JP2024035604A - Resin materials, cured products, circuit boards with insulation layers, and multilayer printed wiring boards - Google Patents

Abstract

[Problem] To provide a resin material that can be cured well even at a relatively low temperature. [Solution] 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. TIFF2024035604000025.tif47139 In the formula (1), * represents a bond position. [Selected Figure] None

Description

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

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, and to form an insulating layer located on a surface layer. Wiring, which is generally metal, is laminated on the surface of the insulating layer. Further, a film-like resin material (resin film) may be used to form the above-mentioned insulating layer. The above-mentioned resin materials are used as insulating materials for multilayer printed wiring boards including build-up films.

Patent Document 1 below discloses a polyimide having a functional group having a triple bond and a specific repeating structural unit. Further, Patent Document 1 describes that an insulating film can be formed by printing a printing composition containing the polyimide and a curing agent on a base material, etc. and then drying the printing composition. has been done.

Patent Document 2 below discloses a curable imide compound having a triple bond represented by a specific chemical structural formula. Further, Patent Document 2 discloses a curable resin composition containing the above-mentioned curable imide compound and an epoxy compound.

WO2016/093310A1 Japanese Patent Application Publication No. 2014-080494

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 with excellent heat resistance can be obtained.

However, conventional resin materials containing an imide compound having a triple bond and a curable compound cannot be cured well unless heated at a relatively high temperature.

An object of the present invention is to provide a resin material that can be cured well even at relatively low temperatures. Another object of the present invention is to provide a cured product of the above resin material. Furthermore, another object of the present invention is to provide a circuit board with an insulating layer and a multilayer printed wiring board using the above resin material.

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

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

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

In the formula (2), R ₁ represents an arbitrary group.

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

In the formula (21), R ₁ and R ₂ each independently represent an aliphatic diamine residue or an aromatic diamine residue, R ₃ represents an acid dianhydride residue, and n is 0 or 1. Represents an integer greater than or equal to

In a particular aspect of the resin material according to the present invention, the curable compound includes an epoxy compound.

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

In a particular aspect of the resin material according to the present invention, the curing accelerator includes an amine compound, an imidazole compound, or an organic phosphorus compound.

In a certain aspect of the resin material according to the present invention, the resin material further includes an inorganic filler.

In a particular aspect of the resin material according to the present invention, the inorganic filler is silica.

In a particular aspect of the resin material according to the present invention, the resin material further includes a curing agent.

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

In a particular 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 differential scanning calorimetry is performed.

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

In a particular aspect of the resin material according to the present invention, the resin material is a resin film.

In a particular aspect of the resin material according to the present invention, the resin material is an adhesive material.

In a particular aspect of the resin material according to the present invention, the resin material is an interlayer insulation material.

According to a broad aspect of the present invention, a cured product of the resin material described above is provided.

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 above-mentioned resin material. provided.

According to a broad aspect of the present invention, the invention includes 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. A multilayer printed wiring board is provided, in which at least one layer is a cured product of the resin material described above.

Since the resin material according to the present invention contains the imide compound X having the structure represented by formula (1), a curable compound, and a curing accelerator, it can be cured well even at a relatively low temperature.

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

The details of the present invention will be explained below.

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

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

Since the resin material according to the present invention has the above configuration, it can be cured well even at a relatively low temperature.

Conventional resin materials containing an imide compound having a triple bond and a curable compound (eg, an epoxy compound) cannot be cured well unless heated at a relatively high temperature. Note that when conventional resin materials containing an imide compound having a triple bond and a curable compound are heated at a relatively low temperature, the curing reaction does not proceed sufficiently. etc.) is difficult to obtain.

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 the imide compound Therefore, 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 curability. Moreover, with the resin material according to the present invention, heat resistance and adhesive strength can be increased in a cured product obtained by heating the resin material at a relatively low temperature.

Furthermore, since the resin material according to the present invention can improve thermal dimensional stability and dielectric properties in a cured product, the resin material can be suitably used in applications where these performances are required (for example, printed wiring board applications, etc.). be able to.

The resin material according to the present invention may be a resin composition or a resin film. The resin composition has fluidity. The resin composition may be in the form of a paste. The pasty state includes a liquid state. The resin material according to the present invention is preferably a resin film because of its excellent handling properties.

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.

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

In addition, in the following explanation, "100% by weight of the components excluding the inorganic filler and solvent in the resin material" means "the inorganic filler in the resin material" when the resin material contains an inorganic filler and a solvent. and 100% by weight of components excluding solvent. "100% by weight of the components in the resin material excluding inorganic fillers and solvents" means "100% by weight of the components in the resin material excluding inorganic fillers" when the resin material contains inorganic fillers and does not contain solvents. %” means. "100% by weight of the components in the resin material excluding inorganic fillers and solvents" means "100% by weight of the components in the resin material excluding the solvent" when the resin material does not contain inorganic fillers and contains a solvent. means. "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 the inorganic filler and the solvent. "100% by weight of the components in the resin material excluding the solvent" means "100% by weight of the components in the resin material excluding the solvent" when the resin material contains 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 does not contain a solvent.

[Imide compound X]
The resin material contains 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 phenylethynyl trimellitic anhydride (PETA). Only one kind of the imide compound X may be used, or two or more kinds thereof may be used in combination.

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

The above-mentioned imide compound 5 or less.

It is preferable that the imide compound X has two structures represented by the above formula (1). It is preferable that the imide compound X has a structure represented by the above formula (1) at both ends. In this case, the effects of the present invention can be exhibited even more effectively. Furthermore, the heat resistance, adhesive strength, thermal dimensional stability, and dielectric properties of the cured product can be further improved.

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 exhibited even more effectively. Furthermore, the heat resistance, adhesive strength, thermal dimensional stability, and dielectric properties of the cured product can be further improved.

In the above formula (2), R ₁ represents an arbitrary group.

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 exhibited even more effectively. Furthermore, the heat resistance, adhesive strength, thermal dimensional stability, and dielectric properties of the cured product can be further improved.

In the above formula (21), R ₁ and R ₂ each independently represent an aliphatic diamine residue or an aromatic diamine residue, R ₃ represents an acid dianhydride residue, and n is 0 or 1. Represents an integer greater than or equal to

In the above formula (21), R ₁ and R ₂ may be the same group or different groups. When n in the above formula (21) is 2 or more, a plurality of R ₂ may be the same or different. When n in the above formula (21) is 2 or more, a plurality of R ₃ 's may be the same or different.

The number of carbon atoms in the aliphatic diamine residue in R ₁ and R ₂ in the formula (21) is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, preferably 60 or less, and more preferably 50 It is as follows. When the number of carbon atoms is not less than the lower limit and not more than the upper limit, the effects of the present invention can be exhibited even more effectively. Furthermore, the heat resistance, adhesive strength, thermal dimensional stability, and dielectric properties of the cured product can be further improved.

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

The aliphatic diamine compounds from which the above aliphatic diamine residues are derived include aliphatic diamine compounds derived from dimer acids, linear or branched aliphatic diamine compounds, aliphatic ether diamine compounds, and aliphatic alicyclic Examples include diamine compounds.

Examples of the aliphatic diamine compound derived from the above dimer acid include dimer diamine, hydrogenated dimer diamine, and the like. The linear or branched aliphatic diamine compounds 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. Examples of the aliphatic ether diamine compounds include 2,2'-oxybis(ethylamine), 3,3'-oxybis(propylamine), and 1,2-bis(2-aminoethoxy)ethane. Examples of the aliphatic alicyclic diamine compounds include 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, cyclohexanediamine, methylcyclohexanediamine, and isophoronediamine.

The aliphatic diamine residue is preferably an aliphatic diamine residue derived from dimer acid.

The aromatic diamine residues in R ₁ and R ₂ in the above formula (21) are preferably divalent groups represented by the following formula (21A) or the following formula (21B).

In the above formula (21A) and the above 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, or a linear or branched divalent hydrocarbon which may have an oxygen atom at the bonding position. represents a group or a divalent group having an aromatic ring which may have an oxygen atom at the bonding position.

The hydrogen atom of the aromatic ring in the above formula (21A) and the above formula (21B) may be substituted.

Even if 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 linear or branched divalent hydrocarbon group which may have an oxygen atom at the bonding position, In the case of divalent groups having a good aromatic ring, these groups may be substituted. Substituents in this case include halogen atoms, linear or branched alkyl groups, linear or branched alkenyl groups, alicyclic groups, aryl groups, alkoxy groups, nitro groups, and cyano groups. etc.

The acid dianhydride residue in R ₃ in the above formula (21) is preferably a tetravalent group having one or two aromatic rings, and is represented by the following formula (21C) or the following formula (21D). It is more preferable that it is a tetravalent group represented by: In this case, the effects of the present invention can be exhibited even more effectively. Furthermore, the heat resistance, adhesive strength, thermal dimensional stability, and dielectric properties of the cured product can be further improved.

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

The hydrogen atom of the aromatic ring in the above formula (21C) and the above formula (21D) may be substituted.

Even if 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 linear or branched divalent hydrocarbon group which may have an oxygen atom at the bonding position, In the case of divalent groups having a good aromatic ring, these groups may be substituted. Substituents in this case include halogen atoms, linear or branched alkyl groups, linear or branched alkenyl groups, alicyclic groups, aryl groups, alkoxy groups, nitro groups, and cyano groups. etc.

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, preferably 150 or less, and more preferably 100 or less. When n is greater than or equal to the above lower limit and less than or equal to the above upper limit, the effects of the present invention can be exhibited even more effectively. Furthermore, the heat resistance, adhesive strength, thermal dimensional stability, and dielectric properties of the cured product can be further improved.

The molecular weight of the imide compound X is preferably 500 or more, more preferably 600 or more, preferably 20,000 or less, and more preferably 15,000 or less. When the molecular weight is not less than the lower limit and not more than the upper limit, the effects of the present invention can be exhibited even more effectively. Furthermore, the heat resistance, adhesive strength, thermal dimensional stability, and dielectric properties of the cured product can be further improved.

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

The imide compound X can be obtained, for example, by reacting phenylethynyl trimellitic anhydride and an amine compound.

The content of the imide compound X is preferably 5% by weight or more, more preferably 10% by weight or more, preferably 60% by weight or less, based on 100% by weight of the components excluding the inorganic filler and solvent in the resin material. Preferably it is 55% by weight or less. When the content of the imide compound X is not less than the above lower limit and not more than the above upper limit, the effects of the present invention can be exhibited even more effectively. Furthermore, the heat resistance, adhesive strength, thermal dimensional stability, and dielectric properties of the cured product can be further improved.

[Curable compound]
The resin material includes a curable compound. The above-mentioned curable compound is a curable compound different from the imide compound (imide compound X) having the structure represented by the above formula (1). As for the said curable compound, only 1 type may be used, and 2 or more types may be used together.

It is preferable that the said curable compound contains a thermosetting compound, and it is more preferable that it is a thermosetting compound.

Examples of the curable compounds include epoxy compounds, vinyl compounds, phenoxy compounds, oxetane compounds, maleimide compounds, cyanate compounds, polyarylate compounds, diallylphthalate compounds, episulfide compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, and silicone compounds. etc.

The curable compound preferably contains an epoxy compound, a maleimide compound, or a cyanate compound, more preferably contains an epoxy compound, and still more preferably an epoxy compound. In this case, the dielectric loss tangent of the cured product can be further lowered, and the thermal dimensional stability of the cured product can be further improved.

The above epoxy compounds 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, and biphenyl novolac type epoxy compounds. 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, Examples include epoxy compounds having a cyclodecane skeleton, naphthylene ether type epoxy compounds, and epoxy compounds having a triazine nucleus in the skeleton. The above epoxy compounds may be used alone or in combination of two or more.

The epoxy compound may be a glycidyl ether compound. The above-mentioned glycidyl ether compound is a compound having at least one glycidyl ether group.

The epoxy compound preferably includes an epoxy compound having an aromatic ring, more preferably an epoxy compound having a naphthalene skeleton or a phenyl skeleton, and even more preferably an epoxy compound having an aromatic ring. In this case, the dielectric loss tangent of the cured product can be further lowered, and the thermal dimensional stability of the cured product can be further improved.

From the viewpoint of further lowering the dielectric loss tangent of the cured product and improving the coefficient of linear expansion (CTE) of the cured product, the epoxy compound preferably contains an epoxy compound that is liquid at 25°C. It is more preferable to include a liquid epoxy compound and a solid epoxy compound at 25°C.

The viscosity at 25° C. of the epoxy compound which is liquid at 25° C. is preferably 1000 mPa·s or less, more preferably 500 mPa·s or less.

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

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 with high fluidity can be obtained during formation of the insulating layer. Therefore, when an uncured resin material or a B-staged resin material is laminated on a circuit board, the inorganic filler can be easily present uniformly.

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

The content of the epoxy compound in 100% by weight of the curable compound may be 50% by weight or more, 60% by weight or more, 70% by weight or more, or 80% by weight. It may be 90% by weight or more, 95% by weight or more, 100% by weight or less, or less than 100% by weight.

The content of the epoxy compound is preferably 10% by weight or more, more preferably 20% by weight or more, preferably 80% by weight or less, more preferably 100% by weight of the components excluding the inorganic filler and solvent in the resin material. is 70% by weight or less. When the content of the epoxy compound is not less than the above lower limit and not more than the above upper limit, the thermal dimensional stability of the cured product can be further improved.

In the resin material, the weight ratio of the epoxy compound content to the imide compound X content (epoxy compound content/imide compound X content) is preferably 0.5 or more, more preferably 0. .75 or more, more preferably 0.9 or more, preferably 10 or less, more preferably 7 or less, still more preferably 5 or less. When the weight ratio (epoxy compound content/imide compound X content) is equal to or higher than the lower limit, the adhesive strength of the cured product can be further increased. When the weight ratio (epoxy compound content/imide compound X content) is below the above upper limit, the heat resistance of the cured product can be further improved. When the weight ratio (epoxy compound content/imide compound X content) is not less than the above lower limit and not more than the above upper limit, the effects of the present invention can be exhibited even more effectively.

The content of the curable compound is preferably 10% by weight or more, more preferably 20% by weight or more, preferably 80% by weight or less, based on 100% by weight of the components excluding the inorganic filler and solvent in the resin material. Preferably it is 70% by weight or less. When the content of the curable compound is not less than the above lower limit and not more than the above upper limit, the thermal dimensional stability of the cured product can be further improved.

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 is 0.75 or more, more preferably 0.9 or more, preferably 10 or less, more preferably 7 or less, still more preferably 5 or less. When the weight ratio (curable compound content/imide compound X content) is equal to or higher than the lower limit, the adhesive strength of the cured product can be further increased. When the above weight ratio (content of curable compound/content of imide compound X) is below the above upper limit, the heat resistance of the cured product can be further improved. When the weight ratio (content of curable compound/content of imide compound X) is not less than the above lower limit and not more than the above upper limit, the effects of the present invention can be exhibited even more effectively.

[Curing accelerator]
The resin material includes a curing accelerator. By using the above-mentioned curing accelerator, the curing speed becomes even faster. By rapidly curing the resin material, the crosslinked structure in the cured product becomes uniform, the number of unreacted functional groups decreases, and the crosslinking density increases as a result. Moreover, by using the above-mentioned curing accelerator, the resin material can be cured well even at a relatively low temperature. As for the said hardening accelerator, only 1 type may be used, and 2 or more types may be used together.

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 organic phosphorus compounds and organometallic compounds. Agents include radical curing accelerators such as peroxides.

The above imidazole compounds include 2-undecylimidazole, 2-heptadecyl imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl- 2-Methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-un Decylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2' -Methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino- 6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s -triazine 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 etc.

The above amine compounds include diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, diethylenetriamine, ethylenediamine, tris(dimethylaminomethyl)phenol, benzyldimethylamine, m-xylylene di(dimethylamine), N,N'-dimethylpiperazine, N -methylpyrrolidine, N-methylhydroxypiperidine, m-xylylenediamine, isophoronediamine, N-aminoethylpiperazine, polyoxypropylene polyamine, and 4,4-dimethylaminopyridine. Moreover, the amine compound may be a modified product of these amine compounds.

The organic phosphorus compounds include 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, dialkyl Examples include organic phosphine compounds such as arylphosphines and alkyldiarylphosphines, and phosphonium salt compounds such as tetraphenylphosphonium/tetraphenylborate.

Examples of the organometallic compound include zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, cobalt (II) bisacetylacetonate, and cobalt (III) trisacetylacetonate.

Examples of the peroxides include diacyl peroxide, peroxy ester, peroxy dicarbonate, monoperoxy carbonate, peroxy ketal, dialkyl peroxide, dibenzyl peroxide, dicumyl peroxide, hydroperoxide, and ketone peroxide. Examples include oxide.

The curing accelerator preferably contains an amine compound, an imidazole compound, or an organic phosphorus compound. In this case, the effects of the present invention can be exhibited even more effectively.

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, based on 100 parts by weight of the total content of the imide compound X and the curable compound. The amount is at least 10 parts by weight, preferably 10 parts by weight or less, and more preferably 5 parts by weight or less. When the content of the curing accelerator is not less than the above lower limit and not more than the above upper limit, the effects of the present invention can be exhibited even more effectively.

[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 above inorganic filler, the dielectric loss tangent of the cured product can be further lowered. Moreover, by using the above-mentioned inorganic filler, the dimensional change due to heat of the cured product is further reduced. Only one kind of the above-mentioned inorganic filler may be used, or two or more kinds may be used in combination.

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

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 surface of the cured product can be reduced, and the adhesive strength between the cured product and the metal layer can be further increased. Further, fine wiring can be formed on the surface of the cured product, and better insulation reliability can be imparted to the cured product. When the inorganic filler is silica, the coefficient of thermal expansion of the cured product becomes even lower, and the dielectric loss tangent of the cured product becomes even lower. Note that the silica may be hollow silica.

From the viewpoint of increasing thermal conductivity and insulation, the inorganic filler is preferably alumina or boron nitride. In particular, since boron nitride has anisotropy, it is possible to further reduce the coefficient of linear thermal expansion.

The average particle size of the inorganic filler is preferably 50 nm or more, more preferably 100 nm or more, even more preferably 500 nm or more, preferably 5 μm or less, more preferably 3 μm or less, and still more preferably 1 μm or less. When the average particle size of the inorganic filler is 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 bond between the insulating layer and the metal layer can be reduced. Adhesion can be further improved.

As the average particle size of the inorganic filler, a value of the median diameter (d50) that is 50% is adopted. The above average particle size can be measured using a laser diffraction scattering type particle size distribution measuring device. In addition, when the inorganic filler is agglomerated particles, the average particle size of the inorganic filler means the primary particle size.

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

The inorganic filler is preferably surface-treated, more preferably surface-treated with a coupling agent, and even more preferably surface-treated with a silane coupling agent. By surface-treating the inorganic filler, the surface roughness of the surface of the roughened cured product becomes even smaller, and the adhesive strength between the cured product and the metal layer becomes even higher. Furthermore, since the inorganic filler is surface-treated, finer wiring can be formed on the surface of the cured product, and even better inter-wiring insulation reliability and interlayer insulation reliability can be achieved on the cured product. can be granted.

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 methacrylsilane, acrylicsilane, aminosilane, imidazolesilane, vinylsilane, and epoxysilane.

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, and more preferably 80% by weight. % or less. When the content of the inorganic filler is equal to or higher than the lower limit, the dielectric loss tangent effectively decreases. When the content of the inorganic filler is below the upper limit, thermal dimensional stability can be improved and warping of the cured product can be effectively suppressed. When the content of the inorganic filler is not less than the above lower limit and not more than the above upper limit, the surface roughness of the surface of the cured product can be further reduced, and finer wiring can be formed on the surface of the cured product. Can be done. Furthermore, with the content of this inorganic filler, it is possible to lower the coefficient of thermal expansion of the cured product and at the same time improve smear removability.

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

The above curing agents include phenol compounds (phenol curing agents), active ester compounds, cyanate ester compounds (cyanate ester curing agents), benzoxazine compounds (benzoxazine curing agents), carbodiimide compounds (carbodiimide curing agents), amine compounds (amine curing agent), thiol compounds (thiol curing agent), phosphine compounds, dicyandiamide, acid anhydrides, and the like. The curing agent preferably has a functional group capable of reacting with the epoxy group of the epoxy compound.

From the viewpoint of further increasing the thermal dimensional stability of the cured product, the curing agent preferably contains a phenol 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 phenol compound, an active ester compound, a cyanate ester compound, a benzoxazine compound, or a carbodiimide compound, and preferably contains an active ester compound. is even more preferable.

From the viewpoint of further increasing 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.

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

Commercially available products of the above-mentioned phenol compounds include novolac type phenol ("TD-2091" manufactured by DIC Corporation), biphenyl novolac type phenol ("MEH-7851" manufactured by Meiwa Kasei Co., Ltd.), and aralkyl type phenol compound ("MEH" manufactured by Meiwa Kasei Co., Ltd.). -7800''), and phenols having an aminotriazine skeleton (“LA-1356” and “LA-3018-50P” manufactured by DIC Corporation).

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

In the above formula (A), X ₁ represents a group having an aliphatic chain, a group having an aliphatic ring, or a group having an aromatic ring, and X ₂ 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, a naphthalene ring which may have a substituent, and the like. Examples of the above-mentioned substituents include hydrocarbon groups. The number of carbon atoms in the hydrocarbon group is preferably 12 or less, more preferably 6 or less, still more preferably 4 or less.

In the above formula (A), the combination of X ₁ and X ₂ is a combination of a benzene ring that may have a substituent and a benzene ring that may have a substituent, Examples include a combination of a benzene ring which may have a substituent and a naphthalene ring which may have a substituent. Furthermore, in the above formula (A), examples of the combination of X ₁ and X ₂ include a combination of a naphthalene ring that may have a substituent and a naphthalene ring that may have a substituent.

The above active ester compound is not particularly limited. From the viewpoint of further enhancing the thermal dimensional stability and flame retardance 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 loss tangent of the cured product and increasing the thermal dimensional stability of the cured product, it is more preferable that the active ester compound has a naphthalene ring or a dicyclopentadiene skeleton in the main chain skeleton.

Examples of commercially available active ester compounds include "HPC-8000-65T", "EXB9416-70BK", "HPC-8150-62T", "EXB-8" and "EXB8100-65T" manufactured by DIC. .

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

Commercial products of the above cyanate ester compounds include phenol novolak cyanate ester resins (PT-30 and PT-60 manufactured by Lonza Japan), and prepolymers in which bisphenol cyanate ester resins are trimerized (Lonza Japan). ``BA-230S'', ``BA-3000S'', ``BTP-1000S'', and ``BTP-6020S'' manufactured by the company.

Examples of the above-mentioned benzoxazine compounds include Pd type benzoxazine and Fa type benzoxazine.

Commercially available products of the benzoxazine compound include "P-d type" manufactured by Shikoku Kasei Kogyo Co., Ltd. and "ODA-BOZ" manufactured by JFE Chemical Company.

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 left end are bonding sites with other groups. Only one kind of the above-mentioned carbodiimide compound may be used, or two or more kinds thereof may be used in combination.

In the above formula (C), represents a group, and p represents an integer of 1 to 5. When a plurality of Xs exist, the plurality of Xs may be the same or different.

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

Commercially available carbodiimide compounds include "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", "Carbodilite V-09", and "Carbodilite V-04K" manufactured by Nisshinbo Chemical Co., Ltd. 10M-SP" and "Carbodilite 10M-SP (revised)," as well as Rhein Chemie's "Stavaxol P," "Stavaxol P400," and "Hikasil 510."

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

Examples of commercially available acid anhydrides include "Rikacid TDA-100" manufactured by Shin Nippon Rika Co., Ltd.

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, with respect to 100 parts by weight of the total content of the imide compound X and the curable compound. is 120 parts by weight or less, more preferably 100 parts by weight or less. When the content of the curing agent is at least the above lower limit and below the above upper limit, the curability is even better, the thermal dimensional stability is further improved, and the volatilization of residual unreacted components can be further suppressed.

[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. Only one kind of the above-mentioned thermoplastic resin may be used, or two or more kinds thereof may be used in combination.

From the viewpoint of improving handling properties 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.

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

The above-mentioned weight average molecular weight of the above-mentioned thermoplastic resin means the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The content of the thermoplastic resin is preferably 1% by weight or more, more preferably 2% by weight or more, preferably 30% by weight or less, based on 100% by weight of the components excluding the inorganic filler and solvent in the resin material. Preferably it is 20% by weight or less. When the content of the thermoplastic resin is not less than the lower limit and not more than the upper limit, the resin film has good embedding properties in holes or irregularities of the circuit board. When the content of the thermoplastic resin is equal to or higher than the lower limit, the resin film can be formed even more easily, and an even better insulating layer can be obtained. When the content of the thermoplastic resin is below the above upper limit, the coefficient of thermal expansion of the cured product becomes even lower. When the content of the thermoplastic resin is below the 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.

[solvent]
The resin material does not contain or contains a solvent. The resin material may or may not contain 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 improved. Moreover, the above-mentioned solvent may be used to obtain a slurry containing the above-mentioned inorganic filler. Only one type of the above solvent may be used, or two or more types may be used in combination.

The above solvents include acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane, toluene, xylene, methyl ethyl ketone, Examples include N,N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidone, n-hexane, cyclohexane, cyclohexanone, and naphtha as a mixture.

It is preferable that most of the solvent be removed when the 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 solvent in the resin composition is not particularly limited. The content of the solvent can be changed as appropriate in consideration of the coatability of the resin composition.

When the resin material is a B-stage film, the content of the solvent is preferably 1% by weight or more, more preferably 2% by weight or more, and preferably 10% by weight or less based on 100% by weight of the B-stage film. , more preferably 5% by weight or less.

[Other ingredients]
In order to improve impact resistance, heat resistance, resin compatibility, workability, etc., the above resin materials contain organic fillers, leveling agents, flame retardants, coupling agents, coloring agents, antioxidants, and UV deterioration prevention. The composition may also contain agents, antifoaming agents, thickeners, thixotropy imparting agents, and the like.

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 vinylsilane, aminosilane, imidazolesilane, and epoxysilane.

(resin film)
A resin film (B-staged product/B-stage film) is obtained by molding the above-described resin composition into a film. It is preferable that the resin material is a resin film. Preferably, the resin film is a B-stage film.

Examples of methods for obtaining a resin film by molding a resin composition into a film include the following methods. An extrusion molding method in which a resin composition is melt-kneaded using an extruder, extruded, and then molded into a film using a T-die, a circular die, or the like. A casting method in which a resin composition containing a solvent is cast and formed into a film. Other conventionally known film forming methods. An extrusion molding method or a casting molding method is preferable because it is possible to reduce the thickness. The film includes sheets.

A resin film, which is a B-stage film, can be obtained by forming a resin composition into a film and heating and drying it 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. can.

A film-like resin composition that can be obtained by the drying process as described above is referred to as a B-stage film. The B-stage film is in a semi-cured state. A semi-cured product is not completely cured and may be further cured.

The resin film does not need to be prepreg. If the resin film is not a prepreg, migration will not occur along the glass cloth or the like. Moreover, when laminating or pre-curing the resin film, unevenness caused by the glass cloth will not occur on the surface.

The 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 base film. Preferably, the metal foil is copper foil.

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

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

(Other details of resin material)
The resin material preferably has an exothermic peak top temperature of 200°C or lower, more preferably 195°C or lower, and 190°C or lower when differential scanning calorimetry (DSC) is performed. It is further preferable that the exothermic peak top temperature is . In this case, the effects of the present invention can be exhibited even more effectively. In addition, when the resin material has a plurality of exothermic peaks, "having an exothermic peak top temperature below T°C" means that the peak top temperature of at least one exothermic peak is below T°C.

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

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 higher than the lower limit, the resin material can be suitably used as an adhesive material, an interlayer insulation material, and the like. The initial adhesive strength may be 15 N/cm or less, or 10 N/cm or less.

The initial adhesive strength of the cured product to copper foil is measured as follows. A 35 μm thick copper foil is laminated on both sides of a 40 μm thick resin film (resin material) to obtain a laminate (1). The obtained laminate (1) was temporarily cured by heating at 180°C for 30 minutes, and then heated at 200°C for 90 minutes to harden the resin film placed between the copper foils. ). The laminate (2) is cut into a 1 cm wide piece to obtain a measurement sample. Within 24 hours after producing the laminate (2), the peel strength of the measurement sample was measured using a tensile tester when T-peel was performed at 25°C and a peel rate of 20 mm/min. The peel strength obtained is taken as the initial adhesive strength. In addition, examples of the above-mentioned copper foil include "UN series" manufactured by Fukuda Metal Foil and Powder Industries Co., Ltd. In this commercial product, the glossy side of the copper foil can be used as the surface to be bonded to the resin film. Examples of the tensile tester include "UCT-500" manufactured by ORIENTEC.

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.

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 temporarily cure it, and then heated at 200° C. for 90 minutes to obtain a cured product. The tan δ obtained when the obtained cured product was measured using a dynamic viscoelasticity measuring device at a heating rate of 10° C./min, a frequency of 10 Hz, and a distance between chucks of 24 mm from 0° C. to 300° C. The peak temperature of the curve is defined as the glass transition temperature. As the dynamic viscoelasticity measuring device, for example, “DMS6100” manufactured by Hitachi High-Tech Science Co., Ltd. can be used. In addition, 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.

The above resin material can be used for various purposes. The resin material described above is suitably used, for example, to form a mold resin in which a semiconductor chip is embedded in a semiconductor device. Further, the above resin material is suitably used as a substitute for liquid crystal polymer (LCP), as a millimeter wave antenna, and as a redistribution layer. The above-mentioned resin material is not limited to the above-mentioned applications, but can be suitably used for wiring formation applications in general.

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

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

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

(Laminated structure and copper clad laminate)
A laminated structure can be obtained by laminating a lamination target member having a metal layer on one or both surfaces of the resin film. The laminated structure includes a member to be laminated 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 resin material described above. The method for laminating the resin film and the member to be laminated is not particularly limited, and any known method can be used. For example, the resin film can be laminated on the member to be laminated using a device such as a parallel plate press or a roll laminator while heating or pressing without heating.

The material of the metal layer is preferably copper.

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

The above resin material is suitably used to obtain a copper-clad laminate. An example of the above-mentioned copper-clad laminate includes a copper-clad laminate including a copper foil and a resin film laminated on one surface of the copper foil, where the resin film is the resin material mentioned above.

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. Moreover, in order to increase the adhesive strength between the cured product of the resin material and the copper foil, it is preferable that the copper foil has fine irregularities on its surface. The method of forming the unevenness is not particularly limited. Examples of the method for forming the above-mentioned unevenness include a method of forming the unevenness by a treatment using a known chemical solution.

(Circuit board with insulation layer)
The above resin material is suitably used to obtain a circuit board with an insulating layer. An example of the circuit board with an insulating layer includes a circuit board and an insulating layer disposed on the surface of the circuit board, the insulating layer being a cured product of the resin material described above. Can be mentioned.

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

The above circuit board with an insulating layer can be obtained by a conventionally known method.

(Multilayer board and multilayer printed wiring board)
The above resin material is suitably used to obtain a multilayer substrate. An example of the multilayer board is a multilayer board that includes a circuit board and an insulating layer laminated on the circuit board. The insulating layer of the multilayer substrate is a cured product of the resin material described above. The insulating layer is preferably laminated on the surface of the circuit board on which the circuit (metal layer) is provided. Preferably, a portion of the insulating layer is embedded between the circuits.

In the multilayer board, it is preferable that the surface of the insulating layer opposite to the surface on which the circuit board is laminated is subjected to a roughening treatment.

A conventionally known roughening treatment method can be used as the roughening treatment method, and is not particularly limited. The surface of the insulating layer may be subjected to swelling treatment before roughening treatment.

Preferably, the multilayer substrate further includes a copper plating layer laminated on the roughened surface of the insulating layer.

Another example of the multilayer board is a circuit board, an insulating layer laminated on the surface of the circuit board, and a copper layer laminated on the surface of the insulating layer opposite to the surface on which the circuit board is laminated. For example, a multilayer substrate including a foil may be mentioned. It is preferable that the insulating layer is formed by using a copper-clad laminate including a copper foil and a resin film laminated on one surface of the copper foil, and by curing the resin film. Furthermore, it is preferable that the copper foil is etched and is a copper circuit.

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

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

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. In the multilayer printed wiring board, at least one of the insulating layers is a cured product of the resin material described above.

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

In the multilayer printed wiring board 11 shown in FIG. 1, a plurality of insulating layers 13 to 16 are laminated on the upper surface 12a of the circuit board 12. The insulating layers 13 to 16 are cured material layers. A metal layer 17 is formed in a part of the upper surface 12 a of the circuit board 12 . Among the plurality of insulating layers 13 to 16, a metal layer 17 is formed in a part of the upper surface 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. ing. Metal layer 17 is a circuit. A metal layer 17 is arranged between the circuit board 12 and the insulating layer 13, and between each 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).

In the multilayer printed wiring board 11, the insulating layers 13 to 16 are formed of a cured product of the resin material described above. In this embodiment, the surfaces of the insulating layers 13 to 16 are roughened, so that fine holes (not shown) are formed in the surfaces of the insulating layers 13 to 16. Further, a metal layer 17 extends inside the fine hole. Furthermore, in the multilayer printed wiring board 11, the widthwise dimension (L) of the metal layer 17 and the widthwise dimension (S) of the portion where the metal layer 17 is not formed can be made smaller. Furthermore, 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 or through hole connection (not shown).

Hereinafter, the present invention will be specifically explained by giving Examples and Comparative Examples. The invention is not limited to the following examples.

The following materials were prepared.

(Imide compound X)
Imide compound X1:
Imide compound X1 (molecular weight 810) represented by the following formula (X1) was synthesized according to Synthesis Example X1 below.

<Synthesis example X1>
In a reaction vessel equipped with a stirrer, a water separator, and a nitrogen gas introduction tube, 10.0 parts by weight of 1,3-bis(4-aminophenoxy)benzene and 20.8 parts by weight of phenylethynyl trimellitic anhydride. was dissolved in 70 parts by weight of N-methylpyrrolidone. After the resulting solution was stirred at room temperature for 24 hours, 10.8 parts by weight of pyridine and 14.0 parts by weight of acetic anhydride were added to this solution, and the mixture was further stirred for 15 minutes. The obtained solution was added to 300 mL of methanol, and the precipitated solid was collected. The collected solid was dried in a vacuum oven at 40° C. for 24 hours to obtain imide compound X1 represented by the following formula (X1).

Imide compound X2:
Imide compound X2 (molecular weight 820) represented by the following formula (X2) was synthesized according to Synthesis Example X2 below.

<Synthesis example X2>
In a reaction vessel equipped with a stirrer, a water separator, and a nitrogen gas introduction 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. Ta. The resulting solution was stirred under reflux for 24 hours. Next, the solution was added to 200 mL of water, and the precipitated solid was collected. Further, a liquid 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 liquid was added to the collected solids and 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 vacuum oven at 40° C. for 24 hours to obtain an amine compound MA represented by the following formula (MA).

Next, in a reaction vessel equipped with a stirrer, a water separator, and a nitrogen gas introduction tube, 10 parts by weight of the amine compound MA and 20.2 parts by weight of phenylethynyl trimellitic anhydride were added to 70 parts by weight of N-methylpyrrolidone. Dissolved. After the resulting solution was stirred at room temperature for 24 hours, 10.5 parts by weight of pyridine and 13.6 parts by weight of acetic anhydride were added to this solution, and the mixture was further stirred for 15 minutes. The obtained solution was added to 300 mL of methanol, and the precipitated solid was collected. The collected solid was dried in a vacuum oven at 40° C. for 24 hours to obtain imide compound X2 represented by the following formula (X2).

Imide compound X3:
Imide compound X3 (molecular weight 8600) represented by the following formula (X3) was synthesized according to Synthesis Example X3 below.

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

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

(curable compound)
Imide compound Y1:
An imide compound Y1 (molecular weight 750) represented by the following formula (Y1) was synthesized according to Synthesis Example Y1 below.

<Synthesis example Y1>
Represented by the following formula (Y1) in the same manner as Synthesis Example X1 except that 18.7 parts by weight of phenylethynylphthalic anhydride was used instead of 20.8 parts by weight of phenylethynyl trimellitic anhydride. Imide compound Y1 was obtained.

Phenylethynyl trimellitic anhydride (“NEXIMID300” manufactured by NEXUM)
Bisphenol F type epoxy compound (“EXA-830CRP” manufactured by DIC, liquid at 25°C)
Biphenylaralkyl epoxy compound (Nippon Kayaku Co., Ltd. "NC3000", solid at 25°C)

(hardening accelerator)
Imidazole compound (2-ethyl-4-methylimidazole)
Organic phosphorus compound (triphenylphosphine)

(hardening agent)
Active ester compound-containing liquid (“HPC-8000-65T” manufactured by DIC, solid content 65% by weight)

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

(Thermoplastic resin)
Polyimide resin-containing liquid (polyimide resin-containing liquid containing a reaction product of tetracarboxylic dianhydride and dimer diamine (nonvolatile content 26.8% by weight), synthesized according to Synthesis Example T below)

<Synthesis example T>
300.0 g of tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan LLC) and 665.5 g of cyclohexanone were placed in a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube. 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 Company) were added dropwise into the reaction vessel. Next, 121.0 g of methylcyclohexane and 423.5 g of ethylene glycol dimethyl ether were added into 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. Note that the molar ratio of acid component/amine component was 1.04.

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

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

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

Preparation of resin film:
After applying the obtained resin material onto the release-treated surface of a polyethylene terephthalate film (PET film, "XG284" manufactured by Toray Industries, Inc., thickness 25 μm) using an applicator, the film was heated in a gear oven at 100°C. The solution was dried for 2 minutes and 30 seconds in a vacuum chamber to evaporate 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) having a thickness of 40 μm was laminated on a PET film was obtained.

(1) Low-temperature curing properties of resin materials (1-1) Curing temperature (exothermic peak top temperature)
Using a differential scanning calorimetry device ("EXTEAR DSC6100" manufactured by Hitachi High-Tech Science), 10 mg of the obtained 40 μm thick resin film was weighed out and heated from 30 to 350 °C at a heating rate of 10 °C/min. The exothermic peak was measured by increasing the temperature. The curing temperature was evaluated based on the following criteria.

[Criteria for curing temperature]
○: Exothermic peak top temperature is 200°C or less △: Exothermic peak top temperature exceeds 200°C and 300°C or less ×: Exothermic peak top temperature exceeds 300°C or no exothermic peak is observed

(1-2) Curing reaction rate (heating conditions: 190°C and 1 hour)
The calorific value was determined from the peak area of the exothermic peak of the resin film obtained in the measurement of the above "(1-1) curing temperature (exothermic peak top temperature)". Further, 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 (exothermic peak top temperature)" above. The calorific value was determined from the peak area of the exothermic peak of the obtained cured product. The curing reaction rate was determined by the following formula and evaluated based on the following criteria.

Curing reaction rate (%) = (AB)/A x 100
A: Calorific value determined from the peak area of the exothermic peak of the resin film B: Calorific value determined from the peak area of the exothermic peak of the cured product

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

(2) Heat resistance of cured product (2-1) Glass transition temperature of cured product The obtained resin films with a thickness of 40 μm were laminated to obtain a resin film with a thickness of 400 μm. The obtained resin film with a thickness of 400 μm was heated at 180° C. for 30 minutes to temporarily cure it, and then heated at 200° C. for 90 minutes to obtain a cured product. The obtained cured product was heated from 0°C to 300°C using a dynamic viscoelasticity measurement device (“DMS6100” manufactured by Hitachi High-Tech Science Co., Ltd.) at a heating rate of 10°C/min, a frequency of 10Hz, and a distance between chucks of 24 mm. Measured under warm conditions. The peak temperature of the obtained tan δ curve was defined as the glass transition temperature. Glass transition temperature was evaluated based on the following criteria.

[Judgment criteria for glass transition temperature of cured product]
○: Glass transition temperature is 150°C or higher △: Glass transition temperature is 120°C or higher and lower than 150°C ×: Glass transition temperature is lower than 120°C

(2-2) Heat decomposition resistance of cured product (5% weight loss temperature)
A cured resin film was obtained according to the method described in "(2-1) Glass transition temperature of cured product" above. The obtained cured product was measured at a 5% weight loss temperature using a thermogravimetric measuring device (“TG/DTA6200” manufactured by Hitachi High-Tech Science Co., Ltd.) in a temperature range of 30°C to 500°C and under heating conditions of 10°C/min. was measured. The heat decomposition resistance of the cured product was evaluated based on the following criteria.

[Criteria for determining thermal decomposition resistance of cured product]
○○: 5% weight loss temperature is 350°C or higher ○: 5% weight loss temperature is 330°C or higher and lower than 350°C △: 5% weight loss temperature is 300°C or higher and lower than 330°C ×: 5% weight loss temperature is 300°C less than

(3) Initial adhesive strength of cured product to copper foil Copper foils with a thickness of 35 μm were laminated on both sides of the obtained resin film with a thickness of 40 μm to obtain a laminate (1). The laminate (1) was heated at 180°C for 30 minutes to temporarily cure it, and then heated at 200°C for 90 minutes to harden the resin film placed between the copper foils to obtain a laminate (2). Ta. The laminate (2) was cut into a 1 cm wide piece to obtain a measurement sample. Within 24 hours after producing the laminate (2), the measurement sample was tested in a T-shape at 25°C and a peeling rate of 20 mm/min using a tensile tester ("UCT-500" manufactured by ORIENTEC). The peel strength at the time of peeling was measured, and the obtained peel strength was taken as the initial adhesive strength. Note that "UN series" manufactured by Fukuda Metal Foil and Powder Industries Co., Ltd. was used as the copper foil. When producing the laminate (1), the glossy side of this commercially available product was used as the surface to be adhered to the resin film. The initial adhesive strength of the cured product to copper foil was evaluated based on the following criteria.

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

(4) Thermal dimensional stability of cured product The obtained resin film with a thickness of 40 μm 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 obtained cured product was cut into a size of 3 mm x 25 mm. Using a thermomechanical analyzer (“EXSTAR TMA/SS6100” manufactured by Hitachi High-Tech Science Co., Ltd.), the cut cured material was measured at a temperature of 25°C to 150°C under the conditions of a tensile load of 33 mN and a temperature increase rate of 5°C/min. The average coefficient of linear expansion (ppm/°C) was calculated.

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

The compositions and results are shown in Tables 1 to 4 below. Note that the evaluation of "(3) Initial adhesive strength of cured product to copper foil" was performed on the resin films obtained in Examples 1 to 6 and Comparative Examples 1 to 4. In addition, evaluation of "(4) thermal dimensional stability of cured product" was performed on the resin films obtained in Examples 7 to 12 and Comparative Examples 5 and 6.

11...Multilayer printed wiring board 12...Circuit board 12a...Top surface 13-16...Insulating layer 17...Metal layer

Claims (18)

A resin material containing an imide compound X having a structure represented by the following formula (1), a curable compound, and a curing accelerator.

In the formula (1), * represents a bonding position. The resin material according to claim 1, wherein the imide compound X is a compound represented by the following formula (2).

In the formula (2), R ₁ represents an arbitrary group. The resin material according to claim 1 or 2, wherein the imide compound X is a compound represented by the following formula (21).

In the formula (21), R ₁ and R ₂ each independently represent an aliphatic diamine residue or an aromatic diamine residue, R ₃ represents an acid dianhydride residue, and n is 0 or 1. Represents an integer greater than or equal to The resin material according to any one of claims 1 to 3, wherein the curable compound contains an epoxy compound. The resin material according to claim 4, wherein the epoxy compound includes an epoxy compound that is liquid at 25°C. The resin material according to any one of claims 1 to 5, wherein the curing accelerator contains an amine compound, an imidazole compound, or an organic phosphorus compound. The resin material according to any one of claims 1 to 6, further comprising an inorganic filler. The resin material according to claim 7, wherein the inorganic filler is silica. The resin material according to any one of claims 1 to 8, further comprising a curing agent. The resin material according to claim 9, wherein the curing agent includes an active ester compound. The resin material according to any one of claims 1 to 10, which has an exothermic peak top temperature of 200° C. or less when differential scanning calorimetry is performed. The resin material according to any one of claims 1 to 11, wherein the cured product has an initial adhesive strength of 3 N/cm or more to copper foil. The resin material according to any one of claims 1 to 12, which is a resin film. The resin material according to any one of claims 1 to 13, which is an adhesive material. The resin material according to any one of claims 1 to 14, which is an interlayer insulation material. A cured product of the resin material according to any one of claims 1 to 15. a circuit board;
an insulating layer disposed on the 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 any one of claims 1 to 14. a circuit board;
a plurality of insulating layers disposed on the surface of the circuit board;
a metal layer disposed between the plurality of insulating layers,
A multilayer printed wiring board, wherein at least one of the plurality of insulating layers is a cured product of the resin material according to any one of claims 1 to 15.

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