WO2015151628A1 - Method for producing conductive film and composition for forming conductive film - Google Patents

Abstract

The purpose of the present invention is to provide: a method for producing a conductive film, which is capable of producing a conductive film having excellent electrical conductivity and excellent transferability, while having less defects; and a composition for forming a conductive film. The present invention is a method for producing a conductive film, which comprises: a coating film formation step wherein a composition for forming a conductive film containing (A) copper oxide particles, (B) at least one compound selected from the group consisting of polyalkylene glycols and organic compounds having a boiling point of 250°C or more and containing at least one hydroxy group in each molecule and (C) an organic solvent having a boiling point less than 100°C is applied onto a temporary supporting body, thereby forming a coating film; a removal step wherein a part of the coating film is removed; a transfer step wherein the coating film remaining on the temporary supporting body is transferred to a base, thereby forming a precursor film of a conductive film; and a sintering step wherein the copper oxide particles (A) in the precursor film are reduced and fusion bonded by having the precursor film irradiated with light, thereby forming a conductive film. In this connection, the content of the copper oxide particles (A) is from 50% by mass to 95% by mass (inclusive) of the total mass of the copper oxide particles (A) and the compound (B), and the content of the organic solvent (C) is 10% by mass or more of the total mass of the composition for forming a conductive film.

Description

Method for producing conductive film and composition for forming conductive film

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

A technique for forming a conductive film such as a wiring on a base material by applying a dispersion of metal oxide particles on the base material by a printing method and then sintering it is known.
The above method is highly anticipated in the development of next-generation electronics because it is simpler, energy-saving, and resource-saving than the conventional high-heat / vacuum process (sputtering) or plating process.
For example, Patent Document 1 is a method of forming a conductive film, in which a film containing a plurality of copper nanoparticles is deposited on the surface of a substrate, and at least a part of the film is exposed, And making the exposed portion conductive.

Special table 2010-528428

In recent years, there has been a demand for improved performance of various devices. Along with this, there has been a demand for further improvement in the conductivity of conductive films used for wiring boards in devices.
On the other hand, as a printing method for forming a fine pattern of several micrometers, a reversal printing method (for example, using a printing plate) is attracting attention as a printing method different from conventional general relief printing, intaglio printing, planographic printing, and stencil printing. Yes.
Under these circumstances, the present inventors printed a dispersion containing copper oxide nanoparticles by reversal printing with reference to Patent Document 1, and produced a conductive film by light irradiation. It has been clarified that the conductivity of the obtained conductive film and the number of defects in the conductive film (ablation resistance) do not necessarily satisfy the level required recently.
Accordingly, in view of the above circumstances, a method for producing a conductive film that is excellent in conductivity, has few defects, and is excellent in transferability, and a conductive film forming composition used therefor are provided. This is the issue.

As a result of diligent research to solve the above problems, the present inventors have reversed a composition for forming a conductive film containing copper oxide particles (A), a specific compound (B), and a specific organic solvent (C). It was found that a conductive film having excellent conductivity and few defects can be formed by transferring onto a base material by a printing method and irradiating light, and that transferability is also excellent. In addition, the present inventor has a conductive film-forming composition containing copper oxide particles (A), a specific compound (B), and a specific organic solvent (C) in a predetermined amount, and has excellent conductivity. The present invention was completed by discovering that a conductive film with few defects can be formed and transferability in the reverse printing method is excellent. That is, the present inventors have found that the above problem can be solved by the following configuration.

(1) Copper oxide particles (A), at least one compound (B) selected from the group consisting of an organic compound having a boiling point of 250 ° C. or higher and having at least one hydroxy group per molecule and polyalkylene glycol A coating film forming step of forming a coating film by applying a conductive film forming composition containing an organic solvent (C) having a boiling point of less than 100 ° C. on a temporary support;
A removal step of removing a part of the coating film;
A transfer step of transferring the remaining coating film on the temporary support onto a substrate to form a precursor film of a conductive film;
A process of forming a conductive film by irradiating the precursor film with light and reducing and fusing the copper oxide particles (A) in the precursor film,
Content of the said copper oxide particle (A) is 50 mass% or more and 95 mass% or less in the total amount of the said copper oxide particle (A) and the said compound (B),
The manufacturing method of the electrically conductive film whose content of the said organic solvent (C) is 10 mass% or more in the whole quantity of the said composition for electrically conductive film formation.
(2) The manufacturing method of the electrically conductive film as described in said (1) in which the said composition for electrically conductive film formation contains surfactant (D) further.
(3) The conductive film according to (1) or (2), wherein the copper oxide particles (A) are cupric oxide, and the average primary particle diameter of the copper oxide particles (A) is 100 nm or less. Production method.
(4) The organic compound according to any one of (1) to (3), wherein the organic compound having a boiling point of 250 ° C. or more and having at least one hydroxy group per molecule has two or three hydroxy groups per molecule. The manufacturing method of the electrically conductive film of description.
(5) The content of the compound (B) is 6% by mass or more and 100% by mass or less with respect to the total amount of the copper oxide particles (A), according to any one of the above (1) to (4). Manufacturing method of electrically conductive film.
(6) The method for producing a conductive film according to any one of (1) to (5), wherein the compound (B) includes at least one selected from the group consisting of polyethylene glycol, glycerin, and trimethylolpropane.
(7) The method for producing a conductive film according to any one of (1) to (6), wherein the compound (B) comprises polyethylene glycol and glycerin and / or trimethylolpropane.
(8) The content of the polyethylene glycol is 4% by mass or more and less than 50% by mass with respect to the total amount of the copper oxide particles (A), and the total amount of the glycerin and / or the trimethylolpropane is the copper oxide particles. The manufacturing method of the electrically conductive film as described in said (7) which is 10 to 30 mass% with respect to the whole quantity of (A).
(9) The method for producing a conductive film according to any one of (6) to (8), wherein the polyethylene glycol has a weight average molecular weight of 3000 or more.
(10) The above (1), wherein the conductive film-forming composition further comprises a metal catalyst (E) containing at least one metal element selected from the group consisting of Groups 8 to 11 of the periodic table. The manufacturing method of the electrically conductive film in any one of (9).
(11) The method for forming a conductive film according to any one of (1) to (10), wherein the composition for forming a conductive film further contains water.
(12) The method for producing a conductive film according to any one of (1) to (11), wherein the substrate is a resin substrate.
(13) The method for producing a conductive film according to any one of (1) to (12), wherein the base material has an insulating film layer having a thickness of 0.1 μm or more and 1.5 μm or less on the surface thereof.
(14) The conductive film according to any one of (1) to (13), wherein in the sintering step, the light irradiation is performed twice or more using pulsed light with a pulse width of 2 milliseconds or less. Production method.
(15) A composition for forming a conductive film used in the method for manufacturing a conductive film according to any one of (1) to (14),
Cupric oxide particles having an average primary particle size of 50 nm or less;
At least one selected from the group consisting of polyethylene glycol, glycerin and trimethylolpropane;
An organic solvent (C) having a boiling point of less than 100 ° C.,
Including water,
Content of the said copper oxide particle (A) is 50 mass% or more and 95 mass% or less in the total amount of the said copper oxide particle (A) and the said compound (B),
The composition for electrically conductive film formation whose content of the said organic solvent (C) is 10 mass% or more in the whole quantity of the said composition for electrically conductive film formation.
(16) The polyethylene glycol and the glycerin and / or the trimethylolpropane, wherein the content of the polyethylene glycol is 4% by mass or more and less than 50% by mass with respect to the total amount of the cupric oxide particles, The content of glycerin and / or the trimethylolpropane is 10% by mass or more and less than 30% by mass with respect to the total amount of the cupric oxide particles, and is further selected from the group consisting of Groups 8 to 11 of the periodic table A metal catalyst (E) containing at least one metal element, wherein the amount of the metal catalyst (E) is 0.1% by mass or more and less than 8% by mass with respect to the total amount of the cupric oxide particles. The composition for electrically conductive film formation as described in said (15).
(17) The composition for forming a conductive film according to the above (15) or (16), further comprising a surfactant (D).

According to the present invention, it is possible to provide a conductive film manufacturing method and a conductive film forming composition that can form a conductive film with excellent conductivity, few defects, and excellent transferability.

FIG. 1 is a schematic view showing a step of forming a conductive film by a reverse printing method.

The present invention will be described in detail below.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
One of the features of the present invention is that the amount of each component in the composition, in particular, the oxidation with respect to the total mass of the copper oxide particles (A) and the compound (B) can be suitably used in the reverse printing method. The point which has controlled the mass ratio in the electroconductive composition of the organic solvent (C) and the mass ratio of a copper particle (A) is mentioned. As will be described later, in the reverse printing method, a composition for forming a conductive film is once applied on a temporary support, a coating film is formed, a part of the coating film is removed, and then a predetermined substrate is applied. Transcription. Normally, when a part of the coating film is removed, a plate having a convex portion (also referred to as a punched plate) is pressed against the coating film to transfer the coating film to the surface of the convex portion. When a coating film is prepared by applying the composition for forming a conductive film of the present invention on a temporary support, the organic solvent (C) having a low boiling point described later volatilizes and other components remain in the coating film. In particular, the hardness in the coating film is greatly influenced by the mass ratio of the copper oxide particles (A) to the total mass of the copper oxide particles (A) and the compound (B). Therefore, the present invention has found that by controlling the mass ratio within a predetermined range, the transfer from the coating film to the convex portion and the transfer from the temporary support to the substrate proceed well. ing. Furthermore, if it is the range of the said mass ratio, it has discovered that it is excellent also in the electroconductivity and ablation resistance of the electrically conductive film obtained.

First, the manufacturing method of the electrically conductive film of this invention is demonstrated.
The conductive film manufacturing method of the present invention (the manufacturing method of the present invention) includes a coating film forming step of forming a coating film by applying a conductive film forming composition described later on a temporary support, and a coating film At least a removal step of removing the portion and a transfer step of transferring the remaining coating film on the temporary support onto the substrate to form a precursor film of the conductive film.
In the manufacturing method of the present invention, a conductive film precursor film (a pattern of a conductive film forming composition) is formed on a substrate by reverse printing, and this is irradiated with light and sintered to form a conductive film. Thus, a conductive film having excellent conductivity and few defects can be formed, and the conductive film-forming composition of the present invention is excellent in transferability (printing and / or transfer to a substrate). Moreover, the electrically conductive film manufactured by the manufacturing method of this invention can also make a surface smooth with a thin film.
Below, after explaining in detail about the aspect of the composition for electrically conductive film formation used at a coating-film formation process first, the procedure of each process is explained in full detail.

[Composition for forming conductive film (composition)]
In the production method of the present invention, at least one compound selected from the group consisting of copper oxide particles (A), an organic compound having a boiling point of 250 ° C. or higher and having at least one hydroxy group per molecule and polyalkylene glycol A conductive film forming composition (composition) containing (B) and an organic solvent (C) having a boiling point of less than 100 ° C. is used.

<Copper oxide particles (A)>
In the present invention, the copper oxide particles (A) contained in the composition are not particularly limited as long as they are particulate copper oxide.
The particulate form refers to a small granular form, and specific examples thereof include a spherical shape and an ellipsoidal shape. It does not have to be a perfect sphere or ellipsoid, and some may be distorted.

The copper oxide particles (A) are preferably copper oxide (I) particles (Cu ₂ O particles) or copper oxide (II) particles (CuO particles), and are excellent in conductivity and available at low cost. From the viewpoint of excellent stability in air and excellent reduction reactivity, copper (II) oxide particles are more preferable.

The average primary particle diameter of the copper oxide particles (A) is preferably 100 nm or less, and preferably 10 to 50 nm. The lower limit of the average primary particle size is not particularly limited, but is preferably 1 nm or more, and more preferably 10 nm or more. When the average primary particle diameter of the copper oxide particles exceeds 100 nm, the dispersion stability decreases, and the smoothness and conductivity of the obtained conductive film become insufficient.
The copper oxide particles (A) are preferably cupric oxide particles having an average primary particle diameter of 100 nm or less, and more preferably cupric oxide particles having an average primary particle diameter of 50 nm or less.
The average primary particle size is a particle size (equivalent to a circle) of 1000 primary particles arbitrarily selected from an image taken using a transmission electron microscope TEM2010 (pressurized voltage 200 kV) manufactured by JEOL Ltd. (Diameter) are measured, and they are obtained by arithmetic averaging. The equivalent circle diameter is the diameter of the circle when assuming a true circle having the same projected area as the projected area of the particles at the time of observation.

In the present invention, a part of the copper oxide particles (A) may be aggregated. When the copper oxide particles (A) are aggregated, the copper oxide particles (A) are excellent in that the resulting conductive film has excellent smoothness and conductivity. ) Is preferably 70 to 150 nm, more preferably 80 to 130 nm.
Further, when a part of the copper oxide particles (A) is aggregated, the degree of association of the copper oxide particles (A) (the volume average secondary particle diameter / the average primary particle diameter) is not particularly limited, but is obtained. In terms of the smoothness and conductivity of the conductive film, it is preferably more than 1.0 and 5.0 or less, and more preferably 1.5 to 3.0.

In the present invention, the content of the copper oxide particles (A) is 50 to 95% by mass of the total amount of the copper oxide particles (A) and the compound (B), and the effect of the present invention is more excellent. It is preferably from 90% by mass. In addition, when a part of copper oxide particle (A) has aggregated, the quantity of a copper oxide particle (A) shall be the quantity containing the said aggregate.

<Compound (B)>
In the present invention, the compound (B) contained in the composition has a boiling point of 250 ° C. or higher and at least one selected from the group consisting of an organic compound having at least one hydroxy group per molecule and a polyalkylene glycol. If it is, it will not be restrict | limited in particular.
When the composition contains the compound (B), the transferability is excellent, and the reduction from copper oxide to metallic copper proceeds more efficiently. As a result, a conductive film having excellent conductivity is obtained, and defects in the conductive film are obtained. Can be reduced.
The upper limit of the boiling point of the organic compound having at least one hydroxy group per molecule is not particularly limited, but is preferably 400 ° C. or lower because it is difficult to remain in the conductive film.
The polyalkylene glycol is preferably a substance that decomposes and volatilizes at 450 ° C. or lower when heated in an inert atmosphere in a state of being mixed with the copper oxide particles (A).
In the present specification, “boiling point” means a boiling point under a pressure of 1 atm.

The organic compound having a boiling point of 250 ° C. or more and having at least one hydroxy group per molecule is superior in at least one of transferability, conductivity of the conductive film, and defect generation suppressing property of the conductive film (hereinafter, It is preferable to have 2 or 3 hydroxy groups per molecule simply as “the point where the effect of the present invention is more excellent”.

As an organic compound, alcohol is mentioned, for example.
Specific examples of the alcohol include monohydric alcohols such as 1-eicosanol (boiling point 372 ° C.) and 1-tetracosanol (boiling point 395 ° C.); 1,6-hexanediol (boiling point 250 ° C.), 1,7 Divalent alcohols such as heptanediol (boiling point 259 ° C.), triethylene glycol (boiling point 287 ° C.), tripropylene glycol (boiling point 273 ° C.); glycerin (propane-1,2,3-triol) (boiling point 290 ° C.) Trivalent alcohols such as trimethylolpropane (boiling point 292 ° C.); tetravalent alcohols such as erythritol (boiling point 329 ° C.); pentavalent alcohols such as pentaerythritol (boiling point 250 ° C. or higher); mannitol (boiling point 290 ° C.) And hexavalent alcohols.
Especially, it is preferable that at least 1 sort (s) chosen from the group which consists of glycerol and a trimethylol propane is included at the point which the effect of this invention is more excellent.

The polyalkylene glycol is not particularly limited as long as it is a compound having an oxyalkylene repeating unit and having two hydroxy groups in one molecule. The alkylene group is not particularly limited. Examples thereof include alkylene groups having 1 to 10 carbon atoms such as ethylene group and propylene group.
Examples of the polyalkylene glycol include polyethylene glycol and polypropylene glycol, and polyethylene glycol is preferably used.
The weight average molecular weight of the polyalkylene glycol is not particularly limited, but is preferably 1,000 or more, more preferably 3,000 to 500,000, and more preferably 4,000, in terms of more excellent effects of the present invention. More preferred is ˜20,000. The weight average molecular weight is a polystyrene equivalent value obtained by the GPC method (solvent: N-methylpyrrolidone).

The compound (B) is mentioned as one of preferable embodiments containing at least one selected from the group consisting of polyethylene glycol, glycerin and trimethylolpropane.
A compound (B) can be used individually or in combination of 2 types or more, respectively.
Examples of the combination of the compound (B) include the combined use of polyethylene glycol and a dihydric or higher alcohol in that the effect of the present invention is more excellent. Among these, it is preferable to contain polyethylene glycol and glycerin and / or trimethylolpropane. One of the preferred embodiments is that polyethylene glycol and trimethylolpropane are used in combination because of superior transferability.

In the present invention, the content of the compound (B) is preferably 6% by mass or more and 100% by mass or less with respect to the total amount of the copper oxide particles (A), and can be less than 100% by mass, and 8% by mass. % To 60% by mass is more preferable. When the content of the compound (B) is 6% by mass or more, transferability and conductivity can be further improved. Moreover, the defect of a electrically conductive film can be decreased more because content of a compound (B) is 100 mass% or less.
When the compound (B) contains at least one selected from the group consisting of polyethylene glycol, glycerin and trimethylolpropane, the lower limit of the content of at least one selected from the group consisting of polyethylene glycol, glycerin and trimethylolpropane is The total amount of the copper oxide particles (A) is preferably 6% by mass or more, and more preferably 8% by mass or more. The upper limit of the content of at least one selected from the group consisting of polyethylene glycol, glycerin and trimethylolpropane can be 100% by mass or less or less than 100% by mass with respect to the total amount of the copper oxide particles (A). 60 mass% or less is preferable.

In the present invention, the content of polyalkylene glycol (for example, polyethylene glycol) is preferably 0 to 50% by mass with respect to the total amount of the copper oxide particles (A), and is 4% by mass or more and less than 50% by mass. Is more preferable, and it is still more preferable that it is 4 mass% or more and 30 mass%.
The total amount of glycerin and / or trimethylolpropane (when both are combined, the total amount, the same shall apply hereinafter) is 0% by mass or more and less than 100% by mass with respect to the total amount of the copper oxide particles (A). The content is preferably 0 to 50% by mass, more preferably 10% by mass or more and less than 30% by mass, and particularly preferably 10 to 20% by mass.

When the compound (B) includes polyethylene glycol and glycerin and / or trimethylolpropane, the content of polyethylene glycol is preferably less than 50% by mass with respect to the total amount of the copper oxide particles (A). The content is more preferably 1 to 30% by mass, and further preferably 4 to 30% by mass. In this case, the total amount of glycerin and / or trimethylolpropane is preferably less than 100% by mass with respect to the total amount of the copper oxide particles (A), and is from 1% by mass to less than 50% by mass. Is more preferably 1% by mass or more and less than 30% by mass, particularly preferably 5 to 20% by mass, and most preferably 10 to 15% by mass. In this case, the total amount of polyethylene glycol and glycerin and / or trimethylolpropane is preferably 8% by mass or more based on the total amount of the copper oxide particles (A).

<Organic solvent (C)>
In the present invention, the organic solvent (C) contained in the composition is an organic solvent having a boiling point of less than 100 ° C. The boiling point is preferably 90 ° C. or lower and more preferably 85 ° C. or lower in that the effect of the present invention is more excellent. In addition, although a minimum in particular is not restrict | limited, From the point which is excellent by handleability, 50 degreeC or more is preferable and 55 degreeC or more is more preferable.

The type of the organic solvent (C) is not particularly limited as long as it satisfies the above boiling point requirements. For example, alcohol solvents such as methanol and ethanol, ketone solvents such as acetone and methyl ethyl ketone, amide solvents, acetonitrile and the like. Nitrile solvents, ester solvents such as methyl acetate, carbonate solvents such as dimethyl carbonate, and other solvents such as ether solvents, glycol solvents, amine solvents, thiol solvents, and halogen solvents.
Of these, ketone-based solvents and alcohol-based solvents are preferable because they are excellent in transferability (particularly transferability to a printing plate) and further improve the solubility of the metal catalyst (E) described later in the composition.
As an organic solvent (C), only 1 type may be used and 2 or more types may be used together.

In the present invention, the content of the organic solvent (C) is 10% by mass or more in the total amount of the composition for forming a conductive film. By this, the applicability | paintability of the composition of this invention can be made excellent. From the viewpoint of superior coating properties, the content of the organic solvent (C) is preferably 10% by mass or more and 60% by mass or less, and preferably 10% by mass or more and 50% by mass or less in the total amount of the composition for forming a conductive film. The following is more preferable.

<Surfactant (D)>
In the present invention, the composition can further improve the wettability to the temporary support by containing a surfactant.
In the present invention, the type of surfactant (D) contained in the composition is not particularly limited. For example, an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, etc. are mentioned.
Specific examples of the anionic surfactant include fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, alkyl phosphates, polyoxyethylenes. Alkyl sulfate ester salt, polyoxyethylene alkyl allyl sulfate ester salt, naphthalene sulfonic acid formalin condensate, polycarboxylic acid type polymer surfactant, polyoxyethylene alkyl phosphate ester and the like can be mentioned.

Specific examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene acetylenic glycol ether, polyoxyethylene derivatives (excluding polyethylene glycol), oxyethylene oxy Examples include propylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, and alkylalkanolamides.
More specifically, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauryl ether and the like can be mentioned.

Specific examples of the cationic surfactant and the amphoteric surfactant include alkylamine salts, quaternary ammonium salts, alkylbetaines, amine oxides and the like.

Besides these, fluorine-based surfactants and silicon-based surfactants can also be used. Among the above surfactants, nonionic surfactants are preferable in that the conductivity of the conductive film to be formed is more excellent.

The surfactant (D) can be used alone or in combination of two or more.
The content of the surfactant (D) is not particularly limited, but is preferably 0.05 to 1.5% by mass, more preferably 0.05 to 1% by mass in the total amount of the composition, and 0.05 to 0.5% by mass is most preferred.

In the present invention, the total amount of the copper oxide particles (A) and the compound (B) is that the effects of the present invention are more excellent, and the copper oxide particles (A), the compound (B) and the surfactant (D). The total amount is preferably 90 to 99.99% by mass, and more preferably 95 to 99.99% by mass.

<Metal catalyst (E)>
In the present invention, it is preferable that the composition for forming a conductive film further includes a metal catalyst (E) containing at least one metal element selected from the group consisting of Groups 8 to 11 of the periodic table.
A metal catalyst (E) can contribute to the electroconductivity improvement of a electrically conductive film while improving the reducibility of the copper oxide particle (A) mentioned above.
The metal catalyst (E) contains at least one metal element (metal) selected from the group consisting of groups 8 to 11 of the periodic table. The metal element is at least one metal element selected from the group consisting of gold, silver, copper, platinum, palladium, rhodium, iridium, ruthenium, osmium, and nickel in that the conductivity of the conductive film is more excellent. Preferably, it is at least one metal element selected from the group consisting of silver, platinum, palladium, and nickel, more preferably palladium or platinum, and most preferably palladium. That is, the metal catalyst (E) is preferably a metal catalyst containing palladium because the conductivity of the obtained conductive film is more excellent.

As a suitable aspect of a metal catalyst (E), palladium salt and a palladium complex are mentioned, for example.
The kind of the palladium salt is not particularly limited, and specific examples thereof include palladium hydrochloride, nitrate, sulfate, carboxylate, sulfonate, phosphate, and phosphonate. Of these, carboxylate is preferable.
The number of carbon atoms of the carboxylic acid forming the carboxylate is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5. The carboxylic acid forming the carboxylate may have a halogen atom (preferably a fluorine atom).

The kind of the palladium complex is not particularly limited, and examples of the ligand include 2,2′-bipyridyl, 1,10-phenanthroline, methylenebisoxazoline, N, N, N′N′-tetramethylethylenediamine, Examples include triphenylphosphine, tolylphosphine, tributylphosphine, triphenoxyphosphine, 1,2-bisdiphenylphosphinoethane, 1,3-bisdiphenylphosphinopropane, and the like.
Of these, triphenylphosphine is preferable.
The kind of palladium complex having triphenylphosphine as a ligand is not particularly limited, and specific examples thereof include tetrakis (triphenylphosphine) palladium and dichlorobis (triphenylphosphine) palladium. Of these, tetrakis (triphenylphosphine) palladium is preferable.

The palladium salt or palladium complex is preferably at least one compound selected from the group consisting of palladium acetate, palladium trifluoroacetate and tetrakis (triphenylphosphine) palladium, more preferably palladium acetate.

Although the content of the metal catalyst (E) in the composition is not particularly limited, the content of the metal catalyst (E) is based on the total amount of the copper oxide particles (A) in that the conductivity of the conductive film is more excellent. 0.1 to 10 mass% is preferable, 0.1 to 8 mass% is preferable, and 0.5 to 8 mass% is more preferable.

In the present invention, the composition may further contain a polymer compound (excluding polyalkylene glycol) from the viewpoint of superior transferability. Examples of the polymer compound include polyvinyl pyrrolidone and polyvinyl alcohol. However, since the conductivity deteriorates when the amount of the polymer compound added is large, the content of the polymer compound is preferably 0 to 10% by mass or less based on the copper oxide particles (A), and 0 to 8%. The mass% or less is more preferable. The weight average molecular weight is preferably 3,000 to 500,000, and more preferably 3,000 to 100,000.
By using these polymer compounds, transferability can be improved.

In the present invention, from the viewpoint that the composition is more excellent in transferability, the composition further includes water as one of preferred embodiments.
The water content is not particularly limited, but is preferably 1 to 80% by mass in the total amount of the conductive film-forming composition in terms of excellent transferability and excellent storage stability of the conductive film-forming composition. 60% by mass is more preferable, and 10 to 50% by mass is further preferable.

The composition may contain other components other than the above components. For example, an organic compound having a boiling point of less than 250 ° C. (excluding the above organic solvent), an organic compound having a functional group other than a hydroxy group, and a release agent may be mentioned.
The organic compound having a boiling point of less than 250 ° C. (excluding the organic solvent) is not particularly limited as long as it is an organic compound having a boiling point of 100 ° C. or more and less than 250 ° C. Examples thereof include 1-butanol and 1,2-hexanediol.

The method for preparing the composition is not particularly limited, and a known method can be adopted. For example, the components are mixed and then prepared by dispersing the components by a known means such as an ultrasonic method (for example, treatment with an ultrasonic homogenizer), a mixer method, a three-roll method, a ball mill method, or a bead mill method. be able to.

[Each step of the manufacturing method]
Hereinafter, each process in the manufacturing method of this invention is demonstrated with reference to drawings. In addition, the method of manufacturing a precursor film | membrane on a base material explained in full detail below corresponds to what is called a reverse printing method.

(Coating film formation process)
First, in a coating film formation process, the composition for electrically conductive film formation is provided on a temporary support body, and a coating film is formed on a temporary support body. More specifically, as shown to Fig.1 (a), the composition for electrically conductive film formation is provided to the temporary support body 10, and the temporary support body 1 which has the coating film 12 is formed. In addition, when forming a coating film, it is preferable to process so that most organic solvents mentioned above may volatilize.
As a temporary support used in the reversal printing method, for example, a blanket is mentioned as one of the preferred embodiments. Specifically, a silicone blanket is mentioned. The temporary support may have a liquid repellent surface. The material for forming the liquid repellent surface is not particularly limited. For example, a conventionally well-known thing is mentioned.

In the present invention, the method for applying the composition to the temporary support is not particularly limited. For example, a coating film having a predetermined film thickness can be formed by slit coating, bar coating, or spin coating.
The thickness of the applied coating film is preferably adjusted to 0.1 to 15 μm, more preferably 0.15 to 10 μm, from the viewpoint of conductivity obtained by subsequent fine pattern formation and drying properties.
In addition, you may provide the drying process which dries a coating film between a coating-film formation process and the removal process mentioned later so that it may mention later.

(Removal process)
A removal process is a process of removing a part of coating film obtained at the said coating-film formation process. A part of the coating film is removed to form a predetermined pattern, and this pattern is transferred to the substrate in a transfer step described later. This pattern becomes a precursor film of a conductive film described later.
In addition, the procedure in particular of a removal process is not restrict | limited, A well-known method is employable. Especially, the aspect which uses the board (cutting plate which has a convex part) which has a convex part from the point which productivity is more excellent is preferable. That is, as shown in FIG. 1B, the punching plate 14 having a convex portion and the temporary support 1 are made to face each other, and the convex coating 16 of the punching plate 14 having a convex portion is included in the temporary support 1. (Not shown). Next, as shown in FIG. 1 (c), the punching plate 14 having the convex portion is separated from the temporary support 1, and the portion 18 in contact with the convex portion 16 is removed from the temporary support 1 having the coating film 12. An embodiment in which the temporary support 3 having the pattern 20 is formed on the temporary support 10 is exemplified.

The material of the punching plate is not particularly limited as long as a part of the coating film can be removed from the temporary support, and for example, various metals such as glass, silicon, stainless steel, and various resins can be used.
Further, the processing method of the surface of the punched plate is not particularly limited, and an optimum method can be selected according to the material, pattern accuracy, relief plate depth, and the like. For example, when glass or silicon is used as a material, a processing method such as wet etching or dry etching can be applied. In the case of metal, wet etching, electroforming, sandblasting, etc. can be applied. Further, when a resin is used as a material, a processing method such as photolithography etching, laser, or focused ion beam can be suitably applied.

In addition, in FIG. 1, although the method of contacting the temporary support body which has the printing plate which is a relief printing plate which has a negative pattern with a parallel lithographic system, and a coating film was shown, especially the method of forming a pattern in a temporary support body has a restriction | limiting. No, for example, a method of rolling and contacting a temporary support having a coating film wound around a roll on a flat plate, a rolling plate on a temporary support having a flat coating film by forming a cutting plate on the roll side A method, a method of forming a temporary support having a coating film and a punching plate on a roll and bringing them into contact with each other can be applied.

(Transfer process)
The transfer step is a step of transferring the coating film (pattern) remaining on the temporary support obtained in the removing step onto the base material to form a precursor film of the conductive film on the base material. More specifically, first, the temporary support 3 and the base material 22 are opposed to each other as shown in FIG. 1 (d), and then the temporary support 3 and the base material 22 are set as shown in FIG. 1 (e). As shown in FIG. 1 (f), the pattern 20 on the temporary support 3 is transferred to the base material 22 to make the base material 5 having the pattern 20. That is, the coating film (pattern) remaining on the temporary support corresponds to the precursor film after transfer.
The procedure of the transfer process is not particularly limited, but usually, the coating film on the temporary support after the removal process is opposed to the substrate, and both are lightly pressed, and the coating film remaining on the temporary support is the substrate. It is preferable to transfer all the images to

The type of the substrate used in the reverse printing method is not particularly limited, and examples thereof include a metal substrate and a resin substrate, and a resin substrate is preferable from the viewpoint of handleability. Examples of the resin base material include low-density polyethylene resin, high-density polyethylene resin, polyolefin resin such as polypropylene and polybutylene; methacrylic resin such as polymethyl methacrylate; polystyrene, ABS (acrylonitrile-butadiene-styrene copolymer), Polystyrene resin such as AS (acrylonitrile-styrene copolymer); acrylic resin; styrene resin; vinyl chloride resin; polyester resin (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, poly 1,4-cyclohexyldimethylene terephthalate, etc.) Polyamide resin selected from nylon resin and nylon copolymer; polyvinyl chloride resin; polyoxymethylene; polycarbonate resin; Modified polyphenylene ether resin; polyacetal resin, polysulfone resin, polyether sulfone resin; polyketone resin; polyether nitrile resin; polyether ether ketone resin; polyetherimide resin, polyether ketone resin, polyether ketone ketone resin; Resins, polyamideimide resins; fluororesins; cellulose derivatives and the like are preferably used.

The base material may have an insulating film layer on its surface. Examples of the material for the insulating film layer include polyvinylphenol, polyimide, and a crosslinked product of polyvinylphenol and melamine resin.
The thickness of the insulating film layer is preferably 0.1 μm or more and 1.5 μm or less.

(Drying process)
Moreover, the manufacturing method of this invention can further be equipped with the drying process which dries the temporary support body after a coating-film formation process between a coating-film formation process and a removal process. By providing the drying step, transferability can be further improved.
The temperature in the drying step is preferably less than 110 ° C. By being within this temperature range, the organic solvent can be removed from the composition.

(Sintering process)
Next, in the sintering step, the precursor film is irradiated with light, and the conductive film is formed by reducing and fusing the copper oxide particles (A) in the precursor film.
By irradiating with light (hereinafter also referred to as light irradiation treatment), the copper oxide in the copper oxide particles (A) is reduced and further fused to obtain metallic copper. More specifically, copper oxide is reduced to form metallic copper particles, the produced metallic copper particles are fused together to form grains, and the grains are bonded and fused together to contain copper. Forming a conductive thin film.
Light irradiation treatment enables reduction and sintering to metallic copper by irradiating light at a room temperature for a short time to the part to which the coating film is applied, and does not cause deterioration of the substrate due to prolonged heating. The adhesion of the conductive film to the base material becomes better.

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. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Also, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are used.
Specific examples of preferred embodiments include scanning exposure with an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure.

The light irradiation is preferably light irradiation with a flash lamp, and more preferably pulsed light irradiation (eg, pulsed light irradiation with a Xe flash lamp). Irradiation with high-energy pulsed light can concentrate and heat the surface of the portion to which the coating film has been applied in a very short time, so that the influence of heat on the substrate can be extremely reduced.
The irradiation energy of the pulse light is preferably 0.5 ~ 100J / cm ^2, more preferably 1 ~ 30J / cm ^2, more preferably 1 ~ 10J / cm ^2. In the present invention, the irradiation energy when light irradiation is performed a plurality of times is the sum of the irradiation energy of each light irradiation.
The pulse width is preferably 1 microsecond to 100 milliseconds, more preferably 10 microseconds to 10 milliseconds, and further preferably 0.1 milliseconds to 2 milliseconds.

The light irradiation treatment may be performed once or more using a flash lamp, but it is preferable to perform the light irradiation treatment twice or more with a pulse width of 2 milliseconds or less.
The number of times of light irradiation is preferably 2 to 10 times, and more preferably 2 to 4 times.

The atmosphere for performing the light irradiation treatment is not particularly limited, and examples thereof include an air atmosphere, an inert atmosphere, and a reducing atmosphere. The inert atmosphere is, for example, an atmosphere filled with an inert gas such as argon, helium, neon, or nitrogen, and the reducing atmosphere is a reducing gas such as hydrogen or carbon monoxide. Refers to the atmosphere.

[Conductive film]
By carrying out the above steps, a conductive film (metal copper film) containing metal copper is obtained.
The film thickness of the conductive film is not particularly limited, and an optimum film thickness is appropriately adjusted according to the intended use. Among these, from the viewpoint of thin film transistor use, 0.8 μm or less is preferable, and 0.05 to 0.3 μm is more preferable.
The film thickness is a value (average value) obtained by measuring three or more thicknesses at arbitrary points on the conductive film and arithmetically averaging the values.
The volume resistivity of the conductive film is preferably less than 100 μΩ · cm, and more preferably less than 40 μΩ · cm from the viewpoint of conductive characteristics.
The volume resistivity can be calculated by multiplying the obtained surface resistivity by the film thickness after measuring the surface resistivity of the conductive film by the four-probe method.

In the present invention, the conductive film can be provided in a pattern on the substrate. The patterned conductive film is useful as a conductor wiring (wiring) such as a printed wiring board.

When a patterned conductive film is configured as a multilayer wiring board, an insulating layer (insulating resin layer, interlayer insulating film, solder resist) is further laminated on the surface of the patterned conductive film, and further wiring (metal) is formed on the surface. Pattern) may be formed.

The material of the insulating layer is not particularly limited. For example, epoxy resin, glass epoxy resin, aramid resin, crystalline polyolefin resin, amorphous polyolefin resin, fluorine-containing resin (polytetrafluoroethylene, perfluorinated polyimide, perfluorinated) Amorphous resin), polyimide resin, polyether sulfone resin, polyphenylene sulfide resin, polyether ether ketone resin, liquid crystal resin, polyvinyl phenol, a crosslinked product of polyvinyl phenol and melamine resin, and the like.
Among these, from the viewpoint of adhesion, an epoxy resin, a polyimide resin, or a crosslinked product of polyvinylphenol and a melamine resin is preferable. Specific examples include ABF GX-13 manufactured by Ajinomoto Fine Techno Co., Ltd.

The base material (base material with a conductive film) having the conductive film obtained above can be used for various applications. For example, a printed wiring board, TFT, FPC, RFID, etc. are mentioned.

One preferred embodiment of the composition for forming a conductive film of the present invention is a composition for forming a conductive film used in the method for producing a conductive film of the present invention,
Cupric oxide particles having an average primary particle size of 50 nm or less;
At least one selected from the group consisting of polyethylene glycol, glycerin and trimethylolpropane;
An organic solvent (C) having a boiling point of less than 100 ° C.,
Including water,
The content of the copper oxide particles (A) is 50% by mass or more and 95% by mass or less in the total amount of the copper oxide particles (A) and the compound (B),
The composition for electrically conductive film formation whose content of an organic solvent (C) is 10% or more in the whole quantity of the composition for electrically conductive film formation is mentioned. If it is this composition, it can be conveniently used by the reverse printing method mentioned above.

In the composition of the present invention, the aspect of the cupric oxide particles having an average primary particle diameter of 50 nm or less is as described above. The same applies to polyethylene glycol, glycerin, trimethylolpropane, organic solvent (C) having a boiling point of less than 100 ° C., and water.

The content of at least one selected from the group consisting of polyethylene glycol, glycerin and trimethylolpropane is preferably 6% by mass or more and 100% by mass or less based on the total amount of the copper oxide particles (A).
The composition of the present invention contains polyethylene glycol, and the content of polyethylene glycol is preferably less than 50% by mass with respect to the total amount of cupric oxide particles, and is preferably 4% by mass or more and less than 50% by mass. More preferred.
The composition of the present invention contains glycerin and / or trimethylolpropane, and the content of glycerin and / or trimethylolpropane is preferably 100% by mass or less based on the total amount of cupric oxide particles, and is 100% by mass. More preferably, it is more preferably 1% by mass or more and less than 50% by mass, and particularly preferably 10% by mass or more and less than 30% by mass.
The composition of the present invention contains polyethylene glycol and glycerin and / or trimethylolpropane, and the content of polyethylene glycol is less than 50% by mass with respect to the total amount of cupric oxide particles, and glycerin and / or trimethylolpropane. The content of is preferably less than 50% by mass with respect to the total amount of cupric oxide particles.
Moreover, it contains polyethylene glycol and glycerin and / or trimethylolpropane, and the content of polyethylene glycol is 4% by mass or more and less than 50% by mass with respect to the total amount of cupric oxide particles, and glycerin and / or trimethylolpropane. The content of is 10% by mass or more and less than 30% by mass with respect to the total amount of cupric oxide particles, and further contains at least one metal element selected from the group consisting of Groups 8 to 11 of the periodic table One preferred embodiment includes the metal catalyst (E) and the amount of the metal catalyst (E) is 0.1% by mass or more and less than 8% by mass with respect to the total amount of the cupric oxide particles.

The conductive film-forming composition of the present invention can further contain a surfactant (D) and a polymer compound (excluding polyalkylene glycol). The surfactant (D) and the polymer compound are the same as described above.

Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

<Preparation of copper oxide dispersion a>
45 parts by mass of cupric oxide particles (Cai Kasei Co., Ltd., NanoTek CuO, average primary particle size (48 nm)) and 55 parts by mass of ion-exchanged water were mixed, and a ready mill disperser (bead mill manufactured by IMEX Co., Ltd.) was mixed. Using a disperser), dispersion was performed with zirconia beads having a bead diameter of 0.05 mmφ until the average particle diameter became 130 nm or less to obtain a copper oxide dispersion. Let the obtained copper oxide dispersion be the copper oxide dispersion a. The average particle size was measured using a Zetasizer Nano manufactured by Malvern. The liquid for measurement was prepared by diluting with ion-exchanged water so that the concentration of the copper oxide dispersion was 0.1% by mass. In addition, this average particle diameter means not a primary particle diameter but a secondary particle diameter. Moreover, this average particle diameter is a volume average particle diameter. Specifically, Nanotrac particle size distribution analyzer UPA-EX150 (manufactured by Nikkiso Co., Ltd.) was used for the measurement. The copper oxide dispersion a contains aggregates.

<Manufacture of the composition for electrically conductive film formation>
The components shown in Tables 1 and 2 below were mixed in the blending amounts (mass%) shown in the same table, and the mixture was stirred for 10 minutes with a stirrer to prepare a conductive film forming composition. In addition, the quantity of the copper oxide particle (A) in a table | surface is the quantity of solid content (an aggregate is included) contained in the copper oxide dispersion a, and is the quantity of copper oxide particle itself.

<Manufacture of conductive film for transferability evaluation>
-Coating-film formation process Bar coating is applied on a temporary support (silicone blanket) so that the thickness of the conductive film after sintering the conductive film-forming composition produced as described above becomes the thickness described in Tables 1 and 2. A temporary support having a coating film was formed.

-Drying process The temporary support body formed as mentioned above was dried at 23 degreeC for 60 second.

Removal step Using a glass plate having projections (L / S = 20 μm / 20 μm fine-line projections), the projections on the temporary support obtained as described above were coated on the temporary support. Pressed against. Next, the glass plate was separated from the temporary support, unnecessary portions of the coating film were removed from the temporary support, and fine lines (patterns) of L / S = 20 μm / 20 μm were formed on the temporary support.

-Transfer process Next, the substrate to be transferred was lightly pressed against the temporary support on which the fine lines were formed as described above, and the pattern on the temporary support was transferred to the substrate.
The base material used for the compositions in Table 1 is polyimide (Kapton 500H, manufactured by Toray DuPont, the same applies hereinafter).
The base material used for the composition of Table 2 is a base material in which an insulating film layer, which is a crosslinked product of polyvinylphenol, is formed on a polyimide (Kapton 500H) with a thickness of 500 nm.
The insulating film layer, which is a cross-linked product of the polyvinylphenol, was produced as follows. First, 9.1 g of poly (4-vinylphenol) (manufactured by Nippon Soda, trade name VP-8000), melamine crosslinking agent (trade name: Nikalac MW-100LM, 3.9 g) by 1-butanol and ethanol Were mixed and dissolved to obtain a mixed solution. Next, after UV irradiation of the base material, the mixed liquid obtained as described above was applied to the base material by spin coating, and heat treatment was performed at 180 ° C. for 1 hour to insulate the base material as a crosslinked product of polyvinylphenol. A film layer was prepared.

-Sintering process After the base material obtained as described above was dried at 23 ° C for 60 minutes, this was subjected to pulsed light irradiation treatment using a Xenon light sintering apparatus Sinteron 2000 to produce a conductive film. And observed. In the above pulsed light irradiation process, when the pulse width and the number of irradiations shown in each table are used, the distance between the lamp and the sample and the capacitor charge so that the light irradiation energy becomes the amount of light irradiation energy described in each table. This was done by adjusting the voltage. When the number of times of irradiation is plural, the amount of light irradiation energy is the total amount of light irradiation energy.

<Manufacture of conductive film for conductivity evaluation>
The same composition for forming a conductive film as that used in the manufacture of the conductive film for evaluation of transferability was bar-coated on the temporary support so that the thickness of the conductive film after sintering was the thickness described in Tables 1 and 2. , Dried at 23 ° C. for 60 seconds, transferred to the substrate in the same manner as in the transfer step without passing through the removal step, and irradiated with pulsed light in the same manner as in the sintering step in the production of the conductive film for evaluation of transferability. The process was performed and the electrically conductive film was manufactured.

<Evaluation>
The following evaluation was performed using each electrically conductive film manufactured as mentioned above. The results are shown in each table.
(Conductivity evaluation)
About each electrically conductive film manufactured in preparation of the electrically conductive film for electroconductivity evaluation, the volume resistivity was measured using the four-probe method resistance meter. From the measured volume resistivity, conductivity was evaluated based on the following criteria. Practically, it is preferably A to D.
“A”: When the volume resistivity was less than 15 μΩ · cm, the conductivity evaluation result was indicated as A.
“B”: When the volume resistivity was 15 μΩ · cm or more and less than 40 μΩ · cm, the evaluation result of conductivity was indicated as B.
“C”: When the volume resistivity was 40 μΩ · cm or more and less than 100 μΩ · cm, the evaluation result of conductivity was indicated as C.
“D”: When the volume resistivity was 100 μΩ · cm or more and less than 500 μΩ · cm, the conductivity evaluation result was indicated as D.
“E”: When the volume resistivity was 500 μΩ · cm or more, the evaluation result of conductivity was indicated as E.

(Defects in conductive film)
The area of any 0.25 mm ² (0.5 mm length, 0.5 mm width) among the respective conductive films produced in the production of the conductive film for conductivity evaluation was observed at a magnification of 450 times using an optical microscope. . The size of the defect within the area of 0.25 mm ² was evaluated based on the following criteria. Practically, it is preferably A to B.
“A”: When there was no defect or a defect with a size of less than 5 μmφ but no defect with a size of 5 μmφ or more, the evaluation result of the defect of the conductive film was indicated as A.
“B”: When there was a defect with a size of 5 μmφ or more and less than 20 μmφ, but there was no defect with a size of 20 μmφ or more, the evaluation result of the defect of the conductive film was indicated as B.
“C”: When there was a defect of 20 μmφ or more, the evaluation result of the defect of the conductive film was indicated as C.

(Transferability)
An arbitrary area of 0.25 mm ² (0.5 mm length, 0.5 mm width) of the substrate on which fine lines were formed in the conductive film for transferability evaluation was observed at a magnification of 450 times using an optical microscope. The transferability within the 0.25 mm ² area was evaluated based on the following criteria. Practically, it is preferably A to C.
“A”: When the transfer rate of fine lines was almost 100%, the evaluation result of transferability was indicated as A.
“B”: When the transfer rate of fine lines was 90% or more, the transferability evaluation result was indicated as B.
“C”: When the transfer rate of the thin line was 70% or more and less than 90%, the evaluation result of transferability was indicated as C.
“D”: When the transfer rate of thin lines was less than 70%, or when the conductive film was not in the form of thin lines, the transferability evaluation result was indicated as D.

 

Details of the components shown in each table are as follows.
Cupric oxide (A): Copper oxide dispersion a prepared as described above
Polyethylene glycol (Mw: 1000), polyethylene glycol (Mw: 4000), polyethylene glycol (Mw: 20000): “polyethylene glycol 1000”, “polyethylene glycol 4000”, “polyethylene glycol 8000”, “polyethylene glycol 20000”. All are manufactured by Wako Pure Chemical Industries, Ltd. Mw in a table | surface shows a weight average molecular weight.
・ Glycerin: (boiling point: 290 ° C.)
・ Trimethylolpropane (boiling point: 292 ° C)
・ Ethanol (boiling point: 78 ° C)
Acetone (boiling point: 56 ° C)
Surfactant (D): Olfine E1010, manufactured by Nissin Chemical Industry Co., Ltd. 1,2-hexanediol: boiling point 223-224 ° C.
Palladium acetate: (CH ₃ COO) ₂ Pd
Polyvinylpyrrolidone (Mw. 58000): manufactured by Alfa Aesar.

As is clear from the results shown in the tables, when the method for producing a conductive film of the present invention and the composition for forming a conductive film of the present invention are used, the conductive film has excellent transferability, excellent conductivity, and few defects. It was confirmed that can be formed. Moreover, even if a defect arises, it was confirmed that the magnitude | size is small.

Especially, when Examples 1 and 4 are compared, when polyethylene glycol is used as the compound (B), it is excellent in transferability, excellent in conductivity, even if there are fewer defects or defects in the conductive film. It was confirmed that the size was small.
When Examples 1, 2, and 3 were compared, it was confirmed that when polyethylene glycol and trimethylolpropane or glycerin were used in combination as the compound (B), the conductivity and transferability were superior.
When Examples 1, 6, and 7 were compared, it was confirmed that the higher the weight average molecular weight of polyethylene glycol as the compound (B), the better the transferability.

When Examples 12, 13, and 14 were compared, it was confirmed that when the composition for forming a conductive film further contained a metal catalyst (E), it was more excellent in conductivity.

On the other hand, it was confirmed that Comparative Example 1 containing no compound (B) was inferior in transferability and conductivity. Comparative Examples 2 and 3 in which the content of the copper oxide particles (A) is not 50 mass% or more and 95 mass% or less in the total amount of the copper oxide particles (A) and the compound (B) are transferred as compared with Example 1. It was confirmed that the conductivity and conductivity were inferior and the conductive film had large defects.
It was confirmed that Comparative Example 4 which does not contain 10% by mass or more of the organic solvent (C) in the total amount of the conductive composition was inferior in transferability.
It was confirmed that the comparative example 5 which does not contain a compound (B) and the boiling point of an organic compound is 100 degreeC or more and less than 250 degreeC is inferior in electroconductivity.

DESCRIPTION OF SYMBOLS 1 Temporary support body which has coating film 3 Temporary support body which has pattern 5 Base material 10 Temporary support body 12 Composition for electrically conductive film formation, Coating film 14 Extraction plate 16 Convex part 18 Part 20 Pattern 22 Base material

Claims (17)

1. Copper oxide particles (A), at least one compound (B) selected from the group consisting of an organic compound having a boiling point of 250 ° C. or higher and having at least one hydroxy group per molecule and polyalkylene glycol, and a boiling point of 100 A coating film forming step of forming a coating film by applying a composition for forming a conductive film containing an organic solvent (C) of less than ° C. on a temporary support;
   A removal step of removing a part of the coating film;
   A transfer step of transferring the remaining coating film on the temporary support onto a substrate to form a precursor film of a conductive film;
   A process of forming a conductive film by irradiating the precursor film with light and reducing and fusing the copper oxide particles (A) in the precursor film,
   The content of the copper oxide particles (A) is 50% by mass or more and 95% by mass or less in the total amount of the copper oxide particles (A) and the compound (B),
   The manufacturing method of an electrically conductive film whose content of the said organic solvent (C) is 10 mass% or more in the whole quantity of the said composition for electrically conductive film formation.
2. The method for producing a conductive film according to claim 1, wherein the composition for forming a conductive film further contains a surfactant (D).
3. The method for producing a conductive film according to claim 1 or 2, wherein the copper oxide particles (A) are cupric oxide, and the average primary particle diameter of the copper oxide particles (A) is 100 nm or less.
4. The conductive film according to any one of claims 1 to 3, wherein the organic compound having a boiling point of 250 ° C or higher and having at least one hydroxy group per molecule has two or three hydroxy groups per molecule. Manufacturing method.
5. The production of the conductive film according to any one of claims 1 to 4, wherein the content of the compound (B) is 6% by mass or more and 100% by mass or less with respect to the total amount of the copper oxide particles (A). Method.
6. The method for producing a conductive film according to any one of claims 1 to 5, wherein the compound (B) contains at least one selected from the group consisting of polyethylene glycol, glycerin and trimethylolpropane.
7. The method for producing a conductive film according to any one of claims 1 to 6, wherein the compound (B) comprises polyethylene glycol and glycerin and / or trimethylolpropane.
8. The polyethylene glycol content is 4% by mass or more and less than 50% by mass with respect to the total amount of the copper oxide particles (A), and the total amount of the glycerin and / or the trimethylolpropane is the copper oxide particles (A). The manufacturing method of the electrically conductive film of Claim 7 which is 10 to less than 30 mass% with respect to the whole quantity.
9. The method for producing a conductive film according to any one of claims 6 to 8, wherein the polyethylene glycol has a weight average molecular weight of 3000 or more.
10. 10. The conductive film forming composition further comprises a metal catalyst (E) containing at least one metal element selected from the group consisting of groups 8 to 11 of the periodic table. The manufacturing method of the electrically conductive film of Claim 1.
11. The method for forming a conductive film according to any one of claims 1 to 10, wherein the composition for forming a conductive film further contains water.
12. The method for producing a conductive film according to any one of claims 1 to 11, wherein the substrate is a resin substrate.
13. 13. The method for producing a conductive film according to claim 1, wherein the substrate has an insulating film layer having a thickness of 0.1 μm or more and 1.5 μm or less on the surface thereof.
14. The method for manufacturing a conductive film according to any one of claims 1 to 13, wherein, in the sintering step, the light irradiation is performed twice or more using pulsed light with a pulse width of 2 milliseconds or less.
15. A composition for forming a conductive film used in the method for producing a conductive film according to any one of claims 1 to 14,
    Cupric oxide particles having an average primary particle size of 50 nm or less;
    At least one selected from the group consisting of polyethylene glycol, glycerin and trimethylolpropane;
    An organic solvent (C) having a boiling point of less than 100 ° C.,
    Including water,
    The content of the copper oxide particles (A) is 50% by mass or more and 95% by mass or less in the total amount of the copper oxide particles (A) and the compound (B),
    The composition for electrically conductive film formation whose content of the said organic solvent (C) is 10 mass% or more in the whole quantity of the said composition for electrically conductive film formation.
16. The polyethylene glycol and the glycerin and / or the trimethylolpropane, wherein the content of the polyethylene glycol is 4% by mass or more and less than 50% by mass with respect to the total amount of the cupric oxide particles. Or the content of the trimethylolpropane is 10% by mass or more and less than 30% by mass with respect to the total amount of the cupric oxide particles, and at least one selected from the group consisting of Groups 8 to 11 of the periodic table The metal catalyst (E) containing a seed metal element, wherein the amount of the metal catalyst (E) is 0.1% by mass or more and less than 8% by mass with respect to the total amount of the cupric oxide particles. The composition for electrically conductive film formation of description.
17. The composition for forming a conductive film according to claim 15 or 16, further comprising a surfactant (D).

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