JP2023057021A - Manufacturing method of structure with conductive pattern, kit, and system - Google Patents

Abstract

To provide a manufacturing method of a structure with a conductive pattern capable of forming the structure with the conductive pattern having a good interlayer adhesion.SOLUTION: A manufacturing method of a structure with a conductive pattern includes: a coating film forming step where a coating film is obtained by applying particles containing a metal compound and/or a dispersion containing the particles containing a metal; and a pre-treatment step and/or a post-treatment step. The pre-treatment step is a step in which, before the coating film formation step, one or more treatments selected from the group consisting of a UV ozone treatment, an organic solvent treatment, and an alkaline treatment is performed to the substrate. The post-treatment step is a step in which, after the coating film formation step, a humidification treatment and/or a heat treatment is performed.SELECTED DRAWING: Figure 2

Description

TECHNICAL FIELD The present invention relates to a method for manufacturing a structure with a conductive pattern.

A circuit board has a structure in which conductive wiring is provided on a base material. A method of manufacturing a circuit board is generally as follows. First, a photoresist is applied on a base material 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 circuit board 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, a direct printing technique for directly printing a desired wiring pattern on a base material with a dispersion in which metal or metal oxide particles are dispersed has attracted attention. This technique has a small number of steps, does not require the use of a photoresist material, and is highly productive. However, when metal particles are used, there may be a problem in stability due to oxidation of the metal particles themselves. On the other hand, when metal oxide particles are used, a reduction firing process is required to obtain conductivity, so the substrate that can be used is limited, and a reducing gas is required, resulting in high cost. There is a problem.

With respect to the above, for example, Patent Document 1 describes a method of forming a conductive film in which a conductive film having a predetermined pattern is formed on a substrate. In this method, a metal film containing metal particles is formed on a substrate by a droplet discharge method so as to have a pattern substantially equal to the pattern of the conductive film, and then electroless plating is performed at least once to deposit the metal film. A conductive film is obtained by forming a plated film so as to cover the surface of the film.

JP 2006-128228 A

The method described in Patent Document 1 attempts to form a conductive film having excellent conductivity and reliability by combining pattern formation using metal particles and plating. The adhesion between the substrate and/or the adhesion between the layers in the conductive film is still insufficient.
In view of such circumstances, an object of one aspect of the present invention is to provide a method for manufacturing a conductive patterned structure that can form a conductive patterned structure with good interlayer adhesion.

This disclosure includes the following items.
[Item 1]
A coating film forming step of coating a substrate with a dispersion containing the metal compound-containing particles and/or the metal-containing particles to obtain a coating film;
a pretreatment step and/or a posttreatment step;
A method for manufacturing a structure with a conductive pattern, comprising
The pretreatment step is a step of subjecting the substrate to one or more treatments selected from the group consisting of UV ozone treatment, organic solvent treatment, and alkali treatment before the coating film forming step,
The method for manufacturing a conductive patterned structure, wherein the post-treatment step is a step of performing a humidification treatment and/or a heat treatment after the coating film formation step.
[Item 2]
The method for manufacturing a conductive patterned structure according to item 1, wherein the pretreatment step is an organic solvent treatment using an organic solvent having an SP value of 7.5 or more and 12.6 or less.
[Item 3]
3. The method for producing a conductive patterned structure according to item 2, wherein the SP value of the organic solvent is 9.9 or more and 11.6 or less.
[Item 4]
4. The method for producing a conductive patterned structure according to item 2 or 3, wherein the organic solvent contains at least one selected from the group consisting of N-methylpyrrolidone, 1-propanol, and 1-heptanol.
[Item 5]
5. The method for producing a conductive patterned structure according to any one of items 2 to 4, wherein the organic solvent contains N-methylpyrrolidone.
[Item 6]
Any one of items 1 to 5, wherein the pretreatment step is an organic solvent treatment using an organic solvent in which the difference between the SP value of the substrate and the SP value of the organic solvent is 0.01 or more and 4.6 or less. and a method for manufacturing a structure with a conductive pattern.
[Item 7]
7. The method for producing a conductive patterned structure according to any one of items 1 to 6, further comprising a reduction step after the coating film forming step.
[Item 8]
8. A method for manufacturing a conductive patterned structure according to item 7, wherein the reduction step is a wet reduction step.
[Item 9]
9. The method for manufacturing a structure with a conductive pattern according to any one of items 1 to 8, further comprising a plating step of plating after the coating film forming step.
[Item 10]
10. The method for manufacturing a structure with a conductive pattern according to item 9, wherein a plating solution containing EDTA (ethylenediaminetetraacetic acid) is used in the plating step.
[Item 11]
11. The method for manufacturing a conductive patterned structure according to any one of items 1 to 10, further comprising a reduction step after the coating film forming step, and a plating step after the reduction step.
[Item 12]
12. The method for manufacturing a conductive patterned structure according to any one of items 1 to 11, including both the pretreatment step and the posttreatment step.
[Item 13]
13. The method for producing a conductive patterned structure according to any one of items 1 to 12, wherein the substrate is polyimide.
[Item 14]
14. The method for producing a conductive patterned structure according to any one of items 1 to 13, wherein the dispersion contains at least one selected from the group consisting of 1-hexanol, 1-heptanol and 1-octanol.
[Item 15]
15. The method for producing a conductive patterned structure according to any one of items 1 to 14, wherein the metal compound-containing particles and/or the metal-containing particles are copper oxide-containing particles and/or copper-containing particles.
[Item 16]
a dispersion containing metal compound-containing particles and/or metal-containing particles;
A plating solution containing EDTA (ethylenediaminetetraacetic acid), and a substrate subjected to one or more treatments selected from the group consisting of UV ozone treatment, organic solvent treatment, and alkali treatment,
A conductive patterned structure manufacturing kit, comprising:
[Item 17]
a dispersion containing metal compound-containing particles and/or metal-containing particles;
a plating solution containing EDTA (ethylenediaminetetraacetic acid);
one or more treating agents selected from the group consisting of organic solvents and alkaline treating agents; and a substrate;
A conductive patterned structure manufacturing kit, comprising:
[Item 18]
a dispersion comprising metal compound-containing particles and/or metal-containing particles, and an organic solvent for organic solvent treatment;
and the SP value of the organic solvent is 7.5 or more and 12.6 or less.
[Item 19]
19. The kit for producing a structure with a conductive pattern according to any one of items 16 to 18, wherein the metal compound-containing particles and/or the metal-containing particles are copper oxide-containing particles and/or copper-containing particles.
[Item 20]
A pretreatment mechanism for applying an organic solvent treatment to a substrate using an organic solvent having an SP value of 7.5 or more and 12.6 or less;
a coating mechanism for obtaining a coating film by coating a substrate with a dispersion containing metal compound-containing particles and/or metal-containing particles;
a plating mechanism for plating the coating film that has passed through the coating mechanism;
comprising
A manufacturing system for structures with conductive patterns.

According to one aspect of the present invention, it is possible to provide a method for manufacturing a structure with a conductive pattern, which can form a structure with a conductive pattern having good interlayer adhesion.

FIG. 3 is a schematic cross-sectional view showing the relationship between copper oxide and a phosphate ester salt in a dispersion that can be used in one embodiment of the present invention. It is a cross-sectional schematic diagram which shows the manufacturing procedure of the structure with a conductive pattern which concerns on one aspect|mode of this invention. It is a schematic diagram which shows an example of the laser irradiation apparatus for manufacturing a structure with a conductive pattern.

Embodiments of the present invention are exemplified below, but the present invention is not limited to these embodiments.

One aspect of the present invention provides a method of manufacturing a conductive patterned structure. In one aspect, the method comprises:
A coating film forming step of coating a substrate with a dispersion containing the metal compound-containing particles and/or the metal-containing particles to obtain a coating film;
a pretreatment step and/or a posttreatment step;
including.
In one aspect, the pretreatment step is a step of subjecting the substrate to one or more treatments selected from the group consisting of UV ozone treatment, organic solvent treatment, and alkali treatment before the coating film forming step. .
In one aspect, the post-treatment step is a step of performing a humidification treatment and/or a heat treatment after the coating film formation step.

The pretreatment process and post-treatment process each contribute to an improvement in interlayer adhesion between the base material and the metal compound and/or metal layer formed on the base material. In one aspect, one or both of the pre-treatment and post-treatment steps may be performed, preferably both. The method of this embodiment can be advantageous in reducing the resistance of the structure with a conductive pattern.
Preferred examples of each step are described below.

[Base material]
The substrate used in the present embodiment has a surface on which a coating film is formed, and can be exemplified by a substrate material for a circuit board sheet for forming a wiring pattern. The substrate may be composed of an inorganic material or an organic material, or a combination thereof, and may have an adhesion layer in one aspect.

Examples of inorganic materials include glasses such as soda lime glass, alkali-free glass, borosilicate glass, and quartz glass, and ceramic materials such as alumina.

Examples of organic materials include paper materials such as cellulose, and polymeric materials such as resin films. Polymer materials include polyimide (PI), polyester (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), etc.), polyethersulfone (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), polyphthalamide (PPA), polyethernitrile (PENt), polybenzimidazole (PBI), polycarbodiimide, silicone polymer (poly siloxane), 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, polyethylene (PE), poly Vinyl chloride (PVC), polyvinylidene fluoride (PVDF), polyetheretherketone (PEEK), phenol novolak, 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 the like. Polyimide (PI), polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are preferred from the viewpoint of flexibility and cost. Among them, polyimide (PI) is preferable because it has an imide bond and can satisfactorily exhibit the effect of improving adhesion by the pretreatment step and/or posttreatment step of the present disclosure.

The substrate may be, for example, a composite substrate such as a glass composite substrate, a glass epoxy substrate, a Teflon (registered trademark) substrate, an alumina substrate, a low temperature and low humidity co-fired ceramics (LTCC), a silicon wafer, or the like. .

The thickness of the substrate is preferably 1 μm or more, or 25 μm or more, and preferably 10 mm or less, or 1 mm or less, or 250 μm or less. When the thickness of the substrate is 250 μm or less, the produced electronic device can be made lightweight, space-saving, and flexible, which is preferable.

<Pretreatment process>
One aspect of the method of the present disclosure includes a pretreatment step for the purpose of improving adhesion between the substrate and the metal compound and/or metal layer. The pretreatment step is a step of subjecting the substrate to one or more treatments selected from the group consisting of UV ozone treatment, organic solvent treatment, and alkali treatment prior to the coating film forming step. By using two or more of the above treatments in combination, there is a tendency for the effect of improving the adhesion to be better.

UV ozone treatment is a treatment that promotes decomposition of organic matter adhering to the substrate surface with UV (ultraviolet) light and ozone generated thereby. The UV ozone treatment can improve the adhesion between the substrate and the metal compound and/or metal layer by exposing the functional groups inherent in the substrate to the surface. Substrates particularly suitable for UV ozone treatment are especially polyimides.

The UV ozone treatment can be carried out using a device such as a UV cleaning and reforming device and a slide type UV cleaning device (both of which are manufactured by Sen Special Light Source Co., Ltd., for example), a UV ozone cleaning and modifying device (eg, by Sun Energy Co., Ltd.), and the like. . The treatment conditions may be appropriately adjusted so that only the surface of the substrate is treated. For example, the UV ozone treatment time is preferably 1 minute or more, or 2 minutes or more, preferably 30 minutes or less, or 20 minutes or less.

Organic solvent treatment is a treatment in which the substrate is brought into contact with an organic solvent. The contact may be immersion of the substrate in an organic solvent, spraying of the organic solvent onto the substrate, etc., preferably immersion of the substrate in the organic solvent. As the organic solvent, a solvent that dissolves or swells the substrate is preferable. By bringing such a solvent into contact with the substrate under controlled conditions, it is possible to dissolve or swell only the surface of the substrate. From the viewpoint of effectively swelling the base material and improving adhesion, the solubility parameter of the organic solvent (hereinafter simply referred to as "SP value") is 7.5 or more and 16.0 or less. It is preferably 7.5 or more and 12.6 or less, and most preferably 9.9 or more and 11.6 or less. From the same viewpoint, the difference between the SP value of the base material and the SP value of the organic solvent is preferably 0.01 or more and 4.6 or less, more preferably 0.01 or more and 2.2 or less, It is most preferably 0.01 or more and 0.7 or less. The SP value in the present disclosure means the Hansen solubility parameter, and the unit is (cal/cm ³ ). The Hansen solubility parameter is the Hildebrand solubility parameter divided into three components, the dispersion force term (δD), the polar term (δP), and the hydrogen bond term (δH), and expressed in a three-dimensional space. Denoting the solubility parameter as δ, there is a relationship of δ ² =(δD) ² +(δP) ² +(δH) ² . Since two substances having similar SP values are likely to dissolve in each other, the use of an organic solvent having a SP value close to that of the base material can effectively swell the base material. For example, when polyimide is used as the base material, the SP value of polyimide is generally in the range of 12.0 to 12.1. For example, the SP value of pyromellitic anhydride-4,4 oxydianiline type polyimide Since it is 12.1, the polyimide base material can be effectively swollen when the SP value of the organic solvent is 7.5 or more and 16.0 or less. The SP value can be calculated using the Hoy method using software (Hoy Solubility Parameter Software manufactured by Computer Chemistry Consultancy). Specific examples of organic solvents include: amide solvents such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide; γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ- cyclic ester solvents such as caprolactone, ε-caprolactone and α-methyl-γ-butyrolactone; chain ester solvents such as butyl acetate, ethyl acetate and isobutyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate; Glycol solvents such as triethylene glycol; Glycol ether solvents such as ethyl cellosolve and butyl cellosolve; Glycol ester solvents such as propylene glycol methyl acetate, 2-methyl cellosolve acetate, ethyl cellosolve acetate and butyl cellosolve acetate; Phenolic solvents such as m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol; acetophenone, 1,3-dimethyl-2-imidazolidinone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclo Ketone solvents such as xanone, methyl ethyl ketone and acetone; Sulfone solvents such as sulfolane and dimethyl sulfoxide; Hydrocarbon solvents such as xylene, toluene, chlorobenzene, hexane and benzene; Halogen solvents such as chloroform; solvent; ether solvents such as tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether and diethylene glycol dimethyl ether; alcohol solvents such as ethanol, 1-propanol, 1-butanol, 2-butanol, 1-heptanol and 1-octanol; is preferred. In particular, when a polyimide base material is used, N-methylpyrrolidone, 1-propanol, and 1-heptanol are preferred, and N-methylpyrrolidone is most preferred, in terms of swelling the polyimide. By swelling the substrate, after the dispersion is applied to the substrate, an anchor effect works between the layer of the metal compound and/or the metal and the substrate, resulting in good adhesion therebetween.

The treatment conditions for the organic solvent treatment may be appropriately adjusted so that only the surface of the substrate is treated. For example, the immersion time is preferably 5 minutes or longer, or 10 minutes or longer, preferably 120 minutes. or less, or 60 minutes or less. The immersion temperature is preferably 10°C or higher, or 20°C or higher, and preferably 100°C or lower, or 60°C or lower.

Alkaline treatment is a treatment in which the substrate is brought into contact with an alkaline treatment agent. The contact may be immersion of the substrate in the alkaline treating agent, spraying of the alkaline treating agent on the substrate, or the like, preferably immersion of the substrate in the alkaline treating agent. Examples of the alkaline treating agent include potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, 2-aminoethanol aqueous solution, diethylenetriamine aqueous solution and the like. The pH of the alkaline treatment agent is preferably 8 or higher, or 9 or higher, or 10 or higher, and preferably 13 or lower. Alkaline treatment chemically modifies the base material surface to form a chemical structure capable of firmly holding the metal compound and/or metal layer on the base material surface. In one aspect, the base material surface is partially hydrolyzed by alkali treatment, and hydrogen-bonding functional groups such as hydroxy groups and carboxy groups are generated to form a metal compound and/or metal layer and the base material. A hydrogen bond is formed between and the adhesion is improved. For example, when using a polyimide base material, by cutting the imide bond of the polyimide by alkali treatment, the hydrogen bond by the amide site derived from the imide group, the metal (copper in one aspect) to the carboxylate anion generated by the cutting. Coordination, etc. improves the adhesion between the metal compound and/or metal layer and the substrate.

The treatment conditions for the alkali treatment may be appropriately adjusted so that only the surface of the substrate is treated. For example, the immersion time is preferably 5 minutes or longer, or 10 minutes or longer, and preferably 120 minutes or shorter. , or 60 minutes or less. The immersion temperature is preferably 10°C or higher, or 20°C or higher, and preferably 100°C or lower, or 60°C or lower.

<Coating film forming process>
In this step, a coating film is obtained by applying a dispersion containing metal compound-containing particles and/or metal-containing particles (also simply referred to as a dispersion in the present disclosure) to a substrate.

[Dispersion containing metal compound-containing particles and/or metal-containing particles]
In one aspect, the dispersion comprises metal compound-containing particles and/or metal-containing particles. The metal compound-containing particles are typically made of a metal compound, but may contain other components as long as the effects of the present invention are not impaired. Similarly, the metal-containing particles are typically made of metal, but may contain other components as long as they do not impair the effects of the present invention. The dispersion may further comprise a dispersion medium, dispersant and/or reducing agent.

The metal, in one aspect, is aluminum, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, ruthenium, rhodium, palladium, silver, indium, tin, antimony, iridium, platinum, gold, thallium. , lead, and bismuth, or an alloy or mixture of two or more. The metal is preferably copper or silver, and particularly preferably copper, from the viewpoints of stably producing particles having a particle size described later, having good conductivity, and being easy to handle.

The metal compound may be a compound of one or more metals as exemplified above. Examples of the metal compound include metal oxides and metal hydroxides, and oxides are preferred. The metal oxide is preferably copper oxide or silver oxide in that it can be easily reduced to form a uniform conductive pattern. Further, the metal oxide is preferably copper oxide because of its relatively high stability in air and its low cost availability and commercial advantages. As copper oxide, cuprous oxide and/or cupric oxide can be used. The copper oxide-containing particles may have a core/shell structure, and either the core or the shell may contain cuprous oxide and/or cupric oxide.

(copper oxide or copper)
Copper oxides include cuprous oxide (Cu ₂ O) and cupric oxide (CuO), with cuprous oxide being preferred. Cuprous oxide is also advantageous in that it is inexpensive compared to noble metals such as silver because it is copper, and that migration is less likely to occur. Cuprous oxide is also advantageous in that it has a high absorbance to laser light, can be sintered at a low temperature, and can form a low-resistance sintered product. As copper oxide or copper, commercially available products or synthetic products may be used.

For example, the method for synthesizing cuprous oxide includes the following method.
(1) Water and a copper acetylacetonato complex are added to a polyol solvent, and the organocopper compound is once heated and dissolved. A method of heating and reducing by heating.
(2) A method of heating an organocopper compound (eg, copper-N-nitrosophenylhydroxyamine complex) at a high temperature of about 300° C. in the presence of a protective agent such as hexadecylamine in an inert atmosphere.
(3) A method of reducing a copper salt dissolved in an aqueous solution with hydrazine.
Among these, the method (3) is preferable because the operation is simple and cuprous oxide having a small average particle size can be obtained.

Methods for synthesizing cupric oxide include the following methods.
(1) A method of adding sodium hydroxide to an aqueous solution of cupric chloride or copper sulfate to generate copper hydroxide, followed by heating.
(2) A method of thermally decomposing copper nitrate, copper sulfate, copper carbonate, copper hydroxide or the like by heating to a temperature of about 600° C. in air.
Among them, the method (1) is preferable because cupric oxide having a small particle size can be obtained.

After completion of copper oxide synthesis, the product solution (as supernatant) and copper oxide (as precipitate) may be separated using known methods such as centrifugation. As described above, copper oxide-containing particles can be obtained.

When preparing the dispersion, the metal compound-containing particles and/or the metal-containing particles may be added with a dispersion medium described later and optionally a dispersant described later, and stirred by a known method such as a homogenizer for dispersion. Depending on the dispersion medium, the metal compound or the metal (copper oxide in one embodiment) may be difficult to disperse and may be insufficiently dispersed. After dispersing the metal compound or metal using an alcohol that is easy to disperse (for example, 1-butanol, etc.) as a dispersion medium, the metal compound is substituted with a desired dispersion medium and adjusted to a desired concentration. Alternatively, the metal can be well dispersed in the desired dispersion medium. Examples of the method include concentration using a UF membrane, a method of repeating dilution and concentration using an appropriate dispersion medium, and the like. In this manner, a dispersion containing metal compound-containing particles and/or metal-containing particles can be obtained.

In one aspect, the average particle size of the metal compound-containing particles and/or the metal-containing particles (when both the metal compound-containing particles and the metal-containing particles are present, the average particle size of the entirety thereof) is preferably 1 nm or more, or It is 3 nm or more, or 5 nm or more, preferably 100 nm or less, or 50 nm or less, or 40 nm or less. Here, the average particle size is the particle size at the time of dispersion in a dispersion, and is a value measured by a cumulant method (for example, using FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.). That is, the average particle size is not limited to the primary particle size, and may be the secondary particle size. When the average particle diameter is 100 nm or less, the pattern can be formed at a low temperature, which is preferable in terms of widening the versatility of the base material and tending to facilitate the formation of a fine pattern on the base material. In addition, when the average particle size is 1 nm or more, the dispersion stability of the metal compound-containing particles and the metal-containing particles in the dispersion is good, the long-term storage stability of the dispersion is good, and a uniform thin film It is preferable in that it can be produced. In one aspect, the particles in the dispersion are substantially exclusively metal compound-containing particles and/or metal-containing particles. In this case, the value of the average particle size measured for the dispersion can be regarded as the average particle size of the metal compound-containing particles and the metal-containing particles.

In one aspect, the metal compound-containing particles and/or metal-containing particles comprise hydrazine. Hydrazine may form a hydrate (that is, hydrazine in the present disclosure is a concept that also includes hydrazine hydrate). Hydrazine is, for example, residual hydrazine used as a reducing agent for metal oxide (copper oxide in one embodiment) in the production of metal oxide (copper oxide in one embodiment)-containing particles or metal (copper in one embodiment)-containing particles. It may be a substance, or it may be added separately during the production of the particles.

The content of the metal compound in the metal compound-containing particles and the content of the metal in the metal-containing particles are preferably 10% by mass or more, or 30% by mass or more, or 50% by mass or more, or 70% by mass or more. Yes, preferably 100% by mass or less, or 99% by mass or less, or 98% by mass or less.

The hydrazine content of the metal compound-containing particles or metal-containing particles is preferably 0.000000001% by mass or more, or 0.0000001% by mass or more, or 0.0000005% by mass or more, and preferably 10% by mass or less. , or 5% by mass or less, or 1% by mass or less.

The mass ratio of hydrazine to the metal compound in the metal compound-containing particles or the metal in the metal-containing particles is preferably 0.00001 or more, or 0.0001 or more, or 0.0002 or more, preferably 1 or less, or 0.1 or less, or 0.01 or less.

The mass ratio of the metal compound, the mass ratio of the metal, or the total mass ratio of the metal compound and the metal in 100% by mass of the dispersion is preferably 5% by mass or more, or 10% by mass or more, or 15% by mass or more. and preferably 60% by mass or less, or 55% by mass or less, or 50% by mass or less.

(dispersion medium)
The dispersion medium is capable of dispersing the metal compound-containing particles and/or the metal-containing particles. In one aspect, the dispersion medium can dissolve the dispersant. From the viewpoint of forming a conductive pattern using a dispersion, the volatility of the dispersion medium affects workability. Therefore, it is preferable that the dispersion medium is suitable for the conductive pattern forming method, for example, the coating method (especially printing). That is, it is preferable to select the dispersion medium in accordance with dispersibility and printing workability.

As the dispersion medium, alcohols (monohydric alcohol and polyhydric alcohol (eg, glycol)), ethers of alcohol (eg, glycol), esters of alcohol (eg, glycol), and the like can be used. Specific examples of dispersion media include 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, and propylene glycol. Tertiary butyl ether, dipropylene glycol monomethyl ether, ethylene glycol butyl ether, ethylene glycol ethyl ether, ethylene glycol methyl 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-ethylhexane-1,3-diol, diethylene glycol, hexanediol, octanediol, triethylene glycol, tri-1,2- Propylene glycol, glycerol, ethylene glycol monohexyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monobutyl acetate, diethylene glycol monoethyl ether acetate, methanol, ethanol, n-propanol, i-propanol, n-butanol, i- butanol, 2-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, 2-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, 2-hexanol, 2-ethylbutanol, 1-heptanol, 2-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, 2-octanol, n-nonyl alcohol, 2,6 dimethyl-4-heptanol, n- decanol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol and the like. These may be used alone or in combination of multiple types. Depending on the coating method, consideration should be given to the evaporativity, the equipment used for coating, the solvent resistance of the substrate (that is, the substrate to be coated), etc. and select. The dispersion is 1-hexanol, 1 -heptanol and 1-octanol.

The boiling point of the dispersion medium is preferably as high as possible from the viewpoint of improving printing continuity. On the other hand, the boiling point is preferably 400° C. or lower, more preferably 300° C. or lower, and even more preferably 250° C. or lower, from the viewpoint of obtaining a good function as a dispersion medium.

The content of the dispersion medium is preferably 30% by mass or more, or 40% by mass or more, or 50% by mass or more, and preferably 95% by mass or less, or 90% by mass or less, in the entire dispersion.

(dispersant)
As the dispersant, metal compound-containing particles and/or a compound capable of dispersing metal-containing particles in a dispersion medium can be used. The number average molecular weight of the dispersant is preferably 300 or more, or 350 or more, or 400 or more, preferably 300,000 or less, or 200,000 or less, or 150,000 or less. Note that the number average molecular weight of the present disclosure is a value determined in terms of standard polystyrene using gel permeation chromatography. When the number average molecular weight is 300 or more, the insulating property is excellent and tends to contribute greatly to the dispersion stability of the dispersion. The dispersant preferably has a group that has an affinity for the metal compound-containing particles and/or the metal-containing particles, especially the copper oxide-containing particles. From this point of view, the dispersant preferably comprises or is a phosphorus-containing organic substance, or comprises or is a phosphate ester, or comprises or is a polymeric phosphate ester, or comprises or is a polymeric phosphate ester. Acid ester. As the polymer phosphate ester, for example, the following formula (1):

(Wherein l is an integer from 1 to 10000, m is an integer from 1 to 10000, and n is an integer from 1 to 10000.)
The structure represented by is excellent in adsorption to metal compounds, particularly metal oxides, particularly copper oxide, particularly cuprous oxide, and adhesion to substrates, and is therefore preferable.
In the chemical formula (1), l is more preferably 1-5000, still more preferably 1-3000.
In the chemical formula (1), m is more preferably 1-5000, more preferably 1-3000.
In the chemical formula (1), n is more preferably 1-5000, still more preferably 1-3000.

In one aspect, the decomposition temperature of the phosphorus-containing organic substance 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 50° C. or higher, 80° C. or higher, or 100° C. or higher from the viewpoint of facilitating the selection of a dispersant that is excellent in improving the dispersion stability of the dispersion. In one aspect, the boiling point of the phosphorus-containing organic substance is preferably 300° C. or lower, more preferably 200° C. or lower, and even more preferably 150° C. or lower. The boiling point may be 30°C or higher, or 50°C or higher, or 80°C or higher. In the present disclosure, decomposition temperature is a value measured by thermogravimetric differential thermal analysis.

In one aspect, the phosphorus-containing organic substance is preferable in that peeling of the coating film and the plating layer is less likely to occur when plating is performed.

A known dispersant may be used. For example, polymers having basic groups, such as salts of long-chain polyaminoamides and polar acid esters, unsaturated polycarboxylic acid polyaminoamides, polycarboxylic acid salts of polyaminoamides, salts of long-chain polyaminoamides and acid polymers, etc. is mentioned. Also included are alkylammonium salts, amine salts and amidoamine salts of polymers such as acrylic (co)polymers, modified polyester acids, polyether ester acids, polyether carboxylic acids and polycarboxylic acids.

A commercially available dispersant can also be used as the dispersant of the present disclosure. Commercially available dispersing agents include, for example, DISPERBYK (registered trademark)-101, DISPERBYK-102, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-118, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164, DISPERBYK-180, DISPERBYK-2000, DISPERBYK-2164, DISPERBYK-180, DISPERBYK-2000, DISPER6BYK-2025, K- 2164, BYK-9076, BYK-9077, TERRA-204, and TERRA-U (manufactured by BYK-Chemie), Floren DOPA-15B, Floren DOPA-15BHFS, Floren DOPA-22, Floren DOPA-33, Floren DOPA-44, Floren DOPA-17HF, Floren TG-662C, and Floren KTG-2400 (manufactured by Kyoeisha Chemical Co., Ltd.), ED-117, ED-118, ED-212, ED-213, ED-214, ED-216, ED- 350, and ED-360 (manufactured by Kusumoto Kasei Co., Ltd.), Plysurf M208F, and Plysurf DBS (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). These may be used alone, or may be used in combination of multiple types.

The acid value (mgKOH/g) of the dispersant is preferably 20 or more, or 30 or more, and preferably 130 or less, or 100 or less. When the acid value is within the above range, the dispersion stability of the dispersion is good, which is preferable. In particular, when the average particle size of the metal compound-containing particles and/or the metal-containing particles is small, the acid value within the above range is effective. Specifically, BYK Chemie "DISPERBYK-102" (acid value 101), "DISPERBYK-140" (acid value 73), "DISPERBYK-142" (acid value 46), "DISPERBYK-145" (acid value 76 ), “DISPERBYK-118” (acid value 36), “DISPERBYK-180” (acid value 94) and the like are preferred.

Further, the difference between the amine value (mgKOH/g) and the acid value of the dispersant ([amine value]−[acid value]) is preferably −50 or more and 0 or less. The amine number indicates the total amount of free base and free base-derived moieties, and the acid number indicates the total amount of free fatty acids and free fatty acid-derived moieties. Amine value and acid value are each measured by a method based on JIS K 7700 or ASTM D2074. When the value of [amine value] - [acid value] is -50 or more and 0 or less, the dispersion stability of the dispersion is good, which is preferable. The value of [amine value]-[acid value] is more preferably -40 or more and 0 or less, and still more preferably -20 or more and 0 or less.

The content of the dispersant should be adjusted in proportion to the amounts of the metal compound and the metal, considering the required dispersion stability. The mass ratio of the dispersant to the metal compound and metal in the dispersion (mass of dispersant/total mass of metal compound and metal) is preferably 0.0050 or more, or 0.050 or more, or 0.10 or more. , preferably 0.30 or less, or 0.25 or less, or 0.23 or less. The amount of the dispersant affects the dispersion stability of the dispersion. If the amount is small, the metal compound-containing particles and/or the metal-containing particles tend to aggregate, and if the amount is large, the dispersion stability of the dispersion tends to improve. However, when the content of the dispersant in the dispersion is 35% by mass or less, the metal (e.g., copper)-containing film, particularly the metal (e.g., copper)-containing film obtained after the plating process when the plating process is performed, has a dispersant-derived It is possible to suppress the influence of the residue of and improve the conductivity. In one aspect, the amount of dispersant in 100% by weight of the dispersion is preferably 0.5% by weight or more, or 0.8% by weight or more, or 1.0% by weight or more, preferably 35% by weight. %, or 30% by mass or less, or 25% by mass or less.

(reducing agent)
When the dispersion contains metal oxide (eg, copper oxide)-containing particles, the dispersion may contain a reducing agent. Reducing agents include hydrazine, sodium, sodium borohydride, potassium iodide, sulfite, sodium thiosulfate, formic acid, oxalic acid, ascorbic acid, iron (II) sulfide, tin (II) chloride, and diisobutylaluminum hydride. , carbon, etc., preferably hydrazine. Hydrazine may be in the form of hydrazine hydrate (that is, hydrazine in the present disclosure is a concept that also includes hydrazine hydrate). By containing hydrazine in the dispersion, hydrazine contributes to the reduction of metal oxides, especially copper oxide, especially cuprous oxide, in the plating process, for example, when the plating process is performed, resulting in a reduced metal layer with lower resistance ( as a metal-containing film), in particular a reduced copper layer (as a copper-containing film). Hydrazine is also advantageous in maintaining the dispersion stability of the dispersion, and is also preferable from the viewpoint of improving productivity during plating. Hydrazine in the dispersion may be present as a component in the metal oxide-containing particles and/or separately from the metal oxide-containing particles.

The content of the reducing agent in the dispersion (in the case of a hydrate, the amount excluding water of hydration) is proportional to the amount of the metal oxide and should be adjusted in consideration of the required reducibility. In one aspect, the mass ratio of reducing agent to metal oxide in the dispersion (reducing agent mass/metal oxide mass) is preferably 0.0001 or more, preferably 0.1 or less, or 0.05. or less, or 0.03 or less. When the mass ratio of the reducing agent is 0.0001 or more, the dispersion stability of the dispersion is good, and the resistance of the reduced metal layer (reduced copper layer in one aspect) is low, which is preferable. In some cases, the long-term stability of the dispersion is good.

Two or more reducing agents may be used in combination. For example, when hydrazine and a reducing agent other than hydrazine are used in combination, the total content of hydrazine and a reducing agent other than hydrazine in the dispersion is proportional to the amount of metal oxide, and the required reducibility is considered. Better to adjust. In one aspect, the total mass ratio of hydrazine and a reducing agent other than hydrazine to the metal oxide in the dispersion (total mass of reducing agent/mass of metal oxide) is preferably 0.0001 or more, preferably 0 .1 or less, or 0.05 or less, or 0.03 or less. When the total mass ratio of the reducing agent is 0.0001 or more, the dispersion stability of the dispersion is good and the resistance of the reduced metal layer (reduced copper layer in one aspect) is low, which is preferable, and 0.1 The long-term stability of the dispersion is good if:

Dispersion is prepared by mixing ingredients and using a mixer method, ultrasonic wave method, three-roll method, two-roll method, attritor, homogenizer, Banbury mixer, paint shaker, kneader, ball mill, sand mill, rotation/revolution mixer, etc. It can be manufactured by dispersing treatment with The viscosity of the dispersion can be designed according to the intended mode of application. For example, the viscosity of the dispersion for inkjet printing is preferably 4 mPa·s or more, more preferably 6 mPa·s or more, even more preferably 8 mPa·s or more, preferably 15 mPa·s or less, more preferably 13 mPa·s. Below, more preferably 11 mPa·s or less. Further, for example, the viscosity of the dispersion for screen printing is preferably 50 mPa·s or more, more preferably 100 mPa·s or more, still more preferably 200 mPa·s or more, preferably 50000 mPa·s or less, more preferably 10000 mPa·s. s or less, more preferably 5000 mPa·s or less. The viscosity of the dispersion is a value measured at 23° C. using a cone-plate type rotational viscometer.

(Relationship between copper oxide and dispersant in dispersion)
FIG. 1 is a schematic cross-sectional view showing the relationship between copper oxide and a phosphate ester salt in a dispersion (copper oxide ink) that can be used in one embodiment of the present invention. Referring to FIG. 1, in one aspect of the present invention, when copper oxide ink 10 contains copper oxide 12 and phosphoric acid ester salt 13 (an example of phosphoric acid ester as a dispersant), the surroundings of copper oxide 12 are , the phosphate ester salt 13 surrounds the phosphorus 13a toward the inside and the ester salt 13b toward the outside. Since the phosphate ester salt 13 exhibits electrical insulating properties, the electrical conduction between the copper oxides 12 adjacent to each other is prevented by the phosphate ester salt 13 . Further, the phosphate ester salt 13 suppresses aggregation of the copper oxide ink 10 due to the steric hindrance effect. Therefore, although the copper oxide 12 is a semiconductor (that is, has some degree of conductivity), the copper oxide ink 10 exhibits electrical insulation because it is coated with the phosphate ester salt 13 that exhibits electrical insulation.

On the other hand, when the copper oxide 12 is reduced to copper, such as in a plating process, a conductive pattern area having excellent electrical conductivity is formed. When a phosphorus-containing organic substance is used as the dispersant, elemental phosphorus remains in the conductive pattern region. The elemental phosphorus exists as at least one of elemental elemental phosphorus, phosphorus oxide, and phosphorus-containing organic matter. However, since such residual phosphorus elements are usually segregated in the conductive pattern region, there is no risk of increasing the resistance of the conductive pattern region.

[Formation of coating film]
As a method for applying the dispersion, inkjet printing, screen printing, intaglio direct printing, intaglio offset printing, flexographic printing, offset printing, or the like can be used. Coating can be performed using methods such as die coating, spin coating, slit coating, bar coating, knife coating, spray coating, and dip coating. The application method is preferably inkjet printing. Since the ink jet method does not require a printing plate and does not deposit excess components between wirings, it has excellent resistance to migration, which is a phenomenon in which wiring components migrate when an electric field is applied to the wirings.

The layer thickness of the coating film after drying is preferably 1 nm or more, 10 nm or more, or 100 nm or more, and preferably 10000 nm or less, or 8000 nm or less, or 7000 nm or less, in that a uniform conductive pattern can be formed. is.

The substrate may have an adhesion layer (also referred to as an ink-receiving layer), and the coating film may be formed by printing the dispersion onto the adhesion layer. The compound forming the adhesion layer (also referred to as “coating compound” in the present disclosure) preferably has —OH groups and/or Ar—O structure and/or MO structure. Here, Ar represents an aromatic structure and M represents a metal atom. When the adhesion layer is present, the metal compound and/or metal layer can be formed on the substrate with good adhesion, and furthermore, heat is difficult to be transmitted to the substrate body, so that a resin with low heat resistance, such as polyethylene terephthalate ( PET) resin can also be used as the base material, which is advantageous in terms of versatility.

The —OH group is particularly an aromatic hydroxyl group (that is, an —OH group that constitutes an —Ar—OH group) or a hydroxyl group that is bonded to a metal atom (that is, an —OH group that constitutes a —M—OH group) is preferred. —OH groups constituting —Ar—OH groups and —M—OH groups are highly active, and provide adhesion between the adhesion layer and the substrate body, and/or adhesion between the metal compound and/or metal layer and the adhesion layer. It tends to be excellent in adhesion.

The aromatic structure (Ar) in the —Ar—OH group includes, for example, aromatic hydrocarbons such as benzene, naphthalene, anthracene, tetracene, pentacene, phenanthrene, pyrene, perylene, and triphenylene; Heteroaromatic compounds such as furan, pyridine, pyrazole, imidazole, pyridazine, pyrimidine, and pyrazine; be done. The number of electrons contained in the π-electron system of the aromatic structure is preferably 22 or less, more preferably 14 or less, even more preferably 10 or less. When the number of electrons contained in the π electron system is 22 or less, the crystallinity does not become too high, and it becomes easy to obtain a flexible and highly smooth adhesion layer. The aromatic structure may have some of the hydrogens attached to the aromatic ring replaced by functional groups. Functional groups include, for example, halo groups, alkyl groups (e.g., methyl group, isopropyl group, tertiary butyl group, etc.), aryl groups (e.g., phenyl group, naphthyl group, etc.), heteroaromatic groups (e.g., thienyl group, etc.), Haloaryl group (e.g. pentafluorophenyl group, 3-fluorophenyl group, 3,4,5-trifluorophenyl group, etc.), alkenyl group, alkynyl group, amide group, acyl group, alkoxy group (e.g. methoxy group, etc.), aryl Examples include an oxy group (eg, phenoxy group, naphthoxy group, etc.), haloalkyl group (eg, perfluoroalkyl group, etc.), thiocyano group, hydroxyl group, and the like. As the -Ar-OH group, a hydroxyphenyl group (-Ph-OH) is particularly preferred.

The metal atom (M) in the -M-OH group includes silicon, silver, copper, aluminum, zirconium, titanium, hafnium, tantalum, tin, calcium, cerium, chromium, cobalt, holmium, lanthanum, magnesium, manganese, molybdenum, Nickel, antimony, samarium, terbium, tungsten, yttrium, zinc, indium, and the like. A --Si--OH group or --Zr--OH group is preferred when the adhesion layer requires insulation, and a ---Ti--OH group or --Zn--OH group is preferred when the adhesion layer requires conductivity.

The aromatic structure (Ar) in the Ar—O structure may be a structure obtained by removing one or more hydrogen atoms from the same aromatic compound as the aromatic compound exemplified for the —Ar—OH group. A Ph—O structure is particularly preferable as the Ar—O structure.

As the metal atom in the MO structure, the same metal atoms as those exemplified for the -M-OH group can be used. In particular, Si--O structure, Ti--O structure, Zn--O structure and Zr--O structure are preferable as the MO structure.

Examples of coating compounds having a Si—O structure include silica-based compounds (eg, silicon dioxide (SiO ₂ )) and silicone-based compounds (eg, polysiloxanes, such as alkylpolysiloxanes, such as dimethylpolysiloxanes).

Examples of coating compounds include polyimide, polyester (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc.), polyethersulfone (PES), polycarbonate (PC), polyvinyl alcohol (PVA), and polyvinyl butyral (PVB). , polyacetal, polyarylate (PAR), polyamide (PA), polyamideimide (PAI), polyetherimide (PEI), polyphenylene ether (PPE), polyphenylene sulfide (PPS), polyetherketone (PEK), polyphthalamide ( PPA), polyether nitrile (PENt), polybenzimidazole (PBI), polycarbodiimide, silicone polymer (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, polychloroprene, ethylene-propylene-diene copolymer, Nitrile rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, urethane rubber, butyl rubber, fluororubber, polymethylpentene (PMP), polystyrene (PS), styrene-butadiene copolymer, polyethylene (PE), polyvinyl chloride ( PVC), polyvinylidene fluoride (PVDF), polyether ether ketone (PEEK), phenol novolak resin, benzocyclobutene, polyvinylphenol, polychloropyrene, polyoxymethylene, polysulfone (PSF), etc., the above -OH group, Ar Examples include materials into which one or more of the —O structure and the MO structure are introduced. Phenolic resins, phenol novolac resins, polyvinylphenols, and polyimides are particularly preferred as coating compounds.

Although the upper limit of the thickness of the adhesion layer is not particularly limited, it is preferably 20 μm or less, more preferably 5 μm or less, and still more preferably 1 μm or less, and the lower limit is preferably 0.01 μm or more, more preferably 0.05 μm or more. More preferably, it is 0.2 μm or more.

<Drying process>
The method of the present disclosure may include a drying step of drying the coating film obtained in the coating film forming step. The drying step is a step for vaporizing the dispersion medium. The dispersion medium may be vaporized at room temperature, or may be vaporized by a method such as oven drying or vacuum drying. Considering the heat resistance of the substrate, it is preferable to dry at a temperature of 150° C. or less, more preferably at a temperature of 100° C. or less. Also, nitrogen or hydrogen-mixed nitrogen (for example, a mixed gas containing about 3% by volume of hydrogen in 100% by volume of hydrogen and nitrogen in total) may be introduced during drying.

<Reduction process>
When the dispersion contains metal oxide (copper oxide in one embodiment) containing particles, one embodiment of the method of the present disclosure may include a reduction step after the coating film formation step. In the reducing step, the metal-containing film is obtained by reducing the metal oxide-containing film that is the coating film after the coating film forming step (after the drying step in one aspect). In this step, the metal oxide-containing particles in the metal oxide-containing film are reduced to generate metal, and the metal itself is fused and integrated to form a metal-containing film (reduced metal layer). However, when the metal oxide-containing particles are directly plated, this step may be omitted. As a reduction method, a method of reducing at a temperature of 100 ° C. or higher and 500 ° C. or lower in a nitrogen atmosphere, a hydrogen mixed nitrogen (for example, a mixed gas containing about 3% by volume of hydrogen in a total of 100% by volume of hydrogen and nitrogen) Among them, a method of reducing at a temperature of 100° C. or higher and 500° C. or lower, a method of reducing by laser irradiation, a method of immersing the metal oxide-containing film in a reducing solution (that is, wet reduction), and the like can be mentioned.

As a reduction method using a laser, various laser light irradiation devices 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 temperature of the 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 coating film and/or the light absorption wavelength of the base material.
Furthermore, according to the laser light method, since exposure by beam scanning is possible, it is easy to adjust the exposure range, for example, selective light irradiation only to the target area of the coating film without using a mask. (drawing) is possible.

YAG (yttrium aluminum garnet), YVO (yttrium vanadate), Yb (ytterbium), semiconductors (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-containing particles are used as the metal oxide-containing particles, the cuprous oxide is uniformly reduced to favorably absorb laser light having a central wavelength within the above range, and a conductive pattern with low resistance is obtained. can form

The laser light is preferably applied to the coating film through a galvanometer scanner. A conductive pattern of any shape can be obtained by scanning the coating film with a laser beam using a galvanometer scanner.

The laser light irradiation output is preferably 50 mW or more, or 80 mW or more, or 90 mW or more from the viewpoint of efficiently performing desired baking (for example, reduction of cuprous oxide). From the viewpoint of suppressing destruction of the conductive pattern due to ablation and obtaining a low-resistance conductive pattern, the power is preferably 1000 mW or less, 850 mW or less, or 500 mW or less.

FIG. 3 is a schematic diagram showing an example of a laser irradiation apparatus for manufacturing a structure with a conductive pattern. The laser irradiation device 100 may have a sample case 101 , a beam oscillator 102 that oscillates laser light, a gas supply section 103 , a galvanometer scanner 104 , a scanner control section 105 and a computer 106 . The sample case may have a window portion, and the window portion may have optical transparency that allows the laser light L to reach the coating film 2d through the window portion. The sample case 101 may have a gas inlet, for example, so that gas from a gas supply unit 103 (which may be, for example, a blower, a compressor, etc.) is introduced into the sample case through the gas inlet. may be configured to Alternatively, the laser irradiation device may not have a sample case. In this case, the gas may flow directly to the coating film 2d on the substrate 1. FIG.

A galvanometer scanner 104 scans the laser beam L emitted from the beam oscillator 102 . The galvanometer scanner 104 may have an X-axis galvanometer mirror 104a, an X-axis galvanometer motor 104b, a Y-axis galvanometer mirror 104c and a Y-axis galvanometer motor 104d. The galvanometer scanner may have an fθ lens (not shown), a driving lens for Z-axis adjustment (not shown), and the like. The X-axis galvano-motor 104b and the Y-axis galvano-motor 104d are electrically connected to the scanner control section 105. As shown in FIG. The galvanometer scanner is configured to be able to control the rotation angle and rotation speed of the X-axis galvanometer motor 104b and the Y-axis galvanometer motor 104d according to the control signal from the scanner controller 105. FIG. Scanner control unit 105 is controlled by computer 106 .
The laser light L is scanned by the galvanometer scanner 104 and irradiated onto the surface of the coating film 2 d formed on the substrate 1 .

The scanner control unit 105 calculates the length (L) of the scanning line based on scanning data (coordinate data) indicating the desired shape, position and size of the conductive pattern, and then calculates the length of the scanning line. Based on the height (L), the laser beam scanning speed (hereinafter referred to as scanning speed) (V) is calculated by the following equation.
Scanning speed (V)=scanning cycle (F)×scanning line length (L)
The scanner control unit 105 causes the galvanometer scanner 104 to move the irradiation point P of the laser light L according to the scanning speed, thereby executing desired scanning.

The laser irradiation device 100 includes an output adjustment mechanism (for example, an attenuator) that adjusts the output of the laser light, a pulse suppression mechanism (for example, a first pulse suppression function (FPS function)) when the laser light is pulsed light, and/or A spot adjustment mechanism (for example, a beam expander) that adjusts the spot diameter at the focal position of the laser beam may be provided. These mechanisms can be advantageous in suppressing ablation and/or carbonization of the coating film during laser light irradiation.

Any reduction method may be used in the reduction step, but in one aspect, the reduction step is a step of immersing the metal oxide-containing film in a reducing solution, that is, a wet reduction step. The reducing liquid contains a reducing agent. The reducing agent may be inorganic or organic. Examples of inorganic reducing agents include sodium borohydride, sulfur dioxide, sodium nitrite, metallic aluminum, cerium chloride, sodium thiosulfate, etc. Examples of organic reducing agents include hydrazine, formaldehyde, methanol, citric acid and their salts, oxalic acid and its salts, formic acid and its salts, glycerin, glucose, ethylene glycol, the following formula (2):
(R ¹ ) ₂ N—C(R ² ) ₂ —COOR ³ (2)
(In the formula, R ¹ , R ² and R ³ are each independently hydrogen or a monovalent group, and a plurality of R ¹ and R ² in the formula may be the same or different.)
(Glycine compound when both R ² are hydrogen) represented by the following formula (3):
(R ¹ ) ₂ N—(CH ₂ ) _x —COOR ² (3)
(wherein R ¹ and R ² are each independently hydrogen or a monovalent group, and x is an integer from 0 to 10),
L-ascorbic acid and its salts, thioglycolic acid, hydroxylamine hydrochloride, hydroquinone, hydrosulfite, erythorbic acid, erythorbate, thiourea, tin-based reducing agents, iron-based reducing agents, zinc-based reducing agents, etc. .

In one embodiment, the compound represented by formula (2) above is glycine or a derivative thereof. Glycine derivatives include, for example, N-[N-(benzyloxycarbonyl)glycyl]-L-proline, N-carbobenzoxyglycine 4-nitrophenyl, L-(2-chlorophenyl)glycine chloride, BOC-NA-methyl -L-phenylglycine, ethyl acetylamino(cyano)acetate, xylenol orange, D-(-)-2-(2,5-dihydrophenyl)glycine, Cbz-cyclohexyl-L-glycine, (R)-α -[(3-ethoxy-1-methyl-3-oxo-1-propenyl)amino]benzene potassium acetate, N-(diphenylmethylene)glycine tert-butyl, D-propargylglycine, (S)-α-amino-4 -fluorobenzeneacetic acid, N-(tert-butoxycarbonyl)-L-2-cyclohexylglycine, glycine methyl hydrochloride, D-2-allylglycine hydrochloride, (S)-2-cyclohexyl-2-aminoacetic acid, (2S )-N-[[(carboxymethyl)aminocarbonyl]methyl]-2-amino-4-methylpentanamide, (R)-2-amino-4-pentynoic acid, (R)-N-BOC-propargylglycine, N-benzylglycine, (S)-N-BOC-α-allylglycine dicyclohexylamine, BOC-D-cyclopropylglycine, N-(tert-butoxycarbonyl)-D-2-phenylglycine, (R)-(- )-N-(3,5-dinitrobenzoyl)-α-phenylglycine, L-2-chlorophenylglycine, 4-fluoro-D-phenylglycine, BOC-L-cyclopropylglycine, glycinebenzyl p-toluenesulfonate, (S)-N-BOC-allylglycine, (R)-N-BOC-allylglycine, (R)-4-hydroxy-α-[(3-methoxy-1-methyl-3-oxo-1-propenyl) amino]benzene potassium acetate, N-[(9H-fluoren-9-ylmethoxy)carbonyl]-D-2-phenylglycine, DL-leucylglycylglycine, glycylglycylglycine, N-(tert-butoxycarbonyl)- L-propargylglycine, 2-amino-2-[3-(trifluoromethyl)phenyl]acetic acid, (S)-N-BOC-3-hydroxyadamantylglycine, N-[tris(hydroxymethyl)methyl]glycine, 2 -propargyl-L-glycine, N-(triphenylmethyl)glycine, N-benzylglycineethyl, 2-(2-oxo-2-hydroxyethylamino)benzoic acid, FMOC-D-allylglycine, L-2-( 4-chlorophenyl)glycine, D-2-cyclohexylglycine, N,N-di(2-hydroxyethyl)glycine, N-(benzyloxycarbonyl)-D-phenylglycine, N-[(9H-fluoren-9-ylmethoxy ) carbonyl]-L-2-phenylglycine, benzyloxycarbonylamino(dimethoxyphosphinyl)methyl acetate, N-(tert-butoxycarbonyl)glycinemethyl, 4-(trifluoromethyl)phenylglycine, glycyl-DL-leucine , N-tosylglycine, N-(tert-butoxycarbonyl)-D-2-cyclohexylglycine, N-formylglycine, N-T-butylglycine HCL, (R)-2-allylglycine, H-glycine benzyl ester hydrochloride salt, N-carbobenzoxy-L-2-phenylglycine, ethyl (diphenylmethyleneamino)acetate (diphenylmethyleneamino)ethyl acetate, oxphenicine, L-methionylglycine, (4-hydroxyphenyl)(amino)acetic acid , (R)-α-aminobenzene methyl acetate hydrochloride, L-α-cyclopropylglycine, N-benzylglycine hydrochloride, D-cyclopropylglycine, α-amino-4-fluorobenzeneacetic acid, glycine tert-butyl hydrochloride, N-(tert-butoxycarbonyl)-2-phosphonoglycine trimethyl, N-[(9H-fluoren-9-ylmethoxy)carbonyl]glycine, N-(4-hydroxyphenyl)glycine, DL-2-( 4-chlorophenyl)glycine, L-α-cyclohexylglycine, ethyl glycine hydrochloride, benzyl N-[(methoxycarbonyl)methyl]carbamate, DL-2-(2-chlorophenyl)glycine, L-cyclopentylglycine, N-BOC -2-(4′-chlorophenyl)-D-glycine, BOC-L-cyclopentylglycine, D-(2-chlorophenyl)glycine chloride, N-phthaloylglycine, N-formylglycine ethyl, N-(tert-butoxy carbonyl)-L-2-phenylglycine, N-(tert-butoxycarbonyl)glycine, N-(2-aminoethyl)glycine, N-phenylglycine, N,N-dimethylglycine hydrochloride, (S)-N- FMOC-allylglycine, D-(-)-2-(4-hydroxyphenyl)glycine, L(+)-2-phenylglycine methyl ester hydrochloride, trisodium edetate, N-(tert-butoxycarbonyl)glycyl glycine, ethyl (2R)-2-amino-2-phenylacetate/hydrochloride, ethyl N-acetylglycine, L-leucylglycine hydrate, L-2-allylglycine hydrochloride, and the like.

As the glycine derivative, a compound having a structure having two or more hydroxy groups in the molecule is suitable. The use of a glycine derivative having two or more hydroxyl groups is advantageous in that when a plating step is performed as a post-step, the speed of the plating step can be increased, and peeling of the film is less likely to occur during the step. Preferred examples of compounds having a structure having two or more hydroxy groups in the molecule are N,N-di(2-hydroxyethyl)glycine, N-[tris(hydroxymethyl)methyl]glycine, and the like.

When the reduction step is a wet reduction step, the concentration of the reducing agent in the reducing liquid is, for example, 1.0 g/L or more, or 3.0 g/L or more, from the viewpoint of achieving a good reduction rate and stable reduction, or 5.0 g/L or more, or 10.0 g/L or more, such as 600 g/L or less, or 570 g/L or less, or 550 g/L or less, or 520 g/L or less, or 500 g/L or less. It's okay.

The concentration of the reducing agent in the reducing liquid is, for example, 0.1% by mass or more, or 0.3% by mass or more, or 0.5% by mass or more, or 1.5% by mass or more, from the viewpoint of achieving a good reduction rate and stable reduction. It may be 0% by mass or more, and may be, for example, 60% by mass or less, or 57% by mass or less, or 55% by mass or less, or 52% by mass or less, or 50% by mass or less.

In one aspect, the reducing liquid contains the compound represented by the above formula (2). The concentration of the compound in the reducing liquid is preferably 1 mass % or more, 8 mass % or more, or 16 mass % or more, and preferably 50 mass % or less, or 32 mass % or less.

In typical embodiments, the reducing liquid comprises a solvent. The solvent system may be water-based or organic solvent-based. Examples of solvents include water, ethanol, 1-butanol, 2-propanol, toluene, hexane, benzene, chloroform, methylene chloride, acetic acid, ethyl acetate, tetrahydrofuran, acetone, acetonitrile, N,N-dimethylformamide, dimethylsulfoxide, and the like. is mentioned. Water, ethanol, 1-butanol, and 2-propanol are particularly preferred from the viewpoint of reuse.

Water is particularly preferable as the solvent in the reducing liquid, and a combination of a glycine compound and water is particularly preferable from the viewpoint of cost and productivity. The reducing liquid is particularly preferably an aqueous solution having a glycine compound concentration of 1% by mass or more and 50% by mass or less.

In one aspect, the reducing liquid preferably contains N,N-di(2-hydroxyethyl)glycine and/or citric acid from the viewpoint of productivity, that is, from the viewpoint of rapid reduction. Especially when N,N-di(2-hydroxyethyl)glycine is used, aluminum, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, ruthenium, rhodium, palladium, A metal selected from silver, indium, tin, antimony, iridium, platinum, gold, thallium, lead, and bismuth (copper in one embodiment) becomes ions and forms a complex with glycine to form a metal oxide (copper oxide in one embodiment). ) to metal (copper in one embodiment).

During the reduction, it is preferable to immerse the coating film while stirring so that the concentration of the reducing agent in the reducing solution is constant.

The reducing liquid preferably contains a predetermined amount or more of metal ions and/or metal oxides (in one aspect, copper ions and/or copper oxides). This makes it possible to prevent the coating film from coming off during the wet reduction. The concentration of metal ions, or the concentration of metal oxides, or the total concentration of metal ions and metal oxides in the reducing liquid is preferably 1% by mass or more, or 5% by mass or more, and preferably 99% by mass or less. , or 90% by mass or less. In one aspect, when the reducing liquid contains copper ions and/or copper oxide, it is selected from the group consisting of copper acetate, copper chloride, copper oxide, metallic copper, and a dispersion containing the copper oxide-containing particles of the present disclosure. Copper ions and/or copper oxide may be included in the reducing solution by adding one or more of them to the solvent to prepare the reducing solution. In one embodiment, the reducing solution may contain copper oxide by diffusing the copper oxide from the coating film into the solvent.

From the viewpoint of productivity, the temperature in the wet reduction step is preferably 20° C. or higher, more preferably 30° C. or higher, and even more preferably 40° C. or higher, so that the reduction proceeds quickly. From the viewpoint of obtaining a uniform metal (copper in one aspect) containing film, the temperature is preferably 100° C. or lower, more preferably 90° C. or lower.

The wet reduction process and the electroless plating in the plating process can be performed simultaneously. From the viewpoint of improving productivity, it is preferable to perform the wet reduction step and the plating step at the same time. Specifically, the wet reduction process and the plating process can be performed at the same time by including a reducing agent in the plating solution, which will be described later. In this case, the amount of the solvent may be adjusted so that the reducing agent concentration and the plating substance concentration (copper concentration in one aspect) in the plating solution are within the ranges exemplified for the reducing solution and the plating solution in the present disclosure. preferable.

<Washing process>
When wet reduction is performed, an appropriate washing liquid may be used to remove the unreduced portion and the reducing liquid after the wet reduction. This leaves a clean reduced area on the substrate. On the other hand, the washing process may not be performed. In either case, a substrate (hereinafter also referred to as a conductive substrate) imparted with conductivity by the reduced region as the conductive pattern is obtained. However, when the metal oxide (copper oxide in one aspect) containing film is directly plated, this step may be omitted in some cases.

As a cleaning liquid for cleaning, a liquid that disperses or dissolves a metal oxide (copper oxide in one embodiment) can be used. Specific examples include water, 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 tarsier. libbutyl ether, dipropylene glycol monomethyl ether, ethylene glycol butyl ether, ethylene glycol ethyl ether, ethylene glycol methyl 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-ethylhexane-1,3-diol, diethylene glycol, hexanediol, octanediol, triethylene glycol, tri-1,2-propylene Glycol, glycerol, ethylene glycol monohexyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monobutyl acetate, diethylene glycol monoethyl ether acetate, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol , 2-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, 2-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, 2 -Hexanol, 2-ethylbutanol, 1-heptanol, 2-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, 2-octanol, n-nonyl alcohol, 2,6 dimethyl-4-heptanol, n-decanol , cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol, and acetone. The above solvents are particularly suitable for washing off metal oxides (in one aspect, copper oxide) well when the coating film contains a dispersant. Particularly preferred solvents are water, ethanol, 1-butanol, i-propanol, and acetone. Note that the above cleaning liquid may contain a dispersant in addition to the solvent. As the dispersant, those mentioned above can be used, and a phosphorus-containing organic substance is more preferable.

<Degreasing process>
When the plating process is performed, a process of degreasing the coating film may be included before the plating process. In one aspect, the productivity can be improved by directly degreasing the metal oxide (in one aspect, copper oxide) without reducing it. In yet another aspect, the metal oxide may be reduced (eg, in the reduction step described above) and then degreased. Examples of degreasing methods include a UV method and a wet degreasing method. The degreasing process increases the growth rate of the subsequent plating and improves productivity. In addition, this step reduces the porosity of the conductive layer after plating (that is, the plating layer and the layer when the metal compound and / or metal layer contains copper), that is, the final conductive layer contributes to the porosity of Note that degreasing may be performed along with the electroless plating, and in this case, the degreasing step may be omitted.

From the viewpoint of interlayer adhesion of the conductive patterned structure, the degreasing step is preferably carried out by immersing the coating film in a degreasing solution containing a compound containing an amino group. Compounds containing an amino group include amino acids such as alanine, arginine, asparagine, cysteine, glutamine, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine, and methylamine. , dimethylamine, ethylamine, trimethylamine, diethylamine, triethylamine, propylamine, isopropylamine, diisopropylamine and other alkylamines, 2-aminoethanol, diethanolamine, triethanolamine, N-methylethanolamine, N,N-dimethylethanolamine alkanolamines such as ethylenediamine, diethylenetriamine, tetraethylenepentamine, tris(hydroxymethyl)aminomethane, m-xylylenediamine, p-xylylenediamine, 1,3-bis(aminomethyl)cyclohexane and other polyamines, Examples include aminosulfonic acids such as taurine, aminothiols such as 2-aminoethanethiol, and nitrogen-containing heterocyclic compounds such as 3-picolylamine and 3-pyridinemethanol. 2-Aminoethanol is particularly preferred from the viewpoint of contributing to the plating growth rate.

The degreasing liquid may be a commercial product, specifically, ALC-009 (including 2-aminoethanol as a compound having an amino group) available from Uyemura Kogyo Co., Ltd., available from Atotech Japan Co., Ltd. and Cleaner Securigant 902 (containing 2-aminoethanol as a compound having an amino group).

The concentration of the compound containing an amino group in the degreasing liquid is preferably 5 mmol/L or more, more preferably 10 mmol/L or more, and more preferably 20 mmol/L or more from the viewpoint of removing inhibitors of the plating reaction. From the viewpoint of promoting the plating reaction, it is preferably 100 mmol/L or less, more preferably 90 mmol/L or less, and more preferably 80 mmol/L or less.

The immersion time of the coating film in the degreasing solution is preferably 1 minute or longer, more preferably 2 minutes or longer, from the viewpoint of contributing to the plating growth rate. Moreover, from the viewpoint of reducing damage to the substrate, it is preferably within 15 minutes, more preferably within 10 minutes. Immersion under stirring is preferable from the viewpoint of uniform degreasing.

The immersion temperature is preferably 15° C. or higher, more preferably 30° C. or higher, and even more preferably 40° C. or higher, in order to enhance the effect of accelerating the growth rate of the plating. Moreover, from the viewpoint of reducing damage to the substrate, the temperature is preferably 70° C. or lower, more preferably 60° C. or lower.

<Plating process>
In one aspect of the method of the present disclosure, the plating step may be performed after the coating film forming step. The plating process contributes to the formation of conductive regions with relatively low porosity. In one embodiment, after the drying step, the coating film that has undergone or has not undergone the reduction step and/or the degreasing step may be plated. In a preferred embodiment, the reduction step is performed after the coating film formation step, and the plating step is performed after the reduction step, but either the reduction step or the plating step may be performed first. In one aspect, the productivity can be improved by directly plating the metal oxide (copper oxide in one aspect) containing film without reducing it. The plating is electroless plating in one aspect. Electroless plating may reduce some or all of the metal oxide (copper oxide in one embodiment) in the metal oxide (copper oxide in one embodiment) containing film, or may not reduce the metal oxide. good too. In another aspect, electroless plating is performed on a metal (copper in one aspect)-containing film obtained by reducing (e.g., wet reduction) a metal oxide (copper oxide in one aspect)-containing film to obtain a conductive film. can be improved. Electroless plating can form a conductive pattern composed of a metal compound and/or metal layer and a plated layer. Thereby, a structure with a conductive pattern can be manufactured. Electroless plating is advantageous in terms of wide applicability to patterns. As a plating method, a general electroless plating method may be applied. For example, electroless plating may be performed along with a degreasing or cleaning step.

A plating solution is used for electroless plating. When the drying process is performed, the coating film after the drying process is likely to peel off due to external stress, so if the plating deposition varies and the stress concentrates on one part, the coating film may peel off during the plating process. Regardless of the type of plating solution, one containing EDTA (ethylenediaminetetraacetic acid) or Rochelle salt (potassium sodium L-tartrate tetrahydrate) as a complexing agent may be used. In one aspect, the plating solution comprises EDTA. EDTA functions as a complexing agent and can be used for aluminum, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, ruthenium, rhodium, palladium, silver, indium, tin, antimony, iridium, platinum, Since it forms a highly stable complex with metal (in one aspect, copper) ions selected from gold, thallium, lead, and bismuth, it suppresses side reactions in the plating bath, stabilizes the bath, and promotes plating deposition. It is considered that the uniform progression contributes to the prevention of peeling of the coating film. Therefore, the use of a plating solution containing EDTA contributes to the production of a conductive patterned structure with excellent interlayer adhesion. In addition, EDTA is stable even in a high-temperature liquid, and thus contributes to increasing the plating rate when a plating solution containing EDTA is used under heating (for example, 30° C. or higher). In addition, it is particularly preferable to perform plating with a plating solution containing EDTA (ethylenediaminetetraacetic acid) after wet reduction, because the growth of metal (copper in one aspect) plating is promoted, thereby improving productivity. The amount of EDTA in the plating solution is preferably 7 g/L or more, or 10 g/L or more, or 15 g/L or more, from the viewpoint of obtaining the advantages of EDTA well, to reduce impurities in the plating deposit. , preferably 50 g/L or less, or 45 g/L or less, or 40 g/L or less, from the viewpoint of lowering the electrical resistance.

In typical embodiments, the plating solution includes a copper ion source and a reducing agent. The copper ion source may exist as ions in the liquid. For example, the coating film may be immersed in the plating solution while performing air bubbling. Copper ions in the plating solution are reduced by electroless plating, and copper is deposited on the surface of the coating film to form a plated copper layer. When the coating film contains a metal oxide (copper oxide in one aspect), in electroless plating, part or all of the metal oxide may or may not be reduced by the plating solution. . Accordingly, a plated copper layer is formed on the layer containing the metal compound and/or the metal.

From the viewpoint of improving the plating speed, the copper concentration of the plating solution is preferably 1.5 g/L or more, or 1.8 g/L or more, or 2.0 g/L or more, and the uniformity of the plating film is improved. From the viewpoint, it is preferably 5.0 g/L or less, or 4.0 g/L or less, or 3.5 g/L or less, or 3.0 g/L or less. In particular, when wet reduction and plating are combined, the copper concentration of the plating solution is preferably 1.8 g/L or more and 3.5 g/L or less.

CuSO _{4 ,} CuCl _{2 ,} CuCl, CuNO ₃ , Cu ₃ (PO ₄ ) ₂ and the like can be exemplified as the copper ion source contained in the plating solution. is preferred.

The plating solution may contain, as a reducing agent, one or more selected from the group consisting of formaldehyde (CH ₂ O), potassium tetrahydrochloride, dimethylamine borane, glyoxylic acid, and phosphinic acid. The amount of reducing agent in the plating solution is preferably 0.1 g/L or more, or 0.5 g/L or more, or 1.0 g/L or more, and preferably 15.0 g/L or less, or 12 .0 g/L or less, or 9.0 g/L or less.

The plating solution may further contain an additional complexing agent in addition to EDTA (ethylenediaminetetraacetic acid). Additional complexing agents include Rochelle's salt, triethanolamine, ammonium sulfate, citric acid, glycine, and the like. or 40 g/L or less.

The plating solution may further contain a surfactant as desired.

The plating solution may be a commercially available product. Commercially available products include Sulcup ELC-SP available from Uyemura & Co., Ltd., Melplate CU-390 and Melplate CU-5100P available from Meltex Inc., and Okuno Chemical Industry Co., Ltd. OPC Copper NCA, C4500 available from Rohm and Haas Co., Ltd., Printganth UPlus available from Atotech Co., Ltd., Cu-510 available from MacDermid Japan Co., Ltd., and the like can be used.

The temperature of the electroless plating bath of the plating solution is preferably 25° C. or higher, or 30° C. or higher, or 35° C. or higher, and preferably 80° C. or lower, or 70° C., since faster plating growth can be expected. or less, or 65° C. or less. The plating time is preferably 5 minutes or longer, or 10 minutes or longer, and preferably 60 minutes or shorter, or 50 minutes or shorter, or 40 minutes or shorter.

The layer thickness of the plated layer (plated copper layer in one aspect) is preferably 300 nm or more, or 500 nm or more, or 1 μm or more, in that the current required for the conductive patterned structure can flow, or 2 μm or more, preferably 100 μm or less, or 50 μm or less, or 30 μm or less.

In one aspect, electroless plating may be followed by electroplating. A general electroplating method can be applied to the electroplating. For example, an electrode and a conductive substrate to be plated are placed in a solution (plating bath) containing copper ions. Then, a DC current is applied between the electrode and the conductive substrate from an external DC power supply. In one aspect, a reduced metal layer (reduced copper in one aspect) on a conductive substrate is connected to a jig (e.g., a clip) connected to one of the electrode pairs of an external DC power source, whereby a current is applied to the reduced metal layer. can be applied. As a result, copper is deposited on the surface of the reduced metal layer on the conductive substrate by reduction of the copper ions to form a plated copper layer.

As the electrolytic plating bath, for example, a copper sulfate bath, a copper borofluoride bath, a copper cyanide bath, and a copper pyrophosphate bath can be used. A copper sulfate bath and a copper pyrophosphate bath are preferred from the viewpoint of safety and productivity.

As the copper sulfate plating bath, for example, a sulfuric acid acid copper sulfate plating bath containing copper sulfate pentahydrate, sulfuric acid and chlorine is preferably used. The concentration of copper sulfate pentahydrate in the copper sulfate plating bath is preferably 50 g/L or more, or 100 g/L or more, and preferably 300 g/L or less, or 200 g/L or less. The concentration of sulfuric acid is preferably 40 g/L or more, or 80 g/L or more, and preferably 160 g/L or less, or 120 g/L or less. The solvent of the plating bath is usually water. The temperature of the plating bath is preferably 20° C. or higher, or 30° C. or higher, and preferably 60° C. or lower, or 50° C. or lower. The current density during electrolytic treatment is preferably 1 A/dm ² or more, or 2 A/dm ² or more, and preferably 15 A/dm ² or less, or 10 A/dm ² or less.

As the copper pyrophosphate plating bath, for example, a plating bath containing copper pyrophosphate and potassium pyrophosphate is suitable. The concentration of copper pyrophosphate in the copper pyrophosphate plating bath is preferably 60 g/L or more, or 70 g/L or more, and preferably 110 g/L or less, or 90 g/L or less. The concentration of potassium pyrophosphate is preferably 240 g/L or more, or 300 g/L or more, preferably 470 g/L or less, or 400 g/L or less. The solvent of the plating bath is usually water. The pH of the plating bath is preferably 8.0 or higher, or 8.2 or higher, and preferably 9.0 or lower, or 8.8 or lower. Ammonia water or the like may be added to adjust the pH value. The temperature of the plating bath is preferably 20° C. or higher, or 30° C. or higher, and preferably 60° C. or lower, or 50° C. or lower. The current density during electrolytic treatment is preferably 0.5 A/dm ² or more, or 1 A/dm ² or more, and preferably 10 A/dm ² or less, or 7 A/dm ² or less.

A plating bath for electrolytic plating may further contain a surfactant.

<Post-treatment process>
One aspect of the method of the present disclosure includes a post-treatment step for the purpose of improving the adhesion between the substrate and the layer of metal compound and/or metal. The post-treatment process is performed after the coating film forming process. In one aspect, the humidification treatment and/or heat treatment may be performed after the coating film forming step, for example, between the coating film forming step and the drying step, between the drying step and the plating step, and after the plating step. In one or more of , the humidification treatment and/or the heat treatment may be performed. When both the moistening treatment and the heating treatment are performed, they may be performed simultaneously or sequentially. In the case of sequential, the order of humidification treatment and heat treatment is not limited.

According to the humidification treatment, moisture enters the interface between the substrate and the layer of the metal compound and/or the metal, so that an effect of improving the adhesion between layers can be obtained. Although not bound by theory, the above interlayer adhesion improvement is due to the combination of the components contained in the metal compound and/or metal layer (e.g., the dispersant component derived from the dispersion) and the moisture provided in the humidification process. , is thought to be caused by forming a hydrogen bond with the substrate. Base materials include polyimide (PI), polyester (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc.), polyethersulfone (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) and the like are preferable because the base material contains a chemical structure capable of forming a hydrogen bond, so that the effect of improving interlayer adhesion is good. In particular, when the base material is polyimide, the effect of improving interlayer adhesion is improved due to the contribution of imide bonds, which is more preferable.

Moreover, it is believed that the heat treatment improves the interlayer adhesion between the substrate and the layer of the metal compound and/or metal due to the improvement of the mechanical strength of the substrate. In one aspect, when the material of the substrate is polyimide, the imide bond in the polyimide may be broken in the plating process, but the once broken imide bond can be repaired by heat treatment. It is believed that such a change in molecular structure due to heat treatment brings about an improvement in the mechanical strength of the base material.

A constant temperature and humidity chamber, a desiccator, or the like can be used as the humidification treatment device.

A drying furnace, an oven, or the like can be used as the heat treatment apparatus.

The relative humidity of the humidification treatment is preferably 50% or higher, or 60% or higher, or 70% or higher, and preferably 100% or lower.

The duration of the humidification treatment is preferably 1 hour or longer, or 10 hours or longer, or 24 hours or longer, and preferably 14 days or shorter, or 10 days or shorter, or 8 days or shorter.

The temperature of the humidification treatment is preferably 5° C. or higher, or 15° C. or higher, or 20° C. or higher, and preferably 100° C. or lower, or 80° C. or lower, or 50° C. or lower.

Heat treatment may be performed, for example, in air. In one aspect, the humidification treatment and the heating treatment may be carried out simultaneously in a gas (air, inert gas, etc.) whose humidity is controlled within the range exemplified above. The temperature of the heat treatment is preferably 100° C. or higher, or 200° C. or higher, or It is 250° C. or higher, and preferably 400° C. or lower, or 350° C. or lower, or 300° C. or lower from the viewpoint of avoiding thermal deterioration of the base material (in one aspect, from the viewpoint of heat resistance of the polyimide base material).

<Preferred example of method for manufacturing structure with conductive pattern>
Hereinafter, a more specific preferred example of the method for manufacturing a structure with a conductive pattern will be described with reference to FIG. In addition, below, the case where a dispersion contains a copper oxide particle as a metal compound content particle is demonstrated to an example.
First, copper acetate B is dissolved in mixed solvent A of water and propylene glycol (PG), hydrazine C is added, and the mixture is stirred (Fig. 2(a)).
Then, by centrifugation, the product solution (supernatant 2a) and cuprous oxide (precipitate 2b) are solid-liquid separated (Fig. 2(b)).
Next, dispersing agent D and alcohol E are added to precipitate 2b (Fig. 2(c)) to disperse the precipitate to obtain dispersion 2c containing copper oxide (Fig. 2(d)).
Separately, a substrate 1 is prepared (FIG. 2(e)), and a treated surface S is formed on the substrate 1 by the pretreatment process of the present disclosure (FIG. 2(f)).
Next, the dispersion 2c containing copper oxide is printed on the treated surface S of the base material 1 by an inkjet method, gravure printing method, or the like to form a coating film, which is then dried. As a result, a copper oxide-containing film (copper oxide layer) 2d containing copper oxide and a dispersing agent is formed on the substrate 1 (FIG. 2(g)).

Next, the copper oxide-containing film is immersed in a degreasing solution containing an amino group-containing compound to perform a degreasing step, followed by a plating step. Note that the degreasing step may be omitted. Part or all of the copper oxide in the copper oxide layer may be reduced in the plating step. As a result, a copper oxide and/or copper layer 2e and a plated copper layer 2f are formed on the substrate 1 (FIG. 2(h)).
A structure with a conductive pattern can be manufactured by the above procedure.

As described above, according to the method of the present disclosure, a conductive layer can be produced at a very low cost and with low energy, so a structure with a conductive pattern can be produced more easily.

<Formation of additional layers>
The conductive patterned structures of the present disclosure may have additional layers in addition to the substrate and conductive layers as previously described. A resin layer and a solder layer can be exemplified as additional layers.

[Resin layer]
In one aspect, it is preferable that part of the conductive layer is covered with a resin layer. By partially covering the conductive layer with the resin layer, oxidation of the conductive pattern is prevented and reliability is improved. In addition, since there is a part of the conductive layer that is not covered with the resin layer, the components can be electrically joined.

An example of a resin layer is a sealing material layer. The resin layer can be formed by, for example, transfer molding, compression molding, or the like. Examples of resins that can be used include polyethylene (PE), polypropylene (PP), polyimide (PI), polyester (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), etc.), polyethersulfone. (PES), polycarbonate (PC), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyacetal (POM), polyarylate (PAR), polyamide (PA) (PA6, PA66, etc.), polyamideimide (PAI), poly Etherimide (PEI), polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyphenylene sulfide (PPS), polyetherketone (PEK), polyetheretherketone (PEEK), polyphthalamide (PPA), poly Ether nitrile (PENt), polybenzimidazole (PBI), polycarbodiimide, silicone polymer (polysiloxane), 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, polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), phenol novolak, benzocyclobutene, polyvinylphenol, polychloropyrene, polyoxymethylene, polysulfone (PSF), Polyphenylsulfone resin (PPSU), cycloolefin polymer (COP), acrylonitrile-butadiene-styrene resin (ABS), acrylonitrile-styrene resin (AS), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), etc. are mentioned. The thickness of the resin layer is preferably 0.1 μm or more, or 0.5 μm or more, and preferably 1 mm or less, or 800 μm or less.

The encapsulant layer protects the conductive pattern from external stress in the finished product (the conductive patterned structure itself and the product including the same) after manufacturing, and enhances the long-term stability of the conductive patterned structure. can improve.

From the viewpoint of ensuring good long-term stability, the moisture permeability of the sealing material layer, which is an example of the resin layer, is preferably 1.0 g/m ² /day or less, more preferably 0.8 g/m ² /day. 0.6 g/m 2 /day or less, more preferably 0.6 g/m ² /day or less. By reducing the moisture permeability, it is possible to prevent moisture from entering the sealing material layer from the outside and suppress oxidation of the conductive pattern. The lower the moisture permeability, the better. The moisture permeability is a value measured by the cup method.

The encapsulant layer can be a functional layer that provides an oxygen barrier function to the conductive patterned structure even after peeling off an oxygen barrier layer that may be used during manufacturing. Other functions include scratch resistance when handling a structure with a conductive pattern, antifouling properties to protect the structure with a conductive pattern from contamination from the outside, and a conductive pattern when a tough resin is used. It may have a function such as improving the rigidity of the structure.

[Solder layer]
In one aspect, it is preferable that a solder layer is formed on part of the conductive layer on the side opposite to the substrate side. A solder layer can connect the conductive layer to another member. A solder layer can be formed by, for example, a reflow method. The solder layer includes Sn--Pb system, Pb--Sn--Sb system, Sn--Sb system, Sn--Pb--Bi system, Bi--Sn system, Sn--Cu system, Sn--Pb--Cu system, Sn--In system, It may be a solder layer of Sn--Ag system, Sn--Pb--Ag system, Pb--Ag system, or the like. The thickness of the solder layer is preferably 0.1 μm or more, or 0.5 μm or more, and preferably 2 mm or less, or 1 mm or less.

<Conductive patterned structure manufacturing kit>
One aspect of the present disclosure provides a conductive patterned structure manufacturing kit that includes a dispersion of the present disclosure, a plating solution of the present disclosure, and a substrate that has undergone a specific treatment of the present disclosure. The kit can be advantageous for manufacturing a conductive patterned structure with good interlayer adhesion.

One aspect of the present disclosure is
a dispersion containing metal compound-containing particles and/or metal-containing particles;
A plating solution containing EDTA (ethylenediaminetetraacetic acid), and a substrate subjected to one or more treatments selected from the group consisting of UV ozone treatment, organic solvent treatment, and alkali treatment,
A conductive patterned structure manufacturing kit is provided.

It is preferable that the base material is polyimide because the adhesion between the dispersion and the base material is excellent.

One aspect of the present disclosure is
a dispersion containing metal compound-containing particles and/or metal-containing particles;
a plating solution containing EDTA (ethylenediaminetetraacetic acid);
one or more treating agents selected from the group consisting of organic solvents and alkaline treating agents; and a substrate;
A conductive patterned structure manufacturing kit is provided.

In addition, one aspect of the present disclosure is
a dispersion comprising metal compound-containing particles and/or metal-containing particles; and an organic solvent for organic solvent treatment;
Provided is a kit for manufacturing a structure with a conductive pattern, wherein the SP value of the organic solvent is 7.5 or more and 12.6 or less. The SP value of the organic solvent is more preferably 9.9 or more and 11.6 or less. The organic solvent preferably contains N-methylpyrrolidone.

Preferable configuration examples of each of the dispersion, the plating solution, and the base material that can be included in the kit for manufacturing a structure with a conductive pattern of the present disclosure may be as described above in the present disclosure, and the description will not be repeated here.

<Manufacturing system for structure with conductive pattern>
One aspect of the present disclosure also provides a conductive patterned structure manufacturing system. The conductive patterned structure manufacturing system includes a pretreatment mechanism for applying an organic solvent treatment to a base material using an organic solvent having an SP value of 7.5 or more and 12.6 or less;
a coating mechanism for obtaining a coating film by coating a substrate with a dispersion containing metal compound-containing particles and/or metal-containing particles;
a plating mechanism for plating the coating film that has passed through the coating mechanism;
Prepare. The conductive patterned structure manufacturing system may further include a drying mechanism for drying the coating film.
The conductive patterned structure manufacturing system of the present disclosure can be suitably applied to the conductive patterned structure manufacturing method of the present disclosure. Therefore, as each element of the conductive patterned structure manufacturing system, those having the configuration or function as exemplified above in the manufacturing method of the conductive patterned structure may be employed.

In one aspect, the pretreatment mechanism may be an organic solvent dipper or an organic solvent sprayer.

In one aspect, the application mechanism may be an inkjet printer, a screen printer, an intaglio direct printer, an intaglio offset printer, a flexographic printer, or an offset printer, preferably an inkjet printer. In one aspect, the coating mechanism may comprise a die coater, a spin coater, a slit coater, a bar coater, a knife coater, a spray coater, or a dip coater.

In one aspect, the drying mechanism may be an oven or vacuum dryer. Also, in one aspect, the plating station may be a bath of plating solution.

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

<Evaluation method>
[Method for quantifying hydrazine]
Hydrazine was quantified by the standard addition method.
33 μg of hydrazine, 33 μg of surrogate substance (hydrazine ¹⁵ N ₂ H ₄ ), and 1 ml of acetonitrile solution of 1 mass % benzaldehyde were added to 50 μL of sample (dispersion). Finally, 20 μL of phosphoric acid was added, and 4 hours later, GC/MS (gas chromatography/mass spectrometry) measurement was performed.

Similarly, 66 μg of hydrazine, 33 μg of surrogate substance (hydrazine ¹⁵ N ₂ H ₄ ), and 1 ml of acetonitrile solution of 1 mass % benzaldehyde were added to 50 μL of sample (dispersion). Finally, 20 μL of phosphoric acid was added, and 4 hours later, GC/MS measurement was performed.

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

Finally, to 50 μL of the sample (dispersion), add 33 μg of a surrogate substance (hydrazine ¹⁵ N ₂ H ₄ ), 1 mL of benzaldehyde 1% by mass acetonitrile solution without adding hydrazine, and finally add 20 μL of phosphoric acid. After 4 hours, GC/MS measurements were performed.

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

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

[Average particle size measurement]
The average particle size of the dispersion was measured by the cumulant method using FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.

[Adhesion evaluation]
Adhesion was evaluated by a tape peel test. A Kapton adhesive tape (6563 #50) is attached to the surface of the copper-containing film side of the sample, and the angle between the surface and the adhesive tape is 60 degrees (that is, peeled off at 60 degrees). rice field. Evaluation was made according to the following criteria.
AA: Visually visible peeling is 10% or less of the entire portion where the adhesive tape is attached A: Visually visible peeling is more than 10% and 25% or less of the entire portion where the adhesive tape is attached B: Visually visible peeling is adhesive More than 25% to 50% or less of the entire tape-attached portion C: More than 50% to 60% or less of the entire portion to which the adhesive tape is attached that is visually visible peeling D: The entire portion to which the adhesive tape is attached that is visually visibly peeled over 61% of

<Example 1>
[Manufacturing of Dispersion]
3224 g of copper (II) acetate monohydrate (manufactured by Nippon Kagaku Sangyo Co., Ltd.) is dissolved in a mixed solvent consisting of 30240 g of water and 13976 g of 1,2-propylene glycol (manufactured by AGC), hydrazine hydrate ( (manufactured by Japan Finechem Co., Ltd.) was added and stirred, and then separated into a supernatant and a precipitate using centrifugation.
794 g of the mixture liquid was added to 345 g of the obtained precipitate, and dispersed using a homogenizer in a nitrogen atmosphere to obtain a dispersion containing cuprous oxide particles (as metal compound-containing particles). The above mixed solution was prepared by adding 72 g of DISPERBYK-145 (trade name, manufactured by BYK-Chemie) (BYK-145) as a phosphorus-containing organic compound and 764 g of 1-heptanol (manufactured by Toyo Gosei Co., Ltd.) as a dispersion medium. prepared. Further, 5 g of DISPERBYK-145 and 82 g of 1-heptanol were added to 1,063 g of the above dispersion, and dispersed using a homogenizer under a nitrogen atmosphere to obtain the desired dispersion. Also, the amount of hydrazine in the dispersion was 0.2% by mass. 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 26.1% by mass.

[Substrate washing and pretreatment process]
A polyimide base material (thickness: 25 μm, SP value: 12.1 cal/cm ³ ) was cleaned by irradiating ultrasonic waves in ultrapure water for 5 minutes and then in ethanol for 5 minutes. Then, the surface of the substrate was subjected to UV ozone treatment for 3 minutes. The substrate was then immersed in N-methylpyrrolidone at room temperature (23° C.) for 15 minutes. After that, the substrate was washed with water, and the surface of the substrate was air-blown to remove the water.

[Application and drying of dispersion]
Printing was performed on the surface with an inkjet printer (Fuji Film, DIMATIX Material Printer DMP-2831). The head was DMC-11610, the voltage was 25 V, the frequency was 25 kHz, and the resolution was 1018 dpi. A pattern of 50 mm x 50 mm was drawn. Then, the substrate was dried by heating at 60° C. for 1 hour to obtain a sample in which a dry coating film, which is a copper oxide-containing film, was formed on the substrate.

[Post-treatment process]
After drying, it was stored for 24 hours in a room under normal pressure, room temperature of 23°C and relative humidity of 100%.

[Reduction step]
Wet reduction was used. N,N-di(2-hydroxyethyl)glycine was dissolved in water to prepare a 35 wt% solution. Using this as a reducing solution, the copper oxide-containing film was immersed in the reducing solution heated to 60° C. for 30 minutes. Then, it was washed with water to obtain a copper film.

[Plating process]
Next, an electroless plating solution containing EDTA, OPC Copper NCA (containing 2.2 g/L of formaldehyde) manufactured by Okuno Chemical Industry Co., Ltd. was heated to 60° C., and the sample was immersed for 10 minutes. After treatment, the samples were removed and washed with water.

[Adhesion evaluation]
As a result of the tape peeling test, peeling of the copper-containing film was not observed, and the adhesion evaluation was AA.

<Example 2>
The same method as in Example 1 was performed, except that the reduction step was a heat treatment at 300° C. for 1 hour in a nitrogen atmosphere.

<Example 3>
The post-treatment process was carried out in the same manner as in Example 2, except that after plating, heat treatment was performed at 300° C. for 1 hour in a nitrogen atmosphere.

<Example 4>
It was carried out in the same manner as in Example 1, except that the post-treatment step was not carried out.

<Example 5>
The same method as in Example 3 was used except that the substrate washing and pretreatment steps, the coating and drying of the dispersion, and the posttreatment steps were performed as follows.
[Substrate washing and pretreatment process]
The polyimide substrate was cleaned by irradiating ultrasonic waves in ultrapure water for 5 minutes and then in ethanol for 5 minutes. Then, the surface of the substrate was subjected to UV ozone treatment for 3 minutes. The substrate was then immersed in N-methylpyrrolidone at room temperature (23° C.) for 60 minutes. After that, it was washed with water, and the surface of the substrate was air-blown to remove the water.
[Application and drying of dispersion]
After dropping 1 ml of the dispersion onto the surface and spin coating (300 rpm, 60 seconds), drying was performed at 60° C. for 1 hour to obtain a sample having a dry coating film formed on the substrate.
[Post-treatment process]
did not implement.

<Example 6>
It was carried out in the same manner as in Example 2, except that the post-treatment step was not carried out.

<Example 7>
The same method as in Example 5 was used except that the UV ozone treatment was not performed in the pretreatment step.

<Example 8>
The same method as in Example 6 was used except that the UV ozone treatment was not performed in the pretreatment step.

<Example 9>
It was carried out in the same manner as in Example 6, except that the reduction method was as follows.
[Reduction step]
Laser irradiation was performed using the laser irradiation apparatus 100 configured as shown in FIG. Nitrogen gas was supplied from the gas supply unit 103 to the sample case 101 at 1.0 L/min. The upper surface of the sample case 101 is made of glass, and has a structure that allows the laser light L to pass therethrough. Using the galvanometer scanner 104, while moving the focal position at a maximum speed of 25 mm / sec, a laser beam (center wavelength 355 nm, frequency 300 kHz, pulse width 10 ns, output 230 mW, spot diameter 20 μm) is applied to the coating film 2d in the sample case 101. irradiated. At this time, after moving the laser beam by 5 mm in the scanning direction (first irradiation), it was moved by 30 μm in the direction perpendicular to the scanning direction, and was moved again in the scanning direction at a maximum speed of 25 mm/sec (second irradiation). irradiation). By repeating this operation, the laser beam was scanned while being moved by 30 μm in a direction perpendicular to the scanning direction, and a copper-containing film containing copper having a desired dimension of 5 mm long×5 mm wide was obtained.

<Example 10>
The same method as in Example 6 was used, except that the substrate cleaning and pretreatment steps were performed as follows.
[Substrate washing and pretreatment process]
The polyimide substrate was cleaned by irradiating ultrasonic waves in ultrapure water for 5 minutes and then in ethanol for 5 minutes. Then, the surface of the substrate was subjected to UV ozone treatment for 3 minutes. The substrate was then immersed in 1-heptanol at room temperature (23° C.) for 15 minutes. After that, the surface of the substrate was blown with air to remove 1-heptanol.

<Example 11>
The same method as in Example 6 was used, except that the substrate cleaning and pretreatment steps were performed as follows.
[Substrate washing and pretreatment process]
The polyimide substrate was cleaned by irradiating ultrasonic waves in ultrapure water for 5 minutes and then in ethanol for 5 minutes. Then, the surface of the substrate was subjected to UV ozone treatment for 3 minutes. The substrate was then immersed in propanol at room temperature (23° C.) for 15 minutes. After that, the surface of the substrate was air-blown to remove the propanol.

<Example 12>
The same method as in Example 6 was followed except that the preparation of the dispersion, the coating and drying of the dispersion were performed as follows.
[Manufacturing of Dispersion]
3224 g of copper (II) acetate monohydrate (manufactured by Nippon Kagaku Sangyo Co., Ltd.) is dissolved in a mixed solvent consisting of 30240 g of water and 13976 g of 1,2-propylene glycol (manufactured by AGC), hydrazine hydrate ( (manufactured by Japan Finechem Co., Ltd.) was added and stirred, and then 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 1-butanol (manufactured by Sankyo Chemical Co., Ltd.) as a dispersion medium were added, and a nitrogen atmosphere was added. A homogenizer was used to obtain a dispersion containing cuprous oxide particles (as metal compound-containing particles). The amount of hydrazine in the dispersion was 0.2% by mass. 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.
[Application and drying of dispersion]
After dropping 1 ml of the dispersion onto the surface and spin coating (200 rpm, 100 seconds), drying was performed at 60° C. for 1 hour to obtain a sample having a dry coating film formed on the substrate.

<Example 13>
The same method as in Example 6 was used, except that the substrate cleaning and pretreatment steps were performed as follows.
[Substrate washing and pretreatment process]
The polyimide substrate was cleaned by irradiating ultrasonic waves in ultrapure water for 5 minutes and then in ethanol for 5 minutes. Then, the surface of the substrate was subjected to UV ozone treatment for 3 minutes. The substrate was then immersed in ethanol at room temperature (23° C.) for 15 minutes. After that, the surface of the substrate was air-blown to remove the ethanol.

<Example 14>
The same method as in Example 6 was used, except that the substrate cleaning and pretreatment steps were performed as follows.
[Substrate washing and pretreatment process]
The polyimide substrate was cleaned by irradiating ultrasonic waves in ultrapure water for 5 minutes and then in ethanol for 5 minutes. Then, the surface of the substrate was subjected to UV ozone treatment for 3 minutes. The substrate was then immersed in hexane for 15 minutes at room temperature (23°C). After that, the surface of the substrate was air-blown to remove the hexane.

<Example 15>
The same method as in Example 6 was used, except that the substrate cleaning and pretreatment steps were performed as follows.
[Substrate washing and pretreatment process]
The polyimide substrate was cleaned by irradiating ultrasonic waves in ultrapure water for 5 minutes and then in ethanol for 5 minutes. Then, the surface of the substrate was subjected to UV ozone treatment for 3 minutes. The substrate was then immersed in propylene glycol at room temperature (23° C.) for 15 minutes. After that, the surface of the substrate was air-blown to remove the propylene glycol.

<Example 16>
The same method as in Example 6 was used, except that the substrate cleaning and pretreatment steps and the posttreatment step were performed as follows.
[Substrate washing and pretreatment process]
The polyimide substrate was cleaned by irradiating ultrasonic waves in ultrapure water for 5 minutes and then in ethanol for 5 minutes. Then, the surface of the substrate was subjected to UV ozone treatment for 3 minutes.
[Post-treatment process]
After drying, it was stored for 24 hours in a room under normal pressure, room temperature of 23°C and relative humidity of 100%.

<Example 17>
The same method as in Example 6 was used, except that the substrate cleaning and pretreatment steps were performed as follows.
[Substrate washing and pretreatment process]
The polyimide substrate was cleaned by irradiating ultrasonic waves in ultrapure water for 5 minutes and then in ethanol for 5 minutes. The substrate was then immersed in a 4% by mass sodium hydroxide aqueous solution at room temperature (23° C.) for 15 minutes. After that, the substrate was washed with water, and the surface of the substrate was air-blown to remove the water.

<Example 18>
It was carried out in the same manner as in Example 16, except that the post-treatment step was not carried out.

<Example 19>
The same method as in Example 6 was used, except that the plating step was not performed.

<Comparative Example 1>
It was carried out in the same manner as in Example 5, except that the cleaning of the base material, the pretreatment step, and the posttreatment step were not performed.
As a result of the tape peeling test, peeling of the copper-containing film was observed.

<Comparative Example 2>
It was carried out in the same manner as in Example 6, except that the pretreatment process and the posttreatment process were not carried out.
As a result of the tape peeling test, peeling of the copper-containing film was observed.

Tables 1 and 2 show the results of Examples and Comparative Examples. As shown in Tables 1 and 2, it was found that pretreatment and/or posttreatment improved adhesion.

<Examples 20 to 23>
[Evaluation of inkjet suitability]
Same as Example 1 except that the dispersion solvent was changed to 1-butanol (Example 20), 1-hexanol (Example 21), 1-heptanol (Example 22), or 1-octanol (Example 23). A dispersion (ink) was prepared in the same manner. The obtained ink was evaluated for intermittent ink jet stability. The time until clogging of the nozzle occurred during intermittent ejection was measured and evaluated as follows: 1 hour or more: A, 30 minutes or more and less than 1 hour: B, and less than 30 minutes: C. Evaluation conditions for intermittent stability are as follows.
Equipment: DIMATIX material printer DMP-2831
Head: DMC-11610
Voltage: 25V
Number of ejection nozzles: 7 (No. 5 to 11)
Judgment of ejection presence/absence: Visual observation with DropWatcher Table 3 shows the results.

The 1-butanol solvent ink was evaluated C, the 1-hexanol solvent ink was evaluated B, and the 1-heptanol solvent ink and the 1-octanol solvent ink were evaluated A. From these results, it was found that inks using 1-heptanol or 1-octanol as a solvent have good inkjet suitability.

It should be noted that the present invention is not limited to the above embodiments or examples. Based on the knowledge of a person skilled in the art, design changes or the like may be added to the above embodiments or examples, and the above embodiments or examples may be combined arbitrarily. Included within the scope of the present invention.

One aspect of the present invention can be suitably applied to the production of printed wiring boards, electronic devices, electromagnetic wave shields, antistatic films, and the like.

10 copper oxide ink 12 copper oxide 13 phosphate ester salt 13a phosphorus 13b ester salt 1 substrate 2a supernatant 2b precipitate 2c dispersion 2d copper oxide-containing film 2e copper oxide and/or copper layer 2f plated copper layer 100 laser irradiation device 101 Sample case 102 Light beam oscillator 103 Gas supply unit 104 Galvanometer scanner 104a X-axis galvanometer mirror 104b X-axis galvanometer motor 104c Y-axis galvanometer mirror 104d Y-axis galvanometer motor 105 Scanner controller 106 Computer L Laser beam

Claims (20)

A coating film forming step of coating a substrate with a dispersion containing the metal compound-containing particles and/or the metal-containing particles to obtain a coating film;
a pretreatment step and/or a posttreatment step;
A method for manufacturing a structure with a conductive pattern, comprising
The pretreatment step is a step of subjecting the substrate to one or more treatments selected from the group consisting of UV ozone treatment, organic solvent treatment, and alkali treatment before the coating film forming step,
The method for manufacturing a conductive patterned structure, wherein the post-treatment step is a step of performing a humidification treatment and/or a heat treatment after the coating film formation step. 2. The method for manufacturing a conductive patterned structure according to claim 1, wherein said pretreatment step is an organic solvent treatment using an organic solvent having an SP value of 7.5 or more and 12.6 or less. 3. The method for producing a conductive patterned structure according to claim 2, wherein the organic solvent has an SP value of 9.9 or more and 11.6 or less. 3. The method for producing a conductive patterned structure according to claim 2, wherein said organic solvent contains at least one selected from the group consisting of N-methylpyrrolidone, 1-propanol and 1-heptanol. 3. The method for producing a conductive patterned structure according to claim 2, wherein the organic solvent contains N-methylpyrrolidone. The conductive according to claim 1 or 2, wherein the pretreatment step is an organic solvent treatment using an organic solvent having a difference between the SP value of the base material and the SP value of the organic solvent of 0.01 or more and 4.6 or less. A method for manufacturing a structure with a patterned structure. 3. The method for manufacturing a structure with a conductive pattern according to claim 1, further comprising a reduction step after said coating film forming step. 8. The method for manufacturing a conductive patterned structure according to claim 7, wherein said reduction step is a wet reduction step. 3. The method for manufacturing a structure with a conductive pattern according to claim 1, further comprising a plating step of plating after said coating film forming step. 10. The method for manufacturing a structure with a conductive pattern according to claim 9, wherein a plating solution containing EDTA (ethylenediaminetetraacetic acid) is used in said plating step. 3. The method for manufacturing a structure with a conductive pattern according to claim 1, further comprising a reduction step after said coating film forming step, and a plating step after said reduction step. 3. The method for manufacturing a structure with a conductive pattern according to claim 1, comprising both the pretreatment step and the posttreatment step. 3. The method for producing a structure with a conductive pattern according to claim 1, wherein the base material is polyimide. 3. The method for producing a conductive patterned structure according to claim 1, wherein said dispersion contains at least one selected from the group consisting of 1-hexanol, 1-heptanol and 1-octanol. 3. The method for producing a conductive patterned structure according to claim 1, wherein said metal compound-containing particles and/or said metal-containing particles are copper oxide-containing particles and/or copper-containing particles. a dispersion containing metal compound-containing particles and/or metal-containing particles;
A plating solution containing EDTA (ethylenediaminetetraacetic acid), and a substrate subjected to one or more treatments selected from the group consisting of UV ozone treatment, organic solvent treatment, and alkali treatment,
A conductive patterned structure manufacturing kit, comprising: a dispersion containing metal compound-containing particles and/or metal-containing particles;
a plating solution containing EDTA (ethylenediaminetetraacetic acid);
one or more treating agents selected from the group consisting of organic solvents and alkaline treating agents; and a substrate;
A conductive patterned structure manufacturing kit, comprising: a dispersion comprising metal compound-containing particles and/or metal-containing particles, and an organic solvent for organic solvent treatment;
and the SP value of the organic solvent is 7.5 or more and 12.6 or less. The conductive patterned structure manufacturing kit according to any one of claims 16 to 18, wherein the metal compound-containing particles and/or the metal-containing particles are copper oxide-containing particles and/or copper-containing particles. A pretreatment mechanism for applying an organic solvent treatment to a substrate using an organic solvent having an SP value of 7.5 or more and 12.6 or less;
a coating mechanism for obtaining a coating film by coating a substrate with a dispersion containing metal compound-containing particles and/or metal-containing particles;
a plating mechanism for plating the coating film that has passed through the coating mechanism;
comprising
A manufacturing system for structures with conductive patterns.

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