JP2020059820A - Resin material and multilayer printed wiring board - Google Patents

Abstract

To provide a resin material which is excellent in storage stability and whose cured product is hardly cracked or broken even when receiving a thermal shock.SOLUTION: The resin material according to the present invention contains an epoxy compound, an inorganic filler, and a curing agent. The curing agent contains an active ester compound having a structure represented by formula (1). The content of the inorganic filler is 55 wt.% or more in 100 wt.% of components except a solvent in the resin material. (However, a resin material used by being impregnated into a fiber base material is excluded). In the formula (1), R1, R2 and X1 each represent an organic group; X2 represents a group containing an aliphatic chain skeleton, a group containing an aliphatic skeleton, or a group containing an aromatic skeleton; m represents an integer from 1 to 6 inclusive; and n represent an integer from 1 to 5 inclusive.SELECTED DRAWING: Figure 1

Description

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

  Conventionally, various resin materials have been used to obtain electronic parts 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 the inner layers and to form an insulating layer located in the surface layer portion. Wiring, which is generally metal, is laminated on the surface of the insulating layer. Further, in order to form the insulating layer, a resin film obtained by filmizing the resin material may be used. The resin material and the resin film are used as an insulating material for a multilayer printed wiring board including a build-up film.

  As an example of the above resin material, the following Patent Document 1 discloses a heat containing an epoxy resin and an active ester resin having a resin structure having specific structural sites and both ends of which are monovalent aryloxy groups. A curable resin composition is disclosed. Moreover, in the Example of patent document 1, the said thermosetting resin composition is used by making glass cloth impregnate.

  In addition, Patent Document 2 below discloses a resin composition containing an active ester resin having a specific structure and an epoxy resin. Further, in the example of Patent Document 2, glass cloth is impregnated with the above resin composition for use.

WO2016 / 098488A1 JP, 2008-080264, A

  The conventional resin material may have low storage stability. For example, in the conventional resin material, the melt viscosity of the resin material after storage may be higher than that of the resin material before storage. In addition, in the conventional resin material, when the resin material after storage is used, the embedding property (pattern embedding property) in the unevenness of the substrate or the like is deteriorated and the fine wiring is formed as compared with the resin material before storage. It may be difficult to do.

  In order to lower the dielectric loss tangent of the insulating layer (cured product), the resin material is often mixed with an inorganic filler. However, with a resin material containing a large amount of inorganic filler, the storage stability of the resin material is likely to decrease. In the example of Patent Document 1, no inorganic filler is used. Further, in the example of Patent Document 2, the compounding amount of the inorganic filler is only 50% by weight with respect to 100% by weight of the resin material. Even with the resin materials described in Patent Documents 1 and 2, if the compounding amount of the inorganic filler is increased, the storage stability of the resin material may decrease.

  Further, when an insulating layer (cured product) is formed using a conventional resin material, the insulating layer may be cracked or cracked due to thermal shock. When the insulating layer is cracked or cracked, the conduction reliability is reduced.

  An object of the present invention is to provide a resin material which has excellent storage stability and is less likely to cause cracks or cracks in a cured product even when subjected to thermal shock. Another object of the present invention is to provide a multilayer printed wiring board using the above resin material.

  According to a broad aspect of the present invention, an epoxy compound, an inorganic filler, and a curing agent are contained, and the curing agent contains an active ester compound having a structure represented by the following formula (1). There is provided a resin material (excluding a resin material used by impregnating a fiber base material) in which the content of the inorganic filler is 55% by weight or more based on 100% by weight of the component excluding the solvent.

  In the formula (1), R1, R2 and X1 each represent an organic group, X2 represents a group containing an aliphatic chain skeleton, a group containing an aliphatic skeleton or a group containing an aromatic skeleton, and m is 1 It represents an integer of 6 or more and n, and n represents an integer of 1 or more and 5 or less.

  In a specific aspect of the resin material according to the present invention, in the formula (1), X1 is an organic group having 5 or more carbon atoms.

  In one specific aspect of the resin material according to the present invention, in the formula (1), X1 is a group having an aromatic skeleton.

  In a specific aspect of the resin material according to the present invention, in the above formula (1), X1 is a group having two or more aromatic skeletons.

  In one specific aspect of the resin material according to the present invention, in the above formula (1), X1 is a group having no reactive group.

  In a particular aspect of the resin material according to the present invention, in the formula (1), R1 or R2 is a group having a heteroaromatic ring skeleton.

  In a specific aspect of the resin material according to the present invention, in the formula (1), R1 or R2 is a group having an imide skeleton.

  In a specific aspect of the resin material according to the present invention, in the formula (1), R1 or R2 is a group having a naphthalene skeleton.

  In one specific aspect of the resin material according to the present invention, in the formula (1), R1, R2, X1 and X2 are each a group having no phosphorus atom.

  In a particular aspect of the resin material according to the present invention, in the formula (1), R1, R2, X1 and X2 are each a group having no aliphatic hydrocarbon chain having 2 to 4 carbon atoms. is there.

  In one specific aspect of the resin material according to the present invention, the melt viscosity at 100 ° C. is 5 Pa · s or more and 500 Pa · s or less.

  In one specific aspect of the resin material according to the present invention, the curing agent contains an active ester compound having no side chain.

  In one specific aspect of the resin material according to the present invention, the curing agent contains a carbodiimide compound.

  In a specific aspect of the resin material according to the present invention, the active ester equivalent of the active ester compound having the structure represented by the formula (1) is 200 eq / g or more and 500 eq / g or less.

  On the specific situation with the resin material which concerns on this invention, the said epoxy compound contains a naphthol aralkyl type epoxy compound.

  In one specific aspect of the resin material according to the present invention, the inorganic filler is silica.

  On the specific situation with the resin material which concerns on this invention, the said resin material contains a hardening accelerator.

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

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

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

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

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

  The resin material according to the present invention includes an epoxy compound, an inorganic filler, and a curing agent, and the curing agent includes an active ester compound having a structure represented by formula (1), and a solvent in the resin material. The content of the above-mentioned inorganic filler is 55% by weight or more in 100% by weight of components excluding. Since the resin material according to the present invention is provided with the above-mentioned constitution, it has excellent storage stability, and the cured product is unlikely to crack or crack even when subjected to thermal shock.

FIG. 1 is a 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 contains an epoxy compound, an inorganic filler, and a curing agent, and the curing agent contains an active ester compound having a structure represented by the following formula (1). A resin material (excluding a resin material used by impregnating a fiber base material) in which the content of the inorganic filler is 55% by weight or more in 100% by weight of components excluding a solvent.

  In the above formula (1), R1, R2 and X1 each represent an organic group, X2 represents a group containing an aliphatic chain skeleton, a group containing an aliphatic skeleton or a group containing an aromatic skeleton, and m is 1 It represents an integer of 6 or more and n, and n represents an integer of 1 or more and 5 or less.

  Since the resin material according to the present invention is provided with the above-mentioned constitution, it has excellent storage stability, and the cured product is unlikely to crack or crack even when subjected to thermal shock.

  Further, since the resin material according to the present invention is provided with the above configuration, the dielectric loss tangent of the cured product can be lowered.

  The resin material according to the present invention is different from the resin material used by impregnating the fiber base material. The impregnated base material in which the fiber material is impregnated with the resin material is, for example, a prepreg. The resin material according to the present invention can be used for purposes different from those of prepreg. Examples of the fibrous base material include inorganic fibers such as glass fibers and organic fibers such as polyester fibers. Therefore, the resin material according to the present invention is different from the resin material used by impregnating the inorganic fiber and the organic fiber.

  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 a paste form. A liquid is included in the paste form. The resin material according to the present invention is preferably a resin film because of its excellent handleability.

  When the resin material is a resin film, storage stability is likely to be further reduced. With the resin material according to the present invention, storage stability can be improved even when the resin material is a resin film.

  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.

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

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

  Examples of the epoxy compound 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, 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, adamantane skeleton epoxy compound, tricyclodecane skeleton epoxy compound, naphthylene ether type Examples thereof include epoxy compounds and epoxy compounds having a triazine nucleus in the skeleton.

  From the viewpoint of lowering the dielectric loss tangent and enhancing the thermal dimensional stability and flame retardancy of the cured product, the epoxy compound preferably contains an epoxy compound having an aromatic skeleton, and an epoxy having a naphthalene skeleton or a phenyl skeleton. It is more preferable to include a compound, and it is further preferable to include an epoxy compound having a naphthylene ether skeleton. The naphthylene ether skeleton means a skeleton in which an oxygen atom is bonded to a carbon atom forming a naphthalene ring.

  From the viewpoint of further lowering the dielectric loss tangent and further enhancing the thermal dimensional stability and flame retardancy of the cured product, the epoxy compound contains a naphthol aralkyl type epoxy compound (epoxy compound having a naphthylene ether skeleton). It is preferable.

  The naphthol aralkyl type epoxy compound preferably has one or more naphthylene ether skeletons, more preferably two or more, more preferably three or more, and particularly preferably four or more. When the number of the naphthylene ether skeletons is not less than the above lower limit, the dielectric loss tangent can be further lowered.

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

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

  The viscosity of the epoxy compound can be measured using, for example, a dynamic viscoelasticity measuring device (“VAR-100” manufactured by Rheological Instruments).

  The molecular weight of the epoxy compound is more preferably 1000 or less. In this case, even if the content of the inorganic filler is 55% by weight or more in 100% by weight of the component excluding the solvent in the resin material, a resin material having high fluidity can be obtained when the insulating layer is formed. Therefore, when an uncured resin material or a B-staged resin material is laminated on a circuit board, the inorganic filler can be uniformly present.

  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. Further, the molecular weight of the epoxy compound means a weight average molecular weight when the epoxy compound is a polymer.

  From the viewpoint of further enhancing the thermal dimensional stability of the cured product, the content of the epoxy compound is preferably 10% by weight or more, more preferably 15% by weight or more, in 100% by weight of the component excluding the solvent in the resin material. It is preferably less than 45% by weight, more preferably 40% by weight or less.

  In 100% by weight of the component excluding the inorganic filler and the solvent in the resin material, the content of the epoxy compound is preferably 10% by weight or more, more preferably 15% by weight or more, further preferably 25% by weight or more, particularly preferably Is 30% 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 epoxy compound is preferably 60% by weight or less, more preferably 50% by weight or less, further preferably 45% by weight or less, particularly preferably Is 40% by weight or less. When the content of the epoxy compound is at least the above lower limit and at most the above upper limit, the thermal dimensional stability of the cured product can be further enhanced.

[Inorganic filler]
The resin material includes an inorganic filler. The use of the inorganic filler can further lower the dielectric loss tangent of the cured product. Further, the use of the above-mentioned inorganic filler further reduces the dimensional change of the cured product due to heat. 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, and finer wiring is formed on the surface of the cured product, and the cured product has better insulation reliability. From the viewpoint of providing the above, the inorganic filler is preferably silica or alumina, more preferably silica, and further preferably fused silica. The use of silica results in a lower coefficient of thermal expansion of the cured product and a lower dielectric loss tangent of the cured product. Further, by using silica, the surface roughness of the surface of the cured product is effectively reduced, and the adhesive strength between the cured product and the metal layer is effectively increased. The shape of silica is preferably spherical.

  The inorganic filler is spherical silica from the viewpoint of promoting the curing of the resin regardless of the curing environment, 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, still more preferably 1 μm or less. When the average particle diameter of the inorganic filler is not less than the above lower limit and not more than the above upper limit, it is possible to reduce the surface roughness after etching and to increase the plating peel strength, and also between the insulating layer and the metal layer. The adhesiveness can be further enhanced.

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

  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 further preferably a surface-treated product with a silane coupling agent. By the surface treatment of the inorganic filler, the surface roughness of the surface of the roughened cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further enhanced. Further, since the inorganic filler is surface-treated, it is possible to form finer wiring on the surface of the cured product, and further improve the inter-wiring insulation reliability and interlayer insulation reliability in the cured product. Can be granted.

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

  The content of the inorganic filler is 55% by weight or more based on 100% by weight of the component excluding the solvent in the resin material.

  In 100% by weight of the component excluding the solvent in the resin material, the content of the inorganic filler is preferably 60% by weight or more, more preferably 65% by weight or more, particularly preferably 68% by weight or more, preferably 90% by weight. The amount is below, more preferably 85% by weight or less, further preferably 80% by weight or less, and particularly preferably 75% by weight or less. When the content of the inorganic filler is at least the above lower limit, the dielectric loss tangent becomes effectively low. When the content of the inorganic filler is less than or equal to the above upper limit, the storage stability of the resin material can be increased, and the thermal dimensional stability of the cured product can be increased. When the content of the inorganic filler is not less than the lower limit and not more than the upper limit, it is possible to further reduce the surface roughness of the surface of the cured product, and to form finer wiring on the surface of the cured product. You can Furthermore, if the content of this inorganic filler is used, it is possible to reduce the coefficient of thermal expansion of the cured product and at the same time improve the smear removability.

[Curing agent]
The resin material contains a curing agent. As for the said hardening | curing agent, only 1 type may be used and 2 or more types may be used together.

<First active ester compound>
The resin material contains, as a curing agent, an active ester compound having a structure represented by the following formula (1) (hereinafter sometimes referred to as “first active ester compound”). As for the said 1st active ester compound, only 1 type may be used and 2 or more types may be used together.

  In the above formula (1), R1, R2 and X1 each represent an organic group, X2 represents a group containing an aliphatic chain skeleton, a group containing an aliphatic skeleton or a group containing an aromatic skeleton, and m is 1 It represents an integer of 6 or more and n, and n represents an integer of 1 or more and 5 or less.

  In the above formula (1), m is preferably 2 or more, and preferably 4 or less.

  In the above formula (1), n is preferably 3 or less.

  In the above formula (1), X1 may be a group in which the same structural unit is repeated. In the above formula (1), when X1 is a group in which the same structural unit is repeated, the number of repeating structural units is preferably 1 or more and 6 or less.

  In the above formula (1), X1 is preferably an organic group having 5 or more carbon atoms, more preferably an organic group having 7 or more carbon atoms, and an organic group having 10 or more carbon atoms. Is more preferable. In the above formula (1), X1 is preferably an organic group having 50 or less carbon atoms, more preferably an organic group having 40 or less carbon atoms, and an organic group having 30 or less carbon atoms. Is more preferable. In this case, it is possible to effectively suppress cracks or cracks of the cured product when it is subjected to thermal shock.

  In the above formula (1), X1 is preferably a group having an aromatic skeleton. In this case, it is possible to effectively suppress cracks or cracks of the cured product when it is subjected to thermal shock.

  Examples of the group having an aromatic skeleton include a group having a benzene ring which may have a substituent and a group having a naphthalene ring which may have a substituent.

  In the above formula (1), X1 is preferably a group having two or more aromatic skeletons, and more preferably a group having three or more aromatic skeletons. In this case, cracking or cracking of the cured product when subjected to thermal shock can be suppressed even more effectively.

  In the above formula (1), X1 is preferably a group represented by the following formula (1a). In this case, cracking or cracking of the cured product when subjected to thermal shock can be suppressed even more effectively.

  In the above formula (1a), k represents an integer of 1 or more and 6 or less.

  In the above formula (1a), k is preferably 2 or more, more preferably 3 or more, and preferably 5 or less.

  In the above formula (1), X1 is preferably a group having no reactive group. In this case, the storage stability of the resin material can be enhanced, and cracks or cracks of the cured product when subjected to thermal shock can be suppressed even more effectively.

  The reactive group means a group having a carbon-carbon unsaturated bond such as a vinyl group, a hydroxyl group, a glycidyl group, an isocyanate group, an amino group, a carboxyl group, an acid anhydride group, and a group having an active ester structure. To do.

  In the above formula (1), X2 is preferably a group containing an aromatic skeleton, and more preferably a group represented by the following formula (1b).

  In the above formula (1), R1 and R2 may be the same group or different groups.

  In the above formula (1), R1 or R2 is preferably a group having a heteroaromatic ring skeleton. In this case, cracking or cracking of the cured product when subjected to thermal shock can be suppressed even more effectively.

  The heterocycle means a ring composed of two or more kinds of elements, and examples thereof include a pyridine ring, a pyrrole ring, an imidazole ring, a dicyclopentadiene ring and a thiophene ring.

  In the above formula (1), R1 or R2 is preferably a group having an imide skeleton. In this case, cracking or cracking of the cured product when subjected to thermal shock can be suppressed even more effectively.

  In the above formula (1), R1 or R2 is preferably a group having a naphthalene skeleton. In this case, cracking or cracking of the cured product when subjected to thermal shock can be suppressed even more effectively.

  In the above formula (1), R1, R2, X1 and X2 are each preferably a group having no phosphorus atom. That is, it is preferable that the first active ester compound does not have a phosphorus atom. In this case, the storage stability of the resin material can be enhanced, and cracks or cracks of the cured product when subjected to thermal shock can be suppressed even more effectively.

  In the above formula (1), each of R1, R2, X1 and X2 is preferably a group having 2 to 4 carbon atoms and no aliphatic hydrocarbon chain, and fat having 2 or more carbon atoms. The group having no group hydrocarbon chain is more preferable. That is, the first active ester compound preferably does not have an aliphatic hydrocarbon chain having 2 or more and 4 or less carbon atoms, and does not have an aliphatic hydrocarbon chain having 2 or more carbon atoms. Is more preferable. In this case, the storage stability of the resin material can be enhanced, and cracks or cracks of the cured product when subjected to thermal shock can be suppressed even more effectively.

  The active ester equivalent of the first active ester compound is preferably 200 eq / g or more, more preferably 210 eq / g or more, even more preferably 220 eq / g or more, preferably 500 eq / g or less, more preferably 400 eq / g or less. And more preferably 350 eq / g or less. When the active ester equivalent is not less than the above lower limit and not more than the above upper limit, the effects of the present invention can be more effectively exhibited.

  The content of the first active ester compound with respect to 100 parts by weight of the epoxy compound is preferably 70 parts by weight or more, more preferably 85 parts by weight or more, preferably 250 parts by weight or less, more preferably 220 parts by weight or less, further It is preferably 150 parts by weight or less, particularly preferably 120 parts by weight or less. When the content of the first active ester compound is at least the above lower limit and not more than the above upper limit, curability is more excellent, thermal dimensional stability is further enhanced, and volatilization of residual unreacted components can be further suppressed.

  The content of the first active ester compound in 100% by weight of the curing agent is preferably 30% by weight or more, more preferably 50% by weight or more, and most preferably 100% by weight (total amount). When the content of the first active ester compound is not less than the lower limit and not more than the upper limit, the effects of the present invention can be more effectively exhibited.

<Curing agent X>
The resin material may include a curing agent having no structure represented by the following formula (X) (hereinafter, also referred to as “curing agent X”). The curing agent X is a curing agent different from the first active ester compound. As for the said hardening | curing agent X, only 1 type may be used and 2 or more types may be used together.

  In the above formula (X), R1, R2 and X1 each represent an organic group, X2 represents a group containing an aliphatic chain skeleton, a group containing an aliphatic skeleton or a group containing an aromatic skeleton, and m is 1 It represents an integer of 6 or more and n, and n represents an integer of 1 or more and 5 or less.

  Examples of the curing agent X include cyanate ester compounds (cyanate ester curing agents), amine compounds (amine curing agents), thiol compounds (thiol curing agents), imidazole compounds, phosphine compounds, dicyandiamide, phenol compounds (phenol curing agents), acids. An anhydride, an active ester compound having no structure represented by the above formula (X) (active ester curing agent, carbodiimide compound (carbodiimide curing agent), benzoxazine compound (benzoxazine curing agent) and the like can be mentioned. The curing agent X preferably has a functional group capable of reacting with the epoxy group of the epoxy compound.

  In the present specification, the “active ester compound having no structure represented by the above formula (X)” may be referred to as the “second active ester compound”.

  The curing agent X is preferably the second active ester compound or the carbodiimide compound. The curing agent preferably contains the second active ester compound and preferably the carbodiimide compound.

  The second active ester compound is a compound containing at least one ester bond and having an aliphatic chain, an aliphatic ring or an aromatic ring bonded to both sides of the ester bond. The second active ester compound is obtained, for example, by a condensation reaction between a carboxylic acid compound or a thiocarboxylic acid compound and a hydroxy compound or a thiol compound. Examples of the second active ester compound include compounds represented by the following formula (2).

  In the above formula (2), X1 represents a group containing an aliphatic chain, a group containing an aliphatic ring or a group containing an aromatic ring, and X2 represents a group containing an aromatic ring. Preferred examples of the group containing an aromatic ring include a benzene ring which may have a substituent and a naphthalene ring which may have a substituent. X1 is preferably a naphthalene ring. 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 further preferably 4 or less.

  In the above formula (2), the combination of X1 and X2 is a combination of a benzene ring which may have a substituent and a benzene ring which may have a substituent, and a combination of which has a substituent. And a naphthalene ring which may have a substituent. 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 second active ester compound is not particularly limited. From the viewpoint of enhancing thermal dimensional stability and flame retardancy, the second active ester compound is preferably an active ester compound having two or more aromatic skeletons. From the viewpoint of lowering the dielectric loss tangent of the cured product and enhancing the thermal dimensional stability of the cured product, it is more preferred to have a naphthalene ring in the main chain skeleton of the second active ester compound.

  The second active ester compound is preferably an active ester compound having no side chain. The curing agent preferably contains an active ester compound having no side chain. In this case, the effects of the present invention can be exhibited even more effectively.

  Since the first active ester compound has a side chain (a group represented by X1 in the formula (1)), the active ester compound having no side chain is the second active ester compound. Is.

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

  The carbodiimide compound is a compound having a structural unit represented by the following formula (3). In the following formula (3), 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 (3), X is an alkylene group, a group in which a substituent is bonded to an alkylene group, a cycloalkylene group, a group in which a substituent is bonded to a cycloalkylene group, an arylene group, or a substituent is bonded to an arylene group. Represents a group, and p represents an integer of 1 or more and 5 or less. When a plurality of Xs are present, the plurality of Xs may be the same or different.

  In the above formula (3), at least one X is preferably an alkylene group, a group in which a substituent is bonded to an alkylene group, a cycloalkylene group, or a group in which a substituent is bonded to a cycloalkylene group.

  Examples of commercially available products of the above carbodiimide compound include "carbodilite V-02B", "carbodilite V-03", "carbodilite V-04K", "carbodilite V-07", "carbodilite V-09", and "carbodilite" manufactured by Nisshinbo Chemical Inc. 10M-SP "," carbodilite 10M-SP (modification) ", and" Stabaxol P "," Stabaxol P400 "," Hikasil 510 "etc. by the line Chemie company are mentioned.

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

  Commercially available products of the above-mentioned phenol compound include novolac 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 a phenol having an aminotriazine skeleton (" LA1356 "and" LA3018-50P "manufactured by DIC) and the like.

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

  As commercial products of the above cyanate ester compounds, phenol novolac type cyanate ester resins (“PT-30” and “PT-60” manufactured by Lonza Japan Co., Ltd.), and a prepolymer obtained by trimerizing a bisphenol type cyanate ester resin (Lonza Japan "BA-230S", "BA-3000S", "BTP-1000S", and "BTP-6020S") manufactured by the company are listed.

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

  Examples of commercially available products of the acid anhydride include "Rikacid TDA-100" manufactured by Shin Nippon Rika Co., Ltd. and the like.

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

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

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

  Examples of the imidazole compound include 2-undecyl imidazole, 2-heptadecyl imidazole, 2-methyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 2-phenyl-4-methyl imidazole, 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 triphenylphosphine compounds.

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

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

  From the viewpoint of further suppressing the curing temperature and effectively suppressing the warp of the cured product, the curing accelerator preferably contains the anionic curing accelerator, and more preferably contains the imidazole compound.

  From the viewpoint of further suppressing the curing temperature and effectively suppressing the warp of the cured product, the content of the anionic curing accelerator in 100% by weight of the curing accelerator is preferably 20% by weight or more, more preferably Is 50% by weight or more, more preferably 70% by weight or more, and most preferably 100% by weight (total amount). Therefore, the curing accelerator is most preferably the anionic curing accelerator.

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

[Bismaleimide compound]
The resin material preferably contains a bismaleimide compound. The bismaleimide compound is not particularly limited. The bismaleimide compound has a maleimide group. As the bismaleimide compound, a conventionally known bismaleimide compound can be used. The above-mentioned bismaleimide compound includes a citraconimide compound. The above citraconimide compound is a compound in which a methyl group is bonded to one of the carbon atoms constituting the double bond between carbon atoms in the maleimide group. The bismaleimide compounds may be used alone or in combination of two or more.

  The bismaleimide compound preferably has a skeleton derived from the dimer diamine at both ends of the main chain. In this case, the bismaleimide compound may have a skeleton derived from the dimer diamine in the skeleton other than both ends of the main chain and both ends of the main chain, the dimer diamine only at both ends of the main chain It may have a skeleton derived from. In the case of having a skeleton derived from the dimer diamine, the skeletons derived from the dimer diamine are likely to associate with each other, thereby effectively increasing the glass transition temperature of the cured product of the resin material by forming a phase separation structure. You can Therefore, the thermal dimensional stability of the cured product can be further enhanced, and the adhesion between the insulating layer and the metal layer can be further enhanced.

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

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

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

  From the viewpoint of further lowering the dielectric loss tangent of the cured product and further improving the adhesion between the insulating layer and the metal layer, the N-alkyl bismaleimide compound has an aliphatic skeleton bonded to the nitrogen atom in the maleimide group. It is preferable to have a structure. Further, from the viewpoint of enhancing etching performance, the N-alkyl bismaleimide compound preferably has an imide bond or a dimer diamine skeleton, and preferably has both an imide bond and a dimer diamine skeleton.

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

  The bismaleimide compound can be obtained, for example, by reacting a tetracarboxylic dianhydride and a diamine compound to obtain a reaction product, and then reacting the reaction product with maleic anhydride.

  Further, the bismaleimide compound having the skeleton derived from the dimer diamine only at both ends of the main chain can be obtained, for example, as follows. A tetracarboxylic dianhydride, a dimer diamine, and a diamine compound other than the dimer diamine are reacted to obtain a first reaction product. The obtained first reaction product and dimer diamine are reacted to obtain a second reaction product. The obtained second reactant is reacted with maleic anhydride.

  Further, the N-alkyl bismaleimide compound having a skeleton derived from the dimer diamine is obtained by, for example, reacting a tetracarboxylic acid dianhydride with dimer diamine to obtain a reaction product, and then the reaction product and maleic anhydride. Can be obtained by reacting.

  Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetra Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether Tetracarboxylic acid dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3 ′, 4,4′-Tetraphenylsilane tetracarboxylic acid dianhydride, 1,2 , 3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis (3,4-dicarboxypheno Si) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidene diphthalic acid 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'-diphenylether dianhydride, and bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride. .

  Examples of the diamine compound include 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (aminomethyl) norbornane, 3 (4), 8 (9) -bis (aminomethyl). Tricyclo [5.2.1.02,6] decane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, isophoronediamine, 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (2 -Methylcyclohexylamine), 1,4-diaminobutane, 1,10-diaminodecane, 1,12-diaminododecane, 1,7-diaminoheptane, 1,6-diaminohexane, 1,5-diaminopentane, 1, 8-diaminooctane, 1,3-diaminopropane, 1,11-diaminoundecane, 2-me Le-1,5-diaminopentane, and dimer diamine, and the like.

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

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

  Examples of commercially available products of the N-alkyl bismaleimide compound include Designer Molecules Inc. "BMI-1500", "BMI-1700", "BMI-3000" and the like manufactured by the company are listed.

  The molecular weight of the bismaleimide compound is preferably 500 or more, more preferably 1000 or more, preferably less than 20,000, more preferably less than 15,000. When the molecular weight of the bismaleimide compound is at least the above lower limit and less than the above upper limit, the dielectric loss tangent of the cured product can be further reduced, and the adhesion between the insulating layer and the metal layer can be further enhanced. When the molecular weight of the bismaleimide compound is less than the above upper limit, the embeddability of the resin material into the irregularities of the substrate or the like can be further enhanced.

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

  In 100% by weight of the component excluding the solvent in the resin material, the content of the bismaleimide compound is preferably 3% by weight or more, more preferably 5% by weight or more, preferably 25% by weight or less, more preferably It is 20% by weight or less, particularly preferably 15% by weight or less. When the content of the bismaleimide compound is not less than the lower limit and not more than the upper limit, a sea-island structure can be formed more easily, the dielectric loss tangent can be further lowered, the thermal dimensional stability, the elastic modulus and the insulating layer can be formed. The adhesion between the metal layer and the metal layer can be further enhanced.

  The content of the bismaleimide compound in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 15% by weight or more, more preferably 20% by weight or more, and preferably 65% by weight or less. , More preferably 50% by weight or less, particularly preferably 40% by weight or less. When the content of the bismaleimide compound is not less than the lower limit and not more than the upper limit, a sea-island structure can be formed more easily, the dielectric loss tangent can be further lowered, the thermal dimensional stability, the elastic modulus and the insulating layer can be formed. The adhesion between the metal layer and the metal layer can be further enhanced.

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

  The thermoplastic resin is preferably a phenoxy resin from the viewpoint of effectively lowering the dielectric loss tangent and effectively improving the adhesion of the metal wiring regardless of the curing environment. By using the phenoxy resin, it is possible to suppress the deterioration of the embedding property of the resin film in the holes or the unevenness of the circuit board and the nonuniformity of the inorganic filler. Further, by using the phenoxy resin, the melt viscosity can be adjusted, so that the dispersibility of the inorganic filler is improved, and the resin composition or the B-staged product is less likely to spread in an unintended region during the curing process.

  The phenoxy resin contained in the resin material is not particularly limited. As the phenoxy resin, a conventionally known phenoxy resin can be used. The phenoxy resin may be used alone or in combination of two or more.

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

  Examples of commercially available products of the phenoxy resin include, for example, "YP50", "YP55" and "YP70" manufactured by Nippon Steel & Sumitomo Metal Corporation, and "1256B40", "4250", "4256H40", and "4256H40" manufactured by Mitsubishi Chemical Corporation. 4275 ”,“ YX6954BH30 ”,“ YX8100BH30 ”and the like.

  The thermoplastic resin is preferably a polyimide resin (polyimide compound) from the viewpoints of handling property, plating peel strength at low roughness, and adhesion between the insulating layer and the metal layer.

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

  Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetra Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether Tetracarboxylic acid dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3 ′, 4,4′-Tetraphenylsilane tetracarboxylic acid dianhydride, 1,2 , 3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis (3,4-dicarboxypheno Si) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidene diphthalic acid 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'-diphenylether dianhydride, and bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride. .

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

  In addition, the said polyimide compound may have an acid anhydride structure, a maleimide structure, and a citraconimide structure at the terminal. In this case, the polyimide compound and the epoxy resin can be reacted. By reacting the polyimide compound with an epoxy resin, the thermal dimensional stability of the cured product can be enhanced.

  From the viewpoint of obtaining a more excellent resin material due to storage stability, the weight average molecular weight of the thermoplastic resin, the polyimide resin and the phenoxy resin is preferably 5,000 or more, more preferably 10,000 or more, preferably 100,000 or less, more preferably Is 50,000 or less.

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

  The contents of the thermoplastic resin, the polyimide resin and the phenoxy resin are not particularly limited. In 100% by weight of the components excluding the inorganic filler and the solvent in the resin material, the content of the thermoplastic resin (when the thermoplastic resin is a polyimide resin or a phenoxy resin, the content of the polyimide resin or the phenoxy resin) is , Preferably 1% by 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 into the holes or the irregularities of the circuit board becomes good. When the content of the thermoplastic resin is at least the above lower limit, formation of the resin film becomes easier, and a better insulating layer can be obtained. When the content of the thermoplastic resin is at most the above upper limit, the coefficient of thermal expansion of the cured product will be even lower. When the content of the thermoplastic resin is less than or equal to 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 enhanced.

[solvent]
The resin material contains no solvent or contains no solvent. By using the above solvent, the viscosity of the resin material can be controlled within a suitable range, and the coating property of the resin material can be improved. Further, the solvent may be used to obtain a slurry containing the inorganic filler. As for the said solvent, only 1 type may be used and 2 or more types may be used together.

  As the solvent, 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 a mixture of naphtha.

  Most of the solvent is preferably removed when the resin composition is molded into a film. Therefore, the boiling point of the solvent is preferably 200 ° C. or lower, more preferably 180 ° C. or lower. The content of the solvent in the resin composition is not particularly limited. The content of the solvent can be appropriately changed in consideration of the coatability of the resin composition.

  When the resin material is a B stage film, the content of the solvent in 100% by weight of the B stage film is preferably 1% by weight or more, more preferably 2% by weight or more, preferably 10% by weight or less. , And more preferably 5% by weight or less.

[Other ingredients]
For the purpose of improving impact resistance, heat resistance, resin compatibility, workability, etc., the above resin materials include leveling agents, flame retardants, coupling agents, coloring agents, antioxidants, ultraviolet deterioration inhibitors, and defoaming agents. A thermosetting resin other than the agent, the thickener, the thixotropic agent and the epoxy compound may be contained.

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

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

(Other details of resin material)
The melt viscosity at 100 ° C. of the resin material is preferably 5 Pa · s or more, more preferably 10 Pa · s or more, preferably 500 Pa · s or less, more preferably 400 Pa · s or less. When the melt viscosity is not less than the lower limit and not more than the upper limit, storage stability can be further enhanced.

  The melt viscosity of the resin material at 100 ° C. was measured using a Rheometer device (for example, “AR-2000” manufactured by TA Instruments) at a frequency of 6.28 rad / sec, a starting temperature of 60 ° C., and a measurement interval temperature of 2.5. It is determined by measuring the dynamic viscoelasticity under conditions of a temperature of 5 ° C., a heating rate of 5 ° C./min, and a strain of 21.8%.

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

  The following methods are mentioned as a method of forming a resin film by molding the resin composition into a film. An extrusion molding method in which a resin composition is melt-kneaded using an extruder, extruded, and then formed into a film by a T die, a circular die, or the like. A casting method for casting a resin composition containing a solvent to form a film. Other conventionally known film forming methods. The extrusion molding method or the casting molding method is preferable because it can be made thinner. The film includes a sheet.

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

  The film-shaped 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 be further advanced.

  The resin film can be used in the form of a laminated film including a metal foil or a base film and a resin film laminated on the surface of the metal foil or the base film. The metal foil is preferably copper foil.

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

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

(Semiconductor devices, printed wiring boards, copper clad laminated boards 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 is obtained, for example, by heat-press molding the resin material.

  A member to be laminated having a metal layer on one surface or both surfaces thereof can be laminated on the resin film. It is possible to suitably obtain a laminated structure including a member to be laminated having a metal layer on the surface and a resin film laminated on the surface of the metal layer, and the resin film being the resin material described above. The method for laminating the resin film and the member to be laminated having the metal layer on the surface is not particularly limited, and a known method can be used. For example, the above-mentioned resin film can be laminated on a lamination target member having a metal layer on its surface while heating or pressurizing without heating using a device such as a parallel plate press or a roll laminator.

  The material of the metal layer is preferably copper.

  The lamination target member having the metal layer on its surface may be a metal foil such as a copper foil.

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

  The thickness of the copper foil of the copper-clad laminate is not particularly limited. The thickness of the copper foil is preferably in the range of 1 μm to 50 μm. Further, in order to enhance 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 of forming the unevenness include a method of forming by using a known chemical solution.

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

  An example of the above-mentioned multilayer substrate is a multilayer substrate including a circuit board and an insulating layer laminated on the circuit board. The insulating layer of this multilayer substrate is formed of the above resin material. Moreover, the insulating layer of the multilayer substrate may be formed of the resin film of the laminated film 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 board is laminated is roughened.

  As the roughening treatment method, a conventionally known roughening treatment method can be used and is not particularly limited. The surface of the insulating layer may be swollen before the roughening treatment.

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

  As another example of the multilayer board, a circuit board, an insulating layer laminated on the surface of the circuit board, and an insulating layer laminated on the surface opposite to the surface on which the circuit board is laminated. And a copper foil. It is preferable that the insulating layer is formed by 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 has been subjected to an etching treatment and has a copper circuit.

  Another example of the above-mentioned multilayer board is a multilayer board including a circuit board and a plurality of insulating layers laminated on the surface of the circuit board. At least one layer of the plurality of insulating layers arranged on the circuit board is formed using the resin material. 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 boards, a multilayer printed wiring board is required to have a low dielectric loss tangent and high insulation reliability due to an insulating layer. With the resin material according to the present invention, the dielectric loss tangent is low, and cracking or cracking of the cured product is less likely to occur even when subjected to thermal shock, so that the insulation reliability can be effectively improved. Therefore, the resin material according to the present invention is preferably 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 layer of the insulating layer is a cured product of the resin material.

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

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

  In the multilayer printed wiring board 11, the insulating layers 13 to 16 are formed of a cured product of the above 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 minute holes. Further, in the multilayer printed wiring board 11, the widthwise dimension (L) of the metal layer 17 and the widthwise dimension (S) of the portion where the metal layer 17 is not formed can be reduced. Further, in the multilayer printed wiring board 11, good insulation reliability is provided between the upper metal layer and the lower metal layer which are not connected by the via hole connection and the through hole connection (not shown).

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

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

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

  For the roughening treatment, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound or a persulfate compound is used. These chemical oxidizing agents are used as an aqueous solution or an organic solvent dispersion solution after adding water or an organic solvent. The roughening liquid used for the roughening treatment generally contains an alkali as a pH adjuster or the like. The roughening liquid preferably contains sodium hydroxide.

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

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

(Desmear processing)
Through holes may be formed in a cured product obtained by pre-curing the resin material. In the above-mentioned multilayer substrate or the like, vias or through holes are formed as through holes. For example, the via can be formed by irradiation with a laser such as a CO ₂ laser. The diameter of the via is not particularly limited, but is about 60 μm to 80 μm. Due to the formation of the through holes, smear, which is a residue of the resin 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 the roughening process.

  Similar to the roughening treatment, for example, a chemical oxidizer such as a manganese compound, a chromium compound or a persulfate compound is used in the desmear treatment. These chemical oxidizing agents are used as an aqueous solution or an organic solvent dispersion solution after adding water or an organic solvent. The desmear processing liquid used for the desmear processing generally contains an alkali. The desmear treatment liquid preferably contains sodium hydroxide.

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

  The following materials were prepared.

(Epoxy compound)
Biphenyl type epoxy compound ("NC-3000" manufactured by Nippon Kayaku Co., solid at 25 ° C)
Naphthol aralkyl type epoxy compound (“ESN-475V” manufactured by Nippon Steel & Sumitomo Metal Corporation, solid at 25 ° C.)
Dicyclopentadiene type epoxy compound (“EP-4088S” manufactured by ADEKA, viscosity at 25 ° C. is 230 mPa · s)
Glycidylamine type epoxy compound (“GAN” manufactured by Nippon Kayaku Co., viscosity at 25 ° C. is 130 mPa · s)

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

(Curing agent)
<First active ester compound>
Active ester compound 1 (active ester equivalent 270 eq / g)
Active ester compound 2 (active ester equivalent 305 eq / g)
Active ester compound 3 (active ester equivalent 265 eq / g)
Active ester compound 4 (active ester equivalent 315 eq / g)
Active ester compound 5 (active ester equivalent 290 eq / g)
Active ester compound 6 (active ester equivalent weight 288 eq / g)

  Active ester compound 1 was synthesized according to Synthesis Example 1 below.

<Synthesis example 1>
320 g (2.0 mol) of 2,7-dihydroxynaphthalene, 301 g (1.7 mol) of cyclohexylmethyl bromide, and paratoluene were placed in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer. 5.0 g of sulfonic acid monohydrate was added, and the mixture was stirred at room temperature while blowing nitrogen. After that, the temperature was raised to 150 ° C., and the produced water was distilled out of the system and stirred for 4 hours. After completion of the reaction, 900 g of methyl isobutyl ketone and 5.4 g of 20% aqueous sodium hydroxide solution were added to neutralize, the aqueous layer was removed by liquid separation, and the mixture was washed 3 times with 280 g of water to remove methyl isobutyl ketone. Removal under reduced pressure gave 470 g of a cyclohexylmethyl-modified naphthalene compound. The obtained cyclohexylmethyl-modified naphthalene compound was a black solid. The hydroxyl equivalent of the obtained cyclohexylmethyl-modified naphthalene compound was 185 g / equivalent.

  In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, put 203.0 g of isophthalic acid chloride (the number of moles of acid chloride group: 2.0 mol) and 1400 g of toluene, and put the system inside. It was replaced with nitrogen under reduced pressure and dissolved. Next, 72.4 g (0.67 mol) of benzyl alcohol and 246 g (the number of moles of phenolic hydroxyl group: 1.33 mol) of the obtained cyclohexyl-modified naphthalene compound were added, and the system was evacuated and replaced with nitrogen to dissolve. . Thereafter, 0.70 g of tetrabutylammonium bromide was dissolved, and the inside of the system was controlled at 60 ° C. or lower while purging with nitrogen gas, and 400 g of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Then, stirring was continued for 1.0 hour under these conditions. After the completion of the reaction, the solution was allowed to stand still for liquid separation and the aqueous layer was removed. Next, water was added to the toluene layer in which the reaction product was dissolved, and the mixture was stirred and mixed for 15 minutes, and allowed to stand still for liquid separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Then, water was removed by decanter dehydration to obtain an active ester compound 1 in a toluene solution state having a nonvolatile content of 65% by weight. The viscosity of the toluene solution having a nonvolatile content of 65% by weight was 12000 mPa · s (25 ° C.). The softening point after drying was 146 ° C.

  The obtained active ester compound 1 was an active ester compound having a structure represented by the above formula (1). In the obtained active ester compound 1, in the above formula (1), R1 and R2 are each a benzyl group, X1 is an organic group having no aromatic skeleton and has 6 carbon atoms, and X2 is a naphthalene skeleton. It was confirmed that an active ester compound having a group, m = 2, and n = 1 was included.

  Active ester compound 2 was synthesized according to Synthesis Example 2 below.

<Synthesis example 2>
A cyclohexylmethyl-modified naphthalene compound was obtained in the same manner as in Synthesis Example 1.

  In the same manner as in Synthesis Example 1 except that 72.4 g (0.67 mol) of benzyl alcohol was changed to 96.0 g (0.67 mol) of α-naphthol, a toluene solution having a nonvolatile content of 65% by weight was prepared. To obtain the active ester compound 2. The viscosity of the toluene solution having a nonvolatile content of 65% by weight was 15000 mPa · s (25 ° C.). The softening point after drying was 150 ° C.

  The obtained active ester compound 2 was an active ester compound having a structure represented by the above formula (1). In the obtained active ester compound 2, in the above formula (1), R1 and R2 are each a naphthyl group, X1 is an organic group having no aromatic skeleton and 6 carbon atoms, and X2 is a naphthalene skeleton. It was confirmed that an active ester compound having a group, m = 2, and n = 1 was included.

  Active ester compound 3 was synthesized according to Synthesis Example 3 below.

<Synthesis example 3>
Same as Synthesis Example 2 except that 301 g (1.7 mol) of cyclohexylmethyl bromide was replaced with 290 g (1.7 mol) of benzyl bromide to obtain a benzyl-modified naphthalene compound (the number of moles of phenolic hydroxyl group was To obtain an active ester compound 3 in a toluene solution state having a nonvolatile content of 65% by weight. The viscosity of the toluene solution having a nonvolatile content of 65% by weight was 16000 mPa · s (25 ° C.). The softening point after drying was 157 ° C.

  The obtained active ester compound 3 was an active ester compound having a structure represented by the above formula (1). In the obtained active ester compound 3, in the above formula (1), R1 and R2 are each a naphthyl group, X1 is a benzyl group, X2 is a group having a naphthalene skeleton, m is 2 and n is 1. It was confirmed that the compound was contained.

  Active ester compound 4 was synthesized according to Synthesis Example 4 below.

<Synthesis example 4>
In the same manner as in Synthesis Example 2 (matching the number of moles of phenolic hydroxyl groups) except that 301 g (1.7 mol) of cyclohexylmethyl bromide was changed to 376 g (1.7 mol) of 1-naphthylmethyl bromide. The active ester compound 4 in a toluene solution state having a nonvolatile content of 65% by weight was obtained. The toluene solution having a nonvolatile content of 65% by weight had a viscosity of 17,000 mPa · s and a softening point of 163 ° C.

  The obtained active ester compound 4 was an active ester compound having a structure represented by the above formula (1). In the obtained active ester compound 4, in the above formula (1), R1 and R2 are each a naphthyl group, X1 is a naphthyl group, X2 is a group having a naphthalene skeleton, m is 2 and n is 1. It was confirmed that the compound was contained.

  Active ester compound 5 was synthesized according to Synthesis Example 5 below.

<Synthesis example 5>
The same procedure as in Synthesis Example 2 (matching the number of moles of phenolic hydroxyl groups) was performed except that 301 g (1.7 mol) of cyclohexylmethyl bromide was changed to 335 g (1.7 mol) of 3- (bromomethyl) styrene. Thus, an active ester compound 5 in a toluene solution state having a nonvolatile content of 65% by weight was obtained. The toluene solution having a nonvolatile content of 65% by weight had a viscosity of 16000 mPa · s and a softening point of 152 ° C.

  The obtained active ester compound 5 was an active ester compound having a structure represented by the above formula (1). In the obtained active ester compound 5, in the above formula (1), R1 and R2 are each a naphthyl group, X1 is a styryl group, X2 is a group having a naphthalene skeleton, m is 2 and n is 2. It was confirmed that the compound was contained.

  Active ester compound 6 was synthesized according to Synthesis Example 6 below.

<Synthesis example 6>
Non-volatile components were obtained in the same manner as in Synthesis Example 2 (with the same number of moles of phenolic hydroxyl groups) except that 301 g (1.7 mol) of cyclohexylmethyl bromide was changed to 233 g (1.7 mol) of 1-bromobutane. Active ester compound 7 in a 65 wt% toluene solution state was obtained. The toluene solution having a nonvolatile content of 65% by weight had a viscosity of 14,000 mPa · s and a softening point of 135 ° C.

  The obtained active ester compound 6 was an active ester compound having a structure represented by the above formula (1). In the obtained active ester compound 6, in the above formula (1), R1 and R2 are each a naphthyl group, X1 is a butyl group, X2 is a group having a naphthalene skeleton, m is 2 and n is 1. It was confirmed that the compound was contained.

<Curing agent X>
Active ester compound having no side chain ("HPC-8000-65T" manufactured by DIC)
Aminotriazine phenol ("LA1356" manufactured by DIC)
Liquid containing carbodiimide compound (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., solid content 50% by weight)

(Curing accelerator)
Imidazole compound (2-phenyl-4-methylimidazole, "2P4MZ" manufactured by Shikoku Chemicals, anionic curing accelerator)

(Bismaleimide compound)
Bismaleimide compound ("BMI-3000J" manufactured by Digimoner Molecule Inc. (DMI))

(Thermoplastic resin)
Phenoxy resin ("YX-6954" manufactured by Mitsubishi Chemical Corporation)
Polyimide resin synthesized according to Synthesis Example A below

(Synthesis example A)
300.0 g of tetracarboxylic acid dianhydride ("BisDA-1000" manufactured by SABIC Japan LLC) and 665.5 g of cyclohexanone were placed in a reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen gas inlet tube. Then, the solution in the container was heated to 60 ° C. Then, 137.4 g of 4,4′-methylenebis (2-methylcyclohexylamine) (manufactured by Tokyo Chemical Industry Co., Ltd., having an aliphatic structure having 15 carbon atoms) was added dropwise. Then, 121.0 g of methylcyclohexane and 423.5 g of ethylene glycol dimethyl ether were added, and an imidization reaction was performed at 140 ° C. for 10 hours to obtain a polyimide resin-containing solution (nonvolatile content 26.6% by weight). The molecular weight (weight average molecular weight) of the obtained polyimide resin was 20,000. The acid component / amine component molar ratio was 1.04.

  The molecular weight of the polyimide resin synthesized in Synthesis Example A was determined as follows.

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

(Examples 1 to 15, Comparative Examples 1 to 4)
The components shown in Tables 1 to 3 below were mixed in the blending amounts shown in Tables 1 to 3 below (unit: parts by weight of solid content), and the mixture was stirred at room temperature until a uniform solution was obtained to obtain a resin material.

Production of resin film:
Using an applicator, the obtained resin material was applied onto the release-treated surface of the release-treated PET film (“XG284” manufactured by Toray Industries, Inc., thickness 25 μm), and then 2 minutes in a gear oven at 100 ° C. After drying for 30 seconds, the solvent was evaporated. Thus, a laminated film (a laminated film of a PET film and a resin film) in which a resin film (B stage film) having a thickness of 40 μm was laminated on the PET film was obtained.

(Evaluation)
(1) Storage stability (1-1) Melt viscosity at 100 ° C (melt viscosity before storage and storage stability of melt viscosity)
Melt viscosity of the obtained resin film at 100 ° C. Using a Rheometer device (“AR-2000” manufactured by TA Instruments), frequency 6.28 rad / sec, starting temperature 60 ° C., measurement interval temperature 2.5 ° C., It was determined by measuring the dynamic viscoelasticity under the conditions of a temperature rising rate of 5 ° C./min and a strain of 21.8%. The obtained melt viscosity was taken as the melt viscosity before storage.

  The obtained resin film was stored at 25 ° C. for 50 hours. The melt viscosity of the resin film after storage was measured in the same manner as above. The obtained melt viscosity was defined as the melt viscosity after storage.

  The ratio of the melt viscosity after storage to the melt viscosity before storage (melt viscosity after storage / melt viscosity before storage) was determined.

[Criteria for melt viscosity before storage]
A: Melt viscosity before storage is 5 Pa · s or more and 500 Pa · s or less B: Melt viscosity before storage is less than 5 Pa · s or more than 500 Pa · s

[Criteria for determination of storage stability of melt viscosity]
A: Ratio (melt viscosity after storage / melt viscosity before storage) is less than 2 B: Ratio (melt viscosity after storage / melt viscosity before storage) is 2 or more and less than 3 C: Ratio (melt viscosity after storage / Melt viscosity before storage) is 3 or more

  Regarding the melt viscosity before storage, the result of A is relatively better than the result of B. Regarding the storage stability of melt viscosity, the result of A is relatively better than the result of B, and the result of B is relatively better than the result of C.

(1-2) Pattern Embedding Property A copper-clad laminate (a laminate of a glass epoxy substrate having a thickness of 150 μm and a copper foil having a thickness of 35 μm) was prepared. The copper foil was subjected to etching treatment to prepare 26 copper patterns having L / S of 50 μm / 50 μm and length of 1 cm to obtain an uneven substrate. The resin film (B stage film) side of the laminated film was overlaid on the copper clad laminate using "Batch type vacuum laminator MVLP-500 / 600-IIA" manufactured by Meiki Seisakusho on both sides of the obtained uneven substrate. Laminated. The lamination conditions were such that the pressure was reduced for 30 seconds to an atmospheric pressure of 13 hPa or less, and then the pressure was applied at 100 ° C. and a pressure of 0.4 MPa for 30 seconds. Thus, a laminate in which the resin film was laminated on the uneven substrate was obtained. After peeling off the PET film, the concave portion of the uneven substrate was observed using an optical microscope, and the presence or absence of floating of the resin film was confirmed in the concave portion.

  Further, the same evaluation was performed on the resin film stored at 25 ° C. for 50 hours.

[Pattern embedding judgment criteria]
◯: No floating occurred in the resin film before and after storage. Δ: Three or less floating occurred in the resin film before and after storage. ×: Lifting in the resin film before or after storage. Occurs over 3

(1-3) FLS (Fine Line and Space)
1) Laminating process:
A double-sided copper clad laminate (copper foil thickness 18 μm on each surface, substrate thickness 0.7 mm, substrate size 100 mm × 100 mm, “MCL-E679FG” manufactured by Hitachi Chemical Co., Ltd.) was prepared. Both surfaces of the copper foil surface of this double-sided copper-clad laminate were immersed in "Cz8101" manufactured by MEC Co., Ltd. to roughen the surface of the copper foil. The resin film (B stage film) side of the laminated film was copper clad laminated on both surfaces of the roughened copper clad laminated board using "Batch type vacuum laminator MVLP-500 / 600-IIA" manufactured by Meiki Seisakusho. Laminated on a board. The lamination conditions were such that the pressure was reduced for 30 seconds to an atmospheric pressure of 13 hPa or less, and then the pressure was applied at 100 ° C. and a pressure of 0.4 MPa for 30 seconds. After peeling off the PET film, it was heated at 130 ° C. for 60 minutes to semi-cure (pre-cure) the resin film. Thus, a laminate (1) in which the semi-cured resin film was laminated on the CCL substrate was obtained.

2) Via hole formation process:
A CO ₂ laser beam machine (“LC-4KF212” manufactured by Via Mechanics) was used to form a via hole having a diameter of about 60 μm under the conditions of burst mode, energy 0.4 mJ, pulse 27 μsec, and 3 shots.

3) Desmear treatment and roughening treatment:
3-1) Swelling treatment:
The obtained laminated body (1) was put into a swelling liquid (“Swelling Dip Securigant P” manufactured by Atotech Japan Co., Ltd.) at 60 ° C. and shaken for 10 minutes. Then, it was washed with pure water.

3-2) Permanganate treatment (roughening treatment and desmear treatment):
The laminated body (1) after the swelling treatment was put into a roughened aqueous solution of potassium permanganate (“Concentrate Compact CP” manufactured by Atotech Japan Co., Ltd.) at 80 ° C. and shaken for 30 minutes. Next, after treating with a 25 ° C. washing liquid (“Reduction Securigant P” manufactured by Atotech Japan Co., Ltd.) for 2 minutes, washing with pure water was performed to obtain a roughened laminate (1).

4) Electroless plating treatment:
The surface of the cured product of the laminate (1) after the roughening treatment was treated with an alkaline cleaner (“Cleaner Seculigant 902” manufactured by Atotech Japan Co., Ltd.) at 60 ° C. for 5 minutes and degreased and washed. After washing, the cured product was treated with a pre-dip solution at 25 ° C. (“Pre-dip Neo Gantt B” manufactured by Atotech Japan) for 2 minutes. Thereafter, the cured product was treated with an activator solution (“Activator Neogant 834” manufactured by Atotech Japan Co., Ltd.) at 40 ° C. for 5 minutes, and a palladium catalyst was attached. Next, the cured product was treated with a reducing solution (“Reducer Neogant WA” manufactured by Atotech Japan Co., Ltd.) at 30 ° C. for 5 minutes.

  Next, the above-mentioned hardened material is put into a chemical copper solution ("Basic Print Gantt MSK-DK", "Kappa Print Gantt MSK", "Stabilizer Print Gantt MSK", and "Reducer Cu" manufactured by Atotech Japan Co., Ltd.), and electroless plating is performed. Was carried out until the plating thickness became about 0.5 μm. After the electroless plating, an annealing treatment was performed at a temperature of 120 ° C. for 30 minutes in order to remove the residual hydrogen gas. In addition, all the processes up to the electroless plating process were performed while the treated liquid was set to 2 L on a beaker scale and the cured product was shaken.

5) Resist formation:
A dry film resist (“RY5125” manufactured by Hitachi Chemical Co., Ltd.) was attached using a hot roll laminator. The laminating conditions were a temperature of 100 ° C., a pressure of 0.4 MPa, and a laminating speed of 1.5 m / min, and then a holding time of 15 minutes. Then, with a UV exposure machine (“EXA-1201” manufactured by Oak Manufacturing Co., Ltd.), after exposing at 85 mJ / cm ² through a pattern mask of L / S = 10 μm and L / S = 20 μm, 1% by weight Development was performed by spraying an aqueous solution of sodium carbonate at 27 ° C. for a spray pressure of 1.2 MPa for 30 seconds.

6) Electrolytic plating treatment:
Next, the electroless-plated cured product was subjected to electrolytic plating until the plating thickness became 25 μm. Copper sulfate solution as electrolytic copper plating (“copper sulfate pentahydrate” manufactured by Wako Pure Chemical Industries, Ltd., “sulfuric acid” manufactured by Wako Pure Chemical Industries, Ltd., “Basic Leveler Caparaside HL” manufactured by Atotech Japan, “Atotech Japan” Electrolytic plating was carried out using a corrector Kaparaside GS ") by applying a current of 0.6 A / cm ² until the plating thickness became about 25 μm.

7) DFR stripping and etching process:
The dry film resist (DFR) was removed by spraying with a 3 wt% sodium hydroxide aqueous solution. Then, quick etching was performed using a perhydrous sulfuric acid-based acidic etching solution (“SAC process” manufactured by JCU).

8) Main curing process:
Heated at 190 ° C. for 1.5 hours.

  In this way, an evaluation sample A having wiring formed on the cured product of the resin film was produced.

  Further, with respect to the resin film stored at 25 ° C. for 50 hours, the above steps 1) to 8) were performed to prepare an evaluation sample B in which wiring was formed on the cured resin film after storage.

  Using a scanning electron microscope (SEM), the wiring formability of the evaluation sample A and the evaluation sample B was observed.

[Criteria for FLS]
◯: L / S = 10 μm can be formed in evaluation sample A and evaluation sample B: L / S = 10 μm cannot be formed in evaluation sample A and evaluation sample B, but L / S = 20 μm Can be formed. ×: L / S = 20 μm cannot be formed in the evaluation sample A or the evaluation sample B.

(2) Dielectric loss tangent The obtained resin film was cut into a size having a width of 2 mm and a length of 80 mm and five sheets were stacked to obtain a laminate having a thickness of 200 μm. The obtained laminated body was heated at 190 ° C. for 90 minutes to obtain a cured product. The obtained cured product was subjected to a cavity resonance method at room temperature (23 ° C.) by using “cavity resonance perturbation method dielectric constant measuring device CP521” manufactured by Kanto Electronics Application Development Co., Ltd. and “Network Analyzer N5224A PNA” manufactured by Keysight Technology Co., Ltd. Then, the dielectric loss tangent was measured at a frequency of 1.0 GHz.

[Judgment standard of dielectric loss tangent]
◯: Dielectric loss tangent is 0.005 or less Δ: Dielectric loss tangent exceeds 0.005 and less than 0.01 x: Dielectric loss tangent exceeds 0.01

(3) Thermal shock test The PET film of the obtained laminated film is peeled off, both sides of the resin film are sandwiched between a copper foil with a thickness of 35 μm and a copper plate with a thickness of 1 mm, and vacuum pressed under the conditions of a temperature of 200 ° C. and a pressure of 3 MPa. A laminate was prepared by. By etching the copper foil in the obtained laminate, the copper foil was patterned into a circle having a diameter of 2 cm to obtain a test sample. Using the obtained test sample, using a tank-type thermal shock tester (“TSB-51” manufactured by ESPEC), the temperature was maintained at −40 ° C. for 5 minutes, and then the temperature was raised to 120 ° C. A cooling / heating cycle test was carried out, in which the process of holding for a minute and then lowering the temperature to −40 ° C. was one cycle. Test samples were taken out after 1000 cycles and after 2000 cycles, respectively. The presence or absence of cracks or cracks in the cured product of the resin film was observed using an optical microscope ("STM6" manufactured by Olympus Corp.).

[Criteria for thermal shock test]
◯: No cracks or cracks in the cured product after 2000 cycles Δ: No cracks or cracks in the cured product after 1000 cycles, and cracks or cracks in the cured product after 2000 cycles ×: After 1000 cycles There are cracks or cracks in the cured product

  The composition and results are shown in Tables 1-3 below.

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

Claims (22)

Including an epoxy compound, an inorganic filler, and a curing agent,
The curing agent contains an active ester compound having a structure represented by the following formula (1),
A resin material in which the content of the inorganic filler is 55% by weight or more based on 100% by weight of the component excluding the solvent in the resin material (excluding the resin material used by impregnating the fiber base material).

In the formula (1), R1, R2 and X1 each represent an organic group, X2 represents a group containing an aliphatic chain skeleton, a group containing an aliphatic skeleton or a group containing an aromatic skeleton, and m is 1 It represents an integer of 6 or more and n, and n represents an integer of 1 or more and 5 or less.   The resin material according to claim 1, wherein X1 in the formula (1) is an organic group having 5 or more carbon atoms.   The resin material according to claim 1 or 2, wherein in the formula (1), X1 is a group having an aromatic skeleton.   The resin material according to any one of claims 1 to 3, wherein in the formula (1), X1 is a group having two or more aromatic skeletons.   The resin material according to any one of claims 1 to 4, wherein in the formula (1), X1 is a group having no reactive group.   The resin material according to any one of claims 1 to 5, wherein R1 or R2 in the formula (1) is a group having a heteroaromatic ring skeleton.   The resin material according to any one of claims 1 to 6, wherein in the formula (1), R1 or R2 is a group having an imide skeleton.   The resin material according to any one of claims 1 to 7, wherein R1 or R2 in the formula (1) is a group having a naphthalene skeleton.   The resin material according to any one of claims 1 to 8, wherein in the formula (1), R1, R2, X1 and X2 are each a group having no phosphorus atom.   In the formula (1), each of R1, R2, X1 and X2 is a group having no aliphatic hydrocarbon chain with a carbon number of 2 or more and 4 or less. The resin material described.   The resin material according to any one of claims 1 to 10, which has a melt viscosity at 100 ° C of 5 Pa · s or more and 500 Pa · s or less.   The resin material according to any one of claims 1 to 11, wherein the curing agent contains an active ester compound having no side chain.   The resin material according to any one of claims 1 to 12, wherein the curing agent contains a carbodiimide compound.   The resin material according to any one of claims 1 to 13, wherein an active ester equivalent of the active ester compound having the structure represented by the formula (1) is 200 eq / g or more and 500 eq / g or less.   The resin material according to any one of claims 1 to 14, wherein the epoxy compound includes a naphthol aralkyl type epoxy compound.   The resin material according to any one of claims 1 to 15, wherein the inorganic filler is silica.   The resin material according to any one of claims 1 to 16, which contains a curing accelerator.   The resin material according to any one of claims 1 to 17, containing a bismaleimide compound.   The resin material according to any one of claims 1 to 18, which comprises a thermoplastic resin.   The resin material according to any one of claims 1 to 19, which is a resin film.   The resin material according to any one of claims 1 to 20, which is used for forming an insulating layer in a multilayer printed wiring board. Circuit board,
A plurality of insulating layers disposed on the surface of the circuit board,
A metal layer disposed between the plurality of insulating layers,
A multilayer printed wiring board, wherein at least one layer of the plurality of insulating layers is a cured product of the resin material according to any one of claims 1 to 21.

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