Resin material, cured product, circuit board with insulating layer and multilayer printed wiring board

Abstract

To provide a resin material capable of achieving sufficient curing at relatively low temperatures.SOLUTION: A resin material according to the present invention comprises an imide compound with a structure X represented by the formula (1), a curable compound, and a curing accelerator. In the formula (1), * denotes a bond position.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin material containing an imide compound. The present invention also relates to a cured product of the resin material. Furthermore, the present invention also relates to a circuit board with an insulating layer and a multilayer printed wiring board using the resin material. [Background technology]

[0002] Conventionally, various resin materials have been used to obtain electronic components such as semiconductor devices, laminates, and printed wiring boards. For example, in 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 on a surface portion. Wiring, which is generally metal, is laminated on the surface of the insulating layer. In addition, a film-like resin material (resin film) may be used to form the insulating layer. The resin material is used as an insulating material for a multilayer printed wiring board including a build-up film.

[0003] The following Patent Document 1 discloses a polyimide having a functional group with a triple bond and a specific repeating structural unit. Patent Document 1 also describes that an insulating film can be formed by printing a printing composition containing the polyimide and a curing agent on a substrate or the like and then drying the printing composition.

[0004] The following Patent Document 2 discloses a curable imide compound having a triple bond represented by a specific chemical structural formula, and also discloses a curable resin composition containing the above curable imide compound and an epoxy compound. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] WO2016 / 093310A1 [Patent Document 2] JP 2014-080494 A Summary of the Invention [Problem to be solved by the invention]

[0006] By curing a resin material containing an imide compound having a triple bond and a curable compound (for example, an epoxy compound), a cured product having excellent heat resistance can be obtained.

[0007] However, conventional resin materials containing an imide compound having a triple bond and a curable compound cannot be cured satisfactorily unless they are heated at a relatively high temperature.

[0008] An object of the present invention is to provide a resin material that can be cured well even at a relatively low temperature. Another object of the present invention is to provide a cured product of the resin material. A further object of the present invention is to provide a circuit board with an insulating layer and a multilayer printed wiring board using the resin material. [Means for solving the problem]

[0009] According to a broad aspect of the present invention, there is provided a resin material comprising an imide compound X having a structure represented by the following formula (1), a curable compound, and a curing accelerator.

[0010] [ka]

[0011] In the formula (1), * represents a bonding position.

[0012] In a specific aspect of the resin material according to the present invention, the imide compound X is a compound represented by the following formula (2).

[0013] [ka]

[0014] In the formula (2), R1 represents any group.

[0015] In a specific aspect of the resin material according to the present invention, the imide compound X is a compound represented by the following formula (21).

[0016] [ka]

[0017] In the formula (21), R1 and R2 each independently represent an aliphatic diamine residue or an aromatic diamine residue, R3 represents an acid dianhydride residue, and n represents 0 or an integer of 1 or more.

[0018] In a specific aspect of the resin material according to the present invention, the curable compound includes an epoxy compound.

[0019] In a specific aspect of the resin material according to the present invention, the epoxy compound includes an epoxy compound that is liquid at 25°C.

[0020] In a specific aspect of the resin material according to the present invention, the curing accelerator includes an amine compound, an imidazole compound, or an organophosphorus compound.

[0021] In a specific aspect of the resin material according to the present invention, the resin material further contains an inorganic filler.

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

[0023] In a specific aspect of the resin material according to the present invention, the resin material further includes a curing agent.

[0024] In a specific aspect of the resin material according to the present invention, the curing agent includes an active ester compound.

[0025] In a specific aspect of the resin material according to the present invention, the resin material has an exothermic peak top temperature of 200° C. or less when subjected to differential scanning calorimetry.

[0026] In a specific aspect of the resin material according to the present invention, the initial adhesive strength of the cured product to copper foil is 3 N / cm or more.

[0027] In a specific aspect of the resin material according to the present invention, the resin material is a resin film.

[0028] In a specific aspect of the resin material according to the present invention, the resin material is an adhesive material.

[0029] In a specific aspect of the resin material according to the present invention, the resin material is an interlayer insulating material.

[0030] According to a broad aspect of the present invention, there is provided a cured product of the above-described resin material.

[0031] According to a broad aspect of the present invention, there is provided a circuit board with an insulating layer, comprising a circuit board and an insulating layer disposed on a surface of the circuit board, the insulating layer being a cured product of the resin material described above.

[0032] According to a broad aspect of the present invention, there is provided a multilayer printed wiring board comprising a circuit board, a plurality of insulating layers disposed on a surface of the circuit board, and a metal layer disposed between the plurality of insulating layers, wherein at least one of the plurality of insulating layers is a cured product of the resin material described above. Effect of the Invention

[0033] The resin material according to the present invention contains the imide compound X having a structure represented by formula (1), a curable compound, and a curing accelerator, and therefore can be cured well even at a relatively low temperature. [Brief description of the drawings]

[0034] [Figure 1] FIG. 1 is a cross-sectional view showing a schematic diagram of a multilayer printed wiring board using a resin material according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0035] The present invention will be described in detail below.

[0036] (Resin material) The resin material according to the present invention contains an imide compound X having a structure represented by the following formula (1), a curable compound, and a curing accelerator.

[0037] [ka]

[0038] In the above formula (1), * represents a bonding position.

[0039] Since the resin material according to the present invention has the above-mentioned features, it can be cured well even at a relatively low temperature.

[0040] Conventional resin materials containing an imide compound having a triple bond and a curable compound (e.g., an epoxy compound) cannot be cured well unless they are heated at a relatively high temperature. When a conventional resin material containing an imide compound having a triple bond and a curable compound is heated at a relatively low temperature, the curing reaction does not proceed sufficiently, making it difficult to obtain a cured product that exhibits the desired performance (e.g., heat resistance, adhesive strength, etc.).

[0041] In contrast, in the resin material according to the present invention, an imide compound having a triple bond (imide compound X), a curable compound, and a curing accelerator are used in combination, and since the imide compound X has a specific structure, it can be cured well even at a relatively low temperature. That is, the resin material according to the present invention has excellent low-temperature curing properties. In addition, the resin material according to the present invention can enhance heat resistance and adhesive strength in a cured product obtained by heating the resin material at a relatively low temperature.

[0042] Furthermore, the resin material according to the present invention can improve the thermal dimensional stability and dielectric properties of the cured product, and therefore can be suitably used in applications where these properties are required (e.g., printed wiring board applications, etc.).

[0043] The resin material according to the present invention may be a resin composition or a resin film. The resin composition has fluidity. The resin composition may be in a paste form. The paste form includes a liquid form. In view of excellent handling properties, the resin material according to the present invention is preferably a resin film.

[0044] 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.

[0045] Hereinafter, details of each component used in the resin material according to the present invention and applications of the resin material according to the present invention will be described.

[0046] In the following description, "100% by weight of the components in the resin material excluding the inorganic filler and the solvent" means "100% by weight of the components in the resin material excluding the inorganic filler and the solvent" when the resin material contains an inorganic filler and a solvent. "100% by weight of the components in the resin material excluding the inorganic filler and the solvent" means "100% by weight of the components in the resin material excluding the inorganic filler" when the resin material contains an inorganic filler and does not contain a solvent. "100% by weight of the components in the resin material excluding the inorganic filler and the solvent" means "100% by weight of the components in the resin material excluding the solvent" when the resin material does not contain an inorganic filler and contains a solvent. "100% by weight of the components in the resin material excluding the inorganic filler and the solvent" means "100% by weight of the resin material" when the resin material does not contain an inorganic filler and a solvent. "100% by weight of the components in the resin material excluding the inorganic filler and the solvent" means "100% by weight of the resin material" when the resin material does not contain an inorganic filler and a solvent. "100% by weight of the components in the resin material excluding the solvent" means "100% by weight of the resin material" when the resin material contains a solvent. The expression "100% by weight of the components in the resin material excluding the solvent" means "100% by weight of the resin material" when the resin material does not contain a solvent.

[0047] [Imide compound X] The resin material includes an imide compound X. The imide compound X is an imide compound having a structure represented by the following formula (1). The structure represented by the following formula (1) is, for example, a structure derived from phenylethynyltrimellitic anhydride (PETA). The imide compound X may be used alone or in combination of two or more kinds.

[0048] [ka]

[0049] In the above formula (1), * represents a bonding position.

[0050] The imide compound X may have one structure represented by the above formula (1), may have two or more structures, may have 10 or less structures, or may have 5 or less structures represented by the above formula (1).

[0051] The imide compound X preferably has two structures represented by the formula (1). The imide compound X preferably has the structures represented by the formula (1) at both ends. In this case, the effects of the present invention can be more effectively exhibited. In addition, the heat resistance, adhesive strength, thermal dimensional stability and dielectric properties of the cured product can be further improved.

[0052] The imide compound X is preferably a compound represented by the following formula (2). In this case, the effects of the present invention can be more effectively exhibited. In addition, the heat resistance, adhesive strength, thermal dimensional stability, and dielectric properties of the cured product can be further improved.

[0053] [ka]

[0054] In the above formula (2), R1 represents any group.

[0055] The imide compound X is preferably a compound represented by the following formula (21). In this case, the effects of the present invention can be more effectively exhibited. In addition, the heat resistance, adhesive strength, thermal dimensional stability, and dielectric properties of the cured product can be more effectively improved.

[0056] [ka]

[0057] In the above formula (21), R1 and R2 each independently represent an aliphatic diamine residue or an aromatic diamine residue, R3 represents an acid dianhydride residue, and n represents 0 or an integer of 1 or more.

[0058] In the above formula (21), R1 and R2 may be the same group or different groups. When n in the above formula (21) is 2 or more, multiple R2 may be the same or different. When n in the above formula (21) is 2 or more, multiple R3 may be the same or different.

[0059] The number of carbon atoms in the aliphatic diamine residue in R1 and R2 in the formula (21) is preferably 4 or more, more preferably 5 or more, even more preferably 6 or more, and preferably 60 or less, more preferably 50 or less. When the number of carbon atoms is equal to or more than the lower limit and equal to or less than the upper limit, the effects of the present invention can be more effectively exhibited. In addition, the heat resistance, adhesive strength, thermal dimensional stability, and dielectric properties of the cured product can be further improved.

[0060] The aliphatic diamine residue may be linear or have a branched structure.

[0061] Examples of the aliphatic diamine compound from which the aliphatic diamine residue is derived include aliphatic diamine compounds derived from dimer acids, linear or branched aliphatic diamine compounds, aliphatic ether diamine compounds, and aliphatic alicyclic diamine compounds.

[0062] Examples of the aliphatic diamine compound derived from the dimer acid include dimer diamine, hydrogenated dimer diamine, etc. Examples of the linear or branched aliphatic diamine compound include 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, 1,18-octadecanediamine, 1,20-eicosanediamine, 2-methyl-1,8-octanediamine, 2-methyl-1,9-nonanediamine, and 2,7-dimethyl-1,8-octanediamine, etc. Examples of the aliphatic ether diamine compound include 2,2'-oxybis(ethylamine), 3,3'-oxybis(propylamine), 1,2-bis(2-aminoethoxy)ethane, etc. Examples of the aliphatic alicyclic diamine compound include 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, cyclohexanediamine, methylcyclohexanediamine, isophoronediamine, etc.

[0063] The aliphatic diamine residue is preferably an aliphatic diamine residue derived from a dimer acid.

[0064] The aromatic diamine residue in R1 and R2 in the above formula (21) is preferably a divalent group represented by the following formula (21A) or (21B).

[0065] [ka]

[0066] In the above formula (21A) and formula (21B), * represents a bonding position. In the above formula (21A), Z represents a bond, an oxygen atom, a carbonyl group, a sulfur atom, a sulfonyl group, a linear or branched divalent hydrocarbon group which may have an oxygen atom at the bonding position, or a divalent group having an aromatic ring which may have an oxygen atom at the bonding position.

[0067] The hydrogen atoms in the aromatic rings in the above formula (21A) and formula (21B) may be substituted.

[0068] When Z in the above formula (21A) is a linear or branched divalent hydrocarbon group which may have an oxygen atom at the bonding position, or a divalent group having an aromatic ring which may have an oxygen atom at the bonding position, these groups may be substituted. In this case, examples of the substituent include a halogen atom, a linear or branched alkyl group, a linear or branched alkenyl group, an alicyclic group, an aryl group, an alkoxy group, a nitro group, and a cyano group.

[0069] The acid dianhydride residue in R3 in the above formula (21) is preferably a tetravalent group having one or two aromatic rings, and more preferably a tetravalent group represented by the following formula (21C) or (21D). In this case, the effects of the present invention can be more effectively exhibited. In addition, the heat resistance, adhesive strength, thermal dimensional stability, and dielectric properties of the cured product can be further improved.

[0070] [ka]

[0071] In the above formula (21C) and formula (21D), * represents a bonding position. In the above formula (21C), Z represents a bond, an oxygen atom, a carbonyl group, a sulfur atom, a sulfonyl group, a linear or branched divalent hydrocarbon group which may have an oxygen atom at the bonding position, or a divalent group having an aromatic ring which may have an oxygen atom at the bonding position.

[0072] The hydrogen atoms in the aromatic rings in the above formula (21C) and formula (21D) may be substituted.

[0073] When Z in the above formula (21C) is a linear or branched divalent hydrocarbon group which may have an oxygen atom at the bonding position, or a divalent group having an aromatic ring which may have an oxygen atom at the bonding position, these groups may be substituted. In this case, examples of the substituent include a halogen atom, a linear or branched alkyl group, a linear or branched alkenyl group, an alicyclic group, an aryl group, an alkoxy group, a nitro group, and a cyano group.

[0074] In the above formula (21), n ​​may be 0 or 1 or more. In the above formula (21), n ​​is preferably 1 or more, more preferably 2 or more, and preferably 150 or less, more preferably 100 or less. When n is equal to or more than the above lower limit and equal to or less than the above upper limit, the effects of the present invention can be more effectively exhibited. In addition, the heat resistance, adhesive strength, thermal dimensional stability, and dielectric properties of the cured product can be further improved.

[0075] The molecular weight of the imide compound X is preferably 500 or more, more preferably 600 or more, and preferably 20,000 or less, more preferably 15,000 or less. When the molecular weight is equal to or more than the lower limit and equal to or less than the upper limit, the effects of the present invention can be more effectively exhibited. In addition, the heat resistance, adhesive strength, thermal dimensional stability, and dielectric properties of the cured product can be further improved.

[0076] The molecular weight of the imide compound X means a molecular weight that can be calculated from the structural formula when the imide compound X is not a polymer and when the structural formula of the imide compound X can be specified. When the imide compound X is a polymer, the molecular weight means a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0077] The imide compound X can be obtained, for example, by reacting phenylethynyltrimellitic anhydride with an amine compound.

[0078] The content of the imide compound X in 100% by weight of the components in the resin material excluding the inorganic filler and the solvent is preferably 5% by weight or more, more preferably 10% by weight or more, preferably 60% by weight or less, more preferably 55% by weight or less. When the content of the imide compound X is equal to or more than the lower limit and equal to or less than the upper limit, the effects of the present invention can be more effectively exhibited. In addition, the heat resistance, adhesive strength, thermal dimensional stability, and dielectric properties of the cured product can be further improved.

[0079] [Curable compound] The resin material includes a curable compound. The curable compound is a curable compound different from the imide compound (imide compound X) having the structure represented by the formula (1). The curable compounds may be used alone or in combination of two or more.

[0080] The curable compound preferably includes a thermosetting compound, and more preferably is a thermosetting compound.

[0081] Examples of the curable compound include epoxy compounds, vinyl compounds, phenoxy compounds, oxetane compounds, maleimide compounds, cyanate compounds, polyarylate compounds, diallyl phthalate compounds, episulfide compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, and silicone compounds.

[0082] The curable compound preferably contains an epoxy compound, a maleimide compound or a cyanate compound, more preferably contains an epoxy compound, and further preferably is an epoxy 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 improved.

[0083] Examples of the epoxy compound include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, bisphenol E type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, biphenyl type epoxy compounds, biphenyl novolac type epoxy compounds, biphenol type epoxy compounds, naphthalene type epoxy compounds, fluorene type epoxy compounds, phenol aralkyl type epoxy compounds, naphthol aralkyl type epoxy compounds, dicyclopentadiene type epoxy compounds, anthracene type epoxy compounds, epoxy compounds having an adamantane skeleton, epoxy compounds having a tricyclodecane skeleton, naphthylene ether type epoxy compounds, and epoxy compounds having a triazine nucleus in the skeleton. The epoxy compounds may be used alone or in combination of two or more.

[0084] The epoxy compound may be a glycidyl ether compound, which is a compound having at least one glycidyl ether group.

[0085] The epoxy compound preferably contains an epoxy compound having an aromatic ring, more preferably contains an epoxy compound having a naphthalene skeleton or a phenyl skeleton, and further preferably is an epoxy compound having an aromatic ring. 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 improved.

[0086] From the viewpoint of further lowering the dielectric tangent of the cured product and improving the coefficient of linear expansion (CTE) of the cured product, it is preferable that the epoxy compound contains an epoxy compound that is liquid at 25°C, and it is more preferable that the epoxy compound contains an epoxy compound that is liquid at 25°C and an epoxy compound that is solid at 25°C.

[0087] 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.

[0088] The viscosity of the epoxy compound can be measured, for example, using a dynamic viscoelasticity measuring device ("VAR-100" manufactured by Rheologica Instruments).

[0089] It is more preferable that the molecular weight of the epoxy compound is 1000 or less. In this case, even if the content of the inorganic filler is 50% by weight or more in 100% by weight of the components excluding the solvent in the resin material, a resin material having high fluidity during the formation of an insulating layer is obtained. Therefore, when the uncured or B-staged resin material is laminated on a circuit board, the inorganic filler is easily uniformly present.

[0090] The molecular weight of the epoxy compound means a molecular weight that can be calculated from the structural formula when the epoxy compound is not a polymer and when the structural formula of the epoxy compound can be specified, and means a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) when the epoxy compound is a polymer.

[0091] In 100% by weight of the curable compound, the content of the epoxy compound may be 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, 100% by weight or less, or less than 100% by weight.

[0092] The content of the epoxy compound is preferably 10% by weight or more, more preferably 20% by weight or more, and preferably 80% by weight or less, more preferably 70% by weight or less, based on 100% by weight of the components in the resin material excluding the inorganic filler and the solvent. When the content of the epoxy compound is equal to or more than the lower limit and equal to or less than the upper limit, the thermal dimensional stability of the cured product can be further improved.

[0093] In the resin material, the weight ratio of the content of the epoxy compound to the content of the imide compound X (content of the epoxy compound / content of the imide compound X) is preferably 0.5 or more, more preferably 0.75 or more, even more preferably 0.9 or more, preferably 10 or less, more preferably 7 or less, and even more preferably 5 or less. When the weight ratio (content of the epoxy compound / content of the imide compound X) is equal to or more than the lower limit, the adhesive strength of the cured product can be further increased. When the weight ratio (content of the epoxy compound / content of the imide compound X) is equal to or less than the upper limit, the heat resistance of the cured product can be further increased. When the weight ratio (content of the epoxy compound / content of the imide compound X) is equal to or more than the lower limit and equal to or less than the upper limit, the effects of the present invention can be more effectively exhibited.

[0094] The content of the curable compound in 100% by weight of the components in the resin material excluding the inorganic filler and the solvent is preferably 10% by weight or more, more preferably 20% by weight or more, and preferably 80% by weight or less, more preferably 70% by weight or less. When the content of the curable compound is equal to or more than the lower limit and equal to or less than the upper limit, the thermal dimensional stability of the cured product can be further improved.

[0095] In the resin material, the weight ratio of the content of the curable compound to the content of the imide compound X (content of the curable compound / content of the imide compound X) is preferably 0.5 or more, more preferably 0.75 or more, even more preferably 0.9 or more, preferably 10 or less, more preferably 7 or less, and even more preferably 5 or less. When the weight ratio (content of the curable compound / content of the imide compound X) is equal to or more than the lower limit, the adhesive strength of the cured product can be further increased. When the weight ratio (content of the curable compound / content of the imide compound X) is equal to or less than the upper limit, the heat resistance of the cured product can be further increased. When the weight ratio (content of the curable compound / content of the imide compound X) is equal to or more than the lower limit and equal to or less than the upper limit, the effect of the present invention can be more effectively exhibited.

[0096] [Cure accelerator] The resin material includes a curing accelerator. The use of the curing accelerator further accelerates the curing speed. By quickly curing the resin material, the crosslinked structure in the cured product becomes uniform, and the number of unreacted functional groups is reduced, resulting in a high crosslink density. In addition, the use of the curing accelerator allows the resin material to be cured well even at a relatively low temperature. The curing accelerator may be used alone or in combination of two or more types.

[0097] Examples of the 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 organophosphorus compounds and organometallic compounds; and radical curing accelerators such as peroxides.

[0098] Examples of the imidazole compound include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, and 1-cyanoethyl-2-phenylimidazolium trimethylolate. remellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-dihydroxymethylimidazole.

[0099] Examples of the amine compound include diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, diethylenetriamine, ethylenediamine, tris(dimethylaminomethyl)phenol, benzyldimethylamine, m-xylylenedi(dimethylamine), N,N'-dimethylpiperazine, N-methylpyrrolidine, N-methylhydroxypiperidine, m-xylylenediamine, isophoronediamine, N-aminoethylpiperazine, polyoxypropylenepolyamine, and 4,4-dimethylaminopyridine. The amine compound may be a modified product of these amine compounds.

[0100] Examples of the organic phosphorus compound include organic phosphine compounds such as triphenylphosphine, tricyclohexylphosphine, tribenzylphosphine, diphenyl(alkylphenyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkylalkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, and alkyldiarylphosphine, as well as phosphonium salt compounds such as tetraphenylphosphonium tetraphenylborate.

[0101] Examples of the organometallic compound include zinc naphthenate, cobalt naphthenate, tin octoate, cobalt octoate, cobalt bisacetylacetonate (II), and cobalt trisacetylacetonate (III).

[0102] Examples of the peroxide include diacyl peroxides, peroxy esters, peroxy dicarbonates, monoperoxy carbonates, peroxy ketals, dialkyl peroxides, dibenzyl peroxide, dicumyl peroxide, hydroperoxides, and ketone peroxides.

[0103] The curing accelerator preferably contains an amine compound, an imidazole compound, or an organic phosphorus compound, in which case the effects of the present invention can be more effectively exhibited.

[0104] In the resin material, the content of the curing accelerator is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, and preferably 10 parts by weight or less, more preferably 5 parts by weight or less, relative to 100 parts by weight of the total content of the imide compound X and the curable compound. When the content of the curing accelerator is equal to or more than the lower limit and equal to or less than the upper limit, the effects of the present invention can be more effectively exhibited.

[0105] [Inorganic filler] The resin material does not contain or contains an inorganic filler. The resin material may or may not contain an inorganic filler. The resin material preferably contains an inorganic filler. By using the inorganic filler, the dielectric tangent of the cured product can be further reduced. In addition, by using the inorganic filler, the dimensional change of the cured product due to heat can be further reduced. The inorganic filler may be used alone or in combination of two or more types.

[0106] Examples of the inorganic filler include silica, talc, clay, mica, hydrotalcite, alumina, magnesium oxide, aluminum hydroxide, diamond, aluminum nitride, and boron nitride.

[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 can be reduced, and the adhesive strength between the cured product and the metal layer can be further increased. In addition, fine wiring can be formed on the surface of the cured product, and the cured product can be provided with better insulation reliability. When the inorganic filler is silica, the thermal expansion coefficient of the cured product is further reduced, and the dielectric loss tangent of the cured product is further reduced. The silica may be hollow silica.

[0108] From the viewpoint of increasing the thermal conductivity and the insulating property, the inorganic filler is preferably alumina or boron nitride. In particular, boron nitride has anisotropy, and therefore the coefficient of linear thermal expansion can be further reduced.

[0109] The inorganic filler has an average particle size of preferably 50 nm or more, more preferably 100 nm or more, even more preferably 500 nm or more, and preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less. When the inorganic filler has an average particle size of not less than the lower limit and not more than the upper limit, the surface roughness after etching can be reduced and the plating peel strength can be increased, and the adhesion between the insulating layer and the metal layer can be further improved.

[0110] The median diameter (d50) at 50% is used as the average particle diameter of the inorganic filler. The average particle diameter can be measured using a particle size distribution measuring device using a laser diffraction scattering method. In addition, when the inorganic filler is an aggregated particle, the average particle diameter of the inorganic filler means the primary particle diameter.

[0111] The inorganic filler is preferably spherical, more preferably spherical silica. In this case, the surface roughness of the cured product is effectively reduced, and the adhesive strength between the cured product and the metal layer is effectively increased. When the inorganic filler is spherical, the aspect ratio of the inorganic filler is preferably 2 or less, more preferably 1.5 or less.

[0112] The inorganic filler is preferably surface-treated, more preferably surface-treated with a coupling agent, and even more preferably surface-treated with a silane coupling agent.By surface-treating the inorganic filler, the surface roughness of the roughened cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased.In addition, by surface-treating the inorganic filler, finer wiring can be formed on the surface of the cured product, and better inter-wiring insulation reliability and inter-layer insulation reliability can be imparted to the cured product.

[0113] The coupling agent includes a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, etc. The silane coupling agent includes a methacrylsilane, an acrylsilane, an aminosilane, an imidazole silane, a vinylsilane, an epoxysilane, etc.

[0114] The content of the inorganic filler in 100% by weight of the components excluding the solvent in the resin material is preferably 10% by weight or more, more preferably 20% by weight or more, preferably 90% by weight or less, more preferably 80% by weight or less. When the content of the inorganic filler is equal to or more than the lower limit, the dielectric loss tangent is effectively lowered. When the content of the inorganic filler is equal to or less than the upper limit, the thermal dimensional stability is improved and the warping of the cured product can be effectively suppressed. When the content of the inorganic filler is equal to or more than the lower limit and equal to or less than the upper limit, the surface roughness of the cured product can be further reduced and finer wiring can be formed on the surface of the cured product. Furthermore, with this content of the inorganic filler, it is possible to lower the thermal expansion coefficient of the cured product and at the same time improve the smear removability.

[0115] [Hardening agent] The resin material does not contain a curing agent or contains a curing agent. The resin material may contain a curing agent or may not contain a curing agent. The resin material preferably contains a curing agent. The curing agent is not particularly limited. As the curing agent, a conventionally known curing agent can be used. Only one type of the curing agent may be used, or two or more types may be used in combination.

[0116] Examples of the curing agent include a phenol compound (phenol curing agent), an active ester compound, a cyanate ester compound (cyanate ester curing agent), a benzoxazine compound (benzoxazine curing agent), a carbodiimide compound (carbodiimide curing agent), an amine compound (amine curing agent), a thiol compound (thiol curing agent), a phosphine compound, a dicyandiamide, and an acid anhydride. The curing agent preferably has a functional group capable of reacting with the epoxy group of the epoxy compound.

[0117] From the viewpoint of further increasing the thermal dimensional stability of the cured product, the curing agent preferably contains a phenolic compound, an active ester compound, a cyanate ester compound, a benzoxazine compound, a carbodiimide compound, or an acid anhydride. From the viewpoint of further increasing the thermal dimensional stability of the cured product, the curing agent more preferably contains a phenolic compound, an active ester compound, a cyanate ester compound, a benzoxazine compound, or a carbodiimide compound, and even more preferably contains an active ester compound.

[0118] From the viewpoint of further enhancing the thermal dimensional stability of the cured product, it is preferable that the curable compound contains an epoxy compound and the curing agent contains an active ester compound.

[0119] Examples of the phenol compound include novolak type phenols, biphenol type phenols, naphthalene type phenols, dicyclopentadiene type phenols, aralkyl type phenols, and dicyclopentadiene type phenols.

[0120] Commercially available phenol compounds include novolac phenols ("TD-2091" manufactured by DIC Corporation), biphenyl novolac phenols ("MEH-7851" manufactured by Meiwa Kasei Co., Ltd.), aralkyl phenol compounds ("MEH-7800" manufactured by Meiwa Kasei Co., Ltd.), and phenols having an aminotriazine skeleton ("LA-1356" and "LA-3018-50P" manufactured by DIC Corporation).

[0121] The above-mentioned active ester compound refers to a compound having at least one ester bond and having an aliphatic chain, an aliphatic ring, or an aromatic ring bonded to both sides of the ester bond. The above-mentioned 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. The above-mentioned active ester compound includes a compound represented by the following formula (A).

[0122] [ka]

[0123] In the above formula (A), X1 represents a group having an aliphatic chain, a group having an aliphatic ring, or a group having an aromatic ring, and X2 represents a group having an aromatic ring.Preferred examples of the group having an aromatic ring include a benzene ring which may have a substituent, and a naphthalene ring which may have a substituent.The above-mentioned substituent includes a hydrocarbon group.The number of carbon atoms of the hydrocarbon group is preferably 12 or less, more preferably 6 or less, and even more preferably 4 or less.

[0124] In the above formula (A), the combination of X1 and X2 includes a combination of an optionally substituted benzene ring and an optionally substituted benzene ring, and a combination of an optionally substituted benzene ring and an optionally substituted naphthalene ring.Furthermore, in the above formula (A), the combination of X1 and X2 includes a combination of an optionally substituted naphthalene ring and an optionally substituted naphthalene ring.

[0125] The active ester compound is not particularly limited. From the viewpoint of further improving the thermal dimensional stability and flame retardancy of the cured product, the active ester compound is preferably an active ester compound having two or more aromatic rings. From the viewpoint of lowering the dielectric tangent of the cured product and improving the thermal dimensional stability of the cured product, the active ester compound more preferably has a naphthalene ring or a dicyclopentadiene skeleton in the main chain skeleton.

[0126] Commercially available products of the above active ester compound include "HPC-8000-65T", "EXB9416-70BK", "HPC-8150-62T", "EXB-8" and "EXB8100-65T" manufactured by DIC Corporation.

[0127] Examples of the cyanate ester compound include novolac-type cyanate ester resins, bisphenol-type cyanate ester resins, and prepolymers obtained by partially trimerizing these. Examples of the novolac-type cyanate ester resins include phenol novolac-type cyanate ester resins and alkylphenol-type cyanate ester resins. Examples of the bisphenol-type cyanate ester resins include bisphenol A-type cyanate ester resins, bisphenol E-type cyanate ester resins, and tetramethylbisphenol F-type cyanate ester resins.

[0128] Commercially available products of the cyanate ester compound include phenol novolac type cyanate ester resins ("PT-30" and "PT-60" manufactured by Lonza Japan) and prepolymers in which bisphenol type cyanate ester resins are trimerized ("BA-230S", "BA-3000S", "BTP-1000S" and "BTP-6020S" manufactured by Lonza Japan).

[0129] Examples of the benzoxazine compound include Pd-type benzoxazine and Fa-type benzoxazine.

[0130] Commercially available products of the above benzoxazine compound include "Pd type" manufactured by Shikoku Chemical Industry Co., Ltd. and "ODA-BOZ" manufactured by JFE Chemical Corporation.

[0131] The carbodiimide compound is a compound having a structural unit represented by the following formula (C). In the following formula (C), the right end and the left end are bonding sites with other groups. The above carbodiimide compounds may be used alone or in combination of two or more kinds.

[0132] [ka]

[0133] In the above formula (C), X represents an alkylene group, a group in which a substituent is bonded to an alkylene group, a cycloalkylene group, a group in which a substituent is bonded to a cycloalkylene group, an arylene group, or a group in which a substituent is bonded to an arylene group, and p represents an integer of 1 to 5. When a plurality of Xs are present, the plurality of Xs may be the same or different.

[0134] In one preferred embodiment, in the above formula (C), at least one X is an alkylene group, a group in which a substituent is bonded to an alkylene group, a cycloalkylene group, or a group in which a substituent is bonded to a cycloalkylene group.

[0135] Commercially available examples of the carbodiimide compound 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 Inc., as well as "Stavaxol P", "Stavaxol P400", and "Hi-Kasil 510" manufactured by Rhein Chemie.

[0136] Examples of the acid anhydride include tetrahydrophthalic anhydride and alkylstyrene-maleic anhydride copolymer.

[0137] Commercially available products of the above acid anhydrides include "Rikacid TDA-100" manufactured by New Japan Chemical Co., Ltd.

[0138] In the resin material, the content of the curing agent is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, preferably 120 parts by weight or less, and more preferably 100 parts by weight or less, relative to 100 parts by weight of the total content of the imide compound X and the curable compound. When the content of the curing agent is equal to or more than the lower limit and equal to or less than the upper limit, the curability is more excellent, the thermal dimensional stability is further improved, and the volatilization of the remaining unreacted components can be further suppressed.

[0139] [Thermoplastic resin] The resin material does not contain or contains a thermoplastic resin. The resin material may or may not contain a thermoplastic resin. Examples of the thermoplastic resin include polyimide resin, phenoxy resin, and polyvinyl acetal resin. The thermoplastic resin may be used alone or in combination of two or more.

[0140] From the viewpoint of improving the handleability and the heat resistance of the cured product, the thermoplastic resin is preferably a polyimide resin or a phenoxy resin, and more preferably a polyimide resin. The resin material preferably contains a polyimide resin or a phenoxy resin, and more preferably contains a polyimide resin.

[0141] The weight average molecular weight of the thermoplastic resin is preferably 5,000 or more, more preferably 10,000 or more, and is preferably 100,000 or less, more preferably 50,000 or less.

[0142] The weight average molecular weight of the thermoplastic resin means a weight average molecular weight measured by gel permeation chromatography (GPC) and calculated as polystyrene.

[0143] The content of the thermoplastic resin in 100% by weight of the components in the resin material excluding the inorganic filler and the solvent is preferably 1% by weight or more, more preferably 2% by weight or more, preferably 30% by weight or less, more preferably 20% by weight or less. When the content of the thermoplastic resin is equal to or more than the lower limit and equal to or less than the upper limit, the resin film has good embedding properties in holes or irregularities in the circuit board. When the content of the thermoplastic resin is equal to or more than the lower limit, the resin film is formed more easily, and a better insulating layer is obtained. When the content of the thermoplastic resin is equal to or less than the upper limit, the thermal expansion coefficient of the cured product is further reduced. When the content of the thermoplastic resin is equal to or less than the upper limit, the surface roughness of the cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased.

[0144] [solvent] The resin material does not contain or contains a solvent. The resin material may or may not contain a solvent. By using the solvent, the viscosity of the resin material can be controlled within a suitable range, and the coatability of the resin material can be improved. The solvent may be used to obtain a slurry containing the inorganic filler. Only one type of the solvent may be used, or two or more types may be used in combination.

[0145] Examples of the solvent include acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane, toluene, xylene, methyl ethyl ketone, N,N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidone, n-hexane, cyclohexane, cyclohexanone, and naphtha, which is a mixture.

[0146] It is preferable that most of the solvent is removed when the resin composition is molded into a film. Therefore, the boiling point of the solvent is preferably 200°C or less, more preferably 180°C or less. The content of the solvent in the resin composition is not particularly limited. The content of the solvent can be appropriately changed in consideration of the coatability of the resin composition.

[0147] 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, more preferably 5% by weight or less.

[0148] [Other ingredients] For the purpose of improving impact resistance, heat resistance, resin compatibility, workability, and the like, the resin material may contain an organic filler, a leveling agent, a flame retardant, a coupling agent, a colorant, an antioxidant, an ultraviolet degradation inhibitor, a defoaming agent, a thickener, a thixotropy imparting agent, and the like.

[0149] The coupling agent includes a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, etc. The silane coupling agent includes a vinyl silane, an amino silane, an imidazole silane, an epoxy silane, etc.

[0150] (Resin film) The above-mentioned resin composition is molded into a film to obtain a resin film (B-stage product / B-stage film). The above-mentioned resin material is preferably a resin film. The resin film is preferably a B-stage film.

[0151] Examples of methods for forming a resin composition into a film to obtain a resin film include the following: an extrusion molding method in which a resin composition is melt-kneaded and extruded using an extruder, and then molded into a film using a T-die or a circular die; a casting molding method in which a resin composition containing a solvent is cast into a film; and other conventionally known film molding methods. The extrusion molding method and the casting molding method are preferred because they can be made thinner. Films include sheets.

[0152] The resin composition is molded into a film and dried by heating at, for example, 50° C. to 150° C. for 1 minute to 10 minutes to the extent that curing by heat does not proceed too much, to obtain a resin film that is a B-stage film.

[0153] The film-like resin composition obtained by the drying process as described above is called a B-stage film. The B-stage film is in a semi-cured state. The semi-cured product is not completely cured and can be further cured.

[0154] The resin film does not have to be a prepreg. When the resin film is not a prepreg, migration does not occur along the glass cloth, etc. In addition, when the resin film is laminated or precured, unevenness due to the glass cloth does not occur on the surface.

[0155] The resin film can be used in the form of a laminated film comprising a metal foil or a base film and a resin film laminated on the surface of the metal foil or the base film. The metal foil is preferably a copper foil.

[0156] Examples of the base film of the laminated film include polyester resin films such as polyethylene terephthalate film and polybutylene terephthalate film, olefin resin films such as polyethylene film and polypropylene film, and polyimide resin films. The surface of the base film may be subjected to a release treatment as necessary.

[0157] From the viewpoint of controlling the degree of cure of the resin film more uniformly, the thickness of the resin film is preferably 5 μm or more and preferably 200 μm or less. When the resin film is used as an insulating layer of a circuit, the thickness of the insulating layer formed by the resin film is preferably equal to or more than the thickness of the conductor layer (metal layer) forming the circuit. The thickness of the insulating layer is preferably 5 μm or more and preferably 200 μm or less.

[0158] (Other details of resin material) When differential scanning calorimetry (DSC) is performed on the resin material, it is preferable that the resin material has an exothermic peak top temperature of 200°C or less, more preferably an exothermic peak top temperature of 195°C or less, and even more preferably an exothermic peak top temperature of 190°C or less. In this case, the effects of the present invention can be more effectively exhibited. When the resin material has a plurality of exothermic peaks, "having an exothermic peak top temperature of T°C or less" means that the peak top temperature of at least one exothermic peak is T°C or less.

[0159] The differential scanning calorimetry is performed by using a differential scanning calorimeter to heat the resin material at a temperature increase rate of 10° C. / min from 30° C. to 350° C. Examples of the differential scanning calorimeter include "EXTEAR DSC6100" manufactured by Hitachi High-Tech Science Corporation.

[0160] In the above resin material, the initial adhesive strength of the cured product to the copper foil is preferably 1 N / cm or more, more preferably 3 N / cm or more, and even more preferably 3.5 N / cm or more. When the initial adhesive strength is equal to or greater than the lower limit, the above resin material can be suitably used as an adhesive material, an interlayer insulating material, etc. The initial adhesive strength may be 15 N / cm or less, or may be 10 N / cm or less.

[0161] The initial adhesive strength of the cured product to the copper foil is measured as follows. A copper foil having a thickness of 35 μm is laminated on both sides of a resin film (resin material) having a thickness of 40 μm to obtain a laminate (1). The obtained laminate (1) is heated at 180° C. for 30 minutes to be temporarily cured, and then heated at 200° C. for 90 minutes to cure the resin film disposed between the copper foils to obtain a laminate (2). The laminate (2) is cut into a width of 1 cm to obtain a measurement sample. Within 24 hours after the production of the laminate (2), the measurement sample is subjected to T-shaped peeling at 25° C. and a peeling speed of 20 mm / min using a tensile tester to measure the peel strength, and the obtained peel strength is defined as the initial adhesive strength. In addition, examples of the copper foil include the “UN series” manufactured by Fukuda Metal Foil and Powder Co., Ltd. In this commercially available product, the shiny side of the copper foil can be used as the surface to be bonded to the resin film. An example of the tensile tester is ORIENTEC's "UCT-500."

[0162] In the above resin material, the glass transition temperature of the cured product is preferably 120° C. or higher, more preferably 140° C. or higher, and even more preferably 150° C. or higher. When the glass transition temperature is equal to or higher than the lower limit, the mechanical strength and long-term heat resistance of the cured product can be further improved. The glass transition temperature of the cured product may be 350° C. or lower, 300° C. or lower, or 250° C. or lower.

[0163] The glass transition temperature of the cured product is measured as follows. A resin film (resin material) having a thickness of 400 μm is heated at 180° C. for 30 minutes to be temporarily cured, and then heated at 200° C. for 90 minutes to obtain a cured product. The glass transition temperature is determined by measuring the cured product obtained under the conditions of a temperature rise rate of 10° C. / min, a frequency of 10 Hz, and a chuck distance of 24 mm from 0° C. to 300° C. using a dynamic viscoelasticity measuring device. For example, the "DMS6100" manufactured by Hitachi High-Tech Science Corporation can be used as the dynamic viscoelasticity measuring device. When the thickness of the resin film is less than 400 μm, a resin film having a thickness of 400 μm may be obtained by laminating a plurality of resin films.

[0164] The resin material can be used for various purposes. For example, the resin material is preferably used for forming a mold resin in which a semiconductor chip is embedded in a semiconductor device. The resin material is also preferably used for replacing liquid crystal polymer (LCP), for millimeter wave antennas, and for rewiring layers. The resin material is not limited to the above uses, and is preferably used for wiring formation in general.

[0165] The resin material is preferably used as an adhesive material. The resin material is preferably used as, for example, an adhesive material for a power overlay package, an adhesive material for a printed wiring board, an adhesive material for a coverlay of a flexible printed circuit board, or an adhesive material for semiconductor bonding. The resin material is preferably an adhesive material.

[0166] The resin material is preferably used as an insulating material. The resin material is preferably used to form an insulating layer in a printed wiring board, and more preferably used to form an insulating layer in a multilayer printed wiring board. The resin material is preferably an insulating material, and more preferably an interlayer insulating material. The insulating material may also serve as an adhesive material.

[0167] The cured product according to the present invention is a cured product of a resin material obtained by curing the above-mentioned resin material. The cured product according to the present invention is a cured product of a resin material, and the resin material is the above-mentioned resin material. The cured product according to the present invention can be obtained by curing the above-mentioned resin material. The heating conditions of the resin material when obtaining the cured product according to the present invention are not particularly limited as long as the resin material is cured.

[0168] (Laminated structures and copper-clad laminates) A laminated structure can be obtained by laminating a laminated target member having a metal layer on one or both sides of the resin film. The laminated structure includes a laminated target member having a metal layer on its surface and a resin film laminated on the surface of the metal layer, and the resin film is the above-mentioned resin material. The method of laminating the resin film and the laminated target member is not particularly limited, and a known method can be used. For example, the resin film can be laminated on the laminated target member while applying pressure with or without heating using a device such as a parallel plate press or a roll laminator.

[0169] The material of the metal layer is preferably copper.

[0170] The lamination target member having the metal layer on the surface thereof may be a metal foil such as a copper foil.

[0171] The resin material is preferably used to obtain a copper-clad laminate. An example of the copper-clad laminate is a copper-clad laminate including a copper foil and a resin film laminated on one surface of the copper foil, the resin film being made of the resin material described above.

[0172] The thickness of the copper foil of the copper-clad laminate is not particularly limited. The thickness of the copper foil is preferably 1 μm or more and 100 μm or less. In addition, in order to increase the adhesive strength between the cured resin material and the copper foil, the copper foil preferably has fine irregularities on its surface. The method 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.

[0173] (Insulating layer circuit board) The resin material is preferably used to obtain a circuit board with an insulating layer. One example of the circuit board with an insulating layer is a circuit board with an insulating layer that includes a circuit board and an insulating layer disposed on a surface of the circuit board, the insulating layer being a cured product of the resin material described above.

[0174] In the circuit board with an insulating layer, the insulating layer is preferably laminated on a surface of the circuit board on which the circuits are provided, and a part of the insulating layer is preferably embedded between the circuits.

[0175] The above-mentioned circuit board with an insulating layer can be obtained by a conventionally known method.

[0176] (Multilayer boards and multilayer printed wiring boards) The resin material is preferably used to obtain a multilayer board. An example of the multilayer board is a multilayer board including a circuit board and an insulating layer laminated on the circuit board. The insulating layer of the multilayer board is a cured product of the resin material. The insulating layer is preferably laminated on the surface of the circuit board on which the circuit (metal layer) is provided. A part of the insulating layer is preferably embedded between the circuits.

[0177] In the multilayer board, the surface of the insulating layer opposite to the surface on which the circuit board is laminated is preferably roughened.

[0178] The roughening treatment method is not particularly limited and may be any conventionally known roughening treatment method. The surface of the insulating layer may be subjected to a swelling treatment before the roughening treatment.

[0179] Preferably, the multilayer substrate further comprises a copper plating layer laminated on the roughened surface of the insulating layer.

[0180] Another example of the multilayer board is a multilayer board comprising a circuit board, an insulating layer laminated on the surface of the circuit board, and a copper foil laminated on the surface of the insulating layer opposite to the surface on which the circuit board is laminated. The insulating layer is preferably formed by using a copper-clad laminate comprising copper foil and a resin film laminated on one surface of the copper foil, and curing the resin film. Furthermore, the copper foil is preferably etched to form a copper circuit.

[0181] Another example of the multilayer board is a multilayer board including a circuit board and a plurality of insulating layers laminated on a surface of the circuit board. At least one of the insulating layers arranged on the circuit board is formed using the resin material. The multilayer board preferably further includes a circuit laminated on at least one surface of the insulating layer formed using the resin film.

[0182] The above-mentioned resin material is suitably used for forming an insulating layer in a multilayer printed wiring board.

[0183] The multilayer printed wiring board includes, for example, a circuit board, a plurality of insulating layers disposed on a surface of the circuit board, and a metal layer disposed between the plurality of insulating layers, and at least one of the insulating layers is a cured product of the resin material described above.

[0184] FIG. 1 is a cross-sectional view showing a schematic diagram of a multilayer printed wiring board using a resin material according to one embodiment of the present invention.

[0185] In the multilayer printed wiring board 11 shown in FIG. 1, a plurality of insulating layers 13-16 are laminated on the upper surface 12a of the circuit board 12. The insulating layers 13-16 are cured layers. A metal layer 17 is formed on a partial region of the upper surface 12a of the circuit board 12. Of the plurality of insulating layers 13-16, the insulating layers 13-15 other than the insulating layer 16 located on the outer surface opposite to the circuit board 12 side have the metal layer 17 formed on a partial region of the upper surface. The metal layer 17 is a circuit. The metal layer 17 is disposed between the circuit board 12 and the insulating layer 13, and between each of the laminated insulating layers 13-16. The lower metal layer 17 and the upper metal layer 17 are connected to each other by at least one of a via hole connection and a through hole connection not shown.

[0186] In the multilayer printed wiring board 11, the insulating layers 13-16 are formed of a cured product of the above-mentioned resin material. In this embodiment, the surfaces of the insulating layers 13-16 are roughened, so that fine holes (not shown) are formed on the surfaces of the insulating layers 13-16. The metal layer 17 reaches the inside of the fine holes. In the multilayer printed wiring board 11, the width dimension (L) of the metal layer 17 and the width dimension (S) of the portion where the metal layer 17 is not formed can be reduced. In the multilayer printed wiring board 11, good insulation reliability is provided between the upper metal layer and the lower metal layer that are not connected by via hole connection and through hole connection (not shown).

[0187] The present invention will be specifically described below by way of examples and comparative examples, but the present invention is not limited to the following examples.

[0188] The following materials were prepared:

[0189] (Imide compound X) Imide compound X1: According to the following Synthesis Example X1, an imide compound X1 (molecular weight 810) represented by the following formula (X1) was synthesized.

[0190] <Synthesis Example X1> In a reaction vessel equipped with a stirrer, a water divider, and a nitrogen gas inlet tube, 10.0 parts by weight of 1,3-bis(4-aminophenoxy)benzene and 20.8 parts by weight of phenylethynyltrimellitic anhydride were dissolved in 70 parts by weight of N-methylpyrrolidone. The resulting solution was stirred at room temperature for 24 hours, and then 10.8 parts by weight of pyridine and 14.0 parts by weight of acetic anhydride were added to the solution and stirred for another 15 minutes. The resulting solution was added to 300 mL of methanol, and the precipitated solid was collected. The collected solid was dried in a reduced pressure oven at 40°C for 24 hours to obtain an imide compound X1 represented by the following formula (X1).

[0191] [ka]

[0192] Imide compound X2: According to the following Synthesis Example X2, an imide compound X2 (molecular weight 820) represented by the following formula (X2) was synthesized.

[0193] <Synthesis example X2> In a reaction vessel equipped with a stirrer, a water divider, and a nitrogen gas inlet tube, 10 parts by weight of dibromohexane, 14.8 parts by weight of hydroxyacetanilide, and 25.5 parts by weight of potassium carbonate were dissolved in 80 parts by weight of acetone. The obtained solution was stirred under reflux for 24 hours. Next, the solution was added to 200 mL of water, and the precipitated solid was collected. In addition, a solution was prepared by dissolving 8.2 parts by weight of sodium hydroxide in a mixed solvent of 60 mL of water and 60 mL of ethanol. This solution was added to the collected solid, and the mixture was stirred under reflux for 24 hours. The obtained solution was added to 200 mL of water, and the precipitated solid was collected. The collected solid was dried in a reduced pressure oven at 40°C for 24 hours, to obtain an amine compound MA represented by the following formula (MA).

[0194] [ka]

[0195] Next, in a reaction vessel equipped with a stirrer, a water divider, and a nitrogen gas inlet tube, 10 parts by weight of an amine compound MA and 20.2 parts by weight of phenylethynyltrimellitic anhydride were dissolved in 70 parts by weight of N-methylpyrrolidone. The resulting solution was stirred at room temperature for 24 hours, and then 10.5 parts by weight of pyridine and 13.6 parts by weight of acetic anhydride were added to the solution and stirred for another 15 minutes. The resulting solution was added to 300 mL of methanol, and the precipitated solid was collected. The collected solid was dried in a reduced pressure oven at 40°C for 24 hours to obtain an imide compound X2 represented by the following formula (X2).

[0196] [ka]

[0197] Imide Compound X3: According to the following Synthesis Example X3, an imide compound X3 (molecular weight 8600) represented by the following formula (X3) was synthesized.

[0198] <Synthesis example X3> In a reaction vessel equipped with a stirrer, a water divider, and a nitrogen gas inlet tube, 52.0 parts by weight of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 200 parts by weight of cyclohexanone were dissolved. 32.1 parts by weight of 1,3-bis(4-aminophenoxy)benzene was added to the obtained solution and stirred at 150°C for 6 hours. Next, 5.5 parts by weight of phenylethynyltrimellitic anhydride was added to the solution and stirred for 3 hours. The moisture generated during this reaction was removed, and an imidization reaction was carried out. The obtained solution was added to 400 mL of methanol, and the precipitated solid was collected. The collected solid was dried in a reduced pressure oven at 40°C for 24 hours to obtain an imide compound X3 represented by the following formula (X3).

[0199] [ka]

[0200] In the above formula (X3), X represents a group represented by the following formula (X31).

[0201] [ka]

[0202] (curable compound) Imide compound Y1: According to the following Synthesis Example Y1, an imide compound Y1 (molecular weight 750) represented by the following formula (Y1) was synthesized.

[0203] <Synthetic Example Y1> An imide compound Y1 represented by the following formula (Y1) was obtained in the same manner as in Synthesis Example X1, except that 18.7 parts by weight of phenylethynylphthalic anhydride was used instead of 20.8 parts by weight of phenylethynyltrimellitic anhydride.

[0204] [ka]

[0205] Phenylethynyltrimellitic anhydride ("NEXIMID300" manufactured by Nexam) Bisphenol F epoxy compound (DIC "EXA-830CRP", liquid at 25°C) Biphenyl aralkyl type epoxy compound ("NC3000" manufactured by Nippon Kayaku Co., Ltd., solid at 25°C)

[0206] (Cure accelerator) Imidazole compounds (2-ethyl-4-methylimidazole) Organophosphorus compounds (triphenylphosphine)

[0207] (hardening agent) Active ester compound-containing liquid (DIC "HPC-8000-65T", solid content 65% by weight)

[0208] (Inorganic filler) Silica-containing slurry (75% silica by weight: Admatechs "SC4050-HOA", average particle size 1.0 μm, aminosilane treatment, cyclohexanone 25% by weight)

[0209] (thermoplastic resin) Polyimide resin-containing liquid (polyimide resin-containing liquid containing a reaction product of tetracarboxylic dianhydride and dimer diamine (non-volatile content 26.8% by weight), synthesized according to Synthesis Example T below)

[0210] <Synthesis example T> In a reaction vessel equipped with a stirrer, a water divider, a thermometer, and a nitrogen gas inlet tube, 300.0 g of tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan LLC) 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 dimer diamine ("PRIAMINE1075" manufactured by Croda Japan) and 54.7 g of 1,3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 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 the imidization reaction was carried out at 140°C for 10 hours. In this way, a polyimide compound-containing solution (non-volatile content 26.8% by weight) was obtained. The molecular weight (weight average molecular weight) of the obtained polyimide compound was 20,000. The molar ratio of acid component / amine component was 1.04.

[0211] The weight average molecular weights of the imide compound and the thermoplastic resin were determined as follows.

[0212] GPC (Gel Permeation Chromatography) Measurement: The measurements were performed using a Shimadzu high-performance liquid chromatograph system, with tetrahydrofuran (THF) as the developing medium, at a column temperature of 40°C and a flow rate of 1.0 ml / min. The detector used was an SPD-10A, and two Shodex KF-804L columns (with an exclusion limit of 400,000) were connected in series. Tosoh TSK Standard Polystyrene was used as the standard polystyrene, and a calibration curve was 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.

[0213] (Examples 1 to 12 and Comparative Examples 1 to 6) The components shown in Tables 1 to 4 below were mixed in the amounts (unit: parts by weight of solid content) shown in Tables 1 to 4 below, and stirred at room temperature until a homogeneous solution was obtained, to obtain a resin material.

[0214] Preparation of resin film: The obtained resin material was applied to the release-treated surface of a release-treated polyethylene terephthalate film (PET film, Toray Industries, Inc., "XG284", thickness 25 μm) using an applicator, and then dried for 2 minutes and 30 seconds in a gear oven at 100°C to volatilize the solvent. In this way, a laminated film (a laminated film of a PET film and a resin film) was obtained in which a resin film (B-stage film) with a thickness of 40 μm was laminated on the PET film.

[0215] (1) Low-temperature curing of resin materials (1-1) Curing temperature (exothermic peak top temperature) Using a differential scanning calorimeter (Hitachi High-Tech Science Corporation, "EXTEAR DSC6100"), 10 mg of the resulting resin film having a thickness of 40 μm was weighed out and heated from 30° C. to 350° C. at a heating rate of 10° C. / min to measure the exothermic peak. The curing temperature was evaluated according to the following criteria.

[0216] [Criteria for Curing Temperature] ○: Heat generation peak top temperature is 200℃ or less △: Heat generation peak top temperature is over 200℃ and 300℃ or less ×: The top temperature of the exothermic peak exceeds 300° C. or no exothermic peak is observed.

[0217] (1-2) Curing reaction rate (heating conditions: 190°C and 1 hour) The amount of heat generated was calculated from the peak area of ​​the exothermic peak of the resin film obtained in the measurement of "(1-1) Curing temperature (top temperature of exothermic peak)" above. The obtained resin film having a thickness of 40 μm was heated at 190° C. for 1 hour to obtain a cured product. The exothermic peak of this cured product was measured under the conditions described in "(1-1) Curing temperature (top temperature of exothermic peak)" above. The amount of heat generated was calculated from the peak area of ​​the exothermic peak of the obtained cured product. The curing reaction rate was calculated using the following formula and evaluated according to the following criteria.

[0218] Curing reaction rate (%) = (AB) / A x 100 A: The amount of heat generated calculated from the peak area of ​​the heat generation peak of the resin film B: Heat generation amount calculated from the peak area of ​​the heat generation peak of the cured product

[0219] [Criteria for determining the curing reaction rate] ○: Curing reaction rate is 95% or more △: Curing reaction rate is 90% to 95% ×: Curing reaction rate is less than 90%

[0220] (2) Heat resistance of the cured product (2-1) Glass transition temperature of the cured product The obtained resin films each having a thickness of 40 μm were laminated to obtain a resin film having a thickness of 400 μm. The obtained resin film having a thickness of 400 μm was heated at 180° C. for 30 minutes to be temporarily cured, and then heated at 200° C. for 90 minutes to obtain a cured product. The obtained cured product was measured using a dynamic viscoelasticity measuring device (Hitachi High-Tech Science Corporation, "DMS6100") under the conditions of a temperature rise rate of 10° C. / min, a frequency of 10 Hz, and a chuck distance of 24 mm from 0° C. to 300° C. The peak temperature of the obtained tan δ curve was taken as the glass transition temperature. The glass transition temperature was evaluated according to the following criteria.

[0221] [Criteria for determining the glass transition temperature of the cured product] ○: Glass transition temperature is 150℃ or higher △: Glass transition temperature is 120℃ or higher and less than 150℃ ×: Glass transition temperature is less than 120°C

[0222] (2-2) Thermal decomposition resistance of cured product (5% weight loss temperature) A cured resin film was obtained according to the method described above in "(2-1) Glass transition temperature of the cured product". The 5% weight loss temperature of the obtained cured product was measured using a thermogravimetric analyzer (Hitachi High-Tech Science Corporation "TG / DTA6200") in the temperature range of 30°C to 500°C at a temperature increase rate of 10°C / min. The thermal decomposition resistance of the cured product was evaluated according to the following criteria.

[0223] [Criteria for determining thermal decomposition resistance of cured products] ○○: 5% weight loss temperature is 350℃ or higher ○: 5% weight loss temperature is 330℃ or more and less than 350℃ △: 5% weight loss temperature is 300℃ or higher but less than 330℃ ×: 5% weight loss temperature is less than 300℃

[0224] (3) Initial adhesion of the cured product to copper foil Copper foils of 35 μm in thickness were laminated on both sides of the obtained resin film of 40 μm in thickness to obtain a laminate (1). The laminate (1) was heated at 180° C. for 30 minutes to be temporarily cured, and then heated at 200° C. for 90 minutes to cure the resin film disposed between the copper foils to obtain a laminate (2). The laminate (2) was cut into a width of 1 cm to obtain a measurement sample. Within 24 hours after the production of the laminate (2), the measurement sample was subjected to T-shaped peeling at 25° C. and a peeling speed of 20 mm / min using a tensile tester (ORIENTEC Corporation's "UCT-500"), and the peel strength obtained was taken as the initial adhesive strength. The copper foil used was "UN series" manufactured by Fukuda Metal Foil and Powder Co., Ltd. When the laminate (1) was produced, the glossy side of this commercially available product was used as the surface to be bonded to the resin film. The initial adhesive strength of the cured product to the copper foil was evaluated according to the following criteria.

[0225] [Criteria for determining initial adhesion of cured product to copper foil] ○: Initial adhesive strength is 3N / cm or more △: Initial adhesive strength is 1N / cm or more and less than 3N / cm ×: Initial adhesive strength is less than 1N / cm

[0226] (4) Thermal dimensional stability of the cured product The resulting 40 μm thick resin film was temporarily cured by heating at 180° C. for 30 minutes, and then heated at 200° C. for 90 minutes to obtain a cured product. The resulting cured product was cut into pieces measuring 3 mm×25 mm. Using a thermomechanical analyzer (Hitachi High-Tech Science Corporation, “EXSTAR TMA / SS6100”), the average linear expansion coefficient (ppm / ° C.) of the cut cured product from 25° C. to 150° C. was calculated under conditions of a tensile load of 33 mN and a heating rate of 5° C. / min.

[0227] [Criteria for determining thermal dimensional stability of cured product] ○○: Average linear expansion coefficient is 23ppm / ℃ or less ○: Average linear expansion coefficient is more than 23 ppm / ℃ and less than 30 ppm / ℃ ×: Average linear expansion coefficient exceeds 30 ppm / ℃

[0228] The compositions and results are shown in the following Tables 1 to 4. The evaluation of "(3) Initial adhesive strength of the cured product to copper foil" was performed on the resin films obtained in Examples 1 to 6 and Comparative Examples 1 to 4. The evaluation of "(4) Thermal dimensional stability of the cured product" was performed on the resin films obtained in Examples 7 to 12 and Comparative Examples 5 and 6.

[0229] [Table 1]

[0230] [Table 2]

[0231] [Table 3]

[0232] [Table 4] [Explanation of symbols]

[0233] 11...Multilayer printed wiring board 12...Circuit board 12a…Top surface 13~16…Insulating layer 17...Metal layer

Claims

1. A resin material comprising an imide compound X having a structure represented by the following formula (1), a curable compound, and a curing accelerator: 【Chemical 1】 In the formula (1), * represents a bonding position.

2. The resin material according to claim 1 , wherein the imide compound X is a compound represented by the following formula (2): 【Chemistry 2】 In the formula (2), R １ represents any group.

3. The resin material according to claim 1 or 2, wherein the imide compound X is a compound represented by the following formula (21): 【Chemistry 3】 In the formula (21), R １ and R ２ each independently represents an aliphatic diamine residue or an aromatic diamine residue, R ３ represents an acid dianhydride residue, and n represents an integer of 0 or 1 or more.

4. The resin material according to claim 1 or 2, wherein the curable compound includes an epoxy compound.

5. The resin material according to claim 4 , wherein the epoxy compound comprises an epoxy compound that is liquid at 25° C.

6. The resin material according to claim 1 or 2, wherein the curing accelerator comprises an amine compound, an imidazole compound, or an organic phosphorus compound.

7. The resin material according to claim 1 or 2, further comprising an inorganic filler.

8. The resin material according to claim 7 , wherein the inorganic filler is silica.

9. The resin material according to claim 1 or 2, further comprising a curing agent.

10. The resin material according to claim 9 , wherein the curing agent comprises an active ester compound.

11. The resin material according to claim 1 or 2, which has an exothermic peak top temperature of 200°C or less when measured by differential scanning calorimetry.

12. The resin material according to claim 1 or 2, wherein the cured product has an initial adhesive strength to copper foil of 3 N / cm or more.

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

14. The resin material according to claim 1 or 2, which is an adhesive material.

15. The resin material according to claim 1 or 2, which is an interlayer insulating material.

16. A cured product of the resin material according to claim 1 or 2.

17. A circuit board; an insulating layer disposed on a surface of the circuit board; A circuit board with an insulating layer, wherein the insulating layer is a cured product of the resin material according to claim 1 or 2.

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

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