US20130199830A1 - Resin composition, cured resin product, wiring board, and manufacturing method for wiring board - Google Patents

Resin composition, cured resin product, wiring board, and manufacturing method for wiring board Download PDF

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Publication number
US20130199830A1
US20130199830A1 US13/816,206 US201113816206A US2013199830A1 US 20130199830 A1 US20130199830 A1 US 20130199830A1 US 201113816206 A US201113816206 A US 201113816206A US 2013199830 A1 US2013199830 A1 US 2013199830A1
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Prior art keywords
resin layer
insulating resin
wiring board
wiring
support
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Abandoned
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US13/816,206
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English (en)
Inventor
Masaki Morita
Konatsu Nakamura
Shin Takanezawa
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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Filing date
Publication date
Priority claimed from JP2010179754A external-priority patent/JP5664008B2/ja
Priority claimed from JP2011171338A external-priority patent/JP5803399B2/ja
Priority claimed from JP2011171339A external-priority patent/JP5790272B2/ja
Priority claimed from JP2011171340A external-priority patent/JP5879801B2/ja
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Assigned to HITACHI CHEMICAL COMPANY, LTD. reassignment HITACHI CHEMICAL COMPANY, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MORITA, MASAKI, NAKAMURA, KONATSU, TAKANEZAWA, SHIN
Publication of US20130199830A1 publication Critical patent/US20130199830A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
    • C08G59/4269—Macromolecular compounds obtained by reactions other than those involving unsaturated carbon-to-carbon bindings
    • C08G59/4276—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • 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
    • 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
    • H05K3/0055—After-treatment, e.g. cleaning or desmearing of holes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
    • H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
    • H05K3/4632—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials laminating thermoplastic or uncured resin sheets comprising printed circuits without added adhesive materials between the sheets
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits

Definitions

  • the present invention relates to a resin composition, a cured resin product, a wiring board, and a method for manufacturing a wiring board.
  • the present invention relates to an insulating resin capable of revealing a high adhesive force to a wiring conductor even in a state where an irregular shape of the surface of an insulating resin layer is small, and also to a wiring board and a method for manufacturing a wiring board.
  • an insulating resin layer is formed on a substrate having a circuit. Then, after curing the insulating resin layer, in order to ensure the adhesive force to a wiring conductor, the surface of an insulating resin layer is subjected to a roughening treatment upon being dipped in an oxidizing treatment liquid. Subsequently, a plating pre-treatment is performed to achieve electroless plating. Furthermore, a resist pattern is formed on an electroless plated layer; thick deposition is performed by means of electrolytic plating; the resist pattern is peeled off; and the electroless plated layer is then removed to form a wiring board.
  • the oxidizing treatment liquid which is used for forming the irregularities on the surface of the insulating resin layer a strong alkali liquid containing sodium permanganate and sodium hydroxide is in general used. Though sodium permanganate dissolves a resin therein in the presence of a strong alkali, heptavalent manganese is consumed by an oxidizing treatment, and therefore, it is needed to regenerate manganese by an electrolytic regeneration system.
  • the insulating resin layer which is used for the wiring board of a build-up system is required to be able to ensure an adhesive force even if the irregularities are small.
  • Patent Document 1 proposes a method in which after irradiating an insulating resin layer using a polyphenylene ether resin with ultraviolet rays in the presence of oxygen to provide a conductor layer, the conductor layer is subjected to a heat treatment, and a circuit is then formed on the conductor layer, or a circuit is formed, and a heat treatment is then performed (see Patent Document 1, claim 1).
  • a surface roughness of the insulating layer can be controlled to be small; and that adhesion between the insulating layer and the conductor layer can be made favorable (see Patent Document 1, paragraph [0006]).
  • Patent Document 2 discloses a technology for treating an insulating resin layer with ultraviolet rays in an ozone solution. According to the subject technology, it is disclosed that excessive impartment of a plating catalyst to the surface of an insulating layer can be suppressed while ensuring an adhesion force between a wiring and an insulating layer; and that the deterioration of insulation resistance between the wirings can be suppressed (see Patent Document 2, claim 1 and paragraph [0006]).
  • Patent Document 1 According to the technology disclosed in the foregoing Patent Document 1, it is described that the surface roughness of the insulating layer can be controlled to be small; and that the adhesion between the insulating layer and the conductor layer can be made favorable. However, the strength of an adhesive force at the time of roughening treatment is not specifically disclosed, and a degree of its effect is unclear.
  • the polyphenylene ether resin which is used as the insulating resin in Patent Document 1 involves a problem in view of manufacture such that a xenon excimer lamp or a low pressure mercury vapor lamp each having a wavelength of not more than 300 nm, which is different from an ultraviolet ray lamp usually used for many purposes for post-exposure of a solder resist, or the like, cannot help being used.
  • the insulating resin composition is not mentioned at all, and therefore, a degree of its effect is unclear.
  • a step of dipping in an ozone solution having an ozone concentration of 100 ppm or more is substantially essential, so that there is involved such a problem that the operation is complicated.
  • a first object thereof is to provide a resin composition which has a high adhesive force to a wiring conductor even in a state where an irregular shape of the surface of an insulating resin layer is small and in which even when allowed to stand at a high temperature for a long period of time, the insulating resin layer keeps a high adhesive force to the wiring conductor, a cured resin product obtained by curing the resin composition, a wiring board using the cured resin product, and a method for manufacturing the wiring board.
  • a second object thereof is to provide a method for manufacturing a wiring board, which is capable of obtaining a wiring board in which nevertheless irregularities of the surface of an insulating resin layer are small, not only an adhesive force of the insulating resin layer to a wiring conductor is high, but a smear within a hole is sufficiently removed.
  • the present inventors made extensive and intensive investigations. As a result, it has been found that the foregoing first object can be achieved by using a resin composition containing an epoxy resin having a specified structure, an ultraviolet ray active ester group-containing compound, and an epoxy resin curing accelerator.
  • the objective wiring board is efficiently obtained by providing an uncured resin layer on a substrate having a circuit by using the resin composition, thermally curing the uncured resin layer, and then irradiating this with ultraviolet rays to obtain an insulating resin layer, followed by forming a wiring thereon by a plating method.
  • a first invention has been accomplished on the basis of such knowledge.
  • the first invention provides:
  • a resin composition containing (A) an epoxy resin having two or more epoxy groups in one molecule thereof and having a structural unit derived from an alkylene glycol having a carbon number of from 3 to 10 in a main chain thereof, (B) an ultraviolet ray active ester group-containing compound, and (C) an epoxy resin curing accelerator; (2) The resin composition as set forth above in (1), wherein the alkylene glycol having a carbon number of from 3 to 10 is hexanediol; (3), A cured resin product obtained by thermally curing the resin composition as set forth above in (1) or (2) and irradiating with ultraviolet rays; (4) A wiring board obtained by disposing a cured resin layer composed of the cured resin product as set forth above in (3) on a substrate having a circuit of a wiring conductor and forming a wiring on the cured resin layer by plating; and (5) A method for manufacturing a wiring board including (a) a step of forming an uncured resin layer on a substrate having a circuit of a wiring conductor
  • the cured resin layer in the first invention has insulating properties, there may be the case where it is hereunder called an “insulating resin layer”.
  • a second invention has been accomplished on the basis of such knowledge.
  • the second invention provides:
  • a method for manufacturing a wiring board having an insulating resin layer and a wiring formed on the surface of the insulating resin layer which performs successively a laminate forming step of forming a laminate having the insulating resin layer and a support, a hole forming step of providing a hole in the laminate, a desmearing treatment step of removing a smear within the hole with a desmearing treatment liquid, a support removal step of removing the support from the laminate, and a wiring forming step of forming the wiring on the surface of the insulating resin layer from which the support has been removed, wherein an ultraviolet ray irradiation step of irradiating ultraviolet rays on the surface of the insulating resin layer from which the support has been removed, to enhance an adhesive force to the wiring is included after the laminate forming step and before, the wiring forming step; (7) The method for producing a wiring board as set forth above in (6), which performs successively a laminate forming step of forming a laminate having a support,
  • the first invention it is possible to provide a resin composition which reveals a high adhesive force to a wiring conductor even in a state where an irregular shape of the surface of an insulating resin layer is small and in which even when treated with a sodium permanganate based roughening liquid or the like for the purpose of removing a smear on the bottom of a via hole, not only a roughened irregular shape of the surface of the insulating resin layer is small, but a high adhesive force to the wiring conductor can be kept, a wiring board, and a method for manufacturing a wiring board.
  • FIG. 1 is a cross-sectional view explaining an example of a manufacturing method of a wiring board according to the second invention.
  • FIG. 2 is a cross-sectional view explaining another example of a manufacturing method of a wiring board according to the second invention.
  • the resin composition of the first invention contains (A) an epoxy resin having two or more epoxy groups in one molecule thereof and having a structural unit derived from an alkylene glycol having a carbon number of from 3 to 10 in a main chain thereof, (B) an ultraviolet ray active ester group-containing compound, and (C) an epoxy resin curing accelerator.
  • the epoxy resin which is used as the component (A) may be an epoxy resin having two or more epoxy groups in one molecule thereof and having a structural unit derived from an alkylene glycol having a carbon number of from 3 to 10 in a main chain thereof.
  • Examples thereof include a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, a naphthol novolak type epoxy resin, a biphenyl novolak type resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol T type epoxy resin, a bisphenol Z type epoxy resin, a tetrabromobisphenol A type epoxy resin, a biphenyl type epoxy resin, a biphenyl aralkyl type epoxy resin, a tetramethylbiphenyl type epoxy resin, a triphenyl type epoxy resin, a tetraphenyl type epoxy resin, a naphthol aralkyl type epoxy resin, a naphthalenediol aralkyl type epoxy resin, a naphthol aralkyl type epoxy resin, a fluorene type epoxy resin, an epoxy resin having a dicyclopentadiene skeleton, an epoxy resin
  • these epoxy resins may also be used in combination of two or more kinds thereof.
  • the alkylene glycol having a carbon number of from 3 to 10 is more preferably an alkylene glycol having a carbon number of from 4 to 8, and especially preferably hexanediol.
  • component (A) is, for example, a bisphenol A type epoxy resin having a structural unit derived from hexanediol in a main chain thereof, it is one represented by the following chemical formula (I).
  • Each of m and n is an integer expressing a repeating unit number.
  • the ultraviolet ray active ester group-containing compound as the component (B) is a compound having an ester group which is activated upon irradiation with ultraviolet rays and is a component which can also be used as a curing agent of the epoxy resin as the component (A). More specifically, the ultraviolet ray active ester group-containing compound is a compound containing one or more ester groups in one molecule thereof, not containing a hydroxyl group, and being capable of curing an epoxy resin, and examples thereof include ester compounds obtained from an aliphatic or aromatic carboxylic acid and an aliphatic or aromatic hydroxy compound, and the like.
  • an ester compound constituted of an aliphatic carboxylic acid, an aliphatic hydroxy compound, or the like contains an aliphatic chain, it is able to increase solubility in an organic solvent or compatibility with an epoxy resin.
  • an ester compound constituted of an aromatic carboxylic acid, an aromatic hydroxy compound, or the like has an aromatic ring, it is able to enhance heat resistance of the resin composition.
  • Suitable examples of the ultraviolet ray active ester group-containing compound include aromatic esters obtained by using, as a raw material, a mixture of an aromatic carboxylic acid, a monohydric phenol based compound, and a polyhydric phenol based compound and subjecting the aromatic carboxylic acid and the phenolic hydroxyl groups of the monohydric based compound and the polyhydric phenol based compound to a condensation reaction.
  • Examples of the aromatic carboxylic acid include compounds in which from 2 to 4 hydrogen atoms of the aromatic ring of benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, diphenylsulfone, benzophenone, or the like are substituted with a carboxy group.
  • Examples of the monohydric phenol based compound include compounds in which one hydrogen atom of the foregoing aromatic ring is substituted with a hydroxyl group.
  • Examples of the polyhydric phenol based compound include compounds in which from 2 to 4 hydrogen atoms of the foregoing aromatic ring are substituted with a hydroxyl group.
  • examples of the aromatic carboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, benzenetricarboxylic acid, and the like.
  • examples of the monohydric phenol based compound include phenol, a variety of cresols, ⁇ -naphthol, ⁇ -naphthol, and the like.
  • examples of the polyhydric phenol based compound include hydroquinone, resorcin, catechol, 4,4′-biphenol, 4,4′-dihydroxydiphenyl ether, bisphenol A, bisphenol F, bisphenol S, bisphenol Z, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, methylated bisphenol S; a variety of dihydroxynaphthalenes, a variety of dihydroxybenzophenones, a variety of trihydroxybenzophenones, a variety of tetrahydroxybenzophenones, fluoroglycine, and the like.
  • the ultraviolet ray active ester group-containing compound may also be a resin having one or more ester groups in one molecule thereof and is available as a commercial product. Examples thereof include “EXB-9460”, “EXB-9460S”, “EXB-9470”, “EXB-9480”, and “EXB-9420”, all of which are manufactured by DIC Corporation; “BPN80”, manufactured by Mitsui Chemicals, Inc.; and the like.
  • ultraviolet ray active ester group-containing compounds may be used solely, or may be used in combination of two or more kinds thereof.
  • the ultraviolet ray active ester group-containing compound as the component (B) in the resin composition of the first invention is preferably contained in an amount of from 0.75 to 1.25 equivalents relative to one epoxy equivalent of the epoxy resin (A).
  • amount of the ultraviolet ray active ester group-containing compound as the component (B) is 0.75 equivalents or more, tack properties or curing properties are sufficient, whereas when it is not more than 1.25 equivalents, sufficient curing properties, heat resistance, and chemical resistance are obtained.
  • the epoxy resin curing accelerator as the component (C) is not particularly limited, and general curing accelerators which are used for curing of epoxy resins can be used.
  • imidazole based compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, etc.; organic phosphine based compounds such as triphenylphosphine, tributylphosphine, etc.; organic phosphite based compounds such as trimethyl phosphite, triethyl phosphite, etc.; phosphonium salt compounds such as ethyltriphenylphosphonium bromide, tetraphenylphosphonium tetraphenyl borate, etc.; trialkylamines such as triethylamine, tributylamine, etc., amine based compounds such as 4-d
  • a content of the curing accelerator in the resin composition of the first invention is preferably from 0.02 to 1.5 parts by mass based on 100 parts by mass of the epoxy resin as the component (A).
  • the content of the curing accelerator is 0.02 parts by mass or more, curing of the epoxy resin is sufficient, and heat resistance can be kept, whereas when it is not more than 1.5 parts by mass, storage stability of the resin composition and handling properties of a B-stage resin composition are favorable.
  • the content of the curing accelerator (C) is more preferably in the range of from 0.8 to 1.3 parts by mass.
  • the resin composition of the first invention containing the foregoing components (A) to (C) can be formed into a cured resin product by thermally curing it and irradiating with ultraviolet rays and developed into a variety of applications.
  • a wiring board can be obtained by disposing a cured resin layer composed of the cured resin product on a substrate having a circuit of a wiring conductor, to prepare a cured insulating resin layer and forming a wiring on the resin layer by means of plating, as described later.
  • the ester group or groups of the ultraviolet ray active ester group-containing compound as the component (B) is/are decomposed to form an oxygen-containing group on the surface of the insulating resin layer, and this oxygen-containing group brings about a high adhesive force to the wiring conductor.
  • an amount of the oxygen atom of the oxygen-containing group formed on the surface of the insulating resin can be measured by the X-ray photoelectron spectroscopy.
  • an ultraviolet ray lamp capable of undergoing radiation at a maximum wavelength in the range of from 300 to 450 nm and to irradiate ultraviolet rays in an amount of light of from about 1,000 to 5,000 mJ/cm 2 , and preferably from 3,000 to 4,000 mJ/cm 2 under an atmospheric pressure atmosphere.
  • the foregoing amount of light (mJ/cm 2 ) is expressed by “illuminance (mW/cm 2 ) ⁇ irradiation time (sec)”.
  • a condition of the foregoing thermal curing is described later.
  • a temperature of the insulating resin layer at the time of ultraviolet ray irradiation is preferably from about 50 to 80° C., and more preferably from 60 to 70° C.
  • an inorganic filler or various additive components, for example, a leveling agent, an antioxidant, a flame retardant, a thixotropy-imparting agent, a thickener, a solvent, etc., can be contained as the need arises, within the range where the object of the first invention is not impaired.
  • the inorganic filler is contained for the purpose of suppressing the coefficient of thermal expansion or increasing the coating film strength, and for example, a material selected among silica, fused silica, talc, alumina, aluminum hydroxide, barium sulfate, calcium hydroxide, Aerosil, and calcium carbonate can be used. These may be used solely, or may be used in combination of two or more kinds thereof. Incidentally, it is preferable to use silica in view of dielectric characteristic or low thermal expansion.
  • a content of the inorganic filler is preferably from 5 to 35% by volume, and more preferably from 10 to 30% by volume in a solids content of the resin composition exclusive of the solvent.
  • the content of the inorganic filler is 5% by volume or more, the increases of the coefficient of thermal expansion and the dielectric loss can be suppressed, whereas when it is not more than 35% by volume, a necessary flow at the time of forming an insulating resin in an inner layer circuit is sufficient so that an unfilled area is hardly generated.
  • such an inorganic filler may be treated with a coupling agent, and it may be homogeneously dispersed in the resin composition by means already-known kneading with a kneader, a ball mill, a bead mill, three rollers, or the like.
  • examples of the coupling agent which is used for a surface treatment of the inorganic filler include silane based, titanate based, or aluminum based coupling agents, and the like. Of these, silane based coupling agents are preferable.
  • aminosilane compounds such as N-phenyl- ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -(2-aminoethyl)aminopropyltrimethoxysilane, ⁇ -(2-aminoethyl)aminopropyltriethoxysilane, ⁇ -anilinopropyltrimethoxysilaane, ⁇ -anilinopropyltriethoxysilane, N- ⁇ -(N-vinylbenzylaminoethyl)- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -(N-vinylbenzylaminoethyl)- ⁇ -aminopropyltriethoxysilane, etc.; epoxysilane compounds such as ⁇ -glycidoxypropyltrimethoxys
  • the resin composition of the first invention can be used upon being diluted with a solvent.
  • a solvent for example, there are exemplified methyl ethyl ketone, xylene, toluene, acetone, ethylene glycol monoethyl ether, cyclohexanone, ethyl ethoxypropionate, N,N-dimethylformamide, N,N-dimethylacetamide, propylene glycol monomethyl ether, and the like. These may be used solely, or may be used in admixture of two or more kind thereof.
  • a use proportion of this solvent relative to the foregoing resin composition may be a conventionally used proportion, and the use amount can be adjusted in conformity with the equipment for forming a coating film of the insulating resin as desired.
  • a preparation method of the resin composition of the first invention is not particularly limited, and a conventionally known preparation method can be adopted.
  • the resin composition of the first invention can be prepared as a varnish by not only adding the epoxy resin as the component (A), the ultraviolet ray active ester group-containing compound as the component (B), and the epoxy resin curing accelerator as the component (C) in the foregoing solvent but adding an inorganic filler or various additive components to be used as the need arises, and then mixing and stirring the contents using a mixing machine of every kind inclusive of an ultrasonic dispersion system, a high-pressure collision dispersion system, a high-speed rotating dispersion system, a bead mill system, a high-speed shearing dispersion system, an autorotation revolution dispersion system, and the like.
  • a solids content concentration in this varnish exclusive of the solvent is preferably from 20 to 70% by mass.
  • the wiring board of the first invention is a wiring board obtained by forming an uncured resin layer on a substrate having a circuit of a wiring conductor by using the foregoing resin composition, thermally curing this, and then irradiating with ultraviolet rays to obtain a cured insulating resin layer, followed by forming a wiring thereon by means of plating.
  • a resin composition (varnish) is coated on a carrier film and then subjected to a drying treatment at a temperature of from about 80 to 180° C. for from 1 to 10 minutes, to fabricate an insulating resin layer-provided carrier film.
  • a drying treatment at a temperature of from about 80 to 180° C. for from 1 to 10 minutes, to fabricate an insulating resin layer-provided carrier film.
  • the temperature of the drying treatment is 80° C. or higher, but the time is one minute or longer, the drying sufficiently proceeds, and the generation of a void within the insulating resin layer can be suppressed, and hence, such is preferable.
  • the resin composition (varnish) coated on the carrier film is in an uncured state where the solvent in the varnish is vaporized due to drying, and a curing treatment is not performed.
  • a thickness (thickness after drying) of the insulating resin layer is preferably a minimum film thickness at which a minimum insulation distance can be ensured or more. Though this minimum insulation distance varies with a composition of the insulating resin, in general, it is preferably 3 ⁇ m or more. Though in view of insulating properties, it is advantageous to make the film thickness of the insulating resin layer thick, from the viewpoint of economy, it is preferable that the film thickness of the insulating resin layer is usually not more than about 60 ⁇ m.
  • a thickness of the carrier film is not particularly limited, it is preferably from about 10 to 200 ⁇ m, and more preferably from 20 to 100 ⁇ m.
  • a polyethylene terephthalate (PET) film is frequently used, and a PET film, a surface of which has been subjected to a release agent treatment, may also be used.
  • the substrate having a circuit of a wiring conductor to be used for the wiring board of the first invention (hereinafter also referred to as “circuit-provided insulating substrate”) is not particularly limited so far as it is an insulating substrate which is provided with a circuit on at least one surface thereof, and it may be an insulating substrate in which a circuit is formed on only one surface thereof, or an insulating substrate in which a circuit is formed on both surfaces thereof, such as those obtained by using a double-sided copper clad laminate.
  • known laminates which are used for usual wiring boards for example, glass cloth-epoxy resin, paper-phenol resin, paper-epoxy resin, glass cloth.glass paper-epoxy resin, etc., can be used.
  • the circuit may be formed by any known method, and known manufacturing methods of a wiring board, such as a subtractive method in which a copper clad laminate obtained by sticking a copper foil and the foregoing insulating substrate to each other is used, and an unnecessary portion of the copper foil is removed by etching; an additive method in which a circuit is formed by means of electroless plating in a necessary area of the foregoing insulating substrate; and the like, can be adopted.
  • a subtractive method in which a copper clad laminate obtained by sticking a copper foil and the foregoing insulating substrate to each other is used, and an unnecessary portion of the copper foil is removed by etching
  • an additive method in which a circuit is formed by means of electroless plating in a necessary area of the foregoing insulating substrate; and the like, can be adopted.
  • this circuit surface may be subjected to a circuit surface treatment for enhancing the adhesiveness.
  • This treatment method is not particularly limited, and known methods, for example, a method in which a needle crystal of copper oxide is formed with an alkali aqueous solution of sodium hypochlorite on the circuit surface, and the formed needle crystal of copper oxide is dipped in and reduced with a dimethylamine borane aqueous solution, etc., can be adopted.
  • the insulating resin layer can be formed using the foregoing insulating resin layer-provided carrier film by a lamination system or a pressing system.
  • the lamination system is a method in which the insulating resin layer-provided cast film is brought into contact with the circuit of the circuit-provided insulating substrate in such a manner that the insulating resin layer thereof faces it, the insulating resin layer is laminated using, for example, a vacuum pressure laminator lamination apparatus, and the carrier film is then peeled off.
  • a temperature is from about 50 to 170° C., and a pressure is 0.2 MPa or more. Similar to the heating temperature, while a preferred pressure value varies with a thickness of the substrate, a residual copper ratio, and the like, there is a concern that if the pressure is too high, the substrate is deformed. Therefore, the pressure is preferably not more than 1.0 MPa. In addition, when a degree of vacuum is not more than 15 hPa, embedding properties into the inner layer circuit board become favorable. It is preferable that the degree of vacuum is low as far as possible.
  • a time of heat-press bonding is preferably from about 10 to 90 seconds.
  • the time of heat-press bonding is more preferably from 20 to 60 seconds.
  • the insulating resin layer-provided cast film is brought into contact with the circuit of the circuit-provided insulating substrate in such a manner that the insulating resin layer thereof faces it, and it is desirable to perform the treatment under an adequate condition in conformity with the insulating resin layer to be used.
  • the insulating resin layer can be formed on the circuit of the circuit-provided insulating substrate by adopting a method of elevating the temperature at a temperature elevating rate of about 3° C./min from about 35° C. to 190° C. while spending about 50 minutes, keeping that temperature under a pressure of from about 2.0 to 3.0 MPa for from about 60 to 90 minutes, and then cooling to room temperature while spending about 30 minutes.
  • the insulating resin layer formed on the circuit of the circuit-provided insulating substrate as described above is first subjected to a thermal curing treatment.
  • this thermal curing treatment is desirable to perform this thermal curing treatment at a temperature for a time taking into consideration a plating treatment, an annealing treatment of the wiring conductor, and the like to be performed later. This is because when the curing is made to excessively proceed, there is a concern that the adhesiveness to the wiring conductor is lowered at the time of the plating treatment to be performed later, whereas when the curing is insufficient, there is a concern that the insulating resin layer is corroded with an alkali treatment liquid at the time of the plating treatment and dissolved in the plating liquid. Taking into consideration these matters, for example, it is preferable to cure the insulating resin layer by subjecting it to a heat treatment at from 150 to 190° C. for about 30 to 90 minutes.
  • the insulating resin layer which has been subjected to a thermal curing treatment as described above is subjected to an ultraviolet ray irradiation treatment.
  • the purpose of this ultraviolet ray irradiation treatment is one explained above regarding the resin composition.
  • an ultraviolet ray lamp having a maximum wavelength in the range of from 300 to 450 nm and to irradiate ultraviolet rays in an amount of light in the range of from about 1,000 to 5,000 mJ/cm 2 under an atmospheric pressure atmosphere.
  • a method for irradiating the insulating resin layer with ultraviolet rays under an atmospheric pressure atmosphere varies with an ultraviolet ray apparatus, and hence, it is not particularly limited. However, taking into consideration the productivity, a conveyor type ultraviolet ray irradiation system is preferable.
  • a mercury short arc lamp a high pressure mercury vapor lamp, a capillary ultra-high pressure lamp, a high pressure lamp, a metal halide lamp, and the like can be used as an ultraviolet ray lamp having a maximum wavelength in the range of from 300 to 450 nm.
  • a metal halide lamp with a wide wavelength of ultraviolet rays in the whole area is preferable.
  • the reason why the ultraviolet ray lamp having a maximum wavelength of ultraviolet rays in the range of from 300 to 450 nm is used resides in general-purpose properties and a wavelength region of ultraviolet rays. That is, this is because the ultraviolet ray lamp exhibiting a maximum wavelength of from 300 to 450 nm is generally used as a conveyor type ultraviolet ray irradiation apparatus, for example, a post-exposure apparatus of solder resist. Furthermore, this is because a metal halide type conveyor irradiation apparatus has a wide ultraviolet ray wavelength region, and by using such an apparatus as a substitution, the effects of the first invention can be exhibited without requiring a special apparatus.
  • the amount of light of the ultraviolet rays is 1,000 mJ/cm 2 or more, even if the insulating resin layer is not treated with an oxidizing roughening liquid, the adhesive force to the plated conductor is sufficient, whereas when it is not more than 5,000 mJ/cm 2 , the adhesive force is favorably revealed, and such is economically advantageous.
  • the amount of light is more preferably in the range of from 2,000 to 4,000 mJ/cm 2 .
  • a removal treatment with an oxidizing roughening liquid can be performed.
  • this oxidizing roughening liquid a chromium/sulfuric acid roughening liquid, an alkali permanganic acid roughening liquid, a sodium fluoride/chromium/sulfuric acid roughening liquid, fluoroboric acid roughening liquid, and the like can be used.
  • the treatment with an oxidizing roughening liquid after dipping in a solvent or an alkaline liquid, or a mixed liquid thereof (in general, a swelling liquid or a primitive liquid), the treatment with an oxidizing roughening liquid may be performed.
  • the solvent alcohol based solvents, for example, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, isopropyl alcohol, etc.
  • the alkaline liquid is not particularly limited so far as it is a liquid exhibiting alkalinity at the time of dissolving in water, and a sodium hydroxide solution, a potassium hydroxide solution, and the like can be used.
  • the solvent or the alkaline liquid may be mixed, and for example, a mixture having a composition of 3 g/L of sodium hydroxide and 300 mL/L of diethylene glycol monobutyl ether can be used.
  • the surface of the insulating resin layer which has been treated as described above is subjected to a plating treatment as follows.
  • the foregoing insulating resin layer is dipped in a hydrochloric acid aqueous solution of stannous chloride to achieve a neutralization treatment and further subjected to a plating catalyst imparting treatment for attaching palladium.
  • the plating catalyst imparting treatment is performed by dipping the foregoing insulating resin layer in a palladium chloride based plating catalyst liquid.
  • this insulating resin layer is dipped in an electroless plating liquid to deposit an electroless plated layer having a thickness of from about 0.3 to 1.5 ⁇ m on the plating catalyst attached onto the insulating resin layer.
  • electroplating can be further performed.
  • the electroless plating liquid which is used for the electroless plating treatment a known electroless plating liquid can be used without particular limitations.
  • a known method can be adopted without particular limitations.
  • a multi-layered wiring board can also be fabricated by repeating such a technique.
  • the first invention also provides a manufacturing method of a wiring board.
  • the manufacturing method of a wiring board of the first invention comprises including (a) a step of forming an uncured resin layer (insulating resin layer) on a substrate having a circuit of a wiring conductor by using the resin composition of the first invention, (b) a step of thermally curing the uncured resin layer and subsequently irradiating with ultraviolet rays to form a cured resin layer, and (c) a step of subjecting the cured resin layer to an electroless plating treatment.
  • a step of applying an electroplating treatment onto the electroless plating can be further included, and (c′) a step of subjecting the surface of the cured resin layer to a roughening treatment with an oxidizing roughening liquid can be included between the step (b) and the step (c).
  • the manufacturing method of a wiring board according to the second invention is a method for manufacturing a wiring board having an insulating resin layer and a wiring formed on the surface of the insulating resin layer, which includes a laminate forming step of forming a laminate having the insulating resin layer and a support; a hole forming step of providing a hole in the laminate; a desmearing treatment step of removing a smear within the hole with a desmearing treatment liquid; a support removal step of removing the support from the laminate; a wiring forming step of forming the wiring on the surface of the insulating resin layer from which the support has been removed; and after the laminate forming step and before the wiring forming step, an ultraviolet ray irradiation step of irradiating ultraviolet rays on the surface of the insulating resin layer from which the support has been removed, to enhance an adhesive force to the wiring.
  • a support-provided insulating resin layer composed of a laminate having an insulating resin layer and a support is formed.
  • a material of this support is not particularly limited so far as it is sparingly soluble in a desmearing treatment liquid which is used in a desmearing treatment step as described later, and a synthetic resin, a metal, and the like are useful.
  • a synthetic resin polyester films with heat resistance, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc., are preferable.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • copper is preferable.
  • a thickness of this support is not particularly limited so far as it is a thickness such that the occurrence of exposure of a part of the surface of the insulating resin layer to be caused due to dissolution in a process of the desmearing treatment step is prevented.
  • the thickness of the support is preferably from about 10 to 200 ⁇ m, and more preferably from 20 to 100 ⁇ m.
  • this support is copper, from the viewpoint of making the irregularities of the surface of the insulating resin layer small, a low profile foil is more preferable than a general copper foil, and a profile-free foil is more preferable.
  • a surface roughness Ra of this support is preferably not more than 0.12 ⁇ m, and more preferably not more than 0.1 ⁇ m. According to this, the irregularities of the surface of the insulating resin layer coming into contact with the surface of this support can be suppressed, and it is possible to contrive to make the wiring of the surface of the insulating resin layer fine.
  • An insulating resin composition serving as a material of this insulating resin layer is not particularly limited so far as its adhesive force to the wiring is enhanced due to the irradiation with ultraviolet rays, and a thermosetting resin is suitably used.
  • a composition containing (A) an epoxy resin, (B) an active ester group-containing compound, and (C) an epoxy resin curing accelerator is used as the insulating resin composition serving as a material of the insulating resin layer.
  • an inorganic filler or various additive components can be contained within the range where the object of the second invention is not impaired.
  • the resin composition in the first invention as described above can be suitably used.
  • an epoxy resin the same as that in the first invention is suitable.
  • the smear can be easily removed and that a minute roughened irregular shape can be uniformly formed on the surface of the insulating resin, a material in which a hydrocarbon is contained in a skeleton of the epoxy resin is preferable.
  • a material in which a large amount of a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or an epoxy resin having an ethylenically unsaturated compound in a skeleton thereof is contained in an insulating resin blend is suitable. Furthermore, from the viewpoint of insulation reliability or heat resistance, one or more kinds of the foregoing epoxy resins may be properly mixed.
  • any compound can be used without particular limitations so far as it is a compound containing one or more ester groups in one molecule thereof, not containing a hydroxyl group, and being capable of curing an epoxy resin.
  • an ultraviolet ray active ester group-containing compound the same as that in the first invention is suitable.
  • the active ester group-containing compound which is used as a curing agent of the epoxy resin it is preferable to use the active ester group-containing compound in an amount of from 0.75 to 1.25 equivalents relative to one epoxy equivalent of the epoxy resin. When the content falls within this range, the heat resistance is favorable.
  • the epoxy resin curing accelerator a general curing accelerator which is used for curing of an epoxy resin can be used.
  • an epoxy resin curing accelerator the same as that in the first invention is suitable.
  • a content of the curing accelerator in the insulating resin is also the same as that described regarding the epoxy resin curing accelerator in the first invention.
  • an inorganic filler may be blended for the purpose of increasing the coefficient of thermal expansion or the coating film strength.
  • the kind and content of the inorganic filler are the same as those described regarding the inorganic filler in the first invention.
  • the foregoing insulating resin composition may be blended with a coupling agent which is used for the surface treatment of the inorganic filler.
  • a coupling agent which is used for the surface treatment of the inorganic filler.
  • a coupling agent the same as that in the first invention is suitable.
  • additive components for example, a leveling agent, an antioxidant, a flame retardant, a thixotropy-imparting agent, a thickener, and the like can be contained.
  • the insulating resin composition is used upon being diluted with a solvent.
  • a solvent the same as that in the first invention is suitable.
  • the materials described in Patent Documents 1 to 2 may also be used.
  • a polyphenylene ether resin disclosed in Patent Document 1 may be adopted.
  • An epoxy resin, a phenol resin, a polyimide resin, a polyamide-imide resin, a bismaleimide resin, an unsaturated polyester resin, a silicon resin, and the like exemplified in Patent Document 2 may be adopted.
  • the insulating resin composition may be an epoxy resin composition containing an epoxy resin having two or more epoxy groups in one molecule thereof, di ( ⁇ -naphthyl) isophthalate, and a curing accelerator.
  • a cyclic olefin based resin and a compound having an active ester group may also be used.
  • a thickness (thickness after drying) of the insulating resin layer is not particularly limited, and it is preferably in the range of from 3 to 60 ⁇ m depending upon an application. To make the film thickness of the insulating resin layer thick is advantageous in view of insulation properties. On the other hand, however, from the viewpoint of economy, in general, the thickness of the insulating resin layer is preferably not more than about 60 ⁇ m, and for the purpose of ensuring the insulation, it is preferably 3 ⁇ m or more.
  • the laminate (the support and the insulating resin layer) is provided with a hole (a via hole, a through-hole, or a part insertion hole).
  • This hole is preferably performed by using a drill, a laser, a plasma, or a combined method thereof.
  • a laser a carbonic acid gas laser, a YAG laser, and the like are generally used.
  • an oxidizing roughening liquid the same as that in the first invention is suitable.
  • the laminate is dipped in a hydrochloric acid aqueous solution of stannous chloride to achieve a neutralization treatment, and after washing with water, the resulting laminate is dried for the purpose of moisture removal.
  • the support is removed from the laminate.
  • This removal of the support can be performed by means of peeling off, etching, or the like.
  • the support is a synthetic resin
  • the removal by means of peeling off is preferable
  • the removal by means of etching is preferable.
  • a sulfuric acid/hydrogen peroxide based aqueous solution a cupric chloride aqueous solution, a ferric chloride aqueous solution, an ammonium peroxodisulfate aqueous solution, a sodium peroxodisulfate aqueous solution, and the like
  • a sulfuric acid/hydrogen peroxide based aqueous solution a cupric chloride aqueous solution, a ferric chloride aqueous solution, an ammonium peroxodisulfate aqueous solution, a sodium peroxodisulfate aqueous solution, and the like
  • a sulfuric acid/hydrogen peroxide based aqueous solution a cupric chloride aqueous
  • the adhesive force of the surface of the insulating resin layer to the wiring is enhanced.
  • the wiring can be formed with a strong adhesive force on the surface of the insulating resin layer in the subsequent wiring forming step.
  • This method for irradiating ultraviolet rays is not particularly limited, and the ultraviolet rays may be irradiated in the atmosphere, or may be irradiated in an ozone solution as in Patent Document 2.
  • this ultraviolet ray irradiation step is performed after the foregoing support removal step, the ultraviolet ray irradiation step may also be performed at any timing after the foregoing laminate forming step and before a wiring forming step as described later.
  • the foregoing wiring is formed on the surface of the foregoing insulating resin layer from which the support has been removed. Since the wiring is formed on the surface of the insulating resin layer whose adhesive force to the wiring has been enhanced by the irradiation with ultraviolet rays as described above, an adhesion of the wiring to the insulating resin layer increases.
  • a prescribed resist pattern is formed on the surface of the insulating layer, and a conductive layer is formed by means of electroless plating, followed by removing the resist pattern.
  • an electroplating treatment may be further applied onto the electroless plating.
  • the ultraviolet ray irradiation step is carried out after the support removal step and before the wiring forming step, but it should not be construed that the second invention is limited thereto.
  • the ultraviolet ray irradiation step may be carried out after the hole forming step and before the desmearing treatment step.
  • ultraviolet rays are irradiated on the insulating resin layer from the support side of the laminate.
  • the ultraviolet rays transmit through the support to reach the surface of the insulating resin layer, thereby enhancing an adhesive force of this surface of the insulating resin layer to the wiring.
  • a material of the support which is used in this Modification Example 1 is not particularly limited so far as it is sparingly soluble in the desmearing treatment liquid which is used in the desmearing treatment step and is able to transmit ultraviolet rays therethrough, and a synthetic resin is useful.
  • a synthetic resin polyester films with heat resistance, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc., are preferable.
  • the wiring can be formed with a strong adhesive force on the surface of the insulating resin layer in the subsequent wiring forming step.
  • This method for irradiating ultraviolet rays is not particularly limited, and the ultraviolet rays may be irradiated in the atmosphere.
  • ultraviolet rays can be irradiated on the surface of a smooth support plate before the desmearing treatment, and ultraviolet rays can be uniformly irradiated on the surface of the insulating resin layer.
  • the ultraviolet ray irradiation step may also be carried out after the desmearing step and before the support removal step.
  • ultraviolet rays are irradiated on the insulating resin layer from the support side of the laminate. The ultraviolet rays transmit through the support to reach the surface of the insulating resin layer, thereby enhancing an adhesive force of this surface of the insulating resin layer to the wiring.
  • a material of the support which is used in this Modification Example 2 is not particularly limited so far as it is sparingly soluble in the desmearing treatment liquid which is used in the desmearing treatment step and is able to transmit ultraviolet rays therethrough, and a synthetic resin is useful.
  • a synthetic resin polyester films with heat resistance, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc., are preferable.
  • the wiring can be formed with a strong adhesive force on the surface of the insulating resin layer in the subsequent wiring forming step.
  • This method for irradiating ultraviolet rays is not particularly limited, and the ultraviolet rays may be irradiated in the atmosphere.
  • FIG. 1 is a cross-sectional view explaining a manufacturing method of a wiring board according to Embodiment B of the second invention.
  • this wiring board 10 is composed of a substrate 2 having a first wiring circuit 1 on the back surface side and a second wiring circuit 3 on the front surface side, an insulating resin layer 4 on the second wiring circuit 3 , a third wiring circuit 5 on this insulating resin layer 4 , a first via hole 6 extending from the third wiring circuit 5 to the second wiring circuit 3 , and a second via hole 7 extending from the third wiring circuit 5 to the first wiring circuit 1 .
  • the substrate 2 having the first and second wiring circuits 1 and 3 (hereinafter also referred to as “circuit-provided insulating substrate”) is not particularly limited so far as it is an insulating substrate having a circuit provided on the both surfaces of the substrate 2 , and examples thereof include a double-sided copper clad laminate.
  • this insulating substrate known laminates which are used for usual wiring boards, for example, glass cloth-epoxy resin, paper-phenol resin, paper-epoxy resin, glass cloth.glass paper-epoxy resin, etc., can be used without particular limitations.
  • the circuit may be formed by any known method, and known manufacturing methods of a wiring board, such as a subtractive method in which a copper clad laminate obtained by sticking a copper foil and the foregoing insulating substrate to each other is used, and an unnecessary portion of the copper foil is removed by etching; an additive method in which a circuit is formed by means of electroless plating in a necessary area of the foregoing insulating substrate; and the like, can be adopted.
  • a subtractive method in which a copper clad laminate obtained by sticking a copper foil and the foregoing insulating substrate to each other is used, and an unnecessary portion of the copper foil is removed by etching
  • an additive method in which a circuit is formed by means of electroless plating in a necessary area of the foregoing insulating substrate; and the like, can be adopted.
  • each of the circuits 1 and 3 may be subjected to a circuit surface treatment for enhancing the adhesiveness.
  • This treatment method is not particularly limited, and known methods, for example, a method in which a needle crystal of copper oxide is formed with an alkali aqueous solution of sodium hypochlorite on the circuit surface, and the formed needle crystal of copper oxide is dipped in and reduced with a dimethylamine borane aqueous solution, etc., can be adopted.
  • a resin composition containing (A) an epoxy resin, (B) an active ester group-containing compound, and (C) an epoxy resin curing accelerator as described above is used as the insulating resin composition constituting the insulating resin layer.
  • thermosetting insulating resin composition A preparation method of a thermosetting insulating resin composition is not particularly limited, and a conventionally known preparation method can be adopted.
  • thermosetting insulating resin composition can be prepared as a varnish by not only adding the epoxy resin as the component (A), the active ester group-containing compound as the component (B), and the epoxy resin curing accelerator as the component (C) in the foregoing solvent but adding an inorganic filler or various additive components to be used as the need arises, and then mixing and stirring the contents using a mixing machine of every kind inclusive of an ultrasonic dispersion system, an autorotation revolution dispersion system, and the like.
  • a solids content concentration of this varnish exclusive of the solvent is preferably from 20 to 70% by mass.
  • the thus prepared insulating resin varnish is coated on a support 9 made of a synthetic resin or a copper foil and then dried to obtain the insulating resin layer 4 .
  • the drying after coating the insulating resin varnish on the support 9 can be performed at from 80 to 180° C. for from about 1 to 10 minutes.
  • the drying temperature is higher than 80° C., or the time is one minute or longer, the drying sufficiently proceeds, and an amount of the residual solvent within the insulating resin layer 4 becomes small.
  • an amount of the resin flow is suppressed, and the generation of a void within the insulating resin layer 4 to be caused due to volatilization of the residual solvent can be prevented.
  • a thickness (thickness after drying) of the insulating resin layer 4 is not particularly limited, and it is preferably in the range of from 3 to 60 ⁇ m depending upon an application. To make the film thickness of the insulating resin layer 4 thick is advantageous in view of insulation properties. On the other hand, however, from the viewpoint of economy, in general, the thickness of the insulating resin layer 4 is preferably not more than about 60 ⁇ m, and for the purpose of ensuring the insulation, it is preferably 3 ⁇ m or more.
  • a thickness of the support 9 is not particularly limited, it is preferably from about 10 to 200 ⁇ m, and more preferably from 20 to 100 ⁇ m.
  • a polyethylene terephthalate (PET) film or a copper foil is suitably used as the support 9 .
  • Lamination of the insulating resin layer 4 provided with the support 9 and the insulating substrate 2 provided with the circuits 1 and 3 can be performed by a lamination process or a pressing process.
  • the insulating resin layer 4 provided with the support 9 is superimposed on the wiring circuit 3 of the insulating substrate 2 provided with the circuits 1 and 3 in such a manner that the insulating resin layer 4 faces it, and the insulating resin layer 4 is laminated using, for example, a vacuum pressure laminator.
  • a temperature is from 50 to 170° C., and a pressure is 0.2 MPa or more. Similar to the heating temperature, while a preferred pressure value varies with a thickness of the substrate, a residual copper ratio, and the like, in order to suppress the deformation of the substrate, the pressure is preferably not more than 1.0 MPa ⁇ s. In addition, when a degree of vacuum is not more than 15 hPa, embedding properties into the inner layer circuit board are enhanced. On the other hand, it is preferable that the degree of vacuum is high as far as possible.
  • the treatment is preferable to perform the treatment at a degree of vacuum in the range of from 5 to 10 hPa.
  • a time of heat-press bonding is 10 seconds or longer, the time required for flowing of the resin into the inner layer circuit is sufficient, whereas when it is not longer than 90 seconds, the productivity is enhanced, and therefore, the time of heat-press bonding is preferably from 20 to 60 seconds.
  • the insulating resin layer 4 provided with the support 9 is superimposed on the circuit 3 of the insulating substrate 2 provided with the circuits 1 and 3 in such a manner that the insulating resin layer 4 faces it, and it is desirable to perform the pressing under an adequate condition in conformity with the insulating resin layer 4 to be used.
  • the insulating resin 4 provided with the support 9 can be formed on the circuit 3 of the insulating substrate 4 provided with the circuits 1 and 3 by elevating the temperature at a temperature elevating rate of 3° C./min for 50 minutes, keeping at 190° C. under a pressure of from 2.0 to 3.0 MPa for from 60 to 90 minutes, and then cooling to room temperature for 30 minutes.
  • the insulating resin layer 4 formed on the circuit 3 of the insulating substrate 2 provided with the circuits 1 and 3 as described above is first thermally cured. It is desirable to perform this thermal curing at a temperature for a time taking into consideration a plating treatment, an annealing treatment of the wiring conductor, and the like to be performed later. This is because when the curing is made to excessively proceed, there is a concern that the adhesiveness to the wiring conductor is lowered at the time of the subsequent plating treatment, whereas when the curing is reversely insufficient, there is a concern that the insulating resin layer 4 is corroded with an alkali treatment liquid at the time of the plating treatment and dissolved in the plating liquid. Taking into consideration these matters, for example, in the case of the epoxy resin based insulating resin 4 , it is preferable to cure the insulating resin layer 4 by applying a heat treatment at from 150 to 190° C. for about 30 to 90 minutes.
  • boring processing is performed to form the via hole 6 and the through-hole 7 . Details of this boring processing are those described above.
  • desmearing within the via hole 6 and the through-hole 7 is performed with a desmearing treatment liquid. Details of this desmearing treatment liquid are those described above for the hole forming step.
  • the synthetic resin film or the copper foil as the support 9 is removed.
  • the synthetic resin film is preferably removed by peeling off.
  • the copper foil is preferably removed by means of etching.
  • an oxygen-containing group is formed due to decomposition of the active ester group in the active ester group-containing compound as the component (B) on the surface of the insulating resin layer 4 , and this oxygen-containing group brings about a high adhesive force to the wiring conductor.
  • An amount of the oxygen atom of the oxygen-containing group formed on the surface of the insulating resin 4 can be measured by the X-ray photoelectron spectroscopy.
  • an ultraviolet ray lamp capable of undergoing radiation in the range of from 300 to 450 nm and to irradiate ultraviolet rays in an amount of light of from about 1,000 to 5,000 mJ/cm 2 , and preferably from 2,000 to 4,000 mJ/cm 2 under an atmospheric pressure atmosphere.
  • the foregoing amount of light (mJ/cm 2 ) is expressed by “illuminance (mW/cm 2 ) ⁇ irradiation time (sec)”.
  • a temperature of the insulating resin layer 4 at the time of ultraviolet ray irradiation is preferably from about 50 to 90° C., and more preferably from 60 to 80° C.
  • a method for irradiating the insulating resin 4 with ultraviolet rays under an atmospheric pressure atmosphere varies with an ultraviolet ray apparatus, and hence, it is not particularly limited. However, taking into consideration the productivity, conveyor type ultraviolet ray irradiation is preferable.
  • the ultraviolet ray lamp a mercury short arc lamp, a high pressure mercury vapor lamp, a capillary ultra-high pressure lamp, a high pressure lamp, a metal halide lamp, and the like can be used as an ultraviolet ray lamp having a wavelength in the range of from 300 to 450 nm. Of these lamps, a metal halide lamp with a wide wavelength of ultraviolet rays in the whole area is preferable.
  • An object of the use of the ultraviolet ray lamp having a wavelength of ultraviolet rays in the range of from 300 to 450 nm is related to general-purpose properties and a wavelength region of ultraviolet rays. That is, this is because the ultraviolet ray lamp having a wavelength of from 300 to 450 nm is generally used as a conveyor type ultraviolet ray irradiation apparatus, for example, a post-exposure apparatus of solder resist.
  • a metal halide type conveyor irradiation apparatus has a wide ultraviolet ray wavelength region, and by using such an apparatus as a substitution, the effects of the second invention can be exhibited without requiring a special apparatus.
  • an amount of the ultraviolet rays is 1,000 mJ/cm 2 or more, in the case where the insulating resin layer 4 is not treated with an oxidizing roughening liquid, the adhesive force to the plated conductor is sufficient, whereas even when it exceeds 5,000 mJ/cm 2 , the adhesive force does not change, and therefore, it is preferably from 1,000 to 5,000 mJ/cm 2 .
  • the amount of the ultraviolet rays is more preferably in the range of from 2,000 mJ/cm 2 to 4,000 mJ/cm 2 .
  • the surface of the insulating resin layer 4 which has been treated with ultraviolet rays is subjected to a plating treatment as follows.
  • the foregoing insulating resin layer 4 is subjected to a plating catalyst imparting treatment for attaching palladium.
  • the plating catalyst treatment is performed by dipping in a palladium chloride based plating catalyst liquid.
  • the insulating resin layer 4 is dipped in an electroless plating liquid to deposit an electroless plated layer having a thickness of from 0.3 to 1.5 ⁇ m thereon.
  • electroplating is further performed.
  • the electroless plating liquid which is used for the electroless plating a known electroless plating liquid can be used without particular limitations.
  • a known method can be adopted without particular limitations.
  • the wiring board 10 can be manufactured by forming the wiring circuit 5 on the insulating resin layer 4 by the plating treatment.
  • a single-sided wiring board may be used.
  • a multi-layered wiring board can also be fabricated by repeating such a technique to form plural layers of each of the insulating resin layer and the wiring circuit.
  • the ultraviolet ray irradiation is carried out after the support removal and before the plating treatment, but it should not be construed that the second invention is limited thereto.
  • the ultraviolet ray irradiation may be carried out after the boring processing and before the desmearing treatment.
  • the insulating resin layer 4 is subjected to an ultraviolet ray irradiation treatment from the side of the support 9 under the following condition in a state where the support 9 is present on the surface of the insulating resin layer 4 .
  • the surface of the insulating resin layer 4 reveals a high adhesive form to the wiring conductor.
  • the ultraviolet ray irradiation may also be carried out after the desmearing treatment and before the removal of the support.
  • the insulating resin layer 4 is subjected to an ultraviolet ray irradiation treatment from the side of the support 9 under the following condition in a state where the support 9 is present on the surface of the insulating resin layer 4 . According to this, the surface of the insulating resin layer 4 reveals a high adhesive form to the wiring conductor.
  • the foregoing synthetic resin is useful as the support.
  • FIG. 2 is a cross-sectional view explaining another example of a manufacturing method of a wiring board.
  • a wiring board 20 has a prepreg laminate 21 , insulating resin layers 4 laminated on both the upper and lower sides thereof, third wiring circuits 5 laminated on both the upper and lower sides thereof, and a through-hole 7 penetrating these layers.
  • thermosetting insulating resin composition is prepared.
  • the insulating resin layer 4 provided with the support 9 is formed.
  • the insulating resin layer 4 provided with the support 9 is superimposed on each of the front and back surfaces of the prepreg laminate 21 in such a manner that the side of the insulating resin layer 4 comes into contact therewith, and these are laminated. Similar to the foregoing Embodiment B of the second invention, this lamination method can be performed by a lamination process or a pressing process.
  • thermal curing of the insulating resin layer 4 is performed.
  • boring processing for penetration in the thickness direction is performed to form the through-hole 7 , and then, a desmearing treatment within the through-hole 7 is performed. Details of the boring processing and the desmearing treatment are the same as those in the first example ( FIG. 1 ).
  • the insulating resin layers 4 on the both surfaces are subjected to an ultraviolet ray irradiation treatment.
  • the insulating resin layers 4 on the both surfaces are subjected to a plating treatment to manufacture the third wiring circuits 5 and 5 .
  • the wiring board 20 can be manufactured.
  • each of the insulating resin layer 4 and the wiring circuit 5 may be formed by repeating such a technique.
  • the ultraviolet ray irradiation is carried out after the support removal and before the plating treatment, but it should not be construed that the second invention is limited thereto.
  • the ultraviolet ray irradiation may be carried out after the boring processing and before the desmearing treatment.
  • the insulating resin layers 4 on the both surfaces are subjected to an ultraviolet ray irradiation treatment.
  • the ultraviolet ray irradiation may also be carried out after the desmearing treatment and before the removal of the support. In that case, after the desmearing treatment, the insulating resin layers 4 on the both surfaces are subjected to an ultraviolet ray irradiation treatment.
  • the foregoing synthetic resin is useful as the support.
  • a portion having a width of 10 mm and a length of 100 mm was formed in a part of an outer layer circuit layer (third circuit layer), and one end thereof was peeled off and gripped by a gripper. Then, a load at the time of ripping off a portion of about 50 mm in the vertical direction at room temperature was measured.
  • a test piece in which an outer layer circuit is subjected to an etching treatment to remove copper is fabricated.
  • This test piece was cut into a size of 2 mm square; different three areas in the test piece were measured using an ultra-high depth shape measurement microscope “VK-8500 Model”, manufactured by Keyence Corporation under a condition at a measuring length of 149 ⁇ m, a magnification of 2,000 times, and a resolution of 0.05 ⁇ m; a value obtained by subtracting a minimum part from a maximum part in roughness in the measuring length of 149 ⁇ m was defined as a surface roughness of the insulating resin layer; and an average value of the roughness in the three areas was calculated.
  • a multi-layered wiring board was cut into a size of 25 mm square and immediately thereafter, floated on a solder bath prepared at 288° C. ⁇ 2° C., and a time until swelling was generated was examined.
  • a glass cloth base material epoxy resin double-sided copper clad laminate (a trade name: “MCL-E-67”, manufactured by Hitachi Chemical Co., Ltd., having a thickness of a copper foil of 18 ⁇ m and a thickness of a substrate of 0.8 mm and having a roughened foil on the both surfaces thereof) was subjected to etching to fabricate a circuit board having a circuit layer (hereinafter referred to as “first circuit layer”) on one surface thereof.
  • the resin composition (varnish) obtained above in (3) was coated on a polyethylene terephthalate (PET) film (thickness: 38 ⁇ m) as a carrier film and subjected to a drying treatment at 100° C. for 10 minutes, thereby fabricating an insulating resin layer-provided carrier film roll having a film thickness of 50 ⁇ 3 ⁇ m.
  • PET polyethylene terephthalate
  • the foregoing insulating resin layer-provided carrier film was laminated on one surface of the circuit board obtained above in (1) by using a batch type vacuum pressure laminator “MVLP-500” (a trade name, manufactured by Meiki Co., Ltd.) in such a manner that the insulating resin layer came into contact with the circuit layer.
  • MVLP-500 a trade name, manufactured by Meiki Co., Ltd.
  • the insulating resin layer was subjected to a thermal curing treatment under a curing condition at 170° C. for 60 minutes and then irradiated with ultraviolet rays in an amount of light of 3,000 mJ/cm 2 by a metal halide lamp (maximum wavelength: 350 to 380 nm) using a conveyor type ultraviolet ray irradiation apparatus.
  • the insulating resin layer-provided substrate obtained above in (4) was dipped in a conditioner liquid “CLC-601” (a trade name, manufactured by Hitachi Chemical Co., Ltd.) at 60° C. for 5 minutes, and thereafter, the resulting insulating resin layer-provided substrate was washed with water and dipped in a pre-dipping liquid “PD-201” (a trade name, manufactured by Hitachi Chemical Co., Ltd.) at room temperature for 2 minutes.
  • a conditioner liquid “CLC-601” a trade name, manufactured by Hitachi Chemical Co., Ltd.
  • the insulating resin layer-provided substrate was subjected to a dipping treatment with “HS-202B” (a trade name, manufactured by Hitachi Chemical Co., Ltd.) as an electroless plating catalyst containing PdCl 2 at room temperature for 10 minutes, and thereafter, the resulting insulating resin layer-provided substrate was washed with water, dipped in a “CUST-201 plating liquid” (a trade name, manufactured by Hitachi Chemical Co., Ltd.) as an electroless copper plating liquid at room temperature for 15 minutes, and further subjected to electroplating with copper sulfate. Thereafter, annealing was performed at 170° C. for 30 minutes to form a conductor layer having a thickness of 20 ⁇ m on the surface of the insulating resin layer.
  • HS-202B a trade name, manufactured by Hitachi Chemical Co., Ltd.
  • an oxide film on the copper surface was removed by means of polishing with a #600 buff roll. Thereafter, a resist film for etching was formed and subjected to an etching treatment, and the resist film for etching was then removed to form a second circuit containing a via hole connected to the first circuit. Furthermore, for the purpose of multi-layering, the surface of the second circuit conductor was dipped in an aqueous solution containing 50 g/L of sodium chlorite, 20 g/L of NaOH, and 10 g/L of trisodium phosphate at 85° C. for 20 minutes and then washed with water, followed by drying at 80° C. for 20 minutes, thereby forming irregularities of copper oxide on the surface of the second circuit conductor.
  • Example 1 Various multi-layered wiring boards were fabricated by following the same operations as those in Example 1, except that in Example 1, the composition of the resin composition was changed as shown in Table 1. Results obtained by evaluation in the same manners as those in Example 1 are shown in Table 1.
  • a multi-layered wiring board was fabricated by following the same operations as those in Example 1, except that in Example 1, a resin composition in which spherical silica “SO-25R” (a trade name, manufactured by Admatechs Company Limited) having an average particle diameter of 0.5 ⁇ m was added as the inorganic filler as shown in Table 1 was used; and that the amount of the solvent was changed to 51 parts by mass. Results obtained by evaluation in the same manners as those in Example 1 are shown in Table 1.
  • the insulating resin layer-provided substrate was irradiated with ultraviolet rays in an amount of light of 3,000 mJ/cm 2 by using a conveyor type ultraviolet ray irradiation apparatus with a metal halide lamp as the lamp (maximum wavelength: 350 to 380 nm).
  • an aqueous solution containing 200 mL/L of diethylene glycol monobutyl ether and 5 g/L of NaOH as a swelling liquid was heated to 80° C., and the insulating resin layer-provided substrate was dipped therein for 5 minutes.
  • an aqueous solution containing 60 g/L of KMnO 4 and 40 g/L of NaOH as a roughening liquid was heated to 80° C., and the insulating resin layer-provided substrate was dipped therein for 10 minutes.
  • a multi-layered wiring board was fabricated by following the same operations as those in Example 1. Results obtained by evaluation in the same manners as those in Example 1 are shown in Table 1.
  • a multi-layered wiring board was fabricated by following the same operations as those in Example 1, except that in Example 1, the lamp for ultraviolet ray irradiation was changed to a conveyor type ultraviolet ray irradiation apparatus with a high pressure mercury vapor lamp (maximum wavelength: 310 to 370 nm). Incidentally, similar to Example 1, the ultraviolet rays were irradiated in an amount of light of 3,000 mJ/cm 2 .
  • a multi-layered wiring board was fabricated by following the same operations as those in Example 1, except that in Example 1, the composition of the resin composition was changed so as to not use the ultraviolet ray active ester group-containing compound as shown in Table 1. Results obtained by evaluation in the same manners as those in Example 1 are shown in Table 1.
  • a multi-layered wiring board was fabricated by following the same operations as those in Example 1, except that in the resin composition of Example 1, a phenol novolak type epoxy resin (a trade name: “N-770”, manufactured by DIC Corporation, hydroxyl group equivalent: 190) that is an epoxy resin not having a structural unit derived from hexanediol was used as the component (A) as shown in Table 1. Results obtained by evaluation in the same manners as those in Example 1 are shown in Table 1.
  • a multi-layered wiring board was fabricated by following the same operations as those in Example 1, except that in the resin composition of Example 1, a phenol novolak type epoxy resin (a trade name: “TD-2131”, manufactured by DIC Corporation, ester equivalent: 105) was used as the component (B) as shown in Table 1. Results obtained by evaluation in the same manners as those in Example 1 are shown in Table 1.
  • A1 Epoxy resin having hexanediol in a skeleton thereof (prepared in Example 1(2))
  • A2 Phenol novolak type epoxy resin, “N-770” (a trade name, manufactured by DIC Corporation, as a comparative component)
  • C1 Curing accelerator, imidazole derivative compound, 1-cyanoethyl-2-phenylimidazolium trimellitate (a trade name: “2PZ-CNS”, manufactured by Shikoku Chemicals Corporation)
  • E1 Inorganic filler, spherical silica having an average particle diameter of 0.5 ⁇ m, “SO-25R” (a trade name, manufactured by Admatechs Company Limited)
  • the wiring board having an insulating resin layer prepared by thermally curing a resin composition and irradiating it with ultraviolet rays is favorable in the adhesive strength to the outer layer copper in a state where the surface roughness of the insulating resin layer is small, so that it is suitable for realization of fine wiring.
  • the subject wiring board is excellent in the solder heat resistance at 288° C. and also excellent in lead-free solder mounting.
  • a portion having a width of 10 mm and a length of 100 mm was formed in a part of an outermost layer circuit layer (a third circuit layer in a multi-layered wiring board and a first circuit layer in a single-layered wiring board, respectively), and one end thereof was peeled off and gripped by a gripper. Then, a load at the time of ripping off a portion of about 50 mm in the vertical direction at room temperature was measured.
  • a test piece in which an outer layer circuit is subjected to an etching treatment to remove copper is fabricated.
  • This test piece was cut into a size of 2 mm square; different three areas in the test piece were measured using an ultra-high depth shape measurement microscope “VK-8500 Model”, manufactured by Keyence Corporation under a condition at a measuring length of 149 ⁇ m, a magnification of 2,000 times, and a resolution of 0.05 ⁇ m; a value obtained by subtracting a minimum part from a maximum part in roughness in the measuring length of 149 ⁇ m was defined as a surface roughness of the insulating resin layer; and an average value of the roughness in the three areas was calculated.
  • a wiring board was cut into a size of 25 mm square and immediately thereafter, floated on a solder bath prepared at 288° C. ⁇ 2° C., and a time until swelling was generated was examined.
  • a glass cloth base material epoxy resin double-sided copper clad laminate (a trade name: “MCL-E-67”, manufactured by Hitachi Chemical Co., Ltd., having a thickness of a copper foil of 18 ⁇ m and a thickness of a substrate of 0.8 mm and having a roughened foil on the both surfaces thereof) was subjected to etching to fabricate a circuit board having a circuit layer (hereinafter referred to as “first circuit layer”) on one surface thereof.
  • a composition of an insulating resin is shown in Table 2. 49 parts by mass of the epoxy resin prepared in (2) as the component (A), 27 parts by mass of an ultraviolet ray active ester group-containing resin (a trade name: “EXB-9460S”, manufactured by DIC Corporation, ester equivalent: 223) as the component (B), and 0.15 parts by mass of 1-cyanoethyl-2-phenylimidazoliumtrimellitate (a trade name: “2PZ-CNS”, manufactured by Shikoku Chemicals Corporation) as the component (C) were dissolved in 40 parts by mass of methyl ethyl ketone (hereinafter referred to as “MEK”) as a solvent, thereby obtaining an insulating resin composition (varnish).
  • MEK methyl ethyl ketone
  • the insulating resin composition obtained above in (3) was coated on a polyethylene terephthalate (PET) film (thickness: 38 ⁇ m) and subjected to a drying treatment at 100° C. for 10 minutes, thereby fabricating a support-provided insulating resin layer having a film thickness of 50 ⁇ 3 ⁇ m.
  • PET polyethylene terephthalate
  • the foregoing support-provided insulating resin layer and the circuit board obtained above in (1) were superimposed in such a manner that the insulating resin layer and the circuit layer came into contact with each other, followed by lamination by using a batch type vacuum pressure laminator “MVLP-500” (a trade name, manufactured by Meiki Co., Ltd.). Subsequently, the insulating resin layer was subjected to a thermal curing treatment under a curing condition at 170° C. for 60 minutes, thereby obtaining an insulating resin layer-provided substrate.
  • MVLP-500 a trade name, manufactured by Meiki Co., Ltd.
  • Via holes for interlayer connection extending from the support to the circuit layer were processed and fabricated on this insulating resin layer-provided substrate by using a CO 2 laser drilling machine “LCO-1B21 Model”, manufactured by Hitachi Via Mechanics, Ltd. under a condition at a beam diameter of 80 ⁇ m, a frequency of 500 Hz, a pulse width of 5 ⁇ sec, and a shot number of 7.
  • an aqueous solution containing 200 mL/L of diethylene glycol monobutyl ether and 5 g/L of NaOH as a swelling liquid was heated to 80° C., and the insulating resin layer-provided substrate was dipped therein for 5 minutes.
  • an aqueous solution containing 60 g/L of KMnO 4 and 40 g/L of NaOH as a desmearing treatment liquid was heated to 80° C., and the insulating resin layer-provided substrate was dipped therein for 20 minutes.
  • the resulting insulating resin layer-provided substrate was dipped in an aqueous solution of a neutralizing liquid (5 nCl 2 : 30 g/L, H 2 SO 4 having a concentration of 98% by mass: 300 mL/L) at room temperature for 5 minutes, thereby achieving neutralization. Thereafter, the insulating resin layer-provided substrate was washed with water for 5 minutes and then dried at 100° C. for 10 minutes.
  • a neutralizing liquid 5 nCl 2 : 30 g/L, H 2 SO 4 having a concentration of 98% by mass: 300 mL/L
  • the support PET film was peeled off from the insulating resin composition and removed.
  • the foregoing insulating resin-provided substrate was irradiated with ultraviolet rays at 3,000 mJ/cm 2 by using a conveyor type ultraviolet ray irradiation apparatus with a metal halide lamp as the lamp (wavelength: 350 to 380 nm).
  • the surface of the insulating resin layer was dipped in a conditioner liquid “CLC-601” (a trade name, manufactured by Hitachi Chemical Co., Ltd.) at 60° C. for 5 minutes. Thereafter, the resulting insulating resin layer-provided substrate was washed with water and dipped in a pre-dipping liquid “PD-201” (a trade name, manufactured by Hitachi Chemical Co., Ltd.) at room temperature for 2 minutes.
  • a conditioner liquid “CLC-601” a trade name, manufactured by Hitachi Chemical Co., Ltd.
  • the insulating resin layer-provided substrate was subjected to a dipping treatment with “HS-202B” (a trade name, manufactured by Hitachi Chemical Co., Ltd.) as an electroless plating catalyst containing PdCl 2 at room temperature for 10 minutes, and thereafter, the resulting insulating resin layer-provided substrate was washed with water and dipped in a “CUST-201 plating liquid” (a trade name, manufactured by Hitachi Chemical Co., Ltd.) as an electroless copper plating liquid at room temperature for minutes. Subsequently, the insulating resin layer-provided substrate was further subjected to electroplating with copper sulfate. Thereafter, annealing was performed at 170° C. for 30 minutes to form a conductor layer having a thickness of 20 ⁇ m on the surface of the insulating resin layer.
  • HS-202B a trade name, manufactured by Hitachi Chemical Co., Ltd.
  • an oxide film on the copper surface was removed by means of polishing with a #600 buff roll. Thereafter, an etching resist was formed and subjected to etching, and the etching resist was then removed. There was thus formed a second circuit layer connected to the foregoing first circuit layer via the foregoing via holes.
  • the surface of the second circuit layer was dipped in an aqueous solution containing 50 g/L of sodium chlorite, 20 g/L of NaOH, and 10 g/L of trisodium phosphate at 85° C. for 20 minutes and then washed with water, followed by drying at 80° C. for 20 minutes, thereby forming irregularities of copper oxide on the surface of the second circuit layer.
  • An insulating resin composition shown in Table 2 was coated on a profile-free copper foil (a trade name: HLN-18, manufactured by Nippon Denkai, Ltd., thickness: 18 ⁇ m) as a support and subjected to a drying treatment at 100° C. for 10 minutes, thereby fabricating a copper foil-provided insulating resin layer of 10 ⁇ 1 ⁇ m.
  • a profile-free copper foil a trade name: HLN-18, manufactured by Nippon Denkai, Ltd., thickness: 18 ⁇ m
  • boring processing with 2,000 holes was performed using a drill having a diameter of 0.105 mm (a trade name: KMD J464, manufactured by Union Tool Co.) under a condition at a rotation number of 300 krpm, a feed speed of 2.1 m/min, and a chip load of 7.0 ⁇ m/rev. There were thus formed through-holes penetrating from the front surface to the back surface of the foregoing copper clad laminate.
  • KMD J464 manufactured by Union Tool Co.
  • an aqueous solution containing 200 mL/L of diethylene glycol monobutyl ether and 5 g/L of NaOH as a swelling liquid was heated to 80° C., and the copper clad laminate was dipped therein for 5 minutes.
  • an aqueous solution containing 60 g/L of KMnO 4 and 40 g/L of NaOH as a desmearing treatment liquid was heated to 80° C., and the copper clad laminate was dipped therein for 20 minutes.
  • the resulting copper clad laminate was dipped in an aqueous solution of a neutralizing liquid (5 nCl 2 : 30 g/L, H 2 SO 4 having a concentration of 98% by mass: 300 mL/L) at room temperature for 5 minutes, thereby achieving neutralization. Thereafter, the copper clad laminate was washed with water for 5 minutes and then dried at 100° C. for 10 minutes.
  • a neutralizing liquid 5 nCl 2 : 30 g/L, H 2 SO 4 having a concentration of 98% by mass: 300 mL/L
  • the support (copper foil as the outermost layer) was entirely removed by means of etching.
  • the foregoing insulating resin-provided substrate was irradiated with ultraviolet rays at 3,000 mJ/cm 2 by treating with a conveyor type ultraviolet ray irradiation apparatus with a metal halide lamp as the lamp (wavelength: 350 to 380 nm).
  • each of the surfaces of the insulating resin layers of two layers in total, which were formed on the upper surface side and the lower surface side of the foregoing insulating resin layer-provided substrate was dipped in a conditioner liquid “CLC-601” (a trade name, manufactured by Hitachi Chemical Co., Ltd.) at 60° C. for 5 minutes. Thereafter, the resulting insulating resin layer-provided substrate was washed with water and dipped in a pre-dipping liquid “PD-201” (a trade name, manufactured by Hitachi Chemical Co., Ltd.) at room temperature for 2 minutes.
  • a conditioner liquid “CLC-601” a trade name, manufactured by Hitachi Chemical Co., Ltd.
  • the insulating resin layer-provided substrate was subjected to a dipping treatment with “HS-202B” (a trade name, manufactured by Hitachi Chemical Co., Ltd.) as an electroless plating catalyst containing PdCl 2 at room temperature for 10 minutes, and thereafter, the resulting insulating resin layer-provided substrate was washed with water and dipped in a “CUST-201 plating liquid” (a trade name, manufactured by Hitachi Chemical Co., Ltd.) as an electroless copper plating liquid at room temperature for 15 minutes. Subsequently, the insulating resin layer-provided substrate was further subjected to electroplating with copper sulfate. Thereafter, annealing was performed at 170° C. for 30 minutes to form a conductor layer having a thickness of 20 ⁇ m on each of the surfaces of the insulating resin layers of two layers on the upper surface side and the lower surface side.
  • an oxide film on the copper surface was removed by means of polishing with a #600 buff roll. Thereafter, an etching resist was formed and subjected to etching, and the etching resist was then removed. There was thus formed a circuit layer connected to the internal copper foil via the foregoing through-holes.
  • Multi-layered wiring boards were fabricated by following the same operations as those in Example 12, except that in Example 12, the composition of the insulating resin composition was changed as shown in Table 2.
  • a multi-layered wiring board was fabricated by following the same operations as those in Example 12, except that in Example 12, an insulating resin composition in which spherical silica “SO-25R” (a trade name, manufactured by Admatechs Company Limited) having an average particle diameter of 0.5 ⁇ m was used as the inorganic filler as shown in Table 2 was used; and that the composition of the insulating resin composition was changed as shown in Table 2.
  • SO-25R a trade name, manufactured by Admatechs Company Limited
  • a multi-layered wiring board was fabricated by following the same operations as those in Example 12, except that in Example 12, the lamp for ultraviolet ray irradiation was changed to a conveyor type ultraviolet ray irradiation apparatus with a high pressure mercury vapor lamp (maximum wavelength: 310 to 370 nm). Incidentally, similar to Example 12, the ultraviolet rays were irradiated in an amount of light of 3,000 mJ/cm 2 .
  • a multi-layered wiring board was fabricated in the same manner as that in Example 12, except that the order of the desmearing treatment (7) and the support removal treatment (8) was reversed.
  • a wiring board was fabricated in the same manner as that in Example 13, except that the order of the desmearing treatment (3) and the support removal treatment (4) was reversed.
  • a wiring board was fabricated by following the same operations as those in Example 13, except that the ultraviolet ray irradiation (5) was not performed.
  • Examples 12 to 19 the surface of the insulating resin layer was protected by the support at the time of the desmearing treatment within the via hole, and thereafter, the support was removed, and therefore, the occurrence of an increase of the irregularities on the surface of the insulating resin layer could be prevented.
  • the roughening of the surface of the insulating resin layer at the time of the desmearing treatment was omitted in this way, the adhesive force to the wiring was revealed by irradiating ultraviolet rays on the surface of the insulating resin layer, and therefore, the adhesive strength between this insulating resin layer surface and the wiring circuit was excellent.
  • the solder heat resistance was excellent.
  • Comparative Example 6 the ultraviolet ray irradiation was not performed, and therefore, the adhesive strength between the insulating resin layer and the wiring circuit was low, and the solder heat resistance was poor.
  • Example 12 The same operations as those in Example 12 were followed, except that the ultraviolet ray irradiation was performed after the formation of via holes and before the desmearing treatment.
  • An insulating resin composition shown in Table 4 was coated on a supporting plate made of a polyethylene naphthalate (PEN) film (thickness: 50 ⁇ m) as a support and subjected to a drying treatment at 100° C. for 10 minutes, thereby fabricating an insulating resin layer of 10 ⁇ 1 ⁇ m.
  • PEN polyethylene naphthalate
  • boring processing with 2,000 holes was performed using a drill having a diameter of 0.105 mm (a trade name: KMD J464, manufactured by Union Tool Co.) under a condition at a rotation number of 300 krpm, a feed speed of 2.1 m/min, and a chip load of 7.0 ⁇ m/rev. There were thus formed through-holes penetrating from the front surface to the back surface of the foregoing laminate.
  • a drill having a diameter of 0.105 mm (a trade name: KMD J464, manufactured by Union Tool Co.) under a condition at a rotation number of 300 krpm, a feed speed of 2.1 m/min, and a chip load of 7.0 ⁇ m/rev.
  • the foregoing insulating resin-provided substrate was irradiated with ultraviolet rays at 3,000 mJ/cm 2 by treating with a conveyor type ultraviolet ray irradiation apparatus with a metal halide lamp as the lamp (wavelength: 350 to 380 nm).
  • an aqueous solution containing 200 mL/L of diethylene glycol monobutyl ether and 5 g/L of NaOH as a swelling liquid was heated to 80° C., and the insulating resin layer-provided substrate was dipped therein for 5 minutes.
  • an aqueous solution containing 60 g/L of KMnO 4 and 40 g/L of NaOH as a desmearing treatment liquid was heated to 80° C., and the insulating resin layer-provided substrate was dipped therein for 20 minutes.
  • the resulting insulating resin layer-provided substrate was dipped in an aqueous solution of a neutralizing liquid (SnCl 2 : G/L, H 2 SO 4 having a concentration of 98% by mass: 300 mL/L) at room temperature for 5 minutes, thereby achieving neutralization. Thereafter, the insulating resin layer-provided substrate was washed with water for 5 minutes and then dried at 100° C. for 10 minutes.
  • a neutralizing liquid SnCl 2 : G/L, H 2 SO 4 having a concentration of 98% by mass: 300 mL/L
  • the support (PEN film) was peeled and removed from the insulating resin composition.
  • each of the surfaces of the insulating resin layers of two layers in total, which were formed on the upper surface side and the lower surface side of the foregoing insulating resin layer-provided substrate was dipped in a conditioner liquid “CLC-601” (a trade name, manufactured by Hitachi Chemical Co., Ltd.) at 60° C. for 5 minutes. Thereafter, the resulting insulating resin layer-provided substrate was washed with water and dipped in a pre-dipping liquid “PD-201” (a trade name, manufactured by Hitachi Chemical Co., Ltd.) at room temperature for 2 minutes.
  • a conditioner liquid “CLC-601” a trade name, manufactured by Hitachi Chemical Co., Ltd.
  • the insulating resin layer-provided substrate was subjected to a dipping treatment with “HS-202B” (a trade name, manufactured by Hitachi Chemical Co., Ltd.) as an electroless plating catalyst containing PdCl 2 at room temperature for 10 minutes, and thereafter, the resulting insulating resin layer-provided substrate was washed with water and dipped in a “CUST-201 plating liquid” (a trade name, manufactured by Hitachi Chemical Co., Ltd.) as an electroless copper plating liquid at room temperature for 15 minutes. Subsequently, the insulating resin layer-provided substrate was further subjected to electroplating with copper sulfate. Thereafter, annealing was performed at 170° C. for 30 minutes to form a conductor layer having a thickness of 20 ⁇ m on each of the surfaces of the insulating resin layers of two layers on the upper surface side and the lower surface side.
  • an oxide film on the copper surface was removed by means of polishing with a #600 buff roll. Thereafter, an etching resist was formed and subjected to etching, and the etching resist was then removed. There was thus formed a circuit layer connected to the internal copper foil via the foregoing through-holes.
  • Multi-layered wiring boards were fabricated by following the same operations as those in Example 20, except that in Example 20, the composition of the insulating resin composition was changed as shown in Table 4.
  • a multi-layered wiring board was fabricated by following the same operations as those in Example 20, except that in Example 20, an insulating resin composition in which spherical silica “SO-25R” (a trade name, manufactured by Admatechs Company Limited) having an average particle diameter of 0.5 ⁇ m was used as the inorganic filler as shown in Table 4 was used; and that the composition of the insulating resin composition was changed as shown in Table 4.
  • SO-25R a trade name, manufactured by Admatechs Company Limited
  • a multi-layered wiring board was fabricated by following the same operations as those in Example 20, except that in Example 20, the lamp for ultraviolet ray irradiation was changed to a conveyor type ultraviolet ray irradiation apparatus with a high pressure mercury vapor lamp (maximum wavelength: 310 to 370 nm). Incidentally, similar to Example 20, the ultraviolet rays were irradiated in an amount of light of 3,000 mJ/cm 2 .
  • a multi-layered wiring board was fabricated in the same manner as that in Example 20, except that the order of the desmearing treatment ( 8 ) and the support removal treatment ( 9 ) was reversed.
  • a wiring board was fabricated in the same manner as that in Example 21, except that the order of the desmearing treatment ( 4 ) and the support removal treatment ( 5 ) was reversed.
  • a wiring board was fabricated by following the same operations as those in Example 21, except that the ultraviolet ray irradiation ( 3 ) was not performed.
  • Example 20 to 27 the surface of the insulating resin layer was protected by the support at the time of the desmearing treatment within the via hole, and thereafter, the support was removed, and therefore, the roughness (Ra) of the surface of the insulating resin layer was all not more than 0.05, and the occurrence of an increase of the irregularities could be prevented.
  • the roughening of the surface of the insulating resin layer at the time of the desmearing treatment was omitted in this way, the adhesive force to the wiring was revealed by irradiating ultraviolet rays on the surface of the insulating resin layer, and therefore, the adhesive strength between this insulating resin layer surface and the wiring circuit was excellent.
  • the solder heat resistance was excellent.
  • Example 12 The same operations as those in Example 12 were followed, except that the ultraviolet ray irradiation was performed after the desmearing treatment and before the support removal treatment; and that the dipping treatment time of the insulating resin layer-provided substrate in the desmearing treatment liquid at the time of the desmearing treatment was changed to 10 minutes.
  • Example 21 The same operations as those in Example 21 were followed, except that the ultraviolet ray irradiation was performed after the desmearing treatment and before the support removal treatment; and that the dipping treatment time of the laminate in the desmearing treatment liquid at the time of the desmearing treatment was changed to 10 minutes.
  • Multi-layered wiring boards were fabricated by following the same operations as those in Example 28, except that in Example 28, the composition of the insulating resin composition was changed as shown in Table 6.
  • a multi-layered wiring board was fabricated by following the same operations as those in Example 28, except that in Example 28, an insulating resin composition in which spherical silica “SO-25R” (a trade name, manufactured by Admatechs Company Limited) having an average particle diameter of 0.5 ⁇ m was used as the inorganic filler as shown in Table 6 was used; and that the composition of the insulating resin composition was changed as shown in Table 6.
  • SO-25R a trade name, manufactured by Admatechs Company Limited
  • a multi-layered wiring board was fabricated by following the same operations as those in Example 28, except that in Example 28, the lamp for ultraviolet ray irradiation was changed to a conveyor type ultraviolet ray irradiation apparatus with a high pressure mercury vapor lamp (wavelength: 310 to 370 nm). Incidentally, similar to Example 27, the ultraviolet rays were irradiated in an amount of light of 3,000 mJ/cm 2 .
  • a multi-layered wiring board was fabricated in the same manner as that in Example 28, except that the support removal treatment ( 9 ) was performed after the formation of via hole ( 6 ) and before the desmearing treatment.
  • a multi-layered wiring board was fabricated in the same manner as that in Example 29, except that the support removal treatment ( 5 ) was performed after the formation of through-hole ( 2 ) and before the desmearing treatment ( 3 ).
  • a wiring board was fabricated by following the same operations as those in Example 29, except that the ultraviolet ray irradiation ( 4 ) was not performed.
  • Examples 28 to 35 the surface of the insulating resin layer was protected by the support at the time of the desmearing treatment within the via hole, and thereafter, the support was removed, and therefore, the roughness (Ra) of the surface of the insulating resin layer was all not more than 0.05, and the occurrence of an increase of the irregularities could be prevented.
  • the roughening of the surface of the insulating resin layer at the time of the desmearing treatment was omitted in this way, the adhesive force to the wiring was revealed by irradiating ultraviolet rays on the surface of the insulating resin layer, and therefore, the adhesive strength between this insulating resin layer surface and the wiring circuit was excellent.
  • the solder heat resistance was excellent.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Epoxy Resins (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Laminated Bodies (AREA)
US13/816,206 2010-08-10 2011-08-05 Resin composition, cured resin product, wiring board, and manufacturing method for wiring board Abandoned US20130199830A1 (en)

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JP2010179754A JP5664008B2 (ja) 2010-08-10 2010-08-10 樹脂組成物、樹脂硬化物、配線板及び配線板の製造方法
JP2011171338A JP5803399B2 (ja) 2011-08-04 2011-08-04 配線板の製造方法
JP2011171339A JP5790272B2 (ja) 2011-08-04 2011-08-04 配線板の製造方法
JP2011171340 2011-08-04
JP2011171338 2011-08-04
JP2011171339 2011-08-04
JP2011171340A JP5879801B2 (ja) 2011-08-04 2011-08-04 配線板の製造方法
PCT/JP2011/067984 WO2012020713A2 (ja) 2010-08-10 2011-08-05 樹脂組成物、樹脂硬化物、配線板及び配線板の製造方法

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US20140118964A1 (en) * 2012-11-01 2014-05-01 Ajinomoto Co., Inc. Method for producing printed wiring board
US20150002924A1 (en) * 2012-01-13 2015-01-01 Taica Corporation Method for producing transparent adhesive sheet for optical applications, transparent adhesive sheet for optical applications, and display device using same
US20150190845A1 (en) * 2014-01-09 2015-07-09 Nano And Advanced Materials Institute Limited Surface Treatment of Mirror Finish
US20150216056A1 (en) * 2013-08-15 2015-07-30 Hitachi Metals, Ltd. Ceramic circuit substrate and its production method
US20150351251A1 (en) * 2012-12-27 2015-12-03 Ushio Denki Kabushiki Kaisha Desmearing method and desmearing device
US20160227680A1 (en) * 2015-01-29 2016-08-04 Lg Innotek Co., Ltd. Structure for shielding electronomagnetic waves
US20160324007A1 (en) * 2013-12-20 2016-11-03 Ushio Denki Kabushiki Kaisha Desmear treatment method for wiring board material, method of manufacturing wiring board material, and composite insulating layer forming material
WO2017039624A1 (en) * 2015-08-31 2017-03-09 Robert Alan May Method of forming a via opening
JP2017202606A (ja) * 2016-05-10 2017-11-16 日立化成株式会社 樹脂付きポリイミドフィルム、樹脂層を備えたポリイミドフィルム、プリント配線板用積層体、及びプリント配線板の製造方法
US10763031B2 (en) 2016-08-30 2020-09-01 Samsung Electro-Mechanics Co., Ltd. Method of manufacturing an inductor
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TWI657730B (zh) * 2012-05-31 2019-04-21 日商味之素股份有限公司 多層印刷配線板之製造方法
JP2016072419A (ja) * 2014-09-30 2016-05-09 日本ゼオン株式会社 積層体の製造方法
JP2016221953A (ja) * 2015-06-03 2016-12-28 日立化成株式会社 積層体の製造方法及び配線板の製造方法
JP2017011194A (ja) * 2015-06-25 2017-01-12 日立化成株式会社 アディティブ工法用プリント配線板
JP6699148B2 (ja) * 2015-12-03 2020-05-27 日立化成株式会社 積層体及びその製造方法、並びに、プリント配線板の製造方法
JP7114214B2 (ja) * 2016-05-24 2022-08-08 味の素株式会社 接着フィルム
KR102225796B1 (ko) * 2017-03-21 2021-03-11 미쓰이금속광업주식회사 배선판의 제조 방법
KR102450598B1 (ko) * 2017-11-09 2022-10-07 삼성전기주식회사 지지체 부착 인쇄회로기판 및 지지체 부착 인쇄회로기판의 제조방법
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US8872040B2 (en) * 2011-08-29 2014-10-28 Fujitsu Limited Wiring structure and manufacturing method thereof, and electronic apparatus and manufacturing method thereof
US20130048358A1 (en) * 2011-08-29 2013-02-28 Fujitsu Limited Wiring structure and manufacturing method thereof, and electronic apparatus and manufacturing method thereof
US20150002924A1 (en) * 2012-01-13 2015-01-01 Taica Corporation Method for producing transparent adhesive sheet for optical applications, transparent adhesive sheet for optical applications, and display device using same
US9776387B2 (en) * 2012-01-13 2017-10-03 Taica Corporation Method for producing transparent adhesive sheet for optical applications, transparent adhesive sheet for optical applications, and display device using same
US9516765B2 (en) * 2012-11-01 2016-12-06 Ajinomoto Co., Inc. Method for producing printed wiring board
US20140118964A1 (en) * 2012-11-01 2014-05-01 Ajinomoto Co., Inc. Method for producing printed wiring board
US11102889B2 (en) * 2012-12-27 2021-08-24 Ushio Denki Kabushiki Kaisha Desmearing method and desmearing device
US20150351251A1 (en) * 2012-12-27 2015-12-03 Ushio Denki Kabushiki Kaisha Desmearing method and desmearing device
US20150216056A1 (en) * 2013-08-15 2015-07-30 Hitachi Metals, Ltd. Ceramic circuit substrate and its production method
US10057992B2 (en) * 2013-08-15 2018-08-21 Hitachi Metals, Ltd. Ceramic circuit substrate and its production method
US20160324007A1 (en) * 2013-12-20 2016-11-03 Ushio Denki Kabushiki Kaisha Desmear treatment method for wiring board material, method of manufacturing wiring board material, and composite insulating layer forming material
US10420221B2 (en) * 2013-12-20 2019-09-17 Ushio Denki Kabushiki Kaisha Wiring board desmear treatment method
US9205455B2 (en) * 2014-01-09 2015-12-08 Nano And Advanced Materials Institute Limited Surface treatment of mirror finish
US20150190845A1 (en) * 2014-01-09 2015-07-09 Nano And Advanced Materials Institute Limited Surface Treatment of Mirror Finish
US20160227680A1 (en) * 2015-01-29 2016-08-04 Lg Innotek Co., Ltd. Structure for shielding electronomagnetic waves
US9832914B2 (en) * 2015-01-29 2017-11-28 Lg Innotek Co., Ltd. Structure for shielding electronomagnetic waves
WO2017039624A1 (en) * 2015-08-31 2017-03-09 Robert Alan May Method of forming a via opening
JP2017202606A (ja) * 2016-05-10 2017-11-16 日立化成株式会社 樹脂付きポリイミドフィルム、樹脂層を備えたポリイミドフィルム、プリント配線板用積層体、及びプリント配線板の製造方法
US10763031B2 (en) 2016-08-30 2020-09-01 Samsung Electro-Mechanics Co., Ltd. Method of manufacturing an inductor
US11600430B2 (en) 2016-08-30 2023-03-07 Samsung Electro-Mechanics Co., Ltd. Inductor including high-rigidity insulating layers
US11523518B2 (en) * 2017-11-28 2022-12-06 Sumitomo Electric Printed Circuits, Inc. Method of making flexible printed circuit board and flexible printed circuit board

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EP2604639A4 (en) 2017-02-01
TW201206979A (en) 2012-02-16
WO2012020713A2 (ja) 2012-02-16
US20190218415A1 (en) 2019-07-18
KR101807901B1 (ko) 2017-12-11
TWI618726B (zh) 2018-03-21
CN104797093B (zh) 2018-01-02
CN103140537A (zh) 2013-06-05
TWI529191B (zh) 2016-04-11
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US11319457B2 (en) 2022-05-03
CN103140537B (zh) 2016-10-12

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