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WO2025070797A1 - Copolymère, matériau de base en résine, composition de résine, liquide de revêtement, polyimide, film de résine, stratifié plaqué de métal, carte de circuit imprimé, dispositif électronique et appareil électronique, et procédé de fabrication - Google Patents

Copolymère, matériau de base en résine, composition de résine, liquide de revêtement, polyimide, film de résine, stratifié plaqué de métal, carte de circuit imprimé, dispositif électronique et appareil électronique, et procédé de fabrication Download PDF

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Publication number
WO2025070797A1
WO2025070797A1 PCT/JP2024/034823 JP2024034823W WO2025070797A1 WO 2025070797 A1 WO2025070797 A1 WO 2025070797A1 JP 2024034823 W JP2024034823 W JP 2024034823W WO 2025070797 A1 WO2025070797 A1 WO 2025070797A1
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WO
WIPO (PCT)
Prior art keywords
component
resin
polyimide
resin composition
resin film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/034823
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English (en)
Japanese (ja)
Inventor
杏菜 永易
麻織人 藤
芳樹 須藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Chemical and Materials Co Ltd
Original Assignee
Nippon Steel Chemical and Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Steel Chemical and Materials Co Ltd filed Critical Nippon Steel Chemical and Materials Co Ltd
Publication of WO2025070797A1 publication Critical patent/WO2025070797A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a copolymer useful as a material for circuit boards and the like, a resin substrate, a resin composition, a coating liquid, a polyimide, a resin film, a metal-clad laminate, a circuit board, an electronic device, and an electronic equipment, and a manufacturing method thereof.
  • This application claims priority based on Japanese Patent Application No. 2023-169699 filed in Japan on September 29, 2023, and Japanese Patent Application No. 2023-169700 filed in Japan on September 29, 2023, the contents of which are incorporated herein by reference.
  • Polyimide is a resin with excellent heat resistance, mechanical properties, and electrical properties. Resin films using this polyimide are increasingly being used for applications such as the insulating layers of circuit boards, such as flexible printed circuits (FPCs).
  • FPCs flexible printed circuits
  • Patent Document 1 proposes a polyimide film that contains a structural unit (A1) derived from an ester bond-containing tetracarboxylic anhydride, a structural unit (A2) derived from a biphenyl skeleton-containing tetracarboxylic anhydride, and a structural unit (B1) derived from a biphenyl skeleton-containing diamine.
  • non-thermoplastic polyimides are polyimides that contain an abundance of constituent units with rigid chemical structures and are characterized by a high elastic modulus, a low CTE, and a high glass transition temperature (Tg), and are useful for ensuring the heat resistance and dimensional stability of circuit boards, but it is difficult to reduce the dielectric loss tangent to a low level (e.g., 0.0030 or less at 10 GHz) required for the fifth generation mobile communication system (5G) and beyond.
  • a low level e.g., 0.0030 or less at 10 GHz
  • polyimides rich in structural units containing an aliphatic chain or an alicyclic skeleton are thermoplastic, have excellent adhesive properties, are soluble in solvents, and can have a low dielectric tangent due to the low polarity structure derived from the structural units containing an aliphatic chain or an alicyclic skeleton.
  • aliphatic polyimides are thermoplastic, have excellent adhesive properties, are soluble in solvents, and can have a low dielectric tangent due to the low polarity structure derived from the structural units containing an aliphatic chain or an alicyclic skeleton.
  • Polymer alloys are known as a technology that makes it possible to impart new functions to polymer materials.
  • Polymer alloys are polymer materials that have new properties by mixing or chemically bonding multiple polymers, and include polymer blends (non-reactive and reactive systems) and block copolymers. Polymer alloys are considered to be effective for i) correcting the defects and improving the physical properties of polymer materials made of a single polymer, and ii) creating polymer materials with completely new physical properties that have never been seen before (Non-Patent Document 1).
  • Patent Document 2 proposes a composition containing thermoplastic polyimide and polystyrene elastomer (thermoplastic).
  • thermoplastic polystyrene elastomer
  • the film formed from the composition of Patent Document 2 has a low dielectric tangent, but a low tensile modulus and is prone to tack. A lower dielectric tangent than that of Patent Document 2 is also required.
  • Patent Document 3 proposes a composition containing polyimide and an amorphous resin. However, the film formed from the composition of Patent Document 3 has a high dielectric tangent.
  • the object of the present invention is therefore to provide a copolymer, a resin composition, a coating liquid, and a polyimide that can form a resin film with an excellent tensile modulus and a low dielectric tangent using polymer alloy technology, a resin film, a metal-clad laminate, a circuit board, an electronic device, and an electronic equipment that contain the resin composition, and a method for producing the resin composition.
  • the copolymer according to aspect 1 of the present invention is a first structure comprising two or more aromatic rings; a second structure having a chain structure in which carbon atoms are bonded to each other by single bonds; Including, The number of carbon atoms constituting the chain structure is 6 or more, In the first structure, the distance between the aromatic rings is 8.0 ⁇ or less, The content of the first structure is 15 to 85 mass %, The content of the second structure is 15 to 85% by mass.
  • the resin substrate according to the second aspect of the present invention contains the copolymer according to the first aspect.
  • the first structure constitutes a continuous phase.
  • the resin composition according to aspect 4 of the present invention comprises a component (A1) which is a non-thermoplastic polyimide precursor, A component (B1) which is a soluble polyimide precursor having a structural unit containing at least one of an aliphatic chain and an alicyclic skeleton; a first reactant to which is covalently linked ⁇ 5>
  • the resin composition of aspect 5 of the present invention is Component (A1) which is a thermoplastic polyimide precursor; A component (B2) which is a soluble polyimide having a structural unit containing at least one of an aliphatic chain and an alicyclic skeleton; a second reactant to which is covalently linked ⁇ 6>
  • Aspect 6 of the present invention is the resin composition of aspect 4, In the first reactant, the component (A1) and the component (B1) are bonded via an amide bond at the polymer chain terminal.
  • Aspect 7 of the present invention is the resin composition of aspect 5, In the second reactant, the component (A1) and the component (B2) are bonded via an amide bond at the polymer chain terminal.
  • Aspect 8 of the present invention is the resin composition of aspect 4 or 6, The weight ratio (A1/B1) of the component (A1) to the component (B1) is within the range of 15/85 to 85/15.
  • Aspect 9 of the present invention is the resin composition of aspect 5 or 7, The weight ratio (A1/B2) of the component (A1) to the component (B2) is within the range of 15/85 to 85/15.
  • the coating liquid of aspect 10 of the present invention is The resin composition according to any one of aspects 4 to 9, and further a first organic solvent having an SP value in the range of 10.3 to 19.5 (J/cm 3 ) 1/2 ; a second organic solvent having an SP value in the range of 19.7 to 30.8 (J/cm 3 ) 1/2 ; Contains: ⁇ 11>
  • the polyimide of aspect 11 of the present invention comprises: (A2) a first polyimide which is a non-thermoplastic polyimide; (B2) a second polyimide which is a soluble polyimide having a structural unit including at least one of an aliphatic chain and an alicyclic skeleton; has.
  • Aspect 21 of the present invention is a method for producing a resin composition according to aspect 19 or aspect 20,
  • the weight ratio (A1/B2) of the component (A1) and the component (B2) mixed in the step 3 is within the range of 15/85 to 85/15.
  • the first structure includes two or more aromatic rings, and the distance between the aromatic rings is 8.0 ⁇ or less.
  • the structure represented by the formula (A1) and the structure represented by the formula (A2) may be mixed.
  • the aromatic ring A is also included in the first structure.
  • the carbon atoms constituting the first chain structure are preferably bonded to a hydrogen atom or a fluorine atom in addition to a carbon atom.
  • the first chain structure may have at least one of -CH 2 - and -CF 2 - as a repeating structural unit.
  • carbon atom A When the carbon atom (carbon atom A) of the first chain structure is bonded to an atom other than a carbon atom, or when carbon atom A is bonded to an aromatic ring, carbon atom A is considered to be the terminal carbon atom of the second structure.
  • that structure if there is a structure between the first structure and the second structure that has a molecular weight of 100 or less and is not included in the first structure, that structure is considered to be part of the second structure. Note that when the structure of the repeating unit is clear, that repeating unit may be considered to be the second structure.
  • the content of the second structure is 15 to 85 mass% relative to the total mass of the copolymer according to the first embodiment.
  • the content of the second structure is preferably 20 mass% or more.
  • the content of the second structure is more preferably 40 mass% or more.
  • the content of the second structure is preferably 75 mass% or less.
  • the content of the second structure is more preferably 65 mass% or less.
  • the content of other structures relative to the total mass of the copolymer according to the first embodiment is, for example, 0% by mass to 30% by mass. Since the other structures are not necessary, the lower limit is 0%.
  • the first structure and the second structure can be determined by identifying the chemical structure of the copolymer by a known method. For example, if the copolymer is soluble, the identification can be performed by analyzing using nuclear magnetic resonance analysis ( 1 H-NMR, 13 C-NMR). After identifying the chemical structure of the copolymer, the obtained structure is specified as the first structure and the second structure according to the above criteria. The parts that cannot be assigned to the first structure and the second structure are set as other structures, and the mass ratio of each structure can be calculated by calculating the molecular weight of each structure. Note that, if the copolymer is insoluble, the mass ratio of each structure may be calculated by decomposing it to the monomer level and determining the ratio of the monomers.
  • the weight average molecular weight of the copolymer is preferably 500,000 or less.
  • the weight average molecular weight of the copolymer is preferably 300,000 or less. It is even more preferable that the weight average molecular weight of the copolymer is 250,000 or less. If the weight average molecular weight of the copolymer is small, the phase separation state of the resin composition changes and it is more likely to become a uniform phase. In addition, in the case of a coating liquid, it becomes easier to adjust the viscosity.
  • the number average molecular weight of the copolymer is preferably 250,000 or less.
  • the number average molecular weight of the copolymer is preferably 200,000 or less. It is even more preferable that the number average molecular weight of the copolymer is 100,000 or less. If the number average molecular weight of the copolymer is small, the phase separation state of the resin composition changes, and it is easy for a homogeneous phase to form.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • the weight average molecular weight and number average molecular weight are measured by a gel permeation chromatograph (e.g., HLC-8420GPC, manufactured by Tosoh Corporation).
  • Polystyrene is used as a standard substance, and a developing solvent can be appropriately selected depending on the solubility of the resin.
  • the solvent that can be used include tetrahydrofuran (THF) and N,N-dimethylacetamide (DMAc).
  • the copolymer according to the first embodiment can be obtained by selecting a substrate (monomer) and polymerizing it by a known method so as to obtain the first and second structures described above.
  • the resin composition according to the first embodiment contains the copolymer according to the first embodiment.
  • the resin composition according to the first embodiment may further contain, as necessary, an organic filler, an inorganic filler, a cyclization agent, a curing agent, a curing accelerator, a plasticizer, an elastomer, a coupling agent, a pigment, a flame retardant, a heat dissipation agent, and the like, as an optional component, within a range that does not impair the effects of the invention.
  • examples of inorganic fillers include silicon dioxide, aluminum oxide, beryllium oxide, niobium oxide, titanium oxide, magnesium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, calcium fluoride, magnesium fluoride, potassium silicofluoride, and metal phosphinate. These may be used alone or in combination of two or more.
  • a resin component other than the second structure and the first structure may be added, within a range that does not impair the effects of the invention.
  • the first structure constitutes a continuous phase (continuous structure).
  • the first structure constitutes a continuous phase means that the region in which the first structure exists is continuously connected in the entire resin composition.
  • the phase structure of the resin composition is not particularly limited.
  • the resin composition may be a homogeneous phase (homogeneous compatible structure) in which the second structure and the first structure are compatible with each other, or may be a phase-separated structure such as a sea-island structure or an interconnected structure.
  • the number density of island phases having a circle equivalent diameter of 500 nm or more is preferably 0.01 to 0.300 pieces/ ⁇ m 2. Since the number density is 0.01 to 0.200 pieces/ ⁇ m 2 , the linear expansion coefficient can be further reduced.
  • the phase structure of the resin composition according to the first embodiment is a homogeneous compatible structure
  • the number density of the island phase having a circle equivalent diameter of 500 nm or more is preferably less than 0.01 pieces/ ⁇ m2 . If the number density is less than 0.01 pieces/ ⁇ m2 , the linear expansion coefficient can be further reduced.
  • the phase structure of the resin composition according to the first embodiment is a homogeneous compatible structure, there is basically no island phase, so the lower limit of the number density is 0 pieces.
  • the continuous phase can be confirmed and the average circle equivalent diameter and number density of the island phases can be measured by the following method.
  • the resin film is cut and embedded in epoxy resin, and then the cross section of the film is exposed using a cross section polisher (CP). Osmium is vapor-deposited on the obtained cross section depending on the sample, and a sample for cross-sectional observation of approximately 7 mm is prepared.
  • CP cross section polisher
  • the above-mentioned cross-sectional observation samples are observed in the thickness direction using a scanning electron microscope (SEM, for example, JEOL Ltd., product name: JSM-IT500HR) with an acceleration voltage of 10 kV, an irradiation current of 80 ⁇ A, and a magnification of 3000 times.
  • SEM scanning electron microscope
  • the dark colored parts are regarded as the second structure and the light colored parts are judged as the first structure.
  • Image analysis is performed using each analysis software (for example, Image Pro 10), and based on the above definition, the continuous phase is confirmed, and the average circle equivalent diameter of the island phases and the number density of island phases of 500 nm or more per unit area are calculated (the number of islands of 500 nm or more per unit area is calculated). Specifically, the three SEM images obtained by observing the phase separation structure are analyzed using analysis software (Image Pro 10), and the average is used as each evaluation value (average circular equivalent diameter of islands, number density of islands 500 nm or larger per unit area).
  • the analysis conditions can be changed as appropriate depending on the sample, but for example, the analysis process can be performed after removing noise using spatial calibration, a median filter, etc.
  • the region where the first structure exists is determined as follows.
  • the phase structure of the resin composition according to the first embodiment is a phase-separated structure such as a sea-island structure
  • the proportion of resin constituting each phase e.g., sea phase, island phase
  • the phase (region) where the proportion of the first structure is greater than the proportion of the second structure is determined to be the region where the first structure exists.
  • the first structure is determined to form a continuous phase.
  • the resin film according to the first embodiment preferably has a CTE of 50.0 ppm/K or less, more preferably in the range of 0 to 30.0 ppm/K.
  • a CTE of 50.0 ppm/K or less the dimensional change rate can be easily controlled when the resin film is made into a resin film or a metal-clad laminate.
  • the CTE can be measured by the method described above.
  • the linear expansion coefficient of a resin can be measured by the following method. Using a thermomechanical analyzer (e.g., Hitachi High-Technologies Corporation (formerly Seiko Instruments Inc.), product name: TMA/7100), a sample (width 3 mm x length 20 mm) is heated from 30° C. to 180° C. at a constant heating rate while applying a load of 5.0 g, and then the sample is held at that temperature for 10 minutes and cooled at a rate of 5° C./min to determine the average thermal expansion coefficient (linear expansion coefficient) from 180° C. to 100° C.
  • a thermomechanical analyzer e.g., Hitachi High-Technologies Corporation (formerly Seiko Instruments Inc.), product name: TMA/7100
  • the resin film according to the first embodiment preferably has a relative dielectric constant (Dk) of 3.5 or less, more preferably 3.0 or less at 10 GHz after 24 hours of humidity conditioning under conditions of a temperature of 24 to 26°C and a relative humidity of 45 to 55%. If the relative dielectric constant exceeds 3.5, problems such as loss of an electric signal are likely to occur on the transmission path of a high-frequency signal when used in a circuit board such as an FPC.
  • the relative dielectric constant can be measured by the method described above.
  • the dielectric constant and dielectric loss tangent can be evaluated by the following method.
  • the resin composition is molded into a film to obtain a resin film.
  • the resin composition may be dissolved in a solvent to prepare a coating liquid, which is then applied to a support substrate and dried to obtain a resin film for evaluation.
  • the dielectric constant (Dk) and dielectric loss tangent (Df) of the resin film at a specified frequency (e.g., 10 GHz) are measured using a vector network analyzer (e.g., Agilent, product name: E8363C) and a split post dielectric resonator (SPDR resonator).
  • the dielectric constant and dielectric loss tangent are measured after the film used for the measurement is left for 24 hours under conditions of a temperature of 24 to 26°C and a relative humidity of 45 to 55%.
  • the resin film according to the first embodiment has a storage modulus at 180° C. of preferably 1.0 ⁇ 10 6 Pa or more, more preferably 1.0 ⁇ 10 7 Pa or more, and most preferably in the range of 1.0 ⁇ 10 7 to 1.0 ⁇ 10 10 Pa.
  • the resin film according to the first embodiment has a storage modulus at 260° C. of preferably 1 ⁇ 10 5 Pa or more, more preferably 1.0 ⁇ 10 6 Pa or more, and most preferably in the range of 1.0 ⁇ 10 6 Pa to 5.0 ⁇ 10 9 Pa.
  • Glass transition temperature When the resin film according to the first embodiment is amorphous and has no melting point, the glass transition temperature (Tg) is preferably 180° C. or higher, and more preferably within the range of 180 to 400° C. When the Tg of the resin film is 180° C. or higher, heat resistance that enables use in mounting and high-temperature environments can be achieved.
  • the storage modulus and glass transition temperature of a resin can be measured by the following method.
  • a film or resin sheet is cut into a size of 5 mm x 20 mm to prepare a sample for evaluation.
  • a dynamic viscoelasticity device e.g., DMA: manufactured by TA Instruments, product name: RSA-G2
  • the sample is heated stepwise from 30°C to 500°C at a heating rate of 4°C/min, and measurements are taken at a frequency of 1 Hz.
  • the temperature at the peak of tan ⁇ is taken as the glass transition temperature Tg. Note that if multiple tan ⁇ peaks appear, the highest temperature among the multiple peak temperatures is taken as Tg.
  • tan ⁇ refers to the loss factor, and means the ratio of the loss modulus G'' to the storage modulus G' (G''/G').
  • the melting point (Tm) is preferably 260° C. or higher, and more preferably in the range of 260 to 450° C.
  • Tm melting point
  • the resin film has a melting point Tm of 260° C. or higher, heat resistance that enables use in mounting and high-temperature environments can be achieved.
  • the melting point can be measured by the method described above. When multiple peaks appear in the measurement with a differential scanning calorimeter, the maximum temperature among the peak temperatures is taken as the melting point.
  • the melting point of the resin can be measured, for example, by a method conforming to JIS K7121:2012. When multiple melting peaks appear, the highest peak temperature is taken as the melting point.
  • the resin film according to the first embodiment has a tensile modulus of elasticity of 1.0 GPa or more.
  • the tensile modulus of elasticity of the resin film according to the first embodiment is preferably in the range of 1.5 to 6.0 GPa, and more preferably in the range of 1.5 GPa to 5.0 GPa. If the tensile modulus of elasticity is less than 1.0 GPa, tack occurs, and it is not possible to obtain a film that is easy to process.
  • the resin film according to the first embodiment has an elongation of preferably 1% or more, more preferably 5% or more. If the elongation is less than 1%, it leads to a deterioration in toughness.
  • the tensile modulus and elongation of a resin can be measured by the following method.
  • a Strograph R-1 manufactured by Toyo Seiki Seisakusho Co., Ltd.
  • a tensile test is used to perform a tensile test on a resin film with a width of 12.7 mm and a length of 127 mm at a temperature of 23°C and a relative humidity of 50% RH at a rate of 50 mm/min. From the results obtained, the tensile modulus and elongation of the resin film can be calculated.
  • phase structure of the resin film according to the first embodiment is similar to the phase structure of the resin composition according to the first embodiment.
  • the metal-clad laminate according to the first embodiment includes an insulating resin layer and a metal layer laminated on one or both surfaces of the insulating resin layer, and at least one of the insulating resin layers is made of the resin film. Note that the metal-clad laminate according to the first embodiment may include any layer other than those described above.
  • the material of the metal layer is not particularly limited, but examples include copper, stainless steel, iron, nickel, beryllium, aluminum, zinc, indium, silver, gold, tin, zirconium, tantalum, titanium, lead, magnesium, manganese, and alloys thereof. Among these, copper or copper alloys are particularly preferred.
  • the material of the wiring layer in the circuit board of this embodiment, which will be described later, is the same as that of the metal layer.
  • the thickness of the metal layer is not particularly limited, but when a metal foil such as copper foil is used, it is preferably 35 ⁇ m or less, and more preferably in the range of 5 to 25 ⁇ m. From the viewpoint of production stability and handling, it is preferable that the lower limit of the thickness of the metal foil is 5 ⁇ m.
  • copper foil When copper foil is used, it may be rolled copper foil or electrolytic copper foil. Furthermore, commercially available copper foil may be used as the copper foil.
  • the dielectric loss tangent is deteriorated due to an increase in the terminal functional group.
  • the weight average molecular weight exceeds 300,000, the steric hindrance becomes large and the reaction from the terminal group becomes difficult to proceed.
  • the concentration of the terminal group during the reaction with the component B1 or B2 is reduced, and the reaction rate is reduced.
  • the viscosity increases excessively and the film becomes insoluble in a solvent.
  • the weight average molecular weight of the non-thermoplastic polyimide of the component (A2) described below is the same as that of the component (A1). The weight average molecular weight can be measured by the method described above.
  • an acid dianhydride having an ester group in the molecule represented by the following general formula (4) which is capable of increasing the linearity of the polyimide molecular chain and is expected to improve the tensile modulus and reduce the CTE due to in-plane orientation
  • an acid anhydride having a biphenyl skeleton or a naphthalene skeleton such as 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) or 2,3,6,7-naphthalenetetracarboxylic dianhydride (NTCDA).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • NTCDA 2,3,6,7-naphthalenetetracarboxylic dianhydride
  • these tetracarboxylic acid anhydrides can be used alone or in combination of two or more.
  • R1 represents an alkyl group having 1 to 3 carbon atoms
  • the compound represented by the general formula (4) is an ester group-containing acid dianhydride, and although it has a relatively large molecular weight and can reduce the concentration of imide groups, it has the effect of suppressing the CTE low.
  • the ester structure has the effect of imparting an ordered structure to the entire polymer through intermolecular interactions.
  • the molecule contains a biphenyl skeleton or a naphthalene skeleton and two ester structures (-CO-O-) bonded to the biphenyl skeleton or the naphthalene skeleton, it is preferable because the biphenyl skeleton and the naphthalene skeleton have rigidity and therefore tend to form an ordered structure.
  • dianhydrides include 1,3-dihydro-1,3-dioxo-5,5'-(3,3'-dimethyl[1,1'-biphenyl]-4,4'-diyl) ester, 1,3-dihydro-1,3-dioxo-5,5'-(3,3',5,5'-tetramethyl[1,1'-biphenyl]-4,4'-di
  • tetracarboxylic acid residues having a biphenyl or naphthalene skeleton have high planarity and linearity, which promotes in-plane orientation by improving the linearity of the polyimide molecular chains, improves the tensile modulus, and further improves the CTE. Furthermore, by contributing to the stacking of molecular chains, they facilitate the formation of an ordered structure, and by suppressing molecular motion, they can improve the dielectric tangent.
  • the content of the acid dianhydride residues (1) in the non-thermoplastic polyimide precursor of component (A1) is preferably 20 mol % or more, more preferably 25 mol % or more, and most preferably within the range of 40 to 100 mol %, based on the total tetracarboxylic dianhydride residues of component (A1). If the content of the acid dianhydride residues (1) is less than 20 mol %, the effects of improving the ordered structure of the molecules and lowering the dielectric tangent and CTE by suppressing their motion are not fully exerted.
  • the same effect can be achieved by using a tetracarboxylic acid residue having a biphenyl skeleton or a naphthalene skeleton (excluding those that overlap with the acid dianhydride residue (1)) instead of the acid dianhydride residue (1) in the non-thermoplastic polyimide precursor of component (A1), and the content is preferably 20 mol % or more, more preferably 25 mol % or more, and most preferably in the range of 40 to 100 mol % based on the total tetracarboxylic acid dianhydride residues.
  • the non-thermoplastic polyimide precursor of component (A1) can be any diamine compound generally used in non-thermoplastic polyimide precursors without any restrictions.
  • diamine compounds include 1,4-diaminobenzene (p-PDA; paraphenylenediamine), 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB), 2,2'-diethyl-4,4'-diaminobiphenyl (m-EB), 2,2'-diethoxy-4,4'-diaminobiphenyl (m-EOB), 2,2'-dipropoxy-4,4'-diaminobiphenyl (m-POB), 2,2'-di-n-propyl-4,4'-diaminobiphenyl (m-NPB), 2,2'-divinyl-4,4'-diaminobiphenyl (VAB), 4,4'-diaminobiphenyl, 4,4'-diaminobiphenyl
  • diamines represented by the following general formula (5) and diamines having a naphthalene skeleton are particularly preferred, which can increase the linearity of the polyimide molecular chain and are expected to have a low CTE effect due to in-plane orientation.
  • diamine residue (2) the diamine residue derived from the diamine compound represented by the general formula (5) may be referred to as "diamine residue (2)".
  • the linking group X is a divalent group selected from a single bond, -CONH-, or -COO-; Y is independently hydrogen, a monovalent hydrocarbon group having 1 to 3 carbon atoms, or an alkoxy group; n is an integer from 0 to 2; and p and q are independently integers from 0 to 4.
  • the diamine compound represented by the general formula (5) has a rigid structure, and by improving the planarity and rigidity of the polyimide, it is possible to improve the stacking interaction between molecular chains. Therefore, the diamine residue (2) has low mobility, and it is possible to lower the dielectric tangent of the polyimide. In addition, by increasing the planarity of the molecular skeleton of the polyimide, it is possible to lower the CTE in the plane direction. In addition, by preferably containing a biphenyl group in the diamine residue (2), the molecular weight of the monomer-derived unit can be increased, so that the imide group concentration is decreased and a polyimide with low moisture absorption can be obtained.
  • the dielectric tangent can be decreased in that the moisture inside the molecular chain can be reduced. Furthermore, when the acid dianhydride residue (1) contains a biphenyl skeleton as a structure common to the diamine residue (2), an ordered structure of the entire polymer is easily formed, which is effective in reducing the dielectric tangent.
  • diamine compounds represented by general formula (5) include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB), 2,2'-diethyl-4,4'-diaminobiphenyl (m-EB), 2,2'-diethoxy-4,4'-diaminobiphenyl (m-EOB), 2,2'-dipropoxy-4,4'-diaminobiphenyl (m-POB), 2,2'-di-n-propyl-4,4'-diaminobiphenyl (m-NPB), 2,2'-divinyl-4,4'-diaminobiphenyl (VAB), 4,4'-diaminobiphenyl, 4,4''-diamino-p-terphenyl, etc. Of these, 2,2'-dimethyl-4,4'-diaminobipheny
  • the content of diamine residue (2) in the non-thermoplastic polyimide precursor of component (A1) is preferably 30 mol % or more, more preferably 40 mol % or more, and most preferably in the range of 50 to 100 mol %, based on the total diamine residues of component (A1). If the content of diamine residue (2) is less than 50 mol %, the effect of lowering the CTE and dielectric tangent is not fully exerted. From the viewpoint of lowering the CTE and dielectric tangent, it is preferable to make the proportion of diamine residue (2) in the total diamine residues as large as possible, and the content of diamine residue (2) may be 100 mol %.
  • the non-thermoplastic polyimide precursor of component (A1) can control the moisture absorption, dielectric properties, toughness, CTE, storage modulus, tensile modulus, etc. by selecting the type of tetracarboxylic dianhydride residue and diamine residue, or the molar ratio of each when two or more types of tetracarboxylic dianhydride residues or diamine residues are contained.
  • the non-thermoplastic polyimide precursor of component (A1) has multiple structural units (constituent units), they may exist as blocks or randomly, but it is preferable that they exist randomly.
  • the non-thermoplastic polyimide precursor of component (A1) preferably comprises tetracarboxylic dianhydride residues and diamine residues derived from aromatic tetracarboxylic dianhydrides and aromatic diamine residues derived from aromatic diamines.
  • tetracarboxylic dianhydride residues and diamine residues contained in the polyamic acid and polyimide to only residues having aromatic groups, the dimensional accuracy of the resin film in a high-temperature environment can be improved.
  • the non-thermoplastic polyimide precursor of component (A1) can be produced by reacting the above-mentioned tetracarboxylic anhydride component and diamine component in a solvent.
  • the tetracarboxylic anhydride component and diamine component are dissolved in approximately equimolar amounts in an organic solvent, and the mixture is stirred at a temperature in the range of 0 to 100°C for 30 minutes to 24 hours to cause a polymerization reaction, thereby obtaining the non-thermoplastic polyimide precursor (polyamic acid) of component (A1).
  • the reaction components are dissolved so that the resulting precursor is in the range of 5 to 50% by weight, preferably 10 to 40% by weight, in the organic solvent.
  • organic solvents used in the polymerization reaction include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N,N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), 2-butanone, dimethylsulfoxide (DMSO), hexamethylphosphoramide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, methylcyclohexane, dioxane, tetrahydrofuran, diglyme, triglyme, methanol, ethanol, benzyl alcohol, and cresol.
  • DMF N,N-dimethylformamide
  • DMAc N,N-dimethylacetamide
  • NMP N-diethylacetamide
  • NMP N-methyl-2-pyrrolidone
  • 2-butanone dimethylsulfoxide (DMSO)
  • DMSO dimethylsulfoxide
  • HE hexamethylphospho
  • organic solvents Two or more of these solvents can be used in combination, and aromatic hydrocarbons such as xylene and toluene can also be used in combination.
  • the amount of such organic solvents is not particularly limited, but it is preferable to adjust the amount of organic solvent used so that the concentration of the solution of the non-thermoplastic polyimide precursor of the component (A1) obtained by the polymerization reaction is about 5 to 50% by weight.
  • the synthesized non-thermoplastic polyimide precursor of component (A1) generally has excellent solvent solubility, so it is advantageous to use it as a reaction solvent solution, but it can be concentrated, diluted, or replaced with another organic solvent if necessary.
  • the viscosity of the solution of the non-thermoplastic polyimide precursor of component (A1) is preferably within the range of 100 cP to 100,000 cP.
  • the (B1) component is a soluble polyimide precursor having a structural unit containing at least one of an aliphatic chain and an alicyclic skeleton
  • the (B2) component is a soluble polyimide having a structural unit containing at least one of an aliphatic chain and an alicyclic skeleton.
  • the (B2) component is a thermoplastic polyimide having solvent solubility, and its precursor is the (B1) component.
  • the soluble polyimide of the (B2) component is obtained by imidizing the polyimide precursor (polyamic acid) of the (B1) component obtained by reacting a tetracarboxylic anhydride component with a diamine component.
  • the soluble polyimide of the (B2) component has a structural unit containing an aliphatic chain or an alicyclic skeleton, which enables the resin film to have a low dielectric tangent.
  • the (B1) and (B2) components preferably contain 20% by weight or more of structural units containing an aliphatic chain or alicyclic skeleton in the polymer chain, and more preferably in the range of 30 to 70% by weight. If the content of structural units containing an aliphatic chain or alicyclic skeleton is less than 20% by weight, it becomes difficult to achieve a low dielectric loss tangent when a resin film is formed.
  • the structural unit containing an aliphatic chain or alicyclic skeleton may be derived from a tetracarboxylic anhydride component or a diamine component.
  • the (B1) and (B2) components preferably have an aliphatic chain with 10 or more carbon atoms, and more preferably have an aliphatic chain with 10 to 54 carbon atoms. If they do not have an aliphatic chain with 10 or more carbon atoms, the imide group concentration increases, which may deteriorate the dielectric loss tangent when made into a film.
  • the weight average molecular weight of the (B1) component and the (B2) component is preferably in the range of 5,000 to 150,000, and more preferably in the range of 10,000 to 150,000. If the weight average molecular weight of the (B1) component and the (B2) component is less than 5,000, the toughness cannot be fully expressed. Furthermore, the dielectric loss tangent is deteriorated due to an increase in the terminal functional group concentration. On the other hand, if the weight average molecular weight exceeds 150,000, the steric hindrance becomes large, and the reaction from the terminal group becomes difficult to proceed. Furthermore, the reaction rate is decreased due to a decrease in the terminal group concentration during alloying. Furthermore, the viscosity increases excessively, and the material becomes insoluble in a solvent. The weight average molecular weight can be measured by the above-mentioned method.
  • the number average molecular weight of the (B1) component and the (B2) component is preferably in the range of 2,000 to 100,000, and more preferably in the range of 4,000 to 70,000. If the number average molecular weight of the (B1) component and the (B2) component is less than 2,000, the toughness cannot be fully expressed. Furthermore, the dielectric loss tangent is deteriorated due to an increase in the terminal functional group concentration. On the other hand, if the number average molecular weight exceeds 100,000, the steric hindrance becomes large, and the reaction from the terminal group becomes difficult to proceed. Furthermore, the reaction rate is reduced due to a decrease in the terminal group concentration during alloying. Furthermore, the viscosity increases excessively, and the material becomes insoluble in a solvent. The number average molecular weight can be measured by the above-mentioned method.
  • the soluble polyimide of component (B2) when formed into a film by itself, preferably has a dielectric loss tangent (Df) of 0.0022 or less, more preferably 0.0020 or less, at 10 GHz after 24 hours of humidity conditioning under conditions of temperature: 24 to 26°C and humidity: 45 to 55%. If the dielectric loss tangent exceeds 0.0022, the dielectric loss tangent after alloying becomes insufficient.
  • the dielectric loss tangent of component (B2) may be 0.0002 or more.
  • the soluble polyimide of component (B2) preferably has a tensile modulus of 2.5 GPa or less when formed into a film by itself, and more preferably has a modulus of 0.2 to 2.0 GPa.
  • the modulus is 2.5 GPa or less, stress can be relaxed when alloyed, and toughness is improved.
  • the modulus is more than 2.5 GPa, stress relaxation does not occur, and toughness during alloying deteriorates.
  • the modulus of tensile elasticity can be measured by the method described above.
  • thermoplastic polyimides can be used as raw materials without any particular restrictions, but it is preferable to use tetracarboxylic anhydrides represented by the following general formula (6) and/or (7).
  • tetracarboxylic anhydrides represented by the following general formula (6) and/or (7) it is preferable to use raw materials containing tetracarboxylic anhydrides represented by the following general formula (6) and/or (7) in a total of 90 mol % or more based on the total tetracarboxylic anhydride components.
  • the (B1) component and the (B2) component it is preferable for the (B1) component and the (B2) component to contain tetracarboxylic acid residues derived from tetracarboxylic acid anhydrides represented by the following general formula (6) and/or (7) in a total of 90 mol % or more based on the total tetracarboxylic acid residues.
  • tetracarboxylic acid residues derived from tetracarboxylic acid anhydrides represented by the following general formula (6) and/or (7) it is preferable to achieve both flexibility and heat resistance of the (B1) component and the (B2) component.
  • X represents a single bond or a divalent group selected from the following formulas
  • the cyclic portion represented by Y represents a cyclic saturated hydrocarbon group selected from a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, or an 8-membered ring.
  • examples of tetracarboxylic acid anhydrides represented by general formula (7) include 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 1,2,4,5-cyclohexane tetracarboxylic acid dianhydride, 1,2,4,5-cycloheptane tetracarboxylic acid dianhydride, and 1,2,5,6-cyclooctane tetracarboxylic acid dianhydride.
  • Components (B1) and (B2) can contain tetracarboxylic acid residues derived from acid anhydrides generally used as raw materials for polyimides, in addition to the tetracarboxylic acid anhydrides represented by the above general formulas (6) and (7), to the extent that the effects of the invention are not impaired.
  • (Diamine component) For the (B1) and (B2) components, diamine compounds generally used in the synthesis of thermoplastic polyimides can be used as raw materials, but from the viewpoint of lowering the dielectric tangent and improving the dielectric properties, it is preferable to use a diamine component containing an aliphatic diamine in a range of preferably 40 mol % or more, more preferably 60 mol % or more, and most preferably 80 to 100 mol % relative to the total diamine components of the (B1) and (B2) components.
  • the (B1) and (B2) components contain diamine residues derived from aliphatic diamines in a range of preferably 40 mol % or more, more preferably 60 mol % or more, and most preferably 80 to 100 mol % relative to the total diamine residues.
  • the diamine residues derived from aliphatic diamines in the above amount, the dielectric properties of the polyimide can be improved, and the thermocompression bonding properties can be improved by lowering the glass transition temperature (lowering Tg) of the polyimide, and the internal stress can be alleviated by lowering the elastic modulus.
  • the dimer acid diamine is a mixture containing the following component (a) as a main component and optionally containing components (b) and (c), and it is preferable to use a purified product in which the amounts of components (b) and (c) are controlled.
  • the dimer diamine of the component (a) means a diamine in which two terminal carboxylic acid groups (-COOH) of a dimer acid are replaced by primary aminomethyl groups (-CH 2 -NH 2 ) or amino groups (-NH 2 ).
  • Dimer acid is a known dibasic acid obtained by intermolecular polymerization of unsaturated fatty acids, and its industrial production process is almost standardized in the industry, and is obtained by dimerizing unsaturated fatty acids having 11 to 22 carbon atoms using a clay catalyst or the like.
  • dimer acid is mainly composed of a dibasic acid having 36 carbon atoms obtained by dimerizing unsaturated fatty acids having 18 carbon atoms, such as oleic acid, linoleic acid, and linolenic acid, but contains any amount of monomer acid (having 18 carbon atoms), trimer acid (having 54 carbon atoms), and other polymerized fatty acids having 20 to 54 carbon atoms depending on the degree of purification.
  • monomer acid having 18 carbon atoms
  • trimer acid having 54 carbon atoms
  • other polymerized fatty acids having 20 to 54 carbon atoms depending on the degree of purification.
  • double bonds remain after the dimerization reaction, in the present invention, those which have been further subjected to a hydrogenation reaction to reduce the degree of unsaturation are also included in the dimer acid.
  • the dimer diamine of the component (a) can be defined as a diamine compound obtained by substituting the terminal carboxylic acid group of a dibasic acid compound having a carbon number of 18 to 54, preferably 22 to 44, with a primary aminomethyl group or an amino group.
  • Aliphatic diamines can be commercially available, such as Diamine H20 (manufactured by Okamura Oil Mills, Ltd.) and PRIAMINE 1073 (product name), PRIAMINE 1074 (product name), and PRIAMINE 1075 (product name) manufactured by Croda Japan.
  • Components (B1) and (B2) can contain diamine residues derived from diamine compounds that are generally used as raw materials for polyimides, as long as the effects of the invention are not impaired.
  • the (R1) and (R2) components are reactants linked by a covalent bond.
  • the covalent bond include a single bond (carbon-carbon), an amide bond, an ester bond, an imide bond, an ether bond, and a sulfide bond.
  • general covalent bonds can also be included.
  • Weight average molecular weight The weight average molecular weight of the reactants (R1) and (R2) determined from the main peak with an area ratio of 50% or more in gel permeation chromatography (GPC) is preferably in the range of 10,000 to 1,000,000, more preferably in the range of 20,000 to 500,000, and most preferably in the range of 20,000 to 300,000. If the weight average molecular weight of the (R1) and (R2) components is less than 10,000, the film properties are impaired and low CTE characteristics cannot be achieved. In addition, the dielectric loss tangent is deteriorated due to an increase in the terminal functional groups.
  • the absolute value of the difference (SP C - SP D ) between the SP value (SP C ) of the first solvent and the SP value ( SP D ) of the second solvent is preferably 0.5 ( cal /cm 3 ) 1/2 ((1.0 (J/cm 3 ) 1/2 ) or more, and more preferably 1.0 (cal/cm 3 ) 1/2 ((2.1 (J/cm 3 ) 1/2 ) or more.
  • the absolute value of the difference (SP C - SP D ) is preferably less than 5.0 (cal/cm 3 ) 1/2 ((10.3 (J/cm 3 ) 1/2 ). When the ratio is 1/2 or more, the components (A1) and (B1) are easily mixed together.
  • the weight ratio of the first solvent to the second solvent in the coating liquid is preferably within the range of 5/95 to 95/5, more preferably within the range of 10/90 to 90/10, and even more preferably 25/75 to 75/25. If it is within the above range, it becomes easier to prepare a varnish by mixing components (A) and (B).
  • the resin composition can be produced by mixing the (A1) component with the (B1) component or the (B2) component. In this case, it is preferable to mix each component in the form of a resin solution dissolved in a solvent.
  • a resin solution of the non-thermoplastic polyimide precursor of the (A1) component may be added to a resin solution (varnish) of the (B1) component or the (B2) component and mixed, or a resin solution of the (B1) component or the (B2) component may be added to a resin solution (varnish) of the non-thermoplastic polyimide precursor of the (A1) component and mixed.
  • the (A1) component when it has a reactive functional group, it is preferable to use a (B2) component having a site that reacts with the functional group.
  • a (B2) component having a site that reacts with the functional group.
  • the (A1) component and the (B1) component or the (B2) component are linked by a covalent bond such as an amide bond
  • an acid-terminated (A1) component when an acid-terminated (A1) component is used, an amine-terminated (B1) component or a (B2) component is used
  • an acid-terminated (B1) component or a (B2) component when an acid-terminated (B1) component is used, an acid-terminated (B1) component or a (B2) component is used.
  • the method for producing a resin composition of the present invention includes the steps of: preparing a resin solution of component (A1); A step 2 of preparing a resin solution of the component (B2); and step 3 of mixing the resin solution of the component (A1) with the resin solution of the component (B2) to synthesize the second reactant component (R2).
  • the (A1) component and the (B2) component can have a covalent bond.
  • a resin solution of the (A1) component and a resin solution of the (B2) component are mixed and an amide bond is generated at the polymer chain end of a part of the (A1) component and a part of the (B2) component to form the (R2) component, it is preferable to carry out the process under an inert gas atmosphere.
  • the formation of a new chemical bond such as an amide bond can be confirmed, for example, by nuclear magnetic resonance spectroscopy (NMR).
  • the polyimide according to the second embodiment has a block structure in which a first polyimide and a second polyimide are linked by a covalent bond, the first polyimide being a non-thermoplastic polyimide of component (A2), and the second polyimide being a soluble polyimide having a structural unit containing at least one of an aliphatic chain and an alicyclic skeleton of component (B2). Due to such a block structure, the polyimide of the present invention contributes to a low dielectric tangent and a low CTE when made into a film. In the resin film, the polyimide of the present invention may be referred to as "component (R3)".
  • the polyimide of the present invention can be produced by imidizing the polyamic acid contained in the (R1) component or the (R2) component.
  • the method of imidization is not particularly limited, and for example, a heat treatment such as heating at a temperature condition in the range of 80 to 400° C. for 1 to 24 hours is preferably adopted. The temperature may be constant or may be changed during the process.
  • the polyimide of the present invention is most preferably a completely imidized structure. However, a part of the polyimide may be an amic acid.
  • the resin film according to the second embodiment is a resin film consisting of a single layer or multiple layers, and at least one of the layers contains a polyimide ((R3) component) in which a non-thermoplastic polyimide (A2) component and a soluble polyimide (B2) component having a structural unit containing an aliphatic chain or an alicyclic skeleton are covalently bonded.
  • the resin film according to the second embodiment is a polyimide layer (X) formed by imidizing a polyimide precursor and forming a film using the above-mentioned resin composition.
  • the non-thermoplastic polyimide of the (A2) component is the non-thermoplastic polyimide precursor of the (A1) component described in the resin composition.
  • the components (A2), (B2), and (R3) are most preferably completely imidized.
  • a part of the polyimide may be an amic acid.
  • the imidization rate can be calculated from the ratio of the absorbance of the benzene ring absorption band near 1015 cm ⁇ 1 to the absorbance of the C ⁇ O stretching derived from the imide group at 1780 cm ⁇ 1 and the calibration curve by measuring the infrared absorption spectrum of the polyimide thin film by the single reflection ATR method using a Fourier transform infrared spectrophotometer (commercially available: manufactured by JASCO Corporation, product name: FT/IR620). Note that by using a metal foil as the supporting substrate, the metal-clad laminate of the present invention described below can be produced.
  • the weight ratio (A2/B2) of the (A2) component to the (B2) component in the resin film is preferably within the range of 15/85 to 85/15, more preferably within the range of 20/80 to 80/20, even more preferably within the range of 35/65 to 65/35, and most preferably 40/60 to 60/40. If the weight ratio (A2/B2) is less than 15/85, the effect of lowering the CTE may not be fully manifested. On the other hand, if the weight ratio (A2/B2) exceeds 85/15, the dielectric tangent may not improve and the high-frequency characteristics may deteriorate.
  • the total amount of the (A2), (B2) and (R3) components in the resin film should exceed 25% by weight, preferably 40% by weight or more, more preferably within the range of 50 to 100% by weight, and most preferably within the range of 80 to 100% by weight, based on the entire polyimide layer (X).
  • the resin film of the present invention is not particularly limited as long as it is an insulating resin film containing the above-mentioned polyimide layer (X), and may be a film (sheet) consisting of insulating resin only, or may be an insulating resin film laminated onto a substrate such as a resin sheet, such as a copper foil, a glass plate, a polyimide film, a polyamide film, or a polyester film.
  • a resin sheet such as a copper foil, a glass plate, a polyimide film, a polyamide film, or a polyester film.
  • the (A2) component constitutes a continuous phase (continuous structure).
  • the (A2) component constitutes a continuous phase means that the region in which the (A2) component exists is continuously connected in the entire resin composition.
  • the phase structure of the resin composition is not particularly limited.
  • the resin composition may be a homogeneous phase (homogeneous compatible structure) in which the (A2) component and the (B2) component are compatible with each other, or may be a phase-separated structure such as a sea-island structure or an interconnected structure.
  • the phase structure of the resin composition according to the second embodiment is a sea-island structure
  • the (A2) component becomes a sea phase.
  • the island phase is preferably made of (B2 component).
  • the average equivalent circle diameter of the island phase is preferably 0.001 ⁇ m to 20 ⁇ m. By making the average equivalent circle diameter of the island phase 0.010 ⁇ m to 10 ⁇ m, the linear expansion coefficient can be reduced.
  • the equivalent circle diameter of the island phase means the diameter of a circle having an area equal to the area of the island phase.
  • the number density of island phases having a circle equivalent diameter of 500 nm or more is preferably 0.01 to 0.300 pieces/ ⁇ m2 . Since the number density is 0.01 to 0.200 pieces/ ⁇ m2 , the linear expansion coefficient can be further reduced. The number density can be evaluated by the above-mentioned method.
  • the thickness of the resin film of the present invention is preferably within the range of, for example, 5 to 150 ⁇ m, and more preferably within the range of, for example, 8 to 125 ⁇ m. If the thickness of the resin film is less than 5 ⁇ m, there is a risk of problems such as wrinkles occurring during transportation in the production of the resin film, or there is a risk of the resin film not exhibiting sufficient toughness and not being able to obtain a self-supporting film. On the other hand, if the thickness of the resin film exceeds 150 ⁇ m, there is a risk of a decrease in productivity of the resin film.
  • the resin film according to the second embodiment has a relative dielectric constant at 10 GHz after 24 hours of humidity conditioning under conditions of a temperature of 24 to 26°C and a humidity of 45 to 55%, which is preferably 3.5 or less, more preferably 3.1 or less, and even more preferably 3.0 or less. If the relative dielectric constant exceeds 3.5, problems such as loss of electric signals are likely to occur on the transmission path of high-frequency signals when used in a circuit board such as an FPC.
  • the relative dielectric constant can be measured by the method described above.
  • the resin film according to the second embodiment preferably has a dielectric loss tangent (Tan ⁇ ) of 0.0030 or less, more preferably 0.0022 or less at 10 GHz after 24 hours of humidity conditioning under conditions of a temperature of 24 to 26°C and a humidity of 45 to 55%. If the dielectric loss tangent exceeds 0.0030, for example, when used in a circuit board such as an FPC, problems such as loss of an electric signal tend to occur on the transmission path of a high-frequency signal.
  • the dielectric loss tangent can be measured by the method described above.
  • the resin film of the present invention preferably has a CTE of 50 ppm/K or less, more preferably in the range of 0 to 30 ppm/K.
  • a CTE of 50 ppm/K or less By having a CTE of 50 ppm/K or less, the dimensional change rate can be easily controlled when the resin film is made into a resin film or a metal-clad laminate.
  • the CTE can be measured by the method described above.
  • the resin film of the present invention preferably has a glass transition temperature (Tg) of 180° C. or higher, and more preferably in the range of 180 to 400° C.
  • Tg glass transition temperature
  • the glass transition temperature can be measured by the method described above.
  • the resin film according to the second embodiment has a tensile modulus of elasticity of 1.0 GPa or more. It is more preferable that the modulus is within the range of 1.5 to 6.0 GPa, and even more preferable that the modulus is within the range of 1.5 to 5.0 GPa. If the tensile modulus is less than 1.0 GPa, tack occurs, and it is not possible to obtain a film that is easy to process.
  • the resin film according to the second embodiment preferably has a storage modulus at 180° C. of 1.0 ⁇ 10 6 Pa or more, and more preferably within the range of 1.0 ⁇ 10 6 Pa to 10 ⁇ 10 9 Pa.
  • a storage modulus at 180° C. of 1.0 ⁇ 10 6 Pa or more, and more preferably within the range of 1.0 ⁇ 10 6 Pa to 10 ⁇ 10 9 Pa.
  • the resin film according to the second embodiment preferably has an elongation of 1% or more, more preferably 5% or more. If the elongation is less than 1%, the toughness is deteriorated.
  • the elongation can be measured by the method shown in the examples below.
  • the resin film according to the second embodiment preferably has an edge tear resistance of 0.1 N or more, more preferably 1 N or more, when the film has a thickness of 25 ⁇ m. If the edge tear resistance is less than 0.1 N, the film becomes brittle and may crack during circuit processing.
  • the edge tear resistance can be measured by the method shown in the examples below.
  • the resin film of the present invention combines a low dielectric tangent with an excellent tensile modulus, and is also expected to have a low CTE, making it useful as an insulating layer material for circuit boards, etc.
  • the metal-clad laminate according to the second embodiment includes an insulating resin layer and a metal layer laminated on one or both surfaces of the insulating resin layer, and at least one of the insulating resin layers is made of the resin film.
  • the metal-clad laminate of the present invention may include any layer other than those described above.
  • the material of the metal layer is not particularly limited, but examples include copper, stainless steel, iron, nickel, beryllium, aluminum, zinc, indium, silver, gold, tin, zirconium, tantalum, titanium, lead, magnesium, manganese, and alloys thereof. Among these, copper or copper alloys are particularly preferred.
  • the material of the wiring layer in the circuit board of this embodiment, which will be described later, is the same as that of the metal layer.
  • the thickness of the metal layer is not particularly limited, but when a metal foil such as copper foil is used, it is preferably 35 ⁇ m or less, and more preferably in the range of 5 to 25 ⁇ m. From the viewpoint of production stability and handling, it is preferable that the lower limit of the thickness of the metal foil is 5 ⁇ m.
  • copper foil When copper foil is used, it may be rolled copper foil or electrolytic copper foil. Furthermore, commercially available copper foil may be used as the copper foil.
  • the surface roughness of the metal layer is not particularly limited, but from the viewpoint of ensuring adhesion to the adhesive layer while reducing conductor loss, it is preferable for the metal layer to have a roughened surface with a ten-point average roughness (Rzjis) in the range of 0.3 to 1.5 ⁇ m.
  • the metal foil may be subjected to a surface treatment, for example, with siding, aluminum alcoholate, aluminum chelate, silane coupling agent, etc., for the purpose of, for example, rust prevention treatment or improving adhesive strength.
  • the circuit board according to the second embodiment is formed by wiring the metal layer of the metal-clad laminate.
  • One or more metal layers of the metal-clad laminate are patterned by a conventional method to form a wiring layer (conductor circuit layer), thereby manufacturing a circuit board such as an FPC.
  • the circuit board may include a coverlay film that covers the wiring layer.
  • the electronic device and electronic device according to the second embodiment include the circuit board.
  • Examples of the electronic device of the present invention include display devices such as liquid crystal displays, organic EL displays, and electronic paper, organic EL lighting, solar cells, touch panels, camera modules, inverters, converters, and components thereof.
  • Examples of the electronic device include HDDs, DVDs, mobile phones, smartphones, tablet terminals, automotive electronic control units (ECUs), power control units (PCUs), and the like.
  • the circuit board is preferably used as a component such as wiring for moving parts, cables, and connectors.

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Ce copolymère comprend : une première structure qui comprend deux cycles aromatiques ou plus ; et une seconde structure qui présente une structure de chaîne dans laquelle des atomes de carbone sont liés l'un à l'autre par des liaisons simples. Le nombre d'atomes de carbone constituant la structure de chaîne est supérieur ou égal à 6. Dans la première structure, la distance entre les cycles aromatiques est égale ou inférieure à 8,0 Å. La quantité incluse de la première structure est de 15 à 85 % en masse, et la quantité incluse de la seconde structure est de 15 à 85 % en masse.
PCT/JP2024/034823 2023-09-29 2024-09-27 Copolymère, matériau de base en résine, composition de résine, liquide de revêtement, polyimide, film de résine, stratifié plaqué de métal, carte de circuit imprimé, dispositif électronique et appareil électronique, et procédé de fabrication Pending WO2025070797A1 (fr)

Applications Claiming Priority (4)

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JP2023169700 2023-09-29
JP2023169699 2023-09-29
JP2023-169700 2023-09-29
JP2023-169699 2023-09-29

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WO2025070797A1 true WO2025070797A1 (fr) 2025-04-03

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WO (1) WO2025070797A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08208835A (ja) * 1995-01-31 1996-08-13 Japan Synthetic Rubber Co Ltd ポリイミド系共重合体の製造方法、薄膜形成剤、並びに液晶配向膜およびその製造方法
JP2022062784A (ja) * 2020-10-09 2022-04-21 株式会社カネカ ポリイミド積層フィルム
JP2022099778A (ja) * 2020-12-23 2022-07-05 日鉄ケミカル＆マテリアル株式会社 ポリイミド組成物、樹脂フィルム、積層体、カバーレイフィルム、樹脂付き銅箔、金属張積層板及び回路基板
JP2023041626A (ja) * 2021-09-13 2023-03-24 荒川化学工業株式会社 （メタ）アクリロイル基含有ポリイミド前駆体、（メタ）アクリロイル基含有ポリイミド前駆体の硬化物、多官能アミン伸長（メタ）アクリロイル基含有ポリイミド前駆体及び多官能アミン伸長（メタ）アクリロイル基含有ポリイミド前駆体の硬化物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08208835A (ja) * 1995-01-31 1996-08-13 Japan Synthetic Rubber Co Ltd ポリイミド系共重合体の製造方法、薄膜形成剤、並びに液晶配向膜およびその製造方法
JP2022062784A (ja) * 2020-10-09 2022-04-21 株式会社カネカ ポリイミド積層フィルム
JP2022099778A (ja) * 2020-12-23 2022-07-05 日鉄ケミカル＆マテリアル株式会社 ポリイミド組成物、樹脂フィルム、積層体、カバーレイフィルム、樹脂付き銅箔、金属張積層板及び回路基板
JP2023041626A (ja) * 2021-09-13 2023-03-24 荒川化学工業株式会社 （メタ）アクリロイル基含有ポリイミド前駆体、（メタ）アクリロイル基含有ポリイミド前駆体の硬化物、多官能アミン伸長（メタ）アクリロイル基含有ポリイミド前駆体及び多官能アミン伸長（メタ）アクリロイル基含有ポリイミド前駆体の硬化物

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