WO2017057301A1 - 導電層形成用塗布液及び導電層の製造方法 - Google Patents
導電層形成用塗布液及び導電層の製造方法 Download PDFInfo
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- WO2017057301A1 WO2017057301A1 PCT/JP2016/078328 JP2016078328W WO2017057301A1 WO 2017057301 A1 WO2017057301 A1 WO 2017057301A1 JP 2016078328 W JP2016078328 W JP 2016078328W WO 2017057301 A1 WO2017057301 A1 WO 2017057301A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/68—Particle size between 100-1000 nm
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0263—Details about a collection of particles
- H05K2201/0266—Size distribution
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/0709—Catalytic ink or adhesive for electroless plating
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0756—Uses of liquids, e.g. rinsing, coating, dissolving
- H05K2203/0759—Forming a polymer layer by liquid coating, e.g. a non-metallic protective coating or an organic bonding layer
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1131—Sintering, i.e. fusing of metal particles to achieve or improve electrical conductivity
Definitions
- the present invention relates to a coating liquid for forming a conductive layer and a method for producing a conductive layer.
- a substrate for printed wiring boards has been proposed in which a copper thin layer is laminated on a heat-resistant insulating base film without an adhesive layer (see JP-A-9-136378).
- a copper thin film layer having a thickness of 0.25 to 0.30 ⁇ m is formed on the surface of the heat-resistant insulating base film by sputtering.
- This printed wiring board base material has a copper thick film layer laminated on the outer surface of the copper thin film layer using an electroplating method, thereby ensuring sufficient adhesive strength between the base film and the copper thin film layer. It is said that the density can be increased.
- the conductive layer forming coating solution according to one embodiment of the present invention is a conductive layer forming coating solution containing fine metal particles, a dispersion medium, and a dispersant, and has a pH of 4 to 8 and an electrical conductivity of 100 ⁇ S / cm.
- the content of the metal fine particles is 20% by mass or more and 80% by mass or less.
- a method for producing a conductive layer according to another aspect of the present invention is a method for producing a conductive layer using a coating liquid for forming a conductive layer containing metal fine particles, a dispersion medium, and a dispersing agent.
- a coating step of coating the coating solution; and a heating step of heating the coating solution for forming the conductive layer after coating is 4 to 8, and the electrical conductivity is 100 ⁇ S / cm or more and 800 ⁇ S / cm or less, and the content of the metal fine particles is 20% by mass or more and 80% by mass or less.
- the substrate for printed wiring boards described in the above publication can be said to meet the demand for high-density printed wiring in that a copper thin film layer can be directly laminated on a base film.
- this printed wiring board base material has a copper thin film layer formed by a sputtering method, vacuum equipment is required, and the equipment costs such as construction, maintenance, and operation of the equipment increase.
- this printed wiring board base material since it is necessary to form this printed wiring board base material under vacuum conditions using a vacuum facility, there is a limit to increasing the size of the base material.
- the present invention has been made based on such circumstances, and a conductive layer forming coating solution capable of easily and reliably forming a conductive layer having a certain thickness at a relatively low cost, and the conductive layer forming coating.
- An object is to provide a method for producing a conductive layer using a liquid.
- the conductive layer forming coating liquid and the conductive layer manufacturing method of the present invention can easily and reliably form a conductive layer having a certain thickness at a relatively low cost.
- the conductive layer forming coating solution according to one embodiment of the present invention is a conductive layer forming coating solution containing fine metal particles, a dispersion medium, and a dispersant, and has a pH of 4 to 8 and an electrical conductivity of 100 ⁇ S / cm.
- the content of the metal fine particles is 20% by mass or more and 80% by mass or less.
- the conductive layer forming coating solution contains a dispersion medium and a dispersant, and the pH and electrical conductivity are within the above ranges, so that even if the content of the metal fine particles is as large as within the above range, the dispersion medium. It is excellent in the uniform dispersibility of the metal fine particles. Therefore, the coating liquid for forming a conductive layer is applied and heated, for example, on the surface of the base film constituting the substrate for a printed wiring board, so that the metal fine particles are arranged at a high density with a certain thickness. The conductive layer can be easily and reliably formed.
- the said coating liquid for conductive layer formation can form a conductive layer at comparatively low cost, without using the expensive vacuum equipment required for physical vapor deposition, such as sputtering. Furthermore, since the conductive layer forming coating solution does not require the use of vacuum equipment when forming the conductive layer, the size of the conductive layer can be prevented from being limited by the size of the vacuum equipment. As a result, according to the coating liquid for forming a conductive layer, it is easy to form a conductive layer having a large outer dimension.
- the dispersing agent may be a polymer compound.
- the dispersant is a polymer dispersant, it is easy to uniformly disperse the metal fine particles in the dispersion medium while preventing aggregation of the metal fine particles. Thereby, it is easy to form a dense and unbroken conductive layer.
- the polymer compound preferably has an imino group.
- the polymer compound has an imino group, it is easy to disperse the metal fine particles more uniformly in the dispersion medium while preventing aggregation of the metal fine particles easily and reliably.
- the polymer compound may be polyethyleneimine or a polyethyleneimine-ethylene oxide adduct. As described above, when the polymer compound is polyethyleneimine or a polyethyleneimine-ethylene oxide adduct, the metal fine particles can be more uniformly dispersed in the dispersion medium while preventing aggregation of the metal fine particles easily and reliably. .
- the average particle diameter D 50 which is calculated from the cumulative distribution measured by laser diffraction, of the metal fine particles is preferably 1nm or more 500nm or less. According to the coating liquid for forming a conductive layer, the metal fine particles can be uniformly dispersed in the dispersion medium even if the average particle diameter D 50 of the metal fine particles is relatively small as in the above range. Therefore, the average particle diameter D 50 of the metal particles by the above range, it is possible to form a dense conductive layer easily and reliably.
- the “average particle diameter D 50 ” refers to a value calculated from the cumulative volume distribution.
- the viscosity at 25 ° C. of the conductive layer forming coating solution is preferably 100 mPa ⁇ s or less.
- paintability of the said coating liquid for conductive layer formation can be improved because the viscosity in 25 degreeC is below the said upper limit.
- the main component of the metal fine particles is preferably copper or a copper alloy.
- the main component of the metal fine particles is copper or a copper alloy, a conductive layer having excellent conductivity can be formed.
- a method for producing a conductive layer according to another aspect of the present invention is a method for producing a conductive layer using a coating liquid for forming a conductive layer containing metal fine particles, a dispersion medium, and a dispersing agent.
- a coating step of coating the coating solution; and a heating step of heating the coating solution for forming the conductive layer after coating is 4 to 8, and the electrical conductivity is 100 ⁇ S / cm or more and 800 ⁇ S / cm or less, and the content of the metal fine particles is 20% by mass or more and 80% by mass or less.
- the coating liquid for forming a conductive layer contains a dispersion medium and a dispersing agent, the pH and electrical conductivity of the coating liquid for forming a conductive layer at the time of coating are within the above ranges. Even if the content of the metal fine particles is within the above range, the metal particles are excellent in uniform dispersibility during coating. Therefore, the manufacturing method of the said conductive layer can form the conductive layer which has fixed thickness and a metal fine particle is arrange
- the manufacturing method of the said conductive layer does not need to use a vacuum installation, it can prevent that the magnitude
- electrical conductivity refers to a value measured in accordance with JIS-K0130: 2008.
- “Viscosity” refers to a value measured according to JIS-Z8803: 2011.
- “Main component” refers to a component having the highest content, for example, a component having a content of 50% by mass or more, and preferably a component having a content of 80% by mass or more.
- the said coating liquid for conductive layer formation is for printed wiring board base material formation, for example. Specifically, the coating liquid for forming the conductive layer is applied to the surface of the base film constituting the printed wiring board, and then dried and heated to be laminated on the surface of the base film, so that the metal fine particles To form a conductive layer (metal fine particle sintered layer).
- the conductive layer forming coating solution contains fine metal particles, a dispersion medium, and a dispersant.
- the conductive layer forming coating solution has a pH of 4 or more and 8 or less, an electrical conductivity of 100 ⁇ S / cm or more and 800 ⁇ S / cm or less, and a metal fine particle content of 20% by mass or more and 80% by mass or less.
- the conductive layer forming coating solution contains a dispersion medium and a dispersant, and the pH and electrical conductivity are within the above ranges, so that even if the content of the metal fine particles is as large as within the above range, the dispersion medium. It is excellent in the uniform dispersibility of the metal fine particles.
- the conductive layer forming coating solution is applied and heated, for example, on the surface of the base film, thereby easily and reliably forming a conductive layer having a certain thickness and finely arranged metal fine particles. can do.
- the said coating liquid for conductive layer formation can form a conductive layer at comparatively low cost, without using the expensive vacuum equipment required for physical vapor deposition, such as sputtering.
- the conductive layer forming coating solution does not require the use of vacuum equipment when forming the conductive layer, the size of the conductive layer can be prevented from being limited by the size of the vacuum equipment.
- the coating liquid for forming a conductive layer it is easy to form a conductive layer having a large outer dimension.
- the dispersion medium contained in the conductive layer forming coating solution is not particularly limited, but water is typically used.
- Examples of the main component of the fine metal particles contained in the conductive layer forming coating solution include copper (Cu), nickel (Ni), aluminum (Al), gold (Au), silver (Ag), and alloys thereof. Can be mentioned. Among these, copper or a copper alloy is preferable because it is excellent in conductivity and easily increases the adhesion with the base film.
- the lower limit of the content of the metal fine particles in the conductive layer forming coating solution is 20% by mass, and more preferably 25% by mass.
- the upper limit of the content of the metal fine particles is 80% by mass, more preferably 50% by mass, and further preferably 35% by mass. If the content of the metal fine particles is less than the lower limit, it may be difficult to form a conductive layer having a sufficient thickness and density. Conversely, if the content of the metal fine particles exceeds the upper limit, it may be difficult to uniformly disperse the metal fine particles in the dispersion medium.
- the lower limit of the average particle diameter D 50 calculated from the volume cumulative distribution measured by the laser diffraction method of the metal fine particles is preferably 1 nm, and more preferably 30 nm.
- the upper limit of the average particle diameter D 50, 500 nm is preferred, 200 nm, and still more preferably 100 nm.
- the average particle diameter D 50 is less than the above lower limit, the dispersibility and stability of the fine metal particles in a dispersion medium may be lowered.
- the average particle diameter D 50 exceeds the upper limit, the density of the metal fine particles when the conductive layer forming coating solution is applied tends to be uneven, and as a result, a sufficiently dense conductive layer is formed. May be difficult.
- the average particle diameter D50SEM As a minimum of average particle diameter D50SEM computed based on the measurement by the scanning electron microscope (SEM) of the said metal microparticle, 1 nm is preferable and 30 nm is more preferable.
- the upper limit of the average particle diameter D50SEM is preferably 550 nm, more preferably 250 nm, and even more preferably 150 nm. If the average particle diameter D50SEM is less than the lower limit, the dispersibility and stability of the metal fine particles in the dispersion medium may be reduced.
- the average particle diameter D 50 SEM means that the surface of the metal fine particles was observed with a scanning electron microscope (SEM), and 100 arbitrarily extracted metal fine particles were measured and the volumes were integrated in ascending order of the particle diameter. The particle diameter at which the cumulative volume is 50%.
- the ratio of the average particle diameter D 50SEM calculated based on the measurement by a scanning electron microscope of the metallic fine particles to the average particle diameter D 50 which is calculated from the cumulative distribution measured by laser diffraction, of the metal fine particles is preferably 1.5, more preferably 1.3.
- the ratio (D 50 SEM / D 50 ) exceeds the upper limit, the shape of individual metal fine particles tends to be non-uniform. As a result, the smoothness of the surface of the coating film formed by applying the conductive layer forming coating solution becomes insufficient, which may make it difficult to form a sufficiently dense conductive layer.
- the lower limit of the ratio (D 50SEM / D 50) is not particularly limited, it may be 1, for example.
- the dispersant is not particularly limited as long as it can disperse the metal fine particles well in the dispersion medium, but a polymer compound is preferably used.
- the dispersing agent is a polymer dispersing agent, the metal fine particles can be easily dispersed uniformly in the dispersion medium while preventing the aggregation of the metal fine particles. Therefore, when the dispersant is a polymer dispersant, it is easy to form a dense and unbroken conductive layer using the conductive layer forming coating solution.
- the polymer compound preferably does not contain sulfur, phosphorus, boron, halogen elements and alkali metals.
- polyalkyleneimine such as polyethyleneimine, polypropyleneimine, polyhexamethyleneimine
- Amine polymer compounds such as pyrrolidone
- hydrocarbon polymer compounds having a carboxylic acid group in the molecule such as polyacrylic acid and carboxymethylcellulose
- poval polyvinyl alcohol
- styrene-maleic acid copolymer olefin-maleic acid A copolymer
- a polyethyleneimine-ethylene oxide adduct having a polyethyleneimine moiety and a polyethylene oxide moiety in one molecule.
- the polymer compound a compound having an imino group is preferable, and a polyethyleneimine and a polyethyleneimine-ethylene oxide adduct are particularly preferable.
- the metal fine particles can be uniformly dispersed in the dispersion medium while preventing aggregation of the metal fine particles easily and reliably.
- the coating liquid for forming a conductive layer can increase the content of nitrogen atoms in the polymer compound because the polymer compound is polyethyleneimine or a polyethyleneimine-ethylene oxide adduct.
- the metal fine particles can be more uniformly dispersed in the dispersion medium while preventing the aggregation of the particles more easily and reliably.
- the lower limit of the weight average molecular weight of the polymer compound is preferably 2,000, and more preferably 5,000.
- the upper limit of the weight average molecular weight of the polymer compound is preferably 750,000, and more preferably 100,000. If the weight average molecular weight of the polymer compound is less than the lower limit, there is a risk that the effect of preventing the aggregation of the metal fine particles and maintaining the dispersion of the metal fine particles may not be obtained. It may be difficult to form a conductive layer that does not exist.
- the weight average molecular weight of the polymer compound exceeds the upper limit, the bulk of the dispersant is too large and inhibits sintering of the metal fine particles in the heat treatment performed after application of the conductive layer forming coating solution. May cause voids.
- the bulk of the dispersant is too large, the denseness of the conductive layer may decrease, or the conductivity of the conductive layer may decrease due to the decomposition residue of the dispersant.
- the lower limit of the content of the dispersant in the conductive layer forming coating solution is preferably 0.01% by mass, and more preferably 0.02% by mass.
- the upper limit of the content of the dispersant is preferably 2% by mass, and more preferably 1% by mass. If the content of the dispersant is less than the lower limit, the metal fine particles cannot be sufficiently surrounded by the dispersant, and aggregation of the metal fine particles may not be sufficiently prevented.
- the content of the dispersant exceeds the upper limit, an excessive dispersant inhibits firing including sintering of the metal fine particles during the heat treatment after the application of the coating liquid for forming the conductive layer, resulting in voids. May occur. Further, the decomposition residue of the dispersant may remain in the conductive layer as an impurity, and the conductivity of the conductive layer may be reduced.
- the conductive layer forming coating solution may contain an organic solvent as required.
- organic solvent various water-soluble organic solvents can be used.
- methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert- Examples include alcohols such as butyl alcohol; ketones such as acetone and methyl ethyl ketone; polyhydric alcohols such as ethylene glycol and glycerin and other esters; glycol ethers such as ethylene glycol monoethyl ether and diethylene glycol monobutyl ether.
- the lower limit of the content of the organic solvent in the conductive layer forming coating solution is preferably 25% by mass, more preferably 30% by mass.
- the upper limit of the content of the organic solvent is preferably 75% by mass, and more preferably 70% by mass. If the content of the organic solvent is less than the lower limit, the effects such as viscosity adjustment and vapor pressure adjustment by the organic solvent may not be sufficiently obtained. Conversely, if the content of the organic solvent exceeds the upper limit, the swelling effect of the dispersant due to water becomes insufficient, and the metal fine particles may aggregate in the conductive layer forming coating solution.
- the pH of the conductive layer forming coating solution is 4 or more and 8 or less as described above. Moreover, as a minimum of pH of the said coating liquid for conductive layer formation in case the said dispersing agent is a polyethyleneimine, 6 is preferable and 6.5 is more preferable. On the other hand, as the upper limit of the pH of the coating liquid for forming a conductive layer when the dispersant is polyethyleneimine, 7.5 is preferable. Further, when the dispersant is a polyethyleneimine-ethylene oxide adduct, the lower limit of the pH of the conductive layer forming coating solution is preferably 4.5 and more preferably 5.
- the upper limit of the pH of the conductive layer forming coating solution is preferably 7, and more preferably 6.0. If the pH is less than the lower limit, the metal fine particles may be easily dissolved. On the contrary, when the pH exceeds the upper limit, the uniform dispersibility of the metal fine particles may be lowered by the action of hydroxide ions.
- the lower limit of the electrical conductivity of the conductive layer forming coating solution is 100 ⁇ S / cm, preferably 150 ⁇ S / cm, and more preferably 200 ⁇ S / cm.
- the upper limit of the electric conductivity is 800 ⁇ S / cm, preferably 700 ⁇ S / cm, and more preferably 600 ⁇ S / cm. If the electrical conductivity is less than the lower limit, the metal fine particles may be easily aggregated. On the other hand, when the electrical conductivity exceeds the upper limit, decomposition residues such as a dispersant easily remain as impurities in the conductive layer formed from the coating liquid for forming the conductive layer. May decrease.
- the upper limit of the viscosity at 25 ° C. of the conductive layer forming coating solution is preferably 100 mPa ⁇ s, more preferably 30 mPa ⁇ s, and even more preferably 2 mPa ⁇ s.
- the lower limit of the viscosity is preferably 1 mPa ⁇ s. If the viscosity exceeds the upper limit, applicability may be reduced. Conversely, if the viscosity is less than the lower limit, the moldability of the coating film may be reduced.
- the conductive layer forming coating liquid manufacturing method includes a metal fine particle manufacturing process for manufacturing metal fine particles, a cleaning process for cleaning the metal fine particles manufactured in the metal fine particle manufacturing process, and the metal fine particles cleaned in the cleaning process are dispersed. A dispersion step of dispersing in a medium.
- the metal fine particle production step can be performed by a high temperature treatment method, a liquid phase reduction method, a gas phase method, or the like. Below, the method by a liquid phase reduction method is demonstrated as a preferable aspect of the said metal microparticle manufacturing process.
- a water-soluble metal compound that is a source of metal ions that form fine metal particles in water and the dispersant are dissolved, and a reducing agent and A complexing agent as an optional component may be added and the metal ion may be reduced for a certain time.
- the produced metal fine particles have a spherical or granular shape and can be made into fine particles.
- copper copper (II) nitrate (Cu (NO 3 ) 2 ), copper (II) sulfate pentahydrate (CuSO 4 .5H 2 ) as the water-soluble metal compound that is the basis of the metal ions.
- the reducing agent various reducing agents capable of reducing and precipitating metal ions in a liquid phase (aqueous solution) reaction system can be used.
- the reducing agent include sodium borohydride, sodium hypophosphite, hydrazine, transition metal ions such as trivalent titanium ions and divalent cobalt ions, reducing sugars such as ascorbic acid, glucose and fructose, ethylene Examples thereof include polyhydric alcohols such as glycol and glycerin.
- the titanium redox method is a method in which metal ions are reduced by redox action when trivalent titanium ions are oxidized to tetravalent, and metal fine particles are precipitated.
- the metal fine particles obtained by the titanium redox method have a small and uniform particle size, and the titanium redox method can make the metal fine particles spherical or granular. Therefore, by using the titanium redox method, it is possible to promote densification of the conductive layer formed from the conductive layer forming coating solution.
- the complexing agent examples include sodium citrate, sodium gluconate, sodium acetate, sodium propionate, malic acid, lactic acid, Rochelle salt, sodium thiosulfate, sodium tartrate, ethylenediaminetetraacetic acid, ammonia and the like.
- the types and blending ratios of the metal compound, dispersant, reducing agent, complexing agent are adjusted, and when the metal compound is reduced, the stirring speed, temperature, time, pH Etc. may be adjusted.
- the pH of the reaction system is preferably 7 or more and 13 or less in order to obtain metal fine particles having a minute particle size as in this embodiment.
- the pH of the reaction system can be adjusted to the above range by using a pH adjuster.
- a general acid or alkali such as hydrochloric acid, sulfuric acid, sodium hydroxide, sodium carbonate or the like is used.
- alkali metal or alkaline earth metal Nitric acid or ammonia that does not contain a halogen element such as chlorine, or an impurity element such as sulfur, phosphorus, or boron may be used.
- the metal fine particles deposited in the metal fine particle production step are washed with water.
- the metal fine particles and the liquid are separated by centrifugation, and the metal fine particles are washed by adding water to the separated metal fine particles and stirring.
- count of performing water washing For example, it can be 1 to 3 times, and 2 times is more preferable.
- the manufacturing method of the said coating liquid for conductive layer formation can reduce pH of the said coating liquid for conductive layer formation, electrical conductivity, and content of a dispersing agent by increasing the frequency
- the conductive layer forming coating solution adjusts the pH, electrical conductivity, and dispersant content of the conductive layer forming coating solution to the above ranges by setting the number of water washings within the above range. easy.
- the manufacturing method of the said coating liquid for conductive layer formation uses the metal fine particle of this powder form in the below-mentioned dispersion
- the metal fine particles after the washing step are dispersed in a dispersion medium.
- the dispersion step can be performed, for example, by containing powdered metal fine particles obtained by drying after the washing step in water as a dispersion medium.
- the fine metal particles after the washing step exist in a state surrounded by the dispersing agent, it is not always necessary to add the dispersing agent to the dispersion medium in the dispersing step, but it is necessary in the dispersing step. Accordingly, the dispersant may be added to the dispersion medium.
- the method for producing the coating liquid for forming a conductive layer can easily and reliably produce the coating liquid for forming a conductive layer capable of easily and reliably forming a conductive layer at a relatively low cost.
- the method for producing the conductive layer includes a coating process for coating the conductive layer forming coating liquid and a heating process for heating the conductive layer forming coating liquid after coating.
- the method for producing a conductive layer may further include a metal plating layer forming step of forming a metal plating layer on the outer surface of the metal fine particle sintered layer formed by sintering the metal fine particles by the heating.
- the pH at the time of application of the coating liquid for forming the conductive layer is 4 or more and 8 or less
- the electric conductivity is 100 ⁇ S / cm or more and 800 ⁇ S / cm or less
- the content of the metal fine particles is 20% by mass or more. 80% by mass or less.
- a laminate of the metal fine particle sintered layer and the metal plating layer is formed as a conductive layer.
- the coating liquid for forming a conductive layer contains a dispersion medium and a dispersing agent, and the pH and electric conductivity of the coating liquid for forming a conductive layer at the time of coating are within the above ranges. Therefore, even if the content of the metal fine particles is increased within the above range, the uniform dispersibility of the metal fine particles during coating is excellent. Therefore, the manufacturing method of the said conductive layer can form the conductive layer which has fixed thickness and a metal fine particle is arrange
- the manufacturing method of the said conductive layer does not need to use a vacuum installation, it can prevent that the magnitude
- the conductive layer forming application liquid is applied to one surface of the base film 1.
- a flexible resin such as polyimide, liquid crystal polymer, fluororesin, polyethylene terephthalate, polyethylene naphthalate, paper phenol, paper epoxy, glass composite, glass epoxy, Teflon (registered trademark) And rigid materials such as glass substrates, rigid flexible materials composed of hard materials and soft materials, and the like.
- polyimide is preferred because of its high bonding strength with metal oxides and the like.
- the surface of the base film 1 on which the coating liquid for forming the conductive layer is applied is subjected to a hydrophilic treatment.
- a hydrophilic treatment for example, plasma treatment for irradiating plasma to make the coated surface hydrophilic, or alkali treatment for hydrophilizing the coated surface with an alkaline solution can be employed.
- plasma treatment is preferable as the hydrophilic treatment.
- Examples of the method for applying the conductive layer forming coating solution on one surface of the base film 1 include spin coating, spray coating, bar coating, die coating, slit coating, roll coating, and dip coating. Conventionally known coating methods can be used. Alternatively, the conductive layer forming coating solution may be applied to only a part of one surface of the base film 1 by screen printing, a dispenser, or the like.
- the coating film 3 containing the metal fine particles 2 is formed, for example, by drying at a temperature of room temperature or higher. As an upper limit of drying temperature, 100 degreeC is preferable and 40 degreeC is more preferable. When the drying temperature exceeds the above upper limit, a crack may occur in the coating film 3 due to rapid drying of the coating film 3.
- the lower limit of the average thickness of the coating film 3 (the average thickness when the conductive layer forming coating solution is applied once) is preferably 0.1 ⁇ m, and more preferably 0.2 ⁇ m.
- the upper limit of the average thickness of the coating film 3 is preferably 0.5 ⁇ m, more preferably 0.4 ⁇ m. If the average thickness of the coating film 3 is less than the above lower limit, there is a possibility that the thickness of the metal fine particle sintered layer 4 obtained by the heating step described later cannot be sufficiently increased.
- the “average thickness” refers to an average value obtained by measuring the thickness of the portion where the metal fine particles are present in the coating film with a fluorescent X-ray film thickness meter. Moreover, the said average value can be calculated
- the upper limit of the surface roughness Sa of the coating film 3 is preferably 0.12 ⁇ m, and more preferably 0.08 ⁇ m. If the surface roughness Sa of the coating film 3 exceeds the above upper limit, it may be difficult to form a sufficiently dense metal fine particle sintered layer 4. In addition, as a minimum of surface roughness Sa of the coating film 3, it does not specifically limit, For example, it can be set as 0.01 micrometer. “Surface roughness Sa” refers to a value based on ISO25178.
- the metal fine particle sintered layer 4 is formed by firing the coating film 3.
- the metal fine particles 2 are sintered together by firing the coating film 3, and the sintered body of the metal fine particles 2 is fixed to one surface of the base film 1.
- the dispersant and other organic substances contained in the coating film 3 are volatilized or decomposed by this baking.
- the metal fine particles are oxidized by heating to generate a metal hydroxide based on the metal of the metal fine particles or a group derived from the metal hydroxide.
- a metal oxide based on the above metal or a group derived from the metal oxide is generated.
- copper oxide and copper hydroxide are generated in the vicinity of the interface between the metal fine particle sintered layer 4 and the base film 1, but more copper oxide is generated.
- the adhesion between the metal fine particle sintered layer 4 and the base film 1 is strong. Becomes larger.
- the above heating process is performed in an atmosphere containing a certain amount of oxygen.
- the oxygen concentration of the atmosphere at the time of heat processing 1 ppm is preferable and 10 ppm is more preferable.
- the upper limit of the oxygen concentration is preferably 10,000 ppm, more preferably 1,000 ppm. If the oxygen concentration is less than the lower limit, the amount of copper oxide produced in the vicinity of the interface of the metal fine particle sintered layer 4 is reduced, and sufficient adhesion between the metal fine particle sintered layer 4 and the base film 1 cannot be obtained. There is a fear. On the other hand, when the oxygen concentration exceeds the upper limit, the metal fine particles are excessively oxidized, and the conductivity of the metal fine particle sintered layer 4 may be lowered.
- the lower limit of the heating temperature is preferably 150 ° C, more preferably 200 ° C.
- an upper limit of heating temperature 500 degreeC is preferable and 400 degreeC is more preferable. If the heating temperature is less than the lower limit, the amount of copper oxide produced in the vicinity of the interface of the metal fine particle sintered layer 4 is reduced, and the adhesion between the metal fine particle sintered layer 4 and the base film 1 may not be sufficiently obtained. There is. Conversely, if the heating temperature exceeds the upper limit, the base film 1 may be deformed when the base film 1 is an organic resin such as polyimide.
- the metal plating layer forming step includes a first metal plating layer forming step and a second metal plating layer forming step.
- First metal plating layer forming step In the first metal plating layer forming step, as shown in FIG. 3, the first metal plating layer 5 is formed on the outer surface of the metal fine particle sintered layer 4. Specifically, in the first metal plating layer forming step, the voids of the metal fine particle sintered layer 4 are filled with the plating metal, and the plated metal is laminated on one surface of the metal fine particle sintered layer 4.
- the manufacturing method of the said conductive layer can improve the adhesive force of a conductive layer and the base film 1 by having the said 1st metal plating layer formation process.
- the plating method for forming the first metal plating layer 5 is not particularly limited, and may be electroless plating or electroplating, but the space between the metal fine particles forming the metal fine particle sintered layer 4 Electroless plating that can easily and reliably improve the peel strength of the metal fine particle sintered layer 4 and the base film 1 is preferable by filling in more accurately.
- the procedure in the case of adopting the above electroless plating is not particularly limited. What is necessary is just to perform electroless plating by a well-known means.
- the procedure is not particularly limited, and may be appropriately selected from known electrolytic plating baths and plating conditions, for example.
- the copper oxide in the vicinity of the interface between the metal fine particle sintered layer 4 and the base film 1 is further increased, so that the adhesion between the metal fine particle sintered layer 4 and the base film 1 can be further improved.
- the second metal plating layer forming step In the second metal plating layer forming step, the second metal plating layer 6 is formed on the outer surface of the first metal plating layer 5 as shown in FIG.
- the manufacturing method of the said conductive layer can adjust the thickness of a conductive layer easily and reliably by having the said 2nd metal plating layer formation process.
- the plating method for forming the second metal plating layer 6 is not particularly limited and may be electroless plating or electroplating, but the thickness can be adjusted easily and accurately. In addition, electroplating capable of forming the second metal plating layer 6 in a relatively short time is preferable.
- the procedure in the case of employing the above electroless plating is not particularly limited, and can be performed by the same procedure as that for forming the first metal plating layer 5 described above. Moreover, also when employ
- the conductive layer manufactured with the manufacturing method of the said conductive layer is formed as a conductive pattern laminated
- stacked on one surface of the base film 1 and the base film 1 is manufactured.
- the conductive layer forming coating solution is not necessarily used for forming a printed wiring board substrate.
- the manufacturing method of the said conductive layer does not necessarily need to be implemented as a manufacturing method of the conductive layer of the base material for printed wiring boards.
- the manufacturing method of the said conductive layer is a case where it implements as a manufacturing method of the conductive layer of the base material for printed wiring boards, it does not necessarily need to provide a metal plating layer formation process.
- the manufacturing method of the said conductive layer may manufacture a conductive layer by performing the above-mentioned application
- the manufacturing method of the said conductive layer is equipped with a metal plating layer formation process, it does not necessarily need to have both a 1st metal plating layer formation process and a 2nd metal plating layer formation process, and a 1st metal plating layer formation process You may have only. Furthermore, the manufacturing method of the said conductive layer does not need to form a conductive layer only in one side of a base film, and may form a conductive layer in both surfaces of a base film.
- No. 6-No. 9 No. 1 except that the content of the copper fine particles in the coating liquid for forming the conductive layer was as shown in Table 1. No. 1 as in No. 1. 6-No. Nine conductive layer forming coating solutions were obtained. No. 6-No. No. 9 conductive layer forming coating solution is No. 9. In the same manner as in No. 1, each was applied by a bar coating method onto a polyimide film (10 cm square) subjected to a hydrophilic treatment.
- No. 10 No. 1 except that 1 g of polyethyleneimine-ethylene oxide adduct was used as a dispersant. No. 1 as in No. 1.
- Ten conductive layer forming coating solutions were obtained.
- No. No. 10 conductive layer forming coating solution was prepared as No. 10; 1 was applied onto a polyimide film (10 cm square) that had been subjected to a hydrophilic treatment by a bar coating method.
- No. 11 No. 1 except that 1 g of polyethyleneimine-ethylene oxide adduct was used as a dispersant and the amount of water per washing step was as shown in Table 1. No. 1 as in No. 1. Eleven conductive layer forming coating solutions were obtained. No. No. 11 conductive layer forming coating solution. 1 was applied onto a polyimide film (10 cm square) that had been subjected to a hydrophilic treatment by a bar coating method.
- the coating thickness was measured using a fluorescent X-ray film thickness meter “FT9500” manufactured by Hitachi High-Tech Science Co., Ltd.
- the thickness of the coating film was determined by measuring the thickness of the copper fine particles at 10 locations at a rate of 1 location per 10 cm 2 area and averaging the thickness at these 10 locations. The measurement results are shown in Table 1.
- ⁇ Average particle diameter D 50> The average particle diameter D 50 [nm] of the metal fine particles (copper fine particles) calculated from the volume cumulative distribution was measured using a particle size distribution measuring device “Nanotrac Wave-EX150” manufactured by Microtrack Bell Co., Ltd. The measurement results are shown in Table 1.
- the conductive layer forming coating solution No. 11 has a pH of 4 or more and 8 or less, an electric conductivity of 100 ⁇ S / cm or more and 800 ⁇ S / cm or less, and a content of metal fine particles (copper fine particles) of 20 mass% or more and 80 mass% or less.
- a relatively small coating film having a thickness of 0.1 ⁇ m or more and a relatively large thickness and a surface roughness Sa of 0.12 ⁇ m or less can be formed.
- Conductive layer forming coating liquid 11 since the ratio of the average particle diameter D 50SEM / average particle diameter D 50 of 1.1 or less and small, the shape of the individual metal particles (copper particles) are aligned in a substantially spherical shape As a result, it was found that the surface roughness Sa of the coating film can be reduced to 0.063 ⁇ m or less because these metal fine particles are easily dispersed uniformly at high density in the coating film. In contrast, no. 12-No.
- the coating liquid for forming a conductive layer 16 has a relatively large thickness and a relatively small surface roughness Sa because the pH, electrical conductivity, and content of metal fine particles (copper fine particles) are not adjusted to the above ranges. It turned out that it was difficult to form a coating film.
- the average particle diameter D 50SEM is relatively large, and since the ratio of the average particle diameter D 50SEM / average particle diameter D 50 is as large as 2.1 or more, the surface roughness of the coating film It was found that Sa could not be kept sufficiently small and it was difficult to form a sufficiently dense conductive layer. Furthermore, no.
- the coating liquid for forming the conductive layer 15 has a viscosity of 123 mPa ⁇ s and a high viscosity exceeding 100 mPa ⁇ s, so the coating film is difficult to spread uniformly on the polyimide film, and the coating film is found to be faint. It was.
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Abstract
Description
本出願は、2015年9月30日出願の日本出願第2015-193141号に基づく優先権を主張し、上記日本出願に記載された全ての記載内容を援用するものである。
上記公報に記載のプリント配線板用基材は、ベースフィルムに銅薄膜層を直接積層できる点において高密度プリント配線の要求に沿うといえる。しかしながら、このプリント配線板用基材は、銅薄膜層をスパッタリング法によって形成しているため、真空設備を必要とし、設備の建設、維持、運転等、設備コストが高くなるという不都合を有する。また、このプリント配線板用基材は、真空設備を用いた真空条件下で形成する必要があるため、基材のサイズを大きくすることに限界がある。
本発明の導電層形成用塗布液及び導電層の製造方法は、一定の厚みを有する導電層を比較的低コストで容易かつ確実に形成することができる。
最初に本発明の実施態様を列記して説明する。
<導電層形成用塗布液>
当該導電層形成用塗布液は、例えばプリント配線板基材形成用である。具体的には、当該導電層形成用塗布液は、プリント配線板を構成するベースフィルムの表面に塗布された上、乾燥及び加熱処理されることで、このベースフィルムの表面に積層され、金属微粒子が焼結された導電層(金属微粒子焼結層)を形成する。
当該導電層形成用塗布液の製造方法は、金属微粒子を製造する金属微粒子製造工程と、上記金属微粒子製造工程で製造した金属微粒子を洗浄する洗浄工程と、上記洗浄工程で洗浄した金属微粒子を分散媒中に分散させる分散工程とを備える。
上記金属微粒子製造工程は、高温処理法、液相還元法、気相法等によって行うことができる。以下では、上記金属微粒子製造工程の好ましい態様として、液相還元法による方法について説明する。
上記洗浄工程では、上記金属微粒子製造工程で析出させた金属微粒子を水洗浄する。具体的には、上記洗浄工程では、遠心分離により上記金属微粒子と液体とを分離した上、分離後の上記金属微粒子に水を添加して撹拌することで金属微粒子を洗浄する。水洗浄を行う回数としては、特に限定されるものではないが、例えば1回以上3回以下とすることができ、2回がより好ましい。当該導電層形成用塗布液の製造方法は、水洗浄回数を増加させることで当該導電層形成用塗布液のpH、電気伝導率及び分散剤の含有量を低下させることができる。この点に関し、当該導電層形成用塗布液は、水洗浄回数を上記範囲内とすることによって、当該導電層形成用塗布液のpH、電気伝導率及び分散剤の含有量を上記範囲に調整し易い。
上記分散工程では、上記洗浄工程後の金属微粒子を分散媒中に分散させる。上記分散工程は、例えば上記洗浄工程後に乾燥して得られた粉末状の金属微粒子を分散媒である水に含有させることで行うことができる。なお、上記洗浄工程後の金属微粒子は、分散剤によって取り囲まれた状態で存在しているため、上記分散工程では必ずしも分散媒中に分散剤を添加する必要はないが、上記分散工程では必要に応じて分散媒中に上記分散剤を添加してもよい。
次に、図1~図4を参照しつつ、当該導電層形成用塗布液を用いた導電層の製造方法を説明する。なお、以下では、当該導電層形成用塗布液を用いてプリント配線板用基材の導電層を製造する場合について説明する。
上記塗布工程では、図1に示すように、ベースフィルム1の一方の面に当該導電層形成用塗布液を塗布する。
上記加熱工程では、図2に示すように、塗膜3を焼成することで金属微粒子焼結層4を形成する。上記加熱工程では、塗膜3の焼成によって金属微粒子2同士を焼結すると共に、金属微粒子2の焼結体をベースフィルム1の一方の面に固着させる。なお、塗膜3に含まれる分散剤等やその他の有機物はこの焼成によって揮発又は分解される。
上記金属めっき層形成工程は、第1金属めっき層形成工程と、第2金属めっき層形成工程とを有する。
上記第1金属めっき層形成工程では、図3に示すように、金属微粒子焼結層4の外面に第1金属めっき層5を形成する。具体的には、上記第1金属めっき層形成工程では、金属微粒子焼結層4の空隙をめっき金属で充填すると共に、このめっき金属を金属微粒子焼結層4の一方の面に積層する。当該導電層の製造方法は、上記第1金属めっき層形成工程を有することによって、導電層とベースフィルム1との密着力を高めることができる。
上記第2金属めっき層形成工程では、図4に示すように、第1金属めっき層5の外面に第2金属めっき層6を形成する。当該導電層の製造方法は、上記第2金属めっき層形成工程を有することによって、導電層の厚みを容易かつ確実に調整することができる。
今回開示された実施の形態は全ての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は、上記実施形態の構成に限定されるものではなく、請求の範囲によって示され、請求の範囲と均等の意味及び範囲内での全ての変更が含まれることが意図される。
[No.1]
還元剤としての三塩化チタン溶液80g(0.1M)、pH調整剤としての炭酸ナトリウム50g、錯化剤としてのクエン酸ナトリウム90g、及び分散剤としてのポリエチレンイミン1gをビーカー内で純水1Lに溶解させ、この水溶液を35℃に保温した。また、この水溶液に同温度(35℃)で保温した硝酸銅三水和物10g(0.04M)の水溶液を添加し撹拌させることで銅微粒子を析出させた。さらに、遠心分離により分離した銅微粒子に対し、200mLの純水による洗浄工程を2回繰り返した上、この銅微粒子を乾燥させることで粉末状の銅微粒子を得た。続いて、この粉末状の銅微粒子に純水を加えて含有量調整を行うことでNo.1の導電層形成用塗布液を得た。このNo.1の導電層形成用塗布液300μLを親水化処理を行ったポリイミドフィルム(10cm角)上にバーコート法により塗布した。
洗浄工程1回当たりの水量を表1の通りとした以外はNo.1と同様にしてNo.2~No.5の導電層形成用塗布液を得た。また、No.2~No.5の導電層形成用塗布液を、No.1と同様にして、親水化処理を行ったポリイミドフィルム(10cm角)上にそれぞれバーコート法により塗布した。
導電層形成用塗布液における銅微粒子の含有量を表1の通りとした以外はNo.1と同様にしてNo.6~No.9の導電層形成用塗布液を得た。また、No.6~No.9の導電層形成用塗布液を、No.1と同様にして、親水化処理を行ったポリイミドフィルム(10cm角)上にそれぞれバーコート法により塗布した。
分散剤としてポリエチレンイミン-エチレンオキサイド付加物1gを用いた以外はNo.1と同様にしてNo.10の導電層形成用塗布液を得た。また、No.10の導電層形成用塗布液を、No.1と同様にして、親水化処理を行ったポリイミドフィルム(10cm角)上にバーコート法により塗布した。
分散剤としてポリエチレンイミン-エチレンオキサイド付加物1gを用いると共に洗浄工程1回当たりの水量を表1の通りとした以外はNo.1と同様にしてNo.11の導電層形成用塗布液を得た。また、No.11の導電層形成用塗布液を、No.1と同様にして、親水化処理を行ったポリイミドフィルム(10cm角)上にバーコート法により塗布した。
[No.12,No.13]
洗浄工程1回当たりの水量を表1の通りとした以外はNo.1と同様にしてNo.12及びNo.13の導電層形成用塗布液を得た。また、No.12及びNo.13の導電層形成用塗布液をNo.1と同様にして、親水化処理を行ったポリイミドフィルム(10cm角)上にそれぞれバーコート法により塗布した。
導電層形成用塗布液における銅微粒子の含有量を表1の通りとした以外はNo.1と同様にしてNo.14及びNo.15の導電層形成用塗布液を得た。また、No.14及びNo.15の導電層形成用塗布液をNo.1と同様にして、親水化処理を行ったポリイミドフィルム(10cm角)上にそれぞれバーコート法により塗布した。
分散剤としてポリエチレンイミン-エチレンオキサイド付加物1gを用い、洗浄工程における1回当たりの水量をNo.11と同様とし、粉末状の銅微粒子に純水を加えた後に塩酸0.2gを添加した以外はNo.1と同様にしてNo.16の導電層形成用塗布液を得た。また、No.16の導電層形成用塗布液をNo.1と同様にして、親水化処理を行ったポリイミドフィルム(10cm角)上にバーコート法により塗布した。
導電層形成用塗布液の電気伝導率[μS/cm]をJIS-K0130:2008に準拠して、株式会社堀場製作所製のコンパクト電気伝導率計「LAQUAtwin B-771」を用いて測定した。この測定結果を表1に示す。
導電層形成用塗布液の粘度[mPa・s]を、JIS-Z8803:2011に準拠して、東機産業株式会社製のコーンプレート型粘度計「TV22L」を用いて25℃、20rpmの条件で測定した。この測定結果を表1に示す。
株式会社日立ハイテクサイエンス製の蛍光X線膜厚計「FT9500」を用いて塗膜厚みを測定した。この塗膜厚みは、銅微粒子の存在部分の厚みを面積10cm2当たり1箇所の割合で10箇所測定し、この10箇所の厚みを平均することで求めた。この測定結果を表1に示す。
株式会社キーエンス製のレーザ顕微鏡「VK-X150」を用い、対物レンズ100倍、デジタルズーム1倍で、導電層形成用塗布液を塗布して形成される塗膜表面を観察し、高さカットレベル90として30μm×30μmの範囲を分析し、ISO25178に準拠して表面粗さSa[μm]を測定した。この測定結果を表1に示す。
導電層形成用塗布液を塗布して形成される塗膜を目視にて観察し、白抜けの有無を確認した。白抜けがある場合はかすれ有り、白抜けがない場合はかすれ無しとして評価した。この評価結果を表1に示す。
金属微粒子(銅微粒子)の表面を100k~300k倍の倍率で走査型電子顕微鏡(SEM)にて観察し、任意に抽出した金属微粒子100個を測長して粒子径の小さい順に体積を積算した際の累積体積が50%となる粒子径[nm]を測定した。この測定結果を表1に示す。
マイクロトラック・ベル株式会社製の粒子径分布測定装置「Nanotrac Wave-EX150」を用い、体積累積分布から算出される金属微粒子(銅微粒子)の平均粒子径D50[nm]を測定した。この測定結果を表1に示す。
表1に示すように、No.1~No.11の導電層形成用塗布液は、pHが4以上8以下、電気伝導率が100μS/cm以上800μS/cm以下、及び金属微粒子(銅微粒子)の含有量が20質量%以上80質量%以下に調整されることで、厚みが0.1μm以上で比較的厚く、かつ表面粗さSaが0.12μm以下の比較的小さい塗膜を形成できることが分かった。特に、No.1,No.10及びNo.11の導電層形成用塗布液は、平均粒子径D50SEM/平均粒子径D50の比が1.1以下と小さいことから、個々の金属微粒子(銅微粒子)の形状が略球状に揃っており、その結果塗膜中でこれらの金属微粒子が高密度で均一分散され易いので、塗膜の表面粗さSaを0.063μm以下と小さくすることができることが分かった。これに対し、No.12~No.16の導電層形成用塗布液は、pH、電気伝導率及び金属微粒子(銅微粒子)の含有量が上記の範囲に調整されていないため、比較的厚みが厚くかつ表面粗さSaが比較的小さい塗膜を形成することが困難であることが分かった。特に、No.12,No.13,No.15及びNo.16の導電層形成用塗布液は、平均粒子径D50SEMが比較的大きく、かつ平均粒子径D50SEM/平均粒子径D50の比が2.1以上と大きいことから、塗膜の表面粗さSaを十分に小さく抑えることができず、十分に緻密な導電層を形成し難いことが分かった。さらに、No.15の導電層形成用塗布液は、粘度が123mPa・sと、100mPa・sを超える高い粘度のため、塗膜がポリイミドフィルム上に均一に広がり難く、塗膜にかすれが生じていることが分かった。
2 金属微粒子
3 塗膜
4 金属微粒子焼結層
5 第1金属めっき層
6 第2金属めっき層
Claims (8)
- 金属微粒子、分散媒及び分散剤を含有する導電層形成用塗布液であって、
pHが4以上8以下、電気伝導率が100μS/cm以上800μS/cm以下、上記金属微粒子の含有量が20質量%以上80質量%以下である導電層形成用塗布液。 - 上記分散剤が、高分子化合物である請求項1に記載の導電層形成用塗布液。
- 上記高分子化合物がイミノ基を有する請求項2に記載の導電層形成用塗布液。
- 上記高分子化合物が、ポリエチレンイミン又はポリエチレンイミン-エチレンオキサイド付加物である請求項3に記載の導電層形成用塗布液。
- 上記金属微粒子のレーザ回折法で測定した体積累積分布から算出される平均粒子径D50が1nm以上500nm以下である請求項1から請求項4のいずれか1項に記載の導電層形成用塗布液。
- 25℃における粘度が100mPa・s以下である請求項1から請求項5のいずれか1項に記載の導電層形成用塗布液。
- 上記金属微粒子の主成分が銅又は銅合金である請求項1から請求項6のいずれか1項に記載の導電層形成用塗布液。
- 金属微粒子、分散媒及び分散剤を含有する導電層形成用塗布液を用いた導電層の製造方法であって、
上記導電層形成用塗布液を塗布する塗布工程と、
上記塗布後の導電層形成用塗布液を加熱する加熱工程と
を備え、
上記塗布時の上記導電層形成用塗布液のpHが4以上8以下、電気伝導率が100μS/cm以上800μS/cm以下、上記金属微粒子の含有量が20質量%以上80質量%以下である導電層の製造方法。
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JP2019140280A (ja) * | 2018-02-13 | 2019-08-22 | 住友電気工業株式会社 | フレキシブルプリント配線板用基板製造方法及びフレキシブルプリント配線板用基板 |
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JP7158819B1 (ja) | 2022-06-22 | 2022-10-24 | 石原ケミカル株式会社 | 銅インク、導電膜形成方法、及びrfタグ |
WO2024038701A1 (ja) * | 2022-08-17 | 2024-02-22 | 株式会社ダイセル | 積層体および積層体の製造方法 |
JP7490528B2 (ja) | 2020-01-10 | 2024-05-27 | 東邦チタニウム株式会社 | 銅粉体 |
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JP2021170617A (ja) * | 2020-04-17 | 2021-10-28 | イビデン株式会社 | プリント配線板 |
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