WO2012073814A1 - Procédé de production de stratifié comportant un film métallique - Google Patents

Procédé de production de stratifié comportant un film métallique Download PDF

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WO2012073814A1
WO2012073814A1 PCT/JP2011/077164 JP2011077164W WO2012073814A1 WO 2012073814 A1 WO2012073814 A1 WO 2012073814A1 JP 2011077164 W JP2011077164 W JP 2011077164W WO 2012073814 A1 WO2012073814 A1 WO 2012073814A1
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group
polymer layer
metal film
substrate
silane coupling
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PCT/JP2011/077164
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Japanese (ja)
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鶴見　光之
貴胤 河野
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富士フイルム株式会社
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
    • H05K3/387—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive for electroless plating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1168—Graft-polymerization
    • 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
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/108—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by semi-additive methods; masks therefor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane

Definitions

  • the present invention relates to a method for manufacturing a laminate having a metal film.
  • 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.
  • the 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 corrosive acid such as chromic acid. There was a problem that a process was necessary. Especially for glass substrates and ceramic substrates, there is no good way to roughen the surface.
  • a graft polymer directly bonded to the substrate is formed on a substrate having a silane coupling agent layer to form a polymer layer, and the polymer layer is plated to form a polymer layer on the polymer layer.
  • a method of etching a metal film obtained in the above is known (Patent Document 1). According to this method, the adhesion between the substrate and the metal film can be improved without roughening the substrate surface.
  • Patent Document 1 discloses a laminate having a metal film using a silane coupling agent layer, and to a more severe high temperature condition as required recently.
  • the adhesion of the metal film after exposure was examined. As a result, the metal film after being exposed to high-temperature conditions often shows “swelling” due to insufficient adhesion of the metal film, and the adhesion of the metal film is not always satisfactory in practice. I found that it was not a possible result.
  • the present invention provides a method for producing a laminate, which can easily form a laminate having a metal film that exhibits excellent adhesion to a substrate even when exposed to a high temperature environment. With the goal.
  • the present inventors have found that the above problems can be solved by using a polymerizable compound containing a P ⁇ O group. That is, the present inventors have found that the above object can be achieved by the following means.
  • a polymer layer forming step of forming a polymer layer; A catalyst application step of applying a plating catalyst or a precursor thereof to the polymer layer; Plating a plating catalyst or a precursor thereof and forming a metal film on a polymer layer, and a method for producing a laminate having a metal film comprising: The manufacturing method of the laminated body which has a metal film in which P O group containing polymeric compound is contained in the composition for base layer formation and / or the composition for polymer layer formation.
  • the manufacturing method of the laminated body as described in (1) whose P O group containing polymeric compound is a compound represented by General formula (1) mentioned later.
  • the reactive group is a methacryloyl group, acryloyl group, glycidyl group, amino group, styryl group, vinyl group, mercapto group, ureido group, sulfide group, isocyanate group, or carboxyl group, (1) or ( The manufacturing method of the laminated body as described in 2).
  • the present invention it is possible to provide a method for producing a laminate that can easily form a laminate having a metal film exhibiting excellent adhesion to a substrate even when exposed to a high temperature environment.
  • FIG. 1 A) to (E) are schematic cross-sectional views from a substrate to a laminate having a patterned metal film, which sequentially show the respective production steps in the laminate production method of the present invention.
  • FIG.D are schematic cross-sectional views sequentially showing a manufacturing process of a metal pattern material having a patterned metal film.
  • (A) to (E) are schematic cross-sectional views sequentially showing a manufacturing process of a metal pattern material having a patterned metal film.
  • FIG. to (C) are schematic cross-sectional views sequentially showing a manufacturing process of a metal pattern material having a patterned metal film.
  • FIG.) to (F) are schematic cross-sectional views sequentially showing steps for producing a metal pattern material having a patterned metal film.
  • the present invention is characterized in that a silane coupling agent-containing underlayer is used, and that a P ⁇ O group-containing polymerizable compound is used when forming a silane coupling agent-containing underlayer and / or a polymer layer.
  • Silane coupling agent A polymer layer forming composition containing a polymer having a polymerizable group and a functional group that interacts with a plating catalyst or its precursor is brought into contact with the containing underlayer, and then energy is applied to the polymer.
  • Catalyst applying step for applying a plating catalyst or its precursor to the polymer layer (4) Plating the plating catalyst or its precursor to form a metal film on the polymer layer The plating process to be performed In the following, the materials used in each process and the operation method thereof are described in detail.
  • step (1) Underlayer forming step>
  • a base layer forming composition containing a reactive group-containing silane coupling agent is brought into contact with the substrate to form a silane coupling agent-containing base layer (hereinafter also simply referred to as a base layer). It is a process to do.
  • a silane coupling agent-containing underlayer chemically bonded to the substrate surface can be formed via the hydrolyzable group of the silane coupling agent, and the layer functions as an underlayer of the polymer layer described later.
  • the underlayer can form a chemical bond with a polymer layer described later via a reactive group, and as a result, a metal film formed on the surface of the polymer layer and the substrate are formed.
  • the silane coupling agent-containing underlayer 12 is formed on the substrate 10 as shown in FIG.
  • materials a silane coupling agent, a P ⁇ O group-containing polymerizable compound, an underlayer-forming composition, a substrate, etc.
  • the silane coupling agent used in this step has a reactive group.
  • the reactive group preferably reacts with a polymer to be described later to form a covalent bond between the polymer layer and the underlayer.
  • the type of reactive group is not particularly limited as long as it reacts with the polymer described later. For example, methacryloyl group, acryloyl group, glycidyl group, amino group, carboxyl group, vinyl group, mercapto group, styryl group, ureido group, sulfide group And isocyanate groups.
  • methacryloyl group, acryloyl group, glycidyl group, amino group, styryl group, isocyanate group and the like are preferable because they have good reactivity with the polymer layer and better adhesion of the metal film.
  • Two or more reactive groups may be contained in the silane coupling agent.
  • a preferred embodiment of the silane coupling agent used in this step includes a compound represented by the following general formula (3).
  • Z a represents a reactive group.
  • the definition of the reactive group is as described above.
  • Each R independently represents a hydrogen atom or a hydrocarbon group.
  • the hydrocarbon group include aliphatic hydrocarbon groups (eg, alkyl groups, alkenyl groups, etc., preferably having 1 to 12 carbon atoms), or aromatic hydrocarbon groups (eg, phenyl groups, naphthyl groups, etc.). .
  • the hydrocarbon group is preferably a methyl group or an ethyl group. When there are a plurality of R, they may be the same or different.
  • W represents a hydrolyzable group.
  • an alkoxy group preferably an alkoxy group having 1 to 8 carbon atoms, such as a methoxy group or an ethoxy group
  • a halogen atom fluorine atom, chlorine atom, bromine atom, iodine atom
  • an acyloxy group acetoxy group
  • a methoxy group, an ethoxy group, and a chlorine atom are preferable in terms of good reactivity.
  • L c represents a single bond or a divalent organic group.
  • a divalent organic group a substituted or unsubstituted aliphatic hydrocarbon group (for example, an alkylene group, preferably 1 to 8 carbon atoms), a substituted or unsubstituted aromatic hydrocarbon group (for example, an arylene group, preferably).
  • M represents an integer of 0 to 2
  • n represents an integer of 1 to 3
  • satisfies the relationship of n + m 3.
  • m is preferably 0 to 1.
  • n is preferably 2 to 3.
  • silane coupling agent examples include ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, and ⁇ -glycidoxypropylmethyl.
  • the composition for forming an underlayer contains the silane coupling agent described above.
  • the content of the silane coupling agent in the underlayer-forming composition is not particularly limited, but the composition is easy to handle, easy to control the thickness of the underlayer, and the adhesion strength of the formed metal film.
  • the amount is preferably 0.1 to 100% by mass, more preferably 0.5 to 20% by mass based on the total amount.
  • the underlayer forming composition and / or the polymer layer forming composition to be described later include a P ⁇ O group-containing polymerizable compound.
  • the P ⁇ O group-containing polymerizable compound is a compound having a P ⁇ O group (phosphine oxide group) and a polymerizable group.
  • phosphine oxide group phosphine oxide group
  • a strong interaction is formed with the silane coupling agent via the P ⁇ O group, and the compound is uniformly in the silane coupling agent. scatter.
  • a strong covalent bond can be formed with the polymer layer mentioned later by having a polymeric group. As a result, a laminate including a metal film having excellent adhesion can be obtained.
  • the P ⁇ O group-containing polymerizable compound only needs to contain a P ⁇ O group and a polymerizable group.
  • the polymerizable group include a radical polymerizable group and a cationic polymerizable group. Of these, a radical polymerizable group is preferable from the viewpoint of reactivity.
  • the radical polymerizable group include a methacryloyl group, an acryloyl group, an itaconic acid ester group, a crotonic acid ester group, an isocrotonic acid ester group, a maleic acid ester group, a styryl group, a vinyl group, an acrylamide group, and a methacrylamide group. It is done.
  • a methacryloyl group, an acryloyl group, a vinyl group, a styryl group, an acrylamide group, and a methacrylamide group are preferable, and an acryloyl group, a methacryloyl group, and a styryl group are particularly preferable.
  • a preferred embodiment of the P ⁇ O group-containing polymerizable compound includes a compound represented by the following general formula (1).
  • X a represents a polymerizable group.
  • the definition of the polymerizable group is as described above.
  • L a represents a single bond or a divalent organic group. Definition of the organic group is the same as the organic group represented by the above-mentioned L c.
  • Y a represents a hydrogen atom or a substituent having no polymerizable group.
  • substituent not having a polymerizable group include an aliphatic hydrocarbon group (for example, an alkyl group), an aromatic hydrocarbon group (for example, an aryl group), or a group in which these are combined.
  • the substituent may contain a divalent organic group such as —O—, —CO—, —NH—, or a combination thereof.
  • the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 9 carbon atoms, and still more preferably 1 to 6 carbon atoms.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
  • the alkyl group may be linear, branched or cyclic, but is preferably a linear alkyl group.
  • the alkyl group may be substituted with an alkoxy group, an aryl group, an aryloxy group, or the like.
  • the aryl group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.
  • Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • the aryl group may be substituted with an alkyl group, an alkoxy group, an aryloxy group, or the like.
  • P represents an integer of 1 to 3
  • q represents an integer of 0 to 2
  • p is preferably 1 or 2
  • q is preferably 1 or 2.
  • a preferred embodiment of the compound represented by the general formula (1) includes a compound represented by the general formula (2).
  • Y ⁇ a> , p, and q is synonymous with each group in general formula (1).
  • Xb represents an acryloyl group or a methacryloyl group.
  • L b represents an alkylene group, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, or a combination thereof.
  • alkylene moiety of the alkylene group, alkyleneoxy group, alkyleneoxycarbonyl group, and alkylenecarbonyloxy group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.
  • the alkylene group may be linear or branched, but is preferably a linear alkylene group.
  • an alkylene group, an alkyleneoxy group, an alkyleneoxycarbonyl group, or an alkylenecarbonyloxy group in which the alkylene moiety has 2 or more carbon atoms is included in L b in terms of better adhesion of the metal film.
  • the number of carbon atoms is more preferably 3 to 12, and particularly preferably 5 to 8.
  • the compound prepared may be used.
  • the underlayer-forming composition is used in terms of the adhesion between the underlayer and the substrate and the adhesion between the underlayer and the polymer layer.
  • the mass ratio of the P ⁇ O group-containing polymerizable compound to the silane coupling agent in (P ⁇ O group-containing polymerizable compound / silane coupling agent) is preferably 1/1000 to 1/2, and 1/10 to 1 / 3 is more preferable.
  • the underlayer forming composition may contain a solvent, if necessary.
  • the solvent is not particularly limited as long as it can dissolve or disperse the silane coupling agent used.
  • water alcohol solvents (methanol, ethanol, propanol, etc.), ketone solvents (e.g.
  • acetone Methyl ethyl ketone, cyclohexanone, cyclopentanone, etc.
  • amide solvents eg, formamide, dimethylacetamide, N-methylpyrrolidone, etc.
  • nitrile solvents eg, acetonitrile, propionitrile, etc.
  • ester solvents eg, acetic acid, etc.
  • carbonate solvents eg, dimethyl carbonate, diethyl carbonate, etc.
  • ether solvents eg, ethylene glycol, glycerin, etc.
  • halogen solvents eg, chloroform, etc.
  • the content of the solvent in the composition for forming the underlayer is not particularly limited, but the silane coupling agent and P in the composition for forming the underlayer are from the viewpoints of handleability, control of the layer thickness of the underlayer, and stability. It is preferable to adjust the amount of the solvent so that the total concentration of the ⁇ O group-containing polymerizable compound is 0.1 to 50% by mass.
  • the underlayer-forming composition may contain other additives (for example, pH adjusters such as acids and bases (for example, acetic acid, phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, carbonic acid, oxalic acid, formic acid and the like).
  • pH adjusters such as acids and bases (for example, acetic acid, phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, carbonic acid, oxalic acid, formic acid and the like).
  • An acid, a base such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, and aqueous ammonia) may be contained.
  • any conventionally known substrate can be used, and one that can withstand the processing conditions described later is preferable.
  • a plastic substrate, a glass substrate, a ceramic substrate, a metal substrate, etc. are mentioned.
  • a glass substrate and a ceramic substrate are mentioned preferably at the point which is excellent in the reactivity with the said silane coupling agent.
  • the material for the plastic substrate include a thermosetting resin (eg, epoxy resin, phenol resin, polyimide resin, polyester resin, etc.) or a thermoplastic resin (eg, phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, etc.). It is done.
  • Examples of the material for the ceramic substrate include alumina, aluminum nitride, zirconia, silicon, silicon nitride, silicon carbide, and the like.
  • Examples of the glass substrate material include soda glass, potash glass, borosilicate glass, quartz glass, aluminum silicate glass, and lead glass.
  • Examples of the material for the metal substrate include aluminum, zinc, and copper.
  • 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 substrate may have metal wiring on one side or both sides thereof.
  • the metal wiring may be formed in a pattern with respect to the surface of the substrate or may be formed on the entire surface. Typically, those formed by a subtractive method using an etching process and those formed by a semi-additive method using electroplating may be used, and those formed by any method may be used. Examples of the material constituting the metal wiring include copper, silver, tin, palladium, gold, nickel, chromium, tungsten, indium, zinc, and gallium.
  • the method for bringing the substrate into contact with the underlayer-forming composition containing the reactive group-containing silane coupling agent is not particularly limited.
  • the method for immersing the substrate in the underlayer-forming composition or the underlayer-forming composition And a method of applying an object on a substrate. From the viewpoint of easily controlling the thickness of the resulting underlayer, a method of applying the composition onto the substrate is preferable.
  • the coating method is not particularly limited, and specific methods include a double roll coater, slit coater, air knife coater, wire bar coater, slide hopper, spray coating, blade coater, doctor coater, squeeze coater, reverse roll coater, transfer.
  • Known methods such as a roll coater, an extrusion coater, a curtain coater, a dip coater, a die coater, a gravure roll coating method, an extrusion coating method, and a roll coating method can be used.
  • the amount applied to the substrate is converted to the amount of the silane coupling agent in terms of the adhesion between the underlayer and the polymer layer and the adhesion of the metal film to be formed.
  • 0.001 to 0.1 g / m 2 is preferable, and 0.0015 to 0.05 g / m 2 is more preferable.
  • the substrate After bringing the composition for forming an underlayer into contact with the substrate, the substrate may be heat-treated as necessary to remove the solvent.
  • the heating conditions an optimal temperature is appropriately selected depending on the solvent contained in the composition.
  • the heating temperature is preferably 30 to 200 ° C., and the heating time is preferably 1 minute to 1 hour.
  • the substrate it is preferable to wash the substrate using a solvent after the composition for forming an underlayer is brought into contact with the substrate (or after the above heat treatment).
  • a solvent By washing with a solvent, the unreacted silane coupling agent deposited on the substrate can be removed, and the adhesion of the resulting metal film is further improved.
  • the solvent to be used is appropriately selected according to the type of the silane coupling agent, and examples thereof include a solvent that may be contained in the underlayer forming composition. Of these, water, alcohol solvents, and ketone solvents are preferred, and isopropyl alcohol, methanol, ethanol, cyclopentanone, and cyclohexanone are often used.
  • drying conditions are not particularly limited, but it is preferable to dry at a temperature of 20 to 100 ° C. for a time of 1 minute to 1 hour.
  • silane coupling agent-containing underlayer The silane coupling agent-containing underlayer formed by the above procedure is mainly formed of the above-described silane coupling agent and serves as an underlayer for the polymer layer described later.
  • the thickness of the underlayer is not particularly limited, but is preferably about a few molecules from a monomolecular film of the silane coupling agent used.
  • the contact angle of the underlayer with respect to water can be controlled by the silane coupling agent used. By performing a silane coupling treatment using the composition for forming the underlayer and observing that the value of the contact angle on the substrate surface changes, it can be determined whether or not the underlayer has been formed on the substrate surface.
  • the preferred contact angle on the substrate surface varies depending on the combination of the constituent component of the underlayer and the polymer component constituting the polymer layer.
  • the contact angle refers to a static contact angle, and was measured at 27 ° C. using a contact angle measuring device by a droplet method.
  • the “static contact angle” refers to a contact angle under a condition in which a state change with time due to flow or the like does not occur.
  • the underlayer preferably contains the silane coupling agent as a main component.
  • the main component means that the content of the silane coupling agent is 50% by mass or more, and preferably 70% by mass or more, based on the total amount of the underlayer. The maximum value is 100% by mass.
  • Step (2) is a polymer layer forming composition comprising a polymer having a polymerizable group and a functional group that interacts with a plating catalyst or a precursor thereof on the underlayer obtained in step (1).
  • the polymerizable group in the active compound is activated to form crosslinks between the polymers and covalent bonds between the underlayer and the polymer layer.
  • a polymer layer 14a is formed on the silane coupling agent-containing underlayer 12.
  • the polymer used in the present invention has a polymerizable group and a functional group that interacts with the plating catalyst or its precursor (hereinafter referred to as an interactive group as appropriate).
  • an interactive group as appropriate.
  • the polymerizable group is a functional group that can form a chemical bond between polymers or between a polymer and an underlayer by applying energy.
  • the interacting group is a functional group that interacts with the plating catalyst or its precursor (coordinating group, metal ion adsorbing group), and a functional group that can form an electrostatic interaction with the plating catalyst or its precursor.
  • a nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group or the like that can form a coordination with the plating catalyst or its precursor can be used.
  • interactive groups include non-dissociable functional groups (functional groups that do not generate protons by dissociation).
  • Nitrogen-containing functional groups such as nitro group, nitroso group, azo group, diazo group, azido group, cyano group, cyanate group (R—O—CN); ether group, hydroxyl group, phenolic hydroxyl group, carboxyl group, Carbonate group, carbonyl group, ester group, group containing N-oxide structure, S Oxy
  • a salt thereof can also be used.
  • an ionic polar group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a boronic acid group, an ether group, or A cyano group is particularly preferable, and a carboxyl group or a cyano group is more preferable.
  • Two or more of these functional groups as interactive groups may be contained in the polymer.
  • equation (X) is preferable.
  • L 4 represents an alkylene group
  • R c represents an alkyl group.
  • n represents a number from 1 to 30. * Represents a bonding position.
  • the alkylene group preferably has 1 to 3 carbon atoms, and specific examples include an ethylene group and a propylene group.
  • the alkyl group preferably has 1 to 10 carbon atoms, and specific examples include a methyl group and an ethyl group.
  • n represents a number of 1 to 30, preferably 3 to 23.
  • n represents an average value, and the numerical value can be measured by a known method (NMR) or the like.
  • the weight average molecular weight of the polymer 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. Further, the degree of polymerization of the polymer is not particularly limited, but it is preferable to use a polymer of 10-mer or more, and more preferably a polymer of 20-mer or more. Moreover, 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.
  • a unit having a polymerizable group represented by the following formula (a) (hereinafter also referred to as a polymerizable group unit as appropriate) and an interaction property represented by the following formula (b) Examples thereof include a copolymer containing a unit having a group (hereinafter also referred to as an interactive group unit as appropriate).
  • a unit means a repeating unit.
  • R 1 to R 5 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • R 1 to R 5 are substituted or unsubstituted alkyl groups
  • examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • examples of the substituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group substituted with a methoxy group, a chlorine atom, a bromine atom, or a fluorine atom.
  • R 1 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a bromine atom.
  • R 2 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a bromine atom.
  • R 3 is preferably a hydrogen atom.
  • R 4 is preferably a hydrogen atom.
  • R 5 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a bromine atom.
  • X, Y, and Z each independently represent a single bond or a substituted or unsubstituted divalent organic group.
  • divalent organic group a substituted or unsubstituted aliphatic hydrocarbon group (for example, an alkylene group, preferably 1 to 8 carbon atoms), a substituted or unsubstituted aromatic hydrocarbon group (for example, an arylene group, preferably).
  • 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.
  • X, Y, and Z are preferably a single bond, an ester group (—COO—), an amide group (—CONH—), an ether group (—O—), or a substituted or unsubstituted aromatic hydrocarbon group. More preferred are a single bond, an ester group (—COO—), and an amide group (—CONH—).
  • L 1 and L 2 each independently represent a single bond or a substituted or unsubstituted divalent organic group.
  • a divalent organic group it is synonymous with the divalent organic group described by X, Y, and Z mentioned above.
  • L 1 is preferably an aliphatic hydrocarbon group or a divalent organic group having a urethane bond or urea bond (for example, an aliphatic hydrocarbon group), more preferably a divalent organic group having a urethane bond, Among them, those having 1 to 9 carbon atoms are preferable.
  • the total number of carbon atoms of L 1 means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L 1. More specifically, the structure of L 1 is preferably a structure represented by the following formula (1-1) or formula (1-2).
  • R a and R b each independently represent two or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom. It is a divalent organic group formed by using. Preferably, it is a substituted or unsubstituted methylene group, ethylene group, propylene group, or butylene group, or ethylene oxide group, diethylene oxide group, triethylene oxide group, tetraethylene oxide group, dipropylene oxide group, tripropylene oxide group, tetra A propylene oxide group is mentioned.
  • L 2 is preferably a single bond, a linear, branched, or cyclic alkylene group, an aromatic group, or a group obtained by combining these.
  • the group obtained by combining the alkylene group and the aromatic group may further be via an ether group, an ester group, an amide group, a urethane group, or a urea group.
  • L 2 preferably has a single bond or a total carbon number of 1 to 15, and is particularly preferably unsubstituted.
  • the total number of carbon atoms of L 2 means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L 2.
  • a methylene group an ethylene group, a propylene group, a butylene group, a phenylene group, and those groups substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom, etc., The group which combined these is mentioned.
  • W represents a functional group that interacts with the plating catalyst or its precursor.
  • the definition of the functional group is as described above.
  • a preferred embodiment of the polymerizable group unit represented by the above formula (a) includes a unit represented by the following formula (c).
  • R 1 , R 2 , Z and L 1 are the same as the definitions of each group in the unit represented by the formula (a).
  • A represents an oxygen atom or NR (R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms).
  • a preferred embodiment of the unit represented by the formula (c) is a unit represented by the formula (d).
  • R 1 , R 2 , and L 1 are the same as the definitions of each group in the unit represented by the formula (a).
  • a and T each represents an oxygen atom or NR (R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms).
  • T is preferably an oxygen atom.
  • L 1 is preferably an unsubstituted alkylene group or a divalent organic group having a urethane bond or a urea bond, and a divalent organic group having a urethane bond.
  • those having 1 to 9 carbon atoms are particularly preferable.
  • R 5 and L 2 are the same as the definition of each group in the unit represented by the formula (b).
  • Q represents an oxygen atom or NR ′ (R ′ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms).
  • L 2 in the formula (e) is preferably a linear, branched, or cyclic alkylene group, an aromatic group, or a group obtained by combining these.
  • the linking site with the interactive group in L 2 is a divalent organic group having a linear, branched, or cyclic alkylene group.
  • the valent organic group preferably has 1 to 10 carbon atoms.
  • the connecting portion between the interactive group in L 2 in Formula (e) is preferably a divalent organic group having an aromatic group, among others, of the divalent
  • the organic group preferably has a total carbon number of 6 to 15.
  • the polymerizable group unit is preferably contained in an amount of 5 to 50 mol%, more preferably 5 to 40 mol%, based on all units in the polymer. If it is less than 5 mol%, the reactivity (curability, polymerizability) may be lowered, and if it exceeds 50 mol%, gelation tends to occur during synthesis and synthesis is difficult. Further, from the viewpoint of adsorptivity to the plating catalyst or its precursor, the interactive group unit is preferably contained in an amount of 5 to 95 mol%, more preferably 10 to 95, based on all units in the polymer. Mol%.
  • the unit represented by the formula (A) is the same as the unit represented by the formula (a), and the description of each group is also the same.
  • R 5, X and L 2 in the unit represented by formula (B) is the same as R 5, X and L 2 in the unit represented by the above formula (b), same explanation of each group It is.
  • Wa in the formula (B) represents a functional group that interacts with the plating catalyst or its precursor, excluding the hydrophilic group represented by V described later or its precursor group.
  • each R 6 independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • the definition of the alkyl group is the same as the alkyl group represented by R 1 to R 5 described above.
  • U represents a single bond or a substituted or unsubstituted divalent organic group.
  • the definition of a bivalent organic group is synonymous with the divalent organic group represented by X, Y, and Z mentioned above.
  • L 3 represents a single bond or a substituted or unsubstituted divalent organic group.
  • the definition of a divalent organic group is synonymous with the divalent organic group represented by L 1 and L 2 described above.
  • V represents a hydrophilic group or a precursor group thereof.
  • the hydrophilic group is not particularly limited as long as it is a hydrophilic group, and examples thereof include a hydroxyl group and a carboxylic acid group.
  • the precursor group of the hydrophilic group means a group that generates a hydrophilic group by a predetermined treatment (for example, treatment with acid or alkali). For example, carboxy protected with THP (2-tetrahydropyranyl group) Group and the like.
  • the hydrophilic group is preferably an ionic polar group in that the polymer layer is easily wetted with various aqueous treatment liquids and plating solutions, and the effects of the present invention are more manifested.
  • the ionic polar group examples include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a boronic acid group.
  • a carboxylic acid group is preferable from the viewpoint of moderate acidity (does not decompose other functional groups).
  • the unit represented by the formula (C) is moderately acidic (does not decompose other functional groups), shows hydrophilicity in an aqueous alkali solution, and tends to show hydrophobicity due to the cyclic structure when water is dried.
  • V is a carboxylic acid group
  • the L 3 linking portion to V has a 4- to 8-membered ring structure.
  • examples of the 4- to 8-membered ring structure include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a phenyl group, and among them, a cyclohexyl group and a phenyl group are preferable.
  • the unit represented by the formula (C) is moderately acidic (does not decompose other functional groups), hydrophilic in an alkaline aqueous solution, and hydrophobic due to the long-chain alkyl group structure when water is dried.
  • V is a carboxylic acid group, and it is also preferable chain length of L 3 is 6 to 18 atoms.
  • the chain length of L 3 represents the distance between U and V in the formula (C), and it is preferable that the distance between U and V is preferably in the range of 6 to 18 atoms. To do.
  • the chain length of L 3 is more preferably 6 to 14 atoms, still more preferably 6 to 12 atoms.
  • each unit in the second preferred embodiment of the polymer is as follows.
  • the unit represented by the formula (A) is contained in an amount of 5 to 50 mol% with respect to all units in the polymer from the viewpoint of reactivity (curability and polymerizability) and suppression of gelation during synthesis. It is preferably 5 to 30 mol%.
  • the unit represented by the formula (B) is preferably contained in an amount of 5 to 75 mol%, more preferably 10 to 70 mol%.
  • the unit represented by the formula (C) is preferably contained in an amount of 10 to 70 mol%, more preferably 20 to 60 mol%, based on the total unit in the polymer, from the viewpoint of developability with an aqueous solution and moisture-resistant adhesion.
  • the mol% is particularly preferably 30 to 50 mol%.
  • the ionic polarity (in the case where the ionic polar group is a carboxylic acid group) in the second preferred embodiment of the polymer is preferably 1.5 to 7.0 mmol / g, and preferably 1.7 to 5. 0 mmol / g is more preferable, and 1.9 to 4.0 mmol / g is particularly preferable.
  • the ionic polarity value is within this range, it is possible to achieve both the development of the aqueous solution and the suppression of the decrease in the adhesion strength with time of wet heat.
  • polymers described in paragraphs [0106] to [0112] of JP-A-2009-007540 can be used as a polymer having a radical polymerizable group and an interactive group.
  • polymers described in paragraphs [0065] to [0070] of JP-A-2006-135271 can be used.
  • polymers described in paragraphs [0030] to [0108] of US2010-080964 can be used.
  • the following polymers are also mentioned.
  • the method for synthesizing the polymer is not particularly limited, and the monomer used may be a commercially available product or one synthesized by combining known synthesis methods.
  • the above polymer can be synthesized with reference to the methods described in paragraphs [0120] to [0164] of Japanese Patent Publication No. 2009-7662. More specifically, when the polymerizable group is a radical polymerizable group, the following method is preferably exemplified as a polymer synthesis method.
  • a monomer having a radical polymerizable group a method of copolymerizing a monomer having an interactive group
  • a monomer having an interactive group and a monomer having a radical polymerizable group precursor are copolymerized and then a base
  • a method of introducing a radical polymerizable group by a treatment such as iii) a method of introducing a radical polymerizable group by copolymerizing a monomer having an interactive group and a monomer having a reactive group for introducing a radical polymerizable group Is mentioned. From the viewpoint of synthesis suitability, preferred methods are the methods ii) and iii).
  • the kind of polymerization reaction at the time of synthesis is not particularly limited, and it is preferably performed by radical polymerization.
  • a copolymer containing the units represented by the above formula (A), formula (B), and formula (C) a monomer having a hydrophilic group or a precursor group thereof, a hydrophilic group
  • a desired copolymer can be synthesized by the above methods i) to iii) using a monomer having an interactive group excluding its precursor group.
  • the polymer layer forming composition contains the polymer.
  • the content of the polymer in the composition for forming a polymer layer is not particularly limited, but is preferably 2 to 50% by mass and 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 polymer layer.
  • the composition for forming a polymer layer preferably contains a solvent.
  • the solvent which can be used is not specifically limited, For example, the solvent etc. which are used with the composition for base layer formation are mentioned. Of these, water, amide solvents, ketone solvents, nitrile solvents, carbonate solvents, alcohol solvents are preferred. Specifically, water, acetone, dimethylacetamide, methyl ethyl ketone, cyclohexanone, acetonitrile, propionitrile, N -Methylpyrrolidone, dimethyl carbonate, 1-methoxy-2-propanol and the like are preferable.
  • the content of the solvent in the polymer layer forming composition is not particularly limited, but is preferably 50 to 95% by mass, more preferably 70 to 90% 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 polymer layer.
  • the composition for forming a polymer layer may contain a silane coupling agent having the above-described reactive group, if necessary.
  • a silane coupling agent having the above-described reactive group, if necessary.
  • the kind of silane coupling agent used is as described above, and the preferred embodiment is also the same.
  • the silane coupling agent When the silane coupling agent is contained in the composition for forming a polymer layer, the polymer layer is improved in terms of handleability, better adhesion of the polymer layer to the base layer, and better adhesion of the metal film.
  • the mass ratio of the silane coupling agent to the polymer (silane coupling agent / polymer) in the forming composition is preferably 1/1000 to 1/5, more preferably 1/100 to 1/10.
  • the P O group-containing polymerizable compound
  • the P O group-containing polymerizable compound is contained in the underlayer forming composition and / or the polymer layer forming composition described below.
  • the compound is contained in the composition for forming a polymer layer, a strong interaction is formed with the underlayer via the P ⁇ O group. Further, it forms a strong covalent bond with the polymer via a polymerizable group, and plays a role of improving the adhesion between the underlayer and the polymer layer.
  • the mass ratio of the P ⁇ O group-containing polymerizable compound to the polymer in the composition is preferably 1/1000 to 1/5, and preferably 1/100 to 1/10. More preferred.
  • the method of bringing the polymer layer forming composition into contact with the underlayer is not particularly limited, and there are a method of immersing a substrate in the polymer layer forming composition, a method of applying the polymer layer forming composition on the underlayer, and the like. Can be mentioned. From the viewpoint of easily controlling the thickness of the resulting polymer layer, a method of applying the composition on a substrate is preferred. As a coating method, the coating method described in the above step (1) can be used.
  • the coating amount is 0.1 to 10 g / m in terms of solid content from the viewpoint of sufficient interaction formation with a plating catalyst or a precursor thereof described later. 2 is preferable, and 0.5 to 5 g / m 2 is particularly preferable.
  • radiation irradiation such as heating or exposure
  • light irradiation with a UV lamp, visible light, or the like, heating with a hot plate, or the like is possible.
  • the light source for exposure include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp, and an LED 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.
  • a general heat heat roller, laminator, hot stamp, electric heating plate, thermal head, laser, blower dryer, oven, hot plate, infrared dryer, heating drum, or the like can be used.
  • the time required for energy application varies depending on the light source, but is usually between 10 seconds and 5 hours. Moreover, you may provide combining these energy provision methods. For example, exposure and heating may be combined.
  • the exposure power is in the range of 10 to 8000 mJ / cm 2 in order to facilitate the graft polymerization and to suppress the decomposition of the produced graft polymer.
  • the range is preferably 100 to 3000 mJ / cm 2 .
  • irradiation with an inert gas such as nitrogen, helium, or carbon dioxide may be performed, and irradiation may be performed in an atmosphere in which the oxygen concentration is suppressed to 600 ppm or less, preferably 400 ppm or less.
  • energy may be applied in a pattern as necessary.
  • the unreacted polymer may be appropriately removed from the composition after the energy application.
  • the removal method include a method using a solvent.
  • a solvent that dissolves a polymer or an alkali-soluble polymer an alkaline developer (sodium carbonate, sodium bicarbonate, aqueous ammonia, aqueous sodium hydroxide) Etc. can be removed.
  • the thickness of the resulting polymer layer is not particularly limited, but is preferably from 0.01 to 10 ⁇ m, more preferably from 0.05 to 5 ⁇ m, from the viewpoint of 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 polymer layer is preferably from 0.01 to 0.3 ⁇ m, more preferably from 0.02 to 0.15 ⁇ m, from the viewpoint of the wiring shape and 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.
  • the polymer content in the polymer layer is preferably 2% by mass to 100% by mass, more preferably 10% by mass to 100% by mass with respect to the total amount of the polymer layer.
  • Step (3) is a step of applying a plating catalyst or a precursor thereof to the polymer layer obtained in step (2).
  • the interactive group in the polymer layer adheres (adsorbs) the applied plating catalyst or its precursor depending on its function. More specifically, as shown in FIG. 1C, a polymer layer 14b to which a plating catalyst or a precursor thereof is applied is formed.
  • a plating catalyst or its precursor what functions as a catalyst or electrode of a plating process in the process (4) mentioned later is mentioned. Therefore, although a plating catalyst or its precursor is determined by the kind of plating process in a process (4), 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 imparted to the polymer layer 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.
  • those capable of multidentate coordination are preferable, and Ag ions, Pd ions, and Cu ions are particularly preferable in terms of the number of types of functional groups capable of coordination and catalytic ability.
  • a palladium compound can be mentioned.
  • 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.
  • 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.
  • a zero-valent metal can be used as a catalyst used for direct electroplating without performing electroless plating on the polymer layer.
  • the zero-valent metal include Pd, Ag, Cu, Ni, Pt, Au, and Co.
  • those capable of multidentate coordination are preferable, and in particular, adsorptive (adhesive) property to an interactive group, Pd, Ag, and Cu are preferable because of their high catalytic ability.
  • the plating catalyst or a precursor thereof as described above is preferably applied to the polymer layer as a dispersion or solution (plating catalyst solution).
  • Water or an organic solvent is used as a solvent for the plating catalyst solution.
  • 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.
  • the organic solvent used in the plating catalyst solution is not particularly limited as long as it is a solvent that can penetrate the polymer layer.
  • a water-soluble organic solvent is preferable from the viewpoint of compatibility with a plating catalyst or a precursor thereof and permeability to a polymer layer.
  • 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 polymer layer is not particularly limited.
  • a dispersion in which a metal is dispersed in an appropriate dispersion medium or a solution containing a dissociated metal ion by dissolving a metal salt in an appropriate solvent is prepared, and the dispersion or solution (plating catalyst solution) is used as a polymer layer.
  • the method include a method of applying on the substrate, a method of immersing a substrate on which a polymer layer is formed in a dispersion or solution thereof, and the like.
  • the contact time between the polymer layer and the plating catalyst solution is preferably about 30 seconds to 24 hours, and more preferably about 1 minute to 1 hour.
  • the temperature of the plating catalyst solution at the time of contact is preferably about 5 to 80 ° C., more preferably about 15 to 60 ° C.
  • the interaction group in the polymer layer can interact with an intermolecular force such as van der Waals force or electrostatic interaction such as ionic bond.
  • the plating catalyst or its precursor can be adsorbed by utilizing the interaction due to the coordinate bond by the lone pair of electrons.
  • the metal concentration or metal ion concentration in the plating catalyst solution is preferably in the range of 0.001 to 50% by mass, and 0.005 to 30% by mass. A range is more preferable.
  • Step (4) is a step of forming a metal film on the polymer layer by plating the polymer layer to which the plating catalyst or its precursor has been applied in step (3).
  • the metal film formed by this process has excellent conductivity and adhesion. More specifically, as shown in FIG. 1D, a metal film 16 is formed on the polymer layer 14b, and a laminate 18 is obtained. Examples of the plating treatment performed in this step include electroless plating, electroplating, and the like, and in the above step (3), depending on the function of the plating catalyst or its precursor that forms an interaction with the polymer layer, You can choose.
  • electroless plating is preferably performed from the viewpoint of improving the formability and adhesion of the hybrid structure expressed in the polymer layer. Moreover, in order to obtain the metal film 16 having a desired film thickness, it is a more preferable aspect that electroplating is further performed after the electroless plating. Hereinafter, 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.
  • the electroless plating bath used a known electroless plating bath can be used.
  • the substrate to which the electroless plating catalyst precursor has been applied is immersed in an electroless plating bath in a state where the electroless plating catalyst precursor is adsorbed or impregnated on the polymer layer, the substrate is washed with excess precursor.
  • electroless plating bath After removing the body (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.
  • 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.
  • the concentration of the electroless plating catalyst or its precursor in the vicinity of the surface of the polymer layer with which the electroless plating catalyst or its precursor comes in contact may be immersed while stirring or shaking. preferable.
  • 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 copper, tin, lead, nickel, gold, silver, palladium, and rhodium are known, and copper and gold are particularly preferable from the viewpoint of conductivity.
  • 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 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.
  • the metal film obtained by electroless plating obtained as described above has a high-density dispersion of fine particles of a plating catalyst and a plating metal in the polymer layer by cross-sectional observation using a scanning electron microscope (SEM). Further, it is confirmed that the plating metal is deposited on the polymer layer. Since the interface between the polymer layer and the metal film is a hybrid state of the resin composite and the fine particles, the adhesion is good even if the interface between the polymer layer and the metal film is smooth.
  • SEM scanning electron microscope
  • the plating catalyst or its precursor applied in the step (3) has a function as an electrode
  • electroplating is performed on the polymer layer to which the catalyst or its precursor is applied. be able to.
  • the formed metal film may be used as an electrode, and electroplating may be further 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.
  • the electroplating method a conventionally known method can be used.
  • a metal used for electroplating copper, chromium, lead, nickel, gold
  • the film thickness of the metal film obtained by electroplating 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 electroplating is not limited to the above and can be arbitrarily set.
  • the substrate 10, the silane coupling agent-containing underlayer 12, the polymer layer 14b, and the metal film 16 are in this order.
  • the laminated body 18 (laminated body with a metal film) provided with can be obtained.
  • the obtained laminate 18 is used, for example, for a metal wiring board, and more specifically, a printed wiring board, an electromagnetic wave prevention film, a coating film, a two-layer CCL (Copper Clad Laminate) material, an electric wiring material, and the like. It can be applied to various electronic device applications.
  • Heating process> You may heat-process with respect to the laminated body which has a metal film as needed after the said plating process (heating process). By performing the heat treatment after the plating treatment, the adhesion of the metal film (plating film) formed in the plating step may be further improved.
  • the heating process may be performed after the electroless plating process, and the heating process may be performed after the electroplating process.
  • the heating conditions in the heating step vary depending on the polymer and metal film material used, but the heating temperature is preferably 80 to 200 ° C., more preferably 100 to 140 ° C., in order to further improve the adhesion of the metal film.
  • the heating time is preferably 5 minutes to 2 hours, more preferably 30 minutes to 1 hour from the viewpoint of improving productivity and adhesion. Note that in this heating step, heat treatment under different conditions may be continuously performed twice or more.
  • a metal pattern material laminated body
  • a pattern forming step of etching the metal film 16 on the surface of the above laminated body 18 into a pattern
  • This step is a step of forming a patterned metal film by etching the metal film into a pattern in the plating step. More specifically, as shown in FIG. 1 (E), in this step, the patterned metal film 20 is formed on the polymer layer 14b by removing unnecessary portions of the metal film 16. Any method can be used to form this pattern. Specifically, a generally known subtractive method (a patterned mask is provided on a metal film and an unformed region of the mask is etched). After that, the mask is removed and a patterned metal film is formed), a semi-additive method (a patterned mask is provided on the metal film, and a plating process is performed so as to form a metal film in a non-mask formation region). And a method of forming a patterned metal film by removing the mask and performing an etching process).
  • a generally known subtractive method a patterned mask is provided on a metal film and an unformed region of the mask is etched. After that, the mask is removed and a patterned metal film is
  • FIG. 2 shows an embodiment of a pattern forming process using the subtractive method.
  • a laminate including the substrate 10, the silane coupling agent-containing underlayer 12, the polymer layer 14b, and the metal film 16 shown in FIG. 2A by performing the plating step of the above step (4). 18 is prepared.
  • the metal film 16 is provided on one side of the substrate 10, but it may be provided on both sides.
  • a patterned mask 22 is provided on the metal film 16.
  • the metal film 16 in the region where the mask 22 is not provided is removed by an etching process (for example, dry etching or wet etching) to obtain a patterned metal film 20.
  • the mask 22 is removed, and the metal pattern material 24 is obtained.
  • a known resist material can be used for manufacturing the mask 22.
  • a mask having the same pattern as the patterned metal film can be formed by providing a resist layer on the metal film and performing pattern exposure and development. Any material can be used as the resist material, and negative, positive, liquid, and film-like materials can be used.
  • the etching method any known method can be used, and wet etching, dry etching, or the like can be used, and any etching method may be selected. In terms of operation, wet etching is preferable from the viewpoint of simplicity of the apparatus.
  • an etching solution for example, an aqueous solution of cupric chloride, ferric chloride, or the like can be used.
  • FIG. 3 shows an embodiment of a pattern forming process using the semi-additive method.
  • substrate 10, the silane coupling agent containing base layer 12, the polymer layer 14b, and the metal film 16 which are shown to FIG. 3 (A) is prepared.
  • a patterned mask 22 is provided on the metal film 16.
  • a plating process for example, electroplating
  • FIG. 3C a metal film is formed in an area where the mask 22 is not provided, and a metal film 16b having a convex part and a concave part is formed. obtain.
  • FIG. 3 shows an embodiment of a pattern forming process using the semi-additive method.
  • the mask 22 is removed, and the metal film (particularly, the recesses) is removed by an etching process (for example, dry etching or wet etching), as shown in FIG.
  • a metal pattern material 24 including the patterned metal film 20 is obtained.
  • the resist, the etching solution, etc. can use the same material as the subtractive method.
  • the above-mentioned method can be used as the electroplating method.
  • the silane coupling agent-containing underlayer 12 and the polymer layer 14b may be removed together by a known means (for example, dry etching, plasma ashing).
  • the obtained metal pattern material can be used in various fields, for example, electricity / electronic / communication, agriculture, forestry and fisheries, mining, construction, food, textile, clothing, medical, coal, petroleum, rubber, leather, automobile It can be used in a wide range of industrial fields such as precision equipment, wood, building materials, civil engineering, furniture, printing and musical instruments. More specifically, printers, personal computers, word processors, keyboards, PDAs (small information terminals), telephones, copiers, facsimiles, ECRs (electronic cash registers), calculators, electronic notebooks, cards, holders, stationery, etc.
  • AV equipment such as liquid crystal displays, connectors, relays, capacitors, switches, printed boards, coil bobbins, semiconductor sealing materials, LED sealing materials, electric wires, cables, transformers, deflection yokes, distribution boards, semiconductor chips, wiring boards
  • an insulating resin layer (interlayer insulating film) may be further laminated on the surface of the metal pattern material, and further wiring (metal pattern) may be formed on the surface.
  • a solder resist may be formed on the surface of the metal pattern material.
  • Part 2 ⁇ Production Method of Metal Pattern Material (Part 2)> As another embodiment of the method for producing a metal pattern material having a patterned metal film on the surface, there is a method using a patterned polymer layer.
  • step (2) energy is applied (for example, exposure) in a pattern, and then development processing is performed, whereby the substrate 10 is exposed.
  • a silane coupling agent-containing underlayer 12 and a patterned polymer layer 14c are formed.
  • a predetermined mask may be used as necessary.
  • the method of a development process is not specifically limited, The method of using well-known developing solution (For example, sodium hydrogen carbonate solution, alkaline aqueous solution (for example, sodium hydroxide aqueous solution)) etc. are mentioned. Thereafter, as shown in FIG.
  • the catalyst application step described in the above step (3) is performed on the polymer layer 14c, and the patterned polymer layer 14d provided with the plating catalyst or its precursor is applied. Get.
  • the patterned metal film 20 is formed on the polymer layer 14d.
  • the silane coupling agent-containing underlayer 12 is formed on the substrate 10 through the above-described step (1).
  • energy is imparted (for example, exposure) to the silane coupling agent-containing base layer 12 in a pattern.
  • FIG. 5B there is a method in which a mask 30 having a predetermined pattern is provided on the silane coupling agent-containing underlayer 12, and exposure processing is performed through the mask 30.
  • FIG. 5C the polymer layer 14a is formed on the silane coupling agent-containing underlayer 12 through the above-described step (2).
  • the polymer layer 14a is developed, as shown in FIG. 4D, a pattern is formed only in the unexposed areas that are not exposed by the mask 30 of the silane coupling agent-containing underlayer 12.
  • a polymer layer 14c is obtained.
  • the polymerizable group of the P ⁇ O group-containing polymerizable compound in the silane coupling agent-containing underlayer 12 reacts and disappears, or the reactive group in the silane coupling agent-containing underlayer 12 ( For example, since the radical polymerizable group) is deactivated, no chemical bond is generated between the silane coupling agent-containing base layer 12 and the polymer layer 14a even if the step (2) is performed.
  • the resistance to the development treatment differs between the polymer layer on the exposed region of the silane coupling agent-containing underlayer 12 and the polymer layer on the unexposed region, and in the unexposed region of the silane coupling agent-containing underlayer 12
  • the polymer layer 14c can be selectively formed.
  • the method of a development process is not specifically limited, The method of using well-known developing solution (For example, sodium hydrogen carbonate solution, alkaline aqueous solution (for example, sodium hydroxide aqueous solution)) etc. are mentioned.
  • the catalyst application step described in the above step (3) is performed on the polymer layer 14c, and the patterned polymer layer 14d provided with the plating catalyst or its precursor is applied. Get.
  • the patterned metal film 20 is formed on the polymer layer 14d as shown in FIG. 5 (F).
  • 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.
  • 47.4 g of raw material A, 22 g of pyridine, and 150 mL of ethyl acetate were placed in a 500 mL three-necked flask and cooled in an ice bath.
  • 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.
  • N containing 14.3 g of monomer M, 3.0 g of acrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), 6.5 g of acrylic acid (manufactured by Tokyo Chemical Industry), 0.4 g of V-65 (manufactured by Wako Pure Chemical Industries, Ltd.)
  • N-dimethylacetamide 8 g solution was added dropwise over 4 hours. After completion of the dropwise addition, the reaction solution was further stirred for 3 hours.
  • 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 3 0.9 mmol / g.
  • the obtained polymer A 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, which is a cyano 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
  • Ditertiary butyl hydroquinone 0.29 g, dibutyltin dilaurate 0.29 g, Karenz AOI (manufactured by Showa Denko KK) 18.56 g, and N-methylpyrrolidone 19 g are added to the above reaction solution, and the reaction is carried out at 55 ° C. for 6 hours. Went. Thereafter, 3.6 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was carried out with water, the solid was taken out, and 25 g of polymer B was obtained.
  • Example 1 [Preparation of silane coupling agent-containing underlayer] Including 3- (acryloxy) propyltrimethoxysilane (KBM-5103) and KAYAMER PM-21 (Nippon Kayaku Co., Ltd.) on a glass substrate (Corning Eagle 2000 (50 mm ⁇ 50 mm ⁇ 0.7 mm))
  • the formation composition X1 was applied by spin coating and dried at 110 ° C. for 5 minutes. Thereafter, the substrate was washed with isopropyl alcohol, further washed with water, and air-dried to obtain a silane coupling agent-containing underlayer.
  • the mass ratio of 3- (acryloxy) propyltrimethoxysilane to KAYAMER PM-21 was 1: 0.25.
  • the underlayer-forming composition X1 contained cyclopentanone as a solvent, and its content was 94% by mass with respect to the total amount of the composition.
  • the surface water contact angle of the glass substrate and the surface water contact angle of the glass substrate after the treatment were measured to be 3 ° and 25 °, respectively, and the silane coupling agent-containing underlayer was formed on the glass substrate by the treatment. It was confirmed that was formed.
  • a polymer layer forming composition Y1 containing polymer A and 3- (acryloxy) propyltrimethoxysilane was applied onto a substrate having a silane coupling agent-containing underlayer by a spin coating method, and then at 80 ° C. for 5 minutes. Dried. Thereafter, UV exposure (exposure amount: 12000 mJ / cm 2 ) was performed on the entire surface of the substrate at 254 nm, and the substrate was washed with 1% sodium bicarbonate water. As a result, a polymer layer (thickness: 1 ⁇ m) directly bonded to the silane coupling agent-containing underlayer on the substrate was obtained.
  • Electroless plating uses an electroless plating bath with the following composition using sulcup PGT (manufactured by Uemura Kogyo Co., Ltd.). The polymer layer is immersed at a bath temperature of 30 ° C. so that the plating deposition thickness is 0.5 ⁇ m. (Metal film) was formed.
  • the preparation order and raw materials of the electroless plating solution are as follows. Approximately 60% by volume of distilled water PGT-A 9.0% by volume PGT-B 6.0% by volume PGT-C 3.5% by volume Formalin solution * 2.3% by volume Finally, the liquid level was adjusted with distilled water so that the total amount would be 100% by volume. * The formalin used here is a Wako Pure Chemical formaldehyde solution (special grade).
  • the obtained substrate was subjected to a heat treatment at 100 ° C. for 30 minutes, and further subjected to a heat treatment at 140 ° C. for 30 minutes.
  • the metal film surface was degreased using a 1% by mass sulfuric acid aqueous solution.
  • electrolytic copper plating (3 A / dm 2 : 30 minutes) is performed using an electrolytic copper plating bath having the following composition so that the copper thickness becomes 12 ⁇ m.
  • a laminate having a film was obtained.
  • Composition of electrolytic copper plating bath Water 1000 parts by weight-Copper sulfate pentahydrate 110 parts by weight-298 parts by weight of 98% sulfuric acid-0.2 parts by weight of 35% hydrochloric acid-Made by Meltex, 30 parts by weight of Capper Gream ST-901M
  • the obtained substrate was subjected to heat treatment at 100 ° C. for 30 minutes.
  • Example 2 The composition for forming the underlayer X2 having the following composition was used in place of the composition for forming the underlayer X1, and the composition for forming the polymer layer Y2 having the following composition was used in place of the composition for forming the polymer layer Y1.
  • Example 2 The composition for forming the underlayer X2 having the following composition was used in place of the composition for forming the underlayer X1, and the composition for forming the polymer layer Y2 having the following composition was used in place of the composition for forming the polymer layer Y1.
  • Example 3 A laminate was obtained according to the same procedure as in Example 1 except that the polymer layer forming composition Y2 was used instead of the polymer layer forming composition Y1.
  • Example 4 Example 3 and Example 3 except that 3- (acryloxy) propyltrimethoxysilane used in the underlayer forming composition X1 and the polymer layer forming composition Y2 was changed to 3-trimethoxysilylpropyl methacrylate. A laminate was obtained according to the same procedure.
  • Example 5 A laminate was obtained according to the same procedure as Example 1 except that the polymer layer forming composition Y3 having the following composition was used instead of the polymer layer forming composition Y1.
  • Example 6 The same procedure as in Example 3 except that KAYAMER PM-21 used in the underlayer-forming composition X1 and the polymer layer-forming composition Y2 was changed to KAYAMER PM-2 (manufactured by Nippon Kayaku Co., Ltd.). Thus, a laminate was obtained.
  • Example 7 A laminate was obtained according to the same procedure as in Example 1, except that the polymer layer forming composition Y4 having the following composition was used instead of the polymer layer forming composition Y1.
  • Example 8 Except for changing the 3- (acryloxy) propyltrimethoxysilane used in the underlayer-forming composition X1 and the polymer layer-forming composition Y2 to 3-glycididoxypropyltrimethoxysilane (LS2940), A laminate was obtained according to the same procedure as in Example 3.
  • the “Si agent” column represents the presence or absence of a silane coupling agent in each composition. When it is contained, it is represented as “ ⁇ ”, and when it is not contained, it is represented as “x”.
  • the “P ⁇ O agent” column indicates the presence or absence of a P ⁇ O group-containing polymerizable compound in each composition. The case where it is contained is represented as “ ⁇ ”, and the case where it is not contained is represented as “x”. To do. “-” In Table 1 means not implemented.
  • Example 3 and 8 it was confirmed that Furthermore, it was confirmed from the comparison with Example 3 and 8 that the more excellent effect will be acquired when the silane coupling agent which has acryloyl group which is a radically polymerizable group as a reactive group is used. On the other hand, in Comparative Examples 1 and 2 in which neither the composition for forming an underlayer nor the composition for forming a polymer layer contains a P ⁇ O group-containing polymerizable compound, a laminate exhibiting a predetermined effect was not obtained. .
  • a dry resist film (manufactured by Hitachi Chemical Co., Ltd .; RY3315, film thickness: 15 ⁇ m) is vacuum laminator (manufactured by Meiki Seisakusho: MVLP-600) on the metal film surface of the laminate obtained in Example 1 above.
  • MVLP-600 vacuum laminator
  • a glass mask capable of forming a comb-type wiring (compliant with JPCA-BU01-2007) defined in JPCA-ET01 is closely attached to the substrate laminated with the dry resist film, and light of 70 mJ is applied to the resist with an exposure device having a central wavelength of 405 nm. Irradiated with energy.
  • Development was performed by spraying a 1% Na 2 CO 3 aqueous solution onto the exposed substrate at a spray pressure of 0.2 MPa. Thereafter, the substrate was washed with water and dried to form a subtractive resist pattern on the copper plating film. Etching was performed by immersing the substrate on which the resist pattern was formed in an FeCl 3 / HCl aqueous solution (etching solution) at a temperature of 40 ° C. to remove the copper plating film present in the region where the resist pattern was not formed.
  • etching solution FeCl 3 / HCl aqueous solution
  • the resist pattern is swollen and peeled off by spraying a 3% NaOH aqueous solution onto the substrate at a spray pressure of 0.2 MPa, neutralized with a 10% sulfuric acid aqueous solution, and washed with water to form a comb-like wiring (pattern shape). Copper plating film) was obtained.
  • the polymer layer and the base layer between the wirings were removed by plasma ashing.
  • a solder resist (PFR800; manufactured by Taiyo Ink Manufacturing Co., Ltd.) is vacuum laminated on the obtained comb-shaped wiring under the conditions of 70 ° C. and 0.2 MPa, and light energy of 420 mJ is applied with an exposure machine having a central wavelength of 365 nm. Irradiated.
  • the substrate was heat-treated at 80 ° C. for 10 minutes, and then a 1% aqueous solution of Na 2 CO 3 was sprayed onto the substrate surface at a spray pressure of 0.2 MPa, developed, washed with water 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 comb-shaped wiring (wiring substrate) covered with a solder resist.
  • Example 1 [Preparation of Silane Coupling Agent-Containing Underlayer] was carried out to obtain a glass substrate having a silane coupling agent-containing underlayer.
  • the polymer layer forming composition Y1 was applied onto a substrate provided with a silane coupling agent-containing underlayer by a spin coating method and dried at 80 ° C. for 5 minutes. Thereafter, UV exposure (exposure amount: 12000 mJ / cm 2 ) is performed on the entire surface of the substrate at 254 nm in a pattern through a glass mask capable of forming a comb-shaped wiring (JPCA-BU01-2007 compliant) defined in JPCA-ET01. Washed with aqueous sodium bicarbonate. As a result, a patterned polymer layer (thickness: 1 ⁇ m) directly bonded to the silane coupling agent-containing underlayer on the substrate was obtained.
  • Example 1 [Catalyst application] and [Plating treatment and heat treatment] of Example 1 were performed to obtain a laminate including a patterned metal film.
  • Example 1 [Preparation of Silane Coupling Agent-Containing Underlayer] was carried out to obtain a glass substrate having a silane coupling agent-containing underlayer.
  • UV exposure (exposure amount: 12000 mJ / cm 2 ) at 254 nm on the entire surface of the underlayer containing the silane coupling agent is formed in a glass mask pattern capable of forming a comb wiring (JPCA-BU01-2007 compliant) defined in JPCA-ET01. went.
  • [Formation of polymer layer] in Example 1 was performed, and the silane coupling agent-containing underlayer was directly bonded only to the unexposed areas of the silane coupling agent-containing underlayer that had not been subjected to the patterned UV exposure.
  • a patterned polymer layer (thickness: 1 ⁇ m) was obtained.
  • [Catalyst application] and [Plating treatment and heat treatment] of Example 1 were performed to obtain a laminate including a patterned metal film.
  • Example 13> A laminated body was obtained according to the same procedure as in Example 1 except that a sapphire substrate (Kyocera Corporation, SEMI standard) was used instead of the glass substrate used in Example 1.
  • a sapphire substrate Korean Chemical Company, SEMI standard
  • the same results as in Example 1 were obtained.
  • the same results as in Example 1 were obtained when an alumina substrate (manufactured by Kyocera Corporation, thin film substrate) or silicon wafer (Opttostar, 4-inch standard single crystal) was used instead of the sapphire substrate. It was.
  • Substrate 12 Silane coupling agent-containing base layers 14a, 14b, 14c, 14d: Polymer layers 16, 16b: Copper-containing plating film 18: Laminate 20: Patterned metal film 22, 30: Mask 24: Metal pattern material

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

Abstract

La présente invention se rapporte à un procédé de production d'un stratifié, grâce auquel on peut facilement former un stratifié comportant un film métallique qui présente une excellente adhérence à un substrat même s'il est exposé à des environnements à température élevée. Ce procédé de production d'un stratifié comportant un film métallique comprend : une étape de formation de couche de base dans laquelle une couche de base contenant un agent de couplage au silane est formée par la mise en contact d'une composition pour formation de couche de base avec un substrat ; une étape de formation de couche polymère dans laquelle une couche polymère est formée par la mise en contact d'un groupe polymérisable et d'une composition pour formation de couche polymère avec la couche de base contenant un agent de couplage au silane puis par l'application d'énergie à ceux-ci ; une étape de transmission de catalyseur dans laquelle un catalyseur de placage ou un précurseur de celui-ci est transmis à la couche polymère ; et une étape de placage dans laquelle un film métallique est formé sur la couche polymère par la réalisation d'un placage par rapport au catalyseur de placage ou à un précurseur de celui-ci. A ce sujet, la composition pour formation de couche de base et/ou la composition pour formation de couche polymère contient un composé polymérisable contenant un groupe P=O.
PCT/JP2011/077164 2010-12-02 2011-11-25 Procédé de production de stratifié comportant un film métallique WO2012073814A1 (fr)

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CN110753458A (zh) * 2018-07-23 2020-02-04 精工爱普生株式会社 配线基板及配线基板的制造方法
TWI735731B (zh) * 2017-01-17 2021-08-11 日商太陽油墨製造股份有限公司 感光性薄膜層合體及使用其所形成之硬化物

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JP6281762B2 (ja) * 2013-12-10 2018-02-21 住友電工プリントサーキット株式会社 プリント配線板
KR20200010362A (ko) * 2017-05-19 2020-01-30 베지 사사키 전자 부품 탑재용 기판 및 그 제조 방법

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JP2009035809A (ja) * 2007-07-06 2009-02-19 Fujifilm Corp 表面金属膜材料、その作製方法、金属パターン材料、その作製方法、ポリマー層形成用組成物、及び新規ポリマー

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CN110753458B (zh) * 2018-07-23 2022-09-16 精工爱普生株式会社 配线基板及配线基板的制造方法

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