Curable resin composition

Abstract

To provide a curable resin composition that does not penetrate through holes when laminated to a glass core, has high adhesion to glass and copper after curing, and exhibits low dielectric constant and low dielectric loss tangent. [Solution] (A) A cyclic imide resin represented by the following formula (1) TIFF2026123538000017.tif37156 A curable resin composition comprising (B) a curing catalyst, wherein the composition satisfies the following minimum complex viscosities at 40 to 150°C: (α) 100 to 10,000 Pa·s (measurement frequency 1 Hz) and (β) 10 to 2,000 Pa·s (measurement frequency 2 Hz), and the cured product of the composition satisfies the following die shear strengths at 25°C: (γ) die shear strength with glass and (δ) die shear strength with copper, each of which is 10 MPa or more.

Description

[Technical Field]

[0001] This invention relates to a curable resin composition. [Background technology]

[0002] In recent years, mobile communication devices such as mobile phones, their base station equipment, network infrastructure equipment such as servers and routers, and electronic devices such as large computers have seen a continuous increase in the speed and capacity of signals used. Consequently, high-frequency bands such as the 20GHz range are used in printed circuit boards mounted on these electronic devices, requiring insulating materials for printed circuit boards to have properties such as low dielectric constant and low dielectric loss tangent. Materials that may satisfy these properties include epoxy resins, modified polyphenylene ether resins, and maleimide resins (Patent Documents 1-4).

[0003] Furthermore, recent semiconductor packaging has seen an increase in the number of dies mounted on a single package due to the adoption of chiplets. This increase in the number of dies has led to larger package sizes, and package warping has become a problem.

[0004] Therefore, glass cores are attracting attention as cores for package substrates. Unlike cores made of organic resin containing glass fibers, glass cores have superior flatness, dimensional stability, and thermal stability, making them ideal as cores for large package substrates, and their development has been active in recent years (Patent Documents 5-8). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2019-1965 [Patent Document 2] Japanese Patent Publication No. 2018-28044 [Patent Document 3] Japanese Patent Publication No. 2020-176190 [Patent Document 4] Japanese Patent Publication No. 2021-181531 [Patent Document 5] Japanese Patent Publication No. 2024-72809 [Patent Document 6] Japanese Patent Publication No. 2024-80860 [Patent Document 7] Japanese Patent Publication No. 2024-89922 [Patent Document 8] Japanese Patent Publication No. 2019-102572 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, glass cores have the disadvantage of being difficult to manufacture because they cannot be directly copper-plated. Another method involves applying a thin resin layer to the surface of the glass core and then copper-plating it, but this method results in the resin filling the through-holes of the glass core, requiring the removal of the resin from within the through-holes. Therefore, the present invention aims to provide a curable resin composition that does not penetrate through holes when laminated to a glass core, and further exhibits high adhesion to glass and copper after curing, as well as low dielectric constant and low dielectric loss tangent. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the inventors of the present invention have found that the following curable resin composition can achieve the above objectives, and have completed the present invention. In other words, the present invention provides the following curable resin compositions, etc.

[0008] [1] (A) Cyclic imide resin represented by the following formula (1): 20.0 to 99.0% by mass of the total composition [ka] (In formula (1), A independently represents a tetravalent organic group containing a cyclic structure. Q independently represents a divalent aliphatic hydrocarbon group having 6 or more carbon atoms which may contain a heteroatom or a divalent hydrocarbon group derived from a dimer acid skeleton. B independently represents an arylene group having 6 or more carbon atoms which may contain a heteroatom. X is a hydrogen atom or a methyl group, n is 0 to 200, and m is 0 to 200. Also, the order of each repeating unit enclosed by n and m is not limited.) and (B) Curing catalyst containing (A) component is composed of a cyclic imide resin (A1) in which n + m is 21 or more in formula (1) and a cyclic imide resin (A2) in which n is 0 to 10 and m is 0 to 10, and contains them in a mass ratio of (A1):(A2) = 98:2 to 50:50, and a curable resin composition that simultaneously satisfies the following conditions (α) to (δ). (α) In the resin composition, the minimum complex viscosity at 40 to 150 °C measured at a frequency of 1 Hz is 100 to 10,000 Pa·s (β) In the resin composition, the minimum complex viscosity at 40 to 150 °C measured at a frequency of 2 Hz is 10 to 2,000 Pa·s (γ) The shear strength at 25 °C between the cured product of the resin composition and glass is 10 MPa or more (δ) The shear strength at 25 °C between the cured product of the resin composition and copper is 10 MPa or more [2] The curable resin composition according to [1], wherein the weight average molecular weight of the cyclic imide resin (A1) is 10,000 to 1,000,000. [3] The curable resin composition according to [1] or [2], wherein the weight average molecular weight of the cyclic imide resin (A2) is 500 to 30,000. [4] The curable resin composition according to any one of [1] to [3], wherein the (B) component is an imidazole compound. [5] The curable resin composition according to any one of [1] to [4], which is an adhesive film for a glass core. [6] An adhesive for a glass core comprising a curable resin composition according to any one of [1] to [4].

Advantages of the Invention

[0009] When the curable resin composition of the present invention is laminated on a glass core, it does not penetrate into the through holes, and after curing, it has a high adhesive strength with glass and copper, and becomes a cured product with a low relative dielectric constant and a low dielectric loss tangent. Therefore, the curable resin composition of the present invention is useful as an adhesive film for a glass core or an adhesive for a glass core.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, the curable resin composition of the present invention will be described in detail.

[0011] [(A) Cyclic Imide Resin] The cyclic imide resin of component (A) is the main component of the curable resin composition of the present invention, and is represented by the following formula (1) and contains two types of cyclic imide resins (A1) and (A2) having different degrees of polymerization. By containing component (A), the cured product of the curable resin composition has a low relative dielectric constant and a low dielectric loss tangent, and after curing, it becomes a cured product with a high adhesive strength with glass and copper.

Chemical formula

[0012] Here, the organic group represented by A in formula (1) is independently a tetravalent organic group containing a cyclic structure, and is particularly preferably any one of the tetravalent organic groups represented by the following formula.

Chemical formula

[0013] The organic group represented by Q in formula (1) is a divalent aliphatic hydrocarbon group having 6 or more carbon atoms, which may independently contain a heteroatom, or a divalent hydrocarbon group derived from a dimer acid skeleton, preferably a divalent hydrocarbon group represented by any of the following structural formulas or a divalent hydrocarbon group derived from a dimer acid skeleton. [ka]

[0014] The bonds in the above formula that are not bonded to substituents are bonded to the nitrogen atom that forms the cyclic imide structure in formula (1). In the above formula, R 1 R independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. 1 Preferably, it is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or a linear alkyl group having 1 to 10 carbon atoms. In the above formula, p 1 and p 2 Each of these numbers is 5 or greater, preferably between 5 and 12, more preferably between 6 and 10, and may be the same or different. In the above formula, p 3 and p 4 Each of these is a number greater than or equal to 0, preferably a number between 0 and 4, more preferably a number between 0 and 3, and may be the same or different. In the above formula, p 5 and p 6 Each of these is a number greater than or equal to 0, preferably a number between 0 and 4, more preferably a number between 0 and 2, and may be the same or different.

[0015] The divalent hydrocarbon group derived from the dimer acid skeleton is a group derived from dimer acid, which is a liquid fatty acid mainly composed of a dicarboxylic acid having 36 carbon atoms and is produced by dimerization of an unsaturated fatty acid having 18 carbon atoms using natural products such as vegetable oils as raw materials. Dimer acid has not a single skeleton but has a plurality of structures and there exist several isomers. The dimer acid skeleton means a group derived from a dimerdiamine having a structure in which the carboxy group of such dimer acid is substituted with a primary aminomethyl group. Among the divalent hydrocarbon groups derived from the dimer acid skeleton, those having a structure in which the carbon-carbon double bond in the hydrocarbon group derived from the dimer acid skeleton is reduced by a hydrogenation reaction are more preferable from the viewpoints of the heat resistance and reliability of the cured product. In general, dimer acid may contain a trimer (trimer acid) due to using natural products such as vegetable oils as raw materials. However, it is preferable that the proportion of the hydrocarbon group derived from dimer acid among the hydrocarbon groups derived from dimer acid and trimer acid is, for example, 95% by mass or more, because the dielectric properties are excellent, the viscosity during heating is likely to decrease, the moldability is excellent, and the influence of moisture absorption tends to be small. As described above, since the dimer acid skeleton has a plurality of structures, in this specification, the divalent hydrocarbon group derived from the dimer acid skeleton may be represented as -C 36 H 70 - as its average structure.

[0016] The organic group represented by B in the formula (1) is an arylene group having 6 or more carbon atoms which may independently contain a hetero atom, and is preferably an arylene group represented by any of the following structural formulas.

Chemical formula

[0017] The bond to which no substituent is bonded in the above formula is bonded to the nitrogen atom forming a cyclic imide structure in the formula (1). In the above formula, R 2 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, and are preferably a hydrogen atom or a methyl group. In the above formula, R 3 These are independently a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, preferably a methyl group or a trifluoromethyl group. In the above formula, Z is an oxygen atom, a sulfur atom, or a methylene group, and is preferably an oxygen atom.

[0018] In formula (1), X is a hydrogen atom or a methyl group. In formula (1), n ​​is between 0 and 200, preferably between 5 and 100, and more preferably between 10 and 50. In formula (1), m is between 0 and 200, preferably between 0 and 100, and more preferably between 0 and 50. (A) One of the components, the cyclic imide resin (A1), has n+m of 21 or more, and the other, the cyclic imide resin (A2), has n between 0 and 10 and m between 0 and 10 (i.e., n+m between 0 and 20). The cyclic imide resin (A1) is preferably one in which n+m has a value of 21 to 300, more preferably 21 to 250, and even more preferably 21 to 200. Furthermore, the cyclic imide resin (A1) is not particularly limited as long as n+m satisfies 21 or more, but for example, when m=0, n is preferably 21 to 200, and more preferably 25 to 150. Also, when m≠0, n and m are preferably 11 to 100, and more preferably 15 to 50, respectively. The cyclic imide resin (A2) preferably has an n+m value of 0 to 16, more preferably 2 to 10. Furthermore, the cyclic imide resin (A2) preferably has n and m values ​​of 0 to 10, more preferably 0 to 8, and even more preferably 0 to 5.

[0019] There are no particular restrictions on the weight-average molecular weight (Mw) of the cyclic imide resin represented by formula (1), but it is preferably 500 to 1,000,000, more preferably 1,000 to 100,000, and even more preferably 3,000 to 50,000. If the weight-average molecular weight (Mw) is within this range, the curable resin composition will have sufficient strength and the terminal cyclic imide groups can be reacted efficiently. The weight-average molecular weight of the cyclic imide resin (A1) is preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000, and even more preferably 40,000 to 300,000. The weight-average molecular weight of the cyclic imide resin (A2) is preferably 500 to 30,000, more preferably 500 to 20,000, and even more preferably 1,000 to 10,000.

[0020] In this specification, the weight-average molecular weight (Mw) refers to the weight-average molecular weight measured by GPC with polystyrene as the standard substance under the following conditions. [GPC measurement conditions] Developing solvent: tetrahydrofuran Flow rate: 0.6mL / min Column: TSK Guardcolumn SuperH-L TSKgel SuperH4000(6.0mmI.D.×15cm×1) TSKgel SuperH3000(6.0mmI.D.×15cm×1) TSKgel SuperH2000(6.0mmI.D.×15cm×2) (All manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 20 μL (Sample concentration: 0.5% by mass - tetrahydrofuran solution) Detector: Differential refractometer (RI)

[0021] Each of the components (A1) and (A2) may be used individually or in combination of two or more. Using two cyclic imide resins with different degrees of polymerization as component (A) is preferable because it prevents the minimum complex viscosity from becoming too low, reduces the degree of TGV penetration, and improves adhesion to copper and glass.

[0022] The mixing ratio of component (A1) to component (A2) is (A1):(A2) = 98:2 to 50:50 by mass ratio, with 95:5 to 60:40 being preferred. A composition containing component (A1) and component (A2) within this range will have a minimum complex viscosity that is not too low, a low degree of TGV penetration, and high adhesion to copper and glass.

[0023] There are no particular restrictions on the method for producing the cyclic imide resin of component (A). For example, an amine-terminated compound may be synthesized by reacting an acid anhydride with a diamine, and then the amine-terminated compound may be reacted with an excess of maleic anhydride or citraconic anhydride to produce the resin.

[0024] Examples of acid anhydrides include pyromellitic anhydride, maleic anhydride, succinic anhydride, 4,4'-carbonyl diphthalic anhydride, 4,4'-diphthalic anhydride, 4,4'-sulfonyl diphthalic anhydride, 4,4'-oxydiphthalic anhydride, and 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride. These acid anhydrides may be used individually or in combination of two or more, depending on the purpose and application. From the viewpoint of the electrical properties of the cyclic imide resin, pyromellitic anhydride, 4,4'-oxydiphthalic anhydride, and 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride are preferred as acid anhydrides.

[0025] Examples of diamines include 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane, bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4'-diaminodiphenylmethane, and 1,3-bis(4-aminophenoxy)benzene. Aliphatic diamines such as 1,12-diaminododecane, 1,10-diaminodecane, octyldiamine, 1,3-di(aminomethyl)cyclohexane, 1-amino-4-(aminomethyl)cyclohexane, 1,3-diaminoadamantane, isophoronediamine, 2,4,4-trimethylhexane-1,6-diamine, 2-methylpentane-1,5-diamine, and 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0(2,6)]decane; dimeramines, etc. These diamines may be used individually or in combination of two or more, depending on the purpose and application. From the viewpoint of the electrical properties of the cyclic imide compound, the diamine is preferably an aromatic diamine such as 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane; aliphatic diamines such as 1,12-diaminododecane, 1,10-diaminodecane, octyldiamine, 1,3-di(aminomethyl)cyclohexane, 1-amino-4-(aminomethyl)cyclohexane, 1,3-diaminoadamantane, isophoronediamine, 2,4,4-trimethylhexane-1,6-diamine, 2-methylpentane-1,5-diamine; and dimeramine is preferred, with 1,12-diaminododecane, dimeramine, and isophoronediamine being particularly preferred.

[0026] The equivalent amount of the cyclic imide group in component (A) is preferably 0.001 to 0.5 mol / 100g, more preferably 0.003 to 0.4 mol / 100g, even more preferably 0.01 to 0.3 mol / 100g, and even more preferably 0.02 to 0.2 mol / 100g. Within this range, the cured product of the curable resin composition has a low dielectric constant and a low dielectric loss tangent, which is preferable.

[0027] The amount of component (A) is 20.0 to 99.0% by mass of the entire composition in order to satisfy the conditions (α) to (δ) described later. However, if the inorganic or organic filler described later is not included, it is preferably 50.0 to 99.0% by mass of the resin composition, more preferably 60.0 to 99.0% by mass. If the inorganic or organic filler described later is included, it is preferably 20.0 to 80.0% by mass of the resin composition, more preferably 25.0 to 75.0% by mass.

[0028] [(B) Curing catalyst] Component (B) is a curing catalyst, intended to accelerate the curing of the resin composition. There are no particular restrictions on the curing catalyst for component (B), but examples include thermal radical polymerization initiators and thermal anionic polymerization initiators.

[0029] Examples of thermal radical polymerization initiators include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetacetate peroxide, acetylacetone peroxide, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, and 2,2-bis(4,4-di-t -Butyl peroxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl-4,4-bis(t-butylperoxy)valerate, 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, t-butyl hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl Tyl-2,5-bis(t-butylperoxy)hexane, α,α'-bis(t-butylperoxy)diisopropylbenzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyn-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, cinnamate peroxide, m-toluyl peroxide, benzoyl peroxide, diisopropyl Pill peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxyneodecanoate, 1,1,3,3-Tetramethylbutyl peroxyneodecanoate, 1-Cyclohexyl-1-methylethyl peroxyneodecanoate, t-Hexyl peroxyneodecanoate, t-Butyl peroxyneodecanoate, t-Hexyl peroxypivalate, t-Butyl peroxypivalate, 2,5-Dimethyl-2,5-Bis(2-ethylhexanoyl peroxy)hexane, 1,1,3,3-Tetramethylbutyl peroxy-2-ethylhexanoate, 1-Cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate, t-Hexyl peroxy Xy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, t-butyl peroxymalic acid, t-butyl peroxylaurate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butyl peroxyacetate, t-hexyl peroxybenzoate, t-butyl peroxy Organic peroxides such as -oxy-m-butyloylbenzoate, t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate, t-butylperoxyallyl monocarbonate, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide), 2,2'-azobis[N-(2-methylpropyl)-2-methylpropionamide], 2,2'-azobis[N-(2-methyl 2,2'-Azobis(N-Hexyl-2-methylpropionamide), 2,2'-Azobis(N-Propyl-2-methylpropionamide), 2,2'-Azobis(N-Ethyl-2-methylpropionamide), 2,2'-Azobis[2-Methyl-N-(2-hydroxyethyl)propionamide], 2,2'-Azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-Azobis{2-Methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, 2,Examples of azo compounds include 2'-azobis[N-(2-propenyl)-2-methylpropionamide] and dimethyl-1,1'-azobis(1-cyclohexanecarboxylate).

[0030] Examples of thermal anionic polymerization initiators include amine compounds such as triethylamine, triethylenediamine, 2-(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo[5.4.0]undecene-7, tris(dimethylaminomethyl)phenol, and benzyldimethylamine; and amine compounds such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, and 2-phenyl-4-hydroxy-5-methylimidazole. Midazole compounds include organophosphorus compounds such as triphenylphosphine, tributylphosphine, trioctylphosphine, tetrabutylphosphonium hexafluorophosphate, tetrabutylphosphonium tetraphenyl borate, tetrabutylphosphonium acetate, tetraphenylphosphonium tetraphenyl borate, tetraphenylphosphonium bromide, tetrabutylphosphonium bromide, tetrabutylphosphonium laurate, tetraphenylphosphonium hydrogen phthalate, bis(tetraphenylphosphonium) dihydrogen pyromelitate, and bis(tetrabutylphosphonium) dihydrogen pyromelitate.

[0031] Among these, thermal anionic polymerization initiators are preferred, and among them, imidazole compounds such as 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, and 2-phenyl-4-hydroxy-5-methylimidazole are particularly preferred.

[0032] These curing catalysts may be used individually or in combination of two or more types.

[0033] The amount of component (B) is 0.1 to 5.0% by mass of the entire composition, preferably 0.2 to 4.5 parts by mass, and more preferably 0.3 to 4.0 parts by mass, per 100 parts by mass of component (A). A concentration of component (B) within the range of 0.1 to 5.0% by mass of the entire composition is preferable because it does not adversely affect the physical properties of the cured resin composition and allows the resin composition to cure sufficiently.

[0034] The curable resin composition of the present invention is characterized by satisfying all of the following conditions (α) to (δ). Each of these conditions will be described in detail below.

[0035] [(α) The minimum complex viscosity of the resin composition measured at a frequency of 1 Hz at 40-150°C is 100-10,000 Pa·s.] One reason why resin can seep into the through-holes of a glass core is that the viscosity of the adhesive film for the glass core becomes too low when it is bonded to the core. This occurs when molten resin seeps into the through-holes during the heating and pressurizing process that bonds the adhesive film to the glass core. Therefore, the minimum complex viscosity of the resin composition at 40-150°C measured at a frequency of 1 Hz is 100-10,000 Pa·s, preferably 300-7,000 Pa·s, and more preferably 500-5,000 Pa·s. If the minimum complex viscosity measured at a frequency of 1 Hz is lower than 100 Pa·s, the resin will penetrate into the through-holes of the glass core. If the minimum complex viscosity measured at a frequency of 1 Hz is higher than 10,000 Pa·s, the adhesion to the glass core will be poor.

[0036] In this specification, the minimum complex viscosity is the value measured by the following method. (Measurement conditions) The prepared curable resin composition was coated onto a PET film to a thickness of 25 μm. One g of the resulting uncured film was folded so that it could be sandwiched between 18 mm diameter parallel plates to prepare a measurement sample. Using this sample, the minimum complex viscosity was measured using a Rheosol-G3000 rheometer (manufactured by UBM Co., Ltd.) under the following measurement conditions: starting temperature from 40°C to 150°C, heating rate of 5°C / min, measurement temperature interval of 2°C, and frequency of 1 Hz or 2 Hz.

[0037] [(β) The minimum complex viscosity of the resin composition at 40-150°C measured at a frequency of 2 Hz is 10-2,000 Pa·s.] Complex viscosity due to differences in frequency is also important in order to prevent resin from entering the through-holes of the glass core. Therefore, the minimum complex viscosity of the resin composition at 40-150°C, measured at a frequency of 2 Hz, is 10-2,000 Pa·s, preferably 20-1,500 Pa·s, and more preferably 50-1,000 Pa·s. If the minimum complex viscosity measured at 2 Hz is lower than 10 Pa·s, the resin will penetrate into the through-holes of the glass core. If the minimum complex viscosity measured at 2 Hz is higher than 2,000 Pa·s, the adhesion to the glass core will be poor.

[0038] [(γ) The die shear strength between the cured resin composition and the glass at 25°C is 10 MPa or higher.] To prevent delamination of the cured glass and resin composition, the die shear strength of the cured glass and resin composition after curing at 180°C for 2 hours is 10 MPa or higher, preferably 15 MPa or higher, and more preferably 20 MPa or higher. If the die shear strength of the cured glass and resin composition is less than 10 MPa, the resin composition will easily delaminate from the glass during reliability testing.

[0039] In this specification, the die shear strength is a value measured by the following method. (Measurement conditions) The prepared curable resin composition was coated onto a PET film to a thickness of 25 μm. The resulting film was laminated using a vacuum laminator V-130 (manufactured by Nikko Materials Co., Ltd.) so that the curable resin composition coated on the PET film was in contact with (facing) the substrate (glass or copper), at 80°C, a vacuum of 0.6 hPa, and a pressure of 0.3 MPa for 60 seconds. After cooling to room temperature, the PET film was peeled off, a 3 mm x 3 mm silicon chip was placed on the curable resin composition surface, and laminated again using the vacuum laminator V-130 at 100°C, a vacuum of 0.6 hPa, and a pressure of 0.3 MPa for 60 seconds, followed by heat curing at 180°C for 2 hours. The die shear strength was measured by flicking the silicon chip using a Bond Tester 4000 universal bond tester (manufactured by Daigi Co., Ltd.).

[0040] [(δ) The die shear strength between the cured resin composition and copper at 25°C is 10 MPa or higher.] To prevent delamination of the cured copper-resin composition, the die shear strength of the cured copper-resin composition after curing at 180°C for 2 hours is 10 MPa or higher, preferably 15 MPa or higher, and more preferably 20 MPa or higher. If the die shear strength of the cured copper-resin composition is less than 10 MPa, the resin composition will easily delaminate from the copper during reliability testing.

[0041] There are no particular limitations on the use of the curable resin composition of the present invention, but it is preferably used as an adhesive film for glass cores.

[0042] [Inorganic fillers] The curable resin composition of the present invention may further contain an inorganic filler, if necessary. There are no particular restrictions on the inorganic fillers, but examples include: silica, titanium dioxide, yttrium oxide, aluminum oxide, magnesium oxide, zinc oxide, beryllium oxide and other metal oxides; metal nitrides such as boron nitride, aluminum nitride, silicon nitride; carbon-containing particles such as silicon carbide, diamond, graphene; hollow particles such as silica balloons (hollow silica), carbon balloons, alumina balloons, aluminosilicate balloons; elemental metals such as gold, silver, copper, palladium, aluminum, nickel, iron, cobalt, titanium, manganese, zinc, tungsten, platinum, lead, tin; alloys such as solder and steel; stainless steel. Examples of magnetic metal alloys include stainless steel, Fe-Cr-Al-Si alloy, Fe-Si-Al alloy, Fe-Ni alloy, Fe-Cu-Si alloy, Fe-Si alloy, Fe-Si-B(-Cu-Nb) alloy, Fe-Si-Cr-Ni alloy, Fe-Si-Cr alloy, and Fe-Si-Al-Ni-Cr alloy; and ferrites such as hematite (Fe2O3), magnetite (Fe3O4), Mn-Zn ferrite, Ni-Zn ferrite, Mg-Mn ferrite, Zr-Mn ferrite, Ti-Mn ferrite, Mn-Zn-Cu ferrite, barium ferrite, and strontium ferrite. These may be used individually or in combination of two or more.

[0043] Adding metal oxides, metal nitrides, or carbon-containing particles can lower the coefficient of linear expansion of the cured resin material and increase its thermal conductivity. Adding hollow particles can lower the relative permittivity, dielectric loss tangent, density, etc., of the cured resin material. Adding metals or alloys can increase the electrical conductivity, thermal conductivity, etc., of the cured resin material. Furthermore, adding ferrites can impart electromagnetic wave absorption capabilities to the cured resin material. There are no particular restrictions on the shape of the inorganic filler, and examples include spherical, flaky, needle-shaped, rod-shaped, and elliptical shapes. Among these, spherical, flaky, flake-shaped, elliptical, and rod-shaped are preferred, and spherical, flaky, flake-shaped, and elliptical are even more preferred.

[0044] There are no particular restrictions on the primary particle size of the inorganic filler, but a median diameter of 0.05 to 500 μm, more preferably 0.1 to 300 μm, and even more preferably 1 to 100 μm, as measured by a laser diffraction particle size distribution analyzer, is preferred. Within this range, it is easy to uniformly disperse the inorganic filler in the curable resin composition, and the inorganic filler does not settle, separate, or become unevenly distributed over time, which is preferable.

[0045] There are no particular restrictions on the amount of the inorganic filler used, but it is preferably 5 to 300 parts by mass, more preferably 10 to 250 parts by mass, and even more preferably 50 to 200 parts by mass, per 100 parts by mass of component (A) in the curable resin composition of the present invention.

[0046] [Organic fillers] The curable resin composition of the present invention may further contain an organic filler. There are no particular restrictions on the organic fillers, but examples include thermoplastic resin particles such as acrylic-butadiene copolymers, styrene-butadiene copolymers, acrylonitrile-styrene-butadiene copolymers, and acrylic block copolymers, as well as carbon fibers, cellulose fibers, silicone powder, acrylic powder, polytetrafluoroethylene powder, polyethylene powder, and polypropylene powder. These may be used individually or in combination of two or more.

[0047] There are no particular restrictions on the shape of the organic filler, and examples include spherical, fibrous, flake-shaped, needle-shaped, rod-shaped, and elliptical shapes. Among these, spherical, fibrous, flake-shaped, elliptical, and rod-shaped are preferred, and spherical, fibrous, flake-shaped, and elliptical are even more preferred.

[0048] There are no particular restrictions on the primary particle size of the organic filler, but a median diameter of 0.05 to 500 μm, more preferably 0.1 to 300 μm, and even more preferably 1 to 100 μm, as measured by a laser diffraction particle size distribution analyzer, is preferred. Within this range, it is easy to uniformly disperse the organic particles in the curable resin composition, and the organic particles do not settle, separate, or become unevenly distributed over time, which is preferable.

[0049] There are no particular restrictions on the amount of the organic filler used, but it is preferably 1 to 400 parts by mass, more preferably 5 to 200 parts by mass, and even more preferably 10 to 100 parts by mass, per 100 parts by mass of component (A) in the curable resin composition of the present invention. Within this range, the strength of the curable resin composition can be increased.

[0050] [Adhesion-enhancing agent] The curable resin composition of the present invention may contain an adhesion promoter as needed to impart adhesiveness or tackiness (pressure-sensitive adhesion). Examples of adhesion promoters include epoxy resins, acrylic resins, urethane resins, phenolic resins, terpene resins, and silane coupling agents. Among these, epoxy resins, acrylic resins, and silane coupling agents are preferred for imparting adhesiveness, and terpene resins are preferred for imparting tackiness (pressure-sensitive adhesion).

[0051] There are no particular restrictions on the epoxy resin, but examples include known epoxy resins that are liquid or solid at room temperature, such as biphenol-type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, 3,3',5,5'-tetramethyl-4,4'-biphenol type epoxy resin and 4,4'-biphenol type epoxy resin, biphenyl aralkyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, naphthalenediol type epoxy resin, trisphenylol methane type epoxy resin, tetrakisphenylolethane type epoxy resin and phenol dicyclopentadiene novolac type epoxy resin, and alicyclic epoxy resins.

[0052] There are no particular restrictions on the acrylic resin, but examples include lauryl acrylate, stearyl acrylate, isostearyl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl acid phosphate, polyethylene glycol diacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane triacrylate, and dipentaerythritol. Examples include xaacrylate, dioxane glycol diacrylate, 9,9-bis[4-(2-hydroxyethoxy)phenyl]ful orange acrylate, lauryl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, 2-methacryloyloxyethyl phthalate, 2-methacryloyloxyethyl acid phosphate, polyethylene glycol dimethacrylate, dimethylol tricyclodecane dimethacrylate, and the like.

[0053] There are no particular restrictions on the terpene resin, but examples include homopolymers of terpenes such as monoterpenes like α-pinene, β-pinene, dipentene, and limonene; sesquiterpenes like cedrene and farnesene; and diterpenes like abietic acid; aromatic modified terpene resins, which are copolymers of aromatic vinyl compounds such as styrene and α-methylstyrene with the aforementioned terpenes; and terpene phenol resins, which are copolymers of phenols such as phenol, cresol, hydroquinone, naphthol, and bisphenol A with the aforementioned terpenes. Hydrogenated terpene resins, which are obtained by hydrogenating these terpene resins, can also be used.

[0054] There are no particular restrictions on the silane coupling agent, but examples include silane coupling agents such as n-propyltrimethoxysilane, n-propyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 2-[methoxy(polyethyleneoxy)propyl]-trimethoxysilane, methoxytri(ethyleneoxy)propyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-isocyanatopropyltrimethoxysilane.

[0055] There are no particular restrictions on the amount of the adhesion-imparting agent, but it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 5 parts by mass per 100 parts by mass of component (A). Within this range, the adhesive strength or tackiness of the curable resin composition can be further improved without changing the mechanical properties of the resin composition.

[0056] [Antioxidant] The resin composition of the present invention may optionally contain an antioxidant. There are no particular restrictions on the antioxidants used, but examples include n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)acetate, neododecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, dodecyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, and ethyl acetate. α-(4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octadecyl-α-(4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octadecyl-α-(4-hydroxy-3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2-(n-octylthio)ethyl-3,5-di-t-butyl-4-hydroxyphenyl acetate, 2-(n-octadecylthio)ethyl-3, 5-di-t-butyl-4-hydroxyphenyl acetate, 2-(n-octadecylthio)ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2-(2-stearoyloxyethylthio)ethyl-7-(3-methyl-5-t-butyl-4-hydroxyphenyl)heptanoate, 2-hydroxyethyl-7-(3-methyl-5-t-butyl-4-hydroxyphenyl)propionate, pentae Phenolic antioxidants such as lysritol tetrakiss [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]; sulfur-based antioxidants such as dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, and pentaerythrityl tetrakiss (3-laurylthiopropionate);Examples of phosphorus-based antioxidants include tridecyl phosphite, triphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, 2-ethylhexyl diphenyl phosphite, diphenyl tridecyl phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite, distearyl pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, and 2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosfepin-6-yl]oxy]-N,N-bis[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosfepin-6-yl]oxy]-ethyl]ethanamine.

[0057] There are no particular restrictions on the amount of the antioxidant added, but it is preferably 0.00001 to 5 parts by mass, more preferably 0.0001 to 4 parts by mass, and even more preferably 0.001 to 3 parts by mass per 100 parts by mass of component (A). Within this range, oxidation of the curable resin composition can be prevented without changing the mechanical properties of the resin composition.

[0058] [Flame retardant] The curable resin composition of the present invention may contain a flame retardant as needed to impart flame retardancy. There are no particular restrictions on the flame retardants, but examples include phosphorus-based flame retardants, metal hydrates, halogen-based flame retardants, and guanidine-based flame retardants. Examples of phosphorus-based flame retardants include red phosphorus, ammonium phosphate such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and polyammonium phosphate, inorganic nitrogen-containing phosphorus compounds such as guanidine phosphate and phosphate amides, phosphoric acid, phosphine oxide, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis(diphenyl phosphate), 1,3-phenylene bis(di-2,6-xylenyl phosphate), bisphenol A-bis(diphenyl phosphate), and 1,3-phenylene bis( Examples of phosphazene compounds include diphenylphosphate, divinyl phenylphosphonate, diallyl phenylphosphonate, bis(1-butenyl) phenylphosphonate, phenyl diphenylphosphinate, methyl diphenylphosphinate, bis(2-allylphenoxy)phosphazene, dicresylphosphazene, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melem polyphosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. Examples of metal hydrates include aluminum hydroxide hydrate and magnesium hydroxide hydrate. Examples of halogenated flame retardants include hexabromobenzene, pentabromotoluene, ethylenebis(pentabromopenyne), ethylenebistetrabromophthalimide, 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene, and 2,4,6-tris(tribromophenoxy)-1,3,5-triazine. Examples of guanidine-based flame retardants include guanidine sulfamate and guanidine phosphate. There are no particular restrictions on the amount of the flame retardant added, but it is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and even more preferably 0.1 to 3 parts by mass per 100 parts by mass of component (A). Within this range, flame retardancy can be imparted to the curable resin composition without changing its mechanical properties.

[0059] [Manufacturing method] A method for producing the curable resin composition of the present invention includes mixing components (A) and (B) and other additives as needed using, for example, a planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.) or a stirrer (THINKY CONDITIONING MIXER, manufactured by Thinky Co., Ltd.), and preferably, further mixing with an organic solvent (for example, cyclopentanone, cyclohexanone, mesitylene, anisole, dibutyl ether, diphenyl ether, 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, etc.). Adding an organic solvent lowers the viscosity of the curable resin composition, allowing for more uniform mixing. The curable resin composition is obtained by distilling off the organic solvent under reduced pressure after mixing, but when used as a film or the like, it may be used as is without distillation, or adjusted to the desired concentration. [Examples]

[0060] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0061] The molecular weights shown in the following examples are weight-average molecular weights (Mw) measured by gel permeation chromatography (GPC) using polystyrene as the standard substance. The measurement conditions are shown below. [GPC measurement conditions] Developing solvent: tetrahydrofuran Flow rate: 0.6mL / min Column: TSK Guardcolumn SuperH-L TSKgel SuperH4000(6.0mmI.D.×15cm×1) TSKgel SuperH3000(6.0mmI.D.×15cm×1) TSKgel SuperH2000(6.0mmI.D.×15cm×2) (All manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 20 μL (Sample concentration: 0.5% by mass - tetrahydrofuran solution) Detector: Differential refractometer (RI)

[0062] (A) Cyclic imide resin (A-1) To 2,000 g of N-methylpyrrolidone (0.5% moisture content), 575 g (1.1 mol) of dimer amine and 520 g (1.0 mol) of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride were added and stirred at 25°C for 3 hours, then further stirred at 150°C for 5 hours. To the resulting solution, 196 g (2.0 mol) of maleic anhydride, 82 g (1.0 mol) of sodium acetate, and 204 g (2.0 mol) of acetic anhydride were added and stirred at 80°C for 1 hour. Subsequently, 5,000 g of toluene was added, followed by washing with water, dehydration, and removal of the solvent under reduced pressure to obtain bismaleimide (A-1) represented by the following formula: (Weight-average molecular weight 70,000, maleimide equivalent 0.0077 mol / 100 g) [ka] n ≈ 25 (mean value)

[0063] (A-2) To 2,000 g of N-methylpyrrolidone (0.5% moisture content), 210 g (1.05 mol) of 1,12-dodecanediamine and 218 g (1.0 mol) of pyromellitic anhydride were added and stirred at 25°C for 3 hours, then further stirred at 150°C for 5 hours. To the resulting solution, 196 g (2.0 mol) of maleic anhydride, 82 g (1.0 mol) of sodium acetate and 204 g (2.0 mol) of acetic anhydride were added and stirred at 80°C for 1 hour. Subsequently, 5,000 g of toluene was added, followed by washing with water, dehydration, and removal of the solvent under reduced pressure to obtain bismaleimide (A-2) represented by the following formula: (Weight-average molecular weight 80,000, maleimide equivalent 0.0043 mol / 100 g) [ka] n ≈ 110 (average value)

[0064] (A-3) To 2,000 g of N-methylpyrrolidone (0.6% moisture content), 94 g (0.55 mol) of isophorone diamine, 278 g (0.55 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and 520 g (1.0 mol) of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride were added, and the mixture was stirred at 25°C for 3 hours, followed by stirring at 150°C for 5 hours. To the resulting solution, 196 g (2.0 mol) of maleic anhydride, 82 g (1.0 mol) of sodium acetate, and 204 g (2.0 mol) of acetic anhydride were added, and the mixture was stirred at 80°C for 1 hour. Then, 5,000 g of toluene was added, followed by further washing with water, dehydration, and removal of the solvent under reduced pressure to obtain bismaleimide (A-3) represented by the following formula. (Weight average molecular weight 95,000, maleimide equivalent 0.0065mol / 100g) [ka] n ≈ 20 (mean), m ≈ 20 (mean)

[0065] (A-4) To 900 g of xylene, 300 g (1.5 mol) of 1,12-dodecanediamine and 310 g (1.0 mol) of 4,4'-oxydiphthalic anhydride were added and stirred at 25°C for 3 hours, then further stirred at 140°C for 5 hours. To the resulting solution, 196 g (2.0 mol) of maleic anhydride, 82 g (1.0 mol) of sodium acetate and 204 g (2.0 mol) of acetic anhydride were added and stirred at 80°C for 1 hour. Subsequently, 2,000 g of toluene was added, followed by washing with water, dehydration, and removal of the solvent under reduced pressure to obtain bismaleimide (A-4) represented by the following formula. (Weight-average molecular weight 2,200, maleimide equivalent 0.16 mol / 100 g) [ka] n ≈ 2 (mean value)

[0066] (A-5) Maleimide resin represented by the following formula (BMI-3000, manufactured by Designer Molecules Inc.) (weight-average molecular weight 10,000, maleimide equivalent 0.044 mol / 100g) [ka] n ≈ 8 (mean value)

[0067] (A-6) Maleimide resin represented by the following formula (BMI-1500, manufactured by Designer Molecules Inc.) (weight-average molecular weight 3,000, maleimide equivalent 0.067 mol / 100g) [ka] n ≈ 4 (mean value)

[0068] (A-7) Maleimide resin represented by the following formula (SLK-6895, manufactured by Shin-Etsu Chemical Co., Ltd.) (weight-average molecular weight 700, maleimide equivalent 0.29 mol / 100g) [ka] n=0

[0069] (A-8) To 1,300 g of xylene, 150 g (0.75 mol) of 1,12-dodecanediamine, 258 g (0.75 mol) of 4,4'-(1,4-phenylenediisopropylidene)bisaniline, and 310 g (1.0 mol) of 4,4'-oxydiphthalic anhydride were added and stirred at 25°C for 3 hours, followed by stirring at 140°C for 5 hours. To the resulting solution, 196 g (2.0 mol) of maleic anhydride, 82 g (1.0 mol) of sodium acetate, and 204 g (2.0 mol) of acetic anhydride were added and stirred at 80°C for 1 hour. Subsequently, 2,000 g of toluene was added, followed by washing with water, dehydration, and removal of the solvent under reduced pressure to obtain bismaleimide (A-8) represented by the following formula: (Weight-average molecular weight 3,300, maleimide equivalent 0.11 mol / 100 g) [ka] n ≈ 2 (mean), m ≈ 2 (mean)

[0070] (A'-1) To 1,300 g of xylene, 455 g (0.90 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 196 g (2.0 mol) of maleic anhydride, 82 g (1.0 mol) of sodium acetate, and 204 g (2.0 mol) of acetic anhydride were added, and the mixture was stirred at 80°C for 1 hour. Then, 2,000 g of toluene was added, followed by further washing with water, dehydration, and removal of the solvent under reduced pressure to obtain bismaleimide (A'-1) represented by the following formula. (Weight-average molecular weight 570, maleimide equivalent 0.35 mol / 100 g) [ka]

[0071] (B) Curing catalyst (B-1)2-ethyl-4-methylimidazole

[0072] (C) Adhesion-improving agent (C-1) Phenoxy epoxy resin (product name "jER-1256" (manufactured by Mitsubishi Chemical Corporation)) (C-2) Biphenyl aralkyl type epoxy resin (product name: "NC-3000" (manufactured by Nippon Kayaku Co., Ltd.))

[0073] (D) Inorganic fillers (D-1) Silica "SFP-130MC" (primary particle size median diameter 0.6 μm) (manufactured by Denka Co., Ltd.)

[0074] [Method for preparing a curable resin composition] For Examples 1-6 and Comparative Examples 1-6, in addition to the formulations (parts by mass) shown in Table 1, 100 parts by mass of cyclopentanone was added to a total of 100 parts by mass of each component and mixed. The mixture was then kneaded at 80°C for 30 minutes using a planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.), and then cooled to 25°C. The resulting solution was transferred to a flask, and the solvent was removed by vacuum distillation to prepare a curable resin composition.

[0075] [Minimum complex viscosity at frequencies of 1 Hz and 2 Hz] The prepared curable resin composition was coated onto a PET film to a thickness of 25 μm. One g of the resulting film was folded so that it could be sandwiched between 18 mm diameter parallel plates, and the minimum complex viscosity was measured using a Rheosol-G3000 rheometer (manufactured by UBM Co., Ltd.) under the following measurement conditions: starting temperature from 40°C to 150°C, heating rate of 5°C / min, measurement temperature interval of 2°C, and frequency of 1 Hz or 2 Hz. The results are shown in Table 1.

[0076] [Die share strength] The prepared curable resin composition was coated onto a PET film to a thickness of 25 μm. The resulting film was laminated using a vacuum laminator V-130 (manufactured by Nikko Materials Co., Ltd.) with the PET film and the opposite side in contact with the substrate, at 80°C, a vacuum of 0.6 hPa, and a pressure of 0.3 MPa for 60 seconds. After cooling to room temperature, the PET film was peeled off, a 3 mm x 3 mm silicone chip was placed on top, and the film was laminated again using the vacuum laminator V-130 at 100°C, a vacuum of 0.6 hPa, and a pressure of 0.3 MPa for 60 seconds, followed by heat curing at 180°C for 2 hours. The die shear strength was measured by flicking the silicone chip using a Bond Tester 4000 universal bond tester (manufactured by Daigi Co., Ltd.). The results using glass or copper as the substrate are shown in Table 1. In Table 1, "×" indicates that the resin composition could not be laminated to the glass core, and therefore the die shear strength could not be measured.

[0077] [TGV (Through Glass Via) penetration degree] The prepared curable resin composition was coated onto a PET film to a thickness of 25 μm. The resulting film was then placed on a glass core measuring 50 mm x 50 mm x 500 μm in length, width, and thickness, with through-hole vias of 100 μm in diameter and 300 μm in pitch, using a vacuum laminator V-130, with the opposite side of the PET film in contact with the glass core. The lamination was performed at 100°C, a vacuum of 0.6 hPa, and a pressure of 0.3 MPa for 60 seconds, followed by heat curing at 180°C for 2 hours. The cross-sectional view of the through-holes was observed using an electron microscope D-500 (manufactured by Keyence Corporation), and the distance of the resin that penetrated into the through-holes was measured. The results are shown in Table 1.

[0078] [Relative permittivity and dielectric loss tangent] A test sample was prepared by sandwiching the prepared curable resin composition between mold frames measuring 30 mm (length) x 40 mm (width) x 100 μm (thickness) and press-curing it at 180°C and 3 MPa for 1 hour. A network analyzer E5063-2D5 (manufactured by Keysight Corporation) and a stripline (manufactured by Keycom Corporation) were connected to the prepared test sample, and the relative permittivity and dielectric loss tangent at a frequency of 10 GHz were measured. The results are shown in Table 1.

[0079] [Table 1]

[0080] In Examples 1-6, the cured products of the curable resin compositions exhibited low dielectric constant and low dielectric loss tangent, high die shear strength between glass and copper, and minimal resin penetration into the through-holes of the glass core. In Comparative Example 1, the die-shear strength between the glass and copper was low, resulting in delamination during the reliability test. In Comparative Examples 2 and 4, the minimum complex viscosity was high, making it impossible to laminate the resin composition onto the glass core. In Comparative Example 3, the low minimum complex viscosity resulted in a high degree of resin penetration into the through-holes. In Comparative Example 5, because it did not contain component (A) and had a low minimum complex viscosity, the degree of resin penetration into the through-hole was high. In Comparative Example 6, the dielectric loss tangent became high because it did not contain component (A).

Claims

1. (A) Cyclic imide resin represented by the following formula (1): 20.0 to 99.0% by mass of the entire composition 【Chemistry 1】 (In formula (1), A independently represents a tetravalent organic group containing a cyclic structure. Q independently represents a divalent aliphatic hydrocarbon group having 6 or more carbon atoms, which may contain a heteroatom, or a divalent hydrocarbon group derived from a dimer acid skeleton. B independently represents an arylene group having 6 or more carbon atoms, which may contain a heteroatom. X is a hydrogen atom or a methyl group, n is between 0 and 200, and m is between 0 and 200. The order of each repeating unit enclosed by n and m is not limited.) and (B) Curing catalyst: 0.1 to 5.0% by mass of the entire composition It contains, Component (A) comprises a cyclic imide resin (A1) in formula (1) where n+m is 21 or more, and a cyclic imide resin (A2) in which n is 0 to 10 and m is 0 to 10, in a mass ratio of (A1):(A2) = 98:2 to 50:

50. Furthermore, a curable resin composition that satisfies all of the following conditions (α) to (δ). (α) In the resin composition, the minimum complex viscosity measured at 40 to 150°C at a frequency of 1 Hz is 100 to 10,000 Pa·s. (β) In the resin composition, the minimum complex viscosity measured at 40 to 150°C at a frequency of 2 Hz is 10 to 2,000 Pa·s. (γ) The die shear strength between the cured resin composition and the glass at 25°C is 10 MPa or more. (δ) The die shear strength between the cured resin composition and copper at 25°C is 10 MPa or more.

2. The curable resin composition according to claim 1, wherein the weight-average molecular weight of the cyclic imide resin (A1) is 10,000 to 1,000,000.

3. The curable resin composition according to claim 1, wherein the weight-average molecular weight of the cyclic imide resin (A2) is 500 to 30,000.

4. The curable resin composition according to claim 1, wherein the component (B) is an imidazole compound.

5. The curable resin composition according to claim 1, which is an adhesive film for glass cores.

6. An adhesive for glass cores comprising the curable resin composition described in claim 1.

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