JP7226954B2 - Resin materials and multilayer printed wiring boards - Google Patents

Description

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.

2. Description of the Related Art 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.

As an example of the resin material, Patent Document 1 below discloses a thermosetting resin composition containing a thermosetting resin, an active ester compound having an active ester group, and a carbodiimide compound having a carbodiimide group. It is

JP 2006-335834 A

With the resin material described in Patent Document 1, the dielectric loss tangent of the insulating layer (cured material) can be lowered to some extent. However, with the conventional resin material as described in Patent Document 1, a cured product obtained by curing the resin material may warp. When the cured product is warped, the circuit board and the metal layer are also warped along with the cured product, resulting in a decrease in yield.

In addition, with a resin material containing an inorganic filler, the peel strength of the insulating layer after etching and the metal layer laminated on the surface of the insulating layer by plating may vary.

In recent years, in order to respond to the increase in the amount of information transmission and to achieve high-speed communication, printed wiring boards and the like have become multi-layered, enlarged, and have finer wiring. is more likely to occur.

An object of the present invention is to provide a resin material capable of suppressing warping of a cured product and variations in plating peel strength. 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, an inorganic filler, and a curing agent are included, and the curing agent includes a compound having a structure represented by the following formula (11) or the following formula (12). , a resin material is provided.

In formula (11), R1 and R2 each represent a hydrogen atom or an organic group having 1 to 20 carbon atoms.

In the formula (12), R3 represents a group forming a heterocyclic ring together with the nitrogen atom.

In a specific aspect of the resin material according to the present invention, the compound having the structure represented by formula (11) or (12) is a compound having an alicyclic skeleton or an aromatic skeleton.

In a specific aspect of the resin material according to the present invention, the compound having the structure represented by formula (11) or (12) has a molecular weight of 400 or more and 10,000 or less.

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

In a specific aspect of the resin material according to the present invention, the curing agent contains an active ester compound, a maleimide compound, or a cyanate ester compound.

On the specific situation with the resin material which concerns on this invention, the said 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.

The resin material according to the present invention contains an epoxy compound, an inorganic filler, and a curing agent, and the curing agent contains a compound having a structure represented by formula (11) or formula (12). It is possible to suppress the warp of the product and variations in plating peel strength.

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 present invention will be described in detail below.

A resin material according to the present invention includes an epoxy compound, an inorganic filler, and a curing agent, and the curing agent includes a compound having a structure represented by the following formula (11) or (12).

In formula (11) above, R1 and R2 each represent a hydrogen atom or an organic group having from 1 to 20 carbon atoms.

In the above formula (12), R3 represents a group forming a heterocyclic ring together with the nitrogen atom.

Since the resin material according to the present invention has the above configuration, it is possible to suppress warpage of the cured product and variations in plating peel strength.

Moreover, since the resin material according to the present invention has the above configuration, it is possible to reduce the dielectric loss tangent of the cured product.

Moreover, since the resin material according to the present invention has the above configuration, it is possible to increase the plating peel strength. Therefore, with the resin material according to the present invention, it is possible to increase the peel strength of the plating, and to suppress variations in the increased peel strength of the plating.

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 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.

From the viewpoint of further lowering the dielectric loss tangent 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, such as a naphthalene skeleton or a phenyl skeleton. and more preferably an epoxy compound having an aromatic skeleton.

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

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).

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

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. Further, the molecular weight of the epoxy compound means the weight average molecular weight when the epoxy compound is a polymer.

The content of the epoxy compound is preferably 4% by weight or more, more preferably 8% by weight or more, preferably 30% by weight or less, and more preferably 25% 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 lower limit and not more than the upper limit, the thermal dimensional stability of the cured product can be further enhanced, and warping of the cured product can be more effectively suppressed.

The content of the epoxy compound is preferably 15% by weight or more, more preferably 20% by weight or more, and still more preferably 50% by weight or more, in 100% by weight of the resin material excluding the inorganic filler and the solvent. is 45% by weight or less. When the content of the epoxy compound is not less than the lower limit and not more than the upper limit, the thermal dimensional stability of the cured product can be further enhanced, and warping of the cured product can be more effectively suppressed.

[Inorganic filler]
The resin material 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. Only one kind of the inorganic filler may be used, or two or more kinds thereof may be used in combination.

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

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

From the viewpoint of promoting curing of the resin, effectively increasing the glass transition temperature of the cured product, and effectively decreasing the thermal linear expansion coefficient of the cured product, regardless of the curing environment, the inorganic filler is spherical silica. is preferred.

The average particle diameter of the inorganic filler is preferably 50 nm or more, more preferably 100 nm or more, still more preferably 500 nm or more, and 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 more than the lower limit and equal to or less than the upper limit, the surface roughness after etching can be reduced and the peel strength of the plating can be increased. Adhesion can be further enhanced.

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

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. 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, it is possible to form finer wiring on the surface of the cured product, and the cured product has better inter-wiring insulation reliability and interlayer insulation reliability. can be granted.

Examples of the coupling agent 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.

The content of the inorganic filler is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 65% by weight or more, and particularly preferably 68% by weight in 100% by weight of the components excluding the solvent in the resin material. % or more, preferably 90% by weight or less, more preferably 85% by weight or less, still more preferably 80% by weight or less, and particularly preferably 75% by weight or less. When the content of the inorganic filler is at least the lower limit, the dielectric loss tangent is effectively lowered. When the content of the inorganic filler is equal to or less than the above upper limit, the storage stability of the resin material can be enhanced, the thermal dimensional stability of the cured product can be enhanced, and variations in plating peel strength can be reduced. can be effectively suppressed. When the content of the inorganic filler is not less than the lower limit and not more 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 done. Furthermore, with this inorganic filler content, it is possible to lower the coefficient of thermal expansion of the cured product and to improve the smear removability.

[Curing agent]
The resin material contains a curing agent. Only one kind of the curing agent may be used, or two or more kinds thereof may be used in combination.

<Compound A>
The resin material contains, as a curing agent, a compound having a structure represented by the following formula (11) or (12). In this specification, "a compound having a structure represented by the following formula (11)" may be described as "compound A1", and "a compound having a structure represented by the following formula (12)" may be referred to as a "compound A2". In addition, in this specification, "a compound having a structure represented by the following formula (11) or the following formula (12)" may be referred to as "compound A". Therefore, the resin material according to the present invention contains compound A. As the compound A, the resin material according to the present invention may contain only the compound A1, may contain only the compound A2, or may contain both the compound A1 and the compound A2. Only one kind of compound A may be used, or two or more kinds thereof may be used in combination.

In formula (11) above, R1 and R2 each represent a hydrogen atom or an organic group having from 1 to 20 carbon atoms.

In the above formula (12), R3 represents a group forming a heterocyclic ring together with the nitrogen atom.

When a carbodiimide compound is used as the curing agent, the curing reaction of the epoxy compound proceeds rapidly, and the cured product tends to warp. In addition, the carbodiimide group (-N=C=N-) tends to excessively interact with the metal layer, so that the plating peel strength tends to vary. In addition, when a carbodiimide compound is used as a curing agent and a relatively large amount of inorganic filler is blended in the resin material (for example, the content of the inorganic filler is 50% by weight or more), the dispersibility of the inorganic filler deteriorates, the surface roughness after desmearing tends to vary, and the plating peel strength tends to vary more.

On the other hand, when compound A having a structure represented by formula (11) or (12) is used, the curing reaction of the epoxy compound progresses more slowly than when the carbodiimide compound is used. can be made Moreover, the structure represented by the above formula (11) or the above formula (12) can improve the interaction with the metal layer as compared with the carbodiimide group. Therefore, with the resin material according to the present invention, warping of the cured product can be suppressed, and variations in plating peel strength can be suppressed. The resin material according to the present invention can effectively suppress variations in plating peel strength even when the resin material contains a relatively large amount of inorganic filler.

Moreover, the resin material containing the compound A can reduce the dielectric loss tangent of the cured product, and can increase the plating peel strength.

The compound A may have one structure represented by the formula (11) or the formula (12), or may have a plurality of structures. The compound A1 may have one structure represented by the formula (11), or may have a plurality of structures. The compound A2 may have one structure represented by the formula (12), or may have a plurality of structures.

In formula (11) above, R1 and R2 each represent a hydrogen atom or an organic group having from 1 to 20 carbon atoms. In formula (11) above, R1 and R2 may be the same or different.

In the above formula (11), examples of combinations of R1 and R2 include the following first to third combinations.

First combination: a combination of a hydrogen atom and a hydrogen atom.

Second combination: a combination of a hydrogen atom and an organic group having 1 to 20 carbon atoms.

Third combination: a combination of an organic group having 1 to 20 carbon atoms and an organic group having 1 to 20 carbon atoms.

In R1 and R2 in the formula (11), the number of carbon atoms in the organic group having 1 to 20 carbon atoms is preferably 2 or more, more preferably 3 or more, preferably 18 or less, and more preferably 16 or less. be. When the number of carbon atoms in the organic group having a carbon number of 1 to 20 is at least the lower limit and at most the upper limit, warping of the cured product and variations in plating peel strength can be more effectively suppressed, and curing can be performed. The dielectric loss tangent of the object can be further reduced, and the plating peel strength can be further increased.

From the viewpoint of more effectively suppressing the warpage of the cured product and variations in plating peel strength, the organic group having 1 to 20 carbon atoms in R1 and R2 in the above formula (11) is an alkyl group or an oil group. An organic group having a cyclic skeleton is preferred.

In the above formula (12), R3 represents a group forming a heterocyclic ring together with the nitrogen atom. In formula (12) above, the hetero ring formed by R3 and a nitrogen atom is preferably a pyrazole ring or an imidazole ring. In addition, the pyrazole ring and the imidazole ring may have a substituent.

The compound A is preferably the compound A1 having the second combination or the third combination, or the compound A2, and is the compound A1 having the third combination, or the compound A2. is more preferable. In this case, the warpage of the cured product and variations in the peel strength of the plating can be more effectively suppressed, the dielectric loss tangent of the cured product can be further reduced, and the peel strength of the cured product can be further increased. can be done.

The above compound A is preferably a compound having an alicyclic skeleton or an aromatic skeleton. In this case, the compound A may have only the alicyclic skeleton, may have only the aromatic skeleton, or may have both the alicyclic skeleton and the aromatic skeleton. You may have

The alicyclic skeleton may be a saturated alicyclic skeleton having no double bond or an unsaturated alicyclic skeleton having a double bond.

Examples of the alicyclic skeleton include a cyclohexane skeleton, a norbornene skeleton, a dicyclopentadiene skeleton, and the like.

The alicyclic skeleton is preferably a cyclohexane skeleton or a dicyclopentadiene skeleton from the viewpoint of more effectively suppressing the warp of the cured product and variations in plating peel strength.

Examples of the aromatic skeleton include a phenyl skeleton, a naphthalene skeleton, a fluorene skeleton, a biphenyl skeleton, an anthracene skeleton, a pyrene skeleton, a xanthene skeleton, an adamantane skeleton, and a bisphenol A skeleton.

The aromatic skeleton is preferably a phenyl skeleton, a biphenyl skeleton, or a naphthalene skeleton, from the viewpoint of more effectively suppressing the warp of the cured product and variations in plating peel strength.

When the compound A has the alicyclic skeleton or the aromatic skeleton, the compound A has the alicyclic skeleton or the aromatic skeleton represented by the above formula (11) or the above formula (12). It may be present in the structure represented by the above formula (11) or the portion other than the structure represented by the above formula (12). Further, the compound A1 has the alicyclic skeleton or the aromatic skeleton in both the structure represented by the formula (11) and the portion other than the structure represented by the formula (11). may Further, the compound A2 has the alicyclic skeleton or the aromatic skeleton in both the structure represented by the formula (12) and the portion other than the structure represented by the formula (12). may

The molecular weight of compound A is preferably 400 or more, more preferably 500 or more, preferably 10,000 or less, and more preferably 5,000 or less. When the molecular weight of the compound A is at least the above lower limit and below the above upper limit, it is possible to more effectively suppress the warpage of the cured product and variations in plating peel strength, and further reduce the dielectric loss tangent of the cured product. It is possible to further increase the plating peel strength.

The content of compound A relative to 100 parts by weight of the epoxy compound is preferably 1 part by weight or more, more preferably 3 parts by weight or more, preferably 50 parts by weight or less, and more preferably 40 parts by weight or less. When the content of the compound A is at least the above lower limit and at most the above upper limit, it is possible to more effectively suppress variations in warpage and plating peel strength of the cured product, and further lower the dielectric loss tangent of the cured product. It is possible to further increase the plating peel strength. Further, when the content of the compound A is at least the lower limit and at most the upper limit, the curability is further improved, the thermal dimensional stability is further improved, and volatilization of residual unreacted components can be further suppressed.

The content of the compound A in 100% by weight of the curing agent is preferably 1% by weight or more, more preferably 3% by weight or more, preferably 50% by weight or less, and more preferably 40% by weight or less. When the content of compound A is at least the lower limit and at most the upper limit, the effects of the present invention can be exhibited more effectively.

<Curing agent X>
The resin material is a curing agent that does not have a structure represented by the following formula (X1) or a structure represented by the following formula (X2) (hereinafter referred to as “curing agent X”). may be used). The curing agent X is a curing agent different from the compound A described above. Only one kind of the curing agent X may be used, or two or more kinds thereof may be used in combination.

In formula (X1) above, R1 and R2 each represent a hydrogen atom or an organic group having 1 to 20 carbon atoms.

In formula (X2) above, R3 represents a group forming a heterocyclic ring together with the nitrogen atom.

As the curing agent X, cyanate ester compound (cyanate ester curing agent), amine compound (amine curing agent), thiol compound (thiol curing agent), imidazole compound, phosphine compound, dicyandiamide, phenol compound (phenol curing agent), acid Examples include anhydrides, active ester compounds (active ester curing agents), 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.

From the viewpoint of more effectively suppressing the warpage of the cured product and variations in plating peel strength, the curing agent X is preferably the active ester compound, the maleimide compound, or the cyanate ester compound. Compounds are more preferred. The curing agent preferably contains the active ester compound, the maleimide compound, or the cyanate ester compound, and more preferably contains the active ester compound.

The active ester compound is a compound having at least one ester bond, and an aliphatic chain, an aliphatic ring, or an aromatic ring bonded to both sides of the ester bond. The active ester compound is obtained, for example, by a condensation reaction between a carboxylic acid compound or a thiocarboxylic acid compound and a hydroxy compound or a thiol compound. Examples of the active ester compound include compounds represented by the following formula (2).

In formula (2) above, 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 (2), 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 (2), the combination of X1 and X2 includes a combination of an optionally substituted naphthalene ring and an optionally substituted naphthalene ring.

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 enhancing the thermal dimensional stability of the cured product, it is more preferable to have a naphthalene ring in the main chain skeleton of the active ester compound.

Commercially available products of the active ester compound include DIC's "HPC-8000-65T", "EXB9416-70BK", "EXB8100-65T" and "HPC-8150-60T".

The content of the active ester compound with respect to 100 parts by weight of the epoxy compound is preferably 30 parts by weight or more, more preferably 35 parts by weight or more, preferably 150 parts by weight or less, and more preferably 120 parts by weight or less. When the content of the active ester compound is not less than the above lower limit and not more than the above upper limit, the curability is further improved, and warpage of the cured product and variation in plating peel strength can be more effectively suppressed.

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% by weight or less, and more preferably 98% by weight or less. When the content of the active ester compound is equal to or more than the lower limit and equal to or less than the upper limit, the effects of the present invention can be exhibited more effectively.

The maleimide compound may be a bismaleimide compound.

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

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

The maleimide compound is preferably an N-alkylbismaleimide compound from the viewpoint of lowering the dielectric loss tangent and keeping the curing temperature low.

Commercially available products of the above N-alkylbismaleimide compound include Designer Molecules Inc.; "BMI-1500", "BMI-1700", and "BMI-3000" manufactured by the same company.

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.

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).

The content of the cyanate ester compound with respect to 100 parts by weight of the epoxy compound is preferably 20 parts by weight or more, more preferably 25 parts by weight or more, preferably 150 parts by weight or less, and more preferably 120 parts by weight or less. When the content of the cyanate ester compound is not less than the above lower limit and not more than the above upper limit, the curability is further improved, and warping of the cured product and variations in plating peel strength can be more effectively suppressed.

The content of the cyanate ester compound in 100% by weight of the curing agent is preferably 15% by weight or more, more preferably 20% by weight or more, preferably 80% by weight or less, and more preferably 70% by weight or less. When the content of the cyanate ester compound is not less than the lower limit and not more than the upper limit, the effects of the present invention can be exhibited more effectively.

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 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 “LA1356” and “LA3018-50P”).

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

Commercially available products of the above acid anhydrides include "Rikashid TDA-100" manufactured by Shin Nippon Rika Co., Ltd., and the like.

The resin material according to the present invention may contain the carbodiimide compound as long as the effects of the present invention are not impaired.

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 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 (3), 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 represents an integer of 1 or more and 5 or less. When there are multiple X's, the multiple X's 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 Co., Ltd. "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", "Carbodilite V-09", "Carbodilite 10M-SP" and "Carbodilite 10M-SP (improved)", and "Stabaxol P", "Stabaxol P400" and "Hykasil 510" manufactured by Rhein Chemie.

From the viewpoint of effectively exhibiting the effects of the present invention, it is most preferable that the resin material according to the present invention does not contain the carbodiimide compound. When the resin material according to the present invention contains the carbodiimide compound, the content of the carbodiimide compound with respect to 100 parts by weight of the epoxy compound is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and still more preferably 1 part by weight. It is below the department.

The content of the curing agent X 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, and more preferably 120 parts by weight or less. When the content of the curing agent X is not less than the above lower limit and not more than the above upper limit, the curability is further improved, the thermal dimensional stability is further improved, and volatilization of residual unreacted components can be further suppressed.

The content of the curing agent X in 100% by weight of the curing agent is preferably 30% by weight or more, more preferably 40% by weight or more, preferably 99% by weight or less, and more preferably 98% 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 can be exhibited more effectively.

[Curing accelerator]
The resin material preferably contains 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, the number of unreacted functional groups is reduced, and the crosslink density is increased. 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 compound 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 peroxide include dicumyl peroxide, perhexyl 25B, and the like.

From the viewpoint of further suppressing the curing temperature and effectively suppressing 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 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 in 100% by weight of the components excluding the inorganic filler and solvent in the resin material. % or less, more preferably 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.

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

The thermoplastic resin is preferably a phenoxy resin 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 use of the phenoxy resin suppresses the deterioration of the embedding properties of the resin film in holes or unevenness 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 phenoxy resin contained in the resin material 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, "YP50", "YP55" and "YP70" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and "1256B40", "4250", "4256H40" manufactured by Mitsubishi Chemical Corporation, " 4275”, “YX6954BH30” and “YX8100BH30”.

The thermoplastic resin is preferably a polyimide resin (polyimide compound) from the viewpoint 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 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), Versamin 552 (trade name, PRIAMINE 1075, PRIAMINE 1074 (trade names, both manufactured by Croda Japan), and the like.

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

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

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

Contents of the thermoplastic resin, the polyimide resin, and the phenoxy resin are not particularly limited. In 100% by weight of the components excluding the inorganic filler and the solvent in the resin material, 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) is , preferably 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 at least the above lower limit and at most the above upper limit, the embedding property of the resin material into the holes or unevenness of the circuit board is improved. When the content of the thermoplastic resin is at least the above lower limit, the formation of the resin film becomes even easier, and an even better insulating layer can be obtained. If the content of the thermoplastic resin is equal to or less than the above upper limit, the thermal expansion coefficient of the cured product will be even lower. If the content of the thermoplastic resin is equal to or less than the above upper limit, the surface roughness of the cured product will be further reduced, and the adhesive strength between the cured product and the metal layer will be 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 within a suitable range, and the coatability of the resin material can be improved. Also, 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 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 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. A thermosetting resin other than an agent, a thickener, a thixotropic agent, and an epoxy compound may also be included.

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

Other thermosetting resins include polyphenylene ether resins, divinylbenzyl ether resins, polyarylate resins, diallyl phthalate resins, benzoxazine resins, benzoxazole resins, and acrylate resins.

(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 the method for obtaining a resin film by molding the resin composition into a film include the following methods. An extrusion molding method in which a resin composition is melt-kneaded using an extruder, extruded, and then molded into a film using a T-die, 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 by 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 may not 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 controlling the degree of curing of the resin film more uniformly, the thickness of the resin film is preferably 5 μm or more and preferably 200 μm or less. When the resin film is used as an insulating layer of a circuit, the thickness of the insulating layer formed of the resin film is preferably 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.

(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 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 side 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 a 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 in the range of 1 μm to 50 μm. 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 multilayer board is a multilayer board that includes a circuit board and an insulating layer laminated on the circuit board. The insulating layer of this multilayer 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 as 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.

Moreover, 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 substrates, a multilayer printed wiring board is required to have a low dielectric loss tangent and high insulation reliability due to an insulating layer. The resin material according to the present invention can effectively improve the insulation reliability by lowering the dielectric loss tangent and improving the adhesion between the insulating layer and the metal layer and the etching performance. 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.

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. As shown in FIG. 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 . A metal layer 17 is formed on a partial region of the upper surface of each of the insulating layers 13 to 15 other than the insulating layer 16 positioned on the outer surface opposite to the circuit board 12 among the multiple insulating layers 13 to 16. It is 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 of 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).

(Swelling treatment and roughening treatment)
The resin material is preferably used to obtain a cured product that is subjected to swelling treatment and roughening treatment. 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.

A chemical oxidizing agent such as a manganese compound, a chromium compound, or a persulfate compound is used for the roughening treatment. 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 surface arithmetic mean roughness Ra of the cured product is preferably 10 nm or more, preferably less than 300 nm, more preferably less than 200 nm, and even more preferably less than 150 nm. In this case, the adhesive strength between the cured product and the metal layer is increased, and finer wiring is formed on the surface of the insulating layer. 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, as in 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 desmeared cured product is sufficiently reduced.

EXAMPLES The present invention will now be described in detail with reference to examples and comparative examples. The invention is not limited to the following examples.

The following materials were prepared.

(epoxy compound)
Biphenyl novolac type epoxy compound ("NC-3000" manufactured by Nippon Kayaku Co., Ltd.)
Naphthalene aralkyl type epoxy compound ("ESN-475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
Dicyclopentadiene type epoxy compound (manufactured by ADEKA "EP-4088S"

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

(curing agent)
<Compound A>
Compound A-1 (molecular weight 3150) synthesized according to Synthesis Example A-1 below.

<Synthesis Example A-1>
Synthesis of carbodiimide compound A-1:
The following ingredients were prepared.

Tolylene diisocyanate (mixture of 80% by weight of 2,4-tolylene diisocyanate and 20% by weight of 2,6-tolylene diisocyanate) 100 parts by weight Polyalkylene carbonate diol ("DURANOL T-5651" manufactured by Asahi Kasei Chemicals, Molecular weight 1000) 71.8 parts by weight Phenyl isocyanate 17.1 parts by weight Toluene (boiling point 110.6°C) 245 parts by weight Carbodiimidation catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide) 1.0 parts by weight Department

The above components were put into a reaction vessel equipped with a reflux tube and a stirrer, and stirred at 100° C. for 3 hours under a nitrogen stream for reaction to obtain polycarbodiimide compound A-1. In the obtained polycarbodiimide compound A-1, the infrared absorption (IR) spectrum measurement showed that the absorption peak due to the isocyanate group at a wavelength of about 2270 cm ^-1 almost disappeared, and that the carbodiimide at a wavelength of about 2150 cm ^-1 It was confirmed that an absorption peak due to the group was present.

Synthesis of compound A-1:
Polycarbodiimide compound A-1 in the reactor was cooled to 50°C. Then, 107.2 parts by weight of dicyclohexylamine (DcyHA) was added to the reaction vessel and reacted with stirring for 5 hours to obtain compound A-1. In the obtained compound A-1, an absorption peak due to the guanidine group is present at a wavelength of around 1660 cm ^-1 by infrared absorption (IR) spectrum measurement, and an absorption due to the carbodiimide group at a wavelength of around 2150 cm ^-1 . It was confirmed that the peak almost disappeared.

Compound A-2 (molecular weight: 2890) synthesized according to Synthesis Example A-2 below.

<Synthesis Example A-1>
Synthesis of carbodiimide compound A-2:
The following ingredients were prepared.

Tolylene diisocyanate (mixture of 80% by weight of 2,4-tolylene diisocyanate and 20% by weight of 2,6-tolylene diisocyanate) 100 parts by weight Polyalkylene carbonate diol ("DURANOL T-5651" manufactured by Asahi Kasei Chemicals, Molecular weight 1000) 71.8 parts by weight Phenyl isocyanate 17.1 parts by weight Cyclohexanone 245 parts by weight Carbodiimidation catalyst (3-methyl-1-phenyl-2-phosphorene-1-oxide) 1.0 parts by weight

The above components were put into a reaction vessel equipped with a reflux tube and a stirrer, and stirred at 100° C. for 3 hours under a nitrogen stream for reaction to obtain a polycarbodiimide compound A-2. In the obtained polycarbodiimide compound A-2, the infrared absorption (IR) spectrum measurement showed that the absorption peak due to the isocyanate group at a wavelength of about 2270 cm ^-1 almost disappeared, and that the carbodiimide at a wavelength of about 2150 cm ^-1 It was confirmed that an absorption peak due to the group was present.

Synthesis of compound A-2:
Polycarbodiimide compound A-2 in the reactor was cooled to 50°C. Then, 56.3 parts by weight of 3,5-dimethylpyrazole was added to the reaction vessel and reacted with stirring for 5 hours to obtain compound A-2. In addition, in the obtained compound A-2, an absorption peak due to the guanidine group is present at a wavelength of around 1660 cm ^-1 by infrared absorption (IR) spectrum measurement, and an absorption due to the carbodiimide group at a wavelength of around 2150 cm ^-1 . It was confirmed that the peak almost disappeared.

<Curing agent X>
Active ester compound-containing liquid (manufactured by DIC "EXB-9416-70BK", solid content 70% by weight)
Liquid containing cyanate ester compound (“BA-3000S” manufactured by Lonza Japan Co., Ltd., solid content 75% by weight)
N-alkylbismaleimide compound (Designer Molecules Inc. "BMI-1700")
Carbodiimide compound-containing liquid (manufactured by Nisshinbo Chemical Co., Ltd. "V-03", solid content 50% by weight)

(polyimide compound)
A solution containing a polyimide compound (26.8% by weight of nonvolatile matter), which is a reaction product of tetracarboxylic dianhydride and dimer diamine, was synthesized according to Synthesis Example 2 below.

(Synthesis example 2)
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 compound-containing solution (non-volatile content: 26.8% by weight) 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 molecular weight of the polyimide compound synthesized in Synthesis Example 2 was determined as follows.

GPC (gel permeation chromatography) measurement:
Using a high-performance liquid chromatograph system manufactured by Shimadzu Corporation, measurement was performed using tetrahydrofuran (THF) as a developing medium at a column temperature of 40° C. and a flow rate of 1.0 ml/min. "SPD-10A" was used as a detector, and two "KF-804L" 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.

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

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

Preparation of resin film:
Using an applicator, the obtained resin material was applied onto the release-treated surface of a release-treated PET film ("XG284" manufactured by Toray Industries, Inc., thickness 25 μm), and then placed in a gear oven at 100° C. for 2 minutes. Dry and 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 The obtained resin film was cut into a size of 2 mm in width and 80 mm in length, and five sheets were laminated to obtain a laminate having a thickness of 200 μm. The resulting laminate was heated at 200° C. for 90 minutes to obtain a cured product. The resulting cured product was measured at room temperature (23°C) by the cavity resonance method using Kanto Denshi Applied Development Co., Ltd.'s "Cavity Resonance Perturbation Method Dielectric Constant Measurement Device CP521" and Keysight Technologies, Inc.'s "Network Analyzer N5224A PNA". Then, the dielectric loss tangent was measured at a frequency of 5.8 GHz.

[Dielectric loss tangent criterion]
○○: dielectric loss tangent is 0.0037 or less ○: dielectric loss tangent exceeds 0.0037 and 0.0040 or less △: dielectric loss tangent exceeds 0.0040 and less than 0.0045 ×: dielectric loss tangent exceeds 0.0045

(2) Warp The obtained laminated film was cut into a size of 50 mm x 50 mm. The cut laminated film is overlaid on a copper plate (50 mm × 50 mm × thickness 100 μm) from the resin film side, and a diaphragm type vacuum laminator ("Batch type vacuum laminator MVLP-500-IIA" manufactured by Meiki Seisakusho Co., Ltd.) is used. After depressurizing for 1 second to an air pressure of 13 hPa or less, lamination was performed at 100° C. and a pressure of 0.7 MPa for 30 seconds, and further pressing was performed at a pressing pressure of 0.8 MPa and a pressing temperature of 100° C. for 60 seconds. Thus, a laminate was obtained in which the laminated film (the uncured resin film and the PET film) was laminated on the copper plate.

With the PET film attached, the resulting laminate was heated at 100° C. for 30 minutes and then further heated at 180° C. for 30 minutes. The PET film was then peeled off and heated at 200° C. for 90 minutes. Thus, a laminate was obtained in which the cured product of the resin film was laminated on the copper plate. The laminate was placed on flat glass so that the copper plate was on the bottom side and the cured product was on the top side, and how much the four corners were warped was measured. Each distance from the upper surface of the flat glass to the four corners was defined as the amount of warpage, and the average value of the amounts of warp at the four corners was obtained. Curvature of the cured product was determined according to the following criteria.

[Warpage criteria]
○○: The average value of the warp amount is 3 mm or less ○: The average value of the warp amount is more than 3 mm and 5 mm or less △: The average value of the warp amount is more than 5 mm and 10 mm or less ×: The average value of the warp amount is more than 10 mm

(3) Variation in plating peel strength and plating peel strength Lamination process and semi-curing treatment:
A 100 mm square double-sided copper-clad laminate (CCL substrate) (“E679FG” manufactured by Hitachi Chemical Co., Ltd.) was prepared. Both sides of the copper foil surface of this double-sided copper-clad laminate were immersed in "Cz8101" manufactured by MEC Co., Ltd. to roughen the surface of the copper foil. Using Meiki Seisakusho's "Batch Type Vacuum Laminator MVLP-500-IIA", on both sides of the roughened copper clad laminate, the resin film (B stage film) side of the laminate film is placed on the copper clad laminate. to obtain a laminated structure. The lamination conditions were as follows: pressure was reduced for 30 seconds to 13 hPa or less, followed by lamination for 30 seconds at 100° C. and pressure of 0.7 MPa, followed by press pressure of 0.8 MPa and press temperature of 100° C. for 60 seconds. After that, with the PET film attached, the resin film in the laminated structure was heated at 100° C. for 30 minutes, and then further heated at 180° C. for 30 minutes to semi-harden the resin film. After that, the PET film was peeled off to obtain a laminate in which the semi-cured resin film was laminated on the CCL substrate.

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

(b) Permanganate treatment (roughening treatment and desmear treatment):
The laminate 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 and roughened.

Electroless plating process:
The surface of the resulting roughened cured product was treated with an alkaline cleaner (“Cleaner Securigant 902” manufactured by Atotech Japan Co., Ltd.) at 60° C. for 5 minutes to be degreased and washed. 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, “ Electroplating was carried out using a correction agent "Capalacid GS") and applying a current of 0.6 A/cm ² until the plating thickness reached about 25 μm. 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 cured 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 copper plating layer with a notch with a gripper, and remove the copper The plating layer was peeled off by 20 mm and the peel strength (plating peel strength) was measured. The peel strength (plating peel strength) was measured for each of the six incisions, and the average value and standard deviation of the plating peel strength were determined. Plating peel strength and variations in plating peel strength were evaluated according to the following criteria.

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

[Criteria for determination of variations in plating peel strength]
○○: Standard deviation of plating peel strength is less than 0.03 kgf/cm ○: Standard deviation of plating peel strength is 0.03 kgf/cm or more and less than 0.05 kgf/cm △: Standard deviation of plating peel strength is 0.05 kgf/cm cm or more and less than 0.07 kgf/cm ×: Standard deviation of plating peel strength is 0.07 kgf/cm or more

Compositions 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 (8)

including an epoxy compound, an inorganic filler, and a curing agent;
The epoxy compound comprises an epoxy compound that is liquid at 25°C and an epoxy compound that is solid at 25°C,
The epoxy compound that is liquid at 25°C has a viscosity at 25°C of 1000 mPa s or less,
The resin material, wherein the curing agent contains a compound having a structure represented by the following formula (11) or (12).

In formula (11), R1 and R2 each represent a hydrogen atom or an organic group having 1 to 20 carbon atoms.

In the formula (12), R3 represents a group forming a heterocyclic ring together with the nitrogen atom. 2. The resin material according to claim 1, wherein the compound having the structure represented by formula (11) or formula (12) is a compound having an alicyclic skeleton or an aromatic skeleton. The resin material according to claim 1 or 2, wherein the compound having the structure represented by formula (11) or formula (12) has a molecular weight of 400 or more and 10,000 or less. 4. The resin material according to any one of claims 1 to 3, wherein the content of the inorganic filler is 50% by weight or more in 100% by weight of components excluding the solvent in the resin material. The resin material according to any one of claims 1 to 4, wherein the curing agent comprises an active ester compound, a maleimide compound, or a cyanate ester compound. The resin material according to any one of claims 1 to 5, which is a resin film. 7. The resin material according to claim 1, 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 7.

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