Resin material and multilayer printed wiring board

Abstract

To provide a resin material which can increase compatibility, and can reduce a dielectric loss tangent and can increase thermal dimensional stability and a glass transition temperature in a cured product of a resin material.SOLUTION: A resin material contains a first compound having a skeleton derived from an acid dianhydride having a norbornane skeleton, and a second compound having an aromatic skeleton, in which the first compound has a structural unit having an imide bond as a repeating structural unit, the second compound does not have the structural unit having the imide skeleton as the repeating structural unit, a molecular weight of the first compound exceeds 1,000, and the second compound is a thermosetting compound.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a resin material containing a compound having a skeleton derived from an acid dianhydride having a norbornane skeleton and a compound having an aromatic skeleton. The present invention also relates to a multilayer printed wiring board using the above resin material.

Background Art

[0002] Conventionally, various resin materials have been used to obtain electronic components such as semiconductor devices, laminates, and printed wiring boards. For example, in a multilayer printed wiring board, a resin material is used to form an insulating layer for insulating between internal layers or to form an insulating layer located in the surface layer portion. Wiring, which is generally made of metal, is laminated on the surface of the insulating layer. Further, in order to form the insulating layer, a resin film obtained by forming the resin material into a film may be used. The resin material and the resin film are used as an insulating material for a multilayer printed wiring board including a build-up film.

[0003] Patent Document 1 below discloses a polyimide alloy containing a cyclic aliphatic polyimide and a wholly aromatic polyimide, wherein the content of the cyclic aliphatic polyimide is 62% by mass to 95% by mass with respect to the total amount of the cyclic aliphatic polyimide and the wholly aromatic polyimide. The cyclic aliphatic polyimide is a polycondensate of a cyclic aliphatic tetracarboxylic dianhydride having an aliphatic 6-membered ring structure and at least one diamine compound selected from the group consisting of an aromatic diamine and an aliphatic diamine. The wholly aromatic polyimide is a polycondensate of at least one aromatic tetracarboxylic dianhydride selected from the group consisting of diphenyl-3,3',4,4'-tetracarboxylic dianhydride and benzene-1,2,4,5-tetracarboxylic dianhydride and an aromatic diamine.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0005] In Patent Document 1, a resin material containing a compound having a skeleton derived from an acid dianhydride is used. However, in a conventional resin material containing a compound having a skeleton derived from an acid dianhydride, when an insulating layer is formed using the resin material, the dielectric tangent of the cured product may not be sufficiently low, or the thermal dimensional stability may not be sufficiently high.

[0006] Further, in a resin material containing a compound having a skeleton derived only from an aliphatic acid dianhydride as the acid dianhydride, for example, it may be difficult to enhance the compatibility with a compound having an aromatic skeleton, or it may be difficult to enhance the heat resistance (glass transition temperature) of the cured product.

[0007] An object of the present invention is to provide a resin material that can enhance compatibility, can lower the dielectric tangent in the cured product of the resin material, and can enhance the thermal dimensional stability and the glass transition temperature. Another object of the present invention is to provide a multilayer printed wiring board using the above resin material.

MEANS FOR SOLVING THE PROBLEMS

[0008] According to a broad aspect of the present invention, there is provided a resin material including a first compound having a skeleton derived from an acid dianhydride having a norbornane skeleton and a second compound having an aromatic skeleton, wherein the first compound has a structural unit having an imide bond as a repeating structural unit, the second compound does not have a structural unit having an imide skeleton as a repeating structural unit, the molecular weight of the first compound exceeds 1000, and the second compound is a thermosetting compound.

[0009] In a specific aspect of the resin material according to the present invention, the molecular weight of the second compound is 1000 or less.

[0010] In a specific aspect of the resin material according to the present invention, the first compound has an aromatic ring.

[0011] In a specific aspect of the resin material according to the present invention, the first compound has a skeleton derived from an acid dianhydride having no norbornane skeleton and having a phthalimide skeleton.

[0012] In a specific aspect of the resin material according to the present invention, the first compound has a skeleton derived from an aliphatic diamine compound.

[0013] In a specific aspect of the resin material according to the present invention, the first compound has a skeleton derived from an aliphatic diamine compound having a cyclohexane skeleton.

[0014] In a specific aspect of the resin material according to the present invention, the first compound has a skeleton derived from a dimer diamine.

[0015] In a specific aspect of the resin material according to the present invention, in the first compound, among 100 mol% of the skeletons derived from all diamine compounds, the average ratio of the skeleton derived from the dimer diamine is 10 mol% or more and 90 mol% or less.

[0016] In a specific aspect of the resin material according to the present invention, the first compound has a maleimide skeleton or a benzoxazine skeleton.

[0017] In a specific aspect of the resin material according to the present invention, the first compound has a skeleton derived from an acid dianhydride having no norbornane skeleton and no phthalimide skeleton.

[0018] In a specific aspect of the resin material according to the present invention, the molecular weight of the first compound is 50,000 or less.

[0019] In a specific aspect of the resin material according to the present invention, the second compound contains an epoxy compound.

[0020] In a specific aspect of the resin material according to the present invention, the resin material includes an inorganic filler.

[0021] In a specific aspect of the resin material according to the present invention, the resin material includes a curing agent, and the curing agent includes an active ester compound.

[0022] In a specific aspect of the resin material according to the present invention, the resin material is a resin film.

[0023] The resin material according to the present invention is suitably used for forming an insulating layer in a multilayer printed wiring board.

[0024] According to a broad aspect of the present invention, there is provided a multilayer printed wiring board including 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 above-described resin material.

Advantages of the Invention

[0025] The resin material according to the present invention includes a first compound having a skeleton derived from an acid dianhydride having a norbornane skeleton and a second compound having an aromatic skeleton. The first compound has a structural unit having an imide bond as a repeating structural unit, and the second compound does not have a structural unit having an imide skeleton as a repeating structural unit. In the resin material according to the present invention, since the above configuration is provided, the compatibility can be enhanced, and in the cured product of the resin material, the dielectric tangent can be lowered, and the thermal dimensional stability and the glass transition temperature can be increased.

Brief Description of the Drawings

[0026]

Figure 1

Embodiments for Carrying Out the Invention

[0027] Hereinafter, the present invention will be described in detail.

[0028] The resin material according to the present invention includes a first compound having a skeleton derived from an acid dianhydride having a norbornane skeleton and a second compound having an aromatic skeleton. The first compound has a structural unit having an imide bond as a repeating structural unit, and the second compound does not have a structural unit having an imide skeleton as a repeating structural unit. In the resin material according to the present invention, the molecular weight of the first compound exceeds 1000, and the second compound is a thermosetting compound.

[0029] In the resin material according to the present invention, since the above configuration is provided, the compatibility can be enhanced, the dielectric loss tangent can be lowered in the cured product of the resin material, and the thermal dimensional stability and the glass transition temperature can be increased. In the resin material according to the present invention, since the first compound having a specific skeleton and the second compound having a specific skeleton are used, the compatibility and the glass transition temperature of the cured product can be particularly increased.

[0030] The resin material according to the present invention may be a resin composition or a resin film. The resin composition has fluidity. The resin composition may be in the form of a paste. The paste form includes a liquid state. Since it has excellent handleability, the resin material according to the present invention is preferably a resin film.

[0031] 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.

[0032] Hereinafter, the details of each component used in the resin material according to the present invention, the uses of the resin material according to the present invention, etc. will be described.

[0033] [First Compound] The resin material according to the present invention contains a first compound having a skeleton derived from an acid dianhydride having a norbornane skeleton. The above-mentioned first compound has a structural unit having an imide bond as a repeating structural unit. Only one kind of the above-mentioned first compound may be used, or two or more kinds may be used in combination.

[0034] The above-mentioned first compound may be a thermosetting compound or a thermoplastic compound.

[0035] The above-mentioned first compound has a skeleton derived from an acid dianhydride having a norbornane skeleton (norbornane skeleton-containing acid dianhydride; first acid dianhydride).

[0036] Examples of the acid dianhydride having a norbornane skeleton (first acid dianhydride) include an acid dianhydride represented by the following formula (1A), an acid dianhydride represented by the following formula (1B), an acid dianhydride represented by the following formula (1C), and an acid dianhydride represented by the following formula (1D). When these acid dianhydrides are used, the above-mentioned first compound has a skeleton derived from the acid dianhydride represented by the following formula (1A), (1B), (1C) or (1D).

[0037]

Chemical formula

[0038]

Chemical formula

[0039]

Chemical formula

[0040]

Chemical formula

[0041] In the above first compound, in 100 mol% of the skeletons derived from all the acid dianhydrides, the average ratio of the skeleton derived from the acid dianhydride having a norbornane skeleton (the first acid dianhydride) is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more. In the above first compound, in 100 mol% of the skeletons derived from all the acid dianhydrides, the average ratio of the skeleton derived from the acid dianhydride having a norbornane skeleton (the first acid dianhydride) is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less. When the average ratio of the skeleton derived from the above first acid dianhydride is not less than the above lower limit and not more than the above upper limit, the effects of the present invention can be more effectively exerted.

[0042] The above first compound preferably has a skeleton derived from an acid dianhydride having no norbornane skeleton and having a phthalimide skeleton (a norbornane-skeleton-free - phthalimide-skeleton-containing - acid dianhydride; the second acid dianhydride). In this case, the dielectric tangent of the cured product can be further lowered, and the thermal dimensional stability of the cured product can be further enhanced. Note that a compound having a norbornane skeleton and a phthalimide skeleton is classified as the above first acid dianhydride.

[0043] Examples of the acid dianhydride having no norbornane skeleton and having a phthalimide skeleton (the second acid dianhydride) include pyromellitic dianhydride, 4,4'-oxydiphthalic anhydride, and 4,4'-biphthalic anhydride.

[0044] In the above-mentioned first compound, in 100 mol% of the skeletons derived from all the acid dianhydrides, the average proportion of the skeleton derived from the acid dianhydride having no norbornane skeleton and having a phthalimide skeleton (the second acid dianhydride) is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more. In the above-mentioned first compound, in 100 mol% of the skeletons derived from all the acid dianhydrides, the average proportion of the skeleton derived from the acid dianhydride having no norbornane skeleton and having a phthalimide skeleton (the second acid dianhydride) is preferably 80 mol% or less, more preferably 70 mol% or less, still more preferably 60 mol% or less. When the average proportion of the skeleton derived from the acid dianhydride having no norbornane skeleton and having a phthalimide skeleton is not less than the above lower limit and not more than the above upper limit, the effects of the present invention can be more effectively exerted.

[0045] The above-mentioned first compound preferably has a skeleton derived from an acid dianhydride having no norbornane skeleton and no phthalimide skeleton (norbornane skeleton-free - phthalimide skeleton-free - acid dianhydride; the third acid dianhydride).

[0046] The above-mentioned acid dianhydride having no norbornane skeleton and no phthalimide skeleton (the third acid dianhydride) may or may not have an aromatic skeleton. It is preferable that the above-mentioned third acid dianhydride has no aromatic skeleton. From the viewpoint of enhancing the desmian property, it is preferable that the above-mentioned third acid dianhydride has a non-aromatic double bond.

[0047] Examples of the above-mentioned acid dianhydride having no norbornane skeleton and no phthalimide skeleton (the third acid dianhydride) include bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, and 1,2,4,5-cyclohexanetetracarboxylic dianhydride.

[0048] In the above-mentioned first compound, in 100 mol% of the skeletons derived from all the acid dianhydrides, the average ratio of the skeleton derived from the acid dianhydride having no norbornane skeleton and no phthalimide skeleton (the third acid dianhydride) is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more. In the above-mentioned first compound, in 100 mol% of the skeletons derived from all the acid dianhydrides, the average ratio of the skeleton derived from the acid dianhydride having no norbornane skeleton and no phthalimide skeleton (the third acid dianhydride) is preferably 70 mol% or less, more preferably 60 mol% or less, still more preferably 50 mol% or less. When the average ratio of the skeleton derived from the above-mentioned third acid dianhydride is not less than the above lower limit and not more than the above upper limit, the effects of the present invention can be more effectively exerted.

[0049] The above-mentioned first compound preferably has a skeleton derived from an aliphatic diamine compound. In this case, the dielectric tangent of the cured product can be further lowered, and the thermal dimensional stability of the cured product can be further enhanced.

[0050] The above-mentioned aliphatic diamine compound preferably has a cyclohexane skeleton, preferably has a polycyclic skeleton, and more preferably has a tricyclodecane skeleton or a norbornane skeleton. That is, the above-mentioned first compound preferably has a skeleton derived from an aliphatic diamine compound having a cyclohexane skeleton (an aliphatic diamine compound containing a cyclohexane skeleton). The above-mentioned first compound preferably has a skeleton derived from an aliphatic diamine compound having a polycyclic skeleton (an aliphatic diamine compound containing a polycyclic skeleton). The above-mentioned first compound more preferably has a skeleton derived from an aliphatic diamine compound having a tricyclodecane skeleton (an aliphatic diamine compound containing a tricyclodecane skeleton). The above-mentioned first compound more preferably has a skeleton derived from an aliphatic diamine compound having a norbornane skeleton (an aliphatic diamine compound containing a norbornane skeleton). In these cases, the dielectric tangent of the cured product can be further lowered, and the thermal dimensional stability of the cured product can be further enhanced.

[0051] A polycyclic skeleton refers to a structure having a plurality of cyclic skeletons connected in series. Specifically, a polycyclic skeleton is a skeleton in which two or more rings are integrated in a form where each of them shares two or more atoms, and it is a skeleton having a condensed ring. The above polycyclic skeleton is not, for example, a skeleton in which an alkylene group exists between two rings.

[0052] The above polycyclic skeleton preferably includes a cyclohexane skeleton. Examples of the polycyclic skeleton including the cyclohexane skeleton include a tricyclodecane skeleton, a norbornane skeleton, and an adamantane skeleton. The polycyclic skeleton including the cyclohexane skeleton may be a tricyclodecane skeleton.

[0053] For example, the tricyclodecane skeleton in the above first compound may be a skeleton represented by the following formula (11). In the following formula (11), the right end and the left end are bonding sites with other groups.

[0054]

Chemical formula

[0055] Examples of the above aliphatic diamine compound include dimer diamine, tricyclodecane diamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(aminomethyl)norbornane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.02,6]decane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, isophoronediamine, 4,4'-methylenebis(cyclohexylamine), and 4,4'-methylenebis(2-methylcyclohexylamine). Only one kind of the above aliphatic diamine compound may be used, or two or more kinds may be used in combination.

[0056] From the viewpoint of further reducing the dielectric tangent of the cured product, it is preferable that the first compound has a skeleton derived from a dimer diamine. The skeleton derived from the dimer diamine is a flexible skeleton. Therefore, when the first compound has a skeleton derived from the dimer diamine, the sheet property of a resin film such as a B-stage film can be improved. In addition, since the stress relaxation property of the cured product can be enhanced, the occurrence of warpage can be effectively suppressed, and the reliability of a multilayer printed wiring board or the like can be enhanced.

[0057] 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 Cognis Japan, Ltd., a hydrogenated product of Versamine 551), PRIAMINE 1075, and PRIAMINE 1074 (trade names, both manufactured by Croda Japan, Ltd.).

[0058] In the first compound, in 100 mol% of the skeleton derived from all diamine compounds, the average ratio of the skeleton derived from the dimer diamine is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 25 mol% or more, preferably 90 mol% or less, more preferably 70 mol% or less, and still more preferably 50 mol% or less. When the average ratio of the skeleton derived from the dimer diamine is below the above upper limit, the dielectric tangent of the cured product can be further reduced, and the flexibility of the resin film can be enhanced. When the average ratio of the skeleton derived from the dimer diamine is above the above lower limit, smear can be more effectively removed by desmear treatment while keeping the linear expansion coefficient low, and the compatibility of the resin material can be further enhanced.

[0059] From the viewpoint of more effectively exerting the effects of the present invention, the above-mentioned first compound preferably has an aromatic ring. The above-mentioned first compound may have only one aromatic ring or may have a plurality of aromatic rings. The above-mentioned first compound may be derived from an aromatic diamine compound and may have the above-mentioned aromatic ring. The above-mentioned first compound may have a skeleton derived from an aromatic diamine compound.

[0060] From the viewpoint of further lowering the dielectric tangent of the cured product and enhancing the thermal dimensional stability of the cured product, the above-mentioned first compound has a structural unit having an imide bond as a repeating structural unit.

[0061] The structural unit having the above-mentioned imide bond may contain a skeleton derived from an acid dianhydride having the above-mentioned norbornane skeleton (first acid dianhydride). The structural unit having the above-mentioned imide bond may contain a skeleton derived from an acid dianhydride having no above-mentioned norbornane skeleton and having a phthalimide skeleton (second acid dianhydride). The structural unit having the above-mentioned imide bond may contain a skeleton derived from an acid dianhydride having no above-mentioned norbornane skeleton and no phthalimide skeleton (third acid dianhydride).

[0062] The above-mentioned first compound preferably has a maleimide skeleton or a benzoxazine skeleton, more preferably has a maleimide skeleton or a benzoxazine skeleton at the terminal, and even more preferably has a maleimide skeleton or a benzoxazine skeleton at both terminals. From the viewpoint of setting the curing temperature to 200°C or lower, the above-mentioned first compound is particularly preferably a bismaleimide compound.

[0063] The molecular weight of the above-mentioned first compound exceeds 1000, preferably 1500 or more, more preferably 3000 or more, even more preferably 3100 or more, preferably 50000 or less, more preferably 20000 or less, even more preferably 10000 or less, and particularly preferably 7000 or less. When the molecular weight of the above-mentioned first compound is within the above lower limit and the above upper limit, the effects of the present invention can be more effectively exerted.

[0064] When the first compound is not a polymer and the structural formula of the first compound can be specified, the molecular weight of the first compound means the molecular weight calculated from the structural formula. When the first compound is a polymer, the molecular weight of the first compound indicates the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0065] In 100% by weight of the components excluding the filler and the solvent in the resin material, the content of the first compound is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 12% by weight or more, particularly preferably 15% by weight or more, and preferably 40% by weight or less, more preferably 30% by weight or less. When the content of the first compound is within the above lower limit and the above upper limit, the effects of the present invention can be more effectively exerted.

[0066] In 100% by weight of the total content of the first compound and the second compound, the content of the first compound is preferably 20% by weight or more, more preferably 40% by weight or more, preferably 80% by weight or less, more preferably 70% by weight or less. When the content of the first compound is within the above lower limit and the above upper limit, the effects of the present invention can be more effectively exerted.

[0067] [Second Compound] The resin material according to the present invention contains a second compound having an aromatic skeleton. The second compound does not have a structural unit having an imide skeleton as a repeating structural unit. The second compound is a thermosetting compound. Only one kind of the second compound may be used, or two or more kinds may be used in combination.

[0068] Examples of the second compound include maleimide compounds, epoxy compounds, cyanate compounds, vinyl compounds, phenoxy compounds, oxetane compounds, polyarylate compounds, diallyl phthalate compounds, episulfide compounds, (meth)acrylic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, and silicone compounds.

[0069] The second compound preferably contains a maleimide compound, an epoxy compound, or a vinyl compound, more preferably contains a maleimide compound or an epoxy compound, and still more preferably contains an epoxy compound.

[0070] The molecular weight of the second compound is preferably 1000 or less, more preferably 900 or less, still more preferably 800 or less, and particularly preferably 700 or less. The molecular weight of the second compound is preferably 100 or more, more preferably 200 or more. When the molecular weight of the second compound is not less than the lower limit and not more than the upper limit, the effects of the present invention can be more effectively exerted. Further, when the molecular weight of the second compound is not more than the upper limit, the embedding property of the resin material into irregularities on a substrate or the like and the flexibility of the B-stage film can be enhanced.

[0071] The second compound preferably contains a compound having a molecular weight of 1000 or less, more preferably contains a compound having a molecular weight of 900 or less, still more preferably contains a compound having a molecular weight of 800 or less, and particularly preferably contains a compound having a molecular weight of 700 or less. Further, the second compound preferably contains a compound having a molecular weight of 1000 or less and a compound having a molecular weight exceeding 1000. In this case, the effects of the present invention can be more effectively exerted.

[0072] The resin material preferably contains a second compound having a molecular weight of 1000 or less, more preferably contains a second compound having a molecular weight of 900 or less, still more preferably contains a second compound having a molecular weight of 800 or less, and particularly preferably contains a second compound having a molecular weight of 700 or less. In this case, the effects of the present invention can be more effectively exerted.

[0073] When the second compound is not a polymer and its structural formula can be specified, the molecular weight of the second compound means the molecular weight calculated from the structural formula. When the first compound is a polymer, the molecular weight of the second compound indicates the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0074] <Maleimide compound> The maleimide compound, which is the second compound, is a maleimide compound having an aromatic skeleton. The maleimide compound, which is the second compound, is a maleimide compound that does not have a structural unit having an imide skeleton as a repeating structural unit. Only one kind of the maleimide compound may be used, or two or more kinds may be used in combination.

[0075] In the maleimide compound, which is the second compound, it is preferable that a nitrogen atom in the maleimide skeleton is bonded to an aromatic ring.

[0076] Examples of commercially available products of the maleimide compound, which is the second compound, include "BMI-2300", "BMI-4000", and "BMI-5100" manufactured by Daiwa Kasei Kogyo Co., Ltd., and "MIR-3000" manufactured by Nippon Kayaku Co., Ltd., etc.

[0077] In 100% by weight of the components excluding the filler and the solvent in the resin material, the content of the maleimide compound, which is the second compound, is preferably 1% by weight or more, more preferably 2% by weight or more, still more preferably 3% by weight or more, and preferably 50% by weight or less. When the content of the maleimide compound is within the above lower limit and the above upper limit, the thermal dimensional stability of the cured product can be further enhanced.

[0078] <Epoxy compound> The epoxy compound which is the second compound described above is an epoxy compound having an aromatic skeleton. The epoxy compound which is the second compound described above is an epoxy compound that does not have a structural unit having an imide skeleton as a repeating structural unit. As the epoxy compound, a conventionally known epoxy compound can be used. The epoxy compound is an organic compound having at least one epoxy group. Only one kind of the epoxy compound may be used, or two or more kinds may be used in combination.

[0079] The resin material may contain both the epoxy compound which is the second compound described above and the epoxy compound which is the thermosetting compound X described later. When the resin material contains the second compound other than the epoxy compound, the resin material may not contain the epoxy compound which is the second compound described above, and may contain the epoxy compound which is the thermosetting compound X described later.

[0080] Examples of the epoxy compound which is the second compound described above include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, phenol novolac type epoxy compound, biphenyl type epoxy compound, biphenyl novolac type epoxy compound, bisphenol type epoxy compound, naphthalene type epoxy compound, fluorene type epoxy compound, phenol aralkyl type epoxy compound, naphthol aralkyl type epoxy compound, anthracene type epoxy compound, naphthylene ether type epoxy compound, and the like.

[0081] The epoxy compound which is the second compound described above may be a glycidyl ether compound. The glycidyl ether compound is a compound having at least one glycidyl ether group.

[0082] From the viewpoint of further lowering the dielectric tangent of the cured product and enhancing the thermal dimensional stability and flame retardancy of the cured product, it is preferable that the epoxy compound which is the second compound described above contains an epoxy compound having a naphthalene skeleton or a phenyl skeleton.

[0083] From the viewpoint of further reducing the dielectric loss tangent of the cured product and improving the coefficient of thermal expansion (CTE) of the cured product, the epoxy compound as the second compound preferably contains an epoxy compound that is liquid at 25°C and an epoxy compound that is solid at 25°C.

[0084] The viscosity at 25°C of the epoxy compound that is liquid at 25°C is preferably 1000 mPa·s or less, and more preferably 500 mPa·s or less.

[0085] The viscosity of the epoxy compound as the second compound can be measured using, for example, a dynamic viscoelasticity measuring device (such as "VAR-100" manufactured by Rheologica Instruments).

[0086] From the viewpoint of further enhancing the thermal dimensional stability of the cured product, in 100% by weight of the components excluding the solvent in the resin material, the content of the epoxy compound as the second compound is preferably 3% by weight or more, more preferably 6% by weight or more, preferably 15% by weight or less, and more preferably 12% by weight or less.

[0087] In 100% by weight of the components excluding the filler and the solvent in the resin material, the content of the epoxy compound as the second compound is preferably 10% by weight or more, more preferably 20% by weight or more, preferably 50% by weight or less, and more preferably 40% by weight or less. When the content of the epoxy compound is within the above lower limit and the above upper limit, the thermal dimensional stability of the cured product can be further enhanced.

[0088] <Vinyl compound> The vinyl compound as the second compound is a vinyl compound having an aromatic skeleton. The vinyl compound as the second compound is a vinyl compound that does not have a structural unit having an imide skeleton as a repeating structural unit. As the vinyl compound, conventionally known vinyl compounds can be used. Only one kind of the vinyl compound may be used, or two or more kinds may be used in combination.

[0089] Examples of the vinyl compound as the second compound include styrene compounds, acrylate compounds, divinyl compounds, etc. Examples of the divinyl compound include divinyl benzyl ether compounds. The vinyl compound may be a divinyl compound having an aliphatic skeleton or a divinyl ether compound.

[0090] Examples of commercially available products of the vinyl compound (styrene compound) as the second compound include "OPE-2St" manufactured by Mitsubishi Gas Chemical Company, Inc.

[0091] The resin material may contain both the vinyl compound as the second compound and the vinyl compound as the thermosetting compound X described later. When the resin material contains a second compound other than the vinyl compound, the resin material may not contain the vinyl compound as the second compound, or may contain the vinyl compound as the thermosetting compound X described later.

[0092] In 100% by weight of the components excluding the filler and solvent in the resin material, the content of the vinyl compound as the second compound is preferably 1% by weight or more, more preferably 5% by weight or more, still more preferably 10% by weight or more, preferably 70% by weight or less, and more preferably 60% by weight or less. When the content of the vinyl compound is not less than the lower limit and not more than the upper limit, the thermal dimensional stability of the cured product can be further enhanced.

[0093] [Thermosetting compound other than the second compound (thermosetting compound X)] The resin material according to the present invention preferably contains a thermosetting compound other than the second compound (hereinafter sometimes referred to as thermosetting compound X). The thermosetting compound X is different from the second compound. The thermosetting compound X is different from the first compound. The thermosetting compound X is a thermosetting compound having no aromatic skeleton or a thermosetting compound having a structural unit having an imide bond as a repeating structural unit. Only one kind of the thermosetting compound X may be used, or two or more kinds may be used in combination.

[0094] Examples of the above-mentioned thermosetting compound X include maleimide compounds, epoxy compounds, cyanate compounds, vinyl compounds, phenoxy compounds, oxetane compounds, polyarylate compounds, diallyl phthalate compounds, episulfide compounds, (meth)acrylic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, and silicone compounds.

[0095] The above-mentioned thermosetting compound X preferably contains a maleimide compound, an epoxy compound, or a vinyl compound, more preferably contains a maleimide compound or an epoxy compound, and even more preferably contains an epoxy compound.

[0096] Examples of the epoxy compound as the above-mentioned thermosetting compound X include epoxy compounds having an adamantane skeleton and epoxy compounds having a tricyclodecane skeleton.

[0097] Commercially available products of the epoxy compound as the above-mentioned thermosetting compound X include, for example, "PB3600" (polybutadiene-type skeleton epoxy resin) manufactured by Daicel Corporation and "Foldi E101" manufactured by Nissan Chemical Industries, Ltd.

[0098] Commercially available products of the maleimide compound as the above-mentioned thermosetting compound X include, for example, "BMI-3000" and "BMI-689" manufactured by Designer Molecules Inc.

[0099] In 100% by weight of the components excluding the filler and the solvent in the above resin material, the content of the above-mentioned thermosetting compound X is preferably 1% by weight or more, more preferably 3% by weight or more, even more preferably 5% by weight or more, preferably 50% by weight or less, and more preferably 30% by weight or less. When the content of the above-mentioned thermosetting compound X is within the above lower limit and the above upper limit, the flexibility of the cured product can be further enhanced. Also, when the content of the above-mentioned thermosetting compound X is within the above lower limit and the above upper limit, the thermal dimensional stability of the cured product may also be further enhanced.

[0100] Filling material The resin material preferably contains a filling material.

[0101] Examples of the filling material include organic filling materials and inorganic filling materials. The filling material is preferably an insulating filling material. Only one type of the filling material may be used, or two or more types may be used in combination.

[0102] Examples of the organic filling material include particulate materials composed of benzoxazine resin, benzoxazole resin, fluororesin, acrylic resin, styrene resin, etc. Examples of the fluororesin include polytetrafluoroethylene (PTFE). By using fluororesin particles as the organic filling material, the relative permittivity and dielectric loss tangent of the cured product of the resin material can be further reduced.

[0103] Examples of the inorganic filling material include silica, talc, clay, mica, hydrotalcite, alumina, magnesium oxide, aluminum hydroxide, aluminum nitride, boron nitride, diamond, etc.

[0104] From the viewpoint of further reducing the dielectric loss tangent of the cured product of the resin material and further reducing the dimensional change due to heat of the cured product of the resin material, the filling material is preferably an inorganic filling material. The resin material preferably contains an inorganic filling material.

[0105] The inorganic filling material is preferably an inorganic filling material having a thermal conductivity of 10 W / mK or more, such as alumina and boron nitride. In this case, the heat dissipation performance can be enhanced.

[0106] From the viewpoint of enhancing the thermal dimensional stability, the inorganic filling material is preferably an anisotropic inorganic filling material.

[0107] The inorganic filler is preferably silica or alumina, more preferably silica, and even more preferably fused silica. In this case, the surface roughness of the cured product of the resin material can be reduced, the adhesion strength between the cured product and the metal layer can be further increased, a finer wiring can be formed on the surface of the cured product, and good insulation reliability can be imparted to the cured product. In particular, by using silica as the inorganic filler, the thermal expansion coefficient of the cured product becomes even lower, and the dielectric tangent of the cured product becomes even lower. Also, the dielectric constant of the cured product can be improved. The shape of the silica is preferably spherical.

[0108] From the viewpoint of increasing the thermal conductivity and enhancing the insulation, the inorganic filler is preferably alumina.

[0109] The inorganic filler is preferably spherical, and more preferably spherical silica. In this case, the surface roughness of the surface of the cured product is effectively reduced, and furthermore, the adhesion strength between the cured product and the metal layer is effectively increased. When the inorganic filler is spherical, the aspect ratio of the inorganic filler is preferably 2 or less, and more preferably 1.5 or less.

[0110] The inorganic filler is preferably surface-treated, more preferably a surface-treated product with a coupling agent, and even more preferably a surface-treated product with a silane coupling agent. By surface-treating the inorganic filler, the surface roughness of the surface of the roughened cured product becomes even smaller, and the adhesion strength between the cured product and the metal layer becomes even higher. Also, by surface-treating the inorganic filler, a finer wiring can be formed on the surface of the cured product, and better insulation reliability between wirings and interlayer insulation reliability can be imparted to the cured product.

[0111] Examples of the coupling agent include silane coupling agents, titanium coupling agents, aluminum coupling agents, etc. Examples of the silane coupling agent include methacryl silane, acrylic silane, amino silane, imidazole silane, vinyl silane, epoxy silane, etc.

[0112] The average particle size of the organic filler as the filler is preferably 1 μm or less. When the average particle size of the organic filler is below the above 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 enhanced. The average particle size of the organic filler may be 50 nm or more.

[0113] The average particle size of the inorganic filler as the filler is preferably 50 nm or more, more preferably 100 nm or more, still more preferably 500 nm or more, and preferably 5 μm or less, more preferably 3 μm or less, still more preferably 1 μm or less. When the average particle size of the inorganic filler is above the above lower limit and below the above 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 enhanced.

[0114] As the average particle size of the filler, the value of the median diameter (d50) at 50% is adopted. The average particle size can be measured using a particle size distribution measuring device based on the laser diffraction scattering method.

[0115] In 100% by weight of the components excluding the solvent in the above resin material, the content of the above filler is preferably 50% by weight or more, more preferably 55% by weight or more, still more preferably 60% by weight or more, particularly preferably 70% by weight or more, preferably 90% by weight or less, more preferably 85% by weight or less, still more preferably 80% by weight or less, particularly preferably 75% by weight or less. When the content of the above filler is at least the above lower limit, the dielectric tangent is effectively reduced. When the content of the above filler is at most the above upper limit, the thermal dimensional stability can be enhanced and the warpage of the cured product can be effectively suppressed. When the content of the above filler is at least the above lower limit and at most the above upper limit, the surface roughness of the surface of the cured product can be further reduced, and a finer wiring can be formed on the surface of the cured product.

[0116] In 100% by weight of the components excluding the solvent in the above resin material, the content of the above organic filler is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 15% by weight or more, particularly preferably 20% by weight or more, preferably 75% by weight or less, more preferably 60% by weight or less, still more preferably 50% by weight or less, particularly preferably 40% by weight or less. When the content of the above organic filler is at least the above lower limit, the dielectric tangent is effectively reduced. When the content of the above organic filler is at most the above upper limit, the thermal dimensional stability can be enhanced and the warpage of the cured product can be effectively suppressed. When the content of the above organic filler is at least the above lower limit and at most the above upper limit, the surface roughness of the surface of the cured product can be further reduced, and a finer wiring can be formed on the surface of the cured product.

[0117] In 100% by weight of the components excluding the solvent in the above resin material, the content of the above inorganic filler is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 65% by weight or more, particularly preferably 68% by weight or more, preferably 90% by weight or less, more preferably 85% by weight or less, still more preferably 80% by weight or less, and particularly preferably 75% by weight or less. When the content of the above inorganic filler is at least the above lower limit, the dielectric loss tangent is effectively reduced. When the content of the above inorganic filler is at most the above upper limit, the thermal dimensional stability can be enhanced and the warpage of the cured product can be effectively suppressed. When the content of the above inorganic filler is at least the above lower limit and at most the above upper limit, the surface roughness of the surface of the cured product can be further reduced, and a finer wiring can be formed on the surface of the cured product. Further, with such a content of the inorganic filler, it is possible to lower the coefficient of thermal expansion of the cured product and at the same time improve the smear removability.

[0118] [Curing agent] The above resin material preferably contains a curing agent. The above curing agent is not particularly limited. As the above curing agent, a conventionally known curing agent can be used. Only one kind of the above curing agent may be used, or two or more kinds may be used in combination.

[0119] Examples of the above curing agent include phenolic compounds (phenolic curing agents), active ester compounds, carbodiimide compounds (carbodiimide curing agents), amine compounds (amine curing agents), thiol compounds (thiol curing agents), phosphine compounds, dicyandiamide, and acid anhydrides. The above curing agent preferably has a functional group capable of reacting with the epoxy group of the above epoxy compound.

[0120] From the viewpoint of further enhancing the thermal dimensional stability, it is preferable that the above curing agent contains at least one component selected from a phenol compound, an active ester compound, a carbodiimide compound, and an acid anhydride. From the viewpoint of further enhancing the thermal dimensional stability, it is more preferable that the above curing agent contains at least one component selected from a phenol compound, an active ester compound, and a carbodiimide compound, it is still more preferable to contain an active ester compound, and it is particularly preferable to contain both a phenol compound and an active ester compound.

[0121] From the viewpoint of further enhancing the thermal dimensional stability, it is preferable that the above thermosetting compound contains an epoxy compound and the above curing agent contains both a phenol compound and an active ester compound.

[0122] Examples of the above phenol compound include novolak-type phenol, biphenyl-type phenol, naphthalene-type phenol, dicyclopentadiene-type phenol, aralkyl-type phenol, and dicyclopentadiene-type phenol.

[0123] Examples of commercially available products of the above phenol compound include novolak-type phenol ("TD-2091" manufactured by DIC Corporation), biphenyl novolak-type phenol ("MEH-7851" manufactured by Meiwafosis Co., Ltd.), aralkyl-type phenol compound ("MEH-7800" manufactured by Meiwafosis Co., Ltd.), and phenol having an aminotriazine skeleton ("LA-1356" and "LA-3018-50P" manufactured by DIC Corporation).

[0124] The above active ester compound refers to a compound containing at least one ester bond in the structure and having an aliphatic chain, an aliphatic ring, or an aromatic ring bonded to both sides of the ester bond. The active ester compound is obtained, for example, by a condensation reaction between a carboxylic acid compound or a thiocarboxylic acid compound and a hydroxy compound or a thiol compound. Examples of the active ester compound include the compound represented by the following formula (1).

[0125]

Chemical formula

[0126] 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 a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, and the like. Examples of the substituent include a hydrocarbon group. The number of carbon atoms of the hydrocarbon group is preferably 12 or less, more preferably 6 or less, and still more preferably 4 or less.

[0127] In the above formula (1), examples of the combination 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. Further, in the above formula (1), examples of the combination of X1 and X2 include a combination of a naphthalene ring which may have a substituent and a naphthalene ring which may have a substituent.

[0128] The above active ester compound is not particularly limited. From the viewpoint of further enhancing the thermal dimensional stability and flame retardancy, the active ester compound is preferably an active ester compound having two or more aromatic skeletons. From the viewpoint of lowering the dielectric tangent of the cured product and enhancing the thermal dimensional stability of the cured product, it is more preferable that the main chain skeleton of the active ester compound has a naphthalene ring.

[0129] Examples of commercially available products of the above active ester compound include "HPC-8000-65T", "EXB9416-70BK", and "EXB8100-65T" manufactured by DIC Corporation.

[0130] The above carbodiimide compound is a compound having a structural unit represented by the following formula (2). In the following formula (2), the right end and the left end are bonding sites with other groups. Only one kind of the above carbodiimide compound may be used, or two or more kinds may be used in combination.

[0131] [Chemical formula]

[0132] In the above formula (2), X represents an alkylene group, a group in which a substituent is bonded to the alkylene group, a cycloalkylene group, a group in which a substituent is bonded to the cycloalkylene group, an arylene group, or a group in which a substituent is bonded to the arylene group, and p represents an integer from 1 to 5. When there are a plurality of X, the plurality of X may be the same or different.

[0133] In one preferred embodiment, at least one X is an alkylene group, a group in which a substituent is bonded to the alkylene group, a cycloalkylene group, or a group in which a substituent is bonded to the cycloalkylene group.

[0134] Examples of commercially available products of the above 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., and "Stabaxol P", "Stabaxol P400", and "Hy-Cadyl 510" manufactured by Rhein Chemie Co., Ltd.

[0135] Examples of the above acid anhydrides include tetrahydrophthalic anhydride and alkylstyrene-maleic anhydride copolymer.

[0136] Examples of commercially available products of the above acid anhydrides include "Ricacid TDA-100" manufactured by Shin Nippon Rika Co., Ltd.

[0137] The total content of the above active ester compound and the above phenolic compound with respect to 100 parts by weight of the above epoxy compound is preferably 70 parts by weight or more, more preferably 85 parts by weight or more, preferably 150 parts by weight or less, and more preferably 120 parts by weight or less. When the total content of the above active ester compound and the above phenolic compound is within the above lower limit and the above 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] In 100% by weight of the components excluding the filler and the solvent in the above resin material, the total content of the above first compound, the above second compound, the above thermosetting compound X, and the above curing agent is preferably 50% by weight or more, more preferably 60% by weight or more, and preferably 95% by weight or less. When the total content is within the above lower limit and the above upper limit, the curability is further improved, and the thermal dimensional stability can be further enhanced.

[0139] [Curing accelerator] The above resin material preferably contains a curing accelerator. By using the above curing accelerator, the curing rate becomes even faster. By quickly curing the resin material, the crosslinked structure in the cured product becomes uniform, the number of unreacted functional groups decreases, and as a result, the crosslink density increases. The above curing accelerator is not particularly limited, and conventionally known curing accelerators can be used. Only one kind of the above curing accelerator may be used, or two or more kinds may be used in combination.

[0140] Examples of the above curing accelerator include anionic curing accelerators such as imidazole compounds, cationic curing accelerators such as amine compounds, curing accelerators other than anionic and cationic curing accelerators such as phosphorus compounds and organometallic compounds, and radical curing accelerators such as peroxides.

[0141] 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-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-dihydroxymethylimidazole, and the like.

[0142] Examples of the amine compound include diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, 4,4-dimethylaminopyridine, and the like.

[0143] Examples of the phosphorus compound include triphenylphosphine compounds and the like.

[0144] Examples of the organometallic compound include zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonato cobalt(II), trisacetylacetonato cobalt(III), and the like.

[0145] Examples of the peroxide include dicumyl peroxide, perhexyl 25B, and the like.

[0146] From the viewpoint of further suppressing the curing temperature and effectively suppressing the warpage of the cured product, the curing accelerator preferably contains the anionic curing accelerator, and more preferably contains the imidazole compound.

[0147] A curing accelerator that is a peroxide and an anionic curing accelerator may be used in combination. In particular, when a vinyl compound and an epoxy compound are used in combination, a better cured product may be obtained by using the above two kinds of curing accelerators.

[0148] From the viewpoint of further suppressing the curing temperature and effectively suppressing the warpage of the cured product, in 100% by weight of the curing accelerator, the content of the anionic curing accelerator is preferably 20% by weight or more, more preferably 50% by weight or more, still more preferably 70% by weight or more, and most preferably 100% by weight (total amount). Therefore, the curing accelerator is most preferably the anionic curing accelerator.

[0149] The content of the curing accelerator is not particularly limited. In 100% by weight of the components excluding the filler and the solvent in the resin material, 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 within the above lower limit and above upper limit, the resin material cures efficiently. If the content of the curing accelerator is in a more preferable range, the storage stability of the resin material becomes even higher, and a better cured product can be obtained.

[0150] [Thermoplastic resin] The resin material preferably contains a thermoplastic resin. Examples of the thermoplastic resin include polyvinyl acetal resin, polyimide resin, and phenoxy resin. Only one kind of the thermoplastic resin may be used, or two or more kinds may be used in combination.

[0151] From the viewpoint of effectively reducing the dielectric loss tangent and effectively enhancing the adhesion of the metal wiring regardless of the curing environment, the above thermoplastic resin is preferably a phenoxy resin. By using the phenoxy resin, deterioration of the embedding property of the resin film into the holes or unevenness of the circuit board and non-uniformity of the inorganic filler can be suppressed. Further, by using the phenoxy resin, the dispersibility of the inorganic filler becomes good because the melt viscosity can be adjusted, and in the curing process, it becomes difficult for the resin composition or the B-stage product to wet and spread in an unintended area.

[0152] The phenoxy resin contained in the above resin material is not particularly limited. As the above phenoxy resin, conventionally known phenoxy resins can be used. Only one kind of the above phenoxy resin may be used, or two or more kinds may be used in combination.

[0153] Examples of the above phenoxy resin include phenoxy resins having skeletons such as a bisphenol A type skeleton, a bisphenol F type skeleton, a bisphenol S type skeleton, a biphenyl skeleton, a novolak skeleton, a naphthalene skeleton, and an imide skeleton.

[0154] Examples of commercially available products of the above phenoxy resin include "YP50", "YP55", and "YP70" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and "1256B40", "4250", "4256H40", "4275", "YX6954BH30", and "YX8100BH30" manufactured by Mitsubishi Chemical Corporation.

[0155] From the viewpoints of handleability, plating peel strength at low roughness, and adhesion between the insulating layer and the metal layer, the above thermoplastic resin is preferably a polyimide resin (polyimide compound).

[0156] From the viewpoint of improving solubility, the above polyimide compound is preferably a polyimide compound obtained by a method of reacting a tetracarboxylic dianhydride with a diamine dimer.

[0157] Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyl diphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl propane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, and bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, etc.

[0158] 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 Cognis Japan Ltd., hydrogenated product of Versamine 551), PRIAMINE 1075, PRIAMINE 1074 (trade names, both manufactured by Croda Japan Ltd.), etc.

[0159] Incidentally, the above polyimide compound may have an acid anhydride structure, a maleimide structure, or a citraconimide structure at its terminals. In this case, the above polyimide compound and the epoxy resin can be reacted with each other. By reacting the above polyimide compound with the epoxy resin, the thermal dimensional stability of the cured product can be enhanced.

[0160] From the viewpoint of obtaining a resin material with even better storage stability, the weight average molecular weight of the above thermoplastic resin, the above polyimide resin, and the above phenoxy resin is preferably 5000 or more, more preferably 10000 or more, preferably 100000 or less, and more preferably 50000 or less.

[0161] The above weight average molecular weight of the above thermoplastic resin, the above polyimide resin, and the above phenoxy resin indicates the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0162] The content of the above thermoplastic resin, the above polyimide resin, and the above phenoxy resin is not particularly limited. In 100% by weight of the components excluding the above inorganic filler and the above solvent in the resin material, the content of the above thermoplastic resin (when the thermoplastic resin is a polyimide resin or a phenoxy resin, the content of the polyimide resin or the phenoxy resin) is preferably 1% by weight or more, more preferably 2% by weight or more, preferably 30% by weight or less, and more preferably 20% by weight or less. When the content of the above thermoplastic resin is equal to or more than the above lower limit and equal to or less than the above upper limit, the embedding property of the resin material into the holes or unevenness of the circuit board becomes good. When the content of the above thermoplastic resin is equal to or more than the above lower limit, the formation of the resin film becomes even easier, and a better insulating layer can be obtained. When the content of the above thermoplastic resin is equal to or less than the above upper limit, the thermal expansion coefficient of the cured product becomes even lower. When the content of the above thermoplastic resin is equal to or less than the above upper limit, the surface roughness of the surface of the cured product becomes even smaller, and the adhesive strength between the cured product and the metal layer becomes even higher.

[0163] [Elastomer] The above resin material either does not contain or contains an elastomer. By using the above elastomer, the flexibility of the B-stage film and the flexibility of the cured product can be enhanced. The above elastomer may have a thermosetting functional group.

[0164] Examples of the above elastomer include an elastomer having a polybutadiene structure, an elastomer having a polysiloxane structure, an elastomer having a polyisoprene structure, an elastomer having a polyisobutylene structure, and an elastomer having a polyalkylene structure.

[0165] [Solvent] The above resin material either does not contain or contains a solvent. By using the above solvent, the viscosity of the resin material can be controlled within a suitable range, and the coatability of the resin material can be enhanced. Further, the above solvent may be used to obtain a slurry containing the above inorganic filler. Only one type of the above solvent may be used, or two or more types may be used in combination.

[0166] Examples of the above 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.

[0167] Most of the above solvents are preferably removed when the above resin composition is formed into a film. Therefore, the boiling point of the above solvent is preferably 200°C or lower, more preferably 180°C or lower. The content of the above solvent in the above resin composition is not particularly limited. In consideration of the coatability of the above resin composition, etc., the content of the above solvent can be appropriately changed.

[0168] 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 10% by weight or less, and more preferably 5% by weight or less.

[0169] [Other components] For the purpose of improving impact resistance, heat resistance, resin compatibility, workability, etc., the resin material may contain a leveling agent, a flame retardant, a coupling agent, a coloring agent, an antioxidant, an ultraviolet degradation inhibitor, an antifoaming agent, a thickening agent, a thixotropic agent, and the like.

[0170] Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent. Examples of the silane coupling agent include vinyl silane, amino silane, imidazole silane, and epoxy silane.

[0171] (Resin film) A resin film (B-stage product / B-stage film) can be obtained by molding the above-described resin composition into a film shape. The resin material is preferably a resin film. The resin film is preferably a B-stage film.

[0172] Examples of the method for molding the resin composition into a film shape to obtain a resin film include the following methods. An extrusion molding method in which the resin composition is melt-kneaded using an extruder and then molded into a film shape by a T-die or a circular die, etc. A casting molding method in which a resin composition containing a solvent is cast and molded into a film shape. Other conventionally known film molding methods. Since it is possible to cope with thinning, the extrusion molding method or the casting molding method is preferred. The film includes a sheet.

[0173] By molding the resin composition into a film shape and heating and drying it at, for example, 50°C to 150°C for 1 minute to 10 minutes so that the curing by heat does not proceed too much, a resin film that is a B-stage film can be obtained.

[0174] A film-like resin composition obtainable by the drying process as described above is referred to as a B-stage film. The above B-stage film is in a semi-cured state. The semi-cured product is not completely cured and the curing can further proceed.

[0175] The above resin film does not have to be a prepreg. When the above resin film is not a prepreg, migration does not occur along a glass cloth or the like. Also, when laminating or pre-curing the resin film, unevenness caused by the glass cloth does not occur on the surface.

[0176] The above resin film can be used in the form of a laminated film including a metal foil or a base film and a resin film laminated on the surface of the metal foil or the base material. The above metal foil is preferably a copper foil.

[0177] Examples of the above base film of the laminated film include polyester resin films such as polyethylene terephthalate films and polybutylene terephthalate films, olefin resin films such as polyethylene films and polypropylene films, and polyimide resin films. The surface of the above base film may be subjected to a release treatment as necessary.

[0178] From the viewpoint of more uniformly controlling the degree of curing of the resin film, the thickness of the above resin film is preferably 5 μm or more and preferably 200 μm or less. When the above resin film is used as an insulating layer of a circuit, the thickness of the insulating layer formed by the above resin film is preferably not less than the thickness of the conductor layer (metal layer) forming the circuit. The thickness of the above insulating layer is preferably 5 μm or more and preferably 200 μm or less.

[0179] (Other details of the resin material) After heating the above resin material at 130°C for 60 minutes for preliminary curing, it is heated at 200°C for 90 minutes to obtain a cured product of the resin material. In this case, the dielectric tangent (Df) of the obtained cured product at 23°C and a frequency of 5.8 GHz is preferably 3.0×10 -3 Hereinafter, more preferably 2.8×10 -3 Hereinafter, even more preferably 2.5×10 -3 Hereinafter, particularly preferably 2.3×10 -3 Hereinafter. The dielectric tangent (Df) of the above cured product may be 1.5×10 -3 or more, and may be 1.8×10 -3 or more.

[0180] The dielectric tangent (Df) of the above cured product is more specifically measured as follows.

[0181] The film-shaped resin material (resin film) is heated at 130°C for 60 minutes for preliminary curing, and then heated at 200°C for 90 minutes to obtain a cured product of the resin material. The obtained cured product is cut into pieces with a width of 2 mm and a length of 80 mm, and 10 pieces are stacked. Using the "Dielectric Constant Measuring Device CP521 by Cavity Resonance Perturbation Method" manufactured by Kanto Electronic Application Development Co., Ltd. and the "Network Analyzer N5224A PNA" manufactured by Keysight Technologies, the dielectric tangent is measured at room temperature (23°C) and a frequency of 5.8 GHz by the cavity resonance method.

[0182] After heating the above resin material at 130°C for 60 minutes for preliminary curing, it is heated at 200°C for 90 minutes to obtain a cured product of the resin material. In this case, the average coefficient of linear expansion (CTE) of the obtained cured product from 25°C to 150°C at a tensile load of 33 mN is preferably 33 ppm / °C or less, more preferably 30 ppm / °C or less, even more preferably 27 ppm / °C or less, particularly preferably 24 ppm / °C or less, and most preferably 22 ppm / °C or less. The average coefficient of linear expansion (CTE) of the above cured product may be 17 ppm / °C or more, and may be 19 ppm / °C or more.

[0183] The average coefficient of linear expansion (CTE) of the above cured product is more specifically measured as follows.

[0184] The film-shaped resin material (resin film) is heated at 130°C for 60 minutes for temporary curing, and then heated at 200°C for 90 minutes to obtain a cured product of the resin material. The obtained cured product is cut into a size of 3 mm × 25 mm. Using a thermomechanical analyzer (for example, "EXSTAR TMA / SS6100" manufactured by SII NanoTechnology Inc.), the average linear expansion coefficient (ppm / °C) of the cut cured product from 25°C to 150°C is calculated under the conditions of a tensile load of 33 mN and a heating rate of 5°C / min.

[0185] (Semiconductor device, printed wiring board, copper-clad laminate, and multilayer printed wiring board) The above resin material is suitably used for forming a mold resin for embedding a semiconductor chip in a semiconductor device.

[0186] The above resin material is suitably used for alternative applications of liquid crystal polymer (LCP), millimeter-wave antenna applications, and rewiring layer applications. Further, the above resin material is suitably used not only for the above applications but also for wiring formation applications in general.

[0187] The above resin material is suitably used as an insulating material. The above resin material is suitably used for forming an insulating layer in a printed wiring board.

[0188] The above printed wiring board can be obtained, for example, by thermocompression molding of the above resin material.

[0189] A laminated target member having a metal layer on one or both surfaces can be laminated on the above resin film. A laminated structure can be suitably obtained, which includes a laminated target member having a metal layer on its surface and a resin film laminated on the surface of the above metal layer, and the above resin film is the resin material described above. The method of laminating the above resin film and the laminated target member having a metal layer on its surface is not particularly limited, and a known method can be used. For example, using a device such as a parallel plate press or a roll laminator, the above resin film can be laminated on the laminated target member having a metal layer on its surface while heating or while applying pressure without heating.

[0190] The material of the above metal layer is preferably copper.

[0191] The member to be laminated having the above metal layer on its surface may be a metal foil such as a copper foil.

[0192] The above resin material is preferably used to obtain a copper-clad laminate. As an example of the above copper-clad laminate, a copper-clad laminate including a copper foil and a resin film laminated on one surface of the copper foil can be mentioned.

[0193] The thickness of the copper foil of the above copper-clad laminate is not particularly limited. The thickness of the copper foil is preferably in the range of 1 μm to 50 μm. Further, in order to increase the adhesion strength between the cured product of the above resin material and the copper foil, the copper foil preferably has fine irregularities on its surface. The method of forming the irregularities is not particularly limited. Examples of the method of forming the irregularities include a forming method by treatment using a known chemical solution.

[0194] The above resin material is preferably used to obtain a multilayer substrate.

[0195] As an example of the above multilayer substrate, a multilayer substrate including a circuit board and an insulating layer laminated on the circuit board can be mentioned. The insulating layer of this multilayer substrate is formed of the above resin material. Further, the insulating layer of the multilayer substrate may be formed of the above resin film of the laminated film using the laminated film. The insulating layer is preferably laminated on the surface of the circuit board where the circuit is provided. A part of the insulating layer is preferably embedded between the above circuits.

[0196] In the above multilayer substrate, it is preferable that the surface of the multilayer substrate on the side opposite to the surface on which the circuit board of the insulating layer is laminated is roughened.

[0197] As the roughening treatment method, a conventionally known roughening treatment method can be used and is not particularly limited. The surface of the insulating layer may be swollen before the roughening treatment.

[0198] Further, it is preferable that the multilayer substrate further includes a copper plating layer laminated on the roughened surface of the insulating layer.

[0199] As another example of the multilayer substrate, there is a multilayer substrate including 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. It is preferable that the insulating layer is formed by curing the resin film using a copper-clad laminate including a copper foil and a resin film laminated on one surface of the copper foil. Further, the copper foil is preferably an etched copper circuit.

[0200] As another example of the multilayer substrate, there is a multilayer substrate including 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 disposed on the circuit board is formed using the resin material. It is preferable that the multilayer substrate further includes a circuit laminated on at least one surface of the insulating layer formed using the resin film.

[0201] In a multilayer printed wiring board among multilayer substrates, a low dielectric tangent is required, and high insulation reliability by an insulating layer is required. In the resin material according to the present invention, the insulation reliability can be effectively increased by reducing the dielectric tangent and increasing the adhesion and etching performance between the insulating layer and the metal layer. Therefore, the resin material according to the present invention is suitably used for forming an insulating layer in a multilayer printed wiring board.

[0202] The multilayer printed wiring board includes, 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. At least one of the insulating layers is a cured product of the resin material.

[0203] 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.

[0204] In the multilayer printed wiring board 11 shown in FIG. 1, a plurality of insulating layers 13 to 16 are laminated on the upper surface 12a of the circuit board 12. The insulating layers 13 to 16 are cured layers. A metal layer 17 is formed in a part of the region of the upper surface 12a of the circuit board 12. Among the plurality of insulating layers 13 to 16, the metal layer 17 is formed in a part of the upper surface region of the insulating layers 13 to 15 other than the insulating layer 16 located on the outer surface opposite to the circuit board 12 side. 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 the respective layers 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 a via hole connection and a through hole connection (not shown).

[0205] In the multilayer printed wiring board 11, the insulating layers 13 to 16 are formed of a cured product of the above resin material. In the present embodiment, since the surfaces of the insulating layers 13 to 16 are roughened, fine holes (not shown) are formed on the surfaces of the insulating layers 13 to 16. Further, the metal layer 17 reaches the inside of the fine holes. In the multilayer printed wiring board 11, the width direction dimension (L) of the metal layer 17 and the width direction dimension (S) of the portion where the metal layer 17 is not formed can be reduced. In the multilayer printed wiring board 11, good insulation reliability is imparted between the upper metal layer and the lower metal layer that are not connected by a via hole connection and a through hole connection (not shown).

[0206] (Roughening treatment and swelling treatment) The above resin material is preferably used to obtain a cured product that is roughened or desmianized. The cured product includes a pre-cured product that can be further cured.

[0207] In order to form fine irregularities on the surface of the cured product obtained by pre-curing the above resin material, it is preferable that the cured product is roughened. Before the roughening treatment, it is preferable that the cured product is swollen. It is preferable that the cured product is swollen after pre-curing and before being roughened, and is further cured after the roughening treatment. However, the cured product does not necessarily have to be swollen.

[0208] As the above swelling treatment method, for example, a method of treating the cured product with an aqueous solution or an organic solvent dispersion solution of a compound mainly composed of ethylene glycol or the like is used. The swelling liquid used for the swelling treatment generally contains an alkali as a pH adjuster or the like. The swelling liquid preferably contains sodium hydroxide. Specifically, for example, the above swelling treatment is performed by treating the cured product with a 40 wt% ethylene glycol aqueous solution or the like at a treatment temperature of 30°C to 85°C for 1 minute to 30 minutes. The temperature of the above swelling treatment is preferably within the range of 50°C to 85°C. If the temperature of the above swelling treatment is too low, the swelling treatment takes a long time, and the adhesive strength between the cured product and the metal layer tends to be low.

[0209] For the above roughening treatment, for example, chemical oxidants such as manganese compounds, chromium compounds, or persulfate compounds are used. These chemical oxidants are used as an aqueous solution or an organic solvent dispersion solution after adding water or an organic solvent. The roughening liquid used for the roughening treatment generally contains an alkali as a pH adjuster or the like. The roughening liquid preferably contains sodium hydroxide.

[0210] Examples of the above manganese compounds include potassium permanganate and sodium permanganate. Examples of the above chromium compounds include potassium dichromate and potassium chromic anhydride. Examples of the above persulfate compounds include sodium persulfate, potassium persulfate, and ammonium persulfate.

[0211] The arithmetic mean roughness Ra of the surface of the cured product is preferably 10 nm or more, preferably less than 300 nm, more preferably less than 200 nm, and still more preferably less than 150 nm. In this case, the adhesive strength between the cured product and the metal layer increases, and finer wiring is formed on the surface of the insulating layer. Furthermore, conductor loss can be suppressed, and signal loss can be kept low. The arithmetic mean roughness Ra is measured in accordance with JIS B0601:1994.

[0212] (Desmear treatment) Through holes may be formed in the cured product obtained by pre-curing the resin material. In the above multilayer substrate or the like, vias, through-holes, or the like are formed as through holes. For example, vias can be formed by irradiation with a laser such as a CO2 laser. The diameter of the via is not particularly limited, but is about 60 μm to 80 μm. Due to the formation of the above through holes, smears, which are residues of resin derived from the resin components contained in the cured product, are often formed at the bottom inside the vias.

[0213] In order to remove the above smears, the surface of the cured product is preferably subjected to desmear treatment. The desmear treatment may also serve as a roughening treatment.

[0214] For the above desmear treatment, similar to the above roughening treatment, for example, chemical oxidizing agents such as manganese compounds, chromium compounds, or persulfate compounds are used. These chemical oxidizing agents are used as an aqueous solution or an organic solvent dispersion solution after adding water or an organic solvent. The desmear treatment liquid used for the desmear treatment generally contains an alkali. The desmear treatment liquid preferably contains sodium hydroxide.

[0215] By using the above resin material, the surface roughness of the surface of the desmear-treated cured product becomes sufficiently small.

[0216] Hereinafter, the present invention will be specifically described by giving examples and comparative examples. The present invention is not limited to the following examples.

[0217] The following materials were prepared.

[0218] (First compound) The first compound synthesized according to Synthesis Example 1 below (molecular weight: 4000) The first compound synthesized according to Synthesis Example 2 below (molecular weight: 4600)

[0219] <Synthesis Example 1> 115 g of toluene, 35 g of N-methyl-2-pyrrolidone (NMP), 8.7 g of dimer diamine (“Priamine 1075” manufactured by Clariant Japan), and 10.00 g of norbornanediamine (“Pro-NBDA” manufactured by Mitsui Chemicals Fine) were placed in a 500 mL three-necked flask and stirred. Next, 3.0 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the above three-necked flask, and stirring was carried out using a stirring bar with a three-way motor. Also, a mixed solution of 7.78 g of 4,4'-biphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 7.99 g of D of NDA (manufactured by DAXIN MATERIALS) was obtained. The obtained mixed solution was placed in the above three-necked flask and stirred. Next, a reflux tube equipped with a Dean-Stark tube was attached to one mouth of the three-necked flask, the temperature was set to 130 °C in an oil bath, and reflux was carried out for 4 hours while stirring. Next, 6.22 g of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the three-necked flask and refluxed for 4 hours. After reflux, the organic layer was washed 3 times with a mixed solvent of water and ethanol to obtain an organic layer in which the maleimide compound was dissolved. After distilling off water and ethanol from the organic layer, it was slowly dropped into 2 L of methanol, and reprecipitation was carried out to obtain a solid content. The solid content was collected by suction filtration and dried in a vacuum oven to obtain a product (yield 80%).

[0220] <Synthesis Example 2> 115 g of toluene, 35 g of N-methyl-2-pyrrolidone (NMP), 8.7 g of dimer diamine (“Priamine 1075” manufactured by Clariant Japan), and 10.00 g of norbornanediamine (“Pro-NBDA” manufactured by Mitsui Chemicals Fine) were placed in a 500 mL three-necked flask and stirred. Next, 3.0 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry) was added to the above three-necked flask, and stirring was carried out using a stir bar with a three-one motor. Also, a mixed solution of 5.77 g of pyromellitic dianhydride (manufactured by Tokyo Chemical Industry) and 10.7 g of BzDA (manufactured by JXTG) was obtained. The obtained mixed solution was placed in the above three-necked flask and stirred. Next, a reflux tube with a Dean-Stark tube was attached to one of the mouths of the three-necked flask, the temperature was set to 130 °C in an oil bath, and reflux was carried out for 4 hours while stirring. Next, 6.22 g of maleic anhydride (manufactured by Tokyo Chemical Industry) was added to the three-necked flask and refluxed for 4 hours. After reflux, the organic layer was washed 3 times with a mixed solvent of water and ethanol to obtain an organic layer in which the maleimide compound was dissolved. After distilling off water and ethanol from the organic layer, it was slowly dropped into 2 L of methanol, and reprecipitation was carried out to obtain a solid content. The solid content was collected by suction filtration and dried in a vacuum oven to obtain a product (yield 78%).

[0221] (Second compound) Resorcinol diglycidyl ether (“EX-201” manufactured by Nagase ChemteX, molecular weight: 1000 or less) Biphenyl type epoxy compound (“NC-3000H” manufactured by Nippon Kayaku Co., Ltd.: molecular weight: exceeding 1000) Naphthalene type epoxy compound (“ESN-475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.: molecular weight: exceeding 1000) Epoxy compound having an amino group (“630” manufactured by Mitsubishi Chemical Corporation, molecular weight: 1000 or less) Phenylene ether skeleton-containing styrene compound (“OPE-2St-2200” manufactured by Mitsubishi Gas Chemical Company, molecular weight: exceeding 1000)

[0222] (Thermosetting compound X) Epoxy compound having a butadiene skeleton (“PB3600” manufactured by Daicel Corporation, molecular weight 5900) Multi-branched aliphatic epoxy compound (manufactured by Nissan Chemical Industries, Ltd., "FoldiE101", molecular weight: 1000 or less) Hydrogenated bisphenol A diglycidyl ether (manufactured by Nagase ChemteX Corporation, "EX-252", molecular weight: 1000 or less) Maleimide compound 1 (manufactured by Designer Molecules Inc., "BMI-689": molecular weight 1000 or less) Maleimide compound 2 (N-alkyl bis maleimide compound, manufactured by Designer Molecules Inc., "BMI-1700") Maleimide compound 3 (synthesized according to the following Synthesis Example 3: molecular weight 4100) Maleimide compound 4 (synthesized according to the following Synthesis Example 4: molecular weight 4700)

[0223] <Synthesis Example 3> 115 g of toluene, 35 g of N-methyl-2-pyrrolidone (NMP), 8.7 g of dimer diamine (manufactured by Croda Japan, "Priamine 1075"), and 10.00 g of norbornanediamine (manufactured by Mitsui Chemicals Fine Co., Ltd., "Pro-NBDA") were placed in a 500 mL three-necked flask and stirred. Next, 3.0 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the above three-necked flask, and stirring was carried out using a stirring bar with a three-way motor. Also, a mixed solution with 11.5 g of pyromellitic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was obtained. The obtained mixed solution was placed in the above three-necked flask and stirred. Next, a reflux tube with a Dean-Stark tube was attached to one of the mouths of the three-necked flask, the temperature was set to 130 °C in an oil bath, and reflux was carried out for 4 hours while stirring. Next, 6.22 g of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the three-necked flask and refluxed for 4 hours. After reflux, the organic layer was washed 3 times with a mixed solvent of water and ethanol to obtain an organic layer in which the maleimide compound was dissolved. After distilling off water and ethanol from the organic layer, it was slowly dropped into 2 L of methanol, and reprecipitation was carried out to obtain a solid content. The solid content was collected by suction filtration and dried in a vacuum oven to obtain a product (yield 75%).

[0224] <Synthesis Example 4> 115 g of toluene, 35 g of N-methyl-2-pyrrolidone (NMP), 8.7 g of dimer diamine (“Priamine 1075” manufactured by Clariant Japan), and 10.00 g of norbornanediamine (“Pro-NBDA” manufactured by Mitsui Chemicals Fine) were placed in a 500 mL three-necked flask and stirred. Next, 3.0 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry) was added to the above three-necked flask, and stirring was carried out using a stirring rod with a three-one motor. Further, a mixed solution with 14.0 g of 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry) was obtained. The obtained mixed solution was placed in the above three-necked flask and stirred. Next, a reflux tube with a Dean-Stark tube was attached to one of the mouths of the three-necked flask, the temperature was set to 130 °C in an oil bath, and reflux was carried out for 4 hours while stirring. Next, 6.22 g of maleic anhydride (manufactured by Tokyo Chemical Industry) was added to the three-necked flask and refluxed for 4 hours. After reflux, the organic layer was washed 3 times with a mixed solvent of water and ethanol to obtain an organic layer in which the maleimide compound was dissolved. After distilling off water and ethanol from the organic layer, it was slowly dropped into 2 L of methanol, and reprecipitation was carried out to obtain a solid content. The solid content was collected by suction filtration and dried in a vacuum oven to obtain a product (yield 82%).

[0225] (Inorganic filler) Silica-containing slurry (silica 75 wt%: “SC4050-HOA” manufactured by Admatechs, average particle size 1.0 μm, aminosilane treatment, cyclohexanone 25 wt%)

[0226] (Hardener) Liquid containing active ester compound 1 (“HPC-8000L-65T” manufactured by DIC, solid content 65 wt%) Liquid containing active ester compound 2 (“HPC-8150-62T” manufactured by DIC, solid content 62 wt%) Liquid containing phenol compound (“LA-1356” manufactured by DIC, solid content 60 wt%)

[0227] (Hardening accelerator) Dimethylaminopyridine (“DMAP” manufactured by Wako Pure Chemical Industries, Ltd.) 2-Phenyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., "2P4MZ", an anionic curing accelerator)

[0228] (Thermoplastic resin) Polyimide compound (polyimide resin): A polyimide compound-containing solution (nonvolatile content: 26.8% by weight), which is a reaction product of a tetracarboxylic dianhydride and a dimer diamine, was synthesized according to the following Synthesis Example 5.

[0229] <Synthesis Example 5> Into a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas inlet tube, 300.0 g of a tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan Co., Ltd.) and 665.5 g of cyclohexanone were placed, and the solution in the reaction vessel was heated to 60°C. Next, 89.0 g of a dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan Co., Ltd.) and 54.7 g of 1,3-bis(aminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Company, Inc.) were dropped into the reaction vessel. Next, 121.0 g of methylcyclohexane and 423.5 g of ethylene glycol dimethyl ether were added to the reaction vessel, and an imidization reaction was carried out at 140°C for 10 hours. In this way, a polyimide compound-containing solution (nonvolatile content: 26.8% by weight) was obtained. The molecular weight (weight average molecular weight) of the obtained polyimide compound was 20,000. The molar ratio of the acid component to the amine component was 1.04.

[0230] Except for the compounds whose structural formulas could not be specified, the molecular weights of the above first and second compounds and the polyimide compound synthesized in Synthesis Example 5 were determined as follows.

[0231] GPC (gel permeation chromatography) measurement: Using a high-performance liquid chromatography system manufactured by Shimadzu Corporation, measurements were carried out at a column temperature of 40 °C and a flow rate of 1.0 ml / min with tetrahydrofuran (THF) as the developing solvent. "SPD-10A" was used as the detector, and two columns of "KF-804L" (exclusion limit molecular weight 400,000) manufactured by Shodex were connected in series and used. As the standard polystyrene, "TSK Standard Polystyrene" manufactured by Tosoh Corporation was used, and calibration curves were created using substances with weight-average molecular weights Mw = 354,000, 189,000, 98,900, 37,200, 17,100, 9,830, 5,870, 2,500, 1,050, and 500, and the molecular weights were calculated.

[0232] (Examples 1 to 3 and Comparative Examples 1 to 4) The components shown in Table 1 below were blended in the blending amounts (unit: parts by weight of solid content) shown in Table 1 below, and stirred at room temperature until a uniform solution was obtained to obtain a resin material.

[0233] Production of resin film: Using an applicator, the resin material obtained was coated on the release-treated surface of a release-treated PET film ("XG284" manufactured by Toray Industries, Inc., thickness 25 μm), and then dried in a gear oven at 100 °C for 2 minutes and 10 seconds to volatilize the solvent. In this way, a laminated film (a laminated film of a PET film and a resin film) in which a resin film (B-stage film) with a thickness of 40 μm was laminated on the PET film was obtained.

[0234] (Evaluation) (1) Compatibility of resin material The obtained resin film was vacuum laminated on a CCL substrate ("E679FG" manufactured by Hitachi Chemical Co., Ltd.), heated at 130 °C for 30 minutes, and then heated at 170 °C for 30 minutes to be semi-cured. In this way, a laminate in which a semi-cured product of the resin film was laminated on the CCL substrate was obtained.

[0235] The glossiness of the laminate was measured using a handy gloss meter ("IG-331" manufactured by HORIBA). Note that a higher glossiness indicates higher compatibility of the resin material and better fluidity. A lower glossiness indicates lower compatibility of the resin material, with the resin material being phase-separated or the fluidity of the inorganic filler (silica) being reduced.

[0236] [Criteria for Judging Compatibility of Resin Material] ○: Glossiness is 90 or more △: Glossiness is 80 or more and less than 90 ×: Glossiness is less than 80

[0237] (2) Surface Roughness after Etching <Swelling Treatment> The laminate obtained in "

[0238] (1) Compatibility of Resin Material" was placed in a swelling solution ("Swelling Dip Security Gallant P" manufactured by Atotech Japan) at 60°C and shaken for 10 minutes. Then, it was washed with pure water. <Permanganate Treatment (Roughening Treatment and Desmear Treatment)>

[0239] <Measurement of Surface Roughness> On the surface of the evaluation sample (roughened cured product), 10 regions of 94 μm × 123 μm were arbitrarily selected. For each of these 10 regions, the arithmetic mean roughness Ra was measured using a non-contact three-dimensional surface shape measuring device ("WYKO NT1100" manufactured by Veeco). The following surface roughness was evaluated from the average value of the arithmetic mean roughness Ra measured at the 10 locations, and the uniformity of the following surface roughness was evaluated from the absolute value of the difference between the maximum value and the minimum value of the arithmetic mean roughness Ra measured at the 10 locations. Note that the arithmetic mean roughness Ra was measured in accordance with JIS B0601:1994.

[0240] [Criterion for Judging Surface Roughness after Etching] ○: The average value of the arithmetic mean roughness Ra is less than 70 nm △: The average value of the arithmetic mean roughness Ra is 70 nm or more and less than 150 nm ×: The average value of the arithmetic mean roughness Ra is 150 nm or more

[0241] (3) Embeddability for Uneven Surfaces Only the copper foil of a 100 mm square copper-clad laminate (a laminate of a glass epoxy substrate with a thickness of 400 μm and a copper foil with a thickness of 25 μm) was etched to form depressions (openings) with a diameter of 100 μm and a depth of 25 μm linearly in an area of 30 mm square at the center of the substrate and with a center-to-center distance of adjacent holes of 900 μm. In this way, an evaluation substrate having a total of 900 depressions was prepared.

[0242] The resin film side of the obtained laminated film was overlaid on the evaluation substrate, and using a "Batch Type Vacuum Laminator MVLP-500-IIA" manufactured by Meiki Seisakusho Co., Ltd., heating and pressurization were performed at a lamination pressure of 0.4 MPa for 20 seconds, a press pressure of 0.8 MPa for 20 seconds, and a temperature of 90 °C for lamination and pressing. After cooling to room temperature, the PET film was peeled off. In this way, an evaluation sample with a resin film laminated on the evaluation substrate was obtained.

[0243] Regarding the obtained evaluation sample, voids in the depressions were observed using an optical microscope. By evaluating the ratio of the depressions in which voids were observed, the embeddability for uneven surfaces was judged according to the following criteria.

[0244] [Criterion for Judging Embeddability for Uneven Surfaces] ○: The ratio of the depressions in which voids were observed is 0% △: The ratio of the depressions in which voids were observed exceeds 0% and is less than 5% ×: The ratio of the depressions in which voids were observed is 5% or more

[0245] (4) Dielectric Loss Tangent The obtained resin film was heated at 130 °C for 60 minutes for pre-curing, and then heated at 200 °C for 90 minutes to obtain a cured product. The obtained cured product was cut into pieces with a width of 2 mm and a length of 80 mm, and 10 pieces were stacked. Using the "Cavity Resonance Perturbation Method Dielectric Constant Measuring Device CP521" manufactured by Kanto Electronic Application Development Co., Ltd. and the "Network Analyzer N5224A PNA" manufactured by Keysight Technologies, the dielectric loss tangent was measured at room temperature (23 °C) and a frequency of 5.8 GHz by the cavity resonance method.

[0246] [Criteria for Dielectric Loss Tangent] ○: Dielectric loss tangent is less than 2.3×10 -3 less than △: Dielectric loss tangent is 2.3×10 -3 or more and less than 2.5×10 -3 less than ×: Dielectric loss tangent is 2.5×10 -3 or more

[0247] (5) Thermal Dimension Stability (Coefficient of Thermal Expansion (CTE)) The obtained resin film (B-stage film) with a thickness of 40 μm was heated at 130 °C for 60 minutes for pre-curing, and then the cured product obtained by heating at 200 °C for 90 minutes was cut into pieces with a size of 3 mm × 25 mm. Using a thermomechanical analyzer ("EXSTAR TMA / SS6100" manufactured by SII NanoTechnology Inc.), the coefficient of thermal expansion (ppm / °C) of the cut cured product from 25 °C to 150 °C was calculated under the conditions of a tensile load of 33 mN and a heating rate of 5 °C / min.

[0248] [Criteria for Coefficient of Thermal Expansion] ○: Coefficient of thermal expansion is 23 ppm / °C or less △: Coefficient of thermal expansion exceeds 23 ppm / °C and is 27 ppm / °C or less ×: Coefficient of thermal expansion exceeds 27 ppm / °C

[0249] (6) Glass Transition Temperature (Tg) The obtained resin film (B-stage film) with a thickness of 40 μm was heated at 130 °C for 60 minutes for temporary curing, and then the cured product obtained by heating at 200 °C for 90 minutes was cut into a size of 5 mm × 25 mm. Using a thermomechanical analyzer ("DMS6100" manufactured by SII NanoTechnology Inc.), the conditions were as follows: the distance between chucks was 20 mm, the amplitude was 10 μm, the initial value of the tension amplitude was 400 mN, the temperature was raised from 50 °C to 330 °C at a heating rate of 5 °C / min, and the measurement was carried out under the condition of a frequency of 10 Hz. In the obtained measurement results, the peak temperature of the loss tangent was taken as the glass transition temperature Tg (°C).

[0250] [Criteria for Glass Transition Temperature (Tg)] ○: The glass transition temperature exceeds 180 °C △: The glass transition temperature exceeds 170 °C and is 180 °C or less ×: The glass transition temperature is 170 °C or less

[0251] The composition and results are shown in Table 1 below.

[0252]

Table 1

Explanation of Symbols

[0253] 11… Multilayer printed wiring board 12… Circuit board 12a… Upper surface 13 - 16… Insulating layer 17… Metal layer

Claims

1. A first compound having a skeleton derived from an acid dianhydride having a norbornane skeleton, a second compound having an aromatic skeleton, and an inorganic filler, wherein the first compound has a structural unit having an imide bond as a repeating structural unit, the second compound does not have a structural unit having an imide skeleton as a repeating structural unit, the molecular weight of the first compound exceeds 1000, the second compound is a thermosetting compound, A resin material used for forming an insulating layer in a multilayer printed wiring board.

2. The resin material according to claim 1, wherein the molecular weight of the second compound is 1000 or less.

3. The resin material according to claim 1 or 2, wherein the first compound has an aromatic ring.

4. The resin material according to any one of claims 1 to 3, wherein the first compound has a skeleton derived from an acid dianhydride having no norbornane skeleton and having a phthalimide skeleton.

5. The resin material according to any one of claims 1 to 4, wherein the first compound has a skeleton derived from an aliphatic diamine compound.

6. The resin material according to any one of claims 1 to 5, wherein the first compound has a skeleton derived from an aliphatic diamine compound having a cyclohexane skeleton.

7. The resin material according to any one of claims 1 to 6, wherein the first compound has a skeleton derived from a dimer diamine.

8. The resin material according to claim 7, wherein in the first compound, the average ratio of the skeleton derived from the dimer diamine is 10 mol% or more and 90 mol% or less in 100 mol% of all the skeletons derived from diamine compounds.

9. The resin material according to any one of claims 1 to 8, wherein the first compound has a maleimide skeleton or a benzoxazine skeleton.

10. The resin material according to any one of claims 1 to 9, wherein the first compound has a skeleton derived from an acid dianhydride having no norbornane skeleton and no phthalimide skeleton.

11. The resin material according to any one of claims 1 to 10, wherein the molecular weight of the first compound is 50000 or less.

12. The resin material according to any one of claims 1 to 11, wherein the second compound contains an epoxy compound.

13. Containing a curing agent, The resin material according to any one of claims 1 to 12, wherein the curing agent contains an active ester compound.

14. The resin material according to any one of claims 1 to 13, which is a resin film.

15. 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 claims 1 to 14, a multilayer printed wiring board.

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