WO2022234823A1

WO2022234823A1 - Resin material and multilayer printed wiring board

Info

Publication number: WO2022234823A1
Application number: PCT/JP2022/019363
Authority: WO
Inventors: 久美子西中; 達史林; 英寛出口; 悠太大當
Original assignee: 積水化学工業株式会社
Priority date: 2021-05-07
Filing date: 2022-04-28
Publication date: 2022-11-10
Also published as: KR20240004223A; CN117255820A; JPWO2022234823A1; TW202311340A

Abstract

The present invention provides a resin material which is capable of: (1) decreasing the dielectric loss tangent of a cured product thereof; (2) effectively removing smear by means of a desmear treatment; (3) enhancing the plating peel strength; and (4) making a cured product layer at the edge of a substrate less susceptible to the occurrence of cracks.　A resin material according to the present invention contains 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 contains a first curing agent which has a carbonate structure, while having a functional group that is reactive with an epoxy group.

Description

Resin materials and multilayer printed wiring boards

The present invention relates to resin materials containing epoxy compounds. 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 insulation between internal layers and to form an insulating layer positioned on a surface layer. Wiring, which is generally made of metal, is laminated on the surface of the insulating layer. Moreover, in order to form the insulating layer, a resin film obtained by forming the resin material into a film may be used. The above resin materials and resin films are used as insulating materials for multilayer printed wiring boards including build-up films.

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. there is In this resin composition, (B) the polymer compound is selected from 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 polycarbonate structure. It is a polymer compound having one or more structures that are

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.

JP 2018-150440 A JP 2007-284555 A

Conventional resin materials, which are designed to have a low dielectric loss tangent of cured products, cannot effectively remove smears by desmearing, and cannot increase the peel strength of the plating to the metal layer. There is

In addition, substrates that require a low dielectric loss tangent are becoming larger and more multilayered, and the weight of the substrate is increasing. Along with this, chipping of the cured material layer at the edges of the substrate tends to occur during handling and transportation of the substrate.

By the way, the above Patent Documents 1 and 2 describe a resin material containing a resin having a polycarbonate structure. However, the resins having a polycarbonate structure described in Patent Documents 1 and 2 are not curing agents. When 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, the desmear property may be lowered, or chipping may occur in the cured material layer at the edges of the substrate.

The objects of the present invention are 1) to reduce the dielectric loss tangent of the cured product, 2) to effectively remove smear by desmear treatment, 3) to increase the plating peel strength, and 4) to provide a substrate. It is an object of the present invention to provide a resin material capable of making it difficult for chipping to occur in a cured material layer at the end. Another object of the present invention is to provide a multilayer printed wiring board using the resin material.

According to a broad aspect of the present invention, an epoxy compound, a filler, and a curing agent are included, wherein the filler has an average particle size of 2.0 μm or less, and the curing agent has a carbonate structure and an epoxy group. A resin material is provided that includes a first curing agent having reactive functional groups.

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 in 100% by weight of the components excluding the solvent in the resin material.

In a specific aspect of the resin material according to the present invention, the first curing agent has a molecular weight of 20,000 or less.

In a specific aspect of the resin material according to the present invention, the curing agent contains a second curing agent that does not have a carbonate structure.

In a specific aspect 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 contains 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 for forming insulating layers in multilayer printed wiring boards.

According to a broad aspect of the present invention, the present invention comprises 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, wherein A multilayer printed wiring board is provided in which at least one layer is a cured product of the resin material described above.

A resin material according to the present invention includes an epoxy compound, a filler, and a curing agent, wherein the filler has an average particle size of 2.0 μm or less, and the curing agent has a carbonate structure and reacts with an epoxy group. A first curing agent with possible functional groups is included. 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). The plating peel strength can be increased, and 4) chipping of the cured product layer at the edge of the substrate can be prevented.

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

The details of the present invention will be described below.

A resin material according to the present invention includes an epoxy compound, a filler, and a curing agent, wherein the filler has an average particle size of 2.0 μm or less, and the curing agent has a carbonate structure and reacts with an epoxy group. A first curing agent with possible functional groups is included.

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). All of the effects of 1)-4) can be exhibited, namely that the peel strength of the plating can be increased and 4) chipping of the cured product layer at the edge of the substrate can be prevented.

In the resin material according to the present invention, the curing agent contains the first curing agent having a carbonate structure and a functional group capable of reacting with an epoxy group. The carbonate structure inside is less likely to undergo phase separation in the cured product. Therefore, since a uniform cured product can be obtained, chipping of the cured product layer at the edge of the substrate can be prevented. In addition, in the resin material according to the present invention, since the curing agent contains the first curing agent, uniform cross-linking of the first curing agent and the epoxy compound can be achieved after the formation of the through-holes. The resulting smear can be uniformly etched by the desmear treatment, and the smear can be effectively removed. Furthermore, in the resin material according to the present invention, since the curing agent contains the first curing agent, it is possible to prevent smear from being partially excessively etched due to phase separation of the carbonate structure. Peel strength can be increased.

In addition, in the resin material according to the present invention, since the filler has an average particle size of 2.0 μm or less, the first curing agent and the epoxy compound are uniformly crosslinked even in the vicinity of the filler. It is possible to make it difficult for chipping to occur in the cured product layer of the part. As a result, smear can be removed 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 the form of a paste. The pasty form includes a liquid form. The resin material according to the present invention is preferably a resin film because of its excellent handleability.

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

Details of each component used in the resin material according to the present invention and applications of the resin material according to the present invention will be described below.

[Epoxy compound]
The resin material includes an epoxy compound. Conventionally known epoxy compounds can be used as the epoxy compound. The epoxy compound is an organic compound having at least one epoxy group. Only one type of the epoxy compound may be used, or two or more types may be used in combination.

Examples of the epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenol novolac 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 adamantane skeleton, epoxy compound having tricyclodecane skeleton, naphthylene ether type Epoxy compounds, epoxy compounds having a triazine core in the skeleton, and the like are included.

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

From the viewpoint of further lowering the dielectric loss tangent of the cured product and improving the thermal dimensional stability and flame retardancy of the cured product, the epoxy compound preferably contains an epoxy compound having an aromatic skeleton, a naphthalene skeleton or More preferably, it contains an epoxy compound having a phenyl skeleton.

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

The viscosity at 25°C of the epoxy compound that 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 Rheological 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 in 100% by weight of the components excluding the solvent in the resin material, a resin material with high fluidity can be obtained when forming the insulating layer. Therefore, when an uncured resin material or a B-stage resin material is laminated on a circuit board, the filler can be uniformly present. "100% by weight of the components excluding the solvent in the resin material" means "100% by weight of the components excluding the solvent in the resin material" when the resin material contains the solvent, and when the resin material does not contain the solvent means "100% by weight of resin material".

The molecular weight of the epoxy compound means the 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. Moreover, when the said epoxy compound is a polymer, it means the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The content of the epoxy compound is preferably 5% by weight or more, more preferably 10% by weight or more, preferably 25% by weight or less, and more preferably 20% by weight in 100% by weight of the components excluding the solvent in the resin material. It is below. When the content of the epoxy compound is not less than the above lower limit and not more than the above upper limit, the above effects 1) to 4) can be exhibited more effectively.

The content of the epoxy compound is preferably 15% by weight or more, more preferably 25% by weight or more, still more preferably 35% by weight or more, and preferably 60% by weight in 100% by weight of the components excluding the filler and solvent in the resin material. % 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 above effects 1) to 4) can be exhibited even more effectively.

[Curing agent]
The resin material contains a curing agent. From the viewpoint of exhibiting the effects of 1) to 4) above, the curing agent includes a first curing agent having 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 Curing Agent>
The first curing agent is a compound (curing agent) having a carbonate structure and a functional group capable of reacting with an epoxy group. The first curing agent has a carbonate structure (--OC(=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 capable of reacting with the epoxy group of the epoxy compound. Only one kind of the first curing agent may be used, or two or more kinds thereof may be used in combination.

Examples of functional groups that can react with the epoxy groups include amino groups, hydroxyl groups, active ester groups, cyanate ester groups, carbodiimide groups, maleimide groups, and benzoxazine groups.

From the viewpoint of further lowering the dielectric loss tangent of the cured product, the functional group capable of reacting with the epoxy group is preferably 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, the first curing agent preferably has an aliphatic ring. From the viewpoint of enhancing the heat resistance of the cured product, the first curing agent preferably 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, the first curing agent preferably has an aliphatic ring and an aromatic ring.

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

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) above in a well-balanced manner, the first curing agent preferably contains a phenol carbonate compound (a compound having a carbonate structure and a phenol structure), and a phenol carbonate compound ( A compound having a carbonate structure and a phenol structure) is more preferred. In particular, by using a phenol carbonate compound (a compound having a carbonate structure and a phenol structure), the effect of 3) above can be exhibited more effectively.

From the viewpoint of exhibiting the above effects 1) to 4) in a well-balanced manner, the first curing agent is preferably a compound represented by the following formula (3).

In the above formula (3), X1 and X2 each represent a hydroxyl group or an active ester group, R1 represents an aliphatic ring, R2 and R3 each represent a skeleton derived from a bisphenol compound, and n is 1 or more. represents an integer of In formula (3) above, X1 and X2 may be the same or different. In formula (3) above, R2 and R3 may be the same or different. In the formula (3), n may represent an integer of 500 or less, an integer of 200 or less, an integer of 100 or less, or an integer of 50 or less. In the formula (3), n preferably represents an integer such that the molecular weight of the first curing agent is 2000 or more. In the formula (3), n preferably represents an integer such that the molecular weight of the first curing agent is 20,000 or less.

From the viewpoint of exhibiting the above effects 1), 2) and 4), particularly the above effect 1) more effectively, the first curing agent should be an active ester carbonate compound (a carbonate structure and an active compound having an ester structure). From the viewpoint of exhibiting the effects of 1), 2), and 4) above, particularly the effect of 1) above more effectively, the first curing agent is an active ester carbonate compound (a carbonate structure and an active compound having an ester structure).

The molecular weight of the first curing agent is preferably 2000 or more, more preferably 3000 or more, preferably 20000 or less, more preferably 15000 or less. When the molecular weight of the first curing agent is not less than the lower limit and not more than the upper limit, the above effects 1) to 4) can be exhibited more effectively.

When the structural formula of the first curing agent can be identified, the molecular weight of the first curing agent means the molecular weight that can be calculated from the structural formula. Moreover, when the said 1st hardening|curing agent is a polymer, it means the weight average molecular weight in polystyrene conversion measured by the 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, and preferably 150°C or lower, more preferably 120°C or lower. When the glass transition temperature of the first curing agent is equal to or higher than the lower limit, the plating peel strength can be further increased. When the glass transition temperature of the first curing agent is equal to or lower than 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 Gunei Chemical Co., Ltd., and "T6002" and "T6001" manufactured by Asahi Kasei Chemicals.

The content of the first curing agent in 100% by weight of the 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. . When the content of the first curing agent is at least the above lower limit, the above effects 1) and 2) can be exhibited more effectively. When the content of the first curing agent is equal to or less than the upper limit, the above effects 3) and 4) can be exhibited more effectively.

The content of the first curing agent with respect 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, and more preferably 60 parts by weight or less. When the content of the first curing agent is equal to or more than the lower limit and equal to or less than the upper limit, the above effects 1) to 4) can be exhibited more effectively.

The content of the first curing agent in 100% by weight of the components excluding the solvent in the resin material is preferably 0.5% by weight or more, more preferably 1% by weight or more, and preferably 20% by weight or less. Preferably, it is 15% by weight or less. When the content of the first curing agent is not less than the lower limit and not more than the upper limit, the above effects 1) to 4) can be exhibited more effectively.

The content of the first curing agent is preferably 2.5% by weight or more, more preferably 5% by weight or more, and preferably 35% by weight or less in 100% by weight of the components excluding the filler and solvent in the resin material. , more preferably 30% by weight or less. When the content of the first curing agent is not less than the lower limit and not more than the upper limit, the above effects 1) to 4) can be exhibited more effectively. "100% by weight of components excluding fillers and solvents in the resin material" means "100% by weight of components excluding fillers and solvents in the resin material" when the resin material contains a solvent. When not containing, it means "100% by weight of the components excluding the filler in the resin material".

<Second Curing Agent>
The second curing agent is a compound (curing agent) that does not have a carbonate structure. The curing agent preferably contains the second curing agent. Only one kind of the second curing agent may be used, or two or more kinds thereof may be used in combination.

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, benzoxazine compounds (benzo oxazine curing agent), amine compounds (amine curing agent), thiol compounds (thiol curing agent), phosphine compounds, dicyandiamide, acid anhydrides, and the like.

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, more preferably an active ester compound or a phenol compound, and an active ester More preferably, it contains a compound. In this case, the dielectric loss tangent of the cured product can be further reduced, and the thermal dimensional stability of the cured product can be further enhanced. From the viewpoint of further lowering the dielectric loss tangent of the cured product, the second curing agent preferably contains an active ester compound. From the viewpoint of further increasing the plating peel strength, the second curing agent preferably contains a phenol compound.

Active ester compound:
The active ester compound is a compound that contains at least one ester bond in its structure and that has an aliphatic chain, an aliphatic ring, or an aromatic ring bonded to both sides of the ester bond. An 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). Only one kind of the active ester compound may be used, or two or more kinds thereof may be used in combination.

In the above formula (1), X1 represents an aliphatic chain-containing group, an aliphatic ring-containing group, or an aromatic ring-containing group, and X2 represents an aromatic ring-containing group. Preferred examples of the aromatic ring-containing group include an optionally substituted benzene ring and an optionally substituted naphthalene ring. A hydrocarbon group is mentioned as said substituent. 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 includes a combination of a benzene ring which may have a substituent and a benzene ring which may have a substituent, and a combination of a benzene ring, which may have a substituent, and a naphthalene ring, which may have a substituent. Furthermore, in the above formula (1), the combination of X1 and X2 includes a combination of an optionally substituted naphthalene ring and an optionally substituted naphthalene ring.

The above 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 reducing the dielectric loss tangent of the cured product and enhancing the thermal dimensional stability of the cured product, the active ester compound more preferably has a naphthalene ring in the main chain skeleton.

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

Phenolic compounds:
Examples of the phenol compound include novolak-type phenol, biphenol-type phenol, naphthalene-type phenol, dicyclopentadiene-type phenol, aralkyl-type phenol, and dicyclopentadiene-type phenol. As for the said phenol compound, only 1 type may be used and 2 or more types may be used together.

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

Cyanate ester compound:
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 novolak-type cyanate ester resins include phenol novolac-type cyanate ester resins and alkylphenol-type 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. 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 above cyanate ester compounds include phenol novolac type cyanate ester resins (“PT-30” and “PT-60” manufactured by Lonza Japan Co., Ltd.) and prepolymers in which bisphenol type cyanate ester resins are trimerized (Lonza Japan "BA-230S", "BA-3000S", "BTP-1000S" and "BTP-6020S" manufactured by the same company).

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 left end are bonding sites with other groups. Only one kind of the carbodiimide compound may be used, or two or more kinds thereof may be used in combination.

In the above formula (2), X is an alkylene group, an alkylene group to which a substituent is bonded, a cycloalkylene group, a cycloalkylene group to which a substituent is bonded, an arylene group, or an arylene group to which a substituent is bonded group, and p is an integer of 1-5. When there are multiple X's, the multiple X's may be the same or different.

In one preferred embodiment, at least one X is an alkylene group, a group in which a substituent is bonded to an alkylene group, a cycloalkylene group, or a group in which a substituent is 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-09" manufactured by Nisshinbo Chemical Co., Ltd. 10M-SP" and "Carbodilite 10M-SP (improved)", and "Stabaxol P", "Stabaxol P400" and "Hykasil 510" manufactured by Rhein Chemie.

Maleimide compounds:
Examples of the maleimide compound include N-phenylmaleimide and N-alkylbismaleimide. The maleimide compound may be a bismaleimide compound. Only one type of the maleimide compound may be used, or two or more types may be used in combination.

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

In the above 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 effects 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.

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

Examples of commercially available maleimide compounds include "BMI-4000" and "BMI-5100" manufactured by Daiwa Kasei Kogyo Co., Ltd., and Designer Molecules Inc. and "BMI-3000" manufactured by K.K.

Benzoxazine compounds:
Examples of the benzoxazine compound include Pd-type benzoxazine and Fa-type benzoxazine. Only one kind of the benzoxazine compound may be used, or two or more kinds thereof may be used in combination.

Commercially available products of the above benzoxazine compounds include "Pd type" manufactured by Shikoku Kasei Kogyo Co., Ltd.

Acid anhydride:
Examples of the acid anhydride include tetrahydrophthalic anhydride and alkylstyrene-maleic anhydride copolymer. Only one kind of the acid anhydride may be used, or two or more kinds thereof may be used in combination.

Commercially available products of the above acid anhydrides include "Rikacid TDA-100" manufactured by Shin Nippon Rika.

The content of the second curing agent with respect 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, and more preferably 85 parts by weight or less. When the content of the second curing agent is the above lower limit or more and the above upper limit or less, the curability can be further improved, the thermal dimensional stability of the cured product is further improved, and the remaining unreacted components are reduced. Volatilization can be further suppressed.

The content of the curing agent (total content of the first curing agent and the second curing agent) with respect 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. is 135 parts by weight or less, more preferably 130 parts by weight or less. When the content of the curing agent is not less than the above lower limit and not more than the above upper limit, the curability can be further improved, the thermal dimensional stability of the cured product is further improved, and the remaining unreacted components are more volatilized. can be further suppressed.

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) in 100% by weight of the components excluding the 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, and more preferably 95% by weight or less. When the total content is equal to or more than the lower limit and equal to or less than the upper limit, the curability can be further improved, and the thermal dimensional stability of the cured product can be further improved.

[Filler]
The resin material contains a filler. The average particle size 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 kind of the filler may be used, or two or more kinds thereof may be used in combination.

Examples of the organic filler include benzoxazine resin particles, benzoxazole resin particles, fluororesin 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. Only one kind of the inorganic filler may be used, or two or more kinds thereof may be used in combination.

The filler is preferably an inorganic filler. In this case, the dielectric loss tangent of the cured product can be further reduced. In addition, it is possible to further reduce the dimensional change of the cured product due to heat.

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, finer wiring is formed on the surface of the cured product, and Better insulation reliability can be imparted to the cured product. 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. Also, the dielectric constant of the cured product can be improved. The shape of silica is preferably spherical.

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

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 surface of the roughened cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased. In addition, 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 are imparted to the cured product. can do.

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

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

The average particle size 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. When the average particle size of the filler is the lower limit or more and the upper limit or less, 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 increase The average particle size of the filler may exceed 0.5 μm, may be 1.0 μm or more, may be 1 μm or less, may be less than 1 μm, or may be 0.5 μm or less. may be less than 0.5 μm, and may be 0.3 μm or less.

When the filler is an inorganic filler, the average particle size 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. When the average particle size of the inorganic filler is at least the lower limit and at most the upper limit, the surface roughness after etching can be reduced and the peel strength of the plating can be increased, and the adhesion between the insulating layer and the metal layer is improved. can enhance sexuality. The average particle size of the inorganic filler may exceed 0.5 μm, may be 1.0 μm or more, may be 1 μm or less, may be less than 1 μm, or may be 0.5 μm or less. It may be less than 0.5 μm, or it may be 0.3 μm or less.

When the filler is an organic filler, the average particle size 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. . When the average particle size of the organic filler is the lower limit or more and the upper limit or less, 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. can enhance sexuality. The average particle size of the organic filler may exceed 0.5 μm, may be 1.0 μm or more, may be 1 μm or less, may be less than 1 μm, or may be 0.5 μm or less. It may be less than 0.5 μm, or it may be 0.3 μm or less.

A median diameter (d50) value of 50% is adopted as the average particle diameter of the above fillers (inorganic filler and organic filler). The average particle size is preferably the average particle size of primary particles. The average particle size can be measured using a laser diffraction scattering type particle size distribution analyzer.

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, and more preferably 85% by weight or less in 100% by weight of the components excluding the solvent in the resin material. , more preferably 80% by weight or less. When the filler content is at least the lower limit, the dielectric loss tangent is effectively lowered. When the content of the filler is equal to or less than the above upper limit, the thermal dimensional stability of the cured product can be enhanced, and warpage of the cured product can be effectively suppressed. When the content of the filler is at least the lower limit and at most the 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. . Furthermore, when the content of the filler is equal to or more than the lower limit and equal to or less than the upper limit, it is possible to lower the coefficient of thermal expansion of the cured product and to improve the smear removability.

[Curing accelerator]
The resin material preferably contains a curing accelerator. However, the resin material may not contain a curing accelerator. The use of the curing accelerator makes the curing speed even faster. By rapidly curing the resin material, the crosslinked structure in the cured product becomes uniform and the number of unreacted functional groups is reduced, resulting in a high crosslink density. The curing accelerator is not particularly limited, and conventionally known curing accelerators can be used. Only one kind of the curing accelerator may be used, or two or more kinds thereof may be used in combination.

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

Examples of the imidazole compound include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl- 2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-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 isocyanurate, 2-phenylimidazole isocyanurate, 2-methylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-dihydroxymethylimidazole etc.

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

Examples of the phosphorus compounds include triphenylphosphine compounds.

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

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

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

From the viewpoint of further suppressing the curing temperature and effectively suppressing the warp of the cured product, the content of the anionic curing accelerator is preferably 20% by weight or more, more preferably 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 hardening accelerator is most preferably the anionic hardening accelerator.

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 or less in 100% by weight of the components excluding the filler and solvent in the resin material, More preferably, it is 3% by weight or less. When the content of the curing accelerator is equal to or more than the lower limit and equal to or less than the upper limit, the resin material is efficiently cured. If the content of the curing accelerator is within a more preferable range, the storage stability of the resin material will be further increased, and a more favorable cured product will be obtained.

[Thermosetting compound other than epoxy compound]
The resin material may or may not contain a thermosetting compound other than the epoxy compound. As for the thermosetting compounds other than the epoxy compound, only one type may be used, or two or more types may be used in combination.

Thermosetting compounds other than the above epoxy compounds include vinyl compounds, styrene compounds, oxetane compounds, polyarylate compounds, diallyl phthalate compounds, acrylate compounds, episulfide compounds, (meth)acrylic compounds, amino compounds, unsaturated polyester compounds, polyurethanes. 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 kind of the thermoplastic resin may be used, or two or more kinds thereof may be used in combination.

From the viewpoint of effectively exhibiting the effects of the present invention, the thermoplastic resin is preferably a polyimide resin or a phenoxy resin, more preferably a polyimide resin. From the viewpoint of effectively exhibiting the effects of the present invention, the resin material preferably contains a polyimide resin or a phenoxy resin, and more preferably contains a polyimide resin. The resin material does not contain or contains a polyimide resin. The resin material may or may not contain a polyimide resin. The resin material does not contain or contains a phenoxy resin. The resin material may contain no phenoxy resin or 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 may not contain a phenoxy resin.

From the viewpoint of improving solubility, the polyimide resin is preferably 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′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenylsulfonetetra 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′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3′,4,4′-tetraphenylsilanetetracarboxylic 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'-diphenylether dianhydride, and bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride.

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

The polyimide resin may have an acid anhydride structure, a maleimide structure, or a citraconimide structure at its 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 enhanced.

From the viewpoint of effectively lowering the dielectric loss tangent and effectively increasing the adhesion of the metal wiring regardless of the curing environment, the thermoplastic resin preferably 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 in the holes or irregularities of the circuit board and the non-uniformity of the inorganic filler. In addition, the use of a phenoxy resin makes it possible to adjust the melt viscosity, so that the dispersibility of the inorganic filler is improved, and in the curing process, the resin composition or B-staged product is less likely to wet and spread in unintended regions.

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

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

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

From the viewpoint of obtaining a resin film 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, and preferably 100,000 or less. Preferably it is 50000 or less.

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

The contents of the thermoplastic resin, the polyimide resin and the phenoxy resin are not particularly limited. The content of the thermoplastic resin (when the thermoplastic resin is a polyimide resin or a phenoxy resin, the content of the polyimide resin or the phenoxy resin) in 100% by weight of the components excluding the filler and solvent in the resin material is preferably is 1% by weight or more, more preferably 2% by weight or more, preferably 30% by weight or less, and more preferably 20% by weight or less. When the content of the thermoplastic resin is equal to or more than the lower limit and equal to or less than the upper limit, the embedding property of the resin film into the holes or unevenness of the circuit board is improved. When the content of the thermoplastic resin is equal to or higher than the lower limit, formation of the resin film becomes easier, and an even better insulating layer can be obtained. If the content of the thermoplastic resin is equal to or less than the upper limit, the thermal expansion coefficient of the cured product will be even lower. When the content of the thermoplastic resin is equal to or less than the upper limit, the surface roughness of the cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased.

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

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

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

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, and preferably 10% by weight. % or less, more preferably 5 wt % or less.

[Other ingredients]
For the purpose of improving impact resistance, heat resistance, resin compatibility, workability, etc., the above resin materials contain leveling agents, flame retardants, coupling agents, coloring agents, antioxidants, ultraviolet degradation inhibitors, antifoaming agents, etc. agents, thickeners, thixotropic agents, and the like.

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

(resin film)
A resin film (B-stage product/B-stage film) is obtained by molding the resin composition described above into a film. The resin material is preferably a resin film. The resin film is preferably 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 molding method in which a resin composition containing a solvent is cast and molded into a film. Other film forming methods known in the art. An extrusion molding method or a casting molding method is preferable because it can be used for thinning. Film includes sheets.

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

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

The resin film does not have to be a prepreg. If the resin film is not a prepreg, no migration occurs along the glass cloth or the like. In addition, when the resin film is laminated or precured, the 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 comprising 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, if necessary.

From the viewpoint of more uniformly controlling the degree of curing of the resin film, the thickness of the resin film is preferably 5 μm or more and preferably 200 μm or less. When the resin film is used as an insulating layer of a circuit, the thickness of the insulating layer formed of the resin film is preferably equal to or greater than the thickness of the conductor layer (metal layer) forming the circuit. The thickness of the insulating layer is preferably 5 μm or more and preferably 200 μm or less.

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

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

A film-shaped resin material (resin film) is heated at 130°C for 60 minutes for temporary curing, 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×25 mm. Using a thermomechanical analyzer (for example, "EXSTAR TMA/SS6100" manufactured by SII Nanotechnology Co., Ltd.), under the conditions of a tensile load of 33 mN and a temperature increase rate of 5 ° C./min, the cut cured product was measured from 25 ° C. to Calculate the average coefficient of linear expansion (ppm/°C) up to 150°C.

(Semiconductor devices, printed wiring boards, copper clad laminates and multilayer printed wiring boards)
The above resin material is suitably used for forming a mold resin for embedding a semiconductor chip in a semiconductor device.

The above resin material is suitably used for liquid crystal polymer (LCP) substitute applications, millimeter wave antenna applications, and rewiring layer applications. In addition, the above resin material is not limited to the above applications, and is suitable for general wiring formation applications.

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

The printed wiring board is obtained, for example, by heating and pressurizing the resin material.

A member to be laminated having a metal layer on its surface can be laminated on one or both sides of the resin film. It is possible to suitably obtain 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. A method for laminating the resin film and the member to be laminated having the metal layer on the surface thereof is not particularly limited, and a known method can be used. For example, using a device such as a parallel plate press or a roll laminator, the resin film can be laminated on a member to be laminated having a metal layer on its surface while applying pressure with or without heating.

The material of the metal layer is preferably copper.

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

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

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

An example of the multi-layer board is a multi-layer board comprising a circuit board and an insulating layer laminated on the circuit board. The insulating layer of this multilayer substrate is formed of the above resin material. Moreover, the insulating layer of the multilayer substrate may be formed of the resin film of the laminated film by using the laminated film. The insulating layer is preferably laminated on the surface of the circuit board on which the circuit is provided. A part of the insulating layer is preferably embedded between the circuits.

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

A conventionally known roughening treatment method can be used for the 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.

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

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

Another example of the multilayer board is a multilayer board that includes a circuit board and a plurality of insulating layers laminated on the surface of the circuit board. At least one of the plurality of insulating layers arranged on the circuit board is formed 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 boards, multilayer printed wiring boards require high insulation reliability due to insulating layers. In the resin material according to the present invention, insulation reliability can be effectively improved by exhibiting the effects of the present invention. Therefore, the resin material according to the present invention is suitably used for forming insulating layers in multilayer printed wiring boards.

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

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 hardened layers. A metal layer 17 is formed on a partial region of the upper surface 12 a of the circuit board 12 . Of the plurality of insulating layers 13 to 16, the insulating layers 13 to 15 other than the insulating layer 16 positioned on the outer surface opposite to the circuit board 12 side have a metal layer 17 formed on a partial region of the upper surface. ing. Metal layer 17 is a circuit. A metal layer 17 is arranged between the circuit board 12 and the insulating layer 13 and between 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 via-hole connection and through-hole connection (not shown).

In the multilayer printed wiring board 11, the insulating layers 13 to 16 are formed from the cured resin material. In this embodiment, since the surfaces of the insulating layers 13-16 are roughened, fine holes (not shown) are formed in the surfaces of the insulating layers 13-16. Also, the metal layer 17 reaches inside the fine holes. Moreover, 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 reduced. Moreover, in the multilayer printed wiring board 11, good insulation reliability is imparted between the upper metal layer and the lower metal layer that are not connected by via-hole connections and through-hole connections (not shown).

(Roughening treatment and swelling treatment)
The resin material is preferably used to obtain a cured product that is roughened or desmeared. The cured product also includes a pre-cured product that can be further cured.

In order to form fine unevenness on the surface of the cured product obtained by precuring the resin material, the cured product is preferably subjected to a roughening treatment. The cured product is preferably subjected to a swelling treatment before the roughening treatment. The cured product is preferably subjected to swelling treatment after precuring and before roughening treatment, and further cured after roughening treatment. However, the cured product does not necessarily have to be subjected to a swelling treatment.

As the swelling treatment method, 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 as a main component is used. The swelling liquid used for the swelling treatment generally contains an alkali as a pH adjuster or the like. The swelling liquid preferably contains sodium hydroxide. Specifically, for example, the swelling treatment is performed by treating the cured product with 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 in the range of 50.degree. C. to 85.degree. When 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 persulfate compound is used. These chemical oxidants are used as aqueous solutions or organic solvent dispersion solutions after water or organic solvents are added. The roughening liquid used for the roughening treatment generally contains an alkali as a pH adjuster or the like. The roughening liquid preferably contains sodium hydroxide.

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

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, still more preferably less than 150 nm. In this case, the adhesive strength between the cured product and the metal layer is increased, and 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 according to JIS B0601:1994.

(Desmear treatment)
Through-holes may be formed in the cured product obtained by precuring the resin material. Vias, through holes, or the like are formed as through holes in the multilayer substrates and the like. For example, vias can be formed by irradiation with a laser such as a _CO2 laser. Although the diameter of the via is not particularly limited, it is about 60 μm to 80 μm. Due to the formation of the through-holes, smears, which are residues of the resin derived from the resin component contained in the cured product, are often formed at the bottom of the vias.

In order to remove the smear, the surface of the cured product is preferably desmeared. The desmearing treatment may also serve as the roughening treatment.

For the desmear treatment, chemical oxidizing agents such as manganese compounds, chromium compounds, or persulfate compounds are used in the same manner as the roughening treatment. These chemical oxidants are used as aqueous solutions or organic solvent dispersion solutions after water or organic solvents are added. A desmearing liquid used for desmearing generally contains an alkali. The desmear treatment liquid preferably contains sodium hydroxide.

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

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

"I prepared the following materials."

(epoxy compound)
Biphenyl-type epoxy compound ("NC3000L" manufactured by Nippon Kayaku)
Bisphenol F type epoxy compound ("830S" manufactured by DIC)

(curing agent)
First Curing Agent:
Phenol carbonate compound ("FTC509" manufactured by Gunei Chemical Co., Ltd., molecular weight 4000, glass transition temperature 110 ° C.)
Active ester carbonate compound-containing liquid ("FTC509ES" manufactured by Gunei Chemical Co., Ltd., molecular weight 4000, solid content 55% by weight, glass transition temperature 33°C)

Second curing agent:
Phenolic compound-containing liquid ("LA-1356" manufactured by DIC, solid content 60% by weight)
Active ester compound-containing liquid (manufactured by DIC "HPC-8000L-65T", solid content 65% by weight)

(Curing accelerator)
Imidazole compound (2-phenyl-4-methylimidazole, "2P4MZ" manufactured by Shikoku Kasei Kogyo Co., Ltd.)

(Filler: inorganic filler)
Slurry containing silica 1 (slurry containing spherical silica that is surface-treated with a silane coupling agent, average particle size 0.1 μm, prepared by the following preparation method)
Slurry containing silica 2 (slurry containing spherical silica that is surface-treated with a silane coupling agent, average particle size 0.5 μm, prepared by the following preparation method)
Slurry containing silica 3 (slurry containing spherical silica that is surface-treated with a silane coupling agent, average particle size 2.0 μm, prepared by the following preparation method)
Slurry containing silica 4 (slurry containing spherical silica that is surface-treated with a silane coupling agent, average particle size 2.5 μm, prepared by the following preparation method)

<Method for preparing silica 1-containing slurry>
Silica (“Seahoster KE-S10” manufactured by Nippon Shokubai Co., Ltd.) was surface-treated with a silane coupling agent having an N-phenyl-3-aminopropyl group (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.). Cyclohexanone (“037-05096” manufactured by Wako Pure Chemical Industries, Ltd.) was added to the resulting surface-treated product so as to have a content of 50% by weight to obtain a silica 1-containing slurry.

<Method for preparing slurry containing silica 2>
Silica (“SO-C2” manufactured by Admatechs) was surface-treated with a silane coupling agent having an N-phenyl-3-aminopropyl group (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.). Cyclohexanone (“037-05096” manufactured by Wako Pure Chemical Industries, Ltd.) was added to the resulting surface-treated product so as to have a content of 50% by weight to obtain a silica 2-containing slurry.

<Method for preparing slurry containing silica 3>
Silica ("SO-C6" manufactured by Admatechs) was surface-treated with a silane coupling agent having an N-phenyl-3-aminopropyl group ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.). Cyclohexanone (“037-05096” manufactured by Wako Pure Chemical Industries, Ltd.) was added to the resulting surface-treated product so as to have a content of 50% by weight to obtain a silica 3-containing slurry.

<Method for preparing slurry containing silica 4>
Silica (“Seahoster KE-S250” manufactured by Nippon Shokubai Co., Ltd.) was surface-treated with a silane coupling agent having an N-phenyl-3-aminopropyl group (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.). Cyclohexanone (“037-05096” manufactured by Wako Pure Chemical Industries, Ltd.) was added to the obtained surface-treated product so as to have a content of 50% by weight to obtain a silica 4-containing slurry.

(Thermoplastic resin)
Polyimide resin-containing liquid (polyimide resin-containing liquid (nonvolatile content 26.8% by weight) which is a reaction product of tetracarboxylic dianhydride and dimer diamine, 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 Co., Ltd.)

<Synthesis Example 1>
A reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen gas inlet tube was charged with 300.0 g of tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan LLC) and 665.5 g of cyclohexanone. and the solution in the reaction vessel was heated to 60°C. Then, 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, Inc.) were dropped into the reaction vessel. Then, 121.0 g of methylcyclohexane and 423.5 g of ethylene glycol dimethyl ether were added to the reactor, and imidization reaction was carried out at 140° C. for 10 hours. Thus, a polyimide resin-containing liquid (26.8% by weight of non-volatile content) was obtained. The molecular weight (weight average molecular weight) of the obtained polyimide compound was 20,000. 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) as follows.

Using a high-performance liquid chromatograph system manufactured by Shimadzu Corporation, tetrahydrofuran (THF) was used as a developing medium, and measurement was performed 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" columns (exclusion limit molecular weight: 400,000) manufactured by Shodex were connected in series. As 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, A calibration curve was generated using 500, 1,050, 500 substances and molecular weight calculations were performed.

(Examples 1 to 7 and Comparative Examples 1 to 3)
The components shown in Tables 1 and 2 below were blended in the amounts shown in Tables 1 and 2 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, apply the obtained resin material on the release-treated surface of a release-treated PET film (“XG284” manufactured by Toray Industries, Inc., thickness 25 μm), and then place in a gear oven at 100° C. for 2 minutes. Dry for 30 seconds to evaporate the solvent. Thus, a laminated film (laminated film of PET film and resin film) in which a resin film (B stage film) having a thickness of 40 μm was laminated on the PET film was obtained.

[evaluation]
(1) Dielectric loss tangent (Df) of cured product
The resulting resin film was heated at 180° C. for 30 minutes for temporary curing, and then heated at 200° C. for 90 minutes to obtain a cured product. The resulting cured product was cut into a size of 2 mm in width and 80 mm in length, and 10 sheets were superimposed and measured by Kanto Denshi Applied Development Co., Ltd.'s "Cavity Resonance Perturbation Method Dielectric Constant Measurement Device CP521" and Keysight Technologies, Inc.'s " Using a network analyzer N5224A PNA, the dielectric loss tangent was measured at room temperature (23° C.) and a frequency of 5.8 GHz by the cavity resonance method.

[Criteria for Dielectric Loss Tangent (Df) of Cured Material]
○○○: Dielectric loss tangent is less than 2.8×10 ^{-3 ○○: Dielectric loss tangent is 2.8×10 -3} ^or more and less than 2.9×10 ^-3 〇: Dielectric loss tangent is 2.9×10 ^-3 or more Less than 3.0×10 ⁻³ ×: Dielectric loss tangent is 3.0×10 ⁻³ or more

(2) Desmear property (removability of residue on bottom of via)
Lamination/semi-curing treatment:
A CCL substrate (“E-679FGR” manufactured by Hitachi Chemical Co., Ltd.) was immersed in a copper surface roughening agent (“Mec Etch Bond CZ-8201” manufactured by MEC Co., Ltd.) to form a 100 mm square CCL with a roughened copper surface. got the substrate. Using a vacuum pressurized laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.), the resulting laminated film was laminated on a roughened CCL substrate at a lamination pressure of 0.7 MPa and a lamination temperature of 100° C. for 20 seconds. and further pressed at a press pressure of 1.0 MPa and a press temperature of 100° C. for 40 seconds. After peeling off the PET film of the laminated film, the resin film was semi-cured by heating at 100° C. for 30 minutes and then at 180° C. for 30 minutes. Thus, a laminate A was obtained in which semi-cured resin films were laminated on both sides of the CCL substrate.

Via (through hole) formation:
A CO ₂ laser (manufactured by Hitachi Via Mechanics Co., Ltd.) was applied to the semi-cured product of the resin film of the obtained laminate A, and a via (through hole) having a diameter of 65 μm at the upper end and a diameter of 45 μm at the lower end (bottom) holes) were formed. Thus, a laminate B was obtained in which the semi-cured resin film was laminated on the CCL substrate and vias (through holes) were formed in the semi-cured resin film.

Via bottom residue removal process:
(a) Swelling Treatment The obtained laminate B was placed in a swelling liquid (“Swelling Dip Securigant P” manufactured by Atotech Japan) at 60° C. and shaken for 10 minutes. After that, it was washed with pure water.

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

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

[Desmear property (removability of residue on via bottom) criteria]
○○: Maximum smear length less than 1 μm ○: Maximum smear length 1 μm or more and less than 2 μm △: Maximum smear length 2 μm or more and less than 3 μm ×: Maximum smear length 3 μm or more

(3) Plating peel strength Electroless plating treatment:
The surface of the roughened cured product of the evaluation sample obtained in the evaluation of “(2) desmear property (removability of residue at bottom of via)” was washed with an alkaline cleaner (“Cleaner Securigant” manufactured by Atotech Japan Co., Ltd.) at 60 ° C. 902") for 5 minutes and degreased. After washing, the cured product was treated with a pre-dip liquid ("Pre-dip Neogant B" manufactured by Atotech Japan Co., Ltd.) at 25°C for 2 minutes. Thereafter, the cured product was treated with an activator liquid (“Activator Neogant 834” manufactured by Atotech Japan Co., Ltd.) at 40° C. for 5 minutes to attach a palladium catalyst. Next, the cured product was treated with a reducing liquid (“Reducer Neogant WA” manufactured by Atotech Japan Co., Ltd.) at 30° C. for 5 minutes.

Next, the cured product is placed in a chemical copper solution ("Basic Printgant MSK-DK", "Copper Printgant MSK", "Stabilizer Printgant MSK", and "Reducer Cu" manufactured by Atotech Japan Co., Ltd.) for electroless plating. was carried out until the plating thickness reached about 0.5 μm. After electroless plating, an annealing treatment was performed at a temperature of 120° C. for 30 minutes in order to remove residual hydrogen gas. All the steps up to the step of electroless plating were carried out with a beaker scale of 2 liters of the processing liquid, while shaking the cured product.

Electroplating treatment:
Next, the electroless-plated cured product was electroplated until the plating thickness reached 25 μm. As electrolytic copper plating, copper sulfate solution (“Copper sulfate pentahydrate” manufactured by Wako Pure Chemical Industries, “Sulfuric acid” manufactured by Wako Pure Chemical Industries, Ltd. “Basic Leveler Cupalaside HL” manufactured by Atotech Japan, “ Electrolytic plating was carried out until the thickness of the plating reached about 25 μm by applying a current of 0.6 A/cm ² using a correction agent "Capalacid GS"). After the copper plating treatment, the cured product was heated at 200° C. for 60 minutes to further cure the cured product. Thus, a cured product having a copper plating layer laminated on the upper surface was obtained.

Plating peel strength measurement:
In the surface of the copper plating layer of the hardened product on which the obtained copper plating layer was laminated, 10 mm-wide strip-shaped cuts were made at 5 mm intervals at a total of 6 locations. Set the hardened product with the copper plating layer laminated on the upper surface in a 90° peel tester ("TE-3001" manufactured by Tester Sangyo Co., Ltd.), pick up the edge of the notched copper plating layer with a gripper, and make a via The peel strength (plating peel strength) was measured by peeling the copper plating layer by 20 mm while avoiding the portion where was formed. The peel strength (plating peel strength) was measured for each of the six notch points, and the average value of the plating peel strength was obtained. Plating peel strength was determined according to the following criteria.

[Criteria for plating peel strength]
○○: The average value of plating peel strength is 0.50 kgf/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 0.40 kgf/cm cm or more and less than 0.45 kgf/cm ×: Average value of plating peel strength is less than 0.40 kgf/cm

(4) Chipping in the cured product layer at the edge of the substrate “(2) Desmear property (removability of residue at via bottom)” (a) swelling treatment and (b) permanganate treatment. Then, it was heated at 200° C. for 60 minutes to obtain a laminate C. Using a vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.), the obtained laminated film was laminated to the obtained laminate C at a lamination pressure of 0.7 MPa and a lamination temperature of 100 ° C. for 20 seconds. It was laminated and further pressed at a press pressure of 1.0 MPa and a press temperature of 100° C. for 40 seconds. After peeling off the PET film of the laminated film, the resin film was semi-cured by heating at 100° C. for 30 minutes and then at 180° C. for 30 minutes. Then, (a) swelling treatment and (b) permanganate treatment were performed in the same manner as in the evaluation of “(2) desmear property (removability of residue on via bottom)”. Then, 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 treatment, a laminate E was obtained in which 8 cured resin film layers were laminated on both sides of the CCL substrate.

The obtained laminate E was dropped from a height of 1 m a total of 20 times. The presence or absence of chipping of the cured product layer of the resin film at the edge of the substrate was checked using a microscope each time the substrate was dropped.

[Determination Criteria for Chipping in Cured Material Layer at Edge of Substrate]
○○: No chipping occurs in the cured product layer at the edge of the substrate after 20 drops ○: Chipping occurs in the cured product layer at the edge of the substrate after dropping 11 times or more and 19 times or less △: 6 times or more Cracking occurs in the cured product layer at the edge of the substrate when dropped 10 times or less. ×: Chipping occurs in the cured product layer at the edge of the substrate when dropped 1 to 5 times.

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

DESCRIPTION OF SYMBOLS 11... Multilayer printed wiring board 12... Circuit board 12a... Upper surface 13-16... Insulating layer 17... Metal layer

Claims

including an epoxy compound, a filler, and a curing agent;
The average particle size of the filler is 2.0 μm or less,
The resin material, wherein the curing agent includes a first curing agent having a carbonate structure and 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 in 100% by weight of the components excluding the solvent in the resin material.
The resin material according to claim 1 or 2, wherein the first curing agent has a molecular weight of 20,000 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.
The resin material according to claim 4, wherein the second curing agent contains an active ester compound.
The resin material according to any one of claims 1 to 5, which contains a polyimide resin.
The resin material according to any one of claims 1 to 6, which is a resin film.
The resin material according to any one of claims 1 to 7, 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 8.