KR20240004223A - Resin materials and multilayer printed wiring boards - Google Patents

Abstract

1) The dielectric loss tangent of the cured product can be lowered, 2) Smear can be effectively removed by desmear treatment, 3) The plating peel strength can be increased, and 4) The notch in the cured material layer at the end of the substrate can be reduced. A resin material that can make it difficult to produce is provided. The resin material according to the present invention includes an epoxy compound, a filler, and a curing agent, the filler has an average particle diameter of 2.0 μm or less, and the curing agent has a carbonate structure and a first curing agent having a functional group capable of reacting with an epoxy group. Includes.

Description

Resin materials and multilayer printed wiring boards

The present invention relates to a resin material containing an epoxy compound. Additionally, the present invention relates to a multilayer printed wiring board using the above resin material.

Conventionally, various resin materials have been used to obtain electronic components such as semiconductor devices, laminated boards, and printed wiring boards. For example, in multilayer printed wiring boards, resin materials are used to form an insulating layer to insulate the internal layers or to form an insulating layer located in the surface layer. Wiring, generally made of metal, is laminated on the surface of the insulating layer. Additionally, in order to form the insulating layer, a resin film in which the resin material is formed into a film may be used. The resin material and the resin film are used as an insulating material for a multilayer printed wiring board including a build-up film, etc.

Patent Document 1 below discloses a resin composition containing (A) an epoxy resin, (B) a polymer compound, (C) a fluorine atom-containing alkoxysilane compound, and (D) an inorganic filler. In this resin composition, the polymer compound (B) has a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarboxylic structure. It is a polymer compound having one or more structures selected from the bonate structure.

Patent Document 2 below discloses a resin composition containing (A) a resin having an aliphatic polycarbonate skeleton and (B) an inorganic and/or organic filler.

Japanese Patent Publication No. 2018-150440 Japanese Patent Publication No. 2007-284555

In conventional resin materials designed to lower the dielectric loss tangent of the cured product, there are cases where smear cannot be effectively removed by desmear treatment or the plating peel strength to the metal layer cannot be increased.

Additionally, in substrates that require a low dielectric loss tangent, the size and multilayering are progressing, and the weight of the substrate is becoming heavier. Along with this, notches are more likely to occur in the cured material layer at the end of the substrate when handling and transporting the substrate.

However, the above-mentioned patent documents 1 and 2 describe a resin material containing a resin having a polycarbonate structure. However, the resin having a polycarbonate structure described in Patent Documents 1 and 2 is not a curing agent. If a resin having a polycarbonate structure as described in Patent Documents 1 and 2 is used, the dielectric loss tangent of the cured product can be reduced to some extent. However, even when a resin having a polycarbonate structure is used, desmearability may decrease or notches may occur in the cured layer at the end of the substrate.

The purpose of the present invention is to 1) lower the dielectric loss tangent of the cured product, 2) effectively remove smear by desmear treatment, 3) increase the plating peel strength, and 4) reduce the dielectric loss tangent of the cured product at the end of the substrate. The object is to provide a resin material that can make it difficult to generate notches in the layer. Furthermore, the present invention also aims to provide a multilayer printed wiring board using the above resin material.

According to a broad aspect of the present invention, a first curing agent comprising an epoxy compound, a filler, and a curing agent, wherein the filler has an average particle diameter of 2.0 μm or less, and wherein the curing agent has a carbonate structure and has a functional group capable of reacting with an epoxy group. A resin material comprising:

In a specific aspect of the resin material according to the present invention, the content of the filler is 50% by weight or more and 90% by weight or less among 100% by weight of components excluding the solvent in the resin material.

In a specific aspect of the resin material according to the present invention, the molecular weight of the first curing agent is 20000 or less.

In certain aspects of the resin material according to the present invention, the curing agent includes a second curing agent that does not have a carbonate structure.

In certain aspects of the resin material according to the present invention, the second curing agent contains an active ester compound.

In a specific aspect of the resin material according to the present invention, the resin material includes a polyimide resin.

In a specific 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 to form an insulating layer in a multilayer printed wiring board.

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

The resin material according to the present invention includes an epoxy compound, a filler, and a curing agent, the filler has an average particle diameter of 2.0 μm or less, and the curing agent has a carbonate structure and a first curing agent having a functional group capable of reacting with an epoxy group. Includes. Since the resin material according to the present invention has the above configuration, 1) the dielectric loss tangent of the cured product can be lowered, 2) smear can be effectively removed by desmear treatment, and 3) plating peel strength can be increased. 4) It can be difficult to cause notches in the cured layer at the end of the substrate.

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

Hereinafter, the details of the present invention will be described.

The resin material according to the present invention includes an epoxy compound, a filler, and a curing agent, the filler has an average particle diameter of 2.0 μm or less, and the curing agent has a carbonate structure and a first curing agent having a functional group capable of reacting with an epoxy group. Includes.

Since the resin material according to the present invention has the above configuration, 1) the dielectric loss tangent of the cured product can be lowered, 2) smear can be effectively removed by desmear treatment, and 3) plating peel strength can be increased. and 4) it is possible to exert all of the effects of 1) to 4), which can make it difficult to generate notches in the cured material layer at the end of the substrate.

In the resin material according to the present invention, the curing agent has a carbonate structure and includes a first curing agent having a functional group capable of reacting with an epoxy group, so that when the resin material is cured, the carbonate structure in the first curing agent is hardened. It is difficult to phase separate in cargo. Therefore, since a uniform cured product is obtained, it is possible to make it difficult to cause notches in the cured product layer at the end of the substrate. In addition, in the resin material according to the present invention, since the curing agent contains the first curing agent, the first curing agent and the epoxy compound are uniformly crosslinked, and the smear that occurs after the formation of the through hole is uniformly treated by desmear treatment. Since it can be etched easily, smears can be effectively removed. In addition, in the resin material according to the present invention, since the curing agent contains the first curing agent, it is possible to prevent the smear from being partially excessively etched by phase separation of the carbonate structure, and thus the plating peel strength can be increased. .

In addition, in the resin material according to the present invention, since the average particle diameter of the filler is 2.0 μm or less, the first curing agent and the epoxy compound are uniformly crosslinked even in the vicinity of the filler, so that there is no notch in the cured material layer at the end of the substrate. can make it difficult to generate. As a result, smears can be removed even more efficiently.

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 paste form. The paste phase includes a liquid phase. From the viewpoint of excellent handling properties, it is preferable that the resin material according to the present invention is a resin film.

It is preferable that the resin material according to the present invention is a thermosetting resin 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.

[Epoxy compound]

The resin material includes an epoxy compound. As the epoxy compound, a conventionally known epoxy compound can be used. The epoxy compound is an organic compound having at least one epoxy group. Only one type of the said epoxy compound may be used, and two or more types may be used together.

Examples of the 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, Naphthalene type epoxy compound, fluorene type epoxy compound, phenol aralkyl type epoxy compound, naphthol aralkyl type epoxy compound, dicyclopentadiene type epoxy compound, anthracene type epoxy compound, epoxy compound with adamantane skeleton, tricyclodecane Examples include epoxy compounds having a skeleton, naphthylene ether type epoxy compounds, and epoxy compounds having a triazine nucleus in the 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 retardancy of the cured product, the epoxy compound preferably contains an epoxy compound having an aromatic skeleton, and an epoxy compound having a naphthalene skeleton or a phenyl skeleton. It is more desirable to include it.

From the viewpoint of further lowering the dielectric loss tangent of the cured product, the epoxy compound preferably contains a liquid epoxy compound at 25°C and a solid epoxy compound at 25°C.

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

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

The molecular weight of the epoxy compound is preferably 1000 or less. In this case, even if the filler content is 50% by weight or more out of 100% by weight of components excluding the solvent in the resin material, a resin material with high fluidity can be obtained when forming an insulating layer. For this reason, when the uncured product or B-stage product of the resin material is laminated on a circuit board, the filler can be uniformly present. “100% by weight of the component excluding the solvent in the resin material” means “100% by weight of the component excluding the solvent in the resin material” when the resin material contains a solvent. , means “100% by weight of resin material.”

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

The content of the epoxy compound in 100% by weight of components excluding the solvent in the resin material is preferably 5% by weight or more, more preferably 10% by weight or more, preferably 25% by weight or less, more preferably 20% by weight. It is less than % by weight. If the content of the epoxy compound is more than the above lower limit and less than the above upper limit, the effects of 1) to 4) above can be exhibited even more effectively.

Among 100% by weight of components excluding fillers and solvents in the resin material, the content of the epoxy compound is preferably 15% by weight or more, more preferably 25% by weight or more, further preferably 35% by weight or more, preferably 35% by weight or more. is 60% by weight or less. If the content of the epoxy compound is more than the lower limit and less than the upper limit, the effects of 1) to 4) can be achieved more effectively.

[Hardener]

The resin material contains a curing agent. From the viewpoint of exerting the effects of 1) to 4), the curing agent includes a first curing agent that has a carbonate structure and a functional group capable of reacting with an epoxy group. The curing agent may or may not contain a second curing agent that does not have a carbonate structure.

<First hardener>

The first curing agent is a compound (curing agent) that has a carbonate structure and a functional group capable of reacting with an epoxy group. The first curing agent has a carbonate structure (-O-C(=O)-O-). The first curing agent has a functional group capable of reacting with an epoxy group. The first curing agent has a functional group that can react with the epoxy group of the epoxy compound. As for the said 1st hardening|curing agent, only 1 type may be used, and 2 or more types may be used together.

Examples of the functional group capable of reacting with the epoxy group include amino group, hydroxyl group, active ester group, cyanate ester group, carbodiimide group, maleimide group, and benzoxazine group.

From the viewpoint of further lowering the dielectric loss tangent of the cured product, it is preferable that the functional group capable of reacting with the epoxy group is a maleimide group, a hydroxyl group, or an active ester group.

From the viewpoint of further lowering the dielectric loss tangent of the cured product, it is preferable that the first curing agent has an aliphatic ring. From the viewpoint of increasing the heat resistance of the cured product, it is preferable that the first curing agent has an aromatic ring. From the viewpoint of further lowering the dielectric loss tangent of the cured product and increasing the heat resistance of the cured product, it is preferable that the first curing agent has an aliphatic ring and an aromatic ring.

The first curing agent preferably has a phenol structure or an active ester structure.

In addition, the active ester structure is, for example, a structure represented by the following formula (10A).

In the above formula (10A), R1 represents an aliphatic chain, an aliphatic ring, or an aromatic ring, and R2 represents an aromatic ring.

From the viewpoint of exhibiting the effects of 1) to 4) in a good balance, the first curing agent preferably contains a phenol carbonate compound (a compound having a carbonate structure and a phenol structure), and the phenol carbonate It is more preferable that it is a compound (a compound having a carbonate structure and a phenol structure). In particular, the effect of the phenol carbonate compound (3) above can be exhibited more effectively by using a compound having a carbonate structure and a phenol structure.

From the viewpoint of exhibiting the effects of 1) to 4) in a good balance, the first curing agent is preferably a compound represented by the following formula (3).

In the above formula (3), X1 and In the above formula (3), X1 and X2 may be the same or different. In the above formula (3), R2 and R3 may be the same or different. In the above formula (3), n may represent an integer of 500 or less, may represent an integer of 200 or less, may represent an integer of 100 or less, or may represent an integer of 50 or less. In the above formula (3), n preferably represents an integer at which the molecular weight of the first curing agent is 2000 or more. In the above formula (3), n preferably represents an integer at which the molecular weight of the first curing agent is 20000 or less.

From the viewpoint of more effectively demonstrating the effects of 1), 2), and 4), especially the effect of 1), the first curing agent is an active ester carbonate compound (a compound having a carbonate structure and an active ester structure). ) is preferably included. From the viewpoint of more effectively demonstrating the effects of 1), 2), and 4), especially the effect of 1), the first curing agent is an active ester carbonate compound (a compound having a carbonate structure and an active ester structure). ) is more preferable.

The molecular weight of the first curing agent is preferably 2000 or more, more preferably 3000 or more, preferably 20000 or less, and more preferably 15000 or less. If the molecular weight of the first curing agent is equal to or greater than the lower limit and equal to or lower than the upper limit, the effects of 1) to 4) can be achieved even more effectively.

When the structural formula of the first curing agent can be specified, the molecular weight of the first curing agent means the molecular weight that can be calculated from the structural formula. In addition, when the first curing agent is a polymer, it means the weight average molecular weight calculated in terms of polystyrene measured by gel permeation chromatography (GPC).

The glass transition temperature of the first curing agent is preferably 30°C or higher, more preferably 50°C or higher, preferably 150°C or lower, and more preferably 120°C or lower. If the glass transition temperature of the first curing agent is more than the above lower limit, the plating peeling strength can be further increased. If the glass transition temperature of the first curing agent is below the upper limit, the curability of the resin material can be further improved, and the dielectric loss tangent of the cured product can be further improved.

Commercially available products of the first curing agent include, for example, “FTC509” and “FTC509ES” manufactured by Kunei Chemicals, and “T6002” and “T6001” manufactured by Asahi Chemicals.

Among 100% by weight of the curing agent, the content of the first curing agent is preferably 10% by weight or more, more preferably 20% by weight or more, preferably 60% by weight or less, and more preferably 55% by weight or less. If the content of the first curing agent is more than the above lower limit, the above effects 1) and 2) can be exhibited even more effectively. If the content of the first curing agent is below the upper limit, the effects of 3) and 4) can be achieved even more effectively.

The content of the first curing agent relative to 100 parts by weight of the epoxy compound is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, preferably 70 parts by weight or less, more preferably 60 parts by weight or less. . If the content of the first curing agent is more than the lower limit and less than the upper limit, the effects of 1) to 4) can be achieved even more effectively.

Among 100% by weight of components excluding the solvent in the resin material, the content of the first curing agent is preferably 0.5% by weight or more, more preferably 1% by weight or more, preferably 20% by weight or less, and more preferably 15% by weight. It is less than % by weight. If the content of the first curing agent is more than the lower limit and less than the upper limit, the effects of 1) to 4) can be achieved more effectively.

Among 100% by weight of components excluding fillers and solvents in the resin material, the content of the first curing agent is preferably 2.5% by weight or more, more preferably 5% by weight or more, preferably 35% by weight or less, more preferably is 30% by weight or less. If the content of the first curing agent is more than the lower limit and less than the upper limit, the effects of 1) to 4) can be achieved more effectively. “100% by weight of components in the resin material excluding fillers and solvents” means “100% by weight of components in the resin material excluding fillers and solvents” when the resin material contains a solvent. In cases where it is not specified, it means “100% by weight of components excluding fillers in the resin material.”

<Second hardener>

The second curing agent is a compound (curing agent) that does not have a carbonate structure. The curing agent preferably includes the second curing agent. As for the said 2nd hardening|curing agent, only 1 type may be used, and 2 or more types may be used together.

The second curing agent preferably has a functional group capable of reacting with an epoxy group. The second curing agent preferably has a functional group capable of reacting with the epoxy group of the epoxy compound.

Examples of the second curing agent include active ester compounds, phenol compounds (phenol curing agents), cyanate ester compounds (cyanate ester curing agents), carbodiimide compounds (carbodiimide curing agents), oxazoline compounds, maleimide compounds, and benzoxazine. Examples include compounds (benzoxazine curing agent), amine compounds (amine curing agents), thiol compounds (thiol curing agents), phosphine compounds, dicyandiamide, and acid anhydrides.

The second curing agent preferably contains an active ester compound, a phenol compound, a cyanate ester compound, a carbodiimide compound, an oxazoline compound, or a maleimide compound, and more preferably contains an active ester compound or a phenol compound, It is more preferred that it contains an active ester compound. In this case, the dielectric loss tangent of the cured product can be further lowered, and the thermal dimensional stability of the cured product can be further improved. From the viewpoint of further lowering the dielectric loss tangent of the cured product, it is preferable that the second curing agent contains an active ester compound. From the viewpoint of further increasing the plating peeling strength, it is preferable that the second curing agent contains a phenol compound.

Active ester compounds:

The active ester compound refers to a compound that contains at least one ester bond in the 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 of a carboxylic acid compound or thiocarboxylic acid compound and a hydroxy compound or thiol compound. Examples of active ester compounds include compounds represented by the following formula (1). As for the said active ester compound, only 1 type may be used, and 2 or more types may be used together.

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 that may have a substituent, a naphthalene ring that may have a substituent, etc. Examples of the substituent include a hydrocarbon group. The carbon number of the hydrocarbon group is preferably 12 or less, more preferably 6 or less, and still more preferably 4 or less.

In the formula (1), examples of the combination of X1 and there is. In addition, 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 active ester compound is not particularly limited. From the viewpoint of further improving the thermal dimensional stability and flame retardancy of the cured product, the active ester compound is preferably an active ester compound having two or more aromatic rings. 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 the main chain skeleton.

Commercially available products of the active ester compound include "HPC-8000-65T", "EXB9416-70BK", and "HPC8150-62T" manufactured by DIC.

Phenolic compounds:

Examples of the phenolic compounds include novolak-type phenol, biphenol-type phenol, naphthalene-type phenol, dicyclopentadiene-type phenol, aralkyl-type phenol, and dicyclopentadiene-type phenol. Only one type of the said phenol compound may be used, and two or more types may be used together.

Commercially available products of the above phenolic compounds include novolac-type phenol (“TD-2091” manufactured by DIC), biphenyl novolac-type phenol (“MEH-7851” manufactured by Meiwa Chemical Company), and aralkyl-type phenol compound (manufactured by Meiwa Chemical Company). “MEH-7800”), and phenol having an aminotriazine skeleton (“LA-1356” and “LA-3018-50P” manufactured by DIC).

Cyanate ester compound:

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

Commercially available products of the cyanate ester compound include phenol novolak-type cyanate ester resin (“PT-30” and “PT-60” manufactured by Lonza Japan), and a prepolymer in which bisphenol-type cyanate ester resin is trimerized (manufactured by Lonza Japan). “BA-230S”, “BA-3000S”, “BTP-1000S”, and “BTP-6020S”).

Carbodiimide Compounds:

The carbodiimide compound is a compound having a structural unit represented by the following formula (2). In the following formula (2), the right end and the left end are binding sites with other groups. Only one type of the said carbodiimide compound may be used, and two or more types may be used together.

In the formula (2), represents an integer from 1 to 5. When there are multiple Xs, the multiple Xs may be the same or different.

In one suitable form, at least one

Commercially available products of the carbodiimide compound include “Carbodilyte V-02B”, “Carbodilyte V-03”, “Carbodilyte V-04K”, “Carbodilyte V-07”, and “Carbodilyte V-07” manufactured by Nisshinbo Chemical Co., Ltd. Carbodelight V-09”, “Carbodelight 10M-SP” and “Carbodelight 10M-SP (Correct)”, and “Starvaczol P”, “Starvaczol P400” and “Hycadil” manufactured by Line Chemistry. 510” and the like.

Maleimide compounds:

Examples of the maleimide compound include N-phenylmaleimide and N-alkylbismaleimide. The maleimide compound may be a bismaleimide compound. As for the said maleimide compound, only 1 type may be used, and 2 or more types may be used together.

The maleimide compound may or may not have an aromatic ring. The maleimide compound preferably has an aromatic ring.

In the maleimide compound, it is preferable that the nitrogen atom in the maleimide skeleton and the aromatic ring are bonded.

From the viewpoint of effectively exhibiting the effect of the present invention, the molecular weight of the maleimide compound is preferably 500 or more, more preferably 1000 or more, preferably less than 30,000, and more preferably less than 20,000.

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

Commercially available products of the maleimide compound include, for example, “BMI-4000” and “BMI-5100” manufactured by Daiwa Kasei Industries, Ltd., and “BMI-3000” manufactured by Designer Molecules Inc.

Benzoxazine Compound:

Examples of the benzoxazine compounds include P-d type benzoxazine and F-a type benzoxazine. Only one type of the said benzoxazine compound may be used, and two or more types may be used together.

Commercially available products of the benzoxazine compound include "P-d type" manufactured by Shikoku Kasei Industries, Ltd., and the like.

Acid anhydride:

Examples of the acid anhydride include tetrahydrophthalic anhydride and alkyl styrene-maleic anhydride copolymer. Only one type of the said acid anhydride may be used, and two or more types may be used together.

Commercially available products of the acid anhydride include “Likacid TDA-100” manufactured by Nippon Rika Co., Ltd.

The content of the second curing agent relative to 100 parts by weight of the epoxy compound is preferably 40 parts by weight or more, more preferably 45 parts by weight or more, preferably 90 parts by weight or less, more preferably 85 parts by weight or less. . If the content of the second curing agent is more than the lower limit and less than the upper limit, the curability can be further improved, the thermal dimensional stability of the cured product can be further improved, and volatilization of remaining unreacted components can be further suppressed.

The content of the curing agent (the total content of the first curing agent and the second curing agent) relative to 100 parts by weight of the epoxy compound is preferably 80 parts by weight or more, more preferably 85 parts by weight or more, preferably 135 parts by weight. or less, more preferably 130 parts by weight or less. If the content of the curing agent is more than the lower limit and less than the upper limit, the curability can be further improved, the thermal dimensional stability of the cured product can be further improved, and volatilization of remaining unreacted components can be further suppressed.

Among 100% by weight of components excluding fillers and solvents in the resin material, the total content of the epoxy compound and the curing agent (the total content of the epoxy compound, the first curing agent, and the second curing agent) 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. If the total content is equal to or greater than the lower limit and equal to or lower than the upper limit, curability can be further improved and the thermal dimensional stability of the cured product can be further improved.

[filler]

The resin material includes filler. The average particle diameter of the filler is 2.0 μm or less. The filler may be an organic filler, an inorganic filler, or a mixture of an organic filler and an inorganic filler. Only one type of the above filler may be used, or two or more types may be used together.

Examples of the organic filler include benzoxazine resin particles, benzoxazole resin particles, fluorine resin particles, acrylic resin particles, and styrene resin particles. By using fluororesin particles as the organic filler, the dielectric constant of the cured product can be further lowered. As for the said organic filler, only 1 type may be used, and 2 or more types may be used together.

Examples of the inorganic filler include silica, talc, clay, mica, hydrotalcite, alumina, magnesium oxide, aluminum hydroxide, aluminum nitride, and boron nitride. As for the said inorganic filler, only one type may be used, and two or more types may be used together.

The filler is preferably an inorganic filler. In this case, the dielectric loss tangent of the cured product can be further lowered. Additionally, dimensional changes due to heat in the cured product can be further reduced.

The inorganic filler is preferably silica or alumina, more preferably silica, and even more preferably fused silica. In this case, the surface roughness of the surface of the cured product of the resin material is reduced, the adhesive strength between the cured product and the metal layer is further increased, further finer wiring is formed on the surface of the cured product, and the cured product provides good insulation reliability. can be granted. In particular, by using silica as a filler, the coefficient of thermal expansion of the cured product is further lowered, and the dielectric loss tangent of the cured product is further lowered. Additionally, the dielectric constant of the cured product can be improved. The shape of the silica is preferably spherical.

The inorganic filler is preferably spherical, and more preferably spherical silica. In this case, the surface roughness of the surface of the cured product is effectively reduced, and the adhesive strength between the cured product and the metal layer is effectively increased. Additionally, when the inorganic filler is spherical silica, curing of the resin can proceed regardless of the curing environment, effectively increase the glass transition temperature of the cured product, and effectively reduce the coefficient of thermal linear expansion of the cured product.

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 using a coupling agent, and even more preferably surface-treated using a silane coupling agent. By surface-treating the inorganic filler, the surface roughness of the surface of the roughened cured product becomes smaller, and the adhesive strength between the cured product and the metal layer further increases. In addition, by surface-treating the inorganic filler, finer wiring can be formed on the surface of the cured product, and better inter-wire insulation reliability and interlayer insulation reliability can be imparted to the cured product.

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

From the viewpoint of more effectively demonstrating the effects of 1) to 4), especially the effects of 2) and 4), the average particle diameter of the filler is 2.0 μm or less.

The average particle diameter of the filler is preferably 0.1 μm or more, more preferably 0.3 μm or more, preferably 1.8 μm or less, and more preferably 1.6 μm or less. If the average particle diameter of the filler is equal to or greater than the lower limit and equal to or less than the upper limit, the surface roughness after etching can be reduced, the plating peel strength can be increased, and the adhesion between the insulating layer and the metal layer can be improved. The average particle diameter of the filler may exceed 0.5 ㎛, 1.0 ㎛ or more, 1 ㎛ or less, less than 1 ㎛, 0.5 ㎛ or less, less than 0.5 ㎛, or 0.3 ㎛ or less.

When the filler is an inorganic filler, the average particle diameter of the inorganic filler is preferably 0.1 μm or more, more preferably 0.3 μm or more, preferably 1.8 μm or less, and more preferably 1.6 μm or less. If the average particle diameter of the inorganic filler is equal to or greater than the lower limit and equal to or less than the upper limit, the surface roughness after etching can be reduced, the plating peel strength can be increased, and the adhesion between the insulating layer and the metal layer can be improved. The average particle diameter of the inorganic filler may exceed 0.5 ㎛, 1.0 ㎛ or more, 1 ㎛ or less, less than 1 ㎛, 0.5 ㎛ or less, 0.5 ㎛ or less, or 0.3 ㎛ or less. .

When the filler is an organic filler, the average particle diameter of the organic filler is preferably 0.1 μm or more, more preferably 0.3 μm or more, preferably 1.8 μm or less, and more preferably 1.6 μm or less. If the average particle diameter of the organic filler is more than the above lower limit and less than the above upper limit, the surface roughness after etching can be reduced, the plating peel strength can be increased, and the adhesion between the insulating layer and the metal layer can be improved. The average particle diameter of the organic filler may exceed 0.5 ㎛, may be 1.0 ㎛ or more, may be 1 ㎛ or less, may be less than 1 ㎛, may be 0.5 ㎛ or less, may be less than 0.5 ㎛, or may be 0.3 ㎛ or less. .

As the average particle diameter of the filler (inorganic filler and organic filler), the value of the median diameter (d50) equal to 50% is adopted. It is preferable that the average particle diameter is the average particle diameter of primary particles. The average particle diameter can be measured using a laser diffraction scattering type particle size distribution measuring device.

Among 100% by weight of components excluding the solvent in the resin material, the content of the filler is preferably 50% by weight or more, more preferably 60% by weight or more, preferably 90% by weight or less, more preferably 85% by weight. or less, more preferably 80% by weight or less. If the content of the filler is more than the above lower limit, the dielectric loss tangent is effectively lowered. If the content of the filler is below the upper limit, the thermal dimensional stability of the cured product can be increased and warping of the cured product can be effectively suppressed. If the content of the filler is more than the above lower limit and less than the above upper limit, the surface roughness of the surface of the cured product can be further reduced, and further finer wiring can be formed on the surface of the cured product. Moreover, if the content of the filler is equal to or greater than the lower limit and equal to or lower than the upper limit, it is possible to lower the coefficient of thermal expansion of the cured product and improve smear removability.

[Curing accelerator]

The resin material preferably contains a curing accelerator. However, the resin material does not need to contain a curing accelerator. By using the curing accelerator, the curing speed is further accelerated. By quickly curing the resin material, the crosslinked structure in the cured product becomes uniform, the number of unreacted functional groups decreases, and as a result, the crosslinking density increases. The curing accelerator is not particularly limited, and conventionally known curing accelerators can be used. Only one type of the said hardening accelerator may be used, and two 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, curing accelerators other than anionic and cationic curing accelerators such as phosphorus compounds and organometallic compounds, and peroxides, etc. radical hardening accelerators, etc.

Examples of the imidazole compounds include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl. -4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole Sol, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyano Ethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1' )]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6 -[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1') ]-Ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid adduct, 2-methylimidazoleisocyanuric acid adduct, 2-phenyl-4,5-dihyde Roxymethylimidazole, 2-phenyl-4-methyl-5-dihydroxymethylimidazole, etc. are mentioned.

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

Examples of the phosphorus compound include triphenylphosphine compounds.

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

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

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

From the viewpoint of suppressing the curing temperature further lower and effectively suppressing bending of the cured product, the content of the anionic curing accelerator in 100 wt% of the curing accelerator is preferably 20 wt% or more, more preferably 50 wt% or more. , more preferably 70% by weight or more, and most preferably 100% by weight (total amount). Therefore, it is most preferable that the curing accelerator is the anionic curing accelerator.

The content of the curing accelerator is not particularly limited. Among 100% by weight of components excluding fillers and solvents in the resin material, the content of the curing accelerator is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, preferably 5% by weight or less, more preferably 3% by weight. It is less than % by weight. If the content of the curing accelerator is equal to or greater than the lower limit and equal to or lower than the 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 is further improved, and a better cured product is obtained.

[Thermosetting compounds other than epoxy compounds]

The resin material may or may not contain a thermosetting compound other than an epoxy compound. Only 1 type of thermosetting compound other than the said epoxy compound may be used, and 2 or more types may be used together.

Thermosetting compounds other than the epoxy compounds include vinyl compounds, styrene compounds, oxetane compounds, polyarylate compounds, diallyl phthalate compounds, acrylate compounds, episulfide compounds, (meth)acrylic compounds, amino compounds, and unsaturated polyesters. compounds, polyurethane compounds, and silicone compounds.

[Thermoplastic resin]

The resin material may contain a thermoplastic resin. Examples of the thermoplastic resin include polyimide resin, phenoxy resin, and polyvinyl acetal resin. Only one type of the said thermoplastic resin may be used, and two or more types may be used together.

From the viewpoint of effectively demonstrating the effect of the present invention, the thermoplastic resin is preferably a polyimide resin or a phenoxy resin, and more preferably a polyimide resin. From the viewpoint of effectively demonstrating the effect of the present invention, the resin material preferably contains polyimide resin or phenoxy resin, and more preferably contains polyimide resin. The resin material does not contain or contains polyimide resin. The resin material may contain polyimide resin or may not contain polyimide resin. The resin material does not contain or contains phenoxy resin. The resin material does not need to contain a phenoxy resin, and may contain a phenoxy resin.

From the viewpoint of more effectively exhibiting the effects of 1) to 4) above and from the viewpoint of improving handling properties, the thermoplastic resin is preferably a polyimide resin. The resin material preferably contains polyimide resin. When the resin material contains a polyimide resin, the resin material does not need to contain a phenoxy resin.

From the viewpoint of improving solubility, it is preferable that the polyimide resin is a polyimide resin obtained by a method of reacting tetracarboxylic dianhydride and dimer diamine.

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, and 3,3',4,4'-biphenyl sulfone tetracarboxylic acid. Boxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic Acid dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4- Furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride , 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4 ,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, Bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride and bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride.

Examples of the dimer diamine include Basamine 551 (brand name, BASF Japan, 3,4-bis(1-aminoheptyl)-6-hexyl-5-(1-octenyl)cyclohexene), and Basamine 552 ( Examples include brand name, Cognicus Japan Co., Ltd., hydrogenated product of Vasamine 551), PRIAMINE1075, and PRIAMINE1074 (brand name, both manufactured by Croda Japan Co., Ltd.).

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

From the viewpoint of effectively lowering the dielectric loss tangent regardless of the curing environment and effectively increasing adhesion to metal wiring, it is preferable that the thermoplastic resin contains a phenoxy resin. The resin material preferably contains a phenoxy resin. In addition, the use of the phenoxy resin suppresses the deterioration of the embedding properties of the resin film into holes or irregularities of the circuit board and the unevenness of the inorganic filler. In addition, by using a phenoxy resin, the melt viscosity can be adjusted, so the dispersibility of the inorganic filler improves, and it becomes difficult for the resin composition or B-stage product to spread to unintended areas during the curing process.

The phenoxy resin is not particularly limited. As the phenoxy resin, conventionally known phenoxy resins can be used. Only one type of the said phenoxy resin may be used, and two or more types may be used together.

Examples of the phenoxy resin include, for example, a phenoxy resin having a skeleton 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, etc. can be mentioned.

Commercially available products of the phenoxy resin include, for example, "YP50", "YP55", and "YP70" manufactured by Shin-Niptetsu Sumikin Chemicals, and "1256B40", "4250", "4256H40", and "4275" manufactured by Mitsubishi Chemical Corporation. , “YX6954BH30”, and “YX8100BH30”.

From the viewpoint of obtaining a resin film with even more excellent storage stability, the weight average molecular weight of the thermoplastic resin, the polyimide resin, and the phenoxy resin is preferably 5000 or more, more preferably 10000 or more, and preferably 100000 or less. , more preferably 50000 or less.

The weight average molecular weight of the thermoplastic resin, polyimide resin, and phenoxy resin means the weight average molecular weight measured by gel permeation chromatography (GPC) and converted to polystyrene.

The content of the thermoplastic resin, polyimide resin, and phenoxy resin is not particularly limited. The content of the thermoplastic resin (when the thermoplastic resin is a polyimide resin or a phenoxy resin, the content of the polyimide resin or phenoxy resin) in 100% by weight of the components excluding the filler and solvent in the resin material is preferably 1. It is % by weight or more, more preferably 2% by weight or more, preferably 30% by weight or less, and more preferably 20% by weight or less. If the content of the thermoplastic resin is more than the lower limit and less than the upper limit, the embedding properties of the resin film into holes or irregularities of the circuit board become good. If the content of the thermoplastic resin is more than the above lower limit, the formation of the resin film becomes easier and a better insulating layer is obtained. If the content of the thermoplastic resin is below the upper limit, the coefficient of thermal expansion of the cured product is further lowered. If the content of the thermoplastic resin is below the upper limit, the surface roughness of the surface of the cured product becomes smaller, and the adhesive strength between the cured product and the metal layer becomes higher.

[solvent]

The resin material does not contain or contains a solvent. The resin material may or may not contain a solvent. By using the above solvent, the viscosity of the resin material can be controlled to an appropriate range and the coatability of the resin material can be improved. Additionally, the solvent may be used to obtain a slurry containing the inorganic filler. Only one type of the said solvent may be used, and two or more types may be used together.

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

It is preferable that most of the solvent is removed when molding the resin composition into a film. Therefore, the boiling point of the solvent is preferably 200°C or lower, more preferably 180°C or lower. The content of the solvent in the resin composition is not particularly limited. Considering the coating properties of the resin composition, etc., the content of the solvent can be appropriately changed.

When the resin material is a B-stage film, the content of the solvent in 100% by weight of the B-stage film is preferably 0.5% by weight or more, more preferably 1% by weight or more, preferably 10% by weight or less, More preferably, it is 5% by weight or less.

[Other ingredients]

For the purpose of improving impact resistance, heat resistance, resin compatibility and workability, etc., the resin materials include leveling agents, flame retardants, coupling agents, colorants, antioxidants, UV deterioration inhibitors, anti-foaming agents, thickeners and thixotropy imparting agents. It may include .

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

(resin film)

A resin film (B stage cargo/B stage film) is obtained by molding the above-described resin composition into a film form. The resin material is preferably a resin film. It is preferable that the resin film is a B stage film.

Methods for obtaining a resin film by molding the 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 or circular die. A casting molding method in which a resin composition containing a solvent is cast and molded into a film. Other conventionally known film forming methods. Since it can accommodate thinning, the extrusion molding method or casting molding method is preferable. Film includes sheets.

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

The film-like resin composition obtained through the above-described drying process is called a B-stage film. The B stage film is in a semi-cured state. The semi-hardened product is not completely hardened, so hardening may proceed further.

The resin film does not need to be a prepreg. If the resin film is not a prepreg, migration does not occur depending on the glass cloth or the like. Additionally, when laminating or precuring the resin film, unevenness due to the glass cloth does not occur on the surface.

The resin film can be used in the form of a laminated film including a metal foil or base film and a resin film laminated on the surface of the metal foil or base film. The metal foil is preferably 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 release treatment as needed.

From the viewpoint of controlling the curing degree of the resin film more uniformly, the thickness of the resin film is preferably 5 μm or more, and preferably 200 μm or less. When using the resin film as an insulating layer of a circuit, the thickness of the insulating layer formed by 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 materials)

The resin material is temporarily cured by heating at 130°C for 60 minutes, and then heated at 200°C for 90 minutes to obtain a cured resin material. In this case, the average coefficient of linear expansion (CTE) from 25° C. to 150° C. at a tensile load of 33 mN of the obtained cured product is preferably 33 ppm/° C. or lower, more preferably 30 ppm/° C. or lower, and even more preferably 27 ppm/° C. ℃ or lower, particularly preferably 24 ppm/℃ or lower, and most preferably 22 ppm/℃ or lower. The average coefficient of linear expansion (CTE) of the cured product may be 17 ppm/°C or higher, and may be 19 ppm/°C or higher.

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

The film-like resin material (resin film) is temporarily cured by heating at 130°C for 60 minutes, and then heated at 200°C for 90 minutes to obtain a cured product of the resin material. The obtained cured product is cut into a size of 3 mm x 25 mm. Using a thermomechanical analysis device (e.g., “EXSTAR TMA/SS6100” manufactured by SII Nanotechnology), the cut cured material was measured from 25°C to 150°C under conditions of a tensile load of 33 mN and a temperature increase rate of 5°C/min. Calculate the average coefficient of linear expansion (ppm/°C).

(Semiconductor devices, printed wiring boards, copper clad laminates and multilayer printed wiring boards)

The resin material is suitably used to form a mold resin for embedding a semiconductor chip in a semiconductor device.

The resin material is suitable for use as a replacement for liquid crystal polymer (LCP), for use as a millimeter wave antenna, and for use as a redistribution layer. Additionally, the resin material is not limited to the above-mentioned applications and is suitably used for all applications for forming wiring.

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

The printed wiring board is obtained, for example, by heat-pressing and 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. A laminated structure comprising a member to be laminated having a metal layer on its surface and a resin film laminated on the surface of the metal layer, wherein the resin film is the resin material described above, can be suitably obtained. The method of laminating the resin film and the member to be laminated having the metal layer on its surface is not particularly limited, and a known method can be used. For example, the resin film can be laminated on a member to be laminated having a metal layer on its surface while being pressed with or without heating using an apparatus such as a parallel plate press or roll laminator.

The material of the metal layer is preferably copper.

The member to be laminated, which has 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 copper clad laminate is a copper clad laminate including 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 1 μm or more and 100 μm or less. Additionally, in order to increase the adhesive strength between the cured product of the resin material and the copper foil, the copper foil preferably has fine irregularities on its surface. The method of forming the irregularities is not particularly limited. Examples of the method of forming the irregularities include a method of forming them by 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 including a circuit board and an insulating layer laminated on the circuit board. The insulating layer of this multilayer substrate is formed from the above resin material. Additionally, the insulating layer of the multilayer substrate may be formed using a laminated film and the resin film of the laminated film. The insulating layer is preferably laminated on the surface of the circuit board on which the circuit is provided. It is preferable that a portion of the insulating layer is buried between the circuits.

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

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

In addition, the multilayer substrate preferably further includes a copper plating layer laminated on the surface of the insulating layer that has been roughened.

Additionally, another example of the multilayer board includes a circuit board, an insulating layer laminated on a surface of the circuit board, and copper foil laminated on a surface of the insulating layer opposite to the surface on which the circuit board is laminated. A multilayer substrate may be mentioned. It is preferable that the insulating layer is formed by curing the resin film using a copper clad laminate including copper foil and a resin film laminated on one surface of the copper foil. Additionally, the copper foil is etched and is preferably a copper circuit.

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

Among multilayer substrates, multilayer printed wiring boards require high insulation reliability by the insulating layer. In the resin material according to the present invention, insulation reliability can be effectively improved by exhibiting the effect of the present invention. Therefore, the resin material according to the present invention is suitably used to form 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 a surface of the circuit board, and a metal layer disposed between the plurality of insulating layers. At least one layer in the insulating layer is a cured product of the resin material.

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 layers. A metal layer 17 is formed in a portion of the upper surface 12a of the circuit board 12. Among the plurality of insulating layers 13 to 16, the insulating layers 13 to 15 other than the insulating layer 16 located on the outer surface opposite to the circuit board 12 side have a metal layer ( 17) is formed. The metal layer 17 is a circuit. Metal layers 17 are disposed between the circuit board 12 and the insulating layer 13 and between each layer of the laminated insulating layers 13 to 16, respectively. The lower metal layer 17 and the upper metal layer 17 are connected to each other by at least one of a via hole connection and a through hole connection (not shown).

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

(Roughening treatment and swelling treatment)

The resin material is preferably used to obtain a cured product that is subjected to roughening or desmear treatment. The cured product also includes a pre-cured material that can be 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 roughening treatment. Before roughening treatment, the cured product is preferably subjected to swelling treatment. The cured product is preferably subjected to swelling treatment after pre-curing and before roughening treatment, and is preferably cured after roughening treatment. However, the cured product does not necessarily have to undergo swelling treatment.

As a method of the swelling treatment, for example, a method of treating the cured product with an aqueous solution or an organic solvent dispersion solution of a compound containing ethylene glycol or the like as a main component is used. The swelling liquid used in the swelling treatment generally contains an alkali as a pH adjuster or the like. The swelling liquid preferably contains sodium hydroxide. Specifically, for example, the swelling treatment is performed by treating the cured product using a 40% by weight ethylene glycol aqueous 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 requires a long time, and the adhesive strength between the cured product and the metal layer tends to be low.

For the roughening treatment, chemical oxidizing agents such as manganese compounds, chromium compounds, or persulfate compounds are used, for example. These chemical oxidizing agents are used as an aqueous solution or organic solvent dispersion solution after water or an organic solvent is added. The roughening liquid used for roughening treatment generally contains an alkali as a pH adjuster or the like. The conditioned liquid preferably contains sodium hydroxide.

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

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

(desmear processing)

There are cases where through holes are formed in the cured product obtained by pre-curing the resin material. In the multilayer substrate, etc., vias, through holes, etc. are formed as through holes. For example, vias can be formed by irradiation with a laser such as a CO ₂ laser. The diameter of the via is not particularly limited, but is approximately 60 μm to 80 μm. Due to the formation of the through hole, a smear, which is a residue of resin derived from the resin component contained in the cured product, is often formed at the bottom of the via.

In order to remove the smear, the surface of the cured product is preferably desmeared. In some cases, the desmear process also serves as a roughening process.

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

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

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

The following materials were prepared.

(Epoxy compound)

Biphenyl type epoxy compound (“NC3000L” manufactured by Nippon Kayaku)

Bisphenol F type epoxy compound (“830S” manufactured by DIC)

(hardener)

First hardener:

Phenol carbonate compound (“FTC509” manufactured by Kunei Chemical, molecular weight 4000, glass transition temperature 110°C)

Liquid containing active ester carbonate compound (“FTC509ES” manufactured by Kunei Chemical, molecular weight 4000, solid content 55% by weight, glass transition temperature 33°C)

Secondary hardener:

Phenol compound-containing liquid (“LA-1356” manufactured by DIC, solid content: 60% by weight)

Liquid containing active ester compound (“HPC-8000L-65T” manufactured by DIC, solid content: 65% by weight)

(curing accelerator)

Imidazole compound (2-phenyl-4-methylimidazole, “2P4MZ” manufactured by Shikoku Chemicals)

(Filler: Inorganic filler)

Silica 1-containing slurry (slurry containing spherical silica, a surface-treated product with a silane coupling agent, average particle diameter 0.1 ㎛, produced by the following production method)

Silica 2-containing slurry (slurry containing spherical silica, a surface-treated product with a silane coupling agent, average particle diameter 0.5 ㎛, produced by the following production method)

Silica 3-containing slurry (slurry containing spherical silica, a surface-treated product using a silane coupling agent, average particle diameter 2.0 ㎛, produced by the following production method)

Silica 4-containing slurry (slurry containing spherical silica, a surface-treated product using a silane coupling agent, average particle diameter 2.5 ㎛, produced by the following production method)

<Method for producing slurry containing silica 1>

Silica (“Seahoster KE-S10” manufactured by Nippon Shokubai Co., Ltd.) was surface treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) having an N-phenyl-3-aminopropyl group. To the obtained surface treatment, cyclohexanone (“037-05096” manufactured by Wako Pure Chemical Industries, Ltd.) was added to a content of 50% by weight, thereby obtaining a slurry containing silica 1.

<Method for producing silica 2-containing slurry>

Silica (“SO-C2” manufactured by Admatex) was surface treated with a silane coupling agent having an N-phenyl-3-aminopropyl group (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.). To the obtained surface-treated material, cyclohexanone (“037-05096” manufactured by Wako Pure Chemical Industries, Ltd.) was added to a content of 50% by weight, thereby obtaining a silica 2-containing slurry.

<Method for producing silica 3-containing slurry>

Silica (“SO-C6” manufactured by Admatex) was surface treated with a silane coupling agent having an N-phenyl-3-aminopropyl group (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.). To the obtained surface treatment, cyclohexanone (“037-05096” manufactured by Wako Pure Chemical Industries, Ltd.) was added to a content of 50% by weight, thereby obtaining a silica 3-containing slurry.

<Method for producing silica 4-containing slurry>

Silica (“Seahostar KE-S250” manufactured by Nippon Shokubai Co., Ltd.) was surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) having an N-phenyl-3-aminopropyl group. Cyclohexanone (“037-05096” manufactured by Wako Pure Chemical Industries, Ltd.) was added to the obtained surface treatment material to a content of 50% by weight, thereby obtaining a silica 4-containing slurry.

(thermoplastic resin)

Polyimide resin-containing liquid (polyimide resin-containing liquid that is a reaction product of tetracarboxylic dianhydride and dimer diamine (non-volatile matter 26.8% by weight), synthesized according to Synthesis Example 1 below)

Phenoxy resin-containing liquid (weight average molecular weight 39000, “YX6954BH30” manufactured by Mitsubishi Chemical Corporation, solid content 30% by weight)

Carbonate resin (weight average molecular weight 1000, “C-1015N” manufactured by Kuraray Corporation)

<Synthesis Example 1>

In a reaction vessel equipped with a stirrer, water fountain, thermometer, and nitrogen gas introduction tube, 300.0 g of tetracarboxylic dianhydride (“BisDA-1000” manufactured by SABIC Japan Kodo Kaisha) and 665.5 g of cyclohexanone were added. was added, and the solution in the reaction vessel was heated to 60°C. Next, 89.0 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) and 54.7 g of 1,3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Company) were added dropwise to the reaction container. Next, 121.0 g of methylcyclohexane and 423.5 g of ethylene glycol dimethyl ether were added to the reaction container, and an imidization reaction was performed at 140°C for 10 hours. In this way, a polyimide resin-containing liquid (non-volatile matter 26.8% by weight) was obtained. The molecular weight (weight average molecular weight) of the obtained polyimide compound was 20000. Additionally, the molar ratio of acid component/amine component was 1.04.

The weight average molecular weights of the first curing agent and the thermoplastic resin were determined by GPC (gel permeation chromatography) measurement as follows.

Measurements were performed using a high-performance liquid chromatograph system manufactured by Shimadzu Seisakusho, using tetrahydrofuran (THF) as the development medium, at a column temperature of 40°C and a flow rate of 1.0 ml/min. “SPD-10A” was used as a detector, and two “KF-804L” (exclusion limit molecular weight 400,000) columns manufactured by Shodex were used connected in series. As standard polystyrene, "TSK Standard Polystyrene" manufactured by Tosoh Corporation was used, and a calibration curve was created using materials with weight average molecular weights Mw = 354,000, 189,000, 98,900, 37,200, 17,100, 9,830, 5,870, 2,500, 1,050,500, and the molecular weight Calculations were made.

(Examples 1 to 7 and Comparative Examples 1 to 3)

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

Production of resin film:

Using an applicator, the obtained resin material was applied onto the release-treated surface of a PET film (“XG284” manufactured by Toray Co., Ltd., thickness 25 μm), dried in a gear oven at 100°C for 2 minutes and 30 seconds, and then dissolved in solvent. was volatilized. In this way, a laminated film (laminated film of PET film and resin film) in which a resin film (B stage film) with a thickness of 40 μm was laminated on a PET film was obtained.

[evaluation]

(1) Dielectric loss tangent (Df) of the cured product

The obtained resin film was temporarily cured by heating at 180°C for 30 minutes, and then heated at 200°C for 90 minutes to obtain a cured product. The obtained cured product was cut to a size of 2 mm in width and 80 mm in length, and 10 sheets were overlapped, using “cavitary resonance perturbation method permittivity measurement device CP521” manufactured by Kanto Denshi Oyo Kaihatsu and “Network Analyzer N5224A PNA” manufactured by Keysight Technologies. Dielectric loss tangent was measured at room temperature (23°C) and frequency of 5.8GHz using the cavity resonance method.

[Judgement criteria for dielectric loss tangent (Df) of hardened products]

○○○: Dielectric loss tangent is less than 2.8×10 ^-3

○○: Dielectric loss tangent is 2.8×10 ^-3 or more but less than 2.9×10 ^-3

○: Dielectric loss tangent is 2.9×10 ^-3 or more but less than 3.0×10 ^-3

×: Dielectric loss tangent is 3.0×10 ^-3 or more

(2) Desmearability (removability of residues at the bottom of via)

Laminate/semi-hardened treatment:

A CCL substrate (“E-679FGR” manufactured by Hitachi Kasei Industries) was immersed in a copper surface roughening agent (“McEtch Bond CZ-8201” manufactured by Mack Corporation), and the copper surface was roughened to form a square CCL substrate with a side of 100 mm. got it Using a vacuum pressurized laminator (“MVLP-500” manufactured by Makey Seisakusho Co., Ltd.), the obtained laminated film was laminated on the roughened CCL substrate for 20 seconds at a laminating pressure of 0.7 MPa and a laminating temperature of 100°C, and further press pressure was applied. It was pressed for 40 seconds at 1.0 MPa and a press temperature of 100°C. After peeling off the PET film of the laminated film, it was heated at 100°C for 30 minutes and then at 180°C for 30 minutes to semi-cure the resin film. In this way, a laminate A in which the semi-cured product of the resin film was laminated on both sides of the CCL substrate was obtained.

Forming a via (through hole):

Using a CO ₂ laser (manufactured by Hitachi Via Mechanics), a via (through hole) with a diameter of 65 ㎛ at the upper end and a diameter of 45 ㎛ at the lower end (bottom) was created on the semi-cured product of the resin film of the obtained laminate A. was formed. In this way, a laminate B was obtained in which a semi-cured product of a resin film was laminated on a CCL substrate, and a via (through hole) was formed in the semi-cured product of the resin film.

Removal of residues at the bottom of the via:

(a) Swelling treatment

The obtained laminate B was placed in a swelling liquid (“Swelling Deep Securigant P” manufactured by Atotech Japan) at 60°C and shaken for 10 minutes. Afterwards, it was washed with pure water.

(b) Permanganate treatment (coarse treatment and desmear treatment)

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

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

[Criteria for judging desmearability (removability of residues at the bottom of vias)]

○○: Maximum smear length is less than 1㎛

○: Maximum smear length is 1㎛ or more and less than 2㎛

△: Maximum smear length is 2㎛ or more and less than 3㎛

×: Maximum smear length is 3㎛ or more

(3) Plating peel strength

Electroless plating process:

The surface of the roughened cured product of the evaluation sample obtained in the evaluation of “(2) Desmearability (removability of residues at the bottom of the via)” was cleaned with an alkaline cleaner at 60°C (“Cleaner Securigant 902” manufactured by Atotech Japan). was treated for 5 minutes and degreased and washed. After washing, the cured product was treated with a 25°C predip solution (“Predip Neogant B” manufactured by Atotech Japan) for 2 minutes. Thereafter, the cured product was treated with an activator solution at 40°C (“Activator Neogant 834” manufactured by Atotech Japan) for 5 minutes to provide a palladium catalyst. Next, the cured product was treated with a reducing solution at 30°C (“Reducer Neogant WA” manufactured by Atotech Japan) for 5 minutes.

Next, the cured product is placed in a chemical copper solution (“Basic Printogant MSK-DK,” “Copper Printogant MSK,” “Stabilizer Printogant MSK,” and “Reducer Cu” manufactured by Atotech Japan), and electroless plating is applied. This was carried out until the thickness reached about 0.5㎛. After electroless plating, annealing was performed at a temperature of 120°C for 30 minutes to remove remaining hydrogen gas. In addition, all processes up to the electroless plating process were performed on a beaker scale with the treatment liquid set at 2 L and the cured product shaken.

Electrolytic plating treatment:

Next, electrolytic plating was performed on the cured product that had undergone the electroless plating treatment until the plating thickness reached 25 μm. As 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, and “Corrective Agent Caparacid GS” manufactured by Atotech Japan. ), a current of 0.6A/cm ² was passed, and electrolytic plating was performed until the plating thickness reached about 25㎛. 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 with a copper plating layer laminated on the upper surface was obtained.

Measurement of plating peel strength:

A total of 6 rectangular cuts with a width of 10 mm were formed at 5 mm intervals on the surface of the copper plating layer of the cured product in which the obtained copper plating layer was laminated on the upper surface. Set the cured product with the copper plating layer laminated on the upper surface on a 90° peel tester (Tester Sangyo's "TE-3001"), pick up the end of the copper plating layer where the indentation is formed with a gripping tool, and remove the copper plating layer, avoiding the area where the via is formed. was peeled off by 20 mm and the peel strength (plating peel strength) was measured. The peel strength (plating peel strength) was measured at each of the six incision points, and the average value of the plating peel strength was obtained. The plating peel strength was determined based on the following criteria.

[Judgment criteria for plating peel strength]

○○: The average value of plating peel strength is 0.50kgf/cm or more.

○: The average value of plating peel strength is 0.45 kgf/cm or more and less than 0.50 kgf/cm

△: The average value of plating peel strength is 0.40kgf/cm or more and less than 0.45kgf/cm

×: The average value of plating peel strength is less than 0.40 kgf/cm

(4) Defects in the cured layer at the end of the substrate

In the same manner as the method described in the evaluation of “(2) Desmearability (removability of residues from the bottom of vias)” for the laminate A obtained in the evaluation of “(2) Desmearability (removability of residues from the bottom of vias)” Thus, (a) swelling treatment and (b) permanganate treatment were performed. Next, it was heated at 200°C for 60 minutes to obtain laminate C. For the obtained laminate C, the obtained laminate film was laminated for 20 seconds at a laminating pressure of 0.7 MPa and a laminating temperature of 100°C using a vacuum pressurized laminator machine (“MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.), and further press pressure was applied to the obtained laminate C. It was pressed for 40 seconds at 1.0 MPa and a press temperature of 100°C. After peeling off the PET film of the laminated film, it was heated at 100°C for 30 minutes and then at 180°C for 30 minutes to semi-cure the resin film. Next, (a) swelling treatment and (b) permanganate treatment were performed in the same manner as the method described in the evaluation of “(2) Desmearability (removability of residue at the bottom of via)”. Next, it was heated at 200°C for 60 minutes to obtain a laminate D in which two cured resin film layers were laminated on both sides of the CCL substrate. By repeating the same process, a laminate E was obtained in which eight layers of the cured resin film were laminated on both sides of the CCL substrate.

The obtained laminate E was dropped a total of 20 times from a height of 1 m. The presence or absence of notches in the cured layer of the resin film at the end of the substrate was confirmed using a microscope each time it was dropped.

[Criteria for judging notches in the cured layer at the end of the substrate]

○○: After dropping 20 times, no notches occur in the cured layer at the end of the substrate.

○: When dropped more than 11 times and less than 19 times, notches occur in the cured material layer at the end of the substrate.

△: When dropped more than 6 times and less than 10 times, notches occur in the cured layer at the end of the substrate.

×: Notches occur in the cured material layer at the end of the substrate when dropped more than once or more than five times.

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

11: Multilayer printed wiring board
12: circuit board
12a: top surface
13 to 16: insulating layer
17: metal layer

Claims (9)

Contains epoxy compounds, fillers and hardeners,
The average particle diameter of the filler is 2.0 μm or less,
A resin material, wherein the curing agent has a carbonate structure and includes a first curing agent having a functional group capable of reacting with an epoxy group. The resin material according to claim 1, wherein the content of the filler is 50% by weight or more and 90% by weight or less among 100% by weight of components excluding the solvent in the resin material. The resin material according to claim 1 or 2, wherein the molecular weight of the first curing agent is 20000 or less. The resin material according to any one of claims 1 to 3, wherein the curing agent includes a second curing agent that does not have a carbonate structure. 5. The resin material of claim 4, wherein the second curing agent comprises an active ester compound. The resin material according to any one of claims 1 to 5, comprising a polyimide resin. The resin material according to any one of claims 1 to 6, wherein the resin material is a resin film. The resin material according to any one of claims 1 to 7, used to form an insulating layer in a multilayer printed wiring board. circuit board,
a plurality of insulating layers disposed on the surface of the circuit board,
Provided with a metal layer disposed between the plurality of insulating layers,
A multilayer printed wiring board, wherein at least one layer in the plurality of insulating layers is a cured product of the resin material according to any one of claims 1 to 8.

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