JP2024092800A - Resin material, cured article, and multilayer printed wiring board - Google Patents

Abstract

To provide a resin material capable of lowering the dielectric constant and dielectric loss tangent of a cured article and improving the insulation reliability after the HAST test.SOLUTION: There is provided a resin material which comprises a radical polymerizable compound (A), hollow aluminosilicate particles (B) and a curing accelerator (C) and has the following first configuration or the following second configuration. The first configuration: the content of the radical polymerizable compound (A) in 100 wt.% of components excluding the solvent in the resin material is 20 wt.% or more. The second configuration: after the resin material is heated at 180°C for 30 minutes, and then when the dielectric loss tangent of a cured article (1) of the resin material obtained by heating at 200°C for 60 minutes and the dielectric loss tangent of a cured article (2) of the resin material after the cured article (1) is left to stand at 130°C and 85%RH for 100 hours are measured, respectively, the rate of change in the dielectric loss tangent calculated by the specific expression (Df) is 225% or less.SELECTED DRAWING: Figure 1

Description

The present invention relates to a resin material containing a radically polymerizable compound. The present invention also relates to a cured product of the resin material. Furthermore, the present invention also relates to a multilayer printed wiring board using the resin material.

Conventionally, various resin materials have been used to obtain electronic components such as semiconductor devices, laminates, and printed wiring boards. For example, in multilayer printed wiring boards, resin materials are used to form insulating layers for insulating between internal layers and to form insulating layers located on the surface. Wiring, which is generally metal, is laminated on the surface of the insulating layer. Also, film-like resin materials (resin films) may be used to form the insulating layers. The resin materials are used as insulating materials for multilayer printed wiring boards, including build-up films.

The following Patent Document 1 discloses a resin composition that contains (A) an epoxy resin, (B) a curing agent, and (C) hollow inorganic particles, in which the (C) hollow inorganic particles satisfy a specific configuration.

JP 2020-083966 A

As described in Patent Document 1, a resin material containing an epoxy compound and hollow inorganic particles is known. By using hollow inorganic particles, the dielectric constant and dielectric tangent of the cured resin material can be lowered to a certain degree.

In addition, electronic components such as printed wiring boards may undergo a High Accelerated Stress Test (HAST test). However, with conventional resin materials containing hollow inorganic particles as described in Patent Document 1, the insulation reliability may decrease after the HAST test.

The object of the present invention is to provide a resin material that can reduce the dielectric constant and dielectric tangent of the cured product and can increase the insulation reliability after HAST testing. Another object of the present invention is to provide a cured product of the above resin material. Furthermore, the present invention is also to provide a multilayer printed wiring board using the above resin material.

This specification discloses the following resin material, cured product, and multilayer printed wiring board.

Item 1. A resin material containing a radically polymerizable compound (A), hollow aluminosilicate particles (B), and a curing accelerator (C), and having the following first configuration or the following second configuration.

First configuration: The content of the radical polymerizable compound (A) is 20% by weight or more out of 100% by weight of the components excluding the solvent in the resin material.

Second configuration: When the dielectric tangent of a cured product (1) of the resin material obtained by heating a resin material at 180° C. for 30 minutes and then at 200° C. for 60 minutes and the dielectric tangent of a cured product (2) of the resin material obtained by leaving the cured product (1) of the resin material at rest for 100 hours at 130° C. and 85% RH are measured, the rate of change in the dielectric tangent calculated by the following formula (Df) is 225% or less.

Change in dielectric tangent (%) = (|Df1-Df2|/Df1) x 100 ... (Df)

Df1: Dielectric tangent of the cured resin material (1) Df2: Dielectric tangent of the cured resin material (2)

Item 2. The resin material according to item 1, which has the first configuration.

Item 3. The resin material according to item 1, which has the second configuration.

Item 4. The resin material according to item 1, comprising the first configuration and the second configuration.

Item 5. The resin material according to any one of items 1 to 4, in which the content of the hollow aluminosilicate particles (B) is 55% by weight or less in 100% by weight of the components excluding the solvent in the resin material.

Item 6. The resin material according to any one of items 1 to 5, wherein the hollow aluminosilicate particles (B) are surface-treated hollow aluminosilicate particles.

Item 7. The resin material according to any one of items 1 to 6, which is a resin film.

Item 8. The resin material according to any one of items 1 to 7, which is used to form an insulating layer in a multilayer printed wiring board.

Item 9. A cured product of a resin material, the resin material being the resin material described in any one of items 1 to 8.

Item 10. A multilayer printed wiring board comprising a circuit board, a plurality of insulating layers arranged on a surface of the circuit board, and a metal layer arranged between the plurality of insulating layers, at least one of the plurality of insulating layers being a cured product of the resin material described in any one of items 1 to 8.

The resin material according to the present invention contains a radically polymerizable compound (A), hollow aluminosilicate particles (B), and a curing accelerator (C), and has a specific first configuration or a specific second configuration. Since the resin material according to the present invention has the above configuration, it is possible to reduce the dielectric constant and dielectric tangent of the cured product, and to increase the insulation reliability after the HAST test.

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

The details of the present invention are explained below.

(Resin material)
The resin material according to the present invention contains a radically polymerizable compound (A), hollow aluminosilicate particles (B), and a curing accelerator (C), and has the following first configuration or the following second configuration.

First configuration: The content of the radical polymerizable compound (A) is 20% by weight or more out of 100% by weight of the components excluding the solvent in the resin material.

Second configuration: When the dielectric tangent of the cured resin material (1) obtained by heating the resin material at 180°C for 30 minutes and then at 200°C for 60 minutes and the dielectric tangent of the cured resin material (2) obtained after leaving the cured resin material (1) at 130°C and 85% RH for 100 hours are measured, the rate of change in the dielectric tangent calculated by the following formula (Df) is 225% or less.

Change in dielectric tangent (%) = (|Df1-Df2|/Df1) x 100 ... (Df)

Df1: Dielectric tangent of the cured resin material (1) Df2: Dielectric tangent of the cured resin material (2)

The resin material according to the present invention has the above-mentioned configuration, and therefore the dielectric constant and dielectric tangent of the cured product can be reduced, and the insulation reliability after the HAST test can be improved. The resin material according to the present invention uses a combination of a radical polymerizable compound (A), hollow aluminosilicate particles (B), which are hollow inorganic particles, and a curing accelerator (C), and has a specific first configuration or a specific second configuration, and therefore can exert the above-mentioned effects.

In addition, the resin material according to the present invention can suppress the decrease in plating peel strength after moisture absorption. Furthermore, the resin material according to the present invention can suppress the decrease in dielectric tangent after moisture absorption.

Therefore, the resin material according to the present invention can be suitably used in applications where these properties are required (e.g., printed wiring board applications, etc.).

The resin material according to the present invention may have the first configuration, the second configuration, or both the first and second configurations. From the viewpoint of more effectively exerting the effects of the present invention and more effectively suppressing the decrease in plating peel strength and dielectric tangent after moisture absorption, it is preferable that the resin material according to the present invention has both the first and second configurations.

The second configuration is described in more detail below.

The resin material is heated at 180°C for 30 minutes, then heated at 200°C for 60 minutes to obtain a cured resin material (1). More specifically, a 40 μm thick resin material (resin film) is heated at 180°C for 30 minutes, then heated at 200°C for 60 minutes to obtain a cured resin material (1). The obtained cured resin material (1) is left to stand at 130°C and 85% RH for 100 hours to obtain a cured resin material (2). The dielectric tangent of the cured resin material (1) and the dielectric tangent of the cured resin material (2) are measured.

The dielectric tangent of the cured resin material (1) and the dielectric tangent of the cured resin material (2) are measured by the cavity resonance method at room temperature (23°C) and a frequency of 10 GHz using, for example, a "Cavity Resonance Perturbation Method Dielectric Constant Measuring Device CP521" manufactured by Kanto Electronics Application Development Co., Ltd. and a "Network Analyzer N5224A PNA" manufactured by Keysight Technologies, Inc.

In the resin material having the second configuration, the rate of change of the dielectric tangent calculated by the formula (Df) is 225% or less. The rate of change of the dielectric tangent calculated by the formula (Df) is preferably 225% or less, more preferably 200% or less, even more preferably 180% or less, and particularly preferably 150% or less. When the rate of change of the dielectric tangent is equal to or less than the upper limit, the effect of the present invention can be exhibited even more effectively.

Methods for effectively reducing the rate of change in the dielectric tangent include a method using surface-treated hollow aluminosilicate particles (B) and a method using a radically polymerizable compound.

The dielectric loss tangent (Df1) of the cured resin material (1) is preferably 0.007 or less, more preferably 0.005 or less, and even more preferably 0.003 or less.

The dielectric tangent (Df1) of the cured resin material (1) may be greater or smaller than the dielectric tangent (Df2) of the cured resin material (2). The dielectric tangent (Df1) of the cured resin material (1) may be the same as the dielectric tangent (Df2) of the cured resin material (2). However, the dielectric tangent (Df1) of the cured resin material (1) is usually smaller than the dielectric tangent (Df2) of the cured resin material (2).

The resin material according to the present invention may be a resin composition or a resin film. The resin composition has fluidity. The resin composition may be in a paste form. The paste form includes a liquid form. Since the resin material according to the present invention has excellent handleability, it is preferable that the resin material is a resin film.

The resin material according to 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.

In the following description, "100% by weight of the components in the resin material excluding the solvent" means 100% by weight of the components in the resin material excluding the solvent 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 in the resin material excluding the hollow aluminosilicate particles (B) and the solvent" means 100% by weight of the components in the resin material excluding the hollow aluminosilicate particles (B) and the solvent when the resin material contains hollow aluminosilicate particles (B) and a solvent. "100% by weight of the components in the resin material excluding the hollow aluminosilicate particles (B) and the solvent" means 100% by weight of the components in the resin material excluding the hollow aluminosilicate particles (B) and the solvent when the resin material contains hollow aluminosilicate particles (B) and does not contain a solvent.

Below, we will explain the details of each component used in the resin material of the present invention, as well as the uses of the resin material of the present invention.

[Radically polymerizable compound (A)]
The resin material contains a radical polymerizable compound (radical polymerizable compound (A)). The radical polymerizable compound is preferably a thermosetting compound. The radical polymerizable compound (A) may be used alone or in combination of two or more kinds.

The radically polymerizable compound (A) preferably has a radically polymerizable unsaturated group. Examples of the radically polymerizable unsaturated group include a maleimide group, a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, and a styryl group. The radically polymerizable compound (A) may have only one type of radically polymerizable unsaturated group, or may have two or more types.

The radical polymerizable compound (A) preferably has a maleimide group, a vinyl group, a styryl group, or an allyl group, and more preferably has a maleimide group, a vinyl group, or a styryl group. The radical polymerizable compound (A) is preferably a maleimide compound, a vinyl compound, a styryl compound, or an allyl compound, and more preferably a maleimide compound, a vinyl compound, or a styryl compound. In this case, the effects of the present invention can be exerted even more effectively.

The molecular weight of the radically polymerizable compound (A) is preferably 100 or more, more preferably 200 or more, even more preferably 300 or more, and preferably 200,000 or less, more preferably 100,000 or less, even more preferably 50,000 or less. When the molecular weight is equal to or greater than the lower limit and equal to or less than the upper limit, a resin material with high fluidity is easily obtained when forming an insulating layer, and good lamination properties can be obtained. In addition, good lamination properties can be obtained, so that the plating peel strength of the cured product can be further increased.

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

In the resin material having the first configuration, the content of the radical polymerizable compound (A) is 20% by weight or more in 100% by weight of the components excluding the solvent in the resin material. The content of the radical polymerizable compound (A) is preferably 20% by weight or more, more preferably 30% by weight or more, even more preferably 40% by weight or more, preferably 70% by weight or less, and more preferably 65% by weight or less in 100% by weight of the components excluding the solvent in the resin material. When the content of the radical polymerizable compound (A) is equal to or more than the lower limit and equal to or less than the upper limit, the effects of the present invention can be more effectively exhibited. In addition, the lamination property can be further improved. Furthermore, the surface roughness after the roughening treatment can be further reduced, and the plating peel strength of the cured product can be further increased.

The content of the radical polymerizable compound (A) in 100% by weight of the components excluding the hollow aluminosilicate particles (B) and the solvent in the resin material is preferably 20% by weight or more, more preferably 30% by weight or more, preferably less than 100% by weight, more preferably 98% by weight or less. When the content of the radical polymerizable compound (A) is equal to or more than the above lower limit and less than the above upper limit (or equal to or less than the above upper limit), the effects of the present invention can be more effectively exhibited. In addition, the lamination properties can be further improved. Furthermore, the surface roughness after the roughening treatment can be further reduced, and the plating peel strength of the cured product can be further increased.

The radical polymerizable compound (A) is further described below.

<Maleimide Compound>
The radical polymerizable compound (A) preferably contains a maleimide compound. The maleimide compound that is the radical polymerizable compound (A) may have one maleimide group, two maleimide groups, two or more maleimide groups, three or more maleimide groups, four or more maleimide groups, 800 or less maleimide groups, 500 or less maleimide groups, or 300 or less maleimide groups. The maleimide compound may be used alone or in combination of two or more maleimide compounds.

From the viewpoint of further increasing the curability of the resin material, it is preferable that the radically polymerizable compound (A) contains a maleimide compound having two or more maleimide groups.

The maleimide 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 effects of the present invention can be more effectively exhibited. In addition, the desmear property and plating peel strength can be improved.

The aliphatic skeleton may be a chain aliphatic skeleton, for example, a saturated hydrocarbon group and an unsaturated hydrocarbon group. The aliphatic skeleton is preferably an aliphatic skeleton having 4 or more carbon atoms. The number of carbon atoms in the aliphatic skeleton having 4 or more carbon atoms is preferably 5 or more, more preferably 6 or more, even more preferably 7 or more, preferably 60 or less, more preferably 50 or less, and even more preferably 40 or less. More specifically, the aliphatic skeleton may be an alkyl group having 4 to 60 carbon atoms (preferably an alkyl group having 6 to 40 carbon atoms). The maleimide compound may have only one type of the aliphatic skeleton, or may have two or more types.

The alicyclic skeleton may include a monocycloalkane ring, a bicycloalkane ring, a tricycloalkane ring, a tetracycloalkane ring, and a dicyclopentadiene ring. The maleimide compound may have only one type of alicyclic skeleton, or two or more types.

From the viewpoint of further increasing the glass transition temperature of the cured product, it is preferable that the maleimide compound has an aromatic skeleton.

The aromatic skeleton includes a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, a chrysene ring, a triphenylene ring, a tetraphene ring, a pyrene ring, a pentacene ring, a picene ring, and a perylene ring. The maleimide compound may have only one type of aromatic skeleton, or two or more types.

The maleimide compound preferably has a skeleton derived from dimer diamine. Since the maleimide compound (A) having a skeleton derived from dimer diamine has an aliphatic skeleton and an alicyclic skeleton, the use of the maleimide compound (A) can further reduce the dielectric constant and dielectric tangent of the cured product.

Examples of the above dimer diamines (commercially available dimer diamines) 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. Only one type of the above dimer diamines may be used, or two or more types may be used in combination.

It is preferable that the maleimide compound has a skeleton derived from a dimer diamine and a skeleton derived from a second diamine compound other than the dimer diamine. In this case, the effect of the present invention can be more effectively exerted.

Examples of the second diamine compound include tricyclodecane diamine, norbornane diamine, isophorone diamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(aminomethyl)norbornane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.02,6]decane, 1,3-cyclohexane diamine, 1,4-cyclohexane diamine, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), 1,4-diaminobutane diamine, Examples of the second diamine compound include benzene, 1,10-diaminodecane, 1,12-diaminododecane, 1,7-diaminoheptane, 1,6-diaminohexane, 1,5-diaminopentane, 1,8-diaminooctane, 1,3-diaminopropane, 1,11-diaminoundecane, 2-methyl-1,5-diaminopentane, 1,1-bis(4-aminophenyl)cyclohexane, 2,7-diaminofluorene, 4,4'-ethylenedianiline, 4,4'-methylenebis(2,6-diethylaniline), and 4,4'-methylenebis(2-ethyl-6-methylaniline). Only one type of the second diamine compound may be used, or two or more types may be used in combination.

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 preferably contains a diamine compound having an alicyclic skeleton other than dimer diamine. The maleimide compound preferably has a skeleton derived from dimer diamine and a skeleton derived from a diamine compound having an alicyclic skeleton other than dimer diamine. In this case, the effect of the present invention can be more effectively achieved.

The diamine compound having an alicyclic skeleton other than the dimer diamine is preferably tricyclodecane diamine, norbornane diamine, or isophorone diamine. In this case, the effects of the present invention can be more effectively achieved.

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 even more preferably has a skeleton derived from a reaction product of a dimer diamine and an acid dianhydride.

Examples of the acid dianhydride include tetracarboxylic dianhydrides. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone 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)diphenylsulfonate, and 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfonate. Examples of the dianhydride include 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylether dianhydride, and bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride. The above dianhydrides may be used alone or in combination of two or more.

The molecular weight of the maleimide compound is preferably 200 or more, more preferably 500 or more, even more preferably 1,000 or more, and preferably 200,000 or less, more preferably 100,000 or less, even more preferably 50,000 or less. When the molecular weight is equal to or greater than the lower limit and equal to or less than the upper limit, a resin material with high fluidity is easily obtained when forming an insulating layer, and good lamination properties can be obtained. In addition, since good lamination properties can be obtained, the plating peel strength of the cured product can be further increased.

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

Commercially available maleimide compounds include "MIR-5000-60T" and "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., "NE-X-9470S" manufactured by DIC Corporation, "BMI-3000J", "BMI-2500", "BMI-1500" and "BMI-689" manufactured by Designer Molecules Inc., and "BMI", "BMI-70" and "BMI-80" manufactured by Kei-I Chemicals Co., Ltd.

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

The content of the maleimide compound in the resin material (100% by weight, excluding the solvent) is preferably 5% by weight or more, more preferably 10% by weight or more, even more preferably 15% by weight or more, preferably 90% by weight or less, more preferably 80% by weight or less, and even more preferably 70% by weight or less. When the content of the maleimide compound is equal to or more than the lower limit and equal to or less than the upper limit, the effects of the present invention can be more effectively exhibited. In addition, the lamination properties can be further improved. Furthermore, the surface roughness after the roughening treatment can be further reduced, and the plating peel strength of the cured product can be further increased.

The content of the maleimide compound in 100% by weight of the components in the resin material excluding the hollow aluminosilicate particles (B) and the solvent is preferably 10% by weight or more, more preferably 20% by weight or more, preferably less than 100% by weight, more preferably 90% by weight or less. When the content of the maleimide compound is equal to or more than the lower limit and less than the upper limit (or equal to or less than the upper limit), the effects of the present invention can be more effectively exhibited. In addition, the lamination properties can be further improved. Furthermore, the surface roughness after the roughening treatment can be further reduced, and the plating peel strength of the cured product can be further increased.

<Vinyl Compounds>
The radical polymerizable compound (A) preferably contains a vinyl compound.The vinyl compound, which is the radical polymerizable compound (A), may have one vinyl group, may have two, may have two or more, may have three or more, may have five or more, may have 800 or less, may have 500 or less, or may have 300 or less.The vinyl compound may be used alone or in combination of two or more.

The vinyl compound may be a divinylbenzyl ether compound.

The content of the vinyl compound is preferably 5% by weight or more, more preferably 10% by weight or more, and preferably 90% by weight or less, more preferably 80% by weight or less, based on 100% by weight of the components excluding the solvent in the resin material. When the content of the vinyl compound is equal to or more than the lower limit and equal to or less than the upper limit, the dielectric constant and dielectric tangent of the cured product can be further reduced, and the thermal dimensional stability of the cured product can be further improved.

<Styryl compounds>
The radical polymerizable compound (A) preferably contains a styryl compound.The styryl compound, which is the radical polymerizable compound (A), may have one styryl group, may have two, may have two or more, may have three or more, may have five or more, may have 800 or less, may have 500 or less, or may have 300 or less.The styryl compound may be used alone or in combination of two or more.

Commercially available products of the above styryl compounds include "OPE-2St" and "OPE-1200" manufactured by Mitsubishi Gas Chemical Co., Ltd.

The content of the styryl compound is preferably 5% by weight or more, more preferably 10% by weight or more, and preferably 90% by weight or less, more preferably 80% by weight or less, based on 100% by weight of the components excluding the solvent in the resin material. When the content of the styryl compound is equal to or more than the lower limit and equal to or less than the upper limit, the dielectric constant and dielectric tangent of the cured product can be further reduced, and the thermal dimensional stability of the cured product can be further improved.

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

The hollow aluminosilicate particles (B) are aluminosilicate particles having a hollow space. The hollow aluminosilicate particles (B) have a hollow space and an outer shell surrounding the hollow space. The number of the hollow spaces surrounded by the outer shell is preferably one, but may be two or more.

The hollow aluminosilicate particles (B) are formed from an aluminosilicate. More specifically, the outer shell of the hollow aluminosilicate particles (B) is formed from an aluminosilicate.

In 100% by weight of hollow aluminosilicate particles (B), the content of aluminosilicate is preferably 90% by weight or more, more preferably 95% by weight or more, even more preferably 98% by weight or more, and particularly preferably 99% by weight or more. In 100% by weight of hollow aluminosilicate particles (B), the content of aluminosilicate may be 100% by weight or less, may be less than 100% by weight, or may be 99% by weight or less.

The average particle size of the hollow aluminosilicate particles (B) is preferably 50 nm or more, more preferably 75 nm or more, even more preferably 100 nm or more, and preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 2 μm or less. When the average particle size is equal to or greater than the lower limit and equal to or less than the upper limit, the surface roughness after etching can be reduced and the plating peel strength can be increased, and the adhesion between the insulating layer and the metal layer can be further improved.

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

The shape of the hollow aluminosilicate particles (B) is not particularly limited, but it is preferable that the hollow aluminosilicate particles (B) are spherical. In this case, the surface roughness of the cured product is effectively reduced, and the adhesive strength between the cured product and the metal layer is effectively increased. When the hollow aluminosilicate particles (B) are spherical, the aspect ratio of the hollow aluminosilicate particles (B) is preferably 2 or less, more preferably 1.5 or less.

The porosity of the hollow aluminosilicate particles (B) is preferably 20% by volume or more, more preferably 30% by volume or more, even more preferably 50% by volume or more, and preferably 90% by volume or less, more preferably 85% by volume or less, and even more preferably 80% by volume or less. When the porosity is equal to or more than the lower limit and equal to or less than the upper limit, the dielectric constant and dielectric tangent of the cured product of the resin material can be further reduced.

The porosity when the number of holes (number of hollows) contained inside the hollow aluminosilicate particles (B) is one can be calculated as follows. The hollow aluminosilicate particles (B) are photographed using a transmission electron microscope (TEM). From the obtained micrograph, the particle diameters of 50 arbitrary hollow aluminosilicate particles (B) are measured, and the average value is taken as the average particle diameter (X). In addition, the hollow aluminosilicate particles (B) are cut in half, and the cut hollow aluminosilicate particles (B) are photographed using a transmission electron microscope (TEM). From the obtained micrograph, the diameters of the cavities of the cut surfaces of 50 arbitrary cut hollow aluminosilicate particles (B) are measured, and the average value is taken as the average diameter of the cavities (Y). The porosity is calculated using the following formula.

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

When the number of holes (number of hollows) contained inside the hollow aluminosilicate particles (B) is 2 or more, the above porosity can also be determined using a transmission electron microscope (TEM) from the volume of the hollow aluminosilicate particles (B) calculated from the particle diameter of the hollow aluminosilicate particles (B) and the volume of the hollow portion calculated from the diameter of the hollow portion.

The hollow aluminosilicate particles (B) are preferably surface-treated hollow aluminosilicate particles, and more preferably surface-treated with a coupling agent. By surface-treating the hollow aluminosilicate particles (B), the rate of change in the dielectric tangent can be further reduced, and the insulation reliability after the HAST test can be further improved. In addition, by surface-treating the hollow aluminosilicate particles (B), the surface roughness of the roughened cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased. In addition, by surface-treating the hollow aluminosilicate particles (B), finer wiring can be formed on the surface of the cured product, and better inter-wiring insulation reliability and inter-layer insulation reliability can be imparted to the cured product.

Examples of the coupling agent include silane coupling agents, titanium coupling agents, and aluminum coupling agents. Examples of the silane coupling agent include methacrylsilane, acrylic silane, phenylaminosilane, phenylsilane, imidazole silane, vinyl silane, and epoxy silane.

The hollow aluminosilicate particles (B) are preferably hollow aluminosilicate particles surface-treated with a silane coupling agent, and more preferably hollow aluminosilicate particles surface-treated with vinylsilane, phenylaminosilane, or phenylsilane. In this case, the rate of change of the dielectric tangent can be further reduced, and the insulation reliability after the HAST test can be further improved. In addition, the lamination property can be further improved. In addition, since the lamination property can be improved, the plating peel strength of the cured product can be further improved.

Commercially available hollow aluminosilicate particles (B) include "CellSpheres" and "CellSpheres NF" manufactured by Taiheiyo Cement Corporation.

The content of hollow aluminosilicate particles (B) in 100% by weight of the components excluding the solvent in the resin material is preferably 10% by weight or more, more preferably 15% by weight or more, preferably 60% by weight or less, more preferably 55% by weight or less. When the content of hollow aluminosilicate particles (B) is equal to or more than the lower limit, the dielectric constant and dielectric tangent of the cured product of the resin material can be further reduced. When the content of hollow aluminosilicate particles (B) is equal to or more than the lower limit, the thermal dimensional stability can be improved and the warping of the cured product can be effectively suppressed. When the content of hollow aluminosilicate particles (B) is equal to or more than the lower limit and equal to or less than the upper limit, the surface roughness of the cured product can be further reduced and finer wiring can be formed on the surface of the cured product. Furthermore, with this content of hollow aluminosilicate particles (B), it is possible to lower the thermal expansion coefficient of the cured product and at the same time improve the smear removal properties.

In the above resin material, the weight ratio of the content of hollow aluminosilicate particles (B) to the content of radically polymerizable compound (A) (content of hollow aluminosilicate particles (B)/content of radically polymerizable 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. When the weight ratio (content of hollow aluminosilicate particles (B)/content of radically polymerizable compound (A)) is equal to or more than the above lower limit and equal to or less than the above upper limit, the effects of the present invention can be more effectively exhibited.

[Curing Accelerator (C)]
The resin material contains a curing accelerator (curing accelerator (C)). The use of the curing accelerator (C) further accelerates the curing speed. By quickly curing the resin material, the crosslinked structure in the cured product becomes uniform, and the number of unreacted functional groups is reduced, resulting in a high crosslink density. In addition, the use of the curing accelerator (C) allows the resin material to be cured well even at a relatively low temperature. Only one type of curing accelerator (C) may be used, or two or more types may be used in combination.

Examples of the curing accelerator (C) 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 organophosphorus compounds and organometallic compounds; and radical curing accelerators such as peroxides.

Examples of the imidazole compound include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, and 1-cyanoethyl-2-phenylimidazolium trimethylolate. Limellitate, 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.

Examples of the amine compounds include diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, diethylenetriamine, ethylenediamine, tris(dimethylaminomethyl)phenol, benzyldimethylamine, m-xylylenedi(dimethylamine), N,N'-dimethylpiperazine, N-methylpyrrolidine, N-methylhydroxypiperidine, m-xylylenediamine, isophoronediamine, N-aminoethylpiperazine, polyoxypropylenepolyamine, and 4,4-dimethylaminopyridine. The amine compounds may also be modified versions of these amine compounds.

The above-mentioned organic phosphorus compounds include organic phosphine compounds such as triphenylphosphine, tricyclohexylphosphine, tribenzylphosphine, diphenyl(alkylphenyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkylalkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, and alkyldiarylphosphine, as well as phosphonium salt compounds such as tetraphenylphosphonium and tetraphenylborate.

The organometallic compounds include zinc naphthenate, cobalt naphthenate, tin octoate, cobalt octoate, cobalt bisacetylacetonate (II), and cobalt trisacetylacetonate (III).

Examples of the peroxides include diacyl peroxides, peroxy esters, peroxy dicarbonates, monoperoxy carbonates, peroxy ketals, dialkyl peroxides, dibenzyl peroxide, dicumyl peroxide, hydroperoxides, and ketone peroxides.

The curing accelerator (C) preferably contains an amine compound, an imidazole compound, a peroxide, or an organic phosphorus compound, and more preferably contains an imidazole compound or a peroxide. In this case, the effect of the present invention can be exerted even more effectively.

In the above resin material, the content of the curing accelerator (C) relative to 100 parts by weight of the radical polymerizable compound (A) is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less. When the content of the curing accelerator (C) is equal to or more than the above lower limit and equal to or less than the above upper limit, the effects of the present invention can be more effectively exhibited.

[solvent]
The resin material does not contain or contains 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 a suitable range, and the coatability of the resin material can be improved. The solvent may be used to obtain a slurry containing hollow aluminosilicate particles (B). Only one type of the solvent may be used, or two or more types may be used in combination.

Note that 100% by weight of the components in the resin material excluding the solvent means 100% by weight of the components in the resin material excluding the solvent if the resin material contains a solvent, and means 100% by weight of the resin material if the resin material does not contain a solvent.

The above-mentioned solvents include acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane, toluene, xylene, methyl ethyl ketone, N,N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidone, n-hexane, cyclohexane, cyclohexanone, and naphtha, which is a mixture.

It is preferable that most of the solvent is removed when the resin composition is molded into a film. Therefore, the boiling point of the solvent is preferably 200°C or less, more preferably 180°C or less. The content of the solvent in the resin composition is not particularly limited. The content of the solvent can be changed as appropriate, taking into account the coatability of the resin composition, etc.

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

[Other ingredients]
For the purpose of improving impact resistance, heat resistance, resin compatibility, workability, etc., the resin material may contain other components other than the above-mentioned components (radical polymerizable compound (A), hollow aluminosilicate particles (B), curing accelerator (C) and solvent). The other components include anionically polymerizable compounds; curing agents for anionically polymerizable compounds; thermoplastic resins; fillers such as organic fillers and inorganic fillers; leveling agents; flame retardants; coupling agents; colorants; antioxidants; ultraviolet degradation inhibitors; defoamers; thickeners; thixotropy-imparting agents, etc. The other components may be used alone or in combination of two or more.

The anionically polymerizable compound may include an epoxy compound, a lactone compound, a carbonate ester compound, etc. The curing agent for the anionically polymerizable compound may include an active ester curing agent, a cyanate curing agent, a carbodiimide curing agent, a phenol curing agent, a thiol curing agent, an amine curing agent, etc.

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 above-mentioned fillers include solid silica, hollow silica, solid organic particles, and hollow organic particles.

The resin material may or may not contain glass cloth. The resin material preferably does not contain glass cloth. The resin material is preferably not a prepreg.

(Resin film)
The above-mentioned resin composition is molded into a film to obtain a resin film (B-stage product/B-stage film). The above-mentioned resin material is preferably a resin film. The resin film is preferably a B-stage film.

Methods for forming a resin composition into a film to obtain a resin film include the following: Extrusion molding, in which the resin composition is melt-kneaded and extruded using an extruder, and then molded into a film using a T-die or circular die. Casting molding, in which a resin composition containing a solvent is cast into a film. Other conventionally known film molding methods. Extrusion molding and casting molding are preferred because they can be made thinner. Films include sheets.

The resin composition is molded into a film and dried by heating at, for example, 50°C to 150°C for 1 to 10 minutes to a degree that does not cause excessive curing due to heat, to obtain a resin film that is a B-stage film.

The film-like resin composition that can be obtained by the drying process described above is called a B-stage film. The B-stage film is in a semi-cured state. A semi-cured product is not completely cured, and curing can continue.

The resin film does not have to be a prepreg. If the resin film is not a prepreg, migration will not occur along the glass cloth or the like. In addition, when the resin film is laminated or precured, irregularities caused by the glass cloth will not occur on the surface.

The resin film can be used in the form of a laminated film comprising a metal foil or a base film and a resin film laminated on the surface of the metal foil or 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 subjected to a release treatment, if necessary.

From the viewpoint of controlling the degree of cure of the resin film more uniformly, the thickness of the resin film is preferably 5 μm or more and preferably 200 μm or less. When the resin film is used as an insulating layer of a circuit, the thickness of the insulating layer formed by the resin film is preferably equal to or greater than the thickness of the conductor layer (metal layer) that forms 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)
In 100% by weight of the components excluding the solvent in the resin material, the total content of the radical polymerizable compound (A) and the hollow aluminosilicate particles (B) is preferably 60% by weight or more, more preferably 70% by weight or more, even more preferably 80% by weight or more, particularly preferably 90% by weight or more, preferably less than 100% by weight, more preferably 99% by weight or less. When the total content is equal to or more than the lower limit and less than the upper limit (or equal to or less than the upper limit), the effects of the present invention can be more effectively exhibited.

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 (1). The dielectric constant (Dk) at 10 GHz of the cured resin material (1) is preferably 2.8 or less, more preferably 2.5 or less, and even more preferably 2.2 or less.

The dielectric constant (Dk) of the cured resin material (1) 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 the cured resin material (1). The dielectric constant (Dk) of the obtained cured resin material (1) is measured by the cavity resonance method using a dielectric constant measuring device (for example, the "Cavity Resonance Perturbation Method Dielectric Constant Measuring Device CP521" manufactured by Kanto Electronics Application Development Co., Ltd.) at room temperature (23°C) and a frequency of 10 GHz.

When using the above resin material to manufacture components such as multilayer boards, the resin material may be heated at 180°C for 30 minutes and then at 200°C for 60 minutes to obtain a cured product, or the resin material may be heated under other heating conditions to obtain a cured product.

The resin material can be used for various purposes. For example, the resin material is suitable for use in forming a mold resin for embedding a semiconductor chip in a semiconductor device. The resin material is also suitable for use as an alternative to liquid crystal polymer (LCP), for use as a millimeter wave antenna, and for use as a rewiring layer. The resin material is not limited to the above uses, and is suitable for use in wiring formation in general.

The resin material is preferably used as an adhesive material. The resin material is preferably used as, for example, an adhesive material for power overlay packages, an adhesive material for printed wiring boards, an adhesive material for coverlays of flexible printed circuit boards, and an adhesive material for semiconductor bonding. The resin material is preferably an adhesive material.

The resin material is preferably used as an insulating material. The resin material is preferably used to form an insulating layer in a printed wiring board, and more preferably used to form an insulating layer in a multilayer printed wiring board. The resin material is preferably an insulating material, and more preferably an interlayer insulating material. The insulating material may also function as an adhesive material.

The cured product according to the present invention is a cured product of a resin material obtained by curing the resin material described above. The cured product according to the present invention is a cured product of a resin material, and the resin material is the resin material described above. The cured product according to the present invention can be obtained by curing the resin material described above. The heating conditions of the resin material when obtaining the cured product according to the present invention are not particularly limited, as long as the resin material is cured.

(Laminated structure and copper-clad laminate)
A laminated structure can be obtained by laminating a laminated target member having a metal layer on one or both sides of the resin film. The laminated structure includes a laminated target member having a metal layer on its surface and a resin film laminated on the surface of the metal layer, and the resin film is the above-mentioned resin material. The method of laminating the resin film and the laminated target member is not particularly limited, and a known method can be used. For example, the resin film can be laminated on the laminated target member while applying pressure with or without heating using a device such as a parallel plate press or a roll laminator.

The material of the metal layer is preferably copper.

The lamination target component having the above-mentioned metal layer on its surface may be a metal foil such as copper foil.

The above resin material is preferably used to obtain a copper-clad laminate. One example of the above copper-clad laminate is a copper-clad laminate that includes a copper foil and a resin film laminated on one surface of the copper foil, the resin film being the above-mentioned resin material.

The thickness of the copper foil of the copper-clad laminate is not particularly limited. The thickness of the copper foil is preferably 1 μm or more and 100 μm or less. In addition, in order to increase the adhesive strength between the cured resin material and the copper foil, the copper foil preferably has fine irregularities on its surface. The method of forming the irregularities is not particularly limited. Examples of the method of forming the irregularities include a method of forming the irregularities by treatment using a known chemical solution, a method of forming the irregularities by known plasma treatment, and a method of forming the irregularities by known UV treatment.

(Circuit board with insulating layer)
The resin material is preferably used to obtain a circuit board with an insulating layer. One example of the circuit board with an insulating layer is a circuit board with an insulating layer that includes a circuit board and an insulating layer disposed on a surface of the circuit board, the insulating layer being a cured product of the resin material described above.

In the circuit board with an insulating layer, the insulating layer is preferably laminated on the surface of the circuit board on which the circuits are provided. In the circuit board with an insulating layer, a portion of the insulating layer is preferably embedded between the circuits.

The above-mentioned circuit board with insulating layer can be obtained by a conventional method.

(Multilayer boards and multilayer printed wiring boards)
The resin material is preferably used to obtain a multilayer board. An example of the multilayer board is a multilayer board including a circuit board and an insulating layer laminated on the circuit board. The insulating layer of the multilayer board is a cured product of the resin material. The insulating layer is preferably laminated on the surface of the circuit board on which the circuit (metal layer) is provided. A part of the insulating layer is preferably embedded between the circuits.

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

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

It is also preferable that the multilayer substrate further comprises a copper plating layer laminated on the roughened surface of the insulating layer.

Another example of the multilayer board is a multilayer board comprising a circuit board, an insulating layer laminated on a surface of the circuit board, and copper foil laminated on the surface of the insulating layer opposite to the surface on which the circuit board is laminated. It is preferable that the insulating layer is formed by using a copper-clad laminate comprising copper foil and a resin film laminated on one surface of the copper foil, and curing the resin film. Furthermore, it is preferable that the copper foil is etched and is a copper circuit.

Another example of the multilayer board is a multilayer board including a circuit board and a plurality of insulating layers laminated on a surface of the circuit board. At least one of the insulating layers arranged on the circuit board is formed using the resin material. The multilayer board preferably further includes a circuit laminated on at least one surface of the insulating layer formed using the resin film.

The above resin materials are suitable for use in forming insulating layers in multilayer printed wiring boards.

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 insulating layers. In the multilayer printed wiring board, at least one of the insulating layers is a cured product of the resin material described above.

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

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

In the multilayer printed wiring board 11, the insulating layers 13 to 16 are formed from the cured product of the resin material. In this embodiment, the surfaces of the insulating layers 13 to 16 are roughened, so that fine holes (not shown) are formed in the surfaces of the insulating layers 13 to 16. The metal layer 17 extends into the fine holes. In the multilayer printed wiring board 11, the width dimension (L) of the metal layer 17 and the width dimension (S) of the portion where the metal layer 17 is not formed can be reduced. In the multilayer printed wiring board 11, good insulation reliability is provided between the upper metal layer and the lower metal layer that are not connected by via hole connections and through hole connections (not shown).

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

The following materials were prepared:

(Radically Polymerizable Compound (A))
Maleimide compound (A1) ("BMI3000J" manufactured by Designer Molecules Inc., weight average molecular weight: 3000)
Maleimide compound (A2) (DIC Corporation "NE-X-9470S")
Maleimide compound (A3) ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.)
Oligophenylene ether-styrene compound (styryl compound, "OPE-2St" manufactured by Mitsubishi Gas Chemical Company, Inc.)

(Anionically polymerizable compound)
Epoxy compound (DIC Corporation "830")

(Hollow Aluminosilicate Particles (B))
Hollow aluminosilicate particles 1 (commercially available product ("CellSpheres NF" particles manufactured by Pacific Cement Corporation) surface-treated according to the following surface treatment method B, surface-treated with vinylsilane, average particle size: 1 μm, porosity: 75% by volume)
Hollow aluminosilicate particles 2 ("CellSpheres NF" manufactured by Taiheiyo Cement Corporation, no surface treatment, average particle size: 1 μm, porosity: 75% by volume)

(Inorganic particles not corresponding to hollow aluminosilicate particles)
Hollow silica particles (particles prepared according to the preparation method B described below and surface-treated according to the surface treatment method B described below, surface-treated with vinylsilane, average particle size: 1 μm, porosity: 50% by volume)
Solid silica particles ("SC2050-HNF" manufactured by Admatechs Co., Ltd., surface treated with vinylsilane, average particle size: 0.5 μm)

<Production Method B>
4.5 g of EO-PO-EO type block copolymer (EO80-PO30-EO80, ADEKA "Pluronic F68") was added to 965.5 g of pure water and stirred until dissolved. 30 g of n-dodecane was added to the obtained aqueous solution, and then preliminary emulsification was performed using a shaft generator (IKA "T50 digital ULTRA TURRAX"). Next, emulsification was performed three times at a pressure of 40 MPa using a high-pressure emulsifier (SMT "LAB2000") to obtain a fine emulsion. 30 g of diluted sodium silicate aqueous solution ( _SiO2 concentration 10 mass%, _Na2O concentration 3.6 mass%) was slowly added to the obtained fine emulsion together with 2M hydrochloric acid so that the pH was 2, and the mixture was thoroughly stirred while maintaining the temperature at 25°C. Next, a 1M aqueous solution of sodium hydroxide was slowly added dropwise so that the pH became 6, to obtain an oil core-silica shell particle dispersion liquid.

The resulting oil core-silica shell particle dispersion was heated to 70°C, and 1M aqueous sodium hydroxide solution was slowly added with stirring to adjust the pH to 9. Next, a diluted aqueous sodium silicate solution was gradually added together with 0.5M hydrochloric acid so that the pH was maintained at around 9. The mixture was then kept at 70°C for 2 days and then slowly cooled to room temperature to obtain a hollow silica precursor dispersion.

The obtained hollow silica precursor dispersion was filtered under pressure (pressure 0.28 MPa) using a hydrophilic polytetrafluoroethylene (PTFE) membrane filter with a pore size of 0.45 μm. The hollow silica cake after filtration was calcined in a nitrogen atmosphere at 60°C for 1 hour and at 400°C for 4 hours (heating rate 5°C/min) to remove organic components and obtain hollow silica precursor. The obtained hollow silica precursor was fired at 800°C for 4 hours (heating rate 5°C/min) to obtain hollow silica particles.

<Surface treatment method B>
100 parts by weight of the hollow inorganic particles obtained by Preparation Method B or 100 parts by weight of a commercially available product ("CellSpheres NF" manufactured by Pacific Cement Corporation) hollow inorganic particles were charged into a Henschel type mixer and heated to 100° C. while stirring. 1 part by weight of vinyltrimethoxysilane ("KBM-1003" manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed onto the hollow inorganic particles while stirring. 10 minutes after the completion of spraying, the surface-treated hollow inorganic particles were collected.

(Curing Accelerator (C))
Peroxide (NOF Corp. "Perbutyl P")
Imidazole compound (2-phenyl-4-methylimidazole, "2P4MZ" manufactured by Shikoku Chemical Industry Co., Ltd., anionic curing accelerator)

(Examples 1 to 9 and Comparative Examples 1 to 4)
The components shown in Tables 1 to 3 below were mixed in the amounts (unit: parts by weight of solid content) shown in Tables 1 to 3 below, and stirred at room temperature until a homogeneous solution was obtained, to obtain a resin material.

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

(evaluation)
(1) Dielectric loss tangent (Df) and rate of change of dielectric loss tangent of the cured resin material (1) The obtained 40 μm thick resin film was heated at 180 ° C for 30 minutes to be temporarily cured, and then heated at 200 ° C for 60 minutes to obtain a cured resin material (1). The obtained cured resin material (1) was left to stand at 130 ° C and 85% RH for 100 hours to obtain a cured resin material (2). The cured resin material (1) was cut into a size of 2 mm wide and 80 mm long, and 10 sheets were stacked together to obtain a measurement sample. Similarly, the cured resin material (2) was cut into a size of 2 mm wide and 80 mm long, and 10 sheets were stacked together to obtain a measurement sample. The dielectric loss tangent of the cured resin material (1) and the dielectric loss tangent of the cured resin material (2) were measured by the cavity resonance method at room temperature (23° C.) and a frequency of 10 GHz using a cavity resonance perturbation dielectric constant measuring device CP521 manufactured by Kanto Electronics Application Development Co., Ltd. and a network analyzer N5224A PNA manufactured by Keysight Technologies, Inc.

The rate of change in the dielectric tangent was calculated from the dielectric tangent of the cured resin material (1) and the dielectric tangent of the cured resin material (2) using the following formula (Df).

Change in dielectric tangent (%) = (|Df1-Df2|/Df1) x 100 ... (Df)

Df1: Dielectric tangent of the cured resin material (1) Df2: Dielectric tangent of the cured resin material (2)

[Criteria for determining dielectric tangent (Df) of cured resin material (1)]
○○: The dielectric loss tangent of the cured resin material (1) is 0.003 or less. ○: The dielectric loss tangent of the cured resin material (1) is greater than 0.003 and less than 0.005. △: The dielectric loss tangent of the cured resin material (1) is greater than 0.005 and less than 0.007. ×: The dielectric loss tangent of the cured resin material (1) is greater than 0.007.

[Criteria for the rate of change of dielectric tangent]
○: The rate of change in the dielectric tangent is 150% or less. △: The rate of change in the dielectric tangent is more than 150% and less than 225%. ×: The rate of change in the dielectric tangent is more than 225%.

(2) Dielectric constant (Dk) of the cured resin material (1)
The cured resin material (1) obtained in the above "(1) Dielectric loss tangent (Df) and rate of change of dielectric loss tangent of the cured resin material (1)" was cut into a size of 2 mm wide and 80 mm long, and 10 pieces were stacked to prepare a measurement sample. The dielectric constant (Dk) of the cured resin material (1) was measured by the cavity resonance method at room temperature (23°C) and a frequency of 10 GHz using a "Cavity Resonance Perturbation Dielectric Constant Measuring Device CP521" manufactured by Kanto Electronics Application Development Co., Ltd. and a "Network Analyzer N5224A PNA" manufactured by Keysight Technologies, Inc.

[Criteria for dielectric constant (Dk) of cured resin material (1)]
○○: The dielectric constant of the cured resin material (1) is 2.2 or less. ○: The dielectric constant of the cured resin material (1) is greater than 2.2 and less than 2.5. △: The dielectric constant of the cured resin material (1) is greater than 2.5 and less than 2.8. ×: The dielectric constant of the cured resin material (1) is greater than 2.8.

(3) Insulation reliability after HAST test Both sides of a copper-clad laminate having a predetermined dumbbell-shaped wiring pattern were surface-treated (roughened) with "CZ-8101" manufactured by MEC. Using "Batch-type vacuum laminator MVLP-500-IIA" manufactured by Meiki Seisakusho, the resin film (B stage film) side of the laminate film was laminated on the copper-clad laminate on both sides of the roughened copper-clad laminate to obtain a laminated structure. The lamination conditions were as follows: decompression for 30 seconds to make the air pressure 13 hPa or less, then lamination at 100 ° C and pressure 0.7 MPa for 30 seconds, and further pressing at a press pressure of 0.8 MPa and a press temperature of 100 ° C for 60 seconds. Thereafter, the PET film was peeled off, and the resin film was semi-cured by heating in a 180 ° C gear oven for 30 minutes. In this way, a laminate in which a semi-cured resin film was laminated on a copper-clad laminate was obtained.

Roughening treatment:
(a) Swelling treatment:
The obtained laminate was placed in a swelling liquid (Swelling Dip Securigant P, manufactured by Atotech Japan, containing sodium hydroxide) at 60° C. and shaken for 10 minutes, and then washed with pure water.

(b) Permanganate Treatment:
The laminate after the swelling treatment was placed in a potassium permanganate (Concentrate Compact CP, manufactured by Atotech Japan, containing sodium hydroxide) roughening solution at 80° C. and swung for 20 minutes. Next, it was washed for 5 minutes with a cleaning solution (Reduction Securigant P, manufactured by Atotech Japan) at 40° C., and then further washed with pure water.

The resulting roughened laminate was subjected to electroless copper plating and electrolytic copper plating in the following procedure.

(c) Electroless plating treatment:
The surface of the cured resin film in the roughened laminate (referred to as cured product A) was treated with an alkaline cleaner (Cleaner Securigant 902, manufactured by Atotech Japan) at 60°C for 5 minutes, followed by degreasing and cleaning. After cleaning, the cured product A was treated with a pre-dip liquid (Pre-dip Neoganth B, manufactured by Atotech Japan) at 25°C for 2 minutes. Thereafter, the cured product A was treated with an activator liquid (Activator Neoganth 834, manufactured by Atotech Japan) at 40°C for 5 minutes to attach a palladium catalyst. Next, the cured product A was treated with a reducing liquid (Reducer Neoganth WA, manufactured by Atotech Japan) at 30°C for 5 minutes.

Next, the cured material A was placed in a chemical copper solution (Atotech Japan's "Basic Printganth MSK-DK", "Copper Printganth MSK", "Stabilizer Printganth MSK", and "Reducer Cu") and electroless plating was performed until the plating thickness reached approximately 1 μm. After electroless plating, in order to remove any remaining hydrogen gas, annealing was performed at a temperature of 120°C for 30 minutes to obtain a cured material B that had been roughened and electrolessly plated. All steps up to the electroless plating step were performed using 2 L of treatment solution on a beaker scale while the cured material was rocked.

(d) Electrolytic plating treatment:
Next, a copper sulfate solution ("Copper Sulfate Pentahydrate" manufactured by Wako Pure Chemical Industries, Ltd., "Sulfuric Acid" manufactured by Wako Pure Chemical Industries, Ltd., "Basic Leveller Cupracid HL" manufactured by Atotech Japan, "Correction Agent Cupracid GS" manufactured by Atotech Japan) was used as the electrolytic plating solution, and a current of 0.6 A/ ^cm2 was passed to perform electrolytic plating until the plating thickness reached about 15 μm.

(e) Formation of outer layer copper wiring pattern:
Next, a dry film resist (Sunfort UFG-155, manufactured by Asahi Kasei E-materials Corporation) was laminated on the electrolytic plating using a hot roll laminator. Contact UV exposure was performed using a pattern photomask so that one circle of the dumbbell-shaped copper wiring of the outer layer was placed on top of one circle of the dumbbell-shaped copper pattern of the inner layer, sandwiching a resin film. Next, the UV-unexposed portion was dissolved and removed using a 1 wt% aqueous solution of sodium bicarbonate at 23°C to expose the electrolytic plating. The exposed electrolytic plating was removed by etching, and the UV-exposed dry film resist was peeled and removed using a 1 wt% aqueous solution of sodium hydroxide at 23°C to expose the electrolytic plating, and final curing was performed at 200°C for 60 minutes.

A polytetrafluoroethylene (PTFE)-coated electric wire C was connected to the laminate obtained in this manner using Sn-Pb eutectic solder. In the outer region of the laminate, the cured material was scraped off with a utility knife to expose the surface of the inner layer circuit board. A PTFE-coated electric wire D was connected to the exposed surface of the circuit board using Sn-Pb eutectic solder.

Wires C and D were connected to a highly accelerated life test (HAST) device, and the resistance value within the layer was measured after applying a DC voltage of 3.3 V for 200 hours in an environment of 130°C and 85% RH.

[Criteria for insulation reliability after HAST test]
◯: Resistance value is 1×10 ⁸ Ω or more △: Resistance value is 1×10 ⁷ Ω or more and less than 1×10 ⁸ Ω ×: Resistance value is less than 1×10 ⁷ Ω

The compositions and results are shown in Tables 1 to 3 below.

11: multilayer printed wiring board 12: circuit board 12a: upper surface 13-16: insulating layers 17: metal layer

Claims (10)

A radical polymerizable compound (A),
Hollow aluminosilicate particles (B);
and a curing accelerator (C),
A resin material having the following first configuration or the following second configuration.
First configuration: the content of the radically polymerizable compound (A) is 20% by weight or more based on 100% by weight of the components excluding the solvent in the resin material.
Second configuration: When the dielectric tangent of a cured product (1) of the resin material obtained by heating a resin material at 180° C. for 30 minutes and then at 200° C. for 60 minutes and the dielectric tangent of a cured product (2) of the resin material obtained by leaving the cured product (1) of the resin material at rest for 100 hours at 130° C. and 85% RH are measured, the rate of change in the dielectric tangent calculated by the following formula (Df) is 225% or less.
Rate of change of dielectric tangent (%) = (|Df1-Df2|/Df1) x 100 ... (Df)
Df1: Dielectric tangent of the cured resin material (1) Df2: Dielectric tangent of the cured resin material (2) The resin material according to claim 1, comprising the first configuration. The resin material according to claim 1, which has the second configuration. The resin material according to claim 1, comprising the first configuration and the second configuration. The resin material according to any one of claims 1 to 4, wherein the content of the hollow aluminosilicate particles (B) is 55% by weight or less in 100% by weight of the components excluding the solvent in the resin material. The resin material according to any one of claims 1 to 4, wherein the hollow aluminosilicate particles (B) are surface-treated hollow aluminosilicate particles. The resin material according to any one of claims 1 to 4, which is a resin film. The resin material according to any one of claims 1 to 4, which is used to form an insulating layer in a multilayer printed wiring board. A cured product of a resin material,
A cured product, wherein the resin material is the resin material according to any one of claims 1 to 4. A circuit board;
a plurality of insulating layers disposed on a surface of the circuit board;
a metal layer disposed between a plurality of the insulating layers;
A multilayer printed wiring board, wherein at least one of the insulating layers is a cured product of the resin material according to any one of claims 1 to 4.

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