CN111417683B - 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
CN111417683B
CN111417683B CN201980006114.8A CN201980006114A CN111417683B CN 111417683 B CN111417683 B CN 111417683B CN 201980006114 A CN201980006114 A CN 201980006114A CN 111417683 B CN111417683 B CN 111417683B
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curable resin
resin composition
cured product
present
weight
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CN111417683A (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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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)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (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 which can obtain a cured product excellent in heat resistance at high temperatures for a long period of time, moisture absorption and reflow resistance, and plating resistance. The present invention also provides an adhesive comprising the curable resin composition, an adhesive film using the curable resin composition, and a cover film and a flexible copper-clad laminate each comprising a cured product of the curable resin composition. The present invention provides a curable resin composition comprising 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.

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 obtaining a cured product excellent in heat resistance at high temperature for a long period of time, moisture 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 cover 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 excellent adhesion, insulation and chemical resistance, are used in a wide variety of industrial products. Particularly, in the use of electronic devices, curable resin compositions are used in large amounts, which give good results in reflow tests for heat resistance in a short period of time and in cold and hot cycle tests for repeated heat resistance.
In recent years, attention has been paid to an in-vehicle Electrical Control Unit (ECU), a power device using SiC or GaN, and the like, but a curable resin composition used for these applications is required to have heat resistance when exposed to high temperature for a long period of time (high-temperature long-term heat resistance) rather than short-time heat resistance and repeated heat resistance.
As a curing agent used in a 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 this polyimide, an adhesive layer that does not deteriorate the adhesion between the wiring layer and the cover film can be formed even in a use environment exposed to repeated high temperatures. However, it is difficult for a conventional curable resin composition using such polyimide to maintain adhesion under a more severe temperature environment. In addition, there is a need for curable resin compositions that also have excellent effects in terms of resistance to moisture reflow.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open 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 which can obtain a cured product that has excellent high-temperature long-term heat resistance, moisture absorption reflow resistance, and plating resistance. The present invention also provides an adhesive comprising the curable resin composition, an adhesive film using the curable resin composition, and a cover film and a flexible copper-clad laminate each comprising a cured product of the curable resin composition.
Means for solving the problems
The present invention provides a curable resin composition comprising 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.
The present invention will be described in detail below.
The inventors consider that: the reason why the conventional curable resin composition is deteriorated in heat resistance at a high temperature for a long period or moisture reflow resistance under a severe temperature environment is that it is derived from specific ions such as chloride ions in a raw material of the curable resin composition and a cleaning solution for a copper foil used for a printed wiring board or the like.
Thus, the present inventors found that: the present invention has been completed by further blending an ion scavenger into a curable resin composition containing a curable resin and an imide oligomer having a specific structure, thereby obtaining a cured product excellent in heat resistance and moisture reflow resistance at a high temperature for a long period.
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, the cured product of the curable resin composition of the present invention is excellent in heat resistance and moisture reflow resistance at high temperatures over a long period of time.
In the present specification, the "ion scavenger" refers to an organic compound or an inorganic compound having a function of adsorbing, capturing, 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 them, the anion exchanger or the amphoteric ion exchanger is preferable, the anion exchanger is more preferable, and the magnesium-aluminum compound as the anion exchanger is further preferable.
The ion scavenger may be used alone or in combination of 2 or more.
From the viewpoint of ion trapping ability, the ion trapping agent is preferably particles having an average particle diameter of 10 μm or less. The above-mentioned ion scavenger is particles having an average particle diameter of 10 μm or less, whereby the cured product of the obtained curable resin composition is further excellent in heat resistance at high temperature for a long period and resistance to moisture absorption reflow. 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 diameter 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 diameter of 0.01 μm or more, more preferably particles having an average particle diameter of 0.1 μm or more.
The average particle diameters of the ion scavenger, the inorganic filler, and the flow regulator described later can be measured by dispersing the particles in a solvent (water, an organic solvent, or the like) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).
The content of the ion scavenger is preferably limited to 0.1 part by weight, and the content is preferably limited to 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 within this range, the cured product of the obtained curable resin composition is more excellent in long-term heat resistance at high temperature and resistance to moisture absorption reflow. The content of the ion scavenger is more preferably 1 part by weight, still more preferably 50 parts by weight, and still 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 curable resins such as epoxy resins. The curable resin composition of the present invention contains the imide oligomer of the present invention, and thus the cured product is excellent in mechanical strength at high temperature and long-term heat resistance at high temperature.
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. Of these, at least 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 may have the crosslinkable functional group at both ends. In the case where the crosslinkable functional groups are present at both ends, the crosslinking density is increased, and thus the resulting 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 functional group equivalent is increased, 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 is more excellent in long-term heat resistance at high temperature.
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 the structure containing the crosslinkable functional group. By having a structure represented by the following formula (1-1) or the following formula (1-2), the imide oligomer of the present invention is more excellent in reactivity and compatibility with a curable resin such as an epoxy resin.
[ chemical 1]
In the formulae (1-1) and (1-2), A is a 4-valent group represented by the following formula (2-1) or the following formula (2-2), B is a 2-valent group represented by the following formula (3-1) or the following formula (3-2), and Ar is an optionally substituted 2-valent aromatic group in the formula (1-2).
[ chemical 2]
In the formulae (2-1) and (2-2), Z is a bond, an oxygen atom, or a hydrocarbon group of 2 valences which is optionally substituted and optionally has an oxygen atom at the bond position, in the formula (2-1). The hydrogen atoms of the aromatic rings in the formula (2-1) and the formula (2-2) are optionally substituted.
[ chemical 3]
In the formulae (3-1) and (3-2), X is a bonding position, and in the formula (3-1), Y is a bonding bond, an oxygen atom, or an optionally substituted hydrocarbon group of 2 valency. The hydrogen atoms of the aromatic rings in the formula (3-1) and the formula (3-2) are optionally substituted.
In addition, since the glass transition temperature after curing is lowered or an adherend is contaminated to cause poor adhesion, the imide oligomer of the present invention is preferably an imide oligomer having no siloxane skeleton in its structure.
The preferred upper limit of the number average molecular weight of the imide oligomer described in the present invention is 4000. The number average molecular weight of 4000 or less makes the cured product of the obtained curable resin composition more excellent in long-term heat resistance at high temperatures. The number average molecular weight of the imide oligomer of the present invention is more preferably limited to 3400, and still more preferably limited to 2800.
In particular, the number average molecular weight of the imide oligomer according to the present invention is preferably 900 to 4000 in the case of having the structure represented by the above formula (1-1), and is preferably 550 to 4000 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 having 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 having 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 by measuring by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent and converting the obtained value into polystyrene. Examples of the column used for measuring the number average molecular weight in terms of polystyrene by GPC include JAIGEL-2H-A (manufactured by Japanese analytical industries Co., 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).
[ chemical 4]
In the formula (4-1) (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 formula (4-1) (4-4), B is a group having a valence of 2 represented by the following formula (7-1) or the following formula (7-2), and in the formula (4-3) and the formula (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 hydrocarbon group of 1 valence, and in the formula (4-4), W is a hydrogen atom, a halogen atom or an optionally substituted hydrocarbon group of 1 valence.
[ chemical 5]
In the formula (5-1) (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 formula (5-3) and the formula (5-4), A may be the same or different. In the formula (5-1) (5-4), R is a hydrogen atom, a halogen atom or an optionally substituted 1-valent hydrocarbon group, and in the formula (5-1) and the formula (5-3), R may be the same or different. In the formula (5-2) and the formula (5-4), W is a hydrogen atom, a halogen atom or an optionally substituted 1-valent hydrocarbon group, and in the formula (5-3) and the formula (5-4), B is a 2-valent group represented by the following formula (7-1) or the following formula (7-2).
[ chemical 6]
In the formulae (6-1) and (6-2), Z is a bond, an oxygen atom, or a hydrocarbon group of 2 valences which is optionally substituted and optionally has an oxygen atom at the bond position, in the formula (6-1). The hydrogen atoms of the aromatic rings in the formula (6-1) and the formula (6-2) are optionally substituted.
[ chemical 7]
In the formulae (7-1) and (7-2), X is a bonding position, and in the formula (7-1), Y is a bonding bond, an oxygen atom, or an optionally substituted hydrocarbon group of 2 valency. The hydrogen atoms of the aromatic rings in the formula (7-1) and the formula (7-2) are optionally substituted.
Among the imide oligomers of the present invention, examples of the method for producing an imide oligomer having the 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).
[ chemical 8]
In the formula (8), A is the same 4-valent group as that of the above formula (1-1).
[ chemical 9]
In the formula (9), B is the same 2-valent group as that of the B in the formula (1-1), and R1 to R4 are each independently a hydrogen atom or a 1-valent hydrocarbon group.
Hereinafter, a specific example of a method of reacting the acid dianhydride represented by the above formula (8) with the diamine represented by the above formula (9) will be described.
The following methods are exemplified: first, a diamine represented by the above formula (9) is dissolved in a solvent (for example, N-methylpyrrolidone) in which an amic acid oligomer obtained by the reaction can be dissolved, and an acid dianhydride represented by the above formula (8) is added to the obtained solution to react the solution, thereby obtaining an amic acid oligomer solution; then, the solvent is removed by heating or reducing pressure, and the mixture is heated at about 200℃or higher for 1 hour or longer to react the amic acid oligomer. By adjusting the molar ratio of the acid dianhydride represented by the above formula (8) to the diamine represented by the above formula (9) and the imidization conditions, an imide oligomer having a desired number average molecular weight and having a structure represented by the above formula (1-1) at both terminals 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, having a structure represented by the above formula (1-1) at one end and having 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 the monoamine represented by the following formula (11), an imide oligomer having a desired number average molecular weight, having the structure represented by the above formula (1-1) at one end, and having 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.
[ chemical 10]
In formula (10), ar is an optionally substituted 2-valent aromatic group.
[ chemical 11]
In the formula (11), ar is an optionally substituted 1-valent aromatic group, R 5 R is R 6 Each independently is a hydrogen atom or a hydrocarbyl group of valence 1.
Among the imide oligomers of the present invention, examples of the method for producing an imide oligomer having the 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 phenolic hydroxyl group-containing monoamine represented by the following formula (12).
[ chemical 12]
In the formula (12), ar is an optionally substituted 2-valent aromatic group, R 7 R is R 8 Each independently is a hydrogen atom or a hydrocarbyl group of valence 1.
Hereinafter, a specific example of a method of reacting the acid dianhydride represented by the above formula (8) with the phenolic hydroxyl group-containing monoamine represented by the above formula (12) will be described.
The following methods are exemplified: first, a phenolic hydroxyl group-containing monoamine represented by the formula (12) is dissolved in a solvent (for example, N-methylpyrrolidone, etc.) in which the amic acid oligomer obtained by the reaction is soluble, and an acid dianhydride represented by the formula (8) is added to the obtained solution to react the solution, thereby obtaining an amic acid oligomer solution; then, the solvent is removed by heating or reducing pressure, and the mixture is heated at about 200℃or higher for 1 hour or longer to react the amic acid oligomer. By adjusting the molar ratio of the acid dianhydride represented by the above formula (8) to the phenolic hydroxyl group-containing monoamine represented by the above formula (12) and the imidization conditions, an imide oligomer having a desired number average molecular weight and having a structure represented by the above formula (1-2) at both terminals can be obtained.
Further, by replacing a part of the monoamine having a phenolic hydroxyl group represented by the above formula (12) with the monoamine represented by the above formula (11), an imide oligomer having a desired number average molecular weight and having the structure represented by the above formula (1-2) at one end and having a structure derived from the monoamine represented by the above formula (11) at the other end can be obtained. In this case, the monoamine having a phenolic hydroxyl group 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' -oxydiphthalic dianhydride, 3,4' -oxydiphthalic dianhydride, 4' - (4, 4' -isopropylidenediphenoxy) diphthalic anhydride, 4' -bis (2, 3-dicarboxyphenoxy) diphenyl ether dianhydride, p-phenylene bis (trimellitic anhydride), 2, 3',4' -biphenyl tetracarboxylic dianhydride, and the like.
Among them, the acid dianhydride used in 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, particularly preferably 3,4' -oxydiphthalic dianhydride (melting point 180 ℃) or 4,4' - (4, 4' -isopropylidenediphenoxy) diphthalic anhydride (melting point 190 ℃), from the viewpoint of more excellent solubility and heat resistance.
In the present specification, the term "melting point" means: a differential scanning calorimeter was used as a value measured at 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.).
As the diamine represented by the above formula (9), examples thereof 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, and bis (4- (4-aminophenoxy) phenyl) methane, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-bis (2- (4-aminophenyl) -2-propyl) benzene, 1, 4-bis (2- (4-aminophenyl) -2-propyl) benzene, 3 '-diamino-4, 4' -dihydroxyphenyl methane 4,4 '-diamino-3, 3' -dihydroxyphenyl methane, 3 '-diamino-4, 4' -dihydroxyphenyl ether, diaminophenyl fluorene, dithianilide 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, 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 1, 3-bis (2- (4-aminophenyl) -2-propyl) benzene are preferable, and 1, 4-bis (2- (4-aminophenyl) -2-propyl) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, and 1, 4-bis (4-aminophenoxy) benzene are more preferable from the viewpoints of excellent solubility and heat resistance.
Examples of the acid anhydride represented by the formula (10) include phthalic anhydride, 3-methylphthalic anhydride, 4-methylphthalic anhydride, 1, 2-naphthalenedicarboxylic anhydride, 2, 3-naphthalenedicarboxylic anhydride, 1, 8-naphthalenedicarboxylic anhydride, 2, 3-anthracenedicarboxylic anhydride, 4-tert-butylphthalic anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4-fluorophthalic anhydride, 4-chlorophthalic anhydride, 4-bromophthalic anhydride, 3, 4-dichlorophthalic anhydride, and the like.
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-t-butylaniline, 3-t-butylaniline, 4-t-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- (methylthio) aniline, and N, N-dimethyl-1, 4-phenylenediamine.
Examples of the phenolic hydroxyl group-containing monoamine 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, 4-amino-2, 6-diphenylphenol, and the like. Among them, 4-amino-o-cresol, 5-amino-o-cresol, 3-aminophenol are preferable in terms of excellent availability and storage stability and a high glass transition temperature after curing.
In the case of producing the imide oligomer of the present invention by the above production method, the imide oligomer of the present invention is obtained in the form of an imide oligomer contained in a mixture (imide oligomer composition) of a plurality of imide oligomers having the structure represented by the above formula (1-1) or a plurality of imide oligomers having the structure represented by the above formula (1-2) and each raw material. When the imide oligomer composition has an imidization rate of 70% or more, a cured product having more excellent mechanical strength at high temperature and long-term heat resistance at high temperature can be obtained when the imide oligomer composition is used as a curing agent.
The imide oligomer composition preferably has a lower limit of 75% of the imidization rate, and more preferably has a lower limit of 80%. The preferable upper limit of the imidization ratio of the imide oligomer composition is not particularly limited, but the substantial upper limit is 98%.
The "imidization rate" can be measured by total reflection measurement (ATR method) using fourier transform infrared spectrophotometer (FT-IR), and is 1660cm of carbonyl group derived from amic acid by the following formula -1 The area of the nearby peak absorbance. Examples of the fourier transform infrared spectrophotometer include UMA600 (manufactured by Agilent Technologies corporation). 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 phenolic 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))
In the imide oligomer composition, from the viewpoint of solubility when used as a curing agent in a curable resin composition, it is preferable that 3g or more of the imide oligomer composition is dissolved in 10g of tetrahydrofuran at 25 ℃.
The imide oligomer composition preferably has a melting point of 200℃or lower from the viewpoint of handling properties 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 is preferably 20 parts by weight, and the upper limit is preferably 80 parts by weight. When the content of the imide oligomer of the present invention is within this range, the cured product of the obtained curable resin composition is further excellent in mechanical strength at high temperature and long-term heat resistance at high temperature. The lower limit of the content of the imide oligomer described in the present invention is more preferably 25 parts by weight, and the upper limit is more preferably 75 parts by weight.
In order to improve the processability in the uncured state, etc., the curable resin composition of the present invention may further contain other curing agents in addition to the imide oligomer of the present invention within a range that does not hinder the object of the present invention.
Examples of the other curing agent include phenol curing agents, thiol curing agents, amine curing agents, acid anhydride curing agents, cyanate curing agents, and active ester curing agents. Among them, a phenol-based curing agent, an acid anhydride-based curing agent, a cyanate-based curing agent, and an active ester-based curing agent are preferable.
In the case where the curable resin composition of the present invention contains the other curing agent, the content ratio of the other curing agent in the entire curing agent is preferably up to 70% by weight, more preferably up to 50% by weight, and even more preferably up to 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, phenolic 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 kinds.
In addition, in the case of film processing, the curable resin is preferably in a liquid or semisolid form at 25 ℃ in order to improve the handleability, and more preferably in a liquid form.
Examples of the epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2' -diallyl bisphenol a type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide addition bisphenol a type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, 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, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified type epoxy resin, and glycidyl ester compound. Among them, bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, resorcinol type epoxy resin are preferable in terms of low viscosity and easy adjustment of processability of the resulting curable resin composition at room temperature.
The curable resin composition of the present invention preferably contains a curing accelerator. By containing the above-mentioned curing accelerator, the curing time can be shortened and 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 preferable from the viewpoints of storage stability and curability.
The curing accelerators may be used alone or in combination of 2 or more.
The content of the curing accelerator is preferably limited to 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 improved by the content of the curing accelerator being 0.8 wt% or more. The lower limit of the content of the above-mentioned curing accelerator is more preferably 1% by weight.
The upper limit of the content of the curing accelerator is preferably 10% by weight, more preferably 5% by weight, from the viewpoint of adhesion and the like.
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 is further excellent in moisture-absorbing reflow resistance, plating resistance and processability while maintaining excellent adhesion and long-term heat resistance at high temperature.
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 further excellent in resistance to moisture reflow, 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 in combination of 2 or more.
The average particle diameter of the inorganic filler is preferably 50nm in lower limit and 4 μm in upper limit. When the average particle diameter of the inorganic filler is within this range, the obtained curable resin composition is further excellent in coatability and processability. The average particle diameter of the inorganic filler is more preferably limited to 100nm, and still more preferably to 3. Mu.m.
The content of the inorganic filler is preferably 10 parts by weight, and more preferably 150 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 inorganic filler is within this range, the resulting curable resin composition is more excellent in resistance to moisture reflow, plating resistance, and processability. The lower limit of the content of the inorganic filler is more preferably 20 parts by weight.
The curable resin composition of the present invention may contain a flow regulator for the purpose of improving the coatability to an adherend in a short period of time, shape retention, and the like.
Examples of the flow regulator include fumed silica such as AEROSIL and layered silicate.
The above-mentioned flow regulators may be used alone or in combination of 2 or more.
The flow control agent preferably has an average particle diameter of less than 100 nm.
The content of the flow regulator is preferably limited to 0.1 part by weight, and more preferably to 50 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 flow regulator is within this range, the effect of improving the coating property and shape retention property on the adherend in a short time becomes more excellent. The content of the flow regulator is more preferably limited to 0.5 parts by weight, and the content of the flow regulator is more preferably limited to 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 filler may be used alone or in combination of 2 or more.
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 within this range, the toughness and the like of the cured product of the obtained curable resin composition become more excellent while maintaining excellent adhesion and the like. The more preferable upper limit of the content of the organic filler is 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, aluminum hydroxide and magnesium hydroxide, halogen-based compounds, phosphorus-based compounds and nitrogen compounds. Among them, boehmite type aluminum hydroxide is preferable.
The above flame retardants may be used alone or in combination of 2 or more.
The content of the flame retardant is preferably limited to 5 parts by weight, and more preferably to 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 flame retardant is within this range, the obtained curable resin composition has excellent flame retardancy while maintaining excellent adhesion 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 that does not hinder the object of the present invention. The polymer compound serves 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 urethane group, an imide group, a hydroxyl group, a carboxyl group, and an epoxy group.
The polymer compound may or may not have a phase separation structure in the cured product. In the case where the polymer compound does not form a phase separation structure in the cured product, the polymer compound having an epoxy group as the reactive functional group is preferable from the viewpoint of more excellent mechanical strength at high temperature, long-term heat resistance at high temperature, 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, etc.
Examples of the nonpolar solvent having a boiling point of 120 ℃ or less or the aprotic polar solvent having a boiling point of 120 ℃ or less 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 solvents 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 methylene chloride, 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 viewpoints of operability, 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 solvents include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, 1, 4-dioxane, 1, 3-dioxolane, and tetrahydrofuran.
The "boiling point" refers to a value measured under the 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 within 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 that does not hinder 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 dispersing agent, a storage stabilizer, a barrier agent, a flux, a leveling agent, an anticorrosive agent, 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 using a mixer such as a homodispenser, a universal mixer, a Banbury mixer, or a kneader.
The curable resin composition of the present invention can be 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 can be cured to obtain a cured product.
The curable resin composition of the present invention preferably has an initial adhesion to a copper foil of 3N/cm or more. The curable resin composition of the present invention can be suitably used as an adhesive for covering a flexible printed circuit board, etc., 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 may be measured as a peel strength when a test piece cut to a width of 1cm is subjected to a 90 ° peel test at a peel speed of 50mm/min at 25 ℃ using a tensile tester. As the test piece, a test piece was used in which a polyimide substrate (made by "KAPTON 100H", 25 μm by eastern dupont) 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 test piece was heated at 190 ℃ for 1 hour. The initial adhesion force mentioned above means: the test piece was measured within 24 hours after production. The curable resin composition film can be obtained by coating a substrate film with the curable resin composition and drying the coated substrate film. As the copper foil, an electrolytic copper foil (manufactured by Fufield Metal foil powder industry Co., ltd., "UN series", gloss surface roughness (Ra) of 0.25 μm) was used. Examples of the tensile testing machine include UCT-500 (manufactured by ORIENTEC Co.).
The curable resin composition of the present invention preferably has an adhesion to a copper foil of 3N/cm or more after storage at 200℃for 100 hours. The curable resin composition of the present invention can be suitably used in a heat-resistant adhesive for vehicles and the like, since the adhesion to a copper foil is 3N/cm or more after the cured product is stored at 200 ℃ for 100 hours. The adhesion to the copper foil after storage at 200℃for 100 hours 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 to a copper foil of 3N/cm or more even after storage at 200℃for 200 hours. This can further suppress the decrease in adhesion even after storage at 175 ℃ for 1000 hours or the like under a long-term high-temperature condition.
The adhesion to the copper foil after the cured product was stored at 200 ℃ for 100 hours is: the test piece produced in the same manner as the initial adhesion measurement method was stored at 200℃for 100 hours, cooled to 25℃and cooled to 24 hours or less, and the value measured by the same method as the initial adhesion was used.
The water absorption rate of the cured product of the curable resin composition of the present invention after exposure to a high-temperature and high-humidity environment of 85 ℃ and 85% RH for 24 hours is preferably 1.5% or less. The water absorption of the cured product is 1.5% or less, and thus the initial adhesion, high-temperature long-term heat resistance, and reliability in moisture absorption of the curable resin composition of the present invention are further improved. The water absorption rate 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 24 hours of exposure to a high-temperature and high-humidity environment at 85 ℃ and 85% RH was determined from the weight change of the cured product before and after exposure. Specifically, after measuring the weight of the cured product before exposure, the cured product was exposed to a high-temperature and high-humidity environment of 85 ℃ and 85% rh for 24 hours, and the weight of the cured product after exposure was measured, whereby the water absorption rate of the cured product was derived from the following formula.
Water absorption (%) =100× (((weight after exposure) - (weight before exposure))/(weight before exposure))
As a cured product for measuring the water absorption, a cured product obtained by heating a curable resin composition film having a thickness of 50mm×50mm and 400 μm at 190℃for 1 hour can be used.
The curable resin composition of the present invention can be used in a wide variety of applications, and is particularly suitable for use in electronic materials requiring high heat resistance. For example, the resin composition can be used in applications such as aviation and vehicle-mounted Electric Control Units (ECU), chip mounting agents for power device applications using SiC or GaN, adhesives for power supply cover packaging, curable resin compositions for printed wiring boards, adhesives for covering flexible printed circuit boards, copper-clad laminates, adhesives for bonding semiconductors, interlayer insulating films, prepregs, LED sealants, and curable resin compositions for structural materials. Among them, it is suitable for adhesive applications. In addition, an adhesive comprising the curable resin composition of the present invention is also one of the present invention.
The curable resin composition film can be suitably used as an adhesive film. An adhesive film using the curable resin composition of the present invention is also one of the present invention.
The present invention also provides a cover film comprising a base film and a layer formed of a cured product of the curable resin composition of the present invention provided on the base film.
Further, a flexible copper-clad laminate comprising a base film, a layer formed of a cured product of the curable resin composition of the present invention provided on the base film, and a copper foil is also one of the present invention.
Effects of the invention
According to the present invention, a curable resin composition capable of obtaining a cured product excellent in heat resistance at high temperature for a long period of time, moisture reflow resistance and plating resistance can be provided. Further, according to the present invention, an adhesive agent containing the curable resin composition, an adhesive film using the curable resin composition, and a cover film and a flexible copper-clad laminate each having a cured product of the curable resin composition can be provided.
Detailed Description
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Synthesis example 1 (preparation of imide oligomer composition A)
17.2 parts by weight of 1, 4-bis (2- (4-aminophenyl) -2-propyl) benzene (MITSUI FINE CHEMICAL Inc., manufactured by Bisaniline P ") was dissolved in 400 parts by weight of N-methylpyrrolidone (manufactured by Wako pure chemical industries, ltd.," NMP "). To the obtained solution, 52.0 parts by weight of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride (manufactured by tokyo chemical industry Co., ltd.) was added, and the mixture was stirred at 25℃for 2 hours to react, thereby obtaining an amic acid oligomer solution. N-methylpyrrolidone was removed from the obtained amic acid oligomer solution under reduced pressure, and then heated at 300℃for 2 hours, whereby an imide oligomer composition A (imidization rate 97%) was obtained.
By the way, by 1 H-NMR, GPC and FT-IR analysis revealed that: the imide oligomer composition A contains an 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) is 1390. Further, it was confirmed that: the imide oligomer composition A contains the imide oligomer represented by the formula (4-1) as the imide oligomer having the structure represented by the formula (1-1) (A is a group represented by the formula (13) below, and B is a group represented by the formula (14) below).
[ chemical 13]
/>
In formula (13), the bond position is.
[ chemical 14]
In formula (14), the bond position is.
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 (manufactured by Wako pure chemical industries, ltd., "NMP"). 17.2 parts by weight of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride was added to the obtained solution, and the mixture was stirred at 25℃for 2 hours to react, thereby obtaining an amic acid oligomer solution. N-methylpyrrolidone was removed from the obtained amic acid oligomer solution under reduced pressure, and then heated at 300℃for 2 hours, whereby an imide oligomer composition B (imidization rate 96%) was obtained.
By the way, by 1 H-NMR, GPC and FT-IR analysis revealed 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)). The number average molecular weight of the imide oligomer having the structure represented by the formula (1-2) was 630. Further, it was confirmed that: the imide oligomer composition B contains an imide oligomer represented by the above formula (5-1) as an imide oligomer having the structure represented by the above formula (1-2) (A is a group represented by the above formula (13), and R is a hydrogen atom).
[ 15]
In formula (15), the bond position is.
Examples 1 to 10 and comparative examples 1 and 2
The curable resin compositions of examples 1 to 10 and comparative examples 1 and 2 were prepared by mixing the materials with stirring according to the blending ratios shown in tables 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, whereby a curable resin composition film was obtained.
< evaluation >
The curable resin compositions and curable resin composition films obtained in examples and comparative examples were evaluated as follows. The results are shown in tables 1 and 2.
(initial adhesiveness)
The curable resin compositions obtained in examples and comparative examples were applied to polyimide substrates (manufactured by Toli DuPont, "KAPTON 100H", 25 μm) so as to have a thickness of about 20 μm, and dried to obtain adhesive films. The obtained adhesive film was cut into 1cm wide, a copper foil (glossy surface of electrolytic copper foil, "CF-T8G-UN-35" manufactured by Fufield Metal foil powder industry Co., ltd.) having a thickness of 35 μm was laminated on the adhesive surface side, and the adhesive layer was cured by hot pressing at 190℃under 3MPa for 1 hour to obtain a test piece. The peel strength of the test piece was measured by a tensile tester (manufactured by ORIENTEC, inc. 'UCT-500') at a peel speed of 50mm/min at 25℃and a 90℃peel test was performed, and the peel strength thus obtained was used as the initial adhesive force.
The initial adhesiveness was evaluated by setting the initial adhesiveness to 6N/cm or more as "verygood", setting the initial adhesiveness to 3N/cm or more and less than 6N/cm as "good", setting the initial adhesiveness to 3N/cm or less as "X".
(high temperature Long-term Heat resistance)
The test piece obtained in the same manner as the "(initial adhesion)" was stored at 175℃for 1000 hours, cooled to 25℃and the peel strength was measured by the same method as the "(initial adhesion)" for the test piece within 24 hours after cooling, and the obtained peel strength was set to an adhesion after 1000 hours at 175 ℃.
The adhesion at 175℃after 1000 hours was set to 6N/cm or more as "verygood", 3N/cm or more and less than 6N/cm as "good", and less than 3N/cm as "X", and the high-temperature long-term heat resistance (175℃for 1000 hours) was evaluated.
Further, the test piece obtained in the same manner as the "(initial adhesion)" was stored at 200℃for 100 hours or 200 hours, then cooled to 25℃and the peel strength was measured by the same method as the "(initial adhesion)" for the test piece within 24 hours after cooling, and the obtained peel strength was used as the adhesion after 100 hours at 200℃or the adhesion after 200 hours at 200 ℃.
The high-temperature long-term heat resistance (200 ℃ C., 100 hours) was evaluated by setting the adhesion at 200 ℃ C. For 6N/cm or more as "verygood", setting the adhesion at 3N/cm or more and less than 6N/cm as "good", setting the adhesion at less than 3N/cm as "×".
The high-temperature long-term heat resistance (200 ℃ C., 200 hours) was evaluated by setting the adhesion at 200 ℃ C. For 6N/cm or more as "verygood", setting the adhesion at 3N/cm or more and less than 6N/cm as "good", setting the adhesion at less than 3N/cm as "×".
(moisture absorption reflow resistance)
The test piece obtained in the same manner as the "(initial adhesion)" was allowed to stand at 40℃for 72 hours under 90% RH, and then subjected to a moisture absorption reflux test by heating at 260℃for 20 seconds. The presence or absence of air bubbles was visually confirmed on the test piece after the moisture absorption reflow test.
The moisture absorption reflow resistance was evaluated by setting "o" when no bubble was confirmed, "Δ" when no bubble was confirmed at 1 or 2, and "x" when no bubble was confirmed at 3 or more.
(plating resistance)
The curable resin compositions obtained in examples and comparative examples were applied to polyimide substrates (manufactured by Toli DuPont, "KAPTON 100H", thickness 25 μm) so as to have a thickness of about 20 μm, and dried to obtain adhesive films. An opening of 10mm×10mm was provided in the obtained adhesive film, and the adhesive film was bonded to a copper-clad laminate including a copper wiring pattern having an L/s=100 μm/100 μm and a thickness of 18 μm and a polyimide film having a thickness of 50 μm, to prepare a sample for FPC evaluation. The lamination was performed by hot pressing at 190℃under 3MPa for 1 hour.
The obtained samples for evaluating FPC were plated with 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. Mu.m. The plating resistance was evaluated by observing the end of the adhesive film at the opening with an optical microscope, and by setting "o" when the leaching of the plating solution was not confirmed, setting "Δ" when the leaching of the plating solution was confirmed in a range of less than 200 μm from the end of the adhesive film, and setting "x" when the leaching of the plating solution was confirmed in a range of 200 μm or more from the end of the adhesive film.
(Water absorption)
The base PET film was peeled from each of 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 50mm by 50mm and 400. Mu.m. The resulting laminate film was heated at 190℃for 1 hour to obtain a cured product. After measuring the weight of the obtained cured product (weight before exposure), the cured product was exposed to a high-temperature and high-humidity environment at 85℃and 85% RH for 24 hours. The weight of the cured product after exposure to a 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
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TABLE 2
Industrial applicability
According to the present invention, a curable resin composition capable of obtaining a cured product excellent in heat resistance at high temperature for a long period of time, moisture reflow resistance and plating resistance can be provided. Further, according to the present invention, an adhesive agent containing the curable resin composition, an adhesive film using the curable resin composition, and a cover film and a flexible copper-clad laminate each having a cured product of the curable resin composition can be provided.

Claims (10)

1. A curable resin composition comprising 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,
the curable resin comprises an epoxy resin and,
the crosslinkable functional group has at least one of an acid anhydride group and a phenolic hydroxyl group,
the number average molecular weight of the imide oligomer is 4000 or less.
2. The curable resin composition according to claim 1, wherein the ion scavenger is an anion exchanger or a zwitterionic exchanger.
3. The curable resin composition according to claim 1 or 2, wherein the ion scavenger is particles having an average particle diameter of 10 μm or less.
4. The curable resin composition according to claim 1 or 2, wherein the content of the ion scavenger is 0.1 parts by weight or more and 200 parts by weight or less relative to 100 parts by weight of the total of the curable resin and the imide oligomer.
5. The curable resin composition according to claim 1 or 2, wherein the cured product has an initial adhesion to a copper foil of 3N/cm or more and an adhesion to a copper foil after storage at 200 ℃ for 100 hours of the cured product is 3N/cm or more.
6. The curable resin composition according to claim 1 or 2, wherein the water absorption of the cured product after exposure to a high-temperature and high-humidity environment of 85 ℃ and 85% RH for 24 hours is 1.5% or less.
7. An adhesive comprising the curable resin composition according to claim 1, 2, 3, 4, 5 or 6.
8. An adhesive film comprising the curable resin composition according to claim 1, 2, 3, 4, 5 or 6.
9. A cover film comprising a base film and a layer formed of a cured product of the curable resin composition according to claim 1, 2, 3, 4, 5 or 6 provided on the base film.
10. A flexible copper-clad laminate comprising a base film, a layer formed of the cured product of the curable resin composition according to claim 1, 2, 3, 4, 5 or 6 provided on the base film, and a copper foil.
CN201980006114.8A 2018-03-20 2019-03-14 Curable resin composition, adhesive film, coverlay film, and flexible copper-clad laminate Active CN111417683B (en)

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