JP7437215B2 - Resin materials and multilayer printed wiring boards - Google Patents

Description

The present invention relates to a resin material containing a maleimide compound or a benzoxazine compound. The present invention also relates to a multilayer printed wiring board using the above resin material.

Conventionally, various resin materials have been used to obtain electronic components such as semiconductor devices, laminates, and printed wiring boards. For example, in a multilayer printed wiring board, a resin material is used to form an insulating layer for insulating between internal layers, and to form an insulating layer located on a surface layer. Wiring, which is generally metal, is laminated on the surface of the insulating layer. Moreover, in order to form the above-mentioned insulating layer, a resin film obtained by forming the above-mentioned resin material into a film may be used. The resin material and the resin film are used as insulating materials for multilayer printed wiring boards including build-up films.

Patent Document 1 below discloses a resin composition containing a compound having a maleimide group, a divalent group having at least two imide bonds, and a saturated or unsaturated divalent hydrocarbon group. . Patent Document 1 describes that a cured product of this resin composition can be used as an insulating layer of a multilayer printed wiring board or the like.

Patent Document 2 below discloses a resin composition for electronic materials containing a bismaleimide compound, in which the bismaleimide compound has two maleimide groups and one or more polyimide groups having a specific structure. . In the bismaleimide compound, the two maleimide groups are each independently bonded to both ends of the polyimide group through at least a first linking group in which 8 or more atoms are connected in a linear chain. .

Furthermore, the above resin materials are also widely used in applications other than electronic components.

For example, Patent Document 3 listed below describes an insulating composition (resin material) that can be used for insulated wires. The insulating composition includes a low molecular weight bismaleimide having a molecular weight of less than 1000, a high molecular weight bismaleimide having a molecular weight of 3000 or more, and a curing agent.

WO2016/114286A1 JP2018-90728A WO2014/181456A1

Cured products of conventional resin materials may not have sufficiently high thermal dimensional stability or may not have sufficiently high elongation properties. It is difficult to improve the elongation characteristics of a cured product with a resin material whose formulation is designed to have sufficiently high thermal dimensional stability.

An object of the present invention is to provide a resin material that can improve the thermal dimensional stability of a cured product and the elongation characteristics of the cured product. Another object of the present invention is to provide a multilayer printed wiring board using the above resin material.

According to a broad aspect of the present invention, there is provided a resin material containing the following first compound and at least one of the following second compound and the following third compound.

First compound: a maleimide compound with a molecular weight of less than 1,500 and a trifunctional or higher functionality; or a benzoxazine compound with a molecular weight of less than 1,500 and a trifunctional or higher functional group; Second compound: a maleimide compound with a molecular weight of 1,500 or higher; or a benzoxazine compound having a molecular weight of 1500 or more Third compound: aromatic bismaleimide compound

In a particular aspect of the resin material according to the present invention, the first compound is an alkylmaleimide compound having a molecular weight of less than 1500 and having trifunctional or higher functionality.

In a particular aspect of the resin material according to the present invention, the first compound is a benzoxazine compound having a molecular weight of 1000 or less and a trifunctional or higher functionality.

In a particular aspect of the resin material according to the present invention, the first compound has an ester bond.

In a particular aspect of the resin material according to the present invention, the first compound has an isocyanuric acid skeleton.

In a certain aspect of the resin material according to the present invention, the resin material includes the second compound.

In a particular aspect of the resin material according to the present invention, the second compound is an alkylmaleimide compound having a molecular weight of 1500 or more.

In a particular aspect of the resin material according to the present invention, the second compound has an imide skeleton.

In a particular aspect of the resin material according to the present invention, the second compound has a molecular weight of 50,000 or less.

In a particular aspect of the resin material according to the present invention, the second compound has a skeleton derived from dimer diamine.

In a particular aspect of the resin material according to the present invention, the second compound has a cyclohexyl ring skeleton.

In a particular aspect of the resin material according to the present invention, the resin material includes the third compound.

In a certain aspect of the resin material according to the present invention, the resin material includes an epoxy compound.

In a particular aspect of the resin material according to the present invention, the resin material includes a curing agent, and the curing agent includes an active ester compound.

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

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

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

The resin material according to the present invention includes a maleimide compound having a molecular weight of less than 1500 and having three or more functionalities, or a benzoxazine compound (first compound) having a molecular weight of less than 1500 and having three or more functionalities. The resin material according to the present invention is a maleimide compound having a molecular weight of 1500 or more, or at least one of a benzoxazine compound (second compound) and an aromatic bismaleimide compound (third compound) having a molecular weight of 1500 or more. including. Since the resin material according to the present invention has the above configuration, the thermal dimensional stability of the cured product can be improved, and the elongation characteristics of the cured product can be improved.

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

The present invention will be explained in detail below.

The resin material according to the present invention includes the following first compound, and at least one of the following second compound and the following third compound. The resin material according to the present invention may contain a first compound and a second compound, may contain a first compound and a third compound, or may contain a first compound and a second compound. The compound and a third compound may be included.

First compound: a maleimide compound with a molecular weight of less than 1,500 and a trifunctional or higher functionality; or a benzoxazine compound with a molecular weight of less than 1,500 and a trifunctional or higher functional group; Second compound: a maleimide compound with a molecular weight of 1,500 or higher; or a benzoxazine compound having a molecular weight of 1500 or more Third compound: aromatic bismaleimide compound

Since the resin material according to the present invention has the above configuration, the thermal dimensional stability of the cured product can be improved, and the elongation characteristics of the cured product can be improved.

In addition, since the resin material according to the present invention has the above configuration, smear can be effectively removed by desmear treatment, the bending properties of the cured product can be improved, and the plating peel strength can be increased. be able to.

The resin material according to the present invention may be a resin composition or a resin film. The resin composition has fluidity. The resin composition may be in the form of a paste. The pasty state includes a liquid state. The resin material according to the present invention is preferably a resin film because of its excellent handling properties.

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

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

In this specification, the first compound "a maleimide compound having a molecular weight of less than 1500 and having trifunctional or higher functionality" may be referred to as "maleimide compound (1)", and the first compound "a maleimide compound having a molecular weight of is less than 1500 and is trifunctional or more functional," is sometimes referred to as "benzoxazine compound (1)." In addition, in this specification, the second compound "maleimide compound having a molecular weight of 1500 or more" may be referred to as "maleimide compound (2)", and the second compound "maleimide compound having a molecular weight of 1500 or more" "A certain benzoxazine compound" is sometimes referred to as "benzoxazine compound (2)."

[First compound]
The first compound is a maleimide compound (1) or a benzoxazine compound (1). The first compound may be a maleimide compound (1), a benzoxazine compound (1), or both a maleimide compound (1) and a benzoxazine compound (1). . It is preferable that the first compound is a thermosetting compound. Only one type of maleimide compound (1) and benzoxazine compound (1) may be used, or two or more types thereof may be used in combination.

From the viewpoint of exhibiting the effects of the present invention even more effectively, the maleimide compound (1) is preferably an alkylmaleimide compound. The first compound is preferably an alkylmaleimide compound having a molecular weight of less than 1500 and having trifunctional or higher functionality.

From the viewpoint of further improving desmear properties, the first compound preferably has an ester bond.

From the viewpoint of improving water absorption during desmearing and lowering the dielectric loss tangent of the cured product, it is preferable that the first compound has a skeleton with a large number of heteroatoms and high symmetry, and an isocyanuric acid skeleton. It is more preferable to have.

The maleimide compound (1) is a trifunctional or higher functional maleimide compound. The maleimide compound (1) may be a trifunctional maleimide compound, a tetrafunctional maleimide compound, or a tetrafunctional or higher functional maleimide compound.

The benzoxazine compound (1) is a trifunctional or more functional benzoxazine compound. The benzoxazine compound (1) may be a trifunctional benzoxazine compound, a tetrafunctional benzoxazine compound, or a tetrafunctional or more functional benzoxazine compound.

The first compound has a molecular weight of less than 1500. The molecular weight of the first compound is preferably 400 or more, more preferably 500 or more, preferably 1000 or less, and more preferably 850 or less. When the molecular weight of the first compound is not less than the above lower limit and not more than the above upper limit, the crosslink density can be increased and the linear thermal expansion coefficient of the cured product can be lowered.

The molecular weight of maleimide compound (1) is less than 1500. The molecular weight of the maleimide compound (1) is preferably 400 or more, more preferably 500 or more, preferably 1000 or less, and more preferably 850 or less. When the molecular weight of the maleimide compound (1) is not less than the above lower limit and not more than the above upper limit, the crosslinking density can be increased and the linear thermal expansion coefficient of the cured product can be lowered.

The molecular weight of the benzoxazine compound (1) is less than 1500. The molecular weight of the benzoxazine compound (1) is preferably 400 or more, more preferably 500 or more, even more preferably 600 or more, preferably 1200 or less, and more preferably 1000 or less. When the molecular weight of the benzoxazine compound (1) is not less than the above lower limit and not more than the above upper limit, the crosslinking density can be increased and the linear thermal expansion coefficient of the cured product can be reduced.

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

Examples of the maleimide compound (1) (alkylmaleimide compound) include compounds represented by the following formula (1A), the following formula (1B), and the following formula (1C).

The maleimide compound (1) represented by the above formula (1C) can be synthesized by a dehydration condensation reaction between 1,2,4-butanetriol and 6-maleimidohexanoic acid.

Benzoxazine compound (1) can be synthesized, for example, by the method described in JP-A-2018-503623.

The content of the first compound is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, and even more preferably The content is 0.5% by weight or more, preferably 20% by weight or less, more preferably 10% by weight or less. When the content of the first compound is equal to or higher than the lower limit, the effects of the present invention can be exhibited even more effectively. In addition, when the content of the first compound is equal to or higher than the lower limit, smear can be removed more effectively by desmear treatment, the bending properties of the cured product can be further improved, and the plating peel strength can be improved. can be further enhanced.

The content of the maleimide compound (1) is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, and even more preferably The content is 0.5% by weight or more, preferably 20% by weight or less, more preferably 10% by weight or less. When the content of the maleimide compound (1) is at least the above lower limit, the effects of the present invention can be exhibited even more effectively. In addition, when the content of the maleimide compound (1) is equal to or higher than the lower limit, smear can be removed even more effectively by desmear treatment, the bending properties of the cured product can be further improved, and plating peeling can be achieved. Strength can be further increased.

The content of the benzoxazine compound (1) is preferably 0.15% by weight or more, more preferably 0.45% by weight or more, and even more preferably is 0.75% by weight or more, preferably 30% by weight or less, more preferably 15% by weight or less. When the content of the benzoxazine compound (1) is at least the above lower limit, the effects of the present invention can be exhibited even more effectively. In addition, when the content of the benzoxazine compound (1) is equal to or higher than the lower limit, smear can be removed even more effectively by desmear treatment, the bending properties of the cured product can be further improved, and plating Peel strength can be further increased.

[Second compound]
The second compound is a maleimide compound (2) or a benzoxazine compound (2). The second compound may be a maleimide compound (2), a benzoxazine compound (2), or both a maleimide compound (2) and a benzoxazine compound (2). . Preferably, the second compound is a thermosetting compound. Only one type of maleimide compound (2) and benzoxazine compound (2) may be used, or two or more types thereof may be used in combination.

From the viewpoint of exhibiting the effects of the present invention even more effectively, the resin material preferably contains the second compound.

From the viewpoint of exhibiting the effects of the present invention even more effectively, the maleimide compound (2) is preferably an alkylmaleimide compound. The second compound is preferably an alkylmaleimide compound having a molecular weight of 1500 or more.

From the viewpoint of further improving desmear properties and lowering the dielectric loss tangent of the cured product, it is preferable that the second compound has an imide skeleton.

From the viewpoint of further enhancing the elongation characteristics of the cured product and lowering the dielectric loss tangent of the cured product, it is preferable that the second compound has a skeleton derived from dimer diamine. Conventional resin materials containing a second compound having a skeleton derived from dimer diamine can improve the elongation properties of the cured product, but the thermal dimensional stability of the cured product tends to decrease. That is, with conventional resin materials containing a second compound having a skeleton derived from dimer diamine, it is difficult to achieve both the thermal dimensional stability of the cured product and the elongation properties of the cured product. Have difficulty. In contrast, in the present invention, even if the second compound having a skeleton derived from dimer diamine is used, a specific first compound is used in combination, so that the thermal dimensional stability of the cured product is improved. It is possible to improve the elongation properties of the cured product.

The skeleton derived from the dimer diamine is preferably a skeleton derived from a reaction product of the dimer diamine and an acid dianhydride. The skeleton derived from the reaction product of the dimer diamine and the acid dianhydride has a skeleton derived from the dimer diamine.

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

Examples of the acid dianhydride include tetracarboxylic dianhydride.

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetra Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether Tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2 , 3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl Sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3 ',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenyl phthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, and bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride.

From the viewpoint of reducing the linear thermal expansion coefficient of the cured product and the dielectric loss tangent of the cured product, it is preferable that the second compound has a cyclohexyl ring skeleton.

The maleimide compound (2) may be a monofunctional maleimide compound or a polyfunctional maleimide compound. The maleimide compound (2) may be a bifunctional maleimide compound, a bifunctional or more functional maleimide compound, or a trifunctional or more functional maleimide compound. From the viewpoint of exhibiting the effects of the present invention even more effectively, the maleimide compound (2) is preferably a difunctional maleimide compound.

The benzoxazine compound (2) may be a monofunctional benzoxazine compound or may be a polyfunctional benzoxazine compound. The benzoxazine compound (2) may be a bifunctional benzoxazine compound, a bifunctional or more functional benzoxazine compound, or a trifunctional or more functional benzoxazine compound. From the viewpoint of exhibiting the effects of the present invention even more effectively, the benzoxazine compound (2) is preferably a difunctional benzoxazine compound.

The second compound has a molecular weight of 1500 or more. The molecular weight of the second compound is preferably 2,000 or more, more preferably 3,000 or more, still more preferably 4,000 or more, preferably 50,000 or less, more preferably 20,000 or less, still more preferably 10,000 or less. When the molecular weight of the second compound is not less than the above lower limit and not more than the above upper limit, surface unevenness and waviness can be reduced particularly when embedded in a patterned substrate.

The molecular weight of the maleimide compound (2) is 1500 or more. The molecular weight of the maleimide compound (2) is preferably 2,000 or more, more preferably 3,000 or more, still more preferably 4,000 or more, preferably 50,000 or less, more preferably 20,000 or less, still more preferably 10,000 or less. When the molecular weight of the maleimide compound (2) is at least the above lower limit and below the above upper limit, surface unevenness and waviness can be reduced, particularly when embedded in a patterned substrate.

The molecular weight of the benzoxazine compound (2) is 1500 or more. The molecular weight of the benzoxazine compound (2) is preferably 2,000 or more, more preferably 3,000 or more, even more preferably 4,000 or more, preferably 50,000 or less, more preferably 20,000 or less, still more preferably 10,000 or less. When the molecular weight of the benzoxazine compound (2) is at least the above lower limit and below the above upper limit, surface unevenness and waviness can be reduced, especially when embedded in a patterned substrate.

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

Commercially available maleimide compound (2) (alkylmaleimide compound) is available from Designer Molecules Inc. Examples include "BMI-1500", "BMI-1700", and "BMI-3000" manufactured by Manufacturer.

The benzoxazine compound (2) can be obtained, for example, by reacting an acid dianhydride with a diamine compound to synthesize a compound having an amine structure at both ends and having a molecular weight of 1200 or more, and then combining the compound with paraform and phenol. It can be synthesized by reaction.

The content of the second compound is preferably 10% by weight or more, more preferably 25% by weight or more, even more preferably 35% by weight or more in 100% by weight of the components excluding the inorganic filler and solvent in the resin material. , preferably 90% by weight or less, more preferably 80% by weight or less. When the content of the second compound is equal to or higher than the lower limit, the effects of the present invention can be exhibited even more effectively. In addition, when the content of the second compound is equal to or higher than the lower limit, smear can be removed more effectively by desmear treatment, the bending properties of the cured product can be further improved, and the thermal decomposition can be suppressed, the dielectric loss tangent of the cured product can be lowered, and the plating peel strength can be further increased.

The content of the maleimide compound (2) is preferably 10% by weight or more, more preferably 25% by weight or more, even more preferably 35% by weight or more in 100% by weight of the components excluding the inorganic filler and solvent in the resin material. , preferably 90% by weight or less, more preferably 80% by weight or less. When the content of the maleimide compound (2) is at least the above lower limit, the effects of the present invention can be exhibited even more effectively. In addition, when the content of the maleimide compound (2) is equal to or higher than the lower limit, smear can be removed even more effectively by desmear treatment, the bending properties of the cured product can be further improved, and thermal decomposition The dielectric loss tangent of the cured product can be lowered, and the plating peel strength can be further increased.

The content of the benzoxazine compound (2) is preferably 15% by weight or more, more preferably 30% by weight or more, and still more preferably 40% by weight in 100% by weight of the components excluding the inorganic filler and solvent in the resin material. The content is preferably 90% by weight or less, more preferably 80% by weight or less. When the content of the benzoxazine compound (2) is at least the above lower limit, the effects of the present invention can be exhibited even more effectively. Furthermore, when the content of the benzoxazine compound (2) is at least the above lower limit, smear can be removed even more effectively by desmear treatment, the bending properties of the cured product can be further improved, and the plating Peel strength can be further increased.

The weight ratio of the content of the second compound to the content of the first compound (content of the second compound/content of the first compound) is preferably 1 or more, more preferably 3 or more. , more preferably 5 or more, particularly preferably 10 or more, preferably 30 or less, more preferably 20 or less. When the weight ratio is not less than the lower limit and not more than the upper limit, the effects of the present invention can be exhibited even more effectively. Further, when the weight ratio is at least the above lower limit and below the above upper limit, thermal decomposition can be suppressed and the dielectric loss tangent of the cured product can be lowered.

[Third compound]
The third compound is an aromatic bismaleimide compound. As the third compound, a conventionally known aromatic bismaleimide compound can be used. As for the said 3rd compound, only 1 type may be used, and 2 or more types may be used together.

From the viewpoint of exhibiting the effects of the present invention even more effectively, it is preferable that the resin material contains the third compound.

The molecular weight of the third compound is preferably 250 or more, more preferably 300 or more, preferably 1000 or less, and more preferably 800 or less. When the molecular weight of the third compound is not less than the above lower limit and not more than the above upper limit, the thermal linear expansion coefficient of the cured product can be further lowered and the heat resistance can be improved.

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

Commercially available products of the third compound include "BMI-80" manufactured by KI Kasei Co., Ltd. and "BMI-5100" manufactured by Daiwa Kasei Co., Ltd.

The content of the third compound is preferably 1% by weight or more, more preferably 3% by weight or more, and even more preferably 5% by weight or more in 100% by weight of the components excluding the inorganic filler and solvent in the resin material. , preferably 20% by weight or less, more preferably 15% by weight or less. When the content of the third compound is equal to or higher than the lower limit, the effects of the present invention can be exhibited even more effectively. In addition, when the content of the third compound is equal to or higher than the lower limit, smear can be removed even more effectively by desmear treatment, the bending properties of the cured product can be further improved, and the plating peel strength can be improved. can be further enhanced.

The weight ratio of the content of the third compound to the content of the first compound (content of the third compound/content of the first compound) is preferably 0.1 or more, more preferably The number is 1 or more, more preferably 2 or more, preferably 30 or less, and more preferably 15 or less. When the weight ratio is not less than the lower limit and not more than the upper limit, the effects of the present invention can be exhibited even more effectively. Furthermore, when the weight ratio is above the above lower limit and below the above upper limit, smear can be removed more effectively by desmear treatment, the bending properties of the cured product can be further improved, and the plating peel strength can be improved. It can be further improved.

[Epoxy compound]
Preferably, the resin material includes an epoxy compound. As the epoxy compound, conventionally known epoxy compounds can be used. The epoxy compound is an organic compound having at least one epoxy group. The above epoxy compounds may be used alone or in combination of two or more.

The above-mentioned epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenol novolak type epoxy compounds, biphenyl type epoxy compounds, biphenyl novolac type epoxy compounds, biphenol type epoxy compounds, and naphthalene type epoxy compounds. , fluorene type epoxy compound, phenol aralkyl type epoxy compound, naphthol aralkyl type epoxy compound, dicyclopentadiene type epoxy compound, anthracene type epoxy compound, epoxy compound having an adamantane skeleton, epoxy compound having a tricyclodecane skeleton, naphthylene ether type Examples include epoxy compounds and epoxy compounds having a triazine nucleus in their skeleton.

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

From the viewpoint of further lowering the dielectric loss tangent of the cured product and increasing the thermal dimensional stability and flame retardance of the cured product, the epoxy compound preferably contains an epoxy compound having an aromatic skeleton, and a naphthalene skeleton or a naphthalene skeleton. It is preferable to include an epoxy compound having a phenyl skeleton, and more preferably an epoxy compound having an aromatic skeleton.

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

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

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

It is more preferable that the molecular weight of the epoxy compound is 1000 or less. In this case, even if the content of the inorganic filler is 50% by weight or more in 100% by weight of the components excluding the solvent in the resin material, a resin material with high fluidity can be obtained during formation of the insulating layer. Therefore, when an uncured resin material or a B-staged resin material is laminated on a circuit board, the inorganic filler can be uniformly present.

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

From the viewpoint of further increasing the thermal dimensional stability of the cured product, the content of the epoxy compound is preferably 4% by weight or more, more preferably 7% by weight or more in 100% by weight of the components excluding the solvent in the resin material. , preferably 15% by weight or less, more preferably 12% by weight or less.

The content of the epoxy compound is preferably 15% by weight or more, more preferably 25% by weight or more, preferably 50% by weight or less, more preferably 100% by weight of the components excluding the inorganic filler and solvent in the resin material. is 40% by weight or less. When the content of the epoxy compound is not less than the above lower limit and not more than the above upper limit, the thermal dimensional stability of the cured product can be further improved.

Weight ratio of the content of the epoxy compound to the total content of the first compound, the second compound, the third compound, and the curing agent described below (content of the epoxy compound/first compound The total content of the second compound, the third compound, and the curing agent described below) is preferably 0.1 or more, more preferably 0.5 or more, preferably 1.5 or less, and more preferably 1 It is as follows. When the weight ratio is not less than the lower limit and not more than the upper limit, the dielectric loss tangent can be further lowered and the thermal dimensional stability can be further improved.

[Vinyl compound]
Preferably, the resin material includes a vinyl compound. As the vinyl compound, conventionally known vinyl compounds can be used. The vinyl compound is an organic compound having at least one vinyl group. Only one kind of the above-mentioned vinyl compound may be used, or two or more kinds thereof may be used in combination.

Examples of the vinyl compound include divinylbenzyl ether compounds.

The content of the vinyl compound is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 20% by weight or more, based on 100% by weight of the components excluding the inorganic filler and solvent in the resin material. is 80% by weight or less, more preferably 70% by weight or less. When the content of the vinyl compound is not less than the above lower limit and not more than the above upper limit, the thermal dimensional stability of the cured product can be further improved.

[Inorganic filler]
The resin material preferably contains an inorganic filler. By using the above inorganic filler, the dielectric loss tangent of the cured product can be further lowered. Further, by using the above-mentioned inorganic filler, the dimensional change due to heat of the cured product is further reduced. Only one kind of the above-mentioned inorganic filler may be used, or two or more kinds thereof may be used in combination.

Examples of the inorganic filler include silica, talc, clay, mica, hydrotalcite, alumina, magnesium oxide, aluminum hydroxide, aluminum nitride, and boron nitride. The above-mentioned inorganic filler may be an inorganic filler containing fluorine atoms.

The surface roughness of the cured product is reduced, the adhesive strength between the cured product and the metal layer is further increased, finer wiring is formed on the surface of the cured product, and the cured product has better insulation reliability. From the viewpoint of imparting this, the inorganic filler is preferably silica or alumina, more preferably silica, and even more preferably fused silica. By using silica, the coefficient of thermal expansion of the cured product becomes even lower, and the dielectric loss tangent of the cured product becomes even lower. Moreover, by using silica, the surface roughness of the surface of the cured product is effectively reduced, and the adhesive strength between the cured product and the metal layer is effectively increased. The shape of the silica is preferably spherical.

The inorganic filler is spherical silica from the viewpoint of curing the resin, effectively increasing the glass transition temperature of the cured product, and effectively reducing the linear thermal expansion coefficient of the cured product regardless of the curing environment. It is preferable.

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

The average particle size of the inorganic filler is preferably 50 nm or more, more preferably 100 nm or more, even more preferably 500 nm or more, preferably 5 μm or less, more preferably 3 μm or less, and still more preferably 1 μm or less. When the average particle size of the inorganic filler is not less than the lower limit and not more than the upper limit, the surface roughness after etching can be reduced and the plating peel strength can be increased, and the bond between the insulating layer and the metal layer can be reduced. Adhesion can be further improved.

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

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

The inorganic filler is preferably surface-treated, more preferably surface-treated with a coupling agent, and even more preferably surface-treated with a silane coupling agent. By surface-treating the inorganic filler, 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. Furthermore, since the inorganic filler is surface-treated, finer wiring can be formed on the surface of the cured product, and even better inter-wiring insulation reliability and interlayer insulation reliability can be achieved on the cured product. can be granted.

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

The content of the inorganic filler is preferably 50% by weight or more, more preferably 60% by weight or more, even more preferably 65% by weight or more, and particularly preferably 68% by weight in 100% by weight of the components excluding the solvent in the resin material. % or more, preferably 90% by weight or less, more preferably 85% by weight or less, still more preferably 80% by weight or less, particularly preferably 75% by weight or less. When the content of the inorganic filler is equal to or higher than the lower limit, the dielectric loss tangent effectively decreases. When the content of the inorganic filler is below the upper limit, thermal dimensional stability can be improved and warping of the cured product can be effectively suppressed. When the content of the inorganic filler is not less than the above lower limit and not more than the above upper limit, the surface roughness of the surface of the cured product can be further reduced, and finer wiring can be formed on the surface of the cured product. I can do it. Furthermore, with the content of this inorganic filler, it is possible to lower the coefficient of thermal expansion of the cured product and at the same time improve smear removability.

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

The above curing agents include phenol compounds (phenol curing agents), active ester compounds, cyanate ester compounds (cyanate ester curing agents), carbodiimide compounds (carbodiimide curing agents), amine compounds (amine curing agents), thiol compounds (thiol curing agents). ), phosphine compounds, dicyandiamide, acid anhydrides, and the like. The curing agent preferably has a functional group capable of reacting with the epoxy group of the epoxy compound.

From the viewpoint of further lowering the dielectric loss tangent of the cured product and further increasing the thermal dimensional stability of the cured product, the curing agent is selected from among phenol compounds, active ester compounds, cyanate ester compounds, carbodiimide compounds, and acid anhydrides. Preferably, it contains at least one component. From the viewpoint of further lowering the dielectric loss tangent and further increasing the thermal dimensional stability, the curing agent may contain at least one component of a phenol compound, an active ester compound, a cyanate ester compound, and a carbodiimide compound. More preferably, it contains an active ester compound.

From the viewpoint of further increasing thermal dimensional stability, further lowering the dielectric loss tangent, and increasing plating peel strength, the resin material contains an epoxy compound, and the curing agent contains both a phenol compound and an active ester compound. It is preferable.

Examples of the above-mentioned phenol compounds include novolac-type phenol, biphenol-type phenol, naphthalene-type phenol, dicyclopentadiene-type phenol, aralkyl-type phenol, and dicyclopentadiene-type phenol.

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

The above-mentioned active ester compound refers to a compound that contains at least one ester bond in its structure and has an aliphatic chain, an aliphatic ring, or an aromatic ring bonded to both sides of the ester bond. The active ester compound is obtained, for example, by a condensation reaction between a carboxylic acid compound or a thiocarboxylic acid compound and a hydroxy compound or a thiol compound. Examples of active ester compounds include compounds represented by the following formula (1).

In the above formula (1), X1 represents a group containing an aliphatic chain, a group containing an aliphatic ring, or a group containing an aromatic ring, and X2 represents a group containing an aromatic ring. Preferred examples of the group containing the aromatic ring include a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, and the like. Examples of the above-mentioned substituents include hydrocarbon groups. The number of carbon atoms in the hydrocarbon group is preferably 12 or less, more preferably 6 or less, still more preferably 4 or less.

In the above formula (1), the combination of X1 and X2 is a combination of a benzene ring which may have a substituent and a benzene ring which may have a substituent, Examples include a combination of a benzene ring which may have a substituent and a naphthalene ring which may have a substituent. Further, in the above formula (1), examples of the combination of X1 and X2 include a combination of a naphthalene ring that may have a substituent and a naphthalene ring that may have a substituent.

The above active ester compound is not particularly limited. From the viewpoint of further enhancing thermal dimensional stability and flame retardancy, the active ester compound is preferably an active ester compound having two or more aromatic skeletons. From the viewpoint of lowering the dielectric loss tangent of the cured product and increasing the thermal dimensional stability of the cured product, it is more preferable that the active ester compound has a naphthalene ring in its main chain skeleton.

Examples of commercially available active ester compounds include "HPC-8000-65T", "EXB9416-70BK" and "EXB8100-65T" manufactured by DIC Corporation.

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

Commercial products of the above cyanate ester compounds include phenol novolak cyanate ester resins (PT-30 and PT-60 manufactured by Lonza Japan), and prepolymers in which bisphenol cyanate ester resins are trimerized (Lonza Japan). ``BA-230S'', ``BA-3000S'', ``BTP-1000S'', and ``BTP-6020S'' manufactured by the company.

The content of the cyanate ester compound is preferably 10% by weight or more, more preferably 15% by weight or more, even more preferably 20% by weight or more, based on 100% by weight of the components excluding the inorganic filler and solvent in the resin material. Preferably it is 85% by weight or less, more preferably 75% by weight or less. When the content of the cyanate ester compound is not less than the above lower limit and not more than the above upper limit, the thermal dimensional stability of the cured product can be further improved.

The above carbodiimide compound is a compound having a structural unit represented by the following formula (2). In the following formula (2), the right end and left end are bonding sites with other groups. Only one kind of the above-mentioned carbodiimide compound may be used, or two or more kinds thereof may be used in combination.

In the above formula (2), represents a group, and p represents an integer of 1 to 5. When a plurality of Xs exist, the plurality of Xs may be the same or different.

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

Commercially available carbodiimide compounds include "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", "Carbodilite V-09", and "Carbodilite V-04K" manufactured by Nisshinbo Chemical Co., Ltd. 10M-SP" and "Carbodilite 10M-SP (revised)," as well as Rhein Chemie's "Stavaxol P," "Stavaxol P400," and "Hikasil 510."

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

Examples of commercially available acid anhydrides include "Rikacid TDA-100" manufactured by Shin Nippon Rika Co., Ltd.

The content of the curing agent based on 100 parts by weight of the epoxy compound is preferably 70 parts by weight or more, more preferably 85 parts by weight or more, preferably 150 parts by weight or less, and more preferably 120 parts by weight or less. When the content of the curing agent is at least the above lower limit and below the above upper limit, the curability is even better, the thermal dimensional stability is further improved, and the volatilization of residual unreacted components can be further suppressed.

The total content of the first compound, the epoxy compound, and the curing agent is preferably 50% by weight or more, more preferably 60% by weight of the 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. It is at least 98% by weight, more preferably at most 95% by weight. When the above-mentioned total content is at least the above-mentioned lower limit and below the above-mentioned upper limit, the curability is even more excellent, and the thermal dimensional stability can be further improved.

The total content of the first compound, the second compound, the third compound, the epoxy compound, and the curing agent in 100% by weight of the components excluding the inorganic filler and solvent in the resin material is , preferably 50% by weight or more, more preferably 60% by weight or more, preferably 98% by weight or less, more preferably 95% by weight or less. When the above-mentioned total content is at least the above-mentioned lower limit and below the above-mentioned upper limit, the curability is even more excellent, and the thermal dimensional stability can be further improved.

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

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

The above imidazole compounds include 2-undecylimidazole, 2-heptadecyl imidazole, 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-un Decylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2' -Methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino- 6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s -triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-dihydroxymethylimidazole etc.

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

Examples of the phosphorus compounds include triphenylphosphine compounds.

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

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

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

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

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

When the vinyl compound is used as the thermosetting compound, radical curing proceeds, so the curing accelerator preferably contains the radical curing accelerator and is dicumyl peroxide or perhexine 25B. is even more preferable. When efficiently curing the resin material after precure, a radical curing accelerator having a 1-minute half-life temperature of 170° C. or more and 200° C. or less is more preferable. Commercially available radical curing accelerators with a 1-minute half-life temperature of 170° C. or more and 200° C. or less include “Perhexin 25B” manufactured by NOF Corporation.

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

[Thermoplastic resin]
Preferably, the resin material includes a thermoplastic resin. Examples of the thermoplastic resin include polyvinyl acetal resin, polyimide resin, and phenoxy resin. Only one kind of the above-mentioned thermoplastic resin may be used, or two or more kinds thereof may be used in combination.

From the viewpoint of effectively lowering the dielectric loss tangent and effectively increasing the adhesion of metal wiring regardless of the curing environment, the thermoplastic resin is preferably a phenoxy resin. By using the phenoxy resin, deterioration in the ability of the resin film to fill holes or irregularities in the circuit board and non-uniformity of the inorganic filler can be suppressed. Further, by using a phenoxy resin, the melt viscosity can be adjusted, so the dispersibility of the inorganic filler is improved, and the resin composition or B-staged product is less likely to wet and spread to unintended areas during the curing process.

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

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

Commercial products of the above phenoxy resin include, for example, "YP50", "YP55", and "YP70" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and "1256B40", "4250", "4256H40", and "4275" manufactured by Mitsubishi Chemical Corporation. , "YX6954BH30" and "YX8100BH30".

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

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

Examples of the above-mentioned tetracarboxylic dianhydride include the tetracarboxylic dianhydride described in the section of the above-mentioned second compound.

Examples of the dimer diamine include the dimer diamines described in the column of the second compound above.

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

From the viewpoint of obtaining a resin material with even better storage stability, the weight average molecular weight of the thermoplastic resin, the polyimide resin, and the phenoxy resin is preferably 5,000 or more, more preferably 10,000 or more, preferably 100,000 or less, and more. Preferably it is 50,000 or less.

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

The contents of the thermoplastic resin, the polyimide resin, and the phenoxy resin are not particularly limited. The content of the thermoplastic resin in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material (if the thermoplastic resin is a polyimide resin or phenoxy resin, the content of the polyimide resin or phenoxy resin) ) is preferably 1% by weight or more, more preferably 2% by weight or more, preferably 30% by weight or less, more preferably 20% by weight or less. When the content of the thermoplastic resin is not less than the lower limit and not more than the upper limit, the resin material has good embedding properties in holes or irregularities of the circuit board. When the content of the thermoplastic resin is equal to or higher than the lower limit, the resin film can be formed even more easily, and an even better insulating layer can be obtained. When the content of the thermoplastic resin is below the above upper limit, the coefficient of thermal expansion of the cured product becomes even lower. When the content of the thermoplastic resin is below the upper limit, the surface roughness of the surface of the cured product becomes even smaller, and the adhesive strength between the cured product and the metal layer becomes even higher.

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

The above 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, Examples include N,N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidone, n-hexane, cyclohexane, cyclohexanone, and naphtha as a mixture.

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

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

[Other ingredients]
In order to improve impact resistance, heat resistance, resin compatibility, workability, etc., the above resin materials contain organic fillers, leveling agents, flame retardants, coupling agents, coloring agents, antioxidants, and UV deterioration prevention. The composition may also contain agents, antifoaming agents, thickeners, thixotropy imparting agents, and the like.

Examples of the organic filler include particulate materials made of benzoxazine resin, benzoxazole resin, fluororesin, acrylic resin, styrene resin, and the like. By using fluororesin particles as the organic filler, the dielectric constant of the cured product can be further lowered. The average particle size of the organic filler is preferably 1 μm or less. When the average particle size of the organic filler is below the above 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 improved. It can be further improved. The average particle size of the organic filler may be 50 nm or more.

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

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

(resin film)
A resin film (B-staged product/B-stage film) is obtained by molding the above-described resin composition into a film. It is preferable that the resin material is a resin film. Preferably, the resin film is a B-stage film.

Examples of methods for obtaining a resin film by molding a resin composition into a film include the following methods. An extrusion molding method in which a resin composition is melt-kneaded using an extruder, extruded, and then molded into a film using a T-die, a circular die, or the like. A casting method in which a resin composition containing a solvent is cast and formed into a film. Other conventionally known film forming methods. An extrusion molding method or a casting molding method is preferable because it is possible to reduce the thickness. The film includes sheets.

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

A film-like resin composition that can be obtained by the drying process as described above is referred to as a B-stage film. The B-stage film is in a semi-cured state. A semi-cured product is not completely cured and may be further cured.

The resin film does not need to be prepreg. If the resin film is not a prepreg, migration will not occur along the glass cloth or the like. Moreover, when laminating or pre-curing the resin film, unevenness caused by the glass cloth will not occur on the surface.

The resin film can be used in the form of a laminated film including a metal foil or a base film and a resin film laminated on the surface of the metal foil or the base film. Preferably, the metal foil is 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 mold release treatment, if necessary.

From the viewpoint of controlling the degree of curing of the resin film more uniformly, the thickness of the resin film is preferably 5 μm or more, and preferably 200 μm or less. When the resin film is used as an insulating layer of a circuit, the thickness of the insulating layer formed of the resin film is preferably greater than or equal to 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 190° C. for 90 minutes to obtain a cured resin material, the dielectric loss tangent (Df) at 23° C. and a frequency of 5.8 GHz is preferably 3.3. ×10 ⁻³ or less, more preferably 3.0×10 ⁻³ or less, even more preferably 2.7×10 ⁻³ or less. The dielectric loss tangent (Df) of the cured product may be 1.0×10 ⁻³ or more, or 1.5×10 ⁻³ or more.

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

A film-like resin material (resin film) is heated at 190° C. for 90 minutes to obtain a cured resin material. The obtained cured product is cut into pieces with a width of 2 mm and a length of 80 mm, and 10 pieces are stacked on top of each other. Using the "Cavity Resonance Perturbation Method Permittivity Measurement Device CP521" manufactured by Kanto Denshi Applied Development Co., Ltd. and the "Network Analyzer N5224A PNA" manufactured by Keysight Technologies, the frequency was measured at 5.8 GHz using the cavity resonance method at room temperature (23 degrees Celsius). Measure the dielectric loss tangent.

When the above resin material is heated at 190°C for 90 minutes to obtain a cured resin material, the average coefficient of linear expansion (CTE) from 25°C to 150°C at a tensile load of 33 mN is as follows: Preferably it is 33 ppm/°C or less, more preferably 30 ppm/°C or less, still more preferably 27 ppm/°C or less, particularly preferably 24 ppm/°C or less, and most preferably 22 ppm/°C or less. The average coefficient of linear expansion (CTE) of the cured product may be 17 ppm/°C or more, or 19 ppm/°C or more.

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

A film-like resin material (resin film) is heated at 190° C. for 90 minutes to obtain a cured resin material. The obtained cured product is cut into a size of 3 mm x 25 mm. Using a thermomechanical analyzer (for example, "EXSTAR TMA/SS6100" manufactured by SII Nanotechnology), the cut cured product was measured at 25 ° C. The average linear expansion coefficient (ppm/°C) up to 150°C is calculated.

(Semiconductor devices, printed wiring boards, copper-clad laminates, and multilayer printed wiring boards)
The resin material described above is suitably used to form a mold resin in which a semiconductor chip is embedded in a semiconductor device.

The above resin material is suitably used as a substitute for liquid crystal polymer (LCP), as a millimeter wave antenna, and as a redistribution layer. Further, the resin material is suitably used not only for the above-mentioned applications but also for wiring formation applications in general.

The above resin material is suitably used as an insulating material. The above resin material is suitably used to form an insulating layer in a printed wiring board.

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

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

The material of the metal layer is preferably copper.

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

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

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

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

An example of the multilayer board is a multilayer board that includes a circuit board and an insulating layer laminated on the circuit board. The insulating layer of this multilayer board is formed from the above resin material. Further, the insulating layer of the multilayer substrate may be formed of the resin film of the laminated film using a laminated film. The insulating layer is preferably laminated on the surface of the circuit board on which the circuit is provided. Preferably, a portion of the insulating layer is embedded between the circuits.

In the multilayer board, it is preferable that the surface of the insulating layer opposite to the surface on which the circuit board is laminated is subjected to a roughening treatment.

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

Preferably, the multilayer substrate further includes a copper plating layer laminated on the roughened surface of the insulating layer.

Another example of the multilayer board is a circuit board, an insulating layer laminated on the surface of the circuit board, and a surface of the insulating layer on the opposite side of the surface on which the circuit board is laminated. For example, a multilayer board may include a copper foil. It is preferable that the insulating layer is formed by using a copper-clad laminate including a copper foil and a resin film laminated on one surface of the copper foil, and by 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 that includes a circuit board and a plurality of insulating layers stacked on the surface of the circuit board. At least one layer of the plurality of insulating layers arranged on the circuit board is formed using the resin material. Preferably, the multilayer board further includes a circuit laminated on at least one surface of the insulating layer formed using the resin film.

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

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

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

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

In the multilayer printed wiring board 11, the insulating layers 13 to 16 are formed of a cured product of the resin material described above. 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. Further, a metal layer 17 extends inside the fine hole. Furthermore, in the multilayer printed wiring board 11, the widthwise dimension (L) of the metal layer 17 and the widthwise dimension (S) of the portion where the metal layer 17 is not formed can be made smaller. Furthermore, 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 connection or through hole connection (not shown).

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

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

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

For the roughening treatment, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound, or a persulfuric compound is used. These chemical oxidants are used as an aqueous solution or an organic solvent dispersion solution after water or an organic solvent is added. The roughening liquid used in the roughening treatment generally contains an alkali as a pH adjuster. It is preferable that the roughening liquid contains sodium hydroxide.

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

The arithmetic mean roughness Ra of the surface of the cured product is preferably 10 nm or more, preferably less than 300 nm, more preferably less than 200 nm, even more preferably less than 150 nm. In this case, the adhesive strength between the cured product and the metal layer is increased, and further finer wiring is formed on the surface of the insulating layer. Furthermore, conductor loss can be suppressed, and signal loss can be kept low. The arithmetic mean roughness Ra is measured in accordance with JIS B0601:1994.

(desmear processing)
Through holes may be formed in the cured product obtained by pre-curing the resin material. In the above-mentioned multilayer substrate, a via, a through hole, or the like is formed as a through hole. For example, vias can be formed by irradiation with a laser such as a CO ₂ laser. The diameter of the via is not particularly limited, but is approximately 60 μm to 80 μm. Due to the formation of the above-described through holes, a smear, which is a resin residue derived from a resin component contained in the cured product, is often formed at the bottom of the via.

In order to remove the smear, the surface of the cured product is preferably subjected to a desmear treatment. Desmear treatment may also serve as roughening treatment.

Similar to the roughening treatment, the desmear treatment uses, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound, or a persulfate compound. These chemical oxidants are used as an aqueous solution or an organic solvent dispersion solution after water or an organic solvent is added. Desmear processing liquid used for desmear processing generally contains an alkali. It is preferable that the desmear treatment liquid contains sodium hydroxide.

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

Hereinafter, the present invention will be specifically explained by giving Examples and Comparative Examples. The invention is not limited to the following examples.

The following materials were prepared.

(First compound)
Alkylmaleimide compound represented by the following formula (1A) (trifunctional, molecular weight 840, synthesized according to Synthesis Example 1)

<Synthesis example 1>
26.1 g of tris(2-hydroxyethyl) isocyanurate and 65.0 g of 6-maleimidohexanoic acid were added to 200 mL of toluene, followed by 3 g of methanesulfonic acid and stirred. Next, reflux was performed for 3 hours using a reflux tube equipped with a Dean-Stark tube. Next, the organic layer was washed three times with 50 cc of water to obtain a washed organic layer. The solvent was distilled off from this organic layer to obtain an alkylmaleimide compound represented by the above formula (1A).

(Second compound)
N-alkyl bismaleimide compound having a skeleton derived from dimer diamine (molecular weight 7000, synthesized according to Synthesis Example 2)

<Synthesis example 2>
In a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas inlet tube, 26.7 g of bis(aminomethyl)norbornane (manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight 154.26) and dimer diamine (manufactured by Croda Japan Co., Ltd.) were added. 46.0 g of "PRIAMINE 1075"), 100 g of toluene, and 50 g of N-methyl-2-pyrrolidone were added, and the solution in the reaction vessel was heated to 60°C. Next, 55 g of pyromellitic dianhydride (manufactured by Tokyo Kasei Co., Ltd., molecular weight 254.15) was added to the reaction vessel, a Dean-Stark trap and a condenser were attached to the flask, and the mixture was heated to reflux for 4 hours. A reaction product having a diamine terminal was obtained. Next, 8.7 g of maleic anhydride was added, and the resulting mixture was further refluxed for 4 hours to perform maleimidation. Next, the organic layer was washed with pure water, and water was removed using an evaporator. Subsequently, reprecipitation was performed using methanol to obtain a maleimide compound having a skeleton derived from dimer diamine only at both ends of the main chain. The yield of maleimide compound was 80%.

(Third compound)
Aromatic bismaleimide compound (“BMI-80” manufactured by KI Kasei Co., Ltd.)

(epoxy compound)
Biphenyl type epoxy compound (“NC-3000” manufactured by Nippon Kayaku Co., Ltd.)
Naphthalene type epoxy compound (“ESN-475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
Resorcinol diglycidyl ether (“EX-201” manufactured by Nagase ChemteX)
Hyperbranched aliphatic epoxy compound (“FoldiE101” manufactured by Nissan Chemical Co., Ltd.)
Epoxy compound with butadiene skeleton (“PB3600” manufactured by Daicel Corporation)

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

(hardening agent)
Liquid containing active ester compound 1 (“EXB-9416-70BK” manufactured by DIC, solid content 70% by weight)
Active ester compound 2-containing liquid (“HPC-8150-62T” manufactured by DIC, solid content 62% by weight)
Phenol compound-containing liquid (“LA-1356” manufactured by DIC, solid content 60% by weight)

(hardening accelerator)
Dimethylaminopyridine (“DMAP” manufactured by Wako Pure Chemical Industries, Ltd.)
2-phenyl-4-methylimidazole (“2P4MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd., anionic curing accelerator)

(Thermoplastic resin)
Polyimide compound (polyimide resin, molecular weight 20,000, synthesized according to Synthesis Example 3)

<Synthesis example 3>
300.0 g of tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan LLC) and 665.5 g of cyclohexanone were placed in a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube. The solution in the reaction vessel was heated to 60°C. Next, 89.0 g of dimer diamine ("PRIAMINE1075" manufactured by Croda Japan) and 54.7 g of 1,3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Company) were added dropwise into the reaction vessel. Next, 121.0 g of methylcyclohexane and 423.5 g of ethylene glycol dimethyl ether were added into the reaction vessel, and an imidization reaction was carried out at 140° C. for 10 hours. In this way, a polyimide compound-containing solution (nonvolatile content: 26.8% by weight) was obtained. The molecular weight (weight average molecular weight) of the obtained polyimide compound was 20,000. Note that the molar ratio of acid component/amine component was 1.04.

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

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

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

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

(evaluation)
(1) Thermal dimensional stability (average coefficient of linear expansion (CTE))
The resulting resin film (B stage film) with a thickness of 40 μm was heated at 190° C. for 90 minutes, and the resulting cured product was cut into a size of 3 mm×25 mm. Using a thermomechanical analysis device ("EXSTAR TMA/SS6100" manufactured by SII Nanotechnology), the cured product was cut at 25 to 150 °C under the conditions of a tensile load of 33 mN and a temperature increase rate of 5 °C/min. The average coefficient of linear expansion (ppm/°C) was calculated.

[Judgment criteria for average linear expansion coefficient]
○○: Average linear expansion coefficient is 26 ppm/℃ or less ○: Average linear expansion coefficient exceeds 26 ppm/℃ and 30 ppm/℃ or less ×: Average linear expansion coefficient exceeds 30 ppm/℃

(2) Elongation properties The obtained resin film (B stage film) with a thickness of 40 μm was heated at 190° C. for 90 minutes, and the obtained cured product was cut into a size of 10 mm×100 mm. The maximum elongation was measured using a tensile tester ("AGS-J 100N" manufactured by SHIMADZU) under conditions of a distance between chucks of 60 mm and a tensile speed of 5 mm/min. The initial tension was 0.35N. The measurement was repeated five times, and the average value of elongation at break (average elongation at break) was calculated.

[Judgment criteria for elongation properties]
○○: Average elongation at break is 2.0% or more ○: Average elongation at break is 1.5% or more and less than 2.0% ×: Average elongation at break is less than 1.5%

(3) Bending properties (repetitive bendability)
The resulting resin film (B stage film) with a thickness of 40 μm was heated at 190° C. for 90 minutes, and the resulting cured product was cut into a size of 30 mm×150 mm. A folding test was conducted using a sheet U-shaped folding tester (manufactured by Yuasa Corporation) under the conditions of 200 times/min, 180°C folding (bending gap 5 mm), and film stroke 70 mm. The measurement was repeated 5 times and the average value was calculated.

[Judgment criteria for bending properties (repetitive bendability)]
○○: No cracking after 2000 bends ○: Cracking after 100 or more bends but less than 2000 times ×: Cracking after bending less than 100 times

(4) Dielectric loss tangent (Df)
The obtained resin film was heated at 190° C. for 90 minutes to obtain a cured product. The obtained cured product was cut into pieces 2 mm wide and 80 mm long, and 10 pieces were stacked on top of each other. The dielectric loss tangent was measured at room temperature (23° C.) and a frequency of 5.8 GHz using a cavity resonance method using “Network Analyzer N5224A PNA”.

[Judgment criteria for dielectric loss tangent]
○: Dielectric loss tangent is less than 2.7×10 ⁻³ ×: Dielectric loss tangent is 2.7×10 ⁻³ or more

(5) Desmear property (removability of residue at via bottom)
Lamination/semi-curing treatment:
The obtained resin film was vacuum laminated on a CCL substrate (“E679FG” manufactured by Hitachi Chemical Co., Ltd.) and heated at 180° C. for 30 minutes to semi-cure it. In this way, a laminate A was obtained in which a semi-cured resin film was laminated on a CCL substrate.

Via (through hole) formation:
A via (through-hole) with a diameter of 60 μm at the upper end and 40 μm at the lower end (bottom) was formed into the semi-cured resin film of laminate A using a CO ₂ laser (manufactured by Hitachi Via Mechanics). holes) were formed. In this way, a laminate B was obtained in which a semi-cured resin film was laminated on a CCL substrate, and a via (through hole) was formed in the semi-cured resin film.

Removal of residue at the bottom of vias:
(a) Swelling treatment The obtained laminate B was placed in a 60° C. swelling liquid (“Swelling Dip Securigant P” manufactured by Atotech Japan) and rocked for 10 minutes. Thereafter, it was washed with pure water.

(b) Permanganate treatment (roughening treatment and desmear treatment)
The laminate B after the swelling treatment was placed in a roughened aqueous solution of potassium permanganate ("Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd.) at 80° C., and the mixture was shaken for 30 minutes. Next, after processing for 2 minutes using a 25° C. cleaning solution (“Reduction Securigant P” manufactured by Atotech Japan), the sample was washed with pure water to obtain an evaluation sample.

The bottom of the via of the evaluation sample was observed using a scanning electron microscope (SEM), and the maximum smear length from the wall of the via bottom was measured. The removability of the residue on the bottom of the via was evaluated based on the following criteria.

[Determination criteria for desmear property (removability of residue at the bottom of via)]
○○: Maximum smear length is less than 1 μm ○: Maximum smear length is 1 μm or more and less than 3 μm ×: Maximum smear length is 3 μm or more

(6) Surface roughness after etching (surface roughness)
Lamination process and semi-curing process:
A double-sided copper-clad laminate (CCL board) (“E679FG” manufactured by Hitachi Chemical) was prepared. Both sides of the copper foil side of this double-sided copper-clad laminate were immersed in "Cz8101" manufactured by MEC Corporation to roughen the surface of the copper foil. Both sides of the roughened copper clad laminate are coated with the resin film (B stage film) side of the laminate film on the copper clad laminate using Meiki Seisakusho's "Batch Vacuum Laminator MVLP-500-IIA". These were stacked and laminated to obtain a laminated structure. The lamination conditions were that the pressure was reduced to 13 hPa or less by reducing the pressure for 30 seconds, and then pressing was performed for 30 seconds at 100° C. and a pressure of 0.4 MPa. Thereafter, the resin film was semi-cured by heating at 180° C. for 30 minutes. In this way, a laminate in which a semi-cured resin film was laminated on a CCL substrate was obtained.

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

(b) Permanganate treatment (roughening treatment and desmear treatment):
The laminate after the swelling treatment was placed in a roughened aqueous solution of potassium permanganate ("Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd.) at 80° C. and rocked for 30 minutes. Next, after processing for 2 minutes using a 25° C. cleaning solution (“Reduction Securigant P” manufactured by Atotech Japan), the sample was washed with pure water to obtain an evaluation sample.

Surface roughness measurement:
On the surface of the evaluation sample (cured material subjected to roughening treatment), 10 areas of 94 μm x 123 μm were arbitrarily selected. For each of these 10 regions, the arithmetic mean roughness Ra was measured using a non-contact three-dimensional surface shape measuring device ("WYKO NT1100" manufactured by Veeco). Note that the arithmetic mean roughness Ra was measured in accordance with JIS B0601:1994.

[Judgment criteria for surface roughness after etching]
○: The average value of the arithmetic mean roughness Ra is less than 70 nm △: The average value of the arithmetic mean roughness Ra is 70 nm or more and less than 150 nm ×: The average value of the arithmetic mean roughness Ra is 150 nm or more

(6) Plating peel strength Lamination process and semi-hardening treatment:
A 100 mm square double-sided copper-clad laminate (CCL substrate) (“E679FG” manufactured by Hitachi Chemical) was prepared. Both sides of the copper foil side of this double-sided copper-clad laminate were immersed in "Cz8101" manufactured by MEC Corporation to roughen the surface of the copper foil. Using Meiki Seisakusho's "Batch Type Vacuum Laminator MVLP-500-IIA", place the resin film (B stage film) side of the laminated film on both sides of the roughened copper clad laminate. These were stacked and laminated to obtain a laminated structure. The lamination conditions were as follows: reduce the pressure for 30 seconds to bring the atmospheric pressure below 13 hPa, then laminate at 100°C and 0.7 MPa for 30 seconds, and then press for 60 seconds at a press pressure of 0.8 MPa and a press temperature of 100°C. . Thereafter, with the PET film attached, the resin film in the laminated structure was heated at 100°C for 30 minutes, and then further heated at 180°C for 30 minutes to semi-cure the resin film. Thereafter, the PET film was peeled off to obtain a laminate in which a semi-cured resin film was laminated on a CCL substrate.

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

(b) Permanganate treatment (roughening treatment and desmear treatment):
The laminate after the swelling treatment was placed in a roughened aqueous solution of potassium permanganate ("Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd.) at 80° C., and was shaken for 30 minutes. Next, after processing for 2 minutes using a 25° C. cleaning solution (“Reduction Securigant P” manufactured by Atotech Japan), it was washed with pure water and roughened.

Electroless plating process:
The surface of the obtained roughened cured product was treated with an alkaline cleaner ("Cleaner Securigant 902" manufactured by Atotech Japan Co., Ltd.) at 60° C. for 5 minutes to degrease and wash. After washing, the cured product was treated with a 25° C. pre-dip solution (“Pre-dip Neogant B” manufactured by Atotech Japan) for 2 minutes. Thereafter, the cured product was treated with a 40° C. activator solution (“Activator Neogant 834” manufactured by Atotech Japan Co., Ltd.) for 5 minutes to attach a palladium catalyst. Next, the cured product was treated with a 30° C. reducing solution (“Reducer Neogant WA” manufactured by Atotech Japan) for 5 minutes.

Next, the cured product was placed in a chemical copper solution (“Basic Print Gant MSK-DK”, “Copper Print Gant MSK”, “Stabilizer Print Gant MSK”, and “Reducer Cu” manufactured by Atotech Japan), and electroless plating was performed. This was carried out until the plating thickness was approximately 0.5 μm. After electroless plating, annealing treatment was performed at a temperature of 120° C. for 30 minutes to remove residual hydrogen gas. All steps up to the electroless plating step were carried out using a beaker scale with a treatment liquid of 2 L and shaking the cured product.

Electroplating treatment:
Next, electrolytic plating was performed on the cured product subjected to electroless plating until the plating thickness reached 25 μm. For electrolytic copper plating, copper sulfate solution ("Copper sulfate pentahydrate" manufactured by Wako Pure Chemical Industries, Ltd., "Sulfuric acid" manufactured by Wako Pure Chemical Industries, Ltd., "Basic Leveler Caparacid HL" manufactured by Atotech Japan, "Basic Leveler Caparacid HL" manufactured by Atotech Japan) Electrolytic plating was carried out using a correcting agent Caparaside GS) by flowing a current of 0.6 A/cm ² until the plating thickness became approximately 25 μm. After the copper plating treatment, the cured product was heated at 200° C. for 60 minutes to further harden the cured product. In this way, a cured product having a copper plating layer laminated on the upper surface was obtained.

Measurement of plating peel strength:
A total of six strip-shaped incisions each having a width of 10 mm were made at 5 mm intervals on the surface of the copper plating layer of the cured product on which the obtained copper plating layer was laminated. Set the cured product with the copper plating layer laminated on the top surface in a 90° peel tester (TE-3001 manufactured by Tester Sangyo Co., Ltd.), pick up the notched end of the copper plating layer with a grip, and remove the copper. The plating layer was peeled off by 20 mm and the peel strength (plating peel strength) was measured. The peel strength (plating peel strength) was measured for each of the six cut locations, and the average value of the plating peel strength was determined. Plating peel strength was evaluated using the following criteria.

[Judgment criteria for plating peel strength]
○○: The average value of plating peel strength is 0.5 kgf/cm or more ○: The average value of plating peel strength is 0.45 kgf/cm or more and less than 0.5 kgf/cm △: The average value of plating peel strength is 0.35 kgf/cm cm or more and less than 0.45 kgf/cm ×: Average value of plating peel strength is less than 0.35 kgf/cm

The composition and results are shown in Table 1 below.

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

Claims (15)

comprising the following first compound,
A resin material containing at least one of the following second compound and the following third compound.
First compound: an alkylmaleimide compound having a molecular weight of less than 1500 and having trifunctional or higher functionality
Second compound: a maleimide compound with a molecular weight of 1500 or more, or a benzoxazine compound with a molecular weight of 1500 or more Third compound: aromatic bismaleimide compound The resin material according to claim 1 , wherein the first compound has an ester bond. The resin material according to claim 1 or 2 , wherein the first compound has an isocyanuric acid skeleton. The resin material according to any one of claims 1 to 3 , comprising the second compound. The resin material according to claim 4 , wherein the second compound is an alkylmaleimide compound having a molecular weight of 1500 or more. The resin material according to claim 4 or 5 , wherein the second compound has an imide skeleton. The resin material according to any one of claims 4 to 6 , wherein the second compound has a molecular weight of 50,000 or less. The resin material according to any one of claims 4 to 7 , wherein the second compound has a skeleton derived from dimer diamine. The resin material according to any one of claims 4 to 8 , wherein the second compound has a cyclohexyl ring skeleton. The resin material according to any one of claims 1 to 9 , comprising the third compound. The resin material according to any one of claims 1 to 10 , comprising an epoxy compound. Contains a hardening agent,
The resin material according to any one of claims 1 to 11 , wherein the curing agent contains an active ester compound. The resin material according to any one of claims 1 to 12 , which is a resin film. The resin material according to any one of claims 1 to 13 , which is used for forming an insulating layer in a multilayer printed wiring board. a circuit board;
a plurality of insulating layers disposed on the surface of the circuit board;
a metal layer disposed between the plurality of insulating layers,
A multilayer printed wiring board, wherein at least one of the plurality of insulating layers is a cured product of the resin material according to any one of claims 1 to 14 .

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