KR102401175B1 - Thermosetting resin composition and its use - Google Patents

Abstract

Provided is a thermosetting resin composition which has a low resin fluidity during a hot pressing step, and which, after curing, can form a cured product having excellent laser processability, heat resistance, cold/hot cycle resistance, and impact absorption properties. The present invention relates to a thermosetting resin composition comprising: 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); a hardening agent (B) which is at least one selected from a group consisting of an epoxy compound (B-1), a maleimide compound (B-2), an isocyanate group-containing compound (B-3), a metal chelating compound (B-4) and a carbodiimide group-containing compound (B-5); and a filler (C), and in the thermosetting resin composition, a cured product obtained by heating the thermosetting resin composition at 180 ℃ for 60 minutes shows a specific storage elastic coefficient at a predetermined temperature.

Description

Thermosetting resin composition, and its use {THERMOSETTING RESIN COMPOSITION AND ITS USE}

The present invention relates to a thermosetting resin composition containing a polyimide resin and a cured product thereof. The thermosetting adhesive sheet and the thermosetting cover sheet with a release film formed from the thermosetting resin composition of this invention are used suitably for manufacture of a copper clad laminated board, and protection of the circuit surface of a printed wiring board.

In recent years, further dimensional stability and excellent high frequency characteristic are calculated|required also in the material used for the printed wiring board used with progress of high density-ization and high functionalization of an electronic device.

For example, in patent document 1, the storage elastic modulus at 50 degreeC of the adhesive layer in a metal clad laminated board is 1800 Mpa, and the maximum value of the storage elastic modulus in a temperature range of 180 degreeC - 260 degreeC is 800 Mpa or less, and a glass transition A multilayer circuit board provided with an adhesive layer which is excellent in dimensional stability of a conductor and can reduce transmission loss also in transmission of a high frequency signal is disclosed when the temperature Tg is 180 degrees C or less.

Japanese Patent Laid-Open No. 2020-72198

By the way, with the downsizing of electronic devices and communication devices, materials used for printed wiring boards have, in addition to dimensional stability and reduction of transmission loss, high workability such as via formation, and high-level various Reliability is required.

In order to ensure conduction between the inner circuit and the outer circuit in a printed wiring board, openings such as blind vias and through holes may be formed by laser processing or drilling, and workability for forming the opening becomes important. . Along with space saving and new viewpoints on circuit design, materials that can be processed even with smaller hole diameters are required. In addition, resistance to a treatment liquid for removing a residue called smear generated by processing is also required.

Moreover, from a viewpoint of environmental protection, the request|requirement to the use of lead-free solder is increasing more and more in recent years instead of the conventional solder containing lead. 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 is heating up (eg, a solder reflow process, etc.). Then, the high temperature heat resistance of 260 degreeC or more is calculated|required also for the material used for a printed wiring board etc.

On the other hand, with the global spread of electronic devices, such as smartphones and tablet terminals, in recent years, reliability in the wide temperature range from low temperature to high temperature is calculated|required. Conventional printed wiring boards cause a problem of peeling between the interlayer adhesive layer and adjacent layers when exposed to extreme temperature changes, and the interlayer adhesive layer constituting the printed wiring board is required to be highly resistant to cooling and heating cycles.

Moreover, in recent years, electronic devices, such as a smart phone and a tablet terminal, are calculated|required to withstand physical shocks, such as a fall.

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, it goes through the process of pressing under heating. Then, in order to increase the density of an electronic device, the material with a small resin flow in the case of a hot press process is needed.

The present invention has been made in view of the above problems, it is a thermosetting resin composition with a small resin flow during the hot pressing process, and after curing, a cured product excellent in laser processability, heat resistance, cold-heat cycle resistance, and shock absorption is formed. An object of the present invention is to provide a thermosetting resin composition that can be used.

When this inventor earnestly examined, in the following aspects, it found out that the subject of this invention was solved, and came to complete this invention.

That is, the thermosetting resin composition according to the present invention includes a polyimide resin (A) which is a product of a reaction product of a group of monomers including dimer diamine (a-1) and tetracarboxylic anhydride (a-2), and an epoxy compound (B-) 1), at least one selected from the group consisting of 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) A thermosetting resin composition comprising a curing agent (B) and a filler (C), the cured product obtained by heating the thermosetting resin composition at 180° C. for 60 minutes satisfies the following (A) to (C).

(A) The storage modulus at 30°C is 1.0×10 ⁶ to 1.0×10 ¹¹ Pa.

(B) The storage modulus at 150°C is 1.0×10 ⁴ to 1.0×10 ⁹ Pa.

(C) The storage modulus at 280°C is 1.0×10 ³ to 1.0×10 ⁹ Pa.

ADVANTAGE OF THE INVENTION According to this invention, the resin flow is small at the time of hot pressing, and after hardening, it can form the hardened|cured material excellent in laser processability, heat resistance, cold-heat cycle resistance, and shock absorption.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the cross section of the blind via vicinity by laser processing of a printed wiring board.

Hereinafter, an example of embodiment to which this invention is applied is demonstrated. In addition, the size and ratio of each member in a subsequent drawing are for convenience of description, and are not limited to this. In addition, in this specification, description of "arbitrary number A - arbitrary number B" is contained in the said range with the number A as a lower limit and the number B as an upper limit. In addition, the "sheet" in this specification shall include not only the "sheet" defined in JIS but also a "film". In addition, the numerical value specified in this specification is a value calculated|required by the method disclosed in embodiment or an Example.

<Thermosetting resin composition>

The thermosetting resin composition in the present invention refers to a polyimide resin (A) which is a reaction product product of a group of monomers containing dimer diamine (a-1) and tetracarboxylic anhydride (a-2), and 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) several curing agents It is a thermosetting resin composition containing (B) and a filler (C), Comprising: The hardened|cured material obtained by heating the said thermosetting resin composition at 180 degreeC for 60 minutes satisfy|fills the following (A)-(C).

(A) The storage modulus at 30°C is 1.0×10 ⁶ to 1.0×10 ¹¹ Pa.

(B) The storage modulus at 150°C is 1.0×10 ⁴ to 1.0×10 ⁹ Pa.

(C) The storage modulus at 280°C is 1.0×10 ³ to 1.0×10 ⁹ Pa.

<Polyimide resin (A)>

The polyimide resin (A) of this invention is a thermosetting resin formed by making the monomer group containing dimer diamine (a-1) and tetracarboxylic anhydride (a-2) react. Polyimide resin (A) functions as binder resin in the thermosetting resin composition of this invention. The binder resin becomes the base body of the said thermosetting resin composition, and bears functions, such as holding|maintenance of the filler (C) mentioned later.

<Dimer diamine (a-1)>

The dimer diamine (a-1) of the present invention is a polybasic acid compound having a cyclic structure of 5 to 10 carbon atoms obtained by reacting a monobasic unsaturated fatty acid having at least one double bond or triple bond having 10 to 24 carbon atoms. and polyamine compounds converted to amino groups. For example, natural fatty acids such as soybean oil fatty acid, tall oil fatty acid, and rapeseed oil fatty acid, and their purified oleic acid, linoleic acid, linolenic acid, erucic acid, etc. The compound in which the carboxy group of the contained polybasic acid compound was converted into an amino group can be illustrated. The number of cyclic structures may be one or two, and in the case of two, two rings may be independent and may be continuous. Moreover, it is not necessary to have a cyclic structure, and the mixture of a cyclic structure and the compound which does not have a cyclic structure may be sufficient. By using the polyamine compound derived from a dimer acid, a dimer skeleton can be introduce|transduced into polyimide resin easily.

Examples of the cyclic structure include a saturated alicyclic structure, an unsaturated alicyclic structure, and an aromatic ring. The amino group (an amino group converted from a carboxyl group) may be directly bonded to the cyclic structure, but from the viewpoint of improving solubility and improving flexibility, the amino group is preferably bonded to the cyclic structure through an aliphatic chain. It is preferable that carbon number between an amino group and a cyclic structure is 2-25. Moreover, it is preferable that the dimer diamine (a-1) in this invention has a high degree of freedom and a high hydrophobicity chain|strand-type alkyl group as a part other than a cyclic structure from a viewpoint of a solubility improvement and a softness|flexibility improvement. It is preferable to have two or more alkyl groups with respect to one cyclic structure. It is preferable that carbon number of an alkyl group is 2-25.

Dimer diamine (a-1) has as a main component (70 mass % or more) a monomer containing a dimer skeleton derived from dimer acid (dimerized fatty acid) as a residue as a main component (70 mass % or more). It is preferably obtained by converting the carboxy group of the composition of the trimerized or higher fatty acid to an amino group. Moreover, the thing in which the degree of unsaturation was lowered by hydrogenation (hydrogenation reaction) with respect to a dimer skeleton is used especially suitably from a viewpoint of oxidation resistance (especially coloring in a high temperature range), and gelation suppression at the time of synthesis.

Commercially available products of dimer diamine (a-1) are, for example, preamine 1071, preamine 1073, preamine 1074, preamine 1075 (above, manufactured by Kuroda Japan); Basamine 551 (made by BASF Japan) etc. are mentioned. Dimer diamine can be used individually or 2 or more types can be used together.

As the polyamine compound used for polymerization of the polyimide resin (A), the above-mentioned dimer diamine (a-1) may be solely used, but other polyamine compounds may be used within a range not departing from the spirit of the present invention. It is preferable to set it as 50 mol% or less in polyamine compound whole quantity used for polyimide resin (A), and, as for another polyamine compound, it is more preferable to set it as 25 mol% or less.

<Other polyamine compounds>

Examples of other polyamine compounds include 1,4-diaminobenzene, 1,3-diaminobenzene, 1,2-diaminobenzene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,6-diaminotoluene, 2,4-diaminotoluene, 3,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 3,4'-diamino Diphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diamino-1,2-diphenylethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodi aromatic diamines such as phenylmethane, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, and 3,3'-diaminodiphenylsulfone; Ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,9-nonanediamine, 1,12-dodecamethylenediamine, metaxylene aliphatic diamines such as diamine; Alicyclics such as isophoronediamine, norbornanediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-diaminodicyclohexylmethane, piperazine, etc. group diamine; and the like. Moreover, it cannot be overemphasized that another polyamine compound is not limited to the said structure.

You may use another polyamine compound for superposition|polymerization of polyimide resin (A) in the range which does not deviate from the meaning of this invention. It is preferable to set it as 50 mol% or less in polyamine compound whole quantity used for polyimide resin (A), and, as for another polyamine compound, it is more preferable to set it as 25 mol% or less.

As another polyamine compound, it is especially preferable to use the monomer which contains as a residue the trimer which is a triamine derived from a C10-C24 monobasic unsaturated fatty acid and obtained by inverting a tricarboxylic acid. By using a trifunctional or more functional thing for a polyamine compound, a branched structure can be introduce|transduced into polyimide resin, it can make high molecular weight, and the heat resistance of the polyimide resin obtained can be enlarged.

<Tetracarboxylic anhydride (a-2)>

A well-known monomer can be used for the tetracarboxylic anhydride (a-2) of this invention. Specifically, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4 ,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2 ',3,3'-benzophenonetetracarboxylic dianhydride, 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride, 4,4'-(hexa Fluoroisopropylidene) diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride, 1,2,4,5- Benzenetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic acid Dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic acid Dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, p- Phenylenebis(trimellitate anhydride), thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic 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]benzenedianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzenedianhydride, bis[3-(3, 4-dicarboxyphenoxy)phenyl]methandianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methandianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy) ) phenyl] propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, bis (3,4-dicarboxyphenoxy) dimethylsilane dianhydride, 1,3 -bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalene Tet Lacarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, cyclobutane Tetracarboxylic dianhydride (for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, etc. ), cyclohexanetetracarboxylic dianhydride (eg, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, etc.), 9,9-bis[4-(3,1-, 3,2-, 3 ,3- or 3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, norbornane-2-spiro-α-cyclopentanone-α′-spiro-2′′-norbornane-5,5 '',6,6''-tetracarboxylic dianhydride, and 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 1,4,5,8-decahydronaphthalenetetracarboxylic dianhydride, 4,8-dimethyl-1,2,5,6-hexahydronaphthalenetetracarboxylic dianhydride, 2,6- Dichloro-1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,7-dichloro-1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-tetrachloro-1,4 ,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propanedianhydride, 1,1-bis( 3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methandianhydride, bis (3,4- Dicarboxyphenyl) methandianhydride, bis (3,4-dicarboxyphenyl) sulfonic anhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3',4'-benzophenonetetra Carboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho (1,2-C) furan-1,3 -Dion, etc. are mentioned. Among these, the tetracarboxylic anhydride which has two or less aromatic rings in 1 molecule from a viewpoint of heat resistance and shock absorption is more preferable. Among these, from the viewpoint of compatibility with the polyamine compound at the time of synthesis, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylether tetracarboxylic dianhydride, 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride, 1,3,3a,4,5,9b-hexahydro-5 (tetrahydro-2 Particular preference is given to ,5-dioxo-3-furanyl)naphtho(1,2-C)furan-1,3-dione. Tetracarboxylic anhydride can be used individually by 1 type or in 2 or more types.

The polyimide resin (A) has a reactive functional group that reacts with a curing agent (B) described later. Although the reactive functional group of polyimide resin (A) is not limited, At least one of an amino group and an acid anhydride group is suitable. The reactive functional group has at the side chain or terminal of the polyimide resin. The polyimide resin having an amine or acid anhydride group at the molecular terminal can be easily obtained by adjusting the amount ratio of the polyamine compound and the tetracarboxylic dianhydride. More preferably, polyimide resin which mix|blends tetracarboxylic dianhydride excessively (blends 50 mol% or more) and has an acid-anhydride group at the terminal is mentioned. Moreover, after mix|blending a polyamine compound excessively (blending 50 mol% or more) and obtaining the polyimide resin which has a polyamine compound at the terminal, you may make it react with maleic anhydride and introduce|transduce an acid anhydride group into the terminal.

<curing agent (B)>

It is preferable that a hardening|curing agent (B) has a functional group which can react with the reactive functional group which polyimide resin (A) has, and it is preferable to have two or more 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 a hardening|curing agent (B) is these compounds, the fall of the storage elastic modulus at the time of high temperature can be prevented, and the side etching at the time of laser processing can be suppressed. A hardening|curing agent can be used individually or in combination of 2 or more types.

<Epoxy group-containing compound (B-1)>

The epoxy group-containing compound (B-1) may be a compound having an epoxy group in the molecule, and is not particularly limited, but one having an average of two or more epoxy groups in one molecule can be preferably used. As the epoxy group-containing compound, for example, an epoxy resin such as a glycidyl ether type epoxy resin, a glycidylamine 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 novolak type epoxy resin, phenol novolak type epoxy resin , α-naphthol novolac type epoxy resin, bisphenol A novolak type epoxy resin, dicyclopentadiene type epoxy resin, tetrabromine bisphenol A type epoxy resin, brominated phenol novolak type epoxy resin, tris(glycidyloxyphenyl ) methane or tetrakis (glycidyloxyphenyl) ethane.

Examples of the glycidylamine-type epoxy resin include tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidyl metaaminophenol, or tetraglycidyl metaxylylenediamine. have.

As a glycidyl ester type epoxy resin, diglycidyl phthalate, diglycidyl hexahydrophthalate, or diglycidyl tetrahydrophthalate etc. are mentioned, for example.

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

An epoxy group containing compound can be used individually by 1 type or in combination of 2 or more type.

Examples of the epoxy group-containing compound include bisphenol A epoxy resin, cresol novolak epoxy resin, phenol novolak epoxy resin, tris(glycidyloxyphenyl)methane, tetrakis(glycidyloxyphenyl) from the viewpoint of high adhesiveness. It is preferable to use ethane or tetraglycidyl metaxylylenediamine, and it is more preferable from a viewpoint of high heat resistance that it contains trifunctional or more than trifunctional epoxy group.

<Maleimide group-containing compound (B-2)>

As the maleimide group-containing compound (B-2), any compound having a maleimide group in the molecule is not particularly limited, but one having an average of two or more maleimide groups in one molecule can be preferably used.

Specific examples of the maleimide group-containing compound in the present invention include o-phenylenebismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, and 4-methyl-1,3-phenylenebismaleimide. mide, N,N'-(toluene-2,6-diyl)bismaleimide, 4,4'-diphenylmethanebismaleimide, bisphenol A diphenyletherbismaleimide, 3,3'-dimethyl-5, 5'-diethyl-4,4'-diphenylmethanebismaleimide, 4,4'-diphenyl etherbismaleimide, 4,4'-diphenylsulfonebismaleimide, 1,3-bis(3- Maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, polyphenylmethanemaleimide (CASNO: 67784-74-1, a reaction product of a polymer consisting of formaldehyde and aniline and maleic anhydride) , N,N'-ethylenebismaleimide, N,N'-trimethylenebismaleimide, N,N'-propylenebismaleimide, N,N'-tetramethylenebismaleimide, N,N'-pentamethylene Bismaleimide, N,N'-(1,3-pentanediyl)bis(maleimide), N,N'-hexamethylenebismaleimide, N,N'-(1,7-heptanediyl)bis Maleimide, N,N'-(1,8-octanediyl)bismaleimide, N,N'-(1,9-notanediyl)bismaleimide, N,N'-(1,10-decanediyl) Bismaleimide, N,N'-(1,11-undecanediyl)bismaleimide, N,N'-(1,12-dodecanediyl)bismaleimide, N,N'-[(1,4 -Phenylene)bismethylene]bismaleimide, N,N'-[(1,2-phenylene)bismethylene]bismaleimide, N,N'-[(1,3-phenylene)bismethylene]bis Maleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, N,N'-[(methylimino)bis(4,1-phenylene)]bismaleimide, N, N'-(2-hydroxypropane-1,3-diylbisiminobiscarbonylbisethylene)bismaleimide, N,N'-(dithiobisethylene)bismaleimide, N,N'-[hexamethylenebis (iminocarbonylmethylene)]bismaleimide, N,N'-carbonylbis(1,4-phenylene)bismaleimide, N,N',N''-[nitrilotris(ethylene)]tris Maleimide, 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)]bis Maleimide, N,N'-[methylenebis(oxy-p-phenylene)]bis(maleimide), N,N'-[dimethylsilylenebis[(4,1-phenylene)(1, 3,4,-Oxadiazole-5,2-diyl)(4,1-phenylene)]]bismaleimide, N,N'-[(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)bismaleimide, 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'-[sulfonylbis(4,1-phenylene)bis(oxy)bis(4,1-phenylene)]bismaleimide, N ,N'-[naphthalene-2,7-diylbis(oxy)bis(4,1-phenylene)]bismaleimide, N,N'-[p-phenylenebis(oxy-p-phenylene)] Bismaleimide, N,N'-[(1,3-phenylene)bisoxybis(3,1-phenylene)]bismaleimide, N,N'-(3,6,9-trioxaundecane -1,11-diyl)bismaleimide, N,N'-[isopropylidenebis[p-phenyleneoxycarbonyl(m-phenylene)]]bismaleimide, N,N'-[isopropylidene Bis[p-phenyleneoxycarbonyl (p-phenylene)]]bismaleimide, N,N'-[isopropylidenebis[(2,6-dichlorobenzene-4,1-diyl)oxycarbonyl ( p-phenylene)]]bismaleimide, N,N'-[(phenylimino)bis(4,1-phenylene)]bismaleimide, N,N'-[azobis(4,1-phenyl) Ren)]bismaleimide, N,N'-[1,3,4-oxadiazole-2,5-diyl Bis(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-yl]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-phenyleneoxyp- Phenylene)bismaleimide, N,N'-[5-tert-butyl-1,3-phenylenebis[(1,3,4-oxadiazole-5,2-diyl)(4,1-phenyl) Ren)]]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)]bismaleimide, N,N'-(3,6,9-tri Oxaundecan-1,11-diyl)bismaleimide, N,N'-(ethylenebis-p-phenylene)bismaleimide, Designer Molecules company BMI-689, BMI-1500, BMI-1700, BMI- Polyfunctional maleimide, such as 3000, BMI-5000, BMI-9000, ODA-BMI by JFE Chemicals, and BAF-BMI, is mentioned.

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

<Isocyanate group-containing compound (B-3)>

As an isocyanate group containing compound (B-3), what is necessary is just a compound which has an isocyanate group in a molecule|numerator, and it does not specifically limit.

Specifically, as an isocyanate group-containing compound having one isocyanate group in one molecule, n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, benzyl isocyanate, (meth)acryloyloxyethyl isocyanate, 1,1-bis[( and meth)acryloyloxymethyl]ethyl isocyanate, vinyl isocyanate, allyl isocyanate, (meth)acryloyl isocyanate, and isopropenyl-α,α-dimethylbenzyl isocyanate.

In addition, 1,6-diisocyanatohexane, diisocyanate isophorone, diisocyanate 4,4'-diphenylmethane, polymeric diphenylmethane diisocyanate, xylylene diisocyanate, 2,4-diisocyanate Tolylene, diisocyanate toluene, 2,4-diisocyanate toluene, diisocyanate hexamethylene, diisocyanate 4-methyl-m-phenylene, naphthylene diisocyanate, paraphenylene diisocyanate, tetramethylxylylenedi Isocyanate, cyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, tolidine diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, m-tetra A compound obtained by reacting a diisocyanate compound such as methylxylylene diisocyanate, P-tetramethylxylylene diisocyanate, dimer acid diisocyanate and a vinyl monomer containing hydroxyl, carboxyl and amide groups in equimolar amounts can also be used as the isocyanate ester compound. have.

Specifically, as an isocyanate group-containing compound having two isocyanate groups in one molecule, 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-di Phenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, Aromatic diisocyanate, such as dianisidine diisocyanate, 4,4'- diphenyl ether diisocyanate, and 4,4', 4''- triphenylmethane triisocyanate;

trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, aliphatic diisocyanates such as 2,4,4-trimethylhexamethylene diisocyanate;

ω,ω'-diisocyanate-1,3-dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-diisocyanate-1,4-diethylbenzene, 1,4- aromatic aliphatic diisocyanates such as tetramethylxylylene diisocyanate and 1,3-tetramethylxylylene diisocyanate;

3-isocyanatemethyl-3,5,5-trimethylcyclohexylisocyanate [alias: isophorone diisocyanate], 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate , methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), 1,3-bis(isocyanatemethyl)cyclohexane, 1, Alicyclic diisocyanate, such as 4-bis (isocyanate methyl) cyclohexane, is mentioned.

In addition, specific examples of the isocyanate group-containing compound having three isocyanate groups in one molecule include aliphatic polyisocyanates such as aromatic polyisocyanate and lysine triisocyanate, aromatic aliphatic polyisocyanate, alicyclic polyisocyanate, and the like. The trimethylolpropane adduct body of the demonstrated diisocyanate, the biuret body which reacted with water, and the trimer which has an isocyanurate ring are 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 is protected by ?-caprolactam, MEK oxime, or the like can also be used.

Specific examples 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, or the like. In particular, the hexamethylene diisocyanate trimer having an isocyanurate ring and blocked by MEK oxime or pyrazole, when used in the present invention, has excellent adhesive strength and heat resistance to polyimide or copper. desirable. Moreover, it is preferable to have a trifunctional or more than trifunctional isocyanate group from a heat resistant viewpoint.

<Metal Chelate Compound (B-4)>

A metal chelate compound (B-4) is an organometallic compound which consists of a metal and an organic substance, and reacts with the reactive functional group of binder resin, and forms a bridge|crosslinking. Although the kind of organometallic compound is not specifically limited, An organoaluminum compound, an organotitanium compound, an organozirconium compound, etc. are mentioned. In addition, a metal-oxygen bond may be sufficient as the bond between a metal and an organic substance, and it is not limited to a metal-carbon bond. In addition, any of a chemical bond, a coordination bond, and an ionic bond may be sufficient as the bonding mode of a metal and an organic substance. Moreover, it is preferable from a viewpoint of heat resistance that it is trifunctional or more.

The organoaluminum compound is preferably an aluminum metal chelate compound. The aluminum metal chelate compound is, for example, ethylacetoacetate aluminum diisopropylate, aluminum tris(ethylacetoacetate), alkylacetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bis(ethylacetoacetate), aluminum tris (acetyl acetate), aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum di-n-butoxide monomethyl acetoacetate, aluminum diisobutoxide monomethyl acetoacetate, aluminum di-sec-butoxide monomethyl acetoacetate; aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum-sec-butylate, aluminum ethylate, etc. are mentioned.

The organic titanium compound is preferably a titanium metal chelate compound. The titanium metal chelate compound is, for example, titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethyl acetoacetate, titanium octylene glycolate, titanium ethyl acetoacetate, titanium-1,3-propanedioxybis (ethyl aceto). acetate), polytitanyl acetylacetylacetonato, tetraisopropyl titanate, tetran-butyl titanate, butyl titanate dimer, tetraoctyl titanate, tert-amyl titanate, tetratert-butyl titanate, tetrastearyl titanate Nate, titanium isostearate, tri-n-butoxytitanium monostearate, di-i-propoxytitanium distearate, titanium stearate, di-i-propoxytitanium diisostearate, (2-n -Butoxycarbonylbenzoyloxy)tributoxytitanium etc. are mentioned.

The organic zirconium compound is preferably a zirconium metal chelate compound. The zirconium metal chelate compound is, for example, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate), zirconium tetra Acetylacetonate, n-propyl zirconate, n-butyl zirconate, zirconium stearate, zirconium octylate, etc. are mentioned. Among these, an organic titanium compound and an organic zirconium compound are preferable at the point 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. As the carbodiimide group-containing compound, for example, carbodilite V-01, V-03, V-05, V-07, V-09 (Nissinbo Chemical Co., Ltd.), cyclic carbodiimide (Teijin) Corporation) and the like. It is preferable to have an average of 3 or more carbodiimide groups in 1 molecule from a heat resistant viewpoint.

It is preferable that the hardening|curing agent (B) used for this invention contains an aromatic ring structure in a hardening|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 effect of relieving stress occurring during a cooling/heating cycle is exhibited.

The hardening|curing agent (B) used for this invention is an epoxy compound (B-1), a maleimide compound (B-2), an isocyanate group containing compound (B-3) with respect to 100 mass parts of said polyimide resins (A) , a metal chelate compound (B-4), and the total of the carbodiimide group-containing compound (B-5) are preferably contained in a range from 1 to 20 parts by mass, more preferably from 1 to 15 parts, , it is more preferable to contain 3-10 parts. By setting the addition amount of the curing agent (B) to 1 to 20 parts, the effect of suppressing the storage elastic modulus of the cured product and suppressing the occurrence of cracks with respect to the stress caused by a sudden temperature change during the cooling/heating cycle can be expressed.

<Filler (C)>

Next, the filler (C) used by this invention is demonstrated in detail. The thermosetting resin composition of this invention contains a filler for the purpose of storage elastic modulus control of hardened|cured material.

Although it does not specifically limit as a filler (C), As a shape, a spherical shape, a powder shape, fibrous shape, needle shape, scale shape, etc. are mentioned. As the filler (C), for example, a fluorine filler: polytetrafluoroethylene powder or a modified product thereof, tetrafluoroethylene-perfluoroalkylvinyl ether powder, tetrafluoroethylene-ethylene powder, tetrafluoroethylene-hexa Fluoropropylene powder, tetrafluoroethylene-vinylidene fluoride powder, tetrafluoroethylene-hexafluoropropylene-perfluoroalkylvinyl ether powder, polychlorotrifluoroethylene powder, chlorotrifluoroethylene-ethylene powder, Chlorotrifluoroethylene-vinylidene fluoride powder, polyvinylidene fluoride powder, polyvinyl fluoride powder, etc. are mentioned. As other fillers, polyethylene powder, polyacrylic acid ester powder, epoxy resin powder, polyamide powder, polyimide powder, polyurethane powder, liquid crystal polymer beads, polysiloxane powder, etc., silicone, acrylic, styrene-butadiene rubber, butadiene rubber, etc. Polymer fillers, such as a core shell of a multilayer structure using; (poly)phosphate-based compounds such as melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium amide phosphate, ammonium polyphosphate, carbamate phosphate, and carbamate polyphosphate, and organic phosphate esters Phosphinic acid compounds, such as a compound, a phosphazene compound, a phosphonic acid compound, diethyl phosphinate aluminum, methyl ethyl phosphinate aluminum, diphenyl phosphinate aluminum, ethyl butyl phosphinate aluminum, methyl butyl phosphinate aluminum, and polyethylene phosphinate aluminum; phosphorus fillers such as a phosphine oxide compound, a phosphorane compound, and a phosphoramide compound;

nitrogen-based fillers such as benzoguanamine, melamine, melam, melem, melon, melamine cyanurate, cyanuric acid compound, isocyanuric acid compound, triazole-based compound, tetrazole compound, diazo compound, and urea;

Silica, hollow silica, porous silica, mica, talc, kaolin, clay, hydrotalcite, wollastonite, zonolite, silicon nitride, boron nitride, aluminum nitride, calcium hydrogen phosphate, calcium phosphate, glass flake, 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, antimony oxide, oxide and inorganic fillers such as nickel, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, and aluminum borate.

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

It is preferable that the average particle _diameter D50 of a filler (C) is 0.1-25 micrometers. When the average particle diameter 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. As for the average particle _diameter D50 of a filler (C), it is more preferable that it is the range of 2-10 micrometers.

It is preferable that content of a filler (C) is 5-60 mass parts with respect to 100 mass parts of said polyimide resins (A). By setting the amount of filler (C) to 60 parts by mass or less, the storage elastic modulus of the cured film can be controlled to a certain level or less, and the effect of suppressing the occurrence of cracks or peeling with respect to the stress caused by a sudden temperature change during the cooling/heating cycle is obtained. indicates. In addition, when the content of the filler (C) is 5 parts by mass or more, it is possible to maintain a high storage elastic modulus near room temperature, and it becomes difficult to swell in the desmear process after laser processing, and at the interface between the copper clad laminate and the thermosetting resin composition of the present invention Therefore, peeling and lifting are less likely to occur. As for content of a filler, it is more preferable that it is 5-40 mass parts, It is still more preferable that it is 5-30 mass parts, It is most preferable that it is 5-20 mass parts or less.

As for the filler (C), when the thermosetting resin composition of the present invention is a thermosetting adhesive sheet to be described later, the relationship between the average particle diameter D ₅₀ of the filler (C) and the film thickness of the thermosetting adhesive sheet is calculated from (Equation 1) It is preferable that the value used is 0.8 or less, It is more preferable that it is 0.1 or less, It is more preferable that it is 0.05 or less. By setting it as 0.8 or less, the binder resin component can fully coat the filler surface, and favorable adhesive force etc. can be expressed to a to-be-adhered body, and peeling and lifting hardly occur at the time of a cooling/heat cycle.

(Equation 1)

Average particle diameter 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 polymerization of the binder resin, using three rolls, etc. The method of kneading a filler with binder resin, the method of preparing the dispersion liquid containing a filler, and mixing this with binder resin, etc. are mentioned. In addition, in order to disperse the filler well and to stabilize the dispersed state, a dispersant, a thickener, etc. may be used in a range that does not affect the physical properties of the thermosetting resin composition.

<Other additives>

In addition, in the thermosetting resin composition of the present invention, an energy ray absorber, a dye, a pigment, an antioxidant, a polymerization inhibitor, an antifoaming agent, a leveling agent, an ion scavenger, a moisturizing agent, a viscosity A modifier, preservative, antibacterial agent, antistatic agent, anti-blocking agent, infrared absorber, electromagnetic wave shielding agent, etc. can be added, and it is preferable to mix|blend an energy-beam absorber from the point of laser processability improvement.

<Storage modulus of thermosetting resin composition>

The method of calculating|requiring a storage elastic modulus is demonstrated. The storage modulus can be measured using a DVA method (dynamic viscoelasticity analysis method) measuring device or the like. The storage modulus of each temperature can be calculated|required from the viscoelasticity curve with respect to the hardened|cured material obtained by the said apparatus.

The hardened|cured material obtained by heating the thermosetting resin composition of this invention at 180 degreeC for 60 minutes satisfy|fills (A)-(C).

(A) The storage modulus at 30°C is 1.0×10 ⁶ to 1.0×10 ¹¹ Pa.

(B) The storage modulus at 150°C is 1.0×10 ⁴ to 1.0×10 ⁹ Pa.

(C) The storage 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., preferably 1.0×10 ⁷ to 1.0×10 ¹⁰ Pa, and , more preferably 1.0×10 ⁸ to 1.0×10 ⁹ Pa.

By setting the storage elastic modulus at 30°C to 1.0×10 ¹¹ Pa or less, the effect of suppressing the occurrence of cracks and the like is exhibited with respect to the stress caused by the rapid temperature change during the cooling/heating cycle. In addition, by setting it as 1.0 × 10 ⁶ Pa or more, the penetration of the desmear liquid in the desmear step is suppressed, and the occurrence of peeling and lifting at the interface between the copper clad laminate and the thermosetting resin composition of the present invention can be suppressed, , desmear liquid resistance can be improved. The storage elastic modulus in 30 degreeC is controllable by adjusting the kind and addition amount of a filler (C).

[Storage modulus at 150°C]

Then, the cured product obtained by heating the thermosetting resin composition of the present invention at 180° C. for 60 minutes has a storage modulus at 150° C. of 1.0×10 ⁴ to 1.0×10 ⁹ Pa, and 1.0×10 ⁵ to 1.0×10 ⁸ Pa This is preferable, and 1.0×10 ⁶ to 1.0×10 ⁷ Pa is more preferable.

By setting the storage elastic modulus at 150° C. to 1.0×10 ⁹ Pa or less, as in the case of 30° C., the effect of suppressing the occurrence of cracks with respect to the stress caused by a sudden temperature change during the cooling/heating cycle is exhibited. In addition, 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 increased, and when used as an interlayer adhesion thermosetting resin composition of a multilayer printed wiring board, the resin flow can be suppressed, and dimensional stability can be ensured. . The storage elastic modulus in 150 degreeC is also controllable by adjusting the kind and addition amount of a filler (C).

In the range of about -30 degreeC to about 150 degreeC, since cold-heat cycle tolerance repeats a cold-heat cycle, the storage elastic modulus of both in a room temperature range and a high temperature area|region is related. Therefore, the cold-heat cycle resistance has a storage modulus of 1.0×10 ¹¹ Pa or less at 30° C. and a storage elastic modulus of 1.0×10 ⁹ Pa or less at 150° C. , it exhibits the effect of suppressing the occurrence of cracks. 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 resistance to cooling/heating cycle can be expressed.

[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., preferably 1.0×10 ⁴ to 1.0×10 ⁸ Pa, and , and more preferably 1.0×10 ⁵ to 1.0×10 ⁷ Pa.

By setting the storage elastic modulus at 280°C to 1.0×10 ⁹ Pa or less, stress when high-temperature heat is applied in the solder mounting process can be relieved, the occurrence of cracks can be suppressed, and heat resistance is improved. In addition, by setting it to 1.0×10 ³ Pa or more, in the laser processing process for forming blind vias or through-hole vias, even when high-temperature heat from the laser is applied, heat does not leak, side etching can be suppressed, and laser processability is improved. . The storage elastic modulus in 280 degreeC can be adjusted according to the kind of hardening|curing agent (B).

<Loss tangent (tanδ) peak>

A method for obtaining the peak value of the loss tangent (tanδ) will be described. The storage modulus can be measured using a DVA method (dynamic viscoelasticity analysis method) measuring device or the like. From the viscoelastic curve for the cured product obtained by the apparatus, the loss tangent (tanδ) was calculated at each temperature from the storage elastic modulus at each temperature and the loss elastic modulus, and by performing a plot based on (Formula 2), the tanδ curve was Let the maximum point be the peak value. Moreover, when two or more local maximums exist, let the value whose temperature is closest to room temperature (23 degreeC) most be the tan-delta peak of the hardened|cured material.

(Equation 2)

(loss tangent; tanδ) = (loss modulus)/(storage modulus)

The cured product obtained by heating the thermosetting resin composition of the present invention at 180° C. for 60 minutes has a loss tangent (tanδ) peak value at 0 to 280° C. of preferably 0.3 or more, more preferably 0.5 or more, and further preferably 0.7 or more. desirable. When the loss tangent (tanδ) peak value is 0.3 or more, the impact diffusivity becomes large, and the impact from the outside can be missed. The loss tangent (tanδ) is two or less aromatic rings contained in one structural unit derived from the tetracarboxylic anhydride (a-2) in the polyimide resin (A), and thus the degree of freedom of molecular movement of the polyimide resin (A). It is possible to increase the impact diffusivity by flexibly generating molecular motion against external impact.

Embodiments of the thermosetting resin composition of the present invention, 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 and knitted on a printed wiring board, whereby the thermosetting resin composition is a printed wiring board functions as a thermosetting composition for interlayer adhesion of

<Thermosetting adhesive sheet>

A thermosetting adhesive sheet made the thermosetting resin composition in this invention into a sheet form. A thermosetting adhesive sheet is used as a member for adhesion|attachment of a printed wiring board and an electronic device, and has a function which adhere|attaches and holds another member. A thermosetting adhesive sheet is hardened|cured by passing through a heating or a hot press process after performing temporary bonding between members to be adhere|attached, and adhere|attaching to-be-adhered body.

<Method for producing thermosetting adhesive sheet>

In the method for producing a thermosetting adhesive sheet, for example, a coating solution containing a polyimide resin (A), a curing agent (B), a filler (C), and other optional components and a solvent is applied to one side of the release film after application A thermosetting adhesive sheet with a double-sided release film can be obtained by removing and drying a liquid medium such as an organic solvent contained therein, usually at 40 to 150° C., and laminating another release film on the surface of the formed thermosetting adhesive sheet. By laminating both surfaces with a release film, surface contamination of the thermosetting adhesive sheet can be prevented. By peeling off the release film, the thermosetting adhesive sheet can be isolated.

Two peeling films can be used either of the same type or different types. Since strength and weakness can be provided to peeling force by using the peeling film from which peeling property differs, it becomes easy to peel in order.

As the coating method, for example, comma coating, knife coating, die coating, lip coating, roll coating, curtain coating, bar coating, gravure printing, flexographic printing, screen printing, dip coating, spray coating, spin coating, etc. are known. method can be selected.

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

<Thermosetting cover sheet with release film>

In a thermosetting cover sheet with a release film, a thermosetting adhesive sheet is sandwiched between the release film and the cover resin layer. In other words, the thermosetting cover sheet replaces the peelable film on one side in the thermosetting adhesive sheet with a double-sided peeling film by the 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, poly At least one resin selected from the group consisting of ether ether ketone and fluorine-based resins may be used.

The fluorine-based resin as the insulating film is not particularly limited, and for example, polytetrafluoroethylene, polytetrafluoroethylene-perfluoroalkylvinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, di and at least one selected from the group consisting of fluoroethylene-trifluoroethylene copolymer, tetrafluoroethylene-ethylene copolymer, polychlorotrifluoroethylene, and polyvinylidene fluoride.

<Usage of thermosetting adhesive sheet, thermosetting adhesive sheet with release film, thermosetting cover sheet with release film>

A copper clad laminate and a printed wiring board can be obtained using the thermosetting adhesive sheet etc. with a peeling film of this invention.

A copper clad laminated board is a copper foil and an insulating film laminated|stacked through the adhesive layer which is hardened|cured material of the thermosetting adhesive sheet obtained from the thermosetting resin composition of this invention.

In such a copper clad laminate, for example, the release film is sequentially peeled off from the thermosetting adhesive sheet with a release film of the present invention, and a copper foil and an insulating film are respectively stacked on each side of the thermosetting adhesive sheet (this step is sometimes referred to as temporary adhesion). It is obtained by thermosetting the thermosetting adhesive sheet between copper foil and an insulating film by passing through a ), a heating, or a hot press process.

Alternatively, a thermosetting adhesive sheet between the copper foil and the insulating film is applied and dried on the insulating film by applying and drying a solution for forming the thermosetting adhesive sheet, and by overlapping the copper foil on the formed thermosetting adhesive sheet, heating or hot pressing. By thermosetting a copper clad laminate, a copper clad laminate can also be obtained.

As for a copper clad laminated board, like copper foil/adhesive layer/insulating film/adhesive layer/copper foil, all both-sided outermost layers may be copper foil, and can also provide the inner layer of copper foil. When laminating a copper foil or an insulating film using a plurality of thermosetting adhesive sheets, the plurality of thermosetting adhesive sheets may be heat-cured at once after the temporary bonding has been performed a plurality of times.

<Printed wiring board>

A printed wiring board can be obtained by processing the copper foil in a copper clad laminated board by etching etc., forming a signal circuit and a ground circuit. By peeling the release film from the thermosetting cover sheet with the release film, bonding the thermosetting adhesive sheet surface to the circuit surface, and heat curing, a cover layer made of a cured product of the cover resin layer/adhesive sheet is formed to protect the signal circuit, or further It can also be used as a base body for multilayering.

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, only the exposed portion is cured, and then After the copper foil of the unexposed portion is removed by etching, the remaining resist layer may be peeled off to form a conductive circuit from the copper foil.

In addition, the printed wiring board of this invention can also be obtained, without using a copper clad laminated board.

For example, on a flexible and insulating plastic film such as polyester, polyimide, liquid crystal polymer, or PTFE film, a conductor pattern is formed by a printing technique, and then the thermosetting adhesive of the present invention is applied to cover the conductor pattern. By overlapping a protective layer through a sheet|seat, and heating and pressurizing, a thermosetting adhesive sheet can be hardened, and the flexible printed wiring board in which the protective layer was provided can also be obtained.

Alternatively, a flexible printed wiring board provided with a protective layer may be obtained by providing only the necessary circuits by means such as sputtering or plating on a flexible and insulating plastic film, and similarly below, through the cured product of the thermosetting adhesive sheet of the present invention. have.

In addition, between a plurality of flexible printed wiring, a thermosetting adhesive sheet obtained by peeling a release film from the thermosetting adhesive sheet with a release film of the present invention is sandwiched therebetween, and the thermosetting adhesive sheet is cured by heating and pressurization to form a multilayer flexible printed wiring board. you may get

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

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

In general, after forming a via opening by laser processing or drill processing, there is a desmear process in which the remaining resin (smear) is removed. As for this desmear process, there exist a dry process using plasma, and a wet process using etching liquids, such as potassium permanganate. Although the dry process is suitable for desmear of small diameter vias, there are many problems such as when a special gas is required or it takes time to set the vacuum time, so the desmear by the wet process is often used even in development is becoming

By setting the storage elastic modulus at 30°C to 1.0×10 ⁶ to 1.0×10 ¹¹ Pa, penetration of the desmear liquid in the desmear process is suppressed, and peeling at the interface between the copper clad laminate and the thermosetting resin composition of the present invention In addition, the occurrence of floating can be suppressed.

Various electronic devices, such as a smart phone, a tablet terminal, and a camera, can be manufactured using the printed wiring board of this invention.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. In addition, let "part" in an Example represent "mass part", and "%" shall represent "mass %", respectively.

In addition, the acid value, amine value, and weight average molecular weight (Mw) measurement of resin were performed by the following method.

《Acid value measurement》

The acid value was measured according to JIS K0070. Approximately 1 g of the sample is precisely weighed in a static Erlenmeyer flask, and 100 mL of a tetrahydrofuran/ethanol (volume ratio: tetrahydrofuran/ethanol=2/1) mixture is added and dissolved. To this, a 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 maintained a pink color for 30 seconds. The acid value was calculated|required 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

《Amine value measurement》

Approximately 1 g of the sample is precisely weighed in a static Erlenmeyer flask, and 100 mL of a cyclohexanone solvent is added and dissolved. To this, add 2 or 3 drops of indicator prepared by mixing a solution of 0.20 g of Methyl Orange in 50 mL of distilled water and a solution of 0.28 g of Xylene Cyanol FF in 50 mL of methanol, and hold for 30 seconds. Then, titrate with 0.1N alcoholic hydrochloric acid solution until the solution turns blue-grey. The amine titer was calculated|required by the following formula (unit: mgKOH/g).

Amine value (mgKOH/g) = (5.611 × a × F) / S

step,

S: Sample collection amount (g)

a: Consumption of 0.1N alcoholic hydrochloric acid solution (mL)

F: titer of 0.1N alcoholic hydrochloric acid solution

<<Measurement of Weight Average Molecular Weight (Mw)>>

For the measurement of Mw, GPC (Gel Permeation Chromatography) "GPC-101" manufactured by Showa Denko Co., Ltd. was used. THF (tetrahydrofuran) was used as a solvent, and what connected two "KF-805L" (Showa Denko Corporation: GPC column: 8 mmID x 300 mm size) in series was used as a column. The sample concentration was 1% by mass, the flow rate was 1.0 mL/min, the pressure was 3.8 MPa, and the column temperature was 40°C, and Mw was determined in terms of polystyrene. Data analysis used a manufacturer's built-in software to calculate a calibration curve, molecular weight, and peak area, and calculated Mw for a range of 17.9 to 30.0 minutes of holding time as an analysis target.

[Synthesis Example 1] <Synthesis of polyimide resin (P1)>

378.7 g of dimer diamine (preamine 1075) having 36 carbon atoms as a polyamine compound and bisphenol A type acid dianhydride (4 380.0 g of ,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride) (BISDA-1000) and 1100 g of cyclohexanone as a solvent were added, and when uniform stirred until After becoming uniform, the temperature is raised to 110 ° C. After 30 minutes, the temperature is raised to 140 ° C. When the temperature is 140 ° C., the reaction is continued at the same temperature for 10 hours, the dehydration reaction is continued, a weight average molecular weight of 54,000, an acid value A polyimide resin (A1) having 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, except having changed the kind and quantity of dimer diamine (a-1), tetracarboxylic anhydrides (a-2), etc., it carried out similarly to Synthesis Example 1, and polyimide resin (A2) - (A6) was obtained similarly, respectively.

[Table 1]

[Example 1]

<<Preparation of thermosetting resin composition (coating liquid)>>

In terms of solid content, 100 parts of polyimide resin (A1), 5 parts of an epoxy group-containing compound (B-1-1) described later, and 20 parts of boron nitride are put into a container, and a mixed solvent ( Toluene:MEK=9:1 (weight ratio)) was added, and the mixture was stirred with a disper for 10 minutes to obtain a thermosetting resin composition (coating solution).

According to the method to be described later, the storage elastic modulus and loss elastic modulus of the cured product are obtained, the resin flow as a thermosetting adhesive sheet, laser workability before and after desmear solution immersion, heat resistance, cold/heat cycle resistance, and shock absorption are evaluated, and the results are shown in Tables 2 to 4 is shown in

[Examples 2 to 22, Comparative Examples 1 to 5]

As shown in Tables 2-4, except having changed the kind and quantity of binder resin, a hardening|curing agent, and a filler, it carried out similarly to Example 1, the thermosetting resin composition (coating liquid) was obtained, and it evaluated similarly.

《Raw material: Binder resin》

Polyimide resin (A): Synthesis Examples 1 to 6 described (A1) to (A6)

(A7): Byron 637, an acid value of 5 mgKOH/g, a weight average molecular weight of 30000, and a Tg of 21°C polyester resin (manufactured by Toyobo Corporation)

《Raw material: curing agent (B)》

Epoxy group-containing compound (B-1-1): "ELM-434" (glycidylamine type epoxy resin, epoxy equivalent 100 g/eq, tetrafunctional) manufactured by Sumitomo Chemical

Epoxy group-containing compound (B-1-2): “YX-8800” (glycidyl ether type epoxy resin, epoxy equivalent 180 g/eq, bifunctional) manufactured by Mitsubishi Chemical

Maleimide group-containing compound (B-2): "MIR-3000" (biphenyl aralkyl maleimide resin, polyfunctional) manufactured by Nippon Kayaku Co., Ltd.

Isocyanate group-containing compound (B-3): "TKA-100" (isocyanurate-type isocyanate compound, isocyanate equivalent: 180 g/eq, trifunctional) manufactured by Asahi Kasei Corporation

Metal chelate compound (B-4): "Orgatyx ZC-150" (organic zirconia compound, tetrafunctional) manufactured by Matsumoto Fine Chemicals

Carbodiimide group-containing compound (B-5): "Carbodilite V-05" (carbodiimide equivalent: 262 g/eq, polyfunctional) manufactured by Nisshinbo Chemical

Polyamino group-containing compound: "BAPP" (bifunctional) manufactured by Seika Corporation

《Raw material: Filler (C)》

Boron nitride: "SP-2" (average particle diameter D ₅₀ ; 4.0 µm) manufactured by Denka Corporation

Silica: "SC2050-MB" (average particle diameter D ₅₀ ; 0.5 µm) manufactured by Adomatex Corporation

Alumina: "HT grade" (average particle diameter D ₅₀ = 1.2 µm, average circularity = 0.90) manufactured by Tokuyama Corporation

PTFE: "KT-300" (average particle diameter D ₅₀ ; 10.0 µm) manufactured by Kitamura Corporation

Liquid crystal polymer: "E101-S" (average particle diameter D ₅₀ ; 17.5 µm) manufactured by Sumitomo Chemical

<<Measurement of storage modulus of cured product and loss tangent>>

<Production of cured product for measurement>

Heavy peeling film (polyethylene terephthalate (PET) film coated with a heavy release agent) having a thickness of 50 µm so that the coating solution obtained in each Example and each comparative example becomes 200 µm after drying using a doctor blade After uniform coating on the top and drying at 100 degreeC for 2 minutes, it cooled to room temperature, and the thermosetting adhesive sheet with a single-sided peeling film was formed.

Next, the thermosetting adhesive sheet side of the obtained thermosetting adhesive sheet with a single-sided release film is superimposed on a 50 µm thick light release film (polyethylene terephthalate (PET) film coated with a light release agent), and a heavy release film/thermosetting adhesive sheet / The thermosetting adhesive sheet with double-sided peeling film which consists of a light peeling film was obtained.

The obtained thermosetting adhesive sheet was thermosetted at 180 degreeC, 1 hour, 2 Mpa, and the hardened|cured material of the 200 micrometers thermosetting resin composition was obtained by peeling a heavy peeling film and a light peeling film.

<Measurement method of storage modulus and loss tangent>

About the test piece for measurement cut out to the size of 5 mm x 30 mm from the obtained hardened|cured material, using the dynamic viscoelasticity measuring apparatus "DVA200" (made by ITI Keisoku Seikyo Co., Ltd.), after cooling to 0 degreeC, the temperature increase rate 10 The temperature was raised from °C/min to 300 °C, and the viscoelasticity was measured at a vibration frequency of 10 Hz.

From the obtained viscoelastic curves, the storage modulus at 30°C, 150°C, and 280°C is calculated, and the loss tangent (tanδ) is calculated from the loss modulus at each temperature, plotted, and the point at which the tanδ curve is maximized is calculated did. Moreover, when two or more local maximums exist, let the value whose temperature is closest to room temperature (23 degreeC) most be the tan-delta peak of the hardened|cured material.

In Tables 2-4, the value of the storage elastic modulus like "1.0x10 ⁶ " was described as "1.0E+06", for example.

(resin flow)

[Production of Sample A for Evaluation]

<<Production of thermosetting adhesive sheet with double-sided release film>>

In the same manner as in the case of preparation of samples for measurement of storage elastic modulus and loss elastic modulus, using the coating liquid obtained in each Example and each comparative example, both sides of a thermosetting adhesive sheet having a thickness of 25 µm after drying were coated with a thickness of 50 µm, respectively. A thermosetting adhesive sheet with a double-sided release film was obtained which was covered with a medium release film and a light release film having a thickness of 50 µm.

The light release film was peeled off from the said thermosetting adhesive sheet with a double-sided release film, and the exposed thermosetting adhesive sheet surface was temporarily adhered to DuPont's Kapton 100H. Thereafter, a circular hole having a diameter of 7 mm was formed by a punching machine.

Next, the heavy release film is peeled off, and on the exposed thermosetting adhesive sheet surface, 12 µm copper foil is laminated on both sides of a 50 µm polyimide film. After carrying out, it thermosetted at 180 degreeC, 1 hour, and 2 Mpa by hot press, and the sample A for evaluation was produced.

[Assessment Methods]

In the sample A for evaluation prepared above, a hole with a diameter of 7 mm from the Kapton 100H side was observed at about 20 to 300 times with an optical microscope (VHX-7000 manufactured by Keyence), and the resin exuded from the end of the circle. was measured and evaluated on the basis of the following criteria.

(double-circle): The resin flow is 100 micrometers or less. This is a very good result.

(circle): The resin flow exceeds 100 micrometers - 150 micrometers or less. This is a good result.

(triangle|delta): The resin flow exceeds 150 micrometers - 200 micrometers or less. It is within the practical range.

x: The resin flow exceeds 200 micrometers. impractical.

(Laser processability (before desmear solution treatment))

[Production of sample B for evaluation]

In the same manner as in the case of preparation of samples for measurement of storage elastic modulus and loss elastic modulus, using the coating liquid obtained in each Example and each comparative example, both sides of a thermosetting adhesive sheet having a thickness of 25 µm after drying were coated with a thickness of 50 µm, respectively. A thermosetting adhesive sheet with a double-sided release film was obtained which was covered with a medium release film and a light release film having a thickness of 50 µm.

The light release film was peeled off from the thermosetting adhesive sheet with a double-sided release film, and the exposed thermosetting adhesive sheet surface was placed on one side of a double-sided copper clad laminate in which a 12 μm copper foil was laminated on both sides of a 50 μm polyimide film. Temporarily attached with a vacuum laminator.

Then, the heavy release film is 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 are laminated on the exposed thermosetting adhesive sheet surface is similarly temporarily adhered with a vacuum laminator. , heat-cured at 180° C., 1 hour, 2 MPa by heat press, copper foil (1) / polyimide film (2) / copper foil (1) / cured product of thermosetting adhesive sheet (3) / polyimide film (2) / The sample B for evaluation of the same laminated constitution as copper foil (1) was obtained.

[Assessment Methods]

For the above evaluation sample B, using a UV-YAG laser (Model5330, manufactured by ESI), laser is irradiated from the upper surface of FIG. Blind via processing was performed.

Then, the cross section of the blind via is observed with a laser microscope (VK-X100 manufactured by Keyence Corporation) at a magnification of 20 to 500 times, and side etching generated in the cured product of the thermosetting adhesive sheet (cutting in the horizontal direction beyond the designed opening diameter) ) was measured and evaluated on the basis of the following criteria.

(double-circle): 5 micrometers or less. This is a very good result.

(circle): Larger than 5 micrometers and 7 micrometers or less. This is a good result.

(triangle|delta): Larger than 7 micrometers and 10 micrometers or less. It is within the practical range.

x: It is larger than 10 micrometers. impractical.

(Laser processability (after desmear solution treatment))

A sample subjected to blind via processing with a diameter of 150 μm up to the boundary between the cured product of the thermosetting adhesive sheet and the double-sided copper clad laminate was placed in “Marcutizer 9221-S” manufactured by Nippon Macdamid Co., Ltd. at 60° C. for 7 minutes, and “Marcutai After sequential immersion at 75° C. for 7 minutes and “Marcutizer 9276” at 45° C. for 7 minutes, it was washed with water at 23° C. for 5 minutes and dried in an oven at 40° C. for 10 minutes.

Then, the cross-section of the blind via part was observed with a laser microscope (VK-X100 manufactured by Keyence Corporation) at a magnification of 20 to 500 times, peeling off the boundary between the copper foil and the cured product of the thermosetting adhesive sheet, and the diameter of the polyimide film and the thermosetting adhesive sheet. The condition of the cargo and the peeling of the boundary was evaluated.

(double-circle): 3 or less holes in which peeling generate|occur|produced among 30 holes. This is a very good result.

(circle): 4 or more - 6 or less holes in which peeling generate|occur|produced among 30 holes. This is a good result.

(triangle|delta): 7 or more - 10 or less holes in which peeling generate|occur|produced among 30 holes. It is within the practical range.

x: 11 or more holes in which peeling arose out of 30 holes. impractical.

(Heat resistance)

[Assessment Methods]

The sample B for evaluation was prepared, stored for 24 hours or more in the atmosphere of 23 degreeC relative humidity of 50%, and the solder float test which floated to 288 degreeC molten solder for 3 minutes after that was done. Thereafter, the cross section was observed with a laser microscope (VK-X100 manufactured by Keyence Corporation) at a magnification of 20 to 500 times, peeling off the boundary between the cured product of the copper foil and the thermosetting adhesive sheet, and the boundary between the cured product of the polyimide film and the thermosetting adhesive sheet. The state of peeling was evaluated. The sample for evaluation was made into 30 pieces.

(double-circle): The number of generation|occurrence|production of peeling is 10 % or less. This is a very good result.

(circle): The number of generation|occurrence|production of peeling exceeds 10 % - 20 % or less. This is a good result.

(triangle|delta): The number of generation|occurrence|production holes of peeling exceeds 20 % - 30 % or less. It is within the practical range.

x: The number of generation|occurrence|production holes of peeling exceeds 30 %. impractical.

(Cold heat cycle resistance)

The sample B for evaluation was prepared and the cooling/heating cycle characteristic was evaluated. Treatment conditions were 15 minutes at -30°C and 15 minutes at 150°C 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 sample for evaluation was made into 30 pieces.

(double-circle): generation|occurrence|production of peeling is less than 10 %. This is a very good result.

(circle): The generation|occurrence|production number of peeling is less than 10 to 20 %. This is a good result.

(triangle|delta): The number of generation|occurrence|production of peeling holes is 20 % - less than 30 %. It is within the practical range.

x: 30% or more of the number of generation|occurrence|production holes of peeling. impractical.

(Shock absorption test)

[Production of Sample C for Evaluation]

In the same manner as in the case of preparation of samples for measurement of storage elastic modulus and loss elastic modulus, using the coating liquid obtained in each Example and each comparative example, both sides of a thermosetting adhesive sheet having a thickness of 25 µm after drying were coated with a thickness of 50 µm, respectively. A thermosetting adhesive sheet with a double-sided release film was obtained which was covered with a medium release film and a light release film having a thickness of 50 µm.

The light release film was peeled off from the said thermosetting adhesive sheet with a double-sided peeling film, and the exposed thermosetting adhesive sheet surface was temporarily adhered to the 3 mm-thick float glass made from the test piece company with a vacuum laminator.

Then, the heavy release film is 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 are laminated on the exposed thermosetting adhesive sheet surface is similarly temporarily adhered with a vacuum laminator, The sample C for evaluation of the same laminated constitution as float glass/hardened|cured material/polyimide film/copper foil which was thermosetted at 180 degreeC, 1 hour, and 2 Mpa by hot press was obtained.

[Assessment Methods]

Next, a 300 g cone was free-falling downward from a height of 20 cm on the test surface (single-sided copper clad laminate side) of the test piece. The float glass side of the test piece was visually observed, it was confirmed whether there was a crack or the trace of a cone|cone, and the following criteria evaluated it. The test sample was made into 10 pieces.

(double-circle): None of cracks and traces are present. This is a very good result.

○: 1 to 2 cracks and traces in total. This is a good result.

△: a total of 3 to 4 cracks and traces. It is within the practical range.

×: A total of 5 or more cracks and traces. impractical.

[Table 2]

[Table 3]

[Table 4]

ADVANTAGE OF THE INVENTION According to this invention, the hardened|cured material excellent in laser processability, heat resistance, cold-heat cycle resistance, and shock absorption can be provided, and the thermosetting resin composition with a small resin flow can be provided. These are suitable for manufacture of various printed wiring boards, electronic devices, etc. for which high workability and reliability are required.

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 product of a reaction product of a group of monomers comprising dimer diamine (a-1) and tetracarboxylic anhydride (a-2);
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) At least one curing agent (B) selected from;
Filler (C)
As a thermosetting resin composition comprising:
A thermosetting resin composition, characterized in that a cured product obtained by heating the thermosetting resin composition at 180° C. for 60 minutes satisfies (A) to (C).
(A) The storage modulus at 30°C is 1.0×10 ⁶ to 1.0×10 ¹¹ Pa.
(B) The storage modulus at 150°C is 1.0×10 ⁴ to 1.0×10 ⁹ Pa.
(C) The storage modulus at 280°C is 1.0×10 ³ to 1.0×10 ⁹ Pa. The method of claim 1,
A thermosetting resin composition, characterized in that the cured product has a loss tangent (tanδ) peak value of 0.3 or more at 0 to 280°C. According to claim 1,
The curing agent (B) is a thermosetting resin composition, characterized in that it contains three or more reactive functional groups capable of reacting with the polyimide resin (A) in one molecule. According to claim 1,
A thermosetting resin composition comprising 0.1 to 20 parts by mass of the curing agent (B) with respect to 100 parts by mass of the polyimide resin (A). According to claim 1,
The thermosetting resin composition characterized by containing 5-60 mass parts of said fillers (C) with respect to 100 mass parts of said polyimide resins (A). According to claim 1,
The filler (C) is at least one selected from the group consisting of a fluorine filler, boron nitride, a liquid crystal polymer and silica. According to claim 1,
It is used as a member for interlayer adhesion of a printed wiring board, The thermosetting resin composition characterized by the above-mentioned. The thermosetting adhesive sheet formed from the thermosetting resin composition in any one of Claims 1-7. A thermosetting cover sheet with a peeling film provided with the thermosetting adhesive sheet of Claim 8, and a peeling film. Copper clad laminate in which copper foil and an insulating film are laminated|stacked through the adhesive layer which is hardened|cured material of the thermosetting resin composition in any one of Claims 1-7. The printed wiring board formed using the thermosetting adhesive sheet of Claim 8. An electronic device provided with the printed wiring board of Claim 11. A polyimide resin (A), which is a product of a reaction product of a group of monomers comprising dimer diamine (a-1) and tetracarboxylic anhydride (a-2);
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) At least one curing agent (B) selected from;
Filler (C)
As a cured product of a thermosetting resin composition comprising:
A cured product that satisfies (A) to (C).
(A) The storage modulus at 30°C is 1.0×10 ⁶ to 1.0×10 ¹¹ Pa.
(B) The storage modulus at 150°C is 1.0×10 ⁴ to 1.0×10 ⁹ Pa.
(C) The storage modulus at 280°C is 1.0×10 ³ to 1.0×10 ⁹ Pa.

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