KR102508097B1 - Resin materials, laminated films and multi-layer printed wiring boards - Google Patents

Abstract

To provide a resin material capable of suppressing the occurrence of blisters and having excellent storage stability, so that even after storage, the embeddability to holes or concavo-convex surfaces can be improved. The resin material according to the present invention includes an epoxy compound, a curing agent, and silica, and the curing agent includes a cyanate ester compound and a carbodiimide compound.

Description

Resin materials, laminated films and multi-layer printed wiring boards

The present invention relates to a resin material containing an epoxy compound, a curing agent, and an inorganic filler. Further, the present invention relates to a laminated film and a multilayer printed wiring board using the above resin material.

Conventionally, in order to obtain electronic parts, such as a laminated board and a printed wiring board, various resin compositions are used. For example, in a multilayer printed wiring board, a resin composition is used to form an insulating layer for insulating between internal layers or to form an insulating layer located on a surface layer portion. On the surface of the insulating layer, wiring, which is generally metal, is laminated. Moreover, in order to form an insulating layer, the B stage film which made the said resin composition into a film may be used. The resin composition and the B-stage film are used as insulating materials for printed wiring boards including build-up films.

An example of the resin composition is disclosed in Patent Document 1 below. The resin composition described in Patent Literature 1 includes (A) an epoxy resin, (B) a cyanate ester resin, (C) an adduct of an imidazole compound and an epoxy resin, and (D) a metal-based curing catalyst.

Japanese Unexamined Patent Publication No. 2013-151700

Some conventional resin compositions described in Patent Literature 1 or B-stage films in which the resin composition is B-staged have low storage stability. For example, in some cases, an insulating layer is formed on wiring to obtain a multilayer printed wiring board using a resin composition or a B-stage film stored for a certain period of time. In this case, there are cases where the resin composition or the B-stage film is not sufficiently embedded in the uneven surface of the wiring. As a result, voids may occur.

In addition, when a conventional resin composition or B-stage film is used, blisters may occur due to moisture absorption.

An object of the present invention is to provide a resin material capable of suppressing the occurrence of blisters and having excellent storage stability, so that even after storage, the embeddability to holes or concavo-convex surfaces can be improved. Moreover, this invention provides the laminated|multilayer film and multilayer printed wiring board using the said resin material.

According to the broad aspect of this invention, the resin material containing an epoxy compound, a hardening|curing agent, and silica, and the said hardening|curing agent containing a cyanate ester compound and a carbodiimide compound is provided.

In a specific aspect of the resin material according to the present invention, the content of the silica is 50% by weight or more in 100% by weight of components excluding the solvent in the resin material.

In a specific aspect of the resin material according to the present invention, the ratio of the content of the cyanate ester compound to the content of the carbodiimide compound is 0.2 or more and 4.0 or less in terms of weight ratio.

In a specific aspect of the resin material according to the present invention, the ratio of the content of the epoxy compound to the content of the curing agent is 1.0 or more and 3.0 or less in terms of weight ratio.

In a specific aspect of the resin material according to the present invention, the carbodiimide compound has an alicyclic skeleton.

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

In a specific aspect of the resin material according to the present invention, the resin material is a resin material for a multilayer printed wiring board used to form an insulating layer in a multilayer printed wiring board.

In a specific aspect of the resin material according to the present invention, the resin material is used to obtain a cured product subjected to roughening treatment.

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

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

Since the resin material according to the present invention includes an epoxy compound, a curing agent, and silica, and the curing agent includes a cyanate ester compound and a carbodiimide compound, the occurrence of blisters can be suppressed and storage stability is excellent. Even after preservation, it is possible to improve embedding into holes or uneven surfaces.

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

Hereinafter, the present invention will be described in detail.

The resin material according to the present invention contains an epoxy compound, a curing agent and silica. In the resin material according to the present invention, the curing agent contains a cyanate ester compound and a carbodiimide compound.

In the present invention, since the above structure is provided, the generation of blisters can be suppressed. For example, even if a resin film (resin material) or a cured product of a resin material absorbs moisture, blisters are less likely to occur.

Moreover, since the said structure is provided in this invention, storage stability can be improved. Even after the resin material according to the present invention has been stored for a certain period of time, the resin material can be satisfactorily embedded in the hole or the concave-convex surface. For example, in a multilayer printed wiring board, an insulating layer is formed on wiring. On the surface on which the insulating layer is formed, there are wires and irregularities exist. By using the resin material according to the present invention, it is possible to satisfactorily embed the insulating layer on the wiring, and the occurrence of voids can be suppressed.

Moreover, since the said structure is provided in this invention, the adhesiveness of hardened|cured material (insulation layer etc.) and a metal layer can also be improved. For example, the peel strength of the metal layer to the cured product can be increased.

In addition, since the above structure is provided in the present invention, the uniformity of the film can be improved when the resin composition is formed into a film after storage for a certain period of time, and the uniformity of the cured product can also be improved when the resin material is cured.

The resin material according to the present invention may be a resin composition or a resin film. The resin composition has fluidity. The resin composition may be in the form of a paste. The paste phase includes a liquid phase. From the standpoint of excellent handleability, the resin material according to the present invention is preferably a resin film. Further, in the present invention, even if the resin material is a resin film, the resin film can be satisfactorily embedded in a hole or an uneven surface.

Since the resin material according to the present invention is excellent in the above properties, it is suitably used for forming an insulating layer in a multilayer printed wiring board. The resin material according to the present invention is preferably a resin material for a multilayer printed wiring board, more preferably a resin material for interlayer insulation used in a multilayer printed wiring board, from the viewpoint of having the above properties.

In the above multilayer printed wiring board, it is preferable that the thickness of the insulating layer formed of the resin material (thickness per layer) is equal to or greater than the thickness of the conductor layer (metal layer) forming the circuit. The thickness of the insulating layer (thickness per layer) is preferably 5 μm or more, and preferably 200 μm or less.

The resin material according to the present invention is suitably used to obtain a cured product subjected to a roughening process.

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 are described.

[Epoxy compound]

The epoxy compound contained in the resin material is not particularly limited. As the epoxy compound, conventionally known epoxy compounds can be used. The epoxy compound refers to an organic compound having at least one epoxy group. As for the said epoxy compound, only 1 type may be used and 2 or more types may be used together.

Examples of the epoxy compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolak type epoxy resins, biphenyl type epoxy resins, biphenyl novolak type epoxy resins, biphenol type epoxy resins, Naphthalene type epoxy resin, fluorene type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type epoxy resin, epoxy resin having an adamantane skeleton, tricyclodecane Epoxy resins having skeletons, and epoxy resins having triazine nuclei as skeletons, and the like are exemplified.

From the viewpoint of more effectively exhibiting the effect of improving storage stability, suppressing the occurrence of blisters, and improving the adhesion between the cured product and the metal layer, the epoxy compound preferably has an aromatic skeleton, and has a biphenyl skeleton. It is preferable, and it is preferable that it is a biphenyl type epoxy compound. Moreover, when the said epoxy compound has a biphenyl skeleton, the adhesive strength of hardened|cured material and a metal layer further increases.

As for the molecular weight of the said epoxy compound, it is more preferable that it is 1000 or less. In this case, even if the content of silica in 100% by weight of components excluding the solvent in the resin material is 30% by weight or more or even if the content of silica is 60% by weight or more, a resin composition with high fluidity is obtained. For this reason, when the resin material is disposed on the substrate, silica can be uniformly present.

The molecular weight of the epoxy compound and the molecular weight of the curing agent described below mean the molecular weight that can be calculated from the structural formula when the epoxy compound or curing agent is not a polymer and when the structural formula of the epoxy compound or curing agent can be specified. In addition, when an epoxy compound or a hardening|curing agent is a polymer, it means a weight average molecular weight.

The weight average molecular weight of the epoxy compound and the curing agent (cyanate ester compound and carbodiimide compound) described later indicates the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[curing agent]

The resin material contains a cyanate ester compound and a carbodiimide compound as a curing agent.

As a curing agent for curing the epoxy compound, various curing agents exist. As the curing agent for curing the epoxy compound, cyanate ester compound (cyanate ester curing agent), phenolic compound (phenol curing agent), amine compound (amine curing agent), thiol compound (thiol curing agent), imidazole compound, phosphine compound, acid Anhydrides, active ester compounds, dicyandiamide and carbodiimide compounds (carbodiimide curing agent), and the like are exemplified. In this invention, at least 2 types of a cyanate ester compound and a carbodiimide compound are used as a hardening|curing agent.

Examples of the cyanate ester compound include novolak-type cyanate ester resins, bisphenol-type cyanate ester resins, and prepolymers obtained by partially trimerizing these. Examples of the novolak-type cyanate ester resin include phenol novolak-type cyanate ester resins and alkylphenol-type cyanate ester resins. As said bisphenol type cyanate ester resin, bisphenol A type cyanate ester resin, bisphenol E type cyanate ester resin, tetramethyl bisphenol F type cyanate ester resin, etc. are mentioned. As for the said cyanate ester compound, only 1 type may be used and 2 or more types may be used together.

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

From the viewpoint of more effectively exhibiting the effect of improving storage stability, suppressing the occurrence of blisters, and improving the adhesion between the cured product and the metal layer, the molecular weight of the cyanate ester compound is preferably 200 or more, more preferably It is 300 or more, Preferably it is 4000 or less, More preferably, it is 2000 or less.

The said carbodiimide compound has a structural unit represented by following formula (1). In the following formula (1), the right end and the left end are bonding 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 (1), X represents an alkylene group, a group having a substituent bonded to an alkylene group, a cycloalkylene group, a group having a substituent bonded to a cycloalkylene group, an arylene group, or a group having a substituent bonded to an arylene group, and p represents an integer from 1 to 5. When a plurality of X's exist, the plurality of X's may be the same or different.

When X is an alkylene group or a group having a substituent bonded to the alkylene group, the number of carbon atoms in the alkylene group is preferably 1 or more, preferably 20 or less, more preferably 10 or less, still more preferably 6 or less. , particularly preferably 4 or less, most preferably 3 or less. Preferable examples of the alkylene group include a methylene group, an ethylene group, a propylene group and a butylene group.

When X is a cycloalkylene group or a group having a substituent bonded to the cycloalkylene group, the number of carbon atoms in the cycloalkylene group is preferably 3 or more, preferably 20 or less, more preferably 12 or less, still more preferably is less than 6. Preferable examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group and a cyclohexylene group.

When X is an arylene group or a group having a substituent bonded to the arylene group, the arylene group is a group obtained by removing two hydrogen atoms on the aromatic ring from an aromatic hydrocarbon. The number of carbon atoms in the arylene group is preferably 6 or more, preferably 24 or less, more preferably 18 or less, still more preferably 14 or less, and particularly preferably 10 or less. Preferable examples of the arylene group include a phenylene group, a naphthylene group and an anthracenylene group.

X may be a group having a substituent bonded to an alkylene group, a group having a substituent bonded to a cycloalkylene group, or a group having a substituent bonded to an arylene group. In this case, the substituent is not particularly limited, and examples thereof include a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, an aryl group, an aryloxy group, an acyl group, and an acyloxy group. As a halogen atom as a substituent, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example. The alkyl group and alkoxy group as a substituent may be linear or branched. The number of carbon atoms in the alkyl group and alkoxy group as a substituent is preferably 1 or more, preferably 20 or less, more preferably 10 or less, still more preferably 6 or less, particularly preferably 4 or less, and most preferably 3 or less. below The number of carbon atoms in the cycloalkyl group and cycloalkyloxy group as substituents is preferably 3 or more, preferably 20 or less, more preferably 12 or less, still more preferably 6 or less. An aryl group as a substituent is a group obtained by removing one hydrogen atom on an aromatic ring from an aromatic hydrocarbon. The number of carbon atoms in the aryl group as a substituent is preferably 6 or more, preferably 24 or less, more preferably 18 or less, still more preferably 14 or less, and particularly preferably 10 or less. The number of carbon atoms in the aryloxy group as a substituent is preferably 6 or more, preferably 24 or less, more preferably 18 or less, still more preferably 14 or less, and particularly preferably 10 or less. The acyl group as a substituent is a group represented by the formula: -C(=O)-R1, in which R1 represents an alkyl group or an aryl group. The alkyl group represented by R1 may be linear or branched. The number of carbon atoms in the alkyl group represented by R1 is preferably 1 or more, preferably 20 or less, more preferably 10 or less, still more preferably 6 or less, particularly preferably 4 or less, and most preferably 3 or less. am. The number of carbon atoms in the aryl group represented by R1 is preferably 6 or more, preferably 24 or less, more preferably 18 or less, still more preferably 14 or less, and particularly preferably 10 or less. The acyloxy group as a substituent is a group represented by the formula: -O-C(=O)-R1, and in the formula, R1 represents the same meaning as R1 of the acyl group. As a substituent, an alkyl group, an alkoxy group, or an acyloxy group is preferable, and an alkyl group is more preferable.

In one suitable embodiment, at least one X is 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.

In one preferred embodiment, the amount of the carbodiimide compound is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably, when the weight of the entire molecule of the carbodiimide compound is 100% by weight. is 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more, and has a structural unit represented by formula (1). That is, it is preferable that the carbodiimide compound contains the structural unit represented by formula (1) so as to satisfy the lower limit of the above-mentioned content. The carbodiimide compound may be a structural unit whose structure except for the terminal structure is substantially represented by formula (1). The terminal structure of the carbodiimide compound is not particularly limited, but examples include an alkyl group, a group in which a substituent is bonded to an alkyl group, a cycloalkyl group, a group in which a substituent is bonded to a cycloalkyl group, an aryl group, and a group in which a substituent is bonded to an aryl group. there is. The substituent in the group having a substituent bonded to an alkyl group as a terminal structure, the group having a substituent bonded to a cycloalkyl group, and the group having a substituent bonded to an aryl group is referred to as substituent A. Examples of the substituent A include substituents exemplified as substituents in the group in which X in the formula (1) has a substituent bonded to an alkylene group, a group in which a substituent is bonded to a cycloalkylene group, or a group in which a substituent is bonded to an arylene group. there is. In addition, the substituent A may be the same as the substituent in the group in which X in the formula (1) has a substituent bonded to an alkylene group, a group in which a substituent is bonded to a cycloalkylene group, or a group in which a substituent is bonded to an arylene group, It may be different.

In addition, the carbodiimide compound may have an isocyanate group (-N=C=O) derived from its production method. From the viewpoint of further enhancing the storage stability of the resin material and realizing an insulating layer exhibiting even better characteristics, the content of isocyanate groups in the carbodiimide compound (also referred to as "NCO content") is preferably 5% by weight. or less, more preferably 4% by weight or less, even more preferably 3% by weight or less, still more preferably 2% by weight or less, particularly preferably 1% by weight or less, and most preferably 0.5% by weight or less. The content of the isocyanate group in the carbodiimide compound may be 0% by weight (non-containing).

From the viewpoint of more effectively exhibiting the effects of improving storage stability, suppressing the occurrence of blisters, and improving the adhesion between the cured product and the metal layer, the carbodiimide compound preferably has an alicyclic skeleton. In particular, when the carbodiimide compound has an alicyclic skeleton, the storage stability is further enhanced. In addition, when the carbodiimide compound does not have an aromatic skeleton and has an alicyclic skeleton, storage stability is significantly increased.

Examples of commercially available products of the carbodiimide compound include carbodilite (registered trademark) V-02B, V-03, V-04K, V-07, V-09, 10M-SP and 10M-SP manufactured by Nisshinbo Chemical Co., Ltd. ), and Stavaczol (registered trademark) P, P400 and Hycardil 510 manufactured by Rhein Chemistry.

From the viewpoint of more effectively exhibiting the effect of improving storage stability, suppressing the occurrence of blisters, and improving the adhesion between the cured product and the metal layer, the molecular weight of the carbodiimide compound is preferably 500 or more, more preferably It is 1000 or more, Preferably it is 5000 or less, More preferably, it is 3000 or less.

The ratio of the content of the cyanate ester compound to the content of the carbodiimide compound is described as ratio (content of the cyanate ester compound/content of the carbodiimide compound). From the viewpoint of more effectively exhibiting the effect of improving the storage stability, suppressing the occurrence of blisters, and improving the adhesion between the cured product and the metal layer, the ratio (content of cyanate ester compound / content of carbodiimide compound) is In terms of weight ratio, it is preferably 0.2 or more, more preferably 0.3 or more, preferably 4.0 or less, and more preferably 3.8 or less.

The ratio of the content of the epoxy compound to the content of the curing agent is described as ratio (content of the epoxy compound/content of the curing agent). From the viewpoint of more effectively exhibiting the effect of improving storage stability, suppressing the occurrence of blisters, and improving the adhesion between the cured product and the metal layer, the above ratio (content of the epoxy compound / content of the curing agent) is a weight ratio, preferably is 1.0 or more, more preferably 1.2 or more, preferably 3.0 or less, more preferably 2.8 or less. The content of the curing agent is the total content of the content of the cyanate ester compound, the content of the carbodiimide compound, and other curing agents when blended with other curing agents.

The total content of the epoxy compound and the curing agent in 100% by weight of components excluding the silica and the solvent in the resin material is preferably 65% by weight or more, more preferably 70% by weight or more, and preferably 99% by weight or more. % by weight or less, more preferably 97% by weight or less. When the total content of the epoxy compound and the curing agent is equal to or more than the lower limit and equal to or less than the upper limit, a better cured product is obtained, and the dimensional change of the insulating layer due to heat can be further suppressed. The content ratio of the epoxy compound and the curing agent is appropriately selected so that the epoxy compound is cured.

[Thermoplastic resin]

The resin material may contain a thermoplastic resin.

As said thermoplastic resin, a polyimide resin, a polyvinyl acetal resin, a phenoxy resin, etc. are mentioned. As for the said thermoplastic resin, only 1 type may be used and 2 or more types may be used together.

It is preferable that the thermoplastic resin is a phenoxy resin from the viewpoint of effectively lowering the dielectric loss tangent and effectively increasing the adhesion of the metal wiring regardless of the curing environment. By use of the phenoxy resin, deterioration of embeddability of the resin material in holes or irregularities of the circuit board and non-uniformity of silica are suppressed. In addition, since the melt viscosity can be adjusted by using the phenoxy resin, the dispersibility of the silica becomes good, and the resin material does not spread to an unintended area during the curing process. The phenoxy resin is not particularly limited. As the phenoxy resin, conventionally known phenoxy resins can be used. As for the said phenoxy resin, only 1 type may be used and 2 or more types may be used together.

Examples of the phenoxy resin include phenoxy resins having skeletons such as bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, biphenyl skeleton, novolac skeleton, naphthalene skeleton, and imide skeleton. can be heard

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

From the viewpoint of further enhancing the storage stability, the weight average molecular weight of the thermoplastic resin is preferably 5000 or more, more preferably 10000 or more, and preferably 100000 or less, more preferably 50000 or less.

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

Content of the said thermoplastic resin is not specifically limited. The content of the thermoplastic resin (content of the phenoxy resin when the thermoplastic resin is a phenoxy resin) in 100% by weight of components excluding the silica and the solvent in the resin material is preferably 2% by weight or more, more preferably It is 4 weight% or more, Preferably it is 15 weight% or less, More preferably, it is 10 weight% or less. When the content of the thermoplastic resin is equal to or greater than the lower limit and equal to or less than the upper limit, the embedding of the resin material into holes or irregularities of the circuit board becomes good. If content of the said thermoplastic resin is more than the said minimum, film formation of a resin composition will become still more easy, and a much better insulating layer will be obtained. The thermal expansion coefficient of hardened|cured material becomes further low as content of the said thermoplastic resin is below the said upper limit. In addition, the surface roughness of the surface of the insulating layer is further reduced, and the adhesive strength between the insulating layer and the metal layer is further increased.

[Silica]

The resin material contains silica as an inorganic filler. The use of silica further reduces the dimensional change of the cured product due to heat. Moreover, the dielectric loss tangent of hardened|cured material becomes still smaller. Moreover, compared with other inorganic fillers, the adhesive strength of hardened|cured material and a metal layer can also be further raised.

From the viewpoint of reducing the surface roughness of the surface of the insulating layer, further increasing the adhesive strength between the insulating layer and the metal layer, forming finer wiring on the surface of the cured product, and imparting good insulation reliability by the cured product. , It is more preferable that the silica is fused silica. It is preferable that the shape of silica is spherical.

The average particle diameter of the silica is preferably 10 nm or more, more preferably 50 nm or more, still more preferably 150 nm or more, preferably 20 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, Especially preferably, it is 1 micrometer or less. When the average particle diameter of the silica is equal to or greater than the lower limit and equal to or less than the upper limit, the size of pores formed by roughening treatment or the like becomes smaller, and the number of pores increases. As a result, the adhesive strength between the cured product and the metal layer is further increased.

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

It is preferable that the said silica is spherical, and it is more preferable that it is 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 silica is spherical, the aspect ratio of the silica is preferably 2 or less, more preferably 1.5 or less.

The silica is preferably surface treated, more preferably surface treated with a coupling agent, and still more preferably surface treated with a silane coupling agent. As a result, the surface roughness of the surface of the cured product is further 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 furthermore, insulation reliability between wiring and interlayer is improved. Insulation reliability can be given to hardened|cured material.

As said coupling agent, a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, etc. are mentioned. As said silane coupling agent, methacrylsilane, acrylsilane, aminosilane, imidazolesilane, vinylsilane, epoxysilane, etc. are mentioned.

The silica content is preferably 30% by weight or more, more preferably 40% by weight or more, still more preferably 50% by weight or more, and particularly preferably 60% by weight in 100% by weight of the components excluding the solvent in the resin material. % or more, preferably 90% by weight or less, more preferably 85% by weight or less, still more preferably 80% by weight or less, and particularly preferably 75% by weight or less. When the content of the silica is equal to or more than the lower limit, the dimensional change of the cured product due to heat becomes smaller. In addition, when the content of the silica is equal to or more than the lower limit and equal to or less than the upper limit, 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.

[Curing accelerator]

It is preferable that the said resin material contains a hardening accelerator. By use of the said hardening accelerator, the hardening speed is further accelerated. By rapidly curing the resin material, the number of unreacted functional groups is reduced, resulting in a high cross-linking density. 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.

As said hardening accelerator, an imidazole compound, a phosphorus compound, an amine compound, and an organic metal compound etc. are mentioned, for example.

As said imidazole compound, 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl -4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole Sol, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyano Ethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1' )]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6 -[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1') ]-Ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydride oxymethylimidazole and 2-phenyl-4-methyl-5-dihydroxymethylimidazole; and the like.

Triphenylphosphine etc. are mentioned as said phosphorus compound.

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

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

Content of the said hardening accelerator is not specifically limited. The content of the curing accelerator is preferably 0.01% by weight or more, more preferably 0.9% by weight or more, and more preferably 5.0% by weight or less, more preferably It is preferably 3.0% by weight or less. The resin material is efficiently cured as the content of the curing accelerator is equal to or more than the lower limit and equal to or less than the upper limit. When the content of the curing accelerator is within a more preferable range, the storage stability of the resin material is further increased, and a further improved cured product is obtained.

[solvent]

The resin material does not contain or contains a solvent. By use of the above solvent, the viscosity of the resin material can be controlled within a suitable range, and when the resin material is a resin composition, the coatability of the resin composition can be improved. Moreover, the said solvent may be used in order to obtain the slurry containing the said silica. As for the said solvent, only 1 type may be used and 2 or more types may be used together.

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

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

[Other Ingredients]

For the purpose of improving impact resistance, heat resistance, resin compatibility and workability, etc., the resin material includes a leveling agent, a flame retardant, a coupling agent, a colorant, an antioxidant, an ultraviolet deterioration inhibitor, an antifoaming agent, a thickener, and a thixotropy imparting agent. And you may add other thermosetting resins other than an epoxy compound.

As said coupling agent, a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, etc. are mentioned. Examples of the silane coupling agent include vinylsilane, aminosilane, imidazolesilane, and epoxysilane.

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

(Resin film (B stage film) and laminated film)

It is preferable that the said resin material is a resin film. A resin film (B stage film) is obtained by molding the resin composition into a film shape. It is preferable that a resin film is a B-stage film.

From the viewpoint of controlling the curing degree of the resin film more uniformly, the thickness of the resin film is preferably 5 μm or more, and preferably 200 μm or less.

As a method of forming the resin composition into a film shape, for example, an extrusion molding method in which a resin material is melt-kneaded and extruded using an extruder, and then formed into a film shape by a T-die or circular die, etc., and a resin containing a solvent. A casting molding method in which a material is cast and formed into a film shape, and other conventionally known film molding methods, and the like may be mentioned. In terms of being able to respond to thinning, an extrusion molding method or a casting molding method is preferable. A film includes a sheet.

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

The film-shaped resin material obtained by the above drying process is called a B-stage film. The B-stage film is a film-shaped resin material in a semi-cured state. The semi-hardened material is not completely hardened, and hardening may proceed further.

The resin film may not be a prepreg. When the resin film is not a prepreg, migration does not occur due to a glass cloth or the like. Further, when the resin film is laminated or pre-cured, irregularities caused by the glass cloth are not generated on the surface. The resin material can be suitably used in the form of a laminated film comprising a substrate and a resin film laminated on the surface of the substrate. The resin film in the laminated film is formed of the resin composition.

Examples of the base material of the laminated film include metal foil, polyester resin films such as polyethylene terephthalate films and polybutylene terephthalate films, olefin resin films such as polyethylene films and polypropylene films, and polyimide films. The surface of the base material may be subjected to release treatment as needed. The substrate may be a metal foil or a resin film. It is preferable that the said metal foil is a copper foil.

(multilayer printed wiring board)

A multilayer printed wiring board according to the present invention includes a circuit board, a plurality of insulating layers disposed on the circuit board, and a metal layer disposed between the plurality of insulating layers. At least one layer in the insulating layer is a cured product of the resin material described above. The insulating layer in contact with the circuit board may be a cured product of the resin material described above. The insulating layer disposed between the two insulating layers may be a cured product of the resin material described above. The insulating layer farthest from the circuit board may be a cured product of the above-described resin material. Among the plurality of insulating layers, a metal layer may be disposed on an outer surface of the insulating layer furthest away from the circuit board.

The said multilayer printed wiring board is obtained by heat-pressing molding the said resin film, for example.

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

Moreover, the insulating layer of a multilayer printed wiring board may be formed of the said resin film of the said laminated film using laminated|multilayer film. It is preferable that the said insulating layer is laminated|stacked on the surface of the circuit board on which the circuit was provided. Part of the insulating layer is preferably buried between the circuits.

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

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

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

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

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

(Harmonization treatment and swelling treatment)

It is preferable that the said resin material is used in order to obtain the hardened|cured material subjected to the roughening process or the desmear process. The cured product includes a precured product that can be further cured.

Since fine irregularities are formed on the surface of the cured product obtained by pre-curing the resin material, the cured product is preferably subjected to a roughening treatment. Before the roughening treatment, the cured product is preferably subjected to a swelling treatment. It is preferable that the hardened|cured material is subjected to the swelling treatment after the pre-curing and before the roughening treatment, and also to be cured after the roughening treatment. However, the hardened|cured material does not necessarily need to be subjected to swelling treatment.

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

Chemical oxidizing agents, such as a manganese compound, a chromium compound, or a persulfuric acid compound, etc. are used for the said roughening process, for example. These chemical oxidizing agents are used as an aqueous solution or an organic solvent dispersion solution after water or an organic solvent is added. A roughening liquid used for a roughening process generally contains an alkali as a pH adjuster or the like. It is preferable that the crude liquid 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 persulfuric acid compound include sodium persulfate, potassium persulfate, and ammonium persulfate.

The method of the said roughening process is not specifically limited. As a method of the roughening treatment, for example, using a 30 to 90 g / L permanganic acid or permanganate solution and a 30 to 90 g / L sodium hydroxide solution, under conditions of a treatment temperature of 30 to 85 ° C. and 1 to 30 minutes, the cured product How to handle is suitable. It is preferable that the temperature of the said roughening process exists in the range of 50-85 degreeC. It is preferable that the frequency|count of the said roughening process is 1 time or 2 times.

The surface arithmetic average roughness Ra of the cured product is preferably 10 nm or more, preferably less than 200 nm, more preferably less than 100 nm, still more preferably less than 50 nm. When the arithmetic average roughness Ra is equal to or greater than the lower limit and less than the upper limit, the conductor loss of the electrical signal can be effectively suppressed, and the transmission loss can be largely suppressed. Further, finer wiring can be formed on the surface of the insulating layer. The said arithmetic average roughness Ra is measured based on JIS B0601 (1994).

(Desmear treatment)

A through hole may be formed in the cured product obtained by pre-curing the resin material. In the above multi-layer substrate or the like, vias or through holes are formed as through holes. For example, vias can be formed by irradiation of a laser such as a CO ₂ laser. The diameter of the via is not particularly limited, but is about 60 to 80 μm. Due to the formation of the through hole, a smear, which is a residue of a resin derived from a resin component contained in the cured product, is formed in the bottom portion of the via in many cases.

In order to remove the smear, the surface of the cured product is preferably subjected to a desmear treatment. In some cases, the desmear treatment also serves as a reconciliation treatment.

Chemical oxidizing agents, such as a manganese compound, a chromium compound, or a persulfuric acid compound, etc. are used for the said desmear process similarly to the said roughening process, for example. These chemical oxidizing agents are used as an aqueous solution or an organic solvent dispersion solution after water or an organic solvent is added. The desmear treatment liquid used for the desmear treatment generally contains an alkali. The desmear treatment liquid preferably contains sodium hydroxide.

The method of the said desmear process is not specifically limited. As a method of the desmear treatment, for example, using 30 to 90 g / L permanganic acid or permanganate solution and 30 to 90 g / L sodium hydroxide solution, under conditions of a treatment temperature of 30 to 85 ° C. and 1 to 30 minutes, 1 A method of treating ash or 2 cured products is suitable. The temperature of the desmear treatment is preferably in the range of 50 to 85 ° C.

By use of the resin material, the surface roughness of the surface of the insulating layer subjected to the desmear treatment is sufficiently reduced.

Hereinafter, the present invention will be described in detail with examples and comparative examples. The present invention is not limited to the following examples.

(epoxy compound)

Bisphenol A type epoxy resin ("850-S" manufactured by DIC Corporation)

Naphthalene type epoxy resin ("HP-4032D" manufactured by DIC Corporation)

Biphenyl novolac type epoxy resin ("NC-3000" manufactured by Nippon Kayaku Co., Ltd.)

Bisphenol F-type epoxy resin ("830-S" manufactured by DIC Corporation)

Biphenyl type epoxy resin ("YX-4000H" manufactured by Mitsubishi Chemical Corporation)

Dicyclopentadiene type epoxy resin (“XD-1000” manufactured by Nippon Kayaku Co., Ltd.)

(curing agent)

Carbodiimide resin-containing liquid ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., solid content 50% by weight)

Carbodiimide resin (“10M-SP (unit)” manufactured by Nisshinbo Chemical Co., Ltd.)

Novolak-type phenolic resin ("H-4" manufactured by Maywa Kasei Co., Ltd.)

Liquid containing cyanate ester resin ("BA-3000S" manufactured by Lonza Japan, 75% by weight of solid content)

Cyanate ester resin (“PT-30” manufactured by Lonza Japan)

(curing accelerator)

Imidazole compound (2-phenyl-4-methylimidazole, "2P4MZ" manufactured by Shikoku Kasei Kogyo Co., Ltd.)

(silica)

Silica-containing slurry (70% by weight of silica: “SC-2050-HNK” manufactured by Admatechs, 0.5 μm in average particle diameter, treated with aminosilane, 30% by weight of cyclohexanone)

(alumina)

Alumina-containing slurry (70% by weight of alumina: "AC-2050-MOE" manufactured by Admatechs, average particle diameter: 0.6 µm, treated with aminosilane, 25% by weight of methyl ethyl ketone)

(thermoplastic resin)

Phenoxy resin-containing liquid (manufactured by Mitsubishi Chemical Corporation "YX6954BH30", solid content 30% by weight)

(Examples 1 to 11 and Comparative Examples 1 to 4)

The components shown in Tables 1 and 2 below were blended in the compounding amounts shown in Tables 1 and 2 below, and stirred at 1200 rpm for 4 hours using a stirrer to obtain a resin composition varnish.

Using an applicator, the obtained resin material (resin composition varnish) was coated on the release-treated surface of a polyethylene terephthalate (PET) film (“XG284” manufactured by Toray Co., Ltd., thickness: 25 μm), followed by 3 in a 100° C. gear oven. After drying for a minute, the solvent was volatilized. In this way, a laminated film having a PET film and a resin film (B stage film) having a thickness of 40 μm and a residual amount of solvent of 1.0% by weight or more and 3.0% by weight or less was obtained on the PET film.

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

(evaluation)

(1) Peel strength (90° peel strength)

Both sides of a square CCL substrate ("E679FG" manufactured by Hitachi Chemical Industry Co., Ltd.) having a side of 100 mm on which an inner layer circuit is formed by etching are immersed in a copper surface roughening agent ("Mack Etch Bond CZ-8101" manufactured by Mack Corporation), The copper surface was roughened. The obtained laminated film was set on both surfaces of the CCL substrate from the resin film side to obtain a laminated body. With respect to this laminated body, using a vacuum pressurized laminator (“MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.), the pressure is reduced for 20 seconds, the air pressure is set to 13 hPa or less, and then at a lamination pressure of 0.4 MPa and a lamination temperature of 100° C. It laminated for 20 seconds, and also pressed for 40 seconds at a press pressure of 1.0 MPa and a press temperature of 100°C.

Then, the resin film was cured under curing conditions of 180°C and 30 minutes. After that, the PET film was peeled from the resin film to obtain a cured laminated sample.

The cured laminated sample was put into a swelling solution at 60°C (an aqueous solution prepared from "Swelling Deep Securigant P" manufactured by Atotech Japan and "Sodium Hydroxide" manufactured by Wako Pure Chemical Industries, Ltd.), and the cured laminated sample was placed at a swelling temperature of 60°C for 10 minutes. stirred up After that, it was washed with pure water.

The cured laminated sample subjected to the swelling treatment was placed in an 80°C sodium permanganate roughened aqueous solution (“Concentrate Compact CP” manufactured by Atotech Japan, “Sodium Hydroxide” manufactured by Wako Pure Chemical Industries, Ltd.), and shaken at a roughening temperature of 80°C for 20 minutes. . After that, it was washed for 2 minutes with a 25°C washing liquid (“Reduction Securigant P” manufactured by Atotech Japan, “Sulfuric Acid” manufactured by Wako Pure Chemical Industries, Ltd.), and then further washed with pure water. In this way, the hardened|cured material which carried out the roughening process was formed on the CCL board|substrate on which the inner-layer circuit was formed by etching.

The surface of the cured product subjected to the roughening treatment was treated with an alkaline cleaner (“Cleaner Securigant 902” manufactured by Atotech Japan Co., Ltd.) at 60° C. for 5 minutes, followed by degreasing and washing. After washing, the cured product was treated with a 25°C pre-dip liquid ("Pre-dip Neogant B" manufactured by Atotech Japan) for 2 minutes. Thereafter, the cured product was treated with a 40°C activator liquid ("Activator Neogant 834" manufactured by Atotech Japan) for 5 minutes, and a palladium catalyst was added. Then, the cured product was treated for 5 minutes with a 30°C reducing liquid ("Reducer Neogant WA" manufactured by Atotech Japan).

Subsequently, the cured product was put into a chemical copper liquid (all of which were manufactured by Atotech Japan, “Basic Printogant MSK-DK”, “Copper Printogant MSK”, “Stabilizer Printogant MSK”, “Reducer Cu”), and electroless plating was performed. This was carried out until the plating thickness reached about 0.5 μm. After electroless plating, annealing was performed at a temperature of 120° C. for 30 minutes in order to remove residual hydrogen gas. All the steps up to the step of electroless plating were carried out while shaking the cured product with a treatment liquid of 2 L on a beaker scale.

Subsequently, electrolytic plating was performed on the cured product subjected to the electroless plating process until the plating thickness reached 25 μm. As electrolytic copper plating, a copper sulfate solution ("copper sulfate pentahydrate" manufactured by Wako Pure Chemical Industries, Ltd., "sulfuric acid" manufactured by Wako Pure Chemical Industries, Ltd., "Basic Leveler Caparacid HL" manufactured by Atotech Japan, "Corrector Caparacid GS" manufactured by Atotech Japan, Ltd.) ) was used to apply a current of 0.6 A/cm ² to electrolytic plating until the plating thickness reached about 25 μm. After the copper plating treatment, the cured product was heated at 190°C for 90 minutes to further cure the cured product. In this way, a cured product in which the copper plating layer was laminated on the upper surface was obtained.

In the obtained cured product in which the copper plating layer was laminated, a notch was made on the surface of the copper plating layer with a width of 10 mm. Then, using a tensile tester ("AG-5000B" manufactured by Shimadzu Corporation), the peel strength (90° peel strength) of the cured product (insulation layer) and the metal layer (copper plating layer) under the conditions of a crosshead speed of 5 mm/min. ) was measured.

[Judgment Criteria for Peeling Strength]

○: peel strength of 0.5 kgf/cm or more

△: peel strength of 0.4 kgf/cm or more and less than 0.5 kgf/cm

×: peel strength less than 0.4 kgf/cm

(2) Storage stability of resin materials

The obtained laminated film was stored at 25°C for 3 days and 5 days, respectively.

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 etched, and 26 copper patterns having an L/S of 50 µm/50 µm and a length of 1 cm were fabricated to obtain a concavo-convex substrate. The laminated film after storage was stacked on the concave-convex surface of the concavo-convex substrate from the resin film side and set on both sides to obtain a laminate. With respect to this laminated body, using a vacuum pressurized laminator (“MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.), the pressure is reduced for 20 seconds, the air pressure is set to 13 hPa or less, and then at a lamination pressure of 0.4 MPa and a lamination temperature of 100° C. It laminated for 20 seconds, and also pressed for 40 seconds at a press pressure of 1.0 MPa and a press temperature of 100°C. In this way, a laminate A in which a resin film was laminated on the concave-convex substrate was obtained. In the state of the layered product A, the concavo-convex value of the upper surface of the resin film in the layered product A was measured using "WYKO" manufactured by Biko Corporation. Specifically, the maximum value of the height difference between the concave portion and the convex portion adjacent to the concavo-convex portion was employed as the value of the concavo-convex portion. In this way, the presence or absence of the uneven state in the lamination test was evaluated. The storage stability of the resin material was determined according to the following criteria.

[Criterion for determining storage stability of resin material]

○: In the resin film after 3 days and 5 days, resin is filled in the copper pattern, and the value of concavo-convex is 0.5 μm or less

Δ: In the resin film after 3 days, the copper pattern is filled with resin, and the unevenness value is 0.5 μm or less, but in the resin film after 5 days, the copper pattern is not filled with resin, or the unevenness value is 0.5 μm or less. exceeds ㎛

×: In the resin film after 3 days and 5 days, the copper pattern was not filled with resin, or the value of irregularities exceeded 0.5 μm.

(3) Blister inhibition

A square cured product with a side of 100 mm on which a copper plating layer was laminated was used, and the substrate was subjected to moisture absorption (at a temperature of 60°C and a humidity of 60RH% for 40 hours) in accordance with LEVEL3 of JEDEC. After that, the substrate was subjected to nitrogen reflow treatment (peak top temperature: 260°C). In addition, reflow was repeated 30 times. The presence or absence of occurrence of blisters after reflow was visually confirmed.

[Criterion for determining blister suppression]

○: no occurrence of blisters in 30 reflows

△: No blisters occurred in 20 reflows, blisters occurred in 21 to 29 reflows

×: Blister generation in 20 or less reflows

(4) mean coefficient of linear expansion (CTE)

The obtained cured product (a resin film having a thickness of 40 µm was used) was cut into a size of 3 mm x 25 mm. Using a thermomechanical analysis device ("EXSTAR TMA/SS6100" manufactured by SI Nano Technology Co., Ltd.), the average linear expansion of the cut cured product from 25°C to 150°C under the conditions of a tensile load of 33 mN and a temperature increase rate of 5°C/min. Coefficient (ppm/°C) was calculated.

Compositions and results are shown in Tables 1 and 2 below.

11... multilayer printed wiring board
12... circuit board
12a... upper face
13 to 16... insulation layer
17... metal layer

Claims (10)

Contains an epoxy compound, a curing agent and silica,
A resin material in which the curing agent contains a cyanate ester compound and a carbodiimide compound. The resin material according to claim 1, wherein the content of the silica is 50% by weight or more in 100% by weight of components excluding the solvent in the resin material. The resin material according to claim 1 or 2, wherein the ratio of the content of the cyanate ester compound to the content of the carbodiimide compound is 0.2 or more and 4.0 or less in terms of weight ratio. The resin material according to claim 1 or 2, wherein the ratio of the content of the epoxy compound to the content of the curing agent is 1.0 or more and 3.0 or less in terms of weight ratio. The resin material according to claim 1 or 2, wherein the carbodiimide compound has an alicyclic skeleton. The resin material according to claim 1 or 2, which is a resin film. The resin material according to claim 1 or 2, which is a resin material for a multilayer printed wiring board used for forming an insulating layer in a multilayer printed wiring board. The resin material according to claim 1 or 2, which is used to obtain a cured product subjected to a roughening treatment. equipment and
A resin film laminated on the surface of the substrate,
The laminated film in which the said resin film is the resin material of Claim 1 or 2. a circuit board;
a plurality of insulating layers disposed on the circuit board;
A metal layer disposed between the plurality of insulating layers,
A multilayer printed wiring board in which at least one layer in the plurality of insulating layers is a cured product of the resin material according to claim 1 or 2.

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