JP2020094212A - Resin material and multilayer printed wiring board - Google Patents

Abstract

To provide a resin material capable of lowering a dielectric loss tangent of a hardened product over a wide frequency band from a low frequency band to a high frequency band, and effectively removing smear by desmear treatment.SOLUTION: A resin material contains a first compound having a naphthylene ether skeleton, and a second compound having a skeleton derived from dimer diamine or a skeleton derived from trimer triamine. The second compound is a compound different from a polyimide compound.SELECTED DRAWING: Figure 1

Description

The present invention relates to a resin material containing a compound having a naphthylene ether skeleton. The present invention also relates to a multilayer printed wiring board using the above resin material.

Conventionally, various resin materials have been used to obtain electronic components such as semiconductor devices, 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 inner layers or to form an insulating layer located on the 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 filmizing the resin material 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.

As an example of the above resin material, the following Patent Document 1 discloses (A) a polyfunctional epoxy resin (excluding a phenoxy resin), (B) a phenol-based curing agent and/or an active ester-based curing agent, (C). A resin composition containing a thermoplastic resin, (D) an inorganic filler, and (E) a quaternary phosphonium-based curing accelerator is disclosed. The (C) thermoplastic resin is a thermoplastic resin selected from a phenoxy resin, a polyvinyl acetal resin, a polyimide, a polyamideimide resin, a polyether sulfone resin, and a polysulfone resin. The (E) quaternary phosphonium-based curing accelerator is one or more quaternary phosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. It is a phosphonium-based curing accelerator.

In addition, Patent Document 2 below discloses a cured product of a resin composition containing an epoxy compound, a curing agent, an inorganic filler, and a polyimide. The cured product has a sea-island structure having a sea part and an island part, the island part has an average major axis of 5 μm or less, and the island part contains the polyimide. The content of the inorganic filler is 30% by weight or more and 90% by weight or less based on 100% by weight of the cured body. The cured product can be used as a material for the insulating layer.

JP, 2005-145498, A WO2018/062405A1

When the insulating layer is formed by using the conventional resin materials described in Patent Documents 1 and 2, the cured product may not have a sufficiently low dielectric loss tangent. When the insulating layer is formed using the conventional resin material as described in Patent Document 1, for example, even if the dielectric loss tangent in a specific narrow frequency band such as a low frequency band can be lowered, It is difficult to lower the dielectric loss tangent of the cured product over a wide frequency band from the low frequency band to the high frequency band.

In addition, when a large amount of a polyimide compound having a large molecular weight is mixed in the resin material in order to lower the dielectric loss tangent, the embeddability on the uneven surface of the substrate or the like may deteriorate.

Further, in the conventional resin material, the smear in the via may not be sufficiently removed by the desmearing treatment when the insulating layer is formed.

An object of the present invention is to provide a resin material capable of reducing the dielectric loss tangent of a cured product over a wide frequency band from a low frequency band to a high frequency band, and capable of effectively removing smear by a desmear treatment. It is to be. 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, a first compound having a naphthylene ether skeleton and a second compound having a skeleton derived from dimerdiamine or a skeleton derived from trimertriamine are included, and the second compound There is provided a resin material, wherein the compound is a compound different from the polyimide compound.

In one specific aspect of the resin material according to the present invention, the first compound is a compound having two or more naphthylene ether skeletons.

In one specific aspect of the resin material according to the present invention, the first compound contains at least one of an epoxy compound having a naphthylene ether skeleton and an active ester compound having a naphthylene ether skeleton.

In a specific aspect of the resin material according to the present invention, the first compound includes both an epoxy compound having a naphthylene ether skeleton and an active ester compound having a naphthylene ether skeleton.

In a particular aspect of the resin material according to the present invention, as the first compound, an epoxy compound having a naphthylene ether skeleton and a softening point of more than 90° C., and a naphthylene ether skeleton and 145° C. At least one of the active ester compounds having a softening point of more than.

In a specific aspect of the resin material according to the present invention, the first compound includes an epoxy compound having a naphthylene ether skeleton and having a softening point of higher than 90°C.

One specific aspect of the resin material according to the present invention includes an active ester compound having a naphthylene ether skeleton and having a softening point of higher than 145°C.

In one specific aspect of the resin material according to the present invention, an epoxy compound having a naphthylene ether skeleton and a softening point of more than 90° C., and an activity having a naphthylene ether skeleton and a softening point of more than 145° C. Includes both ester compounds.

In a specific aspect of the resin material according to the present invention, the resin material contains an epoxy compound and a curing agent, and the first compound is at least one of the epoxy compound and the curing agent. The content of the first compound is 50% by weight or more in a total of 100% by weight of all the epoxy compounds and all the curing agents in the resin material.

In a specific aspect of the resin material according to the present invention, the second compound has a skeleton derived from dimer diamine, and has at least one skeleton of a maleimide skeleton, a benzoxazine skeleton, and a phenol skeleton. It is a compound that has.

On the specific situation with the resin material which concerns on this invention, the said resin material contains an inorganic filler.

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

The resin material according to the present invention is preferably used 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 a surface of the circuit board, and a metal layer arranged between the plurality of insulating layers, the plurality of insulating layers Provided is a multilayer printed wiring board, in which at least one layer is a cured product of the above resin material.

The resin material according to the present invention includes a first compound having a naphthylene ether skeleton and a second compound having a skeleton derived from dimer diamine or a skeleton derived from trimer triamine, and the second compound The compound is a compound different from the polyimide compound. In the resin material according to the present invention, since the above configuration is provided, it is possible to reduce the dielectric loss tangent of the cured product over a wide frequency band from the low frequency band to the high frequency band, and to eliminate smear by the desmear treatment. It can be effectively removed.

FIG. 1 is a 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 has a skeleton derived from a first compound having a naphthylene ether skeleton (hereinafter sometimes referred to as “first compound”) and a skeleton derived from dimerdiamine or derived from trimertriamine. And a second compound having a skeleton (hereinafter, sometimes referred to as “second compound”). In the resin material according to the present invention, the second compound is a compound different from the polyimide compound.

In the resin material according to the present invention, since the above configuration is provided, it is possible to reduce the dielectric loss tangent of the cured product over a wide frequency band from the low frequency band to the high frequency band, and to eliminate smear by the desmear treatment. It can be effectively removed.

The insulating layer in the multilayer printed wiring board preferably has a low dielectric loss tangent over a wide frequency band. However, when the insulating layer is formed by using the resin material containing the first compound and not containing the second compound, the dielectric loss tangent in a low frequency band (for example, 1 GHz or more and 10 GHz or less) can be lowered. Even if it is possible, it is difficult to lower the dielectric loss tangent in a high frequency band (for example, 10 GHz or more and 40 GHz or less). When the insulating layer is formed using a resin material that does not include the first compound and does not include the second compound, a low frequency band (for example, 1 GHz or more and 10 GHz or less) to a high frequency band (for example, 10 GHz or more). It is difficult to lower the dielectric loss tangent over a wide frequency band (40 GHz or less).

On the other hand, since the resin material according to the present invention contains both the first compound and the second compound, the dielectric loss tangent of the cured product over a wide frequency band from a low frequency band to a high frequency band. Can be lowered. In the cured product of the resin material according to the present invention, the dielectric loss tangent of the cured product can be lowered over a wide frequency band of 1 GHz or more and 40 GHz or less. With the resin material according to the present invention, the dielectric loss tangent of the cured product in the high frequency band, which was particularly difficult with conventional resin materials, can be made sufficiently low, and it is possible to cover a wide frequency band from a low frequency band to a high frequency band. The dielectric loss tangent of the cured product can be lowered.

Further, a cured product of a resin material containing the first compound and not containing the second compound is less likely to be etched, and smear is likely to remain after the desmear treatment.

On the other hand, in the resin material according to the present invention, since the first compound and the second compound are both contained, the cured product is appropriately easily etched, and the smear is effectively removed by the desmear treatment. be able to. When the degree of unsaturation of the second compound is high, the smear can be more effectively removed by the desmear treatment.

Further, with the resin material according to the present invention, the surface roughness after etching can be reduced, and the uniformity of the surface roughness can be improved.

Further, with the resin material according to the present invention, it is possible to prevent the melt viscosity from becoming excessively high, and it is possible to enhance the embeddability on the uneven surface of the substrate or the like.

Further, the resin material according to the present invention can improve the thermal dimensional stability of the cured product.

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

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

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

The resin material according to the present invention preferably contains an epoxy compound. The resin material according to the present invention preferably contains a curing agent. The resin material according to the present invention preferably contains an epoxy compound and a curing agent. The first compound is preferably at least one of the epoxy compound and the curing agent. The first compound may be an epoxy compound or the curing agent. The resin material according to the present invention may contain an epoxy compound different from the first compound, and may contain a curing agent different from the first compound.

[Compound having naphthylene ether skeleton (first compound)]
The resin material according to the present invention includes a compound having a naphthylene ether skeleton (first compound). The naphthylene ether skeleton exists as a partial skeleton in the first compound. The naphthylene ether skeleton refers to a skeleton in which an oxygen atom is bonded to the carbon atom forming the naphthalene ring. The oxygen atom bonded to the carbon atom forming the naphthalene ring may be bonded to a carbonyl group. That is, the oxygen atom bonded to the carbon atom forming the naphthalene ring may be an oxygen atom forming the ester skeleton. As for the said 1st compound, only 1 type may be used and 2 or more types may be used together. Two or more kinds of the first compound are preferably used.

The first compound has at least one naphthylene ether skeleton.

The first compound preferably has two or more naphthylene ether skeletons, more preferably three or more, even more preferably four or more, preferably 15 or less, and 10 or less. It is more preferable to have, and it is still more preferable to have 8 or less. When the number of the naphthylene ether skeletons is equal to or more than the lower limit, the dielectric loss tangent in the low frequency band can be further lowered. When the number of the naphthylene ether skeleton is not more than the above upper limit, the smear can be more effectively removed by the desmear treatment. Further, when the number of the naphthylene ether skeleton is not more than the upper limit, the flexibility of the resin film and the embeddability on the uneven surface can be improved.

The first compound preferably has a naphthylene ether skeleton at both ends. The first compound preferably has a naphthylene ether skeleton at both ends and portions other than both ends.

Examples of the first compound include an epoxy compound having a naphthylene ether skeleton, an active ester compound having a naphthylene ether skeleton, a naphthol compound, and a cyanate compound having a naphthylene ether skeleton.

Hereinafter, the epoxy compound having the naphthylene ether skeleton and the active ester compound having the naphthylene ether skeleton will be described in detail.

<Epoxy compound having naphthylene ether skeleton>
The resin material preferably contains, as the first compound, an epoxy compound having a naphthylene ether skeleton. The epoxy compound having a naphthylene ether skeleton is a compound having at least one naphthylene ether skeleton and at least one epoxy group. The epoxy compounds having a naphthylene ether skeleton may be used alone or in combination of two or more.

The epoxy compound having a naphthylene ether skeleton preferably has two or more naphthylene ether skeletons, more preferably three or more, more preferably four or more, and further preferably 15 or less. It is preferable to have 10 or less, and more preferable to have 8 or less. When the number of the naphthylene ether skeletons is equal to or more than the lower limit, the dielectric loss tangent in the low frequency band can be further lowered. Further, when the number of the naphthylene ether skeleton is not less than the lower limit, the thermal dimensional stability can be further enhanced. When the number of the naphthylene ether skeleton is not more than the above upper limit, the smear can be more effectively removed by the desmear treatment. Further, when the number of the naphthylene ether skeleton is not more than the upper limit, the flexibility of the resin film and the embeddability on the uneven surface can be improved.

Examples of the epoxy compound having a naphthylene ether skeleton include naphthol aralkyl type epoxy compounds.

The epoxy compound having a naphthylene ether skeleton is preferably a solid epoxy compound at 25°C.

The molecular weight of the epoxy compound having a naphthylene ether skeleton is preferably 5000 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 resin material is laminated on the circuit board, the inorganic filler can be uniformly present.

The molecular weight of the epoxy compound having a naphthylene ether skeleton means a molecular weight that can be calculated from the structural formula when the epoxy compound is not a polymer and when the structural formula of the epoxy compound can be specified. The molecular weight of the epoxy compound having the naphthylene ether skeleton is the weight in terms of polystyrene measured by gel permeation chromatography (GPC) when the epoxy compound having the naphthylene ether skeleton is a polymer. The average molecular weight is shown.

The softening point of the epoxy compound having the naphthylene ether skeleton is preferably higher than 90°C, more preferably 95°C or higher, further preferably 100°C or higher, preferably 200°C or lower, more preferably 150°C or lower, More preferably, it is 130° C. or lower. When the softening point of the epoxy compound having the naphthylene ether skeleton satisfies the above lower limit and the above upper limit, the thermal dimensional stability of the cured product can be further enhanced, and the adhesion between the insulating layer and the metal layer can be further improved. It can be further enhanced.

The softening point of the epoxy compound having a naphthylene ether skeleton is -30°C to 200 at a temperature rising rate of 3°C/min using a differential scanning calorimeter (for example, "Q2000" manufactured by TA Instruments Co., Ltd.). It can be determined from the inflection point of reverse heat flow by heating up to ℃ in a nitrogen atmosphere.

<Active ester compound having naphthylene ether skeleton>
The resin material preferably contains an active ester compound having a naphthylene ether skeleton as the first compound. The active ester compound having a naphthylene ether skeleton is a curing agent. The active ester compound having a naphthylene ether skeleton is a compound having a naphthylene ether skeleton and an ester bond, and an aliphatic chain, an aliphatic ring or an aromatic ring bonded to both sides of the ester bond. .. The active ester compound having a naphthylene ether skeleton may be used alone or in combination of two or more.

From the viewpoint of accelerating the curing reaction, the active ester compound having a naphthylene ether skeleton preferably has 3 or more naphthylene ether skeletons and 2 or more ester bonds. If the number of naphthylene ether skeletons in the active ester compound having the naphthylene ether skeleton is less than 3 or the number of ester bonds is less than 2, the curing reaction cannot be favorably advanced. It may not be able to function as a curing agent.

The active ester compound having a naphthylene ether skeleton preferably has 3 or more naphthylene ether skeletons, more preferably 4 or more, more preferably 15 or less, and preferably 10 or less. It is more preferable to have 8 or less. When the number of the naphthylene ether skeletons is equal to or more than the lower limit, the dielectric loss tangent in the low frequency band can be further lowered. Further, when the number of the naphthylene ether skeleton is not less than the lower limit, the thermal dimensional stability can be further enhanced. When the number of the naphthylene ether skeleton is not more than the above upper limit, the smear can be more effectively removed by the desmear treatment. Moreover, when the number of the naphthylene ether skeletons is not more than the upper limit, the flexibility of the B stage film (sheet) can be increased. In addition, the embeddability on the uneven surface can be improved.

Examples of the active ester compound having a naphthylene ether skeleton include compounds 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, X2 represents a group containing an aromatic ring, and among X1 and X2 At least one of them has a naphthylene ether skeleton.

In the above formula (1), X1 and X2 preferably have any of the following configurations (i) to (iii).

(I) 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 a naphthylene ether skeleton.

(Ii) In the above formula (1), X1 represents a group containing a naphthylene ether skeleton, and X2 represents a group containing an aromatic ring.

(Iii) In the above formula (1), X1 represents a group containing a naphthylene ether skeleton, and X2 represents a group containing a naphthylene ether skeleton.

In the formula (1), when X1 is a group containing a naphthylene ether skeleton, the X1 may further have an aliphatic chain or an aliphatic ring, and the naphthylene ether skeleton is Alternatively, it may further have an aromatic ring. Further, in the above formula (1), when X2 is a group containing a naphthylene ether skeleton, the X2 may further have an aromatic ring in addition to the naphthylene ether skeleton. Further, in the above formula (1), when X2 is a group containing a naphthylene ether skeleton, X2 may have a structure derived from a naphthalene diol compound, and a structure derived from a naphthalene diol compound is It may have a continuous structure. Further, the structure derived from the naphthalenediol compound may have two or more oxygen atoms. The naphthalene skeleton in the structure derived from the naphthalene diol compound may have a substituent.

Preferable examples of the group containing an aromatic ring in the above formula (1) include a benzene ring which may have a substituent and a naphthalene ring which may have a substituent. A hydrocarbon group is mentioned as said substituent.

For example, the active ester compound having a naphthylene ether skeleton may be a compound represented by the following formula (1A).

In the above formula (1A), R represents a group having an aliphatic skeleton or an aromatic skeleton, and n represents an integer of 1 or more. R in the above formula (1A) is a side chain. Examples of R in the above formula (1A) include a benzyl group.

From the viewpoint of enhancing thermal dimensional stability and flame retardancy, the active ester compound having the naphthylene ether skeleton preferably has at least one aromatic ring that does not form the naphthylene ether skeleton, and preferably two aromatic rings. It is more preferable to have the above.

From the viewpoint of further enhancing the thermal dimensional stability of the cured product and further enhancing the adhesion between the insulating layer and the metal layer, the softening point of the active ester compound having a naphthylene ether skeleton preferably exceeds 145°C. , More preferably 150° C. or higher, preferably 200° C. or lower, more preferably 190° C. or lower, still more preferably 180° C. or lower.

The softening point of the active ester compound having the naphthylene ether skeleton is from -30°C at a temperature rising rate of 3°C/min using a differential scanning calorimeter (for example, "Q2000" manufactured by TA Instruments Co., Ltd.). It can be determined from the inflection point of reverse heat flow by heating up to 200° C. in a nitrogen atmosphere.

<Other details of epoxy compound having naphthylene ether skeleton and active ester compound having naphthylene ether skeleton>
From the viewpoint of effectively exerting the effect of the present invention, the resin material is, as the first compound, an epoxy compound having the naphthylene ether skeleton and an active ester compound having the naphthylene ether skeleton. It is preferable to include at least one. In this case, the resin material may contain only the epoxy compound having the naphthylene ether skeleton as the first compound, or may contain only the active ester compound having the naphthylene ether skeleton. .. Further, in this case, the resin material may include, as the first compound, both an epoxy compound having the naphthylene ether skeleton and an active ester compound having the naphthylene ether skeleton. As for the epoxy compound having a naphthylene ether skeleton, only one kind may be used, two kinds may be used, or three kinds or more may be used. As the active ester compound having a naphthylene ether skeleton, only one type may be used, two types may be used, or three or more types may be used.

From the viewpoint of more effectively exhibiting the effects of the present invention, the resin material includes, as the first compound, an epoxy compound having the naphthylene ether skeleton and an active ester compound having the naphthylene ether skeleton. Both are preferably included.

The content of the epoxy compound having a naphthylene ether skeleton is preferably 10% by weight or more, more preferably 15% by weight or more, still more preferably 20% based on 100% by weight of the component excluding the inorganic filler and the solvent in the resin material. It is at least 50% by weight, preferably at most 45% by weight, more preferably at most 35% by weight. When the content of the epoxy compound having the naphthylene ether skeleton is at least the above lower limit, the dielectric loss tangent in the low frequency band can be further lowered, and the thermal dimensional stability can be improved. When the content of the epoxy compound having the naphthylene ether skeleton is not more than the upper limit, smear can be more effectively removed by the desmear treatment, and the heating temperature at the time of main curing the resin material is low. Can be suppressed.

The content of the active ester compound having the naphthylene ether skeleton in 100% by weight of the component excluding the inorganic filler and the solvent in the resin material is preferably 15% by weight or more, more preferably 20% by weight or more, and further preferably It is 30% by weight or more, preferably 45% by weight or less, and more preferably 35% by weight or less. When the content of the active ester compound having the naphthylene ether skeleton is at least the above lower limit, the dielectric loss tangent in the low frequency band can be further lowered, and the thermal dimensional stability of the cured product can be increased. .. When the content of the active ester compound having the naphthylene ether skeleton is not more than the above upper limit, smear can be more effectively removed by the desmear treatment, and the heating temperature for the main curing of the resin material is It can be kept low.

The total content of the epoxy compound having the naphthylene ether skeleton and the active ester compound having the naphthylene ether skeleton in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 20% by weight. As described above, the content is more preferably 30% by weight or more, preferably 70% by weight or less, and more preferably 60% by weight or less. When the total content is at least the above lower limit, the dielectric loss tangent in the low frequency band can be further lowered, and the flame retardancy can be enhanced. When the total content is less than or equal to the upper limit, the smear can be more effectively removed by the desmear treatment, and the heating temperature for the main curing of the resin material can be suppressed to be low.

The content of the active ester compound having the naphthylene ether skeleton with respect to 100 parts by weight of the epoxy compound having the naphthylene ether skeleton is preferably 40 parts by weight or more, more preferably 50 parts by weight or more, and preferably 200 parts by weight. The amount is preferably 150 parts by weight or less, more preferably 150 parts by weight or less.

From the viewpoint of effectively exerting the effect of the present invention and from the viewpoint of enhancing the thermal dimensional stability of the cured product, the resin material has, as the first compound, a naphthylene ether skeleton and a softening temperature exceeding 90° C. It is preferable to contain at least one of an epoxy compound having a point and an active ester compound having a naphthylene ether skeleton and having a softening point of higher than 145° C. In this case, the resin material may include, as the first compound, only an epoxy compound having the naphthylene ether skeleton and having a softening point of higher than 90° C., and having the naphthylene ether skeleton. And may include only active ester compounds having a softening point above 145°C. Further, the resin material has, as the first compound, an epoxy compound having a naphthylene ether skeleton and a softening point of more than 90° C., and a naphthylene ether skeleton and a softening point of more than 145° C. It may contain both an active ester compound.

From the viewpoint of more effectively exerting the effects of the present invention, the resin material contains, as the first compound, an epoxy compound having the naphthylene ether skeleton and having a softening point of more than 90° C. Is preferable, and it is preferable to include an active ester compound having the naphthylene ether skeleton and having a softening point of higher than 145°C.

From the viewpoint of exerting the effects of the present invention even more effectively, and from the viewpoint of enhancing the thermal dimensional stability of the cured product, the resin material has, as the first compound, a naphthylene ether skeleton and a temperature of 90° C. It is preferable to include both an epoxy compound having a softening point of more than 1 and an active ester compound having a naphthylene ether skeleton and having a softening point of more than 145°C.

The content of the epoxy compound having the above-mentioned naphthylene ether skeleton and having a softening point of more than 90° C. is preferably 10% by weight or more, more preferably 100% by weight in the resin material excluding the inorganic filler and the solvent. Is 12% by weight or more, preferably 40% by weight or less, and more preferably 30% by weight or less. When the content of the epoxy compound having the naphthylene ether skeleton and having a softening point of more than 90° C. is at least the above lower limit, the dielectric loss tangent in the low frequency band can be further lowered, and the cured product can be obtained. Thermal dimensional stability can be improved. When the content of the epoxy compound having the naphthylene ether skeleton and having a softening point of more than 90° C. is not more than the above upper limit, smear can be more effectively removed by the desmear treatment, and the resin material can be used. It is possible to suppress the heating temperature at the time of main curing of the composition to a low level, and it is possible to enhance the laminating property.

The content of the active ester compound having the above-mentioned naphthylene ether skeleton and having a softening point of higher than 145° C. is preferably 10% by weight or more, and more preferably 100% by weight, based on 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. It is preferably 12% by weight or more, preferably 40% by weight or less, and more preferably 30% by weight or less. When the content of the active ester compound having the naphthylene ether skeleton and having a softening point of higher than 145° C. is at least the above lower limit, the dielectric loss tangent in the low frequency band can be further lowered, and a cured product can be obtained. The thermal dimensional stability of can be improved. When the content of the active ester compound having the naphthylene ether skeleton and having a softening point of higher than 145° C. is equal to or lower than the upper limit, smear can be more effectively removed by the desmear treatment, and the resin The heating temperature for the main curing of the material can be kept low, and the laminating property can be improved.

An epoxy compound having a naphthylene ether skeleton and having a softening point of more than 90° C. and a softening point of more than 145° C. having a naphthylene ether skeleton in 100% by weight of components excluding an inorganic filler and a solvent in a resin material. The total content with the active ester compound having is preferably 20% by weight or more, more preferably 30% by weight or more. An epoxy compound having a naphthylene ether skeleton and having a softening point of more than 90° C. and a softening point of more than 145° C. having a naphthylene ether skeleton in 100% by weight of components excluding an inorganic filler and a solvent in a resin material. The total content with the active ester compound having is preferably 80% by weight or less, more preferably 60% by weight or less. When the total content is at least the above lower limit, the dielectric loss tangent in the low frequency band can be further lowered, and the thermal dimensional stability of the cured product can be enhanced. When the total content is less than or equal to the above upper limit, smear can be more effectively removed by desmearing, and the heating temperature at the time of main curing the resin material can be suppressed to a low level. The laminating property can be enhanced.

The content of the first compound in 100% by weight of the component excluding the inorganic filler and the solvent in the resin material is preferably 25% by weight or more, more preferably 35% by weight or more, and preferably 85% by weight or less. , And more preferably 65% by weight or less. When the content of the first compound is at least the above lower limit, the dielectric loss tangent in the low frequency band can be further reduced. When the content of the first compound is less than or equal to the upper limit, the smear can be more effectively removed by the desmearing treatment, and the heating temperature for the main curing of the resin material can be suppressed to be low. .. The content of the first compound is the total content of all the first compounds in the resin material.

From the viewpoint of more effectively exhibiting the effects of the present invention, the content of the first compound in the total 100% by weight of all the epoxy compounds and all the curing agents in the resin material is preferably 35. The content is preferably at least 50% by weight, more preferably at least 50% by weight, still more preferably at least 55% by weight, preferably at most 95% by weight, more preferably at most 80% by weight. The content of all the epoxy compounds contained in the resin material is the total content of the epoxy compound having the naphthylene ether skeleton and the second epoxy compound described later. The content of all the curing agents contained in the resin material is the total content of the active ester compound having the naphthylene ether skeleton and the second curing agent described later.

[Compound having skeleton derived from dimer diamine or skeleton derived from trimer triamine (second compound)]
The resin material according to the present invention includes a compound (second compound) having a skeleton derived from dimer diamine or a skeleton derived from trimer triamine. The second compound is a compound different from the polyimide compound. The second compound may have a skeleton derived from dimer diamine, may have a skeleton derived from trimer triamine, between the skeleton derived from dimer diamine and the skeleton derived from trimer triamine You may have both. As for the said 2nd compound, only 1 type may be used and 2 or more types may be used together.

The skeleton derived from the dimer diamine or the skeleton derived from the trimer triamine is preferably present as a partial skeleton in the second compound.

From the viewpoint of more effectively exhibiting the effect of the present invention, the second compound is preferably a compound having a skeleton derived from dimer diamine, and has a skeleton derived from dimer diamine, and A compound having at least one of a maleimide skeleton, a benzoxazine skeleton, and a phenol skeleton is more preferable.

Examples of the second compound include maleimide compounds, benzoxazine compounds and phenol compounds.

From the viewpoint of further increasing the dielectric loss tangent in the high frequency band, the second compound is preferably a maleimide compound. That is, the second compound is preferably a maleimide compound having a skeleton derived from dimer diamine or a skeleton derived from trimer triamine.

The maleimide compound is preferably a bismaleimide compound. That is, the second compound is preferably a bismaleimide compound having a skeleton derived from dimer diamine or a skeleton derived from trimer triamine.

The maleimide compound includes a citracone imide compound. The above citraconimide compound is a compound in which a methyl group is bonded to one of the carbon atoms constituting the double bond between carbon atoms in the maleimide group. The maleimide compound may be a citracone imide compound. Since the citraconic imide compound has lower reactivity than the maleimide compound, the storage stability of the resin material can be improved.

The second compound may have a skeleton derived from a diamine compound other than dimerdiamine or a skeleton derived from a triamine compound other than trimertriamine. In this case, the second compound may have a skeleton derived from a diamine compound other than dimerdiamine, or may have a skeleton derived from a triamine compound other than trimertriamine.

The second compound preferably has a skeleton derived from dimer diamine or trimer triamine in the main chain and a skeleton derived from a diamine compound other than dimer diamine or a triamine compound other than trimer triamine. In this case, the miscibility with each compounding component when obtaining the resin material can be increased, the softening point of the second compound can be increased, and the thermal dimensional stability of the cured product can be increased.

From the viewpoint of enhancing the thermal dimensional stability of the cured product, the diamine compound other than the dimer diamine or the triamine compound other than the trimer triamine is a diamine compound having a tricyclodecane skeleton or a triamine compound having a tricyclodecane skeleton. Is preferred.

The second compound preferably has a skeleton derived from the dimer diamine or a skeleton derived from trimer triamine at both ends of the main chain. In this case, the second compound may have a skeleton derived from the dimerdiamine at both ends of the main chain, or may have a skeleton derived from the trimertriamine at both ends of the main chain. Well, it may have a skeleton derived from the dimer diamine at one end of the main chain and a skeleton derived from the trimertriamine at the other end of the main chain. In this case, the second compound may have a skeleton derived from the dimer diamine or a skeleton derived from trimer triamine in the skeleton other than both ends of the main chain and both ends of the main chain, It may have a skeleton derived from the above-mentioned dimer diamine or a skeleton derived from trimer triamine only at both ends of the main chain.

The second compound may have a skeleton derived from the dimer diamine or a skeleton derived from trimer triamine at a portion other than both ends of the main chain.

The second compound more preferably has a skeleton derived from the dimer diamine or a skeleton derived from the trimer triamine only at both ends of the main chain. When the second compound has a skeleton derived from the dimer diamine or a skeleton derived from the trimer triamine only at both ends of the main chain, the main chain skeleton can be made relatively rigid, The softening point of the second compound can be increased more effectively. Therefore, the thermal dimensional stability of the cured product can be further enhanced.

From the viewpoint of more effectively exhibiting the effect of the present invention, the second compound has a skeleton derived from the dimer diamine or a skeleton derived from trimer triamine only at both ends of the main chain, and It is preferable to have a skeleton derived from a reaction product of a diamine compound and an acid dianhydride at a portion other than both ends of the chain.

The second compound may have a skeleton derived from an acid dianhydride having an ester bond in the main chain. In this case, the smear can be more effectively removed by the desmear processing.

The second compound (maleimide compound) is an acid dianhydride such as tetracarboxylic acid dianhydride, dimer diamine or trimer triamine, and, if necessary, a diamine compound other than dimer diamine or a triamine compound other than trimer triamine. It can be obtained by reacting with and a reaction product, and then reacting the reaction product with maleic anhydride.

The second compound (maleimide compound) having a skeleton derived from the dimer diamine or a skeleton derived from the trimer triamine only at both ends of the main chain can be obtained, for example, as follows. An acid dianhydride such as tetracarboxylic acid dianhydride is reacted with a diamine compound other than dimerdiamine or a triamine compound other than trimertriamine to obtain a first reaction product. The obtained first reaction product is reacted with dimer diamine or trimer triamine to obtain a second reaction product. The obtained second reactant is reacted with maleic anhydride.

The above-mentioned second compound (maleimide compound) having a skeleton derived from the reaction product of a diamine compound and an acid dianhydride at a portion other than both ends of the main chain can be obtained, for example, as follows. An acid dianhydride such as tetracarboxylic acid dianhydride is reacted with a diamine compound other than dimer diamine to obtain a first reaction product. The obtained first reaction product is reacted with dimer diamine or trimer triamine to obtain a second reaction product. The obtained second reactant is reacted with maleic anhydride.

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetra Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3′,4,4′-biphenyl ether Tetracarboxylic acid dianhydride, 3,3′,4,4′-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3′,4,4′-Tetraphenylsilane tetracarboxylic acid dianhydride, 1,2 ,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl Sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3 ',4,4'-Biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenyl Phthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4′-diphenylether dianhydride, and bis(triphenylphthalic acid)-4,4′-diphenylmethane dianhydride.

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

Examples of the trimer triamine include PRIAMINE1071 (trade name, manufactured by Croda Japan) and the like. However, since PRIAMINE 1071 contains the triamine component in an amount of about 20% by mass to 25% by mass, it is necessary to use it in the reaction in consideration of the ratio.

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

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

The skeleton derived from the trimer triamine has or does not have an aliphatic ring. The skeleton derived from the trimertriamine may or may not have an aliphatic ring.

The skeleton derived from the diamine compound may or may not have an aromatic ring. The skeleton derived from the diamine compound may or may not have an aromatic ring.

The skeleton derived from the triamine compound has or does not have an aromatic ring. The skeleton derived from the triamine compound may or may not have an aromatic ring.

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

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

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

From the viewpoint of enhancing the thermal dimensional stability of the cured product and enhancing the adhesion between the insulating layer and the metal layer, the softening point of the second compound is preferably 70° C. or higher, more preferably 75° C. or higher, and even more. The temperature is preferably 80°C or higher, more preferably 85°C or higher, particularly preferably 90°C or higher, and most preferably 95°C or higher. The upper limit of the softening point of the second compound is not particularly limited. The softening point of the second compound may be 190° C. or lower in view of easiness of synthesis of the second compound.

The softening point of the second compound is measured using a differential scanning calorimeter (for example, “Q2000” manufactured by TA Instruments Co., Ltd.) at a temperature rising rate of 3° C./min from −30° C. to 200° C. in a nitrogen atmosphere. It can be obtained from the inflection point of reverse heat flow by heating below.

The molecular weight of the second compound is preferably 1,000 or more, more preferably more than 1500, further preferably 2,500 or more, particularly preferably 3,000 or more, preferably 50,000 or less, more preferably 40,000 or less, further preferably 20,000. It is particularly preferably 15,000 or less. When the molecular weight of the second compound is at least the above lower limit, the linear expansion coefficient of the resin material can be suppressed low. In addition, when the molecular weight of the second compound exceeds 50,000, the melt viscosity of the resin material increases and the embeddability on the uneven surface decreases as compared with the case where the molecular weight of the second compound is 50,000 or less. There is.

The molecular weight of the second compound means a molecular weight that can be calculated from the structural formula when the second compound is not a polymer and when the structural formula of the second compound can be specified. Moreover, when the said 2nd compound is a polymer, the molecular weight of the said 2nd compound shows the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC). Therefore, it is preferable that the weight average molecular weight of the second compound satisfies the preferable range described above.

The weight ratio of the content of the second compound to the content of the first compound (content of the second compound/content of the first compound) is preferably 0.1 or more, and more preferably It is preferably 0.15 or more, more preferably 0.2 or more, preferably 1.5 or less, more preferably 1.2 or less. When the weight ratio is not less than the lower limit and not more than the upper limit, the effects of the present invention can be more effectively exhibited. Further, when the weight ratio is not less than the above lower limit and not more than the above upper limit, the thermal dimensional stability can be further enhanced, the surface roughness after etching can be further reduced, and the plating peel strength can be further enhanced. it can. The content of the first compound is the total content of all the first compounds in the resin material. The content of the second compound is the total content of all the second compounds in the resin material.

The content of the second compound in 100% by weight of the component 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, further preferably 15% by weight or more. It is preferably 60% by weight or less, more preferably 50% by weight or less. When the content of the second compound is equal to or more than the lower limit, the dielectric loss tangent in the high frequency band can be further reduced, and the smear can be more effectively removed by the desmear treatment. When the content of the second compound is at least the above lower limit, the adhesiveness between the insulating layer and the metal layer can be further enhanced. When the content of the second compound is not more than the upper limit, the thermal dimensional stability can be further enhanced. Further, the surface roughness after etching can be reduced, and the uniformity of the surface roughness can be improved.

[Inorganic filler]
The resin material preferably contains an inorganic filler. The use of the inorganic filler can further lower the dielectric loss tangent of the cured product. Moreover, the use of the above-mentioned inorganic filler further reduces the dimensional change of the cured product due to heat. As for the said inorganic filler, only 1 type may be used and 2 or more types may be used together.

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

The surface roughness of the cured product is reduced, the adhesive strength between the cured product and the metal layer is further increased, and finer wiring is formed on the surface of the cured product, and the cured product has better insulation reliability. From the viewpoint of providing the above, the inorganic filler is preferably silica or alumina, more preferably silica, and further preferably fused silica. The use of silica results in a lower coefficient of thermal expansion of the cured product and a lower dielectric loss tangent of the cured product. 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 promoting 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. Preferably.

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 The adhesiveness can be further enhanced.

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

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

The inorganic filler is preferably surface-treated, more preferably a surface-treated product with a coupling agent, and further 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 enhanced. Further, since the inorganic filler is surface-treated, it is possible to form finer wiring on the surface of the cured product, and further improve the inter-wiring insulation reliability and interlayer insulation reliability to the cured product. Can be granted.

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

In 100% by weight of the component excluding the solvent in the resin material, the content of the inorganic filler is preferably 50% by weight or more, more preferably 60% by weight or more, further preferably 65% by weight or more, particularly preferably 68% by weight. % Or more, preferably 90% by weight or less, more preferably 85% by weight or less, further preferably 80% by weight or less, 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 becomes effectively low. When the content of the inorganic filler is less than or equal to the above upper limit, the thermal dimensional stability can be increased and the warp of the cured product can be effectively suppressed. When the content of the inorganic filler is not less than the lower limit and not more than the upper limit, it is possible to further reduce the surface roughness of the surface of the cured product, and to form finer wiring on the surface of the cured product. You can Further, the content of this inorganic filler can reduce the coefficient of thermal expansion of the cured product and at the same time improve the smear removing property.

[Epoxy compound having no naphthylene ether skeleton (second epoxy compound)]
It is preferable that the resin material contains an epoxy compound having no naphthylene ether skeleton (hereinafter sometimes referred to as “second epoxy compound”). The second epoxy compound is different from the first compound and the second compound. As the second epoxy compound, a conventionally known epoxy compound having no naphthylene ether skeleton can be used. The second epoxy compound is a compound having at least one epoxy group and not having a naphthylene ether skeleton. As for the said 2nd epoxy compound, only 1 type may be used and 2 or more types may be used together.

Examples of the second epoxy compound include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenol novolac type epoxy compounds, biphenyl type epoxy compounds, biphenyl novolac type epoxy compounds, biphenol type epoxy compounds, naphthalene. Type epoxy compound, fluorene type epoxy compound, phenol aralkyl type epoxy compound, dicyclopentadiene type epoxy compound, anthracene type epoxy compound, epoxy compound having adamantane skeleton, epoxy compound having tricyclodecane skeleton, and triazine nucleus in skeleton An epoxy compound etc. are mentioned.

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

From the viewpoint of further lowering the dielectric loss tangent, improving the linear expansion coefficient (CTE) of the cured product, improving the embeddability on the uneven surface, and suppressing the curing temperature to a low level, the second epoxy compound described above is used. Preferably contains a liquid epoxy compound at 25° C., and more preferably contains a liquid epoxy compound at 25° C. and a solid epoxy compound at 25° C.

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

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

The molecular weight of the second 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 resin material is laminated on the circuit board, the inorganic filler can be uniformly present.

The molecular weight of the second epoxy compound means a molecular weight that can be calculated from the structural formula when the second epoxy compound is not a polymer and when the structural formula of the second epoxy compound can be specified. . The molecular weight of the second epoxy compound means the weight average molecular weight when the second epoxy compound is a polymer.

From the viewpoint of further enhancing the thermal dimensional stability of the cured product, the content of the second epoxy compound is preferably 1% by weight or more, and more preferably 2% in 100% by weight of the component excluding the solvent in the resin material. It is not less than 30% by weight, preferably not more than 30% by weight, more preferably not more than 20% by weight, still more preferably not more than 15% by weight.

The content (1) is the content of all the epoxy compounds contained in the resin material (the total content of the epoxy compound having the naphthylene ether skeleton and the second epoxy compound). The content of the second compound contained in the resin material is referred to as content (2). The content (3) of all the curing agents contained in the resin material (the total content of the active ester compound having the naphthylene ether skeleton and the second curing agent described later) is defined as the content (3). Weight ratio of the content (1) to the total content of the content (2) and the content (3) (the content (1)/the content (2) and the content (3 Content)) is preferably 0.2 or more, more preferably 0.3 or more, preferably 1 or less, more preferably 0.8 or less. When the above weight ratio is not less than the above lower limit and not more than the above upper limit, the dielectric loss tangent can be further lowered and the thermal dimensional stability can be further enhanced.

[Maleimide compound having neither skeleton derived from dimer diamine nor skeleton derived from trimer triamine (maleimide compound X)]
The resin material preferably contains a maleimide compound (hereinafter sometimes referred to as “maleimide compound X”) that does not have both the skeleton derived from dimerdiamine and the skeleton derived from trimertriamine. The maleimide compound X is different from the first compound and the second compound. By using the second compound and the maleimide compound X in combination, the effect of the present invention can be further exerted. As for the said maleimide compound X, only 1 type may be used and 2 or more types may be used together.

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

The maleimide compound X preferably has an aromatic skeleton.

In the maleimide compound X, the nitrogen atom in the maleimide skeleton and the aromatic ring are preferably bonded.

Examples of the maleimide compound X include N-phenylmaleimide.

The content of the maleimide compound X in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 2% by weight or more, more preferably 3% by weight or more, and preferably 50% by weight or less. , And more preferably 35% by weight or less. When the content of the maleimide compound X is at least the above lower limit and at most the above upper limit, the effects of the present invention can be further exerted.

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

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

Examples of commercially available maleimide compound X include “BMI4000” and “BMI5100” manufactured by Daiwa Kasei Kogyo Co., Ltd.

[Curing agent (second curing agent)]
The resin material preferably contains a curing agent different from the active ester compound having a naphthylene ether skeleton (hereinafter sometimes referred to as “second curing agent”). The second curing agent is different from the first compound and the second compound. The second curing agent is not particularly limited. A conventionally known curing agent can be used as the second curing agent. As for the said 2nd hardening|curing agent, only 1 type may be used and 2 or more types may be used together.

As the second curing agent, a cyanate ester compound (cyanate ester curing agent), an active ester compound having no naphthylene ether skeleton, an amine compound (amine curing agent), a thiol compound (thiol curing agent), a phosphine compound, Examples thereof include dicyandiamide, a phenol compound (phenol curing agent), an acid anhydride, a carbodiimide compound (carbodiimide curing agent), and a benzoxazine compound (benzoxazine curing agent). The second curing agent preferably has a functional group capable of reacting with the epoxy group of the epoxy compound.

From the viewpoint of further enhancing the thermal dimensional stability, the second curing agent is a phenol compound, a cyanate ester compound, an acid anhydride, a carbodiimide compound, an active ester compound having no naphthylene ether skeleton, and a benzoxazine compound. It is preferable to include at least one component of the above. That is, the resin material is a curing agent containing at least one component selected from a phenol compound, a cyanate ester compound, an acid anhydride, a carbodiimide compound, an active ester compound having no naphthylene ether skeleton, and a benzoxazine compound. It is preferable to include.

In the present specification, "component X" means "at least one component of a phenol compound, a cyanate ester compound, an acid anhydride, a carbodiimide compound, an active ester compound having no naphthylene ether skeleton, and a benzoxazine compound". May be described.

Therefore, the resin material preferably contains the second curing agent containing the component X. As the component X, only one type may be used, or two or more types may be used in combination.

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

As commercial products of the above-mentioned phenol compounds, novolac type phenols (“TD-2091” manufactured by DIC), biphenyl novolac type phenols (“MEH-7851” manufactured by Meiwa Kasei Co., Ltd.), aralkyl type phenol compounds (“MEH manufactured by Meiwa Kasei Co., Ltd.” -7800"), and a phenol having an aminotriazine skeleton ("LA1356" and "LA3018-50P" manufactured by DIC) and the like.

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

As commercial products of the above cyanate ester compounds, phenol novolac type cyanate ester resins (“PT-30” and “PT-60” manufactured by Lonza Japan Co., Ltd.), and a prepolymer obtained by trimerizing a bisphenol type cyanate ester resin (Lonza Japan "BA-230S", "BA-3000S", "BTP-1000S", and "BTP-6020S") manufactured by the company can be used.

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

Examples of commercially available products of the acid anhydride include "Rikacid TDA-100" manufactured by Shin Nippon Rika Co., Ltd. and the like.

The carbodiimide compound has a structural unit represented by the following formula (2). In the following formula (2), the right end and the left end are binding sites with other groups. Only 1 type may be used for the said carbodiimide compound, and 2 or more types may be used together.

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 is bonded to an arylene group. Represents a group, and p represents an integer of 1 to 5. When there are a plurality of Xs, the plurality of Xs may be the same or different.

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

Commercially available products of the above-mentioned carbodiimide compounds include "carbodilite V-02B", "carbodilite V-03", "carbodilite V-04K", "carbodilite V-07", "carbodilite V-09", and "carbodilite" manufactured by Nisshinbo Chemical Inc. 10M-SP", "Carbodilite 10M-SP (modified)", and "Stabaxol P", "Stabaxol P400", "Hikasil 510" manufactured by Rhein Chemie.

The active ester compound having no naphthylene ether skeleton has no naphthylene ether skeleton, has at least one ester bond, and has an aliphatic chain, an aliphatic ring, or an aromatic group on both sides of the ester bond. A compound in which a group ring is bonded. The active ester compound having no naphthylene ether skeleton 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.

The active ester compound having no naphthylene ether skeleton is preferably an active ester compound having no naphthylene ether skeleton and having a dicyclopentadiene skeleton.

Examples of commercially available active ester compounds having no naphthylene ether skeleton include "HPC-8000L-65T" manufactured by DIC.

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

As a commercial item of the said benzoxazine compound, "Pd type" by Shikoku Chemicals Co., Ltd. etc. are mentioned.

Content of all curing agents with respect to 100 parts by weight of all epoxy compounds (total 100 parts by weight of the epoxy compound having the naphthylene ether skeleton and the second epoxy compound) (active ester compound having the naphthylene ether skeleton) And the total content of the second curing agent) is preferably 70 parts by weight or more, more preferably 80 parts by weight or more. Content of all curing agents with respect to 100 parts by weight of all epoxy compounds (total 100 parts by weight of the epoxy compound having the naphthylene ether skeleton and the second epoxy compound) (active ester compound having the naphthylene ether skeleton) And the total content of the second curing agent) is preferably 150 parts by weight or less, more preferably 120 parts by weight or less. When the content is equal to or more than the lower limit and equal to or less than the upper limit, curability is more excellent, thermal dimensional stability is further enhanced, and volatilization of residual unreacted components can be further suppressed.

In 100% by weight of the components excluding the inorganic filler and solvent in the resin material, the total content of all epoxy compounds and all curing agents is preferably 40% by weight or more, more preferably 60% by weight or more. %, preferably 90% by weight or less, more preferably 85% by weight or less. When the total content is not less than the above lower limit and not more than the above upper limit, the curability is more excellent and the thermal dimensional stability can be further enhanced. The above-mentioned "total content of all epoxy compounds and all curing agents" means "the epoxy compound having the naphthylene ether skeleton, the second epoxy compound, and the active ester compound having the naphthylene ether skeleton. The total content with the second curing agent".

[Curing accelerator]
The resin material preferably contains a curing accelerator. By using the above curing accelerator, the curing speed is further increased. 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 crosslink density increases. The curing accelerator is not particularly limited, and conventionally known curing accelerators can be used. The curing accelerator is different from the first compound and the second compound. As for the said hardening accelerator, only 1 type may be used and 2 or more types may be used together.

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

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

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

Examples of the phosphorus compound include triphenylphosphine compounds and the like.

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

Examples of the above-mentioned peroxides 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. It is more preferable to include a radical curing accelerator and a radical curing accelerator.

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

The content of the curing accelerator is not particularly limited. The content of the curing accelerator is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and preferably 5% by weight based on 100% by weight of the component excluding the inorganic filler and the solvent in the resin material. It is not more than 3% by weight, more preferably not more than 3% by weight. When the content of the curing accelerator is not less than the lower limit and not more than the 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 will be further enhanced, and a better cured product will be obtained.

[Thermoplastic resin]
The resin material preferably contains a thermoplastic resin different from both the first compound and the second compound (hereinafter, may be referred to as “thermoplastic resin X”). Examples of the thermoplastic resin X include polyvinyl acetal resin, polyimide resin, and phenoxy resin. As for the said thermoplastic resin X, only 1 type may be used and 2 or more types may be used together.

The thermoplastic resin X is preferably a phenoxy resin from the viewpoint of effectively lowering the dielectric loss tangent and effectively enhancing the adhesion of the metal wiring regardless of the curing environment. By using the phenoxy resin, it is possible to suppress the deterioration of the embedding property of the resin film in the holes or the irregularities of the circuit board and the nonuniformity 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 it becomes difficult for the resin composition or the B-staged product 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. The phenoxy resin may be used alone or in combination of two or more.

Examples of the phenoxy resin include a phenoxy resin having a skeleton such as a bisphenol A type skeleton, a bisphenol F type skeleton, a bisphenol S type skeleton, a biphenyl skeleton, a novolac skeleton, a naphthalene skeleton, and an imide skeleton.

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

The thermoplastic resin X is preferably a polyimide resin (polyimide compound) from the viewpoints of handling property, plating peel strength at low roughness, and adhesion between the insulating layer and the metal layer.

From the viewpoint of improving solubility, the polyimide compound is preferably a polyimide compound obtained by a method of reacting tetracarboxylic dianhydride and dimer diamine.

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetra Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3′,4,4′-biphenyl ether Tetracarboxylic acid dianhydride, 3,3′,4,4′-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3′,4,4′-Tetraphenylsilane tetracarboxylic acid dianhydride, 1,2 ,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl Sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3 ',4,4'-Biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenyl Phthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4′-diphenylether dianhydride, and bis(triphenylphthalic acid)-4,4′-diphenylmethane dianhydride.

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

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

From the viewpoint of obtaining a resin material that is more excellent in storage stability, the weight average molecular weight of the thermoplastic resin X is preferably 10,000 or more, preferably 100,000 or less, and more preferably 50,000 or less.

The weight average molecular weight of the thermoplastic resin X is a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

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

[solvent]
The resin material does not include or includes a solvent. By using the above solvent, the viscosity of the resin material can be controlled within a suitable range, and the coatability of the resin material can be improved. Further, the solvent may be used to obtain a slurry containing the inorganic filler. As for the said solvent, only 1 type may be used and 2 or more types may be used together.

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

Most of the above solvents are 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.

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 leveling agents, flame retardants, coupling agents, coloring agents, antioxidants, ultraviolet deterioration inhibitors, and defoaming agents. A thermosetting resin other than the agent, the thickener, the thixotropic agent and the epoxy compound may be contained.

Examples of the coupling agent include a silane coupling agent, a titanium coupling agent and an aluminum coupling agent. Examples of the silane coupling agent include vinyl silane, amino silane, imidazole silane, and epoxy silane. The silane coupling agent may be a silane coupling agent containing a silane compound having a triazine ring or a benzotriazole unit.

Examples of the other thermosetting resin include polyphenylene ether resin, divinylbenzyl ether resin, polyarylate resin, diallyl phthalate resin, benzoxazine resin, benzoxazole resin, bismaleimide resin and acrylate resin.

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

The following methods are mentioned as a method of forming a resin film by molding a resin composition into a film. An extrusion molding method in which a resin composition is melt-kneaded using an extruder, extruded, and then formed into a film by a T die, a circular die, or the like. A casting method for casting a resin composition containing a solvent to form 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 which is a B-stage film can be obtained by molding the resin composition into a film and heating and drying at 50° C. to 150° C. for 1 minute to 10 minutes to such an extent that curing by heat does not proceed excessively. it can.

The film-shaped resin composition that can be obtained by the above-described drying process 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 curing can be further advanced.

The resin film may not be a prepreg. When the resin film is not a prepreg, migration does not occur along the glass cloth or the like. Further, when laminating or pre-curing the resin film, 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. The metal foil is preferably 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 film. The surface of the base film may be subjected to a release treatment, if necessary.

From the viewpoint of controlling the degree of curing of the resin film more uniformly, the thickness of the resin film is preferably 5 μm or more, and preferably 200 μm or less. When the resin film is used as an insulating layer of a circuit, the thickness of the insulating layer formed of the resin film is preferably 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 for forming an insulating layer in a printed wiring board.

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

A member to be laminated having a metal layer on one surface or both surfaces thereof can be laminated on the resin film. It is possible to suitably obtain a laminated structure that includes a member to be laminated having a metal layer on the surface and a resin film laminated on the surface of the metal layer, and the resin film is the resin material described above. The method for laminating the resin film and the lamination target member having the metal layer on the surface is not particularly limited, and a known method can be used. For example, the above-mentioned resin film can be laminated on a lamination target member having a metal layer on its surface while heating or pressurizing without heating using a device such as a parallel plate press or a roll laminator.

The material of the metal layer is preferably copper.

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

The resin material is preferably used for obtaining a copper clad laminate. An example of the copper-clad laminate is a copper-clad laminate including a copper foil and a resin film laminated on one surface of the copper foil.

The 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 enhance the adhesive strength between the cured product of the resin material and the copper foil, the copper foil preferably has fine irregularities on the surface. The method for forming the unevenness is not particularly limited. Examples of the method of forming the unevenness include a method of forming by using a known chemical solution.

The resin material is preferably used for obtaining 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. Moreover, the insulating layer of the multilayer substrate may be formed of the resin film of the laminated film using a laminated film. The insulating layer is preferably laminated on the surface of the circuit board on which the circuit is provided. A part of the insulating layer is preferably 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 swollen before the roughening treatment.

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

As another example of the multilayer board, a circuit board, an insulating layer laminated on the surface of the circuit board, and an insulating layer laminated on the surface opposite to the surface on which the circuit board is laminated are laminated. And 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. Furthermore, it is preferable that the copper foil has been subjected to an etching treatment and is a copper circuit.

Another example of the above-mentioned multilayer board 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 layer of the plurality of insulating layers arranged on the circuit board is formed using the resin material. It is preferable that the multilayer substrate further includes a circuit laminated on at least one surface of the insulating layer formed by using the resin film.

Among multilayer boards, a multilayer printed wiring board is required to have a low dielectric loss tangent and high insulation reliability due to an insulating layer. Therefore, the resin material according to the present invention is preferably 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 layer of the insulating layers is a cured product of the resin material.

FIG. 1 is a 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 on a part of the upper surface 12 a of the circuit board 12. Of the plurality of insulating layers 13 to 16, the insulating layers 13 to 15 other than the insulating layer 16 located on the outer surface opposite to the circuit board 12 side are provided with the metal layer 17 in a part of the upper surface. Has been done. The metal layer 17 is a circuit. A metal layer 17 is arranged between the circuit board 12 and the insulating layer 13 and between the 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 via hole connection and through hole connection (not shown).

In the multilayer printed wiring board 11, the insulating layers 13 to 16 are formed of a cured product of the above resin material. In this 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 minute holes. Further, in the multilayer printed wiring board 11, the widthwise dimension (L) of the metal layer 17 and the widthwise dimension (S) of the portion where the metal layer 17 is not formed can be reduced. Further, in the multilayer printed wiring board 11, good insulation reliability is provided between the upper metal layer and the lower metal layer which are not connected by the via hole connection and the through hole connection (not shown).

(Roughening treatment and swelling treatment)
The resin material is preferably used for obtaining a cured product that is subjected to roughening treatment or desmear treatment. The above-mentioned cured product also includes a pre-cured product that can be further cured.

In order to form fine irregularities on the surface of the cured product obtained by pre-curing the resin material, the cured product is preferably roughened. Before the roughening treatment, the cured product is preferably subjected to a swelling treatment. The cured product is preferably subjected to a swelling treatment after the preliminary curing and before the roughening treatment, and is further cured after the roughening treatment. However, the cured product does not necessarily have to be subjected to the swelling treatment.

As a method of the swelling treatment, for example, a method of treating a 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 performed by treating the cured product with a 40 wt% ethylene glycol aqueous solution or the like at a treatment temperature of 30°C to 85°C for 1 minute to 30 minutes. The temperature of the 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 adding water or an organic solvent. The roughening liquid used for the roughening treatment generally contains an alkali as a pH adjuster and the like. The roughening liquid 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 average 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 further finer wiring is formed on the surface of the insulating layer. Furthermore, conductor loss can be suppressed and signal loss can be suppressed to a low level. The arithmetic mean roughness Ra is measured according to JIS B0601:1994.

(Desmear processing)
Through holes may be formed in a cured product obtained by pre-curing the resin material. In the above-mentioned multilayer substrate or the like, vias or through holes are formed as through holes. For example, the via 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 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 desmeared. The desmear process may also serve as the roughening process.

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

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

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

The following materials were prepared.

(Epoxy compound)
First compound:
Epoxy compound 1 having a naphthylene ether skeleton (“TX-1507B” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., solid content: 75% by weight)
Epoxy compound 2 having naphthylene ether skeleton (“ESN-475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
Second epoxy compound:
Biphenyl type epoxy compound ("NC-3000" manufactured by Nippon Kayaku Co., Ltd.)
Resorcinol diglycidyl ether ("EX-201" manufactured by Nagase Chemtex)

(Maleimide compound)
Second compound:
N-alkyl bismaleimide compound 1 having a skeleton derived from dimer diamine ("BMI-1500" manufactured by Designer Molecular Inc.)
N-alkyl bismaleimide compound 2 having a skeleton derived from dimer diamine ("BMI-689" manufactured by Designer Moleculars Inc.)
N-alkyl bismaleimide compound having a skeleton derived from dimer diamine synthesized according to Synthesis Example 1 below (molecular weight 8700)

<Synthesis example 1>
In a reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen gas introduction tube, 55 g of pyromellitic dianhydride (manufactured by Tokyo Kasei Co., molecular weight 254.15), toluene and N-methyl-2-pyrrolidone. And 300 g of the mixed solution of was added, and the solution in the reaction vessel was heated to 60°C. Then, a solution prepared by dissolving 26.7 g of bis(aminomethyl)norbornane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 154.26) in cyclohexanone was dropped into the reaction vessel. A Dean Stark trap and a condenser were attached to a flask, and the mixture was heated at reflux for 2 hours to cause a reaction, thereby obtaining a reaction product having acid anhydrides at both ends. Next, 46.0 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan Co., Ltd.) was slowly added to the reaction vessel, and then 45.0 g of methylcyclohexane was added to the reaction vessel. The mixture was heated to reflux for 2 hours to obtain an imide compound having an amine structure at both ends. Then, 8.7 g of maleic anhydride was added, and the resulting mixture was refluxed for another 12 hours for maleimidization. Then, the organic layer was washed with pure water, dried, and then reprecipitated with methanol to remove low-molecular components. The yield of the maleimide compound was 80%.

The molecular weight of the maleimide compound synthesized in Synthesis Example 1 was determined as follows.

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

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

(Curing agent)
First compound:
Active ester compound-containing liquid having a naphthylene ether skeleton ("HPC-8150-62T" manufactured by DIC, solid content 62% by weight)

Second curing agent:
Active ester compound-containing liquid having a dicyclopentadiene skeleton ("HPC-8000L-65T" manufactured by DIC, solid content 65% by weight)
Phenolic compound-containing liquid having an aminotriazine skeleton (“LA-1356” manufactured by DIC, 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, anionic curing accelerator)
Dicumyl peroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)

(Thermoplastic resin X)
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 Synthesis Example 2 below.

<Synthesis example 2>
300.0 g of tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan LLC) and 665.5 g of cyclohexanone were placed in a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube. Then, 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 Co., Inc.) were dropped into the reaction vessel. Next, 121.0 g of methylcyclohexane and 423.5 g of ethylene glycol dimethyl ether were added to the reaction vessel, and the imidization reaction was performed at 140° C. for 10 hours. Thus, a polyimide compound-containing solution (nonvolatile content: 26.8% by weight) was obtained. The molecular weight (weight average molecular weight) of the obtained polyimide compound was 20,000. The acid component/amine component molar ratio was 1.04.

The molecular weight of the polyimide compound synthesized in Synthesis Example 2 was determined as follows.

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

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

Production of resin film:
Using an applicator, the obtained resin material was applied onto the release-treated surface of the release-treated PET film (“XG284” manufactured by Toray Industries, Inc., thickness 25 μm), and then 2 minutes in a gear oven at 100° C. After drying for 30 seconds, the solvent was evaporated. Thus, a laminated film (a laminated film of a PET film and a resin film) in which a resin film (B stage film) having a thickness of 40 μm was laminated on the PET film was obtained.

(Evaluation)
(1) Softening Point of First Compound Using a differential scanning calorimeter (“Q2000” manufactured by TA Instruments Co., Ltd.) at a temperature rising rate of 3° C./min from −30° C. to 200° C. under a nitrogen atmosphere. Heating was performed and the softening point of the first compound was determined from the inflection point of reverse heat flow.

(2) Dielectric loss tangent The obtained resin film was heated at 190° C. for 90 minutes to obtain a cured product. The obtained cured product was cut into a piece having a width of 2 mm and a length of 80 mm, and 10 pieces of them were overlapped with each other, and a "cavity resonance perturbation method dielectric constant measuring device CP521" manufactured by Kanto Electronics Development Co., Ltd. Using a network analyzer N5224A PNA, the dielectric loss tangent was measured at a frequency of 1.0 GHz at room temperature (23° C.) by the cavity resonance method. Moreover, the dielectric loss tangent was measured at a frequency of 40 GHz at room temperature (23° C.) by a cavity resonance method using a jig for a flat plate. The dielectric loss tangent measured at a frequency of 1.0 GHz is expressed as a dielectric loss tangent (1.0 GHz), and the dielectric loss tangent measured at a frequency of 40 GHz is expressed as a dielectric loss tangent (40 GHz).

[Judgment criteria of dielectric loss tangent]
◯: Absolute value of difference between dielectric loss tangent (1.0 GHz) and dielectric loss tangent (40 GHz) is 1.00×10 ³ or less ◯: Absolute difference between dielectric loss tangent (1.0 GHz) and dielectric loss tangent (40 GHz) The value is more than 1.00×10 ³ and less than 1.50×10 ³ ×: The absolute value of the difference between the dielectric loss tangent (1.0 GHz) and the dielectric loss tangent (40 GHz) is 1.50×10 ³ or more.

(3) Thermal dimensional stability (average linear expansion coefficient (CTE))
The cured film obtained by heating the obtained 40 μm-thick resin film (B stage film) at 190° C. for 90 minutes was cut into a size of 3 mm×25 mm. Using a thermo-mechanical analyzer (“EXSTAR TMA/SS6100” manufactured by SII Nano Technology Inc.), a cured product cut at 25° C. to 150° C. under conditions of a tensile load of 33 mN and a heating rate of 5° C./min. The average coefficient of linear expansion (ppm/°C.) was calculated.

[Criteria for thermal dimensional stability]
◯: Average linear expansion coefficient of 25 ppm/° C. or less ○: Average linear expansion coefficient of more than 25 ppm/° C. and less than 30 ppm/° C. ×: Average linear expansion coefficient of 30 ppm/° C. or more

(4) Glass transition temperature Tg
The cured film obtained by heating the obtained 40 μm-thick resin film (B stage film) at 190° C. for 90 minutes was cut into a size of 5 mm×50 mm. Using a thermomechanical analyzer (“DMS6100” manufactured by SII Nano Technology Inc.), chuck distance 20 mm, amplitude 10 μm, tension amplitude initial value 400 mN, 50° C. to 330° C. at a heating rate of 5° C./min. The measurement was performed under the conditions of increasing the temperature and the frequency of 10 Hz. In the obtained measurement results, the peak temperature of the loss tangent was defined as the glass transition temperature Tg (°C).

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

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

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

(B) Permanganate treatment (roughening treatment and desmear treatment)
The laminated body B after the swelling treatment was put into a roughened aqueous solution of potassium permanganate (“Concentrate Compact CP” manufactured by Atotech Japan Co., Ltd.) at 80° C. and shaken for 30 minutes. Next, the sample was treated with a cleaning liquid at 25° C. (“Reduction Securigant P” manufactured by Atotech Japan Co., Ltd.) for 2 minutes and then washed with pure water to obtain an evaluation sample 1.

The bottom of the via of the evaluation sample 1 was observed by a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the via bottom was measured. The removability of the residue on the bottom of the via was judged according to the following criteria.

[Criteria for Desmearability (Removability of Residue on Via Bottom)]
○ ○: Maximum smear length is less than 2 μm ◯: Maximum smear length is 2 μm or more and less than 3 μm ×: Maximum smear length is 3 μm or more

(6) Embedding property on uneven surface 100 mm square copper-clad laminate (a laminate of a glass epoxy substrate having a thickness of 400 μm and a copper foil having a thickness of 25 μm) is etched to obtain a diameter of 100 μm and a depth of 25 μm. The dents (openings) were formed in a straight line with respect to an area of 30 mm square in the center of the substrate so that the distance between the centers of adjacent holes 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 overlaid on the evaluation substrate, and using "Batch type vacuum laminator MVLP-500-IIA" manufactured by Meiki Seisakusho Co., Ltd., a laminating pressure of 0.4 MPa for 20 seconds and a pressing pressure of 0.8 MPa. It was heated and pressed at a laminating and pressing temperature of 90° C. for 20 seconds. After cooling at room temperature, the PET film was peeled off. In this way, an evaluation sample in which the resin film was laminated on the evaluation substrate was obtained.

The voids in the depressions were observed for the obtained evaluation sample using an optical microscope. The embeddability on the uneven surface was evaluated according to the following criteria by evaluating the ratio of the depressions in which voids were observed.

[Judgment criteria of embeddability on uneven surface]
◯: Ratio of dents in which voids were observed 0%
Δ: Proportion of cavities in which voids were observed was more than 0% and less than 5% x: Proportion of cavities in which voids were observed 5% or more

The composition and results are shown in Table 1 below.

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

Claims (14)

A first compound having a naphthylene ether skeleton,
A second compound having a skeleton derived from dimer diamine or having a skeleton derived from trimer triamine,
A resin material, wherein the second compound is a compound different from a polyimide compound. The resin material according to claim 1, wherein the first compound is a compound having two or more naphthylene ether skeletons. The resin material according to claim 1 or 2, which contains at least one of an epoxy compound having a naphthylene ether skeleton and an active ester compound having a naphthylene ether skeleton as the first compound. The resin material according to claim 3, wherein both the first compound include an epoxy compound having a naphthylene ether skeleton and an active ester compound having a naphthylene ether skeleton. At least one of an epoxy compound having a naphthylene ether skeleton and a softening point of more than 90° C. and an active ester compound having a naphthylene ether skeleton and a softening point of more than 145° C. as the first compound. The resin material according to any one of claims 1 to 4, containing one of them. The resin material according to any one of claims 1 to 5, which comprises an epoxy compound having a naphthylene ether skeleton and a softening point of higher than 90°C as the first compound. The resin material according to any one of claims 1 to 5, which comprises an active ester compound having a naphthylene ether skeleton and a softening point of higher than 145°C as the first compound. As the first compound, both an epoxy compound having a naphthylene ether skeleton and a softening point of more than 90° C. and an active ester compound having a naphthylene ether skeleton and a softening point of more than 145° C. are used. The resin material according to any one of claims 1 to 5, which comprises: Including an epoxy compound and a curing agent,
The first compound is at least one of the epoxy compound and the curing agent,
The content of the first compound is 50% by weight or more in a total of 100% by weight of all the epoxy compounds and all the curing agents in a resin material, In any one of claims 1 to 8. The resin material described. The second compound is a compound having a skeleton derived from dimer diamine and having at least one of a maleimide skeleton, a benzoxazine skeleton, and a phenol skeleton. The resin material according to item 1. The resin material according to any one of claims 1 to 10, which contains an inorganic filler. The resin material according to any one of claims 1 to 11, which is a resin film. The resin material according to any one of claims 1 to 12, which is used for forming an insulating layer in a multilayer printed wiring board. Circuit board,
A plurality of insulating layers disposed on the surface of the circuit board,
A metal layer disposed between the plurality of insulating layers,
A multilayer printed wiring board, wherein at least one layer of the plurality of insulating layers is a cured product of the resin material according to any one of claims 1 to 13.

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