JP2022001615A - Resin material and multilayer print circuit board - Google Patents

Abstract

To provide a resin material which can 1) improve storage stability, 2) be cured well, and 3) make a dielectric loss tangent of a cured product smaller.SOLUTION: A resin material according to the present invention comprises: a first curable compound having a group represented by the following formula (1) and a curing agent, where a glass transition temperature of the first curable compound is less than 75°C. In the formula (1), R1 represents an alkyl group and R2 represents a hydrogen atom or an alkyl group.SELECTED DRAWING: Figure 1

Description

The present invention relates to a resin material containing a curable compound and a curing accelerator. 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 components such as semiconductor devices, laminated boards and printed wiring boards. For example, in a multilayer printed wiring board, a resin material is used to form an insulating layer for insulating the internal layers and to form an insulating layer located on a 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 forming the resin material into a film 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.

Patent Document 1 below discloses a resin composition containing an epoxy resin (A) and a salt (B) of an imidazole compound (b1) and a carboxylic acid anhydride (b2). Patent Document 1 describes that a cured product of this resin composition can be used as an insulating layer for a multilayer printed wiring board or the like.

Japanese Unexamined Patent Publication No. 2018-62570

In a resin material containing a compound having a relatively low glass transition temperature and a curing accelerator, a curing reaction may proceed during storage of the resin material. In order to improve the storage stability of the resin material, it is conceivable to use a compound having a curable functional group having low reactivity. However, when a compound having a curable functional group having a small reactivity is simply used, the resin material cannot be cured satisfactorily, or the dielectric loss tangent of the cured product of the resin material becomes large.

In a resin material containing a compound having a relatively low glass transition temperature and a curing accelerator, it is difficult to improve storage stability, improve curability, and reduce the dielectric loss tangent of the cured product.

An object of the present invention is to provide a resin material capable of 1) enhancing storage stability, 2) being able to be cured satisfactorily, and 3) being able to reduce the dielectric loss tangent of the cured product. It is also an object of the present invention to provide a multilayer printed wiring board using the above resin material.

According to a broad aspect of the present invention, the first curable compound having a group represented by the following formula (1) and a curing accelerator are contained, and the glass transition temperature of the first curable compound is 75. Resin materials that are below ° C are provided.

In the formula (1), R ₁ represents an alkyl group and R ₂ represents a hydrogen atom or an alkyl group.

In a specific aspect of the resin material according to the present invention, the first curable compound has two or more groups represented by the formula (1).

In certain aspects of the resin material according to the invention, the first curable compound has a skeleton derived from dimerdiamine.

In a specific aspect of the resin material according to the present invention, the first curable compound is a compound represented by the following formula (11).

In the formula (11), R ₁ represents a linear hydrocarbon group _{having 6 or more and 10 or less carbon atoms, and R 2} represents a linear hydrocarbon group having 6 or more and 10 or less carbon atoms. ₃ represents a straight-chain hydrocarbon group having 6 to 10 carbon atoms, R ₄ represents a straight-chain hydrocarbon group having 6 to 10 carbon atoms. In the above formula (11), the total number of carbon atoms of _{R 1} , R ₂ , R ₃ and R _{4 is 30.}

In certain aspects of the resin material according to the present invention, the curing accelerator is an anionic curing accelerator.

In certain aspects of the resin material according to the present invention, the anionic curing accelerator is dimethylaminopyridine.

In certain aspects of the resin material according to the present invention, the curing accelerator is a radical curing accelerator.

In certain aspects of the resin material according to the invention, the resin material further comprises a thermosetting compound, the thermosetting compound comprises a bismaleimide compound, and the bismaleimide compound has a glass transition temperature of 75. It is above ℃.

In certain aspects of the resin material according to the present invention, the bismaleimide compound has a structural unit having an imide bond as a repeating structural unit.

In certain aspects of the resin material according to the present invention, the thermosetting compound further comprises a thermosetting compound other than the bismaleimide compound.

In certain aspects of the resin material according to the invention, the thermosetting compound comprises a vinyl compound or an epoxy compound.

In certain aspects of the resin material according to the invention, the resin material comprises a curing agent, wherein the curing agent comprises a phenol compound and an active ester compound.

In certain aspects of the resin material according to the invention, the resin material comprises a filler.

In certain aspects of the resin material according to the present invention, the filler is an insulating filler.

In certain aspects 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 are provided, and the plurality of insulating layers are provided. A multilayer printed wiring board is provided in which at least one of the layers is a cured product of the resin material described above.

The resin material according to the present invention contains a first curable compound having a group represented by the above formula (1) and a curing accelerator, and the glass transition temperature of the first curable compound is 75 ° C. Is less than. Since the resin material according to the present invention has the above-mentioned structure, 1) storage stability can be improved, 2) good curing can be performed, and 3) the dielectric loss tangent of the cured product can be reduced. Can be done.

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

Hereinafter, the present invention will be described in detail.

The resin material according to the present invention contains a first curable compound having a group represented by the following formula (1) and a curing accelerator. The glass transition temperature of the first curable compound is less than 75 ° C.

In the above formula (1), R ₁ represents an alkyl group, and R ₂ represents a hydrogen atom or an alkyl group.

Since the resin material according to the present invention has the above-mentioned structure, 1) storage stability can be improved, 2) good curing can be performed, and 3) the dielectric loss tangent of the cured product can be reduced. Can be done. In the resin material according to the present invention, all the effects of 1) -3) above can be exhibited even though the first curable compound having a relatively small glass transition temperature and the curing accelerator are used. can.

Further, the resin material according to the present invention can enhance the embedding property of the resin material in the uneven surface of a substrate or the like. Further, in the resin material according to the present invention, the surface roughness after etching can be reduced.

The resin material according to the present invention may be a resin composition or a resin film. The resin composition has fluidity. The resin composition may be in the form of a paste. The paste form contains a liquid. The resin material according to the present invention is preferably a resin film because of its excellent handleability.

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

[First curable compound]
The resin material according to the present invention contains a first curable compound having a group represented by the following formula (1). The group represented by the following formula (1) is present at the terminal in the first curable compound. In the following formula (1), the right end is a binding site with another group. As the first curable compound, only one kind may be used, or two or more kinds may be used in combination.

In the above formula (1), R ₁ represents an alkyl group, and R ₂ represents a hydrogen atom or an alkyl group. In the above formula (1), R ₂ may be a hydrogen atom or an alkyl group. Further, in the above formula (1), when R ₂ is an alkyl group, the alkyl group of R _{1 and} the alkyl group of R ₂ may be the same alkyl group or different alkyl groups. ..

From the viewpoint of exhibiting the effects of the invention more effectively, in formula (1), the carbon number of the alkyl group of R ₁ is not particularly limited, but is preferably 12 or less, more preferably 8 or less, more preferably Is 6 or less.

From the viewpoint of exhibiting the effects of the invention more effectively, in formula (1), the carbon number of the alkyl group of R ₂ is not particularly limited, but is preferably 12 or less, more preferably 8 or less, more preferably Is 6 or less.

From the viewpoint of exerting the effect of the present invention even more effectively, in the above formula (1), R ₁ is preferably a methyl group or an ethyl group, and more preferably a methyl group.

From the viewpoint of exerting the effect of the present invention even more effectively, in the above formula (1), R ₂ is preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom or a methyl group. It is preferably a hydrogen atom, more preferably a hydrogen atom.

The first curable compound may have only one group represented by the above formula (1), may have two groups, or may have two or more groups. It may have three or more.

From the viewpoint of more effectively exerting the effect of the present invention, the first curable compound preferably has two groups represented by the above formula (1), and more preferably has two or more groups. preferable.

In the first curable compound, the functional group equivalent of the group represented by the above formula (1) is preferably 100 g / mol or more, more preferably 140 g / mol or more, and preferably 600 g / mol or less. It is preferably 500 g / mol or less.

The first curable compound preferably has a skeleton derived from dimerdiamine. In this case, the dielectric loss tangent of the cured product of the resin material can be further lowered, and the flexibility and elongation characteristics of the resin material (resin film) can be enhanced. Further, the dielectric loss tangent at high frequency and the dielectric loss tangent at high temperature can be lowered.

From the viewpoint of more effectively exerting the effects of the present invention, the first curable compound preferably contains a compound represented by the following formula (11), and the compound represented by the following formula (11). Is more preferable. From the viewpoint of exerting the effect of the present invention even more effectively, the first curable compound having a skeleton derived from dimerdiamine preferably contains a compound represented by the following formula (11), and the following formula ( It is more preferable that the compound is represented by 11). The first curable compounds represented by the following formula (11) has two groups represented by the above formula (1), R ₁ in formula (1) is a methyl group, R ₂ is a hydrogen atom.

In the above formula (11), R ₁ represents a linear hydrocarbon group _{having 6 or more and 10 or less carbon atoms, and R 2} represents a linear hydrocarbon group having 6 or more and 10 or less carbon atoms. ₃ represents a straight-chain hydrocarbon group having 6 to 10 carbon atoms, R ₄ represents a straight-chain hydrocarbon group having 6 to 10 carbon atoms. In the above formula (11), the total number of carbon atoms of _{R 1} , R ₂ , R ₃ and R _{4 is 30.} That is, in the above formula (11), the skeleton derived from dimer diamine has 36 carbon atoms. In the above formula (11), R ₁ may be a hydrocarbon group having a double bond or may be a hydrocarbon group having no double bond. In the above formula (11), R ₂ may be a hydrocarbon group having a double bond or may be a hydrocarbon group having no double bond. In the above formula (11), R ₃ may be a hydrocarbon group having a double bond or may be a hydrocarbon group having no double bond. In the formula (11), R ₄ may be a hydrocarbon group having a double bond or a hydrocarbon group having no double bonds.

The compound represented by the above formula (11) can be suitably produced by using dimerdiamine as one of the raw materials. However, for example, since dimer diamine is a natural product, the structure of diamine diamine is not uniquely determined. Therefore, in the above formula (11), R ₁ , R ₂ , R ₃ , and R ₄ may each be a linear hydrocarbon group having a double bond, and may be a direct hydrocarbon group having no double bond. It may be a chain hydrocarbon group.

From the viewpoint of exerting the effects of the present invention even more effectively, the first curable compound preferably contains a compound represented by the following formula (12). The compound represented by the above formula (11) preferably contains a compound represented by the following formula (12). The compound represented by the following formula (12) has a skeleton derived from dimerdiamine. The compound represented by the following formula (12) _{has a structure in which R 1} , R ₂ , R ₃ and R ₄ in the above formula (11) do not have a double bond, respectively.

The glass transition temperature (Tg) of the first curable compound is less than 75 ° C. The glass transition temperature (Tg) of the first curable compound is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, still more preferably 30 ° C. or lower. When the glass transition temperature (Tg) of the first curable compound is not more than the above upper limit, the effect of the present invention can be exhibited even more effectively.

The glass transition temperature (Tg) of the first curable compound can be measured from the inflection point of the reverse heat flow in the differential scanning calorimetry.

The molecular weight of the first curable compound is preferably 600 or more, more preferably 700 or more, preferably 2000 or less, more preferably 1000 or less, still more preferably 900 or less. When the molecular weight of the first curable compound is not less than the lower limit and not more than the upper limit, the reactivity of the first curable compound becomes high, and the resin material can be cured more satisfactorily. , The dielectric loss tangent of the cured product can be further reduced. Further, since the melt viscosity of the resin material can be lowered, the embedding property of the resin material in the uneven surface of the substrate or the like can be improved. Further, when the resin material is a resin film containing an inorganic filler in an amount of 50% by weight or more, the uniformity of the surface of the resin film can be improved.

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

When the first curable compound has a skeleton derived from the dimer diamine, the ratio of the molecular weight of the skeleton portion derived from the dimer diamine to the molecular weight of the first curable compound (skeleton derived from the diamine diamine). The molecular weight of the portion / the molecular weight of the first curable compound) is defined as the ratio (X). The ratio (X) is preferably 0.5 or more, more preferably 0.6 or more, preferably 0.9 or less, and more preferably 0.8 or less.

The content of the first curable compound is preferably 0.1% by weight or more, more preferably 1% by weight or more, and preferably 10% by weight in 100% by weight of the component excluding the solvent in the resin material. Below, it is more preferably 5% by weight or less. When the content of the first curable compound is not less than the above lower limit and not more than the above upper limit, the effect of the present invention can be exhibited even more effectively. Further, when the content of the first curable compound is at least the above lower limit, the surface roughness after etching can be further reduced, and the plating peel strength can be increased.

The content of the first curable compound is preferably 1% by weight or more, more preferably 2% by weight or more, still more preferably 4% by weight in 100% by weight of the components excluding the filler and the solvent in the resin material. The above is preferably 30% by weight or less, more preferably 20% by weight or less, still more preferably 10% by weight or less. When the content of the first curable compound is not less than the above lower limit and not more than the above upper limit, the effect of the present invention can be exhibited even more effectively. Further, when the content of the first curable compound is at least the above lower limit, the surface roughness after etching can be further reduced, and the plating peel strength can be increased. Further, the elongation characteristics of the resin material (resin film) can be enhanced, and the thermal dimensional stability of the cured product can be enhanced.

The first curable compound can be synthesized, for example, by subjecting citraconic anhydride and dimerdiamine to a dehydration condensation reaction under an acid catalyst.

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

Examples of the acid catalyst include amberlyst 36 dry (trade name, manufactured by DuPont) and the like.

[Thermosetting compound]
The resin material preferably contains a thermosetting compound. The resin material preferably contains the first curable compound and a thermosetting compound as a compound different from the first curable compound. In the resin material, the first curable compound is the first thermosetting compound, and a thermosetting compound (second thermosetting compound) is used as a compound different from the first thermosetting compound. It is preferable to include it. Only one type of the thermosetting compound may be used, or two or more types may be used in combination.

Examples of the thermosetting compound include bismaleimide compounds, epoxy compounds and vinyl compounds. The thermosetting compound preferably contains a bismaleimide compound, more preferably contains a bismaleimide compound and a thermosetting compound other than the bismaleimide compound, and contains a bismaleimide compound, an epoxy compound and a vinyl compound. It is more preferable to include it.

<Bismaleimide compound>
The resin material preferably contains a bismaleimide compound. When the resin material contains a bismaleimide compound, the effect of the present invention can be exhibited even more effectively. Only one kind of the above-mentioned bismaleimide compound may be used, or two or more kinds may be used in combination.

The bismaleimide compound may be an aliphatic bismaleimide compound or an aromatic bismaleimide compound.

The bismaleimide compound preferably has a structural unit having an imide bond. It is more preferable that the bismaleimide compound has a structural unit having an imide bond as a repeating structural unit. In this case, the dielectric loss tangent of the cured product of the resin material can be further lowered, and the thermal dimensional stability of the cured product can be improved.

The bismaleimide compound may or may not have a skeleton derived from dimerdiamine.

The glass transition temperature of the bismaleimide compound is preferably 75 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 85 ° C. or higher, preferably 200 ° C. or lower, more preferably 170 ° C. or lower, still more preferably 150 ° C. or higher. Below, it is particularly preferably 120 ° C. or lower. When the glass transition temperature of the bismaleimide compound is equal to or higher than the lower limit and lower than the upper limit, the effect of the present invention can be more effectively exhibited.

The molecular weight of the bismaleimide compound is preferably 500 or more, more preferably 1000 or more, still more preferably 3000 or more, particularly preferably 3500 or more, preferably 30,000 or less, more preferably 20,000 or less, still more preferably 15,000 or less. Particularly preferably, it is 5500 or less. When the molecular weight of the bismaleimide compound is at least the above lower limit and at least the above upper limit, the melt viscosity of the resin material can be lowered. Further, the glass transition temperature of the cured product can be increased, and the thermal dimensional stability of the cured product can be improved.

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

Examples of commercially available products of the aromatic bismaleimide compound include "BMI-4000" and "BMI-5100" manufactured by Daiwa Kasei Kogyo Co., Ltd. and "MIR-3000" manufactured by Nippon Kayaku Co., Ltd.

The content of the bismaleimide compound is preferably 0.5% by weight or more, more preferably 1% by weight or more, and preferably 25% by weight or less, based on 100% by weight of the component excluding the solvent in the resin material. It is preferably 15% by weight or less. When the content of the bismaleimide compound is not less than the above lower limit and not more than the above upper limit, the dielectric loss tangent of the cured product can be further lowered, and the thermal dimensional stability of the cured product can be enhanced.

The content of the bismaleimide compound is preferably 2.5% by weight or more, more preferably 5% by weight or more, still more preferably 7.5% by weight in 100% by weight of the components excluding the filler and the solvent in the resin material. % Or more, preferably 70% by weight or less, and more preferably 50% by weight or less. When the content of the bismaleimide compound is not less than the above lower limit and not more than the above upper limit, the dielectric loss tangent of the cured product can be further lowered, and the thermal dimensional stability of the cured product can be enhanced.

<Epoxy compound>
The resin material preferably contains an epoxy compound. As the epoxy compound, a conventionally known epoxy compound can be used. The epoxy compound is an organic compound having at least one epoxy group. Only one kind of the epoxy compound may be used, or two or more kinds may be used in combination.

Examples of the epoxy compound include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, phenol novolac type epoxy compound, biphenyl type epoxy compound, biphenyl novolac type epoxy compound, biphenol type epoxy compound, and naphthalene type epoxy compound. , Fluolene type epoxy compound, phenol aralkyl type epoxy compound, naphthol aralkyl type epoxy compound, dicyclopentadiene type epoxy compound, anthracene type epoxy compound, adamantan skeleton epoxy compound, tricyclodecane skeleton epoxy compound, naphthylene ether type Examples thereof include epoxy compounds and epoxy compounds having a triazine nucleus as a skeleton.

The epoxy compound may be a glycidyl ether compound. The glycidyl ether compound is a compound having at least one glycidyl ether group.

From the viewpoint of further lowering the dielectric adjacency of the cured product 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 has a naphthalene skeleton or a naphthalene skeleton. It is preferable to contain an epoxy compound having a phenyl skeleton, and more preferably an epoxy compound having an aromatic skeleton.

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

The viscosity of the epoxy compound liquid 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 Leologica Instruments) or the like.

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 50% by weight or more in 100% by weight of the component excluding the solvent in the resin material, a resin material having high fluidity at the time of forming the insulating layer can be obtained. Therefore, when the uncured resin material or the B-staged product is laminated on the circuit board, the inorganic filler can be uniformly present.

The molecular weight of the epoxy compound means a molecular weight that can be calculated from the structural formula when the epoxy compound is not a polymer and the structural formula of the epoxy compound can be specified. When the epoxy compound is a polymer, it means a weight average molecular weight.

The content of the epoxy compound is preferably 4% by weight or more, more preferably 7% by weight or more, preferably 20% by weight or less, and more preferably 15 in 100% by weight of the component excluding the solvent in the resin material. It is less than% by weight. When the content of the epoxy compound is not less than the above lower limit and not more than the above upper limit, the thermal dimensional stability of the cured product of the resin material can be further improved.

The content of the epoxy compound is preferably 15% by weight or more, more preferably 25% by weight or more, and preferably 60% by weight or less, based on 100% by weight of the components excluding the filler and the solvent in the resin material. It is preferably 50% by weight or less. When the content of the epoxy compound is not less than the above lower limit and not more than the above upper limit, the thermal dimensional stability of the cured product of the resin material can be further improved.

Weight ratio of the content of the epoxy compound to the total content of the first curable compound and the curing agent described later (content of the epoxy compound / total of the first curing compound and the curing agent described later). Content) is preferably 0.25 or more, more preferably 0.5 or more, preferably 1 or less, and more preferably 0.85 or less. When the weight ratio is equal to or higher than the lower limit and lower than the upper limit, the dielectric loss tangent can be further lowered.

<Vinyl compound>
The resin material preferably contains a vinyl compound. As the vinyl compound, a conventionally known vinyl compound can be used. The vinyl compound is an organic compound having at least one vinyl group. Only one kind of the vinyl compound may be used, or two or more kinds thereof may be used in combination.

Examples of the vinyl compound include divinyl compounds. Examples of the divinyl compound include a divinylbenzyl ether compound and the like. The vinyl compound may be a divinyl compound having an aliphatic skeleton, or may be a divinyl ether compound.

The content of the vinyl compound in 100% by weight of the components excluding the filler and the solvent in the resin material is preferably 2.5% by weight or more, more preferably 5% by weight or more, still more preferably 7.5% by weight. The above is preferably 70% by weight or less, and more preferably 50% by weight or less. When the content of the vinyl compound is not less than the above lower limit and not more than the above upper limit, the thermal dimensional stability of the cured product can be further improved.

[Filler]
The resin material preferably contains a filler.

Examples of the filler include an organic filler and an inorganic filler. The filler is preferably an insulating filler. As the filler, only one kind may be used, or two or more kinds may be used in combination.

Examples of the organic filler include particulate matter made of benzoxazine resin, benzoxazole resin, fluororesin, acrylic resin, styrene resin and the like. Examples of the fluororesin include polytetrafluoroethylene (PTFE) and the like. By using fluororesin particles as the organic filler, the relative permittivity of the cured product of the resin material can be further reduced.

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

From the viewpoint of further reducing the dielectric loss tangent of the cured product of the resin material and further reducing the dimensional change due to heat of the cured product of the resin material, the filler is preferably an inorganic filler.

The inorganic filler is preferably an inorganic filler having a thermal conductivity of 10 W / mK or more, such as alumina and boron nitride. In this case, heat dissipation can be improved.

From the viewpoint of enhancing the embedding property in the uneven surface and enhancing the thermal dimensional stability, the inorganic filler is preferably an anisotropic filler having anisotropy.

The inorganic filler is preferably silica or alumina, more preferably silica, and even more preferably fused silica. In this case, the surface roughness of the surface of the cured product of the resin material 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. Good insulation reliability can be imparted to the cured product. In particular, by using silica as the inorganic filler, the coefficient of thermal expansion of the cured product becomes even lower, and the dielectric loss tangent of the cured product becomes even lower. In addition, the dielectric constant of the cured product can be improved. The shape of silica is preferably spherical.

From the viewpoint of increasing the thermal conductivity and the insulating property, the inorganic filler is preferably alumina.

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

The inorganic filler is preferably surface-treated, more preferably a surface-treated product with a coupling agent, and even more preferably a surface-treated product with a silane coupling agent. By surface-treating the inorganic filler, the surface roughness of the surface of the roughened cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased. Further, since the inorganic filler is surface-treated, finer wiring can be formed on the surface of the cured product, and even better inter-wiring insulation reliability and interlayer insulation reliability can be obtained in the cured product. Can be granted.

Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, and the like. Examples of the silane coupling agent include methacrylic silane, acrylic silane, aminosilane, imidazole silane, vinylsilane, and epoxysilane.

The average particle size of the organic filler, which is the filler, is preferably 1 μm or less. When the average particle size of the organic filler is not more than the above upper limit, the surface roughness after etching can be reduced, the plating peel strength can be increased, and the adhesion between the insulating layer and the metal layer can be further improved. Can be enhanced. The average particle size of the organic filler may be 50 nm or more.

The average particle size of the inorganic filler as the filler is preferably 50 nm or more, more preferably 100 nm or more, further preferably 500 nm or more, preferably 5 μm or less, more preferably 3 μm or less, still more preferably 1 μm or less. be. When the average particle size of the inorganic filler is equal to or higher than the lower limit and lower than the upper limit, the surface roughness after etching can be reduced, the plating peel strength can be increased, and the insulating layer and the metal layer can be adhered to each other. The sex can be further enhanced.

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

The content of the filler is preferably 50% by weight or more, more preferably 55% by weight or more, still more preferably 60% by weight or more, and particularly preferably 70% by weight in 100% by weight of the component 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 filler is at least the above lower limit, the dielectric loss tangent is effectively lowered. When the content of the filler is not more than the upper limit, the thermal dimensional stability can be improved and the warp of the cured product can be effectively suppressed. When the content of the filler is not less than the above lower limit and not more than the above upper limit, the surface roughness of the surface of the cured product can be further reduced, and finer wiring can be formed on the surface of the cured product. can.

The content of the organic filler is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 15% by weight or more, and particularly preferably 20% by weight of the component excluding the solvent in the resin material. It is 5% by weight or more, preferably 75% by weight or less, more preferably 60% by weight or less, still more preferably 50% by weight or less, and particularly preferably 40% by weight or less. When the content of the organic filler is at least the above lower limit, the dielectric loss tangent is effectively lowered. When the content of the organic filler is not more than the above upper limit, the thermal dimensional stability can be improved and the warp of the cured product can be effectively suppressed. When the content of the organic filler is not less than the above lower limit and not more than the above upper limit, the surface roughness of the surface of the cured product can be further reduced, and finer wiring can be formed on the surface of the cured product. Can be done.

The content of the inorganic filler is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 65% by weight or more, and particularly preferably 68 in 100% by weight of the component excluding the solvent in the resin material. It is 0% by weight 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 inorganic filler is at least the above lower limit, the dielectric loss tangent is effectively lowered. When the content of the inorganic filler is not more than the above upper limit, the thermal dimensional stability can be improved and the warp of the cured product can be effectively suppressed. When the content of the inorganic filler is not less than the above lower limit and not more than the above upper limit, the surface roughness of the surface of the cured product can be further reduced, and finer wiring can be formed on the surface of the cured product. Can be done. Further, 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 to improve the smear removing property.

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

Examples of the curing agent include a phenol compound (phenol curing agent), an active ester compound, a cyanate ester compound (cyanate ester curing agent), a benzoxazine compound (benzoxazine curing agent), a carbodiimide compound (carbodiimide curing agent), and an amine compound (amine). Hardener), thiol compound (thiol hardener), phosphine compound, dicyandiamide, acid anhydride and the like. The curing agent preferably has a functional group capable of reacting with the epoxy group of the epoxy compound.

From the viewpoint of further lowering the dielectric adjacency of the cured product, the curing agent contains at least one component of a phenol compound, an active ester compound, a cyanate ester compound, a benzoxazine compound, a carbodiimide compound and an acid anhydride. Is preferable. From the viewpoint of further lowering the dielectric adjacency, the curing agent more preferably contains at least one component of a phenol compound, an active ester compound, a cyanate ester compound, a benzoxazine compound, and a carbodiimide compound, and is an active ester. It is more preferable to contain a compound.

From the viewpoint of further lowering the dielectric loss tangent, when the resin material contains an epoxy compound, the curing agent preferably contains a phenol compound and an active ester compound.

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

Commercially available products of the above phenol compounds include novolak-type phenol (“TD-2091” manufactured by DIC), biphenyl novolac-type phenol (“MEH-7851” manufactured by Meiwa Kasei Co., Ltd.), and aralkyl-type phenol compound (“MEH” manufactured by Meiwa Kasei Co., Ltd.). -7800 "), and phenols having an aminotriazine skeleton ("LA-1356 "and" LA-3018-50P "manufactured by DIC Corporation) and the like can be mentioned.

The active ester compound means a compound containing at least one ester bond in the structure and having an aliphatic chain, an aliphatic ring or an aromatic ring bonded to both sides of the ester bond. The active ester compound is obtained, for example, by a condensation reaction between a carboxylic acid compound or a thiocarboxylic acid compound and a hydroxy compound or a thiol compound. Examples of the active ester compound include a compound represented by the following formula (3).

In the above formula (3), 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, a naphthalene ring which may have a substituent, and the like. Examples of the substituent include a hydrocarbon group. The hydrocarbon group has preferably 12 or less carbon atoms, more preferably 6 or less carbon atoms, and even more preferably 4 or less carbon atoms.

In the above formula (3), the combination of X1 and X2 includes a combination of a benzene ring which may have a substituent and a benzene ring which may have a substituent, and a substituent. Examples thereof include a combination of a benzene ring and a naphthalene ring which may have a substituent. Further, in the above formula (3), 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 above active ester compound is not particularly limited. From the viewpoint of further enhancing thermal dimensional stability and flame retardancy, the 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 increasing the thermal dimensional stability of the cured product, it is more preferable to have a naphthalene ring in the main chain skeleton of the active ester compound.

Commercially available products of the above active ester compounds include "HPC-8000L", "HPC-8000-65T", "EXB-9416-70BK", "EXB8100-65T", "HPC-8150-62T" and "HPC-8150-62T" manufactured by DIC Corporation. EXB-8 ”and the like.

Examples of the cyanate ester compound include a novolak type cyanate ester resin, a bisphenol type cyanate ester resin, and a prepolymer in which these are partially triquantized. Examples of the novolak type cyanate ester resin include phenol novolac type cyanate ester resin and alkylphenol type cyanate ester resin. Examples of the bisphenol type cyanate ester resin include bisphenol A type cyanate ester resin, bisphenol E type cyanate ester resin, and tetramethyl bisphenol F type cyanate ester resin.

Commercially available products of the above cyanate ester compound include a phenol novolac type cyanate ester resin (“PT-30” and “PT-60” manufactured by Lonza Japan Co., Ltd.) and a prepolymer in which a bisphenol type cyanate ester resin is triquantized (Lonza Japan). Examples thereof include "BA-230S", "BA-3000S", "BTP-1000S" and "BTP-6020S") manufactured by the same company.

The content of the cyanate ester compound is preferably 10% by weight or more, more preferably 15% by weight or more, still more preferably 20% by weight or more in 100% by weight of the components excluding the filler and the solvent in the resin material. It is preferably 85% by weight or less, more preferably 75% by weight or less. When the content of the cyanate ester compound is at least the above lower limit and at least the above upper limit, the thermal dimensional stability of the cured product can be further enhanced.

Examples of the benzoxazine compound include P-d type benzoxazine and Fa type benzoxazine.

Examples of commercially available products of the benzoxazine compound include "P-d type" manufactured by Shikoku Chemicals Corporation.

The content of the benzoxazine compound is preferably 1% by weight or more, more preferably 5% by weight or more, still more preferably 10% by weight or more in 100% by weight of the components excluding the filler and the solvent in the resin material. It is preferably 70% by weight or less, more preferably 60% by weight or less. When the content of the benzoxazine compound is at least the above lower limit and at least the above upper limit, the thermal dimensional stability of the cured product can be further enhanced.

The carbodiimide compound is a compound having a structural unit represented by the following formula (4). In the following formula (4), the right end portion and the left end portion are binding sites for other groups. Only one kind of the carbodiimide compound may be used, or two or more kinds thereof may be used in combination.

In the above formula (4), 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 bonded to an arylene group. It represents a group and p represents an integer of 1-5. When there are a plurality of X's, the plurality of X's may be the same or different.

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

Commercially available products of the above carbodiimide compounds include "carbodilite V-02B", "carbodilite V-03", "carbodilite V-04K", "carbodilite V-07", "carbodilite V-09", and "carbodilite" manufactured by Nisshinbo Chemical Co., Ltd. Examples thereof include "10M-SP" and "Carbodilite 10M-SP (revised)", and "Stavaxol P", "Stavaxol P400" and "Hikazil 510" manufactured by Rheinchemy.

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

Examples of the commercially available product of the acid anhydride include "Ricacid TDA-100" manufactured by Shin Nihon Rika Co., Ltd.

The content of the curing agent 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 is not less than the above lower limit and not more than the above upper limit, the curability is further improved, the thermal dimensional stability is further enhanced, and the volatilization of the residual unreacted component can be further suppressed.

The total content of the first curable compound, the epoxy compound, and the curing agent in 100% by weight of the components excluding the filler and the solvent in the resin material is preferably 30% by weight or more, more preferably. It is 50% by weight or more, preferably 98% by weight or less, and more preferably 95% by weight or less. When the total content is not less than the above lower limit and not more than the above upper limit, the curability is further improved and the thermal dimensional stability can be further improved.

[Hardening accelerator]
The resin material contains a curing accelerator. By using the above-mentioned curing accelerator, the curing rate becomes even faster. 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 crosslinked density increases. The curing accelerator is not particularly limited, and conventionally known curing accelerators can be used. As the curing accelerator, only one kind may be used, or two or more kinds may be used in combination.

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

Examples of the imidazole compound include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-. 2-Methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-un Decylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2' -Methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino- 6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s -Triazine 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 And so on.

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

When the curing agent contains the active ester compound, the curing accelerator preferably contains dimethylaminopyridine.

Examples of the phosphorus compound include triphenylphosphine compounds and the like.

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

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

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

A curing accelerator which is a peroxide and an anionic curing accelerator may be used in combination. In particular, when a vinyl compound and an epoxy compound are used in combination, a better cured product may be obtained by using the above two types of curing accelerators.

From the viewpoint of further suppressing the curing temperature and effectively suppressing the warpage of the cured product, the content of the anionic curing accelerator is preferably 20% by weight or more, more preferably 20% by weight or more, based on 100% by weight of the curing accelerator. 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.

When the vinyl compound is used as the thermosetting compound, radical curing proceeds. Therefore, the curing accelerator preferably contains the radical curing accelerator, and is preferably dicumyl peroxide or 2,5-dimethyl-2. , 5-Bis (t-butylperoxy) hexin-3 is more preferred. When the resin material is efficiently cured after pre-cure, a radical curing accelerator having a 1-minute half-life temperature of 170 ° C. or higher and 200 ° C. or lower is more preferable. Examples of commercially available products of radical curing accelerators having a 1-minute half-life temperature of 170 ° C. or higher and 200 ° C. or lower include "Perhexin 25B" manufactured by NOF CORPORATION.

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

[Thermoplastic resin]
The resin material preferably contains a thermoplastic resin. Examples of the thermoplastic resin include polyvinyl acetal resin, polyimide resin, and phenoxy resin. Only one type of the above-mentioned thermoplastic resin may be used, or two or more types 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 enhancing the adhesion of the metal wiring regardless of the curing environment. By using the phenoxy resin, deterioration of embedding property in holes or irregularities of the circuit board of the resin film and non-uniformity of the inorganic filler can be suppressed. 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 wet and spread in an unintended region during the curing process.

The phenoxy resin contained in the above resin material is not particularly limited. As the phenoxy resin, a conventionally known phenoxy resin can be used. Only one kind of the phenoxy resin may be used, or two or more kinds thereof may be used in combination.

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

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

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

From the viewpoint of improving the solubility, the polyimide compound is preferably a polyimide compound obtained by a method of reacting a tetracarboxylic dianhydride with a dimerdiamine.

The polyimide compound may have an acid anhydride structure, a maleimide structure, or a citraconic imide structure at the terminal. In this case, the polyimide compound and the epoxy compound can be reacted. By reacting the polyimide compound with the epoxy compound, the thermal dimensional stability of the cured product can be improved.

From the viewpoint of obtaining a resin material having more excellent storage stability, the weight average molecular weights of the thermoplastic resin, the polyimide resin and the phenoxy resin are preferably 5000 or more, more preferably 10,000 or more, and preferably 100,000 or less. , More preferably 50,000 or less.

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

The contents of the thermoplastic resin, the polyimide resin and the phenoxy resin are not particularly limited. The content of the thermoplastic resin in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material (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, and more preferably 20% by weight or less. When the content of the thermoplastic resin is not less than the above lower limit and not more than the above upper limit, the embedding property of the resin material in the holes or irregularities of the circuit board is improved. When the content of the thermoplastic resin is at least the above lower limit, the formation of the resin film becomes easier and a better insulating layer can be obtained. When the content of the thermoplastic resin is not more than the upper limit, the coefficient of thermal expansion of the cured product is further lowered. When the content of the thermoplastic resin is not more than the above upper limit, the surface roughness of the surface of the cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased.

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

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

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

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, and preferably 10% by weight. % Or less, 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, colorants, antioxidants, UV deterioration inhibitors, and defoamers. It may contain an agent, a thickener, a rocking denaturing agent and the like.

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

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

Examples of a method for obtaining a resin film by molding the resin composition into a film form include the following methods. An extrusion molding method in which a resin composition is melt-kneaded using an extruder, extruded, and then molded into a film by a T-die, a circular die, or the like. A casting molding method in which a resin composition containing a solvent is cast and molded into a film. Other 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 as a B stage film can be obtained by molding the resin composition into a film and heating and drying it at 50 ° C. to 150 ° C. for 1 to 10 minutes to the extent that curing by heat does not proceed too much. can.

The film-like resin composition obtained by the drying step 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 can be further cured.

The resin film does not have to be a prepreg. When the resin film is not a prepreg, migration does not occur along the glass cloth or the like. Further, when the resin film is laminated or pre-cured, unevenness due to the glass cloth does not occur on the surface.

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 a 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 films. The surface of the base film may be mold-released, 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, 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 by 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.

(Other details of resin material)
The resin material is heated at 190 ° C. for 90 minutes to obtain a cured product of the resin material. The dielectric loss tangent (Df) of the obtained cured product at 23 ° C. and a frequency of 5.8 GHz is preferably 3.00 × 10 ^-3 or less, more preferably 2.75 × 10 ^-3 or less, and further preferably 2. It is 50 × 10 ^-3 or less, particularly preferably 2.30 × 10 ^-3 or less, and most preferably 2.10 × 10 ^-3 or less. The dielectric loss tangent (Df) may be 2.10 × 10 ^-3 or more, or 2.30 × 10 ^-3 or more.

More specifically, the dielectric loss tangent (Df) of the cured product is measured as follows.

A film-shaped resin material (resin film) is heated at 190 ° C. for 90 minutes to obtain a cured product of the resin material. The obtained cured product is cut into a size of 2 mm in width and 80 mm in length, and 10 sheets are stacked. Using the "Cavity Resonance Permittivity Measuring Device CP521" manufactured by Kanto Electronics Application Development Co., Ltd. and the "Network Analyzer N5224A PNA" manufactured by Keysight Technology Co., Ltd., the frequency is 5.8 GHz at room temperature (23 ° C) by the cavity resonance method. Measure the dielectric loss tangent.

The resin material is heated at 190 ° C. for 90 minutes to obtain a cured product of the resin material. In this case, the average coefficient of linear expansion (CTE) from 25 ° C. to 150 ° C. under a tensile load of 33 mN of the obtained cured product is preferably 33 ppm / ° C. or lower, more preferably 30 ppm / ° C. or lower, still more preferably 27 ppm. It is / ° C. or lower, more preferably 26 ppm / ° C. or lower, particularly preferably 24 ppm / ° C. or lower, and most preferably 22 ppm / ° C. or lower. The average coefficient of linear expansion (CTE) may be 17 ppm / ° C. or higher, or 19 ppm / ° C. or higher.

More specifically, the average coefficient of linear expansion (CTE) of the cured product is measured as follows.

A film-shaped resin material (resin film) is heated at 190 ° C. for 90 minutes to obtain a cured product of the resin material. The obtained cured product is cut into a size of 3 mm × 25 mm. Using a thermomechanical analyzer (for example, "EXSTAR TMA / SS6100" manufactured by SII Nanotechnology), the cured product cut from 25 ° C to 25 ° C under the conditions of a tensile load of 33 mN and a heating rate of 5 ° C / min. The average linear expansion coefficient (ppm / ° C.) up to 150 ° C. is calculated.

(Semiconductor devices, printed wiring boards, copper-clad laminated boards and multi-layer printed wiring boards)
The resin material is suitably used for forming a mold resin for embedding a semiconductor chip in a semiconductor device.

The resin material is suitably used for a substitute application of a liquid crystal polymer (LCP), a millimeter wave antenna application, a rewiring layer application, and a low dielectric substrate application. Further, the resin material is suitably used not only for the above applications but also for all wiring forming applications.

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

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

A member to be laminated having a metal layer on one side or both sides can be laminated on the resin film. A laminated structure comprising a member to be laminated having a metal layer on its surface and a resin film laminated on the surface of the metal layer, wherein the resin film is the above-mentioned resin material can be suitably obtained. The method of 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, using a device such as a parallel flat plate press or a roll laminator, the resin film can be laminated on a member to be laminated having a metal layer on the surface while applying pressure with or without heating.

The material of the metal layer is preferably copper.

The member to be laminated having the metal layer on the 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 comprising a copper foil and a resin film laminated on one surface of the copper foil.

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

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

As an example of the multilayer board, there is a multilayer board provided with a circuit board and an insulating layer laminated on the circuit board. The insulating layer of this multilayer board is formed of the above resin material. Further, the insulating layer of the multilayer substrate may be formed of the resin film of the laminated film by using the laminated film. The insulating layer is preferably laminated on the surface on which the circuit of the circuit board is provided. It is preferable that a part of the insulating layer is embedded between the circuits.

In the multilayer board, 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 swelled before the roughening treatment.

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

Further, as another example of the multilayer board, the circuit board, the insulating layer laminated on the surface of the circuit board, and the insulating layer laminated on the surface opposite to the surface on which the circuit board is laminated are laminated. A multilayer substrate provided with a copper foil can be mentioned. It is preferable that the insulating layer is formed by curing the resin film using a copper-clad laminate having a copper foil and a resin film laminated on one surface of the copper foil. Further, the copper foil is etched and preferably a copper circuit.

As another example of the multilayer board, there 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 of the plurality of insulating layers arranged on the circuit board is formed by using the resin material. It is preferable that the multilayer board further includes a circuit laminated on at least one surface of the insulating layer formed by using the resin film.

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

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

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

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

In the multilayer printed wiring board 11, the insulating layers 13 to 16 are formed of the cured product of the resin material. In the present embodiment, since the surface of the insulating layers 13 to 16 is roughened, fine holes (not shown) are formed on the surface of the insulating layers 13 to 16. Further, the metal layer 17 reaches the inside of the fine pores. Further, 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 portion where the metal layer 17 is not formed can be reduced. Further, in the multilayer printed wiring board 11, good insulation reliability is imparted between the upper metal layer and the lower metal layer which are not connected by via hole connection and through hole connection (not shown).

(Roughening treatment and swelling treatment)
The resin material is preferably used to obtain a cured product to be roughened or desmeared. The 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, it is preferable that the cured product is roughened. Prior to the roughening treatment, the cured product is preferably swelled. It is preferable that the cured product is swelled and further cured after the roughening treatment after the pre-curing and before the roughening treatment. However, the cured product does not necessarily have to be swelled.

As the method for the swelling treatment, for example, a method for treating a cured product with an aqueous solution of a compound containing ethylene glycol or the like as a main component, an organic solvent dispersion solution, or the like is used. The swelling liquid used for the swelling treatment generally contains an alkali as a pH adjuster or the like. The swelling liquid preferably contains sodium hydroxide. Specifically, for example, the swelling treatment is carried out by treating the cured product at a treatment temperature of 30 ° C. to 85 ° C. for 1 minute to 30 minutes using a 40 wt% ethylene glycol aqueous solution or the like. 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 water or an organic solvent is added. The roughening liquid used for the roughening treatment generally contains an alkali as a pH adjuster or the like. The roughening 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 average roughness Ra of the surface of the cured product is preferably 10 nm or more, preferably 300 nm or less, more preferably 200 nm or less, and further preferably 150 nm or less. In this case, the adhesive strength between the cured product and the metal layer is increased, and the surface of the insulating layer forms finer wiring. Further, the conductor loss can be suppressed and the signal loss can be suppressed low. The arithmetic mean roughness Ra is measured according to JIS B0601: 1994.

(Desmia processing)
Through holes may be formed in the cured product obtained by pre-curing the resin material. In the multilayer board or the like, vias, through holes, or the like are formed as through holes. For example, vias 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, it is preferable that the surface of the cured product is desmear-treated. The desmear treatment may also serve as the roughening treatment.

In the desmear treatment, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound or a persulfate compound is used in the same manner as in the roughening treatment. 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.

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

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.

The following materials were prepared.

(First curable compound)
Compound represented by the above formula (11) (synthesized according to Synthesis Example 1 below, glass transition temperature: less than 50 ° C., molecular weight 723)

The compound represented by the above formula (11) includes at least the compound represented by the above formula (12).

<Synthesis example 1>
Toluene (200 g) and diamine diamine ("Priamine 1075" manufactured by Croda Japan) (68.6 g) were placed in a 500 mL three-necked flask and stirred. Next, 28.9 g of anhydrous citraconic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 6.25 g of an insoluble acid catalyst (“amberlyst 36 dry” manufactured by DuPont) were placed in the above three-necked flask and stirred. A reflux tube with a Dean-Stark tube was attached, the temperature was adjusted to 130 ° C. in an oil bath, and the mixture was refluxed for 4 hours with stirring. Then, after cooling with air and filtering, the acid catalyst was removed. In addition, the solvent and excess citraconic anhydride were removed by evaporation and air purging.

(Compound that does not correspond to the first curable compound)
1,3-bis (citraconimidemethyl) benzene (glass transition temperature: 75 ° C)
A maleimide compound having a maleimide group at both ends and having a skeleton derived from dimerdiamine (“BMI-689” manufactured by DMI, glass transition temperature: less than 50 ° C., molecular weight 695, represented by the following formula (X1)). Including at least a compound having a structure)
A benzoxazine compound having a benzoxazine group at both ends and having a skeleton derived from dimerdiamine (synthesized according to Synthesis Example 2 below, glass transition temperature: less than 50 ° C., molecular weight 771, represented by the following formula (X2)). (Including at least a compound having such a structure)

<Synthesis example 2>
Toluene (100 g) and diamine diamine ("Priamine 1075" manufactured by Croda Japan Co., Ltd.) (20.5 g) were placed in a 250 mL three-necked flask and stirred. Next, 22.5 g of formaldehyde solution (paraformaldehyde, manufactured by Tokyo Chemical Industry Co., Ltd.) and 14.12 g of phenol were added little by little to the above-mentioned three-necked flask, and the mixture was stirred. A reflux tube with a Dean-Stark tube was attached, the temperature was adjusted to 130 ° C. in an oil bath, and the mixture was refluxed for 4 hours with stirring. Then, it was air-cooled to remove the solvent, excess paraform and phenol.

In the above formula (X1), R ₁ represents a linear hydrocarbon group having 8 carbon atoms, R ₂ represents a linear hydrocarbon group having 6 carbon atoms, and R ₃ represents 8 carbon atoms. It represents a linear hydrocarbon group, R ₄ represents a straight-chain hydrocarbon group having 8 carbon atoms.

In the above formula (X2), R ₁ represents a linear hydrocarbon group having 8 carbon atoms, R ₂ represents a linear hydrocarbon group having 6 carbon atoms, and R ₃ represents 8 carbon atoms. It represents a linear hydrocarbon group, R ₄ represents a straight-chain hydrocarbon group having 8 carbon atoms.

(Thermosetting compound (second thermosetting compound))
<Bismaleimide compound>
Bismaleimide compound 1 (synthesized according to Synthesis Example 3 below, glass transition temperature: 80 ° C to 120 ° C)

<Synthesis example 3>
In a 500 mL three-necked flask, 115 g of toluene, 35 g of N-methyl-2-pyrrolidone (NMP), 8.7 g of dimerdiamine ("Priamine 1075" manufactured by Croda Japan), and norbornane diamine ("Pro-" manufactured by Mitsui Kagaku Fine Co., Ltd.). NBDA ") 10.00 g was added and stirred. Next, 3.0 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in the above three-necked flask and stirred using a stirring rod equipped with a three-one motor. In addition, 7.78 g of 4,4'-biphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid. A mixed solution with 6.99 g of anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was obtained. The obtained mixed solution was placed in the above-mentioned three-necked flask and stirred. Next, a reflux tube with a Dean-Stark tube was attached to one mouth of the three-necked flask, the temperature of the oil bath was adjusted to 130 ° C., and the mixture was refluxed for 4 hours with stirring. Then, 6.22 g of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a three-necked flask and refluxed for 4 hours. After refluxing, the organic layer was washed with water three times to obtain an organic layer in which the bismaleimide compound was dissolved. After distilling off water from the organic layer, it was slowly added dropwise to 2 L of methanol and reprecipitated to obtain a solid content. The solids were collected by suction filtration and dried in a vacuum oven to give the product (recovery rate 80%). The above reprecipitation may or may not be performed.

Bismaleimide compound 2 (synthesized according to Synthesis Example 4 below, glass transition temperature: 80 ° C to 120 ° C)

<Synthesis example 4>
In a 500 mL three-necked flask, 115 g of toluene, 35 g of N-methyl-2-pyrrolidone (NMP), 16.3 g of dimerdiamine ("Priamine 1075" manufactured by Croda Japan), and norbornane diamine ("Pro-" manufactured by Mitsui Kagaku Fine Co., Ltd.). NBDA ") 7.81 g was added and stirred. Next, 3.0 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in the above three-necked flask and stirred using a stirring rod equipped with a three-one motor. In addition, 7.78 g of 4,4'-biphthalic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and bicyclo [2.2.2] Oct-7-en-2,3,5,6-tetracarboxylic dianhydride. A mixed solution with 6.56 g of a product (manufactured by Tokyo Chemical Industry Co., Ltd.) was obtained. The obtained mixed solution was placed in the above-mentioned three-necked flask and stirred. Next, a reflux tube with a Dean-Stark tube was attached to one mouth of the three-necked flask, the temperature of the oil bath was adjusted to 130 ° C., and the mixture was refluxed for 4 hours with stirring. Then, 6.22 g of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a three-necked flask and refluxed for 4 hours. After refluxing, the organic layer was washed with water three times to obtain an organic layer in which the bismaleimide compound was dissolved. After distilling off water from the organic layer, it was slowly added dropwise to 2 L of methanol and reprecipitated to obtain a solid content. The solids were collected by suction filtration and dried in a vacuum oven to give the product (recovery rate 81%). The above reprecipitation may or may not be performed.

<Epoxy compound>
Biphenyl type epoxy compound ("NC-3000L" manufactured by Nippon Kayaku Co., Ltd.)
Naphthalene type epoxy compound ("ESN-475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
Resorcinol diglycidyl ether (“EX-201” manufactured by Nagase ChemteX Corporation)
Multi-branched aliphatic epoxy compound ("FoldiE101" manufactured by Nissan Chemical Industries, Ltd.)
Epoxy compound with amide skeleton ("WHR991S" manufactured by Nippon Kayaku Co., Ltd.)
Epoxy compound with amino group ("630" manufactured by Mitsubishi Chemical Corporation)
Epoxy compound with butadiene skeleton ("PB3600" manufactured by Daicel)

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

(Hardener)
Liquid containing 1 active ester compound ("EXB-9416-70BK" manufactured by DIC Corporation, solid content 70% by weight)
Active ester compound 2 containing liquid ("HPC-8000L" manufactured by DIC Corporation, solid content 65% by weight)
Active ester compound 3 containing liquid ("HPC-8150-62T" manufactured by DIC Corporation, solid content 62% by weight)
Active ester compound 4 (“EXB-8” manufactured by DIC Corporation, solid content 100% by weight, small molecule active ester compound)
Phenol compound-containing liquid ("LA-1356" manufactured by DIC Corporation, solid content 60% by weight)

(Hardening accelerator)
Dimethylaminopyridine ("DMAP" manufactured by Wako Pure Chemical Industries, Ltd., anionic curing accelerator)
2-Phenyl-4-methylimidazole ("2P4MZ" manufactured by Shikoku Chemicals Corporation, anionic curing accelerator)

(Thermoplastic resin)
Polyimide compound (polyimide resin, synthesized according to Synthesis Example 5 below, molecular weight 20000)

<Synthesis Example 5>
300.0 g of tetracarboxylic dianhydride (“BisDA-1000” manufactured by SABIC Japan GK) and 665.5 g of cyclohexanone were placed in a reaction vessel equipped with a stirrer, water divider, thermometer and nitrogen gas introduction tube. And the solution in the reaction vessel was heated to 60 ° C. Next, 89.0 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan Co., Ltd.) and 54.7 g of 1,3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Company, Inc.) were added dropwise to the reaction vessel. Next, 121.0 g of methylcyclohexane and 423.5 g of ethylene glycol dimethyl ether were added to the reaction vessel, and an imidization reaction was carried out at 140 ° C. for 10 hours. In this way, a polyimide compound-containing solution (nonvolatile content 26.8% by weight) was obtained. The molecular weight (weight average molecular weight) of the obtained polyimide compound was 20000. The molar ratio of the acid component / amine component was 1.04.

(Measurement of molecular weight)
The molecular weights of the first curable compound and the polyimide compound were determined as follows.

GPC (Gel Permeation Chromatography) Measurement:
A high performance liquid chromatograph system manufactured by Shimadzu Corporation was used, and measurement was carried out using tetrahydrofuran (THF) as a developing medium at a column temperature of 40 ° C. and a flow velocity 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 Co., Ltd. were connected in series and used. Tosoh's "TSK standard polystyrene" is used as the standard polystyrene, and the weight average molecular weight Mw = 354,000, 189,000, 98,900, 37,200, 17,100, 9,830, 5,870, 2, Calibration curves were made using 500, 1,050, and 500 materials and the molecular weight was calculated.

(Examples 1 and 2 and Comparative Examples 1 to 4)
The components shown in Tables 1 and 2 below were blended in the blending amounts (unit: parts by weight of solid content) shown in Tables 1 and 2 below, and stirred at room temperature until a uniform solution was obtained to obtain a resin material.

Preparation of resin film:
After applying the obtained resin material on the release-treated surface of the release-treated PET film (Toray Industries, Inc. "XG284", thickness 25 μm) using an applicator, 2 minutes in a gear oven at 100 ° C. It was dried for 30 seconds to volatilize the solvent. In this way, a laminated film (laminated film of PET film and resin film) in which a resin film (B stage film) having a thickness of 40 μm is laminated on the PET film was obtained.

(evaluation)
(1) Storage stability The obtained resin film (B stage film) was allowed to stand at room temperature for 3 days. The melt viscosity of the B stage film before and after standing was measured. The melt viscosity increases from the minimum value of the melt viscosity of the B stage film before standing at 100 ° C (minimum melt viscosity) and the minimum value of the melt viscosity of the B stage film after standing at 100 ° C (minimum melt viscosity). The ratio was calculated. Storage stability was judged according to the following criteria. The melt viscosity was determined by using a rheometer device (“AR2000” manufactured by TA Instruments) under the conditions of a temperature rise rate of 5 ° C./min, strain of 20%, and frequency of 1 Hz in the range of 60 ° C to 180 ° C. Measured at.

[Criteria for storage stability]
◯: The rate of increase in melt viscosity is less than 25% ×: The rate of increase in melt viscosity is 25% or more

(2) Curing performance The exothermic peak associated with curing of the obtained resin film (B stage film) was evaluated using a differential scanning calorimetry device (“Q2000” manufactured by TA Instrument Co., Ltd.). 8 mg of the resin film was taken on a special aluminum pan and covered with a special jig. This dedicated aluminum pan and an empty aluminum pan (reference) are installed in the heating unit and heated from -30 ° C to 250 ° C at a heating rate of 3 ° C / min under a nitrogen atmosphere, and reverse heat flow and non-reverse. The heat flow was observed. The curing temperature was confirmed by the exothermic peak observed in the non-reverse heat flow. The curing performance was judged according to the following criteria.

[Criteria for curing performance]
◯: All exothermic peaks at 200 ° C. or lower ×: At least one exothermic peak at a temperature higher than 200 ° C. (an exothermic peak at a temperature higher than 200 ° C. and an exothermic peak at 200 ° C. or lower Including those with)

(3) Dissipation factor (Df)
The obtained resin film was heated at 190 ° C. for 90 minutes to obtain a cured product. The obtained cured product was cut into a size of 2 mm in width and 80 mm in length, and 10 sheets were stacked. Using a network analyzer N5224A PNA, the dielectric loss tangent was measured at room temperature (23 ° C.) and at a frequency of 5.8 GHz by the cavity resonance method.

[Criteria for determining dielectric loss tangent]
○ ○: Dissipation factor is 2.10 × 10 ^-3 or less ○: Dissipation factor ^{exceeds 2.10 × 10 -3} 2.30 × 10 ^-3 or less ×: Dissipation factor exceeds ^{2.30 × 10 -3}

(4) Embedding property in uneven surface Only the copper foil of a 100 mm square copper-clad laminate (a laminate of a glass epoxy board with a thickness of 400 μm and a copper foil with a thickness of 25 μm) is etched to have a diameter of 100 μm and a depth of 25 μm. The recess (opening) was made so that the distance between the centers of the holes linearly and adjacent to the area of 30 mm square at the center of the substrate was 900 μm. In this way, an evaluation board having a recess of 900 holes in total was prepared.

The resin film side of the obtained laminated film is laminated on the evaluation substrate, and a "batch type vacuum laminator MVLP-500-IIA" manufactured by Meiki Seisakusho Co., Ltd. is used, the laminating pressure is 0.4 MPa for 20 seconds, and the pressing pressure is 0.8 MPa. The laminate and press were heated and pressurized at a temperature of 85 ° C. for 20 seconds. After cooling at room temperature, the PET film was peeled off. In this way, an evaluation sample in which a resin film was laminated on the evaluation substrate was obtained.

Voids in the depressions were observed in the obtained evaluation sample using an optical microscope. By evaluating the ratio of the number of dents in which voids were observed, the embedding property in the uneven surface was determined according to the following criteria.

[Criteria for embedding on uneven surfaces]
◯: Percentage of the number of depressions in which voids were observed 0%
Δ: Percentage of the number of depressions in which voids were observed More than 0% and less than 5% ×: Percentage of the number of depressions in which voids were observed 5% or more

(5) Surface roughness after etching (surface roughness)
Laminating process and semi-hardening process:
A double-sided copper-clad laminate (CCL substrate) (“E679FG” manufactured by Hitachi Kasei Co., Ltd.) was prepared. Both sides of the copper foil surface of this double-sided copper-clad laminate were immersed in "Cz8101" manufactured by MEC to roughen the surface of the copper foil. Using "Batch type vacuum laminator MVLP-500-IIA" manufactured by Meiki Seisakusho Co., Ltd. on both sides of the roughened copper-clad laminate, the resin film (B stage film) side of the laminate film is placed on the copper-clad laminate. A laminated structure was obtained by laminating on top of each other. The laminating conditions were such that the pressure was reduced for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then the press was performed at 100 ° C. and a pressure of 0.4 MPa for 30 seconds. Then, the resin film was semi-cured by heating at 180 ° C. for 30 minutes. In this way, a laminated body in which a semi-cured product of a resin film was laminated on a CCL substrate was obtained.

Roughening process:
(A) Swelling treatment:
The obtained laminate was placed in a swelling solution at 60 ° C. (“Swelling Dip Securigant P” manufactured by Atotech Japan) and shaken for 10 minutes. Then, it was washed with pure water.

(B) Permanganate treatment (roughening treatment and desmear treatment):
The swelling-treated laminate was placed in a crude aqueous solution of potassium permanganate (“Concentrate Compact CP” manufactured by Atotech Japan) at 80 ° C. and shaken for 30 minutes. Next, it was treated with a cleaning solution at 25 ° C. (“Reduction Securigant P” manufactured by Atotech Japan) for 2 minutes, and then washed with pure water to obtain an evaluation sample.

Measurement of surface roughness:
On the surface of the evaluation sample (roughened cured product), 10 regions of 94 μm × 123 μm were arbitrarily selected. Arithmetic mean roughness Ra was measured for each of these 10 regions using a non-contact three-dimensional surface shape measuring device (“WYKO NT1100” manufactured by Veeco). From the average value of the measured arithmetic mean roughness Ra at 10 points, the surface roughness after etching was determined according to the following criteria. The arithmetic mean roughness Ra was measured according to JIS B0601: 1994.

[Criteria for determining surface roughness after etching]
○ ○: The average value of the arithmetic average roughness Ra is less than 50 nm ○: The average value of the arithmetic average roughness Ra is 50 nm or more and less than 120 nm ×: The average value of the arithmetic average roughness Ra is 120 nm or more

The composition and results are shown in Tables 1 and 2 below.

11 ... Multi-layer printed wiring board 12 ... Circuit board 12a ... Top surface 13-16 ... Insulation layer 17 ... Metal layer

Claims (17)

The first curable compound having a group represented by the following formula (1) and
Contains curing accelerators
A resin material having a glass transition temperature of the first curable compound of less than 75 ° C.

In the formula (1), R ₁ represents an alkyl group and R ₂ represents a hydrogen atom or an alkyl group. The resin material according to claim 1, wherein the first curable compound has two or more groups represented by the formula (1). The resin material according to claim 1 or 2, wherein the first curable compound has a skeleton derived from dimerdiamine. The resin material according to any one of claims 1 to 3, wherein the first curable compound is a compound represented by the following formula (11).

In the formula (11), R ₁ represents a linear hydrocarbon group _{having 6 or more and 10 or less carbon atoms, and R 2} represents a linear hydrocarbon group having 6 or more and 10 or less carbon atoms. ₃ represents a straight-chain hydrocarbon group having 6 to 10 carbon atoms, R ₄ represents a straight-chain hydrocarbon group having 6 to 10 carbon atoms. In the above formula (11), the total number of carbon atoms of _{R 1} , R ₂ , R ₃ and R _{4 is 30.} The resin material according to any one of claims 1 to 4, wherein the curing accelerator is an anionic curing accelerator. The resin material according to claim 5, wherein the anionic curing accelerator is dimethylaminopyridine. The resin material according to any one of claims 1 to 4, wherein the curing accelerator is a radical curing accelerator. Further containing a thermosetting compound,
The thermosetting compound contains a bismaleimide compound and contains.
The resin material according to any one of claims 1 to 7, wherein the glass transition temperature of the bismaleimide compound is 75 ° C. or higher. The resin material according to claim 8, wherein the bismaleimide compound has a structural unit having an imide bond as a repeating structural unit. The resin material according to claim 8 or 9, wherein the thermosetting compound further contains a thermosetting compound other than the bismaleimide compound. The resin material according to any one of claims 8 to 10, wherein the thermosetting compound contains a vinyl compound or an epoxy compound. Contains hardener,
The resin material according to any one of claims 1 to 11, wherein the curing agent contains a phenol compound and an active ester compound. The resin material according to any one of claims 1 to 12, which comprises a filler. The resin material according to claim 13, wherein the filler is an insulating filler. The resin material according to any one of claims 1 to 14, which is a resin film. The resin material according to any one of claims 1 to 15, which is used for forming an insulating layer in a multilayer printed wiring board. With the circuit board
A plurality of insulating layers arranged on the surface of the circuit board,
With a metal layer arranged between the plurality of insulating layers,
A multilayer printed wiring board in which at least one of the plurality of insulating layers is a cured product of the resin material according to any one of claims 1 to 16.

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