Classifications

• • 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
  • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
• • 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
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • 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
  • C08G73/1003—Preparatory processes
  • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
  • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
  • C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
• • 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
  • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
• • 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
  • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
  • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
• • 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
  • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
  • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
• • 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
  • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
• • 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
  • 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
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • 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
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
  • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
• • 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
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
• • 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
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
• • 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
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
• • 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
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
• • 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
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
• • 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
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
  • C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
• • 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
  • C09J2479/00—Presence of polyamine or polyimide
  • C09J2479/08—Presence of polyamine or polyimide polyimide
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/01—Manufacture or treatment
  • H10W72/013—Manufacture or treatment of die-attach connectors
  • H10W72/01351—Changing the shapes of die-attach connectors
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/071—Connecting or disconnecting
  • H10W72/073—Connecting or disconnecting of die-attach connectors
  • H10W72/07331—Connecting techniques
  • H10W72/07332—Compression bonding, e.g. thermocompression bonding
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/071—Connecting or disconnecting
  • H10W72/073—Connecting or disconnecting of die-attach connectors
  • H10W72/07331—Connecting techniques
  • H10W72/07335—Applying EM radiation, e.g. induction heating or using a laser
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/071—Connecting or disconnecting
  • H10W72/073—Connecting or disconnecting of die-attach connectors
  • H10W72/07351—Connecting or disconnecting of die-attach connectors characterised by changes in properties of the die-attach connectors during connecting
  • H10W72/07352—Connecting or disconnecting of die-attach connectors characterised by changes in properties of the die-attach connectors during connecting changes in structures or sizes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/30—Die-attach connectors
  • H10W72/321—Structures or relative sizes of die-attach connectors
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/30—Die-attach connectors
  • H10W72/351—Materials of die-attach connectors
  • H10W72/353—Materials of die-attach connectors not comprising solid metals or solid metalloids, e.g. ceramics
  • H10W72/354—Materials of die-attach connectors not comprising solid metals or solid metalloids, e.g. ceramics comprising polymers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/30—Die-attach connectors
  • H10W72/351—Materials of die-attach connectors
  • H10W72/355—Materials of die-attach connectors of outermost layers of multilayered die-attach connectors, e.g. material of a coating

Definitions

• the present invention relates to an adhesive, an adhesive-attached substrate, a laminate, and a method for manufacturing a semiconductor device using the same. More specifically, the present invention relates to adhesive compositions suitably used for temporary adhesion and mounting of semiconductor elements, and methods for producing adhesive-attached substrates, laminates, and semiconductor devices using them.
• semiconductor elements that are incorporated into semiconductor devices are transferred and mounted on circuit boards and the like using a pick-and-place method using a flip chip bonder. 2. Description of the Related Art In recent years, semiconductor devices have become more sophisticated and smaller, and along with this, semiconductor elements incorporated in semiconductor devices have also become smaller and thinner, and the number of mounted semiconductor devices has increased.
• Patent Documents 1 and 2 In recent years, in devices using semiconductor chips such as gallium-arsenide and indium-phosphorus, the heat generated when the device is driven has become a problem. Studies have been made on directly bonding a chip to a substrate to promote heat dissipation from the device and improve drivability (Patent Documents 1 and 2).
• such adhesive resins are used not only for transferring and mounting semiconductor elements, but also as adhesives for bonding substrates together.
• the device substrate in order to prevent warpage and cracking of the substrate during thinning processing of the device substrate, the device substrate is passed through the process after being bonded with a support substrate.
• voids are generated during high-temperature processing such as ion implantation, which is essential in the production of power semiconductors. can be suppressed, and can be easily removed with a solvent after treatment (Patent Document 5).
• the polyimide copolymers presented in Patent Documents 5 and 6 have high heat resistance, but are specialized for process passability after bonding to substrates and copper foils, so they have very high adhesiveness and semiconductors. When trying to apply it to the application of transferring minute devices such as elements, it is difficult to apply because the transfer itself is difficult and there is a lot of residue due to the adhesive on the chip surface after transfer. there were.
• the present invention solves the problems of the prior art as described above, and finds a technique that allows a large number of semiconductor elements to be transferred and mounted at once even under conditions where high temperatures are applied during processing such as direct bonding. rice field.
• the pressure-sensitive adhesive of the present invention has the following constitution. i.e. [1] A pressure-sensitive adhesive containing a polyimide copolymer (A) having at least an acid dianhydride residue and a diamine residue and a dimer acid epoxy resin (B),
• the diamine residue is represented by formula (1), wherein n is a natural number of 1 to 15 (hereinafter referred to as diamine residue (A1)), represented by formula (1), n is a natural number of 16 to 50 (hereinafter referred to as diamine residue (A2)), and a diamine residue (A3) having a phenolic hydroxyl group (hereinafter referred to as diamine residue (A3)) death, Containing 50.0 mol% or more and 95.0 mol% or less of diamine residues (A1) with respect to 100.0 mol% of all diamine residues in the polyimide copolymer (A), diamine residues (A2) and a diamine residue (A3) of 1.0 mol
• R 1 and R 2 may be the same or different and represent an alkylene group or a phenylene group having 1 to 30 carbon atoms.
• R 3 to R 6 may be the same or different. may be an alkyl group having 1 to 30 carbon atoms, a phenyl group or a phenoxy group. * indicates a bond.
• [2] The pressure-sensitive adhesive according to [1] above, which contains 5 parts by weight or more and 50 parts by weight or less of the dimer acid epoxy resin (B) with respect to 100 parts by weight of the polyimide copolymer (A).
• the total amount of diamine residues (A1) and diamine residues (A2) is 70.0 mol% or more with respect to 100.0 mol% of all diamine residues in the polyimide copolymer (A). 0 mol% or less, and the molar ratio of the diamine residue (A1) to the diamine residue (A2) is in the range of 5:1 to 30:1 [1] to [3].
• Adhesive Adhesive.
• [5] The adhesive according to [3] or [4], which has 0.1 parts by weight or more and 1.5 parts by weight or less of the crosslinking agent (C) with respect to 100 parts by weight of the polyimide copolymer (A) .
• [6] A substrate with an adhesive layer, wherein an adhesive layer comprising the adhesive according to any one of [1] to [5] is formed on a supporting substrate.
• the substrate with an adhesive layer according to [6] wherein the thickness of the adhesive layer formed on the support substrate is 0.1 ⁇ m or more and 10 ⁇ m or less.
• [8] A laminate in which a semiconductor element is held on the pressure-sensitive adhesive layer side surface of the pressure-sensitive adhesive layer-attached substrate according to [6] or [7] above.
• a method for manufacturing a semiconductor device using the laminate according to [8] or [9] A step of making the surface of the laminate on which the semiconductor elements are laminated and the circuit board face each other, and electrically joining the semiconductor element and the circuit board by thermocompression bonding; After that, a step of removing the adhesive layer-attached substrate portion of the laminate from the semiconductor element, A method of manufacturing a semiconductor device.
• [14] A laminate in which a semiconductor element is held on the adhesive layer-side surface of the circuit board with an adhesive layer according to [13].
• [15] A method for manufacturing a semiconductor device using the laminate according to [14], Manufacture of a semiconductor device, comprising a step of applying pressure to the laminate in the lamination direction to break the pressure sensitive adhesive layer, bring the circuit board and the semiconductor element into contact, and electrically join the circuit board and the semiconductor element. Method.
• [16] A step of facing a circuit board to the semiconductor-laminated surface of a laminate in which a substrate, an adhesive layer, and a plurality of semiconductor elements are laminated in this order; A step of applying heat of 80° C. or more and less than 300° C.
• a method of manufacturing a semiconductor device In a laminate in which a circuit board, an adhesive layer, and a plurality of semiconductor elements are laminated in this order, A method for manufacturing a semiconductor device, comprising a step of applying pressure in a stacking direction to break an adhesive layer to bring a circuit board and a semiconductor element into contact with each other, thereby electrically joining the circuit board and the semiconductor element. [18] The method for manufacturing a semiconductor device according to the above [16] or [17], wherein the adhesive layer contains polyimide.
• the adhesive of the present invention is excellent in adhesiveness and heat resistance, it becomes possible to transfer and mount a large amount of semiconductor elements at once even when there is a step of applying heat to the semiconductor elements. .
• the pressure-sensitive adhesive of the present invention is A pressure-sensitive adhesive containing a polyimide copolymer (A) having at least an acid dianhydride residue and a diamine residue and a dimer acid epoxy resin (B),
• the diamine residue (A1) wherein the diamine residue is represented by the formula (1), where n is a natural number of 1 or more and 15 or less, a diamine represented by the formula (1), where n is a natural number of 16 or more and 50 or less Having a residue (A2) and a diamine residue (A3) having a phenolic hydroxyl group, Containing 50.0 mol% or more and 95.0 mol% or less of diamine residues (A1) with respect to 100.0 mol% of all diamine residues in the polyimide copolymer (A), diamine residues (A2) and a diamine residue (A3) of 1.0 mol% to 30.0 mol%.
• R 1 and R 2 which may be the same or different, represent an alkylene group having 1 to 30 carbon atoms or a phenylene group.
• R 3 to R 6 may be the same or different and represent an alkyl group having 1 to 30 carbon atoms, a phenyl group or a phenoxy group. * indicates a joint.
• the adhesive of the present invention has adhesiveness even after it is reacted with a cross-linking agent or a curing agent or subjected to curing treatment such as heat treatment, and the article held by the adhesive is reversibly held, It is characterized by being able to detach.
• the polyimide copolymer (A) of the present invention has an acid dianhydride residue and a diamine residue, and a diamine having at least a diamine residue (A1) as a diamine component when polymerizing the polyimide copolymer, It can be prepared by copolymerizing a diamine having a diamine residue (A2) and a diamine having a diamine residue (A3).
• the polyimide copolymer (A) is represented by the formula (1), wherein n is a natural number of 1 or more and 15 or less, and a diamine residue (A1) represented by the formula (1), where n is 16 or more and 50 or less.
• the polyimide copolymer (A) has a diamine residue (A3), it is possible to form a crosslinked structure with a dimer acid-modified epoxy resin (B), which will be described later.
• a more preferable range of n in formula (1) of the diamine having a diamine residue (A2) is a natural number of 16 or more and 25 or less. With this range, the heat resistance can be improved.
• the polyimide copolymer (A) constituting the adhesive of the present invention contains 50.0 mol% or more and 95.0 mol% or less of diamine residues (A1) in 100.0 mol% of all diamine residues. .
• diamine residues (A1) in 100.0 mol% of all diamine residues. .
• a more preferable range of the content of the diamine residue (A1) is 70.0 mol% or more and 90.0 mol% or less with respect to 100.0 mol% of the total diamine residues in the polyimide copolymer (A). .
• the polyimide copolymer (A) contains 70.0 mol% or more of the diamine residue (A1) with respect to 100.0 mol% of the total diamine residues in the polyimide copolymer (A), thereby causing excessive
• the semiconductor element can be held without applying pressure, and damage to the semiconductor element can be prevented.
• the polyimide copolymer (A) contains 90.0 mol% or less of the diamine residue (A1) with respect to 100.0 mol% of the total diamine residues in the polyimide copolymer (A). It is possible to prevent the semiconductor element from being buried in the adhesive when the laminated body holding the semiconductor element is formed.
• the polyimide copolymer (A) constituting the pressure-sensitive adhesive of the present invention contains 1.0% of diamine residues (A2) per 100.0 mol % of all diamine residues in the polyimide copolymer (A). It contains 0 mol % or more and 40.0 mol % or less.
• the site of the structure of the diamine residue (A2) aggregates on the outermost layer of the pressure-sensitive adhesive layer, and the adhesiveness of the outermost layer of the pressure-sensitive adhesive layer can be reversibly retained and adjusted to a range in which detachment is possible. .
• a more preferable range of the content of the diamine residue (A2) is 2.0 mol% or more and 30.0 mol% or less with respect to 100.0 mol% of the total diamine residues in the polyimide copolymer (A). be.
• the structure of the diamine residue (A2) in the outermost layer are uniformly distributed, and unevenness of adhesiveness can be reduced.
• the pressure-sensitive adhesive layer is less likely to decompose during the heat treatment in the transfer/mounting process of the semiconductor element, and good heat resistance is exhibited.
• the total amount of diamine residues (A1) and diamine residues (A2) is 70.0 mol% or more and 98.0 mol% or less with respect to 100.0 mol% of all diamine residues in the polyimide copolymer (A) and the molar ratio of the diamine residue (A1) to the diamine residue (A2) is preferably in the range of 5:1 to 30:1.
• the total amount of diamine residues (A1) and diamine residues (A2) is 70.0 mol% or more and 98.0 mol% with respect to 100.0 mol% of all diamine residues in the polyimide copolymer (A)
• the glass transition temperature of the polyimide copolymer (A) is lowered to around room temperature, so that it is possible to laminate semiconductor elements without applying an excessive temperature.
• a more preferable range of the total amount of diamine residues (A1) and diamine residues (A2) is 75.0 mol% or more and 95 mol % or less, more preferably 80.0 mol % or more and 90.0 mol % or less. If the total amount of diamine residues (A1) and diamine residues (A2) is 80.0 mol % or more, the semiconductor device can be laminated at room temperature. When the total amount of the diamine residues (A1) and the diamine residues (A2) is 90.0 mol % or less, the film does not become too soft at room temperature and the substrate can be easily handled after forming the pressure-sensitive adhesive layer.
• the diamine The molar ratio of the residue (A1) to the diamine residue (A2) is in the range of 5:1 to 30:1, so that adhesiveness suitable for holding the semiconductor device can be obtained.
• n in formula (1) and its ratio can be determined by measuring the molecular weight of the diamine corresponding to the monomer of the diamine residue (A1) and the diamine residue (A2).
• a gel permeation chromatography method can be used to measure the molecular weight of the diamine.
• the weight ratio of n different diamines contained in the diamine can be calculated from the ratio of the slice area at each molecular weight. By dividing the obtained weight ratio by the corresponding molecular weight, the mole fraction of diamines with different molecular weights can be calculated.
• the proportion of the diamine residue (A1) and the diamine residue (A2) contained in the polyimide copolymer (A) is the diamine residue (A1 ) and the diamine residue (A2), which is the monomer of the diamine residue (A2).
• the diamine residue (A1) and the diamine residue (A2) include ⁇ , ⁇ -bis(3-aminopropyl)polydimethylsiloxane, ⁇ , ⁇ -bis(3-aminopropyl)polydiethylsiloxane, ⁇ , ⁇ - Bis(3-aminopropyl)polydipropylsiloxane, ⁇ , ⁇ -bis(3-aminopropyl)polydibutylsiloxane, ⁇ , ⁇ -bis(3-aminopropyl)polydiphenoxysiloxane, ⁇ , ⁇ -bis(2-amino ethyl)polydimethylsiloxane, ⁇ , ⁇ -bis(2-aminoethyl)polydiphenoxysiloxane, ⁇ , ⁇ -bis(4-aminobutyl)polydimethylsiloxane, ⁇ , ⁇ -bis(4-aminobutyl)
• the polyimide copolymer that constitutes the adhesive of the present invention contains a diamine residue (A3) having a phenolic hydroxyl group.
• A3 diamine residue having a phenolic hydroxyl group.
• the introduction of a crosslinked structure formed by reacting with the dimer acid-modified epoxy resin (B) increases the cohesive force of the adhesive, thereby increasing the semiconductor element held by the adhesive.
• the adhesive is peeled off, tearing of the adhesive is reduced, and it is possible to prevent the adhesive from remaining on the surface of the semiconductor element.
• the residue of the adhesive when the semiconductor element is peeled off is referred to as "adhesive residue".
• a preferable content of diamine residues (A3) is 1.0 mol % or more and 30.0 mol % or less with respect to 100.0 mol % of all diamine residues in the polyimide copolymer (A).
• a more preferable content of the diamine residue (A3) is 5.0 mol% or more and 20.0 mol% or less with respect to 100.0 mol% of the total diamine residues in the polyimide copolymer (A). is.
• the polyimide copolymer (A) contains Since cross-linking proceeds uniformly on the film surface as well, adhesive residue is further suppressed and chemical resistance is improved. Further, the polyimide copolymer (A) contains 20.0 mol% or less of the diamine residue (A3) with respect to 100.0 mol% of the total diamine residues in the polyimide copolymer (A). , the semiconductor element can be stably held.
• diamine residue (A3) of the present invention examples include 2,5-diaminophenol, 3,5-diaminophenol, 3,3′-dihydroxybenzidine, 2,2-bis(3-amino-4hydroxyphenyl ) propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4′-dihydroxy-3,3′-diaminodiphenylsulfone, 4,4′-dihydroxy-3,3′-diamino diphenyl ether, 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 4,4'-dihydroxy-3,3'-diaminodiphenylmethane, 4,4'-dihydroxy-3,3'-diaminobenzophenone, 1,3 -bis(4-amino-3-hydroxyphenyl)benzene, 1,3-bis(3-amino-4-hydroxyphenyl)benzene, bis(4-d
• the polyimide copolymer (A) may have a diamine residue other than the diamine residue (A1), the diamine residue (A2), and the diamine residue (A3).
• Diamine residues other than diamine residues (A1), diamine residues (A2), and diamine residues (A3) are 0 in 100.0 mol% of all diamine residues in the polyimide copolymer (A). .1 mol % or more and 40.0 mol % or less is preferable.
• diamine residue other than the diamine residue (A1), the diamine residue (A2), and the diamine residue (A3) include p-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene, 2 ,4-diaminotoluene, 3,5-diaminobenzoic acid, 2,6-diaminobenzoic acid, 2-methoxy-1,4-phenylenediamine, 4,4′-diaminobenzanilide, 3,4′-diaminobenzanilide , 3,3′-diaminobenzanilide, 3,3′-dimethyl-4,4′-diaminobenzanilide, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(3-aminophenyl) Fluorene, 9,9-bis(3-methyl-4-aminophenyl)fluorene, 9,9-bis(3,5-
• the polyimide copolymer (A) contains an acid dianhydride residue, preferably an aromatic tetracarboxylic dianhydride residue.
• the acid dianhydride residue can contain a known acid dianhydride residue.
• residues of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2'dimethyl-3, 3',4,4'-biphenyltetracarboxylic dianhydride, 5,5'dimethyl-3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'- biphenyltetracarboxylic dianhydride, 2,2′,3,3′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-diphenylethertetracarboxylic dianhydride, 2,3,
• the polyimide copolymer (A) may contain a residue of a tetracarboxylic dianhydride having an aliphatic ring to the extent that the heat resistance of the polyimide copolymer (A) is not impaired. can.
• tetracarboxylic dianhydride residue having an aliphatic ring examples include 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexenetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, Residues derived from 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione etc.
• the tetracarboxylic dianhydride residue may be contained alone or in combination of two or more.
• the molecular weight of the polyimide copolymer (A) can be adjusted by equimolarizing the acid dianhydride component and the diamine component used in the synthesis, or by making either of them excessive. Either the acid dianhydride component or the diamine component may be in excess and the polymer chain ends may be capped with a terminal capping agent such as an acid component or an amine component.
• a dicarboxylic acid or its anhydride is preferably used as the terminal blocking agent for the acid component, and a monoamine is preferably used as the terminal blocking agent for the amine component.
• Known monoamines can be used as a terminal blocking agent for the amine component, and among them, aniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6 -aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 3-amino-4,6-dihydroxypyrimidine , 2-aminophenol, 3-aminophenol, 4-aminophenol, and the like are preferred. Two or more of these may be used as the terminal blocking agent for the amine component.
• Acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, and cyclohexanedicarboxylic anhydride can be used as terminal blockers for acid components, and monocarboxylic acids and monoacid chloride compounds as monoactive ester compounds.
• Monocarboxylic acids such as monocarboxylic acids, 3-carboxyphenol, 4-carboxyphenol, 1-hydroxy-6-carboxynaphthalene, and monoacid chloride compounds in which the carboxyl group is acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexane
• Dicarboxylic acids monoacid chloride compounds in which only one carboxyl group of dicarboxylic acids such as 1,5-dicarboxynaphthalene and 1,6-dicarboxynaphthalene is acid-chlorinated, monoacid chloride compounds and N-hydroxybenzotriazole and imidazole , N-hydroxy-5-norbornene-2,3-dicarboximide, and the like are preferred. Two or more of these acid component terminal blocking agents may be used.
• the molar ratio of the acid dianhydride component/diamine component of the polyimide copolymer (A) can be appropriately adjusted so that the viscosity of the resin composition is within a range that is easy to use in coating or the like, and is 100/100. It is common to adjust the molar ratio of the acid dianhydride component/diamine component in the range of ⁇ 100/95, or 100/100 to 95/100. If the molar ratio of the acid dianhydride component/diamine component of the polyimide copolymer (A) is changed significantly beyond the above range in the direction of making one of them excessive, the molecular weight of the resin will decrease and the mechanical properties of the formed film will deteriorate. It is preferable to adjust the molar ratio within a range in which the adhesive strength is stable.
• the polyimide copolymer (A) is a polyimide precursor that is ring-closed by heating to become a polyimide copolymer, or a polyimide copolymer that is ring-closed by heating. It may be a ring-closed polyimide precursor.
• the method for polymerizing the polyimide copolymer (A) is not particularly limited.
• polyamic acid which is a polyimide precursor
• acid dianhydride and diamine are stirred in a solvent at 0 to 100° C. for 1 to 100 hours to obtain a polyamic acid resin solution.
• the polyimide resin becomes soluble in the solvent, after the polyamic acid is polymerized, the temperature is raised to 120 to 300° C. and stirred for 1 to 100 hours to convert to polyimide to obtain a polyimide resin solution.
• toluene, o-xylene, m-xylene, p-xylene, or the like may be added to the reaction solution, and the water produced by the imidization reaction may be azeotropically removed with these solvents.
• the adhesive of the present invention further contains a dimer acid epoxy resin (B) as an essential component.
• the dimer acid-modified epoxy resin has a structure in which the terminal of the dimer acid is epoxidized and has a flexible skeleton.
• the dimer acid epoxy resin (B) undergoes a cross-linking reaction with the phenolic hydroxyl groups contained in the polyimide copolymer (A), thereby cross-linking the polyimide copolymer (A) of the adhesive, thereby removing the semiconductor element held by the adhesive.
• the chemical resistance is improved by cross-linking the polyimide copolymer (A).
• by using a particularly flexible dimer acid-modified epoxy resin (B) it is possible to crosslink without reducing the flexibility of the film. Retains gender.
• the adhesive of the present invention preferably further contains 5 parts by weight or more and 50 parts by weight or less of a dimer acid-modified epoxy resin (B) with respect to 100 parts by weight of the polyimide copolymer (A).
• a dimer acid-modified epoxy resin (B) is within this range, it is effective in further suppressing adhesive residue and improving chemical resistance.
• the content of the dimer-residual-modified epoxy resin (B) is within this range, it effectively forms a crosslinked structure with the polyimide copolymer (A) and improves heat resistance.
• the dimer acid-modified epoxy resin (B) is obtained by introducing a glycidyl group into a dibasic acid obtained by dimerizing an unsaturated fatty acid.
• 11-22 higher unsaturated fatty acids are preferred.
• higher unsaturated fatty acids include oleic acid, elaidic acid, octadecenoic acid, linoleic acid, palmitoleic acid, myristoleic acid, linolenic acid, isoleic acid, eicosenoic acid, docosenoic acid, branched octadecenoic acid, branched hexadecenoic acid, undecylenic acid, and the like. can be mentioned.
• JER871, JER872 (above, trade name, manufactured by Mitsubishi Chemical Corporation), ERISYSGS-120 (above, trade name, manufactured by CVC), etc., in which a glycidyl group is introduced into a dimer of linolenic acid, are included, but are not limited thereto. .
• the adhesive of the present invention may contain a curing accelerator to accelerate the curing of the polyimide copolymer (A) and the dimer acid-modified epoxy resin (B), if necessary.
• curing accelerators include imidazoles, tertiary amines or salts thereof, and organic boron salt compounds, among which imidazoles are preferred.
• imidazoles include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-n-propylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2- Phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2 -ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-didazo
• Curezol C17Z Curezol 2MZ, Curezol 1B2MZ, Curezol 2E4MZ, Curezol 2E4MZ-CN, Curezol 2MZ-AZINE, and Curezol 2MZ-OK (manufactured by Shikoku Kasei Co., Ltd.). ) and the like.
• a preferable addition amount of the curing accelerator is 0.1 parts by weight or more and 5.0 parts by weight or less with respect to 100 parts by weight of the polyimide copolymer (A).
• a more preferable content of the curing accelerator is 0.5 parts by weight or more and 2.0 parts by weight or less with respect to 100 parts by weight of the polyimide copolymer (A).
• the pressure-sensitive adhesive of the present invention preferably further contains a cross-linking agent (C) having an alkoxymethyl group or a methylol group.
• Chemical resistance can be further improved by containing a cross-linking agent (C) having an alkoxymethyl group or a methylol group.
• the semiconductor element can be passed through the chemical solution treatment step while being held by the pressure-sensitive adhesive layer.
• a preferable content of the cross-linking agent (C) having an alkoxymethyl group or a methylol group is 0.1 parts by weight or more and 5.0 parts by weight or less with respect to 100 parts by weight of the polyimide copolymer (A).
• the lower range of the more preferable content of the cross-linking agent (C) having a methylol group is 0.5 parts by weight or more relative to 100 parts by weight of the polyimide copolymer (A), and the more preferable upper range is the polyimide copolymer. It is 3.0 parts by weight or less per 100 parts by weight of the coalescence (A), and a more preferable upper range is 1.5 parts by weight or less per 100 parts by weight of the polyimide copolymer (A).
• cross-linking agent (C) having an alkoxymethyl group or a methylol group examples include those with the following structures.
• Me in the formula represents a methyl group.
• the adhesive of the present invention may also contain an imidization accelerator.
• the polyimide copolymer (A) is a polyamic acid resin, it can be converted into a polyimide resin by heating at a low temperature for a short period of time with an imidization accelerator. The heat resistance is improved by converting the polyamic acid resin into the polyimide resin.
• imidization accelerators include pyridine, trimethylpyridine, ⁇ -picoline, quinoline, isoquinoline, imidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, 2,6-lutidine, triethylamine, m-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, p-hydroxyphenylacetic acid, 4-hydroxyphenylpropionic acid, p-phenolsulfonic acid, p-aminobenzoic acid and the like, but are limited to these. isn't it.
• the content of the imidization accelerator is preferably 3 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the polyimide copolymer (A). If the content of the imidization accelerator is within this range, the imidization can be completed even at a lower temperature heat treatment, and the amount of the imidization accelerator remaining in the resin layer after the heat treatment can be minimized, and the volatile content can suppress the occurrence of The imidization accelerator may be added during the polymerization of the polyimide copolymer (A) or after the polymerization.
• the substrate with an adhesive layer of the present invention is a substrate with an adhesive layer in which an adhesive layer made of an adhesive is formed on a support substrate.
• the substrate with an adhesive layer is obtained by forming a film-like layer of the adhesive of the present invention on one side of a supporting substrate, and may have another layer between the supporting substrate and the adhesive layer. .
• the supporting substrate is not particularly limited, but substrates such as glass, quartz, silicon wafers, sapphire substrates, ceramic substrates, metal substrates, semiconductor substrates and ceramic substrates, and circuit substrates in which circuit constituent materials are arranged on these substrates are used. be done.
• the thickness of the support substrate is preferably 0.3 mm or more and 5 mm or less from the viewpoint of substrate handling.
• circuit constituent materials include conductors containing metals such as silver, gold, copper, and aluminum, resistors containing inorganic oxides, etc., glass-based materials and/or resins, and the like. low-dielectric containing, high-dielectric containing resin or high-dielectric-constant inorganic particles, and insulator containing glass-based material. It is also possible to previously form an anisotropic conductive film (AFC) on the surface of the circuit board, or to mount solder bumps on the joints with the semiconductor elements.
• AFC anisotropic conductive film
• the film thickness of the adhesive layer formed on the support substrate is preferably 0.1 ⁇ m or more and 10 ⁇ m or less.
• the film thickness of the pressure-sensitive adhesive layer is 0.1 ⁇ m or more, the semiconductor element can be reliably held by the pressure-sensitive adhesive layer. Further, when the thickness of the adhesive layer is 10 ⁇ m or less, unevenness of the surface of the adhesive layer is reduced, and the semiconductor elements can be held uniformly.
• a more preferable range of the film thickness of the pressure-sensitive adhesive layer is 0.5 ⁇ m or more and 7 ⁇ m or less. When the thickness of the pressure-sensitive adhesive layer is 0.5 ⁇ m or more, it is possible to reduce adhesion failure due to foreign matter being caught when the semiconductor element is held on the surface of the pressure-sensitive adhesive layer. Moreover, since the film thickness of the adhesive layer is 7 ⁇ m or less, embedding of the semiconductor element into the adhesive layer can be reduced.
• the film thickness of the adhesive layer can be measured with a scanning electron microscope, optical film thickness meter, step meter, laser microscope, or the like.
• a method of forming a film-like adhesive layer on a support substrate includes a method of diluting the adhesive of the present invention with a solvent to form a varnish and applying it to the support substrate.
• solvents used in varnishes include polar aprotic solvents such as gamma-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n- Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropy
• cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, etc. are particularly preferable because the polyimide copolymer (A) has high solubility.
• a plurality of solvents may be mixed and used as long as the effects of storage stability and solubility of the polyimide copolymer (A) are not impaired.
• the solvent used as the polymerization solvent can also be used as the solvent for the varnish without removing it from the polymerization solution.
• the amount of the solvent for diluting the adhesive can be adjusted according to the thickness of the adhesive layer to be formed and the film formation method, and 30 parts by weight per 100 parts by weight of the polyimide copolymer (A) More than 1000 parts by weight or less is preferable.
• the method of applying the varnish onto the support substrate includes spin coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, A method using a gravure coater, a screen coater, a slit die coater, or the like can be mentioned.
• the pressure-sensitive adhesive layer on the support substrate obtained by the above method is preferably heat-treated.
• the polyimide copolymer (A) is polyamic acid resin, it can be converted into polyimide by heat treatment. Ovens, hot plates, infrared rays, etc. can be used for the heat treatment.
• the drying temperature and drying time should be at least the temperature necessary for volatilizing the solvent used for dilution and for the polyimide copolymer (A) and the dimer acid-modified epoxy resin (B) to undergo a cross-linking reaction. is preferred. Specifically, the temperature is 100° C. to 300° C., and the time is several minutes to several tens of minutes.
• the laminate of the present invention is a laminate in which a semiconductor element is held on the adhesive layer-side surface of a substrate with an adhesive layer.
• a laminate in which a semiconductor element is held on a substrate with an adhesive layer refers to one in which a semiconductor element is laminated on the adhesive layer side of the aforementioned substrate with an adhesive layer.
• the semiconductor element of the laminate include, but are not limited to, elements made from semiconductors such as GaN, AlN, InN, InP, GaAs, Si, and SiC. These semiconductor elements include those in which different types of semiconductors are laminated, and those in which electrode materials, sapphire substrates, glass substrates, and the like are laminated.
• the size of the semiconductor element is not limited, and a plurality of semiconductor elements may be held on the adhesive layer.
• the adhesive layer of the laminate described above is patterned.
• the adhesive layer By patterning the adhesive layer, it is possible to reduce the amount of the adhesive in the portions unnecessary for holding the semiconductor elements, and to reduce the adhesion of foreign substances to the portions where the semiconductor elements are not held.
• the semiconductor element held on the adhesive layer is bonded to the circuit board in the process described later, it is possible to prevent the adhesive unnecessary for holding the semiconductor element from coming into contact with the circuit board.
• the surface of the adhesive layer-attached substrate on the adhesive layer side is dry-etched through a mask for patterning, and the adhesive layer side of the adhesive layer-attached substrate.
• a photosensitive resist is formed on the adhesive layer side surface of the support substrate with the adhesive layer, and the photosensitive resist is Examples include a method of exposing, developing, and patterning the pressure-sensitive adhesive layer according to the pattern of the photosensitive resist.
• the method for holding the semiconductor element on the adhesive layer-attached substrate is not particularly limited, but the semiconductor element is transferred by bringing the substrate or film in which the semiconductor element is temporarily adhered to the adhesive layer-attached substrate of the present invention into contact with the substrate or film.
• the pressure when laminating the semiconductor element can be selected to be the optimum value depending on the adhesive strength of the adhesive layer, and is selected in the range of 0.05 MPa to 5.0 MPa. From the viewpoint of being able to prevent embedding in the pressure-sensitive adhesive layer, the pressure when laminating the semiconductor element is preferably 2.0 MPa or less. Moreover, when laminating
• the method for producing a laminate of the present invention includes at least a surface of a laser-transmitting substrate with a semiconductor element and a semiconductor element-laminated surface in which a laser-transmitting substrate and a semiconductor element are laminated in order, and an adhesive of the above-mentioned substrate with an adhesive layer.
• a laser-transmitting substrate with a semiconductor element refers to a substrate in which a semiconductor element is held directly on the laser-transmitting substrate or via another layer.
• the laser-transmissive substrate refers to a substrate that is transparent to the laser wavelength used, and the absorbance of the laser-transmissive substrate to the laser wavelength used is preferably 0.1 or less.
• inorganic substrates such as quartz, sapphire, alkali glass, non-alkali glass, and borosilicate glass
• organic substrates such as PET, aramid, polyester, polypropylene, and cycloolefin.
• a method of holding a semiconductor device on a laser-transmissive substrate includes epitaxially growing a compound semiconductor on the laser-transmissive substrate to form a compound semiconductor layer, and then forming a device directly on the laser-transmissive substrate.
• another layer is formed on a conductive substrate, and a semiconductor element is laminated thereon.
• another layer refers to a layer of a metal thin film or a resin film.
• a method of forming a metal thin film on a laser-transmitting substrate by a sputtering method or a vapor deposition method, and then forming a semiconductor device on the metal thin film can be used.
• a method of forming a resin film on a laser-transmitting substrate and laminating a semiconductor element on the resin film can be used.
• the resin film any resin such as polyimide resin, polyimidesiloxane resin, silicone resin, polybenzoxazole resin, and acrylic resin can be selected. It is more preferable if the resin constituting the resin film is a resin having adhesiveness, since the semiconductor elements can be easily laminated.
• the above-described laser-transmitting substrate with a semiconductor element and the substrate with an adhesive layer of the present invention are separated from each other by separating the semiconductor element-holding surface of the laser-transmitting substrate with a semiconductor element and the adhesive layer-side surface of the substrate with an adhesive layer.
• the substrates are fixed so that the laser-transmitting substrate with the semiconductor element and the substrate with the adhesive layer are parallel to each other.
• the laser-transmitting substrate with the semiconductor element and the substrate with the adhesive layer facing each other are preferably arranged so that the laser-transmitting substrate with the semiconductor element faces upward.
• the laser-transmitting substrate with the semiconductor element and the substrate with the adhesive layer are arranged at a constant interval. It is chosen in the range of 100 ⁇ m. Also, each substrate may have an alignment mark for transfer alignment.
• the semiconductor element is transferred to the adhesive layer-attached substrate by irradiating the laser-transmissive substrate with a laser beam from the opposite side of the semiconductor element-attached laser-transmissive substrate to the surface on which the semiconductor element is laminated.
• the process will be explained.
• the semiconductor element is irradiated with a laser beam from the laser-transmitting substrate side of the laser-transmitting substrate with a semiconductor element through the laser-transmitting substrate.
• Types of laser light include solid lasers such as YAG lasers, YVO 4 lasers, fiber lasers and semiconductor lasers, and gas lasers such as carbonic acid lasers, excimer lasers and argon lasers, and can be selected according to the wavelength used.
• the energy density of the laser light is preferably 1 mJ/cm 2 or more from the viewpoint of the stability of the energy density of the laser light, and is preferably 1000 mJ/cm 2 or less from the viewpoint of preventing damage to the semiconductor element and shortening the processing time. .
• the substrate it is also possible to heat the substrate with the adhesive layer when transferring the semiconductor element. Thereby, the holding property of the transferred semiconductor element can be improved.
• the temperature is preferably 100° C. or less because warping of the adhesive layer-coated substrate due to heat can be prevented and transfer can be performed with high positional accuracy.
• step of removing part of the adhesive layer on the adhesive layer-attached substrate in the above-described steps.
• the step of removing part of the adhesive layer may be performed before or after the transfer of the semiconductor element to the adhesive layer-attached substrate in the above-described steps.
• the specific method of removing the adhesive layer before transferring the semiconductor element and the specific method of removing the adhesive layer after transferring the semiconductor element are as described above.
• a method of manufacturing a semiconductor device according to the present invention is a method of manufacturing a semiconductor device using the laminate described above, wherein the surface of the laminate on which the semiconductor elements are laminated faces a circuit board, and the semiconductor element and the circuit are bonded together by thermocompression bonding.
• the method includes a step of electrically connecting the substrates, and then a step of removing the adhesive layer-attached substrate portion of the laminate from the semiconductor element.
• the surface of the laminate on which the semiconductor element is laminated refers to the surface of the semiconductor element opposite to the surface on which the semiconductor element is held by the adhesive layer.
• circuit board facing the surface of the laminate on which the semiconductor elements are stacked is the same as the description of the circuit board described above.
• thermocompression bonding Between the laminate and the circuit board can be performed by using a device such as a mounting bonder or a wafer bonder.
• the laminate is attached to the bonder head of the bonding apparatus, and the circuit board is further installed on the bonder stage side. Make sure the faces are facing each other.
• the semiconductor element surface of the laminate and the circuit surface of the circuit board may be directly overlapped to face each other.
• the optimum temperature for bonding can be selected according to the configuration of the semiconductor elements and circuit boards to be bonded. Particularly in the case of a circuit board having solder bumps, it is preferable to select a temperature higher than the temperature at which solder melts.
• the pressure-sensitive adhesive of the present invention has high heat resistance and does not cause degassing or voids even when heated in the electrical bonding process, so that a plurality of semiconductor elements can be uniformly bonded.
• the pressure at the time of bonding can be selected within a range that allows bonding without destroying the semiconductor element.
• the step of removing the substrate portion with the adhesive layer from the laminate bonded to the circuit board will be described.
• a method for removing the substrate portion with the adhesive layer from the semiconductor element electrically bonded to the circuit board there is a method of mechanically peeling off and removing, and a method of penetrating the adhesive layer from the support substrate side through the support substrate. Examples include a method of removing the adhesive layer by ablating the adhesive layer by irradiating it with a laser of a wavelength, and a method of removing the adhesive layer by dissolving it with a solvent. Since the pressure-sensitive adhesive of the present invention has a composition that does not leave an adhesive residue, it is preferably removed by mechanical peeling.
• the substrate may be immersed in a solvent to swell the adhesive layer and then mechanically peeled off.
• the pressure-sensitive adhesive layer By swelling the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer is softened, and the substrate with the pressure-sensitive adhesive layer can be removed without applying a load to the semiconductor element.
• semiconductor device refers to all devices that can function by utilizing the characteristics of semiconductor elements, and electro-optical devices, semiconductor circuit boards, and electronic components including these are all included in semiconductor devices.
• the circuit board with an adhesive layer of the present invention is a circuit board with an adhesive layer in which an adhesive layer comprising the adhesive of the present invention is formed on a circuit board.
• the circuit board with an adhesive layer of the present invention means that the supporting substrate of the above-mentioned substrate with an adhesive layer is a circuit board, and the adhesive layer is formed on the circuit surface of the circuit board.
• the method for forming the pressure-sensitive adhesive layer on the circuit board is the same as the method for forming the pressure-sensitive adhesive layer on the support substrate described above.
• the preferable film thickness of the pressure-sensitive adhesive layer on the circuit board is a film thickness that can cover the steps of the circuit board, and the optimum film thickness can be selected according to the steps of the circuit board.
• the present invention is a laminate in which a semiconductor element is held on the adhesive layer side surface of the adhesive layer-attached circuit board in which the adhesive layer is formed on the circuit board described above.
• laminated body refers to a semiconductor element laminated on the surface of the adhesive formed on the circuit surface of the aforementioned circuit board.
• the type of semiconductor element of the laminate is the same as the semiconductor element mentioned above for the laminate.
• the size of the semiconductor element is not limited, and a plurality of semiconductor elements may be held on the adhesive layer.
• the same method as the method for laminating the semiconductor element in the laminate can be used. It is preferable that the arrangement pattern of the semiconductor elements is set so as to match the junction with the circuit board that is in contact via the adhesive layer.
• the optimum value can be selected for the pressure when laminating the semiconductor element depending on the adhesiveness of the adhesive layer, and is selected in the range of 0.05 MPa to 5.0 MPa. From the viewpoint of preventing the semiconductor element from being buried in the pressure-sensitive adhesive layer, the pressure when laminating the semiconductor element is preferably 2.0 MPa or less. Moreover, when laminating
• the present invention is a method for manufacturing a semiconductor device using the laminate described above, wherein pressure is applied to the laminate in the lamination direction to push and break the adhesive layer to bring the circuit board and the semiconductor element into contact with each other,
• a method of manufacturing a semiconductor device includes a step of electrically connecting a circuit board and a semiconductor element.
• the method of applying pressure in the stacking direction of the laminate can be implemented using a device such as a mounting bonder or a wafer bonder, similar to the electrical bonding of the laminate and the circuit board described above. Since the pressure-sensitive adhesive of the present invention has a low elastic modulus, the semiconductor element pushes and breaks the pressure-sensitive adhesive layer by applying a certain or more pressure in the stacking direction of the laminate, and as a result, the semiconductor element and the circuit board come into contact with each other. , the semiconductor element and the circuit board can be electrically connected.
• the pressure during electrical bonding can be selected within a range that can push and break the adhesive layer without destroying the semiconductor element.
• pressure bonding can be performed while heating, and the optimum temperature can be selected depending on the configuration of the semiconductor element to be bonded and the circuit board. Since the adhesive layer is softened by heating, the semiconductor element can be pressure-bonded at a lower pressure. In the case of a configuration having solder bumps on the circuit board, the solder must be melted for electrical connection, so a temperature at which the solder melts or higher is selected.
• the adhesive layer may be left as it is or removed. Since the pressure-sensitive adhesive layer of the present invention is insulative, if it remains on the semiconductor device, it can serve as an underfill to prevent short-circuiting of the circuit board. When removing the adhesive layer, it can be removed by dissolving the adhesive layer with a solvent, or by swelling the adhesive layer with a solvent and peeling it off.
• the method for manufacturing a semiconductor device includes a step of facing a circuit board to a semiconductor-laminated surface of a laminate in which a substrate, an adhesive layer, and a plurality of semiconductor elements are laminated in this order;
• a method for manufacturing a semiconductor device comprising the steps of applying heat of 80° C. or more and less than 300° C. to pressure-bond a substrate to electrically join the substrate, and then removing the adhesive layer and the substrate portion of the laminate from the semiconductor element. is.
• the types of substrates used are the same as those described above for the support substrate.
• the adhesive a film made of a resin such as polyimide, silicone resin, or acrylic resin, or a tape material such as a die attach film can be used.
• the pressure-sensitive adhesive layer contains polyimide. Since the pressure-sensitive adhesive layer contains polyimide, the heat resistance of the pressure-sensitive adhesive layer itself is greatly improved, so that high heat resistance can be imparted, and the semiconductor element and the circuit board can be thermocompression bonded even in a high temperature range.
• the manufacturing method of the semiconductor device of the present invention has a step of applying heat of 80° C. or more and less than 300° C. to crimp the semiconductor element and the circuit board to electrically join them.
• a temperature of 80° C. or higher the semiconductor element and the circuit board can be reliably bonded.
• the bonding temperature is 300° C. or less, bonding can be performed without adversely affecting the semiconductor element due to heat.
• a laminate in which a circuit board, an adhesive layer, and a plurality of semiconductor elements are laminated in this order pressure is applied in the lamination direction to push and break the adhesive layer, thereby forming the circuit board and the adhesive layer.
• a method of manufacturing a semiconductor device comprising the steps of bringing a semiconductor element into contact with the semiconductor element and electrically connecting the circuit board and the semiconductor element.
• pressure is applied in the lamination direction to push and break the adhesive layer to bring the circuit board and the semiconductor element into contact with each other.
• a specific method of the step of electrically connecting the elements is the same as described above.
• a dicing tape (UDC-1025MC, manufactured by Denka Co., Ltd.) was attached to a silicon wafer whose back surface was polished so that the thickness of the silicon wafer was 300 ⁇ m, and diced with a dicing machine (DAD300, manufactured by DISCO Co., Ltd.). , a dummy chip of a semiconductor element was produced. The size of the manufactured dummy chips was 500 ⁇ m ⁇ 500 ⁇ m, and the chip interval was 150 ⁇ m.
• the dicing tape was irradiated with UV light to reduce the adhesiveness of the dicing tape, and the surrounding dummy chips were removed with tweezers, leaving dummy chips of a total of 100 semiconductor elements in 10 rows ⁇ 10 columns.
• the adhesive layer side of the aforementioned 4-inch glass substrate and the dummy chip on the dicing tape were overlaid with their chip surfaces facing each other.
• a vacuum laminator was used at room temperature with a pressure of 0.6 MPa for 1 minute, and a dummy chip was crimped onto the adhesive layer. After that, the dicing tape was peeled off to produce a laminated body in which an adhesive layer and a dummy chip were laminated in order on the glass substrate. The surface of the adhesive layer was visually observed with an optical microscope, and the number of chips that could be held on the adhesive layer at room temperature was counted.
• dummy chips were laminated in the same manner as described above, except that the temperature during crimping in the vacuum laminator was 100°C, and the number of chips that could be held at 100°C was counted.
• a Kapton film cut into strips of 9 cm x 1 cm was overlaid on the surface of the substrate with the adhesive layer on the adhesive layer side, and the Kapton film was pressed with a vacuum laminator at 0.1 MPa and 25°C. After that, the substrate to which the Kapton film was pressure-bonded was placed on a hot plate at 200° C. and heated for 10 minutes. The sample was set in a tensile tester (Nidec-Shimpo Corporation, FGS-VC), and the crimped Kapton film was peeled off vertically from the silicon wafer at a constant speed of 2 mm/sec. The measurement was performed three times with different samples.
• a to D The areas of adhesive residue on the surface of the Kapton film of these peeled samples were measured, and the sample with the largest amount of adhesive residue was selected and evaluated by A to D as follows.
• a 4-inch silicon wafer was coated with a varnish of an adhesive prepared by the method described later with a spinner, pre-baked on a hot plate at 120 ° C. for 3 minutes, and then heated and cured at 225 ° C. for 10 minutes.
• a substrate on which a pressure-sensitive adhesive layer of about 5 ⁇ m was formed was produced. After the heat treatment, the substrate on which the adhesive layer was formed was immersed in N-methylpyrrolidone (NMP) at 25° C. for 10 minutes. After the immersion, the substrate with the pressure-sensitive adhesive layer was taken out, washed with pure water, and dried on a hot plate at 120°C for 5 minutes.
• NMP N-methylpyrrolidone
• Remaining film ratio (%) film thickness after chemical resistance test ( ⁇ m) / film thickness before chemical resistance test ( ⁇ m) ⁇ 100
• the obtained residual film ratio was evaluated by A to D as follows. A: 95% or more, B: 90% or more and less than 95%, C: 80% or more and less than 90%, D: less than 80%.
• ⁇ Raw materials used in production examples> Abbreviated names of acid dianhydrides, diamines, additives and solvents used in the following production examples are as follows.
• PMDA pyromellitic dianhydride (corresponds to acid dianhydride residue)
• PA Phthalic anhydride (corresponds to the terminal blocking agent for acid components)
• BAHF 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (corresponding to diamine residue (A3))
• DABS 4,4'-dihydroxy-3,3'-diaminodiphenylsulfone (corresponding to diamine residue (A3))
• ABP-N 1,3-bis(3-aminophenoxy)benzene (diamine residues not corresponding to diamine residues (A1) to (A3))
• CHN Cyclohexanone
• JER871 Dimer acid-modified epoxy resin (manufactured by Mitsubishi Chemical) (corresponding to dimer acid epoxy resin (B))
• CG500 Cardo-based epoxy resin (manufactured by Osaka Gas Chemicals) 2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei)
• 100LM a cross-linking agent having a methylol group represented by the following structure
• Me in the formula represents a methyl group.
• Production Example 1 (polymerization of polyimide copolymer) 95.0 g of APPS2 (containing 108.5 mmol of component A1 and 1.1 mmol of component A2) was placed in a reactor equipped with a thermometer, a dry nitrogen inlet, a heating/cooling device using hot water/cooling water, and a stirring device. 67.7 g of APPS3 (containing 0.4 mmol of A1 component and 43.4 mmol of A2 component) and 15.4 g of BAHF (corresponding to (A3), 45.8 mmol) were charged together with 225 g of CHN and dissolved, and then PA5.
• the ratio of diamine residues (A1) in 100.0 mol% of all diamine residues in the polyimide copolymer is 54.7 mol%
• the ratio of diamine residues (A2) is 22.3 mol %.
• Production Example 2 (polymerization of polyimide copolymer) 160.0 g of APPS2 (containing 182.7 mmol of A1 component and 1.8 mmol of A2 component), 9.3 g of APPS3 (containing 0.1 mmol of A1 component and 6.0 mmol of A2 component), 2.7 g of BAHF ( (A3), 8.0 mmol), and the polyimide copolymer solution was polymerized in the same manner as in Production Example 1, except that 217 g of CHN was used. The solid content of the resulting polyimide polymer solution was measured and found to be 50.8% by weight.
• Production Example 3 (polymerization of polyimide copolymer) 137.7 g of APPS2 (containing 157.3 mmol of A1 component and 1.6 mmol of A2 component), 6.3 g of APPS3 (containing 0.04 mmol of A1 component and 4.0 mmol of A2 component), 12.0 g of BAHF ( (A3), 35.8 mmol), and the polyimide copolymer solution was polymerized in the same manner as in Production Example 1, except that 202 g of CHN was used. The solid content of the resulting polyimide polymer solution was measured and found to be 51.8% by weight.
• Production Example 4 (polymerization of polyimide copolymer) 103.6 g of APPS2 (containing 118.3 mmol of A1 component and 1.2 mmol of A2 component), 107.9 g of APPS3 (containing 0.7 mmol of A1 component and 69.2 mmol of A2 component), 3.4 g of BAHF ( (A3), 10.0 mmol), and the polyimide copolymer solution was polymerized in the same manner as in Production Example 1, except that 260 g of CHN was used. The solid content of the obtained polyimide polymer solution was measured and found to be 52.0% by weight.
• Production Example 5 (polymerization of polyimide copolymer) 149.8 g of APPS2 (containing 171.1 mmol of A1 component and 1.7 mmol of A2 component), 30.7 g of APPS3 (containing 0.2 mmol of A1 component and 19.7 mmol of A2 component), 2.0 g of BAHF ( (A3), 6.0 mmol), and the polyimide copolymer solution was polymerized in the same manner as in Production Example 1, except that 228 g of CHN was used. The solid content of the resulting polyimide polymer solution was measured and found to be 50.5% by weight.
• Production Example 6 (polymerization of polyimide copolymer) 120.6 g of APPS2 (containing 137.7 mmol of A1 component and 1.4 mmol of A2 component), 6.3 g of APPS3 (containing 0.04 mmol of A1 component and 4.0 mmol of A2 component), 18.7 g of BAHF ( (A3), 55.7 mmol), and the polyimide copolymer solution was polymerized in the same manner as in Production Example 1, except that 192 g of CHN was used. The solid content of the resulting polyimide polymer solution was measured and found to be 50.5% by weight.
• Production Example 7 (polymerization of polyimide copolymer) 120.8 g of APPS2 (containing 137.9 mmol of A1 component and 1.4 mmol of A2 component), 15.1 g of APPS3 (containing 0.1 mmol of A1 component and 9.7 mmol of A2 component), 16.7 g of BAHF ( (A3), 49.8 mmol), and the polyimide copolymer solution was polymerized in the same manner as in Production Example 1, except that 199 g of CHN was used. The solid content of the resulting polyimide polymer solution was measured and found to be 51.6% by weight.
• PIS-7 polyimide copolymer solution
• the ratio of diamine residues (A1) in 100.0 mol% of all diamine residues in the polyimide copolymer is 69.4 mol%
• the ratio of diamine residues (A2) is 5. 0.6 mol %.
• Production Example 8 (polymerization of polyimide copolymer) 137.8 g of APPS2 (containing 157.3 mmol of A1 component and 1.6 mmol of A2 component), 40.0 g of APPS3 (containing 0.3 mmol of A1 component and 25.6 mmol of A2 component), 4.7 g of BAHF ( (A3), 14.0 mmol), and the polyimide copolymer solution was polymerized in the same manner as in Production Example 1, except that 228 g of CHN was used. The solid content of the resulting polyimide polymer solution was measured and found to be 53.0% by weight.
• Production Example 9 (polymerization of polyimide copolymer) 149.9 g of APPS2 (containing 171.1 mmol of A1 component and 1.7 mmol of A2 component), 9.2 g of APPS3 (0.mmol of A1 component and 5.9 mmol of A2 component), 6.7 g of BAHF ( (A3), 19.8 mmol), and the polyimide copolymer solution was polymerized in the same manner as in Production Example 1 except that CHN was changed to 211 g. The solid content of the obtained polyimide polymer solution was measured and found to be 52.0% by weight.
• Production Example 10 (polymerization of polyimide copolymer) 137.8 g of APPS2 (containing 157.3 mmol of A1 component and 1.6 mmol of A2 component), 15.4 g of APPS3 (containing 0.1 mmol of A1 component and 9.9 mmol of A2 component), 10.0 g of BAHF ( (A3), 29.9 mmol), and the polyimide copolymer solution was polymerized in the same manner as in Production Example 1, except that 209 g of CHN was used. The solid content of the resulting polyimide polymer solution was measured and found to be 52.8% by weight.
• Production Example 11 (polymerization of polyimide copolymer) 137.8 g of APPS2 (containing 157.3 mmol of A1 component and 1.6 mmol of A2 component), 15.4 g of APPS3 (containing 0.1 mmol of A1 component and 9.9 mmol of A2 component), and DABS instead of BAHF.
• a polyimide copolymer solution was polymerized in the same manner as in Production Example 1 except that 8.4 g (corresponding to (A3), 29.9 mmol) and 206 g of CHN were used. The solid content of the obtained polyimide polymer solution was measured and found to be 52.0% by weight.
• Production Example 12 (polymerization of polyimide copolymer) 77.9 g of APPS2 (containing 89.0 mmol of A1 component and 0.9 mmol of A2 component), 107.6 g of APPS3 (containing 0.27 mmol of A1 component and 69.1 mmol of A2 component), 13.4 g of BAHF ( (A3), 40.0 mmol), and the polyimide copolymer solution was polymerized in the same manner as in Production Example 1, except that 246 g of CHN was used. The solid content of the resulting polyimide polymer solution was measured and found to be 50.1% by weight.
• Production Example 13 (polymerization of polyimide copolymer) 168.5 g of APPS2 (containing 192.5 mmol of A1 component and 1.9 mmol of A2 component), 3.1 g of APPS3 (containing 0.02 mmol of A1 component and 2.0 mmol of A2 component), 0.7 g of BAHF ( (A3), 2.0 mmol), and the polyimide copolymer solution was polymerized in the same manner as in Production Example 1, except that 217 g of CHN was used. The solid content of the obtained polyimide polymer solution was measured and found to be 53.8% by weight.
• Production Example 14 (polymerization of polyimide copolymer) 146.2 g of APPS2 (containing 167.0 mmol of A1 component and 1.7 mmol of A2 component), 0.3 g of APPS3 (containing 0.01 mmol of A1 component and 0.2 mmol of A2 component), 10.0 g of BAHF ( (A3), 29.8 mmol), and the polyimide copolymer solution was polymerized in the same manner as in Production Example 1, except that 202 g of CHN was used. The solid content of the obtained polyimide polymer solution was measured and found to be 52.0% by weight.
• Production Example 15 (polymerization of polyimide copolymer) 86.6 g of APPS2 (containing 98.9 mmol of A1 component and 1.0 mmol of A2 component), 138.3 g of APPS3 (containing 0.9 mmol of A1 component and 88.7 mmol of A2 component), 3.4 g of BAHF ( (A3), 10.1 mmol), and the polyimide copolymer solution was polymerized in the same manner as in Production Example 1, except that 274 g of CHN was used. The solid content of the resulting polyimide polymer solution was measured and found to be 54.1% by weight.
• Production Example 16 (polymerization of polyimide copolymer) 138.0 g of APPS2 (containing 157.6 mmol of A1 component and 1.6 mmol of A2 component), 61.2 g of APPS3 (containing 0.4 mmol of A1 component and 39.3 mmol of A2 component), without using BAHF, A polyimide copolymer solution was polymerized in the same manner as in Production Example 1, except that 245 g of CHN was used. The solid content of the resulting polyimide polymer solution was measured and found to be 51.0% by weight.
• Production Example 17 (polymerization of polyimide copolymer) 103.7 g of APPS2 (containing 118.4 mmol of A1 component and 1.2 mmol of A2 component), 15.1 g of APPS3 (containing 0.1 mmol of A1 component and 9.7 mmol of A2 component), 23.4 g of BAHF ( (A3), 69.7 mmol), and the polyimide copolymer solution was polymerized in the same manner as in Production Example 1, except that 189 g of CHN was used. The solid content of the resulting polyimide polymer solution was measured and found to be 51.5% by weight.
• PIS-17 having a solid content of 50% by weight.
• the ratio of diamine residues (A1) in 100.0 mol% of all diamine residues in the polyimide copolymer is 59.5 mol%
• the ratio of diamine residues (A2) is 5. 0.5 mol %.
• Production Example 18 (polymerization of polyimide copolymer) 163.3 g of APPS2 (containing 186.5 mmol of A1 component and 1.9 mmol of A2 component), 6.4 g of APPS3 (containing 0.04 mmol of A1 component and 4.1 mmol of A2 component), and 2.0 g of BAHF (( The polyimide copolymer solution was polymerized in the same manner as in Production Example 1, except that 5.9 mmol corresponding to A3) and 218 g of CHN were used. The solid content of the obtained polyimide polymer solution was measured and found to be 52.0% by weight.
• Production Example 19 (polymerization of polyimide copolymer) 156.4 g of APPS2 (containing 178.6 mmol of A1 component and 1.8 mmol of A2 component), 23.5 g of APPS3 (containing 0.2 mmol of A1 component and 15.1 mmol of A2 component), 1.0 g of BAHF (( A3), 3.0 mmol), and 227 g of CHN were used to polymerize the polyimide copolymer solution in the same manner as in Production Example 1. The solid content of the resulting polyimide polymer solution was measured and found to be 51.4% by weight.
• Production Example 20 (polymerization of polyimide copolymer) 103.6 g of APPS2 (containing 118.4 mmol of A1 component and 1.2 mmol of A2 component), 15.1 g of APPS3 (containing 0.1 mmol of A1 component and 9.7 mmol of A2 component), 16.7 g of BAHF (( A3), 49.8 mmol), 5.8 g of ABP-N (a diamine residue not corresponding to (A1) to (A3), 19.9 mmol), and 187 g of CHN in the same manner as in Production Example 1.
• a polyimide copolymer solution was polymerized. The solid content of the resulting polyimide polymer solution was measured and found to be 50.9% by weight.
• Production Example 21 (polymerization of polyimide copolymer) 104.3 g of APPS2 (containing 117.2 mmol of A1 component and 1.2 mmol of A2 component), 28.9 g of APPS4 (containing 0.1 mmol of A1 component and 9.6 mmol of A2 component) instead of APPS3, and 16 of BAHF .6 g (corresponding to (A3), 49.2 mmol), 5.8 g of ABP-N (diamine residue not corresponding to (A1) to (A3), 19.8 mmol), and 203 g of CHN.
• the polyimide copolymer solution was polymerized in the same manner as in 1.
• the solid content of the resulting polyimide polymer solution was measured and found to be 50.5% by weight. CHN was added and stirred so that the solid content of this polymer solution was 50.0% by weight, to obtain a polyimide copolymer solution PIS-21 with a solid content of 50% by weight.
• PIS-21 the ratio of diamine residues (A1) in 100.0 mol% of all diamine residues in the polyimide copolymer is 59.5 mol%, and the ratio of diamine residues (A2) is 5. 0.5 mol %.
• Production Example 22 (polymerization of polyimide copolymer) 121.9 g of APPS2 (containing 139.2 mmol of A1 component and 1.4 mmol of A2 component), 22.4 g of APPS3 (containing 139.2 mmol of A1 component and 1.4 mmol of A2 component), 12.0 g of BAHF (( A3), 35.8 mmol), 2.3 g of ABP-N (a diamine residue not corresponding to (A1) to (A3), 8.0 mmol), and 204 g of CHN in the same manner as in Production Example 1.
• a polyimide copolymer solution was polymerized. The solid content of the obtained polyimide polymer solution was measured and found to be 51.2% by weight.
• Production Example 23 (polymerization of polyimide copolymer) 142.5 g of APPS2 (containing 162.8 mmol of A1 component and 1.6 mmol of A2 component), 26.8 g of APPS3 (containing 0.2 mmol of A1 component and 17.2 mmol of A2 component), and 5.7 g of BAHF (( A3), 17.0 mmol), and 222 g of CHN were used to polymerize the polyimide copolymer solution in the same manner as in Production Example 1. The solid content of the obtained polyimide polymer solution was measured and found to be 52.0% by weight.

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