WO2023286872A1 - 積層体および積層体を備えた電子機器 - Google Patents

積層体および積層体を備えた電子機器 Download PDF

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Publication number
WO2023286872A1
WO2023286872A1 PCT/JP2022/027941 JP2022027941W WO2023286872A1 WO 2023286872 A1 WO2023286872 A1 WO 2023286872A1 JP 2022027941 W JP2022027941 W JP 2022027941W WO 2023286872 A1 WO2023286872 A1 WO 2023286872A1
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Prior art keywords
resin
primer layer
layer
laminate
compound
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PCT/JP2022/027941
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English (en)
French (fr)
Japanese (ja)
Inventor
雅弘 滝澤
陽祐 広田
亘 冨士川
潤 白髪
Original Assignee
太陽インキ製造株式会社
Dic株式会社
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Application filed by 太陽インキ製造株式会社, Dic株式会社 filed Critical 太陽インキ製造株式会社
Priority to CN202280042830.3A priority Critical patent/CN117561164A/zh
Priority to KR1020237043520A priority patent/KR20240037880A/ko
Publication of WO2023286872A1 publication Critical patent/WO2023286872A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • 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
    • B32B15/092—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 comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09D171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C09D171/12—Polyphenylene oxides
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives

Definitions

  • the present invention relates to laminates, and more particularly to laminates that can be suitably used in electronic devices such as electromagnetic wave shields, printed wiring boards, integrated circuits, and organic transistors, and electronic devices using the laminates.
  • FCCL flexible copper-clad laminate
  • Patent Document 2 discloses that inorganic nanoparticles and a phthalocyanine-based ligand are used as a plating underlayer provided between a support and a metal plating layer. It has been proposed to improve the adhesion between the support and the plating layer by using a composition containing a solvent (dispersion medium). Further, in Patent Document 3, a layer containing a compound having an aminotriazine ring is provided as a primer layer on a support, and a metal nanoparticle layer is provided on the primer layer, whereby the support and the metal plating layer are formed.
  • Patent Document 4 a metal particle layer containing metal particles and a reaction product of a specific epoxy compound and a blocked polyisocyanate is interposed between the support and the plating layer, thereby It has been proposed that the adhesion to is improved.
  • an object of the present invention is to provide a laminate that can maintain the adhesion of the plating layer not only in normal conditions but also after a long-term heat resistance test.
  • the present inventors have found that by using a high-molecular-weight phenoxy resin in the primer layer, the elongation of the primer layer is increased and the elastic modulus is improved, so that the plating immediately after plating (normal state) It has been found that the layer adhesion can be improved.
  • a high-molecular-weight phenoxy resin by using a high-molecular-weight phenoxy resin, deterioration such as decomposition of the polymer in the primer layer is suppressed during the long-term heat resistance test, so that the adhesion of the plating layer can be maintained even after the long-term heat resistance test. I have learned that I can.
  • the present invention has been completed based on such findings. That is, the gist of the present invention is as follows.
  • a laminate comprising a support, a primer layer, a metal particle layer and a metal plating layer on the support in this order, wherein the primer layer has a weight average molecular weight of 10,000 to 100,000.
  • the primer layer further contains an epoxy resin.
  • the primer layer contains the phenoxy resin and the epoxy resin in a mass ratio of 90:10 to 10:90.
  • the present invention in a laminate sequentially comprising a support, a primer layer, a metal particle layer, and a metal plating layer, by using a phenoxy resin having a weight average molecular weight of 10,000 to 100,000 as the primer layer, the adhesion of the metal plating layer can be maintained not only in the normal state but also after the long-term heat resistance test.
  • a laminate according to the present invention comprises a support and, on the support, a primer layer, a metal particle layer and a metal plating layer in this order. Each element constituting the laminate of the present invention will be described below.
  • any material can be used without particular limitation as long as it has mechanical strength that allows successive lamination of a primer layer, a metal particle layer, and a metal plating layer, which will be described later.
  • Examples include polyimide resin and polyamide.
  • Imid resin polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polycarbonate resin, acrylonitrile-butadiene-styrene (ABS) resin, polystyrene, cycloolefin polymer, liquid crystal polymer, polyether ether ketone, polyphenylene sulfide resin , acrylic resins such as polyphenylsulfone, polyphenylene ether, polymethyl(meth)acrylate, polyvinylidene fluoride resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polyethylene resin, polypropylene resin, urethane resin, silicon, Silicon carbide, gallium nitride, sapphire, ceramics, glass, glass epoxy resin, glass polyimide, paper phenol, diamond-like carbon, alumina, polyester fiber, polyamide fiber, synthetic fiber such as polyaramid fiber, inorganic fiber such as
  • a base material made of synthetic fibers such as polyester fibers, polyamide fibers, aramid fibers, etc., natural fibers such as cotton, hemp, etc. can be used.
  • the fibers may be processed in advance.
  • the support is preferably made of a flexible resin material in order to impart flexibility to the laminate and obtain a bendable final product. Specifically, it is preferably in the form of a film or sheet formed by uniaxial or biaxial stretching.
  • film-like or sheet-like supports include polyimide film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film and the like.
  • the thickness is not particularly limited. More preferably 1 to 200 ⁇ m.
  • the surface of the support may, if necessary, have fine irregularities that do not lose its smoothness, or may have functional groups such as hydroxyl, carbonyl, and carboxyl groups.
  • the primer layer has the function of improving the adhesion between the support and the metal particle layer described later.
  • the primer layer contains, as an essential component, a phenoxy resin having a weight average molecular weight in the range of 10,000 to 100,000.
  • a high-molecular-weight phenoxy resin in the primer layer by using a high-molecular-weight phenoxy resin in the primer layer, the elongation of the polymer is improved, and furthermore the elastic modulus is improved, thereby improving the adhesion between the support and the metal plating layer. can.
  • the use of a high-molecular-weight phenoxy resin can suppress deterioration such as decomposition of the polymer due to heat during the long-term heat resistance test, so the adhesion of the metal plating layer can be maintained even after the long-term heat resistance test.
  • a phenoxy resin is a polyhydroxy polyether obtained by reacting a dihydric phenol compound and epichlorohydrin or by reacting a dihydric epoxy compound and a dihydric phenol compound.
  • dihydric phenol compounds include bisphenols.
  • phenoxy resins include phenoxy resins having a bisphenol A structure (skeleton), phenoxy resins having a bisphenol F structure, phenoxy resins having a bisphenol S structure, phenoxy resins having a bisphenol M structure, phenoxy resins having a bisphenol P structure, Examples include phenoxy resins having a bisphenol Z structure.
  • phenoxy resins having a skeletal structure such as a novolac structure, anthracene structure, fluorene structure, dicyclopentadiene structure, norbornene structure, naphthalene structure, biphenyl structure, and adamantane structure are also included. These phenoxy resins may be used singly or in combination of two or more. Among these, those having a bisphenol structure are preferred, and bisphenol A skeleton, bisphenol F skeleton, and bisphenol S skeleton are more preferred. Moreover, the terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.
  • the weight average molecular weight of the phenoxy resin used in the present invention is in the range of 10,000 to 100,000. If the molecular weight is 10,000 or more, the plating adhesion after a long-term heat resistance test will be high. Since the viscosity of the working fluid becomes appropriate, the handling is improved.
  • the weight average molecular weight of the phenoxy resin is preferably 20,000-50,000, more preferably 22,000-50,000.
  • the weight average molecular weight of the phenoxy resin can be adjusted by the molar ratio of the epoxy resin and the phenol resin and the reaction time in the above reaction. In addition, in this specification, the weight average molecular weight employ
  • a high-speed GPC device (HLC-8420GPC, manufactured by Tosoh Corporation) is used as a measurement device, and columns TSKgelG5000HxL / G4000HxL / G3000HxL / G2000HxL (manufactured by Tosoh Corporation) are used in series and used for elution. Tetrahydrofuran was used as a liquid, and the measurement was performed using an RI detector.
  • phenoxy resin generally means a high molecular weight epoxy resin. It shall be distinguished from resin.
  • phenoxy resins may be used, for example, Mitsubishi Chemical Corporation 1256, 4250 (both bisphenol A skeleton-containing phenoxy resins), 4275 (bis A/bis F mixed type), YL6794, YL7213, YL7290, YL7482, YL7553, YX8100 (phenoxy resin containing bisphenol S skeleton), X6954 (phenoxy resin containing bisphenolacetophenone skeleton, YX7200 (phenoxy resin containing cyclohexane skeleton), YP-70 (bisphenol F-type phenoxy resin), ZX-1356-2 (phenoxy resin containing bisphenol A and bisphenol F skeleton), YPB-40PXM40 (bromine-containing phenoxy resin), ERF-001M30 (phosphorus-containing phenoxy resin), FX-280, FX-293 , FX-310 (fluorene skeleton-containing phenoxy resin), PKHA, PKHB, PKHB+,
  • the primer layer preferably contains an epoxy resin in combination with the phenoxy resin described above.
  • the combined use of the phenoxy resin and the epoxy resin further improves the adhesion of the metal plating layer under normal conditions and after the long-term heat resistance test.
  • Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol A novolak type epoxy resin, alcohol ether type epoxy resin, tetrabromobisphenol.
  • epoxy resin to be used in combination with the phenoxy resin bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, cresol novolac type epoxy resin, and phenol novolac type epoxy resin can be used because they can further improve the adhesion of the metal plating layer.
  • Aromatic epoxy resins such as bisphenol A novolac type epoxy resins are preferred, and bisphenol A type epoxy resins are particularly preferred.
  • the epoxy equivalent of the epoxy resin is preferably 100 to 5,000 g/equivalent, more preferably 120 to 2,000 g/equivalent, and 120 to 250 g/equivalent, because it can further improve adhesion. is more preferred.
  • the mixing ratio of the phenoxy resin and the epoxy resin is preferably 90:10 to 10:90, preferably 85:15 to 15:10 by mass. 80 is more preferred.
  • the primer layer preferably contains a compound having an aminotriazine ring.
  • a compound having an aminotriazine ring may be a low molecular weight compound or a higher molecular weight compound such as a resin.
  • Various additives having an aminotriazine ring can be used as the low-molecular-weight compound having an aminotriazine ring.
  • Commercially available products include VT, VD-3 and VD-4 (all of which are from Shikoku Kasei Co., Ltd.), which are compounds having an aminotriazine ring and a hydroxyl group, and VD-5 (which is a compound having an aminotriazine ring and an ethoxysilyl group). Shikoku Kasei Co., Ltd.) and the like. These may be used individually by 1 type, and may be used together 2 or more types.
  • the amount of the low-molecular-weight compound having an aminotriazine ring is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the resin component.
  • resins having aminotriazine rings include resins in which aminotriazine rings are covalently introduced into the polymer chain of the resin. Specifically, an aminotriazine-modified novolak resin is preferred.
  • Aminotriazine-modified novolak resin is a novolac resin in which an aminotriazine ring structure and a phenol structure are bonded via a methylene group.
  • Aminotriazine-modified novolak resins are prepared, for example, by combining aminotriazine compounds such as melamine, benzoguanamine and acetoguanamine; In the presence or absence of a weakly alkaline catalyst, a co-condensation reaction is carried out near neutrality, or an alkyl etherified product of an aminotriazine compound such as methyl-etherified melamine is reacted with a phenol compound.
  • the aminotriazine-modified novolac resin preferably has substantially no methylol groups.
  • the aminotriazine-modified novolac resin may also contain molecules in which only the aminotriazine structure is methylene-bonded, molecules in which only the phenol structure is methylene-bonded, and the like, which are produced as by-products during the production of the aminotriazine-modified novolac resin. In addition, it may contain some unreacted raw materials.
  • Phenolic structures include, for example, phenol residues, cresol residues, butylphenol residues, bisphenol A residues, phenylphenol residues, naphthol residues, resorcin residues, and the like.
  • the term "residue” as used herein means a structure in which at least one hydrogen atom bonded to a carbon atom of an aromatic ring is removed.
  • phenol means a hydroxyphenyl group.
  • triazine structures include structures derived from aminotriazine compounds such as melamine, benzoguanamine, and acetoguanamine.
  • the phenol structure and triazine structure may be used singly or in combination of two or more. Further, the phenol structure is preferably a phenol residue, and the triazine structure is preferably a melamine-derived structure, since the adhesion can be further improved.
  • the hydroxyl value of the aminotriazine-modified novolac resin is preferably 50 to 200 mgKOH/g, more preferably 80 to 180 mgKOH/g, because it can further improve adhesion.
  • the aminotriazine-modified novolak resin may be used singly or in combination of two or more.
  • the phenolic hydroxyl group (x) in the aminotriazine-modified novolak resin and the epoxy group (y) in the epoxy resin is preferably in the range of 0.1-5, more preferably in the range of 0.2-3.
  • the primer layer may further contain a cross-linking agent, if necessary, in addition to the epoxy resin and the compound having an aminotriazine ring described above.
  • a cross-linking agent it is preferable to use a polyvalent carboxylic acid.
  • polycarboxylic acids include trimellitic anhydride, pyromellitic anhydride, maleic anhydride, and succinic acid.
  • These crosslinking agents may be used individually by 1 type, and may use 2 or more types together. Among these cross-linking agents, trimellitic anhydride is preferable because it can further improve adhesion.
  • a curing catalyst may also be used to promote the reaction between the epoxy group and various curing agents.
  • the curing catalyst include tertiary amines, imidazole compounds, organic phosphines, and Lewis acid catalysts.
  • Tertiary amines include, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, trioctylamine, trilaurylamine, dimethylethylamine, dimethylpropylamine, dimethylbutylamine, dimethylamylamine, dimethylhexylamine, dimethylcyclohexylamine, dimethyloctylamine, dimethyllaurylamine, triallylamine, tetramethylethylenediamine, triethylenediamine (triethylenetetramine: TETA), N-methylmorpholine, 4,4'-(oxydi-2,1 -ethanediyl)bis-morpholine, N,N-dimethylbenzylamine, pyridine, picoline, dimethylaminomethylphenol, trisdimethylaminomethylphenol, triethanolamine, N,N'-dimethylpiperazine, tetramethylbutanediamine
  • imidazole compounds include 1-benzyl-2-imidazole (1B2MZ), 2-ethyl-4-imidazole, 2-undelimidazole, 1,2-dimethylimidazole, 1-benzyl-2-phenylimidazole, 2- Methylimidazole, 2-ethyl-4-methylimidazole (2E4MZ), 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P4MHZ), 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole (TBZ) and the like.
  • organic phosphines examples include triphenylphosphine (TPP), triphenylphosphine-triphenylborate, tris(p-methoxyphenyl)phosphine, tetraphenylphosphonium/tetraphenylborate, and the like.
  • Lewis acid catalysts include Lewis acid catalysts such as boron trifluoride amine complexes, boron trichloride amine complexes, and boron trifluoride ethylamine complexes.
  • these curing catalysts it is preferable to use tertiary amines and imidazole compounds, and more preferably to use imidazole compounds, because the adhesion can be further improved.
  • these curing catalysts can be used alone or in combination of two or more.
  • the preferred amount of the curing catalyst is 0.3 to 20 parts by mass, preferably 0.5 to 15 parts by mass, based on the total amount of 100 parts by mass of all the resins contained in the primer layer, in terms of solid content. part is more preferred.
  • the primer layer may contain other resins as components other than those described above, if necessary.
  • Other resins include, for example, urethane resins, acrylic resins, imide resins, amide resins, melamine resins, phenol resins, urea-formaldehyde resins, blocked polyisocyanates using phenol as a blocking agent, polyvinyl alcohol, polyvinylpyrrolidone, and the like. be done.
  • These binder resins may be used individually by 1 type, and may use 2 or more types together.
  • organic solvent examples include toluene, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isopropyl alcohol.
  • the amount of the organic solvent used can be appropriately adjusted according to the coating method used when coating the support and the desired thickness of the primer layer.
  • the coating solution for forming the primer layer may contain known additives such as film-forming aids, leveling agents, thickeners, water repellents, antifoaming agents, antioxidants, etc., as necessary. You may add and use it.
  • the primer layer can be formed by applying a coating liquid containing the above-described components to part or all of the surface of the support, and removing the organic solvent contained in the coating liquid by heating or drying. .
  • the coating method is not particularly limited, and conventionally known coating methods can be applied. Examples thereof include gravure, coating, screen, roller, rotary, spray, and capillary methods. .
  • the method for removing the organic solvent contained in the coating film is generally, for example, drying with a dryer to volatilize the organic solvent.
  • the drying temperature may be set within a range in which the organic solvent used can be volatilized and the support is not adversely affected by heat deformation or the like.
  • the thickness of the primer layer may be appropriately adjusted depending on the use of the laminate of the present invention, but it is preferably within a range that further improves the adhesion between the support and the metal particle layer described later, and the thickness of the primer layer is 10 nm. It is preferably ⁇ 1 ⁇ m, more preferably 10 nm to 500 nm. The thickness of the primer layer can be adjusted by the amount of the coating liquid applied to the support.
  • the surface of the primer layer may be treated, if necessary, by a plasma discharge treatment method such as a corona discharge treatment method, a dry treatment method such as an ultraviolet treatment method, water or an acidic or alkaline chemical solution.
  • a plasma discharge treatment method such as a corona discharge treatment method, a dry treatment method such as an ultraviolet treatment method, water or an acidic or alkaline chemical solution.
  • the surface treatment may be performed by a wet treatment method using an organic solvent or the like.
  • the metal particle layer is provided on the primer layer described above, and is a layer provided for forming the metal plating layer described later.
  • the metal particle layer is preferably a layer containing a composite of metal particles and an organic compound.
  • the metal particle layer more preferably contains metal particles and a compound having a cationic group.
  • the metals that make up the metal particles include transition metals and their compounds, and among these, ionic transition metals are preferred.
  • ionic transition metals include copper, silver, gold, nickel, palladium, platinum, cobalt, etc. From the viewpoint of formability of the metal plating layer described later, silver is preferable.
  • the term "metal particles" refers to particulate or fibrous particles made of the metals described above.
  • the average particle diameter is preferably 1 to 100 nm, more preferably 1 to 50 nm, from the viewpoint of further reducing the resistance value.
  • the average particle diameter means the volume average value (D50) measured by the dynamic light scattering method after diluting the metal particles with a good dispersion solvent.
  • the fiber diameter is preferably 5 to 100 nm, more preferably 5 to 50 nm, from the viewpoint of further reducing the resistance value.
  • the fiber length is preferably 0.1 to 100 ⁇ m, more preferably 0.1 to 30 ⁇ m.
  • a compound having a cationic group can be preferably used as the organic compound used in combination with the metal particles.
  • the compound having a cationic group disperses the metal particles satisfactorily, and reacts with the functional groups contained in the components of the primer layer, such as the epoxy groups contained in the epoxy resin, to form the primer layer and the metal particle layer. It is preferable in that it has a function of further improving the adhesion of the interface.
  • the compound having a cationic group may be a surface-treated metal particle contained in the metal particle layer.
  • a compound having a basic nitrogen atom-containing group can be preferably used.
  • polyalkyleneimine such as polyethyleneimine and polypropyleneimine, a compound obtained by adding polyoxyalkylene to polyalkyleneimine, and the like are used. can do.
  • a compound in which polyoxyalkylene is added to polyalkyleneimine is preferable because it can improve the water dispersion stability of metal particles.
  • polyoxyalkylene for example, a random structure or block structure such as polyoxyethylene and poly(oxyethylene-oxypropylene) can be used.
  • polyoxyalkylene it is preferable to use one having an oxyethylene unit from the viewpoint of the water dispersion stability of the metal particles. It is preferred to use the one with
  • polyoxyalkylene for example, a compound having a structure composed of polyethyleneimine and a polyoxyalkylene structure such as a polyethylene oxide structure can be used.
  • the polyethyleneimine and the polyoxyalkylene may be linearly bonded, or may be a main chain composed of polyethyleneimine and a side chain grafted with the polyoxyalkylene.
  • polyalkyleneimine examples include a copolymer of polyethyleneimine and polyoxyethylene, a part of the imino groups present in the main chain, and ethylene oxide.
  • a compound or the like obtained by the reaction can be used. They preferably have a block structure.
  • polyoxyalkylene As the compound in which polyoxyalkylene is added to polyalkyleneimine, those obtained by reacting the amino group of polyalkyleneimine, the hydroxyl group of polyoxyethylene glycol, and the epoxy group of epoxy resin are used. You can also
  • polyalkyleneimine commercially available products may be used. 1000 (above, Nippon Shokubai Co., Ltd.) can be used.
  • the metal particle layer may contain an epoxy resin in addition to the metal particles described above.
  • the epoxy resin the same one as described in the primer layer can be used.
  • the epoxy resin Aliphatic epoxy resins are preferably used, and alicyclic epoxy resins are more preferably used, from the viewpoint of suppressing reaction with a compound having a basic nitrogen atom-containing group.
  • aliphatic epoxy resins include neopentyl glycol diglycidyl ether, dimethylolcyclohexanediglycidyl ether, 1,4-cyclohexanediglycidyl ether, 1,3-cyclohexanediglycidyl ether, 1,2-cyclohexanediglycidyl ether, Acyclic fatty acids such as dimethylol dicyclopentadiene diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hexahydroterephthalic acid diglycidyl ester, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether group epoxy resins, 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, ⁇ -caprolactone-modified 3′,4′-epoxycyclohexy
  • alicyclic epoxy resins are preferred, particularly from the viewpoint of the suppression of reaction with compounds having basic nitrogen atom-containing groups in the metal particle layer-forming coating solution and the compatibility with solvents described later.
  • 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and ⁇ -caprolactone-modified 3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate can be preferably used.
  • the metal particle layer is formed by dissolving or dispersing the above components in an appropriate solvent to prepare a coating solution, coating the primer layer to form a coating film, and drying the coating film to remove the solvent. can be formed.
  • Solvents used in the coating solution for forming the metal particle layer include aqueous media such as distilled water, ion-exchanged water, pure water, and ultrapure water, as well as organic solvents such as alcohols, ethers, esters, and ketones. can do.
  • alcohols examples include methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butanol, tert-butanol, heptanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol.
  • pentadecanol stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, terpineol, dihydroterpineol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, Tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol Monobutyl ether and the like can be used.
  • the coating liquid can be used in combination with ketone solvents such as acetone, cyclohexanone, and methyl ethyl ketone to adjust physical properties.
  • ketone solvents such as acetone, cyclohexanone, and methyl ethyl ketone to adjust physical properties.
  • ester solvents such as ethyl acetate, butyl acetate, 3-methoxybutyl acetate, 3-methoxy-3-methyl-butyl acetate, etc.
  • hydrocarbon solvents such as toluene, especially hydrocarbon solvents having 8 or more carbon atoms can be used. can be done.
  • Hydrocarbon solvents having 8 or more carbon atoms include nonpolar solvents such as octane, nonane, decane, dodecane, tridecane, tetradecane, cyclooctane, xylene, mesitylene, ethylbenzene, dodecylbenzene, tetralin, and trimethylbenzenecyclohexane. can also be used in combination depending on the Furthermore, mixed solvents such as mineral spirit and solvent naphtha can be used together.
  • nonpolar solvents such as octane, nonane, decane, dodecane, tridecane, tetradecane, cyclooctane, xylene, mesitylene, ethylbenzene, dodecylbenzene, tetralin, and trimethylbenzenecyclohexane.
  • mixed solvents such as mineral spirit and solvent naphtha can be used together.
  • solvents include, for example, 2-ethyl 1,3-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,4-butanediol, 2,3-butanediol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ether acetate, diethylene glycol monobutyl ether acetate and the like can be used.
  • the coating solution for forming the metal particle layer may contain surfactants, antifoaming agents, rheology modifiers, and the like as necessary from the viewpoint of improving the wettability and the like when applied to the primer layer. good.
  • the content of the metal particles contained in the coating solution for forming the metal particle layer is preferably 1 to 90% by mass, more preferably 5 to 60% by mass, more preferably 10% by mass, based on the total coating solution. More preferably, it is up to 40% by mass.
  • the content of the compound having a cationic group is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, relative to the entire coating liquid.
  • the epoxy resin is preferably contained in the metal particle layer in an amount of 0.01 to 10% by mass. , more preferably 0.05 to 5% by mass.
  • the metal particle layer may be a layer provided on the entire surface of the primer layer, or may be a layer provided on part of the surface of the primer layer.
  • a fine line-shaped layer formed by drawing lines on the surface of the primer layer can be mentioned.
  • the fine line-shaped layer is suitable when the laminate according to the present invention is used for a printed wiring board or the like.
  • the width (line width) of the fine line-shaped layer (pattern) is generally about 0.01 to 200 ⁇ m, preferably about 0.01 to 150 ⁇ m.
  • the metal particle layer preferably has a thickness of 0.01 to 100 ⁇ m in order to form a conductive pattern with low resistance and excellent conductivity. Further, when the metal particle layer is in the form of thin wires, its thickness (height) is preferably in the range of 0.05 to 50 ⁇ m. The thickness of the metal particle layer can be adjusted by the amount of the coating liquid applied to the primer layer.
  • Examples of methods for applying the metal particle layer-forming coating solution to the primer layer include reverse printing such as letterpress reverse printing, inkjet printing, screen printing, offset printing, gravure printing, and spin coating. , a spray coating method, a bar coating method, a die coating method, a slit coating method, a roll coating method, a dip coating method, and the like.
  • reverse printing such as letterpress reverse printing, inkjet printing, screen printing, offset printing, gravure printing, and spin coating.
  • a spray coating method a bar coating method, a die coating method, a slit coating method, a roll coating method, a dip coating method, and the like.
  • inkjet printing method In the case of applying (printing) thin lines of approximately 0.01 to 100 ⁇ m, which is required when realizing high density electronic circuits, it is preferable to adopt an inkjet printing method.
  • the metal plating layer constituting the laminate of the present invention has a reliability that can maintain good conductivity without causing disconnection or the like for a long period of time, for example, when the laminate is used for a printed wiring board, an electromagnetic wave shield, or the like. This layer is provided for the purpose of forming a wiring pattern with a high density.
  • the metal plating layer is a layer formed on the metal particle layer described above, and the method of forming it is preferably a method of forming by plating.
  • the plating treatment include wet plating methods such as electroplating and electroless plating, which can easily form a metal plating layer. Also, two or more of these plating methods may be combined. For example, after performing electroless plating, electroplating may be performed to form a metal plating layer.
  • electroless plating method for example, by bringing an electroless plating solution into contact with the metal that constitutes the metal particle layer, a metal such as copper contained in the electroless plating solution is deposited to form an electroless plating layer consisting of a metal coating.
  • electroless plating solutions include those containing metals such as copper, silver, gold, nickel, chromium, cobalt and tin, reducing agents, and solvents such as aqueous media and organic solvents.
  • reducing agents include dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, and phenol.
  • monocarboxylic acids such as acetic acid and formic acid
  • dicarboxylic acid compounds such as malonic acid, succinic acid, adipic acid, maleic acid and fumaric acid
  • malic acid lactic acid, glycolic acid and gluconate hydroxycarboxylic acid compounds such as acid and citric acid
  • amino acid compounds such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid, and glutamic acid
  • Organic acids such as carboxylic acid compounds, soluble salts of these organic acids (sodium salts, potassium salts, ammonium salts, etc.), complexing agents such as amine compounds such as ethylenediamine, diethylenetriamine, and triethylenetetramine are used. be able to.
  • the metal forming the metal particle layer or the surface of the electroless plated layer (coating) formed by the electroless treatment is energized while the electrolytic plating solution is in contact with the electroplating.
  • a metal such as copper contained in a liquid is deposited on the surface of the metal particles constituting the metal particle layer placed on the cathode or on the surface of the electroless plated layer formed by electroless treatment to form an electrolytic plated layer.
  • electrolytic plating solutions examples include those containing sulfides of metals such as copper, nickel, chromium, cobalt, and tin, sulfuric acid, and an aqueous medium. Specific examples include those containing copper sulfate, sulfuric acid, and an aqueous medium.
  • the method of electroplating after electroless plating is preferable because it is easy to control the thickness of the metal plating layer to a desired thickness from a thin film to a thick film.
  • the film thickness of the metal plating layer is preferably 1 to 50 ⁇ m.
  • the film thickness of the metal plating layer can be adjusted by controlling the treatment time, current density, amount of plating additive used, etc. in the plating process for forming the metal plating layer.
  • the metal plating layer formed on the surface does not peel off under normal conditions, and even when placed at a high temperature of 150 ° C. for a long time, the adhesion of the metal plating layer is maintained. maintained. Therefore, formation of circuit forming substrates used for electronic circuits, integrated circuits, etc., formation of peripheral wiring constituting organic solar cells, electronic book terminals, organic EL, organic transistors, flexible printed circuit boards, RFID, etc., plasma display It can be suitably used for applications in which durability is particularly required, such as wiring for electromagnetic shielding.
  • the conductive pattern subjected to the plating treatment can form a highly reliable wiring pattern that can maintain good conductivity without causing disconnection or the like for a long period of time. It can be used for electronic equipment applications such as FPC) and electromagnetic wave shielding.
  • a laminate in which a primer layer, a metal particle layer and a metal plating layer are sequentially provided on one surface of a support has been described as an example.
  • a layered product may also be formed in which a primer layer, a metal particle layer and a metal plating layer are sequentially provided on the opposite side of the body.
  • Phenoxy Resin (P-1) 100 mass of bisphenol A type epoxy resin (Epiclon EXA-850CRP manufactured by DIC Corporation, solid content 100%, epoxy equivalent 173 g/eq) was placed in a reactor equipped with a stirrer, thermometer, nitrogen blowing tube, and cooling tube.
  • Preparation Example 1 Preparation of Primer Layer Forming Coating Solution (1)
  • the phenoxy resin (P-1) obtained in Synthesis Example 1 was diluted with cyclohexanone so that the nonvolatile content was 2% by mass, and mixed uniformly to obtain a primer layer forming coating solution (1). got
  • Novolak resin B (DIC Corporation "PHENOLITE TD-2131", hydroxyl equivalent 104 g / equivalent) 3 parts by mass, and Shikoku Kasei Co., Ltd. as a curing catalyst 1 "TBZ" 0.5 parts by mass were mixed, and cyclohexanone was mixed. was used to dilute the non-volatile matter to 2% by mass, and mixed uniformly to obtain a primer layer-forming coating liquid (4).
  • Preparation Example 5 Preparation of primer layer-forming coating liquid (5)] 267 parts by mass of the phenoxy resin (P-2) obtained in Synthesis Example 2, and 60 parts by mass of epoxy resin A ("EPICLON 850-S" manufactured by DIC Corporation; bisphenol A type epoxy resin, epoxy group equivalent: 188 g/equivalent). , And, as a curing catalyst 1, 0.5 parts by mass of “TBZ” manufactured by Shikoku Kasei Co., Ltd. is mixed, diluted with cyclohexanone so that the nonvolatile content is 2% by mass, and mixed uniformly to form a primer layer. A forming coating liquid (5) was obtained.
  • Preparation Example 6 Preparation of primer layer-forming coating solution (6)] 133 parts by mass of the phenoxy resin (P-2) obtained in Synthesis Example 1, and 70 parts by mass of epoxy resin A ("EPICLON 850-S" manufactured by DIC Corporation; bisphenol A type epoxy resin, epoxy group equivalent: 188 g/equivalent). , 10 parts by mass of the modified novolak resin C obtained in Synthesis Example 4, and 5 parts by mass of "2E4MZ" manufactured by Shikoku Kasei Co., Ltd. as a curing catalyst 2, are mixed, and cyclohexanone is used so that the nonvolatile content is 2% by mass. By diluting and mixing uniformly, a primer layer-forming coating liquid (6) was obtained.
  • Preparation Example 7 Preparation of primer layer-forming coating liquid (7)] 67 parts by mass of the phenoxy resin (P-3) obtained in Synthesis Example 3, and 76 parts by mass of epoxy resin A ("EPICLON 850-S" manufactured by DIC Corporation; bisphenol A type epoxy resin, epoxy group equivalent: 188 g/equivalent). , Novolak resin B (DIC Corporation "PHENOLITE TD-2131", hydroxyl equivalent 104 g / equivalent) 14 parts by weight, and Shikoku Kasei Co., Ltd. as curing catalyst 1 "TBZ" 0.5 parts by weight were mixed, and cyclohexanone was mixed. was used to dilute the non-volatile matter to 2% by mass, and mixed uniformly to obtain a primer layer-forming coating liquid (7).
  • Preparation Example 8 Preparation of Primer Layer Forming Coating Solution (8)
  • modified novolak resin C obtained in Synthesis Example 4
  • epoxy resin A (“EPICLON 850-S” manufactured by DIC Corporation; bisphenol A type epoxy resin, epoxy group equivalent weight: 188 g/equivalent)
  • the mixed resin solution of the aminotriazine-modified novolac resin and the epoxy resin was obtained by diluting with methyl ethyl ketone so that the non-volatile content was 2% by mass and mixing uniformly.
  • chloroform (30 ml) containing 9.6 parts by weight of p-toluenesulfonyl chloride was added to a mixture containing 20 parts by weight of methoxypolyethylene glycol (number average molecular weight of 2,000), 8.0 parts by weight of pyridine and 20 ml of chloroform.
  • the solution was added dropwise for 30 minutes with ice-cooling and stirring, then stirred at a bath temperature of 40° C. for 4 hours, and mixed with 50 ml of chloroform.
  • the obtained product is washed with 100 ml of 5% by mass hydrochloric acid aqueous solution, then with 100 ml of saturated sodium bicarbonate aqueous solution, then with 100 ml of saturated saline solution, dried with anhydrous magnesium sulfate, and filtered. , concentrated under reduced pressure, washed several times with hexane, filtered and dried at 80° C. under reduced pressure to obtain methoxypolyethylene glycol having a p-toluenesulfonyloxy group.
  • a mixed solvent of 200 ml of isopropyl alcohol and 200 ml of hexane was added to the resulting silver dispersion, and after stirring for 2 minutes, centrifugal concentration was performed at 3000 rpm for 5 minutes. After removing the supernatant, a mixed solvent of 50 ml of isopropyl alcohol and 50 ml of hexane was added to the precipitate, stirred for 2 minutes, and concentrated by centrifugation at 3000 rpm for 5 minutes. After removing the supernatant, 20 parts by mass of water was added to the precipitate, and the mixture was stirred for 2 minutes to remove the organic solvent under reduced pressure.
  • the obtained powder of cationic silver particles is dispersed in a mixed solvent of 45 parts by mass of ethylene glycol and 55 parts by mass of deionized water to form a metal particle layer containing 5% by mass of cationic silver particles.
  • a coating solution was prepared.
  • each primer layer forming coating solution (1) to (8) obtained above is applied to a desktop small coater ( Using a K printing prober (RK Print Coat Instrument Co., Ltd.), coating was performed so that the coating thickness after drying was 300 nm. Then, a primer layer was formed on the surface of the polyimide film by drying at 155° C. for 5 minutes using a hot air dryer.
  • the coating solution for forming a metal particle layer obtained above was applied to the surface of the primer layer using a bar coater so that the coating thickness after drying was 100 nm.
  • a metal particle layer was then formed by drying at 140° C. for 5 minutes.
  • the metal particle layer formed as described above is set on the cathode side, the phosphorous copper is set on the anode side, and electrolytic plating is performed for 18 minutes at a current density of 2 A/dm 2 using an electrolytic plating solution containing copper sulfate.
  • a copper plating layer (film thickness: 8 ⁇ m) was formed on the metal particle layer.
  • As an electrolytic plating solution 70 g/L of copper sulfate, 200 g/L of sulfuric acid, 50 mg/L of chloride ion, and 5 ml/L of additive (Top Lucina SF-M, Okuno Chemical Industry Co., Ltd.) were used.
  • laminates (1) to (8) were obtained in which the support, the primer layer, the metal particle layer, and the metal plating layer were sequentially laminated.
  • the number of the primer layer forming coating liquid corresponds to the number of the laminate, for example, the primer layer forming coating liquid (1) corresponds to the laminate (1).
  • Adhesion evaluation (under normal conditions)> For each laminate obtained above, the peel strength was measured using 4000Plus manufactured by Nordson DAGE in a room temperature environment. The lead width used for measurement was 5 mm, and the peel angle was 90°. In addition, the peel strength tends to show a higher value as the thickness of the metal plating layer increases. In this specification, the peel strength was measured based on the measurement value at a thickness of 8 ⁇ m of the metal plating layer. Adhesion was evaluated according to the following criteria from the measured peel strength before heating. A: The value of peel strength is 600 N/m or more. B: The peel strength value is 450 N/m or more and less than 600 N/m. C: The peel strength value is 250 N/m or more and less than 450 N/m. D: The peel strength value is less than 250 N/m. The evaluation results were as shown in Table 1 below.
  • the laminates (laminates (1) to (7)) using a phenoxy resin having a specific molecular weight as the primer layer are all good at normal conditions.
  • the peel strength is 450 N/m or more, and even after the long-term heat resistance test, it has a retention rate of 80% or more of the peel strength in the normal state. In other words, it can be seen that the adhesion evaluation is excellent both in the normal state and after the long-term heat resistance test.

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JP2015156459A (ja) * 2014-02-21 2015-08-27 Dic株式会社 積層体、導電性パターン及び電子回路
JP2016112704A (ja) * 2014-12-11 2016-06-23 Dic株式会社 導電性積層体及びその製造方法
WO2019013040A1 (ja) * 2017-07-10 2019-01-17 Dic株式会社 積層体、それを用いたプリント配線板、フレキシブルプリント配線板及び成形品
JP2019014188A (ja) * 2017-07-10 2019-01-31 Dic株式会社 積層体、それを用いたプリント配線板、フレキシブルプリント配線板及び成形品
JP2020059185A (ja) * 2018-10-09 2020-04-16 Dic株式会社 積層体、電子機器及びこれらの製造方法

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JP6090148B2 (ja) 2013-12-19 2017-03-08 住友金属鉱山株式会社 金属薄膜／ポリイミド積層体の密着強度判定方法、及び、それを用いた金属化ポリイミドフィルム基板
JP6775240B2 (ja) 2016-06-10 2020-10-28 株式会社Ｃ−Ｉｎｋ めっき下地用の組成物、それによるめっき下地及び金属被膜を形成する方法
CN110753617A (zh) 2017-07-10 2020-02-04 Dic株式会社 层叠体、使用其的印刷布线板、挠性印刷布线板及成形品

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Publication number Priority date Publication date Assignee Title
JP2015156459A (ja) * 2014-02-21 2015-08-27 Dic株式会社 積層体、導電性パターン及び電子回路
JP2016112704A (ja) * 2014-12-11 2016-06-23 Dic株式会社 導電性積層体及びその製造方法
WO2019013040A1 (ja) * 2017-07-10 2019-01-17 Dic株式会社 積層体、それを用いたプリント配線板、フレキシブルプリント配線板及び成形品
JP2019014188A (ja) * 2017-07-10 2019-01-31 Dic株式会社 積層体、それを用いたプリント配線板、フレキシブルプリント配線板及び成形品
JP2020059185A (ja) * 2018-10-09 2020-04-16 Dic株式会社 積層体、電子機器及びこれらの製造方法

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