JP2019173009A - Cured body, resin material and multilayer printed board - Google Patents

Abstract

To provide a cured body that 1) can lower a dielectric loss tangent and can improve 2) thermal dimensional stability, 3) elastic moduli, 4) plating peel strength, 5) adhesion between an insulating layer and a metal layer.SOLUTION: The present invention provides a cured body of a resin material containing a bismaleimide compound or bisbenzoxazine compound, an epoxy compound, and an inorganic filler, the cured body having a sea-island structure having a sea part and an island part.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a cured body of a resin material containing an epoxy compound and an inorganic filler. The present invention also relates to a resin material containing an epoxy compound and an inorganic filler. Moreover, this invention relates to the multilayer printed wiring board using the said hardening body.

  Conventionally, various resin materials have been used to obtain electronic components such as semiconductor devices, laminated boards, and printed wiring boards. For example, in a multilayer printed wiring board, a resin material is used to form an insulating layer for insulating internal layers or to form an insulating layer located in a surface layer portion. On the surface of the insulating layer, a wiring generally made of metal is laminated. Moreover, in order to form the said insulating layer, the resin film in which the said resin material was turned into a film may be used. The resin material and the resin film are used as insulating materials for multilayer printed wiring boards including build-up films.

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

  Patent Document 2 below includes (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-based curing accelerator is disclosed. (C) The thermoplastic resin is a thermoplastic resin selected from phenoxy resin, polyvinyl acetal resin, polyimide, polyamideimide resin, polyethersulfone resin, and polysulfone resin. (E) The quaternary phosphonium curing accelerator is one or more quaternary compounds selected from tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. It is a phosphonium-based curing accelerator.

WO2016 / 114286A1 JP2015-145498A

  When an insulating layer (cured product) is formed using a conventional resin composition (resin material) as described in Patent Document 1, the electrical characteristics of the cured product can be enhanced to some extent. However, when the insulating layer is formed using a conventional resin material as described in Patent Document 1, the thermal dimensional stability of the cured product is not sufficiently increased. As a result, connection reliability may be lowered when a thermal cycle test is performed. In addition, when an insulating layer is formed using a conventional resin material, the elastic modulus of the insulating layer is small and sufficient strength may not be obtained. Furthermore, when a multilayer printed wiring board or the like is manufactured using a conventional resin material by a semi-additive method, the surface roughness of the insulating layer is increased due to high etching properties, and as a result, the plating peel strength is sufficiently high. It may not be. In addition, when an insulating layer is formed using a conventional resin material as described in Patent Document 2, the surface roughness of the insulating layer may be excessively increased, or the dielectric loss tangent may not be sufficiently reduced. There is.

  In this way, 1) lowering the dielectric tangent, 2) thermal dimensional stability, 3) elastic modulus, 4) plating peel strength, 5) enhancing adhesion between the insulating layer and the metal layer, 1) -5) It is extremely difficult to obtain a cured product that exhibits all of the above effects.

  The objects of the present invention are: 1) a cured product capable of reducing dielectric loss tangent, 2) thermal dimensional stability, 3) elastic modulus, 4) plating peel strength, and 5) enhancing adhesion between an insulating layer and a metal layer. Is to provide. Another object of the present invention is to provide a resin material from which the cured product can be obtained. Another object of the present invention is to provide a multilayer printed wiring board using the cured body.

  According to a wide aspect of the present invention, a cured body of a resin material including a bismaleimide compound or a bisbenzoxazine compound, an epoxy compound, and an inorganic filler, the cured body has a sea-island structure having a sea part and an island part. A cured body is provided.

  On the specific situation with the hardening body which concerns on this invention, the said bismaleimide compound is a N-alkyl bismaleimide compound.

  In a specific aspect of the cured product according to the present invention, the N-alkylbismaleimide compound is an N-alkylbismaleimide compound having a skeleton derived from dimer diamine.

  On the specific situation with the hardening body which concerns on this invention, the average major axis of the said island part is 5 micrometers or less.

  On the specific situation with the hardening body which concerns on this invention, the said island part contains the said bismaleimide compound or the said bisbenzoxazine compound.

  In a specific aspect of the cured product according to the present invention, the resin material is a benzoxazine compound different from a phenol compound, a cyanate ester compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a bisbenzoxazine compound. A curing agent comprising at least one component is included.

  On the specific situation with the hardening body which concerns on this invention, the said component is a component which has an aromatic skeleton.

  On the specific situation with the hardening body which concerns on this invention, the said epoxy compound is an epoxy compound which has an aromatic skeleton.

  On the specific situation with the hardening body which concerns on this invention, the molecular weight of the said bismaleimide compound is 500-15000.

  On the specific situation with the hardening body which concerns on this invention, content of the said inorganic filler is 50 weight% or more in 100 weight% of said hardening bodies.

  On the specific situation with the hardening body which concerns on this invention, the average particle diameter of the said inorganic filler is 5 micrometers or less.

  On the specific situation with the hardening body which concerns on this invention, the said resin material contains a thermoplastic resin, Content of the said thermoplastic resin in 100 weight% of components except the said inorganic filler and solvent in the said resin material. Is 1% by weight or more and 20% by weight or less.

  On the specific situation with the hardening body which concerns on this invention, the molecular weight of the said thermoplastic resin is 15000 or more.

  On the specific situation with the hardening body which concerns on this invention, the said thermoplastic resin is a polyimide compound.

  In a specific aspect of the cured body according to the present invention, the resin material includes a curing accelerator, and the curing accelerator includes an anionic curing accelerator or a radical curing accelerator.

  On the specific situation with the hardening body which concerns on this invention, the said resin material contains the said anionic hardening accelerator, and the said anionic hardening accelerator is an imidazole compound.

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

  According to a wide aspect of the present invention, there is provided a resin material having a sea-island structure including a bismaleimide compound or a bisbenzoxazine compound, an epoxy compound, and an inorganic filler, and a cured body of the resin material having a sea part and an island part. Is done.

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

  The cured body according to the present invention is a cured body of a resin material containing a bismaleimide compound, an epoxy compound, and an inorganic filler. The cured body according to the present invention has a sea-island structure having a sea part and an island part. Since the cured body according to the present invention has the above-described configuration, 1) the dielectric loss tangent is lowered, 2) thermal dimensional stability, 3) elastic modulus, 4) plating peel strength, 5) insulating layer and metal. All the effects 1) -5) that the adhesion to the layer can be enhanced can be exhibited.

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

  Hereinafter, the present invention will be described in detail.

  The cured product according to the present invention is a cured product of a resin material containing a bismaleimide compound or a bisbenzoxazine compound, an epoxy compound, and an inorganic filler. The cured body according to the present invention has a sea-island structure having a sea part and an island part. The cured product according to the present invention may contain a bismaleimide compound, may contain a bisbenzoxazine compound, and may contain a bismaleimide compound and a bisbenzoxazine compound.

  Since the cured body according to the present invention has the above-described configuration, 1) the dielectric loss tangent is lowered, 2) thermal dimensional stability, 3) elastic modulus, 4) plating peel strength, 5) insulating layer and metal. All the effects 1) -5) that the adhesion to the layer can be enhanced can be exhibited. For example, 2) As the thermal dimensional stability, the linear expansion coefficient can be reduced. As a result, connection reliability can be enhanced, for example, in a thermal cycle test. 4) As the plating peel strength, the peel strength between the roughened cured product (insulating layer) and the metal layer laminated by plating on the surface of the insulating layer can be increased. Moreover, even if the roughness of the roughened cured product (insulating layer) is small, the plating peel strength can be increased. Moreover, in the hardened | cured material (insulating layer) containing a bisbenzoxazine compound, a linear expansion coefficient can be made still lower and the adhesive strength of an insulating layer and a metal layer can be raised further.

  In addition, since the cured body according to the present invention has the above-described configuration, the surface roughness after etching can be reduced and the surface can be improved. Moreover, in the hardening body which concerns on this invention, hardening temperature can be restrained low (for example, 200 degrees C or less). Moreover, in the cured body according to the present invention, conductor loss due to the skin effect can be reduced in a multilayer substrate such as a multilayer printed wiring board obtained using the cured body.

  The cured body according to the present invention has a sea-island structure having a sea part and an island part.

  The resin material according to the present invention includes a bismaleimide compound or a bisbenzoxazine compound, an epoxy compound, and an inorganic filler. In the resin material according to the present invention, the cured body of the resin material has a sea-island structure having a sea part and an island part. The resin material according to the present invention may contain a bismaleimide compound, may contain a bisbenzoxazine compound, and may contain a bismaleimide compound and a bisbenzoxazine compound.

  From the viewpoint of lowering the dielectric loss tangent and increasing the peel strength of the plating and the adhesion between the insulating layer and the metal layer, the island part preferably contains the bismaleimide compound or the bisbenzoxazine compound. When the bismaleimide compound or the bisbenzoxazine compound is reacted in the cured product, the bismaleimide compound or the bisbenzoxazine compound contained in the island is a reactant. In particular, when the island portion contains a bismaleimide compound having a skeleton derived from dimer diamine, which is a relatively flexible skeleton, the linear expansion coefficient can be further reduced. Therefore, it is possible to increase the content of the skeleton derived from dimer diamine which the bismaleimide compound has.

  From the viewpoint of lowering the dielectric loss tangent, increasing the thermal dimensional stability and elastic modulus, and reducing the surface roughness of the insulating layer, the sea part contains the component derived from the epoxy compound and the inorganic filler. Is preferred. Moreover, when the said resin material contains a hardening | curing agent, it is preferable that the said sea part contains the component originating in the said hardening | curing agent. Moreover, when the said resin material contains a hardening accelerator, it is preferable that the said sea part contains the component originating in a hardening accelerator.

  The content of the inorganic filler contained in 100% by weight of the sea part is preferably larger than the content of the inorganic filler present in 100% by weight of the island part. In this case, thermal dimensional stability and elastic modulus can be further increased. A particularly excellent effect is obtained when the content of the inorganic filler contained in 100% by weight of the sea part is 30% by weight or more.

  From the viewpoint of reducing the dielectric loss tangent, increasing the thermal dimensional stability, and reducing the surface roughness of the insulating layer, the average major axis of the island is preferably 5 μm or less, more preferably 3 μm or less, and still more preferably. It is 1.5 μm or less. The lower limit of the average major axis of the island is not particularly limited. The average major axis of the island part may be 0.1 μm or more.

  The average linear expansion coefficient (CTE) at 25 ° C. or more and 150 ° C. or less of the cured body is preferably 30 ppm / ° C. or less, more preferably 25 ppm / ° C. or less. When the average linear expansion coefficient is not more than the above upper limit, the thermal dimensional stability is further improved.

  When the cured product is heated at 190 ° C. for 90 minutes to obtain a cured product (insulating layer), the average linear expansion coefficient (CTE) of the cured product at 25 ° C. to 150 ° C. is preferably 30 ppm / ° C. Hereinafter, it is more preferably 25 ppm / ° C. or less. When the average linear expansion coefficient is not more than the above upper limit, the thermal dimensional stability is further improved.

  The dielectric loss tangent of the cured body at a frequency of 1.0 GHz is preferably 0.005 or less, more preferably 0.004 or less. When the dielectric loss tangent is less than or equal to the upper limit, transmission loss is further suppressed.

  When the cured body is heated at 190 ° C. for 90 minutes to obtain a cured product (insulating layer), the dielectric loss tangent of the cured product at a frequency of 1.0 GHz is preferably 0.005 or less, more preferably 0.8. 004 or less. When the dielectric loss tangent is less than or equal to the upper limit, transmission loss is further suppressed.

  In addition, at the time of use of the said hardening body, the said hardening body may be hardened by heating on conditions other than 190 degreeC and 90 minutes.

  Hereinafter, the details of each component used for the cured body according to the present invention and the resin material for obtaining the cured body, and the use of the cured body according to the present invention will be described.

[Bismaleimide compounds]
The resin material preferably contains a bismaleimide compound. The bismaleimide compound is not particularly limited. The bismaleimide compound has a maleimide group. A conventionally known bismaleimide compound can be used as the bismaleimide compound. The bismaleimide compound according to the present invention includes a citraconimide compound. The citraconimide compound is a compound in which a methyl group is bonded to one of carbon atoms constituting a double bond between carbon atoms in a maleimide group. As for the said bismaleimide compound, only 1 type may be used and 2 or more types may be used together.

  Examples of the bismaleimide compound include aromatic bismaleimide compounds and aliphatic bismaleimide compounds.

  Examples of the aliphatic bismaleimide compound include N-alkyl bismaleimide compounds.

  From the viewpoint of lowering the dielectric loss tangent and keeping the curing temperature low, the bismaleimide compound is preferably an N-alkyl bismaleimide compound.

  From the viewpoint of more effectively exerting the effects of the present invention 1) -5) described above, the N-alkylbismaleimide compound has a structure in which an aliphatic skeleton is bonded to a nitrogen atom in a maleimide group. preferable. From the viewpoint of improving the etching performance, the N-alkylbismaleimide compound preferably has an imide bond or a skeleton derived from dimer diamine.

  From the viewpoint of further reducing the dielectric loss tangent, the N-alkylbismaleimide compound is more preferably an N-alkylbismaleimide compound having a skeleton derived from dimer diamine. In the N-alkyl bismaleimide compound having a skeleton derived from dimeramine amine, the dimeramine skeleton exists as a partial skeleton.

  The bismaleimide compound can be obtained, for example, by reacting a tetracarboxylic dianhydride and a diamine compound to obtain a compound having amino groups at both ends, and then reacting the compound with maleic anhydride. . In addition, the N-alkylbismaleimide compound having a skeleton derived from dimeramine is obtained by reacting, for example, tetracarboxylic dianhydride and dimeramine to obtain a compound having a skeleton derived from dimeramine at both ends. It can be obtained by reacting the compound with maleic anhydride.

  Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and 3,3 ′, 4,4′-biphenylsulfonetetra. Carboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether Tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic dianhydride, 1,2 , 3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxypheno) Ii) 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, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, etc. .

  Examples of the diamine compound include 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (aminomethyl) norbornane, and 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-me Le-1,5-diaminopentane, and dimer diamine, and the like.

  The diamine compound is preferably a diamine compound having an alicyclic skeleton because it is more excellent due to the effects of the present invention. In this case, the bismaleimide compound may have a skeleton derived from a reaction product of a tetracarboxylic dianhydride and a diamine compound having an aliphatic skeleton, and the tetracarboxylic dianhydride and the aliphatic It may have a skeleton derived from a reaction product of a diamine compound having a skeleton and an amine compound different from the diamine compound having an aliphatic skeleton. The bismaleimide compound has a diamine skeleton derived from a diamine compound in which both diamine skeletons have the aliphatic skeleton, and a diamine skeleton derived from a diamine compound in which the diamine skeleton other than both ends has an aromatic skeleton. It may have a skeleton.

  Examples of commercially available dimeramine amines include Versamine 551 (trade name, manufactured by BASF Japan, 3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl) cyclohexene), Versamine 552. (Brand name, Cognics Japan Co., Ltd., hydrogenated product of Versamine 551), PRIAMINE 1075, PRIAMINE 1074 (Brand name, both manufactured by Claude Japan Co., Ltd.) and the like.

  As a commercial item of the said N-alkyl bismaleimide compound, Designer Molecules Inc. is mentioned. “BMI-1500”, “BMI-1700”, “BMI-3000” and the like manufactured by the company are listed.

  The weight ratio of the content of the bismaleimide compound to the total content of the epoxy compound and the component X described later is expressed as a weight ratio (content of the bismaleimide compound / total of the epoxy compound and the component X). Content). When the resin material contains the bismaleimide compound, the weight ratio (the content of the bismaleimide compound / the total content of the epoxy compound and the component X) is preferably 0.05 or more, more preferably Is 0.1 or more, more preferably 0.15 or more. The weight ratio (content of the bismaleimide compound / total content of the epoxy compound and the component X) is preferably 0.75 or less, more preferably 0.6 or less, and even more preferably 0.5 or less. It is. When the weight ratio (content of the bismaleimide compound / total content of the epoxy compound and the component X) is not less than the lower limit and not more than the upper limit, the sea-island structure can be formed more easily. Further, the dielectric loss tangent can be further lowered, and the thermal dimensional stability, the elastic modulus, and the adhesion between the insulating layer and the metal layer can be further enhanced. From the viewpoint of easily forming an island portion containing the bismaleimide compound and forming a sea-island structure even more easily, the weight ratio (content of the bismaleimide compound / total of the epoxy compound and the component X) Is preferably 0.1 or more and 0.5 or less.

  When the resin material contains the bismaleimide compound, the content of the bismaleimide compound is preferably 8% by weight or more, more preferably 100% by weight of the component excluding the inorganic filler and the solvent in the resin material. It is 10% by weight or more, preferably 65% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less. When the content of the bismaleimide compound is not less than the above lower limit and not more than the above upper limit, the sea-island structure can be more easily formed, the dielectric loss tangent is further lowered, the thermal dimensional stability, the elastic modulus, and the insulating layer And the metal layer can be further improved in adhesion.

  When the cured body contains the bismaleimide compound, the content of the bismaleimide compound is preferably 8% by weight or more, more preferably 10% by weight in 100% by weight of the component excluding the inorganic filler in the cured body. % Or more, preferably 65% 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 bismaleimide compound is not less than the above lower limit and not more than the above upper limit, the sea-island structure can be more easily formed, the dielectric loss tangent is further lowered, the thermal dimensional stability, the elastic modulus, and the insulating layer And the metal layer can be further improved in adhesion.

  By changing the molecular weight of the bismaleimide compound, it is possible to arbitrarily control the ease of forming a sea-island structure and the size of the island. From the viewpoint of further increasing the storage stability of the resin material and further enhancing the embedding property of the B stage film in the holes or irregularities of the circuit board, the molecular weight of the bismaleimide compound is preferably 500 or more, more preferably 600 or more, preferably 15000 or less, more preferably less than 10,000, and still more preferably less than 5000. Moreover, when the molecular weight of the bismaleimide compound satisfies the above range, it becomes easy to form a sea-island structure, the thermal expansion coefficient can be further reduced, and the elastic modulus can be increased. In particular, when the molecular weight of the bismaleimide compound is 15000 or less, it can be sufficiently mixed with other resin components, and thus the rough surface can be further improved. Further, when the molecular weight of the bismaleimide compound is 15000 or less, an increase in melt viscosity can be effectively suppressed as compared with the case where a high molecular weight component having a molecular weight of 15000 or more is added. Therefore, the addition amount of the bismaleimide compound having a molecular weight of 15000 or less can be made larger than the addition amount of the high molecular weight component. As a result, both the dielectric loss tangent and the embedding property can be improved.

  The molecular weight of the bismaleimide compound means a molecular weight that can be calculated from the structural formula when the bismaleimide compound is not a polymer and when the structural formula of the bismaleimide compound can be specified. Moreover, the molecular weight of the said bismaleimide compound shows the weight average molecular weight in polystyrene conversion measured by gel permeation chromatography (GPC), when the said bismaleimide compound is a polymer.

[Bisbenzoxazine compound]
The resin material preferably contains a bisbenzoxazine compound. The bisbenzoxazine compound is not particularly limited. As the bisbenzoxazine compound, a conventionally known bisbenzoxazine compound can be used. As for the said bisbenzoxazine compound, only 1 type may be used and 2 or more types may be used together.

  Examples of the bisbenzoxazine compound include aromatic bisbenzoxazine compounds and aliphatic bisbenzoxazine compounds.

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

  Examples of the aliphatic bisbenzoxazine compound include N-alkylbisbenzoxazine compounds.

  From the viewpoint of lowering the dielectric loss tangent and keeping the curing temperature low, the bisbenzoxazine compound is preferably an N-alkylbisbenzoxazine compound.

  From the viewpoint of improving the etching performance, the N-alkylbisbenzoxazine compound preferably has an imide bond or a skeleton derived from dimer diamine.

  The bisbenzoxazine compound is obtained by, for example, reacting the above-described tetracarboxylic dianhydride with the above-described diamine compound to obtain a compound having both amino groups, and then reacting the compound with phenol and paraformaldehyde. Can be obtained. In addition, the N-alkylbisbenzoxazine compound having a skeleton derived from dimerized amine was obtained by, for example, reacting tetracarboxylic dianhydride and dimerized amine to obtain a compound having a skeleton derived from dimerized amine at both ends. Thereafter, the compound can be obtained by reacting phenol with paraformaldehyde.

  The weight ratio of the content of the bisbenzoxazine compound to the total content of the epoxy compound and the component X described later is expressed as a weight ratio (content of the bisbenzoxazine compound / the epoxy compound and the component X). Total content). When the resin material contains the bisbenzoxazine compound, the weight ratio (content of the bisbenzoxazine compound / total content of the epoxy compound and the component X) is preferably 0.05 or more, More preferably, it is 0.1 or more, More preferably, it is 0.15 or more. The weight ratio (content of the bisbenzoxazine compound / total content of the epoxy compound and the component X) is preferably 0.75 or less, more preferably 0.6 or less, and still more preferably 0.5. It is as follows. When the weight ratio (content of the bisbenzoxazine compound / total content of the epoxy compound and the component X) is not less than the above lower limit and not more than the above upper limit, the sea-island structure can be more easily formed. In addition, the dielectric loss tangent can be further lowered, and the thermal dimensional stability, the elastic modulus, and the adhesion between the insulating layer and the metal layer can be further enhanced. From the viewpoint of easily forming an island portion containing the bisbenzoxazine compound and further easily forming a sea-island structure, the weight ratio (content of the bisbenzoxazine compound / epoxy compound and the component X) Is preferably 0.1 or more and 0.5 or less.

  When the resin material contains the bisbenzoxazine compound, the content of the bisbenzoxazine compound is preferably 8% by weight or more in 100% by weight of the component excluding the inorganic filler and the solvent in the resin material. Preferably it is 10 weight% or more, Preferably it is 65 weight% or less, More preferably, it is 50 weight% or less, Most preferably, it is 40 weight% or less. When the content of the bisbenzoxazine compound is not less than the above lower limit and not more than the above upper limit, the sea-island structure can be more easily formed, the dielectric loss tangent is further lowered, the thermal dimensional stability, the elastic modulus and the insulation. The adhesion between the layer and the metal layer can be further enhanced.

  When the cured body contains the bisbenzoxazine compound, the content of the bisbenzoxazine compound is preferably 8% by weight or more, more preferably 100% by weight of the component excluding the inorganic filler in the cured body. It is 10% by weight or more, preferably 65% 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 bisbenzoxazine compound is not less than the above lower limit and not more than the above upper limit, the sea-island structure can be more easily formed, the dielectric loss tangent is further lowered, the thermal dimensional stability, the elastic modulus and the insulation. The adhesion between the layer and the metal layer can be further enhanced.

  By changing the molecular weight of the bisbenzoxazine compound, it is possible to arbitrarily control the ease of forming the sea-island structure and the size of the island. From the viewpoint of further increasing the storage stability of the resin material and further enhancing the embedding property of the B-stage film in the holes or irregularities of the circuit board, the molecular weight of the bisbenzoxazine compound is preferably 500 or more, more preferably Is 600 or more, preferably 15000 or less, more preferably less than 10,000, and still more preferably less than 5000. Moreover, when the molecular weight of the bisbenzoxazine compound satisfies the above range, a sea-island structure is easily formed, the thermal expansion coefficient can be further reduced, and the elastic modulus can be increased. In particular, when the molecular weight of the bisbenzoxazine compound is 15000 or less, it can be sufficiently mixed with other resin components, so that the rough surface can be further improved. Further, when the molecular weight of the bisbenzoxazine compound is 15000 or less, an increase in melt viscosity can be effectively suppressed as compared with the case where a high molecular weight component having a molecular weight of 15000 or more is added. Therefore, the addition amount of the bisbenzoxazine compound having a molecular weight of 15000 or less can be made larger than the addition amount of the high molecular weight component. As a result, both the dielectric loss tangent and the embedding property can be improved.

  The molecular weight of the bisbenzoxazine compound means a molecular weight that can be calculated from the structural formula when the bisbenzoxazine compound is not a polymer and when the structural formula of the bisbenzoxazine compound can be specified. Moreover, the molecular weight of the said bisbenzoxazine compound shows the weight average molecular weight in polystyrene conversion measured by gel permeation chromatography (GPC), when the said bisbenzoxazine compound is a polymer.

[Epoxy compound]
The resin material includes an epoxy compound. A conventionally well-known epoxy compound can be used as said epoxy compound. The epoxy compound refers to an organic compound having at least one epoxy group. As for the said epoxy compound, only 1 type may be used and 2 or more types may be used together.

  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 novolac type epoxy compounds, biphenol type epoxy compounds, and naphthalene type epoxy compounds. Fluorene type epoxy compound, phenol aralkyl type epoxy compound, naphthol aralkyl type epoxy compound, dicyclopentadiene type epoxy compound, anthracene type epoxy compound, epoxy compound having adamantane skeleton, epoxy compound having tricyclodecane skeleton, naphthylene ether type Examples thereof include an epoxy compound and an epoxy compound having a triazine nucleus in the skeleton.

  From the viewpoint of further lowering the dielectric loss tangent, the epoxy compound preferably includes an epoxy compound having an aromatic skeleton, preferably includes an epoxy compound having a naphthalene skeleton or a phenyl skeleton, and an epoxy having an aromatic skeleton. More preferably, it is a compound. Further, when the epoxy compound is an epoxy compound having an aromatic skeleton, phase separation is likely to occur, and a sea-island structure can be formed more easily. Further, when the epoxy compound is an epoxy compound having a naphthalene skeleton, the dielectric loss tangent can be further reduced, and the linear expansion coefficient can be further reduced.

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

  The viscosity of the epoxy compound that is liquid at 25 ° C. at 25 ° C. is preferably 1000 mPa · s or less, and 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 Rheologicala Instruments) or the like is used.

  The molecular weight of the epoxy compound is more preferably 1000 or less. In this case, a resin material with high fluidity can be obtained when the insulating layer is formed even if the component in the resin material is 100% by weight excluding the solvent and the content of the inorganic filler is 50% by weight or more. For this reason, when an uncured resin material or a B-stage product is laminated on the circuit board, the inorganic filler can be uniformly present.

  The molecular weight of the epoxy compound means a 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, a weight average molecular weight is meant.

  From the viewpoint of further enhancing the adhesive strength between the insulating layer and the metal layer, the content of the epoxy compound is preferably 15% by weight or more, more preferably 20% by weight in 100% by weight of the component excluding the solvent in the resin material. % Or more, preferably 50% by weight or less, more preferably 40% by weight or less.

  The weight ratio of the content of the epoxy compound to the total content of the bismaleimide compound and the component X described later is expressed as a weight ratio (content of the epoxy compound / total of the bismaleimide compound and the component X). Content). When the resin material contains the bismaleimide compound, the weight ratio (content of the epoxy compound / total content of the bismaleimide compound and the component X) is preferably 0.2 or more, more preferably Is 0.25 or more, preferably 0.5 or less, more preferably 0.45 or less. When the weight ratio (content of the epoxy compound / total content of the bismaleimide compound and the component X) is not less than the lower limit and not more than the upper limit, a sea-island structure can be formed more easily. Further, the dielectric loss tangent can be further lowered, and the flame retardancy, thermal dimensional stability and elastic modulus can be further increased.

  The weight ratio of the content of the epoxy compound to the total content of the bisbenzoxazine compound and the component X described later is the weight ratio (content of the epoxy compound / the content of the bisbenzoxazine compound and the component X). Total content). When the resin material contains the bisbenzoxazine compound, the weight ratio (content of the epoxy compound / total content of the bisbenzoxazine compound and the component X) is preferably 0.2 or more, More preferably, it is 0.25 or more, preferably 0.5 or less, more preferably 0.45 or less. When the weight ratio (content of the epoxy compound / total content of the bisbenzoxazine compound and the component X) is not less than the above lower limit and not more than the above upper limit, the sea-island structure can be more easily formed. The dielectric loss tangent can be further reduced, and the flame retardancy, thermal dimensional stability and elastic modulus can be further increased.

[Inorganic filler]
The resin material includes an inorganic filler. By using the inorganic filler, the dielectric loss tangent of the cured product can be further reduced. Moreover, thermal dimensional stability can be improved by using the said inorganic filler. As for the said inorganic filler, only 1 type may be used and 2 or more types may be used together.

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

  The surface roughness of the insulating layer is reduced, the adhesive strength between the insulating layer and the metal layer is further increased, finer wiring is formed on the surface of the cured product, and better insulation reliability is achieved by the cured product. From the viewpoint of imparting 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 reduced. Further, the use of silica effectively reduces the surface roughness of the insulating layer, and effectively increases the adhesive strength between the insulating layer and the metal layer. The shape of silica is preferably spherical.

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

  The average particle size of the inorganic filler is preferably 50 nm or more, more preferably 100 nm or more, further preferably 500 nm or more, preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 2 μm or less. The adhesiveness of an insulating layer and a metal layer can be improved further as the average particle diameter of the said inorganic filler is more than the said minimum and below the said upper limit.

  A median diameter (d50) value of 50% is employed as the average particle diameter of the inorganic filler. The average particle size can be measured using a laser diffraction / scattering particle size distribution measuring apparatus.

  The inorganic filler is preferably spherical and more preferably spherical silica. In this case, the surface roughness of the surface of the insulating layer is effectively reduced, and the adhesive strength between the insulating layer 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 a surface-treated product with a coupling agent, and still more preferably a surface-treated product with a silane coupling agent. Since the inorganic filler is surface-treated, the surface roughness of the surface of the insulating layer is further reduced, and the adhesive strength between the insulating layer and the metal layer is further increased. Further, since the inorganic filler is surface-treated, it is possible to form finer wiring on the surface of the cured product, and to further improve the inter-wiring insulation reliability and interlayer insulation reliability to the cured product. Can be granted.

  Examples of the coupling agent include silane coupling agents, titanium coupling agents, and aluminum coupling agents. Examples of the silane coupling agent include aminophenyl silane, methacryl silane, acrylic silane, amino silane, imidazole silane, vinyl silane, and epoxy silane.

  The content of the inorganic filler is preferably 50% by weight or more, more preferably 60% by weight or more, and still more preferably 65% by weight in 100% by weight of the component excluding the solvent in the resin material and in 100% by weight of the cured product. % Or more, particularly preferably 68% by weight or more. In 100% by weight of the component excluding the solvent in the resin material, 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, particularly preferably 75% by weight. % Or less. When the content of the inorganic filler is equal to or more than the lower limit, the inorganic filler is likely to be unevenly distributed in the sea-island structure portion that does not contain the bismaleimide compound due to phase separation after curing. For this reason, the combination of the bismaleimide compound and the inorganic filler can effectively reduce the coefficient of thermal expansion, and can effectively reduce the dimensional change due to heat of the insulating layer. This effect is particularly exerted when the inorganic filler is the silica and when the content of the inorganic filler is 30% by weight or more. In addition, this effect is that the content of the inorganic filler is 30% by weight or more, and the weight ratio of the content of the bismaleimide compound to the total content of the epoxy compound and the component X described later ( This is particularly exhibited when the content of the bismaleimide compound / the total content of the epoxy compound and the component X) is 0.1 or more and 0.6 or less. Further, the effect is that the content of the inorganic filler is 30% by weight or more, and the weight ratio of the content of the bisbenzoxazine compound to the total content of the epoxy compound and the component X described later. This is particularly exhibited when the content of the bisbenzoxazine compound / the total content of the epoxy compound and the component X is 0.1 or more and 0.6 or less. When the content of the inorganic filler is not more than the above upper limit, the plating peel strength at low roughness can be increased. When the content of the inorganic filler is not less than the above lower limit and not more than the above upper limit, the surface roughness of the surface of the insulating layer can be further reduced, and finer wiring can be formed on the surface of the cured product. Can do. Furthermore, with this amount of the inorganic filler, it is possible to improve the elastic modulus and improve the smear removability at the same time as reducing the coefficient of thermal expansion of the cured product.

[Curing agent]
The resin material preferably contains a curing agent. The said hardening | curing agent is not specifically limited. As the curing agent, a conventionally known curing agent can be used. As for the said hardening | curing agent, only 1 type may be used and 2 or more types may be used together.

  Examples of the curing agent include a cyanate ester compound (cyanate ester curing agent), an amine compound (amine curing agent), a thiol compound (thiol curing agent), a phosphine compound, dicyandiamide, a phenol compound (phenol curing agent), an acid anhydride, and an activity. Examples include ester compounds, carbodiimide compounds (carbodiimide curing agents), and benzoxazine compounds (benzoxazine curing agents) different from bisbenzoxazine compounds. The curing agent preferably has a functional group capable of reacting with the epoxy group of the epoxy compound.

  From the viewpoint of increasing thermal dimensional stability and elastic modulus, the curing agent is at least one of benzoxazine compounds different from phenol compounds, cyanate ester compounds, acid anhydrides, active ester compounds, carbodiimide compounds, and bisbenzoxazine compounds. It preferably contains one component. That is, the resin material includes a curing agent including 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 different from a bisbenzoxazine compound. It is preferable.

  In this specification, “component at least one of benzoxazine compounds different from phenolic compounds, cyanate ester compounds, acid anhydrides, active ester compounds, carbodiimide compounds, and bisbenzoxazine compounds” is referred to as “component X”. May be described.

  Therefore, the resin material preferably contains a curing agent containing component X, and more preferably contains a curing agent containing a phenol compound. As for the said component X, only 1 type may be used and 2 or more types may be used together.

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

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

  Examples of the cyanate ester compounds include novolak-type cyanate ester resins, bisphenol-type cyanate ester resins, and prepolymers in which these are partially trimerized. Examples of the novolac type cyanate ester resin 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 novolac type cyanate ester resins ("PT-30" and "PT-60" manufactured by Lonza Japan) and prepolymers (Lonza Japan) in which bisphenol type cyanate ester resins are trimerized. "BA-230S", "BA-3000S", "BTP-1000S", and "BTP-6020S") manufactured by the company.

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

  Examples of commercially available acid anhydrides include “Ricacid TDA-100” manufactured by Shin Nippon Chemical Co., Ltd.

  The active ester compound means a compound containing at least one ester bond in the structure and having an aromatic ring bonded to both sides of the ester bond. The active ester compound is obtained, for example, by a condensation reaction between a carboxylic acid compound or thiocarboxylic acid compound and a hydroxy compound or thiol compound. Examples of the active ester compound include a compound represented by the following formula (1).

  In the above formula (1), X1 represents a group containing an aliphatic chain, a group containing an aliphatic ring or a group containing an aromatic ring, and X2 represents a group containing an aromatic ring. Preferable examples of the group containing an aromatic ring include a benzene ring which may have a substituent and a naphthalene ring which may have a substituent. A hydrocarbon group is mentioned as said substituent. The carbon number of the hydrocarbon group is preferably 12 or less, more preferably 6 or less, and still more preferably 4 or less.

  As a combination of X1 and X2, a combination of a benzene ring which may have a substituent and a benzene ring which may have a substituent, a benzene ring which may have a substituent and a substitution The combination with the naphthalene ring which may have a group is mentioned. Furthermore, examples of the combination of X1 and X2 include a combination of a naphthalene ring which may have a substituent and a naphthalene ring which may have a substituent.

  The active ester compound is not particularly limited. From the viewpoint of further improving thermal dimensional stability and elastic modulus, the active ester 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 increasing 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.

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

  The carbodiimide compound has a structural unit represented by the following formula (2). In the following formula (2), the right end and the left end are binding sites with other groups. As for the said carbodiimide compound, only 1 type may be used and 2 or more types may be used together.

  In the above formula (2), X is an alkylene group, a group having a substituent bonded to an alkylene group, a cycloalkylene group, a group having a substituent bonded to a cycloalkylene group, an arylene group, or a substituent bonded to an arylene group. Represents a group, and p represents an integer of 1 to 5. When two or more X exists, several X may be the same and may differ.

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

  Commercially available products of the above carbodiimide compounds include “Carbodilite V-02B”, “Carbodilite V-03”, “Carbodilite V-04K”, “Carbodilite V-07”, “Carbodilite V-09”, “Carbodilite” manufactured by Nisshinbo Chemical Co., Ltd. 10M-SP "and" Carbodilite 10M-SP (modified) ", and" STABAXOL P "," STABAXOL P400 ", and" HIKAZIL 510 "manufactured by Rhein Chemie.

  As said benzoxazine compound, Pd type benzoxazine, Fa type benzoxazine, etc. are mentioned.

  As a commercial item of the said benzoxazine compound, "Pd type" by Shikoku Kasei Kogyo Co., Ltd. etc. are mentioned.

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

  In 100% by weight of the component excluding the inorganic filler and the solvent in the resin material, the total content of the epoxy compound and the component X is preferably 50% by weight or more, more preferably 60% by weight or more, preferably It is 90 weight% or less, More preferably, it is 85 weight% or less. When the total content of the epoxy compound and the component X is not less than the above lower limit and not more than 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. By using the curing accelerator, the curing rate is further increased. By quickly curing the resin material, the crosslinked structure in the cured product becomes uniform, the number of unreacted functional groups is reduced, and as a result, the crosslinking density is increased. The said hardening accelerator is not specifically limited, A conventionally well-known hardening accelerator can be used. As for the said hardening accelerator, only 1 type may be used and 2 or more types may be used together.

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

  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 ′ -Methyl Midazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6 [2′-Ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine Isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-dihydroxymethylimidazole Can be mentioned.

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

  Examples of the phosphorus compound include a triphenylphosphine compound.

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

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

  The curing accelerator preferably contains an anionic curing accelerator or a radical curing accelerator. In this case, the curing accelerator may include an anionic curing accelerator, may include a radical curing accelerator, and includes both an anionic curing accelerator and a radical curing accelerator. You may go out.

  The curing accelerator preferably contains an anionic curing accelerator, and the anionic curing accelerator is preferably an imidazole compound. When the curing of the resin material does not proceed sufficiently, the dielectric loss tangent increases and the linear expansion coefficient may increase. However, the curing of the resin material proceeds favorably by using these curing accelerators. be able to. The curing accelerator preferably contains the radical curing accelerator and the imidazole compound. The radical curing accelerator is preferably a radical curing accelerator whose reaction temperature in the presence of the radical curing accelerator is higher than the temporary curing temperature before etching and lower than the main curing temperature after etching.

  The content of the curing accelerator is not particularly limited. The content of the curing accelerator is preferably 0.01% by weight or more in 100% by weight of the component excluding the inorganic filler and solvent in the resin material and in 100% by weight of the component excluding the inorganic filler in the cured body. , More preferably 0.05% by weight or more, preferably 5% by weight or less, more preferably 3% by weight or less. When the content of the curing accelerator is not less than the above lower limit and not more than the above upper limit, the resin material is efficiently cured. If content of the said hardening accelerator is a more preferable range, the storage stability of a resin material will become still higher and a much more preferable hardening body will be obtained.

[Thermoplastic resin]
The resin material preferably contains a thermoplastic resin. Examples of the thermoplastic resin include polyvinyl acetal resin, polyimide resin, and phenoxy resin. As for the said thermoplastic resin, only 1 type may be used and 2 or more types may be used together.

  Regardless of the curing environment, the thermoplastic resin is preferably a phenoxy resin from the viewpoint of effectively reducing the dielectric loss tangent and effectively improving the adhesion of the metal wiring. By using the phenoxy resin, deterioration of the embedding property of the resin film with respect to the holes or irregularities of the circuit board and non-uniformity of the inorganic filler can be suppressed. In addition, since the melt viscosity can be adjusted by using a phenoxy resin, the dispersibility of the inorganic filler is improved, and the resin material or the B-staged product is difficult to wet and spread in an unintended region during the curing process.

  The phenoxy resin contained in the resin material is not particularly limited. A conventionally known phenoxy resin can be used as the phenoxy resin. As for the said phenoxy resin, only 1 type may be used and 2 or more types may be used together.

  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.

  Examples of commercially available phenoxy resins include “YP50”, “YP55” and “YP70” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and “1256B40”, “4250”, “4256H40” manufactured by Mitsubishi Chemical Corporation, “ 4275 "," YX6954BH30 "," YX8100BH30 ", and the like.

  From the viewpoint of reducing the dielectric loss tangent, handling properties, plating peel strength at low roughness, and the adhesion between the insulating layer and the metal layer, the thermoplastic resin is preferably a polyimide resin (polyimide compound).

  From the viewpoint of improving solubility, the polyimide compound is preferably a polyimide compound obtained by a method of reacting tetracarboxylic dianhydride and dimer diamine.

  Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and 3,3 ′, 4,4′-biphenylsulfonetetra. Carboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether Tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic dianhydride, 1,2 , 3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxypheno) Ii) 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, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, etc. .

  Examples of the dimeramine include Versamine 551 (trade name, manufactured by BASF Japan, 3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl) cyclohexene), Versamine 552 (trade name, Cognix Japan Co., Ltd., hydrogenated product of Versamine 551), PRIAMINE 1075, PRIAMINE 1074 (trade names, both of which are manufactured by Claude Japan Co., Ltd.) and the like.

  From the viewpoint of obtaining a more excellent resin material due to storage stability, the weight average molecular weight of the thermoplastic resin, the polyimide resin, and the phenoxy resin is preferably 5000 or more, more preferably 10,000 or more, still more preferably 15000 or more, Preferably it is 100,000 or less, More preferably, it is 50000 or less.

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

  Content of the said thermoplastic resin, the said polyimide resin, and the said phenoxy resin is not specifically limited. The content of the thermoplastic resin in 100% by weight of the component excluding the inorganic filler and solvent in the resin material and 100% by weight of the cured body (if the thermoplastic resin is a polyimide resin or a phenoxy resin, polyimide The content of the resin or phenoxy resin) is preferably 1% by weight or more, more preferably 2% by weight or more. The content of the thermoplastic resin in 100% by weight of the component excluding the inorganic filler and solvent in the resin material and 100% by weight of the cured body (if the thermoplastic resin is a polyimide resin or a phenoxy resin, polyimide The content of the resin or phenoxy resin) is preferably 30% by weight or less, more preferably 20% by weight or less. When the content of the thermoplastic resin is not less than the above lower limit and not more than the above upper limit, the embedding property of the resin material in the holes or irregularities of the circuit board becomes good. When the content of the thermoplastic resin is not less than the above lower limit, the resin film can be formed more easily, and a better insulating layer can be obtained. When the content of the thermoplastic resin is not more than the above upper limit, the thermal expansion coefficient of the cured product is further reduced. When the content of the thermoplastic resin is not more than the above upper limit, the surface roughness of the surface of the insulating layer is further reduced, and the adhesive strength between the insulating layer 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. Moreover, the said solvent may be used in order to obtain the slurry containing the said inorganic filler. As for the said solvent, only 1 type may be used and 2 or more types may be used together.

  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, Examples thereof include N, N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidone, n-hexane, cyclohexane, cyclohexanone, and naphtha as a mixture.

  Most of the solvent is preferably removed when the resin material 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 material is not particularly limited. The content of the solvent can be appropriately changed in consideration of the coating property of the resin material.

[Other ingredients]
For the purpose of improving impact resistance, heat resistance, resin compatibility and workability, etc., the above resin materials include leveling agents, flame retardants, coupling agents, colorants, antioxidants, UV degradation inhibitors, You may add foaming agents, thickeners, thixotropic agents, and other thermosetting compounds other than bismaleimide compounds, bisbenzoxazine compounds and epoxy compounds.

  Examples of the coupling agent include silane coupling agents, titanium coupling agents, and aluminum coupling agents. Examples of the silane coupling agent include vinyl silane, amino silane, imidazole silane, and epoxy silane.

  Other thermosetting compounds include polymaleimide compounds, polyphenylene ether compounds, divinyl benzyl ether compounds, polyarylate compounds, diallyl phthalate compounds, benzoxazine compounds, benzoxazole compounds, and acrylate compounds that are different from bisbenzoxazine compounds. Is mentioned. For example, even when the polymaleimide compound is included as the other thermosetting compound, the effect of the present invention is exhibited. Moreover, even if it is a case where other thermosetting compounds other than a polymaleimide compound are included, the effect of this invention is exhibited.

(Resin film and laminated film)
A resin film (B-staged product / B-stage film) can be obtained by molding the resin material described above into a film. The resin material is preferably a resin film. The resin film is preferably a B stage film. By curing the resin film, the film-shaped cured body can be obtained. The cured body is preferably in the form of a film.

  Examples of a method for forming a resin composition into a film to obtain a resin film include the following methods. An extrusion molding method in which a resin composition is melt-kneaded and extruded using an extruder, and then molded into a film shape by a T die or a circular die. A casting molding method in which a resin composition containing a solvent is cast to form a film. Other known film forming methods. The extrusion molding method or the casting molding method is preferable because it can cope with the reduction in thickness. The film includes a sheet.

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

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

  The resin film may not be a prepreg. When the resin film is not a prepreg, migration does not occur along the glass cloth or the like. Further, when laminating or precuring the resin film, the surface is not uneven due to the glass cloth. The said resin film can be used with the form of a laminated film provided with metal foil or a base material, and the resin film laminated | stacked on the surface of this metal foil or base material. The metal foil is preferably a copper foil.

  Examples of the substrate of the laminated film include polyester resin films such as polyethylene terephthalate film and polybutylene terephthalate film, olefin resin films such as polyethylene film and polypropylene film, and polyimide resin film. The surface of the base material may be subjected to a release treatment as necessary.

  From the viewpoint of more uniformly controlling the degree of cure of the resin film, the thickness of the resin film is preferably 5 μm or more, and preferably 200 μm or less. When using the said resin film as an insulating layer of a circuit, it is preferable that the thickness of the insulating layer formed with the said resin film is more than the thickness of the conductor layer (metal layer) which forms a circuit. The thickness of the insulating layer is preferably 5 μm or more, and preferably 200 μm or less.

  From the viewpoint of easily forming the island portion and easily forming the sea-island structure, the drying temperature when the resin material is dried to obtain a cured product is preferably 80 ° C. or higher and 110 ° C. or lower.

(Semiconductor devices, printed wiring boards, copper-clad laminates and multilayer printed wiring boards)
The resin material and the cured body are suitably used for forming an insulating layer in a printed wiring board.

  The printed wiring board can be obtained, for example, by heat-pressing the resin material.

  A metal foil can be laminated on one side or both sides of the resin film. The 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 using an apparatus such as a parallel plate press or a roll laminator while applying pressure while heating or without heating.

  The resin material and the cured body are suitably used for obtaining a copper-clad laminate. An example of the copper-clad laminate includes a copper-clad laminate including a copper foil and a resin film laminated on one surface of the copper foil.

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

  The resin material and the cured body are preferably used for obtaining a multilayer substrate.

  As an example of the multilayer substrate, a multilayer substrate including a circuit substrate and an insulating layer stacked on the circuit substrate can be given. The material of the insulating layer of this multilayer substrate is the above-described cured body. Moreover, the insulating layer of the multilayer substrate may be formed of the resin film of the laminated film using a laminated film. The insulating layer is preferably laminated on the surface of the circuit board on which the circuit is provided. 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 substrate is laminated is roughened.

  As the roughening treatment method, a conventionally known roughening treatment method can be used, and it 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 said multilayer substrate is further equipped with the copper plating layer laminated | stacked on the surface by which the roughening process of the said insulating layer was carried out.

  As another example of the multilayer board, the circuit board, the insulating layer laminated on the surface of the circuit board, and the surface of the insulating layer opposite to the surface on which the circuit board is laminated are laminated. And a multilayer substrate provided with copper foil. The material of the insulating layer of this multilayer substrate is the above-described cured body. The insulating layer is preferably formed by curing the resin film using a copper-clad laminate including a copper foil and a resin film laminated on one surface of the copper foil. Furthermore, it is preferable that the copper foil is etched and is a copper circuit.

  Another example of the multilayer substrate is a multilayer substrate including a circuit board and a plurality of insulating layers stacked on the surface of the circuit board. At least one of the plurality of insulating layers disposed on the circuit board is formed using the resin material. The material of the insulating layer of this multilayer substrate is the above-described cured body. It is preferable that the multilayer substrate further includes a circuit laminated on at least one surface of the insulating layer formed using the resin film.

  Among multilayer substrates, multilayer printed wiring boards are required to have a low dielectric loss tangent and to have high insulation reliability due to an insulating layer. In the resin material according to the present invention, the dielectric loss tangent can be lowered, the thermal dimensional stability can be increased, and the insulation reliability can be effectively increased. Therefore, the cured body according to the present invention is suitably used for forming an insulating layer in a multilayer printed wiring board.

  The multilayer printed wiring board includes, for example, a circuit board, a plurality of insulating layers arranged on the surface of the circuit board, and a metal layer arranged between the plurality of insulating layers. The material of at least one of the insulating layers is the above-described cured body.

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

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

  In the multilayer printed wiring board 11, the insulating layers 13-16 are formed with the said hardening body. In the multilayer printed wiring board 11, the material of the insulating layers 13-16 is the said hardening body. In this embodiment, since the surfaces of the insulating layers 13 to 16 are roughened, fine holes (not shown) are formed on the surfaces of the insulating layers 13 to 16. Further, the metal layer 17 reaches the inside of the fine hole. Moreover, in the multilayer printed wiring board 11, the width direction dimension (L) of the metal layer 17 and the width direction dimension (S) of the part in which the metal layer 17 is not formed can be made small. In the multilayer printed wiring board 11, good insulation reliability is imparted between an upper metal layer and a lower metal layer that are not connected by via-hole connection and through-hole connection (not shown).

(Roughening treatment and swelling treatment)
The resin material is preferably used for obtaining a cured body to be roughened or desmeared. The cured body includes a precured body that can be further cured. From the viewpoint of easily forming a sea-island structure, the cured body is preferably a pre-cured body that can be further cured. Moreover, in order to obtain the said precured body, it is preferable that the curing temperature at the time of hardening a resin material is 120 degreeC or more and 180 degrees C or less.

  In order to form fine irregularities on the surface of the cured body obtained by pre-curing the resin material, the cured body is preferably roughened. Prior to the roughening treatment, the cured body is preferably subjected to a swelling treatment. The cured body is preferably swelled after preliminary curing and before the roughening treatment, and further cured after the roughening treatment. However, the cured body does not necessarily have to undergo a swelling treatment.

  As a method for the swelling treatment, for example, a method of treating a cured product with an aqueous solution or an organic solvent dispersion of a compound mainly composed of ethylene glycol or the like 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 body with a 40 wt% ethylene glycol aqueous solution at a treatment temperature of 30 ° C. to 85 ° C. for 1 minute to 30 minutes. The swelling treatment temperature is preferably in the range of 50 ° C to 85 ° C. When the temperature of the swelling treatment is too low, it takes a long time for the swelling treatment, and the adhesive strength between the cured body and the metal layer tends to be low.

  For the roughening treatment, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound, or a persulfuric acid compound is used. These chemical oxidizers are used as an aqueous solution or an organic solvent dispersion after water or an organic solvent is added. The roughening liquid used for the roughening treatment generally contains an alkali as a pH adjuster or the like. The roughening solution 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 arithmetic average roughness Ra of the surface of the cured body is preferably 10 nm or more, preferably less than 300 nm, more preferably less than 200 nm, and still more preferably less than 150 nm. In this case, the adhesive strength between the insulating layer and the metal layer is increased, and further finer wiring is formed on the surface of the insulating layer. Furthermore, conductor loss can be suppressed and signal loss can be suppressed low. The arithmetic average roughness Ra is measured in accordance with JIS B0601: 1994.

(Desmear treatment)
A through-hole may be formed in the cured body obtained by precuring the resin material. In the multilayer substrate or the like, a via or a through hole is formed as a through hole. For example, the via can be formed by irradiation with a laser such as a CO ₂ laser. The diameter of the via is not particularly limited, but is about 60 μm to 80 μm. Due to the formation of the through hole, a smear that is a resin residue derived from the resin component contained in the cured body is often formed at the bottom of the via.

  In order to remove the smear, the surface of the cured body is preferably desmeared. The desmear process may also serve as a roughening process.

  In the desmear treatment, for example, a chemical oxidant such as a manganese compound, a chromium compound, or a persulfate compound is used as in the roughening treatment. These chemical oxidizers are used as an aqueous solution or an organic solvent dispersion after water or an organic solvent is added. The desmear treatment liquid used for the desmear treatment generally contains an alkali. The desmear treatment liquid preferably contains sodium hydroxide.

  By using the resin material, the surface roughness of the desmeared insulating layer becomes sufficiently small.

  Hereinafter, the present invention will be specifically described by giving examples and comparative examples. The present invention is not limited to the following examples.

(Bismaleimide compound)
N-alkyl bismaleimide compound 1 (designer Moleculars Inc. "BMI-1500", molecular weight 1500)
N-alkyl bismaleimide compound 2 (Designer Moleculars Inc. "BMI-1700", molecular weight 1700)
N-alkyl bismaleimide compound 3 (designer Moleculars Inc. "BMI-3000", molecular weight 3000 (weight average molecular weight 8000))
N-alkylbismaleimide compound 4 (“BMI-3000J” manufactured by Designer Molecules Inc., molecular weight 3000 (weight average molecular weight 11000))
N-alkyl bismaleimide compound 5 (designer molecules Inc. "BMI-3000J" was dissolved in a toluene solution, isopropanol was added, and the reprecipitated polymer component was recovered (BMI-3000J treatment in the table) And weight average molecular weight 15000)

(Bisbenzoxazine compound)
N-alkylbenzoxazine compound (synthesized according to Synthesis Example 1, molecular weight 3000, weight average molecular weight 7700)

(Synthesis Example 1)
In a reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen gas introduction tube, 65 g of pyromellitic dianhydride (Tokyo Chemical Industry Co., Ltd., molecular weight 218.12) and 500 mL of cyclohexanone were added, After 164 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan Co., Ltd.) was dissolved in cyclohexanone, it was added dropwise. Thereafter, a Dean-Stark trap and a condenser were attached to the flask, and the mixture was heated to reflux for 2 hours to obtain an imide compound having an amine structure at both ends. A mixture obtained by mixing 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.) was further refluxed for 12 hours to obtain benzoxazine. Made. Then, N-alkylbenzoxazine compound was obtained by reprecipitation with isopropanol.

(Other)
N-phenylmaleimide compound (“BMI-4000” manufactured by Daiwa Kasei Kogyo Co., Ltd.)

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

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

(Curing agent)
Component X:
Cyanate ester compound-containing liquid (Lonza Japan "BA-3000S", solid content 75 wt%)
Active ester compound 1-containing liquid (DIC Corporation "EXB-9416-70BK", solid content 70 wt%)
Active ester compound 2 containing liquid (“HPC-8000L” manufactured by DIC, solid content 65% by weight)
Active ester compound 3 containing liquid (“HPC-8150” manufactured by DIC, 62 wt% solid content)
Phenol compound-containing liquid (DIC Corporation "LA-1356", solid content 60% by weight)
Carbodiimide compound-containing liquid (Nisshinbo Chemical "V-03", solid content 50 wt%)

(Curing accelerator)
Dimethylaminopyridine (“DMAP” manufactured by Wako Pure Chemical Industries, Ltd.)
2-Phenyl-4-methylimidazole (“2P4MZ” manufactured by Shikoku Chemicals)
2-Ethyl-4-methylimidazole (“2E4MZ” manufactured by Shikoku Chemicals)
Park Mill D (manufactured by NOF Corporation)

(Thermoplastic resin)
Phenoxy resin (Mitsubishi Chemical "YX6954BH30")
Polyimide compound (polyimide resin):
A polyimide compound-containing solution (nonvolatile content: 26.8% by weight), which is a reaction product of tetracarboxylic dianhydride and dimer diamine, was synthesized according to Synthesis Example 2 below.

(Synthesis Example 2)
In a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube, 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. Subsequently, 89.0 g of dimer diamine (“PRIAMINE 1075” manufactured by Claude Japan) and 54.7 g of 1,3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Company) were dropped into the reaction vessel. Next, 121.0 g of methylcyclohexane and 423.5 g of ethylene glycol dimethyl ether were added to the reaction vessel, and an imidization reaction was performed at 140 ° C. for 10 hours. In this way, 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 20000. The molar ratio of acid component / amine component was 1.04.

  The molecular weight of the polyimide compound synthesized in Synthesis Example 2 was determined as follows.

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

(Examples 1-17 and Comparative Examples 1-3)
The components shown in Tables 1 and 2 below were blended in the blending amounts shown in Tables 1 and 2 (units are solid parts by weight) and stirred at room temperature until a uniform solution was obtained, to obtain resin materials.

  Using an applicator, the resin material obtained on the release-treated surface of the release-treated PET film (“XG284” manufactured by Toray Industries Inc., thickness 25 μm) was applied, and then in a gear oven at 100 ° C. for 2 minutes. It was dried for 30 seconds to volatilize the solvent. In this way, 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.

  Thereafter, the laminated film was heated at 190 ° C. for 90 minutes to produce a cured body in which the resin film was cured.

(Evaluation)
(1) State of sea-island structure A cross section of the obtained cured body was observed with a scanning electron microscope (SEM) at a magnification of 1500 times in a reflected electron mode, and the presence or absence of phase separation within 3200 μm ² was evaluated. Furthermore, when the sea-island structure exists, the major axis of each island part was measured from the observation image. The average major axis of each island was obtained by averaging the measured values of the major axis of each island.

(2) 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 obtained laminate was heated at 190 ° C. for 90 minutes to obtain a cured body. About the obtained hardened | cured material, it uses a "cavity resonance perturbation method dielectric constant measuring device CP521" made by Kanto Electronics Application Development Co., Ltd. and "Network Analyzer N5224A PNA" made by Keysight Technology Co., Ltd. at room temperature (23 ° C) by the cavity resonance method. The dielectric loss tangent was measured at a frequency of 1.0 GHz.

(3) Thermal dimensional stability (average coefficient of linear expansion (CTE))
The cured body obtained by heating the obtained resin film (B stage film) having a thickness of 40 μm at 190 ° C. for 90 minutes was cut into a size of 3 mm × 25 mm. Using a thermomechanical analyzer (“EXSTAR TMA / SS6100” manufactured by SII Nano Technology), the cured product cut at 25 ° C. to 150 ° C. under conditions of a tensile load of 33 mN and a heating rate of 5 ° C./min. The average linear expansion coefficient (ppm / ° C.) was calculated. The average linear expansion coefficient was determined according to the following criteria.

[Criteria for average linear expansion coefficient]
○○: Average linear expansion coefficient is 25 ppm / ° C. or less ○: Average linear expansion coefficient exceeds 25 ppm / ° C. and 30 ppm / ° C. or less X: Average linear expansion coefficient exceeds 30 ppm / ° C.

(4) Elastic modulus The cured product obtained by heating the obtained resin film (B stage film) having a thickness of 40 μm at 190 ° C. for 90 minutes was cut into a size of 10 mm × 100 mm. Using a tensile tester (“AGS-J 100N” manufactured by SHIMADZU), distance between chucks: 60 mm, tensile speed: 5 mm / min, initial tension: 0.35 N, preload speed: 100 mm / min, sampling cycle: 50 ms The tensile test was performed under the conditions of the above, and the elastic modulus at the maximum inclination of the stroke (displacement) and the test force was calculated. The measurement was performed 5 times, and the average value of the elastic modulus was calculated to obtain the average elastic modulus. The elastic modulus was determined according to the following criteria.

[Criteria for elastic modulus]
◯: Average elastic modulus exceeds 7 MPa ○: Average elastic modulus exceeds 4 MPa and 7 MPa or less X: Average elastic modulus is 4 MPa or less

(5) Surface roughness (surface roughness after roughening treatment)
Lamination process and semi-curing treatment:
A double-sided copper-clad laminate (CCL substrate) (“E679FG” manufactured by Hitachi Chemical Co., Ltd.) was prepared. Both surfaces of the copper foil surface of this double-sided copper-clad laminate were immersed in “Cz8101” manufactured by MEC, and the surface of the copper foil was roughened. Using a “batch type vacuum laminator MVLP-500-IIA” manufactured by Meiki Seisakusho on both sides of the roughened copper clad laminate, the resin film (B stage film) side of the laminate film is on the copper clad laminate. And laminated to obtain a laminated structure. The laminating conditions were such that the pressure was reduced to 30 hPa or less by reducing the pressure for 30 seconds, and then pressing was performed at 100 ° C. and a pressure of 0.4 MPa for 30 seconds. Then, it heated at 180 degreeC for 30 minute (s), and the resin film was semi-hardened. Thus, the laminated body by which the hardening body was laminated | stacked on the CCL board | substrate was obtained.

Roughening process:
(A) Swelling treatment:
The obtained laminate was put in a swelling liquid at 60 ° C. (“Swelling Dip Securigant P” manufactured by Atotech Japan Co., Ltd.) and rocked for 10 minutes. Thereafter, it was washed with pure water.

(B) Permanganate treatment (roughening treatment and desmear treatment):
The layered product after the swelling treatment was put into a roughened aqueous solution of potassium permanganate (“Concentrate Compact CP” manufactured by Atotech Japan Co., Ltd.) at 80 ° C. and rocked for 30 minutes. Next, after processing for 2 minutes using a 25 degreeC washing | cleaning liquid ("Reduction securigant P" by Atotech Japan), it wash | cleaned with the pure water and the evaluation sample was obtained.

Surface roughness measurement:
Using a non-contact three-dimensional surface shape measuring device (“WYKO NT1100” manufactured by Veeco), the arithmetic average roughness Ra is measured on the surface of the evaluation sample (roughened cured body) in a measurement area of 94 μm × 123 μm. did. The arithmetic average roughness Ra was measured according to JIS B0601 (1994). The surface roughness was determined according to the following criteria.

[Surface roughness criteria]
○○: Ra is less than 50 nm ○: Ra is 50 nm or more and less than 200 nm ×: Ra is 200 nm or more

(6) Peeling peel strength Electroless plating treatment:
(5) The surface of the roughened cured body obtained by the evaluation of the surface roughness was treated with a 60 ° C. alkaline cleaner (“Cleaner Securigant 902” manufactured by Atotech Japan) for 5 minutes and degreased and washed. After washing, the cured product was treated with a 25 ° C. pre-dip solution (“Pre-Dip Neogant B” manufactured by Atotech Japan) for 2 minutes. Thereafter, the cured body was treated with an activator solution at 40 ° C. (“Activator Neo Gantt 834” manufactured by Atotech Japan) for 5 minutes to attach a palladium catalyst. Next, the cured body was treated with a reducing solution at 30 ° C. (“Reducer Neogant WA” manufactured by Atotech Japan) for 5 minutes.

  Next, the cured product is placed in a chemical copper solution (“Basic Print Gantt MSK-DK”, “Copper Print Gantt MSK”, “Stabilizer Print Gantt MSK”, and “Reducer Cu” manufactured by Atotech Japan) and electroless plating. Was carried out until the plating thickness reached about 0.5 μm. After electroless plating, annealing was performed at a temperature of 120 ° C. for 30 minutes in order to remove the remaining hydrogen gas. In addition, all the processes up to the electroless plating process were performed while using a beaker scale with a treatment liquid of 2 L and swinging the cured body.

Electroplating treatment:
Next, electrolytic plating was performed on the cured body subjected to the electroless plating treatment until the plating thickness became 25 μm. As an electrolytic copper plating, a copper sulfate solution (“copper sulfate pentahydrate” manufactured by Wako Pure Chemical Industries, “sulfuric acid” manufactured by Wako Pure Chemical Industries, “basic leveler kaparaside HL” manufactured by Atotech Japan, “ using the correction agent Cupracid GS "), plating thickness passing a current of 0.6 a / cm ² was carried out electrolytic plating until approximately 25 [mu] m. After the copper plating treatment, the cured body was heated at 190 ° C. for 90 minutes to further cure the cured body. Thus, the hardened | cured material with which the copper plating layer was laminated | stacked on the upper surface was obtained.

Measurement of plating peel strength:
A strip-shaped cut having a width of 0.5 cm was made on the surface of the copper plating layer of the cured product obtained by laminating the obtained copper plating layer on the upper surface. Set a cured product with a copper plating layer laminated on the top surface in a 90 ° peel tester ("TE-3001" manufactured by Tester Sangyo Co., Ltd.), pick up the end of the copper plating layer with the notch, The plating layer was peeled by 15 mm and the peel strength (plating peel strength) was measured.

[Criteria for plating peel strength]
◯: Plating peel strength is 0.5 kgf or more ○: Plating peel strength is 0.3 kgf or more and less than 0.5 kgf ×: Plating peel strength is less than 0.3 kgf

(7) Adhesion between the insulating layer and the metal layer (peel strength)
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 surfaces of the copper foil surface of this double-sided copper-clad laminate were immersed in “Cz8101” manufactured by MEC, and the surface of the copper foil was roughened. Using a “batch type vacuum laminator MVLP-500-IIA” manufactured by Meiki Seisakusho on both sides of the roughened copper clad laminate, the resin film (B stage film) side of the laminate film is on the copper clad laminate. And laminated to obtain a laminated structure. The laminating conditions were such that the pressure was reduced to 30 hPa or less by reducing the pressure for 30 seconds, and then pressing was performed at 100 ° C. and a pressure of 0.4 MPa for 30 seconds.

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

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

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

[Judgment 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

(8) Thermal shock test An evaluation board (an evaluation board provided with a copper-clad laminate and six insulating-wiring circuit composite layers) for a thermal shock test was produced according to the following. In the evaluation substrate, via holes formed in each layer are connected. That is, the following evaluation was performed on an evaluation board having a multistage stacked via.

Formation of the first insulation-wiring circuit composite layer:
(A1) Laminating step:
A double-sided copper-clad laminate (CCL substrate) (copper foil thickness 18 μm on each side, substrate thickness 0.7 mm, substrate size 100 mm × 100 mm, “MCL-E679FG” manufactured by Hitachi Chemical Co., Ltd.) was prepared. Both surfaces of the copper foil surface of this double-sided copper-clad laminate were immersed in “Cz8101” manufactured by MEC, and the surface of the copper foil was roughened. Using a “batch type vacuum laminator MVLP-500 / 600-IIA” manufactured by Meiki Seisakusho on both sides of the roughened copper clad laminate, the resin film (B stage film) side of the laminate film is copper clad. Laminated on the plate. The laminating conditions were such that the pressure was reduced to 30 hPa or less by reducing the pressure for 30 seconds, and then pressing was performed at 100 ° C. and a pressure of 0.4 MPa for 30 seconds. After peeling off the PET film, it was heated at 130 ° C. for 60 minutes to semi-cure (pre-cure) the resin film. Thus, the laminated body (1) by which the semi-cured material of the resin film was laminated | stacked on the CCL board | substrate was obtained.

(B1) Via hole forming step:
Using a CO ₂ laser processing machine (“LC-4KF212” manufactured by Via Mechanics, Inc.), a via hole having a diameter of about 60 μm was formed under the conditions of burst mode, energy 0.4 mJ, pulse 27 μsec, and 3 shots.

(C1) Desmear treatment and roughening treatment:
(C1-1) Swelling treatment:
The obtained laminate (1) was placed in a swelling liquid at 60 ° C. (“Swelling Dip Securigant P” manufactured by Atotech Japan Co., Ltd.) and rocked for 10 minutes. Thereafter, it was washed with pure water.

(C1-2) Permanganate treatment (roughening treatment and desmear treatment):
The layered product (1) after the swelling treatment was placed in a roughened aqueous solution of potassium permanganate (“Concentrate Compact CP” manufactured by Atotech Japan Co., Ltd.) at 80 ° C. and rocked for 30 minutes. Next, after processing for 2 minutes using a 25 degreeC washing | cleaning liquid ("Reduction securigant P" by Atotech Japan), it wash | cleaned with the pure water and obtained the laminated body (1) after a roughening process.

(C1-3) Measurement of surface roughness:
Using a non-contact three-dimensional surface shape measuring device (“Contour GT-K” manufactured by Bruker), the surface of the layered product (1) (roughened cured product) after the roughening treatment was 95.6 μm × Arithmetic mean roughness Ra was measured in a measurement area of 71.7 μm. The arithmetic average roughness Ra was measured according to JIS B0601: 1994. It was confirmed that the surface roughness of the roughened cured product was 200 nm or less.

(D1) Electroless plating treatment:
The surface of the cured product of the laminate (1) after the roughening treatment was treated with an alkali cleaner (“Cleaner Securigant 902” manufactured by Atotech Japan) for 5 minutes and degreased and washed. After washing, the cured product was treated with a 25 ° C. pre-dip solution (“Pre-Dip Neogant B” manufactured by Atotech Japan) for 2 minutes. Thereafter, the cured product was treated with an activator solution at 40 ° C. (“Activator Neo Gantt 834” manufactured by Atotech Japan) for 5 minutes to attach a palladium catalyst. Next, the cured product was treated with a reducing solution at 30 ° C. (“Reducer Neogant WA” manufactured by Atotech Japan) for 5 minutes.

  Next, the cured product is placed in a chemical copper solution (“Basic Print Gantt MSK-DK”, “Copper Print Gantt MSK”, “Stabilizer Print Gantt MSK”, and “Reducer Cu” manufactured by Atotech Japan), and electroless plating is performed. Was carried out until the plating thickness reached about 0.5 μm. After the electroless plating, annealing was performed at a temperature of 120 ° C. for 30 minutes in order to remove the remaining hydrogen gas. In addition, all processes up to the electroless plating process were performed while setting the treatment liquid to 2 L on a beaker scale and swinging the cured product.

(E1) Resist formation:
A dry film resist (“RY5125” manufactured by Hitachi Chemical Co., Ltd.) was attached using a hot roll laminator. Lamination conditions were set to a temperature of 100 ° C., a pressure of 0.4 MPa, and a lamination speed of 1.5 m / min, and then held for 15 minutes. Next, after exposure at 85 mJ / cm ² , development was performed by spraying a 1 wt% sodium carbonate aqueous solution at 27 ° C. and a spray pressure of 1.2 MPa for 30 seconds.

(F1) Electroplating treatment:
Next, electrolytic plating was performed on the cured product that had been subjected to electroless plating until the plating thickness reached 25 μm. As an electrolytic copper plating, a copper sulfate solution (“copper sulfate pentahydrate” manufactured by Wako Pure Chemical Industries, “sulfuric acid” manufactured by Wako Pure Chemical Industries, “basic leveler kaparaside HL” manufactured by Atotech Japan, “ using the correction agent Cupracid GS "), plating thickness passing a current of 0.6 a / cm ² was carried out electrolytic plating until approximately 25 [mu] m.

(G1) DFR peeling and etching treatment:
The dry film resist (DFR) was peeled off by spraying using a 3 wt% aqueous sodium hydroxide solution. Next, quick etching was performed with a perhydrosulfuric acid-based acidic etching solution (“SAC process” manufactured by JCU).

(H1) Main curing step:
With respect to the peak temperature T, it heated at 190 degreeC for 1.5 hours.
In this way, a first insulating-wiring circuit composite layer was formed on the copper clad laminate.
Formation of the second insulating-wiring circuit composite layer:

(A2) Lamination process:
(A1) The roughening process of the 1st wiring circuit layer was performed like the roughening process conditions implemented at the lamination process. Thereafter, the resin film (B stage film) side of the laminated film was laminated on the first insulating-wiring circuit composite layer under the laminating conditions carried out in the (a1) laminating step. Then, after peeling off the PET film, the resin film was semi-cured by heating at 130 ° C. for 60 minutes. In this way, a laminate (2) in which a semi-cured resin film was laminated on the first insulating-wiring circuit composite layer was obtained.

(B2) Via hole formation process:
(B1) A via hole was formed in the same manner as in the step of forming the via hole except that the stacked body (1) was changed to the stacked body (2).

(C2) Desmear treatment and roughening treatment:
(C1) Except having changed the laminated body (1) into the laminated body (2), the process implemented by the desmear process and the roughening process was performed similarly, and the laminated body (2) after the roughening process was obtained.

(D2) Electroless plating treatment:
(D1) The electroless plating treatment is performed in the same manner as in the step performed by the electroless plating treatment except that the roughened laminate (1) is changed to the roughened laminate (2). It was.

(F2) Electroplating treatment:
(D2) After performing the electroless plating treatment, the electroless plating treatment was performed in the same manner as (f1) electrolytic plating treatment.

(H2) Main curing step:
(H1) It heated at 190 degreeC for 1.5 hours similarly to this hardening process.

  In this way, a second insulating-wiring circuit composite layer was formed on the first insulating-wiring circuit composite layer.

Formation of third layer insulation-wiring circuit composite layer:
A third insulating-wiring circuit composite layer was formed on the second insulating-wiring circuit composite layer in the same manner as the process performed in the formation of the second insulating-wiring circuit composite layer.

Formation of the fourth insulation-wiring circuit composite layer:
A fourth insulating-wiring circuit composite layer was formed on the third insulating-wiring circuit composite layer in the same manner as in the process of forming the second insulating-wiring circuit composite layer.

Formation of fifth-layer insulation-wiring circuit composite layer:
(A5) Lamination process:
(A2) A laminate (5) in which a semi-cured product of a resin film was laminated on the fourth insulating-wiring circuit composite layer was obtained in the same manner as in the laminating step.

(B5) Via hole formation process:
(B1) A via hole was formed in the same manner as in the step of forming the via hole, except that the laminate (1) was changed to the laminate (5).

(C5) Desmear treatment and roughening treatment:
(C1) Except having changed the laminated body (1) into the laminated body (5), the process implemented by the desmear process and the roughening process was performed similarly, and the laminated body (5) after the roughening process was obtained.

(D5) Electroless plating treatment:
(D1) The electroless plating treatment is performed in the same manner as in the step performed by the electroless plating treatment except that the roughened laminate (1) is changed to the roughened laminate (5). It was.

(E5) Resist formation:
(E1) Development was performed in the same manner as in the step performed for resist formation.

(F5) Electroplating treatment:
After the pattern of the dry film resist was formed, electroless plating treatment was performed in the same manner as (f1) electrolytic plating treatment.

(G5) DFR peeling and etching treatment:
(G1) DFR peeling and etching were performed in the same manner as the steps performed in DFR peeling and etching.

(H5) Main curing step:
(H1) It heated at 190 degreeC for 1.5 hours similarly to this hardening process.
In this way, a fifth insulating-wiring circuit composite layer was formed on the fourth insulating-wiring circuit composite layer.

Formation of the sixth insulating-wiring circuit composite layer:
A sixth insulating-wiring circuit composite layer was formed on the fifth insulating-wiring circuit composite layer in the same manner as the process performed in the formation of the second insulating-wiring circuit composite layer.

  Thus, the evaluation board | substrate with which the 1st-6th insulating-wiring circuit composite layer was formed on the copper clad laminated board was produced. In the obtained evaluation board, only the first and fifth wiring circuit layers have patterns in the first to sixth wiring circuit layers.

The obtained evaluation substrate was subjected to a liquid-cooling thermal shock test under the following conditions.
Test conditions: -55 ° C to 125 ° C, 5 minutes each, 1000 cycles

  Before and after the liquid-cooling thermal shock test, the resistance at the via connection site was measured using a resistance meter ("RM3545" manufactured by Hioki Electric Co., Ltd.). Before and after the liquid-cooling thermal shock test, the resistance value change rate of the evaluation substrate (resistance value after the liquid-cooling thermal shock test / resistance value after the liquid-cooling thermal shock test × 100) was determined.

[Criteria for thermal shock test]
○: Resistance value change rate is less than 10% ×: Resistance value change rate is 10% or more

  The compositions and results are shown in Tables 1 and 2 below. In Tables 1 and 2, the contents of the polyimide compound, the curing agent, and silica are described in pure amounts.

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

Claims (19)

A cured product of a resin material containing a bismaleimide compound or a bisbenzoxazine compound, an epoxy compound, and an inorganic filler,
The said hardening body is a hardening body which has a sea island structure which has a sea part and an island part.   The cured body according to claim 1, wherein the bismaleimide compound is an N-alkyl bismaleimide compound.   The cured body according to claim 2, wherein the N-alkyl bismaleimide compound is an N-alkyl bismaleimide compound having a skeleton derived from dimer diamine.   The hardening body of any one of Claims 1-3 whose average major axis of the said island part is 5 micrometers or less.   The hardened | cured material of any one of Claims 1-4 in which the said island part contains the said bismaleimide compound or the said bisbenzoxazine compound.   The resin material includes a curing agent including at least one component of a phenol compound, a cyanate ester compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a benzoxazine compound different from a bisbenzoxazine compound. Item 6. The cured product according to any one of items 1 to 5.   The cured body according to claim 6, wherein the component is a component having an aromatic skeleton.   The cured body according to any one of claims 1 to 7, wherein the epoxy compound is an epoxy compound having an aromatic skeleton.   The cured body according to any one of claims 1 to 8, wherein the molecular weight of the bismaleimide compound is 500 or more and 15000 or less.   The cured body according to any one of claims 1 to 9, wherein a content of the inorganic filler is 50% by weight or more in 100% by weight of the cured body.   The hardened | cured material of any one of Claims 1-10 whose average particle diameter of the said inorganic filler is 5 micrometers or less. The resin material includes a thermoplastic resin;
The content of the thermoplastic resin is 1% by weight or more and 20% by weight or less in 100% by weight of the component excluding the inorganic filler and the solvent in the resin material. Cured body.   The hardening body of Claim 12 whose molecular weight of the said thermoplastic resin is 15000 or more.   The cured body according to claim 12 or 13, wherein the thermoplastic resin is a polyimide compound. The resin material includes a curing accelerator;
The hardened | cured material of any one of Claims 1-14 in which the said hardening accelerator contains an anionic hardening accelerator or a radical hardening accelerator. The curing accelerator comprises the anionic curing accelerator;
The cured body according to claim 15, wherein the anionic curing accelerator is an imidazole compound.   The cured body according to any one of claims 1 to 16, which is used for forming an insulating layer in a multilayer printed wiring board. A bismaleimide compound or a bisbenzoxazine compound, an epoxy compound and an inorganic filler,
A resin material having a sea-island structure in which a cured body of the resin material has a sea part and an island part. A circuit board;
A plurality of insulating layers disposed on a surface of the circuit board;
A metal layer disposed between the plurality of insulating layers,
The multilayer printed wiring board whose material of the at least 1 layer of the said insulating layer of the said some insulating layers is the hardening body of any one of Claims 1-17.

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