WO2023085246A1 - 非感光性表面改質剤、積層体、プリント基板及び電子デバイス - Google Patents

非感光性表面改質剤、積層体、プリント基板及び電子デバイス Download PDF

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WO2023085246A1
WO2023085246A1 PCT/JP2022/041485 JP2022041485W WO2023085246A1 WO 2023085246 A1 WO2023085246 A1 WO 2023085246A1 JP 2022041485 W JP2022041485 W JP 2022041485W WO 2023085246 A1 WO2023085246 A1 WO 2023085246A1
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group
layer
laminate
heterocyclic compound
resin
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PCT/JP2022/041485
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English (en)
French (fr)
Japanese (ja)
Inventor
浩了 有田
恵美子 御子柴
淳 原
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コニカミノルタ株式会社
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Priority to KR1020247010870A priority Critical patent/KR20240055049A/ko
Priority to CN202280073097.1A priority patent/CN118202008A/zh
Priority to JP2023559629A priority patent/JPWO2023085246A1/ja
Publication of WO2023085246A1 publication Critical patent/WO2023085246A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
    • C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
    • C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2363/00—Epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards

Definitions

  • the present invention relates to a non-photosensitive surface modifier, a laminate, a printed circuit board, and an electronic device, and in particular, a non-photosensitive surface modifier that can further improve the adhesion between a metal layer and a resin layer. Regarding.
  • printed wiring boards also referred to as “printed boards” having high-density and high-definition wiring are in demand.
  • a resin material such as an etching resist, a plating resist, a solder resist, or a prepreg is bonded to the surface of a metal layer or metal wiring.
  • High adhesiveness is required between the metal layer and the resin layer in the manufacturing process of the printed wiring board and in the manufactured product.
  • Patent Document 1 a method of forming a film for improving adhesiveness for improving the adhesiveness with the resin layer on the surface of the metal layer (see, for example, Patent Document 1), a method of incorporating a sulfur-containing compound and a nitrogen-containing compound into a photosensitive resin to improve adhesiveness (see, for example, Patent Document 2).
  • Patent Documents 1 and 2 Although the adhesion between the metal layer and the resin layer is improved to some extent, sufficient adhesion has not yet been obtained.
  • 5G mobile communication and high-density mounting technology for semiconductor packages have progressed, and the demand for low-roughness metal layers on printed wiring boards and narrower metal wiring lines has increased. is required more than ever before.
  • the present invention has been made in view of the above problems and circumstances, and the problem to be solved is a non-photosensitive surface modifier that can further improve the adhesion between the metal layer and the resin layer.
  • An object of the present invention is to provide a laminate, a printed circuit board and an electronic device using a photosensitive surface modifier.
  • the present inventors in the process of studying the causes of the above problems, found that a specific The present inventors have found that the adhesion between the metal layer and the resin layer can be further improved by including a heterocyclic compound having a structure, and have completed the present invention. That is, the above problems related to the present invention are solved by the following means.
  • a non-photosensitive surface modifier that forms a surface modification layer between the metal layer and the resin layer A non-photosensitive surface modifier containing at least one heterocyclic compound having a structure represented by the following general formula (1), (2), (3) or (4).
  • R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, and may further have a substituent.
  • R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an ester group, an amide group, a heteroaryl group or a halogen atom.
  • each substituent R 2 may be the same or different.
  • each n may be the same or different, and when there are multiple m's, each m may be the same or different. may ]
  • a laminate in which a surface-modified layer and a resin layer are sequentially provided on a metal layer A laminate in which the surface-modified layer contains at least one heterocyclic compound having a structure represented by the following general formula (1), (2), (3) or (4).
  • R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, and may further have a substituent.
  • R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an ester group, an amide group, a heteroaryl group or a halogen atom.
  • each substituent R 2 may be the same or different.
  • each n may be the same or different, and when having a plurality of m, each m may be the same or different. good too. ]
  • heterocyclic compound is a heterocyclic compound having a structure represented by the following general formula (5).
  • R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, and may further have a substituent.
  • the non-photosensitive surface modifier of the present invention contains at least one heterocyclic compound having a structure represented by the general formula (1), (2), (3) or (4).
  • a nitrogen atom (N atom) present in the structure of the ring compound interacts with the metal, and a phenolic hydroxy group interacts with the resin.
  • the presence of the surface-modified layer formed by such a non-photosensitive surface-modifying agent between the metal layer and the resin layer allows the metal layer and the resin layer to form a surface having the above interaction. Adhesion is improved by the modified layer.
  • Phenolic hydroxy groups can form covalent bonds with polar groups present in resins and polymerizable resins represented by hydrogen bonds or epoxy groups, with stronger interaction forces than ⁇ - ⁇ interactions and van der Waals forces. can adhere.
  • the heterocyclic compound for example, the exemplary compound (1- The molecular skeleton of 1)
  • the nitrogen atoms (N) interact with the metal of the metal layer 10
  • the phenolic hydroxyl groups (OH) It is presumed that the resin layer 20 can be approached and a stronger interaction can be obtained.
  • FIG. 1 represents the same as in FIG.
  • Diagram showing the process of forming a metal wiring pattern (metal-clad laminate) A diagram showing the formation process of a metal wiring pattern (formation of a surface modification layer)
  • a diagram showing a process of forming a metal wiring pattern formation of a resist layer
  • a diagram showing a process of forming a metal wiring pattern pattern (patterning of a resist layer)
  • the non-photosensitive surface modifier of the present invention is a non-photosensitive surface modifier that forms a surface modification layer between a metal layer and a resin layer, and comprises at least the general formulas (1), (2), It contains one or more heterocyclic compounds having a structure represented by (3) or (4).
  • This feature is a technical feature common to or corresponding to each of the following embodiments.
  • the heterocyclic compound is preferably a heterocyclic compound having a structure represented by the general formula (1).
  • a heterocyclic compound having a structure represented by is preferable from the viewpoint of improving the adhesion between the metal layer and the resin layer. In terms of solubility, it is preferable to contain at least water or alcohols.
  • the laminate of the present invention is a laminate in which a surface-modified layer and a resin layer are sequentially provided on a metal layer,
  • the surface-modifying layer contains at least one heterocyclic compound having a structure represented by formula (1), (2), (3) or (4). This makes it possible to provide a laminate with improved adhesion between the metal layer and the resin layer.
  • the resin layer is a photosensitive resin composition containing an alkali-soluble resin, or a thermosetting resin composition containing at least a resin having an epoxy structure, and the phenolic hydroxyl group contained in the heterocyclic compound. is preferable from the point of view of improvement in adhesion due to the interaction of
  • the laminate of the present invention can be suitably used for printed circuit boards or electronic devices.
  • the non-photosensitive surface modifier of the present invention is a non-photosensitive surface modifier that forms a surface modification layer between a metal layer and a resin layer, and comprises at least the following general formulas (1), (2), It contains one or more heterocyclic compounds having a structure represented by (3) or (4).
  • R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, preferably an aryl group, and may further have a substituent.
  • substituents include a hydroxy group and an amide group.
  • R 2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an ester group, an amide group, a halogen atom, or a heteroaryl group; In particular, it is preferable to represent an alkyl group.
  • n and m are each an integer of 0 to 5
  • n + m an integer of 0 to 5 (however, with respect to general formula (1), an integer of 0 to 4) represents Moreover, in each general formula, when having a plurality of substituents R 2 , the respective substituents R 2 may be the same or different from each other. In addition, when there are multiple n's, each n may be the same or different, and when there are multiple m's, each m may be the same or different. may
  • the heterocyclic compound according to the present invention is a heterocyclic compound having a structure represented by the general formula (1) among the heterocyclic compounds having the structures represented by the general formulas (1) to (4). This is preferable in that the adhesion between the metal layer and the resin layer is improved as a result of the interaction between the metal layer and the surface modified layer and between the surface modified layer and the resin layer.
  • heterocyclic compound according to the present invention is preferably a heterocyclic compound having a structure represented by the following general formula (5) from the viewpoint of improving adhesion between the metal layer and the resin layer.
  • R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, preferably an aryl group, and may further have a substituent.
  • substituents include a hydroxy group and an amide group.
  • heterocyclic compounds having structures represented by the general formulas (1) to (5) are listed below, but the heterocyclic compound according to the present invention is not limited to these.
  • the heterocyclic compound contained in the non-photosensitive surface modifier of the present invention may be one type or two or more types.
  • the non-photosensitive surface modifier of the present invention preferably contains at least water or alcohol as a solvent.
  • the alcohol include methanol, ethanol, 2-propanol and the like. Two or more kinds of water or alcohols may be used in combination as the solvent.
  • the mass ratio (% by mass) of water and alcohol is preferably in the range of 100:0 to 50:50, more preferably in the range of 100:0 to 75:25.
  • the aromatic heterocyclic compound is contained in the range of 0.00001 (0.1 ppm) to 0.1 (1000 ppm) mass% with respect to the total non-photosensitive surface modifier from the viewpoint of film formation. Preferably, it is contained within the range of 0.00001 (0.1 ppm) to 0.01 (100 ppm) mass %.
  • non-photosensitive surface modifier of the present invention may contain other components other than the above, but does not contain polymers, polymerizable monomers or oligomers, that is, does not contain resins. shall consist only of non-polymeric materials;
  • the other components include surfactants, preservatives, stabilizers, acids, bases, pH adjusters and the like.
  • the laminate of the present invention is a laminate in which a surface-modified layer and a resin layer are sequentially provided on a metal layer, wherein the surface-modified layer comprises at least the general formulas (1), (2), and (3). or contains one or more heterocyclic compounds having a structure represented by (4).
  • heterocyclic compounds having the structures represented by the general formulas (1) to (4) are omitted because they are as described above.
  • the heterocyclic compound is a heterocyclic compound having a structure represented by the general formula (1) among the heterocyclic compounds having the structures represented by the general formulas (1) to (4).
  • the interaction between the metal layer and the modified surface layer and between the modified surface layer and the resin layer results in improved adhesion between the metal layer and the resin layer.
  • the heterocyclic compound is preferably a heterocyclic compound having the structure represented by the general formula (5) from the viewpoint of improving the adhesion between the metal layer and the resin layer.
  • the heterocycle of the heterocyclic compound is oriented substantially perpendicularly to the metal layer, and the phenolic hydroxy group of the heterocyclic compound is oriented substantially perpendicularly to the resin layer.
  • Orientation is preferable in that the phenolic hydroxy groups can be brought closer to the resin layer, a stronger interaction can be obtained, and the adhesion can be improved.
  • quantum chemical calculation software Gaussian16 (manufactured by Gaussian) is used to optimize the structure using B3LYP (density functional theory) in DFT calculation.
  • SDD Stttgart/Dresden ECP
  • 6-31G(d) is used for other elements.
  • the Grid scan module of the soft Material Science Suite manufactured by Schrodinger in the space around the ligand, the position at which the copper ion is restabilized is set as the initial configuration.
  • the optimum structure calculated above will be explained by taking, for example, the exemplary compound (1-1) as an example. As shown in FIG.
  • the interaction between the compound (exemplary compound (1-1)) and copper (Cu) When a central line A perpendicular to the axial direction is drawn at the center position of the compound with the site as the axial direction, the interaction site with copper (Cu) and the phenolic It is preferred that the hydroxy groups (OH) are oriented in opposite directions to each other. Specifically, when the optimized structure calculated above is presented in Winmostar, at least one angle shown by selecting a copper atom (Cu)-nitrogen atom (N)-oxygen atom (O)-is 140 ° The above is preferable (see FIG. 2).
  • the angle formed by the copper atom-nitrogen atom-oxygen atom is 169° in Exemplified Compound (1-1), 168° in Exemplified Compound (2-2), and 71° in Exemplified Compound (3-8).
  • the nitrogen atom (N) and the phenolic hydroxy group (OH) in the structure of the heterocyclic compound are present on the diagonal of the molecular skeleton, so that the nitrogen atom (N) 10, the phenolic hydroxy group (OH) can be brought closer to the resin layer 20, resulting in a stronger interaction (see FIG. 1).
  • the laminate of the present invention can be applied to printed circuit boards (printed wiring boards) or electronic devices, for example.
  • the printed circuit board can be formed by a method of forming a metal wiring pattern by photolithography, as will be described later.
  • examples of the electronic devices include smartphones, tablet terminals, personal computers, servers, routers, communication base stations, display devices, home appliances, and the like.
  • the laminate of the present invention is a laminate obtained by sequentially providing a surface-modified layer and a resin layer on a metal layer. That is, the metal layer and the surface modification layer are adjacent, and the surface modification layer and the resin layer are adjacent.
  • the metal layer is a layer containing metal as a main component.
  • the main component means a component containing 50% by mass or more.
  • metals used for the metal layer include gold, silver, platinum, zinc, palladium, rhodium, osmium, ruthenium, iridium, copper, nickel, cobalt, iron, tin, chromium, titanium, tantalum, tungsten, indium, Metals such as aluminum, lead, molybdenum, or alloys thereof can be used. Among these, from the viewpoint of workability and conductivity, it is preferable to use copper or a copper alloy as a main component.
  • the metal layer can be formed by metal foil, plating, or a vacuum film forming method.
  • the thickness of the metal layer is not particularly limited, and may be set according to the thickness of the metal wiring pattern to be formed, for example.
  • the laminate of the present invention preferably has an insulating layer under the metal layer.
  • the insulating layer is not particularly limited, and a resin sheet or prepreg that is generally used as an insulating layer can be used.
  • the laminated body having the insulating layer as described above corresponds to the laminated body 6 in FIG. 5 showing the resist layer forming process described later.
  • the surface-modifying layer can be formed by applying the non-photosensitive surface-modifying agent of the present invention to the surface of the metal layer and drying.
  • the thickness of the surface-modified layer is not particularly limited, it is preferably within the range of 0.1 to 20 nm from the viewpoint of the effects of the present invention.
  • the resin layer used in the present invention is not particularly limited, but acrylonitrile/styrene copolymer resin (AS resin), acrylonitrile/butadiene/styrene copolymer resin (ABS resin), fluororesin, polyamide, polyethylene, polyethylene terephthalate, polychlorinated Thermoplastic resins such as vinylidene, polyvinyl chloride, polycarbonate, polystyrene, polysulfone, polypropylene, cyclopolyolefin resin, liquid crystal polymer, epoxy resin, phenol resin, polyimide, polyurethane, bismaleimide/triazine resin, modified polyphenylene ether, cyanate ester, etc. thermosetting resins, or UV-curable resins such as UV-curable epoxy resins and UV-curable acrylic resins. These resins may be modified with functional groups, and may be reinforced with glass fibers, aramid fibers, other fibers, or the like
  • the laminate of the present invention is a printed circuit board laminate (when it is a printed circuit board laminate), a commercially available resin film or prepreg (a sheet-like fiber impregnated with a liquid resin) can be used as the resin layer.
  • a commercially available resin film or prepreg a sheet-like fiber impregnated with a liquid resin
  • fluorine resins, cyclopolyolefin resins, liquid crystal polymers, epoxy resins, phenol resins, polyimides, bismaleimide-triazine resins, modified polyphenylene ethers, and cyanate esters when the laminate of the present invention forms the wiring of a printed circuit board (when it is a metal wiring pattern), the resin layer can be a commercially available liquid resist or dry film resist, and contains an alkali-soluble resin. UV-curable epoxy resins, UV-curable acrylic resins, and polyimides are preferably used.
  • the method for forming a metal wiring pattern according to the present invention is a method for forming a metal wiring pattern by photolithography, wherein the non-photosensitive surface modifier of the present invention is used to form a surface modified layer between the metal layer and the resist. It is preferable to have a step of forming
  • a metal wiring pattern is formed by having the following steps (A) to (F).
  • step (A) the metal-clad laminate 5 (see FIG. 3) in which the metal layer 2 is formed on the insulating layer 1 is washed with an acid.
  • an acid cleaning liquid is not particularly limited, and conventionally known liquids can be used. Moreover, you may wash with water after acid washing.
  • the insulating layer 1 is an insulating layer that serves as a base material for metal wiring patterns.
  • the insulating layer 1 is made of an insulating material such as resin, and may be a prepreg in which a base material such as paper or glass is impregnated with resin.
  • the metal layer 2 is the same as the metal layer of the laminate.
  • step (B) the surface-modified layer 3 is formed on the metal layer 2 of the metal-clad laminate 5 using the non-photosensitive surface-modifying agent of the present invention (see FIG. 4). Specifically, a non-photosensitive surface modifier is applied onto the metal layer 2 to form the surface modified layer 3 .
  • the thickness of the surface modification layer 3 is not particularly limited, it is preferably within the range of 0.1 to 20 nm from the viewpoint of the effects of the present invention.
  • step (B) and the next step (C) it is preferable to have a step of washing the metal-clad laminate 5 with the surface-modified layer 3 formed thereon. This allows removal of excess non-photosensitive surface modifiers that interact poorly with the metal layer.
  • step (C) a resist layer 4 containing a photosensitive resin is formed on the surface modified layer 3 (see FIG. 5). Since the laminate 6 in this state includes the metal layer 2, the surface modification layer 3 and the resist layer 4, it corresponds to the laminate of the present invention.
  • the resist layer 4 is not particularly limited as long as it contains a photosensitive resin that can be patterned by photolithography in the same manner as the resist layer of the laminate. can be formed by applying
  • step (D) the resist layer 4 is patterned by exposure and development (see FIG. 6). Specifically, by exposing the resist layer 4 using a photomask that can expose the resist layer 4 in an arbitrary pattern, and then dissolving and removing unnecessary portions of the resist layer 4 using a developer, Patterning. It is preferable to wash with water after development.
  • the exposure conditions and development conditions are not particularly limited, and conventionally known conditions can be applied.
  • step (E) the surface modification layer 3 and the metal layer 2 are etched through the resist layer 4 (see FIG. 7). Specifically, the surface modification layer 3 and the metal layer 2 are patterned by dissolving the surface modification layer 3 and the metal layer 2 in the portions where the resist layer 4 has been removed by wet etching using an etchant. .
  • the etching conditions are not particularly limited, and conventionally known conditions can be applied.
  • step (F) the resist layer 4 is peeled off from the metal-clad laminate 5 (see FIG. 8).
  • the surface-modified layer 3 is easily separated from the resist layer 4, so the surface-modified layer 3 is likely to remain on the metal layer 2 of the metal-clad laminate 5.
  • the surface modification layer 3 may remain on the metal layer 2 or may be peeled off together with the resist layer 4 .
  • the method for removing the resist layer 4 is not particularly limited, it is preferable to remove it using a remover.
  • the stripping liquid is not particularly limited, and conventionally known ones can be applied.
  • the metal wiring pattern 7 can be formed.
  • the method for forming a metal wiring pattern it is possible to form a high-density and high-definition metal wiring pattern. It becomes possible to manufacture the printed circuit board (printed wiring board) of the present invention.
  • the method for forming a laminate (printed circuit board laminate) according to the present invention is a method for forming a resin layer on a metal layer, wherein the non-photosensitive surface modifier of the present invention is used to form a metal layer and a resin layer. a step of forming a surface modified layer between The metal layer may be solid or patterned with wiring, and a known method such as hot pressing can be used as the lamination method.
  • the resin layer a commercially available resin film or prepreg (sheet-like fiber impregnated with liquid resin) can be used, and fluorine resin, cyclopolyolefin resin, liquid crystal polymer, epoxy resin, phenol resin, polyimide, bismaleimide resin, etc.
  • a resin containing a triazine resin, a modified polyphenylene ether, or a cyanate ester is preferably used, and surface treatment such as corona treatment or plasma treatment may be performed on the bonding surface of the resin layer before lamination.
  • Example 1 The orientation of each compound shown in Tables I and II below was evaluated. Specifically, quantum chemical calculation software Gaussian16 (manufactured by Gaussian) was used to perform structure optimization using B3LYP (density functional theory) in DFT calculation. As a basis function for copper, SDD (Stuttgart/Dresden ECP) was used for calculation, and 6-31G(d) was used for other elements. In the Grid scan module of the soft Material Science Suite manufactured by Schrodinger, the position where the copper ion is restabilized in the space around the ligand was set as the initial configuration.
  • Gaussian16 quantum chemical calculation software
  • B3LYP density functional theory
  • SDD Sttgart/Dresden ECP
  • Example 2 ⁇ Preparation of non-photosensitive surface modifier> Each compound in Table I below was added to a solvent consisting of 20% by mass of ethanol and 80% by mass of ion-exchanged water so as to be 20 ppm by mass, and non-photosensitive surface modifiers 1 to 8 and 12 to 15 were prepared, respectively. bottom. Further, for non-photosensitive surface modifiers 10 and 11, the ratio of ethanol and ion-exchanged water was changed as shown in Table I below. It was prepared in the same manner except that the concentration was changed as shown in Table I below.
  • a metal wiring pattern 1 was formed by performing the following steps (A) to (F).
  • Step (A) A copper clad laminate (Megtron 7 R-5785 manufactured by Panasonic Corporation) in which a metal layer is formed on an insulating layer is acid-cleaned using an acid cleaning solution (CP-30 manufactured by Sanwa Chemical Industry Co., Ltd.) and a spray-type cleaning device. and then washed with water.
  • an acid cleaning solution CP-30 manufactured by Sanwa Chemical Industry Co., Ltd.
  • Step (B) The non-photosensitive surface modifier 1 prepared above was applied onto the metal layer of the copper-clad laminate that had been acid-washed and water-washed using a spray-type applicator, and was then washed with water. After washing with water, water was removed with a PVA roller and dried with an air knife at 80° C. to form a surface modified layer with a thickness of 5 nm.
  • Step (C) A dry film resist (AK-4034 manufactured by Asahi Kasei Co., Ltd.) (a photocurable acrylic resin containing an alkali-soluble resin) was applied as a resin layer on the surface-modified layer by a hot roll laminator at a roll temperature of 105° C. and an air pressure of 0.5°C. A resist layer was formed by lamination under conditions of 35 MPa and a lamination speed of 1.5 m/min.
  • the dry film resist used (AK-4034 manufactured by Asahi Kasei Co., Ltd.) has a support made of a polyethylene terephthalate film on one side and a protective layer made of a polyethylene film on the other side. Lamination was carried out by allowing the surface on which the protective layer was present to adhere to the metal layer via the surface-modified layer while peeling off the protective layer.
  • Step (D) Using a chromium glass mask, the resist layer was exposed by a parallel light exposure machine (HMW-801 manufactured by ORC Co., Ltd.). As the exposure condition, 60 mj/cm 2 , which is the recommended condition for dry film resist, was adopted. The support was peeled off from the resist layer after exposure. After that, the unexposed portions of the resist layer are dissolved and removed at 30°C using a developer consisting of an aqueous solution of 1% by mass of sodium carbonate (Na 2 CO 3 ) and an alkaline developer, and then washed with water. Developed. The resist layer was patterned by the above operation.
  • a parallel light exposure machine HMW-801 manufactured by ORC Co., Ltd.
  • As the exposure condition 60 mj/cm 2 , which is the recommended condition for dry film resist, was adopted.
  • the support was peeled off from the resist layer after exposure. After that, the unexposed portions of the resist layer are dissolved and removed at 30°C using a
  • Step (E) In a dip method, using an etchant consisting of an aqueous solution of 2% by mass of hydrochloric acid (HCl) and 2% by mass of ferric chloride (FeCl 3 ), the surface was reformed under the conditions of a temperature of 30 ° C. and a dipping time of 1 minute. The quality layer and the metal layer were etched.
  • HCl hydrochloric acid
  • FeCl 3 ferric chloride
  • Step (F) The resist layer was stripped from the copper-clad laminate at a temperature of 50° C. using a stripping solution consisting of an aqueous solution of 3% by mass of sodium hydroxide (NaOH).
  • metal wiring patterns 2 to 15 were formed in the same manner except that the non-photosensitive surface modifier 1 was changed to each of the non-photosensitive surface modifiers 2 to 15 shown in Table I below. formed.
  • Example 3 ⁇ Preparation of non-photosensitive surface modifier>
  • Non-photosensitive surface modifiers 1-15 similar to Example 2 were prepared.
  • a printed circuit board laminate 1 was formed by carrying out the following steps (I) to (III).
  • Step (I) A copper clad laminate (R-1766 manufactured by Panasonic Corporation) in which a metal layer is formed on an insulating layer is acid-cleaned using an acid cleaning solution (CP-30 manufactured by Sanwa Chemical Industry Co., Ltd.) and a spray-type cleaning device, It was then washed with water.
  • an acid cleaning solution CP-30 manufactured by Sanwa Chemical Industry Co., Ltd.
  • Step (II) The non-photosensitive surface modifier 1 prepared above was applied onto the metal layer of the copper-clad laminate that had been acid-washed and water-washed using a spray-type applicator, and was then washed with water. After washing with water, water was removed with a PVA roller and dried with an air knife at 80° C. to form a surface modifier layer with a thickness of 5 nm.
  • Step (III) A prepreg (Panasonic R-1661) (epoxy resin) is laminated on the surface modifier layer, and the temperature is increased from room temperature (25 ° C.) to 10 ° C./min at a pressure of 3.0 MPa. was heated to 120° C. and held for 30 minutes, and heated to 190° C. at a rate of temperature increase of 10° C./min and held for 2 hours for lamination and adhesion, thereby fabricating a printed circuit board laminate 1 .
  • the heterocyclic compound contained in the non-photosensitive surface modifier of the present invention has a nitrogen atom and a phenolic hydroxy group in its structure that are diagonally opposite to each other. It can be seen that is coordinated in the vertical direction.
  • the resist adhesion and prepreg adhesion are improved as compared with the case of using the surface modifier of the comparative example. It is recognized that it is superior to
  • the present invention can be used for non-photosensitive surface modifiers, laminates, printed circuit boards, and electronic devices that can further improve the adhesion between a metal layer and a resin layer.

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PCT/JP2022/041485 2021-11-11 2022-11-08 非感光性表面改質剤、積層体、プリント基板及び電子デバイス WO2023085246A1 (ja)

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JPH05281722A (ja) * 1992-03-31 1993-10-29 Dainippon Toryo Co Ltd ネガ型感光性電着塗料樹脂組成物、これを用いた電着塗装浴及びレジストパターンの製造法
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JP2011515542A (ja) * 2008-03-21 2011-05-19 エントン インコーポレイテッド 多官能分子システムを用いた積層体への金属の接着促進
JP2017125226A (ja) * 2016-01-12 2017-07-20 ナガセケムテックス株式会社 無電解めっき用プライマー組成物、無電解めっき用プライマー部材及びめっき物
JP2018044241A (ja) * 2016-09-13 2018-03-22 ローム アンド ハース エレクトロニック マテリアルズ エルエルシーＲｏｈｍ ａｎｄ Ｈａａｓ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＬＬＣ 選択的な金属被覆のための遮断コーティング

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EP2871260B1 (en) * 2012-07-09 2019-03-06 Shikoku Chemicals Corporation Copper film-forming agent and method for forming copper film
JP6232605B2 (ja) 2016-05-10 2017-11-22 メック株式会社 被膜形成用組成物、表面処理金属部材の製造方法、および金属‐樹脂複合体の製造方法
JP6612485B1 (ja) 2018-03-27 2019-11-27 東京応化工業株式会社 めっき造形物の製造方法
US12091430B2 (en) * 2019-09-06 2024-09-17 Shikoku Chemicals Corporation Metal surface treatment liquid and liquid concentrate thereof, metal surface treatment liquid set, metal surface treatment method, and method for manufacturing printed wiring board

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04314895A (ja) * 1991-04-15 1992-11-06 Nikko Kyodo Co Ltd 表面処理液及び方法
JPH05281722A (ja) * 1992-03-31 1993-10-29 Dainippon Toryo Co Ltd ネガ型感光性電着塗料樹脂組成物、これを用いた電着塗装浴及びレジストパターンの製造法
JPH0853427A (ja) * 1994-07-27 1996-02-27 Ciba Geigy Ag 赤色側にシフトされたトリス−アリール−ｓ−トリアジンおよびそれらにより安定化された組成物
JP2011515542A (ja) * 2008-03-21 2011-05-19 エントン インコーポレイテッド 多官能分子システムを用いた積層体への金属の接着促進
JP2017125226A (ja) * 2016-01-12 2017-07-20 ナガセケムテックス株式会社 無電解めっき用プライマー組成物、無電解めっき用プライマー部材及びめっき物
JP2018044241A (ja) * 2016-09-13 2018-03-22 ローム アンド ハース エレクトロニック マテリアルズ エルエルシーＲｏｈｍ ａｎｄ Ｈａａｓ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＬＬＣ 選択的な金属被覆のための遮断コーティング

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