JP2019173010A - Resin material, laminate film and multilayer printed wiring board - Google Patents

Abstract

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

Description

  The present invention relates to a resin material containing a polyimide compound. Moreover, this invention relates to the multilayer printed wiring board using the said resin material.

  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 the insulating layer is formed using a conventional resin material as described in Patent Document 1, the embedding property of the resin material into the unevenness of the substrate or the like is not sufficiently high, or the resin material is excessively excessive from the periphery of the substrate at the time of lamination. It may become difficult to control the film thickness. In addition, when an insulating layer is formed using a conventional resin material as described in Patent Document 2, the dielectric loss tangent of the insulating layer does not become sufficiently low, or the adhesion between the insulating layer and the copper substrate May not be high enough.

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

  Moreover, in the conventional resin material, the bending stability of the cured product may not be sufficiently high.

  As described above, 1) the embedding property to the uneven surface is increased, 2) excessive protrusion of the resin material from the periphery of the substrate during lamination is suppressed, 3) the curing temperature is suppressed, and 4) the dielectric loss tangent of the cured product is decreased. 5) There is a present situation that it is extremely difficult to improve adhesion to metal and 6) to improve the bending stability of the cured product. In other words, it is extremely difficult to obtain a resin material that exhibits all the effects 1) -6).

  The object of the present invention is to 1) increase embedding on uneven surfaces, 2) suppress excessive protrusion of the resin material from the periphery of the substrate during lamination, 3) suppress the curing temperature, and 4) reduce the dielectric loss tangent of the cured product. It is to provide a resin material that can be lowered, 5) enhanced adhesion to metal, and 6) enhanced bending stability of a cured product. Another object of the present invention is to provide a laminated film and a multilayer printed wiring board using the resin material.

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

  On the specific situation which concerns on this invention, the said aliphatic skeleton has couple | bonded with the nitrogen atom which has formed the maleimide skeleton or the benzoxazine skeleton in the said aliphatic skeleton containing compound.

  On the specific situation which concerns on this invention, the weight average molecular weight of the said polyimide compound is 15000 or more, and the weight average molecular weight of the said aliphatic skeleton containing compound is less than 15000.

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

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

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

  On the specific situation with the resin material which concerns on this invention, the said resin material contains a thermosetting compound and an inorganic filler.

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

  On the specific situation with the resin material which concerns on this invention, content of the said inorganic filler is 50 weight% or more in 100 weight% of components except the solvent in a resin material.

  On the specific situation with the resin material which concerns on this invention, content of the said polyimide compound is 3 to 80 weight% in the total of 100 weight% of the said polyimide compound and the said aliphatic skeleton containing compound.

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

  In a specific aspect of the resin material according to the present invention, the total content of the polyimide compound and the aliphatic skeleton-containing compound is 10% by weight or more and 98% by weight in 100% by weight of the organic component excluding the solvent in the resin material. % By weight or less.

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

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

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

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

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

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

  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 at least one of the layers is a cured product of the resin material described above.

  The resin material according to the present invention includes a polyimide compound and at least one aliphatic skeleton-containing compound among a maleimide compound having an aliphatic skeleton and a benzoxazine compound having an aliphatic skeleton. Since the resin material according to the present invention has the above-described configuration, 1) the embedding on the uneven surface is enhanced, 2) excessive protrusion of the resin material from the periphery of the substrate during lamination is suppressed, and 3) the curing temperature. 4) the dielectric loss tangent of the cured product can be lowered, 5) the adhesion to the metal can be increased, and 6) the folding stability of the cured product can be increased. In the resin material according to the present invention, all the effects 1) to 6) can be exhibited.

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

  Hereinafter, the present invention will be described in detail.

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

  Since the resin material according to the present invention has the above-described configuration, 1) the embedding on the uneven surface is enhanced, 2) excessive protrusion of the resin material from the periphery of the substrate during lamination is suppressed, and 3) the curing temperature. 4) the dielectric loss tangent of the cured product can be lowered, 5) the adhesion to the metal can be increased, and 6) the bending stability of the cured product can be increased. In the resin material according to the present invention, all the effects 1) to 6) can be exhibited. In the resin material according to the present invention, 5) As the adhesion to the metal, for example, the peel strength between the insulating layer and the metal layer (copper layer) can be increased.

  Moreover, in the resin material which concerns on this invention, since said structure is provided, thermal dimensional stability can be improved. In addition, since the resin material according to the present invention has the above-described configuration, handling properties can be improved.

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

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

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

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

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

  Hereinafter, the detail of each component used for the resin material which concerns on this invention, the use of the resin material which concerns on this invention, etc. are demonstrated.

[Polyimide compound]
The resin material according to the present invention includes a polyimide compound. The polyimide compound is a compound different from the maleimide compound. The polyimide compound may or may not have a maleimide skeleton at the terminal. In addition, the said polyimide compound may have an acid anhydride structure and a citraconic structure at the terminal. A conventionally known polyimide compound can be used as the polyimide compound. As for the said polyimide compound, only 1 type may be used and 2 or more types may be used together.

  The polyimide compound is a method of reacting a tetracarboxylic dianhydride and an isocyanate ester compound, a method of reacting a tetracarboxylic dianhydride and a diamine compound, and a method of reacting a tetracarboxylic dianhydride and a triamine compound. Etc. can be obtained.

  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, 1,1-bis (4-aminophenyl) cyclohexane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 2,7-diaminofluorene, 4, 4'-ethylenedianiline, isophoronediamine, 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (2,6-diethylaniline), 4,4'-methylenebis (2-ethyl-6-methyl) Aniline), 4,4′-methylenebis (2-methylcyclohexylamine), 1,4-diaminobutane, 10-diaminodecane, 1,12-diaminododecane, 1,7-diaminoheptane, 1,6-diaminohexane, 1,5-diaminopentane, 1,8-diaminooctane, 1,3-diaminopropane, 1,11 -Diaminoundecane, 2-methyl-1,5-diaminopentane, dimer diamine, etc. are mentioned.

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

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

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

  Examples of the 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). , Manufactured by Cognics Japan, hydrogenated product of Versamine 551), PRIAMINE 1075, PRIAMINE 1074 (trade names, both of which are manufactured by CRODA JAPAN).

  In a total of 100% by weight of the polyimide compound and the aliphatic skeleton-containing compound, the content of the polyimide compound is preferably 3% by weight or more, more preferably 5% by weight or more, still more preferably 10% by weight or more, preferably Is 80% by weight or less, more preferably 60% by weight or less, and still more preferably 50% by weight or less. When the content of the polyimide compound is not less than the above lower limit and not more than the above upper limit, the viscosity of the resin material does not become too high, and the handling property and the embedding property to the uneven surface can be further enhanced. Moreover, it can suppress that the flow amount at the time of lamination becomes too large that content of the said polyimide compound is more than the said minimum and below the said upper limit.

  In 100% by weight of the component excluding the inorganic filler and the solvent in the resin material, the content of the polyimide compound is preferably 3% by weight or more, more preferably 5% by weight or more, and further preferably 7% by weight or more. . In 100% by weight of the component excluding the inorganic filler and the solvent in the resin material, the content of the polyimide compound is preferably 40% by weight or less, more preferably 30% by weight or less, still more preferably 25% by weight or less, particularly Preferably it is 20 weight% or less. When the content of the polyimide compound is not less than the above lower limit, the dielectric loss tangent of the cured product can be lowered, the flow amount can be controlled well, and the adhesion between the insulating layer and the metal layer can be further enhanced. When the content of the polyimide compound is not more than the above upper limit, the embedding property to the uneven surface can be further enhanced. Handling property can be improved as content of the said polyimide compound is more than the said minimum and below the said upper limit.

  From the viewpoint of further enhancing the embedding property with respect to the uneven surface, the weight average molecular weight of the polyimide compound is preferably 15000 or more, more preferably 20000 or more, preferably less than 50000, more preferably less than 40000.

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

  When the polyimide compound has a maleimide skeleton at the end, the weight molecular weight of the polyimide compound is preferably 15000 or more, and more preferably 20000 or more.

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

<Maleimide compound having an aliphatic skeleton>
The resin material according to the present invention preferably contains a maleimide compound having an aliphatic skeleton (hereinafter sometimes referred to as maleimide compound X) as the aliphatic skeleton-containing compound. The maleimide compound X is a compound different from the polyimide compound. The maleimide compound X has a maleimide group. The maleimide compound X has a maleimide group at the terminal. The maleimide compound X has an aliphatic skeleton. Therefore, the maleimide compound X has a maleimide group and an aliphatic skeleton. In the maleimide compound X, it is preferable that the aliphatic skeleton is bonded to the nitrogen atom forming the maleimide skeleton. The maleimide compound X may have an imide skeleton. As the maleimide compound X, a conventionally known maleimide compound can be used. The maleimide compound X includes a citraconic imide 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. The maleimide compound X may have a citraconimide structure at the terminal. As for the said maleimide compound X, only 1 type may be used and 2 or more types may be used together.

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

  The maleimide compound X having a skeleton derived from the reaction product of the polyamine compound having an aliphatic skeleton and a carboxylic dianhydride can be obtained, for example, by reacting a polyamine compound having an aliphatic skeleton with a carboxylic dianhydride. After obtaining a reaction product having an amino group at the end, it can be obtained by reacting the reaction product with maleic anhydride.

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

  The maleimide compound X having a skeleton derived from the reaction product of the diamine compound having an aliphatic skeleton and a carboxylic dianhydride can be obtained by reacting, for example, a diamine compound having an aliphatic skeleton with a carboxylic dianhydride at both ends. Can be obtained by reacting the reactant with maleic anhydride.

  The maleimide compound X having a skeleton derived from the reaction product of the triamine compound having an aliphatic skeleton and a carboxylic dianhydride is obtained by reacting, for example, a triamine compound having an aliphatic skeleton with a carboxylic dianhydride at both ends. Can be obtained by reacting the reactant with maleic anhydride.

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

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

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

  Examples of the carboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, and 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic acid. Acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetra Carboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic dianhydride, 1,2, 3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) Phenylsulfone 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 (tri Phenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, and the like.

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

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

  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). , Manufactured by Cognics Japan, hydrogenated product of Versamine 551), PRIAMINE 1075, PRIAMINE 1074 (trade names, both of which are manufactured by CRODA JAPAN).

  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. .

  The maleimide compound X is preferably an N-alkylbismaleimide compound having a skeleton derived from dimer diamine from the viewpoint of more effectively exerting the effects of the present invention 1) -6) described above.

  Examples of commercially available N-alkylbismaleimide compounds having a skeleton derived from dimer diamine include Designers Molecules Inc. “BMI-1500”, “BMI-1700”, and “BMI-3000” manufactured by the company are listed.

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

  The content of the maleimide compound X in 100% by weight of the component excluding the inorganic filler and the solvent in the resin material is preferably 3% by weight or more, more preferably 5% by weight or more, and further preferably 10% by weight or more. Preferably it is 90 weight% or less, More preferably, it is 80 weight% or less. When the content of the maleimide compound X is not less than the above lower limit, the dielectric loss tangent can be further lowered, and the adhesion between the insulating layer and the metal layer can be further enhanced. The embedding property at the time of lamination can be made favorable as content of the said maleimide compound X is below the said upper limit.

  From the viewpoint of further improving the adhesion between the insulating layer and the metal layer, the maleimide compound X preferably has a weight average molecular weight of 500 or more, more preferably 1000 or more, preferably less than 15000, more preferably less than 12000, Preferably it is less than 10,000.

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

<Benzoxazine compound having aliphatic skeleton>
The resin material according to the present invention preferably contains a benzoxazine compound having an aliphatic skeleton (hereinafter sometimes referred to as benzoxazine compound X) as the aliphatic skeleton-containing compound. The benzoxazine compound X has a benzoxazine skeleton. Therefore, the benzoxazine compound X has a benzoxazine skeleton and an aliphatic skeleton. In the benzoxazine compound X, the aliphatic skeleton is preferably bonded to the nitrogen atom forming the benzoxazine skeleton. The benzoxazine compound X may have an imide skeleton. As the benzoxazine compound X, a conventionally known benzoxazine compound can be used. As for the said benzoxazine compound X, only 1 type may be used and 2 or more types may be used together.

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

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

  The benzoxazine compound X is obtained by, for example, reacting the above-described tetracarboxylic dianhydride with the above-described diamine compound to obtain a reaction product having both ends of an amino group, and then reacting the reaction product with phenol, paraformaldehyde, Can be obtained by reacting. In addition, the N-alkylbenzoxazine compound having a skeleton derived from dimerized amine is obtained by reacting, for example, tetracarboxylic dianhydride and dimerized amine to obtain a reactant having a skeleton derived from dimerized amine at both ends. Thereafter, the reaction product can be obtained by reacting phenol with paraformaldehyde.

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

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

  The benzoxazine compound X having a skeleton derived from the reaction product of the polyamine compound having an aliphatic skeleton and a carboxylic dianhydride is obtained by, for example, reacting a polyamine compound having an aliphatic skeleton with a carboxylic dianhydride. After obtaining a reaction product having amino groups at both ends, the reaction product can be obtained by reacting phenol with paraformaldehyde.

  Specifically, the benzoxazine compound X preferably has a skeleton derived from a reaction product between a diamine compound having an aliphatic skeleton or a triamine compound having an aliphatic skeleton and a carboxylic dianhydride. The benzoxazine compound X may have a skeleton derived from a reaction product of a diamine compound having an aliphatic skeleton and a carboxylic dianhydride. The benzoxazine compound X is a reaction product of a diamine compound having an aliphatic skeleton, an amine compound different from the diamine compound having an aliphatic skeleton (for example, a diamine compound having an aromatic skeleton), and a carboxylic dianhydride. It may have a skeleton derived from. The benzoxazine compound X may have a skeleton derived from a reaction product of a triamine compound having an aliphatic skeleton and a carboxylic dianhydride, and has a triamine compound having an aliphatic skeleton and an aliphatic skeleton. You may have the frame | skeleton derived from the reaction material of the amine compound different from a triamine compound, and carboxylic dianhydride. In this case, in order to obtain the reactant, it is preferable to use one of a diamine compound having an aliphatic skeleton and a triamine compound having an aliphatic skeleton. In order to obtain the reaction product, it is more preferable that both a diamine compound having an aliphatic skeleton and a triamine compound having an aliphatic skeleton are used. In this case, the blending amount (wt%) of the triamine compound having an aliphatic skeleton is preferably 5% or less of the blending amount (wt%) of the diamine compound having an aliphatic skeleton.

  The benzoxazine compound X having a skeleton derived from the reaction product of the diamine compound having an aliphatic skeleton and a carboxylic dianhydride is obtained by reacting a diamine compound having an aliphatic skeleton with a carboxylic dianhydride, for example. After obtaining a reaction product having a terminal amino group, the reaction product can be obtained by reacting phenol with paraformaldehyde.

  The benzoxazine compound X having a skeleton derived from the reaction product of the triamine compound having an aliphatic skeleton and a carboxylic dianhydride is obtained by reacting a triamine compound having an aliphatic skeleton with a carboxylic dianhydride, for example. After obtaining a reaction product having a terminal amino group, the reaction product can be obtained by reacting phenol with paraformaldehyde.

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

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

  As said carboxylic dianhydride, the carboxylic dianhydride mentioned above is mentioned.

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

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

  Examples of the dimer amine include the dimer amine described above.

  As said tetracarboxylic dianhydride, the tetracarboxylic dianhydride mentioned above is mentioned.

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

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

  The content of the benzoxazine compound X is preferably 3% by weight or more, more preferably 5% by weight or more, and still more preferably 10% by weight or more in 100% by weight of the resin material excluding the inorganic filler and the solvent. , Preferably 90% by weight or less, more preferably 80% by weight or less. When the content of the benzoxazine compound X is not less than the above lower limit, the dielectric loss tangent can be further lowered, and the adhesion between the insulating layer and the metal layer can be further enhanced. When the content of the benzoxazine compound X is not more than the above upper limit, the embedding property at the time of lamination can be improved.

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

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

  In 100% by weight of the organic component excluding the solvent in the resin material, the total content of the polyimide compound and the aliphatic skeleton-containing compound is preferably 10% by weight or more, more preferably 15% by weight or more, and still more preferably. Is 20% by weight or more. In 100% by weight of the organic component excluding the solvent in the resin material, the total content of the polyimide compound and the aliphatic skeleton-containing compound is preferably 98% by weight or less, more preferably 80% by weight or less. When the total content is not less than the above lower limit and not more than the above upper limit, the effects of the above-described 1) -6) of the present invention can be more effectively exhibited.

[Thermosetting compound]
The resin material preferably contains a thermosetting compound. The thermosetting compound is a thermosetting compound different from the polyimide compound, the maleimide compound X, and the benzoxazine compound X. Examples of the thermosetting compounds include styrene compounds, vinyl compounds, phenoxy compounds, oxetane compounds, epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenolic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, and silicone compounds. Is mentioned. As for the said thermosetting compound, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of more effectively exerting the effects of the present invention 1) -6) described above, and from the viewpoint of improving the thermal dimensional stability, the thermosetting compound is preferably an epoxy compound.

  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.

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

  From the viewpoint of further reducing the dielectric loss tangent and improving the coefficient of thermal expansion (CTE) of the cured product, the epoxy compound includes an epoxy compound that is liquid at 25 ° C. and an epoxy compound that is solid at 25 ° C. 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 increasing the adhesive strength between the cured product and the metal layer, the content of the epoxy compound is preferably 5% by weight or more, more preferably 25% in 100% by weight of the organic component excluding the solvent in the resin material. % By weight 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 aliphatic skeleton-containing compound and the component X described later (content of the epoxy compound / total of the aliphatic skeleton-containing compound and the component X) The content) is preferably 0.1 or more, more preferably 0.2 or more. The weight ratio of the content of the epoxy compound to the total content of the aliphatic skeleton-containing compound and the component X described later (content of the epoxy compound / total of the aliphatic skeleton-containing compound and the component X) The content is preferably 0.9 or less, more preferably 0.8 or less. When the weight ratio (content of the epoxy compound / total content of the aliphatic skeleton-containing compound and the component X) is not less than the above lower limit and not more than the above upper limit, the dielectric loss tangent can be lowered, and the line An expansion coefficient can be made small, the adhesiveness of an insulating layer and a metal layer can be improved further, and handling property can be improved.

[Inorganic filler]
The resin material preferably contains an inorganic filler. By using the inorganic filler, the dielectric loss tangent of the cured product can be further reduced. In addition, the use of the inorganic filler further reduces the dimensional change due to heat of the cured product. 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 cured product is reduced, the adhesive strength between the cured product and the metal layer is further increased, finer wiring is formed on the surface of the cured product, and 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. In addition, the use of silica effectively reduces the surface roughness of the cured product and effectively increases the adhesive strength between the cured product and the metal layer. The shape of silica is preferably spherical.

  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, still more preferably 500 nm or more, preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less. When the average particle size of the inorganic filler is not less than the above lower limit and not more than the above upper limit, the embedding property with respect to the uneven surface can be further enhanced, and the adhesion between the insulating layer and the metal layer can be further enhanced.

  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 cured product is effectively reduced, and the adhesive strength between the cured product and the metal layer is effectively increased. When the inorganic filler is spherical, the aspect ratio of the inorganic filler is preferably 2 or less, more preferably 1.5 or less.

  The inorganic filler is preferably surface-treated, more preferably a surface-treated product with a coupling agent, and still more preferably a surface-treated product with a silane coupling agent. By the surface treatment of the inorganic filler, the surface roughness of the roughened cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased. 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 methacryl silane, acrylic silane, amino silane, imidazole silane, vinyl silane, and epoxy silane.

  In 100% by weight of the component excluding the solvent in the resin material, the content of the inorganic filler is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 65% by weight or more, 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 not less than the above lower limit, the dielectric loss tangent is effectively lowered, and the linear expansion coefficient can be reduced. When the content of the inorganic filler is not more than the above upper limit, adhesion, embedding with respect to the uneven surface, and etching performance can be improved. When the content of the inorganic filler is not less than the above lower limit and not more than the above upper limit, the surface roughness of the surface of the cured product can be further reduced, and finer wiring can be formed on the surface of the cured product. Can do. Furthermore, with this amount of inorganic filler, it is possible to 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 cyanate ester compound (cyanate ester curing agent), amine compound (amine curing agent), thiol compound (thiol curing agent), imidazole compound, phosphine compound, dicyandiamide, phenol compound (phenol curing agent), and acid anhydride. Products, active ester compounds, carbodiimide compounds (carbodiimide curing agents), benzoxazine compounds having no aliphatic skeleton (benzoxazine curing agents), maleimide compounds having no aliphatic skeleton, and the like. The curing agent preferably has a functional group capable of reacting with the epoxy group of the epoxy compound.

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

  In the present specification, “phenol compound, cyanate ester compound, acid anhydride, active ester compound, carbodiimide compound, and N-phenylbenzoxazine compound in which an aromatic skeleton is bonded to a nitrogen atom forming a benzoxazine skeleton. Of these, at least one component ”may be referred to as“ component X ”.

  The resin material preferably contains a curing agent containing component X. 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 the thermal dimensional stability, the active ester compound is preferably an active ester compound having two or more aromatic skeletons. From the viewpoint of reducing the dielectric loss tangent of the cured product and 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.

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

  Examples of commercially available benzoxazine compounds having no aliphatic skeleton include “Pd type” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  The content of the component X with respect to a total of 100 parts by weight of the polyimide compound, the aliphatic skeleton-containing compound, and the thermosetting compound is preferably 70 parts by weight or more, more preferably 85 parts by weight or more, preferably 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.

  The content of the component X with respect to 100 parts by weight of the thermosetting compound is preferably 70 parts by weight or more, more preferably 85 parts by weight or more, preferably 150 parts by weight or less, 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 polyimide compound, the aliphatic skeleton-containing compound, the thermosetting compound, and the component X is preferably Is 50% by weight or more, more preferably 60% by weight or more, preferably 90% by weight or less, more preferably 85% by weight or less. When the total content of the thermosetting compound and the component X is not less than the above lower limit and not more than the above upper limit, the curability is further improved and the thermal dimensional stability can be further enhanced.

  In 100% by weight of the component excluding the inorganic filler and the solvent in the resin material, the total content of the thermosetting 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 thermosetting compound and the component X is not less than the above lower limit and not more than the above upper limit, the curability is 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.

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

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

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

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

  The curing accelerator may contain a radical curing accelerator and at least one curing accelerator of dimethylaminopyridine, an imidazole compound, and a phosphorus compound.

  The content of the curing accelerator is not particularly limited. The content of the curing accelerator is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and preferably 5% by weight or less, in 100% by weight of the resin material excluding the inorganic filler and the solvent. More preferably, it is 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 better hardened | cured material will be obtained.

[Thermoplastic resin]
The resin material preferably contains a thermoplastic resin. Examples of the thermoplastic resin include polyvinyl acetal resin and phenoxy resin. 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 the phenoxy resin, the dispersibility of the inorganic filler is improved, and the resin composition 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 obtaining a more excellent resin material due to storage stability, the weight average molecular weight of the thermoplastic resin and the phenoxy resin is preferably 5,000 or more, more preferably 10,000 or more, preferably 100,000 or less, more preferably 50,000 or less. It is.

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

  Content of the said thermoplastic resin and the said phenoxy resin is not specifically limited. The content of the thermoplastic resin (the content of the phenoxy resin when the thermoplastic resin is a phenoxy resin) in 100% by weight of the component excluding the inorganic filler and the solvent in the resin material is preferably 1 weight. % Or more, more preferably 2% by weight or more, preferably 30% by weight or less, more preferably 20% by weight or less. When the content of the thermoplastic resin is not less than the 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 cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased.

[solvent]
The resin material does not contain or contains a solvent. By using the solvent, the viscosity of the resin material can be controlled within a suitable range, and the coatability of the resin material can be improved. 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 composition is formed into a film. Therefore, the boiling point of the solvent is preferably 200 ° C. or lower, more preferably 180 ° C. or lower. The content of the solvent in the resin composition is not particularly limited. The content of the solvent can be appropriately changed in consideration of the coating property of the resin composition.

[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, A thermosetting resin other than a foaming agent, a thickener, a thixotropic agent, and an epoxy compound may be added.

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

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

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

  The resin material is preferably a thermosetting material.

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

  The film-like resin composition that can be obtained by the drying process as described above is referred to as a B-stage film. The B-stage film is in a semi-cured state. 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 resin film can be suitably used in the form of a laminated film.

  The laminated film includes a base material and a resin film laminated on the surface of the base material. The resin film is the resin material described above. The said laminated | multilayer film may be equipped with the protective film laminated | stacked on the surface on the opposite side to the said base material of a resin film.

  Examples of the substrate include polyester resin films such as polyethylene terephthalate film and polybutylene terephthalate film, olefin resin films such as polyethylene film and polypropylene film, polyimide resin film, and metal foil such as copper foil. 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.

(Semiconductor devices, printed wiring boards, copper-clad laminates and multilayer printed wiring boards)
The resin material is preferably used for forming a mold resin for embedding a semiconductor chip in a semiconductor device.

  The resin material is 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 is 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 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 is 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 insulating layer of the multilayer substrate is formed of the resin material. 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 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. 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, it is possible to effectively increase the insulation reliability by reducing the dielectric loss tangent and enhancing the adhesion between the insulating layer and the metal layer and the etching performance. Therefore, the resin material according to the present invention is suitably used for forming an insulating layer in a multilayer printed wiring board.

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

  FIG. 1 is a cross-sectional view schematically showing a multilayer printed wiring board using a resin material according to 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 to 16 are formed of a cured product of the resin material. 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 in order to obtain a cured product that is roughened or desmeared. The cured product includes a precured product that can be further cured.

  In order to form fine irregularities on the surface of the cured product obtained by precuring the resin material, the cured product is preferably roughened. Prior to the roughening treatment, the cured product is preferably subjected to a swelling treatment. The cured product is preferably subjected to a swelling treatment after preliminary curing and before the roughening treatment, and is further cured after the roughening treatment. However, the cured product is not necessarily subjected to the 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 product with a 40 wt% ethylene glycol aqueous solution at a treatment temperature of 30 to 85 ° C. for 1 to 30 minutes. The swelling treatment temperature is preferably in the range of 50 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 product 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 product is preferably 10 nm or more, preferably less than 300 nm, more preferably less than 200 nm, and even more preferably less than 150 nm. In this case, the adhesive strength between the cured product and the metal layer is increased, and further finer wiring is formed on the surface of the insulating layer. Furthermore, conductor loss can be suppressed and signal loss can be suppressed low. The arithmetic average roughness Ra is measured in accordance with JIS B0601: 1994.

(Desmear treatment)
Through holes may be formed in a cured product 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 to 80 μm. Due to the formation of the through hole, a smear, which is a resin residue derived from the resin component contained in the cured product, is often formed at the bottom of the via.

  In order to remove the smear, the surface of the cured product is preferably 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 surface of the cured product subjected to the desmear treatment is sufficiently reduced.

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

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

(Synthesis Example 1)
In a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube, 135.0 g of tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan GK) and 400 g of cyclohexanone were added, The solution in the reaction vessel was heated to 60 ° C. Next, 17.5 g of 1,3-bisaminomethylcyclohexane (Mitsubishi Gas Chemical Co., Ltd.) was dropped into the reaction vessel and reacted to obtain a reaction product whose both ends were acid anhydrides. Next, 148 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan Co., Ltd.) was slowly added to the reaction vessel, and then 60.0 g of methylcyclohexane was added to the reaction vessel. 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. Then 28 g of maleic anhydride was added and the resulting mixture was refluxed for an additional 12 hours. After completion of the reaction, isopropanol was added and reprecipitated, and then the precipitate was collected and dried to obtain an N-alkylbismaleimide compound having a skeleton derived from dimer diamine. The recovery rate of the N-alkylbismaleimide compound having a skeleton derived from dimer diamine was 83%. (Weight average molecular weight 10,000)

(Synthesis Example 2)
After stirring, 55 g of pyromellitic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 254.15) and 300 g of cyclohexanone were placed in a reaction vessel equipped with a water separator, a thermometer, and a nitrogen gas introduction tube. The solution was heated to 60 ° C. Next, a solution in which 26.7 g of bis (aminomethyl) norbornane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 154.26) is dissolved in cyclohexanone is dropped into the reaction vessel and reacted, and both ends are acid anhydrides. A reaction product was obtained. Thereafter, isopropanol was added to recover an imide compound having acid anhydrides at both ends. Next, the precipitate was dissolved again in cyclohexane, and 46.0 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan Co., Ltd.) was slowly added to the reaction vessel, and then 45.0 g of methylcyclohexane was added to the reaction vessel. 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. The recovery rate of the maleimide compound was 70%. (Weight average molecular weight 8700)

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

(Synthesis Example 3)
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 (weight average molecular weight 7700) was obtained by reprecipitation with isopropanol.

(Maleimide compound having no aliphatic skeleton (maleimide compound having an aromatic skeleton)) N-phenylmaleimide compound 1 (“BMI-2300” manufactured by Daiwa Kasei Kogyo Co., Ltd.)
N-phenylmaleimide compound 2 (“BMI-4000” manufactured by Daiwa Kasei Kogyo Co., Ltd.)

(Polyimide compound)
A 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 4 below.

(Synthesis Example 4)
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 4 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.

(Thermoplastic resin)
Phenoxy resin (Mitsubishi Chemical "YX6954BH30")

(Thermosetting 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)
Dicumyl peroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)

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

Production of resin film:
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 placed 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.

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

[Handling criteria]
○: The number of occurrences of cracks or cracks is less than 3 during 10 times. Δ: The number of occurrences of cracks or cracks is 10 times or more and less than 6 times during 10 times. The number of occurrences is 6 or more

(2) Embeddability to uneven surface and prevention of protrusion (prevention of excessive wetting and spreading)
Only a copper foil of a 100 mm square copper-clad laminate (a laminate of a 400 μm thick glass epoxy substrate and a 25 μm thick copper foil) is etched to form a recess (opening) having a diameter of 100 μm and a depth of 25 μm, The substrate was opened in a straight line with respect to the 30 mm square area of the substrate so that the distance between the centers of adjacent holes was 900 μm. Thus, the evaluation board | substrate with a hollow of a total of 900 holes was prepared.

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

  About the obtained evaluation sample, the void in a hollow was observed using the optical microscope. By evaluating the ratio of depressions where voids were observed, the embedding property with respect to the uneven surface was determined according to the following criteria.

[Criteria for embedding on uneven surfaces]
○: Ratio of depression where void was observed 0%
Δ: Ratio of depressions where voids were observed exceeded 0% and less than 5% ×: Ratio of depressions where voids were observed 5% or more

  About the obtained evaluation sample, using an optical microscope, it was observed whether the resin film protruded from the predetermined | prescribed area | region on a board | substrate, and the protrusion prevention property was determined on the following references | standards.

[Judgment criteria for protrusion prevention]
○: The protrusion of the resin film from the periphery of the evaluation substrate after lamination is 2 mm or less Δ: The protrusion of the resin film from the periphery of the evaluation substrate after lamination exceeds 2 mm and 3 mm or less ×: From the periphery of the evaluation substrate after lamination The protrusion of the resin film exceeds 3 mm

(3) Curing temperature The exothermic peak accompanying the hardening of the obtained resin film (B stage film) was evaluated using a differential scanning calorimeter ("Q2000" manufactured by TA Instruments). 8 mg of resin film was taken in a special aluminum pan and covered with a special jig. This special aluminum pan and an empty aluminum pan (reference) are installed in the heating unit and heated in a nitrogen atmosphere from -30 ° C to 250 ° C at a rate of temperature increase of 3 ° C / min. Reverse heat flow and non-reverse The heat flow was observed. The curing temperature was confirmed by the exothermic peak observed in the non-reverse heat flow.

[Criteria for curing temperature]
○: all exothermic peaks at 200 ° C. or lower ×: at least one exothermic peak at a temperature higher than 200 ° C.

(4) Dielectric loss tangent The obtained resin film was cut into a size of 2 mm in width and 80 mm in length, and 5 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 product. 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.

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

(5) 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

(6) Average linear expansion coefficient (CTE)
A 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 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.

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

(7) Bending stability of hardened | cured material The hardened | cured material obtained by heating the obtained resin film (B stage film) of 40 micrometers in thickness at 190 degreeC for 90 minutes was cut | judged to the magnitude | size of 30 mm x 150 mm. Using a planar U-shaped folding tester (manufactured by Yuasa Co., Ltd.), a descending bending test was performed under the conditions of 200 times / minute, 180 ° C. bending (bending gap 5 mm), and film stroke 70 mm. The measurement was repeated 5 times, and the average value was calculated.

[Criteria for bending stability of cured products]
〇 ○: No crack after 2000 bending 〇: Crack occurs when the number of folding times is 100 times or more and less than 2000 times ×: Cracking occurs when the number of folding times is less than 100 times

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

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

Claims (19)

A polyimide compound;
A resin material comprising a maleimide compound having an aliphatic skeleton and at least one aliphatic skeleton-containing compound of a benzoxazine compound having an aliphatic skeleton.   The resin material according to claim 1, wherein in the aliphatic skeleton-containing compound, the aliphatic skeleton is bonded to a nitrogen atom forming a maleimide skeleton or a benzoxazine skeleton. The weight average molecular weight of the polyimide compound is 15000 or more,
The resin material according to claim 1 or 2, wherein the aliphatic skeleton-containing compound has a weight average molecular weight of less than 15,000.   The resin material according to any one of claims 1 to 3, wherein the aliphatic skeleton-containing compound has a skeleton derived from a reaction product of a polyamine compound having an aliphatic skeleton and a carboxylic dianhydride.   The resin material according to any one of claims 1 to 4, wherein the aliphatic skeleton-containing compound has a skeleton derived from a reaction product of a diamine compound having an aliphatic skeleton and a carboxylic dianhydride.   The resin material according to claim 5, wherein the diamine compound having an aliphatic skeleton is a diamine compound having a skeleton derived from dimer diamine.   The resin material according to any one of claims 1 to 6, comprising a thermosetting compound and an inorganic filler.   The resin material according to claim 7, wherein the thermosetting compound is an epoxy compound.   The resin material according to claim 7 or 8, wherein a content of the inorganic filler is 50% by weight or more in 100% by weight of a component excluding a solvent in the resin material.   The total content of the polyimide compound and the aliphatic skeleton-containing compound is 100% by weight, and the content of the polyimide compound is 3% by weight to 80% by weight. Resin material.   The resin material according to any one of claims 1 to 10, wherein the polyimide compound is a polyimide compound having a skeleton derived from dimer diamine.   The total content of the polyimide compound and the aliphatic skeleton-containing compound in 10% by weight of the organic component excluding the solvent in the resin material is 10% by weight or more and 98% by weight or less. The resin material according to claim 1. Contains a curing accelerator,
The resin material according to claim 1, wherein the curing accelerator includes at least one of a radical curing accelerator and an anionic curing accelerator.   The curing accelerator includes a radical curing accelerator and dimethylaminopyridine, or includes a radical curing accelerator and an imidazole compound, or includes a radical curing accelerator and a phosphorus compound. 13. The resin material according to 13. A curing agent and a curing accelerator,
The resin material according to claim 1, wherein the curing accelerator contains an imidazole compound.   The resin material according to any one of claims 1 to 15, which is a resin film.   The resin material of any one of Claims 1-16 used in order to form an insulating layer in a multilayer printed wiring board. A substrate;
A resin film laminated on the surface of the substrate,
A laminated film in which the resin film is the resin material according to claim 1. 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 at least 1 layer of the said some insulating layers is the hardened | cured material of the resin material of any one of Claims 1-17.

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