TW201513139A - Method for producing conductive film - Google Patents

Method for producing conductive film Download PDF

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Publication number
TW201513139A
TW201513139A TW103129767A TW103129767A TW201513139A TW 201513139 A TW201513139 A TW 201513139A TW 103129767 A TW103129767 A TW 103129767A TW 103129767 A TW103129767 A TW 103129767A TW 201513139 A TW201513139 A TW 201513139A
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Taiwan
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conductive film
substrate
mass
copper oxide
laser light
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TW103129767A
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Chinese (zh)
Inventor
Misato Sasada
Hiroshi Ohta
Yoshihisa Usami
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Fujifilm Corp
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Publication of TW201513139A publication Critical patent/TW201513139A/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/105—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0145—Polyester, e.g. polyethylene terephthalate [PET], polyethylene naphthalate [PEN]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/10—Using electric, magnetic and electromagnetic fields; Using laser light
    • H05K2203/107—Using laser light
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method

Abstract

A method for producing a conductive film is provided, which can produce the conductive film which suppresses generations of defects and has excellent conductivity. The method for producing the conductive film of the invention includes: a step of forming a precursor film including containing cupric oxide particles by applying a dispersion containing the cupric oxide particles having an average particle diameter of 100 nm or less on a substrate; and a step of forming the conductive film including containing metal copper by irradiating a lazer having a wavelength of 9-11 [mu]m to the precursor film while scanning relatively to reduce the cupric oxide particles in a scanning area irradiated by the lazer. A film thickness of the precursor film is 0.5-30 [mu]m, and a scanning speed is 10-120 mm/s. A thermal conductivity A [W/(m,K)] of the substrate and an output of the lazer W [W] satisfy a relation of formula 1, and the thermal conductivity A of the substrate is 0.014 or more. Formula 1 1.39+0.3252Ln (A) ≤ W ≤ 3.00+0.3252Ln (A).

Description

導電膜的製造方法 Method for manufacturing conductive film

本發明是有關於一種導電膜的製造方法，特別是有關於一種藉由以既定的條件照射雷射光而製造導電膜的方法。 The present invention relates to a method for producing a conductive film, and more particularly to a method for producing a conductive film by irradiating laser light under predetermined conditions.

關於在基材上形成金屬膜的方法，已知有以下技術：藉由印刷法將金屬氧化物粒子的分散體塗佈於基材上，並進行光照射處理而使其燒結，藉此形成金屬膜或電路基板的配線等電性導通部位。 Regarding a method of forming a metal film on a substrate, a technique is known in which a dispersion of metal oxide particles is applied onto a substrate by a printing method, and is subjected to light irradiation treatment to be sintered, thereby forming a metal. An electrical conduction portion such as a wiring of a film or a circuit board.

與現有的利用高熱．真空製程(濺鍍)或鍍敷處理的配線製作法相比較，所述方法由於簡便、節能且省資源，故而於下一代電子設備(electronics)開發中備受期待。 With the existing use of high heat. Compared with the wiring manufacturing method of the vacuum process (sputtering) or the plating process, the method is expected to be developed in the next generation of electronic devices because of its simplicity, energy saving, and resource saving.

例如，於專利文獻1(特別是實施例)中揭示有一種導電圖案的形成方法，其對含有包含金屬或複合金屬的膠體粒子的微粒子層以既定的條件(線速、輸出等)進行雷射照射。 For example, Patent Document 1 (particularly, an embodiment) discloses a method of forming a conductive pattern which performs laser irradiation on a fine particle layer containing colloidal particles containing a metal or a composite metal under predetermined conditions (linear velocity, output, etc.). Irradiation.

[現有技術文獻] [Prior Art Literature]

[專利文獻] [Patent Literature]

[專利文獻1]日本專利特開2004-143571號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-143571

另一方面，近年來，就低成本化的觀點而言，要求開發出以下方法：使用含有氧化銅粒子的組成物，形成導電性優異的含有金屬的導電膜。 On the other hand, in recent years, from the viewpoint of cost reduction, it has been required to develop a method of forming a metal-containing conductive film having excellent conductivity by using a composition containing copper oxide particles.

另外，近年來為了應對電子設備的小型化、高功能化的要求，而於印刷配線板等中正在推進配線的進一步的微細化及高積體化。伴隨於此，要求所形成的導電膜並無缺陷，及進一步提高導電膜的導電性等。 In addition, in recent years, in order to cope with the demand for miniaturization and high functionality of electronic equipment, further miniaturization and high integration of wiring are being promoted in printed wiring boards and the like. Along with this, it is required that the formed conductive film has no defects, and the conductivity of the conductive film or the like is further improved.

本發明者等人參照專利文獻1，將含有氧化銅粒子的分散液塗佈於基材上而形成含有氧化銅粒子的層，並對含有氧化銅粒子的層掃描雷射光，藉此進行導電膜的製作，結果發現，於專利文獻1中具體揭示的條件下，所得的導電膜含有缺陷，導電性不足。 The inventors of the present invention have referred to Patent Document 1 to apply a dispersion containing copper oxide particles to a substrate to form a layer containing copper oxide particles, and to scan a layer containing copper oxide particles to scan a laser beam, thereby performing a conductive film. As a result of the production, it was found that under the conditions specifically disclosed in Patent Document 1, the obtained conductive film contained defects and the conductivity was insufficient.

鑒於所述實際情況，本發明的目的在於提供一種導電膜的製造方法，其可製造抑制缺陷的產生、導電性優異的導電膜。 In view of the above circumstances, an object of the present invention is to provide a method for producing a conductive film which can produce a conductive film which is excellent in conductivity and which suppresses generation of defects.

本發明者等人對現有技術的問題進行了潛心研究，結果發現，藉由控制雷射光的掃描條件、照射條件等，可解決所述課題。 The inventors of the present invention have conducted intensive studies on the problems of the prior art, and as a result, have found that the problem can be solved by controlling scanning conditions, irradiation conditions, and the like of laser light.

即發現，可藉由以下的構成來達成所述目的。 That is, it was found that the object can be achieved by the following constitution.

(1)一種導電膜的製造方法，包括以下步驟：將含有平均粒徑為100nm以下的氧化銅粒子的分散液塗佈於 基材上，形成含有氧化銅粒子的前驅物膜的步驟；以及對前驅物膜一面照射波長為9μm~11μm的雷射光一面相對地掃描，將經雷射光照射的掃描區域中的氧化銅粒子還原，形成含有金屬銅的導電膜的步驟；並且前驅物膜的膜厚為0.5μm~30μm，掃描的速度為10mm/s~120mm/s，基材的熱傳導率A[W/(m．K)]與雷射光的輸出W[W]滿足式1的關係，基材的熱傳導率A為0.014以上，式1 1.39+0.3252Ln(A)≦W≦3.00+0.3252Ln(A)。 (1) A method for producing a conductive film, comprising the steps of: applying a dispersion containing copper oxide particles having an average particle diameter of 100 nm or less to a step of forming a precursor film containing copper oxide particles on the substrate; and relatively scanning the precursor film with a laser beam having a wavelength of 9 μm to 11 μm, and reducing the copper oxide particles in the scanning region irradiated with the laser light a step of forming a conductive film containing metallic copper; and a film thickness of the precursor film of 0.5 μm to 30 μm, a scanning speed of 10 mm/s to 120 mm/s, and a thermal conductivity of the substrate A [W/(m.K) The output W [W] of the laser light satisfies the relationship of Formula 1, and the thermal conductivity A of the substrate is 0.014 or more, and Equation 1 1.39 + 0.3252 Ln (A) ≦ W ≦ 3.00 + 0.3252 Ln (A).

(2)如(1)所記載的導電膜的製造方法，其中基材的熱傳導率A[W/(m．K)]與雷射光的輸出W[W]滿足式2的關係，式2 1.39+0.3252Ln(A)≦W≦2.40+0.3252Ln(A)。 (2) The method for producing a conductive film according to (1), wherein the thermal conductivity A [W/(m.K)] of the substrate and the output W[W] of the laser light satisfy the relationship of Formula 2, and Equation 2 1.39 +0.3252Ln(A)≦W≦2.40+0.3252Ln(A).

(3)如(1)或(2)所記載的導電膜的製造方法，其中於利用雷射光對與經雷射光照射的第1掃描區域鄰接的區域進行掃描時，以與第1掃描區域局部重複的方式照射雷射光，重複區域的寬度相當於雷射光的點徑的15%~30%的大小。 (3) The method for producing a conductive film according to the above aspect, wherein the region adjacent to the first scanning region irradiated with the laser light is scanned by the laser light, and the first scanning region is partially The laser light is irradiated in a repeated manner, and the width of the repeating region is equivalent to 15% to 30% of the spot diameter of the laser light.

(4)如(1)至(3)中任一項所記載的導電膜的製造方法，其中基材為選自由聚對苯二甲酸乙二酯基材、聚萘二甲酸乙二酯 基材、聚醯亞胺基材及玻璃環氧樹脂基材所組成的組群中的任一種。 The method for producing a conductive film according to any one of (1) to (3) wherein the substrate is selected from the group consisting of polyethylene terephthalate substrate and polyethylene naphthalate. Any one of a group consisting of a substrate, a polyimide substrate, and a glass epoxy substrate.

(5)如(1)至(4)中任一項所記載的導電膜的製造方法，其中於分散液中含有選自由乙烯系聚合物、聚醚及糖所組成的組群中的至少一種有機化合物。 The method for producing a conductive film according to any one of the above aspects, wherein the dispersion contains at least one selected from the group consisting of a vinyl polymer, a polyether, and a sugar. Organic compound.

(6)如(5)所記載的導電膜的製造方法，其中有機化合物含有選自由聚乙烯基吡咯啶酮、聚乙二醇及糖所組成的組群中的至少一種。 (6) The method for producing a conductive film according to the above aspect, wherein the organic compound contains at least one selected from the group consisting of polyvinylpyrrolidone, polyethylene glycol, and sugar.

(7)如(5)或(6)所記載的導電膜的製造方法，其中相對於氧化銅粒子的總質量，有機化合物的含量為8質量%~20質量%。 (7) The method for producing a conductive film according to (5) or (6), wherein the content of the organic compound is from 8 to 20% by mass based on the total mass of the copper oxide particles.

(8)如(1)至(7)中任一項所記載的導電膜的製造方法，其中於分散液中含有平均粒徑為0.4μm~3.5μm的銅粒子，且掃描的速度為10mm/s~80mm/s。 (8) The method for producing a conductive film according to any one of (1), wherein the dispersion contains copper particles having an average particle diameter of 0.4 μm to 3.5 μm, and the scanning speed is 10 mm/ s~80mm/s.

(9)如(8)所記載的導電膜的製造方法，其中相對於氧化銅粒子的總質量，銅粒子的含量為30質量%~200質量%。 (9) The method for producing a conductive film according to the item (8), wherein the content of the copper particles is from 30% by mass to 200% by mass based on the total mass of the copper oxide particles.

(10)如(1)至(9)中任一項所記載的導電膜的製造方法，其中掃描的速度為10mm/s~60mm/s；基材為聚對苯二甲酸乙二酯基材或聚萘二甲酸乙二酯基材；於分散液中含有聚乙二醇，相對於氧化銅粒子的總質量，聚乙二醇的含量為8質量%~14質量%； 於分散液中含有平均粒徑為1.0μm~3.5μm的銅粒子，相對於氧化銅粒子的總質量，銅粒子的含量為30質量%~70質量%；基材的熱傳導率A[W/(m．K)]與雷射光的輸出W[W]滿足式3的關係，式3 1.39+0.3252Ln(A)≦W≦1.75+0.3252Ln(A)。 (10) The method for producing a conductive film according to any one of (1) to (9) wherein the scanning speed is from 10 mm/s to 60 mm/s; and the substrate is a polyethylene terephthalate substrate. Or a polyethylene naphthalate substrate; the polyethylene glycol is contained in the dispersion, and the content of the polyethylene glycol is 8% by mass to 14% by mass based on the total mass of the copper oxide particles; The copper particles having an average particle diameter of 1.0 μm to 3.5 μm are contained in the dispersion, and the content of the copper particles is 30% by mass to 70% by mass based on the total mass of the copper oxide particles; the thermal conductivity of the substrate A [W/( m.K)] and the output of the laser light W[W] satisfy the relationship of Equation 3, Equation 3 1.39+0.3252Ln(A)≦W≦1.75+0.3252Ln(A).

根據本發明，可提供一種導電膜的製造方法，其可高效地將氧化銅粒子還原成金屬銅，製造抑制缺陷的產生、導電性優異的導電膜。 According to the present invention, it is possible to provide a method for producing a conductive film which can efficiently reduce copper oxide particles to metallic copper and produce a conductive film which is excellent in conductivity and which suppresses generation of defects.

10‧‧‧基材 10‧‧‧Substrate

12‧‧‧前驅物膜 12‧‧‧Precursor film

14‧‧‧雷射光源 14‧‧‧Laser light source

16‧‧‧雷射光 16‧‧‧Laser light

18‧‧‧導電膜 18‧‧‧Electrical film

20‧‧‧掃描區域 20‧‧‧Scanning area

22‧‧‧鄰接區域 22‧‧‧Adjacent areas

24‧‧‧重複區域 24‧‧‧Repeating area

D‧‧‧點徑 D‧‧‧ Point

W‧‧‧寬度 W‧‧‧Width

圖1為表示照射步驟的態樣的概略圖。 Fig. 1 is a schematic view showing an aspect of an irradiation step.

圖2為表示式1的範圍的圖。 FIG. 2 is a view showing the range of Formula 1.

圖3為表示照射步驟的較佳態樣的概略圖。 Fig. 3 is a schematic view showing a preferred aspect of the irradiation step.

以下，對本發明的導電膜的製造方法的較佳態樣加以詳述。再者，本說明書中使用「~」所表示的數值範圍是指包括「~」的前後所記載的數值作為下限值及上限值的範圍。 Hereinafter, preferred aspects of the method for producing a conductive film of the present invention will be described in detail. In addition, the numerical range represented by "~" in this specification is the range which shows the numerical value of the before and the

首先，對本發明的與現有技術相比較的特徵加以詳述。 First, the features of the present invention which are compared with the prior art will be described in detail.

如上文所述，本發明的特徵可列舉控制雷射光的照射條件、 以及雷射光與被照射物(前驅物膜)的掃描條件的方面。更具體而言發現，藉由控制掃描速度以及所使用的基材的熱傳導率及雷射光的輸出的關係，可獲得所需效果。藉由如上所述般控制條件可獲得所需效果的機制，將如以下般加以說明。 As described above, the features of the present invention can be exemplified by controlling the irradiation conditions of the laser light, And aspects of the scanning conditions of the laser light and the object to be irradiated (precursor film). More specifically, it has been found that the desired effect can be obtained by controlling the scanning speed and the relationship between the thermal conductivity of the substrate used and the output of the laser light. The mechanism by which the desired effect can be obtained by controlling the conditions as described above will be explained as follows.

首先，若對含有既定大小的氧化銅粒子的前驅物膜(被照射物)照射雷射光，則被照射物所吸收的雷射光被轉變成熱能。所轉變的熱能局部傳導至鄰接的基材中，但此時，前驅物中的熱能的量視基材的熱傳導率而變化。具體而言，於基材的熱傳導率過高的情形時，前驅物膜中的熱能大部分移動至基材中，導致氧化銅粒子的還原未充分進行，於基材的熱傳導率過低的情形時，前驅物膜中的熱能殘存而進行不需要的副反應。本發明根據所述見解發現適於氧化銅粒子的還原的基材的熱傳導率與雷射光的輸出的較佳關係、較佳的掃描速度及較佳的前驅物膜的厚度。 First, when a precursor film (an object to be irradiated) containing a predetermined size of copper oxide particles is irradiated with laser light, the laser light absorbed by the object to be irradiated is converted into heat energy. The converted thermal energy is locally conducted into the adjacent substrate, but at this point, the amount of thermal energy in the precursor varies depending on the thermal conductivity of the substrate. Specifically, when the thermal conductivity of the substrate is too high, most of the thermal energy in the precursor film moves into the substrate, resulting in insufficient reduction of the copper oxide particles, and the thermal conductivity of the substrate is too low. At the time, the thermal energy in the precursor film remains and an unnecessary side reaction is performed. The present invention finds, based on the above findings, a preferred relationship between the thermal conductivity of a substrate suitable for reduction of copper oxide particles and the output of laser light, a preferred scanning speed, and a preferred thickness of the precursor film.

本發明的導電膜的製造方法的較佳態樣包括至少兩個步驟，即，形成前驅物膜的步驟(前驅物膜形成步驟)、以及對前驅物膜照射雷射光的步驟(照射步驟)。 A preferred aspect of the method for producing a conductive film of the present invention includes at least two steps, a step of forming a precursor film (precursor film forming step), and a step of irradiating the precursor film with laser light (irradiation step).

以下，對各步驟中使用的材料、順序分別加以詳述。 Hereinafter, the materials and the order used in each step will be described in detail.

[前驅物膜形成步驟] [Precursor film formation step]

前驅物膜形成步驟為以下步驟：將含有平均粒徑為100nm以下的氧化銅粒子的分散液塗佈於基材上，形成含有氧化銅粒子的前驅物膜。藉由實施該步驟，而形成後述經雷射光照射的前驅物膜。 The precursor film forming step is a step of applying a dispersion liquid containing copper oxide particles having an average particle diameter of 100 nm or less to a substrate to form a precursor film containing copper oxide particles. By performing this step, a precursor film irradiated with laser light, which will be described later, is formed.

以下，首先對該步驟中使用的材料加以詳述，其後對步驟的順序加以詳述。 Hereinafter, the materials used in the steps will be described in detail first, and the order of the steps will be described in detail later.

(氧化銅粒子) (copper oxide particles)

於分散液中含有氧化銅粒子。氧化銅粒子藉由後述雷射光照射處理而被還原，構成導電膜中的金屬銅。 The copper oxide particles are contained in the dispersion. The copper oxide particles are reduced by laser light irradiation treatment described later to constitute metallic copper in the conductive film.

本發明中所謂「氧化銅」，是實質上不含未經氧化的銅的化合物，具體而言是指於由X射線繞射所得的結晶分析中，檢測到來源於氧化銅的峰值、且未檢測到來源於金屬的峰值的化合物。所謂實質上不含銅，並無限定，是指銅的含量相對於氧化銅粒子而為1質量%以下。 In the present invention, "copper oxide" is a compound which does not substantially contain copper which is not oxidized, and specifically means that a peak derived from copper oxide is detected in the crystallization analysis obtained by X-ray diffraction. A compound derived from the peak of the metal was detected. The content of copper is not particularly limited, and the content of copper is 1% by mass or less based on the copper oxide particles.

氧化銅較佳為氧化銅(I)或氧化銅(II)，就可廉價地獲取且穩定的方面而言，更佳為氧化銅(II)。 The copper oxide is preferably copper (I) oxide or copper (II) oxide, and is preferably copper oxide (II) in terms of being inexpensively obtained and stable.

氧化銅粒子的平均粒徑為100nm以下。若平均粒徑為100nm以下，則良好地將氧化銅還原成金屬銅，可獲得所需的導電膜。其中，就效果更優異的方面而言，更佳為50nm以下。下限亦無特別限制，就粒子表面的活性不會變得過高、操作性優異的方面而言，較佳為10nm以上。 The average particle diameter of the copper oxide particles is 100 nm or less. When the average particle diameter is 100 nm or less, the copper oxide is favorably reduced to metallic copper, and a desired conductive film can be obtained. Among them, in terms of more excellent effects, it is more preferably 50 nm or less. The lower limit is not particularly limited, and is preferably 10 nm or more from the viewpoint that the activity on the surface of the particles does not become excessively high and the workability is excellent.

於氧化銅粒子的平均粒徑超過100nm的情形時，所得的導電膜中容易產生缺陷，另外，還原成銅的還原性劣化，故導電膜的導電性差。 When the average particle diameter of the copper oxide particles exceeds 100 nm, defects are likely to occur in the obtained conductive film, and the reduction property of reduction to copper is deteriorated, so that the conductivity of the conductive film is poor.

再者，平均粒徑是指平均一次粒徑。平均粒徑是藉由穿透式電子顯微鏡(Trasmission Electron Microscope，TEM)觀察或掃描 式電子顯微鏡(Scanning Electron Microscope，SEM)觀察來測定至少50個以上的氧化銅粒子的粒徑(直徑)，並對該等加以算術平均而求出。再者，觀察圖中，於氧化銅粒子的形狀並非正圓狀的情形時，將長徑作為直徑來進行測定。 Further, the average particle diameter means an average primary particle diameter. The average particle size is observed or scanned by a Trasmission Electron Microscope (TEM) The particle diameter (diameter) of at least 50 or more copper oxide particles was measured by a scanning electron microscope (SEM), and these were arithmetically averaged. In the observation chart, when the shape of the copper oxide particles is not a perfect circular shape, the long diameter is measured as the diameter.

(含有氧化銅粒子的分散液) (dispersion containing copper oxide particles)

於分散液中含有所述氧化銅粒子。另外，視需要亦可含有溶劑。溶劑作為氧化銅粒子的分散介質而發揮功能。 The copper oxide particles are contained in the dispersion. Further, a solvent may be contained as needed. The solvent functions as a dispersion medium of the copper oxide particles.

溶劑的種類並無特別限制，例如可使用水或醇類、醚類、酯類等有機溶劑等。再者，醇可列舉多元醇(具有2個以上的羥基的化合物)，例如可列舉：乙二醇、二乙二醇、1,2-丙二醇(propylene glycol，丙二醇)、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、戊二醇、己二醇、辛二醇等二醇類，1,2,3-丙三醇(甘油)、1,2,4-丁三醇等三醇類等。 The type of the solvent is not particularly limited, and for example, water or an organic solvent such as an alcohol, an ether or an ester can be used. Further, examples of the alcohol include a polyhydric alcohol (a compound having two or more hydroxyl groups), and examples thereof include ethylene glycol, diethylene glycol, 1,2-propylene glycol (propylene glycol), and 1,3-propanediol. 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, pentanediol, hexanediol, octanediol and other glycols, 1, Triols such as 2,3-propanetriol (glycerol) and 1,2,4-butanetriol.

另外，其中就氧化銅粒子的分散性更優異的方面而言，可較佳地使用水、一價~三價的具有羥基的脂肪族醇、來源於該脂肪族醇的烷基醚、來源於該脂肪族醇的烷基酯或該等的混合物。 Further, in the aspect in which the dispersibility of the copper oxide particles is more excellent, water, a monovalent to trivalent aliphatic alcohol having a hydroxyl group, an alkyl ether derived from the aliphatic alcohol, and the like can be preferably used. An alkyl ester of the aliphatic alcohol or a mixture of the same.

更具體可列舉：乙二醇、二乙二醇、1,2-丙二醇(丙二醇)、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、戊二醇、己二醇、辛二醇等二醇類，1,2,3-丙三醇(甘油)、1,2,4-丁三醇等三醇類。 More specifically, ethylene glycol, diethylene glycol, 1,2-propylene glycol (propylene glycol), 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butylene Glycols such as diol, 2,3-butanediol, pentanediol, hexanediol, and octanediol, 1,2,3-propanetriol (glycerol), 1,2,4-butanetriol, etc. Triols.

再者，分散液中，視需要亦可含有其他成分(例如有機化合物、金屬粒子等)。以下，對其他成分加以詳述。 Further, the dispersion may contain other components (for example, an organic compound or a metal particle) as needed. Hereinafter, other components will be described in detail.

(有機化合物) (organic compound)

分散液中，亦可含有選自由乙烯系聚合物、聚醚及糖所組成的組群中的一種有機化合物。該些有機化合物作為前驅物膜的黏合劑材料發揮功能，並且於後述雷射光照射時亦作為氧化銅粒子的還原劑發揮作用。 The dispersion may further contain an organic compound selected from the group consisting of a vinyl polymer, a polyether, and a sugar. These organic compounds function as a binder material of the precursor film, and also function as a reducing agent for the copper oxide particles when irradiated with laser light to be described later.

乙烯系聚合物例如可列舉：羧基乙烯基聚合物(卡波姆(Carbomer))、聚乙烯醇、聚乙烯基甲基醚、聚乙烯基吡咯啶酮、聚馬來酸、聚衣康酸、聚富馬酸、聚(對苯乙烯羧酸等)等。該等中，較佳為聚乙烯醇、聚乙烯基吡咯啶酮，更佳為聚乙烯基吡咯啶酮。 Examples of the vinyl polymer include a carboxyvinyl polymer (Carbomer), polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, polymaleic acid, polyitaconic acid, Polyfumaric acid, poly(p-styrenecarboxylic acid, etc.), and the like. Among these, polyvinyl alcohol and polyvinylpyrrolidone are preferred, and polyvinylpyrrolidone is more preferred.

聚醚較佳為重複單元為碳數2~6的伸烷基的直鏈狀脂肪族聚醚化合物。直鏈狀脂肪族聚醚化合物亦可為二元以上的聚醚共聚物或聚醚嵌段共聚物。 The polyether is preferably a linear aliphatic polyether compound in which the repeating unit is an alkylene group having 2 to 6 carbon atoms. The linear aliphatic polyether compound may also be a binary polyether copolymer or a polyether block copolymer.

直鏈狀聚醚化合物例如除了聚乙二醇、聚丙二醇、聚丁二醇般的聚醚均聚物以外，可列舉：乙二醇/丙二醇、乙二醇/丁二醇的二元共聚物，乙二醇/丙二醇/乙二醇、丙二醇/乙二醇/丙二醇、乙二醇/丁二醇/乙二醇等的直鏈狀的三元共聚物，但不限定於該等。嵌段共聚物可列舉：聚乙二醇聚丙二醇、聚乙二醇聚丁二醇般的二元嵌段共聚物，進而聚乙二醇聚丙二醇聚乙二醇、聚丙二醇聚乙二醇聚丙二醇、聚乙二醇聚丁二醇聚乙二醇等直鏈狀的三元嵌段共聚物般的聚醚嵌段共聚物。 The linear polyether compound is, for example, a polyether homopolymer such as polyethylene glycol, polypropylene glycol or polybutylene glycol, and examples thereof include a binary copolymer of ethylene glycol/propylene glycol and ethylene glycol/butanediol. A linear terpolymer of ethylene glycol/propylene glycol/ethylene glycol, propylene glycol/ethylene glycol/propylene glycol, ethylene glycol/butanediol/ethylene glycol, etc., but is not limited thereto. The block copolymer may be exemplified by polyethylene glycol polypropylene glycol, polyethylene glycol polybutylene glycol-like diblock copolymer, and further polyethylene glycol polypropylene glycol polyethylene glycol, polypropylene glycol polyethylene glycol polymerization. A polyether block copolymer such as a linear ternary block copolymer such as propylene glycol or polyethylene glycol polybutylene glycol polyethylene glycol.

糖的種類並無特別限制，例如可列舉：核酮糖(ribulose)、木酮糖(xylulose)、核糖(ribose)、***糖、木糖、 來蘇糖(lyxose)、脫氧核糖、阿洛酮糖(psicose)、果糖、山梨糖、塔格糖(tagatose)、阿洛糖、阿卓糖(altrose)、葡萄糖、甘露糖、古洛糖(gulose)、艾杜糖、半乳糖、塔羅糖、岩藻糖(fucose)、墨角藻糖(fuculose)、鼠李糖、庚糖、景天庚酮糖(sedoheptulose)等。 The type of the sugar is not particularly limited, and examples thereof include ribulose, xylulose, ribose, arabinose, and xylose. Lyxose, deoxyribose, psicose, fructose, sorbose, tagatose, allose, altrose, glucose, mannose, gulose Gulose), idose, galactose, talose, fucose, fuculose, rhamnose, heptose, sedoheptulose, and the like.

分散液中的有機化合物的含量並無特別限制，就所得的導電膜的缺陷更少、導電性更優異的方面而言，相對於氧化銅粒子的總質量，較佳為6質量%~40質量%，更佳為8質量%~20質量%，進而佳為8質量%~14質量%。 The content of the organic compound in the dispersion is not particularly limited, and the obtained conductive film has less defects and more excellent conductivity, and is preferably 6 mass% to 40 mass with respect to the total mass of the copper oxide particles. % is more preferably 8 mass% to 20 mass%, and further preferably 8 mass% to 14 mass%.

(銅粒子) (copper particles)

於分散液中，亦可更含有銅粒子。銅粒子與藉由後述雷射光照射處理將氧化銅還原所生成的金屬銅一起構成導電膜中的金屬銅。藉由與氧化銅粒子一起而含有銅粒子，所形成的導電膜的導電性變得更優異。 In the dispersion, it is also possible to further contain copper particles. The copper particles constitute metal copper in the conductive film together with the metal copper formed by reducing the copper oxide by the laser light irradiation treatment described later. By containing copper particles together with the copper oxide particles, the conductivity of the formed conductive film is further improved.

銅粒子的平均粒徑並無特別限制，就所得的導電膜的缺陷更少、導電性更優異的方面而言，較佳為0.3μm~10μm，更佳為0.40μm~3.5μm，進而佳為1.0μm~3.5μm。 The average particle diameter of the copper particles is not particularly limited, and the obtained conductive film has less defects and more excellent conductivity, and is preferably 0.3 μm to 10 μm, more preferably 0.40 μm to 3.5 μm, and further preferably 1.0μm~3.5μm.

再者，平均粒徑是指平均一次粒徑。平均粒徑是藉由穿透式電子顯微鏡(TEM)觀察或掃描式電子顯微鏡(SEM)觀察來測定至少50個以上的銅粒子的粒徑(直徑)，並將該等加以算術平均而求出。再者，觀察圖中，於銅粒子的形狀並非正圓狀的情形時，將長徑作為直徑來進行測定。 Further, the average particle diameter means an average primary particle diameter. The average particle diameter is measured by a transmission electron microscope (TEM) observation or a scanning electron microscope (SEM) to measure the particle diameter (diameter) of at least 50 or more copper particles, and these are arithmetically averaged. . In the observation chart, when the shape of the copper particles is not a perfect circular shape, the long diameter is measured as the diameter.

分散液中的銅粒子的含量並無特別限制，就所得的導電膜的缺陷更少、導電性更優異的方面而言，相對於氧化銅粒子的總質量，較佳為30質量%~500質量%，更佳為30質量%~200質量%。再者，於基材為聚萘二甲酸乙二酯基材的情形時，最佳為30質量%~70質量%。 The content of the copper particles in the dispersion is not particularly limited, and the obtained conductive film has less defects and more excellent electrical conductivity, and is preferably 30% by mass to 500% by mass based on the total mass of the copper oxide particles. %, more preferably 30% by mass to 200% by mass. Further, in the case where the substrate is a polyethylene naphthalate substrate, it is preferably from 30% by mass to 70% by mass.

(基材) (substrate)

該步驟中使用的基材只要為與雷射光的輸出W滿足後述式1的關係的基材，則並無特別限制。基材所使用的材料例如可列舉：樹脂、紙、玻璃、矽系半導體、化合物半導體、金屬氧化物、金屬氮化物、木材或該等的複合物。 The base material used in this step is not particularly limited as long as it is a substrate that satisfies the relationship of the following formula 1 with respect to the output W of the laser light. Examples of the material used for the substrate include resin, paper, glass, lanthanide semiconductor, compound semiconductor, metal oxide, metal nitride, wood, or a composite thereof.

更具體可列舉：低密度聚乙烯樹脂、高密度聚乙烯樹脂、丙烯腈-丁二烯-苯乙烯(Acrylonitrile-Butadiene-Styrene，ABS)樹脂、丙烯酸系樹脂、苯乙烯樹脂、氯乙烯樹脂、聚酯樹脂(聚對苯二甲酸乙二酯)、聚縮醛樹脂、聚碸樹脂、聚醚醯亞胺樹脂、聚醚酮樹脂、纖維素衍生物等樹脂基材；非塗佈印刷用紙、微塗佈印刷用紙、塗佈印刷用紙(銅版紙、塗層紙)、特殊印刷用紙、影印用紙(普通紙複印機(Plain Paper Copier，PPC)用紙)、未漂白包裝紙(重袋用未上光牛皮紙、未上光牛皮紙)、漂白包裝紙(漂白牛皮紙、純白卷紙)、塗佈紙板、萬花板(chipboard)、硬紙板等紙基材；鈉玻璃、硼矽酸玻璃、二氧化矽玻璃、石英玻璃等玻璃基材；非晶矽、多晶矽等矽系半導體基材；CdS、CdTe、GaAs等化合物半導體基材；銅板、鐵板、鋁板等金屬基材；氧化鋁、藍 寶石、氧化鋯、氧化鈦、氧化釔、氧化銦、氧化銦錫(Indium Tin Oxide，ITO)、氧化銦鋅(Indium Zinc Oxide，IZO)、奈塞(Nesa，氧化錫)、ATO(摻銻的氧化錫)、摻氟的氧化錫、氧化鋅、AZO(摻鋁的氧化鋅)、摻鎵的氧化鋅、氮化鋁基材、碳化矽等其他無機基材；紙-酚樹脂、紙-環氧樹脂、紙-聚酯樹脂等紙-樹脂複合物，玻璃布-環氧樹脂、玻璃布-聚醯亞胺系樹脂、玻璃布-氟樹脂等玻璃-樹脂複合物等複合基材等。 More specifically, low density polyethylene resin, high density polyethylene resin, acrylonitrile-butadiene-Styrene (ABS) resin, acrylic resin, styrene resin, vinyl chloride resin, poly Resin resin (polyethylene terephthalate), polyacetal resin, polyfluorene resin, polyether phthalimide resin, polyether ketone resin, cellulose derivative and other resin substrates; non-coated printing paper, micro Coated printing paper, coated printing paper (coated paper, coated paper), special printing paper, photocopying paper (Plain Paper Copier (PPC) paper), unbleached wrapping paper (uncoated kraft paper for heavy bags) , non-glazed kraft paper), bleached wrapper (bleached kraft paper, pure white roll paper), coated paperboard, chipboard, cardboard and other paper substrates; soda glass, borosilicate glass, cerium oxide glass, Glass substrate such as quartz glass; lanthanide semiconductor substrate such as amorphous yttrium or polycrystalline yttrium; compound semiconductor substrate such as CdS, CdTe, GaAs; metal substrate such as copper plate, iron plate, aluminum plate; alumina, blue Gems, zirconia, titania, yttria, indium oxide, indium tin oxide (ITO), indium zinc oxide (Indium Zinc Oxide, IZO), Nessai (Nesa, tin oxide), ATO (ytterbium-doped Tin oxide), fluorine-doped tin oxide, zinc oxide, AZO (aluminum-doped zinc oxide), gallium-doped zinc oxide, aluminum nitride substrate, tantalum carbide, and other inorganic substrates; paper-phenol resin, paper-ring A paper-resin composite such as an oxygen resin or a paper-polyester resin, a composite substrate such as a glass cloth-epoxy resin, a glass cloth-polyimine resin, or a glass-resin composite such as a glass cloth-fluoro resin.

其中，基材例如較佳為選自由聚醯亞胺基材、聚對苯二甲酸乙二酯基材、聚萘二甲酸乙二酯基材、聚碳酸酯基材、纖維素酯基材、聚氯乙烯基材、聚乙酸乙烯酯基材、聚胺基甲酸酯基材、矽酮基材、聚乙烯基乙基醚基材、聚硫醚基材、聚烯烴基材、聚丙烯酸酯基材及玻璃環氧基材所組成的組群中的至少一種。進而佳為選自由聚對苯二甲酸乙二酯基材、聚萘二甲酸乙二酯基材、聚醯亞胺基材及玻璃環氧基材所組成的組群中的任一種。 Wherein, the substrate is preferably selected from the group consisting of a polyimide substrate, a polyethylene terephthalate substrate, a polyethylene naphthalate substrate, a polycarbonate substrate, a cellulose ester substrate, Polyvinyl chloride material, polyvinyl acetate substrate, polyurethane substrate, anthrone substrate, polyvinyl ethyl ether substrate, polysulfide substrate, polyolefin substrate, polyacrylate At least one of a group consisting of a substrate and a glass epoxy substrate. Further, it is preferably selected from the group consisting of a polyethylene terephthalate substrate, a polyethylene naphthalate substrate, a polyimide substrate, and a glass epoxy substrate.

基材的熱傳導率A[W/(m．K)]為0.014以上，只要滿足後述式1的關係即可，就操作性優異、所得的導電膜的缺陷更少、導電性更優異的方面而言，較佳為0.1W/(m．K)~1.0W/(m．K)，更佳為0.1W/(m．K)~0.6W/(m．K)。 The thermal conductivity A [W/(m.K)] of the substrate is 0.014 or more, and the relationship of the following formula 1 is satisfied, and the workability is excellent, the obtained conductive film has fewer defects, and the conductivity is more excellent. Preferably, it is 0.1 W/(m.K) to 1.0 W/(m.K), more preferably 0.1 W/(m.K) to 0.6 W/(m.K).

(步驟的順序) (order of steps)

將所述分散液賦予至基材上的方法並無特別限制，可採用公知的方法。例如可列舉：網版印刷法、浸漬塗佈法、噴霧塗佈法、旋轉塗佈法、噴墨法等塗佈法。 The method of imparting the dispersion to the substrate is not particularly limited, and a known method can be employed. For example, a coating method such as a screen printing method, a dip coating method, a spray coating method, a spin coating method, or an inkjet method can be mentioned.

塗佈的形狀並無特別限制，可為覆蓋基材整個面的面狀，亦可為圖案狀(例如配線狀、點狀)。 The shape to be applied is not particularly limited, and may be a planar shape covering the entire surface of the substrate, or may be a pattern (for example, a wiring shape or a dot shape).

該步驟中，視需要亦可於將分散液塗佈於基材上後進行乾燥處理，將溶劑去除。藉由將殘存的溶劑去除，可於後述照射步驟中，抑制由溶劑的氣化膨脹所引起的微小裂縫或空隙的產生，於導電膜的導電性及導電膜與基材的密接性的方面而言較佳。 In this step, if necessary, the dispersion may be applied to a substrate, followed by drying treatment to remove the solvent. By removing the remaining solvent, it is possible to suppress generation of minute cracks or voids caused by vaporization expansion of the solvent in the irradiation step described later, and to improve the conductivity of the conductive film and the adhesion between the conductive film and the substrate. Better words.

乾燥處理的方法可使用利用溫風乾燥機、熱板等的基材的加熱等，溫度較佳為不發生氧化銅粒子的還原的溫度，較佳為於40℃~200℃下進行加熱處理，更佳為於50℃以上、小於150℃的溫度下進行加熱處理，進而佳為於70℃~120℃下進行加熱處理。 The drying treatment method may be a heating using a substrate such as a warm air dryer or a hot plate, and the temperature is preferably a temperature at which reduction of the copper oxide particles does not occur, and it is preferably heat-treated at 40 to 200 ° C. More preferably, it is heat-treated at a temperature of 50 ° C or more and less than 150 ° C, and is preferably heat-treated at 70 ° C to 120 ° C.

(前驅物膜) (precursor film)

前驅物膜含有氧化銅粒子，藉由後述光照射將氧化銅粒子還原成金屬銅，成為導電膜。 The precursor film contains copper oxide particles, and the copper oxide particles are reduced to metallic copper by light irradiation described later to form a conductive film.

前驅物膜中含有氧化銅粒子，尤佳為作為主成分而含有。此處所謂主成分，是指於前驅物膜總質量中，氧化銅粒子所佔的質量為20質量%以上，較佳為50質量%以上。上限並無特別限制，可列舉100質量%。 The precursor film contains copper oxide particles, and is preferably contained as a main component. The term "main component" as used herein means that the mass of the copper oxide particles is 20% by mass or more, preferably 50% by mass or more, based on the total mass of the precursor film. The upper limit is not particularly limited, and may be 100% by mass.

前驅物膜中，亦可含有氧化銅位子以外的成分(例如有機化合物、銅粒子)。 The precursor film may contain components other than the copper oxide site (for example, an organic compound or copper particles).

前驅物膜的厚度為0.5μm~30μm。其中，就由後述光照射所得的氧化銅粒子的還原效率更優異的方面而言，較佳為1.0μm~30μm，更佳為5μm~30μm。 The thickness of the precursor film is from 0.5 μm to 30 μm. In particular, from the viewpoint of more excellent reduction efficiency of the copper oxide particles obtained by light irradiation described later, it is preferably 1.0 μm to 30 μm, and more preferably 5 μm to 30 μm.

於前驅物膜的厚度小於0.5μm的情形時，導電膜中容易產生缺陷，導電性差，於前驅物膜的厚度超過30μm的情形時，導電膜的導電性差。 When the thickness of the precursor film is less than 0.5 μm, defects are likely to occur in the conductive film, and conductivity is poor. When the thickness of the precursor film exceeds 30 μm, the conductivity of the conductive film is poor.

再者，所述前驅物膜的厚度為平均厚度，為測定任意10點的厚度並將該等加以算術平均而成。 Further, the thickness of the precursor film is an average thickness, and is obtained by measuring the thickness of any 10 points and arithmetically averaging the same.

另外，前驅物膜可設置於基材整個面上，亦能以圖案狀而設置。 Further, the precursor film may be provided on the entire surface of the substrate, or may be provided in a pattern.

[照射步驟] [Irradiation step]

照射步驟為以下步驟：對所述步驟中獲得的前驅物膜一面照射雷射光一面相對地掃描，將經雷射光照射的掃描區域中的氧化銅粒子還原，形成含有金屬銅的導電膜。藉由進行雷射光照射，氧化銅粒子、有機化合物、溶劑吸收光，所吸收的光被轉變成熱，熱滲透至前驅物膜內部，藉此於內部亦進行將氧化銅還原成金屬銅的還原反應。即，藉由實施所述處理，氧化銅的粒子被還原，所得的金屬銅粒子彼此相互熔合而形成顆粒(grain)，進而顆粒彼此接著、熔合而形成導電膜。 The irradiation step is a step of relatively scanning the precursor film obtained in the step while irradiating the laser light, and reducing the copper oxide particles in the scanning region irradiated with the laser light to form a conductive film containing metal copper. By irradiating with laser light, the copper oxide particles, the organic compound, and the solvent absorb light, and the absorbed light is converted into heat, and the heat penetrates into the interior of the precursor film, thereby reducing the reduction of the copper oxide to the metallic copper internally. reaction. That is, by performing the treatment, particles of copper oxide are reduced, and the obtained metal copper particles are fused to each other to form grains, and the particles are then adhered to each other to form a conductive film.

以下，參照圖式對該步驟加以詳細說明。 Hereinafter, this step will be described in detail with reference to the drawings.

圖1中，示出自雷射光源14對配置於基材10上的前驅物膜12照射雷射光16的態樣。於圖1中，藉由未圖示的掃描機構使雷射光源14朝箭頭的方向移動，一面於前驅物膜12表面上掃描，一面對既定的區域進行照射。於經雷射光16照射的區域(雷射光16的掃描區域)中，進行將氧化銅粒子還原成金屬銅的還原反應， 形成含有金屬銅的導電膜18。 In Fig. 1, a state in which the precursor light 12 disposed on the substrate 10 is irradiated with the laser light 16 from the laser light source 14 is shown. In FIG. 1, the laser light source 14 is moved in the direction of the arrow by a scanning mechanism (not shown), and is scanned on the surface of the precursor film 12 to be irradiated toward a predetermined area. In the region irradiated by the laser light 16 (the scanning region of the laser light 16), a reduction reaction for reducing the copper oxide particles to metallic copper is performed. A conductive film 18 containing metallic copper is formed.

圖1中，導電膜18為直線狀的圖案，但該形狀不限定於圖1的態樣。例如，亦可為曲線狀，亦可遍及基材整個面而形成導電膜。 In FIG. 1, the conductive film 18 is a linear pattern, but the shape is not limited to the aspect of FIG. For example, it may be curved or may form a conductive film over the entire surface of the substrate.

圖1中，例示了藉由掃描機構來移動雷射光源14的態樣，但不限定於該態樣，只要使雷射光與作為被照射物的前驅物膜相對地掃描即可。例如可列舉以下方法：將作為被照射物的帶有前驅物膜的基材載置於相對於掃描面而可於水平方向上移動的X-Y軸平台上，於將雷射光固定的狀態下使平台移動，藉此使雷射光於前驅物膜表面上掃描。當然，亦可為雷射光與作為被照射物的前驅物膜一起移動的態樣。 In FIG. 1, the aspect in which the laser light source 14 is moved by the scanning mechanism is exemplified, but the invention is not limited thereto, and it is only necessary to scan the laser light against the precursor film as the object to be irradiated. For example, a method in which a substrate with a precursor film as an object to be irradiated is placed on an XY-axis stage movable in a horizontal direction with respect to a scanning surface, and a platform is fixed in a state where laser light is fixed. Moving, thereby causing the laser to scan on the surface of the precursor film. Of course, it is also possible to move the laser light together with the precursor film as the object to be irradiated.

雷射光的波長為9μm~11μm。若為該波長的雷射光，則亦可侵入至前驅物膜的內部，前驅物膜內部的有機化合物、溶劑、氧化銅粒子吸收光並轉變成熱，由此可將氧化銅粒子高效地還原成金屬銅。 The wavelength of the laser light is from 9 μm to 11 μm. If the laser light of this wavelength is infiltrated into the precursor film, the organic compound, the solvent, and the copper oxide particles inside the precursor film absorb light and convert it into heat, thereby efficiently reducing the copper oxide particles into Metal copper.

所述雷射較佳為CO2雷射(二氧化碳雷射)。 The laser is preferably a CO 2 laser (carbon dioxide laser).

該步驟中，掃描的速度為10mm/s~120mm/s。其中，就於前驅物膜中更高效地將氧化銅還原成銅、並且可進一步抑制導電膜的缺陷的方面而言，較佳為10mm/s~80mm/s，更佳為10mm/s~60mm/s。 In this step, the scanning speed is 10 mm/s to 120 mm/s. Among them, in terms of reducing the copper oxide to copper more efficiently in the precursor film and further suppressing the defects of the conductive film, it is preferably 10 mm/s to 80 mm/s, more preferably 10 mm/s to 60 mm. /s.

於掃描的速度小於10m/s的情形時，獲得導電性差的導電膜。另外，於掃描的速度超過120mm/s的情形時，導電膜容易產 生缺陷。 When the scanning speed is less than 10 m/s, a conductive film having poor conductivity is obtained. In addition, when the scanning speed exceeds 120 mm/s, the conductive film is easy to produce. Health defects.

該步驟中，基材的熱傳導率A[W/(m．K)]與雷射光的輸出W[W]滿足以下的式1的關係。 In this step, the thermal conductivity A [W/(m.K)] of the substrate and the output W [W] of the laser light satisfy the relationship of the following formula 1.

式1 1.39+0.3252Ln(A)≦W≦3.00+0.3252Ln(A) Equation 1 1.39+0.3252Ln(A)≦W≦3.00+0.3252Ln(A)

若對前驅物膜照射雷射光，則前驅物膜中的氧化銅粒子、有機化合物、溶劑吸收雷射光並轉變成熱能。所生成的熱能傳導至前驅物膜中，引起氧化銅粒子的還原。另一方面，前驅物膜中的熱能亦傳導至與前驅物膜鄰接的基材中。此時，於基材的熱傳導率高的情形時，前驅物膜中的熱能更多地傳導至基材側，故導致氧化銅粒子的還原難以進行。另一方面，於基材的熱傳導率低的情形時，熱能容易滯留於前驅物膜中，有時產生不需要的副反應。因此，前驅物膜中的氧化銅粒子的還原的進行容易程度視雷射光的輸出與基材的熱傳導率而不同。所述式1表示於基材具有既定的熱傳導率A的情形時，用以於前驅物膜中高效地進行氧化銅粒子的還原的必要的雷射光的輸出。 When the precursor film is irradiated with laser light, the copper oxide particles, the organic compound, and the solvent in the precursor film absorb the laser light and convert it into heat energy. The generated thermal energy is conducted into the precursor film, causing reduction of the copper oxide particles. On the other hand, the thermal energy in the precursor film is also conducted into the substrate adjacent to the precursor film. At this time, when the thermal conductivity of the substrate is high, the thermal energy in the precursor film is more transmitted to the substrate side, so that the reduction of the copper oxide particles is difficult to proceed. On the other hand, when the thermal conductivity of the substrate is low, thermal energy is likely to remain in the precursor film, and an unnecessary side reaction may occur. Therefore, the ease of reduction of the copper oxide particles in the precursor film is different depending on the output of the laser light and the thermal conductivity of the substrate. The above formula 1 shows an output of laser light necessary for efficiently performing reduction of copper oxide particles in the precursor film when the substrate has a predetermined thermal conductivity A.

將式1的關係具體示於圖2中。於以雷射光的輸出W為縱軸、以基材的熱傳導率A的Ln(A)(再者，Ln表示自然對數)為橫軸的二維座標中，所謂滿足式1的關係，是指如圖2所示般，只要W及Ln(A)在由以下的式(A)~式(B)所表示的直線所包圍的範圍內即可。 The relationship of Formula 1 is specifically shown in FIG. 2. In the two-dimensional coordinate in which the output W of the laser light is the vertical axis and the Ln (A) of the thermal conductivity A of the substrate (again, Ln represents the natural logarithm) is the horizontal axis, the relationship that satisfies the expression 1 means As shown in FIG. 2, W and Ln (A) may be in a range surrounded by a straight line represented by the following formulas (A) to (B).

式(A)：W=0.3252Ln(A)+1.39 Formula (A): W = 0.3252Ln (A) + 1.39

式(B)：W=0.3252Ln(A)+3.00 Formula (B): W = 0.3252Ln (A) + 3.00

其中，就於前驅物膜中更高效地將氧化銅粒子還原成金屬銅、並且所得的導電膜的缺陷少、導電性更優異的方面而言，較佳為滿足以下的式2的關係，更佳為滿足式3的關係。 In the case where the copper oxide particles are reduced to metal copper more efficiently in the precursor film, and the obtained conductive film has fewer defects and more excellent conductivity, it is preferable to satisfy the following formula 2 and Good to satisfy the relationship of Formula 3.

式2 1.39+0.3252Ln(A)≦W≦2.40+0.3252Ln(A) Equation 2 1.39+0.3252Ln(A)≦W≦2.40+0.3252Ln(A)

式3 1.39+0.3252Ln(A)≦W≦1.75+0.3252Ln(A) Equation 3 1.39+0.3252Ln(A)≦W≦1.75+0.3252Ln(A)

再者，若將式2的關係換言之，則於圖2中，只要W及Ln(A)在由以下的式(A)所表示的直線、及式(C)所表示的直線所包圍的範圍內即可。 In other words, in the case of the relationship of the formula 2, in the range of W and Ln(A) surrounded by a straight line represented by the following formula (A) and a straight line represented by the formula (C), Just inside.

式(A)：W=0.3252Ln(A)+1.39 Formula (A): W = 0.3252Ln (A) + 1.39

式(C)：W=0.3252Ln(A)+2.40 Formula (C): W = 0.3252Ln(A) + 2.40

另外，若將式3的關係換言之，則於圖2中，只要W及Ln(A)在由以下的式(A)所表示的直線、及式(D)所表示的直線所包圍的範圍內即可。 In other words, in the case of the relationship of the formula 3, in the range of W and Ln(A) surrounded by a straight line represented by the following formula (A) and a straight line represented by the formula (D), Just fine.

式(A)：W=0.3252Ln(A)+1.39 Formula (A): W = 0.3252Ln (A) + 1.39

式(D)；W=0.3252Ln(A)+1.75 Formula (D); W = 0.3252Ln (A) + 1.75

再者，如上所述，基材的熱傳導率A的較佳範圍可列舉0.1W/(m．K)~0.6W/(m．K)，表示該較佳範圍的Ln(A)為-2.303~-0.511。 Further, as described above, a preferred range of the thermal conductivity A of the substrate is 0.1 W/(m.K) to 0.6 W/(m.K), and Ln(A) of the preferred range is -2.330. ~-0.511.

於該步驟中，雷射光的輸出(雷射功率)只要滿足所述式1的關係，則並無特別限制，超過0W，且就導電膜的缺陷更少、導電性更優異的方面而言，較佳為0.6W~2.9W，更佳為0.8W~2.4W。 In this step, the output of the laser light (the laser power) is not particularly limited as long as it satisfies the relationship of the above formula 1, and is more than 0 W, and the conductive film has fewer defects and more excellent electrical conductivity. It is preferably 0.6 W to 2.9 W, more preferably 0.8 W to 2.4 W.

對前驅物膜表面照射的雷射光的點徑並無特別限制，是根據形成的導電膜的寬度而適當調整。例如於使用導電膜作為印刷配線基板的配線的情形時，就可形成線細的配線的方面而言，點徑較佳為5μm~200μm，更佳為9μm~150μm，進而佳為25μm~150μm。 The spot diameter of the laser light irradiated to the surface of the precursor film is not particularly limited, and is appropriately adjusted depending on the width of the formed conductive film. For example, when a conductive film is used as the wiring of the printed wiring board, the dot diameter is preferably 5 μm to 200 μm, more preferably 9 μm to 150 μm, and still more preferably 25 μm to 150 μm.

該步驟中，前驅物膜表面的每一地點的照射時間並無特別限制，就導電膜的缺陷更少、導電性更優異的方面而言，較佳為1000μs~9000μs，更佳為1500μs~8000μs。 In this step, the irradiation time at each point on the surface of the precursor film is not particularly limited, and in terms of less defects of the conductive film and more excellent conductivity, it is preferably from 1000 μs to 9000 μs, more preferably from 1,500 μs to 8000 μs. .

此處，照射時間是指照射雷射光的前驅物膜表面上的任意一地點的照射雷射光的時間。照射時間可根據掃描速度及點徑來計算。例如，於照射至前驅物膜表面上的連續振盪雷射光的掃描方向上的點徑(直徑)為60μm、且其掃描速度為10m/s的情形時， 計算出照射時間為6μs。 Here, the irradiation time refers to the time of irradiating the laser light at any point on the surface of the precursor film irradiated with the laser light. The irradiation time can be calculated based on the scanning speed and the spot diameter. For example, when the spot diameter (diameter) in the scanning direction of the continuous oscillating laser light irradiated onto the surface of the precursor film is 60 μm and the scanning speed is 10 m/s, The irradiation time was calculated to be 6 μs.

實施所述雷射光照射處理的環境並無特別限制，可列舉大氣環境下、惰性環境下或還原性環境下等。再者，所謂惰性環境，例如為由氬氣、氦氣、氖氣、氮氣等惰性氣體充滿的環境，另外所謂還原性環境，是指氫氣、一氧化碳等還原性氣體存在的環境。 The environment in which the laser light irradiation treatment is performed is not particularly limited, and examples thereof include an atmospheric environment, an inert environment, or a reducing environment. In addition, the inert environment is, for example, an environment filled with an inert gas such as argon gas, helium gas, neon gas or nitrogen gas, and the so-called reducing environment means an environment in which a reducing gas such as hydrogen gas or carbon monoxide is present.

雷射光的掃描條件的較佳態樣可列舉以下態樣：於利用雷射光對與經雷射光照射的第1掃描區域鄰接的區域進行掃描時，以與第1掃描區域局部重複的方式照射雷射光，且重複區域的寬度為雷射光的點徑的15%~30%的大小。 In a preferred aspect of the scanning condition of the laser light, when scanning a region adjacent to the first scanning region irradiated with the laser light by the laser light, the laser is irradiated in a manner partially overlapping the first scanning region. The light is emitted, and the width of the repeating region is 15% to 30% of the spot diameter of the laser light.

使用圖3對所述態樣加以說明。如圖3所示，對於配置於基材10上的前驅物膜12，於利用雷射光16對與自雷射光源14照射了雷射光16的第1掃描區域20鄰接的鄰接區域22進行掃描時，以第1掃描區域20與鄰接區域22局部重複的方式照射雷射光16。此時，以重複區域24(斜線部)的寬度W相當於雷射光16的點徑D的15%~30%的大小的方式，照射雷射光16。換言之，以重複區域24的寬度W相對於雷射光16的點徑D之比例{(W/D)×100}(重疊率)成為15%~30%的方式，照射雷射光。藉由實施該掃描方法，可獲得缺陷更少、導電性優異的導電膜。 The aspect will be described using FIG. As shown in FIG. 3, when the precursor film 12 disposed on the substrate 10 is scanned by the laser beam 16 adjacent to the adjacent region 22 adjacent to the first scanning region 20 from which the laser light 14 is irradiated with the laser light 16, The laser light 16 is irradiated in such a manner that the first scanning region 20 and the adjacent region 22 partially overlap. At this time, the laser light 16 is irradiated so that the width W of the repeating region 24 (hatched portion) corresponds to the size of the spot diameter D of the laser light 16 by 15% to 30%. In other words, the laser light is irradiated so that the ratio of the width W of the overlap region 24 to the spot diameter D of the laser light 16 ((W/D) × 100} (overlap ratio) is 15% to 30%. By carrying out this scanning method, a conductive film having fewer defects and excellent conductivity can be obtained.

再者，於圖3中，第1掃描區域20為直線狀的圖案，但不限定於該態樣。 In addition, in FIG. 3, although the 1st scanning area 20 is a linear pattern, it is not limited to this aspect.

(導電膜) (conductive film)

藉由實施所述步驟，可獲得含有金屬銅的導電膜(金屬膜)。 By carrying out the above steps, a conductive film (metal film) containing metallic copper can be obtained.

導電膜的膜厚較佳為0.5μm~30μm。其中，就印刷配線基板用途的方面而言，更佳為1μm~30μm，進而佳為5μm~30μm。 The film thickness of the conductive film is preferably from 0.5 μm to 30 μm. In particular, the use of the printed wiring board is preferably from 1 μm to 30 μm, and more preferably from 5 μm to 30 μm.

再者，膜厚為對導電膜的任意點的厚度測定3處以上，並將其值加以算術平均所得的值(平均率)。 In addition, the film thickness is a value (average ratio) obtained by measuring the thickness of any point of the conductive film at three or more places and arithmetically averaging the values.

就導電性的方面而言，導電膜的體積電阻率較佳為小於3×10-4Ωcm，更佳為小於5×10-5Ωcm。 The conductive film preferably has a volume resistivity of less than 3 × 10 -4 Ωcm, more preferably less than 5 × 10 -5 Ωcm, in terms of electrical conductivity.

體積電阻率可藉由四探針法測定導電膜的表面電阻值後，對所得的表面電阻值乘以膜厚而算出。 The volume resistivity can be calculated by multiplying the obtained surface resistance value by the film thickness by measuring the surface resistance value of the conductive film by the four-probe method.

導電膜可設置於基材的整個面上或以圖案狀而設置。圖案狀的導電膜作為印刷配線基板等的導體配線(配線)而有用。 The conductive film may be disposed on the entire surface of the substrate or in a pattern. The patterned conductive film is useful as a conductor wiring (wiring) such as a printed wiring board.

獲得圖案狀的導電膜的方法可列舉：將所述分散液以圖案狀賦予至基材上，進行所述雷射光照射處理的方法；或對設置於基材整個面上的導電膜以圖案狀進行蝕刻的方法；或對設置於基材整個面上的前驅物膜以圖案狀照射雷射光的方法等。 The method of obtaining a pattern-shaped conductive film may be a method of applying the dispersion liquid to a substrate in a pattern to perform the laser light irradiation treatment, or patterning the conductive film provided on the entire surface of the substrate. A method of performing etching; or a method of irradiating a laser beam with a pattern of a precursor film provided on the entire surface of the substrate.

再者，蝕刻的方法並無特別限制，可採用公知的減成法、半加成法等。 Further, the etching method is not particularly limited, and a known subtractive method, semi-additive method, or the like can be employed.

於以圖案狀設置導電膜的情形時，視需要亦可將未經雷射光照射的前驅物膜的未照射區域去除。未照射區域的去除方法並無特別限制，可列舉使用酸等蝕刻溶液進行蝕刻的方法。 In the case where the conductive film is provided in a pattern, the unirradiated region of the precursor film which is not irradiated with the laser light may be removed as needed. The method of removing the unirradiated region is not particularly limited, and a method of etching using an etching solution such as an acid can be mentioned.

於將圖案狀的導電膜構成為印刷配線基板的情形時，亦可於圖案狀的導電膜的表面上進一步積層絕緣層(絕緣樹脂層、 層間絕緣膜、阻焊劑)，並於其表面上進一步形成配線(金屬圖案)。 When the patterned conductive film is formed as a printed wiring substrate, an insulating layer (insulating resin layer, further may be laminated on the surface of the patterned conductive film) An interlayer insulating film, a solder resist), and further wiring (metal pattern) is formed on the surface thereof.

絕緣膜的材料並無特別限制，例如可列舉：環氧樹脂、芳族聚醯胺樹脂、結晶性聚烯烴樹脂、非晶性聚烯烴樹脂、含氟樹脂(聚四氟乙烯、全氟化聚醯亞胺、全氟化非晶樹脂等)、聚醯亞胺樹脂、聚醚碸樹脂、聚苯硫醚樹脂、聚醚醚酮樹脂、液晶樹脂等。 The material of the insulating film is not particularly limited, and examples thereof include an epoxy resin, an aromatic polyamide resin, a crystalline polyolefin resin, an amorphous polyolefin resin, and a fluorine-containing resin (polytetrafluoroethylene, perfluorinated poly醯imine, perfluorinated amorphous resin, etc.), polyimide resin, polyether oxime resin, polyphenylene sulfide resin, polyetheretherketone resin, liquid crystal resin, and the like.

該等中，就密接性、尺寸穩定性、耐熱性、電氣絕緣性等觀點而言，較佳為含有環氧樹脂、聚醯亞胺樹脂或液晶樹脂，更佳為環氧樹脂。具體可列舉味之素精密技術(Ajinomoto Finetechno)(股)製造的ABF GX-13等。 Among these, from the viewpoints of adhesion, dimensional stability, heat resistance, electrical insulation, and the like, it is preferred to contain an epoxy resin, a polyimide resin, or a liquid crystal resin, and more preferably an epoxy resin. Specifically, ABF GX-13 manufactured by Ajinomoto Finetechno Co., Ltd., and the like can be cited.

另外，關於作為用於保護配線的絕緣層的材料的一種的阻焊劑，例如是詳細記載於日本專利特開平10-204150號公報或日本專利特開2003-222993號公報等中，視需要亦可將其中記載的材料應用於本發明中。阻焊劑亦可使用市售品，具體而言，例如可列舉：太陽油墨製造(股)製造的PFR800、PSR4000(商品名)，日立化成工業(股)製造的SR7200G等。 In addition, the solder resist which is one of the materials for protecting the insulating layer of the wiring is, for example, described in Japanese Patent Laid-Open No. Hei 10-204150, or Japanese Patent Laid-Open No. 2003-222993, and the like. The materials described therein are applied to the present invention. A commercially available product may be used as the solder resist. Specific examples thereof include PFR800 and PSR4000 (trade name) manufactured by Sun Ink Manufacturing Co., Ltd., and SR7200G manufactured by Hitachi Chemical Co., Ltd.

上文所得的具有導電膜的基材(帶有導電膜的基材)可用於各種用途。例如可列舉印刷配線基板、薄膜電晶體(Thin Film Transistor，TFT)、可撓性印刷電路(Flexible Printed Circuit，FPC)、射頻識別(Radio Frequency Identification，RFID)等。 The substrate having a conductive film (substrate with a conductive film) obtained above can be used for various purposes. For example, a printed wiring board, a thin film transistor (TFT), a flexible printed circuit (FPC), a radio frequency identification (RFID), or the like can be given.

[實施例] [Examples]

以下，藉由實施例對本發明加以更詳細說明，但本發明不限定於該些實施例。 Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto.

再者，於後述實施例欄的記載中，氧化銅粒子及銅粒子的「平均粒徑」是指「平均一次粒徑」。 In the description of the column of the examples to be described later, the "average particle diameter" of the copper oxide particles and the copper particles means "average primary particle diameter".

<實施例1> <Example 1>

(氧化銅分散液1的製備) (Preparation of copper oxide dispersion 1)

將氧化銅粒子(C.I.化成製造，NanoTekR CuO，平均粒徑為48nm)58質量份、聚乙烯基吡咯啶酮K15(東京化成(股)公司製造)8.1質量份、甘油11.6質量份及離子交換水22.3質量份混合，利用自轉公轉混合機(新基(THINKY)公司製造，消泡攪拌太郎ARE-310)進行3分鐘處理，由此獲得氧化銅分散液1。 58 parts by mass of copper oxide particles (manufactured by CI, NanoTekR CuO, average particle diameter: 48 nm), polyvinylpyrrolidone K15 (manufactured by Tokyo Chemical Industry Co., Ltd.), 8.1 parts by mass, glycerin, 11.6 parts by mass, and ion-exchanged water 22.3 parts by mass of the mixture was subjected to a treatment for 3 minutes using a spinning revolution mixer (manufactured by THINKY Co., Ltd., defoaming and stirring Taro ARE-310), thereby obtaining a copper oxide dispersion liquid 1.

(前驅物膜的製作) (Preparation of precursor film)

藉由棒式塗佈將氧化銅分散液1賦予至玻璃環氧樹脂基材(基材的熱傳導率為0.3W/(m．K))上，形成厚度為12μm的塗膜，其後，使用熱板於100℃下對具有塗膜的基材進行60分鐘乾燥處理，製作帶有前驅物膜的基材。 The copper oxide dispersion 1 was applied to a glass epoxy substrate (thermal conductivity of the substrate of 0.3 W/(m.K)) by bar coating to form a coating film having a thickness of 12 μm, and thereafter, used. The hot plate was dried at 100 ° C for 60 minutes on a substrate having a coating film to prepare a substrate with a precursor film.

繼而，使用基恩斯(Keyence)公司製造的ML-Z9550T(二氧化碳雷射，波長為9.3μm)，將點徑為90μm的二氧化碳雷射以線速(掃描速度)10mm/s、輸出1.8W於前驅物膜上掃描1次，製作導電膜。將所得的樣品稱為樣品1。 Then, using ML-Z9550T (carbon dioxide laser, wavelength 9.3 μm) manufactured by Keyence Corporation, a carbon dioxide laser with a spot diameter of 90 μm was output at a line speed (scanning speed) of 10 mm/s and output of 1.8 W in the precursor. The film was scanned once to prepare a conductive film. The resulting sample was referred to as Sample 1.

另外，對於另行準備的帶有前驅物膜的基材的前驅物膜，以65μm的間距交替掃描二氧化碳雷射，製作導電性評價用的6mm 見方的正方形的導電膜。此時的重疊率為28%。將所得的樣品稱為樣品2。 Further, a precursor film of a substrate having a precursor film prepared separately was alternately scanned with a carbon dioxide laser at a pitch of 65 μm to prepare a 6 mm for conductivity evaluation. See the square of the conductive film. The overlap ratio at this time was 28%. The resulting sample is referred to as Sample 2.

再者，所謂重疊率，是指圖3中說明的第1掃描區域20與鄰接區域22的重複區域24的寬度W相對於雷射光16的點徑D之比例{(W/D)×100}。以下為相同規定。 In addition, the overlap ratio means the ratio of the width W of the overlap region 24 of the first scanning region 20 and the adjacent region 22 described in FIG. 3 to the spot diameter D of the laser light 16 {(W/D)×100} . The following are the same rules.

<評價> <evaluation>

(導電膜的外觀評價(導體的形成狀態)) (Evaluation of Appearance of Conductive Film (Formation State of Conductor))

使用光學顯微鏡，以200倍的倍率對所得的樣品1中的導電膜的橫向3mm進行觀察，按照以下的基準進行評價。將結果示於表1中。再者，實用上，較佳為A~C。 The transverse direction of the conductive film in the obtained sample 1 was observed by an optical microscope at a magnification of 200 times, and was evaluated according to the following criteria. The results are shown in Table 1. Furthermore, in practice, it is preferably A to C.

A：無缺損 A: no defect

B：10μm見方以下的大小的缺損有1處~5處 B: There are 1 to 5 defects in the size of 10 μm square or less.

C：10μm見方以下的大小的缺損有6處以上 C: There are 6 or more defects of the size below 10 μm square.

D：存在大於10μm見方的缺損 D: There is a defect larger than 10 μm square

E：導電膜斷裂/無法形成導電膜 E: The conductive film is broken / the conductive film cannot be formed

再者，所謂10μm見方以下的大小的缺損，是指控制在縱向10μm×橫向10μm的範圍內的大小的缺損。 In addition, the defect of the size of 10 μm square or less is a defect which is controlled in the range of 10 μm in the longitudinal direction and 10 μm in the lateral direction.

(導電性評價) (Electrical evaluation)

導電性是以藉由四端子法測定、算出的體積電阻率(Ω．cm)的形式求出。 The conductivity was determined as a volume resistivity (Ω.cm) measured by a four-terminal method.

導電膜的厚度是使用SEM(電子顯微鏡S800：日立製作所製造)自導電膜剖面中測量導電膜的厚度(再者，導電膜的厚度是 將任意3處的厚度加以算術平均所得)。使用電阻率測定器(低阻計(Loresta)；三菱化學(股)公司製造)，於該測定器中輸入所述實測的導電膜的厚度並進行測定。將結果示於表1中。再者，實用上，較佳為A~C。 The thickness of the conductive film is measured by a SEM (Electron Microscope S800: manufactured by Hitachi, Ltd.) from the thickness of the conductive film in the cross section of the conductive film (further, the thickness of the conductive film is The thickness of any three places is arithmetically averaged). Using a resistivity meter (Loresta; manufactured by Mitsubishi Chemical Corporation), the thickness of the actually-measured conductive film was input into the measuring device and measured. The results are shown in Table 1. Furthermore, in practice, it is preferably A to C.

A：小於5×10-5Ωcm A: less than 5 × 10 -5 Ωcm

B：5×10-5Ωcm以上、小於1×10-4Ωcm B: 5 × 10 -5 Ωcm or more, less than 1 × 10 -4 Ωcm

C；1×10-4Ωcm以上、小於3×10-4Ωcm C; 1 × 10 -4 Ωcm or more, less than 3 × 10 -4 Ωcm

D：3×10-4Ωcm以上 D: 3 × 10 -4 Ωcm or more

E：導電膜有損傷。 E: The conductive film is damaged.

<比較例1> <Comparative Example 1>

使用平均粒徑為1μm的氧化銅粒子代替氧化銅粒子(C.I.化成製造，NanoTekR CuO，平均粒徑為48nm)，除此以外，依照與實施例1相同的順序製造導電膜，實施各種評價。將結果匯總示於表1中。 A conductive film was produced in the same manner as in Example 1 except that copper oxide particles having an average particle diameter of 1 μm were used instead of the copper oxide particles (manufactured by C.I., manufactured by Nano-Chemical Co., Ltd., and the average particle diameter was 48 nm), and various evaluations were carried out. The results are summarized in Table 1.

<比較例2> <Comparative Example 2>

使用精密元件(Fine Device)公司製造的半導體雷射(波長為940nm)代替基恩斯(Keyence)公司製造的ML-Z9550T，且將輸出設定為3W、點徑設定為1.5mm，除此以外，依照與實施例1相同的順序製造導電膜，實施各種評價。將結果匯總示於表1中。 A semiconductor laser manufactured by Fine Equipment Co., Ltd. (wavelength: 940 nm) was used instead of the ML-Z9550T manufactured by Keyence, and the output was set to 3 W and the spot diameter was set to 1.5 mm. In the same procedure as in Example 1, a conductive film was produced, and various evaluations were carried out. The results are summarized in Table 1.

<實施例2~實施例8及比較例3~比較例9> <Example 2 to Example 8 and Comparative Example 3 to Comparative Example 9>

除了如表1般變更所使用的基材、線速、前驅物膜的厚度及 輸出等以外，依照與實施例1相同的順序製造導電膜，實施各種評價。將結果匯總示於表1中。 In addition to the substrate used in Table 1, the wire speed, the thickness of the precursor film, and A conductive film was produced in the same manner as in Example 1 except for the output, and various evaluations were performed. The results are summarized in Table 1.

<實施例9~實施例12> <Example 9 to Example 12>

以重疊率成為表1般的方式將掃描間距變更為76.5μm(實施例8)、63μm(實施例9)、81μm(實施例10)、58.5μm(實施例11)，除此以外，依照與實施例1相同的順序製造導電膜，實施各種評價。將結果匯總示於表1中。 The scanning pitch was changed to 76.5 μm (Example 8), 63 μm (Example 9), 81 μm (Example 10), and 58.5 μm (Example 11) in such a manner that the overlap ratio was as shown in Table 1, except that In the same procedure as in Example 1, a conductive film was produced, and various evaluations were carried out. The results are summarized in Table 1.

<實施例13~實施例15> <Example 13 to Example 15>

使用聚萘二甲酸乙二酯基材(PEN基材，基材的熱傳導率為0.1W/(m．K))、聚對苯二甲酸乙二酯基材(PET基材，基材的熱傳導率為0.15W/(m．K))或聚醯亞胺基材(PI基材，基材的熱傳導率為0.16W/(m．K))代替玻璃環氧樹脂基材，如表2般變更輸出，除此以外，依照與實施例1相同的順序製造導電膜，實施各種評價。將結果匯總示於表2中。 Use polyethylene naphthalate substrate (PEN substrate, substrate thermal conductivity: 0.1W / (m. K)), polyethylene terephthalate substrate (PET substrate, substrate thermal conduction The ratio is 0.15 W/(m.K)) or the polyimide substrate (PI substrate, the substrate has a thermal conductivity of 0.16 W/(m.K)) instead of the glass epoxy substrate, as shown in Table 2. A conductive film was produced in the same manner as in Example 1 except that the output was changed, and various evaluations were carried out. The results are summarized in Table 2.

<實施例16> <Example 16>

將氧化銅粒子(C.I.化成製造，NanoTekR CuO，平均粒徑為48nm)58質量份、聚乙二醇20000(和光純藥(股)公司製造)6.5質量份、聚乙二醇2000000(和光純藥(股)公司製造)1.6質量份、甘油11.6質量份及離子交換水22.3質量份混合，利用自轉公轉混合機(新基(THINKY)公司製造，消泡攪拌太郎ARE-310)進行3分鐘處理，由此獲得氧化銅分散液2。 58 parts by mass of copper oxide particles (manufactured by CI, NanoTekR CuO, average particle diameter: 48 nm), polyethylene glycol 20000 (manufactured by Wako Pure Chemical Industries, Ltd.), 6.5 parts by mass, polyethylene glycol 2,000,000 (Wako Pure Chemicals Co., Ltd.) (manufactured by the company) 1.6 parts by mass, 11.6 parts by mass of glycerin, and 22.3 parts by mass of ion-exchanged water, and mixed for 3 minutes by a self-rotating revolution mixer (manufactured by THINKY Co., Ltd., defoaming and stirring Taro ARE-310). Thus, a copper oxide dispersion 2 was obtained.

使用氧化銅分散液2代替氧化銅分散液1，依照與實施例1 相同的順序製作前驅物膜，且如表3般變更線速、輸出，除此以外，依照與實施例1相同的順序製造導電膜，實施各種評價。將結果匯總示於表3中。 Copper oxide dispersion 2 was used instead of copper oxide dispersion 1, in accordance with Example 1. A conductive film was produced in the same manner as in Example 1 except that the precursor film was produced in the same order, and the wire speed and the output were changed as in Table 3, and various evaluations were carried out. The results are summarized in Table 3.

<實施例17> <Example 17>

將氧化銅粒子(C.I.化成製造，NanoTekR CuO，平均粒徑為48nm)58質量份、葡萄糖11.0質量份、甘油11.6質量份及離子交換水22.5質量份混合，利用自轉公轉混合機(新基(THINKY)公司製造，消泡攪拌太郎ARE-310)進行3分鐘處理，由此獲得氧化銅分散液3。 58 parts by mass of copper oxide particles (manufactured by CI, NanoTekR CuO, average particle diameter: 48 nm), 11.0 parts by mass of glucose, 11.6 parts by mass of glycerin, and 22.5 parts by mass of ion-exchanged water were mixed, and a self-rotating revolution mixer (new one (THINKY) was used. The company manufactured, defoaming and stirring Taro ARE-310) was treated for 3 minutes, thereby obtaining a copper oxide dispersion 3.

使用氧化銅分散液3代替氧化銅分散液1，依照與實施例1相同的順序來製作前驅物膜，且如表3般變更線速、輸出，除此以外，依照與實施例1相同的順序製造導電膜，實施各種評價。將結果匯總示於表3中。 A copper oxide dispersion liquid 3 was used instead of the copper oxide dispersion liquid 1, and a precursor film was produced in the same manner as in Example 1, and the line speed and output were changed as shown in Table 3, except that the same procedure as in Example 1 was carried out. A conductive film was produced and various evaluations were performed. The results are summarized in Table 3.

<實施例18~實施例21> <Example 18 to Example 21>

於氧化銅分散液1的製備時，以成為表3中記載的量的方式變更聚乙烯基吡咯啶酮K15的量，製作氧化銅分散液4~氧化銅分散液7，依照與實施例1相同的順序製造導電膜，實施各種評價。將結果匯總示於表3中。 In the preparation of the copper oxide dispersion 1, the amount of the polyvinylpyrrolidone K15 was changed so as to have the amount shown in Table 3, and the copper oxide dispersion 4 to the copper oxide dispersion 7 was produced, and the same as in the first embodiment. The conductive film was produced in the order, and various evaluations were performed. The results are summarized in Table 3.

<實施例22> <Example 22>

將氧化銅粒子(C.I.化成製造，NanoTekR CuO，平均粒徑為48nm)29質量份、銅粒子(1020Y，三井金屬礦業(股)，平均粒徑為0.34μm)29質量份、聚乙二醇20000(和光純藥(股)公 司製造)3.2質量份、聚乙二醇2000000(和光純藥(股)公司製造)0.8質量份、甘油6.9質量份及離子交換水31.1質量份混合，利用自轉公轉混合機(新基(THINKY)公司製造，消泡攪拌太郎ARE-310)進行3分鐘處理，由此獲得氧化銅分散液8。 29 parts by mass of copper oxide particles (manufactured by CI, manufactured by NanoTekR CuO, average particle diameter: 48 nm), copper particles (1020Y, Mitsui Metals Mining Co., Ltd., average particle diameter: 0.34 μm), 29 parts by mass, polyethylene glycol 20000 (Wako Pure Medicine (share)) Manufactured by the company, 3.2 parts by mass, polyethylene glycol 2000000 (manufactured by Wako Pure Chemical Industries, Ltd.), 0.8 parts by mass, 6.9 parts by mass of glycerin, and 31.1 parts by mass of ion-exchanged water, using a self-rotating revolution mixer (New Base (THINKY) The company manufactured, defoaming and stirring Taro ARE-310) was treated for 3 minutes, thereby obtaining a copper oxide dispersion 8.

使用氧化銅分散液8代替氧化銅分散液1，依照與實施例1相同的順序來製作前驅物膜，且如表4般變更線速、輸出，除此以外，依照與實施例1相同的順序製造導電膜，實施各種評價。 A copper oxide dispersion liquid 8 was used instead of the copper oxide dispersion liquid 1, and a precursor film was produced in the same manner as in Example 1, and the line speed and output were changed as shown in Table 4, except that the same procedure as in Example 1 was carried out. A conductive film was produced and various evaluations were performed.

將結果匯總示於表4中。 The results are summarized in Table 4.

<實施例23~實施例26> <Example 23 to Example 26>

於氧化銅分散液8的製備時，分別使用平均粒徑為0.49μm的銅粒子(1030Y，三井金屬礦業(股)製造)、平均粒徑為1.1μm的銅粒子(1100Y，三井金屬礦業(股)製造)、平均粒徑為3.2μm的銅粒子(1200YP，三井金屬礦業(股)製造)、或平均粒徑為6.3μm的銅粒子(1400Y，三井金屬礦業(股)製造)代替銅粒子(1020Y，三井金屬礦業(股)，平均粒徑為0.34μm)，製作氧化銅分散液9~氧化銅分散液12，並使用該些氧化銅分散液，除此以外，依照與實施例22相同的順序製造導電膜，實施各種評價。將結果匯總示於表4中。 In the preparation of the copper oxide dispersion 8, copper particles having an average particle diameter of 0.49 μm (1030Y, manufactured by Mitsui Mining & Mining Co., Ltd.) and copper particles having an average particle diameter of 1.1 μm (1100Y, Mitsui Metals Mining Co., Ltd.) were used. (manufacturing), copper particles (1200YP, manufactured by Mitsui Mining & Mining Co., Ltd.) having an average particle diameter of 3.2 μm, or copper particles (1400Y, manufactured by Mitsui Mining & Mining Co., Ltd.) having an average particle diameter of 6.3 μm instead of copper particles (manufactured) 1020Y, Mitsui Metals Mining Co., Ltd., having an average particle diameter of 0.34 μm), producing a copper oxide dispersion liquid 9 to a copper oxide dispersion liquid 12, and using the copper oxide dispersion liquid, except that the same procedure as in Example 22 was carried out. The conductive film was sequentially produced, and various evaluations were performed. The results are summarized in Table 4.

<實施例27~實施例29> <Example 27 to Example 29>

於實施例25中，如表4所示般變更線速，除此以外，依照與實施例25相同的順序製造導電膜，實施各種評價將。將結果匯總示於表4中。 In the same manner as in Example 25 except that the line speed was changed as shown in Table 4, the conductive film was produced in the same manner as in Example 25, and various evaluations were carried out. The results are summarized in Table 4.

<實施例30> <Example 30>

將氧化銅粒子(C.I.化成製造，NanoTekR CuO，平均粒徑為48mm)29質量份、銅粒子(1200YP，三井金屬礦業(股)製造，平均粒徑為3.2μm)29質量份、聚乙烯基吡咯啶酮K15 4質量份、甘油6.9質量份及離子交換水31.1質量份混合，利用自轉公轉混合機(新基(THINKY)公司製造，消泡攪拌太郎ARE-310)進行3分鐘處理，由此獲得氧化銅分散液13。 29 parts by mass of copper oxide particles (manufactured by CI, manufactured by NanoTekR CuO, average particle diameter: 48 mm), copper particles (1200 YP, manufactured by Mitsui Mining Co., Ltd., average particle diameter: 3.2 μm), 29 parts by mass, polyvinylpyrrole 4 parts by mass of pyridine ketone K15, 6.9 parts by mass of glycerin, and 31.1 parts by mass of ion-exchanged water were mixed, and a 3-minute treatment was carried out by a self-rotating revolution mixer (manufactured by THINKY Co., Ltd., defoaming stirring Taro ARE-310). Copper oxide dispersion 13.

使用氧化銅分散液13代替氧化銅分散液1，依照與實施例1相同的順序製作前驅物膜，且如表4般變更線速，除此以外，依照與實施例1相同的順序製造導電膜，實施各種評價。將結果匯總示於表4中。 A conductive film was produced in the same manner as in Example 1 except that the copper oxide dispersion 13 was used instead of the copper oxide dispersion 1, and a precursor film was produced in the same manner as in Example 1, and the line speed was changed as shown in Table 4. , carry out various evaluations. The results are summarized in Table 4.

<實施例31> <Example 31>

將氧化銅粒子(C.I.化成製造，NanoTekR CuO，平均粒徑為48nm)48.3質量份、平均粒徑為3.2μm的銅粒子(1200YP，三井金屬礦業(股)製造)9.7質量份、聚乙二醇20000(和光純藥(股)公司製造)5.4質量份、聚乙二醇2000000(和光純藥(股)公司製造)1.4質量份、甘油6.9質量份及離子交換水28.3質量份混合，利用自轉公轉混合機(新基(THINKY)公司製造，消泡攪拌太郎ARE-310)進行3分鐘處理，由此獲得氧化銅分散液14。使用氧化銅分散液14，依照與實施例25相同的順序製造導電膜，實施各種評價。將結果匯總示於表4中。 Copper particles (manufactured by CI, NanoTekR CuO, average particle diameter: 48 nm), 48.3 parts by mass, copper particles having an average particle diameter of 3.2 μm (1200 YP, manufactured by Mitsui Mining Co., Ltd.), 9.7 parts by mass, polyethylene glycol 1500 parts by mass of 20,000 parts by mass, polyethylene glycol 2000000 (manufactured by Wako Pure Chemicals Co., Ltd.), 6.9 parts by mass of glycerin, and 28.3 parts by mass of ion-exchanged water were mixed with 20000 (manufactured by Wako Pure Chemical Co., Ltd.). A mixer (manufactured by THINKY Co., Ltd., defoaming and stirring Taro ARE-310) was subjected to treatment for 3 minutes, thereby obtaining a copper oxide dispersion liquid 14. A conductive film was produced in the same manner as in Example 25 using the copper oxide dispersion 14, and various evaluations were carried out. The results are summarized in Table 4.

<實施例32> <Example 32>

將氧化銅粒子(C.I.化成製造，NanoTekR CuO，平均粒徑為48nm)44.6質量份、平均粒徑為3.2μm的銅粒子(1200YP，三井金屬礦業(股)製造)13.4質量份、聚乙二醇20000(和光純藥(股)公司製造)5質量份、聚乙二醇2000000(和光純藥(股)公司製造)1.3質量份、甘油6.9質量份及離子交換水27.8質量份混合，利用自轉公轉混合機(新基(THINKY)公司製造，消泡攪拌太郎ARE-310)進行3分鐘處理，由此獲得氧化銅分散液15。使用氧化銅分散液15，依照與實施例25相同的順序製造導電膜，實施各種評價。將結果匯總示於表4中。 44.6 parts by mass of copper oxide particles (manufactured by CI, NanoTekR CuO, average particle diameter: 48 nm), copper particles (1200 YP, manufactured by Mitsui Mining Co., Ltd.) having an average particle diameter of 3.2 μm, 13.4 parts by mass, polyethylene glycol 2000 parts (manufactured by Wako Pure Chemical Co., Ltd.), 5 parts by mass, polyethylene glycol 2,000,000 (manufactured by Wako Pure Chemical Industries, Ltd.), 1.3 parts by mass, 6.9 parts by mass of glycerin, and 27.8 parts by mass of ion-exchanged water, and rotated by rotation A mixer (manufactured by THINKY Co., Ltd., defoaming and stirring Taro ARE-310) was subjected to treatment for 3 minutes, thereby obtaining a copper oxide dispersion liquid 15. A conductive film was produced in the same manner as in Example 25 using the copper oxide dispersion 15, and various evaluations were carried out. The results are summarized in Table 4.

<實施例33> <Example 33>

將氧化銅粒子(C.I.化成製造，NanoTekR CuO，平均粒徑為48nm)19.3質量份、平均粒徑為3.2μm的銅粒子(1200YP，三井金屬礦業(股)製造)38.7質量份、聚乙二醇20000(和光純藥(股)公司製造)2.2質量份、聚乙二醇2000000(和光純藥(股)公司製造)0.7質量份、甘油6.9質量份及離子交換水32.2質量份混合，利用自轉公轉混合機(新基(THINKY)公司製造，消泡攪拌太郎ARE-310)進行3分鐘處理，由此獲得氧化銅分散液16。使用氧化銅分散液16，依照與實施例25相同的順序製造導電膜，實施各種評價。將結果匯總示於表4中。 17.3 parts by mass of copper oxide particles (manufactured by CI, NanoTekR CuO, average particle diameter: 48 nm), copper particles (1200 YP, manufactured by Mitsui Mining Co., Ltd.) having an average particle diameter of 3.2 μm, 38.7 parts by mass, polyethylene glycol 2000 parts (manufactured by Wako Pure Chemical Co., Ltd.), 2.2 parts by mass, polyethylene glycol 2000000 (manufactured by Wako Pure Chemical Industries, Ltd.), 0.7 parts by mass, 6.9 parts by mass of glycerin, and 32.2 parts by mass of ion-exchanged water, and rotated by rotation A mixer (manufactured by THINKY Co., Ltd., defoaming and stirring Taro ARE-310) was subjected to treatment for 3 minutes, thereby obtaining a copper oxide dispersion 16. A conductive film was produced in the same manner as in Example 25 using the copper oxide dispersion 16, and various evaluations were carried out. The results are summarized in Table 4.

<實施例34> <Example 34>

將氧化銅粒子(C.I.化成製造，NanoTekR CuO，平均粒徑為48nm)16.6質量份、平均粒徑為3.2μm的銅粒子(1200YP，三 井金屬礦業(股)製造)41.4質量份、聚乙二醇20000(和光純藥(股)公司製造)1.8質量份、聚乙二醇2000000(稱光純藥(股)公司製造)0.5質量份、甘油6.9質量份及離子交換水32.8質量份混合，利用自轉公轉混合機(新基(THINKY)公司製造，消泡攪拌太郎ARE-310)進行3分鐘處理，由此獲得氧化銅分散液17。使用氧化銅分散液17，依照與實施例25相同的順序製造導電膜，實施各種評價。將結果匯總示於表4中。 Copper oxide particles (1200 YP, three) having 16.6 parts by mass of copper oxide particles (manufactured by C.I., NanoTekR CuO, average particle diameter: 48 nm) and an average particle diameter of 3.2 μm 41.4 parts by mass of Polyethylene Glycol 20000 (manufactured by Wako Pure Chemicals Co., Ltd.), 1.8 parts by mass of polyethylene glycol 2,000,000 (manufactured by Wako Pure Chemicals Co., Ltd.), 0.5 parts by mass, 6.9 parts by mass of glycerin and 32.8 parts by mass of ion-exchanged water were mixed, and the copper oxide dispersion liquid 17 was obtained by performing a treatment for 3 minutes using a spinning revolution mixer (manufactured by THINKY Co., Ltd., defoaming stirring Taro ARE-310). Using a copper oxide dispersion liquid 17, a conductive film was produced in the same manner as in Example 25, and various evaluations were carried out. The results are summarized in Table 4.

<實施例35> <Example 35>

於實施例32中，使用PEN基材代替玻璃環氧樹脂基材，且如表5般變更線速、輸出，除此以外，依照與實施例32相同的順序製造導電膜，實施各種評價。將結果匯總示於表5中。 In the same manner as in Example 32 except that the PEN substrate was used instead of the glass epoxy resin substrate, and the wire speed and the output were changed as shown in Table 5, various evaluations were carried out in the same manner as in Example 32. The results are summarized in Table 5.

<實施例36> <Example 36>

將氧化銅粒子(C.I.化成製造，NanoTekR CuO，平均粒徑為48nm)34.1質量份、銅粒子(1200YP，三井金屬礦業(股)製造，平均粒徑為3.2μm)23.9質量份、聚乙二醇20000(和光純藥(股)公司製造)3.8質量份、聚乙二醇2000000(和光純藥(股)公司製造)1質量份、甘油6.9質量份及離子交換水30.3質量份混合，利用自轉公轉混合機(新基(THINKY)公司製造，消泡攪拌太郎ARE-310)進行3分鐘處理，由此獲得氧化銅分散液18。 34.1 parts by mass of copper oxide particles (manufactured by CI, NanoTekR CuO, average particle diameter: 48 nm), copper particles (1200 YP, manufactured by Mitsui Mining & Mining Co., Ltd., average particle diameter: 3.2 μm), 23.9 parts by mass, polyethylene glycol 2000 parts (manufactured by Wako Pure Chemical Co., Ltd.), 3.8 parts by mass, polyethylene glycol 2,000,000 (manufactured by Wako Pure Chemical Industries, Ltd.), 1 part by mass, 6.9 parts by mass of glycerin, and 30.3 parts by mass of ion-exchanged water, and rotated by rotation A mixer (manufactured by THINKY Co., Ltd., defoaming and stirring Taro ARE-310) was subjected to treatment for 3 minutes, thereby obtaining a copper oxide dispersion liquid 18.

使用氧化銅分散液18代替氧化銅分散液15，除此以外，依照與實施例35相同的順序製造導電膜，實施各種評價。將結果匯總示於表5中。 A conductive film was produced in the same manner as in Example 35 except that the copper oxide dispersion liquid 18 was used instead of the copper oxide dispersion liquid 15, and various evaluations were carried out. The results are summarized in Table 5.

<實施例37> <Example 37>

將氧化銅粒子(C.I.化成製造，NanoTekR CuO，平均粒徑為48nm)46.4質量份、銅粒子(1200YP，三井金屬礦業(股)製造，平均粒徑為3.2μm)11.6質量份、聚乙二醇20000(和光純藥(股)公司製造)5.2質量份、聚乙二醇2000000(和光純藥(股)公司製造)1.3質量份、甘油6.9質量份及離子交換水28.6質量份混合，利用自轉公轉混合機(新基(THINKY)公司製造，消泡攪拌太郎ARE-310)進行3分鐘處理，由此獲得氧化銅分散液19。 46.4 parts by mass of copper oxide particles (manufactured by CI, NanoTekR CuO, average particle diameter: 48 nm), copper particles (1200 YP, manufactured by Mitsui Mining & Mining Co., Ltd., average particle diameter: 3.2 μm), 11.6 parts by mass, polyethylene glycol 20000 (manufactured by Wako Pure Chemicals Co., Ltd.) 5.2 parts by mass, polyethylene glycol 2000000 (manufactured by Wako Pure Chemicals Co., Ltd.), 1.3 parts by mass, 6.9 parts by mass of glycerin, and 28.6 parts by mass of ion-exchanged water, and rotated by rotation A mixer (manufactured by THINKY Co., Ltd., defoaming and stirring Taro ARE-310) was subjected to treatment for 3 minutes, thereby obtaining a copper oxide dispersion liquid 19.

使用氧化銅分散液19代替氧化銅分散液18，除此以外，依照與實施例36相同的順序製造導電膜，實施各種評價。將結果匯總示於表5中。 A conductive film was produced in the same manner as in Example 36 except that the copper oxide dispersion liquid 19 was used instead of the copper oxide dispersion liquid 18, and various evaluations were carried out. The results are summarized in Table 5.

<實施例38> <Example 38>

將氧化銅粒子(C.I.化成製造，NanoTekR CuO，平均粒徑為48nm)33.1質量份、銅粒子(1200YP，三井金屬礦業(股)製造，平均粒徑為3.2μm)24.9質量份、聚乙二醇20000(和光純藥(股)公司製造)3.7質量份、聚乙二醇2000000(和光純藥(股)公司製造)0.9質量份、甘油6.9質量份及離子交換水30.5質量份混合，利用自轉公轉混合機(新基(THINKY)公司製造，消泡攪拌太郎ARE-310)進行3分鐘處理，由此獲得氧化銅分散液20。 33.1 parts by mass of copper oxide particles (manufactured by CI, NanoTekR CuO, average particle diameter: 48 nm), copper particles (1200 YP, manufactured by Mitsui Mining & Mining Co., Ltd., average particle diameter: 3.2 μm), 24.9 parts by mass, polyethylene glycol 20000 (manufactured by Wako Pure Chemical Co., Ltd.), 3.7 parts by mass, polyethylene glycol 2000000 (manufactured by Wako Pure Chemical Industries, Ltd.), 0.9 parts by mass, 6.9 parts by mass of glycerin, and 30.5 parts by mass of ion-exchanged water, and rotated by rotation A mixer (manufactured by THINKY Co., Ltd., defoaming and stirring Taro ARE-310) was subjected to treatment for 3 minutes, thereby obtaining a copper oxide dispersion 20.

使用氧化銅分散液20代替氧化銅分散液18，除此以外，依照與實施例36相同的順序製造導電膜，實施各種評價。將結果匯總示於表5中。 A conductive film was produced in the same manner as in Example 36 except that the copper oxide dispersion liquid 20 was used instead of the copper oxide dispersion liquid 18, and various evaluations were carried out. The results are summarized in Table 5.

<實施例39> <Example 39>

將氧化銅粒子(C.I.化成製造，NanoTekR CuO，平均粒徑為48nn)34.1質量份、銅粒子(1200YP，三井金屬礦業(股)製造，平均粒徑為3.2μm)23.9質量份、聚乙二醇20000(和光純藥(股)公司製造)2.2質量份、聚乙二醇2000000(和光純藥(股)公司製造)0.6質量份、甘油6.9質量份及離子交換水32.3質量份混合，利用自轉公轉混合機(新基(THINKY)公司製造，消泡攪拌太郎ARE-310)進行3分鐘處理，由此獲得氧化銅分散液21。 34.1 parts by mass of copper oxide particles (manufactured by CI, NanoTekR CuO, average particle diameter: 48 nn), copper particles (1200 YP, manufactured by Mitsui Mining & Mining Co., Ltd., average particle diameter: 3.2 μm), 23.9 parts by mass, polyethylene glycol 2000 parts (manufactured by Wako Pure Chemicals Co., Ltd.), 2.2 parts by mass, polyethylene glycol 2,000,000 (manufactured by Wako Pure Chemical Industries, Ltd.), 0.6 parts by mass, 6.9 parts by mass of glycerin, and 32.3 parts by mass of ion-exchanged water, and rotated by rotation A mixer (manufactured by THINKY Co., Ltd., defoaming and stirring Taro ARE-310) was subjected to treatment for 3 minutes, thereby obtaining a copper oxide dispersion liquid 21.

使用氧化銅分散液21代替氧化銅分散液18，除此以外，依照與實施例36相同的順序製造導電膜，實施各種評價。將結果匯總示於表5中。 A conductive film was produced in the same manner as in Example 36 except that the copper oxide dispersion liquid 21 was used instead of the copper oxide dispersion liquid 18, and various evaluations were carried out. The results are summarized in Table 5.

<實施例40> <Example 40>

將氧化銅粒子(C.I.化成製造，NanoTekR CuO，平均粒徑為48nm)34.1質量份、銅粒子(1200YP，三井金屬礦業(股)製造，平均粒徑為3.2μm)23.9質量份、聚乙二醇20000(和光純藥(股)公司製造)1.6質量份、聚乙二醇2000000(和光純藥(股)公司製造)0.4質量份、甘油6.9質量份及離子交換水33.1質量份混合，利用自轉公轉混合機(新基(THINKY)公司製造，消泡攪拌太郎ARE-310)進行3分鐘處理，由此獲得氧化銅分散液22。 34.1 parts by mass of copper oxide particles (manufactured by CI, NanoTekR CuO, average particle diameter: 48 nm), copper particles (1200 YP, manufactured by Mitsui Mining & Mining Co., Ltd., average particle diameter: 3.2 μm), 23.9 parts by mass, polyethylene glycol 2000 parts (manufactured by Wako Pure Chemical Co., Ltd.), 1.6 parts by mass, polyethylene glycol 2,000,000 (manufactured by Wako Pure Chemical Industries, Ltd.), 0.4 parts by mass, 6.9 parts by mass of glycerin, and 33.1 parts by mass of ion-exchanged water, and rotated by rotation A mixer (manufactured by THINKY Co., Ltd., defoaming and stirring Taro ARE-310) was subjected to treatment for 3 minutes, thereby obtaining a copper oxide dispersion liquid 22.

使用氧化銅分散液22代替氧化銅分散液18，除此以外，依照與實施例36相同的順序製造導電膜，實施各種評價。將結果匯總示於表5中。 A conductive film was produced in the same manner as in Example 36 except that the copper oxide dispersion liquid 22 was used instead of the copper oxide dispersion liquid 18, and various evaluations were carried out. The results are summarized in Table 5.

<實施例41> <Example 41>

將氧化銅粒子(C.I.化成製造，NanoTekR CuO，平均粒徑為48nm)34.1質量份、銅粒子(1200YP，三井金屬礦業(股)製造，平均粒徑為3.2μm)23.9質量份、聚乙二醇20000(和光純藥(股)公司製造)4.4質量份、聚乙二醇2000000(和光純藥(股)公司製造)1.1質量份、甘油6.9質量份及離子交換水29.6質量份混合，利用自轉公轉混合機(新基(THINKY)公司製造，消泡攪拌太郎ARE-310)進行3分鐘處理，由此獲得氧化銅分散液23。 34.1 parts by mass of copper oxide particles (manufactured by CI, NanoTekR CuO, average particle diameter: 48 nm), copper particles (1200 YP, manufactured by Mitsui Mining & Mining Co., Ltd., average particle diameter: 3.2 μm), 23.9 parts by mass, polyethylene glycol 20000 (manufactured by Wako Pure Chemical Co., Ltd.), 4.4 parts by mass, polyethylene glycol 2000000 (manufactured by Wako Pure Chemical Industries, Ltd.), 1.1 parts by mass, 6.9 parts by mass of glycerin, and 29.6 parts by mass of ion-exchanged water, and rotated by rotation A mixer (manufactured by THINKY Co., Ltd., defoaming and stirring Taro ARE-310) was subjected to treatment for 3 minutes, thereby obtaining a copper oxide dispersion liquid 23.

使用氧化銅分散液23代替氧化銅分散液18，除此以外，依照與實施例36相同的順序製造導電膜，實施各種評價。將結果匯總示於表5中。 A conductive film was produced in the same manner as in Example 36 except that the copper oxide dispersion liquid 23 was used instead of the copper oxide dispersion liquid 18, and various evaluations were carried out. The results are summarized in Table 5.

<實施例42~實施例44> <Example 42 to Example 44>

於實施例36的氧化銅分散液18的製備時，分別使用平均粒徑為1.1μm的銅粒子(1100Y，三井金屬礦業(股)製造)、平均粒徑為0.49μm的銅粒子(1030Y，三井金屬礦業(股)製造)、平均粒徑為6.3μm的銅粒子(1400Y，三井金屬礦業(股)製造)代替銅粒子(1200YP，三井金屬礦業(股)製造，平均粒徑為3.2μm)，製備氧化銅分散液24~氧化銅分散液26，依照與實施例36相同的順序製造導電膜，實施各種評價。將結果匯總示於表5中。 In the preparation of the copper oxide dispersion liquid 18 of Example 36, copper particles (1100Y, manufactured by Mitsui Mining & Mining Co., Ltd.) having an average particle diameter of 1.1 μm and copper particles having an average particle diameter of 0.49 μm (1030Y, Mitsui, respectively) were used. Metallic mining (manufactured by metal mining), copper particles with an average particle diameter of 6.3 μm (1400Y, manufactured by Mitsui Mining & Mining Co., Ltd.) instead of copper particles (1200YP, manufactured by Mitsui Mining & Mining Co., Ltd., average particle size 3.2 μm), A copper oxide dispersion liquid 24 to a copper oxide dispersion liquid 26 was prepared, and a conductive film was produced in the same manner as in Example 36, and various evaluations were carried out. The results are summarized in Table 5.

<實施例45~實施例47、比較例10> <Example 45 to Example 47, Comparative Example 10>

於實施例36中，如表5所示般變更輸出，除此以外，依照與實施例36相同的順序製造導電膜，實施各種評價。將結果匯總示 於表5中。 In the same manner as in Example 36 except that the output was changed as shown in Table 5, the conductive film was produced in the same manner as in Example 36, and various evaluations were carried out. Summary results In Table 5.

<實施例48~實施例50> <Example 48 to Example 50>

於實施例45中，如表5所示般變更線速，除此以外，依照與實施例45相同的順序製造導電膜，實施各種評價。將結果匯總示於表5中。 In the same manner as in Example 45 except that the line speed was changed as shown in Table 5, the conductive film was produced in the same manner as in Example 45, and various evaluations were carried out. The results are summarized in Table 5.

<實施例51> <Example 51>

於實施例46中，使用PET基材代替PEN基材，除此以外，依照與實施例46相同的順序製造導電膜，實施各種評價。將結果匯總示於表5中。 A conductive film was produced in the same manner as in Example 46 except that a PET substrate was used instead of the PEN substrate, and various evaluations were carried out. The results are summarized in Table 5.

於表1~表3中，「式1的範圍內」、「式2的範圍內」、「式3的範圍內」欄中，將各實施例及比較例的條件滿足式1~式3的各條件的情形視為「A」，將不滿足的情形視為「B」。 In Tables 1 to 3, in the "in the range of Formula 1", "In the range of Formula 2", and "In the range of Formula 3" column, the conditions of the respective examples and comparative examples satisfy the formulas 1 to 3. The case of each condition is regarded as "A", and the case of unsatisfaction is regarded as "B".

如表1~表5所示，根據本發明的製造方法，可獲得缺陷少、導電性優異的導電膜。 As shown in Tables 1 to 5, according to the production method of the present invention, a conductive film having few defects and excellent conductivity can be obtained.

其中，如由實施例1、實施例5、實施例6的比較所得知般，確認到滿足式2的關係的實施例1、實施例5與不滿足式2的關係的實施例6相比，導電膜的缺陷更少。 As described in the comparison of the first embodiment, the fifth embodiment, and the sixth embodiment, it is confirmed that the first embodiment and the fifth embodiment satisfying the relationship of the formula 2 are compared with the sixth embodiment in which the relationship of the formula 2 is not satisfied. The conductive film has fewer defects.

另外，如由實施例9~實施例12的比較所得知般，確認到於重疊率為15%~30%的情形時，可獲得導電性更優異的導電膜。 In the case where the overlap ratio is 15% to 30%, it is confirmed that the conductive film having more excellent conductivity can be obtained as compared with the comparison of Examples 9 to 12.

另外，如由實施例18~實施例21的比較所得知般，確認到於既定的有機化合物的量為8質量%~20質量%的情形時，可獲得缺陷更少、導電性更優異的導電膜。 In the case where the amount of the predetermined organic compound is from 8 to 20% by mass, it is confirmed that the conductivity is more excellent and the conductivity is more excellent. membrane.

另外，如由實施例22~實施例26的比較所得知般，確認到於銅粒子的平均粒徑為0.4μm~3.5μm的情形時，可獲得導電性更優異的導電膜。 In the case where the average particle diameter of the copper particles is from 0.4 μm to 3.5 μm, it is confirmed that the conductive film having more excellent conductivity can be obtained as compared with the comparison of the examples 22 to 26.

另外，如由實施例25、實施例27~實施例29的比較所得知般，確認到於線速為10mm/s~80mm/s的情形時，可獲得導電性更優異的導電膜。 In the case where the linear velocity is 10 mm/s to 80 mm/s, it is confirmed that the conductive film having more excellent conductivity can be obtained as compared with the comparison between the embodiment 25 and the embodiment 27 to the embodiment 29.

另外，如由實施例25、實施例31~實施例34的比較所得知般，確認到於相對於氧化銅粒子的總質量而銅粒子的含量為30質量%~200質量%的情形時，可獲得缺陷更少、導電性更優異的導電膜。 In addition, as seen from the comparison between Example 25 and Example 31 to Example 34, when the content of the copper particles is 30% by mass to 200% by mass based on the total mass of the copper oxide particles, A conductive film having fewer defects and more excellent conductivity is obtained.

另外，如由實施例13、實施例35~實施例38的比較所得知般，確認到於相對於氧化銅粒子的總質量而銅粒子的含量為30質 量%~70質量%時，可獲得缺陷更少、導電性更優異的導電膜。 Further, as seen from the comparison of Example 13 and Example 35 to Example 38, it was confirmed that the content of the copper particles was 30% with respect to the total mass of the copper oxide particles. When the amount is from % to 70% by mass, a conductive film having fewer defects and more excellent conductivity can be obtained.

另外，如由實施例36、實施例39~實施例41的比較所得知般，確認到於聚乙二醇的含量為氧化銅粒子的總質量的8質量%~14質量%時，可獲得導電性更優異的導電膜。 Further, as seen from the comparison between Example 36 and Example 39 to Example 41, it was confirmed that the conductive content was obtained when the content of the polyethylene glycol was 8 mass% to 14 mass% of the total mass of the copper oxide particles. More excellent conductive film.

另外，如由實施例36、實施例42~實施例44的比較所得知般，確認到於含有平均粒徑為1.0μm~3.5μm的銅粒子時，可獲得導電性更優異的導電膜。 In the case of the copper particles having an average particle diameter of 1.0 μm to 3.5 μm, it was confirmed that the conductive film having more excellent conductivity was obtained as compared with the comparison between Example 36 and Example 42 to Example 44.

另外，如由實施例36、實施例45~實施例47的比較所得知般，確認到滿足式3的關係的實施例36、實施例45、實施例46與不滿足式3的關係的實施例47相比，導電膜的缺陷更少且導電性更優異。 Further, as seen from the comparison of Example 36 and Example 45 to Example 47, examples of the relationship between Example 36, Example 45, and Example 46 satisfying the relationship of Expression 3 and the relationship not satisfying Expression 3 were confirmed. Compared with 47, the conductive film has fewer defects and is more excellent in electrical conductivity.

另外，如由實施例45、實施例48~實施例50的比較所得知般，確認到於雷射的掃描速度為10mm/s~60mm/s的情形時，導電性更優異。 Further, as seen from the comparison between Example 45 and Example 48 to Example 50, it was confirmed that the conductivity was more excellent when the scanning speed of the laser was 10 mm/s to 60 mm/s.

另一方面，不滿足本發明的製造方法的要件的比較例1~比較例10中，導電膜中存在大量的缺陷，或導電性差。 On the other hand, in Comparative Examples 1 to 10 which did not satisfy the requirements of the production method of the present invention, a large number of defects were present in the conductive film, or the conductivity was poor.

10‧‧‧基材 10‧‧‧Substrate

12‧‧‧前驅物膜 12‧‧‧Precursor film

14‧‧‧雷射光源 14‧‧‧Laser light source

16‧‧‧雷射光 16‧‧‧Laser light

18‧‧‧導電膜 18‧‧‧Electrical film

Claims (10)

一種導電膜的製造方法，包括：將含有平均粒徑為100nm以下的氧化銅粒子的分散液塗佈於基材上，形成含有所述氧化銅粒子的前驅物膜的步驟；以及對所述前驅物膜一面照射波長為9μm~11μm的雷射光一面相對地掃描，將經所述雷射光照射的掃描區域中的所述氧化銅粒子還原，形成含有金屬銅的導電膜的步驟；並且所述前驅物膜的膜厚為0.5μm~30μm，所述掃描的速度為10mm/s~120mm/s，所述基材的熱傳導率A[W/(m．K)]與所述雷射光的輸出W[W]滿足式1的關係，所述基材的熱傳導率A為0.014以上，式1 1.39+0.3252Ln(A)≦W≦3.00+0.3252Ln(A)再者，式中，Ln表示自然對數。 A method for producing a conductive film, comprising: applying a dispersion liquid containing copper oxide particles having an average particle diameter of 100 nm or less to a substrate to form a precursor film containing the copper oxide particles; and the precursor The film is irradiated with respect to the laser light having a wavelength of 9 μm to 11 μm, and the copper oxide particles in the scanning region irradiated with the laser light are reduced to form a conductive film containing metal copper; and the precursor The film thickness of the film is 0.5 μm to 30 μm, the scanning speed is 10 mm/s to 120 mm/s, and the thermal conductivity A [W/(m.K)] of the substrate and the output of the laser light are W. [W] satisfying the relationship of Formula 1, the thermal conductivity A of the substrate is 0.014 or more, and Formula 1 1.39+0.3252Ln(A)≦W≦3.00+0.3252Ln(A), wherein Ln represents the natural logarithm . 如申請專利範圍第1項所述的導電膜的製造方法，其中所述基材的熱傳導率A[W/(m．K)]與所述雷射光的輸出W[W]滿足式2的關係，式2 1.39+0.3252Ln(A)≦W≦2.40+0.3252Ln(A)。 The method for producing a conductive film according to claim 1, wherein the thermal conductivity A [W/(m.K)] of the substrate and the output W[W] of the laser light satisfy the relationship of Formula 2. , Equation 2 1.39 + 0.3252 Ln (A) ≦ W ≦ 2.40 + 0.3252 Ln (A). 如申請專利範圍第1項或第2項所述的導電膜的製造方 法，其中於利用所述雷射光對與經所述雷射光照射的第1掃描區域鄰接的區域進行掃描時，以與所述第1掃描區域局部重複的方式照射雷射光，且所述重複區域的寬度相當於所述雷射光的點徑的15%~30%的大小。 The manufacturer of the conductive film as described in claim 1 or 2 In the method of scanning, by using the laser light, an area adjacent to the first scanning area irradiated by the laser light, irradiating the laser light in a manner partially overlapping the first scanning area, and the overlapping area The width is equivalent to 15% to 30% of the spot diameter of the laser light. 如申請專利範圍第1項或第2項所述的導電膜的製造方法，其中所述基材為選自由聚對苯二甲酸乙二酯基材、聚萘二甲酸乙二酯基材、聚醯亞胺基材及玻璃環氧樹脂基材所組成的組群中的任一種。 The method for producing a conductive film according to claim 1 or 2, wherein the substrate is selected from the group consisting of polyethylene terephthalate substrate, polyethylene naphthalate substrate, and poly Any one of a group consisting of a quinone imine substrate and a glass epoxy substrate. 如申請專利範圍第1項或第2項所述的導電膜的製造方法，其中於所述分散液中含有選自由乙烯系聚合物、聚醚及糖所組成的組群中的至少一種有機化合物。 The method for producing a conductive film according to the above aspect, wherein the dispersion contains at least one organic compound selected from the group consisting of a vinyl polymer, a polyether, and a sugar. . 如申請專利範圍第5項所述的導電膜的製造方法，其中所述有機化合物含有選自由聚乙烯基吡咯啶酮、聚乙二醇及糖所組成的組群中的至少一種。 The method for producing a conductive film according to claim 5, wherein the organic compound contains at least one selected from the group consisting of polyvinylpyrrolidone, polyethylene glycol, and sugar. 如申請專利範圍第5項所述的導電膜的製造方法，其中相對於所述氧化銅粒子的總質量，所述有機化合物的含量為8質量%~20質量%。 The method for producing a conductive film according to claim 5, wherein the content of the organic compound is from 8 to 20% by mass based on the total mass of the copper oxide particles. 如申請專利範圍第1項或第2項所述的導電膜的製造方法，其中於所述分散液中含有平均粒徑為0.4μm~3.5μm的銅粒子，且所述掃描的速度為10mm/s~80mm/s。 The method for producing a conductive film according to claim 1 or 2, wherein the dispersion contains copper particles having an average particle diameter of 0.4 μm to 3.5 μm, and the scanning speed is 10 mm/ s~80mm/s. 如申請專利範圍第8項所述的導電膜的製造方法，其中相 對於所述氧化銅粒子的總質量，所述銅粒子的含量為30質量%~200質量%。 The method for producing a conductive film according to claim 8, wherein the phase The content of the copper particles is from 30% by mass to 200% by mass based on the total mass of the copper oxide particles. 如申請專利範圍第1項或第2項所述的導電膜的製造方法，其中所述掃描的速度為10mm/s~60mm/s；所述基材為聚對苯二甲酸乙二酯基材或聚萘二甲酸乙二酯基材；於所述分散液中含有聚乙二醇，相對於所述氧化銅粒子的總質量，所述聚乙二醇的含量為8質量%~14質量%；於所述分散液中含有平均粒徑為1.0μm~3.5μm的銅粒子，相對於所述氧化銅粒子的總質量，所述銅粒子的含量為30質量%~70質量%；所述基材的熱傳導率A[W/(m．K)]與所述雷射光的輸出W[W]滿足式3的關係，式3 1.39+0.3252Ln(A)≦W≦1.75+0.3252Ln(A)。 The method for producing a conductive film according to claim 1 or 2, wherein the scanning speed is 10 mm/s to 60 mm/s; and the substrate is a polyethylene terephthalate substrate. Or a polyethylene naphthalate substrate; the polyethylene glycol is contained in the dispersion, and the content of the polyethylene glycol is 8% by mass to 14% by mass based on the total mass of the copper oxide particles. And containing, in the dispersion, copper particles having an average particle diameter of 1.0 μm to 3.5 μm, and the content of the copper particles is 30% by mass to 70% by mass based on the total mass of the copper oxide particles; The thermal conductivity A[W/(m.K)] of the material and the output W[W] of the laser light satisfy the relationship of Equation 3, Equation 3 1.39+0.3252Ln(A)≦W≦1.75+0.3252Ln(A) .
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