WO2013024767A1 - Procédé de fabrication d'un motif de câblage et élément pour le placage - Google Patents

Procédé de fabrication d'un motif de câblage et élément pour le placage Download PDF

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Publication number
WO2013024767A1
WO2013024767A1 PCT/JP2012/070206 JP2012070206W WO2013024767A1 WO 2013024767 A1 WO2013024767 A1 WO 2013024767A1 JP 2012070206 W JP2012070206 W JP 2012070206W WO 2013024767 A1 WO2013024767 A1 WO 2013024767A1
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Prior art keywords
plating
parent
wiring pattern
support
manufacturing
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PCT/JP2012/070206
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English (en)
Japanese (ja)
Inventor
翔平 小泉
敬 杉▲崎▼
宮本　健司
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株式会社ニコン
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Publication of WO2013024767A1 publication Critical patent/WO2013024767A1/fr

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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
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4685—Manufacturing of cross-over conductors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • C23C18/1641—Organic substrates, e.g. resin, plastic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • 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
    • H05K3/185—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 by making a catalytic pattern by photo-imaging
    • 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
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0108—Transparent
    • 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
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • 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
    • H05K2201/0242—Shape of an individual particle
    • H05K2201/0245—Flakes, flat particles or lamellar particles
    • 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
    • H05K2201/0242—Shape of an individual particle
    • H05K2201/0248—Needles or elongated particles; Elongated cluster of chemically bonded particles
    • 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
    • H05K2203/05—Patterning and lithography; Masks; Details of resist
    • H05K2203/0562—Details of resist
    • H05K2203/0565—Resist used only for applying catalyst, not for plating itself
    • 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
    • H05K2203/05—Patterning and lithography; Masks; Details of resist
    • H05K2203/0562—Details of resist
    • H05K2203/0585—Second resist used as mask for selective stripping of first 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
    • H05K2203/14—Related to the order of processing steps
    • H05K2203/1415—Applying catalyst after applying plating resist

Definitions

  • the present invention relates to a method for manufacturing a wiring pattern and a member for plating. This application claims priority based on Japanese Patent Application No. 2011-177423 for which it applied on August 15, 2011, and uses the content here.
  • electroless plating which is a plating method using reduction by contact action of a material surface. Since electroless plating does not use electrical energy, it is possible to apply plating to resin materials and glass that are nonconductors.
  • the plating film obtained in this way it is necessary that the plating film does not peel off in the environment where the plated product is used.
  • difficult-to-plat materials such as resin materials and glass have weak adhesion to the formed plating film, and the plating is easily peeled off due to the internal stress of the plating film, resulting in peeling such as swelling.
  • the surface of the resin material is preliminarily etched with a chromic acid solution to chemically roughen the surface. Yes. Thereby, since the plating film to be formed is formed so as to bite into the unevenness of the roughened resin material, adhesion can be obtained (anchor effect).
  • a general resin plating process is represented by washing ⁇ etching ⁇ catalyst application ⁇ electroless plating.
  • the catalyst application is a step of attaching palladium (Pd) or the like, which becomes a reaction initiator (catalyst) for electroless plating, to the surface.
  • a process of reducing and activating palladium by applying a colloidal solution of divalent palladium salt and divalent tin (Sn) salt and then immersing it in an acid or alkali solution called an accelerator.
  • the electroless plating include electroless Cu plating and electroless NiP plating.
  • the process is the same as the resin plating process.
  • a method is generally used in which irregularities are formed on the surface of the glass by etching treatment such as hydrofluoric acid and the adhesion is improved by an anchor effect.
  • an SOG (Spin-on Glass) or porous SOG base film is provided on the surface of the hard-plated substrate, and electroless plating is performed on the base film (see Patent Document 1).
  • a method of providing a base film made of a filler component such as powdered silica and a resin composition component and performing electroless plating on the base film is disclosed.
  • Plating products formed using electroless plating are used as constituent materials for various products.
  • plated products with metal plating on glass or transparent resin can be applied to products that can utilize the light transmittance of glass and transparent resin, such as displays and solar cells that require high light transmittance. Application is expected.
  • An object of an aspect of the present invention is to provide a wiring pattern manufacturing method and a plating member capable of forming a wiring satisfactorily without impairing the transparency of a light-transmitting difficult plating material.
  • a base film including a light-transmitting base material and alumina particles having an average particle diameter of 100 nm or less is selected on a light-transmitting support.
  • the plating member according to the second aspect of the present invention includes a light-transmissive support and a base film selectively formed on the surface of the support, and the base film is light-transmissive. And an alumina particle having an average particle diameter of 100 nm or less.
  • the wiring pattern can be satisfactorily formed without impairing the transparency of the light-transmitting difficult plating material.
  • Example 2 is a photograph showing the results of Example 1.
  • FIG. 2 is a photograph showing the results of Example 1.
  • FIG. 2 is a photograph showing the results of Example 1.
  • FIG. 2 is a photograph showing the results of Example 1.
  • FIG. 2 is a photograph showing the results of Example 1.
  • FIG. 2 is a photograph showing the results of Example 1.
  • FIG. 2 is a table showing the results of Example 1.
  • 6 is a photograph showing the results of Example 2.
  • 6 is a photograph showing the results of Example 3.
  • 6 is a photograph showing the results of Example 3.
  • 6 is a photograph showing the results of Example 4.
  • 6 is a photograph showing the results of Example 4.
  • FIGS. 1 to 5C a method for manufacturing a wiring pattern according to the present embodiment will be described with reference to FIGS. 1 to 5C.
  • the basic reaction of the wiring pattern manufacturing method of the present embodiment will be described with reference to FIGS. 1 to 3E, and then the wiring pattern manufacturing method of the present embodiment will be described with reference to FIGS. 4A to 5C. Will be explained.
  • the dimensions and ratios of the constituent elements are appropriately changed in order to make the drawings easy to see.
  • FIG. 1 is a schematic diagram showing an example of a plating member 1 used in the wiring pattern manufacturing method of the present embodiment.
  • the plating member 1 includes a support 2 that is difficult to plate and has light transmittance, and a parent plating layer (undercoat film) 3 formed on one surface side of the support 2.
  • the support 2 examples include inorganic polymers such as glass, quartz glass, and silicon nitride, and organic polymers (resins) such as acrylic resins, polycarbonate resins, polyester resins such as PET (polyethylene terephthalate) and PBT (polybutylene terephthalate). Can be used. These materials are light transmissive and do not form metal bonds with a metal plating film formed as a result of electroless plating. For this reason, in the present embodiment, these materials are handled as difficult-to-platable materials in which it is difficult to directly form a plating film and the formed plating film is easily peeled off. For the same reason, any material can be used as the material for forming the support 2 as long as the plating film is easily peeled off and has light transmittance.
  • inorganic polymers such as glass, quartz glass, and silicon nitride
  • organic polymers such as acrylic resins, polycarbonate resins, polyester resins such as PET (polyethylene terephthalate) and
  • the parent plating layer 3 has alumina particles having an average particle diameter of about 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, 40 nm, 30 nm, 20 nm, or 10 nm or less.
  • an alumina particle if an average particle diameter is about 100 nm or less, shapes, such as a granular form, rod shape, and feather shape, are employable.
  • the “average particle diameter” is obtained by employing a volume average particle diameter, an area average particle diameter, a cumulative median diameter (Median diameter), etc., using a known method such as a dynamic light scattering method as a measurement principle. This is a possible value.
  • the maximum diameter (size in the longitudinal direction) in one particle is the above average particle size, and the short direction in one particle The size of shows a value smaller than the above-mentioned average particle diameter.
  • the parent plating layer 3 has a binder (base material) for dispersing the alumina particles.
  • the binder is a resin material having optical transparency.
  • a photocurable resin can be used, and in particular, an ultraviolet curable resin can be used.
  • resin materials include epoxy resins, acrylic resins, acrylic urethane resins, phenol resins, ene / thiol resins, and polysiloxanes. In the following description, it is assumed that an ultraviolet curable resin is used as the binder of the parent plating layer 3.
  • FIG. 2A and FIG. 2B are process diagrams showing the manufacturing process of the plating member 1 of the present embodiment.
  • a coating solution in which the above-described alumina molecules are uniformly dispersed in a solution containing a precursor of the above-described resin material is applied to the surface of the support 2 to form a coating film 3A.
  • the application method include generally known methods such as spin coating, dip coating, spray coating, roll coating, brush coating, printing methods such as flexographic printing and screen printing.
  • a polar solvent can be used as a solvent for the coating solution.
  • Usable solvents include, for example, alcohols such as methanol, ethanol, 1-propanol and 2-propanol (isopropyl alcohol, IPA), ethers such as propylene glycol monomethyl ether acetate (PGMEA), and aromatics such as toluene.
  • IPA isopropyl alcohol
  • ethers such as propylene glycol monomethyl ether acetate (PGMEA)
  • aromatics such as toluene.
  • hydrocarbons hydrocarbons
  • nitriles such as acetonitrile
  • esters such as acetate.
  • the viscosity of the whole coating solution can be adjusted and the film thickness of the coating film 3A can be controlled by changing the concentration and the type of the solvent. That is, the layer thickness of the parent plating layer 3 formed from the coating film 3A can be controlled by appropriately selecting the concentration of the coating solution and the type of solvent.
  • the viscosity of the coating liquid increases, so that the coating liquid can be applied thickly.
  • a coating liquid suitable for thick coating can be obtained by selecting a relatively high viscosity solvent from among a number of solvents, it becomes easy to thicken the coating film 3A. If a relatively low viscosity is selected, a coating solution suitable for thin coating can be obtained, so that it is easy to form the coating film 3A thinly.
  • a coating solution using a low-boiling point solvent it may dry immediately upon application, resulting in uneven coating or streaks on the surface of the coating film 3A. Therefore, it is preferable to select a solvent having an appropriate boiling point according to the working environment in which the coating liquid is applied so that coating unevenness and coating stripes do not occur. On the other hand, it is preferable that the solvent has a low boiling point to such an extent that the solvent can be easily removed after application of the coating solution.
  • solvents may be used alone or as a mixture of two or more thereof.
  • PGMEA which is a high boiling point / high viscosity solvent
  • methanol which is a low boiling point / low viscosity solvent
  • the precursor is cured by ultraviolet irradiation to form the parent plating layer 3.
  • the curing step can be performed at room temperature in the production of the plating member 1, so that the resulting plating member 1 is unlikely to contain residual stress. Therefore, for example, when a material having a low elastic modulus is used as the support 2 or when a material that is thin enough to be wound into a roll is used, the problem that the plating member 1 is distorted by residual stress can be suppressed.
  • the reaction may be completed (so-called post-bake) by heating for a certain time after the curing reaction by ultraviolet irradiation. Even in this case, since most of the precursor is cured before post-baking, residual stress is hardly generated and the advantage of using an ultraviolet curable resin can be enjoyed.
  • the plating member 1 as described above hardly scatters light because the particle diameter of the alumina particles of the parent plating layer 3 is about 100 nm or less and is shorter than the wavelength in the visible light region. Therefore, the parent plating layer 3 becomes a transparent film, and the plating member 1 becomes a transparent member.
  • the shape of the alumina particles contained in the parent plating layer 3 is a rod shape or a feather shape
  • the alumina particles are smaller than the average particle size with respect to light that vibrates in the direction intersecting the longitudinal direction of the particles. Acts like a particle with a diameter. That is, when the vibration direction of visible light passing through the parent plating layer 3 is a direction intersecting with the longitudinal direction of the alumina particles, the alumina particles are less likely to be a scattering source with respect to the visible light and transmit visible light. It becomes easy to do. Therefore, it shows high light transmittance.
  • 3A to 3E are explanatory views showing a method of manufacturing a wiring pattern, and are process diagrams for manufacturing a plated product 10 by performing electroless plating on the plating member 1.
  • a description will be given on the assumption that the plated wiring product 10 is manufactured by forming metal wiring by plating.
  • a resist material is applied on the parent plating layer 3 of the plating member 1 and pre-baked to form a resist layer 4.
  • a positive photoresist is used as the resist material.
  • the resist layer 4 is irradiated with ultraviolet light L through a mask M provided with an opening Ma at a position corresponding to a region where the metal wiring is formed and a light shielding portion Mb in a region where the metal wiring is not formed. Layer 4 is exposed.
  • a part of the resist layer 4 is removed by developing with a developing solution that dissolves the resist layer irradiated with ultraviolet rays, and an opening 4a is formed.
  • a catalyst (electroless plating catalyst) 5 used for electroless plating is applied to the parent plating layer 3 exposed in the opening 4 a formed in the resist layer 4.
  • the catalyst 5 include metallic palladium. Specifically, a colloidal solution of a divalent palladium salt and a divalent tin (Sn) salt is applied, and then immersed in an acid or alkali solution called an accelerator to reduce palladium to zero valence. A catalyst 5 made of palladium is applied.
  • the parent plating layer 3 contains alumina particles having extremely fine irregularities, it is considered that metal palladium as a plating catalyst adheres to the extremely minute irregularities. Thereby, it is considered that the bond at the interface between the parent plating layer 3 and the catalyst 5 becomes strong.
  • the entire surface of the remaining resist layer is exposed to ultraviolet rays, and then the resist layer is removed with a developer.
  • the plated product 10 on which a target pattern is formed can be manufactured.
  • 4A to 5C are process diagrams showing a method for manufacturing a wiring pattern of the present embodiment.
  • a description will be given on the assumption that a metal wiring is formed by a plating process to manufacture a plated product in which two metal wirings intersect.
  • a coating liquid 3A is formed on the surface of the support 2 by applying a coating solution using an ultraviolet curable resin as a binder. Thereafter, the coating film 3A is irradiated with ultraviolet rays L through a mask M provided with an opening Ma at a position corresponding to a region where the metal wiring is formed and a light shielding portion Mb in a region where the metal wiring is not formed. To expose.
  • a catalyst (not shown) used for electroless plating is applied to the parent plating layer 13 over the entire surface of the support 2, and then the electroless plating solution is brought into contact with the surface of the support 2.
  • the metal ions dissolved in the electroless plating solution can be reduced and deposited, and the metal wiring 16 can be formed on the surface of the parent plating layer 13.
  • the catalyst adheres to a portion (indicated by reference numeral 2x in the figure) where the parent plating layer 13 is not formed on the surface of the support 2. It is conceivable that plating is also applied to a portion where the parent plating layer 13 is not formed by contacting the plating solution. However, unlike the parent plating layer 13, the portion indicated by reference numeral 2x does not contain alumina particles having extremely fine irregularities, and therefore metal palladium that is an electroless plating catalyst is difficult to adhere.
  • the metal deposited by reduction of metal ions in the electroless plating solution is formed so as to bite into the extremely fine irregularities of the alumina particles, so that adhesion can be obtained by a so-called anchor effect.
  • the anchor effect is hardly exhibited.
  • the metal wiring (conductive member) 16 is selectively formed on the surface of the parent plating layer 13. Can be formed.
  • a coating liquid containing an ultraviolet curable resin as a binder is applied to the surface of the support 2 and exposed and developed through a mask while partially overlapping the metal wiring 16.
  • Crossing parent plating layers 23 are formed.
  • a resist layer 24 having an opening 24a is formed on the parent plating layer 23 by the same method as in the above-described FIGS. 3A and 3B, and the same method as in the above-described FIG. 3C.
  • a catalyst (electroless plating catalyst) 25 used for electroless plating is applied to the parent plating layer 23 exposed in the opening 24a of the resist layer 24.
  • the electroless plating solution ES is brought into contact with the parent plating layer 23 exposed in the opening 24a, thereby depositing metal on the surface of the catalyst 25 and selectively forming the metal wiring 26 in the opening 24a. be able to. Since the catalyst 25 is formed at a position on the surface of the parent plating layer 23 and not in contact with the lower metal wiring 16, the metal wiring 16 and the metal wiring 26 are not in contact with each other.
  • the plated product 20 in which the metal wiring 16 and the metal wiring 26 intersect can be manufactured.
  • the parent plating layer 23 has insulating properties as a whole. Therefore, by changing the concentration of the coating solution and the type of solvent for forming the parent plating layer 23, the thickness of the parent plating layer 23 is increased to such an extent that dielectric breakdown does not occur at the voltage used. An insulating layer between the metal wiring 16 and the metal wiring 26 can be formed.
  • the metal wiring formed on the catalyst can hardly be peeled off. Since the member for plating has high transparency, the portion where the metal wiring of the plated product is not formed exhibits high transparency.
  • the plated product 10 manufactured by the method of the present embodiment can be increased in thickness or formed as a multilayer metal film by performing further electroless plating or electroplating as necessary. It is.
  • the present invention is not limited to this.
  • FIGS. 6A to 6E after forming the metal wiring 6 on the parent plating layer 3 provided on the surface of the support 2 (FIG. 6A), the metal wiring 6 is covered, A parent plating layer 33 having a thickness that can be used as an insulating layer of the metal wiring 6 is selectively formed (FIG. 6B). Then, after forming the resist 34 having the opening 34a (FIG. 6C), a catalyst 35 for electroless plating (electroless plating catalyst) 35 is applied, and electroless plating is performed to form the metal wiring 36 (FIG. 6). 6D). Thereafter, by removing the resist, it is possible to form a plated product 30 in which metal wirings are laminated in multiple layers.
  • the parent plating layer is patterned by selectively exposing the photocurable resin.
  • the present invention is not limited to this.
  • the parent plating layer is formed on the entire surface of the support. After that, the parent plating layer may be patterned by selectively removing unnecessary portions of the parent plating layer.
  • the metal wiring can be formed on the PET substrate by forming the metal wiring with the formed plating film.
  • the plating member having a parent plating layer formed on the film is wound up in a roll shape, and conveyed while unwinding the plating member.
  • the metal wiring can be formed on the PET film in a so-called roll-to-roll process in which the manufactured plated product is wound into a roll.
  • the plating member When performing electroless plating using such a process, in the manufacturing method described above, since the alumina particles contained in the parent plating layer are as small as 100 nm or less, the plating member exhibits high transparency, and the film is rolled. When the film is wound on, the parent plating layer exhibits high followability, and the parent plating layer is less likely to crack or peel off. Therefore, it is possible to manufacture a high-quality plated product with high productivity.
  • a resist material (SUMIRESIST PFI-34A6, manufactured by Sumitomo Chemical Co., Ltd.) is spin-coated on the surface of the plating member on which the parent plating layer is formed or the surface on which the treatment layer is formed, and heated at 90 ° C. for 30 minutes ( A resist layer was formed by pre-baking.
  • the spin coating conditions were 1000 rpm for 10 seconds, and a resist layer having a thickness of about 1 ⁇ m was formed.
  • an ultraviolet ray having an intensity of 30 mW / cm 2 is exposed through a photomask for 6 seconds, heated at 110 ° C. for 30 minutes (post-baked), and then immersed in a 2.38% TMAH solution for 5 minutes.
  • the mask pattern was developed on the layer to form openings.
  • Electroless plating method About the member for plating in which the resist layer was formed, ultrasonic water washing was performed at room temperature for 30 seconds, and then the catalyst colloid solution for electroless plating (Melplate Activator 7331, manufactured by Meltex) was added at room temperature. It was immersed for 300 seconds, and the catalyst was attached to the parent plating layer or the treatment layer exposed at the opening of the resist layer.
  • the catalyst adhering to the opening of the resist layer was immersed in a catalyst activator for electroless plating (Melplate PA-7340, manufactured by Meltex) at room temperature for 300 seconds. Activated.
  • a catalyst activator for electroless plating Melplate PA-7340, manufactured by Meltex
  • the surface is washed with water and dried, and the entire surface including the remaining resist layer is exposed to ultraviolet light having an intensity of 30 mW / cm 2 for 2 minutes, and then immersed in an aqueous NaOH solution having a concentration of 50 g / L for 2 minutes. The layer was removed, and a plated product was produced.
  • FIG. 7A and 7B are photographs showing the results of a reference example in which electroless plating was applied to a plating member having a parent plating layer or a treatment layer formed on the surface of a 50 mm ⁇ 50 mm square glass plate by a vacuum deposition method. is there.
  • FIG. 7A is a photograph showing the result of electroless plating on the Al 2 O 3 layer
  • FIG. 7B is a photograph showing the result of electroless plating on the SiO 2 layer.
  • dark colored parts (indicated by symbol A in the figure) expressing letters and patterns are parts where a plating film is formed by electroless plating.
  • a pattern by metal plating is formed on the Al 2 O 3 layer, whereas a pattern by metal plating is not formed on the SiO 2 layer as shown in FIG. 7B.
  • FIG. 8 is an enlarged photograph after electroless plating is performed on the Al 2 O 3 layer shown in FIG. 7A, and it was confirmed that a good pattern could be formed up to 3 ⁇ m / 3 ⁇ m by L / S.
  • Example 1 colloidal alumina particles (manufactured by Aldrich) are used as the alumina particles, and a parent plating layer using an ultraviolet curable acrylic resin (Art Resin UN-3220HA, manufactured by Negami Kogyo Co., Ltd.) as the binder is used. A member was created. The sample of the obtained member for plating was subjected to electroless plating, and the adhesion and transparency of the parent plating layer were evaluated.
  • an ultraviolet curable acrylic resin Article Resin UN-3220HA, manufactured by Negami Kogyo Co., Ltd.
  • FIG. 9 is a TEM image of the colloidal alumina particles used in this example, and is a granular nanoparticle having a volume average particle diameter of about 20 nm using a separate measuring instrument based on the dynamic light scattering method. It was confirmed.
  • a plurality of coating solutions having different alumina concentrations relative to the binder are prepared, applied to a 50 mm ⁇ 50 mm square PET substrate, dried, and then cured by irradiating with ultraviolet rays, and a plurality of parent plating layers Formed.
  • the coating liquid is applied onto a substrate by spin coating (3000 rpm ⁇ 30 seconds) and dried, and then ultraviolet rays of 365 nm are emitted using an ultraviolet irradiation device (Multilight, manufactured by USHIO INC.). Irradiation was performed under the conditions of illuminance: 37 mW / cm 2 and irradiation time: 40 seconds (irradiation amount: 1480 mJ / cm 2 ). Then, it heated at 120 degreeC for 2 minute (s), and formed the parent plating layer.
  • an ultraviolet irradiation device Multilight, manufactured by USHIO INC.
  • concentration of the alumina with respect to the binder in a coating liquid was prescribed
  • the alumina density was 3.97 g / cm 3 and the binder density was 1.19 g / cm 3, which was converted to weight from these values.
  • the coating solution was prepared by mixing with a 2% by mass methanol solution. In addition, 3% by mass of a polymerization initiator (irgacure 1173, manufactured by Ciba Specialty Chemicals) was added to the coating solution and used.
  • the solution was adjusted to form a parent plating layer.
  • concentration of alumina with respect to the binder may be referred to as “alumina content”.
  • FIGS. 10A to 10C are photographs of metal wiring prepared by electroless nickel-phosphorus (NiP) plating on the parent plating layer.
  • FIGS. 10A and 10B are parent plating layers having an alumina content of 5% by volume.
  • the photograph shown about a sample and FIG. 10C are photographs shown about the parent plating layer sample of alumina content rate 0 volume%.
  • FIG. 12A is a diagram showing the evaluation results of translucency in a portion where each metal-plated product is not subjected to metal plating, and shows the transmittance with respect to d-line (587 nm). As shown in the figure, it can be seen that when the alumina content is 5% by volume or more, the transmittance is 98% or more, and there is almost no decrease in the transmittance.
  • FIG. 12B shows the wavelength dependence of translucency of a parent plating layer produced with an alumina content of 30% by volume.
  • the alumina particles used in this example have an average particle size (volume average) of about 20 nm, and since the particle size is smaller than the visible light wavelength, light scattering is extremely small, so long as the light has a wavelength in the visible light region. It was found that the transmittance decrease is very small even in the short wavelength region.
  • FIG. 13 is a photograph showing an evaluation result of a cross-cut tape test evaluation after plating for a plated product having electroless plating applied to the entire surface.
  • the evaluation was performed in accordance with JISK5600-5-6 (General coating test method-Part 5: Mechanical properties of coating film-Section 6: Adhesion (cross-cut method)).
  • FIG. 14 is a table summarizing the evaluation results shown in FIGS.
  • the alumina content in the parent plating layer is preferably 5% by volume or more and 99% by volume or less in this example. Even when the alumina content is 99% by volume (that is, the binder content is 1% by volume), the parent plating layer in this example can sufficiently exhibit adhesion to the substrate and is difficult to peel off. Was found to be possible.
  • Example 2 In this example, a coating solution having an alumina content of 5% by volume was applied to a 50 mm ⁇ 50 mm square PET substrate in the same manner as in Example 1 and dried, and then 365 nm via a photomask. Were irradiated under the conditions of irradiance: 30 mW / cm 2 and irradiation time: 30 seconds (irradiation amount: 900 mJ / cm 2 ). Next, after heating at 120 ° C. for 2 minutes, the whole substrate was developed by sonication while being immersed in acetone to form a parent plating layer. The immersion time was 10 seconds.
  • Example 3 In this example, first, a 1% by mass epoxysilane coupling agent was applied to a 50 mm ⁇ 50 mm square PET substrate by spin coating, dried, and heated at 120 ° C. for 5 minutes for surface treatment.
  • the coating solution was prepared by mixing 0.1 g of 20 mass% colloidal alumina (manufactured by Aldrich), 0.35 g of 10 mass% methanol solution of binder, and 0.35 g of 10 mass% PGMEA solution of binder.
  • As the binder an ultraviolet curable acrylic resin (Art Resin UN-3220HA, manufactured by Negami Kogyo Co., Ltd.) was used, and 3% by mass of the above polymerization initiator was added.
  • the whole substrate was subjected to ultrasonic treatment for 10 seconds while being immersed in acetone to form a parent plating layer.
  • electroless plating was performed by the method described above.
  • FIG. 16A is a photograph of the metal wiring obtained by performing electroless plating on the 1 mm-wide parent plating layer
  • FIG. 16B is an optical microscope image of the obtained metal wiring.
  • metal wiring was formed along the parent plating layer formed by selective ultraviolet irradiation (FIG. 16A), and no rough or missing portions (that is, portions that were not plated) were found on the surface of the metal wiring. . Therefore, it was confirmed that a patterned metal wiring can be created without forming a resist layer.
  • Example 4 In this example, first, a parent plating layer having an alumina content of 5% by volume is formed on the entire surface of a 50 mm ⁇ 50 mm square PET substrate by the same method as in Example 1, and the resist layer is formed by the above-described method. After creation, electroless plating was selectively performed to create NiP wiring (metal wiring). In the following description, this metal wiring is referred to as “first metal wiring”.
  • the coating liquid was prepared by mixing 0.25 g of a 2% by mass methanol dispersion of colloidal alumina (manufactured by Aldrich) and 1.43 g of a 2% by mass methanol solution of a binder, and further adding 1 g of 1-propanol. It adjusted by mixing.
  • an ultraviolet curable acrylic resin (Art Resin UN-3220HA, manufactured by Negami Industrial Co., Ltd.) was used.
  • FIG. 17A is a photograph of the created first metal wiring
  • FIG. 17B is an enlarged photograph of the first metal wiring. It can be seen that a flat wiring with few irregularities is formed.
  • a silane coupling agent (KBE903, manufactured by Shin-Etsu Silicone) was applied by spin coating on the entire surface of the PET substrate where the first metal wiring was formed.
  • Example 2 After applying a coating solution having an alumina content of 5% by volume, selectively irradiating with ultraviolet rays through a photomask and heating at 120 ° C. for 1 minute, Development with acetone selectively formed a parent plating layer.
  • the selectively formed parent plating layer is referred to as a “selective parent plating layer”.
  • FIG. 18A is a photograph of the substrate on which the selective parent plating layer is formed
  • FIG. 18B is an enlarged photograph of the selective parent plating layer in the region surrounded by the broken line in FIG. 18A.
  • the filler was sufficiently dispersed in the selective parent plating layer, and aggregates and the like were not confirmed.
  • the film thickness was about 350 nm.
  • the metal patterned on the selective parent plating layer by performing the formation of the resist layer and the electroless plating on the entire surface of the PET substrate where the selective parent plating layer is formed by the above-described method.
  • a wiring (NiP wiring) was formed.
  • the surface of the metal wiring could be covered with Au by performing electroless gold (Au) plating.
  • Au electroless gold
  • FIG. 19 is a cross-sectional SEM image of the multilayer wiring structure produced by the above procedure.
  • continuity between the first metal wiring and the second metal wiring was measured with a tester, no leakage current was confirmed. Therefore, it was confirmed that the parent plating layer of this example can also be used as an insulating layer.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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  • Manufacturing & Machinery (AREA)
  • Chemically Coating (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un motif de câblage, comprenant les étapes consistant à : former de façon sélective une couche de placage parente (13) sur un support optiquement transparent (2), la couche de placage parente comprenant un matériau de base optiquement transparent et des particules d'alumine ayant un diamètre moyen de particule de 100 nm ou moins ; amener un catalyseur à être supporté sur au moins une partie de la surface de la couche de placage parente (13) ; et amener une solution de dépôt autocatalytique en contact avec la surface de la couche de placage parente (13) et effectuer un dépôt autocatalytique.
PCT/JP2012/070206 2011-08-15 2012-08-08 Procédé de fabrication d'un motif de câblage et élément pour le placage WO2013024767A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014197143A (ja) * 2013-03-29 2014-10-16 Jsr株式会社 導電性パターン形成方法、樹脂組成物、導電性パターンおよび電子回路
JP2015089951A (ja) * 2013-11-05 2015-05-11 キヤノン・コンポーネンツ株式会社 金属皮膜付物品及びその製造方法並びに配線板

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006150353A (ja) * 2004-11-26 2006-06-15 Rohm & Haas Electronic Materials Llc Ｕｖ硬化性触媒組成物
JP2008208389A (ja) * 2007-02-23 2008-09-11 Kaneka Corp 無電解めっき用材料、積層体及びプリント配線板
JP2009068106A (ja) * 2007-08-22 2009-04-02 Osaka Prefecture 金属皮膜を有するポリマー基材の製造方法及びポリマー基材。
JP2010173170A (ja) * 2009-01-29 2010-08-12 Toppan Printing Co Ltd カード

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006150353A (ja) * 2004-11-26 2006-06-15 Rohm & Haas Electronic Materials Llc Ｕｖ硬化性触媒組成物
JP2008208389A (ja) * 2007-02-23 2008-09-11 Kaneka Corp 無電解めっき用材料、積層体及びプリント配線板
JP2009068106A (ja) * 2007-08-22 2009-04-02 Osaka Prefecture 金属皮膜を有するポリマー基材の製造方法及びポリマー基材。
JP2010173170A (ja) * 2009-01-29 2010-08-12 Toppan Printing Co Ltd カード

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014197143A (ja) * 2013-03-29 2014-10-16 Jsr株式会社 導電性パターン形成方法、樹脂組成物、導電性パターンおよび電子回路
JP2015089951A (ja) * 2013-11-05 2015-05-11 キヤノン・コンポーネンツ株式会社 金属皮膜付物品及びその製造方法並びに配線板

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