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WO2010067696A1 - Encre pour la formation de motifs métalliques, et motifs métalliques associés - Google Patents

Encre pour la formation de motifs métalliques, et motifs métalliques associés Download PDF

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Publication number
WO2010067696A1
WO2010067696A1 PCT/JP2009/069608 JP2009069608W WO2010067696A1 WO 2010067696 A1 WO2010067696 A1 WO 2010067696A1 JP 2009069608 W JP2009069608 W JP 2009069608W WO 2010067696 A1 WO2010067696 A1 WO 2010067696A1
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WO
WIPO (PCT)
Prior art keywords
ink
metal
palladium
metal pattern
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2009/069608
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English (en)
Japanese (ja)
Inventor
眞一 鈴木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta IJ Technologies Inc
Original Assignee
Konica Minolta IJ Technologies Inc
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Filing date
Publication date
Application filed by Konica Minolta IJ Technologies Inc filed Critical Konica Minolta IJ Technologies Inc
Priority to JP2010542067A priority Critical patent/JPWO2010067696A1/ja
Publication of WO2010067696A1 publication Critical patent/WO2010067696A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
    • 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
    • H05K2203/01—Tools for processing; Objects used during processing
    • H05K2203/0104—Tools for processing; Objects used during processing for patterning or coating
    • H05K2203/013—Inkjet printing, e.g. for printing insulating material or resist
    • 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

Definitions

  • the present invention relates to a metal pattern forming ink used for forming a metal pattern, and more particularly to a metal pattern forming ink and a metal pattern used for circuit formation by an inkjet method.
  • Formation of a metal pattern used for a circuit has been conventionally performed by a method using a resist material. That is, after applying a resist material on a thin metal layer and exposing the required pattern to light, the unnecessary resist is removed by development, the exposed thin metal is removed by etching, and the remaining resist portion is peeled off. As a result, a metal thin film on which a metal pattern was recorded was formed.
  • This metal pattern forming method is a method of forming a circuit by firing at a temperature of about 200 to 300 ° C. utilizing the fact that the melting point is lowered by minimizing the particle size of the metal nanoparticles.
  • a soluble palladium metal salt is contained in an ink, and the ink is printed on a substrate by an ink jet method to form a palladium catalyst pattern. Thereafter, electroless plating is performed to form a metal pattern on the catalyst pattern.
  • the palladium metal salt has poor dissolution stability, the palladium metal salt is precipitated in the ink, or the palladium metal salt is in a non-uniform state on the printed circuit board, and the electroless plating is adversely affected. There was also a problem.
  • the present invention has been made in view of the above-mentioned problems, and has as its object the storage stability of the palladium metal salt in the ink and the good dischargeability from the ink jet recording head, and the palladium metal salt is electroless plated. It is an object of the present invention to provide a metal pattern forming ink which functions as a catalyst for the metal pattern and is excellent in the drawability and film thickness uniformity of the formed metal pattern and a metal pattern formed using the same.
  • the catalyst is palladium
  • An ink for forming a metal pattern comprising a metal salt and a complexing agent, wherein a complex is formed by the palladium metal salt and the complexing agent.
  • the inventor of the present invention provides a metal pattern forming ink used for printing a pattern portion on a substrate by ink-jet ink containing a catalyst and forming a metal pattern on the pattern portion by electroless plating.
  • the catalyst contains a palladium metal salt and a complexing agent, and is complexed with the palladium metal salt and the complexing agent.
  • a palladium metal salt used as a catalyst is unstable and has a characteristic of easily causing precipitation in a solution.
  • the palladium metal salt In order for the palladium metal salt to function as a catalyst, it is necessary to perform a reduction reaction from palladium ions (Pd 2+ ) to palladium metal (Pd 0 ). However, in the reduction reaction from palladium ion (Pd 2+ ) to palladium metal (Pd 0 ), the reaction rate often changes drastically depending on the reduction conditions (eg, reducing agent, temperature, pH, etc.). If the reaction is slow, it becomes difficult to produce palladium metal, and conversely, if the reaction is too fast and produced in the state of agglomerated palladium metal, there is often a problem that adversely affects metal formation in the next electroless plating process.
  • the reduction conditions eg, reducing agent, temperature, pH, etc.
  • the present inventor has found that the object effect of the present invention can be efficiently expressed by including a palladium metal salt and a complexing agent in the ink, and has led to the present invention. It depends on you.
  • Palladium ions (Pd 2+ ) are complexed with a complexing agent (Ch), which is an electrostatically coordinating compound (Pd-Ch), which has increased solubility and stability in ink. It has been found that the occurrence of precipitation and the like can be suppressed. At the same time, the reactivity of the complexed compound (Pd—Ch) with the reducing agent is alleviated, so the application range of the reduction reaction condition is widened and it can be controlled as a gradual reduction reaction. It became possible to make the metal uniform and dense. With this uniform and dense catalyst, it was possible to demonstrate excellent results in the reproducibility of thin wires and copper film thickness of metals produced by subsequent electroless plating, such as copper.
  • Ch complexing agent
  • Pd-Ch electrostatically coordinating compound
  • One feature of the metal pattern forming ink (hereinafter also simply referred to as ink) used for pattern formation by the inkjet method of the present invention is that the catalyst contains a palladium metal salt and a complexing agent.
  • the form of the catalyst used in the ink of the present invention is not a metal fine particle or a metal salt colloid (for example, palladium-tin colloid), but a palladium metal salt and a complexing agent complex to form a solution in the ink.
  • the palladium metal salt present is preferred. This means that the ink is a homogeneously dissolved ink. As a result, there is no occurrence of clogging of the ink jet head, and stable emission can be realized.
  • Examples of the palladium metal salt applicable to the present invention include palladium fluoride, palladium chloride, palladium bromide, palladium iodide, palladium nitrate, palladium sulfate, palladium acetate, palladium acetoacetate, palladium trifluoroacetate, palladium hydroxide. , Palladium oxide, palladium sulfide and the like, among which palladium chloride is preferable.
  • the content of the palladium metal salt in the ink is preferably 0.01% by mass or more and 1.0% by mass or less. If the concentration of the palladium metal salt is 0.01% by mass or more, the necessary activity of the electroless plating reaction as the next step can be obtained, and if it is 1.0% by mass or less, the palladium metal in the ink is obtained. This is preferable in that the stability of the salt can be maintained.
  • Examples of the complexing agent applicable to the ink of the present invention include compounds capable of forming a complex with the palladium metal salt.
  • Examples of the compound include an organic acid having a carboxyl group, and examples thereof include oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, tartaric acid, and citric acid. And it is preferably an amine compound or a nitrogen-containing heterocyclic compound.
  • An amine compound is a compound in which one or more hydrogen atoms of ammonia are substituted with a hydrocarbon residue R, and is a complexing agent for Pd ions. Here, ammonia is also included.
  • the amine retains an unshared electron pair on the N atom and tends to complex with palladium ions.
  • amines ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, pyridine, 2-aminopyridine, 3-aminopyridine
  • Linear amine compounds such as 4-aminopyridine, ethylenediamine, ethanolamine, triethanolamine, and ethylenediaminetetraacetic acid, and cyclic amine compounds.
  • the nitrogen-containing heterocyclic compound include pyridine, bipyridine, phenanthroline and the like.
  • the molar ratio of the palladium metal salt (Pd) and the complexing agent (Ch) is preferably in the range of 1: 0.5 or more and 1:10 or less.
  • the ratio of the complex formed by the palladium metal salt and the complexing agent increases, so that the solubility in the ink and the reduction reactivity are increased. Becomes better.
  • the molar ratio is 1:10 or less in order to suppress reaction inhibition by an excessive complexing agent.
  • the pH of the ink is preferably adjusted to a range of 8.0 or more, more preferably pH 9.
  • the pH is from 0 to 14.0, more preferably from pH 9.0 to 13.5, and particularly preferably from 10.0 to 13.5.
  • the complex formed by the palladium metal salt and the complexing agent is preferably formed at a pH of 8.0 or higher because the formation proceeds more easily as the pH of the ink is more alkaline. In combination with a non-ink-absorbing resin substrate, the higher the pH of the ink, the better the adhesion and the better.
  • an aqueous liquid medium is preferably used from the viewpoint of solubility of the palladium metal salt and the complexing agent, and the aqueous liquid medium is a mixed solvent such as water and a water-soluble organic solvent. Is more preferably used.
  • the composition of these solvents is preferably selected in consideration of the dissolved state of the complex formed with the palladium metal salt and the complexing agent.
  • water-soluble organic solvent examples include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, etc.) and polyhydric alcohols (for example, ethylene glycol, diethylene glycol).
  • alcohols for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, etc.
  • polyhydric alcohols for example, ethylene glycol, diethylene glycol
  • Triethylene glycol polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.
  • polyhydric alcohol ethers eg, ethylene glycol monomethyl ether
  • Ethylene glycol monoethyl ether ethylene glycol monobutyl ether
  • a simple catalyst solution containing only water is not suitable as an ink-jet ink.
  • the presence of the organic solvent gives an appropriate viscosity (viscosity) for the ink to be stably ejected from the ink jet head, and the viscosity can be adjusted in the range of 1.5 to 30 mPa / s.
  • viscosity viscosity
  • moisture retention is imparted in order to avoid solidification and ejection failure in the head nozzle
  • the surface tension of the ink can be adjusted to 50 to 25 mN / m suitable for inkjet by using an organic solvent. is important.
  • the organic solvent is preferably 5 to 90% by mass in the ink, and more preferably 30 to 80% by mass. Moreover, as a boiling point of an organic solvent, 80 degreeC or more and 250 degrees C or less are preferable at the point of moisture retention and drying property.
  • Surfactants applicable to the ink of the present invention include, for example, alkyl sulfates, alkyl ester sulfates, dialkyl sulfosuccinates, alkyl naphthalene sulfonates, alkyl phosphates, polyoxyalkylene alkyl ether phosphates, Anionic surfactants such as fatty acid salts, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyalkylene alkyl phenyl ethers, acetylene glycols, polyoxyethylene-polyoxypropylene block copolymers, glycerin esters, Examples include surfactants such as sorbitan esters, polyoxyethylene fatty acid amides, and amine oxides, and cationic surfactants such as alkylamine salts and quaternary ammonium salts.
  • the ink of the present invention may contain various conventionally known additives for other metal pattern forming inks as required.
  • additives for other metal pattern forming inks for example, fluorescent brighteners, antifoaming agents, lubricants, preservatives, thickeners, antistatic agents, matting agents, water-soluble polyvalent metal salts, acid bases, pH adjusters such as buffers, antioxidants, surfaces
  • Tension modifiers, non-resistance modifiers, rust inhibitors, inorganic pigments and the like can be mentioned.
  • the substrate on which the metal pattern is formed is not particularly limited as long as it has insulating properties.
  • the substrate on which the metal pattern is formed is not particularly limited as long as it has insulating properties.
  • a highly rigid material such as glass or ceramics, PET ( Polyethylene terephthalate) and a film-like material composed of a resin such as polyimide.
  • a non-ink-absorbing resin substrate it is preferable to use a non-ink-absorbing resin substrate.
  • a non-ink-absorbing resin substrate particularly a resin film, as the base material, excellent flexibility can be obtained, and it can be applied to a wide range of fields, and in addition, a non-ink-absorbing substrate can be obtained. Therefore, the expansion and contraction of the substrate in the metal pattern forming process is suppressed, so that a highly precise metal pattern can be formed.
  • the non-ink-absorbing resin is not particularly limited as long as it has insulating properties.
  • a film having a material such as, for example, is preferable.
  • a film-like material composed of a resin such as PET (polyethylene terephthalate) or polyimide is preferable, and a polyimide film is more preferable.
  • the substrate used in the present invention may be subjected to surface modification treatment from the viewpoint of improving adhesion.
  • an undercoat layer may be provided on the substrate.
  • the material for the undercoat layer include a coupling agent such as a silane coupling agent.
  • the metal pattern forming method using the ink of the present invention includes 1) pattern printing in which an ink containing a palladium metal salt and a complexing agent is ejected from a inkjet head onto a non-ink-absorbing resin substrate to print a pattern portion. And 2) an electroless plating process for forming a metal pattern by performing an electroless plating process on the pattern portion, and further between the above 1) pattern printing process and 2) electroless plating process 3) It is preferable to provide a catalyst activation step.
  • the ink of the present invention containing a palladium metal salt and a complexing agent is ejected from an inkjet head onto a non-ink-absorbing resin substrate to form a pattern.
  • the size of the ink droplets to be ejected is not particularly limited. However, in the case of circuit wiring or the like, it is necessary to form fine lines, and therefore the amount is preferably 50 pl or less, and more preferably 20 pl or less.
  • the ink jet head is not particularly limited, and either a piezo type or a thermal type head can be used.
  • the catalyst activation is performed between the step of printing on the substrate the ink containing the palladium metal salt of the catalyst and the complexing agent and the step of performing the electroless plating process described later. It is preferable to have a process.
  • the step of making the catalyst palladium metal zero is referred to as the catalyst activation step.
  • the catalyst activation step it is necessary to select an appropriate method depending on the type of catalyst, and examples thereof include application of acid, heating, and application of a reducing agent.
  • a preferable reducing agent for palladium ions is a boron-based compound. Specifically, sodium borohydride, trimethylamine borane, dimethylamine borane (DMAB), and the like are preferable.
  • an electroless plating process is performed to obtain a metal pattern in which a metal is formed on the pattern portion.
  • the step of immersing the non-ink-absorbing resin substrate printed with the above pattern in an electroless plating solution (bath) is a common method.
  • the electroless plating solution mainly contains 1) metal ions, 2) complexing agent for electroless plating solution, and 3) reducing agent.
  • the metal formed by electroless plating include gold, silver, copper, palladium, nickel, and alloys thereof, and silver or copper is preferable from the viewpoint of conductivity and safety, and copper is more preferable. . Therefore, metal ions corresponding to the above metals are contained as metal ions used in the electroless plating bath. Accordingly, copper ions are preferable, and examples thereof include copper sulfate.
  • the complexing agent and reducing agent for the electroless plating solution are also selected to be suitable for metal ions.
  • EDTA ethylenediaminetetraacetic acid
  • Rochelle salt D-mannitol, D-sorbitol, dulcitol, iminodiacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, and the like.
  • EDTA is preferred.
  • the reducing agent include formaldehyde, potassium tetrahydroborate, dimethylamine borane, glyoxylic acid, sodium hypophosphite and the like, and formaldehyde is preferable.
  • the metal formation speed and film thickness can be controlled by controlling the temperature, pH, immersion time, and metal ion concentration of the plating bath.
  • the metal film thickness formed in the present invention is preferably 0.01 ⁇ m or more and 30 ⁇ m or less.
  • Ink 2 was prepared in the same manner as in the preparation of Ink 1, except that the amount of sodium hydroxide added was appropriately adjusted to change the pH of the ink to 7.5, 8.5, 13.2, and 13.6, respectively. ⁇ 5 were prepared. As a result of visual observation of the appearance of the prepared inks 2 and 5, it was confirmed that some undissolved palladium chloride was present.
  • Ink 6 was prepared in the same manner as in Preparation of Ink 1 except that the amount of addition of 2-aminopyridine as a complexing agent was changed to 0.047% by mass.
  • the molar ratio (Pd: Ch) of palladium chloride (Pd) to 2-aminopyridine (Ch) in the ink 6 is 1: 0.38.
  • Ink 7 was prepared in the same manner as in Preparation of Ink 1 except that the amount of addition of 2-aminopyridine as a complexing agent was changed to 0.055% by mass.
  • the molar ratio (Pd: Ch) of palladium chloride (Pd) to 2-aminopyridine (Ch) in ink 7 is 1: 0.50.
  • Ink 8 was prepared in the same manner as in Preparation of Ink 1 except that the addition amount of palladium chloride was changed to 0.01% by mass and the addition amount of 2-aminopyridine as a complexing agent was changed to 0.026% by mass. did.
  • the molar ratio (Pd: Ch) of palladium chloride (Pd) to 2-aminopyridine (Ch) in ink 8 is 1: 4.9.
  • Ink 9 was prepared in the same manner as in Preparation of Ink 1 except that the addition amount of palladium chloride was changed to 0.9% by mass and the addition amount of 2-aminopyridine as a complexing agent was changed to 0.9% by mass. did.
  • the molar ratio (Pd: Ch) of palladium chloride (Pd) to 2-aminopyridine (Ch) in ink 9 is 1: 1.9.
  • Ink 10 was prepared in the same manner as in Preparation of Ink 1 except that the addition amount of palladium chloride was changed to 1.1% by mass and the addition amount of 2-aminopyridine as a complexing agent was changed to 1.1% by mass. did.
  • the molar ratio (Pd: Ch) of palladium chloride (Pd) to 2-aminopyridine (Ch) in the ink 10 is 1: 1.9.
  • Ink 11 was prepared in the same manner as in Preparation of Ink 1 except that the amount of addition of 2-aminopyridine as a complexing agent was changed to 1.0% by mass.
  • the molar ratio (Pd: Ch) of palladium chloride (Pd) to 2-aminopyridine (Ch) in the ink 11 is 1: 9.5.
  • Ink 12 was prepared in the same manner as in the preparation of Ink 1, except that the amount of addition of 2-aminopyridine as a complexing agent was changed to 1.16% by mass.
  • the molar ratio (Pd: Ch) of palladium chloride (Pd) to 2-aminopyridine (Ch) in the ink 12 is 1: 11.0.
  • Ink 14 Comparative Example
  • Ink was prepared using 0.1% by mass of palladium chloride as a catalyst, 30% by mass of ethylene glycol, 10% by mass of glycerin, and pure water as a residue as a water-soluble organic solvent.
  • ink 14 was prepared by slowly dropping hydrochloric acid until the palladium chloride was dissolved. As a result of measuring the pH of the ink 14, it was 1.0 or less.
  • Comparative ink 15 As a metal colloidal solution of palladium / tin, 3.0% by mass of Predep PN-104 (manufactured by World Metal), 27.0% by mass of catalyst PN105 (manufactured by World Metal), 30% by mass of water-soluble solvent ethylene glycol, Comparative ink 15 was prepared by adding 20% by mass of glycerin and using pure water as a residue.
  • Ink 16 Present Invention
  • Ink was prepared using 0.2% by mass of palladium chloride as a catalyst, 0.2% by mass of bipyridine as a complexing agent, 30% by mass of ethylene glycol, 10% by mass of glycerin as a water-soluble organic solvent, and pure water as a residue. did.
  • the pH of the ink was adjusted to 10.0 using sodium hydroxide to obtain ink 16.
  • the molar ratio (Pd: Ch) of palladium chloride (Pd) and bipyridine (Ch) in the ink 16 is 1: 1.5.
  • [Preparation of Ink 17: Present Invention] Prepare an ink using 0.2% by mass of palladium chloride as a catalyst, 0.2% by mass of ethylenediamine as a complexing agent, 30% by mass of ethylene glycol, 10% by mass of glycerin as a water-soluble organic solvent, and pure water as a residue. did. Next, the pH of the ink was adjusted to 10.0 using sodium hydroxide to obtain ink 17. As a result of visual observation of the appearance of the prepared ink 17, it was confirmed that palladium chloride was completely dissolved. The molar ratio (Pd: Ch) of palladium chloride (Pd) to ethylenediamine (Ch) in the ink 17 is 1: 1.5.
  • ⁇ The number of missing nozzles is less than 2% with respect to the total number of nozzles.
  • the number of missing nozzles is 2% or more and less than 5% with respect to the total number of nozzles.
  • ⁇ The number of missing nozzles is 5% or more and less than 10% with respect to the total number of nozzles x: Number of missing nozzles is 10% or more with respect to the total number of nozzles [Evaluation of storage stability] Put each ink prepared above in a glass bottle, 1) store at 50 ° C. for 8 hours, then 2) return the temperature to room temperature, 3) store at ⁇ 10 ° C. for 8 hours, and repeat the cycle from 1) to 3) for 10 cycles. The cycle was repeated. Subsequently, the ink after cycle storage and the ink before storage were compared and observed visually, and the storage stability of the ink was evaluated according to the following criteria.
  • a polyimide sheet (substrate 1) having a thickness of 75 ⁇ m is attached to the stage as a non-ink-absorbing resin substrate, and ink 1 is ejected, wiring width 50 ⁇ m, wiring distance 50 ⁇ m, wiring length 30 mm, 100 fine line patterns and 10 mm A square metal pattern of ⁇ 10 mm was formed.
  • activation step 1 The substrate 1 after pattern formation by the above method was dried at 80 ° C. for 5 minutes, and then immersed in the following activation liquid containing a boron-based reducing agent for 15 minutes at room temperature. In this step, the Pd complex was reduced to form Pd metal. The substrate 1 after immersion was washed with pure water.
  • the following electroless copper plating solution has a copper concentration of 2.5% by mass, a formalin concentration of 1% by mass, and an ethylenediaminetetraacetic acid (EDTA) concentration of 2.5% by mass.
  • the pH of the electroless copper plating solution was adjusted to 13.0 with sodium hydroxide.
  • the metal wiring pattern 3 was formed in the same manner except that the substrate 2 (75 ⁇ m thick polyethylene terephthalate film) was used instead of the substrate 1 (75 ⁇ m thick polyimide sheet). .
  • metal wiring patterns 4 to 16 In the formation of the metal wiring pattern 1, metal wiring patterns 4 to 16 were formed in the same manner except that the inks 2 to 14 were used instead of the ink 1, respectively.
  • metal wiring pattern 17 In the formation of the metal wiring pattern 1, the metal wiring pattern 17 was formed in the same manner except that the ink 1 was changed to the ink 15 and the activation process 1 was changed to the activation process 2 described below.
  • activation step 2 A square metal pattern was formed using palladium / tin colloidal ink 6 and then immersed in the following solution at room temperature for 2 minutes to remove tin, leaving palladium metal. By this step, a wiring pattern of palladium metal of ink 6 was formed.
  • metal wiring patterns 18 and 19 were formed in the same manner except that the inks 16 and 17 were used in place of the ink 1, respectively.
  • ⁇ There is no chipping (disconnection) or contact between the thin wires, and the line shape disorder (thinning or thickening) is less than 5%.
  • ⁇ There is no chipping (disconnection), there is no contact between the thin wires, and The line shape disorder (thinning or thickening) is also 5% or more and less than 10%.
  • Fine line breakage (breakage), no contact between the thin lines, and line shape disorder (thinning or thickening) is 10% or more.
  • the average film thickness T and the film thickness variation were measured, and the film thickness uniformity was evaluated according to the following criteria.
  • T ( ⁇ m) (T1 + T2 +... + T50) / 50 ⁇ 100
  • T1, T2,... represent the film thickness at the first measurement position, the film thickness at the second measurement position,.
  • Film thickness variation ⁇ (maximum film thickness ⁇ minimum film thickness) / average film thickness ⁇ ⁇ 100
  • a metal pattern having a size of 10 mm ⁇ 10 mm was formed by the method for forming each metal pattern. The adhesion of the metal pattern was evaluated by a tape peeling test according to JIS C5600.
  • notches in a grid pattern of 25 mm in length and width at intervals of 2 mm were formed with a cutter, and cellophane tape was attached from above the grid pattern.
  • the number of pieces peeled off to the tape side was counted and evaluated according to the following rank, and used as an index of adhesion.
  • A The peeled metal pattern is not recognized.
  • B The peeled metal pattern is recognized, but the number of occurrence is less than 5%.
  • C The peeled metal pattern is recognized, but the number of occurrence is 5% or more and less than 9%.
  • D Although a peeled metal pattern is observed, the number of occurrences is 9% or more and less than 13%.
  • E A peeled metal pattern is recognized and the number of occurrences is 13% or more.
  • a rank C or higher in both adhesion was evaluated as a practically favorable range.
  • Table 2 shows the evaluation results obtained as described above.
  • the metal wiring pattern of the present invention is excellent in fine line delineability and film thickness uniformity as compared with the comparative example.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

La présente invention concerne une encre pour la formation d'un motif métallique qui présente une bonne stabilité au stockage d'un sel de palladium métallique contenu dans l'encre et servant de catalyseur de dépôt sans courant, et qui permet d'obtenir une bonne décharge depuis une tête d'impression à jet d'encre, et d'excellentes caractéristiques de dessin, d'uniformité d'épaisseur et d'adhérence du motif métallique. L'invention concerne également des motifs métalliques formés avec cette encre. L'encre est utilisée quand des sections de motifs sont imprimées sur un substrat par un système à jet d'encre utilisant une encre contenant un catalyseur, et des motifs métalliques sont formés sur les sections de motifs par dépôt sans courant. L'encre pour formation de motifs métalliques se caractérise en ce que le catalyseur contient un sel de palladium métallique et un agent complexant, et en ce qu'un complexe se forme entre le sel de palladium métallique et l'agent complexant.
PCT/JP2009/069608 2008-12-08 2009-11-19 Encre pour la formation de motifs métalliques, et motifs métalliques associés Ceased WO2010067696A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2010542067A JPWO2010067696A1 (ja) 2008-12-08 2009-11-19 金属パターン形成用インク及び金属パターン

Applications Claiming Priority (2)

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JP2008311886 2008-12-08
JP2008-311886 2008-12-08

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WO2010067696A1 true WO2010067696A1 (fr) 2010-06-17

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PCT/JP2009/069608 Ceased WO2010067696A1 (fr) 2008-12-08 2009-11-19 Encre pour la formation de motifs métalliques, et motifs métalliques associés

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190117587A (ko) 2017-02-14 2019-10-16 닛산 가가쿠 가부시키가이샤 배선 형성 방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56157091A (en) * 1980-05-08 1981-12-04 Fujitsu Ltd Method of manufacturing printed circuit board
JPH07131135A (ja) * 1993-11-05 1995-05-19 Ibiden Co Ltd プリント配線基板のイニシェータパターンの形成に水性インクを用いた製造方法
JPH08316612A (ja) * 1995-05-15 1996-11-29 Ibiden Co Ltd プリント配線板及びその製造方法
JP2002299833A (ja) * 2001-03-30 2002-10-11 Harima Chem Inc 多層配線板およびその形成方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56157091A (en) * 1980-05-08 1981-12-04 Fujitsu Ltd Method of manufacturing printed circuit board
JPH07131135A (ja) * 1993-11-05 1995-05-19 Ibiden Co Ltd プリント配線基板のイニシェータパターンの形成に水性インクを用いた製造方法
JPH08316612A (ja) * 1995-05-15 1996-11-29 Ibiden Co Ltd プリント配線板及びその製造方法
JP2002299833A (ja) * 2001-03-30 2002-10-11 Harima Chem Inc 多層配線板およびその形成方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190117587A (ko) 2017-02-14 2019-10-16 닛산 가가쿠 가부시키가이샤 배선 형성 방법

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