WO2010064602A1 - Procédé de fabrication de carte de circuit imprimé et carte de circuit imprimé obtenue au moyen dudit procédé - Google Patents

Procédé de fabrication de carte de circuit imprimé et carte de circuit imprimé obtenue au moyen dudit procédé Download PDF

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Publication number
WO2010064602A1
WO2010064602A1 PCT/JP2009/070106 JP2009070106W WO2010064602A1 WO 2010064602 A1 WO2010064602 A1 WO 2010064602A1 JP 2009070106 W JP2009070106 W JP 2009070106W WO 2010064602 A1 WO2010064602 A1 WO 2010064602A1
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WIPO (PCT)
Prior art keywords
resin
film
circuit board
resin film
manufacturing
Prior art date
Application number
PCT/JP2009/070106
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English (en)
Japanese (ja)
Inventor
愼悟 吉岡
弘明 藤原
Original Assignee
パナソニック電工株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US12/326,169 external-priority patent/US8240036B2/en
Priority claimed from JP2009251269A external-priority patent/JP5583384B2/ja
Application filed by パナソニック電工株式会社 filed Critical パナソニック電工株式会社
Priority to CN2009801480376A priority Critical patent/CN102224770A/zh
Priority to US13/131,402 priority patent/US8698003B2/en
Priority to KR1020117013186A priority patent/KR101238966B1/ko
Priority to EP09830368A priority patent/EP2367405A4/fr
Publication of WO2010064602A1 publication Critical patent/WO2010064602A1/fr
Priority to US14/196,370 priority patent/US9082438B2/en

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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
    • H05K3/107—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 by filling grooves in the support with conductive material
    • 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
    • H05K3/184—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 using masks
    • 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
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0364—Conductor shape
    • H05K2201/0376—Flush conductors, i.e. flush with the surface of the printed circuit
    • 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
    • H05K2201/09—Shape and layout
    • H05K2201/09209—Shape and layout details of conductors
    • H05K2201/09654—Shape and layout details of conductors covering at least two types of conductors provided for in H05K2201/09218 - H05K2201/095
    • H05K2201/09736—Varying thickness of a single conductor; Conductors in the same plane having different thicknesses
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0017—Etching of the substrate by chemical or physical means
    • H05K3/0026—Etching of the substrate by chemical or physical means by laser ablation
    • H05K3/0032—Etching of the substrate by chemical or physical means by laser ablation of organic insulating material

Definitions

  • the present invention relates to a circuit board manufacturing method and a circuit board obtained by the manufacturing method.
  • the subtractive method is a method of forming an electric circuit by removing (subtractive) a metal foil other than a portion where the electric circuit on the surface of the metal foil-clad laminate is desired to be formed.
  • the additive method is a method of forming an electric circuit by performing electroless plating only on a portion where a circuit on an insulating substrate is to be formed.
  • the subtractive method is a method in which a thick metal foil is etched to leave only a portion where the electric circuit is to be formed (circuit formation portion), and other portions are removed.
  • This method is disadvantageous from the viewpoint of manufacturing cost because the portion of the metal to be removed is wasted.
  • metal wiring can be formed by electroless plating only in a portion where an electric circuit is desired to be formed. For this reason, metal is not wasted and resources are not wasted. Also from such a point, the additive method is a preferable circuit forming method.
  • FIG. 5 is a schematic cross-sectional view for explaining each step of forming a metal wiring by a conventional full additive method.
  • a plating catalyst 102 is deposited on the surface of the insulating base material 100 on which the through holes 101 are formed. Note that the surface of the insulating substrate 100 is roughened in advance.
  • a photoresist layer 103 is formed on the insulating base material 100 on which the plating catalyst 102 is deposited.
  • the photoresist layer 103 is exposed through a photomask 110 on which a predetermined circuit pattern is formed.
  • the exposed photoresist layer 103 is developed to form a circuit pattern 104. Then, as shown in FIG.
  • the metal wiring 105 is formed on the surface of the circuit pattern 104 and the inner wall surface of the through hole 101 formed by development. .
  • a circuit made of the metal wiring 105 is formed on the insulating base material 100.
  • the plating catalyst 102 is deposited on the entire surface of the insulating substrate 100.
  • the following problems have arisen. That is, when the photoresist layer 103 is developed with high accuracy, plating can be formed only on a portion that is not protected by the photoresist.
  • an unnecessary plated portion 106 may remain in a portion where the plating is not originally formed as shown in FIG. This occurs because the plating catalyst 102 is deposited on the entire surface of the insulating substrate 100.
  • the unnecessary plated portion 106 causes a short circuit or migration between adjacent circuits. Such a short circuit or migration is more likely to occur when a circuit having a narrow line width and line interval is formed.
  • FIG. 6 is a schematic cross-sectional view for explaining the contour shape of a circuit formed by a conventional full additive method.
  • examples of the manufacturing method different from the above-described method for manufacturing a circuit board include the manufacturing methods described in Patent Document 1 and Patent Document 2.
  • Patent Document 1 discloses the following method as another additive method.
  • a solvent-soluble first photosensitive resin layer and an alkali-soluble second photosensitive resin layer are formed on an insulating substrate (insulating base material). Then, the first and second photosensitive resin layers are exposed through a photomask having a predetermined circuit pattern. Next, the first and second photosensitive resin layers are developed. Next, after the catalyst is adsorbed on the entire surface including the concave portions generated by development, only the unnecessary catalyst is removed by dissolving the alkali-soluble second photosensitive resin with an alkali solution. Then, after that, electroless plating is performed to accurately form a circuit only in a portion where the catalyst exists.
  • Patent Document 2 Further, the following method is disclosed in Patent Document 2 below.
  • a resin protective film is coated on an insulating substrate (insulating base material) (first step).
  • a groove and a through hole corresponding to the wiring pattern are drawn or formed on the insulating substrate coated with the protective film alone or simultaneously by machining or laser beam irradiation (second step).
  • an activation layer is formed on the entire surface of the insulating substrate (third step).
  • the protective film is peeled off, the activation layer on the insulating substrate is removed, and the activation layer is left only on the inner wall surface of the groove and the through hole (fourth step).
  • the insulating substrate is plated without using a plating protective film, and a conductive layer is selectively formed only on the inner surfaces of the activated grooves and through holes (fifth step).
  • Patent Document 2 describes that after a thermosetting resin is coated on an insulating substrate as a protective film and heated and cured, the protective film and the insulating substrate are cut according to a predetermined wiring pattern, or the surface of the insulating substrate is heated. It is described that the curable resin is removed with a solvent (Patent Document 2, page 2, lower left column, line 16 to lower right column, line 11).
  • An object of the present invention is to provide a circuit board manufacturing method capable of easily forming a highly accurate electric circuit on an insulating substrate.
  • One aspect of the present invention is a circuit pattern portion formed by forming a resin film on a surface of an insulating substrate, and forming a recess having a depth equal to or greater than the thickness of the resin film on the basis of the outer surface of the resin film.
  • a circuit board manufacturing method comprising: a removal step; and a plating treatment step of forming an electroless plating film only in a portion where the plating catalyst or its precursor remains after removing the resin film.
  • inspection process for making a resin film contain a fluorescent substance and test
  • inspection process for making a resin film contain a fluorescent substance and test
  • inspection process for making a resin film contain a fluorescent substance and test
  • inspection process for making a resin film contain a fluorescent substance and test
  • inspection process for making a resin film contain a fluorescent substance and test
  • Patent Document 2 does not specifically describe the type of thermosetting resin used as the protective film.
  • a general thermosetting resin has a problem that it is difficult to remove with a simple solvent because of its excellent solvent resistance.
  • such a thermosetting resin has too high adhesion to the resin substrate, and it is difficult to accurately remove only the protective film without leaving a fragment of the protective film on the surface of the resin substrate. there were.
  • the plating catalyst on the surface of the substrate is also removed. In this case, the conductive layer is not formed in the portion where the plating catalyst is removed.
  • the protective film made of thermosetting resin may collapse so that the plating catalyst in the protective film is redispersed in the solvent. there were.
  • the plating catalyst redispersed in the solvent may be reattached to the surface of the resin base material, and an unnecessary plating film may be formed in that portion. Therefore, according to a method such as the method disclosed in Patent Document 2, it is difficult to form a circuit having an accurate contour.
  • the method for manufacturing a circuit board according to the present embodiment includes a film forming step of forming a resin film on the surface of an insulating base, and a recess having a depth equal to or greater than the thickness of the resin film with reference to the outer surface of the resin film
  • FIG. 1 is a schematic cross-sectional view for explaining each step in the circuit board manufacturing method according to the first embodiment.
  • a resin film 2 is formed on the surface of the insulating substrate 1. This process corresponds to a film forming process.
  • a circuit pattern portion is formed by forming a recess having a depth equal to or greater than the thickness of the resin coating 2 with the outer surface of the resin coating 2 as a reference.
  • the circuit pattern portion may be a recess that allows the resin coating 2 to reach the surface of the insulating base material 1, or may be a circuit groove 3 in which the insulating base material 1 is dug. Moreover, you may drill the hole for forming the through-hole 4 as a part of the said circuit groove 3 in the said insulating base material 1 as needed.
  • the circuit groove 3 defines a portion where an electroless plating film is formed by electroless plating, that is, a portion where an electric circuit is formed. This step corresponds to a circuit pattern forming step.
  • the circuit pattern portion will be described focusing on the circuit groove 3.
  • a plating catalyst or its precursor 5 is deposited on the surface of the circuit groove 3 and the surface of the resin film 2 on which the circuit groove 3 is not formed. This step corresponds to a catalyst deposition step.
  • the resin coating 2 is removed from the insulating substrate 1.
  • a plating catalyst or its precursor 5 can be made to remain only on the surface of the insulating substrate 1 where the circuit groove 3 is formed.
  • the plating catalyst or its precursor 5 deposited on the surface of the resin film 2 is removed together with the resin film 2 while being supported on the resin film 2. This process corresponds to a film removal process.
  • electroless plating is performed on the insulating substrate 1 from which the resin coating 2 has been removed.
  • an electroless plating film is formed only in the portion where the plating catalyst or its precursor 5 remains. That is, as shown in FIG. 1E, an electroless plating film to be an electric circuit 6 is formed in the portion where the circuit groove 3 is formed. And this electric circuit 6 may consist of this electroless-plated film, or the electroless-plated film is further thickened by further electroless plating (fill-up plating). There may be. Specifically, for example, as shown in FIG.
  • an electric circuit 6 made of an electroless plating film is formed so as to fill the circuit groove 3 and the entire through hole 4, and the insulating substrate 1 and You may make it eliminate the level
  • This process corresponds to a plating process.
  • the circuit board 10 as shown in FIG. 1E is formed by the above steps.
  • the circuit board 10 thus formed is obtained by forming the electric circuit 6 on the insulating base material 1 with high accuracy.
  • the film forming process is a process of forming the resin film 2 on the surface of the insulating substrate 1.
  • the insulating base material 1 used in the film forming step is not particularly limited as long as it can be used for manufacturing a circuit board. Specifically, for example, a resin substrate containing a resin can be used.
  • organic substrates that can be used for manufacturing a circuit board, for example, a multilayer circuit board, can be used without any particular limitation.
  • organic substrates include those conventionally used in the manufacture of multilayer circuit boards, such as epoxy resins, acrylic resins, polycarbonate resins, polyimide resins, polyphenylene sulfide resins, polyphenylene ether resins, cyanate resins, benzoxazine resins, bis Examples include a substrate made of maleimide resin or the like.
  • the epoxy resin is not particularly limited as long as it is an epoxy resin constituting various organic substrates that can be used for manufacturing a circuit board.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol S type epoxy resin, aralkyl epoxy resin, phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, biphenol type epoxy resin, naphthalene type epoxy resin , Dicyclopentadiene type epoxy resins, epoxidized products of condensates of phenols and aromatic aldehydes having a phenolic hydroxyl group, triglycidyl isocyanurate, alicyclic epoxy resins, and the like.
  • epoxy resin nitrogen-containing resin, and silicone-containing resin that are brominated or phosphorus-modified to impart flame retardancy are also included.
  • said epoxy resin and resin said each epoxy resin and resin may be used independently, and may be used in combination of 2 or more type.
  • a curing agent is contained for curing.
  • the curing agent is not particularly limited as long as it can be used as a curing agent. Specific examples include dicyandiamide, phenolic curing agents, acid anhydride curing agents, aminotriazine novolac curing agents, and cyanate resins.
  • curing agent a novolak type, an aralkyl type, a terpene type etc. are mentioned, for example. Further examples include phosphorus-modified phenolic resins or phosphorus-modified cyanate resins for imparting flame retardancy.
  • curing agent may be used independently, and may be used in combination of 2 or more type.
  • a resin or the like having good laser light absorption in the wavelength range of 100 to 400 nm because a circuit pattern is formed by laser processing.
  • a polyimide resin or the like can be given.
  • the insulating base material may contain a filler.
  • the filler may be inorganic fine particles or organic fine particles, and is not particularly limited. By containing the filler, the filler is exposed to the laser processed portion, and it is possible to increase the adhesion between the plating due to the unevenness of the filler and the resin.
  • the material constituting the inorganic fine particles include aluminum oxide (Al 2 O 3 ), magnesium oxide (MgO), boron nitride (BN), aluminum nitride (AlN), silica (SiO 2 ), High dielectric constant fillers such as barium titanate (BaTiO 3 ) and titanium oxide (TiO 2 ); magnetic fillers such as hard ferrite; magnesium hydroxide (Mg (OH) 2 ), aluminum hydroxide (Al (OH) 2 ), Antimony trioxide (Sb 2 O 3 ), antimony pentoxide (Sb 2 O 5 ), guanidine salts, zinc borate, molybdate compounds, zinc stannate, and other inorganic flame retardants; talc (Mg 3 (Si 4 O 10) (OH) 2), barium sulfate (BaSO 4), calcium carbonate (CaCO 3), mica, and the like.
  • Al 2 O 3 magnesium oxide
  • MgO magnesium oxide
  • BN boro
  • the said inorganic fine particle may be used independently, and may be used in combination of 2 or more type. Since these inorganic fine particles have high thermal conductivity, relative dielectric constant, flame retardancy, particle size distribution, color tone freedom, etc., when selectively exerting a desired function, appropriate blending and particle size design should be performed. And high filling can be easily performed. Although not particularly limited, it is preferable to use a filler having an average particle diameter equal to or smaller than the thickness of the insulating layer, more preferably 0.01 to 10 ⁇ m, and still more preferably a filler having an average particle diameter of 0.05 ⁇ m to 5 ⁇ m. Is good.
  • the inorganic fine particles may be surface-treated with a silane coupling agent in order to enhance dispersibility in the insulating base material.
  • the insulating base material may contain a silane coupling agent in order to increase the dispersibility of the inorganic fine particles in the insulating base material.
  • the silane coupling agent is not particularly limited. Specific examples include silane coupling agents such as epoxy silane, mercapto silane, amino silane, vinyl silane, styryl silane, methacryloxy silane, acryloxy silane, and titanate.
  • the said silane coupling agent may be used independently, and may be used in combination of 2 or more type.
  • the insulating base material may contain a dispersant in order to improve the dispersibility of the inorganic fine particles in the insulating base material.
  • the dispersant is not particularly limited. Specific examples include dispersants such as alkyl ether, sorbitan ester, alkyl polyether amine, and polymer.
  • the said dispersing agent may be used independently, and may be used in combination of 2 or more type.
  • the resin film 2 is not particularly limited as long as it can be removed in the film removal step. Specifically, for example, a soluble resin that can be easily dissolved in an organic solvent or an alkaline solution, a swellable resin film made of a resin that can be swollen with a predetermined liquid (swelling liquid) described later, and the like. Among these, a swellable resin film is particularly preferable because accurate removal is easy. Moreover, as said swelling resin film, it is preferable that the swelling degree with respect to the said liquid (swelling liquid) is 50% or more, for example.
  • the swellable resin film is not limited to the resin film that does not substantially dissolve in the liquid (swelling liquid) and easily peels off from the surface of the insulating substrate 1 due to swelling.
  • a resin film that swells with respect to the swelling liquid dissolves at least partly and easily peels off from the surface of the insulating substrate 1 due to the swelling or dissolution, or the liquid (swelling liquid).
  • dissolution is also contained.
  • the method for forming the resin coating 2 is not particularly limited. Specifically, for example, it is formed by applying a liquid material capable of forming a resin film on the surface of the insulating base material 1 and then drying it, or by applying the liquid material to a support substrate and then drying it. And a method of transferring the resin film to be transferred onto the surface of the insulating substrate 1.
  • the method for applying the liquid material is not particularly limited. Specifically, for example, conventionally known spin coating method, bar coater method and the like can be mentioned.
  • the thickness of the resin coating 2 is preferably 10 ⁇ m or less, and more preferably 5 ⁇ m or less. On the other hand, the thickness of the resin coating 2 is preferably 0.1 ⁇ m or more, and more preferably 1 ⁇ m or more. When the resin coating 2 is too thick, the accuracy of circuit pattern portions such as circuit grooves and through holes formed by laser processing or machining in the circuit pattern forming process tends to be reduced. Moreover, when the thickness of the resin film 2 is too thin, it tends to be difficult to form a resin film having a uniform film thickness.
  • a resin film having a swelling degree of 50% or more with respect to the swelling liquid can be preferably used. Furthermore, a resin film having a swelling degree with respect to the swelling liquid of 100% or more is more preferable. In addition, when the said swelling degree is too low, there exists a tendency for a swelling resin film to become difficult to peel in the said film removal process.
  • the method for forming the swellable resin film is not particularly limited as long as it is the same as the method for forming the resin film 2 described above. Specifically, for example, a liquid material capable of forming a swellable resin film is applied to the surface of the insulating base material 1 and then dried, or the liquid material is applied to a support substrate and then dried. And a method of transferring the swellable resin film formed by the method to the surface of the insulating substrate 1.
  • liquid material that can form the swellable resin film examples include an elastomer suspension or emulsion.
  • the elastomer include a diene elastomer such as a styrene-butadiene copolymer, an acrylic elastomer such as an acrylate ester copolymer, and a polyester elastomer. According to such an elastomer, it is possible to easily form a swellable resin film having a desired degree of swelling by adjusting the degree of crosslinking or gelation of the elastomer resin particles dispersed as a suspension or emulsion.
  • the swellable resin film is particularly preferably a film whose degree of swelling changes depending on the pH of the swelling liquid.
  • the liquid condition in the catalyst deposition step is different from the liquid condition in the coating removal step, so that the swellable resin can be obtained at the pH in the catalyst deposition step.
  • the coating maintains high adhesion to the insulating substrate, and the swellable resin coating can be easily peeled off at the pH in the coating removal step.
  • the catalyst deposition step includes a step of treating in an acidic plating catalyst colloid solution (acid catalyst metal colloid solution) having a pH in the range of 1 to 3, for example, and the coating removal step has a pH of 12 to 12.
  • an acidic plating catalyst colloid solution acid catalyst metal colloid solution
  • the coating removal step has a pH of 12 to 12.
  • the step of swelling the swellable resin film in an alkaline solution in the range of 14 is provided, the swelling degree of the swellable resin film with respect to the acidic plating catalyst colloid solution is less than 50%, and further 40% or less.
  • the resin film preferably has a degree of swelling with respect to the alkaline solution of 50% or more, more preferably 100% or more, and even more preferably 500% or more.
  • Examples of such a swellable resin film include photocuring used for a sheet formed from an elastomer having a predetermined amount of carboxyl groups, a dry film resist (hereinafter also referred to as DFR) for patterning printed wiring boards, and the like. And a sheet obtained by curing the entire surface of a curable alkali-developing resist, and thermosetting or alkali-developing sheet.
  • the elastomer having a carboxyl group examples include diene elastomers such as a styrene-butadiene copolymer having a carboxyl group in the molecule by containing a monomer unit having a carboxyl group as a copolymerization component; acrylic acid Examples include acrylic elastomers such as ester copolymers; and polyester elastomers. According to such an elastomer, a swellable resin film having a desired alkali swelling degree can be formed by adjusting the acid equivalent, the degree of crosslinking or the degree of gelation of the elastomer dispersed as a suspension or emulsion. .
  • the carboxyl group in the elastomer swells the swellable resin film with respect to the alkaline aqueous solution and acts to peel the swellable resin film from the surface of the insulating substrate.
  • the acid equivalent is the polymer weight per equivalent of carboxyl groups.
  • the monomer unit having a carboxyl group examples include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and the like.
  • the content ratio of the carboxyl group in the elastomer having such a carboxyl group is preferably 100 to 2000, more preferably 100 to 800 in terms of acid equivalent.
  • the acid equivalent is too small, the compatibility with the solvent or other composition tends to decrease, whereby the resistance to the plating pretreatment liquid tends to decrease.
  • an acid equivalent is too large, there exists a tendency for the peelability with respect to aqueous alkali solution to fall.
  • the molecular weight of the elastomer is preferably 10,000 to 1,000,000, more preferably 20,000 to 60,000.
  • the molecular weight of the elastomer is too large, the releasability tends to decrease, and when it is too small, the viscosity decreases, so that it is difficult to maintain a uniform thickness of the swellable resin film, and plating pretreatment The resistance to the liquid also tends to deteriorate.
  • the resin coating includes (a) at least one monomer of carboxylic acid or acid anhydride having at least one polymerizable unsaturated group in the molecule and (b) the monomer (a). And a polymer resin obtained by polymerizing at least one monomer that can be polymerized with or a resin composition containing the polymer resin.
  • the polymer resin may be an essential component as a main resin, and at least one of oligomers, monomers, fillers and other additives may be added.
  • the main resin is preferably a linear polymer having thermoplastic properties. In order to control fluidity, crystallinity, etc., it may be grafted and branched.
  • the molecular weight is about 1,000 to 500,000 in terms of weight average molecular weight, and preferably 5000 to 50,000. If the molecular weight is too small, the flexibility of the film and the resistance to the plating nucleation solution (acid resistance) tend to decrease. Moreover, when molecular weight is too large, there exists a tendency for the sticking property at the time of using alkali peelability or a dry film to worsen.
  • a cross-linking point may be introduced for improving the resistance to plating nucleus chemicals, suppressing thermal deformation during laser processing, and controlling flow.
  • the composition of the polymer resin as the main resin includes (a) a carboxylic acid or acid anhydride monomer having at least one polymerizable unsaturated group in the molecule, and (b) the above ( a) It is obtained by polymerizing a monomer that can be polymerized with the monomer.
  • a monomer that can be polymerized with the monomer for example, those described in JP-A-7-281437, JP-A-2000-231190, JP-A-2001-201851 and the like can be mentioned.
  • Examples of (a) include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester, butyl acrylate, etc., alone or in combination of two or more May be combined.
  • Examples of (b) are generally non-acidic and have (1) a polymerizable unsaturated group in the molecule, but are not limited thereto. It is selected so as to maintain various properties such as resistance in the plating process and flexibility of the cured film. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert. -Butyl (meth) acrylate, 2-hydroxylethyl (meth) acrylate, 2-hydroxylpropyl (meth) acrylates.
  • esters of vinyl alcohol such as vinyl acetate, (meth) acrylonitrile, styrene or polymerizable styrene derivatives. It can also be obtained by polymerization of only a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule.
  • a monomer having a plurality of unsaturated groups is selected as a monomer used in the polymer so that it can be three-dimensionally cross-linked, such as an epoxy group, a hydroxyl group, an amino group, an amide group, a vinyl group in the molecular skeleton. Reactive functional groups can be introduced.
  • the amount of the carboxyl group contained in the resin is preferably 100 to 2000, preferably 100 to 800, as an acid equivalent.
  • the acid equivalent means the weight of the polymer having 1 equivalent of a carboxyl group therein.
  • compatibility with a solvent or other composition is lowered or plating pretreatment solution resistance is lowered.
  • plating pretreatment solution resistance is lowered.
  • peelability there exists a tendency for peelability to fall.
  • the composition ratio of the monomer (a) is 5 to 70% by mass.
  • Any monomer or oligomer may be used as long as it is resistant to plating nucleation chemicals and can be easily removed with alkali. Further, in order to improve the sticking property of the dry film (DFR), it can be considered that it is used as a tackifier as a plasticizer. Further, a crosslinking agent is added to increase various resistances. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert.
  • esters of vinyl alcohol such as vinyl acetate, (meth) acrylonitrile, styrene or polymerizable styrene derivatives. It can also be obtained by polymerization of only a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Furthermore, a polyfunctional unsaturated compound may be included. Any of the above monomers or oligomers obtained by reacting the monomers may be used. In addition to the above monomers, it is possible to include two or more other photopolymerizable monomers.
  • Examples of monomers include 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polyoxyethylene Polyoxyalkylene glycol di (meth) acrylate such as polyoxypropylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, dipentaerythritol penta (meth) Acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether tri (meth) acrylate, 2,2-bis (4-methacryloxy) Pointer ethoxyphenyl) propane, there is a polyfunctional (meth) acrylate containing urethane groups. Any
  • a filler may be contained.
  • the filler is not particularly limited, but silica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, clay, kaolin, titanium oxide, barium sulfate, alumina, zinc oxide, talc, mica, glass, potassium titanate, wollastonite, sulfuric acid Magnesium, aluminum borate, an organic filler, etc. are mentioned.
  • the resist thickness is generally as thin as 1 to 10 ⁇ m, it is preferable to have a small filler size. Although it is preferable to use a material having a small average particle size and cut coarse particles, the coarse particles can be crushed during dispersion or removed by filtration.
  • additives include, for example, photopolymerizable resins (photopolymerization initiators), polymerization inhibitors, colorants (dyes, pigments, coloring pigments), thermal polymerization initiators, and crosslinking agents such as epoxies and urethanes. Can be mentioned.
  • laser processing may be used.
  • a carbon dioxide laser, an excimer laser, a UV-YAG laser, or the like is selected.
  • These laser processing machines have various intrinsic wavelengths, and productivity can be improved by using a material having a high absorption rate for these wavelengths.
  • the UV-YAG laser is suitable for fine processing, and the laser wavelength is the third harmonic 355 nm and the fourth harmonic 266 nm. Therefore, it is desirable that the absorptance is high with respect to these wavelengths.
  • a material having a somewhat low absorption rate may be preferable.
  • the UV light transmits through the resist, so that energy can be concentrated on the underlying insulating layer processing. That is, since the advantages differ depending on the absorption rate of laser light, it is preferable to use a resist in which the absorption rate of the laser beam of the resist is adjusted according to the situation.
  • a sheet of a resin composition can be used.
  • DFR for example, light such as disclosed in Japanese Patent Application Laid-Open Nos. 2000-231190, 2001-201851, and 11-212262 may be mentioned. Examples thereof include a sheet obtained by fully curing a dry film of a polymerizable resin composition, and a commercially available as an alkali development type DFR such as UFG series manufactured by Asahi Kasei Corporation.
  • a resin containing a carboxyl group and containing rosin as a main component for example, “NAZDAR229” manufactured by Yoshikawa Chemical Co., Ltd.
  • a resin containing phenol as a main component for example, LEKTRACHEM “104F”
  • the swellable resin film was formed on the surface of the insulating substrate by applying a resin suspension or emulsion using a conventionally known application method such as a spin coat method or a bar coater method, followed by drying or a support substrate. After the DFR is bonded to the surface of the insulating substrate using a vacuum laminator or the like, it can be easily formed by curing the entire surface.
  • examples of the resin film include the following.
  • the following are mentioned as a resist material which comprises the said resin film.
  • Properties required for the resist material constituting the resin coating include, for example, (1) resistance to a liquid (plating nucleation chemical) in which an insulating substrate on which the resin coating is formed is immersed in a catalyst deposition step described later. (2) The film coating process described later, for example, the resin film (resist) can be easily removed by the step of immersing the insulating base material on which the resin film is formed in alkali, and (3) High film formability. (4) easy dry film (DFR) formation, (5) high storage stability, and the like.
  • the plating nucleation chemical solution As the plating nucleation chemical solution, as will be described later, for example, in the case of an acidic Pd—Sn colloid catalyst system, all are acidic (pH 1-2) aqueous solutions.
  • the catalyst imparting activator is a weak alkali (pH 8 to 12), and the others are acidic. From the above, it is necessary to withstand pH 1 to 11, preferably pH 1 to 12, as the resistance to the plating nucleating solution. Note that being able to withstand is that when a sample on which a resist is formed is immersed in a chemical solution, swelling and dissolution of the resist are sufficiently suppressed, and the resist serves as a resist.
  • the immersion temperature is from room temperature to 60 ° C.
  • the immersion time is from 1 to 10 minutes
  • the resist film thickness is from about 1 to 10 ⁇ m, but is not limited thereto.
  • an aqueous NaOH solution or an aqueous sodium carbonate solution is common. Its pH is 11 to 14, and it is desirable that the resist film can be easily removed preferably at pH 12 to 14.
  • the concentration of the aqueous NaOH solution is about 1 to 10%
  • the processing temperature is room temperature to 50 ° C.
  • the processing time is 1 to 10 minutes
  • the immersion or spray treatment is generally performed, but is not limited thereto.
  • a resist is formed on an insulating material, film formability is also important. A uniform film formation without repelling or the like is necessary. Moreover, although it is made into a dry film for the simplification of a manufacturing process, reduction of material loss, etc., the flexibility of a film is required in order to ensure handling property. Also, a dry film resist is pasted on the insulating material with a laminator (roll, vacuum). The pasting temperature is room temperature to 160 ° C., and the pressure and time are arbitrary. Thus, adhesiveness is required at the time of pasting. For this reason, the resist formed into a dry film is generally used as a three-layer structure sandwiched by a carrier film and a cover film to prevent dust from adhering, but is not limited thereto.
  • Storability is best when it can be stored at room temperature, but it must be refrigerated or frozen. As described above, it is necessary to prevent the composition of the dry film from being separated at low temperatures or to be cracked due to a decrease in flexibility.
  • the resin composition of the resist material may include a main resin (binder resin) as an essential component, and at least one of oligomers, monomers, fillers, and other additives may be added.
  • a main resin binder resin
  • the main resin should be a linear polymer with thermoplastic properties. In order to control fluidity and crystallinity, it may be branched by grafting.
  • the molecular weight is about 1,000 to 500,000 in terms of number average molecular weight, preferably 5000 to 50,000. If the molecular weight is too small, the flexibility of the film and the resistance to the plating nucleation solution (acid resistance) tend to decrease. Moreover, when molecular weight is too large, there exists a tendency for the sticking property at the time of using alkali peelability or a dry film to worsen.
  • a cross-linking point may be introduced for improving the resistance to plating nucleus chemicals, suppressing thermal deformation during laser processing, and controlling flow.
  • composition of the main resin (a) a carboxylic acid or acid anhydride monomer having at least one polymerizable unsaturated group in the molecule and (b) (a) a monomer that can be polymerized with the monomer It is obtained by polymerizing.
  • a monomer that can be polymerized with the monomer It is obtained by polymerizing.
  • Examples of (a) include, for example, (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester, butyl acrylate, etc., alone or 2 More than one type may be combined.
  • Examples of (b) are generally non-acidic and have (one) polymerizable unsaturated group in the molecule, but are not limited thereto. It is selected so as to maintain various properties such as resistance in the plating process and flexibility of the cured film. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert. -Butyl (meth) acrylate, 2-hydroxylethyl (meth) acrylate, 2-hydroxylpropyl (meth) acrylates and the like.
  • esters of vinyl alcohol such as vinyl acetate, (meth) acrylonitrile, styrene, or a polymerizable styrene derivative may be used. It can also be obtained by polymerization of only a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule.
  • a monomer having a plurality of unsaturated groups is selected as a monomer used in the polymer so that it can be three-dimensionally cross-linked, such as an epoxy group, a hydroxyl group, an amino group, an amide group, a vinyl group in the molecular skeleton. Reactive functional groups can be introduced.
  • the amount of the carboxyl group contained in the resin is preferably 100 to 2000, preferably 100 to 800, in terms of acid equivalent.
  • the acid equivalent means the weight of the polymer having 1 equivalent of a carboxyl group therein.
  • compatibility with a solvent or other composition is lowered or plating pretreatment solution resistance is lowered.
  • an acid equivalent is too high, there exists a tendency for peelability to fall.
  • the composition ratio of the monomer (a) is 5 to 70% by weight.
  • Any monomer or oligomer may be used as long as it is resistant to plating nucleation chemicals and can be easily removed with alkali. Further, in order to improve the sticking property of the dry film (DFR), it can be considered that it is used as a tackifier as a plasticizer. Further, a crosslinking agent is added to increase various resistances. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert.
  • esters of vinyl alcohol such as vinyl acetate, (meth) acrylonitrile, styrene, or a polymerizable styrene derivative are also included. It can also be obtained by polymerization of only a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Furthermore, a polyfunctional unsaturated compound may be included. Any of the above monomers or oligomers obtained by reacting the monomers may be used.
  • this monomer examples include, for example, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Polyoxyalkylene glycol di (meth) acrylate such as polyoxyethylene polyoxypropylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, dipentaerythritol penta (Meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether tri (meth) acrylate, 2,2-bis (4-methyl) Methacryloxy penta
  • a filler may be contained.
  • the filler is not particularly limited. Specifically, for example, silica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, clay, kaolin, titanium oxide, barium sulfate, alumina, zinc oxide, talc, mica, glass, titanic acid. Examples include potassium, wollastonite, magnesium sulfate, aluminum borate, and an organic filler.
  • the resist thickness is generally as thin as 1 to 10 ⁇ m, it is preferable to have a small filler size. Although it is preferable to use a material having a small average particle size and cut coarse particles, the coarse particles can be crushed during dispersion or removed by filtration.
  • additives include, for example, photopolymerizable resins (photopolymerization initiators), polymerization inhibitors, colorants (dyes, pigments, coloring pigments), thermal polymerization initiators, and crosslinking agents such as epoxies and urethanes. Can be mentioned.
  • laser processing may be used.
  • the laser processing machine for example, a carbon dioxide laser, an excimer laser, a UV-YAG laser, or the like is selected.
  • These laser processing machines have various intrinsic wavelengths, and productivity can be improved by using a material having a high absorption rate for these wavelengths.
  • the UV-YAG laser is suitable for fine processing, and the laser wavelength is 3rd harmonic 355 nm and 4th harmonic 266 nm. Therefore, the resist material has a high absorption rate for these wavelengths. Is desirable.
  • a material having a somewhat low absorption rate may be preferable.
  • the UV light transmits through the resist, so that energy can be concentrated on the underlying insulating layer processing. That is, since the advantages differ depending on the absorption rate of laser light, it is preferable to use a resist in which the absorption rate of the laser beam of the resist is adjusted according to the situation.
  • the circuit pattern forming step is a step of forming a circuit pattern portion such as a circuit groove 3 on the insulating substrate 1.
  • the circuit pattern portion may be not only the circuit groove 3 but also a recess that reaches the surface of the insulating base material 1 to the resin coating 2, or may be a through hole 4.
  • the method for forming the circuit pattern portion is not particularly limited. Specifically, for example, on the insulating base material 1 on which the resin coating 2 is formed, from the outer surface side of the resin coating 2, machining such as laser processing and dicing processing, and mechanical processing such as embossing processing, etc.
  • the method of forming the circuit groove 3 of a desired shape and depth by giving is mentioned.
  • laser processing the cutting depth or the like can be freely adjusted by changing the output of the laser or the like.
  • the stamping process for example, a stamping process using a fine resin mold used in the field of nanoimprinting can be preferably used.
  • a through hole 4 for forming a via hole or the like may be formed as a part of the circuit groove 3.
  • This step defines the shape of the circuit pattern portion such as the shape and depth of the circuit groove 3 and the diameter and position of the through-hole 4.
  • the circuit pattern forming step may be performed by dug more than the thickness of the resin film 2, or may be dug by the thickness of the resin film 2 or may be dug beyond the thickness of the resin film 2.
  • the width of the circuit pattern portion such as the circuit groove 3 formed in the circuit pattern forming step is not particularly limited. When laser processing is used, a fine circuit having a line width of 20 ⁇ m or less can be easily formed.
  • the depth of the circuit groove is the depth of the electric circuit formed in the present embodiment when the step is eliminated between the electric circuit and the insulating base material by fill-up plating.
  • the catalyst deposition step is a step of depositing a plating catalyst or its precursor on the surface of the circuit pattern portion such as the circuit groove 3 and the surface of the resin coating 2. At this time, when the through hole 4 is formed, the plating catalyst or its precursor is also applied to the inner wall surface of the through hole 4.
  • the plating catalyst or its precursor 5 is a catalyst applied to form an electroless plating film only in a portion where it is desired to form an electroless plating film by electroless plating in the plating treatment step.
  • Any plating catalyst can be used without particular limitation as long as it is known as a catalyst for electroless plating.
  • a plating catalyst precursor may be deposited in advance, and the plating catalyst may be generated after removing the resin film.
  • Specific examples of the plating catalyst include, for example, metal palladium (Pd), platinum (Pt), silver (Ag), etc., or a precursor that generates these.
  • Examples of the method of depositing the plating catalyst or its precursor 5 include a method of treating with an acidic Pd—Sn colloidal solution treated under acidic conditions of pH 1 to 3 and then treating with an acid solution. It is done. Specific examples include the following methods.
  • oil or the like adhering to the surface of the insulating base material 1 in which the circuit grooves 3 and the through holes 4 are formed is washed in hot water in a surfactant solution (cleaner / conditioner) for a predetermined time.
  • a surfactant solution cleaning / conditioner
  • a soft etching treatment is performed with a sodium persulfate-sulfuric acid based soft etching agent.
  • an acidic solution such as a sulfuric acid aqueous solution or a hydrochloric acid aqueous solution having a pH of 1 to 2.
  • a pre-dip treatment is performed in which a chloride ion is adsorbed on the surface of the insulating base material 1 by being immersed in a pre-dip solution mainly containing a stannous chloride aqueous solution having a concentration of about 0.1%.
  • Pd and Sn are aggregated and adsorbed by further dipping in an acidic plating catalyst colloidal solution such as acidic Pd—Sn colloid having a pH of 1 to 3 containing stannous chloride and palladium chloride.
  • an oxidation-reduction reaction SnCl 2 + PdCl 2 ⁇ SnCl 4 + Pd ⁇
  • the metal palladium which is a plating catalyst precipitates.
  • the acidic plating catalyst colloid solution a known acidic Pd—Sn colloid catalyst solution or the like can be used, and a commercially available plating process using an acidic plating catalyst colloid solution may be used. Such a process is systematized and sold by Rohm & Haas Electronic Materials Co., Ltd., for example.
  • the plating catalyst or its precursor 5 can be deposited on the surface of the circuit groove 3, the inner wall surface of the through hole 4, and the surface of the resin coating 2.
  • the coating removal step is a step of removing the resin coating 2 from the insulating base material 1 subjected to the catalyst deposition step.
  • the method for removing the resin coating 2 is not particularly limited. Specifically, for example, after the resin film 2 is swollen with a predetermined solution (swelling liquid), the resin film 2 is peeled off from the insulating substrate 1, or the resin with a predetermined solution (swelling liquid). A method of removing the resin film 2 from the insulating substrate 1 after the film 2 is swollen and further partially dissolved, and a method of removing the resin film 2 by dissolving it with a predetermined solution (swelling liquid) Etc.
  • the swelling liquid is not particularly limited as long as it can swell the resin film 2.
  • the swelling or dissolution is performed by immersing the insulating base material 1 covered with the resin coating 2 in the swelling liquid for a predetermined time. And removal efficiency may be improved by irradiating with ultrasonic waves during the immersion. In addition, when it swells and peels, you may peel off with a light force.
  • the swellable resin film 2 can be used without substantially decomposing or dissolving the insulating substrate 1 and the plating catalyst or its precursor 5. Any liquid that can be swollen or dissolved can be used without particular limitation. Moreover, the liquid which can swell so that the said swellable resin film 2 can be peeled easily is preferable. Such a swelling liquid can be appropriately selected depending on the type and thickness of the swellable resin film 2.
  • the swelling resin film is an elastomer such as a diene elastomer, an acrylic elastomer, and a polyester elastomer, or (a) a carboxylic acid or an acid having at least one polymerizable unsaturated group in the molecule.
  • a polymer resin obtained by polymerizing at least one monomer of an anhydride and (b) at least one monomer that can be polymerized with the monomer (a) or the polymer resin In the case where the resin composition is formed from a carboxyl group-containing acrylic resin, an alkaline aqueous solution such as a sodium hydroxide aqueous solution having a concentration of about 1 to 10% can be preferably used.
  • the swelling resin film 2 has a degree of swelling of less than 50%, preferably 40% or less under acidic conditions.
  • the degree of swelling is 50% or more under alkaline conditions
  • elastomers such as diene elastomers, acrylic elastomers, and polyester elastomers, (a) at least one polymerizable unsaturated group in the molecule
  • Polymer resin obtained by polymerizing at least one monomer of carboxylic acid or acid anhydride having at least one monomer and (b) at least one monomer that can be polymerized with monomer
  • it is preferably formed from a resin composition containing the polymer resin and a carboxyl group-containing acrylic resin.
  • Such a swellable resin film easily swells and peels off with an alkaline aqueous solution having a pH of 12 to 14, for example, a sodium hydroxide aqueous solution having a concentration of about 1 to 10%.
  • an alkaline aqueous solution having a pH of 12 to 14 for example, a sodium hydroxide aqueous solution having a concentration of about 1 to 10%.
  • Examples of the method of swelling the swellable resin film 2 include a method of immersing the insulating base material 1 coated with the swellable resin film 2 in a swelling solution for a predetermined time. Moreover, in order to improve peelability, it is particularly preferable to irradiate with ultrasonic waves during immersion. In addition, when not peeling only by swelling, you may peel off with a light force as needed.
  • the plating process is a process of performing an electroless plating process on the insulating substrate 1 after the resin film 2 is removed.
  • the insulating base material 1 partially coated with the plating catalyst or its precursor 5 is immersed in an electroless plating solution, and the plating catalyst or its precursor 5 is applied.
  • a method of depositing an electroless plating film (plating layer) only on the portion may be used.
  • Examples of the metal used for electroless plating include copper (Cu), nickel (Ni), cobalt (Co), and aluminum (Al).
  • the plating which has Cu as a main component is preferable from the point which is excellent in electroconductivity.
  • Ni is included, it is preferable from the point which is excellent in corrosion resistance and adhesiveness with a solder.
  • the film thickness of the electroless plating film 6 is not particularly limited. Specifically, for example, it is preferably about 0.1 to 10 ⁇ m, more preferably about 1 to 5 ⁇ m. In particular, by increasing the depth of the circuit groove 3, it is possible to easily form a metal wiring having a large thickness and a large cross-sectional area. In this case, it is preferable because the strength of the metal wiring can be improved.
  • an electroless plating film is deposited only on the portion of the surface of the insulating substrate 1 where the plating catalyst or its precursor 5 remains. Therefore, it is possible to accurately form the conductive layer only in the portion where the circuit pattern portion is desired to be formed. On the other hand, the deposition of the electroless plating film on the portion where the circuit pattern portion is not formed can be suppressed. Therefore, even when a plurality of fine circuits having a narrow line width with a narrow pitch interval are formed, an unnecessary plating film does not remain between adjacent circuits. Therefore, the occurrence of a short circuit and the occurrence of migration can be suppressed.
  • the resin coating 2 contains a fluorescent material, and after the coating removal step, the coating removal failure is inspected using light emitted from the fluorescent material.
  • An inspection process may be further included. That is, by including a fluorescent substance in the resin film 2, the film removal failure is caused by using light emitted from the fluorescent substance by irradiating the inspection target surface with ultraviolet light or near ultraviolet light after the film removal step. It is possible to inspect the presence or absence of the film and the location where the film removal is defective.
  • an electric circuit having an extremely narrow line width and line interval can be formed.
  • FIG. 2 is an explanatory diagram for explaining an inspection process for inspecting a film removal failure by using a light emission from the fluorescent substance by adding a fluorescent substance to the resin film.
  • the fluorescent substance that can be contained in the resin film 2 used in the inspection process is not particularly limited as long as it exhibits light emission characteristics when irradiated with light from a predetermined light source. Specific examples thereof include Fluoresceine, Eosine, Pyroline G, and the like.
  • the portion where light emission from the fluorescent substance is detected by this inspection process is a portion where the residue 2a of the resin film 2 remains. Therefore, by removing the portion where luminescence is detected, it is possible to suppress the formation of an electroless plating film on that portion. Thereby, generation
  • the circuit board manufacturing method further includes a desmear treatment step of performing a desmear treatment after the plating treatment step, specifically, before or after the fill-up plating. May be.
  • a desmear treatment step of performing a desmear treatment after the plating treatment step specifically, before or after the fill-up plating. May be.
  • desmear treatment unnecessary resin adhered to the electroless plating film can be removed.
  • the surface of the insulating base material where the electroless plating film is not formed is roughened, and the adhesion with the upper layer of the circuit board is improved. Can be improved.
  • a desmear process may be performed on the via bottom. By doing so, unnecessary resin adhered to the via bottom can be removed.
  • a well-known desmear process can be used. Specifically, the process etc. which are immersed in a permanganic acid solution etc. are mentioned, for example.
  • an electric circuit composed of the electroless plating film 6a is formed in a deep portion of the insulating substrate 1 as shown in FIG. be able to.
  • a circuit can be formed at a position where the depths are different between a plurality of conductive layers (for example, 6a and 6b in FIG. 3).
  • a circuit is formed so as to embed the circuit groove by an electroless plating process. Since a circuit having a large cross-sectional area can be easily formed, it is preferable from the viewpoint that the electric capacity of the circuit can be increased.
  • the circuit board obtained by forming an electric circuit on a flat insulating base material has been described, but the present invention is not particularly limited thereto. Specifically, even when a three-dimensional insulating base material having a stepped three-dimensional surface is used as the insulating base material, a circuit board (stereoscopic circuit board) having an accurate electric circuit of wiring can be obtained.
  • FIG. 4 is a schematic cross-sectional view for explaining each step of manufacturing the three-dimensional circuit board according to the second embodiment.
  • the resin coating 2 is formed on the surface of the three-dimensional insulating substrate 51 having a stepped portion. This process corresponds to a film forming process.
  • the three-dimensional insulating base material 51 various resin molded bodies that can be used in the manufacture of conventionally known three-dimensional circuit boards can be used without any particular limitation. It is preferable from the viewpoint of production efficiency that such a molded body is obtained by injection molding.
  • the resin material for obtaining the resin molding include polycarbonate resin, polyamide resin, various polyester resins, polyimide resin, polyphenylene sulfide resin, and the like.
  • the formation method of the resin film 2 is not particularly limited. Specifically, for example, the same formation method as in the first embodiment can be used.
  • a circuit pattern portion such as a circuit groove 3 having a depth equal to or greater than the thickness of the resin coating 2 is formed with the outer surface of the resin coating 2 as a reference.
  • the method for forming the circuit pattern portion is not particularly limited. Specifically, for example, the same formation method as in the first embodiment can be used.
  • the circuit pattern portion such as the circuit groove 3 defines a portion where an electroless plating film is formed by electroless plating, that is, a portion where an electric circuit is formed. This step corresponds to a circuit pattern forming step.
  • a plating catalyst or its precursor 5 is coated on the surface of the circuit pattern portion such as the circuit groove 3 and the surface of the resin film 2 where the circuit pattern portion is not formed.
  • the method for depositing the plating catalyst or its precursor 5 is not particularly limited. Specifically, for example, the same method as in the first embodiment can be used.
  • This step corresponds to a catalyst deposition step.
  • the plating catalyst or its precursor 5 can be deposited on the surface of the circuit pattern portion such as the circuit groove 3 and the surface of the resin coating 2 as shown in FIG. it can.
  • the resin coating 2 is removed from the three-dimensional insulating base material 51.
  • the plating catalyst or its precursor 5 can remain only on the surface of the portion of the three-dimensional insulating substrate 51 where the circuit pattern portion such as the circuit groove 3 is formed.
  • the plating catalyst or its precursor 5 deposited on the surface of the resin film 2 is removed together with the resin film 2 while being supported on the resin film 2.
  • the method for removing the resin film 2 is not particularly limited. Specifically, for example, the same method as in the first embodiment can be used. This process corresponds to a film removal process.
  • electroless plating is applied to the three-dimensional insulating substrate 51 from which the resin coating 2 has been removed.
  • the electroless plating film 6 is formed only in the portion where the plating catalyst or its precursor 5 remains. That is, an electroless plating film 6 that becomes an electric circuit is formed in a portion where the circuit groove 3 and the through hole 4 are formed.
  • the formation method of the electroless plating film 6 is not particularly limited. Specifically, for example, the same formation method as in the first embodiment can be used. This process corresponds to a plating process.
  • the circuit board 60 formed in this way can form an electric circuit with high accuracy even if the line width and line interval of the electric circuit formed on the insulating base material are narrow.
  • the circuit board according to the present embodiment is accurately and easily formed on the surface of the three-dimensional circuit board having the stepped portion.
  • Example 1 A 2 ⁇ m thick styrene-butadiene copolymer (SBR) film was formed on the surface of a 100 ⁇ m thick epoxy resin substrate (R1766 manufactured by Panasonic Electric Works Co., Ltd.). The coating was formed on the main surface of the epoxy resin base material with a methylstyrene ketone (MEK) suspension (manufactured by Nippon Zeon Co., Ltd., acid equivalent 600, particle diameter 200 nm, solid content) of styrene-butadiene copolymer (SBR). 15%) was applied and dried at 80 ° C. for 30 minutes.
  • MEK methylstyrene ketone
  • a groove forming process of a substantially rectangular cross section having a width of 20 ⁇ m and a depth of 30 ⁇ m was performed by laser processing on the epoxy resin base material on which the film was formed.
  • laser processing MODEL 5330 manufactured by ESI equipped with a UV-YAG laser was used.
  • the grooved epoxy resin base material was immersed in a cleaner conditioner (surfactant solution, pH ⁇ 1: C / N 3320 manufactured by Rohm & Haas Electronic Materials Co., Ltd.), and then washed with water. Then, a soft etching treatment was performed with a soft etching agent of sodium persulfate-sulfuric acid pH ⁇ 1. And the pre-dip process was performed using PD404 (Shipley Far East Co., Ltd., pH ⁇ 1).
  • a cleaner conditioner surfactant solution, pH ⁇ 1: C / N 3320 manufactured by Rohm & Haas Electronic Materials Co., Ltd.
  • An electroless copper plating film having a thickness of 3 to 5 ⁇ m was deposited by the electroless copper plating treatment.
  • an SEM scanning microscope
  • the swelling degree of the swellable resin film was determined as follows.
  • the SBR suspension applied to form the swellable resin film on the release paper was applied and dried at 80 ° C. for 30 minutes. Thereby, a 2 ⁇ m thick resin film was formed. And the sample was obtained by forcibly peeling the formed film.
  • the weight of the sample at this time is defined as the weight m (b) before swelling.
  • the weighed sample was immersed in 10 ml of 5% aqueous sodium hydroxide solution at 20 ⁇ 2 ° C. for 15 minutes.
  • another sample was immersed in 10 ml of a 5% aqueous hydrochloric acid solution (pH 1) at 20 ⁇ 2 ° C. for 15 minutes.
  • the swelling degree with respect to a 5% aqueous solution of sodium hydroxide at pH 14 was 750%.
  • the degree of swelling with respect to a 5% hydrochloric acid aqueous solution at pH 1 was 3%.
  • Example 2 Instead of methyl ethyl ketone (MEK) suspension (manufactured by Nippon Zeon Co., Ltd., acid equivalent 600, particle size 200 nm, solid content 15%) of styrene-butadiene copolymer (SBR), a carboxyl group-containing polymer (Nippon Zeon Co., Ltd.) ), Acid equivalent 500, weight average molecular weight 25000, solid content 20%).
  • MEK methyl ethyl ketone
  • the swelling degree with respect to a 5% aqueous solution of sodium hydroxide at pH 14 was 1000%.
  • the degree of swelling with respect to a 5% hydrochloric acid aqueous solution at pH 1 was 30%.
  • the plating catalyst can be deposited only on the portion of the substrate surface where the circuit is desired to be formed by peeling the swellable resin film. Therefore, an electroless plating film is accurately formed only on the portion where the plating catalyst is deposited. Further, since the swellable resin film can be easily peeled off by the swelling action, the film removal step can be easily and accurately performed.
  • One aspect of the present invention is a circuit pattern portion formed by forming a resin film on a surface of an insulating substrate, and forming a recess having a depth equal to or greater than the thickness of the resin film on the basis of the outer surface of the resin film.
  • a circuit board manufacturing method comprising: a removal step; and a plating treatment step of forming an electroless plating film only in a portion where the plating catalyst or its precursor remains after removing the resin film.
  • a predetermined circuit pattern portion is formed using laser processing or the like, and a portion where a plating film is not formed is protected by the resin film.
  • a plating catalyst or a precursor thereof is deposited on the surface of the circuit pattern portion and the surface of the resin coating. Thereafter, by removing the resin film from the insulating substrate, the plating catalyst or its precursor is easily left only in the portion where the plating film is to be formed, and the plating catalyst or its precursor is removed from other portions. Can be removed.
  • a highly accurate electric circuit can be easily formed on the insulating substrate. That is, the outline of the formed circuit can be maintained with high accuracy. As a result, for example, even when a plurality of circuits are formed at regular intervals, it is possible to suppress the remaining pieces of the electroless plating film between the circuits, and thus suppress the occurrence of short circuits and migration. . In addition, a circuit having a desired depth can be formed.
  • the insulating base material may be formed after the film removing step swells the resin film with a predetermined liquid, or after dissolving a part of the resin film with a predetermined liquid. It is preferable that it is the process of peeling the said resin film from. According to such a manufacturing method, the resin film can be easily peeled from the insulating base material. Therefore, a highly accurate electric circuit can be more easily formed on the insulating substrate.
  • the swelling degree of the resin film with respect to the liquid is preferably 50% or more.
  • the resin film can be easily peeled from the insulating substrate. Therefore, a highly accurate electric circuit can be more easily formed on the insulating substrate.
  • the said resin film has a large degree of swelling with respect to the said liquid, and what melt
  • the catalyst deposition step includes a step of treating in an acidic catalyst metal colloid solution, the predetermined liquid in the coating removal step is an alkaline solution, and the resin coating is
  • the degree of swelling with respect to the acidic catalyst metal colloid solution is preferably less than 50%, and the degree of swelling with respect to the alkaline solution is preferably 50% or more.
  • the resin film is hardly peeled off in the catalyst deposition process treated under acidic conditions, and is easily peeled off in the film removal process treated with an alkaline solution after the catalyst deposition process. Therefore, the resin coating is selectively peeled off in the coating removal step. Accordingly, the portion where the electroless plating film is not formed can be accurately protected in the catalyst deposition step, and the resin coating can be easily peeled off in the coating removal step after deposition of the plating catalyst or its precursor. For this reason, more accurate circuit formation becomes possible.
  • the coating film removing step is preferably a step of dissolving and removing the resin coating film with a predetermined liquid. According to such a manufacturing method, the resin film can be easily removed from the insulating base material. Therefore, a highly accurate electric circuit can be more easily formed on the insulating substrate.
  • the resin film is preferably a resin film formed by applying an elastomer suspension or emulsion to the surface of the insulating base material and then drying the resin film. If such a resin film is used, the resin film can be easily formed on the surface of the insulating substrate. Therefore, a highly accurate electric circuit can be more easily formed on the insulating substrate.
  • the resin film is preferably a resin film formed by transferring a resin film formed on a support substrate to the surface of the insulating base material.
  • the resin film used for this transfer is more preferably a resin film formed by applying an elastomer suspension or emulsion to the surface of the support substrate and then drying. If such a resin film is used, a large number of resin films can be prepared in advance, which is preferable from the viewpoint of excellent mass productivity.
  • the elastomer is preferably selected from the group consisting of a diene elastomer, an acrylic elastomer, and a polyester elastomer having a carboxyl group.
  • the diene elastomer is more preferably a styrene-butadiene copolymer. According to such an elastomer, it is possible to easily form a resin film having a desired degree of swelling by adjusting the degree of crosslinking or the degree of gelation. In addition, the degree of swelling of the liquid used in the film removal step can be increased, and a resin film that dissolves in the liquid can be easily formed.
  • a film mainly composed of a resin composed of an acrylic resin having a carboxyl group with an acid equivalent of 100 to 800 is also preferably used.
  • the resin film may include (a) at least one monomer of carboxylic acid or acid anhydride having at least one polymerizable unsaturated group in the molecule; b) It is preferable that it consists of a polymer resin obtained by polymerizing the monomer (a) with at least one monomer that can be polymerized or a resin composition containing the polymer resin. . If such a resin film is used, the resin film can be easily formed on the surface of the insulating substrate. Therefore, a highly accurate electric circuit can be more easily formed on the insulating substrate. In addition, many of these resin films can be dissolved by the liquid used in the film removal step, and not only peeling and removal but also dissolution and removal can be used effectively.
  • the acid equivalent of the polymer resin is preferably 100 to 800 in the resin film.
  • the thickness of the resin film is preferably 10 ⁇ m or less from the viewpoint that a fine circuit can be formed with high accuracy.
  • the circuit pattern portion has a width of 20 ⁇ m or less because an antenna circuit or the like that requires fine processing can be formed.
  • the circuit pattern forming step is a step of forming a circuit pattern portion by laser processing
  • the cutting depth and the like can be easily adjusted by changing the laser output and the like, and thus the depth of the formed circuit groove and the like can be easily adjusted.
  • a through hole used for interlayer connection can be formed, or a capacitor can be embedded in an insulating base material.
  • the circuit pattern forming step is a step of forming a circuit pattern portion using a mold pressing method
  • the circuit pattern portion can be easily formed by mold stamping. It is preferable from the point which can be performed.
  • a through hole is formed in the insulating base material when the circuit pattern portion is formed in the circuit pattern forming step.
  • a through-hole that can be used for a via hole or an inner via hole can be formed when the circuit pattern portion is formed.
  • a via hole or an inner via hole is formed by electroless plating the formed through hole.
  • the insulating base material has a stepped surface formed in a step shape, and the surface of the insulating base material is the stepped surface. That is, the insulating substrate has a step surface formed in a step shape, and the coating film forming step, the circuit pattern forming step, the catalyst deposition step, the coating film removing step, and the plating treatment are formed on the step surface. It is also a preferable form to perform the process. According to such a manufacturing method, a circuit that can overcome a step can be easily formed.
  • the resin coating contains a fluorescent substance, and an inspection for inspecting a defective film removal using light emitted from the fluorescent substance after the coating removal step. It is preferable to further include a process.
  • the resin film that should originally be removed is completely between the adjacent circuit pattern portions. There is also a concern that it cannot be removed and remains slightly. There is also a concern that the resin film fragments removed during the formation of the circuit pattern portion may enter and remain in the formed circuit pattern portion. When the resin film remains between the circuit pattern portions, an electroless plating film is formed in the portion, which may cause migration or short circuit.
  • the resin film is made to contain a fluorescent substance as described above, and after the film removal step, only a portion where the resin film remains by irradiating a predetermined light source on the surface from which the film has been removed. By emitting light with the fluorescent substance, it is possible to inspect the presence or absence of the film removal failure or the location of the film removal failure.
  • another aspect of the present invention is a circuit board obtained by the method for manufacturing a circuit board. According to such a configuration, a circuit board on which a highly accurate electric circuit is formed on the insulating base material can be obtained.
  • the manufacturing method of the circuit board which can form easily the high precision electric circuit which can maintain the outline of the electric circuit formed of an electroless plating film with high precision on an insulating base material Is provided. Thereby, it is possible to suppress an unnecessary electroless plating film fragment or the like from remaining in a portion other than the circuit formation portion, thereby suppressing occurrence of a short circuit, migration, or the like. Is provided.

Landscapes

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

Abstract

L’invention concerne un procédé de fabrication de carte de circuit imprimé comprenant les étapes suivantes : formation d’un film de résine sur la surface d’un matériau de base isolant ; formation d’une partie de motifs de circuit par formation d’une partie évidée de profondeur équivalente à l’épaisseur de film de résine ou plus, la surface extérieure du film de résine étant une référence; application d’un catalyseur de placage ou d’un précurseur de celui-ci sur la surface de la partie de motifs de circuit et sur la surface du film de résine ; retrait du film de résine du matériau de base isolant ; formation d’un film de placage sans électrodes uniquement sur une partie sur laquelle le catalyseur de placage ou de précurseur de celui-ci reste après retrait du film de résine.
PCT/JP2009/070106 2008-12-02 2009-11-30 Procédé de fabrication de carte de circuit imprimé et carte de circuit imprimé obtenue au moyen dudit procédé WO2010064602A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN2009801480376A CN102224770A (zh) 2008-12-02 2009-11-30 电路基板的制造方法以及由该制造方法获得的电路基板
US13/131,402 US8698003B2 (en) 2008-12-02 2009-11-30 Method of producing circuit board, and circuit board obtained using the manufacturing method
KR1020117013186A KR101238966B1 (ko) 2008-12-02 2009-11-30 회로 기판의 제조 방법, 및 상기 제조 방법에 의해 얻어진 회로 기판
EP09830368A EP2367405A4 (fr) 2008-12-02 2009-11-30 Procédé de fabrication de carte de circuit imprimé et carte de circuit imprimé obtenue au moyen dudit procédé
US14/196,370 US9082438B2 (en) 2008-12-02 2014-03-04 Three-dimensional structure for wiring formation

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US12/326,169 2008-12-02
US12/326,169 US8240036B2 (en) 2008-04-30 2008-12-02 Method of producing a circuit board
JP2009251269A JP5583384B2 (ja) 2008-12-02 2009-10-30 回路基板の製造方法、及び前記製造方法により得られた回路基板
JP2009-251269 2009-10-30

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US12/326,169 Continuation-In-Part US8240036B2 (en) 2008-04-30 2008-12-02 Method of producing a circuit board

Related Child Applications (4)

Application Number Title Priority Date Filing Date
US13/131,402 A-371-Of-International US8698003B2 (en) 2008-12-02 2009-11-30 Method of producing circuit board, and circuit board obtained using the manufacturing method
US13/144,112 Continuation-In-Part US8482137B2 (en) 2009-01-27 2010-01-26 Method of mounting semiconductor chips, semiconductor device obtained using the method, method of connecting semiconductor chips, three-dimensional structure in which wiring is provided on its surface, and method of producing the same
PCT/JP2010/050971 Continuation-In-Part WO2010087336A1 (fr) 2008-12-02 2010-01-26 Procédé de montage de puces semi-conductrices, dispositif à semi-conducteurs obtenus par ce procédé, procédé de connexion de puces semi-conductrices, et structure tridimensionnelle, à la surface de laquelle est prévu un câblage et son procédé de fabrication
US14/196,370 Continuation-In-Part US9082438B2 (en) 2008-12-02 2014-03-04 Three-dimensional structure for wiring formation

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JPS57134996A (en) 1981-02-16 1982-08-20 Nippon Electric Co Method of producing printed circuit board
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JPS57134996A (en) 1981-02-16 1982-08-20 Nippon Electric Co Method of producing printed circuit board
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JPS63183445A (ja) * 1987-01-27 1988-07-28 Okuno Seiyaku Kogyo Kk 水溶性レジストフイルム用剥離剤
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JPH07509322A (ja) * 1992-07-14 1995-10-12 コーツ　ブラザーズ　ピーエルシー 基板の処理
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JP2003264359A (ja) * 2002-03-07 2003-09-19 Citizen Electronics Co Ltd 立体回路基体の製造方法
JP2003309346A (ja) * 2002-04-15 2003-10-31 National Institute Of Advanced Industrial & Technology プリント基板高速作成方法
JP2004048030A (ja) * 2002-07-15 2004-02-12 Toshiba Corp 電子回路の製造方法および電子回路の製造装置
JP2004281427A (ja) * 2003-03-12 2004-10-07 Mitsubishi Electric Corp 立体回路基板の製造方法及び立体回路基板
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JP2008058710A (ja) * 2006-08-31 2008-03-13 Jsr Corp ポジ型感放射線性樹脂組成物、転写フィルムおよびメッキ造形物の製造方法

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