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WO2013065628A1 - Procédé de fabrication d'un stratifié ayant une couche métallique - Google Patents

Procédé de fabrication d'un stratifié ayant une couche métallique Download PDF

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Publication number
WO2013065628A1
WO2013065628A1 PCT/JP2012/077854 JP2012077854W WO2013065628A1 WO 2013065628 A1 WO2013065628 A1 WO 2013065628A1 JP 2012077854 W JP2012077854 W JP 2012077854W WO 2013065628 A1 WO2013065628 A1 WO 2013065628A1
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Prior art keywords
group
layer
plated
composition
forming
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English (en)
Japanese (ja)
Inventor
貴胤 河野
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Fujifilm Corp
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Fujifilm Corp
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    • 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
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first

Definitions

  • the present invention relates to a method for producing a laminate having a metal layer.
  • 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 layer formed on the surface of the substrate, the photosensitive layer is exposed imagewise, and then developed to form a resist image.
  • the metal layer 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.
  • a graft polymer directly bonded to the substrate is formed on a substrate having an adhesion auxiliary layer (underlying layer) to form a layer to be plated (polymer layer).
  • a method of obtaining a laminate having a metal layer by plating is known (for example, Patent Document 1). According to this method, the adhesion between the substrate and the metal layer can be improved without roughening the substrate surface.
  • an object of the present invention is to provide a method for producing a laminate having a metal layer exhibiting excellent adhesion to a substrate even when exposed to a high temperature environment.
  • composition layer then applying energy to the composition layer to form a layer to be plated,
  • the underlayer forming composition and / or the plated layer forming composition contains a P ⁇ O group-containing polymerizable compound,
  • the manufacturing method of the laminated body which has a metal layer whose Young's modulus of the said to-be-plated layer is 1200 Mpa or less.
  • composition for forming a layer to be plated further contains a sulfonic acid group-containing monomer.
  • a P O group-containing polymerizable compound;
  • the underlayer is a layer containing a silane coupling agent bonded onto the substrate via a hydrolyzable group;
  • the Young's modulus of the layer to be plated is 1200 MPa or less,
  • FIG. 1 A) to (E) are schematic cross-sectional views from a substrate to a laminated body having a patterned metal layer, which sequentially show the respective production steps in the laminated body production method of the present invention.
  • the first feature of the present invention is that a reactive silane coupling agent and a P ⁇ O group-containing polymerizable compound are used. Specifically, a silane coupling agent having a reactive group is blended with the underlayer-forming composition and the plated layer-forming composition, and the underlayer-forming composition and / or the plated layer-forming. It is a point which mix
  • blends a P O group containing polymeric compound with a composition.
  • the second feature of the present invention is that a layer to be plated having a Young's modulus belonging to a specific range is used.
  • the manufacturing method of the laminated body of this invention is equipped with the following four processes.
  • Plating step of plating the layer to be plated to which the plating catalyst or its precursor is applied to form a metal layer on the layer to be plated
  • the Young's modulus of the layer to be plated is 1200 MPa or less.
  • Step (1) is a step of forming a base layer on the substrate using a base layer forming composition containing a silane coupling agent having a reactive group.
  • a base layer chemically bonded to the substrate surface can be formed via the hydrolyzable group of the silane coupling agent, and the layer functions as a base layer of a layer to be plated which will be described later.
  • this base layer can form a chemical bond through a reactive group even with a layer to be plated, which will be described later.
  • the metal layer formed on the surface of the layer to be plated and the substrate Excellent adhesion is exhibited between them.
  • the base layer 12 is formed on the substrate 10 as shown in FIG. First, materials (a silane coupling agent, a P ⁇ O group-containing polymerizable compound, an underlayer-forming composition, a substrate, etc.) used in this step will be described in detail, and then the procedure of the step will be described in detail.
  • the silane coupling agent used in this step has a reactive group.
  • the reactive group preferably reacts with a polymer described later to form a covalent bond between the layer to be plated 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.
  • a methacryloyl group, an acryloyl group, a glycidyl group, an amino group, a styryl group, an isocyanate group and the like are preferable because they have good reactivity with the layer to be plated and better adhesion of the metal layer.
  • 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 is a compound represented by the 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 P 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 composition for forming the underlayer is not particularly limited, but the composition is excellent in terms of handleability, ease of controlling the layer thickness of the underlayer, and adhesion strength of the generated metal layer.
  • the amount is preferably 0.1 to 100% by mass, more preferably 0.5 to 20% by mass based on the total amount of the product.
  • the underlayer-forming composition and / or the later-described plated layer-forming composition contains 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.
  • 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.
  • substituents that does not have 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.
  • the number of carbon atoms in the alkylene moiety is 2 or more, alkylene group, an alkyleneoxy group, an alkyleneoxy group or alkylene carbonyloxy group, it is contained in L b
  • the number of carbon atoms is more preferably 3 to 12, and particularly preferably 5 to 8.
  • the compound prepared may be used.
  • the adhesion between the underlayer and the substrate and the adhesion between the underlayer and the layer to be plated are more excellent.
  • the mass ratio of the P ⁇ O group-containing polymerizable compound and the silane coupling agent in the composition is preferably 1/1000 to 1/2. 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 a substrate 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 preferable at the point which the reactivity with the said silane coupling agent is excellent, and a glass substrate is more preferable.
  • 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.).
  • 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.
  • substrate may have metal wiring in the single side
  • 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.
  • a method for forming an underlayer using a composition for forming an underlayer containing a silane coupling agent having a reactive group on the substrate is not particularly limited, and a method of immersing the substrate in the composition for forming an underlayer And a method of applying an underlayer-forming composition 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 silane because the adhesion between the underlayer and the layer to be plated and the adhesion of the metal layer to be formed are further improved.
  • amount of coupling agent 0.001 to 0.1 g / m 2 is preferable, and 0.0015 to 0.05 g / m 2 is more preferable.
  • 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, but from the viewpoint of better productivity, 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 layer 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.
  • the underlayer formed by the above procedure is mainly formed of the above-described silane coupling agent, and plays a role as an underlayer for a later-described plated layer.
  • 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 components of the underlayer and the polymer component constituting the layer to be plated.
  • the contact angle is 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) Plated layer forming step>
  • a polymer having a polymerizable group, a functional group that interacts with a plating catalyst or a precursor thereof, and a silane having a reactive group are formed on the underlayer obtained in the step (1).
  • a composition layer is formed using a composition for forming a layer to be plated containing a coupling agent, and then the energy is applied to the composition layer to form a layer to be plated.
  • the reactive group of the silane coupling agent, the polymerizable group in the polymer, and the P ⁇ O group are contained.
  • the polymerizable group in the polymerizable compound is activated, and a cross-link between polymers and a covalent bond between the underlayer and the layer to be plated are formed. As a result, the layer to be plated and the base layer are more firmly adhered. More specifically, as shown in FIG. 1B, a layer to be plated 14 a is formed on the base layer 12.
  • the polymer used in this step has a polymerizable group and an interactive group.
  • the polymerizable group is a functional group capable of forming a chemical bond between polymers or between the polymer and the underlayer by applying energy, and examples thereof include a radical polymerizable group and a cationic polymerizable group.
  • a radical polymerizable group is preferable from the viewpoint of reactivity.
  • examples of radical polymerizable groups include acrylic acid ester groups (acryloyloxy groups), methacrylic acid ester groups (methacryloyloxy groups), itaconic acid ester groups, crotonic acid ester groups, isocrotonic acid ester groups, maleic acid ester groups, and the like.
  • Examples include unsaturated carboxylic acid ester groups, styryl groups, vinyl groups, acrylamide groups, and methacrylamide groups.
  • a methacryloyloxy group, an acryloyloxy group, a vinyl group, a styryl group, an acrylamide group, and a methacrylamide group are preferable, and a methacryloyloxy group, an acryloyloxy group, and a styryl group are particularly preferable.
  • An interactive group is a functional group that interacts with a plating catalyst or a precursor thereof, a functional group that can form an electrostatic interaction with the plating catalyst or a precursor thereof, or a coordination group with a plating catalyst or a precursor thereof.
  • Nitrogen-containing functional groups, sulfur-containing functional groups, oxygen-containing functional groups and the like that can be formed can be used.
  • Examples of interactive groups include non-dissociable functional groups (functional groups that do not generate protons by dissociation).
  • an interactive group amino group, amide group, imide group, urea group, tertiary amino group, ammonium group, amidino group, triazine ring, triazole ring, benzotriazole group, imidazole group, benzimidazole Group, quinoline group, pyridine group, pyrimidine group, pyrazine group, solooline group, quinoxaline group, purine group, triazine group, piperidine group, piperazine group, pyrrolidine group, pyrazole group, aniline group, group containing alkylamine structure, isocyanuric structure
  • Nitrogen-containing functional groups such as nitro group, nitroso group, azo group, diazo group, azide 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 An oxygen-containing functional
  • 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.
  • the weight average molecular weight of the polymer is not particularly limited, but is preferably 1000 or more and 700,000 or less, more preferably 2000 or more and 200,000 or less. In particular, from the viewpoint of polymerization sensitivity, it is preferably 20000 or more.
  • the degree of polymerization of the polymer is not particularly limited, but is preferably a 10-mer or more, and more preferably a 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).
  • the unit means a repeating unit.
  • R 1 to R 5 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc. ).
  • the substituent is not particularly limited, and examples thereof include 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.
  • the divalent organic group include a substituted or unsubstituted divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, for example, an alkylene group such as a methylene group, an ethylene group, and a propylene group), a substituted or unsubstituted group.
  • a divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms, such as a phenylene group), —O—, —S—, —SO 2 —, —N (R) — (R: alkyl group), And —CO—, —NH—, —COO—, —CONH—, or a combination thereof (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, and the like).
  • a single bond, an ester group (—COO—), an amide group (—) can be used because the polymer can be easily synthesized and the functions of the layer to be plated are excellent (catalyst adsorption, hydrolysis resistance).
  • CONH— an ether group (—O—), a substituted or unsubstituted divalent aromatic hydrocarbon group, and the like are preferable, and a single bond, an ester group (—COO—), 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 a divalent organic compound having an aliphatic hydrocarbon group, a urethane bond, or a urea bond in that the polymer is easily synthesized and the functions of the plated layer (catalyst adsorption, hydrolysis resistance) are excellent.
  • a group for example, an aliphatic hydrocarbon group
  • a group having a total carbon number of 1 to 9 is particularly 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.
  • L 2 is easy to synthesize a polymer and has excellent functions (catalyst adsorbability, hydrolysis resistance) of the layer to be plated.
  • a single bond, a divalent aliphatic hydrocarbon group, or a divalent aroma is used. It is preferably a group hydrocarbon group or a combination thereof.
  • L 2 is preferably a single bond or an aliphatic hydrocarbon group having 1 to 15 carbon atoms in total, and 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.
  • W represents a functional group that interacts with the plating catalyst or its precursor.
  • the definition of the functional group is the same as the definition of the interactive group described above.
  • 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 above formula (a), and the explanation 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 a plating catalyst or a precursor thereof excluding a hydrophilic group represented by V described later or a precursor group thereof. Of these, a cyano group and an ether group are preferable.
  • each R 6 independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • 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.
  • U is a single bond, an ester group (—COO—), an amide group (—CONH—), an ether in terms of easy polymer synthesis and excellent functions (catalytic adsorption, hydrolysis resistance) of the layer to be plated.
  • the group (—O—) or a substituted or unsubstituted divalent aromatic hydrocarbon group is preferred.
  • L 3 represents a single bond or a substituted or unsubstituted divalent organic group. Defining divalent organic group has the same meaning as divalent organic group represented by L 1 and L 2 as described above.
  • L 3 is a single bond, a divalent aliphatic hydrocarbon group or a divalent aromatic in that the polymer is easily synthesized and the functions of the layer to be plated (catalyst adsorption, hydrolysis resistance) are excellent. It is preferably a hydrocarbon group or a group obtained by combining these.
  • 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, a carboxyl group protected with THP (2-tetrahydropyranyl group). Groups and the like.
  • the hydrophilic group is preferably an ionic polar group because the layer to be plated is easily wetted with various aqueous treatment solutions and plating solutions.
  • 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).
  • 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 5%, based on the total unit in the polymer, from the viewpoint of adsorptivity to the plating catalyst or its precursor. 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 polymer can be produced by known methods (eg, the methods in the literature listed above).
  • composition for plating layer formation contains the polymer.
  • the content of the polymer in the composition for forming a layer to be plated is not particularly limited, but is preferably 1 to 50% by mass and more preferably 3 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 includes the silane coupling agent described above.
  • the silane coupling agent By including the silane coupling agent, the adhesion between the base layer and the layer to be plated is further improved, and the film physical properties of the layer to be plated can be easily controlled.
  • the kind of silane coupling agent used is as described above, and the preferred embodiment is also the same.
  • the content of the silane coupling agent in the composition for forming a layer to be plated is not particularly limited, but the handling property, the adhesion of the layer to be plated with the underlayer is more excellent, and the adhesion of the metal layer is more excellent.
  • the mass ratio of the silane coupling agent to the polymer (silane coupling agent / polymer) in the composition for forming a plating layer is preferably 1/1000 to 1/5, and 1/100 to 1/10. Is more preferable.
  • the P O group-containing polymerizable compound
  • the P O group-containing polymerizable compound is contained in the underlayer forming composition and / or the later-described plated layer forming composition.
  • the compound is contained in the composition for forming a layer to be plated, a strong interaction is formed with the base layer via the P ⁇ O group. Furthermore, 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 layer to be plated.
  • the composition for forming a layer to be plated is because the adhesion of the layer to be plated to the underlayer and the adhesion to the metal layer are more excellent.
  • the content of the P ⁇ O group-containing polymerizable compound in the content is preferably less than 30.0% by mass, and more than 0.1% by mass and less than 30.0% by mass with respect to the content of the polymer. It is more preferable that the content is 0.5% by mass or more and 10.0% by mass or less.
  • the composition for forming a layer to be plated of the present invention preferably contains a photopolymerization initiator.
  • a bond between the polymer and the base layer is further formed, and as a result, a metal layer having better adhesion can be obtained.
  • photopolymerization initiators include benzophenones, acetophenones, ⁇ -aminoalkylphenones, benzoins, ketones, thioxanthones, benzyls, benzyl ketals, oxime esters, anthrones, tetramethylthiuram mono Mention may be made of sulfides, bisacylphosphinoxides, acylphosphine oxides, anthraquinones, azo compounds and their derivatives. Details of these are described in “UV Curing System” (1989, General Technology Center), pages 63 to 147.
  • a cationic polymerization initiator can also be mentioned as a polymerization initiator for ring-opening polymerization.
  • the cationic polymerization initiator include aromatic onium salts, sulfonium salts of Group VIa elements of the periodic table, and derivatives thereof.
  • the composition for forming a layer to be plated 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 composition for forming a plating layer is not particularly limited, but 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.
  • the method for forming the composition layer on the underlayer using the composition for forming a layer to be plated is not particularly limited, and a known method can be used.
  • coating the to-be-plated layer forming composition on a base layer, etc. are mentioned.
  • a method of applying the composition on the substrate is preferable.
  • the coating method described in the above step (1) can be used.
  • the coating amount is 0.1 to 10 g in terms of solid content from the viewpoint of sufficient interaction formation with a plating catalyst or a precursor thereof described later.
  • / M 2 is preferable, and 0.5 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 coating and drying.
  • heat treatment or exposure treatment is preferably used, and exposure treatment is preferred because the treatment is completed in a short time.
  • exposure treatment 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.
  • Specific examples of preferred embodiments include scanning exposure with an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure.
  • 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 10,000 mJ, and is preferably in the range of 100 to 8000 mJ.
  • an air dryer, oven, an infrared dryer, a heating drum, etc. can be used. You may provide combining these energy provision methods. For example, exposure and heating may be combined.
  • 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 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 adhesion of the metal layer 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 Young's modulus of the plated layer of the present invention is 1200 MPa or less. Since the layer to be plated of the present invention has a Young's modulus belonging to such a specific range, even if the layer to be plated is thermally contracted by being exposed to a severe high temperature environment (specifically, 200 ° C. or more). The generation of stress between the metal layer is suppressed, and as a result, the adhesion between the substrate and the metal layer is maintained.
  • the Young's modulus of the plated layer of the present invention is preferably 10 MPa or more from the viewpoint of the strength of the plated layer, and the adhesion between the substrate and the metal layer is maintained even when exposed to higher temperature conditions.
  • the Young's modulus of the layer to be plated is measured based on JIS K 7127: 1999 by producing a model film having only the layer to be plated.
  • the composition for forming the layer to be plated is cast on a Teflon petri dish, and the solvent is removed by drying, followed by UV exposure (wavelength: 254 nm, exposure amount: 6000 mJ / cm 2 ). Can be produced.
  • the method for adjusting the Young's modulus of the layer to be plated to the specific Young's modulus is not particularly limited.
  • the method of changing the crosslink density in the layer to be plated the method of containing a plasticizer in the layer to be plated, examples thereof include a method of containing an elastomer such as natural rubber and synthetic rubber in the layer, a method of containing a filler in the layer to be plated, and the like.
  • the method of making a to-be-plated layer forming composition contain a plasticizer, an elastomer, and a filler is mentioned.
  • Examples of the method for changing the crosslink density in the layer to be plated include, for example, a method for reducing the content of the polymerizable group in the polymer described above, and a monomer (preferably a monofunctional monomer) in the composition for forming the layer to be plated. ) And the like.
  • a method of adding a plasticizer to the composition for forming a layer to be plated hereinafter referred to as Method A
  • Method B a monomer in the composition for forming a layer to be plated Is preferable
  • the plasticizer is a compound that enhances the flexibility of the layer to be plated, and is preferably compatible with the polymer and the silane coupling agent in the composition for forming the layer to be plated.
  • the plasticizer include aliphatic dibasic acid esters, phosphate esters, trimellitic acid esters, glycol esters, epoxidized esters, citrate esters, and silicone compounds.
  • a silicone compound is preferable and an amine-modified silicone compound is more preferable because it can be easily adjusted to an appropriate Young's modulus and has higher compatibility.
  • a preferred embodiment of the amine-modified silicone compound is, for example, a compound represented by the general formula (6).
  • R 21 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.). . Of these, the hydrocarbon group is preferably a methyl group or an ethyl group.
  • R 21 may be the same or different.
  • X and Y represent a hydrogen atom, a hydrocarbon group (examples and preferred embodiments of the hydrocarbon group are the same as those for R 21 above) or an amino group, At least one is an amino group.
  • the content of the plasticizer in the composition for forming a plated layer is appropriately adjusted so that the obtained plated layer is in the Young's modulus range.
  • the amount of the plasticizer used in the composition for forming a layer to be plated is preferably 1 to 60 parts by mass with respect to 100 parts by mass of the polymer in terms of more excellent adhesion of the metal layer. Part by mass is more preferable.
  • the procedure for forming the layer to be plated is the same as that described above.
  • the monomer added to adjust the layer to be plated is not particularly limited as long as it reacts with the polymerizable group of the polymer, but it can be easily adjusted to an appropriate Young's modulus, and has higher compatibility. From the viewpoint, it is preferably a sulfonic acid group-containing monomer having a polymerizable group and a sulfonic acid group, and more preferably monofunctional.
  • the kind and suitable aspect of a polymeric group are the same as the polymeric group of the said polymer.
  • a preferred embodiment of the sulfonic acid group-containing monomer is a compound represented by the following general formula (4).
  • R 10 represents a hydrogen atom, a metal cation, or a quaternary ammonium cation.
  • metal cations include alkali metal cations (sodium ions, calcium ions), copper ions, palladium ions, silver ions, and the like.
  • a metal cation a monovalent or bivalent thing is mainly used, and when divalent thing (for example, palladium ion) is used, n mentioned later represents 2.
  • the quaternary ammonium cation include tetramethylammonium ion and tetrabutylammonium ion.
  • L 10 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.
  • R 11 to R 13 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • 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 11 is preferably a hydrogen atom or a methyl group.
  • R 12 is preferably a hydrogen atom.
  • R 13 is preferably a hydrogen atom.
  • N represents an integer of 1 or 2. Especially, it is preferable that n is 1 from a viewpoint of the availability of a compound.
  • L 11 represents an ester group (—COO—), an amide group (—CONH—), or a phenylene group.
  • L 12 represents a single bond, a divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, more preferably 3 to 5 carbon atoms), or a divalent aromatic hydrocarbon group.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic.
  • the molecular weight of the compound represented by the general formula (4) is not particularly limited, but is preferably from 100 to 1,000, and preferably from 100 to 300, from the viewpoints of volatility, solubility in a solvent, film formability, and handling properties. More preferred.
  • the content of the monomer in the composition for forming a plated layer is appropriately adjusted so that the obtained plated layer is in the range of the Young's modulus.
  • the amount of the monomer used in the composition for forming a layer to be plated is preferably 1 to 60 parts by mass, preferably 5 to 20 parts by mass with respect to 100 parts by mass of the polymer, in that the adhesion of the metal layer is more excellent. Part is more preferred.
  • the procedure for forming the layer to be plated is the same as that described above.
  • the thermal contraction rate of the layer to be plated is preferably 0.100 or less, and is preferably 0.050 or less because the adhesion between the substrate and the metal layer is maintained even when exposed to a higher temperature environment. More preferably, it is more preferably 0.035 or less.
  • the thermal contraction rate of the layer to be plated was measured as follows.
  • the thermal contraction rate of the layer to be plated can be in the specific range by setting the composition for forming a layer to be plated in the above-described preferred mode.
  • the product of X and Y is 50.0 or less. It is preferable that it is 30.0 or less.
  • the laminate When a laminate is manufactured using a layer to be plated such that the product of X and Y is in the above range, the laminate is generated between the metal layer and the substrate even when exposed to a high temperature environment. Since the stress is suppressed to a lower level, it exhibits better adhesion between the metal layer and the substrate. Specifically, even when exposed to a high temperature environment of 200 ° C. for 1 h, it exhibits an adhesion force of 0.2 kN or more.
  • the Young's modulus and thermal shrinkage rate of the layer to be plated are determined by the same method as described above. Moreover, the adhesive force was calculated
  • the metal layer was spaced by 5 mm, a 130 mm cut was made in parallel, and the end was cut by a cutter and raised by 10 mm.
  • a tensile tester RTM-100, manufactured by A & D Co., Ltd.
  • the peeled metal layer was gripped and the 90 ° peel strength was measured (tensile speed: 10 mm / min).
  • the product of X and Y can belong to the specific range by setting the composition for forming a plated layer to the above-described preferred mode.
  • the product of the Young's modulus X and the heat shrinkage Y simply represents the magnitude of the stress generated during heat shrinkage. If the value is small, the stress generated when the layer to be plated is subjected to heat treatment tends to be small, and as a result, there is a correlation with better adhesion of the metal layer.
  • Step (3) is a step of applying a plating catalyst or a precursor thereof to the layer to be plated obtained in step (2).
  • the interactive group in the layer to be plated adheres (adsorbs) the applied plating catalyst or its precursor depending on its function. More specifically, as shown in FIG. 1C, a layer to be plated 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.
  • 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 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.
  • 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.
  • Zero-valent metals other than those described above can also be used as a catalyst used for direct electroplating without electroless plating.
  • the plating catalyst or a precursor thereof is preferably used in the form of a dispersion or solution in which these are dispersed or dissolved in a solvent (hereinafter also referred to as a plating catalyst solution as appropriate).
  • a solvent hereinafter also referred to as a plating catalyst solution as appropriate.
  • an organic solvent and / or water is used as the solvent used in the plating catalyst solution.
  • the plating catalyst solution contains an organic solvent, the permeability of the plating catalyst solution to the layer to be plated is improved, and the plating catalyst or its precursor can be efficiently adsorbed to the interactive group.
  • the organic solvent used for the plating catalyst solution is not particularly limited as long as it is a solvent that can penetrate into the layer to be plated. Specifically, 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 and the like can be used.
  • 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.
  • the above plating catalyst solution (dispersion in which metal is dispersed in an appropriate dispersion medium or solution containing metal ions dissolved in an appropriate solvent and dissociated metal ions), and applied onto the layer to be plated And 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 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 layer to be plated 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 action or the interaction by 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 layer on the layer to be plated by plating the layer to be plated to which the plating catalyst or its precursor has been applied in step (3).
  • the metal layer formed by this process has excellent conductivity and adhesion. More specifically, as shown in FIG. 1D, the metal layer 16 is formed on the layer to be plated 14b, and the laminate 18 is obtained. Examples of the plating treatment performed in this step include electroless plating and electroplating.
  • the step (3) depending on the function of the plating catalyst or its precursor that has formed an interaction with the layer to be plated. Can be selected.
  • electroless plating is preferably performed from the viewpoint of improving the formability and adhesion of the hybrid structure that appears in the layer to be plated. Moreover, in order to obtain the metal layer 16 having a desired film thickness, it is a more preferable aspect that electroplating is further performed after 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 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 process 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 water-soluble solvent, 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 layer 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 layer 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.
  • electroplating is applied to the layer to be plated to which the catalyst or its precursor is applied. It can be carried out.
  • the formed metal layer may be used as an electrode, and electroplating may be further performed. Accordingly, a new metal layer having an arbitrary thickness can be easily formed on the electroless plating film having excellent adhesion to the substrate.
  • the metal layer can be formed to a thickness according to the purpose, which is suitable for applying the metal layer 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 layer obtained by electroplating can be controlled by adjusting the metal concentration contained in the plating bath or the current density.
  • the thickness of the metal layer is preferably 0.5 ⁇ m or more, more preferably 1 to 30 ⁇ m from the viewpoint of conductivity.
  • the thickness of the electrical wiring becomes thinner in order to maintain the aspect ratio as the line width of the electrical wiring becomes narrower, that is, as it becomes finer. Therefore, the thickness of the metal layer formed by electroplating is not limited to the above and can be arbitrarily set.
  • 18 laminated body with a metal layer
  • 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> After the said plating process, you may heat-process with respect to the laminated body which has a metal layer as needed (heating process). By performing the heat treatment after the plating treatment, the adhesion of the metal layer (plating film) formed in the plating step may be further improved.
  • the heating process may be performed after the electroless plating process, and the heat treatment may be performed after the electroplating process.
  • the heating conditions in the heating step vary depending on the polymer used and the material of the metal layer, but the heating temperature is preferably from 80 to 200 ° C, more preferably from 100 to 140 ° C, from the viewpoint of further improving the adhesion of the metal layer.
  • 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. In addition, in this heating process, you may perform the heat processing from which conditions differ twice or more continuously.
  • etching step (5) By performing the process of etching the metal layer in the laminate in a pattern, a laminate (metal pattern material) having the pattern-like metal layer on the surface can be produced. This etching step (step (5)) will be described in detail below.
  • An etching process is a process of etching the metal layer (plating film) formed above in a pattern shape. That is, in this step, a desired metal pattern can be formed by removing unnecessary portions of the formed metal layer by etching. More specifically, as shown in FIG. 1E, a patterned metal layer 20 is formed in this step. Any method can be used to form the metal pattern, and specifically, a generally known subtractive method or semi-additive method is used.
  • a dry film resist layer is provided on the formed metal layer, the same pattern as the metal pattern part is formed by pattern exposure and development, and the metal layer is removed with an etching solution using the dry film resist pattern as a mask.
  • This is a method of forming a metal pattern. Any material can be used as the dry film resist, and negative, positive, liquid, and film-like ones can be used.
  • an etching method any method used at the time of manufacturing a printed wiring board can be used, and wet etching, dry etching, and the like can be used, and may be arbitrarily 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.
  • the semi-additive method is to provide a dry film resist layer on the formed metal layer, form the same pattern as the non-metal pattern part by pattern exposure and development, and perform electroplating using the dry film resist pattern as a mask,
  • quick etching is performed after the dry film resist pattern is removed, and the metal layer is removed in a pattern to form a metal pattern.
  • the dry film 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.
  • a pattern-form to-be-plated layer can be obtained by implementing the following processes (6) instead of a process (2).
  • a developer capable of dissolving and removing the polymer-containing layer is appropriately used.
  • the process of forming a pattern-like to-be-plated layer Metal pattern material provided with a pattern-like metal layer by performing process (3) and (4) with respect to the pattern-like to-be-plated layer obtained at process (6) Can also be manufactured (full additive method).
  • the obtained laminate having a patterned metal layer is used in various applications such as semiconductor chips, various electric wiring boards (for example, printed wiring boards), FPC, COF, TAB, antennas, multilayer wiring boards, motherboards, etc. Can be applied to. Especially, the use used as a wiring board is preferable.
  • the raw material A 47.4 g
  • pyridine 22 g
  • ethyl acetate 150 mL
  • the acrylic acid chloride 25g was dripped there, adjusting so that it might become 20 degrees C or less of internal temperature. Then, it was raised to room temperature and reacted for 3 hours.
  • distilled water 300 mL was added to stop the reaction. Thereafter, the ethyl acetate layer was washed four times with distilled water (300 mL), and then dried over magnesium sulfate, and further ethyl acetate was distilled off. Then, it refine
  • N, N-dimethylacetamide (8 g) was placed in a 500 mL three-necked flask and heated to 65 ° C. under a nitrogen stream.
  • the monomer M (14.3 g), acrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) (3.0 g), acrylic acid (manufactured by Tokyo Chemical Industry) (6.5 g) and V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) (0.4 g) of N, N-dimethylacetamide solution (8 g) was added dropwise over 4 hours. After completion of dropping, the mixture 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 aqueous sodium hydroxide solution as a titrant, and found to be 3.9 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 around 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
  • the numerical value in the chemical formula of the following polymer B represents the mol% of each unit.
  • Example 1 Formation of an underlayer containing 3- (acryloxy) propyltrimethoxysilane (KBM-5103 (manufactured by Shin-Etsu Silicone)) and KAYAMER PM-21 (manufactured by Nippon Kayaku) on a glass substrate (Corning Eagle 2000) Composition X1 was applied by spin coating and dried at 110 ° C. for 5 minutes. Thereafter, the glass substrate was washed with isopropyl alcohol, further washed with water, and air-dried to obtain a glass substrate on which an underlayer was formed.
  • KBM-5103 manufactured by Shin-Etsu Silicone
  • KAYAMER PM-21 manufactured by Nippon Kayaku
  • 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 an underlayer was formed on the glass substrate by the treatment. was confirmed.
  • composition Y1 for forming a layer to be plated was applied to the substrate on which the underlayer was formed by spin coating, and dried at 80 ° C. for 5 minutes. Thereafter, UV exposure (wavelength: 254 nm, exposure amount: 6000 mJ / cm 2 ) was performed on the entire surface of the substrate and washed with 1% sodium bicarbonate water. This obtained the to-be-plated layer (thickness: 0.6 micrometer) directly couple
  • Catalyst application A 1% by mass aqueous silver nitrate solution was prepared and used as a plating catalyst solution. A substrate having a layer to be plated was immersed in the plating catalyst solution for 10 minutes, and then washed with pure water.
  • a substrate having a plating layer provided with a plating catalyst was immersed in an electroless plating bath having the following composition at 26 ° C. for 60 minutes to perform electroless plating.
  • the obtained metal layer (plating layer) had a thickness of about 0.5 ⁇ m.
  • the electroless plating film (electroless copper plating film) obtained above was used as a power feeding layer, electroplating was performed for 20 minutes under the condition of 3 A / dm 2 using an electrolytic copper plating bath having the following composition, and metal A laminate having a layer was produced.
  • the thickness of the obtained electrolytic copper plating film was 15 ⁇ m.
  • Example 2 A laminated body was obtained according to the same procedure as in Example 1 except that the composition for forming a layer to be plated Y2 having the following composition was used instead of the composition for forming a layer to be plated Y1.
  • Example 3 A laminate was obtained according to the same procedure as in Example 1 except that the composition for forming a layer to be plated Y3 having the following composition was used instead of the composition for forming a layer to be plated Y1.
  • Example 4 A laminated body was obtained according to the same procedure as in Example 1 except that the composition Y4 to be plated layer having the following composition was used instead of the composition Y1 to be plated.
  • Example 5 A laminated body was obtained according to the same procedure as in Example 1 except that instead of the composition for forming a plating layer Y1, a composition for forming a plating layer Y5 having the following composition was used.
  • composition Y5 for forming a layer to be plated
  • the composition of the to-be-plated layer forming composition Y5 is 5.38% by mass of polymer A, 0.27% by mass of 3- (acryloxy) propyltrimethoxysilane, 1.62% by mass of KAYAMER PM-21, and Irgacure.
  • Example 6> A laminate was obtained according to the same procedure as in Example 1 except that a glass substrate (Matsunami Glass Industrial Co., Ltd., quartz) was used instead of the glass substrate (Corning Eagle 2000).
  • Example 7 A laminate was obtained according to the same procedure as in Example 1 except that a ceramic substrate (Kyocera Corporation) was used instead of the glass substrate (Corning Eagle 2000).
  • Example 8> A laminate was obtained according to the same procedure as in Example 1 except that a glass substrate (manufactured by Matsunami Glass Industry Co., Ltd., 0050) was used instead of the glass substrate (Corning Eagle 2000).
  • composition Y10 for plating layer formation contains polymer A and 3- (acryloxy) propyltrimethoxysilane.
  • the content ratio of 3- (acryloxy) propyltrimethoxysilane was 5.7% by mass with respect to the total mass of the polymer A.
  • model film In order to measure the Young's modulus and thermal shrinkage of the layer to be plated, a model film consisting only of the layer to be plated was prepared. Specifically, the composition for forming a layer to be plated is cast on a Teflon petri dish, then air-dried, and after completely removing the solvent in an oven (180 ° C. for 1 h), UV exposure (wavelength: 254 nm, exposure amount: 6000 mJ / cm 2 ) to produce a model film consisting only of the layer to be plated.
  • Substrate 1 Glass substrate (Corning Eagle 2000)
  • Substrate 2 Glass substrate (Matsunami Glass Industry Co., Ltd., quartz)
  • Substrate 3 Ceramic substrate (Kyocera Corporation)
  • Substrate 4 Glass substrate (Matsunami Glass Industry Co., Ltd., 0050)
  • Silane coupling agent 1 3- (acryloxy) propyltrimethoxysilane (KBM-5103 (manufactured by Shin-Etsu Silicone))
  • P O group-containing polymerizable compound 1: KAYAMER PM-21 (manufactured by Nippon Kayaku Co., Ltd.)
  • P O group-containing compound 1: Triethyl phosphate
  • Solvent 1 Cyclopentanone
  • Polymer B Polymer
  • Examples 1 to 8 were confirmed to be excellent in adhesion after being exposed to a high temperature environment.
  • the content of the P ⁇ O group-containing polymerizable compound in the composition for forming a plated layer was 30% relative to the content of the polymer.
  • Examples 1 to 4 which are less than the above, it was confirmed that the adhesion is more excellent.
  • Examples 1, 3 and 4 in which both the silicone compound and the sulfonic acid group-containing monomer are contained in the composition for forming a plating layer are further excellent in adhesion.
  • Substrate 12 Underlayer 14a, 14b: Plated layer 16: Metal layer 18: Laminate 20: Patterned metal layer

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Chemically Coating (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Laminated Bodies (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

La présente invention a pour but de proposer un procédé de fabrication d'un stratifié ayant une couche métallique qui présente une excellente adhésion à un substrat même dans un environnement à température élevée. Ce procédé de fabrication d'un stratifié ayant une couche métallique comprend : une étape de formation d'une couche de base, dans laquelle une couche de base est formée sur un substrat; une étape de formation d'une couche à plaquer, dans laquelle une couche à plaquer est formée sur la couche de base à l'aide d'une composition pour former une couche à plaquer, ladite composition contenant un agent de couplage de type silane ayant un groupe réactif et un polymère qui a un groupe polymérisable et un groupe fonctionnel interagissant avec un catalyseur de placage ou un précurseur de celui-ci; une étape de fourniture de catalyseur, dans laquelle un catalyseur de placage ou un précurseur de celui-ci est disposé sur la couche à plaquer; et une étape de placage, dans laquelle une couche métallique est formée sur la couche à plaquer en soumettant la couche à plaquer, sur laquelle le catalyseur de placage ou un précurseur de celui-ci a été disposé, à un placage. La composition de formation d'une couche de base et/ou la composition de formation d'une couche à plaquer contient un composé polymérisable à teneur en groupe P=O et la couche à plaquer a un module d'Young de 1 200 MPa ou moins.
PCT/JP2012/077854 2011-10-31 2012-10-29 Procédé de fabrication d'un stratifié ayant une couche métallique Ceased WO2013065628A1 (fr)

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WO2019171990A1 (fr) * 2018-03-09 2019-09-12 株式会社有沢製作所 Stratifié, et procédé de fabrication de celui-ci
CN111979533A (zh) * 2016-03-11 2020-11-24 麦克赛尔控股株式会社 镀覆部件的制造方法、镀覆部件、催化活性妨碍剂及无电解镀用复合材料

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CA2954867A1 (fr) 2014-07-16 2016-01-21 Lixil Corporation Composition de revetement et de traitement hydrophile et procede de traitement d'hydrophilisation
US11152294B2 (en) 2018-04-09 2021-10-19 Corning Incorporated Hermetic metallized via with improved reliability
EP3853394A1 (fr) * 2018-09-20 2021-07-28 Industrial Technology Research Institute Métallisation cuivre destinée à des trous d'interconnexion traversant le verre sur du verre mince
JP7618331B1 (ja) * 2023-07-06 2025-01-21 株式会社イオックス 無電解めっきの前処理塗料組成物

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JP2011094192A (ja) * 2009-10-29 2011-05-12 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、及び金属パターン材料
JP2011213019A (ja) * 2010-03-31 2011-10-27 Fujifilm Corp めっき受容性フィルム及びそれを用いた金属膜材料の製造方法

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CN111979533A (zh) * 2016-03-11 2020-11-24 麦克赛尔控股株式会社 镀覆部件的制造方法、镀覆部件、催化活性妨碍剂及无电解镀用复合材料
WO2019171990A1 (fr) * 2018-03-09 2019-09-12 株式会社有沢製作所 Stratifié, et procédé de fabrication de celui-ci
JPWO2019171990A1 (ja) * 2018-03-09 2021-04-08 株式会社有沢製作所 積層体及びその製造方法
US11317507B2 (en) 2018-03-09 2022-04-26 Arisawa Mfg. Co., Ltd. Laminate and method for manufacturing the same
JP7457645B2 (ja) 2018-03-09 2024-03-28 株式会社有沢製作所 積層体及びその製造方法
KR102865315B1 (ko) 2018-03-09 2025-09-29 가부시키가이샤 아리사와 세이사쿠쇼 적층체 및 그의 제조 방법

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