WO2006027947A1 - 無電解めっき前処理剤及びフレキシブル基板用銅張り積層体 - Google Patents

無電解めっき前処理剤及びフレキシブル基板用銅張り積層体 Download PDF

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Publication number
WO2006027947A1
WO2006027947A1 PCT/JP2005/015228 JP2005015228W WO2006027947A1 WO 2006027947 A1 WO2006027947 A1 WO 2006027947A1 JP 2005015228 W JP2005015228 W JP 2005015228W WO 2006027947 A1 WO2006027947 A1 WO 2006027947A1
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Prior art keywords
copper
electroless plating
clad laminate
pretreatment agent
flexible board
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Ceased
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PCT/JP2005/015228
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English (en)
French (fr)
Inventor
Toshifumi Kawamura
Toru Imori
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Nippon Mining Holdings Inc
Original Assignee
Nippon Mining and Metals Co Ltd
Nikko Materials Co Ltd
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Priority to JP2006535103A priority Critical patent/JP4859232B2/ja
Priority to US11/662,046 priority patent/US20070269680A1/en
Publication of WO2006027947A1 publication Critical patent/WO2006027947A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • C23C18/1641—Organic substrates, e.g. resin, plastic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/208—Multistep pretreatment with use of metal first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • 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
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • 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
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12903—Cu-base component

Definitions

  • Electroless plating pretreatment agent and copper-clad laminate for flexible substrate are Electroless plating pretreatment agent and copper-clad laminate for flexible substrate
  • the present invention relates to an electroless plating pretreatment agent used as a base material for a copper-clad laminate that is a material for a flexible substrate for printed wiring, and a copper-clad laminate for a flexible substrate produced using the same. .
  • Polyimide substrates are frequently used as insulating substrate materials for electronic components. Recently, as electronic devices have become thinner and smaller, a more flexible two-layer copper polyimide substrate, in which a metal layer is formed directly on the polyimide film, is attracting attention. Although the initial adhesion in the normal condition is practical, the characteristics such as adhesion in a heat-resistant, high-temperature and high-humidity environment are considered uneasy.
  • Patent Document 1 discloses a method for producing a metal layer by a sputtering method using a polyimide film flexible copper-clad laminate.
  • this method is expensive, and the adhesion in a heat-resistant, high-temperature, high-humidity environment is not satisfactory.
  • Patent Document 2 also includes five processes including a process for forming a resin composition coating on a polyimide film, a film activation process, a catalyst application process, a catalyst activation process, and an electroless metal plating process.
  • a method for performing electrolytic copper plating after performing electroless copper plating is described. This method is intended to produce a resin composition layer as an adhesion-imparting layer, and as a result, the film thickness of the resin composition layer is 1 to 20 ⁇ m, and the process is complicated.
  • Patent Document 1 Japanese Patent Laid-Open No. 9-136378
  • Patent Document 2 Japanese Patent Laid-Open No. 2001-168496
  • the present invention relates to a flexible substrate in which the initial adhesion strength between the base material and the copper plating layer in a normal state and the adhesion strength in a heat aging test (in the atmosphere, 150 ° C, 168 hours) are 0.4 kgfZcm or more.
  • An object of the present invention is to provide an electroless plating pretreatment liquid used for a copper clad laminate for a plate, and a copper clad laminate for a flexible substrate produced using the electroless plating pretreatment liquid.
  • the present inventors have found that a silane coupling agent having a metal-capturing ability and thermosetting as a pretreatment agent for electroless plating of a copper-clad laminate for a flexible substrate.
  • the present inventors have found that the above-mentioned problems can be solved by using an electroless plating pretreatment agent containing soluble rosin. That is, the present invention is as follows.
  • a pretreatment agent for electroless plating used for a base material of a copper-clad laminate for a flexible substrate comprising a silane coupling agent having a metal scavenging ability and a thermosetting resin.
  • a pretreatment agent for electroless plating used for a base material of a copper-clad laminate for a flexible substrate, comprising a silane coupling agent having a metal scavenging ability and a thermosetting resin.
  • thermosetting resin is an epoxy resin
  • a copper plating layer is formed by electroless plating, and an electric plating is formed thereon.
  • the substrate is treated with the electroless plating pretreatment agent of the present invention, and then the electroless copper plating layer
  • the copper-clad laminate for flexible printed circuit boards with an electric copper plating layer is the initial adhesion between the base material and the copper plating layer in the normal state, and the heat aging test (in air, 150 ° C, 168 hours).
  • the electroless plating pretreatment agent of the present invention comprises a silane coupling agent having a metal scavenging ability and a thermal treatment. Including curable rosin.
  • the noble metal catalyst can be more uniformly and more reliably fixed to the surface to be bonded via the silane coupling agent.
  • the silane coupling agent is preferably obtained by reacting an azole compound or an amine compound with an epoxy compound.
  • azole compounds include imidazole, oxazole, thiazole, selenazole, pyrazole, isoxazole, isothiazole, triazole, oxadiazole, thiadiazole, tetrazole, oxatriazole, thiatriazole, benzazole, indazole, benzimidazole, and benzotriazole. It is done. Although not limited to these, imidazole is particularly preferred.
  • Examples of the amine compound include saturated hydrocarbon amines such as propylamine, unsaturated hydrocarbon amines such as berylamine, and aromatic amines such as phenylamine.
  • the silane coupling agent is a compound having a -six X X group in addition to the noble metal capturing group derived from the azole compound or the amine compound, wherein X, X, and X are alkyl.
  • X, X, and X may be the same or different.
  • the silane coupling agent can be obtained by reacting the azole compound or amine compound with an epoxy silane compound.
  • R 2 is hydrogen or an alkyl group having 1 to 3 carbon atoms, n is 0 to 3)
  • the epoxy coupling agent shown by these is preferable.
  • the reaction between the azole compound and the epoxy group-containing silane compound is, for example, This can be done under the conditions described in Kaihei 6-256358.
  • R or hydrogen or an alkyl group having 1 to 3 carbon atoms R 3 is hydrogen or an alkyl group having 1 to 20 carbon atoms, R 4 is a bur group, or an alkyl group having 1 to 5 carbon atoms, n is 0 to 3 Indicates.
  • thermosetting resin used in the electroless plating pretreatment agent of the present invention examples include epoxy resin, urea resin, phenol resin, melamine resin, and urethane resin.
  • thermosetting resin epoxy resin It is preferable that the effect of improving the adhesion is particularly large.
  • the electroless plating pretreatment agent it is not essential for the electroless plating pretreatment agent to contain a noble metal compound.
  • the dipping activity can be obtained by dipping in an aqueous palladium chloride solution.
  • the pretreatment agent for plating contains a catalyst such as a noble metal compound.
  • the catalyst include noble metal compounds such as palladium, silver, platinum, and gold, for example, their halides, hydroxides, sulfates, carbonates, noble metal sarcophagus, and the like, and palladium compounds are particularly preferable.
  • Conventional catalysts such as tin chloride can also be included within the scope of the object of the present invention.
  • the noble metal stalagmite can be obtained by the reaction of a fatty acid, succinic acid, or naphthenic acid with a noble metal compound, and can be preferably used in the present invention.
  • the fatty acid is preferably one having 5 to 25 carbon atoms, more preferably 8 to 16. If the fatty acid has 4 or less carbon atoms, it will be difficult to dissolve in an organic solvent and become unstable. On the other hand, when the number of carbon atoms is 26 or more, the amount soluble in an organic solvent is limited and the content of noble metal is reduced, so that the amount added is not practical.
  • fatty acid examples include saturated fatty acids such as octylic acid, neodecanoic acid, dodecanoic acid, pentadecanoic acid, and octadecanoic acid, unsaturated fatty acids such as oleic acid and linoleic acid, and oxygen-containing substances such as hydroxytetradecanoic acid and carboxydecanoic acid. Mention may be made of fatty acids or mixtures thereof.
  • fatty acids succinic acid, and naphthenic acid
  • preferable examples include naphthenic acid, octylic acid, neodecanoic acid, pentadecanoic acid and the like.
  • halides such as palladium, silver, platinum, gold, etc., which exhibit a catalytic effect when copper or nickel is deposited on the surface of an electroless plating liquid force deposit
  • hydroxide A compound capable of forming a sarcophagus with a fatty acid or the like, particularly a palladium compound is particularly a palladium compound.
  • the noble metal stalagmite used in the present invention can be obtained by a conventional method for producing a metal stannic acid such as a metathesis method or a direct method using the fatty acid or the like and the noble metal compound.
  • the noble metal sarcophagus used in the present invention is soluble in an organic solvent and is stable as a solution.
  • organic solvents include alcohols such as butanol, 2-ethylhexanol, and octyl alcohol, aromatic hydrocarbons such as xylene, aliphatic hydrocarbons such as hexane, black-form, dioxane, and the like. Etc.
  • the electroless plating pretreatment agent of the present invention includes the above-mentioned silane coupling agent having a metal scavenging ability, thermosetting resin, noble metal stalagmite, etc., for example, butanol, 2-ethylhexanol, octyl It is used after being dissolved in an alcohol such as alcohol, an aromatic hydrocarbon such as xylene, an aliphatic hydrocarbon such as hexane, an organic solvent such as chloroform, dioxane and the like.
  • an alcohol such as alcohol, an aromatic hydrocarbon such as xylene, an aliphatic hydrocarbon such as hexane, an organic solvent such as chloroform, dioxane and the like.
  • the concentration of the silane coupling agent having a metal scavenging ability in the electroless plating pretreatment agent is not limited to this, but 0.001 to 10% by weight is preferable 0.05 to 3% by weight. % Is more preferred.
  • the amount is less than 001% by weight, the amount of the compound adhering to the surface of the substrate tends to be low, and it is difficult to obtain an effect.
  • it exceeds 10% by weight it is difficult to dry because the amount of adhesion is too much, and the powder tends to agglomerate.
  • the concentration of the thermosetting ⁇ in an electroless-plating pretreatment agent is preferably 0.001 to 30 wt%, preferably from 0.05 to 10 weight 0/0 power! / ⁇ . 0. less than 001 weight 0/0! /, The effect force without, since the liquid viscosity is more than 30% by weight too high, uneven comes into with plating.
  • the precious metal sarcophagus can be used in a concentration of 1 to 30000 mgZL, preferably 50 to LOOOOmgZL (in terms of precious metal) in the solution of the electroless plating pretreatment agent.
  • polyimide films As the base material of the copper-clad laminate for a flexible substrate of the present invention, various polyimide films, PET and the like are preferably used.
  • polyimide films include Kapton (Torayde Lupine (manufactured by Toray Industries, Inc.) can be listed as an isotropic PET (upon) and Upilex (manufactured by Ube Industries).
  • a method for treating a substrate with an electroless plating pretreatment agent methods such as dipping, brushing, and spin coating are generally used, but the surface treatment is not limited to these methods. As long as it is a method to attach the agent.
  • the film thickness of the electroless plating pretreatment agent layer of the present invention is preferably 1 to 200 nm.
  • the copper-clad laminate for a flexible substrate of the present invention is obtained by forming a copper plating layer on a base material subjected to the pretreatment described so far by a conventional electroless plating method.
  • a copper plating layer is formed by electrical plating.
  • imidazole silane (equimolar reaction product of imidazole and 3-glycidoxypropyltrimethoxysilane) lgZL and Pd stone wall (naphthene acid Pd, Nikko Materials) 0.5gZL (Pd equivalent lOOmg ZL) and epoxy resin (Epicoat EP828, Japan Epoxy Resin) lgZL-containing organic solvent (butanol) electroless plating pretreatment agent was applied.
  • the electroless copper plating (plating solution: NKM554, manufactured by Nippon Mining Metal Plating) has a thickness of 0.5 m.
  • electrolytic copper plating (plating solution: copper sulfate, manufactured by Nikko Metal Plating) was performed at a current density of 2AZdm 2 to form a copper plating layer with a thickness of 35 ⁇ m.
  • the peel strength under normal conditions, and then the peel strength after aging in air at 150 ° C for 168 hours were measured. Peel strength ⁇ O IS C— Based on 90 degree peel test based on 6481. The same applies to the following examples and comparative examples. The results are as shown in Table 1. The strength after aging is as high as 0.7 kgfZcm. The numerical value was shown.
  • imidazole silane (equimolar reaction product of imidazole and 3-glycidoxypropyltrimethoxysilane) lgZL and Pd sarcophagus (naphthoic acid Pd, Nikko Materials) 0.5gZL (Pd equivalent lOOmg ZL) and phenolic resin (XLC-4L, manufactured by Mitsui Chemicals) 2gZL-containing organic solvent (butanol) electroless plating pretreatment agent was applied .
  • the electroplated copper plating (plating solution: NKM554, manufactured by Nikko Metal Plateing) was used to deposit the copper film with a thickness of 0.5 m.
  • electrolytic copper plating (plating solution: copper sulfate, manufactured by Nikko Metal Plating) was performed to form a copper plating layer having a thickness of 35 ⁇ m. The peel strength under normal conditions, and then the peel strength after aging in air at 150 ° C for 168 hours were measured.
  • Example 1 A treatment test was conducted in the same manner as in Example 1 except that aminosilane ( ⁇ -aminopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of imidazolesilane in Example 1. As a result, as shown in Table 1, the strength after aging was as high as 0.4 kgfZcm.
  • aminosilane ⁇ -aminopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Example 1 A treatment and test was conducted in the same manner as in Example 1 except that epoxy resin was not included. As shown in Table 1, the initial peel strength was as high as 0.9 kgfZcm, but the peel strength after aging was as low as 0.1 kgfZcm.
  • Example 1 After forming a copper seed layer by 0.5 m by sputtering, a 35 m copper plating layer was formed by electrolytic copper plating in the same manner as in Example 1, and the test was performed in the same manner as in Example 1. As shown in Table 1, the initial peel strength was as high as 0.9 kgfZcm, but became low after aging.

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  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Inorganic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

　基材と銅めっき層の常態での初期密着力、及び耐熱エージング試験（大気中、１５０°C、１６８時間）での密着力が０．４ｋｇｆ／ｃｍ以上となるフレキシブル基板用銅張り積層体に用いる無電解めっき前処理液、及び該無電解めっき前処理液を用いて作製されたフレキシブル基板用銅張り積層体を提供する。 　フレキシブル基板用銅張り積層体の基材に用いる無電解めっき前処理剤であって、金属捕捉能を有するシランカップリング剤と、熱硬化性樹脂とを含むことを特徴とする無電解めっき前処理剤。基材を前記無電解めっき前処理剤で処理した後、無電解めっきにより銅めっき層を形成し、その上に電気めっきにより銅めっき層を形成したことを特徴とするフレキシブル基板用銅張り積層体。

Description

明 細 書
無電解めつき前処理剤及びフレキシブル基板用銅張り積層体
技術分野
[0001] 本発明は、プリント配線用フレキシブル基板の素材等となる銅張り積層体の基材に 用いる無電解めつき前処理剤、及びそれを用いて作製されたフレキシブル基板用銅 張り積層体に関する。
背景技術
[0002] ポリイミド基板は、電子部品用の絶縁基板材料として多用されている。最近では電 子機器の薄型化、小型化に伴い、ポリイミドフィルムに直接金属層を形成した、より自 由度の高い 2層銅ポリイミド基板が注目されている力 この基板は、ポリイミドフィルム と金属層の常態での初期密着力は実用レベルだが、耐熱 ·高温高湿環境での密着 力などの特性が不安視されて 、る。
[0003] また、ポリイミドフィルムのフレキシブル銅張り積層板にっ 、て、金属層をスパッタリ ング法により製造する方法が例えば特許文献 1に開示されて 、る。しかしこの方法で はコスト高であり、耐熱 ·高温高湿環境での密着力は満足できるものではな力つた。
[0004] ポリイミドフィルムと金属層の密着性を向上するための方法としてはプラズマ、 UV等 の乾式プロセス、アルカリ等での湿式プロセスがあるが、使用液の安全性'作業性や 、過度に処理すると金属層表面に凹凸ができ、微細配線形成に悪影響を与える可能 '性がある。
[0005] また、特許文献 2には、ポリイミドフィルムに榭脂組成物被膜を形成する工程、該被 膜活性化工程、触媒付与工程、触媒活性化工程、無電解金属めつき工程の 5工程 力もなる無電解銅めつきを行なった後電気銅めつきを行う方法が記載されて 、る。こ の方法は密着付与層として榭脂組成物層を生成させることを主題としており、その結 果榭脂組成物層の膜厚は 1〜20 μ mを有し、工程が煩雑である。
特許文献 1：特開平 9— 136378号公報
特許文献 2：特開 2001— 168496号公報
発明の開示 発明が解決しょうとする課題
[0006] 本発明は、基材と銅めつき層の常態での初期密着力、及び耐熱エージング試験（ 大気中、 150°C、 168時間）での密着力が 0. 4kgfZcm以上となるフレキシブル基 板用銅張り積層体に用いる無電解めつき前処理液、及び該無電解めつき前処理液 を用いて作製されたフレキシブル基板用銅張り積層体を提供することを目的とする。 課題を解決するための手段
[0007] 本発明者らは、上記課題につ!、て鋭意検討した結果、フレキシブル基板用銅張り 積層体の無電解めつき前処理剤として、金属捕捉能を有するシランカップリング剤と 熱硬化性榭脂とを含む無電解めつき前処理剤を用いることにより、上記課題を解決 することができることを見出した。即ち、本発明は以下の通りである。
[0008] (1)フレキシブル基板用銅張り積層体の基材に用いる無電解めつき前処理剤であつ て、金属捕捉能を有するシランカップリング剤と、熱硬化性榭脂とを含むことを特徴と する無電解めつき前処理剤。
[0009] (2)前記熱硬化性榭脂がエポキシ榭脂であることを特徴とする前記（1)記載の無電 解めつき前処理剤。
[0010] (3)基材を前記（1)又は（2)記載の無電解めつき前処理剤で処理した後、無電解め つきにより銅めつき層を形成し、その上に電気めつきにより銅めつき層を形成したこと を特徴とするフレキシブル基板用銅張り積層体。
発明の効果
[0011] 本発明の無電解めつき前処理剤を用いて基材を処理し、その後無電解銅めつき層
、電気銅めつき層を積層したフレキシブル基板用銅張り積層体は、基材と銅めつき層 の常態での初期密着力、及び耐熱エージング試験 (大気中、 150°C、 168時間）で の密着力が 0. 4kgfZcm以上となる、密着性に優れた 2層銅張りフレキシブル基板 用銅張り積層体となる。基材表面へは乾式'湿式前処理を全く行なわずに密着力を 付与できる。
発明を実施するための最良の形態
[0012] 本発明の無電解めつき前処理剤は、金属捕捉能を有するシランカップリング剤と熱 硬化性榭脂とを含む。
[0013] 金属捕捉能を有するシランカップリング剤を添加することにより、被めつき面に対し てシランカップリング剤を介して貴金属触媒をより均一に、より確実に固着することが できる。
[0014] 前記シランカップリング剤として、好ましいものはァゾール系化合物またはアミンィ匕 合物とエポキシ系化合物との反応により得られるものである。
ァゾール系化合物としては、イミダゾール、ォキサゾール、チアゾール、セレナゾー ル、ピラゾール、イソォキサゾール、イソチアゾール、トリァゾール、ォキサジァゾール 、チアジアゾール、テトラゾール、ォキサトリァゾール、チアトリァゾール、ベンダゾー ル、インダゾール、ベンズイミダゾール、ベンゾトリアゾールなどが挙げられる。これら に制限されるものではな 、が、イミダゾールが特に好ま U、。
[0015] また、ァミン化合物としては、例えばプロピルアミン等の飽和炭化水素ァミン、ビ- ルァミン等の不飽和炭化水素ァミン、フ ニルァミン等の芳香族アミン等を挙げること ができる。
[0016] また前記シランカップリング剤とは、前記ァゾール系化合物またはアミンィ匕合物由来 の貴金属捕捉基の他に、 -six X X基を有する化合物であり、 X、 X、 Xはアルキ
1 2 3 1 2 3 ル基、ハロゲンやアルコキシ基などを意味し、被めつき物への固定が可能な官能基 であれば良い。 X、 X、 Xは同一でもまた異なっていても良い。
1 2 3
[0017] 前記シランカップリング剤は、前記ァゾール系化合物またはアミンィ匕合物とエポキシ シランィ匕合物を反応させることにより得ることができる。
[0018] このようなエポキシシラン化合物としては、
[化 1]
C H2 - C H- C H2 0 (C H2) 3 S 1 (O R ^ n R 2 (S-n)
(式中、
Figure imgf000004_0001
R2は水素または炭素数が 1〜3のアルキル基、 nは 0〜3)
で示されるエポキシカップリング剤が好ましい。
前記ァゾール系化合物と前記エポキシ基含有シランィ匕合物との反応は、例えば特 開平 6— 256358号公報に記載されている条件で行うことができる。
[0020] 例えば、 80〜200°Cでァゾール系化合物 1モルに対して 0. 1〜10モルのエポキシ 基含有シランィ匕合物を滴下して 5分〜 2時間反応させることにより得ることができる。 その際、溶媒は特に不要である力 クロ口ホルム、ジォキサン、メタノール、エタノール 等の有機溶媒を用いてもよい。
[0021] 特に好ま 、例としてイミダゾールイ匕合物とエポキシシラン系化合物の反応を下記 に示す。
Figure imgf000005_0001
(式中、
Figure imgf000005_0002
R ま水素または炭素数が 1〜3のアルキル基、 R3は水素、または炭素数 1〜20のアルキル基、 R4はビュル基、または炭素数 1〜5のアルキル基、 nは 0〜3を 示す。）
[0022] 本発明に使用する金属捕捉能を持つ官能基を有するシランカップリング剤のその 他の例として、 γ—ァミノプロピルトリメトキシシラン、 γ—ァミノプロピルトリエトキシシ ラン、 Ν— β (アミノエチル） γ—ァミノプロピルトリメトキシシラン、 Ν— β (アミノエチル ) γ—ァミノプロピルトリエトキシシラン、 γ—メルカプトプロピルトリメトキシシラン等が 挙げられる。
[0023] 本発明の無電解めつき前処理剤に用いる熱硬化性榭脂としては、エポキシ榭脂、 尿素樹脂、フエノール榭脂、メラミン榭脂、ウレタン榭脂等が挙げられる。熱硬化性榭 脂を添加することにより、密着力が向上する。熱硬化性榭脂としては、エポキシ榭脂 を用いると特に密着力向上の効果が大きぐ好ましい。
[0024] 本発明において、無電解めつき前処理剤に貴金属化合物が含有されることは必須 ではない。本めつき前処理剤に浸漬後、塩化パラジウム水溶液に浸漬することでめつ き活性を得ることができる。しかし、めっき前処理剤が貴金属化合物等の触媒を含有 することがより好ましい。触媒としては、パラジウム、銀、白金、金等の貴金属化合物、 例えば、それらのハロゲン化物、水酸化物、硫酸塩、炭酸塩、貴金属石鹼等を挙げ ることができ、特にパラジウム化合物が好ましい。また、従来の塩化スズなどの触媒も 本発明の目的の範囲内において含有させることができる。
[0025] 貴金属石鹼は、脂肪酸、榭脂酸、またはナフテン酸と、貴金属化合物との反応によ り得ることができ、本発明にお 、て好ましく用いることができる。
[0026] 脂肪酸としては、炭素原子数が 5〜25のものが好ましぐより好ましくは 8〜16であ る。脂肪酸の炭素数が 4以下であると、有機溶媒に溶解しにくくなり、不安定となる。 また炭素原子数が 26以上であると有機溶媒への可溶分が限定されること、貴金属含 有量が低下することで添加量が多くなり実用的でない。
[0027] 前記脂肪酸としては、ォクチル酸、ネオデカン酸、ドデカン酸、ペンタデカン酸、ォ クタデカン酸等の飽和脂肪酸、ォレイン酸、リノール酸等の不飽和脂肪酸、ヒドロキシ テトラデカン酸、カルボキシデカン酸等の含酸素脂肪酸、あるいはこれらの混合物を 挙げることができる。
[0028] また、前記脂肪酸、榭脂酸、ナフテン酸のうち、好ましいものを例示すると、ナフテン 酸、ォクチル酸、ネオデカン酸、ペンタデカン酸等を挙げることができる。
[0029] また、前記貴金属化合物としては無電解めつき液力 被めつき物表面に銅やニッケ ルなどを析出させる際の触媒効果を示すパラジウム、銀、白金、金等のハロゲン化物 、水酸化物、硫酸塩、炭酸塩等の化合物であって、脂肪酸等と石鹼を形成し得る化 合物を挙げることができる力 特にパラジウム化合物が好ましい。
[0030] 本発明に使用する貴金属石鹼は、前記脂肪酸等と前記貴金属化合物とを複分解 法、直接法等の金属石酸製造法の常法により得ることができる。
[0031] 本発明に使用する貴金属石鹼として好ましいナフテン酸パラジウムを下記に示す。
[化 3]
Figure imgf000007_0001
n = 9〜 1 3の混合物 酸パラジウムの構造式
[0032] 本発明に使用する前記貴金属石鹼は、有機溶剤に可溶性であり、また溶液として 安定である。このような有機溶剤としては、例えば、ブタノール、 2—ェチルへキサノ ール、ォクチルアルコール等のアルコール、キシレン等の芳香族炭化水素、へキサ ン等の脂肪族炭化水素、クロ口ホルム、ジォキサン等を挙げることができる。
[0033] 本発明の無電解めつき前処理剤は、上記金属捕捉能を有するシランカップリング剤 、熱硬化性榭脂、貴金属石鹼等を、例えば、ブタノール、 2—ェチルへキサノール、 ォクチルアルコール等のアルコール、キシレン等の芳香族炭化水素、へキサン等の 脂肪族炭化水素、クロ口ホルム、ジォキサン等の有機溶剤に溶解させて用いる。
[0034] 無電解めつき前処理剤中の金属捕捉能を有するシランカップリング剤の濃度はこれ に限ったものではないが、 0. 001〜10重量％が好ましぐ 0. 05〜3重量％がより好 ましい。 0. 001重量％未満の場合、基材の表面に付着する化合物量が低くなりやす ぐ効果が得にくい。また、 10重量％を超えると付着量が多すぎて乾燥しにくかったり 、粉末の凝集を起こしやすくなる。
[0035] 無電解めつき前処理剤中の熱硬化性榭脂の濃度は 0. 001〜30重量％が好ましく 、 0. 05〜10重量0 /0力より好まし!/ヽ。 0. 001重量0 /0より少な!/、と効果力なく、 30重量 %を超えると液粘度が高くなりすぎるため、めっき付きにむらが出る。
[0036] また、貴金属石鹼は、無電解めつき前処理剤の溶液中において、 l〜30000mgZ L、好ましくは 50〜： LOOOOmgZLの濃度（貴金属換算）で使用することができる。
[0037] 本発明のフレキシブル基板用銅張り積層体の基材としては、各種ポリイミドフィルム 、 PET等が好ましく用いられる。ポリイミドフィルムとしては、例えば、カプトン (東レデ ュポン製）、ユーピレックス (宇部興産製)等力 PETとしては、ルミラー (東レ製）が挙 げられる。
[0038] 基材を無電解めつき前処理剤で処理する方法としては、浸漬、刷毛塗り、スピンコ ート等の方法が一般的であるが、これらに限定されるものではなぐ表面に前処理剤 を付着させる方法であれば良 、。
[0039] 表面処理後に使用した溶剤を揮発させるにはこの溶媒の揮発温度以上に加熱して 表面を乾燥すれば十分である力 さらに 60〜120°Cで 3〜60分間加熱することが好 ましい。
また、本発明の無電解めつき前処理剤層の膜厚は l〜200nmが好ましい。
[0040] 本発明のフレキシブル基板用銅張り積層体は、これまで述べてきた前処理を施した 基材上に、常法の無電解めつき法により銅めつき層を形成し、更に常法の電気めつき により銅めつき層を形成したものである。こうして、本発明により、均一で密着性に優 れたフレキシブル基板用銅張り積層体を得ることができる。
実施例
[0041] 以下、実施例によって本発明を更に詳細に説明する。
[0042] 実施例 1
市販のポリイミドフィルムカプトン（200H、東レデュポン製）の表面に、イミダゾール シラン (イミダゾールと 3 -グリシドキシプロピルトリメトキシシランの等モル反応生成物 ) lgZLと、 Pd石鹼（ナフテン酸 Pd、 日鉱マテリアルズ製） 0. 5gZL (Pd換算 lOOmg ZL)と、エポキシ榭脂（ェピコート EP828、ジャパンエポキシレジン製） lgZLを含ん だ有機溶媒 (ブタノール)系無電解めつき前処理剤を塗布した。 150°Cで溶媒除去し 、膜厚 70nmの前処理剤層を形成した後、無電解銅めつき（めっき液: NKM554、 日 鉱メタルプレーティング製）により膜厚 0. 5 mの銅めつき層を形成し、次に、電流密 度 2AZdm2で電気銅めつき（めっき液:硫酸銅系、 日鉱メタルプレーティング製)を行 ない、膜厚 35 μ mの銅めつき層を形成した。その常態でのピール強度、その後空気 中 150°C、 168時間エージングした後のピール強度をそれぞれ測定した。ピール強 度 ίお IS C— 6481に基づく 90度引き剥がし試験による。以下の実施例、比較例に おいても同様である。結果は表 1の通り、エージング後での強度も 0. 7kgfZcmと高 い数値を示した。
[0043] 実施例 2
市販のポリイミドフィルムカプトン（200H、東レデュポン製）の表面に、イミダゾール シラン (イミダゾールと 3 -グリシドキシプロピルトリメトキシシランの等モル反応生成物 ) lgZLと Pd石鹼（ナフテン酸 Pd、 日鉱マテリアルズ製） 0. 5gZL (Pd換算 lOOmg ZL)と、フ ノール榭脂 (XLC— 4L、三井ィ匕学製) 2gZLを含んだ有機溶媒 (ブタノ ール)系無電解めつき前処理剤を塗布した。 150°Cで溶媒除去し、膜厚 70nmの前 処理剤層を形成した後、無電解銅めつき（めっき液: NKM554、 日鉱メタルプレーテ イング製）により膜厚 0. 5 mの銅めつき層を形成し、次に、電気銅めつき（めっき液： 硫酸銅系、 日鉱メタルプレーティング製)を行な 、、膜厚 35 μ mの銅めつき層を形成 した。その常態でのピール強度、その後空気中 150°C、 168時間エージングした後 のピール強度をそれぞれ測定した。
[0044] 実施例 3
実施例 1のイミダゾールシランの変わりにアミノシラン（ γ—ァミノプロピルトリエトキシ シラン、信越ィ匕学製)を用いた以外は実施例 1と同様に処理'試験を行なった。結果 は表 1の通り、エージング後での強度も 0. 4kgfZcmと高い数値を示した。
[0045] 比較例 1
エポキシ榭脂を含まな 、以外は実施例 1と同様に処理 ·試験を行なった。結果は表 1の通り、初期ピール強度は 0. 9kgfZcmと高かったが、エージング後のピール強度 は 0. lkgfZcmと低いものとなった。
[0046] 比較例 2
スパッタリング法により銅シード層を 0. 5 m形成した後、実施例 1と同様に電気銅 めっきで 35 mの銅めつき層を形成し、実施例 1と同様に試験を行なった。結果は表 1の通り、初期ピール強度は 0. 9kgfZcmと高かったが、エージング後は低いものと なった。
[0047] [表 1] 初期ピール強度 耐熱エージング試験 (kgfZ cm) ピール強度 (kgf/cm) 実施例 1 0. 9 0. 7 実施例 2 0. 8 0. 6 実施例 3 0. 6 0. 4 比較例 1 0. 9 0. 1 比較例 2 0. 9 0. 1

Claims

請求の範囲
[1] フレキシブル基板用銅張り積層体の基材に用いる無電解めつき前処理剤であって
、金属捕捉能を有するシランカップリング剤と、熱硬化性榭脂とを含むことを特徴とす る無電解めつき前処理剤。
[2] 前記熱硬化性榭脂がエポキシ榭脂であることを特徴とする請求の範囲 1記載の無 電解めつき前処理剤。
[3] 基材を請求の範囲 1又は 2記載の無電解めつき前処理剤で処理した後、無電解め つきにより銅めつき層を形成し、その上に電気めつきにより銅めつき層を形成したこと を特徴とするフレキシブル基板用銅張り積層体。
PCT/JP2005/015228 2004-09-10 2005-08-22 無電解めっき前処理剤及びフレキシブル基板用銅張り積層体 Ceased WO2006027947A1 (ja)

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JP2006535103A JP4859232B2 (ja) 2004-09-10 2005-08-22 無電解めっき前処理剤及びフレキシブル基板用銅張り積層体
US11/662,046 US20070269680A1 (en) 2004-09-10 2005-08-22 Electroless Plating Pretreatment Agent and Copper-Clad Laminate for Flexible Substrate

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JP2004-263861 2004-09-10
JP2004263861 2004-09-10

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TW (1) TWI305237B (ja)
WO (1) WO2006027947A1 (ja)

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JP2008156702A (ja) * 2006-12-22 2008-07-10 Fujitsu Ltd 樹脂筐体及びその製造方法
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JP2011155196A (ja) * 2010-01-28 2011-08-11 Kyocera Corp 配線基板の製造方法及び配線基板
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JP2008007849A (ja) * 2006-06-01 2008-01-17 Nippon Paint Co Ltd 無電解めっき用プライマー組成物及び無電解めっき方法
JP2008156702A (ja) * 2006-12-22 2008-07-10 Fujitsu Ltd 樹脂筐体及びその製造方法
JP2008210892A (ja) * 2007-02-23 2008-09-11 Sekisui Chem Co Ltd 電磁波遮蔽材料の製造方法、及び、電磁波遮蔽材料
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JP2011155196A (ja) * 2010-01-28 2011-08-11 Kyocera Corp 配線基板の製造方法及び配線基板
JP2015229788A (ja) * 2014-06-05 2015-12-21 奥野製薬工業株式会社 無電解めっき下地層形成用組成物
JP2019104925A (ja) * 2014-12-29 2019-06-27 四国化成工業株式会社 樹脂組成物及びその利用

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US20070269680A1 (en) 2007-11-22
JP4859232B2 (ja) 2012-01-25
JPWO2006027947A1 (ja) 2008-07-31
JP2012007244A (ja) 2012-01-12
KR20070088611A (ko) 2007-08-29
TWI305237B (en) 2009-01-11

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