TW202511385A - Resin materials, hardeners and multi-layer printed wiring boards - Google Patents

Abstract

Provided is a resin material with which the dielectric constant of a cured product can be lowered and in which hollow inorganic particles are resistant to cracking even when subjected to ultrasonic treatment. A resin material according to the present invention contains a thermosetting compound (A) and hollow inorganic particles (B), the root mean square height Rq of the outer surface of the hollow inorganic particles (B) being 2 nm or greater.

Description

Resin materials, hardeners and multi-layer printed wiring boards

The present invention relates to a resin material containing a thermosetting compound. The present invention also relates to a cured product of the resin material. Furthermore, the present invention relates to a multi-layer printed wiring board using the resin material.

In the past, various resin materials have been used to obtain electronic components such as semiconductor devices, laminated boards, and printed wiring boards. For example, in a multi-layer printed wiring board, a resin material is used to form an insulating layer for insulating the internal layers or to form an insulating layer located on the surface. The surface of the insulating layer is generally laminated with metal wiring. In addition, a film-like resin material (resin film) is sometimes used to form the insulating layer. The resin material is used as an insulating material for a multi-layer printed wiring board including a build-up film, etc.

The following patent document 1 discloses a resin composition comprising (A) epoxy resin, (B) hardener, (C) hollow silica, and (D) molten silica. When the non-volatile components in the resin composition are set to 100% by mass, the content of the hollow silica (C) is 5-22% by mass, and the total content of the hollow silica (C) and the molten silica (D) is 50-70% by mass.

The following patent document 2 discloses a resin composition comprising a thermosetting resin (A) and a filler (B), wherein the filler (B) comprises hollow particles (b) satisfying a specific formula and having an average particle size of 0.01 to 10 μm. [Prior art document] [Patent document]

[Patent Document 1] Japanese Patent Publication No. 2013-173841 [Patent Document 2] WO2019/230661A1

[The problem the invention is trying to solve]

As described in the above-mentioned patent documents 1 and 2, a resin material containing a thermosetting compound and hollow inorganic particles is known. By using the hollow inorganic particles, the dielectric constant of the cured product of the resin material can be reduced to a certain extent.

When manufacturing electronic components such as printed wiring boards, wiring is sometimes formed by laminating, heating, degumming, and ultrasonic treatment of resin materials on substrates. However, when using a previous resin material containing hollow inorganic particles, the hollow inorganic particles sometimes break during these treatments. Among these treatments, hollow inorganic particles are particularly prone to breakage during ultrasonic treatment. If the hollow inorganic particles break, the wiring forming solution penetrates into the broken part, increasing the penetration of copper, so that short circuits sometimes occur between the wiring.

The object of the present invention is to provide a resin material that can reduce the dielectric constant of a cured product and the hollow inorganic particles are not easily broken even after ultrasonic treatment. In addition, the object of the present invention is to provide a cured product of the above resin material. Furthermore, the object of the present invention is to provide a multi-layer printed wiring board using the above resin material. [Technical means for solving the problem]

This specification discloses the following resin materials, cured products, and multi-layer printed wiring boards.

Item 1. A resin material comprising a thermosetting compound (A) and hollow inorganic particles (B), wherein the root mean square height Rq of the outer surface of the hollow inorganic particles (B) is greater than 2 nm.

Item 2. The resin material as described in Item 1, wherein the hollow inorganic particles (B) are hollow silica particles.

Item 3. The resin material as described in Item 1 or 2, wherein the above-mentioned thermosetting compound (A) comprises a thermosetting compound having an epoxy group, a vinyl group, a styrene group, a benzophenone group, a cyanate group, an allyl group, a methacryl group, an acryl group or a succinimidyl group.

Item 4. The resin material as described in any one of Items 1 to 3, wherein the thermosetting compound (A) comprises a succinimidyl compound.

Item 5. The resin material as described in any one of Items 1 to 4, further comprising solid inorganic particles (C).

Item 6. The resin material according to any one of Items 1 to 5, wherein the content of the hollow inorganic particles (B) is 60% by weight or less in 100% by weight of the components other than the solvent in the resin material.

Item 7. A resin material as described in any one of Items 1 to 6, wherein when the resin material is heated at 180°C for 30 minutes and then heated at 200°C for 60 minutes to obtain a cured resin material, the dielectric constant of the cured resin material obtained at 10 GHz is less than 2.5.

Item 8. The resin material as described in any one of Items 1 to 7, which is a resin film.

Item 9. The resin material as described in any one of Items 1 to 8, which is used to form an insulating layer in a multi-layer printed wiring board.

Item 10. A hardened product, which is a hardened product of a resin material, and the resin material is the resin material described in any one of Items 1 to 9.

Item 11. A multi-layer printed wiring board comprising: a circuit substrate, a plurality of insulating layers disposed on a surface of the circuit substrate, and a metal layer disposed between the plurality of insulating layers, wherein at least one of the plurality of insulating layers is a cured product of the resin material described in any one of Items 1 to 9. [Effect of the Invention]

The resin material of the present invention comprises a thermosetting compound (A) and hollow inorganic particles (B), and the root mean square height Rq of the outer surface of the hollow inorganic particles (B) is greater than 2 nm. Since the resin material of the present invention has the above-mentioned structure, the dielectric constant of the cured product can be reduced, and even after ultrasonic treatment, the hollow inorganic particles are not easily broken.

The following is a detailed description of the present invention.

(Resin Material) The resin material of the present invention comprises a thermosetting compound (A) and hollow inorganic particles (B), and the root mean square height Rq of the outer surface of the hollow inorganic particles (B) is greater than 2 nm.

Since the resin material of the present invention has the above-mentioned structure, the dielectric constant of the cured product can be reduced, and even after ultrasonic treatment, the hollow inorganic particles are not prone to breakage.

The resin material of the present invention can maintain a low dielectric constant of the cured product before and after ultrasonic treatment.

When the previous resin material containing hollow inorganic particles is pressed, the hollow inorganic particles are also easily broken. In contrast, even if the resin material of the present invention is pressed, the hollow inorganic particles are not easily broken. Therefore, even when the resin material of the present invention is pressed for use, the dielectric constant of the cured product can be reduced.

In addition, the resin material of the present invention can effectively suppress short circuits between wirings because the hollow inorganic particles are not easily broken.

The resin material of the present invention can be a resin composition or a resin film. The resin composition has fluidity. The resin composition can also be a paste. The paste includes a liquid. In terms of excellent operability, the resin material of the present invention is preferably a resin film.

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

Furthermore, in the following description, "100% by weight of the components other than the solvent in the resin material" means 100% by weight of the components other than the solvent in the resin material when the resin material contains a solvent, and means 100% by weight of the resin material when the resin material does not contain a solvent. "100% by weight of the components other than the hollow inorganic particles (B), the solid inorganic particles (C) and the solvent in the resin material" means 100% by weight of the components other than the hollow inorganic particles (B), the solid inorganic particles (C) and the solvent in the resin material when the resin material contains the hollow inorganic particles (B), the solid inorganic particles (C) and the solvent. “100% by weight of the components other than the hollow inorganic particles (B), the solid inorganic particles (C) and the solvent in the resin material” means 100% by weight of the components other than the hollow inorganic particles (B) and the solvent in the resin material when the resin material contains the hollow inorganic particles (B) and the solvent but does not contain the solid inorganic particles (C). “100% by weight of the components other than the hollow inorganic particles (B), the solid inorganic particles (C) and the solvent in the resin material” means 100% by weight of the components other than the hollow inorganic particles (B) in the resin material when the resin material contains the hollow inorganic particles (B) but does not contain the solid inorganic particles (C) and the solvent.

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

[Thermosetting compound (A)] The resin material includes a thermosetting compound (A). As the thermosetting compound (A), a conventionally known thermosetting compound can be used. The thermosetting compound (A) may be used alone or in combination of two or more.

The thermosetting compound (A) is preferably a thermosetting compound containing an epoxy group, a vinyl group, a styryl group, a benzophenone group, a cyanate group, an allyl group, a methacryl group, an acryl group, or a cis-butylene diimide group. The thermosetting compound (A) is more preferably a thermosetting compound containing an epoxy group, a vinyl group, a styryl group, a benzophenone group, a cyanate group, an allyl group, a methacryl group, or a cis-butylene diimide group. In this case, the effect of the present invention can be further effectively exerted.

The molecular weight of the thermosetting compound (A) is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more, and preferably 200,000 or less, more preferably 100,000 or less, and further preferably 50,000 or less. If the molecular weight is above the lower limit and below the upper limit, a resin material with high fluidity can be easily obtained when forming an insulating layer, and the layer compressibility can be improved. In addition, since the layer compressibility can be improved, the plating peeling strength of the cured product can be further improved.

The molecular weight of the thermosetting compound (A) refers to the molecular weight that can be calculated from the structural formula when the thermosetting compound (A) is not a polymer and when the structural formula of the thermosetting compound (A) can be specified. Furthermore, when the thermosetting compound (A) is a polymer, it refers to the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

In the above resin material, the content of the thermosetting compound (A) is preferably 1% by weight or more, more preferably 3% by weight or more, further preferably 10% by weight or more, particularly preferably 20% by weight or more, and preferably 60% by weight or less, more preferably 50% by weight or less. If the content of the thermosetting compound (A) is above the above lower limit and below the above upper limit, the dielectric constant and dielectric dissipation factor of the cured product can be further reduced, and the thermal dimensional stability of the cured product can be further improved.

In the resin material, the content of the thermosetting compound (A) is preferably 5% by weight or more, more preferably 10% by weight or more, further preferably 20% by weight or more, further preferably 30% by weight or more, further preferably 40% by weight or more, particularly preferably 50% by weight or more, and preferably 100% by weight or less, and more preferably 95% by weight or less. If the content of the thermosetting compound (A) is above the lower limit and below the upper limit, the dielectric constant and dielectric dissipation factor of the cured product can be further reduced, and the thermal dimensional stability of the cured product can be further improved.

<Thermosetting compound having epoxy group (epoxy compound)> Thermosetting compound (A) may include a thermosetting compound having epoxy group (epoxy compound), or may be a thermosetting compound having epoxy group (epoxy compound). The above-mentioned epoxy compound may be used alone or in combination of two or more.

Examples of the epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, bisphenol E type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, biphenyl type epoxy compounds, biphenyl novolac type epoxy compounds, biphenol type epoxy compounds, naphthalene type epoxy compounds, fluorene type epoxy compounds, phenol aralkyl type epoxy compounds, naphthol aralkyl type epoxy compounds, dicyclopentadiene type epoxy compounds, anthracene type epoxy compounds, epoxy compounds having an adamantane skeleton, epoxy compounds having a tricyclodecane skeleton, naphthyl ether type epoxy compounds, and epoxy compounds having a trioxane nucleus as the skeleton.

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

The epoxy compound is preferably an epoxy compound having an aromatic ring, more preferably an epoxy compound having a naphthalene skeleton or a phenyl skeleton, and even more preferably an epoxy compound having an aromatic ring. In this case, the dielectric constant and dielectric dissipation factor of the cured product can be further reduced, and the thermal dimensional stability of the cured product can be further improved.

From the viewpoint of further reducing the dielectric constant and dielectric dissipation factor of the cured product and improving the coefficient of linear expansion (CTE) of the cured product, the epoxy compound is preferably an epoxy compound that is liquid at 25°C, and more preferably an epoxy compound that is liquid at 25°C and an epoxy compound that is solid at 25°C. In particular, when the epoxy compound is an epoxy compound that is liquid at 25°C, a resin material with high fluidity can be easily obtained when forming an insulating layer, and the layer compressibility can be improved. In addition, since the layer compressibility can be improved, the plating peeling strength of the cured product can be further improved.

The viscosity of the epoxy compound that is liquid at 25°C at 25°C is preferably 10000 mPa·s or less, more preferably 5000 mPa·s or less. The viscosity of the epoxy compound that is liquid at 25°C at 25°C may be 1 mPa·s or more, 10 mPa·s or more, or 100 mPa·s or more.

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

The molecular weight of the epoxy compound is preferably 1000 or less. In this case, a resin material with high fluidity can be easily obtained when forming the insulating layer, and the layer compressibility can be improved. In addition, since the layer compressibility can be improved, the coating peel strength of the cured product can be further improved. The molecular weight of the epoxy compound may be 100 or more, or 200 or more.

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

In 100 wt % of the components other than the solvent in the resin material, the content of the epoxy compound is preferably 1 wt % or more, more preferably 3 wt % or more, and preferably 60 wt % or less, more preferably 50 wt % or less. If the content of the epoxy compound is above the lower limit and below the upper limit, the dielectric constant and dielectric dissipation factor of the cured product can be further reduced, and the thermal dimensional stability of the cured product can be further improved.

<Thermosetting compound (vinyl compound) having a vinyl group> Thermosetting compound (A) may include a thermosetting compound (vinyl compound) having a vinyl group, or may be a thermosetting compound (vinyl compound) having a vinyl group. The above-mentioned vinyl compound may be used alone or in combination of two or more.

Examples of the vinyl compound include divinyl benzyl ether compounds.

In the resin material, the content of the vinyl compound is preferably 1% by weight or more, more preferably 3% by weight or more, and preferably 60% by weight or less, more preferably 50% by weight or less, out of 100% by weight of the components other than the solvent. If the content of the vinyl compound is above the lower limit and below the upper limit, the dielectric constant and dielectric dissipation factor of the cured product can be further reduced, and the thermal dimensional stability of the cured product can be further improved.

<Thermosetting compound having styryl group (styryl compound)> Thermosetting compound (A) may include a thermosetting compound having styryl group (styryl compound), or may be a thermosetting compound having styryl group (styryl compound). The above-mentioned styryl compound may be used alone or in combination of two or more.

Examples of commercially available products of the styryl compound include "OPE-2St" and "OPE-1200" manufactured by Mitsubishi Gas Chemical Co., Ltd.

In 100 wt % of the components other than the solvent in the resin material, the content of the styrene-based compound is preferably 1 wt % or more, more preferably 3 wt % or more, and preferably 60 wt % or less, more preferably 50 wt % or less. If the content of the styrene-based compound is above the lower limit and below the upper limit, the dielectric constant and dielectric dissipation factor of the cured product can be further reduced, and the thermal dimensional stability of the cured product can be further improved.

<Thermosetting compound having a benzothiazol group (benzothiazol compound)> Thermosetting compound (A) may include a thermosetting compound having a benzothiazol group (benzothiazol compound), or may be a thermosetting compound having a benzothiazol group (benzothiazol compound). The above-mentioned benzothiazol compound may be used alone or in combination of two or more.

Examples of the benzophenone compound include P-d type benzophenone and F-a type benzophenone.

Examples of commercially available products of the benzophenone compound include "P-d type" manufactured by Shikoku Chemical Industries, Ltd.

The content of the benzophenone compound in 100% by weight of the components other than the solvent in the resin material is preferably 1% by weight or more, more preferably 3% by weight or more, and preferably 60% by weight or less, more preferably 50% by weight or less. If the content of the benzophenone compound is above the lower limit and below the upper limit, the dielectric constant and dielectric dissipation factor of the cured product can be further reduced, and the thermal dimensional stability of the cured product can be further improved.

<Thermosetting compound having cyanate group (cyanate compound)> Thermosetting compound (A) may include a thermosetting compound having cyanate group (cyanate compound), or may be a thermosetting compound having cyanate group (cyanate compound). The above-mentioned cyanate compound may be used alone or in combination of two or more.

The cyanate compound is preferably a cyanate ester compound.

Examples of the cyanate compound include novolac cyanate resins, bisphenol cyanate resins, and prepolymers obtained by trimerization of a part of the novolac cyanate resins. Examples of the novolac cyanate resins include phenol novolac cyanate resins and alkylphenol cyanate resins. Examples of the bisphenol cyanate resins include bisphenol A cyanate resins, bisphenol E cyanate resins, and tetramethylbisphenol F cyanate resins.

Examples of commercially available cyanate compounds include bisphenol A type cyanate resins ("P-201" manufactured by Mitsubishi Gas Chemical Co., Ltd.), phenol novolac type cyanate resins ("PT-30" and "PT-60" manufactured by Lonza Corporation of Japan), and prepolymers of bisphenol type cyanate resins obtained by trimerization ("BA-230S", "BA-3000S", "BTP-1000S" and "BTP-6020S" manufactured by Lonza Corporation of Japan).

In the resin material, the content of the cyanate compound is preferably 1% by weight or more, more preferably 3% by weight or more, and preferably 60% by weight or less, more preferably 50% by weight or less, out of 100% by weight of the components other than the solvent. If the content of the cyanate compound is above the lower limit and below the upper limit, the dielectric constant and dielectric dissipation factor of the cured product can be further reduced, and the thermal dimensional stability of the cured product can be further improved.

<Thermosetting compound having a methacryloyl group (methacryloyl compound)> The thermosetting compound (A) may include a thermosetting compound having a methacryloyl group (methacryloyl compound), or may be a thermosetting compound having a methacryloyl group (methacryloyl compound). The above-mentioned methacryloyl compound may be used alone or in combination of two or more.

Examples of commercially available products of the methacryloyl compound include "SA9000-111" manufactured by SABIC.

In the resin material, the content of the methacrylic compound is preferably 1% by weight or more, more preferably 3% by weight or more, and preferably 60% by weight or less, more preferably 50% by weight or less, in 100% by weight of the components other than the solvent. If the content of the methacrylic compound is above the lower limit and below the upper limit, the dielectric constant and dielectric dissipation factor of the cured product can be further reduced, and the thermal dimensional stability of the cured product can be further improved.

<Thermosetting compound having cis-butenediamide group (cis-butenediamide compound)> Thermosetting compound (A) may also include a thermosetting compound having cis-butenediamide group (cis-butenediamide compound), or may be a thermosetting compound having cis-butenediamide group (cis-butenediamide compound). The above-mentioned cis-butenediamide compound may be used alone or in combination of two or more.

The cis-butylenediimide compound may have one cis-butylenediimide group, or two, or more, or more, or more, or more than 4, or less than 800, or less than 500, or less than 300.

From the viewpoint of further reducing the dielectric constant and dielectric dissipation factor of the cured product, the cis-butylene diimide compound is preferably a cis-butylene diimide compound having two cis-butylene diimide groups, and more preferably a cis-butylene diimide compound having two cis-butylene diimide groups. Therefore, the cis-butylene diimide compound is preferably a bis-cis-butylene diimide compound, and more preferably a bis-cis-butylene diimide compound.

The cis-butylenediimide compound preferably has an aliphatic skeleton or an alicyclic skeleton, and more preferably has an aliphatic skeleton and an alicyclic skeleton. In this case, the effect of the present invention can be further effectively exerted. In addition, the desmearing property and the coating peeling strength can also be improved.

As the above-mentioned aliphatic skeleton, a chain aliphatic skeleton and the like can be exemplified, for example, a saturated alkyl group and an unsaturated alkyl group and the like can be exemplified. The above-mentioned aliphatic skeleton is preferably an aliphatic skeleton having 4 or more carbon atoms. The carbon number of the aliphatic skeleton having 4 or more carbon atoms is preferably 5 or more, more preferably 6 or more, further preferably 7 or more, and is preferably 60 or less, more preferably 50 or less, further preferably 40 or less. As the above-mentioned aliphatic skeleton, more specifically, an alkyl group having 4 or more carbon atoms and 60 or less (preferably an alkyl group having 6 or more carbon atoms and 40 or less) and the like can be exemplified. The above-mentioned cis-butylene diimide compound may have only one of the above-mentioned aliphatic skeletons, or may have two or more of them.

Examples of the alicyclic skeleton include a monocyclic alkane ring, a bicyclic alkane ring, a tricyclic alkane ring, a tetracyclic alkane ring, and a dicyclopentadiene ring. The cis-butylenediimide compound may have only one type of the alicyclic skeleton, or may have two or more types.

From the viewpoint of further increasing the glass transition temperature of the cured product, the maleimide compound preferably has an aromatic skeleton.

Examples of the aromatic skeleton include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fused tetraphenyl ring, The cis-butylenediimide compound may have only one of the above aromatic skeletons, or may have two or more of the above aromatic skeletons.

The cis-butylene diimide compound preferably has a skeleton derived from dimerized diamine. The cis-butylene diimide compound having a skeleton derived from dimerized diamine has an aliphatic skeleton and an alicyclic skeleton, so by using the cis-butylene diimide compound, the dielectric constant and dielectric dissipation factor of the cured product can be further reduced.

Examples of the dimer diamine (commercially available dimer diamine) include "VERSAMINE 551" (3,4-bis(1-aminoheptyl)-6-hexyl-5-(1-octenyl)cyclohexene) manufactured by BASF Japan, "VERSAMINE 552" (hydrogenated product of VERSAMINE 551) manufactured by Cognix Japan, and "PRIAMINE 1075" and "PRIAMINE 1074" manufactured by Croda Japan. The dimer diamine may be used alone or in combination of two or more.

The cis-butylenediimide compound preferably has a skeleton derived from dimerized diamine and a skeleton derived from a second diamine compound other than dimerized diamine. In this case, the effect of the present invention can be more effectively exerted.

Examples of the second diamine compound include tricyclodecanediamine, northanediamine, isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(aminomethyl)northane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.02,6]decane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), 1,4-butanediamine, amine, 1,10-decanediamine, 1,12-dodecanediamine, 1,7-heptanediamine, 1,6-hexanediamine, 1,5-pentanediamine, 1,8-octanediamine, 1,3-propylenediamine, 1,11-undecanediamine, 2-methyl-1,5-pentanediamine, 1,1-bis(4-aminophenyl)cyclohexane, 2,7-diaminofluorene, 4,4'-ethylenediphenylamine, 4,4'-methylenebis(2,6-diethylaniline), and 4,4'-methylenebis(2-ethyl-6-methylaniline). The second diamine compound may be used alone or in combination of two or more.

The second diamine compound may or may not have an aliphatic skeleton. The second diamine compound may or may not have an alicyclic skeleton. The second diamine compound may or may not have an aromatic skeleton.

The second diamine compound is preferably a diamine compound having an alicyclic skeleton other than dimerized diamine. The cis-butylenediimide compound is preferably a diamine compound having a skeleton derived from dimerized diamine and a skeleton derived from a diamine compound having an alicyclic skeleton other than dimerized diamine. In this case, the effect of the present invention can be further effectively exerted.

The diamine compound having an alicyclic skeleton other than the above-mentioned dimerized diamine is preferably tricyclic decanediamine, northanediamine or isophoronediamine. In this case, the effect of the present invention can be further effectively exerted.

The maleimide compound preferably has a skeleton derived from an acid dianhydride, more preferably has a skeleton derived from a reaction product of a diamine compound and an acid dianhydride, and further preferably has a skeleton derived from a reaction product of a dimerized diamine and an acid dianhydride.

Examples of the acid dianhydride include tetracarboxylic dianhydride and the like. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl sulfide tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4 '-Bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, and bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride. The above acid dianhydrides may be used alone or in combination of two or more.

The molecular weight of the cis-butylenediimide compound is preferably 200 or more, more preferably 500 or more, and further preferably 1000 or more, and preferably 200,000 or less, more preferably 100,000 or less, and further preferably 50,000 or less. If the molecular weight is above the lower limit and below the upper limit, a resin material with high fluidity can be easily obtained when forming an insulating layer, and the layer compressibility can be improved. In addition, since the layer compressibility can be improved, the plating peel strength of the cured product can be further improved.

The molecular weight of the cis-butylene diimide compound, when the cis-butylene diimide compound (A) is not a polymer and when the structural formula of the cis-butylene diimide compound can be specified, means a molecular weight that can be calculated from the structural formula. Furthermore, when the cis-butylene diimide compound is a polymer, it means a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

Examples of commercially available products of the above-mentioned cis-butylenediimide compounds include "NE-X-9470S" manufactured by DIC Corporation, "MIR-5000-60T" and "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., "BMI-3000J", "BMI-2500", "BMI-1500" and "BMI-689" manufactured by Designer Molecules Inc., and "BMI", "BMI-70" and "BMI-80" manufactured by Ki-chemical Co., Ltd.

The maleic anhydride compound can also be obtained by reacting an acid dianhydride such as tetracarboxylic dianhydride with a diamine compound to obtain a reaction product, and then reacting the reaction product with maleic anhydride.

The content of the cis-butylene diimide compound in 100% by weight of the components other than the solvent in the resin material is preferably 1% by weight or more, more preferably 3% by weight or more, and preferably 60% by weight or less, more preferably 50% by weight or less. If the content of the cis-butylene diimide compound is above the lower limit and below the upper limit, the lamination property can be further improved. In addition, the surface roughness after the roughening treatment can be further reduced, and further, the plating peeling strength of the hardened material can be further improved.

[Hollow Inorganic Particles (B)] The resin material contains hollow inorganic particles (B). The hollow inorganic particles (B) may be used alone or in combination of two or more.

The hollow inorganic particle (B) is an inorganic particle having a hollow portion. The hollow inorganic particle (B) has a hollow portion and a shell surrounding the hollow portion. The number of the hollow portions surrounded by the shell is usually one.

The hollow inorganic particle (B) is formed of an inorganic substance. More specifically, the shell of the hollow inorganic particle (B) is formed of an inorganic substance.

Examples of the inorganic material forming the hollow inorganic particles (B) include silicon dioxide, aluminum silicate, silsesquioxane, aluminum oxide, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, aluminum magnesium carbonate, alumina, aluminum hydroxide, and the like. , magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. The above inorganic substances may be used alone or in combination of two or more.

The inorganic substance forming the hollow inorganic particles (B) preferably includes silica, aluminosilicate or silsesquioxane, more preferably includes silica or aluminosilicate, further preferably includes silica, and particularly preferably includes silica. The hollow inorganic particles (B) preferably include hollow silica particles, hollow aluminosilicate particles or hollow silsesquioxane particles, more preferably include hollow silica particles or hollow aluminosilicate particles, further preferably include hollow silica particles, and particularly preferably include hollow silica particles. In this case, the dielectric constant and dielectric dissipation factor of the cured resin material can be further reduced.

From the viewpoint of suppressing the breakage of the hollow inorganic particles during ultrasonic treatment, the root mean square height Rq of the outer surface of the hollow inorganic particles (B) is 2 nm or more. In addition, by making the root mean square height Rq of the outer surface of the hollow inorganic particles (B) 2 nm or more, the breakage of the hollow inorganic particles during lamination can also be suppressed.

The root mean square height Rq of the outer surface of the hollow inorganic particle (B) is preferably 2.1 nm or more, more preferably 2.5 nm or more, and preferably 50 nm or less, more preferably 30 nm or less. If the root mean square height Rq is above the lower limit and below the upper limit, the rupture of the hollow inorganic particle during ultrasonic treatment and lamination can be further effectively suppressed.

The root mean square height Rq of the outer surface of the hollow inorganic particle (B) can be obtained using an atomic force microscope (AFM). Specifically, it can be obtained as follows.

Epoxy resin is thinly coated on the surface of a silicon wafer. Hollow inorganic particles are scattered on the surface of the coated epoxy resin to prepare a sample. The sample is placed in an atomic force microscope (AFM) (e.g., "Cypher ES" manufactured by Oxford Instruments). Using an AC160 probe, measurements are performed at a scanning rate of 1 Hz and in AM-FM mode. A square area is set with a side length that is the same as the radius of the hollow inorganic particle (B). For the square area, the shape is measured with 256×256 pixels and a smoothing correction is performed using a cubic equation. In this way, the root mean square height Rq of the outer surface of the hollow inorganic particle (B) can be calculated.

The average particle size of the hollow inorganic particles (B) is preferably 50 nm or more, more preferably 75 nm or more, and further preferably 100 nm or more, and preferably 10 μm or less, more preferably 5 μm or less, and further preferably 2 μm or less. If the average particle size is above the lower limit and below the upper limit, the surface roughness after etching can be reduced, the plating peeling strength can be improved, and the adhesion between the insulating layer and the metal layer can be further improved. In addition, short circuits between wirings can be further suppressed.

As the average particle size of the hollow inorganic particles (B), the value of the median diameter (d50) at 50% is adopted. The above average particle size can be measured using a particle size distribution measuring device using a laser diffraction scattering method. In addition, when the hollow inorganic particles (B) are agglomerated particles, the average particle size of the hollow inorganic particles (B) refers to the primary particle size.

The shape of the hollow inorganic particle (B) is not particularly limited, but is preferably spherical. In this case, the surface roughness of the surface of the hardened material is effectively reduced, and the bonding strength between the hardened material and the metal layer is effectively increased. When the hollow inorganic particle (B) is spherical, the aspect ratio of the hollow inorganic particle (B) is preferably greater than 1 and preferably less than 2, and more preferably less than 1.5.

The number of pores (number of hollow spaces) contained inside the hollow inorganic particles (B) is not particularly limited, but is preferably one.

The porosity of the hollow inorganic particles (B) is preferably 20 volume % or more, more preferably 30 volume % or more, further preferably 40 volume % or more, and preferably 90 volume % or less, more preferably 85 volume % or less, further preferably 80 volume % or less. If the porosity is above the lower limit and below the upper limit, the dielectric constant and dielectric dissipation factor of the cured resin material can be further reduced.

The porosity when the number of pores (the number of hollows) contained inside the hollow inorganic particle (B) is 1 can be calculated as follows. Use a transmission electron microscope (TEM) to photograph the hollow inorganic particle (B). Based on the obtained microscope photograph, the particle sizes of 50 arbitrary hollow inorganic particles (B) are measured respectively, and the average value is set as the average particle size (X). In addition, the hollow inorganic particle (B) is cut in half, and the cut hollow inorganic particle (B) is photographed using a transmission electron microscope (TEM). Based on the obtained microscope photograph, the diameter of the cavity portion of the cross-section of 50 arbitrary cut hollow inorganic particles (B) is measured, and the average value is set as the average diameter of the cavity portion (Y). The porosity was calculated by the following formula.

Porosity (volume %) = (Y ³ /X ³ ) × 100 X: average particle size (X) Y: average diameter of the cavity (Y)

The above porosity when the number of pores (number of hollows) contained inside the hollow inorganic particle (B) is 2 or more can also be determined using a transmission electron microscope (TEM) based on the volume of the hollow inorganic particle (B) obtained from the particle size of the hollow inorganic particle (B) and the volume of the cavity portion obtained from the diameter of the cavity portion.

The hollow inorganic particles (B) are preferably hollow inorganic particles that have been surface treated, and more preferably hollow inorganic particles that have been surface treated with a coupling agent. By surface treating the hollow inorganic particles (B), the surface roughness of the surface of the hardened material is further reduced, and the bonding strength between the hardened material and the metal layer is further increased. In addition, by surface treating the hollow inorganic particles (B), it is possible to form a finer wiring on the surface of the hardened material, and to give the hardened material a better insulation reliability between wiring and between layers.

Examples of the coupling agent include silane coupling agents, titanium coupling agents, and aluminum coupling agents. Examples of the silane coupling agent include methacryloylsilane, acrylsilane, phenylaminosilane, phenylsilane, imidazole silane, vinyl silane, alkylaminosilane, and epoxysilane.

The hollow inorganic particles (B) are preferably hollow inorganic particles surface-treated with a silane coupling agent, and more preferably hollow inorganic particles surface-treated with vinyl silane, phenylamino silane or phenyl silane. In this case, the lamination properties can be further improved. In addition, since the lamination properties can be improved, the plating peeling strength of the cured product can be further improved.

In the above resin material, the content of the hollow inorganic particles (B) is preferably 5% by weight or more, more preferably 10% by weight or more, and further preferably 15% by weight or more, and preferably 60% by weight or less, more preferably 55% by weight or less, and further preferably 50% by weight or less in 100% by weight of the components other than the solvent. If the content of the hollow inorganic particles (B) is above the above lower limit, the dielectric constant and dielectric dissipation factor of the cured product of the resin material can be further reduced. In addition, the thermal dimensional stability can be improved, and the warping of the cured product can be effectively suppressed. If the content of the hollow inorganic particles (B) is above the lower limit and below the upper limit, the surface roughness of the cured product can be further reduced, and short circuits between wirings can be further suppressed, so that finer wiring can be formed on the surface of the cured product. Furthermore, if the content of the hollow inorganic particles (B) is 100%, the thermal expansion rate of the cured product can be reduced, and the desmearing property can be improved.

In the resin material, the weight ratio of the content of the hollow inorganic particles (B) to the content of the thermosetting compound (A) (the content of the hollow inorganic particles (B)/the content of the thermosetting compound (A)) is preferably 0.1 or more, more preferably 0.2 or more, and preferably 3 or less, more preferably 2.5 or less. If the weight ratio (the content of the hollow inorganic particles (B)/the content of the thermosetting compound (A)) is above the lower limit and below the upper limit, the effect of the present invention can be further effectively exerted.

[Solid Inorganic Particles (C)] The resin material may contain solid inorganic particles (C). The solid inorganic particles (C) may be used alone or in combination of two or more.

Solid inorganic particles (C) are inorganic particles that are not hollow.

Examples of the solid inorganic particles (C) include solid silica particles, solid talc particles, solid clay particles, solid mica particles, solid magnesium aluminum carbonate particles, solid aluminum oxide particles, solid magnesium oxide particles, solid aluminum hydroxide particles, solid aluminum nitride particles, and solid boron nitride particles.

From the viewpoint of reducing the surface roughness of the hardened material, further improving the bonding strength between the hardened material and the metal layer, forming further fine wiring on the surface of the hardened material, and providing the hardened material with better insulation reliability, the solid inorganic particles (C) are preferably solid silicon dioxide particles or solid aluminum oxide particles, and more preferably solid silicon dioxide particles.

The average particle size of the solid inorganic particles (C) is preferably 50 nm or more, more preferably 100 nm or more, and further preferably 500 nm or more, and preferably 5 μm or less, more preferably 3 μm or less, and further preferably 1 μm or less. If the average particle size of the solid inorganic particles (C) is above the lower limit and below the upper limit, the surface roughness after etching can be reduced, the plating peeling strength can be increased, and the adhesion between the insulating layer and the metal layer can be further improved.

The average particle size of the solid inorganic particles (C) is a value that is a median diameter (d50) of 50%. The average particle size can be measured using a particle size distribution measuring device using a laser diffraction scattering method.

The shape of the solid inorganic particle (C) is not particularly limited, but is preferably spherical. In this case, the surface roughness of the surface of the hardened material is effectively reduced, and the bonding strength between the hardened material and the metal layer is effectively increased. When the solid inorganic particle (C) is spherical, the aspect ratio of the solid inorganic particle (C) is preferably greater than 1 and preferably less than 2, and more preferably less than 1.5.

The solid inorganic particles (C) are preferably surface treated, more preferably surface treated with a coupling agent, and more preferably surface treated with a silane coupling agent. By surface treating the solid inorganic particles (C), the surface roughness of the surface of the hardened material is further reduced, and the bonding strength between the hardened material and the metal layer is further increased. In addition, by surface treating the solid inorganic particles (C), it is possible to form a finer wiring on the surface of the hardened material, and the hardened material can be given better insulation reliability between wiring and insulation reliability between layers.

Examples of the coupling agent include silane coupling agents, titanium coupling agents, and aluminum coupling agents. Examples of the silane coupling agent include methacryloylsilane, acrylsilane, aminosilane, imidazolesilane, vinylsilane, and epoxysilane.

In the above-mentioned resin material, the content of the solid inorganic particles (C) is preferably 1% by weight or more, more preferably 5% by weight or more, and preferably 75% by weight or less, more preferably 70% by weight or less, and further preferably 65% by weight or less in 100% by weight of the components other than the solvent. If the content of the solid inorganic particles (C) is above the above lower limit, the dielectric constant and dielectric loss tangent of the cured product of the resin material can be further reduced. In addition, the thermal dimensional stability can be improved, and the warping of the cured product can be effectively suppressed. If the content of the solid inorganic particles (C) is above the above lower limit and below the above upper limit, the surface roughness of the surface of the cured product can be further reduced, and a further fine wiring can be formed on the surface of the cured product. Furthermore, if the content of the solid inorganic particles (C) is 0.0447 W, the thermal expansion coefficient of the cured product can be reduced and the desmearing property can be improved.

[Hardening accelerator (D)] The resin material preferably contains a hardening accelerator (D). By using a hardening accelerator (D), the hardening speed is further accelerated. By rapidly hardening the resin material, the cross-linking structure in the hardened material becomes uniform, and the number of unreacted functional groups decreases, resulting in a higher cross-linking density. In addition, by using a hardening accelerator (D), the resin material can be well hardened even at a relatively low temperature. Only one hardening accelerator (D) may be used, or two or more hardening accelerators may be used in combination.

Examples of the curing accelerator (D) include anionic curing accelerators such as imidazole compounds; cationic curing accelerators such as amine compounds; curing accelerators other than anionic and cationic curing accelerators such as organic phosphorus compounds and organic metal compounds; free radical curing accelerators such as peroxides and azo compounds, etc.

Examples of the imidazole compound include 2-undecyl imidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino- 6-[2'-methylimidazolyl-(1')]-ethyl-symmetric tris(imidazolyl), 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-symmetric tris(imidazolyl), 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-symmetric tris(imidazolyl), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-symmetric tris(imidazolyl) 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, etc.

Examples of the amine compound include diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, diethylenetriamine, ethylenediamine, tris(dimethylaminomethyl)phenol, benzyldimethylamine, meta-xylene di(dimethylamine), N,N'-dimethylpiperidinium, N-methylpyrrolidine, N-methylhydroxypiperidinium, meta-xylene diamine, isophorone diamine, N-aminoethylpiperidinium, polyoxypropylene polyamine, and 4,4-dimethylaminopyridine. The amine compound may be a modified product of the amine compound.

Examples of the organophosphorus compound include triphenylphosphine, tricyclohexylphosphine, tribenzylphosphine, diphenyl(alkylphenyl)phosphine, tri(alkylphenyl)phosphine, tri(alkoxyphenyl)phosphine, tri(alkylalkoxyphenyl)phosphine, tri(dialkylphenyl)phosphine, tri(trialkylphenyl)phosphine, tri(tetraalkylphenyl)phosphine, tri(dialkoxyphenyl)phosphine, tri(trialkoxyphenyl)phosphine, tri(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, and alkyldiarylphosphine; and phosphonium salt compounds such as tetraphenylphosphonium tetraphenylborate.

Examples of the organic metal compound include zinc cycloalkanoate, cobalt cycloalkanoate, tin octylate, cobalt octylate, cobalt(II) diacetylacetonate, and cobalt(III) triacetylacetonate.

Examples of the peroxide include diacyl peroxide, peroxyester, peroxydicarbonate, monoperoxycarbonate, peroxyketal, dialkyl peroxide, dibenzyl peroxide, diisopropyl peroxide, hydrogen peroxide, and ketone peroxide.

The hardening accelerator (D) preferably comprises an amine compound, an imidazole compound, a peroxide, an azo compound or an organophosphorus compound, and more preferably comprises an imidazole compound or a peroxide. In this case, the effect of the present invention can be further effectively exerted.

In the resin material, the content of the curing accelerator (D) is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, and preferably 10 parts by weight or less, more preferably 5 parts by weight or less, relative to 100 parts by weight of the thermosetting compound (A). If the content of the curing accelerator (D) is above the lower limit and below the upper limit, the effect of the present invention can be further effectively exerted.

[Hardener (E)] The resin material preferably contains a hardener (E). The hardener (E) is not particularly limited. As the hardener (E), a previously known hardener can be used. The hardener (E) may be used alone or in combination of two or more.

Examples of the hardener (E) include compounds having an active ester group (active ester compound), compounds having a hydroxyl group, compounds having a thiol group, and compounds having an amine group. The hardener (E) preferably contains an active ester compound.

The content of the hardener (E) in the resin material can be appropriately selected, for example, according to the content of the thermosetting compound (A) in the resin material.

[Solvent] The resin material may or may not contain a solvent. The resin material may or may not contain a solvent. By using the solvent, the viscosity of the resin material can be controlled within an appropriate range, and the coating property of the resin material can be improved. In addition, the solvent can also be used to obtain a slurry containing hollow inorganic particles (B). The solvent can be used alone or in combination of two or more.

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

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 below 200°C, more preferably below 180°C. The boiling point of the solvent may be above 30°C, above 50°C, or above 100°C. The content of the solvent in the resin composition is not particularly limited. The content of the solvent may be appropriately changed in consideration of the coating properties of the resin composition.

When the resin material is a B-stage film, the content of the solvent in 100 wt % of the B-stage film is preferably 1 wt % or more, more preferably 2 wt % or more, and preferably 15 wt % or less, more preferably 10 wt % or less.

[Other components] For the purpose of improving impact resistance, heat resistance, compatibility of resins and workability, the above-mentioned resin material may also contain other components other than the above-mentioned components (thermosetting compound (A), hollow inorganic particles (B), solid inorganic particles (C), curing accelerator (D), curing agent (E) and solvent). Examples of the above-mentioned other components include: thermoplastic resin; organic filler; leveling agent; flame retardant; coupling agent; coloring agent; antioxidant; anti-ultraviolet degradation agent; defoaming agent; thickening agent; thixotropic agent, etc. The above-mentioned other components may be used alone or in combination of two or more.

Examples of the thermoplastic resin include polyimide resin, phenoxy resin, and polyvinyl acetal resin.

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

The resin material may or may not contain glass cloth. Preferably, the resin material does not contain glass cloth. Preferably, the resin material is not a prepreg.

(Resin film) By forming the resin composition into a film, a resin film (B-stage compound/B-stage film) can be obtained. The resin material is preferably a resin film. The resin film is preferably a B-stage film.

As a method of forming a resin composition into a film to obtain a resin film, the following methods can be cited. Extrusion molding method: using an extruder, the resin composition is melt-kneaded and extruded, and then formed into a film by a T-die or a circular mold. Casting molding method: a resin composition containing a solvent is cast to form a film. Other previously known film forming methods. In terms of being able to cope with thinning, extrusion molding method or casting molding method is preferred. The film includes a sheet.

The resin composition is formed into a film shape and heat-dried at, for example, 50° C. to 150° C. for 1 minute to 10 minutes to a degree where thermal curing does not proceed excessively, thereby obtaining a resin film as a B-stage film.

The film-like resin composition obtained by the drying step as described above is called a B-stage film. The B-stage film is in a semi-cured state. The semi-cured material is not completely cured and can be further cured.

The resin film may not be a prepreg. In the case where the resin film is not a prepreg, it will not migrate along the glass cloth, etc. Also, when the resin film is laminated or pre-cured, the surface will not be uneven due to the glass cloth.

The resin film can be used in the form of a laminated film, which comprises: a metal foil or a substrate film; and a resin film laminated on the surface of the metal foil or the substrate film. The metal foil is preferably a copper foil.

Examples of the substrate film of the laminate 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 substrate film may be subjected to release treatment as needed.

From the viewpoint of further uniformly controlling the curing degree of the resin film, the thickness of the resin film is preferably 5 μm or more and preferably 200 μm or less. When the resin film is used as an insulating layer of a circuit, the thickness of the insulating layer formed by the resin film is preferably greater 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) When the resin material is heated at 180°C for 30 minutes and then at 200°C for 60 minutes to obtain a cured resin material, the dielectric constant (Dk) of the cured material at 10 GHz is preferably 2.5 or less, more preferably less than 2.5, further preferably less than 2.2, further preferably less than 2.0, and particularly preferably less than 2.0. The dielectric constant (Dk) of the cured material at 10 GHz may be greater than 0, or may exceed 0.

The dielectric constant (Dk) of the above-mentioned cured product at 10 GHz can be measured as follows. The resin material is heated at 180°C for 30 minutes and then heated at 200°C for 60 minutes to obtain a cured product of the resin material. The dielectric constant (Dk) of the cured product is measured by the resonant cavity method at room temperature (23°C) and a frequency of 10 GHz using a dielectric constant measuring device (e.g., "Resonant Cavity Perturbation Dielectric Constant Measuring Device CP521" manufactured by Kanto Electronics Application Development Co., Ltd.).

Furthermore, when the above-mentioned resin material is used to manufacture electronic parts such as multi-layer substrates, a hardened product can be obtained by heating at 180°C for 30 minutes and then at 200°C for 60 minutes. The resin material can also be heated under heating conditions other than the above heating conditions to obtain a hardened product.

The resin material can be used for various purposes. For example, the resin material can be suitably used as a mold resin for forming an embedded semiconductor chip in a semiconductor device. In addition, the resin material can be suitably used as a replacement for liquid crystal polymer (LCP), millimeter wave antenna, and redistribution layer. The resin material is not limited to the above-mentioned uses, and can be suitable for all wiring formation uses.

The resin material can be suitably used as a bonding material. For example, the resin material can be suitably used as a bonding material for power cover packaging, a bonding material for printed wiring substrates, a bonding material for cover layers of flexible printed circuit substrates, and a bonding material for semiconductor bonding. The resin material is preferably a bonding material.

The resin material can be suitably used as an insulating material. The resin material can be suitably used to form an insulating layer on a printed wiring board, and more suitably used to form an insulating layer on a multi-layer printed wiring board. The resin material is preferably an insulating material, and more preferably an interlayer insulating material. The insulating material can also function as a bonding material.

The hardened product of the present invention is a hardened product of a resin material obtained by hardening the above-mentioned resin material. The hardened product of the present invention is a hardened product of a resin material, and the resin material is the above-mentioned resin material. The hardened product of the present invention can be obtained by hardening the above-mentioned resin material. The heating conditions of the above-mentioned resin material when obtaining the hardened product of the present invention are not particularly limited, as long as the resin material is hardened.

(Laminated structure and copper foil laminate) A laminated structure can be obtained by laminating a laminated component having a metal layer on one or both surfaces of the resin film. The laminated structure comprises: a laminated component 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 resin material. There is no particular limitation on the method of laminating the resin film and the laminated component, and a known method can be used. For example, the resin film can be laminated on the member to be laminated using a parallel plate press or a roll laminator while applying heat or pressure without heating.

The material of the metal layer is preferably copper.

The laminated component having a metal layer on the surface may also be a metal foil such as copper foil.

The resin material can be suitably used to obtain a copper foil laminate. As an example of the copper foil laminate, there can be cited the following copper foil laminate, which has a copper foil and a resin film laminated on one surface of the copper foil, and the resin film is the resin material.

The thickness of the copper foil of the copper foil laminate is not particularly limited. The thickness of the copper foil is preferably greater than 1 μm and less than 100 μm. In order to improve the bonding strength between the cured resin material and the copper foil, the copper foil preferably has fine concavities and convexities on the surface. The method for forming the concavities and convexities is not particularly limited. Examples of the method for forming the concavities and convexities include: a method for forming using a known chemical solution, a method for forming using a known plasma treatment, and a method for forming using a known UV treatment.

(Circuit board with insulating layer) The above-mentioned resin material can be suitably used to obtain a circuit board with insulating layer. As an example of the above-mentioned circuit board with insulating layer, the following circuit board with insulating layer can be cited, which has a circuit board and an insulating layer arranged on the surface of the circuit board, and the above-mentioned insulating layer is a cured product of the above-mentioned resin material.

In the above-mentioned circuit substrate with insulating layer, the above-mentioned insulating layer is preferably laminated on the surface of the circuit substrate on which the circuit is provided. In the above-mentioned circuit substrate with insulating layer, a part of the above-mentioned insulating layer is preferably embedded between the above-mentioned circuits.

The above-mentioned circuit substrate with insulating layer can be obtained by a previously known method.

(Multilayer substrate and multilayer printed wiring board) The resin material can be suitably used to obtain a multilayer substrate. As an example of the multilayer substrate, there can be cited a multilayer substrate having a circuit substrate and an insulating layer laminated on the circuit substrate. The insulating layer of the multilayer substrate is a hardened product of the resin material. The insulating layer is preferably laminated on the surface of the circuit substrate on which the circuit (metal layer) is provided. A portion of the insulating layer is preferably embedded between the circuits.

In the multi-layer substrate, it is preferred that the surface of the insulating layer opposite to the surface on which the circuit substrate is laminated is roughened.

The roughening treatment method may be any known roughening treatment method, and is not particularly limited. The surface of the insulating layer may also be subjected to swelling treatment before the roughening treatment. After the roughening treatment, the hollow inorganic particles (B) (and solid inorganic particles (C)) on the surface of the insulating layer are preferably subjected to ultrasonic treatment in order to remove the hollow inorganic particles (B) (and solid inorganic particles (C)).

Furthermore, the multi-layer substrate preferably further comprises: a copper-plated layer laminated on the roughened surface of the insulating layer.

As another example of the multilayer substrate, there can be cited a multilayer substrate comprising: a circuit substrate, an insulating layer laminated on the surface of the circuit substrate, and a copper foil laminated on the surface of the insulating layer opposite to the surface on which the circuit substrate is laminated. The insulating layer is preferably formed by using a copper foil laminate having a copper foil and a resin film laminated on one surface of the copper foil, and curing the resin film. Furthermore, the copper foil is preferably etched and is a copper circuit.

As another example of the multilayer substrate, there can be cited: a multilayer substrate having a circuit substrate and a plurality of insulating layers laminated on the surface of the circuit substrate. At least one of the plurality of insulating layers disposed on the circuit substrate is formed using the resin material. The multilayer substrate preferably further has a circuit laminated on at least one surface of the insulating layer formed using the resin film.

The above resin material can be suitably used to form an insulating layer on a multi-layer printed wiring board.

The multi-layer printed wiring board includes, for example, a circuit substrate, a plurality of insulating layers disposed on the surface of the circuit substrate, and a metal layer disposed between the plurality of insulating layers. In the multi-layer printed wiring board, 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 multi-layer printed wiring board using a resin material according to an embodiment of the present invention.

In the multi-layer printed wiring board 11 shown in FIG. 1, a plurality of insulating layers 13 to 16 are stacked on the upper surface 12a of the circuit substrate 12. The insulating layers 13 to 16 are hardened layers. A metal layer 17 is formed on a portion of the upper surface 12a of the circuit substrate 12. Among the plurality of insulating layers 13 to 16, a metal layer 17 is formed on a portion 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 side of the circuit substrate 12. The metal layer 17 is a circuit. Metal layers 17 are disposed between the circuit substrate 12 and the insulating layer 13 and between the stacked insulating layers 13 to 16. The lower metal layer 17 and the upper metal layer 17 are connected to each other by at least one of via connection and through-hole connection (not shown).

In the multi-layer printed wiring board 11, the insulating layers 13 to 16 are formed by the hardened material of the above-mentioned resin material. In the present embodiment, since the surfaces of the insulating layers 13 to 16 are roughened, fine holes not shown are formed on the surfaces of the insulating layers 13 to 16. In addition, the metal layer 17 reaches the inside of the fine holes. In addition, in the multi-layer 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. Furthermore, in the multi-layer 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 connection and through-hole connection (not shown).

The present invention is specifically described below by giving examples and comparative examples. The present invention is not limited to the following examples.

Prepare the following materials.

(Thermosetting compound (A)) Cis-butylene diimide compound ("BMI3000J" manufactured by Designer Molecules Inc., a cis-butylene diimide compound having an aliphatic skeleton, the number of cis-butylene diimide groups: 2, weight average molecular weight: 3000) Polyphenylene ether-methacrylic acid compound ("SA9000-111" manufactured by SABIC, solid at 25°C) Divinylbenzene (viscosity at 25°C: 1 mPa・s) Oligophenylene ether-styrene compound ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd.) P-d type benzophenone ("P-d" manufactured by Shikoku Chemical Industries, Ltd., solid at 25°C) Biphenyl type epoxy compound ("NC-3000" manufactured by Nippon Kayaku Co., Ltd., solid at 25°C) Bisphenol A cyanate resin ("P-201" manufactured by Mitsubishi Gas Chemical Co., Ltd., viscosity at 25°C: 100 mPa・s)

(Hollow Inorganic Particles (B)) Hollow silica particles B1 ("HS-070" manufactured by AGC, RMS height Rq of the outer surface: 3 nm, average particle size: 0.6 μm, porosity: 70% by volume) Hollow silica particles B2 ("HS-200" manufactured by AGC, RMS height Rq of the outer surface: 15 nm, average particle size: 2.0 μm, porosity: 75% by volume)

(Hollow inorganic particles not equivalent to hollow inorganic particles (B)) Hollow silica particles X ("L6SZ-AC1" manufactured by Admatechs, RMS height Rq of the outer surface: 1 nm, average particle size: 0.6 μm, porosity: 40% by volume) Hollow aluminosilicate particles ("Cell spheres-NF (small particle size)" manufactured by Pacific Cement), RMS height Rq of the outer surface: 1 nm, average particle size: 1 μm, porosity: 75% by volume

The root mean square height Rq, average particle size, and porosity of the outer surface of the hollow inorganic particles are measured according to the above method. In addition, as an atomic force microscope (AFM) for obtaining the root mean square height Rq, "Cypher ES" manufactured by Oxford Instruments was used.

FIG2 shows an atomic force microscope photograph of the hollow silica particle B1.

(Solid inorganic particles (C)) Solid silica particles (“SC2050-HNG” manufactured by Admatechs, average particle size: 0.5 μm)

(Hardening accelerator (D)) Peroxide ("PERBUTYL P" manufactured by NOF Corporation) Imidazole compound (2-phenyl-4-methylimidazole, "2P4MZ" manufactured by Shikoku Chemical Industries, Ltd., anionic hardening accelerator)

(Hardening agent (E)) Liquid containing an active ester compound ("HPC-8000L-65T" manufactured by DIC Corporation, solid content 65% by weight)

(Examples 1 to 20 and Comparative Examples 1 to 5) The components shown in Tables 1 to 5 below were mixed in the amounts shown in Tables 1 to 5 below (in parts by weight of solid components), and stirred at room temperature until a uniform solution was obtained to obtain a resin material.

Preparation of resin film: The obtained resin material was applied on the release-treated surface of a release-treated polyethylene terephthalate film (PET film, "XG284" manufactured by Toray, 25 μm thick) using an applicator, and then dried in a heat aging oven at 100°C for 2 minutes and 30 seconds to evaporate the solvent. In this way, a laminated film (laminated film of PET film and resin film) was obtained in which a resin film (B-stage film) with a thickness of 40 μm was laminated on the PET film.

(Evaluation) (1) Dielectric constant (Dk) of cured product The obtained resin film (B-stage film) with a thickness of 40 μm was heated at 180°C for 30 minutes and then at 200°C for 60 minutes to obtain a cured product. The obtained cured product was cut into pieces with a width of 2 mm and a length of 80 mm and 10 pieces were stacked to prepare a measurement sample. The dielectric constant (Dk) of the cured product was measured at room temperature (23°C) and a frequency of 10 GHz using the "Resonant Cavity Perturbation Dielectric Constant Measurement Device CP521" manufactured by Kanto Electronics Application Development Co., Ltd. and the "Network Analyzer N5224A PNA" manufactured by Keysight Technologies, using the resonant cavity method.

[Criteria for determination of dielectric constant (Dk) of cured product] ○: Dielectric constant less than 2.0 Δ: Dielectric constant greater than 2.0 and less than 2.5 ×: Dielectric constant greater than 2.5

(2) Lamination A mask was attached to a copper layer with a thickness of 18 μm to etch a rectangular area of 1 mm in length and 2 mm in width. A 100 mm square substrate with a 1 mm × 2 mm rectangular depression was produced by etching the copper. Both sides of the copper foil surface of the substrate were immersed in "Cz8101" manufactured by MEC to roughen the surface of the copper foil. Using the "Batch Vacuum Laminating Machine MVLP-500-IIA" manufactured by Meiki Manufacturing Co., Ltd., the resin film (B-stage film) side of the laminated film was superimposed on the substrate on both sides of the roughened substrate and laminated to obtain a laminated structure. The lamination conditions were as follows: decompression for 30 seconds to reduce the pressure to 13 hPa or less, followed by lamination at 100°C and 0.7 MPa for 30 seconds, and then lamination at 0.8 MPa and 100°C for 60 seconds. The PET film was peeled off, heated at 100°C for 30 minutes, and then further heated at 180°C for 30 minutes to semi-harden the resin film. The surface of the semi-cured resin film where the copper pattern existed (the surface on the opposite side to the substrate) and the surface of the semi-cured resin film where the copper pattern did not exist (the surface on the opposite side to the substrate) were observed, and the maximum value of the height difference between the adjacent concave and convex parts was obtained using an optical profiler.

[Laminar compressive strength criteria] ○○: Maximum height difference is less than 1.3 μm ○: Maximum height difference is 1.3 μm or more and less than 1.5 μm Δ: Maximum height difference is 1.5 μm or more and less than 2 μm ×: Maximum height difference is 2 μm or more

(3) Fracture of particles (hollow inorganic particles or solid inorganic particles) after lamination After the evaluation of "(2) Lamination properties" above, the semi-cured resin film was cut into a size of 2 cm × 1 cm. After the obtained cut material was embedded in the resin, the resin and the cut material were polished to expose the cross section of the cut material (the cross section along the thickness direction of the semi-cured resin film). The exposed cross section was observed at a magnification of 5000 times using a scanning electron microscope (SEM, "JSM-561 0LV" manufactured by JEOL Datum). Confirm whether 30 randomly selected particles were cracked.

[Criteria for determining cracks in particles after lamination] ○: The number of cracked particles is less than 3 out of 30 particles ×: The number of cracked particles is more than 4 out of 30 particles

(4) Fracture of particles (hollow inorganic particles or solid inorganic particles) after ultrasonic treatment After the evaluation of "(2) Lamination compressibility" described above, the following "(4-1) Roughening treatment" and the following "(4-2) Observation using a scanning electron microscope" were performed.

(4-1) Roughening treatment: (a) Swelling treatment: The laminate of the semi-cured substrate and resin film obtained in "(2) Lamination" was placed in a 60°C swelling liquid ("Swelling Dip Securiganth P" manufactured by Atotech Japan) and shaken for 10 minutes. Thereafter, it was washed with pure water.

(b) Permanganate treatment (roughening and degumming): The stratified body after swelling treatment was placed in a roughening aqueous solution of potassium permanganate ("Concentrate Compact CP" manufactured by Atotech Japan) at 80°C and shaken for 30 minutes. Then, it was treated with a cleaning solution ("Reduction Securigant P" manufactured by Atotech Japan) at 25°C for 2 minutes, and then ultrasonically vibrated at a frequency of 40 kHz for 200 seconds in pure water for cleaning.

(4-2) Observation using a scanning electron microscope: The ultrasonically treated hardened material (hardened material after roughening treatment) was cut into a size of 2 cm × 1 cm. After the obtained cut material was embedded in resin, the resin and the cut material were ground to expose the cross section of the cut material (the cross section along the thickness direction of the hardened material). The exposed cross section was observed using a scanning electron microscope (SEM, "JSM-561 0LV" manufactured by JEOL Datum) at a magnification of 5000 times. Confirm whether 30 randomly selected particles were cracked.

[Criteria for judging the fracture of particles after ultrasonic treatment] ○: The number of fractured particles is less than 3 out of 30 particles ×: The number of fractured particles is more than 4 out of 30 particles

(5) Plating penetration After the above-mentioned "(4-1) Roughening treatment", the following "(5-1) Electroless plating treatment" is performed to obtain a hardened product with a copper-plated layer deposited on the upper surface. The following "(5-2) Measurement of plating penetration" is performed using the hardened product with the copper-plated layer deposited on the upper surface.

(5-1) Electroless plating treatment: The surface of the roughened hardened product was treated with an alkaline cleaning solution at 60°C ("Cleaner Securigant 902" manufactured by Atotech Japan) for 5 minutes to degrease and clean. After cleaning, the hardened product was treated with a pre-dip solution at 25°C ("Pre-dip Neogant B" manufactured by Atotech Japan) for 2 minutes. Thereafter, the hardened product was treated with an activator solution at 40°C ("Activator Neogant 834" manufactured by Atotech Japan) for 5 minutes and a palladium catalyst was attached. Subsequently, the hardened product was treated with a reducing solution at 30°C ("Reducer Neogant WA" manufactured by Atotech Japan) for 5 minutes. Next, the hardened product was placed in a chemical copper solution ("Basic Printganth MSK-DK", "Copper Printganth MSK", "Stabilizer Printganth MSK", and "Reducer Cu" manufactured by Atotech Japan) and electroless plating was performed until the coating thickness reached about 0.5 μm. After electroless plating, annealing was performed at 120°C for 30 minutes to remove the residual hydrogen. In addition, all steps before the electroless plating step were performed while shaking the hardened product while the treatment solution was adjusted to 2 L using a beaker scale. In this way, a hardened product with a copper-plated layer on the upper surface was obtained.

(5-2) Determination of coating penetration: The interface between the copper-plated layer and the hardened material in the hardened material with the copper-plated layer on the upper surface was observed using FE-SEM at a magnification of 5000 times. Furthermore, during the observation, the hardened material with the copper-plated layer on the upper surface was arranged in such a way that the copper-plated layer was the upper side, the hardened material side was the lower side, and the interface between the copper-plated layer and the hardened material was horizontal. As shown in FIG3, in the area with a width of 20 μm in the obtained microscope image, a line that was in contact with the hardened material existing at the uppermost part of the microscope image and was parallel to the interface between the copper-plated layer and the hardened material was set as line L1. As shown in FIG3, in the area of the microscope image with a width of 20 μm, a line that is in contact with the copper plating existing at the bottom of the microscope image and parallel to the interface between the copper plating layer and the hardened material is set as line L2. As shown in FIG3, the distance between line L1 and line L2 is set as plating penetration D. The smaller the plating penetration D, the more short circuits between wirings can be suppressed.

[Criteria for judging the coating penetration] ○: The coating penetration D is less than 3 μm ×: The coating penetration D is more than 3 μm

The compositions and results are shown in Tables 1 to 5 below.

[Table 1] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Thermosetting compound (A) Cis-butylene diimide compounds BM13000J Weight 50 Polyphenylene ether-methacrylic acid compound SA9000-111 Weight 50 Divinylbenzene Weight 50 Oligophenylene ether-styrene compounds OPE-2St Weight 50 Pd-type benzophenone Pd Weight 50 Biphenyl type epoxy compounds NC-3000 Weight Bisphenol A cyanate resin P-201 Weight Hollow Inorganic Particles (B) Hollow silica particles B1 (Rq = 3 nm) HS-070 Weight 50 50 50 50 50 Hollow silica particles B2 (Rq = 15 nm) HS-200 Weight Hollow Inorganic Particles Not Equivalent to Hollow Inorganic Particles (B) Hollow silica particles X (Rq = 1 nm) L6SZ-AC1 Weight Hollow aluminum silicate particles (Rq＝1 nm) Cell spheres-NF(small particle size) Weight Solid Inorganic Particles (C) Solid silica particles SC2050-HNG Weight Hardening accelerator (D) Peroxide PERBUTYL P Weight 1 1 1 1 Imidazole compounds 2P4MZ Weight 1 Hardener (E) Active ester compounds HPC-8000L-65T Weight Reviews Dielectric constant of hardened material (Dk) ○ Δ ○ Δ Δ Compressive strength ○ ○ ○ ○ ○ Cracking of particles (hollow inorganic particles or solid inorganic particles) after lamination ○ ○ ○ ○ ○ Rupture of particles (hollow inorganic particles or solid inorganic particles) after ultrasonic treatment ○ ○ ○ ○ ○ Coating penetration ○ ○ ○ ○ ○

[Table 2] Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Thermosetting compound (A) Cis-butylene diimide compounds BMI3000J Weight 25 25 25 Polyphenylene ether-methacrylic acid compound SA9000-111 Weight 25 Divinylbenzene Weight 25 Oligophenylene ether-styrene compounds OPE-2St Weight 25 Pd-type benzophenone Pd Weight Biphenyl type epoxy compounds NC-3000 Weight 25 25 Bisphenol A cyanate resin P-201 Weight 25 Hollow Inorganic Particles (B) Hollow silica particles B1 (Rq = 3 nm) HS-070 Weight 50 50 50 50 50 Hollow silica particles B2 (Rq = 15 nm) HS-200 Weight Hollow Inorganic Particles Not Equivalent to Hollow Inorganic Particles (B) Hollow silica particles X (Rq = 1 nm) L6SZ-AC1 Weight Hollow aluminum silicate particles (Rq＝1 nm) Cell spheres-NF(small particle size) Weight Solid Inorganic Particles (C) Solid silica particles SC2050-HNG Weight Hardening accelerator (D) Peroxide PERBUTYL P Weight 1 1 1 Imidazole compounds 2P4MZ Weight 1 1 Hardener (E) Active ester compounds HPC-8000L-65T Weight 25 Reviews Dielectric constant of hardened material (Dk) Δ Δ ○ ○ ○ Compressive strength ○○ ○○ ○ ○○ ○○ Cracking of particles (hollow inorganic particles or solid inorganic particles) after lamination ○ ○ ○ ○ ○ Rupture of particles (hollow inorganic particles or solid inorganic particles) after ultrasonic treatment ○ ○ ○ ○ ○ Coating penetration ○ ○ ○ ○ ○

[Table 3] Embodiment 11 Embodiment 12 Embodiment 13 Embodiment 14 Embodiment 15 Thermosetting compound (A) Cis-butylene diimide compounds BMI3000J Weight 25 25 25 25 25 Polyphenylene ether-methacrylic acid compound SA9000-111 Weight Divinylbenzene Weight Oligophenylene ether-styrene compounds OPE-2St Weight Pd-type benzophenone Pd Weight 25 Biphenyl type epoxy compounds NC-3000 Weight 25 12.5 12.5 Bisphenol A cyanate resin P-201 Weight 25 12.5 Hollow Inorganic Particles (B) Hollow silica particles B1 (Rq = 3 nm) HS-070 Weight 50 50 50 50 50 Hollow silica particles B2 (Rq = 15 nm) HS-200 Weight Hollow Inorganic Particles Not Equivalent to Hollow Inorganic Particles (B) Hollow silica particles X (Rq = 1 nm) L6SZ-AC1 Weight Hollow aluminum silicate particles (Rq＝1 nm) Cell spheres-NF(small particle size) Weight Solid Inorganic Particles (C) Solid silica particles SC2050-HNG Weight Hardening accelerator (D) Peroxide PERBUTYL p Weight Imidazole compounds 2P4MZ Weight 1 1 1 1 1 Hardener (E) Active ester compounds HPC-8000L-65T Weight 12.5 Reviews Dielectric constant of hardened material (Dk) Δ Δ Δ Δ Δ Compressive strength ○ ○ ○ ○○ ○○ Cracking of particles (hollow inorganic particles or solid inorganic particles) after lamination ○ ○ ○ ○ ○ Rupture of particles (hollow inorganic particles or solid inorganic particles) after ultrasonic treatment ○ ○ ○ ○ ○ Coating penetration ○ ○ ○ ○ ○

[Table 4] Embodiment 16 Embodiment 17 Embodiment 18 Embodiment 19 Embodiment 20 Thermosetting compound (A) Cis-butylene diimide compounds BMI3000J Weight 50 50 80 40 Polyphenylene ether-methacrylic acid compound SA9000-111 Weight Divinylbenzene Weight Oligophenylene ether-styrene compounds OPE-2St Weight Pd-type benzophenone Pd Weight Biphenyl type epoxy compounds NC-3000 Weight 25 Bisphenol A cyanate resin P-201 Weight Hollow Inorganic Particles (B) Hollow silica particles B1 (Rq = 3 nm) HS-070 Weight 25 20 60 Hollow silica particles B2 (Rq = 15 nm) HS-200 Weight 50 50 Hollow Inorganic Particles Not Equivalent to Hollow Inorganic Particles (B) Hollow silica particles X (Rq = 1 nm) L6SZ-AC1 Weight Hollow aluminum silicate particles (Rq＝1 nm) Cell spheres-NF(small particle size) Weight Solid Inorganic Particles (C) Solid silica particles SC2050-HNG Weight 25 Hardening accelerator (D) Peroxide PERBUTYL P Weight 1 1 1 1 Imidazole compounds 2P4MZ Weight 1 Hardener (E) Active ester compounds HPC-8000L-65T Weight 25 Reviews Dielectric constant of hardened material (Dk) Δ ○ Δ Δ ○ Compressive strength ○○ ○ ○ ○○ Δ Cracking of particles (hollow inorganic particles or solid inorganic particles) after lamination ○ ○ ○ ○ ○ Rupture of particles (hollow inorganic particles or solid inorganic particles) after ultrasonic treatment ○ ○ ○ ○ ○ Coating penetration ○ ○ ○ ○ ○

[Table 5] Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 Comparison Example 5 Thermosetting compound (A) Cis-butylene diimide compounds BMI3000J Weight 50 50 50 Polyphenylene ether-methacrylic acid compound SA9000-111 Weight 50 Divinylbenzene Weight Oligophenylene ether-styrene compounds OPE-2St Weight Pd-type benzophenone Pd Weight Biphenyl type epoxy compounds NC-3000 Weight 25 Bisphenol A cyanate resin P-201 Weight Hollow Inorganic Particles (B) Hollow silica particles B1 (Rq = 3 nm) HS-070 Weight Hollow silica particles B2 (Rq = 15 nm) HS-200 Weight Hollow Inorganic Particles Not Equivalent to Hollow Inorganic Particles (B) Hollow silica particles X (Rq = 1 nm) L6SZ-AC1 Weight 50 50 50 Hollow aluminum silicate particles (Rq＝1 nm) Cell spheres-NF(small particle size) Weight 50 Solid Inorganic Particles (C) Solid silica particles SC2050-HNG Weight 50 Hardening accelerator (D) Peroxide PERBUTYL P Weight 1 1 1 1 Imidazole compounds 2P4MZ Weight 1 Hardener (E) Active ester compounds HPC-8000L-65T Weight 25 Reviews Dielectric constant of hardened material (Dk) ○ ○ × Δ Δ Compressive strength ○ Δ ○ ○ ○ Cracking of particles (hollow inorganic particles or solid inorganic particles) after lamination × × ○ × × Rupture of particles (hollow inorganic particles or solid inorganic particles) after ultrasonic treatment × × ○ × × Coating penetration × × ○ × ×

11: Multilayer printed wiring board 12: Circuit board 12a: Top surface 13: Insulation layer 14: Insulation layer 15: Insulation layer 16: Insulation layer 17: Metal layer D: Plating penetration L1: Line L2: Line

Fig. 1 is a schematic cross-sectional view of a multi-layer printed wiring board using a resin material according to an embodiment of the present invention. Fig. 2 is an atomic force microscope photograph of a hollow silica particle B1 used in the embodiment. Fig. 3 is a diagram for explaining a method for calculating the coating penetration amount evaluated in the embodiment.

Claims (11)

A resin material comprises a thermosetting compound (A) and hollow inorganic particles (B), wherein the root mean square height Rq of the outer surface of the hollow inorganic particles (B) is greater than 2 nm. The resin material of claim 1, wherein the hollow inorganic particles (B) are hollow silica particles. The resin material of claim 1 or 2, wherein the thermosetting compound (A) comprises a thermosetting compound having an epoxy group, a vinyl group, a styrene group, a benzophenone group, a cyanate group, an allyl group, a methacryl group, an acryl group or a succinimidyl group. The resin material of claim 1 or 2, wherein the thermosetting compound (A) comprises a succinimidyl compound. The resin material of claim 1 or 2, further comprising solid inorganic particles (C). The resin material of claim 1 or 2, wherein the content of the hollow inorganic particles (B) is 60% by weight or less in 100% by weight of the components other than the solvent in the resin material. In the resin material of claim 1 or 2, when the resin material is heated at 180°C for 30 minutes and then heated at 200°C for 60 minutes to obtain a cured resin material, the dielectric constant of the cured resin material obtained at 10 GHz is less than 2.5. The resin material of claim 1 or 2, which is a resin film. A resin material as claimed in claim 1 or 2, which is used to form an insulating layer in a multi-layer printed wiring board. A hardened product, which is a hardened product of a resin material, wherein the resin material is the resin material as claimed in any one of claims 1 to 9. A multi-layer printed wiring board comprises: a circuit substrate, a plurality of insulating layers arranged on the surface of the circuit substrate, and a metal layer arranged between the plurality of insulating layers, wherein at least one of the plurality of insulating layers is a cured product of the resin material as described in any one of claims 1 to 9.