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

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

Conductive film forming composition and method of producing conductive film using the same

The present invention relates to a composition for forming a conductive film and a method for producing a conductive film using the same.

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.

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.

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.

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.).

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-528428

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.

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.

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.

In other words, the inventors of the present invention have found that the above problems can be solved by the following configuration.

(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) 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) 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).

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.

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) 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) The method for producing a conductive film according to the above (6), wherein the light irradiation treatment is pulsed light irradiation treatment.

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.

[Conductive film forming composition]

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).

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.

The details are not clear, but they are roughly speculated as follows.

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.

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.

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.

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.

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.

<Copper oxide particles and/or copper particles>

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.

(copper oxide particles)

The copper oxide particles contained in the composition of the present invention are not particularly limited as long as they are particulate copper oxide.

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.

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.

The copper oxide particles are preferably nano particles.

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.

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.

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.

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.

(copper particles)

The copper particles contained in the composition of the present invention are not particularly limited as long as they are particulate copper.

The definition of the particle shape is the same as that of the above copper oxide particles.

The copper particles are preferably nano particles.

A preferred aspect of the average particle diameter of the copper particles is the same as that of the above copper oxide particles.

<polymer>

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).

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.

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.

In the above formula (1), L ₁ represents a single bond or a divalent organic group.

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.

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.

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).

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 .

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.

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.

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.

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.

In the above formula (7), * represents a bonding position.

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.

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.

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.

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.

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).

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.

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.

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).

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.

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.

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.

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.

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).

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.

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.

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.

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.

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.

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.

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).

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.

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.

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.

In the above formula (6), p represents an integer of 1 to 100. Among them, an integer of 5 to 30 is preferred.

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).

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.

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.

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.

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.

Further, various initiators (e.g., a radical polymerization initiator, etc.) may be used as needed in each polymerization form.

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.

<hardener>

The composition of the present invention contains a curing agent which reacts with the crosslinkable group represented by B in the above formula (2).

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.

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.

H ₂ NL ₁₆ -NH ₂ formula (16)

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.

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.

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.

In the above formula (9), s is 0 or 1.

In the above formula (9), t is 2 or 3.

In the above formula (9), s and t satisfy the relational expression of s+t=3.

Further, preferred examples of the above alcohols include, for example, two or more A compound of a partial structure represented by the formula (13).

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.

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).

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.

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.

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.

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.

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.

The above aldehyde is preferably glyoxal.

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).

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.

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 -.

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.

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-L ₁₅ -COOH type (15)

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.

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.

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.

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.

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.

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).

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.

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.

<solvent>

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.

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.

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.

<Other ingredients>

The composition of the present invention may contain components other than the above components.

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.

<Viscosity of Composition for Conductive Film Formation>

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.

<Method for Preparing Composition for Conductive Film Formation>

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.

[Method of Manufacturing Conductive Film]

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.

<Coating film forming step>

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.

The composition for forming a conductive film to be used is as described above.

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.

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.

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.

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.

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).

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.

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.

For example, a blower dryer, an oven, an infrared dryer, a drum, or the like can be used for the heat treatment.

<Restore step>

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.

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.

The specific aspect can be suitably enumerated: scanning exposure by infrared laser, xe (Xe) High-illumination flash exposure, infrared lamp exposure, etc.

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.

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.

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.

<conductive film>

A conductive film is obtained by carrying out the above steps.

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.

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.

The volume resistivity of the conductive film is preferably 2.0×10 ^-4 Ω in terms of conductive properties. Below cm.

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.

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.

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.

The etching method is not particularly limited, and a known subtractive process, semiadiditive process, or the like can be employed.

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.

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.

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.

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.

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.

[Examples]

Hereinafter, the present invention will be further described in detail by way of examples, but the invention is not limited thereto.

(Synthesis Example 1: Polymer 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.

(Synthesis Example 2: Polymer 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.

(Synthesis Example 3: Polymer 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.

(Synthesis Example 4: Polymer 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.

(Synthesis Example 5: Polymer 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.

(Synthesis Example 6: Polymer 6)

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.

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.

(Synthesis Example 7: Polymer 7)

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.

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.

(Polymer 8)

PVA500 (manufactured by Kanto Chemical Co., Ltd.) was used as the polymer 8.

(Polymer 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.

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.

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).

(Preparation of aqueous solution of polymer and ethanol solution)

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.

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.

<Example 1>

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%).

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).

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.

(hardening treatment)

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.

(light irradiation treatment)

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).

<Example 2>

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.

Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<Example 3>

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.

Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<Example 4>

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.

Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<Example 5>

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).

Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<Example 6>

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.

Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<Example 7>

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.

Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<Example 8>

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.

Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<Example 9>

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.

Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<Example 10>

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.

Further, the obtained conductive composition was used in the same manner as in Example 1. A conductive film (copper film) is obtained in sequence.

<Example 11>

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.

Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<Example 12>

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.

Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<Example 13>

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.

Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<Example 14>

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.

Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<Comparative Example 1>

A conductive composition was obtained according to the same procedure as in Example 1 except that the hardener was not added.

Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<Comparative Example 2>

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.

Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<Comparative Example 3>

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.

Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<Comparative Example 4>

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.

Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<Comparative Example 5>

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.

Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<Comparative Example 6>

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.

Further, using the obtained conductive composition, a conductive film (copper film) was obtained in accordance with the same procedure as in Example 1.

<Comparative Example 7>

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.

Further, the obtained conductive composition was used in the same manner as in Example 1. A conductive film (copper film) is obtained in sequence.

<Comparative Example 8>

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.

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.

<Comparative Example 9>

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).

Further, using the obtained conductive composition, a film was obtained in accordance with the same procedure as in Example 1.

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.

The structure of the hardener used in each of the examples is summarized below.

<Volume resistivity>

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.

<Adhesiveness>

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.

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".

The results are shown in the first table.

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.

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.

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). .

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)

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). 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). 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). 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. 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). 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 . The method for producing a conductive film according to claim 6, wherein the light irradiation treatment is pulsed light irradiation treatment.