WO2023149581A1 - Solution de traitement de surface, et procédé de fabrication de résine traitée en surface et stratifié de film de résine - Google Patents

Solution de traitement de surface, et procédé de fabrication de résine traitée en surface et stratifié de film de résine Download PDF

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Publication number
WO2023149581A1
WO2023149581A1 PCT/JP2023/003885 JP2023003885W WO2023149581A1 WO 2023149581 A1 WO2023149581 A1 WO 2023149581A1 JP 2023003885 W JP2023003885 W JP 2023003885W WO 2023149581 A1 WO2023149581 A1 WO 2023149581A1
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resin
group
surface treatment
treatment liquid
acid
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PCT/JP2023/003885
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English (en)
Japanese (ja)
Inventor
宏 倉光
克彦 安
敏憲 井上
光信 平林
和弘 光田
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豊光社テクノロジーズ株式会社
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Priority claimed from JP2022016783A external-priority patent/JP7120695B1/ja
Application filed by 豊光社テクノロジーズ株式会社 filed Critical 豊光社テクノロジーズ株式会社
Publication of WO2023149581A1 publication Critical patent/WO2023149581A1/fr

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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • 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
    • C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
    • 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
    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/02—Polyamines
    • 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
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups

Definitions

  • the present invention relates to a surface treatment liquid used by applying it to a resin, and a method for producing a surface treated resin, a method for producing a resin film laminate, and a method for producing a metal-coated resin using the surface treatment liquid.
  • Polyimide is a thermosetting resin with high heat resistance, and its physical properties change very little over a wide temperature range from a low temperature of -269°C to a high temperature of +300°C, so its use in the electrical and electronic fields is expanding. In the electrical field, for example, it is used for the insulation of industrial motor coils and superconducting wires. ), etc.
  • polyimide Since polyimide is mainly produced as a polyimide film by solution film formation by casting, it is difficult to produce thick sheets and boards due to the production method, and even if it can be produced, it has the disadvantage of lacking homogeneity.
  • a method of manufacturing a thick sheet or block by subjecting polyimide-polyimide block copolymer powder to high-temperature compression molding but this method is expensive and not suitable for mass production. Therefore, various methods for producing a polyimide film laminate have been proposed in which a plurality of polyimide films are laminated and adhered to each other in order to ensure a sufficient thickness.
  • a method of crimping at high temperature a method of applying a special plasma treatment to the surface of the polyimide film before crimping, a method of bonding with an adhesive made of thermoplastic resin such as epoxy resin or acrylic resin, and a thermoplastic polyimide film interposed as an adhesive layer. and the like.
  • thermoplastic resin such as epoxy resin or acrylic resin
  • thermoplastic polyimide film interposed as an adhesive layer and the like.
  • all of these methods have drawbacks such as requiring expensive equipment for mass production, generating volatile gas, and impairing the properties of polyimide as a non-thermoplastic resin.
  • a compound having two or more functional groups can form a chemical bond by utilizing the properties of each functional group.
  • IMB interface molecular bonding
  • Patent Document 1 discloses a method for producing a polyimide film laminate by laminating a plurality of polyimide films via an interfacial molecular binder and pressing them at a temperature of about 200°C.
  • the interfacial molecular binder disclosed in this document is a silane compound having a functional group such as an amino group or a silanol group in one molecule, such as (3-aminopropyl)triethoxysilane (hereinafter referred to as "ATES").
  • ATES (3-aminopropyl)triethoxysilane
  • Patent Document 2 in order to avoid the above disadvantages, a polyvalent amine compound having a molecular weight of approximately 300 or less, such as ethylenediamine, is used as an interfacial molecular binder instead of a silane compound, and is heated at a temperature of 40 ° C. to 180 ° C.
  • a technique for producing a polyimide film laminate by pressing with is disclosed.
  • this technique has the disadvantage that if the polyimide film to which the polyvalent amine compound is added is not laminated and pressure-bonded immediately, and if it is left in an air atmosphere for several days and then laminated and pressure-bonded, the adhesion will be significantly reduced. Since it is necessary to press-bond immediately after applying the polyvalent amine compound, there is no flexibility in constructing the mass production process of the laminate, and the cost is high.
  • Patent Document 3 in a substrate having both a portion made of silica and a portion made of metal on the surface, two agents are sequentially applied or applied to selectively only the portion made of silica.
  • the first agent is a composition containing a polymer having a cationic functional group, such as polyethyleneimine
  • the second agent is a coating liquid containing a polycarboxylic acid having an aromatic ring or an anhydride thereof, the first agent may contain an aromatic monocarboxylic acid such as benzoic acid, and the second agent may contain organic acids such as maleic acid.
  • These two agents are agents (varnishes) used for the purpose of forming a resin layer as described above, and an interfacial molecular binder used for the purpose of interposing between two substances to form a bond between them. have different uses. Moreover, as described above, the combination of two agents described in Patent Document 3 is not suitable for joining metal and resin.
  • An object of one aspect of the present invention is to provide a surface treatment liquid that does not contain a silane compound and is used by applying it to a resin, and even if the resin treated with the surface treatment liquid is left in an air atmosphere for several days, other To provide a surface treatment liquid which scarcely deteriorates adhesion in bonding with a substance.
  • An object of another aspect of the present invention is to provide a method for producing a surface treatment substance, a method for producing a resin film laminate, or a method for producing a metal-coated resin using the surface treatment liquid.
  • a surface treatment liquid that is applied and used contains a polymer having a repeating unit having a primary amino group or an imino group and a compound ⁇ each at a concentration of 0.01% by mass or more, and a total concentration of 5% by mass or less.
  • the compound ⁇ is a compound having an azide group, a diazomethyl group or an azidosulfonyl group and an OH group or an alkoxy group in one molecule, and a surface treatment having a pH of 5.0 or less at 25°C. Liquid.
  • a second embodiment of the present invention is the surface treatment liquid according to the first embodiment, which has a pH of 4.5 or less at 25°C.
  • the surface treatment liquid further contains an acid or an anhydride of the acid, and the acid has an acid dissociation constant pKa at 25° C. of 4.0 or less. It is a surface treatment liquid.
  • a fourth aspect of the present invention is the surface treatment liquid according to the second or third aspect, wherein the OH group or alkoxy group is contained in the carboxy group or alkoxycarbonyl group of the compound ⁇ .
  • a fifth aspect of the present invention is the surface treatment liquid according to the fourth aspect, wherein the compound ⁇ contains an aromatic ring.
  • a sixth aspect of the present invention is the surface treatment according to the fifth aspect, wherein the aromatic ring is a benzene ring, and the azide group, diazomethyl group or azidosulfonyl group is directly bonded to the benzene ring. Liquid.
  • a seventh form of the present invention is the surface treatment liquid according to the first form, wherein the repeating unit is a repeating unit represented by any one of the following formulas (2) to (7).
  • a is an integer of 0 or more, for example an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 4 or less, more preferably 1, and R, R 1 , R 2 and R 3 are each independently is an H atom, a substituted or unsubstituted alkyl group (e.g., 1 to 25 carbon atoms, or 1 to 5 carbon atoms) or an aryl group (e.g., phenyl group), and Z - represents an anion in solution. It is not included in the above polymer.
  • at least one of R, R 1 , R 2 and R 3 is an H atom.
  • An eighth aspect of the present invention comprises the steps of applying the surface treatment liquid according to the first aspect to the surface of a resin, and heating the surface of the resin coated with the surface treatment liquid.
  • a method for producing a surface-treated resin is a method for producing a surface-treated resin.
  • a ninth aspect of the present invention comprises a step of applying the surface treatment liquid according to the first aspect to the surface of a resin, and a step of irradiating the surface of the resin coated with the surface treatment liquid with ultraviolet rays. It is a manufacturing method of the surface treatment resin which comprises.
  • a tenth form of the present invention is the eighth or ninth form, wherein the resin is subjected to washing treatment, acid treatment, alkali treatment, A method for producing a surface-treated resin, further comprising a step of performing one or more pretreatments selected from the group consisting of corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, silicifying flame treatment and defluorination treatment.
  • An eleventh form of the present invention includes a step of preparing and superimposing a plurality of resin films, wherein any two adjacent resin films A and B in the plurality of superimposed resin films are: At least one of the resin films A is treated by the method for producing a surface-treated resin according to the eighth or ninth embodiment on at least the surface of the resin film A facing the resin film B among the front and back surfaces of the resin film A.
  • a method for producing a resin film laminate comprising a step of integrally bonding the plurality of resin films that are superimposed by applying a force.
  • a twelfth form of the present invention is a resin film laminate obtained by laminating at least one set of a plurality of resin films with a condensate layer interposed between two adjacent resin films,
  • the condensate layer contains a dehydration condensate or hydrolytic dehydration condensate of a compound ⁇ and a polymer having a repeating unit having a primary amino group or an imino group, and the compound ⁇ contains, in one molecule
  • the resin film laminate is a compound having an azide group, a diazomethyl group or an azidosulfonyl group and an OH group or an alkoxy group.
  • a thirteenth form of the present invention is the resin film laminate according to the twelfth form, wherein all of the plurality of resin films are polyimide films.
  • the surface-treated surface of the surface-treated resin produced by the method for producing a surface-treated resin according to the eighth or ninth aspect is wet-plated or affixed with a metal foil.
  • a method for producing a metal-coated resin comprising the step of forming a metal coating by combining.
  • a surface treatment liquid containing no silane compound is applied to a resin, and even if the resin treated with the surface treatment liquid is left in an air atmosphere for several days, other It is possible to provide a surface treatment liquid that hardly reduces adhesion in bonding with a substance.
  • the surface treatment liquid contains a combination of a plurality of compounds such that chemical reactions related to surface treatment and interfacial molecular bonding proceed by irradiation with ultraviolet rays or by heat treatment alone without irradiation of ultraviolet rays.
  • FIG. 1A is an explanatory diagram showing how to superimpose a surface-treated resin film.
  • FIG. 1B is an explanatory diagram showing another method of superimposing surface-treated resin films.
  • FIG. 1C is an explanatory diagram showing still another method of superimposing the surface-treated resin films.
  • FIG. 2 is an explanatory diagram of the interfacial molecular bonding mechanism in the condensate layer.
  • FIG. 3 is a flowchart of a method for producing a surface-treated resin.
  • FIG. 4 is a chart showing experimental results.
  • the It is a surface treatment liquid used for the surface treatment, and contains a compound ⁇ and a polymer having a repeating unit having a primary amino group or an imino group at a concentration of 0.01% by mass or more and a total concentration of 5% by mass or less.
  • the compound ⁇ is a compound having an azide group, a diazomethyl group or an azidosulfonyl group and an OH group or an alkoxy group in one molecule, and a surface treatment liquid having a pH of 4.5 or less at 25°C. can provide.
  • the present surface treatment liquid is preferably used by being applied to a resin for the purpose of ensuring adhesion in order to form a resin-to-resin or resin-to-metal bond.
  • a surface treatment capable of interfacial molecular bonding can be performed by irradiation with ultraviolet rays or by heat treatment alone without irradiation with ultraviolet rays.
  • the effect of the surface treatment is hardly lost even after leaving it for 3 or 7 days under a light-shielded atmospheric atmosphere to form a composite.
  • the present surface treatment liquid does not contain Si atoms.
  • thermoplastic resins examples include general-purpose resins, engineering resins, super engineering resins, and the like.
  • General-purpose resins include, for example, polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene (AS), polymethyl methacrylic ( PMMA), polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), cycloolefin polymer (COP) and the like.
  • PVC polyvinyl chloride
  • PE polyethylene
  • PP polypropylene
  • PS polystyrene
  • ABS acrylonitrile-butadiene-styrene
  • AS acrylonitrile-styrene
  • PMMA polymethyl methacrylic
  • PMMA polyvinyl alcohol
  • PVDC polyvinyliden
  • Examples of engineering resins include polyamide (PA), polyacetal (POM), polycarbonate (PC), polyphenylene ether (PPE (modified PPO)), polybutylene terephthalate (PBT), ultra-high molecular weight polyethylene (U-PE), polyfluoro Examples include vinylidene dichloride (PVDF) and the like.
  • Examples of super engineering resins include polysulfone (PSU), polyethersulfone (PES), polyphenylene sulfide (PPS), polyarylate (PAR), polyamideimide (PAI), polyetherimide (PEI), polyetheretherketone ( PEEK), thermoplastic polyimide (TPI), liquid crystal polymer (LCP), polytetrafluoroethylene (PTFE).
  • Thermosetting resins include phenol resin (PF), epoxy resin (EP), melamine resin (MF), urea resin (urea resin, UF), unsaturated polyester resin (UP), alkyd resin, polyurethane (PUR), Examples include polyimide (PI), modified polyimide (MPI), and thermosetting polyimide.
  • Thermosetting resin product forms include C-stage (cured) sheets such as polyimide, B-stage (uncured) sheets such as build-up sheets, prepregs, die-bond sheets, and ACF (anisotropic conductive sheets). Sheets, conductive or insulating compounds, pastes, inks, and other A-stage materials can be used.
  • the surface treatment liquid of the present invention is particularly a resin containing one or more compounds having a carboxy group, a primary amino group, a secondary amino group, or a tertiary amino group, or one or more such It is suitable for resins containing polymers of compounds, such as polyimides, polyamides, polyamideimides, and the like.
  • the present surface treatment liquid contains a solvent.
  • the solvent is not particularly limited as long as it can dissolve the compound ⁇ and the polymer. Examples include methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, cellosolve, carbitol, 3-methoxy-3- alcohols such as methyl-1-butanol (hereinafter referred to as "SF"); ketones such as acetone, methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene and xylene; Aliphatic hydrocarbons, esters such as ethyl acetate, methyl propionate and methyl phthalate, ethers such as tetrahydrofuran (THF), ethyl butyl ether, anisole, propylene glycol monomethyl ether acetate (PGMEA), water and the like can be used.
  • alcohol, ether and water are examples of alcohol, ether and water
  • the present surface treatment liquid contains a polymer having repeating units having primary amino groups (--NH 2 ) or imino groups (--NH--).
  • the polymer forms an ionic bond or an amide bond with the compound ⁇ having an OH group or an alkoxy group, and contributes to the formation of an interfacial molecular bond.
  • Examples of the above repeating units are repeating units represented by any of the above formulas (2) to (7).
  • the alkyl or aryl groups represented by R, R 1 , R 2 and R 3 may have one or more substituents.
  • Suitable substituents include cationic groups, eg quaternary ammonium groups, or amine groups, eg primary, secondary or tertiary alkyl or arylamines.
  • Examples of other suitable substituents include hydroxy groups, alkoxy groups, alkyl groups, aryl groups, poly(alkyleneimines) such as poly(ethyleneimine), and the like.
  • the repeating unit is preferably selected from the group consisting of poly-lower alkyleneimine ([ CmH2mNH ] n , m is an integer of 1 or more and 4 or less, n is an integer of 2 or more), polyvinylamine, and polyallylamine. More preferably, it is a repeating unit contained in one or more polymers selected from the group consisting of polyethyleneimine, polyvinylamine and polyallylamine.
  • the polymer having a repeating unit having a primary amino group or imino group may have any of a linear structure, a branched structure, and a dendrimer structure. It may also be crosslinked with a bifunctional crosslinker such as epichlorohydrin.
  • a bifunctional crosslinker such as epichlorohydrin.
  • the weight-average molecular weight of the polymer having a repeating unit having a primary amino group or imino group is preferably 10,000 or less, more preferably 5,000 or less, from the viewpoint of suppressing uneven coating of the surface treatment liquid. More preferably, it is 1500 or less.
  • the weight average molecular weight is preferably 200 or more, more preferably 450 or more, and even more preferably 900 or more, from the viewpoint of suppressing non-uniformity of the coating film thickness.
  • the weight average molecular weight of a polymer means the weight average molecular weight of polystyrene conversion measured by a gel permeation chromatography (GPC method).
  • the concentration of the polymer in the present surface treatment liquid is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and more preferably 0.05% by mass or more, from the viewpoint of ensuring adhesion in interfacial molecular bonding. More preferred. Moreover, from the viewpoint of suppressing coating unevenness, the concentration is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.
  • the present surface treatment liquid contains compound ⁇ .
  • Compound ⁇ is a compound having an azide group, a diazomethyl group or an azidosulfonyl group (X) and an OH group or an alkoxy group (Y) in one molecule. Since the compound ⁇ has an azide group, a diazomethyl group, or an azidosulfonyl group (X) (hereinafter referred to as an azide group or the like (X)), the present surface treatment liquid exhibits interfacial molecular bonding by irradiation with ultraviolet rays or heat treatment. Possible surface treatments can be performed.
  • Compound ⁇ preferably has a structure represented by the following formula (8).
  • m and n are integers of 1 or more.
  • A represents an (m+n) valent organic group or an empty group (direct bond).
  • E's each independently represent a (l+1)-valent group.
  • Y's each independently represent an OH group or an alkoxy group.
  • m is preferably 3 or less, more preferably 2 or less, and even more preferably 1.
  • the alkoxy group is preferably a methoxy group, an ethoxy group or a benzyloxy group.
  • the group E is such that the atom of the group E to which the OH group or the alkoxy group (Y) is directly bonded is less than the other atoms of the group E to which it is directly bonded. is preferably a group with low electronegativity. In such a case, the OH group or alkoxy group (Y) and the primary amino group or imino group of the polymer are likely to form a bond even at low temperatures.
  • the group (E-(Y) l ) is a carboxy group or an alkoxycarbonyl group and the integer n is preferably one.
  • the (m+n)-valent organic group A is, in an alkane or in a compound in which 0 or more alkyl groups are bonded to an aromatic ring, 0 or more carbon-carbon single bonds (C-C) between carbon atoms , an ether bond (--O--), a thioether bond (--S--) or a compound in which an amide bond is inserted, from which (m+n) H atoms are removed.
  • the aromatic ring is preferably a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, biphenyl, or the like.
  • the organic group A preferably contains an aromatic ring from the viewpoint of ensuring adhesion in interfacial molecular bonding that accompanies pressure pressing after surface treatment of the resin. Moreover, from the viewpoint of ensuring higher adhesion, it is preferable that the azide group or the like in the compound ⁇ is directly bonded to the aromatic ring. This is because an azide group or the like directly bonded to an aromatic ring is highly reactive.
  • the compound ⁇ is a benzene ring. and more preferably the azide group or the like is directly bonded to the benzene ring.
  • the organic group A has an aromatic ring and is a benzene ring
  • preferred examples of the compound ⁇ are 2-azidobenzoic acid, 3-azidobenzoic acid, 4-azidobenzoic acid, 2-azidobenzene sulfonic acid, 3-azidobenzenesulfonic acid, 4-azidobenzenesulfonic acid and the like.
  • preferred examples of the compound ⁇ include ethyl azide acetate and diethyl phosphate azide.
  • the organic group A has an aromatic ring and the compound ⁇ has a carbonyl group
  • preferred examples of the compound ⁇ are compounds represented by the following formula (9) or (10).
  • X is the above-mentioned azide group or the like.
  • Y is an OH group or an alkoxy group.
  • the divalent organic group A 1 is a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring or biphenyl, preferably a benzene ring or a naphthalene ring, more preferably a benzene ring, from which two hydrogen atoms directly bonded to the aromatic ring are removed. It is the basis for One or more H atoms directly bonded to the aromatic ring in A 1 are each independently substituted with a monovalent organic group such as halogen, methyl group, ethyl group, methoxy group, ethoxy group, OH group or formyl group.
  • a monovalent organic group such as halogen, methyl group, ethyl group, methoxy group, ethoxy group, OH group or formyl group.
  • the method for synthesizing compound ⁇ as shown in formulas (9) and (10) is not particularly limited.
  • compound Q having both an alkoxycarbonyl group and a functional group c other than an alkoxycarbonyl group and can be obtained by reacting a reactive group d capable of bonding reaction with a compound L having both a benzene ring and the like and an azide group and the like by a known method.
  • a combination of the functional group c and the reactive group d a combination of an isocyanate group, an epoxy group, an amino group, etc., and a carboxy group can be considered.
  • concentration of compound ⁇ in the present surface treatment liquid is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and further preferably 0.05% by mass or more, from the viewpoint of ensuring adhesion in interfacial molecular bonding. preferable.
  • the concentration is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.
  • the pH of this surface treatment liquid at 25 ° C. is 5.0. It is preferably 4.5 or less, more preferably 4.0 or less.
  • the pH of the present surface treatment liquid at 25° C. is preferably 1.0 or more, and is 2.0 or more. is more preferable, and 3.0 or more is even more preferable.
  • the resin treated with the present surface treatment liquid is placed in a room with a temperature of 23° C. and a humidity of 50% in a light-shielded atmospheric atmosphere for 7 days. Adhesion in bonding with other substances (resin or metal) hardly deteriorates even after being left for days. On the other hand, when the pH of the present surface treatment liquid is in the neutral to alkaline range, the adhesion is remarkably lowered when left for 7 days in a non-dry air atmosphere shielded from light.
  • the pH of the surface treatment liquid means a value measured with a pH test paper (UNIVERSAL test paper, manufactured by Advantec Toyo Co., Ltd.) at 25° C., and the measurement error is about ⁇ 0.5. be.
  • An acid can be further added to the present surface treatment liquid.
  • the compound ⁇ is Arrhenius acid, and its acid dissociation constant (when the compound dissociates in multiple steps, it is the dissociation constant of the first step dissociation. Value in water at 25° C. The same shall apply hereinafter.)
  • pKa is about 4.
  • the pH of the surface treatment solution can be lowered to 5.0 or less, more preferably 5.0 or less, even without the addition of an acid. 4.5 or less.
  • an acid to the present surface treatment liquid to adjust the pH of the present surface treatment liquid to 5.0 or less, more preferably 4.5 or less.
  • the acid dissociation constant pKa is less than or equal to about 4.0.
  • Various acids such as inorganic acids and organic acids can be used as the acid to be added to the present surface treatment liquid.
  • Inorganic acids include, but are not limited to, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, hydrofluoric acid, carbonic acid, and the like.
  • organic acids include, but are not limited to, short-chain monocarboxylic acids such as formic acid, acetic acid and propionic acid, and lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid and erucic acid.
  • short-chain monocarboxylic acids such as formic acid, acetic acid and propionic acid, and lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid and erucic acid.
  • Long-chain monocarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, glycolic acid, lactic acid, hydroxyacrylic acid, glyceric acid, malic acid , hydroxycarboxylic acids such as tartaric acid and citric acid, polycarboxylic acids such as polyglutamic acid, acidic amino acids such as glutamic acid and aspartic acid, alkyl sulfates, alkyl sulfonates, and alkyl phosphates.
  • dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, glycolic acid, lactic acid, hydroxyacrylic acid, glyceric acid, malic acid , hydroxycarboxylic acids such as tartaric acid and citric acid
  • inorganic acids short-chain monocarboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, acidic amino acids are commonly used, as well as hydrochloric acid, sulfuric acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, succinic acid, maleic acid.
  • Acids, glycolic acid, lactic acid, malic acid, citric acid, glutamic acid are especially used.
  • One or more acids selected from these acids may be used at the same time, and anhydrides of the one or more acids may be added. By adding one or more acid anhydrides to the present surface treatment liquid, adhesion in bonding is remarkably improved as compared with the case where one or more acids are added.
  • the concentration thereof is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, from the viewpoint of ensuring adhesion in interfacial molecular bonding. , more preferably 0.05% by mass or more. Moreover, from the viewpoint of suppressing coating unevenness, the concentration is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less. As described above, when the compound ⁇ is Arrhenius acid having a certain degree of strength, it is not necessary to add the acid or its anhydride to the present surface treatment liquid.
  • a step of applying the surface treatment liquid of any one of the above aspects to the surface of a resin (application step (S2)); It is possible to provide a method for producing a surface-treated resin comprising a step of heating the surface of the applied resin (heat activation step (S4)).
  • a treatment liquid such as the present surface treatment liquid is applied to a resin such as a polyimide film.
  • coating means “adhering” or “existing in contact with” the treatment liquid on the surface of the resin.
  • the coating method include conventionally known coating methods such as brush coating, inkjet, gravure coating, lip coating, comma coating, blade coating, roll coating, knife coating, spray coating, and bar coating.
  • a coating method, a spin coating method, and a dip coating method can be used.
  • the lower limit of the thickness of the coating film when the treatment liquid is applied is preferably 0.5 ⁇ m, for example, from the viewpoint of ensuring the adhesion between the surface treatment resin and other substances (resins and metals). 1.5 ⁇ m is more preferred, and 5 ⁇ m is even more preferred.
  • the lower limit of the thickness (dry film thickness) of the coating film is preferably 1 nm, more preferably 3 nm, and still more preferably 10 nm.
  • the upper limit of the thickness of the coating film (wet film thickness) is preferably, for example, 500 ⁇ m, more preferably 150 ⁇ m, and even more preferably 50 ⁇ m, from the viewpoint of ease of coating and suppression of coating unevenness.
  • the upper limit of the thickness (dry film thickness) of the coating film is preferably 1 ⁇ m, more preferably 300 nm, and still more preferably 100 nm.
  • the immersion time when the dip coating method is used is preferably, for example, 3 seconds or more and 60 seconds or less.
  • "Application" may be performed on a part of the surface of the resin, or may be performed on the entire surface of the resin. Further, when the resin is in the form of a film or a sheet, the "coating" may be performed only on one side of the resin, or may be performed on both the front and back sides of the resin. .
  • drying process of drying the surface of the resin coated with the treatment liquid by natural drying, air drying, or hot air blowing at about 40°C to 70°C. done.
  • the compound ⁇ contained in the present surface treatment liquid and the polymer having a repeating unit having a primary amino group or imino group are arranged on the surface of the resin by the coating step and the drying step described above.
  • heat activation step In the heat activation step (S4), the surface of the resin coated with the present surface treatment liquid is heated. By heating, the surface is brought into a state suitable for thermocompression bonding with other resins, metal plating, or the like.
  • the temperature of the surface of the resin during heating is, for example, 80 to 160° C., preferably 90 to 120° C., and the time for which the surface of the resin is maintained at that temperature is, for example, 30 seconds to 60 minutes, preferably 5 to 120° C. 20 minutes.
  • the heat treatment will decompose the azide group of the compound ⁇ , liberate N 2 gas, generate radicals, and bring the compound ⁇ into a state suitable for bonding with resins, metals and the above polymers. Further, by heating, the OH group or alkoxy group possessed by the compound ⁇ forms an amide bond with the primary amino group or imino group possessed by the polymer through a dehydration condensation reaction or a hydrolytic dehydration condensation reaction to form an amide bond with the compound ⁇ . The polymer will condense to form a very thin layer of condensate.
  • the OH group or alkoxy group of the compound ⁇ will undergo dehydration condensation or hydrolytic dehydration condensation with the OH group or the like on the surface of the resin to form a bond between the compound ⁇ and the surface of the resin.
  • the heat activation step forms a very thin layer of condensate that adheres to the surface of the resin, leaving the surface of the condensate in a state suitable for bonding with another resin or metal.
  • the surface-treated resin produced by the method for producing a surface-treated resin according to the present embodiment of the present invention maintains its activated state even after being placed in a room with a temperature of 23° C. and a humidity of 50% in a light-shielded atmosphere for 7 days. It is sagging, and adhesion to other substances (resin or metal) is hardly reduced.
  • the rate of decrease in peel strength due to leaving for 7 days is within 10% or within 25%.
  • UV activation step the coating step and the step of irradiating the surface of the resin coated with the surface treatment liquid of any aspect of the present invention with ultraviolet rays (UV activation step (S6)). It is possible to provide a method for producing a surface-treated resin comprising In the above heat activation step, the azide group of the compound ⁇ was decomposed by heating, but in the UV activation step, the azide group of the compound ⁇ was decomposed by the ultraviolet irradiation treatment and N gas was released. Then, it is thought that radicals are generated and the compound .alpha. is brought into a state suitable for bonding with the resin, the metal and the polymer.
  • the wavelength of the ultraviolet rays to be irradiated is preferably 260 to 350 nm, more preferably 330 to 350 nm, from the viewpoint of ensuring adhesion and preventing deterioration of resins such as polyimide films due to ultraviolet rays.
  • Any of a mercury lamp, a metal halide lamp, and a UV-LED may be used as the ultraviolet light source.
  • the heat activation step may be performed in addition to the UV activation step. In that case, the order of the heat activation step and the UV activation step does not matter, and either of them may be performed first, or they may be performed simultaneously.
  • the coating step, the heat activation step, and the UV activation step may be combined with or not combined with other treatments such as the post-activation cleaning treatment step (S8) for removing by-products, or in any order. can be applied iteratively.
  • the surface-treated resin produced by the method for producing a surface-treated resin according to the present embodiment of the present invention also retains its activated state even after being left in a room with a temperature of 23° C. and a humidity of 50% in a shaded atmosphere for 7 days. It is sagging, and adhesion to other substances (resin or metal) is hardly reduced. The rate of decrease in peel strength due to leaving for 7 days is within 10% or within 25%.
  • Pretreatment step Before the step of applying the surface treatment liquid according to any aspect of the present invention to the surface of the resin, the resin is subjected to washing treatment, acid treatment, alkali treatment, A step of performing one or more pretreatments (pretreatment step (S1 )), a method for producing a surface-treated resin can be provided.
  • the pretreatment step is a step of pretreating the surface of a resin such as a polyimide film. It is carried out for the purpose of facilitating fixation of the polymer having repeating units on the surface, and also for the purpose of efficiently performing the subsequent heat activation step and/or UV activation step.
  • the resin By performing the pretreatment step, the resin is in an activated state in which functional groups such as OH groups, carboxyl groups, carbonyl groups, primary amino groups, imino groups, etc. are present on the surface of the resin, and bonding with the compound ⁇ is achieved. easier to form.
  • the pretreatment process includes cleaning treatment, acid treatment, alkali treatment, corona discharge treatment in which the surface of the resin is irradiated with corona discharge, and plasma treatment in which the surface of the resin is treated with plasma such as argon plasma, oxygen plasma, or atmospheric plasma. , ultraviolet irradiation treatment, and silicification flame treatment (itro treatment) in which the surface of the resin is exposed to combustion flames of combustion gas mixed with a coupling agent such as a silane compound.
  • the surface-treated resin produced by the method for producing a surface-treated resin according to the present embodiment of the present invention also retains its activated state even after being left in a room with a temperature of 23° C. and a humidity of 50% in a shaded atmosphere for 7 days. It is sagging, and adhesion to other substances (resin or metal) is hardly reduced. The rate of decrease in peel strength due to leaving for 7 days is within 10% or within 25%.
  • a step of preparing and stacking a plurality of resin films is included, and in the plurality of stacked resin films, any two adjacent resin films A are and B, at least one of the resin film A is treated by the method for producing a surface-treated resin according to any one of the embodiments of the present invention, at least on the surface of the side facing the resin film B among the front and back of the resin film A.
  • Manufacturing of a resin film laminate comprising a step (pressing step) in which the plurality of resin films are integrally bonded by applying force. can provide a method.
  • the pressurizing step for example, plate pressing, roll pressing, or the like is performed under an air atmosphere, a nitrogen atmosphere, or in a vacuum.
  • a nitrogen atmosphere or in a vacuum.
  • flat plate press or roll press under an air atmosphere is preferable.
  • pressing in a nitrogen atmosphere or in vacuum is preferred.
  • the pressing pressure is preferably 1-100 MPa, more preferably 30-70 MPa.
  • the time for which the pressure is applied is, for example, 5 to 60 minutes, more preferably 10 to 20 minutes. Heating is preferably performed at the same time as the pressing step.
  • the temperature of the resin film in the pressing step should be within a range not exceeding the heat resistant temperature.
  • the temperature is, for example, 40° C. or higher and 350° C. or lower, preferably 120° C. or higher and 250° C. or lower, more preferably 150° C. or higher and 230° C. or lower.
  • FIGS. 1A, 1B, and 1C show some of the surface treatments of the four surface-treated resin films (hereinafter simply referred to as films) 1, 2, 3, and 4 superimposed in the superimposing step. Show possible patterns.
  • film 1 is a film (U) that is surface-treated only on the upper surface
  • films 2 and 3 are both films that are surface-treated (B) on both sides
  • film 4 is a film on the lower surface. It is a film (D) in which only the surface treatment is applied.
  • This pattern can be represented as (UBBD).
  • the pattern can similarly be represented as (UUUN).
  • the film 4 is a film (N) in which no surface treatment is applied.
  • the pattern can be represented as (UUUD).
  • the number of resin films and the thickness of each film constituting the laminate are arbitrary.
  • the film can be used to produce a resin film laminate.
  • a resin film laminate obtained by laminating at least one set of a plurality of resin films with a condensate layer interposed between two adjacent resin films,
  • the condensate layer contains a dehydration condensate or hydrolytic dehydration condensate of a compound ⁇ and a polymer having a repeating unit having a primary amino group or an imino group, and the compound ⁇ contains, in one molecule,
  • a resin film laminate that is a compound having an azide group, a diazomethyl group or an azidosulfonyl group and an OH group or an alkoxy group can be provided.
  • FIG. 2 shows a resin film laminate 9 in which three resin films 5, 6 and 7 are laminated. The resin films 5 and 6 are joined via the condensate layer 8 according to the present invention.
  • the resin films 6 and 7 may be joined in the same manner as the resin films 5 and 6, or may be joined by other methods such as hot pressing.
  • An OH group, a carboxyl group, a carbonyl group, a primary amino group, an imino group, or the like is present on the surface of the resin films 5 and 6 originally or generated in the pretreatment step.
  • the azidobenzoic acid-derived portion A1 is radically bonded to the surface of the resin film 5 by radicals generated by decomposition of the azide group.
  • the carboxy group of A1 and the imino group of the polyethyleneimine structure P undergo dehydration condensation to form an amide bond.
  • A2 is radically bonded to the polyethyleneimine structure P by a radical generated by decomposition of the azide group.
  • the azidobenzoic acid-derived moiety A3 is radically bonded to the surface of the resin film 5 by radicals generated by decomposition of the azide group.
  • the carboxy group of A3 and the carboxy group of the azidobenzoic acid-derived moiety A4 form an acid anhydride through dehydration condensation.
  • the azide group of A4 is radically bonded to the polyethyleneimine structure P by a radical generated by decomposition of the azide group.
  • the carboxy group of the azidobenzoic acid-derived portion A5 forms an acid anhydride with the carboxy group on the surface of the resin film 6 through dehydration condensation.
  • the carboxyl group of A6 and the imino group of the polyethyleneimine structure P undergo dehydration condensation to form an amide bond.
  • ⁇ Polyimide film laminate> it is possible to provide a resin film laminate (polyimide film laminate) in which all of the plurality of resin films are polyimide films.
  • the polyimide film laminate of the present embodiment inherits the properties of polyimide as a highly heat-resistant non-thermoplastic resin without impairing the properties of the polyimide film. Even if the polyimide film laminate is constructed by leaving it in the atmosphere for 7 days and then pressurizing it, the adhesiveness is maintained, so there is an advantage that the degree of freedom in the manufacturing process increases. The rate of decrease in peel strength due to leaving for 7 days is within 10% or within 25%.
  • the polyimide used as the resin is a known substance, and can be obtained by a polycondensation reaction using a diamine component and a tetracarboxylic dianhydride component as main components.
  • a polyimide film is generally prepared by applying a polyamic acid solution obtained by reacting a diamine component and a tetracarboxylic dianhydride component in a solvent to a support, drying it to form a green film, and then performing dehydration ring closure by high-temperature heat treatment. It is obtained by allowing the reaction to take place.
  • the diamine component and the tetracarboxylic dianhydride component used as raw materials are suitably selected in consideration of various properties required according to the application of the resin film laminate and the metal-coated resin.
  • the tetracarboxylic dianhydride component constituting the polyamic acid includes aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides that are commonly used in polyimide synthesis. Objects can be used. Among them, aromatic tetracarboxylic dianhydrides and alicyclic tetracarboxylic dianhydrides are preferred. Aromatic tetracarboxylic dianhydrides are more preferable from the viewpoint of heat resistance, and alicyclic tetracarboxylic dianhydrides are more preferable from the viewpoint of light transmittance.
  • the aromatic tetracarboxylic dianhydride is not particularly limited, but when the compound ⁇ has a benzene ring, from the viewpoint of affinity with the compound ⁇ and ease of bonding, It is preferably an acid dianhydride having a benzene ring, and more preferably an acid dianhydride having no aromatic ring other than a benzene ring or a substituted benzene ring.
  • aromatic tetracarboxylic dianhydrides having no aromatic ring other than a benzene ring or a substituted benzene ring include pyromellitic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 3,4,3′,4′-benzophenonetetracarboxylic dianhydride, 3,4 ,3′,4′-diphenylsulfonetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)sulfide dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, p-terphenyl-3,4,3′,4′-tetracarboxylic dianhydride, m-terphenyl
  • aromatic tetracarboxylic dianhydride having a benzene ring or a substituted benzene ring other than a benzene ring examples include naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1, 2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 1,4 ,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride , 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,
  • Examples of alicyclic tetracarboxylic dianhydrides include cyclobutane-1,2,3,4-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, Cyclohexane-1,2,4,5-tetracarboxylic dianhydride, bicyclohexyl-3,3′,4,4′-tetracarboxylic dianhydride, 1-carboxymethyl-cyclopentane-2,3,5 -carboxylic acid-2,6:3,5-dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride.
  • aliphatic tetracarboxylic dianhydrides include ethane-1,1,2,2-tetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, propane-1,1,3,3-tetracarboxylic dianhydride, Carboxylic dianhydride and butane-1,2,3,4-tetracarboxylic dianhydride can be mentioned.
  • the tetracarboxylic dianhydride component may be used alone or in combination of two or more.
  • aromatic diamines As the diamine component that constitutes polyamic acid, aromatic diamines, alicyclic diamines, and aliphatic diamines that are commonly used in polyimide synthesis can be used. Among them, aromatic diamines and alicyclic diamines are preferred. Aromatic diamines are more preferable from the viewpoint of heat resistance, and alicyclic diamines are more preferable from the viewpoint of light transmittance.
  • the aromatic diamines are not particularly limited, but when the compound ⁇ has a benzene ring, it has a benzene ring or a substituted benzene ring from the viewpoint of affinity with the compound ⁇ and ease of bonding. It is preferably an aromatic diamine, more preferably an aromatic diamine having no aromatic ring other than a benzene ring or a substituted benzene ring.
  • aromatic diamines having no aromatic ring other than a benzene ring or a substituted benzene ring include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,6-dihydroxy-1, 3-phenylenediamine, 3,5-diaminobenzoic acid, m-aminobenzylamine, p-aminobenzylamine, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3',4,4'-tetraaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'- Diamin
  • aromatic diamines having a benzene ring or a substituted benzene ring other than a benzene ring examples include 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 1,5-diaminonaphthalene, 1,4-diamino Naphthalene is mentioned.
  • Alicyclic diamines include, for example, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 1,4-diaminocyclohexane, and bis(4-amino-2,6-dimethylcyclohexyl)methane. mentioned.
  • aliphatic diamines examples include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,8-diaminooctane , 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane.
  • the diamine component may be used alone or in combination of two or more.
  • the polyimide film used in the present invention preferably contains an aromatic ring from the viewpoint of heat resistance, and regardless of whether it is non-thermoplastic or thermoplastic, the type is not particularly limited, but specific examples For example, Kapton series manufactured by Toray DuPont Co., Ltd., Upilex series manufactured by Ube Industries, Ltd., Apical series manufactured by Kanegafuchi Chemical Industry Co., Ltd., U-Film series manufactured by Nitto Denko Corporation, etc. A non-thermoplastic polyimide film can be preferably used.
  • a polyimide film containing a benzene ring is preferable from the viewpoint of ensuring affinity and adhesion with the compound ⁇ .
  • the glass transition temperature of the polyimide constituting the film for high heat resistance is preferably 300° C. or higher, more preferably 350° C. or higher.
  • the thickness of the polyimide film is not particularly limited, but examples thereof include 12.5 ⁇ m, 25 ⁇ m, 30 ⁇ m, 40 ⁇ m, 50 ⁇ m, 75 ⁇ m, 100 ⁇ m, 125 ⁇ m, and 250 ⁇ m.
  • a metal coating is formed by wet plating on the surface-treated surface of the surface-treated resin produced by the method for producing a surface-treated resin according to any one of the aspects of the present invention. It is possible to provide a method for producing a metal-coated resin having steps.
  • a metal coating is formed on the surface of the surface-treated resin by, for example, electroless plating, vapor deposition, or sputtering (seed layer forming step). After that, the metal coating may be thickened by electroplating (electroplating step).
  • the metal coating may be formed over the entire surface, or may be formed in a pattern by a known technique such as photolithography.
  • the metal-coated resin produced according to this embodiment is suitable for flexible metal-clad laminates and printed wiring boards.
  • the thickness of the metal coating formed by electroless plating, vapor deposition or sputtering is preferably 0.1 to 2 ⁇ m, more preferably 0.2 to 1 ⁇ m.
  • the thickness of the metal coating after thickening is preferably 0.2 to 50 ⁇ m, more preferably 0.5 to 20 ⁇ m.
  • Metals that are electrolessly plated are, for example, Cu and Ni.
  • the metal of the metal coating formed by vapor deposition or sputtering is, for example, Al, Cr, Sn, Ti, Cu, In, Au, Pt, Ag, and the like.
  • the metal to be electrolytically plated is, for example, Cu, Ni, Ag, Pd, Au, Pt, Zn, Cr, Sn, Bi, or the like.
  • the metal coating may be a single metal or an alloy.
  • annealing treatment is performed at a temperature of 100° C. to 250° C. for 5 to 60 minutes after the seed layer forming step and/or the electroplating step.
  • the adhesion between the resin and the plated metal of the metal-coated resin produced by the production method of the present embodiment is evaluated by applying the surface-treated resin to an atmosphere with a temperature of 23° C. and a humidity of 50% in a light-shielded atmosphere after the surface treatment.
  • Metallization after 7 days of rest in an atmospheric chamber provides little degradation compared to metallization without rest.
  • the rate of decrease in peel strength due to leaving for 7 days is within 10% or within 25%.
  • the surface-treated surface of the surface-treated resin produced by the method for producing a surface-treated resin according to any one of the aspects of the present invention is coated with a metal foil by attaching a metal foil. It is possible to provide a method for producing a metal-coated resin having a step of forming
  • the thickness of the metal foil to be laminated is preferably 0.2-50 ⁇ m, more preferably 0.5-20 ⁇ m.
  • Metals constituting the metal foil are, for example, Cu, Ni, Ag, Pd, Au, Pt, Zn, Cr, Sn, Bi, Al, Ti, In, particularly Cu, Ag, Au, Pt, Al, etc. is mentioned.
  • the metal foil may be a single metal or an alloy.
  • the surface of the metal foil to be bonded to the resin may or may not be roughened.
  • a process of superimposing a metal foil on the surface treated with a surface-treated resin (superposition process) and a process of integrally bonding the two by applying force (pressing process) are performed. equip.
  • the pressurizing step for example, plate pressing, roll pressing, or the like is performed under an air atmosphere, a nitrogen atmosphere, or in a vacuum. From the viewpoint of productivity improvement and processing cost reduction, flat plate press or roll press under an air atmosphere is preferable. From the viewpoint of quality stability of the metal coating resin to be produced, pressing under a nitrogen atmosphere or in a vacuum is preferred.
  • the pressing pressure is preferably 1-100 MPa, more preferably 30-70 MPa. In general, the higher the press pressure, the higher the adhesion strength of the metal-coated resin produced, which is preferable. However, if the press pressure is too high, the support may be damaged.
  • the time for which the pressure is applied is, for example, 5 to 60 minutes, more preferably 10 to 20 minutes. Heating is preferably performed at the same time as the pressing step.
  • the temperature of the resin in the pressurizing step should be within a range that does not exceed the heat resistance temperature. The temperature is, for example, 40° C. or higher and 350° C. or lower, preferably 120° C. or higher and 250° C. or lower, more preferably 150° C. or higher and 230° C. or lower.
  • the adhesion between the resin and the metal foil of the metal-coated resin manufactured by the manufacturing method of the present embodiment is evaluated by applying the surface-treated resin to an atmosphere with a temperature of 23° C. and a humidity of 50% in a light-shielded atmosphere after the surface treatment. Even if the metal foil is stuck together after leaving it in an atmospheric room for 7 days, it hardly deteriorates compared to the case where the metal foil is stuck together without leaving it. The rate of decrease in peel strength due to leaving for 7 days is within 10% or within 25%.
  • Example 1 (Preparation of surface treatment liquid) Powder of 4-azidobenzoic acid as the "compound ⁇ " and polyethyleneimine (trade name: Epomin (registered trademark), product number: SP-012, as the "polymer having a repeating unit having a primary amino group or imino group”) Nippon Shokubai Co., Ltd.) liquid and maleic acid powder as “acid” are each weighed by the required mass, and mixed with 3-methoxy-3-methyl-1-butanol (hereinafter referred to as "SF"). By dissolution, a pale yellow to orange surface treatment liquid was obtained.
  • SF 3-methoxy-3-methyl-1-butanol
  • the concentration of each component is 0.10% 4-azidobenzoic acid, 0.10% polyethyleneimine, and 0.15% maleic acid. and the pH of the solution measured with pH test paper was 4.0.
  • the average molecular weight of the polyethyleneimine used was about 1200, and the amine ratio was 35% primary amino groups, 35% secondary amino groups (imino groups), and 30% tertiary amino groups.
  • a force gauge ZTA-50N was attached to a vertical electric measuring stand MX2-500N (manufactured by Imada Co., Ltd.) to configure a peel strength tester for 90° peeling.
  • the peeling speed was 50 mm/min.
  • the peel strength was continuously measured for 4 cm of the total length of 6 cm, excluding 1 cm at both ends, and the average value was obtained.
  • Example 2 The concentration of each component of the surface treatment liquid to be prepared is 4-azidobenzoic acid 0.40%, polyethyleneimine 0.40%, maleic acid 0.15% (Example 2), or all three components 0.04% ( Example 3) or 0.02% (Example 4), and Examples 3 and 4 were the same as Example 1 except that the surface treatment liquid was filtered through a filter with a pore size of 0.22 ⁇ m immediately before coating. Then, the pH of the surface treatment liquid was measured, a polyimide film laminate was produced, and the peel strength was measured.
  • Example 1-B The pH of the surface treatment liquid was measured in the same manner as in Example 1-A, except that the surface treatment liquid in Example 1-A was applied at a wet film thickness of 1.5 ⁇ m instead of 25 ⁇ m, and the polyimide film was A laminate was produced and the peel strength was measured.
  • Comparative Examples 1 to 8 For each of Comparative Examples 1 to 8, the pH of the surface treatment liquid was adjusted in the same manner as in Example 1, except that the concentration of each component of the surface treatment liquid to be prepared was set to the value shown in the table of FIG. A polyimide film laminate was prepared and the peel strength was measured.
  • the pH of the surface treatment liquid is preferably 5.0 or less, more preferably 4.5 or less.
  • the coating step and the activation step (and the optional post-activation washing treatment step) can be repeated two or more times. It is possible to obtain a peel strength comparable to that of Example 4.
  • a surface treatment liquid having a concentration of less than 0.01% by mass for any one of the three components is not practical for mass production.
  • the peel strength was estimated to be 10 N/3 cm or more, although accurate values could not be measured due to breakage occurring inside the polyimide film.
  • Example 1 From the comparison between Example 1 and Example 1-A, it can be seen that the peel strength is remarkably improved by adding an acid anhydride instead of an acid to the present surface treatment liquid.
  • Example 1-A observation of peeling during the peel test revealed that the breakage occurred not in the bonding layer but inside the base material (inside the polyimide film), indicating that interfacial molecular bonds are extremely strong.
  • Example 1-B breakage occurred inside the substrate, and the peel strength was estimated to be 10 N/3 cm or more. It can be seen that by adding an acid anhydride to the surface treatment liquid, a high peel strength can be obtained even if the coating thickness is as thin as 1.5 ⁇ m.
  • Example 4-U> A polyimide film laminate was produced and the peel strength was measured in the same manner as in Example 4, except that air drying and UV activation steps were performed instead of the heat activation step in Example 4.
  • the coating surface was irradiated with ultraviolet rays from a UV-LED with an irradiation energy of 200 mJ/cm 2 .
  • a peel strength of 7.0 N/3 cm was obtained. This value slightly exceeds the peel strength (6.8 N/3 cm) in Example 4.
  • Example 1 a surface treatment liquid was prepared using benzoic acid instead of 4-azidobenzoic acid, and the concentration of each component in the surface treatment liquid was 0.10% benzoic acid, 0.10% polyethyleneimine, malein The pH of the surface treatment liquid was measured, a polyimide film laminate was produced, and the peel strength was measured in the same manner as in Example 1, except that the acid was 0.15%.
  • Example 1-L In the same manner as in Example 1, two sheets of surface-treated polyimide film were prepared, and then placed in a room with a temperature of 23 ° C. and a humidity of 50% in a light-shielded air atmosphere for 7 days, followed by a superposition process and pressurization. A polyimide film laminate was produced and the peel strength was measured in the same manner as in Example 1 except that the steps were performed. As a result, a value of 7.3 N/3 cm was obtained. This value is slightly lower than that of Example 1 (8.0 N/3 cm) in which the drawing was not performed, and the rate of decrease in the peel strength due to the drawing was 9%.
  • Example 1-BL> Two surface-treated polyimide films were prepared in the same manner as in Example 1-B, and then placed in a light-shielded atmospheric room at a temperature of 23 ° C. and a humidity of 50% for 7 days and 30 days, then stacked. A polyimide film laminate was produced and the peel strength was measured in the same manner as in Example 1-B, except that the laminating step and the pressing step were performed. As a result, the peel strength after being left for 7 days was 9.0 N/3 cm, and the peel strength after being left for 30 days was also 9.0 N/3 cm. . This value is not much different from that of Example 1-B (10 N/3 cm or more) in which no separation is performed. It can be seen that the rate of decrease in strength is as small as about 10%.
  • Example 3-L In the same manner as in Example 3, two surface-treated polyimide films were prepared, and then left in a room with a temperature of 23 ° C. and a humidity of 50% in a light-shielded atmosphere for 3 days, followed by a superposition process and pressurization. A polyimide film laminate was produced and the peel strength was measured in the same manner as in Example 3 except that the steps were performed. As a result, a value of 8.7 N/3 cm was obtained. This value is slightly lower than that of Example 3 (9.0 N/3 cm) in which no drawing was performed, and the rate of decrease in peel strength due to drawing was 3%.
  • Example 5 Four sheets of the same polyimide film as in Example 1 were prepared, and surface treatment similar to that in Example 1 was performed using the same surface treatment liquid as in Example 1 on one side of three sheets. After leaving these three surface-treated polyimide films in a room with a temperature of 23° C. and a humidity of 50% in a light-shielded atmosphere for 7 days, they were superimposed with the surface-treated surface facing up. , One sheet of untreated polyimide film is placed on top, and the cushion plates attached to the top and bottom are placed on top of each other. A laminate was produced (pressing step). This polyimide film laminate was placed in an oven at 300° C. and left for 30 minutes (annealing step). As a result, a polyimide film laminate having good adhesion was obtained.
  • Example 6 The same polyimide film as in Example 1 was prepared, and one surface thereof was subjected to the same surface treatment as in Example 1 using the same surface treatment liquid as in Example 1. Next, an electroless plating process was carried out using the surface-treated polyimide film as a sample. In the electroless plating process, a pre-dip treatment in which the sample is immersed in a pre-dip solution, followed by a catalyst application treatment in which the sample is immersed in Cataposit 44 (manufactured by Rohm & Haas Electronic Materials Co., Ltd.), and then the sample.
  • a pre-dip treatment in which the sample is immersed in a pre-dip solution
  • Cataposit 44 manufactured by Rohm & Haas Electronic Materials Co., Ltd.
  • a post-electroless plating annealing treatment was carried out at a temperature of .
  • the plating thickness of electroless plating was 0.2 ⁇ m.
  • an electrolytic plating process was performed in which electrolytic copper plating was applied to the sample.
  • the film thickness of the plating film was 20 ⁇ m.
  • a post-electroplating annealing treatment was performed in which the samples were kept at a temperature of 150° C. for 60 minutes to reduce the plating stress.
  • a metal-coated polyimide film was obtained. After that, the metal-coated polyimide film was cut to a width of 10 mm, and the peel strength was measured in the same manner as in Example 1. As a result, a peel strength of 7.0 N/cm was obtained.
  • Example 6-L> After producing a surface-treated polyimide film in the same manner as in Example 6, before carrying out the electroless plating process, except that it was left in a room with a light-shielded atmospheric atmosphere at a temperature of 23 ° C. and a humidity of 50% for 7 days. A metal-coated polyimide film was prepared in the same manner as in Example 6, and the peel strength was measured. As a result, a value of 6.6 N/cm was obtained. This value is slightly lower than that of Example 6 (7.0 N/cm) in which no drawing was performed, and the rate of decrease in peel strength due to drawing was 6%.
  • Example 7 The same polyimide film as in Example 1 was prepared and subjected to the same surface treatment as in Example 1 to obtain a surface-treated polyimide film. Next, a step of bonding the surface-treated polyimide film and the copper foil was performed. A rolled copper foil having a thickness of 18 ⁇ m was used as the copper foil. The above-mentioned rolled copper foil is superimposed on the surface-treated surface of the surface-treated polyimide film, and it is heated with a flat plate press at a press temperature of 180 ° C., a press time of 5 minutes, and a press pressure of 56 MPa through cushion plates attached above and below. A metal-coated polyimide film was produced by pressing (pressing step).
  • the metal-coated polyimide film was cut to a width of 10 mm without performing the annealing step, and the peel strength was measured in the same manner as in Example 1. As a result, a peel strength of 8.0 N/cm was obtained.
  • a metal-coated polyimide film was prepared in the same manner as in Example 7 except for and the peel strength was measured. As a result, a value of 7.8 N/cm was obtained. This value is almost the same as that of Example 7 (8.0 N/cm) in which the holding was not carried out, and the reduction rate of the peel strength due to the holding was 3%.
  • ⁇ Reference example 2> Instead of the surface treatment liquid in Example 7, a 0.2% ethanol solution of a silane coupling agent (trade name: X-12-972F, manufactured by Shin-Etsu Chemical Co., Ltd.) having multiple amino groups in one molecule. Using it as a surface treatment liquid, the pH of the surface treatment liquid was measured in the same manner as in Example 7, and a metal-coated polyimide film was produced to measure the peel strength. As a result, the pH was 8.0 and the peel strength was 7.6 N/cm.
  • a silane coupling agent trade name: X-12-972F, manufactured by Shin-Etsu Chemical Co., Ltd.
  • the polyimide film laminate produced using the surface treatment liquid of the present invention has high heat resistance and can be used as a substitute for inorganic materials such as glass and ceramics. can also be manufactured, and by machining, it can be used like an engineering plastic. It can be suitably used for applications such as reinforcement of FPC boards, lightweight spacers, and probe sockets (test jigs) for semiconductor testing equipment.
  • the surface-treated resin substrate of the present invention maintains close contact even when a laminate is produced with a resin or metal by lamination/compression bonding or wet plating after being left in a non-dry atmosphere for several days. It has the advantage that the process can be made flexible, and the degree of freedom in manufacturing process design and division of labor/collaboration management increases.

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Abstract

Le but de la présente invention est de fournir : une solution de traitement de surface qui ne contient pas d'atomes de Si et ne présente presqu'aucune détérioration de l'adhérence même lorsqu'elle est appliquée à la surface d'une résine et laissée sur la résine traitée en surface dans une atmosphère non sèche pendant plusieurs jours avant stratification et compression; et un procédé de fabrication d'un substrat de résine traité en surface et d'un stratifié de film de résine.　La solution de traitement de surface de la présente invention contient un composé α et un polymère ayant une unité de répétition ayant un groupe amino primaire ou un groupe imino, a un pH de 4,5 ou moins à 25 °C, et est utilisée en étant appliquée à une résine pour liaison moléculaire interfaciale. Le composé α a un groupe azide, un groupe diazométhyle ou un groupe azidosulfonyle, et un groupe OH ou un groupe alcoxy dans une molécule. De préférence, la solution de traitement de surface contient, en outre, un acide ou un anhydride de ce dernier ayant une constante de dissociation d'acide pKa de 4,0 ou moins. Il est préférable que le composé α ait un groupe carbonyle et que le groupe carbonyle soit directement lié au groupe OH ou au groupe alcoxy. Il est également préférable que le composé α ait un cycle benzénique et que le groupe azide ou similaire soit directement lié au cycle benzénique.
PCT/JP2023/003885 2022-02-06 2023-02-06 Solution de traitement de surface, et procédé de fabrication de résine traitée en surface et stratifié de film de résine WO2023149581A1 (fr)

Applications Claiming Priority (4)

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JP2022016783A JP7120695B1 (ja) 2022-02-06 2022-02-06 樹脂フィルム積層体とその製造方法、及び金属被覆樹脂の製造方法
JP2022-016783 2022-02-06
JP2022-100599 2022-06-22
JP2022100599A JP2023114962A (ja) 2022-02-06 2022-06-22 表面処理液、表面処理樹脂及び樹脂フィルム積層体の製造方法

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03141300A (ja) * 1989-07-26 1991-06-17 Millipore Corp 不溶性支持体に対する蛋白及びペプチドの固定化
JP2016047849A (ja) * 2005-09-15 2016-04-07 ジェンザイム コーポレーション アミンポリマー用サシェ製剤
JP6438747B2 (ja) * 2014-11-27 2018-12-19 三井化学株式会社 複合体の製造方法
JP2020521574A (ja) * 2017-05-30 2020-07-27 ズーゾズ アクチェンゲゼルシャフト 切替可能な湿潤−乾燥潤滑性コーティングを有するデバイス

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03141300A (ja) * 1989-07-26 1991-06-17 Millipore Corp 不溶性支持体に対する蛋白及びペプチドの固定化
JP2016047849A (ja) * 2005-09-15 2016-04-07 ジェンザイム コーポレーション アミンポリマー用サシェ製剤
JP6438747B2 (ja) * 2014-11-27 2018-12-19 三井化学株式会社 複合体の製造方法
JP2020521574A (ja) * 2017-05-30 2020-07-27 ズーゾズ アクチェンゲゼルシャフト 切替可能な湿潤−乾燥潤滑性コーティングを有するデバイス

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