JP2023156362A - Resin materials, laminated films and multilayer printed wiring boards - Google Patents

Abstract

To provide a resin material which 1) enhances embedding properties to an uneven surface, 2) suppresses excess squeeze out from a periphery of a substrate of a resin material during lamination, 3) keeps curing temperature low, 4) reduces dielectric loss tangent of a cured article, 5) enhances adhesiveness with a metal, and 6) can enhance bending stability of the cured article.SOLUTION: The resin material contains a polyimide compound, and at least one of aliphatic skeleton-containing compound of a maleimide compound having an aliphatic skeleton and a benzoxazine compound having the aliphatic skeleton.SELECTED DRAWING: Figure 1

Description

The present invention relates to a resin material containing a polyimide compound. The present invention also relates to a multilayer printed wiring board using the above resin material.

Conventionally, various resin materials have been used to obtain electronic components such as semiconductor devices, laminates, and printed wiring boards. For example, in a multilayer printed wiring board, a resin material is used to form an insulating layer for insulating between internal layers, and to form an insulating layer located on a surface layer. Wiring, which is generally metal, is laminated on the surface of the insulating layer. Moreover, in order to form the above-mentioned insulating layer, a resin film obtained by forming the above-mentioned resin material into a film may be used. The resin material and the resin film are used as insulating materials for multilayer printed wiring boards including build-up films.

Patent Document 1 below discloses a resin composition containing a compound having a maleimide group, a divalent group having at least two imide bonds, and a saturated or unsaturated divalent hydrocarbon group. . Patent Document 1 describes that a cured product of this resin composition can be used as an insulating layer of a multilayer printed wiring board or the like.

Patent Document 2 below describes (A) polyfunctional epoxy resin (excluding phenoxy resin), (B) phenolic curing agent and/or active ester curing agent, (C) thermoplastic resin, (D) A resin composition containing an inorganic filler and (E) a quaternary phosphonium curing accelerator is disclosed. (C) Thermoplastic resin is a thermoplastic resin selected from phenoxy resin, polyvinyl acetal resin, polyimide, polyamideimide resin, polyethersulfone resin, and polysulfone resin. (E) The quaternary phosphonium curing accelerator is one or more quaternary phosphonium thiocyanates selected from tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. It is a phosphonium curing accelerator.

WO2016/114286A1 Japanese Patent Application Publication No. 2015-145498

When an insulating layer is formed using a conventional resin material as described in Patent Document 1, the embedding ability of the resin material into the irregularities of the substrate etc. may not be sufficiently high, or the resin material may be excessively removed from the periphery of the substrate during lamination. The film may protrude, making it difficult to control the film thickness. Furthermore, when an insulating layer is formed using a conventional resin material as described in Patent Document 2, the dielectric loss tangent of the insulating layer may not be sufficiently low, or the adhesion between the insulating layer and the copper substrate may be insufficient. may not be high enough.

On the other hand, in conventional resin materials containing only a maleimide compound having an aromatic skeleton, it is difficult to lower the curing temperature (eg, 200° C. or lower) because the maleimide compound has a high Tg. Furthermore, when the curing temperature is lowered, sufficient molecular movement is difficult to occur, which may result in poor curing. In addition, when the curing temperature is lowered, during the production of multilayer printed wiring boards, the resin material laminated in the early stages is heated more times and for a longer time than the resin materials laminated in the later stages. Therefore, the electrical properties and physical properties of the insulating layer may change.

Furthermore, with conventional resin materials, the bending stability of the cured product may not be sufficiently high.

In this way, 1) the ability to embed into uneven surfaces is improved, 2) excessive protrusion of the resin material from the substrate periphery during lamination is suppressed, 3) the curing temperature is kept low, and 4) the dielectric loss tangent of the cured product is reduced. , 5) It is extremely difficult to improve the adhesion to metals, and 6) to improve the bending stability of the cured product. That is, the current situation is that it is extremely difficult to obtain a resin material that exhibits all of the effects 1) to 6) above.

The objects of the present invention are 1) to improve the embeddability into uneven surfaces, 2) to suppress excessive extrusion of the resin material from the periphery of the substrate during lamination, 3) to keep the curing temperature low, and 4) to reduce the dielectric loss tangent of the cured product. 5) improve adhesion to metal; and 6) provide a resin material that can increase the bending stability of a cured product. Another object of the present invention is to provide a laminated film and a multilayer printed wiring board using the above resin material.

According to a broad aspect of the present invention, there is provided a resin material comprising a polyimide compound and an aliphatic skeleton-containing compound of at least one of a maleimide compound having an aliphatic skeleton and a benzoxazine compound having an aliphatic skeleton. .

In a particular aspect of the present invention, in the aliphatic skeleton-containing compound, the aliphatic skeleton is bonded to a nitrogen atom forming a maleimide skeleton or a benzoxazine skeleton.

In a particular aspect of the present invention, the polyimide compound has a weight average molecular weight of 15,000 or more, and the aliphatic skeleton-containing compound has a weight average molecular weight of less than 15,000.

In a particular aspect of the resin material according to the present invention, the aliphatic skeleton-containing compound has a skeleton derived from a reaction product of a polyamine compound having an aliphatic skeleton and a carboxylic dianhydride.

In a particular aspect of the resin material according to the present invention, the aliphatic skeleton-containing compound has a skeleton derived from a reaction product of a diamine compound having an aliphatic skeleton and a carboxylic dianhydride.

In a particular aspect of the resin material according to the present invention, the diamine compound having an aliphatic skeleton is a diamine compound having a skeleton derived from a dimer diamine.

In a particular aspect of the resin material according to the present invention, the resin material includes a thermosetting compound and an inorganic filler.

In a particular aspect of the resin material according to the present invention, the thermosetting compound is an epoxy compound.

In a particular aspect of the resin material according to the present invention, the content of the inorganic filler is 50% by weight or more based on 100% by weight of the components excluding the solvent in the resin material.

In a particular aspect of the resin material according to the present invention, the content of the polyimide compound is 3% by weight or more and 80% by weight or less out of the total 100% by weight of the polyimide compound and the aliphatic skeleton-containing compound.

In a particular aspect of the resin material according to the present invention, the polyimide compound is a polyimide compound having a skeleton derived from dimer diamine.

In a particular aspect of the resin material according to the present invention, the total content of the polyimide compound and the aliphatic skeleton-containing compound is 10% by weight or more in 100% by weight of the organic components excluding the solvent in the resin material. % by weight or less.

In a particular aspect of the resin material according to the present invention, the resin material includes a curing accelerator, and the curing accelerator includes at least one of a radical curing accelerator and an anionic curing accelerator.

In a certain aspect of the resin material according to the present invention, the curing accelerator contains a radical curing accelerator and dimethylaminopyridine, or a radical curing accelerator and an imidazole compound, or a radical curing accelerator and an imidazole compound. Contains a hardening accelerator and a phosphorus compound.

In a particular aspect of the resin material according to the present invention, the resin material includes a curing agent and a curing accelerator, and the curing accelerator includes an imidazole compound.

In a particular aspect of the resin material according to the present invention, the resin material is a resin film.

The resin material according to the present invention is suitably used for forming an insulating layer in a multilayer printed wiring board.

According to a broad aspect of the present invention, there is provided a laminated film comprising a base material and a resin film laminated on the surface of the base material, the resin film being the resin material described above.

According to a broad aspect of the present invention, the invention includes a circuit board, a plurality of insulating layers disposed on a surface of the circuit board, and a metal layer disposed between the plurality of insulating layers. A multilayer printed wiring board is provided, in which at least one layer is a cured product of the resin material described above.

The resin material according to the present invention includes a polyimide compound and at least one aliphatic skeleton-containing compound selected from a maleimide compound having an aliphatic skeleton and a benzoxazine compound having an aliphatic skeleton. Since the resin material according to the present invention has the above-mentioned configuration, 1) it improves embeddability into uneven surfaces, 2) suppresses excessive protrusion of the resin material from the periphery of the substrate during lamination, and 3) lowers the curing temperature. 4) the dielectric loss tangent of the cured product can be lowered, 5) the adhesion to metals can be improved, and 6) the bending stability of the cured product can be improved. The resin material according to the present invention can exhibit all of the effects 1) to 6) above.

FIG. 1 is a cross-sectional view schematically showing a multilayer printed wiring board using a resin material according to an embodiment of the present invention.

The present invention will be explained in detail below.

The resin material according to the present invention includes a polyimide compound and at least one aliphatic skeleton-containing compound selected from a maleimide compound having an aliphatic skeleton and a benzoxazine compound having an aliphatic skeleton.

Since the resin material according to the present invention has the above-mentioned configuration, 1) it improves embeddability into uneven surfaces, 2) suppresses excessive protrusion of the resin material from the periphery of the substrate during lamination, and 3) lowers the curing temperature. 4) the dielectric loss tangent of the cured product can be lowered, 5) the adhesion to metals can be improved, and 6) the bending stability of the cured product can be improved. The resin material according to the present invention can exhibit all of the effects 1) to 6) above. In the resin material according to the present invention, as for 5) adhesion to metal, for example, the peel strength between the insulating layer and the metal layer (copper layer) can be increased.

Further, since the resin material according to the present invention has the above-mentioned configuration, thermal dimensional stability can be improved. Further, since the resin material according to the present invention has the above-mentioned configuration, handling properties can be improved.

The resin material according to the present invention may be a resin composition or a resin film. The resin composition has fluidity. The resin composition may be in the form of a paste. The pasty state includes a liquid state. The resin material according to the present invention is preferably a resin film because of its excellent handling properties. When the resin material according to the present invention is a resin composition, it is possible to improve handling properties during coating or film forming. When the resin material according to the present invention is a resin film, handling properties during lamination can be improved.

In particular, when both the polyimide compound and the aliphatic skeleton-containing compound have a structure represented by the following formula (X), the compatibility between the polyimide compound and the aliphatic skeleton-containing compound is improved. Therefore, the bending stability of the cured product can be further improved.

In the above formula (X), R1 represents a tetravalent organic group.

The resin material according to the present invention is preferably a thermosetting material. When the resin material is a resin film, the resin film is preferably a thermosetting resin film.

In the present invention, the combination of a polyimide compound and a specific aliphatic skeleton-containing compound is an important and technically significant configuration. When the resin material contains a polyimide compound and does not contain a specific aliphatic skeleton-containing compound, it is difficult to effectively exhibit all of the effects of the present invention described in 1) to 6) above. In particular, when the resin material contains a polyimide compound but does not contain a specific aliphatic skeleton-containing compound, it is possible to improve the embeddability on uneven surfaces, lower the dielectric loss tangent, lower the curing temperature, or cure the cured product. It is difficult to increase the bending stability of In particular, when the maleimide compound is an N-phenylmaleimide compound (for example, a maleimide compound having a structure in which all nitrogen atoms are bonded to aromatic rings), the N-phenylmaleimide compound Since Tg is high, it is difficult to lower the curing temperature and it is difficult to lower the dielectric loss tangent. On the other hand, even when the resin material does not contain a polyimide compound but contains a specific aliphatic skeleton-containing compound, it is difficult to effectively exhibit all of the effects of the present invention described in 1) to 6) above. In particular, if the resin material does not contain a polyimide compound but contains a specific aliphatic skeleton-containing compound, the resin material may protrude excessively from the periphery of the substrate during lamination, making it difficult to control the thickness of the insulating layer. , surrounding substrates, etc. may be contaminated. Further, when the resin material is a resin film, the amount of flow during lamination may become large. As a result, the thickness of the insulating layer may become uneven.

Hereinafter, details of each component used in the resin material according to the present invention, uses of the resin material according to the present invention, etc. will be explained.

[Polyimide compound]
The resin material according to the present invention includes a polyimide compound. The above polyimide compound is a compound different from a maleimide compound. The polyimide compound may or may not have a maleimide skeleton at the end. In addition, the said polyimide compound may have an acid anhydride structure or a citraconimide structure at the terminal. As the polyimide compound, conventionally known polyimide compounds can be used. Only one kind of the above-mentioned polyimide compound may be used, or two or more kinds thereof may be used in combination.

Polyimide compounds can be produced by reacting tetracarboxylic dianhydride with an isocyanate ester compound, by reacting tetracarboxylic dianhydride with a diamine compound, and by reacting tetracarboxylic dianhydride with a triamine compound. etc. can be obtained by

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetra Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether Tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2 , 3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl Sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3 ',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenyl phthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, and bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride.

Examples of the diamine compounds include 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(aminomethyl)norbornane, 3(4),8(9)-bis(aminomethyl) Tricyclo[5.2.1.02,6]decane, 1,1-bis(4-aminophenyl)cyclohexane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 2,7-diaminofluorene, 4, 4'-ethylenedianiline, isophoronediamine, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(2-ethyl-6-methyl aniline), 4,4'-methylenebis(2-methylcyclohexylamine), 1,4-diaminobutane, 1,10-diaminodecane, 1,12-diaminododecane, 1,7-diaminoheptane, 1,6-diamino Examples include hexane, 1,5-diaminopentane, 1,8-diaminooctane, 1,3-diaminopropane, 1,11-diaminoundecane, 2-methyl-1,5-diaminopentane, and dimer diamine.

An imide skeleton is formed by the reaction between the tetracarboxylic dianhydride and the diamine compound.

From the viewpoint of effectively exhibiting the effects of the present invention described in 1) to 6) above, the polyimide compound is preferably a polyimide compound having a skeleton derived from dimer diamine. The skeleton derived from the dimer diamine is present as a partial skeleton in the polyimide compound.

The polyimide compound having a skeleton derived from the dimer diamine is preferably obtained by reacting the tetracarboxylic dianhydride with the dimer diamine.

Examples of the dimer diamine include Versamine 551 (trade name, manufactured by BASF Japan, 3,4-bis(1-aminoheptyl)-6-hexyl-5-(1-octenyl)cyclohexene), Versamine 552 (trade name) , manufactured by Cognix Japan Co., Ltd., hydrogenated product of Versamine 551), PRIAMINE 1075, PRIAMINE 1074 (trade names, all manufactured by Croda Japan Co., Ltd.).

The content of the polyimide compound is preferably 3% by weight or more, more preferably 5% by weight or more, still more preferably 10% by weight or more, out of the total 100% by weight of the polyimide compound and the aliphatic skeleton-containing compound. is 80% by weight or less, more preferably 60% by weight or less, even more preferably 50% by weight or less. When the content of the polyimide compound is not less than the lower limit and not more than the upper limit, the viscosity of the resin material does not become too high, and the handleability and embeddability into uneven surfaces can be further improved. Further, when the content of the polyimide compound is at least the above lower limit and at most the above upper limit, it is possible to prevent the flow amount during lamination from becoming too large.

The content of the polyimide compound is preferably 3% by weight or more, more preferably 5% by weight or more, and even more preferably 7% by weight or more in 100% by weight of the components excluding the inorganic filler and solvent in the resin material. . The content of the polyimide compound is preferably 40% by weight or less, more preferably 30% by weight or less, still more preferably 25% by weight or less, especially in 100% by weight of the components excluding the inorganic filler and solvent in the resin material. Preferably it is 20% by weight or less. When the content of the polyimide compound is at least the above lower limit, the dielectric loss tangent of the cured product can be lowered, the flow amount can be favorably controlled, and the adhesion between the insulating layer and the metal layer can be further improved. When the content of the polyimide compound is at most the above upper limit, the embeddability into the uneven surface can be further improved. Handlability can be improved when the content of the polyimide compound is at least the above lower limit and at most the above upper limit.

From the viewpoint of further improving the embeddability into the uneven surface, the weight average molecular weight of the polyimide compound is preferably 15,000 or more, more preferably 20,000 or more, preferably less than 50,000, and more preferably less than 40,000.

The weight average molecular weight of the polyimide compound means, when the polyimide compound is not a polymer and when the structural formula of the polyimide compound can be specified, the molecular weight that can be calculated from the structural formula. Furthermore, when the polyimide compound is a polymer, the weight average molecular weight of the polyimide compound indicates the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

When the polyimide compound has a maleimide skeleton at the end, the weight molecular weight of the polyimide compound is preferably 15,000 or more, more preferably 20,000 or more.

[Aliphatic skeleton-containing compound]
The resin material according to the present invention contains an aliphatic skeleton-containing compound. The aliphatic skeleton-containing compound is at least one of a maleimide compound having an aliphatic skeleton and a benzoxazine compound having an aliphatic skeleton. The resin material according to the present invention may contain only a maleimide compound having an aliphatic skeleton, or may contain only a benzoxazine compound having an aliphatic skeleton, as the aliphatic skeleton-containing compound. It may contain both a maleimide compound having an aliphatic skeleton and a benzoxazine compound having an aliphatic skeleton.

<Maleimide compound having an aliphatic skeleton>
The resin material according to the present invention preferably contains a maleimide compound having an aliphatic skeleton (hereinafter sometimes referred to as maleimide compound X) as the aliphatic skeleton-containing compound. The maleimide compound X is a compound different from a polyimide compound. Maleimide compound X has a maleimide group. Maleimide compound X has a maleimide group at the end. Maleimide compound X has an aliphatic skeleton. Therefore, maleimide compound X has a maleimide group and an aliphatic skeleton. In the maleimide compound X, the aliphatic skeleton is preferably bonded to the nitrogen atom forming the maleimide skeleton. Note that the maleimide compound X may have an imide skeleton. As the maleimide compound X, conventionally known maleimide compounds can be used. Note that the maleimide compound X includes a citraconimide compound. The above-mentioned citraconimide compound is a compound in which a methyl group is bonded to one of the carbon atoms forming a double bond between carbon atoms in a maleimide group. The maleimide compound X may have a citraconimide structure at its terminal. Only one kind of the maleimide compound X may be used, or two or more kinds thereof may be used in combination.

The maleimide compound X preferably has a skeleton derived from a reaction product of a polyamine compound having an aliphatic skeleton and a carboxylic dianhydride. The above polyamine compound means a compound having two or more primary amino groups. The maleimide compound X may have a skeleton derived from a reaction product of a polyamine compound having an aliphatic skeleton and a carboxylic dianhydride, and the maleimide compound It may have a skeleton derived from a reaction product of a carboxylic dianhydride and an amine compound different from the above.

For example, the maleimide compound It can be obtained by obtaining a reactant having an amino group at the end and then reacting the reactant with maleic anhydride.

Specifically, the maleimide compound X preferably has a skeleton derived from a reaction product of a diamine compound having an aliphatic skeleton or a triamine compound having an aliphatic skeleton and a carboxylic dianhydride. The maleimide compound X may have a skeleton derived from a reaction product of a diamine compound having an aliphatic skeleton and a carboxylic dianhydride. The above-mentioned maleimide compound It may have a skeleton derived from it. The above-mentioned maleimide compound It may have a skeleton derived from a reaction product of an amine compound different from the compound and a carboxylic dianhydride. In this case, it is preferable that one of a diamine compound having an aliphatic skeleton and a triamine compound having an aliphatic skeleton be used to obtain the reactant. In order to obtain the reactant, it is more preferable that both a diamine compound having an aliphatic skeleton and a triamine compound having an aliphatic skeleton are used. In this case, the amount (wt%) of the triamine compound having an aliphatic skeleton is preferably 5% or less of the amount (wt%) of the diamine compound having an aliphatic skeleton.

For example, the maleimide compound After obtaining a reactant in which is an amino group, it can be obtained by reacting the reactant with maleic anhydride.

For example, the maleimide compound After obtaining a reactant in which is an amino group, it can be obtained by reacting the reactant with maleic anhydride.

In the case where the maleimide compound X is a reaction product of a diamine compound and a carboxylic dianhydride, the maleimide compound X preferably satisfies the following (1) or (2), ) is more preferable. (1) It has a diamine skeleton at both ends. (2) In the amino group of the diamine compound that is not directly bonded to the carboxylic dianhydride, the skeleton having the amino group is a maleimide skeleton.

Examples of the diamine compounds having an aliphatic skeleton include 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(aminomethyl)norbornane, 3(4),8(9)- Bis(aminomethyl)tricyclo[5.2.1.02,6]decane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, isophoronediamine, 4,4'-methylenebis(cyclohexylamine), 4,4 '-Methylenebis(2-methylcyclohexylamine), 1,4-diaminobutane, 1,10-diaminodecane, 1,12-diaminododecane, 1,7-diaminoheptane, 1,6-diaminohexane, 1,5- Examples include diaminopentane, 1,8-diaminooctane, 1,3-diaminopropane, 1,11-diaminoundecane, 2-methyl-1,5-diaminopentane, and diamine compounds having skeletons derived from dimer diamine. .

Examples of the diamine compounds having an aromatic skeleton include 1,1-bis(4-aminophenyl)cyclohexane, 2,7-diaminofluorene, 4,4'-ethylenedianiline, 4,4'-methylenebis(2,6 -diethylaniline), and 4,4'-methylenebis(2-ethyl-6-methylaniline).

Examples of the carboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride. Acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetra Carboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2, 3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfone Dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3' , 4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, and bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride.

From the viewpoint of lowering the dielectric loss tangent, the diamine compound having an aliphatic skeleton is preferably a diamine compound having a skeleton derived from dimer diamine.

The diamine compound having a skeleton derived from a dimer diamine is preferably a reaction product of a dimer diamine and a tetracarboxylic dianhydride. In addition, when the diamine compound having a skeleton derived from dimer diamine is a reaction product of dimer diamine and tetracarboxylic dianhydride, the reactant (the diamine compound) has a skeleton other than the skeleton derived from dimer diamine. may have a diamine skeleton.

Examples of the dimer diamine include Versamine 551 (trade name, manufactured by BASF Japan, 3,4-bis(1-aminoheptyl)-6-hexyl-5-(1-octenyl)cyclohexene), Versamine 552 (trade name) , manufactured by Cognix Japan Co., Ltd., hydrogenated product of Versamine 551), PRIAMINE 1075, PRIAMINE 1074 (trade names, all manufactured by Croda Japan Co., Ltd.).

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetra Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether Tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2 , 3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl Sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3 ',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenyl phthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, and bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride.

From the viewpoint of more effectively exhibiting the effects of the present invention described in 1) to 6) above, the maleimide compound X is preferably an N-alkyl bismaleimide compound having a skeleton derived from dimer diamine.

A commercially available N-alkyl bismaleimide compound having a skeleton derived from the dimer diamine is available from Designer Molecules Inc. Examples include "BMI-1500," "BMI-1700," and "BMI-3000" manufactured by the company.

Weight ratio of the content of the maleimide compound X to the total content of the thermosetting compound described below and the component X described below (content of the maleimide compound ) is preferably 0.05 or more, more preferably 0.1 or more, preferably 0.9 or less, and more preferably 0.75 or less. When the above weight ratio (content of maleimide compound X/total content of thermosetting compound and component It is possible to further improve the adhesion with.

The content of the maleimide compound X is preferably 3% by weight or more, more preferably 5% by weight or more, even more preferably 10% by weight or more, based on 100% by weight of the components excluding the inorganic filler and solvent in the resin material. It is preferably 90% by weight or less, more preferably 80% by weight or less. When the content of the maleimide compound X is at least the above lower limit, the dielectric loss tangent can be further lowered, and the adhesion between the insulating layer and the metal layer can be further improved. When the content of the maleimide compound X is at most the above upper limit, embeddability during lamination can be improved.

From the viewpoint of further increasing the adhesion between the insulating layer and the metal layer, the weight average molecular weight of the maleimide compound Preferably it is less than 10,000.

The weight average molecular weight of the maleimide compound X means the molecular weight that can be calculated from the structural formula when the maleimide compound X is not a polymer and when the structural formula of the maleimide compound X can be specified. Furthermore, when the maleimide compound X is a polymer, the weight average molecular weight of the maleimide compound X indicates the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

<Benzoxazine compound having an aliphatic skeleton>
The resin material according to the present invention preferably contains a benzoxazine compound having an aliphatic skeleton (hereinafter sometimes referred to as benzoxazine compound X) as the aliphatic skeleton-containing compound. Benzoxazine compound X has a benzoxazine skeleton. Therefore, benzoxazine compound X has a benzoxazine skeleton and an aliphatic skeleton. In the benzoxazine compound X, it is preferable that the aliphatic skeleton is bonded to the nitrogen atom forming the benzoxazine skeleton. Note that the benzoxazine compound X may have an imide skeleton. As the benzoxazine compound X, conventionally known benzoxazine compounds can be used. The benzoxazine compound X may be used alone or in combination of two or more.

Examples of the benzoxazine compound X include N-alkylbenzoxazine compounds.

The benzoxazine compound X is preferably a compound in which the maleimide skeleton of the maleimide compound X described above is substituted with a benzoxazine skeleton.

The above-mentioned benzoxazine compound It can be obtained by reacting. Further, the N-alkylbenzoxazine compound having a skeleton derived from a dimer diamine can be obtained by, for example, reacting a tetracarboxylic dianhydride with a dimer diamine to obtain a reactant having a skeleton at both ends derived from a dimer diamine. After that, it can be obtained by reacting the reactant with phenol and paraformaldehyde.

The benzoxazine compound X preferably has an imide skeleton in its main chain. In this case, since the compatibility with the polyimide compound can be improved, the bending stability of the cured product can be further improved.

The benzoxazine compound X preferably has a skeleton derived from a reaction product of a polyamine compound having an aliphatic skeleton and a carboxylic dianhydride. The above polyamine compound means a compound having two or more primary amino groups. The above-mentioned benzoxazine compound It may have a skeleton derived from a reaction product of an amine compound different from the compound and a carboxylic dianhydride.

The above benzoxazine compound After obtaining a reactant having amino groups at both ends, it can be obtained by reacting the reactant with phenol and paraformaldehyde.

Specifically, the benzoxazine compound X preferably has a skeleton derived from a reaction product of a diamine compound having an aliphatic skeleton or a triamine compound having an aliphatic skeleton and a carboxylic dianhydride. The benzoxazine compound X may have a skeleton derived from a reaction product of a diamine compound having an aliphatic skeleton and a carboxylic dianhydride. The above-mentioned benzoxazine compound It may have a skeleton derived from. The benzoxazine compound X may have a skeleton derived from a reaction product of a triamine compound having an aliphatic skeleton and a carboxylic dianhydride; It may have a skeleton derived from a reaction product of an amine compound different from the triamine compound and a carboxylic dianhydride. In this case, it is preferable that one of a diamine compound having an aliphatic skeleton and a triamine compound having an aliphatic skeleton be used to obtain the reactant. In order to obtain the reactant, it is more preferable that both a diamine compound having an aliphatic skeleton and a triamine compound having an aliphatic skeleton are used. In this case, the amount (wt%) of the triamine compound having an aliphatic skeleton is preferably 5% or less of the amount (wt%) of the diamine compound having an aliphatic skeleton.

The benzoxazine compound After obtaining a reactant having an amino group at the end, it can be obtained by reacting the reactant with phenol and paraformaldehyde.

The benzoxazine compound After obtaining a reactant having an amino group at the end, it can be obtained by reacting the reactant with phenol and paraformaldehyde.

Examples of the diamine compound having an aliphatic skeleton include the diamine compounds described above.

Examples of the diamine compound having an aromatic skeleton include the diamine compounds described above.

Examples of the carboxylic dianhydride include the carboxylic dianhydrides mentioned above.

From the viewpoint of lowering the dielectric loss tangent, the diamine compound having an aliphatic skeleton is preferably a diamine compound having a skeleton derived from dimer diamine.

The diamine compound having a skeleton derived from a dimer diamine is preferably a reaction product of a dimer diamine and a tetracarboxylic dianhydride. In addition, when the diamine compound having a skeleton derived from dimer diamine is a reaction product of dimer diamine and tetracarboxylic dianhydride, the reactant (the diamine compound) has a skeleton other than the skeleton derived from dimer diamine. may have a diamine skeleton.

Examples of the above-mentioned dimer diamine include the above-mentioned dimer diamine.

Examples of the above-mentioned tetracarboxylic dianhydride include the above-mentioned tetracarboxylic dianhydride.

From the viewpoint of more effectively exhibiting the effects of the present invention described in 1) to 6) above, the benzoxazine compound preferable.

Weight ratio of the content of the benzoxazine compound X to the total content of the thermosetting compound described below and the component X described below (content of the benzoxazine compound content) is preferably 0.05 or more, more preferably 0.1 or more, preferably 0.9 or less, and more preferably 0.75 or less. When the above weight ratio (content of benzoxazine compound X/total content of thermosetting compound and component The adhesion between the layers can be further improved.

The content of the benzoxazine compound X is preferably 3% by weight or more, more preferably 5% by weight or more, even more preferably 10% by weight or more in 100% by weight of the components excluding the inorganic filler and solvent in the resin material. , preferably 90% by weight or less, more preferably 80% by weight or less. When the content of the benzoxazine compound X is at least the above lower limit, the dielectric loss tangent can be further lowered, and the adhesion between the insulating layer and the metal layer can be further improved. When the content of the benzoxazine compound X is at most the above upper limit, embeddability during lamination can be improved.

From the perspective of further increasing the adhesion between the insulating layer and the metal layer, the weight average molecular weight of the benzoxazine compound X is preferably 500 or more, more preferably 1000 or more, preferably less than 15000, more preferably less than 12000 More preferably, it is less than 10,000.

The weight average molecular weight of the benzoxazine compound X means the molecular weight that can be calculated from the structural formula when the benzoxazine compound X is not a polymer and when the structural formula of the benzoxazine compound X can be specified. Further, the weight average molecular weight of the benzoxazine compound X, when the benzoxazine compound X is a polymer, indicates the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The total content of the polyimide compound and the aliphatic skeleton-containing compound in 100% by weight of the organic components excluding the solvent in the resin material is preferably 10% by weight or more, more preferably 15% by weight or more, and even more preferably is 20% by weight or more. The total content of the polyimide compound and the aliphatic skeleton-containing compound in 100% by weight of the organic components excluding the solvent in the resin material is preferably 98% by weight or less, more preferably 80% by weight or less. When the above-mentioned total content is at least the above-mentioned lower limit and below the above-mentioned upper limit, the above-mentioned effects 1)-6) of the present invention can be exhibited even more effectively.

[Thermosetting compound]
The resin material preferably contains a thermosetting compound. The thermosetting compound is a thermosetting compound different from the polyimide compound, the maleimide compound X, and the benzoxazine compound X. Examples of the thermosetting compounds include styrene compounds, vinyl compounds, phenoxy compounds, oxetane compounds, epoxy compounds, episulfide compounds, (meth)acrylic compounds, phenol compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, and silicone compounds. can be mentioned. The above thermosetting compounds may be used alone or in combination of two or more.

From the viewpoint of more effectively exhibiting the effects of the present invention described in 1) to 6) above, and from the viewpoint of increasing thermal dimensional stability, the thermosetting compound is preferably an epoxy compound.

The above-mentioned epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenol novolak type epoxy compounds, biphenyl type epoxy compounds, biphenyl novolac type epoxy compounds, biphenol type epoxy compounds, and naphthalene type epoxy compounds. , fluorene type epoxy compound, phenol aralkyl type epoxy compound, naphthol aralkyl type epoxy compound, dicyclopentadiene type epoxy compound, anthracene type epoxy compound, epoxy compound having an adamantane skeleton, epoxy compound having a tricyclodecane skeleton, naphthylene ether type Examples include epoxy compounds and epoxy compounds having a triazine nucleus in their skeleton.

The epoxy compound preferably includes an epoxy compound having an aromatic skeleton, preferably an epoxy compound having a naphthalene skeleton or a phenyl skeleton, and more preferably an epoxy compound having an aromatic skeleton. More preferably, it is an epoxy compound having In this case, the dielectric loss tangent can be further lowered, and the heat resistance, flame retardance, and thermal dimensional stability can be improved.

From the viewpoint of further lowering the dielectric loss tangent and improving the coefficient of linear thermal expansion (CTE) of the cured product, the epoxy compound includes an epoxy compound that is liquid at 25°C and an epoxy compound that is solid at 25°C. It is preferable.

The viscosity at 25° C. of the epoxy compound which is liquid at 25° C. is preferably 1000 mPa·s or less, more preferably 500 mPa·s or less.

When measuring the viscosity of the epoxy compound, for example, a dynamic viscoelasticity measuring device ("VAR-100" manufactured by Rheologica Instruments) or the like is used.

It is more preferable that the molecular weight of the epoxy compound is 1000 or less. In this case, even if the components excluding the solvent in the resin material are 100% by weight and the content of the inorganic filler is 50% by weight or more, a resin material with high fluidity can be obtained when forming the insulating layer. Therefore, when an uncured resin material or a B-staged resin material is laminated on a circuit board, the inorganic filler can be uniformly present.

When the epoxy compound is not a polymer and when the structural formula of the epoxy compound can be specified, the molecular weight of the epoxy compound means the molecular weight that can be calculated from the structural formula. Moreover, when the above-mentioned epoxy compound is a polymer, it means the weight average molecular weight.

From the viewpoint of further increasing the adhesive strength between the cured product and the metal layer, the content of the epoxy compound is preferably 5% by weight or more, more preferably 25% by weight of the 100% by weight of the organic components excluding the solvent in the resin material. It is at least 50% by weight, preferably at most 50% by weight, and more preferably at most 40% by weight.

Weight ratio of the content of the epoxy compound to the total content of the aliphatic skeleton-containing compound and component X described below (content of the epoxy compound/total of the aliphatic skeleton-containing compound and component content) is preferably 0.1 or more, more preferably 0.2 or more. Weight ratio of the content of the epoxy compound to the total content of the aliphatic skeleton-containing compound and component X described below (content of the epoxy compound/total of the aliphatic skeleton-containing compound and component content) is preferably 0.9 or less, more preferably 0.8 or less. When the weight ratio (content of the epoxy compound/total content of the aliphatic skeleton-containing compound and component The coefficient of expansion can be reduced, the adhesion between the insulating layer and the metal layer can be further improved, and the handling properties can be improved.

[Inorganic filler]
The resin material preferably contains an inorganic filler. By using the above inorganic filler, the dielectric loss tangent of the cured product can be further lowered. Further, by using the above-mentioned inorganic filler, the dimensional change due to heat of the cured product is further reduced. Only one kind of the above-mentioned inorganic filler may be used, or two or more kinds thereof may be used in combination.

Examples of the inorganic filler include silica, talc, clay, mica, hydrotalcite, alumina, magnesium oxide, aluminum hydroxide, aluminum nitride, and boron nitride.

The surface roughness of the cured product is reduced, the adhesive strength between the cured product and the metal layer is further increased, finer wiring is formed on the surface of the cured product, and the cured product has better insulation reliability. From the viewpoint of imparting this, the inorganic filler is preferably silica or alumina, more preferably silica, and even more preferably fused silica. By using silica, the coefficient of thermal expansion of the cured product becomes even lower, and the dielectric loss tangent of the cured product becomes even lower. Moreover, by using silica, the surface roughness of the surface of the cured product is effectively reduced, and the adhesive strength between the cured product and the metal layer is effectively increased. The shape of the silica is preferably spherical.

The inorganic filler is spherical silica from the viewpoint of curing the resin, effectively increasing the glass transition temperature of the cured product, and effectively reducing the linear thermal expansion coefficient of the cured product regardless of the curing environment. It is preferable.

The average particle size of the inorganic filler is preferably 50 nm or more, more preferably 100 nm or more, even more preferably 500 nm or more, preferably 5 μm or less, more preferably 3 μm or less, and still more preferably 1 μm or less. When the average particle diameter of the inorganic filler is not less than the above lower limit and not more than the above upper limit, it is possible to further improve the embeddability into the uneven surface and further improve the adhesion between the insulating layer and the metal layer.

As the average particle size of the inorganic filler, a value of the median diameter (d50) that is 50% is adopted. The above average particle size can be measured using a laser diffraction scattering type particle size distribution measuring device.

The inorganic filler is preferably spherical, more preferably spherical silica. In this case, the surface roughness of the surface of the cured product is effectively reduced, and furthermore, the adhesive strength between the cured product and the metal layer is effectively increased. When the inorganic filler is spherical, the aspect ratio of the inorganic filler is preferably 2 or less, more preferably 1.5 or less.

The inorganic filler is preferably surface-treated, more preferably surface-treated with a coupling agent, and even more preferably surface-treated with a silane coupling agent. By surface-treating the inorganic filler, the surface roughness of the roughened cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased. Furthermore, since the inorganic filler is surface-treated, finer wiring can be formed on the surface of the cured product, and even better inter-wiring insulation reliability and interlayer insulation reliability can be achieved on the cured product. can be granted.

Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent. Examples of the silane coupling agent include methacrylsilane, acrylicsilane, aminosilane, imidazolesilane, vinylsilane, and epoxysilane.

The content of the inorganic filler is preferably 50% by weight or more, more preferably 60% by weight or more, even more preferably 65% by weight or more, and particularly preferably 68% by weight in 100% by weight of the components excluding the solvent in the resin material. % or more. The content of the inorganic filler is preferably 90% by weight or less, more preferably 85% by weight or less, even more preferably 80% by weight or less, particularly preferably 75% by weight in 100% by weight of the components excluding the solvent in the resin material. % or less. When the content of the inorganic filler is equal to or higher than the lower limit, the dielectric loss tangent becomes effectively low, and the coefficient of linear expansion can be reduced. When the content of the inorganic filler is equal to or less than the upper limit, adhesiveness, embeddability to an uneven surface, and etching performance can be improved. When the content of the inorganic filler is not less than the above lower limit and not more than the above upper limit, the surface roughness of the surface of the cured product can be further reduced, and finer wiring can be formed on the surface of the cured product. I can do it. Furthermore, with this amount of inorganic filler, it is possible to lower the coefficient of thermal expansion of the cured product and at the same time improve smear removability.

[Curing agent]
The resin material preferably contains a curing agent. The above curing agent is not particularly limited. As the curing agent, conventionally known curing agents can be used. Only one kind of the above curing agent may be used, or two or more kinds thereof may be used in combination.

The above curing agents include cyanate ester compounds (cyanate ester curing agents), amine compounds (amine curing agents), thiol compounds (thiol curing agents), imidazole compounds, phosphine compounds, dicyandiamide, phenol compounds (phenol curing agents), acid anhydrides. Examples include active ester compounds, carbodiimide compounds (carbodiimide curing agents), benzoxazine compounds without an aliphatic skeleton (benzoxazine curing agents), and maleimide compounds without an aliphatic skeleton. The curing agent preferably has a functional group capable of reacting with the epoxy group of the epoxy compound.

From the viewpoint of lowering the dielectric loss tangent and increasing thermal dimensional stability, the above-mentioned curing agent is a phenolic compound, a cyanate ester compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a benzoxazine compound having no aliphatic skeleton. It is preferable to include at least one component of the following. That is, the resin material includes a curing agent containing at least one component of a phenol compound, a cyanate ester compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a benzoxazine compound having no aliphatic skeleton. It is preferable. The benzoxazine compound having no aliphatic skeleton is preferably an N-phenylbenzoxazine compound in which an aromatic skeleton is bonded to the nitrogen atom forming the benzoxazine skeleton.

In this specification, "phenol compounds, cyanate ester compounds, acid anhydrides, active ester compounds, carbodiimide compounds, and N-phenylbenzoxazine compounds in which an aromatic skeleton is bonded to the nitrogen atom forming the benzoxazine skeleton. "at least one component of the following" may be referred to as "component X".

The resin material preferably contains a curing agent containing component X. The above component X may be used alone or in combination of two or more.

Examples of the above-mentioned phenol compounds include novolac-type phenol, biphenol-type phenol, naphthalene-type phenol, dicyclopentadiene-type phenol, aralkyl-type phenol, and dicyclopentadiene-type phenol.

Commercially available products of the above-mentioned phenol compounds include novolac type phenol ("TD-2091" manufactured by DIC Corporation), biphenyl novolac type phenol ("MEH-7851" manufactured by Meiwa Kasei Co., Ltd.), and aralkyl type phenol compound ("MEH" manufactured by Meiwa Kasei Co., Ltd.). -7800''), and phenols having an aminotriazine skeleton (“LA1356” and “LA3018-50P” manufactured by DIC Corporation).

Examples of the cyanate ester compound include novolak-type cyanate ester resins, bisphenol-type cyanate ester resins, and prepolymers obtained by partially trimerizing these. Examples of the novolac cyanate ester resins include phenol novolac cyanate ester resins and alkylphenol cyanate ester resins. Examples of the bisphenol type cyanate ester resin include bisphenol A type cyanate ester resin, bisphenol E type cyanate ester resin, and tetramethylbisphenol F type cyanate ester resin.

Commercial products of the above cyanate ester compounds include phenol novolak cyanate ester resins (PT-30 and PT-60 manufactured by Lonza Japan), and prepolymers in which bisphenol cyanate ester resins are trimerized (Lonza Japan). ``BA-230S'', ``BA-3000S'', ``BTP-1000S'', and ``BTP-6020S'' manufactured by the company.

Examples of the acid anhydride include tetrahydrophthalic anhydride, alkylstyrene-maleic anhydride copolymer, and the like.

Examples of commercially available acid anhydrides include "Rikacid TDA-100" manufactured by Shin Nippon Rika Co., Ltd.

The above-mentioned active ester compound refers to a compound that contains at least one ester bond in its structure and has aromatic rings bonded to both sides of the ester bond. The active ester compound is obtained, for example, by a condensation reaction between a carboxylic acid compound or a thiocarboxylic acid compound and a hydroxy compound or a thiol compound. Examples of active ester compounds include compounds represented by the following formula (1).

In the above formula (1), X1 represents a group containing an aliphatic chain, a group containing an aliphatic ring, or a group containing an aromatic ring, and X2 represents a group containing an aromatic ring. Preferred examples of the group containing the aromatic ring include a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, and the like. Examples of the above-mentioned substituents include hydrocarbon groups. The number of carbon atoms in the hydrocarbon group is preferably 12 or less, more preferably 6 or less, still more preferably 4 or less.

Examples of the combination of X1 and A combination with a naphthalene ring which may have a group is exemplified. Further, examples of the combination of X1 and X2 include a combination of a naphthalene ring that may have a substituent and a naphthalene ring that may have a substituent.

The above active ester compound is not particularly limited. From the viewpoint of further increasing thermal dimensional stability, the active ester compound is preferably an active ester compound having two or more aromatic skeletons. From the viewpoint of lowering the dielectric loss tangent of the cured product and increasing the thermal dimensional stability of the cured product, it is more preferable that the active ester has a naphthalene ring in its main chain skeleton.

Examples of commercially available active ester compounds include "HPC-8000-65T", "EXB9416-70BK", "EXB8100-65T", and "HPC-8150-60T" manufactured by DIC.

The carbodiimide compound has a structural unit represented by the following formula (2). In the following formula (2), the right end and left end are bonding sites with other groups. Only one kind of the above-mentioned carbodiimide compound may be used, or two or more kinds thereof may be used in combination.

In the above formula (2), represents a group, and p represents an integer of 1 to 5. When a plurality of Xs exist, the plurality of Xs may be the same or different.

In one preferred form, at least one X is an alkylene group, a group having a substituent bonded to an alkylene group, a cycloalkylene group, or a group having a substituent bonded to a cycloalkylene group.

Commercially available carbodiimide compounds include "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", "Carbodilite V-09", and "Carbodilite V-04K" manufactured by Nisshinbo Chemical Co., Ltd. 10M-SP" and "Carbodilite 10M-SP (revised)," as well as Rhein Chemie's "Stavaxol P," "Stavaxol P400," and "Hikasil 510."

Examples of the benzoxazine compounds without an aliphatic skeleton include Pd-type benzoxazine and Fa-type benzoxazine.

Examples of commercially available benzoxazine compounds having no aliphatic skeleton include "P-d type" manufactured by Shikoku Kasei Kogyo Co., Ltd.

The content of the component X is preferably 70 parts by weight or more, more preferably 85 parts by weight or more, and preferably It is 150 parts by weight or less, more preferably 120 parts by weight or less. When the content of the component X is not less than the lower limit and not more than the upper limit, the curability is even better, the thermal dimensional stability is further improved, and the volatilization of remaining unreacted components can be further suppressed.

The content of the component X based on 100 parts by weight of the thermosetting compound is preferably 70 parts by weight or more, more preferably 85 parts by weight or more, preferably 150 parts by weight or less, and more preferably 120 parts by weight or less. When the content of the component X is not less than the lower limit and not more than the upper limit, the curability is even better, the thermal dimensional stability is further improved, and the volatilization of remaining unreacted components can be further suppressed.

The total content of the polyimide compound, the aliphatic skeleton-containing compound, the thermosetting compound, and the component X in 100% by weight of the components excluding the inorganic filler and solvent in the resin material is preferably is 50% by weight or more, more preferably 60% by weight or more, preferably 90% by weight or less, more preferably 85% by weight or less. When the total content of the thermosetting compound and the component X is not less than the above lower limit and not more than the above upper limit, the curability is even better and the thermal dimensional stability can be further improved.

Out of 100% by weight of the components excluding the inorganic filler and solvent in the resin material, the total content of the thermosetting compound and the component It is preferably 90% by weight or less, more preferably 85% by weight or less. When the total content of the thermosetting compound and the component X is not less than the above lower limit and not more than the above upper limit, the curability is even better and the thermal dimensional stability can be further improved.

[Curing accelerator]
The resin material preferably contains a curing accelerator. By using the above-mentioned curing accelerator, the curing speed becomes even faster. By rapidly curing the resin material, the crosslinked structure in the cured product becomes uniform, the number of unreacted functional groups decreases, and the crosslinking density increases as a result. The curing accelerator is not particularly limited, and conventionally known curing accelerators can be used. As for the said hardening accelerator, only 1 type may be used, and 2 or more types may be used together.

Examples of the curing accelerator include anionic curing accelerators such as imidazole compounds, cationic curing accelerators such as amine compounds, and curing accelerators other than anionic and cationic curing accelerators such as phosphorus compounds and organometallic compounds. , and radical curing accelerators such as peroxides.

The above imidazole compounds include 2-undecylimidazole, 2-heptadecyl imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl- 2-Methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-un Decylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2' -Methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino- 6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s -triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-dihydroxymethylimidazole etc.

Examples of the above amine compounds include diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, and 4,4-dimethylaminopyridine.

Examples of the phosphorus compounds include triphenylphosphine compounds.

Examples of the organometallic compound include zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, cobalt (II) bisacetylacetonate, and cobalt (III) trisacetylacetonate.

Examples of the peroxides include dicumyl peroxide and perhexyl 25B.

From the viewpoint of keeping the curing temperature even lower, the curing accelerator preferably contains the anionic curing accelerator, and more preferably contains the imidazole compound.

From the viewpoint of keeping the curing temperature even lower, the content of the anionic curing accelerator in 100% by weight of the curing accelerator is preferably 50% by weight or more, more preferably 70% by weight or more, and even more preferably 80% by weight. % by weight or more, most preferably 100% by weight (total amount).

The curing accelerator preferably includes at least one of a radical curing accelerator and an anionic curing accelerator. The anionic curing accelerator is preferably an imidazole compound. The curing accelerator preferably contains a radical curing accelerator and dimethylaminopyridine, a radical curing accelerator and an imidazole compound, or a radical curing accelerator and a phosphorus compound. . If the curing of the resin material does not proceed sufficiently, the dielectric loss tangent and linear expansion coefficient may increase. The curing accelerator may include the radical curing accelerator and the imidazole compound. The radical curing accelerator is preferably one whose reaction temperature in the presence of the radical curing accelerator is higher than the temporary curing temperature before etching and lower than the main curing temperature after etching. When Perhexyl 25B is used as the radical curing accelerator, the above effects are exhibited even more effectively.

When the curing accelerator contains a radical curing accelerator and an imidazole compound, or contains a radical curing accelerator and a phosphorus compound, the curing of the resin material can proceed favorably, An even better cured product can be obtained.

The curing accelerator may include a radical curing accelerator and at least one curing accelerator selected from dimethylaminopyridine, an imidazole compound, and a phosphorus compound.

The content of the curing accelerator is not particularly limited. The content of the curing accelerator is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and preferably 5% by weight or less in 100% by weight of the components excluding inorganic fillers and solvents in the resin material. , more preferably 3% by weight or less. When the content of the curing accelerator is not less than the above lower limit and not more than the above upper limit, the resin material is efficiently cured. If the content of the curing accelerator is in a more preferable range, the storage stability of the resin material will be even higher, and an even better cured product will be obtained.

[Thermoplastic resin]
Preferably, the resin material includes a thermoplastic resin. Examples of the thermoplastic resin include polyvinyl acetal resin and phenoxy resin. Only one kind of the above-mentioned thermoplastic resin may be used, or two or more kinds thereof may be used in combination.

From the viewpoint of effectively lowering the dielectric loss tangent and effectively increasing the adhesion of metal wiring regardless of the curing environment, the thermoplastic resin is preferably a phenoxy resin. By using the phenoxy resin, deterioration in the ability of the resin film to fill holes or irregularities in the circuit board and non-uniformity of the inorganic filler can be suppressed. Further, by using a phenoxy resin, the melt viscosity can be adjusted, so the dispersibility of the inorganic filler is improved, and the resin composition or B-staged product is less likely to wet and spread to unintended areas during the curing process.

The phenoxy resin contained in the resin material is not particularly limited. As the phenoxy resin, conventionally known phenoxy resins can be used. Only one type of the above phenoxy resin may be used, or two or more types may be used in combination.

Examples of the phenoxy resin include phenoxy resins having skeletons such as a bisphenol A type skeleton, a bisphenol F type skeleton, a bisphenol S type skeleton, a biphenyl skeleton, a novolak skeleton, a naphthalene skeleton, and an imide skeleton.

Commercially available products of the above phenoxy resin include, for example, "YP50", "YP55" and "YP70" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., and "1256B40", "4250", "4256H40" and "4256H40" manufactured by Mitsubishi Chemical Corporation. 4275'', ``YX6954BH30'', and ``YX8100BH30''.

From the viewpoint of obtaining a resin material with even better storage stability, the weight average molecular weight of the thermoplastic resin and the phenoxy resin is preferably 5,000 or more, more preferably 10,000 or more, preferably 100,000 or less, and more preferably 50,000 or less. It is.

The weight average molecular weight of the thermoplastic resin and the phenoxy resin indicates the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The contents of the thermoplastic resin and the phenoxy resin are not particularly limited. The content of the thermoplastic resin (if the thermoplastic resin is a phenoxy resin, the content of the phenoxy resin) is preferably 1% by weight of the components excluding the inorganic filler and the solvent in the resin material. % or more, more preferably 2% by weight or more, preferably 30% by weight or less, more preferably 20% by weight or less. When the content of the thermoplastic resin is not less than the lower limit and not more than the upper limit, the resin material has good embedding properties in holes or irregularities of the circuit board. When the content of the thermoplastic resin is equal to or higher than the lower limit, the resin film can be formed even more easily, and an even better insulating layer can be obtained. When the content of the thermoplastic resin is below the above upper limit, the coefficient of thermal expansion of the cured product becomes even lower. When the content of the thermoplastic resin is below the upper limit, the surface roughness of the surface of the cured product becomes even smaller, and the adhesive strength between the cured product and the metal layer becomes even higher.

[solvent]
The resin material does not contain or contains a solvent. By using the above solvent, the viscosity of the resin material can be controlled within a suitable range, and the coatability of the resin material can be improved. Moreover, the above-mentioned solvent may be used to obtain a slurry containing the above-mentioned inorganic filler. Only one type of the above solvent may be used, or two or more types may be used in combination.

The above solvents include acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane, toluene, xylene, methyl ethyl ketone, Examples include N,N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidone, n-hexane, cyclohexane, cyclohexanone, and naphtha as a mixture.

It is preferable that most of the solvent be removed when the resin composition is formed into a film. Therefore, the boiling point of the above solvent is preferably 200°C or lower, more preferably 180°C or lower. The content of the solvent in the resin composition is not particularly limited. The content of the solvent can be changed as appropriate in consideration of the coatability of the resin composition.

[Other ingredients]
In order to improve impact resistance, heat resistance, resin compatibility, workability, etc., the above resin materials contain leveling agents, flame retardants, coupling agents, coloring agents, antioxidants, ultraviolet deterioration inhibitors, and erasers. Foaming agents, thickeners, thixotropic agents, thermosetting resins other than epoxy compounds, etc. may be added.

Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent. Examples of the silane coupling agent include vinylsilane, aminosilane, imidazolesilane, and epoxysilane.

Examples of the other thermosetting resins include polyphenylene ether resin, divinylbenzyl ether resin, polyarylate resin, diallyl phthalate resin, polyimide resin, benzoxazine resin, benzoxazole resin, bismaleimide resin, and acrylate resin.

(Resin film and laminated film)
A resin film (B-staged product/B-stage film) is obtained by molding the above-described resin composition into a film. It is preferable that the resin material is a resin film. Preferably, the resin film is a B-stage film.

The resin material is preferably a thermosetting material.

Examples of methods for obtaining a resin film by molding a resin composition into a film include the following methods. An extrusion molding method in which a resin composition is melt-kneaded using an extruder, extruded, and then molded into a film using a T-die, a circular die, or the like. A casting method in which a resin composition containing a solvent is cast and formed into a film. Other conventionally known film forming methods. An extrusion molding method or a casting molding method is preferable because it is possible to reduce the thickness. The film includes sheets.

A resin film, which is a B-stage film, can be obtained by forming a resin composition into a film and heating and drying it at, for example, 50 to 150° C. for 1 to 10 minutes to the extent that thermal curing does not proceed too much.

A film-like resin composition that can be obtained by the drying process as described above is referred to as a B-stage film. The B-stage film is in a semi-cured state. A semi-cured product is not completely cured and may be further cured.

The resin film does not need to be prepreg. If the resin film is not a prepreg, migration will not occur along the glass cloth or the like. Moreover, when laminating or pre-curing the resin film, unevenness caused by the glass cloth will not occur on the surface.

The above resin film can be suitably used in the form of a laminated film.

The laminated film includes a base material and a resin film laminated on the surface of the base material. The resin film is the resin material described above. The laminated film may include a protective film laminated on the surface of the resin film opposite to the base material.

Examples of the base material include polyester resin films such as polyethylene terephthalate film and polybutylene terephthalate film, olefin resin films such as polyethylene film and polypropylene film, polyimide resin films, and metal foils such as copper foil. The surface of the base material may be subjected to a mold release treatment, if necessary.

From the viewpoint of controlling the degree of curing of the resin film more uniformly, the thickness of the resin film is preferably 5 μm or more, and preferably 200 μm or less. When the resin film is used as an insulating layer of a circuit, the thickness of the insulating layer formed of the resin film is preferably greater than or equal to the thickness of the conductor layer (metal layer) forming the circuit. The thickness of the insulating layer is preferably 5 μm or more, and preferably 200 μm or less.

(Semiconductor devices, printed wiring boards, copper-clad laminates, and multilayer printed wiring boards)
The resin material described above is suitably used to form a mold resin in which a semiconductor chip is embedded in a semiconductor device.

The above resin material is suitably used to form an insulating layer in a printed wiring board.

The printed wiring board can be obtained, for example, by heating and press-molding the resin material.

Metal foil can be laminated on one or both sides of the resin film. The method of laminating the resin film and metal foil is not particularly limited, and any known method can be used. For example, the resin film can be laminated onto the metal foil using a device such as a parallel plate press or a roll laminator while heating or pressing without heating.

The above resin material is suitably used to obtain a copper-clad laminate. An example of the above-mentioned copper-clad laminate includes a copper-clad laminate including a copper foil and a resin film laminated on one surface of the copper foil.

The thickness of the copper foil of the copper-clad laminate is not particularly limited. The thickness of the copper foil is preferably within the range of 1 to 50 μm. Moreover, in order to increase the adhesive strength between the cured product of the resin material and the copper foil, it is preferable that the copper foil has fine irregularities on its surface. The method of forming the unevenness is not particularly limited. Examples of the method for forming the above-mentioned unevenness include a method of forming the unevenness by a treatment using a known chemical solution.

The above resin material is suitably used to obtain a multilayer substrate.

An example of the multilayer board is a multilayer board that includes a circuit board and an insulating layer laminated on the circuit board. The insulating layer of this multilayer board is formed from the above resin material. Further, the insulating layer of the multilayer substrate may be formed of the resin film of the laminated film using a laminated film. The insulating layer is preferably laminated on the surface of the circuit board on which the circuit is provided. Preferably, a portion of the insulating layer is embedded between the circuits.

In the multilayer board, it is preferable that the surface of the insulating layer opposite to the surface on which the circuit board is laminated is subjected to a roughening treatment.

A conventionally known roughening treatment method can be used as the roughening treatment method, and is not particularly limited. The surface of the insulating layer may be subjected to swelling treatment before roughening treatment.

Preferably, the multilayer substrate further includes a copper plating layer laminated on the roughened surface of the insulating layer.

Another example of the multilayer board is a circuit board, an insulating layer laminated on the surface of the circuit board, and a surface of the insulating layer on the opposite side of the surface on which the circuit board is laminated. For example, a multilayer board may include a copper foil. It is preferable that the insulating layer is formed by using a copper-clad laminate including a copper foil and a resin film laminated on one surface of the copper foil, and by curing the resin film. Furthermore, it is preferable that the copper foil is etched and is a copper circuit.

Another example of the multilayer board is a multilayer board that includes a circuit board and a plurality of insulating layers stacked on the surface of the circuit board. At least one layer of the plurality of insulating layers arranged on the circuit board is formed using the resin material. Preferably, the multilayer board further includes a circuit laminated on at least one surface of the insulating layer formed using the resin film.

Among multilayer substrates, multilayer printed wiring boards are required to have a low dielectric loss tangent and high insulation reliability due to the insulating layers. In the resin material according to the present invention, insulation reliability can be effectively improved by lowering the dielectric loss tangent and improving the adhesion between the insulating layer and the metal layer and the etching performance. Therefore, the resin material according to the present invention is suitably used for forming an insulating layer in a multilayer printed wiring board.

The multilayer printed wiring board includes, for example, a circuit board, a plurality of insulating layers disposed on the surface of the circuit board, and a metal layer disposed between the plurality of insulating layers. At least one of the insulating layers is a cured product of the resin material.

FIG. 1 is a cross-sectional view schematically showing a multilayer printed wiring board using a resin material according to an embodiment of the present invention.

In the multilayer printed wiring board 11 shown in FIG. 1, a plurality of insulating layers 13 to 16 are laminated on the upper surface 12a of the circuit board 12. The insulating layers 13 to 16 are cured material layers. A metal layer 17 is formed in a part of the upper surface 12 a of the circuit board 12 . Among the plurality of insulating layers 13 to 16, a metal layer 17 is formed in a part of the upper surface of the insulating layers 13 to 15 other than the insulating layer 16 located on the outer surface opposite to the circuit board 12 side. has been done. Metal layer 17 is a circuit. A metal layer 17 is arranged between the circuit board 12 and the insulating layer 13, and between each of the laminated insulating layers 13 to 16. The lower metal layer 17 and the upper metal layer 17 are connected to each other by at least one of a via hole connection and a through hole connection (not shown).

In the multilayer printed wiring board 11, the insulating layers 13 to 16 are formed of a cured product of the resin material described above. In this embodiment, the surfaces of the insulating layers 13 to 16 are roughened, so that fine holes (not shown) are formed in the surfaces of the insulating layers 13 to 16. Further, a metal layer 17 extends inside the fine hole. Furthermore, in the multilayer printed wiring board 11, the widthwise dimension (L) of the metal layer 17 and the widthwise dimension (S) of the portion where the metal layer 17 is not formed can be made smaller. Furthermore, in the multilayer printed wiring board 11, good insulation reliability is provided between the upper metal layer and the lower metal layer that are not connected by via hole connection or through hole connection (not shown).

(Roughening treatment and swelling treatment)
The resin material is preferably used to obtain a cured product that is subjected to a roughening treatment or a desmear treatment. The above-mentioned cured products also include pre-cured products that can be further cured.

In order to form fine irregularities on the surface of the cured product obtained by pre-curing the resin material, the cured product is preferably subjected to a roughening treatment. It is preferable that the cured product is subjected to a swelling treatment before the roughening treatment. It is preferable that the cured product is subjected to a swelling treatment after preliminary curing and before roughening treatment, and further hardened after roughening treatment. However, the cured product does not necessarily need to be subjected to swelling treatment.

As a method for the above-mentioned swelling treatment, for example, a method of treating the cured product with an aqueous solution or an organic solvent dispersion solution of a compound whose main component is ethylene glycol or the like is used. The swelling liquid used in the swelling treatment generally contains an alkali as a pH adjuster. Preferably, the swelling liquid contains sodium hydroxide. Specifically, for example, the swelling treatment is performed by treating the cured product using a 40% by weight aqueous ethylene glycol solution or the like at a treatment temperature of 30 to 85° C. for 1 to 30 minutes. The temperature of the swelling treatment is preferably within the range of 50 to 85°C. If the temperature of the swelling treatment is too low, the swelling treatment takes a long time and the adhesive strength between the cured product and the metal layer tends to decrease.

For the roughening treatment, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound, or a persulfuric compound is used. These chemical oxidants are used as an aqueous solution or an organic solvent dispersion solution after water or an organic solvent is added. The roughening liquid used in the roughening treatment generally contains an alkali as a pH adjuster. It is preferable that the roughening liquid contains sodium hydroxide.

Examples of the manganese compound include potassium permanganate and sodium permanganate. Examples of the chromium compound include potassium dichromate and potassium chromate anhydride. Examples of the persulfate compound include sodium persulfate, potassium persulfate, ammonium persulfate, and the like.

The arithmetic mean roughness Ra of the surface of the cured product is preferably 10 nm or more, preferably less than 300 nm, more preferably less than 200 nm, even more preferably less than 150 nm. In this case, the adhesive strength between the cured product and the metal layer is increased, and further finer wiring is formed on the surface of the insulating layer. Furthermore, conductor loss can be suppressed, and signal loss can be kept low. The arithmetic mean roughness Ra is measured in accordance with JIS B0601:1994.

(desmear processing)
Through holes may be formed in the cured product obtained by pre-curing the resin material. In the above-mentioned multilayer substrate, a via, a through hole, or the like is formed as a through hole. For example, vias can be formed by irradiation with a laser such as a CO ₂ laser. The diameter of the via is not particularly limited, but is approximately 60 to 80 μm. Due to the formation of the above-described through holes, a smear, which is a resin residue derived from a resin component contained in the cured product, is often formed at the bottom of the via.

In order to remove the smear, the surface of the cured product is preferably subjected to a desmear treatment. Desmear treatment may also serve as roughening treatment.

Similar to the roughening treatment, the desmear treatment uses, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound, or a persulfate compound. These chemical oxidants are used as an aqueous solution or an organic solvent dispersion solution after water or an organic solvent is added. Desmear processing liquid used for desmear processing generally contains an alkali. It is preferable that the desmear treatment liquid contains sodium hydroxide.

By using the above resin material, the surface roughness of the desmeared cured product becomes sufficiently small.

Hereinafter, the present invention will be specifically explained by giving Examples and Comparative Examples. The invention is not limited to the following examples.

(Maleimide compound with aliphatic skeleton)
N-alkyl bismaleimide compound 1 (“BMI-1700” manufactured by Designer Molecules Inc., has a skeleton derived from dimer diamine, which is a reaction product of tetracarboxylic dianhydride and dimer diamine)
N-alkyl bismaleimide compound 2 (“BMI-3000” manufactured by Designer Molecules Inc., has a skeleton derived from dimer diamine, which is a reaction product of tetracarboxylic dianhydride and dimer diamine)
N-alkyl bismaleimide compound 3 (“BMI-1500” manufactured by Designer Molecules Inc.)
N-alkyl bismaleimide compound 4 (“BMI-3000J” manufactured by Designer Molecules Inc.)
N-alkyl bismaleimide compound 5 (synthesized according to Synthesis Example 1 below, has a skeleton derived from dimer diamine)
N-alkyl bismaleimide compound 6 (synthesized according to Synthesis Example 2 below, has a skeleton derived from dimer diamine)

(Synthesis example 1)
Put 135.0 g of tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan LLC) and 400 g of cyclohexanone into a reaction container equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube, The solution in the reaction vessel was heated to 60°C. Next, 17.5 g of 1,3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added dropwise into the reaction vessel and reacted to obtain a reaction product having acid anhydride at both ends. Next, 148 g of dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan) was slowly added into the reaction container, and then 60.0 g of methylcyclohexane was added into the reaction container. A Dean-Stark trap and a condenser were attached to the flask, and the mixture was heated to reflux for 2 hours to obtain an imide compound having amine structures at both ends. 28 g of maleic anhydride were then added and the resulting mixture was refluxed for a further 12 hours. After the reaction was completed, isopropanol was added to cause reprecipitation, and the precipitate was collected and dried to obtain an N-alkyl bismaleimide compound having a skeleton derived from dimer diamine. The recovery rate of the N-alkyl bismaleimide compound having a skeleton derived from dimer diamine was 83%. (Weight average molecular weight 10000)

(Synthesis example 2)
After stirring, 55 g of pyromellitic dianhydride (manufactured by Tokyo Kasei Co., Ltd., molecular weight 254.15) and 300 g of cyclohexanone were placed in a reaction container equipped with a water separator, a thermometer, and a nitrogen gas inlet tube. solution was heated to 60°C. Next, a solution in which 26.7 g of bis(aminomethyl)norbornane (manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight 154.26) was dissolved in cyclohexanone was added dropwise into the reaction vessel, and the reaction was carried out to form an acid anhydride at both ends. A reaction product was obtained. Thereafter, isopropanol was added, and an imide compound having acid anhydride at both ends was recovered. Next, the precipitate was dissolved in cyclohexane again, and 46.0 g of dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan) was slowly added into the reaction container, and then 45.0 g of methylcyclohexane was added into the reaction container. A Dean-Stark trap and a condenser were attached to the flask, and the mixture was heated to reflux for 2 hours to obtain an imide compound having amine structures at both ends. The recovery rate of maleimide compound was 70%. (Weight average molecular weight 8700)

(Benzoxazine compound having an aliphatic skeleton)
N-alkylbisbenzoxazine compound (synthesized according to Synthesis Example 3 below)

(Synthesis example 3)
65 g of pyromellitic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 218.12) and 500 mL of cyclohexanone were placed in a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube, and then, After dissolving 164 g of dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan) in cyclohexanone, it was added dropwise. Thereafter, a Dean-Stark trap and a condenser were attached to the flask, and the mixture was heated to reflux for 2 hours to obtain an imide compound having amine structures at both ends. The resulting imide compound, 38 g of phenol (manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight 94.11), and 12 g of paraformaldehyde (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were mixed, and the resulting mixture was further refluxed for 12 hours to form benzoxazine. . Thereafter, by reprecipitation with isopropanol, an N-alkylbenzoxazine compound (weight average molecular weight 7,700) was obtained.

(Maleimide compound without an aliphatic skeleton (maleimide compound with an aromatic skeleton)) N-phenylmaleimide compound 1 (“BMI-2300” manufactured by Daiwa Kasei Kogyo Co., Ltd.)
N-phenylmaleimide compound 2 (“BMI-4000” manufactured by Daiwa Kasei Kogyo Co., Ltd.)

(Polyimide compound)
A solution containing a polyimide compound (non-volatile content: 26.8% by weight), which is a reaction product of tetracarboxylic dianhydride and dimer diamine, was synthesized according to Synthesis Example 4 below.

(Synthesis example 4)
300.0 g of tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan LLC) and 665.5 g of cyclohexanone were placed in a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube. The solution in the reaction vessel was heated to 60°C. Next, 89.0 g of dimer diamine ("PRIAMINE1075" manufactured by Croda Japan) and 54.7 g of 1,3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Company) were added dropwise into the reaction vessel. Next, 121.0 g of methylcyclohexane and 423.5 g of ethylene glycol dimethyl ether were added into the reaction vessel, and an imidization reaction was carried out at 140° C. for 10 hours. In this way, a polyimide compound-containing solution (nonvolatile content: 26.8% by weight) was obtained. The molecular weight (weight average molecular weight) of the obtained polyimide compound was 20,000. Note that the molar ratio of acid component/amine component was 1.04.

The molecular weight of the polyimide compound synthesized in Synthesis Example 4 was determined as follows.

GPC (gel permeation chromatography) measurement:
Measurement was performed using a high performance liquid chromatography system manufactured by Shimadzu Corporation, using tetrahydrofuran (THF) as a developing medium, at a column temperature of 40° C., and at a flow rate of 1.0 ml/min. "SPD-10A" was used as a detector, and two columns "KF-804L" manufactured by Shodex (exclusion limit molecular weight 400,000) were connected in series. As the standard polystyrene, "TSK Standard Polystyrene" manufactured by Tosoh Corporation was used, and weight average molecular weight Mw = 354,000, 189,000, 98,900, 37,200, 17,100, 9,830, 5,870, 2, Calibration curves were created using 500, 1,050, and 500 substances, and molecular weight calculations were performed.

(Thermoplastic resin)
Phenoxy resin (“YX6954BH30” manufactured by Mitsubishi Chemical Corporation)

(thermosetting compound)
Biphenyl type epoxy compound (“NC-3000” manufactured by Nippon Kayaku Co., Ltd.)
Naphthalene type epoxy compound (“HP-4032D” manufactured by DIC Corporation)
Resorcinol diglycidyl ether (“EX-201” manufactured by Nagase ChemteX)
Dicyclopentadiene type epoxy compound (“EP4088S” manufactured by Adeka)
Naphthol aralkyl type epoxy compound (“ESN-475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)

(Inorganic filler)
Silica-containing slurry (75% by weight silica: “SC4050-HOA” manufactured by Admatex, average particle size 1.0 μm, aminosilane treatment, 25% by weight cyclohexanone)

(hardening agent)
Ingredient X:
Cyanate ester compound-containing liquid (“BA-3000S” manufactured by Lonza Japan, solid content 75% by weight)
Liquid containing active ester compound 1 (“EXB-9416-70BK” manufactured by DIC, solid content 70% by weight)
Active ester compound 2-containing liquid (“HPC-8000L” manufactured by DIC, solid content 65% by weight)
Liquid containing active ester compound 3 (“HPC-8150” manufactured by DIC, solid content 62% by weight) Liquid containing phenol compound (“LA-1356” manufactured by DIC, solid content 60% by weight)
Carbodiimide compound-containing liquid (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., solid content 50% by weight)

(hardening accelerator)
Dimethylaminopyridine (“DMAP” manufactured by Wako Pure Chemical Industries, Ltd.)
2-phenyl-4-methylimidazole (“2P4MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.)
2-ethyl-4-methylimidazole (“2E4MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.)
Dicumyl peroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)

(Examples 1 to 16 and Comparative Examples 1 to 6)
The components shown in Tables 1 and 2 below were blended in the amounts shown in Tables 1 and 2 below, and stirred at room temperature until a uniform solution was obtained to obtain a resin material.

Preparation of resin film:
Using an applicator, the resulting resin material was applied onto the release-treated surface of a release-treated PET film ("XG284" manufactured by Toray Industries, Inc., thickness 25 μm), and then placed in a gear oven at 100°C for 2 minutes. It was dried for 30 seconds to evaporate the solvent. In this way, a laminated film (a laminated film of a PET film and a resin film) in which a resin film (B stage film) having a thickness of 40 μm was laminated on a PET film was obtained.

(evaluation)
(1) Handling property The obtained resin film (B stage film) was bent 10 times at 180 degrees. Out of 10 tests, the number of times the resin film cracked or cracked was observed.

[Handling performance criteria]
○: Out of 10 times, cracks or cracks occur less than 3 times. △: Out of 10 times, cracks or breaks occur more than 3 times but less than 6 times. ×: Out of 10 times, cracks or breaks occur less than 3 times. Occurs 6 or more times

(2) Ability to embed into uneven surfaces and prevent extrusion (prevent excessive wetting and spreading)
By etching only the copper foil of a 100 mm square copper-clad laminate (a laminate of a 400 μm thick glass epoxy board and a 25 μm thick copper foil), a recess (opening) with a diameter of 100 μm and a depth of 25 μm was created. Holes were drilled in a straight line in a 30 mm square area at the center of the substrate so that the distance between the centers of adjacent holes was 900 μm. In this way, an evaluation board having a total of 900 depressions was prepared.

The resin film side of the obtained laminated film was stacked on the evaluation substrate, and using a "batch type vacuum laminator MVLP-500-IIA" manufactured by Meiki Seisakusho Co., Ltd., the lamination pressure was 0.4 MPa for 20 seconds, and the press pressure was 0.8 MPa. Heat and pressure was applied for 20 seconds at a lamination and press temperature of 90°C. After cooling to room temperature, the PET film was peeled off. In this way, an evaluation sample was obtained in which a resin film was laminated on an evaluation substrate.

The voids in the depressions of the obtained evaluation sample were observed using an optical microscope. By evaluating the proportion of depressions in which voids were observed, the embeddability into the uneven surface was determined according to the following criteria.

[Criteria for determining embeddability on uneven surfaces]
○: Percentage of depressions where voids were observed 0%
△: Proportion of depressions in which voids were observed exceeds 0% and less than 5% ×: Proportion of depressions in which voids were observed is 5% or more

Using an optical microscope, it was observed whether or not the resin film protruded from a predetermined area on the substrate for the obtained evaluation sample, and the protrusion prevention property was determined based on the following criteria.

[Criteria for determining protrusion prevention properties]
○: The protrusion of the resin film from the periphery of the evaluation board after lamination is 2 mm or less. △: The protrusion of the resin film from the periphery of the evaluation board after lamination is more than 2 mm and 3 mm or less. ×: From the periphery of the evaluation board after lamination. The protrusion of the resin film exceeds 3 mm.

(3) Curing temperature The exothermic peak accompanying curing of the obtained resin film (B-stage film) was evaluated using a differential scanning calorimetry device ("Q2000" manufactured by TA Instruments). 8 mg of resin film was placed in a special aluminum pan, and a lid was placed using a special jig. This dedicated aluminum pan and an empty aluminum pan (reference) were placed in a heating unit and heated from -30°C to 250°C in a nitrogen atmosphere at a heating rate of 3°C/min. Heat flow was observed. The curing temperature was confirmed by the exothermic peak observed in non-reverse heat flow.

[Criteria for curing temperature]
○: All exothermic peaks are below 200°C ×: At least one exothermic peak is above 200°C

(4) Dielectric Dissipation Tangent The obtained resin film was cut into pieces with a width of 2 mm and a length of 80 mm, and five pieces were stacked on top of each other to obtain a laminate with a thickness of 200 μm. The obtained laminate was heated at 190° C. for 90 minutes to obtain a cured product. The obtained cured product was heated to room temperature (23°C) using the cavity resonance method using the "Cavity Resonance Perturbation Method Permittivity Measurement Device CP521" manufactured by Kanto Denshi Application Development Co., Ltd. and the "Network Analyzer N5224A PNA" manufactured by Keysight Technologies. The dielectric loss tangent was measured at a frequency of 1.0 GHz.

[Judgment criteria for dielectric loss tangent]
○: Dielectric loss tangent is 3.5×10 ⁻³ or less ×: Dielectric loss tangent exceeds 3.5×10 ⁻³

(5) Adhesion between insulating layer and metal layer (peel strength)
Lamination process:
A double-sided copper-clad laminate (copper foil thickness on each side of 18 μm, substrate thickness of 0.7 mm, substrate size of 100 mm×100 mm, “MCL-E679FG” manufactured by Hitachi Chemical) was prepared. Both sides of the copper foil side of this double-sided copper-clad laminate were immersed in "Cz8101" manufactured by MEC Corporation to roughen the surface of the copper foil. Both sides of the roughened copper clad laminate are coated with the resin film (B stage film) side of the laminate film on the copper clad laminate using Meiki Seisakusho's "Batch Vacuum Laminator MVLP-500-IIA". These were stacked and laminated to obtain a laminated structure. The lamination conditions were that the pressure was reduced to 13 hPa or less by reducing the pressure for 30 seconds, and then pressing was performed for 30 seconds at 100° C. and a pressure of 0.4 MPa.

Film peeling process:
In the obtained laminated structure, the PET films on both sides were peeled off.

Copper foil pasting process:
The shiny surface of a copper foil (35 μm thick, manufactured by Mitsui Kinzoku Co., Ltd.) was subjected to Cz treatment (“Cz8101” manufactured by MEC Corporation), and the surface of the copper foil was etched by about 1 μm. An etched copper foil was bonded to the laminated structure from which the PET film had been peeled off, to obtain a substrate with copper foil. The obtained substrate with copper foil was heat treated at 190° C. for 90 minutes in a gear oven to obtain an evaluation sample.

Measuring peel strength:
A rectangular incision with a width of 1 cm was made on the surface of the copper foil of the evaluation sample. Set the evaluation sample in a 90° peel tester (TE-3001 manufactured by Tester Sangyo Co., Ltd.), pick up the notched end of the copper foil with a grip, peel off 20 mm of the copper foil, and test the peel strength (peel strength). strength) was measured.

[Criteria for adhesion (peel strength) between insulating layer and metal layer]
○○: Peel strength is 0.6 kgf or more ○: Peel strength is 0.4 kgf or more and less than 0.6 kgf ×: Peel strength is less than 0.4 kgf

(6) Average coefficient of linear expansion (CTE)
The resulting resin film (B stage film) with a thickness of 40 μm was heated at 190° C. for 90 minutes, and the resulting cured product was cut into a size of 3 mm×25 mm. Using a thermomechanical analysis device ("EXSTAR TMA/SS6100" manufactured by SII Nanotechnology), the cured product was cut at 25 to 150 °C under the conditions of a tensile load of 33 mN and a temperature increase rate of 5 °C/min. The average coefficient of linear expansion (ppm/°C) was calculated.

[Judgment criteria for average linear expansion coefficient]
○: Average linear expansion coefficient is 25 ppm/℃ or less △: Average linear expansion coefficient exceeds 25 ppm/℃ and 30 ppm/℃ or less ×: Average linear expansion coefficient exceeds 30 ppm/℃

(7) Bending stability of cured product The obtained resin film (B stage film) with a thickness of 40 μm was heated at 190° C. for 90 minutes, and the obtained cured product was cut into a size of 30 mm×150 mm. Using a sheet U-shaped folding tester (manufactured by Yuasa Corporation), a downward bending test was conducted under the conditions of 200 times/minute of bending at 180° C. (bending gap of 5 mm) and film stroke of 70 mm. The measurement was repeated 5 times and the average value was calculated.

[Criteria for determining bending stability of cured product]
〇〇: No cracking after 2000 times of bending 〇: Cracking occurs when the number of bending is 100 or more and less than 2000 times ×: Cracking occurs when the number of bending is less than 100 times

The composition and results are shown in Tables 1 and 2 below. In addition, in Table 1, the content of each component is described in pure amount.

11...Multilayer printed wiring board 12...Circuit board 12a...Top surface 13-16...Insulating layer 17...Metal layer

(Examples 1 to 13, Reference Example 14, Examples 15 and 16, and Comparative Examples 1 to 6)
The components shown in Tables 1 and 2 below were blended in the amounts shown in Tables 1 and 2 below, and stirred at room temperature until a uniform solution was obtained to obtain a resin material.

Claims (19)

polyimide compound,
A resin material comprising at least one aliphatic skeleton-containing compound of a maleimide compound having an aliphatic skeleton and a benzoxazine compound having an aliphatic skeleton. The resin material according to claim 1, wherein in the aliphatic skeleton-containing compound, the aliphatic skeleton is bonded to a nitrogen atom forming a maleimide skeleton or a benzoxazine skeleton. The weight average molecular weight of the polyimide compound is 15,000 or more,
The resin material according to claim 1 or 2, wherein the aliphatic skeleton-containing compound has a weight average molecular weight of less than 15,000. The resin material according to any one of claims 1 to 3, wherein the aliphatic skeleton-containing compound has a skeleton derived from a reaction product of a polyamine compound having an aliphatic skeleton and a carboxylic dianhydride. The resin material according to any one of claims 1 to 4, wherein the aliphatic skeleton-containing compound has a skeleton derived from a reaction product of a diamine compound having an aliphatic skeleton and a carboxylic dianhydride. The resin material according to claim 5, wherein the diamine compound having an aliphatic skeleton is a diamine compound having a skeleton derived from dimer diamine. The resin material according to any one of claims 1 to 6, comprising a thermosetting compound and an inorganic filler. The resin material according to claim 7, wherein the thermosetting compound is an epoxy compound. The resin material according to claim 7 or 8, wherein the content of the inorganic filler is 50% by weight or more in 100% by weight of components excluding the solvent in the resin material. According to any one of claims 1 to 9, the content of the polyimide compound is 3% by weight or more and 80% by weight or less in a total of 100% by weight of the polyimide compound and the aliphatic skeleton-containing compound. resin material. The resin material according to any one of claims 1 to 10, wherein the polyimide compound has a skeleton derived from dimer diamine. Any one of claims 1 to 11, wherein the total content of the polyimide compound and the aliphatic skeleton-containing compound is 10% by weight or more and 98% by weight or less in 100% by weight of the organic component excluding the solvent in the resin material. The resin material according to item 1. Contains curing accelerator,
The resin material according to any one of claims 1 to 12, wherein the curing accelerator includes at least one of a radical curing accelerator and an anionic curing accelerator. A claim in which the curing accelerator contains a radical curing accelerator and dimethylaminopyridine, or a radical curing accelerator and an imidazole compound, or a radical curing accelerator and a phosphorus compound. 13. The resin material according to item 13. Contains a curing agent and a curing accelerator,
The resin material according to any one of claims 1 to 12, wherein the curing accelerator contains an imidazole compound. The resin material according to any one of claims 1 to 15, which is a resin film. The resin material according to any one of claims 1 to 16, which is used for forming an insulating layer in a multilayer printed wiring board. base material and
a resin film laminated on the surface of the base material,
A laminated film, wherein the resin film is the resin material according to any one of claims 1 to 17. a circuit board;
a plurality of insulating layers disposed on the surface of the circuit board;
a metal layer disposed between the plurality of insulating layers,
A multilayer printed wiring board, wherein at least one of the plurality of insulating layers is a cured product of the resin material according to any one of claims 1 to 17.

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