CN115968113A - Method for manufacturing structure with conductive pattern, kit and system - Google Patents

Method for manufacturing structure with conductive pattern, kit and system Download PDF

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Publication number
CN115968113A
CN115968113A CN202211205287.2A CN202211205287A CN115968113A CN 115968113 A CN115968113 A CN 115968113A CN 202211205287 A CN202211205287 A CN 202211205287A CN 115968113 A CN115968113 A CN 115968113A
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China
Prior art keywords
conductive pattern
treatment
metal
dispersion
substrate
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CN202211205287.2A
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Chinese (zh)
Inventor
大桥瞳
汤本徹
古川雅志
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Asahi Kasei Corp
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Asahi Kasei Corp
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Abstract

The present invention relates to a method, a kit, and a system for manufacturing a structure with a conductive pattern. The invention provides a method for manufacturing a structure with a conductive pattern, which can form a structure with a conductive pattern with good interlayer adhesion. A method for manufacturing a structure with a conductive pattern, comprising the steps of: a coating film forming step of applying a dispersion containing particles containing a metal compound and/or particles containing a metal to a substrate to obtain a coating film; and a pretreatment step and/or a post-treatment step, wherein the pretreatment step is a step of subjecting the substrate to UV ozone treatment and organic solvent treatment before the coating film formation step, and the post-treatment step is a step of performing humidification treatment and/or heat treatment after the coating film formation step.

Description

Method for manufacturing structure with conductive pattern, kit and system
Technical Field
The present invention relates to a method for manufacturing a structure with a conductive pattern.
Background
The circuit board has a structure in which conductive wiring is provided on a base material. The method of manufacturing the circuit board is generally as follows. First, a photoresist is applied to a substrate to which a metal foil is bonded. Subsequently, the photoresist is exposed and developed to obtain a desired shape of a circuit pattern in a form of a bottom plate. Thereafter, the metal foil is removed from the portion not covered with the photoresist by chemical etching to form a pattern. Thereby, a high-performance circuit board can be manufactured. However, the conventional method has disadvantages of a large number of steps, complexity, and the need for a photoresist material.
In contrast, a direct printing technique for directly printing a desired wiring pattern on a substrate using a dispersion in which metal or metal oxide particles are dispersed has been attracting attention. The number of steps in this technique is extremely high, and the use of a photoresist material or the like is not necessary. However, in the case of using the metal particles, there is a possibility that a problem arises in stability due to oxidation or the like of the metal particles themselves. On the other hand, when metal oxide particles are used, a reduction firing step is required to obtain conductivity, which causes problems such as limitation of usable substrates and an increase in cost due to the need for a reducing gas.
In relation to the above, for example, patent document 1 describes a method for forming a conductive film in a predetermined pattern 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 that of a conductive film, and thereafter a plating film is formed by electroless plating at least 1 time so as to cover the surface of the metal film, thereby obtaining the conductive film.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2006-128228
Disclosure of Invention
Problems to be solved by the invention
In the method described in patent document 1, a conductive film having excellent conductivity and reliability can be formed by combining pattern formation using metal particles with plating, but in this method, the adhesion between the conductive film and a substrate and/or the interlayer adhesion in the conductive film still have disadvantages.
In view of the above circumstances, an object of one embodiment of the present invention is 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.
Means for solving the problems
The present disclosure includes the following items.
[ item 1]
A method for manufacturing a structure with a conductive pattern, comprising the steps of:
a coating film forming step of applying a dispersion containing particles containing a metal compound and/or particles containing a metal to a substrate to obtain a coating film; and
a pre-treatment step and/or a post-treatment step,
wherein the content of the first and second substances,
the pretreatment step is a step of subjecting the substrate to 1 or more kinds of treatment selected from the group consisting of UV ozone treatment, organic solvent treatment and alkali treatment before the coating film formation step,
the post-treatment step is a step of performing a humidification treatment and/or a heating treatment after the coating film formation step.
[ item 2]
The method of manufacturing a structure with a conductive pattern according to item 1, wherein the pretreatment step is an organic solvent treatment using an organic solvent having an SP value of 7.5 to 12.6.
[ item 3]
The method of manufacturing a structure with a conductive pattern according to item 2, wherein the SP value of the organic solvent is 9.9 to 11.6.
[ item 4]
The method for producing a structure with a conductive pattern according to item 2 or 3, wherein the organic solvent contains at least 1 selected from the group consisting of N-methylpyrrolidone, 1-propanol, and 1-heptanol.
[ item 5]
The method for producing a structure with a conductive pattern according to any one of items 2 to 4, wherein the organic solvent contains N-methylpyrrolidone.
[ item 6]
The method of manufacturing a structure with a conductive pattern according to any one of items 1 to 5, wherein the pretreatment step is an organic solvent treatment using an organic solvent in which a difference between an SP value of the base material and an SP value of the organic solvent is 0.01 to 4.6.
[ item 7]
The method for manufacturing a structure with a conductive pattern according to any one of items 1 to 6, further comprising a reducing step after the coating film forming step.
[ item 8]
The method of manufacturing a structure with a conductive pattern according to item 7, wherein the reducing step is a wet reducing step.
[ item 9]
The method of manufacturing a structure with a conductive pattern according to any one of items 1 to 8, further comprising a plating step of performing plating after the coating film forming step.
[ item 10]
The method of manufacturing a structure with a conductive pattern according to item 9, wherein in the plating step, a plating solution containing EDTA (ethylenediaminetetraacetic acid) is used.
[ item 11]
The method for manufacturing a structure with a conductive pattern according to any one of items 1 to 10, further comprising a reducing step after the coating film forming step, and further comprising a plating step after the reducing step.
[ item 12]
The method for producing a structure with a conductive pattern according to any one of items 1 to 11, comprising two steps of the pretreatment step and the post-treatment step.
[ item 13]
The method for producing a structure with a conductive pattern according to any one of items 1 to 12, wherein the substrate is polyimide.
[ item 14]
The method for producing a structure with a conductive pattern according to any one of items 1 to 13, wherein the dispersion contains at least 1 selected from the group consisting of 1-hexanol, 1-heptanol, and 1-octanol.
[ item 15]
The method of manufacturing a structure with a conductive pattern according to any one of items 1 to 14, wherein the particles containing a metal compound and/or the particles containing a metal are/is copper oxide-containing particles and/or copper-containing particles.
[ item 16]
A structure manufacturing kit with a conductive pattern, comprising:
a dispersion comprising particles comprising a metal compound and/or particles comprising a metal;
a plating solution containing EDTA (ethylenediaminetetraacetic acid); and
a substrate subjected to 1 or more treatments selected from the group consisting of UV ozone treatment, organic solvent treatment and alkali treatment.
[ item 17]
A structure manufacturing kit with a conductive pattern, comprising:
a dispersion comprising particles comprising a metal compound and/or particles comprising a metal;
a plating solution containing EDTA (ethylenediaminetetraacetic acid);
1 or more treating agents selected from the group consisting of organic solvents and alkali treating agents; and
a substrate.
[ item 18]
A structure manufacturing kit with a conductive pattern, comprising:
a dispersion comprising particles comprising a metal compound and/or particles comprising a metal; and
an organic solvent for the treatment of the organic solvent,
the SP value of the organic solvent is 7.5 to 12.6.
[ item 19]
The conductive-patterned structure production kit 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 system for manufacturing a structure with a conductive pattern, comprising:
a pretreatment mechanism for subjecting the base material to an organic solvent treatment using an organic solvent having an SP value of 7.5 to 12.6;
a coating mechanism that coats a dispersion containing particles containing a metal compound and/or particles containing a metal to a substrate to obtain a coating film; and
and a plating mechanism for plating the coating film passing through the coating mechanism.
ADVANTAGEOUS EFFECTS OF INVENTION
According to one embodiment of the present invention, a method for manufacturing a structure with a conductive pattern, which can form a structure with a conductive pattern having good interlayer adhesion, can be provided.
Drawings
Fig. 1 is a schematic sectional view showing the relationship between copper oxide and phosphate in a dispersion that can be used in one embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view showing a manufacturing process of a structure with a conductive pattern according to an embodiment of the present invention.
Fig. 3 is a schematic diagram showing an example of a laser irradiation apparatus for manufacturing a structure with a conductive pattern.
Description of the symbols
10. Copper oxide ink
12. Copper oxide
13. Phosphoric ester salts
13a phosphorus
13b ester salt
1. Base material
2a supernatant
2b precipitate
2c Dispersion
2d film containing copper oxide
2e layer of copper oxide and/or copper
2f plating copper layer
100. Laser irradiation device
101. Sample box
102. Optical oscillator
103. Gas supply unit
104. Galvanometer scanner
104a X-axis galvanometer
104b X-axis galvanometer motor
104c Y-axis galvanometer
104d Y-axis galvanometer motor
105. Scanner control unit
106. Computer with a memory card
L laser
Detailed Description
The following examples illustrate embodiments of the present invention, but the present invention is not limited to these embodiments.
One embodiment of the present invention provides a method for manufacturing a structure with a conductive pattern. In one embodiment, the method comprises the steps of:
a coating film forming step of applying a dispersion containing particles containing a metal compound and/or particles containing a metal to a substrate to obtain a coating film; and
a pretreatment step and/or a post-treatment step.
In one embodiment, the pretreatment step is a step of subjecting the substrate to 1 or more kinds of treatment selected from the group consisting of UV ozone treatment, organic solvent treatment, and alkali treatment before the coating film formation step.
In one embodiment, the post-treatment step is a step of performing a humidification treatment and/or a heating treatment after the coating film formation step.
The pretreatment step and the post-treatment step contribute to improvement in interlayer adhesion between the base material and the metal compound and/or metal layer formed on the base material. In one embodiment, one or both of the pretreatment step and the post-treatment step may be performed, and preferably both of them are performed. The method of the present embodiment can be advantageous for reducing the resistance of the structure with a conductive pattern.
Suitable examples of the respective steps are explained below.
[ base Material ]
The substrate used in the present embodiment has a surface on which a coating film is formed, and examples thereof include a substrate material for a circuit substrate 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 embodiment.
Examples of the inorganic material include glass such as soda lime glass, alkali-free glass, borosilicate glass, and quartz glass, and ceramic materials such as alumina.
Examples of the organic material include paper materials such as cellulose and polymer materials such as resin films. Examples of the polymer material include Polyimide (PI), polyester (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and the like), polyethersulfone (PES), polycarbonate (PC), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyacetal (POM), polyarylate (PAR), polyamide (PA) (PA 6, PA66, and the like), polyamideimide (PAI), polyetherimide (PEI), polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyphenylene sulfide (PPS), polyether ketone (PEK), polyphthalamide (PPA), polyether nitrile (PENt), polybenzimidazole (PBI), polycarbodiimide, silicone polymer (polysiloxane), polymethacrylamide, nitrile rubber, acrylic rubber, polytetrafluoroethylene, epoxy resin, phenol resin, melamine resin, urea resin, polymethylmethacrylate resin (PMMA), polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene-diene copolymer, polybutadiene, polyisoprene, ethylene-propylene-pentene copolymer, butyl rubber, polymethylene (PMP), polystyrene (PS), polyvinylidene fluoride (PVC), polyvinyl chloride-styrene copolymer (PVC), polyvinyl chloride-vinylidene fluoride (PVC), polyvinyl chloride (PVC), and the like, polyether ether ketone (PEEK), novolac, benzocyclobutene, polyvinylphenol, polypyrene, 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. From the viewpoints of flexibility and cost, polyimide (PI), polyethylene terephthalate (PET), and polyethylene naphthalate (PEN) are preferable. Among them, polyimide (PI) is preferable because it has an imide bond, and thus can exhibit an effect of improving adhesion by the pretreatment step and/or the post-treatment step of the present disclosure.
The substrate may be, for example, a glass composite substrate, a composite substrate such as a glass epoxy substrate, a teflon (registered trademark) substrate, an alumina substrate, a low temperature low humidity co-fired ceramic (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 10mm or less, or 1mm or less, or 250 μm or less. When the thickness of the substrate is 250 μm or less, the electronic device to be manufactured can be reduced in weight, space, and flexibility, and is preferable.
< pretreatment step >
One embodiment of the method of the present disclosure includes a pretreatment step for the purpose of improving adhesion between a substrate and a layer of a metal compound and/or a metal. The pretreatment step is a step of subjecting the substrate to 1 or more kinds of treatment selected from the group consisting of UV ozone treatment, organic solvent treatment, and alkali treatment before the coating film formation step. By using 2 or more of the above treatments in combination, the adhesion improving effect tends to be more excellent.
The UV ozone treatment is a treatment for promoting decomposition of organic substances attached to the surface of a substrate by UV (ultraviolet) light and ozone generated therefrom. The UV ozone treatment can improve the adhesion between the substrate and the metal compound and/or the metal layer by exposing the functional group originally present in the substrate to the surface. Substrates particularly suitable for UV ozone treatment are in particular polyimides.
The UV ozone treatment can be performed using a UV cleaning/modifying device, a slide type ultraviolet cleaning machine (both manufactured by SEN special light source co., ltd., for example), a UV ozone cleaning/modifying device (manufactured by Sun Energy co., ltd., for example), or the like. The treatment conditions may be appropriately adjusted so that only the surface of the substrate is treated, and for example, the UV ozone treatment time is preferably 1 minute or more, or 2 minutes or more, and preferably 30 minutes or less, or 20 minutes or less.
The organic solvent treatment is a treatment of bringing a substrate into contact with an organic solvent. The contact may be impregnation of the substrate in an organic solvent, spraying of the substrate with an organic solvent, or the like, and preferably impregnation of the substrate in an organic solvent. As the organic solvent, a solvent that dissolves or swells the base material is preferable. By bringing such a solvent into contact with the substrate under controlled conditions, only the surface of the substrate can be dissolved or swollen. The solubility parameter (hereinafter also referred to as "SP value") of the organic solvent is preferably 7.5 to 16.0, more preferably 7.5 to 12.6, and most preferably 9.9 to 11.6, from the viewpoint of effectively swelling the base material and improving the adhesion. In addition, 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 to 4.6, more preferably 0.01 to 2.2, and most preferably 0.01 to 0.7. In the present disclosure, the SP value refers to hansen solubility parameter and is expressed in (cal/cm) 3 ). The hansen solubility parameter is a parameter that divides the Hildebrand solubility parameter into 3 types of components of a dispersion force term (δ D), a polarity term (δ P), and a hydrogen bond term (δ H) and represents the 3-dimensional space. When the solubility parameter is recorded as delta, delta is present 2 ＝(δD) 2 +(δP) 2 +(δH) 2 The relationship (c) in (c). 2 kinds of substances having similar SP values are easily dissolved in each other, and when an organic solvent having a SP value similar to that of the base material is used, the base material can be effectively swelled. For example, in the case of using polyimide as the base material, polyimideThe SP value of (b) is in the range of approximately 12.0 to 12.1, and for example, the SP value of pyromellitic anhydride-4, 4 oxydiphenylamine type polyimide is 12.1, and therefore if the SP value of the organic solvent is 7.5 to 16.0, the polyimide substrate can be effectively swollen. The SP value can be calculated by the Hoy method using Software (Hoy Solubility Parameter Software manufactured by Computer Chemistry Consultancy). As the organic solvent, specifically, preferred are: amide solvents such as N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide; cyclic ester solvents such as γ -butyrolactone, γ -valerolactone, δ -valerolactone, γ -caprolactone, e-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 propylene glycol and triethylene glycol; glycol ether solvents such as ethyl cellosolve and butyl cellosolve; ethylene glycol ester solvents such as propylene glycol methyl acetate, 2-methyl cellosolve acetate, ethyl cellosolve acetate, and butyl cellosolve acetate; phenol solvents such as phenol, o-cresol, m-cresol, p-cresol, 3-chlorophenol, and 4-chlorophenol; ketone solvents such as acetophenone, 1, 3-dimethyl-2-imidazolidinone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, and acetone; sulfone solvents such as sulfolane and dimethyl sulfoxide; hydrocarbon solvents such as xylene, toluene, chlorobenzene, hexane, and benzene; halogen-based solvents such as chloroform; aniline solvents such as dimethylaniline; 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. Particularly when a polyimide substrate is used, N-methylpyrrolidone, 1-propanol, and 1-heptanol are preferable, and N-methylpyrrolidone is most preferable, since polyimide can be swelled. When the base material swells and the dispersion is applied to the base material, an anchor effect is exerted between the layer of the metal compound and/or metal and the base material, and these adhesion properties are good.
The treatment conditions for the organic solvent treatment may be appropriately adjusted so that only the surface of the base material is treated, and for example, the immersion time is preferably 5 minutes or more, or 10 minutes or more, and preferably 120 minutes or less, or 60 minutes or less. The impregnation temperature is preferably 10 ℃ or more, or 20 ℃ or more, and preferably 100 ℃ or less, or 60 ℃ or less.
The alkali treatment is a treatment of bringing a substrate into contact with an alkali treatment agent. The contact may be immersion of the base material in an alkaline treatment agent, spraying of the alkaline treatment agent to the base material, or the like, and immersion of the base material in an alkaline treatment agent is preferable. Examples of the alkaline treatment agent include an aqueous potassium hydroxide solution, an aqueous sodium hydroxide solution, an aqueous 2-aminoethanol solution, and an aqueous diethylenetriamine solution. The pH of the alkaline treatment agent is preferably 8 or more, or 9 or more, or 10 or more, and preferably 13 or less. In the alkali treatment, the chemical structure of the layer capable of firmly holding the metal compound and/or the metal can be formed on the surface of the substrate by chemically modifying the surface of the substrate. In one embodiment, the surface of the substrate is partially hydrolyzed by alkali treatment to generate a hydrogen-bonding functional group such as a hydroxyl group or a carboxyl group, whereby hydrogen bonds can be formed between the metal compound and/or the metal layer and the substrate, and the adhesion can be improved. For example, when a polyimide substrate is used, the imide bond of the polyimide is cleaved by alkali treatment, and thus adhesion between the metal compound and/or the metal layer and the substrate is improved by hydrogen bonds derived from the amide site of the imide group, coordination of the metal (copper in one embodiment) with the carboxylate anion generated by the cleavage, and the like.
The treatment conditions for the alkali treatment may be appropriately adjusted so that only the surface of the base material is treated, and for example, the immersion time is preferably 5 minutes or more, or 10 minutes or more, and preferably 120 minutes or less, or 60 minutes or less. The impregnation temperature is preferably 10 ℃ or higher, or 20 ℃ or higher, and preferably 100 ℃ or lower, or 60 ℃ or lower.
< coating film Forming step >
In this step, a dispersion containing particles containing a metal compound and/or particles containing a metal (also simply referred to as a dispersion in the present disclosure) is applied to a substrate to obtain a coating film.
[ Dispersion containing particles containing a Metal Compound and/or particles containing a Metal ]
In one embodiment, the dispersion comprises particles comprising a metal compound and/or particles comprising a metal. The particles containing a metal compound are typically formed of a metal compound, but may contain other components within a range not impairing the effects of the present invention. Similarly, the metal-containing particles are typically formed of a metal, but may contain other components within a range not impairing the effects of the present invention. The dispersion may further comprise a dispersing medium, a dispersing agent and/or a reducing agent.
In one embodiment, the metal may be 1 or an alloy or a mixture of 2 or more metals selected from 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. The metal is preferably copper or silver, and particularly preferably copper, in view of ease of stable production of particles having a particle diameter described below, good conductivity, and ease of handling.
The metal compound may be a compound of 1 or 2 or more metals as exemplified above. Examples of the metal compound include metal oxides and metal hydroxides, and oxides are preferable. The metal oxide is preferably copper oxide or silver oxide because it is easily reduced and can form a uniform conductive pattern. Further, the metal oxide is preferably copper oxide in view of high stability in air and commercial advantage in view of low cost availability. As the copper oxide, monovalent copper oxide and/or divalent copper oxide can be used. The copper oxide-containing particle may have a core/shell structure, and either one of the core and the shell may contain copper monooxide and/or copper bioxide.
(copper oxide or copper)
Examples of the copper oxide include cuprous oxide (Cu) 2 O) and cupric oxide (CuO), preferably cuprous oxide. The cuprous oxide is advantageous in that it is copper and therefore less expensive than noble metals such as silver, and in that migration is less likely to occur. Absorption of cuprous oxide from laserIt is also advantageous in that the light intensity is high and low-temperature sintering is possible, and that a sintered product with low resistance can be formed. As the copper oxide or copper, commercially available products or synthetic products can be used.
For example, the following method can be mentioned as a method for synthesizing cuprous oxide.
(1) A method for thermal reduction, wherein water and a copper acetylacetonate complex are added to a polyol solvent to dissolve an organic copper compound by heating once, and then water required for the reaction is added thereto, and the temperature is further raised to heat the mixture at a reduction temperature of the organic copper.
(2) A method of heating an organocopper compound (for example, a copper-N-nitrosophenylhydroxylamine complex) at a high temperature of about 300 ℃ in an inert atmosphere in the presence of a protective agent such as hexadecylamine.
(3) A method of reducing a copper salt dissolved in an aqueous solution with hydrazine.
Among them, the method (3) is preferable because it is easy to handle and can obtain cuprous oxide having a small average particle size.
The following method can be mentioned as a method for synthesizing cupric oxide.
(1) Adding sodium hydroxide into the aqueous solution of copper chloride or copper sulfate to generate copper hydroxide, and heating.
(2) A method of heating copper nitrate, copper sulfate, copper carbonate, copper hydroxide, etc. in the air to a temperature of about 600 ℃ for thermal decomposition.
Among them, the method (1) is preferable because divalent copper oxide having a small particle size can be obtained.
After completion of the synthesis of copper oxide, the resultant solution (as a supernatant) and copper oxide (as a precipitate) can be separated by a known method such as centrifugation. Particles containing copper oxide can be obtained as described above.
In the preparation of the dispersion, the dispersion medium described later and optionally the dispersant described later may be added to the metal compound-containing particles and/or the metal-containing particles, and the mixture may be dispersed by stirring by a known method such as a homogenizer. In the case where the metal compound or the metal (copper oxide in one embodiment) is difficult to disperse and insufficient in dispersion depending on the dispersion medium, for example, an alcohol (for example, 1-butanol or the like) in which the metal compound or the metal (copper oxide in one embodiment) is easily dispersed may be used as the dispersion medium to disperse the metal compound or the metal, and the dispersion medium may be replaced with a desired dispersion medium and adjusted to a desired concentration to disperse the metal compound or the metal in the desired dispersion medium satisfactorily. Examples of the method include a method of concentrating with a UF membrane and a method of repeating dilution and concentration with an appropriate dispersion medium. This may result in a dispersion comprising particles comprising a metal compound and/or particles comprising a metal.
In one embodiment, the average particle diameter of the metal compound-containing particles and/or the metal-containing particles (the average particle diameter of the metal compound-containing particles and the metal-containing particles in their entirety when they are present together) is preferably 1nm or more, or 3nm or more, or 5nm or more, and preferably 100nm or less, or 50nm or less, or 40nm or less. The average particle diameter herein means a particle diameter when dispersed in a dispersion, and is a value measured by an accumulation method (for example, using an Otsuka electronic FPAR-1000). That is, the average particle diameter is not limited to the primary particle diameter, and may be a secondary particle diameter. When the average particle size is 100nm or less, patterning at a low temperature is possible, and it is preferable in terms of widening the versatility of the substrate and in terms of a tendency to easily form a fine pattern on the substrate. When the average particle diameter is 1nm 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 can be formed. In one embodiment, the particles in the dispersion are substantially only metal compound-containing particles and/or metal-containing particles. In this case, the value of the average particle diameter measured for the dispersion may be regarded as the average particle diameter of the metal compound-containing particles and the metal-containing particles.
In one embodiment, the metal compound-containing particles and/or the metal-containing particles comprise hydrazine. Hydrazine can form hydrates (i.e., hydrazine hydrate is also included in the concept of hydrazine of the present disclosure). The hydrazine may be, for example, a residual hydrazine used as a reducing agent for a metal oxide (copper oxide in one embodiment) in producing particles containing a metal oxide (copper oxide in one embodiment) or particles containing a metal (copper oxide in one embodiment), or may be separately added in producing 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 mass% or more, or 30 mass% or more, or 50 mass% or more, or 70 mass% or more, and preferably 100 mass% or less, or 99 mass% or less, or 98 mass% or less.
The content of hydrazine in the metal compound-containing particles or the metal-containing particles is preferably 0.000000001 mass% or more, or 0.0000001 mass% or more, or 0.0000005 mass% or more, and preferably 10 mass% or less, or 5 mass% or less, or 1 mass% or less.
The mass ratio of hydrazine to the metal compound in the metal compound-containing particle or the metal in the metal-containing particle is preferably 0.00001 or more, or 0.0001 or more, or 0.0002 or more, and 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 mass% of the dispersion is preferably 5 mass% or more, or 10 mass% or more, or 15 mass% or more, and preferably 60 mass% or less, or 55 mass% or less, or 50 mass% or less.
(dispersing Medium)
The dispersion medium is a substance that can disperse the metal compound-containing particles and/or the metal-containing particles. In one embodiment, the dispersing medium may dissolve the dispersing agent. From the aspect of forming a conductive pattern using a dispersion, the volatility of the dispersion medium affects workability. Therefore, the dispersion medium is preferably suitable for a method for forming a conductive pattern, for example, a method suitable for coating (particularly printing). That is, the dispersion medium is preferably selected in accordance with dispersibility and printing workability.
As the dispersion medium, alcohols (monohydric alcohols and polyhydric alcohols (e.g., glycols)), ethers of alcohols (e.g., glycols), esters of alcohols (e.g., glycols), and the like can be used. <xnotran> , ,3- -3- - , , , , , , , , , , ,1,2- ,1,3- ,2- ,2- -2,4- ,2,5- ,2,4- ,2- -1,3- , , , , , -1,2- , , , , , , , , , , , , ,2- , , , ,2- ,2- , ,3- , ,2- ,2- ,2- , 1- ,2- ,3- , ,2- ,2- , ,2,6 -4- , , , ,3,3,5- , , . </xnotran> These may be used alone or in combination, and may be selected in consideration of evaporation property, equipment used for coating, solvent resistance of the substrate (i.e., substrate to be coated), and the like, depending on the coating method. From the viewpoint that drying is slow and aggregation of ink is not likely to occur when continuous printing is used; and in the case of ink jet printing, the dispersion particularly preferably contains 1 or more kinds of dispersion media selected from the group consisting of 1-hexanol, 1-heptanol, and 1-octanol in view of good batch stability and less abnormal flight.
From the viewpoint of improving the printing continuity, the boiling point of the dispersion medium is preferably high, and is, for example, preferably 50 ℃ or higher, more preferably 100 ℃ or higher, and still more preferably 150 ℃ or higher. On the other hand, the boiling point is preferably 400 ℃ or lower, more preferably 300 ℃ or lower, and still more preferably 250 ℃ or lower, from the viewpoint of obtaining a function as a dispersion medium satisfactorily.
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.
(dispersing agent)
As the dispersant, a compound capable of dispersing the metal compound-containing particles and/or the metal-containing particles in the dispersion medium may be used. The number average molecular weight of the dispersant is preferably 300 or more, or 350 or more, or 400 or more, and preferably 300,000 or less, or 200,000 or less, or 150,000 or less. The number average molecular weight of the present disclosure is a value obtained by gel permeation chromatography in terms of standard polystyrene. When the number average molecular weight is 300 or more, the insulation property is excellent, and the contribution to the dispersion stability of the dispersion tends to increase; a content of 300,000 or less is preferable from the viewpoint of handling properties. The dispersant preferably has a group having affinity for particles containing a metal compound and/or particles containing a metal, particularly particles containing copper oxide. From this point of view, the dispersant preferably contains or is a phosphorus-containing organic substance, or contains or is a phosphate ester of a polymer. The phosphate ester as a polymer is preferably a structure represented by the following formula (1) because it has excellent adsorbability to a metal compound, particularly a metal oxide, particularly copper oxide, particularly cuprous oxide, and adhesion to a substrate.
[ solution 1]
Figure BDA0003871492790000141
(wherein l is an integer of 1 to 10000, m is an integer of 1 to 10000, and n is an integer of 1 to 10000.)
In the chemical formula (1), l is more preferably 1 to 5000, and still more preferably 1 to 3000.
In chemical formula (1), m is more preferably 1 to 5000, and still more preferably 1 to 3000.
In chemical formula (1), n is more preferably 1 to 5000, and still more preferably 1 to 3000.
In one embodiment, the decomposition temperature of the phosphorus-containing organic substance is preferably 600 ℃ or lower, more preferably 400 ℃ or lower, and still more preferably 200 ℃ or lower. The decomposition temperature may be 50 ℃ or higher, or 80 ℃ or higher, or 100 ℃ or higher, because it is easy to select a dispersant having an excellent effect of improving the dispersion stability of the dispersion. In one embodiment, the boiling point of the phosphorus-containing organic substance is preferably 300 ℃ or lower, more preferably 200 ℃ or lower, and still more preferably 150 ℃ or lower. The boiling point may be 30 ℃ or higher, or 50 ℃ or higher, or 80 ℃ or higher. In the present disclosure, the decomposition temperature is a value measured by thermogravimetric analysis.
In one embodiment, a phosphorus-containing organic substance is preferable because peeling between the coating film and the plating layer is less likely to occur when plating is performed.
As the dispersant, known ones can be used. Examples thereof include polymers having a basic group such as salts of long-chain polyaminoamides with polar acid esters, unsaturated polycarboxylic acid polyaminoamides, polycarboxylic acid salts of polyaminoamides, and salts of long-chain polyaminoamides with acid polymers. Further, there may be mentioned 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.
As the dispersant of the present disclosure, commercially available products can be used. As a commercially available product of the dispersant, examples thereof include 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, DISPERBYRK-2025, DISPERBYK-2163, DISPERBYK-2164, BYK-9076, BYK-77, DISPERBYK-90180, DISPERBYK-2000, DISPERBYK-2025, DISPERBYK-2163, DISPERYK-2164, DISPERBYK-9076, DISPERB-21677, and DISPERBYK-2164 TERRA-204 and TERRA-U (manufactured by Bikk chemical Co., ltd.), flowen DOPA-15B, flowen DOPA-15BHFS, flowen DOPA-22, flowen DOPA-33, flowen DOPA-44, flowen DOPA-17HF, flowen TG-662C and Flowen KTG-2400 (manufactured by Kyowa chemical Co., ltd.), ED-117, ED-118, ED-212, ED-213, ED-214, ED-216, ED-350 and ED-360 (manufactured by Machinoki chemical Co., ltd.), plusturf M208F and Plusturf DBS (manufactured by first Industrial pharmaceutical Co., ltd.), and the like. These may be used alone or in combination of two or more.
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, and it is preferable. In particular, when the average particle diameter of the metal compound-containing particles and/or the metal-containing particles is small, an acid value in the above range is effective. Specifically, examples thereof include "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) and "DISPERBYK-180" (acid value 94) manufactured by Bikk chemical company.
The difference between the amine value (mgKOH/g) and the acid value ([ amine value ] - [ acid value ]) of the dispersant is preferably from-50 to 0. The amine number represents the total amount of free base and sites derived from free base, and the acid number represents the total amount of free fatty acid and sites derived from free fatty acid. The amine value and acid value were measured by the methods according to JIS K7700 or ASTM D2074, respectively. When the value of [ amine value ] - [ acid value ] is not less than-50 and not more than 0, the dispersion stability of the dispersion is good, and it is preferable. The value of [ amine value ] - [ acid value ] is more preferably from-40 to 0, and still more preferably from-20 to 0.
The content of the dispersant may be adjusted in proportion to the amounts of the metal compound and the metal in consideration of the desired dispersion stability. The mass ratio of the dispersant to the metal compound and the metal in the dispersion (mass of the dispersant/total mass of the metal compound and the metal) is preferably 0.0050 or more, or 0.050 or more, or 0.10 or more, and preferably 0.30 or less, or 0.25 or less, or 0.23 or less. The amount of the dispersant influences the dispersion stability of the dispersion, and when the amount is small, the metal compound-containing particles and/or the metal-containing particles are liable to aggregate, and when the amount is large, the dispersion stability of the dispersion tends to be improved. However, when the content of the dispersant in the dispersion is 35% by mass or less, the influence of the residue derived from the dispersant in the film containing a metal (e.g., copper), particularly in the film containing a metal (e.g., copper) obtained after the plating step in the case of performing the plating step, is suppressed, and the conductivity can be improved. In one embodiment, the amount of the dispersant in 100 mass% of the dispersion is preferably 0.5 mass% or more, or 0.8 mass% or more, or 1.0 mass% or more, and is preferably 35 mass% or less, or 30 mass% or less, or 25 mass% or less.
(reducing agent)
Where the dispersion comprises particles comprising a metal oxide, for example copper oxide, the dispersion may comprise a reducing agent. Examples of the reducing agent include hydrazine, sodium borohydride, potassium iodide, sulfite, sodium thiosulfate, formic acid, oxalic acid, ascorbic acid, iron (II) sulfide, tin (II) chloride, diisobutylaluminum hydride, carbon, and the like, and hydrazine is preferable. Hydrazine may be in the form of hydrazine hydrate (i.e., hydrazine hydrate is also included in the concept of hydrazine of the present disclosure). By the dispersion containing hydrazine, for example, in the plating step in the case of performing the plating step, hydrazine contributes to reduction of a metal oxide, particularly copper oxide, particularly cuprous oxide, and a reduced metal layer (as a metal-containing film), particularly a reduced copper layer (as a copper-containing film) having a lower resistance can be formed. Hydrazine is also advantageous in maintaining dispersion stability of the dispersion, and is also preferable in terms of improving productivity in plating. The 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) may be adjusted in proportion to the amount of the metal oxide in consideration of the desired reducibility. In one embodiment, the mass ratio of the reducing agent to the 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 electrical resistance of the reduced metal layer (reduced copper layer in one embodiment) is low, which is preferable; when the content is 0.1 or less, 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 the reducing agent other than hydrazine in the dispersion may be adjusted in consideration of the desired reducibility in proportion to the amount of the metal oxide. In one embodiment, the total mass ratio of hydrazine and the reducing agent other than hydrazine (total mass of reducing agent/mass of metal oxide) to the metal oxide in the dispersion is preferably 0.0001 or more, preferably 0.1 or less, or 0.05 or less, or 0.03 or less. When the above total mass ratio of the reducing agent is 0.0001 or more, the dispersion stability of the dispersion is good and the electrical resistance of the reduced metal layer (reduced copper layer in one embodiment) is low, which is preferable from the viewpoint of; when the content is 0.1 or less, the long-term stability of the dispersion is good.
The dispersion can be produced by mixing the components to be mixed and dispersing the mixture using a mixer method, an ultrasonic method, a three-roll method, a two-roll method, an attritor, a homogenizer, a banbury mixer, a paint shaker, a kneader, a ball mill, a sand mill, a revolution mixer, or the like. The viscosity of the dispersion can be designed according to the intended application. For example, the viscosity of the dispersion for inkjet printing is preferably 4mPa · s or more, more preferably 6mPa · s or more, further preferably 8mPa · s or more, preferably 15mPa · s or less, more preferably 13mPa · s or less, further preferably 11mPa · s or less. For example, the viscosity of the dispersion for screen printing is preferably 50mPa · s or more, more preferably 100mPa · s or more, and even more preferably 200mPa · s or more, and is preferably 50000mPa · s or less, more preferably 10000mPa · s or less, and even more preferably 5000mPa · s or less. In addition, the viscosity of the dispersion is a value measured at 23 ℃ using a cone-plate type rotary viscometer.
(relationship of copper oxide in Dispersion to dispersant)
Fig. 1 is a schematic sectional view showing the relationship between copper oxide and a phosphate salt in a dispersion (copper oxide ink) that can be used in one embodiment of the present invention. Referring to fig. 1, in one embodiment of the present invention, when the copper oxide ink 10 contains copper oxide 12 and a phosphate ester 13 (an example of a phosphate ester as a dispersant), the phosphate ester 13 surrounds the periphery of the copper oxide 12 so that the phosphorus 13a faces inward and the ester 13b faces outward. The phosphate ester 13 exhibits electrical insulation, and therefore the phosphate ester 13 interferes with electrical conduction between the copper oxides 12 adjacent to each other. In addition, the phosphate ester salt 13 suppresses aggregation of the copper oxide ink 10 by a steric hindrance effect. Therefore, although the copper oxide 12 is a semiconductor (i.e., has a certain degree of conductivity), the copper oxide ink 10 exhibits electrical insulation because it is covered with the phosphate ester 13 exhibiting electrical insulation.
On the other hand, when the copper oxide 12 is reduced to copper in the plating step or the like, a conductive pattern region having excellent electrical conductivity is formed. When an organic substance containing phosphorus is used as the dispersant, phosphorus remains in the conductive pattern region. The phosphorus element exists in the form of at least 1 of phosphorus element simple substance, phosphate and phosphorus-containing organic substance. However, since such a residual phosphorus element is usually segregated in the conductive pattern region, there is no concern that the resistance of the conductive pattern region increases.
[ formation of coating film ]
As a coating method of the dispersion, inkjet printing, screen printing, gravure direct printing, gravure offset printing, flexographic printing, offset printing, and the like can be used. Coating can be performed using a method such as die coating, spin coating, slit coating, bar coating, blade coating, spray coating, or dip coating. The coating method is preferably ink jet printing. The ink jet method does not require a printing plate and does not cause an excessive component to adhere between the wirings, and therefore has excellent resistance to migration (a phenomenon in which a component of the wirings moves when an electric field is applied to the wirings).
The thickness of the coating film after drying is preferably 1nm or more, or 10nm or more, or 100nm or more, and preferably 10000nm or less, or 8000nm or less, or 7000nm or less, from the viewpoint of forming a uniform conductive pattern.
The substrate may have an adhesion layer (also referred to as an ink-receiving layer), and a coating film may be formed by printing the dispersion on the adhesion layer. The compound forming the adhesion layer (also referred to as "coating compound" in the present disclosure) preferably has an — OH group, and/or has an Ar-O structure and/or an M-O structure. Here, ar represents an aromatic structure, and M represents a metal atom. In the case where the adhesion layer is present, a layer of a metal compound and/or a metal can be formed on the base material with good adhesion, and heat is hardly transferred to the base material body, and thus even a resin with low heat resistance, for example, a polyethylene terephthalate (PET) resin can be used as the base material body, which is advantageous in view of versatility.
the-OH group is particularly preferably an aromatic hydroxyl group (i.e. -OH group constituting the-Ar-OH group) or a hydroxyl group bonded to a metal atom (i.e., -OH group constituting-M-OH group). The — OH groups constituting the — Ar — OH groups and the — M — OH groups have high activity, and tend to have excellent adhesion between the adhesion layer and the base material main body and/or adhesion between the metal compound and/or the metal layer and the adhesion layer.
Examples of the aromatic structure (Ar) in the — Ar — OH group include a 2-valent group derived from (i.e., 2 hydrogen atoms are removed from) an aromatic compound: aromatic hydrocarbons such as benzene, naphthalene, anthracene, tetracene, pentacene, phenanthrene, pyrene, perylene, and triphenylene; and heteroaromatic compounds such as thiophene, thiazole, pyrrole, furan, pyridine, pyrazole, imidazole, pyridazine, pyrimidine, and pyrazine; and so on. The number of electrons contained in the n-electron system having an aromatic structure is preferably 22 or less, more preferably 14 or less, and still more preferably 10 or less. When the number of electrons contained in the pi-electron system is 22 or less, the crystallinity is not excessively increased, and a soft and smooth sealing layer can be easily obtained. In the aromatic structure, a part of hydrogen bonded to the aromatic ring may be substituted with a functional group. Examples of the functional group include a halogen group, an alkyl group (e.g., methyl, isopropyl, tert-butyl, etc.), an aryl group (e.g., phenyl, naphthyl, etc.), a heteroaromatic group (e.g., thienyl, etc.), a haloaryl group (e.g., pentafluorophenyl, 3-fluorophenyl, 3,4, 5-trifluorophenyl, etc.), an alkenyl group, an alkynyl group, an amide group, an acyl group, an alkoxy group (e.g., methoxy, etc.), an aryloxy group (e.g., phenoxy, naphthyloxy, etc.), a haloalkyl group (e.g., perfluoroalkyl, etc.), a thiocyano group, a hydroxyl group, and the like. As the-Ar-OH group, a hydroxyphenyl group (-Ph-OH) is particularly preferable.
Examples of the metal atom (M) in the-M-OH group include 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. In the case where the adhesion layer needs to be insulating, -Si-OH group or-Zr-OH group is preferable, and in the case where the adhesion layer needs to be conductive, -Ti-OH group or-Zn-OH group is preferable.
The aromatic structure (Ar) in the Ar — O structure may be a structure obtained by removing 1 or more hydrogen atoms from an aromatic compound similar to the aromatic compound exemplified in the above-mentioned — Ar — OH group. In particular, the Ar-O structure is preferably a Ph-O structure.
As the metal atom in the M-O structure, the same metal atoms as exemplified above for the-M-OH group can be used. Particularly, as the M-O structure, a Si-O structure, a Ti-O structure, a Zn-O structure and a Zr-O structure are preferable.
Examples of the coating compound having a Si-O structure include a silicon oxide compound (e.g., silicon dioxide (SiO) 2 ) And silicone compounds (e.g., polysiloxanes, e.g., alkyl polysiloxanes, e.g., dimethyl polysiloxane), and the like.
Examples of the compound for coating include a compound obtained by introducing 1 or more of the above-mentioned-OH group, ar-O structure and M-O structure into the following compounds: polyimide, 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), polyether ketone (PEK), polyphthalamide (PPA), polyether nitrile (PENt), polybenzimidazole (PBI), polycarbodiimide, silicone polymer (polysiloxane), polymethacrylamide, nitrile rubber, acrylic rubber, polytetrafluoroethylene, epoxy resin, poly (ethylene terephthalate) (PPA), poly (ethylene terephthalate), poly (ethylene naphthalate) (PEN), etc phenol 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), novolac resin, phenol resin, polyvinyl chloride (PVC), polyvinyl chloride (PVDF), polyether ether ketone (PEEK), polyvinyl chloride (PVC), and the like, benzocyclobutene, polyvinylphenol, polychloropyrene, polyoxymethylene, polysulfone (PSF), and the like. As the compound for coating, a phenol resin, a novolac resin, polyvinyl phenol, and polyimide are particularly preferable.
The upper limit of the thickness of the adhesion layer is not particularly limited, but 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, and still more preferably 0.2 μm or more.
< drying step >
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 or vacuum drying. In view of the heat resistance of the substrate, the drying is preferably performed at a temperature of 150 ℃ or lower, more preferably at a temperature of 100 ℃ or lower. Nitrogen or nitrogen mixed with hydrogen (for example, a mixed gas containing about 3 vol% of hydrogen in 100 vol% of the total of hydrogen and nitrogen) may be introduced during drying.
< reduction step >
In the case where the dispersion contains particles containing a metal oxide (in one embodiment, copper oxide), one embodiment of the method of the present disclosure may include a reduction step after the coating film formation step. In the reduction step, a film containing a metal oxide, which is a coating film after the coating film formation step (in one embodiment, after the drying step), is reduced to obtain a film containing a metal. In this step, the metal oxide-containing particles in the metal oxide-containing film are reduced to produce a metal, and the metal-containing film (reduced metal layer) can be formed by welding and integrating the metal itself. In the case where the particles containing the metal oxide are directly plated, this step can be omitted. Examples of the reduction method include a method of reducing at a temperature of 100 ℃ or higher and 500 ℃ or lower in a nitrogen atmosphere, a method of reducing at a temperature of 100 ℃ or higher and 500 ℃ or lower in nitrogen mixed with hydrogen (for example, a mixed gas containing about 3% by volume of hydrogen in total 100% by volume of hydrogen and nitrogen), a method of reducing by irradiation with a laser, and a method of immersing a film containing a metal oxide in a reducing solution (that is, wet reduction).
As a method of reducing by laser light, various laser irradiation apparatuses having a laser irradiation section can be used. A laser beam is preferable because it can be exposed to high-intensity light for a short time and the temperature of the coating film formed on the substrate is raised to a high temperature in a short time to perform firing. The laser method is advantageous in that it can be applied to a base material (for example, a resin film substrate) having low heat resistance because the firing time can be shortened, and thus the damage to the base material is small. In addition, the laser system is advantageous in that the degree of freedom in selecting the wavelength is large, and the wavelength can be selected in consideration of the light absorption wavelength of the coating film and/or the light absorption wavelength of the substrate.
Further, since exposure by beam scanning can be performed by the laser system, the exposure range can be easily adjusted, and selective light irradiation (drawing) can be performed only on a target region of the coating film without using a mask, for example.
Examples of the laser source include YAG (yttrium aluminum garnet), YVO (yttrium vanadate), yb (ytterbium), semiconductors (GaAs, gaAlAs, gaInAs), and carbon dioxide. As the laser light, not only the fundamental wave but also a harmonic wave can be picked up as necessary for use.
The center wavelength of the laser light is preferably 350nm to 600 nm. In particular, when particles containing cuprous oxide are used as the particles containing a metal oxide, cuprous oxide can well absorb laser light having a central wavelength in the above range, and thus can be uniformly reduced to form a conductive pattern having a low resistance.
The laser light is preferably irradiated to the coating film by a galvanometer scanner. By scanning the laser beam on the coating film with a galvanometer scanner, a conductive pattern having an arbitrary shape can be obtained.
The irradiation output of the laser is preferably 50mW or more, or 80mW or more, or 90mW or more from the viewpoint of efficiently performing desired firing (for example, reduction of monovalent copper oxide), and is preferably 1000mW or less, or 850mW or less, or 500mW or less from the viewpoint of suppressing destruction of the conductive pattern by ablation due to excessive output of the laser and obtaining a low-resistance conductive pattern.
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 apparatus 100 may have a sample cell 101, a light oscillator 102 that oscillates laser light, a gas supply unit 103, a galvanometer scanner 104, a scanner control unit 105, and a computer 106. The sample cell may have a window portion that may have a light transmittance that allows the laser light L to reach the coating film 2d via the window portion. The sample cell 101 may have a gas inlet, and may be configured such that, for example, gas from the gas supply unit 103 (which may be, for example, a blower, a compressor, or the like) is introduced into the sample cell through the gas inlet. Alternatively, the laser irradiation device may not include a sample cell. In this case, the gas may be directly blown to the coating film 2d on the substrate 1.
The galvanometer scanner 104 scans the laser light L emitted from the optical oscillator 102. The galvanometer scanner 104 may have an X-axis galvanometer 104a, an X-axis galvanometer motor 104b, a Y-axis galvanometer 104c, and a Y-axis galvanometer motor 104d. The galvanometer scanner may include an f θ lens (not shown), a driving lens for Z-axis adjustment (not shown), and the like. The X-axis galvanometer motor 104b and the Y-axis galvanometer motor 104d are electrically connected to the scanner control unit 105. The galvanometer scanner is configured to be capable of controlling the rotation angles and the rotation speeds of the X-axis galvanometer motor 104b and the Y-axis galvanometer motor 104d based on a control signal from the scanner control unit 105. The scanner control unit 105 is controlled by a computer 106.
The laser light L is scanned by the galvanometer scanner 104 and irradiated on the surface of the coating film 2d formed on the substrate 1.
The scanner control unit 105 calculates the length (L) of the scanning line based on the scanning data (coordinate data) indicating the desired shape, position, and size of the conductive pattern, and then calculates the speed at which the laser beam is scanned (hereinafter referred to as scanning speed) (V) based on the length (L) of the scanning line by the following equation.
Scanning speed (V) = scanning period (F) × length of scanning line (L)
The scanner control unit 105 moves the irradiation point P of the laser light L on the galvanometer scanner 104 at the scanning speed described above, thereby executing a desired scan.
The laser irradiation device 100 may include an output adjustment mechanism (e.g., an attenuator) that adjusts the output of the laser light, a pulse suppression mechanism (e.g., a first pulse suppression function (FPS function)) when the laser light is pulsed light, and/or a spot adjustment mechanism (e.g., a beam expander) that adjusts the spot diameter of the focal position of the laser light. These mechanisms can be advantageous in suppressing ablation and/or carbonization of the coating film upon laser irradiation.
In one embodiment, the reduction step is a wet reduction step, which is a step of immersing the film containing the metal oxide in a reducing solution. The reducing liquid contains a reducing agent. The reducing agent may be inorganic or organic. Examples of the inorganic reducing agent include sodium borohydride, sulfur dioxide, sodium nitrite, metallic aluminum, cerium chloride, and sodium thiosulfate, and examples of the organic reducing agent include hydrazine, formaldehyde, methanol, citric acid and a salt thereof, oxalic acid and a salt thereof, formic acid and a salt thereof, glycerol, glucose, and ethylene glycol, and the following formula (2):
(R 1 ) 2 N-C(R 2 ) 2 -COOR 3 (2)
(wherein R is 1 And R 2 And R 3 Each independently is hydrogen or a 1-valent group, a plurality of R in the formula 1 And R 2 May be the same or different from each other. )
The compound represented by (2R) 2 All hydrogen are referred to as glycine compounds), the following formula (3):
(R 1 ) 2 N-(CH 2 ) x -COOR 2 (3)
(in the formula, R 1 And R 2 Each independently hydrogen or a 1-valent group, x is an integer of 0 to 10), L-ascorbic acid and salts thereof, thioglycolic acid, hydroxylamine hydrochloride, hydroquinone, bisulfite, isoascorbic acid, isoascorbate, thiourea, tin-based reducing agents, iron-based reducing agents, zinc-based reducing agents, and the like.
In one embodiment, the compound represented by the formula (2) is glycine or a derivative thereof. <xnotran> , N- [ N- ( ) ] -L- , N- 4- , L- (2- ) , BOC-NA- -L- , () , , D- (-) -2- (2,5- ) , cbz- -L- , (R) - α - [ (3- -1- -3- -1- ) ] , N- ( ) , D- , (S) - α - -4- , N- ( ) -L-2- , , D-2- , (S) -2- -2- , (2S) -N- [ [ ( ) ] ] -2- -4- , (R) -2- -4- , (R) -N-BOC- , N- , (S) -N-BOC-A- , </xnotran> 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, glycine benzyl p-toluenesulfonate, (S) -N-BOC-allylglycine, (R) -4-hydroxy- α - [ (3-methoxy-1-methyl-3-oxo-1-propenyl) amino ] phenylacetic acid potassium, N- [ (9H-fluoren-9-ylmethoxy) carbonyl ] -D-2-phenylglycine, DL-leucyldiglycine, glycylglycine, N- (tert-butoxycarbonyl) -L-propargylglycine, 2-amino-2- [3- (trifluoromethyl) phenyl ] acetic acid, (S) -N-BOC-3-hydroxyadaminoalkylglycine, N- [ tris (hydroxymethyl) methyl ] glycine, 2-propargyl-L-phenylglycine, N- (triphenylmethyl) glycine, 2-oxoethyl-2- (2-oxoethyl) phenylcarboxylate, 2-oxoethyl-aminobenzoate, FMOC-D-allylglycine, L-2- (4-chlorophenyl) glycine, D-2-cyclohexylglycine, N-bis (2-hydroxyethyl) glycine, N- (benzyloxycarbonyl) -D-phenylglycine, N- [ (9H-fluoren-9-ylmethoxy) carbonyl ] -L-2-phenylglycine, benzyloxycarbonylamino (dimethoxyphosphino) acetic acid methyl ester, N- (tert-butoxycarbonyl) glycine methyl ester, 4- (trifluoromethyl) phenylglycine, glycyl-DL-leucine, N-p-toluenesulfonylglycine, N- (tert-butoxycarbonyl) -D-2-cyclohexylglycine, N-formylglycine, N-tert-butylglycine HCL, (R) -2-allylglycine, H-glycine benzyl ester hydrochloride, N-benzyloxycarbonyl-L-2-phenylglycine, (diphenylmethyleneamino) acetic acid ethyl ester (diphenylmethyleneamino) acetic acid, hydroxyphenylglycine, L-methionylglycine, (4-hydroxyphenyl) (amino) acetic acid, (R) -alpha-aminophenylacetic acid methyl ester hydrochloride, L-A-cyclopropylglycine hydrochloride, N-benzylglycine, D-fluorophenylglycine, alpha-fluorophenylglycine hydrochloride, tert-butyl glycinate hydrochloride, trimethyl N- (tert-butoxycarbonyl) -2-phosphonoglycine, N- [ (9H-fluoren-9-ylmethoxy) carbonyl ] glycine, N- (4-hydroxyphenyl) glycine, DL-2- (4-chlorophenyl) glycine, L-A-cyclohexylglycine, glycine ethyl ester 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) glycinyl chloride, N-phthalaylglycine, ethyl N-formylglycine, N- (tert-butoxycarbonyl) -L-2-phenylglycine, N- (tert-butoxycarbonyl) glycine, N- (2-aminoethyl) glycine, N-phenylglycine, N-dimethylglycine hydrochloride, (S) -N-FMOC-allylglycine, D- (-) -2- (4-hydroxyphenyl) glycine, L (+) -2-phenylglycine methyl ester hydrochloride, trisodium hydrochloride, N- (tert-butoxycarbonyl) glycine hydrochloride, N- (2-aminocarbonyl) glycine hydrochloride, N- (2-aminophenyl) glycine hydrochloride, N- (2-aminocarbonyl) glycine hydrochloride, ethyl N-acetylglycine, L-leucyl glycine hydrate, L-2-allylglycine hydrochloride, and the like.
The glycine derivative is preferably a compound having a structure having 2 or more hydroxyl groups in the molecule. When a glycine derivative having 2 or more hydroxyl groups is used, the plating process can be performed at a higher speed in the subsequent step, and the film is less likely to peel off in the subsequent step, which is advantageous. Preferable examples of the compound having a structure having 2 or more hydroxyl groups in the molecule include N, N-bis (2-hydroxyethyl) glycine and N- [ tris (hydroxymethyl) methyl ] glycine.
In the case where the reduction step is a wet reduction step, the concentration of the reducing agent in the reducing solution may be, for example, 1.0g/L or more, or 3.0g/L or more, or 5.0g/L or more, or 10.0g/L or more, or 600g/L or less, or 570g/L or less, or 550g/L or less, or 520g/L or less, or 500g/L or less, from the viewpoint of achieving a good reduction rate and stable reduction.
The reducing agent concentration in the reducing solution may be, for example, 0.1 mass% or more, or 0.3 mass% or more, or 0.5 mass% or more, or 1.0 mass% or more, or may be, for example, 60 mass% or less, or 57 mass% or less, or 55 mass% or less, or 52 mass% or less, or 50 mass% or less, from the viewpoint that the reduction rate is good and stable reduction can be obtained.
In one embodiment, the reducing solution contains a compound represented by the above formula (2). The concentration of the compound in the reducing solution is preferably 1 mass% or more, or 8 mass% or more, or 16 mass% or more, and preferably 50 mass% or less, or 32 mass% or less.
In a representative embodiment, the reducing solution contains a solvent. The solvent system may be aqueous or organic. Examples of the solvent include water, ethanol, 1-butanol, 2-propanol, toluene, hexane, benzene, chloroform, dichloromethane, acetic acid, ethyl acetate, tetrahydrofuran, acetone, acetonitrile, N-dimethylformamide, and dimethyl sulfoxide. From the viewpoint of reuse, water, ethanol, 1-butanol and 2-propanol are particularly preferable.
As the solvent in the reducing solution, water is particularly preferable, and a combination of a glycine compound and water is particularly preferable from the viewpoints of cost and productivity. The reducing solution is particularly preferably an aqueous solution having a glycine compound concentration of 1 to 50 mass%.
In one embodiment, the reducing solution preferably contains N, N-bis (2-hydroxyethyl) glycine and/or citric acid in terms of productivity, i.e., in terms of rapid reduction. In particular, when N, N-bis (2-hydroxyethyl) glycine is used, it is preferable from the viewpoint that a metal (copper in one embodiment) selected from 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 in the reducing solution becomes an ion and forms a complex with glycine, thereby promoting the reduction from a metal oxide (copper oxide in one embodiment) to a metal (copper in one embodiment).
In the reduction, the coating film is preferably immersed while stirring so that the concentration of the reducing agent in the reducing solution is constant.
The reducing liquid preferably contains metal ions and/or metal oxides (in one embodiment, copper ions and/or copper oxide) of a predetermined level or more. This can suppress the falling off of the coating film during wet reduction. The concentration of the metal ions, or the concentration of the metal oxide, or the total concentration of the metal ions and the metal oxide in the reducing solution is preferably 1 mass% or more, or 5 mass% or more, and preferably 99 mass% or less, or 90 mass% or less. In one embodiment, in the case where the reducing solution contains copper ions and/or copper oxide, the reducing solution may be prepared by adding 1 or more selected from the group consisting of copper acetate, copper chloride, copper oxide, metallic copper, and a dispersion containing particles containing copper oxide of the present disclosure to a solvent, so that the reducing solution contains copper ions and/or copper oxide. In one embodiment, the reducing solution may contain copper oxide by diffusing copper oxide from the coating film into the solvent.
In view of productivity, the temperature in the wet reduction step is preferably 20 ℃ or higher, more preferably 30 ℃ or higher, and still more preferably 40 ℃ or higher, in order to rapidly perform the reduction. In addition, the temperature is preferably 100 ℃ or lower, more preferably 90 ℃ or lower, from the viewpoint of obtaining a uniform metal (copper in one embodiment) containing film.
The wet reduction step may be performed simultaneously with the electroless plating in the plating step. From the viewpoint of improving productivity, it is preferable that the wet reduction step and the plating step are performed simultaneously. Specifically, the reducing agent is also included in the plating solution described later, whereby the wet reduction step and the plating step can be performed simultaneously. In this case, the amount of the solvent is preferably adjusted so that the concentration of the reducing agent and the concentration of the plating substance (in one embodiment, the concentration of copper) in the plating solution are within the ranges exemplified in the reducing solution and the plating solution in the present disclosure.
< cleaning step >
In the case of performing wet reduction, after the wet reduction, the unreduced part and the reduced solution may be removed by using an appropriate cleaning solution. Thereby leaving a clean reduced area on the substrate. On the other hand, the cleaning step may not be performed. In either case, a substrate (hereinafter, also referred to as a conductive substrate) to which conductivity is imparted by the reduced region as a conductive pattern can be obtained. In the case where a film containing a metal oxide (copper oxide in one embodiment) is directly plated, this step may be omitted.
As the cleaning liquid used for cleaning, a liquid in which a metal oxide (in one embodiment, copper oxide) is dispersed or dissolved may be used. <xnotran> , , ,3- -3- - , , , , , , , , , , ,1,2- ,1,3- ,2- ,2- -2,4- ,2,5- ,2,4- ,2- -1,3- , , , , , -1,2- , , , , , , , , , , , , ,2- , , , ,2- ,2- , ,3- , ,2- ,2- ,2- , 1- ,2- ,3- , ,2- ,2- , ,2,6 -4- , , , ,3,3,5- , , , . </xnotran> In particular, when the coating film contains a dispersant, the solvent is preferable because the metal oxide (copper oxide in one embodiment) can be washed off well. As the solvent, water, ethanol, 1-butanol, isopropanol and acetone are particularly preferred. The cleaning solution may contain a dispersant in addition to the solvent. The dispersant may be any of those described above, and is preferably a phosphorus-containing organic substance.
< degreasing step >
In the case of performing the plating step, a step of degreasing the coating film may be provided before the plating step. In one embodiment, the metal oxide (copper oxide in one embodiment) is directly degreased without being reduced, whereby productivity can be improved. In another embodiment, the metal oxide may be reduced (for example, by the above-described reduction step) and then degreased. Examples of the degreasing method include a UV method and a wet degreasing method. By performing the degreasing step, the growth rate of the subsequent plating is increased, and the productivity is improved. In addition, this step contributes to a reduction in the porosity of the conductive layer after plating (i.e., the plating layer and the layer of the metal compound and/or metal in the case where the layer contains copper), that is, contributes to the porosity of the final conductive layer. In this case, the degreasing step may be omitted.
In view of interlayer adhesion of the structure with the conductive pattern, the degreasing step is preferably performed by immersing the coating film in a degreasing liquid containing an amino group-containing compound. Examples of the amino group-containing compound include amino acids such as alanine, arginine, asparagine, cysteine, glutamine, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine, alkylamines such as methylamine, dimethylamine, ethylamine, trimethylamine, diethylamine, triethylamine, propylamine, isopropylamine, and diisopropylamine, alkylamines such as 2-aminoethanol, diethanolamine, triethanolamine, N-methylethanolamine, and N, N-dimethylethanolamine, alkanolamines such as ethylenediamine, diethylenetriamine, tetraethylenepentamine, tris (hydroxymethyl) aminomethane, m-xylylenediamine, p-xylylenediamine, and 1, 3-bis (aminomethyl) cyclohexane, polyamines such as taurine, sulfamic acid such as taurine, aminothiols such as 2-aminoethanethiol, 3-pyridinemethylamine, and nitrogen-containing heterocyclic compounds such as 3-pyridinemethanol. 2-aminoethanol is particularly preferable from the viewpoint of contributing to the growth rate of plating.
The degreasing solution may be a commercially available product, and specifically, ALC-009 (containing 2-aminoethanol as a compound having an amino group) available from wakame corporation, cleaner Securigant 902 (containing 2-aminoethanol as a compound having an amino group) available from Atotech Japan corporation, and the like may be mentioned.
The concentration of the amino group-containing compound in the degreasing solution is preferably 5mmol/L or more, more preferably 10mmol/L or more, and still more preferably 20mmol/L or more, from the viewpoint of removing substances that inhibit the plating reaction. From the viewpoint of promoting the plating reaction, the concentration is preferably 100mmol/L or less, more preferably 90mmol/L or less, and still more preferably 80mmol/L or less.
The immersion time of the coating film in the degreasing solution is preferably 1 minute or more, and more preferably 2 minutes or more, from the viewpoint of contributing to the growth rate of the plating. In addition, from the viewpoint of reducing damage to the base material, it is preferably within 15 minutes, more preferably within 10 minutes. From the viewpoint of uniform degreasing, dipping under stirring is preferable.
In order to enhance the effect of accelerating the growth rate of plating, the immersion temperature is preferably 15 ℃ or more, more preferably 30 ℃ or more, and still more preferably 40 ℃ or more. In addition, from the viewpoint of reducing damage to the substrate, it is preferably 70 ℃ or lower, and more preferably 60 ℃ or lower.
< plating Process >
In one embodiment 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 a conductive region having a relatively low porosity. In one embodiment, the coating film may be plated after the drying step, with or without undergoing the reduction step and/or the degreasing step. 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 of the reduction step and the plating step may be performed in advance. In one embodiment, a film containing a metal oxide (in one embodiment, copper oxide) is directly plated without reduction, thereby improving productivity. In one embodiment, the plating is electroless plating. In the electroless plating, a part or all of the metal oxide (copper oxide in one embodiment) in the film containing the metal oxide (copper oxide in one embodiment) may be reduced, or the metal oxide may not be reduced. In another embodiment, the conductivity can be improved by reducing (for example, wet reduction) a film containing a metal oxide (copper oxide in one embodiment) and subjecting the resulting film containing a metal (copper in one embodiment) to electroless plating. By electroless plating, a conductive pattern composed of a layer of a metal compound and/or a metal and a plating layer can be formed. This enables the production of a structure with a conductive pattern. Electroless plating is advantageous in view of the wide range of applicability to patterns. As the plating method, a general electroless plating method can be applied. For example, electroless plating may be performed together with the degreasing step or the cleaning step.
The plating solution is used for electroless plating. In the case of performing the drying step, the coating film after the drying step is likely to peel off due to external stress, and therefore if plating deposition is uneven and stress is concentrated in a part, the coating film may peel off during the plating step. The type of the plating solution is not limited, and a plating solution containing EDTA (ethylenediaminetetraacetic acid), rochelle salt (potassium sodium L-tartrate tetrahydrate), or the like as a complexing agent can be used. In one embodiment, the plating solution contains EDTA. Since EDTA functions as a complexing agent and forms a highly stable complex with a metal ion (in one embodiment, copper) selected from 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, it is considered that side reactions in the plating bath are suppressed, the plating bath is stabilized, and plating deposition is uniformly performed, thereby contributing to prevention of peeling of the coating film. Therefore, the use of the plating solution containing EDTA contributes to the production of a structure with a conductive pattern having excellent interlayer adhesion. In addition, since EDTA is stable even in a high-temperature liquid, it contributes to an increase in plating speed when a plating liquid containing EDTA is used under heating (for example, 30 ℃ or higher). In addition, when plating is performed using a plating solution containing EDTA (ethylenediaminetetraacetic acid) after wet reduction, the productivity can be improved by promoting the growth of metal (in one embodiment, copper) plating, which is particularly preferable. The amount of EDTA in the plating solution is preferably 7g/L or more, or 10g/L or more, or 15g/L or more from the viewpoint of obtaining the advantages of EDTA, and is preferably 50g/L or less, or 45g/L or less, or 40g/L or less from the viewpoint of reducing impurities in the plating deposit and reducing the electric resistance.
In a representative manner, the plating solution comprises a copper ion source and a reducing agent. The source of copper ions may be present in the plating solution in ionic form. For example, the coating film may be immersed in the plating solution while air bubbling is performed. The 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 (in one embodiment, copper oxide), a part or all of the metal oxide may be reduced or not reduced by the plating solution in the electroless plating. Thus, a plated copper layer is formed on the layer containing the metal compound and/or the metal.
The copper concentration of the plating solution is preferably 1.5g/L or more, or 1.8g/L or more, or 2.0g/L or more from the viewpoint of increasing the plating rate, and is preferably 5.0g/L or less, or 4.0g/L or less, or 3.5g/L or less, or 3.0g/L or less from the viewpoint of uniformity of the plating film. Particularly, when the wet reduction and plating are combined, the copper concentration of the plating solution is preferably 1.8g/L to 3.5 g/L.
Examples of the copper ion source contained in the plating solution include CuSO 4 、CuCl 2 、CuCl、CuNO 3 、Cu 3 (PO 4 ) 2 For example, cuCl is preferable from the viewpoint of forming a plating layer having excellent adhesion 2 And CuSO 4 。
The plating solution may contain a compound selected from the group consisting of formaldehyde (CH) 2 O), potassium tetrahydrolate, dimethylamine borane, glyoxylic acid and phosphinic acid as reducing agents. The amount of the reducing agent in the plating solution is preferably 0.1g/L or more, or 0.5g/L or more, or 1.0g/L or more, and preferably 15.0g/L or less, or 12.0g/L or less, or 9.0g/L or less.
The plating solution may further contain an additional complexing agent in addition to EDTA (ethylenediaminetetraacetic acid). Examples of the additional complexing agent include rochelle salt, triethanolamine, ammonium sulfate, citric acid, glycine, and the like. The amount of the complexing agent added to the plating solution is preferably 5g/L or more, or 7g/L or more, or 10g/L or more, and preferably 50g/L or less, or 45g/L or less, or 40g/L or less.
The plating liquid may further contain a surfactant as desired.
The plating solution may be a commercially available one. As commercially available products, thru-cup ELC-SP available from Tomura industries, inc., melplate CU-390 available from Meltex corporation, melplate CU-5100P, OPC Copper NCA available from Olympic pharmaceuticals, inc., C4500 available from Rohm and Haas, printganthUPlus available from Atotech, cu-510 available from Mac Dermid, japan, and the like can be used.
The temperature of the electroless plating bath by the plating solution is preferably 25 ℃ or higher, or 30 ℃ or higher, or 35 ℃ or higher, and preferably 80 ℃ or lower, or 70 ℃ or lower, or 65 ℃ or lower, from the viewpoint of desiring a higher plating growth rate. The plating time is preferably 5 minutes or more, or 10 minutes or more, and preferably 60 minutes or less, or 50 minutes or less, or 40 minutes or less.
The thickness of the plating layer (in one embodiment, the plating copper layer) is preferably 300nm or more, or 500nm or more, or 1 μm or more, or 2 μm or more, and preferably 100 μm or less, or 50 μm or less, or 30 μm or less, from the viewpoint of allowing a desired current to flow through the structure with the conductive pattern.
In one embodiment, the electrolytic plating may be performed after the electroless plating. The electrolytic plating can be carried out by a conventional electroplating method. For example, an electrode and a conductive base material as an object to be plated are put in a solution (plating bath) containing copper ions. Then, a direct current is applied between the electrode and the conductive substrate by an external direct current power supply. In one embodiment, the current may be applied to the reduced metal layer by connecting a jig (e.g., a clip) connected to one electrode of the pair of electrodes of the external dc power supply to the reduced metal (in one embodiment, reduced copper) layer on the conductive substrate. As a result, copper is deposited on the surface of the reduced metal layer on the conductive base material by reduction of copper ions, thereby forming a plated copper layer.
As the electrolytic plating bath, for example, a copper sulfate bath, a copper fluoroborate bath, a copper cyanide bath, and a copper pyrophosphate bath can be used. From the viewpoint of safety and productivity, copper sulfate baths and copper pyrophosphate baths are preferred.
As the copper sulfate plating bath, for example, a sulfuric acid copper sulfate plating bath containing copper sulfate pentahydrate, sulfuric acid, and chlorine can be suitably used. The concentration of copper sulfate pentahydrate in the copper sulfate plating bath is preferably 50g/L or more, or 100g/L or more, and preferably 300g/L or less, or 200g/L or less. The concentration of sulfuric acid is preferably 40g/L or more, or 80g/L or more, and preferably 160g/L or less, or 120g/L or less. The solvent of the plating bath is typically water. The temperature of the plating bath is preferably 20 ℃ or higher, or 30 ℃ or higher, and preferably 60 ℃ or lower, or 50 ℃ or lower. The current density at the time of electrolytic treatment is preferably 1A/dm 2 Above, or 2A/dm 2 Above, preferably 15A/dm 2 Below, or 10A/dm 2 The following.
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 60g/L or more, or 70g/L or more, and preferably 110g/L or less, or 90g/L or less. The concentration of potassium pyrophosphate is preferably 240g/L or more, or 300g/L or more, and preferably 470g/L or less, or 400g/L or less. The solvent of the plating bath is typically water. The pH of the plating bath is preferably 8.0 or more, or 8.2 or more, and preferably 9.0 or less, or 8.8 or less. In order to adjust the pH, ammonia water or the like may be added. The temperature of the plating bath is preferably 20 ℃ or more, or 30 ℃ or more, and preferably 60 ℃ or less, or 50 ℃ or less. The current density at the time of electrolytic treatment is preferably 0.5A/dm 2 Above, or 1A/dm 2 Above, it is preferably 10A/dm 2 The following, or 7A/dm 2 The following.
The plating bath for electrolytic plating may further contain a surfactant.
< post-treatment step >
One embodiment of the method of the present disclosure includes a post-treatment step for the purpose of improving adhesion between the base material and the layer of the metal compound and/or the metal. The post-treatment step is performed after the coating film formation step. In one embodiment, the humidifying treatment and/or the heating treatment may be performed after the coating film forming step, and for example, the humidifying treatment and/or the heating treatment may be performed 1 or more times between the coating film forming step and the drying step, between the drying step and the plating step, and after the plating step. When both the humidification treatment and the heating treatment are performed, they may be performed simultaneously or sequentially. When the humidification processing and the heating processing are successively performed, the order of the humidification processing and the heating processing is not limited.
Moisture enters the interface between the base material and the metal compound and/or metal layer by the humidification treatment, thereby obtaining the effect of improving the interlayer adhesiveness. Although not bound by theory, the above-described improvement in interlayer adhesion is thought to be caused by hydrogen bond formation by components (e.g., dispersant components from the dispersion) contained in the layer of the metal compound and/or the metal, moisture supplied by the humidification treatment, and the substrate. The base material is preferably Polyimide (PI), polyester (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc.), polyether sulfone (PES), polycarbonate (PC), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyacetal, polyarylate (PAR), polyamide (PA), polyamideimide (PAI), polyetherimide (PEI), polyphenylene ether (PPE), polyphenylene sulfide (PPS), polyether ketone (PEK), polyphthalamide (PPA), polyether nitrile (PENt), polybenzimidazole (PBI), etc., since the base material contains a chemical structure having hydrogen bond formation, the effect of improving interlayer adhesiveness is excellent. In particular, when the base material is polyimide, the effect of improving interlayer adhesiveness is more preferable because of the contribution of imide bonds.
It is also considered that the interlayer adhesion between the base material and the layer of the metal compound and/or the metal can be improved by improving the mechanical strength of the base material by the heat treatment. In one embodiment, when the material of the base material is polyimide, the imide bond in the polyimide may be broken in the plating step, but the temporarily broken imide bond can be repaired by heat treatment. It is considered that such a change in the molecular structure by the heat treatment leads to an improvement in the mechanical strength of the base material.
As the humidification processing device, a constant temperature and humidity chamber, a dryer, or the like can be used.
As the heat treatment device, a drying furnace, an oven, or the like can be used.
The relative humidity of the humidification treatment is preferably 50% or more, or 60% or more, or 70% or more, and preferably 100% or less.
The time of the humidification treatment is preferably 1 hour or more, or 10 hours or more, or 24 hours or more, and preferably 14 days or less, or 10 days or less, or 8 days or less.
The temperature of the humidification treatment is preferably 5 ℃ or more, or 15 ℃ or more, or 20 ℃ or more, and preferably 100 ℃ or less, or 80 ℃ or less, or 50 ℃ or less.
The heat treatment may be performed in air, for example. In one embodiment, the heating treatment may be performed in a gas (air, inert gas, or the like) whose humidity is controlled to be within the above-exemplified range (that is, the humidification treatment and the heating treatment may be performed simultaneously). The temperature of the heat treatment is preferably 100 ℃ or more, or 200 ℃ or more, or 250 ℃ or more in view of obtaining a favorable effect of improving the mechanical strength of the substrate (in one embodiment, an effect of forming an imide bond in the case of using a polyimide substrate), and is preferably 400 ℃ or less, or 350 ℃ or less, or 300 ℃ or less in view of avoiding thermal deterioration of the substrate (in one embodiment, in view of heat resistance of the polyimide substrate).
< preferred example of method for producing structure with conductive Pattern >
A more specific preferred example of the method for producing a structure with a conductive pattern will be described below with reference to fig. 2. In addition, a case where the dispersion contains copper oxide particles as the particles containing the metal compound will be described below as an example.
First, copper acetate B is dissolved in a mixed solvent a of water and Propylene Glycol (PG), and hydrazine C is added thereto and stirred (fig. 2 (a)).
Subsequently, the resultant solution (supernatant 2 a) and the monovalent copper oxide (precipitate 2 b) were subjected to solid-liquid separation by centrifugation (fig. 2 (b)).
Next, a dispersant D and an alcohol E are added to the precipitate 2b (fig. 2 (c)), and the precipitate is dispersed to obtain a dispersion 2c containing copper oxide (fig. 2 (D)).
The substrate 1 is separately prepared (fig. 2 (e)), and the 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 substrate 1 by an ink-jet method, a gravure printing method, or the like to form a coating film, followed by drying. As a result, a copper oxide-containing film (copper oxide layer) 2d containing copper oxide and a dispersant is formed on the substrate 1 (fig. 2 g).
Next, the film containing copper oxide is immersed in a degreasing solution containing an amino group-containing compound to perform a degreasing step, and then a plating step is performed. In addition, the degreasing step may be omitted. In the plating step, a part or all of the copper oxide in the copper oxide layer may be reduced. As a result, a copper oxide and/or copper layer 2e and a plated copper layer 2f are formed on the base material 1 (fig. 2 h).
Through the above steps, a structure with a conductive pattern can be manufactured.
As described above, according to the method of the present disclosure, the conductive layer can be produced at a very low cost and with low energy, and thus the structure with the conductive pattern can be produced more easily.
< formation of additional layer >
The structure with a conductive pattern of the present disclosure may have an additional layer in addition to the above-described substrate and conductive layer. As additional layers, a resin layer and a solder layer can be exemplified.
[ resin layer ]
In one embodiment, a part of the conductive layer is preferably covered with a resin layer. By covering a part of the conductive layer with the resin layer, oxidation of the conductive pattern can be prevented, and reliability can be improved. Further, the conductive layer is provided in a portion not covered with the resin layer, whereby the components can be electrically joined.
One example of the 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 the resin used include Polyethylene (PE), polypropylene (PP), polyimide (PI), polyester (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and the like), polyether Sulfone (PEs), polycarbonate (PC), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyacetal (POM), polyarylate (PAR), polyamide (PA) (PA 6, PA66, and the like), polyamideimide (PAI), polyetherimide (PEI), polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyphenylene Sulfide (PPs), polyether ketone (PEK), polyether ether ketone (PEEK), polyphthalamide (PPA), polyether nitrile (PENt), polybenzimidazole (PBI), polycarbodiimide, silicone polymer (polysiloxane), polymethacrylamide, nitrile rubber, acrylic rubber, polytetrafluoroethylene, epoxy resin, phenol resin, melamine resin, urea resin, polymethyl methacrylate resin (PMMA), polybutene, polypentene, ethylene-propylene copolymer, ethylene-butylene copolymer, isoprene-isoprene copolymer, styrene-butadiene copolymer, polybutadiene-butadiene copolymer (PS), polybutadiene-styrene copolymer, and the like, polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), novolac, 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), and the like. The thickness of the resin layer is preferably 0.1 μm or more, or 0.5 μm or more, and preferably 1mm or less, or 800 μm or less.
The sealing material layer can protect the conductive pattern from external stress in a finished product (the conductive pattern-provided structure itself and a product including the conductive pattern) after production, and can improve long-term stability of the conductive pattern-provided structure.
The moisture permeability of the sealing material layer as an example of the resin layer is preferably 1.0g/m in terms of ensuring good long-term stability 2 A value of not more than day, more preferably 0.8g/m 2 A value of not more than day, more preferably 0.6g/m 2 And/day is less. By reducing the moisture permeability, it is possible to prevent the mixing of moisture from the outside of the sealing material layer and suppress the oxidation of the conductive pattern. The lower the moisture permeability, the more preferable. The moisture permeability is a value measured by a cup method.
The sealing material layer may be a functional layer that can impart an oxygen barrier function to the structure with a conductive pattern even after an oxygen barrier layer that may be used in the production is peeled off. As other functions, there may be mentioned a scratch resistance at the time of handling of the structure with the conductive pattern, an antifouling property for protecting the structure with the conductive pattern from contamination from the outside, and a function of improving rigidity for the structure with the conductive pattern in the case of using a tough resin.
[ solder layer ]
In one embodiment, the solder layer is preferably formed on a part of the opposite side of the conductive layer from the substrate side. The conductive layer may be connected to other components using a solder layer. The solder layer can be formed by reflow, for example. <xnotran> Sn-Pb , pb-Sn-Sb , sn-Sb , sn-Pb-Bi , bi-Sn , sn-Cu , sn-Pb-Cu , sn-In , sn-Ag , sn-Pb-Ag , pb-Ag . </xnotran> The thickness of the solder layer is preferably 0.1 μm or more, or 0.5 μm or more, and preferably 2mm or less, or 1mm or less.
< kit for manufacturing Structure with conductive Pattern >
One embodiment of the present disclosure provides a structure manufacturing kit with a conductive pattern, which includes the dispersion of the present disclosure, the plating solution of the present disclosure, and the substrate subjected to a specific treatment of the present disclosure. The kit is advantageous for producing a structure with a conductive pattern having excellent interlayer adhesiveness.
One aspect of the present disclosure provides a structure manufacturing kit with a conductive pattern, including:
a dispersion comprising particles comprising a metal compound and/or particles comprising a metal;
a plating solution containing EDTA (ethylenediaminetetraacetic acid); and
a substrate subjected to 1 or more treatments selected from the group consisting of UV ozone treatment, organic solvent treatment and alkali treatment.
When the base material is polyimide, the dispersion is preferably excellent in adhesion to the base material.
One aspect of the present disclosure provides a structure manufacturing kit with a conductive pattern, including:
a dispersion comprising particles comprising a metal compound and/or particles comprising a metal;
a plating solution containing EDTA (ethylenediaminetetraacetic acid);
1 or more treating agents selected from the group consisting of organic solvents and alkali treating agents; and
a substrate.
In addition, one aspect of the present disclosure provides a structure manufacturing kit with a conductive pattern, including:
a dispersion comprising particles comprising a metal compound and/or particles comprising a metal; and
an organic solvent for the treatment of the organic solvent,
the SP value of the organic solvent is 7.5 to 12.6.
The SP value of the organic solvent is more preferably 9.9 to 11.6. The organic solvent preferably contains N-methylpyrrolidone.
Preferred configuration examples of the dispersion, the plating solution, and the base material that can be contained in the structure manufacturing kit with a conductive pattern according to the present disclosure may be the same as those described above in the present disclosure, and a description thereof will not be repeated.
< System for producing Structure with conductive Pattern >
One embodiment of the present disclosure also provides a structure manufacturing system with a conductive pattern. The system for manufacturing a structure with a conductive pattern includes: a pretreatment mechanism for subjecting the base material to an organic solvent treatment using an organic solvent having an SP value of 7.5 to 12.6;
a coating mechanism that applies a dispersion containing particles containing a metal compound and/or particles containing a metal to a substrate to obtain a coating film; and
and a plating mechanism for plating the coating film passing through the coating mechanism.
The structure manufacturing system with a conductive pattern may further include a drying mechanism for drying the coating film.
The conductive-patterned structure manufacturing system of the present disclosure can be suitably used for the conductive-patterned structure manufacturing method of the present disclosure. Therefore, as each element of the conductive pattern-provided structure manufacturing system, each element having the configuration or function illustrated above in the conductive pattern-provided structure manufacturing method can be adopted.
In one embodiment, the pretreatment mechanism may be an organic solvent impregnator or an organic solvent sprayer.
In one embodiment, the coating mechanism may be an ink jet printer, a screen printer, a gravure direct printer, a gravure offset printer, a flexographic printer, or an offset printer, preferably an ink jet printer. In one embodiment, the coating mechanism may include a die coater, a spin coater, a slit coater, a bar coater, a knife coater, a spray coater, or a dip coater.
In one approach, the drying mechanism may be an oven or a vacuum dryer. In one embodiment, the plating mechanism may be a plating bath.
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 >
[ hydrazine quantitation method ]
The hydrazine was quantified by standard addition methods.
To 50. Mu.L of the sample (dispersion), 33. Mu.g of hydrazine and a substitute substance (hydrazine) were added 15 N 2 H 4 ) 33. Mu.g, 1ml of benzaldehyde 1 mass% acetonitrile solution. Finally 20. Mu.L of phosphoric acid was added and GC/MS (gas chromatography/mass spectrometry) measurement was carried out after 4 hours.
Similarly, 66. Mu.g of hydrazine and a substitute substance (hydrazine) were added to 50. Mu.L of the sample (dispersion) 15 N 2 H 4 ) 33 μ g, benzyl1ml of aldehyde 1 mass% acetonitrile solution. Finally 20. Mu.L of phosphoric acid was added and GC/MS measurement was carried out after 4 hours.
Similarly, 133. Mu.g of hydrazine and a substitute substance (hydrazine) were added to 50. Mu.L of the sample (dispersion) 15 N 2 H 4 ) 33. Mu.g, 1ml of benzaldehyde 1 mass% acetonitrile solution. Finally, 20. Mu.L of phosphoric acid was added, and GC/MS measurement was carried out after 4 hours.
Finally, 50. Mu.L of sample (dispersion) was charged with a substitute substance (hydrazine) without adding hydrazine 15 N 2 H 4 ) 33. Mu.g, 1ml of benzaldehyde 1 mass% acetonitrile solution, 20. Mu.L of phosphoric acid was finally added, and GC/MS measurement was carried out after 4 hours.
The peak area value of hydrazine was obtained from the chromatogram with m/z =207 according to the above 4 parts GC/MS measurement. Alternative peak area values were then obtained from the mass spectrum with m/z = 209. The x-axis is the mass of hydrazine added/the mass of the alternative substance added, and the y-axis is the peak area value of hydrazine/the peak area value of the alternative substance, to obtain a calibration curve based on the standard addition method.
The value of the Y-intercept obtained from the calibration curve was divided by the mass of hydrazine added/mass of surrogate added to obtain the mass of hydrazine.
[ measurement of average particle diameter ]
The average particle diameter of the dispersion was measured by the accumulation method using FPAR-1000 manufactured by Otsuka Denshi Co.
[ evaluation of adhesion ]
The adhesion was evaluated by a tape peeling test. On the surface of the copper-containing film side of the sample, KAPTON tape (6563 # 50) was adhered, and the surface was peeled off at an angle of 60 degrees to the tape (i.e., in a 60-degree peeling manner). Evaluation was performed according to the following criteria.
AA: the peeling rate is 10% or less of the whole part of the adhesive tape
A: the peeling rate which can be visually observed is more than 10% and less than 25% of the whole part of the adhesive tape
B: the peeling rate which can be visually observed is more than 25% and less than 50% of the whole part of the adhesive tape
C: the peeling rate which can be visually observed is more than 50% and less than 60% of the whole part of the adhesive tape
D: the peel-off rate is more than 61% of the whole part of the adhesive tape
< example 1>
[ production of Dispersion ]
3224g of copper (II) acetate monohydrate (manufactured by Nippon chemical Co., ltd.) was dissolved in a mixed solvent composed of 30240g of water and 13976g of 1, 2-propanediol (manufactured by AGC Co., ltd.), 940g of hydrazine hydrate (manufactured by Nippon Finechem Co., ltd.) was added thereto and stirred, and then separated into a supernatant and a precipitate by centrifugation.
To 345g of the obtained precipitate was added 794g of the mixing liquid, and dispersion was performed using a homogenizer under a nitrogen atmosphere, to obtain a dispersion containing cuprous oxide particles (as particles containing a metal compound). The above-mentioned liquid mixture was prepared by adding 764g of 1-heptanol (manufactured by TOYOBO SYNTHETIC CO., LTD.) as a dispersion medium to 72g of DISPER BYK-145 (BYK-145), a trade name of which is a phosphorus-containing organic compound. Further, 5g of DISPER BYK-145 and 82g of 1-heptanol were added to 1063g of the above dispersion, and the mixture was dispersed with a homogenizer under a nitrogen atmosphere to obtain the objective dispersion. The amount of hydrazine in the dispersion was 0.2 mass%. At this time, the solid content residue (cuprous oxide particles) obtained by heating the dispersion at 60 ℃ under normal pressure for 4.5 hours was 26.1% by mass.
[ substrate cleaning and pretreatment Processes ]
Polyimide substrates (thickness 25 μm, SP value 12.1 cal/cm) were treated in ultrapure water 3 ) Ultrasonic irradiation was performed for 5 minutes, followed by ultrasonic irradiation in ethanol for 5 minutes, and cleaning was performed. The surface of the substrate was then subjected to UV ozone treatment for 3 minutes. The substrate was then immersed in N-methylpyrrolidone for 15 minutes at room temperature (23 ℃). Thereafter, the substrate was washed with water, and air was blown to the surface of the substrate to remove water.
[ coating and drying of the Dispersion ]
Printing was performed on this surface using an ink jet printer (Fuji Film, DIMATIX Material jet printer DMP-2831). Let the print head be DMC-11610, voltage 25V, frequency 25kHz, and resolution 1018dpi. A50 mm by 50mm pattern was depicted. Subsequently, the resultant was dried by heating at 60 ℃ for 1 hour to obtain a sample in which a dried coating film as a film containing copper oxide was formed on a substrate.
[ post-treatment Process ]
After drying, the mixture was kept at room temperature of 23 ℃ and relative humidity of 100% for 24 hours under normal pressure.
[ reduction Process ]
The reduction is carried out by wet reduction. N, N-bis (2-hydroxyethyl) glycine was dissolved in water to prepare a 35 mass% solution. The film containing copper oxide was used as a reducing solution, and the film was immersed in the reducing solution heated to 60 ℃ for 30 minutes. Then, the copper film was washed with water to obtain a copper film.
[ plating Process ]
Next, OPC Copper NCA (containing 2.2g/L of formaldehyde) of Oneye pharmaceutical industry Co., ltd, which is an electroless plating solution containing EDTA, was heated to 60 ℃ and the sample was immersed for 10 minutes. After the treatment, the sample was taken out and washed with water.
[ evaluation of adhesion ]
According to the results of the tape peeling test, peeling of the film containing copper was not observed, and the adhesion was evaluated as AA.
< example 2>
The reduction step was performed in the same manner as in example 1, except that the heating treatment was performed at 300 ℃ for 1 hour in a nitrogen atmosphere.
< example 3>
The post-treatment step was carried out in the same manner as in example 2, except that the heat treatment was carried out at 300 ℃ for 1 hour in a nitrogen atmosphere after the plating.
< example 4>
The procedure was carried out in the same manner as in example 1, except that the post-treatment step was not carried out.
< example 5>
The procedure of example 3 was repeated except that the substrate was cleaned and pretreated, the dispersion was applied and dried, and the post-treatment step was as follows.
[ substrate cleaning and pretreatment Processes ]
The polyimide substrate was cleaned by irradiating ultrasonic waves in ultrapure water for 5 minutes and then in ethanol for 5 minutes. The surface of the substrate was then subjected to UV ozone treatment for 3 minutes. The substrate was then immersed in N-methylpyrrolidone at room temperature (23 ℃) for 60 minutes. Thereafter, the substrate was washed with water, and air was blown to the surface of the substrate to remove water.
[ coating and drying of the Dispersion ]
1ml of the dispersion was dropped onto the surface, spin-coated (300 rpm, 60 seconds), and then dried at 60 ℃ for 1 hour to obtain a sample in which a dried coating film was formed on a substrate.
[ post-treatment Process ]
It is not implemented.
< example 6>
The procedure 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 procedure as in example 5 was repeated except that the UV ozone treatment was not performed in the pretreatment step.
< example 8>
The same procedure as in example 6 was repeated except that the UV ozone treatment was not performed in the pretreatment step.
< example 9>
The procedure 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 having the configuration shown in fig. 3. Nitrogen gas was fed from the gas supply section 103 into the sample cell 101 at 1.0L/min. The upper surface of the sample cell 101 is made of glass, and is made transparent to the laser light L. The laser light (center wavelength 355nm, frequency 300kHz, pulse width 10ns, output 230mW, spot diameter 20 μm) was irradiated to the coating film 2d in the sample cell 101 while moving the focal position at a maximum speed of 25 mm/sec using a galvanometer scanner 104. At this time, the laser was moved 5mm in the scanning direction (1 st shot), then moved 30 μm in the direction perpendicular to the scanning direction, and again moved in the scanning direction at a maximum speed of 25 mm/sec (2 nd shot). This operation was repeated, whereby laser scanning was performed while moving by 30 μm each in a direction perpendicular to the scanning direction, to obtain a copper-containing film containing copper having a desired dimension of 5mm in length × 5mm in width.
< example 10>
The procedure was carried out in the same manner as in example 6, except that the substrate cleaning and pretreatment steps were carried out as follows.
[ substrate cleaning and pretreatment Processes ]
The polyimide substrate was cleaned by irradiating ultrasonic waves in ultrapure water for 5 minutes and then in ethanol for 5 minutes. The surface of the substrate was then subjected to UV ozone treatment for 3 minutes. The substrate was then immersed in 1-heptanol at room temperature (23 ℃) for 15 minutes. Then, air was blown to the surface of the substrate to remove 1-heptanol.
< example 11>
The procedure was carried out in the same manner as in example 6, except that the substrate cleaning and pretreatment steps were carried out as follows.
[ substrate cleaning and pretreatment Processes ]
The polyimide substrate was cleaned by irradiating ultrasonic waves in ultrapure water for 5 minutes and then in ethanol for 5 minutes. The surface of the substrate was then subjected to a UV ozone treatment for 3 minutes. The substrate was then immersed in propanol at room temperature (23 ℃) for 15 minutes. Thereafter, air was blown to the surface of the substrate to remove propanol.
< example 12>
The same procedure as in example 6 was used except that the preparation of the dispersion, the application of the dispersion and the drying were carried out as described below.
[ production of Dispersion ]
3224g of copper (II) acetate monohydrate (manufactured by Nippon chemical Co., ltd.) was dissolved in a mixed solvent composed of water 30240g and 1, 2-propanediol (manufactured by AGC Co., ltd.) 13976g, and 940g of hydrazine hydrate (manufactured by Nippon Finechem Co., ltd.) was added thereto, followed by stirring and separation into a supernatant and a precipitate by centrifugation.
To 858g of the obtained precipitate, 113g of DISPER BYK-145 (BYK-145) as a phosphorus-containing organic compound and 916g of 1-butanol (Sanko chemical Co., ltd.) as a dispersion medium were added, and dispersion was carried out by using a homogenizer under a nitrogen atmosphere to obtain a dispersion containing monovalent copper oxide particles (particles containing a metal compound). The amount of hydrazine in the dispersion was 0.2 mass%. At this time, the solid content residue (monovalent copper oxide particles) obtained by heating the dispersion at 60 ℃ for 4.5 hours under normal pressure was 34.7% by mass.
[ coating and drying of the Dispersion ]
1ml of the dispersion was dropped onto the surface, spin-coated (200 rpm, 100 seconds), and then dried at 60 ℃ for 1 hour to obtain a sample having a dried coating film formed on a substrate.
< example 13>
The procedure was carried out in the same manner as in example 6, except that the substrate cleaning and pretreatment steps were as follows.
[ substrate cleaning and pretreatment Processes ]
The polyimide substrate was cleaned by irradiating ultrasonic waves in ultrapure water for 5 minutes and then in ethanol for 5 minutes. The surface of the substrate was then subjected to a UV ozone treatment for 3 minutes. The substrate was then immersed in ethanol at room temperature (23 ℃) for 15 minutes. Thereafter, air was blown to the surface of the substrate to remove ethanol.
< example 14>
The procedure was carried out in the same manner as in example 6, except that the substrate cleaning and pretreatment steps were as follows.
[ substrate cleaning and pretreatment Processes ]
The polyimide substrate was cleaned by irradiating ultrasonic waves in ultrapure water for 5 minutes and then in ethanol for 5 minutes. The surface of the substrate was then subjected to UV ozone treatment for 3 minutes. The substrate was then immersed in hexane at room temperature (23 ℃) for 15 minutes. Thereafter, air was blown to the surface of the substrate to remove hexane.
< example 15>
The procedure was carried out in the same manner as in example 6, except that the substrate cleaning and pretreatment steps were as follows.
[ substrate cleaning and pretreatment Processes ]
The polyimide substrate was cleaned by irradiating ultrasonic waves in ultrapure water for 5 minutes and then in ethanol for 5 minutes. The surface of the substrate was then subjected to a UV ozone treatment for 3 minutes. The substrate was then immersed in propylene glycol at room temperature (23 ℃) for 15 minutes. Air was then blown onto the substrate surface to remove the propylene glycol.
< example 16>
The procedure was carried out in the same manner as in example 6, except that the substrate cleaning and pretreatment steps and the post-treatment step were carried out as follows.
[ substrate cleaning and pretreatment Processes ]
The polyimide substrate was cleaned by irradiating ultrasonic waves in ultrapure water for 5 minutes and then in ethanol for 5 minutes. The surface of the substrate was then subjected to a UV ozone treatment for 3 minutes.
[ post-treatment Process ]
After drying, the resultant was stored at room temperature of 23 ℃ and relative humidity of 100% for 24 hours under normal pressure.
< example 17>
The procedure was carried out in the same manner as in example 6, except that the substrate cleaning and pretreatment steps were carried out as follows.
[ substrate cleaning and pretreatment Processes ]
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 mass% aqueous solution of sodium hydroxide at room temperature (23 ℃) for 15 minutes. Thereafter, the substrate was washed with water, and air was blown to the surface of the substrate to remove water.
< example 18>
The procedure was carried out in the same manner as in example 16, except that the post-treatment step was not carried out.
< example 19>
The process was carried out in the same manner as in example 6, except that the plating step was not carried out.
< comparative example 1>
The same procedure as in example 5 was repeated, except that the substrate cleaning and pretreatment and post-treatment steps were not performed.
Peeling of the copper-containing film was observed in the results of the tape peeling test.
< comparative example 2>
The procedure was carried out in the same manner as in example 6, except that the pretreatment step and the post-treatment step were not carried out.
Peeling of the copper-containing film was observed in the results of the tape peeling test.
The results of examples and comparative examples are shown in tables 1 and 2. As shown in tables 1 and 2, it is understood that the adhesion is improved by the pretreatment and/or the post-treatment.
Figure BDA0003871492790000411
/>
Figure BDA0003871492790000421
< examples 20 to 23>
[ evaluation of suitability for ink jetting ]
A dispersion (ink) was prepared by the same procedure as in example 1, except that the solvent of the dispersion was changed to 1-butanol (example 20), 1-hexanol (example 21), 1-heptanol (example 22), or 1-octanol (example 23). The obtained ink was evaluated for the stability of ink jetting in a batch. The time until the nozzle was clogged when the intermittent discharge was performed was measured, and 1 hour or more, 30 minutes or more and less than 1 hour, B and less than 30 minutes, C were evaluated. The conditions for evaluating the batch stability are as follows.
The device comprises the following steps: DIMATIX material jet printing machine DMP-2831
A print head: DMC-11610
Voltage: 25V
Number of ejection nozzles: 7 (No. 5 to 11)
Judging whether ejection exists or not: visual observation by DropWatcher
The results are shown in Table 3.
The ink of the 1-butanol solvent was evaluation C, the ink of the 1-hexanol solvent was evaluation B, the ink of the 1-heptanol solvent and the ink of the 1-octanol solvent was evaluation A. From these results, it was found that the ink jet suitability was good in the ink using 1-heptanol or 1-octanol as a solvent.
[ Table 3]
Solvent(s) Evaluation of intermittent stability
Example 20 1-Butanol C
Example 21 1-hexanol B
Example 22 1-heptanol A
Example 23 1-octanol A
The present invention is not limited to the above-described embodiments or examples. The above embodiments and examples may be modified in design based on common knowledge of those skilled in the art, may be arbitrarily combined, and may be included in the scope of the present invention.
Industrial applicability
One embodiment of the present invention can be suitably applied to the production of printed wiring boards, electronic devices, electromagnetic wave shielding materials, antistatic films, and the like.

Claims (20)

1. A method for manufacturing a structure with a conductive pattern, comprising the steps of:
a coating film forming step of applying a dispersion containing particles containing a metal compound and/or particles containing a metal to a substrate to obtain a coating film; and
a pre-treatment step and/or a post-treatment step,
wherein the content of the first and second substances,
the pretreatment step is a step of subjecting the substrate to 1 or more kinds of treatment selected from the group consisting of UV ozone treatment, organic solvent treatment and alkali treatment before the coating film formation step,
the post-treatment step is a step of performing humidification treatment and/or heating treatment after the coating film formation step.
2. The method for producing a structure with a conductive pattern according to claim 1, wherein the pretreatment step is an organic solvent treatment using an organic solvent having an SP value of 7.5 to 12.6.
3. The method for producing a structure with a conductive pattern according to claim 2, wherein the SP value of the organic solvent is 9.9 or more and 11.6 or less.
4. The method for producing a structure with a conductive pattern according to claim 2, wherein the organic solvent contains at least 1 selected from the group consisting of N-methylpyrrolidone, 1-propanol, and 1-heptanol.
5. The method for manufacturing a structure with a conductive pattern according to claim 2, wherein the organic solvent contains N-methylpyrrolidone.
6. The method for producing a structure with a conductive pattern according to claim 1 or 2, wherein the pretreatment step is an organic solvent treatment using an organic solvent in which a difference between an SP value of the base material and an SP value of the organic solvent is 0.01 to 4.6.
7. The method for manufacturing a structure with a conductive pattern according to claim 1 or 2, further comprising a reduction step after the coating film formation step.
8. The method for manufacturing a structure with a conductive pattern according to claim 7, wherein the reducing step is a wet reducing step.
9. The method of manufacturing a structure with a conductive pattern according to claim 1 or 2, further comprising a plating step of performing plating after the coating film forming step.
10. The method of manufacturing a structure with a conductive pattern according to claim 9, wherein in the plating step, a plating solution containing ethylenediaminetetraacetic acid (EDTA) is used.
11. The method for manufacturing a structure with a conductive pattern according to claim 1 or 2, further comprising a reduction step after the coating film formation step, and further comprising a plating step after the reduction step.
12. The method for manufacturing a structure with a conductive pattern according to claim 1 or 2, comprising two steps of the pretreatment step and the post-treatment step.
13. The method for manufacturing a structure with a conductive pattern according to claim 1 or 2, wherein the base material is polyimide.
14. The method for manufacturing a structure with a conductive pattern according to claim 1 or 2, wherein the dispersion contains at least 1 selected from the group consisting of 1-hexanol, 1-heptanol, and 1-octanol.
15. The method for manufacturing a structure with a conductive pattern according to claim 1 or 2, wherein the particles containing a metal compound and/or the particles containing a metal are/is copper oxide-containing particles and/or copper-containing particles.
16. A structure manufacturing kit with a conductive pattern, comprising:
a dispersion comprising particles comprising a metal compound and/or particles comprising a metal;
a plating solution containing EDTA (ethylenediaminetetraacetic acid); and
a substrate subjected to 1 or more treatments selected from the group consisting of UV ozone treatment, organic solvent treatment and alkali treatment.
17. A structure manufacturing kit with a conductive pattern, comprising:
a dispersion comprising particles comprising a metal compound and/or particles comprising a metal;
a plating solution containing EDTA (ethylenediaminetetraacetic acid);
1 or more treating agents selected from the group consisting of organic solvents and alkali treating agents; and
a substrate.
18. A structure manufacturing kit with a conductive pattern, comprising:
a dispersion comprising particles comprising a metal compound and/or particles comprising a metal; and
an organic solvent for the treatment of the organic solvent,
the SP value of the organic solvent is 7.5 to 12.6.
19. The structure manufacturing kit with a conductive pattern according to any one of claims 16 to 18, wherein the particle containing the metal compound and/or the particle containing the metal is a particle containing copper oxide and/or a particle containing copper.
20. A system for manufacturing a structure with a conductive pattern, comprising:
a pretreatment mechanism for subjecting the base material to an organic solvent treatment using an organic solvent having an SP value of 7.5 to 12.6;
a coating mechanism that applies a dispersion containing particles containing a metal compound and/or particles containing a metal to a substrate to obtain a coating film; and
and a plating mechanism for plating the coating film passing through the coating mechanism.
CN202211205287.2A 2021-10-08 2022-09-29 Method for manufacturing structure with conductive pattern, kit and system Pending CN115968113A (en)

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