WO2016121749A1 - 金属粉末、インク、焼結体及びプリント配線板用基材並びに金属粉末の製造方法 - Google Patents
金属粉末、インク、焼結体及びプリント配線板用基材並びに金属粉末の製造方法 Download PDFInfo
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- WO2016121749A1 WO2016121749A1 PCT/JP2016/052159 JP2016052159W WO2016121749A1 WO 2016121749 A1 WO2016121749 A1 WO 2016121749A1 JP 2016052159 W JP2016052159 W JP 2016052159W WO 2016121749 A1 WO2016121749 A1 WO 2016121749A1
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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
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
- B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0425—Copper-based alloys
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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
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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
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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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
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/10—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2304/00—Physical aspects of the powder
- B22F2304/05—Submicron size particles
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
Definitions
- the present invention relates to a metal powder, an ink, a sintered body, a substrate for a printed wiring board, and a method for producing the metal powder.
- a technique for forming a conductive film made of a metal sintered body on a substrate surface such as a resin film by applying and baking an ink containing a metal powder is known. Yes.
- the crystallite diameter of the metal powder dispersed in the ink is set to a certain value or more, and the porosity of the sintered body layer is set to 1% or less.
- a metal sintered body with a reduced porosity is not sufficiently flexible because stress concentrates on a portion adjacent to few voids and is easily broken.
- a flexible printed wiring board is manufactured by forming a conductive pattern by applying and baking an ink in which metal powder is dispersed on a polyimide film, the flexibility of the metal sintered body is insufficient. There is a risk that the conductive pattern is disconnected due to the bending of the wiring board.
- the present invention has been made based on the circumstances as described above, metal powder and ink capable of forming a sintered body excellent in flexibility, a sintered body excellent in flexibility, and a substrate for a printed wiring board, It is another object of the present invention to provide a method for producing a metal powder capable of forming a sintered body having excellent flexibility.
- Metal powder according to one embodiment of the present invention has been made to solve the above problems, an average particle diameter D 50BET calculated by BET method 1nm or 200nm or less, the average crystallite diameter D Cryst by X-ray analysis 20nm or less
- the ratio of the average crystallite diameter D Cryst to the average particle diameter D 50 BET is less than 0.4.
- the method for producing a metal powder according to another aspect of the present invention made to solve the above-described problem is that the average particle diameter D50BET calculated by the BET method is 1 nm to 200 nm, and the average crystallite by X-ray analysis
- a method for producing a metal powder having a diameter D Cryst of 20 nm or less and a ratio of the average crystallite diameter D Cryst to the average particle diameter D 50 BET (D Cryst / D 50 BET ) of less than 0.4 in an aqueous solution A step of reducing metal ions with a reducing agent is provided, and this reduction step is performed at 100 ° C. or lower.
- the metal powder according to one embodiment of the present invention and the metal powder produced by the method for producing a metal powder according to another embodiment of the present invention can form a sintered body having excellent flexibility.
- FIG. 1 is an electron micrograph of a metal powder according to an embodiment of the present invention.
- FIG. 2 is an electron micrograph of a cross section of the printed wiring board substrate according to one embodiment of the present invention.
- FIG. 3 is a flowchart showing a manufacturing procedure of the printed wiring board substrate according to the embodiment of the present invention.
- the metal powder according to one embodiment of the present invention has an average particle diameter D 50 BET calculated by the BET method of 1 nm to 200 nm, an average crystallite diameter D Cryst by X-ray analysis of 20 nm or less, and the average particle diameter D 50 BET the average crystallite size D Cryst the ratio of the (D Cryst / D 50BET) is less than 0.4.
- the metal powder can form a dense sintered body by sintering.
- the metal powder by the average crystallite diameter D Cryst is more than the above-described upper limit, and the ratio of the average crystallite diameter D Cryst to the average particle diameter D 50BET (D Cryst / D 50BET ) is less than the upper limit Even when a sintered body is formed, the crystallite is small. Accordingly, when stress is applied to the sintered body of the metal powder, the stress is relieved by forming fine cracks between the crystallites, and thus the sintered body is excellent in flexibility.
- the main component is preferably copper or copper alloy.
- the sintered compact which is excellent in electroconductivity can be formed because a main component is copper or a copper alloy.
- the metal powder may contain a metal different from the main component.
- the metal powder contains a metal different from the main component, the growth of crystallites of the main metal serving as the main component during the formation and firing of the metal powder is suppressed.
- It may be formed by a liquid phase reduction method in which metal ions are reduced with a reducing agent in an aqueous solution.
- a liquid phase reduction method in which metal ions are reduced with a reducing agent in an aqueous solution, it can have a fine and nearly spherical shape, and an average crystallite diameter D Cryst with respect to an average particle diameter D 50 BET . The ratio can be easily reduced.
- trivalent titanium ions may be used as a reducing agent.
- the particle diameter and the particle shape can be made uniform.
- the ink according to an aspect of the present invention includes the metal powder and a dispersion medium.
- the ink includes a metal powder capable of forming a sintered body having excellent flexibility as a dispersoid
- a sintered body having excellent flexibility can be formed by coating and baking.
- the sintered body according to one embodiment of the present invention is formed by applying and firing the ink, and has an average crystallite diameter DCryst of 25 nm or less.
- the sintered body is excellent in flexibility because the above-described ink is used and the average crystallite diameter DCryst is less than or equal to the above upper limit, so that fine cracks can be formed and stress can be relieved.
- a printed wiring board base material includes an insulating base film and the film-like sintered body laminated on at least one surface side of the base film.
- the printed wiring board base material includes the film-like sintered body laminated on at least one surface side of the base film, the printed wiring board is excellent in flexibility because the sintered body is not easily broken by bending. Can be manufactured.
- the average particle diameter D 50 BET calculated by the BET method is 1 nm or more and 200 nm or less
- the average crystallite diameter D Cryst by X-ray analysis is 20 nm or less
- a diameter D ratio of the average crystallite diameter D Cryst for 50BET (D Cryst / D 50BET) are provided methods for producing the metal powder is less than 0.4, comprising the step of reducing the metal ions with a reducing agent in an aqueous solution, This reduction step is performed at 100 ° C. or lower.
- the method for producing the metal powder includes a step of reducing metal ions with a reducing agent in an aqueous solution, and since this reduction step is performed at 100 ° C. or less, the growth of crystallites can be suppressed and the crystallite diameter can be reduced. Easy. Thereby, the metal powder which can form the sintered compact excellent in flexibility can be manufactured easily.
- average particle diameter D 50 BET means that the BET specific surface area measured using nitrogen gas is A [m 2 / g], the density of the bulk metal is ⁇ [g / cm 3 ], and the following formula: This is the value [nm] calculated by (1).
- D 50 BET [nm] 6 ⁇ 10 3 / (A [m 2 / g] ⁇ ⁇ [g / cm 3 ]) (1)
- the “average crystallite diameter D Cryst ” is a value measured according to JIS-H7805 (2005).
- the “main component” means a component having the largest mass content, preferably a component containing 90% by mass or more.
- the metal powder according to one embodiment of the present invention illustrated in FIG. 1 is used for forming a conductive sintered body by applying and baking ink formed by dispersing in a dispersion medium.
- the lower limit of the average particle diameter D 50 BET calculated by the BET method of the metal powder is 1 nm, and preferably 20 nm.
- the upper limit of the average particle diameter D50BET of the metal powder is 200 nm, preferably 150 nm, and more preferably 100 nm.
- the average particle diameter D50BET of the metal powder is less than the lower limit, the dispersibility and stability of the metal powder in the ink may be lowered.
- the average particle diameter D50BET of the metal powder exceeds the upper limit, the metal powder may be easily precipitated, or the density of the metal powder may not be uniform when the ink is applied. .
- the lower limit of the average crystallite diameter DCryst by X-ray analysis of the metal powder is preferably 0.1 nm, and more preferably 1 nm.
- the upper limit of the average crystallite diameter DCryst of the metal powder is 20 nm, preferably 18 nm, and more preferably 10 nm.
- the metal powder may not be easily manufactured.
- the average crystallite diameter DCryst of the metal powder exceeds the upper limit, there is a possibility that the flexibility of the sintered body formed by firing the metal powder may be insufficient.
- the lower limit of the ratio (D Cryst / D 50 BET ) of the average crystallite diameter D Cryst to the average particle diameter D 50 BET of the metal powder is preferably 0.05, and more preferably 0.1.
- the upper limit of the ratio of the average crystallite diameter D Cryst to the average particle diameter D 50 BET of the metal powder is less than 0.4, and more preferably less than 0.3. When the ratio of the average crystallite diameter D Cryst to the average particle diameter D 50 BET of the metal powder is less than the lower limit, the metal powder may not be easily manufactured.
- the ratio of the average crystallite diameter D Cryst to the average particle diameter D 50 BET of the metal powder is not less than the above upper limit, the flexibility and fatigue strength of the sintered body formed by firing the metal powder are poor . May be sufficient.
- the average particle diameter D50BET is different from the particle diameter measured by many other methods such as a volume equivalent diameter, and the measured value tends to be smaller as the particle diameter of the primary particles is smaller.
- the primary particles are large, DCryst is likely to be large.
- the sintered body has appropriate voids (1% or more), fine cracks that do not cause the entire destruction can be formed, and it is considered that the flexibility and fatigue strength of the sintered body are improved.
- the metal powder by the ratio of the average crystallite diameter D Cryst to the average particle diameter D50BET (D Cryst / D 50BET) is small, a lot smaller average crystallite size D Cryst crystal grains in the primary particles Therefore, it is presumed that a sintered body resistant to bending can be formed.
- metal powder copper or a copper alloy that is relatively inexpensive and excellent in conductivity is preferable.
- the metal powder preferably contains a small amount of a secondary metal (a different metal) in addition to the main metal as a main component.
- a secondary metal a different metal
- the secondary metal for example, when the metal powder is formed by a liquid phase reduction method described later, a metal that is deposited simultaneously with the main metal is preferable.
- the secondary metal when the main metal is copper include titanium, silver, nickel, and zinc.
- the secondary metal is titanium, since the secondary metal is a metal species contained in the reducing agent, it is easy to incorporate the secondary metal into the particle during the period from when the main metal forms a nucleus until the particle grows. . Thereby, since it is relatively easy to contain the secondary metal in the metal powder, the growth of the main metal crystallites can be more reliably suppressed during the sintering of the metal powder.
- the lower limit of the content of the secondary metal relative to the main metal in the metal powder is preferably 0.02% by mass, and more preferably 0.05% by mass.
- the upper limit of the content of the secondary metal relative to the main metal in the metal powder is preferably 5% by mass, and more preferably 1% by mass.
- the metal powder can be produced by a high temperature treatment method, a liquid phase reduction method, a gas phase method, or the like.
- the metal powder by the liquid phase reduction method which deposits metal powder by reduce
- the metal powder can have a fine and nearly spherical shape, and the ratio of the average crystallite diameter D Cryst to the average particle diameter D 50 BET can be relatively easily reduced.
- a solution in which a water-soluble metal compound that is a source of metal ions forming a metal powder in water and a dispersant are dissolved for example, a method comprising a reduction step in which a metal ion is reduced by a reducing agent for a certain period of time can be used.
- copper copper nitrate trihydrate (II) (Cu (NO 3 ) 2 .3H 2 O), copper sulfate (II) pentahydrate as the water-soluble metal compound that is the source of the metal ions.
- Japanese CuSO 4 .5H 2 O
- silver silver nitrate (I) (AgNO 3 ), silver methanesulfonate (CH 3 SO 3 Ag), etc.
- tetrachloroauric (III) acid tetrahydrate HuCl 4 .4H 2 O
- nickel nickel chloride (II) hexahydrate (NiCl 2 ⁇ 6H 2 O)
- nickel nitrate (II) hexahydrate Ni (NO 3 ) 2 ⁇ 6H 2 O
- water-soluble compounds such as chlorides, nitrate compounds, and sulfate compounds can be used.
- reducing agent in the case of producing metal powder by the liquid phase reduction method, 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
- polyhydric alcohols such as glycol and glycerin.
- a method of reducing metal ions by redox action when trivalent titanium ions are oxidized to tetravalent and depositing metal powder that is, a liquid phase reduction method using trivalent titanium ions as a reducing agent (titanium Also called redox method).
- the metal powder obtained by the titanium redox method has a small and uniform particle size and a shape close to a sphere. That is, in the titanium redox method, the average particle diameter D 50BET of the obtained metal powder is close to the diameter measured by a method such as a volume equivalent diameter, whereby the ratio of the average crystallite diameter D Cryst to the average particle diameter D 50BET is set. It is relatively easy to reduce the size.
- the lower limit of the temperature in the reduction step is preferably 0 ° C, more preferably 15 ° C.
- the upper limit of the temperature in the reduction step is 100 ° C, preferably 60 ° C, and more preferably 50 ° C. If the temperature in the reduction step is less than the lower limit, the reduction reaction efficiency may be insufficient. On the other hand, when the temperature in the reduction step exceeds the above upper limit, crystallites may grow and the flexibility of the fired body of the metal powder may be insufficient.
- the pH of the reaction system in the reduction step is preferably 7 or more and 13 or less in order to obtain a metal powder with a fine 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 pH adjuster common acids or alkalis such as hydrochloric acid, sulfuric acid, sodium hydroxide, sodium carbonate and the like are used, but sodium carbonate which functions as a buffer capable of fine pH adjustment is preferable.
- the metal powder formed by the liquid phase reduction method is preferably used after being separated from the aqueous solution and then washed.
- Examples of the solid-liquid separation method for separating the metal powder formed from the aqueous solution include a filtration method and a centrifugation method, among which the centrifugation method is preferable. Centrifugation can be efficiently washed with a small amount of water because the dehydration efficiency of solids is higher than that of filtration using an ultrafiltration membrane.
- the metal powder after centrifugation may be washed by further centrifuging the separated metal powder with pure water added and stirred, and this washing may be repeated a plurality of times.
- the lower limit of the amount of pure water used in this single washing is preferably 1% by mass and more preferably 3% by mass with respect to the amount of pure water in the aqueous solution for liquid phase reduction.
- the upper limit of the amount of pure water used in one washing is preferably 20% by mass and more preferably 15% by mass with respect to the amount of pure water in the aqueous solution for liquid phase reduction.
- the amount of pure water used in one washing is less than the lower limit, it may be necessary to increase the number of washings due to insufficient removal of impurities.
- the amount of pure water used in one washing exceeds the above upper limit, when pure water is added, metal particles may aggregate due to a solvent shock and the dispersibility of the metal powder may be impaired.
- the number of washings is preferably 1 to 3 times.
- cleaning is less than the said minimum, there exists a possibility that the dispersibility of the said metal powder may become inadequate by the residue of an impurity.
- the number of washings exceeds the above upper limit, the metal particles tend to aggregate due to excessive removal of the dispersant originating from the liquid phase reducing aqueous solution and adhering to the periphery of the metal particles. The dispersibility of the resin may be impaired.
- the metal powder can form a dense sintered body by sintering.
- the metal powder by the average crystallite diameter D Cryst is more than the above-described upper limit, and the ratio of the average crystallite diameter D Cryst to the average particle diameter D 50BET (D Cryst / D 50BET ) is less than the upper limit Even when a sintered body is formed, the crystallite is small. Thereby, when stress is applied to the sintered body of the metal powder, the stress is relieved by forming fine cracks between the crystallites, so that the sintered body is excellent in flexibility.
- the ink includes the metal powder and the dispersion medium. That is, the ink includes the above-described metal powder as a dispersoid.
- the ink may contain an additive such as a dispersant.
- Dispersion medium for the ink a mixture of one or more of water and a highly polar solvent is used, and among them, a mixture of water and a highly polar solvent compatible with water is preferably used.
- a dispersion medium for the ink one prepared by adjusting a reducing agent aqueous solution after the metal powder is deposited can be used. That is, a dispersion medium containing a certain amount of metal powder in advance by adding a highly polar solvent to a reducing agent aqueous solution containing metal powder in advance, which has been subjected to treatment such as ultrafiltration, centrifugation, and electrodialysis to remove impurities. Is obtained.
- a volatile organic solvent that can evaporate in a short time during firing is preferable.
- the high polarity solvent volatilizes in a short time during firing, and the viscosity of the ink applied to the surface of the substrate is rapidly increased without causing movement of the metal powder.
- any of various organic solvents having volatility at room temperature 5 ° C. or more and 35 ° C. or less
- a volatile organic solvent having a boiling point at normal pressure of, for example, 60 ° C. or higher and 140 ° C. or lower is preferable.
- an aliphatic having 1 to 5 carbon atoms having high volatility and excellent compatibility with water. Saturated alcohol is preferred.
- Examples of the aliphatic saturated alcohol having 1 to 5 carbon atoms include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and n-amyl. Alcohol, isoamyl alcohol, etc. are mentioned, What mixed these 1 type (s) or 2 or more types is used.
- the lower limit of the content of the volatile organic solvent in the total dispersion medium is preferably 30% by mass, and more preferably 40% by mass.
- the upper limit of the content of the volatile organic solvent in the total dispersion medium is preferably 80% by mass, and more preferably 70% by mass. If the content of the volatile organic solvent in the total dispersion medium is less than the above lower limit, the viscosity of the ink may not be increased in a short time during firing. In addition, when the content of the volatile organic solvent in the total dispersion medium exceeds the above upper limit, the content of water is relatively reduced, so that the ink on the surface of various substrates such as glass, ceramic, plastic, etc. There is a risk that wettability will be insufficient.
- examples of the highly polar solvent other than the volatile organic solvent include ethylene glycol, propylene glycol, glycerin and the like, and a mixture of one or more of these is used. These highly polar solvents function as a binder that prevents the metal powder from moving during firing.
- the lower limit of the content of the total dispersion medium in the ink is preferably 100 parts by mass and more preferably 400 parts by mass per 100 parts by mass of the metal powder.
- the upper limit of the content of the total dispersion medium in the ink is preferably 3000 parts by mass and more preferably 1000 parts by mass per 100 parts by mass of the metal powder.
- the ink includes the metal powder described above as a dispersoid, a sintered body having excellent flexibility can be formed by coating and baking.
- the sintered body is formed by applying and firing the ink.
- the lower limit of the average crystallite diameter DCryst of the sintered body is preferably 0.1 nm, and more preferably 1 nm.
- the upper limit of the average crystallite diameter DCryst of the sintered body is 25 nm, and preferably 20 nm.
- the sintered body is fired after the ink described above is applied to the surface of the substrate, dried.
- the remaining metal powder adheres to each other in the pre-sintering state or before the sintering process by volatilizing and decomposing and removing the dispersant and other organic substances contained in the coated ink. As a result, it becomes a state of solid bonding.
- the lower limit of the firing temperature is preferably 150 ° C., more preferably 200 ° C.
- an upper limit of baking temperature 500 degreeC is preferable and 400 degreeC is more preferable.
- the firing temperature is less than the above lower limit, the metal powders may be insufficiently joined.
- the firing temperature exceeds the upper limit, crystallites may grow and the flexibility of the sintered body may be insufficient, or the substrate may be deformed when the substrate is an organic resin such as polyimide. There is.
- the firing step is preferably performed in an atmosphere containing a certain amount of oxygen.
- a minimum of the oxygen concentration of the atmosphere at the time of baking 1 volume ppm is preferable and 10 volume ppm is more preferable.
- an upper limit of the said oxygen concentration 10,000 volume ppm is preferable and 1,000 volume ppm is more preferable.
- the oxygen concentration is less than the lower limit, the amount of metal oxide generated in the vicinity of the interface between the base material and the sintered body is reduced, and the adhesion between the base material and the sintered body due to the metal oxide is insufficient. There is a risk.
- the oxygen concentration exceeds the upper limit the metal powder is excessively oxidized, and the conductivity and fatigue strength of the sintered body may be insufficient.
- the sintered body is excellent in flexibility because a fine crack can be formed and stress can be relieved.
- the printed wiring board substrate includes an insulating base film and the film-like sintered body directly laminated on at least one surface of the base film.
- the printed wiring board substrate is used for producing a printed wiring board by forming a conductive pattern by a subtractive method or a semi-additive method using the sintered body.
- 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), It is possible to use a rigid material such as a glass substrate, or a rigid flexible material in which a hard material and a soft material are combined.
- polyimide is particularly preferable because of its high bonding strength with metal oxides.
- the thickness of the base film is not particularly limited and is set according to the specifications of the printed wiring board using the substrate for the printed wiring board, for example, as the lower limit of the average thickness of the base film, 5 ⁇ m is preferable and 12 ⁇ m is more preferable.
- the upper limit of the average thickness of the base film is preferably 2 mm, and more preferably 1.6 mm. When the average thickness of the base film is less than the lower limit, the strength of the base film may be insufficient. Conversely, if the average thickness of the base film exceeds the upper limit, it may be difficult to make the printed wiring board thinner.
- the base film is preferably subjected to a hydrophilic treatment on the surface on which ink is applied.
- a hydrophilic treatment for example, plasma treatment for irradiating plasma to make the surface hydrophilic, alkali treatment for making the surface hydrophilic with an alkaline solution, or the like can be employed.
- the sintered body is laminated on one surface of the base film by applying and baking ink containing the metal powder according to the embodiment of the present invention.
- the printed wiring board substrate since a sintered body is formed by applying and sintering ink, one surface of the base film can be easily covered with a flexible and conductive film.
- the lower limit of the average thickness of the sintered body is preferably 0.05 ⁇ m, more preferably 0.1 ⁇ m.
- the upper limit of the average thickness of the sintered body is preferably 2 ⁇ m, and more preferably 1.5 ⁇ m.
- the sintered body may be electroplated or electrolessly plated.
- the sintered body can be densified by filling the gaps between the sintered bodies, and the conductor layer can be thickened by further laminating metal on the surface of the sintered body.
- the printed wiring board base material uses the metal powder obtained in the step of producing the metal powder (step S1: metal powder production step) and the metal powder production step.
- the manufacturing process step S2: ink manufacturing process
- step S3 coating process
- step S4 baking process
- the average particle diameter D 50BET and the average crystallite are preferably obtained by a liquid phase reduction method, more preferably by a titanium redox method using trivalent titanium ions as a reducing agent.
- a metal powder having a ratio of the average crystallite diameter D Cryst to the diameter D Cryst and the average particle diameter D 50BET is manufactured.
- the ink is manufactured by dispersing the metal powder in the dispersion medium.
- step S3 the ink is applied to at least one surface of the base film.
- ink coating method conventionally known coating methods such as a spin coating method, a spray coating method, a bar coating method, a die coating method, a slit coating method, a roll coating method, and a dip coating method can be used. Further, ink may be applied to only a part of one surface of the base film by screen printing, a dispenser or the like.
- step S4 the coating film of the ink formed on the base film is baked to volatilize and decompose the dispersion medium, the dispersant and other organic substances, and the remaining metal powders are joined together. To form a sintered body.
- the printed wiring board base material includes the film-like sintered body laminated on at least one surface side of the base film, the printed wiring board is excellent in flexibility because the sintered body is not easily broken by bending. Can be manufactured.
- a layer such as a primer layer may be interposed between the base film and the sintered body.
- liquid phase reduction method of the above embodiment copper ions are reduced to produce three types of metal powders, and the inks are adjusted using those obtained by separating these metal powders from the aqueous solution, and applied to the polyimide base material. The resulting substrate was fired to obtain three types of printed wiring board substrates.
- ⁇ Metal powder No. 1> In a beaker, dissolve 80 g of titanium trichloride solution as a reducing agent, 50 g of sodium carbonate as a pH adjusting agent, 90 g of sodium citrate as a complexing agent, and 1 g of polyvinylpyrrolidone (molecular weight 30000) as a dispersing agent in 1 L of pure water. The aqueous solution was kept at 35 ° C. An aqueous solution of 10 g of copper sulfate kept at the same temperature was added to this aqueous solution while stirring to precipitate copper particles.
- Dispersion treatment is performed for 10 minutes by adding 100 mL of pure water to copper particles separated by centrifugation at 10000 rpm and adding ultrasonic vibration while stirring with a 400 rpm stirrer. It was. This process was repeated twice to obtain a metal powder No. 1 containing copper as a main component. 1 was obtained.
- Metal powder No. 2 The above metal powder No. 1 is that the copper particles are precipitated under the same conditions except that the temperature of the aqueous solution is 60 ° C. An aqueous dispersion of 2 was obtained.
- Metal powder No. 3 The above metal powder No. 1 is that the reducing agent is ethylene glycol, and the copper particles are deposited under the same conditions except that the temperature of the aqueous solution is 200 ° C. An aqueous dispersion of 3 was obtained.
- metal powder No. 1 having an average particle diameter DSEM of 120 nm As a concrete measurement result, metal powder No. 1 having an average particle diameter DSEM of 120 nm, No. 2 has an average particle diameter DSEM of 50 nm. The average particle size DSEM of 3 was 50 nm.
- metal powder No. 1 has an average crystallite diameter D Cryst of 18 nm.
- 2 has an average crystallite diameter D Cryst of 8 nm.
- 3 had an average crystallite diameter DCryst of 15 nm.
- ⁇ Average particle size by BET method> These metal powder Nos.
- the specific surface area was measured by the BET method, and the average particle diameter D 50 BET was calculated from the measured specific surface area.
- “ASAP 2010” manufactured by Mamlomerics was used, and nitrogen gas was used as a measurement gas.
- metal powder No. No. 1 has an average particle diameter D 50 BET of 85 nm.
- No. 2 has an average particle diameter D 50 BET of 30 nm.
- 3 had an average particle diameter D50BET of 30 nm.
- Metal composition These metal powder Nos.
- the metal composition was measured by ICP analysis (high frequency inductively coupled plasma emission spectroscopy).
- ICP analysis “iCAP6300 DUO” manufactured by Thermo Fisher Scientific was used.
- metal powder No. 1 and metal powder no. No. 2 contained copper as a main metal and contained 0.1% by mass of titanium as a sub metal.
- metal powder no. 2 contained copper as a main metal, it did not contain any secondary metal other than copper (content is less than the detection limit).
- ⁇ Sintered body No. 1-3> The above metal powder No. 1 to 3 were used to prepare three types of ink having a copper concentration of 25% by mass using water as a solvent. These inks were applied to a polyimide base material serving as a base film with a bar coater and dried to form a copper particle coating film having an average thickness of 150 nm. By sintering the polyimide substrate on which the copper particle coating film was formed in a nitrogen atmosphere at a temperature of 300 ° C. for 2 hours, 1-3 were obtained.
- sintered body No. 1 has an average crystallite diameter D Cryst of 20 nm.
- 2 has an average crystallite diameter D Cryst of 15 nm.
- 3 had an average crystallite diameter DCryst of 30 nm.
- the sintered body No. By applying electroless copper plating to the surface of 1 to 3 sintered bodies, the total average thickness of the sintered body and the electroless plating layer is 1 ⁇ m, and further, by applying electrolytic copper plating, it is sintered on the base film
- Three types of substrates for printed wiring boards were obtained in which a metal layer having an average thickness of 10 ⁇ m composed of a body, an electroless plating layer and an electroplating layer was laminated. Further, using these wiring board base materials, a printed wiring board No. 1 was obtained by a subtractive method. 1-3 were formed. Specifically, after forming a resist film on each wiring board substrate and performing etching, the resist film is removed to pattern the metal layer, thereby forming a conductive pattern. 1-3 were obtained.
- Printed wiring board No. 1 to 3 are bonded to a polyimide base material provided with an adhesive layer to obtain a sample for evaluation of flexibility, and the conductive pattern is repeatedly bent by a bending tester under conditions of a radius of curvature of 2 mm, a speed of 1500 rpm and a sliding distance of 20 mm. The number of flexing until the fracture occurred was examined.
- a bending tester “SEK-31B4S” manufactured by Shin-Etsu Engineering Co., Ltd. was used.
- Specific test results include printed wiring board No. 1 and printed wiring board No. 1 For No. 2, the test was terminated at that point because it was not broken when it was bent 250 million times. On the other hand, printed wiring board No. The number of bends until the break of No. 3 was about 50 million.
- the above metal powder No. The average particle diameter D SEM by 1-3 SEM observation, the average crystallite diameter D Cryst, average particle diameter D 50BET by BET method, the ratio of the average crystallite diameter D Cryst to the average particle diameter D 50BET by metal composition, and the BET method (D Cryst / D 50 BET ), the sintered body No. 1 to 3 crystallite diameter D Cryst and printed circuit board No. Table 1 below shows the number of bendings until breakage in the bending tests 1 to 3.
- the printed wiring board No. 1 and no. No. 2 has good flexibility and fatigue strength, but printed circuit board No. 2 No. 3 was confirmed to be inferior in fatigue strength.
- Factors that suppress the average crystallite diameter C Cryst of the sintered body include the temperature during reduction of the metal powder, the ratio of the average crystallite diameter C Cryst to the average particle diameter D 50 BET by the BET method, the metal composition, and the metal
- the temperature during the reduction of the powder can be considered.
- the ratio of the average crystallite diameter D Cryst to the average particle diameter D 50BET by BET method of the metal powder below a certain upper limit value
- the average crystallite diameter D Cryst during sintering It is considered that the flexibility and fatigue strength of the sintered body can be improved. Further, it is considered that the crystallite growth is suppressed when the temperature during reduction is lower. In addition, it is considered that the growth of crystallites is suppressed when the metal powder contains a small amount of a sub-metal.
- the present invention is suitably used to form a flexible conductive pattern that is repeatedly bent and stretched.
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Abstract
Description
本発明の一態様に係る金属粉末は、BET法により算出される平均粒径D50BETが1nm以上200nm以下、X線解析による平均結晶子径DCrystが20nm以下であり、上記平均粒径D50BETに対する平均結晶子径DCrystの比(DCryst/D50BET)が0.4未満である。
D50BET[nm]=6×103/(A[m2/g]×ρ[g/cm3]) ・・・(1)
以下、本発明に係る金属粉末の一実施形態について詳説する。
続いて、当該金属粉末の製造方法について詳説する。当該金属粉末は、高温処理法、液相還元法、気相法等で製造することができる。
当該金属粉末は、平均粒径D50BETが上記範囲内であることによって、焼結により緻密な焼結体を形成可能である。また、当該金属粉末は、平均結晶子径DCrystが上記上限以下であり、かつ平均粒径D50BETに対する平均結晶子径DCrystの比(DCryst/D50BET)が上記上限未満であることによって、焼結体を形成した場合にも結晶子が小さい。これにより、当該金属粉末の焼結体に応力が加わった場合には、結晶子間で微細なクラックが形成されることで応力を緩和するので、焼結体が可撓性に優れる。
さらに、本発明の一実施形態に係るインクについて詳説する。当該インクは、当該金属粉末と、その分散媒とを備える。つまり、当該インクは、分散質として、上述の金属粉末を備える。また、当該インクは分散剤等の添加物を含んでもよい。
当該インクの分散媒としては、水、高極性溶媒の1種又は2種以上を混合したものが使用され、中でも水及び水と相溶する高極性溶媒を混合したものが好適に利用される。このようなインクの分散媒としては、金属粉末析出後の還元剤水溶液を調整したものを使用することができる。つまり、予め金属粉末を含む還元剤水溶液を限外ろ過、遠心分離、電気透析等の処理に供して不純物を除去したものに高極性溶媒を加えることで、予め一定量の金属粉末を含む分散媒が得られる。
当該インクは、分散質として上述の当該金属粉末を備えるので、塗工及び焼成により可撓性に優れる焼結体を形成することができる。
さらに、本発明の一実施形態に係る焼結体について詳説する。当該焼結体は、当該インクの塗工及び焼成により形成される。
当該焼結体は、上述のインクを基材の表面に塗工し、乾燥した後に焼成する。焼成工程において、塗工されたインクに含まれる分散剤やその他の有機物を揮発及び分解させて除去することにより、残る金属粉末が焼結状態又は焼結に至る前段階にあって相互に密着して固体接合したような状態となる。
当該焼結体は、平均結晶子径DCrystが上記上限以下であることによって、微細なクラックを形成して応力を緩和することができるので、可撓性に優れる。
さらに、図2に例示する本発明の一実施形態に係るプリント配線板用基材について詳説する。当該プリント配線板用基材は、絶縁性を有するベースフィルムと、このベースフィルムの少なくとも一方の面に直接積層される上記フィルム状の焼結体とを備える。
上記ベースフィルムの材料としては、例えばポリイミド、液晶ポリマー、フッ素樹脂、ポリエチレンテレフタレート、ポリエチレンナフタレート等の可撓性を有する樹脂、紙フェノール、紙エポキシ、ガラスコンポジット、ガラスエポキシ、テフロン(登録商標)、ガラス基材等のリジッド材、硬質材料と軟質材料とを複合したリジッドフレキシブル材を用いることが可能である。これらの中でも、金属酸化物等との結合力が大きいことから、ポリイミドが特に好ましい。
上記焼結体は、上述のように、本発明の一実施形態の金属粉末を含むインクの塗工及び焼成により、ベースフィルムの一方の面に積層される。当該プリント配線板用基材では、インクの塗工及び焼結により焼結体を形成するので、ベースフィルムの一方の面を容易に可撓性かつ導電性の皮膜で覆うことができる。
当該プリント配線板用基材は、図3に示すように、上記金属粉末を製造する工程(ステップS1:金属粉末製造工程)と、この金属粉末製造工程で得られる金属粉末を用いて上記インクを製造する工程(ステップS2:インク製造工程)と、このインク製造工程で得られるインクを塗工する工程(ステップS3:塗工工程)と、この塗工工程で塗工したインクの塗膜を焼成する工程(ステップS4:焼成工程)とを備える方法によって製造することができる。
ステップS1の金属粉末製造工程では、上述のように、好ましくは液相還元法、より好ましくは3価のチタンイオンを還元剤とするチタンレドックス法により、上記平均粒径D50BET、上記平均結晶子径DCryst及び上記平均粒径D50BETに対する平均結晶子径DCrystの比を有する金属粉末を製造する。
ステップS2のインク製造工程では、上述のように、金属粉末を分散媒中に分散してインクを製造する。
ステップS3の塗工工程では、上述のように、ベースフィルムの少なくとも一方の面に上記インクを塗工する。
ステップS4の焼成工程では、上述のように、ベースフィルム上に形成したインクの塗膜を焼成することにより、分散媒、分散剤及びその他の有機物を揮発及び分解させ、残る金属粉末同士を接合させて焼結体を形成する。
当該プリント配線板用基材は、ベースフィルムの少なくとも一方の面側に積層されるフィルム状の上記焼結体を備えるので、曲げによって焼結体が破断し難く可撓性に優れるプリント配線板を製造することができる。
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、特許請求の範囲によって示され、特許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。
ビーカーに還元剤としての三塩化チタン溶液80g、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ビニルピロリドン(分子量30000)1gを純水1Lに溶解し、この水溶液を35℃に保温した。この水溶液に同温度で保温した硫酸銅10gの水溶液を撹拌しながら投入して、銅粒子を析出させた。10000rpmの遠心分離により分離した銅粒子に100mL(上記液相還元用水溶液量に対して10質量%)の純水を加え、400rpmのスターラーで撹拌しながら超音波振動を加える分散処理を10分間行った。この工程を2回繰り返して銅を主成分とする金属粉末No.1を得た。
上記金属粉末No.1とは、水溶液の保温温度を60℃とした以外は同じ条件で銅粒子を析出させ、同様の洗浄を行って金属粉末No.2の水分散体を得た。
上記金属粉末No.1とは、還元剤をエチレングリコールとし、水溶液の保温温度を200℃とした以外は同じ条件で銅粒子を析出させ、同様の洗浄を行って金属粉末No.3の水分散体を得た。
これらの金属粉末No.1~3について、走査型電子顕観察による撮影画像上で平均粒径DSEM(体積換算値)を測定した。
これらの金属粉末No.1~3について、(1,1,1)面からのX線回折により平均結晶子径DCrystを測定した。なお、平均結晶子径DCrystの測定には、フィリップス社の「X’PERT PRO」を使用した。
これらの金属粉末No.1~3について、BET法により比表面積を測定し、測定した比表面積から平均粒径D50BETを算出した。なお、比表面積の測定には、メイクロメリティックス社の「アサップ2010」を使用し、測定ガスとして窒素ガスを用いた。
これらの金属粉末No.1~3について、ICP分析(高周波誘導結合プラズマ発光分光分析)により金属組成を測定した。なお、ICP分析には、サーモフィッシャーサイエンティフィック社の「iCAP6300 DUO」を使用した。
上記金属粉末No.1~3を使用して、水を溶媒とする銅濃度25質量%の3種類のインクを調製した。これらのインクをベースフィルムとなるポリイミド基材にバーコーターで塗工及び乾燥し、平均厚さ150nmの銅粒子塗膜を形成した。この銅粒子塗膜を形成したポリイミド基材を温度300℃の窒素雰囲気中で2時間焼成することにより、ポリイミド基材上に積層された焼結体No.1~3を得た。
これらの焼結体No.1~3について、X線回折により平均結晶子径DCrystを測定した。なお、この測定には、金属粉末No.1~3の平均結晶子径の測定と同じ装置を使用した。
上記焼結体No.1~3の焼結体の表面に無電解銅メッキを施すことにより焼結体と無電解メッキ層との合計平均厚さを1μmとし、さらに電気銅メッキを施すことによりベースフィルム上に焼結体、無電解メッキ層及び電気メッキ層からなる平均厚さ10μmの金属層を積層した3種類のプリント配線板用基材を得た。さらにこれらの配線板用基材を用いてサブトラクティブ法によりプリント配線板No.1~3を形成した。詳しくは、各配線板用基材にレジスト膜を形成しエッチングを行った後にレジスト膜を除去することで金属層をパターニングして導電パターンを形成したプリント配線板No.1~3を得た。
プリント配線板No.1~3を接着剤層が設けられたポリイミド基材と貼り合せて屈曲性評価用サンプルとし、曲率半径2mm、速度1500rpm及び摺動距離20mmの条件で屈曲試験機により繰り返し屈曲させて、導電パターンが破断するまでの屈曲回数を調べた。なお、屈曲試験機としては、信越エンジニアリング社の「SEK-31B4S」を使用した
S2 インク製造工程
S3 塗工工程
S4 焼成工程
Claims (9)
- BET法により算出される平均粒径D50BETが1nm以上200nm以下、X線解析による平均結晶子径DCrystが20nm以下であり、
上記平均粒径D50BETに対する平均結晶子径DCrystの比(DCryst/D50BET)が0.4未満である金属粉末。 - 主成分が銅又は銅合金である請求項1に記載の金属粉末。
- 主成分と異なる金属を含有する請求項1又は請求項2に記載の金属粉末。
- 水溶液中で還元剤により金属イオンを還元する液相還元法により形成される請求項1、請求項2又は請求項3に記載の金属粉末。
- 上記液相還元法が3価のチタンイオンを還元剤とする請求項4に記載の金属粉末。
- 請求項1から請求項5のいずれか1項に記載の金属粉末と、その分散媒とを備えるインク。
- 請求項6に記載のインクの塗工及び焼成により形成され、
平均結晶子径DCrystが25nm以下である焼結体。 - 絶縁性を有するベースフィルムと、
このベースフィルムの少なくとも一方の面側に積層される請求項7に記載のフィルム状の焼結体と
を備えるプリント配線板用基材。 - BET法により算出される平均粒径D50BETが1nm以上200nm以下、X線解析による平均結晶子径DCrystが20nm以下であり、
上記平均粒径D50BETに対する平均結晶子径DCrystの比(DCryst/D50BET)が0.4未満である金属粉末の製造方法であって、
水溶液中で還元剤により金属イオンを還元する工程を備え、
この還元工程を100℃以下で行う金属粉末の製造方法。
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