JP2020132880A - Resin material and multilayer printed wiring board - Google Patents

Abstract

To provide a resin material that can, in the cured product of the resin material, 1) lower the dielectric loss tangent, 2) enhance the thermal dimensional stability, 3) enhance the elongation property, and 4) enhance the bending property.SOLUTION: The resin material according to the present invention contains a polymaleimide compound that has three or more maleimide skeletons and that has one or more imide skeletons, and a curing accelerator.SELECTED DRAWING: Figure 1

Description

The present invention relates to a resin material containing a polymaleimide compound. The present invention also relates to a multilayer printed wiring board using the above resin material.

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

Patent Document 1 below discloses a resin composition containing a compound having a maleimide group, a divalent group having at least two imide bonds, and a saturated or unsaturated divalent hydrocarbon group. .. Patent Document 1 describes that a cured product of this resin composition can be used as an insulating layer for a multilayer printed wiring board or the like.

Patent Document 2 below discloses a resin composition for an electronic material containing a bismaleimide compound, wherein the bismaleimide compound has two maleimide groups and one or more polyimide groups having a specific structure. .. In the bismaleimide compound, the two maleimide groups are independently bonded to both ends of the polyimide group via at least a first linking group in which eight or more atoms are linearly linked. ..

WO2016 / 114286A1 JP-A-2018-90728

When the insulating layer is formed by using the conventional resin material as described in Patent Documents 1 and 2, the dielectric loss tangent of the cured product is not sufficiently low, and the thermal dimensional stability is not sufficiently high. Sometimes.

Further, when the insulating layer is formed by using a conventional resin material, the elongation characteristics of the cured product may not be sufficiently high, or the bending characteristics of the cured product may not be sufficiently high.

An object of the present invention is that in a cured product of a resin material, 1) the dielectric loss tangent can be lowered, 2) the thermal dimensional stability can be improved, 3) the elongation characteristics can be improved, and 4) the bending characteristics Is to provide a resin material which can enhance. Another object of the present invention is to provide a multilayer printed wiring board using the above resin material.

According to a broad aspect of the present invention, there is provided a resin material containing a polymaleimide compound having three or more maleimide skeletons and one or more imide skeletons, and a curing accelerator.

In certain aspects of the resin material according to the present invention, the polymaleimide compound has three or more ends due to having a branched structure, and has the maleimide skeleton at three or more ends.

In certain aspects of the resin material according to the present invention, the polymaleimide compound has at least one skeleton derived from dimerdiamine.

In certain aspects of the resin material according to the present invention, the polymaleimide compound has at least one skeleton derived from dimerdiamine, and the skeleton derived from diaminediamine is directly bonded to the maleimide skeleton at the terminal. are doing.

In certain aspects of the resin material according to the present invention, the maleimide skeleton at the terminal is bonded to the main chain via an ester bond.

In a specific aspect of the resin material according to the present invention, the molecular weight of the polymaleimide compound is 1000 or more and 50,000 or less.

In certain aspects of the resin material according to the present invention, the resin material comprises an inorganic filler.

In a specific aspect of the resin material according to the present invention, 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.

In certain aspects of the resin material according to the present invention, the inorganic filler is silica.

In certain aspects of the resin material according to the present invention, the resin material comprises a thermosetting compound different from the polymaleimide compound having three or more maleimide skeletons and one or more imide skeletons.

In certain aspects of the resin material according to the present invention, the thermosetting compound is a maleimide compound, an epoxy compound, a vinyl compound, a benzoxazine compound, or a cyanate ester compound.

In certain aspects of the resin material according to the invention, the resin material comprises the thermosetting compound and a curing agent, the thermosetting compound comprises an epoxy compound, and the curing agent is a phenol compound. , Active ester compound, and at least one component of the carbodiimide compound.

In certain aspects of the resin material according to the present invention, the curing agent comprises a phenolic compound and an active ester compound.

In certain aspects of the resin material according to the present invention, at least one of the thermosetting compound and the curing agent has an amide bond or an imide bond.

In certain aspects of the resin material according to the present invention, the thermosetting compound has an amide bond or an imide bond.

In certain aspects of the resin material according to the present invention, the resin material is a resin film.

The resin material according to the present invention is preferably used as an insulating material.

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

According to a broad aspect of the present invention, a circuit board, a plurality of insulating layers arranged on the surface of the circuit board, and a metal layer arranged between the plurality of insulating layers are provided, and the plurality of insulating layers are provided. A multilayer printed wiring board is provided in which at least one of the layers is a cured product of the resin material described above.

The resin material according to the present invention includes a polymaleimide compound having three or more maleimide skeletons and one or more imide skeletons, and a curing accelerator. Since the resin material according to the present invention has the above-mentioned structure, 1) the dielectric loss tangent can be lowered, 2) the thermal dimensional stability can be improved, and 3) the cured product of the resin material can be provided. It is possible to exert all the effects of 1) to 4) that the elongation characteristics can be enhanced and the bending characteristics can be enhanced 4).

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.

Hereinafter, the present invention will be described in detail.

The resin material according to the present invention includes a polymaleimide compound having three or more maleimide skeletons and one or more imide skeletons, and a curing accelerator. The maleimide skeleton and the imide skeleton exist as partial skeletons in the polymaleimide compound.

The present specification discloses a resin material that may contain trimaleimide derived from trimertriamine as the polymaleimide compound. In the resin material according to the present invention, the polymaleimide compound is preferably a polymaleimide compound (excluding trimaleimide derived from trimertriamine). The resin material according to the present invention may contain a polymaleimide compound having three or more maleimide skeletons and one or more imide skeletons (excluding trimaleimide derived from trimertriamine) and a curing accelerator. preferable. In the present specification, there is also an invention of a resin material containing a polymaleimide compound having three or more maleimide skeletons and one or more imide skeletons (excluding trimaleimide derived from trimertriamine) and a curing accelerator. Disclose.

Since the resin material according to the present invention has the above-mentioned structure, 1) the dielectric loss tangent can be lowered, 2) the thermal dimensional stability can be improved, and 3) the cured product of the resin material can be provided. It is possible to exert all the effects of 1) to 4) that the elongation characteristics can be enhanced and the bending characteristics can be enhanced 4).

In the resin material according to the present invention, the elongation characteristics of the cured product can be enhanced, so that the plating peel strength can be enhanced. Further, the resin material according to the present invention has high bending characteristics of the cured product and can increase the flexibility of the cured product, so that the occurrence of cracks can be suppressed. Therefore, the reliability of the multilayer printed wiring board or the like obtained by using the resin material of the present invention can be improved.

Further, since the cured product of the resin material according to the present invention can enhance stress relaxation property, the occurrence of warpage can be effectively suppressed, and the occurrence of cracks due to thermal shock, physical shock, etc. is effective. Can be suppressed to.

Further, since the resin material according to the present invention has the above-mentioned structure, smear can be effectively removed by desmear treatment. Further, since the resin material according to the present invention has the above-mentioned structure, the uniformity of the surface roughness after etching can be improved, and the adhesion between the insulating layer and the metal layer can be improved. it can.

The resin material according to the present invention may be a resin composition or a resin film. The resin composition has fluidity. The resin composition may be in the form of a paste. The paste form contains a liquid. The resin material according to the present invention is preferably a resin film because it is excellent in handleability.

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

Hereinafter, the details of each component used in the resin material according to the present invention, the use of the resin material according to the present invention, and the like will be described.

[Polymaleimide compound having 3 or more maleimide skeletons and 1 or more imide skeletons]
The resin material according to the present invention includes a polymaleimide compound having three or more maleimide skeletons and one or more imide skeletons (hereinafter, may be referred to as "polymaleimide compound A"). The polymaleimide compound A is preferably a polymaleimide compound (excluding trimaleimide derived from trimertriamine). The maleimide skeleton and the imide skeleton each exist as partial skeletons in the polymaleimide compound A. The polymaleimide compound A contained in the resin material according to the present invention is preferably a compound different from the trimaleimide derived from trimertriamine. As the polymaleimide compound A, only one kind may be used, or two or more kinds may be used in combination.

The polymaleimide compound A is a thermosetting compound.

The polymaleimide compound A preferably has a branched structure. The polymaleimide compound A having a branched structure has three or more ends. Therefore, the polymaleimide compound A preferably has three or more ends due to having a branched structure. Since the polymaleimide compound A has a branched structure, when the molecular weight of the polymaleimide compound A is 1000 or more and 100,000 or less, the thermal dimensional stability of the cured product can be improved, and particularly when the molecular weight is 10,000 or less. In some cases, the melt viscosity of the resin material can be lowered, and the embedding property in the unevenness of the substrate or the like can be improved. Further, since the polymaleimide compound A has a branched structure, the flexibility of the resin film can be increased when the molecular weight of the polymaleimide compound A is 10,000 or more.

From the viewpoint of lowering the melt viscosity of the resin material, lowering the dielectric loss tangent of the cured product, and increasing the thermal dimensional stability of the cured product, the polymaleimide compound A has three or more branched structures. It is preferable to have a terminal and to have the maleimide skeleton at three or more of the terminals. In this case, all the terminals of the polymaleimide compound A may or may not have the maleimide skeleton.

The polymaleimide compound A has a branched structure from the viewpoint of further lowering the melt viscosity of the resin material, further lowering the dielectric loss tangent of the cured product, and further enhancing the thermal dimensional stability of the cured product. Therefore, it is more preferable to have three or more ends and to have the maleimide skeleton at all the ends.

From the viewpoint of exerting all the effects of 1) to 4) above, it is preferable that the maleimide skeleton at the terminal is bonded to the main chain of the polymaleimide compound A via an ester bond. The polymaleimide compound A preferably has an ester bond in the branched chain having the maleimide skeleton at the terminal.

From the viewpoint of exerting all the effects of 1) to 4) above, the number of the maleimide skeletons in the polymaleimide compound A is 3 or more.

The number of the maleimide skeletons in the polymaleimide compound A is preferably 4 or more, preferably 25 or less, more preferably 10 or less, and further preferably 5 or less. When the number of the maleimide skeletons is equal to or more than the above lower limit and equal to or less than the above upper limit, the effects of the above 1) to 4) can be more effectively exhibited. The number of the maleimide skeletons in the polymaleimide compound A may be three.

The polymaleimide compound A may have a maleimide skeleton at a portion other than the terminal.

From the viewpoint of exerting all the effects of 1) to 4) above, the number of the imide skeletons in the polymaleimide compound A is one or more.

The number of the imide skeletons in the polymaleimide compound A is preferably 3 or more, preferably 25 or less, more preferably 10 or less, still more preferably 5 or less, and particularly preferably 4 or less. When the number of the imide skeletons is not less than the above lower limit and not more than the above upper limit, the effects of the above 1) to 4) can be exhibited even more effectively. The number of the imide skeletons in the polymaleimide compound A may be one.

In the polymaleimide compound A, the number of the maleimide skeletons and the number of the imide skeletons may be the same or different.

The number of the maleimide skeletons in the polymaleimide compound A and the number of the imide skeletons are the same from the viewpoint of further lowering the dielectric adjacency of the cured product and further enhancing the thermal dimensional stability of the cured product. Alternatively, it is preferable that the number of the maleimide skeletons is larger than the number of the imide skeletons.

When the number of the maleimide skeletons is larger than the number of the imide skeletons, the number of the maleimide skeletons is preferably one or more and more preferably two or more than the number of the imide skeletons. When the number of the maleimide skeletons is larger than the number of the imide skeletons, the number of the maleimide skeletons is preferably 6 or less, more preferably 5 or less, more preferably 4 than the number of the imide skeletons. It is more preferably less than 3 pieces, and particularly preferably more than 3 pieces. In these cases, 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.

In the polymaleimide compound A, the number of maleimide skeletons may be smaller than the number of the imide skeletons. When the number of the maleimide skeletons is smaller than the number of the imide skeletons, the ratio of the number of the maleimide skeletons to the number of the imide skeletons (the number of maleimide skeletons / the number of imide skeletons) is preferably 0.05 or more. It is more preferably 0.1 or more, preferably 0.5 or less, and more preferably 0.3 or less. 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 polymaleimide compound A may have, for example, a structure represented by the following formula (10A) or a structure represented by the following formula (10B). The structure represented by the following formula (10A) or the following formula (10B) may be present in the side chain of the polymaleimide compound A. The structure represented by the following formula (10A) uses, for example, a diamine compound having a hydroxyl group such as 1,3-Diamino-2-propanol and a carboxylic acid such as 6-Malelimidohexanoic acid to form the above hydroxyl group. It can be obtained by reacting with a carboxyl group. The structure represented by the following formula (10B) is, for example, a compound obtained by reacting a monoamine compound such as serinol with a compound having a plurality of hydroxyl groups at the terminal, and a carboxylic acid such as 6-Maleimidiohexanoic acid. It can be obtained by reacting the above-mentioned hydroxyl group with a carboxyl group using and.

In the above formula (10A), R1 and R2 each represent a tetravalent organic group.

In the above formula (10B), R1 represents a tetravalent organic group.

The polymaleimide compound A preferably has at least one skeleton derived from dimerdiamine. The skeleton derived from the diamine diamine is a flexible skeleton. Therefore, when the polymaleimide compound A has a skeleton derived from the diamine diamine, it is possible to improve the sheet property of a resin film such as a B stage film. Further, since the stress relaxation property of the cured product can be enhanced, the occurrence of warpage can be effectively suppressed, and the reliability of the multilayer printed wiring board or the like can be enhanced. Further, since the etching property can be improved, smear can be effectively removed by the desmear treatment.

From the viewpoint of further enhancing the thermal dimensional stability of the cured product and further enhancing the adhesion between the insulating layer and the metal layer, the number of skeletons derived from the diamine diamine in the polymaleimide compound A is preferably 1. The number is more than 2, more preferably 2 or more, preferably 10 or less, and more preferably 25 or less. Further, at the time of synthesizing the polymaleimide compound A, the number of moles of the diamine diamine is preferably 10% or more and 80% or less in 100% of the moles of amine in the synthetic material.

In the polymaleimide compound A, the skeleton derived from the dimerdiamine is preferably directly bonded to the maleimide skeleton at the terminal of the polymaleimide compound A. More specifically, it is preferable that one of the nitrogen atoms in the skeleton derived from the dimer diamine is the nitrogen atom in the maleimide skeleton at the terminal. In this case, the reactivity of the maleimide group can be further enhanced, and the curing reaction can be sufficiently advanced. As a result, the thermal dimensional stability of the cured product can be further enhanced, and the adhesion between the insulating layer and the metal layer can be further enhanced.

In the polymaleimide compound A, all the maleimide skeletons may or may not be directly bonded to the skeleton derived from the dimerdiamine.

The number of the maleimide skeletons in the polymaleimide compound A and the number of skeletons derived from the dimerdiamine may be the same or different.

The polymaleimide compound A may have a skeleton derived from a diamine compound other than the diamine diamine.

When the polymaleimide compound A has a skeleton derived from the polycarboxylic acid, the polymaleimide compound A preferably has a skeleton derived from a reaction product of diamine diamine and acid dianhydride. The skeleton derived from the reaction product of the diamine diamine and the acid dianhydride preferably has the imide skeleton. 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 skeleton derived from the reaction product of the diamine diamine and the acid dianhydride has a skeleton derived from the diamine diamine.

The polymaleimide compound A preferably has a skeleton derived from a reaction product of the diamine diamine and an acid dianhydride between the maleimide skeleton and the skeleton derived from the diamine compound.

Examples of the acid dianhydride include tetracarboxylic dianhydride and the like.

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfonetetra. Carcarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3', 4,4'-biphenyl ether Tetetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2 , 3,4-Flantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl Sethylene dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3', 4,4'-perfluoroisopropyridenediphthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphinoxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenyl) Examples thereof include phthalic dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, and bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride.

Examples of the dimer diamine include Versamine 551 (trade name, manufactured by BASF Japan Ltd., 3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl) cyclohexene), Versamine 552 (trade name). , Cognix Japan Co., Ltd., hydrogenated Versamine 551), and PRIAMINE 1075, PRIAMINE 1074 (trade name, all manufactured by Claude Japan Co., Ltd.) and the like.

Examples of diamine compounds other than the above diamine diamines include 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (aminomethyl) norbornane, 3 (4), 8 (9) -bis. (Aminomethyl) tricyclo [5.2.1.02,6] decane, 1,1-bis (4-aminophenyl) cyclohexane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 2,7-diamino Fluorene, 4,4'-ethylenedianiline, isophorone diamine, 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (2,6-diethylaniline), 4,4'-methylenebis (2-ethyl) -6-methylaniline), 4,4'-methylenebis (2-methylcyclohexylamine), 1,4-diaminobutane, 1,10-diaminodecane, 1,12-diaminododecane, 1,7-diaminoheptane, 1 , 6-Diaminohexane, 1,5-diaminopentane, 1,8-diaminooctane, 1,3-diaminopropane, 1,11-diaminoundecane, 2-methyl-1,5-diaminopentane and the like.

The skeleton derived from the diamine diamine has or does not have an aliphatic ring. The skeleton derived from the diamine diamine may or may not have an aliphatic ring.

Skeletons derived from diamine compounds other than the diamine diamine have or do not have an aromatic ring. The skeleton derived from a diamine compound other than the diamine diamine may or may not have an aromatic ring.

Skeletons derived from diamine compounds other than the above diamine diamine have or do not have an aliphatic ring. The skeleton derived from the diamine compound other than the diamine diamine may or may not have an aliphatic ring.

Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, a chrysene ring, a triphenylene ring, a tetraphen ring, a pyrene ring, a pentacene ring, a picene ring and a perylene ring.

Examples of the aliphatic ring include a monocycloalkane ring, a bicycloalkane ring, a tricycloalkane ring, a tetracycloalkane ring, and a dicyclopentadiene.

The molecular weight of the polymaleimide compound A is preferably 1000 or more, more preferably more than 5000, still more preferably 7500 or more, particularly preferably 8000 or more, preferably 70,000 or less, more preferably 50,000 or less, still more preferably 25,000 or less. It is particularly preferably 18,000 or less, and most preferably 15,000 or less. When the molecular weight of the polymaleimide compound A is at least the above lower limit, the coefficient of linear expansion of the resin material can be suppressed to a low level. Further, when the molecular weight of the polymaleimide compound A exceeds 70,000, the melt viscosity of the resin material becomes higher and the embedding property in the uneven surface is lowered as compared with the case where the molecular weight of the polymaleimide compound A is 70,000 or less. There is. Further, when the molecular weight of the polymaleimide compound A exceeds 50,000, the melt viscosity of the resin material becomes higher and the embedding property on the uneven surface is lowered as compared with the case where the molecular weight of the polymaleimide compound A is 50,000 or less. There is. The molecular weight of the maleimide compound is particularly preferably 1000 or more and 50,000 or less.

The molecular weight of the polymaleimide compound A means a molecular weight that can be calculated from the structural formula when the polymaleimide compound A is not a polymer and when the structural formula of the polymaleimide compound A can be specified. The molecular weight of the polymaleimide compound A indicates the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) when the polymaleimide compound A is a polymer.

From the viewpoint of further enhancing the thermal dimensional stability of the cured product and further enhancing the adhesion between the insulating layer and the metal layer, the softening point of the polymaleimide compound A is preferably 70 ° C. or higher, more preferably 80 ° C. or higher. That is all.

The inflection point is heated from −30 ° C. to 260 ° C. in a nitrogen atmosphere at a heating rate of 3 ° C./min using a differential scanning calorimetry device (for example, “Q2000” manufactured by TA Instruments). It can be obtained from the inflection point of the reverse heat flow.

The content of the polymaleimide compound A in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 15% by weight or more. , Preferably 80% by weight or less, more preferably 70% by weight or less. When the content of the polymaleimide compound A is at least the above lower limit, the thermal dimensional stability of the cured product can be further enhanced, and the adhesion between the insulating layer and the metal layer can be further enhanced. When the content of the polymaleimide compound A is not more than the above upper limit, the melt viscosity of the resin material can be lowered, and the embedding property in unevenness of a substrate or the like can be improved.

[Thermosetting compound]
The resin material preferably contains a thermosetting compound different from the polymaleimide compound having three or more maleimide skeletons and three or more imide skeletons. The thermosetting compound is a thermosetting compound different from the polymaleimide compound A. The thermosetting compound may be a compound that reacts with the polymaleimide compound A. Only one type of the thermosetting compound may be used, or two or more types may be used in combination.

Examples of the thermosetting compound include styrene compounds, phenoxy compounds, oxetane compounds, maleimide compounds, epoxy compounds, vinyl compounds, benzoxazine compounds, cyanate ester compounds, polyarylate compounds, diallylphthalate compounds, acrylate compounds, episulfide compounds, and (meth). ) Acrylic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds and the like can be mentioned.

The thermosetting compound is preferably a maleimide compound, an epoxy compound, a vinyl compound, a benzoxazine compound, or a cyanate ester compound, more preferably an epoxy compound or a vinyl compound, and further preferably an epoxy compound. preferable. 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.

It is preferable that at least one of the thermosetting compound and the curing agent described later has an amide bond or an imide bond. The thermosetting compound preferably has an amide bond or an imide bond. The curing agent preferably has an amide bond or an imide bond. It is preferable that both the thermosetting compound and the curing agent have an amide bond or an imide bond. By using a thermosetting compound having an amide bond or an imide bond, the compatibility between the thermosetting compound and the maleimide compound can be enhanced, and the desmear property can be further enhanced. By using a curing agent having an amide bond or an imide bond, the compatibility between the curing agent and the maleimide compound can be enhanced, and the desmear property can be further enhanced. The thermosetting compound and the curing agent may each have an amide bond or an imide bond. It is particularly preferable that the resin material contains an epoxy compound having an amide bond or an imide bond.

<Maleimide compound>
The maleimide compound is a maleimide compound (hereinafter, may be referred to as "maleimide compound X") that is different from the polymaleimide compound having three or more maleimide skeletons and one or more imide skeletons. The maleimide compound X is a maleimide compound different from the polymaleimide compound A. Only one type of the maleimide compound X may be used, or two or more types may be used in combination.

The maleimide compound X may be a bismaleimide compound.

Examples of the maleimide compound X include N-phenylmaleimide and N-alkylbismaleimide.

The maleimide compound X preferably has a skeleton derived from a diamine compound other than diamine diamine or a triamine compound other than trimer triamine.

The maleimide compound X preferably has an aromatic skeleton.

In the maleimide compound X, it is preferable that the nitrogen atom in the maleimide skeleton and the aromatic ring are bonded.

From the viewpoint of further enhancing the thermal dimensional stability of the cured product, the content of the maleimide compound X is preferably 0.5% by weight or more, more preferably 1 in 100% by weight of the components excluding the solvent in the resin material. By weight or more, preferably 15% by weight or less, more preferably 10% by weight or less.

The content of the maleimide compound X in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 2.5% by weight or more, more preferably 5% by weight or more, still more preferably 7.5. By weight or more, preferably 50% by weight or less, more preferably 35% by weight or less. When the content of the maleimide compound X 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 enhanced.

From the viewpoint of effectively exerting the effects of the present invention, the molecular weight of the maleimide compound X is preferably 500 or more, more preferably 1000 or more, preferably less than 30,000, and more preferably less than 20,000.

The molecular weight of the maleimide compound X means a molecular weight that can be calculated from the structural formula when the maleimide compound X is not a polymer and when the structural formula of the maleimide compound X can be specified. The molecular weight of the maleimide compound X indicates the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) when the maleimide compound X is a polymer.

Examples of commercially available products of the maleimide compound X include "BMI4000" and "BMI5100" manufactured by Daiwa Kasei Kogyo Co., Ltd., Designer Molecule's Inc. Examples include "BMI-3000" manufactured by Nippon Kayaku Co., Ltd. and "MIR-3000" manufactured by Nippon Kayaku Co., Ltd.

<Epoxy compound>
As the epoxy compound, a conventionally known epoxy compound can be used. The epoxy compound is an organic compound having at least one epoxy group. Only one type of the epoxy compound may be used, or two or more types may be used in combination.

Examples of the epoxy compound include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, phenol novolac type epoxy compound, biphenyl type epoxy compound, biphenyl novolac type epoxy compound, biphenol type epoxy compound, and naphthalene type epoxy compound. , Fluorene type epoxy compound, phenol aralkyl type epoxy compound, naphthol aralkyl type epoxy compound, dicyclopentadiene type epoxy compound, anthracene type epoxy compound, adamantan skeleton epoxy compound, tricyclodecane skeleton epoxy compound, naphthylene ether type Examples thereof include epoxy compounds and epoxy compounds having a triazine nucleus as a skeleton.

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

From the viewpoint of further lowering the dielectric loss tangent and enhancing the thermal dimensional stability and flame retardancy of the cured product, the epoxy compound preferably contains an epoxy compound having an aromatic skeleton, and has a naphthalene skeleton or a phenyl skeleton. It is preferable to contain an epoxy compound having an epoxy compound, and more preferably an epoxy compound having an aromatic skeleton.

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

The viscosity of the epoxy compound liquid at 25 ° C. at 25 ° C. is preferably 1000 mPa · s or less, and 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 Leologica Instruments) or the like.

The molecular weight of the epoxy compound is more preferably 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 component excluding the solvent in the resin material, a resin material having high fluidity at the time of forming the insulating layer can be obtained. Therefore, when the uncured resin material or the B-staged product is laminated on the circuit board, the inorganic filler can be uniformly present.

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. When the epoxy compound is a polymer, it means the weight average molecular weight.

From the viewpoint of further enhancing the thermal dimensional stability of the cured product, the content of the epoxy compound is preferably 4% by weight or more, more preferably 7% by weight or more, based on 100% by weight of the components excluding the solvent in the resin material. It is preferably 15% by weight or less, more preferably 12% by weight or less.

The content of the epoxy compound in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 15% by weight or more, more preferably 25% by weight or more, still more preferably 50% by weight or more. Is 40% by weight or less. When the content of the epoxy compound is at least the above lower limit and at least the above upper limit, the thermal dimensional stability of the cured product can be further enhanced.

Weight ratio of the content of the epoxy compound to the total content of the polymaleimide compound A, the phenol compound described later, and the active ester compound (content of the epoxy compound / the polymaleimide compound A and the phenol compound described later) The total content with the active ester compound) is preferably 0.2 or more, more preferably 0.3 or more. Weight ratio of the content of the epoxy compound to the total content of the polymaleimide compound A, the phenol compound described later, and the active ester compound (content of the epoxy compound / the polymaleimide compound A and the phenol compound described later) The total content with the active ester compound) is preferably 0.9 or less, more preferably 0.8 or less. When the weight ratio is at least the above lower limit and at least the above upper limit, the dielectric loss tangent can be further lowered and the thermal dimensional stability can be further improved.

<Vinyl compound>
As the vinyl compound, a conventionally known vinyl compound can be used. The vinyl compound is an organic compound having at least one vinyl group. Only one kind of the vinyl compound may be used, or two or more kinds thereof may be used in combination.

Examples of the vinyl compound include a divinylbenzyl ether compound.

The content of the vinyl compound in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 20% by weight or more. Is 80% by weight or less, more preferably 70% by weight or less. When the content of the vinyl compound is at least the above lower limit and at least the above upper limit, the thermal dimensional stability of the cured product can be further enhanced.

<Benzoxazine compound>
Examples of the benzoxazine compound include Pd-type benzoxazine and Fa-type benzoxazine. Only one kind of the benzoxazine compound may be used, or two or more kinds thereof may be used in combination.

Examples of commercially available products of the benzoxazine compound include "Pd type" manufactured by Shikoku Chemicals Corporation. In addition, it may be an aliphatic benzoxazine.

The content of the benzoxazine compound in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 1% by weight or more, more preferably 5% by weight or more, still more preferably 10% by weight or more. It is preferably 70% by weight or less, more preferably 60% by weight or less. When the content of the benzoxazine compound is at least the above lower limit and at least the above upper limit, the thermal dimensional stability of the cured product can be further enhanced.

<Cyanate ester compound>
Examples of the cyanate ester compound include a novolak type cyanate ester resin, a bisphenol type cyanate ester resin, and a prepolymer in which these are partially triquantized. Examples of the novolak type cyanate ester resin include phenol novolac type cyanate ester resin and alkylphenol type cyanate ester resin. Examples of the bisphenol type cyanate ester resin include bisphenol A type cyanate ester resin, bisphenol E type cyanate ester resin, and tetramethyl bisphenol F type cyanate ester resin. Only one type of the cyanate ester compound may be used, or two or more types may be used in combination.

Commercially available products of the above cyanate ester compounds include a phenol novolac type cyanate ester resin (“PT-30” and “PT-60” manufactured by Lonza Japan) and a prepolymer in which a bisphenol type cyanate ester resin is triquantized (Lonza Japan). Examples thereof include "BA-230S", "BA-3000S", "BTP-1000S" and "BTP-6020S") manufactured by the same company.

The content of the cyanate ester compound in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 10% by weight or more, more preferably 15% by weight or more, still more preferably 20% by weight or more. It is preferably 85% by weight or less, more preferably 75% by weight or less. When the content of the cyanate ester compound is at least the above lower limit and at least the above upper limit, the thermal dimensional stability of the cured product can be further enhanced.

[Inorganic filler]
The resin material preferably contains an inorganic filler. By using the above-mentioned inorganic filler, the dielectric loss tangent of the cured product can be further lowered. Further, by using the above-mentioned inorganic filler, the dimensional change due to heat of the cured product is further reduced. As the inorganic filler, only one kind may be used, or two or more kinds may be used in combination.

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

The surface roughness of the surface of the cured product is reduced, the adhesive strength between the cured product and the metal layer is further increased, finer wiring is formed on the surface of the cured product, and the cured product has better insulation reliability. From the viewpoint of imparting, the inorganic filler is preferably silica or alumina, more preferably silica, and even more preferably fused silica. By using silica, the coefficient of thermal expansion of the cured product is further reduced, and the dielectric loss tangent of the cured product is further reduced. Further, by using silica, the surface roughness of the surface of the cured product is effectively reduced, and the adhesive strength between the cured product and the metal layer is effectively increased. The shape of silica is preferably spherical.

The inorganic filler is spherical silica from the viewpoint of advancing the curing of the resin regardless of the curing environment, effectively increasing the glass transition temperature of the cured product, and effectively reducing the coefficient of linear thermal expansion of the cured product. Is preferable.

The average particle size of the inorganic filler is preferably 50 nm or more, more preferably 100 nm or more, still more preferably 500 nm or more, preferably 5 μm or less, more preferably 3 μm or less, still more preferably 1 μm or less. When the average particle size of the inorganic filler is not less than the above lower limit and not more than the above upper limit, the surface roughness after etching can be reduced and the plating peel strength can be increased, and the insulating layer and the metal layer can be combined. Adhesion can be further improved.

As the average particle size of the inorganic filler, a value of median diameter (d50) of 50% is adopted. The average particle size can be measured using a laser diffraction / scattering type particle size distribution measuring device.

The inorganic filler is preferably spherical, and more preferably spherical silica. In this case, the surface roughness of the surface of the cured product is effectively reduced, and 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 a surface-treated product with a coupling agent, and even more preferably a surface-treated product with a silane coupling agent. By surface-treating the inorganic filler, the surface roughness of the surface of the roughened cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased. Further, 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 obtained in the cured product. Can be granted.

Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, and the like. 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 component excluding the solvent in the resin material is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 65% by weight or more, and particularly preferably 68% by weight. % Or more, preferably 90% by weight or less, more preferably 85% by weight or less, still more preferably 80% by weight or less, and particularly preferably 75% by weight or less. When the content of the inorganic filler is at least the above lower limit, the dielectric loss tangent is effectively lowered. When the content of the inorganic filler is not more than the above upper limit, thermal dimensional stability can be improved and warpage of the cured product can be effectively suppressed. When the content of the inorganic filler is at least the above lower limit and at least 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. Further, the content of this inorganic filler makes it possible to reduce the coefficient of thermal expansion of the cured product and at the same time improve the smear removability.

[Hardener]
The resin material preferably contains a curing agent. The curing agent is not particularly limited. Conventionally known hardeners can be used as the hardeners. Only one kind of the above-mentioned curing agent may be used, or two or more kinds may be used in combination.

Examples of the curing agent include phenol compound (phenol curing agent), active ester compound, carbodiimide compound (carbodiimide curing agent), amine compound (amine curing agent), thiol compound (thiol curing agent), phosphine compound, dicyandiamide, and acid anhydride. Things etc. can be mentioned. The curing agent preferably has a functional group capable of reacting with the epoxy group of the epoxy compound.

From the viewpoint of further enhancing thermal dimensional stability, the curing agent preferably contains at least one component of a phenol compound, an active ester compound, a carbodiimide compound and an acid anhydride. From the viewpoint of further enhancing thermal dimensional stability, the curing agent more preferably contains at least one component of a phenol compound, an active ester compound, and a carbodiimide compound, and both the phenol compound and the active ester compound. It is more preferable to include.

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

Examples of the phenol compound include novolak-type phenol, biphenol-type phenol, naphthalene-type phenol, dicyclopentadiene-type phenol, aralkyl-type phenol, and dicyclopentadiene-type phenol.

Commercially available products of the above phenol compounds include novolak-type phenol (“TD-2091” manufactured by DIC), 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) and the like can be mentioned.

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

In the above formula (1), X1 represents a group containing an aliphatic chain, a group containing an aliphatic ring or a group containing an aromatic ring, and X2 represents a group containing an aromatic ring. Preferred examples of the group containing an aromatic ring include a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, and the like. Examples of the substituent include a hydrocarbon group. The hydrocarbon group has preferably 12 or less carbon atoms, more preferably 6 or less carbon atoms, and even more preferably 4 or less carbon atoms.

In the above formula (1), the combination of X1 and X2 includes a combination of a benzene ring which may have a substituent and a benzene ring which may have a substituent, and a substituent. Examples thereof include a combination of a good benzene ring and a naphthalene ring which may have a substituent. Further, in the above formula (1), examples of the combination of X1 and X2 include a combination of a naphthalene ring which may have a substituent and a naphthalene ring which may have a substituent.

The active ester compound is not particularly limited. From the viewpoint of further enhancing thermal dimensional stability and flame retardancy, the active ester compound is preferably an active ester compound having two or more aromatic skeletons. From the viewpoint of lowering the dielectric loss tangent of the cured product and increasing the thermal dimensional stability of the cured product, it is more preferable to have a naphthalene ring in the main chain skeleton of the active ester compound.

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

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

In the above formula (2), X is 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 substituent bonded to an arylene group. Represents a group and p represents an integer of 1-5. When a plurality of X's exist, the plurality of X's may be the same or different.

In one preferred form, at least one X is an alkylene group, a group having a substituent attached to an alkylene group, a cycloalkylene group, or a group having a substituent attached to a cycloalkylene group.

Commercially available products of the above carbodiimide compounds include "carbodilite V-02B", "carbodilite V-03", "carbodilite V-04K", "carbodilite V-07", "carbodilite V-09", and "carbodilite" manufactured by Nisshinbo Chemical Co., Ltd. Examples thereof include "10M-SP" and "carbodilite 10M-SP (revised)", and "Stavaxol P", "Stavaxol P400" and "Hikazil 510" manufactured by Rheinchemy.

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

Examples of commercially available products of the acid anhydride include "Ricacid TDA-100" manufactured by New Japan Chemical Co., Ltd.

The total content of the active ester compound and the phenol compound with respect to 100 parts by weight of the epoxy compound is preferably 70 parts by weight or more, more preferably 85 parts by weight or more, preferably 150 parts by weight or less, and more preferably 120 parts by weight. It is less than a part. When the total content of the active ester compound and the phenol compound is at least the above lower limit and at least the above upper limit, the curability is further improved, the thermal dimensional stability is further enhanced, and the volatilization of the residual unreacted component is further further enhanced. Can be suppressed.

The total content of the polymaleimide compound A, the thermosetting compound, and the curing agent in 100% by weight of the components excluding the inorganic filler and the solvent in the resin film is preferably 50% by weight or more, more preferably. Is 60% by weight or more, preferably 95% by weight or less, and more preferably 95% by weight or less. When the total content of the polymaleimide compound A, the thermosetting compound, and the curing agent is not less than the above lower limit and not more than the above upper limit, the curability is further improved and the thermal dimensional stability can be further enhanced. ..

[Curing accelerator]
The resin material contains a curing accelerator. By using the above-mentioned curing accelerator, the curing rate 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 as a result, the crosslinked density increases. The curing accelerator is not particularly limited, and conventionally known curing accelerators can be used. Only one type of the curing accelerator may be used, or two or more types may be used in combination.

Examples of the curing accelerator include anionic curing accelerators such as imidazole compounds, cationic curing accelerators such as amine compounds, and curing accelerators other than anionic and cationic curing accelerators such as phosphorus compounds and organic metal compounds. , And radical curing accelerators such as peroxides.

Examples of the imidazole compound include 2-undecyl imidazole, 2-heptadecyl imidazole, 2-methyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 2-phenyl-4-methyl imidazole and 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 trimerite, 1-cyanoethyl-2-phenylimidazolium trimerite, 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 And so on.

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

Examples of the phosphorus compound include triphenylphosphine compounds.

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

Examples of the peroxide include dicumyl peroxide and perhexyl 25B.

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

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

From the viewpoint of further suppressing the curing temperature and effectively suppressing the warp of the cured product, the content of the anionic curing accelerator is preferably 20% by weight or more, more preferably 20% by weight or more, based on 100% by weight of the curing accelerator. Is 50% by weight or more, more preferably 70% by weight or more, and most preferably 100% by weight (total amount). Therefore, the curing accelerator is most preferably the anionic curing accelerator.

The content of the curing accelerator is not particularly limited. The content of the curing accelerator is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and preferably 5% by weight in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. Hereinafter, it is more preferably 3% 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 resin material is efficiently cured. If the content of the curing accelerator is in a more preferable range, the storage stability of the resin material becomes even higher, and a better cured product can be obtained.

[Thermoplastic resin]
The resin material preferably contains a thermoplastic resin. Examples of the thermoplastic resin include polyvinyl acetal resin, polyimide resin, and phenoxy resin. Only one type of the above-mentioned thermoplastic resin may be used, or two or more types may be used in combination.

The thermoplastic resin is preferably a phenoxy resin from the viewpoint of effectively lowering the dielectric loss tangent and effectively improving the adhesion of the metal wiring regardless of the curing environment. By using the phenoxy resin, deterioration of embedding property in holes or irregularities of the circuit board of the resin film and non-uniformity of the inorganic filler can be suppressed. Further, by using the phenoxy resin, the melt viscosity can be adjusted, so that the dispersibility of the inorganic filler is improved, and the resin composition or the B-staged product is less likely to wet and spread in an unintended region during the curing process.

The phenoxy resin contained in the resin material is not particularly limited. As the phenoxy resin, a conventionally known phenoxy resin can be used. Only one type of the phenoxy resin may be used, or two or more types may be used in combination.

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

Examples of commercially available phenoxy resins include "YP50", "YP55" and "YP70" manufactured by Nippon Steel & Sumikin Chemical Corporation, and "1256B40", "4250", "4256H40" and "4275" manufactured by Mitsubishi Chemical Corporation. , "YX6954BH30" and "YX8100BH30" and the like.

The thermoplastic resin is preferably a polyimide resin (polyimide compound) from the viewpoint of improving handleability, plating peel strength at low roughness, and adhesion between the insulating layer and the metal layer.

From the viewpoint of improving the solubility, the polyimide compound is preferably a polyimide compound obtained by a method of reacting a tetracarboxylic dianhydride with a dimerdiamine.

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfonetetra. Carcarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3', 4,4'-biphenyl ether Tetetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2 , 3,4-Flantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl Sethylene dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3', 4,4'-perfluoroisopropyridenediphthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphinoxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenyl) Examples thereof include phthalic dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, and bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride.

Examples of the dimer diamine include Versamine 551 (trade name: 3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl) cyclohexene manufactured by BASF Japan Ltd.) and Versamine 552 (trade name: Examples thereof include Cognix Japan Co., Ltd., a hydrogenated product of Versamine 551), PRIAMINE1075, and PRIAMINE1074 (trade names, all manufactured by Crowder Japan Co., Ltd.).

The polyimide compound may have an acid anhydride structure, a maleimide structure, or a citraconimide structure at the terminal. In this case, the polyimide compound can be reacted with the epoxy resin. By reacting the polyimide compound with the epoxy resin, the thermal dimensional stability of the cured product can be improved.

From the viewpoint of obtaining a resin material having more excellent storage stability, the weight average molecular weights of the thermoplastic resin, the polyimide resin and the phenoxy resin are preferably 5000 or more, more preferably 10000 or more, preferably 100,000 or less, and more. It is preferably 50,000 or less.

The weight average molecular weights of the thermoplastic resin, the polyimide resin, and the phenoxy resin indicate the polystyrene-equivalent weight average molecular weights measured by gel permeation chromatography (GPC).

The contents of the thermoplastic resin, the polyimide resin, and the phenoxy resin are not particularly limited. The content of the thermoplastic resin in 100% by weight of the component excluding the inorganic filler and the solvent in the resin material (when the thermoplastic resin is a polyimide resin or a phenoxy resin, the content of the polyimide resin or the phenoxy resin). ) Is preferably 1% by weight or more, more preferably 2% by weight or more, preferably 30% by weight or less, and more preferably 20% by weight or less. When the content of the thermoplastic resin is at least the above lower limit and at least the above upper limit, the embedding property of the resin material in the holes or irregularities of the circuit board is improved. When the content of the thermoplastic resin is at least the above lower limit, the formation of the resin film becomes easier and a better insulating layer can be obtained. When the content of the thermoplastic resin is not more than the above upper limit, the coefficient of thermal expansion of the cured product becomes even lower. When the content of the thermoplastic resin is not more than the above upper limit, the surface roughness of the surface of the cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased.

[solvent]
The resin material does not contain or contains a solvent. By using the above solvent, the viscosity of the resin material can be controlled in a suitable range, and the coatability of the resin material can be improved. Further, 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.

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, and methyl ethyl ketone. Examples thereof include N, N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidone, n-hexane, cyclohexane, cyclohexanone and naphtha as a mixture.

Most of the solvent is preferably removed when the resin composition is formed into a film. Therefore, the boiling point of the 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 appropriately changed in consideration of the coatability of the resin composition and the like.

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, and preferably 10% by weight or less. , More preferably 5% by weight or less.

[Other ingredients]
For the purpose of improving impact resistance, heat resistance, resin compatibility, workability, etc., the above resin materials include organic fillers, leveling agents, flame retardants, coupling agents, colorants, antioxidants, and UV deterioration prevention. It may contain an agent, a defoaming agent, a thickener, a shaking denaturing agent and the like.

Examples of the organic filler include particulate matter made of benzoxazine resin, benzoxazole resin, fluororesin, acrylic resin, styrene resin and the like. By using fluororesin particles as the organic filler, the relative permittivity of the cured product can be further reduced. The average particle size of the organic filler is preferably 1 μm or less. When the average particle size of the organic filler is not more than the above upper limit, the surface roughness after etching can be reduced, the plating peel strength can be increased, and the adhesion between the insulating layer and the metal layer can be improved. It can be further enhanced. The average particle size of the organic filler may be 50 nm or more.

As the average particle size of the organic filler, a value of median diameter (d50) of 50% is adopted. The average particle size can be measured using a laser diffraction / scattering type particle size distribution measuring device.

Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, and the like. Examples of the silane coupling agent include vinylsilane, aminosilane, imidazolesilane, and epoxysilane.

(Resin film)
A resin film (B-staged product / B-stage film) can be obtained by molding the above-mentioned resin composition into a film. The resin material is preferably a resin film. The resin film is preferably a B stage film.

Examples of a method for obtaining a resin film by molding the resin composition into a film form 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 by a T-die, a circular die, or the like. A casting molding method in which a resin composition containing a solvent is cast and molded into a film. Other conventionally known film forming methods. An extrusion molding method or a casting molding method is preferable because it can be made thinner. The film includes a sheet.

A resin film as a B stage film can be obtained by molding the resin composition into a film and heating and drying it at 50 ° C. to 150 ° C. for 1 minute to 10 minutes to the extent that curing by heat does not proceed too much. it can.

The film-like resin composition that can be obtained by the drying step as described above is referred to as 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.

The resin film does not have to be a prepreg. When the resin film is not a prepreg, migration does not occur along the glass cloth or the like. Further, when the resin film is laminated or pre-cured, unevenness due to the glass cloth does 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 the base material. The metal foil is preferably a 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 mold-released, 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, preferably 200 μm or less. When the resin film is used as the insulating layer of the circuit, the thickness of the insulating layer formed by the resin film is preferably equal to or larger 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.

(Semiconductor devices, printed wiring boards, copper-clad laminates and multilayer printed wiring boards)
The resin material is suitably used for forming a mold resin for embedding a semiconductor chip in a semiconductor device.

The resin material is preferably used as an insulating material. The resin material is suitably used for forming an insulating layer in a printed wiring board.

The printed wiring board can be obtained, for example, by heat-press molding the resin material.

A member to be laminated having a metal layer on one side or both sides can be laminated on the resin film. A laminated structure comprising 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 being the resin material described above can be preferably obtained. The method of laminating the resin film and the member to be laminated having the metal layer on the surface is not particularly limited, and a known method can be used. For example, using a device such as a parallel flat plate press or a roll laminator, the resin film can be laminated on a member to be laminated having a metal layer on the surface while pressurizing with or without heating.

The material of the metal layer is preferably copper.

The member to be laminated having the metal layer on the surface may be a metal foil such as a copper foil.

The resin material is preferably used to obtain a copper-clad laminate. An example of the copper-clad laminate is a copper-clad laminate comprising a copper foil and a resin film laminated on one surface of the copper foil.

The thickness of the copper foil of the copper-clad laminate is not particularly limited. The thickness of the copper foil is preferably in the range of 1 μm to 50 μm. Further, in order to increase the 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 the surface. The method of forming the unevenness is not particularly limited. Examples of the method for forming the unevenness include a method for forming the unevenness by a treatment using a known chemical solution.

The resin material is preferably used to obtain a multilayer substrate.

An example of the multilayer board is a multilayer board provided with a circuit board and an insulating layer laminated on the circuit board. The insulating layer of this multilayer substrate is formed of the above resin material. Further, the insulating layer of the multilayer substrate may be formed of the resin film of the laminated film by using the laminated film. The insulating layer is preferably laminated on the surface of the circuit board on which the circuit is provided. It is preferable that a part 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 roughened.

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

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

Further, as another example of the multilayer board, the circuit board, the insulating layer laminated on the surface of the circuit board, and the insulating layer are laminated on the surface opposite to the surface on which the circuit board is laminated. Examples thereof include a multilayer substrate provided with a copper foil. It is preferable that the insulating layer is formed by curing the resin film using a copper-clad laminate having a copper foil and a resin film laminated on one surface of the copper foil. Further, the copper foil is etched and preferably a copper circuit.

As another example of the multilayer board, there is a multilayer board including a circuit board and a plurality of insulating layers laminated on the surface of the circuit board. At least one of the plurality of insulating layers arranged on the circuit board is formed by using the resin material. It is preferable that the multilayer substrate further includes a circuit laminated on at least one surface of the insulating layer formed by using the resin film.

Among the multilayer boards, the multilayer printed wiring board is required to have a low dielectric loss tangent and high insulation reliability due to the insulating layer. In the resin material according to the present invention, the insulation reliability can be effectively improved by lowering the dielectric loss tangent and improving the adhesion and etching performance between the insulating layer and the metal layer. Therefore, the resin material according to the present invention is suitably used for forming an insulating layer in a multilayer printed wiring board.

The multilayer printed wiring board includes, for example, a circuit board, a plurality of insulating layers arranged on the surface of the circuit board, and a metal layer arranged between the plurality of insulating layers. At least one of the insulating layers is a cured product of the resin material.

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 product layers. A metal layer 17 is formed in a part of the upper surface 12a of the circuit board 12. Of the plurality of insulating layers 13 to 16, metal layers 17 are 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. Has been done. The metal layer 17 is a circuit. A metal layer 17 is arranged between the circuit board 12 and the insulating layer 13 and between the layers of the laminated insulating layers 13 to 16, respectively. 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 the cured product of the resin material. In the present embodiment, since the surfaces of the insulating layers 13 to 16 are roughened, fine holes (not shown) are formed on the surfaces of the insulating layers 13 to 16. Further, the metal layer 17 reaches the inside of the fine pores. Further, in the multilayer printed wiring board 11, the width direction dimension (L) of the metal layer 17 and the width direction dimension (S) of the portion where the metal layer 17 is not formed can be reduced. Further, in the multilayer printed wiring board 11, good insulation reliability is imparted between the upper metal layer and the lower metal layer which are not connected by via hole connection and through hole connection (not shown).

(Roughening treatment and swelling treatment)
The resin material is preferably used to obtain a cured product to be roughened or desmeared. The cured product also includes a pre-cured product that can be further cured.

In order to form fine irregularities on the surface of the cured product obtained by pre-curing the resin material, the cured product is preferably roughened. Prior to the roughening treatment, the cured product is preferably swelled. It is preferable that the cured product is swelled and further cured after the roughening treatment after the pre-curing and before the roughening treatment. However, the cured product does not necessarily have to be swelled.

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

For the roughening treatment, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound or a persulfate compound is used. These chemical oxidizing agents are used as an aqueous solution or an organic solvent dispersion solution after water or an organic solvent is added. The roughening solution used for the roughening treatment generally contains an alkali as a pH adjuster or the like. The roughening solution preferably contains sodium hydroxide.

Examples of the manganese compound include potassium permanganate and sodium permanganate. Examples of the chromium compound include potassium dichromate and anhydrous potassium chromate. Examples of the persulfate compound include sodium persulfate, potassium persulfate, ammonium persulfate and the like.

The arithmetic mean roughness Ra of the surface of the cured product is preferably 10 nm or more, preferably less than 300 nm, more preferably less than 200 nm, and further preferably less than 150 nm. In this case, the adhesive strength between the cured product and the metal layer is increased, and the surface of the insulating layer forms finer wiring. Further, the conductor loss can be suppressed, and the signal loss can be suppressed low. The arithmetic mean roughness Ra is measured according to JIS B0601: 1994.

(Desmia processing)
Through holes may be formed in the cured product obtained by pre-curing the resin material. Vias, through holes, and the like are formed as through holes in the multilayer substrate and the like. For example, vias can be formed by irradiation with a laser such as a CO ₂ laser. The diameter of the via is not particularly limited, but is about 60 μm to 80 μm. Due to the formation of the through holes, smear, which is a residue of the resin derived from the resin component contained in the cured product, is often formed at the bottom of the via.

In order to remove the smear, the surface of the cured product is preferably desmear-treated. The desmear treatment may also serve as the roughening treatment.

In the desmear treatment, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound or a persulfate compound is used in the same manner as in the roughening treatment. These chemical oxidizing agents are used as an aqueous solution or an organic solvent dispersion solution after water or an organic solvent is added. The desmear treatment liquid used for the desmear treatment generally contains an alkali. The desmear treatment solution preferably contains sodium hydroxide.

By using the above resin material, the surface roughness of the surface of the desmear-treated cured product is sufficiently reduced.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.

The following materials were prepared.

(Polymaleimide Compound A)
Polymaleimide compound 1:
A polymaleimide compound 1 (molecular weight 11000) represented by the following formula (X1) was synthesized according to the following Synthesis Example 1. Among the structures represented by the following formula (X1), the skeleton derived from dimer diamine is a representative structure of the skeleton derived from the diamine diamine. For example, the hydrocarbon chain in the skeleton derived from the diamine diamine is It may have an unsaturated bond. In the following formula (X1), a polymaleimide compound having an unsaturated bond in the hydrocarbon chain in the skeleton derived from the dimer diamine may be contained. The synthesized polymaleimide compound may include a polymaleimide compound in which the hydrocarbon chain in the skeleton derived from dimerdiamine has an unsaturated bond. The obtained polymaleimide compound 1 has four maleimide skeletons, five imide skeletons, and one skeleton derived from dimerdiamine. The number of maleimide skeletons, the number of imide skeletons, and the number of skeletons derived from dimerdiamine are calculated values from the number average molecular weight of the polymaleimide compound.

<Synthesis example 1>
150 mL of toluene and 100 mL of N-methyl-2-pyrrolidone were placed in a 500 mL eggplant flask, and 10.3 g (25 mmol) of preamine 1075 and 11.6 g (75 mmol) of bis (aminomethyl) norbornane were added. Then, 27.3 g (135 mmol) of pyromellitic dianhydride was added little by little. The eggplant flask was then attached to the Dean-Stark apparatus and heated to reflux for 4 hours. In this way, a compound having an acid anhydride structure at the terminal and having a plurality of imide skeletons was obtained. After removing the water discharged during the condensation and returning to room temperature, 4.75 g (50 mmol) of serinol was added, the mixture was stirred, and the mixture was heated and reacted in the same manner. In this way, a compound having diols at both ends was obtained. Then, after returning to room temperature, 21.1 g (100 mmol) of 6-maleimide caproic acid was added, the mixture was stirred, and the mixture was similarly heated for reaction. After completion of the reaction, the reaction was washed with water, the organic layer was added dropwise to methanol, reprecipitated, and then dried to obtain a polymaleimide compound 1.

Polymaleimide compound 2:
According to the following Synthesis Example 2, a polymaleimide compound 2 (molecular weight 56000) represented by the following formula (X2) was synthesized. The obtained polymaleimide compound 2 has three or more maleimide skeletons, one or more imide skeletons, and one or more skeletons derived from dimerdiamine. The number of maleimide skeletons, the number of imide skeletons, and the number of skeletons derived from dimerdiamine are calculated values from the number average molecular weight of the polymaleimide compound.

In the above formula (X2), X21 represents a structure represented by the following formula (X21), X22 represents a structure represented by the following formula (X22), and represents a structure represented by the following formula (X23). L in the following formula (X21), m in the following formula (X22), and n in the following formula (X23) satisfy the formula: n / (l + m + n) = 0.2. Among the structures represented by the following formula (X22), the skeleton derived from dimer diamine is a representative structure of the skeleton derived from the diamine diamine. For example, the hydrocarbon chain in the skeleton derived from the diamine diamine is It may have an unsaturated bond. For example, in the following formula (X22), a polymaleimide compound having an unsaturated bond in the hydrocarbon chain in the skeleton derived from the dimer diamine may be contained. The synthesized polymaleimide compound may include a polymaleimide compound in which the hydrocarbon chain in the skeleton derived from dimerdiamine has an unsaturated bond.

<Synthesis example 2>
Put 150 mL of toluene and 100 mL of N-methyl-2-pyrrolidone in a 500 mL eggplant flask, 20.0 g (48.8 mmol) of preamine 1075, 5.01 g (32.5 mmol) of bis (aminomethyl) norbornane, and diamino. 2.25 g (25 mmol) of propanol was added. Then, 65.7 g (126 mmol) of 4,4'-(4,4'-isopropyridene diphenoxy) diphthalic anhydride was added little by little. The eggplant flask was then attached to the Dean-Stark apparatus and heated to reflux for 4 hours. In this way, a compound having amines at both ends and having a plurality of imide skeletons was obtained. After removing the water discharged during the condensation and returning to room temperature, 2.70 g (27.5 mmol) of maleic anhydride was added, the mixture was stirred, and the mixture was similarly heated and reacted. In this way, a compound having a maleimide skeleton at both ends was obtained. Then, after returning to room temperature, 3.96 g (18.8 mmol) of 6-maleimide caproic acid was added, the mixture was stirred, and the mixture was similarly heated for reaction. Then, after completion of the reaction, the mixture was washed with water, the organic layer was added dropwise to methanol, reprecipitated, and then dried to obtain a polymaleimide compound 2.

The molecular weight of the polymaleimide compound A synthesized in Synthesis Examples 1 and 2 was determined as follows.

GPC (Gel Permeation Chromatography) Measurement:
Using a high performance liquid chromatograph system manufactured by Shimadzu Corporation, measurements were carried out using tetrahydrofuran (THF) as a developing medium at a column temperature of 40 ° C. and a flow rate of 1.0 ml / min. "SPD-10A" was used as a detector, and two columns of "KF-804L" (exclusion limit molecular weight: 400,000) manufactured by Shodex were connected in series. Tosoh's "TSK standard polystyrene" is used as the standard polystyrene, and the weight average molecular weight Mw = 354,000, 189,000, 98,900, 37,200, 17,100, 9,830, 5,870, 2, Calibration curves were made using 500, 1,050, and 500 materials and the molecular weight was calculated.

(Thermosetting compound)
Biphenyl type epoxy compound ("NC-3000" manufactured by Nippon Kayaku Co., Ltd.)
Naphthalene type epoxy compound ("ESN-475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
Resorcinol diglycidyl ether (“EX-201” manufactured by Nagase ChemteX Corporation)
Amide bond-containing epoxy compound ("WHR-991S" manufactured by Nippon Kayaku Co., Ltd.)
Maleimide compound (N-alkylbismaleimide, "BMI-1500" manufactured by Designer Molecules Inc.)

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

(Hardener)
Liquid containing 1 active ester compound ("EXB-9416-70BK" manufactured by DIC Corporation, solid content 70% by weight)
Active ester compound 2 containing liquid (DIC Corporation "HPC-8150-62T", solid content 62% by weight)
Phenol compound-containing liquid ("LA-1356" manufactured by DIC Corporation, solid content 60% by weight)

(Curing accelerator)
Dimethylaminopyridine ("DMAP" manufactured by Wako Pure Chemical Industries, Ltd.)
2-Phenyl-4-methylimidazole ("2P4MZ" manufactured by Shikoku Chemicals Corporation, anionic hardening accelerator)

(Thermoplastic resin)
Polyimide compound (polyimide resin):
A polyimide compound-containing solution (nonvolatile content 26.8% by weight), which is a reaction product of tetracarboxylic dianhydride and dimerdiamine, was synthesized according to the following Synthesis Example 3.

<Synthesis example 3>
300.0 g of tetracarboxylic dianhydride (“BisDA-1000” manufactured by SABIC Japan GK) and 665.5 g of cyclohexanone were placed in a reaction vessel equipped with a stirrer, a water divider, a thermometer and a nitrogen gas introduction tube. And the solution in the reaction vessel was heated to 60 ° C. Next, 89.0 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) and 54.7 g of 1,3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Company) were added dropwise to 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 (nonvolatile content 26.8% by weight) was obtained. The molecular weight (weight average molecular weight) of the obtained polyimide compound was 20000. The molar ratio of the acid component / amine component was 1.04.

The molecular weight of the polyimide compound synthesized in Synthesis Example 3 was determined as follows.

GPC (Gel Permeation Chromatography) Measurement:
Using a high performance liquid chromatograph system manufactured by Shimadzu Corporation, measurements were carried out using tetrahydrofuran (THF) as a developing medium at a column temperature of 40 ° C. and a flow rate of 1.0 ml / min. "SPD-10A" was used as a detector, and two columns of "KF-804L" (exclusion limit molecular weight: 400,000) manufactured by Shodex were connected in series. Tosoh's "TSK standard polystyrene" is used as the standard polystyrene, and the weight average molecular weight Mw = 354,000, 189,000, 98,900, 37,200, 17,100, 9,830, 5,870, 2, Calibration curves were made using 500, 1,050, and 500 materials and the molecular weight was calculated.

(Examples 1 to 3 and Comparative Examples 1 to 3)
The components shown in Table 1 below were blended in the blending amounts shown in Table 1 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 on the release-treated surface of the release-treated PET film (Toray Industries, Inc. "XG284", thickness 25 μm) using an applicator, 2 minutes in a gear oven at 100 ° C. It was dried for 30 seconds to volatilize the solvent. In this way, a laminated film (laminated film of PET film and resin film) in which a resin film (B stage film) having a thickness of 40 μm is laminated on the PET film was obtained.

(Evaluation)
(1) Dielectric Dissipation Factor The obtained resin film was heated at 190 ° C. for 90 minutes to obtain a cured product. The obtained cured product was cut into a size of 2 mm in width and 80 mm in length, and 10 sheets were laminated, and "Cavity Resonance Perturbation Method Permittivity Measuring Device CP521" manufactured by Kanto Electronics Application Development Co., Ltd. and "Keysight Technology Co., Ltd." Using a network analyzer N5224A PNA, the dielectric loss tangent was measured at room temperature (23 ° C.) and at a frequency of 5.8 GHz by the cavity resonance method.

[Criteria for determining dielectric loss tangent]
◯: Dissipation factor is less than 2.8 × 10 ^-3 ×: Dissipation factor is 2.8 × 10 ^-3 or more

(2) Thermal dimensional stability (average coefficient of linear expansion (CTE))
The obtained resin film (B stage film) having a thickness of 40 μm was heated at 190 ° C. for 90 minutes, and the obtained cured product was cut into a size of 3 mm × 25 mm. A cured product cut at 25 ° C to 150 ° C using a thermomechanical analyzer (“EXSTAR TMA / SS6100” manufactured by SII Nanotechnology) under the conditions of a tensile load of 33 mN and a heating rate of 5 ° C / min. The coefficient of linear expansion (ppm / ° C.) up to was calculated.

[Criteria for determining the coefficient of linear expansion]
○ ○: Average coefficient of linear expansion is 23 ppm / ° C or less ○: Average coefficient of linear expansion exceeds 23 ppm / ° C and is 27 ppm / ° C or less ×: Average coefficient of linear expansion exceeds 27 ppm / ° C

(3) Elongation characteristics The obtained resin film (B stage film) having a thickness of 40 μm was heated at 190 ° C. for 90 minutes, and the obtained cured product was cut into a size of 10 mm × 100 mm. Using a tensile tester (“AGS-J 100N” manufactured by SHIMADZU), measurements were made under the conditions of a distance between chucks of 60 mm and a tensile speed of 5 mm / min, and the maximum elongation was measured. The initial tension was 0.35 N. The measurement was repeated 5 times, and the average value of the elongation at break (average elongation at break) was calculated.

[Criteria for elongation characteristics]
○○: Average breaking elongation is 1.5% or more ○: Average breaking elongation is 1.2% or more and less than 1.5% ×: Average breaking elongation is less than 1.2%

(4) Bending characteristics (repeated bending property)
The obtained resin film (B stage film) having a thickness of 40 μm was heated at 190 ° C. for 90 minutes, and the obtained cured product was cut into a size of 30 mm × 150 mm. A bending test was performed using a planar U-shaped folding tester (manufactured by Yuasa) under the conditions of 200 times / min, bending at 180 ° C. (folding gap 5 mm), and film stroke 70 mm. The measurement was repeated 5 times, and the average value was calculated.

[Criteria for bending characteristics (repeated bending property)]
○ ○: No cracking after 2000 bendings ○: Cracking when the number of bendings is 100 or more and less than 2000 ×: Cracking when the number of bendings is less than 100

(5) Desmia (removability of residue on the bottom of via)
Laminating / semi-curing treatment:
The obtained resin film was vacuum-laminated on a CCL substrate (“E679FG” manufactured by Hitachi Chemical Co., Ltd.) and heated at 180 ° C. for 30 minutes to be semi-cured. In this way, a laminated body A in which a semi-cured product of a resin film was laminated on a CCL substrate was obtained.

Via (through hole) formation:
Using a CO ₂ laser (manufactured by Hitachi Via Mechanics) on the semi-cured resin film of the obtained laminate A, a via (penetration) having a diameter of 60 μm at the upper end and a diameter of 40 μm at the lower end (bottom). A hole) was formed. In this way, a laminated body B in which the semi-cured product of the resin film was laminated on the CCL substrate and vias (through holes) were formed in the semi-cured product of the resin film was obtained.

Removal of residue on the bottom of the via:
(A) Swelling treatment The obtained laminate B was placed in a swelling solution at 60 ° C. (“Swelling Dip Securigant P” manufactured by Atotech Japan Co., Ltd.) and shaken for 10 minutes. Then, it was washed with pure water.

(B) Permanganate treatment (roughening treatment and desmear treatment)
The swelling-treated laminate B was placed in a crude aqueous solution of potassium permanganate (“Concentrate Compact CP” manufactured by Atotech Japan) at 80 ° C. and shaken for 30 minutes. Next, the mixture was treated with a cleaning solution at 25 ° C. (“Reduction Securigant P” manufactured by Atotech Japan) for 2 minutes, and then washed with pure water to obtain an evaluation sample.

The bottom of the via of the evaluation sample was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the bottom of the via was measured. The removability of the residue on the bottom of the via was judged according to the following criteria.

[Criteria for removing residue on the bottom of vias]
○ ○: Maximum smear length is less than 2 μm ○: Maximum smear length is 2 μm or more and less than 3 μm ×: Maximum smear length is 3 μm or more

The composition and results are shown in Table 1 below.

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

Claims (19)

A resin material containing a polymaleimide compound having three or more maleimide skeletons and one or more imide skeletons, and a curing accelerator. The resin material according to claim 1, wherein the polymaleimide compound has three or more ends due to having a branched structure, and has the maleimide skeleton at three or more ends. The resin material according to claim 1 or 2, wherein the polymaleimide compound has at least one skeleton derived from diamine diamine. The polymaleimide compound has at least one skeleton derived from dimerdiamine.
The resin material according to claim 2, wherein the skeleton derived from the dimer diamine is directly bonded to the maleimide skeleton at the terminal. The resin material according to any one of claims 2 to 4, wherein the maleimide skeleton at the terminal is bonded to the main chain via an ester bond. The resin material according to any one of claims 1 to 5, wherein the polymaleimide compound has a molecular weight of 1000 or more and 50,000 or less. The resin material according to any one of claims 1 to 6, which comprises an inorganic filler. The resin material according to claim 7, wherein the content of the inorganic filler is 50% by weight or more in 100% by weight of the component excluding the solvent in the resin material. The resin material according to claim 7 or 8, wherein the inorganic filler is silica. The resin material according to any one of claims 1 to 9, which contains a thermosetting compound different from the polymaleimide compound having three or more maleimide skeletons and one or more imide skeletons. The resin material according to claim 10, wherein the thermosetting compound is a maleimide compound, an epoxy compound, a vinyl compound, a benzoxazine compound, or a cyanate ester compound. It contains the thermosetting compound and a curing agent.
The thermosetting compound contains an epoxy compound and contains
The resin material according to claim 10 or 11, wherein the curing agent contains at least one component of a phenol compound, an active ester compound, and a carbodiimide compound. The resin material according to claim 12, wherein the curing agent contains a phenol compound and an active ester compound. The resin material according to claim 12 or 13, wherein at least one of the thermosetting compound and the curing agent has an amide bond or an imide bond. The resin material according to any one of claims 10 to 14, wherein the thermosetting compound has an amide bond or an imide bond. The resin material according to any one of claims 1 to 15, which is a resin film. The resin material according to any one of claims 1 to 16, which is used as an insulating material. The resin material according to any one of claims 1 to 17, which is used for forming an insulating layer in a multilayer printed wiring board. With the circuit board
A plurality of insulating layers arranged on the surface of the circuit board,
It is provided with a metal layer arranged between the plurality of insulating layers.
A multilayer printed wiring board in which 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 18.

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