WO2021085329A1 - Composition de résine, film de résine, corps stratifié, film de couverture, feuille de cuivre avec résine, carte stratifiée revêtue de métal et carte de circuit imprimé - Google Patents

Composition de résine, film de résine, corps stratifié, film de couverture, feuille de cuivre avec résine, carte stratifiée revêtue de métal et carte de circuit imprimé Download PDF

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Publication number
WO2021085329A1
WO2021085329A1 PCT/JP2020/039910 JP2020039910W WO2021085329A1 WO 2021085329 A1 WO2021085329 A1 WO 2021085329A1 JP 2020039910 W JP2020039910 W JP 2020039910W WO 2021085329 A1 WO2021085329 A1 WO 2021085329A1
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Prior art keywords
component
diamine
resin
polyimide
film
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PCT/JP2020/039910
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English (en)
Japanese (ja)
Inventor
祥人 中島
芳樹 須藤
康太 柿坂
哲平 西山
博之 出合
睦人 田中
Original Assignee
日鉄ケミカル＆マテリアル株式会社
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Priority claimed from JP2019238107A external-priority patent/JP7410716B2/ja
Priority claimed from JP2019238108A external-priority patent/JP7398277B2/ja
Application filed by 日鉄ケミカル＆マテリアル株式会社 filed Critical 日鉄ケミカル＆マテリアル株式会社
Priority to KR1020227012505A priority Critical patent/KR20220095186A/ko
Priority to CN202080069299.XA priority patent/CN114502658A/zh
Publication of WO2021085329A1 publication Critical patent/WO2021085329A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of 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 C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
    • 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
    • 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
    • C08K5/17—Amines; Quaternary ammonium compounds
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • 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
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/28—Metal sheet
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • C08J2379/00—Characterised by the use of 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 C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic

Definitions

  • the present invention relates to a resin composition useful as an adhesive in a circuit board such as a printed wiring board, a resin film, a laminate, a coverlay film, a copper foil with resin, a metal-clad laminate, and a circuit board using the resin composition.
  • FPC flexible printed wiring board
  • the high performance of the equipment has advanced, so it is also necessary to deal with the high frequency of the transmission signal.
  • the printed circuit board material has a transmission loss due to the thinning of the insulating layer and the improvement of the dielectric properties of the insulating layer. Is required to decrease.
  • FPCs and adhesives that can handle high frequencies will be required, and it will be important to reduce transmission loss.
  • Patent Document 1 has no examples other than epoxy resins, and detailed studies have not been conducted on thermoplastic resins. Further, it has been proposed to reduce the coefficient of thermal expansion and the relative permittivity by blending silica particles with a polyimide resin used as an insulating resin layer of a circuit board (Patent Documents 2 and 3).
  • a polyimide made from a diamine compound derived from an aliphatic diamine such as dimer acid (dimeric fatty acid) and at least two primary amino groups are functionalized. It has been proposed to apply a crosslinked polyimide resin obtained by reacting an amino compound as a group to an adhesive layer of a coverlay film (for example, Patent Document 4). Further, it has been proposed to apply a resin composition in which such a polyimide, a thermosetting resin such as an epoxy resin, and a cross-linking agent are used in combination to a copper-clad laminate (for example, Patent Document 5).
  • Patent Document 6 It has also been proposed to achieve both low dielectric loss tangent and flame retardancy by blending a metal salt of organic phosphinic acid with polyimide using a diamine-type diamine.
  • Patent Documents 4 to 6 do not consider the influence of by-products other than diamine diamine derived from dimer acid contained in the raw material.
  • Dimer acid is obtained by a deal-alder reaction using natural fatty acids such as soybean oil fatty acid, tall oil fatty acid, rapeseed oil fatty acid and the like and purified oleic acid, linoleic acid, linolenic acid, erucic acid and the like as raw materials. It is known that a dimerized fatty acid and a polybasic acid compound derived from dimer acid can be obtained as a composition of a raw material fatty acid or a fatty acid having a trimerization or higher (for example, Patent Document 7). ..
  • Japanese Patent No. 6295013 Japanese Unexamined Patent Publication No. 2001-185853 Japanese Unexamined Patent Publication No. 2018-012747 Japanese Unexamined Patent Publication No. 2013-1730 JP-A-2017-119361 Japanese Patent No. 6267509 Japanese Unexamined Patent Publication No. 2017-137375
  • Thermoplastic resins such as polyimide made from an aliphatic diamine compound such as dimer diamine (hereinafter, may be referred to as "aliphatic thermoplastic resin") have room for improvement in flame retardancy, but have low dielectric constant.
  • polyamic acid or polyimide which is a precursor of polyimide
  • polyimide which is a precursor of polyimide
  • it is used in a state containing by-products other than diaminediamine derived from dimer acid.
  • by-products make it difficult to control the molecular weight of polyimide, and also affect the dielectric properties over a wide range of frequencies and their humidity dependence.
  • a first object of the present invention is to provide a resin composition and a resin film capable of coping with high frequency of electronic devices by further improving the dielectric properties of the aliphatic thermoplastic resin. ..
  • a second object of the present invention is to provide a resin composition and a resin film capable of responding to higher frequencies of electronic devices by improving the dielectric properties while using dimer diamine as a raw material.
  • the resin composition of the present invention contains the following components (A) and (B); (A) 40 mol% or more of a diamine diamine composition containing diamine diamine as a main component, which is obtained by substituting a primary aminomethyl group or an amino group with two terminal carboxylic acid groups of dimer acid with respect to the total diamine component.
  • a thermoplastic resin containing a structural unit derived from a diamine component, And (B) one or more selected from aromatic condensed phosphoric acid ester, silica particles, or liquid crystal polymer filler. Contains.
  • the resin composition of the present invention comprises reacting the component (A) with a tetracarboxylic acid anhydride component and a diamine component containing 40 mol% or more of the diamine diamine composition with respect to the total diamine component.
  • a tetracarboxylic acid anhydride component and a diamine component containing 40 mol% or more of the diamine diamine composition with respect to the total diamine component.
  • It may be polyimide
  • the component (B) may be the aromatic condensed phosphoric acid ester.
  • the weight ratio of the component (B) to the component (A) may be in the range of 0.05 to 0.7, preferably in the range of 0.2 to 0.5.
  • the weight ratio of phosphorus derived from the aromatic condensed phosphoric acid ester of the component (B) to the component (A) may be in the range of 0.01 to 0.1.
  • the resin composition of the present invention may further contain an amino compound having at least two primary amino groups as functional groups.
  • the resin composition of the present invention comprises reacting the component (A) with a tetracarboxylic acid anhydride component and a diamine component containing 40 mol% or more of the diamine diamine composition with respect to the total diamine component.
  • a tetracarboxylic acid anhydride component and a diamine component containing 40 mol% or more of the diamine diamine composition with respect to the total diamine component.
  • It may be a polyamic acid or a polyimide
  • the component (B) may be silica particles having a cristobalite crystal phase or a quartz crystal phase.
  • the component (B) is in the range of 5 to 60% by weight based on the total of the component (A) (where polyamic acid is converted to imidized polyimide) and the component (B). You may.
  • the ratio of the total area of the derived peaks may be 20% by weight or more.
  • the silica particles of the component (B) have an average particle diameter D 50 of 6 to 20 ⁇ m in which the cumulative value in the frequency distribution curve obtained by the volume-based particle size distribution measurement by the laser diffraction scattering method is 50%. There may be.
  • the resin composition of the present invention comprises reacting the component (A) with a tetracarboxylic acid anhydride component and a diamine component containing 40 mol% or more of the diamine diamine composition with respect to the total diamine component.
  • a tetracarboxylic acid anhydride component and a diamine component containing 40 mol% or more of the diamine diamine composition with respect to the total diamine component.
  • It may be polyimide
  • the component (B) may be the liquid crystal polymer filler.
  • the component (B) may be in the range of 15 to 50% by volume with respect to the total of the component (A) and the component (B).
  • Dfa the dielectric loss tangent of the liquid crystal polymer filler of the component (B) at 10 GHz
  • Dfb even if the Dfb is less than 0.0019.
  • Dfa> Dfb may be used.
  • 15 to 30% by weight of a phosphorus-based flame retardant may be further added to 100%
  • the component (A) is a tetracarboxylic acid represented by the following general formulas (1) and / or (2) with respect to 100 mol parts of the tetracarboxylic acid anhydride component. A total of 90 mol parts or more of the anhydride may be contained.
  • X represents a single bond or a divalent group selected from the following formula
  • the cyclic portion represented by Y is a 4-membered ring or a 5-membered ring. , 6-membered ring, 7-membered ring or 8-membered ring.
  • the resin film of the present invention is a resin film containing a thermoplastic resin layer, and has the following components (A) and (B); (A) 40 mol% or more of a diamine diamine composition containing diamine diamine as a main component, which is obtained by substituting a primary aminomethyl group or an amino group with two terminal carboxylic acid groups of dimer acid with respect to the total diamine component.
  • a thermoplastic resin containing a structural unit derived from a diamine component, And (B) one or more selected from aromatic condensed phosphoric acid ester, silica particles, or liquid crystal polymer filler. Contains.
  • the resin film of the present invention may have a thickness in the range of 15 to 100 ⁇ m.
  • the content thereof is relative to the total of the component (A) and the component (B). It may be in the range of 3 to 41% by volume.
  • the content thereof is within the range of 15 to 40% by volume with respect to the total of the component (A) and the component (B). It may be.
  • the laminate of the present invention has a base material and an adhesive layer laminated on at least one surface of the base material, and the adhesive layer is made of the above resin film.
  • the coverlay film of the present invention has a coverlay film material layer and an adhesive layer laminated on the coverlay film material layer, and the adhesive layer is made of the above resin film.
  • the resin-containing copper foil of the present invention is obtained by laminating an adhesive layer and a copper foil, and the adhesive layer is made of the above resin film.
  • the metal-clad laminate of the present invention has an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer, and at least one layer of the insulating resin layer is made of the resin film. ..
  • the circuit board of the present invention is formed by wiring the metal layer of the metal-clad laminate.
  • the resin composition of the present invention contains the component (A) and the component (B), the resin film formed by using the component (A) and the component (B) have excellent dielectric properties and flexibility derived from diamine diamine. Moreover, it has a dielectric property further improved by blending the component (B). Therefore, the resin composition and the resin film of the present invention can be particularly preferably used as a circuit board material such as FPC in an electronic device that requires high-speed signal transmission, for example.
  • the resin composition of one embodiment of the present invention contains the following components (A) and (B); (A) 40 mol% or more of a diamine diamine composition containing diamine diamine as a main component, which is obtained by substituting a primary aminomethyl group or an amino group with two terminal carboxylic acid groups of dimer acid with respect to the total diamine component.
  • a thermoplastic resin containing a structural unit derived from a diamine component And (B) one or more selected from aromatic condensed phosphoric acid ester, silica particles, or liquid crystal polymer filler. Contains.
  • component (A) component thermoplastic resin is a diamine diamine containing a diamine diamine as a main component, in which the two terminal carboxylic acid groups of the diamine are replaced with a primary aminomethyl group or an amino group with respect to the total diamine component.
  • a resin containing a structural unit derived from a diamine component containing 40 mol% or more of the composition, and the maximum value of loss tangent (tan ⁇ ) measured using a dynamic viscoelasticity measuring device (DMA) is 200 ° C. Means less than resin.
  • thermoplastic resin a thermoplastic polyimide using a diamine component containing 40 mol% or more of a diamine diamine composition as a raw material, a polyamic acid as a precursor thereof, a thermoplastic bismaleimide resin, a thermoplastic epoxy resin, and heat.
  • thermoplastic polyamide resins examples thereof include thermoplastic polyamide resins and cured products thereof.
  • thermoplastic resins can be blended in combination of two or more.
  • the main components are the tetracarboxylic acid anhydride component and the diamine diamine in which the two terminal carboxylic acid groups of dimer acid are replaced with primary aminomethyl groups or amino groups with respect to the total diamine component.
  • thermoplastic polyimide obtained by reacting a diamine component containing 40 mol% or more of the diamine diamine composition with the above, and imidizing the polyamic acid of the precursor (hereinafter, may be referred to as "DDA-based thermoplastic polyimide”).
  • DDA-based thermoplastic polyimide a thermoplastic polyimide obtained by reacting a diamine component containing 40 mol% or more of the diamine diamine composition with the above, and imidizing the polyamic acid of the precursor (hereinafter, may be referred to as "DDA-based thermoplastic polyimide”).
  • DDA-based thermoplastic polyimide a thermoplastic polyimide obtained by reacting a diamine component containing 40 mol% or more of the diamine diamine composition with the above, and imidizing the polyamic acid of the precursor
  • thermoplastic polyimide is generally a polyimide in which the glass transition temperature (Tg) can be clearly confirmed, but in the present invention, it is measured at 30 ° C. using a dynamic viscoelasticity measuring device (DMA).
  • DMA dynamic viscoelasticity measuring device
  • the "non-thermoplastic polyimide” is a polyimide that generally does not soften or show adhesiveness even when heated, but in the present invention, it was measured using a dynamic viscoelasticity measuring device (DMA).
  • DMA dynamic viscoelasticity measuring device
  • the DDA-based thermoplastic polyimide is an aliphatic-based thermoplastic polyimide, which is highly flexible, has sufficient toughness even when a large amount of liquid crystal polymer filler is added, and when a resin film is formed, the DDA-based thermoplastic polyimide is used. High ability to retain shape. Therefore, the content of the DDA-based thermoplastic polyimide in the component (A) is preferably 60% by weight or more, more preferably 70% by weight or more, and most preferably 80% by weight or more. When the content of the DDA-based thermoplastic polyimide in the component (A) is less than 60% by weight, the toughness of the thermoplastic resin is lowered, and the film retention when the resin film is formed is lowered.
  • the DDA-based thermoplastic polyimide contains a tetracarboxylic acid residue derived from the raw material tetracarboxylic dianhydride and a diamine residue derived from the raw material diamine compound.
  • the tetracarboxylic acid anhydride generally used for the thermoplastic polyimide can be used as a raw material without particular limitation, but the following general formula (1) and / Alternatively, it is preferable to contain 90 mol% or more of the tetracarboxylic acid anhydride represented by (2) in total.
  • the DDA-based thermoplastic polyimide is derived from the tetracarboxylic dianhydride represented by the following general formulas (1) and / or (2) for 100 mol parts of all tetracarboxylic acid residues.
  • tetracarboxylic acid residue it is preferable to contain 90 mol parts or more of the tetracarboxylic acid residue in total.
  • a total of 90 mol or more of tetracarboxylic acid residues derived from the tetracarboxylic dianhydride represented by the following general formulas (1) and / or (2) is added to 100 mol of tetracarboxylic acid residue.
  • the solvent solubility of the DDA-based thermoplastic polyimide is high. It tends to decrease.
  • X represents a single bond or a divalent group selected from the following formula
  • the cyclic portion represented by Y is a 4-membered ring or a 5-membered ring. , 6-membered ring, 7-membered ring or 8-membered ring.
  • Examples of the tetracarboxylic dianhydride represented by the general formula (1) include 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3', 4,4'. -Benzophenone tetracarboxylic dianhydride (BTDA), 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4'-oxydiphthalic anhydride (ODPA), 4,4 '-(Hexafluoroisopropylidene) diphthalic anhydride (6FDA), 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride (BPADA), p-phenylenebis (trimerit) Acid monoesteric anhydride) (TAHQ), ethylene glycol bisamhydrotrimeritate (TMEG) and the like can be mentioned.
  • BPDA 4,4'-biphenyltetracarboxylic
  • BTDA 3,3', 4,4'-benzophenone tetracarboxylic dianhydride
  • BTDA 3,3', 4,4'-benzophenone tetracarboxylic dianhydride
  • the carbonyl group (ketone group) contributes to the adhesiveness, the decrease in peel strength when the liquid crystal polymer filler is added as the component (B) is suppressed, and the adhesion of the DDA-based thermoplastic polyimide is suppressed.
  • the sex can be improved.
  • 100 mol parts or more of the tetracarboxylic acid residue derived from BTDA is preferably contained in an amount of 50 parts by mole or more, more preferably 60 parts by mole or more, based on 100 mol parts of the tetracarboxylic acid residue.
  • Examples of the tetracarboxylic dianhydride represented by the general formula (2) include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarboxylic dianhydride. Dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cycloheptantetracarboxylic dianhydride, 1,2,5,6-cyclooctanetetracarboxylic dianhydride Dianhydride and the like can be mentioned.
  • the DDA-based thermoplastic polyimide is a tetracarboxylic acid residue derived from an acid anhydride other than the tetracarboxylic acid anhydride represented by the above general formulas (1) and (2) as long as the effects of the invention are not impaired.
  • Such tetracarboxylic acid residues are not particularly limited, but for example, pyromellitic acid dianhydride, 2,3', 3,4'-biphenyltetracarboxylic acid dianhydride, 2,2', 3 , 3'-or 2,3,3', 4'-benzophenone tetracarboxylic acid dianhydride, 2,3', 3,4'-diphenyl ether tetracarboxylic acid dianhydride, bis (2,3-dicarboxyphenyl) ) Ether dianhydride, 3,3'', 4,4''-, 2,3,3'', 4''-or 2,2'',3,3''-p-terphenyltetracarboxylic Acid dianhydride, 2,2-bis (2,3- or 3,4-dicarboxyphenyl) -propane dianhydride, bis (2,3- or 3,4-dicarboxyphenyl) methane dianhydride, Bis (2,
  • the DDA-based thermoplastic polyimide uses a diamine component containing 40 mol% or more, more preferably 60 mol% or more of the diamine diamine composition with respect to the total diamine component as a raw material.
  • the dimer diamine composition in the above amount, the dielectric property of the polyimide is improved, the thermocompression bonding property is improved by lowering the glass transition temperature of the polyimide (lower Tg), and the internal stress is lowered by lowering the elastic modulus. Can be alleviated.
  • the diamine diamine composition contains the following component (a) as a main component, and the amounts of the components (b) and (c) are controlled.
  • Dimer diamine The dimer diamine component (a), two terminal carboxylic acid groups of dimer acid (-COOH) is replaced in primary aminomethyl group (-CH 2 -NH 2) or an amino group (-NH 2) It means diamine.
  • Dimeric acid is a known dibasic acid obtained by the intermolecular polymerization reaction of unsaturated fatty acids, and its industrial production process is almost standardized in the industry, and unsaturated fatty acids having 11 to 22 carbon atoms are used as clay catalysts. It is obtained by dimerizing with.
  • the industrially obtained dimer acid is mainly composed of a dibasic acid having 36 carbon atoms obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms such as oleic acid, linolenic acid and linolenic acid. Depending on the degree, it contains an arbitrary amount of monomeric acid (18 carbon atoms), trimeric acid (54 carbon atoms), and other polymerized fatty acids having 20 to 54 carbon atoms. Further, although the double bond remains after the dimerization reaction, in the present invention, the dimer acid is also included in which the degree of unsaturation is lowered by the hydrogenation reaction.
  • the dimer diamine of the component (a) is prepared by substituting a primary aminomethyl group or an amino group for the terminal carboxylic acid group of the dibasic acid compound in the range of 18 to 54 carbon atoms, preferably 22 to 44 carbon atoms. It can be defined as the resulting diamine compound.
  • dimer diamine As a characteristic of dimer diamine, it is possible to impart properties derived from the skeleton of dimer acid. That is, since dimer diamine is an aliphatic of macromolecules having a molecular weight of about 560 to 620, the molar volume of the molecule can be increased and the polar groups of the DDA-based thermoplastic polyimide can be relatively reduced. It is considered that such a feature of the dimer acid type diamine contributes to improving the dielectric property by reducing the relative permittivity and the dielectric loss tangent while suppressing the decrease in the heat resistance of the DDA-based thermoplastic polyimide.
  • the DDA-based thermoplastic polyimide since it has two freely moving hydrophobic chains having 7 to 9 carbon atoms and two chain-like aliphatic amino groups having a length close to 18 carbon atoms, it gives flexibility to the DDA-based thermoplastic polyimide. Not only that, since the DDA-based thermoplastic polyimide can have an asymmetrical chemical structure or a non-planar chemical structure, it is considered that the dielectric constant can be lowered.
  • the diamine diamine composition used is such that the diamine diamine content of the component (a) is increased to 96% by weight or more, preferably 97% by weight or more, more preferably 98% by weight or more by a purification method such as molecular distillation. That's good.
  • a purification method such as molecular distillation. That's good.
  • the monobasic acid compound in the range of 10 to 40 carbon atoms is a monobasic unsaturated fatty acid in the range of 10 to 20 carbon atoms derived from the raw material of dimer acid, and a by-product during the production of dimer acid. It is a mixture of monobasic acid compounds in the range of 21 to 40 carbon atoms.
  • the monoamine compound is obtained by substituting the terminal carboxylic acid group of these monobasic acid compounds with a primary aminomethyl group or an amino group.
  • the monoamine compound of the component (b) is a component that suppresses an increase in the molecular weight of polyimide.
  • the monofunctional amino group of the monoamine compound reacts with the terminal acid anhydride group of the polyamic acid or polyimide to seal the terminal acid anhydride group, and the molecular weight of the polyamic acid or polyimide is sealed. Suppress the increase.
  • the polybasic acid compound having a hydrocarbon group having a carbon number of 41 to 80 is mainly composed of a tribasic acid compound having a carbon number of 41 to 80, which is a by-product during the production of dimer acid. It is a polybasic acid compound. Further, it may contain a polymerized fatty acid other than dimer acid having 41 to 80 carbon atoms.
  • the amine compound is obtained by substituting the terminal carboxylic acid group of these polybasic acid compounds with a primary aminomethyl group or an amino group.
  • the amine compound of the component (c) is a component that promotes an increase in the molecular weight of polyimide.
  • a trifunctional or higher amino group containing a triamine derived from trimeric acid as a main component reacts with a polyamic acid or a terminal acid anhydride group of polyimide to rapidly increase the molecular weight of polyimide.
  • an amine compound derived from a polymerized fatty acid other than dimer acid having 41 to 80 carbon atoms also increases the molecular weight of the polyimide and causes gelation of the polyamic acid or the polyimide.
  • the above diamine diamine composition is used to facilitate confirmation of peak start, peak top and peak end of each component of the diamine diamine composition when quantification of each component is performed by measurement using gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • a sample obtained by treating the diamine diamine composition with anhydrous acetic acid and pyridine is used, and cyclohexanone is used as an internal standard substance.
  • each component is quantified by the area percentage of the GPC chromatogram.
  • the peak start and peak end of each component are set to the minimum value of each peak curve, and the area percentage of the chromatogram can be calculated based on this.
  • the total area of the components (b) and (c) is 4% or less, preferably less than 4%, in terms of the area percentage of the chromatogram obtained by GPC measurement.
  • the area percentage of the chromatogram of the component (b) is preferably 3% or less, more preferably 2% or less, still more preferably 1% or less.
  • the area percentage of the chromatogram of the component (c) is 2% or less, preferably 1.8% or less, and more preferably 1.5% or less. Within such a range, a rapid increase in the molecular weight of the polyimide can be suppressed, and an increase in the dielectric loss tangent of the resin film at a wide frequency range can be suppressed.
  • the component (c) may not be contained in the diamine diamine composition.
  • the molar ratio of the tetracarboxylic acid anhydride component and the diamine component is preferably 0.97 or more and less than 1.0, and such a molar ratio makes it easier to control the molecular weight of the polyimide.
  • the ratio (b / c) of the area percentage of the chromatograms of the components (b) and (c) is less than 1, the molar ratio of the tetracarboxylic acid anhydride component and the diamine component (tetracarboxylic acid anhydride component).
  • the / diamine component) is preferably 0.97 or more and 1.1 or less, and such a molar ratio makes it easier to control the molecular weight of the polyimide.
  • the diamine diamine composition used in the present invention is preferably purified for the purpose of reducing components other than diamine diamine as component (a).
  • the purification method is not particularly limited, but a known method such as a distillation method or precipitation purification is preferable.
  • the diamine diamine composition before purification can be obtained as a commercially available product, and examples thereof include PRIAMINE 1073 (trade name), PRIAMINE 1074 (trade name), and PRIAMINE 1075 (trade name) manufactured by Croda Japan.
  • diamine compounds other than dimer diamine used in DDA-based thermoplastic polyimide include aromatic diamine compounds and aliphatic diamine compounds. Specific examples thereof include 1,4-diaminobenzene (p-PDA; paraphenylenediamine), 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB), 2,2'-n-.
  • Propyl-4,4'-diaminobiphenyl (m-NPB), 4-aminophenyl-4'-aminobenzoate (APAB), 2,2-bis- [4- (3-aminophenoxy) phenyl] propane, bis [ 4- (3-Aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) biphenyl, bis [1- (3-aminophenoxy)] biphenyl, bis [4- (3-aminophenoxy) phenyl] methane , Bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy)] benzophenone, 9,9-bis [4- (3-aminophenoxy) phenyl] fluorene, 2,2- Bis- [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis- [4- (3-aminophenoxy) phen
  • the DDA-based thermoplastic polyimide can be produced by reacting the above-mentioned tetracarboxylic acid anhydride component and the diamine component in a solvent to generate polyamic acid, and then heat-closing the ring.
  • the tetracarboxylic dianhydride component and the diamine component are dissolved in an organic solvent in approximately equimolar amounts, and the mixture is stirred at a temperature in the range of 0 to 100 ° C. for 30 minutes to 24 hours to carry out a polymerization reaction to form a polyimide precursor.
  • Polyamic acid is obtained.
  • the reaction components are dissolved in an organic solvent so that the precursor produced is in the range of 5 to 50% by weight, preferably in the range of 10 to 40% by weight.
  • organic solvent used in the polymerization reaction include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N, N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), 2 -Butanone, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, N-methylcaprolactam, dimethylsulfate, cyclohexanone, methylcyclohexane, dioxane, tetrahydrofuran, diglime, triglime, methanol, ethanol, benzyl alcohol, cresol and the like can be mentioned.
  • Two or more of these solvents can be used in combination, and aromatic hydrocarbons such as xylene and toluene can be used in combination.
  • the amount of such an organic solvent used is not particularly limited, but it should be adjusted so that the concentration of the polyamic acid solution obtained by the polymerization reaction is about 5 to 50% by weight. Is preferable.
  • the synthesized polyamic acid is usually advantageous to be used as a reaction solvent solution, but can be concentrated, diluted or replaced with another organic solvent if necessary.
  • polyamic acid is generally excellent in solvent solubility, and is therefore advantageously used.
  • the viscosity of the polyamic acid solution is preferably in the range of 500 cps to 100,000 cps. If it is out of this range, defects such as thickness unevenness and streaks are likely to occur in the film during coating work by a coater or the like.
  • the method of imidizing the polyamic acid to form the polyimide is not particularly limited, and for example, a heat treatment such as heating in the solvent under a temperature condition in the range of 80 to 400 ° C. for 1 to 24 hours is preferably adopted. Will be done. Further, the temperature may be heated under a constant temperature condition, or the temperature may be changed in the middle of the process.
  • the dielectric is selected by selecting the types of the tetracarboxylic acid anhydride component and the diamine component and the molar ratio of each when two or more types of the tetracarboxylic acid anhydride component or the diamine component are applied.
  • the characteristics, coefficient of thermal expansion, tensile elastic modulus, glass transition temperature, etc. can be controlled.
  • when a plurality of structural units of polyimide are present it may exist as a block or randomly, but it is preferable that it exists randomly.
  • the weight average molecular weight of the DDA-based thermoplastic polyimide is preferably in the range of, for example, 10,000 to 200,000, and within such a range, the weight average molecular weight of the polyimide can be easily controlled. Further, for example, when applied as an adhesive for FPC, the weight average molecular weight of the DDA-based thermoplastic polyimide is more preferably in the range of 20,000 to 150,000, and further in the range of 40,000 to 150,000. preferable. When applied as an adhesive for FPC, when the weight average molecular weight of the DDA-based thermoplastic polyimide is less than 20,000, the flow resistance tends to deteriorate.
  • the imide group concentration of the DDA-based thermoplastic polyimide is preferably 22% by weight or less, more preferably 20% by weight or less.
  • the "imide group concentration” means a value obtained by dividing the molecular weight of the imide base portion (-(CO) 2 -N-) in the polyimide by the molecular weight of the entire structure of the polyimide.
  • the imide group concentration exceeds 22% by weight, the molecular weight of the resin itself becomes small, the low hygroscopicity deteriorates due to the increase in polar groups, and the Tg and elastic modulus increase.
  • the DDA-based thermoplastic polyimide most preferably has a completely imidized structure. However, a part of the polyimide may be amic acid.
  • crosslink-forming amino compound an amino compound having the ketone group and at least two primary amino groups as functional groups.
  • tetracarboxylic acid anhydride for forming a DDA-based thermoplastic polyimide having a ketone group for example, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride (BTDA) is used as a diamine compound.
  • BTDA 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride
  • aromatic diamines such as 4,4'-bis (3-aminophenoxy) benzophenone (BABP) and 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene (BABB) can be mentioned. ..
  • the resin composition of the present embodiment particularly contains BTDA residues derived from BTDA in an amount of preferably 50 mol% or more, more preferably 50 mol% or more, based on all tetracarboxylic acid residues. It is preferable to contain a DDA-based thermoplastic polyimide and an amino compound for forming a crosslink in the component (A) containing 60 mol% or more.
  • the "BTDA residue” means a tetravalent group derived from BTDA.
  • crosslink-forming amino compound examples include (I) dihydrazide compound, (II) aromatic diamine, and (III) aliphatic amine.
  • dihydrazide compounds are preferable.
  • Aliphatic amines other than dihydrazide compounds tend to form crosslinked structures even at room temperature, and there is a concern about storage stability of varnishes, while aromatic diamines need to be heated to a high temperature in order to form crosslinked structures.
  • the dihydrazide compound when used, both the storage stability of the varnish and the shortening of the curing time can be achieved at the same time.
  • dihydrazide compound examples include dihydrazide oxalic acid, dihydrazide malonate, dihydrazide succinic acid, dihydrazide glutalide, adipic acid dihydrazide, dihydrazide dihydric acid, dihydrazide sberinate, dihydrazide azeline acid, dihydrazide sebacic acid, and dihydrazide sevacinate.
  • Dihydrazide dihydrazide fumarate, diglycolic acid dihydrazide, tartrate dihydrazide, malic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 2,6-naphthoediic acid dihydrazide, 4,4-bisbenzenedihydrazide, 1,4 Dihydrazide compounds such as -naphthoic acid dihydrazide, 2,6-pyridinediic acid dihydrazide, and itaconic acid dihydrazide are preferred.
  • the above dihydrazide compounds may be used alone or in combination of two or more.
  • amino compounds such as (I) dihydrazide compound, (II) aromatic diamine, and (III) aliphatic amine are, for example, a combination of (I) and (II), a combination of (I) and (III), and the like. It is also possible to use two or more combinations across categories, such as the combination of (I), (II) and (III).
  • the cross-linking amino compound used in the present invention has a molecular weight (when the cross-linking amino compound is an oligomer).
  • the weight average molecular weight is preferably 5,000 or less, more preferably 90 to 2,000, and even more preferably 100 to 1,500.
  • an amino compound for cross-linking having a molecular weight of 100 to 1,000 is particularly preferable.
  • the cross-linking amino compound is added to the resin solution containing the component (A) to form a DDA.
  • the ketone group in the system thermoplastic polyimide is subjected to a condensation reaction with the primary amino group of the amino compound for forming a crosslink.
  • the resin solution is cured to become a cured product.
  • the amount of the amino compound for forming a bridge is 0.004 mol to 1.5 mol, preferably 0.005 mol to 1.2 mol, in total of the primary amino group with respect to 1 mol of the ketone group.
  • the cross-linking amino compound can be more preferably 0.03 mol to 0.9 mol, and most preferably 0.04 mol to 0.6 mol. If the amount of the cross-linking amino compound added so that the total number of primary amino groups is less than 0.004 mol with respect to 1 mol of the ketone group, the cross-linking by the cross-linking amino compound is not sufficient, and therefore after curing. Heat resistance tends to be difficult to develop, and when the amount of the cross-linking amino compound added exceeds 1.5 mol, the unreacted cross-linking amino compound acts as a thermoplastic agent, and the heat resistance as the adhesive layer is lowered. Tends to let.
  • the condition is not particularly limited as long as it is a condition for forming.
  • the temperature of the heat condensation simplifies the condensation step in order to release the water generated by the condensation to the outside of the system or when the heat condensation reaction is subsequently carried out after the synthesis of the DDA-based thermoplastic polyimide in the component (A). For some reason, for example, the temperature is preferably in the range of 120 to 220 ° C, more preferably in the range of 140 to 200 ° C.
  • the reaction time is preferably about 30 minutes to 24 hours.
  • the end point of the reaction is the absorption derived from the ketone group in the polyimide resin near 1670 cm -1 by measuring the infrared absorption spectrum using, for example, a Fourier transform infrared spectrophotometer (commercially available product: FT / IR620 manufactured by JASCO Corporation). It can be confirmed by the decrease or disappearance of the peak and the appearance of the absorption peak derived from the imine group near 1635 cm-1.
  • the thermal condensation of the ketone group of the DDA-based thermoplastic polyimide in the component (A) and the primary amino group of the above-mentioned cross-linking amino compound is, for example, (1) A method of adding and heating an amino compound for forming a crosslink, following the synthesis (imidization) of the DDA-based thermoplastic polyimide in the component (A). (2) An excess amount of an amino compound is charged in advance as a diamine component, and following the synthesis (imidization) of the DDA-based thermoplastic polyimide in the component (A), the remaining amino compounds that are not involved in imidization or amidation are used.
  • a method of heating with a DDA-based thermoplastic polyimide using as an amino compound for cross-linking Or (3) After processing the composition of the DDA-based thermoplastic polyimide in the component (A) to which the above amino acid for cross-linking is added into a predetermined shape (for example, after applying it to an arbitrary base material or forming it into a film). After) how to heat, It can be done by such as.
  • the formation of an imine bond was described in the formation of a crosslinked structure, but the formation is not limited to this, and the curing of the polyimide in the component (A) is not limited to this.
  • a compound having an unsaturated bond such as an epoxy resin, an epoxy resin curing agent, a maleimide, an activated ester resin, or a resin having a styrene skeleton can be blended and cured.
  • the resin composition of the present embodiment contains, as the component (B), one or more selected from aromatic condensed phosphoric acid esters, silica particles, and liquid crystal polymer fillers.
  • the component (B) two or more kinds may be used in combination.
  • the aromatic condensed phosphoric acid ester will be referred to as “(B1) component”
  • the silica particles will be referred to as “(B2) component”
  • the liquid crystal polymer filler will be referred to as “(B3) component” in this order.
  • the "aromatically condensed phosphoric acid ester" of the component (B1) is a phosphoric acid ester compound having a chemical structure in which two or more phosphoric acid ester units are linked by a divalent organic group having an aromatic ring, or an oxy. It means a reaction product of phosphorus chloride, a divalent phenolic compound and a phenol or an alkylphenol.
  • the reason for this is not yet clear, but due to the unique chemical structure of the aromatic condensed phosphate, the dielectric properties of the aromatic condensed phosphate itself and the compatibility with the polyimide obtained using the diamine diamine composition are However, since it does not excessively increase the motility of the molecular chain, it is presumed to contribute to lowering the dielectric constant and lowering the dielectric constant tangent. Further, the resin film obtained by using the component (B1) has low humidity dependence of dielectric properties and is excellent in stability.
  • a preferable example of the aromatic condensed phosphoric acid ester is a compound having the structure of the following general formula (3).
  • a plurality of Rs are aromatic hydrocarbon groups which may independently have a substituent
  • Ar is a divalent organic group having an aromatic ring
  • n is 1. It means the above integers.
  • the aromatic condensed phosphoric acid ester represented by the general formula (3) may be a dimer in which n is 1, or a multimer in which n is 2 or more. Further, the compound is not limited to a single compound, and may be a mixture.
  • an aryl group having 6 to 15 carbon atoms can be mentioned, and more specifically.
  • examples include a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a butylphenyl group, a nonylphenyl group and the like.
  • a preferable example of the divalent organic group represented by Ar for example, an alkylene group, an arylene group and the like can be mentioned, and these have a substituent. May be good. More preferable ones include, for example, a phenylene group and a group represented by the following formula (4).
  • Y 1 is a single bond, -CH 2- , -C (CH 3 ) 2- , -SO 2- , -C 5 H 10- , -C 6 H 12- , -C 7 H 14 -, -C 8 H 16-, etc.
  • a biphenyldiyl group in which Y 1 is a single bond is more preferable.
  • aromatic condensed phosphoric acid ester examples include resorcinol bis-diphenyl phosphate, resorcinol bis-dixylenyl phosphate, and bisphenol A bis-diphenyl phosphate.
  • Commercially available products are available as these aromatic condensed phosphoric acid esters, for example, CR-733S (trade name), CR-741 (trade name), CR-747 (trade name), PX-200 (commodity name). Name), PX-200B (trade name) [above, manufactured by Daihachi Chemical Industry Co., Ltd.] and the like. Two or more kinds of these aromatic condensed phosphoric acid esters may be used in combination.
  • the weight ratio of the component (B1) to the component (A) in the resin composition of the present embodiment is in the range of 0.05 to 0.7, and the film such as the tensile elastic modulus when the resin film is formed. Considering the physical properties, it is preferably in the range of 0.2 to 0.5 (the same applies to the resin film described later). If the weight ratio of the component (B1) to the component (A) is less than 0.05, the improvement of the dielectric property may be insufficient, and if it exceeds 0.7, it may be difficult to form the polyimide. In addition, the obtained polyimide film may be weakened. By setting the blending amount of the component (B1) within the above range, the dielectric properties can be improved. When the component (A) is a polyamic acid, the weight ratio is calculated by converting it into polyimide (the same applies hereinafter).
  • the weight ratio of phosphorus derived from the component (B1) to the thermoplastic resin of the component (A) of the component (B1) is in the range of 0.01 to 0.1. It is preferable that they are blended in such a manner. If the weight ratio of phosphorus derived from the component (B1) is less than 0.01, the improvement of the dielectric property is insufficient, and if it exceeds 0.1, the polyimide film (or the polyimide layer) may be weakened.
  • the component (B1) in the resin composition of the present embodiment is the weight ratio of phosphorus derived from the component (B1) to the diamine diamine composition contained in the component (A) ⁇ phosphorus derived from the component (B1) / (A).
  • the diamine diamine composition in the component is preferably in the range of 0.01 to 0.15. If it is less than the above lower limit, the improvement of the dielectric property may be insufficient, and if it exceeds the above upper limit, it may be difficult to form the polyimide, and the obtained polyimide film may be weakened.
  • silica particles of the component (B2) either crystalline silica particles or amorphous silica particles can be used, but those containing crystalline silica particles having a cristobalite crystal phase or a quartz crystal phase are preferable.
  • the silica particles of the component (B2) By blending the silica particles of the component (B2), the dielectric loss tangent when the resin film is formed can be reduced. From the viewpoint of achieving low dielectric loss tangent when the resin film is formed, it is particularly preferable to use silica particles having a cristobalite crystal phase as the crystalline silica particles.
  • Silica particles having a cristobalite crystal phase have extremely excellent dielectric properties as compared with general silica particles (for example, silica particles containing 90% by weight or more of a cristobalite crystal phase alone have a dielectric loss tangent at 20 GHz. (Approximately 0001), which can greatly contribute to the low dielectric loss tangent of the resin film.
  • spherical silica particles are silica particles having a shape close to a true sphere, and the ratio of the average major axis to the average minor axis is close to 1 or 1.
  • the flame retardancy can be improved by adding silica particles of the component (B2).
  • the ratio of the total area of the peaks derived from the cristobalite crystal phase and the quartz crystal phase to the total area of the peaks is preferably 20% by weight or more, more preferably 40% by weight or more, and preferably 80% by weight or more.
  • the ratio of the area of the peak derived from the cristobalite crystal phase and the quartz crystal phase to the entire silica particles is less than 20% by weight, the effect of improving the dielectric property becomes unclear. If the target peak in the X-ray diffraction analysis spectrum is difficult to separate from the amorphous broad peak or overlaps with other crystal phase peaks, various known analysis methods such as the internal standard method and PONKCS The law etc. can be used.
  • the silica particles preferably have an average particle diameter D 50 in the range of 6 to 20 ⁇ m, and more preferably in the range of 8 to 15 ⁇ m.
  • the average particle size D 50 is a value at which the cumulative value in the frequency distribution curve obtained by the volume-based particle size distribution measurement by the laser diffraction / scattering method is 50%.
  • the average particle size D 50 is within this range, the dielectric properties can be effectively improved, and the surface smoothness when the resin film is formed by the resin composition is not deteriorated, so that a low dielectric film having a good appearance can be obtained. can get.
  • the average particle size D 50 is less than the above range, the specific surface area of the silica particles increases, and the adsorbed water and polar groups on the surface of the silica particles may affect the dielectric properties. If the average particle size D 50 exceeds the above range, it may appear as irregularities on the surface of the resin film, which may deteriorate the smoothness of the film surface.
  • the silica particles having a particle size of 3 ⁇ m or more preferably have a circularity of 0.7 or more, and more preferably 0.9 or more.
  • the circularity of the silica particles can be determined by the image analysis method, assuming a circle having the same projected area as the photographed particles, and the ratio of the peripheral length of the circle to the peripheral length of the particles. If the circularity is less than 0.7, the surface area increases, the dielectric properties may be adversely affected, and the viscosity increases when blended in the resin solution, making handling difficult. Further, even in the sphericity obtained three-dimensionally, a value substantially corresponding to the value of the circularity is preferable.
  • the silica particles preferably have a true specific gravity of 2.3 or more. If the true specific gravity is less than 2.3, it is suggested that the crystallinity of the silica particles is small, and the effect of improving the dielectric properties is reduced.
  • silica particles commercially available products can be appropriately selected and used.
  • spherical cristobalite silica powder manufactured by Nittetsu Chemical & Materials Co., Ltd., trade name; CR10-20
  • spherical amorphous silica powder manufactured by Nittetsu Chemical & Materials Co., Ltd., trade name; SC70-2
  • two or more different types of silica particles may be used in combination as the silica particles.
  • the weight ratio of the component (B2) to the total of the components (A) and (B2) in the resin composition of the present embodiment is in the range of 5 to 60% by weight (the same applies to the resin film described later). .. If the weight ratio of the component (B2) to the total of the components (A) and (B2) is less than 5% by weight, the effect of improving the dielectric property and flame retardancy may be insufficient, and if it exceeds 60% by weight. It may be difficult to form the polyimide, and the obtained polyimide film may be weakened. By setting the blending amount of the component (B2) within the above range, the dielectric properties and flame retardancy can be improved.
  • the peak area derived from the cristobalite crystal phase and the quartz crystal phase is 30% by weight or more. It is preferable to add crystalline silica to the mixture.
  • the volume ratio of the component (B2) to the total of the components (A) and (B2) is in the range of 3 to 41%. It is preferably in the range of 10 to 35% (the same applies to the resin film described later).
  • the volume ratio can be obtained by calculation from the density and weight ratio of the components (A) and (B2) to be blended, or by observing the cross section with a scanning electron microscope.
  • the liquid crystal polymer filler is a particle made of a liquid crystal polymer that forms an optically anisotropic molten phase.
  • Liquid crystal polymers that form an optically anisotropic molten phase are also called thermotropic liquid crystal polymers.
  • the polymer that forms the fused phase that forms optically anisotropy is a polymer that transmits polarized light when a sample in a molten state is observed under a polarizing microscope orthogonal Nicol equipped with a heating device.
  • the liquid crystal polymer has almost no frequency dependence, has very excellent dielectric properties, and also contributes to the improvement of flame retardancy. Therefore, by blending this, the dielectric properties and flame retardancy of the resin film are improved. can do.
  • the liquid crystal polymer is not particularly limited, and examples thereof include known thermotropic liquid crystal polyesters and polyesteramides derived from the compounds classified into the following (1) to (4) and their derivatives. .. (1) Aromatic or aliphatic dihydroxy compounds (2) Aromatic or aliphatic dicarboxylic acids (3) Aromatic hydroxycarboxylic acids (4) Aromatic diamines, aromatic hydroxyamines or aromatic aminocarboxylic acids Aromas in liquid crystal polymers As the number of rings increases, the effect of improving the dielectric properties and flame retardancy can be expected. Therefore, those containing an aromatic dihydroxy compound (aromatic diol) as the above (1) and an aromatic dicarboxylic acid as the above (2) are preferable. ..
  • the liquid crystal polymer obtained from these raw material compounds it is a copolymer having two or more combinations selected from the structural units represented by the following formulas (a) to (g) and is represented by the formula (a).
  • a copolymer containing either a structural unit or a structural unit represented by the formula (b) is preferable, and a copolymer containing the structural unit represented by the formula (a) and the structural unit represented by the formula (b) is more preferable.
  • Formulas (a) and (b) are representative examples of structural units derived from aromatic hydroxycarboxylic acids, and formulas (c), formulas (d) and formulas (e) are derived from aromatic dicarboxylic acids.
  • formulas (f) and (g) are representative examples of a structural unit derived from an aromatic dihydroxy compound (aromatic diol).
  • aromatic diol aromatic diol
  • the aromatic ring may have an arbitrary substituent.
  • the liquid crystal polymer filler alone has a relative permittivity at 10 GHz, preferably in the range of 2.8 to 3.6, more preferably 3. It is preferable to use a film having a dielectric loss tangent in the range of 0.0 to 3.4 and having a dielectric loss tangent at 10 GHz, preferably less than 0.0019, more preferably 0.0015 or less. Further, the liquid crystal polymer filler has a Dfb of less than 0.0019 when the dielectric loss tangent of the component (A) at 10 GHz is Dfa and the dielectric loss tangent of the component (B3) at 10 GHz is Dfb. It is more preferably Dfb.
  • liquid crystal polymer one containing abundant aromatic rings is preferable from the viewpoint of improving flame retardancy.
  • weight ratio of the aromatic ring in the liquid crystal polymer filler it is preferable to use 60% by weight or more, more preferably 70% by weight or more.
  • liquid crystal polymer particles it is preferable to use spherical liquid crystal polymer particles.
  • Spherical liquid crystal polymer particles are liquid crystal polymer particles having a shape close to a true sphere, and the ratio of the average major axis to the average minor axis is close to 1 or 1.
  • the liquid crystal polymer particles preferably have an average particle diameter D 50 in the range of 6 to 20 ⁇ m, and more preferably in the range of 8 to 15 ⁇ m.
  • the average particle size D 50 is a value at which the cumulative value in the frequency distribution curve obtained by the volume-based particle size distribution measurement by the laser diffraction / scattering method is 50%.
  • the average particle size D 50 is within this range, a low-dielectric film having a good appearance can be obtained without deteriorating the surface smoothness when the resin film is formed by the resin composition.
  • the average particle size D 50 is less than the above range, the liquid crystal polymer particles may aggregate when blended as a resin composition, and a uniform resin composition may not be obtained. If the average particle size D 50 exceeds the above range, it may appear as irregularities on the surface of the resin film, which may deteriorate the smoothness of the film surface.
  • the melting point of the liquid crystal polymer is preferably higher than the curing temperature of the resin composition, for example, 250 ° C. or higher.
  • the liquid crystal polymer particles can be appropriately selected and used.
  • a low-dielectric liquid crystal polymer manufactured by JXTG Energy Co., Ltd.
  • two or more different liquid crystal polymer particles may be used in combination as the liquid crystal polymer particles.
  • the ratio of the component (B3) to the total of the components (A) and (B3) in the resin composition of the present embodiment is in the range of 15 to 50% by volume and in the range of 15 to 40% by volume. It is preferable (the same applies to the resin film described later). If the volume ratio of the component (B3) to the total of the components (A) and (B3) is less than 15% by volume, the effect of improving the dielectric property and flame retardancy may be insufficient, and if it exceeds 50% by volume. The formation of polyimide may be difficult, and the resulting resin film may be weakened. By setting the blending amount of the component (B3) within the above range, the dielectric properties and flame retardancy can be improved.
  • the cured film was cross-sectionally observed with a scanning electron microscope or the like, and the liquid crystal polymer filler in the resin composition was observed. It can be obtained by calculating the ratio or the like.
  • the resin composition of the present embodiment can contain an organic solvent.
  • it may be a polyimide solution containing a solvent-soluble DDA-based thermoplastic polyimide and a solvent.
  • the organic solvent include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N, N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), 2-butanone, and dimethyl.
  • Examples thereof include sulfoxide (DMSO), hexamethylphosphoramide, N-methylcaprolactam, dimethylformamide, cyclohexanone, dioxane, tetrahydrofuran, diglime, triglime, cresol and the like. Two or more of these solvents can be used in combination, and aromatic hydrocarbons such as xylene and toluene can be used in combination.
  • the content of the organic solvent is not particularly limited, but it is preferable to adjust the content so that the concentration of the thermoplastic resin is about 5 to 30% by weight.
  • the resin composition of the present embodiment can contain a flame retardant when a liquid crystal polymer filler is used as the component (B).
  • the flame retardant is not particularly limited, but a phosphorus-based flame retardant is preferable.
  • Aliphatic thermoplastic resins such as DDA-based thermoplastic polyimide cannot sufficiently exhibit flame-retardant properties even if a phosphorus-based flame retardant is added because of its low aromatic ring concentration, but the liquidity of the component (B3) is high.
  • the concentration is increased by the aromatic ring derived from the liquid crystal polymer, so that the formation of char (carbonized film) at the time of combustion is promoted and a high flame retardant effect is exhibited.
  • the non-volatile organic compound component means the remaining solid content obtained by removing the solvent and the inorganic solid content from the resin composition. That is, the non-volatile organic compound component contains the thermoplastic resin of the component (A) and the liquid crystal polymer filler of the component (B3), and optional components other than the resin other than the thermoplastic resin and the liquid crystal polymer filler. It can contain an organic filler, a plasticizer, a curing accelerator, a coupling agent, an organic pigment, an organic flame retardant other than a phosphorus flame retardant, and the like.
  • Examples of the phosphorus-based flame retardant include aromatic condensed phosphoric acid ester having the same structure as the above component (B1), a metal salt of organic phosphinic acid, and alkylphosphine (excluding red phosphorus). ..
  • aromatic condensed phosphoric acid ester having the same structure as the above component (B1)
  • a metal salt of organic phosphinic acid excluding red phosphorus
  • alkylphosphine excluding red phosphorus
  • the metal salt of organic phosphinic acid is, for example, a metal salt of phosphoric acid in which two organic groups are bonded to phosphorus, as represented by the following general formula (5).
  • the two organic groups R 11 and R 12 are preferably linear or branched alkyl groups having 1 to 6 carbon atoms, or phenyl groups or tolyl groups, which are the same or different from each other.
  • the metal species M is selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na and K. It is preferable that it is used.
  • M in the general formula (5) is transformed into M1 / n.
  • the two organic groups R 11 and R 12 are preferably an alkyl group having 1 to 3 carbon atoms, and also have flame retardancy and flame retardancy.
  • Aluminum (Al) is preferable as the metal type M in order to improve the flexibility and suppress the solubility in water as a metal salt.
  • Exolit OP930 (trade name), Exolit OP935 (trade name), and Exolit OP940 (trade name), which are aluminum phosphinic acid salts manufactured by Clariant Japan Co., Ltd., are available. ) Etc. can be mentioned.
  • the resin composition of the present embodiment further includes, if necessary, a resin component other than the thermoplastic resin of the component (A), a cross-linking agent, an inorganic filler other than silica particles, and a liquid crystal polymer filler as optional components.
  • a resin component other than the thermoplastic resin of the component (A) e.g., ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, poly(ethylene glycol)-propylene glycol dimethacrylate, poly(ethylene glycol) terpolymer, poly(ethylene glycol) terpolymer, poly(ethylene glycol) terpolymer, poly(ethylene glycol) compound, poly(ethylene glycol) compound, poly(ethylene glycol) compound, poly(ethylene glycol) compound, poly(ethylene glycol) terethacrylate), poly(ethylene glycol) terethacrylate), poly(ethylene glycol) terethacrylate), poly(ethylene glycol)-(
  • inorganic filler examples include aluminum oxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, calcium fluoride and the like. These can be used alone or in admixture of two or more.
  • the viscosity of the resin composition is preferably in the range of, for example, 3000 cps to 100,000 cps, and is preferably in the range of 5000 cps to 100,000 cps as the viscosity range in which the handleability when applying the resin composition is improved and a coating film having a uniform thickness is easily formed. It is more preferably within the range of 50,000 cps. If it is out of the above viscosity range, defects such as thickness unevenness and streaks are likely to occur in the film during coating work by a coater or the like.
  • the resin composition of the present embodiment can be prepared, for example, by preparing a solution of the component (A) using an arbitrary solvent, adding the component (B) to the solution, and mixing them uniformly.
  • the component (B) may be directly added to the resin solution of the DDA-based thermoplastic polyimide.
  • a part of the component (A) may be blended at the same time as the component (B) or after the component (B) is added.
  • the component (B) may be added in the entire amount at one time, or may be added little by little in several times.
  • the raw materials may be added all at once, or may be divided into several times and mixed little by little.
  • the resin composition of the present embodiment has excellent dielectric properties and flame retardancy in addition to excellent flexibility and thermoplasticity when an adhesive layer is formed using the resin composition. Therefore, the resin composition of the present embodiment has preferable properties as an adhesive for a coverlay film that protects wiring portions such as FPCs and rigid flex circuit boards.
  • the resin film of the present embodiment is a resin film containing a thermoplastic resin layer (preferably a DDA-based thermoplastic polyimide layer), and the thermoplastic resin layer is the solid content (remaining portion excluding the solvent) of the resin composition. ) Is the main component and is made into a film. That is, the resin film of the present embodiment contains the component (A) and the component (B), and the weight ratio of the component (B) to the component (A) is in a predetermined range as in the resin composition. It is adjusted within. Since the resin film of the present embodiment has excellent high-frequency characteristics and flame retardancy in addition to flexibility and adhesiveness, it is used for coverlay films that protect wiring portions such as FPCs and rigid flex circuit boards. It can be preferably used in applications such as an adhesive layer of the above and a bonding sheet of a multilayer FPC.
  • a thermoplastic resin layer preferably a DDA-based thermoplastic polyimide layer
  • the thermoplastic resin layer is the solid content (remaining portion excluding the solvent) of
  • the resin film of the present embodiment is not particularly limited as long as it is an insulating resin film containing a thermoplastic resin layer formed from the above resin composition, and is a film (sheet) made of an insulating resin. It may be an insulating resin film laminated on a base material such as a resin sheet such as a copper foil, a glass plate, a polyimide film, a polyamide film, or a polyester film.
  • the resin film of the present embodiment preferably has a glass transition temperature (Tg) of 250 ° C. or lower, more preferably 40 ° C. or higher and 200 ° C. or lower.
  • Tg glass transition temperature
  • the resin film of the present embodiment preferably has a glass transition temperature (Tg) of 250 ° C. or lower, more preferably 40 ° C. or higher and 200 ° C. or lower.
  • the resin film preferably has the following physical properties.
  • SPDR split-post dielectric resonator
  • E 1 value is an index showing the dielectric properties of 10GHz of the original 24-hour moisture adjustment of constant temperature and humidity conditions of RH 50% 0.010 or less, preferably 0.009 or less Is better, more preferably 0.008 or less.
  • E 1 values exceeds the upper limit, for example when used in a circuit board such as an FPC, is likely to occur inconveniences such as loss of electrical signals on the transmission path of the RF signal.
  • the resin film is used at 23 ° C., 50, for ensuring impedance matching when used for a circuit board such as FPC, and for reducing loss of electric signals.
  • the relative permittivity ( ⁇ 1 ) at 10 GHz after humidity control for 24 hours under the constant temperature and humidity condition of% RH is preferably 3.2 or less, and more preferably 3.0 or less. If this relative permittivity exceeds 3.2, inconveniences such as loss of electric signals are likely to occur on the transmission path of high-frequency signals when used for a circuit board such as an FPC.
  • the resin film is used under constant temperature and humidity conditions of 23 ° C. and 50% RH in order to reduce the loss of electric signals when used for a circuit board such as FPC.
  • the dielectric loss tangent (Tan ⁇ 1 ) at 10 GHz after humidity control for 24 hours is preferably less than 0.005, more preferably 0.004 or less. If the dielectric loss tangent is 0.005 or more, inconveniences such as loss of electric signals are likely to occur on the transmission path of high-frequency signals when used for a circuit board such as an FPC.
  • the ratio of the E 2 value to the E 1 value calculated based on the above formula (i) (E 2).
  • / E 1 ) is in the range of 3.0 to 1.0, preferably in the range of 2.5 to 1.0, and more preferably in the range of 2.2 to 1.0. If E 2 / E 1 exceeds the above upper limit, when used for a circuit board such as an FPC, the relative permittivity and the dielectric loss tangent will increase when wet, and the electric signal will be transmitted on the high frequency signal transmission path. Inconveniences such as loss are likely to occur.
  • the resin film has a hygroscopicity of preferably 0.5 weight in order to reduce the influence of humidity when used for a circuit board such as FPC. % Or less is preferable, and more preferably less than 0.3% by weight.
  • the "moisture absorption rate” means the moisture absorption rate after 24 hours or more have elapsed under the constant temperature and humidity conditions of 23 ° C. and 50% RH (the same meaning in the present specification).
  • the hygroscopicity of the resin film exceeds 0.5% by weight, it is easily affected by humidity when used for a circuit board such as an FPC, and inconveniences such as fluctuations in the transmission speed of high-frequency signals are likely to occur. That is, when the moisture absorption rate of the resin film exceeds the above range, it becomes easy to absorb water having a high relative permittivity, which causes an increase in the relative permittivity and the dielectric loss tangent, resulting in loss of an electric signal on the transmission path of a high frequency signal. Inconvenience is likely to occur.
  • the resin film may have a temperature range in which the storage elastic modulus decreases steeply as the temperature rises in the range of 40 to 250 ° C. .. It is considered that such characteristics of the resin film are factors that alleviate internal stresses during thermocompression bonding and maintain dimensional stability after circuit processing, for example.
  • the resin film has a storage modulus at the upper limit temperature of the temperature range is preferably at 5 ⁇ 10 7 [Pa] or less.
  • the resin film preferably has the following physical properties. ⁇ Relative permittivity> When the component (B2) is used as the component (B), the resin film is used at 23 ° C., 50, for ensuring impedance matching when used for a circuit board such as FPC, and for reducing loss of electric signals.
  • the relative permittivity at 20 GHz after humidity control for 24 hours under the constant temperature and humidity condition of% RH is preferably 3.2 or less, and more preferably 3.0 or less. If this relative permittivity exceeds 3.2, inconveniences such as loss of electric signals are likely to occur on the transmission path of high-frequency signals when used for a circuit board such as an FPC.
  • the resin film is used under constant temperature and humidity conditions of 23 ° C. and 50% RH in order to reduce the loss of electric signals when used for a circuit board such as FPC.
  • the dielectric loss tangent at 20 GHz after humidity control for 24 hours is preferably less than 0.005, more preferably 0.004 or less, and most preferably 0.002 or less. If the dielectric loss tangent is 0.005 or more, inconveniences such as loss of electric signals are likely to occur on the transmission path of high-frequency signals when used for a circuit board such as an FPC.
  • the resin film preferably has the following physical properties. ⁇ Relative permittivity> When the component (B3) is used as the component (B), the resin film is used at 23 ° C., 50, for ensuring impedance matching when used for a circuit board such as FPC, and for reducing loss of electric signals.
  • the relative permittivity at 20 GHz after humidity control for 24 hours under the constant temperature and humidity condition of% RH is preferably 3.2 or less, more preferably 3.0 or less. If this relative permittivity exceeds 3.2, inconveniences such as loss of electric signals are likely to occur on the transmission path of high-frequency signals when used for a circuit board such as an FPC.
  • the resin film is used under constant temperature and humidity conditions of 23 ° C. and 50% RH in order to reduce the loss of electric signals when used for a circuit board such as FPC.
  • the dielectric loss tangent at 20 GHz after humidity control for 24 hours is preferably less than 0.005, more preferably 0.004 or less, and most preferably 0.002 or less. If the dielectric loss tangent is 0.005 or more, inconveniences such as loss of electric signals are likely to occur on the transmission path of high-frequency signals when used for a circuit board such as an FPC.
  • the thickness of the resin film is preferably in the range of, for example, 5 ⁇ m or more and 125 ⁇ m or less, and more preferably in the range of 8 ⁇ m or more and 100 ⁇ m or less. If the thickness of the resin film is less than 5 ⁇ m, problems such as wrinkles may occur during transportation in the production of the resin film, while if the thickness of the resin film exceeds 125 ⁇ m, the productivity of the resin film may decrease. There is.
  • the thickness of the resin film is preferably in the range of, for example, 15 to 100 ⁇ m, and more preferably in the range of 20 to 50 ⁇ m. If the thickness of the resin film is less than 15 ⁇ m, problems such as wrinkles may occur during transportation in the production of the resin film, while if the thickness of the resin film exceeds 100 ⁇ m, the productivity of the resin film may decrease. There is. When the thickness of the resin film is in the range of 15 ⁇ m to 20 ⁇ m, the silica particles of the component (B2) or the component (B3) can be used to suppress the unevenness of the surface of the resin film and maintain the smoothness of the film surface. As the liquid crystal polymer filler of the above, it is preferable to use one having an average particle diameter D 50 in the range of 9 to 12 ⁇ m.
  • the laminate according to the embodiment of the present invention has a base material and an adhesive layer laminated on at least one surface of the base material, and the adhesive layer is made of the above resin film. ..
  • the laminated body may include any layer other than the above.
  • the base material in the laminate include a base material of an inorganic material such as a copper foil and a glass plate, and a base material of a resin material such as a polyimide film, a polyamide film, and a polyester film.
  • Preferred embodiments of the laminate include a coverlay film, a copper foil with a resin, and the like.
  • the coverlay film which is one aspect of the laminated body, has a coverlay film material layer as a base material and an adhesive layer laminated on one side of the coverlay film material layer, and is an adhesive layer. Is made of the above resin film.
  • the coverlay film may contain any layer other than the above.
  • the material of the coverlay film material layer is not particularly limited, and for example, a polyimide-based film such as polyimide, polyetherimide, or polyamideimide, a polyamide-based film, or a polyester-based film can be used. Among these, it is preferable to use a polyimide-based film having excellent heat resistance.
  • the coverlay film material can contain a black pigment in order to effectively exhibit light-shielding property, hiding property, design property, etc., and the surface surface is within a range that does not impair the effect of improving the dielectric property. It can contain any component such as a matte pigment that suppresses gloss.
  • the thickness of the coverlay film material layer is not particularly limited, but is preferably in the range of, for example, 5 ⁇ m or more and 100 ⁇ m or less.
  • the thickness of the adhesive layer is not particularly limited, but is preferably in the range of, for example, 10 ⁇ m or more and 75 ⁇ m or less.
  • the coverlay film of the present embodiment can be produced by the method exemplified below.
  • a solvent-containing varnish-like resin composition is applied to one side of a coverlay film material layer, and then dried at a temperature of, for example, 80 to 180 ° C. to form an adhesive layer.
  • a coverlay film material layer By doing so, it is possible to form a coverlay film having a coverlay film material layer and an adhesive layer.
  • a varnish-like resin composition containing a solvent is applied onto an arbitrary base material, dried at a temperature of, for example, 80 to 180 ° C., and then peeled off for an adhesive layer.
  • the coverlay film can be formed by forming the adhesive film of the above and heat-bonding the adhesive film to the film material layer for the coverlay at a temperature of, for example, 60 to 220 ° C.
  • a copper foil with a resin which is another aspect of the laminated body, is obtained by laminating an adhesive layer on at least one side of a copper foil as a base material, and the adhesive layer is made of the above resin film.
  • the resin-coated copper foil of the present embodiment may contain any layer other than the above.
  • the thickness of the adhesive layer in the resin-attached copper foil is preferably in the range of, for example, 2 to 125 ⁇ m, and more preferably in the range of 2 to 100 ⁇ m. If the thickness of the adhesive layer does not reach the above lower limit value, problems such as insufficient adhesiveness cannot be ensured may occur. On the other hand, if the thickness of the adhesive layer exceeds the above upper limit value, problems such as deterioration of dimensional stability occur. Further, from the viewpoint of low dielectric constant and low dielectric loss tangent, the thickness of the adhesive layer is preferably 3 ⁇ m or more.
  • the material of the copper foil in the copper foil with resin is preferably one containing copper or a copper alloy as a main component.
  • the thickness of the copper foil is preferably 35 ⁇ m or less, more preferably in the range of 5 to 25 ⁇ m. From the viewpoint of production stability and handleability, the lower limit of the thickness of the copper foil is preferably 5 ⁇ m.
  • the copper foil may be rolled copper foil or electrolytic copper foil. Further, as the copper foil, a commercially available copper foil can be used.
  • the copper foil with resin may be prepared, for example, by sputtering a metal on a resin film to form a seed layer and then forming a copper layer by, for example, copper plating, or heat the resin film and the copper foil. It may be prepared by laminating by a method such as crimping. Further, in order to form an adhesive layer on the copper foil, the copper foil with resin may be prepared by casting a coating liquid of the resin composition, drying it to form a coating film, and then performing necessary heat treatment. Good.
  • the metal-clad laminate according to the embodiment of the present invention includes an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer, and at least one layer of the insulating resin layer is described above. It is made of a resin film.
  • the metal-clad laminate of the present embodiment may include any layer other than the above.
  • the metal-clad laminate according to another embodiment of the present invention is formed on, for example, an insulating resin layer, an adhesive layer laminated on at least one surface of the insulating resin layer, and an insulating resin layer via the adhesive layer. It is a so-called three-layer metal-clad laminate provided with a laminated metal layer, and the adhesive layer is made of the above resin film.
  • the three-layer metal-clad laminate may include any layer other than the above.
  • the adhesive layer may be provided on one side or both sides of the insulating resin layer, and the metal layer may be provided on one side or both sides of the insulating resin layer via the adhesive layer. Just do it.
  • the three-layer metal-clad laminate may be a single-sided metal-clad laminate or a double-sided metal-clad laminate.
  • a single-sided FPC or a double-sided FPC can be manufactured by processing a wiring circuit by etching the metal layer of the three-layer metal-clad laminate.
  • the insulating resin layer in the three-layer metal-clad laminate is not particularly limited as long as it is composed of a resin having electrical insulating properties, and is, for example, polyimide, epoxy resin, phenol resin, polyethylene, polypropylene, or polytetrafluoroethylene. , Silicone, ETFE, etc., but it is preferably composed of polyimide.
  • the polyimide layer constituting the insulating resin layer may be a single layer or a plurality of layers, but preferably includes a non-thermoplastic polyimide layer.
  • the thickness of the insulating resin layer in the three-layer metal-clad laminate is preferably in the range of, for example, 1 to 125 ⁇ m, and more preferably in the range of 5 to 100 ⁇ m. If the thickness of the insulating resin layer does not reach the above lower limit value, problems such as insufficient electrical insulation cannot be ensured may occur. On the other hand, if the thickness of the insulating resin layer exceeds the above upper limit value, problems such as warpage of the three-layer metal-clad laminate are likely to occur.
  • the thickness of the adhesive layer in the three-layer metal-clad laminate is preferably in the range of, for example, 0.1 to 125 ⁇ m, and more preferably in the range of 0.3 to 100 ⁇ m.
  • the thickness of the adhesive layer if the thickness of the adhesive layer does not reach the above lower limit value, there may be a problem that sufficient adhesiveness cannot be guaranteed.
  • the thickness of the adhesive layer exceeds the above upper limit value, problems such as deterioration of dimensional stability occur.
  • the thickness of the adhesive layer is preferably 3 ⁇ m or more.
  • the ratio of the thickness of the insulating resin layer to the thickness of the adhesive layer is preferably in the range of, for example, 0.1 to 3.0, and is 0.15 to 2 The range of 0.0 is more preferable. With such a ratio, it is possible to suppress the warp of the three-layer metal-clad laminate.
  • the insulating resin layer may contain a filler, if necessary. Examples of the filler include silicon dioxide, aluminum oxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, calcium fluoride, and metal salts of organic phosphinic acid. These can be used alone or in admixture of two or more.
  • the circuit board according to the embodiment of the present invention is formed by wiring the metal layer of the metal-clad laminate according to any one of the above embodiments.
  • a circuit board such as an FPC can be manufactured by processing one or more metal layers of a metal-clad laminate into a pattern by a conventional method to form a wiring layer (conductor circuit layer).
  • the circuit board may include a coverlay film that covers the wiring layer.
  • the amine value is calculated by the following formula (1).
  • Amine value ⁇ (V 2 x C 2 )-(V 1 x C 1 ) ⁇ x M KOH / m ... (1)
  • the amine value is a value expressed by mg KOH / g, M KOH is the molecular weight 56.1 of potassium hydroxide.
  • V and C are the volumes and concentrations of the solutions used for titration, respectively, and the subscripts 1 and 2 are 0.1 mol / L ethanolic potassium hydroxide solution and 0.2 mol / L hydrochloric acid / isopropanol solution, respectively. Represents. Further, m is the sample weight expressed in grams.
  • GPC prepared a sample by diluting a 100 mg solution of a 20 mg diamine diamine composition pretreated with 200 ⁇ L acetic anhydride, 200 ⁇ L pyridine and 2 mL THF with 10 mL THF (containing 1000 ppm cyclohexanone).
  • the prepared sample was manufactured by Tosoh Corporation, trade name: HLC-8220GPC, column: TSK-gel G2000HXL, G1000HXL, flow volume: 1 mL / min, column (oven) temperature: 40 ° C., injection volume: 50 ⁇ L. Measured in. Cyclohexanone was treated as a standard substance to correct the outflow time.
  • the peak top of the main peak of cyclohexanone is adjusted so that the retention time is 27 minutes to 31 minutes, and the peak end is 2 minutes from the peak start of the main peak of cyclohexanone, and the peak of cyclohexanone is excluded.
  • (C) Component represented by the main peak; (B) A component represented by a GPC peak detected at a time later than the minimum value on the time side where the retention time at the main peak is late; (C) A component represented by a GPC peak detected earlier than the minimum value on the time side where the retention time at the main peak is earlier; Was detected.
  • a polyimide film (cured polyimide film) is left for 24 hours under the conditions of temperature; 23 ° C. and humidity; 50% using a vector network analyzer (manufactured by Agent, trade name; vector network analyzer E8633C) and an SPDR resonator. After that, the relative permittivity ( ⁇ 1 ) and the dielectric loss tangent (Tan ⁇ 1 ) at a frequency of 10 GHz were measured. Further, after absorbing water at 23 ° C. for 24 hours, the relative permittivity ( ⁇ 2 ) and the dielectric loss tangent (Tan ⁇ 2 ) of the polyimide film (the cured polyimide film) at a frequency of 10 GHz were measured.
  • Glass transition temperature (Tg) and storage elastic modulus The glass transition temperature (Tg) and storage elastic modulus are 30 ° C. using a polyimide film having a size of 5 mm ⁇ 20 mm and a dynamic viscoelasticity measuring device (DMA: manufactured by UBM, trade name: E4000F). The measurement was carried out from 1 to 400 ° C. at a heating rate of 4 ° C./min and a frequency of 11 Hz. The temperature at which the elastic modulus change (tan ⁇ ) was maximized was defined as the glass transition temperature.
  • DMA dynamic viscoelasticity measuring device
  • the tensile elastic modulus was determined by performing a tensile test at 50 mm / min using a tension tester (manufactured by Orientec Co., Ltd., trade name Tencilon) using a test piece having a width of 12.7 mm and a length of 127 mm. Asked.
  • a circuit of wiring width / wiring interval (L / S) 1 mm / 1 mm is formed by circuit processing a polyimide copper-clad laminate (manufactured by Nippon Steel Chemical & Materials Co., Ltd., trade name: Espanex MB12-25-12UEG). I prepared a printed circuit board. The adhesive surface of the test piece was placed on the wiring of the printed circuit board and pressed under the conditions of a temperature of 160 ° C., a pressure of 3.5 MPa, and a time of 60 minutes.
  • a circuit of wiring width / wiring interval (L / S) 1 mm / 1 mm is formed by circuit processing a polyimide copper-clad laminate (manufactured by Nippon Steel Chemical & Materials Co., Ltd., trade name: Espanex MB12-25-12UEG). I prepared a printed circuit board. The adhesive surface of the test piece was placed on the wiring of the printed circuit board and pressed under the conditions of a temperature of 160 ° C., a pressure of 3.5 MPa, and a time of 60 minutes. This test piece with copper foil was left at 40 ° C.
  • the heat resistance is expressed by the upper limit temperature at which no defect occurs. For example, "260 ° C" means that no defect is found when evaluated in a solder bath at 260 ° C.
  • peel strength For the peel strength, use a Tencilon tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., trade name; Strograph VE-10), and double-sided tape on the resin layer side of a 1 mm wide sample (laminate composed of a base material / resin layer). The force was obtained when the resin layer and the base material were peeled off from each other at a speed of 50 mm / min in the 180 ° direction.
  • Tencilon tester manufactured by Toyo Seiki Seisakusho Co., Ltd., trade name; Strograph VE-10
  • a polyimide film material with a thickness of 25 ⁇ m (manufactured by Toray DuPont, trade name; Kapton 100EN) or a copper foil with a thickness of 12 ⁇ m is coated with a polyimide solution so that the thickness after drying is 25 ⁇ m, and a test is performed. Pieces were made. In this state, place the polyimide film material or copper foil on the lower surface, measure the average of the warped heights at the four corners of the test piece, and measure 5 mm or less as "good” and 5 mm or more as "impossible”. And said.
  • DDA1 Manufactured by Croda Japan Co., Ltd., trade name: PRIAMINE 1075 distilled and purified (a component: 98.2% by weight, b component: 0%, c component: 1.9%, amine value: 206 mgKOH / g)
  • DDA2 manufactured by Croda Japan Co., Ltd., trade name: PRIAMINE 1075 distilled and purified (a component: 99.2% by weight, b component: 0%, c component: 0.8%, amine value: 210 mgKOH / g)
  • APB 1,3-bis (3-aminophenoxy) benzene BTDA: 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride
  • N-12 dihydrazide dodecanedioate
  • NMP N-methyl-2-pyrrolidone
  • PX-200 Phosphate ester (manufactured by Daihachi)
  • Flame Retardant 1 Made by Clariant Japan, trade name; Exolit OP935 (aluminum alkyl phosphate) Flame Retardant 2: Manufactured by Daihachi Chemical Co., Ltd., trade name; SR-3000 (condensed phosphoric acid ester) LCP filler: manufactured by JXTG Energy Co., Ltd.
  • DDA1 and DDA2 low-dielectric liquid crystal polymer, particle size (D 50 ); 9.6 ⁇ m, relative permittivity at 10 GHz; 3.27, dielectric loss tangent at 10 GHz; 0.0009)
  • the "%" of the b component and the c component means the area percentage of the chromatogram in the GPC measurement.
  • a polyimide film 1-1a'with a thickness of 25 ⁇ m was prepared by drying and peeling from the release PET film.
  • This polyimide film 1-1a' was pressed under the conditions of a temperature of 160 ° C., a pressure of 3.5 MPa, and a time of 60 minutes to obtain a polyimide film 1-1a.
  • the various evaluation results of the polyimide film 1-1a are as follows.
  • Example 1-1 10 parts by weight of SR-3000 was added to the polyimide solution 1-1a (100 parts by weight as a solid content) obtained in Preparation Example 1-1 to obtain a polyimide composition 1-1.
  • the obtained polyimide composition 1-1 is applied to one side of the release PET film, dried at 80 ° C. for 15 minutes, and peeled off from the release PET film, whereby the polyimide film 1-1'with a thickness of 25 ⁇ m is removed.
  • This polyimide film 1-1' was heated in an oven at a temperature of 160 ° C. for 2 hours to obtain a polyimide film 1-1.
  • the various evaluation results of the polyimide film 1-1 are as follows. Relative permittivity ( ⁇ 1 ); 2.6, dielectric loss tangent (Tan ⁇ 1 ); 0.0022
  • Example 1-2 to 1-16 Each component was blended in the proportion (part by weight) shown in Table 1-2 to obtain polyimide compositions 1-2 to 1-16 in the same manner as in Example 1-1.
  • DDA composition in Table 1-2 means a diamine diamine composition (the same applies in Table 1-3).
  • polyimide films 1-2 to 1-16 were prepared in the same manner as in Example 1-1.
  • the various evaluation results of the polyimide films 1-2 to 1-16 are as follows.
  • polyimide films 1-17 to 1-34 were prepared in the same manner as in Example 1-1.
  • the various evaluation results of the polyimide films 1-17 to 1-34 are as follows.
  • Example 1-18 The release PET film was laminated on the adhesive layer side of the coverlay film 1-17 so as to be in contact with the adhesive layer, and pressure-bonded with a vacuum laminator at a temperature of 160 ° C. and a pressure of 0.8 MPa for 2 minutes. Then, the polyimide composition 1-2 was applied to the polyimide film material P1 side of the coverlay film 1-17 in a state where the release PET film was pressure-bonded so that the thickness after drying was 25 ⁇ m, and the thickness after drying was 25 ⁇ m, and the temperature was 80 ° C. for 15 minutes. It was dried.
  • the polyimide composition 1-2 was laminated on the coated and dried surface so that the release PET film was in contact with the surface, and the polyimide film material P1 was pressure-bonded at a temperature of 160 ° C. and a pressure of 0.8 MPa for 2 minutes using a vacuum laminator.
  • a laminate 1-18 having an adhesive layer on both sides was obtained.
  • Example 1-19 The polyimide composition 1-2 was applied to one side of an electrolytic copper foil having a thickness of 12 ⁇ m and dried at 80 ° C. for 15 minutes to obtain a resin-coated copper foil 1-19 having an adhesive layer thickness of 25 ⁇ m. The warped state of the obtained resin-attached copper foil 1-19 was "good".
  • Example 1-20 The polyimide composition 1-2 was applied to one side of an electrolytic copper foil having a thickness of 12 ⁇ m and dried at 80 ° C. for 30 minutes to obtain a resin-coated copper foil 1-20 having an adhesive layer thickness of 50 ⁇ m. The warped state of the obtained resin-attached copper foil 1-20 was "good".
  • Example 1-21 The polyimide composition 1-2 was further applied to the surface of the adhesive layer of the resin-attached copper foil 1-19, dried at 80 ° C. for 30 minutes, and the total thickness of the adhesive layer was 100 ⁇ m. I got -21. The warped state of the obtained resin-attached copper foil 1-21 was “good”.
  • Example 1-22 The polyimide composition 1-2 was applied to one side of the release PET film, dried at 80 ° C. for 30 minutes, and peeled off from the release PET film to obtain a polyimide film 1-35 having a thickness of 50 ⁇ m.
  • Example 1-24 Laminated on an electrolytic copper foil having a thickness of 12 ⁇ m so that the adhesive layer side of the coverlay film 1-17 is in contact with the copper foil, pressure-bonded at a temperature of 160 ° C. and a pressure of 0.8 MPa for 2 minutes using a vacuum laminator, and then at room temperature. The temperature was raised to 160 ° C. and heat treatment was performed at 160 ° C. for 2 hours to obtain a copper-clad laminate 1-24.
  • Example 1-25 A polyimide film 1-2 was laminated on a rolled copper foil having a thickness of 12 ⁇ m, and the polyimide film material P1 side of the coverlay film 1-17 was laminated so as to be in contact with the polyimide film 1-2, and further, the coverlay film 1-17 was laminated.
  • Rolled copper film with a thickness of 12 ⁇ m is sequentially laminated on the adhesive layer side, pressure-bonded at a temperature of 160 ° C. and a pressure of 0.8 MPa for 2 minutes using a vacuum laminator, then heated from room temperature to 160 ° C. for 2 hours at 160 ° C. The heat treatment was performed to obtain a copper-clad laminate 1-25.
  • P3 manufactured by DuPont, trade name; Kapton 200-EN, thickness 50 ⁇ m, frequency
  • the temperature is 160 ° C. and the pressure is 4 It was crimped at 0.0 MPa for 120 minutes to obtain a copper-clad laminate 1-27.
  • Example 1-28 Polyimide film 1-2 is laminated on the resin layer side of the single-sided copper-clad laminate M1, and further laminated so that the resin layer side of the single-sided copper-clad laminate M1 is in contact with the polyimide film 1-2.
  • a copper-clad laminate 1-28 was obtained by crimping with a press machine at a temperature of 160 ° C. and a pressure of 4.0 MPa for 120 minutes.
  • Example 1-29 Polyimide composition 1-2 is applied to one side of the release PET film, dried at 80 ° C. for 15 minutes, and the adhesive layer is peeled off from the release PET film to obtain a polyimide film 1-36 having a thickness of 15 ⁇ m.
  • Example 1-30 A double-sided copper-clad laminate M2 (manufactured by Nippon Steel Chemical & Materials Co., Ltd., trade name; Espanex MB12-25-00UEG) was prepared, and the copper foil on one side was subjected to circuit processing by etching to form a conductor circuit layer. A wiring board 1-1A was obtained.
  • the copper foil on one side of the double-sided copper-clad laminate M2 was removed by etching to obtain a copper-clad laminate 1-1B.
  • a polyimide film 1-2 is sandwiched between the surface of the wiring board 1-1A on the conductor circuit layer side and the surface of the copper-clad laminate 1-1B on the resin layer side, and in a laminated state, the temperature is 160 ° C. and the pressure is 4 Thermocompression bonding was performed at 0.0 MPa for 120 minutes to obtain a multilayer circuit board 1-30.
  • the copper foil on one side of the copper-clad laminate 1-1C was removed by etching to obtain a copper-clad laminate 1-1D.
  • a polyimide film 1-2 is sandwiched between the surface of the wiring board 1-1C on the conductor circuit layer side and the surface of the copper-clad laminate 1-1D on the insulating substrate layer side, and the temperature is 160 ° C. in a laminated state. , Pressure 4.0 MPa, thermocompression bonding for 120 minutes to obtain multilayer circuit board 1-31.
  • ⁇ Resin film> Adhesive pressed using a vector network analyzer (manufactured by Keysight Technology, trade name; vector network analyzer E8633C) and a split post dielectric resonator (SPDR) at a temperature of 160 ° C., a pressure of 3.5 MPa, and a time of 60 minutes.
  • the sheet was left to stand for 24 hours under the conditions of temperature; 23 ° C. and humidity; 50%, and then the relative permittivity and dielectric loss tangent at a frequency of 20 GHz were measured.
  • the true specific gravity was measured by the pycnometer method (liquid phase substitution method) using a continuous automatic powder truth density measuring device (manufactured by Seishin Enterprise Co., Ltd., trade name; AUTO TRUE DENSERMAT-7000).
  • Tg glass transition temperature
  • DMA dynamic viscoelasticity measuring device
  • the film retention was evaluated by the following procedure.
  • the adhesive sheet was cut into test pieces having a width of 20 mm and a length of 20 mm, bent so as to make creases along the diagonal line, and then opened to observe the state of the film. At this time, those with no cracks in the test piece even after making creases and opening were rated as "good", and those with some cracks were rated as "impossible”.
  • An adhesive sheet is placed on the foil side, and a polyimide film (manufactured by Toray DuPont Co., Ltd., trade name; Kapton 50EN-S) is further laminated on the adhesive sheet, and the temperature: 160 ° C., pressure: 3.5 MPa, Time: Pressed under the condition of 60 minutes.
  • Example 2-1 1.09 g of N-12 and 7.50 g of filler 1 are mixed with 100 g of the polyimide solution 2-1 prepared in Synthesis Example 2-1 and diluted by adding xylene so that the solid content becomes 30% by weight. Then, the polyimide varnish 2-1a was prepared by stirring.
  • Example 2-2 to 2-8 Polyimide varnishes 2-2a to 2-8a were prepared in the same manner as in Example 2-1 except that the blending amounts of the filler 1 and the filler 2 were changed as shown in Table 2-1.
  • Example 2-9 The polyimide varnish 2-1a prepared in Example 2-1 is applied to one side of the release-treated PET film, dried at 80 ° C. for 15 minutes, and then peeled off to form an adhesive sheet 2-1b ( Thickness; 25 ⁇ m) was prepared.
  • the various evaluation results of the adhesive sheet 2-1b are as follows. Relative permittivity; 2.7, dielectric loss tangent; 0.0015, tensile modulus; 0.6 GPa, maximum elongation; 165%, Tg; 56 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 260 ° C., peel strength; 1.8 kN / m, flame retardancy; good
  • Example 2-10 An adhesive sheet 2-2b was prepared in the same manner as in Example 2-9 using the polyimide varnish 2-2a.
  • the various evaluation results of the adhesive sheet 2-2b are as follows. Relative permittivity; 2.9, dielectric loss tangent; 0.0013, tensile modulus; 0.5 GPa, maximum elongation; 77%, Tg; 56 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 260 ° C., peel strength; 1.8 kN / m, flame retardancy; good
  • Adhesive sheets 2-3b were prepared in the same manner as in Example 2-9 using polyimide varnish 2-3a.
  • the various evaluation results of the adhesive sheet 2-3b are as follows. Relative permittivity; 2.8, dielectric loss tangent; 0.0012, tensile modulus; 0.6 GPa, maximum elongation; 59%, Tg; 56 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 270 ° C, peel strength; 1.8 kN / m, flame retardancy; good
  • Adhesive sheets 2-4b were prepared in the same manner as in Example 2-9 using polyimide varnish 2-4a.
  • the various evaluation results of the adhesive sheet 2-4b are as follows. Relative permittivity; 2.8, dielectric loss tangent; 0.0011, tensile modulus; 0.8 GPa, maximum elongation; 31%, Tg; 56 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 280 ° C, peel strength; 1.9 kN / m, flame retardancy; good
  • Adhesive sheet 2-5b was prepared in the same manner as in Example 2-9 using polyimide varnish 2-5a.
  • the various evaluation results of the adhesive sheet 2-5b are as follows. Relative permittivity; 2.8, dielectric loss tangent; 0.0016, tensile modulus; 0.8 GPa, maximum elongation; 29%, Tg; 56 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 270 ° C, peel strength; 1.9 kN / m, flame retardancy; good
  • Adhesive sheet 2-6b was prepared in the same manner as in Example 2-9 using polyimide varnish 2-6a.
  • the various evaluation results of the adhesive sheet 2-6b are as follows. Relative permittivity; 2.7, dielectric loss tangent; 0.0015, tensile modulus; 0.6 GPa, maximum elongation; 169%, Tg; 56 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 260 ° C., peel strength; 1.7 kN / m, flame retardancy; good
  • Adhesive sheet 2-7b was prepared in the same manner as in Example 2-9 using polyimide varnish 2-7a.
  • the various evaluation results of the adhesive sheet 2-7b are as follows. Relative permittivity; 2.8, dielectric loss tangent; 0.0012, tensile modulus; 0.7 GPa, maximum elongation; 28%, Tg; 56 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 280 ° C, peel strength; 1.8 kN / m, flame retardancy; good
  • Adhesive sheet 2-8b was prepared in the same manner as in Example 2-9 using polyimide varnish 2-8a.
  • the various evaluation results of the adhesive sheet 2-8b are as follows. Relative permittivity; 2.6, dielectric loss tangent; 0.0016, tensile modulus; 0.5 GPa, maximum elongation; 177%, Tg; 56 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 260 ° C., peel strength; 1.7 kN / m, flame retardancy; possible
  • Adhesive sheet 2-9b was prepared in the same manner as in Example 2-9 using polyimide varnish 2-9a.
  • the various evaluation results of the adhesive sheet 2-9b are as follows. Relative permittivity; 2.6, dielectric loss tangent; 0.0017, tensile modulus; 0.4 GPa, maximum elongation; 197%, Tg; 56 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 220 ° C, peel strength; 1.6 kN / m, flame retardancy; not possible
  • the adhesive sheets 2-1b to 2-8b of Examples 2-9 to 2-16 to which the filler 1 and the filler 2 were added as compared with the adhesive sheet 2-9b of Comparative Example 2-2. was confirmed to have improved dielectric properties and solder heat resistance temperature (moisture absorption). From these results, the adhesive sheet as the resin film according to the present embodiment can be expected to reduce the transmission loss in the high frequency band of, for example, 20 GHz. Further, the adhesive sheets 2-1b to 2-8b of Examples 2-9 to 2-16 to which the fillers 1 and 2 were added were more flexible than the adhesive sheets 2-9b of Comparative Example 2-2. It was confirmed that the heat resistance of the moisture-absorbing solder, the peel strength and the flame retardancy were improved while maintaining the film retention.
  • the mechanism of improving the adhesive strength has not been clarified, it is speculated that the improvement of the elastic modulus of the adhesive sheet may have contributed. Further, the solder heat resistance (drying / moisture absorption) of the adhesive sheet obtained in the examples was equal to or higher than that of the comparative example in which the cristobalite silica particles were not blended, and showed suitable characteristics as an adhesive for high-frequency multilayer FPC.
  • the resin film according to this embodiment is suitably used as a material for a flexible printed circuit board compatible with high frequencies.
  • Liquid crystal polymer filler> A dimethylacetamide dispersion of a liquid crystal polymer filler adjusted to a solid content of 30% by weight was applied to a smooth surface of a copper foil and dried at 120 ° C. for 10 minutes. Then, the temperature was gradually raised from 200 ° C. to 360 ° C. over 10 minutes, and the copper foil of the obtained laminate was etched and removed to obtain a liquid crystal polymer film.
  • the obtained liquid crystal polymer film was subjected to temperature; 23 ° C., humidity; After standing for 24 hours under the condition of 50%, the relative permittivity and the dielectric loss tangent at a frequency of 10 GHz were measured.
  • the tensile elastic modulus and the maximum elongation were measured by the following procedure. First, a test piece (width 12.7 mm ⁇ length 127 mm) was prepared from a resin film using a tension tester (Tencilon manufactured by Orientec). Using this test piece, a tensile test was performed at 50 mm / min to determine the tensile elastic modulus and the maximum elongation at 25 ° C.
  • Tg glass transition temperature
  • a resin film pressed under the conditions of a temperature of 160 ° C., a pressure of 3.5 MPa, and a time of 60 minutes was cut into a test piece having a size of 5 mm ⁇ 20 mm, and a dynamic viscoelasticity measuring device (DMA: U.S. Using BM, trade name; E4000F), measurement was performed from 30 ° C to 300 ° C at a temperature rise rate of 4 ° C / min and a frequency of 11 Hz, and the temperature at which the elastic modulus change (tan ⁇ ) was maximized was transferred to glass. The temperature was set.
  • DMA U.S. Using BM, trade name; E4000F
  • the film retention was evaluated by the following procedure.
  • the resin film was cut into test pieces having a width of 20 mm and a length of 20 mm, bent so as to have creases along the diagonal line, and then opened to observe the state of the film. At this time, those with no cracks in the test piece even after making creases and opening were rated as "good", and those with some cracks were rated as "impossible”.
  • a polyimide film (trade name: Kapton 50EN-S manufactured by Toray DuPont Co., Ltd.) is laminated on the surface opposite to the surface of the resin film in contact with the printed circuit board. Pressing was performed under the conditions of ° C., pressure; 3.5 MPa, time; 60 minutes.
  • a polyimide film (trade name: Kapton 50EN-S manufactured by Toray DuPont Co., Ltd.) is laminated on the surface opposite to the surface of the resin film in contact with the printed circuit board. Pressing was performed under the conditions of ° C., pressure; 3.5 MPa, time; 60 minutes.
  • This test piece with copper foil was left at 40 ° C. and 80% relative humidity for 72 hours, then immersed in a solder bath set at each evaluation temperature for 10 seconds, and the adhesive state was observed to foam, blister, and peel. It was confirmed whether there were any problems such as.
  • the heat resistance is expressed by the upper limit temperature at which no defect occurs. For example, "260 ° C" means that no defect is found when evaluated in a solder bath at 260 ° C.
  • the peel strength was measured by the following method. A copper foil on one side of a double-sided polyimide copper-clad laminate (manufactured by Nittetsu Chemical & Materials Co., Ltd., trade name: Espanex MB12-25-12UEG) cut out to a width of 50 mm and a length of 100 mm is etched, and the remaining copper is used.
  • a double-sided polyimide copper-clad laminate manufactured by Nittetsu Chemical & Materials Co., Ltd., trade name: Espanex MB12-25-12UEG
  • a resin film is placed on the foil side, and a polyimide film (manufactured by Toray DuPont Co., Ltd., trade name: Capton 50EN-S) is laminated on the surface opposite to the copper-clad laminate of the resin film, and the temperature; 160 ° C., pressure; 3 Pressed under the conditions of .5 MPa, time; 60 minutes.
  • the flame retardancy was evaluated by the following method.
  • a polyimide film manufactured by Toray DuPont Co., Ltd., trade name: Kapton 50EN-S
  • Kapton 50EN-S was laminated on both sides of four resin films laminated so as to have a thickness of 100 ⁇ m, and the temperature: 160 ° C., pressure: 3.5 MPa, time; 60. Pressed under the condition of minutes.
  • a sample is cut to 200 ⁇ 5 mm ⁇ 50 ⁇ 1 mm, rolled into a tubular shape with a diameter of about 12.7 mm and a length of 200 ⁇ 5 mm, and a test piece conforming to the UL94VTM standard is prepared and a combustion test is performed until the flame is extinguished.
  • Example 3-1 1.09 g of N-12 and 7.50 g of LCP filler are mixed with 100 g of the polyimide solution 3-1 prepared in Synthesis Example 3-1 and diluted by adding xylene so that the solid content becomes 30% by weight. Then, the polyimide varnish 3-1a was prepared by stirring.
  • Example 3-2 to 3-4 Polyimide varnishes 3-2a to 3-4a were prepared in the same manner as in Example 3-1 except that the blending amount of the LCP filler was changed as shown in Table 3-1.
  • Example 3-5 1.09 g of N-12 and 7.50 g of LCP filler and 7.50 g of flame retardant 1 are added to 100 g of the polyimide solution 3-1 prepared in Synthesis Example 3-1 to reduce the solid content to 30% by weight.
  • a polyimide varnish 3-5a was prepared by adding xylene to dilute the mixture and stirring the mixture.
  • Example 3-6 to 3-7 Polyimide varnishes 3-6a to 3-7a were prepared in the same manner as in Example 3-5, except that the blending amount of the LCP filler was changed as shown in Table 3-1.
  • Examples 3-8 to 3-10 Polyimide varnishes 3-8a to 3-8a in the same manner as in Example 3-5, except that the flame retardant 2 was used in place of the flame retardant 1 in the blending amount shown in Table 3-1 and the LCP filler was blended as shown in Table 3-1. 3-10a was prepared.
  • Example 3-11 The polyimide varnish 3-1a prepared in Example 3-1 was applied to one side of the release-treated PET film, dried at 80 ° C. for 15 minutes, and then peeled off to obtain a resin film 3-1b (thickness). (25 ⁇ m) was prepared.
  • the various evaluation results of the resin film 3-1b are as follows. Relative permittivity; 2.7, dielectric loss tangent; 0.0015, tensile modulus; 0.6 GPa, maximum elongation; 131%, Tg; 54 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 260 ° C., peel strength; 1.6 kN / m, flame retardancy; ⁇
  • Example 3-12 Using the polyimide varnish 3-2a, a resin film 3-2b was prepared in the same manner as in Example 3-11.
  • the various evaluation results of the resin film 3-2b are as follows. Relative permittivity; 2.7, dielectric loss tangent; 0.0014, tensile modulus; 0.7 GPa, maximum elongation; 80%, Tg; 54 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 260 ° C., peel strength; 1.5 kN / m, flame retardancy; ⁇
  • Example 3-13 A resin film 3-3b was prepared in the same manner as in Example 3-11 using the polyimide varnish 3-3a.
  • the various evaluation results of the resin film 3-3b are as follows. Relative permittivity; 2.8, dielectric loss tangent; 0.0014, tensile modulus; 0.7 GPa, maximum elongation; 38%, Tg; 58 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 270 ° C, peel strength; 1.2 kN / m, flame retardancy; ⁇
  • Example 3-14 A resin film 3-4b was prepared in the same manner as in Example 3-11 using the polyimide varnish 3-4a.
  • the various evaluation results of the resin film 3-4b are as follows. Relative permittivity; 2.9, dielectric loss tangent; 0.0013, tensile modulus; 0.8 GPa, maximum elongation; 18%, Tg; 58 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 270 ° C, peel strength; 1.2 kN / m, flame retardancy; ⁇
  • Example 3-15 A resin film 3-5b was prepared in the same manner as in Example 3-11 using the polyimide varnish 3-5a.
  • the various evaluation results of the resin film 3-5b are as follows. Relative permittivity; 2.7, dielectric loss tangent; 0.0016, tensile modulus; 0.5 GPa, maximum elongation; 100%, Tg; 54 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 270 ° C, peel strength; 2.0 kN / m, flame retardancy; ⁇
  • Example 3-16 A resin film 3-6b was prepared in the same manner as in Example 3-11 using the polyimide varnish 3-6a.
  • the various evaluation results of the resin film 3-6b are as follows. Relative permittivity; 2.8, dielectric loss tangent; 0.0015, tensile modulus; 0.7 GPa, maximum elongation; 33%, Tg; 58 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 270 ° C, peel strength; 1.3 kN / m, flame retardancy; ⁇
  • a resin film 3-7b was prepared in the same manner as in Example 3-11 using the polyimide varnish 3-7a.
  • the various evaluation results of the resin film 3-7b are as follows. Relative permittivity; 2.8, dielectric loss tangent; 0.0014, tensile modulus; 0.7 GPa, maximum elongation; 11%, Tg; 58 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 280 ° C, peel strength; 0.9 kN / m, flame retardancy; ⁇
  • Example 3-18 A resin film 3-8b was prepared in the same manner as in Example 3-11 using the polyimide varnish 3-8a.
  • the various evaluation results of the resin film 3-8b are as follows. Relative permittivity; 2.7, dielectric loss tangent; 0.0015, tensile modulus; 0.5 GPa, maximum elongation; 114%, Tg; 54 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 280 ° C, peel strength; 1.4 kN / m, flame retardancy; ⁇
  • Example 3-19 Using the polyimide varnish 3-9a, a resin film 3-9b was prepared in the same manner as in Example 3-11.
  • the various evaluation results of the resin film 3-9b are as follows. Relative permittivity; 2.8, dielectric loss tangent; 0.0014, tensile modulus; 0.6 GPa, maximum elongation; 52%, Tg; 56 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 280 ° C, peel strength; 1.0 kN / m, flame retardancy; ⁇
  • Example 3-20 A resin film 3-10b was prepared in the same manner as in Example 3-11 using a polyimide varnish 3-10a.
  • the various evaluation results of the resin film 3-10b are as follows. Relative permittivity; 2.9, dielectric loss tangent; 0.0013, tensile modulus; 0.6 GPa, maximum elongation; 22%, Tg; 56 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 290 ° C, peel strength; 0.7 kN / m, flame retardancy; ⁇
  • a resin film 3-11b was prepared in the same manner as in Example 3-11 using the polyimide varnish 3-11a.
  • the various evaluation results of the resin film 3-11b are as follows. Relative permittivity; 2.6, dielectric loss tangent; 0.0017, tensile modulus; 0.4 GPa, maximum elongation; 197%, Tg; 56 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 220 ° C., peel strength; 1.6 kN / m, flame retardancy; ⁇
  • a resin film 3-12b was prepared in the same manner as in Example 3-11 using the polyimide varnish 3-12a.
  • the various evaluation results of the resin film 3-12b are as follows. Relative permittivity; 2.6, dielectric loss tangent; 0.0018, tensile modulus; 0.8 GPa, maximum elongation; 226%, Tg; 56 ° C., film retention; good, solder heat resistance test (dry); 320 ° C. , Solder heat resistance test (moisture absorption); 280 ° C., peel strength; 1.7 kN / m, flame retardancy; ⁇
  • the resin films 3-1b to 3-4b of Examples 3-11 to 3-14 to which the LCP filler was added as compared with the resin film 3-11b of Comparative Example 3-3 were dielectric loss tangent. It was confirmed that the flame retardancy and the solder heat resistant temperature (moisture absorption) were improved.
  • the dielectric loss tangent of the resin film becomes smaller as the amount of the LCP filler added, which has a lower dielectric loss tangent than the DDA-based thermoplastic polyimide, increases. Further, by blending an LCP filler having a high aromatic ring concentration with the easily combustible DDA-based thermoplastic polyimide, an excellent flame retardant effect is exhibited. Further, it is considered that the addition of the LCP filler reduces the hygroscopicity and improves the elastic modulus, so that the solder heat resistance is improved.
  • the resin films 3-1b to 3-4b retain the film property and the adhesive strength exceeds 0.6 kN / m normally required for producing a flexible printed wiring board, the resin according to the present embodiment.
  • the film is suitable for producing a flexible printed wiring board that uses, for example, a high frequency band of 10 GHz or higher. Since the DDA-based thermoplastic polyimide has a large elongation rate, the film property can be maintained even if an LCP filler is added. Further, since Tg is sufficiently low with respect to the press temperature, it is considered that the resin follows the fine irregularities on the surface of the copper foil and the adhesiveness is ensured by the carbonyl group of BTDA used as the acid anhydride.
  • the resin films 3-5b to 3-10b of Examples 3-15 to 3-20 to which the LCP filler was added as compared with the resin film 3-12b of Comparative Example 3-4 are dielectric.
  • the dissipation factor is reduced and the flame retardancy is greatly improved.
  • it is suitable as a high-frequency flexible printed wiring board material in which the dielectric layer is thickened.
  • the char forming effect of the phosphorus-based flame retardant is often not sufficiently exhibited because the aromatic ring concentration in the DDA-based thermoplastic polyimide is low.
  • the combination of the DDA-based thermoplastic polyimide, the LCP filler, and the phosphorus-based flame retardant increases the aromatic ring concentration in the composition, resulting in the phosphorus-based flame retardant. It is considered that the flame retardant effect is increasing.

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  • Manufacturing & Machinery (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

Composition de résine contenant : (A) une résine thermoplastique qui contient une unité structurale dérivée d'un composant anhydride tétracarboxylique, et un composant diamine contenant, par rapport au composant diamine total, au moins 40 % en moles d'une composition de diamine dimère ayant, en tant que composant principal, une diamine dimère dans laquelle deux groupes acide carboxylique terminaux dans l'acide dimère sont substitués par un groupe aminométhyle primaire ou un groupe amino ; et (B) au moins un élément choisi parmi un ester de phosphate condensé aromatique, des particules de silice et une charge de polymère cristallin liquide.
PCT/JP2020/039910 2019-10-29 2020-10-23 Composition de résine, film de résine, corps stratifié, film de couverture, feuille de cuivre avec résine, carte stratifiée revêtue de métal et carte de circuit imprimé WO2021085329A1 (fr)

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CN202080069299.XA CN114502658A (zh) 2019-10-29 2020-10-23 树脂组合物、树脂膜、层叠体、覆盖膜、带树脂的铜箔、覆金属层叠板及电路基板

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JP7510029B1 (ja) 2023-03-31 2024-07-02 住友電工プリントサーキット株式会社 プリント配線板
JP7529450B2 (ja) 2020-06-12 2024-08-06 日鉄ケミカル＆マテリアル株式会社 樹脂フィルム、その製造方法、金属張積層板及びプリント配線板
JP7572234B2 (ja) 2020-12-23 2024-10-23 日鉄ケミカル＆マテリアル株式会社 樹脂組成物、樹脂フィルム、金属張積層板及びプリント配線板

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JP7510029B1 (ja) 2023-03-31 2024-07-02 住友電工プリントサーキット株式会社 プリント配線板

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