Resin material, cured product, and multilayer printed wiring board

Abstract

To provide a resin material that allows suppression of interlayer delamination between an insulating layer and a metal layer and enables reduction of a dielectric loss tangent in a cured product.SOLUTION: A resin material according to the present invention comprises an epoxy compound (A), an active ester compound (B), a curing accelerator (C), and an inorganic filler (D). When the 25°C density of the resin material is defined as ρA, and the 25°C density of a cured product of the resin material obtained by heating the resin material at 130°C for 30 minutes and then at 180°C for 30 minutes is defined as ρB, the curing shrinkage ratio represented by formula (X) is 2.5% or less. (X): Curing shrinkage ratio (%)=[(ρB-ρA) / ρA]×100.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a resin material containing an epoxy compound, a cured product of the resin material, and a multilayer printed wiring board using the resin material. [Background technology]

[0002] Conventionally, various resin materials have been used to obtain electronic components such as semiconductor devices, laminates, and printed wiring boards. For example, in multilayer printed wiring boards, resin materials are used to form insulating layers for insulating between 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. Furthermore, film-like resin materials (resin films) are sometimes used to form the insulating layers. The resin materials are used as insulating materials for multilayer printed wiring boards, including build-up films.

[0003] Patent Document 1 below discloses a resin composition containing (A) a phosphorus-containing curing catalyst, (B) an epoxy resin, (C) an active ester compound, and (D) an inorganic filler. In this resin composition, the content of component (C) is 10% by mass or more, and the content of component (D) is 60% by mass or more, where the total nonvolatile components in the resin composition is 100% by mass. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2022-109004 Summary of the Invention [Problem to be solved by the invention]

[0005] Resin materials used as materials for insulating layers of electronic components desirably have a low dielectric loss tangent after curing. To lower the dielectric loss tangent of the cured product, resin materials containing active ester compounds, such as those described in Patent Document 1, are sometimes used. However, conventional resin materials containing active ester compounds are prone to delamination between the insulating layer and the metal layer.

[0006] With conventional resin materials, it is difficult to both prevent delamination between the insulating layer and the metal layer and reduce the dielectric loss tangent of the cured product.

[0007] An object of the present invention is to provide a resin material that can suppress delamination between an insulating layer and a metal layer and that can reduce the dielectric loss tangent of the cured product. Another object of the present invention is to provide a cured product of the resin material. A further object of the present invention is to provide a multilayer printed wiring board using the resin material. [Means for solving the problem]

[0008] This specification discloses the following resin material, cured product, and multilayer printed wiring board.

[0009] Item 1. A resin material containing an epoxy compound (A), an active ester compound (B), a curing accelerator (C), and an inorganic filler (D), and the density of the resin material at 25 ° C. is ρ A The density of the cured resin material at 25°C obtained by heating the resin material at 130°C for 30 minutes and then at 180°C for 30 minutes is ρ B The resin material has a cure shrinkage of 2.5% or less, as expressed by the following formula (X):

[0010] Curing shrinkage rate (%)=[(ρ B -ρ A ) / ρ A ]×100 (X)

[0011] Item 2. The resin material according to Item 1, wherein the cure shrinkage represented by formula (X) is 1.7% or less.

[0012] Item 3. The resin material according to Item 1 or 2, wherein the epoxy compound (A) includes an aliphatic epoxy compound having a glycidyl ether skeleton.

[0013] Item 4. The resin material according to any one of Items 1 to 3, further comprising a thermoplastic resin (E).

[0014] Item 5. The resin material according to Item 4, wherein the content of the thermoplastic resin (E) is 10% by weight or more based on 100% by weight of components excluding the inorganic filler (D) and the solvent in the resin material.

[0015] Item 6. The resin material according to any one of Items 1 to 5, wherein the content of the active ester compound (B) is 20% by weight or more based on 100% by weight of components in the resin material excluding the inorganic filler (D) and the solvent.

[0016] Item 7. The resin material according to any one of Items 1 to 6, wherein the content of the epoxy compound (A) is 40% by weight or more based on 100% by weight of components in the resin material excluding the inorganic filler (D) and the solvent.

[0017] Item 8. The resin material according to any one of Items 1 to 7, wherein the content of the inorganic filler (D) is 78% by weight or less based on 100% by weight of the components excluding the solvent in the resin material.

[0018] Item 9. The resin material according to any one of Items 1 to 8, wherein the curing accelerator (C) includes a phosphorus-containing compound or an amine compound having no imidazole skeleton.

[0019] Item 10. The resin material according to any one of Items 1 to 9, wherein the curing accelerator (C) contains a phosphorus-containing compound that is liquid at 25°C.

[0020] Item 11. The resin material according to any one of Items 1 to 10, which is a resin film.

[0021] Item 12. The resin material according to any one of Items 1 to 11, which is used to form an insulating layer in a multilayer printed wiring board.

[0022] Item 13. A cured product of a resin material, wherein the resin material is the resin material according to any one of Items 1 to 12.

[0023] Item 14. A multilayer printed wiring board comprising a circuit board, a plurality of insulating layers arranged on the surface of the circuit board, and a metal layer arranged 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 12. [Effects of the Invention]

[0024] The resin material according to the present invention contains an epoxy compound (A), an active ester compound (B), a curing accelerator (C), and an inorganic filler (D). The resin material according to the present invention has a cure shrinkage of 2.5% or less, as represented by specific formula (X). Because the resin material according to the present invention has the above-described structure, it is possible to suppress delamination between the insulating layer and the metal layer, and to reduce the dielectric loss tangent of the cured product. [Brief explanation of the drawings]

[0025] [Figure 1] FIG. 1 is a cross-sectional view schematically showing a multilayer printed wiring board using a resin material according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0026] The present invention will be described in detail below.

[0027] (resin material) The resin material according to the present invention contains an epoxy compound (A), an active ester compound (B), a curing accelerator (C), and an inorganic filler (D).

[0028] In the resin material according to the present invention, the density of the resin material at 25°C is ρ A The density of the cured resin material at 25°C obtained by heating the resin material at 130°C for 30 minutes and then at 180°C for 30 minutes is ρ BWhen the curing shrinkage is 2.5% or less, the curing shrinkage is represented by the following formula (X).

[0029] Curing shrinkage rate (%)=[(ρ B -ρ A ) / ρ A ]×100 (X)

[0030] The resin material according to the present invention has the above-described structure, and therefore can suppress delamination between the insulating layer and the metal layer, and can reduce the dielectric loss tangent of the cured product.

[0031] Conventional resin materials containing active ester compounds tend to shrink relatively easily when cured. When the resin material shrinks during curing, delamination easily occurs at the interface between the metal layer and the insulating layer (the cured layer of the resin material). In contrast, the resin material according to the present invention has a small cure shrinkage rate, which effectively suppresses shrinkage of the resin material during curing and prevents delamination between the insulating layer and the metal layer. Furthermore, since the resin material according to the present invention has the above-described configuration, and in particular, contains an active ester compound, the dielectric loss tangent of the cured product can be reduced.

[0032] More specifically, the cure shrinkage rate is determined as follows.

[0033] Using a true density measuring device (e.g., manufactured by Anton Paar Japan), the true density of the resin material at 25 °C is measured, and the density ρ A (g / cm 3) Two release-treated polyethylene terephthalate films with a thickness of 25 μm are prepared (hereinafter referred to as polyethylene terephthalate films (1) and (2)). A resin material is placed between the release-treated surface of polyethylene terephthalate film (1) and the release-treated surface of polyethylene terephthalate film (2), and laminated using a vacuum diaphragm laminator. Lamination is performed by reducing the pressure for 30 seconds to 13 hPa or less, and then pressing at 50°C and a pressure of 0.6 MPa for 30 seconds. The resulting laminated film (polyethylene terephthalate film (1) / resin material / polyethylene terephthalate film (2)) is heated at 130°C for 30 minutes, and then at 180°C for 30 minutes to obtain a cured resin material. The true density of the resulting cured material at 25°C is measured using a true density measuring device (e.g., manufactured by Anton Paar Japan), and the density ρ B (g / cm 3 ) The density of the resin material at 25°C (ρ A ) and the density of the cured resin material at 25°C (ρ B ) and calculate the cure shrinkage rate using the above formula (X).

[0034] When the resin material is a resin film, the density ρ A The true density of the resin material at 25°C for measuring the density ρ means the true density of the resin film at 25°C. BThe cured product of the resin material for measuring the density ρ is preferably obtained as follows: A resin film is placed on the release-treated surface of a polyethylene terephthalate film (1). The thickness of the resin film placed on the release-treated surface of the polyethylene terephthalate film (1) is preferably in the range of 25 μm to 50 μm. If the thickness of a single resin film is less than 25 μm, multiple resin films may be used in layers so that the thickness is in the range of 25 μm to 50 μm. If the thickness of a single resin film exceeds 50 μm, a resin film cut out so that the thickness is in the range of 25 μm to 50 μm may be used. Next, the surface of the resin film opposite to the polyethylene terephthalate film (1) side is joined to the release-treated surface of a polyethylene terephthalate film (2). Next, lamination and heating are performed under the above-mentioned conditions to measure the density ρ B A cured resin material is obtained for measuring the cured resin material.

[0035] When the resin material is in a form other than a resin film (a resin composition), the density ρ A The true density of the resin material at 25°C for measuring the density ρ means the true density of the resin material in the form of a film (resin film) at 25°C. The resin material in the form of a film (resin film) is preferably obtained as follows: After the resin material is coated on the release-treated surface of a polyethylene terephthalate film (1), it is dried for 2 minutes and 30 seconds in a gear oven at 100°C to volatilize the solvent, and a resin film with a thickness of 40 μm is obtained. In addition, when the resin material is in a form other than a resin film (resin composition), the density ρ B The cured resin material for measuring the density ρ is preferably obtained as follows: The surface of the 40 μm thick resin film obtained as described above opposite to the polyethylene terephthalate film (1) side is joined to the release-treated surface of the polyethylene terephthalate film (2). Then, lamination and heating are carried out under the above-mentioned conditions, and the density ρ is measured. B A cured resin material is obtained for measuring the cured resin material.

[0036] The polyethylene terephthalate films (1) and (2) may be, for example, "XG284" manufactured by Toray Industries, Inc. The vacuum diaphragm laminator may be, for example, "MVLPα500" manufactured by The Japan Steel Works, Ltd.

[0037] The cure shrinkage is 2.5% or less, preferably 2.0% or less, more preferably 1.7% or less, even more preferably 1.2% or less, even more preferably 1.0% or less, particularly preferably 0.8% or less, and most preferably 0.5% or less. When the cure shrinkage is equal to or less than the upper limit, delamination between the insulating layer and the metal layer can be more effectively suppressed. The cure shrinkage may be 0% or more, may exceed 0%, may be 0.1% or more, may be 0.2% or more, or may be 0.3% or more.

[0038] Examples of methods for reducing the cure shrinkage include the following: (1) The cure shrinkage is likely to be reduced by including an aliphatic epoxy compound having a glycidyl ether skeleton in the resin material. (2) The cure shrinkage is likely to be reduced by including a thermoplastic resin in the resin material. (3) The cure shrinkage is likely to be reduced by increasing the content of an active ester compound in 100% by weight of the components excluding inorganic fillers and solvents in the resin material. (4) The cure shrinkage is likely to be reduced by increasing the content of an epoxy compound in 100% by weight of the components excluding inorganic fillers and solvents in the resin material. (5) The cure shrinkage is likely to be reduced by including a phosphorus-containing compound (curing accelerator) that is liquid at 25°C in the resin material. The cure shrinkage can be reduced by appropriately combining the above-mentioned methods.

[0039] When using the resin material to manufacture electronic components such as multilayer substrates, the resin material may be heated at 130°C for 30 minutes and then at 180°C for 30 minutes to obtain a cured product, or the resin material may be heated under heating conditions other than these to obtain a cured product.

[0040] The resin material according to the present invention may be a resin composition or a resin film. The resin composition has fluidity. The resin composition may be in a paste form. The paste form includes a liquid form. The resin material according to the present invention is preferably a resin film because it is easy to handle.

[0041] The resin material according to the present invention is preferably a thermosetting resin material. When the resin material is a resin film, the resin film is preferably a thermosetting resin film.

[0042] In the following description, "100% by weight of the components in the resin material excluding the solvent" means 100% by weight of the components in the resin material excluding the solvent if the resin material contains a solvent, and means 100% by weight of the resin material if the resin material does not contain a solvent. "100% by weight of the components in the resin material excluding the solvent" means 100% by weight of the non-volatile components in the resin material.

[0043] In the following description, "100% by weight of components in the resin material excluding the inorganic filler (D) and solvent" means 100% by weight of components in the resin material excluding the inorganic filler (D) and the solvent when the resin material contains the inorganic filler (D) and a solvent. "100% by weight of components in the resin material excluding the inorganic filler (D) and solvent" means 100% by weight of components in the resin material excluding the inorganic filler (D) when the resin material contains the inorganic filler (D) but not the solvent. "100% by weight of components in the resin material excluding the inorganic filler (D) and solvent" means 100% by weight of non-volatile components in the resin material excluding the inorganic filler (D).

[0044] Hereinafter, details of each component used in the resin material according to the present invention and uses of the resin material according to the present invention will be described.

[0045] [Epoxy compound (A)] The resin material contains an epoxy compound (A). As the epoxy compound (A), a conventionally known epoxy compound can be used. The epoxy compound (A) may be used alone or in combination of two or more types.

[0046] Examples of the epoxy compound (A) include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, bisphenol E type epoxy compounds, phenol novolac type epoxy compounds, cresol 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 nucleus in the skeleton.

[0047] The epoxy compound (A) may be a glycidyl ether compound, which is a compound having at least one glycidyl ether group.

[0048] The epoxy compound (A) preferably contains an aliphatic epoxy compound having a glycidyl ether skeleton, and more preferably contains an aliphatic epoxy compound having a glycidyl ether skeleton and an epoxy compound having an aromatic ring. In this case, the cure shrinkage can be effectively reduced, and delamination between the insulating layer and the metal layer can be more effectively suppressed. In addition, the thermal dimensional stability of the cured product can be further improved.

[0049] The epoxy compound having an aromatic ring is preferably an epoxy compound having a naphthalene skeleton or a phenyl skeleton. In this case, the dielectric tangent of the cured product can be further reduced. In addition, the thermal dimensional stability of the cured product can be further improved.

[0050] The aliphatic epoxy compound having a glycidyl ether skeleton may include an epoxy compound having one or two epoxy groups, an epoxy compound having three or more epoxy groups, or both an epoxy compound having one or two epoxy groups and an epoxy compound having three or more epoxy groups. The epoxy compound having an aromatic ring may include an epoxy compound having one or two epoxy groups, an epoxy compound having three or more epoxy groups, or both an epoxy compound having one or two epoxy groups and an epoxy compound having three or more epoxy groups.

[0051] The content of the aliphatic epoxy compound having a glycidyl ether skeleton in 100% by weight of the epoxy compound (A) is preferably 15% by weight or more, more preferably 18% by weight or more, and preferably 35% by weight or less, more preferably 30% by weight or less. When the content of the aliphatic epoxy compound having a glycidyl ether skeleton is equal to or more than the above lower limit and equal to or less than the above upper limit, the cure shrinkage rate can be effectively reduced, and delamination between the insulating layer and the metal layer can be more effectively suppressed.

[0052] The molecular weight of the epoxy compound (A) is preferably 1000 or less. When the molecular weight is equal to or less than the upper limit, a resin material with high fluidity is easily obtained when forming an insulating layer, and lamination properties can be improved. Furthermore, since lamination properties can be improved, the plating peel strength of the cured product can be further improved.

[0053] The molecular weight of the epoxy compound (A) means the molecular weight that can be calculated from the structural formula when the epoxy compound (A) is not a polymer and when the structural formula of the epoxy compound (A) can be identified. When the epoxy compound (A) is a polymer, the molecular weight means the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0054] The content of the epoxy compound (A) in the resin material, based on 100% by weight of the components excluding the solvent, is preferably 10% by weight or more, more preferably 15% by weight or more, and preferably 80% by weight or less, more preferably 70% by weight or less. When the content of the epoxy compound (A) is above the above-mentioned lower limit and below the above-mentioned upper limit, the dielectric loss tangent of the cured product can be further reduced. Furthermore, when the content of the epoxy compound (A) is above the above-mentioned lower limit and below the above-mentioned upper limit, the cure shrinkage rate can be effectively reduced, and interlayer delamination between the insulating layer and the metal layer can be more effectively suppressed. Furthermore, the thermal dimensional stability of the cured product can be further improved.

[0055] The content of the epoxy compound (A) in the resin material, based on 100% by weight of the components excluding the inorganic filler (D) and the solvent, is preferably 10% by weight or more, more preferably 40% by weight or more, preferably 80% by weight or less, more preferably 70% by weight or less, and even more preferably 60% by weight or less. When the content of the epoxy compound (A) is above the above-mentioned lower limit and below the above-mentioned upper limit, the dielectric loss tangent of the cured product can be further reduced. Furthermore, when the content of the epoxy compound (A) is above the above-mentioned lower limit and below the above-mentioned upper limit, the cure shrinkage rate can be effectively reduced, and interlayer delamination between the insulating layer and the metal layer can be further effectively suppressed. Furthermore, the thermal dimensional stability of the cured product can be further improved.

[0056] [Active ester compound (B)] The resin material contains an active ester compound (B). By using the active ester compound (B), the dielectric loss tangent of the cured product can be reduced. The active ester compound (B) is a curing agent. Only one type of active ester compound (B) may be used, or two or more types may be used in combination.

[0057] The active ester compound (B) refers to a compound that contains at least one ester bond in its structure and has aromatic rings bonded to both sides of the ester bond. The active ester compound (B) 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.

[0058] Examples of the active ester compound (B) include compounds represented by the following formula (1).

[0059] [ka]

[0060] In the above formula (1), X1 represents a group containing an aliphatic chain, a group containing an aliphatic ring, or a group containing an aromatic ring, and X2 represents a group containing an aromatic ring. Preferred examples of the group containing an aromatic ring include an optionally substituted benzene ring and an optionally substituted naphthalene ring. Examples of the substituent include a hydrocarbon group. The number of carbon atoms in the hydrocarbon group is preferably 12 or less, more preferably 6 or less, and even more preferably 4 or less.

[0061] Examples of the combination of X1 and X2 include a combination of an optionally substituted benzene ring and an optionally substituted benzene ring, and a combination of an optionally substituted benzene ring and an optionally substituted naphthalene ring.Furthermore, examples of the combination of X1 and X2 include a combination of an optionally substituted naphthalene ring and an optionally substituted naphthalene ring.

[0062] The active ester compound (B) is not particularly limited. From the viewpoint of further improving the thermal dimensional stability and flame retardancy of the cured product, the active ester compound (B) is preferably an active ester compound having two or more aromatic skeletons. From the viewpoint of reducing the dielectric tangent of the cured product and improving the thermal dimensional stability of the cured product, the active ester compound (B) more preferably has a naphthalene ring in the skeleton of the main chain.

[0063] Commercially available products of the active ester compound (B) include "HPC-8000-65T," "HPC-8000L-65MT," "HPC-8150-60T," "HPC-8150-62T," "EXB9416-70BK," and "EXB8100-65T," manufactured by DIC Corporation.

[0064] The content of the active ester compound (B) per 100 parts by weight of the epoxy compound (A) is preferably 70 parts by weight or more, more preferably 80 parts by weight or more, even more preferably 85 parts by weight or more, and preferably 150 parts by weight or less, more preferably 130 parts by weight or less, and even more preferably 120 parts by weight or less. When the content of the active ester compound (B) is above the above-mentioned lower limit and below the above-mentioned upper limit, curability can be improved and volatilization of remaining unreacted components can be further suppressed. Furthermore, when the content of the active ester compound (B) is above the above-mentioned lower limit and below the above-mentioned upper limit, the dielectric tangent of the cured product can be further reduced.

[0065] The content of the active ester compound (B) in the resin material, based on 100% by weight of all components excluding the inorganic filler (D) and the solvent, is preferably 20% by weight or more, more preferably 25% by weight or more, even more preferably 30% by weight or more, and preferably 60% by weight or less, more preferably 50% by weight or less. When the content of the active ester compound (B) is above the above-mentioned lower limit and below the above-mentioned upper limit, curability can be improved and volatilization of remaining unreacted components can be further suppressed. Furthermore, when the content of the active ester compound (B) is above the above-mentioned lower limit and below the above-mentioned upper limit, the dielectric tangent of the cured product can be further reduced. Furthermore, when the content of the active ester compound (B) is above the above-mentioned lower limit and below the above-mentioned upper limit, cure shrinkage can be effectively reduced and interlayer delamination between the insulating layer and the metal layer can be further effectively suppressed.

[0066] [Curing accelerator (C)] The resin material contains a curing accelerator (C). The curing accelerator (C) may be used alone or in combination of two or more.

[0067] Examples of the curing accelerator (C) include phosphorus-containing compounds (phosphorus-containing compounds that are liquid at 25°C and phosphorus-containing compounds that are solid at 25°C), amine compounds that do not have an imidazole skeleton, imidazole compounds, organometallic compounds, peroxides, and azo compounds.

[0068] The phosphorus-containing compound refers to a compound containing a phosphorus atom. Examples of the phosphorus-containing compound include organic phosphine compounds such as tetrabutylphosphonium o,o-diethylphosphorodithioate, triphenylphosphine, tricyclohexylphosphine, tribenzylphosphine, 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 tetraphenylborate. The phosphorus-containing compounds may be used alone or in combination.

[0069] Examples of the amine compound not having an imidazole skeleton include diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, diethylenetriamine, ethylenediamine, tris(dimethylaminomethyl)phenol, benzyldimethylamine, m-xylylenedi(dimethylamine), N,N'-dimethylpiperazine, N-methylpyrrolidine, N-methylhydroxypiperidine, m-xylylenediamine, isophoronediamine, N-aminoethylpiperazine, polyoxypropylenepolyamine, and 4,4-dimethylaminopyridine. The amine compound not having an imidazole skeleton may be used alone or in combination of two or more.

[0070] Examples of the imidazole compound include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, and 1-cyanoethyl-2-phenylimidazolium trimethylolate. Examples of the imidazole compounds include methyltrimethylimidazolyl-(1')-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-dihydroxymethylimidazole. The imidazole compounds may be used alone or in combination of two or more.

[0071] Examples of the organometallic compound include zinc naphthenate, cobalt naphthenate, tin octoate, cobalt octoate, bisacetylacetonate cobalt(II), trisacetylacetonate cobalt(III), etc. The organometallic compounds may be used alone or in combination of two or more.

[0072] Examples of the peroxides include diacyl peroxides, peroxyesters, peroxydicarbonates, monoperoxycarbonates, peroxyketals, dialkyl peroxides, dibenzyl peroxide, dicumyl peroxide, hydroperoxides, and ketone peroxides. The peroxides may be used alone or in combination of two or more.

[0073] The curing accelerator (C) preferably contains a phosphorus-containing compound or an amine compound without an imidazole skeleton, more preferably contains a phosphorus-containing compound, and even more preferably contains a phosphorus-containing compound that is liquid at 25°C. In this case, the cure shrinkage can be effectively reduced, and delamination between the insulating layer and the metal layer can be more effectively suppressed. Furthermore, when the curing accelerator (C) contains a phosphorus-containing compound that is liquid at 25°C, the thermal dimensional stability and glass transition temperature of the cured product can be further increased.

[0074] In addition, the phrase "liquid at 25°C" in the phosphorus-containing compound that is liquid at 25°C means that the viscosity measured at 25°C using a Brookfield viscometer is 500 Pa·s or less.

[0075] The viscosity of the phosphorus-containing compound liquid at 25°C, as measured using a Brookfield viscometer at 25°C, is preferably 0.001 Pa·s or more, more preferably 0.01 Pa·s or more, even more preferably 0.1 Pa·s or more, particularly preferably 0.3 Pa·s or more, and preferably 100 Pa·s or less, more preferably 50 Pa·s or less, and even more preferably 10 Pa·s or less. When the viscosity of the phosphorus-containing compound liquid at 25°C is equal to or greater than the lower limit, the phosphorus-containing compound liquid at 25°C can be more uniformly dispersed in the resin material, thereby more effectively achieving the effects of the present invention. Furthermore, when the viscosity of the phosphorus-containing compound liquid at 25°C is equal to or greater than the lower limit and equal to or less than the upper limit, the glass transition temperature of the cured product can be further increased.

[0076] More specifically, the viscosity of the phosphorus-containing compound that is liquid at 25°C can be measured using a B-type viscometer (for example, "TVE33H" manufactured by Oyo Giken Co., Ltd.) under conditions of 25°C and 20 rpm.

[0077] The content of the curing accelerator (C) in the resin material, based on 100% by weight of the components excluding the solvent, is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, even more preferably 0.1% by weight or more, particularly preferably 0.13% by weight or more, and preferably 5% by weight or less, more preferably 2% by weight or less, and even more preferably 1% by weight or less. When the content of the curing accelerator (C) is above the above-mentioned lower limit and below the above-mentioned upper limit, the crosslinked structure in the cured product becomes uniform and the number of unreacted functional groups decreases, resulting in a high crosslink density. Furthermore, the resin material can be cured well even at relatively low temperatures.

[0078] The content of the amine compound not having an imidazole skeleton in 100% by weight of the components excluding the solvent in the resin material is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, even more preferably 0.1% by weight or more, and preferably 5% by weight or less, more preferably 2% by weight or less, and even more preferably 1% by weight or less. When the content of the amine compound not having an imidazole skeleton is equal to or more than the above lower limit and equal to or less than the above upper limit, delamination between the insulating layer and the metal layer can be more effectively suppressed.

[0079] [Inorganic filler (D)] The resin material contains an inorganic filler (D). By using the inorganic filler (D), 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. Only one type of inorganic filler (D) may be used, or two or more types may be used in combination.

[0080] Examples of the inorganic filler (D) include silica, talc, clay, mica, hydrotalcite, alumina, magnesium oxide, aluminum hydroxide, aluminum nitride, and boron nitride.

[0081] The inorganic filler (D) is preferably silica or alumina, more preferably silica, and even more preferably fused silica. In this case, the adhesive strength between the insulating layer and the metal layer can be further increased, and finer wiring can be formed on the surface of the insulating layer. When the inorganic filler (D) is silica, the thermal dimensional stability of the cured product can also be further improved.

[0082] The inorganic filler (D) has an average particle size of preferably 10 nm or more, more preferably 50 nm or more, even more preferably 100 nm or more, and preferably 5 μm or less, more preferably 3 μm or less, even more preferably 1 μm or less, and particularly preferably 0.5 μm or less. When the average particle size of the inorganic filler (D) is equal to or greater than the above lower limit and equal to or less than the above upper limit, the adhesive strength between the insulating layer and the metal layer can be further increased.

[0083] The median diameter (d50) at 50% is used as the average particle diameter of the inorganic filler (D). The average particle diameter can be measured using a laser diffraction / scattering particle size distribution analyzer.

[0084] The inorganic filler (D) is preferably spherical, and more preferably spherical silica. In this case, the surface roughness of the insulating layer is effectively reduced, and the adhesive strength between the insulating layer and the metal layer can be further increased. When the inorganic filler (D) is spherical, the aspect ratio of the inorganic filler (D) is preferably 1 or more, preferably 2 or less, more preferably 1.5 or less.

[0085] The inorganic filler (D) is preferably surface-treated, more preferably with a coupling agent, and even more preferably with a silane coupling agent. In this case, the surface roughness of the roughened cured product is further reduced, and the adhesive strength between the insulating layer and the metal layer is further increased. Furthermore, finer wiring is formed on the surface of the insulating layer, and inter-wiring insulation reliability and inter-layer insulation reliability can be imparted.

[0086] Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent, etc. Examples of the silane coupling agent include methacrylsilane, acrylsilane, aminosilane, imidazolesilane, vinylsilane, and epoxysilane.

[0087] The content of the inorganic filler (D) in the resin material, based on 100% by weight of the components excluding the solvent, is preferably 30% by weight or more, more preferably 40% by weight or more, even more preferably 50% by weight or more, even more preferably 60% by weight or more, particularly preferably 65% ​​by weight or more, most preferably 70% by weight or more, preferably 90% by weight or less, more preferably 85% by weight or less, even more preferably 83% by weight or less, particularly preferably 80% by weight or less, and most preferably 78% by weight or less. When the content of the inorganic filler (D) is above the above-mentioned lower limit and below the above-mentioned upper limit, the surface roughness of the insulating layer is further reduced, and the adhesive strength between the insulating layer and the metal layer is further increased. Furthermore, finer wiring is formed on the surface of the insulating layer. Furthermore, this content of the inorganic filler (D) can reduce the linear expansion coefficient of the cured product and simultaneously improve smear removal properties. Furthermore, when the content of the inorganic filler (D) is above the above-mentioned lower limit, the dielectric loss tangent of the cured product is effectively reduced.

[0088] The content of the inorganic filler (D) in the resin material, based on 100% by volume of the components excluding the solvent, is preferably 30% by volume or more, more preferably 40% by volume or more, even more preferably 50% by volume or more, and preferably 75% by volume or less, more preferably 73% by volume or less, and even more preferably 70% by volume or less. When the content of the inorganic filler (D) is above the above-mentioned lower limit and below the above-mentioned upper limit, the surface roughness of the insulating layer is further reduced, and the adhesive strength between the insulating layer and the metal layer is further increased. Furthermore, finer wiring is formed on the surface of the insulating layer. Furthermore, this content of the inorganic filler (D) can reduce the linear expansion coefficient of the cured product and simultaneously improve smear removal properties. Furthermore, when the content of the inorganic filler (D) is above the above-mentioned lower limit, the dielectric loss tangent of the cured product is effectively reduced.

[0089] [Thermoplastic resin (E)] The resin material preferably contains a thermoplastic resin (E). Examples of the thermoplastic resin (E) include polyvinyl acetal resin, polyimide resin, and phenoxy resin. The thermoplastic resin (E) may be used alone or in combination of two or more.

[0090] From the viewpoint of effectively lowering the dielectric loss tangent of the cured product and effectively improving the adhesion of metal wiring regardless of the curing environment, the thermoplastic resin (E) is preferably a polyimide resin or a phenoxy resin. The use of a polyimide resin or a phenoxy resin prevents the resin film from becoming less able to fill holes or irregularities in the circuit board and prevents the inorganic filler (D) from becoming non-uniform. Furthermore, the use of a polyimide resin or a phenoxy resin allows the melt viscosity to be adjusted, improving the dispersibility of the inorganic filler (D) and making it less likely that the resin material or B-staged product will wet and spread to unintended areas during the curing process.

[0091] The polyimide resin is not particularly limited. Conventionally known polyimide resins can be used as the polyimide resin. The polyimide resins may be used alone or in combination of two or more.

[0092] From the viewpoint of improving solubility, the polyimide resin is preferably a polyimide resin which is a reaction product of tetracarboxylic dianhydride and dimer diamine.

[0093] Examples of the tetracarboxylic dianhydride 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. sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyltert-dianhydride, and bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride.

[0094] Examples of the dimer diamine include VERSAMINE 551 (trade name, manufactured by BASF Japan Ltd., 3,4-bis(1-aminoheptyl)-6-hexyl-5-(1-octenyl)cyclohexene), VERSAMINE 552 (trade name, manufactured by Cognix Japan Ltd., hydrogenated VERSAMINE 551), PRIAMINE 1075, and PRIAMINE 1074 (trade names, all manufactured by Croda Japan Ltd.).

[0095] The polyimide resin may have an acid anhydride structure, a maleimide structure, or a citraconic acid structure at its terminal. In this case, the polyimide resin can be reacted with an epoxy compound (A). By reacting the polyimide resin with the epoxy compound (A), the thermal dimensional stability of the cured product can be improved.

[0096] The phenoxy resin is not particularly limited. Conventionally known phenoxy resins can be used as the phenoxy resin. The phenoxy resins may be used alone or in combination of two or more.

[0097] Examples of the phenoxy resin include phenoxy resins having a skeleton such as a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a biphenyl skeleton, a novolac skeleton, a naphthalene skeleton, and an imide skeleton.

[0098] Commercially available phenoxy resins include, for example, "YP50," "YP55," and "YP70" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., and "1256B40," "4250," "4256H40," "4275," "YX6954BH30," and "YX8100BH30" manufactured by Mitsubishi Chemical Corporation.

[0099] From the viewpoint of obtaining a resin material with even better storage stability, the weight average molecular weight of the thermoplastic resin (E) is preferably 5,000 or more, more preferably 10,000 or more, and preferably 100,000 or less, more preferably 50,000 or less.

[0100] The weight average molecular weight of the thermoplastic resin (E) is a weight average molecular weight measured by gel permeation chromatography (GPC) and calculated as polystyrene.

[0101] The content of the thermoplastic resin (E) is not particularly limited. The content of the thermoplastic resin (E) is preferably 1% by weight or more, more preferably 5% by weight or more, even more preferably 10% by weight or more, even more preferably 12% by weight or more, particularly preferably 14% by weight or more, preferably 30% by weight or less, more preferably 20% by weight or less, and even more preferably 15% by weight or less, based on 100% by weight of the components in the resin material excluding the inorganic filler (D) and the solvent. When the content of the thermoplastic resin (E) is above the lower limit and below the upper limit, the resin material has good embedding properties for holes or irregularities in a circuit board. When the content of the thermoplastic resin (E) is above the lower limit, the formation of a resin film becomes easier, resulting in a better insulating layer. When the content of the thermoplastic resin (E) is above the lower limit, the cure shrinkage rate can be effectively reduced, and delamination between the insulating layer and the metal layer can be more effectively suppressed. When the content of the thermoplastic resin (E) is below the upper limit, the linear expansion coefficient of the cured product becomes even smaller. When the content of the thermoplastic resin (E) is equal to or less than the upper limit, the surface roughness of the insulating layer is further reduced, and the adhesive strength between the insulating layer and the metal layer is further increased.

[0102] [solvent] The resin material contains or does not contain a solvent. The resin material may contain or may not contain a solvent. By using the solvent, the viscosity of the resin material can be controlled within a suitable range, and the coatability of the resin material can be improved. The solvent may also be used to obtain a slurry containing the inorganic filler (D). The solvent may be used alone or in combination of two or more.

[0103] Examples of the solvent include acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane, toluene, xylene, methyl ethyl ketone, N,N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidone, n-hexane, cyclohexane, cyclohexanone, and naphtha, which is a mixture.

[0104] It is preferable that most of the solvent is removed when the resin composition is formed into a film. Therefore, the boiling point of the solvent is preferably 200°C or less, more preferably 180°C or less. The content of the solvent in the resin composition is not particularly limited. The content of the solvent can be appropriately changed taking into account the coatability of the resin composition, etc.

[0105] When the resin material is a B-stage film, the content of the solvent in 100% by weight of the B-stage film is preferably 1% by weight or more, more preferably 2% by weight or more, preferably 15% by weight or less, more preferably 10% by weight or less.

[0106] [Other ingredients] For the purpose of improving impact resistance, heat resistance, resin compatibility, workability, etc., the resin material may contain other components in addition to the above-mentioned components (epoxy compound (A), active ester compound (B), curing accelerator (C), inorganic filler (D), thermoplastic resin (E), and solvent). Examples of the other components include a thermosetting compound other than the epoxy compound; a curing agent other than the active ester compound; an organic filler; a leveling agent; a flame retardant; a coupling agent; a colorant; an antioxidant; an ultraviolet degradation inhibitor; an antifoaming agent; a thickener; a thixotropy-imparting agent, etc. One of the other components may be used alone, or two or more may be used in combination.

[0107] Examples of the thermosetting compound different from the epoxy compound include maleimide compounds.

[0108] Examples of curing agents other than the active ester compounds include phenol compounds, cyanate ester compounds, benzoxazine compounds, carbodiimide compounds, thiol compounds, phosphine compounds, dicyandiamide, and acid anhydrides.

[0109] Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent, etc. Examples of the silane coupling agent include vinyl silane, amino silane, imidazole silane, and epoxy silane.

[0110] The resin material may or may not contain glass cloth. The resin material preferably does not contain glass cloth. The resin material preferably is not a prepreg.

[0111] (resin film) The resin composition described above can be molded into a film to obtain a resin film (B-staged product / B-stage film). The resin material is preferably a resin film. The resin film is preferably a B-stage film.

[0112] Examples of methods for forming a resin composition into a film to obtain a resin film include the following: an extrusion molding method in which a resin composition is melt-kneaded using an extruder, extruded, and then molded into a film using a T-die, circular die, or the like; a casting molding method in which a resin composition containing a solvent is cast into a film; and other conventionally known film molding methods. Extrusion molding and casting molding are preferred because they can be used to make thinner films. Films include sheets.

[0113] The resin composition is formed into a film and dried by heating at, for example, 50°C to 150°C for 1 minute to 10 minutes to an extent that curing by heat does not proceed too much, thereby obtaining a resin film that is a B-stage film.

[0114] The film-like resin composition obtained by the drying process described above is called a B-stage film. The B-stage film is in a semi-cured state. The semi-cured product is not completely cured, and curing can continue.

[0115] The resin film does not have to be a prepreg. When the resin film is not a prepreg, migration does not occur along the glass cloth or the like. Furthermore, when the resin film is laminated or precured, irregularities due to the glass cloth do not occur on the surface.

[0116] The 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 the base film. The metal foil is preferably a copper foil.

[0117] Examples of the substrate 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 substrate film may be subjected to a release treatment, if necessary.

[0118] From the viewpoint of controlling the degree of cure 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 equal to or greater than the thickness of the conductor layer (metal layer) that forms the circuit. The thickness of the insulating layer is preferably 5 μm or more and preferably 200 μm or less.

[0119] (Other details of resin materials) The resin material can be used for various purposes. For example, the resin material is preferably used to form a mold resin in which a semiconductor chip is embedded in a semiconductor device. The resin material is also preferably used as a replacement for liquid crystal polymer (LCP), a millimeter-wave antenna, or a rewiring layer. The resin material is not limited to the above purposes, but is preferably used for wiring formation purposes in general.

[0120] The resin material is preferably used as an adhesive material. The resin material is preferably used as, for example, an adhesive material for power overlay packages, an adhesive material for printed wiring boards, an adhesive material for coverlays of flexible printed circuit boards, or an adhesive material for semiconductor bonding. The resin material is preferably an adhesive material.

[0121] The resin material is preferably used as an insulating material. The resin material is preferably used to form an insulating layer in a printed wiring board, and more preferably to form an insulating layer in a multilayer printed wiring board. The resin material is preferably an insulating material, and more preferably an interlayer insulating material. The insulating material may also serve as an adhesive material.

[0122] The cured product according to the present invention is a cured product of a resin material obtained by curing the resin material described above. The cured product according to the present invention is a cured product of a resin material, and the resin material is the resin material described above. The cured product according to the present invention can be obtained by curing the resin material described above. The heating conditions for the resin material when obtaining the cured product according to the present invention are not particularly limited, as long as the resin material is cured.

[0123] (Laminated structures and copper-clad laminates) A laminated structure can be obtained by laminating a lamination target member having a metal layer on one or both sides of the resin film. The 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, the resin film being the resin material described above. The method for laminating the resin film and the lamination target member is not particularly limited, and known methods can be used. For example, the resin film can be laminated to the lamination target member using a device such as a parallel plate press or a roll laminator while applying pressure with or without heating.

[0124] The material of the metal layer is preferably copper.

[0125] The lamination target member having the metal layer on its surface may be a metal foil such as a copper foil.

[0126] The resin material is preferably used to obtain a copper-clad laminate. An example of the copper-clad laminate is a copper-clad laminate including a copper foil and a resin film laminated on one surface of the copper foil, the resin film being made of the resin material described above.

[0127] The thickness of the copper foil of the copper-clad laminate is not particularly limited. The thickness of the copper foil is preferably 1 μm or more and 100 μm or less. In addition, in order to increase the adhesive strength between the cured resin material and the copper foil, the copper foil preferably has fine irregularities on its surface. The method for forming the irregularities is not particularly limited. Examples of the method for forming the irregularities include a method using a known chemical solution, a known plasma treatment, and a known UV treatment.

[0128] (Circuit board with insulating layer) The resin material is suitably used to obtain a circuit board with an insulating layer. One example of the circuit board with an insulating layer is a circuit board with an insulating layer that includes a circuit board and an insulating layer disposed on the surface of the circuit board, the insulating layer being a cured product of the resin material described above.

[0129] In the circuit board with an insulating layer, the insulating layer is preferably laminated on the surface of the circuit board on which the circuits are provided, and a portion of the insulating layer is preferably embedded between the circuits.

[0130] The above-mentioned circuit board with an insulating layer can be obtained by a conventionally known method.

[0131] (Multilayer boards and multilayer printed wiring boards) The resin material is preferably used to obtain a multilayer substrate. An example of the multilayer substrate is a multilayer substrate including a circuit board and an insulating layer laminated on the circuit board. The insulating layer of the multilayer substrate is a cured product of the resin material described above. The insulating layer is preferably laminated on the surface of the circuit board on which the circuits (metal layer) are provided. A portion of the insulating layer is preferably embedded between the circuits.

[0132] In the multilayer substrate, the surface of the insulating layer opposite to the surface on which the circuit board is laminated is preferably roughened.

[0133] The roughening treatment method is not particularly limited and may be any conventionally known roughening treatment method. The surface of the insulating layer may be subjected to swelling treatment before the roughening treatment.

[0134] Preferably, the multilayer substrate further comprises a copper plating layer laminated on the roughened surface of the insulating layer.

[0135] Another example of the multilayer substrate is a multilayer substrate comprising a circuit board, an insulating layer laminated on the surface of the circuit board, and 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 using a copper-clad laminate comprising copper foil and a resin film laminated on one surface of the copper foil and curing the resin film. Furthermore, the copper foil is preferably etched to form a copper circuit.

[0136] Another example of the multilayer substrate is a multilayer substrate including a circuit board and a plurality of insulating layers laminated on a surface of the circuit board. At least one of the insulating layers arranged on the circuit board is formed using the resin material. Preferably, the multilayer substrate further includes a circuit laminated on at least one surface of the insulating layer formed using the resin film.

[0137] The above resin material is suitably used to form an insulating layer in a multilayer printed wiring board.

[0138] The multilayer printed wiring board includes, for example, a circuit board, a plurality of insulating layers disposed on a surface of the circuit board, and a metal layer disposed between the plurality of insulating layers, and at least one of the insulating layers is a cured product of the resin material described above.

[0139] FIG. 1 is a cross-sectional view schematically showing a multilayer printed wiring board using a resin material according to one embodiment of the present invention.

[0140] In the multilayer printed wiring board 11 shown in FIG. 1, a plurality of insulating layers 13-16 are laminated on the upper surface 12a of a circuit board 12. The insulating layers 13-16 are cured layers. A metal layer 17 is formed on a partial region of the upper surface 12a of the circuit board 12. Of the plurality of insulating layers 13-16, the insulating layers 13-15 other than the insulating layer 16 located on the outer surface opposite the circuit board 12 have the metal layer 17 formed on a partial region of the upper surface. The metal layer 17 is a circuit. The metal layer 17 is disposed between the circuit board 12 and the insulating layer 13, and between each of the laminated insulating layers 13-16. The lower metal layer 17 and the upper metal layer 17 are connected to each other by at least one of via hole connection and through hole connection (not shown).

[0141] In the multilayer printed wiring board 11, the insulating layers 13 to 16 are formed from a cured product of the resin material. In this embodiment, the surfaces of the insulating layers 13 to 16 are roughened, and thus fine holes (not shown) are formed in the surfaces of the insulating layers 13 to 16. The metal layer 17 extends into the fine holes. In the multilayer printed wiring board 11, the width dimension (L) of the metal layer 17 and the width dimension (S) of the portion where the metal layer 17 is not formed can be reduced. In addition, the multilayer printed wiring board 11 provides good insulation reliability between upper and lower metal layers that are not connected by via hole connections or through hole connections (not shown).

[0142] The present invention will be specifically described below by way of examples and comparative examples, but the present invention is not limited to the following examples.

[0143] The following materials were prepared:

[0144] (Epoxy compound (A)) Biphenyl-type epoxy compound (Nippon Kayaku "NC-3000") Phenolic glycidyl ether epoxy compound (Nagase & Co., Ltd. "EX-201-IM") Alcoholic glycidyl ether epoxy compound (Daicel Corporation's "PB3600", an aliphatic epoxy compound with a glycidyl ether skeleton) Alcoholic glycidyl ether epoxy compound (Nagase & Co., Ltd.'s "EX-216L," an aliphatic epoxy compound with a glycidyl ether skeleton) Alcoholic glycidyl ether epoxy compound ("YX8000" manufactured by Mitsubishi Chemical Corporation, an aliphatic epoxy compound with a glycidyl ether skeleton) Alcoholic glycidyl ether epoxy compound (ADEKA "EP-4000", an aliphatic epoxy compound with a glycidyl ether skeleton)

[0145] (hardening agent) Active ester compound (B): Active ester compound-containing liquid (DIC Corporation "HPC-8000L-65MT", solid content 65% by weight) Hardeners other than active ester compounds: Phenol compound-containing liquid (DIC "LA-1356", solid content 60% by weight)

[0146] (Curing accelerator (C)) A phosphorus-containing compound that is liquid at 25°C ("PX-4ET" manufactured by Nippon Chemical Industry Co., Ltd., tetrabutylphosphonium o,o-diethylphosphorodithioate, viscosity at 25°C: 1.29 Pa·s) A phosphorus-containing compound that is solid at 25°C ("TBP-3PC" manufactured by Hokko Chemical Industry Co., Ltd.) Amine compound that is solid at 25°C (Mitsui Fine Chemicals "Bisaniline M") Amine compound that is solid at 25°C ("BAPP" manufactured by TCI)

[0147] (Inorganic filler (D)) Silica-containing slurry (75% by weight of silica: Admatechs "SC4050-HOA", average particle size 1.0 μm, aminosilane treatment, cyclohexanone 25% by weight)

[0148] (Thermoplastic resin (E)) Phenoxy resin (Mitsubishi Chemical Corporation "YX6954BH30")

[0149] (Examples 1 to 10 and Comparative Examples 1 and 2) The components shown in Tables 1 and 2 below were mixed in the amounts (unit: parts by weight of solid content) shown in Tables 1 and 2 below, and stirred at room temperature until a uniform solution was obtained, to obtain a resin material.

[0150] Preparation of resin film: The obtained resin material was applied using an applicator to the release-treated surface of a release-treated polyethylene terephthalate film (PET film, Toray Industries, Inc. "XG284", thickness 25 μm), and then dried for 2 minutes and 30 seconds in a gear oven at 100°C to volatilize the solvent. In this way, a laminated film (a laminated film of PET film and resin film) was obtained in which a 40 μm-thick resin film (B-stage film) was laminated on the PET film.

[0151] (evaluation) (1) Curing shrinkage rate Toray Industries prepared "XG284" polyethylene terephthalate films (1) and (2) with a thickness of 25 μm and release-treated. The resin material was applied to the release-treated surface of the polyethylene terephthalate film (1) using an applicator, and then dried in a gear oven at 100°C for 2 minutes and 30 seconds to volatilize the solvent, yielding a resin film with a thickness of 40 μm. The true density of the resulting resin film at 25°C was measured using a true density measuring device (Anton Paar Japan), and the density ρ of the resin material at 25°C was calculated. A (g / cm 3 ). The surface of the 40 μm-thick resin film opposite the polyethylene terephthalate film (1) was aligned with the release-treated surface of the polyethylene terephthalate film (2), and laminated using a vacuum diaphragm laminator ("MVLPα500" manufactured by The Japan Steel Works, Ltd.). Lamination was performed by reducing the pressure to 13 hPa or less for 30 seconds, and then pressing at 50°C and a pressure of 0.6 MPa for 30 seconds. The resulting laminated film (polyethylene terephthalate film (1) / resin film / polyethylene terephthalate film (2)) was heated at 130°C for 30 minutes, and then at 180°C for 30 minutes to obtain a cured product of the resin material (cured product of the resin film). The true density of the resulting cured product at 25°C was measured using a true density measuring device (manufactured by Anton Paar Japan), and the density ρ of the cured resin material at 25°C was calculated. B (g / cm 3 The density of the resin material at 25°C (ρ A ) and the density of the cured resin material at 25°C (ρ B ) and the cure shrinkage was calculated using the following formula (X).

[0152] Curing shrinkage rate (%)=[(ρ B -ρ A ) / ρ A ]×100 (X)

[0153] [Criteria for determining cure shrinkage rate] 〇〇: Curing shrinkage rate is 1.0% or less ○: Curing shrinkage rate is over 1.0% and 2.0% or less △: Curing shrinkage rate is over 2.0% and 2.5% or less ×: Curing shrinkage rate exceeds 2.5%

[0154] (2) Delamination The resulting resin film was laminated onto a metal layer (copper layer) to obtain a laminate of the resin film and metal layer. Lamination was performed using a Meiki Seisakusho "batch vacuum laminator MVLP-500-IIA." The pressure was reduced for 30 seconds to 13 hPa or less, followed by lamination at 100°C and a pressure of 0.7 MPa for 30 seconds, and then pressing at 100°C and a pressure of 0.8 MPa for 60 seconds. This laminate was heated at 130°C for 30 minutes, then at 160°C for 30 minutes, and then at 110°C for 30 minutes to produce a substrate comprising an insulating layer and a metal layer. The interface between the insulating layer and the metal layer in the resulting substrate was observed using FIB-SEM, and the distance at which delamination occurred was measured.

[0155] [Criteria for determining delamination] 〇〇: The maximum length of the area where delamination has occurred is 1 μm or less ○: The maximum length of the area where delamination has occurred is more than 1 μm and 10 μm or less △: The maximum length of the area where delamination has occurred is more than 10 μm and 15 μm or less ×: The maximum length of the portion where delamination occurs exceeds 15 μm

[0156] (3) Dielectric loss tangent (Df) The resulting 40 μm-thick resin film (B-stage film) was heated at 180°C for 30 minutes, followed by 200°C for 60 minutes to obtain a cured product. The resulting cured product was cut into a 2 mm wide x 80 mm long piece, and 10 pieces were stacked together to form a measurement sample. The dielectric loss tangent (Df) of the cured product was measured at room temperature (23°C) and a frequency of 5.8 GHz using a cavity resonance perturbation dielectric constant measurement device CP521 manufactured by Kanto Electronics Application Development Co., Ltd. and a network analyzer N5224A PNA manufactured by Keysight Technologies, Inc.

[0157] [Dielectric loss tangent (Df) criteria] ○: Dielectric tangent is 4.5×10 -3 below △: Dielectric loss tangent is 4.5×10 -3 Exceeds 5.0 x 10 -3 below ×: Dielectric tangent is 5.0×10 -3 exceed

[0158] The compositions and results are shown in Tables 1 and 2 below.

[0159] [Table 1]

[0160] [Table 2] [Explanation of symbols]

[0161] 11...Multilayer printed wiring board 12...Circuit board 12a…Top surface 13~16...Insulating layer 17...Metal layer

Claims

1. The composition contains an epoxy compound (A), an active ester compound (B), a curing accelerator (C), and an inorganic filler (D), The density of the resin material at 25°C is ρ Ａ The resin material is heated at 130°C for 30 minutes, and then heated at 180°C for 30 minutes to obtain a cured resin material having a density at 25°C of ρ Ｂ When the curing shrinkage of the resin material is expressed by the following formula (X), the curing shrinkage is 2.5% or less. Hardening shrinkage (%) = [(ρ Ｂ -ρ Ａ ) / ρ Ａ ]×100・・・(X)

2. The resin material according to claim 1, wherein the cure shrinkage represented by the formula (X) is 1.7% or less.

3. The resin material according to claim 1 or 2, wherein the epoxy compound (A) comprises an aliphatic epoxy compound having a glycidyl ether skeleton.

4. The resin material according to claim 1 or 2, further comprising a thermoplastic resin (E).

5. The resin material according to claim 4, wherein the content of the thermoplastic resin (E) is 10% by weight or more based on 100% by weight of components in the resin material excluding the inorganic filler (D) and the solvent.

6. 3. The resin material according to claim 1, wherein the content of the active ester compound (B) is 20% by weight or more based on 100% by weight of components in the resin material excluding the inorganic filler (D) and the solvent.

7. 3. The resin material according to claim 1, wherein the content of the epoxy compound (A) is 40% by weight or more based on 100% by weight of components in the resin material excluding the inorganic filler (D) and the solvent.

8. The resin material according to claim 1 or 2, wherein the content of the inorganic filler (D) is 78% by weight or less based on 100% by weight of components excluding the solvent in the resin material.

9. The resin material according to claim 1 or 2, wherein the curing accelerator (C) comprises a phosphorus-containing compound or an amine compound having no imidazole skeleton.

10. The resin material according to claim 1 or 2, wherein the curing accelerator (C) comprises a phosphorus-containing compound that is liquid at 25°C.

11. The resin material according to claim 1 or 2, which is a resin film.

12. The resin material according to claim 1 or 2, which is used to form an insulating layer in a multilayer printed wiring board.

13. A cured product of a resin material, A cured product, wherein the resin material is the resin material according to claim 1 or 2.

14. A circuit board; a plurality of insulating layers disposed on a surface of the circuit board; a metal layer disposed between a plurality of the insulating layers; A multilayer printed wiring board, wherein at least one of the insulating layers is a cured product of the resin material according to claim 1 or 2.

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