drops of phenolphthalein ethanol solution as an indicator were added to the container, and the sample was sufficiently stirred until uniform. It is titrated with a 0.1N potassium hydroxide-ethanol solution, and when the reddish color of the indicator lasts for 30 seconds, it is set as the neutralization end point. The value obtained from the result using the following calculation formula was taken as the acid value of the resin.

酸價(mg-KOH/g)=[B×f×5.611]/S Acid value (mg-KOH/g)=[B×f×5.611]/S

B：0.1N氫氧化鉀-乙醇溶液使用量(ml) B: Use amount of 0.1N potassium hydroxide-ethanol solution (ml)

f：0.1N氫氧化鉀-乙醇溶液之係數 f: coefficient of 0.1N potassium hydroxide-ethanol solution

S：試料採取量(g) S: amount of sample taken (g)

<全光線透過率> <full light transmittance>

於基板上形成之導電圖型切成50mm見方，使用濁度計(NDH 2000，日本電色工業製)測定之值。 The conductive pattern formed on the substrate was cut into 50 mm squares and measured using a turbidity meter (NDH 2000, manufactured by Nippon Denshoku Industries).

<表面電阻> <surface resistance>

利用電阻率計LORESTA(註冊商標)GP MCP-T610 型(三菱化學分析公司製)以4端子法測定。測定模式及使用端子係使用ESP模式。 Using resistivity meter LORESTA (registered trademark) GP MCP-T610 Type (manufactured by Mitsubishi Chemical Analysis Co., Ltd.) was measured by the 4-terminal method. The ESP mode is used for the measurement mode and the use terminal.

<含羧基之聚胺基甲酸酯之合成例> <Synthesis example of carboxyl group-containing polyurethane> [合成例1] [Synthesis Example 1]

於具備攪拌裝置、溫度計、冷凝器之2L三頸燒瓶中，饋入作為多元醇化合物之C-1015N(KURARAY股份有限公司製，聚碳酸酯二醇，原料二醇莫耳比為1,9-壬二醇：2-甲基-1,8-辛二醇=15：85，分子量964)143.6g、作為具有羧基之二羥基化合物之2,2-二羥甲基丁酸(日本化成股份有限公司製)27.32g及作為溶劑之丙二醇單甲醚乙酸酯(商品名：乙酸甲氧基丙酯，DAICEL股份有限公司製)259g，於90℃使上述2,2-二羥甲基丁酸溶解。 In a 2L three-necked flask equipped with a stirring device, a thermometer, and a condenser, C-1015N (manufactured by KURARAY Co., Ltd., polycarbonate diol, raw material diol molar ratio of 1,9- Nonanediol: 2-methyl-1,8-octanediol=15:85, molecular weight 964) 143.6g, 2,2-dimethylolbutyric acid as a dihydroxy compound having a carboxyl group (Nippon Kasei Co., Ltd. Co., Ltd.) 27.32g and propylene glycol monomethyl ether acetate (trade name: methoxypropyl acetate, manufactured by DAICEL Co., Ltd.) 259g as a solvent, and the above 2,2-dimethylol butyric acid was used at 90°C Dissolve.

反應液溫度降至70℃，藉由滴加漏斗，以30分鐘滴加作為聚異氰酸酯之DESMODUR(註冊商標)-W(亞甲基雙(4-環己基異氰酸酯)，住化拜耳胺基甲酸酯股份有限公司製)87.5g。滴加結束後，升溫至120℃，於120℃進行反應6小時，藉由IR確認異氰酸酯大致消失後，添加異丁醇0.5g，進而於120℃進行反應6小時。所得含羧基之聚胺基甲酸酯之重量平均分子量為32300，該樹脂之酸價為40mgKOH/g。 The temperature of the reaction solution was lowered to 70°C, and DESMODUR (registered trademark)-W (methylene bis(4-cyclohexyl isocyanate)) as polyisocyanate was added dropwise through a dropping funnel over 30 minutes. Ester Co., Ltd.) 87.5g. After the dropwise addition, the temperature was raised to 120°C, and the reaction was carried out at 120°C for 6 hours. After IR confirmation that the isocyanate had almost disappeared, 0.5 g of isobutanol was added, and the reaction was further carried out at 120°C for 6 hours. The weight average molecular weight of the resulting carboxyl group-containing polyurethane was 32,300, and the acid value of the resin was 40 mgKOH/g.

[合成例2] [Synthesis Example 2]

除了使用C-1015N(KURARAY股份有限公司製)44.8g、2,2-二羥甲基丁酸(日本化成股份有限公司製)16.1g及作為溶劑之丙二醇單甲醚乙酸酯(DAICEL股份有限公司製)100.3g、DESMODUR(註冊商標)-W(住化拜耳胺基甲酸酯股份有限公司製)40.7g以外，與合成例1同樣操作，獲得含羧基之聚胺基甲酸酯。所得含羧基之聚胺基甲酸酯之重量平均分子量為29200，該樹脂之酸價為60mgKOH/g。 In addition to the use of C-1015N (manufactured by Kuraray Co., Ltd.) 44.8g, 2,2-dimethylol butyric acid (manufactured by Nippon Kasei Co., Ltd.) 16.1g and propylene glycol monomethyl ether acetate (DAICEL Co., Ltd.) as a solvent Except for 100.3 g of the company) and 40.7 g of DESMODUR (registered trademark)-W (manufactured by Sumitomo Bayer Carbamate Co., Ltd.), the same procedure as in Synthesis Example 1 was performed to obtain a carboxyl group-containing polycarbamate. The weight average molecular weight of the resulting carboxyl group-containing polyurethane was 29,200, and the acid value of the resin was 60 mgKOH/g.

[實施例1] [Example 1]

如表1所示，於PET(聚對苯二甲酸乙二酯)基板(東麗(股)製LUMIRROR(註冊商標)125T60)上，將調配有合成例1合成之含羧基之聚胺基甲酸酯樹脂與硬化促進劑的CUREZOL(註冊商標)2P4MHZ-PW(2-苯基-4-甲基-5-羥基甲基咪唑，對於樹脂100質量份添加1質量份)，且以丙二醇單甲醚乙酸酯稀釋至含硬化促進劑之樹脂成分濃度成為30質量%之墨水(相當於第1樹脂組成物)以棒塗佈器進行印刷，於100℃乾燥1小時，形成膜厚10μm(使用MITUTOYO製，高精度數位次微米計MDH-25M 293-100於任意5處測定之其平均值)之底塗層(相當於第1樹脂層)。底塗層厚度係藉由測定形成底塗層、乾燥後之含基板之厚度，並減去基板厚度而求得。 As shown in Table 1, on the PET (polyethylene terephthalate) substrate (LUMIRROR (registered trademark) 125T60 manufactured by Toray Industries, Ltd.), a carboxyl group-containing polyamino group synthesized in Synthesis Example 1 was prepared. CUREZOL (registered trademark) 2P4MHZ-PW (2-phenyl-4-methyl-5-hydroxymethylimidazole, 1 part by mass for 100 parts by mass of resin) of the ester resin and hardening accelerator, and propylene glycol monomethyl Ink diluted with ether acetate until the concentration of the resin component containing the curing accelerator becomes 30% by mass (equivalent to the first resin composition) is printed with a bar coater, dried at 100°C for 1 hour, and formed into a film thickness of 10 μm (use Undercoat layer (equivalent to the first resin layer) of MITUTOYO, high-precision digital submicrometer MDH-25M 293-100 whose average value is measured at any 5 locations). The thickness of the undercoat layer is determined by measuring the thickness of the substrate after forming the undercoat layer and after drying, and subtracting the thickness of the substrate.

乾燥後，基於JIS Z0237實施觸黏性評價。任何球均未停止者記為無觸黏性，任一球停止者記為有觸黏 性。 After drying, the tackiness evaluation was performed based on JIS Z0237. Any ball that has not stopped is recorded as non-tacky, and any ball that is stopped is recorded as tacky Sex.

確認無觸黏性(tack free)後，作成銀奈米線分散液(銀奈米線0.125g(線平均徑約40nm，平均長度約10μm，均藉由SEM任意觀察100個銀奈米線之數平均值)分散於乙醇50g(調製銀奈米線0.25質量%分散液))，使用該分散液0.05g，藉由棒塗佈器以未自底塗層超出之方式進行塗佈。良好地進行銀奈米線分散液之塗佈。塗佈銀奈米線分散液後，於100℃燒成1小時，形成鋪滿狀之導電圖型。燒成後之表面電阻為80Ω/□，全光線透過率為89%。 After confirming tack free, a silver nanowire dispersion liquid (silver nanowire 0.125g (average wire diameter of about 40nm, average length of about 10μm, all arbitrarily observed by 100 SEM nanowires (Number average value) dispersed in 50 g of ethanol (prepared silver nanowire 0.25% by mass dispersion liquid)), and using this dispersion liquid 0.05 g, a bar coater was applied so as not to exceed the undercoat layer. The silver nanowire dispersion liquid was applied well. After the silver nanowire dispersion liquid is applied, it is fired at 100°C for 1 hour to form a covered conductive pattern. The surface resistance after firing is 80Ω/□, and the total light transmittance is 89%.

隨後，作為上覆層(相當於第2樹脂層)，係將於合成例1合成之含羧基之聚胺基甲酸酯樹脂10g與環氧化合物(三菱化學製jER(註冊商標)828)0.69g中，相對於含羧基之聚胺基甲酸酯樹脂與環氧化合物(三菱化學製jER(註冊商標)828)之總量100質量份調配1質量份之硬化促進劑(四國化成製CUREZOL(註冊商標)2P4MHZ-PW)而成之墨水(相當於第2樹脂組成物，以丙二醇單甲醚乙酸酯稀釋至含硬化促進劑之樹脂成分濃度成為30質量%)，以棒塗佈器以覆蓋導電圖型之大致全面之方式進行印刷，於140℃共硬化1小時。包含至底塗層之全體膜厚為20μm。對於合成例1合成之含羧基之聚胺基甲酸酯樹脂100質量份調配6質量份之環氧化合物(三菱化學製jER(註冊商標)828)時，合成例1合成之含羧基之聚胺基甲酸酯樹脂之羧基與環氧化合物 (三菱化學製jER(註冊商標)828)之環氧基成為當量。實施例1之上覆層(相當於第2樹脂層)，係如表1所示，由於合成例1合成之含羧基之聚胺基甲酸酯樹脂與環氧化合物(三菱化學製jER(註冊商標)828)之調配比(質量比)為100比7(表1中記載為100/7)，故成為對於合成例1合成之含羧基之聚胺基甲酸酯樹脂之羧基，環氧化合物(三菱化學製jER(註冊商標)828)之環氧基稍過量存在之組成。 Subsequently, as an overcoat layer (corresponding to the second resin layer), 10 g of the carboxyl group-containing polyurethane resin synthesized in Synthesis Example 1 and an epoxy compound (jER (registered trademark) 828 manufactured by Mitsubishi Chemical Corporation) 0.69 In g, 1 part by mass of hardening accelerator (CUREZOL manufactured by Shikoku Chemicals Co., Ltd.) is blended with the total amount of 100 parts by mass of the carboxyl group-containing polyurethane resin and the epoxy compound (jER (registered trademark) 828 by Mitsubishi Chemical Corporation). (Registered trademark) 2P4MHZ-PW) ink (equivalent to the second resin composition, diluted with propylene glycol monomethyl ether acetate until the concentration of the resin component containing the hardening accelerator becomes 30% by mass), using a bar coater The printing is carried out in a way that covers the entirety of the conductive pattern, and hardened at 140°C for 1 hour. The total film thickness up to the undercoat layer is 20 μm. When 100 parts by mass of the carboxyl group-containing polyurethane resin synthesized in Synthesis Example 1 is mixed with 6 parts by mass of an epoxy compound (jER (registered trademark) 828 manufactured by Mitsubishi Chemical Corporation), the carboxyl group-containing polyamine synthesized in Synthesis Example 1 Carboxyl group of urethane resin and epoxy compound (JER (registered trademark) 828 manufactured by Mitsubishi Chemical Corporation) has an epoxy group equivalent. The overlying layer (corresponding to the second resin layer) in Example 1 is shown in Table 1. Since the carboxyl group-containing polyurethane resin synthesized in Synthesis Example 1 and the epoxy compound (jER (registered by Mitsubishi Chemical Corporation) Trademark) 828) has a compounding ratio (mass ratio) of 100 to 7 (100/7 in Table 1), so it becomes the carboxyl group and epoxy compound of the carboxyl group-containing polyurethane resin synthesized in Synthesis Example 1. (JER (registered trademark) 828 manufactured by Mitsubishi Chemical Corporation) A composition in which epoxy groups are present in a slight excess.

針對所得導電薄膜進行以下特性評價。結果示於表1。 The following characteristic evaluation was performed about the obtained conductive film. The results are shown in Table 1.

[密著性評價(剝離試驗)] [Adhesion Evaluation (Peel Test)]

對於硬化膜進行交叉切割試驗JIS K5600作為密著性評價。結果於表1、2中記載為「剝離試驗」。又，試驗結果之數值越小意指密著性(耐剝離性)越高(0最佳)。表1中，實施例1之剝離試驗結果成為0，可知密著性(耐剝離性)高。 The cured film was subjected to a cross-cut test JIS K5600 as an adhesion evaluation. The results are described in Tables 1 and 2 as "peel test". In addition, the smaller the numerical value of the test result, the higher the adhesion (peel resistance) (0 is the best). In Table 1, the peeling test result of Example 1 becomes 0, and it can be seen that the adhesion (peeling resistance) is high.

[耐擦傷性試驗] [Scratch resistance test]

作為耐擦傷性試驗，藉由紙摩擦簡易判定擦傷性。使用之紙係使用JK擦紙，於上覆層上往返5次。以目視及顯微鏡確認有無傷痕、擦痕。結果於表1、2中記載為「耐擦傷性試驗」。 As an abrasion resistance test, the abrasion resistance is easily determined by paper rubbing. The paper used is JK paper wiping, 5 round trips on the top layer. Visually and microscope confirm whether there are scratches or scratches. The results are described in Tables 1 and 2 as "scratch resistance test".

◎：以目視及顯微鏡確認，並無傷痕、擦痕 ◎: Visually and microscopically confirmed that there are no scratches or scratches

○：以目視雖未見到傷痕，但以顯微鏡稍見到擦痕。 ○: Although scratches were not seen by visual inspection, scratches were slightly seen by microscope.

△：以目視雖未見到傷痕，但以顯微鏡見到傷痕、擦痕。 △: Although no scratches were seen visually, scratches and scratches were seen with a microscope.

×：以目視可判別傷痕、擦痕。 ×: Wounds and scratches can be distinguished visually.

[環境耐性] [Environmental tolerance]

作為環境耐性，係以恆溫恆濕器(ETAC製TH402A)，於85℃、85%RH(相對溼度)氛圍下保存，以自初期表面電阻之比來測定至約1100小時後之表面電阻變化。結果示於圖3。 As environmental resistance, it was stored in a constant temperature and humidity device (TH402A manufactured by ETAC) in an atmosphere of 85° C. and 85% RH (relative humidity), and the change in surface resistance after approximately 1100 hours was measured from the ratio of the initial surface resistance. The results are shown in Figure 3.

[光學特性] [Optical characteristics]

作為光學特性，係使用濁度計NDH 2000(日本電色製)測定所得導電薄膜之濁度(haze)及光線透過率。結果於表1、2中記載為「光學特性」。 As the optical characteristics, the haze and light transmittance of the obtained conductive film were measured using a turbidity meter NDH 2000 (manufactured by Nippon Denshoku). The results are described as "optical characteristics" in Tables 1 and 2.

○：全光線透過率80%以上且濁度20%以下。 ○: The total light transmittance is 80% or more and the haze is 20% or less.

×：全光線透過率80%以上且濁度超過20%。 ×: The total light transmittance is 80% or more and the turbidity exceeds 20%.

[實施例2~6] [Examples 2 to 6]

除了變更為表1所示之材料構成以外，與實施例1同樣使用調製之墨水，藉由同樣厚度構成、同樣步驟形成底塗層、導電圖型及上覆層。進行實施例1同樣之密著性評價(剝離試驗)、耐擦傷性試驗、光學特性評價之結果示於表1。對於實施例2之上覆層中使用之合成例2合成之 含羧基之聚胺基甲酸酯樹脂100質量份調配環氧化合物(三菱化學製jER(註冊商標)828)9質量份時，合成例2合成之含羧基之聚胺基甲酸酯樹脂之羧基與環氧化合物(三菱化學製jER(註冊商標)828)之環氧基成為當量。實施例2之上覆層(相當於第2樹脂層)，如表1所示，合成例2合成之含羧基之聚胺基甲酸酯樹脂與環氧化合物(三菱化學製jER(註冊商標)828)之調配比(質量比)為100比10(表1中記載為100/10)，故成為對於合成例2合成之含羧基之聚胺基甲酸酯樹脂之羧基，環氧化合物(三菱化學製jER(註冊商標)828)之環氧基稍過量存在之組成。 Except for changing to the material composition shown in Table 1, the prepared ink was used in the same manner as in Example 1, and the undercoat layer, the conductive pattern, and the overcoat layer were formed with the same thickness and the same procedure. Table 1 shows the results of the same adhesion evaluation (peel test), scratch resistance test, and optical characteristic evaluation as in Example 1. For the synthesis example 2 used in the overlying layer of example 2, When 100 parts by mass of carboxyl group-containing polyurethane resin is blended with 9 parts by mass of an epoxy compound (jER (registered trademark) 828 manufactured by Mitsubishi Chemical Corporation), the carboxyl group of the carboxyl group-containing polyurethane resin synthesized in Synthesis Example 2 Equivalent to epoxy group of epoxy compound (jER (registered trademark) 828 manufactured by Mitsubishi Chemical Corporation). The overlying layer (corresponding to the second resin layer) of Example 2 is shown in Table 1. The carboxyl group-containing polyurethane resin and epoxy compound (jER (registered trademark) manufactured by Mitsubishi Chemical) synthesized in Synthesis Example 2 are shown in Table 1. 828) has a compounding ratio (mass ratio) of 100 to 10 (100/10 described in Table 1), so it becomes a carboxyl group, epoxy compound (Mitsubishi) for the carboxyl group-containing polyurethane resin synthesized in Synthesis Example 2. The chemical jER (registered trademark) 828) has a slightly excessive amount of epoxy groups.

又，實施例6之底塗層(相當於第1樹脂層)，如表1所示，合成例1合成之含羧基之聚胺基甲酸酯樹脂與環氧化合物(三菱化學製jER(註冊商標)828)之調配比(質量比)為100比3(表1中記載為100/3)，故成為合成例1合成之含羧基之聚胺基甲酸酯樹脂之羧基殘留半量之組成。又，實施例6之上覆層(相當於第2樹脂層)與實施例1相同。 In addition, the undercoat layer of Example 6 (corresponding to the first resin layer) is shown in Table 1. The carboxyl group-containing polyurethane resin synthesized in Synthesis Example 1 and an epoxy compound (jER (registered by Mitsubishi Chemical Corporation) Trademark) 828) has a compounding ratio (mass ratio) of 100 to 3 (100/3 described in Table 1), so it becomes a composition in which the carboxyl group-containing polyurethane resin synthesized in Synthesis Example 1 has a residual amount of carboxyl groups in half. In addition, the overcoat layer (corresponding to the second resin layer) of Example 6 is the same as that of Example 1.

[實施例7] [Example 7]

除了變更為表1所示之材料構成以外，與實施例1同樣使用調製之墨水，藉由同樣厚度構成、同樣步驟形成底塗層、導電圖型及上覆層。此時作為上覆層之硬化促進劑係代替CUREZOL(註冊商標)2P4MHZ-PW(四國化成 製)而使用IRGACURE(註冊商標)184(BASF公司製)。又，改變為140℃硬化1小時，使用小型UV照射裝置QRU-2161-Z11-00(ORC製作所股份有限公司)，曝光約40mW/cm2而共硬化。進行實施例1同樣之密著性評價(剝離試驗)、耐擦傷性試驗、光學特性評價之結果示於表1。 Except for changing to the material composition shown in Table 1, the prepared ink was used in the same manner as in Example 1, and the undercoat layer, the conductive pattern, and the overcoat layer were formed with the same thickness and the same procedure. At this time, as a hardening accelerator for the overcoat layer, IRGACURE (registered trademark) 184 (manufactured by BASF) was used instead of CUREZOL (registered trademark) 2P4MHZ-PW (manufactured by Shikoku Chemicals). In addition, it was changed to 140° C. for 1 hour for curing, using a small UV irradiation device QRU-2161-Z11-00 (ORC Manufacturing Co., Ltd.), and exposed to approximately 40 mW/cm 2 for co-curing. Table 1 shows the results of the same adhesion evaluation (peel test), scratch resistance test, and optical characteristic evaluation as in Example 1.

[比較例1] [Comparative Example 1]

變更為表2所示之材料構成形成底塗層。底塗層為液狀狀態且嚴重沾黏，即使以噴墨等之其他印刷法，亦無法進行銀奈米線墨水之印刷。認為係相對於其他例中，分子量為1萬以上，比較例1之樹脂之分子量小如4100為其原因。 Change to the material composition shown in Table 2 to form an undercoat layer. The undercoat layer is in a liquid state and is very sticky. Even with other printing methods such as inkjet, it is impossible to print silver nanowire ink. It is considered that the molecular weight is 10,000 or more compared to other examples, and the resin of Comparative Example 1 has a molecular weight as small as 4100 for the reason.

[比較例2~5] [Comparative Examples 2 to 5]

除了變更為表2所示之材料構成以外，與實施例1同樣使用調製之墨水，藉由同樣厚度構成、同樣步驟形成底塗層、導電圖型及上覆層。但比較例4曝光約40mW/cm2之UV光，進行相當共硬化之處理。進行實施例1同樣之密著性評價(剝離試驗)、耐擦傷性試驗、光學特性評價之結果示於表2。 Except for changing to the material composition shown in Table 2, the prepared ink was used in the same manner as in Example 1, and the undercoat layer, the conductive pattern, and the overcoat layer were formed with the same thickness and the same procedure. However, Comparative Example 4 was exposed to UV light of about 40 mW/cm 2 and subjected to a relatively co-hardening treatment. Table 2 shows the results of the adhesion evaluation (peel test), scratch resistance test, and optical characteristic evaluation similar to Example 1.

實施例1~4中，於底塗層與上覆層使用相同樹脂成分，於共硬化時，因底塗層與上覆層之化學鍵結而密著，未發生剝離。 In Examples 1 to 4, the same resin component was used for the undercoat layer and the overlying layer. During co-hardening, the undercoat layer and the overlying layer were closely adhered due to chemical bonding, and no peeling occurred.

實施例5中，於底塗層與上覆層雖使用不同樹脂成分，但由於具有可共硬化之官能基，故硬化後底塗層與上覆層之間未剝離。相對於此，比較例4、5中，於底塗層與上覆層使用硬化機制不同之樹脂，比較例4施以UV硬化，比較例5施以熱硬化時，底塗層與上覆層並未共硬化，底塗層與上覆層之間發生剝離。 In Example 5, although different resin components are used for the undercoat layer and the overcoat layer, they have co-hardenable functional groups, so there is no peeling between the undercoat layer and the overcoat layer after hardening. In contrast, in Comparative Examples 4 and 5, resins with different curing mechanisms are used for the undercoat layer and the overcoat layer. In Comparative Example 4, UV curing is applied, and in Comparative Example 5, when the thermosetting is applied, the undercoat layer and the overcoat layer There is no co-hardening, and peeling occurs between the undercoat layer and the overlying layer.

又，實施例6中，作為底塗層，係以於含羧基聚胺基甲酸酯中官能基(羧基)殘留半量之比例添加環氧化合物(三菱化學製jER(註冊商標)828)，以100℃乾燥1小時之條件，成為應稱為半硬化之狀態，由於因殘留官能基，亦與上覆層藉由化學鍵結而密著，故底塗層與上覆層未剝離。相對地，比較例2及3中設為使於底塗層與上覆層使用之樹脂可完全硬化之條件，於形成底塗層(100℃，1小時乾燥)之時點，由於底塗層中與上覆層反應之殘留官能基消失，故底塗層與上覆層之間發生剝離(剝離試驗結果為5)。 Furthermore, in Example 6, as a primer layer, an epoxy compound (jER (registered trademark) 828 manufactured by Mitsubishi Chemical Corporation) was added at a ratio of half of the functional group (carboxyl group) remaining in the carboxyl group-containing polyurethane. The condition of drying at 100°C for 1 hour is a state called semi-hardening. Since the remaining functional groups are also closely bonded to the upper layer by chemical bonding, the primer layer and the upper layer are not peeled off. In contrast, in Comparative Examples 2 and 3, the resin used in the undercoat layer and the overcoat layer was completely cured. At the time when the undercoat layer was formed (100°C, dried for 1 hour), due to the undercoat layer The residual functional groups that reacted with the upper cladding layer disappeared, so peeling occurred between the undercoat layer and the upper cladding layer (peeling test result was 5).

由實施例1~6及比較例2~5可知共硬化優異性。 Examples 1 to 6 and Comparative Examples 2 to 5 show the excellent co-hardening.

Figure 105124155-A0202-12-0022-1
Figure 105124155-A0202-12-0022-1

Figure 105124155-A0202-12-0023-2
Figure 105124155-A0202-12-0023-2

除了未設底塗層以外與實施例1同樣構成。進行實施例1同樣之密著性評價(剝離試驗)、耐擦傷性試驗、光學特性評價之結果示於表2。剝離試驗、耐擦傷試驗雖良好，但由於無底塗層，故若加熱銀奈米線分散液塗佈後之PET基板，則全光線透過率降低5%以上，但仍有80%以上。然而，濁度於加熱前為2%者，但加熱後超過50%，大幅損及光學特性。由於因加熱而自PET基板析出寡聚物使表面粗糙度增大，故損及光學特性。 The structure is the same as in Example 1 except that the undercoat layer is not provided. Table 2 shows the results of the adhesion evaluation (peel test), scratch resistance test, and optical characteristic evaluation similar to Example 1. Although the peeling test and scratch resistance test are good, since there is no primer layer, if the PET substrate coated with the silver nanowire dispersion liquid is heated, the total light transmittance is reduced by more than 5%, but still more than 80%. However, the turbidity was 2% before heating, but more than 50% after heating, greatly impairing the optical characteristics. Precipitation of oligomers from the PET substrate due to heating increases the surface roughness, which impairs the optical properties.

[比較例7] [Comparative Example 7]

係未設上覆層之一比較例。進行實施例1同樣之密著性評價(剝離試驗)、耐擦傷性試驗、光學特性評價之結果示於表2。由於無上覆層，故因耐擦傷性試驗於金屬部產生傷痕，且由圖3所示之實施例1同樣之環境耐性之結果，經過約700小時後，電阻開始顯著上升，可知環境耐性低。 It is a comparative example without an overlying layer. Table 2 shows the results of the adhesion evaluation (peel test), scratch resistance test, and optical characteristic evaluation similar to Example 1. Since there is no overlying layer, scratches are produced on the metal part due to the scratch resistance test, and the results of the same environmental resistance as in Example 1 shown in FIG. 3 show that after about 700 hours, the resistance starts to increase significantly, indicating that the environmental resistance is low .

10‧‧‧基板 10‧‧‧ substrate

12‧‧‧第1樹脂層 12‧‧‧The first resin layer

14‧‧‧導電圖型 14‧‧‧Conductive pattern

16‧‧‧第2樹脂層 16‧‧‧The second resin layer

Claims (12)

一種導電薄膜之製造方法，其包含：使用含第1官能基之第1樹脂組成物於基板上形成第1樹脂層之步驟，於前述第1樹脂層上形成俯視具有開口部之導電圖型之步驟，使用含可與前述第1樹脂層之第1官能基共硬化之第2官能基之第2樹脂組成物，以覆蓋前述導電圖型之至少一部分之方式形成第2樹脂層之步驟，及使前述第1樹脂層與第2樹脂層共硬化之步驟。 A method for manufacturing a conductive film, comprising: a step of forming a first resin layer on a substrate using a first resin composition containing a first functional group, and forming a conductive pattern having an opening in a plan view on the first resin layer A step of forming a second resin layer using a second resin composition containing a second functional group co-hardenable with the first functional group of the first resin layer to cover at least a part of the conductive pattern, and The step of co-hardening the first resin layer and the second resin layer. 如請求項1之導電薄膜之製造方法，其中前述導電圖型係於前述第1樹脂層之表面上黏性消失後而形成。 The method for manufacturing a conductive thin film according to claim 1, wherein the conductive pattern is formed after the viscosity on the surface of the first resin layer disappears. 如請求項1或2之導電薄膜之製造方法，其中前述第1官能基包含羧基、羥基、環氧基、(甲基)丙烯醯基、乙烯基、烯丙基之任一者。 The method for manufacturing a conductive film according to claim 1 or 2, wherein the first functional group includes any one of a carboxyl group, a hydroxyl group, an epoxy group, a (meth)acryloyl group, a vinyl group, and an allyl group. 如請求項1或2之導電薄膜之製造方法，其中前述第1樹脂組成物包含含羧基之聚胺基甲酸酯、酚酚醛清漆型環氧樹脂、苯氧基樹脂、含羧基之聚胺基甲酸酯與以羧基基準未達當量之環氧化合物之混合物、鄰苯二甲酸二烯丙酯樹脂之任一者。 The method for manufacturing a conductive film according to claim 1 or 2, wherein the first resin composition includes a carboxyl group-containing polycarbamate, a phenol novolac epoxy resin, a phenoxy resin, and a carboxyl group-containing polyamine group Either a mixture of formate and an epoxy compound having an equivalent amount based on carboxyl groups, or diallyl phthalate resin. 如請求項1或2之導電薄膜之製造方法，其中前述第2樹脂組成物包含含羧基之聚胺基甲酸酯與環氧化合物之混合物、酚酚醛清漆型環氧樹脂、苯氧基樹脂、含羧基之聚胺基甲酸酯與以羧基基準為當量以上之環氧化合物 之混合物、鄰苯二甲酸二烯丙酯樹脂與丙烯酸酯單體之混合物之任一者。 The method for manufacturing a conductive film according to claim 1 or 2, wherein the second resin composition includes a mixture of a carboxyl group-containing polyurethane and an epoxy compound, a phenol novolac epoxy resin, a phenoxy resin, Carbamate-containing polyurethane and epoxy compound with an equivalent weight based on carboxyl group Any of a mixture of diallyl phthalate resins and a mixture of acrylate monomers. 如請求項1或2之導電薄膜之製造方法，其中前述基板、第1樹脂層、導電圖型及第2樹脂層各為透明。 The method for manufacturing a conductive film according to claim 1 or 2, wherein the substrate, the first resin layer, the conductive pattern, and the second resin layer are each transparent. 如請求項3之導電薄膜之製造方法，其中前述第1樹脂組成物包含含羧基之聚胺基甲酸酯、酚酚醛清漆型環氧樹脂、苯氧基樹脂、含羧基之聚胺基甲酸酯與以羧基基準未達當量之環氧化合物之混合物、鄰苯二甲酸二烯丙酯樹脂之任一者。 The method for manufacturing a conductive film according to claim 3, wherein the first resin composition includes a carboxyl group-containing polyurethane, a phenol novolac epoxy resin, a phenoxy resin, and a carboxyl group-containing polycarbamic acid Either a mixture of an ester and an epoxy compound having an equivalent amount based on a carboxyl group, or diallyl phthalate resin. 如請求項7之導電薄膜之製造方法，其中前述第2樹脂組成物包含含羧基之聚胺基甲酸酯與環氧化合物之混合物、酚酚醛清漆型環氧樹脂、苯氧基樹脂、含羧基之聚胺基甲酸酯與以羧基基準為當量以上之環氧化合物之混合物、鄰苯二甲酸二烯丙酯樹脂與丙烯酸酯單體之混合物之任一者。 The method for manufacturing a conductive film according to claim 7, wherein the second resin composition includes a mixture of a urethane group containing a carboxyl group and an epoxy compound, a phenol novolac epoxy resin, a phenoxy resin, and a carboxyl group Any one of a mixture of a polyurethane and an epoxy compound having an equivalent or more based on a carboxyl group, a mixture of diallyl phthalate resin and an acrylate monomer. 一種導電薄膜，其於基板上具有含第1官能基之第1樹脂層，於該第1樹脂層上具有俯視具有開口部之導電圖型，以覆蓋該導電圖型之至少一部分之方式形成含第2官能基之第2樹脂層，且於前述導電圖型開口部具有前述第1樹脂層之第1官能基與第2樹脂層之第2官能基之硬化反應部分。 A conductive film having a first resin layer containing a first functional group on a substrate, a conductive pattern having an opening in a plan view on the first resin layer, formed to cover at least a part of the conductive pattern The second resin layer of the second functional group has a curing reaction portion of the first functional group of the first resin layer and the second functional group of the second resin layer in the conductive pattern opening. 如請求項9之導電薄膜，其中全光線透過率為70%以上。 According to the conductive film of claim 9, the total light transmittance is more than 70%. 如請求項9或10之導電薄膜，其中前述導電圖 型包含具有無序之交叉接觸部之金屬奈米線。 The conductive film as in claim 9 or 10, where the aforementioned conductive pattern The type includes metal nanowires with disordered cross-contacts. 如請求項9或10之導電薄膜，其中前述導電圖型包含規則或不規則地形成之金屬細線圖型。 The conductive film according to claim 9 or 10, wherein the aforementioned conductive pattern includes a pattern of fine metal lines formed regularly or irregularly.
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