TW201439133A - Composition for forming conductive film and method for producing conductive film with the same - Google Patents

Composition for forming conductive film and method for producing conductive film with the same Download PDF

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TW201439133A
TW201439133A TW103106159A TW103106159A TW201439133A TW 201439133 A TW201439133 A TW 201439133A TW 103106159 A TW103106159 A TW 103106159A TW 103106159 A TW103106159 A TW 103106159A TW 201439133 A TW201439133 A TW 201439133A
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group
formula
conductive film
composition
polymer
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TW103106159A
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Toru Watanabe
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Fujifilm Corp
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Abstract

The object of the invention is to provide a composition for forming conductive film, which can form a conductive film having a good adhesion to a substrate and an excellent electrical conductivity even undergoing a sintering using light irradiation. The composition for forming conductive film of the invention includes: copper oxide particle and/or copper particle, a polymer including a repeating unit represented by a particular formula having a reducing group and a repeating unit represented by a particular formula having a cross linking group, and a curing agent reacting with the cross linking group.

Description

導電膜形成用組成物及使用其的導電膜的製造方法 Conductive film forming composition and method of producing conductive film using the same

本發明是有關於一種導電膜形成用組成物及使用其的導電膜的製造方法。 The present invention relates to a composition for forming a conductive film and a method for producing a conductive film using the same.

已知如下方法：藉由利用印刷法，將金屬粒子或金屬氧化物粒子的分散體塗佈於基材上，進行加熱處理而使其燒結，從而形成配線等導電膜。 A method is known in which a dispersion of metal particles or metal oxide particles is applied onto a substrate by a printing method, followed by heat treatment and sintering to form a conductive film such as a wiring.

與現有的藉由高熱．真空製程(濺鍍)或鍍敷處理的導電膜形成方法相比，上述方法由於簡便．節約能源．節約資源，故而在下一代電子開發中受到很大期待。其中，近年來，就低成本化的觀點而言，如下方法受到關注：藉由使用包含金屬氧化物粒子的組成物，對其進行加熱處理而使其還原，並且使其燒結而形成導電膜。 With existing high heat. Compared with the vacuum process (sputtering) or plating process of the conductive film formation method, the above method is simple. Energy saving. Saving resources, so it is expected in the next generation of electronic development. Among them, in recent years, from the viewpoint of cost reduction, the following method has been attracting attention: by using a composition containing metal oxide particles, it is subjected to heat treatment to be reduced, and sintered to form a conductive film.

另一方面，於以上述方式進行加熱處理而燒結的情況下，基材被暴露於高溫中。因此，存在基材藉由熱而變形，難以獲得均勻的導電膜的問題。 On the other hand, in the case where the heat treatment is performed in the above manner and sintered, the substrate is exposed to a high temperature. Therefore, there is a problem that the substrate is deformed by heat, and it is difficult to obtain a uniform conductive film.

其中，專利文獻1中揭示有如下方法：藉由進行利用光照射的燒結(光燒結)，不會對基材過度加熱，將基材上的氧化銅 墨水燒結而形成金屬銅膜(段落0013、實施例1等)。 Among them, Patent Document 1 discloses a method of performing copper oxide on a substrate by performing sintering (photo sintering) by light irradiation without excessive heating of the substrate. The ink is sintered to form a metallic copper film (paragraph 0013, Example 1, etc.).

[現有技術文獻] [Prior Art Literature]

[專利文獻] [Patent Literature]

[專利文獻1]日本專利特表2010-528428號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-528428

然而，本發明者以專利文獻1為參考，於基材上賦予包含銅粒子或氧化銅粒子及黏合劑(聚乙烯基吡咯啶酮等)的組成物，進行加熱乾燥而形成塗膜，然後對所形成的塗膜照射光而形成導電膜，結果瞭解到基材與導電膜之間的密接性變得不充分。若如上所述，基材與導電膜之間的密接性不充分，則當形成配線等時容易產生斷線或短路等異常，因此成為問題。另外，亦瞭解到存在所得導電膜的導電性變得不充分的情況。 However, the inventors of the present invention gave a composition containing copper particles, copper oxide particles, and a binder (polyvinylpyrrolidone) to a substrate, and dried by heating to form a coating film, and then When the formed coating film was irradiated with light to form a conductive film, it was found that the adhesion between the substrate and the conductive film was insufficient. When the adhesion between the substrate and the conductive film is insufficient as described above, when wiring or the like is formed, an abnormality such as disconnection or short-circuiting is likely to occur, which is a problem. Further, it is also known that the conductivity of the obtained conductive film may be insufficient.

因此，本發明鑒於上述實際情況，目的在於提供一種即便進行利用光照射的燒結，亦可獲得與基材的密接性良好且導電性優異的導電膜的導電膜形成用組成物。 Therefore, the present invention has been made in view of the above-described circumstances, and it is an object of the present invention to provide a conductive film-forming composition which can obtain a conductive film having excellent adhesion to a substrate and excellent conductivity even when sintering by light irradiation is performed.

本發明者為了完成上述課題而進行積極研究，結果發現，藉由製成包含氧化銅粒子及/或銅粒子、包含具有特定還原性基的重複單元及具有特定交聯性基的重複單元的聚合物、以及與上述交聯性基進行反應的硬化劑的組成物，則對由組成物形成的塗膜照射光而獲得的導電膜與基材的密接性良好，且導電性優異，從而完成本發明。 The inventors of the present invention conducted active research to accomplish the above problems, and as a result, found that polymerization is carried out by preparing a copper oxide particle and/or copper particles, a repeating unit having a specific reducing group, and a repeating unit having a specific crosslinkable group. The composition of the hardening agent that reacts with the crosslinkable group is excellent in adhesion between the conductive film obtained by irradiating the coating film formed of the composition and the substrate, and the conductivity is excellent, thereby completing the present invention. invention.

即，本發明者等人發現可藉由以下的構成來解決上述課題。 In other words, the inventors of the present invention have found that the above problems can be solved by the following configuration.

(1)一種導電膜形成用組成物，其含有：氧化銅粒子及/或銅粒子、包含後述式(1)所表示的重複單元及後述式(2)所表示的重複單元的聚合物、以及與後述式(2)中的B所表示的交聯性基進行反應的硬化劑。 (1) A conductive film-forming composition comprising: copper oxide particles and/or copper particles, a polymer comprising a repeating unit represented by the following formula (1), and a repeating unit represented by the following formula (2); A curing agent that reacts with a crosslinkable group represented by B in the following formula (2).

(2)如上述(1)所述的導電膜形成用組成物，其中上述聚合物為：包含後述式(3)所表示的重複單元及後述式(2)所表示的重複單元的聚合物、包含後述式(4)所表示的重複單元及後述式(5)所表示的重複單元的聚合物、或者包含後述式(6)所表示的重複單元的聚合物。 (2) The conductive film-forming composition according to the above-mentioned item (1), wherein the polymer is a polymer comprising a repeating unit represented by the following formula (3) and a repeating unit represented by the following formula (2), A polymer comprising a repeating unit represented by the following formula (4) and a repeating unit represented by the following formula (5), or a polymer comprising a repeating unit represented by the following formula (6).

(3)如上述(2)所述的導電膜形成用組成物，其中上述聚合物為包含上述式(3)所表示的重複單元及上述式(2)所表示的重複單元的聚合物。 (3) The conductive film-forming composition according to the above (2), wherein the polymer is a polymer comprising a repeating unit represented by the above formula (3) and a repeating unit represented by the above formula (2).

(4)如上述(1)~(3)中任一項所述的導電膜形成用組成物，其中上述式(2)中的B為上述式(B-1)或式(B-7)所表示的基，上述硬化劑為胺或醇。 The composition for forming a conductive film according to any one of the above aspects (1), wherein B in the above formula (2) is the above formula (B-1) or formula (B-7). The above-mentioned hardener is an amine or an alcohol.

(5)如上述(1)~(3)中任一項所述的導電膜形成用組成物，其中上述式(2)中的B為上述式(B-2)所表示的基，上述硬化劑為環氧化物、醛、或者具有2個以上的後述式(13)所表示的部分結構的化合物。 The composition for forming a conductive film according to any one of the above aspects (1), wherein B in the formula (2) is a group represented by the above formula (B-2), and the hardening is performed. The agent is an epoxide, an aldehyde, or a compound having two or more partial structures represented by the following formula (13).

(6)一種導電膜的製造方法，其包括：塗膜形成步驟，將如上述(1)~(5)中任一項所述的導電膜形成用組成物賦予至基材上，於上述基材上形成組成物層，然 後，對上述組成物層實施加熱處理而形成塗膜；以及還原步驟，對上述塗膜進行光照射處理，將上述氧化銅粒子及/或銅粒子還原而形成導電膜。 (6) A method of producing a conductive film, comprising: a coating film forming step of imparting a composition for forming a conductive film according to any one of the above (1) to (5) to a substrate, Forming a layer of composition on the material, Thereafter, the composition layer is subjected to heat treatment to form a coating film, and a reduction step is performed, and the coating film is subjected to light irradiation treatment to reduce the copper oxide particles and/or copper particles to form a conductive film.

(7)如上述(6)所述的導電膜的製造方法，其中上述光照射處理為脈衝光照射處理。 (7) The method for producing a conductive film according to the above (6), wherein the light irradiation treatment is pulsed light irradiation treatment.

依據本發明，能夠提供即便進行利用光照射的燒結，亦可獲得與基材的密接性良好，且導電性優異的導電膜的導電膜形成用組成物。 According to the present invention, it is possible to provide a conductive film-forming composition of a conductive film which is excellent in adhesion to a substrate and has excellent conductivity even when sintering by light irradiation is performed.

[導電膜形成用組成物] [Conductive film forming composition]

本發明的導電膜形成用組成物(以下亦稱為本發明的組成物)含有：氧化銅粒子及/或銅粒子、以及包含後述式(1)所表示的重複單元及後述式(2)所表示的重複單元的聚合物。此處，如後所述，式(1)所表示的重複單元具有特定的還原性基。另外，式(2)所表示的重複單元具有特定的交聯性基。另外，本發明的組成物含有與上述式(2)中的B所表示的交聯性基進行反應的硬化劑。 The conductive film-forming composition of the present invention (hereinafter also referred to as the composition of the present invention) contains copper oxide particles and/or copper particles, and a repeating unit represented by the following formula (1) and a formula (2) described later. Represents the polymer of the repeating unit. Here, as described later, the repeating unit represented by the formula (1) has a specific reducing group. Further, the repeating unit represented by the formula (2) has a specific crosslinkable group. Further, the composition of the present invention contains a curing agent which reacts with the crosslinkable group represented by B in the above formula (2).

藉由本發明的組成物採取此種構成，則對由組成物形成的塗膜照射光而獲得的導電膜成為與基材的密接性良好，且導電性優異的膜。 When the composition of the present invention has such a configuration, the conductive film obtained by irradiating light to the coating film formed of the composition has a good adhesion to the substrate and is excellent in conductivity.

其詳情並不明確，但大致推測如下。 The details are not clear, but they are roughly speculated as follows.

於對由含有氧化銅粒子及/或銅粒子的組成物所獲得的塗膜照射光而使其光燒結的情況下，藉由塗膜中的溶劑或黏合劑等成分分解．揮發，塗膜自身會產生微觀或宏觀的破裂，結果，認為所得的導電膜與基材的密接性或導電性變得不充分。 When the coating film obtained from the composition containing copper oxide particles and/or copper particles is irradiated with light to be photo-sintered, it is decomposed by a solvent or a binder in the coating film. When it volatilizes, the coating film itself may cause microscopic or macroscopic fracture, and as a result, it is considered that the adhesion or conductivity of the obtained conductive film to the substrate becomes insufficient.

如上所述，本發明的組成物由於含有特定的聚合物(具有特定的還原性基及特定的交聯性基的聚合物)以及與上述特定的交聯性基進行反應的硬化劑，故而由本發明的組成物形成的塗膜中會形成聚合物彼此的交聯結構。因此，於對由本發明的組成物所獲得的塗膜照射光的情況下，塗膜自身不會發生物理性分解，藉由特定的還原性基等，氧化銅粒子或一部分被氧化的銅粒子被還原，銅粒子彼此熔著，而獲得與基材的密接性優異的導電膜。推測其原因亦在於：於如後述比較例所示，雖含有特定的聚合物但不含硬化劑的情況(比較例1~比較例8)，或雖含有硬化劑但不含特定聚合物(含有雖具有特定的交聯性基但不具有特定的還原性基的聚合物)情況(比較例9)下，密接性變得不充分。 As described above, the composition of the present invention contains a specific polymer (a polymer having a specific reducing group and a specific crosslinkable group) and a curing agent which reacts with the specific crosslinkable group described above. In the coating film formed by the composition of the invention, a crosslinked structure of the polymers is formed. Therefore, in the case where the coating film obtained from the composition of the present invention is irradiated with light, the coating film itself does not physically decompose, and the copper oxide particles or a part of the oxidized copper particles are oxidized by a specific reducing group or the like. After the reduction, the copper particles are fused to each other to obtain a conductive film excellent in adhesion to the substrate. It is presumed that the reason is that, as shown in the comparative example described later, the specific polymer is contained but the curing agent is not contained (Comparative Example 1 to Comparative Example 8), or the curing agent is contained, but the specific polymer is not contained (including In the case of a polymer having a specific crosslinkable group but not having a specific reducing group (Comparative Example 9), the adhesion was insufficient.

另外，如上所述，認為本發明的組成物中所含有的聚合物由於具有特定的還原性基，故而於光燒結時快速產生氧化銅粒子或一部分被氧化的銅粒子的還原，獲得導電性優異的導電膜。 Further, as described above, it is considered that the polymer contained in the composition of the present invention has a specific reducing group, so that copper oxide particles or a part of oxidized copper particles are rapidly reduced during photo sintering, and excellent conductivity is obtained. Conductive film.

此外，於除了具有交聯性基的聚合物以外，另外僅調配並不固定為聚合物的還原劑的情況下，還原劑會於光燒結時揮發，因此氧化銅粒子等的還原並未充分進行，所得導電膜的導電性變得 不充分。即，可以說本發明的其中1個特徵在於使用兼具還原性與交聯性的功能的聚合物。 Further, in addition to the polymer having a crosslinkable group, when only a reducing agent which is not fixed to a polymer is blended, the reducing agent volatilizes during photo sintering, so that reduction of copper oxide particles or the like is not sufficiently performed. The conductivity of the obtained conductive film becomes insufficient. That is, it can be said that one of the features of the present invention resides in the use of a polymer having both a function of reducing property and crosslinkability.

以下，首先，對導電膜形成用組成物的各種成分(氧化銅粒子等、聚合物、硬化劑等)進行詳細說明，然後，對導電膜的製造方法進行詳細說明。 In the following, various components (such as copper oxide particles, a polymer, a curing agent, and the like) of the conductive film-forming composition will be described in detail, and then a method of producing the conductive film will be described in detail.

<氧化銅粒子及/或銅粒子> <Copper oxide particles and/or copper particles>

本發明的組成物中含有氧化銅粒子及/或銅粒子(較佳為氧化銅粒子)。如上所述，於對由本發明的組成物形成的塗膜照射光的情況下，氧化銅粒子或一部分被氧化的銅粒子被快速還原而形成導電性優異的導電膜。 The composition of the present invention contains copper oxide particles and/or copper particles (preferably copper oxide particles). As described above, when the coating film formed of the composition of the present invention is irradiated with light, the copper oxide particles or a part of the oxidized copper particles are rapidly reduced to form a conductive film having excellent conductivity.

(氧化銅粒子) (copper oxide particles)

本發明的組成物中所含有的氧化銅粒子只要是粒子狀的氧化銅，則並無特別限定。 The copper oxide particles contained in the composition of the present invention are not particularly limited as long as they are particulate copper oxide.

所謂粒子狀，是指小的粒狀，其具體例可列舉球狀、橢球(ellipsoid)狀等。不必為完全的球或橢球，亦可為一部分歪斜。 The particulate form refers to a small granular shape, and specific examples thereof include a spherical shape and an ellipsoid shape. It does not have to be a complete ball or ellipsoid, or it can be partially skewed.

氧化銅粒子較佳為氧化銅(I)粒子或氧化銅(II)粒子，就可低廉地獲取，另外，所得導電膜的導電性良好的理由而言，更佳為氧化銅(II)粒子。 The copper oxide particles are preferably copper oxide (I) particles or copper (II) oxide particles, which are inexpensively obtained, and the copper (II) oxide particles are more preferable because the conductivity of the obtained conductive film is good.

氧化銅粒子較佳為奈米粒子。 The copper oxide particles are preferably nano particles.

氧化銅粒子的平均粒徑並無特別限制，但較佳為200nm以下，更佳為100nm以下。下限亦無特別限制，但較佳為1nm以上。 The average particle diameter of the copper oxide particles is not particularly limited, but is preferably 200 nm or less, more preferably 100 nm or less. The lower limit is also not particularly limited, but is preferably 1 nm or more.

若平均粒徑為1nm以上，則粒子表面的活性不會變得過高，在組成物中不會溶解，操作性優異，因此較佳。另外，若平均粒徑為200nm以下，則使用組成物作為噴墨用墨水組成物，容易利用印刷法來進行配線等的圖案形成，當將組成物製成導體時，對金屬銅的還原變得充分，所得導電膜的導電性變得良好，因此較佳。 When the average particle diameter is 1 nm or more, the activity on the surface of the particles does not become too high, and the composition does not dissolve, and the workability is excellent, which is preferable. In addition, when the average particle diameter is 200 nm or less, the composition is used as an ink composition for inkjet, and patterning such as wiring can be easily performed by a printing method, and when the composition is made into a conductor, reduction of metallic copper becomes Since the conductivity of the obtained conductive film is sufficient, it is preferable.

此外，本發明中的平均粒徑是指平均一次粒徑。平均粒徑是藉由穿透型電子顯微鏡(Transmission Electron Microscope，TEM)觀察，測定至少50個以上的氧化銅粒子的粒徑(直徑)，將該些粒徑進行算術平均而求出。此外，於觀察圖中，氧化銅粒子的形狀不為圓球狀的情況下，測定長徑作為直徑。 Further, the average particle diameter in the present invention means an average primary particle diameter. The average particle diameter is measured by a transmission electron microscope (TEM), and the particle diameter (diameter) of at least 50 or more copper oxide particles is measured, and these particle diameters are arithmetically averaged. Further, in the observation chart, when the shape of the copper oxide particles is not spherical, the long diameter is measured as the diameter.

氧化銅粒子例如可較佳地使用關東化學公司製造的CuO奈米粒子、西格瑪奧德里奇(Sigma-Aldrich)公司製造的CuO奈米粒子等。 As the copper oxide particles, for example, CuO nano particles manufactured by Kanto Chemical Co., Ltd., CuO nano particles manufactured by Sigma-Aldrich Co., Ltd., or the like can be preferably used.

(銅粒子) (copper particles)

本發明的組成物中所含的銅粒子只要是粒子狀的銅，則並無特別限定。 The copper particles contained in the composition of the present invention are not particularly limited as long as they are particulate copper.

粒子狀的定義與上述氧化銅粒子相同。 The definition of the particle shape is the same as that of the above copper oxide particles.

銅粒子較佳為奈米粒子。 The copper particles are preferably nano particles.

銅粒子的平均粒徑的較佳態樣與上述氧化銅粒子相同。 A preferred aspect of the average particle diameter of the copper particles is the same as that of the above copper oxide particles.

<聚合物> <polymer>

本發明的組成物中含有包含下述式(1)所表示的重複單元及 下述式(2)所表示的重複單元的聚合物(以下亦稱為特定聚合物)。 The composition of the present invention contains a repeating unit represented by the following formula (1) and A polymer of a repeating unit represented by the following formula (2) (hereinafter also referred to as a specific polymer).

如上所述，由於本發明的組成物中所含的特定聚合物含有特定的交聯性基，故而於對所得的塗膜照射光的情況下，塗膜自身不會發生物理性分解，獲得與基材的密接性優異的導電膜。另外，由於本發明的組成物中所含的特定聚合物具有特定的還原性基，故而光燒結時快速產生氧化銅粒子或一部分被氧化的銅粒子的還原，獲得導電性優異的導電膜。 As described above, since the specific polymer contained in the composition of the present invention contains a specific crosslinkable group, when the obtained coating film is irradiated with light, the coating film itself does not physically decompose and is obtained. A conductive film having excellent adhesion to a substrate. Further, since the specific polymer contained in the composition of the present invention has a specific reducing group, the copper oxide particles or a part of the oxidized copper particles are rapidly reduced during photo sintering, and a conductive film having excellent conductivity is obtained.

上述式(1)中，R1表示氫原子、或者經取代或未經取代的烷基(較佳為碳數1~5的烷基)。其中，較佳為氫原子、甲基，更佳為氫原子。 In the above formula (1), R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group (preferably an alkyl group having 1 to 5 carbon atoms). Among them, a hydrogen atom and a methyl group are preferred, and a hydrogen atom is more preferred.

上述式(1)中，L1表示單鍵或2價有機基。 In the above formula (1), L 1 represents a single bond or a divalent organic group.

2價有機基可列舉：經取代或未經取代的脂肪族烴基(例如伸烷基；較佳為碳數1~8)、經取代或未經取代的芳香族烴基(例如伸芳基；較佳為碳數6~12)、-O-、-S-、-SO2-、-N(R)-(R：烷基)、 -CO-、-NH-、-COO-、-CONH-、或者將該些基組合而成的基團(例如伸烷基氧基、伸烷基氧基羰基、伸烷基羰基氧基等)等。其中，較佳為伸烷基、-O-、-COO-、或者將該些基組合而成的基團。 The divalent organic group may, for example, be a substituted or unsubstituted aliphatic hydrocarbon group (for example, an alkylene group; preferably a carbon number of 1 to 8), a substituted or unsubstituted aromatic hydrocarbon group (for example, an extended aryl group; Preferably, the carbon number is 6~12), -O-, -S-, -SO 2 -, -N(R)-(R:alkyl), -CO-, -NH-, -COO-, -CONH- Or a group in which the groups are combined (for example, an alkyloxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, etc.). Among them, an alkyl group, -O-, -COO-, or a group in which the groups are combined is preferable.

上述式(1)中，A為還原性基，具體而言，表示含有醯胺基(-CON<)的有機基、或者羥基(-OH)。其中，就所得導電膜的密接性更優異的理由而言，較佳為含有醯胺基的有機基。此外，上述還原性基於光燒結時對氧化銅粒子或一部分被氧化的銅粒子表現出還原性。 In the above formula (1), A is a reducing group, and specifically, an organic group containing a guanamine group (-CON<) or a hydroxyl group (-OH). Among them, the organic group containing a guanamine group is preferred because the adhesion of the obtained conductive film is more excellent. Further, the above-described reducing property is based on the reduction of the copper oxide particles or a part of the oxidized copper particles during photo sintering.

上述含有醯胺基的有機基並無特別限制，較佳態樣例如可列舉下述式(7)所表示的基。 The organic group containing a guanamine group is not particularly limited, and a preferred embodiment thereof is a group represented by the following formula (7).

上述式(7)中，R71表示可具有雜原子的烴基。存在多個的R71可分別相同亦可不同。R71可由R71彼此形成環。 In the above formula (7), R 71 represents a hydrocarbon group which may have a hetero atom. There may be a plurality of R 71 which may be the same or different. R 71 may form a ring with each other by R 71 .

上述可具有雜原子的烴基的雜原子例如可列舉氧原子、氮原子、硫原子、磷原子等。 Examples of the hetero atom of the hydrocarbon group which may have a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom and the like.

上述可具有雜原子的烴基例如可列舉：脂肪族烴基、芳香族 烴基、或者將該些基組合而成的基團等。 Examples of the hydrocarbon group which may have a hetero atom include an aliphatic hydrocarbon group and an aromatic group. a hydrocarbon group or a group obtained by combining the groups.

上述脂肪族烴基可為直鏈狀、分支鏈狀、環狀的任一種。上述脂肪族烴基的具體例可列舉：直鏈狀或分支狀的烷基(特別是碳數1~10)、直鏈狀或分支狀的烯基(特別是碳數2~10)、直鏈狀或分支狀的炔基(特別是碳數2~10)等。 The aliphatic hydrocarbon group may be any of a linear chain, a branched chain, and a cyclic group. Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (particularly, a carbon number of 1 to 10), a linear or branched alkenyl group (particularly, a carbon number of 2 to 10), and a linear chain. An alkynyl group (especially a carbon number of 2 to 10) or the like.

上述芳香族烴基例如可列舉芳基、萘基等。上述芳基例如可列舉苯基、甲苯基、二甲苯基等碳數6~18的芳基等。 Examples of the aromatic hydrocarbon group include an aryl group and a naphthyl group. Examples of the aryl group include an aryl group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group and a xylyl group.

上述式(7)中，*表示鍵結位置。 In the above formula (7), * represents a bonding position.

上述式(7)所表示的基的較佳態樣例如可列舉由R71彼此形成環的態樣。其中，較佳為下述式(8)所表示的基。 A preferred aspect of the group represented by the above formula (7) is, for example, a form in which R 71 forms a ring with each other. Among them, a group represented by the following formula (8) is preferred.

上述式(8)中，R81表示氫原子、或可具有雜原子的烴基。存在多個的R81可分別相同亦可不同。R81的具體例與上述R71相同。其中，較佳為氫原子。 In the above formula (8), R 81 represents a hydrogen atom or a hydrocarbon group which may have a hetero atom. There may be a plurality of R 81 which may be the same or different. Specific examples of R 81 are the same as those of R 71 described above. Among them, a hydrogen atom is preferred.

上述式(2)中，R2表示氫原子、或者經取代或未經取代的烷基。R2的具體例及較佳態樣與上述R1相同。 In the above formula (2), R 2 represents a hydrogen atom or a substituted or unsubstituted alkyl group. Specific examples of the same R 2, and preferred aspects of the above-described R 1.

上述式(2)中，L2表示單鍵或2價有機基。L2的具體例及較佳態樣與上述L1相同。 In the above formula (2), L 2 represents a single bond or a divalent organic group. Specific examples of L and preferred aspects. 1 L 2 with said same.

上述式(2)中，B為交聯性基，表示選自由下述式(B-1)~式(B-9)所組成的組群中的基。 In the above formula (2), B is a crosslinkable group and represents a group selected from the group consisting of the following formulas (B-1) to (B-9).

上述式(B-1)~式(B-9)中，Rb表示氫原子、或可具有雜原子的烴基。存在多個的Rb可分別相同亦可不同。*表示鍵結位置。 In the above formula (B-1) to formula (B-9), R b represents a hydrogen atom or a hydrocarbon group which may have a hetero atom. There may be a plurality of R b which may be the same or different. * indicates the bonding position.

上述式(B-1)中，Rb較佳為氫原子或者經取代或未經取代的烷基，更佳為氫原子。 In the above formula (B-1), R b is preferably a hydrogen atom or a substituted or unsubstituted alkyl group, more preferably a hydrogen atom.

上述式(B-3)中，Rb較佳為經取代或未經取代的烷基(特別 是碳數1~5的烷基)。 In the above formula (B-3), R b is preferably a substituted or unsubstituted alkyl group (particularly an alkyl group having 1 to 5 carbon atoms).

上述式(B-6)中，Rb較佳為氫原子或者經取代或未經取代的烷基(特別是碳數1~5的烷基)，更佳為甲基。 In the above formula (B-6), R b is preferably a hydrogen atom or a substituted or unsubstituted alkyl group (particularly, an alkyl group having 1 to 5 carbon atoms), more preferably a methyl group.

上述式(B-7)中，Rb較佳為氫原子或者經取代或未經取代的烷基，更佳為氫原子。m表示0~11的整數。n表示0~2的整數。其中，於n為0的情況下，m表示0~7的整數，於n為1的情況下，m表示0~9的整數，於n為2的情況下，m表示0~11的整數。 In the above formula (B-7), R b is preferably a hydrogen atom or a substituted or unsubstituted alkyl group, more preferably a hydrogen atom. m represents an integer from 0 to 11. n represents an integer from 0 to 2. In the case where n is 0, m represents an integer of 0 to 7, and when n is 1, m represents an integer of 0 to 9, and when n is 2, m represents an integer of 0 to 11.

上述式(B-8)中，Rb較佳為氫原子或者經取代或未經取代的烷基，更佳為氫原子。 In the above formula (B-8), R b is preferably a hydrogen atom or a substituted or unsubstituted alkyl group, more preferably a hydrogen atom.

上述式(B-9)中，Rb較佳為氫原子或者經取代或未經取代的烷基，更佳為氫原子。 In the above formula (B-9), R b is preferably a hydrogen atom or a substituted or unsubstituted alkyl group, more preferably a hydrogen atom.

上述式(2)中，就所得導電膜的密接性更優異的理由而言，B較佳為選自由式(B-1)、式(B-3)、式(B-4)、式(B-5)、式(B-6)及式(B-7)所組成的組群中的基，更佳為選自由式(B-1)、式(B-3)、式(B-4)、式(B-6)及式(B-7)所組成的組群中的基，尤佳為選自由式(B-1)、式(B-3)、式(B-6)及式(B-7)所組成的組群中的基，特佳為式(B-1)或式(B-7)。 In the above formula (2), B is preferably selected from the formula (B-1), the formula (B-3), the formula (B-4), and the formula (4), because the adhesion of the obtained conductive film is more excellent. The group in the group consisting of B-5), (B-6) and (B-7) is more preferably selected from the group consisting of formula (B-1), formula (B-3), and formula (B-). 4) The group in the group consisting of formula (B-6) and formula (B-7) is particularly preferably selected from the group consisting of formula (B-1), formula (B-3), and formula (B-6). The group in the group consisting of the formula (B-7) is particularly preferably a formula (B-1) or a formula (B-7).

此外，於上述式(2)中的B所表示的交聯性基為上述式(B-2)的情況下，上述式(1)所表示的重複單元與上述式(2)所表示的重複單元可相同。另外，於上述式(2)中的B所表示的交聯性基為上述式(B-2)的情況下，上述特定聚合物只要至少包 含上述式(2)所表示的重複單元即可。 In the case where the crosslinkable group represented by B in the above formula (2) is the above formula (B-2), the repeating unit represented by the above formula (1) and the repeat represented by the above formula (2) Units can be the same. In the case where the crosslinkable group represented by B in the above formula (2) is the above formula (B-2), the specific polymer is at least packaged. The repeating unit represented by the above formula (2) may be used.

其原因在於，於上述式(2)中的B所表示的交聯性基為上述式(B-2)的情況下，上述交聯性基亦發揮還原性基的功能。 The reason for this is that when the crosslinkable group represented by B in the above formula (2) is the above formula (B-2), the crosslinkable group also functions as a reducing group.

上述特定聚合物的較佳態樣例如可列舉：包含下述式(3)所表示的重複單元及下述式(2)(與上述式(2)相同)所表示的重複單元的聚合物P、包含下述式(4)所表示的重複單元及下述式(5)所表示的重複單元的聚合物Q、以及包含下述式(6)所表示的重複單元的聚合物R。其中，就所得導電膜的密接性更優異的理由而言，較佳為聚合物P或聚合物R，更佳為聚合物P。 The preferred embodiment of the specific polymer is, for example, a polymer P comprising a repeating unit represented by the following formula (3) and a repeating unit represented by the following formula (2) (same as the above formula (2)) The polymer Q comprising a repeating unit represented by the following formula (4) and a repeating unit represented by the following formula (5), and a polymer R containing a repeating unit represented by the following formula (6). Among them, the reason why the adhesion of the obtained conductive film is more excellent is preferably polymer P or polymer R, more preferably polymer P.

上述式(3)中，R3表示氫原子、或者經取代或未經取代的烷基。R3的具體例及較佳態樣與上述R1相同。 In the above formula (3), R 3 represents a hydrogen atom or a substituted or unsubstituted alkyl group. Specific examples of the same, and R 3 preferred aspects of the above-described R 1.

上述式(3)中，R31表示氫原子、或可具有雜原子的烴基。存在多個的R31可分別相同亦可不同。R31的具體例與上述R71相同。其中，較佳為氫原子。 In the above formula (3), R 31 represents a hydrogen atom or a hydrocarbon group which may have a hetero atom. There may be a plurality of R 31 which may be the same or different. Specific examples of R 31 are the same as those of R 71 described above. Among them, a hydrogen atom is preferred.

上述式(4)及式(5)中，R4及R5分別獨立地表示氫原子、或者經取代或未經取代的烷基。R4及R5的具體例及較佳態樣與上述R1相同。 In the above formula (4) and formula (5), R 4 and R 5 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group. Specific examples and preferred aspects of R 4 and R 5 are the same as those of R 1 described above.

此外，包含上述式(4)所表示的重複單元及下述式(5)所表示的重複單元的聚合物Q中，上述式(4)所表示的重複單元既相當於上述式(1)所表示的重複單元，亦相當於上述式(2)所表示的重複單元。即，上述式(4)中的OH基為上述式(1)中的A(還原性基)，且亦為上述式(2)中的B(交聯性基)。 Further, in the polymer Q including the repeating unit represented by the above formula (4) and the repeating unit represented by the following formula (5), the repeating unit represented by the above formula (4) corresponds to the above formula (1). The repeating unit represented also corresponds to the repeating unit represented by the above formula (2). In other words, the OH group in the above formula (4) is A (reducing group) in the above formula (1), and is also B (crosslinkable group) in the above formula (2).

上述式(6)中，R6表示氫原子、或者經取代或未經取 代的烷基。R6的具體例及較佳態樣與上述R1相同。 In the above formula (6), R 6 represents a hydrogen atom or a substituted or unsubstituted alkyl group. Specific examples and preferred aspects of R 6 are the same as those of R 1 described above.

上述式(6)中，L6表示單鍵或2價有機基。L6的具體例與上述L1相同。其中，較佳為伸烷基、-O-、-COO-、-CO-或者將該些基組合而成的基團，更佳為-CO-。 In the above formula (6), L 6 represents a single bond or a divalent organic group. A specific example of L 6 is the same as L 1 described above. Among them, an alkyl group, -O-, -COO-, -CO- or a combination of these groups is preferred, and -CO- is more preferred.

上述式(6)中，R61表示2價脂肪族烴基。其中，較佳為碳數1~5的伸烷基，更佳為1~3的伸烷基，尤佳為伸乙基。 In the above formula (6), R 61 represents a divalent aliphatic hydrocarbon group. Among them, an alkylene group having 1 to 5 carbon atoms is preferred, and an alkylene group having 1 to 3 carbon atoms is more preferred, and an ethyl group is particularly preferred.

上述式(6)中，p表示1~100的整數。其中，較佳為5~30的整數。 In the above formula (6), p represents an integer of 1 to 100. Among them, an integer of 5 to 30 is preferred.

此外，包含上述式(6)所表示的重複單元的聚合物R中，上述式(6)所表示的重複單元既相當於上述式(1)所表示的重複單元，亦相當於上述式(2)所表示的重複單元。即，位於上述式(6)中的側鏈的末端的OH基為上述式(1)中的A(還原性基)，且亦為上述式(2)中的B(交聯性基)。 Further, in the polymer R containing the repeating unit represented by the above formula (6), the repeating unit represented by the above formula (6) corresponds to the repeating unit represented by the above formula (1), and corresponds to the above formula (2). ) the repeating unit represented. In other words, the OH group at the terminal of the side chain in the above formula (6) is A (reducing group) in the above formula (1), and is also B (crosslinkable group) in the above formula (2).

就粒子分散性良好，所得導電膜的均勻性提高的觀點而言，上述特定聚合物較佳為水溶性。 The specific polymer is preferably water-soluble from the viewpoint that the particle dispersibility is good and the uniformity of the obtained conductive film is improved.

上述特定聚合物的分子量並無特別限制，但就組成物的製備，塗佈性、膜性質提高等觀點而言，較佳為1000~1000000，更佳為10000~500000。 The molecular weight of the specific polymer is not particularly limited, but is preferably from 1,000 to 1,000,000, more preferably from 10,000 to 500,000, from the viewpoints of preparation of the composition, improvement in coatability and film properties, and the like.

此外，本申請案中，使用東曹公司製造的凝膠滲透層析儀(Gel Permeation Chromatograph，GPC)，將N-甲基吡咯啶酮作為溶劑，以聚苯乙烯換算來測定上述特定聚合物的重量平均分子量。 Further, in the present application, a gel permeation chromatograph (GPC) manufactured by Tosoh Corporation was used, and N-methylpyrrolidone was used as a solvent to determine the specific polymer in terms of polystyrene. Weight average molecular weight.

上述特定聚合物的製造方法並無特別限制，可採用公知 的方法。例如，可藉由使用形成所需重複單元的乙烯基系單體，進行自由基聚合、陽離子聚合或者陰離子聚合，而獲得所需的乙烯基系聚合物。 The method for producing the above specific polymer is not particularly limited and can be known. Methods. For example, a desired vinyl-based polymer can be obtained by radical polymerization, cationic polymerization or anionic polymerization using a vinyl-based monomer which forms a desired repeating unit.

此外，各聚合形式中可視需要使用各種起始劑(例如自由基聚合起始劑等)。 Further, various initiators (e.g., a radical polymerization initiator, etc.) may be used as needed in each polymerization form.

本發明的組成物中，就所得導電膜的導電性與組成物的保存穩定性的平衡的觀點而言，相對於上述氧化銅粒子與上述銅粒子的合計含量，上述特定聚合物的含量較佳為1質量%~50質量%，更佳為3質量%~30質量%，尤佳為5質量%~15質量%。 In the composition of the present invention, the content of the specific polymer is preferably based on the total content of the copper oxide particles and the copper particles, from the viewpoint of the balance between the conductivity of the obtained conductive film and the storage stability of the composition. It is 1% by mass to 50% by mass, more preferably 3% by mass to 30% by mass, and particularly preferably 5% by mass to 15% by mass.

<硬化劑> <hardener>

本發明的組成物中含有與上述式(2)中的B所表示的交聯性基進行反應的硬化劑。 The composition of the present invention contains a curing agent which reacts with the crosslinkable group represented by B in the above formula (2).

此種硬化劑只要是與上述式(2)中的B所表示的交聯性基進行反應的硬化劑，則並無特別限制，例如可列舉：胺(含胺基的化合物)、醇(將鏈式或脂環式烴的氫原子以羥基取代的化合物)、環氧化物(含環氧基的化合物)、醛(含醛基的化合物)、自由基起始劑、乙烯基化合物(含乙烯基的化合物)、酸觸媒、羧酸等。 The curing agent is not particularly limited as long as it is a curing agent which reacts with the crosslinkable group represented by B in the above formula (2), and examples thereof include an amine (amine-containing compound) and an alcohol (will a compound in which a hydrogen atom of a chain or alicyclic hydrocarbon is substituted with a hydroxyl group), an epoxide (an epoxy group-containing compound), an aldehyde (an aldehyde group-containing compound), a radical initiator, a vinyl compound (including ethylene) a compound of a base), an acid catalyst, a carboxylic acid, or the like.

上述胺並無特別限制，但較佳為具有多個(特別是2個)胺基的胺。此種胺例如可列舉：二伸乙基三胺或三伸乙基四胺等脂肪族多胺、間苯二胺或二胺基二苯基甲烷或二胺基二苯基碸等芳香族多胺等。其中，較佳為下述式(16)所表示的化合物。 The above amine is not particularly limited, but is preferably an amine having a plurality of (particularly two) amine groups. Examples of such an amine include aromatic polyamines such as di-ethyltriamine or tri-ethylidene tetraamine, and aromatic polyamines such as m-phenylenediamine or diaminodiphenylmethane or diaminodiphenylphosphonium. Amines, etc. Among them, a compound represented by the following formula (16) is preferred.

H2N-L16-NH2 式(16) H 2 NL 16 -NH 2 formula (16)

上述式(16)中，L16表示單鍵或2價有機基。L16的具體例與上述L1相同。其中，較佳為伸烷基、或者伸烷基與-NH-組合而成的基團。 In the above formula (16), L 16 represents a single bond or a divalent organic group. A specific example of L 16 is the same as L 1 described above. Among them, a group derived from an alkyl group or an alkyl group and -NH- is preferred.

上述醇並無特別限制，但較佳為具有多個(特別是2個)羥基的可具有雜原子的脂肪族烴。此種脂肪族烴例如可列舉：乙二醇、丙二醇、二乙二醇、二丙二醇、聚乙二醇、聚丙二醇、二乙醇胺、三乙醇胺、雙羥基甲基脲等。其中，較佳為具有二級胺基(-NR-：R為氫原子或烴基)或者三級胺基(-N<)的化合物，更佳為下述式(9)所表示的化合物。 The above alcohol is not particularly limited, but is preferably an aliphatic hydrocarbon having a plurality of (particularly two) hydroxyl groups which may have a hetero atom. Examples of such an aliphatic hydrocarbon include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, diethanolamine, triethanolamine, and bishydroxymethylurea. Among them, a compound having a secondary amino group (-NR-: R is a hydrogen atom or a hydrocarbon group) or a tertiary amino group (-N <) is preferred, and a compound represented by the following formula (9) is more preferred.

上述式(9)中，R91表示2價脂肪族烴基。R91的具體例與上述R61相同。其中，較佳為碳數1~5的伸烷基。 In the above formula (9), R 91 represents a divalent aliphatic hydrocarbon group. Specific examples of R 91 are the same as those of the above R 61 . Among them, an alkylene group having 1 to 5 carbon atoms is preferred.

上述式(9)中，s為0或1。 In the above formula (9), s is 0 or 1.

上述式(9)中，t為2或3。 In the above formula (9), t is 2 or 3.

上述式(9)中，s及t滿足s+t=3的關係式。 In the above formula (9), s and t satisfy the relational expression of s+t=3.

另外，上述醇的較佳態樣例如可列舉具有2個以上的下 述式(13)所表示的部分結構的化合物。 Further, preferred examples of the above alcohols include, for example, two or more A compound of a partial structure represented by the formula (13).

上述式(13)中，R131表示氫原子、或者經取代或未經取代的烷基。R131的具體例與上述R1相同。R131較佳為氫原子。 In the above formula (13), R 131 represents a hydrogen atom or a substituted or unsubstituted alkyl group. Specific examples of R 131 are the same as those of R 1 described above. R 131 is preferably a hydrogen atom.

具有2個以上的上述式(13)所表示的部分結構的化合物的較佳態樣例如可列舉下述式(14)所表示的化合物。 A preferred embodiment of the compound having a partial structure represented by the above formula (13) is, for example, a compound represented by the following formula (14).

上述式(14)中，R141表示氫原子、或者經取代或未經取代的烷基。R141的具體例與上述R1相同。R141較佳為氫原子。 In the above formula (14), R 141 represents a hydrogen atom or a substituted or unsubstituted alkyl group. Specific examples of R 141 are the same as those of R 1 described above. R 141 is preferably a hydrogen atom.

上述環氧化物只要是含有環氧基的化合物，則並無特別限制，但較佳為含有多個(特別是2個)環氧基的化合物。其中，較佳為下述式(10)所表示的化合物。 The epoxide is not particularly limited as long as it is an epoxy group-containing compound, but is preferably a compound containing a plurality of (particularly two) epoxy groups. Among them, a compound represented by the following formula (10) is preferred.

上述式(10)中，L10表示單鍵或2價有機基。L10的具體例及較佳態樣與上述L1相同。 In the above formula (10), L 10 represents a single bond or a divalent organic group. Specific examples and preferred aspects of L 10 are the same as those of L 1 described above.

上述醛只要是含有醛基的化合物，則並無特別限制，但較佳為含有多個(特別是2個)醛基的化合物。其中，較佳為下述式(11)所表示的化合物。 The aldehyde is not particularly limited as long as it is an aldehyde group-containing compound, but is preferably a compound containing a plurality of (particularly two) aldehyde groups. Among them, a compound represented by the following formula (11) is preferred.

上述式(11)中，L11表示單鍵或2價有機基。L11的具體例與上述L1相同。其中較佳為單鍵。 In the above formula (11), L 11 represents a single bond or a divalent organic group. A specific example of L 11 is the same as L 1 described above. Among them, a single bond is preferred.

上述醛較佳為乙二醛(glyoxal)。 The above aldehyde is preferably glyoxal.

上述自由基起始劑並無特別限制，例如可使用：苯乙酮(acetophenone)類、安息香(benzoin)類、二苯甲酮(benzophenone)類(1-羥基-1,2,3,4,5,6-六氫二苯甲酮等)、氧化膦(phosphine oxide)類、縮酮(ketal)類、蒽醌(anthraquinone)類、硫雜蒽酮(thioxanthone)類、偶氮化合物、過氧化物類、2,3-二烷基二酮 化合物類、二硫醚化合物類、氟胺化合物類、芳香族鋶類、咯吩二聚物(lophine dimer)類、鎓鹽類、硼酸鹽類、活性酯類、活性鹵素類、無機錯合物、香豆素類、有機或無機過氧化物、有機偶氮或者重氮化合物(例如後述VA-080)等。 The above radical initiator is not particularly limited, and for example, acetophenone, benzoin, or benzophenone (1-hydroxy-1, 2, 3, 4, 5,6-hexahydrobenzophenone, etc.), phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxidation Species, 2,3-dialkyldione Compounds, disulfide compounds, fluoroamine compounds, aromatic oximes, lophine dimers, sulfonium salts, borates, active esters, reactive halogens, inorganic complexes A coumarin, an organic or inorganic peroxide, an organic azo or a diazo compound (for example, VA-080 described later).

上述乙烯基化合物只要是含有乙烯基的化合物，則並無特別限制，但較佳為含有多個(特別是2個)乙烯基的化合物。其中，較佳為下述式(12)所表示的化合物。 The vinyl compound is not particularly limited as long as it is a compound containing a vinyl group, but is preferably a compound containing a plurality of (particularly two) vinyl groups. Among them, a compound represented by the following formula (12) is preferred.

上述式(12)中，L12表示單鍵或2價有機基。L12的具體例與上述L1相同。其中較佳為具有硫原子的有機基，更佳為-S-或-SO2-，尤佳為-SO2-。 In the above formula (12), L 12 represents a single bond or a divalent organic group. A specific example of L 12 is the same as L 1 described above. Preferably wherein an organic group having a sulfur atom, more preferably is -S- or -SO 2 -, particularly preferably -SO 2 -.

上述酸觸媒並無特別限制，可使用公知的酸觸媒。具體例可列舉：乙二酸、酒石酸、琥珀酸、檸檬酸、鹽酸、硫酸、對甲苯磺酸等。 The acid catalyst is not particularly limited, and a known acid catalyst can be used. Specific examples thereof include oxalic acid, tartaric acid, succinic acid, citric acid, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid and the like.

上述羧酸並無特別限制，只要是具有羧基的化合物，則並無特別限制，較佳為含有多個(特別是2個)羧基的化合物。其中，較佳為下述式(15)所表示的化合物。 The carboxylic acid is not particularly limited as long as it is a compound having a carboxyl group, and is preferably a compound containing a plurality of (particularly two) carboxyl groups. Among them, a compound represented by the following formula (15) is preferred.

HOOC-L15-COOH 式(15) HOOC-L 15 -COOH type (15)

上述式(15)中，L15表示單鍵或2價有機基。L15的具體例與上述L1相同。其中較佳為伸烷基(特別是碳數1~5)。 In the above formula (15), L 15 represents a single bond or a divalent organic group. A specific example of L 15 is the same as L 1 described above. Among them, an alkyl group (especially a carbon number of 1 to 5) is preferred.

於上述式(2)中的B(交聯性基)為上述式(B-1)或式(B-7)~式(B-9)的情況下，就所得導電膜的密接性及導電性更優異的理由而言，硬化劑較佳為上述胺或上述醇，更佳為上述胺。 When B (crosslinkable group) in the above formula (2) is the above formula (B-1) or formula (B-7) to formula (B-9), the adhesion and conductivity of the obtained conductive film are obtained. For the reason that the properties are more excellent, the hardener is preferably the above amine or the above alcohol, more preferably the above amine.

於上述式(2)中的B(交聯性基)為上述式(B-4)的情況下，就所得導電膜的密接性及導電性更優異的理由而言，硬化劑較佳為上述酸觸媒或上述醇，更佳為上述酸觸媒。 In the case where B (crosslinkable group) in the above formula (2) is the above formula (B-4), the curing agent is preferably the above-mentioned hardening agent and the conductivity. The acid catalyst or the above alcohol is more preferably the above acid catalyst.

於上述式(2)中的B(交聯性基)為上述式(B-5)的情況下，就所得導電膜的密接性及導電性更優異的理由而言，硬化劑較佳為上述羧酸。 In the case where B (crosslinkable group) in the above formula (2) is the above formula (B-5), the curing agent is preferably the above-mentioned hardening agent and the conductivity. carboxylic acid.

於上述式(2)中的B(交聯性基)為上述式(B-2)的情況下，就所得導電膜的密接性及導電性更優異的理由而言，硬化劑較佳為上述環氧化物、具有2個以上的上述式(13)所表示的部分結構的化合物、上述乙烯基化合物或上述醛，更佳為上述環氧化物、、具有2個以上的上述式(13)所表示的部分結構的化合物或上述乙烯基化合物，尤佳為上述環氧化物或具有2個以上的上 述式(13)所表示的部分結構的化合物，特佳為上述環氧化物。 In the case where B (crosslinkable group) in the above formula (2) is the above formula (B-2), the curing agent is preferably excellent in the adhesion and conductivity of the obtained conductive film. An epoxide, a compound having a partial structure represented by two or more of the above formula (13), the above vinyl compound or the aldehyde, more preferably the epoxide, and two or more of the above formula (13) a compound having a partial structure or a vinyl compound as described above, particularly preferably the above epoxide or having two or more The compound having a partial structure represented by the formula (13) is particularly preferably the above epoxide.

於上述式(2)中的B(交聯性基)為上述式(B-3)的情況下，就所得導電膜的密接性及導電性更優異的理由而言，硬化劑較佳為上述醇，更佳為具有2個以上的上述式(13)所表示的部分結構的化合物。 In the case where B (crosslinkable group) in the above formula (2) is the above formula (B-3), the curing agent is preferably the above-mentioned hardening agent and the conductivity. The alcohol is more preferably a compound having two or more partial structures represented by the above formula (13).

於上述式(2)中的B(交聯性基)為上述式(B-6)的情況下，就所得導電膜的密接性及導電性更優異的理由而言，硬化劑較佳為上述自由基起始劑。 In the case where B (crosslinkable group) in the above formula (2) is the above formula (B-6), the curing agent is preferably excellent in the adhesion and conductivity of the obtained conductive film. Free radical initiator.

本發明的組成物中，就效率良好地將聚合物交聯的觀點而言，相對於上述特定聚合物的含量，上述硬化劑的含量較佳為0.01質量%~30質量%，更佳為0.1質量%~20質量%。 In the composition of the present invention, the content of the curing agent is preferably from 0.01% by mass to 30% by mass, more preferably 0.1%, based on the content of the specific polymer, from the viewpoint of efficiently crosslinking the polymer. Mass%~20% by mass.

<溶劑> <solvent>

就黏度調節的容易度、以及印刷性的觀點而言，本發明的組成物較佳為含有溶劑。溶劑發揮氧化銅粒子及/或銅粒子的分散介質的功能。 The composition of the present invention preferably contains a solvent from the viewpoint of easiness of viscosity adjustment and printability. The solvent functions as a dispersion medium of the copper oxide particles and/or the copper 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。其中，就形成均質的膜，結果所形成的導電膜的導電性更優異的理由而言，較佳為使用水、具有1價~3價羥基的脂肪族醇、源自該脂肪族醇的烷基醚、源自該脂肪族醇的烷基酯、或者該些溶劑的混合物。其中，就沸點不會過高的方面而言，特佳為使用水作為主溶劑。所謂主溶劑，是指溶劑中含有率最多的溶劑。 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. In order to form a homogeneous film, it is preferable to use water, an aliphatic alcohol having a monovalent to trivalent hydroxy group, or an alkane derived from the aliphatic alcohol, because the conductivity of the conductive film formed is more excellent. An ether, an alkyl ester derived from the aliphatic alcohol, or a mixture of such solvents. Among them, in terms of the fact that the boiling point is not too high, it is particularly preferable to use water as a main solvent. The main solvent refers to a solvent having the highest content in a solvent.

溶劑的含量並無特別限制，但就抑制黏度的上升，操作性更優異的方面而言，相對於組成物總質量，上述溶劑的含量較佳為5質量%~90質量%，更佳為8質量%~80質量%。 The content of the solvent is not particularly limited, but the content of the solvent is preferably from 5% by mass to 90% by mass, more preferably from 8 to 90% by mass, based on the total mass of the composition, in terms of suppressing an increase in viscosity and further excellent workability. Mass%~80% by mass.

<其他成分> <Other ingredients>

本發明的組成物中可包含上述各成分以外的成分。 The composition of the present invention may contain components other than the above components.

例如，本發明的組成物中可包含界面活性劑。界面活性劑發揮使氧化銅粒子及/或銅粒子的分散性提高的作用。界面活性劑的種類並無特別限制，可列舉陰離子系界面活性劑、陽離子系界面活性劑、非離子系界面活性劑、氟系界面活性劑、兩性界面活性劑等。該些界面活性劑可單獨使用1種，或者將2種以上混合使用。 For example, a surfactant may be included in the composition of the present invention. The surfactant acts to improve the dispersibility of the copper oxide particles and/or the copper particles. The type of the surfactant is not particularly limited, and examples thereof include an anionic surfactant, a cationic surfactant, a nonionic surfactant, a fluorine-based surfactant, and an amphoteric surfactant. These surfactants may be used alone or in combination of two or more.

<導電膜形成用組成物的黏度> <Viscosity of Composition for Conductive Film Formation>

本發明的組成物的黏度較佳為調整為適合於噴墨、網版印刷等印刷用途的黏度。於進行噴墨噴出的情況下，較佳為1cP~50cP，更佳為1cP~40cP。於進行網版印刷的情況下，較佳為1000cP~100000cP，更佳為10000cP~80000cP。 The viscosity of the composition of the present invention is preferably adjusted to a viscosity suitable for printing applications such as inkjet or screen printing. In the case of performing inkjet ejection, it is preferably 1 cP to 50 cP, more preferably 1 cP to 40 cP. In the case of screen printing, it is preferably from 1000 cP to 100,000 cP, more preferably from 10,000 cP to 80,000 cP.

<導電膜形成用組成物的製備方法> <Method for Preparing Composition for Conductive Film Formation>

本發明的組成物的製備方法並無特別限制，可採用公知的方法。例如，可藉由在上述溶劑中添加上述氧化銅粒子及/或銅粒子、上述特定聚合物、以及上述硬化劑後，利用超音波法(例如利用超音波均質機的處理)、混合機法、三輥法、球磨機法等公知的方法，使成分分散而獲得組成物。 The preparation method of the composition of the present invention is not particularly limited, and a known method can be employed. For example, by adding the copper oxide particles and/or copper particles, the specific polymer, and the curing agent to the solvent, an ultrasonic method (for example, treatment using an ultrasonic homogenizer) or a mixer method may be used. A known method such as a three-roll method or a ball mill method disperses the components to obtain a composition.

[導電膜的製造方法] [Method of Manufacturing Conductive Film]

本發明的導電膜的製造方法至少包括塗膜形成步驟及還原步驟。以下，對各步驟進行詳細說明。 The method for producing a conductive film of the present invention includes at least a coating film forming step and a reducing step. Hereinafter, each step will be described in detail.

<塗膜形成步驟> <Coating film forming step>

本步驟是將上述導電膜形成用組成物賦予至基材上，於基材上形成組成物層，然後，對組成物層實施加熱處理而形成塗膜的步驟。藉由本步驟而獲得實施還原處理之前的前驅體膜。 In this step, the composition for forming a conductive film is applied to a substrate, a composition layer is formed on the substrate, and then the composition layer is subjected to heat treatment to form a coating film. The precursor film before the reduction treatment is obtained by this step.

所使用的導電膜形成用組成物如上所述。 The composition for forming a conductive film to be used is as described above.

本步驟中使用的基材可使用公知的基材。基材中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、或者該些材料的複合物。 As the substrate used in this step, a known substrate can be used. Examples of the material used for the substrate include a resin, paper, glass, lanthanide semiconductor, compound semiconductor, metal oxide, metal nitride, wood, or a composite of these materials.

更具體而言，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(art paper)、塗佈紙(coated paper))、特殊印刷用紙、複印用紙(普通紙複印機(plain paper copier，PPC)用紙)、未漂白包裝紙(unbleached wrapping paper)(重袋用運輸袋/牛皮紙(unglazed shipping sacks kraft paper)、運輸袋/牛皮紙(kraft paper))、漂白包裝紙(bleached wrapping paper)(漂白牛皮紙(bleached kraft paper)、純白捲筒紙(pure white roll paper))、塗佈紙板(coated board)、粗紙板(chipboard)、硬紙板(cardboard)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(amorphous silicon)、多晶矽(polysilicon)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、銦錫氧化物(indium tin oxide，ITO)、銦鋅氧化物(indium zinc oxide，IZO)、奈塞(NESA)(氧化錫)、摻銻的氧化錫(antimony-doped tin oxide，ATO)、摻氟的氧化錫、氧化鋅、摻鋁的氧化鋅(aluminum-doped zinc oxide，AZO)、摻鎵的氧化鋅、氮化鋁基材、碳化矽等其他的無機基材；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。該些基材中，較佳為使用聚酯樹脂基材、聚醚醯亞胺樹脂基材、紙基材、玻璃基材、玻璃布-環氧樹脂。 More specifically, low density polyethylene resin, high density polyethylene resin, acrylonitrile butadiene styrene (ABS) resin, acrylic resin, styrene resin, vinyl chloride resin, polyester resin Resin substrate such as (polyethylene terephthalate), polyacetal resin, polyfluorene resin, polyether oxime resin, polyether ketone resin, cellulose derivative; non-coated printing paper, micro coating Printing paper, coated printing paper (art paper, coated paper), special printing paper, copy paper (plain paper copier (PPC) paper), unbleached wrapping paper (unbleached) Wrapping paper) (unglazed shipping sacks kraft paper, kraft paper), bleached wrapping paper (bleached kraft paper, pure white web) (pure white roll Paper)), coated board, chipboard, cardboard, etc.; glass substrate such as soda glass, borosilicate glass, cerium oxide glass, quartz glass; amorphous Lanthanide semiconductor substrates such as amorphous silicon and polysilicon; compound semiconductor substrates such as CdS, CdTe, and GaAs; metal substrates such as copper, iron, and aluminum; alumina, sapphire, zirconia, and titania; Antimony oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), Nesser (NESA) (tin oxide), antimony-doped tin oxide (antimony-doped tin) Oxide, ATO), fluorine-doped tin oxide, zinc oxide, aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide, aluminum nitride substrate, tantalum carbide, and the like; Paper-resin composites such as paper-phenol resin, paper-epoxy resin, paper-polyester resin, glass cloth-epoxy resin, glass cloth-polyimine resin, glass cloth-fluoro resin, etc. Composite substrates such as materials. Among these substrates, a polyester resin substrate, a polyether phthalimide resin substrate, a paper substrate, a glass substrate, and a glass cloth-epoxy resin are preferably used.

將導電膜形成用組成物賦予至基材上而形成組成物層的方法並無特別限制，可採用公知的方法。例如可列舉：於導電膜形成用組成物中浸漬基材的方法、或將導電膜形成用組成物塗佈於基材上的方法等。就容易控制導電膜的厚度的方面而言，較佳為將導電膜形成用組成物塗佈於基材上的方法。 A method of forming a composition for forming a conductive film onto a substrate to form a composition layer is not particularly limited, and a known method can be employed. For example, a method of immersing a substrate in a composition for forming a conductive film, or a method of applying a composition for forming a conductive film on a substrate, or the like can be mentioned. In terms of easily controlling the thickness of the conductive film, a method of applying a composition for forming a conductive film on a substrate is preferred.

塗佈的方法例如可列舉：雙輥塗佈機、狹縫塗佈機、氣刀塗佈機、線棒塗佈機、滑板漏斗(slide hopper)、噴射塗佈、刀片(blade)塗佈機、刮刀塗佈機、壓擠塗佈機(squeeze coater)、逆轉輥塗佈 機、轉送輥塗佈機(transfer roll coater)、擠出塗佈機(extrusion coater)、簾幕塗佈機、浸漬塗佈機、模塗佈機、利用凹版輥的塗佈法、網版印刷法、浸漬塗佈法、噴射塗佈法、旋轉塗佈法、噴墨法等。其中，就簡便且容易製造尺寸大的導電膜的方面而言，較佳為網版印刷法、噴墨法。 Examples of the coating method include a twin roll coater, a slit coater, an air knife coater, a bar coater, a slide hopper, a spray coating, and a blade coater. , knife coater, squeeze coater, reverse roll coating Machine, transfer roll coater, extrusion coater, curtain coater, dip coater, die coater, coating method using gravure roll, screen printing Method, dip coating method, spray coating method, spin coating method, ink jet method, or the like. Among them, a screen printing method or an inkjet method is preferred in terms of being simple and easy to manufacture a conductive film having a large size.

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).

導電膜形成用組成物於基材上的塗佈量只要根據所需的導電膜的膜厚來適當調整即可，通常，塗膜的膜厚較佳為0.01μm~5000μm，更佳為0.1μm~1000μm。 The coating amount of the conductive film-forming composition on the substrate may be appropriately adjusted according to the film thickness of the conductive film to be used. Usually, the film thickness of the coating film is preferably from 0.01 μm to 5000 μm, more preferably 0.1 μm. ~1000μm.

對組成物層的加熱處理的條件並無特別限制，但加熱溫度較佳為80℃~200℃。 The conditions for the heat treatment of the composition layer are not particularly limited, but the heating temperature is preferably from 80 ° C to 200 ° C.

加熱處理中可使用例如送風乾燥機、烘箱、紅外線乾燥機、加熱筒(drum)等。 For example, a blower dryer, an oven, an infrared dryer, a drum, or the like can be used for the heat treatment.

<還原步驟> <Restore step>

本步驟是對上述塗膜形成步驟中形成的塗膜進行光照射處理，將氧化銅粒子及/或銅粒子還原而形成導電膜的步驟。 This step is a step of subjecting the coating film formed in the coating film forming step to a light irradiation treatment to reduce copper oxide particles and/or copper particles to form a conductive film.

光照射處理中使用的光源並無特別限制，例如有：水銀燈、金屬鹵化物燈、氙(Xe)燈、化學燈、碳弧燈等。放射線有：電子束、X射線、離子束、遠紅外線等。另外，亦使用g射線、i射線、深紫外光(Deep-UV光)、高密度能量束(雷射束)。 The light source used in the light irradiation treatment is not particularly limited, and examples thereof include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Radiation: electron beam, X-ray, ion beam, far infrared, etc. In addition, g-rays, i-rays, deep ultraviolet light (Deep-UV light), and high-density energy beams (laser beams) are also used.

具體的態樣可適宜列舉：藉由紅外線雷射的掃描曝光、氙(Xe) 放電燈等高照度閃光曝光(flash exposure)、紅外線燈曝光等。 The specific aspect can be suitably enumerated: scanning exposure by infrared laser, xe (Xe) High-illumination flash exposure, infrared lamp exposure, etc.

光照射處理較佳為利用閃光燈(特別是Xe閃光燈)的光照射處理，更佳為利用閃光燈(特別是Xe閃光燈)的脈衝光照射處理。高能量的脈衝光的照射由於可對賦予塗膜的部分的表面，以極短的時間來集中加熱，故而可極力減小熱對基材的影響。 The light irradiation treatment is preferably a light irradiation treatment using a flash lamp (particularly, a Xe flash lamp), and more preferably a pulse light irradiation treatment using a flash lamp (particularly, a Xe flash lamp). Since the irradiation of the high-energy pulsed light is concentrated and heated in a very short time on the surface of the portion to which the coating film is applied, the influence of heat on the substrate can be minimized.

脈衝光的照射能量較佳為1J/cm2~100J/cm2，更佳為1J/cm2~50J/cm2，尤佳為1J/cm2~30J/cm2。脈衝光的脈衝寬度較佳為1微秒~100毫秒，更佳為10微秒~10毫秒。脈衝光的照射時間較佳為1微秒~1000毫秒，更佳為1毫秒~500毫秒，尤佳為1毫秒~200毫秒。 The irradiation energy of the pulse light is preferably 1J / cm 2 ~ 100J / cm 2, more preferably 1J / cm 2 ~ 50J / cm 2, particularly preferably 1J / cm 2 ~ 30J / cm 2. The pulse width of the pulsed light is preferably from 1 microsecond to 100 milliseconds, more preferably from 10 microseconds to 10 milliseconds. The irradiation time of the pulsed light is preferably from 1 microsecond to 1000 milliseconds, more preferably from 1 millisecond to 500 milliseconds, and particularly preferably from 1 millisecond to 200 milliseconds.

實施上述光照射處理的環境並無特別限制，可列舉：大氣環境下、惰性氣體環境下、或者還原性氣體環境下等。此外，所謂惰性氣體環境，是指例如充滿氬、氦、氖、氮等惰性氣體的環境，另外，所謂還原性氣體環境，是指存在氫氣、一氧化碳、甲酸、醇等還原性氣體的環境。 The environment in which the light irradiation treatment is carried out is not particularly limited, and examples thereof include an atmospheric environment, an inert gas atmosphere, or a reducing gas atmosphere. In addition, the inert gas atmosphere refers to an environment filled with an inert gas such as argon, helium, neon or nitrogen. The term "reducing gas atmosphere" refers to an environment in which a reducing gas such as hydrogen, carbon monoxide, formic acid or alcohol is present.

<導電膜> <conductive film>

藉由實施上述步驟而獲得導電膜。 A conductive film is obtained by carrying out the above steps.

導電膜的膜厚並無特別限制，根據所使用的用途來適當調整最佳的膜厚。其中，就印刷配線基板用途的方面而言，較佳為0.01μm~1000μm，更佳為0.1μm~100μm。 The film thickness of the conductive film is not particularly limited, and an optimum film thickness is appropriately adjusted depending on the use used. Among them, from the viewpoint of the use of the printed wiring board, it is preferably from 0.01 μm to 1000 μm, more preferably from 0.1 μm to 100 μm.

此外，膜厚是對導電膜的任意點的厚度測定3個部位以上，將其值進行算術平均而獲得的值(平均值)。 In addition, the film thickness is a value (average value) obtained by measuring the thickness of any point of the conductive film at three or more places and arithmetically averaging the values.

就導電特性的方面而言，導電膜的體積電阻值較佳為2.0×10-4Ω．cm以下。 The volume resistivity of the conductive film is preferably 2.0×10 -4 Ω in terms of conductive properties. Below cm.

體積電阻值可藉由利用四探針法來測定導電膜的表面電阻值後，將所得的表面電阻值與膜厚相乘來算出。 The volume resistance value can be calculated by measuring the surface resistance value of the conductive film by the four-probe method and multiplying the obtained surface resistance value by the film thickness.

導電膜可設置於基材的整個面、或者設置為圖案狀。圖案狀的導電膜可用作印刷配線基板等的導體配線(配線)。 The conductive film may be provided on the entire surface of the substrate or in a pattern. The patterned conductive film can be used as a conductor wiring (wiring) of a printed wiring board or the like.

獲得圖案狀的導電膜的方法可列舉：將上述導電膜形成用組成物於基材賦予為圖案狀，進行上述光照射處理的方法；或將設置於基材整個面的導電膜蝕刻為圖案狀的方法等。 In the method of obtaining the patterned conductive film, the conductive film forming composition is applied to the substrate in a pattern, and the light irradiation treatment is performed; or the conductive film provided on the entire surface of the substrate is etched into a pattern. Method etc.

蝕刻的方法並無特別限制，可採用公知的減色法(subtractive process)、半加成法(semiadditive process)等。 The etching method is not particularly limited, and a known subtractive process, semiadiditive process, or the like can be employed.

於將圖案狀的導電膜構成為多層配線基板的情況下，可於圖案狀的導電膜的表面進而積層絕緣層(絕緣樹脂層、層間絕緣膜、阻焊層(solder resist))，於其表面形成進一步的配線(金屬圖案)。 When the patterned conductive film is formed as a multilayer wiring substrate, an insulating layer (insulating resin layer, interlayer insulating film, solder resist) may be laminated on the surface of the patterned conductive film. Further wiring (metal pattern) is formed.

絕緣膜的材料並無特別限制，例如可列舉：環氧樹脂、聚芳醯胺(aramid)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、全氟化非晶質樹脂等)、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 aramid resin, a crystalline polyolefin resin, an amorphous polyolefin resin, and a fluorine-containing resin (polytetrafluoroethylene, perfluoro). Polyimide, perfluorinated amorphous resin, polyether oxime resin, polyphenylene sulfide resin, polyetheretherketone resin, liquid crystal resin, and the like.

該些材料中，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、或者液晶樹 脂的材料，更佳為環氧樹脂。具體而言，可列舉味之素精細化學(Ajinomoto Fine-Techno)(股)製造的ABF GX-13等。 Among these materials, from the viewpoints of adhesion, dimensional stability, heat resistance, electrical insulation, etc., it is preferred to contain an epoxy resin, a polyimide resin, or a liquid crystal tree. The material of the grease is more preferably an epoxy resin. Specifically, ABF GX-13 manufactured by Ajinomoto Fine-Techno Co., Ltd., and the like can be mentioned.

另外，作為用於保護配線的絕緣層的材料的一種的阻焊劑，例如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。阻焊劑可使用市售品，具體而言，例如可列舉：太陽墨水製造(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 described in, for example, Japanese Laid-Open Patent Publication No. Hei 10-204150, or Japanese Patent Laid-Open No. 2003-222993, and the like. The materials described therein are used in the present invention. A commercially available product can 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.

上述所獲得的具有導電膜的基材(帶有導電膜的基材)可用於多種用途。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)、無線射頻辨識系統(Radio Frequency Identification system，RFID)等。 The substrate (the substrate with a conductive film) having the above-obtained 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 system (RFID), etc. are mentioned.

[實施例] [Examples]

以下，藉由實施例，對本發明進一步進行詳細說明，但本發明並不限定於該些實施例。 Hereinafter, the present invention will be further described in detail by way of examples, but the invention is not limited thereto.

(合成例1：聚合物1) (Synthesis Example 1: Polymer 1)

於三口燒瓶中添加N-乙烯基吡咯啶酮80質量份、220質量份的二甲基乙醯胺(dimethyl acetamide，DMAc)，於氮氣流下加熱至75℃。向其中，花3小時滴加N-乙烯基吡咯啶酮(下述結構)80質量份、Cyclomer A(下述結構，大賽璐(Daicel)公司製造)29質量份、以及V-601(和光純藥公司製造，下述結構)3.7質量 份的DMAc(220質量份)溶液。滴加結束後，攪拌3小時。然後，將反應溶液冷卻至室溫。反應結束後，以己烷/乙酸乙酯進行再沈澱，取出固形物(聚合物)。所得聚合物的重量平均分子量Mw為31000。將所得的聚合物作為聚合物1。 80 parts by mass of N-vinylpyrrolidone and 220 parts by mass of dimethyl acetamide (DMAc) were added to a three-necked flask, and the mixture was heated to 75 ° C under a nitrogen stream. 80 parts by mass of N-vinylpyrrolidone (structure described below), 29 parts by mass of Cyclomer A (structure described below, manufactured by Daicel Co., Ltd.), and V-601 (and pure light) were added dropwise thereto for 3 hours. Manufactured by a pharmaceutical company, the following structure) 3.7 quality A portion of DMAc (220 parts by mass) solution. After the completion of the dropwise addition, the mixture was stirred for 3 hours. Then, the reaction solution was cooled to room temperature. After completion of the reaction, reprecipitation was carried out with hexane/ethyl acetate, and the solid (polymer) was taken out. The weight average molecular weight Mw of the obtained polymer was 31,000. The obtained polymer was designated as Polymer 1.

(合成例2：聚合物2) (Synthesis Example 2: Polymer 2)

於三口燒瓶中添加N-乙烯基吡咯啶酮62質量份、202質量份的DMAc，於氮氣流下加熱至75℃。向其中，花3小時滴加N-乙烯基吡咯啶酮62質量份、羥基甲基丙烯醯胺(下述結構)49質量份、以及V-601(和光純藥公司製造)3.7質量份的DMAc(202質量份)溶液。滴加結束後，攪拌3小時。然後，將反應溶液冷卻至室溫。反應結束後，以乙酸乙酯進行再沈澱，取出固形物(聚合物)。所得聚合物的重量平均分子量Mw為36000。將所得的聚合物作為聚合物2。 62 parts by mass of N-vinylpyrrolidone and 202 parts by mass of DMAc were added to a three-necked flask, and the mixture was heated to 75 ° C under a nitrogen stream. In this case, 62 parts by mass of N-vinylpyrrolidone, 49 parts by mass of hydroxymethyl acrylamide (the following structure), and 3.7 parts by mass of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were added dropwise for 3 hours. (202 parts by mass) solution. After the completion of the dropwise addition, the mixture was stirred for 3 hours. Then, the reaction solution was cooled to room temperature. After completion of the reaction, reprecipitation was carried out with ethyl acetate, and the solid matter (polymer) was taken out. The weight average molecular weight Mw of the obtained polymer was 36,000. The obtained polymer was designated as Polymer 2.

(合成例3：聚合物3) (Synthesis Example 3: Polymer 3)

於三口燒瓶中添加N-乙烯基吡咯啶酮62質量份、183質量份的DMAc，於氮氣流下加熱至75℃。向其中，花3小時滴加N-乙烯基吡咯啶酮62質量份、4-羥基丁基丙烯酸酯縮水甘油醚(下述結構)32質量份、以及V-601(和光純藥公司製造)3.7質量份的DMAc(183質量份)溶液。滴加結束後，攪拌3小時。然後，將反應溶液冷卻至室溫。反應結束後，以乙酸乙酯進行再沈澱，取出固形物(聚合物)。所得聚合物的重量平均分子量Mw為30000。將所得的聚合物作為聚合物3。 62 parts by mass of N-vinylpyrrolidone and 183 parts by mass of DMAc were added to a three-necked flask, and the mixture was heated to 75 ° C under a nitrogen stream. In this case, 62 parts by mass of N-vinylpyrrolidone, 32 parts by mass of 4-hydroxybutyl acrylate glycidyl ether (structure described below), and V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) 3.7 were added dropwise thereto for 3 hours. Parts by mass of DMAc (183 parts by mass) solution. After the completion of the dropwise addition, the mixture was stirred for 3 hours. Then, the reaction solution was cooled to room temperature. After completion of the reaction, reprecipitation was carried out with ethyl acetate, and the solid matter (polymer) was taken out. The obtained polymer had a weight average molecular weight Mw of 30,000. The obtained polymer was designated as Polymer 3.

(合成例4：聚合物4) (Synthesis Example 4: Polymer 4)

於三口燒瓶中添加N-乙烯基吡咯啶酮62質量份、163質量份 的DMAc，於氮氣流下加熱至75℃。向其中，花3小時滴加N-乙烯基吡咯啶酮62質量份、乙烯基噁唑啉(下述結構)16質量份、以及V-601(和光純藥公司製造)3.7質量份的DMAc(163質量份)溶液。滴加結束後，攪拌3小時。然後，將反應溶液冷卻至室溫。反應結束後，以乙酸乙酯進行再沈澱，取出固形物(聚合物)。所得聚合物的重量平均分子量Mw為24000。將所得的聚合物作為聚合物4。 62 parts by mass of N-vinylpyrrolidone and 163 parts by mass were added to a three-necked flask The DMAc was heated to 75 ° C under a stream of nitrogen. In the above, 62 parts by mass of N-vinylpyrrolidone, 16 parts by mass of vinyloxazoline (structure described below), and 3.7 parts by mass of DMAc (manufactured by Wako Pure Chemical Industries, Ltd.) were added dropwise for 3 hours. 163 parts by mass) solution. After the completion of the dropwise addition, the mixture was stirred for 3 hours. Then, the reaction solution was cooled to room temperature. After completion of the reaction, reprecipitation was carried out with ethyl acetate, and the solid matter (polymer) was taken out. The weight average molecular weight Mw of the obtained polymer was 24,000. The obtained polymer was designated as Polymer 4.

(合成例5：聚合物5) (Synthesis Example 5: Polymer 5)

於三口燒瓶中加入180質量份的DMAc，於氮氣流下加熱至75℃。向其中，花3小時滴加Blemmer AE400(日油公司製造，下述結構)150質量份、以及V-601(和光純藥公司製造)0.7質量份的DMAc(180質量份)溶液。滴加結束後，攪拌3小時後，將反應溶液冷卻至室溫。反應結束後，以己烷/乙酸乙酯進行再沈澱，取出固形物(聚合物)。所得聚合物的重量平均分子量Mw為45000。將所得的聚合物作為聚合物5。 180 parts by mass of DMAc was placed in a three-necked flask and heated to 75 ° C under a nitrogen stream. To this, a solution of 150 parts by mass of Blemmer AE400 (manufactured by NOF Corporation, the following structure) and 0.7 parts by mass of DMAc (180 parts by mass) of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were added dropwise for 3 hours. After completion of the dropwise addition, the mixture was stirred for 3 hours, and then the reaction solution was cooled to room temperature. After completion of the reaction, reprecipitation was carried out with hexane/ethyl acetate, and the solid (polymer) was taken out. The weight average molecular weight Mw of the obtained polymer was 45,000. The obtained polymer was designated as the polymer 5.

(合成例6：聚合物6) (Synthesis Example 6: Polymer 6)

於三口燒瓶中添加Karenz AOI(和光純藥公司製造，下述結構)7質量份、2,5-二-第三戊基對苯二酚(下述結構)0.01質量份、四氫呋喃(tctrahydrofuran，THF)30質量份，於冰浴下滴加2-丁酮肟(下述結構)5質量份。於室溫下攪拌1小時後，以乙酸乙酯進行萃取，藉此獲得單體6(下述結構)。 In a three-necked flask, Karenz AOI (manufactured by Wako Pure Chemical Industries, Ltd., the following structure) was added in an amount of 7 parts by mass, and 2,5-di-third-pentyl hydroquinone (structure described below) was 0.01 parts by mass, and tetrahydrofuran (tctrahydrofuran, THF) was added. 30 parts by mass, 5 parts by mass of 2-butanone oxime (structure described below) was added dropwise under ice bath. After stirring at room temperature for 1 hour, extraction was carried out with ethyl acetate, whereby monomer 6 (structure described below) was obtained.

於三口燒瓶中添加N-乙烯基吡咯啶酮62質量份、188質量份的DMAc，於氮氣流下加熱至75℃。向其中，花3小時滴加N-乙烯基吡咯啶酮62質量份、單體6(37質量份)、以及V-601(和光純藥公司製造)3.7質量份的DMAc(163質量份)溶液。滴加結束後，攪拌3小時。然後，將反應溶液冷卻至室溫。反應結束後，以己烷/乙酸乙酯進行再沈澱，取出固形物(聚合物)。所得聚合物的重量平均分子量Mw為37000。將所得的聚合物作為聚合物6。 62 parts by mass of N-vinylpyrrolidone and 188 parts by mass of DMAc were added to a three-necked flask, and the mixture was heated to 75 ° C under a nitrogen stream. Into this, 62 parts by mass of N-vinylpyrrolidone, monomer 6 (37 parts by mass), and 3.7 parts by mass of DMAc (163 parts by mass) of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were added dropwise for 3 hours. . After the completion of the dropwise addition, the mixture was stirred for 3 hours. Then, the reaction solution was cooled to room temperature. After completion of the reaction, reprecipitation was carried out with hexane/ethyl acetate, and the solid (polymer) was taken out. The weight average molecular weight Mw of the obtained polymer was 37,000. The obtained polymer was designated as Polymer 6.

(合成例7：聚合物7) (Synthesis Example 7: Polymer 7)

於三口燒瓶中添加N-乙烯基吡咯啶酮80質量份、200質量份的DMAc，於氮氣流下加熱至75℃。向其中，花3小時滴加N-乙烯基吡咯啶酮80質量份、丙烯酸(下述結構)12質量份、以及V-601(和光純藥公司製造)3.7質量份的DMAc(200質量份)溶液。滴加結束後，攪拌3小時。然後，將反應溶液冷卻至室溫。 80 parts by mass of N-vinylpyrrolidone and 200 parts by mass of DMAc were added to a three-necked flask, and the mixture was heated to 75 ° C under a nitrogen stream. 80 parts by mass of N-vinylpyrrolidone, 12 parts by mass of acrylic acid (structure described below), and 3.7 parts by mass of DMAc (200 parts by mass) of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were added dropwise thereto for 3 hours. Solution. After the completion of the dropwise addition, the mixture was stirred for 3 hours. Then, the reaction solution was cooled to room temperature.

於該反應液中添加2,5-二-第三戊基對苯二酚0.05質量份、以及苄基三乙基氯化銨(下述結構)5質量份的DMAc(50質量份)溶液，進而添加甲基丙烯酸縮水甘油酯(下述結構)28質量份後，於100℃下攪拌4小時。反應結束後，以乙酸乙酯進行再沈澱，取出固形物(聚合物)。所得聚合物的重量平均分子量Mw為70000。將所得的聚合物作為聚合物7。 To the reaction liquid, 0.05 parts by mass of 2,5-di-p-pentyl hydroquinone and 5 parts by mass of DMAc (50 parts by mass) of benzyltriethylammonium chloride (structure described below) were added, Further, 28 parts by mass of glycidyl methacrylate (structure described below) was added, followed by stirring at 100 ° C for 4 hours. After completion of the reaction, reprecipitation was carried out with ethyl acetate, and the solid matter (polymer) was taken out. The weight average molecular weight Mw of the obtained polymer was 70,000. The obtained polymer was designated as Polymer 7.

(聚合物8) (Polymer 8)

將PVA500(關東化學公司製造)作為聚合物8。 PVA500 (manufactured by Kanto Chemical Co., Ltd.) was used as the polymer 8.

(聚合物9) (Polymer 9)

於三口燒瓶中加入180質量份的DMAc，於氮氣流下加熱至75℃。向其中，花3小時滴加4-羥基丁基丙烯酸酯縮水甘油醚(下述結構)150質量份、以及V-601(和光純藥公司製造)0.7質量份的DMAc(180質量份)溶液。滴加結束後，攪拌3小時後，將反應溶液冷卻至室溫。反應結束後，以己烷/乙酸乙酯進行再沈澱，取出固形物(聚合物)。所得聚合物的重量平均分子量Mw為40000。將所得的聚合物作為聚合物9。 180 parts by mass of DMAc was placed in a three-necked flask and heated to 75 ° C under a nitrogen stream. A solution of 150 parts by mass of 4-hydroxybutyl acrylate glycidyl ether (structure described below) and 0.7 parts by mass of DMAc (180 parts by mass) of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were added dropwise thereto for 3 hours. After completion of the dropwise addition, the mixture was stirred for 3 hours, and then the reaction solution was cooled to room temperature. After completion of the reaction, reprecipitation was carried out with hexane/ethyl acetate, and the solid (polymer) was taken out. The obtained polymer had a weight average molecular weight Mw of 40,000. The obtained polymer was designated as Polymer 9.

關於上述聚合物1~聚合物9，將聚合物中所含的重複 單元歸納示於以下。此處，聚合物1~聚合物8相當於特定聚合物。另外，聚合物9是雖包含上述式(2)所表示的重複單元，但不含上述式(1)所表示的重複單元的聚合物，不相當於特定聚合物。 Regarding the above polymer 1 to polymer 9, the repetition contained in the polymer Unit induction is shown below. Here, the polymer 1 to the polymer 8 correspond to a specific polymer. In addition, the polymer 9 is a polymer which does not contain the repeating unit represented by the above formula (2), but does not contain the repeating unit represented by the above formula (1), and does not correspond to a specific polymer.

此外，聚合物1~聚合物4、聚合物6及聚合物7的所示的重複單元中左側的重複單元相當於上述式(1)所表示的重複單元，且右側的重複單元相當於上述式(2)所表示的重複單元。另外，關於聚合物5，所示的重複單元相當於上述式(1)所表示的重複單元及上述式(2)所表示的重複單元。另外，關於聚合物8，所示的重複單元中左側的重複單元相當於上述式(1)所表示的重複單元及上述式(2)所表示的重複單元。 Further, in the repeating unit of the polymer 1 to the polymer 4, the polymer 6 and the polymer 7, the repeating unit on the left side corresponds to the repeating unit represented by the above formula (1), and the repeating unit on the right side corresponds to the above formula. (2) The repeating unit indicated. Further, the repeating unit shown in the polymer 5 corresponds to the repeating unit represented by the above formula (1) and the repeating unit represented by the above formula (2). Further, regarding the polymer 8, the repeating unit on the left side in the repeating unit shown corresponds to the repeating unit represented by the above formula (1) and the repeating unit represented by the above formula (2).

(聚合物的水溶液及乙醇溶液的製備) (Preparation of aqueous solution of polymer and ethanol solution)

將上述聚合物1~聚合物8分別溶解於水中，獲得聚合物的水溶液(聚合物濃度：35質量%)。將所得的水溶液分別作為水溶液1~水溶液8。 Each of the above polymer 1 to polymer 8 was dissolved in water to obtain an aqueous solution of a polymer (polymer concentration: 35 mass%). The obtained aqueous solution was used as an aqueous solution 1 to an aqueous solution 8, respectively.

將上述聚合物9溶解於乙醇中，獲得聚合物的乙醇溶液(聚合物濃度：35質量%)。將所得的乙醇溶液作為乙醇溶液9。 The above polymer 9 was dissolved in ethanol to obtain an ethanol solution of the polymer (polymer concentration: 35 mass%). The obtained ethanol solution was used as an ethanol solution 9.

<實施例1> <Example 1>

利用練太郎(新基(Thinky)公司製造)(2200rpm，3分鐘)使CuO奈米粒子(關東化學公司製造：粒徑27nm~95nm)65質量份、純水35質量份分散，獲得CuO膏(CuO：65質量%)。 CuO nanoparticle (manufactured by Kanto Chemical Co., Ltd.: particle size: 27 nm to 95 nm), 65 parts by mass, and 35 parts by mass of pure water were dispersed by using Ryotaro (manufactured by Shinky) (2200 rpm, 3 minutes) to obtain a CuO paste ( CuO: 65 mass%).

繼而，於上述CuO膏115質量份中添加上述水溶液1(26質 量份)、40質量% BYK-425(畢克化學日本(BYK-Chemie Japan)公司製造)丙二醇溶液8質量份、作為硬化劑的三伸乙基四胺0.4質量份，利用練太郎(2200rpm，3分鐘)進行混練，獲得組成物(導電膜形成用組成物)。 Then, the above aqueous solution 1 (26 mass) is added to 115 parts by mass of the above CuO paste. 40 parts by mass of BYK-425 (manufactured by BYK-Chemie Japan Co., Ltd.) 8 parts by mass of a propylene glycol solution and 0.4 parts by mass of a tri-ethyltetramine as a curing agent, using a Taro (2200 rpm, After 3 minutes, kneading was carried out to obtain a composition (a composition for forming a conductive film).

此外，上述組成物的組成以質量比計為CuO/聚合物/BYK-425/三伸乙基四胺/溶劑=50.0/6.1/2.1/0.3/41.5。 Further, the composition of the above composition was CuO / polymer / BYK - 425 / tri-extended ethyltetramine / solvent = 50.0 / 6.1 / 2.1 / 0.3 / 41.5 by mass ratio.

(硬化處理) (hardening treatment)

利用40μm間隙的塗佈棒將所得的組成物塗佈於玻璃環氧基板上。然後，將所塗佈的組成物於100℃下加熱乾燥10分鐘，進而於150℃下加熱1小時而使其硬化，獲得氧化銅膜。 The obtained composition was applied onto a glass epoxy substrate using a coating bar having a gap of 40 μm. Then, the applied composition was dried by heating at 100 ° C for 10 minutes, and further heated at 150 ° C for 1 hour to be hardened to obtain a copper oxide film.

(光照射處理) (light irradiation treatment)

藉由對所得的氧化銅膜照射Xe閃光燈(照射能量：4.9J/cm2，脈衝寬度：2毫秒)而獲得導電膜(銅膜)。 A conductive film (copper film) was obtained by irradiating the obtained copper oxide film with a Xe flash lamp (irradiation energy: 4.9 J/cm 2 , pulse width: 2 msec).

<實施例2> <Example 2>

除了代替三伸乙基四胺0.4質量份而使用二乙醇胺0.4質量份以外，依據與實施例1相同的程序獲得導電性組成物。 A conductive composition was obtained according to the same procedure as in Example 1 except that 0.4 parts by mass of diethanolamine was used instead of 0.4 parts by mass of triethylamine.

另外，使用所得的導電性組成物，依據與實施例1相同的程序獲得導電膜(銅膜)。 Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<實施例3> <Example 3>

除了代替水溶液1(26質量份)而使用上述水溶液2(26質量份)，且代替三伸乙基四胺0.4質量份而使用對甲苯磺酸0.3質量份以外，依據與實施例1相同的程序獲得導電性組成物。 The same procedure as in Example 1 was carried out except that the above aqueous solution 2 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.3 parts by mass of p-toluenesulfonic acid was used instead of 0.4 parts by mass of the tri-ethylethylamine. A conductive composition was obtained.

另外，使用所得的導電性組成物，依據與實施例1相同的程序獲得導電膜(銅膜)。 Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<實施例4> <Example 4>

除了代替水溶液1(26質量份)而使用上述水溶液2(26質量份)，且代替三伸乙基四胺0.4質量份而使用二乙醇胺0.5質量份以外，依據與實施例1相同的程序獲得導電性組成物。 Conduction was carried out according to the same procedure as in Example 1 except that the above aqueous solution 2 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.4 parts by mass of diethanolamine was used instead of 0.4 parts by mass of the triethylamine. Sexual composition.

另外，使用所得的導電性組成物，依據與實施例1相同的程序獲得導電膜(銅膜)。 Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<實施例5> <Example 5>

除了代替水溶液1(26質量份)而使用上述水溶液3(26質量份)以外，依據與實施例1相同的程序獲得導電性組成物。 A conductive composition was obtained according to the same procedure as in Example 1 except that the above aqueous solution 3 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass).

另外，使用所得的導電性組成物，依據與實施例1相同的程序獲得導電膜(銅膜)。 Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<實施例6> <Example 6>

除了代替水溶液1(26質量份)而使用上述水溶液4(26質量份)，且代替三伸乙基四胺0.4質量份而使用琥珀酸0.4質量份以外，依據與實施例1相同的程序獲得導電性組成物。 Conduction was carried out according to the same procedure as in Example 1 except that the above aqueous solution 4 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.4 parts by mass of succinic acid was used instead of 0.4 parts by mass of the tri-ethylethylamine. Sexual composition.

另外，使用所得的導電性組成物，依據與實施例1相同的程序獲得導電膜(銅膜)。 Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<實施例7> <Example 7>

除了代替水溶液1(26質量份)而使用上述水溶液5(26質量份)，且代替三伸乙基四胺0.4質量份而使用1,4-丁二醇二縮水 甘油醚0.5質量份以外，依據與實施例1相同的程序獲得導電性組成物。 The above aqueous solution 5 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 1,4-butanediol condensed water was used instead of 0.4 parts by mass of the tri-ethylethylamine. A conductive composition was obtained according to the same procedure as in Example 1 except that the glycerin ether was 0.5 parts by mass.

另外，使用所得的導電性組成物，依據與實施例1相同的程序獲得導電膜(銅膜)。 Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<實施例8> <Example 8>

除了代替水溶液1(26質量份)而使用上述水溶液6(26質量份)，且代替三伸乙基四胺0.4質量份而使用雙羥基甲基脲0.4質量份以外，依據與實施例1相同的程序獲得導電性組成物。 The same procedure as in Example 1 was carried out except that the above aqueous solution 6 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.4 parts by mass of bishydroxymethyl urea was used instead of 0.4 parts by mass of the tri-ethylethylamine. The procedure obtains a conductive composition.

另外，使用所得的導電性組成物，依據與實施例1相同的程序獲得導電膜(銅膜)。 Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<實施例9> <Example 9>

除了代替水溶液1(26質量份)而使用上述水溶液6(26質量份)，且代替三伸乙基四胺0.4質量份而使用二乙醇胺0.4質量份以外，依據與實施例1相同的程序獲得導電性組成物。 Conduction was carried out according to the same procedure as in Example 1 except that the above aqueous solution 6 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.4 parts by mass of diethanolamine was used instead of 0.4 parts by mass of the triethylamine. Sexual composition.

另外，使用所得的導電性組成物，依據與實施例1相同的程序獲得導電膜(銅膜)。 Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<實施例10> <Example 10>

除了代替水溶液1(26質量份)而使用上述水溶液7(26質量份)，且代替三伸乙基四胺0.4質量份而使用VA-080(和光純藥工業公司製造)0.1質量份以外，依據與實施例1相同的程序獲得導電性組成物。 In addition to the aqueous solution 1 (26 parts by mass), the aqueous solution 7 (26 parts by mass) was used instead of the 0.4 parts by mass of the THF-080 (manufactured by Wako Pure Chemical Industries, Ltd.), in place of 0.4 parts by mass of the tri-ethylethylamine. The same procedure as in Example 1 was carried out to obtain a conductive composition.

另外，使用所得的導電性組成物，依據與實施例1相同的程 序獲得導電膜(銅膜)。 Further, the obtained conductive composition was used in the same manner as in Example 1. A conductive film (copper film) is obtained in sequence.

<實施例11> <Example 11>

除了代替水溶液1(26質量份)而使用上述水溶液8(26質量份)，且代替三伸乙基四胺0.4質量份而使用1,4-丁二醇二縮水甘油醚0.5質量份以外，依據與實施例1相同的程序獲得導電性組成物。 The aqueous solution 8 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.5 parts by mass of 1,4-butanediol diglycidyl ether was used instead of 0.4 parts by mass of the tri-ethylethylamine. The same procedure as in Example 1 was carried out to obtain a conductive composition.

另外，使用所得的導電性組成物，依據與實施例1相同的程序獲得導電膜(銅膜)。 Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<實施例12> <Example 12>

除了代替水溶液1(26質量份)而使用上述水溶液8(26質量份)，且代替三伸乙基四胺0.4質量份而使用雙羥基甲基脲0.5質量份以外，依據與實施例1相同的程序獲得導電性組成物。 The same procedure as in Example 1 was carried out except that the above aqueous solution 8 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.5 parts by mass of bishydroxymethyl urea was used instead of 0.4 parts by mass of the triethylethylamine. The procedure obtains a conductive composition.

另外，使用所得的導電性組成物，依據與實施例1相同的程序獲得導電膜(銅膜)。 Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<實施例13> <Example 13>

除了代替水溶液1(26質量份)而使用上述水溶液8(26質量份)，且代替三伸乙基四胺0.4質量份而使用二乙烯基碸0.5質量份以外，依據與實施例1相同的程序獲得導電性組成物。 The same procedure as in Example 1 was carried out except that the above aqueous solution 8 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and 0.4 parts by mass of divinyl fluorene was used instead of 0.4 parts by mass of the tri-ethylethylamine. A conductive composition was obtained.

另外，使用所得的導電性組成物，依據與實施例1相同的程序獲得導電膜(銅膜)。 Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<實施例14> <Example 14>

除了代替水溶液1(26質量份)而使用上述水溶液8(26質 量份)，且代替三伸乙基四胺0.4質量份而使用乙二醛0.5質量份以外，依據與實施例1相同的程序獲得導電性組成物。 The above aqueous solution 8 was used instead of the aqueous solution 1 (26 parts by mass). A conductive composition was obtained according to the same procedure as in Example 1, except that 0.4 parts by mass of glyoxal was used instead of 0.4 parts by mass of tri-ethyltetramine.

另外，使用所得的導電性組成物，依據與實施例1相同的程序獲得導電膜(銅膜)。 Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<比較例1> <Comparative Example 1>

除了不添加硬化劑以外，依據與實施例1相同的程序獲得導電性組成物。 A conductive composition was obtained according to the same procedure as in Example 1 except that the hardener was not added.

另外，使用所得的導電性組成物，依據與實施例1相同的程序獲得導電膜(銅膜)。 Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<比較例2> <Comparative Example 2>

除了代替水溶液1(26質量份)而使用上述水溶液2(26質量份)，且不添加硬化劑以外，依據與實施例1相同的程序獲得導電性組成物。 A conductive composition was obtained according to the same procedure as in Example 1 except that the aqueous solution 2 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and the curing agent was not added.

另外，使用所得的導電性組成物，依據與實施例1相同的程序獲得導電膜(銅膜)。 Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<比較例3> <Comparative Example 3>

除了代替水溶液1(26質量份)而使用上述水溶液3(26質量份)，且不添加硬化劑以外，依據與實施例1相同的程序獲得導電性組成物。 A conductive composition was obtained according to the same procedure as in Example 1 except that the aqueous solution 3 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and the curing agent was not added.

另外，使用所得的導電性組成物，依據與實施例1相同的程序獲得導電膜(銅膜)。 Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<比較例4> <Comparative Example 4>

除了代替水溶液1(26質量份)而使用上述水溶液4(26質量份)，且不添加硬化劑以外，依據與實施例1相同的程序獲得導電性組成物。 A conductive composition was obtained according to the same procedure as in Example 1 except that the aqueous solution 4 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and the curing agent was not added.

另外，使用所得的導電性組成物，依據與實施例1相同的程序獲得導電膜(銅膜)。 Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<比較例5> <Comparative Example 5>

除了代替水溶液1(26質量份)而使用上述水溶液5(26質量份)，且不添加硬化劑以外，依據與實施例1相同的程序獲得導電性組成物。 A conductive composition was obtained according to the same procedure as in Example 1 except that the aqueous solution 5 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and the curing agent was not added.

另外，使用所得的導電性組成物，依據與實施例1相同的程序獲得導電膜(銅膜)。 Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<比較例6> <Comparative Example 6>

除了代替水溶液1(26質量份)而使用上述水溶液6(26質量份)，且不添加硬化劑以外，依據與實施例1相同的程序獲得導電性組成物。 A conductive composition was obtained according to the same procedure as in Example 1 except that the aqueous solution 6 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and the curing agent was not added.

另外，使用所得的導電性組成物，依據與實施例1相同的程序獲得導電膜(銅膜)。 Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<比較例7> <Comparative Example 7>

除了代替水溶液1(26質量份)而使用上述水溶液7(26質量份)，且不添加硬化劑以外，依據與實施例1相同的程序獲得導電性組成物。 A conductive composition was obtained according to the same procedure as in Example 1 except that the aqueous solution 7 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and the curing agent was not added.

另外，使用所得的導電性組成物，依據與實施例1相同的程 序獲得導電膜(銅膜)。 Further, the obtained conductive composition was used in the same manner as in Example 1. A conductive film (copper film) is obtained in sequence.

<比較例8> <Comparative Example 8>

除了代替水溶液1(26質量份)而使用上述水溶液8(26質量份)，且不添加硬化劑以外，依據與實施例1相同的程序獲得導電性組成物。 A conductive composition was obtained according to the same procedure as in Example 1 except that the above aqueous solution 8 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass), and the curing agent was not added.

另外，欲使用所得的導電性組成物，依據與實施例1相同的程序來獲得導電膜，結果，膜飛散，無法獲得導電膜，無法對後述的體積低效率以及密接性進行評價。 Further, in order to obtain the conductive film using the obtained conductive composition, the conductive film was obtained by the same procedure as in Example 1. As a result, the film was scattered, and the conductive film could not be obtained, and the volume inefficiency and adhesion which will be described later could not be evaluated.

<比較例9> <Comparative Example 9>

除了代替水溶液1(26質量份)而使用上述乙醇溶液9(26質量份)以外，依據與實施例1相同的程序獲得導電性組成物。 A conductive composition was obtained according to the same procedure as in Example 1 except that the above ethanol solution 9 (26 parts by mass) was used instead of the aqueous solution 1 (26 parts by mass).

另外，使用所得的導電性組成物，依據與實施例1相同的程序獲得膜。 Further, using the obtained conductive composition, a film was obtained in accordance with the same procedure as in Example 1.

此外，欲對所得的膜測定後述的體積電阻率，結果，由於體積電阻率超過測定上限值，故而無法測定體積電阻率。 Further, in order to measure the volume resistivity described later on the obtained film, as a result, since the volume resistivity exceeds the upper limit of the measurement, the volume resistivity cannot be measured.

將各實施例中使用的硬化劑的結構歸納示於以下。 The structure of the hardener used in each of the examples is summarized below.

<體積電阻率> <Volume resistivity>

對於所得的導電膜，使用四探針法電阻率計來測定體積電阻率。將測定結果示於第1表中。體積電阻率越小，導電性越優異。在實際使用時，較佳為20×10-5Ω．cm以下。 The volume resistivity of the obtained conductive film was measured using a four-probe method resistivity meter. The measurement results are shown in Table 1. The smaller the volume resistivity, the more excellent the conductivity. In actual use, it is preferably 20 × 10 -5 Ω. Below cm.

<密接性> <Adhesiveness>

於所得導電膜的5mm×5mm中，利用切割機切入切口，製作25個網格(1mm見方)。接著，貼附Cellotape(註冊商標)後剝離，查明未剝離而殘留的網格的個數。 In a 5 mm × 5 mm of the obtained conductive film, a slit was cut by a cutter to prepare 25 grids (1 mm square). Next, Cellotape (registered trademark) was attached and peeled off, and the number of meshes remaining without peeling was ascertained.

其結果為，將殘留的網格的個數為20個~25個者評價為「AA」，將15個~19個者評價為「A」，將10個~14個者評價為「B」，將1個~9個者評價為「C」，將0個者(完全剝離者)評價為「D」。 As a result, the number of remaining meshes was 20 to 25, and it was evaluated as "AA", 15 to 19 were evaluated as "A", and 10 to 14 were evaluated as "B". One to nine were evaluated as "C", and 0 (completely stripped) was evaluated as "D".

將結果示於第1表中。 The results are shown in the first table.

根據第1表可知，由本申請案實施例1~實施例14的組成物所獲得的導電膜均表現出優異的密接性及導電性，上述組成物含有包含上述式(1)所表示的重複單元及上述式(2)所表示的重複單元的聚合物以及與上述式(2)中的B所表示的交聯性基進行反應的硬化劑。其中，上述式(1)中的A為含有醯胺基的有機基的實施例1~實施例6以及實施例8~實施例10表現出更優 異的密接性。其中，上述式(2)中的B為上述式(B-7)(脂環式環氧基)且硬化劑為胺的實施例1表現出特別優異的密接性及導電性。 According to the first table, the conductive films obtained by the compositions of Examples 1 to 14 of the present application all exhibit excellent adhesion and conductivity, and the composition contains the repeating unit represented by the above formula (1). The polymer of the repeating unit represented by the above formula (2) and the curing agent which reacts with the crosslinkable group represented by B in the above formula (2). Among them, Examples 1 to 6 and Examples 8 to 10 in which A in the above formula (1) is an organic group containing a guanamine group exhibits superiority. Different adhesion. Among them, Example 1 in which the B in the above formula (2) is the above formula (B-7) (alicyclic epoxy group) and the curing agent is an amine exhibits particularly excellent adhesion and conductivity.

另外，根據上述式(2)中的B為上述式(B-1)(環氧基)或上述式(B-7)(脂環式環氧基)的實施例1、實施例2及實施例5的對比，使用胺作為硬化劑的實施例1及實施例5表現出更優異的密接性及導電性。 Further, Example 1, Example 2, and the embodiment in which B in the above formula (2) is the above formula (B-1) (epoxy group) or the above formula (B-7) (alicyclic epoxy group) In Comparative Example 5, Example 1 and Example 5 using an amine as a curing agent exhibited more excellent adhesion and electrical conductivity.

另一方面，於雖含有包含上述式(1)所表示的重複單元及上述式(2)所表示的重複單元的聚合物，但不含與上述式(2)中的B所表示的交聯性基進行反應的硬化劑的情況下，成為如下結果：膜飛散而無法獲得導電膜(比較例8)，或即便獲得導電膜，密接性亦變得不充分(比較例1~比較例7)。 On the other hand, the polymer containing the repeating unit represented by the above formula (1) and the repeating unit represented by the above formula (2) is not contained in the crosslinking represented by B in the above formula (2). In the case of the curing agent in which the reaction was carried out, the film was scattered and the conductive film could not be obtained (Comparative Example 8), or the adhesion was insufficient even when the conductive film was obtained (Comparative Example 1 to Comparative Example 7). .

另外，於不含包含上述式(1)所表示的重複單元及上述式(2)所表示的重複單元的聚合物(含有不含上述式(1)所表示的重複單元，而包含上述式(2)所表示的重複單元的聚合物)的情況下，即便含有與上述式(2)中的B所表示的交聯性基進行反應的硬化劑，所得的膜的密接性及導電性亦變得不充分(比較例9)。 In addition, the polymer containing the repeating unit represented by the above formula (1) and the repeating unit represented by the above formula (2) is contained (including the repeating unit represented by the above formula (1), and includes the above formula ( In the case of the curing agent which reacts with the crosslinkable group represented by B in the above formula (2), the adhesion and conductivity of the obtained film are changed. Not enough (Comparative Example 9).

Claims (7)

一種導電膜形成用組成物，其含有：氧化銅粒子及/或銅粒子、包含下述式(1)所表示的重複單元及下述式(2)所表示的重複單元的聚合物、以及與下述式(2)中的B所表示的交聯性基進行反應的硬化劑， (式(1)中，R1表示氫原子、或者經取代或未經取代的烷基；L1表示單鍵或2價有機基；A為還原性基，表示含有醯胺基的有機基、或羥基；式(2)中，R2表示氫原子、或者經取代或未經取代的烷基；L2表示單鍵或2價有機基；B為交聯性基，表示選自由下述式(B-1)~式(B-9)所組成的組群中的基) (式(B-1)~式(B-9)中，Rb表示氫原子、或可具有雜原子的烴基；存在多個的Rb可分別相同亦可不同；m表示0~11的整數；n表示0~2的整數；*表示鍵結位置)。 A conductive film-forming composition comprising: copper oxide particles and/or copper particles; a polymer comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and a curing agent that reacts with a crosslinkable group represented by B in the following formula (2), (In the formula (1), R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group; L 1 represents a single bond or a divalent organic group; and A is a reducing group, and represents an organic group containing a decylamino group, Or a hydroxy group; in the formula (2), R 2 represents a hydrogen atom or a substituted or unsubstituted alkyl group; L 2 represents a single bond or a divalent organic group; and B is a crosslinkable group, which is selected from the group consisting of (B-1)~ base in the group consisting of (B-9) (In the formula (B-1) to the formula (B-9), R b represents a hydrogen atom or a hydrocarbon group which may have a hetero atom; and a plurality of R b may be the same or different; m represents an integer of 0 to 11. ;n represents an integer from 0 to 2; * indicates the bonding position). 如申請專利範圍第1項所述的導電膜形成用組成物，其中上述聚合物為包含下述式(3)所表示的重複單元及下述式(2)所表示的重複單元的聚合物、包含下述式(4)所表示的重複單元及下述式(5)所表示的重複單元的聚合物、或者包含下述式(6)所表示的重複單元的聚合物， (式(3)中，R3表示氫原子、或者經取代或未經取代的烷基；R31表示氫原子、或可具有雜原子的烴基；存在多個的R31可分別相同亦可不同；式(2)中，R2表示氫原子、或者經取代或未經取代的烷基；L2表示單鍵或2價有機基；B為交聯性基，表示選自由上述式(B-1)~式(B-9)所組成的組群中的基) (式(4)及式(5)中，R4及R5分別獨立地表示氫原子、或者經取代或未經取代的烷基) (式(6)中，R6表示氫原子、或者經取代或未經取代的烷基；L6表示單鍵或2價有機基；R61表示2價脂肪族烴基；p表示1~100的整數)。 The conductive film-forming composition according to the first aspect of the invention, wherein the polymer is a polymer comprising a repeating unit represented by the following formula (3) and a repeating unit represented by the following formula (2), a polymer comprising a repeating unit represented by the following formula (4) and a repeating unit represented by the following formula (5), or a polymer comprising a repeating unit represented by the following formula (6), (In the formula (3), R 3 represents a hydrogen atom or a substituted or unsubstituted alkyl group; R 31 represents a hydrogen atom or a hydrocarbon group which may have a hetero atom; and a plurality of R 31 may be the same or different In the formula (2), R 2 represents a hydrogen atom or a substituted or unsubstituted alkyl group; L 2 represents a single bond or a divalent organic group; and B is a crosslinkable group, which is selected from the above formula (B- 1) ~ base in the group consisting of (B-9) (In the formulae (4) and (5), R 4 and R 5 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group) (In the formula (6), R 6 represents a hydrogen atom or a substituted or unsubstituted alkyl group; L 6 represents a single bond or a divalent organic group; R 61 represents a divalent aliphatic hydrocarbon group; and p represents a group of 1 to 100. Integer). 如申請專利範圍第2項所述的導電膜形成用組成物，其中上述聚合物為包含上述式(3)所表示的重複單元及上述式(2)所表示的重複單元的聚合物。 The composition for forming a conductive film according to the second aspect of the invention, wherein the polymer is a polymer comprising a repeating unit represented by the above formula (3) and a repeating unit represented by the above formula (2). 如申請專利範圍第1項至第3項中任一項所述的導電膜形成用組成物，其中上述式(2)中的B為上述式(B-1)或式(B-7)所表示的基，上述硬化劑為胺或醇。 The composition for forming a conductive film according to any one of the above-mentioned formula (2), wherein B in the above formula (2) is a formula (B-1) or a formula (B-7). The base represented by the above hardener is an amine or an alcohol. 如申請專利範圍第1項至第3項中任一項所述的導電膜形成用組成物，其中上述式(2)中的B為上述式(B-2)所表示的基，上述硬化劑為環氧化物、醛、或者具有2個以上的下述式(13)所表示的部分結構的化合物， (式(13)中，R131表示氫原子、或者經取代或未經取代的烷基)。 The composition for forming a conductive film according to any one of the above-mentioned formula (2), wherein B in the above formula (2) is a group represented by the above formula (B-2), the hardener An epoxide, an aldehyde, or a compound having two or more partial structures represented by the following formula (13), (In the formula (13), R 131 represents a hydrogen atom or a substituted or unsubstituted alkyl group). 一種導電膜的製造方法，其包括：塗膜形成步驟，將如申請專利範圍第1項至第5項中任一項所述的導電膜形成用組成物賦予至基材上，於上述基材上形成組成物層，然後，對上述組成物層實施加熱處理而形成塗膜；以及還原步驟，對上述塗膜進行光照射處理，將上述氧化銅粒子及/或銅粒子進行還原而形成導電膜。 A method of producing a conductive film, comprising: a coating film forming step of imparting a composition for forming a conductive film according to any one of claims 1 to 5 to a substrate Forming a composition layer thereon, and then subjecting the composition layer to heat treatment to form a coating film; and a reducing step of performing light irradiation treatment on the coating film to reduce the copper oxide particles and/or copper particles to form a conductive film . 如申請專利範圍第6項所述的導電膜的製造方法，其中上述光照射處理為脈衝光照射處理。 The method for producing a conductive film according to claim 6, wherein the light irradiation treatment is pulsed light irradiation treatment.
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