WO2012133032A1 - Procédé de fabrication d'un stratifié possédant des films métalliques à motifs et composition pour formation de couche devant être plaquée - Google Patents

Procédé de fabrication d'un stratifié possédant des films métalliques à motifs et composition pour formation de couche devant être plaquée Download PDF

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Publication number
WO2012133032A1
WO2012133032A1 PCT/JP2012/057148 JP2012057148W WO2012133032A1 WO 2012133032 A1 WO2012133032 A1 WO 2012133032A1 JP 2012057148 W JP2012057148 W JP 2012057148W WO 2012133032 A1 WO2012133032 A1 WO 2012133032A1
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Prior art keywords
group
layer
plated
metal film
plating
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PCT/JP2012/057148
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English (en)
Japanese (ja)
Inventor
加納　丈嘉
植木　志貴
威史 濱
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富士フイルム株式会社
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837—Multistep pretreatment
    • C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • C25D5/022—Electroplating of selected surface areas using masking means
    • 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
    • H05K3/4652—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern
    • H05K3/4658—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern characterized by laminating a prefabricated metal foil pattern, e.g. by transfer

Definitions

  • the present invention relates to a method for producing a laminate having a patterned metal film and a composition for forming a plating layer used in the production method.
  • a metal wiring board in which wiring with a metal pattern is formed on the surface of an insulating substrate has been widely used for electronic components and semiconductor elements.
  • a “subtractive method” is mainly used.
  • a photosensitive layer that is exposed by irradiation with actinic rays is provided on a metal film formed on the surface of the substrate, the photosensitive layer is exposed imagewise, and then developed to form a resist image.
  • the metal film is etched to form a metal pattern, and finally the resist is removed.
  • adhesion between the substrate and the metal pattern is expressed by an anchor effect generated by providing irregularities on the substrate surface. For this reason, when the obtained metal pattern is used as a metal wiring, there is a problem that high frequency characteristics are deteriorated due to the unevenness of the substrate interface portion of the metal pattern.
  • a strong acid such as chromic acid
  • a polymer layer having high adhesion to the substrate is formed on the substrate, and the polymer layer is plated to form a metal layer having excellent adhesion without making the substrate uneven. It can be formed (Patent Document 1). According to this method, the adhesion between the substrate and the metal film can be improved without roughening the surface of the substrate. Further, in relation to the method, a composition for forming a layer to be plated that can form a layer to be plated that is excellent in adsorptivity to the plating catalyst or its precursor is known (Patent Documents 2 and 3).
  • survives between metal wiring was related with the insulation reliability between metal wiring. That is, it has been found that if the layer to be plated remains between the wiring patterns after the pattern-like metal film is formed, the insulation between the pattern-like metal films may be reduced.
  • the present inventors performed a plasma etching process in order to remove the layer to be plated existing in the region where the patterned metal film is not provided, and it took a long time to remove the layer to be plated. It has been found that there is a problem that processing time is required or the plated layer cannot be sufficiently removed.
  • the present invention can easily carry out plasma etching treatment of a layer to be plated, and a method for producing a laminate having a patterned metal film having excellent insulation between the patterned metal films, and
  • An object of the present invention is to provide a composition for forming a plated layer used in the production method.
  • the present inventors use a binary copolymer consisting of two specific units, and an etching solution, and by providing a contact step with a predetermined acidic solution, It has been found that the above problems can be solved. That is, the present inventors have found that the above object can be achieved by the following means.
  • a composition for forming a layer to be plated including a unit copolymer represented by formula (A) described later and a unit copolymer represented by formula (B) described later is brought into contact with the substrate. After that, applying energy to the composition for forming a layer to be plated on the substrate to form a layer to be plated on the substrate, A catalyst application step for applying a plating catalyst or a precursor thereof to the layer to be plated; A plating step of performing a plating treatment on the layer to be plated to which the plating catalyst or its precursor is applied, and forming a metal film on the layer to be plated; After the plating step, a pattern forming step of forming a patterned metal film using an etching solution containing a metal component or hydrogen peroxide, An acidic solution contact step in which a substrate having a patterned metal film is contacted with an acidic solution substantially free of a metal component or hydrogen peroxide; A method for producing a laminate having a patterned metal film, comprising: a
  • the unit represented by formula (B) is a unit represented by formula (B-1) described later, or a unit represented by formula (B-2) described later.
  • the manufacturing method of the laminated body which can perform the plasma etching process of a to-be-plated layer easily, and has the patterned metal film excellent in the insulation between patterned metal films, and this manufacturing method
  • the composition for to-be-plated layer forming used for can be provided.
  • FIG. 1 A) to (E) are schematic cross-sectional views sequentially showing each manufacturing step in the method for manufacturing a laminate having a patterned metal film of the present invention.
  • FIG. 1 A)-(C) are each process drawing which shows one suitable aspect of a pattern formation process.
  • FIG. 1 A) to (E) are process diagrams showing another preferred embodiment of the pattern forming process.
  • Patent Documents 1 to 3 the metal component to be affected. That is, it has been found that the more the metal component remains, the more it affects the subsequent plasma etching process of the layer to be plated.
  • One way to reduce the metal component in the layer to be plated is to reduce the adsorption amount of the plating catalyst. In this case, obtain a metal film (plating film) with sufficient thickness in a certain time during the plating process. In addition, the adhesion of the resulting metal film is inferior.
  • a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a salt thereof has substantially no functional group such as a cyano group. It has been found that the desired effect can be obtained by using the original copolymer, etching the metal film with a predetermined etching solution, and bringing the plating layer into contact with the acidic solution before the plasma etching treatment. More specifically, the predetermined functional group has a property of adsorbing with the plating catalyst, but when the hydrogen ions are supplied from an acidic solution, the plating catalyst is easily desorbed.
  • the constituent components (binary copolymer, etc.) of the composition for forming a layer to be plated of the present invention will be described in detail, and then a method for producing a laminate having a patterned metal film using the composition will be described in detail. To do.
  • the binary copolymer (hereinafter, also simply referred to as polymer) used in the present invention is composed of a unit represented by the formula (A) and a unit represented by the formula (B).
  • the unit represented by the formula (A) in the polymer cross-linking between the polymers and chemical bonds are formed between the substrate and the polymer, and the adhesion of the resulting metal film is further improved.
  • the carboxylic acid group, sulfonic acid group, phosphoric acid group, or salt thereof in the unit represented by the formula (B) can adsorb the plating catalyst, and electroless plating described later is performed. Can do.
  • the plating catalyst adsorbed in the layer to be plated or its precursor can be desorbed by the acidic solution described later, so that the plating catalyst remains in the exposed layer to be plated after the metal film etching process. Hard to do. Therefore, the plated layer can be more efficiently removed during the plasma etching process.
  • R 1 , R 2 , and R 4 each independently represent a hydrogen atom or a methyl group. Preferably it is a hydrogen atom.
  • R 3 represents a hydrogen atom, a methyl group, an ethyl group, a t-butyl group, or an n-butyl group.
  • a hydrogen atom is preferable from the viewpoint that the reaction sensitivity can be improved by increasing the amount of the polymerizable group per unit weight, and that hydrophilicity is imparted to the polymer.
  • V represents a single bond, an ester group, an amide group, or a phenylene group.
  • a single bond, an ester group, or a phenylene group is preferable from the viewpoint of ease of synthesis and the effect of the present invention, and an ester group is preferable.
  • W represents a single bond, an ester group, an amide group, or a phenylene group.
  • a single bond is preferable from the point which increases content of X per unit weight.
  • L 1 represents a divalent hydrocarbon group.
  • the number of carbon atoms of the hydrocarbon group is not particularly limited, but is preferably 1 to 6 carbon atoms and more preferably 1 to 3 carbon atoms from the viewpoint that the effect of the present invention is more excellent.
  • any of a bivalent aliphatic hydrocarbon group for example, a methylene group, ethylene group
  • a bivalent aromatic hydrocarbon group for example, phenylene group
  • the aliphatic hydrocarbon group may be linear, branched or cyclic, and may be substituted with an oxygen atom or an alkyl group.
  • L 1 is a carbon that may be substituted with a group selected from the group consisting of a methyl group, an ethyl group, and a propyl group because the sensitivity can be improved by increasing the amount of the polymerizable group per unit weight.
  • a divalent linear hydrocarbon group having a number of 1 to 3 is preferable.
  • L 2 represents a single bond or a divalent organic group.
  • the divalent organic group include a substituted or unsubstituted aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms), a substituted or unsubstituted aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms), —O —, —S—, —SO 2 —, —N (R) — (R: alkyl group), —CO—, —NH—, —COO—, —CONH—, or a combination thereof (for example, alkylene Oxy group, alkyleneoxycarbonyl group, alkylenecarbonyloxy group, etc.).
  • a substituted or unsubstituted aliphatic hydrocarbon group a methylene group, an ethylene group, a propylene group, or a butylene group, or these groups are substituted with a methoxy group, a chlorine atom, a bromine atom, a fluorine atom, or the like Those are preferred.
  • the substituted or unsubstituted aromatic hydrocarbon group an unsubstituted phenylene group or a phenylene group substituted with a methoxy group, a chlorine atom, a bromine atom, a fluorine atom or the like is preferable.
  • L 2 is a divalent linear chain having 1 to 6 carbon atoms which may be substituted with a group selected from the group consisting of a methyl group, an ethyl group, and a propyl group, from the viewpoint of the hydrophilicity of the polymer.
  • a divalent hydrocarbon group having 2 to 8 carbon atoms having a hydrocarbon group, an ethylene oxide group, a propylene oxide group, an ester group (—COO—), or a single bond is preferred, and a single bond is most preferred.
  • X represents a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a salt thereof.
  • a carboxylic acid group and a sulfonic acid group are preferable from the viewpoint of ease of synthesis, and a carboxylic acid group is more preferable from the viewpoint of stability of the compound.
  • a preferred embodiment of the unit represented by the formula (A) is a unit represented by the formula (A-1).
  • R 1 , R 2 , R 3 , and L 1 are as described above.
  • Y represents an oxygen atom or a —NR 5 — group.
  • an oxygen atom is preferable in that the effect of the present invention is excellent.
  • R 5 represents a hydrogen atom, a methyl group, an ethyl group, a t-butyl group, or an n-butyl group. Of these, a hydrogen atom is preferable from the viewpoint of increasing the amount of the polymerizable group per unit weight.
  • a preferred embodiment of the unit represented by the formula (B) includes a unit represented by the formula (B-1) or a unit represented by the formula (B-2).
  • R 4 , L 2 and X are as described above.
  • Y represents an oxygen atom or a —NR 5 — group.
  • R 5 represents a hydrogen atom, a methyl group, an ethyl group, a t-butyl group, or an n-butyl group. Of these, an oxygen atom is preferable from the viewpoint of ease of synthesis.
  • the definitions of R 4 and X are as described above.
  • the formula (B-2) is a more preferable embodiment.
  • the content of the unit represented by the formula (A) in the binary copolymer is not particularly limited, but from the viewpoint of reactivity (curability and polymerization) and suppression of gelation during synthesis, The amount is preferably 10 to 70 mol%, more preferably 10 to 40 mol%, based on the combined unit.
  • the content of the unit represented by the formula (B) in the binary copolymer is not particularly limited, but from the viewpoint of adsorptivity to the plating catalyst or its precursor, It is preferably ⁇ 90 mol%, more preferably 60 to 90 mol%.
  • the weight average molecular weight of the binary copolymer is not particularly limited, but is preferably 1000 or more and 700,000 or less, and more preferably 2000 or more and 200,000 or less. In particular, from the viewpoint of polymerization sensitivity, it is preferably 20000 or more, and from the viewpoint of suppressing gelation during synthesis, 100,000 or less is preferable.
  • the degree of polymerization of the binary copolymer is not particularly limited, but it is preferable to use a 10-mer or higher, more preferably a 20-mer or higher.
  • 7000-mer or less is preferable, 3000-mer or less is more preferable, 2000-mer or less is still more preferable, 1000-mer or less is especially preferable.
  • the content of the binary copolymer in the composition for forming a layer to be plated is not particularly limited, but is preferably 2 to 50% by mass, more preferably 5 to 30% by mass with respect to the total amount of the composition. If it is in the said range, it is excellent in the handleability of a composition and it is easy to control the layer thickness of a to-be-plated layer.
  • the composition for forming a layer to be plated may contain a solvent as necessary.
  • Solvents that can be used are not particularly limited, for example, alcohol solvents such as water, methanol, ethanol, propanol, ethylene glycol, glycerin, propylene glycol monomethyl ether, acids such as acetic acid, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, Amide solvents such as formamide, dimethylacetamide and N-methylpyrrolidone, nitrile solvents such as acetonitrile and propionitrile, ester solvents such as methyl acetate and ethyl acetate, carbonate solvents such as dimethyl carbonate and diethyl carbonate, and others
  • amide solvents ketone solvents, nitrile solvents, and carbonate solvents are preferable.
  • acetone, dimethylacetamide, methyl ethyl ketone, cyclohexanone, acetonitrile, propionitrile, N-methylpyrrolidone, and dimethyl carbonate are preferable.
  • the content of the solvent is preferably 50 to 98% by mass, more preferably 70 to 95% by mass with respect to the total amount of the composition. If it is in the said range, it is excellent in the handleability of a composition and it is easy to control the layer thickness of a to-be-plated layer.
  • additives In the composition for forming a layer to be plated of the present invention, other additives (for example, polymerization initiator, monomer, sensitizer, curing agent, polymerization inhibitor, antioxidant, antistatic agent, ultraviolet absorber, filler) Particles, flame retardants, surfactants, lubricants, plasticizers, etc.) may be added as necessary.
  • additives for example, polymerization initiator, monomer, sensitizer, curing agent, polymerization inhibitor, antioxidant, antistatic agent, ultraviolet absorber, filler
  • Particles flame retardants, surfactants, lubricants, plasticizers, etc.
  • the manufacturing method mainly includes the following six steps.
  • (Plating layer forming step) After contacting the composition for forming a layer to be plated on a substrate, energy is applied to the composition for forming a layer to be plated on the substrate to form a layer to be plated on the substrate.
  • Step of applying Step of applying (catalyst applying step) Step of applying a plating catalyst or precursor thereof to the layer to be plated (plating step)
  • Plating treatment is applied to the layer of plating to which the plating catalyst or precursor thereof has been applied.
  • Step of forming a metal film After the plating step, forming a pattern metal film using an etching solution containing a metal component or hydrogen peroxide (acid solution contact step) having a pattern metal film
  • a step of bringing a substrate into contact with an acidic solution substantially free of a metal component or hydrogen peroxide (to-be-plated layer removing step) The plated layer in a region where a patterned metal film is not formed
  • the to-be-plated layer forming step is a step of forming the to-be-plated layer on the substrate by bringing the above-mentioned to-be-plated layer forming composition into contact with the substrate and then applying energy to the to-be-plated layer forming composition. is there.
  • the layer to be plated formed by this step is a plating catalyst or The precursor is adsorbed (attached). That is, the layer to be plated functions as a good receiving layer for the plating catalyst or its precursor.
  • the bipolymer bonding group in the unit represented by the formula (A) is used for bonding between polymers and chemical bonding with a substrate (or a close adhesion auxiliary layer described later).
  • a substrate or a close adhesion auxiliary layer described later.
  • excellent adhesion appears between the metal film (plating film) formed on the surface of the layer to be plated and the substrate.
  • the preferable aspect in this process is an aspect in which the to-be-plated layer and the board
  • any conventionally known substrate can be used as long as it has shape retention.
  • the surface has a function which can be chemically bonded with the polymer mentioned later.
  • the substrate itself can form a chemical bond with the polymer by applying energy (for example, exposure), or an intermediate layer on the substrate that can form a chemical bond with the layer to be plated by applying energy.
  • an adhesion auxiliary layer described later may be provided.
  • the material of the substrate is not particularly limited.
  • polymer materials for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polyvinyl acetal, Polyimide, epoxy, bismaleimide resin, polyphenylene oxide, liquid crystal polymer, polytetrafluoroethylene, etc.), metal material (eg, metal alloy, metal-containing material, pure metal, or the like, specifically aluminum , Zinc, copper and other mixtures, alloys, and alloys thereof), other materials (eg, paper, paper laminated with plastic), combinations thereof, or the like.
  • polymer materials for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polyvin
  • the laminate of the present invention can be applied to semiconductor packages, various electric wiring boards, and the like.
  • a substrate containing an insulating resin as shown below specifically, a substrate made of an insulating resin (insulating substrate) or an insulating resin layer (insulating resin layer) ) On the surface (substrate with an insulating resin layer) is preferably used.
  • substrate which has a metal wiring layer and an insulating resin layer alternately on the surface, and the insulating resin layer is arrange
  • a known insulating resin composition is used.
  • the insulating resin may be, for example, a thermosetting resin, a thermoplastic resin, or a mixture thereof.
  • the thermosetting resin include an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, and a bismaleimide. Examples thereof include resins, polyolefin resins, isocyanate resins, and ABS resins.
  • epoxy resin examples include cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, biphenol F type epoxy resin, naphthalene type epoxy resin, dicyclo
  • examples thereof include pentadiene type epoxy resins, epoxidized products of condensates of phenols and aromatic aldehydes having a phenolic hydroxyl group, and alicyclic epoxy resins. These may be used alone or in combination of two or more.
  • thermoplastic resin examples include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and the like.
  • the substrate may contain various additives as long as the effects of the present invention are not impaired.
  • fillers such as inorganic particles (for example, glass fibers, silica particles, alumina, clay, talc, aluminum hydroxide, calcium carbonate, mica, wollastonite) and silane compounds (for example, silane coupling agents) And silane adhesives), organic fillers (eg, cured epoxy resins, crosslinked benzoguanamine resins, crosslinked acrylic polymers), plasticizers, surfactants, viscosity modifiers, colorants, curing agents, impact strength modifiers, adhesives Examples include a property-imparting agent, an antioxidant, and an ultraviolet absorber.
  • the substrate preferably has a surface roughness Rz measured by the 10-point average height method of JIS BJ0601 (1994) of 500 nm or less, more preferably. Is 100 nm or less, more preferably 50 nm or less, and most preferably 20 nm or less. Although a minimum is not specifically limited, About 5 nm is preferable and 0 is more preferable.
  • the adhesion auxiliary layer is an arbitrary layer that may be provided on the surface of the substrate, and plays a role of assisting adhesion between the substrate and a layer to be plated described later. This layer may have an affinity between the substrate and the layer to be plated, and may react with the polymer during curing to form a chemical bond. In addition, if a board
  • the adhesion auxiliary layer a layer that causes a chemical bond when the polymer is cured (particularly during photocuring) is preferable. It is preferable to introduce a polymerization initiator into the adhesion auxiliary layer that generates such a chemical bond.
  • the adhesion auxiliary layer is preferably formed using water-dispersed latex from the viewpoint of workability.
  • the adhesion auxiliary layer is preferably formed using a resin composition having good adhesion to the substrate and a compound capable of generating radicals upon exposure (a polymerization initiator).
  • a resin composition having good adhesion to the substrate and a compound capable of generating radicals upon exposure
  • a polymerization initiator when the resin which comprises a resin composition has the site
  • a conventionally well-known photoinitiator is used as a compound which can generate
  • the amount of the photopolymerization initiator (compound capable of generating radicals upon exposure) to be contained in the adhesion auxiliary layer is preferably 0.1% by mass to 50% by mass in terms of solid content, and 1.0% by mass to 30% by mass. % Is more preferable.
  • the adhesion auxiliary layer in the present invention for example, when the substrate is made of a known insulating resin that has been used as a material for a multilayer laminate, a build-up substrate, or a flexible substrate, the adhesion with the substrate From the viewpoint, an insulating resin composition is preferably used as the resin composition used when forming the adhesion assisting layer.
  • an insulating resin composition is preferably used as the resin composition used when forming the adhesion assisting layer.
  • the insulating resin composition used when forming the adhesion auxiliary layer may contain the same or different one as the electrically insulating resin constituting the substrate, but may have a glass transition point or elastic modulus. It is preferable to use a material having close thermal properties such as a linear expansion coefficient. Specifically, for example, it is preferable to use the same type of insulating resin as the insulating resin constituting the substrate in terms of adhesion.
  • the insulating resin used for the adhesion auxiliary layer means a resin having an insulation property that can be used for a known insulating film, and even if it is not a perfect insulator, Any resin having appropriate insulating properties can be applied to the present invention.
  • Specific examples of the insulating resin may be, for example, a thermosetting resin, a thermoplastic resin, or a mixture thereof.
  • the thermosetting resin include an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, and a bismaleimide. Examples thereof include resins, polyolefin resins, isocyanate resins and the like.
  • thermoplastic resin examples include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and ABS resin.
  • the thermoplastic resin and the thermosetting resin may be used alone or in combination of two or more.
  • the thickness of the adhesion auxiliary layer in the present invention is generally in the range of 0.1 to 10 ⁇ m, and preferably in the range of 0.2 to 5 ⁇ m.
  • the thickness is in the above range, sufficient adhesion strength with the adjacent base material or the layer to be plated can be obtained, and the thickness is smaller than that of using a general adhesive. Nevertheless, adhesion similar to the adhesive layer is achieved.
  • the adhesion auxiliary layer is formed on the substrate surface by applying a known layer forming method such as a coating method, a transfer method, or a printing method.
  • the adhesion auxiliary layer may be formed by a printing method (for example, gravure printing method, screen printing method, flexographic printing method, ink jet printing method, imprinting method, etc.) or a developing method (for example, wet etching, dry etching, ablation, light). It may be patterned by curing / plasticizing (negative type / positive type) or the like.
  • the adhesion auxiliary layer may be cured by applying some energy.
  • the energy to be applied include light, heat, pressure, electron beam, etc., and heat or light is general. In the case of heat, it is preferable to add heat at 100 ° C. to 300 ° C. for 5 minutes to 120 minutes. .
  • This curing treatment may be performed immediately after the formation of the adhesion assisting layer. If a preliminary curing treatment is performed for about 5 to 10 minutes after the formation of the adhesion assisting layer, all other processes performed after the formation of the adhesion assisting layer are performed. You may implement after performing the process of.
  • the method for bringing the composition for forming a layer to be plated into contact with the substrate (or on the adhesion auxiliary layer) is not particularly limited, and the method for laminating the composition for forming a layer to be plated directly on the substrate or the formation of the layer to be plated
  • the composition for use is a liquid containing a solvent
  • a method of coating the composition on a substrate can be mentioned. From the viewpoint of easily controlling the thickness of the obtained layer to be plated, a method of applying the composition on the substrate is preferable.
  • the method of application is not particularly limited, and specific methods include spin coater, dip coater, double roll coater, slit coater, air knife coater, wire bar coater, slide hopper, spray coating, blade coater, doctor coater, squeeze coater, Known methods such as a reverse roll coater, a transfer roll coater, an extrusion coater, a curtain coater, a die coater, a gravure roll coating method, an extrusion coating method, and a roll coating method can be used. From the viewpoint of handleability and production efficiency, a composition containing a binary copolymer is formed by applying and drying a composition for forming a layer to be plated on a substrate (or an adhesion auxiliary layer) to remove the remaining solvent. An embodiment in which a layer is formed is preferred.
  • the coating amount is 0.1 g / m 2 in terms of solid content from the viewpoint of sufficient interaction formation with a plating catalyst or a precursor thereof described later. 10 g / m 2 is preferable, and 0.5 g / m 2 to 5 g / m 2 is particularly preferable.
  • the remaining solvent may be removed by leaving it at 20 to 40 ° C. for 0.5 to 2 hours between application and drying.
  • the method for applying energy to the composition for forming a layer to be plated on the substrate is not particularly limited, but for example, heating or exposure is preferably used.
  • light irradiation with a UV lamp, visible light, or the like is used.
  • the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp.
  • radiation include electron beams, X-rays, ion beams, and far infrared rays.
  • g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are used.
  • the exposure time varies depending on the reactivity of the polymer and the light source, but is usually between 10 seconds and 5 hours.
  • the exposure energy may be about 10 to 8000 mJ, and is preferably in the range of 100 to 3000 mJ.
  • a blower dryer an oven, an infrared dryer, a heating drum, or the like can be used.
  • the thickness of the layer to be plated is not particularly limited, but is preferably 0.01 to 10 ⁇ m, more preferably 0.05 to 5 ⁇ m, from the viewpoint of the adhesion of the metal film to the substrate.
  • the dry film thickness is preferably 0.05 to 20 g / m 2 , particularly preferably 0.1 to 6 g / m 2 .
  • the surface roughness (Ra) of the layer to be plated is preferably 0.01 to 0.3 ⁇ m and more preferably 0.02 to 0.15 ⁇ m from the viewpoint of the wiring shape and the adhesion strength.
  • the surface roughness (Ra) was measured using Surfcom 3000A (manufactured by Tokyo Seimitsu Co., Ltd.) based on Ra described in JIS B 0601 (Revision of 201010120) by non-contact interference method.
  • a catalyst provision process is a process of providing a plating catalyst or its precursor to the to-be-plated layer obtained at the said process.
  • the functional group X (carboxylic acid group or the like) derived from the unit represented by the formula (B) in the layer to be plated adheres a given plating catalyst or its precursor depending on its function ( Adsorb).
  • Adsorb a plating catalyst or its precursor
  • a plating catalyst or its precursor what functions as a catalyst or an electrode of a plating process in the plating process mentioned later is mentioned. Therefore, although a plating catalyst or its precursor is determined by the kind of plating process in a plating process, it is preferable that it is an electroless-plating catalyst or its precursor.
  • the material (electroless plating catalyst or its precursor etc.) used at this process is explained in full detail, and the procedure of this process is explained in full detail after that.
  • any catalyst can be used as long as it becomes an active nucleus at the time of electroless plating.
  • a metal (Ni) having catalytic ability for autocatalytic reduction reaction. And those known as metals capable of electroless plating with a lower ionization tendency).
  • Specific examples include Pd, Ag, Cu, Ni, Pt, Au, and Co.
  • Ag, Pd, Pt, and Cu are particularly preferable because of their high catalytic ability.
  • a metal colloid may be used as the electroless plating catalyst.
  • a metal colloid can be prepared by reducing metal ions in a solution containing a charged surfactant or a charged protective agent. The charge of the metal colloid can be controlled by the surfactant or protective agent used here.
  • the electroless plating catalyst precursor used in this step can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction.
  • the metal ions of the metals mentioned as the electroless plating catalyst are mainly used.
  • the metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction.
  • the metal ion which is an electroless plating catalyst precursor may be converted into a zero-valent metal by a separate reduction reaction before being immersed in the electroless plating bath.
  • the electroless plating catalyst precursor may be immersed in an electroless plating bath and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath.
  • the metal ion that is the electroless plating catalyst precursor is preferably applied to the layer to be plated using a metal salt.
  • the metal salt used is not particularly limited as long as it is dissolved in a suitable solvent and dissociated into a metal ion and a base (anion), and M (NO 3 ) n , MCl n , M 2 / n (SO 4 ), M 3 / n (PO 4 ) (M represents an n-valent metal atom), and the like.
  • a metal ion the thing which said metal salt dissociated can be used suitably.
  • Ag ion, Cu ion, Ni ion, Co ion, Pt ion, Pd ion can be mentioned.
  • Ag ions, Pd ions, and Cu ions are preferable in terms of catalytic ability.
  • One preferred example of the electroless plating catalyst or precursor thereof used in the present invention is a palladium compound.
  • This palladium compound acts as a plating catalyst (palladium) or a precursor thereof (palladium ions), which serves as an active nucleus during plating treatment and serves to precipitate a metal.
  • Palladium (Pd) has an advantage that it is highly active and can be electrolessly plated in a small amount, so that it hardly remains in the polymer layer by the time of plasma etching.
  • the palladium compound is not particularly limited as long as it contains palladium and acts as a nucleus in the plating process, and examples thereof include a palladium (II) salt, a palladium (0) complex, and a palladium colloid.
  • silver or silver ion is mentioned as another preferable example.
  • silver ions those obtained by dissociating silver compounds as shown below can be suitably used.
  • Specific examples of the silver compound include silver nitrate, silver acetate, silver sulfate, silver carbonate, silver cyanide, silver thiocyanate, silver chloride, silver bromide, silver chromate, silver chloranilate, silver salicylate, silver diethyldithiocarbamate, Examples thereof include silver diethyldithiocarbamate and silver p-toluenesulfonate.
  • silver nitrate is preferable from the viewpoint of water solubility.
  • palladium compounds are most preferred.
  • a zero-valent metal can be used as a catalyst used for performing direct electroplating without electroless plating on the layer to be plated.
  • plating catalyst solution The plating catalyst or a precursor thereof as described above is preferably applied to the layer to be plated as a dispersion or solution (plating catalyst solution).
  • Water or an organic solvent is used as a solvent for the plating catalyst solution.
  • the permeability of the plating catalyst or its precursor to the layer to be plated is improved, and the plating catalyst or its precursor can be efficiently adsorbed to the functional group X.
  • the water used in the plating catalyst solution preferably does not contain impurities. From such a viewpoint, it is preferable to use RO water, deionized water, distilled water, purified water, and the like. It is particularly preferred to use water.
  • an organic solvent used for a plating catalyst liquid if it is a solvent which can osmose
  • acetone, methyl acetoacetate, ethyl acetoacetate, ethylene glycol diacetate, cyclohexanone, acetylacetone, acetophenone, 2- (1-cyclohexenyl) cyclohexanone, propylene glycol diacetate, triacetin, diethylene glycol diacetate, dioxane, N-methylpyrrolidone , Dimethyl carbonate, dimethyl cellosolve, etc. can be used.
  • a water-soluble organic solvent is preferable from the viewpoint of compatibility with a plating catalyst or a precursor thereof and permeability to a layer to be plated.
  • Acetone, dimethyl carbonate, dimethyl cellosolve, triethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether is preferred.
  • dispersion or solution may contain other additives depending on the purpose.
  • additives include swelling agents and surfactants.
  • the method for applying the plating catalyst or its precursor to the layer to be plated is not particularly limited.
  • a plating catalyst solution (a dispersion in which a metal is dispersed in an appropriate dispersion medium, or a solution containing metal ions dissolved in an appropriate solvent and dissociated metal ions) is prepared, and the plating catalyst solution is applied to the layer to be plated.
  • a method of immersing a substrate on which a layer to be plated is formed in a plating catalyst solution.
  • the contact time between the layer to be plated and the plating catalyst solution is preferably about 30 seconds to 20 minutes, and more preferably about 1 minute to 10 minutes.
  • the temperature of the plating catalyst solution at the time of contact is preferably about 10 to 60 ° C., more preferably about 10 to 30 ° C.
  • the adsorption amount (applied amount) of the plating catalyst or its precursor in the layer to be plated is not particularly limited, but is preferably 100 mg / m 2 or less from the viewpoint that the layer to be plated removal step described later proceeds better. More preferred is ⁇ 70 mg / m 2 .
  • the functional group X derived from the unit represented by the formula (B) in the layer to be plated interacts with an intermolecular force such as van der Waals force.
  • the plating catalyst or its precursor can be adsorbed by utilizing electrostatic interaction such as ionic bonding, or interaction by coordination bonding by a lone pair of electrons.
  • a plating process is a process of performing a plating process with respect to the to-be-plated layer to which the plating catalyst or its precursor was provided in the said process, and forming a metal film on a to-be-plated layer.
  • the metal film formed by this process has excellent conductivity and adhesion. More specifically, as shown in FIG. 1B, a metal film 14 is formed on the layer to be plated 12, and a laminate is obtained. Examples of the plating treatment performed in this step include electroless plating and electrolytic plating. In the above step, the plating treatment is selected depending on the function of the plating catalyst or its precursor that forms an interaction with the layer to be plated. be able to.
  • electroless plating from the point of the adhesive improvement of a metal film.
  • electrolytic plating is further performed after the electroless plating.
  • the plating suitably performed in this process will be described.
  • Electroless plating refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved.
  • the electroless plating in this step is performed, for example, by rinsing the substrate provided with the electroless plating catalyst to remove excess electroless plating catalyst (metal) and then immersing it in an electroless plating bath.
  • a known electroless plating bath can be used.
  • the electroless plating bath is preferably an alkaline electroless plating bath (preferably having a pH of about 9 to 14) from the viewpoint of availability.
  • the substrate to which the electroless plating catalyst precursor is applied is immersed in an electroless plating bath in a state where the electroless plating catalyst precursor is adsorbed or impregnated in the layer to be plated, the substrate is washed with water to remove excess. After removing the precursor (metal salt, etc.), it is immersed in an electroless plating bath. In this case, reduction of the plating catalyst precursor and subsequent electroless plating are performed in the electroless plating bath.
  • the electroless plating bath used here a known electroless plating bath can be used as described above.
  • the reduction of the electroless plating catalyst precursor may be performed as a separate step before electroless plating by preparing a catalyst activation liquid (reducing liquid) separately from the embodiment using the electroless plating liquid as described above.
  • the catalyst activation liquid is a liquid in which a reducing agent capable of reducing an electroless plating catalyst precursor (mainly metal ions) to zero-valent metal is dissolved, and the concentration of the reducing agent with respect to the whole liquid is 0.1 to 50% by mass. Preferably, 1 to 30% by mass is more preferable.
  • the reducing agent it is possible to use a boron-based reducing agent such as sodium borohydride or dimethylamine borane, or a reducing agent such as formaldehyde or hypophosphorous acid. When dipping, keep the concentration of the electroless plating catalyst or its precursor near the surface of the layer to be plated in contact with the electroless plating catalyst or its precursor, and soak it with stirring or shaking. Is preferred.
  • the plating bath in addition to a solvent (for example, water), 1. 1. metal ions for plating; 2. reducing agent; Additives (stabilizers) that improve the stability of metal ions are mainly included.
  • the plating bath may contain known additives such as a plating bath stabilizer.
  • the organic solvent used in the plating bath needs to be a solvent that can be used in water, and from this point, ketones such as acetone and alcohols such as methanol, ethanol, and isopropanol are preferably used.
  • the types of metals used in the electroless plating bath for example, copper, tin, lead, nickel, gold, silver, palladium, and rhodium are known. Among them, copper and gold are particularly preferable from the viewpoint of conductivity. preferable. Moreover, the optimal reducing agent and additive are selected according to the said metal.
  • the film thickness of the metal film formed by electroless plating can be controlled by the metal ion concentration of the plating bath, the immersion time in the plating bath, or the temperature of the plating bath. From the viewpoint, it is preferably 0.1 ⁇ m or more, and more preferably 0.2 to 2 ⁇ m. However, when performing electroplating to be described later using a metal film formed by electroless plating as a conductive layer, it is preferable that a film of at least 0.1 ⁇ m or more is uniformly applied.
  • the immersion time in the plating bath is preferably about 1 minute to 6 hours, and more preferably about 1 minute to 3 hours.
  • electrolytic plating electrolytic plating (electroplating)
  • the plating catalyst or its precursor applied in the above step has a function as an electrode
  • electrolytic plating can be performed on the layer to be plated to which the catalyst or its precursor is applied. it can.
  • the formed metal film may be used as an electrode, and further electrolytic plating may be performed.
  • a new metal film having an arbitrary thickness can be easily formed on the electroless plating film having excellent adhesion to the substrate.
  • the metal film can be formed to a thickness according to the purpose, which is suitable for applying the metal film to various applications.
  • a conventionally known method can be used.
  • a metal used for electrolytic plating copper, chromium, lead, nickel, gold
  • the film thickness of the metal film obtained by electrolytic plating can be controlled by adjusting the metal concentration contained in the plating bath, the current density, or the like.
  • the thickness of the metal film is preferably 0.5 ⁇ m or more, more preferably 1 to 30 ⁇ m from the viewpoint of conductivity.
  • the thickness of the electrical wiring is reduced in order to maintain the aspect ratio as the line width of the electrical wiring is reduced, that is, as the size is reduced. Therefore, the layer thickness of the metal film formed by electrolytic plating is not limited to the above, and can be arbitrarily set.
  • the pattern forming step is a step of forming a patterned metal film using an etching solution containing a metal component or hydrogen peroxide after the plating step.
  • a metal pattern material having a patterned metal film on the surface is obtained. More specifically, as shown in FIG. 1C, the etching solution is brought into contact with an unnecessary portion of the metal film 14 so that the portion is removed and the patterned metal film 16 is obtained.
  • the etching solution used in this step dissolves the metal component of the metal film.
  • the etching solution is preferably acidic from the viewpoint of the removability of the metal film.
  • the pH is preferably 5 or less, and more preferably 3 or less.
  • the lower limit is not particularly limited, but is preferably 0 or more from the viewpoint of damage to the layer to be plated.
  • the reagent used in particular for adjusting pH is not restrict
  • the solvent used for the etching solution is not particularly limited, and water, an organic solvent, or the like can be used. From the viewpoints of handleability and etching performance, water is preferred.
  • the etching solution used contains a metal component or hydrogen peroxide. By including these components, the metal film (plating film) can be removed.
  • the metal component preferably contains a metal ion.
  • an optimum metal is appropriately selected depending on the metal constituting the metal film, but is preferably a metal ion having a higher ionization tendency than the metal constituting the metal film, for example, when etching copper Examples include copper ions and iron ions.
  • etching solution examples include a ferric chloride solution or a mixed solution of sulfuric acid and hydrogen peroxide, and a ferric chloride solution is preferable.
  • the contact time between the etching solution and the metal film is not particularly limited, but is preferably 10 seconds to 10 minutes, more preferably 30 seconds to 3 minutes, from the viewpoint of productivity and etching properties of the metal film.
  • the method of forming the patterned metal film 16 using the etching solution is not particularly limited, the first embodiment shown in FIG. 2 is preferable from the viewpoint of productivity. This method is based on a so-called subtractive method.
  • a mask 20 is provided at a predetermined position on the metal film 14.
  • the metal film 14 in a region where the mask 20 is not provided is removed with an etching solution, whereby a patterned metal film 16 is obtained.
  • a known resist material can be used as the mask 20.
  • FIG. 2C the mask 20 is removed.
  • the type of the resist material is not particularly limited, and a negative type, a positive type, a liquid type, and a film type can be used.
  • the method for removing the resist layer is not particularly limited, and a known method (removal with an alkaline solution, dry etching) can be used.
  • the method for bringing the etching solution into contact with the metal film 14 is not particularly limited, and there are a method for applying the etching solution to the metal film 14 (for example, spray coating), a method for immersing a substrate having the metal film 14 in the etching solution, and the like. Can be mentioned.
  • the 2nd embodiment shown in FIG. 3 is mentioned as another suitable aspect of a processing method preferably.
  • This method is based on a so-called semi-additive method.
  • a patterned mask is provided on the metal film obtained by electroless plating, and a metal is further formed in the region where the mask is not provided.
  • Electrolytic plating is performed so that a film is formed. More specifically, as shown in FIG. 3A, after forming a metal film 14a on the layer 12 to be plated by electroless plating, a patterned mask 20 is provided on the metal film 14a (see FIG. B)). Thereafter, as shown in FIG.
  • a metal film is further provided in a region where the mask 20 is not provided (a region where the mask 20 is not formed), and includes a convex portion 22 and a concave portion 24.
  • the uneven metal film 14b is obtained.
  • the mask 20 is removed as shown in FIG.
  • the obtained metal film 14b having the concavo-convex structure is subjected to quick etching using the above etching solution, thereby removing the recesses 24 other than the protrusions 22 corresponding to the wiring portions in the metal film 14b.
  • the patterned metal film 16 is obtained.
  • the acidic solution contact step is a step of bringing a substrate having a patterned metal film into contact with an acidic solution that does not substantially contain a metal component or hydrogen peroxide.
  • the acidic solution contact step By performing this step, the layer to be plated in the region where the patterned metal film is not formed and the acidic solution are in contact with each other, and the metal component (for example, the plating catalyst or the metal film) contained in the layer to be plated is contacted.
  • the constituent metal component is removed. By passing through this process, the removal efficiency of a to-be-plated layer improves in the plasma etching process mentioned later.
  • the to-be-plated layer which does not contain a metal component substantially in the area
  • the acidic solution used in this step exhibits acidity.
  • the pH of the acidic solution is preferably 5 or less, and more preferably 0 to 3 from the viewpoint that the removal performance of the metal component in the layer to be plated is more excellent.
  • the solvent contained in the acidic solution is usually water.
  • the organic solvent (For example, ethanol, methanol, propylene glycol monomethyl ether, isopropyl alcohol) may contain.
  • the acidic solution is substantially free of metal components or hydrogen peroxide. That is, an acidic solution substantially free of metal components and an acidic solution substantially free of hydrogen peroxide are used.
  • the pattern property of the formed patterned metal film is maintained while removing the metal component contained in the layer to be plated.
  • substantially not containing means that the content of the metal component (or hydrogen peroxide) is 1% by mass or less with respect to the total amount of the acidic solution, and is 0.1% by mass or less. Preferably there is. In addition, it is most preferable that content is 0 mass%.
  • the acid component contained in the acidic solution is not particularly limited, for example, known acid components such as hydrochloric acid, sulfuric acid, and nitric acid can be used.
  • known acid components such as hydrochloric acid, sulfuric acid, and nitric acid
  • an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, an aqueous nitric acid solution, or the like can be used.
  • the method for contacting the substrate having the patterned metal film with the acidic solution is not particularly limited, and examples thereof include a method of applying the acidic solution on the substrate and a method of immersing the substrate in the acidic solution.
  • the contact time between the substrate and the acidic solution is appropriately selected depending on the type of the acidic solution used, but from the viewpoint of removability of the metal component in the layer to be plated, it is 10 seconds to 10 minutes. Preferably, 1 to 5 minutes is more preferable.
  • the to-be-plated layer removing step is a step of removing the to-be-plated layer in the region where the patterned metal film is not formed by plasma etching. More specifically, the substrate having the patterned metal film is subjected to plasma etching, and as shown in FIGS. 1C and 1D, the substrate in the region 30 where the patterned metal film 16 is not formed. The plating layer 12 is removed. By removing the layer to be plated between the patterned metal films, the insulation performance between the wirings (between the metal films) is further improved.
  • the plasma etching process a known processing method can be performed, and examples thereof include a low-pressure plasma process or an atmospheric plasma process performed under atmospheric pressure.
  • the plasma etching process will be described in detail.
  • the substrate on which the wiring pattern after the pattern formation step is formed is housed in a chamber of a plasma processing apparatus, and plasma is generated in the chamber to generate ions and ions. This is done by causing neutral particles called radicals to collide with the substrate surface.
  • the formed patterned metal film itself functions as an etching resist. Therefore, the plasma etching process causes a layer to be plated that remains exposed between the wirings, and adheres between the wirings. It is possible to effectively remove impurities such as organic matter. Note that it is preferable to perform the plasma etching process under processing conditions that do not affect the formed wiring pattern.
  • a plasma generation method either a low-pressure plasma method or an atmospheric plasma method can be applied, but a general-purpose low-pressure plasma method is preferably used.
  • the atmospheric pressure when performing the plasma etching treatment is preferably 100 Pa or less, and more preferably 10 Pa or less, from the viewpoint of the etching rate. Note that if the atmospheric pressure plasma method is used, there is no need for depressurization, which is an advantage that in-line processing is possible, and this can be expected to improve production efficiency.
  • the gas to be used can be appropriately selected according to various conditions such as the influence on the substrate surface state after the processing, the control of the processing speed and the substrate temperature, and the like.
  • oxygen gas, argon gas, CF 4 , and a mixed gas of oxygen gas and argon gas are preferable, and a mixed gas of argon gas, oxygen gas, and argon gas is more preferable.
  • oxygen gas is used as the plasma gas
  • the oxygen gas can generate hydroxyl groups on the treatment surface, for example, a solder resist mainly composed of an epoxy resin is disposed on the wiring board.
  • the adhesion between the substrate surface and the solder resist can be improved.
  • the CF-based gas can improve the hydrophobicity of the processing surface.
  • the insulation reliability between the wirings can be further improved, such as the intrusion of moisture and the like from the interface between the substrates can be effectively prevented.
  • the atmospheric pressure when performing the plasma etching process is 100 Pa or less from the viewpoint of the etching rate, that is, the amount of plasma generated.
  • oxygen gas, argon gas, CF 4 gas, and C 2 It is preferable to use at least one gas selected from the group consisting of F 4 gas.
  • a laminate having a patterned metal film from which the layer to be plated between the patterned metal films is removed can be obtained (FIG. 1D).
  • the obtained laminated body can be used for various uses. For example, it can be applied to various uses such as semiconductor chips, various electric wiring boards (printed wiring boards, etc.), FPC, COF, TAB, antennas, multilayer wiring boards, motherboards, and the like. Especially, it can utilize suitably as a wiring board. Moreover, when using with a wiring board, you may provide the insulating layer 40 on the laminated body 18 as needed (FIG.1 (E)).
  • the wiring substrate 50 including the laminate 18 and the insulating layer 40 of the present invention can form a wiring having excellent adhesion to a smooth substrate, has good high-frequency characteristics, and is a fine high-density wiring. Excellent insulation reliability between wires.
  • a known material can be used for the insulating layer 40, and examples thereof include a known interlayer insulating film and a solder resist.
  • the ethyl acetate layer was washed four times with 300 mL of distilled water, dried over magnesium sulfate, and 80 g of raw material A was obtained by distilling off ethyl acetate.
  • the raw material A 47.4g
  • pyridine 22g
  • ethyl acetate 150mL
  • 25 g of acrylic acid chloride was added dropwise while adjusting the internal temperature to 20 ° C. or lower. Then, it was raised to room temperature and reacted for 3 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction.
  • the acid value of the obtained polymer A was measured using a potentiometric automatic titrator (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1 M sodium hydroxide aqueous solution as the titrant, the acid value of the polymer A was It was 5.7 mmol / g.
  • the obtained polymer A was dissolved in acetone, and measurement was performed using an KBr crystal with an IR measuring machine (manufactured by Horiba, Ltd.). As a result of IR measurement, no peak was observed in the vicinity of 2240 cm ⁇ 1 , and it was found that the cyano group was not contained in the polymer A. Further, it was found from the acid value measurement that acrylic acid was introduced as a carboxylic acid unit. Further, it was dissolved in heavy DMSO (dimethyl sulfoxide) and measured by Bruker 300 MHz NMR (AV-300).
  • DMSO dimethyl sulfoxide
  • the peak corresponding to the polymerizable group-containing unit is 8.1 to 7.8 ppm (1 H min), 5.8 to 5.6 ppm (1 H min), 5.4 to 5.2 ppm (1 H min), 4.2 Broad peaks were observed at 3.9 ppm (2H min), 3.5-3.3 ppm (2H min), and 2.5-0.7 ppm (6H min), and peaks corresponding to carboxylic acid group units were 2.5- It was observed broadly at 0.7 ppm (3H), and it was confirmed that a polymer composed of a polymerizable group-containing unit and a carboxylic acid group unit was produced.
  • a raw material B 45 g
  • pyridine 22 g
  • ethyl acetate 150 mL
  • 25 g of acrylic acid chloride was added dropwise while adjusting the internal temperature to 20 ° C. or lower.
  • it was raised to room temperature and reacted for 3 hours.
  • 300 mL of distilled water was added to stop the reaction.
  • the acid value of the obtained polymer B was measured using a potentiometric automatic titrator (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1 M sodium hydroxide aqueous solution as the titrant, the acid value of the polymer B was It was 5.8 mmol / g.
  • the obtained polymer B was dissolved in acetone and measured using an KBr crystal with an IR measuring device (manufactured by Horiba, Ltd.). As a result of IR measurement, no peak was observed in the vicinity of 2240 cm ⁇ 1 , and it was found that the cyano group was not contained in the polymer B. Moreover, it turned out that acrylic acid is introduce
  • DMSO dimethyl sulfoxide
  • Peaks corresponding to the polymerizable group-containing unit are 8.1 to 7.8 ppm (2H min), 5.8 to 5.6 ppm (1 H min), 5.4 to 5.2 ppm (1 H min), 3.5- A broad peak was observed at 3.3 ppm (4H min) and 2.5-0.7 ppm (6H min), and a peak corresponding to a carboxylic acid group unit was observed broad at 2.5-0.7 ppm (3H min). It was confirmed that a polymer composed of a polymerizable group-containing unit and a carboxylic acid group unit was produced.
  • a raw material C 72 g
  • pyridine 22 g
  • ethyl acetate 150 mL
  • the acrylic acid chloride 25g was dripped and adjusted so that it might become 20 degrees C or less of internal temperature there. Then, it was raised to room temperature and reacted for 3 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction. Thereafter, the ethyl acetate layer was washed four times with 300 mL of distilled water, dried over magnesium sulfate, and ethyl acetate was distilled off.
  • the monomer C was purified by column chromatography to obtain 25 g.
  • the acid value of the obtained polymer C was measured using a potentiometric automatic titrator (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1 M sodium hydroxide aqueous solution as the titrant, the acid value of the polymer C was It was 4.4 mmol / g.
  • the obtained polymer C was dissolved in acetone, and measurement was performed using an KBr crystal with an IR measuring machine (manufactured by Horiba, Ltd.). As a result of IR measurement, it was found that no peak was observed in the vicinity of 2240 cm ⁇ 1 and that the cyano group was not contained in the polymer C. Further, it was found from the acid value measurement that acrylic acid was introduced as a carboxylic acid unit. Further, it was dissolved in heavy DMSO (dimethyl sulfoxide) and measured by Bruker 300 MHz NMR (AV-300).
  • DMSO dimethyl sulfoxide
  • the peak corresponding to the polymerizable group-containing unit is 8.1 to 7.8 ppm (1 H min), 5.8 to 5.6 ppm (1 H min), 5.4 to 5.2 ppm (1 H min), 4.4 A broad peak was observed at 4.1 ppm (2H min), 3.5-3.3 ppm (2H min), and 2.5-0.7 ppm (21H min), and peaks corresponding to carboxylic acid group units were 2.5- It was observed broadly at 0.7 ppm (3H), and it was confirmed that a polymer composed of a polymerizable group-containing unit and a carboxylic acid group unit was produced.
  • the ethyl acetate layer was washed four times with 300 mL of distilled water, dried over magnesium sulfate, and 90 g of raw material D was obtained by distilling off ethyl acetate.
  • the raw material D (57g), pyridine (22g), and ethyl acetate (150mL) were put into a 500 mL three necked flask, and it cooled in the ice bath.
  • the acrylic acid chloride 25g was dripped and adjusted so that it might become 20 degrees C or less of internal temperature there. Then, it was raised to room temperature and reacted for 3 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction.
  • the acid value of the obtained polymer D was measured using a potentiometric automatic titration apparatus (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1 M sodium hydroxide aqueous solution as a titrant, the acid value of the polymer D was It was 5.0 mmol / g.
  • the obtained polymer D was dissolved in acetone and measured using an KBr crystal with an IR measuring device (manufactured by Horiba, Ltd.). As a result of IR measurement, no peak was observed in the vicinity of 2240 cm ⁇ 1 , and it was found that the cyano group was not contained in the polymer D. Further, it was found from the acid value measurement that acrylic acid was introduced as a carboxylic acid unit. Further, it was dissolved in heavy DMSO (dimethyl sulfoxide) and measured by Bruker 300 MHz NMR (AV-300).
  • DMSO dimethyl sulfoxide
  • the peak corresponding to the polymerizable group-containing unit is 8.1 to 7.8 ppm (1 H min), 5.8 to 5.6 ppm (1 H min), 5.4 to 5.2 ppm (1 H min), 4.2 Broad peaks were observed at 3.9 ppm (2H min), 3.8-3.3 ppm (6H min), and 2.5-0.7 ppm (6H min), and peaks corresponding to carboxylic acid group units were 2.5- It was observed broadly at 0.7 ppm (3H), and it was confirmed that a polymer composed of a polymerizable group-containing unit and a carboxylic acid group unit was produced.
  • a raw material E (57 g), pyridine (24 g), and ethyl acetate (170 mL) were placed in a 500 mL three-necked flask and cooled in an ice bath.
  • the acrylic acid chloride 28g was dripped and adjusted so that it might become 20 degrees C or less of internal temperature there. Then, it was raised to room temperature and reacted for 3 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction.
  • the acid value of the obtained polymer E was measured using a potentiometric automatic titration apparatus (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1 M sodium hydroxide aqueous solution as the titrant, the acid value of the polymer E was It was 5.0 mmol / g.
  • the obtained polymer E was dissolved in acetone and measured using an KBr crystal with an IR measuring device (manufactured by Horiba, Ltd.). As a result of IR measurement, no peak was observed in the vicinity of 2240 cm ⁇ 1 , and it was found that the cyano group was not contained in the polymer E. Further, it was found from the acid value measurement that acrylic acid was introduced as a carboxylic acid unit. Further, it was dissolved in heavy DMSO (dimethyl sulfoxide) and measured by Bruker 300 MHz NMR (AV-300).
  • DMSO dimethyl sulfoxide
  • Peaks corresponding to the polymerizable group-containing unit are 7.8-8.1 ppm (1H min), 7.0-7.5 ppm (4H), 5.8-5.6 ppm (1H min), 5.4-5 .2 ppm (1H min), 4.4-4.6 ppm (2H min), and 2.5-0.7 ppm (6H min) broadly observed, and a peak corresponding to a carboxylic acid group unit is 2.5-0. It was observed broadly at 0.7 ppm (3H), and it was confirmed that a polymer composed of a polymerizable group-containing unit and a carboxylic acid group unit was produced.
  • the acid value of the obtained polymer F was measured using a potentiometric automatic titration apparatus (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1M sodium hydroxide aqueous solution as a titrant, the acid value of the polymer F was It was 3.4 mmol / g.
  • the obtained polymer F was dissolved in acetone, and measurement was performed using an KBr crystal with an IR measuring machine (manufactured by Horiba, Ltd.). As a result of IR measurement, no peak was observed in the vicinity of 2240 cm ⁇ 1 , and it was found that the cyano group was not contained in the polymer F. In addition, it was found from the acid value measurement that 2-methylpropanesulfonic acid was introduced as the sulfonic acid unit. Further, it was dissolved in heavy DMSO (dimethyl sulfoxide) and measured by Bruker 300 MHz NMR (AV-300).
  • DMSO dimethyl sulfoxide
  • the peak corresponding to the polymerizable group-containing unit is 8.1 to 7.8 ppm (1 H min), 5.8 to 5.6 ppm (1 H min), 5.4 to 5.2 ppm (1 H min), 4.2 Broad peaks were observed at 3.9 ppm (2H min), 3.5-3.3 ppm (2H min), and 2.5-0.7 ppm (6H min), and peaks corresponding to sulfonic acid group units were 8.1-.
  • the acid value of the obtained polymer G was measured using a potentiometric automatic titrator (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1 M sodium hydroxide aqueous solution as the titrant, the acid value of the polymer G was It was 3.5 mmol / g.
  • the obtained polymer G was dissolved in acetone and measured using an KBr crystal with an IR measuring device (manufactured by Horiba, Ltd.). As a result of IR measurement, no peak was observed in the vicinity of 2240 cm ⁇ 1 , and it was found that the cyano group was not contained in the polymer G. Moreover, it turned out that the phosmer M was introduce
  • DMSO dimethyl sulfoxide
  • the peak corresponding to the polymerizable group-containing unit is 8.1 to 7.8 ppm (1 H min), 5.8 to 5.6 ppm (1 H min), 5.4 to 5.2 ppm (1 H min), 4.2 Broad peaks were observed at 3.9 ppm (2H min), 3.5-3.3 ppm (2H min), and 2.5-0.7 ppm (6H min), and peaks corresponding to phosphate group units were 4.3- It was observed broadly at 3.8 ppm (4H component) and 2.5-0.7 ppm (5H component), and it was confirmed that a polymer composed of a polymerizable group-containing unit and a phosphate group unit was produced.
  • the acid value of the obtained polymer H was measured using a potentiometric automatic titrator (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1M sodium hydroxide aqueous solution as a titrant, the acid value of the polymer H was It was 3.1 mmol / g.
  • the obtained polymer H was dissolved in acetone, and measurement was performed using an KBr crystal with an IR measuring machine (manufactured by Horiba, Ltd.). As a result of IR measurement, no peak was observed in the vicinity of 2240 cm ⁇ 1 , and it was found that the cyano group was not contained in the polymer H. Further, it was found from the acid value measurement that NK ester A-SA was introduced as a carboxylic acid unit. Further, it was dissolved in heavy DMSO (dimethyl sulfoxide) and measured by Bruker 300 MHz NMR (AV-300).
  • DMSO dimethyl sulfoxide
  • the peak corresponding to the polymerizable group-containing unit is 8.1 to 7.8 ppm (1 H min), 5.8 to 5.6 ppm (1 H min), 5.4 to 5.2 ppm (1 H min), 4.2 Broad peaks were observed at 3.9 ppm (2H min), 3.5-3.3 ppm (2H min), 2.5-0.7 ppm (6H min), and peaks corresponding to carboxylic acid group units were 4.2- It was observed broadly at 3.9 ppm (4H content) and 2.8-0.7 ppm (7H content), and it was confirmed that a polymer composed of a polymerizable group-containing unit and a carboxylic acid group unit was produced.
  • Comparative polymer 1 A 500 mL three-necked flask was charged with 8 g of N, N-dimethylacetamide and heated to 65 ° C. under a nitrogen stream. Thereto, monomer A: 14.3 g obtained above, acrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.0 g, acrylic acid (manufactured by Tokyo Chemical Industry) 6.5 g, V-65 (manufactured by Wako Pure Chemical Industries) 4 g of N, N-dimethylacetamide 8 g solution was added dropwise over 4 hours. After completion of dropping, the mixture was further stirred for 3 hours.
  • monomer A 14.3 g obtained above, acrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.0 g, acrylic acid (manufactured by Tokyo Chemical Industry) 6.5 g, V-65 (manufactured by Wako Pure Chemical Industries) 4 g of N, N-dimethylacetamide 8
  • the obtained comparative polymer 1 was identified using an IR measuring machine (manufactured by Horiba, Ltd.). The measurement was performed by dissolving the polymer in acetone and using KBr crystals. As a result of IR measurement, a peak was observed in the vicinity of 2240 cm ⁇ 1 , and it was found that acrylonitrile as a nitrile unit was introduced into the polymer. Further, it was found from the acid value measurement that acrylic acid was introduced as a carboxylic acid unit. Further, it was dissolved in heavy DMSO (dimethyl sulfoxide) and measured by Bruker 300 MHz NMR (AV-300). 4.
  • DMSO dimethyl sulfoxide
  • a peak corresponding to a cyano group-containing unit is broadly observed at 2.5-0.7 ppm (5H min), and a peak corresponding to a polymerizable group-containing unit is 7.8-8.1 ppm (1H min). 8-5.6 ppm (1H min), 5.4-5.2 ppm (1H min), 4.2-3.9 ppm (2H min), 3.3-3.5 ppm (2H min), 2.5- A broad peak is observed at 0.7 ppm (6H min), and a peak corresponding to a carboxylic acid group unit is observed broadly at 2.5-0.7 ppm (3H min), a polymerizable group-containing unit, a cyano group-containing unit, It was also confirmed that a polymer composed of carboxylic acid group units was produced.
  • Example 1> (Preparation of base insulating substrate) An epoxy insulating film (GX-13, 45 ⁇ m) manufactured by Ajinomoto Fine Techno Co. on a glass epoxy substrate (trade name: FR-4, manufactured by Matsushita Electric Works Co., Ltd.) at a pressure of 0.2 MPa. An electrical insulating layer was formed on the substrate by heating and pressing using a vacuum laminator under the condition of 110 ° C. for adhesion. Thereafter, heat treatment was performed at 170 ° C. for 1 hour, and the electrically insulating layer was formed into a thermal layer.
  • GX-13, 45 ⁇ m manufactured by Ajinomoto Fine Techno Co. on a glass epoxy substrate (trade name: FR-4, manufactured by Matsushita Electric Works Co., Ltd.) at a pressure of 0.2 MPa.
  • An electrical insulating layer was formed on the substrate by heating and pressing using a vacuum laminator under the condition of 110 ° C. for adhesion. Thereafter, heat treatment was
  • a composition for forming an adhesion auxiliary layer having the following composition was applied by spin coating so as to have a thickness of 1.5 ⁇ m, and then dried at 140 ° C. for 30 minutes for adhesion. An auxiliary layer was formed. The substrate after the adhesion auxiliary layer was formed was further subjected to a curing treatment at 180 ° C. for 30 minutes to produce a substrate A1.
  • Adhesion auxiliary layer forming composition 25 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 185, Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) 45 parts of Chemical Industries Co., Ltd. Epicron N-673), 30 parts of phenol novolak resin (phenolic hydroxyl group equivalent 105, Phenolite manufactured by Dainippon Ink & Chemicals, Inc.), 20 parts of ethyl diglycol acetate, solvent naphtha 20 The mixture was heated and dissolved with stirring, and cooled to room temperature.
  • cyclohexanone varnish (YL6747H30 manufactured by Yuka Shell Epoxy Co., Ltd., nonvolatile content 30 mass%, weight average molecular weight 47000) of phenoxy resin composed of the above Epicoat 828 and bisphenol S, 2-phenyl-4,5- 0.8 parts of bis (hydroxymethyl) imidazole, 2 parts of finely pulverized silica, and 0.5 parts of a silicon-based antifoaming agent are added, and 10 parts of polymer P having a polymerization initiating group synthesized by the following method is added to this mixture.
  • a composition for forming an adhesion auxiliary layer was prepared.
  • composition A for forming a layer to be plated was applied on the substrate A1 by a spin coating method so as to have a thickness of 1.5 ⁇ m, and then dried at 80 ° C.
  • the applied composition layer was exposed to ultraviolet light having a wavelength of 254 nm for 2 minutes at room temperature (254 nm) using an exposure machine (ultraviolet irradiation device, UVX-02516S1LP01, manufactured by USHIO INC.). Energy amount at 1200 mJ).
  • the substrate was sufficiently washed with a 1% sodium bicarbonate solution in order to remove an unnecessary composition for forming a layer to be plated.
  • a substrate A2 having a layer to be plated (thickness after cleaning: 0.7 ⁇ m) on the substrate A1 was obtained.
  • composition A for Plating Layer Formation Polymer A 3.1g ⁇ Baking soda 1.2g ⁇ Water 25.9g ⁇ 13.0 g of 1-methoxy-2-propanol
  • Substrate A2 was dipped in an aqueous solution (liquid temperature: 25 ° C.) of 0.1% by mass of palladium nitrate for 10 minutes, and then washed with distilled water.
  • the amount of palladium ion adsorbed at this time was 0.1 g / m 2 when measured with an ICP emission analyzer (manufactured by Shimadzu Corporation).
  • Electroless plating treatment The substrate after the plating catalyst (metal salt) was applied was immersed in an electroless plating bath (alkaline: pH 12.5) having the following composition for 1 hour to form an electroless copper plating layer having a thickness of 0.4 ⁇ m.
  • the substrate on which the electroless copper plating layer was formed was immersed in an electrolytic copper plating bath having the following composition, and electroplating was performed for about 20 minutes under a current density of 3 A / dm 2 .
  • the thickness of the copper plating layer (metal film) after the electrolytic plating was about 18 ⁇ m.
  • the metal film is etched by showering an FeCl 2 / HCl aqueous solution (temperature: 37 ° C.) (pH: 1.5) for 90 seconds with respect to the substrate on which the resist pattern is formed, and exists in the resist pattern non-formation region.
  • the copper plating was removed. Thereafter, a resist pattern was peeled off by forming a 4 mass% NaOH aqueous solution on the substrate at a spray pressure of 2 kg / m 2 .
  • a substrate having a patterned metal film (wiring pattern) is placed in a chamber of a plasma etching apparatus (manufactured by SAMCO, parallel plate type plasma processing apparatus, PC-1000), and the wiring pattern forming surface faces the plasma irradiation surface. Arranged. The inside of the chamber was depressurized to 4 ⁇ 10 ⁇ 1 Pa (3 ⁇ 10 ⁇ 3 Torr), and plasma treatment was performed in an oxygen atmosphere for 1.5 minutes. When the cross section of the treated substrate surface was observed with an SEM image, it was confirmed that the layer to be plated and the adhesion auxiliary layer between the wires were removed.
  • Solder resist (PFR800; manufactured by Taiyo Ink Mfg. Co., Ltd.) is vacuum-laminated on the plasma-treated substrate under conditions of 110 ° C. and 0.2 MPa, and light energy of 420 mJ is irradiated with an exposure machine having a central wavelength of 365 nm did.
  • the substrate was subjected to a heat treatment at 80 ° C./10 minutes, and then developed by applying a NaHCO 3 : 10% aqueous solution to the substrate surface at a spray pressure of 2 kg / m 2 and dried. Thereafter, the substrate was again irradiated with light energy of 1000 mJ with an exposure machine having a center wavelength of 365 nm.
  • a heat treatment at 150 ° C./1 hr was performed to obtain a wiring board coated with a solder resist.
  • Example 2 A wiring board was obtained according to the same procedure as in Example 1 except that the procedure of (application of plating catalyst) in Example 1 was changed to the procedure described below.
  • the substrate A2 was immersed in an aqueous solution (liquid temperature: 60 ° C.) of palladium nitrate of 0.1% by mass for 10 minutes and then washed with distilled water.
  • the amount of palladium ion adsorbed onto the layer to be plated at this time was 0.2 g / m 2 when measured with an ICP issuing analyzer (manufactured by Shimadzu Corporation).
  • Example 3 According to the same procedure as in Example 1, except that the etching process of the metal film using the FeCl 2 / HCl aqueous solution in (Pattern forming step) in Example 1 was changed to the procedure described below. Got.
  • the substrate on which the resist pattern is formed is immersed in a Cu (NH 3 ) 4 Cl 2 aqueous solution (temperature: 37 ° C.) (pH: 8.5) to etch the metal film and exist in the resist pattern non-formation region.
  • the copper plating was removed.
  • Example 4 For the substrate having the electrical insulating layer prepared in (Preparation of base insulating substrate) without carrying out the step (Formation of adhesion auxiliary layer) in Example 1 above (Formation of layer to be plated) A wiring board was obtained according to the same procedure as in Example 1 except that the step was performed and a layer to be plated was formed on the electrically insulating layer. In Example 4, the layer to be plated is disposed on the substrate without using the adhesion auxiliary layer.
  • Example 5 A wiring board was obtained according to the same procedure as in Example 1, except that the composition A for plating layer formation in Example 1 was changed to the following composition B for plating layer formation.
  • composition B for Plating Layer Formation ⁇ Polymer B 3.1g ⁇ Baking soda 1.3g ⁇ Water 26.4g -1-methoxy-2-propanol 13.2g
  • Example 6 Except that the composition A for plating layer formation in Example 1 was changed to the following composition C for plating layer formation, and the exposure conditions in (Formation of the plating layer) were changed as follows: A wiring board was obtained according to the same procedure as in Example 1.
  • composition C for Plating Layer Formation Polymer C 3.1g ⁇ Baking soda 0.9g ⁇ Water 24.0g 1-methoxy-2-propanol 12.0g
  • Example 7 Implementation was performed except that the composition A for plating layer formation in Example 1 was changed to the following composition D for plating layer formation and the exposure conditions in (Formation of the plating layer) were changed as follows.
  • a wiring board was obtained according to the same procedure as in Example 1.
  • composition D for Plating Layer Formation Polymer D 3.1g ⁇ Baking soda 1.1g ⁇ Water 25.0g ⁇ 12.5 g of 1-methoxy-2-propanol
  • UVX-02516S1LP01 ultraviolet light having a wavelength of 254 nm was exposed for 2.5 minutes at room temperature (energy amount at 254 nm: 1500 mJ).
  • Example 8 Implementation was performed except that the composition A for plating layer formation in Example 1 was changed to the following composition E for plating layer formation, and the exposure conditions in (Formation of the plating layer) were changed as follows.
  • a wiring board was obtained according to the same procedure as in Example 1.
  • composition E for Plating Layer Formation Polymer E 3.1g ⁇ Baking soda 1.0g ⁇ Water 24.7g 1-methoxy-2-propanol 12.4g
  • Example 9 The composition A for forming a layer to be plated in Example 1 is changed to the following composition F for forming a layer to be plated, the exposure conditions in (Formation of layer to be plated) are changed as follows, and further (plating) A wiring board was obtained according to the same procedure as in Example 1 except that the amount of palladium deposited in the catalyst application was changed to “0.07 g / m 2 ”.
  • composition F for forming layer to be plated ⁇ Polymer F 3.1g ⁇ Baking soda 0.7g ⁇ Water 22.7g ⁇ 11.3 g of 1-methoxy-2-propanol
  • UVX-02516S1LP01 ultraviolet light having a wavelength of 254 nm was exposed for 2.5 minutes at room temperature (energy amount at 254 nm: 1500 mJ).
  • Example 10 The composition A for forming a layer to be plated in Example 1 is changed to the following composition G for forming a layer to be plated, the exposure conditions in (Formation of layer to be plated) are changed as follows, and further (plating) A wiring board was obtained according to the same procedure as in Example 1 except that the amount of palladium deposited in the catalyst application was changed to “0.12 g / m 2 ”.
  • composition G for Plating Layer Formation Polymer G 3.1g ⁇ Baking soda 1.3g ⁇ Water 22.9g ⁇ 11.5g of 1-methoxy-2-propanol
  • UVX-02516S1LP01 ultraviolet light having a wavelength of 254 nm was exposed for 2.5 minutes at room temperature (energy amount at 254 nm: 1500 mJ).
  • Example 11 The composition A for forming a layer to be plated in Example 1 is changed to the following composition H for forming a layer to be plated, the exposure conditions in (Formation of layer to be plated) are changed as follows, and further (plating) A wiring board was obtained according to the same procedure as in Example 1 except that the amount of palladium deposited in the catalyst application was changed to “0.08 g / m 2 ”.
  • UVX-02516S1LP01 ultraviolet light having a wavelength of 254 nm was exposed for 2.5 minutes at room temperature (energy amount at 254 nm: 1500 mJ).
  • Example 1 A wiring board was produced according to the same procedure as in Example 1 except that Comparative Polymer 1 was used instead of Polymer A used in Example 1. When the cross section of the substrate surface after removal of the plated layer was observed with an SEM image, it was confirmed that the plated layer between the wirings remained.
  • Example 2 A wiring board was manufactured according to the same procedure as in Example 1 except that (to-be-plated layer removal) in Example 1 was not performed.
  • Example 3 A wiring board was obtained according to the same procedure as in Example 1 except that the (acidic solution treatment) step in Example 1 was not performed.
  • C When the resistance value of the wiring board falls below 1 M ⁇ in the evaluation up to less than 750 hours.
  • B When the resistance value of the wiring board falls below 1 M ⁇ in the evaluation from 750 hours to less than 1000 hours.
  • A When the evaluation is performed up to 1000 hours and the resistance value of the wiring board does not fall below 1 M ⁇ .
  • Table 1 shows the etching rate ( ⁇ m / min) of plasma etching when removing the layer to be plated and the adhesion auxiliary layer in Examples 1 to 11 and Comparative Examples 1 and 3 (removal of the layer to be plated). Shown together.
  • “A” in the “Plating catalyst adsorption condition” column indicates that when the temperature of the 0.1 wt% palladium nitrate aqueous solution used in (application of plating catalyst) is 25 ° C., “B” indicates nitric acid. This means that the liquid temperature of the palladium 0.1 mass% aqueous solution is 60 ° C.
  • “A” in the “Type of etchant” column indicates that the etchant used in the (pattern formation step) is an FeCl 2 / HCl aqueous solution, and “B” indicates that the etchant is a Cu (NH 3 ) 4 Cl 2 aqueous solution. Means the case. In Table 1, “-” means not implemented.
  • the wiring board obtained by carrying out the method for producing a laminate having a patterned metal film of the present invention exhibited excellent insulating performance. Further, in Examples 1 to 11, the plasma etching rate of the layer to be plated was excellent. In addition, compared with Example 1 and 2, Example 1 with little adsorption amount of the palladium ion in a to-be-plated layer was more excellent in insulation. This is because the smaller the amount of the metal component in the layer to be plated, the better the etching property of the layer to be plated. Further, from comparison between Examples 1 and 3, it was confirmed that the use of an acidic etching solution (FeCl 2 / HCl aqueous solution) as the etching solution was superior in insulation. This can be said to be because the metal component in the layer to be plated is easily removed when the etching solution is used.
  • an acidic etching solution FeCl 2 / HCl aqueous solution
  • a substrate (laminated body) having a metal film obtained after the (electrolytic plating) step of Example 1 and Comparative Example 4 described later is left at 80 ° C. and 90 RH% for one week, and then JIS-K5600-5-6. : A cross-cut peel test was performed according to 1999. Evaluation was made according to the following criteria. “A”: When 95 or more of 100 eyes remain “B”: When less than 95 of 100 eyes remain
  • Example 1 the moisture resistance evaluation was “A”, but in Comparative Example 4, it was “B”. This is because in the production method of the present invention, the unit represented by the formula (A) has a (meth) acrylamide group, so that it is not easily hydrolyzed, and as a result, the adhesion of the metal film is further improved. it is conceivable that.
  • a wiring board was formed in the same manner as in Example 1 except that the following composition X for plating layer formation was used instead of the composition A for plating layer formation.
  • composition X for Plating Layer Formation ⁇ Comparative polymer 2 0.25g ⁇ Water 5g ⁇ Acetonitrile 3g
  • Substrate 12 Plated layers 14, 14a, 14b: Metal film 16: Patterned metal film 18: Laminated body 18: Patterned metal film 20: Mask 22: Convex part 24: Concave part 30: Patterned metal film formed Unused region 40: insulating layer 50: wiring board

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemically Coating (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un stratifié possédant des films métalliques à motifs, lequel permet d'obtenir un stratifié avec d'excellentes propriétés d'isolation entre les couches métalliques à motifs, ainsi que la mise en oeuvre aisée d'un traitement de gravure au plasma d'une couche devant être plaquée. Plus spécifiquement, ce procédé de fabrication d'un stratifié possédant des films métalliques à motifs comprend: une étape de formation de couche devant être plaquée, dans laquelle une couche devant être plaquée est formée sur un substrat au moyen d'une composition pour formation de couche devant être plaquée contenant un copolymère binaire constitué d'une unité prédéfinie; une étape d'application de catalyseur, dans laquelle un catalyseur de placage ou un précurseur de celui-ci est appliqué sur la couche devant être plaquée; une étape de placage, dans laquelle est effectué un traitement de placage, un film métallique étant formé sur la couche devant être plaquée; une étape de formation de motif, dans laquelle un motif est formé sur le film métallique au moyen d'un liquide de gravure; une étape de mise en contact avec une solution acide, dans laquelle une solution acide est mise en contact avec le substrat possédant un film métallique à motif; et une étape de retrait de couche devant être plaquée, dans laquelle la couche devant être plaquée, dans une zone sur laquelle le film métallique à motif n'a pas été formé, est retirée par gravure au plasma.
PCT/JP2012/057148 2011-03-29 2012-03-21 Procédé de fabrication d'un stratifié possédant des films métalliques à motifs et composition pour formation de couche devant être plaquée WO2012133032A1 (fr)

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JP2011-073189 2011-03-29
JP2011073189A JP2012209392A (ja) 2011-03-29 2011-03-29 パターン状金属膜を有する積層体の製造方法、被めっき層形成用組成物

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Cited By (1)

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CN109776712B (zh) * 2018-08-16 2021-01-15 上海紫剑化工科技有限公司 一种丙烯酸聚合物、硅负极极片及其制备方法和应用

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JP6540540B2 (ja) * 2016-02-24 2019-07-10 三菱マテリアル株式会社 パワーモジュール用基板の製造方法
WO2023119998A1 (fr) * 2021-12-24 2023-06-29 富士フイルム株式会社 Procédé de production d'un stratifié ayant un motif conducteur, composition photosensible et film de transfert

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JP2004311912A (ja) * 2002-12-06 2004-11-04 Sony Corp 回路基板モジュール及びその製造方法
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JP2008135685A (ja) * 2006-10-23 2008-06-12 Fujifilm Corp 配線基板の製造方法及び配線基板、並びに、多層配線基板の製造方法及び多層配線基板
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JP2000204480A (ja) * 1999-01-08 2000-07-25 Origin Electric Co Ltd 部分メッキ方法及びこれを施した物品
JP2001196728A (ja) * 2000-01-11 2001-07-19 Toshiba Chem Corp プリント配線板の製造方法およびプリント配線板の層間接続穴用メッキ装置
JP2004311912A (ja) * 2002-12-06 2004-11-04 Sony Corp 回路基板モジュール及びその製造方法
JP2007287994A (ja) * 2006-04-18 2007-11-01 Fujifilm Corp 金属パターン形成方法、金属パターン、及びプリント配線板
JP2008135685A (ja) * 2006-10-23 2008-06-12 Fujifilm Corp 配線基板の製造方法及び配線基板、並びに、多層配線基板の製造方法及び多層配線基板
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JP2010077322A (ja) * 2008-09-26 2010-04-08 Fujifilm Corp 被めっき層形成用組成物、金属パターン材料の作製方法及びそれにより得られた金属パターン材料、表面金属膜材料の作製方法及びそれにより得られた表面金属膜材料

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109776712B (zh) * 2018-08-16 2021-01-15 上海紫剑化工科技有限公司 一种丙烯酸聚合物、硅负极极片及其制备方法和应用

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