TWI781239B - Curable resin composition, cured product, adhesive, and adhesive film - Google Patents

Abstract

It is an object of the present invention to provide a curable resin composition that is excellent in flame retardancy, adhesiveness, high-temperature long-term heat resistance, and moisture absorption reflow resistance, and has low environmental load. Furthermore, the object of the present invention is to provide a cured product of the curable resin composition, and an adhesive and an adhesive film using the curable resin composition. The present invention is a curable resin composition, which contains curable resin, imide oligomer, and diaspore type aluminum hydroxide.

Description

Curable resin composition, cured product, adhesive, and adhesive film

The present invention relates to a curable resin composition which is excellent in flame retardancy, adhesiveness, high temperature long-term heat resistance, and moisture absorption and reflow resistance, and has low environmental load. Also, the present invention relates to a cured product of the curable resin composition, and an adhesive and an adhesive film using the curable resin composition. Also, the present invention relates to a curable resin composition excellent in adhesiveness, high-temperature long-term heat resistance, moisture absorption reflow resistance, plating resistance, low exudation during rapid pressing, and embedding properties. Also, the present invention relates to a cured product of the curable resin composition, and an adhesive and an adhesive film using the curable resin composition.

In recent years, the use of flexible printed wiring boards (FPCs) has expanded to vehicle applications, and high-temperature and long-term heat resistance is required for adhesives used for FPCs or coverlay films for protecting FPCs. For such adhesives, curable resin compositions using curable resins such as epoxy resins that are low in shrinkage and excellent in adhesiveness, insulation, and chemical resistance are used. In particular, the following curable resins are used in large quantities. Composition, the curable resin composition can obtain good results in the reflow test related to short-term heat resistance, or the cold-heat cycle test related to repeated heat resistance.

As a curable resin composition excellent in heat resistance, for example, Patent Documents 1 and 2 disclose a curable resin composition containing an epoxy resin and an imide oligomer as a curing agent. However, when a large amount of a flame retardant is blended in order to impart flame retardancy required for vehicle applications to such curable resin compositions, there is a problem that adhesiveness and high-temperature long-term heat resistance are lowered. In addition, such curable resin compositions containing a large amount of flame retardants have a problem of poor moisture absorption and reflow resistance. Therefore, there is a need for a curable resin composition that has not only heat resistance but also excellent effects in adhesiveness, moisture absorption reflow resistance, or plating resistance.

Patent Document 3 discloses a curable resin composition containing a modified polyamide epoxy resin, a maleimide oligomer, and a flame retardant. The curable resin composition disclosed in Patent Document 3 is considered to exhibit flame retardancy and to be excellent in adhesiveness and high-temperature long-term heat resistance. However, since a halogenated compound is used as a flame retardant, there are problems from the viewpoint of environmental load and the like, and there are problems that, when a flame retardant other than a halogenated compound is used, sufficient adhesiveness cannot be obtained or The case of high temperature long-term heat resistance.

Patent Document 4 discloses a resin composition containing an inorganic filler having an average particle diameter of not less than 1 nm and not more than 500 nm. The resin composition disclosed in Patent Document 4 is considered to be excellent in moisture absorption reflow resistance, or low exudation when heated or pressurized. However, the resin composition disclosed in Patent Document 4 has insufficient high-temperature long-term heat resistance, or the problem of insufficient suppression of exudation of the resin composition by a pressing method called rapid pressing in FPC manufacturing or processing. [Prior Art Literature] [Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. 2007-91799 Patent Document 2: Japanese Patent Application Laid-Open No. 61-270852 Patent Document 3: Japanese Unexamined Patent Application Publication No. H10-130400 Patent Document 4: Japanese Patent Laid-Open No. 2007-204696

[Problem to be Solved by the Invention]

It is an object of the present invention to provide a curable resin composition that is excellent in flame retardancy, adhesiveness, high-temperature long-term heat resistance, and moisture absorption reflow resistance and has low environmental load. Furthermore, the object of the present invention is to provide a cured product of the curable resin composition, and an adhesive and an adhesive film using the curable resin composition. Another object of the present invention is to provide a curable resin composition excellent in adhesiveness, high-temperature long-term heat resistance, moisture absorption reflow resistance, plating resistance, and low exudation and embedding properties during rapid pressing. Furthermore, the object of the present invention is to provide a cured product of the curable resin composition, and an adhesive and an adhesive film using the curable resin composition. [Technical means to solve the problem]

The present invention 1 is a curable resin composition comprising a curable resin, an imide oligomer, and diaspore-type aluminum hydroxide. Hereinafter, the present invention 1 will be described in detail.

The inventors of the present invention conducted research on the addition of diaspore-type aluminum hydroxide as a flame retardant to a curable resin composition containing a curable resin and an imide oligomer. As a result, they found that a curable resin composition that is excellent in flame retardancy, adhesiveness, high-temperature long-term heat resistance, and moisture absorption reflow resistance and has low environmental load can be obtained, and completed the present invention 1 .

The curable resin composition of the present invention 1 contains a curable resin. An epoxy resin can be used favorably as said curable resin. The above-mentioned epoxy resin is preferably a non-halogen-based epoxy resin produced without using a halogen compound as a raw material from the viewpoint of environmental load and the like.

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-cresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolak epoxy resin, naphthol novolac epoxy resin, glycidylamine epoxy resin, alkyl Polyol-type epoxy resins, rubber-modified epoxy resins, fennel-type epoxy resins, glycidyl ester compounds, etc. Among them, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E-type epoxy resin, resorcinol-type epoxy resin and other epoxy resins that are liquid at room temperature. The above epoxy resins may be used alone or in combination of two or more.

The curable resin composition of the present invention 1 contains an imide oligomer. The above-mentioned imide oligomer preferably has a reactive functional group capable of reacting with the above-mentioned curable resin. The reactive functional group also depends on the type of curable resin used, and when an epoxy resin is used as the curable resin, it is preferably an acid anhydride group and/or a phenolic hydroxyl group. The above-mentioned imide oligomer preferably has the above-mentioned reactive functional group at the terminal of the main chain, more preferably has the above-mentioned reactive functional group at both ends of the main chain.

Regarding the imide oligomer having an acid anhydride group as the above-mentioned reactive functional group, for example, a chain segment derived from an acid dianhydride represented by the following formula (1) and a chain segment derived from an acid dianhydride represented by the following formula (2) can be cited. The imide oligomer of the chain segment of the diamine, etc. In this case, it is preferable to have a segment derived from an acid dianhydride represented by the following formula (1) at the end of the main chain, and more preferably to have a segment derived from the following formula (1) at both ends of the main chain. The segment of the acid dianhydride represented.

In formula (1), A is a tetravalent group represented by the following formula (3-1) or the following formula (3-2).

In the formula (2), B is a divalent group represented by the following formula (4-1) or the following formula (4-2), and R ¹ to R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group.

In formula (3-1) and formula (3-2), * is the bonding position, in formula (3-1), Z is the bonding bond, oxygen atom, carbonyl, sulfur atom, sulfonyl group, bond A linear or branched divalent hydrocarbon group having an oxygen atom at the bonding position, or a divalent group having an aromatic ring which may have an oxygen atom at the bonding position. The hydrogen atoms of the aromatic rings in formula (3-1) and formula (3-2) may also be substituted.

In formula (4-1) and formula (4-2), * is the bonding position, in formula (4-1), Y is the bonding bond, oxygen atom, carbonyl, sulfur atom, sulfonyl group, bond A linear or branched divalent hydrocarbon group having an oxygen atom at the bonding position, or a divalent group having an aromatic ring which may have an oxygen atom at the bonding position. Part or all of the hydrogen atoms of the phenylene groups in the formulas (4-1) and (4-2) may be substituted with hydroxyl groups or monovalent hydrocarbon groups.

As a method of producing an imide oligomer having an acid anhydride group as the above-mentioned reactive functional group, for example, a method of reacting an acid dianhydride represented by the above formula (1) with a diamine represented by the above formula (2) method etc.

The specific example of the method of making the acid dianhydride represented by said formula (1) react with the diamine represented by said formula (2) is shown below. First, the diamine represented by the above formula (2) is dissolved in a solvent that can dissolve the amide acid oligomer obtained by the reaction (for example, N-methylpyrrolidone, dimethylformamide , dimethylacetamide, etc.), the acid dianhydride represented by the above formula (1) is added to the obtained solution, and reacted to obtain an amide acid oligomer solution. Then, remove the solvent from the obtained amide acid oligomer solution by heating or reducing pressure, or put it into a poor solvent such as water, methanol, hexane, etc. to make it reprecipitate, thereby recovering amide acid The oligomer is further heated at a temperature of about 200° C. or higher for 1 hour or more, so that the imidization reaction proceeds. The molar ratio of the acid dianhydride represented by the above formula (1) to the diamine represented by the above formula (2) and the imidization conditions can be adjusted to obtain the desired number average molecular weight and An imide oligomer having acid anhydride groups as reactive functional groups at both ends.

In addition, examples of the imide oligomer having a phenolic hydroxyl group as the reactive functional group include a segment derived from the acid dianhydride represented by the above formula (1) and a segment derived from the following formula (5). The imide oligomer of the chain segment of the monoamine containing the phenolic hydroxyl group etc. is shown. In this case, it is preferable to have a segment derived from a monoamine containing a phenolic hydroxyl group represented by the following formula (5) at the end of the main chain, and it is more preferable to have a segment derived from the following at both ends of the main chain. A chain segment of a monoamine containing a phenolic hydroxyl group represented by formula (5).

In formula (5), Ar is a divalent aromatic group that may be substituted, and R ⁵ and R ⁶ are independently hydrogen atoms or monovalent hydrocarbon groups.

As a method of producing an imide oligomer having a phenolic hydroxyl group as the above-mentioned reactive functional group, the following methods etc. are mentioned, for example. That is, the method of reacting the acid dianhydride represented by the above formula (1) with the phenolic hydroxyl group-containing monoamine represented by the above formula (5), or making the acid dianhydride represented by the above formula (1) A method of reacting a phenolic hydroxyl group-containing monoamine represented by the above formula (5) after reacting with the diamine represented by the above formula (2), and the like.

The specific example of the method of making the acid dianhydride represented by said formula (1) react with the phenolic hydroxyl group containing monoamine represented by said formula (5) is shown below. First, the phenolic hydroxyl group-containing monoamine represented by the above formula (5) is dissolved in a solvent (for example, N-methylpyrrolidone, di Methylformamide, dimethylacetamide, etc.), the acid dianhydride represented by the above formula (1) is added to the obtained solution, and reacted to obtain an amide acid oligomer solution. Then, remove the solvent from the obtained amide acid oligomer solution by heating or reducing pressure, or put it into a poor solvent such as water, methanol, hexane, etc. to make it reprecipitate, thereby recovering amide acid The oligomer is further heated at a temperature of about 200° C. or higher for 1 hour or more, so that the imidization reaction proceeds. The molar ratio of the acid dianhydride represented by the above formula (1) to the monoamine containing phenolic hydroxyl group represented by the above formula (5) and the imidization conditions can be adjusted to obtain the desired An imide oligomer having a number average molecular weight and having phenolic hydroxyl groups as reactive functional groups at both ends.

One of the methods of reacting the acid dianhydride represented by the above formula (1) with the diamine represented by the above formula (2), and then reacting the monoamine containing a phenolic hydroxyl group represented by the above formula (5) Specific examples are shown below. First, the diamine represented by the above formula (2) is dissolved in a solvent that can dissolve the amide acid oligomer obtained by the reaction (for example, N-methylpyrrolidone, dimethylformamide , dimethylacetamide, etc.), add the acid dianhydride represented by the above formula (1) to the obtained solution, and make it react to obtain an amic acid oligomer (A ) solution. Then, the solvent is removed from the solution of the obtained amide acid oligomer (A) by heating or reducing pressure, or it is put into a poor solvent such as water, methanol, hexane to make it reprecipitate, thereby The amide acid oligomer (A) is recovered, and then heated at a temperature of about 200° C. or higher for 1 hour or more, so that the imidization reaction proceeds. The imide oligomer having acid anhydride groups as reactive functional groups at both ends obtained in this way is dissolved again in a solvent (for example, N-methylpyrrolidone, dimethylformamide, dimethyl Acetamide, etc.), and add the phenolic hydroxyl group-containing monoamine represented by the above formula (5) for reaction to obtain a solution of the amide acid oligomer (B). Remove the solvent from the solution of the obtained amide acid oligomer (B) by heating or reducing pressure, or put it into a poor solvent such as water, methanol, or hexane to make it reprecipitate, thereby recovering the amide The amine acid oligomer (B) is further heated at a temperature of about 200° C. or higher for 1 hour or more, so that the imidization reaction proceeds. The molar ratio of the acid dianhydride represented by the above formula (1) to the diamine represented by the above formula (2) and the monoamine containing phenolic hydroxyl group represented by the above formula (5), and the amide The amination conditions are adjusted to obtain an imide oligomer having a desired number average molecular weight and having phenolic hydroxyl groups at both ends as reactive functional groups.

Examples of the acid dianhydride represented by the above formula (1) include pyromelteric dianhydride, 3,3'-oxydiphthalic acid dianhydride, 3,4'-oxydiphthalic acid di anhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, 4,4'-bis( 3,4-dicarboxyphenoxy)diphenyl ether, p-phenylene bis(trimellitic anhydride), 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' -Biphenyltetracarboxylic dianhydride, 4,4'-carbonyldiphthalic dianhydride, and the like. Among them, 4,4'-(4,4'-isopropylidene biphenyl Oxy)diphthalic anhydride, 3,4'-oxydiphthalic anhydride, 4,4'-oxydiphthalic anhydride, 4,4'-carbonyldiphthalic anhydride anhydride.

Examples of the diamine represented by the above formula (2) include: 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane Methane, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,2-phenylenediamine, 1,3- Phenylenediamine, 1,4-phenylenediamine, 3,3'-diaminodiphenylene, 4,4'-diaminodiphenylene, bis(4-(3-aminophenoxy ) phenyl) phenyl, bis (4-(4-aminophenoxy) phenyl) phenyl, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-amino Phenoxy)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) base)-2-propyl)benzene, 3,3'-diamino-4,4'-dihydroxyphenylmethane, 4,4'-diamino-3,3'-dihydroxyphenylmethane, 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, 3,3'-dihydroxybenzidine, etc. Among them, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'- Diaminodiphenyl ether, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, bis(4-(3-aminophenoxy)phenyl)pyridine, bis (4-(4-aminophenoxy)phenyl)phenyl, 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene, 1,3-bis(3-amine phenyloxy)benzene, 1,4-bis(2-(4-aminophenyl)-2-propyl)benzene, 3,3'-dihydroxybenzidine.

Examples of the phenolic hydroxyl-containing monoamine represented by the above formula (5) include 3-aminophenol, 4-aminophenol, 4-amino-o-cresol, and 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, 3-aminophenol, 4-aminophenol, and 4-amino-o-methanol are preferred in terms of excellent availability and storage stability, and the ability to obtain a hardened product having a high glass transition temperature. Phenol, 5-amino-o-cresol.

The preferable lower limit of the imidization rate of the above-mentioned imide oligomer is 70%. By setting the above imidization ratio to 70% or more, a cured product having more excellent mechanical strength at high temperature and high-temperature long-term heat resistance can be obtained. A more preferable lower limit of the imidization rate is 75%, and a more preferable lower limit is 80%. In addition, there is no particularly preferable upper limit for the imidization ratio of the above-mentioned imide oligomer, but the substantial upper limit is 98%. In addition, the said "imidization rate" can be calculated|required by Fourier transform infrared spectroscopy (FT-IR). Specifically, it can be measured by the total reflectance measurement method (ATR method) using a Fourier transform infrared spectrophotometer, and can be derived from the peak absorbance area around 1660 cm ^-1 derived from the carbonyl group of amide acid by the following formula. As said Fourier transform infrared spectrophotometer, UMA600 (made by Agilent Technologies) etc. are mentioned, for example. In addition, the "peak absorbance area of the amide acid oligomer" in the following formula is obtained by removing the solvent without performing the amide imidization step in each of the above-mentioned methods for producing the amide oligomer. The absorbance area of the obtained amide acid oligomer. The above-mentioned solvents can be removed by evaporation. Amidization rate (%)=100×(1-(peak absorbance area after imidization)/(peak absorbance area of amide acid oligomer))

The above-mentioned imide oligomers may be used alone or in combination of two or more.

The preferable lower limit of the number average molecular weight of the above-mentioned imide oligomer is 400, and the preferable upper limit is 5000. By setting the above-mentioned number average molecular weight within this range, the obtained cured product is more excellent in adhesiveness and high-temperature long-term heat resistance. A more preferable lower limit of the number average molecular weight of the above-mentioned imide oligomer is 500, and a more preferable upper limit is 4000. In addition, in this specification, the said "number average molecular weight" is the value calculated|required by polystyrene conversion measured by gel permeation chromatography (GPC). As a column used when measuring the number average molecular weight in terms of polystyrene by GPC, JAIGEL-2H-A (made by Nippon Analytical Industry Co., Ltd.) etc. are mentioned, for example.

The preferred upper limit of the softening point of the above-mentioned imide oligomer is 250°C. By setting the softening point of the above-mentioned imide oligomer to be 250° C. or lower, the obtained cured product has better adhesiveness and high-temperature long-term heat resistance. A more preferable upper limit of the softening point of the above-mentioned imide oligomer is 200°C. There is no particularly preferable lower limit for the softening point of the above-mentioned imide oligomer, and the lower limit is substantially 60°C. In addition, the softening point of the said imide oligomer can be calculated|required by the ring and ball method in accordance with JIS K 2207.

A preferable upper limit of the melting point of the above-mentioned imide oligomer is 300°C. By setting the melting point of the above-mentioned imide oligomer to 300° C. or lower, the obtained curable resin composition is more excellent in adhesiveness and high-temperature long-term heat resistance. A more preferable upper limit of the melting point of the above-mentioned imide oligomer is 250°C. In addition, the melting point of the above-mentioned imide oligomer can be determined by differential scanning calorimetry or a commercially available melting point detector.

The preferable lower limit of content of the said imide oligomer in 100 weight part of totals of the said curable resin and the said imide oligomer is 10 weight part, and a preferable upper limit is 90 weight part. By setting the content of the above-mentioned imide oligomer within this range, the cured product of the obtained curable resin composition has better mechanical strength at high temperature, adhesiveness, and high-temperature long-term heat resistance. A more preferable lower limit of the content of the above-mentioned imide oligomer is 20 parts by weight, and a more preferable upper limit is 80 parts by weight.

The curable resin composition of the present invention 1 may contain other curing agents in addition to the above-mentioned imide oligomers within the range that does not hinder the object of the present invention. Examples of the above-mentioned other curing agents include phenol-based curing agents, mercaptan-based curing agents, amine-based curing agents, acid anhydride-based curing agents, isocyanate-based curing agents, and active ester-based curing agents. Among these, phenol-based curing agents, acid anhydride-based curing agents, isocyanate-based curing agents, and active ester-based curing agents are preferred.

When the curable resin composition of the present invention 1 contains the above-mentioned other curing agent, the preferable upper limit of the content ratio of the above-mentioned other curing agent in the total of 100 parts by weight of the above-mentioned imide oligomer and the above-mentioned other curing agent is 70 parts by weight, a more preferable upper limit is 50 parts by weight, and a more preferable upper limit is 30 parts by weight.

The curable resin composition of the present invention 1 contains diaspore type aluminum hydroxide. By containing the above-mentioned diaspore-type aluminum hydroxide, the curable resin composition of the present invention 1 can have excellent flame retardancy without using halogen compounds and the like while maintaining excellent adhesiveness and high-temperature long-term heat resistance. And resistance to moisture absorption and reflow. Furthermore, it is preferable that the curable resin composition of the present invention 2 also contains diaspore-type aluminum hydroxide as described below.

The preferred lower limit of the average particle size of the above-mentioned diaspore-type aluminum hydroxide is 0.1 μm, and the preferred upper limit is 10 μm. By setting the average particle size of the above-mentioned diaspore-type aluminum hydroxide within this range, the dispersibility in the curable resin composition will not be deteriorated, and the dispersibility in the curable resin composition will not be deteriorated, and it will become a barrier to increase. The one with better flammability effect. A more preferable lower limit of the average particle diameter of the above-mentioned diaspore-type aluminum hydroxide is 0.5 μm, and a more preferable upper limit is 8 μm. In addition, the average particle diameter of the said diaspore type aluminum hydroxide can be measured by dispersing the said diaspore type aluminum hydroxide in a solvent (water, an organic solvent, etc.) using the particle size distribution measuring apparatus. As said particle size distribution measuring apparatus, NICOMP 380ZLS (made by PARTICLE SIZING SYSTEMS, Inc.) etc. are mentioned, for example.

The content of the diaspore-type aluminum hydroxide is preferably 10 parts by weight as the lower limit and 150 parts by weight as 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 diaspore-type aluminum hydroxide 10 weight part or more, the curable resin composition obtained becomes one more excellent in flame retardancy. By making content of the said diaspore-type aluminum hydroxide into 150 weight part or less, the curable resin composition obtained becomes what is more excellent in adhesiveness. The more preferable lower limit of the content of the above-mentioned diaspore-type aluminum hydroxide is 20 parts by weight, and the more preferable upper limit is 100 parts by weight.

The curable resin composition of the present invention 1 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 hardening accelerator include imidazole-based hardening accelerators, tertiary amine-based hardening accelerators, phosphine-based hardening accelerators, phosphorus-based hardening accelerators, photobase generators, and columium salt-based hardening accelerators. Among these, imidazole-based hardening accelerators are preferred in terms of excellent storage stability.

Regarding the content of the hardening accelerator, the lower limit is preferably 0.01 parts by weight, and the upper limit is preferably 10 parts by weight based on 100 parts by weight of the total of the curable resin and the imide oligomer. By making content of the said hardening accelerator into this range, the effect of shortening hardening time becomes more excellent in the state which maintained excellent adhesiveness etc.. A more preferable lower limit of the content of the above-mentioned hardening accelerator is 0.05 parts by weight, and a more preferable upper limit is 5 parts by weight.

The curable resin composition of the present invention 1 may also contain an inorganic filler in order to reduce the linear expansion coefficient after curing to reduce warping, or to further improve bonding reliability.

Examples of the inorganic filler include silicon dioxide (silica), barium sulfate, aluminum oxide, aluminum nitride, boron nitride, silicon nitride, aluminum hydroxide, magnesium hydroxide, glass powder, glass frit, glass fiber , carbon fiber, inorganic ion exchangers, etc.

The content of the inorganic filler is preferably 10 parts by weight in the lower limit and 300 parts by weight in the upper limit with respect 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, it becomes what makes the effect, such as improvement of adhesion|attachment reliability, more excellent in the state which maintained excellent processability etc.. A more preferable lower limit of the content of the above-mentioned inorganic filler is 20 parts by weight, and a more preferable upper limit is 200 parts by weight.

In addition, the inorganic filler can also be used as a flow regulator for the purpose of improving applicability and shape retention to an adherend in a short time, and the like.

Examples of inorganic fillers used as flow regulators include fumed silica such as Aerosil, layered silicates, and the like.

Regarding the content of the above-mentioned inorganic filler used as a flow regulator, the lower limit is preferably 0.1 parts by weight, and the upper limit is preferably 50 parts by weight relative to 100 parts by weight of the total of the above-mentioned curable resin and the above-mentioned imide oligomer. By setting the content of the inorganic filler used as the above-mentioned flow regulator within this range, effects such as improving applicability and shape retention to an adherend in a short period of time are more excellent. A more preferable lower limit of the content of the above-mentioned inorganic filler used as a 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 1 may contain an organic filler for the purpose of stress relaxation, toughness imparting, and the like. Examples of the organic filler include silicone rubber particles, acrylic rubber, urethane rubber particles, polyamide particles, polyamideimide particles, polyimide particles, benzoguanidine particles, and the like. Such as core-shell particles and so on. Among them, polyamide particles, polyamideimide particles, and polyimide particles are preferable.

Regarding content of the said organic filler, a preferable upper limit is 300 weight part with respect to 100 weight part of totals of the said curable resin and the said imide oligomer. By making content of the said organic filler into this range, the hardened|cured material obtained in the state which maintained excellent adhesiveness etc. becomes one more excellent in toughness etc. The more preferable upper limit of the content of the said organic filler is 200 weight part.

The curable resin composition of this invention 1 may contain a polymer compound within the range which does not hinder the object of this invention. The above-mentioned polymer compound functions as a film-forming component.

The above polymer compound may also have a reactive functional group. When the above polymer compound has a reactive functional group, the reactive functional group of the polymer compound includes, for example, an amine group, an urethane group, an imide group, a hydroxyl group, a carboxyl group, an epoxy group, etc. .

The curable resin composition of this invention 1 may contain a reactive diluent within the range which does not hinder the object of this 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. As a reactive functional group which the said reactive diluent has, the thing similar to the reactive functional group which the said polymer compound has is mentioned is mentioned.

The curable resin composition of the present invention 1 may further contain additives such as solvents, coupling agents, dispersants, storage stabilizers, anti-bleeding agents, fluxes, and leveling agents. As the above-mentioned solvent, methyl ethyl ketone can be preferably used.

As a method of producing the curable resin composition of the present invention 1, for example, mixing a curable resin, an imide, and the like with a mixer such as a homodisper, a universal mixer, a Banbury mixer, or a kneader can be enumerated. Polymer, diaspore-type aluminum hydroxide, and if necessary, a hardening accelerator or an inorganic filler, etc. are mixed.

The curable resin composition of the present invention 1 can be used in a wide range of applications, and can be favorably used in electronic material applications requiring high heat resistance. For example, it can be used as a die adhesive in the application of electrical control units (ECU) for aviation and vehicles, or power devices using SiC and GaN. Also, for example, it can be used as an adhesive for power cover packaging, a sealant, an adhesive for a flexible printed circuit board or a coverlay film, a copper-clad laminate, an adhesive for semiconductor bonding, an interlayer insulating film, a prepreg, and an LED. Sealants, adhesives for construction materials, etc. Among these, it can be suitably used for bonding of a flexible printed circuit board or a coverlay film.

Moreover, the cured product of the curable resin composition of the present invention 1 is also one of the present invention. Furthermore, an adhesive using the curable resin composition of the present invention 1 (hereinafter, also referred to as "adhesive of the present invention 1") is also one of the present invention. The adhesive film can be obtained by a method such as applying the adhesive agent of the present invention 1 on the film and then drying it. Moreover, the adhesive film which used the adhesive agent of this invention 1 is also one of this invention.

Invention 2 is a curable resin composition containing a curable resin, an imide oligomer, and an inorganic filler and having a melt viscosity at 180°C of 10 kPa·s or more and less than 1000 kPa·s. Hereinafter, the present invention 2 will be described in detail.

The inventors of the present invention studied to further blend an inorganic filler into a curable resin composition containing a curable resin and an imide oligomer, and to set the melt viscosity of the entire composition within a specific range. As a result, it was found that a curable resin composition excellent in adhesiveness, high-temperature long-term heat resistance, moisture absorption reflow resistance, plating resistance, low exudation during rapid pressing, and embedding property can be obtained, and completed the present invention 2 .

The curable resin composition of the present invention 2 contains a curable resin. An epoxy resin can be used favorably as said curable resin.

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-cresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolak epoxy resin, naphthol novolac epoxy resin, glycidylamine epoxy resin, alkyl Polyol-type epoxy resins, rubber-modified epoxy resins, fennel-type epoxy resins, glycidyl ester compounds, etc. Among them, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E-type epoxy resin, resorcinol-type epoxy resin and other epoxy resins that are liquid at room temperature. The above epoxy resins may be used alone or in combination of two or more.

The curable resin composition of the present invention 2 contains an imide oligomer. The above-mentioned imide oligomer preferably has a reactive functional group capable of reacting with the above-mentioned curable resin. The above-mentioned reactive functional group also depends on the type of curable resin used, and when an epoxy resin is used as the curable resin, it is preferably an acid anhydride group and/or a phenolic hydroxyl group. The above-mentioned imide oligomer preferably has the above-mentioned reactive functional group at the terminal of the main chain, more preferably has the above-mentioned reactive functional group at both ends of the main chain.

Examples of the imide oligomer having an acid anhydride group as the above-mentioned reactive functional group include an acid dianhydride derived segment represented by the following formula (6) and a diamine represented by the following formula (7). Segment-derived imide oligomers, etc. In this case, it is preferable to have an acid dianhydride segment derived from the following formula (6) at the end of the main chain, and more preferably to have an acid dianhydride segment derived from the following formula (6) at both ends of the main chain. Represents the acid dianhydride segment.

In formula (6), A is a tetravalent group represented by the following formula (8-1) or the following formula (8-2).

In the formula (7), B is a divalent group represented by the following formula (9-1) or the following formula (9-2), and R ⁷ to R ¹⁰ are each independently a hydrogen atom or a monovalent hydrocarbon group.

In formula (8-1) and formula (8-2), * is the bonding position, in formula (8-1), Z is the bonding bond, oxygen atom, carbonyl, sulfur atom, sulfonyl group, bond A linear or branched divalent hydrocarbon group having an oxygen atom at the bonding position, or a divalent group having an aromatic ring which may have an oxygen atom at the bonding position. The hydrogen atoms of the aromatic rings in formula (8-1) and formula (8-2) may also be substituted.

In formula (9-1) and formula (9-2), * is the bonding position, in formula (9-1), Y is the bonding bond, oxygen atom, carbonyl, sulfur atom, sulfonyl group, bond A linear or branched divalent hydrocarbon group having an oxygen atom at the bonding position, or a divalent group having an aromatic ring which may have an oxygen atom at the bonding position. Part or all of the hydrogen atoms of the phenylene groups in the formulas (9-1) and (9-2) may be substituted with hydroxyl groups or monovalent hydrocarbon groups.

As a method of producing an imide oligomer having an acid anhydride group as the above-mentioned reactive functional group, for example, the method of reacting the acid dianhydride represented by the above formula (6) with the diamine represented by the above formula (7) method etc.

The specific example of the method of making the acid dianhydride represented by said formula (6) and the diamine represented by said formula (7) react is shown below. First, the diamine represented by the above formula (7) is dissolved in a solvent that can dissolve the amide acid oligomer obtained by the reaction (for example, N-methylpyrrolidone, dimethylformamide , dimethylacetamide, etc.), the acid dianhydride represented by the above formula (6) was added to the obtained solution to react, and an amide acid oligomer solution was obtained. Then, remove the solvent from the obtained amide acid oligomer solution by heating or reducing pressure, or put it into a poor solvent such as water, methanol, hexane, etc. to make it reprecipitate, thereby recovering amide acid The oligomer is further heated at a temperature of about 200° C. or higher for 1 hour or more, so that the imidization reaction proceeds. The molar ratio of the acid dianhydride represented by the above formula (6) to the diamine represented by the above formula (7) and the imidization conditions can be adjusted to obtain the desired number average molecular weight and An imide oligomer having acid anhydride groups as reactive functional groups at both ends.

In addition, examples of the imide oligomer having a phenolic hydroxyl group as the reactive functional group include a segment derived from the acid dianhydride represented by the above formula (6) and a segment derived from the following formula (10). The imide oligomers of monoamine chain segments containing phenolic hydroxyl groups are represented. In this case, it is preferable to have a segment derived from a monoamine containing a phenolic hydroxyl group represented by the following formula (10) at the end of the main chain, and it is more preferable to have a segment derived from the following at both ends of the main chain. A chain segment of a monoamine containing a phenolic hydroxyl group represented by formula (10).

In formula (10), Ar is a divalent aromatic group that may be substituted, and R ¹¹ and R ¹² are independently hydrogen atoms or monovalent hydrocarbon groups.

As a method of producing an imide oligomer having a phenolic hydroxyl group as the above-mentioned reactive functional group, the following methods etc. are mentioned, for example. That is, the method of reacting the acid dianhydride represented by the above formula (6) with the phenolic hydroxyl group-containing monoamine represented by the above formula (10), or the method of reacting the acid dihydride represented by the above formula (6) A method of reacting the diamine represented by the above formula (7) with the anhydride, and then reacting the phenolic hydroxyl group-containing monoamine represented by the above formula (10), etc.

The specific example of the method of making the acid dianhydride represented by said formula (6) and the phenolic hydroxyl group containing monoamine represented by said formula (10) react is shown below. First, the phenolic hydroxyl group-containing monoamine represented by the above formula (10) is dissolved in a solvent (for example, N-methylpyrrolidone, di Methylformamide, dimethylacetamide, etc.), the acid dianhydride represented by the above formula (6) is added to the obtained solution to react, and an amide acid oligomer solution is obtained. Then, remove the solvent from the obtained amide acid oligomer solution by heating or reducing pressure, or put it into a poor solvent such as water, methanol, hexane, etc. to make it reprecipitate, thereby recovering amide acid The oligomer is further heated at a temperature of about 200° C. or higher for 1 hour or more, so that the imidization reaction proceeds. The molar ratio of the acid dianhydride represented by the above formula (6) to the monoamine containing phenolic hydroxyl group represented by the above formula (10) and the imidization conditions can be adjusted to obtain the desired An imide oligomer having a number average molecular weight and having phenolic hydroxyl groups as reactive functional groups at both ends.

A method in which the acid dianhydride represented by the above formula (6) is reacted with the diamine represented by the above formula (7), and then the monoamine containing a phenolic hydroxyl group represented by the above formula (10) is reacted The specific example is shown below. First, the diamine represented by the above-mentioned formula (7) is dissolved in a solvent capable of dissolving the amide acid oligomer obtained by the reaction (for example, N-methylpyrrolidone, dimethylformamide , dimethylacetamide, etc.), add the acid dianhydride represented by the above formula (6) to the obtained solution to react, and obtain the amide acid oligomer (A) having acid anhydride groups at both ends solution. Then, the solvent is removed from the solution of the obtained amide acid oligomer (A) by heating or reducing pressure, or it is put into a poor solvent such as water, methanol, hexane to make it reprecipitate, thereby The amide acid oligomer (A) is recovered, and then heated at a temperature of about 200° C. or higher for 1 hour or more, so that the imidization reaction proceeds. The imide oligomer having acid anhydride groups as reactive functional groups at both ends obtained in this way is dissolved again in a solvent (for example, N-methylpyrrolidone, dimethylformamide, dimethyl Acetamide, etc.), and add the phenolic hydroxyl group-containing monoamine represented by the above formula (10) to react to obtain a solution of the amide acid oligomer (B). The amide is recovered by removing the solvent from the obtained solution of the amide acid oligomer (B) by heating or reducing pressure, or putting it into a poor solvent such as water, methanol, or hexane to reprecipitate it The acid oligomer (B) is further heated at a temperature of about 200° C. or higher for 1 hour or more to advance the imidization reaction. The molar ratio of the acid dianhydride represented by the above formula (6), the diamine represented by the above formula (7) and the monoamine containing phenolic hydroxyl group represented by the above formula (10), and the amide The amination conditions are adjusted to obtain an imide oligomer having a desired number average molecular weight and having phenolic hydroxyl groups at both ends as reactive functional groups.

Examples of the acid dianhydride represented by the above formula (6) include pyromelteric dianhydride, 3,3'-oxydiphthalic acid dianhydride, 3,4'-oxydiphthalic acid di anhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, 4,4'-bis( 3,4-dicarboxyphenoxy)diphenyl ether, p-phenylene bis(trimellitic anhydride), 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' -Biphenyltetracarboxylic dianhydride, 4,4'-carbonyldiphthalic dianhydride, and the like. Among them, 4,4'-(4,4'-isopropylidene biphenyl Oxy)diphthalic anhydride, 3,4'-oxydiphthalic anhydride, 4,4'-oxydiphthalic anhydride, 4,4'-carbonyldiphthalic anhydride anhydride.

Examples of the diamine represented by the above formula (7) include: 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane Methane, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,2-phenylenediamine, 1,3- Phenylenediamine, 1,4-phenylenediamine, 3,3'-diaminodiphenylene, 4,4'-diaminodiphenylene, bis(4-(3-aminophenoxy ) phenyl) phenyl, bis (4-(4-aminophenoxy) phenyl) phenyl, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-amino Phenoxy)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) base)-2-propyl)benzene, 3,3'-diamino-4,4'-dihydroxyphenylmethane, 4,4'-diamino-3,3'-dihydroxyphenylmethane, 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, 3,3'-dihydroxybenzidine, etc. Among them, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'- Diaminodiphenyl ether, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, bis(4-(3-aminophenoxy)phenyl)pyridine, bis (4-(4-aminophenoxy)phenyl)phenyl, 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene, 1,3-bis(3-amine phenyloxy)benzene, 1,4-bis(2-(4-aminophenyl)-2-propyl)benzene, 3,3'-dihydroxybenzidine.

Examples of the phenolic hydroxyl-containing monoamine represented by the above formula (10) include: 3-aminophenol, 4-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, 3-aminophenol, 4-aminophenol, and 4-amino-o-methanol are preferred in terms of excellent availability and storage stability, and the ability to obtain a hardened product having a high glass transition temperature. Phenol, 5-amino-o-cresol.

The preferable lower limit of the imidization rate of the above-mentioned imide oligomer is 70%. By setting the above imidization ratio to 70% or more, a cured product having more excellent mechanical strength at high temperature and high-temperature long-term heat resistance can be obtained. A more preferable lower limit of the imidization rate is 75%, and a more preferable lower limit is 80%. In addition, there is no particularly preferable upper limit for the imidization ratio of the above-mentioned imide oligomer, but the substantial upper limit is 98%. In addition, the said "imidization rate" can be calculated|required by Fourier transform infrared spectroscopy (FT-IR). Specifically, it can be measured by the total reflectance measurement method (ATR method) using a Fourier transform infrared spectrophotometer, and can be derived from the peak absorbance area around 1660 cm ^-1 derived from the carbonyl group of amide acid by the following formula. As said Fourier transform infrared spectrophotometer, UMA600 (made by Agilent Technologies) etc. are mentioned, for example. In addition, the "peak absorbance area of the amide acid oligomer" in the following formula is obtained by removing the solvent without performing the amide imidization step in each of the above-mentioned methods for producing the amide oligomer. The absorbance area of the obtained amide acid oligomer. The above-mentioned solvents can be removed by evaporation. Amidization rate (%)=100×(1-(peak absorbance area after imidization)/(peak absorbance area of amide acid oligomer))

The above-mentioned imide oligomers may be used alone or in combination of two or more.

The preferable lower limit of the number average molecular weight of the above-mentioned imide oligomer is 400, and the preferable upper limit is 5000. By setting the above-mentioned number average molecular weight within this range, the obtained cured product is more excellent in adhesiveness and high-temperature long-term heat resistance. A more preferable lower limit of the number average molecular weight of the above-mentioned imide oligomer is 500, and a more preferable upper limit is 4000. In addition, in this specification, the said "number average molecular weight" is the value calculated|required by polystyrene conversion measured by gel permeation chromatography (GPC). As a column used when measuring the number average molecular weight in terms of polystyrene by GPC, JAIGEL-2H-A (made by Nippon Analytical Industry Co., Ltd.) etc. are mentioned, for example.

The preferred upper limit of the softening point of the above-mentioned imide oligomer is 250°C. By setting the softening point of the above-mentioned imide oligomer to be 250° C. or lower, the obtained cured product has better adhesiveness and high-temperature long-term heat resistance. A more preferable upper limit of the softening point of the above-mentioned imide oligomer is 200°C. There is no particularly preferable lower limit for the softening point of the above-mentioned imide oligomer, and the lower limit is substantially 60°C. In addition, the softening point of the said imide oligomer can be calculated|required by the ring and ball method in accordance with JIS K 2207.

A preferable upper limit of the melting point of the above-mentioned imide oligomer is 300°C. By setting the melting point of the above-mentioned imide oligomer to 300° C. or lower, the obtained curable resin composition is more excellent in adhesiveness and high-temperature long-term heat resistance. A more preferable upper limit of the melting point of the above-mentioned imide oligomer is 250°C. In addition, the melting point of the above-mentioned imide oligomer can be determined by differential scanning calorimetry or a commercially available melting point detector.

The preferable lower limit of content of the said imide oligomer in 100 weight part of totals of the said curable resin and the said imide oligomer is 10 weight part, and a preferable upper limit is 90 weight part. By setting the content of the above-mentioned imide oligomer within this range, the cured product of the obtained curable resin composition has better mechanical strength at high temperature, adhesiveness, and high-temperature long-term heat resistance. A more preferable lower limit of the content of the above-mentioned imide oligomer is 20 parts by weight, and a more preferable upper limit is 80 parts by weight.

The curable resin composition of the present invention 2 may contain other curing agents in addition to the above-mentioned imide oligomers within the range that does not hinder the object of the present invention. Examples of the above-mentioned other curing agents include phenol-based curing agents, mercaptan-based curing agents, amine-based curing agents, acid anhydride-based curing agents, isocyanate-based curing agents, and active ester-based curing agents. Among these, phenol-based curing agents, acid anhydride-based curing agents, isocyanate-based curing agents, and active ester-based curing agents are preferred.

When the curable resin composition of the present invention 2 contains the above-mentioned other curing agent, the preferable upper limit of the content ratio of the above-mentioned other curing agent in a total of 100 parts by weight of the above-mentioned imide oligomer and the above-mentioned other curing agent is 70 parts by weight, a more preferable upper limit is 50 parts by weight, and a more preferable upper limit is 30 parts by weight.

The curable resin composition of the present invention 2 contains an inorganic filler. By containing the above-mentioned inorganic filler, the curable resin composition of the present invention 2 has low moisture absorption reflow resistance, plating resistance, and rapid pressing while maintaining excellent adhesiveness and high-temperature long-term heat resistance. Those with excellent exudation.

The above-mentioned inorganic filler is preferably at least any one of silicon dioxide and barium sulfate. By containing at least one of silicon dioxide and barium sulfate as the above-mentioned inorganic filler, the curable resin composition of the present invention 2 has better moisture absorption reflow resistance, plating resistance, and low exudation during rapid pressing. Excellent.

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

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

The preferable upper limit of the average particle diameter of the said inorganic filler is 4 micrometers. By setting the average particle diameter of the above-mentioned inorganic filler to be 4 μm or less, the obtained curable resin composition is more excellent in low exudation property at the time of rapid pressing. The more preferable upper limit of the average particle diameter of the said inorganic filler is 3 micrometers. In addition, from the viewpoint of better coatability or embedding property during rapid pressing, the lower limit of the average particle diameter of the above-mentioned inorganic filler is preferably 5 nm, and the lower limit is more preferably 10 nm. In addition, the average particle diameter of the above-mentioned inorganic filler or the flow regulator described below can be measured by dispersing the above-mentioned inorganic filler or flow regulator in a solvent (water, organic solvent, etc.) using a particle size distribution measuring device, for example. As said particle size distribution measuring apparatus, NICOMP 380ZLS (made by PARTICLE SIZING SYSTEMS, Inc.) etc. are mentioned, for example.

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 with respect to 100 parts by weight of the total of the curable resin and the imide oligomer. By setting the content of the above-mentioned inorganic filler to be 10 parts by weight or more, the obtained curable resin composition is more excellent in moisture absorption reflow resistance, plating resistance, and low exudation during rapid pressing. By making content of the said inorganic filler into 150 weight part or less, the curable resin composition obtained becomes one more excellent in adhesiveness and embedding property at the time of rapid pressing. The more preferable lower limit of content of the said inorganic filler is 20 weight part.

The curable resin composition of the present invention 2 may contain a flow regulator for the purpose of improving applicability and shape retention to an adherend in a short time, in addition to the above-mentioned inorganic filler. As said flow regulator, fumed silica such as Aerosil, layered silicate, etc. are mentioned, for example. In addition, as the above-mentioned flow regulator, one having an average particle diameter of less than 100 nm can be preferably used.

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 with respect to 100 parts by weight of the total of the curable resin and the imide oligomer. By making content of the said flow regulator into this range, effects, such as improvement of applicability and shape retention property to an adherend in a short time, become 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 2 may contain an organic filler for the purpose of stress relaxation, toughness imparting, and the like. Examples of the organic filler include silicone rubber particles, acrylic rubber, urethane rubber particles, polyamide particles, polyamideimide particles, polyimide particles, benzoguanidine particles, and the like. Such as core-shell particles and so on. Among them, polyamide particles, polyamideimide particles, and polyimide particles are preferable.

Regarding content of the said organic filler, a preferable upper limit is 300 weight part with respect to 100 weight part of totals of the said curable resin and the said imide oligomer. By making content of the said organic filler into this range, the hardened|cured material obtained in the state which maintained excellent adhesiveness etc. becomes one more excellent in toughness 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 2 may contain a flame retardant in order to impart flame retardancy. Examples of the flame retardant include diaspore-type aluminum hydroxide, metal hydrates such as aluminum hydroxide and magnesium hydroxide, halogen compounds, phosphorus compounds, and nitrogen compounds. Among them, diaspore-type aluminum hydroxide is preferred. The average particle diameter and content of the above-mentioned diaspore-type aluminum hydroxide are preferably in the same range as the above-mentioned present invention 1.

Regarding the content of the flame retardant, the lower limit is preferably 5 parts by weight, and the upper limit is preferably 200 parts by weight based on 100 parts by weight of the total of the curable resin and the imide oligomer. By making content of the said flame retardant into this range, the curable resin composition obtained becomes what is more excellent in flame retardancy in the state which maintained 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 2 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 hardening accelerator include imidazole-based hardening accelerators, tertiary amine-based hardening accelerators, phosphine-based hardening accelerators, phosphorus-based hardening accelerators, photobase generators, and columium salt-based hardening accelerators. Among these, imidazole-based hardening accelerators are preferred in terms of excellent storage stability.

Regarding the content of the hardening accelerator, the lower limit is preferably 0.01 parts by weight, and the upper limit is preferably 10 parts by weight based on 100 parts by weight of the total of the curable resin and the imide oligomer. By making content of the said hardening accelerator into this range, the effect of shortening hardening time becomes more excellent in the state which maintained excellent adhesiveness etc.. A more preferable lower limit of the content of the above-mentioned hardening accelerator is 0.05 parts by weight, and a more preferable upper limit is 5 parts by weight.

The curable resin composition of this invention 2 may contain a polymer compound within the range which does not hinder the object of this invention. The above-mentioned polymer compound functions as a film-forming component.

The above polymer compound may also have a reactive functional group. When the above polymer compound has a reactive functional group, the reactive functional group of the polymer compound includes, for example, an amine group, an urethane group, an imide group, a hydroxyl group, a carboxyl group, an epoxy group, etc. .

The curable resin composition of this invention 2 may contain a reactive diluent within the range which does not hinder the object of this 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. As a reactive functional group which the said reactive diluent has, the thing similar to the reactive functional group which the said polymer compound has is mentioned is mentioned.

The curable resin composition of the present invention 2 may further contain additives such as solvents, coupling agents, dispersants, storage stabilizers, anti-bleeding agents, fluxes, and leveling agents. As the above-mentioned solvent, methyl ethyl ketone can be preferably used.

As a method of producing the curable resin composition of the present invention 2, for example, mixing a curable resin, an imide oligomer, etc. , inorganic fillers, and optional hardening accelerators or flow regulators, etc., are mixed.

The curable resin composition of the present invention 2 has a melt viscosity at 180°C of not less than 10 kPa·s and less than 1000 kPa·s. By setting the above-mentioned melt viscosity at 180°C to 10 kPa·s or more, the curable resin composition of the present invention 2 is excellent in moisture absorption reflow resistance, plating resistance, and low exudation during rapid pressing. By keeping the melt viscosity at 180°C below 1000 kPa·s, the curable resin composition of the present invention 2 is excellent in adhesiveness and embedding property at the time of rapid pressing. The lower limit of the melt viscosity at 180°C is preferably 20 kPa·s, the upper limit is 900 kPa·s, the lower limit is 50 kPa·s, and the upper limit is 850 kPa·s. In addition, the above-mentioned melt viscosity at 180°C is for a curable resin composition (curable resin composition film) in a B-stage state in which the solvent has been removed by coating and drying steps, etc., using a rotational rheometer at a frequency It is obtained in the form of the viscosity at 180°C when the viscosity is measured while heating under the condition of 1 Hz and a heating rate of 10°C/min. Examples of the rotational rheometer include HAAKE MARS Series (manufactured by Thermo Fisher Scientific), VAR-100 (manufactured by Reologica), and the like. In addition, the above-mentioned curable resin composition of the present invention 1 also preferably has a melt viscosity at 180° C. of 10 kPa·s or more and less than 1000 kPa·s.

The curable resin composition of the present invention 2 can be used in a wide range of applications, and can be favorably used in electronic material applications requiring high heat resistance. For example, it can be used as a die adhesive in the application of electrical control units (ECU) for aviation and vehicles, or power devices using SiC and GaN. Also, for example, it can be used as an adhesive for power cover packaging, a sealant, an adhesive for a flexible printed circuit board or a coverlay film, a copper-clad laminate, an adhesive for semiconductor bonding, an interlayer insulating film, a prepreg, and an LED. Sealants, adhesives for construction materials, etc. Among these, it can be suitably used for bonding of a flexible printed circuit board or a coverlay film.

The cured product of the curable resin composition of the present invention 2 is also one of the present inventions. Adhesives using the curable resin composition of the present invention 2 (hereinafter also referred to as "adhesives of the present invention 2") are also one of the present inventions. The adhesive film can be obtained by a method such as applying the adhesive agent of the present invention 2 on the film and then drying it. The adhesive film formed by using the adhesive of the present invention 2 is also one of the present inventions. [Effect of Invention]

According to the present invention, it is possible to provide a curable resin composition which is excellent in flame retardancy, adhesiveness, high-temperature long-term heat resistance, and moisture absorption reflow resistance and has low environmental load. Furthermore, according to the present invention, a cured product of the curable resin composition, and an adhesive and an adhesive film using the curable resin composition can be provided. Also, according to the present invention, it is possible to provide a curable resin composition excellent in adhesiveness, high-temperature long-term heat resistance, moisture absorption reflow resistance, plating resistance, low exudation during rapid pressing, and embedding property. Furthermore, according to the present invention, a cured product of the curable resin composition, and an adhesive and an adhesive film using the curable resin composition can be provided.

The following examples are given to illustrate the present invention in further detail, but the present invention is not limited to these examples.

(Synthesis example 1-1 (production of imide oligomer 1-A)) Dissolve 17.2 parts by weight of 1,4-bis(2-(4-aminophenyl)-2-propyl)benzene in N - in 200 parts by weight of methylpyrrolidone. As 1,4-bis(2-(4-aminophenyl)-2-propyl)benzene, Bisaniline P (manufactured by Mitsui Fine Chemicals Co., Ltd.) was used, and as N-methylpyrrolidone, FUJIFILM Wako Pure Chemical was used Reagent manufactured by Corporation. 52.0 parts by weight of 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride was added to the obtained solution, and stirred at 25°C for 2 hours to react to obtain Amino acid oligomer solution. As 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride, the reagent manufactured by Tokyo Chemical Industry Co., Ltd. was used. N-methylpyrrolidone was removed under reduced pressure from the obtained amide acid oligomer solution, and then heated at 300° C. for 2 hours to obtain amide imide oligomer 1-A (amide amide Amination rate 97%). Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the imide oligomer 1-A contains an imide oligomer represented by the following formula (11) as a main component. In addition, the softening point of the imide oligomer 1-A was 155°C, and the melting point was 170°C.

(Synthesis example 1-2 (production of imide oligomer 1-B)) 21.8 parts by weight of 3-aminophenol was dissolved in 200 parts by weight of N-methylpyrrolidone. 17.2 parts by weight of 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride was added to the obtained solution, and stirred at 25°C for 2 hours to react to obtain Amino acid oligomer solution. N-methylpyrrolidone was removed under reduced pressure from the obtained amide acid oligomer solution, and then heated at 300° C. for 2 hours to obtain amide imide oligomer 1-B (amide amide Amination rate 96%). Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the imide oligomer 1-B contains an imide oligomer represented by the following formula (12) as a main component. Also, the softening point of the imide oligomer 1-B was 134°C, and the melting point was 154°C.

(Examples 1 to 13, Comparative Examples 1 to 4) Each material was stirred and mixed according to the blending ratios recorded in Tables 1 and 2 to prepare the curable resin compositions of Examples 1 to 13 and Comparative Examples 1 to 4.

＜Evaluation＞ The following evaluations were performed for each of the curable resin compositions obtained in Examples 1 to 13 and Comparative Examples 1 to 4. The results are shown in Tables 1 and 2.

(flame retardant) Each of the curable resin compositions obtained in Examples 1 to 13 and Comparative Examples 1 to 4 was coated on a polyimide substrate (thickness 25 μm) so that the thickness became about 20 μm, and dried. This results in a bonded film. As the polyimide base material, Kapton 100H (manufactured by TORAY-DUPONT Co., Ltd.) was used. The obtained adhesive film was heated at 190° C. for 1 hour to obtain a cured film in which a cured product was formed on one side of the polyimide substrate. The obtained cured film was cut into a size of 5 inches in length x 1/2 inch in width to prepare a test piece. For the obtained test piece, the flame retardancy was evaluated according to the vertical burning test stipulated in UL-94 of the American UL standard.

(5% weight loss temperature) Each of the curable resin compositions obtained in Examples 1 to 13 and Comparative Examples 1 to 4 was coated on a release PET film and dried to obtain an adhesive film with a thickness of 20 μm. For the cured product obtained by heating the obtained adhesive film at 190°C for 1 hour and hardening, use a thermogravimetric measuring device to measure the temperature of 5% weight loss in the temperature range of 40°C to 450°C and the heating condition of 10°C/min To measure. As a thermogravimetric measuring device, EXTEAR TG/DTA6200 (manufactured by SII Nano Technology Co., Ltd.) was used.

(adherence) Each of the curable resin compositions obtained in Examples 1 to 13 and Comparative Examples 1 to 4 was coated on a release PET film so that the thickness became about 20 μm, and dried to obtain an adhesive film. The PET film was peeled off from the obtained adhesive film, and the polyimide base material (thickness 50 μm) was bonded on both sides of the adhesive layer while heating to 80° C. using a laminating machine. As the polyimide base material, Kapton 200H (manufactured by TORAY-DUPONT Co., Ltd.) was used. Hot pressing was carried out under the conditions of 190°C, 3 MPa, and 1 hour to harden the adhesive layer, and thereafter, a test piece was obtained by cutting into a width of 1 cm. The obtained test piece was subjected to T-peeling with a tensile testing machine at a peeling speed of 20 mm/min, and the adhesive force was measured. As a tensile tester, UCT-500 (manufactured by ORIENTEC) was used. The case where the adhesive force is 3.4 N/cm or more is set as "〇", the case of 2.0 N/cm or more and less than 3.4 N/cm is set as "△", and the case of less than 2.0 N/cm is set as "△". "x" was evaluated for adhesiveness.

(high temperature long-term heat resistance) Heat treatment was performed at 175° C. for 1,000 hours for the test piece obtained in the same manner as the evaluation of the above-mentioned “(adhesion)”. For the heat-treated test piece, use a tensile testing machine to perform T-peeling at a peeling speed of 20 mm/min, and measure the adhesive force. As a tensile tester, UCT-500 (manufactured by ORIENTEC) was used. The case where the adhesive force is 3.4 N/cm or more is set as "〇", the case of 2.0 N/cm or more and less than 3.4 N/cm is set as "△", and the case of less than 2.0 N/cm is set as "△". "x" is evaluated for high-temperature long-term heat resistance.

(Moisture absorption and reflow resistance) For the test piece obtained in the same way as the above "(adhesion)" evaluation, let it stand in an environment of 40°C and 90%RH for 3 days, and then perform moisture absorption by heating at 260°C for 20 seconds. welding test. For the test piece after the moisture absorption reflow test, visually confirm the presence or absence of air bubbles. The case where air bubbles were not confirmed was made "o", and the case where air bubbles were confirmed was made "x", and the moisture absorption reflow resistance was evaluated.

(plating resistance) Each of the curable resin compositions obtained in Examples 1 to 13 and Comparative Examples 1 to 4 was coated on a polyimide substrate (thickness 25 μm) so that the thickness became about 20 μm, and dried. Thereby, an adhesive film is obtained. As the polyimide base material, Kapton 100H (manufactured by TORAY-DUPONT Co., Ltd.) was used. An opening of 10 mm×10 mm was set on the obtained adhesive film, and it was attached 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. The copper-clad laminates with the configuration are used to make samples for FPC evaluation. In addition, bonding was performed by hot pressing under the conditions of 190 degreeC, 3 MPa, and 1 hour. The obtained samples for FPC evaluation were plated under conditions of 5 μm nickel and 0.05 μm gold using commercially available electroless nickel plating bath and electroless gold plating bath at 80°C to 90°C. Use an optical microscope to observe the end of the adhesive film at the opening, and set the case where the leaching of the plating solution was not confirmed as "O", and the case where the leaching of the plating solution was confirmed at the end as "X". repeatable evaluation.

[Table 1]

[Table 2]

(Synthesis example 2-1 (production of imide oligomer 2-A)) Dissolve 17.2 parts by weight of 1,4-bis(2-(4-aminophenyl)-2-propyl)benzene in N - in 200 parts by weight of methylpyrrolidone. As 1,4-bis(2-(4-aminophenyl)-2-propyl)benzene, Bisaniline P (manufactured by Mitsui Fine Chemicals Co., Ltd.) was used, and as N-methylpyrrolidone, FUJIFILM Wako Pure Chemical was used Reagent manufactured by Corporation. 52.0 parts by weight of 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride was added to the obtained solution, and stirred at 25°C for 2 hours to react to obtain Amino acid oligomer solution. As 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride, the reagent manufactured by Tokyo Chemical Industry Co., Ltd. was used. N-methylpyrrolidone was removed under reduced pressure from the obtained amide acid oligomer solution, and then heated at 300°C for 2 hours to obtain amide imide oligomer 2-A (amide amide Amination rate 97%). Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the imide oligomer 2-A contains an imide oligomer represented by the following formula (13) as a main component. In addition, the softening point of the imide oligomer 2-A was 155°C, and the melting point was 170°C.

(Synthesis example 2-2 (production of imide oligomer 2-B)) 21.8 parts by weight of 3-aminophenol was dissolved in 200 parts by weight of N-methylpyrrolidone. 17.2 parts by weight of 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride was added to the obtained solution, and stirred at 25°C for 2 hours to react to obtain Amino acid oligomer solution. N-Methylpyrrolidone was removed under reduced pressure from the obtained amide acid oligomer solution, and then heated at 300°C for 2 hours to obtain amide oligomer 2-B (amide Amination rate 96%). Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the imide oligomer 2-B contains an imide oligomer represented by the following formula (14) as a main component. Also, the softening point of the imide oligomer 2-B was 134°C, and the melting point was 154°C.

(Examples 14 to 22, Comparative Examples 5 to 8) Each material was stirred and mixed according to the blending ratio recorded in Table 3, and each curable resin composition of Examples 14-22 and Comparative Examples 5-8 was prepared. The obtained curable resin composition was coated on a release PET film so that the thickness was about 20 μm, and dried to obtain a curable resin composition film. The PET film was peeled off from the obtained curable resin composition film, and the melt viscosity at 180°C was measured using a rotary rheometer when the viscosity was measured while heating at a frequency of 1 Hz and a temperature increase rate of 10°C/min. Determination. As the rotational rheometer, HAAKE MARS III (manufactured by Thermo Fisher Scientific) was used. The results are shown in Table 3.

＜Evaluation＞ The following evaluations were performed on each of the curable resin compositions obtained in Examples 14 to 22 and Comparative Examples 5 to 8. The results are shown in Table 3.

(adherence) Each of the curable resin compositions obtained in Examples 14 to 22 and Comparative Examples 5 to 8 was coated on a release PET film so that the thickness became about 20 μm, and dried to obtain an adhesive film. The PET film was peeled off from the obtained adhesive film, and the polyimide substrate (50 μm in thickness) was bonded to both sides of the adhesive layer while heating to 80° C. using a laminating machine. As the polyimide base material, Kapton 200H (manufactured by TORAY-DUPONT Co., Ltd.) was used. Hot pressing was carried out at 190°C, 3 MPa, and 1 hour to harden the adhesive layer, and then cut into 1 cm wide to obtain test pieces. The obtained test piece was subjected to T-peeling with a tensile testing machine at a peeling speed of 20 mm/min, and the adhesive force was measured. As a tensile tester, UCT-500 (manufactured by ORIENTEC) was used. The case where the adhesive force was 3.4 N/cm or more was set as "O", the case of 2.0 N/cm or more and less than 3.4 N/cm was set as "△", and the case of less than 2.0 N/cm was set as " ×", the adhesiveness was evaluated.

(high temperature long-term heat resistance) Heat treatment was performed at 175° C. for 1,000 hours for the test piece obtained in the same manner as the evaluation of the above-mentioned “(adhesion)”. For the heat-treated test piece, a tensile tester was used to perform T-peeling at a peeling speed of 20 mm/min, and the adhesive force was measured. As a tensile tester, UCT-500 (manufactured by ORIENTEC) was used. The case where the adhesive force was 3.4 N/cm or more was set as "O", the case of 2.0 N/cm or more and less than 3.4 N/cm was set as "△", and the case of less than 2.0 N/cm was set as " ×", the high temperature long-term heat resistance was evaluated.

(Moisture absorption and reflow resistance) For the test piece obtained in the same way as the above "(adhesion)" evaluation, let it stand for 3 days in an environment of 40°C and 90%RH, and then perform moisture absorption by heating at 260°C for 20 seconds. welding test. For the test piece after the moisture absorption reflow test, visually confirm the presence or absence of air bubbles. The case where air bubbles were not confirmed was made "o", and the case where air bubbles were confirmed was made "x", and the moisture absorption reflow resistance was evaluated.

(quick press) Each of the curable resin compositions obtained in Examples 14 to 22 and Comparative Examples 5 to 8 was coated on a polyimide substrate (thickness 25 μm) so that the thickness became about 20 μm, and dried. Thereby, an adhesive film is obtained. As the polyimide base material, Kapton 100H (manufactured by TORAY-DUPONT Co., Ltd.) was used. An opening of 10 mm×10 mm was set on the obtained adhesive film, and it was attached 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. The copper-clad laminates with the configuration are used to make samples for FPC evaluation. Furthermore, the lamination was carried out in a rapid pressing method using a mobile vacuum heat press at 180° C., under vacuum, at a pressure of 3 MPa, and for 5 minutes. As a mobile vacuum heat press, MKP-3000V (manufactured by MIKADO TECHNOS) was used. The obtained samples for FPC evaluation were observed with an optical microscope at the end of the adhesive film at the opening, and the bleeding amount of the curable resin composition (the length of the most bleeding part) was measured. In addition, the cross-section of the test piece after rapid pressing was polished, and then observed with an optical microscope. The case where no void was confirmed between the copper wiring patterns was rated as "O", and the case where a void was confirmed was rated as "X". , to evaluate embeddedness.

(plating resistance) The samples for FPC evaluation obtained from the evaluation of the above "(rapid pressing)" were carried out 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 plating. Use an optical microscope to observe the end of the adhesive film at the opening, and set the case where the leaching of the plating solution was not confirmed as "O", and the case where the leaching of the plating solution was confirmed at the end as "X". repeatable evaluation.

[產業上之可利用性][table 3]

[Industrial availability]

According to the present invention, it is possible to provide a curable resin composition which is excellent in flame retardancy, adhesiveness, high-temperature long-term heat resistance, and moisture absorption reflow resistance and has low environmental load. Furthermore, according to the present invention, a cured product of the curable resin composition, and an adhesive and an adhesive film using the curable resin composition can be provided. Also, according to the present invention, it is possible to provide a curable resin composition excellent in adhesiveness, high-temperature long-term heat resistance, moisture absorption reflow resistance, plating resistance, low exudation during rapid pressing, and embedding property. Furthermore, according to the present invention, a cured product of the curable resin composition, and an adhesive and an adhesive film using the curable resin composition can be provided.

none

none

Claims (21)

A curable resin composition comprising a curable resin, an imide oligomer, and diaspore-type aluminum hydroxide, the imide oligomer having an acid anhydride group and/or a phenolic hydroxyl group, and the imide The number average molecular weight of the oligomer is 400 or more and 5000 or less. The curable resin composition according to claim 1, wherein the curable resin contains an epoxy resin. The curable resin composition according to claim 1 or 2, wherein the imidization rate of the imide oligomer is 70% or more. The curable resin composition according to claim 1 or 2, wherein the diaspore-type aluminum hydroxide particles have an average particle diameter of 0.1 μm or more and 10 μm or less. The curable resin composition according to claim 1 or 2, wherein the content of the diaspore-type aluminum hydroxide is 10 parts by weight relative to 100 parts by weight of the total of the curable resin and the imide oligomer Above and below 150 parts by weight. The curable resin composition according to claim 1 or 2, which is used for bonding of flexible printed substrates or coverlay films. A cured product, which is a cured product of the curable resin composition described in claim 1, 2, 3, 4, 5 or 6. An adhesive, which is formed by using the curable resin composition described in claim 1, 2, 3, 4, 5 or 6. An adhesive film formed by using the adhesive described in Claim 8. A curable resin composition, which contains a curable resin, an imide oligomer, and an inorganic filler. The imide oligomer has an acid anhydride group and/or a phenolic hydroxyl group, and the melt viscosity at 180°C is Above 10kPa‧s and less than 1000kPa‧s, The number average molecular weight of the said imide oligomer is 400-5000. The curable resin composition according to claim 10, which further contains diaspore-type aluminum hydroxide. The curable resin composition according to claim 11, wherein the diaspore-type aluminum hydroxide particles have an average particle diameter of 0.1 μm or more and 10 μm or less. The curable resin composition according to claim 11 or 12, wherein the content of the diaspore-type aluminum hydroxide is 10 parts by weight relative to 100 parts by weight of the total of the curable resin and the imide oligomer Above and below 150 parts by weight. The curable resin composition according to claim 10 or 11, wherein the inorganic filler contains at least one of silica and barium sulfate. The curable resin composition according to claim 10 or 11, wherein the average particle diameter of the above-mentioned inorganic filler is not less than 5 nm and not more than 4 μm. The curable resin composition according to claim 10 or 11, wherein the content of the inorganic filler is 10 parts by weight or more and 150 parts by weight relative to the total of 100 parts by weight of the curable resin and the imide oligomer. servings or less. The curable resin composition according to claim 10 or 11, wherein the imidization rate of the imide oligomer is 70% or more. The curable resin composition according to claim 10 or 11, which is used for bonding of flexible printed substrates or coverlay films. A cured product, which is a cured product of the curable resin composition described in claim 10, 11, 12, 13, 14, 15, 16, 17 or 18. An adhesive, which is formed by using the curable resin composition described in claim 10, 11, 12, 13, 14, 15, 16, 17 or 18. An adhesive film made using the adhesive described in claim 20.