JP2022171568A - Method for manufacturing metal wiring - Google Patents

Abstract

To provide a method for manufacturing metal wiring that, in a developing step, can reduce a change in resistance value of metal wiring before and after developing while sufficiently removing a coating film remaining between the pieces of metal wiring, and can thereby manufacture high-quality metal wiring.SOLUTION: A method for manufacturing metal wiring includes: an application step of applying, onto a surface of a substrate, a dispersing element including particle components being metal particles and/or metal oxide particles to form a dispersing element layer; a drying step of drying the dispersing element layer to form a structure with a dry film having the substrate and a dry film arranged on the substrate; a laser beam irradiation step of irradiating the dry film with a laser beam to form metal wiring; and a developing step of developing to remove an area other than the metal wiring of the dry film with a developing solution. The developing step includes (1) first developing processing of developing the dry film with a first developing solution, and (2) second developing processing of developing the dry film with a second developing solution. The first developing solution and the second developing solution each include water and/or an organic solvent.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for manufacturing metal wiring.

A circuit board has a structure in which conductive wiring is provided on a substrate. A method of manufacturing a circuit board is generally as follows. First, a photoresist is applied on a substrate to which a metal foil is attached. The photoresist is then exposed and developed to obtain the negative features of the desired circuit pattern. Next, the portion of the metal foil not covered with the photoresist is removed by chemical etching to form a pattern. Thereby, a high-performance conductive substrate can be manufactured.

However, the conventional method has drawbacks such as a large number of steps, being complicated, and requiring a photoresist material.

On the other hand, direct wiring printing in which a desired wiring pattern is directly printed on a substrate with a dispersion (hereinafter also referred to as "paste material") in which particles selected from the group consisting of metal particles and metal oxide particles are dispersed. The focus is on technology. This technique has a small number of steps, does not require the use of a photoresist material, and has extremely high productivity.

As an example of the direct printing wiring technology, a paste material is applied to the entire surface of a substrate to form a coating film, and then the coating film is irradiated with a laser beam in a pattern and selectively thermally baked to obtain a desired pattern. A method for obtaining a wiring pattern is known (see Patent Documents 1 and 2, for example).

In Patent Document 2, when GaAlAs laser light with a wavelength of 830 nm is irradiated to perform drawing, the beam diameter on the copper oxide thin film is 5 μm, and the laser light irradiated part is locally heated, so that copper oxide is formed. It is said to have been reduced to form reduced copper regions of approximately 5 μm diameter.

WO2010/024385 JP-A-5-37126

When wiring is formed by drawing with laser light irradiation as described above, the coating film remains in the regions not irradiated with light. This remaining coating causes problems such as growth of the metal outside the intended wiring pattern and short-circuiting due to migration during the plating operation after the wiring is formed. Therefore, it is necessary to sufficiently remove the remaining coating film by a developing operation after laser light irradiation.

The effect of removing the remaining coating film is enhanced by applying a physical force such as irradiating ultrasonic waves in the developer during development. On the other hand, however, such a physical force damages the metal wiring, causing problems such as breakage of the metal wiring or increased resistance.

The present invention has been made in view of this point, and in the development process, it is possible to sufficiently remove the coating film remaining between the metal wirings and reduce the change in the resistance value of the metal wirings before and after the development. It is an object of the present invention to provide a metal wiring manufacturing method capable of manufacturing high-quality metal wiring (more specifically, low resistance and less variation in resistance value between parts). Furthermore, a specific aspect of the present invention aims to effectively utilize resources by removing and reusing the coating film remaining between the metal wirings.

The present disclosure includes the following aspects.
[1] A coating step of coating a dispersion containing particle components that are metal particles and/or metal oxide particles on the surface of a substrate to form a dispersion layer;
a drying step of drying the dispersion layer to form a structure with a dry coating film having the base material and a dry coating film disposed on the base material;
A laser beam irradiation step of irradiating the dry coating film with a laser beam to form a metal wiring;
and a developing step of developing and removing the area of the dry coating film other than the metal wiring with a developer,
The developing step
(1) a first development process of developing the dry coating film with a first developer; and (2) a second development process of developing the dry coating film with a second developer;
including
A method for manufacturing metal wiring, wherein each of the first developer and the second developer contains water and/or an organic solvent.
[2] the first developer contains water and/or an alcoholic solvent;
2. The method for manufacturing metal wiring according to item 1 above, wherein the second developer contains an organic solvent.
[3] The method for manufacturing metal wiring according to item 1 or 2 above, wherein the first developer and/or the second developer contain an alcoholic solvent.
[4] The method for manufacturing metal wiring according to any one of Items 1 to 3 above, wherein the first developer and/or the second developer contain an amine solvent.
[5] The method for producing metal wiring according to item 4, wherein the amine-based solvent contains diethylenetriamine and/or 2-aminoethanol.
[6] Any one of the above items 1 to 5, wherein the first developer and/or the second developer contains 0.1% by mass or more and 20% by mass or less of a dispersant (A). A method for manufacturing metal wiring.
[7] The method for producing metal wiring according to item 6 above, wherein the dispersant (A) is a phosphorus-containing organic compound.
[8] The method for manufacturing a metal wiring according to item 6 or 7 above, wherein the dispersion contains a dispersant (B), and the main components of the dispersant (A) and the dispersant (B) are the same. .
[9] The metal wiring according to any one of Items 1 to 8 above, wherein the difference between the surface free energy of the first developer and the surface free energy of the dispersion is 0 mN/m or more and 50 mN/m or less. manufacturing method.
[10] The method for manufacturing metal wiring according to any one of Items 1 to 9 above, wherein the solubility of the particle component in the second developer is higher than the solubility of the particle component in the first developer.
[11] The method for producing a metal wiring according to any one of the above items 1 to 10, wherein the particle component is copper particles and/or copper oxide particles.
[12] The method for manufacturing a metal wiring according to Item 11 above, wherein the particle component has a solubility value of 0.1 mg/L or more and 10000 mg/L or less in the second developer.
[13] The method for manufacturing a metal wiring according to any one of Items 1 to 12 above, including a step of recovering the used developer after the developing step.
[14] The method for producing metal wiring according to any one of the above items 1 to 13, wherein the dispersion is prepared from a liquid containing a used developer collected after the development step.
[15] A kit comprising a structure with a dry coating film and a developer,
The structure with a dry coating has a substrate and a dry coating containing a particle component that is metal particles and/or metal oxide particles disposed on the surface of the substrate,
the developer comprises a first developer and a second developer;
A kit, wherein each of the first developer and the second developer contains water and/or an organic solvent.
[16] The kit according to item 15, wherein the organic solvent is an alcoholic solvent.
[17] The kit according to item 15 or 16 above, wherein the first developer and/or the second developer contain 0.1% by mass or more and 20% by mass or less of dispersant (A).
[18] The kit according to item 17 above, wherein the dry coating film contains a dispersant (B), and the main components of the dispersant (A) and the dispersant (B) are the same.
[19] A coating mechanism for forming a dispersion layer by coating a dispersion containing particle components that are metal particles and/or metal oxide particles on the surface of a substrate;
a drying mechanism for drying the dispersion layer to form a structure with a dry coating film having the base material and a dry coating film disposed on the base material;
A laser light irradiation mechanism for forming a metal wiring by irradiating the dry coating film with a laser light;
a developing mechanism that develops and removes a region of the dry coating film other than the metal wiring with a developer;
A metal wiring manufacturing system comprising:
The developing mechanism
(1) a first development station that develops the dry coating with a first developer; and (2) a second development station that develops the dry coating with a second developer;
has
A metal wiring manufacturing system, wherein each of the first developer and the second developer contains water and/or an organic solvent.
[20] The metal wiring manufacturing system according to Item 19, wherein the organic solvent is an alcoholic solvent.
[21] Manufacture of metal wiring according to Item 19 or 20 above, wherein the first developer and/or the second developer contain 0.1% by mass or more and 20% by mass or less of a dispersant (A). system.

According to one aspect of the present invention, in the development step, it is possible to sufficiently remove the coating film remaining between the metal wirings while reducing the change in the resistance value of the metal wirings before and after the development. It is possible to provide a metal wiring manufacturing method capable of manufacturing a metal wiring having a low resistance and little variation in resistance value between parts. Furthermore, according to a specific aspect of the present invention, resources can be effectively utilized by removing and reusing the coating film remaining between the metal wirings.

It is explanatory drawing which shows an example of the manufacturing method of the metal wiring which concerns on this embodiment. It is a schematic diagram explaining overlapping irradiation of a laser beam in the manufacturing method of the metal wiring which concerns on this embodiment. FIG. 4 is a schematic diagram showing an example of a jig for holding a structure with a conductive portion in a developing step of the method for manufacturing metal wiring according to the present embodiment; FIG. 4 is a schematic diagram showing an example of a jig for holding a structure with a conductive portion in a developing step of the method for manufacturing metal wiring according to the present embodiment; FIG. 4 is a schematic diagram showing an example of a jig for holding a structure with a conductive portion in a developing step of the method for manufacturing metal wiring according to the present embodiment; FIG. 5 is an explanatory diagram showing an example of reusing a used developer in the metal wiring manufacturing method according to the present embodiment. FIG. 5 is an explanatory diagram showing an example of a process flow in the case of reusing a used developer in the method for manufacturing metal wiring according to the present embodiment; BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing which shows an example of the metal wiring manufacturing system which concerns on this embodiment.

An embodiment of the present invention (hereinafter abbreviated as "this embodiment") will be described in detail below, but the present invention is not limited to these embodiments.

<Method for manufacturing metal wiring>
One aspect of the present invention is
A coating step of coating a dispersion containing a particle component (which may be simply referred to as a particle component in the present disclosure) that is metal particles and/or metal oxide particles on the surface of a substrate to form a dispersion layer. When,
a drying step of drying the dispersion layer to form a structure with a dry coating film having a substrate and a dry coating film disposed on the substrate;
A laser beam irradiation step of irradiating the dry coating film with a laser beam to form a metal wiring;
and a developing step of developing and removing the area of the dry coating film other than the metal wiring with a developing solution.
In one aspect, the developing step comprises:
(1) a first development process in which the dry coating is developed with a first developer; and (2) a second development process in which the dry coating is developed with a second developer.
including. The first developer and the second developer contain water and/or an organic solvent in one aspect.

The present inventors have found that the area irradiated with the laser beam in the dry coating film placed on the substrate (hereinafter sometimes referred to as the exposed portion) is formed as a metal wiring and the laser beam of the dry coating film is formed. When developing and removing the unexposed area (hereinafter sometimes referred to as the unexposed area) with a developer, the unexposed area may not be sufficiently removed by the developer, and the metal wiring may be removed by development. We paid attention to the fact that it may be damaged or peeled off. The inventors of the present invention conducted various studies on means for avoiding these problems, and found that the combined use of the first and second developers having specific compositions enables good removal of unexposed areas by development and low resistance. It was found that the formation of metal wiring with little variation in value between parts can be compatible.

[Composition of developer]
In the method of the present embodiment, at least two developers, a first developer containing water and/or an organic solvent and a second developer containing water and/or an organic solvent, are used. From the viewpoint of improving developability, the developer preferably contains a dispersant (dispersant (A) of the present disclosure). The dispersant can efficiently disperse (that is, efficiently remove) the metal particles and/or metal oxide particles adhering to the substrate in the developer. The dispersant may be contained in one or both of the first developer and the second developer, but the developer used in the preceding development process (in one aspect, the first development process, the second development process, When the particles are contained only in the first developer when developing in the order of processing, the particles can be collected efficiently in one operation, which is advantageous from the viewpoint of recyclability.

As the dispersant, it is preferable to use one having the same main component as the dispersant contained in the dispersion of the present disclosure. In the present disclosure, the main component of the dispersant is the component present in the largest amount among the components present as the dispersant in the dispersion or developer. When the main component of the dispersant in the dispersion and the main component of the dispersant in the developer are the same, the developability is improved. Furthermore, the developer can be recovered and reused as a dispersion. Dispersants that may be included in the dispersions of the present disclosure are preferably those described below in the section [Composition of dispersions and dried coatings]. For example, when a phosphorus-containing organic compound is used, the metal particles and/or the metal oxide particles (particularly copper oxide particles) are well dispersed in the developer, which facilitates development. Accordingly, in one aspect, examples of suitable compounds for the dispersant in the developer are the same as examples of suitable compounds for the dispersant described below in the section [Dispersion and Dry Coating Composition].

The content of the dispersant in the developer is preferably 0 in that the metal particles and/or metal oxide particles adhering to the substrate can be efficiently dispersed in the developer (that is, efficiently removed). .1% by mass or more, or 0.5% by mass or more, or 1.0% by mass or more, and can suppress dissolution of metal wiring by a dispersant, and is suitable for development even when using a high-viscosity dispersant. It is preferably 20% by mass or less, or 15% by mass, because it can form a low-viscosity developer, prevents excess dispersant from adhering to the base material and metal wiring, and can simplify the washing process after development. % by mass or less, or 10% by mass or less.

The first developer and the second developer contain water and/or an organic solvent. Since the organic solvent can dissolve and remove metals or metal oxides, it is possible to prevent metal from remaining between wirings, and is suitable for finishing development. Suitable organic solvents include amine-based solvents, alcohol-based solvents, hydrocarbon-based solvents, ester-based solvents, ketone-based solvents, and the like, and these may be used singly or in combination of two or more.

Examples of amine-based solvents include amines (primary amines, secondary amines and tertiary amines), alkanolamines, amides, etc. More specifically, diethylenetriamine, 2-aminoethanol, diethanolamine, triethanolamine, mono Examples include isopropanolamine, diisopropanolamine, triisopropanolamine, N-methylethanolamine, N-methyldiethanolamine, dicyclohexylamine, n-methyl-2-pyrrolidone, N,N-dimethylformamide and the like.

Examples of alcohol solvents include monohydric or polyhydric alcohols, and ethers and esters of these alcohols. Said alcohol is preferably a glycol. More specific examples of alcoholic solvents are:
Methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, sec-pentanol, t-pentanol, 2- methylbutanol, 2-ethylbutanol, 3-methoxybutanol, n-hexanol, sec-hexanol, 2-methylpentanol, sec-heptanol, 3-heptanol, n-octanol, sec-octanol, 2-ethylhexanol, n- monohydric alcohols such as nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, phenol, benzyl alcohol, and diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2-pentanediol, 2-methylpentane-2,4-diol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl polyhydric alcohols such as glycols such as hexane-1,3-diol, diethylene glycol, dipropylene glycol, hexanediol, octanediol, triethylene glycol and tri-1,2-propylene glycol; trihydric alcohols such as glycerin;
Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether;
Glycol esters such as propylene glycol monomethyl ether acetate;
etc.

Examples of hydrocarbon solvents include pentane, hexane, octane, nonane, decane, cyclohexane, methylcyclohexane, toluene, xylene, mesitylene, and ethylbenzene.

Ester solvents include 3-methoxy-3-methyl-butyl acetate, ethoxyethyl propionate, glycerol ethyl acetate, normal propyl acetate, isopropyl acetate and the like.

Examples of ketone-based solvents include methyl ethyl ketone, methyl isobutyl ketone, dimethyl carbonate, and the like.

The organic solvent includes or is an alcohol solvent in a preferred embodiment. Water or an alcohol-based solvent is a solvent in which the dispersant can be dispersed well, and when combined with the dispersant, the redispersibility of the particles on the substrate is improved, so that the metal particles attached to the substrate and / or suitable for dispersing metal oxide particles in a developer. From the viewpoint of efficient removal of particles, the alcohol-based solvent is preferably an alcohol having 10 or less carbon atoms, and particularly preferably ethanol, n-butanol, n-heptanol, and n-octanol.

In a preferred embodiment, the first developer contains water and/or an alcoholic solvent, and the second developer contains an organic solvent. In a preferred embodiment, the first developer and/or the second developer contain an alcoholic solvent.

In one aspect, the content of the alcohol solvent in each of the first developer and the second developer is 1% by mass or more, or 2% by mass or more, or 3% by mass or more, or 5% by mass or more, or 10% by mass or more, or 20% by mass or more, or 30% by mass or more, and in one aspect, 99% by mass or less, or 98% by mass or less, or 97% by mass or less, or 95% by mass or less good.

In one aspect, the total content of water and alcohol solvent in each of the first developer and the second developer is 20% by mass or more, or 40% by mass or more, or 50% by mass or more, or 60% by mass. or more. The total content may be 100% by mass in one aspect, or may be 99% by mass or less, or 98% by mass or less, or 97% by mass or less in one aspect.

From the viewpoint of developability, the organic solvent contains or is an amine solvent in a preferred embodiment. In a preferred embodiment, the first developer and/or the second developer contain an amine solvent. In a particularly preferred embodiment, the second developer contains an amine-based solvent when the first development with the first developer is followed by the second development with the second developer. Specific examples of amine solvents include diethylenetriamine, 2-aminoethanol, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-methylethanolamine, N-methyldiethanolamine, dicyclohexylamine, n-methyl-2-pyrrolidone, N,N-dimethylformamide and the like are preferred. From the viewpoint of developability, the amine solvent particularly preferably contains at least one of diethylenetriamine and 2-aminoethanol.

In one aspect, the water content of each of the first developer and the second developer is 1% by mass or more, or 2% by mass or more, or 3% by mass or more, or 5% by mass or more, or 10% by mass. % or more, or 20 mass % or more, or 30 mass % or more. The content may be 100% by mass in one aspect, or may be 99% by mass or less, or 98% by mass or less, or 97% by mass or less, or 95% by mass or less in one aspect.

In one aspect, the content of the organic solvent in each of the first developer and the second developer is 1% by mass or more, or 2% by mass or more, or 3% by mass or more, or 5% by mass or more, or 10% by mass or more. % by mass or more, or 20% by mass or more, or 30% by mass or more. The content may be 100% by mass in one aspect, or may be 99% by mass or less, or 98% by mass or less, or 97% by mass or less, or 95% by mass or less in one aspect. In this case, the balance may include water and/or a dispersant.

(solubility)
In one aspect, the solubility of the particulate component (ie, the metal particles and/or metal oxide particles contained in the dispersion) in the second developer is preferably higher than the solubility of the particulate component in the first developer. The above solubility is a value based on metals measured by inductively coupled plasma (ICP) emission spectrometry. When the metal particles and metal oxide particles are present in the dispersion in a ratio of metal particles: metal oxide particles = A: B (mass ratio), the above solubility is A: B (mass ratio) of the metal particles and the metal oxide particles. ratio) means the solubility of the mixture on a metal basis. Specific evaluation procedures for solubility are as follows. 0.10 g of powder of the particle component, which is metal particles and/or metal oxide particles, is added to 40 ml of developer, and allowed to stand at room temperature of 25° C. for 6 hours. After that, the developer containing the powder is filtered through a 0.2 μm filter and diluted 100 times (mass basis) with 0.10 mol/L nitric acid. The metal concentration (unit: mg/L) of the obtained diluted solution is measured using an ICP light-emitting device (eg, manufactured by SII Nanotechnology Co., Ltd.). From the metal concentration, the metal-based concentration (unit: mg/L) of the particle component is calculated and taken as the solubility of the particle component. According to the solubility as described above, the metal particles and/or metal oxide particles adhering to the substrate can be removed with good development by performing development with the second developer after development with the first developer. Efficiency is obtained.

In particular, the solubility of the particle component in the second developer is higher than the solubility of the particle component in the first developer, and the first developer contains water and/or an alcoholic solvent and a dispersant (A). , the dispersant (A) is in particular a phosphorus-containing compound, the dispersion comprises the dispersant (B), and the main components of the dispersant (A) and the dispersant (B) (i.e., in the additive, on a mass basis component contained in the largest amount) are the same, and development with the first developer and then development with the second developer are preferably performed. In this case, the development removal efficiency of the metal particles and/or metal oxide particles adhering to the substrate is particularly good.

The solubility of the particle components in the first developer, second developer and any additional developer, respectively, is preferably 0.1 mg/L or more, or 1.0 mg/L or more, or 10 mg/L or more. L or more, or 100 mg/L or more, preferably 10000 mg/L or less, or 5000 mg/L or less, or 1000 mg/L or less, or 500 mg/L or less. In particular, when the particle component is copper oxide particles, the solubility of the copper oxide in the first developer is 0.1 mg/L or more, so that the developing effect is high due to the high solubility of the copper oxide particles. When the solubility is 5000 mg/L or less, damage to metal wiring can be reduced particularly well.

In one aspect, the solubility of the particulate component in the first developer is 0.1 mg/L to 100 mg/L, and the solubility of the particulate component in the second developer is 1.0 mg/L to 500 mg/L. be.

(Surface free energy)
The surface free energy of each of the first developer, the second developer and the optional additional developer is preferably 10 mN/m or more, or 15 mN/m or more, or 20 mN/m or more, preferably , 75 mN/m or less, or 60 mN/m or less, or 50 mN/m or less. In the present disclosure, surface free energy is a value measured by the pendant drop method using a contact angle meter.

The difference between the surface free energies of each of the first developer, the second developer and any additional developer and the surface free energy of the dispersion provides good affinity between the developer and the dried coating. From the viewpoint of enhancing the development removal effect, it is preferably 50 mN/m or less, 25 mN/m or less, or 10 mN/m or less. The above difference is most preferably 0 mN/m, but may be, for example, 1 mN/m or more, or 5 mN/m or more from the viewpoint of ease of production of the developer and dispersion.

[Composition of dispersion and dry coating film]
A dry coating comprising a particulate component that is a metal particle and/or a metal oxide particle of the present disclosure is, in one aspect, a dispersion comprising a particulate component, a dispersion medium, and optionally a dispersant and/or reducing agent is applied onto the substrate and then dried. Therefore, in one aspect, the weight ratio of the components other than the dispersion medium in the dry coating may be considered the same as the weight ratio of the components other than the dispersion medium in the dispersion. Alternatively, the content of metal elements in the dry coating film can be confirmed by SEM (Scanning Electron Microscope) and EDX (Energy Dispersive X-ray Analysis) equipment.

The content of the dispersant in the dispersion and in the dried coating film can be confirmed using a TG-DTA (thermogravimetric differential thermal analysis) device.

The content of the reducing agent in the dispersion can be confirmed by a surrogate method using a GC/MS (gas chromatograph/mass spectrometer) device. Moreover, the content of the reducing agent in the dry coating film can be confirmed by a surrogate method using a GC/MS device after redispersing the dry coating film in a dispersion medium.
An example of measurement using hydrazine as a reducing agent is shown below.

(Hydrazine quantification method)
To 50 μL of the dispersion, add 33 μg hydrazine, 33 μg surrogate substance (hydrazine ¹⁵ N ₂ H ₄ ), 1 ml benzaldehyde 1% acetonitrile solution. Finally, 20 μL of phosphoric acid is added, and after 4 hours, GC/MS measurement is performed.

Similarly, 66 μg of hydrazine, 33 μg of a surrogate substance (hydrazine ¹⁵ N ₂ H ₄ ), and 1 ml of 1% benzaldehyde in acetonitrile are added to 50 μL of the dispersion. Finally, 20 μL of phosphoric acid is added, and after 4 hours, GC/MS measurement is performed.

Similarly, 133 μg of hydrazine, 33 μg of surrogate substance (hydrazine ¹⁵ N ₂ H ₄ ) and 1 ml of benzaldehyde 1% acetonitrile solution are added to 50 μL of the dispersion. Finally, 20 μL of phosphoric acid is added, and after 4 hours, GC/MS measurement is performed.

Finally, to 50 μL of the dispersion, no hydrazine was added, 33 μg of a surrogate substance (hydrazine ¹⁵ N ₂ H ₄ ), 1 mL of benzaldehyde 1% acetonitrile solution were added, and finally 20 μL of phosphoric acid was added. After 4 hours, GC/MS measurement was performed. I do.

A peak area value of hydrazine is obtained from the chromatogram at m/z=207 from the 4-point GC/MS measurement. Next, the surrogate peak area value is obtained from the mass chromatogram of m/z=209. The x-axis represents the weight of hydrazine added/the weight of the added surrogate substance, and the y-axis represents the peak area value of hydrazine/the peak area value of the surrogate substance to obtain a calibration curve according to the surrogate method.

The Y-intercept value obtained from the calibration curve is divided by the weight of hydrazine added/weight of surrogate substance added to obtain the weight of hydrazine.

((i) metal particles and/or metal oxide particles)
The metals contained in the particle components, which are metal particles and/or metal oxide particles, are aluminum, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, ruthenium, rhodium, palladium, silver, indium. , tin, antimony, iridium, platinum, gold, thallium, lead, bismuth, etc., and may be an alloy or mixture containing one or more of these. Moreover, as a metal oxide, the oxide of the metal illustrated above is mentioned. Among them, metal oxide particles of silver or copper are preferable because they are easily reduced when irradiated with a laser beam and uniform metal wiring can be formed. In particular, copper metal oxide particles have relatively high stability in the air and are available at low cost, which is advantageous from a business point of view and therefore preferable. Copper oxides include, for example, cuprous oxide and cupric oxide. Cuprous oxide is particularly preferable because it has a high absorbance to laser light, can be sintered at a low temperature, and can form a low-resistance sintered product. Cuprous oxide and cupric oxide may be used alone or in combination.

The metal oxide particles in one aspect comprise or are copper oxide particles. The copper oxide particles may have a core/shell structure, and either the core or the shell may contain cuprous oxide and/or cupric oxide.

The average secondary particle size of each of the metal particles and metal oxide particles (copper oxide particles in one aspect) is not particularly limited, but is preferably 500 nm or less, or 200 nm or less, or 100 nm or less, or 80 nm or less, or 50 nm. or less, or 20 nm or less. The average secondary particle size of the particles is preferably 1 nm or more, or 5 nm or more, or 10 nm or more, or 15 nm or more.

The average secondary particle size is the average particle size of aggregates (secondary particles) formed by aggregating a plurality of primary particles. When the average secondary particle size is 500 nm or less, fine metal wiring tends to be easily formed on the support, which is preferable. When the average secondary particle size is 1 nm or more, particularly 5 nm or more, the long-term storage stability of the dispersion is improved, which is preferable. The average secondary particle size of the particles can be measured using a transmission electron microscope or a scanning electron microscope.

The average primary particle diameter of the primary particles constituting the secondary particles is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 20 nm or less. The average primary particle size is preferably 1 nm or more, more preferably 2 nm or more, and even more preferably 5 nm or more.

When the average primary particle size is 100 nm or less, there is a tendency that the firing temperature, which will be described later, can be lowered. The reason why such low-temperature firing is possible is thought to be that the smaller the particle diameter of the particles, the higher the surface energy and the lower the melting point.

Further, if the average primary particle size is 1 nm or more, it is preferable because good dispersibility can be obtained. When a wiring pattern is formed on a substrate, the thickness is preferably 2 nm or more, or 5 nm or more, and preferably 100 nm or less, or 50 nm or less, from the viewpoint of adhesion to the base and low resistance. This tendency is remarkable when the undercoat is resin. The average primary particle size of the particles can be measured using a transmission electron microscope or a scanning electron microscope.

The dispersion and dry coating may contain copper particles. That is, the dispersions and dry coatings of the present disclosure may contain copper.

The dispersion and dry coating may contain copper oxide particles and copper particles. In this case, the mass ratio of copper particles to copper oxide particles (hereinafter referred to as "copper particles/copper oxide particles") is preferably 1.0 or more, or 1.0 or more, from the viewpoint of conductivity and crack prevention. It is 5 or more, or 2.0 or more, preferably 7.0 or less, or 6.0 or less, or 5.0 or less.

The content of the particle components that are metal particles and/or metal oxide particles in the dispersion is the total content of the metal particles and metal oxide particles, and is 0.50% by mass with respect to 100% by mass of the dispersion. It is preferably 60 mass % or more, more preferably 1.0 mass % or more and 60 mass % or less, and even more preferably 5.0 mass % or more and 50 mass % or less. When the total content is 60% by mass or less, there is a tendency to suppress aggregation of the metal particles and/or metal oxide particles. When the total content is 0.50% by mass or more, the metal wiring (that is, the conductive film) obtained by baking the dry coating film by laser light irradiation does not become too thin, and the conductivity tends to be good. .

The content of the particle components, which are metal particles and/or metal oxide particles, in the dry coating film is the total content of metal particles and metal oxide particles, and is 40% by mass with respect to 100% by mass of the dry coating film. It is preferably at least 55% by mass, more preferably at least 70% by mass. In addition, the content is preferably 98% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less.

In addition, the content of the particle component that is metal particles and / or metal oxide particles in the dry coating is the total content of metal particles and metal oxide particles, and is 10 volumes per 100% by volume of the dry coating. % or more, more preferably 15 volume % or more, and even more preferably 25 volume % or more. The content is preferably 90% by volume or less, more preferably 76% by volume or less, and even more preferably 60% by volume or less.

When the content of the particle component in the dry coating film is 40% by mass or more or 10% by volume or more, the particles are fused to each other by firing, which is preferable because good conductivity is exhibited. The higher the concentration of the particle component is, the more preferable it is in terms of conductivity. Good adhesion, especially when it is 95% by mass or less or 76% by volume or less, is preferable because the adhesion is stronger. Further, when the content is 90% by mass or less or 60% by volume or less, the dried coating film has high flexibility, cracks are less likely to occur during bending, and reliability is enhanced.

((ii) dispersant)
The dispersions and dry coatings may contain a dispersant to better disperse the particulate component, which is the metal particles and/or metal oxide particles.

Although the number average molecular weight of the dispersant is not particularly limited, it is preferably from 300 to 300,000, more preferably from 300 to 30,000, even more preferably from 300 to 10,000. When the number average molecular weight is 300 or more, the dispersion stability of the dispersion tends to increase. The residual amount of the dispersant is less, and the resistance of the metal wiring can be reduced. In the present disclosure, the number average molecular weight is a value obtained by standard polystyrene conversion using gel permeation chromatography.

As the dispersing agent, a phosphorus-containing organic compound is preferable from the viewpoint of excellent dispersibility of the metal particles and/or metal oxide particles. Moreover, the dispersant preferably has a group (for example, a hydroxyl group) that has an affinity for these particles from the viewpoint of adsorbing to the metal particles and/or metal oxide particles and suppressing aggregation of the particles due to the steric hindrance effect. In particular, the combined use of metal oxide particles and a hydroxyl group-containing dispersant is preferred. The dispersant preferably comprises a phosphorus-containing organic compound. A particularly suitable example of a dispersant is a phosphorus-containing organic compound having a phosphate group.

The phosphorus-containing organic compound is preferably easily decomposed or vaporized by light and/or heat. By using an organic substance that easily decomposes or evaporates by light and/or heat, it is possible to obtain a metal wiring with a low resistivity because the residue of the organic substance is less likely to remain after baking.

Although the decomposition temperature of the phosphorus-containing organic compound is not limited, it is preferably 600° C. or lower, more preferably 400° C. or lower, and even more preferably 200° C. or lower. The decomposition temperature may be preferably 60° C. or higher, 90° C. or higher, or 120° C. or higher from the viewpoint of the stability of the phosphorus-containing organic compound. In the present disclosure, the decomposition temperature is the value of the decomposition initiation temperature determined by thermogravimetric differential thermal analysis.

Although the boiling point of the phosphorus-containing organic compound is not limited, it is preferably 300° C. or lower, more preferably 200° C. or lower, and even more preferably 150° C. or lower. From the viewpoint of the stability of the phosphorus-containing organic compound, the boiling point may be preferably 60°C or higher, 90°C or higher, or 120°C or higher.

Although the absorption characteristics of the phosphorus-containing organic compound are not limited, it is preferable that the compound can absorb laser light used for baking. In the present disclosure, being able to absorb the laser beam used for baking means that the absorption coefficient at a wavelength of 532 nm measured with an ultraviolet-visible spectrophotometer is 0.10 cm ⁻¹ or more. More specifically, a phosphorous-containing organic compound that absorbs light of 355 nm, 405 nm, 445 nm, 450 nm, 532 nm, 1064 nm, etc., which is the emission wavelength (center wavelength) of the laser light used for baking, is preferred. In particular, when the base material is a resin base material, a phosphorus-containing organic compound that absorbs light with a center wavelength of 355 nm, 405 nm, 445 nm, and/or 450 nm is preferred.

（式中、Ｒは１価の有機基である。）
で表されるリン酸モノエステルは、金属酸化物粒子への吸着性に優れるとともに、基材に対する適度な密着性を示すことで金属配線の安定形成と未露光部の良好な現像との両立に寄与する点で好ましい。Ｒとしては、置換又は非置換の炭化水素基等を例示できる。 It is preferable that the phosphorus-containing organic compound is a phosphate ester from the viewpoint of improving the atmospheric stability of the dispersion. For example, the following general formula (1):

(Wherein, R is a monovalent organic group.)
Phosphate monoester represented by is excellent in adsorption to metal oxide particles and exhibits moderate adhesion to substrates, which contributes to both stable formation of metal wiring and good development of unexposed areas. It is preferable in that it contributes to Examples of R include substituted or unsubstituted hydrocarbon groups.

で表される構造を有する化合物を例示できる。 As an example of phosphoric acid monoester, the following formula (2):

A compound having a structure represented by can be exemplified.

（式中、ｌ、ｍ及びｎは、それぞれ独立に、１～２０の整数である。）
で表される構造を有する化合物も例示できる。 Further, as an example of phosphoric acid monoester, the following formula (3):

(Wherein, l, m and n are each independently an integer of 1 to 20.)
A compound having a structure represented by can also be exemplified.

In the above formula (3), l is an integer of 1 to 20, preferably an integer of 1 to 15, more preferably an integer of 1 to 10, m is an integer of 1 to 20, preferably an integer of 1 to 15, More preferably an integer of 1-10, n is an integer of 1-20, preferably an integer of 1-15, more preferably an integer of 1-10.

Organic structures possessed by phosphorus-containing organic compounds include polyethylene glycol (PEG), polypropylene glycol (PPG), polyimide, polyester (e.g., polyethylene terephthalate (PET), polyethylene naphthalate (PEN)), and polyether sulfone (PES). , polycarbonate (PC), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyacetal, polyarylate (PAR), polyamide (PA), polyamideimide (PAI), polyetherimide (PEI), polyphenylene ether (PPE), Polyphenylene sulfide (PPS), polyetherketone (PEK), polyphthalamide (PPA), polyethernitrile (PENt), polybenzimidazole (PBI), polycarbodiimide, polysiloxane, polymethacrylamide, nitrile rubber, acrylic rubber, Polyethylene tetrafluoride, epoxy resin, phenolic resin, melamine resin, urea resin, polymethyl methacrylate resin (PMMA), polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene-diene copolymer, polybutadiene, polyisoprene , ethylene-propylene-diene copolymer, butyl rubber, polymethylpentene (PMP), polystyrene (PS), styrene-butadiene copolymer, polyethylene (PE), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), Polyether ether ketone (PEEK), phenol novolac, benzocyclobutene, polyvinylphenol, polychloropyrene, polyoxymethylene, polysulfone (PSF), polysulfide, silicone resin, aldose, cellulose, amylose, pullulan, dextrin, glucan, fructan, chitin It may have a structure derived from a compound such as (specifically, through degeneration or modification of a functional group, polymerization, or the like). A phosphorus-containing organic compound having a polymer skeleton selected from polyethylene glycol, polypropylene glycol, polyacetal, polybutene, and polysulfide is preferable because it is easily decomposed and hardly leaves residue in the metal wiring obtained after firing.

As specific examples of the phosphorus-containing organic compound, commercially available materials can be used. Specifically, DISPERBYK (registered trademark)-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-109, DISPERBYK- 110, DISPERBYK-111, DISPERBYK-118, DISPERBYK-140, DISPERBYK-145, DISPERBYK-168, DISPERBYK-180, DISPERBYK-182, DISPERBYK-187, DISPERBYK-190, DISPERBYK-191, DISPER9, DISPERBYK-193, ＤＩＳＰＥＲＢＹＫ－１９９、ＤＩＳＰＥＲＢＹＫ－２０００、ＤＩＳＰＥＲＢＹＫ－２００１、ＤＩＳＰＥＲＢＹＫ－２００８、ＤＩＳＰＥＲＢＹＫ－２００９、ＤＩＳＰＥＲＢＹＫ－２０１０、ＤＩＳＰＥＲＢＹＫ－２０１２、ＤＩＳＰＥＲＢＹＫ－２０１３、ＤＩＳＰＥＲＢＹＫ－２０１５、ＤＩＳＰＥＲＢＹＫ－２０２２、ＤＩＳＰＥＲＢＹＫ－２０２５、ＤＩＳＰＥＲＢＹＫ－２０５０、ＤＩＳＰＥＲＢＹＫ－ 2152, DISPERBYK-2055, DISPERBYK-2060, DISPERBYK-2061, DISPERBYK-2164, DISPERBYK-2096, DISPERBYK-2200, BYK®-405, BYK-607, BYK-9076, BYK-9077, BYK-P105, Daiichi Kogyo Seiyaku Co., Ltd. Plysurf (registered trademark) M208F, Plysurf DBS, etc. can be mentioned. These may be used alone, or may be used in combination.

In the dispersion and the dry coating film, the content of the dispersant may be 5 parts by volume or more and 900 parts by volume or less when the total volume of the metal particles and metal oxide particles is 100 parts by volume. The lower limit is preferably 10 parts by volume or more, more preferably 30 parts by volume or more, and still more preferably 60 parts by volume or more. The upper limit is preferably 480 parts by volume or less, more preferably 240 parts by volume or less.

When converted to parts by mass, the content of the dispersant is preferably 1 part by mass or more and 150 parts by mass or less with respect to a total of 100 parts by mass of the metal particles and metal oxide particles. The lower limit is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more. The upper limit is preferably 80 parts by mass or less, more preferably 40 parts by mass or less. If the content of the dispersant is 5 parts by volume or more or 1 part by mass or more, a thin film with a thickness of submicrons can be easily formed. Further, when the content of the dispersant is 10 parts by volume or more or 5 parts by mass or more, a thick film having a thickness of several tens of μm can be easily formed. When the content of the dispersant is 30 parts by volume or more or 10 parts by mass or more, a highly flexible dry coating film that is resistant to cracking even when bent can be obtained. Moreover, when the content of the dispersant is 900 parts by volume or less or 150 parts by mass or less, good metal wiring can be obtained by firing.

The content of the dispersant in the dispersion is preferably 0.10% by mass or more and 20% by mass or less, more preferably 0.20% by mass or more and 15% by mass or less, based on the total dispersion. More preferably, it is 0.0% by mass or more and 8.0% by mass or less. When the content is 20% by mass or less, the conductive film obtained by firing tends to have good conductivity without increasing the residue derived from the dispersant. Moreover, when the content is 0.10% by mass or more, the metal particles and/or the metal oxide particles do not aggregate, and good dispersibility can be obtained.

((iii) reducing agent)
Dispersions and dry coatings may further comprise a reducing agent. The reducing agent may remain in the dispersion due to its use in synthesizing the particle component, which is the metal particles and/or metal oxide particles, and thus remain in the dry coating. The reducing agent preferably contains hydrazine and/or hydrazine hydrate, more preferably hydrazine and/or hydrazine hydrate. When the dispersion contains metal oxide particles and the dry coating contains a reducing agent, the metal oxide (e.g., copper oxide) is easily reduced to the metal (e.g., copper) when the dry coating is irradiated with laser light. Also, it is possible to reduce the resistance of the metal (for example, copper) after reduction. The reducing agent remains in the unexposed area (that is, the area not irradiated with the laser beam) of the dried coating film.

The mass ratio of the content of the reducing agent in the dispersion and in the dry coating film to the total content of the metal particles and metal oxide particles is preferably 0.0001 or more, or It is 0.0010 or more, or 0.0020 or more, or 0.0040 or more, and from the viewpoint of obtaining a low-resistance metal wiring by avoiding excessive reducing agent residue, it is preferably 0.10 or less, or 0.0040 or more. 050 or less, or 0.030 or less.

Further, the total content of hydrazine and hydrazine hydrate (hydrazine amount basis) in the dispersion and in the dry coating film and the content of copper oxide preferably satisfy the following relationship.
0.0001 ≤ (mass of hydrazine/mass of copper oxide) ≤ 0.10

((iv) dispersion medium)
A dispersing medium is included in the dispersion and in the dry coating to disperse the particulate component, which is the metal particles and/or metal oxide particles.

Specific examples of dispersion media that can be used include alcohols (monohydric alcohols and polyhydric alcohols (eg, glycol)), ethers of alcohols (eg, glycol), and esters of alcohols (eg, glycol). As a more specific example,
Propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-butyl acetate, ethoxyethyl propionate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether , ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether,
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2-pentanediol, 2-methylpentane-2,4-diol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl hexane-1,3-diol, diethylene glycol, dipropylene glycol, hexanediol, octanediol, triethylene glycol, tri-1,2-propylene glycol, ethyl glycerol acetate, n-propyl acetate, isopropyl acetate,
Pentane, hexane, octane, nonane, decane, cyclohexane, methylcyclohexane, toluene, xylene, mesitylene, ethylbenzene,
methyl ethyl ketone, methyl isobutyl ketone, dimethyl carbonate,
Methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, sec-pentanol, t-pentanol, 2- methylbutanol, 3-methoxybutanol, n-hexanol, sec-hexanol, 2-methylpentanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, sec-octanol, 2-ethylhexanol, n- nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, phenol, benzyl alcohol, diacetone alcohol and the like.

Among them, monoalcohols or polyhydric alcohols having 10 or less carbon atoms are more preferable from the viewpoint of dispersibility of metal particles and/or metal oxide particles. Among monoalcohols having 10 or less carbon atoms, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol and t-butanol are more preferable. These alcohols may be used singly or in combination.

The solid content of the dispersion is preferably 0.6% by mass or more and 80% by mass or less, more preferably 1.2% by mass or more and 75% by mass or less, and 6.0% by mass or more and 58% by mass. More preferably: The solid content of the dispersion is obtained by dividing the weight after heating by the weight before heating when 0.5 to 1.0 g of the dispersion is weighed and heated in air at 60 ° C. for 4.5 hours. can ask. In one aspect, the solids fraction of the dispersion corresponds to the content of particulate components that are metal particles and/or metal oxide particles in the dispersion. When the solid content is 0.6% by mass or more and 80% by mass or less, the dispersion can have a viscosity suitable for application to a substrate.

The viscosity of the dispersion is preferably 0.1 mPa s or more and 100,000 mPa s or less, more preferably 0.1 mPa s or more and 10,000 mPa s or less, and 1 mPa s or more and 1,000 mPa. · It is more preferably s or less. When the viscosity is 0.1 mPa·s or more and 100,000 mPa·s or less, the dispersion can be applied more uniformly to the substrate. In the present disclosure, viscosity is a value measured with an E-type viscometer.

From the viewpoint of preventing dissolution of the metal particles and/or metal oxide particles in the dispersion, the pH of the dispersion is preferably 4.0 or higher, 5.0 or higher, or 6.0 or higher. From the viewpoint of reducing damage to the substrate, the pH may be, for example, 10.0 or less, 9.0 or less, or 8.0 or less.

The surface free energy of the dispersion is preferably 10 mN/m or more, or 12 mN/m or more, or 15 mN/m or more, preferably 50 mN/m in that the dispersion can be uniformly applied to the substrate. or less, or 35 mN/m or less, or 25 mN/m or less.

The thickness of the dry coating film is preferably 0.1 μm or more, or 0.5 μm or more, or 1.0 μm or more from the viewpoint of easily manufacturing metal wiring having low resistance and excellent mechanical properties. From the viewpoint of manufacturing metal wiring with high precision, the thickness may be preferably 50 μm or less, 25 μm or less, or 10 μm or less.

[Base material]
The substrate constitutes the surface on which the metal wiring is arranged. The material of the substrate is preferably an insulating material in order to ensure electrical insulation between metal wirings formed by laser light. However, it is not necessary that the entire base material be an insulating material. It suffices if only the portion forming the surface on which the metal wiring is arranged is made of an insulating material.

In addition, the material of the substrate is preferably a material having a heat resistance temperature of 60° C. or higher in order to prevent the substrate from being burnt by the laser beam and generating smoke when irradiated with the laser beam. The base material does not need to be composed of a single material, and for example, glass fiber or the like may be added to the resin in order to increase the heat resistance temperature.

The surface of the substrate on which the dried coating film is to be placed may be flat or curved, or may be a surface including steps. More specifically, the base material may be a substrate (eg plate, film or sheet) or a three-dimensional object (eg housing). The plate-like body is, for example, a support used for a circuit board such as a printed board. A film or sheet is a base film, which is a thin-film insulator, used for flexible printed circuit boards, for example.

Examples of three-dimensional objects include mobile phone terminals, smart phones, smart glasses, televisions, housings of electrical equipment such as personal computers. Other examples of three-dimensional objects in the field of automobiles include dashboards, instrument panels, steering wheels, chassis, and the like.

Specific examples of the base material include a base material made of an inorganic material (hereinafter referred to as an "inorganic base material") or a base material made of a resin (hereinafter referred to as a "resin base material").

Inorganic substrates are composed of, for example, glass, silicon, mica, sapphire, crystal, clay film, and ceramic materials. Ceramic materials are selected, for example, from alumina, silicon nitride, silicon carbide, zirconia, yttria and aluminum nitride, and mixtures of at least two of these. Also, as the inorganic substrate, a substrate composed of glass, sapphire, crystal, or the like, which has particularly high light transmittance, can be used.

Examples of resin substrates include polypropylene (PP), polyimide (PI), polyester (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), etc.), polyether sulfone (PES), Polycarbonate (PC), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyacetal (POM), polyarylate (PAR), polyamide (PA) (PA6, PA66, etc.), polyamideimide (PAI), polyetherimide (PEI) ), polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyphenylene sulfide (PPS), polyetherketone (PEK), polyetheretherketone (PEEK), polyphthalamide (PPA), polyethernitrile (PENt ), polybenzimidazole (PBI), polycarbodiimide, polymethacrylamide, nitrile rubber, acrylic rubber, polyethylene tetrafluoride, epoxy resin, phenol resin, melamine resin, urea resin, polymethyl methacrylate resin (PMMA), polybutene, Polypentene, ethylene-propylene copolymer, ethylene-butene-diene copolymer, polybutadiene, polyisoprene, ethylene-propylene-diene copolymer, butyl rubber, polymethylpentene (PMP), polystyrene (PS), styrene-butadiene copolymer Polymers, polyethylene (PE), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), phenol novolac, benzocyclobutene, polyvinylphenol, polychloropyrene, polyoxymethylene, polysulfone (PSF), polyphenylsulfone resin (PPSU) ), cycloolefin polymer (COP), acrylonitrile-butadiene-styrene resin (ABS), acrylonitrile-styrene resin (AS), polytetrafluoroethylene resin (PTFE), polychlorotrifluoroethylene (PCTFE), and silicone resin etc. can be used.

In addition to the above, for example, a resin sheet containing cellulose nanofibers can also be used as the base material.

In particular, at least one selected from the group consisting of PI, PET and PEN has excellent adhesion to metal wiring, has good market distribution and is available at low cost, and is significant from a business point of view. ,preferable.

Furthermore, at least one selected from the group consisting of PP, PA, ABS, PE, PC, POM, PBT, m-PPE and PPS has excellent adhesion to metal wiring, especially when it is a housing, and Excellent moldability and mechanical strength after molding. Furthermore, these are preferable because they have heat resistance enough to withstand laser light irradiation or the like when forming metal wiring.

The material of the three-dimensional object is selected from the group consisting of polypropylene resin, polyamide resin, acrylonitrile-butadiene-styrene resin, polyethylene resin, polycarbonate resin, polyacetal resin, polybutylene terephthalate resin, modified polyphenylene ether resin, and polyphenylene sulfide resin, for example. at least one is preferred.

The deflection temperature under load of the resin substrate is preferably 400° C. or lower, more preferably 280° C. or lower, and even more preferably 250° C. or lower. A base material having a deflection temperature under load of 400° C. or less is available at low cost and is advantageous from a business point of view, which is preferable. The deflection temperature under load is preferably 70° C. or higher, or 80° C. or higher, or 90° C. or higher, or 100° C. or higher, from the viewpoint of handleability of the resin substrate. The deflection temperature under load in the present disclosure is a value obtained according to JIS K7191.

The thickness of the substrate is preferably 1 μm or more, or 25 μm or more, and preferably 100 mm or less, or 10 mm or less, or 250 μm or less, when it is a plate, film, or sheet, for example. When the thickness of the substrate is 250 μm or less, the electronic device to be manufactured can be made lighter, more space-saving, and more flexible, which is preferable.

In addition, when the substrate is a three-dimensional object, its maximum dimension (that is, the maximum length of one side) is preferably 1 μm or more, or 200 μm in that the mechanical strength and heat resistance of the substrate are well expressed. or more, preferably 1000 mm or less, or 100 mm or less, or 5 mm or less.

[Each step of the metal wiring manufacturing method]
FIG. 1 is a diagram illustrating an example of a method for manufacturing a metal wiring according to this embodiment. Exemplary aspects of each step are described below with reference to FIG.

(Preparation of dispersion)
In one aspect, the dispersion is prepared prior to the coating step. An example of preparing a dispersion containing cuprous oxide particles will be described below.
Cuprous oxide particles can be synthesized, for example, by the following method.
(1) Add water and a copper acetylacetonato complex to a polyol solvent, heat and dissolve the organocopper compound once, add a necessary amount of water for the reaction, and heat to the reduction temperature of the organocopper for reduction. Method.
(2) A method of heating an organocopper compound (copper-N-nitrosophenylhydroxylamine complex) at a high temperature of about 300° C. in an inert atmosphere in the presence of a protective agent such as hexadecylamine.
(3) A method of reducing a copper salt dissolved in an aqueous solution with hydrazine (Fig. 1(a)).

The method (1) is described in, for example, Angewante Chemi International Edition, No. 40, Vol. 2, p. 359, 2001.

The method (2) is described in, for example, Journal of American Chemical Society, 1999, Vol. 121, p. 11595 can be carried out under the conditions described.

In the above method (3), a divalent copper salt can be suitably used as the copper salt. Examples thereof include copper (II) acetate, copper (II) nitrate, copper (II) carbonate, Copper (II) chloride, copper (II) sulfate and the like can be mentioned. The amount of hydrazine to be used is preferably 0.2 mol to 2 mol, more preferably 0.25 mol to 1.5 mol, per 1 mol of the copper salt.

A water-soluble organic substance may be added to the aqueous solution in which the copper salt is dissolved. Addition of a water-soluble organic substance to the aqueous solution lowers the melting point of the aqueous solution, thereby enabling reduction at a lower temperature. As the water-soluble organic substance, for example, alcohol, water-soluble polymer, or the like can be used.

Examples of alcohol include
Methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, sec-pentanol, t-pentanol, 2- methylbutanol, 2-ethylbutanol, 3-methoxybutanol, n-hexanol, sec-hexanol, 2-methylpentanol, sec-heptanol, 3-heptanol, n-octanol, sec-octanol, 2-ethylhexanol, n- monohydric alcohols such as nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, phenol, benzyl alcohol, and diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2-pentanediol, 2-methylpentane-2,4-diol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl polyhydric alcohols such as glycols such as hexane-1,3-diol, diethylene glycol, dipropylene glycol, hexanediol, octanediol, triethylene glycol and tri-1,2-propylene glycol; trihydric alcohols such as glycerin;
Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether;
Glycol esters such as propylene glycol monomethyl ether acetate;
etc.
As the water-soluble polymer, for example, polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol copolymer, and the like can be used.

The temperature for the reduction in the above method (3) can be, for example, -20°C to 60°C, preferably -10°C to 30°C. The reduction temperature may be constant during the reaction, or may be increased or decreased during the reaction. At the initial stage of the reaction when hydrazine is highly active, the reduction is preferably carried out at 10°C or lower, more preferably 0°C or lower. The reduction time is preferably 30 minutes to 300 minutes, more preferably 90 minutes to 200 minutes. The atmosphere for reduction is preferably an inert atmosphere such as nitrogen or argon.

Among the above methods (1) to (3), the method (3) is preferable because the operation is simple and particles with a small particle size can be obtained.

Next, the reaction solution is centrifuged into a supernatant and a precipitate (FIG. 1(b)), and the copper oxide particles are recovered as a precipitate.

On the other hand, a commercially available product may be used as the copper oxide particles. Examples of commercially available products include cuprous oxide particles having an average primary particle size of 18 nm sold by EM Japan.

Next, a dispersion medium and, in one embodiment, a dispersant are added to the copper oxide particles, and stirred by a known method such as a homogenizer to disperse the copper oxide particles in the dispersion medium (FIG. 1(c)). .

In addition, depending on the dispersion medium, the copper oxide particles may be difficult to disperse, and the dispersion may be insufficient. In such a case, for example, alcohols in which copper oxide particles are easily dispersed, such as butanol, are used to disperse the copper oxide, followed by solvent replacement with a desired dispersion medium and concentration to a desired concentration. is preferred. Examples include a method of concentrating with an ultrafiltration (UF) membrane and a method of repeating dilution and concentration with a desired dispersion medium.
For example, the desired dispersion can be obtained by the procedure described above (FIG. 1(d)).
Further, by concentrating the solvent of the liquid recovered by development by vacuum distillation or membrane distillation, a desired solid content dispersion can be obtained. Moreover, the liquid collected by development can be mixed with the dispersion prepared above and utilized.

(polishing process)
In one aspect, the dispersion-coated surface of the substrate (FIG. 1(e)) may have a controlled arithmetic mean surface roughness. In a typical embodiment, polishing the substrate surface controls the arithmetic mean surface roughness of that surface. Thus, in one aspect, the substrate has a polished surface (FIG. 1(f)). In this disclosure, polishing includes both smoothing and roughening. The method of polishing is not particularly limited. polishing method. An appropriate polishing method may be selected according to the material and surface morphology of the surface to be polished of the substrate, the desired arithmetic mean surface roughness value, and the like.

The arithmetic mean surface roughness Ra of the dispersion-coated surface of the substrate is preferably 70 nm or more, or 100 nm or more, or 150 nm or more, and may preferably be 10000 nm or less, or 5000 nm or less, or 1000 nm or less. In the present disclosure, the arithmetic mean surface roughness Ra is a value measured using a stylus surface profilometer. In addition, the surface roughness of the substrate on which the coating film is already arranged can be measured by the following method. The substrate on which the coating film is arranged is immersed in 0.6% by mass of nitric acid or hydrochloric acid, the amount that the entire substrate is immersed, and shaken at a speed of 60 rpm for 12 hours or more to dissolve the coating film. . When the coating film is completely dissolved, the substrate is washed with 50 ml or more of ultrapure water, and then measured with a stylus surface profiler.

When the value of the arithmetic mean surface roughness Ra is 70 nm or more, the dispersion penetrates into the uneven concave portions of the substrate surface due to the anchor effect, so that the dry coating film and the substrate are in good contact with each other, and the development operation can be performed. A metal wiring is formed which is difficult to peel off even if it is removed. This is preferable because the damage to the metal wiring during the developing operation is further reduced, and the resistance of the metal wiring is less likely to increase after the development. Further, when the arithmetic mean surface roughness Ra is 10000 nm or less, the irregularities on the surface of the base material are not excessively large, so that the coating film can be formed on the surface with a uniform thickness. As a result, it is possible to obtain a metal wiring that is less likely to break and that has less variation in resistance value between portions. Further, the value of the arithmetic mean surface roughness Ra of 10000 nm or less is also advantageous in terms of good development removability of unexposed areas.

(Coating process)
In this step, a dispersion layer is formed by coating a dispersion on the surface of a substrate whose arithmetic mean surface roughness has been controlled (FIG. 1(g)). The method for forming the dispersion layer is not particularly limited, but coating methods such as die coating, spin coating, slit coating, bar coating, knife coating, spray coating, and dip coating can be used. Using these methods, it is desirable to apply a uniform thickness of the dispersion onto the substrate.

(Drying process)
In this step, the substrate and the dispersion layer formed on the substrate are dried to form a dry coating film (FIG. 1(h)). Drying conditions may be adjusted so that the solids content of the dried coating is controlled within the desired range (the range recited in this disclosure in one aspect).

The drying temperature is preferably 40° C. or higher, or 50° C. or higher, or 60° C. or higher in that the drying time can be shortened and the industrial productivity can be improved. ), the temperature is preferably 120° C. or less, or 110° C. or less, or 100° C. or less, or 90° C. or less, in terms of being able to suppress deformation. The drying time prevents excessive volatilization of the dispersion medium in the dispersion layer and controls the solids content of the dry coating above desired, thereby facilitating dispersion of the dry coating during development (i.e. from the viewpoint of improving developability), the time is preferably 8 hours or less, or 4 hours or less, or 2 hours or less, and a minute amount of dispersion medium contained in the dry coating film reacts with the base material (especially the resin base material). However, the base material is dissolved and diffused into the dry coating film, the bond between the dry coating film and the base material is strengthened, and deterioration of developability can be suppressed. It is preferably 10 minutes or more, or 20 minutes or more, or 30 minutes or more in terms of reducing the content of organic components contained in the metal wiring and manufacturing low-resistance metal wiring. Drying pressure may typically be atmospheric pressure. The pressure may be reduced, preferably to -0.05 MPa or less, or -0.1 MPa or less in terms of gauge pressure, from the viewpoint of increasing industrial productivity. A structure with a dry coating film having a base material and a dry coating film disposed on the base material can be formed by the drying process as described above.

The solid content of the dry coating film is preferably 60% by mass or more and 99% by mass or less, more preferably 65% by mass or more and 95% by mass or less, and 70% by mass or more and 90% by mass or less. More preferred. In the present disclosure, the percent solids content of the dried coating can be measured using a TG-DTA (thermogravimetric differential thermal analysis) instrument. When the solid content of the dry coating film is 60% by mass or more, the volume shrinkage of the dry coating film when the metal wiring is obtained by irradiating the laser light is small, the amount of voids in the metal wiring is small, and the sinterability is high. Therefore, it is possible to obtain a wiring having a low resistance and a small variation in resistance value between parts. Further, when the solid content of the dry coating film is 60% by mass or more, the adhesive strength or bonding strength between the unexposed portion and the substrate is small, and good removability by development can be obtained. For example, when the base material is a resin base material, the base material is slightly dissolved by the dispersion medium in the dry coating film, and the components of the base material diffuse in the dry coating film, thereby separating the unexposed area and the base material. In some cases, they are strongly bonded, but such diffusion can be avoided if the solid content is 60% by mass or more. On the other hand, when the solid content of the dry coating film is 99% by mass or less, the metal particles and / or metal oxide particles in the dry coating film are well dispersed in the developer, and on the substrate after development The residual amount of metal particles and/or metal oxide particles can be reduced (that is, the developability is good).

(Storage process)
In one aspect, a storage step of storing the structure with a dry coating film for a predetermined period of time may be performed. In the storage step, the storage temperature is preferably 0° C. or higher, or 5° C. or higher, or 10° C. or higher, and preferably 40° C. or lower, or 30° C. or lower. Furthermore, the relative humidity is preferably 20% or higher, or 30% or higher, and preferably 70% or lower, or 50% or lower. During storage of a structure with a dry coating film, deterioration and migration of components of the coating film may occur, and the migration causes short-circuiting of metal wiring. When the storage temperature and relative humidity are within the above ranges, the dry coating film is stably stored, thereby suppressing deterioration and migration of coating film components. The pressure during storage may typically be normal pressure, but may be reduced, preferably -0.05 MPa or less, or -0.1 MPa or less in gauge pressure.

The storage time of the structure with the dry coating film is such that the heat during the drying process can be released and the change in the coating film composition due to the moisture absorption of the dry coating film by the moisture in the air is suppressed. It is preferably 10 minutes or more, or 20 minutes or more, or 30 minutes or more in terms of suppressing variations in the resistance value of the metal wiring formed by laser irradiation in the process. The dispersion medium reacts with the base material (especially the resin base material), and the base material dissolves and diffuses into the dry coating film, thereby strengthening the bond between the dry coating film and the base material, thereby preventing deterioration in developability. point, preferably 60 days or less, or 30 days or less, or 7 days or less.

(Laser beam irradiation step)
In this step, the dry coating film is irradiated with a laser beam (Fig. 1 (i)), and the conductive portion (exposed portion) and non-conductive portion (unexposed portion) disposed on the substrate, A structure with a conductive portion is formed (FIG. 1(j)). The conductive portion is formed as a metal wiring. For example, when using a dispersion containing copper oxide particles, in the laser light irradiation step, the copper oxide in the dry coating film is reduced to generate copper particles, and the generated copper particles are fused together to form an integral unit. A heat treatment is performed under conditions that cause quenching to form a metal wiring.

For laser light irradiation, a known laser light irradiation device having a laser light irradiation unit may be used. A laser beam is preferable in that high-intensity light can be exposed for a short period of time, and the dried coating film formed on the base material can be raised to a high temperature for a short period of time and baked. The laser beam method is advantageous in that the firing time can be shortened, so that the base material is less damaged and can be applied to base materials with low heat resistance (for example, resin film substrates). In addition, the laser light method has a large degree of freedom in wavelength selection, and is advantageous in that the wavelength can be selected in consideration of the light absorption wavelength of the dry coating film and/or the light absorption wavelength of the base material.

Furthermore, according to the laser light method, exposure by beam scanning is possible, so it is easy to adjust the exposure range. Irradiation (drawing) is possible.

YAG (yttrium aluminum garnet), YVO (yttrium vanadate), Yb (ytterbium), semiconductor lasers (GaAs, GaAlAs, GaInAs), carbon dioxide gas, etc. can be used as the type of laser light source. As for the laser, not only the fundamental wave but also the harmonic wave may be taken out and used as needed.

The center wavelength of the laser light is preferably 350 nm or more and 600 nm or less. In particular, when cuprous oxide is used as the metal oxide, the cuprous oxide absorbs laser light having a center wavelength within the above range, so that it can be uniformly reduced to form a low-resistance metal wiring.

Laser light is preferably applied to the dry coating film through a galvanometer scanner. Metal wiring of any shape can be obtained by scanning the dry coating film with laser light using a galvanometer scanner.

The laser light irradiation output is preferably 100 mW or more, or 200 mW or more, or 300 mW or more from the viewpoint of efficiently performing desired baking (for example, reduction of cuprous oxide). From the viewpoint of suppressing breakage of the metal wiring due to ablation and obtaining a low-resistance metal wiring, the power is preferably 1500 mW or less, 1250 mW or less, or 1000 mW or less.

In one aspect, the laser light may be repeatedly scanned to desired locations on the dry coating. In this case, the amount of movement of the laser light is preferably set such that adjacent scanning lines overlap each other. FIG. 2 is a schematic diagram illustrating overlapping irradiation of laser light in the metal wiring manufacturing method according to the present embodiment. Referring to FIG. 2, the first scanning line R1 and the adjacent second scanning line R2 overlap each other. As a result, the heat storage amount increases in the overlap region where the first scanning line R1 and the second scanning line R2 overlap, so that the degree of sintering of the copper particles is increased, and as a result, the resistance value of the metal wiring is increased. can be lowered.

The overlap rate S is calculated by the following formula from the width S1 of the first scanning line R1 of the laser light and the width S2 of the second scanning line R2 overlapping the first scanning line R1 in the direction perpendicular to the scanning length direction. can be found at
S = S2/S1 x 100 (%)

The overlap ratio is preferably in the range of 5% to 99.5%, more preferably in the range of 10% to 99.5%, further preferably in the range of 15% to 99.5%. preferable. When the overlap ratio is 5% or more, the degree of sintering of the metal wiring can be increased, and the amount of smoke generated can be suppressed. When it is 99.5% or less, the dried coating film can be sintered while moving the laser beam in the direction perpendicular to the scanning length direction at an industrially practical speed. According to the overlapping ratio within the above range, the degree of sintering of the metal wiring can be increased compared to, for example, an overlapping ratio below the above range, so that the metal wiring can be manufactured to be hard and not brittle. As a result, for example, even when the metal wiring is formed on the flexible substrate and bent, the metal wiring can follow the flexible substrate without breaking.

(Development process)
In this step, the unexposed portion of the dried coating film is developed and removed with a developer (FIG. 1(k)). The form of development is not particularly limited. For example, the structure with the conductive portion may be immersed in the developer and shaken, or the structure with the conductive portion may be immersed in the developer and then irradiated with ultrasonic waves using an ultrasonic device. The developer may be directly sprayed onto the structure with a conductive portion by spraying or the like.

The development step includes a first development treatment with a first developer and a second development treatment with a second developer. In one aspect, the developing step is a combination of one or more first development treatments with a first developer and one or more second development treatments with a second developer. be. The type of developer used in the first development treatment performed twice or more may be the same or different, and similarly, the type of developer used in the second development treatment performed twice or more may be the same or different. For example, a combination of a dispersant-containing developer and a dispersant-free developer may be employed as the first or second developer. In this case, it is preferable to carry out development with a developer containing a dispersant and then development with a developer without a dispersant, since this reduces the residual amount of the dispersant on the structure with a conductive portion.

According to the combination of the first development treatment and the second development treatment, the effect of dispersing the coating film in the developer is high, and the removability of the unexposed areas is excellent. In the development step, it is preferable to use the first developer and the second developer separately by replacing them (that is, not to mix them). By replacing the developer, the effect of dispersing the coating film in the developer can be enhanced, and the developability can be improved.

The development step, in addition to the first and second development treatments, may further include an additional development treatment using the additional developer solutions of the present disclosure. The timing of additional development processing is not limited. For example, when performing the second development process after the first development process, before the first development process, between the first development process and the second development process, and/or after the second development process can be later.

The compositions of the first developer, the second developer, and the additional developer may be different from each other, or two or more of them may be the same. Preferred aspects of the additional developer may be the same as listed in this disclosure for the first developer and/or the second developer.

When the structure with a conductive portion is immersed in a developer and irradiated with ultrasonic waves using an ultrasonic device, the irradiation time of ultrasonic waves is preferably 1 minute or more and 30 minutes or less. When the irradiation is performed for 1 minute or more, the effect of dispersing the coating film adhering to the substrate is high, and when the irradiation is performed for 30 minutes or less, damage to the metal wiring can be suppressed.

In the developing step, it is preferable to use a jig for holding the structure with a conductive portion. The shape of the jig is not particularly limited. It is desirable to have a shape that can prevent the metal wiring from being damaged or falling off due to the structures coming into contact with each other when the structures are developed simultaneously. The jig may be, for example, a jig having dents for holding the structures with conductive portions one by one, a clip for holding the structures, or the like.

3 to 5 are schematic diagrams showing an example of a jig for holding the structure with a conductive portion in the developing step of the metal wiring manufacturing method according to the present embodiment. In FIG. 3, a jig 12 having a rack portion 12a is placed in a container 11, and a substrate 13a and a post-irradiation coating film 13b (that is, a film having a conductive portion and a non-conductive portion) are placed on the rack portion 12a. shows an example of placing a structure 13 with a conductive portion. In FIG. 4, a jig 22 for forming a depression 22a is arranged in a container 21, and a structure 23 with a conductive portion having a three-dimensional substrate 23a and a post-irradiation coating film 23b in the depression 22a. shows an example of inserting a . In FIG. 5, the container 31 also functions as a jig by having a jig 32 portion for forming the recessed portion 32a. It shows an example of inserting a structure 33 with a conductive portion. The depressions 22a, 32a shown in FIGS. 4 and 5 are particularly useful when using a three-dimensional substrate.

In particular, when the structures with conductive portions are irradiated with ultrasonic waves during development, the rack portion 12a shown in FIG. 3 and the recessed portions 22a and 32a shown in FIGS. To prevent.

More preferably, the jig has a structure such as a mesh structure that does not interfere with the contact between the developer and the structure with the conductive part while holding the structure with the conductive part well.

Furthermore, the jig may have any desired member or shape, such as a lid for preventing the structure with the conductive portion from floating in the developer.

(Recovery and reuse of developer)
In the present disclosure, a dispersion containing a particle component that is metal particles and/or metal oxide particles is obtained by recovering a developer (spent developer) used for development in a development process after the development process, and recovering the used developer after the development process. It may be a dispersion (regenerated dispersion) prepared from a liquid containing a developer. The recovery method and adjustment method of the used developer are as described later.

There is no particular limitation on the method of collecting the used developer, but it can be a method of extracting the used developer from the developing tank with a pump, a method of draining the used developer from the bottom of the tank, or a method of collecting the used developer from the developing tank. A method of directly charging the used developer into the tank can be used. Further, in order to recover the components in the developer uniformly and efficiently, the liquid may be transferred while being stirred. The collection tank is not particularly limited, but a container made of SUS, polyethylene, polypropylene, or the like, which is resistant to the components of the developer, is preferable.

The spent developer recovered as described above may be used to prepare a regenerated dispersion. It is preferable to collect the used developer and reuse it for preparation of the dispersion from the viewpoint of effective use of resources and cost reduction due to reduction of waste. When the major component of the dispersant in the dispersion and the major component of the dispersant in the developer are of the same type, the recycling efficiency of the developer is better.

In particular, when the developer contains water and the used developer is regenerated to obtain a regenerated dispersion, in addition to the advantage of reusing resources, the use of water makes it possible to use water at a lower cost and in a cleaner environment. It also has the advantage of regenerating

Further, in one aspect, the used developer can be reused as it is as a raw material for the dispersion only by adjusting the concentration as necessary. In this case, for example, since it is not necessary to newly prepare a dispersant, it is possible to recover resources with higher efficiency.

Referring to Figures 6 and 7, a regenerated dispersion can be prepared by collecting spent developer and subjecting it to a regeneration process. A part or all of the used developer may be reused. As dispersions of the present disclosure, virgin dispersions (i.e., freshly prepared dispersions) or regenerated dispersions or combinations thereof can be subjected to the coating step, and in FIGS. An example of subjecting a combination with a dispersion to a coating process is shown. With reference to FIGS. 6 and 7, the virgin dispersion and the regenerated dispersion are applied to a substrate, dried to form a dry coating film, irradiated with a laser beam (i.e., baked), developed with a developer, and wired. complete the The recycled dispersion is formed by recovering part or all of the used developer and subjecting it to a recycling treatment.

Examples of regeneration treatment include concentration adjustment (e.g. concentration or dilution), component adjustment (e.g. addition or removal of a predetermined component), purification (e.g. removal of impurities such as residues), dispersion condition adjustment (e.g. dispersion treatment), and the like. In addition, the components of the used developer may be analyzed prior to the recycling process. In this case, the regeneration treatment conditions may be determined based on the obtained component analysis results. If the used developer contains a dispersant, it is preferred that the reclaim treatment be conducted under conditions that avoid alteration or loss of the dispersant.

More specific examples of regeneration treatments include (1) concentration, (2) addition of one or more of metal particles and/or metal oxide particles, dispersants, reducing agents, and dispersion media, and (3) use dispersing the components in the finished developer. When performing all of these processes, the order is not particularly limited, but the order of (1), (2), and (3) is preferable.

(1) Concentration The method of concentrating the used developer is not particularly limited, but may be a method of evaporative concentration by heating and depressurization with an evaporator or the like, a method of concentrating using a separation membrane, or freeze-drying. and then once again dispersing the obtained powder in the dispersion medium. By concentration, the solid content may be adjusted to preferably 5% by mass or more, or 10% by mass or more, and preferably 60% by mass or less, or 50% by mass or less.

(2) Addition To the used developer, one or more of the components exemplified above as components contained in the dispersion, more specifically, metal particles, for viscosity adjustment and / or solid content adjustment and/or one or more of metal oxide particles, dispersants, reducing agents, and dispersing media are preferably added. In one embodiment, the desired components of the dispersion that are not present in the spent developer or are present in the spent developer but in less than desired amounts may be added.

(3) Dispersion Treatment From the viewpoint of obtaining a high-quality regenerated dispersion, it is preferable to carry out dispersion treatment of the components contained in the spent developer. The dispersion method is not particularly limited. For example, the used developer may be placed in a container and continuously shaken with a shaker to promote dispersion by liquid flow. distributed processing may be performed. From the viewpoint of the stability of the used developer, the dispersion time is preferably 1 minute or longer. The longer the dispersion time, the better, but from the viewpoint of production efficiency, it may be, for example, one hour or less. When the addition of the above (2) is also performed, the dispersion treatment is preferably performed after the addition of the above (2).

Regenerated dispersions can be prepared via the processes exemplified above. The types of components contained in the regenerated dispersion, the content of each component, and various properties (solid content, viscosity, pH, surface free energy, etc.) may be the same as those described above for the dispersion.

<Kit including structure with dry coating film or structure with conductive portion and developer>
One aspect of the present invention also provides a kit comprising the dry coated structure of the present disclosure described above and the developer solution of the present disclosure described above. A structure with a dry coating has a substrate and a dry coating of the present disclosure disposed on the surface of the substrate. That is, the dry coating film, in one aspect, contains a particle component that is metal particles and/or metal oxide particles, and in one aspect, further contains a dispersant and/or a reducing agent.
One aspect of the present invention also provides a kit including the structure with a conductive portion of the present disclosure described above and the developing solution of the present disclosure described above. The structure with a conductive portion has a substrate and a film having (1) a conductive portion region and (2) a non-conductive portion region disposed on the surface of the substrate. In one aspect, (1) conductive portion regions correspond to exposed portions in this disclosure, and (2) non-conductive portion regions correspond to unexposed portions in this disclosure. (1) The conductive portion region is a metal wiring containing copper in one aspect. (2) The non-conductive portion region contains cuprous oxide in one aspect, and further contains a dispersant and/or a reducing agent in one aspect.

In each of the above kits, the developer comprises a first developer of the present disclosure and a second developer of the present disclosure. The first developer and / or the second developer, in one aspect, contains water and / or an organic solvent (in one aspect, an alcoholic solvent), further comprises a dispersant (A) in one aspect, and in one aspect, The dispersant (A) is contained in an amount of 0.1% by mass or more and 20% by mass or less. In one embodiment, the dry coating contains dispersant (B), and the main components of dispersant (A) and dispersant (B) are the same.

By using the structure with a dry coating film and the developer in combination as described above, a low-resistance metal wiring can be formed by irradiating the dry coating film with a laser beam, and the metal wiring can be formed without damaging the metal wiring. By satisfactorily removing the exposed portion by development, a high-quality structure with metal wiring having a base material and metal wiring arranged on the surface of the base material can be manufactured. In addition, by using a combination of the structure with the conductive part and the developer as described above, the non-conductive part can be satisfactorily removed by development without damaging the conductive part, which is the metal wiring, and a high-quality metal wiring can be obtained. Structures can be manufactured.

<Metal wiring manufacturing system>
One aspect of the invention also provides a metal interconnect manufacturing system. Referring to FIG. 8, in one aspect, metal interconnect manufacturing system 100 includes:
a coating mechanism 101 for coating a dispersion containing particle components that are metal particles and/or metal oxide particles on the surface of a substrate to form a dispersion layer;
a drying mechanism 102 that dries the dispersion layer to form a dry coated structure having a substrate and a dry coated film disposed on the substrate;
a laser beam irradiation mechanism 103 for irradiating a dry coating film with a laser beam to form a metal wiring;
a developing mechanism 104 that develops and removes the area of the dry coating film other than the metal wiring with a developer;
Prepare.
The metal wiring manufacturing system of the present disclosure can be suitably applied to the metal wiring manufacturing method of the present disclosure. Therefore, as each element of the metal wiring manufacturing system, those having the configuration or function as exemplified above in the metal wiring manufacturing method may be adopted.

The coating mechanism 101 may be, for example, one or more selected from die coaters, spin coaters, slit coaters, bar coaters, knife coaters, spray coaters, dip coaters, and the like.

The drying mechanism 102 may be one or more selected from ovens, vacuum dryers, nitrogen introduction dryers, IR furnaces, hot plates, and the like.

The laser beam irradiation mechanism 103 may have, for example, a laser beam oscillator (not shown) and a galvanometer scanner (not shown) that irradiates the coating film with the oscillated laser beam.

The development mechanism 104, in one aspect,
(1) a first developer station 104a that develops the dry coating with the first developer of the present disclosure; and (2) a second developer station 104b that develops the dry coating with the second developer of the present disclosure. ,
have The first developer and / or the second developer, in one aspect, contains water and / or an organic solvent (in one aspect, an alcoholic solvent), further comprises a dispersant in one aspect, and in one aspect, the dispersion agent in an amount of 0.1% by mass or more and 20% by mass or less. Although the positional relationship between the first developing portion 104a and the second developing portion 104b is not limited, from the viewpoint of the removal efficiency of metal particles and/or metal oxide particles, as shown in FIG. are provided to the first development station 104a and then to the second development station 104b.

In one aspect, each of the first development section 104a and the second development section 104b may have a developer and a container containing the developer and the structure with a conductive portion. Each of the first developing section 104a and the second developing section 104b preferably has a mechanism for promoting development, for example, a shaker for shaking the structure with the conductive portion, or applying ultrasonic waves to the structure with the conductive portion. It has one or more of ultrasonic irradiators and the like that irradiate. In one aspect, each of the first developing section 104a and the second developing section 104b may be composed of a developer and a sprayer that sprays the developer onto the structure with a conductive portion.

In one aspect, the metal interconnect manufacturing system 100 may further include a developer regeneration mechanism 105 that regenerates the developer recovered from the development mechanism 104 to produce a regenerated dispersion. The developer regeneration mechanism 105 may be, for example, a concentrating device, a diluting device, a mixing device, an impurity removing device, a dispersing device, or the like.

In addition to the elements described above, the metal wiring manufacturing system may optionally include additional elements such as a substrate transport mechanism, a substrate cleaning mechanism, and the like.

<Application example>
As described above, according to the method for manufacturing a metal wiring according to the present embodiment and the combination of the structure with a dry coating film or the structure with a conductive portion and the developer, the change in the resistance value of the metal wiring due to development It is possible to manufacture a structure with metal wiring with good developability while suppressing the The structure with metal wiring according to the present embodiment is formed in, for example, a metal wiring material such as an electronic circuit board (printed circuit board, RFID, substitute for wire harness in automobiles, etc.), portable information device (smartphone, etc.). It can be suitably applied to antennas, mesh electrodes (electrode films for capacitive touch panels), electromagnetic shielding materials, heat dissipation materials, and the like.

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

<Evaluation method>
[Arithmetic mean surface roughness Ra of substrate]
The arithmetic mean surface roughness Ra of the surface of the substrate to which the dispersion was applied was measured by the following method. The surface roughness of the substrate was measured using a stylus surface profiler (DektakXT manufactured by Bruker) and analysis software (Vision64). The measurement conditions are as follows.
Scan type: Standard Scan range: 65.5 μm
Profile: Hills & Valleys
Stylus type: Radius 12.5 μm
Stylus force: 1 mg
Length: 1000 μm
Retention time: 5 seconds Resolution: 0.666 µm/pt
After measuring the shape of the substrate surface, the surface roughness was analyzed. The analysis conditions for roughness are as follows.
Filter type: Gaussian regression long cutoff: long cutoff applied, standard cutoff used (0.25mm)
Roughness profile: Ra
Parameter calculation: ISO4287
Sample length used in calculation: Automatic selection The average value of the surface roughness values obtained under the above conditions and the surface roughness values measured in the direction orthogonal to the above measurement direction is the arithmetic mean of the base material. It was taken as the value of the surface roughness Ra.

[Resistance value of metal wiring and change in resistance value before and after development]
For each metal wiring of the structure with a conductive part, in which three metal wirings are formed by laser light irradiation, a tester is applied to a position 0.5 mm from both ends in the longitudinal direction to measure the resistance value, and the number average of the three metal wirings is measured. _A value RA was calculated. Also, the resistance value of the metal wiring after the structure with the conductive portion was developed was similarly measured, and the number average value RB of the three metal _wirings was calculated. _A value of RB/ _RA of 10 or less was judged to be good, a value of 5 or less to be better, and a value of 2 or less to be even better. Good is indicated by Δ, better is indicated by ◯, and even better is indicated by ⊚. On the other hand, when the value of R _B /R _A is greater than 10, or when the resistance value cannot be measured due to disconnection, the evaluation is expressed as x.

[solubility]
0.10 g of a powder of cuprous oxide particles (as a particle component that is metal particles and/or metal oxide particles) was added to 40 ml of a developer and allowed to stand at room temperature of 25° C. for 6 hours. After that, the developer containing the powder was filtered through a 0.2 μm filter and diluted 100 times (mass basis) with 0.10 mol/L nitric acid. The metal concentration (unit: mg/L) of the obtained diluted solution was measured using an ICP light-emitting device (manufactured by SII Nanotechnology Co., Ltd.) to determine the solubility.

[Surface free energy]
It was measured by the pendant drop method using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., Model No. DM700). A syringe equipped with a 22G injection needle was filled with the measurement solution, a 5 μL droplet was ejected from the injection needle, and the surface free energy was determined from the shape of the droplet at the tip of the needle using the Young-Laplace method.

[Developability of structure with conductive part]
Developability was evaluated by the following method. A structure with a conductive part (that is, a structure including a copper wiring and a dry coating film not irradiated with laser light) prepared in the laser light irradiation step is immersed in an amount of developer (23 ° C. ), and irradiated with ultrasonic waves for 1 minute or more and 30 minutes or less using an ultrasonic device for development.

Of the base material after development, a portion where no metal wiring is present is cut into 10 mm squares, attached to a sample stage for SEM (scanning electron microscope) with carbon tape, and coated with a coater (MSP-1S manufactured by Vacuum Device Co., Ltd.). It was coated with platinum-palladium. At this time, the coating conditions were set to process time: 1.5 minutes. For the sample after coating, SEM (FlexSEM1000 manufactured by Hitachi High-Tech) and EDX (energy dispersive X-ray spectrometer) (AztecOne manufactured by Oxford Instruments) are used to measure the residual concentration of the applied metal on the substrate surface. did. At this time, the conditions of the electron beam were acceleration voltage: 5 kV, spot intensity: 80, and focus position: 10 mm. The conditions for mapping acquisition were resolution: 256, acquisition time: 50 frames, process time: high sensitivity, pixel dwell time: 150 μs, frame live time: 0:00:08. It was also specified that the elements to be measured were carbon, oxygen, nitrogen, and the metal elements applied (ie, contained in the dispersion), and that platinum and palladium used for coating were not included in the elements to be measured. Measurement was performed under the above conditions, and the metal element concentration (% by mass) obtained was used as the concentration of the metal remaining on the substrate due to failure in development.

(Developability evaluation criteria)
In the evaluation of the developability of the structure with a conductive portion, it was judged that the concentration of the metal remaining in the base material was 14% by mass or less, and that it was even better if it was 2.0% by mass or less. Good is indicated by ◯, and better is indicated by ⊚. On the other hand, when the concentration of the metal remaining on the substrate is greater than 14% by mass, or when the coating film is clearly not dispersed in the developer during the developing operation and the coating film remains on the substrate, it is indicated as ×. .

<Example 1>
[Manufacturing of Dispersion]
In a mixed solvent consisting of 30240 g of water and 13976 g of 1,2-propylene glycol (manufactured by Asahi Glass Co., Ltd.), 3224 g of copper (II) acetate monohydrate (manufactured by Nihon Kagaku Sangyo Co., Ltd.) is dissolved, and hydrazine hydrate (manufactured by Nippon Finechem Co., Ltd.) is dissolved. After adding 940 g and stirring, the mixture was separated into a supernatant and a precipitate using centrifugation.

To 858 g of the obtained precipitate, 113 g of DISPERBYK-145 (trade name, manufactured by BYK-Chemie) (BYK-145) as a phosphorus-containing organic compound and 916 g of n-butanol (manufactured by Sankyo Chemical Co., Ltd.) as a dispersion medium were added and stirred under a nitrogen atmosphere. A dispersion containing cuprous oxide particles containing cuprous oxide (copper(I) oxide) was obtained by dispersing using a homogenizer. At this time, the solid content residue (cuprous oxide particles) when the dispersion was heated at normal pressure at 60° C. for 4.5 hours was 34.7% by mass. The surface free energy of the dispersion was measured to be 26 mN/m.

[Polishing of base material]
The surface of an ABS substrate (as a base material) of width x depth x thickness of 50 mm x 50 mm x 1 mm was polished using #1000 abrasive paper. After polishing, the arithmetic mean surface roughness Ra was measured to be 181 nm.

[Application and drying of dispersion]
The substrate after polishing was cleaned by irradiating ultrasonic waves in ultrapure water for 5 minutes and then in ethanol for 5 minutes. Next, after applying UV ozone treatment to the surface of the substrate, 1 ml of the dispersion was dropped onto the surface, spin-coated (300 rpm, 300 seconds), and then dried by heating at 60° C. for 1 hour. After drying, it was stored for 10 minutes in a room under normal pressure, room temperature of 23° C. and relative humidity of 40% to obtain a sample having a dry coating film formed on the substrate.

[Laser beam irradiation]
The above sample was placed in a box with a length of 200 mm, width of 150 mm, and height of 41 mm, the upper surface of which was made of quartz glass, with the dry coating film facing upward, and the compressed air was separated into nitrogen and oxygen by a separation membrane. , the separated nitrogen gas was blown into the box to make the oxygen concentration in the box 0.5% by mass or less. Next, while moving the focal position on the substrate surface at a maximum speed of 25 mm / sec using a galvanometer scanner, the dry coating film is repeatedly irradiated with laser light (center wavelength 355 nm, frequency 300 kHz, pulse, output 79 mW) while scanning. Then, a copper metal wiring having a desired dimension of 5 mm in length and 1 mm in width was obtained. At this time, the laser beam was repeatedly irradiated while being moved in the scanning line width direction so that the overlap ratio was 93.2%. Two more copper wirings were produced under the same conditions to obtain a total of three copper wirings.

[Wiring resistance after laser beam irradiation]
When the resistance of the obtained metal wiring was measured by the method described above, the three copper wirings were 10Ω, 11Ω, and 9.9Ω, respectively, and the average resistance value _RA before development was 10Ω.

[Developability of structure]
After the laser beam irradiation, the structure with a conductive portion was immersed in 50 ml of a 2% by mass DISPERBYK-145 aqueous solution (first developer) (23° C.), and cleaned with an ultrasonic cleaner (USD-4R manufactured by AS ONE) for 5 minutes. After ultrasonic irradiation for minutes, the structure was pulled up with tweezers and washed with 50 ml of ultrapure water under running water. After that, it is immersed in 50 ml (23° C.) of a new 5% by mass diethylenetriamine aqueous solution (second developer) and irradiated with ultrasonic waves for 1 minute. did
After the above developing operation, the copper concentration in the portion where the metal wiring was not present on the base material was measured by the method described above.

[Wiring resistance after development]
When the resistance was measured by the method described above after the development operation, the values of the three copper wirings were 11Ω, 13Ω, and 12Ω, respectively, and the average resistance value RB after development was _12Ω . From this, R _B /R _A was 1.1, and the evaluation was ⊚.

<Example 2>
[Manufacturing of Dispersion]
A dispersion was obtained in the same manner as in Example 1.
[Polishing of base material]
The surface of an ABS substrate having a size of 50 mm×50 mm×1 mm (width×depth×thickness) was polished with #2000 polishing paper. After polishing, the arithmetic mean surface roughness Ra was measured to be 245 nm.
[Application and drying of dispersion]
Coating and drying were performed by the method described in Example 1.
[Laser beam irradiation]
Laser light irradiation was performed in the same manner as in Example 1.
[Wiring resistance after laser beam irradiation]
When the resistance of the obtained metal wiring was measured by the method described above, the three copper wirings were 6.5Ω, 7.3Ω, and 7.2Ω, respectively, and the average resistance value RA before development was _7.0Ω . there were.
[Developability of structure]
After the laser beam irradiation, the structure with a conductive portion was immersed in 50 ml of a 2% by mass DISPERBYK-145 aqueous solution (first developer) (23° C.), and cleaned with an ultrasonic cleaner (USD-4R manufactured by AS ONE) for 5 minutes. After ultrasonic irradiation for minutes, the structure was pulled up with tweezers and washed with 50 ml of ultrapure water under running water. After that, it was newly immersed in 50 ml of ethanol (second developer) (at 23° C.) and irradiated with ultrasonic waves for 5 minutes.
After the above developing operation, the copper concentration in the portion where the metal wiring was not present on the substrate was measured by the method described above, and the result was 8.6% by mass, and the evaluation was ◯.
[Wiring resistance after development]
When the resistance was measured by the method described above after the developing operation, the three copper wirings were 8.9Ω, 7.3Ω, and 7.3Ω, respectively, and the average resistance value RB after development was _7.8Ω . From this, R _B /R _A was 1.1, and the evaluation was ⊚.

<Example 3>
[Manufacturing of Dispersion]
A dispersion was obtained in the same manner as in Example 1.
[Polishing of base material]
The surface of an ABS substrate having a size of 50 mm×50 mm×1 mm (width×depth×thickness) was polished with #2000 polishing paper. After polishing, the arithmetic mean surface roughness Ra was measured to be 267 nm.
[Application and drying of dispersion]
Coating and drying were performed by the method described in Example 1.
[Laser beam irradiation]
Laser light irradiation was performed in the same manner as in Example 1.
[Wiring resistance after laser beam irradiation]
When the resistance of the obtained metal wiring was measured by the method described above, the three copper wirings were 4.8 Ω, 6.2 Ω, and 5.7 Ω, respectively, and the average resistance value _RA before development was 5.6 Ω. there were.
[Developability of structure]
Developed by the method described in Example 1, except that the first developer was a 0.1% by mass DISPERBYK-145 aqueous solution, and the ultrasonic irradiation time in the first developer was 1 minute. performed the operation.
After the above developing operation, the copper concentration in the portion where the metal wiring was not present on the substrate was measured by the method described above, and the result was 2.3% by mass, and the evaluation was ◯.
[Wiring resistance after development]
When the resistance was measured by the method described above after the developing operation, the values of the three copper wirings were 6.8Ω, 5.5Ω, and 7.4Ω, respectively, and the average resistance value RB after development was _6.6Ω . From this, R _B /R _A was 1.2, and the evaluation was ⊚.

<Example 4>
[Manufacturing of Dispersion]
A dispersion was obtained in the same manner as in Example 1.
[Polishing of base material]
The surface of an ABS substrate having a size of 50 mm×50 mm×1 mm (width×depth×thickness) was polished with #2000 polishing paper. After polishing, the arithmetic mean surface roughness Ra was measured to be 185 nm.
[Application and drying of dispersion]
Coating and drying were performed by the method described in Example 1.
[Laser beam irradiation]
Laser light irradiation was performed in the same manner as in Example 1.
[Wiring resistance after laser beam irradiation]
When the resistance of the obtained metal wiring was measured by the method described above, the three copper wirings were 9.0 Ω, 12 Ω, and 8.3 Ω, respectively, and the average resistance value _RA before development was 9.9 Ω. .
[Developability of structure]
Developing operation was performed by the method described in Example 1, except that the first developer was a 20% by mass DISPERBYK-145 aqueous solution, and the ultrasonic irradiation time in the first developer was 1 minute. gone.
After the above developing operation, the copper concentration in the portion where the metal wiring was not present on the substrate was measured by the method described above.
[Wiring resistance after development]
When the resistance was measured by the method described above after the developing operation, the values of the three copper wirings were 11Ω, 27Ω, and _8.5Ω , respectively, and the average resistance value RB after development was 16Ω. From this, R _B /R _A was 1.6, and the evaluation was ⊚.

<Example 5>
[Manufacturing of Dispersion]
A dispersion was obtained in the same manner as in Example 1.
[Polishing of base material]
The surface of an ABS substrate having a size of 50 mm×50 mm×1 mm (width×depth×thickness) was polished with #2000 polishing paper. After polishing, the arithmetic mean surface roughness Ra was measured to be 235 nm.
[Application and drying of dispersion]
Coating and drying were performed by the method described in Example 1.
[Laser beam irradiation]
Laser light irradiation was performed in the same manner as in Example 1.
[Wiring resistance after laser beam irradiation]
When the resistance of the obtained metal wiring was measured by the method described above, the three copper wirings were 19Ω, 21Ω, and 26Ω, respectively, and the average resistance value RA before development was _22Ω .
[Developability of structure]
After the laser beam irradiation, the structure with a conductive portion was immersed in 50 ml of a 20% by mass DISPERBYK-145 aqueous solution (first developer) (at 23° C.) and cleaned with an ultrasonic cleaner (USD-4R manufactured by AS ONE) for 1 minute. After ultrasonic irradiation for minutes, the structure was pulled up with tweezers and washed with 50 ml of ultrapure water under running water. After that, the structure was newly immersed in 50 ml (23° C.) of a 5% by mass diethylenetriamine aqueous solution (second developer) and irradiated with ultrasonic waves for 1 minute. was washed with running water. Further, the structure was newly immersed in 50 ml (23° C.) of a 5% by mass diethylenetriamine aqueous solution (third developer) and irradiated with ultrasonic waves for 1 minute. was washed with running water.
After the above developing operation, the copper concentration in the portion where the metal wiring was not present on the base material was measured by the method described above.
[Wiring resistance after development]
When the resistance was measured by the method described above after the development operation, the three copper wirings were 25Ω, 34Ω, and 31Ω, respectively, and the average resistance value RB after development was _30Ω . From this, R _B /R _A was 1.4, and the evaluation was ⊚.

<Example 6>
[Manufacturing of Dispersion]
In a mixed solvent consisting of 30240 g of water and 13980 g of 1,2-propylene glycol (manufactured by Asahi Glass Co., Ltd.), 3230 g of copper (II) acetate monohydrate (manufactured by Nihon Kagaku Sangyo Co., Ltd.) is dissolved, hydrazine hydrate (manufactured by Nippon Finechem Co., Ltd.). After adding 940 g and stirring in a nitrogen atmosphere, the mixture was separated into a supernatant and a precipitate using centrifugation.
87 g of the liquid for mixing was added to 38 g of the obtained precipitate and dispersed using a homogenizer in a nitrogen atmosphere to obtain a dispersion containing cuprous oxide particles containing cuprous oxide (copper (I) oxide). rice field. The mixed solution was prepared by adding 131 g of DISPERBYK-118 (trade name, manufactured by BYK-Chemie) (BYK-118) as a phosphorus-containing organic compound and 8 g of Mix Ether (manufactured by Sankyo Chemical Co., Ltd.) as a dispersion medium. The solid content residue (cuprous oxide particles) when the dispersion was heated at normal pressure at 60° C. for 4.5 hours was 26.2 mass %.

[Polishing of base material]
The surface of an ABS substrate having a size of 50 mm×50 mm×1 mm (width×depth×thickness) was polished with #2000 polishing paper. After polishing, the arithmetic mean surface roughness Ra was measured to be 205 nm.
[Application and drying of dispersion]
Coating and drying were performed by the method described in Example 1.
[Laser beam irradiation]
Laser light irradiation was performed in the same manner as in Example 1.
[Wiring resistance after laser beam irradiation]
When the resistance of the obtained metal wiring was measured by the method described above, the three copper wirings were 13Ω, 21Ω, and 31Ω, respectively, and the average resistance value RA before development was _22Ω .
[Developability of structure]
The developing operation was performed by the method described in Example 1, except that the first developer was a 2% by mass DISPERBYK-118 aqueous solution, and the ultrasonic irradiation time in the first developer was 1 minute. gone.
After the above developing operation, the copper concentration of the portion where the metal wiring was not present on the base material was measured by the method described above.
[Wiring resistance after development]
When the resistance was measured by the method described above after the developing operation, the values of the three copper wirings were 17Ω, 27Ω, and _37Ω , respectively, and the average resistance value RB after development was 27Ω. From this, R _B /R _A was 1.2, and the evaluation was ⊚.

<Example 7>
[Manufacturing of Dispersion]
A dispersion was obtained in the same manner as in Example 1.
[Polishing of base material]
The surface of an ABS substrate having a size of 50 mm×50 mm×1 mm (width×depth×thickness) was polished with #2000 polishing paper. After polishing, the arithmetic mean surface roughness Ra was measured to be 208 nm.
[Application and drying of dispersion]
Coating and drying were performed by the method described in Example 1.
[Laser beam irradiation]
Laser light irradiation was performed in the same manner as in Example 1.
[Wiring resistance after laser beam irradiation]
When the resistance of the obtained metal wiring was measured by the method described above, the three copper wirings were 10 Ω, 4.0 Ω, and 5.8 Ω, respectively, and the average resistance value _RA before development was 6.6 Ω. .
[Developability of structure]
Example except that the first developer was a 2% by mass DISPERBYK-145 ethanol solution (first developer), and the ultrasonic irradiation time in the first developer was 1 minute. Developing operation was carried out by the method described in Section 1 above.
After the above developing operation, the copper concentration in the portion where the metal wiring was not present on the substrate was measured by the method described above, and the result was 5.1% by mass, and the evaluation was ◯.
[Wiring resistance after development]
When the resistance was measured by the method described above after the developing operation, the three copper wirings were 18Ω, 13Ω, and 6.2Ω, respectively, and the average resistance value RB after development was _12Ω . From this, R _B /R _A was 1.9, and the evaluation was ⊚.

<Example 8>
[Manufacturing of Dispersion]
A dispersion was obtained in the same manner as in Example 1.
[Polishing of base material]
The surface of an ABS substrate having a size of 50 mm×50 mm×1 mm (width×depth×thickness) was polished with #2000 polishing paper. After polishing, the arithmetic mean surface roughness Ra was measured to be 285 nm.
[Application and drying of dispersion]
Coating and drying were performed by the method described in Example 1.
[Laser beam irradiation]
Laser light irradiation was performed in the same manner as in Example 1.
[Wiring resistance after laser beam irradiation]
When the resistance of the obtained metal wiring was measured by the method described above, the three copper wirings were 10 Ω, 7.5 Ω, and 6.5 Ω, respectively, and the average resistance value _RA before development was 8.0 Ω. .
[Developability of structure]
Developing operation by the method described in Example 1 except that the ultrasonic irradiation time in the first developer was 1 minute and the second developer was a 5% by mass 2-aminoethanol aqueous solution. did
After the above development operation, the copper concentration in the portion where the metal wiring was not present on the substrate was measured by the method described above, and the result was 2.8% by mass, and the evaluation was ◯.
[Wiring resistance after development]
When the resistance was measured by the method described above after the developing operation, the three copper wirings were 23Ω, 7.4Ω, and 11Ω, respectively, and the average resistance value RB after development was _14Ω . From this, R _B /R _A was 1.7, and the evaluation was ⊚.

<Example 9>
[Manufacturing of Dispersion]
A dispersion was obtained in the same manner as in Example 1.
[Polishing of base material]
The surface of an ABS substrate having a size of 50 mm×50 mm×1 mm (width×depth×thickness) was polished with #2000 abrasive paper. After polishing, the arithmetic mean surface roughness Ra was measured to be 175 nm.
[Application and drying of dispersion]
Coating and drying were performed by the method described in Example 1.
[Laser beam irradiation]
Laser light irradiation was performed in the same manner as in Example 1.
[Wiring resistance after laser beam irradiation]
When the resistance of the obtained metal wiring was measured by the method described above, the three copper wirings were 6.5 Ω, 7.1 Ω, and 6.5 Ω, respectively, and the average resistance value _RA before development was 6.7 Ω. there were.
[Developability of structure]
Developing operation by the method described in Example 1, except that the first developer was a 2% by mass DISPERBYK-118 aqueous solution, and the ultrasonic irradiation time in the first developer was 1 minute. did
After the above developing operation, the copper concentration of the portion where the metal wiring was not present on the substrate was measured by the method described above, and the result was 6.3% by mass, and the evaluation was ◯.
[Wiring resistance after development]
When the resistance was measured by the method described above after the development operation, the values of the three copper wirings were 8.5Ω, 7.8Ω, and 8.2Ω, respectively, and the average resistance value RB after development was _8.2Ω . From this, R _B /R _A was 1.2, and the evaluation was ⊚.

<Example 10>
[Manufacturing of Dispersion]
A dispersion was obtained in the same manner as in Example 1.
[Polishing of base material]
The surface of an ABS substrate having a size of 50 mm×50 mm×1 mm (width×depth×thickness) was polished with #2000 polishing paper. After polishing, the arithmetic mean surface roughness Ra was measured to be 227 nm.
[Application and drying of dispersion]
Coating and drying were performed by the method described in Example 1.
[Laser beam irradiation]
Laser light irradiation was performed in the same manner as in Example 1.
[Wiring resistance after laser beam irradiation]
When the resistance of the obtained metal wiring was measured by the method described above, the three copper wirings were 10Ω, 9.8Ω, and 23Ω, respectively, and the average resistance value RA before development was _14Ω .
[Developability of structure]
Developing operation by the method described in Example 1 except that the ultrasonic irradiation time in the first developer was 1 minute and the second developer was a 5% by mass N-methyldiethanolamine aqueous solution. did
After the above developing operation, the copper concentration in the portion where the metal wiring was not present on the substrate was measured by the method described above, and the result was 9.4% by mass, and the evaluation was ◯.
[Wiring resistance after development]
When the resistance was measured by the method described above after the development operation, the values of the three copper wirings were 13Ω, 12Ω, and _23Ω , respectively, and the average resistance value RB after development was 16Ω. From this, R _B /R _A was 1.1, and the evaluation was ⊚.

<Example 11>
[Manufacturing of Dispersion]
A dispersion was obtained in the same manner as in Example 1.
[Polishing of base material]
The surface of an ABS substrate having a size of 50 mm×50 mm×1 mm (width×depth×thickness) was polished with #2000 polishing paper. After polishing, the arithmetic mean surface roughness Ra was measured to be 139 nm.
[Application and drying of dispersion]
Coating and drying were performed by the method described in Example 1.
[Laser beam irradiation]
Laser light irradiation was performed in the same manner as in Example 1.
[Wiring resistance after laser beam irradiation]
When the resistance of the obtained metal wiring was measured by the method described above, the three copper wirings were 3.3Ω, 2.4Ω, and 5.7Ω, respectively, and the average resistance value RA before development was _3.8Ω . there were.
[Developability of structure]
The developing operation was performed by the method described in Example 1, except that the second developer was a 2% by mass DISPERBYK-145 aqueous solution, and the ultrasonic irradiation time in the second developer was 15 minutes. gone.
After the above developing operation, the copper concentration in the portion where the metal wiring was not present on the base material was measured by the method described above.
[Wiring resistance after development]
When the resistance was measured by the method described above after the developing operation, the values of the three copper wirings were 21Ω, 13Ω, and 16Ω, respectively, and the average resistance value RB after development was _17Ω . From this, R _B /R _A was 4.5, and the evaluation was ○.

<Example 12>
[Manufacturing of Dispersion]
A dispersion was obtained in the same manner as in Example 1.
[Polishing of base material]
The surface of an ABS substrate having a size of 50 mm×50 mm×1 mm (width×depth×thickness) was polished with #2000 abrasive paper. After polishing, the arithmetic mean surface roughness Ra was measured to be 212 nm.
[Application and drying of dispersion]
Coating and drying were performed by the method described in Example 1.
[Laser beam irradiation]
Laser light irradiation was performed in the same manner as in Example 1.
[Wiring resistance after laser beam irradiation]
When the resistance of the obtained metal wiring was measured by the method described above, the three copper wirings were 11Ω, 18Ω, and 18Ω, respectively, and the average resistance value _RA before development was 16Ω.
[Developability of structure]
Except that the first developer was ultrapure water, the ultrasonic irradiation time in the first developer was 1 minute, and the second developer was a 2% by mass DISPERBYK-145 aqueous solution was developed by the method described in Example 1.
After the above developing operation, the copper concentration in the portion where the metal wiring was not present on the substrate was measured by the method described above.
[Wiring resistance after development]
When the resistance was measured by the method described above after the developing operation, the values of the three copper wirings were 26Ω, 27Ω, and 16Ω, respectively, and the average resistance value RB after development was _22Ω . From this, R _B /R _A was 1.4, and the evaluation was ⊚.

[Preparation of Regenerated Dispersion]
After collecting the first developer after the development operation, it was heated and concentrated at 80° C. to 8 ml to obtain a regenerated dispersion.
[Coating and Drying of Regenerated Dispersion]
1 ml of the regenerated dispersion was dropped onto an ABS substrate having an Ra of 6 nm, and dried by heating at 80° C. for 60 minutes. After drying, it was stored for 10 minutes in a room under normal pressure, room temperature of 23° C. and relative humidity of 40% to obtain a sample having a dry coating film formed on the substrate.
[Laser beam irradiation]
Laser light irradiation was performed in the same manner as in Example 1, except that the output was 135 mW and only one copper wiring was formed.
[Wiring resistance after laser beam irradiation]
When the resistance of the obtained metal wiring was measured by the method described above, it was 1.0 Ω.

<Example 13>
[Manufacturing of Dispersion]
In a mixed solvent consisting of 30240 g of water and 13976 g of 1,2-propylene glycol (manufactured by Asahi Glass Co., Ltd.), 3224 g of copper (II) acetate monohydrate (manufactured by Nihon Kagaku Sangyo Co., Ltd.) is dissolved, and hydrazine hydrate (manufactured by Nippon Finechem Co., Ltd.) is dissolved. After adding 940 g and stirring, the mixture was separated into a supernatant and a precipitate using centrifugation.
To 388 g of the obtained precipitate, 51 g of DISPERBYK-145 (trade name, manufactured by BYK-Chemie) (BYK-145) as a phosphorus-containing organic compound and 415 g of n-butanol (manufactured by Sankyo Chemical Co., Ltd.) as a dispersion medium were added. A dispersion containing cuprous oxide particles containing cuprous oxide (copper(I) oxide) was obtained by dispersing using a homogenizer. Further, 7.3 g of BYK-145 and 115 g of n-butanol were added to 788 g of the resulting dispersion, and dispersed using a homogenizer under a nitrogen atmosphere to obtain the desired dispersion. At this time, the solid content residue (cuprous oxide particles) when the dispersion was heated at normal pressure at 60° C. for 4.5 hours was 35.9 mass %. The surface free energy of the dispersion was measured to be 23 mNm.

[Polishing of base material]
Polycarbonate (PC) substrates of width x depth x thickness of 50 mm x 50 mm x 1 mm were used without polishing. Arithmetic mean surface roughness Ra was measured to be 4 nm.
[Application and drying of dispersion]
The substrate after polishing was cleaned by irradiating ultrasonic waves in ultrapure water for 5 minutes and then in ethanol for 5 minutes. Next, after the surface of the substrate was subjected to UV ozone treatment, 1 ml of the dispersion was added dropwise to the surface and dried by heating at 60° C. for 2 hours. After drying, it was stored for 10 minutes in a room under normal pressure, room temperature of 23° C. and relative humidity of 40% to obtain a sample having a dry coating film formed on the substrate.
[Laser beam irradiation]
Laser light irradiation was performed in the same manner as in Example 1, except that the output was 395 mW.
[Wiring resistance after laser beam irradiation]
When the resistance of the obtained metal wiring was measured by the method described above, the three copper wirings were 0.17 Ω, 0.17 Ω, and 0.18 Ω, respectively, and the average resistance value _RA before development was 0.17 Ω. there were.
[Developability of structure]
The first developer was 30 ml of an aqueous solution of DISPERBYK-145 with a concentration of 0.1% by mass, the amount of the second developer was 30 ml, and the ultrasonic irradiation time in the second developer was 5 minutes. The development operation was carried out in the same manner as in Example 1 except for the above.
After the above developing operation, the copper concentration in the portion where the metal wiring was not present on the base material was measured by the method described above.
[Wiring resistance after development]
When the resistance was measured by the method described above after the developing operation, it was 0.16Ω, 0.15Ω, and 0.15Ω for the three copper wirings, respectively, and the average resistance value RB after development was _0.15Ω . From this, R _B /R _A was 0.9, and the evaluation was ⊚.
[Preparation of Regenerated Dispersion]
After collecting the first developer after the development operation, it was heated and concentrated at 60° C. to 10 ml to obtain a regenerated dispersion.
[Coating and Drying of Regenerated Dispersion]
1 ml of the regenerated dispersion was dropped onto a PC substrate having an Ra of 3 nm, and dried by heating at 60° C. for 30 minutes. After drying, it was stored for 10 minutes in a room under normal pressure, room temperature of 23° C. and relative humidity of 40% to obtain a sample having a dry coating film formed on the substrate.
[Laser beam irradiation]
Laser light irradiation was performed in the same manner as in Example 1, except that the output was 135 mW and only one copper wiring was formed.
[Wiring resistance after laser beam irradiation]
The resistance of the resulting metal wiring was measured by the method described above and found to be 1.1 Ω.

<Example 14>
[Manufacturing of Dispersion]
A dispersion was prepared in the same manner as in Example 1.
[Polishing of base material]
The surface of an ABS substrate of width x depth x thickness of 50 mm x 50 mm x 1 mm was not polished. The measured arithmetic mean surface roughness Ra was 256 nm.
[Application and drying of dispersion]
Coating was performed in the same manner as in Example 1.
[Laser beam irradiation]
Laser light irradiation was performed in the same manner as in Example 1.
[Wiring resistance measurement after laser beam irradiation]
When the resistance was measured by the method described above, the three copper wirings were 6.3Ω, 6.5Ω, and 8.4Ω, respectively, and the average resistance value RA before development was _7.1Ω .
[Developability of structure]
After irradiating the laser beam, the structure with a conductive portion is immersed in 50 ml of ultrapure water (23° C.), subjected to ultrasonic irradiation for 5 minutes in an ultrasonic cleaner (USD-4R manufactured by AS ONE), and then removed with tweezers. It was pulled up and washed with running water with 50 ml of ultrapure water. After that, the structure was newly immersed in 50 ml of ultrapure water (23° C.) and irradiated with ultrasonic waves for 5 minutes.
After the above developing operation, the copper concentration of the portion where the metal wiring was not present on the substrate was measured by the method described above, and the result was 13.3% by mass, and the evaluation was ◯.
[Measurement of wiring resistance after development]
When the resistance was measured by the method described above after the developing operation, it was 6.6Ω, 7.5Ω, and 8.9Ω for the three copper wirings, and the average value was 7.7Ω. From this, R _B /R _A was 1.1, and the evaluation was ⊚.

<Example 15>
[Manufacturing of Dispersion]
A dispersion was prepared in the same manner as in Example 1.
[Polishing of base material]
The surface of an ABS substrate of width x depth x thickness of 50 mm x 50 mm x 1 mm was not polished. The measured arithmetic mean surface roughness Ra was 236 nm.
[Application and drying of dispersion]
Coating was performed in the same manner as in Example 1.
[Laser beam irradiation]
Laser light irradiation was performed in the same manner as in Example 1.
[Wiring resistance measurement after laser beam irradiation]
When the resistance was measured by the method described above, the three copper wirings were 36Ω, _35Ω , and 28Ω, respectively, and the average resistance value RA before development was 33Ω.
[Developability of structure]
The developing operation was carried out by the method described in Example 1 except that the ultrasonic irradiation time in the first development was set to 1 minute and ultrapure water was used as the second developer.
After the above developing operation, the copper concentration in the portion where the metal wiring was not present on the substrate was measured by the method described above, and the result was 10.4% by mass, and the evaluation was ◯.
[Measurement of wiring resistance after development]
When the resistance was measured by the method described above after the developing operation, the values of the three copper wirings were 41Ω, 31Ω, and 33Ω, respectively, and the average value was 37Ω. From this, R _B /R _A was 1.1, and the evaluation was ⊚.

<Example 16>
[Manufacturing of Dispersion]
A dispersion was prepared in the same manner as in Example 13.
[Polishing of base material]
The surface of an ABS substrate measuring 50 mm×50 mm×1 mm (width×depth×thickness) was polished with #2000 abrasive paper. After polishing, the arithmetic mean surface roughness Ra was measured to be 186 nm.
[Application and drying of dispersion]
Coating was performed in the same manner as in Example 13.
[Laser beam irradiation]
Laser light irradiation was performed in the same manner as in Example 13.
[Wiring resistance measurement after laser beam irradiation]
When the resistance was measured by the method described above, the three copper wirings were 0.18Ω, 0.17Ω, and 0.17Ω, respectively, and the average resistance value RA before development was _0.17Ω .
[Developability of structure]
Development was carried out in the same manner as in Example 13.
After the above developing operation, the copper concentration of the portion where the metal wiring was not present on the base material was measured by the method described above.
[Measurement of wiring resistance after development]
When the resistance was measured by the above-described method after the development operation, it was 0.19Ω, 0.15Ω, and 0.15Ω for the three copper wirings, respectively, and the average resistance value RB after development was _0.16Ω . From this, R _B /R _A was 0.9, and the evaluation was ⊚.
[Preparation of Regenerated Dispersion]
After collecting the first developer after the development operation, it was heated and concentrated at 60° C. to 10 ml to obtain a regenerated dispersion.
[Coating and Drying of Regenerated Dispersion]
1 ml of the regenerated dispersion was dropped onto an ABS substrate having an Ra of 6 nm, and dried by heating at 80° C. for 60 minutes. After drying, it was stored for 10 minutes in a room under normal pressure, room temperature of 23° C. and relative humidity of 40% to obtain a sample having a dry coating film formed on the substrate.
[Laser beam irradiation]
Laser light irradiation was performed in the same manner as in Example 1, except that the output was 135 mW and only one copper wiring was formed.
[Wiring resistance after laser beam irradiation]
When the resistance of the obtained metal wiring was measured by the method described above, it was 1.0 Ω.

<Comparative Example 1>
[Manufacturing of Dispersion]
A dispersion was prepared in the same manner as in Example 1.
[Polishing of base material]
The surface of an ABS substrate of width x depth x thickness of 50 mm x 50 mm x 1 mm was not polished. The measured arithmetic mean surface roughness Ra was 230 nm.
[Application and drying of dispersion]
Coating was performed in the same manner as in Example 1.
[Laser beam irradiation]
Laser light irradiation was performed in the same manner as in Example 1.
[Wiring resistance measurement after laser beam irradiation]
When the resistance was measured by the method described above, the three copper wirings were 5.5Ω, 4.6Ω, and 5.0Ω, respectively, and the average resistance value RA before development was _5.0Ω .
[Developability of structure]
After irradiating the laser beam, the structure with a conductive portion is immersed in 50 ml of ultrapure water (23° C.), subjected to ultrasonic irradiation for 5 minutes in an ultrasonic cleaner (USD-4R manufactured by AS ONE), and then removed with tweezers. It was pulled up and washed with running water with 50 ml of ultrapure water.
After the above developing operation, the copper concentration of the portion where the metal wiring was not present on the base material was measured by the method described above.
[Measurement of wiring resistance after development]
When the resistance was measured by the method described above after the developing operation, it was 6.5Ω, 6.8Ω, and 5.9Ω for the three copper wirings, and the average value was 6.4Ω. From this, R _B /R _A was 1.3, and the evaluation was ⊚.

<Comparative Example 2>
[Manufacturing of Dispersion]
A dispersion was prepared in the same manner as in Example 1.
[Polishing of base material]
The surface of an ABS substrate of width x depth x thickness of 50 mm x 50 mm x 1 mm was not polished. The measured arithmetic mean surface roughness Ra was 327 nm.
[Application and drying of dispersion]
Coating was performed in the same manner as in Example 1.
[Laser beam irradiation]
Laser light irradiation was performed in the same manner as in Example 1.
[Wiring resistance measurement after laser beam irradiation]
When the resistance was measured by the method described above, the three copper wirings were 21Ω, 15Ω, and 27Ω, respectively, and the average resistance value RA before development was _21Ω .
[Developability of structure]
Example except that the first developer was a 25% by mass DISPERBYK-145 aqueous solution, the ultrasonic irradiation time in the first development was 1 minute, and the second development was not performed. Developing operation was carried out by the method described in Section 1 above.
After the above developing operation, the copper concentration of the portion where the metal wiring was not present on the base material was measured by the method described above.
[Measurement of wiring resistance after development]
When the resistance was measured by the method described above after the developing operation, the values of the three copper wirings were 14Ω, 16Ω, and 34Ω, respectively, and the average value was 21Ω. From this, R _B /R _A was 1.0, and the evaluation was ⊚.

The above results are summarized in Tables 1 and 2. The level of developability is best in Examples 1, 5, 11, 13 and 16, followed by Examples 2-4, 6-10 and 12. , 14, 15. In Comparative Examples 1 and 2, the concentration of copper remaining in the substrate after development was high, and the development was not sufficient.

According to the present invention, the metal particles and/or metal oxide particles in the unexposed portion can be efficiently removed in the development step, and the resistance value changes little before and after the development. It is possible to provide a structure with low resistance metal wiring that can avoid problems such as short circuits due to external deposition and migration. Also, according to certain aspects of the present invention, waste can be reduced by recycling the developer.

Such a structure with metal wiring can be suitably used for metal wiring materials such as electronic circuit boards, mesh electrodes, electromagnetic shielding materials, heat dissipation materials, and the like.

R1 First scanning line R2 Second scanning line S1 Width S2 Width 11, 21, 31 Containers 12, 22, 32 Jig 12a Racks 22a, 32a Recesses 13, 23, 33 Structures with conductive parts 13a, 23a , 33a base material 13b, 23b, 33b post-irradiation coating film 100 metal wiring manufacturing system 101 coating mechanism 102 drying mechanism 103 laser beam irradiation mechanism 104 developing mechanism 104a first developing section 104b second developing section 105 developer recycling mechanism

Claims (21)

a coating step of coating a dispersion containing particle components that are metal particles and/or metal oxide particles on the surface of a substrate to form a dispersion layer;
a drying step of drying the dispersion layer to form a structure with a dry coating film having the base material and a dry coating film disposed on the base material;
A laser beam irradiation step of irradiating the dry coating film with a laser beam to form a metal wiring;
and a developing step of developing and removing the area of the dry coating film other than the metal wiring with a developer,
The developing step
(1) a first development process of developing the dry coating film with a first developer; and (2) a second development process of developing the dry coating film with a second developer;
including
A method for manufacturing metal wiring, wherein each of the first developer and the second developer contains water and/or an organic solvent. The first developer contains water and/or an alcoholic solvent,
2. The method for manufacturing metal wiring according to claim 1, wherein said second developer contains an organic solvent. 3. The method for manufacturing metal wiring according to claim 1, wherein said first developer and/or said second developer contain an alcoholic solvent. 4. The method for manufacturing metal wiring according to claim 1, wherein said first developer and/or said second developer contain an amine solvent. 5. The method for manufacturing metal wiring according to claim 4, wherein the amine-based solvent contains diethylenetriamine and/or 2-aminoethanol. The metal according to any one of claims 1 to 5, wherein the first developer and / or the second developer contains 0.1% by mass or more and 20% by mass or less of a dispersant (A). Wiring manufacturing method. 7. The method for manufacturing metal wiring according to claim 6, wherein the dispersant (A) is a phosphorus-containing organic compound. 8. The method of manufacturing metal wiring according to claim 6, wherein said dispersion contains a dispersant (B), and said dispersant (A) and said dispersant (B) have the same main components. The metal wiring according to any one of claims 1 to 8, wherein the difference between the surface free energy of the first developer and the surface free energy of the dispersion is 0 mN/m or more and 50 mN/m or less. Production method. 10. The method for manufacturing metal wiring according to claim 1, wherein the solubility of the particle component in the second developer is higher than the solubility of the particle component in the first developer. The method for producing a metal wiring according to any one of claims 1 to 10, wherein the particle component is copper particles and/or copper oxide particles. 12. The method of manufacturing a metal wiring according to claim 11, wherein the particle component has a solubility value of 0.1 mg/L or more and 10000 mg/L or less in the second developer. 13. The method for manufacturing a metal wiring according to claim 1, further comprising a step of collecting used developer after the developing step. 14. The method for manufacturing metal wiring according to claim 1, wherein the dispersion is prepared from a liquid containing a used developer collected after the developing step. A kit comprising a structure with a dry coating and a developer,
The structure with a dry coating has a substrate and a dry coating containing a particle component that is metal particles and/or metal oxide particles disposed on the surface of the substrate,
the developer comprises a first developer and a second developer;
A kit, wherein each of the first developer and the second developer contains water and/or an organic solvent. 16. The kit according to claim 15, wherein said organic solvent is an alcoholic solvent. 17. The kit according to claim 15 or 16, wherein said first developer and/or said second developer contain 0.1% by mass or more and 20% by mass or less of dispersant (A). 18. The kit according to claim 17, wherein the dry coating contains a dispersant (B), and the main components of the dispersant (A) and the dispersant (B) are the same. a coating mechanism for coating a dispersion containing a particle component that is metal particles and/or metal oxide particles on the surface of a substrate to form a dispersion layer;
a drying mechanism for drying the dispersion layer to form a structure with a dry coating film having the base material and a dry coating film disposed on the base material;
A laser light irradiation mechanism for forming a metal wiring by irradiating the dry coating film with a laser light;
a developing mechanism that develops and removes a region of the dry coating film other than the metal wiring with a developer;
A metal wiring manufacturing system comprising:
The developing mechanism
(1) a first development station that develops the dry coating with a first developer; and (2) a second development station that develops the dry coating with a second developer;
has
A metal wiring manufacturing system, wherein each of the first developer and the second developer contains water and/or an organic solvent. 20. The metal wiring manufacturing system according to claim 19, wherein said organic solvent is an alcoholic solvent. 21. The metal wiring manufacturing system according to claim 19 or 20, wherein said first developer and/or said second developer contain 0.1% by mass or more and 20% by mass or less of dispersant (A).

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