JP2020050829A - Resin material and multilayer printed board - Google Patents

Abstract

To provide a resin material that 1) can effectively remove smear by desmear treatment, 2) can reduce a dielectric loss tangent of a cured product, and 3) can improve adhesion between an insulating layer and a metal layer.SOLUTION: A resin material has an epoxy compound and a curing agent, the curing agent containing a first compound having a structure in which two aryl groups are bound to each other through a group containing a nitrogen atom or a sulfur atom, and an active ester compound.SELECTED DRAWING: Figure 1

Description

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

  Conventionally, various resin materials have been used to obtain electronic components such as a semiconductor device, a laminated board, and a printed wiring board. For example, in a multilayer printed wiring board, a resin material is used to form an insulating layer for insulating internal layers or to form an insulating layer located on a surface portion. On the surface of the insulating layer, a wiring generally made of metal is laminated. Further, 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 insulating materials for multilayer printed wiring boards including build-up films.

  As an example of the resin material, Patent Document 1 below describes a resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) a smear suppressing component, and a non-volatile component of the resin composition. Is defined as 100% by mass, and a resin composition containing 0.001 to 10% by mass of the smear suppressing component (C) is disclosed.

JP 2014-564 A

  With a conventional resin material, the dielectric loss tangent of the insulating layer (cured product) may not be sufficiently low.

  When forming the insulating layer, a cured material layer (insulating layer) obtained by curing a resin material is formed, and then, after forming a via in the cured material layer, the cured material layer is desmeared. There is. However, in the conventional resin material, smear in the via may not be sufficiently removed by the desmear process. In particular, it is difficult to sufficiently remove the smear in the via with a conventional resin material simply blended and designed so that the dielectric loss tangent of the cured product is reduced or a conventional resin material containing an active ester compound as a curing agent. is there.

  In the resin material described in Patent Document 1, the dielectric loss tangent of the cured product can be reduced to some extent, and (C) a smear suppressing component is included. Therefore, smear can be removed to some extent by desmear treatment. However, in the resin material described in Patent Document 1, the adhesion between the insulating layer and the metal layer may not be sufficiently high.

  Thus, 1) smear can be effectively removed by the desmear treatment, 2) the dielectric loss tangent of the cured product can be reduced, and 3) the adhesion between the insulating layer and the metal layer can be increased. At present, it is extremely difficult to obtain a resin material exhibiting all the effects of 3) to 3).

  An object of the present invention is to 1) effectively remove smear by desmear treatment, 2) reduce the dielectric loss tangent of the cured product, and 3) increase the adhesion between the insulating layer and the metal layer. It is to provide a resin material which can be used. Another object of the present invention is to provide a multilayer printed wiring board using the above resin material.

  According to a broad aspect of the present invention, a first compound comprising an epoxy compound and a curing agent, wherein the curing agent has a structure in which two aryl groups are bonded via a group containing a nitrogen atom or a sulfur atom. And an active ester compound.

  In a specific aspect of the resin material according to the present invention, the first compound is a compound having a structure in which two aryl groups are bonded via a sulfonyl group.

  In a specific aspect of the resin material according to the present invention, the first compound is a compound having a hydroxy group or an amino group.

  In a specific aspect of the resin material according to the present invention, the first compound has a molecular weight of 150 or more and 500 or less.

  In a specific aspect of the resin material according to the present invention, the resin material includes an inorganic filler.

  In a specific aspect of the resin material according to the present invention, the content of the inorganic filler is 30% by weight or more based on 100% by weight of components other than the solvent in the resin material.

  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 an insulating layer in a multilayer printed wiring board.

  According to a broad aspect of the present invention, a circuit board includes 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 at least one of the layers is a cured product of the resin material described above.

  The resin material according to the present invention includes an epoxy compound and a curing agent, wherein the curing agent has a first compound having a structure in which two aryl groups are bonded via a group containing a nitrogen atom or a sulfur atom. , An active ester compound. Since the resin material according to the present invention has the above configuration, 1) smear can be effectively removed by desmear treatment, 2) the dielectric loss tangent of the cured product can be reduced, and 3) All of the effects 1) to 3) that the adhesion between the insulating layer and the metal layer can be enhanced can be exhibited.

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.

  Hereinafter, the present invention will be described in detail.

  The resin material according to the present invention includes an epoxy compound and a curing agent, wherein the curing agent has a first compound having a structure in which two aryl groups are bonded via a group containing a nitrogen atom or a sulfur atom. , An active ester compound.

  Since the resin material according to the present invention has the above configuration, 1) smear can be effectively removed by desmear treatment, 2) the dielectric loss tangent of the cured product can be reduced, and 3) All of the effects 1) to 3) that the adhesion between the insulating layer and the metal layer can be enhanced can be exhibited. For example, in the resin material according to the present invention, 3) as the adhesion between the insulating layer and the metal layer, the plating peel strength between the insulating layer and the metal layer can be increased, and the reflow resistance can be increased.

  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 paste includes a liquid. 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 material. When the resin material is a resin film, the resin film is preferably a thermosetting resin film.

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

[Epoxy compound]
The resin material contains 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. One of the above epoxy compounds may be used alone, or two or more thereof may be used in combination.

  Examples of the epoxy compound include a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, a phenol novolak epoxy compound, a biphenyl epoxy compound, a biphenyl novolak epoxy compound, a biphenol epoxy compound, and a naphthalene 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 having adamantane skeleton, epoxy compound having tricyclodecane skeleton, naphthylene ether type An epoxy compound and an epoxy compound having a triazine nucleus in a skeleton are exemplified.

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

  From the viewpoint of further reducing the dielectric loss tangent and improving the linear expansion coefficient (CTE) of the cured product, the epoxy compound contains an epoxy compound which is liquid at 25 ° C. and an epoxy compound which is solid at 25 ° C. Is preferred.

  The viscosity at 25 ° C. of the liquid epoxy compound at 25 ° C. is preferably 1,000 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 Rheologicals Instruments).

  The molecular weight of the epoxy compound is more preferably 1,000 or less. In this case, even if the content of the inorganic filler is 50% by weight or more based on 100% by weight of the components excluding the solvent in the resin material, a resin material having high fluidity at the time of forming the insulating layer can be obtained. Therefore, when the uncured resin material or the B-staged resin material is laminated on the circuit board, the inorganic filler can be uniformly present.

  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 or when the structural formula of the epoxy compound can be specified. The molecular weight of the epoxy compound means a weight average molecular weight when the epoxy compound is a polymer.

  The content of the epoxy compound in 100% by weight of the resin material excluding the solvent is preferably 4% by weight or more, more preferably 8% by weight or more, preferably 30% by weight or less, more preferably 25% by weight. It is as follows. When the content of the epoxy compound is equal to or more than the lower limit and equal to or less than the upper limit, the thermal dimensional stability of the cured product can be further increased, and the warpage of the cured product can be suppressed more effectively.

  The content of the epoxy compound in 100% by weight of the resin material excluding the inorganic filler and the solvent is preferably 15% by weight or more, more preferably 20% by weight or more, and preferably 50% by weight or less, more preferably Is 45% by weight or less. When the content of the epoxy compound is equal to or more than the lower limit and equal to or less than the upper limit, the thermal dimensional stability of the cured product can be further increased, and the warpage of the cured product can be suppressed more effectively.

[Curing agent]
The resin material contains a curing agent. The curing agent includes a first compound having a structure in which two aryl groups are bonded via a group containing a nitrogen atom or a sulfur atom, and an active ester compound.

<First compound>
The resin material contains, as a curing agent, a first compound having a structure in which two aryl groups are bonded via a group containing a nitrogen atom or a sulfur atom. The first compound preferably has a functional group capable of reacting with the epoxy group of the epoxy compound. As the first compound, only one kind may be used, or two or more kinds may be used in combination.

  The group containing a nitrogen atom or a sulfur atom may be a group containing a nitrogen atom, a group containing a sulfur atom, or a group containing a nitrogen atom and a sulfur atom.

  In a structure in which two aryl groups are bonded via a group containing a nitrogen atom or a sulfur atom, a ring may be formed by the group containing a nitrogen atom or a sulfur atom and an aryl group.

  Examples of the first compound include a compound represented by the following formula (1A), a compound represented by the following formula (1B), and a compound represented by the following formula (1C).

  In the above formula (1A), X represents a group containing a nitrogen atom or a sulfur atom, and R1 and R2 represent any groups.

  In the above formula (1B), X represents a group containing a nitrogen atom or a sulfur atom, and R1 and R2 represent any groups.

  In the above formula (1C), X represents a group containing a nitrogen atom or a sulfur atom, and R1 and R2 represent any groups.

  In the compound represented by the above formula (1B), a ring is formed by the group containing a nitrogen atom or a sulfur atom and two aryl groups. In the compound represented by the formula (1C), a ring is formed by the group containing a nitrogen atom or a sulfur atom and one aryl group.

  Examples of the compound represented by the above formula (1C) include a compound represented by the following formula (11C).

  In the above formula (11C), R1 and R2 represent an arbitrary group.

  From the viewpoint of more effectively exhibiting the effects of the present invention described in 1) to 3) above, the first compound is a compound represented by the above formula (1A) and a compound represented by the above formula (1B). And the compound represented by the formula (1C), the compound represented by the formula (1A) is preferable.

  In the first compound, the group containing the nitrogen atom (X in the formula (1A), X in the formula (1B), and X in the formula (1C)) includes an amino group, an amide group, Examples include an imide group, a nitrile group, a carbodiimide group, an azo group, and a group having a piperazine skeleton.

  The group containing the sulfur atom (X in the formula (1A), X in the formula (1B), and X in the formula (1C)) in the first compound is a sulfonyl group, a thiol group, And a sulfide group.

  From the viewpoint of more effectively exhibiting the effects of 1) to 3) of the present invention, the group containing a nitrogen atom or a sulfur atom is preferably a group containing a sulfur atom, and is a sulfonyl group. Is more preferable. That is, the first compound is preferably a compound having a structure in which two aryl groups are bonded through a group containing a sulfur atom, and the two aryl groups are bonded through a sulfonyl group. More preferably, the compound has a structure.

  In the above formula (1A), R1 and R2 may be the same or different. In the above formula (1B), R1 and R2 may be the same or different. In the above formula (1C), R1 and R2 may be the same or different.

  In the formulas (1A), (1B), and (1C), R1 and R2 each represent a hydroxy group, an amino group, a cyanato group, an ester group, a maleimide, a carboxyl group, an acid anhydride group, And a group containing an aromatic skeleton.

  The first compound is preferably a compound having an amino group or a hydroxy group. From the viewpoint of more effectively removing smear by desmear treatment, the first compound is preferably a compound having an amino group. From the viewpoint of further increasing the adhesion between the insulating layer and the metal layer, the first compound is preferably a compound having a hydroxy group. In this case, the first compound may have a hydroxy group or an amino group in X in the formula (1A), the formula (1B), or the formula (1C). Alternatively, R2 may have a hydroxy group or an amino group.

  The molecular weight of the first compound is preferably 150 or more, more preferably 200 or more, preferably 500 or less, more preferably 400 or less. When the molecular weight of the first compound is equal to or greater than the lower limit and equal to or less than the upper limit, the effects of 1) to 3) of the present invention described above can be more effectively exerted.

  The content of the first compound with respect to 100 parts by weight of the epoxy compound is preferably 0.25 parts by weight or more, more preferably 0.5 parts by weight or more, preferably 30 parts by weight or less, more preferably 25 parts by weight or less. It is. When the content of the first compound is equal to or more than the lower limit and equal to or less than the upper limit, the effects of 1) to 3) of the present invention described above can be more effectively exerted. Further, when the content of the first compound is not less than the lower limit and not more than the upper limit, the curability is more excellent, the thermal dimensional stability is further increased, and the volatilization of the remaining unreacted components can be further suppressed.

  In 100% by weight of the curing agent, the content of the first compound is preferably 0.2% by weight or more, more preferably 0.4% by weight or more, preferably 30% by weight or less, more preferably 25% by weight. It is as follows. When the content of the first compound is equal to or more than the lower limit and equal to or less than the upper limit, the effects of 1) to 3) of the present invention described above can be more effectively exerted.

<Active ester compound>
The resin material contains an active ester compound (second compound) as a curing agent. The active ester compound preferably has a functional group capable of reacting with the epoxy group of the epoxy compound. One of the active ester compounds may be used alone, or two or more thereof may be used in combination.

  The active ester compound is a compound having at least one ester bond and having 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 a thiocarboxylic acid compound with a hydroxy compound or a thiol compound. Examples of the active ester compound include a compound represented by the following formula (2).

  In the above formula (2), 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 an aromatic ring include a benzene ring which may have a substituent and a naphthalene ring which may have a substituent. Examples of the substituent include a hydrocarbon group. The number of carbon atoms of the hydrocarbon group is preferably 12 or less, more preferably 6 or less, and still more preferably 4 or less.

  In the above formula (2), as the combination of X1 and X2, a combination of a benzene ring which may have a substituent and a benzene ring which may have a substituent, And a naphthalene ring which may have a substituent. Further, in the above formula (2), examples of the combination of X1 and X2 include a combination of a naphthalene ring which may have a substituent and a naphthalene ring which may have a substituent.

  The active ester compound is not particularly limited. From the viewpoint of enhancing thermal dimensional stability and flame retardancy, the active ester compound is preferably an active ester compound having two or more aromatic skeletons. From the viewpoint of reducing 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.

  Commercial products of the active ester compound include "HPC-8000-65T", "EXB9416-70BK", "EXB8100-65T", and "HPC-8150-60T" manufactured by DIC.

  The content of the active ester compound with respect to 100 parts by weight of the epoxy compound is preferably 70 parts by weight or more, more preferably 85 parts by weight or more, preferably 150 parts by weight or less, more preferably 140 parts by weight or less. When the content of the active ester compound is equal to or more than the lower limit, the curability is more excellent, the dielectric loss tangent of the cured product can be reduced, and the adhesion between the insulating layer and the metal layer can be increased. When the content of the active ester compound is equal to or less than the upper limit, smear can be more effectively removed by desmear treatment.

  The content of the active ester compound in 100% by weight of the curing agent is preferably 50% by weight or more, more preferably 60% by weight or more, preferably 99.8% by weight or less, more preferably 99.6% by weight or less. It is. When the content of the active ester compound is at least the lower limit, the dielectric loss tangent of the cured product can be reduced, and the adhesion between the insulating layer and the metal layer can be increased. When the content of the active ester compound is equal to or less than the upper limit, smear can be more effectively removed by desmear treatment.

<Curing agent X>
As the curing agent, a curing agent different from both a compound having a structure in which two aryl groups are bonded via a group containing a nitrogen atom or a sulfur atom and an active ester compound (hereinafter referred to as “curing agent X”) May be described as "). As the curing agent X, only one type may be used, or two or more types may be used in combination.

  Examples of the curing agent X include a cyanate ester compound (cyanate ester curing agent), an amine compound (amine curing agent), a thiol compound (thiol curing agent), an imidazole compound, a phosphine compound, dicyandiamide, a phenol compound (phenol curing agent), and an acid. Examples thereof include anhydrides, carbodiimide compounds (carbodiimide curing agents), maleimide compounds (maleimide curing agents), and benzoxazine compounds (benzoxazine curing agents). The curing agent X preferably has a functional group capable of reacting with the epoxy group of the epoxy compound.

  Examples of the cyanate ester compound include a novolak-type cyanate ester resin, a bisphenol-type cyanate ester resin, and a prepolymer in which these are partially trimerized. Examples of the novolak type cyanate ester resin include a phenol novolak type cyanate ester resin and an alkylphenol type cyanate ester resin. Examples of the bisphenol type cyanate ester resin include a bisphenol A type cyanate ester resin, a bisphenol E type cyanate ester resin, and a tetramethyl bisphenol F type cyanate ester resin.

  Commercially available products of the above cyanate ester compounds include phenol novolak type cyanate ester resins (“PT-30” and “PT-60” manufactured by Lonza Japan) and prepolymers obtained by trimerizing bisphenol type cyanate ester resins (Lonza Japan). “BA-230S”, “BA-3000S”, “BTP-1000S” and “BTP-6020S”).

  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.

  Commercially available phenol compounds include novolak phenol ("TD-2091" manufactured by DIC), biphenyl novolak phenol ("MEH-7851" manufactured by Meiwa Kasei), and aralkyl phenol compounds ("MEH" manufactured by Meiwa Kasei). -7800 "), and phenols having an aminotriazine skeleton (" LA1356 "and" LA3018-50P "manufactured by DIC).

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

  Commercial products of the above-mentioned acid anhydride include "Rikashid TDA-100" manufactured by Shin Nippon Rika Co., Ltd.

  The carbodiimide compound is a compound having a structural unit represented by the following formula (3). In the following formula (3), the right end and the left end are binding sites to other groups. One kind of the carbodiimide compound may be used alone, or two or more kinds may be used in combination.

  In the above formula (3), X represents an alkylene group, a group having a substituent bonded to an alkylene group, a cycloalkylene group, a group having a substituent bonded to a cycloalkylene group, an arylene group, or a substituent having been bonded to an arylene group. And p represents an integer of 1 or more and 5 or less. When there are a plurality of Xs, the plurality of Xs may be the same or different.

  In the above formula (3), at least one X is preferably 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 Nisshinbo Chemical's "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", "Carbodilite V-09", and "Carbodilite V-09". 10M-SP "and" Carbodilite 10M-SP (revised) ", as well as" STABAXOL P "," STABAXOL P400 ", and" HIKAZIL 510 "manufactured by Rhine Chemie.

  The maleimide compound may be a bismaleimide compound.

  Examples of the bismaleimide compound include an aromatic bismaleimide compound and an aliphatic bismaleimide compound.

  Examples of the aliphatic bismaleimide compound include an N-alkylbismaleimide compound.

  From the viewpoint of lowering the dielectric loss tangent and lowering the curing temperature, the maleimide compound is preferably an N-alkylbismaleimide compound.

  Commercially available products of the N-alkylbismaleimide compounds include Designer Molecular Inc. "BMI-1500", "BMI-1700", "BMI-3000" and the like.

  Examples of the benzoxazine compound include Pd-type benzoxazine and Fa-type benzoxazine.

  Commercially available benzoxazine compounds include "Pd type" manufactured by Shikoku Chemicals.

  The content of the curing agent X with respect to 100 parts by weight of the epoxy compound is preferably 2 parts by weight or more, more preferably 5 parts by weight or more, preferably 30 parts by weight or less, more preferably 25 parts by weight or less. When the content of the curing agent X is equal to or more than the lower limit and equal to or less than the upper limit, curability is further improved, thermal dimensional stability is further increased, and volatilization of remaining unreacted components can be further suppressed.

  In 100% by weight of the curing agent, the content of the curing agent X is preferably 1.5% by weight or more, more preferably 3% by weight or more, preferably 40% by weight or less, and more preferably 35% by weight or less. . When the content of the curing agent X is equal to or more than the lower limit and equal to or less than the upper limit, the effects of the present invention of 1) to 3) described above can be more effectively exerted.

[Inorganic filler]
The resin material preferably contains an inorganic filler. By using the inorganic filler, the dielectric loss tangent of the cured product can be further reduced. In addition, the use of the inorganic filler further reduces the dimensional change of the cured product due to heat. As the inorganic filler, only one kind may be used, or two or more kinds may be used in combination.

  Examples of the inorganic filler include silica, talc, clay, mica, hydrotalcite, alumina, magnesium oxide, aluminum hydroxide, aluminum nitride, and boron nitride.

  Reduces the surface roughness of the surface of the cured product, further increases the plating peel strength between the cured product and the metal layer, forms finer wiring on the surface of the cured product, and provides better insulation reliability with the cured product From the viewpoint of imparting properties, the inorganic filler is preferably silica or alumina, more preferably silica, and even more preferably fused silica. By using silica, the coefficient of thermal expansion of the cured product is further reduced, and the dielectric loss tangent of the cured product is further reduced. In addition, by using silica, the surface roughness of the surface of the cured product is effectively reduced, and the adhesive strength between the cured product and the metal layer is effectively increased. The shape of the silica is preferably spherical.

  Regardless of the curing environment, advance the curing of the resin, effectively increase the glass transition temperature of the cured product, from the viewpoint of effectively reducing the coefficient of linear thermal expansion of the cured product, the inorganic filler is spherical silica Is preferred.

  The average particle size of the inorganic filler is preferably 50 nm or more, more preferably 100 nm or more, further preferably 500 nm or more, preferably 5 μm or less, more preferably 3 μm or less, and still more preferably 1 μm or less. When the average particle size of the inorganic filler is equal to or greater than the lower limit and equal to or less than the upper limit, the surface roughness after etching can be reduced, and the plating peel strength can be increased. Adhesion can be further improved.

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

  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. 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 a surface-treated product with a coupling agent, and even more preferably a surface-treated product with a silane coupling agent. By the surface treatment of the inorganic filler, the surface roughness of the surface of the roughened and cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased. Further, since the inorganic filler is subjected to the surface treatment, finer wiring can be formed on the surface of the cured product, and more favorable inter-wiring insulation reliability and interlayer insulation reliability can be obtained in the cured product. Can be granted.

  Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent. Examples of the silane coupling agent include methacryl silane, acryl silane, amino silane, imidazole silane, vinyl silane, and epoxy silane.

  The content of the inorganic filler is preferably 30% by weight or more, more preferably 60% by weight or more, still more preferably 65% by weight or more, particularly preferably 68% by weight in 100% by weight of the components excluding the solvent in the resin material. % Or less, preferably 90% by weight or less, more preferably 85% by weight or less, still more preferably 80% by weight or less, particularly preferably 75% by weight or less. When the content of the inorganic filler is equal to or more than the lower limit, the dielectric loss tangent is effectively reduced. When the content of the inorganic filler is equal to or less than the upper limit, the storage stability of the resin material can be increased, and the thermal dimensional stability of the cured product can be increased. It can be suppressed effectively. When the content 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 of the surface of the cured product can be further reduced, and finer wiring can be formed on the surface of the cured product. Can be. Further, with the content of the inorganic filler, it is possible to lower the coefficient of thermal expansion of the cured product and at the same time to improve the smear removal property.

[Curing accelerator]
The resin material preferably contains a curing accelerator. The use of the curing accelerator further increases the curing speed. By rapidly curing the resin material, the crosslinked structure in the cured product becomes uniform, and the number of unreacted functional groups decreases, resulting in an increase in the crosslink density. The curing accelerator is not particularly limited, and a conventionally known curing accelerator can be used. One type of the above-mentioned curing accelerator may be used alone, or two or more types 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 ′ -Methyl Midazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6 [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine Isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-dihydroxymethylimidazole and the like No.

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

  Examples of the phosphorus compound include a triphenylphosphine compound.

  Examples of the organometallic compound 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 lowering the curing temperature and effectively suppressing the warpage 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 warpage of the cured product, the content of the anionic curing accelerator in 100% by weight of the curing accelerator is preferably 20% by weight or more, more preferably Is 50% by weight or more, more preferably 70% by weight or more, and most preferably 100% by weight (total amount). Therefore, the curing accelerator is most preferably the anionic curing accelerator.

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

[Thermoplastic resin]
The resin material preferably contains a thermoplastic resin. Examples of the thermoplastic resin include a polyvinyl acetal resin, a polyimide resin, and a phenoxy resin. Only one type of thermoplastic resin may be used, or two or more types may be used in combination.

  Regardless of the curing environment, the thermoplastic resin is preferably a phenoxy resin from the viewpoint of effectively improving the adhesion of the metal wiring. By using the phenoxy resin, deterioration of the embedding property of the resin film into holes or irregularities of the circuit board and non-uniformity of the inorganic filler can be suppressed. In addition, the use of the phenoxy resin makes it possible to adjust the melt viscosity, so that the dispersibility of the inorganic filler is improved, and in the laminating and curing processes, the resin composition or the B-staged product is less likely to spread to unintended regions. Become.

  The phenoxy resin contained in the resin material is not particularly limited. As the phenoxy resin, a conventionally known phenoxy resin can be used. The phenoxy resin may be used alone or in combination of two or more.

  Examples of the phenoxy resin include 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.

  Commercially available phenoxy resins include, for example, "YP50", "YP55" and "YP70" manufactured by Nippon Steel & Sumitomo Metal Corporation, and "1256B40", "4250", "4256H40", and "4256H40" manufactured by Mitsubishi Chemical Corporation. 4275 "," YX6954BH30 "and" YX8100BH30 ".

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

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

  Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetraanhydride 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-dicarboxypheno) B) diphenylsulfone 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 (Triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, and the like. .

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

  In addition, the said polyimide compound may have an acid anhydride structure, a maleimide structure, and a citraconimide structure in the terminal. In this case, the polyimide compound can react with the epoxy resin. The thermal dimensional stability of the cured product can be increased by reacting the polyimide compound with the epoxy resin.

  From the viewpoint of obtaining a resin material having more excellent storage stability, the thermoplastic resin, the weight average molecular weight of the polyimide resin and the phenoxy resin is preferably 5,000 or more, more preferably 10,000 or more, preferably 100,000 or less, more preferably Is 50,000 or less.

  The weight average molecular weight of the thermoplastic resin, the polyimide resin, and the phenoxy resin indicates a 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 (in the case where 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 inorganic filler and the solvent in the resin material is , Preferably 1% by weight or more, more preferably 2% by weight or more, preferably 30% by weight or less, more preferably 20% by weight or less. When the content of the thermoplastic resin is equal to or more than the lower limit and equal to or less than the upper limit, the embedding property of the resin material into holes or irregularities of the circuit board is improved. When the content of the thermoplastic resin is equal to or more than the above lower limit, formation of the resin film is further facilitated, and a better insulating layer is obtained. When the content of the thermoplastic resin is equal to or less than the above upper limit, the coefficient of thermal expansion of the cured product is further reduced. When the content of the thermoplastic resin is equal to or less than the upper limit, the surface roughness of the surface 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. By using the solvent, the viscosity of the resin material can be controlled in a suitable range, and the coating property of the resin material can be improved. Further, the solvent may be used to obtain a slurry containing the inorganic filler. The solvent may be used alone or in combination of two or more.

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

  Most of the solvent is preferably removed when the resin composition is formed into a film. Therefore, the boiling point of the solvent is preferably 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 and the like.

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

[Other components]
For the purpose of improving impact resistance, heat resistance, resin compatibility, workability, etc., the above resin materials are used as leveling agents, flame retardants, coupling agents, coloring agents, antioxidants, ultraviolet deterioration inhibitors, defoamers. It may contain a thermosetting resin other than an agent, a thickener, a thixotropic agent and an epoxy compound.

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

  Examples of the other thermosetting resins include polyphenylene ether resin, divinyl benzyl ether resin, polyarylate resin, diallyl phthalate resin, benzoxazine resin, benzoxazole resin, and acrylate resin.

(Resin film)
A resin film (B-staged product / B-stage film) can be obtained by molding the above-described resin composition into a film. The resin material is preferably a resin film. The resin film is preferably a B-stage film.

  As a method of forming the resin composition into a film shape to obtain a resin film, the following method is exemplified. An extrusion molding method in which a resin composition is melt-kneaded using an extruder, extruded, and then formed into a film by a T-die or a circular die. A casting method in which a resin composition containing a solvent is cast to form a film. Other known film forming methods. The extrusion molding method or the casting molding method is preferable because it can cope with thinning. The film includes a sheet.

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

  The film-shaped resin composition obtained by the above-described drying step is referred to as a B-stage film. The B stage film is in a semi-cured state. The semi-cured product is not completely cured, and curing may proceed further.

  The resin film need not be a prepreg. When the resin film is not a prepreg, migration does not occur along a glass cloth or the like. Further, when laminating or pre-curing the resin film, the surface does not have irregularities due to the glass cloth.

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

  Examples of the base film of the laminated film include polyester resin films such as polyethylene terephthalate film and polybutylene terephthalate film, olefin resin films such as polyethylene film and polypropylene film, and polyimide resin films. The surface of the base film may be subjected to a release treatment, if necessary.

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

(Semiconductor devices, printed wiring boards, copper-clad laminates and multilayer printed wiring boards)
The 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 forming an insulating layer in a printed wiring board.

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

  A member to be laminated having a metal layer on one surface or both surfaces can be laminated on the resin film. A laminated structure comprising a member to be laminated having a metal layer on the 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 the surface 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 the surface while heating or pressing without heating.

  Preferably, the material of the metal layer is copper.

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

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

  The thickness of the copper foil of the copper clad laminate is not particularly limited. The thickness of the copper foil is preferably in the range of 1 μm to 50 μm. Further, 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 the surface. The method for forming the irregularities is not particularly limited. Examples of the method for forming the irregularities include a known method using a treatment using a chemical solution.

  The above resin material is suitably used for obtaining a multilayer substrate.

  As an example of the multilayer substrate, there is a multilayer substrate including a circuit board and an insulating layer laminated on the circuit board. The insulating layer of the multilayer substrate is formed of the above resin material. Further, the insulating layer of the multilayer substrate may be formed by using the laminated film and the resin film of the laminated film. The insulating layer is preferably stacked on a surface of the circuit board on which the circuit is provided. It is preferable that a part of the insulating layer is embedded between the circuits.

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

  As the roughening method, a conventionally known roughening method can be used, and there is no particular limitation. The surface of the insulating layer may be swelled before the roughening treatment.

  Preferably, 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 substrate, a circuit board, an insulating layer laminated on the surface of the circuit board, and a surface of the insulating layer opposite to the surface on which the circuit substrate is laminated are laminated on a surface opposite to the surface on which the circuit substrate is laminated. And a multi-layer substrate provided with a copper foil. The insulating layer is preferably formed by curing the resin film using a copper-clad laminate including a copper foil and a resin film laminated on one surface of the copper foil. Further, the copper foil has been subjected to an etching treatment, 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 stacked on the surface of the circuit board. At least one of the plurality of insulating layers disposed on the circuit board is formed using the resin material. It is preferable that the multilayer substrate further includes a circuit laminated on at least one surface of the insulating layer formed using the resin film.

  Among multilayer substrates, a multilayer printed wiring board is required to have a low dielectric loss tangent, and is required to have high insulation reliability by an insulating layer. In the resin material according to the present invention, insulation reliability can be effectively improved by effectively exhibiting the effects of the present invention described in 1) to 3) above. Therefore, the resin material according to the present invention is suitably used for forming an insulating layer in a multilayer printed wiring board.

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

  FIG. 1 is a cross-sectional view schematically showing a multilayer printed wiring board using a resin material according to one 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 product layers. A metal layer 17 is formed in a partial region of the upper surface 12a of the circuit board 12. Among the plurality of insulating layers 13 to 16, a metal layer 17 is formed on a part of the upper surface of the insulating layers 13 to 15 other than the insulating layer 16 located on the outer surface opposite to the circuit board 12 side. Have been. The metal layer 17 is a circuit. The metal layers 17 are respectively arranged between the circuit board 12 and the insulating layer 13 and between the stacked insulating layers 13 to 16. The lower metal layer 17 and the upper metal layer 17 are connected to each other by at least one of a via-hole connection and a through-hole connection (not shown).

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

(Swelling and roughening)
The resin material is preferably used to obtain a cured product that is subjected to a swelling treatment and a roughening treatment. The cured product also includes a pre-cured product that can be further cured.

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

  As a method of the swelling treatment, for example, a method of treating a cured product with an aqueous solution of a compound containing ethylene glycol or the like as a main component or an organic solvent dispersion solution 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 treatment temperature of 30 ° C. to 85 ° C. for 1 minute to 30 minutes using a 40% by weight aqueous solution of ethylene glycol or the like. The temperature of the swelling treatment is preferably in the range of 50C to 85C. 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, 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 an aqueous solution or an organic solvent dispersion after water or an organic solvent is added. The roughening solution 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 bichromate and anhydrous potassium chromate. Examples of the above persulfate compound include sodium persulfate, potassium persulfate, and ammonium persulfate.

  The arithmetic average 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, and even more preferably less than 150 nm. In this case, the adhesive strength between the cured product and the metal layer is increased, and further finer wiring is formed on the surface of the insulating layer. The arithmetic average roughness Ra is measured according to JIS B0601: 1994.

(Desmear treatment)
Through holes may be formed in the cured product obtained by pre-curing the resin material. In the above-mentioned multilayer substrate or the like, a via or a through hole is formed as a through hole. For example, vias can be formed by irradiation with a laser such as a CO ₂ laser. The diameter of the via is not particularly limited, but is about 40 μm to 80 μm. Due to the formation of the through holes, smear, which is a residue of the 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. Desmear processing may also serve as roughening processing.

  In the desmear treatment, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound, or a persulfate compound is used in the same manner as in the roughening treatment. These chemical oxidants are used as an aqueous solution or an organic solvent dispersion after water or an organic solvent is added. The desmear treatment liquid used for the desmear treatment 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 becomes sufficiently small.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.

  The following materials were prepared.

(Epoxy compound)
Biphenyl novolak type epoxy compound ("NC-3000" manufactured by Nippon Kayaku)
Glycidylamine type epoxy compound ("630" manufactured by Mitsubishi Chemical Corporation)
Dicyclopentadiene type epoxy compound (“EP-4088S” manufactured by ADEKA)

(Curing agent)
<First compound>
4,4'-Diaminodiphenyl sulfone (manufactured by Seika, molecular weight 248)
N- (4-Aminophenyl) -4-aminobenzamide (manufactured by Seika, molecular weight 227)
2- (4-Aminophenyl) -6-aminobenzoxazole (Seika, molecular weight 225)
Bis (4-hydroxyphenyl) sulfone (Tokyo Kasei Kogyo Co., Ltd., molecular weight 250)
Bis [4- (4-aminophenoxy) phenyl] sulfone (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 432)

<Active ester compound>
Liquid containing active ester compound ("EXB-9416-70BK" manufactured by DIC, solid content 70% by weight)

<Curing agent X>
2,2-Bis (4-hydroxyphenyl) propane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 228) (a compound not corresponding to the first compound)

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

(Thermoplastic resin)
Phenoxy resin-containing liquid (Mitsubishi Chemical Corporation, "YX6954BH30", solid content 30% by weight)

(Curing accelerator)
Dimethylaminopyridine (“DMAP” manufactured by Wako Pure Chemical Industries, Ltd.)

(Examples 1 to 5 and Comparative Example 1)
The components shown in Table 1 below were blended in the amounts shown in Table 1 (units: parts by weight of solids), and stirred at room temperature until a uniform solution was obtained, to obtain a resin material.

Preparation of resin film:
Using an applicator, the obtained resin material was coated on the release-treated surface of a release-treated PET film (“XG284” manufactured by Toray Industries, Inc., thickness: 25 μm), and then applied in a gear oven at 100 ° C. for 2 minutes. Dry and evaporate the solvent. Thus, a laminated film (a laminated film of a PET film and a resin film) in which a resin film (B-stage film) having a thickness of 40 μm was laminated on the PET film was obtained.

(Evaluation)
(1) Removal of smear Laminating step and semi-curing treatment:
A double-sided copper-clad laminate (CCL substrate) (a copper foil thickness of 18 μm on each surface, a substrate thickness of 0.7 mm, a substrate size of 100 mm × 100 mm, “MCL-E679FG” manufactured by Hitachi Chemical Co., Ltd.) was prepared. Both surfaces of the copper foil surface of this double-sided copper-clad laminate were immersed in “Cz8100” manufactured by MEC to roughen the surface of the copper foil. On both sides of the roughened copper-clad laminate, the resin film (B-stage film) side of the laminated film was placed on the copper-clad laminate using “Machine Seisakusho Co., Ltd.” “Batch type vacuum laminator MVLP-500-IIA”. And laminated to obtain a laminated structure. The lamination was performed by reducing the pressure to 13 hPa or less by reducing the pressure for 30 seconds, laminating at 100 ° C. and a pressure of 0.7 MPa for 30 seconds, and then pressing at 100 ° C. and a pressing pressure of 0.8 MPa for 60 seconds. Thereafter, the PET film was peeled off and heated at 180 ° C. for 30 minutes to semi-cure the resin film. Thus, a laminate in which the semi-cured resin film was laminated on the CCL substrate was obtained.

Via hole forming process:
Using a CO ₂ laser beam machine (“LC-4KF212” manufactured by Via Mechanics Co., Ltd.), a via hole having a diameter of about 60 μm was formed under the conditions of burst mode, energy 0.4 mJ, pulse 27 μsec, and 3 shots.

Roughening and desmearing:
(A) Swelling treatment:
The obtained laminate was put into a swelling liquid at 60 ° C. (“Swelling Dip Securiganto P” manufactured by Atotech Japan) and rocked for 10 minutes. Thereafter, the substrate was washed with pure water.

(B) Permanganate treatment (roughening treatment and desmear treatment):
The laminated body after the swelling treatment was put into a roughened aqueous solution of potassium permanganate (“Concentrate Compact CP” manufactured by Atotech Japan) at 80 ° C. and rocked for 30 minutes. Next, after treating for 2 minutes using a washing liquid at 25 ° C. (“Reduction Securiganto P” manufactured by Atotech Japan), washing was performed with pure water to obtain a laminate after desmear treatment.

Observation of via bottom:
The bottom of the via of the laminate after the desmear treatment was observed with a scanning electron microscope (SEM), and the maximum length of smear from the wall surface of the via bottom was measured. The removability of the residue at the via bottom was determined based on the following criteria.

[Criteria for Smear Removal]
○: The maximum length of smear is less than 2 μm ○: The maximum length of smear is 2 μm or more and less than 3.5 μm △: The maximum length of smear is 3.5 μm or more and less than 5 μm ×: The maximum length of smear is 5 μm or more

(2) Adhesion between insulating layer and metal layer (2-1) Adhesion between insulating layer and metal layer (peel strength)
Laminating process:
A double-sided copper-clad laminate (a copper foil thickness of 18 μm on each surface, a substrate thickness of 0.7 mm, a substrate size of 100 mm × 100 mm, “MCL-E679FG” manufactured by Hitachi Chemical Co., Ltd.) was prepared. Both surfaces of the copper foil surface of this double-sided copper-clad laminate were immersed in “Cz8101” manufactured by MEC to roughen the surface of the copper foil. On both sides of the roughened copper-clad laminate, the resin film (B-stage film) side of the laminated film was placed on the copper-clad laminate using “Machine Seisakusho Co., Ltd.” “Batch type vacuum laminator MVLP-500-IIA”. And laminated to obtain a laminated structure. The lamination conditions were such that the pressure was reduced to 13 hPa or less by reducing the pressure for 30 seconds, and then laminating at 100 ° C. and a pressure of 0.7 MPa for 30 seconds.

Film peeling process:
In the obtained laminated structure, the PET films on both sides were peeled off.

Copper foil attaching process:
The shiny surface of the copper foil (thickness: 35 μm, manufactured by Mitsui Kinzoku Co., Ltd.) was subjected to Cz treatment (“Cz8101” manufactured by MEC), and the copper foil surface was etched by about 1 μm. Using Meiki Seisakusho's “Batch type vacuum laminator MVLP-500-IIA”, an etched copper foil is laminated on the laminated structure from which the PET film has been peeled to obtain a substrate with a copper foil. Was. The conditions for lamination were such that the pressure was reduced to 13 hPa or less by reducing the pressure for 30 seconds, then laminating at 100 ° C. and a pressure of 0.7 MPa for 30 seconds, and further pressing for 60 seconds at a pressing temperature of 100 ° C. and a pressing pressure of 0.8 MPa. .

  The obtained substrate with a copper foil was heated in a gear oven at 180 ° C. for 30 minutes, and then heat-treated at 200 ° C. for 60 minutes to obtain an evaluation sample.

  A 1 cm wide strip was cut into the surface of the copper foil of the evaluation sample. The evaluation sample was set on a 90 ° peel tester (“TE-3001” manufactured by Tester Sangyo Co., Ltd.), the end of the cut copper foil was picked up with a gripper, and the copper foil was peeled off by 20 mm to obtain peel strength (peel). Strength) was measured.

[Judgment criteria for adhesion (peel strength) between insulating layer and metal layer]
○: Peel strength of 0.6 kgf / cm or more 〇: Peel strength of 0.5 kgf / cm or more and less than 0.6 kgf / cm Δ: Peel strength of 0.4 kgf / cm or more and less than 0.5 kgf / cm ×: Peel strength Is less than 0.4kgf / cm

(2-2) Reflow resistance A laminate after desmear treatment prepared in (1) Smear removability described above was prepared.

Electroless plating process:
The surface of the roughened cured product was treated with an alkaline cleaner at 60 ° C. (“Cleaner Securigant 902” manufactured by Atotech Japan) for 5 minutes, and degreased and washed. After washing, the cured product was treated with a pre-dip liquid at 25 ° C. (“Pre-Dip Neo-Gant B” manufactured by Atotech Japan) for 2 minutes. Thereafter, the cured product was treated with an activator solution ("Activator Neo Gant 834" manufactured by Atotech Japan) at 40 ° C for 5 minutes to attach 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 was placed in a chemical copper solution (all "Basic Print Gant MSK-DK", "Copper Print Gant MSK", "Stabilizer Print Gant MSK", "Reducer Cu" manufactured by Atotech Japan), and electroless plating was performed. Was carried out until the plating thickness became about 0.5 μm. After the electroless plating, annealing was performed at a temperature of 120 ° C. for 30 minutes in order to remove the remaining hydrogen gas. All the processes up to the electroless plating process were performed while making the treatment liquid 2 L on a beaker scale and oscillating the cured product.

Electrolytic copper plating process:
After the electroless plating was formed, electrolytic copper plating was performed until the plating thickness became 25 μm to form an electrolytic copper plating layer. Copper sulfate aqueous solution ("Copper sulfate pentahydrate" manufactured by Wako Pure Chemical Industries, "Sulfuric acid" manufactured by Wako Pure Chemical Industries, "Basic Leveler Capparaside HL" manufactured by Atotech Japan, "Atotech Japan" A current of 0.6 A / cm ² was passed using the corrector Capalaside GS ”).

Full curing process:
The laminated structure after the quick etching was heated in a gear oven at 200 ° C. for 60 minutes and fully cured to prepare a sample for evaluation.

Evaluation of reflow resistance:
Using the evaluation sample (100 mm × 100 mm), the evaluation sample was absorbed (at a temperature of 60 ° C. and a humidity of 60 RH% for 40 hours) in accordance with LEVEL3 of JEDEC. Thereafter, the sample for evaluation was subjected to a nitrogen reflow treatment (peak top temperature: 260 ° C.). The reflow was repeated 30 times. The occurrence of blisters after reflow was visually checked.

[Judgment criteria for reflow resistance]
○: No blisters generated after 30 reflows ○: Blisters generated after 25 to 29 reflows △: Blister generated after 21 to 24 reflows ×: Blister generated after 20 or less reflows

(3) Dielectric loss tangent The obtained resin film was cut into a size of 2 mm in width and 80 mm in length, and five sheets were overlapped to obtain a laminate having a thickness of 200 µm. The obtained laminate was heated at 200 ° C. for 90 minutes to obtain a cured product. The obtained cured product was cooled to room temperature (23 ° C.) by the cavity resonance method using “Cavity Resonance Perturbation Method Permittivity Measurement Apparatus CP521” manufactured by Kanto Electronics Application Development Co., Ltd. and “Network Analyzer N5224A PNA” manufactured by Keysight Technology. The dielectric loss tangent was measured at a frequency of 5.8 GHz.

[Judgment criteria for dielectric loss tangent]
：: Dielectric tangent is 0.004 or less Δ: Dielectric tangent is more than 0.004 and less than 0.0045 ×: Dielectric tangent is more than 0.0045

  The composition and results are shown in Table 1 below.

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

Claims (9)

Including an epoxy compound and a curing agent,
A resin material, wherein the curing agent includes a first compound having a structure in which two aryl groups are bonded via a group containing a nitrogen atom or a sulfur atom, and an active ester compound.   The resin material according to claim 1, wherein the first compound is a compound having a structure in which two of the aryl groups are bonded via a sulfonyl group.   The resin material according to claim 1, wherein the first compound is a compound having a hydroxy group or an amino group.   The resin material according to any one of claims 1 to 3, wherein the first compound has a molecular weight of 150 or more and 500 or less.   The resin material according to claim 1, further comprising an inorganic filler.   The resin material according to claim 5, wherein the content of the inorganic filler is 30% by weight or more based on 100% by weight of a component excluding the solvent in the resin material.   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 claim 1.

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