JP7323314B2 - Resin materials, laminated films and multilayer printed wiring boards - Google Patents

Description

TECHNICAL FIELD 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.

2. Description of the Related Art 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 insulation between internal layers and to form an insulating layer positioned on a surface layer. Wiring, which is generally made of metal, is laminated on the surface of the insulating layer. Moreover, in order to form the insulating layer, a resin film obtained by forming the resin material into a film may be used. The above resin materials and resin films 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 Literature 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 discloses (A) a polyfunctional epoxy resin (excluding a phenoxy resin), (B) a phenol-based curing agent and/or an active ester-based curing agent, (C) a thermoplastic resin, and (D) A resin composition containing an inorganic filler and (E) a quaternary phosphonium curing accelerator is disclosed. (C) The thermoplastic resin is a thermoplastic resin selected from phenoxy resins, polyvinyl acetal resins, polyimides, polyamideimide resins, polyethersulfone resins, and polysulfone resins. (E) quaternary phosphonium curing accelerator is selected from tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate one or more quaternary Phosphonium curing accelerator.

WO2016/114286A1 JP 2015-145498 A

When the insulating layer is formed using a conventional resin material such as that described in Patent Document 1, the embedding of the resin material into the unevenness of the substrate is not sufficiently high, or the resin material is excessively spread from the periphery of the substrate during lamination. It may protrude, making it difficult to control the film thickness. In addition, 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 is not sufficiently low, or the adhesion between the insulating layer and the copper substrate is not sufficient. may not be high enough.

On the other hand, it is difficult to lower the curing temperature (for example, 200° C. or lower) in a conventional resin material containing only a maleimide compound having an aromatic skeleton because the Tg of the maleimide compound is high. In addition, when the curing temperature is lowered, sufficient molecular motion is difficult to occur, so curing failure may occur. In addition, when the curing temperature is lowered, the resin material laminated in the early stage is heated more times and for a longer time than the resin material laminated in the latter stage during the production of the multilayer printed wiring board. Therefore, the electrical properties and physical properties of the insulating layer may change.

In addition, with conventional resin materials, the bending stability of cured products may not be sufficiently high.

In this way, 1) the embeddability of the uneven surface is enhanced, 2) excessive protrusion of the resin material from the periphery of the substrate 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 metal and 6) to improve the bending stability of the cured product. In other words, the current situation is that it is extremely difficult to obtain a resin material that exhibits all of the above effects 1) to 6).

The purpose of the present invention is to 1) improve the embedding property of the uneven surface, 2) suppress excessive protrusion of the resin material from the periphery of the substrate during lamination, 3) suppress the curing temperature, and 4) reduce the dielectric loss tangent of the cured product. 5) improved adhesion to metals; and 6) improved bending stability of the cured product. Another object of the present invention is to provide a laminated film and a multilayer printed wiring board using the resin material.

According to a broad aspect of the present invention, there is provided a resin material containing 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. .

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

In a specific 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 specific 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 acid dianhydride.

In a specific 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 acid dianhydride.

In a specific 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 dimer diamine.

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

On the specific situation with the resin material which concerns on this invention, the said thermosetting compound is an epoxy compound.

In a specific aspect of the resin material according to the present invention, 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.

In a specific 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 in a total of 100% by weight of the polyimide compound and the aliphatic skeleton-containing compound.

In a specific 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 specific 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 and 98% by weight in 100% by weight of the organic components excluding the solvent in the resin material. % by weight or less.

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

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

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

On the specific situation with the resin material which concerns on this invention, the said resin material is a resin film.

The resin material according to the present invention is suitably used for forming insulating layers in multilayer printed wiring boards.

A broad aspect of the present invention provides a laminated film comprising a substrate and a resin film laminated on the surface of the substrate, wherein the resin film is the resin material described above.

According to a broad aspect of the present invention, the present invention comprises 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, wherein 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 configuration, it is possible to 1) improve the embedding property of the uneven surface, 2) suppress excessive protrusion of the resin material from the periphery of the substrate during lamination, and 3) cure temperature. 4) the dielectric loss tangent of the cured product is lowered, 5) the adhesion to metal is enhanced, and 6) the bending stability of the cured product can be enhanced. The resin material according to the present invention can exhibit all of the above effects 1) to 6).

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

The present invention will be described 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 configuration, it is possible to 1) improve the embedding property of the uneven surface, 2) suppress excessive protrusion of the resin material from the periphery of the substrate during lamination, and 3) cure temperature. 4) the dielectric loss tangent of the cured product is lowered, 5) the adhesion to metal is enhanced, and 6) the bending stability of the cured product can be enhanced. The resin material according to the present invention can exhibit all of the above effects 1) to 6). In the resin material according to the present invention, as 5) adhesion to metal, for example, the peel strength between the insulating layer and the metal layer (copper layer) can be increased.

In addition, since the resin material according to the present invention has the above structure, the thermal dimensional stability can be enhanced. In addition, since the resin material according to the present invention has the above structure, it is possible to improve the handleability.

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 form includes a liquid form. The resin material according to the present invention is preferably a resin film because of its excellent handleability. When the resin material according to the present invention is a resin composition, it is possible to improve the handleability during application or film formation. When the resin material according to the present invention is a resin film, the handleability 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 enhanced.

In formula (X) above, 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, a 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 in 1) to 6) described above. In particular, when the resin material contains a polyimide compound and does not contain a specific aliphatic skeleton-containing compound, it is possible to improve the embedding of the uneven surface, lower the dielectric loss tangent, lower the curing temperature, and improve the cured product. It is difficult to improve 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 a plurality of maleimide skeletons and all nitrogen atoms are bonded to aromatic rings), the N-phenylmaleimide compound is Due to the high Tg, it is difficult to lower the curing temperature and it is difficult to lower the dielectric loss tangent. On the other hand, even if the resin material does not contain a polyimide compound but contains a specific aliphatic skeleton-containing compound, it is difficult to effectively exhibit all the effects of the present invention in 1) to 6) described above. In particular, when 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 increase. As a result, the thickness of the insulating layer may be uneven.

Hereinafter, details of each component used in the resin material according to the present invention and applications of the resin material according to the present invention will be described.

[Polyimide compound]
The resin material according to the present invention contains a polyimide compound. The above polyimide compound is a compound different from the maleimide compound. The polyimide compound may or may not have a maleimide skeleton at its terminal. The polyimide compound may have an acid anhydride structure or a citraconimide structure at its terminal. Conventionally known polyimide compounds can be used as the polyimide compound. As for the said polyimide compound, only 1 type may be used and 2 or more types may be used together.

A polyimide compound is produced by a method of reacting a tetracarboxylic dianhydride with an isocyanate ester compound, a method of reacting a tetracarboxylic dianhydride with a diamine compound, and a method of reacting a tetracarboxylic dianhydride with a triamine compound. etc. can be obtained.

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenylsulfonetetra 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′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3′,4,4′-tetraphenylsilanetetracarboxylic 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 hexane, 1,5-diaminopentane, 1,8-diaminooctane, 1,3-diaminopropane, 1,11-diaminoundecane, 2-methyl-1,5-diaminopentane, dimer diamine, and the like.

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 above in 1) to 6), the polyimide compound is preferably a polyimide compound having a skeleton derived from dimer diamine. The skeleton derived from the dimer diamine exists 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 and the dimer diamine.

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

In the total 100% by weight of the polyimide compound and the aliphatic skeleton-containing compound, the content of the polyimide compound is preferably 3% by weight or more, more preferably 5% by weight or more, and still more preferably 10% by weight or more. is 80% by weight or less, more preferably 60% by weight or less, and still more preferably 50% by weight or less. When the content of the polyimide compound is equal to or more than the lower limit and equal to or less than the upper limit, the viscosity of the resin material does not become too high, and the handleability and embeddability into the uneven surface can be further improved. Further, when the content of the polyimide compound is equal to or more than the lower limit and equal to or less than the upper limit, it is possible to prevent the amount of flow 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 still more preferably 7% by weight or more in 100% by weight of the components excluding the inorganic filler and solvent in the resin material. . In 100% by weight of components excluding inorganic fillers and solvents 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 Preferably, it is 20% by weight or less. When the content of the polyimide compound is at least the lower limit, the dielectric loss tangent of the cured product can be lowered, the flow rate can be well controlled, and the adhesion between the insulating layer and the metal layer can be further enhanced. When the content of the polyimide compound is equal to or less than the above upper limit, the embedding property to the uneven surface can be further enhanced. Handleability can be improved as content of the said polyimide compound is more than the said minimum and below the said upper limit.

From the viewpoint of further enhancing the embedding property 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.

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

When the polyimide compound has a maleimide skeleton at its terminal, 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 compound containing 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 the polyimide compound. Maleimide compound X has a maleimide group. The maleimide compound X has a terminal maleimide group. Maleimide compound X has an aliphatic skeleton. Therefore, the maleimide compound X has a maleimide group and an aliphatic skeleton. In the maleimide compound X, it is preferable that the above-mentioned aliphatic skeleton is bonded to the nitrogen atom forming the maleimide skeleton. In addition, the maleimide compound X may have an imide skeleton. As the maleimide compound X, conventionally known maleimide compounds can be used. The maleimide compound X includes a citraconimide compound. The citraconimide compound is a compound in which a methyl group is bonded to one of the carbon atoms constituting the double bond between carbon atoms in the 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 acid dianhydride. The 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 acid dianhydride, and a polyamine compound having an aliphatic skeleton and a polyamine compound having an aliphatic skeleton and a skeleton derived from a reaction product of a carboxylic acid dianhydride and an amine compound different from

The maleimide compound X having a skeleton derived from the reaction product of the polyamine compound having an aliphatic skeleton and the carboxylic acid dianhydride can be obtained, for example, by reacting the polyamine compound having an aliphatic skeleton with the carboxylic acid dianhydride. 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 acid 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 acid dianhydride. The maleimide compound X is a reaction product of a diamine compound having an aliphatic skeleton, an amine compound different from the diamine compound having an aliphatic skeleton (for example, a diamine compound having an aromatic skeleton), and a carboxylic acid dianhydride. It may have a skeleton from which it originates. The maleimide compound X may have a skeleton derived from a reaction product of a triamine compound having an aliphatic skeleton and a carboxylic acid dianhydride, and the triamine compound having an aliphatic skeleton and the triamine having an aliphatic skeleton It may have a skeleton derived from a reaction product of an amine compound different from the compound and a carboxylic acid dianhydride. In this case, one of a diamine compound having an aliphatic skeleton and a triamine compound having an aliphatic skeleton is preferably used to obtain the reactant. More preferably, both a diamine compound having an aliphatic skeleton and a triamine compound having an aliphatic skeleton are used to obtain the reactant. In this case, the amount (% by weight) of the triamine compound having an aliphatic skeleton is preferably 5% or less of the amount (% by weight) of the diamine compound having an aliphatic skeleton.

The maleimide compound X having a skeleton derived from the reaction product of the diamine compound having an aliphatic skeleton and the carboxylic acid dianhydride can be obtained, for example, by reacting the diamine compound having an aliphatic skeleton with the carboxylic acid dianhydride to is obtained by obtaining a reactant in which is an amino group, and then reacting the reactant with maleic anhydride.

The maleimide compound X having a skeleton derived from the reaction product of the triamine compound having an aliphatic skeleton and the carboxylic acid dianhydride can be obtained, for example, by reacting the triamine compound having an aliphatic skeleton with the carboxylic acid dianhydride to is obtained by obtaining a reactant in which is an amino group, and then reacting the reactant with maleic anhydride.

When the maleimide compound X is a reaction product of a diamine compound and a carboxylic acid dianhydride, the maleimide compound X preferably satisfies the following (1) or (2), and (1) and (2) ) is more preferably satisfied. (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 acid dianhydride, the skeleton having the amino group is the maleimide skeleton.

Examples of the diamine compound 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- diaminopentane, 1,8-diaminooctane, 1,3-diaminopropane, 1,11-diaminoundecane, 2-methyl-1,5-diaminopentane, and diamine compounds having a skeleton derived from dimer diamine, and the like. .

Examples of the diamine compound 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 acid dianhydride include pyromellitic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenylsulfonetetracarboxylic acid 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′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3′,4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2, 3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic 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, 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 dimer diamine is preferably a reaction product of dimer diamine and tetracarboxylic dianhydride. 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 that derived from dimer diamine. may have a diamine skeleton of

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

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenylsulfonetetra 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′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3′,4,4′-tetraphenylsilanetetracarboxylic 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 above in 1) to 6), the maleimide compound X is preferably an N-alkylbismaleimide compound having a skeleton derived from dimer diamine.

Designer Molecules Inc. has commercially available N-alkylbismaleimide compounds having a skeleton derived from dimer diamine. ``BMI-1500'', ``BMI-1700'', and ``BMI-3000'' manufactured by the same company.

Weight ratio of the content of the maleimide compound X to the total content of the thermosetting compound described later and the component X described later (content of the maleimide compound X/total content of the thermosetting compound and the component X ) is preferably 0.05 or more, more preferably 0.1 or more, preferably 0.9 or less, more preferably 0.75 or less. When the weight ratio (the content of the maleimide compound X/the total content of the thermosetting compound and the component X) is not less than the lower limit and not more than the upper limit, the dielectric loss tangent can be further reduced, and the insulating layer and the metal layer It is possible to further enhance the adhesion with.

The content of the maleimide compound X is preferably 3% by weight or more, more preferably 5% by weight or more, and still more preferably 10% by weight or more in 100% by weight of the resin material excluding the inorganic filler and the solvent, 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 lower limit, the dielectric loss tangent can be further reduced, and the adhesion between the insulating layer and the metal layer can be further enhanced. When the content of the maleimide compound X is equal to or less than the upper limit, embedding properties during lamination can be improved.

From the viewpoint of further enhancing the adhesion between the insulating layer and the metal layer, the weight average molecular weight of the maleimide compound X is preferably 500 or more, more preferably 1000 or more, preferably less than 15000, more preferably less than 12000, and more preferably less than 12000. It is preferably 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. 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, the nitrogen atom forming the benzoxazine skeleton is preferably bound to the aliphatic skeleton. In addition, the benzoxazine compound X may have an imide skeleton. As the benzoxazine compound X, conventionally known benzoxazine compounds can be used. Only one kind of the benzoxazine compound X may be used, or two or more kinds thereof may be used in combination.

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 is substituted with a benzoxazine skeleton.

The benzoxazine compound X is obtained, for example, by reacting the above-described tetracarboxylic dianhydride with the above-described diamine compound to obtain a reactant having amino groups at both ends, and then combining the reactant with phenol and paraformaldehyde. can be obtained by reacting In addition, the above N-alkylbenzoxazine compound having a skeleton derived from dimer diamine can be obtained, for example, by reacting tetracarboxylic dianhydride and dimer diamine to obtain a reactant having a skeleton derived from dimer diamine at both ends. After that, the reactant, phenol and paraformaldehyde are reacted to obtain the compound.

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

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

The benzoxazine compound X having a skeleton derived from the reaction product of the polyamine compound having an aliphatic skeleton and the carboxylic acid dianhydride can be obtained, for example, by reacting the polyamine compound having an aliphatic skeleton and the carboxylic acid dianhydride. 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 acid 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 acid dianhydride. The benzoxazine compound X is a reaction product of a diamine compound having an aliphatic skeleton, an amine compound different from the diamine compound having an aliphatic skeleton (for example, a diamine compound having an aromatic skeleton), and a carboxylic acid dianhydride. You 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 acid dianhydride, and has a triamine compound having an aliphatic skeleton and an aliphatic skeleton. It may have a skeleton derived from a reaction product of an amine compound different from the triamine compound and a carboxylic acid dianhydride. In this case, one of a diamine compound having an aliphatic skeleton and a triamine compound having an aliphatic skeleton is preferably used to obtain the reactant. More preferably, both a diamine compound having an aliphatic skeleton and a triamine compound having an aliphatic skeleton are used to obtain the reactant. In this case, the amount (% by weight) of the triamine compound having an aliphatic skeleton is preferably 5% or less of the amount (% by weight) of the diamine compound having an aliphatic skeleton.

The benzoxazine compound X having a skeleton derived from the reaction product of the diamine compound having an aliphatic skeleton and the carboxylic acid dianhydride can be obtained, for example, by reacting the diamine compound having an aliphatic skeleton and the carboxylic acid dianhydride. It can be obtained by obtaining a reactant having an amino group at the end and then reacting the reactant with phenol and paraformaldehyde.

The benzoxazine compound X having a skeleton derived from the reaction product of the triamine compound having an aliphatic skeleton and the carboxylic acid dianhydride can be obtained, for example, by reacting the triamine compound having an aliphatic skeleton and the carboxylic acid dianhydride. It can be obtained by obtaining a reactant having an amino group at the end and then 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 described 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 dimer diamine is preferably a reaction product of dimer diamine and tetracarboxylic dianhydride. 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 that derived from dimer diamine. may have a diamine skeleton of

Examples of the dimer diamine include the dimer diamines described above.

Examples of the tetracarboxylic dianhydride include the tetracarboxylic dianhydrides described above.

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

Weight ratio of the content of the benzoxazine compound X to the total content of the thermosetting compound described later and the component X described later (content of the benzoxazine compound X/total of the thermosetting compound and component X 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 weight ratio (the content of the benzoxazine compound X/the total content of the thermosetting compound and the component X) is equal to or greater than the lower limit and equal to or lower than the upper limit, the dielectric loss tangent can be further reduced, and the insulating layer and the metal Adhesion to the layer can be further enhanced.

The content of the benzoxazine compound X is preferably 3% by weight or more, more preferably 5% by weight or more, and still more preferably 10% by weight or more in 100% by weight of the resin material excluding the inorganic filler and the solvent. , 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 lower limit, the dielectric loss tangent can be further reduced, and the adhesion between the insulating layer and the metal layer can be further enhanced. When the content of the benzoxazine compound X is equal to or less than the upper limit, the embedding property 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 benzoxazine compound X is preferably 500 or more, more preferably 1000 or more, preferably less than 15000, more preferably less than 12000. It is more preferably 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 is preferably 10% by weight or more, more preferably 15% by weight or more, and still more preferably 10% by weight of the organic components excluding the solvent in the resin material. is 20% by weight or more. The total content of the polyimide compound and the aliphatic skeleton-containing compound is preferably 98% by weight or less, more preferably 80% by weight or less, based on 100% by weight of the organic components excluding the solvent in the resin material. When the total content is equal to or more than the lower limit and equal to or less than the upper limit, the above-described effects 1) to 6) of the present invention can be exhibited 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. is mentioned. As for the said thermosetting compound, only 1 type may be used and 2 or more types may be used together.

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

Examples of the epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenol novolac type epoxy compounds, biphenyl type epoxy compounds, biphenyl novolak 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 adamantane skeleton, epoxy compound having tricyclodecane skeleton, naphthylene ether type Epoxy compounds, epoxy compounds having a triazine core in the skeleton, and the like are included.

The epoxy compound preferably contains an epoxy compound having an aromatic skeleton, preferably an epoxy compound having a naphthalene skeleton or a phenyl skeleton, more preferably an epoxy compound having an aromatic skeleton, and having a naphthalene skeleton. It is more preferable that it is an epoxy compound having In this case, the dielectric loss tangent can be further lowered, and heat resistance, flame retardancy and thermal dimensional stability can be enhanced.

From the viewpoint of further lowering the dielectric loss tangent and improving the coefficient of 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. is preferred.

The viscosity at 25°C of the epoxy compound that 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 Rheological Instruments) or the like is used.

More preferably, the epoxy compound has a molecular weight of 1,000 or less. In this case, even if the content of the components excluding the solvent in the resin material is 100% by weight and the content of the inorganic filler is 50% by weight or more, the resin material has high fluidity when forming the insulating layer. Therefore, when an uncured resin material or B-staged resin material is laminated on a circuit board, the inorganic filler can be uniformly present.

The molecular weight of the epoxy compound means the molecular weight that can be calculated from the structural formula when the epoxy compound is not a polymer and when the structural formula of the epoxy compound can be specified. Moreover, when the said epoxy compound is a polymer, it means a 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, based on 100% by weight of the organic components excluding the solvent in the resin material. % by weight or more, preferably 50% by weight or less, more preferably 40% by weight or less.

Weight ratio of the content of the epoxy compound to the total content of the aliphatic skeleton-containing compound and component X described later (content of the epoxy compound/total of the aliphatic skeleton-containing compound and component X) 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 later (content of the epoxy compound/total of the aliphatic skeleton-containing compound and component X) content) is preferably 0.9 or less, more preferably 0.8 or less. When the weight ratio (the content of the epoxy compound/the total content of the aliphatic skeleton-containing compound and the component X) is not less than the lower limit and not more than the upper limit, the dielectric loss tangent can be lowered, and the wire The coefficient of expansion can be reduced, the adhesion between the insulating layer and the metal layer can be further enhanced, and the handleability can be enhanced.

[Inorganic filler]
The resin material preferably contains an inorganic filler. By using the inorganic filler, the dielectric loss tangent of the cured product can be further reduced. In addition, the use of the inorganic filler further reduces the dimensional change of the cured product due to heat. Only one kind of the 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.

Reduce the surface roughness of the cured product, further increase the adhesive strength between the cured product and the metal layer, form finer wiring on the surface of the cured product, and improve the insulation reliability of the cured product. From the viewpoint of providing the above, the inorganic filler is preferably silica or alumina, more preferably silica, and still more preferably fused silica. By using silica, the thermal expansion coefficient of the cured product is further lowered, and the dielectric loss tangent of the cured product is further lowered. In addition, the use of silica effectively reduces the surface roughness of the cured product and effectively increases the adhesive strength between the cured product and the metal layer. The shape of silica is preferably spherical.

From the viewpoint of promoting curing of the resin, effectively increasing the glass transition temperature of the cured product, and effectively decreasing the thermal linear expansion coefficient of the cured product, regardless of the curing environment, the inorganic filler is spherical silica. is preferred.

The average particle size of the inorganic filler is preferably 50 nm or more, more preferably 100 nm or more, still more preferably 500 nm or more, preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less. When the average particle diameter of the inorganic filler is equal to or more than the lower limit and equal to or less than the upper limit, the embedding property to the uneven surface can be further improved, and the adhesion between the insulating layer and the metal layer can be further improved.

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

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 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 surface of the roughened cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased. In addition, since the inorganic filler is surface-treated, it is possible to form finer wiring on the surface of the cured product, and the cured product has better inter-wiring insulation reliability and interlayer insulation reliability. can be given.

Examples of the coupling agent include silane coupling agents, titanium coupling agents and aluminum coupling agents. Examples of the silane coupling agent include methacrylsilane, acrylsilane, 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, still 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, still more preferably 80% by weight or less, and 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 is effectively lowered, and the coefficient of linear expansion can be reduced. When the content of the inorganic filler is equal to or less than the above upper limit, the adhesiveness, embedding properties for uneven surfaces, and etching performance can be enhanced. When the content of the inorganic filler is not less than the lower limit and not more than the 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. can be done. Furthermore, with this amount of inorganic filler, it is possible to lower the coefficient of thermal expansion of the cured product and to improve the smear removability.

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

As the curing agent, cyanate ester compound (cyanate ester curing agent), amine compound (amine curing agent), thiol compound (thiol curing agent), imidazole compound, phosphine compound, dicyandiamide, phenol compound (phenol curing agent), acid anhydride compounds, active ester compounds, carbodiimide compounds (carbodiimide curing agents), benzoxazine compounds having no aliphatic skeleton (benzoxazine curing agents), and maleimide compounds having no 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 improving the thermal dimensional stability, the above curing agents include phenol compounds, cyanate ester compounds, acid anhydrides, active ester compounds, carbodiimide compounds, and benzoxazine compounds having no aliphatic skeleton. preferably contains at least one component of That is, the resin material contains a curing agent containing at least one component selected from 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. is preferred. 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 the present 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" may be described as "component X".

The resin material preferably contains a curing agent containing component X. As for the component X, only one type may be used, or two or more types may be used in combination.

Examples of the phenol compound include novolak-type phenol, biphenol-type phenol, naphthalene-type phenol, dicyclopentadiene-type phenol, aralkyl-type phenol, and dicyclopentadiene-type phenol.

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

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 novolak-type cyanate ester resins include phenol novolac-type cyanate ester resins and alkylphenol-type 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.

Commercially available products of the above cyanate ester compounds include phenol novolak type cyanate ester resins (“PT-30” and “PT-60” manufactured by Lonza Japan Co., Ltd.) and prepolymers in which bisphenol type cyanate ester resins are trimerized (Lonza Japan "BA-230S", "BA-3000S", "BTP-1000S" and "BTP-6020S" manufactured by the same company).

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

Commercially available products of the above acid anhydrides include "Rikashid TDA-100" manufactured by Shin Nippon Rika Co., Ltd., and the like.

The active ester compound is a compound having at least one ester bond in its structure and having aromatic rings bonded to both sides of the ester bond. An 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 formula (1) above, X1 represents an aliphatic chain-containing group, an aliphatic ring-containing group, or an aromatic ring-containing group, and X2 represents an aromatic ring-containing group. Preferred examples of the aromatic ring-containing group include an optionally substituted benzene ring and an optionally substituted naphthalene ring. A hydrocarbon group is mentioned as said substituent. 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.

The combination of X1 and X2 includes a combination of an optionally substituted benzene ring and an optionally substituted benzene ring, an optionally substituted benzene ring and a substituted A combination with a naphthalene ring optionally having a group is exemplified. Further, the combination of X1 and X2 includes a combination of a naphthalene ring optionally having substituent(s) and a naphthalene ring optionally having substituent(s).

The active ester compound is not particularly limited. From the viewpoint of further improving thermal dimensional stability, the active ester compound is preferably an active ester compound having two or more aromatic skeletons. From the viewpoint of reducing the dielectric loss tangent of the cured product and enhancing the thermal dimensional stability of the cured product, it is more preferable to have a naphthalene ring in the main chain skeleton of the active ester.

Commercially available products of the active ester compound 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 carbodiimide compound may be used, or two or more kinds thereof may be used in combination.

In the above formula (2), X is an alkylene group, an alkylene group to which a substituent is bonded, a cycloalkylene group, a cycloalkylene group to which a substituent is bonded, an arylene group, or an arylene group to which a substituent is bonded group, and p is an integer of 1-5. When there are multiple X's, the multiple X's may be the same or different.

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

Commercially available carbodiimide compounds include Nisshinbo Chemical Co., Ltd. "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", "Carbodilite V-09", "Carbodilite 10M-SP" and "Carbodilite 10M-SP (improved)", and "Stabaxol P", "Stabaxol P400" and "Hykasil 510" manufactured by Rhein Chemie.

Examples of the benzoxazine compound having no aliphatic skeleton include Pd-type benzoxazine and Fa-type benzoxazine.

Examples of commercially available benzoxazine compounds having no aliphatic skeleton include "Pd type" manufactured by Shikoku Kasei Kogyo Co., Ltd., and the like.

The content of component X with respect to a total of 100 parts by weight of the polyimide compound, the aliphatic skeleton-containing compound, and the thermosetting compound is preferably 70 parts by weight or more, more preferably 85 parts by weight or more, preferably It is 150 parts by weight or less, more preferably 120 parts by weight or less. When the content of component X is above the lower limit and below the upper limit, the curability is further improved, the thermal dimensional stability is further enhanced, and volatilization of residual unreacted components can be further suppressed.

The content of component X relative to 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 component X is above the lower limit and below the upper limit, the curability is further improved, the thermal dimensional stability is further enhanced, and volatilization of residual 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 the 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, and more preferably 85% by weight or less. When the total content of the thermosetting compound and the component X is at least the above lower limit and below the above upper limit, the curability is further improved, and the thermal dimensional stability can be further enhanced.

The total content of the thermosetting compound and the component X in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 50% by weight or more, more preferably 60% by weight or more, 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 at least the above lower limit and below the above upper limit, the curability is further improved, and the thermal dimensional stability can be further enhanced.

[Curing accelerator]
The resin material preferably contains a curing accelerator. The use of the curing accelerator makes the curing speed even faster. By rapidly curing the resin material, the crosslinked structure in the cured product becomes uniform and the number of unreacted functional groups is reduced, resulting in a high crosslink density. The curing accelerator is not particularly limited, and conventionally known curing accelerators can be used. Only one kind of the curing accelerator may be used, or two or more kinds thereof may be used in combination.

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.

Examples of the imidazole compound include 2-undecylimidazole, 2-heptadecylimidazole, 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 isocyanurate, 2-phenylimidazole isocyanurate, 2-methylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-dihydroxymethylimidazole etc.

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

Examples of the phosphorus compounds include triphenylphosphine compounds.

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

Examples of the peroxide include dicumyl peroxide, perhexyl 25B, and the like.

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 still more preferably 80% by weight. % by weight or more, most preferably 100% by weight (total amount).

The curing accelerator preferably contains 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, or contains a radical curing accelerator and an imidazole compound, or contains a radical curing accelerator and a phosphorus compound. . If the curing of the resin material does not proceed sufficiently, the dielectric loss tangent becomes high and the coefficient of linear expansion may become large. The curing accelerator may contain the radical curing accelerator and the imidazole compound. As the radical curing accelerator, it is preferable that the reaction temperature in the presence of the radical curing accelerator is higher than the temporary curing temperature before etching and lower than the final curing temperature after etching. When Perhexyl 25B is used as the radical curing accelerator, the above effects are exhibited 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 be favorably progressed, 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 equal to or more than the lower limit and equal to or less than the upper limit, the resin material is efficiently cured. If the content of the curing accelerator is within a more preferable range, the storage stability of the resin material will be further increased, and a more favorable cured product will be obtained.

[Thermoplastic resin]
The resin material preferably contains a thermoplastic resin. Examples of the thermoplastic resin include polyvinyl acetal resin and phenoxy resin. Only one kind of the thermoplastic resin may be used, or two or more kinds thereof may be used in combination.

The thermoplastic resin is preferably a phenoxy resin from the viewpoint of effectively lowering the dielectric loss tangent and effectively increasing the adhesion of the metal wiring regardless of the curing environment. The use of the phenoxy resin suppresses the deterioration of the embedding properties of the resin film in holes or unevenness of the circuit board and the non-uniformity of the inorganic filler. In addition, the use of a phenoxy resin makes it possible to adjust the melt viscosity, so that the dispersibility of the inorganic filler is improved, and the resin composition or B-staged product is less likely to wet and spread in unintended areas during the curing process.

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

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

Commercial products of the phenoxy resin include, for example, "YP50", "YP55" and "YP70" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and "1256B40", "4250", "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. is.

The weight average molecular weights of the thermoplastic resin and the phenoxy resin are weight average molecular weights 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 (when the thermoplastic resin is a phenoxy resin, the content of the phenoxy resin) in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 1 weight. % or more, more preferably 2 wt % or more, preferably 30 wt % or less, more preferably 20 wt % or less. When the content of the thermoplastic resin is equal to or more than the lower limit and equal to or less than the upper limit, the embedding property of the resin material into the holes or unevenness of the circuit board is improved. When the content of the thermoplastic resin is equal to or higher than the lower limit, formation of the resin film becomes easier, and an even better insulating layer can be obtained. If the content of the thermoplastic resin is equal to or less than the upper limit, the thermal expansion coefficient of the cured product will be even lower. When the content of the thermoplastic resin is equal to or less than the upper limit, the surface roughness of the cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased.

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

Examples of the solvent include acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane, toluene, xylene, methyl ethyl ketone, N,N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidone, n-hexane, cyclohexane, cyclohexanone and mixtures such as naphtha.

Most of the solvent is preferably removed when the resin composition is formed into a film. Therefore, the boiling point of the 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 appropriately changed in consideration of the coatability of the resin composition.

[Other ingredients]
For the purpose of improving impact resistance, heat resistance, resin compatibility, workability, etc., the above resin materials contain leveling agents, flame retardants, coupling agents, coloring agents, antioxidants, ultraviolet degradation inhibitors, and anti-degradation agents. A foaming agent, a thickener, a thixotropic agent, and a thermosetting resin other than the epoxy compound may be added.

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

Other thermosetting resins include polyphenylene ether resins, divinylbenzyl ether resins, polyarylate resins, diallyl phthalate resins, polyimide resins, benzoxazine resins, benzoxazole resins, bismaleimide resins and acrylate resins.

(resin film and laminated film)
A resin film (B-stage product/B-stage film) is obtained by molding the resin composition described above into a film. The resin material is preferably a resin film. The resin film is preferably a B-stage film.

The resin material is preferably a thermosetting material.

Examples of the method for obtaining a resin film by molding the 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 molding method in which a resin composition containing a solvent is cast and molded into a film. Other film forming methods known in the art. An extrusion molding method or a casting molding method is preferable because it can be used for thinning. Film includes sheets.

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

A film-like resin composition that can be obtained by the drying process as described above is called 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 may not be a prepreg. If the resin film is not a prepreg, no migration occurs along the glass cloth or the like. In addition, when the resin film is laminated or precured, the unevenness due to the glass cloth does not occur on the surface.

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

The laminated film includes a substrate and a resin film laminated on the surface of the substrate. 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 substrate.

Examples of the substrate 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 substrate may be subjected to 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 equal to or greater than 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 above resin material is suitably used for forming a mold resin for embedding a semiconductor chip in a semiconductor device.

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

The printed wiring board is obtained, for example, by heating and pressurizing the resin material.

A metal foil can be laminated on one side or both sides of the resin film. A method for laminating the resin film and the metal foil is not particularly limited, and a known method can be used. For example, the resin film can be laminated on the metal foil while applying pressure with or without heating using a device such as a parallel plate press or a roll laminator.

The above resin material is suitably used to obtain a copper-clad laminate. An example of the copper-clad laminate is a copper-clad laminate comprising 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 in the range of 1-50 μm. In order to increase the adhesive strength between the cured resin material and the copper foil, the copper foil preferably has fine irregularities on its surface. A method for forming the unevenness is not particularly limited. Examples of the method for forming the unevenness include a forming method 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 substrate is formed of the above resin material. Moreover, the insulating layer of the multilayer substrate may be formed of the resin film of the laminated film by using the laminated film. The insulating layer is preferably laminated on the surface of the circuit board on which the circuit is provided. A part of the insulating layer is preferably embedded between the circuits.

In the multilayer substrate, it is preferable that the surface of the insulating layer opposite to the surface on which the circuit board is laminated is roughened.

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 a swelling treatment before the roughening treatment.

Moreover, it is preferable that the multilayer substrate further includes a copper plating layer laminated on the roughened surface of the insulating layer.

Further, as another example of the multilayer board, a circuit board, an insulating layer laminated on the surface of the circuit board, and a surface of the insulating layer laminated on the surface opposite to the surface on which the circuit board is laminated. and a copper foil. It is preferable that the insulating layer is formed by using a copper clad laminate comprising a copper foil and a resin film laminated on one surface of the copper foil, and curing the resin film. Furthermore, the copper foil is preferably 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 laminated on the surface of the circuit board. At least one of the plurality of insulating layers arranged on the circuit board is formed using the resin material. The multilayer substrate preferably further includes a circuit laminated on at least one surface of the insulating layer formed using the resin film.

Among multilayer substrates, a multilayer printed wiring board is required to have a low dielectric loss tangent and high insulation reliability due to an insulating layer. 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 insulating layers in multilayer printed wiring boards.

The multilayer printed wiring board includes, for example, a circuit board, a plurality of insulating layers arranged on the surface of the circuit board, and metal layers arranged 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 one 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. As shown in FIG. The insulating layers 13 to 16 are hardened layers. A metal layer 17 is formed on a partial region of the upper surface 12 a of the circuit board 12 . A metal layer 17 is formed on a partial region of the upper surface of each of the insulating layers 13 to 15 other than the insulating layer 16 positioned on the outer surface opposite to the circuit board 12 among the multiple insulating layers 13 to 16. It is Metal layer 17 is a circuit. A metal layer 17 is arranged between the circuit board 12 and the insulating layer 13 and between the laminated insulating layers 13 to 16, respectively. The lower metal layer 17 and the upper metal layer 17 are connected to each other by at least one of via-hole connection and through-hole connection (not shown).

In the multilayer printed wiring board 11, the insulating layers 13 to 16 are formed of the cured resin material. In this embodiment, since the surfaces of the insulating layers 13-16 are roughened, fine holes (not shown) are formed in the surfaces of the insulating layers 13-16. Also, the metal layer 17 reaches inside the fine holes. Moreover, 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 reduced. Moreover, in the multilayer printed wiring board 11, good insulation reliability is imparted between the upper metal layer and the lower metal layer that are not connected by via-hole connections and through-hole connections (not shown).

(Roughening treatment and swelling treatment)
The resin material is preferably used to obtain a cured product that is roughened or desmeared. The cured product also includes a pre-cured product that can be further cured.

In order to form fine unevenness on the surface of the cured product obtained by precuring the resin material, the cured product is preferably subjected to a roughening treatment. The cured product is preferably subjected to a swelling treatment before the roughening treatment. The cured product is preferably subjected to swelling treatment after precuring and before roughening treatment, and further cured after roughening treatment. However, the cured product does not necessarily have to be subjected to a swelling treatment.

As the swelling treatment method, for example, a method of treating the cured product with an aqueous solution or an organic solvent dispersion solution of a compound containing ethylene glycol as a main component is used. The swelling liquid used for the swelling treatment generally contains an alkali as a pH adjuster or the like. The swelling liquid preferably contains sodium hydroxide. Specifically, for example, the swelling treatment is performed by treating the cured product with a 40% by weight ethylene glycol aqueous 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 in the range of 50-85°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.

A chemical oxidizing agent such as a manganese compound, a chromium compound, or a persulfate compound is used for the roughening treatment. These chemical oxidants are used as aqueous solutions or organic solvent dispersion solutions after water or organic solvents are added. The roughening liquid used for the roughening treatment generally contains an alkali as a pH adjuster or the like. The roughening liquid preferably contains sodium hydroxide.

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

The surface arithmetic mean roughness Ra of the cured product is preferably 10 nm or more, preferably less than 300 nm, more preferably less than 200 nm, still more preferably less than 150 nm. In this case, the adhesive strength between the cured product and the metal layer is increased, and 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 according to JIS B0601:1994.

(Desmear treatment)
Through-holes may be formed in the cured product obtained by precuring the resin material. Vias, through holes, or the like are formed as through holes in the multilayer substrates and the like. For example, vias can be formed by irradiation with a laser such as a _CO2 laser. Although the diameter of the via is not particularly limited, it is about 60 to 80 μm. Due to the formation of the through-holes, smears, which are residues of the resin derived from the resin component contained in the cured product, are often formed at the bottom of the vias.

In order to remove the smear, the surface of the cured product is preferably desmeared. The desmearing treatment may also serve as the roughening treatment.

For the desmear treatment, chemical oxidizing agents such as manganese compounds, chromium compounds, or persulfate compounds are used, as in the roughening treatment. These chemical oxidants are used as aqueous solutions or organic solvent dispersion solutions after water or organic solvents are added. A desmearing liquid used for desmearing generally contains an alkali. The desmear treatment liquid preferably contains sodium hydroxide.

By using the above resin material, the surface roughness of the desmeared cured product is sufficiently reduced.

EXAMPLES The present invention will now be described in detail with reference to examples and comparative examples. The invention is not limited to the following examples.

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

(Synthesis example 1)
135.0 g of tetracarboxylic dianhydride (“BisDA-1000” manufactured by SABIC Japan LLC) and 400 g of cyclohexanone are 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. Then, 17.5 g of 1,3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Company, Inc.) was added dropwise into the reaction vessel and reacted to obtain a reaction product having acid anhydrides at both ends. Then, 148 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) was slowly added into the reaction vessel, and then 60.0 g of methylcyclohexane was added into the reaction vessel. A Dean-Stark trap and 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 was then added and the resulting mixture was refluxed for an additional 12 hours. After completion of the reaction, isopropanol was added for reprecipitation, and the precipitate was collected and dried to obtain an N-alkylbismaleimide compound having a skeleton derived from dimer diamine. The recovery rate of the N-alkylbismaleimide compound having a skeleton derived from dimer diamine was 83%. (weight average molecular weight 10000)

(Synthesis example 2)
After stirring, put 55 g of pyromellitic dianhydride (manufactured by Tokyo Kasei Co., Ltd., molecular weight: 254.15) and 300 g of cyclohexanone into a reaction vessel equipped with a water divider, a thermometer, and a nitrogen gas introduction tube, and was heated to 60°C. Then, a solution of 26.7 g of bis (aminomethyl) norbornane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 154.26) dissolved in cyclohexanone was added dropwise into the reaction vessel to react, and both ends were acid anhydrides. A reaction product was obtained. Thereafter, isopropanol was added to recover an imide compound having an acid anhydride at both ends. Next, the precipitate was dissolved again in cyclohexane, and 46.0 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) was slowly added into the reaction vessel, and then 45.0 g of methylcyclohexane was added into the reaction vessel. A Dean-Stark trap and 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 the 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 are placed in a reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen gas introduction tube, followed by After dissolving 164 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan Co., Ltd.) in cyclohexanone, it was added dropwise. After that, 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 obtained imide compound, 38 g of phenol (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 94.11) and 12 g of paraformaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and the resulting mixture was further refluxed for 12 hours to obtain benzoxazine. changed. Then, by reprecipitating with isopropanol, an N-alkylbenzoxazine compound (weight average molecular weight: 7700) was obtained.

(Maleimide compound having no aliphatic skeleton (maleimide compound having 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 (26.8% by weight of nonvolatile matter), which is a reaction product of tetracarboxylic dianhydride and dimer diamine, was synthesized according to Synthesis Example 4 below.

(Synthesis Example 4)
A reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen gas inlet tube was charged with 300.0 g of tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan LLC) and 665.5 g of cyclohexanone. and the solution in the reaction vessel was heated to 60°C. Then, 89.0 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) and 54.7 g of 1,3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Company, Inc.) were dropped into the reaction vessel. Then, 121.0 g of methylcyclohexane and 423.5 g of ethylene glycol dimethyl ether were added to the reactor, and imidization reaction was carried out at 140° C. for 10 hours. Thus, a polyimide compound-containing solution (non-volatile content: 26.8% by weight) was obtained. The molecular weight (weight average molecular weight) of the obtained polyimide compound was 20,000. 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:
Using a high-performance liquid chromatograph system manufactured by Shimadzu Corporation, measurement was performed using tetrahydrofuran (THF) as a developing medium at a column temperature of 40° C. and a flow rate of 1.0 ml/min. "SPD-10A" was used as a detector, and two "KF-804L" columns (exclusion limit molecular weight: 400,000) manufactured by Shodex were connected in series. As 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, A calibration curve was generated using 500, 1,050, 500 substances and molecular weight calculations were performed.

(Thermoplastic resin)
Phenoxy resin (manufactured by Mitsubishi Chemical Corporation "YX6954BH30")

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

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

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

(Curing accelerator)
Dimethylaminopyridine ("DMAP" manufactured by Wako Pure Chemical Industries, Ltd.)
2-phenyl-4-methylimidazole ("2P4MZ" manufactured by Shikoku Kasei Co., Ltd.)
2-ethyl-4-methylimidazole ("2E4MZ" manufactured by Shikoku Chemical Industry 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, apply the obtained resin material on the release-treated surface of a release-treated PET film (“XG284” manufactured by Toray Industries, Inc., thickness 25 μm), and then place in a gear oven at 100° C. for 2 minutes. Dry for 30 seconds to evaporate the solvent. Thus, a laminated film (laminated film of PET film and resin film) in which a resin film (B stage film) having a thickness of 40 μm was laminated on the PET film was obtained.

(evaluation)
(1) Handleability The obtained resin film (B stage film) was bent 10 times at 180 degrees. The number of cracks or cracks in the resin film was observed in 10 times.

[Handling Criteria]
○: Less than 3 cracks or cracks in 10 times △: 3 or more and less than 6 times in 10 times Cracks or cracks 6 or more occurrences

(2) Ability to fill irregular surfaces and prevent protrusion (prevention of excessive wetting and spreading)
Etching only the copper foil of a 100 mm square copper-clad laminate (a laminate of a glass epoxy substrate with a thickness of 400 μm and a copper foil with a thickness of 25 μm) to form a recess (opening) with a diameter of 100 μm and a depth of 25 μm. The hole was opened in a straight line with respect to the central 30 mm square area of the substrate so that the interval between the centers of the adjacent holes was 900 μm. Thus, an evaluation board having a total of 900 holes was prepared.

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

Voids in the depressions were observed on the obtained evaluation samples using an optical microscope. By evaluating the percentage of pits in which voids were observed, the embeddability into the uneven surface was determined according to the following criteria.

[Evaluation Criteria for Embedding Capability on Concavo-convex Surface]
○: 0% ratio of depressions in which voids were observed
△: more than 0% of pits in which voids were observed, less than 5% ×: 5% or more of pits in which voids were observed

Using an optical microscope, the resulting evaluation samples were observed to see whether or not the resin film protruded from a predetermined region on the substrate, and the protruding prevention property was determined according to the following criteria.

[Determination criteria for anti-extrusion]
○: Protrusion of the resin film from the periphery of the evaluation board after lamination is 2 mm or less △: Protrusion of the resin film from the periphery of the evaluation board after lamination exceeds 2 mm and is 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 An exothermic peak associated with curing of the obtained resin film (B stage film) was evaluated using a differential scanning calorimeter (“Q2000” manufactured by TA Instruments). 8 mg of the resin film was placed in a special aluminum pan and covered with a special jig. This special aluminum pan and an empty aluminum pan (reference) are placed in a heating unit and heated from -30°C to 250°C at a temperature elevation rate of 3°C/min under a nitrogen atmosphere, and reverse heat flow and non-reverse heat flow are performed. The heat flow was observed. Curing temperature was confirmed by the exothermic peak observed in non-reverse heat flow.

[Criteria for Curing Temperature]
○: All exothermic peaks below 200°C ×: At least one exothermic peak at a temperature higher than 200°C

(4) Dielectric Loss Tangent The obtained resin film was cut into a size of 2 mm in width and 80 mm in length, and five sheets were laminated to obtain a laminate having a thickness of 200 μm. The resulting laminate was heated at 190° C. for 90 minutes to obtain a cured product. The resulting cured product was measured at room temperature (23°C) by the cavity resonance method using Kanto Denshi Applied Development Co., Ltd.'s "Cavity Resonance Perturbation Method Dielectric Constant Measurement Device CP521" and Keysight Technologies, Inc.'s "Network Analyzer N5224A PNA". Then, the dielectric loss tangent was measured at a frequency of 1.0 GHz.

[Dielectric loss tangent criterion]
○: Dielectric loss tangent is 3.5 × 10 ^-3 or less ×: Dielectric loss tangent exceeds 3.5 × 10 ^-3

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

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

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

Peel strength measurement:
A 1-cm-wide strip-shaped cut was made on the surface of the copper foil of the evaluation sample. Set the evaluation sample on a 90° peel tester (“TE-3001” manufactured by Tester Sangyo Co., Ltd.), pick up the edge of the notched copper foil with a gripper, peel the copper foil 20 mm and measure the peel strength (peel strength) was measured.

[Determination 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 obtained 40 μm-thick resin film (B stage film) was heated at 190° C. for 90 minutes, and the cured product was cut into a size of 3 mm×25 mm. Using a thermomechanical analyzer (“EXSTAR TMA/SS6100” manufactured by SII Nanotechnology Co., Ltd.), the cut cured product was measured at 25 ° C 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.

[Criteria for Average Coefficient of Linear Expansion]
○: The average linear expansion coefficient is 25 ppm / ° C. or less △: The average linear expansion coefficient exceeds 25 ppm / ° C. and 30 ppm / ° C. or less ×: The average linear expansion coefficient exceeds 30 ppm / ° C.

(7) Bending Stability of Cured Product A cured product obtained by heating the obtained 40 μm-thick resin film (B stage film) at 190° C. for 90 minutes was cut into a size of 30 mm×150 mm. Using a planar U-shaped folding tester (manufactured by Yuasa Co., Ltd.), a downward bending test was performed under the conditions of 200 times/min, 180° C. bending (bending gap 5 mm), and film stroke 70 mm. The measurement was repeated 5 times and the average value was calculated.

[Criteria for bending stability of cured product]
○○: No cracks after 2000 times of bending ○: Cracks occur when the number of bends is 100 or more and less than 2000 times ×: Cracks occur when the number of bends is less than 100 times

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

DESCRIPTION OF SYMBOLS 11... Multilayer printed wiring board 12... Circuit board 12a... Upper surface 13-16... Insulating layer 17... Metal layer

Claims (14)

a polyimide compound;
at least one aliphatic skeleton-containing compound selected from a maleimide compound having an aliphatic skeleton and a benzoxazine compound having an aliphatic skeleton ;
a thermosetting compound;
an inorganic filler ,
The aliphatic skeleton-containing compound has a skeleton derived from a reaction product of a diamine compound having an aliphatic skeleton and a carboxylic acid dianhydride,
The diamine compound having an aliphatic skeleton is a diamine compound having a skeleton derived from dimer diamine,
A resin material in which 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. 2. The resin material according to claim 1, wherein said thermosetting compound is an epoxy compound. including a curing agent and a curing accelerator;
The resin material according to claim 1 or 2, wherein the curing accelerator contains an imidazole compound. a polyimide compound;
at least one aliphatic skeleton-containing compound selected from a maleimide compound having an aliphatic skeleton and a benzoxazine compound having an aliphatic skeleton;
and a curing accelerator,
The aliphatic skeleton-containing compound has a skeleton derived from a reaction product of a diamine compound having an aliphatic skeleton and a carboxylic acid dianhydride,
The diamine compound having an aliphatic skeleton is a diamine compound having a skeleton derived from dimer diamine,
The curing accelerator contains a radical curing accelerator and dimethylaminopyridine, or contains a radical curing accelerator and an imidazole compound, or contains a radical curing accelerator and a phosphorus compound, resin material . containing a curing agent,
The resin material according to claim 4, wherein the curing accelerator contains an imidazole compound. 6. The resin material according to any one of claims 1 to 5, 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 15000 or more,
The resin material according to any one of claims 1 to 6 , wherein the aliphatic skeleton-containing compound has a weight average molecular weight of less than 15,000. The content of the polyimide compound is 3% by weight or more and 80% by weight or less in the total 100% by weight of the polyimide compound and the aliphatic skeleton-containing compound, according to any one of claims 1 to 7 . resin material. The resin material according to any one of claims 1 to 8 , wherein the polyimide compound is a polyimide compound having a skeleton derived from dimer diamine. Any one of claims 1 to 9 , 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. 1. The resin material according to 1. The resin material according to any one of claims 1 to 10 , which is a resin film. The resin material according to any one of claims 1 to 11 , which is used for forming an insulating layer in a multilayer printed wiring board. a substrate;
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 12 . a circuit board;
a plurality of insulating layers disposed on the surface of the circuit board;
and a metal layer disposed between a plurality of the 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 12 .

Images