JP2022094922A - Thermosetting resin composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition which is reduced in the resin flow in a hot-pressing process and can be cured to form a cured product excellent in laser processability, heat resistance, hot-cold cycle resistance, and impact absorption.

SOLUTION: A thermosetting resin composition comprises: a polyimide resin (A), which is a reactant product of a monomer group comprising a dimer diamine (a-1) and a tetracarboxylic acid anhydride (a-2); at least one hardening agent (B) selected from the group consisting of epoxy compounds (B-1), maleimide compounds (B-2), isocyanate group-containing compounds (B-3), metal chelating compounds (B-4) and carbodiimide group-containing compounds (B-5); and a filler (C). A cured product obtained by heating the thermosetting resin composition at 180°C for 60 minutes shows a specific storage elastic modulus at a predetermined temperature.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention relates to a thermosetting resin composition containing a polyimide resin and a cured product thereof. The thermosetting adhesive sheet formed from the thermosetting resin composition of the present invention and the thermosetting cover sheet with a release film are suitably used for manufacturing copper-clad laminates and protecting the circuit surface of printed wiring boards. ..

In recent years, with the progress of high density and high functionality of electronic devices, further dimensional stability and excellent high frequency characteristics are required for materials used for printed wiring boards used.
For example, in Patent Document 1, the storage elastic modulus of the adhesive layer in a metal-clad laminate at 50 ° C. is 1800 MPa, the maximum value of the storage elastic modulus in the temperature range of 180 ° C. to 260 ° C. is 800 MPa or less, and further, the glass transition. A multilayer circuit board having an adhesive layer having an excellent dimensional stability of a conductor and a reduction in transmission loss even in the transmission of a high frequency signal when the temperature (Tg) is 180 ° C. or lower is disclosed.

Japanese Unexamined Patent Publication No. 2020-721198

By the way, with the miniaturization of electronic devices, communication devices, etc., the materials used for printed wiring boards used have not only dimensional stability and reduction of transmission loss, but also high workability such as via formation and high level. Various reliability is required.

In order to ensure continuity between the inner layer circuit and the outer layer circuit, openings such as blind vias and through holes may be provided on the printed wiring board by laser machining or drilling, and workability for forming the openings is important. Will be. With new ideas about space saving and circuit design, materials that can be machined even with smaller hole diameters are required. Furthermore, resistance to a treatment liquid for removing a residue called smear generated by processing is also required.

Further, in recent years, from the viewpoint of environmental protection, there is an increasing demand for the use of lead-free solder instead of the conventional lead-containing solder. Since lead-free solder has a higher melting point than conventional lead-containing solder, the process of mounting an electronic device on a printed wiring board has become hot (for example, a solder reflow process). Therefore, materials used for printed wiring boards and the like are also required to have high heat resistance of 260 ° C. or higher.

On the other hand, with the worldwide spread of electronic devices such as smartphones and tablet terminals in recent years, reliability in a wide temperature range from low temperature to high temperature is required. The conventional printed wiring board has a problem of peeling between the interlayer adhesive layer and the adjacent layer when exposed to an extreme temperature change, and the interlayer adhesive layer constituting the printed wiring board has a problem. High cold cycle resistance is required.

Further, recent electronic devices such as smartphones and tablet terminals are required to withstand physical impacts such as dropping.

In addition, when manufacturing a multilayer printed wiring board using a thermosetting adhesive sheet or protecting the circuit surface of a printed wiring board using a thermosetting cover sheet with a release film, a process of pressing under heating is performed. Go through. Therefore, in order to increase the density of electronic devices, a material having a small resin flow during the hot pressing process is required.

The present invention has been made in view of the above problems, and is a thermosetting resin composition having a small resin flow during a hot pressing process. After curing, it has laser processability, heat resistance, cold heat cycle resistance, and impact. It is an object of the present invention to provide a thermosetting resin composition capable of forming a cured product having excellent absorbability.

As a result of diligent studies by the present inventor, it has been found that the problems of the present invention can be solved in the following aspects, and the present invention has been completed.
That is, the thermosetting resin composition according to the present invention comprises a dimerdiamine (a-1) and a polyimide resin (A) which is a reaction product of a group of monomers containing a tetracarboxylic acid anhydride (a-2). , Epoxy compound (B-1), maleimide compound (B-2), isocyanate group-containing compound (B-3), metal chelate compound (B-4) and carbodiimide group-containing compound (B-5). A thermosetting resin composition containing at least one curing agent (B) and a filler (C), which is obtained by heating the thermosetting resin composition at 180 ° C. for 60 minutes. The following (a) to (c) are satisfied.
(A) The storage elastic modulus at 30 ° C. is 1.0 × 10 ⁶ to 1.0 × 10 ¹¹ Pa.
(B) The storage elastic modulus at 150 ° C. is 1.0 × 10 ⁴ to 1.0 × 10 ⁹ Pa.
(C) The storage elastic modulus at 280 ° C. is 1.0 × 10 ³ to 1.0 × 10 ⁹ Pa.

According to the present invention, it is possible to form a cured product having a small resin flow during hot pressing and having excellent laser processability, heat resistance, thermal cycle resistance, and impact absorption after curing.

It is a schematic diagram which shows the cross section in the vicinity of a blind via by laser processing of a printed wiring board.

Hereinafter, an example of an embodiment to which the present invention is applied will be described. The sizes and ratios of the members in the following figures are for convenience of explanation and are not limited thereto. Further, in the present specification, the description "arbitrary number A to arbitrary number B" includes the number A as the lower limit value and the number B as the upper limit value in the range. Further, the "sheet" in the present specification includes not only the "sheet" defined in JIS but also the "film". In addition, the numerical value specified in the present specification is a value obtained by the method disclosed in the embodiment or the embodiment.

<Thermosetting resin composition>
The thermosetting resin composition in the present invention includes a polyimide resin (A) which is a reaction product of a group of monomers containing dimerdiamine (a-1) and tetracarboxylic acid anhydride (a-2), and an epoxy. Any one selected from the group consisting of compound (B-1), maleimide compound (B-2), isocyanate group-containing compound (B-3), metal chelate compound (B-4) and carbodiimide group-containing compound (B-5). The thermosetting resin composition containing the curing agent (B) and the filler (C), and the cured product obtained by heating the thermosetting resin composition at 180 ° C. for 60 minutes is as follows ( B)-(c) is satisfied.
(A) The storage elastic modulus at 30 ° C. is 1.0 × 10 ⁶ to 1.0 × 10 ¹¹ Pa.
(B) The storage elastic modulus at 150 ° C. is 1.0 × 10 ⁴ to 1.0 × 10 ⁹ Pa.
(C) The storage elastic modulus at 280 ° C. is 1.0 × 10 ³ to 1.0 × 10 ⁹ Pa.

<Polyimide resin (A)>
The polyimide resin (A) of the present invention is a thermosetting resin obtained by reacting a group of monomers containing a dimer diamine (a-1) and a tetracarboxylic acid anhydride (a-2). The polyimide resin (A) functions as a binder resin in the thermosetting adhesive composition of the present invention. The binder resin serves as a substrate for the thermosetting adhesive composition and has a function of retaining the filler (C) described later.

<Diamine diamine (a-1)>
The dimerdiamine (a-1) of the present invention has a cyclic structure having 5 to 10 carbon atoms obtained by reacting with a monobasic unsaturated fatty acid having one or more double bonds or triple bonds having 10 to 24 carbon atoms. Examples thereof include polyamine compounds obtained by converting the carboxyl group of the polybasic acid compound having the above into an amino group. For example, a dimer obtained by a deal-alder reaction using natural fatty acids such as soybean oil fatty acid, tall oil fatty acid, and rapeseed oil fatty acid and purified oleic acid, linolenic acid, linolenic acid, and erucic acid as raw materials. An example is a compound obtained by converting the carboxyl group of a polybasic acid compound containing linolenic acid (fatty acid) into an amino group. The annular structure may be one or two, and in the case of two, the two rings may be independent or continuous. Further, it does not have to have a cyclic structure, and may be a mixture of a cyclic structure and a compound having no cyclic structure. By using the diamine compound derived from dimer acid, the diamine skeleton can be easily introduced into the polyimide resin.

Examples of the cyclic structure include a saturated alicyclic structure, an unsaturated alicyclic structure, and an aromatic ring. The amino group (amino group converted from the carboxyl group) can be directly bonded to the cyclic structure, but from the viewpoint of improving solubility and flexibility, the amino group is bonded to the cyclic structure via an aliphatic chain. Is preferable. The number of carbon atoms between the amino group and the cyclic structure is preferably 2 to 25. Further, the dimer diamine (a-1) in the present invention preferably has a chain-like alkyl group having a high degree of freedom and hydrophobicity as a portion other than the cyclic structure from the viewpoint of improving solubility and flexibility. It is preferable to have two or more alkyl groups for one cyclic structure. The alkyl group preferably has 2 to 25 carbon atoms.

Dimerdiamine (a-1) is mainly composed of a monomer containing a dimer skeleton derived from fatty acid (dimerized fatty acid) as a residue (70% by mass or more), and is also a raw material fatty acid. It is preferably obtained by converting the carboxyl group of the composition of the fatty acid having a trimerization or more into an amino group. Further, those having a reduced degree of unsaturation by hydrogenating (hydrogenation reaction) to the dimer skeleton are particularly preferably used from the viewpoint of oxidation resistance (particularly coloring in a high temperature range) and suppression of gelation during synthesis. ..

Examples of commercially available diamine diamines (a-1) include preamine 1071, preamine 1073, preamine 1074, preamine 1075 (all manufactured by Croda Japan); and Versamine 551 (manufactured by BASF Japan). Dimer diamine can be used alone or in combination of two or more.

As the polyamine compound used for the polymerization of the polyimide resin (A), the above-mentioned dimer diamine (a-1) may be used exclusively, but other polyamine compounds may be used as long as the gist of the present invention is not deviated. The amount of the other diamine compounds is preferably 50 mol% or less, more preferably 25 mol% or less, based on the total amount of the diamine compound used in the polyimide resin (A).

<Other diamine compounds>
Examples of other diamine compounds include 1,4-diaminobenzene, 1,3-diaminobenzene, 1,2-diaminobenzene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, and 2,3-diaminonaphthalene. , 2,6-diaminotoluene, 2,4-diaminotoluene, 3,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4' -Diamino-1,2-diphenylethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone , 3,3'-Aromatic diamines such as diaminodiphenylsulfone;
Fats such as ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,9-nonanediamine, 1,12-dodecamethylenediamine, metaxylenediamine, etc. Group diamines; examples include alicyclic diamines such as isophorone diamine, norbornan diamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-diaminodicyclohexylmethane, and piperazine. ..
Needless to say, the other diamine compounds are not limited to the above structure.

For the polymerization of the polyimide resin (A), other polyamine compounds may be used as long as the gist of the present invention is not deviated. The content of the other diamine compounds is preferably 50 mol% or less, more preferably 25 mol% or less, based on the total amount of the polyamine compound used in the polyimide resin (A).

As other polyamine compounds, a monomer containing a trimer as a residue, which is a triamine obtained by converting a tricarboxylic acid, which is derived from a monobasic unsaturated fatty acid having 10 to 24 carbon atoms, can be used. preferable. By using a polyamine compound having a trifunctionality or higher, a branched structure can be introduced into the polyimide resin to increase the molecular weight, and the heat resistance of the obtained polyimide resin can be increased.

<Tetracarboxylic acid anhydride (a-2)>
As the tetracarboxylic acid anhydride (a-2) of the present invention, known monomers can be used. Specifically, pyromellitic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid dianhydride, 3, 3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dian Anhydrous, 2,2', 3,3'-benzophenone tetracarboxylic acid dianhydride, 4,4'-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic acid dianhydride, 4 , 4'-(Hexafluoroisopropylidene) diphthalic acid anhydride, 5- (2,5-dioxotetrahydro-3-franyl) -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride, 1,2,3 , 4-benzenetetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic acid dianhydride, methylene-4,4'-diphthalic acid dianhydride, 1,1-ethylidene-4 , 4'-Diphthalic acid dianhydride, 2,2-propyriden-4,4'-diphthalic acid dianhydride, 1,2-ethylene-4,4'-diphthalic acid dianhydride, 1,3-trimethylen- 4,4'-Diphthalic acid dianhydride, 1,4-tetramethylene-4,4'-diphthalic acid dianhydride, 1,5-pentamethylene-4,4'-diphthalic acid dianhydride, 4,4 '-Oxydiphthalic acid dianhydride, p-phenylene bis (trimeritate anhydride), thio-4,4'-diphthalic acid dianhydride, sulfonyl-4,4'-diphthalic acid dianhydride, 1,3-bis ( 3,4-Dicarboxyphenyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride , 1,3-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, 1,4-bis [2- (3,4-dicarboxyphenyl) -2-propyl] Benzene dianhydride, bis [3- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, bis (3,4-di) Carboxyphenoxy) Dimethylsilane dianhydride, 1, 3-Bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5 , 8-naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,3,6,7 -Anthracenetetracarboxylic acid dianhydride, cyclobutanetetracarboxylic acid dianhydride (eg 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,2, 3,4-Cyclobutanetetracarboxylic acid dianhydride, etc.), Cyclohexanetetracarboxylic acid dianhydride (eg, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, etc.), 9,9-bis [4- (3,1-, 3,2-, 3,3- or 3,4-dicarboxyphenoxy) phenyl] Fluolene dianhydride, norbornan-2-spiro-α-cyclopentanone-α'-spiro-2''-Norbornane-5,5'',6,6''-tetracarboxylic acid dianhydride, and 1,2,7,8-phenanthrentetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetra Carboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-decahydronaphthalenetetracarboxylic acid dianhydride, 4,8-dimethyl-1,2, 5,6-Hexahydronaphthalenetetracarboxylic acid dianhydride, 2,6-dichloro-1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,7-dichloro-1,4,5,8- Naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-tetrachloro-1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrentetracarboxylic acid dianhydride , 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-di) Carboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfonate Anhydrous, benzene-1,2,3,4-tetracarboxylic acid dianhydride, 3,4,3', 4'-benzophenone tetracarboxylic acid dianhydride, 1,3,3a,4,5,9b- Hexahydro-5 (Tetrahide) B-2,5-dioxo-3-franyl) naphtho (1,2-C) furan-1,3-dione and the like can be mentioned. Among these, tetracarboxylic acid anhydride having two or less aromatic rings in one molecule is more preferable from the viewpoint of heat resistance and shock absorption. Among these, from the viewpoint of compatibility with the polyamine compound at the time of synthesis, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid. Dianhydride, 4,4'-[Propane-2,2-diylbis (1,4-phenyleneoxy)] Diphthalic acid dianhydride, 1,3,3a,4,5,9b-Hexahydro-5 (tetrahydro- 2,5-Dioxo-3-furanyl) naphtho (1,2-C) furan-1,3-dione is particularly preferred. The tetracarboxylic acid anhydride may be used alone or in combination of two or more.

The polyimide resin (A) has a reactive functional group that reacts with the curing agent (B) described later. The reactive functional group of the polyimide resin (A) is not limited, but at least one of an amino group and an anhydride group is suitable. Reactive functional groups are present on the side chains or ends of the polyimide resin. A polyimide resin having an amine or an anhydride group at the molecular terminal can be easily obtained by adjusting the charging amount ratio of the diamine compound and the tetracarboxylic acid dianhydride. More preferably, a polyimide resin containing an excess of tetracarboxylic acid dianhydride (containing 50 mol% or more) and having an acid anhydride group at the end can be mentioned. Further, the diamine compound may be excessively blended (50 mol% or more) to obtain a polyimide resin having the diamine compound at the terminal, and then the acid anhydride group may be introduced into the terminal by reacting with maleic anhydride. ..

<Curing agent (B)>
The curing agent (B) has a functional group capable of reacting with the reactive functional group of the polyimide resin (A), and preferably has a plurality of reactive functional groups.
The curing agent (B) is an epoxy compound (B-1), a maleimide compound (B-2), an isocyanate group-containing compound (B-3), a metal chelate compound (B-4), and a carbodiimide group-containing compound (B-5). ) Is at least one selected from the group consisting of. When the curing agent (B) is these compounds, it is possible to prevent a decrease in the storage elastic modulus at a high temperature and suppress side etching during laser processing. The curing agent can be used alone or in combination of two or more.

<Epoxy group-containing compound (B-1)>
The epoxy group-containing compound (B-1) may be any compound having an epoxy group in the molecule and is not particularly limited, but a compound having an average of two or more epoxy groups in one molecule is preferable. Can be used. As the epoxy-based compound, for example, an epoxy resin such as a glycisyl ether type epoxy resin, a glycisylamine type epoxy resin, a glycidyl ester type epoxy resin, or a cyclic aliphatic (alicyclic) epoxy resin can be used.

Examples of the glycidyl ether type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, and α-naphthol novolac. Type epoxy resin, bisphenol A type novolak type epoxy resin, dicyclopentadiene type epoxy resin, tetrabrom bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, tris (glycidyloxyphenyl) methane, or tetrakis (glycidyloxyphenyl) Etan and the like can be mentioned.

Examples of the glycidylamine type epoxy resin include tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmethaminophenol, tetraglycidylmethoxylylenediamine and the like.

Examples of the glycidyl ester type epoxy resin include diglycidyl phthalate, diglycidyl hexahydrophthalate, and diglycidyl tetrahydrophthalate.

Examples of the cyclic aliphatic (alicyclic) epoxy resin include epoxycyclohexylmethyl-epoxycyclohexanecarboxylate and bis (epoxycyclohexyl) adipate.

As the epoxy group-containing compound, one of the above compounds may be used alone, or two or more of them may be used in combination.
Examples of the epoxy group-containing compound include bisphenol A type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, tris (glycidyloxyphenyl) methane, tetrakis (glycidyloxyphenyl) ethane, or tetra from the viewpoint of high adhesiveness. It is preferable to use glycidylmethoxylylene diamine, and those containing a trifunctional or higher functional epoxy group are more preferable from the viewpoint of high heat resistance.

<Maleimide group-containing compound (B-2)>
The maleimide group-containing compound (B-2) may be any compound having a maleimide group in the molecule, and is not particularly limited, but a compound having an average of two or more maleimide groups in one molecule is preferable. Can be used.

Specific examples of the maleimide group-containing compound in the present invention include o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, N, N'-(toluene). -2,6-diyl) bismaleimide), 4,4'-diphenylmethane bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4 , 4'-diphenyl ether bismaleimide, 4,4'-diphenylsulphon bismaleimide, 1,3-bis (3-maleimidephenoxy) benzene, 1,3-bis (4-maleimidephenoxy) benzene, polyphenylmethanemaleimide (CASNO) : 67784-74-1, reaction product of maleimide anhydride and polymer composed of formaldehyde and aniline), N, N'-ethylene bismaleimide, N, N'-trimethylethylene bismaleimide, N, N'-propylene bismaleimide, N, N'-tetramethylene bismaleimide, N, N'-pentamethylene bismaleimide, N, N'-(1,3-pentandyl) bis (maleimide), N, N'-hexamethylene bismaleimide, N, N'-(1,7-heptanjiyl) bismaleimide, N, N'-(1,8-octanediyl) bismaleimide, N, N'-(1,9-notanjiyl) bismaleimide, N, N'-( 1,10-decandyl) bismaleimide, N, N'-(1,11-undecandil) bismaleimide, N, N'-(1,12-dodecandyl) bismaleimide, N, N'-[(1,4) -Phenylene) bismethylene] bismaleimide, N, N'-[(1,2-phenylene) bismethylene] bismaleimide, N, N'-[(1,3-phenylene) bismaleimide, 1,6'-bis Maleimide- (2,2,4-trimethyl) hexane, N, N'-[(methylimino) bis (4,1-phenylene)] maleimide, N, N'-(2-hydroxypropane-1,3-diyl) Bisimiminobiscarbonylbisethylene) bismaleimide, N, N'-(dithiobisethylene) bismaleimide, N, N'-[hexamethylenebis (imminocarbonylmethylene)] bismaleimide, N, N'-carbonylbis (1) , 4-Phenylene) Bismaleimide, N, N ′, N ″-[Nitrilotris ( Ethylene)] Trismaleimide, N, N', N''-[Nitrilotris (4,1-phenylene)] Trismaleimide, N, N'-[p-Phenylenebis (oxy-p-Phenylene)] Bismaleimide, N, N'-[methylenebis (oxy) bis (2-methyl-1,4-phenylene)] bismaleimide, N, N'-[methylenebis (oxy-p-phenylene)] bis (maleimide) N, N' -[Dimethylsililenbis [(4,1-phenylene) (1,3,4, -oxadiazol-5,2-diyl) (4,1-phenylene)]] bismaleimide, N, N'-[((4,1-phenylene)] 1,3-Phenylene) Bisoxybis (3,1-Phenylene)] Bismaleimide, 1,1'-[3'-oxospiro [9H-xanthene-9,1'(3'H) -isobenzofuran] -3,6 -Diyl] bis (1H-pyrrole-2,5-dione), N, N'-(3,3'-dichlorobiphenyl-4,4'-diyl) bismalemid, N, N'-(3,3'- Dimethylbiphenyl-4,4'-diyl) bismaleimide, N, N'-(3,3'-dimethoxybiphenyl-4,4'-diyl) bismaleimide, N, N'-[methylenebis (2-ethyl-4) , 1-phenylene)] bismaleimide, N, N'-[methylenebis (2,6-diethyl-4,1-phenylene)] bismaleimide, N, N'-[methylenebis (2-bromo-6-ethyl-4) , 1-phenylene)] bismaleimide, N, N'-[methylenebis (2-methyl-4,1-phenylene)] bismaleimide, N, N'-[ethylenebis (oxyethylene)] bismaleimide, N, N '-[Sulfonyl bis (4,1-phenylene) bis (oxy) bis (4,1-phenylene)] bismaleimide, N, N'-[naphthalen-2,7-diyl bis (oxy) bis (4,1- Phenylene)] bismaleimide, N, N'-[p-phenylene bis (oxy-p-phenylene)] bismaleimide, N, N'-[(1,3-phenylene) bisoxybis (3,1-phenylene)] bis Maleimide, N, N'-(3,6,9-trioxaundecane-1,11-diyl) bismaleimide, N, N'-[isopropylidenebis [p-phenyleneoxycarbonyl (m-phenylene)]] bis Maleimide, N, N'-[isopropylidenebis [p]
-Phenyleneoxycarbonyl (p-phenylene)]] bismaleimide, N, N'-[isopropyridenebis [(2,6-dichlorobenzene-4,1-diyl) oxycarbonyl (p-phenylene)]] bismaleimide, N, N'-[(phenylimino) bis (4,1-phenylene)] bismaleimide, N, N'-[azobis (4,1-phenylene)] bismaleimide, N, N'-[1,3 4-Oxaziazole-2,5-diylbis (4,1-phenylene)] bismaleimide, 2,6-bis [4- (maleimide-N-yl) phenoxy] benzonitrile, N, N'-[1 , 3,4-oxadiazole-2,5-diylbis (3,1-phenylene)] bismaleimide, N, N'-[bis [9-oxo-9H-9-phospha (V) -10-oxaphenanthrene) -9-Il] Methylenebis (p-phenylene)] Bismaleimide, N, N'-[Hexafluoroisopropylidenebis [p-phenyleneoxycarbonyl (m-phenylene)]] Bismaleimide, N, N'-[carbonylbis [(4,1-Phenylene) Thio (4,1-Phenylene)]] Bismaleimide, N, N'-carbonylbis (p-phenyleneoxy p-phenylene) Bismaleimide, N, N'-[5-tert- Butyl-1,3-phenylenebis [(1,3,4-oxadiazole-5,2-diyl) (4,1-phenylene)]] bismaleimide, N, N'-[cyclohexylidenebis (4) , 1-phenylene)] bismaleimide, N, N'-[methylenebis (oxy) bis (2-methyl-1,4-phenylene)] bismaleimide, N, N'-[5- [2- [5- ( Dimethylamino) -1-naphthylsulfonylamino] ethylcarbamoyl] -1,3-phenylene] bismaleimide, N, N'-(oxybisethylene) bismaleimide, N, N'-[dithiobis (m-phenylene)] bis Maleimide, N, N'-(3,6,9-trioxaundecane-1,11-diyl) bismaleimide, N, N'-(ethylenebis-p-phenylene) bismaleimide, BMI-689 manufactured by DesignerMolecules. , BMI-1500, BMI-1700, BMI-3000, BMI-5000, BMI-9000, ODA-BMI, BAF-BMI manufactured by JFE Chemical, and the like.

Further, a polyfunctional maleimide obtained by reacting a polyfunctional amine with maleic anhydride can be mentioned. Examples of the polyfunctional amine include isophoronediamine, dicyclohexylmethane-4,4'-diamine, Jeffamine D-230, HK-511, D-400, XTJ-, manufactured by Huntsman Corporation and having a terminal amination polypropylene glycol skeleton. 582, D-2000, XTJ-578, XTJ-509, XTJ-510, T-403, T-5000, XTJ-500 with terminal amination ethylene glycol skeleton, XTJ-501, XTJ-502, XTJ-504, XTJ-511, XTJ-512, XTJ-542, XTJ-542, XTJ-533, XTJ-536, XTJ-548, XTJ-559, etc. having a XTJ-590 terminal amination polytetramethylene glycol skeleton can be mentioned.

<Isocyanate group-containing compound (B-3)>
The isocyanate group-containing compound (B-3) is not particularly limited as long as it is a compound having an isocyanate group in the molecule.
Specific examples of the isocyanate group-containing compound having one isocyanate group in one molecule include n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, benzyl isocyanate, (meth) acryloyloxyethyl isocyanate, and 1,1-bis [ (Meta) acryloyloxymethyl] ethyl isocyanate, vinyl isocyanate, allyl isocyanate, (meth) acryloyl isocyanate, isopropenyl-α, α-dimethylbenzyl isocyanate and the like can be mentioned.
In addition, 1,6-diisocyanatohexane, isophorone diisosocyanate, 4,4'-diphenylmethane diisocyanate, polypeptide diphenylmethane diisocyanate, xylylene diisocyanate, trilene 2,4-diisocyanate, toluene diisosocyanate, 2,4-diisosocyanate. Toluene, hexamethylene diisosocyanate, 4-methyl-m-phenylene diisosocyanate, naphthylene diisocyanate, paraphenylene diisocyanate, tetramethylxylylene diisocyanate, cyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, trizine diisocyanate, 2,2 , 4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, m-tetramethylxylylene diisocyanate, P-tetramethylxylylene diisocyanate, diisocyanate compounds such as dimerate diisocyanate, hydroxyl group, carboxyl group, A compound obtained by reacting an amide group-containing vinyl monomer with an equimolar reaction can also be used as an isocyanate compound.

Specific examples of the isocyanate group-containing compound having two isocyanate groups in one molecule include 1,3-phenylenediocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylenediocyanate, and 4,4'-diphenylmethane. Diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanatebenzene, dianisidine diisocyanate, Aromatic diisocyanates such as 4,4'-diphenyl ether diisocyanate, 4,4', 4 "-triphenylmethane triisocyanate,
Trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylenedisocyanate, 1,3-butyrenis isocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene An aliphatic diisocyanate such as diisocyanate,
ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate , 1,3-Tetramethylxylylene diisocyanate and other aromatic aliphatic diisocyanates,
3-Isocyanate Methyl-3,5,5-trimethylcyclohexyl isocyanate [also known as isophorone diisocyanate], 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, methyl-2,4-cyclohexane Diisocyanates, methyl-2,6-cyclohexanediisocyanates, 4,4'-methylenebis (cyclohexylisocyanate), 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane and other alicyclic diisocyanates Can be mentioned.

Specific examples of the isocyanate group-containing compound having three isocyanate groups in one molecule include aliphatic polyisocyanates such as aromatic polyisocyanates and lysine triisocyanates, aromatic aliphatic polyisocyanates, and alicyclic polyisocyanates. And the like, the trimethylolpropane adduct body of diisocyanate described above, the burette body reacted with water, and the trimerate having an isocyanurate ring can be mentioned.

As the isocyanate group-containing compound, a blocked isocyanate group-containing compound in which the isocyanate group in the various isocyanate group-containing compounds exemplified above is protected by ε-caprolactam, MEK oxime, or the like can also be used.
Specific examples thereof include those in which the isocyanate group of the isocyanate group-containing compound is blocked with ε-caprolactam, methyl ethyl ketone (hereinafter referred to as MEK) oxime, cyclohexanone oxime, pyrazole, phenol and the like. In particular, a hexamethylene diisocyanate trimer having an isocyanurate ring and blocked with MEK oxime or pyrazole is highly preferable because it has excellent adhesive strength and heat resistance to polyimide and copper when used in the present invention. Further, from the viewpoint of heat resistance, it is preferable to have a trifunctional or higher functional isocyanate group.

<Metal chelate compound (B-4)>
The metal chelate compound (B-4) is an organometallic compound composed of a metal and an organic substance, and reacts with a reactive functional group of a binder resin to form a crosslink. The type of the organometallic compound is not particularly limited, and examples thereof include organoaluminum compounds, organotitanium compounds, and organozirconium compounds. Further, the bond between the metal and the organic substance may be a metal-oxygen bond, and is not limited to the metal-carbon bond. In addition, the bond mode between the metal and the organic substance may be any of a chemical bond, a coordinate bond, and an ionic bond. Further, it is preferable that the number of functional elements is trifunctional or higher from the viewpoint of heat resistance.

The organoaluminum compound is preferably an aluminum metal chelate compound. Examples of the aluminum metal chelate compound include ethyl acetoacetate aluminum diisopropyrate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetonate bis (ethyl acetoacetate), and aluminum tris (acetyl acetoacetate). , Aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum di-n-butoxide monomethyl acetoacetate, aluminum diisobutoxide monomethyl acetoacetate, aluminum di-sec-butoxide monomethyl acetoacetate, aluminum isopropylate, mono sec-butoxyaluminum di Examples thereof include isopropylate, aluminum-sec-butyrate, and aluminum ethylate.

The organic titanium compound is preferably a titanium metal chelate compound. The titanium metal chelate compound is, for example, titanium acetylacetonate, titaniumtetraacetylacetonate, titaniumethylacetoacetate, titaniumoctylene glycolate, titaniumethylacetate acetate, titanium-1.3-propanedioxybis (ethylacetoacetate). , Polytitanium Acetylacetyl Acetnate, Tetraisopropyl Titanate, Tetranormal Butyl Titanate, Butyl Titanium Dimer, Tetraoctyl Titanate, Darshary Amil Titanate, Tetrater Shari Butyl Titanate, Tetrastearyl Titanate, Titanium Isostearate, Tri-n-Butoxy Examples thereof include titanium monostearate, di-i-propoxytitanium distearate, titanium stearate, di-i-propoxytitanium diisostearate, (2-n-butoxycarbonylbenzoyloxy) tributoxytitanium and the like.
The organic zirconium compound is preferably a zirconium metal chelate compound. Zirconium metal chelate compounds include, for example, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetate acetate), zirconium dibutoxybis (ethylacetacetate), zirconium tetraacetylacetonate, Examples thereof include normal propyl zirconate, normal butyl zirconate, zirconium stearate, zirconium octylate and the like. Among these, an organic titanium compound and an organic zirconium compound are preferable from the viewpoint of thermosetting reactivity.

<Carbodiimide group-containing compound (B-5)>
The carbodiimide group-containing compound (B-5) is not particularly limited as long as it has a carbodiimide group in the molecule. Examples of the carbodiimide group-containing compound include carbodilite V-01, V-03, V-05, V-07, V-09 (Nisshinbo Chemical Co., Ltd.), and cyclic carbodiimide (Teijin Co., Ltd.). From the viewpoint of heat resistance, those having an average of 3 or more carbodiimide groups in one molecule are preferable.

The curing agent (B) used in the present invention preferably contains an aromatic ring structure in the curing agent. By including a bulky aromatic ring, the molecular motion of the thermosetting resin composition of the present invention can be suppressed, and the stress generated during the thermal cycle can be alleviated.

The curing agent (B) used in the present invention has a total of 1 to 20 parts by mass of an epoxy group, a maleimide group, an isocyanate group, a metal chelate compound, and a carbodiimide group-containing compound with respect to the polyimide resin (A). It is preferably contained in the above range, more preferably 1 to 15 parts, and even more preferably 3 to 10 parts. By adding the curing agent (B) to 1 to 20 parts, the effect of suppressing the storage elastic modulus of the cured product and suppressing the generation of cracks against the stress caused by a sudden temperature change during the thermal cycle is exhibited. Can be done.

<Filler (C)>
Next, the filler (C) used in the present invention will be described in detail. The thermosetting resin composition of the present invention contains a filler for the purpose of controlling the elastic modulus of the cured product.

The filler (C) is not particularly limited, and examples thereof include a spherical shape, a powder shape, a fibrous shape, a needle shape, and a scale shape. Examples of the filler (C) include fluorine filler: polytetrafluoroethylene powder and its modified products, tetrafluoroethylene-perfluoroalkyl vinyl ether powder, tetrafluoroethylene-ethylene powder, tetrafluoroethylene-hexafluoropropylene powder, and tetrafluoroethylene. -Vinylidene fluoride powder, tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether powder, polychlorotrifluoroethylene powder, chlorotrifluoroethylene-ethylene powder, chlorotrifluoroethylene-vinylidene fluoride powder, polyvinylidene fluoride powder, Polyvinyl fluoride powder and the like can be mentioned. Other fillers include polyethylene powder, polyacrylic acid ester powder, epoxy resin powder, polyamide powder, polyimide powder, polyurethane powder, liquid crystal polymer beads, polysiloxane powder, etc., as well as silicone, acrylic, styrene butadiene rubber, and butadiene rubber. Polymer fillers such as a multi-layered core shell using, etc .; melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium phosphate, ammonium polyphosphate, phosphoric acid (Poly) phosphate compounds such as carbamate and polyphosphate carbamate, organic phosphate ester compounds, phosphazene compounds, phosphonic acid compounds, aluminum diethylphosphinate, aluminum methylethylphosphinate, aluminum diphenylphosphinate, aluminum ethylbutylphosphinate , Phosphoric acid compounds such as aluminum methylbutylphosphinate and aluminum polyethylenephosphinate, phosphorus-based fillers such as phosphinid oxide compounds, phosphoran compounds and phosphoramide compounds;
Nitrogen-based fillers such as benzoguanamine, melamine, melamine, melem, melon, melamine cyanurate, cyanuric acid compound, isocyanuric acid compound, triazole-based compound, tetrazole compound, diazo compound, urea;
Silica, hollow silica, porous silica, mica, talc, kaolin, clay, hydrotalcite, wollastonite, zonotrite, silicon nitride, boron nitride, aluminum nitride, calcium hydrogenphosphate, calcium phosphate, glass flakes, hydrated glass, Calcium titanate, sepiolite, magnesium sulfate, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide, titanium oxide, tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, Examples thereof include inorganic fillers such as antimony oxide, nickel oxide, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate and aluminum borate.

Further, from the viewpoint of shock absorption, it is preferable to use a fluorine filler, boron nitride, a liquid crystal polymer and silica. In the present invention, these fillers (C) can be used alone or in combination of two or more.

The average particle size D ₅₀ of the filler (C) is preferably 0.1 to 25 μm. When the average particle size D ₅₀ of the filler (C) is 0.1 to 25 μm, the mechanical properties of the cured product can be improved and the impact absorption can be improved. The average particle size D ₅₀ of the filler (C) is more preferably in the range of 2 to 10 μm.

The content of the filler (C) is preferably 5 to 60 parts by mass with respect to 100 parts by mass of the binder resin component, and by setting the filler amount to 60 parts by mass or less, the storage elastic modulus of the cured film is kept below a certain level. It can be controlled to the extent that it has the effect of suppressing the occurrence of cracks and peeling against stress caused by sudden temperature changes during the thermal cycle. Further, when the content of the filler (C) is 5 parts by mass or more, the storage elastic modulus near room temperature can be kept high, and it becomes difficult to swell in the desmear process after laser processing. Peeling and floating are less likely to occur at the interface with the thermosetting resin composition. The content of the filler is more preferably 5 to 40 parts by mass, further preferably 5 to 30 parts by mass, and most preferably 5 to 20 parts by mass or less.

When the thermosetting resin composition of the present invention is used as a thermosetting adhesive sheet described later, the filler (C) has a relationship between the average particle size _D50 of the filler (C) and the film thickness of the thermosetting adhesive sheet. The value calculated by (Equation 1) is preferably 0.8 or less, more preferably 0.1 or less, and further preferably 0.05 or less. By setting the content to 0.8 or less, the binder resin component can sufficiently cover the surface of the filler, good adhesive force can be exhibited on the adherend, and peeling and floating are less likely to occur during the cold cycle.
(Equation 1)
Average particle size of filler (C) D ₅₀ (μm) / Thermosetting adhesive sheet film thickness (μm)

The method of adding the filler (C) is not particularly limited, and any conventionally known method may be used. Specifically, a method of adding the filler (C) to the polymerization reaction solution before or during the polymerization of the binder resin 3. Examples thereof include a method of kneading a filler in a binder resin using this roll and a method of preparing a dispersion containing the filler and mixing the filler with the binder resin. Further, in order to disperse the filler well and stabilize the dispersed state, a dispersant, a thickener and the like can be used within a range that does not affect the physical properties of the thermosetting resin composition.

<Other additives>
In addition, the thermosetting resin composition of the present invention further contains energy ray absorbers, dyes, pigments, antioxidants, polymerization inhibitors, defoaming agents, leveling agents, etc. as optional components as long as the purpose is not impaired. Ion collectors, moisturizers, viscosity modifiers, preservatives, antibacterial agents, antistatic agents, antiblocking agents, infrared absorbers, electromagnetic wave shielding agents, etc. can be added, and energy can be added from the viewpoint of improving laser workability. It is preferable to add a ray absorber.

<Storage modulus of thermosetting resin composition>
The method of obtaining the storage elastic modulus will be described. The storage elastic modulus can be measured using a DVA method (dynamic viscoelastic analysis method) measuring device or the like. The storage elastic modulus at each temperature can be obtained from the viscoelastic curve of the cured product obtained by the apparatus.

The cured product obtained by heating the thermosetting resin composition of the present invention at 180 ° C. for 60 minutes satisfies (a) to (c).
(A) The storage elastic modulus at 30 ° C. is 1.0 × 10 ⁶ to 1.0 × 10 ¹¹ Pa.
(B) The storage elastic modulus at 150 ° C. is 1.0 × 10 ⁴ to 1.0 × 10 ⁹ Pa.
(C) The storage elastic modulus at 280 ° C. is 1.0 × 10 ³ to 1.0 × 10 ⁹ Pa.

[Storage modulus at 30 ° C]
The cured product obtained by heating the thermosetting resin composition of the present invention at 180 ° C. for 60 minutes has a storage elastic modulus of 1.0 × 10 ⁶ to 1.0 × 10 ¹¹ Pa at 30 ° C., and 1. 0 × 10 ⁷ to 1.0 × 10 ¹⁰ Pa is preferable, and 1.0 × 10 ⁸ to 1.0 × 10 ⁹ Pa is further preferable.

By setting the storage elastic modulus at 30 ° C. to 1.0 × 10 ¹¹ Pa or less, it is effective in suppressing the occurrence of cracks against stress due to a sudden temperature change during the thermal cycle. Further, by setting it to 1.0 × 10 ⁶ Pa or more, the invasion of the desmear liquid in the desmear process is suppressed, and the occurrence of peeling and floating at the interface between the copper-clad laminate and the thermosetting resin composition of the present invention is suppressed. It is possible to improve the resistance to desmia liquid. The storage elastic modulus at 30 ° C. can be controlled by adjusting the type and amount of the filler (C) added.

[Storage modulus at 150 ° C]
Next, the cured product obtained by heating the thermosetting resin composition of the present invention at 180 ° C. for 60 minutes has a storage elastic modulus of 1.0 × 10 ⁴ to 1.0 × 10 ⁹ Pa at 150 ° C., and 1 .0 × 10 ⁵ to 1.0 × 10 ⁸ Pa is preferable, and 1.0 × 10 ⁶ to 1.0 × 10 ⁷ Pa is further preferable.

By setting the storage elastic modulus at 150 ° C to 1.0 × ¹⁰⁹ Pa or less, it has the effect of suppressing the occurrence of cracks against stress due to sudden temperature changes during the thermal cycle, as in the case of 30 ° C. .. Further, by setting it to 1.0 × 10 ⁴ Pa or more, the cohesive force of the cured film of the thermosetting resin composition can be enhanced, and when it is used as an interlayer adhesive thermosetting resin for a multilayer printed wiring board, it is a resin. The flow can be suppressed and the dimensional stability can be ensured. The storage elastic modulus at 150 ° C. can also be controlled by adjusting the type and amount of the filler (C) added.

Since the cold cycle resistance repeats the cold cycle in the range of about -30 ° C to about 150 ° C, both the storage elastic modulus in the room temperature region and the high temperature region are related. Therefore, the cold cycle resistance is abrupt during the cold cycle because the storage elastic modulus at 30 ° C. is 1.0 × 10 ¹¹ Pa or less and the storage elastic modulus at 150 ° C. is 1.0 × 10 ⁹ Pa or less. It has the effect of suppressing the occurrence of cracks against stress caused by temperature changes. In particular, when the storage elastic modulus at 30 ° C. is 1.0 × 10 ⁹ Pa or less and the storage elastic modulus at 150 ° C. is 1.0 × 10 ⁷ Pa or less, particularly excellent thermal cycle resistance is exhibited. Can be done.

[Storage modulus at 280 ° C]
The cured product obtained by heating the thermosetting resin composition of the present invention at 180 ° C. for 60 minutes has a storage elastic modulus of 1.0 × 10 ³ to 1.0 × 10 ⁹ Pa at 280 ° C., and 1. 0 × 10 ⁴ to 1.0 × 10 ⁸ Pa is preferable, and 1.0 × 10 ⁵ to 1.0 × 10 ⁷ Pa is further preferable.

By setting the storage elastic modulus at 280 ° C. to 1.0 × ¹⁰⁹ Pa or less, stress when high temperature heat is applied in the solder mounting process can be alleviated, crack generation can be suppressed, and heat resistance is improved. .. In addition, by setting it to 1.0 × 10 ³ Pa or more, side etching can be suppressed without heat sagging even if high temperature heat is applied by the laser in the laser processing process for forming blind vias and sulhole vias. And the laser workability is improved. The storage elastic modulus at 280 ° C. can be adjusted by the type of the curing agent (B).

<Loss tangent (tanδ) peak>
A method of obtaining the peak value of the loss tangent (tan δ) will be described. The storage elastic modulus can be measured using a DVA method (dynamic viscoelastic analysis method) measuring device or the like. From the viscoelastic curve of the cured product obtained by the apparatus, the loss tangent (tanδ) is calculated at each temperature from the storage elastic modulus and the loss elastic modulus at each temperature, and plotting is performed based on (Equation 2). The peak value is the point where the tan δ curve becomes maximum. When there are a plurality of maximum points, the value whose temperature is closest to room temperature (23 ° C.) is defined as the tan δ peak of the cured product.
(Equation 2)
(Loss tangent; tanδ) = (Loss modulus) / (Store modulus)

The cured product obtained by heating the thermosetting resin composition of the present invention at 180 ° C. for 60 minutes preferably has a loss tangent (tan δ) peak value of 0.3 or more at 0 to 280 ° C., and 0. 5 or more is more preferable, and 0.7 or more is further preferable. When the loss tangent (tan δ) peak value is 0.3 or more, the impact diffusivity is increased and the impact from the outside can be released. The loss tangent (tan δ) is a molecule of the polyimide resin (A) because the number of aromatic rings contained in one structural unit derived from the tetracarboxylic acid anhydride (a-2) in the polyimide resin (A) is two or less. The degree of freedom of movement can be increased, and the shock diffusivity can be enhanced by flexibly causing molecular motion against an external impact.

To the thermosetting adhesive composition of the present invention, embodiments such as a thermosetting adhesive sheet, a thermosetting cover sheet with a release film, and a copper-clad laminate, which will be described later, are applied, and these embodiments are processed to form a printed wiring board. By incorporating the thermosetting adhesive composition into, the thermosetting adhesive composition functions as a thermosetting composition for interlayer adhesion of a printed wiring board.

<Thermosetting adhesive sheet>
The thermosetting adhesive sheet is a sheet of the thermosetting resin composition of the present invention. The thermosetting adhesive sheet is used as an adhesive member for a printed wiring board and an electronic device, and has a function of adhering and holding other members. The thermosetting adhesive sheet is sandwiched between the members to be bonded to each other, temporarily bonded, and then heated or heat-pressed to be cured to bond the adherends to each other.

<Manufacturing method of thermosetting adhesive sheet>
The method for producing a thermosetting adhesive sheet includes, for example, a coating solution containing a polyimide resin (A), a curing agent (B), a filler (C), and other optional components and a solvent after being applied to one side of a release film. A thermosetting adhesive sheet with a double-sided release film is formed by removing and drying a liquid medium such as an organic solvent at 40 to 150 ° C. and laminating another release film on the surface of the formed thermosetting adhesive sheet. Can be obtained. By laminating both sides with a release film, it is possible to prevent surface contamination of the thermosetting adhesive sheet. The thermosetting adhesive sheet can be isolated by peeling off the release film.
The two release films can be of the same type or different types. By using release films having different peelability, the peeling force can be adjusted to be stronger or weaker, so that the peeling force can be easily peeled off in order.

As the coating method, for example, known methods such as comma coat, knife coat, die coat, lip coat, roll coat, curtain coat, bar coat, gravure printing, flexographic printing, screen printing, dip coat, spray coat, spin coat and the like can be used. You can choose.

The thickness of the thermosetting adhesive sheet after drying is preferably 5 μm to 500 μm, more preferably 10 μm to 100 μm, in order to exhibit sufficient adhesiveness and from the viewpoint of ease of handling.

<Thermosetting cover sheet with release film>
The thermosetting cover sheet with a release film has a thermosetting adhesive sheet sandwiched between the release film and the cover resin layer. In other words, the thermosetting cover sheet is a thermosetting adhesive sheet with a double-sided release film in which the release film on one side is replaced with a cover resin layer, and the manufacturing method is also the same.

The cover resin layer is an insulating film, and examples of the insulating film include polyimide, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polybutylene terephthalate, polyether ether ketone, and the like. One or more resins selected from the group consisting of fluororesins can be used.

The fluororesin as the insulating film is not particularly limited, and for example, polytetrafluoroethylene, polytetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, difluoroethylene- Included is one or more selected from the group consisting of trifluoroethylene copolymers, tetrafluoroethylene-ethylene copolymers, polychlorotrifluoroethylene, and polyvinylidene fluoride.

<Use of thermosetting adhesive sheet, thermosetting adhesive sheet with release film, thermosetting cover sheet with release film>
A copper-clad laminated board or a printed wiring board can be obtained by using the thermosetting adhesive sheet with a release film of the present invention.
The copper-clad laminate is a copper foil and an insulating film laminated via an adhesive layer which is a cured product of a thermosetting adhesive sheet obtained from the thermosetting resin composition of the present invention.
In such a copper-clad laminate, for example, the peelable film is sequentially peeled off from the heat-curable adhesive sheet with a release film of the present invention, and a copper foil and an insulating film are laminated on each surface of the heat-curable adhesive sheet (this step). It is obtained by heat-curing the heat-curable adhesive sheet between the copper foil and the insulating film by undergoing a process of temporary bonding), heating, or heat pressing.
Alternatively, a coating solution for forming a thermosetting adhesive sheet is applied and dried on an insulating film, a copper foil is layered on the formed thermosetting adhesive sheet, and heating or a heat pressing process is performed. A copper-clad laminate can also be obtained by thermosetting the thermosetting adhesive sheet between the copper foil and the insulating film.
In the copper-clad laminate, the outermost layers on both sides may be both copper foils such as copper foil / adhesive layer / insulating film / adhesive layer / copper foil, and the inner layer of the copper foil may be further provided. When a copper foil or an insulating film is laminated using a plurality of thermosetting adhesive sheets, the plurality of thermosetting adhesive sheets can be heat-cured at one time after undergoing temporary bonding a plurality of times.

<Printed wiring board>
A printed wiring board can be obtained by processing a copper foil in a copper-clad laminate by etching or the like to form a signal circuit or a ground circuit. By peeling the release film from the thermosetting cover sheet with a release film, attaching the thermosetting adhesive sheet surface to the circuit surface, and heat-curing, a coverlay made of a cover resin layer / cured product of the adhesive sheet is formed. It can also be used as a substrate for protecting a signal circuit or for further multi-layering.
As a method of providing a signal circuit or a ground circuit, for example, a photosensitive etching resist layer is formed on a copper foil in a copper-clad laminate, exposed through a mask film having a circuit pattern, and only the exposed portion is cured, and then After removing the unexposed copper foil by etching, the remaining resist layer can be peeled off to form a conductive circuit from the copper foil.

Further, the printed wiring board of the present invention can also be obtained without using a copper-clad laminate.
For example, after forming a conductor pattern on a flexible and insulating plastic film such as polyester, polyimide, liquid crystal polymer, or PTFE film by printing technology, the thermosetting adhesive sheet of the present invention covers the conductor pattern. A flexible printed wiring board provided with a protective layer can also be obtained by curing a heat-curable adhesive sheet by stacking protective layers and heating / pressurizing the film.
Alternatively, only circuits necessary for means such as sputtering and plating are provided on a flexible and insulating plastic film, and similarly, a protective layer is provided via a cured product of the thermosetting adhesive sheet of the present invention. It is also possible to obtain a flexible printed wiring board.

Further, a thermosetting adhesive sheet obtained by peeling the release film from the thermosetting adhesive sheet with a release film of the present invention is sandwiched between a plurality of flexible printed wirings, and the thermosetting adhesive sheet is heated and pressed to obtain a thermosetting adhesive sheet. It can also be cured to obtain a multi-layer flexible printed wiring board.

The printed wiring board of the present invention is such as a blind via or a through hole in order to conduct conduction between a cured product layer obtained by curing a thermosetting resin composition or a plurality of copper foils arranged with a protective layer interposed therebetween. Via openings may be provided. The via opening is generally formed by laser processing using a laser beam or drill processing using a drill, but it is preferable to perform laser processing from the viewpoint of improving the shape accuracy of the via opening.

By setting the storage elastic modulus of the cured product layer obtained by curing the thermosetting resin composition at 280 ° C to 1.0 × 10 ³ to 1.0 × 10 ⁹ Pa, even when heat is applied by laser processing. The storage elastic modulus can be maintained and side etching can be suppressed.

Generally, there is a desmear step of removing the remaining resin (smear) after forming a via opening by laser processing or drilling. This desmear process includes a dry process using plasma and a wet process using an etching solution such as potassium permanganate. Although the dry process is suitable for the desmear of small diameter vias, there are many problems such as the need for special gas and the time required for vacuuming, so even at present, there are many desmears in the wet process. It is used.

By setting the storage elastic modulus at 30 ° C. to 1.0 × 10 ⁶ to 1.0 × 10 ¹¹ Pa, the invasion of the desmear liquid in the desmear process is suppressed, and the copper-clad laminate and the thermosetting resin composition of the present invention are formed. It is possible to suppress the occurrence of peeling and floating at the interface with an object.

Using the printed wiring board of the present invention, various electronic devices such as smartphones, tablet terminals, and cameras can be manufactured.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. Further, in the examples, "part" means "part by mass" and "%" means "% by mass".

The acid value of the resin was measured by the following method.
《Acid value measurement》
The acid value was measured according to JIS K0070. Precisely weigh about 1 g of the sample in an Erlenmeyer flask with a stopper, and add 100 ml of a mixed solution of tetrahydrofuran / ethanol (volume ratio: tetrahydrofuran / ethanol = 2/1) to dissolve. Phenolphthalein test solution was added as an indicator, titrated with a 0.1N alcoholic potassium hydroxide solution, and the end point was when the indicator held a pink color for 30 seconds. The acid value was calculated by the following formula (unit: mgKOH / g).
Equation (3)
Acid value (mgKOH / g) = (5.611 × a × F) / S
S: Sample collection amount (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Titer of 0.1N alcoholic potassium hydroxide solution

[Synthesis Example 1] <Synthesis of Polyimide Resin (P1)>
378.7 g of dimerdiamine (priamine 1075) having 36 carbon atoms as a polyamine compound and bisphenol A as a tetracarboxylic acid anhydride in a 4-port flask equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, an introduction tube, and a thermometer. Type Acid Dianhydride (4,4'-[Propane-2,2-diylbis (1,4-phenyleneoxy)] Diphthalic Acid Dianhydride) (BISDA-1)
380.0 g of 000) and 1100 g of cyclohexanone as a solvent were charged and stirred until uniform. After becoming uniform, the temperature is raised to 110 ° C., and after 30 minutes, the temperature is raised to 140 ° C., and when the temperature reaches 140 ° C., the reaction is continued at the same temperature for 10 hours, the dehydration reaction is continued, and the weight is increased. A polyimide resin (A1) having an average molecular weight of 54,000, an acid value of 6.4 mgKOH / g, and an amine value of 0.3 mgKOH / g was obtained.

[Synthesis Examples 2 to 6]
As shown in Table 1, the polyimide resin (A2) is the same as in Synthesis Example 1 except that the types and amounts of dimer diamine (a-1) and tetracarboxylic acid anhydrides (a-2) are changed. ~ (A6) were obtained in the same manner.

[Example 1]
<< Manufacture of thermosetting resin composition (coating liquid) >>
In terms of solid content, 100 parts of the polyimide resin (A1), 5 parts of the epoxy group-containing compound (B-1-1) described later, and 20 parts of boron nitride are placed in a container and mixed so that the non-volatile content concentration becomes 40%. A solvent (toluene: MEK = 9: 1 (weight ratio)) was added and stirred with a disper for 10 minutes to obtain a thermosetting resin composition (coating liquid).
According to the method described later, the storage elastic modulus and loss elastic modulus of the cured product are obtained, and the resin flow as a thermosetting adhesive sheet, laser processability before and after immersion in Desmia liquid, heat resistance, thermal cycle resistance, and shock absorption are evaluated. The results are shown in Tables 2-4.

[Examples 2 to 22, Comparative Examples 1 to 5]
As shown in Tables 2 to 4, a thermosetting resin composition (coating liquid) was obtained in the same manner as in Example 1 except that the types and amounts of the binder resin, the curing agent, and the filler were changed, and evaluated in the same manner. did.

<< Raw material: Binder resin >>
Polyimide resin (A): (A1) to (A6) described in Synthesis Examples 1 to 6.
(A7): Polyester resin having a Byron 637, an acid value of 5 mgKOH / g, a weight average molecular weight of 30,000, and a Tg of 21 ° C. (manufactured by Toyobo Co., Ltd.)

<< Raw material: Hardener (B) >>
Epoxy group-containing compound (B-1-1): "ELM-434" (glycidylamine type epoxy resin, epoxy equivalent 100 g / eq, 4-functional) Epoxy group-containing compound (B-1-2) manufactured by Sumitomo Chemical Co., Ltd .: " YX-8800 "(glycidyl ether type epoxy resin, epoxy equivalent 180 g / eq, bifunctional) Maleimide group-containing compound (B-2) manufactured by Mitsubishi Chemical Co., Ltd .:" MIR-3000 "(biphenylaralkyl type maleimide resin, polyfunctional) Japan Isocyanate group-containing compound (B-3) manufactured by Kayaku Co., Ltd .: "TKA-100" (isocyanurate type isocyanate compound, isocyanate equivalent: 180 g / eq, trifunctional) Asahi Kasei Co., Ltd. metal chelate compound (B-4): "Olga Chix ZC-150 ”(organic zirconia compound, tetrafunctional) Carbodiimide group-containing compound (B-5) manufactured by Matsumoto Fine Chemical Co., Ltd .:“ Carbodilite V-05 ”(carbodiimide equivalent: 262 g / eq, polyfunctional) Polyamino group manufactured by Nisshinbo Chemical Co., Ltd. Containing compound: "BAPP" (bifunctional) manufactured by Seika

<< Raw material: Filler (C) >>
Boron nitride: "SP-2" (average particle size D ₅₀ ; 4.0 μm) Denka silica: "SC2050-MB" (average particle size D ₅₀ ; 0.5 μm) Admatex alumina: "HT" Grade ”(average particle size D ₅₀ = 1.2 μm, average circularity = 0.90) PTFE:“ KT-300 ”(average particle size D ₅₀ ; 10.0 μm) Kitamura liquid crystal polymer:“ E101 -S "(average particle size D ₅₀ ; 17.5 μm) manufactured by Sumitomo Chemical Co., Ltd.

<< Measurement of storage elastic modulus of cured product and loss tangent >>
<Creation of cured product for measurement>
A heavy release film (polyethylene terephthalate coated with a release mold agent) having a thickness of 50 μm so that the coating liquid obtained in each example and each comparative example is dried using a doctor blade to a thickness of 200 μm. (PET) film) was uniformly coated and dried at 100 ° C. for 2 minutes, and then cooled to room temperature to form a thermosetting adhesive sheet with a single-sided release film.
Next, the surface of the obtained heat-curable adhesive sheet with a single-sided release film was superposed on a light release film (polyethylene terephthalate (PET) film coated with a light release agent) having a thickness of 50 μm, and the weight was increased. A heat-curable adhesive sheet with a double-sided release film made of a release film / a heat-curable adhesive sheet / a light release film was obtained.
The obtained thermosetting adhesive sheet was heat-cured at 180 ° C. for 1 hour at 2 MPa, and the heavy release film and the light release film were peeled off to obtain a cured product of a 200 μm thermosetting resin composition.

<Measurement method of storage elastic modulus and loss tangent>
A test piece for measurement cut out from the obtained cured product to a size of 5 mm × 30 mm was cooled to 0 ° C. using a dynamic viscoelasticity measuring device “DVA200” (manufactured by IT Measurement Control Co., Ltd.) and then ascended. The temperature was raised to 300 ° C. at a temperature rate of 10 ° C./min, and viscoelasticity was measured at a vibration frequency of 10 Hz.
From the obtained viscoelasticity curve, the storage elastic modulus at 30 ° C., 150 ° C., and 280 ° C. is obtained, and the loss tangent (tanδ) is calculated at each temperature from the loss elastic modulus, plotted, and the tanδ curve becomes maximum. The points were calculated. When there are a plurality of maximum points, the value whose temperature is closest to room temperature (23 ° C.) is defined as the tan δ peak of the cured product.
In Tables 2 to 4, for example, the value of the storage elastic modulus of "1.0 × 10 ⁶ " is described as “1.0E + 06”.

(Resin flow)
[Preparation of sample A for evaluation]
<< Manufacture of thermosetting adhesive sheet with double-sided release film >>
A thermosetting adhesive sheet having a thickness of 25 μm after drying using the coating liquids obtained in each Example and each Comparative Example in the same manner as in the case of preparing a sample for measuring the storage elastic modulus and the loss elastic modulus. A heat-curable adhesive sheet with a double-sided release film was obtained by covering both sides of the above with a heavy release film having a thickness of 50 μm and a light release film having a thickness of 50 μm, respectively.
The light release film was peeled off from the thermosetting adhesive sheet with the double-sided release film, and the exposed surface of the thermosetting adhesive sheet was temporarily adhered to Kapton 100H manufactured by DuPont. Then, a circular hole having a diameter of 7 mm was formed by a punching machine.
Next, the heavy release film was peeled off, and a 12 μm copper foil was laminated on both sides of a 50 μm polyimide film on the exposed thermosetting adhesive sheet surface. After temporary bonding, the sample A was heat-cured at 180 ° C. for 1 hour at 2 MPa with a hot press to prepare an evaluation sample A.

[Evaluation method]
In the evaluation sample A prepared above, a hole having a diameter of 7 mm from the Kapton 100H side was observed with an optical microscope (VHX-7000 manufactured by KEYENCE Co., Ltd.) at a magnification of about 20 to 300 times, and the resin exuded from the end of the circle was observed. The length was measured and evaluated according to the following criteria.
⊚: Resin flow is 100 μm or less, which is an extremely good result.
◯: Resin flow is more than 100 μm to 150 μm or less. Good results.
Δ: Resin flow is more than 150 μm to 200 μm or less, which is within the practical range.
×: Resin flow exceeds 200 μm, not practical.

(Laser workability (before desmia liquid treatment))
[Preparation of sample B for evaluation]
A thermosetting adhesive sheet having a thickness of 25 μm after drying using the coating liquids obtained in each Example and each Comparative Example in the same manner as in the case of preparing a sample for measuring the storage elastic modulus and the loss elastic modulus. A heat-curable adhesive sheet with a double-sided release film was obtained by covering both sides of the above with a heavy release film having a thickness of 50 μm and a light release film having a thickness of 50 μm, respectively.
The light release film is peeled off from the heat-curable adhesive sheet with the double-sided release film, and the exposed heat-curable adhesive sheet surface is one of the double-sided copper-clad laminates in which 12 μm copper foil is laminated on both sides of a 50 μm polyimide film. Temporarily adhered to the copper foil on the surface of the surface with a vacuum laminator.
Next, the heavy release film was peeled off, and the polyimide film side of the single-sided copper-clad laminate, in which a 50 μm polyimide film and a 12 μm copper foil were laminated on the exposed thermosetting adhesive sheet surface, was similarly tentatively used with a vacuum laminator. After bonding, it is heat-cured at 180 ° C. for 1 hour at 2 MPa with a hot press, and is referred to as copper foil 1 / polyimide film 2 / copper foil 1 / cured product of thermosetting adhesive sheet 3 / polyimide film 2 / copper foil 1. An evaluation sample B having a laminated structure was obtained.

[Evaluation method]
The above sample B is irradiated with a laser from the upper surface of FIG. 1 using a UV-YAG laser (Model 5330, manufactured by ESI) to the boundary between the cured product of the thermosetting adhesive sheet and the double-sided copper-clad laminate. Blind via processing with a diameter of 150 μm was performed.
Next, the cross section of the blind via portion was observed with a laser microscope (VK-X100 manufactured by KEYENCE Co., Ltd.) at a magnification of about 20 to 500 times, and side etching (more than the designed opening diameter) that occurred in the cured product of the thermosetting adhesive sheet. The maximum length of (cutting in the horizontal direction) was measured and evaluated according to the following criteria.
⊚: 5 μm or less Very good result.
〇: Greater than 5 μm and 7 μm or less Good results.
Δ: Greater than 7 μm and 10 μm or less within the practical range.
×: Practical use larger than 10 μm.

(Laser workability (after desmear liquid treatment))
A sample subjected to blind via processing with a diameter of 150 μm to the boundary between the cured product of the thermosetting adhesive sheet and the double-sided copper-clad laminate was placed in a “MacDermid” manufactured by Japan McDermid Co., Ltd. at 60 ° C. for 7 minutes. The sample was sequentially immersed in "Macutizer 9275" at 75 ° C. for 7 minutes and in "Macutizer 9276" at 45 ° C. for 5 minutes, washed in a water shower at 23 ° C. for 5 minutes, and dried in an oven at 40 ° C. for 10 minutes.
Next, the cross section of the blind via portion was observed with a laser microscope (VK-X100 manufactured by Keyence Co., Ltd.) at a magnification of about 20 to 500 times. The state of the cured product of the curable adhesive sheet and the peeling of the boundary was evaluated. ⊚: Of the 30 holes, the number of holes where peeling occurred was 3 or less, which is an extremely good result.
◯: Of the 30 holes, the number of holes where peeling occurred was 4 or more and 6 or less, which is a good result.
Δ: Of the 30 holes, the number of holes in which peeling occurred is 7 or more and 10 or less, which is within the practical range.
×: Of the 30 holes, 11 or more holes with peeling are not practical.

(Heat-resistant)
[Evaluation method]
An evaluation sample B was prepared, stored in an atmosphere of 23 ° C. and 50% relative humidity for 24 hours or more, and then a solder float test was conducted in which the sample B was floated on molten solder at 288 ° C. for 3 minutes. After that, the cross section was observed with a laser microscope (VK-X100 manufactured by Keyence Co., Ltd.) at a magnification of about 20 to 500 times, and the copper foil and the cured product of the thermosetting adhesive sheet and the boundary were peeled off, and the polyimide film and the thermosetting adhesive sheet were peeled off. The state of the cured product and the peeling of the boundary was evaluated. The number of evaluation samples was 30.
⊚: The number of peeling occurrences is 10% or less, which is an extremely good result.
◯: The number of peeling occurrences exceeds 10% to 20% or less, which is a good result.
Δ: The number of holes where peeling occurs is more than 20% to 30% or less, which is within the practical range.
×: The number of holes where peeling occurs exceeds 30%, which is not practical.

(Cold heat cycle resistance)
An evaluation sample B was prepared and the thermal cycle characteristics were evaluated. The treatment conditions were -30 ° C for 15 minutes and 150 ° C for 15 minutes as one cycle, and after 2000 cycles, the cross section was observed with a laser microscope (VK-X100 manufactured by KEYENCE CORPORATION) at a magnification of about 20 to 500 times. The number of evaluation samples was 30.
⊚: The number of peeling occurrences is less than 10%, which is an extremely good result.
◯: The number of peeling occurrences is less than 10 to 20%, which is a good result.
Δ: The number of holes where peeling occurs is within the practical range of 20% to less than 30%.
×: The number of holes where peeling occurs is 30% or more, which is not practical.

(Impact absorption test)
[Preparation of evaluation sample C]
A thermosetting adhesive sheet having a thickness of 25 μm after drying using the coating liquids obtained in each Example and each Comparative Example in the same manner as in the case of preparing a sample for measuring the storage elastic modulus and the loss elastic modulus. A heat-curable adhesive sheet with a double-sided release film was obtained by covering both sides of the above with a heavy release film having a thickness of 50 μm and a light release film having a thickness of 50 μm, respectively.
The light release film was peeled off from the thermosetting adhesive sheet with the double-sided release film, and the exposed thermosetting adhesive sheet surface was temporarily bonded to a float glass having a thickness of 3 mm manufactured by Testpiece Co., Ltd. with a vacuum laminator.
Next, the heavy release film was peeled off, and the polyimide film side of the single-sided copper-clad laminate, in which a 50 μm polyimide film and a 12 μm copper foil were laminated on the exposed thermosetting adhesive sheet surface, was also temporarily bonded with a vacuum laminator. After that, an evaluation sample C having a laminated structure of float glass / cured product / polyimide film / copper foil was obtained by thermosetting at 180 ° C. for 1 hour and 2 MPa with a hot press.
[Evaluation method]
Next, a 300 g circular weight was freely dropped from a height of 20 cm onto the test surface (one-sided copper-clad laminate side) of the test piece with the apex facing down. The float glass side of the test piece was visually observed to confirm that there were no cracks or traces of the weight, and the evaluation was made according to the following criteria. The number of test samples was 10. ⊚: No cracks or traces, very good results.
◯: 1 to 2 cracks and traces in total Good results.
Δ: A total of 3 to 4 cracks and traces are within the practical range.
×: 5 or more cracks and traces are not practical.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a cured product having excellent laser processability, heat resistance, thermal cycle resistance, and shock absorption, and to provide a thermosetting resin composition having a small resin flow. These are suitable for manufacturing various printed wiring boards, electronic devices and the like that require high workability and reliability.

1 Copper foil 2 Polyimide film 3 Cured product of thermosetting adhesive sheet 4 Side etching

Claims (13)

A polyimide resin (A), which is a reaction product of a group of monomers containing a dimer diamine (a-1) and a tetracarboxylic acid anhydride (a-2),
It is selected from the group consisting of an epoxy compound (B-1), a maleimide compound (B-2), an isocyanate group-containing compound (B-3), a metal chelate compound (B-4) and a carbodiimide group-containing compound (B-5). With at least one curing agent (B),
A thermosetting resin composition containing a filler (C).
A thermosetting resin composition characterized in that the cured product obtained by heating the thermosetting resin composition at 180 ° C. for 60 minutes satisfies (a) to (c).
(A) The storage elastic modulus at 30 ° C. is 1.0 × 10 ⁶ to 1.0 × 10 ¹¹ Pa.
(B) The storage elastic modulus at 150 ° C. is 1.0 × 10 ⁴ to 1.0 × 10 ⁹ Pa.
(C) The storage elastic modulus at 280 ° C. is 1.0 × 10 ³ to 1.0 × 10 ⁹ Pa. The thermosetting resin composition according to claim 1, wherein the cured product has a loss tangent (tan δ) peak value of 0.3 or more at 0 to 280 ° C. The thermosetting resin composition according to claim 1 or 2, wherein the curing agent (B) contains three or more reactive functional groups capable of reacting with the polyimide resin (A) in one molecule. The thermosetting resin according to any one of claims 1 to 3, wherein the curing agent (B) is contained in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the polyimide resin (A). Composition. The thermosetting resin composition according to any one of claims 1 to 4, wherein the filler (C) is contained in an amount of 5 to 60 parts by mass with respect to 100 parts by mass of the polyimide resin (A). The thermosetting according to any one of claims 1 to 5, wherein the filler (C) is at least one selected from the group consisting of a fluorine filler, boron nitride, a liquid crystal polymer, and silica. Resin composition. The thermosetting resin composition according to any one of claims 1 to 6, wherein the thermosetting resin composition is used as a member for interlayer adhesion of a printed wiring board. A thermosetting adhesive sheet formed from the thermosetting resin composition according to any one of claims 1 to 7. A thermosetting cover sheet with a release film, comprising the thermosetting adhesive sheet according to claim 8 and a release film. A copper-clad laminate in which a copper foil and an insulating film are laminated via an adhesive layer which is a cured product of the thermosetting resin composition according to any one of claims 1 to 7. A printed wiring board using the thermosetting adhesive sheet according to claim 8. An electronic device comprising the printed wiring board according to claim 11. A polyimide resin (A), which is a reaction product of a group of monomers containing a dimer diamine (a-1) and a tetracarboxylic acid anhydride (a-2),
It is selected from the group consisting of an epoxy compound (B-1), a maleimide compound (B-2), an isocyanate group-containing compound (B-3), a metal chelate compound (B-4) and a carbodiimide group-containing compound (B-5). With at least one curing agent (B),
A cured product of a thermosetting resin composition containing a filler (C).
A cured product characterized by satisfying (a) to (c).
(A) The storage elastic modulus at 30 ° C. is 1.0 × 10 ⁶ to 1.0 × 10 ¹¹ Pa.
(B) The storage elastic modulus at 150 ° C. is 1.0 × 10 ⁴ to 1.0 × 10 ⁹ Pa.
(C) The storage elastic modulus at 280 ° C. is 1.0 × 10 ³ to 1.0 × 10 ⁹ Pa.

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