Thermosetting imide resin composition and uncured resin film, cured resin film, prepreg, substrate, adhesive and semiconductor encapsulant using the same

Abstract

To provide a resin composition capable of yielding a cured product that has excellent dielectric properties with a low dielectric tangent at high frequencies and also has excellent heat resistance with a high Tg.SOLUTION: A heat-curable imide resin composition contains: (A) a modified imide compound represented by the following formula (1) where A independently represents a tetravalent organic group having 4 to 200 carbon atoms; B independently represents a divalent organic group having 2 to 200 carbon atoms; n is 0 to 100; each of m and l is independently 0 to 18; X independently represents a carbon-carbon unsaturated bond-containing organic group; and (B) a reaction promotor.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermosetting imide resin composition and to an uncured resin film, a cured resin film, a prepreg, a substrate, an adhesive, and a semiconductor encapsulant using the same. [Background technology]

[0002] In recent years, electronic devices have become smaller and more high-performance, requiring finer and higher-density wiring in multilayer printed circuit boards. Furthermore, next-generation materials for high-frequency bands are needed, and reducing transmission loss is essential for noise countermeasures, thus requiring the development of insulating materials with excellent dielectric properties.

[0003] While epoxy resin compositions containing epoxy resin, specific phenolic curing agents, phenoxy resin, rubber particles, and polyvinyl acetal resin are known as insulating materials for multilayer printed circuit boards, as disclosed in Patent Documents 1 and 2, it has become clear that these materials are not satisfactory for high-frequency applications, such as those represented by the keyword 5G. In contrast, Patent Document 3 reports that an epoxy resin composition containing epoxy resin, an active ester compound, and a triazine-containing cresol novolac resin is effective in reducing dielectric loss tangent, but even with this material, further reduction in dielectric strength is necessary for high-frequency applications.

[0004] On the other hand, Patent Document 4 reports that a resin film made of a resin composition containing a bismaleimide resin having a long-chain alkyl group and a curing agent as a non-epoxy material exhibits excellent dielectric properties. However, this is essentially a combination of a bismaleimide resin having a long-chain alkyl group and a hard, low-molecular-weight aromatic maleimide, making it extremely difficult to achieve the high glass transition temperature (Tg) of 100°C or higher required for substrate applications.

[0005] Furthermore, recent research has revealed that bismaleimide resins with the aforementioned long-chain alkyl groups have a trade-off relationship in resin design: increasing the Tg (transition rate) worsens the dielectric properties, while improving the dielectric properties lowers the Tg.

[0006] Furthermore, Patent Documents 5 and 6 disclose polyimides using an aromatic tetracarboxylic anhydride, a dimer diamine derived from a dimer acid which is a dimer of an unsaturated fatty acid such as oleic acid, and an alicyclic diamine as raw materials. However, since water is generated by ring-closing dehydration during curing, for example, when used by laminating with a metal foil, swelling may occur depending on the usage conditions.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Summary of the Invention

Problems to be Solved by the Invention

[0008] <{ Therefore, an object of the present invention is to provide a thermosetting resin composition that becomes a cured product having a low dielectric tangent at high frequencies, excellent dielectric properties, and excellent heat resistance with a high Tg, and an uncured resin film, a cured resin film, a prepreg, a substrate, an adhesive, and a semiconductor encapsulant using the same.

Means for Solving the Problems

[0009] As a result of intensive studies to solve the above problems, the present inventors have found that the following thermosetting imide resin composition can achieve the above object, and completed the present invention.

[0010] <1> (A) The following formula (1)

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0011] The thermosetting imide resin composition of the present invention results in a cured product with a low dielectric loss tangent at high frequencies, excellent dielectric properties, and a high Tg, as well as excellent heat resistance. In particular, compared to a bismaleimide resin composition containing a compound in which the groups X at both ends of the modified imide compound of component (A) are maleimide groups, when molded into a film or substrate, it maintains a high glass transition temperature while exhibiting a low dielectric loss tangent and excellent heat resistance and dielectric properties.

Best Mode for Carrying Out the Invention

[0012] The present invention will be described in detail below.

[0013] (A) Modified imide compound The component (A) used in the present invention is a modified imide compound represented by the following formula (1).

Chemical formula

Chemical formula

Chemical formula

[0014] In the formula (1), A independently represents a tetravalent organic group having 4 to 200 carbon atoms, preferably 4 to 100 carbon atoms, more preferably 4 to 50 carbon atoms, and among them, it is preferably any of the tetravalent organic groups represented by the following structural formula.

Chemical formula

Chemical formula

Chemical formula

[0015] Note that A in formula (1) above may be of one type or multiple types.

[0016] In formula (1) above, B is independently a divalent organic group having 2 to 200 carbon atoms, preferably 3 to 100, and more preferably 6 to 50 carbon atoms. Examples of divalent organic groups of B having 2 to 200 carbon atoms include 1,10-diaminodecane, 1,12-diaminododecane, dimeramine, 1,2-diamino-2-methylpropane, 1,2-diaminocyclohexane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminomenthane, 1,8-diaminooctane, 1,9-diaminononane, 3,3'-diamino-N-methyldipropylamine, and diaminomaleonitol. 1,3-diaminopentane, 9,10-diaminophenanthrene, 4,4'-diaminooctafluorobiphenyl, 3,5-diaminobenzoic acid, 3,7-diamino-2,8-dimethoxyfluorene, 4,4'-diaminobenzophenone, 3,4-diaminobenzophenone, 3,4-diaminotoluene, 2,6-diaminoanthraquinone, 2,6-diaminotoluene, 2,3-diaminotoluene, 1,8-diaminonaphthalene, 2,4-diaminotoluene, 2,5-diaminotoluene, 1,4-diamino Anthraquinone, 1,5-diaminoanthraquinone, 1,5-diaminonaphthalene, 1,2-diaminoanthraquinone, 2,4-cumenediamine, 1,3-bis(aminomethyl)benzene(m-xylylenediamine), 1,4-bis(aminomethyl)benzene(p-xylylenediamine), 1,3-bis(aminomethyl)cyclohexane, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 4,4'-diamino-2,2' ―Bistrifluoromethylbiphenyl, 1,2-bis(4-amino-3-chlorophenyl)ethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane, bis(4-amino-3-ethylphenyl)fluorene, 3,4-diaminobenzoic acid, 2,3-diaminonaphthalene, 2,3-diaminophenol, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, 4,4'-diaminophenylsulfone, 3,3'-Diaminophenyl sulfone, bis(4-(4-aminophenoxy)phenyl) sulfone, bis(4-(3-aminophenoxy)phenyl) sulfone, 4,4'-oxydianiline, 4,4'-diaminodiphenyl sulfide, 3,4'-oxydianiline, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-3,3'-dimethoxybiphenyl, bisaniline M(1,3-bis[2-(4-aminophenyl)-2-propyl]benzene), bisaniline P(1,4-bis[2-(4-aminophenyl)-2-propyl]benzene), 9,9-bis(4-aminophenyl)fluorene, 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene, o-tolidine sulfone, methylenebis(anthranilic acid), 1,3-bis(4-aminophenoxy)-2,2-dimethylpropane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3',5,5'-tetramethylbenzidine, 4,4'-diaminobenzanilide, 2,2-bis(4-aminophenyl)hexafluoropropane, polyoxyalkylenediamines (e.g., Jeffamine®, manufactured by Huntsman). Examples include divalent organic groups obtained by removing two amino groups from diamines such as D-230, D-400, D-2000, and D-4000), bis(4-amino-3-methylcyclohexyl)methane, 1,2-bis(2-aminoethoxy)ethane, and 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0(2,6)]decane. Furthermore, from the viewpoint of improving heat resistance, it is preferable that the divalent organic group of B, having 2 to 200 carbon atoms, is a divalent organic group having an alicyclic structure or an aromatic ring. For example, the divalent organic group shown in the following structural formula is an example. [ka] (R6 , R 7 , R 8 and R 9 Z is independently a hydrogen atom, a C1-C5 alkyl group, a methoxy group, a fluoro group, a chloro group, a bromo group, or a trifluoromethyl group. Z is independently a member of the following formula [ka] It is a divalent organic group selected from among several. (Note that 'a' is a number from 0 to 6.)

[0017] Note that B in formula (1) above may be of one type or multiple types.

[0018] Furthermore, in formula (1) above, n is between 0 and 100, preferably between 0 and 90, and more preferably between 0 and 80.

[0019] There are no particular restrictions on the number-average molecular weight (Mn) of the modified imide compound of the present invention, but it is preferably 200 to 80,000, more preferably 200 to 70,000, and even more preferably 200 to 60,000.

[0020] In this specification, the number-average molecular weight (Mn) refers to the number-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] In formula (1) above, m and l are each independently between 0 and 18, where m is preferably between 0 and 12, more preferably between 0 and 6, and l is preferably between 0 and 12, more preferably between 0 and 6.

[0022] In formula (1) above, X is an organic group containing a carbon-carbon unsaturated bond as shown in formula (2) below. [ka]

[0023] In formula (2), R 1 , R 2 , R 3 , R 4 and R 5 These are independently a hydrogen atom, a C1-C5 alkyl group, or a C4-C10 (hetero)aryl group. R 1 , R 2 , R 3 , R 4 and R 5 Examples of C1-C5 alkyl groups represented by include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, and pentyl groups. R 1 , R 2 , R 3 , R 4 and R 5 Examples of (hetero)aryl groups having 4 to 10 carbon atoms, as shown, include aryl groups having 6 to 10 carbon atoms such as phenyl, tolyl, xylyl, and naphthyl groups, and heteroaryl groups having 4 to 10 carbon atoms such as furyl, thienyl, pyridyl, and indolyl groups. R 1 A hydrogen atom, a methyl group, or a phenyl group is preferred. 2 and R 3 A hydrogen atom, a methyl group, or a phenyl group is preferred. 4 and R 5 A hydrogen atom or a methyl group is preferred as the element.

[0024] In formula (2), о and p are each independently 0 or 1, where о is preferably 0 and p is preferably 0.

[0025] In formula (2), Y is one of the divalent organic groups shown in the following structural formula, and is preferably a phenylene group. [ka]

[0026] (A) There are no particular restrictions on the method of producing component (A), but it can be efficiently produced by, for example, the method shown below. In formula (1), an example of a method for producing a modified imide compound in which n is 1 or greater is: Step A involves synthesizing an amic acid from an acid anhydride represented by formula (3) below and a diamine represented by formula (4) below, and then performing ring-closing dehydration. Following step A, step B involves synthesizing an amic acid using the reactant obtained in step A and a monoamine having an unsaturated carbon-carbon bond represented by formula (5) below, followed by ring-closing and dehydration. A manufacturing method having the above is an example. Furthermore, as an example of a method for producing a modified imide compound in formula (1) where n is 0, Step C involves synthesizing an amic acid using an acid anhydride represented by formula (3) below and a monoamine having an unsaturated carbon-carbon bond represented by formula (5) below, followed by ring-closing dehydration. A manufacturing method having the following characteristics can be cited. [ka] (In the formula, A is the same as that shown in formula (1) above.) [ka] (In the formula, B is the same as that shown in formula (1) above.) [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 Y, l, o, and p are the same as those shown in formula (1) above.

[0027] Although the manufacturing method is shown above, the basic procedure involves either synthesizing amicolic acid with an acid anhydride (tetracarboxylic dianhydride) and a diamine, undergoing ring-closing dehydration (step A), reacting it with a monoamine having an unsaturated carbon-carbon bond after step A to synthesize amicolic acid, and finally undergoing ring-closing dehydration to seal the molecular chain ends with an organic group having an unsaturated carbon-carbon bond (step B), or reacting an acid anhydride (tetracarboxylic dianhydride) with a monoamine having an unsaturated carbon-carbon bond to synthesize amicolic acid, and finally undergoing ring-closing dehydration to seal the molecular chain ends with an organic group having an unsaturated carbon-carbon bond (step C) to obtain a modified imide compound.

[0028] In the above manufacturing method, each step can be broadly divided into two parts: the synthesis reaction of amical and the ring-closing dehydration reaction, which will be described in detail below.

[0029] In step A, amical acid is first synthesized by reacting a specific tetracarboxylic dianhydride with a specific diamine. This reaction generally proceeds in an organic solvent (e.g., a nonpolar solvent or a high-boiling point aprotic polar solvent) at room temperature (25°C) to 100°C. The subsequent ring-closing dehydration reaction of amic acid proceeds under conditions of 90-200°C, while removing the by-product water from the system via condensation. Organic solvents (e.g., nonpolar solvents, high-boiling point aprotic polar solvents, etc.) or acid catalysts can be added to accelerate the ring-closing dehydration reaction. Examples of organic solvents include toluene, xylene, anisole, biphenyl, naphthalene, N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO). These may be used individually or in combination of two or more. Examples of acid catalysts include sulfuric acid, methanesulfonic acid, and trifluoromethanesulfonic acid. These may be used individually or in combination of two or more. The molar ratio of the acid anhydride (tetracarboxylic dianhydride) represented by formula (3) to the diamine represented by formula (4) is preferably tetracarboxylic dianhydride / diamine = 1.01 to 1.50 / 1.0, and more preferably tetracarboxylic dianhydride / diamine = 1.01 to 1.35 / 1.0. By blending in this ratio, it is possible to synthesize an imide compound (hereinafter, the reaction product obtained in step A will also be simply called an imide compound) in which both ends are carboxylic acid anhydride groups. In addition, the tetracarboxylic dianhydride and diamine used in step A may be one type each, or one or both of the tetracarboxylic dianhydride and diamine may be multiple types.

[0030] In step B, an amic acid is first synthesized by reacting the imide compound obtained in step A with a monoamine having an unsaturated carbon-carbon bond at room temperature (25°C) to 100°C. Finally, the ring-closing dehydration is performed under conditions of 90 to 200°C while removing the by-product water in the system, thereby sealing both ends of the molecular chain with organic groups having unsaturated carbon-carbon bonds, and the desired modified imide compound can be obtained.

[0031] The molar ratio of the imide compound to the monoamine having an unsaturated carbon-carbon bond is preferably 1.0:1.6-2.5, and more preferably 1.0:1.8-2.2. In addition, one or more types of monoamines having unsaturated carbon-carbon bonds may be used in step B.

[0032] In step C, an amic acid is synthesized by reacting a specific tetracarboxylic dianhydride with a monoamine having an unsaturated carbon-carbon bond in an organic solvent (e.g., a nonpolar solvent or a high-boiling point aprotic polar solvent) at room temperature (25°C) to 100°C. Subsequently, the ring-closing dehydration reaction of the amic acid proceeds under conditions of 90 to 200°C, and the by-product water is removed from the system by the condensation reaction, thereby sealing both ends of the molecular chain with organic groups having unsaturated carbon-carbon bonds, and obtaining the desired modified imide compound. Organic solvents (e.g., nonpolar solvents, high-boiling point aprotic polar solvents, etc.) or acid catalysts may be added to accelerate the ring-closing dehydration reaction. The molar ratio of tetracarboxylic dianhydride to monoamine having an unsaturated carbon-carbon bond is preferably tetracarboxylic dianhydride:monoamine having an unsaturated carbon-carbon bond = 1.0:1.6~2.5, and more preferably 1.0:1.8~2.2. In addition, one or more types of monoamines having unsaturated carbon-carbon bonds may be used in step C.

[0033] The modified imide compound obtained by the method described above can be purified using conventional methods and can be used as is as a varnish.

[0034] (B) Reaction accelerator Component (B) used in this invention is a reaction accelerator. The reaction accelerator, which is component (B) used in the present invention, is added to initiate and accelerate the radical polymerization or anionic polymerization reaction of the modified imide compound, which is component (A). (B) Component is not particularly limited as long as it promotes this reaction, but from the viewpoint of the reaction mechanism, it is preferable to use a radical polymerization initiation catalyst such as an organic peroxide or an anionic polymerization initiation catalyst containing one or more of nitrogen atoms and phosphorus atoms.

[0035] Examples of radical polymerization initiation catalysts include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyn-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

[0036] Examples of anionic polymerization initiation catalysts include ionic catalysts such as imidazoles (e.g., 2-ethyl-4-methylimidazole), tertiary amines, quaternary ammonium salts, boron trifluoride amine complexes, organophosphines (e.g., triphenylphosphine), and organophosphonium salts.

[0037] (B) The reaction accelerator, which is component (B), may be used alone or in combination of two or more types.

[0038] The reaction accelerator, which is component (B), is preferably blended in an amount of 0.01 to 10 parts by mass, particularly 0.1 to 5 parts by mass, per 100 parts by mass of component (A). If the amount of component (B) is greater than this range, unreacted component (B) will remain, which may worsen the dielectric properties. Conversely, if the amount of component (B) is less than the aforementioned range, curing will not proceed sufficiently, and there is a concern that the dielectric properties and heat resistance will decrease. Furthermore, if the amount of component (B) falls outside the above range, the curing of the thermosetting imide resin composition may become extremely slow or extremely fast during molding, which is undesirable, and the balance between the heat resistance and moisture resistance of the resulting cured product may also be poor.

[0039] The amount of component (A) in the thermosetting imide resin composition of the present invention is preferably 5 to 99.99% by mass, and more preferably 10 to 99.9% by mass, based on the total mass of the composition.

[0040] Other additives The thermosetting imide resin composition of the present invention may further contain various additives as needed, provided that the effects of the present invention are not impaired. Examples of other additives are given below.

[0041] Thermosetting resin having reactive groups that can react with organic groups having carbon-carbon unsaturated bonds. In the present invention, a thermosetting resin having a reactive group capable of reacting with an organic group having a carbon-carbon unsaturated bond may be further added. Reactive groups that can react with organic groups having carbon-carbon unsaturated bonds include epoxy groups, maleimide groups, hydroxyl groups, amino groups, and thiol groups. Furthermore, the thermosetting resin having the reactive group is not limited to any particular type, and examples include thermosetting resins having carbon-carbon unsaturated bonds such as alkenyl groups like allyl groups and vinyl groups other than component (A), (meth)acrylic groups, epoxy resins, maleimide resins, phenolic resins, melamine resins, urea resins, silicone resins, modified polyphenylene ether resins, and polyfunctional thiols. The thermosetting resin having a reactive group that can react with the added organic group having a carbon-carbon unsaturated bond may be one type or multiple types.

[0042] The amount of thermosetting resin having a reactive group capable of reacting with an organic group having a carbon-carbon unsaturated bond is 0 to 30% by mass of the total amount of component (A) and the thermosetting resin having a reactive group capable of reacting with an organic group having a carbon-carbon unsaturated bond, preferably 0 to 20% by mass.

[0043] inorganic filler In the present invention, inorganic fillers may be added as needed. Inorganic fillers are added to enhance the strength and rigidity of the cured product of the thermosetting imide resin composition of the present invention, or to adjust the coefficient of thermal expansion and the dimensional stability of the cured product. As inorganic fillers, those commonly used in epoxy resin compositions and silicone resin compositions can be used. Examples include silicas such as spherical silica, fused silica, and crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, barium sulfate, talc, clay, aluminum hydroxide, magnesium hydroxide, calcium carbonate, glass fibers, and glass particles. Furthermore, fluororesins, coating fillers, and / or hollow particles may be used to improve dielectric properties, and conductive fillers such as metal particles, metal-coated inorganic particles, carbon fibers, and carbon nanotubes may be added for purposes such as imparting conductivity. One type of inorganic filler or multiple types may be added.

[0044] The average particle size and shape of the inorganic filler are not particularly limited, but spherical silica with an average particle size of 0.5 to 5 μm is particularly preferred when forming underfill materials, films, or substrates. Spherical silica with an average particle size of 3 to 45 μm is preferred for adhesive and semiconductor encapsulant applications. The average particle size is determined by the mass-mean value D of the particle size distribution measured by laser diffraction. 50 This is the value obtained as (or median diameter).

[0045] There are no particular restrictions on the amount of inorganic filler added, but it is preferably 5 to 3,000 parts by mass, more preferably 10 to 2,500 parts by mass, and even more preferably 50 to 2,000 parts by mass per 100 parts by mass of component (A). Within this range, the functionality of the inorganic particles can be fully exercised while maintaining the strength of the resin composition.

[0046] Furthermore, to improve the properties of the inorganic filler, it is preferable that the surface is treated with a silane coupling agent having an organic group that can react with an organic group having a carbon-carbon unsaturated bond. Examples of such silane coupling agents include epoxy group-containing alkoxysilanes, amino group-containing alkoxysilanes, (meth)acrylic group-containing alkoxysilanes, and alkenyl group-containing alkoxysilanes. As the silane coupling agent, (meth)acrylic group and / or amino group-containing alkoxysilanes are preferably used, specifically, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and the like.

[0047] others In addition to the above, non-functional silicone oil, thermoplastic resin, thermoplastic elastomer, organic synthetic rubber, photosensitizer, light stabilizer, polymerization inhibitor, flame retardant, pigment, dye, adhesive aid, etc. may be added, or ion trapping agents, etc. may be added to improve electrical properties.

[0048] [Manufacturing method] A method for producing the resin composition of the present invention includes adding component (A) and component (B) and other additives as needed, and mixing them using, for example, a planetary mixer or a stirrer. The thermosetting imide resin composition of the present invention can also be dissolved in an organic solvent and treated as a varnish. Varnishing makes it easier to form a film, and also makes it easier to apply to and impregnate glass cloth made of low-dielectric glass such as E glass or quartz glass, thus facilitating the manufacture of prepregs. As for organic solvents, any solvent that dissolves component (A) can be used without restriction.

[0049] The thermosetting imide resin composition of the present invention can be used to obtain an uncured resin sheet or film by coating the above varnish onto a substrate and removing the solvent, or to obtain a cured resin sheet or film by further curing it. The following are examples of methods for manufacturing sheets and films, but are not limited to these.

[0050] For example, after applying a thermosetting imide resin composition dissolved in an organic solvent to a substrate, heating at a temperature of 80°C or higher, preferably 100°C or higher, for 0.5 to 5 hours removes the organic solvent. Further heating at a temperature of 130°C or higher, preferably 150°C or higher, for 0.5 to 10 hours forms a resin-cured film with a flat and strong surface. The temperatures in the drying step to remove the organic solvent and the subsequent heat curing step may be constant, but it is preferable to gradually increase the temperature. This allows for efficient removal of the organic solvent from the composition and efficient advancement of the resin curing reaction. Examples of application methods include spin coaters, slit coaters, sprays, dip coaters, bar coaters, etc., but there are no particular limitations.

[0051] The aforementioned substrate can be one of the most commonly used materials, such as polyolefin resins including polyethylene (PE) resin, polypropylene (PP) resin, and polystyrene (PS) resin, or polyester resins including polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, and polycarbonate (PC) resin. The surface of the substrate may also be treated with a release agent. The thickness of the coating layer is not particularly limited, but the thickness after solvent removal is in the range of 1 to 200 μm, preferably 3 to 80 μm. Furthermore, a cover film may be used on top of the coating layer.

[0052] Alternatively, the components may be pre-mixed and extruded into a sheet or film using a melt kneader to produce an uncured resin film (uncured resin sheet) or a cured resin film (cured resin sheet).

[0053] When using the thermosetting imide resin composition of the present invention as a semiconductor encapsulant, components (A) and (B), and other components as needed, should be blended in a predetermined composition ratio, thoroughly and uniformly mixed using a mixer or the like, then melt-mixed using a hot roll, kneader, extruder or the like, followed by cooling and solidification, and finally crushed to an appropriate size. The resulting resin composition can be used as an encapsulant. Furthermore, when using the thermosetting imide resin composition of the present invention as an adhesive, components (A) and (B), and other components as needed, are blended in a predetermined composition ratio, mixed using a mixer such as a planetary mixer, and then kneaded and mixed using a three-roll mill as needed to improve dispersibility. The resulting resin composition can be used as an adhesive.

[0054] Common molding methods using semiconductor encapsulants include transfer molding and compression molding. In transfer molding, a transfer molding machine is used, and the molding pressure is 5-20 N / mm². 2 The molding process is carried out at a molding temperature of 120-190°C for 30-500 seconds, preferably at a molding temperature of 150-185°C for 30-180 seconds. In the compression molding method, a compression molding machine is used, and the molding temperature is 120-190°C for 30-600 seconds, preferably at a molding temperature of 130-160°C for 120-300 seconds. Furthermore, in any of the molding methods, post-curing may be carried out at 150-225°C for 0.5-20 hours.

[0055] [Prepreg] A prepreg according to one embodiment of the present invention comprises the thermosetting imide resin composition of the present invention and a fibrous substrate. The thermosetting imide resin composition in the prepreg may be a semi-cured product of the resin composition. A semi-cured product is a state in which the resin composition has been partially cured to the extent that it can be further cured. In other words, a semi-cured product is a state in which the resin composition has been partially cured, so-called B-stage. On the other hand, the uncured state is sometimes called A-stage. As mentioned above, the fibrous base material can be low-dielectric glass such as E glass and quartz glass, as well as S glass and T glass, and the type of glass used is not limited, but from the viewpoint of making the most of the properties of the thermosetting imide resin composition of the present invention, quartz glass cloth with low relative permittivity and dielectric loss tangent is preferred. The thickness of the fibrous base material that is generally used is, for example, 0.01 mm or more and 0.3 mm or less.

[0056] When manufacturing a prepreg, it is preferable that the thermosetting imide resin composition be a varnish-like resin varnish prepared for impregnation into the fibrous substrate, which is the base material for forming the prepreg. Such a varnish-like resin composition (resin varnish) can be prepared, for example, as follows.

[0057] First, each component of the resin composition that is soluble in an organic solvent is added to the organic solvent and dissolved. Heating may be used as needed during this process. Then, components that are not soluble in the organic solvent, such as inorganic fillers, are added as needed, and the mixture is dispersed using a ball mill, bead mill, planetary mixer, roll mill, etc., until a predetermined dispersion state is reached, thereby preparing a varnish-like resin composition (resin varnish). The organic solvent used here is not particularly limited as long as it does not inhibit the curing reaction. Specifically, examples include toluene, methyl ethyl ketone (MEK), xylene, and anisole. Next, the varnish-like resin composition (resin varnish) is impregnated into the fibrous substrate by immersion, coating, etc., and then dried. The impregnation process can be repeated multiple times as needed. Furthermore, by repeatedly impregnating with multiple resin compositions of different compositions and concentrations, it is possible to adjust the final composition and impregnation amount to the desired level. A fibrous substrate impregnated with a resin composition (resin varnish) is heated under desired heating conditions, for example, at 80°C to 400°C for 1 minute to 2 hours. Heating yields a prepreg comprising a thermosetting imide resin composition in either a pre-cured state (Stage A) or a semi-cured state (Stage B).

[0058] [substrate] The aforementioned prepreg and copper foil may be layered, pressed, and heat-cured to be used as a substrate. There are no particular restrictions on the method of manufacturing the substrate, but for example, it can be manufactured by using 1 to 20 sheets, preferably 2 to 10 sheets, of the prepreg, placing copper foil on one or both sides thereof, pressing, and heat-curing. There are no particular restrictions on the thickness of the copper foil, but 3 to 70 μm is preferred, 10 to 50 μm is more preferred, and 15 to 40 μm is even more preferred. Within this range, a multilayer substrate with high reliability can be formed. There are no particular restrictions on the molding conditions for the substrate, but for example, it can be molded using a multi-stage press, multi-stage vacuum press, continuous molding, autoclave molding machine, etc., within the range of temperature 100 to 400°C, pressure 1 to 100 MPa, and heating time 0.1 to 4 hours. Alternatively, the substrate can be molded by combining the prepreg, copper foil, and inner layer wiring board of the present invention. [Examples]

[0059] The present invention will be specifically described below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. In the examples, comparative examples, reference examples, and comparative reference examples, "room temperature" means 25°C.

[0060] [Synthesis Example 1] (Preparation of Modified Imide Compound 1, Reaction Equation 1) In a 500 mL three-necked glass flask equipped with a stirrer, Dean-Stark tube, cooling condenser, and thermometer, 41.05 g (0.100 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 54.65 g (0.105 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) and 216 g of anisole were added and the mixture was stirred at 70°C for 2 hours to synthesize amicolic acid. Subsequently, the temperature was raised to 150°C and the mixture was stirred for 5 hours while removing the by-product water to synthesize the polyimide compound. Subsequently, 0.63 g (0.011 moles, equivalent to 2.2 moles per mole of the polyimide compound) of allylamine was added to a flask containing the polyimide compound solution, which had been cooled to room temperature, and the mixture was stirred at room temperature for 1 hour to synthesize amic acid. The mixture was then heated to 150°C and stirred for 6 hours while removing the by-product water by distillation, yielding the target modified imide compound 1 (number-average molecular weight: 42,000), represented by equation (6) of reaction equation 1 below, as a yellow varnish (containing 71% by mass of anisole). [ka]

[0061] [Synthesis Example 2] (Preparation of Modified Imide Compound 2, Reaction Equation 2) In a 500 mL three-necked glass flask equipped with a stirrer, Dean-Stark tube, cooling condenser, and thermometer, 41.05 g (0.100 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 54.65 g (0.105 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) and 216 g of anisole were added and the mixture was stirred at 70°C for 2 hours to synthesize amicolic acid. Subsequently, the temperature was raised to 150°C and the mixture was stirred for 5 hours while removing the by-product water to synthesize the polyimide compound. Subsequently, 0.78 g (0.011 moles, equivalent to 2.2 moles per mole of the polyimide compound) of 3-buten-1-amine was added to a flask containing the polyimide compound solution, which had been cooled to room temperature, and the mixture was stirred at room temperature for 1 hour to synthesize amical. The mixture was then heated to 150°C and stirred for 6 hours while removing the by-product water by distillation, yielding the target modified imide compound 2 (number-average molecular weight: 33,000), represented by equation (7) of reaction equation 2 below, as a brown varnish (containing 66% by mass of anisole). [ka]

[0062] [Synthesis Example 3] (Preparation of Modified Imide Compound 3, Reaction Equation 3) In a 500 mL three-necked glass flask equipped with a stirrer, Dean-Stark tube, cooling condenser, and thermometer, 25.17 g (50.0 mmol) of 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene, 33.74 g (52.5 mmol) of 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorendiohydride, and 172 g of anisole were added and stirred at 70°C for 2 hours to synthesize amicolic acid. Subsequently, the temperature was raised to 150°C and the mixture was stirred for 5 hours while distilling off the by-product water to synthesize the polyimide compound. Subsequently, 0.31 g of allylamine (5.5 mmol, equivalent to 2.2 moles per mole of the polyimide compound) was added to a flask containing the polyimide compound solution, which had been cooled to room temperature, and the mixture was stirred at room temperature for 1 hour to synthesize amic acid. The mixture was then heated to 150°C and stirred for 6 hours while removing the by-product water by distillation, yielding the target modified imide compound 3 (number-average molecular weight: 22,000), represented by equation (8) of reaction equation 3 below, as a yellow varnish (containing 72% by mass of anisole). [ka]

[0063] [Synthesis Example 4] (Preparation of Modified Imide Compound 4, Reaction Equation 4) In a 500 mL three-necked glass flask equipped with a stirrer, Dean-Stark tube, cooling condenser, and thermometer, 20.53 g (50.0 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 27.33 g (52.5 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) and 140 g of anisole were added and stirred at 70°C for 2 hours to synthesize amicolic acid. Subsequently, the temperature was raised to 150°C and the mixture was stirred for 5 hours while distilling off the by-product water to synthesize the polyimide compound. Subsequently, 0.73 g of 4-vinylbenzylamine (5.5 mmol, equivalent to 2.2 moles per mole of the polyimide compound) was added to a flask containing the polyimide compound solution, which had been cooled to room temperature, and the mixture was stirred at room temperature for 1 hour to synthesize amic acid. The mixture was then heated to 150°C and stirred for 6 hours while removing the by-product water by distillation, yielding the target modified imide compound 4 (number-average molecular weight: 28,000), represented by equation (9) of reaction equation 4 below, as a brown varnish (containing 77% by mass of anisole). [ka]

[0064] [Synthesis Example 5] (Preparation of Modified Imide Compound 5, Reaction Equation 5) In a 500 mL three-necked glass flask equipped with a stirrer, Dean-Stark tube, cooling condenser, and thermometer, 20.53 g (50.0 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 27.33 g (52.5 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) and 139 g of anisole were added and stirred at 70°C for 2 hours to synthesize amicolic acid. Subsequently, the temperature was raised to 150°C and the mixture was stirred for 5 hours while removing the by-product water to synthesize the polyimide compound. Subsequently, 0.39 g of methallylamine (5.5 mmol, equivalent to 2.2 moles per mole of the polyimide compound) was added to a flask containing the polyimide compound solution, which had been cooled to room temperature, and the mixture was stirred at room temperature for 1 hour to synthesize amic acid. The mixture was then heated to 150°C and stirred for 6 hours while removing the by-product water by distillation, yielding the target modified imide compound 5 (number-average molecular weight: 38,000), represented by equation (10) of reaction equation 5 below, as a brown varnish (containing 76% by mass of anisole). [ka]

[0065] [Comparative Synthesis Example 1] (Preparation of Bismaleimide Compound 1, Reaction Equation 6) In a 500 mL three-necked glass flask equipped with a stirrer, Dean-Stark tube, cooling condenser, and thermometer, 42.93 g (0.105 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 52.05 g (0.100 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), and 171 g of anisole were added and stirred at 70°C for 2 hours to synthesize amicolic acid. Subsequently, the temperature was raised to 150°C and the mixture was stirred for 5 hours while removing the by-product water to synthesize the polyimide compound. Subsequently, 1.08 g (0.011 mol) of maleic anhydride was added to a flask containing the polyimide solution, which had been cooled to room temperature, and the mixture was stirred at room temperature for 1 hour to synthesize amic acid. The mixture was then heated to 150°C and stirred for 6 hours while removing the by-product water by distillation, yielding the target bismaleimide compound 1 (number-average molecular weight: 20,000), represented by equation (11) of reaction equation 6 below, as a pale yellow varnish (containing 65% by mass of anisole). [ka]

[0066] [Synthesis Example 6] (Preparation of Modified Imide Compound 6, Reaction Equation 7) In a 500 mL three-necked glass flask equipped with a stirrer, Dean-Stark tube, cooling condenser, and thermometer, 12.56 g (0.22 mol) of allylamine, 52.05 g (0.10 mol) of 4,4'-(4,4'-isopropylidene diphenoxy)bis(phthalic anhydride), and 142 g of anisole were added and stirred at 70°C for 2 hours to synthesize amico acid. Subsequently, the temperature was raised to 150°C and the mixture was stirred for 5 hours while distilling off the by-product water to obtain a varnish of modified imide compound 6. The obtained varnish was added dropwise to 1,000 g of heptane, and the precipitate was collected by filtration. By drying the obtained solid, the target modified imide compound 6 (number-average molecular weight: 480), shown in equation (12) of reaction equation 7 below, was obtained as a brown solid. [ka]

[0067] [Synthesis Example 7] (Preparation of Modified Imide Compound 7, Reaction Equation 8) In a 500 mL three-necked glass flask equipped with a stirrer, Dean-Stark tube, cooling condenser, and thermometer, 12.56 g (0.22 mol) of allylamine, 62.84 g (0.10 mol) of 4,4'-(4,4'-hexafluoroisopropylidene diphenoxy)bis(phthalic anhydride), and 168 g of anisole were added and stirred at 70°C for 2 hours to synthesize amicoic acid. Subsequently, the temperature was raised to 150°C and the mixture was stirred for 5 hours while removing the by-product water to obtain a varnish of modified imide compound 7. The obtained varnish was added dropwise to 1,000 g of heptane, and the precipitate was collected by filtration. By drying the obtained solid, the target modified imide compound 7 (number-average molecular weight: 720), shown in equation (13) of reaction equation 8 below, was obtained as a white solid. [ka]

[0068] [Synthesis Example 8] (Preparation of Modified Imide Compound 8, Reaction Equation 9) In a 500 mL three-necked glass flask equipped with a stirrer, Dean-Stark tube, cooling condenser, and thermometer, 12.56 g (0.22 mol) of allylamine, 31.02 g (0.10 mol) of oxydiphthalic anhydride, and 93 g of anisole were added and stirred at 70°C for 2 hours to synthesize amical. Subsequently, the temperature was raised to 150°C and the mixture was stirred for 5 hours while removing the by-product water to obtain a varnish of modified imide compound 8. The obtained varnish was added dropwise to 1,000 g of heptane, and the precipitate was collected by filtration. By drying the obtained solid, the target modified imide compound 8 (number-average molecular weight: 240), shown in equation (14) of reaction equation 9 below, was obtained as a white solid. [ka]

[0069] [Synthesis Example 9] (Preparation of Modified Imide Compound 9, Reaction Equation 10) In a 500 mL three-necked glass flask equipped with a stirrer, Dean-Stark tube, cooling condenser, and thermometer, 12.56 g (0.22 mol) of allylamine, 44.42 g (0.10 mol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, and 125 g of anisole were added and stirred at 70°C for 2 hours to synthesize amical. Subsequently, the temperature was raised to 150°C and the mixture was stirred for 5 hours while removing the by-product water to obtain a varnish of modified imide compound 9. The obtained varnish was added dropwise to 1,000 g of heptane, and the precipitate was collected by filtration. By drying the obtained solid, the target modified imide compound 9 (number-average molecular weight: 430), shown in equation (15) of reaction equation 10 below, was obtained as a white solid. [ka]

[0070] [Synthesis Example 10] (Preparation of Modified Imide Compound 10, Reaction Equation 11) In a 500 mL three-necked glass flask equipped with a stirrer, Dean-Stark tube, cooling condenser, and thermometer, 12.56 g (0.22 mol) of allylamine, 64.26 g (0.10 mol) of 9,9'-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorenodioic anhydride, and 171 g of anisole were added and stirred at 70°C for 2 hours to synthesize amical. Subsequently, the temperature was raised to 150°C and the mixture was stirred for 5 hours while removing the by-product water to obtain a varnish of modified imide compound 10. The obtained varnish was added dropwise to 1,000 g of heptane, and the precipitate was collected by filtration. By drying the obtained solid, the target modified imide compound 10 (number-average molecular weight: 690), shown in equation (16) of reaction equation 11 below, was obtained as a white solid. [ka]

[0071] [Comparative Example 2] (Bismaleimide Compound 2) 2,2-Bis[4-(4-maleimidophenoxy)phenyl]propane (BMI-4000: manufactured by Yamato Chemical Industries, Ltd., number average molecular weight: 620)

[0072] [Examples 1-5, Comparative Example 1] The varnishes of the modified imide compounds 1-5 synthesized in the above synthesis examples 1-5 and the bismaleimide compound 1 synthesized in the above comparative synthesis example 1 were each adjusted to contain 50 g of resin, and 1 g of dicumyl peroxide was dissolved in them to obtain varnishes of the resin compositions. The varnishes of each resin composition prepared above were applied to a 100 μm thick Aflex film using a roller coater to a thickness of 30 μm after drying, and dried at 80°C for 15 minutes to obtain uncured resin films. Subsequently, post-curing was performed at 180°C for 2 hours to prepare film-like samples for dielectric property evaluation. After that, the Aflex film was peeled off before being subjected to measurement.

[0073] [Examples 6-10, Comparative Example 2] A resin composition was obtained by adding 1 g of dicumyl peroxide to 50 g each of the modified imide compounds 6-10 and bismaleimide compound 2 synthesized in the above synthesis examples 6-10, and mixing them. An uncured resin film was obtained by pressing each of the resin compositions prepared above at 180°C for 10 minutes so that the thickness after drying was 200 μm. Subsequently, a film-like sample for dielectric property evaluation was prepared by post-curing at 180°C for 2 hours.

[0074] <Dielectric properties (dielectric loss tangent)> A network analyzer (Keysight E5063-2D5) and a stripline (Keycom Corporation) were connected to the film sample prepared above for dielectric property evaluation, and the dielectric loss tangent of the film at a frequency of 10 GHz was measured.

[0075] <Glass transition temperature (Tg)> The glass transition temperature of the film-like samples prepared as described above for dielectric property evaluation was measured using a Rigaku TMA8140C or a TA Instruments DMA-800.

[0076] [Table 1]

[0077] The resin compositions of modified imide compounds 1 to 5 were found to have improved dielectric properties, with a smaller dielectric loss tangent, while maintaining a high glass transition temperature, compared to the resin composition of bismaleimide compound 1 synthesized in Comparative Synthesis Example 1.

[0078] [Table 2]

[0079] It was revealed that the resin compositions of modified imide compounds 6-10 exhibit improved dielectric properties, with a smaller dielectric loss tangent, while maintaining a high glass transition temperature, compared to the resin composition of bismaleimide compound 2.

[0080] [Examples 11-15, Comparative Example 3] A varnish was obtained by mixing 100 g each of the modified imide compounds 1-5 prepared in the above synthesis examples 1-5, bismaleimide compound 1, 2 g of dicumyl peroxide, 133 g of silica dispersion slurry (average particle size 0.5 μm, solid concentration 75% by mass, solvent: toluene, trade name: 5SV-CT1, manufactured by Admatex Co., Ltd.), and 200 g of anisole.

[0081] [Prepreg manufacturing method] The obtained varnish was impregnated with quartz glass cloth (thickness 90 μm, product name: SQX2116, manufactured by Shin-Etsu Chemical Co., Ltd.), heated at 120°C for 6 minutes to evaporate the solvent, and a prepreg (resin composition impregnation amount: 50% by mass) was produced.

[0082] [Manufacturing method for copper-clad laminates] A copper-clad laminate was manufactured by placing 18 μm thick copper foil (surface roughness: 0.6 μm) on both sides of the prepreg obtained above, pressing it at 1.7 MPa, and heating it at 180°C for 1 hour.

[0083] <Dielectric properties (dielectric loss tangent), glass transition temperature (Tg)> After removing the copper foil from both sides of the copper-clad laminate described above by etching, a network analyzer (Keysight E5063-2D5) and a stripline (Keycom Corporation) were connected, and the dielectric loss tangent of the prepreg at a frequency of 10 GHz was measured. The glass transition temperature was also measured using a TA Instruments DMA-800. The results are shown in Table 3.

[0084] [Table 3]

[0085] As shown in Table 3, we were able to manufacture a material with excellent dielectric properties and heat resistance.

[0086] [Manufacturing method for printed circuit boards] Ten prepregs obtained as described above and eleven 18 μm thick copper foils (surface roughness: 0.6 μm) were stacked in sequence and pressed at 1.7 MPa, then heated at 180°C for 1 hour to produce a copper-clad laminate. A 30 μm thick dry resist film (NIT430E, manufactured by Nikko Materials Co., Ltd.) was vacuum-laminated onto this copper-clad laminate at 0.4 MPa, 80°C, and 60 seconds. A mask with a circuit pattern formed on it was then placed in contact with the laminate, UV light was irradiated from above, and the laminate was developed with a sodium bicarbonate aqueous solution. After that, the laminate was etched by impregnation with an etching solution (H-1000A, manufactured by Sunhayato Co., Ltd.), and then washed with a sodium hydroxide aqueous solution to produce a printed circuit board with the circuit formed on it. [Industrial applicability]

[0087] The thermosetting imide resin composition of the present invention, when molded into a film or substrate, can provide a cured product that exhibits low dielectric loss tangent and excellent dielectric properties at high frequencies, as well as high Tg and excellent heat resistance. Specifically, the thermosetting imide resin composition of the present invention is useful for applications such as multilayer printed circuit boards used in high-frequency electronic equipment that require insulating materials with excellent dielectric properties.

Claims

1. (A) The following formula (1) 【Chemistry 1】 (In formula (1), A is independently one of the tetravalent organic groups shown in the following structural formulas.) 【Chemistry 2-1】 【Chemistry 2-2】 [Chemistry 2-3] 【Chemistry 2-4】 (The bonds in the above structural formula that are not bonded to substituents are bonded to the carbonyl carbon that forms the cyclic imide structure in formula (1).) B independently represents a divalent organic group with 2 to 200 carbon atoms. n is 0 to 100, and m and l independently are 0 to 18. X independently represents the following formula (2) 【Transformation 3】 (In formula (2), R 1 , R 2 , R 3 , R 4 and R 5 is independently a hydrogen atom, a C1-C5 alkyl group, or a C4-C10 (hetero)aryl group. o and p are independently 0 or 1. Y is one of the divalent organic groups shown in the following structural formulas. 【Chemistry 4】 This is an organic group containing a carbon-carbon unsaturated bond, as shown by [the symbol]. Modified imide compounds shown in, and (B) Reaction accelerator It contains, Component (B) is 0.1 to 5 parts by mass per 100 parts by mass of component (A). A thermosetting imide resin composition for insulating material of multilayer printed circuit boards, wherein the dielectric loss tangent at a frequency of 10 GHz after curing is 0.0046 or less and the glass transition temperature is 171°C or higher.

2. In formula (1), A is one of the tetravalent organic groups shown in the following structural formulas, 【Chemistry 5-1】 【Chemistry 5-2】 【Chemistry 5-3】 (The bonds in the above structural formula that are not bonded to substituents are bonded to the carbonyl carbon that forms the cyclic imide structure in formula (1).) A thermosetting imide resin composition for insulating material of a multilayer printed circuit board according to claim 1, wherein B in formula (1) is any of the divalent organic groups shown in the following structural formula. 【Chemistry 6-1】 (R6, R7, R8, and R9 are independently a hydrogen atom, a C1-C5 alkyl group, a methoxy group, a fluoro group, a chloro group, a bromo group, or a trifluoromethyl group. Z is independently a compound of the following formula) 【Chemistry 6-2】 It is a divalent organic group selected from the following. (a is a number from 0 to 6.)

3. The thermosetting imide resin composition for insulating material of multilayer printed circuit boards according to claim 1, wherein the number average molecular weight of the modified imide compound of formula (1) is 200 to 80,000.

4. The thermosetting imide resin composition for insulating material of multilayer printed circuit boards according to claim 1, wherein the reaction accelerator of component (B) is a radical polymerization initiation catalyst or an anionic polymerization initiation catalyst containing one or more nitrogen atoms and phosphorus atoms.

5. An uncured resin film comprising a thermosetting imide resin composition for insulating material of a multilayer printed circuit board according to any one of claims 1 to 4.

6. A cured resin film comprising a cured product of a thermosetting imide resin composition for insulating material of a multilayer printed circuit board according to any one of claims 1 to 4.

7. A prepreg comprising a thermosetting imide resin composition for insulating material of a multilayer printed circuit board and a fibrous substrate, as described in any one of claims 1 to 4.

8. A substrate comprising a thermosetting imide resin composition for insulating material of a multilayer printed circuit board according to any one of claims 1 to 4.

9. An adhesive comprising a thermosetting imide resin composition for insulating material of a multilayer printed circuit board according to any one of claims 1 to 4.

10. A semiconductor encapsulant comprising a thermosetting imide resin composition for insulating material of a multilayer printed circuit board according to any one of claims 1 to 4.

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