TWI805715B - Curable resin composition, adhesive, adhesive film, cover film, and flexible copper-clad laminate - Google Patents

Abstract

An object of the present invention is to provide a curable resin composition capable of obtaining a cured product excellent in high-temperature long-term heat resistance, moisture absorption reflow resistance, and plating resistance. Also, the object of the present invention is to provide an adhesive comprising the curable resin composition, an adhesive film using the curable resin composition, a cover film having a cured product of the curable resin composition, and a flexible adhesive. permanent copper clad laminates. The present invention relates to 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 end, and an ion scavenger.

Description

Curable resin composition, adhesive, adhesive film, cover film, and flexible copper-clad laminate

The present invention relates to a curable resin composition capable of obtaining a cured product excellent in high-temperature long-term heat resistance, moisture absorption reflow resistance, and plating resistance. Also, the present invention relates to an adhesive comprising the curable resin composition, an adhesive film using the curable resin composition, a cover film and a flexible cover having a cured product of the curable resin composition. Copper laminate.

Hardening resins such as epoxy resins that have low shrinkage and are excellent in adhesiveness, insulation, and chemical resistance are used in a large number of industrial products. Especially in electronic equipment applications, curable resin compositions are often used, that is, curable resin compositions that give good results in the short-term heat resistance reflow test or the repeated heat resistance cycle test. thing.

In recent years, electronic control units (ECUs) for vehicles, or power devices using SiC and GaN, etc. have attracted attention, but in curable resin compositions used in these applications, heat resistance when continuously exposed to high temperatures for a long period of time is required Resistance (high temperature long-term heat resistance) rather than short-term and repeated heat resistance.

As a curing agent used in a curable resin composition, for example, Patent Document 1 discloses that an acid anhydride component composed of an aromatic tetracarboxylic dianhydride is reacted with a diamine component composed of an aromatic diamine to form a obtained polyimide. In Patent Document 1, by using this polyimide, it is possible to form an adhesive layer that does not lower the adhesive force between the wiring layer and the cover film even if it is repeatedly exposed to high-temperature usage environments. However, in the conventional curable resin composition using such polyimide, it is difficult to maintain the adhesive force under severer temperature environment. Also, a curable resin composition having an effect of being excellent in moisture absorption and reflow resistance is required. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2017-145344

[Problem to be Solved by the Invention]

An object of the present invention is to provide a curable resin composition capable of obtaining a cured product excellent in high-temperature long-term heat resistance, moisture absorption reflow resistance, and plating resistance. Also, the object of the present invention is to provide an adhesive comprising the curable resin composition, an adhesive film using the curable resin composition, a cover film having a cured product of the curable resin composition, and a flexible adhesive. permanent copper clad laminates. [Technical means to solve the problem]

The present invention relates to 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 end, and an ion scavenger. The present invention will be described in detail below.

The inventors of the present invention believe that the reason for the poor long-term heat resistance or moisture absorption and reflow resistance of the known curable resin composition in a severe temperature environment is that the raw material of the curable resin composition or the printed wiring board, etc. Specific ions such as chloride ions in the copper foil cleaning solution used. Therefore, the inventors of the present invention have found that high-temperature long-term heat resistance and moisture absorption resistance can be obtained by further blending an ion-scavenging agent into a curable resin composition containing a curable resin and an imide oligomer having a specific structure. A cured product excellent in reflowability, and thus completed the present invention. In addition, 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 above-mentioned ion-scavenging agent, the cured product of the curable resin composition of the present invention is excellent in high-temperature long-term heat resistance and moisture absorption reflow resistance. Furthermore, in this specification, the above-mentioned "ion trapping agent" means an organic compound or an inorganic compound having the function of adsorbing, trapping, or exchanging ions.

The aforementioned ion capture agent 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, anion exchangers or amphoteric ion exchangers are preferred, anion exchangers are more preferred, and magnesium-aluminum compounds as anion exchangers are more preferred. The above-mentioned ion-scavenging agents may be used alone, or may be used in combination of two or more.

The above-mentioned ion trapping agent is preferably a particle having an average particle diameter of 10 μm or less from the viewpoint of ion trapping ability. When the above-mentioned ion scavenger has an average particle diameter of 10 μm or less, the cured product of the obtained curable resin composition is more excellent in high-temperature long-term heat resistance and moisture absorption reflow resistance. The above-mentioned ion trapping agent is more preferably particles having an average particle diameter of 6 μm or less, further preferably particles having an average particle diameter of 2 μm or less. Also, the lower limit of the average particle diameter of the ion trapping agent is not particularly limited, and the ion trapping agent is preferably particles having an average particle diameter of 0.01 μm or more, more preferably 0.1 μm or more from the viewpoint of thickening. In addition, the average particle size of the above-mentioned ion scavenger, and the inorganic filler and flow regulator described later can be measured by dispersing the particles in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS) .

The content of the above-mentioned ion scavengers is preferably 0.1 parts by weight in the lower limit and 200 parts by weight in the upper limit relative to 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 high-temperature long-term heat resistance and moisture absorption reflow resistance. A more preferable lower limit of the content of the above-mentioned ion trapping agent is 1 part by weight, a more preferable upper limit is 50 parts by weight, and a more preferable upper limit is 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 end (hereinafter also referred to as "imide oligomer of the present invention") . The imide oligomer of the present invention is excellent in reactivity and compatibility with curable resins such as epoxy resins. When the curable resin composition of the present invention contains the imide oligomer of the present invention, the cured product has excellent mechanical strength at high temperature and long-term heat resistance at high temperature.

The above-mentioned crosslinkable functional group is preferably a functional group that can react 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 them, 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 above-mentioned crosslinkable functional group at one terminal or both terminals. When both terminals have the above-mentioned crosslinkable functional groups, the obtained curable resin composition has a higher glass transition temperature after curing by increasing the crosslink density. On the other hand, when one end has the above-mentioned crosslinkable functional group, since the functional group equivalent becomes larger, the content of the imide oligomer of the present invention in the curable resin composition is increased, so the obtained cured The cured product of the permanent resin composition becomes one with better 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 including the above-mentioned crosslinkable functional group. By having the structure represented by the following formula (1-1) or the following formula (1-2), the imide oligomer of the present invention has better reactivity and compatibility with curable resins such as epoxy resins. Excellent.

In formula (1-1) and formula (1-2), A is a tetravalent group represented by the following formula (2-1) or the following formula (2-2); in formula (1-1), B It is a divalent group represented by the following formula (3-1) or the following formula (3-2); in formula (1-2), Ar is a divalent aromatic group which may be substituted.

In formula (2-1) and formula (2-2), * is the bonding position; in formula (2-1), Z is a bonding bond, an oxygen atom, or can be substituted or have oxygen at the bonding position Atomic divalent hydrocarbon group. The hydrogen atoms of the aromatic rings in formula (2-1) and formula (2-2) may also be substituted.

In formula (3-1) and formula (3-2), * is a bond position; in formula (3-1), Y is a bond, an oxygen atom, or a divalent hydrocarbon group that may be substituted. The hydrogen atoms of the aromatic rings in formula (3-1) and formula (3-2) may also be substituted.

In addition, the imide oligomer of the present invention may cause poor adhesion due to lower glass transition temperature after hardening or contamination of the adherend, so it is preferably an imide that does not have a siloxane skeleton in its structure. Oligomer.

The preferred upper limit of the number average molecular weight of the imide oligomer of the present invention is 4000. By setting the above-mentioned number average molecular weight to 4000 or less, the cured product of the obtained curable resin composition is more excellent in high-temperature long-term heat resistance. The more preferable upper limit of the number average molecular weight of the imide oligomer of the present invention is 3400, and the more preferable upper limit is 2800. In particular, the number average molecular weight of the imide oligomer of the present invention is preferably not less than 900 and not more than 4000 when it has the structure represented by the above formula (1-1), and it is preferably not less than 4000 when it has the structure represented by the above formula (1-2 ) in the case of a structure represented by ), it is preferably not less than 550 and not more than 4000. When having the structure represented by said formula (1-1), the lower limit of the number average molecular weight is more preferable 950, and a more preferable lower limit is 1000. When having the structure represented by said formula (1-2), the lower limit of the number average molecular weight is more preferable 580, and a more preferable lower limit is 600. In addition, in this specification, the said "number average molecular weight" is the value calculated|required by the polystyrene conversion measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. As a column used when measuring the number average molecular weight in terms of polystyrene by GPC, JAIGEL-2H-A (made by Nippon Analytical Industries, Ltd.) etc. are mentioned, for example.

Specifically, the imide oligomer of the present invention is preferably the following formula (4-1), the following formula (4-2), the following formula (4-3), or the following formula (4- 4) The 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) Represented imide oligomer.

In formula (4-1)～(4-4), A is the tetravalent group represented by following formula (6-1) or following formula (6-2); Formula (4-1), formula (4 -3) and formula (4-4), A may be the same or different. In formula (4-1)～(4-4), B is the divalent group represented by following formula (7-1) or following formula (7-2); Formula (4-3) and formula (4 In -4), B may be the same or different. In formula (4-2), X is a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group that may be substituted; in formula (4-4), W is a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group that may be substituted.

In formula (5-1)～(5-4), A is the tetravalent group represented by following formula (6-1) or following formula (6-2); Formula (5-3) and formula (5 In -4), A may be the same or different. In formulas (5-1)~(5-4), R is a hydrogen atom, a halogen atom, or a substituted monovalent hydrocarbon group; in formula (5-1) and formula (5-3), R can be the same , can also be different. In formula (5-2) and formula (5-4), W is a hydrogen atom, a halogen atom, or a substituted monovalent hydrocarbon group; in formula (5-3) and formula (5-4), B is the following A divalent group represented by the above formula (7-1) or the following formula (7-2).

In formula (6-1) and formula (6-2), * is the bonding position; in formula (6-1), Z is a bonding bond, an oxygen atom, or can be substituted or have oxygen at the bonding position Atomic divalent hydrocarbon group. The hydrogen atoms of the aromatic rings in formula (6-1) and formula (6-2) may be substituted.

In formula (7-1) and formula (7-2), * is a bond position; in formula (7-1), Y is a bond, an oxygen atom, or a divalent hydrocarbon group which may be substituted. The hydrogen atoms of the aromatic rings in formula (7-1) and formula (7-2) may be substituted.

As a method for producing an imide oligomer having a structure represented by the above-mentioned formula (1-1) among the imide oligomers of the present invention, for example, the following method can be enumerated. The method is to use the following formula (8 ) The acid dianhydride represented by ) reacts with the diamine represented by the following formula (9).

In formula (8), A is the same tetravalent group as A in the above formula (1-1).

In formula (9), B is the same divalent group as B in the above formula (1-1), and R ¹ to ^{R 4} are each independently a hydrogen atom or a monovalent hydrocarbon group.

The specific example of the method of making the acid dianhydride represented by said formula (8) react with the diamine represented by said formula (9) is shown below. The following method etc. may be enumerated: First, the diamine represented by the above-mentioned formula (9) is dissolved in a solvent (for example, N-methylpyrrolidone, etc.) in which the acrylic acid oligomer obtained by the reaction can be dissolved in advance, The acid dianhydride represented by the above formula (8) was added to the obtained solution and reacted to obtain an amide acid oligomer solution. Next, a method of removing the solvent by heating or reducing pressure, and further, heating at about 200° C. or higher for 1 hour or more to react the amide acid oligomers, etc. 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, the desired number average molecular weight can be obtained. An imide oligomer having a structure represented by the above formula (1-1). In addition, by substituting a part of the acid dianhydride represented by the above formula (8) with an acid anhydride represented by the following formula (10), it is possible to obtain the desired number average molecular weight and the above formula (1) at one end. The structure represented by -1) is an imide oligomer having a structure derived from an acid anhydride represented by the following formula (10) at the other end. In this case, the acid dianhydride represented by said formula (8) and the acid anhydride represented by following formula (10) may be added simultaneously, or may be added separately. Furthermore, by substituting a part of the diamine represented by the above formula (9) with a monoamine represented by the following formula (11), it is possible to obtain a compound having a desired number average molecular weight and having the above formula (1) at one end. The structure represented by -1) is an imide oligomer having a monoamine-derived structure represented by the following formula (11) at the other end. In this case, the diamine represented by said formula (9) and the monoamine represented by following formula (11) may be added simultaneously, or may be added separately.

In formula (10), Ar is a divalent aromatic group which may be substituted.

式（11）中，Ar係可經取代之1價芳香族基；R⁵ 及R⁶ 分別獨立地為氫原子或1價烴基。

In formula (11), Ar is a monovalent aromatic group that may be substituted; R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent hydrocarbon group.

As a method of producing an imide oligomer having a structure represented by the above-mentioned formula (1-2) among the imide oligomers of the present invention, for example, the acid dianhydride represented by the above-mentioned formula (8) and A method of reacting a phenolic hydroxyl-containing monoamine represented by the following formula (12), etc.

In formula (12), Ar is a divalent aromatic group that may be substituted, and R ⁷ and R ⁸ are each independently a hydrogen atom or a monovalent hydrocarbon group.

The specific example of the method of making the acid dianhydride represented by said formula (8) react with the phenolic hydroxyl group containing monoamine represented by said formula (12) is shown below. The following methods can be cited: First, the phenolic hydroxyl-containing monoamine represented by formula (12) is dissolved in a solvent in which the amide acid oligomer obtained by the reaction can be dissolved (such as N-methylpyrrolidone, etc. ), the acid dianhydride represented by the above formula (8) was added to the obtained solution and reacted to obtain an amic acid oligomer solution. Next, the solvent is removed by heating or reducing pressure, and further, the amide acid oligomer is reacted by heating at about 200° C. or higher for 1 hour or more. By adjusting the molar ratio of the acid dianhydride represented by the above formula (8) to the phenolic hydroxyl-containing monoamine represented by the above formula (12), and the imidization conditions, the desired number average molecular weight can be obtained An imide oligomer having a structure represented by the above formula (1-2) at both ends. In addition, by substituting a part of the phenolic hydroxyl-containing monoamine represented by the above formula (12) with the monoamine represented by the above formula (11), it is possible to obtain the desired number-average molecular weight and the above-mentioned monoamine at one end. The structure represented by the formula (1-2) is an imide oligomer having a monoamine-derived structure represented by the above formula (11) at the other end. In this case, the phenolic hydroxyl-containing monoamine represented by said formula (12) and the monoamine represented by said formula (11) may be added simultaneously or separately.

Examples of the acid dianhydride represented by the above formula (8) include pyromelteric dianhydride, 3,3'-oxydiphthalic dianhydride, and 3,4'-oxydiphthalic dianhydride. , 4,4'-oxydiphthalic dianhydride, 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic dianhydride, 4,4'-bis( 2,3-dicarboxyphenoxy)diphenyl ether dianhydride, p-phenylene bis(trimellitic anhydride), 2,3,3,4'-biphenyltetracarboxylic dianhydride, etc. Among them, 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° C. or less in terms of being excellent in solubility and heat resistance. , more preferably an aromatic acid dianhydride with a melting point below 220°C, more preferably an aromatic acid dianhydride with a melting point below 200°C, particularly preferably 3,4'-oxydiphthalic dianhydride (melting point 180°C), 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic dianhydride (melting point 190°C). In addition, in this specification, the said "melting point" means the value measured as the temperature of the endothermic peak when heating at 10 degreeC/min using a differential scanning calorimeter. As said differential scanning calorimeter, EXTEAR DSC6100 (made by SII NanoTechnology company) etc. are mentioned, for example.

Examples of the diamine represented by the above formula (9) include 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane , 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine Amine, 3,3'-diaminodiphenylphenylene, 4,4'-diaminodiphenylene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis( 4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, bis(4-(4-aminophenoxy)phenyl)methane, 2,2-bis( 4-(4-aminophenoxy)phenyl)propane, 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene, 1,4-bis(2-(4 -aminophenyl)-2-propyl)benzene, 3,3'-diamino-4,4'-dihydroxyphenylmethane, 4,4'-diamino-3,3'-dihydroxy Phenylmethane, 3,3'-diamino-4,4'-dihydroxyphenyl ether, bisaminophenyl fluorine, bistoluidine, 4,4'-bis(4-aminophenoxy) Biphenyl, 4,4'-diamino-3,3'-dihydroxyphenyl ether, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino- 2,2'-dihydroxybiphenyl, etc. Among them, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 1,3-bis(2-(4-amine, phenyl)-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 more preferably from the viewpoint of excellent solubility and heat resistance 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 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-anthracene dicarboxylic anhydride, 4-tertiary butylphthalic anhydride, 4-ethynylphthalic anhydride, 4 -Phenylethynyl phthalic anhydride, 4-fluorophthalic anhydride, 4-chlorophthalic anhydride, 4-bromophthalic anhydride, 3,4-dichlorophthalic anhydride, etc. .

Examples of the monoamine represented by the above formula (11) include aniline, o-toluidine, m-toluidine, p-toluidine, 2,4-dimethylaniline, 3,4-dimethylaniline, 3, 5-Dimethylaniline, 2-tertiary butylaniline, 3-tertiary butylaniline, 4-tertiary butylaniline, 1-naphthylamine, 2-naphthylamine, 1-aminoanthracene, 2-amine Anthracene, 9-aminoanthracene, 1-aminopyrene, 3-chloroaniline, o-methoxyaniline, m-methoxyaniline, p-methoxyaniline, 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,N-dimethyl-1,4-phenylenediamine, etc.

Examples of the phenolic hydroxyl-containing monoamine represented by the above formula (12) include: 3-aminophenol, 4-aminophenol, 4-amino-o-cresol, 5-amino-o-cresol, 4-aminophenol, Amino-2,3-xylenol, 4-amino-2,5-xylenol, 4-amino-2,6-xylenol, 4-amino-1-naphthol, 5-amine Base-2-naphthol, 6-amino-1-naphthol, 4-amino-2,6-diphenylphenol, etc. Among them, 4-amino-o-cresol, 5-amino-o-cresol, and 3-aminophenol are preferable because they are excellent in availability and storage stability, and can obtain a high glass transition temperature after curing. .

（醯亞胺化後之峰吸光度面積）÷（醯胺酸低聚物之峰吸光度面積））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 may be contained in a plurality of imides having a structure represented by the above formula (1-1) It is obtained in the form of an oligomer or a mixture (imide oligomer composition) of a plurality of imide oligomers having a structure represented by the above formula (1-2) and various raw materials. When the imide oligomer composition has an imidization rate of 70% or more, it is possible to obtain a cured product having better mechanical strength at high temperature and high-temperature long-term heat resistance when used as a curing agent. The lower limit of the imidization ratio of the above-mentioned imide oligomer composition is preferably 75%, more preferably 80%. Also, the preferable upper limit of the imidization ratio of the above-mentioned imide oligomer composition is not particularly limited, but the substantial upper limit is 98%. Furthermore, the above-mentioned "imidization rate" can be measured by Fourier transform infrared spectrophotometer (FT-IR) by total reflectance measurement method (ATR method), based on the 1660 cm ^{- 1} derived from the carbonyl group of amide acid The nearby peak absorbance area was derived by the following formula. As said Fourier transform infrared spectrophotometer, UMA600 (made by Agilent Technologies) etc. are mentioned, for example. Furthermore, the "peak absorbance area of the amide acid oligomer" in the following formula is obtained by reacting the acid dianhydride with a diamine or a phenolic hydroxyl-containing monoamine without performing an imidization step. The absorbance area of the amide acid oligomer obtained by removing the solvent by evaporation or the like. Imidization rate (%)=100×(1

(Peak absorbance area after imidization) ÷ (Peak absorbance area of amide acid oligomer))

From the viewpoint of the solubility of the above-mentioned imide oligomer composition when using the curable resin composition as a curing agent, it is preferable to dissolve 3 g or more with respect to 10 g of tetrahydrofuran at 25°C.

The above-mentioned imide oligomer composition preferably has a melting point of 200° C. or lower from the viewpoint of usability when a curable resin composition is used as a curing agent. The melting point of the above-mentioned imide oligomer composition is more preferably 190°C or lower, further preferably 180°C or lower. Also, the lower limit of the melting point of the imide oligomer composition is not particularly limited, but is preferably 60° C. or higher.

The preferred lower limit of 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 20 parts by weight, and the upper limit is preferably 80 parts by weight. By setting the content of the imide oligomer of the present invention within this range, the cured product of the obtained curable resin composition is more excellent in mechanical strength at high temperature and high-temperature long-term heat resistance. The more preferable lower limit of the content of the imide oligomer of the present invention is 25 parts by weight, and the more preferable upper limit is 75 parts by weight.

In order to improve processability in an uncured state, the curable resin composition of the present invention may contain other curing agents in addition to the imide oligomer of the present invention within the range that does not interfere with the object of the present invention. Examples of the other curing agents include phenolic curing agents, mercaptan curing agents, amine curing agents, acid anhydride curing agents, cyanate ester curing agents, and active ester curing agents. Among these, phenol-based curing agents, acid anhydride-based curing agents, cyanate-based curing agents, and active ester-based curing agents are preferred.

When the curable resin composition of the present invention contains the above-mentioned other curing agents, the upper limit of the content ratio of the above-mentioned other curing agents in the entire curing agent is preferably 70% by weight, more preferably 50% by weight, and even more preferably The upper limit is 30% by weight.

樹脂、矽酮樹脂、氟樹脂、聚醯亞胺樹脂、苯氧樹脂等。其中，較佳為環氧樹脂。又，該等硬化性樹脂可單獨使用，亦可混合2種以上使用。又，於對上述硬化性樹脂進行膜加工之情形，為了使處理性良好，較佳為於25℃中為液狀或半固形形狀，更佳為液狀。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, benzo

Resin, silicone resin, fluororesin, polyimide resin, phenoxy resin, etc. Among them, epoxy resin is preferable. Moreover, these curable resins may be used individually, and may mix and use 2 or more types. In addition, when processing the above-mentioned curable resin into a film, it is preferably liquid or semi-solid at 25° C., more preferably liquid, in order to improve handleability.

Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, bisphenol S epoxy resin, 2,2'-diallyl Bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether type epoxy resin Oxygen resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, fennel type epoxy resin, naphthyl ether type epoxy resin, phenol novolak type epoxy resin, o-formaldehyde Phenol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolak epoxy resin, naphthol novolac epoxy resin, glycidylamine epoxy resin, alkyl polyol Type epoxy resin, rubber modified epoxy resin, glycidyl ester compound, etc. Among them, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin and bisphenol E type epoxy resin are preferred in terms of low viscosity and easy adjustment of processability at room temperature of the curable resin composition obtained. Oxygen resin, resorcinol type epoxy resin.

The curable resin composition of the present invention preferably contains a curing accelerator. By containing the above-mentioned hardening accelerator, the hardening 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, and columium salt-based curing accelerators. Among these, imidazole-based curing accelerators and phosphine-based curing accelerators are preferred from the viewpoint of storage stability and curability. The above curing accelerators may be used alone or in combination of two or more.

The lower limit of the content of the hardening accelerator is preferably 0.8% by weight relative to the total weight of the curable resin, imide oligomer, and hardening accelerator. By making content of the said hardening accelerator 0.8 weight% or more, the effect of shortening hardening time becomes more excellent. The more preferable lower limit of content of the said hardening accelerator is 1 weight%. Moreover, from viewpoints, such as adhesiveness, the preferable upper limit of content of the said hardening accelerator is 10 weight%, and the more preferable upper limit is 5 weight%.

The curable resin composition of the present invention preferably contains an inorganic filler. By containing the above-mentioned inorganic filler, the curable resin composition of the present invention is more excellent in moisture absorption reflow resistance, plating resistance, and processability while maintaining excellent adhesiveness and high-temperature long-term heat resistance.

The above-mentioned inorganic filler is preferably at least any one of silicon oxide and barium sulfate. By containing at least one of silicon oxide and barium sulfate as the above-mentioned inorganic filler, the curable resin composition of the present invention is more excellent in moisture absorption reflow resistance, plating resistance, and workability.

Examples of inorganic fillers other than the aforementioned silicon oxide and the aforementioned barium sulfate include alumina, aluminum nitride, boron nitride, silicon nitride, glass powder, glass frit, glass fiber, carbon fiber, inorganic ion exchangers, etc. .

The above-mentioned inorganic fillers may be used alone or in combination of two or more.

The preferred lower limit of the average particle diameter of the above-mentioned inorganic filler is 50 nm, and the preferred upper limit is 4 μm. By making the average particle diameter of the said inorganic filler exist in this range, the curable resin composition obtained becomes what is more excellent in applicability and workability. A more preferable lower limit of the average particle diameter of the above-mentioned inorganic filler is 100 nm, and a more preferable upper limit is 3 μm.

The content of the inorganic filler is preferably 10 parts by weight in the lower limit and 150 parts by weight in the upper limit relative to 100 parts by weight of the total of the curable resin and the imide oligomer. By making content of the said inorganic filler into this range, the curable resin composition obtained becomes what is more excellent in moisture absorption reflow resistance, plating resistance, and processability. The more preferable lower limit of content of the said inorganic filler is 20 weight part.

The curable resin composition of the present invention may also contain a flow regulator in order to improve the applicability and shape retention of the adherend in a short period of time. As said flow regulator, fumed silica such as AEROSIL, layered silicates, etc. are mentioned, for example. The above-mentioned flow regulators may be used alone or in combination of two or more. In addition, as the above-mentioned flow regulator, it is suitable to use one having an average particle diameter of less than 100 nm.

The content of the flow regulator is preferably 0.1 parts by weight in the lower limit and 50 parts by weight in the upper limit relative to 100 parts by weight of the total of the curable resin and the imide oligomer. By setting the content of the above-mentioned flow regulator within this range, the effect of improving applicability and shape retention to an adherend in a short time becomes more excellent. A more preferable lower limit of the content of the above-mentioned flow regulator is 0.5 parts by weight, and a more preferable upper limit is 30 parts by weight.

The curable resin composition of the present invention may contain an organic filler for purposes such as stress relaxation and toughness imparting. Examples of the organic filler include silicone rubber particles, acrylic rubber particles, urethane rubber particles, polyamide particles, polyamide imide particles, polyimide particles, benzoguanamine particles, and such core-shell particles, etc. Among them, polyamide particles, polyamideimide particles, and polyimide particles are preferable. The above organic fillers may be used alone or in combination of two or more.

The content of the organic filler is preferably an upper limit of 300 parts by weight relative to 100 parts by weight of the total of the curable resin and the imide oligomer. By making content of the said organic filler into this range, the hardened|cured material of the curable resin composition obtained becomes what was more excellent in toughness etc. in the state which maintained excellent adhesiveness etc.. The more preferable upper limit of the content of the said organic filler is 200 weight part.

The curable resin composition of the present invention may also 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, nitrogen compounds, and the like. Among them, boehmite-type aluminum hydroxide is preferred. The above-mentioned flame retardants may be used alone or in combination of two or more.

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 relative to 100 parts by weight of the total of the curable resin and the imide oligomer. By making content of the said flame retardant into this range, the curable resin composition obtained becomes what is excellent in flame retardancy, maintaining excellent adhesiveness etc.. The more preferable lower limit of the content of the above-mentioned flame retardant is 10 parts by weight, and the more preferable upper limit is 150 parts by weight.

The curable resin composition of the present invention may contain a polymer compound within the range that does not interfere with the object of the present invention. The above-mentioned polymer compound functions as a film-forming component.

The above polymer compound may also have a reactive functional group. As said reactive functional group, an amine group, an urethane group, an imide group, a hydroxyl group, a carboxyl group, an epoxy group etc. are mentioned, for example.

In addition, the above polymer compound may or may not form a phase-separated structure in the cured product. When the polymer compound does not form a phase-separated structure in the cured product, the polymer compound is preferably: A polymer compound having an epoxy group as the above-mentioned reactive functional group.

烷、1,3－二氧戊環等。 作為上述含氮系溶劑，例如可列舉乙腈等。 其中，就操作性或醯亞胺低聚物之溶解性等觀點而言，較佳為選自由沸點為60℃以上之酮系溶劑、沸點為60℃以上之酯系溶劑、及沸點為60℃以上之醚系溶劑所組成之群中之至少1種。作為此種溶劑，例如可列舉：甲基乙基酮、甲基異丁基酮、乙酸乙酯、乙酸異丁酯、1,4－二

烷、1,3－二氧戊環、四氫呋喃等。 再者，上述｢沸點｣意指101 kPa之條件下所測定之值、或藉由沸點換算圖表等換算為101 kPa之值。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° C. or lower or an aprotic polar solvent having a boiling point of 120° C. or lower from the viewpoint of coatability, storage stability, and the like. Examples of the non-polar solvent having a boiling point of 120°C or lower or the aprotic polar solvent having a boiling point of 120°C or lower include ketone-based solvents, ester-based solvents, hydrocarbon-based solvents, halogen-based solvents, ether-based solvents, and nitrogen-containing solvents. Department of solvents, etc. As said ketone type solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone etc. are mentioned, for example. As said ester type solvent, methyl acetate, ethyl acetate, isobutyl acetate, etc. are mentioned, for example. As said hydrocarbon solvent, benzene, toluene, n-hexane, isohexane, cyclohexane, methylcyclohexane, n-heptane, etc. are mentioned, for example. As said halogen type solvent, methylene chloride, chloroform, trichloroethylene etc. are mentioned, for example. Examples of the aforementioned ether-based solvents include diethyl ether, tetrahydrofuran, 1,4-bis

Alkane, 1,3-dioxolane, etc. As said nitrogen-containing solvent, acetonitrile etc. are mentioned, for example. Among them, from the viewpoint of workability and the solubility of imide oligomers, it is preferable to select from ketone solvents with a boiling point of 60°C or higher, ester solvents with a boiling point of 60°C or higher, and solvents with a boiling point of 60°C or higher. At least one selected from the group consisting of the above ether-based solvents. Examples of such solvents include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, 1,4-bis

Alkanes, 1,3-dioxolane, tetrahydrofuran, etc. In addition, the said "boiling point" means the value measured under the condition of 101 kPa, or the value converted to 101 kPa by the boiling point conversion chart etc.

The preferable lower limit of the above-mentioned solvent content in the curable resin composition of this invention is 20 weight%, and the preferable upper limit is 90 weight%. By making content of the said solvent into this range, the curable resin composition of this invention becomes what is more excellent in applicability etc. A more preferable lower limit of the content of the above solvent is 30% by weight, and a more preferable upper limit is 80% by weight.

The curable resin composition of the present invention may contain a reactive diluent within the range that does not interfere with the object of the present invention. As said reactive diluent, it is preferable that it is a reactive diluent which has 2 or more reactive functional groups in 1 molecule from a viewpoint of adhesive reliability.

The curable resin composition of the present invention may further contain additives such as a coupling agent, a dispersant, a storage stabilizer, an anti-bleeding agent, a flux, a leveling agent, a rust inhibitor, and an adhesion imparting agent.

As a method of producing the curable resin composition of the present invention, for example, using a mixer such as a homogeneous disperser, a universal mixer, a Banbury mixer, and a kneader, to mix the curable resin and the imide of the present invention A method of mixing oligomers, ion scavengers, and solvents added as needed, etc.

By applying the curable resin composition of the present invention on a substrate film and drying it, a curable resin composition film composed of the curable resin composition of the present invention can be obtained, and the curable resin can be made The composition film is cured to obtain a cured product.

In the curable resin composition of the present invention, it is preferable that the initial adhesion force of the cured product to copper foil is 3 N/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., by making the initial adhesive force of the above-mentioned cured product to copper foil 3 N/cm or more. The initial adhesive force of the cured product to copper foil is more preferably 5 N/cm or more, and further preferably 6 N/cm or more. Furthermore, the above-mentioned initial adhesive force for copper foil can be used as the peeling test of 90°peeling test at 25°C and a peeling speed of 50 mm/min on a test piece cut to a width of 1 cm using a tensile tester. measured by strength. As the above-mentioned test piece, a single-layered polyimide substrate (manufactured by Toray DuPont, "Kapton 100H", 25 μmt) with a curable resin composition film with a thickness of 20 μm was used, and another single-layered polyimide substrate was used. Copper foil with a thickness of 35 μm obtained by heating at 190°C for 1 hour. The above-mentioned initial adhesive force means the value measured within 24 hours after the test piece was produced. The above-mentioned curable resin composition film can be obtained by applying the curable resin composition on a base film and drying it. As the above-mentioned copper foil, a glossy surface of electrolytic copper foil (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., "UN series", glossy surface roughness (Ra) 0.25 μm) can be used. As said tensile testing machine, UCT-500 (made by ORIENTEC company) etc. are mentioned, for example.

The curable resin composition of the present invention preferably has an adhesive force of 3 N/cm or more to the copper foil of the cured product after storage at 200° C. for 100 hours. The curable resin composition of the present invention can be suitably used as a heat-resistant adhesive for vehicles and the like by making the adhesive force of the cured product after storage at 200°C for 100 hours to copper foil 3 N/cm or more. The adhesive force of the cured product stored at 200° C. for 100 hours to copper foil is more preferably 5 N/cm or more, further preferably 6 N/cm or more. In particular, the curable resin composition of the present invention preferably has an adhesive force of 3 N/cm or more of the cured product to copper foil even after storage at 200° C. for 200 hours. Thereby, even after storage under long-term high-temperature conditions such as 175°C for 1000 hours, the decrease in adhesive force can be further suppressed. In addition, about the adhesive force of the cured product after storage at 200°C for 100 hours to copper foil, it means that the test piece prepared in the same way as the method of measuring the initial adhesion force was stored at 200°C for 100 hours, and then cooled. To 25°C, the value measured within 24 hours after cooling using the same method as the above-mentioned initial adhesion force.

The curable resin composition of the present invention preferably has a water absorption rate of 1.5% or less after being exposed to a high-temperature and high-humidity environment of 85°C and 85%RH for 24 hours. By making the water absorption of the cured product to be 1.5% or less, the curable resin composition of the present invention is more excellent in initial adhesiveness, high-temperature long-term heat resistance, and reliability at the time of moisture absorption. The water absorption of the cured product is more preferably at most 1.2%, and further preferably at most 1.0%. Furthermore, the water absorption rate of the cured product after exposure to the high temperature and high humidity environment of 85°C and 85%RH for 24 hours was obtained from the weight change of the cured product before and after exposure. Specifically, after measuring the weight of the cured product before exposure, it was exposed for 24 hours in a high-temperature, high-humidity environment of 85°C and 85% RH, and the weight of the cured product after exposure was measured, whereby the cured product can be derived from the following formula The water absorption rate of the material. Water absorption (%)=100×(((weight after exposure)－(weight before exposure))÷(weight before exposure)) As a cured product for measuring the above-mentioned water absorption rate, one obtained by heating a curable resin composition film of 50 mm x 50 mm and a thickness of 400 μm at 190° C. for 1 hour can be used.

The curable resin composition of the present invention can be used in a wide range of applications, and can be suitably used in electronic material applications requiring high heat resistance. For example, it can be used as a die bonding agent for aviation and vehicle electronic control units (ECU), or for power devices using SiC and GaN, adhesives for power cover packaging, curable resin compositions for printed wiring boards, flexible Adhesives for covering permanent printed circuit boards, copper clad laminates, adhesives for semiconductor bonding, interlayer insulating films, prepregs, encapsulants for LEDs, curable resin compositions for structural materials, etc. Among these, it can be suitably used for an adhesive agent use. Moreover, the adhesive agent containing the curable resin composition of this invention is also one of this invention.

The aforementioned curable resin composition film can be suitably used as an adhesive film. Moreover, the adhesive film which used the curable resin composition of this invention is also one of this invention. Also, a cover film having 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 is also one of the present invention. Furthermore, a flexible copper-clad laminate having 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 copper foil is also one of the present invention. [Effect of Invention]

According to the present invention, it is possible to provide a curable resin composition capable of obtaining a cured product excellent in high-temperature long-term heat resistance, moisture absorption reflow resistance, and plating resistance. Also, according to the present invention, an adhesive comprising the curable resin composition, an adhesive film using the curable resin composition, a cover film having a cured product of the curable resin composition, and a flexible film can be provided. permanent copper clad laminates.

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 (production of imide oligomer composition A)) 1,4-bis(2-(4-aminophenyl)-2-propyl)benzene (manufactured by Mitsui Fine Chemicals, " Bisaniline P") 17.2 parts by weight was dissolved in 400 parts by weight of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd., "NMP"). 52.0 parts by weight of 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the obtained solution, and stirred at 25°C This was allowed to react for 2 hours to obtain an amide acid oligomer solution. After removing N-methylpyrrolidone under reduced pressure from the obtained amide acid oligomer solution, it was heated at 300°C for 2 hours to obtain amide imide oligomer composition A (the imidization rate was 97%). Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the imide oligomer composition A contained the imide oligomer (A is a group represented by the following formula (13), and B is a group represented by the following formula (14). Moreover, the number average molecular weight of the imide oligomer which has the structure represented by this formula (1-1) was 1390. Furthermore, it was confirmed that the imide oligomer composition A contained the imide oligomer represented by the above-mentioned formula (4-1) and the imide oligomer represented by the above-mentioned formula (4-3) (both A and is a group represented by the following formula (13), and B is a group represented by the following formula (14)) as an imide oligomer having a structure represented by the above formula (1-1).

In formula (13), * is the bonding position.

In formula (14), * is the bonding position.

(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") portion. 17.2 parts by weight of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic dianhydride was added to the obtained solution, and it was stirred at 25° C. for 2 hours to react, thereby A solution of amide acid oligomers was obtained. After removing N-methylpyrrolidone under reduced pressure from the obtained amide acid oligomer solution, it was heated at 300°C for 2 hours to obtain amide imide oligomer composition B (the imidization rate was 96%). Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the imide oligomer composition B contained the imide oligomer (A is a group represented by the above formula (13), Ar is a group represented by the following formula (15)). Moreover, the number average molecular weight of the imide oligomer which has the structure represented by this formula (1-2) was 630. Furthermore, it was confirmed that the imide oligomer composition B contains an imide oligomer represented by the above formula (5-1) (A is a group represented by the above formula (13), and R is a hydrogen atom) as having An imide oligomer having a structure represented by the above formula (1-2).

In formula (15), * is the bonding position.

(Examples 1 to 10, Comparative Examples 1 and 2) According to the blending ratios recorded in Tables 1 and 2, each material was stirred and mixed to prepare each curable resin composition of Examples 1 to 10 and Comparative Examples 1 and 2. Each of the obtained curable resin compositions was applied on a substrate PET film so as to have a thickness of about 20 μm, and dried to obtain a curable resin composition film.

＜Evaluation＞ The following evaluations were performed on each curable resin composition and each curable resin composition film obtained in Examples and Comparative Examples. The results are shown in Tables 1 and 2.

(initial adhesion) Each of the curable resin compositions obtained in Examples and Comparative Examples was coated on a polyimide substrate (manufactured by Toray DuPont, "Kapton 100H", 25 μmt) so as to have a thickness of about 20 μm, By drying it, an adhesive film was obtained. The obtained adhesive film was cut into 1 cm width, and a copper foil with a thickness of 35 μm was laminated on the adhesive side (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., glossy side of electrolytic copper foil, "CF-T8G-UN-35") , under the conditions of 190° C., 3 MPa, and 1 hour, hot pressing was performed to harden the adhesive layer to obtain a test piece. For the test piece within 24 hours after production, the peel strength was measured by performing a 90° peel test at 25°C at a peel speed of 50 mm/min with a tensile tester (manufactured by ORIENTEC, "UCT-500"). The obtained peel strength was defined as the initial adhesive force. The case where the initial adhesive force was 6 N/cm or more was rated as "◎", the case of 3 N/cm or more and less than 6 N/cm was rated as "○", and the case of less than 3 N/cm was rated as "◎" 「×」, so as to evaluate the initial adhesiveness.

(high temperature long-term heat resistance) For the test piece obtained in the same way as above "(Initial Adhesion)", it was stored at 175°C for 1000 hours, and then cooled to 25°C. )” Measure the peel strength in the same way, and set the obtained peel strength as the adhesive force after 1000 hours at 175°C. The case where the adhesive force after 1000 hours at 175°C is 6 N/cm or more is rated as “◎”, the case where it is 3 N/cm or more and less than 6 N/cm is rated as “○”, and the case where it is less than 3 N /cm was marked as “×” to evaluate the high-temperature long-term heat resistance (175°C, 1000 hours). Also, for the test piece obtained in the same manner as above "(Initial Adhesion)", it was stored at 200°C for 100 hours or 200 hours, and then cooled to 25°C. For the test piece within 24 hours after cooling, the "(Initial Adhesion)" Measure the peel strength in the same way, and set the obtained peel strength as the adhesive force after 100 hours at 200°C, or the adhesive force after 200 hours at 200°C. The case where the adhesive force after 100 hours at 200°C was 6 N/cm or more was rated as “◎”, the case where it was 3 N/cm or more and less than 6 N/cm was rated as “○”, and the case where it was less than 3 N /cm was marked as “×” to evaluate the high-temperature long-term heat resistance (200°C, 100 hours). The case where the adhesive force after 200°C and 200 hours was 6 N/cm or more was rated as "◎", the case where it was 3 N/cm or more and less than 6 N/cm was rated as "○", and the case where it was less than 3 N /cm was marked as “×” to evaluate the high-temperature long-term heat resistance (200°C, 200 hours).

(Moisture absorption and reflow resistance) For the test piece obtained in the same manner as above "(Initial Adhesion)", after standing still for 72 hours in an environment of 40°C and 90%RH, a moisture absorption reflow test was performed by heating at 260°C for 20 seconds. For the test piece after the moisture absorption reflow test, the presence or absence of air bubbles was checked visually. Moisture absorption resistance was evaluated by setting "〇" when no air bubbles were confirmed, "△" when one or two air bubbles were confirmed, and "×" when three or more air bubbles were confirmed. Reflowability.

(plating resistance) Each of the curable resin compositions obtained in Examples and Comparative Examples was applied to a polyimide substrate (manufactured by Toray DuPont, "Kapton 100 H", thickness 25 μm) so as to have a thickness of about 20 μm. and dried to obtain an adhesive film. Set an opening of 10 mm×10 mm on the obtained adhesive film, and attach it to a copper wiring pattern with a thickness of 18 μm and a polyimide film with a thickness of 50 μm at L/S=100 μm/100 μm A copper-clad laminate was prepared to prepare a sample for FPC evaluation. In addition, bonding was carried out by hot pressing under the conditions of 190° C., 3 MPa, and 1 hour. The obtained samples for FPC evaluation were plated using a commercially available electroless nickel plating bath and an electroless gold plating bath at 80°C to 90°C under the 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 case where the leaching of the plating solution was not confirmed was marked as "O", and the leaching of the plating solution was confirmed within a range of less than 200 μm from the end of the adhesive film. The case where “△” was selected, and the case where the immersion of the plating solution was confirmed to be within the range of 200 μm or more from the end of the adhesive film was designated as “×” to evaluate the plating resistance.

(water absorption) The substrate PET film was peeled off from each curable resin composition film obtained in Examples and Comparative Examples, laminated and cut to obtain a laminated film of 50 mm×50 mm and 400 μm in thickness. A cured product was obtained by heating the obtained laminated film at 190° C. for 1 hour. After measuring the weight of the obtained hardened product (weight before exposure), it was exposed to a high-temperature and high-humidity environment of 85°C and 85%RH for 24 hours. Measure the weight of the cured product exposed to high temperature and high humidity (weight after exposure), and derive the water absorption rate of the cured product from the above formula.

[Table 1]

[產業上之利用可能性][Table 2]

[Industrial Utilization Possibility]

According to the present invention, it is possible to provide a curable resin composition capable of obtaining a cured product excellent in high-temperature long-term heat resistance, moisture absorption reflow resistance, and plating resistance. Also, according to the present invention, an adhesive comprising the curable resin composition, an adhesive film using the curable resin composition, a cover film having a cured product of the curable resin composition, and a flexible film can be provided. permanent copper clad laminates.

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Claims (11)

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 end, and an ion scavenger; and the above-mentioned imide oligomer The number average molecular weight of the substance is 4000 or less. The curable resin composition according to claim 1, wherein the ion-scavenging agent is an anion exchanger or an amphoteric ion exchanger. The curable resin composition according to claim 1 or 2, wherein the ion-scavenging agent is a particle having an average particle diameter of 10 μm or less. 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 relative to 100 parts by weight of the total of the curable resin and the imide oligomer. parts by weight or less. The curable resin composition according to claim 1 or 2, wherein the initial adhesive force of the cured product to the copper foil is 3 N/cm or more, and the adhesive force of the cured product to the copper foil after storage at 200° C. for 100 hours It is 3 N/cm or more. 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° C. and 85% RH for 24 hours is 1.5% or less. The curable resin composition according to claim 1 or 2, wherein the crosslinkable functional group is at least any one of an acid anhydride group and a phenolic hydroxyl group. An adhesive comprising the curable resin composition described in claim 1, 2, 3, 4, 5, 6 or 7. An adhesive film made of the curable resin composition described in claim 1, 2, 3, 4, 5, 6 or 7. 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, 6 or 7 provided on the base film. A flexible copper-clad laminate, which has a base film, and the hardened product of the curable resin composition described in claim 1, 2, 3, 4, 5, 6 or 7 is provided on the base film Constituent layer, and copper foil.