WO2012165168A1 - 金属膜パターンが形成された樹脂基材 - Google Patents
金属膜パターンが形成された樹脂基材 Download PDFInfo
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- WO2012165168A1 WO2012165168A1 PCT/JP2012/062719 JP2012062719W WO2012165168A1 WO 2012165168 A1 WO2012165168 A1 WO 2012165168A1 JP 2012062719 W JP2012062719 W JP 2012062719W WO 2012165168 A1 WO2012165168 A1 WO 2012165168A1
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- latent image
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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
- H05K3/10—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
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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
- H05K3/10—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/10—Intaglio printing ; Gravure printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/26—Printing on other surfaces than ordinary paper
- B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
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- 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
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
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- 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
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
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- 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
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- 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
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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
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
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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
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
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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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
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- 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
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
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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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
- H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
- H05K2203/0793—Aqueous alkaline solution, e.g. for cleaning or etching
Definitions
- This invention relates to the manufacturing method of the resin base material in which the metal film pattern was formed in the surface.
- the resin material on which the metal film pattern is formed has been used for a long time in the fields of electronic parts and ornaments.
- a film in which a metal film is formed in a circuit pattern on the surface of a resin substrate has been widely used as a flexible printed wiring board or the like.
- the formation of a metal film pattern on the surface of a resin base material involves first producing a copper-clad laminate in which a film-like base material and a copper foil are bonded together with an adhesive, and a desired pattern is formed on this.
- a method of drawing and dissolving and removing a copper foil portion other than a pattern in an etching process has been generally used.
- the conventional method has a problem that the heat resistance of the adhesive for bonding the resin and the copper foil is low and the adhesion of the metal film is low. Further, in the above etching process, since it is difficult to control the dissolution rate of the metal film, it may be difficult to accurately etch the metal film pattern. In addition, it is known that the bonding interface between the metal film and the resin is eroded by the etching solution, and particularly in the case of a fine pattern, there is a risk of reducing the adhesion.
- a method of forming a metal film on the surface of a resin film without using an adhesive has been developed, and a vapor deposition method and a sputtering method are being carried out.
- the adhesion reliability may not be sufficient.
- sputtering methods are expected to have high adhesion strength, but these methods require an etching process to form a metal film pattern, and it is difficult to cope with pattern miniaturization. Is left.
- the direct metallization method is a technique for which high adhesion reliability between a metal film and a resin is expected.
- Patent Documents 1, 2, and 3 a polyimide resin film is alkali-treated to open an imide ring, a metal salt is adsorbed on the formed carboxyl group, and the metal salt is reduced to form a metal film.
- this method since a metal film is formed through a functional group formed on a polyimide resin film without using an adhesive, high adhesion reliability is expected.
- these methods are the same as the conventional methods in that a metal film is formed on the entire surface of the substrate in advance, and then an etching process is required to pattern the metal film. In the etching process, there is a possibility that the metal film at the resin interface may be eroded, and there is still a problem that it is difficult to cope with a fine line pattern with high adhesion reliability.
- Patent Document 4 an alkaline aqueous solution is applied to an inorganic film forming portion of a polyimide resin base material using an inkjet method to open the imide ring, and metal ions are adsorbed to this portion to form a metal salt, A method for reducing the salt to form an inorganic film pattern is disclosed. According to this method, it is shown that an inorganic thin film pattern can be formed on a polyimide resin substrate without using an etching process.
- the inkjet method generally discharges a low-viscosity solution, there are problems such as bleeding and repelling of the alkaline solution on the polyimide resin, and it may be difficult to form a fine pattern.
- the problem to be solved by the present invention is to provide a method capable of efficiently forming a metal film pattern having excellent adhesion and precision on a resin substrate using a low concentration metal ion solution. .
- a method for producing a resin base material having a metal film pattern comprising the following steps (a) to (e): (A) A step of pattern-printing a latent image agent on the surface of a resin substrate (b) A step of bringing a metal ion-containing solution into contact with a portion where the latent image agent is printed to generate a metal salt (c) A step of bringing the metal salt into contact with an acidic treatment solution containing a reducing agent; (d) a step of forming an electroless nickel plating film on the portion where the latent image agent is printed; and (e) an electroless copper on the surface of the nickel plating film.
- the latent image agent is an alkaline solution containing one or more metal hydroxides selected from the group consisting of potassium hydroxide and sodium hydroxide.
- the viscosity of the latent image agent (viscosity when the rotor rotation speed is 0.5 rpm at 25 ° C. using a cone plate viscometer) is 50 to 500 Pa ⁇ s, 1) to 5) The manufacturing method as described in. 7) The production method according to any one of 1) to 6), wherein the latent image agent is pattern-printed using a gravure printing technique. 8) The production method according to 7), wherein the gravure printing plate used in the gravure printing technique has a depth of 1 to 10 ⁇ m and a line width of 10 to 50 ⁇ m.
- a resin substrate having a metal film pattern with high adhesion reliability can be manufactured.
- no adhesive is used at the bonding interface between the metal film and the resin.
- the etching process for pattern formation is not used. Therefore, according to the present invention, it is possible to solve the problem of lowering the adhesion reliability of the metal film due to the erosion of the adhesive and the etching solution, which has been a problem in the prior art.
- an acidic treatment liquid containing a reducing agent is used in the metal salt reduction step, so that metal ions are not easily removed in the subsequent step, and therefore, processing is performed at a metal ion concentration that is lower than that of the conventional technique. Can be practical. Furthermore, it is possible to form a fine pattern with high precision by adjusting the viscosity of the latent image agent or adopting a gravure printing technique.
- the method of the present invention comprises a step (a) (pattern printing step), a step (b) (metal salt generation step), a step (c) (reduction step), a step (d) (nickel plating film forming step), and a step. (E) (Copper plating film forming step).
- a) pattern printing step
- a step (b) metal salt generation step
- a step (c) reduction step
- a step (d) nickel plating film forming step
- E Copper plating film forming step
- the latent image agent (2 in FIG. 1) is pattern-printed on the surface of the resin substrate (1 in FIG. 1).
- the resin base material constituting the present invention any resin substrate whose surface is modified by the latent image agent of the present invention may be used.
- examples thereof include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyimide (PI).
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PI polyimide
- a polyimide resin is a polymer having a cyclic imide structure in the main chain and is excellent in heat resistance, mechanical strength, chemical resistance, electrical insulation, and the like.
- “Kapton” (trade name) manufactured by DuPont and “Upilex” (trade name) manufactured by Ube Industries, Ltd. are known.
- the shape of the substrate is not particularly limited, and a resin film or a resin plate can be used.
- a film having a film thickness of about 12 micrometers ( ⁇ m) to 50 ⁇ m is preferably used.
- a latent image agent is applied to the surface of the resin base material by using a pattern printing method, whereby the imide ring of the resin in contact with the latent image agent is cleaved to generate a carboxyl group.
- a modified layer is formed. That is, the modified layer is formed in a pattern on the surface of the resin substrate by this process.
- the latent image agent is an alkaline solution containing an alkali compound such as potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, ethylenediamine, and preferably potassium hydroxide, sodium hydroxide, calcium hydroxide, And an alkaline solution containing one or more metal hydroxides selected from the group consisting of magnesium hydroxide. From the viewpoint of drug cost, an alkaline solution containing at least one metal hydroxide selected from potassium hydroxide and sodium hydroxide is more preferable.
- an alkaline solution containing at least one metal hydroxide selected from potassium hydroxide and sodium hydroxide is more preferable.
- the alkali concentration (alkali compound concentration) of the latent image agent is not particularly limited, but is preferably 0.01M to 10M, more preferably 0.5M to 5M. If the alkali concentration is lower than the above range, the reforming reaction on the surface of the resin substrate becomes insufficient, and it may be difficult to form a metal film. On the other hand, if the alkali concentration is high, the resin is excessively modified and it becomes difficult to form a fine pattern.
- auxiliary agents such as fillers, thixotropic agents, binder resins, organic solvents, thickeners and the like can be appropriately added to the latent image agent to control the printability.
- the viscosity of the latent image agent can be adjusted with these auxiliaries to improve the printability.
- the viscosity of the latent image agent in the present invention is not particularly limited.
- the viscosity is preferably 50 to 500 Pa ⁇
- the latent image agent in the range of s, more preferably in the range of 100 to 400 Pa ⁇ s.
- the print pattern line width can be reduced, and a fine pattern can be printed.
- the linear shape exemplified in FIG. 2 or the dot shape exemplified in FIG. 3 can be selected.
- 2A shows the width of the engraving groove
- FIG. 2B shows the depth of the engraving groove.
- 3A is the width of one side of the concave portion of the dot-shaped engraving groove
- FIG. 3B is the depth of the concave portion of the dot-shaped engraving groove
- FIG. 3C is the concave portion and the concave portion of the dot-shaped engraving groove. Indicates the distance between the centers.
- the depth of the engraving groove (B in FIG. 2) is 1 ⁇ m to 10 ⁇ m, preferably 3 ⁇ m to 8 ⁇ m. If the depth of the linear engraving groove is small (the depth is shallow), the latent image agent cannot be sufficiently retained, and the print pattern of the latent image agent on the resin may be missing or disconnected. When the depth is large (the depth is deep), the amount of the latent image agent becomes excessive and the line width is thick, so that it may be difficult to print a fine pattern.
- the line width (A in FIG. 2) of the linear engraving groove is 10 ⁇ m to 50 ⁇ m, preferably 15 ⁇ m to 25 ⁇ m. If the line width is narrow, the latent image agent cannot be sufficiently retained, and the printing pattern of the latent image agent on the resin substrate may be missing or disconnected. If the line width is wide, the line width of the print pattern becomes thick, and it may be difficult to print a fine pattern.
- a line may be formed by an intaglio having concave portions of continuous dot-shaped engraving grooves (dots) (FIG. 3).
- the depth of the concave portion of the dot ((B) in FIG. 3) is 1 ⁇ m to 10 ⁇ m, preferably 3 ⁇ m to 8 ⁇ m.
- the width of one side of the dot recess ((A) in FIG. 3) is 10 ⁇ m to 50 ⁇ m, preferably 15 ⁇ m to 25 ⁇ m.
- the distance between the recesses and the center of the recesses ((C) in FIG. 3) is preferably 15 ⁇ m to 25 ⁇ m.
- the line width of the printed pattern thus formed on the resin substrate is not particularly limited, but the preferable line width is 10 to 100 ⁇ m, more preferably 20 to 50 ⁇ m.
- the latent image agent is applied to the resin base material and held for a certain period of time, and then the latent image agent is removed by washing with water.
- the holding time the surface of the resin base material where the latent image agent is adhered is modified to form a carboxyl group.
- the holding time and holding temperature are not particularly limited, but if the holding time is long and the holding temperature is high, the reforming reaction is promoted. Therefore, the holding temperature is preferably 10 ° C. to 80 ° C. in order to avoid excessive or insufficient reaction. Is 20 ° C. to 50 ° C.
- the holding time is 10 seconds or longer, preferably 15 seconds or longer.
- the upper limit of the holding time is not limited, but is preferably about 10 minutes.
- Step (b) Subsequently, in the step (b), a metal salt (3 in FIG. 1) is generated by bringing the metal ion-containing solution into contact with the portion where the latent image agent is printed in the step (a). That is, the metal ion-containing solution is brought into contact with the surface of the resin base material modified with the latent image agent.
- the metal ions include one or more selected from palladium ions, copper ions, and nickel ions.
- the metal ion is coordinated to the carboxyl group generated on the polyimide resin substrate in the step (a), and a metal salt is formed.
- the metal ion concentration in the metal ion-containing solution is preferably 0.01 mM to 50 mM, more preferably 0.05 mM to 20 mM, still more preferably 0.05 mM to 10 mM, and particularly preferably 0.08 mM to 0. .9 mM.
- an acidic treatment liquid containing a reducing agent is used in the metal salt reduction step, there is no loss of metal ions in the subsequent step. Therefore, it can be processed at a metal ion concentration lower than that of the conventional technique, and is characterized by high practicality.
- the solvent used in the metal ion-containing solution is not particularly limited, but is preferably water.
- Examples of the method of bringing the resin base material into contact with the metal ion-containing solution include a method of immersing the resin base material in the metal ion-containing solution and a method of spraying the metal ion-containing solution on the resin base material in a spray form. It is done.
- the reaction temperature when the resin substrate is brought into contact with the metal ion-containing solution is 10 ° C. to 80 ° C., preferably 30 ° C. to 50 ° C.
- the contact time of the metal ion-containing solution is preferably 10 seconds to 800 seconds, more preferably 60 seconds to 500 seconds.
- the resin substrate After contact with the metal ion-containing solution, the resin substrate is washed with water to remove non-specifically attached metal ions. At this time, if ultrasonic cleaning or the like is performed, cleaning can be performed efficiently.
- Step (c) In the step (c), the resin substrate is brought into contact with an acidic treatment liquid containing a reducing agent, and the metal salt formed on the resin substrate surface in the step (b) is reduced (4 in FIG. 1).
- the reducing agent used in the acidic treatment liquid containing the reducing agent include dimethylamine borane, sodium hypophosphite, hydrazine, methanol, diethylmethylamine, and ascorbic acid.
- dimethylamine borane is particularly preferable because it can be used in an acidic region.
- the reducing agent concentration of the acidic treatment solution containing the reducing agent is preferably 1 mM to 100 mM, more preferably 10 mM to 30 mM.
- the solvent used for the acidic processing liquid containing the reducing agent of the present invention is not particularly limited, water or the like is preferable.
- the pH of the acidic treatment liquid containing the reducing agent of the present invention is preferably 6 or less, more preferably 2 to 6, and further preferably 3 to 5.9. If the pH is too high, there is a disadvantage that the metal salt formed on the surface of the resin substrate in step (b) falls off.
- the acidic treatment liquid containing the reducing agent of the present invention can be prepared by appropriately dissolving the reducing agent in an acidic buffer in order to maintain an appropriate pH range.
- Known acidic buffering agents can be used, and examples include 0.1 M citrate buffer and acetate buffer.
- the acidic treatment liquid containing the reducing agent of the present invention neutralizes the alkaline latent image agent applied to the resin, prevents re-modification of the resin, and has an effect of suppressing the dropping of the metal salt formed on the resin. is there. Therefore, as described above, a low-concentration metal ion-containing liquid can be used, and the metal salt can be efficiently reduced.
- the time for bringing the resin base material into contact with the acidic treatment liquid containing a reducing agent is 60 seconds to 600 seconds, preferably 180 seconds to 300 seconds.
- the contact temperature is 10 ° C. to 80 ° C., preferably 30 ° C. to 50 ° C.
- Step (d) In the step (d) of the present invention, an electroless nickel plating film (5 in FIG. 1) is formed at the site where the metal salt has been reduced in the step (c).
- An existing plating bath can be used for electroless nickel plating, and the above-described resin base material may be immersed in this plating bath.
- the plating reaction time and temperature can be appropriately adjusted according to the plating film thickness.
- the film thickness of the electroless nickel plating film in the present invention is 10 nm to 300 nm, preferably 20 nm to 200 nm.
- the electroless nickel plating film has a role as a seed layer for improving the adhesion to the resin base material, and exhibits its effect with a thin film in the above film thickness range.
- the resin base material is washed with water to remove the plating solution adhering non-specifically.
- an electroless copper plating film (6 in FIG. 1) is deposited on the electroless nickel plating film formed in the step (d).
- An existing plating bath can be used for electroless copper plating. Examples thereof include those using Rochelle salt, EDTA, quadrol, etc. as a complexing agent for copper, formaldehyde baths using formaldehyde as a reducing agent, and formaldehyde-free baths using glyoxylic acid or the like as a reducing agent.
- the electroless plating bath used in the present invention is more preferably a plating bath having a weak alkaline to neutral pH range in order to prevent re-modification of the resin base material.
- the reaction time and temperature of electroless copper plating can be appropriately adjusted according to the plating film thickness.
- the film thickness of the electroless copper plating film in the present invention can be adjusted according to the use of the product and is not particularly limited. However, from the viewpoint of productivity, it is preferably 0.5 ⁇ m to 10 ⁇ m, more preferably 1 ⁇ m to 6 ⁇ m. Range.
- the film thickness is preferably 0.5 ⁇ m to 10 ⁇ m, more preferably 1 ⁇ m to 6 ⁇ m, and the line width is preferably 20 to 100 ⁇ m through the above-described steps (a) to (e).
- a resin substrate on which a metal (copper) film pattern of 30 to 50 ⁇ m is formed can be obtained.
- the resin base material thus obtained can be suitably used for applications such as flexible circuit boards and RF tags.
- Example 1 A polyimide film (trade name “Kapton H”; manufactured by Toray DuPont) having a width of 30 cm and a thickness of 25 microns was cut into an appropriate size to obtain a polyimide resin substrate for latent image agent printing. Next, a latent image agent was pattern printed on the polyimide resin substrate using a gravure printing machine.
- a polyimide film (trade name “Kapton H”; manufactured by Toray DuPont) having a width of 30 cm and a thickness of 25 microns was cut into an appropriate size to obtain a polyimide resin substrate for latent image agent printing.
- a latent image agent was pattern printed on the polyimide resin substrate using a gravure printing machine.
- the latent image agent used here was prepared by containing potassium hydroxide (KOH) as an alkali compound at a concentration of 3M, and adding carboxymethylcellulose and a thixotropic agent as appropriate for viscosity adjustment.
- KOH potassium hydroxide
- the viscosity of the latent image agent was 370 Pa ⁇ s when measured using a cone plate viscometer under the conditions of a rotor rotation speed of 0.5 rpm at 25 ° C.
- a gravure plate having a linear engraving groove shown in FIG. 2 was used for gravure printing.
- the line width of the engraving groove of this plate was 21 ⁇ m and the depth was 5 ⁇ m.
- a printed pattern having a line width of 30 ⁇ m was formed on the polyimide resin substrate.
- the polyimide resin base material on which the latent image agent was printed was held at 25 ° C. for 60 seconds, followed by washing with water to remove the latent image agent.
- the polyimide resin substrate was immersed in a 0.1 mM palladium chloride aqueous solution at 40 ° C. for 300 seconds to form a palladium salt on the carboxyl group formed by the latent image agent. Thereafter, the polyimide resin was taken out and washed with water to remove palladium chloride adhering nonspecifically.
- the polyimide resin was immersed in an acidic treatment solution containing a reducing agent (pH 6; 0.1 M citrate buffer; 20 mM dimethylamine borane) at 40 ° C. for 180 seconds to reduce the palladium salt on the polyimide resin.
- a reducing agent pH 6; 0.1 M citrate buffer; 20 mM dimethylamine borane
- the polyimide resin was taken out from the acidic treatment liquid containing the reducing agent and washed with water to remove the non-specifically attached reducing agent.
- the polyimide resin was immersed in an electroless nickel plating bath having the composition shown in Table 1 for 1 minute at 35 ° C. to form a nickel film (film thickness: 100 nm). Thereafter, the polyimide resin was washed with water to remove the nickel plating solution, and then immersed in an electroless copper plating bath having the composition shown in Table 1 at 50 ° C. for 60 minutes to form an electroless copper plating film.
- a polyimide resin substrate on which a metal film pattern having a line width of 30 to 40 ⁇ m and a metal (copper) film thickness of 4 ⁇ m was formed was obtained.
- Example 2 A gravure plate having dot-shaped engraving grooves shown in FIG. 3 was used for gravure printing.
- the width of one side of the engraving groove dot of this plate was 20 ⁇ m, the depth was 6 ⁇ m, and the distance between the dot recess and the center of the recess was 22 ⁇ m.
- Other conditions were the same as in Example 1.
- a printed pattern having a line width of 27 ⁇ m was formed on the polyimide resin substrate.
- a polyimide resin having a metal film pattern with a line width of 30 to 40 ⁇ m and a metal film thickness of 4 ⁇ m was obtained by the same process as in Example 1.
- Example 3 The concentration of the aqueous solution of palladium chloride was 0.85 mM, 0.43 mM, 0.085 mM, 0.0085 mM, and the other conditions were the same as in Example 1 up to the electroless nickel plating step. As a comparison, a sample having a palladium chloride concentration of 0 mM was also carried out at the same time. The selective precipitation of nickel plating was evaluated. ⁇ : Not precipitated ⁇ : Deposited
- Example 3 In Example 3, about the thing by which precipitation of nickel plating was confirmed ((circle) determination), the electroless copper plating similar to Example 1 is performed, and the polyimide resin base material which has a metal film (electroless copper plating film) pattern is used. Obtained. Two polyimide resin base materials having the obtained metal film pattern were prepared, and the metal film surfaces were overlapped and joined by soldering. One of the joined two sheets was fixed and the other was peeled off for evaluation. ⁇ : Metal film peels from polyimide resin substrate ⁇ ; Metal film does not peel from polyimide resin substrate
- Example 4 The processing time (holding time) of the latent image agent with respect to the polyimide resin was set to 15 seconds, 60 seconds, 300 seconds, and 600 seconds, and the deposition properties of the electroless nickel plating and the printed pattern line width were evaluated. For comparison, a sample that was not processed (processing time 0 seconds) was evaluated at the same time. The other conditions were the same as in Example 1, up to the electroless nickel plating step. As a result, selective plating deposition was confirmed at the modified sites patterned with the latent image agent under all conditions of a processing time of 15 seconds or longer. Further, there was no effect on the print pattern line width due to the difference in processing time (Table 3).
- Example 5 A polyimide resin film having a thickness of 25 microns (trade name “Kapton H”; manufactured by Toray DuPont) was cut into an appropriate size to obtain a polyimide resin substrate for printing a latent image agent.
- a latent image agent having a viscosity of 26 to 389 Pa ⁇ s (conditions using a cone plate viscometer at 25 ° C. and a rotor rotational speed of 0.5 rpm) is used, and the polyimide resin base material is obtained using a gravure printing machine. The latent image agent was printed on the pattern.
- a gravure printing plate intaglio plate having the same linear engraving grooves as in Example 1 was used.
- the line width of the engraving groove of this gravure printing plate was 21 ⁇ m, and the depth was 5 ⁇ m.
- Examples 6 and 7 As an acidic treatment solution containing a reducing agent, 20 mM dimethylamine borane solution (0.1 M citrate buffer; pH 5.8) or 20 mM dimethylamine borane solution (0.2 M acetate buffer; pH 4.8). Using. The reduction treatment temperature was 25 ° C., 35 ° C., 50 ° C., and the treatment time (retention time) was 270 seconds. Other conditions were the same as in Example 1.
- the amount of palladium on the polyimide resin substrate was quantitatively determined by fluorescent X-ray analysis before and after contact with an acidic treatment solution containing a reducing agent for a certain period of time, and the residual amount after reduction treatment when the palladium amount before reduction treatment was taken as 100%.
- the amount of palladium was calculated as the metal retention (Table 5).
- a resin substrate having a metal film pattern with high adhesion reliability can be produced without using an adhesive or employing an etching process. Therefore, according to the present invention, it is possible to solve the problem of lowering the adhesion reliability of the metal film due to the erosion of the adhesive or the etching solution. Further, in the present invention, since an acidic treatment liquid containing a reducing agent is used in the metal salt reduction step, the metal ions are less likely to fall off, and therefore can be processed with a metal ion-containing solution having a lower concentration than conventional techniques. High practicality. Furthermore, it is possible to form a fine pattern with high precision by adjusting the viscosity of the latent image agent or adopting a gravure printing technique.
Abstract
Description
ダイレクトライティング技術では、ナノ銀ペーストをパターン印刷し、焼成して導電性パターンを形成する方法、パラジウム等のめっき触媒を含むインクを用いて直接パターンを描画し、インク上に無電解めっき膜を形成する方法などが実施されている。これらの方法では、パターンを直接描画することで、エッチング工程は省略されるという利点がある。しかし、ペーストやインクと樹脂との密着強度に課題がある。また、使用されるペーストやインクは非常に高コストである。さらに、この方法で得られた導電性パターンは電気抵抗が高く、金属膜としての電気特性が十分でないという問題があった。
1)下記(a)~(e)の工程を含むことを特徴とする、金属膜パターンを有する樹脂基材の製造方法。
(a)樹脂基材の表面に潜像剤をパターン印刷する工程
(b)潜像剤を印刷した部位に金属イオン含有溶液を接触させ、金属塩を生成する工程
(c)前記金属塩を、還元剤を含む酸性処理液に接触させ、金属塩を還元する工程
(d)潜像剤を印刷した部位に無電解ニッケルめっき膜を形成する工程
(e)前記ニッケルめっき膜の表面に無電解銅めっきを析出させる工程
4)前記金属イオンがパラジウムイオンである、1)~3)のいずれかに記載の製造方法。
5)前記酸性処理液が、pH6以下であることを特徴とする、1)~4)のいずれかに記載の製造方法。
7)グラビア印刷技術を用いて潜像剤をパターン印刷することを特徴とする、1)~6)のいずれかに記載の製造方法。
8)前記グラビア印刷技術で用いるグラビア印刷版の彫刻溝の深度が1~10μm、線幅が10~50μmである、7)記載の製造方法。
2:潜像剤
3:金属塩
4:金属
5:無電解ニッケルめっき膜
6:無電解銅めっき膜
(A):彫刻溝の幅(ドットの凹部の1辺の幅)
(B):彫刻溝の深度(ドットの凹部の深度)
(C):ドットの凹部と凹部の中心間の距離
本発明の工程(a)では、樹脂基材(図1中、1)の表面に潜像剤(図1中、2)をパターン印刷する。
ここで、本発明を構成する樹脂基材としては、本発明の潜像剤によって樹脂表面が改質されるものであれば良い。たとえばポリエチレンテレフタレート(PET)や、ポリエチレンナフタレート(PEN)、そしてポリイミド(PI)等が挙げられる。中でも、加水分解されやすいことから潜像印刷に有利であるポリイミド樹脂を用いることが好ましい。ポリイミド樹脂は、主鎖に環状イミド構造を持ったポリマーであり、耐熱性、機械的強度、耐薬品性、電気絶縁性等に優れた樹脂である。工業用製品としては、例えばデュポン社製「カプトン」(商品名)や宇部興産(株)製「ユーピレックス」(商品名)などが知られている。
続いて工程(b)では、工程(a)で潜像剤が印刷された部位に、金属イオン含有溶液を接触させて金属塩(図1中、3)を生成させる。すなわち、上述の潜像剤によって改質された樹脂基材表面に、金属イオン含有溶液を接触させる。
樹脂基材を前記金属イオン含有溶液に接触させる方法としては、金属イオン含有溶液中に樹脂基材を浸漬する方法や、樹脂基材にスプレー状に金属イオン含有溶液を噴きかける等の方法が挙げられる。
工程(c)では、樹脂基材を、還元剤を含む酸性処理液に接触させ、工程(b)で樹脂基材表面に形成された金属塩を還元する(図1中、4)。ここで還元剤を含む酸性処理液に用いる還元剤としては、ジメチルアミンボラン、次亜リン酸ナトリウム、ヒドラジン、メタノール、ジエチルメチルアミン、アスコルビン酸等が挙げられる。このうち、より酸性領域で使用できる点からジメチルアミンボランが特に好ましい。
還元剤を含む酸性処理液に接触させた後、樹脂基材を水洗し、非特異的に付着した還元剤溶液を除去する。
本発明の工程(d)では、前記工程(c)で金属塩を還元した部位に、無電解ニッケルめっき膜(図1中、5)を形成する。無電解ニッケルめっきには既存のめっき浴を使用することができ、このめっき浴に前述の樹脂基材を浸漬すればよい。めっきの反応時間と温度は、めっき膜厚に応じて適宜調整することができる。
無電解ニッケルめっき膜を形成後、樹脂基材を水洗し、非特異的に付着しためっき液を除去する。
本発明の工程(e)では、工程(d)で形成された無電解ニッケルめっき膜の上に、無電解銅めっき膜(図1中、6)を析出させる。無電解銅めっきには既存のめっき浴を使用することができる。例えば、銅の錯化剤としてロッシェル塩、EDTA、クワドロールなどを使用したもの、また、還元剤としてホルムアルデヒドを使用したホルムアルデヒド浴、還元剤としてグリオキシル酸等を用いたホルムアルデヒドフリー浴、などが挙げられる。本発明で用いる無電解めっき浴は、樹脂基材の再改質を防ぐため、弱アルカリ性から中性のpH範囲のめっき浴であるとより好ましい。
本発明における無電解銅めっき膜の膜厚は、製品の用途に合わせて調整することができ、特に限定されないが、生産性の観点から、好ましくは0.5μm~10μm、より好ましくは1μm~6μmの範囲である。
30cm幅、25ミクロン厚を有するポリイミド膜(商品名「カプトンH」;東レデュポン社製)を適当な大きさに切断し、潜像剤印刷用のポリイミド樹脂基材とした。次にグラビア印刷機を用いて、前記ポリイミド樹脂基材に潜像剤をパターン印刷した。
これによって、ポリイミド樹脂基材上に線幅30μmの印刷パターンが形成された。
つぎに、還元剤を含む酸性処理液からポリイミド樹脂を取り出して水洗し、非特異的に付着している還元剤を除去した。
上記工程によって、線幅が30~40μm、金属(銅)膜厚が4μmの金属膜パターンが形成されたポリイミド樹脂基材を得た。
グラビア印刷に、図3に示したドット形状の彫刻溝を有するグラビア版を用いた。この版の彫刻溝のドットの一辺の幅は20μm、深度は6μm、ドットの凹部と凹部の中心間の距離は22μmであった。その他の条件は実施例1と同様におこなった。
これによって、ポリイミド樹脂基材上に線幅27μmの印刷パターンが形成された。
また、実施例1と同様の工程によって、線幅が30~40μm、金属膜厚は4μmの金属膜パターンが形成されたポリイミド樹脂を得た。
塩化パラジウム水溶液の濃度を0.85mM、0.43mM、0.085mM、0.0085mMとし、その他の条件は実施例1と同様にして、無電解ニッケルめっき工程までを実施した。比較として、塩化パラジウム濃度0mMのサンプルも同時に実施した。
ニッケルめっきの選択的析出性を評価した。
×;析出しなかった
○;析出した。
実施例3において、ニッケルめっきの析出が確認されたもの(○判定)について、実施例1と同様の無電解銅めっきを行い、金属膜(無電解銅めっき膜)パターンを有するポリイミド樹脂基材を得た。得られた金属膜パターンを有するポリイミド樹脂基材を2枚準備し、金属膜面を重ねてはんだ付けにより接合した。この接合した2枚の一方を固定し、もう一方を引き剥がして評価した。
×;ポリイミド樹脂基材から金属膜が剥離
○;ポリイミド樹脂基材から金属膜が剥離せず
このことから、本発明により得られたポリイミド樹脂基材は、ポリイミド樹脂基材と金属膜との密着性が高いことを確認できた。
ポリイミド樹脂に対する潜像剤の処理時間(保持時間)を15秒、60秒、300秒、600秒とし、無電解ニッケルめっきの析出性、および印刷パターン線幅を評価した。尚、比較として処理を行わないもの(処理時間0秒)を同時に評価した。その他の条件は実施例1と同様にして、無電解ニッケルめっき工程までを実施した。
この結果、処理時間15秒以上のすべての条件において潜像剤によりパターンニングした改質箇所に選択的なめっき析出を確認した。また、処理時間の違いによる印刷パターン線幅への影響はなかった(表3)。
25ミクロン厚を有するポリイミド樹脂膜(商品名「カプトンH」;東レデュポン社製)を適当な大きさに切断し、潜像剤印刷用のポリイミド樹脂基材とした。
潜像剤として粘度が26~389Pa・s(コーンプレート型粘度計を用いて25℃でローター回転数が0.5rpmの条件)のものを使用し、グラビア印刷機を用いて前記ポリイミド樹脂基材に潜像剤をパターン印刷した。
還元剤を含む酸性処理液として、20mMのジメチルアミンボラン溶液(0.1Mクエン酸緩衝液;pH5.8)、または、20mMのジメチルアミンボラン溶液(0.2M酢酸緩衝液;pH4.8)を用いた。還元処理温度は25℃、35℃、50℃とし、処理時間(保持時間)は270秒であった。その他の条件は実施例1と同様におこなった。
還元剤を含む酸性処理液として、20mMジメチルアミンボラン溶液(0.2Mリン酸緩衝液;pH7.0)、及び、20mMの水素化ホウ素ナトリウム溶液(pH12.5)を用いた。その他の条件は実施例6と同様におこなった。酸性条件以外の条件下で還元処理を行うことで、金属保持率は60%以下となり、ポリイミド樹脂基材上のパラジウムの著しい脱離が確認された(表5)。
また、本発明では金属塩の還元工程で還元剤を含む酸性処理液を使用するため、金属イオンの脱落が少なく、したがって従来の技術と比べて低濃度の金属イオン含有溶液で加工することができ、実用性が高い。
さらに、潜像剤の粘度を調整したり、グラビア印刷技術を採用したりすることによって、精密度の高い微細パターンを形成することが可能となる。
Claims (8)
- 下記(a)~(e)の工程を含むことを特徴とする、金属膜パターンを有する樹脂基材の製造方法。
(a)樹脂基材の表面に潜像剤をパターン印刷する工程
(b)潜像剤を印刷した部位に金属イオン含有溶液を接触させ、金属塩を生成する工程
(c)前記金属塩を、還元剤を含む酸性処理液に接触させ、金属塩を還元する工程
(d)潜像剤を印刷した部位に無電解ニッケルめっき膜を形成する工程
(e)前記ニッケルめっき膜の表面に無電解銅めっきを析出させる工程 - 前記潜像剤が、水酸化カリウム及び水酸化ナトリウムからなる群から選ばれる1種以上の金属水酸化物を含むアルカリ性溶液であることを特徴とする、請求項1記載の製造方法。
- 前記金属イオン含有液の金属イオン濃度が0.01mM~0.9mMであることを特徴とする、請求項1又は2記載の製造方法。
- 前記金属イオンがパラジウムイオンである、請求項1~3のいずれかに記載の製造方法。
- 前記酸性処理液が、pH6以下であることを特徴とする、請求項1~4のいずれかに記載の製造方法。
- 前記潜像剤の粘度(コーンプレート型粘度計を用いて25℃でローター回転数を0.5rpmとしたときの粘度)が50~500Pa・sである、請求項1~5のいずれかに記載の製造方法。
- グラビア印刷技術を用いて潜像剤をパターン印刷することを特徴とする、請求項1~6のいずれかに記載の製造方法。
- 前記グラビア印刷技術で用いるグラビア印刷版の彫刻溝の深度が1~10μm、線幅が10~50μmである、請求項7記載の製造方法。
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US14/122,797 US9578751B2 (en) | 2011-05-30 | 2012-05-17 | Method for producing a resin substrate having a metal film pattern formed thereon |
KR1020137034714A KR101940467B1 (ko) | 2011-05-30 | 2012-05-17 | 금속막 패턴이 형성된 수지 기재 |
CN201280026276.6A CN103733738A (zh) | 2011-05-30 | 2012-05-17 | 形成金属膜图案的树脂基材 |
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KR101940467B1 (ko) | 2019-01-21 |
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