CN111417683A - Curable resin composition, adhesive film, coverlay film, and flexible copper-clad laminate - Google Patents

Curable resin composition, adhesive film, coverlay film, and flexible copper-clad laminate Download PDF

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Publication number
CN111417683A
CN111417683A CN201980006114.8A CN201980006114A CN111417683A CN 111417683 A CN111417683 A CN 111417683A CN 201980006114 A CN201980006114 A CN 201980006114A CN 111417683 A CN111417683 A CN 111417683A
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curable resin
resin composition
cured product
composition according
present
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CN111417683B (en
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大当悠太
胁冈纱香
新城隆
竹田幸平
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Sekisui Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • 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
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/12—Copper

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesive Tapes (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

The purpose of the present invention is to provide a curable resin composition that can provide a cured product that has excellent heat resistance at high temperatures for a long period of time, moisture absorption reflow resistance, and plating resistance. Further, an object of the present invention is to provide an adhesive comprising the curable resin composition, an adhesive film using the curable resin composition, and a coverlay film and a flexible copper-clad laminate each having a cured product of the curable resin composition. The present invention is a curable resin composition containing a curable resin, an imide oligomer having an imide skeleton in the main chain and a crosslinkable functional group at the end, and an ion scavenger.

Description

Curable resin composition, adhesive film, coverlay film, and flexible copper-clad laminate
Technical Field
The present invention relates to a curable resin composition capable of providing a cured product excellent in heat resistance at high temperatures for a long period of time, moisture absorption reflow resistance, and plating resistance. The present invention also relates to an adhesive containing the curable resin composition, an adhesive film using the curable resin composition, and a coverlay film and a flexible copper-clad laminate each having a cured product of the curable resin composition.
Background
Curable resins such as epoxy resins, which have low shrinkage and are excellent in adhesion, insulation properties, and chemical resistance, are used in a wide variety of industrial products. In particular, in applications for electronic devices, a curable resin composition which can obtain good results in a reflow test for short-time heat resistance and a cold-heat cycle test for repeated heat resistance is used in a large amount.
In recent years, attention has been paid to an Electrical Control Unit (ECU) for a vehicle, a power device using SiC or GaN, and the like, but a curable resin composition used for these applications is required not to have heat resistance in a short time or repeated heat resistance but to have heat resistance when exposed to high temperatures for a long period of time (high-temperature long-term heat resistance).
As a curing agent used for the curable resin composition, for example, patent document 1 discloses a polyimide obtained by reacting an acid anhydride component containing an aromatic tetracarboxylic dianhydride with a diamine component containing an aromatic diamine. In patent document 1, by using the polyimide, an adhesive layer that does not decrease the adhesion between the wiring layer and the coverlay can be formed even in a use environment exposed to repeated high temperatures. However, it is difficult for conventional curable resin compositions using such polyimides to maintain adhesion in a more severe temperature environment. In addition, a curable resin composition having an excellent effect also on moisture absorption reflow resistance is required.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2017-145344
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a curable resin composition that can provide a cured product that has excellent heat resistance at high temperatures for a long period of time, moisture absorption reflow resistance, and plating resistance. Further, an object of the present invention is to provide an adhesive containing the curable resin composition, an adhesive film using the curable resin composition, and a coverlay film and a flexible copper-clad laminate each having a cured product of the curable resin composition.
Means for solving the problems
The present invention is a curable resin composition containing a curable resin, an imide oligomer having an imide skeleton in the main chain and a crosslinkable functional group at the end, and an ion scavenger.
The present invention will be described in detail below.
The inventors believe that: the reason why the conventional curable resin composition is deteriorated in heat resistance and moisture absorption reflow resistance for a long period at high temperatures under severe temperature environments is that it is derived from a specific ion such as a chloride ion in a raw material of the curable resin composition or a cleaning solution for a copper foil used for a printed wiring board or the like.
Therefore, the present inventors have found that: the present inventors have completed the present invention by further compounding an ion scavenger to a curable resin composition containing a curable resin and an imide oligomer having a specific structure, thereby obtaining a cured product excellent in high-temperature long-term heat resistance and moisture absorption reflow resistance.
The curable resin composition of the present invention is also excellent in initial adhesion and plating resistance.
The curable resin composition of the present invention contains an ion scavenger.
By containing the ion scavenger, a cured product of the curable resin composition of the present invention has excellent high-temperature long-term heat resistance and moisture absorption reflow resistance.
In the present specification, the "ion scavenger" refers to an organic compound or an inorganic compound having a function of adsorbing, trapping, or exchanging ions.
The ion scavenger is preferably an ion exchanger.
Examples of the ion exchanger include zirconium-based compounds, antimony-based compounds, magnesium aluminum-based compounds, antimony bismuth-based compounds, zirconium bismuth-based compounds, and the like. Among these, preferred are anion exchangers and amphoteric ion exchangers, more preferred are anion exchangers, and further preferred are magnesium-aluminum compounds as anion exchangers.
The ion scavenger may be used alone or in combination of 2 or more.
From the viewpoint of ion-capturing ability, the ion-capturing agent is preferably particles having an average particle diameter of 10 μm or less. Since the ion scavenger is particles having an average particle diameter of 10 μm or less, the cured product of the obtained curable resin composition has excellent high-temperature long-term heat resistance and moisture absorption reflow resistance. The ion scavenger is more preferably particles having an average particle diameter of 6 μm or less, and still more preferably particles having an average particle diameter of 2 μm or less.
The lower limit of the average particle size of the ion scavenger is not particularly limited, but from the viewpoint of thickening or the like, the ion scavenger is preferably particles having an average particle size of 0.01 μm or more, more preferably particles having an average particle size of 0.1 μm or more.
The average particle size of the ion scavenger, and the inorganic filler and flow control agent described later can be measured by dispersing the particles in a solvent (water, organic solvent, etc.) using NICOMP 380Z L S (part L E SIZING SYSTEMS).
The lower limit of the content of the ion scavenger is preferably 0.1 part by weight, and the upper limit is preferably 200 parts by weight, based on 100 parts by weight of the total of the curable resin and the imide oligomer. When the content of the ion scavenger is in this range, the cured product of the obtained curable resin composition has excellent high-temperature long-term heat resistance and moisture absorption reflow resistance. The lower limit of the content of the ion scavenger is preferably 1 part by weight, the upper limit is preferably 50 parts by weight, and the upper limit is more preferably 20 parts by weight.
The curable resin composition of the present invention contains an imide oligomer having an imide skeleton in the main chain and a crosslinkable functional group at the terminal (hereinafter also referred to as "imide oligomer of the present invention"). The imide oligomer of the present invention has excellent reactivity and compatibility with a curable resin such as an epoxy resin. The curable resin composition of the present invention contains the imide oligomer of the present invention, and thus a cured product thereof has excellent mechanical strength at high temperatures and excellent long-term heat resistance at high temperatures.
The crosslinkable functional group is preferably a functional group capable of reacting with an epoxy group.
Specific examples of the crosslinkable functional group include an amino group, a carboxyl group, an acid anhydride group, a phenolic hydroxyl group, an unsaturated group, an active ester group, and a maleimide group. Among these, at least any one of an acid anhydride group and a phenolic hydroxyl group is more preferable. The imide oligomer of the present invention may have the crosslinkable functional group at one end or both ends. In the case where the crosslinkable functional group is present at both ends, the crosslinking density is increased, and therefore, the resultant curable resin composition has a higher glass transition temperature after curing. On the other hand, when the crosslinkable functional group is present at one end, the equivalent weight of the functional group becomes large, and the content of the imide oligomer of the present invention in the curable resin composition is increased, so that the cured product of the obtained curable resin composition has more excellent high-temperature long-term heat resistance.
The imide oligomer of the present invention preferably has a structure represented by the following formula (1-1) or the following formula (1-2) as a structure containing the crosslinkable functional group. The imide oligomer of the present invention has a structure represented by the following formula (1-1) or the following formula (1-2), and thus has more excellent reactivity and compatibility with a curable resin such as an epoxy resin.
[ solution 1]
Figure BDA0002515622060000041
In the formulas (1-1) and (1-2), A is a group with a valence of 4 represented by the following formula (2-1) or the following formula (2-2), in the formula (1-1), B is a group with a valence of 2 represented by the following formula (3-1) or the following formula (3-2), in the formula (1-2), Ar is an optionally substituted aromatic group with a valence of 2.
[ solution 2]
Figure BDA0002515622060000042
In the formulae (2-1) and (2-2), ＊ represents a bonding position, and in the formula (2-1), Z represents a bonding bond, an oxygen atom, or a 2-valent hydrocarbon group which is optionally substituted and has an oxygen atom at the bonding position, and the hydrogen atom of the aromatic ring in the formulae (2-1) and (2-2) is optionally substituted.
[ solution 3]
Figure BDA0002515622060000051
In the formulae (3-1) and (3-2), ＊ represents a bonding position, and Y represents a bonding bond, an oxygen atom, or an optionally substituted 2-valent hydrocarbon group in the formula (3-1), and the hydrogen atom of the aromatic ring in the formulae (3-1) and (3-2) is optionally substituted.
Further, the imide oligomer of the present invention is preferably an imide oligomer having no siloxane skeleton in its structure, because the glass transition temperature after curing is lowered or an adherend is contaminated to cause poor adhesion.
The preferred upper limit of the number average molecular weight of the imide oligomer of the present invention is 4000. When the number average molecular weight is 4000 or less, the cured product of the obtained curable resin composition has more excellent high-temperature long-term heat resistance. The upper limit of the number average molecular weight of the imide oligomer of the present invention is preferably 3400, and more preferably 2800.
In particular, the number average molecular weight of the imide oligomer of the present invention is preferably 900 or more and 4000 or less in the case of having the structure represented by the above formula (1-1), and is preferably 550 or more and 4000 or less in the case of having the structure represented by the above formula (1-2). The lower limit of the number average molecular weight in the case of the structure represented by the above formula (1-1) is more preferably 950, and still more preferably 1000. The lower limit of the number average molecular weight in the case of the structure represented by the above formula (1-2) is more preferably 580, and still more preferably 600.
In the present specification, the "number average molecular weight" is a value obtained in terms of polystyrene by measuring the number average molecular weight by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent, and examples of a chromatographic column used in the measurement of the number average molecular weight in terms of polystyrene by GPC include JAIGE L-2H-A (manufactured by Japan analytical industries, Ltd.).
Specifically, the imide oligomer of the present invention is preferably an imide oligomer represented by the following formula (4-1), the following formula (4-2), the following formula (4-3) or the following formula (4-4), or an imide oligomer represented by the following formula (5-1), the following formula (5-2), the following formula (5-3) or the following formula (5-4).
[ solution 4]
Figure BDA0002515622060000061
In the formulae (4-1) and (4-4), A is a group having a valence of 4 represented by the following formula (6-1) or the following formula (6-2), and in the formulae (4-1), (4-3) and (4-4), A may be the same or different. In the formulae (4-1) and (4-4), B is a 2-valent group represented by the following formula (7-1) or the following formula (7-2), and in the formulae (4-3) and (4-4), B may be the same or different. In the formula (4-2), X is a hydrogen atom, a halogen atom or an optionally substituted 1-valent hydrocarbon group, and in the formula (4-4), W is a hydrogen atom, a halogen atom or an optionally substituted 1-valent hydrocarbon group.
[ solution 5]
Figure BDA0002515622060000071
In the formulae (5-1) and (5-4), A is a group having a valence of 4 represented by the following formula (6-1) or the following formula (6-2), and in the formulae (5-3) and (5-4), A may be the same or different. In the formulae (5-1) and (5-4), R is a hydrogen atom, a halogen atom or an optionally substituted 1-valent hydrocarbon group, and in the formulae (5-1) and (5-3), R may be the same or different. In the formulas (5-2) and (5-4), W is a hydrogen atom, a halogen atom or an optionally substituted 1-valent hydrocarbon group, and in the formulas (5-3) and (5-4), B is a 2-valent group represented by the following formula (7-1) or the following formula (7-2).
[ solution 6]
Figure BDA0002515622060000081
In the formulae (6-1) and (6-2), ＊ represents a bonding position, and in the formula (6-1), Z represents a bonding bond, an oxygen atom, or a 2-valent hydrocarbon group which is optionally substituted and has an oxygen atom at the bonding position, the hydrogen atom of the aromatic ring in the formulae (6-1) and (6-2) is optionally substituted.
[ solution 7]
Figure BDA0002515622060000082
In the formulae (7-1) and (7-2), ＊ represents a bonding position, and Y represents a bonding bond, an oxygen atom, or an optionally substituted 2-valent hydrocarbon group in the formula (7-1). the hydrogen atom of the aromatic ring in the formulae (7-1) and (7-2) is optionally substituted.
Among the imide oligomers described in the present invention, examples of the method for producing an imide oligomer having a structure represented by the above formula (1-1) include a method in which an acid dianhydride represented by the following formula (8) is reacted with a diamine represented by the following formula (9).
[ solution 8]
Figure BDA0002515622060000091
In the formula (8), A is the same group having a valence of 4 as A in the formula (1-1).
[ solution 9]
Figure BDA0002515622060000092
In the formula (9), B is the same 2-valent group as B in the formula (1-1), and R1 to R4 are each independently a hydrogen atom or a 1-valent hydrocarbon group.
Specific examples of the method of reacting the acid dianhydride represented by the above formula (8) with the diamine represented by the above formula (9) will be described below.
Examples thereof include the following methods: first, a diamine represented by the above formula (9) is dissolved in advance in a solvent (for example, N-methylpyrrolidone or the like) capable of dissolving an amic acid oligomer obtained by the reaction, and an acid dianhydride represented by the above formula (8) is added to the resulting solution to cause the reaction, thereby obtaining an amic acid oligomer solution; next, the solvent is removed by heating or reduced pressure, and the reaction is further carried out by heating at about 200 ℃ or higher for 1 hour or more to react the amic acid oligomer. By adjusting the molar ratio of the acid dianhydride represented by the formula (8) to the diamine represented by the formula (9) and the imidization conditions, an imide oligomer having a desired number average molecular weight and having a structure represented by the formula (1-1) at both ends can be obtained.
Further, by replacing a part of the acid dianhydride represented by the above formula (8) with an acid anhydride represented by the following formula (10), an imide oligomer having a desired number average molecular weight and having a structure represented by the above formula (1-1) at one end and a structure derived from the acid anhydride represented by the following formula (10) at the other end can be obtained. In this case, the acid dianhydride represented by the above formula (8) and the acid anhydride represented by the following formula (10) may be added simultaneously or separately.
Further, by replacing a part of the diamine represented by the above formula (9) with a monoamine represented by the following formula (11), an imide oligomer having a desired number average molecular weight and having a structure represented by the above formula (1-1) at one end and a structure derived from the monoamine represented by the following formula (11) at the other end can be obtained. In this case, the diamine represented by the above formula (9) and the monoamine represented by the following formula (11) may be added simultaneously or separately.
[ solution 10]
Figure BDA0002515622060000101
In the formula (10), Ar is an optionally substituted aromatic group having a valence of 2.
[ solution 11]
Figure BDA0002515622060000102
In the formula (11), Ar is an optionally substituted 1-valent aromatic group, R5And R6Each independently a hydrogen atom or a 1-valent hydrocarbon group.
Among the imide oligomers described in the present invention, examples of the method for producing an imide oligomer having a structure represented by the above formula (1-2) include a method in which an acid dianhydride represented by the above formula (8) is reacted with a phenol hydroxyl group-containing monoamine represented by the following formula (12).
[ solution 12]
Figure BDA0002515622060000103
In the formula (12), Ar is an optionally substituted 2-valent aromatic group, R7And R8Each independently a hydrogen atom or a 1-valent hydrocarbon group.
Specific examples of the method of reacting the acid dianhydride represented by the above formula (8) with the phenol hydroxyl group-containing monoamine represented by the above formula (12) will be described below.
Examples thereof include the following methods: first, a phenol hydroxyl group-containing monoamine represented by formula (12) is dissolved in advance in a solvent (for example, N-methylpyrrolidone or the like) capable of dissolving an amic acid oligomer obtained by the reaction, and an acid dianhydride represented by formula (8) is added to the resulting solution to cause the reaction, thereby obtaining an amic acid oligomer solution; next, the solvent is removed by heating or reduced pressure, and the reaction is further carried out by heating at about 200 ℃ or higher for 1 hour or more to react the amic acid oligomer. By adjusting the molar ratio of the acid dianhydride represented by the formula (8) to the phenolic hydroxyl group-containing monoamine represented by the formula (12) and the imidization conditions, an imide oligomer having a desired number average molecular weight and having a structure represented by the formula (1-2) at both ends can be obtained.
Further, by replacing a part of the phenol hydroxyl group-containing monoamine represented by the formula (12) with the monoamine represented by the formula (11), an imide oligomer having a desired number average molecular weight and having a structure represented by the formula (1-2) at one end and a structure derived from the monoamine represented by the formula (11) at the other end can be obtained. In this case, the phenol hydroxyl group-containing monoamine represented by the above formula (12) and the monoamine represented by the above formula (11) may be added simultaneously or separately.
Examples of the acid dianhydride represented by the above formula (8) include pyromellitic dianhydride, 3, 3 ' -oxydiphthalic dianhydride, 3, 4 ' -oxydiphthalic dianhydride, 4 ' - (4, 4 ' -isopropylidenediphenoxy) diphthalic anhydride, 4 ' -bis (2, 3-dicarboxyphenoxy) diphenyl ether dianhydride, p-phenylenebis (trimellitic acid anhydride), and 2, 3, 3 ', 4 ' -biphenyltetracarboxylic acid dianhydride.
Among them, from the viewpoint of more excellent solubility and heat resistance, the acid dianhydride used as the raw material of the imide oligomer of the present invention is preferably an aromatic acid dianhydride having a melting point of 240 ℃ or lower, more preferably an aromatic acid dianhydride having a melting point of 220 ℃ or lower, still more preferably an aromatic acid dianhydride having a melting point of 200 ℃ or lower, and particularly preferably 3, 4 ' -oxydiphthalic dianhydride (melting point 180 ℃) or 4, 4 ' - (4, 4 ' -isopropylidenediphenoxy) diphthalic anhydride (melting point 190 ℃).
In the present specification, the "melting point" means: a differential scanning calorimeter was used, and the value was measured as the temperature of the endothermic peak at a temperature rise of 10 ℃/min. Examples of the differential scanning calorimeter include an EXTEAR DSC6100 (manufactured by SII NanoTechnology inc.).
Examples of the diamine represented by the above formula (9) include 3, 3 '-diaminodiphenylmethane, 3, 4' -diaminodiphenylmethane, 4 '-diaminodiphenylmethane, 3' -diaminodiphenyl ether, 3, 4 '-diaminodiphenyl ether, 4' -diaminodiphenyl ether, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3 '-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfone, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, bis (4- (4-aminophenoxy) phenyl) methane, 2-bis (4- (4-aminophenoxy) phenyl) propane, p-phenylenediamine, 3 '-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfone, 1, 1, 3-bis (2- (4-aminophenyl) -2-propyl) benzene, 1, 4-bis (2- (4-aminophenyl) -2-propyl) benzene, 3 '-diamino-4, 4' -dihydroxyphenylmethane, 4 '-diamino-3, 3' -dihydroxyphenylmethane, 3 '-diamino-4, 4' -dihydroxyphenyl ether, bisaminophenylfluorene, bistoluidine fluorene, 4 ' -bis (4-aminophenoxy) biphenyl, 4 ' -diamino-3, 3 ' -dihydroxyphenyl ether, 3 ' -diamino-4, 4 ' -dihydroxybiphenyl, 4 ' -diamino-2, 2 ' -dihydroxybiphenyl, and the like. Among them, from the viewpoint of excellent availability, preferred are 4, 4 '-diaminodiphenylmethane, 4' -diaminodiphenyl ether, 1, 3-bis (2- (4-aminophenyl) -2-propyl) benzene, 1, 4-bis (2- (4-aminophenyl) -2-propyl) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, and from the viewpoint of excellent solubility and heat resistance, more preferred are 1, 3-bis (2- (4-aminophenyl) -2-propyl) benzene, 1, 4-bis (2- (4-aminophenyl) -2-propyl) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene.
Examples of the acid anhydride represented by the above formula (10) include phthalic anhydride, 3-methylphthalic anhydride, 4-methylphthalic anhydride, 1, 2-naphthalic anhydride, 2, 3-naphthalic anhydride, 1, 8-naphthalic anhydride, 2, 3-anthracenedicarboxylic anhydride, 4-tert-butylphthalic anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4-fluorophthalic anhydride, 4-chlorophthalic anhydride, 4-bromophthalic anhydride, and 3, 4-dichlorophthalic anhydride.
Examples of the monoamine represented by the above formula (11) include aniline, o-toluidine, m-toluidine, p-toluidine, 2, 4-dimethylaniline, 3, 5-dimethylaniline, 2-tert-butylaniline, 3-tert-butylaniline, 4-tert-butylaniline, 1-naphthylamine, 2-naphthylamine, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene, 1-aminopyrene, 3-chloroaniline, o-anisidine, m-anisidine, p-anisidine, 1-amino-2-methylnaphthalene, 2, 3-dimethylaniline, 2, 4-dimethylaniline, 2, 5-dimethylaniline, 3, 4-dimethylaniline, 4-ethylaniline, 4-ethynylaniline, 4-isopropylaniline, 4- (methylthio) aniline, N-dimethyl-1, 4-phenylenediamine and the like.
Examples of the monoamine having a phenolic hydroxyl group represented by the above formula (12) include 3-aminophenol, 4-amino-o-cresol, 5-amino-o-cresol, 4-amino-2, 3-xylenol, 4-amino-2, 5-xylenol, 4-amino-2, 6-xylenol, 4-amino-1-naphthol, 5-amino-2-naphthol, 6-amino-1-naphthol, and 4-amino-2, 6-diphenylphenol. Among them, 4-amino-o-cresol, 5-amino-o-cresol, and 3-aminophenol are preferable because they are excellent in acquisition properties and storage stability and can achieve a high glass transition temperature after curing.
In the case of producing the imide oligomer of the present invention by the above-mentioned production method, the imide oligomer of the present invention is obtained as an imide oligomer contained in a mixture (imide oligomer composition) of a plurality of imide oligomers having a structure represented by the above formula (1-1) or a plurality of imide oligomers having a structure represented by the above formula (1-2) and each raw material. When the imide oligomer composition is used as a curing agent, a cured product having more excellent mechanical strength at high temperatures and long-term heat resistance at high temperatures can be obtained by adjusting the imidization rate to 70% or more.
The lower limit of the imidization degree of the imide oligomer composition is preferably 75%, and more preferably 80%. Further, although the preferable upper limit of the imidization ratio of the imide oligomer composition is not particularly limited, the substantial upper limit is 98%.
The "imidization ratio" can be measured by total reflectance measurement (ATR method) using a Fourier transform infrared spectrophotometer (FT-IR), and 1660cm from the carbonyl group derived from amic acid is used in the following formula-1The area of the absorbance of the peak in the vicinity. Examples of the fourier transform infrared spectrophotometer include UMA600 (manufactured by Agilent Technologies). The "peak absorbance area of the amic acid oligomer" in the following formula is the absorbance area of the amic acid oligomer obtained by reacting an acid dianhydride with a diamine or a phenol hydroxyl group-containing monoamine and then removing the solvent by evaporation or the like without performing an imidization step.
Imidization ratio (%) -100 × (1- (peak absorbance area after imidization)/(peak absorbance area of amic acid oligomer))
The imide oligomer composition is preferably dissolved in 10g of tetrahydrofuran at 25 ℃ in view of solubility when used as a curing agent in a curable resin composition.
The imide oligomer composition preferably has a melting point of 200 ℃ or less from the viewpoint of workability when used as a curing agent in a curable resin composition. The melting point of the imide oligomer composition is more preferably 190 ℃ or lower, and still more preferably 180 ℃ or lower.
The lower limit of the melting point of the imide oligomer composition is not particularly limited, but is preferably 60 ℃ or higher.
The content of the imide oligomer of the present invention in 100 parts by weight of the total of the curable resin and the imide oligomer preferably has a lower limit of 20 parts by weight and an upper limit of 80 parts by weight. When the content of the imide oligomer of the present invention is in this range, the cured product of the curable resin composition obtained has more excellent mechanical strength at high temperatures and high-temperature long-term heat resistance. The content of the imide oligomer according to the present invention is more preferably 25 parts by weight in the lower limit, and more preferably 75 parts by weight in the upper limit.
The curable resin composition of the present invention may further contain another curing agent in addition to the imide oligomer of the present invention, within a range not interfering with the object of the present invention, for the purpose of improving the processability in an uncured state, and the like.
Examples of the other curing agent include a phenol curing agent, a thiol curing agent, an amine curing agent, an acid anhydride curing agent, a cyanate curing agent, and an active ester curing agent. Among them, preferred are phenol-based curing agents, acid anhydride-based curing agents, cyanate-based curing agents, and active ester-based curing agents.
When the curable resin composition of the present invention contains the other curing agent, the content of the other curing agent in the entire curing agent is preferably 70% by weight, more preferably 50% by weight, and still more preferably 30% by weight.
The curable resin composition of the present invention contains a curable resin.
Examples of the curable resin include epoxy resins, acrylic resins, phenol resins, cyanate resins, isocyanate resins, maleimide resins, benzoxazine resins, silicone resins, fluorine resins, polyimide resins, and phenoxy resins. Among them, epoxy resins are preferable. These curable resins may be used alone or in combination of 2 or more.
In addition, in the case of film processing, the curable resin is preferably in a liquid or semisolid form at 25 ℃, and more preferably in a liquid form, in order to improve handling properties.
Examples of the epoxy resin include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol E type epoxy resins, bisphenol S type epoxy resins, 2' -diallylbisphenol A type epoxy resins, hydrogenated bisphenol type epoxy resins, propylene oxide-added bisphenol A type epoxy resins, resorcinol type epoxy resins, biphenyl type epoxy resins, thioether type epoxy resins, diphenyl ether type epoxy resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resin, fluorene type epoxy resin, naphthalene ether type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenol novolac type epoxy resin, naphthol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified type epoxy resin, glycidyl ester compound, and the like. Among them, bisphenol a type epoxy resins, bisphenol F type epoxy resins, bisphenol E type epoxy resins, and resorcinol type epoxy resins are preferable in terms of low viscosity and easy adjustment of processability at room temperature of the obtained curable resin composition.
The curable resin composition of the present invention preferably contains a curing accelerator. By containing the curing accelerator, the curing time can be shortened and the productivity can be improved.
Examples of the curing accelerator include imidazole-based curing accelerators, tertiary amine-based curing accelerators, phosphine-based curing accelerators, photobase generators, sulfonium salt-based curing accelerators, and the like. Among them, imidazole-based curing accelerators and phosphine-based curing accelerators are preferred from the viewpoint of storage stability and curability.
The curing accelerator may be used alone, or 2 or more kinds may be used in combination.
The lower limit of the content of the curing accelerator is preferably 0.8% by weight based on the total weight of the curable resin, the imide oligomer, and the curing accelerator. The effect of shortening the curing time is further enhanced by setting the content of the curing accelerator to 0.8 wt% or more. A more preferable lower limit of the content of the curing accelerator is 1% by weight.
From the viewpoint of adhesiveness and the like, the content of the curing accelerator is preferably 10% by weight or more, and more preferably 5% by weight or more.
The curable resin composition of the present invention preferably contains an inorganic filler.
By containing the inorganic filler, the curable resin composition of the present invention has more excellent moisture absorption/reflow resistance, plating resistance, and processability while maintaining excellent adhesiveness and high-temperature long-term heat resistance.
The inorganic filler is preferably at least one of silica and barium sulfate. By containing at least one of silica and barium sulfate as the inorganic filler, the curable resin composition of the present invention is more excellent in moisture absorption reflow resistance, plating resistance, and processability.
Examples of the inorganic filler other than the silica and the barium sulfate include alumina, aluminum nitride, boron nitride, silicon nitride, glass powder, glass frit, glass fiber, carbon fiber, and inorganic ion exchanger.
The inorganic filler may be used alone, or 2 or more kinds may be used in combination.
The lower limit of the average particle diameter of the inorganic filler is preferably 50nm, and the upper limit is preferably 4 μm. When the average particle diameter of the inorganic filler is in this range, the coating property and the processability of the obtained curable resin composition become more excellent. The lower limit of the average particle diameter of the inorganic filler is more preferably 100nm, and the upper limit is more preferably 3 μm.
The content of the inorganic filler is preferably 10 parts by weight at the lower limit and 150 parts by weight at the upper limit, based on 100 parts by weight of the total of the curable resin and the imide oligomer. When the content of the inorganic filler is in this range, the obtained curable resin composition is more excellent in moisture reflow resistance, plating resistance, and processability. A more preferable lower limit of the content of the inorganic filler is 20 parts by weight.
The curable resin composition of the present invention may contain a flow control agent for the purpose of improving coatability and shape retentivity to an adherend in a short time.
Examples of the flow control agent include fumed silica such as AEROSI L, and layered silicate.
The flow control agent can be used alone, also can be combined with more than 2.
As the flow control agent, a flow control agent having an average particle diameter of less than 100nm is suitably used.
The content of the flow control agent is preferably 0.1 part by weight in the lower limit and 50 parts by weight in the upper limit, based on 100 parts by weight of the total of the curable resin and the imide oligomer. When the content of the flow control agent is in this range, the effects of improving the applicability to an adherend in a short time, improving the shape retention property, and the like are further enhanced. The lower limit of the content of the flow control agent is more preferably 0.5 parts by weight, and the upper limit is more preferably 30 parts by weight.
The curable resin composition of the present invention may contain an organic filler for the purpose of relaxing stress, imparting toughness, and the like.
Examples of the organic filler include silicone rubber particles, acrylic rubber particles, urethane rubber particles, polyamide particles, polyamideimide particles, polyimide particles, benzoguanamine particles, and core-shell particles thereof. Among them, polyamide particles, polyamideimide particles, and polyimide particles are preferable.
The organic fillers may be used alone, or 2 or more of them may be used in combination.
The content of the organic filler is preferably up to 300 parts by weight based on 100 parts by weight of the total of the curable resin and the imide oligomer. When the content of the organic filler is in this range, the toughness and the like of the cured product of the obtained curable resin composition become more excellent while maintaining excellent adhesiveness and the like. The content of the organic filler is more preferably 200 parts by weight.
The curable resin composition of the present invention may contain a flame retardant.
Examples of the flame retardant include metal hydrates such as boehmite type aluminum hydroxide, and magnesium hydroxide, halogen compounds, phosphorus compounds, and nitrogen compounds. Among them, boehmite type aluminum hydroxide is preferable.
The flame retardants mentioned above may be used alone, or 2 or more of them may be used in combination.
The content of the flame retardant is preferably 5 parts by weight in the lower limit and 200 parts by weight in the upper limit, based on 100 parts by weight of the total of the curable resin and the imide oligomer. When the content of the flame retardant is in this range, the obtained curable resin composition has excellent flame retardancy while maintaining excellent adhesiveness and the like. The lower limit of the content of the flame retardant is more preferably 10 parts by weight, and the upper limit is more preferably 150 parts by weight.
The curable resin composition of the present invention may contain a polymer compound within a range not interfering with the object of the present invention. The polymer compound functions as a film-forming component.
The polymer compound may have a reactive functional group.
Examples of the reactive functional group include an amino group, a carbamate group, an imide group, a hydroxyl group, a carboxyl group, and an epoxy group.
The polymer compound may or may not form a phase separation structure in the cured product. In the case where the polymer compound does not form a phase separation structure in a cured product, the polymer compound is preferably one having an epoxy group as the reactive functional group, from the viewpoint of further excellent mechanical strength at high temperatures, high-temperature long-term heat resistance, and moisture resistance.
The curable resin composition of the present invention may contain a solvent from the viewpoint of coatability and the like.
The solvent is preferably a nonpolar solvent having a boiling point of 120 ℃ or less or an aprotic polar solvent having a boiling point of 120 ℃ or less, from the viewpoints of coatability, storage stability, and the like.
Examples of the nonpolar solvent having a boiling point of 120 ℃ or lower or the aprotic polar solvent having a boiling point of 120 ℃ or lower include ketone solvents, ester solvents, hydrocarbon solvents, halogen solvents, ether solvents, and nitrogen-containing solvents.
Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
Examples of the ester-based solvent include methyl acetate, ethyl acetate, and isobutyl acetate.
Examples of the hydrocarbon solvent include benzene, toluene, n-hexane, isohexane, cyclohexane, methylcyclohexane, and n-heptane.
Examples of the halogen-based solvent include dichloromethane, chloroform, and trichloroethylene.
Examples of the ether solvent include diethyl ether, tetrahydrofuran, 1, 4-dioxane, and 1, 3-dioxolane.
Examples of the nitrogen-containing solvent include acetonitrile.
Among them, from the viewpoint of handling properties, solubility of the imide oligomer, and the like, at least 1 selected from the group consisting of ketone solvents having a boiling point of 60 ℃ or higher, ester solvents having a boiling point of 60 ℃ or higher, and ether solvents having a boiling point of 60 ℃ or higher is preferable. Examples of such a solvent include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, 1, 4-dioxane, 1, 3-dioxolane, and tetrahydrofuran.
The "boiling point" is a value measured under a condition of 101kPa, or a value converted to 101kPa using a boiling point conversion chart or the like.
The lower limit of the content of the solvent in the curable resin composition of the present invention is preferably 20% by weight, and the upper limit is preferably 90% by weight. When the content of the solvent is in this range, the curable resin composition of the present invention is more excellent in coatability and the like. The lower limit of the content of the solvent is more preferably 30% by weight, and the upper limit is more preferably 80% by weight.
The curable resin composition of the present invention may contain a reactive diluent within a range not interfering with the object of the present invention.
As the reactive diluent, a reactive diluent having 2 or more reactive functional groups in 1 molecule is preferable from the viewpoint of adhesion reliability.
The curable resin composition of the present invention may further contain additives such as a coupling agent, a dispersant, a storage stabilizer, a barrier agent, a flux, a leveling agent, a rust inhibitor, and an adhesion imparting agent.
Examples of the method for producing the curable resin composition of the present invention include a method in which a curable resin, the imide oligomer of the present invention, an ion scavenger, and a solvent added as needed are mixed with a mixer such as a homomixer, a universal mixer, a banbury mixer, or a kneader.
The curable resin composition of the present invention is applied to a substrate film and dried to obtain a curable resin composition film formed from the curable resin composition of the present invention, and the curable resin composition film is cured to obtain a cured product.
The curable resin composition of the present invention preferably has an initial adhesion of a cured product to a copper foil of 3N/cm or more. The curable resin composition of the present invention can be suitably used for an adhesive for covering a flexible printed circuit board or the like, since the initial adhesion of the cured product to a copper foil is 3N/cm or more. The initial adhesion of the cured product to the copper foil is more preferably 5N/cm or more, and still more preferably 6N/cm or more.
The initial adhesion to the copper foil was measured as the peel strength of a test piece cut to a width of 1cm in a 90 ° peel test at a peel speed of 50mm/min at 25 ℃. As the test piece, a polyimide substrate (manufactured by Tolyu DuPont, KaPTON 100H, 25 μmt) was laminated on one surface of a curable resin composition film having a thickness of 20 μm, and a copper foil having a thickness of 35 μm was laminated on the other surface, and the resultant was heated at 190 ℃ for 1 hour to obtain a test piece. The initial adhesion is: the value measured within 24 hours after the production of the test piece. The curable resin composition film can be obtained by coating a curable resin composition on a substrate film and drying the coating. As the copper foil, an electrolytic copper foil (manufactured by Futian Metal foil powder industries, Ltd., "UN series", gloss surface roughness (Ra)0.25 μm) having a gloss surface can be used. The tensile tester may be, for example, UCT-500 (manufactured by ORIENTEC).
The curable resin composition of the present invention preferably has an adhesion to a copper foil of 3N/cm or more after a cured product thereof is stored at 200 ℃ for 100 hours. The curable resin composition of the present invention can be suitably used for a heat-resistant adhesive for vehicle use or the like, because the adhesion to a copper foil after storage of the cured product at 200 ℃ for 100 hours is 3N/cm or more. The cured product is stored at 200 ℃ for 100 hours, and the adhesion to a copper foil is more preferably 5N/cm or more, and still more preferably 6N/cm or more.
In particular, the curable resin composition of the present invention preferably has an adhesion of a cured product to a copper foil of 3N/cm or more even after storage at 200 ℃ for 200 hours. This can further suppress a decrease in adhesion even after a long-term storage under high-temperature conditions, such as 175 ℃ for 1000 hours.
The adhesion strength of the cured product to the copper foil after storage at 200 ℃ for 100 hours is: the test piece prepared in the same manner as the method for measuring the initial adhesive strength was stored at 200 ℃ for 100 hours, then cooled to 25 ℃ and measured by the same method as the initial adhesive strength within 24 hours after cooling.
The curable resin composition of the present invention preferably has a water absorption of 1.5% or less after a cured product thereof is exposed to a high-temperature and high-humidity environment of 85 ℃ and 85% RH for 24 hours. When the water absorption of the cured product is 1.5% or less, the curable resin composition of the present invention has more excellent initial adhesion, high-temperature long-term heat resistance, and reliability upon moisture absorption. The water absorption of the cured product is more preferably 1.2% or less, and still more preferably 1.0% or less.
The water absorption of the cured product after exposure to a high-temperature and high-humidity environment at 85 ℃ and 85% RH for 24 hours was determined from the change in weight of the cured product before and after exposure. Specifically, the water absorption of the cured product can be derived from the following equation by measuring the weight of the cured product before exposure, exposing the cured product to a high-temperature and high-humidity environment of 85 ℃ and 85% RH for 24 hours, and measuring the weight of the cured product after exposure.
Water absorption (%) ═ 100 × (((weight after exposure) - (weight before exposure)) + (weight before exposure))
As the cured product for measuring the water absorption, a cured product obtained by heating a curable resin composition film of 50mm × 50mm and a thickness of 400 μm at 190 ℃ for 1 hour was used.
The curable resin composition of the present invention can be used in a wide range of applications, and is particularly suitable for applications in electronic materials requiring high heat resistance, for example, in applications for aviation and in-vehicle Electrical Control Units (ECUs), die-attach materials for power devices using SiC and GaN, adhesives for power source cover packaging, curable resin compositions for printed wiring boards, adhesives for covering flexible printed circuit boards, copper-clad laminates, adhesives for semiconductor bonding, interlayer insulating films, prepregs, sealants for L ED, curable resin compositions for structural materials, and the like.
The curable resin composition film can be suitably used as an adhesive film. An adhesive film formed using the curable resin composition of the present invention is also one aspect of the present invention.
In addition, a cover film having a base film and a layer formed by a cured product of the curable resin composition of the present invention provided on the base film is also one aspect of the present invention.
Further, a flexible copper-clad laminate having a base film, a layer formed by a cured product of the curable resin composition of the present invention provided on the base film, and a copper foil is also one aspect of the present invention.
Effects of the invention
The present invention provides a curable resin composition which can provide a cured product having excellent heat resistance at high temperatures for a long period of time, moisture absorption reflow resistance, and plating resistance. Further, the present invention provides an adhesive comprising the curable resin composition, an adhesive film using the curable resin composition, and a coverlay film and a flexible copper-clad laminate each having a cured product of the curable resin composition.
Detailed Description
The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
Synthesis example 1 (preparation of imide oligomer composition A)
1, 4-bis (2- (4-aminophenyl) -2-propyl) benzene (product of MiTSUI FINE CHEMICA L Inc., "Bisaniline P") 17.2 parts by weight was dissolved in N-methylpyrrolidone (product of Wako pure chemical industries, Ltd., "NMP") 400 parts by weight, to the resulting solution was added 4, 4 '- (4, 4' -isopropylidenediphenoxy) bisphthalic anhydride (product of Tokyo chemical industries, Ltd.) 52.0 parts by weight, and the mixture was stirred at 25 ℃ for 2 hours to react the mixture to obtain an amic acid oligomer solution, and from the amic acid oligomer solution thus obtained, N-methylpyrrolidone was removed under reduced pressure and then heated at 300 ℃ for 2 hours to obtain an imide oligomer composition A (imidization rate 97%).
By the way of illustration1H-NMR, GPC and FT-IR analyses confirmed that: imide oligomer composition A containingAn imide oligomer having a structure represented by the above formula (1-1) (A is a group represented by the following formula (13) and B is a group represented by the following formula (14)). The number average molecular weight of the imide oligomer having the structure represented by the formula (1-1) was 1390. Further, it was confirmed that: the imide oligomer composition A contains, as an imide oligomer having a structure represented by the formula (1-1), an imide oligomer represented by the formula (4-1) and an imide oligomer represented by the formula (4-3) (both A and B are groups represented by the following formulae (13) and (14)).
[ solution 13]
Figure BDA0002515622060000221
In formula (13), ＊ represents a bonding site.
[ solution 14]
Figure BDA0002515622060000222
In formula (14), ＊ represents a bonding site.
Synthesis example 2 (preparation of imide oligomer composition B)
21.8 parts by weight of 3-aminophenol was dissolved in 400 parts by weight of N-methylpyrrolidone (NMP, Wako pure chemical industries, Ltd.). To the obtained solution, 17.2 parts by weight of 4, 4 '- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride was added, and the mixture was stirred at 25 ℃ for 2 hours to react, thereby obtaining an amic acid oligomer solution. From the obtained amic acid oligomer solution, N-methylpyrrolidone was removed under reduced pressure, and then the resulting solution was heated at 300 ℃ for 2 hours to obtain an imide oligomer composition B (imidization rate 96%).
By the way of illustration1H-NMR, GPC and FT-IR analyses confirmed that: the imide oligomer composition B contains an imide oligomer having a structure represented by the above formula (1-2) (a is a group represented by the above formula (13), and Ar is a group represented by the following formula (15)). Further, an imide having a structure represented by the formula (1-2) is lowThe number average molecular weight of the copolymer was 630. Further, it was confirmed that: the imide oligomer composition B contains an imide oligomer represented by the formula (5-1) (A is a group represented by the formula (13) and R is a hydrogen atom) as an imide oligomer having a structure represented by the formula (1-2).
[ solution 15]
Figure BDA0002515622060000231
In formula (15), ＊ represents a bonding site.
Examples 1 to 10 and comparative examples 1 and 2
The respective materials were mixed with stirring at the mixing ratios shown in tables 1 and 2 to prepare curable resin compositions of examples 1 to 10 and comparative examples 1 and 2.
Each of the obtained curable resin compositions was coated on a base PET film so as to have a thickness of about 20 μm and dried, thereby obtaining a curable resin composition film.
< evaluation >
The following evaluations were made for each of the curable resin compositions and each of the curable resin composition films obtained in examples and comparative examples. The results are shown in tables 1 and 2.
(initial adhesiveness)
Each of the curable resin compositions obtained in examples and comparative examples was coated on a polyimide substrate (made by durpont, tokton 100H, 25 μmt) to a thickness of about 20 μm and dried to obtain an adhesive film. The adhesive film thus obtained was cut into a width of 1cm, a copper foil (a glossy surface of an electrolytic copper foil, "CF-T8G-UN-35", manufactured by Futian Metal foil powder industries, Ltd.) having a thickness of 35 μm was laminated on the adhesive surface side, and hot pressing was carried out at 190 ℃ and 3MPa for 1 hour to cure the adhesive layer, thereby obtaining a test piece. The peel strength of a test piece within 24 hours after the production was measured by a 90 ° peel test using a tensile tester (manufactured by ORIENTEC corporation, "UCT-500") at a peel speed of 50mm/min at 25 ℃, and the peel strength thus obtained was used as the initial adhesion.
The initial adhesion was evaluated by assuming that the initial adhesion was 6N/cm or more as "◎", the initial adhesion was 3N/cm or more and less than 6N/cm as "○", and the initial adhesion was less than 3N/cm as "×".
(high temperature Long term Heat resistance)
The test piece obtained in the same manner as in the above "(initial adhesiveness)" was stored at 175 ℃ for 1000 hours, then cooled to 25 ℃, and the peel strength of the test piece within 24 hours after cooling was measured in the same manner as in the above "(initial adhesiveness)", and the obtained peel strength was set to 175 ℃ and the adhesive strength after 1000 hours.
The high-temperature long-term heat resistance (175 ℃, 1000 hours) was evaluated by assuming that the adhesive strength after 175 ℃, 1000 hours was 6N/cm or more as "◎", the adhesive strength after 3N/cm or more and less than 6N/cm as "○", and the adhesive strength after less than 3N/cm as "×".
The test piece obtained in the same manner as in the above "(initial adhesiveness)" was stored at 200 ℃ for 100 hours or 200 hours, then cooled to 25 ℃, and the peel strength of the test piece within 24 hours after cooling was measured in the same manner as in the above "(initial adhesiveness)", and the obtained peel strength was defined as the adhesive strength after 200 ℃ and 100 hours or the adhesive strength after 200 ℃ and 200 hours.
The high-temperature long-term heat resistance (200 ℃ C., 100 hours) was evaluated by assuming that the adhesive strength after 200 ℃ C., 100 hours was 6N/cm or more as "◎", the adhesive strength after 3N/cm or more and less than 6N/cm as "○", and the adhesive strength after less than 3N/cm as "×".
The high-temperature long-term heat resistance (200 ℃ C., 200 hours) was evaluated by assuming that the adhesive strength after 200 ℃ C., 200 hours was 6N/cm or more as "◎", the adhesive strength after 3N/cm or more and less than 6N/cm as "○", and the adhesive strength after 3N/cm or less than 6N/cm as "×".
(moisture absorption Return resistance)
The test piece obtained in the same manner as in the above "(initial adhesiveness)" was left to stand in an atmosphere of 40 ℃ and 90% RH for 72 hours, and then subjected to a moisture absorption reflow test by heating at 260 ℃ for 20 seconds. The presence or absence of air bubbles was visually confirmed in the test piece after the moisture absorption reflow test.
The moisture absorption and reflow resistance was evaluated by assuming that no bubble was observed as "○", assuming that bubbles at 1 or 2 points were observed as "Δ", and assuming that bubbles at 3 or more points were observed as "×".
(plating resistance)
The respective curable resin compositions obtained in examples and comparative examples were applied to a polyimide substrate (made by Tolyu DuPont, "KAPTON 100H", thickness 25 μm) to a thickness of about 20 μm, and dried to obtain an adhesive film, and a sample for FPC evaluation was prepared by providing an opening of 10mm × 10mm in the obtained adhesive film and bonding the adhesive film to a copper-clad laminate including a copper wiring pattern of L/S100 μm/100 μm and a copper wiring pattern of 18 μm thickness and a polyimide film of 50 μm thickness, and bonding was performed by hot pressing under the conditions of 190 ℃, 3MPa, and 1 hour.
The obtained sample for FPC evaluation was plated using commercially available electroless nickel plating bath and electroless gold plating bath at 80 to 90 ℃ under conditions of nickel 5 μm and gold 0.05 μm, the end of the adhesive film at the opening was observed with an optical microscope, and the plating resistance was evaluated by assuming that no leaching of the plating solution was observed as "○", that leaching of the plating solution was observed within a range of less than 200 μm from the end of the adhesive film as "Δ", and that leaching of the plating solution was observed within a range of 200 μm or more from the end of the adhesive film as "×".
(Water absorption)
The substrate PET films were peeled from the curable resin composition films obtained in examples and comparative examples, and then laminated and cut to obtain a laminated film having a thickness of 400 μm and a thickness of 50mm × 50 mm.A cured product was obtained by heating the laminated film at 190 ℃ for 1 hour.A weight of the obtained cured product (weight before exposure) was measured, and then exposed to a high-temperature and high-humidity environment at 85 ℃ and 85% RH for 24 hours.A weight of the cured product after exposure to the high-temperature and high-humidity environment (weight after exposure) was measured, and the water absorption of the cured product was derived from the above formula.
[ Table 1]
Figure BDA0002515622060000261
[ Table 2]
Figure BDA0002515622060000271
Industrial applicability
The present invention provides a curable resin composition which can provide a cured product having excellent heat resistance at high temperatures for a long period of time, moisture absorption reflow resistance, and plating resistance. Further, the present invention provides an adhesive comprising the curable resin composition, an adhesive film using the curable resin composition, and a coverlay film and a flexible copper-clad laminate each having a cured product of the curable resin composition.

Claims (12)

1. A curable resin composition characterized by containing a curable resin, an imide oligomer having an imide skeleton in the main chain and a crosslinkable functional group at the terminal, and an ion scavenger.
2. The curable resin composition according to claim 1, wherein the ion scavenger is an anion exchanger or an amphoteric ion exchanger.
3. The curable resin composition according to claim 1 or 2, wherein the ion scavenger is a particle having an average particle diameter of 10 μm or less.
4. The curable resin composition according to claim 1, 2 or 3, wherein the content of the ion scavenger is 0.1 to 200 parts by weight, based on 100 parts by weight of the total of the curable resin and the imide oligomer.
5. The curable resin composition according to claim 1, 2, 3 or 4, wherein the initial adhesion of a cured product to a copper foil is 3N/cm or more, and the adhesion of a cured product to a copper foil after storage at 200 ℃ for 100 hours is 3N/cm or more.
6. The curable resin composition according to claim 1, 2, 3, 4 or 5, wherein a cured product thereof has a water absorption of 1.5% or less after being exposed to a high-temperature and high-humidity environment of 85 ℃ and 85% RH for 24 hours.
7. The curable resin composition according to claim 1, 2, 3, 4, 5 or 6, wherein the imide oligomer has a number average molecular weight of 4000 or less.
8. The curable resin composition according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the crosslinkable functional group is at least one of an acid anhydride group and a phenolic hydroxyl group.
9. An adhesive comprising the curable resin composition according to claim 1, 2, 3, 4, 5, 6, 7 or 8.
10. An adhesive film comprising the curable resin composition according to claim 1, 2, 3, 4, 5, 6, 7 or 8.
11. A cover film comprising a base film and a layer formed from a cured product of the curable resin composition according to claim 1, 2, 3, 4, 5, 6, 7 or 8, provided on the base film.
12. A flexible copper-clad laminate comprising a base film, a layer formed on the base film and formed from a cured product of the curable resin composition according to claim 1, 2, 3, 4, 5, 6, 7 or 8, and a copper foil.
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