JP2021025050A - Resin material, and multilayer printed wiring board - Google Patents

Abstract

To provide a resin material 1) capable of heightening embedability to an uneven surface, 2) capable of suppressing the wetting spread, and 3) capable of decreasing the undulation.SOLUTION: The resin material of the present invention includes a maleimide compound, and a hardening accelerator, where the maleimide compound is a maleimide compound exhibiting a property of 5% or more of a haze degree of the maleimide compound-containing liquid when obtaining a maleimide compound-containing liquid including 5 wt.% of the maleimide compound, and 95 wt.% of cyclohexanone, and the content of the maleimide compound in 100 wt.% of constituents excluding an inorganic filler and a solvent in the resin material is 5 wt.% or more.SELECTED DRAWING: Figure 1

Description

The present invention relates to resin materials containing maleimide compounds. 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 8 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 embedding property of the resin material in the unevenness of the substrate or the like is not sufficiently high, or the resin material is excessively wetted and spread. In addition, undulation (waviness) may occur in the formed insulating layer, which may make it difficult to control the thickness of the insulating layer.

An object of the present invention is to provide a resin material capable of 1) enhancing the embedding property in an uneven surface, 2) suppressing wet spread, and 3) reducing undulation. 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, when a maleimide compound-containing liquid containing a maleimide compound and a curing accelerator and containing 5% by weight of the maleimide compound and 95% by weight of cyclohexanone is obtained, the maleimide compound is said to be said. It is a maleimide compound exhibiting a property that the degree of cloudiness of the maleimide compound-containing liquid is 5% or more, and the content of the maleimide compound is 5% by weight or more in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. A resin material is provided.

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

In a specific aspect of the resin material according to the present invention, the maleimide compound has a structure represented by the following formula (X).

In the formula (X), R1 represents a tetravalent organic group.

In certain aspects of the resin material according to the present invention, the maleimide compound has a skeleton derived from an aliphatic diamine compound.

In certain aspects of the resin material according to the present invention, the aliphatic diamine compound has a ring structure containing a cyclohexane skeleton.

In a specific aspect of the resin material according to the present invention, the resin material contains a thermoplastic resin, and the weight average molecular weight of the thermoplastic resin is 20000 or more.

In certain aspects of the resin material according to the present invention, the curing accelerator comprises a photocuring accelerator.

In certain aspects of the resin material according to the present invention, the resin material comprises a curable compound, wherein the curable compound comprises a curable compound having a weight average molecular weight of less than 1500.

In certain aspects of the resin material according to the present invention, a thermosetting compound and a curing agent are included, and the thermosetting compound includes an epoxy compound.

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

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 is a resin film.

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 contains a maleimide compound and a curing accelerator. In the resin material according to the present invention, when a maleimide compound-containing liquid containing 5% by weight of the maleimide compound and 95% by weight of cyclohexanone is obtained, the maleimide compound has a cloudiness of 5% or more in the maleimide compound-containing liquid. It is a maleimide compound that exhibits certain properties. In the resin material according to the present invention, the content of the maleimide compound is 5% by weight or more in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. Since the resin material according to the present invention has the above-mentioned structure, 1) the embedding property in the uneven surface can be enhanced, 2) the wetting spread can be suppressed, and 3) the undulation can be reduced.

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 maleimide compound (hereinafter, may be referred to as "maleimide compound X") and a curing accelerator.

In the resin material according to the present invention, when a maleimide compound-containing liquid containing 5% by weight of the maleimide compound X and 95% by weight of cyclohexanone is obtained, the maleimide compound X has a cloudiness of 5% or more in the maleimide compound-containing liquid. It is a maleimide compound that exhibits the property of.

In the resin material according to the present invention, the content of the maleimide compound X is 5% by weight or more in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material.

Since the resin material according to the present invention has the above-mentioned structure, 1) the embedding property in the uneven surface can be improved, 2) the wetting spread can be suppressed, and 3) the undulation can be reduced. All the effects of 1) and -3) can be exhibited.

Further, when the resin material according to the present invention is a resin film such as a B stage film, the flexibility of the resin film can be increased.

The present inventor has found that by using the maleimide compound X in the resin material, all the effects of 1) -3) above can be exhibited. The maleimide compound X is, for example, a maleimide compound capable of forming aggregates to the extent that it scatters visible light. In the conventional resin material containing a maleimide compound, the cohesiveness of the maleimide compound is not sufficient, and the viscosity of the resin material (crocodile) tends to increase or decrease depending on the molecular weight of the maleimide compound or the like. For this reason, especially when the molecular weight of the maleimide compound is large, the embedding property on the uneven surface is lowered, and especially when the molecular weight of the maleimide compound is small, the wet spread cannot be sufficiently suppressed and the undulation is large. It may become. On the other hand, in the present invention, since the maleimide compound X exhibiting a certain degree of cohesiveness is used, it is possible to prevent the viscosity of the varnish from becoming excessively high, and it is possible to improve the viscosity of the resin material. .. As a result, in the resin material according to the present invention, 1) the embedding property in the uneven surface can be enhanced, 2) the wet spread can be suppressed, and 3) the undulation can be reduced. In the resin material according to the present invention, all the effects of 1) -3) above can be exhibited even when the molecular weight of the maleimide compound X is large.

Further, in the present invention, since the maleimide compound X exhibiting a certain degree of cohesiveness is used, the functional groups can be relatively close to each other even when the reaction equivalent is small. Therefore, the reaction temperature can be lowered and the resin material can be sufficiently cured. Further, since the maleimide compound X has already aggregated, it may be possible to reduce the shrinkage of the resin material during curing. In particular, when the resin material is photocured and used, the reaction temperature is lower than when it is thermally cured and used, so that the molecular mobility is low. In the present invention, since the functional groups can be present relatively close to each other, the reaction efficiency can be improved even when the functional groups are photocured and used. Further, in the present invention, it is possible to prevent the surface roughness of the cured product of the resin material from becoming excessively large when the roughening treatment is performed after the precure, especially in the SAP process.

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 may be heat-cured and used, may be photo-cured and used, or may be heat-cured and photo-cured before use. The resin material according to the present invention is preferably a thermosetting resin material or a photocurable resin material, and more preferably a thermosetting resin material. When the resin material is a resin film, the resin film is preferably a thermocurable resin film or a photocurable resin film, and more preferably a thermocurable 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.

[Maleimide compound X]
The resin material according to the present invention contains the above-mentioned maleimide compound X. The maleimide compound X is preferably a thermosetting compound. 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 is described above when a maleimide compound-containing liquid containing 5% by weight of the maleimide compound X and 95% by weight of cyclohexanone (hereinafter, may be referred to as “first maleimide compound-containing liquid”) is obtained. It is a maleimide compound exhibiting a property that the degree of cloudiness of the maleimide compound-containing liquid (first maleimide compound-containing liquid) is 5% or more.

The cloudiness of the first maleimide compound-containing liquid is preferably 7% or more, more preferably 8% or more. When the degree of cloudiness of the first maleimide compound-containing liquid is at least the above lower limit, the effect of the present invention can be exhibited even more effectively. The upper limit of the cloudiness of the first maleimide compound-containing liquid is not particularly limited. The degree of cloudiness of the first maleimide compound-containing liquid may be 20% or less, 15% or less, or 10% or less.

If the first maleimide compound-containing solution cannot be prepared, such as when the maleimide compound is insoluble in cyclohexanone, the maleimide compound does not fall under the maleimide compound X of the present invention. Further, when the first maleimide compound-containing liquid (5% by weight of the maleimide compound) is allowed to stand at 25 ° C. for 24 hours, and the color of the first maleimide compound-containing liquid after standing is changed, that is, maleimide. When precipitation of the compound occurs, the maleimide compound does not correspond to the maleimide compound X of the present invention.

When a maleimide compound-containing liquid containing 10% by weight of the maleimide compound X and 90% by weight of cyclohexanone (hereinafter, may be referred to as "second maleimide compound-containing liquid") is obtained, the above-mentioned maleimide compound-containing liquid (the first). The degree of cloudiness of the maleimide compound-containing liquid (2) is preferably 8% or more, more preferably 10% or more, still more preferably 15% or more. When the degree of cloudiness of the second maleimide compound-containing liquid is at least the above lower limit, the effect of the present invention can be exhibited even more effectively. The upper limit of the cloudiness of the second maleimide compound-containing liquid is not particularly limited. The degree of cloudiness of the second maleimide compound-containing liquid may be 35% or less, 25% or less, or 20% or less.

It is preferable that the second maleimide compound-containing liquid is allowed to stand at 25 ° C. for 24 hours, and the color of the second maleimide compound-containing liquid after standing is not shaded.

The degree of cloudiness of the first and second maleimide compound-containing liquids can be measured using a haze meter (for example, "HM-150" manufactured by Murakami Color Technology Research Institute).

The first maleimide compound-containing liquid and the second maleimide compound-containing liquid are prepared in order to determine whether or not the maleimide compound X has specific properties. In the resin material according to the present invention, the maleimide compound X may not be added as the first maleimide compound-containing liquid containing 5% by weight of the maleimide compound X and 95% by weight of cyclohexanone, and 10% by weight of the maleimide compound X. It may not be added as a second maleimide compound-containing liquid containing 90% by weight of cyclohexanone. The concentration of the maleimide compound X added when the resin material is produced and the solvent for dissolving the maleimide compound X may be different from the above.

In order to easily satisfy the cloudiness of the first and second maleimide compound-containing liquids within the above range, the maleimide compound X preferably has a skeleton derived from pyromellitic dianhydride, and is aliphatic. It preferably has a skeleton derived from a diamine compound. In order to more easily satisfy the cloudiness of the first and second maleimide compound-containing liquids within the above range, the maleimide compound X is derived from a reaction product of pyromellitic dianhydride and a diamine compound. It preferably has a skeleton, and more preferably has a skeleton derived from a reaction product of pyromellitic dianhydride and an aliphatic diamine compound.

Even if the maleimide compound has a skeleton derived from pyromellitic dianhydride, the degree of cloudiness of the first and second maleimide compound-containing liquids may not satisfy the above range. Further, even if the maleimide compound is a maleimide compound having a skeleton derived from an aliphatic diamine compound, the degree of cloudiness of the first and second maleimide compound-containing liquids may not satisfy the above range. On the other hand, even if the maleimide compound is a maleimide compound having no skeleton derived from pyromellitic dianhydride, the degree of cloudiness of the first and second maleimide compound-containing liquids may satisfy the above range. .. Further, even if the maleimide compound is a maleimide compound having no skeleton derived from an aliphatic diamine compound, the degree of cloudiness of the first and second maleimide compound-containing liquids may satisfy the above range.

Examples of the diamine compound include diamine diamine, tricyclodecanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (aminomethyl) norbornan, 3 (4), 8 ( 9) -Bis (aminomethyl) tricyclo [5.2.1.02,6] decane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, isophoronediamine, 4,4'-methylenebis (cyclohexylamine), 4,4'-Methylenebis (2-methylcyclohexylamine), 1,1-bis (4-aminophenyl) cyclohexane, 2,7-diaminofluorene, 4,4'-ethylenedianiline, 4,4'-methylenebis ( 2,6-diethylaniline), 4,4'-methylenebis (2-ethyl-6-methylaniline), 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, etc. Can be mentioned. Only one type of the diamine compound may be used, or two or more types may be used in combination.

From the viewpoint of exerting the effects of the present invention even more effectively, the diamine compound is preferably an aliphatic diamine compound, and preferably a diamine compound having a dicyclopentadiene skeleton. From the viewpoint of exerting the effects of the present invention even more effectively, the aliphatic diamine compound preferably has a cyclohexyl ring, more preferably has a ring structure containing a cyclohexane skeleton, and has a dicyclopentadiene skeleton. It is more preferable to have. Examples of the ring structure including the cyclohexane skeleton include a tricyclodecane ring, a norbornane ring, and an adamantane skeleton.

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 Croda Japan) and the like.

The maleimide compound X does not have a skeleton derived from diamine diamine, or has a skeleton derived from diamine diamine and is derived from dimer diamine in 100 mol% of all structural units of the skeleton derived from the diamine compound. The average proportion of skeletons is preferably 50 mol% or less. In this case, the coefficient of linear thermal expansion of the cured product can be further reduced. In addition, the degree of cloudiness of the first and second maleimide compound-containing liquids can be easily satisfied within the above range.

Even if the maleimide compound is a maleimide compound having no skeleton derived from dimer diamine, the degree of cloudiness of the first and second maleimide compound-containing liquids may not satisfy the above range. Further, the maleimide compound has a skeleton derived from diamine diamine, and the average ratio of the skeleton derived from diamine diamine is 50 mol% or less in 100 mol% of the total structural units of the skeleton derived from the diamine compound. Even if there is, the degree of cloudiness of the first and second maleimide compound-containing liquids may not satisfy the above range.

The maleimide compound X may have a skeleton derived from a reaction product of a diamine compound and an acid dianhydride other than pyromellitic dianhydride.

Examples of the acid dianhydride other than the pyromellitic dianhydride include tetracarboxylic dianhydride and the like. Examples of the tetracarboxylic dianhydride include 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfonetetracarboxylic dianhydride, 1 , 4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3', 4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-frantetra Caroic acid dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4, 4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3', 4,4'-perfluoroisopropyridenediphthalic acid dianhydride, 3,3', 4,4'- Biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, Examples thereof include bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride and bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride.

From the viewpoint of lowering the dielectric loss tangent of the cured product and increasing the thermal dimensional stability of the cured product, the number of maleimide skeletons in the maleimide compound X is preferably 2 or more, more preferably 3 or more, preferably 10. The number is less than, more preferably 5 or less.

From the viewpoint of further lowering the dielectric loss tangent of the cured product and further enhancing the thermal dimensional stability of the cured product, the maleimide compound X preferably has a maleimide skeleton at both ends.

The maleimide compound X may or may not have a branched structure.

From the viewpoint of exerting the effects of the present invention even more effectively, the maleimide compound X preferably has a structure represented by the following formula (X).

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

The maleimide compound X can be produced, for example, as follows. The diamine compound, the dimer diamine compound, and pyromellitic acid dianhydride are reacted to obtain a first reaction product. The obtained first reactant is reacted with maleic anhydride.

The weight average molecular weight of the maleimide compound X is preferably 1000 or more, more preferably 3000 or more, still more preferably more than 3100, further preferably more than 4500, even more preferably more than 5000, and particularly preferably 7500 or more. Most preferably, it is 8000 or more. The weight average molecular weight of the maleimide compound X is preferably 50,000 or less, more preferably 30,000 or less, still more preferably 20,000 or less, particularly preferably 18,000 or less, and most preferably 15,000 or less. When the weight average molecular weight is at least the above lower limit, the coefficient of linear expansion can be suppressed low, and the viscosity of the resin material can be made appropriate. Further, when the weight average molecular weight exceeds 50,000, the melt viscosity of the resin material becomes higher and the embedding property in the uneven surface may decrease as compared with the case where the weight average molecular weight is 50,000 or less. Further, when the weight average molecular weight is not less than the above lower limit and not more than the above upper limit, the aggregated portion is efficiently etched, so that the desmear property can be enhanced.

The weight average molecular weight indicates the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

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 glass transition temperature of the maleimide compound X is preferably 70 ° C. or higher, more preferably 80 ° C. or higher. That is all.

The glass transition temperature is set by heating in a nitrogen atmosphere from -30 ° C to 260 ° C 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.

From the viewpoint of exerting the effect of the present invention, the content of the maleimide compound X is 5% by weight or more in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material.

From the viewpoint of more effectively exerting the effects of the present invention, the content of the maleimide compound X is preferably 10% by weight or more, preferably 10% by weight or more, based on 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. Is 80% by weight or less, more preferably 70% by weight or less. Further, when the content of the maleimide compound X is at least the above lower limit, the dielectric loss tangent of the cured product can be further lowered.

[Curable compound]
The resin material preferably contains a curable compound different from the maleimide compound X. Only one kind of the curable compound may be used, or two or more kinds may be used in combination.

Examples of the curable compound include thermosetting compounds and photocurable compounds. The curable compound may contain only a thermosetting compound, may contain only a photocurable compound, or may contain a thermosetting compound and a photocurable compound. Further, the curable compound may contain a compound having thermosetting property and photocuring property (heat and photocurable compound). The thermosetting compound may contain heat and photocurable compounds.

The curable compound preferably contains a curable compound having a weight average molecular weight of less than 1500. In this case, the resin material can be cured satisfactorily, and the effects of the present invention can be exhibited even more effectively.

The weight average molecular weight of the curable compound indicates the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

The content of the heat and photocurable 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 20% by weight or more, still more preferably 30% by weight. % Or more, preferably 90% by weight or less, more preferably 80% by weight or less. When the content of the heat and photocurable compound is not less than the above lower limit and not more than the above upper limit, the curing reaction can be sufficiently advanced.

The content of the photocurable 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 20% by weight or more, still more preferably 30% by weight or more. It is preferably 90% by weight or less, more preferably 80% by weight or less. When the content of the photocurable compound is not less than the above lower limit and not more than the above upper limit, the curing reaction can be sufficiently advanced.

[Thermosetting compound]
The resin material preferably contains a thermosetting compound different from the maleimide compound X. 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 a phenoxy compound, an oxetane compound, a maleimide compound different from the maleimide compound X (hereinafter, may be referred to as maleimide compound Y), an epoxy compound, a cyanate compound, a vinyl compound, and a polyarylate compound. Examples thereof include diallyl phthalate compounds, episulfide compounds, (meth) acrylic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds and the like.

The thermosetting compound is preferably a maleimide compound Y, an epoxy compound, or a vinyl compound, more preferably contains an epoxy compound or a vinyl compound, and further preferably contains an epoxy compound. The vinyl compound preferably contains a styrene compound or an acrylate compound, and preferably contains a styrene compound. In this case, the dielectric loss tangent of the cured product can be further lowered, and the thermal dimensional stability of the cured product can be further improved.

<Maleimide compound Y>
When a maleimide compound-containing liquid containing 5% by weight of the maleimide compound Y and 95% by weight of cyclohexanone (hereinafter, may be referred to as "third maleimide compound-containing liquid") is obtained, the maleimide compound Y is described as described above. It is a maleimide compound having a property that the degree of cloudiness of the maleimide compound-containing liquid (third maleimide compound-containing liquid) is less than 5%. The maleimide compound Y is a maleimide compound different from the maleimide compound X. As the maleimide compound Y, only one type may be used, or two or more types may be used in combination.

The third maleimide compound-containing liquid is prepared to determine whether or not the maleimide compound Y has specific properties. In the resin material according to the present invention, the maleimide compound Y may not be added as a third maleimide compound-containing liquid containing 5% by weight of the maleimide compound Y and 95% by weight of cyclohexanone.

The maleimide compound Y may be a heat and photocurable compound.

The maleimide compound Y may be a bismaleimide compound.

Examples of the maleimide compound Y include N-phenylbismaleimide and N-alkylbismaleimide.

The maleimide compound Y preferably has a skeleton derived from a diamine compound other than dimerdiamine or a triamine compound other than trimertriamine.

The maleimide compound Y preferably has an aromatic skeleton.

In the maleimide compound Y, 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 Y 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 Y 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 Y 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.

From the viewpoint of effectively exerting the effects of the present invention, the molecular weight of the maleimide compound Y is preferably 500 or more, more preferably 1000 or more, preferably less than 30,000, and more preferably less than 20,000. When the resin material containing the maleimide compound Y is photocured and used, the molecular weight of the maleimide compound Y is preferably less than 3000, more preferably less than 1500, from the viewpoint of effectively exerting the effect of the present invention. , More preferably less than 1000.

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

Examples of commercially available products of the maleimide compound Y include "BMI-4000" and "BMI-5100" manufactured by Daiwa Kasei Kogyo Co., Ltd., "MIR-3000" manufactured by Nippon Kayaku Co., Ltd., and Designer Moleculars Inc. Examples thereof include "BMI-1500" and "BMI-689" manufactured by Japan.

<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 adjacency of the cured product 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 a naphthalene skeleton or It is preferable to contain an epoxy compound having a phenyl skeleton, and more preferably an epoxy compound having an aromatic skeleton.

From the viewpoint of further lowering the dielectric loss tangent of the cured product and improving the coefficient of linear expansion (CTE) of the cured product, the epoxy compounds are a liquid epoxy compound at 25 ° C and a solid epoxy compound at 25 ° C. And are preferably included.

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 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, preferably 50% by weight or less, more preferably. 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 maleimide compound X and the curing agent described later (content of the epoxy compound / total content of the maleimide compound X and the curing agent described later) Is preferably 0.2 or more, more preferably 0.3 or more, preferably 1 or less, and 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 styrene compounds, acrylate compounds, and divinyl compounds. Examples of the divinyl compound include a divinylbenzyl ether compound. The vinyl compound may be a divinyl compound having an aliphatic skeleton or a divinyl ether compound. The acrylate compound may be a heat and photocurable compound.

Examples of the styrene compound include a phenylene ether compound modified with terminal styrene. Only one kind of the styrene compound may be used, or two or more kinds thereof may be used in combination.

Examples of commercially available styrene compounds include "OPE-2St" manufactured by Mitsubishi Gas Chemical Company, Inc.

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.

[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, diamond, aluminum nitride, and boron nitride.

The inorganic filler is preferably an inorganic filler having a thermal conductivity of 10 W / mK or more, such as alumina and boron nitride. In this case, heat dissipation can be improved.

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. The silica may be hollow silica. Due to the use of 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.

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

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. When the inorganic filler is agglomerated particles, the average particle size of the inorganic filler means the primary particle diameter.

The inorganic filler is preferably spherical, more preferably spherical silica. In this case, the surface roughness of the surface of the cured product is effectively reduced, and 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, the thermal dimensional stability can be improved and the 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. A conventionally known curing agent can be used as the curing agent. 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 a phenol compound (phenol curing agent), an active ester compound, a cyanate ester compound (cyanate ester curing agent), a benzoxazine compound (benzoxazine curing agent), a carbodiimide compound (carbodiimide curing agent), and an amine compound (amine). Hardener), thiol compound (thiol hardener), phosphine compound, dicyandiamide, acid anhydride and the like. The curing agent preferably has a functional group capable of reacting with the epoxy group of the epoxy compound.

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

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 novolac-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 and a naphthalene ring which may have a substituent. 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 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 that the active ester compound has a naphthalene ring or a dicyclopentadiene skeleton in the main chain skeleton.

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

From the viewpoint of lowering the melt viscosity of the resin material, shortening the distance between the cross-linking points, and further reducing the coefficient of linear expansion of the cured product, the active ester compound is preferably an ester compound having low molecular activity. .. Examples of commercially available products of ester compounds having low molecular weight activity include the above-mentioned "EXB-8" manufactured by DIC Corporation.

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.

Commercially available products of the cyanate ester compound 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.

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

Examples of commercially available products of the benzoxazine compound include "P-d type" manufactured by Shikoku Chemicals Corporation and "ODA-BOZ" manufactured by JFE Chemicals Corporation.

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 dielectric loss tangent of the cured product can be lowered and the thermal dimensional stability can be further improved.

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. 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 content of the curing agent 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 or less. When the content of the curing agent is not less than the above lower limit and not more than the above upper limit, the curability is further improved, the thermal dimensional stability is further enhanced, and the volatilization of the residual unreacted component can be further suppressed.

The total content of the maleimide compound X, the thermosetting compound, and the curing agent in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 50% by weight or more, more preferably. It is 60% by weight or more, preferably 98% by weight or less, and more preferably 95% by weight or less. When the total content of the maleimide compound X, 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 warpage of the cured product, the curing accelerator preferably contains the anionic curing accelerator, and more preferably contains the imidazole compound.

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.

When the thermosetting compound contains a radical curable compound such as the vinyl compound, the acrylate compound, and the styrene compound, radical curing proceeds. Therefore, the curing accelerator may contain the radical curing accelerator. preferable.

The curing accelerator preferably contains a photocuring accelerator. When the resin material contains the heat and photocurable compound or the photocurable compound, the curing accelerator preferably contains a photocuring accelerator.

From the viewpoint of enhancing the reactivity, the photocuring accelerator is preferably a photocuring accelerator having an absorption wavelength larger than the absorption wavelength of the maleimide compound Y or the absorption wavelengths not overlapping.

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 at least the above lower limit and at least 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, phenoxy resin, and styrene butadiene 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. The use of the phenoxy resin suppresses deterioration of the embedding property of the resin film in the holes or irregularities of the circuit board and non-uniformity of the inorganic filler. 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 dimer diamine.

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, PRIAMINE1074 (trade name, all manufactured by Croda Japan Co., Ltd.) and the like.

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 compound, 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 10,000 or more, more preferably 15,000 or more, still more preferably 20,000 or more. It is preferably 100,000 or less, more 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 rocking 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. Examples of the fluororesin include polytetrafluoroethylene (PTFE) 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 film. 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 including 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. 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, the metal layer 17 is formed in a part of the upper surface of the insulating layers 13 to 15 other than the insulating layer 16 located on the outer surface opposite to the circuit board 12 side. ing. 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.

The cured product is preferably roughened in order to form fine irregularities on the surface of the cured product obtained by pre-curing the resin material. 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 at a treatment temperature of 30 ° C. to 85 ° C. for 1 minute to 30 minutes using a 40 wt% ethylene glycol aqueous solution or the like. 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.

(Maleimide compound X)
Maleimide compound X-1:
A maleimide compound X-1 (molecular weight 12000) represented by the following formula (X-1) was synthesized according to the following Synthesis Example 1.

<Synthesis example 1>
In a 500 mL eggplant flask, 105 g of toluene, 41 g of N-methyl-2-pyrrolidone (NMP), and 7 g of methanesulfonic acid were placed. Then, 9.3 g (23 mmol) of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) and 10.2 g (53 mmol) of tricyclodecane diamine were added. Then, 13.1 g (60 mmol) of pyromellitic dianhydride was added little by little. An eggplant flask was attached to the Dean-Stark apparatus and heated to reflux for 3.5 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, 4.42 g (45 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. The organic layer was washed with a mixed solvent of water and ethanol, and then the mixed solvent was removed with an evaporator to obtain a toluene solution. Isopropanol was then added to the toluene solution to reprecipitate the product. Then, it was dried in a vacuum oven to obtain maleimide compound X-1. The structure represented by the following formula (X-1) is an example of the maleimide compound X-1. The maleimide compound X-1 is, for example, a mixture containing a compound having a structure in which the position of the amino group is different from the structure represented by the following formula (X-1).

Maleimide compound X-2:
Maleimide compound X-2 (molecular weight 3300) was synthesized according to the following Synthesis Example 2.

<Synthesis example 2>
In a 500 mL eggplant flask, 90 g of toluene, 46 g of N-methyl-2-pyrrolidone (NMP), and 9 g of methanesulfonic acid were placed. Then 15.6 g (80 mmol) of tricyclodecanediamine was added. Then, 13.1 g (60 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 3.5 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, 4.42 g (45 mmol) of maleic anhydride was added and stirred, and the reaction was carried out in the same manner. Then, the organic layer was washed with a mixed solvent of water and ethanol, and then the mixed solvent was removed with an evaporator to obtain a toluene solution. Isopropanol was then added to the toluene solution to reprecipitate the product. Then, it was dried in a vacuum oven to obtain maleimide compound X-2.

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

GPC (Gel Permeation Chromatography) Measurement:
A high performance liquid chromatograph system manufactured by Shimadzu Corporation was used, and measurement was 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" manufactured by Shodex (exclusion limit molecular weight: 400,000) 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)
Maleimide compound Y-1:
Maleimide compound Y-1 (molecular weight 17500) was synthesized according to the following Synthesis Example 3.

<Synthesis example 3>
In a 500 mL eggplant flask, 105 g of toluene, 41 g of N-methyl-2-pyrrolidone (NMP), and 7 g of methanesulfonic acid were placed. 15.5 g (80 mmol) of tricyclodecanediamine and 32.8 g (80 mmol) of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) were added. Then, 62.5 g (120 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 3.5 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, 8.83 g (90 mmol) of maleic anhydride was added and stirred, and the reaction was carried out in the same manner. Then, the organic layer was washed with a mixed solvent of water and ethanol, and then the mixed solvent was removed with an evaporator to obtain a toluene solution. Isopropanol was then added to the toluene solution to reprecipitate the product. Then, it was dried in a vacuum oven to obtain maleimide compound Y-1.

N-alkylbismaleimide compound (“BMI-1500” manufactured by Designer Molecules Inc., maleimide compound Y)
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)
Multi-branched aliphatic epoxy compound (Nissan Chemical Industries, Ltd. "Foldi E101")

(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 curing 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 dimer diamine, was synthesized according to the following Synthesis Example 4.

<Synthesis example 4>
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 an imidization reaction was carried out at 140 ° C. for 10 hours. In this way, a polyimide compound-containing solution (nonvolatile content 26.8% by weight) was obtained. The molecular weight (weight average molecular weight) of the obtained polyimide compound was 20000. The molar ratio of the acid component / amine component was 1.04.

The molecular weight of the polyimide compound synthesized in Synthesis Example 4 was determined as follows.

GPC (Gel Permeation Chromatography) Measurement:
A high performance liquid chromatograph system manufactured by Shimadzu Corporation was used, and measurement was 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" manufactured by Shodex (exclusion limit molecular weight: 400,000) 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 and 2 and Comparative Examples 1 and 2)
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) Cloudiness of Maleimide Compound-Containing Solution 5% by weight of maleimide compound (maleimide compound X-1, maleimide compound X-2, maleimide compound Y-1, N-alkylbismaleimide compound) and 95% by weight of cyclohexanone are mixed. Then, the mixture was sufficiently stirred to prepare a first maleimide compound-containing solution. Further, 10% by weight of the maleimide compound (maleimide compound X-1, maleimide compound X-2, maleimide compound Y-1, N-alkylbismaleimide compound) and 90% by weight of cyclohexanone were mixed and then sufficiently stirred. , A second maleimide compound-containing solution was prepared.

The obtained first and second maleimide compound-containing liquids were placed in a quartz cell (optical path length 1 cm), placed in a haze meter (“HM-150” manufactured by Murakami Color Technology Research Institute), and the degree of cloudiness was measured.

(2) Embedding property on uneven surface and prevention of excessive wetting and spreading (prevention of protrusion)
Only the copper foil of a 100 mm square copper-clad laminate (a laminate of a glass epoxy substrate with a thickness of 400 μm and a copper foil with a thickness of 25 μm) is etched to form a recess (opening) with a diameter of 100 μm and a depth of 25 μm. The holes were formed so that the distance between the centers of the holes linearly and adjacent to the 30 mm square area of the center of the substrate was 900 μm. In this way, an evaluation substrate having a total of 900 holes was prepared.

The resin film side of the obtained laminated film was laminated on the evaluation substrate, and using "Batch type vacuum laminator MVLP-500-IIA" manufactured by Meiki Co., Ltd., the lamination pressure was 0.4 MPa for 20 seconds and the press pressure was 0.8 MPa. The film was heated and pressurized at a temperature of 90 ° C. for laminating and pressing for 20 seconds. After cooling at room temperature, the PET film was peeled off. In this way, an evaluation sample in which a resin film was laminated on the evaluation substrate was obtained.

The voids in the depressions were observed using an optical microscope for the obtained evaluation sample. By evaluating the proportion of dents in which voids were observed, the embedding property in the uneven surface was determined according to the following criteria.

[Criteria for embedding on uneven surfaces]
◯: Percentage of dents in which voids were observed 0%
Δ: Percentage of dents with observed voids Exceeding 0% and less than 5% ×: Percentage of dents with observed voids 5% or more

With respect to the obtained evaluation sample, it was observed whether or not the resin film protruded from a predetermined region on the substrate using an optical microscope, and the protrusion prevention property was judged according to the following criteria.

[Criteria for preventing protrusion]
◯: The protrusion of the resin film from the peripheral part of the evaluation substrate after lamination is 2 mm or less Δ: The protrusion of the resin film from the peripheral part of the evaluation substrate after lamination is more than 2 mm and 3 mm or less ×: From the peripheral part of the evaluation substrate after lamination The protrusion of the resin film exceeds 3 mm

(3) Undulation A mask is attached to a copper layer having a thickness of 18 μm so that a rectangular area of 1 mm in length × 2 mm in width is etched, and the copper is etched to have a rectangular recess of 1 mm × 2 mm. A corner board was prepared. Both sides of the copper foil surface of this substrate were immersed in "Cz8101" manufactured by MEC to roughen the surface of the copper foil. Using "Batch type vacuum laminator MVLP-500-IIA" manufactured by Meiki Co., Ltd., the resin film (B stage film) side of the laminated film is laminated on both sides of the roughened substrate. , A laminated structure was obtained. The laminating conditions were such that the pressure was reduced for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, then laminating at 100 ° C. and pressure 0.7 MPa for 30 seconds, and further pressing at a press pressure of 0.8 MPa and a press temperature of 100 ° C. for 60 seconds. The PET film was peeled off and heated at 100 ° C. for 30 minutes, and then further heated at 180 ° C. for 30 minutes to semi-cure the resin film. The surface of the semi-cured resin film (the surface opposite to the substrate) where the copper pattern is present, and the surface of the semi-cured resin film (the surface opposite the substrate) where the copper pattern is not present. Was observed, and the maximum value of the height difference between the adjacent concave portion and the convex portion was adopted as the undulation value using an optical step meter.

[Criteria for undulation]
◯: The undulation value is 2 μm or less ×: The undulation value exceeds 2 μm

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 (16)

Contains a maleimide compound and a curing accelerator
When a maleimide compound-containing liquid containing 5% by weight of the maleimide compound and 95% by weight of cyclohexanone is obtained, the maleimide compound is a maleimide compound exhibiting a property that the degree of cloudiness of the maleimide compound-containing liquid is 5% or more. ,
A resin material in which the content of the maleimide compound is 5% by weight or more in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. The resin material according to claim 1, wherein the maleimide compound has a weight average molecular weight of 1000 or more and 50,000 or less. The resin material according to claim 1 or 2, wherein the maleimide compound has a structure represented by the following formula (X).

In the formula (X), R1 represents a tetravalent organic group. The resin material according to any one of claims 1 to 3, wherein the maleimide compound has a skeleton derived from an aliphatic diamine compound. The resin material according to claim 4, wherein the aliphatic diamine compound has a ring structure containing a cyclohexane skeleton. Contains thermoplastic resin
The resin material according to any one of claims 1 to 5, wherein the thermoplastic resin has a weight average molecular weight of 20,000 or more. The resin material according to any one of claims 1 to 6, wherein the curing accelerator contains a photocuring accelerator. Contains curable compounds
The resin material according to any one of claims 1 to 7, wherein the curable compound contains a curable compound having a weight average molecular weight of less than 1500. Contains thermosetting compounds and curing agents
The resin material according to any one of claims 1 to 8, wherein the thermosetting compound contains an epoxy compound. The resin material according to claim 9, wherein the curing agent contains an active ester compound. The resin material according to any one of claims 1 to 10, which comprises an inorganic filler. The resin material according to claim 11, 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 11 or 12, wherein the inorganic filler is silica. The resin material according to any one of claims 1 to 13, which is a resin film. The resin material according to any one of claims 1 to 14, 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,
With a plurality of metal layers arranged between the 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 15.

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