Resin material, resin film, laminated film, and multilayer printed wiring board

Abstract

Provided is a resin material with which (1) a dielectric loss tangent of a cured product thereof can be reduced, (2) surface roughness after a desmear treatment can be reduced, (3) plating peel strength can be increased, and (4) occurrence of cracks can be reduced.　A resin material according to the present invention comprises a curable compound, an insulating filler, and a solvent. The solvent includes a ketone compound. The ketone compound has a boiling point of 90-150°C.

Description

Resin materials, resin films, laminated films, and multilayer printed circuit boards

[0001] The present invention relates to a resin material comprising a curable compound, an insulating filler, and a solvent. Furthermore, the present invention relates to a resin film formed from the above resin material and a laminated film comprising the resin film. Moreover, the present invention relates to a multilayer printed circuit board using the above resin material.

[0002] Conventionally, various resin materials have been used to obtain electronic components such as semiconductor devices, laminates, and printed circuit boards. For example, in multilayer printed circuit boards, resin materials are used to form insulating layers to insulate the internal layers and to form insulating layers located on the surface. Wiring, which is generally made of metal, is laminated on the surface of the insulating layer. In addition, a resin film, which is made by molding a resin material into a film shape, may be used to form the insulating layer. The above resin materials are used as insulating materials for multilayer printed circuit boards, including build-up films.

[0003] Patent Document 1 discloses a resin sheet for circuit formation used by laminating it on an insulating resin layer. The resin sheet comprises a support and a resin composition layer bonded to the support, the thickness of the resin composition layer being 0.1 μm to 6 μm, and the resin composition layer containing (A) epoxy resin and (B) an active ester curing agent. Furthermore, an example in Patent Document 1 describes that the resin composition layer was formed using a resin varnish containing methyl ethyl ketone (MEK) and cyclohexanone as solvents.

[0004] Japanese Patent Publication No. 2016-032923

[0005] To suppress transmission loss in printed circuit boards, it is required that the dielectric loss tangent of the insulating layer be small and the surface roughness of the insulating layer after desmearing be small. However, simply reducing the surface roughness of the insulating layer after desmearing reduces the plating peel strength, making it impossible to accurately form fine copper wiring.

[0006] Furthermore, during the manufacturing process of printed circuit boards, the insulating layer is exposed to a wide range of temperatures, from room temperature to the high-temperature environment during the reflow process. As a result, the insulating layer undergoes repeated thermal expansion and contraction, which can lead to cracks forming in the insulating layer.

[0007] The resin composition (resin material) described in Patent Document 1 above can reduce the surface roughness of the insulating layer after desmearing to some extent, and can also improve reflow resistance to some extent. However, even with the resin composition described in Patent Document 1, it is difficult to sufficiently suppress the occurrence of cracks.

[0008] With conventional resin materials, it is difficult to achieve all of the following effects: 1) reducing the dielectric loss tangent of the cured product, 2) reducing the surface roughness after desmearing, 3) increasing the plating peel strength, and 4) suppressing the occurrence of cracks.

[0009] The object of the present invention is to provide a resin material that can 1) reduce the dielectric loss tangent of the cured product, 2) reduce the surface roughness after desmearing, 3) increase the plating peel strength, and 4) suppress the occurrence of cracks. The present invention also aims to provide a resin film formed from the above resin material and a laminated film comprising the resin film. Furthermore, the present invention also aims to provide a multilayer printed circuit board using the above resin material.

[0010] This specification discloses the following resin materials, resin films, laminated films, and multilayer printed circuit boards.

[0011] Item 1. A resin material comprising a curable compound, an insulating filler, and a solvent, wherein the solvent contains a ketone compound, and the boiling point of the ketone compound is 90°C or higher and 150°C or lower.

[0012] Item 2. The resin material according to Item 1, wherein the ketone compound has 4 to 7 carbon atoms.

[0013] Item 3. A resin material comprising a curable compound, an insulating filler, and a solvent, wherein the solvent comprises a ketone compound represented by the following formula (X).

[0014]

[0015] In the above formula (X), R １ R represents a hydrogen atom or a methyl group. ２ R represents a hydrogen atom or a methyl group. ３ R represents a hydrogen atom or a methyl group. ４ represents a hydrogen atom or a methyl group.

[0016] Item 4. In the formula (X), R ３ represents a hydrogen atom, R ４ The resin material described in item 3, where represents a hydrogen atom.

[0017] Item 5. A resin material comprising a curable compound, an insulating filler, and a solvent, wherein the ratio of the Tg(B) of the cured resin material to the Tg(A) of the semi-cured resin material, determined by the glass transition temperature measurement method described below, is 1.0 or more and 1.2 or less.

[0018] Method for measuring glass transition temperature: After vacuum laminating copper foil to both sides of a double-sided copper-clad laminate, the shiny side of the copper foil is treated with Cz to create a substrate in which the surface of the copper foil is etched by approximately 1 μm. After coating the surface of a 25 μm thick polyethylene terephthalate film with resin material, it is dried in a 100°C gear oven for 2 minutes to obtain a laminated film in which a 40 μm thick resin film is laminated on the surface of the polyethylene terephthalate film. The obtained laminated film is vacuum laminated onto the surface of the substrate from the resin film side, heated at 130°C for 30 minutes, and then heated again at 170°C for 30 minutes. After cutting out the copper foil and resin film from the laminated structure of the substrate and resin film, the copper foil portion is treated with iron chloride (FeCl ３ The resin material is etched with an aqueous solution to obtain a semi-cured product. The glass transition temperature of the obtained semi-cured resin material is denoted as Tg(A). A laminated film vacuum-laminated onto the surface of the same substrate is heated at 130°C for 30 minutes, and then further heated at 170°C for 30 minutes. The polyethylene terephthalate film of the laminated film is peeled off, and the resin material is heated at 200°C for 60 minutes to obtain a cured product. The glass transition temperature of the obtained cured resin material is denoted as Tg(B).

[0019] Item 6. The resin material according to any one of items 1 to 4, wherein the content of the ketone compound in 100% by weight of the solvent is 25% by weight or more.

[0020] Item 7. The resin material according to any one of items 1 to 6, wherein the content of the insulating filler is 40% by weight or more and 80% by weight or less of 100% by weight of the components excluding the solvent in the resin material.

[0021] Item 8. The resin material according to any one of items 1 to 7, wherein the insulating filler includes hollow particles.

[0022] Item 9. The resin material according to any one of items 1 to 8, wherein the curable compound is a thermosetting compound.

[0023] Item 10. The resin material according to any one of items 1 to 9, wherein the curable compound comprises an epoxy compound or a maleimide compound.

[0024] Item 11. A resin material according to any one of items 1 to 10, including a curing agent.

[0025] Item 12. The resin material according to item 11, wherein the curing agent comprises an active ester compound.

[0026] Item 13. A resin material according to any one of items 1 to 12, used for forming an insulating layer in a multilayer printed circuit board.

[0027] Item 14. A resin film formed from any one of the resin materials described in items 1 to 13.

[0028] Item 15. A laminated film comprising a metal foil or a base film and a resin film as described in Item 14, wherein the resin film is laminated on the surface of the metal foil or base film.

[0029] Item 16. The laminated film according to item 15, comprising the base film, wherein the base film is a polyethylene terephthalate film.

[0030] Item 17. A multilayer printed wiring board comprising a circuit board, a plurality of insulating layers disposed on the surface of the circuit board, and a metal layer disposed between the plurality of insulating layers, wherein at least one of the plurality of insulating layers is a cured product of the resin material according to any one of Items 1 to 13.

[0031] The resin material according to the present invention contains a curable compound, an insulating filler, and a solvent. The solvent contains a ketone compound, and the boiling point of the ketone compound is 90°C or higher and 150°C or lower. In the resin material according to the present invention, since the above configuration is provided, 1) the dielectric tangent of the cured product can be reduced, 2) the surface roughness after desmear treatment can be reduced, 3) the plating peel strength can be increased, and 4) the occurrence of cracks can be suppressed.

[0032] The resin material according to the present invention contains a curable compound, an insulating filler, and a solvent. The solvent contains a ketone compound represented by a specific formula (X). In the resin material according to the present invention, since the above configuration is provided, 1) the dielectric tangent of the cured product can be reduced, 2) the surface roughness after desmear treatment can be reduced, 3) the plating peel strength can be increased, and 4) the occurrence of cracks can be suppressed.

[0033] The resin material according to the present invention contains a curable compound, an insulating filler, and a solvent. The ratio of Tg(B) of the cured product of the resin material to Tg(A) of the semi-cured product of the resin material, obtained by a specific method for measuring the glass transition temperature, is 1.0 or higher and 1.2 or lower. In the resin material according to the present invention, since the above configuration is provided, 1) the dielectric tangent of the cured product can be reduced, 2) the surface roughness after desmear treatment can be reduced, 3) the plating peel strength can be increased, and 4) the occurrence of cracks can be suppressed.

[0034] FIG. 1 is a cross-sectional view schematically showing a multilayer printed wiring board using the resin material according to an embodiment of the present invention.

[0035] Hereinafter, the details of the present invention will be described.

[0036] (Resin Material) The resin material according to the present invention contains a curable compound, an insulating filler, and a solvent. The resin material according to the present invention has the following configuration (1), the following configuration (2), or the following configuration (3).

[0037] Configuration (1): The solvent contains a ketone compound, and the boiling point of the ketone compound is 90°C or higher and 150°C or lower.

[0038] Configuration (2): The solvent contains a ketone compound represented by the following formula (X).

[0039]

[0040] In the above formula (X), R １ represents a hydrogen atom or a methyl group, and R ２ represents a hydrogen atom or a methyl group, and R ３ represents a hydrogen atom or a methyl group, and R ４ represents a hydrogen atom or a methyl group.

[0041] Configuration (3): The ratio (Tg(B) / Tg(A)) of the Tg(B) of the cured product of the resin material to the Tg(A) of the semi-cured product of the resin material, obtained by the following method for measuring the glass transition temperature, is 1.0 or higher and 1.2 or lower.

[0042] Method for measuring the glass transition temperature: After vacuum laminating copper foils on both sides of a double-sided copper-clad laminate, the shiny surface of the copper foil is Cz-treated to produce a substrate with the surface of the copper foil etched by about 1μm. After applying the resin material on the surface of a polyethylene terephthalate film with a thickness of 25μm, it is dried in a gear oven at 100°C for 2 minutes to obtain a laminated film in which a resin film with a thickness of 40μm is laminated on the surface of the polyethylene terephthalate film. The obtained laminated film is vacuum laminated on the surface of the substrate from the resin film side and heated at 130°C for 30 minutes and then further heated at 170°C for 30 minutes. After cutting out the copper foil and the resin film from the laminated structure of the substrate and the resin film, the copper foil part is treated with iron chloride (FeCl ３The resin material is etched with an aqueous solution to obtain a semi-cured product. The glass transition temperature of the obtained semi-cured resin material is denoted as Tg(A). A laminated film vacuum-laminated onto the surface of the same substrate is heated at 130°C for 30 minutes, and then further heated at 170°C for 30 minutes. The polyethylene terephthalate film of the laminated film is peeled off, and the resin material is heated at 200°C for 60 minutes to obtain a cured product. The glass transition temperature of the obtained cured resin material is denoted as Tg(B).

[0043] The resin material according to the present invention has the above configuration, so that 1) the dielectric loss tangent of the cured product can be reduced, 2) the surface roughness after desmear treatment can be reduced, 3) the plating peel strength can be increased, and 4) the occurrence of cracks can be suppressed.

[0044] The resin material comprising configuration (1) contains a ketone compound with a relatively low boiling point. The resin material comprising configuration (2) contains a ketone compound represented by formula (X). The ketone compound represented by formula (X) has a relatively low boiling point. Because the resin material comprising configuration (1) contains a ketone compound with a relatively low boiling point, and because the resin material comprising configuration (2) contains a specific ketone compound with a relatively low boiling point, the volatility of the solvent can be increased, and the curing of the resin material proceeds smoothly. The reason why the resin material comprising configuration (1) or (2) can exhibit all of the effects described in 1)-4) above is presumed to be because the volatility of the solvent can be increased by containing a ketone compound with a relatively low boiling point, and the curing of the resin material proceeds smoothly, but is not limited to this.

[0045] One method to satisfy configuration (3) is to use a solvent containing a ketone compound as described in configurations (1) and (2).

[0046] The above resin material may have configuration (1), configuration (2), or configuration (3). The above resin material may have configuration (1) and configuration (2), configuration (2) and configuration (3), or configuration (1) and configuration (3). The above resin material may have configuration (1), configuration (2), and configuration (3). The above resin material may have only one of configurations (1), configuration (2), and configuration (3), or it may have two or more configurations.

[0047] The details of each component used in the resin material according to the present invention, and the applications of the resin material according to the present invention will be described below.

[0048] [Curable Compound] The above resin material contains a curable compound. Examples of the curable compound include thermosetting compounds and photocurable compounds. Only one type of curable compound may be used, or two or more types may be used in combination.

[0049] Examples of the above-mentioned thermosetting compounds include styrene compounds, phenoxy compounds, oxetane compounds, epoxy compounds, maleimide compounds, vinyl compounds, benzoxazine compounds, polyarylate compounds, diallyl phthalate compounds, acrylate compounds, episulfide compounds, (meth)acrylic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, and silicone compounds.

[0050] Examples of the above-mentioned photocurable compounds include (meth)acrylic compounds.

[0051] In the above resin material, excluding the solvent, the content of the curable compound is preferably 5% by weight or more, more preferably 10% by weight or more, preferably 80% by weight or less, and more preferably 60% by weight or less. When the content of the curable compound is above the lower limit and below the upper limit, the resin material can be cured well.

[0052] The curable compound is preferably a thermosetting compound. The resin material is preferably a thermosetting compound.

[0053] The above thermosetting compound is preferably an epoxy compound, a maleimide compound, a vinyl compound, or a benzoxazine compound, more preferably containing an epoxy compound or a maleimide compound, and even more preferably containing an epoxy compound. In this case, the dielectric loss tangent of the cured product can be further reduced, and the thermal dimensional stability of the cured product can be further improved.

[0054] <Epoxy Compound> The above resin material preferably contains 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 epoxy compound may be used, or two or more may be used in combination.

[0055] Examples of the epoxy compounds mentioned above 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, naphthalene type epoxy compounds, fluorene type epoxy compounds, phenol aralkyl type epoxy compounds, naphthol aralkyl type epoxy compounds, dicyclopentadiene type epoxy compounds, anthracene type epoxy compounds, epoxy compounds having an adamantane skeleton, epoxy compounds having a tricyclodecane skeleton, naphthylene ether type epoxy compounds, and epoxy compounds having a triazine core as their skeleton.

[0056] The epoxy compound described above may also be a glycidyl ether compound. The glycidyl ether compound described above is a compound having at least one glycidyl ether group.

[0057] The epoxy compound described above preferably includes an epoxy compound having an aromatic skeleton, more preferably includes an epoxy compound having a naphthalene skeleton or a phenyl skeleton, and even more preferably is an epoxy compound having an aromatic skeleton. In this case, the dielectric loss tangent of the cured product can be further reduced. Furthermore, the thermal dimensional stability and flame retardancy of the cured product can be further improved.

[0058] The epoxy compound described above preferably includes an epoxy compound that is liquid at 25°C and an epoxy compound that is solid at 25°C. In this case, the dielectric loss tangent of the cured product can be further reduced, and the coefficient of linear thermal expansion (CTE) of the cured product can be further reduced.

[0059] From the viewpoint of improving the lamination properties of the resin film and effectively preventing cracking of the resin film, the viscosity of the epoxy compound that is liquid at 25°C at 25°C is preferably 2000 mPa·s or less, more preferably 1000 mPa·s or less, and even more preferably 700 mPa·s or less. The content of the epoxy compound having a viscosity of 2000 mPa·s or less at 25°C in 100% by weight of the curable compound is preferably 5% by weight or more, and preferably 50% by weight or less. The content of the epoxy compound having a viscosity of 1000 mPa·s or less at 25°C in 100% by weight of the curable compound is preferably 5% by weight or more, and preferably 50% by weight or less. The content of the epoxy compound having a viscosity of 700 mPa·s or less at 25°C in 100% by weight of the curable compound is preferably 5% by weight or more, and preferably 50% by weight or less.

[0060] The viscosity of the epoxy compound can be measured using, for example, a dynamic viscoelasticity measuring device (such as the "VAR-100" manufactured by Rheological Instruments).

[0061] It is more preferable that the molecular weight of the epoxy compound is 1000 or less. In this case, even if the content of insulating filler is 50% or more of the 100% by weight of the components excluding the solvent in the resin material, a resin material with high fluidity during the formation of the insulating layer can be obtained. Therefore, when the uncured or B-staged resin material is laminated onto a circuit board, the insulating filler can be uniformly distributed.

[0062] The molecular weight of the epoxy compound described above refers to the molecular weight that can be calculated from the structural formula of the epoxy compound, if the epoxy compound is not a polymer, or if the structural formula of the epoxy compound can be identified. If the epoxy compound is a polymer, it refers to the weight-average molecular weight.

[0063] In the above resin material, excluding the solvent, the content of the epoxy compound is preferably 5% by weight or more, more preferably 10% by weight or more, preferably 80% by weight or less, and more preferably 60% by weight or less. If the content of the epoxy compound is above the lower limit, the thermal dimensional stability of the cured product can be further improved. If the content of the epoxy compound is below the upper limit, the dielectric loss tangent of the cured product can be further reduced.

[0064] <Maleimide Compound> The above resin material preferably contains a maleimide compound. Conventionally known maleimide compounds can be used as the above maleimide compound. Only one maleimide compound may be used, or two or more may be used in combination.

[0065] The above maleimide compound may have one maleimide group, two maleimide groups, two or more maleimide groups, three or more maleimide groups, four or more maleimide groups, 800 or fewer maleimide groups, 500 or fewer maleimide groups, or 300 or fewer maleimide groups.

[0066] The above maleimide compound may contain a maleimide compound that is solid at 25°C, a maleimide compound that is liquid at 25°C, or a maleimide compound that is solid at 25°C and a maleimide compound that is liquid at 25°C.

[0067] From the viewpoint of improving the lamination properties of the resin film and effectively preventing cracking of the resin film, the viscosity of the maleimide compound that is liquid at 25°C is preferably 2000 mPa·s or less, more preferably 1000 mPa·s or less, and even more preferably 700 mPa·s or less.

[0068] The viscosity of the above maleimide compound can be measured using, for example, a dynamic viscoelasticity measuring device (such as the "VAR-100" manufactured by Rheological Instruments).

[0069] The above maleimide compound may also be a bismaleimide compound.

[0070] Examples of the bismaleimide compounds mentioned above include N-phenylmaleimide and N-alkylbismaleimide.

[0071] The above maleimide compounds may have an aliphatic or alicyclic skeleton.

[0072] Examples of the above aliphatic skeleton include a chain-like aliphatic skeleton, such as saturated hydrocarbon groups and unsaturated hydrocarbon groups. The above aliphatic skeleton is preferably an aliphatic skeleton having four or more carbon atoms. The number of carbon atoms in the aliphatic skeleton having four or more carbon atoms is preferably five or more, more preferably six or more, even more preferably seven or more, preferably six0 or less, even more preferably five0 or less, and even more preferably four0 or less. More specifically, examples of the above aliphatic skeleton include alkyl groups having four to sixty carbon atoms (preferably alkyl groups having six to fourty carbon atoms). The above maleimide compound may have only one of the above aliphatic skeletons, or it may have two or more of them.

[0073] Examples of the alicyclic skeletons mentioned above include monocycloalkane rings, bicycloalkane rings, tricycloalkane rings, tetracycloalkane rings, and dicyclopentadiene rings. The maleimide compound may have only one of the alicyclic skeletons, or it may have two or more.

[0074] The above maleimide compound preferably has a skeleton derived from a dimeramine. Since maleimide compounds having a skeleton derived from a dimeramine have an aliphatic skeleton and an alicyclic skeleton, using such a maleimide compound can further reduce the dielectric constant and dielectric loss tangent of the cured product.

[0075] The above maleimide compound may or may not have an aromatic skeleton.

[0076] Examples of the above aromatic skeletons include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, tetracene rings, chrysene rings, triphenylene rings, tetrafen rings, pyrene rings, pentacene rings, picene rings, and perylene rings. The above maleimide compound may have only one of the above aromatic skeletons, or it may have two or more.

[0077] Examples of commercially available maleimide compounds include "BMI-3000J" and "BMI-689" manufactured by Designer Molecules Inc., "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., and "BMI" and "BMI-70" manufactured by K.I. Co., Ltd.

[0078] In the above resin material, excluding the solvent, the content of the maleimide compound is preferably 2.5% by weight or more, more preferably 5% by weight or more, preferably 60% by weight or less, and more preferably 50% by weight or less. When the content of the maleimide compound is above the lower limit and below the upper limit, the thermal dimensional stability of the cured product can be further improved.

[0079] <Vinyl Compound> The above resin material preferably contains a vinyl compound. Conventionally known vinyl compounds can be used as the vinyl compound. The vinyl compound is an organic compound having at least one vinyl group. Only one vinyl compound may be used, or two or more may be used in combination.

[0080] Examples of the vinyl compounds mentioned above include divinylbenzyl ether compounds.

[0081] In the above resin material, excluding the solvent, the content of the vinyl compound is preferably 1% by weight or more, more preferably 5% by weight or more, preferably 60% by weight or less, and more preferably 50% by weight or less. When the content of the vinyl compound is above the lower limit and below the upper limit, the dielectric constant and dielectric loss tangent of the cured product can be further reduced, and the thermal dimensional stability of the cured product can be further improved.

[0082] <Benzoxazine Compound> The above resin material preferably contains a benzoxazine compound. Conventionally known benzoxazine compounds can be used as the benzoxazine compound. Only one benzoxazine compound may be used, or two or more may be used in combination.

[0083] Examples of the above-mentioned benzoxazine compounds include P-d type benzoxazine and F-a type benzoxazine.

[0084] Examples of commercially available benzoxazine compounds include "P-d type" manufactured by Shikoku Chemicals Co., Ltd.

[0085] In the above resin material, excluding the solvent, the content of the benzoxazine compound is preferably 1% by weight or more, more preferably 5% by weight or more, preferably 60% by weight or less, and more preferably 50% by weight or less. When the content of the benzoxazine compound is above the lower limit and below the upper limit, the thermal dimensional stability of the cured product can be further improved.

[0086] [Insulating Filler] The above resin material includes an insulating filler. The use of the above insulating filler can further reduce the dielectric loss tangent of the cured product. In addition, the use of the above insulating filler further reduces the dimensional change of the cured product due to heat. The above insulating filler may be used by one type only, or two or more types may be used in combination.

[0087] The volume resistivity of the above insulating filler at 20°C is 1.0 × 10⁻⁶ １４ It is preferable that the density be Ω·cm or greater, and 1.0 × 10 １６It is more preferable that the resistivity is Ω·cm or greater. The volume resistivity of the above insulating filler at 20°C refers to the value measured in accordance with JIS C 2139.

[0088] The above insulating filler is preferably an insulating inorganic filler.

[0089] The insulating filler described above may be a solid particle or a hollow particle. A hollow particle is a particle that has a hollow space inside. A hollow particle has a hollow space and an outer shell surrounding the hollow space. The number of hollow spaces surrounded by the outer shell is usually one.

[0090] From the viewpoint of further reducing the dielectric loss tangent of the cured product, it is preferable that the insulating filler contains hollow particles.

[0091] Examples of the insulating fillers mentioned above include solid silica particles, hollow silica particles, solid aluminosilicate particles, hollow aluminosilicate particles, solid alumina particles, hollow alumina particles, talc, clay, mica, hydrotalcite, magnesium oxide, aluminum hydroxide, diamond, aluminum nitride, and boron nitride.

[0092] The insulating filler is preferably solid silica particles or hollow silica particles. In this case, the surface roughness of the cured product can be reduced, and the adhesive strength between the cured product and the metal layer can be further increased. Furthermore, fine wiring can be formed on the surface of the cured product, providing the cured product with better insulation reliability. When the insulating filler is solid silica particles or hollow silica particles, the thermal expansion coefficient of the cured product becomes even lower, and the dielectric loss tangent of the cured product becomes even smaller.

[0093] The average particle size of the insulating filler is preferably 50 nm or more, more preferably 100 nm or more, even more preferably 500 nm or more, preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less. When the average particle size of the insulating filler is above the lower limit and below the upper limit, the surface roughness after etching can be reduced, the plating peel strength can be increased, and the adhesion between the insulating layer and the metal layer can be further improved.

[0094] The median diameter (d50) value, which represents 50% of the average particle size of the insulating filler, is adopted. The average particle size can be measured using a laser diffraction scattering particle size distribution analyzer. In the case of aggregated particles of the insulating filler, the average particle size of the insulating filler refers to the primary particle size.

[0095] The insulating filler is preferably spherical, and more preferably spherical silica. In this case, the surface roughness of the cured product is effectively reduced, and the adhesive strength between the cured product and the metal layer is effectively increased. When the insulating filler is spherical, the aspect ratio of the insulating filler is preferably 1 or more, preferably 2 or less, and more preferably 1.5 or less.

[0096] The insulating filler is preferably surface-treated, more preferably surface-treated with a coupling agent, and even more preferably surface-treated with a silane coupling agent. Surface treatment of the insulating filler further reduces the surface roughness of the cured product, thereby increasing the adhesive strength between the cured product and the metal layer. Furthermore, surface treatment of the insulating filler allows for the formation of finer wiring on the surface of the cured product, and provides the cured product with even better inter-wiring insulation reliability and inter-layer insulation reliability.

[0097] Examples of the coupling agents mentioned above include silane coupling agents, titanium coupling agents, and aluminum coupling agents. Examples of the silane coupling agents mentioned above include methacrylicsilane, acrylicsilane, aminosilane, imidazolesilane, vinylsilane, and epoxysilane.

[0098] As the insulating filler described above, two or more insulating fillers with different types of coupling agents may be used. Preferably, the insulating filler includes a first insulating filler which is a surface-treated product with a first coupling agent, and a second insulating filler which is a surface-treated product with a second coupling agent different from the first coupling agent. More preferably, the insulating filler includes a first insulating filler which is a surface-treated product with aminosilane, and a second insulating filler which is a surface-treated product with vinylsilane. In this case, the plating peel strength can be further increased.

[0099] In the above resin material, excluding the solvent, the content of the insulating filler is preferably 25% by weight or more, more preferably 30% by weight or more, even more preferably 40% by weight or more, still more preferably 50% by weight or more, particularly preferably 60% by weight or more, most preferably 65% ​​by weight or more, preferably 90% by weight or less, more preferably 85% by weight or less, and still more preferably 80% by weight or less. If the content of the insulating filler is above the lower limit, the dielectric loss tangent of the cured product can be further reduced. If the content of the insulating filler is below the upper limit, the thermal dimensional stability of the cured product can be improved and warping of the cured product can be effectively suppressed. If the content of the insulating filler is above the lower limit and below the upper limit, the surface roughness of the surface of the cured product can be further reduced and finer wiring can be formed on the surface of the cured product. Furthermore, if the content of the insulating filler is above the lower limit and below the upper limit, it is possible to lower the thermal expansion coefficient of the cured product and improve smear removal properties at the same time.

[0100] [Solvent] The above resin material contains a solvent. The above solvent may be used to obtain a slurry containing the above insulating filler. Only one type of solvent may be used, or two or more types may be used in combination.

[0101] Examples of the above-mentioned solvents include acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane, toluene, xylene, methyl ethyl ketone, N,N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidone, n-hexane, cyclohexane, cyclohexanone, cyclopentanone, 2-methyl-2-cyclopenten-1-one, 2-methylcyclopentanone, 3-methylcyclopentanone, 2-ethylcyclopentanone, 3-ethylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, and naphtha, which is a mixture of these solvents.

[0102] The above solvent preferably contains a ketone compound.

[0103] From the viewpoint of achieving the effects described in 1)-4) above, it is preferable that the boiling point of the ketone compound is 90°C or higher and 150°C or lower. That is, it is preferable that the solvent contains a ketone compound having a boiling point of 90°C or higher and 150°C or lower.

[0104] From the viewpoint of making the effects of 1)-4) described above even more effective, the boiling point of the ketone compound is preferably 90°C or higher, more preferably 100°C or higher, even more preferably 110°C or higher, preferably 150°C or lower, and more preferably 140°C or lower.

[0105] The number of carbon atoms in the above ketone compound is preferably 4 or more, more preferably 5 or more, preferably 7 or less, and more preferably 6 or less. When the number of carbon atoms in the above ketone compound is above the lower limit and below the upper limit, it becomes easier to adjust the boiling point of the ketone compound to the above preferred range, and the effects of 1) to 4) described above can be exerted even more effectively.

[0106] From the viewpoint of achieving the effects described in 1)-4) above, it is preferable that the solvent contains a ketone compound represented by the following formula (X). The ketone compound represented by the following formula (X) is a ketone compound having a cyclic ketone structure.

[0107]

[0108] In the above formula (X), R １ R represents a hydrogen atom or a methyl group. ２ R represents a hydrogen atom or a methyl group. ３ R represents a hydrogen atom or a methyl group. ４ represents a hydrogen atom or a methyl group.

[0109] From the viewpoint of making the effects of 1)-4) described above even more effective, in the above formula (X), R ３ It is preferable that R represents a hydrogen atom. ４ It is preferable that this represents a hydrogen atom.

[0110] From the viewpoint of making the effects of 1) to 4) described above even more effective, the ketone compound preferably contains cyclopentanone, 2-methyl-2-cyclopenten-1-one, 2-methylcyclopentanone, 3-methylcyclopentanone, 2-ethylcyclopentanone, 3-ethylcyclopentanone, 2,2-dimethylcyclopentanone, or 2,4,4-trimethylcyclopentanone, and more preferably contains cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, or 2,2-dimethylcyclopentanone.

[0111] In 100% by weight of the above solvent, the content of the above ketone compound is preferably 25% by weight or more, more preferably 30% by weight or more, even more preferably 35% by weight or more, still more preferably 40% by weight or more, even more preferably 50% by weight or more, particularly preferably 60% by weight or more, most preferably 70% by weight or more, and preferably 100% by weight or less. When the content of the above ketone compound is above the lower limit, the effects of 1) to 4) described above can be exhibited more effectively. In 100% by weight of the above solvent, the content of the above ketone compound may be 100% by weight or less, less than 100% by weight, or 95% by weight or less.

[0112] The amount of the solvent in 100% by weight of the resin material can be appropriately selected considering the desired viscosity, etc. The amount of the solvent in 100% by weight of the resin material may be 10% by weight or more, 15% by weight or more, 20% by weight or more, 50% by weight or less, 45% by weight or less, or 40% by weight or less.

[0113] The content of the ketone compound in 100% by weight of the above resin material can be appropriately selected considering the desired viscosity, etc. The content of the ketone compound in 100% by weight of the above resin material may be 5% by weight or more, 10% by weight or more, 15% by weight or more, 40% by weight or less, 35% by weight or less, or 30% by weight or less.

[0114] [Curing agent] The above resin material may or may not contain a curing agent. The above resin material may or may not contain a curing agent. The above resin material may optionally contain a curing agent. It is preferable that the above resin material contains a curing agent. The above curing agent may be a thermosetting agent or a photocuring agent. The above curing agent can be appropriately selected depending on the type of curable compound. Only one type of curing agent may be used, or two or more types may be used in combination.

[0115] Examples of the curing agents mentioned above include active ester compounds (active ester curing agents), phenol compounds (phenol curing agents), cyanate ester compounds (cyanate ester curing agents), carbodiimide compounds (carbodiimide curing agents), amine compounds (amine curing agents), thiol compounds (thiol curing agents), phosphine compounds, dicyandiamides, and acid anhydrides.

[0116] From the viewpoint of further reducing the dielectric loss tangent of the cured product, the curing agent preferably contains an active ester compound, a phenol compound, a cyanate ester compound, or a dicyandiamide, and more preferably contains an active ester compound and a dicyandiamide.

[0117] From the viewpoint of further reducing the dielectric loss tangent of the cured product, it is preferable that the curing agent contains an active ester compound.

[0118] <Activated Ester Compounds> The curing agent preferably contains an activated ester compound. The activated ester compound refers to a compound having at least one ester bond, with aliphatic chains, aliphatic rings, or aromatic rings bonded to both sides of the ester bond. The activated ester compound can be 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. Only one activated ester compound may be used, or two or more may be used in combination.

[0119] Examples of the above-mentioned active ester compounds include compounds represented by the following formula (1).

[0120]

[0121] In formula (1) above, X1 represents a group having an aliphatic chain, a group having an aliphatic ring, or a group having an aromatic ring, and X2 represents a group having an aromatic ring. Preferred examples of the group having an aromatic ring include a benzene ring which may have substituents, and a naphthalene ring which may have substituents. Examples of substituents include hydrocarbon groups. The number of carbon atoms in the hydrocarbon group is preferably 1 or more, preferably 12 or less, more preferably 6 or less, and even more preferably 4 or less.

[0122] In formula (1) above, examples of combinations of X1 and X2 include 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 formula (1) above, examples of combinations 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.

[0123] The above-mentioned active ester compound is not particularly limited. From the viewpoint of further improving the thermal dimensional stability and flame retardancy of the cured product, it is preferable that the above-mentioned active ester compound is an active ester compound having two or more aromatic rings. The above-mentioned active ester compound having two or more aromatic rings may have 10 or fewer aromatic rings, 5 or fewer, 3 or fewer, or 2. From the viewpoint of further reducing the dielectric loss tangent of the cured product and further improving the thermal dimensional stability of the cured product, it is more preferable that the above-mentioned active ester compound has a naphthalene ring or a dicyclopentadiene skeleton in its main chain skeleton.

[0124] Examples of commercially available active ester compounds include DIC Corporation's "HPC-8000-65T", "HPC-8000L-65MT", "EXB9416-70BK", "HPC-8150-62T", "EXB-8", and "EXB8100-65T".

[0125] <Phenol Compounds> The curing agent described above preferably contains phenol compounds. The phenol compounds may be used individually or in combination of two or more.

[0126] Examples of the phenol compounds mentioned above include novolac-type phenols, biphenol-type phenols, naphthalene-type phenols, dicyclopentadiene-type phenols, aralkyl-type phenols, and dicyclopentadiene-type phenols.

[0127] Examples of commercially available phenol compounds include novolac-type phenols (DIC Corporation's "TD-2091"), biphenylnovolac-type phenols (Meiwa Chemical Industries, Ltd.'s "MEH-7851"), aralkyl-type phenols (Meiwa Chemical Industries, Ltd.'s "MEH-7800"), and phenols having an aminotriazine skeleton (DIC Corporation's "LA-1356" and "LA-3018-50P").

[0128] <Cyanate ester compound> The curing agent preferably contains a cyanate ester compound. The cyanate ester compound may be used alone or in combination of two or more.

[0129] Examples of the above-mentioned cyanate ester compounds include novolac-type cyanate ester resins, bisphenol-type cyanate ester resins, and prepolymers in which these are partially trimerized. Examples of the above-mentioned novolac-type cyanate ester resins include phenol novolac-type cyanate ester resins and alkylphenol-type cyanate ester resins. Examples of the above-mentioned bisphenol-type cyanate ester resins include bisphenol A-type cyanate ester resins, bisphenol E-type cyanate ester resins, and tetramethylbisphenol F-type cyanate ester resins.

[0130] Examples of commercially available cyanate ester compounds include phenol novolac type cyanate ester resins (PT-30 and PT-60 from Lonza Japan Co., Ltd.) and prepolymers in which bisphenol type cyanate ester resins have been trimerized (BA-230S, BA-3000S, BTP-1000S, and BTP-6020S from Lonza Japan Co., Ltd.).

[0131] <Carbodiimide Compounds> The curing agent described above preferably contains a carbodiimide compound. The carbodiimide compound may be used alone or in combination of two or more.

[0132] The above carbodiimide compound is a compound having a structural unit represented by the following formula (2). In formula (2), the rightmost and leftmost ends are bonding sites with other groups. The above carbodiimide compound may be used alone, or two or more may be used in combination.

[0133]

[0134] In formula (2) above, X represents an alkylene group, a group to which a substituent is attached to an alkylene group, a cycloalkylene group, a group to which a substituent is attached to a cycloalkylene group, an arylene group, or a group to which a substituent is attached to an arylene group, and p represents an integer from 1 to 5. If there are multiple X's, they may be the same or different.

[0135] In one preferred embodiment, at least one X is an alkylene group, a group to which a substituent is attached to an alkylene group, a cycloalkylene group, or a group to which a substituent is attached to a cycloalkylene group.

[0136] Examples of commercially available carbodiimide compounds include "Carbodilite V-02B," "Carbodilite V-03," "Carbodilite V-04K," "Carbodilite V-07," "Carbodilite V-09," "Carbodilite 10M-SP," and "Carbodilite 10M-SP (modified)" manufactured by Nisshinbo Chemical Co., Ltd., as well as "Stabaczol P," "Stabaczol P400," and "Hycadyl 510" manufactured by Rhein Chemie Corporation.

[0137] <Further Details of the Curing Agent> In the above resin material, the content of the curing agent per 100 parts by weight of the curable 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 140 parts by weight or less. When the content of the curing agent is above the lower limit and below the upper limit, the curability is further improved, the thermal dimensional stability is further enhanced, and the volatilization of residual unreacted components can be further suppressed.

[0138] When the above resin material contains an epoxy compound, the content of the curing agent in the above resin material 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 140 parts by weight or less, per 100 parts by weight of the epoxy compound. When the content of the curing agent is above the lower limit and below the upper limit, the curability is further improved, the thermal dimensional stability is further enhanced, and the volatilization of residual unreacted components can be further suppressed.

[0139] [Curing Accelerator] The above resin material may or may not contain a curing accelerator. The above resin material may or may not contain a curing accelerator. It is preferable that the above resin material contains a curing accelerator. The curing speed is further increased by using the above curing accelerator. By rapidly curing the resin material, the crosslinking structure in the cured product becomes uniform, the number of unreacted functional groups decreases, and as a result the crosslinking density increases. Furthermore, by using the above curing accelerator, the resin material can be cured well even at relatively low temperatures. The above curing accelerator may be used alone, or two or more may be used in combination.

[0140] Examples of the curing accelerators mentioned above include anionic curing accelerators such as imidazole compounds, amine compounds, and organophosphorus compounds; cationic curing accelerators such as organometallic compounds; and radical curing accelerators such as peroxides and azo compounds.

[0141] The above imidazole compounds 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-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, and 1-cyanoethyl-2-phenylimidazole tri Examples include melite, 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 adduct, 2-phenylimidazole isocyanurate adduct, 2-methylimidazole isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-dihydroxymethylimidazole.

[0142] Examples of the above-mentioned amine compounds include diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, diethylenetriamine, ethylenediamine, tris(dimethylaminomethyl)phenol, benzyldimethylamine, m-xylylenedi(dimethylamine), N,N'-dimethylpiperazine, N-methylpyrrolidine, N-methylhydrooxypiperidine, m-xylylenediamine, isophoronediamine, N-aminoethylpiperazine, polyoxypropylene polyamine, and 4,4-dimethylaminopyridine. Furthermore, the amine compounds may be modified versions of these amine compounds.

[0143] Examples of the above-mentioned organophosphorus compounds include organophosphine compounds such as triphenylphosphine, tricyclohexylphosphine, trybenzylphosphine, diphenyl(alkylphenyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkylalkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, and alkyldiarylphosphine, as well as phosphonium salt compounds such as tetraphenylphosphonium and tetraphenylborate.

[0144] Examples of the organometallic compounds mentioned above include zinc naphthenate, cobalt naphthenate, tin octoate, cobalt octoate, bisacetylacetonate cobalt(II), and trisacetylacetonate cobalt(III).

[0145] Examples of the above-mentioned peroxides include diacyl peroxides, peroxyesters, peroxydicarbonates, monoperoxycarbonates, peroxyketals, dialkyl peroxides, dibenzyl peroxides, dicumyl peroxides, hydroperoxides, and ketone peroxides.

[0146] From the viewpoint of further lowering the curing temperature and effectively suppressing the occurrence of cracks, the curing accelerator preferably contains an anionic curing accelerator, and more preferably contains an amine compound and an organophosphorus compound.

[0147] The content of the curing accelerator is not particularly limited. In the resin material, excluding the insulating filler and solvent, the content of the curing accelerator is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, preferably 5% by weight or less, and more preferably 3% by weight or less. When the content of the curing accelerator is above the lower limit and below the upper limit, the resin material cures efficiently. If the content of the curing accelerator is within a more preferable range, the storage stability of the resin material is further improved, and an even better cured product can be obtained.

[0148] [Thermoplastic resin] The above resin material may or may not contain a thermoplastic resin. The above resin material may or may not contain a thermoplastic resin.

[0149] Examples of the thermoplastic resins mentioned above include polyvinyl acetal resin, polyimide resin, and phenoxy resin. Only one type of thermoplastic resin may be used, or two or more types may be used in combination.

[0150] From the viewpoint of effectively reducing the dielectric loss tangent of the cured product and effectively increasing the plating peel strength, regardless of the curing environment, the thermoplastic resin preferably contains a polyimide resin or a phenoxy resin, and more preferably contains a polyimide resin.

[0151] From the viewpoint of effectively suppressing warping of the cured product and further increasing the plating peel strength, it is preferable that the thermoplastic resin includes a thermoplastic resin (A) having a softening point of 120°C or higher and a polyimide resin (B) having a softening point of 110°C or lower.

[0152] The softening point of the above thermoplastic resin can be determined using a differential scanning calorimetry device (for example, TA Instruments' "Q2000"), by heating it from -30°C to 260°C in a nitrogen atmosphere at a heating rate of 3°C / min, and then determining the inflection point of the reverse heat flow.

[0153] <Thermoplastic resin (A) with a softening point of 120°C or higher> The above resin material preferably contains thermoplastic resin (A). Examples of thermoplastic resin (A) include polyvinyl acetal resin, polyimide resin, and phenoxy resin. Only one type of thermoplastic resin (A) may be used, or two or more types may be used in combination.

[0154] From the viewpoint of effectively reducing the dielectric loss tangent of the cured product and effectively improving the adhesion of the metal wiring, the thermoplastic resin (A) is preferably a polyimide resin or a phenoxy resin, and more preferably a polyimide resin. When the thermoplastic resin (A) is a polyimide resin, the dielectric loss tangent of the cured product can be reduced even more effectively.

[0155] The polyimide resin (A) is not particularly limited. Conventional known polyimide resins can be used as the polyimide resin. Only one type of polyimide resin may be used, or two or more types may be used in combination.

[0156] From the viewpoint of improving solubility, the polyimide resin, which is the thermoplastic resin (A), is preferably a polyimide resin that is a reaction product of tetracarboxylic acid and dimeramine. The tetracarboxylic acid may also be a tetracarboxylic dianhydride.

[0157] The softening point of thermoplastic resin (A) is 120°C or higher. Preferably, the softening point of thermoplastic resin (A) is 125°C or higher, more preferably 130°C or higher, more preferably 180°C or lower, and more preferably 150°C or lower. When the softening point is above the lower limit and below the upper limit, the occurrence of cracks can be effectively suppressed, and the plating peel strength can be further increased.

[0158] The weight-average molecular weight of the thermoplastic resin (A) is preferably 5,000 or more, more preferably 10,000 or more, more preferably 100,000 or less, and more preferably 50,000 or less. When the weight-average molecular weight is above the lower limit and below the upper limit, the occurrence of cracks can be effectively suppressed, and the plating peel strength can be further increased.

[0159] The weight-average molecular weight of thermoplastic resin (A) refers to the weight-average molecular weight in polystyrene terms, measured by gel permeation chromatography (GPC).

[0160] In 100% by weight of the above thermoplastic resin, the content of thermoplastic resin (A) is preferably 40% by weight or more, more preferably 45% by weight or more, preferably 99% by weight or less, and more preferably 97% by weight or less. When the content of thermoplastic resin (A) is above the lower limit and below the upper limit, the occurrence of cracks can be effectively suppressed, and the plating peel strength can be further increased.

[0161] In the above resin material, excluding the insulating filler and solvent, the content of thermoplastic resin (A) in 100% by weight of the components is preferably 1% by weight or more, more preferably 5% by weight or more, preferably 30% by weight or less, and more preferably 20% by weight or less. When the content of thermoplastic resin (A) is above the lower limit and below the upper limit, the occurrence of cracks can be effectively suppressed, and the plating peel strength can be further increased.

[0162] <Polyimide resin (B) with a softening point of 110°C or lower> The above resin material preferably contains polyimide resin (B). By using polyimide resin (B), the internal stress of the cured product can be effectively relieved, and therefore, warping of the cured product can be effectively suppressed. The reason why the internal stress can be effectively relieved by using polyimide resin (B) is thought to be due to the softening of the polyimide resin (B) and molecular motion when the resin material is heated, but the reason is not limited to this. Only one type of polyimide resin (B) may be used, or two or more types may be used in combination.

[0163] The polyimide resin (B) is not particularly limited as long as its softening point is 110°C or lower.

[0164] From the viewpoint of improving solubility, the polyimide resin (B) is preferably a polyimide resin which is a reaction product of tetracarboxylic acid and dimeramine. The tetracarboxylic acid may also be a tetracarboxylic dianhydride.

[0165] Examples of the above tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenylethertetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, and 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl Examples include sulfide dianhydrides, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylter dianhydride, and bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride.

[0166] Examples of the above-mentioned dimer amines include Versamin 551 (trade name, manufactured by BASF Japan, 3,4-bis(1-aminoheptyl)-6-hexyl-5-(1-octenyl)cyclohexene), Versamin 552 (trade name, manufactured by Cognics Japan, a hydrogenated version of Versamin 551), PRIAMINE 1075, PRIAMINE 1074 (trade names, both manufactured by Croda Japan), and others.

[0167] The softening point of polyimide resin (B) is 110°C or lower. Preferably, the softening point of polyimide resin (B) is 40°C or higher, more preferably 50°C or higher, more preferably 105°C or lower, and more preferably 100°C or lower. When the softening point is above the lower limit and below the upper limit, crack occurrence can be effectively suppressed, and the plating peel strength can be further increased.

[0168] The weight-average molecular weight of the polyimide resin (B) is preferably 5,000 or more, more preferably 10,000 or more, more preferably 100,000 or less, and more preferably 50,000 or less. When the weight-average molecular weight is above the lower limit and below the upper limit, the occurrence of cracks can be effectively suppressed, and the plating peel strength can be further increased.

[0169] The weight-average molecular weight of polyimide resin (B) refers to the weight-average molecular weight in polystyrene terms, measured by gel permeation chromatography (GPC).

[0170] In 100% by weight of the above thermoplastic resin, the content of polyimide resin (B) is preferably 1% by weight or more, more preferably 3% by weight or more, preferably 55% by weight or less, and more preferably 50% by weight or less. When the content of polyimide resin (B) is above the lower limit and below the upper limit, the occurrence of cracks can be effectively suppressed, and the plating peel strength can be further increased.

[0171] In the above resin material, excluding the insulating filler and solvent, the content of polyimide resin (B) in 100% by weight is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, preferably 7% by weight or less, and more preferably 6% by weight or less. When the content of polyimide resin (B) is above the lower limit and below the upper limit, the occurrence of cracks can be effectively suppressed, and the plating peel strength can be further increased.

[0172] <Further details of the thermoplastic resin> The total content of thermoplastic resin (A) and polyimide resin (B) in 100% by weight of the above thermoplastic resin is preferably 10% by weight or more, more preferably 50% by weight or more, even more preferably 70% by weight or more, still more preferably 80% by weight or more, even more preferably 90% by weight or more, particularly preferably 95% by weight or more, and preferably 100% by weight (total amount) or less. The total content of thermoplastic resin (A) and polyimide resin (B) in 100% by weight of the above thermoplastic resin is most preferably 100% by weight (total amount). When the above total content is above the above lower limit, the occurrence of cracks can be effectively suppressed and the plating peel strength can be further increased. The total content of thermoplastic resin (A) and polyimide resin (B) in 100% by weight of the above thermoplastic resin may be 100% by weight or less, may be less than 100% by weight, or may be 99% by weight or less.

[0173] In the above resin material, excluding the insulating filler and solvent, the content of the thermoplastic resin in 100% by weight of the components is preferably 1% by weight or more, more preferably 3% by weight or more, preferably 20% by weight or less, and more preferably 15% by weight or less. When the content of the thermoplastic resin is above the lower limit and below the upper limit, the occurrence of cracks can be effectively suppressed, and the plating peel strength can be further increased.

[0174] [Other Components] For the purpose of improving impact resistance, heat resistance, resin compatibility, and workability, the above resin material may contain other components in addition to those described above. Examples of these other components include leveling agents, flame retardants, coupling agents, colorants, antioxidants, UV degradation inhibitors, defoamers, thickeners, and thixotropy-inducing agents. Only one of these other components may be used, or two or more may be used in combination.

[0175] The above resin material may or may not contain glass cloth. It is preferable that the above resin material does not contain glass cloth. It is preferable that the above resin material is not a prepreg.

[0176] (Further details of the resin material) In the above resin material, it is preferable that the ratio (Tg(B) / Tg(A)) of the cured resin material's Tg(B), determined by the glass transition temperature measurement method described below, to the semi-cured resin material's Tg(A) is 1.0 or more and 1.2 or less.

[0177] Method for measuring glass transition temperature: A copper foil (e.g., Mitsui Mining & Smelting Co., Ltd. "MT18Ex", 35 μm thick) is vacuum-laminated to both sides of a double-sided copper-clad laminate (e.g., Resonaq "MCL-E679FG"). Then, the shiny side of the copper foil is treated with Cz (e.g., MEC "Cz8101") to create a substrate in which the surface of the copper foil is etched by about 1 μm. A resin material is coated onto the surface of a 25 μm thick polyethylene terephthalate film, and then dried in a 100°C gear oven for 2 minutes to obtain a laminated film in which a 40 μm thick resin film is laminated onto the surface of the polyethylene terephthalate film. The obtained laminated film is vacuum-laminated onto the surface of the substrate from the resin film side, heated at 130°C for 30 minutes, and then heated again at 170°C for 30 minutes. After cutting out the copper foil and resin film from the laminated structure of the substrate and resin film, the copper foil portion is treated with iron chloride (FeCl ３ The resin material is etched with an aqueous solution to obtain a semi-cured product. The glass transition temperature of the obtained semi-cured resin material is denoted as Tg(A). A laminated film vacuum-laminated onto the surface of the same substrate is heated at 130°C for 30 minutes, and then heated at 170°C for another 30 minutes. Next, the polyethylene terephthalate film of the laminated film is peeled off, and the resin material is heated at 200°C for 60 minutes to obtain a cured product. The glass transition temperature of the obtained cured resin material is denoted as Tg(B).

[0178] The glass transition temperature mentioned above is measured more specifically as follows.

[0179] Semi-cured and cured resin materials are cut to a size of 5 mm in width and 20 mm in length to prepare test specimens for measuring the glass transition temperature. Using a tensile-mode dynamic mechanical analyzer (DMA, for example, Hitachi High-Tech Corporation's "DMA7100"), the glass transition temperature is defined as the peak value of tanδ measured at a frequency of 10 Hz while the test specimen is heated at a rate of 5°C / min in the temperature range of 23°C to 330°C.

[0180] From the viewpoint of making the effects of 1)-4) described above even more effective, the above ratio (Tg(B) / Tg(A)) is preferably 1.08 or higher, and preferably 1.18 or lower.

[0181] The above-mentioned resin material can be used in a variety of applications. For example, it is suitably used to form a mold resin for embedding semiconductor chips in semiconductor devices. It is also suitably used as a substitute for liquid crystal polymer (LCP), in millimeter-wave antennas, and in redistribution layers. The above-mentioned resin material is not limited to the above applications and is suitably used in all wiring formation applications.

[0182] The above resin material is suitably used as an adhesive material. For example, the above resin material is suitably used as an adhesive material for power overlay packages, an adhesive material for printed circuit boards, an adhesive material for coverlays of flexible printed circuit boards, and an adhesive material for semiconductor bonding. The above resin material is preferably an adhesive material.

[0183] The above resin material is suitably used as an insulating material. The above resin material is suitably used to form an insulating layer in a printed circuit board (use of the above resin material for forming an insulating layer in a printed circuit board). The above resin material is more suitably used to form an insulating layer in a multilayer printed circuit board (use of the above resin material for forming an insulating layer in a multilayer printed circuit board). The above resin material is preferably an insulating material, and more preferably an interlayer insulating material. The above insulating material may also serve as an adhesive material.

[0184] (Resin Film) A resin film (B-stage compound / B-stage film) is obtained by forming the above-mentioned resin material into a film. The above resin film is a resin film formed from the above-mentioned resin material. The above resin film is preferably a B-stage film.

[0185] The following methods can be used to form the above-mentioned resin material into a film to obtain a resin film: Extrusion molding, in which the resin material is melted and kneaded using an extruder, extruded, and then formed into a film using a T-die or circular die; Casting molding, in which the resin material is cast into a film; and other conventionally known film molding methods. Extrusion molding or casting molding is preferred because it can accommodate thinning. The film includes sheets.

[0186] A resin film, which is a B-stage film, can be obtained by forming a resin material into a film and then heating and drying it for 1 to 10 minutes at, for example, 50°C to 150°C, so as not to cause excessive hardening due to heat.

[0187] The above B-stage film is in a semi-cured state. A semi-cured material is not completely cured and may undergo further curing.

[0188] The above-mentioned resin film does not have to be a prepreg. If the above-mentioned resin film is not a prepreg, migration along the glass cloth, etc., will not occur. Also, when laminating or precuring the resin film, the surface will not become uneven due to the glass cloth.

[0189] The above-mentioned resin film can be used in the form of a laminated film comprising a metal foil or a base film and a resin film laminated on the surface of the metal foil or base film. The metal foil is preferably a copper foil.

[0190] 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 treated with a release agent as needed.

[0191] The base film of the laminated film described above is preferably a polyethylene terephthalate film.

[0192] 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 by the resin film is preferably greater than or equal to the thickness of the conductor layer (metal layer) forming the circuit. The thickness of the insulating layer is preferably 5 μm or more, and preferably 200 μm or less.

[0193] (Laminated Structure and Copper-Clad Laminate) A laminated structure can be obtained by laminating a lamination target member having a metal layer on one or both sides of its surface onto the above resin film. The above laminated structure comprises a lamination target member having a metal layer on its surface and a resin film laminated on the surface of the metal layer, wherein the resin film is formed of the above resin material. The method of laminating the above resin film and the lamination target member is not particularly limited, and known methods can be used. For example, the above resin film can be laminated onto the lamination target member while heating or under pressure without heating using a device such as a parallel plate press or a roll laminator.

[0194] The material of the above metal layer is preferably copper.

[0195] The laminated member having the above-mentioned metal layer on its surface may be a metal foil such as copper foil.

[0196] The above-mentioned resin material is suitably used to obtain a copper-clad laminate. An example of the above-mentioned copper-clad laminate is a copper-clad laminate comprising a copper foil and a resin film laminated on one surface of the copper foil, wherein the resin film is formed of the above-mentioned resin material.

[0197] The thickness of the copper foil in the copper-clad laminate is not particularly limited. Preferably, the thickness of the copper foil is 1 μm or more and 100 μm or less. Furthermore, in order to increase the adhesive strength between the cured resin material and the copper foil, it is preferable that the copper foil has fine irregularities on its surface. The method for forming the irregularities is not particularly limited. Examples of methods for forming the irregularities include methods using known chemical solutions, methods using known plasma treatment, and methods using known UV treatment.

[0198] (Circuit board with insulating layer) The above resin material is suitably used to obtain a circuit board with an insulating layer. An example of the above circuit board with an insulating layer is a circuit board comprising a circuit board and an insulating layer disposed on the surface of the circuit board, wherein the insulating layer is a cured product of the above resin material.

[0199] In the above-described circuit board with insulating layer, it is preferable that the insulating layer is laminated on the surface of the circuit board on which the circuits are provided. In the above-described circuit board with insulating layer, it is preferable that a portion of the insulating layer is embedded between the circuits.

[0200] The above-mentioned circuit board with an insulating layer can be obtained by conventionally known methods.

[0201] (Multilayer substrates and multilayer printed wiring boards) The above resin material is suitably used to obtain multilayer substrates. An example of the above multilayer substrate is a multilayer substrate comprising a circuit board and an insulating layer laminated on the circuit board. The insulating layer of the above multilayer substrate is a cured product of the above resin material. The insulating layer is preferably laminated on the surface of the circuit board on which the circuits (metal layers) are provided. A part of the insulating layer is preferably embedded between the circuits.

[0202] In the above-described 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.

[0203] The roughening treatment method can be any conventionally known roughening treatment method and is not particularly limited. The surface of the insulating layer may be swollen before the roughening treatment.

[0204] Furthermore, it is preferable that the multilayer substrate further comprises a copper plating layer laminated on the roughened surface of the insulating layer.

[0205] Another example of the multilayer substrate described above is a multilayer substrate comprising a circuit board, an insulating layer laminated on the surface of the circuit board, and a copper foil laminated on the surface of the insulating layer opposite to the surface on which the circuit board is laminated. Preferably, the insulating layer is formed by curing the resin film using a copper-clad laminate comprising a copper foil and a resin film laminated on one surface of the copper foil. Furthermore, it is preferable that the copper foil is etched and forms a copper circuit.

[0206] Another example of the multilayer substrate described above is a multilayer substrate comprising 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. Preferably, the multilayer substrate further comprises a circuit laminated on at least one surface of the insulating layers formed using the resin film.

[0207] The above-mentioned resin material is suitably used to form an insulating layer in a multilayer printed circuit board.

[0208] The multilayer printed circuit board described above comprises, for example, a circuit board, a plurality of insulating layers disposed on the surface of the circuit board, and a metal layer disposed between the plurality of insulating layers. In the multilayer printed circuit board described above, at least one of the plurality of insulating layers is a cured product of the resin material described above.

[0209] Figure 1 is a schematic cross-sectional view showing a multilayer printed circuit board using a resin material according to one embodiment of the present invention.

[0210] In the multilayer printed circuit board 11 shown in Figure 1, a plurality of insulating layers 13 to 16 are laminated on the upper surface 12a of the circuit board 12. The insulating layers 13 to 16 are cured material layers. A metal layer 17 is formed in a portion of the upper surface 12a of the circuit board 12. Of the plurality of insulating layers 13 to 16, a metal layer 17 is formed in a portion of the upper surface of insulating layers 13 to 15, excluding insulating layer 16 located on the outer surface opposite to the circuit board 12. The metal layer 17 is a circuit. Metal layers 17 are arranged between the circuit board 12 and the insulating layer 13, and between each layer of the laminated insulating layers 13 to 16. The lower metal layer 17 and the upper metal layer 17 are connected to each other by at least one of via-hole connections and through-hole connections (not shown).

[0211] In the multilayer printed circuit board 11, the insulating layers 13 to 16 are formed from cured resin material. In this embodiment, the surfaces of the insulating layers 13 to 16 are roughened, so fine pores (not shown) are formed on the surfaces of the insulating layers 13 to 16. The metal layer 17 extends into the interior of these fine pores. In addition, in the multilayer printed circuit 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. Furthermore, in the multilayer printed circuit board 11, good insulation reliability is provided between the upper metal layer and the lower metal layer that are not connected by via-hole connections and through-hole connections (not shown).

[0212] The present invention will be specifically described below with reference to examples and comparative examples. The present invention is not limited to the following examples.

[0213] The following materials were prepared.

[0214] (Curable Compounds) Biphenyl novolac type epoxy compound (NC-3000, manufactured by Nippon Kayaku Co., Ltd., solid at 25°C, 2 functional groups, equivalent weight 275 g / eq) Bisphenol type epoxy compound with an imide skeleton (WHR-991S, manufactured by Nippon Kayaku Co., Ltd., solid at 25°C, 2 functional groups, equivalent weight 265 g / eq) Resorcinol diglycidyl ether type epoxy compound (JER630, manufactured by Nagase ChemteX Corporation, liquid at 25°C, 3 functional groups, equivalent weight 96 g / eq) Epoxy compound with a butadiene skeleton (PB3600, manufactured by Daicel Corporation, liquid at 25°C, 2 functional groups, equivalent weight 198 g / eq) Maleimide compound 1-containing solution (Designer Molecules) (BMI-3000J, manufactured by Designer Molecules Inc., solids content 51% by weight, containing 49% by weight of toluene as a solvent, number of maleimide groups: 2, weight-average molecular weight: 3000) Maleimide compound 2 (BMI-689, manufactured by Designer Molecules Inc., liquid at 25°C, number of maleimide groups: 2, weight-average molecular weight: 689)

[0215] (Curing agent) Active ester compound 1-containing liquid (DIC Corporation's "HPC-8150-62T", 60% by weight solids, containing 40% by weight toluene as a solvent) Active ester compound 2-containing liquid (DIC Corporation's "HPC-8000L-65MT", 65% by weight solids, containing 25% by weight methyl ethyl ketone and 10% by weight toluene as solvents) Dicyandiamide

[0216] (Insulating Filler) Solid Silica Particle 1-Containing Slurry A (75% by weight silica, 25% by weight cyclopentanone as solvent, prepared according to Preparation Example 1A below) Solid Silica Particle 1-Containing Slurry B (75% by weight silica, 25% by weight cyclohexanone as solvent, prepared according to Preparation Example 1B below) Solid Silica Particle 2-Containing Slurry A (70% by weight silica, 30% by weight cyclopentanone as solvent, prepared according to Preparation Example 2A below) Solid Silica Particle 2-Containing Slurry B (70% by weight silica, 30% by weight cyclohexanone as solvent, prepared according to Preparation Example 2B below) Hollow Silica Particle 1-Containing Slurry X (28% by weight silica, 72% by weight cyclopentanone as solvent, prepared according to Preparation Example 1X below)

[0217] <Preparation Example 1A> 100 parts by weight of solid silica particles (SO-C4, manufactured by Admatex Co., Ltd.) were surface-treated with 0.6 parts by weight of N-phenyl-3-aminopropyltrimethoxysilane to obtain slurry A containing solid silica particles 1. The average particle size of the obtained solid silica particles 1 was 1.0 μm. Cyclopentanone was used as the solvent.

[0218] <Preparation Example 1B> A slurry B containing solid silica particles was obtained in the same manner as in Preparation Example 1A, except that cyclohexanone was used as the solvent.

[0219] <Preparation Example 2A> 100 parts by weight of solid silica particles (SO-C2, manufactured by Admatex Co., Ltd.) were surface-treated with 0.6 parts by weight of vinyltrimethoxysilane to obtain slurry A containing solid silica particles 2. The average particle size of the obtained solid silica particles 2 was 0.5 μm. Cyclopentanone was used as the solvent.

[0220] <Preparation Example 2B> A slurry B containing 2 solid silica particles was obtained in the same manner as in Preparation Example 2A, except that cyclohexanone was used as the solvent.

[0221] <Preparation Example 1X> 100 parts by weight of hollow silica particles (Kao Corporation's "KP-100-HS") were surface-treated with 0.6 parts by weight of N-phenyl-3-aminopropyltrimethoxysilane to obtain a slurry X containing hollow silica particles 1. The average particle size of the obtained hollow silica particles 1 was 1.0 μm. Cyclopentanone was used as the solvent.

[0222] (Thermoplastic resins) Polyimide resin 1-containing liquid (Arakawa Chemical Co., Ltd. "PIAD300C", softening point 130°C, solids content 30% by weight, containing 45% by weight of cyclopentanone and 25% by weight of cyclohexanone as solvents) Polyimide resin 2-containing liquid (Arakawa Chemical Co., Ltd. "PIAD150LC", softening point 80°C, solids content 30% by weight, containing 55% by weight of cyclopentanone and 15% by weight of cyclohexanone as solvents) Polyimide resin 3-containing liquid (Arakawa Chemical Co., Ltd. "PIAD300", softening point 130°C, solids content 30% by weight, containing 58.4% by weight of cyclohexanone, 4.1% by weight of 1,2-dimethoxyethane and 7.5% by weight of methylcyclohexane as solvents) Polyimide resin 4-containing liquid (Arakawa Chemical Co., Ltd. "PIAD150L", softening point 80°C, solids content 30% by weight, containing 58.4% by weight of cyclohexanone, 4.1% by weight of 1,2-dimethoxyethane, and 7.5% by weight of methylcyclohexane as solvents)

[0223] (Curing accelerators) Organophosphorus compounds (PX4MP, manufactured by Nippon Chemical Industrial Co., Ltd.) Dimethylaminopyridine (DMAP, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Imidazole compounds (2P4MZ, manufactured by Shikoku Chemicals, Ltd.) Peroxides (Parkmill D, manufactured by NOF Corporation)

[0224] (Examples 1-5 and Comparative Examples 1 and 2) The components shown in Tables 2, 4, and 6 below were blended in the amounts shown in Tables 2, 4, and 6 below (units for components other than the solvent are in parts by weight of solids, and units for the solvent are in parts by weight), and stirred at room temperature until a homogeneous solution was obtained to obtain a resin material. In Examples 1-5 and Comparative Examples 1 and 2, the following silica particle-containing slurry and polyimide resin-containing liquid were used.

[0225] Examples 1 and 2: As slurries containing solid silica particles 1 and 2, slurry A containing solid silica particles 1 and slurry A containing solid silica particles 2 were used. As polyimide resin-containing liquids, polyimide resin 1-containing liquid and polyimide resin 2-containing liquid were used.

[0226] Example 3: As slurries containing solid silica particles 1 and 2, slurry A containing solid silica particle 1 and slurry A containing solid silica particle 2 were used. As a polyimide resin-containing liquid, a polyimide resin-containing liquid was used.

[0227] Example 4: As the slurry containing solid silica particles 2, slurry A containing solid silica particles 2 was used. Slurry X containing hollow silica particles 1 was used. As the polyimide resin-containing liquid, polyimide resin-containing liquid 1 was used.

[0228] Example 5: As the slurry containing solid silica particles 2, slurry A containing solid silica particles 2 was used. Slurry X containing hollow silica particles 1 was used.

[0229] Comparative Example 1: As slurries containing solid silica particles 1 and 2, slurry B containing solid silica particle 1 and slurry B containing solid silica particle 2 were used. As the polyimide resin-containing liquid, a polyimide resin-containing liquid 3 was used.

[0230] Comparative Example 2: As slurries containing solid silica particles 1 and 2, slurry B containing solid silica particle 1 and slurry B containing solid silica particle 2 were used. As polyimide resin-containing liquids, polyimide resin-containing liquid 3 and polyimide resin-containing liquid 4 were used.

[0231] The resulting resin material contains a solvent derived from a maleimide compound 1-containing liquid, a commercially available curing agent, a slurry containing solid silica particles, a slurry containing hollow silica particles, and a polyimide resin-containing liquid. The boiling points of the solvents used are as follows.

[0232] Cyclopentanone (boiling point 130°C, in the above formula (X), R １ ~R ４ (Ketone compounds in which the atoms are hydrogen atoms) Cyclohexanone (boiling point 156°C, ketone compound) Methyl ethyl ketone (boiling point 79°C, ketone compound) Toluene (boiling point 110°C, solvent different from ketone compounds) 1,2-dimethoxyethane (boiling point 82°C, solvent different from ketone compounds) Methylcyclohexane (boiling point 101°C, solvent different from ketone compounds)

[0233] Preparation of resin film: Using an applicator, the obtained resin material was coated onto the release-treated surface of a release-treated polyethylene terephthalate film (PET film, Toray Industries "XG284", 25 μm thick), and then dried in a 100°C gear oven for 2 minutes and 30 seconds to evaporate the solvent. In this way, a laminated film (a laminated film of PET film and resin film) was obtained in which a resin film (B-stage film) with a thickness of 40 μm was laminated on the PET film.

[0234] (Evaluation) (1) Measurement of Tg(A) and Tg(B) A copper foil (MT18Ex, 35 μm thick, manufactured by Mitsui Mining & Smelting Co., Ltd.) was vacuum laminated to both sides of a double-sided copper-clad laminate (MCL-E679FG, manufactured by Resonaq Co., Ltd.). Then, the shiny side of the copper foil was treated with Cz (Cz8101, manufactured by MEC Co., Ltd.) to create a substrate in which the surface of the copper foil was etched by about 1 μm. A resin material was coated onto the surface of a 25 μm thick polyethylene terephthalate film, and then dried in a gear oven at 100°C for 2 minutes to obtain a laminated film in which a 40 μm thick resin film was laminated onto the surface of the polyethylene terephthalate film. The obtained laminated film was vacuum laminated onto the surface of the substrate from the resin film side, heated at 130°C for 30 minutes, and then heated again at 170°C for 30 minutes. After cutting out the copper foil and resin film from the laminated structure of the substrate and resin film, the copper foil portion is cut out from iron chloride (FeCl ３ A semi-cured resin material was obtained by etching with an aqueous solution. The glass transition temperature of the obtained semi-cured resin material was defined as Tg(A). A laminated film vacuum-laminated onto the surface of the same substrate was heated at 130°C for 30 minutes, and then further heated at 170°C for 30 minutes. Next, the polyethylene terephthalate film of the laminated film was peeled off, and the resin material was heated at 200°C for 60 minutes to obtain a cured resin material. The glass transition temperature of the obtained cured resin material was defined as Tg(B). Tg(A) and Tg(B) were measured as follows.

[0235] Semi-cured and cured resin materials were cut to a size of 5 mm in width and 20 mm in length to prepare test specimens for measuring the glass transition temperature. Using a tensile-mode dynamic mechanical analyzer (DMA, Hitachi High-Tech Corporation "DMA7100"), the glass transition temperature was defined as the peak value of tanδ measured at a frequency of 10 Hz while the glass transition temperature test specimen was heated at a rate of 5°C / min in the temperature range of 23°C to 330°C.

[0236] (2) Dielectric Loss Tangent (Df) of the Cured Material The obtained resin film was heated at 190°C for 90 minutes to obtain a cured material. The obtained cured material was cut into pieces 2 mm wide and 80 mm long, and 10 pieces were stacked together. The dielectric loss tangent was measured at room temperature (23°C) at a frequency of 5.8 GHz using the cavity resonance method with a "Cavity Resonance Perturbation Method Dielectric Constant Measurement Device CP521" manufactured by Kanto Electronics Applied Development Co., Ltd. and a "Network Analyzer N5224A PNA" manufactured by Keysight Technologies.

[0237] [Criteria for determining the dielectric loss tangent (Df) of hardened material] ○: Dielectric loss tangent is 0.0049 or less ×: Dielectric loss tangent exceeds 0.0049

[0238] (3) Surface roughness after desmear treatment The laminated film obtained was vacuum laminated onto the surface of a double-sided copper-clad laminate (MCL-E679FG manufactured by Resonaq Corporation) from the resin film side, heated at 130°C for 30 minutes, and then heated again at 170°C for 30 minutes. Next, the polyethylene terephthalate film of the laminated film was peeled off to obtain a laminate. The obtained laminate was subjected to the following (a) swelling treatment, followed by (b) desmear treatment.

[0239] (a) Swelling treatment: The laminate was placed in a swelling solution (an aqueous solution of "Swelling Dip Securigant P" manufactured by Atotec Japan Co., Ltd. and "Sodium Hydroxide" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and shaken at 60°C for 10 minutes. In other words, a swelling treatment was performed at 60°C for 10 minutes. After that, it was washed with pure water.

[0240] (b) Desmear treatment: The laminate was placed in a roughening aqueous solution of sodium permanganate (Concentrate Compact CP, manufactured by Atotec Japan Co., Ltd., or sodium hydroxide, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) at 80°C and shaken for 30 minutes to obtain a roughened hardened product. That is, the roughening treatment was performed at 80°C for 30 minutes.

[0241] The roughened laminate was washed for 10 minutes with a neutralizing solution at 40°C (Reduction Solution Securigant P from Atotec Japan, and sulfuric acid from Fujifilm Wako Pure Chemical Industries, Ltd.), and then washed again with pure water. In this way, a roughened cured material was formed on a copper-clad laminate, and evaluation samples were obtained.

[0242] The arithmetic mean roughness (Ra) and ten-point mean roughness (Rz) of the hardened surface of the obtained evaluation samples were measured using a non-contact three-dimensional optical interference microscope (Bruker "CounterGT").

[0243] [Criteria for determining arithmetic mean roughness (Ra) after desmear treatment] ○: Arithmetic mean roughness (Ra) is 0.20 μm or less ×: Arithmetic mean roughness (Ra) is greater than 0.20 μm

[0244] [Criteria for determining the ten-point mean roughness (Rz) after desmearing] ○: Ten-point mean roughness (Rz) is 2.00 μm or less ×: Ten-point mean roughness (Rz) is greater than 2.00 μm

[0245] (4) Plating Peel Strength The surface of the roughened cured material obtained from the evaluation of "(3) Surface Roughness after Desmear Treatment" was treated with an alkaline cleaner at 60°C (Atotec Japan's "Cleaner Securigant 902") for 5 minutes to degrease and clean it. After cleaning, the cured material was treated with a pre-dip solution at 25°C (Atotec Japan's "Pre-dip Neogant B") for 2 minutes. Then, the cured material was treated with an activator solution at 40°C (Atotec Japan's "Activator Neogant 834") for 5 minutes to apply a palladium catalyst. Next, the cured material was treated with a reducing solution at 30°C (Atotec Japan's "Reducer Neogant WA") for 5 minutes.

[0246] Next, the cured material was placed in a chemical copper solution (Atotec Japan's "Basic Print Gant MSK-DK," "Copper Print Gant MSK," "Stabilizer Print Gant MSK," and "Reducer Cu"), and electroless plating was performed until the plating thickness reached approximately 0.5 μm. After electroless plating, the material was annealed at 120°C for 30 minutes to remove any remaining hydrogen gas. All steps up to the electroless plating process were carried out using a beaker scale with a treatment solution of 2 L, while agitating the cured material.

[0247] Electroplating Treatment: Next, electroplating was performed on the electroless plated hardened material until the plating thickness reached 25 μm. A copper sulfate solution (copper sulfate pentahydrate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., sulfuric acid manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., basic leveler caparaside HL manufactured by Attec Japan, and corrective agent caparaside GS manufactured by Attec Japan) was prepared for electroplating. Using this copper sulfate solution for electroplating, the flow rate was 0.6 A / cm. ２ Electroplating was performed by applying an electric current until the plating thickness reached approximately 25 μm. After the copper plating treatment, the cured material was heated at 200°C for 60 minutes to further harden it. In this way, a cured material with a copper plating layer laminated on the upper surface was obtained.

[0248] Measurement of Plating Peel Strength: Six 10 mm wide strip-shaped cuts were made at 5 mm intervals on the surface of the copper plating layer of the hardened material with the obtained copper plating layer laminated on the top surface. The hardened material with the copper plating layer laminated on the top surface was set in a 90° peel tester (TE-3001, manufactured by Tester Sangyo Co., Ltd.), and the edges of the copper plating layer with the cuts were picked up with a gripper, and the copper plating layer was peeled off by 20 mm, avoiding the areas where vias had formed, and the peel strength (plating peel strength) was measured. The peel strength (plating peel strength) was measured for each of the six cut locations, and the average value of the plating peel strength was calculated. The plating peel strength was judged according to the following criteria.

[0249] [Criteria for determining plating peel strength] ○: Average plating peel strength is 0.50 kgf / cm or higher ×: Average plating peel strength is less than 0.50 kgf / cm

[0250] (5) Crack (TS test) The obtained laminated film was vacuum-laminated onto the surface of a double-sided copper-clad laminate (Resonac Co., Ltd. "MCL-E705G", size 100 mm x 100 mm) from the resin film side, heated at 130°C for 30 minutes, and then heated again at 170°C for 30 minutes. Next, the polyethylene terephthalate film of the laminated film was peeled off to obtain laminate (1). The obtained laminate (1) was subjected to desmear treatment in the same manner as in the procedure for "(3) Surface roughness after desmear treatment" above, and then electroless plating and electroplating treatment were carried out in the same manner as in the procedure for "(4) Measurement of plating peel strength" above. In this way, a laminate (2) was obtained in which a copper plating layer with a thickness of approximately 30 μm was formed on the upper surface of the cured resin film. In addition, five circular chemical-resistant seals with a size of 1 inch were prepared. The chemical-resistant seals were attached to both sides of the copper plating layer of laminate (2). The attachment positions of the chemical-resistant seals are as follows.

[0251] The first chemical-resistant seal should be placed 10 mm vertically and 10 mm horizontally from the first corner of the laminate (2). The second chemical-resistant seal should be placed 10 mm vertically and 10 mm horizontally from the second corner of the laminate (2). The third chemical-resistant seal should be placed 10 mm vertically and 10 mm horizontally from the third corner of the laminate (2). The fourth chemical-resistant seal should be placed 10 mm vertically and 10 mm horizontally from the fourth corner of the laminate (2). The fifth chemical-resistant seal should be placed in the center of the laminate (2).

[0252] Next, the copper plating in the areas where the chemical-resistant seals were not applied was removed by etching with a copper chloride aqueous solution. After that, all five chemical-resistant seals were peeled off, and the cured material was heated at 200°C for 60 minutes to further harden it. In this way, an evaluation sample was obtained in which five 1-inch circular copper-plated layers were laminated on both sides.

[0253] Preconditioning: The evaluation samples were heated at 125°C for 2 hours, and then passed through a solder reflow oven (preheat 170°C for 135 seconds, reflow [maximum temperature 260°C]) three times under a nitrogen atmosphere.

[0254] TS Test: Using a liquid bath thermal shock device (TSB-51 manufactured by ESPEC), the following procedure was performed: immersion in a -65°C low-temperature bath for 2 minutes and 30 seconds, followed by immersion in a 150°C high-temperature bath for 2 minutes and 30 seconds. This was considered one cycle, and this procedure was repeated a total of 500 cycles.

[0255] Crack observation: After the TS test was completed, the copper on the surface was etched off, and cross-sections were cut out from three arbitrary locations on each circular pattern. These were observed under an optical microscope, and the number of cracks was counted (a total of six locations, three on each side). Cracks that did not reach the underlying layer were counted as 0.5.

[0256] [Criteria for judging cracks (TS test)] ○: 3.0 or fewer cracks ×: More than 3.0 cracks

[0257] The composition and results are shown in Tables 1 to 7 below. Table 1 contains details of the ingredients listed in Tables 2, 4, and 6. Further details of the ingredients listed in Table 1 are as described above.

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265] 11...Multilayer printed circuit board 12...Circuit board 12a...Top surface 13-16...Insulating layer 17...Metal layer

Claims

1. A resin material comprising a curable compound, an insulating filler, and a solvent, wherein the solvent contains a ketone compound, and the boiling point of the ketone compound is 90°C or higher and 150°C or lower.

2. The resin material according to claim 1, wherein the ketone compound has 4 to 7 carbon atoms.

3. A resin material comprising a curable compound, an insulating filler, and a solvent, wherein the solvent comprises a ketone compound represented by the following formula (X). In the above formula (X), R １ R represents a hydrogen atom or a methyl group. ２ R represents a hydrogen atom or a methyl group. ３ R represents a hydrogen atom or a methyl group. ４ represents a hydrogen atom or a methyl group.

4. In the above formula (X), R ３ represents a hydrogen atom, R ４ The resin material according to claim 3, wherein represents a hydrogen atom.

5. A resin material comprising a curable compound, an insulating filler, and a solvent, wherein the ratio of the Tg(B) of the cured resin material to the Tg(A) of the semi-cured resin material, as determined by the glass transition temperature measurement method described below, is 1.0 or more and 1.2 or less. Method for measuring glass transition temperature: After vacuum laminating copper foil to both sides of a double-sided copper-clad laminate, the shiny side of the copper foil is treated with Cz to create a substrate in which the surface of the copper foil is etched by approximately 1 μm. After coating the surface of a 25 μm thick polyethylene terephthalate film with resin material, it is dried in a 100°C gear oven for 2 minutes to obtain a laminated film in which a 40 μm thick resin film is laminated on the surface of the polyethylene terephthalate film. The obtained laminated film is vacuum laminated onto the surface of the substrate from the resin film side, heated at 130°C for 30 minutes, and then heated again at 170°C for 30 minutes. After cutting out the copper foil and resin film from the laminated structure of the substrate and resin film, the copper foil portion is treated with iron chloride (FeCl ３ The resin material is etched with an aqueous solution to obtain a semi-cured product. The glass transition temperature of the obtained semi-cured resin material is denoted as Tg(A). A laminated film vacuum-laminated onto the surface of the same substrate is heated at 130°C for 30 minutes, and then further heated at 170°C for 30 minutes. The polyethylene terephthalate film of the laminated film is peeled off, and the film is heated at 200°C for 60 minutes to obtain a cured resin material. The glass transition temperature of the obtained cured resin material is denoted as Tg(B).

6. The resin material according to any one of claims 1 to 4, wherein the content of the ketone compound in 100% by weight of the solvent is 25% by weight or more.

7. The resin material according to any one of claims 1 to 6, wherein the content of the insulating filler is 40% by weight or more and 80% by weight or less of 100% by weight of the components excluding the solvent in the resin material.

8. The resin material according to any one of claims 1 to 7, wherein the insulating filler includes hollow particles.

9. The resin material according to any one of claims 1 to 8, wherein the curable compound is a thermosetting compound.

10. The resin material according to any one of claims 1 to 9, wherein the curable compound comprises an epoxy compound or a maleimide compound.

11. A resin material according to any one of claims 1 to 10, comprising a curing agent.

12. The resin material according to claim 11, wherein the curing agent comprises an active ester compound.

13. A resin material according to any one of claims 1 to 12, used for forming an insulating layer in a multilayer printed circuit board.

14. A resin film formed from the resin material described in any one of claims 1 to 13.

15. A laminated film comprising a metal foil or a base film and a resin film according to claim 14, wherein the resin film is laminated on the surface of the metal foil or base film.

16. The laminated film according to claim 15, comprising the base film, wherein the base film is a polyethylene terephthalate film.

17. A multilayer printed circuit board comprising a circuit board, a plurality of insulating layers disposed on the surface of the circuit board, and a metal layer disposed between the plurality of insulating layers, wherein at least one of the plurality of insulating layers is a cured product of the resin material described in any one of claims 1 to 13.

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