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WO2012014657A1 - Procédé de production de motifs métalliques - Google Patents

Procédé de production de motifs métalliques Download PDF

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Publication number
WO2012014657A1
WO2012014657A1 PCT/JP2011/065671 JP2011065671W WO2012014657A1 WO 2012014657 A1 WO2012014657 A1 WO 2012014657A1 JP 2011065671 W JP2011065671 W JP 2011065671W WO 2012014657 A1 WO2012014657 A1 WO 2012014657A1
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WO
WIPO (PCT)
Prior art keywords
anchor layer
electroless plating
metal
catalyst
metal pattern
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2011/065671
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English (en)
Japanese (ja)
Inventor
鈴木　眞一
智史 森
仲島　厚志
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta IJ Technologies Inc
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Konica Minolta IJ Technologies Inc
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Filing date
Publication date
Application filed by Konica Minolta IJ Technologies Inc filed Critical Konica Minolta IJ Technologies Inc
Publication of WO2012014657A1 publication Critical patent/WO2012014657A1/fr
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Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/0709—Catalytic ink or adhesive for electroless plating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0756—Uses of liquids, e.g. rinsing, coating, dissolving
    • H05K2203/0769—Dissolving insulating materials, e.g. coatings, not used for developing resist after exposure

Definitions

  • the present invention relates to a metal pattern manufacturing method for forming a metal pattern having excellent adhesion to a substrate.
  • a method for forming a metal pattern used in a circuit a method using a resist material has been performed. That is, after applying a resist material on a metal thin film and exposing a required pattern to light, unnecessary resist is removed by development, the exposed metal thin film is removed by etching, and the remaining resist portion is peeled off. Thus, a metal thin film forming method for forming a metal pattern has been widely used.
  • This metal pattern formation method uses the characteristic that the melting point is lowered by minimizing the particle size of the metal nanoparticles, and forms a circuit by performing a firing process at a relatively low temperature of about 200 to 300 ° C. It is a method to do. Although this technology certainly has the advantages of reducing man-hours and improving the utilization efficiency of raw materials, it is difficult to completely fuse metal particles together. In the process, there remains a problem that there are severe restrictions on the set temperature and other conditions.
  • a metal pattern forming method utilizing electroless plating technology has been proposed as a means for forming and depositing metal under mild conditions.
  • a method is disclosed in which a metal is formed by electroless plating after forming a circuit pattern with an ink containing a catalyst capable of forming a metal pattern by electroless plating (for example, Patent Document 1, (Refer nonpatent literature 1.).
  • a catalyst (precursor) is contained in an ink, and the ink is printed on a substrate to form a pattern. Thereafter, activation treatment and electroless plating are performed to form a metal pattern on the catalyst pattern.
  • Patent Documents 2 and 3 a method of forming an ink absorption layer made of polymer particles on a substrate and applying a catalyst ink on the ink absorption layer is disclosed (for example, see Patent Documents 2 and 3). Since the method disclosed in Patent Document 2 has a polymer layer, the adhesion is somewhat improved, but it is still not sufficient, and the ink absorption layer itself made of polymer particles has a high hygroscopicity, The reflow resistance (high temperature resistance) after storage for a long time in a humid environment was inferior. In addition, the method disclosed in Patent Document 3 is a method of forming a polymer water dispersion layer and then fusing it with heat to improve the hygroscopicity. At present, high humidity environment characteristics cannot be obtained.
  • the present invention has been made in view of the above problems, and its purpose is to have high adhesion to the substrate of the formed metal pattern, excellent heat resistance after storage in a high humidity environment (moisture absorption reflow resistance), and nothing. It is providing the manufacturing method of the metal pattern excellent in the electroplating property.
  • a method for producing a metal pattern comprising: a step of swelling or dissolving; and 3) a step of performing an electroless plating process.
  • a method for producing a metal pattern in which the formed metal pattern has high adhesion to the substrate, is excellent in heat resistance (moisture reflow resistance) after being stored in a high humidity environment, and is excellent in electroless plating properties. can do.
  • the substrate applied to form the metal pattern is formed of a material that has no absorbability for ink (liquid) such as insulating resin, glass or ceramic.
  • ink liquid
  • the substrate applied to form the metal pattern is formed of a material that has no absorbability for ink (liquid) such as insulating resin, glass or ceramic.
  • the present inventor has found that 1) a step of forming an anchor layer containing a polymer on the substrate, and 2) an electroless plating catalyst or precursor thereof on the anchor layer. And a step of swelling or dissolving the anchor layer, and 3) a step of performing an electroless plating process. It has been found that a metal pattern manufacturing method having high adhesion to a substrate of a metal pattern, excellent heat resistance (moisture reflow resistance) after storage in a high humidity environment, and excellent electroless plating properties can be realized. It is up to the present invention.
  • an anchor layer containing a polymer resin is formed on a substrate, and an ink (hereinafter simply referred to as “catalyst ink”) containing a catalyst or a precursor thereof for dissolving or swelling the anchor layer and a solvent is applied.
  • a catalyst ink hereinafter simply referred to as “catalyst ink”
  • the catalyst ink to be applied to the anchor layer mainly composed of a polymer resin formed on the substrate has a property of dissolving or swelling the anchor layer component, it is applied to the anchor layer.
  • the applied catalyst ink quickly penetrates into the anchor layer after application.
  • electroless plating treatment in the case where the ink contains a catalyst precursor, electroless plating treatment after activation treatment
  • not only the surface region of the anchor layer but also the catalyst ink A metal part is also formed in the penetrated interior.
  • the polymer component constituting the anchor layer and the metal are in a hybrid form, so that the metal is in a “rooted state” inside the anchor layer and high adhesion can be obtained.
  • the anchor layer swells or dissolves with the catalyst ink
  • the polymer is formed (cured) over the anchor layer surface and the inside of the anchor layer into which the catalyst ink has penetrated, and the hydrophobizing effect is expressed.
  • the anchor layer is transformed into a material that hardly absorbs moisture.
  • moisture absorption reflow property (which evaluates whether the metal part swells when exposed to high temperature after being stored in a high humidity environment) is important.
  • the high temperature in the hygroscopic reflow evaluation is assumed to be solder adhesion, and is usually 200 ° C. or higher, and is about 230 ° C. to 260 ° C. in recent lead-free.
  • the water absorption (hygroscopicity) of the base (or substrate) of the metal pattern is high, the hygroscopic reflow property is lowered.
  • the substrate has water absorption (hygroscopicity)
  • the moisture becomes water vapor (gas) when exposed to high temperature, and the bubble pattern swells on the surface of the metal film formed on the top (blister) ) Will occur.
  • film formation and hydrophobization are performed by permeation of the catalyst ink, so that the moisture absorption reflow characteristics are excellent.
  • the substrate on which the metal pattern is formed is not particularly limited as long as it has insulating properties.
  • the substrate on which the metal pattern is formed is not particularly limited as long as it has insulating properties.
  • a highly rigid material such as glass or ceramics, PET (polyethylene terephthalate)
  • PET polyethylene terephthalate
  • a polyimide film made of a resin such as polyimide.
  • the substrate used in the present invention may be subjected to a surface modification treatment such as a hydrophilic treatment on the surface from the viewpoint of improving adhesion or installing an anchor layer.
  • a surface modification treatment such as a hydrophilic treatment on the surface from the viewpoint of improving adhesion or installing an anchor layer.
  • Specific examples include plasma treatment, corona discharge treatment, UV irradiation treatment, silane coupling agent treatment, and the like.
  • Anchor layer containing polymer One feature of the present invention is that it includes a step of forming an anchor layer having a polymer (hereinafter also referred to as a polymer layer) on a substrate.
  • the polymer applicable to the present invention is not particularly limited, but polycarbonate, polyacrylonitrile, polystyrene, polyacrylic acid, polymethacrylic acid, polyacrylic ester, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyester , Polyamides, polyethers, polyurethanes, epoxy resins, phenol resins, and the like, and copolymers thereof.
  • the properties required for these polymers to be applied include 1) good adhesion between the substrate and the polymer of the anchor layer, and 2) adsorption of the electroless plating catalyst or its precursor in the ink and the polymer of the anchor layer. It is preferable to select from polymers having these characteristics.
  • the polymer of the anchor layer has a functional group that interacts with the substrate, and specifically includes a carboxyl group, an amino group, a hydroxyl group, and the like.
  • the functional group that can be adsorbed (coordinated) to the catalyst or its precursor in the ink include a carboxyl group, a hydroxyl group, a sulfonic acid group, an amino group, a cyano group, and an amide group.
  • the type and polymer characteristics such as molecular weight, functional group type, Tg, additive type and amount are appropriately selected so that the polymer constituting the anchor layer has a function of swelling or dissolving in the ink. It is preferable to do.
  • the film thickness of the anchor layer according to the present invention is preferably 0.05 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m. If the film thickness is 0.05 ⁇ m or more, the adhesion to the substrate is sufficient, and if it is 10 ⁇ m or less, it is possible to prevent a decrease in adhesion due to cohesive failure of the polymer in the anchor layer.
  • polymer fine particles (latex) As the polymer used in the step of forming the anchor layer, it is more preferable to use polymer fine particles (latex) as the polymer used in the step of forming the anchor layer.
  • polymer fine particles (latex) that can be used in the present invention include polycarbonate, polyacrylonitrile, polystyrene, polyacrylic acid, polymethacrylic acid, polyacrylic ester, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyester, Examples thereof include polymer fine particles (latex) composed of polyamide, polyether, polyurethane, epoxy resin, phenol resin, and the like.
  • the average particle size of the polymer fine particles is preferably 0.01 ⁇ m to 20 ⁇ m, more preferably 0.1 ⁇ m to 5 ⁇ m.
  • the coating liquid for forming the anchor layer according to the present invention may contain additives such as a solvent and a surfactant in addition to the polymer component.
  • the anchor layer according to the present invention can be formed by applying a polymer solution or a dispersion of polymer fine particles (latex), appropriately selecting from known coating methods, and coating and drying on a substrate.
  • the coating method include a roll coating method, a rod bar coating method, an air knife coating method, a spray coating method, and a dip method.
  • the ink (hereinafter also referred to as catalyst ink) used in the method for producing a metal pattern of the present invention has an electroless plating catalyst or a precursor thereof and a solvent.
  • the catalyst ink according to the present invention has a function of swelling or dissolving the anchor layer when applied onto a substrate having the anchor layer.
  • Swelling or dissolution as used in the present invention means that when the formed anchor layer is immersed in the catalyst ink, taken out and dried, there is no change in the mass of the anchor layer after immersion, but volume increase or cloudiness may be observed. Swelling is defined as dissolution when the mass of the anchor layer decreases after immersion. Therefore, as a criterion for determining whether the catalyst ink swells or dissolves the anchor layer, the anchor layer is immersed in the ink at 25 ° C. for 3 minutes, and the mass change before and after the immersion, the volume change, and visual observation (presence of cloudiness) are determined. Judge based.
  • the catalyst ink according to the present invention contains an electroless plating catalyst or a precursor thereof.
  • the electroless plating catalyst according to the present invention itself becomes a reactive core and forms a metal phase.
  • Specific examples include metals such as palladium, silver, copper, nickel, aluminum, and iron.
  • the catalyst precursor according to the present invention means a compound before being modified into an electroless plating catalyst, and can be a catalyst by an activation treatment step.
  • it is a metal salt compound that becomes a zero-valent metal upon activation, and includes palladium metal salts, silver metal salts, copper metal salts, nickel metal salts, aluminum metal salts, iron metal salts, and the like.
  • palladium metal salts are preferred.
  • the palladium metal salt may be a palladium metal complex complexed with a complexing agent.
  • Examples of the palladium metal salt applicable to the present invention include palladium fluoride, palladium chloride, palladium bromide, palladium iodide, palladium nitrate, palladium sulfate, palladium acetate, palladium acetoacetate, palladium trifluoroacetate, palladium hydroxide. , Palladium oxide, palladium sulfide and the like.
  • the palladium metal salt applicable to the present invention is preferably a compound that is soluble in the ink solvent and insoluble in water, and specifically, palladium acetate, palladium acetoacetate, and the like are preferable.
  • the content of the palladium metal salt in the catalyst ink is preferably 0.01% by mass or more and 1.0% by mass or less. If the concentration of the palladium metal salt is 0.01% by mass or more, the necessary activity of the electroless plating reaction as the next step can be obtained, and if it is 1.0% by mass or less, the palladium metal in the ink is obtained. This is preferable in that the stability of the salt can be maintained.
  • the catalyst ink according to the present invention preferably contains a complexing agent.
  • a complexing agent it is considered that the lipophilicity of the metal or metal salt is improved, and the electroless plating or its precursor is more easily penetrated by the polymer layer.
  • the complexing agent applicable to the present invention include compounds capable of forming a complex such as the palladium metal salt.
  • Such compounds include organic acids having a carboxyl group, and examples thereof include oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, tartaric acid, and citric acid.
  • Other compounds are preferably amine compounds or nitrogen-containing heterocyclic compounds.
  • the amine compound here is a compound in which one or more hydrogen atoms of ammonia or ammonia are substituted with a hydrocarbon residue.
  • An amine compound or a nitrogen-containing heterocyclic compound retains an unshared electron pair on a nitrogen atom, has a high complex-forming ability with respect to a metal, and is particularly easily complexed with a palladium ion.
  • nitrogen-containing heterocyclic compound include pyridine, bipyridine, phenanthroline and the like.
  • the catalyst ink containing the solvent swells or dissolves the anchor layer composed of the polymer. Therefore, the solvent to be applied is preferably one having a function of swelling or dissolving the anchor layer. .
  • Solvents that can be used include, for example, alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, etc.), polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethanol).
  • alcohols eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, etc.
  • polyhydric alcohols eg, ethylene glycol, diethylene glycol, triethanol.
  • Ethylene glycol polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyhydric alcohol monoethers (for example, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dichloropyrene glycol monoethyl ether, dipropylene glycol monobutyl ether, triethylene Glycol monomethyl ether, triethylene glycol monoethyl ether, tri
  • solvents examples include acetone, methyl ethyl ketone, toluene, benzene, cyclohexane, cyclohexanone, tetradecane, ethyl acetate, butyl acetate, ⁇ -butyl lactone, butyl lactate, ethylene carbonate, and propylene carbonate.
  • Preferred solvents for swelling or dissolving the anchor layer according to the present invention and from the viewpoint of stability in the catalyst ink are the polyhydric alcohols described above, in which all alcohol terminals are etherified or esterified. More preferably, the above polyhydric alcohol in which all alcohol terminals are etherified or esterified is contained in the catalyst ink in an amount of 50% by mass or more.
  • the catalyst ink according to the present invention may contain various conventionally known additives in other metal pattern forming inks, if necessary.
  • additives for example, optical brighteners, antifoaming agents, lubricants, preservatives, thickeners, antistatic agents, matting agents, water-soluble polyvalent metal salts, acid-bases, pH adjusters such as buffer solutions, antioxidants, A surface tension adjusting agent, a non-resistance adjusting agent, a rust inhibitor, an inorganic pigment, etc. can be mentioned.
  • ⁇ Metallic pattern manufacturing method As a method for producing a metal pattern using the catalyst ink of the present invention, mainly, (1) forming an anchor layer containing a polymer; (2) A step of applying a catalyst ink on the anchor layer to swell or dissolve the anchor layer, (3) Surface treatment step for modifying the catalyst ink surface or anchor layer surface (4) When the catalyst ink contains a catalyst precursor, an activation treatment step for converting (reducing) the catalyst precursor into a catalyst, (5) An electroless plating process for generating metal with an electroless plating solution, (6) In the electroplating step, the step of increasing the thickness of the metal pattern portion, Through this, a metal pattern is formed. At this time, the formation of the metal pattern may be a method of forming a pattern only on a necessary portion, or a method of forming a metal pattern on the entire anchor layer.
  • FIG. 1 is a manufacturing flowchart for forming a metal pattern on the entire surface of the anchor layer
  • FIG. 2 is a manufacturing flowchart for forming a metal pattern only in a necessary region.
  • Anchor layer forming step In (1) of FIG. 1 and (1) of FIG. 2, in the anchor layer forming step, the anchor layer coating liquid is applied and dried on the substrate 1 using the coater 3 as described above, and the anchor layer 2 is formed. Form on the entire surface.
  • Catalyst ink application step As a step of applying the catalyst ink, in FIG. 1B, the catalyst ink 4 is applied to the entire surface of the anchor layer 2 using the coater 5. On the other hand, in (2) of FIG. 2, the coater 5A (for example, an ink jet recording head) is used on the anchor layer 2 to apply the catalyst ink 4 so as to form separate regions.
  • the coater 5A for example, an ink jet recording head
  • a printing method can be used. Specific examples include screen printing, letterpress printing, gravure printing, offset printing, dispenser printing, and ink jet printing.
  • the application method is not limited to the above printing method, as long as the catalyst ink can be applied to the anchor layer, and wet coating methods such as roll coating, reverse coating, wire bar coating, and dip coating can also be applied. is there.
  • the catalyst ink 4 applied on the anchor layer 2 by the above method penetrates into the anchor layer 2 and swells or dissolves the anchor layer, as shown in FIG. 1 (3) and FIG. 2 (3). Region 6 is formed.
  • the amount of the catalyst ink applied is selected in consideration of the concentration of the electroless plating catalyst in the ink or the precursor concentration, the boiling point of the solvent, the drying property, and the electroless plating property.
  • the specific amount of catalyst ink applied is preferably 0.5 ml / m 2 to 50 ml / m 2 , more preferably 2.0 ml / m 2 to 30 ml / m 2 . If the applied amount is 0.5 ml / m 2 or more, the electroless plating property (metal forming property) is sufficient, and if it is 50 ml / m 2 or less, the uniformity and drying property of the catalyst ink is ensured. Can do.
  • a drying step After applying the catalyst ink, it is preferable to provide a drying step.
  • a drying method a heating method, an air blowing method and the like are preferable from the viewpoint of time reduction and process simplification.
  • the anchor layer is It is preferable to perform surface modification.
  • the affinity of the anchor layer 2 or the application region 6 of the catalyst ink 4 to the plating solution or the activation solution can be improved, and the surface wettability can be further improved.
  • the surface-modified catalyst ink region 7 is shown in FIG. 1 (4) or FIG. 2 (4).
  • the film-forming region 6 containing the catalyst ink becomes hydrophobic.
  • the plating treatment solution or the activation treatment solution is usually an aqueous solution, the wettability with respect to the plating treatment solution or the activation treatment solution used in the subsequent process is lowered, and the plating property may be slightly lowered. Therefore, by applying a hydrophilic surface treatment to the film forming region 6, the affinity of the film forming region to the plating treatment solution or the activation treatment solution can be improved, and a metal pattern with higher adhesion can be formed. can do.
  • the surface treatment is effective. Specifically, a treatment in which the contact angle with water is reduced by 20% or more before and after the surface treatment step is preferable.
  • the surface treatment method there are a method of treating with a solution containing a cation, nonion, or anionic surfactant, and a method of improving wettability with respect to the plating solution by a surface hydrophilization treatment step such as plasma, corona, flame, or UV irradiation. .
  • a surfactant is preferable because it is simple and highly effective.
  • a metal salt compound When a metal salt compound is used as a precursor of the electroless plating catalyst, it is a step of reacting with a zero-valent metal by a reduction reaction, and this activation treatment step can become an electroless plating catalyst. .
  • an activation treatment step it is necessary to select an appropriate method depending on the type of catalyst, and examples thereof include application of acid, heating, and application of a reducing agent.
  • a reducing agent a boron-based compound is preferable, and specifically, sodium borohydride, trimethylamine borane, dimethylamine borane (DMAB) and the like are preferable.
  • a reduction method an activation treatment can be performed by immersing a substrate provided with a catalyst ink in a solution of a reducing agent.
  • it is a step of forming a metal by an electroless plating reaction at a portion of the anchor layer provided with a catalyst ink by immersing in an electroless plating solution (bath).
  • the electroless plating solution mainly contains 1) metal ions, 2) complexing agent for electroless plating solution, and 3) reducing agent.
  • the metal formed by electroless plating include gold, silver, copper, palladium, nickel, and alloys thereof, and copper, nickel, and alloys thereof are preferable from the viewpoint of adhesion and conductivity.
  • a metal ion used for an electroless plating bath a metal ion corresponding to the above metal is contained.
  • the complexing agent and reducing agent for the electroless plating solution are also selected to be suitable for metal ions.
  • the complexing agent examples include ethylenediaminetetraacetic acid (hereinafter abbreviated as EDTA), Rochelle salt, D-mannitol, D-sorbitol, dulcitol, iminodiacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, and the like. Of these, EDTA is preferred.
  • the reducing agent examples include formaldehyde, potassium tetrahydroborate, dimethylamine borane, glyoxylic acid, sodium hypophosphite, etc. Among them, formaldehyde is preferable.
  • the metal formation speed and film thickness can be controlled by controlling the temperature, pH, immersion time, and metal ion concentration of the plating bath.
  • Electroplating process Finally, as shown in (7) of FIG. 1 and (7) of FIG. 2, for the purpose of forming a plating layer (conductive film) 11 by increasing the thickness of the metal film 10 formed by the electroless plating process. After the electroless plating process, an electroplating process is further performed.
  • the electroplating can be performed using the formed metal film 10 as an electrode by the electroless plating process.
  • the electroplating can be performed using the formed metal film 10 as an electrode by the electroless plating process.
  • the conductive film 11 can be formed to a thickness according to the purpose, and the conductive film 11 thus formed is suitable for application to various applications that require high conductivity. is there.
  • a conventionally known method can be used as a method of electroplating applicable to the present invention.
  • the metal used for electroplating in the electroplating step include copper, chromium, lead, nickel, gold, silver, tin, and zinc. From the viewpoint of conductivity, copper, gold, and silver are preferable, and copper Is more preferable.
  • the film thickness of the electrically conductive film 11 obtained by electroplating it can set suitably according to a use, and it forms by adjusting the metal concentration contained in a plating bath, immersion time, or current density.
  • the film thickness of the conductive film 11 can be controlled.
  • the film thickness when used for general electric wiring or the like is preferably 0.3 ⁇ m or more, and more preferably 3 ⁇ m or more.
  • the metal pattern 1 was produced according to the following metal pattern formation process.
  • Anchor layer formation step 1 Anchor layer formation step 2: Catalyst ink application step 3: Surface treatment step 4: Activation step 5: Electroless plating step 6: Electroplating step (1: Anchor layer formation step) After the surface of a polyimide film (Toray Film Processing Co., Ltd., Kapton 100EN film thickness 50 ⁇ m) is subjected to oxygen plasma treatment, the following polymer 1 is applied and dried by a rod bar method, and an anchor layer having a dry film thickness of 0.5 ⁇ m 1 was formed.
  • a polyimide film Toray Film Processing Co., Ltd., Kapton 100EN film thickness 50 ⁇ m
  • Electroless plating catalyst precursor 0.05% by mass of palladium acetate 70% by mass of ethylene glycol diacetate ter-Butyl alcohol 30% by mass ⁇ Application of catalyst ink 1>
  • the prepared catalyst ink 1 was applied on the substrate on which the anchor layer 1 was formed using a wire bar under the condition of 5 ml / m 2 to give a solid pattern of 10 cm ⁇ 10 cm on the anchor layer 1. .
  • the surface treatment method 1 was performed on the sample 1 on which the anchor layer 1 and the catalyst ink 1 were applied to the substrate according to the following method.
  • ⁇ Surface treatment method 1> The sample 1 was immersed in a surfactant aqueous solution containing 0.5% by mass of a surfactant (polyoxyethylene nonylphenyl ether) and having a pH adjusted to about 12 at 60 ° C. for 5 minutes to perform surface treatment. And sample 1A was produced. This surface treatment method is referred to as “surface treatment method 1”.
  • the electroless plating treatment was performed by immersing the sample 1A subjected to 5: activation treatment in the following electroless copper plating solution (50 ° C.) adjusted to pH 13.0 with sodium hydroxide, about 0.2 ⁇ m. A copper plating layer having a thickness of 5 mm was formed.
  • the electroless copper plating solution has a copper concentration of 2.5 mass%, a formalin concentration of 1.0 mass%, and an ethylenediaminetetraacetic acid (EDTA) concentration of 2.5 mass%.
  • EDTA ethylenediaminetetraacetic acid
  • the sample 1A subjected to the above electroless plating treatment is immersed in an electroplating bath having the following composition, a copper plate is used as an anode, and electroplating is performed at a current density of 1.5 A / dm 2 to form a copper film of about 15 ⁇ m.
  • the metal pattern 1 was produced.
  • metal patterns 2 to 15 In the formation of the metal pattern 1, the composition of the anchor layer (detailed in Table 1), the type of catalyst ink (detailed in Table 2), application method and application amount (ml / m 2 ), surface treatment method (4: Surface treatment step) Metal patterns 2 to 15 were produced in the same manner except that the presence or absence of the activation treatment was changed to the combinations shown in Table 3.
  • Table 1 shows the composition of each anchor layer including the anchor layer 1 used to form the metal pattern 1.
  • polymer number 3 is iER807 manufactured by Japan Epoxy Resin Co., Ltd.
  • polymer number 4 is aqueous dispersion 1 described in the examples of JP-A-2009-280904.
  • No. 5 is a thermoplastic resin fine particle (styrene-butadiene latex) described in Examples of Japanese Patent Application Laid-Open No. 2010-16219.
  • Table 2 shows the composition of each catalyst ink including the catalyst ink 1 used for forming the metal pattern 1.
  • ⁇ Surface treatment method 3 Corona discharge treatment> Under an air atmosphere, the distance between the anchor layer surface and the electrode was 1 mm, and the treatment power was 20 W ⁇ min / m 2 .
  • Adhesion strength is 10 N / cm or more
  • B Adhesion strength is 6 N / cm or more and less than 10 N / cm
  • ⁇ Adhesion strength is 2 N / cm or more and less than 6 N / cm
  • X Adhesion strength Is less than 2 N / cm
  • Condition 1 The temperature was raised to 200 ° C. in 30 seconds and held at that temperature for 30 seconds.
  • Condition 2 The temperature was raised to 230 ° C. in 30 seconds and held for 30 seconds.
  • Condition 3 In 30 seconds. The sample was heated to a peak temperature of 260 ° C. and held at that temperature for 30 seconds. The surface of each sample subjected to the treatment under the above conditions 1 to 3 was visually observed, and moisture absorption reflow resistance was evaluated according to the following criteria.
  • A The formation of a 0.2 ⁇ m copper film is less than 10 minutes.
  • ⁇ The formation of a 0.2 ⁇ m copper film is 10 minutes or more and less than 20 minutes.
  • ⁇ The formation of a 0.2 ⁇ m copper film is as follows. 20 minutes or more and less than 40 minutes ⁇ : The formation of a 0.2 ⁇ m copper film is 40 minutes or more.
  • the metal pattern produced by the production method defined in the present invention is superior to the comparative example in adhesion to the substrate, moisture absorption reflow resistance and plating suitability. I understand.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemically Coating (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

La présente invention porte sur un procédé de production de motifs métalliques possédant : une forte adhérence à un substrat sur lequel les motifs métalliques sont formés ; une excellente résistance à la chaleur (résistance à la refusion par absorption d'humidité) après avoir été stockés dans un environnement à forte humidité ; et d'excellentes propriétés de dépôt sans courant. Le procédé de production de motifs métalliques est caractérisé en ce qu'il comprend, sur un substrat, 1) une étape à laquelle une couche d'ancrage contenant un polymère est formée ; 2) une étape à laquelle une encre, qui contient un catalyseur de dépôt sans courant ou un précurseur de celui-ci et un solvant, est appliquée au-dessus de la couche d'ancrage, et la couche d'ancrage est amenée à gonfler ou est dissoute, et 3) une étape à laquelle un traitement de dépôt sans courant est réalisé.
PCT/JP2011/065671 2010-07-28 2011-07-08 Procédé de production de motifs métalliques Ceased WO2012014657A1 (fr)

Applications Claiming Priority (2)

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JP2010168961 2010-07-28
JP2010-168961 2010-07-28

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WO2012014657A1 true WO2012014657A1 (fr) 2012-02-02

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6323390A (ja) * 1986-07-16 1988-01-30 日本曹達株式会社 プリント配線板の製造法
JP2003145709A (ja) * 2001-11-15 2003-05-21 Sumitomo Osaka Cement Co Ltd スクリーン印刷機およびスクリーン印刷方法
JP2010010548A (ja) * 2008-06-30 2010-01-14 Konica Minolta Holdings Inc インク受容基材及びそれを用いた導電性パターンの作製方法
JP2010016219A (ja) * 2008-07-04 2010-01-21 Konica Minolta Ij Technologies Inc 金属パターン形成方法及び金属パターン

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6323390A (ja) * 1986-07-16 1988-01-30 日本曹達株式会社 プリント配線板の製造法
JP2003145709A (ja) * 2001-11-15 2003-05-21 Sumitomo Osaka Cement Co Ltd スクリーン印刷機およびスクリーン印刷方法
JP2010010548A (ja) * 2008-06-30 2010-01-14 Konica Minolta Holdings Inc インク受容基材及びそれを用いた導電性パターンの作製方法
JP2010016219A (ja) * 2008-07-04 2010-01-21 Konica Minolta Ij Technologies Inc 金属パターン形成方法及び金属パターン

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