JP2021025051A - Resin material and multilayer printed wiring board - Google Patents

Abstract

To provide a resin material capable of achieving low dielectric loss tangent, high thermal dimensional stability, high desmearing capability due to desmear processing, small surface roughness after etching and high plating peel strength.SOLUTION: There is provided a resin material containing a specific cyclohexane ring-containing compound and a curing accelerator, wherein the cyclohexane ring-containing compound has a first skeleton derived from an aliphatic diamine compound having a cyclohexane ring and a second skeleton derived from a dimer diamine. The aliphatic diamine compound having a cyclohexane ring is different from a dimer diamine. The average ratio of the first skeleton is 50 mol% or more and 85 mol% or less and the average ratio of the second skeleton is 15 mol% or more and 50 mol% or less based on 100 mol% of the whole structural unit of the skeleton derived from a diamine compound in the cyclohexane ring-containing compound.SELECTED DRAWING: Figure 1

Description

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

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

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

Patent Document 2 below discloses a resin composition for an electronic material containing a bismaleimide compound, wherein the bismaleimide compound has two maleimide groups and one or more polyimide groups having a specific structure. .. In the bismaleimide compound, the two maleimide groups are independently bonded to both ends of the polyimide group via at least a first linking group in which 8 or more atoms are linearly linked. ..

Patent Document 3 below includes (A) an epoxy compound and (B) a maleimide compound, wherein the (B) maleimide compound contains an alkyl group having 5 or more carbon atoms and an alkylene having 5 or more carbon atoms. Resin compositions containing any of the groups are disclosed.

WO2016 / 114286A1 JP-A-2018-90728 JP-A-2019-44128

When the insulating layer is formed by using the conventional resin materials as described in Patent Documents 1 to 3, the dielectric loss tangent of the cured product is not sufficiently low, and the thermal dimensional stability is not sufficiently high. Sometimes.

Further, in the conventional resin material, the smear in the via may not be sufficiently removed by the desmear treatment at the time of forming the insulating layer.

Further, when the insulating layer is formed by using a conventional resin material, the surface roughness after etching is not sufficiently reduced, or the plating peel strength with the metal layer laminated on the surface of the insulating layer by plating treatment. May not be high enough.

The object of the present invention is that 1) the dielectric loss tangent of the cured product can be lowered, 2) the thermal dimensional stability of the cured product can be improved, and 3) smear can be effectively removed by the desmear treatment. 4) To provide a resin material capable of reducing the surface roughness after etching and 5) increasing the plating peel strength. 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, the cyclohexane ring-containing compound comprises at least one cyclohexane ring-containing compound of a maleimide compound having a cyclohexane ring and a benzoxazine compound having a cyclohexane ring, and a curing accelerator, and the cyclohexane ring-containing compound is cyclohexane. The aliphatic diamine compound having a first skeleton derived from an aliphatic diamine compound having a ring and a second skeleton derived from dimerdiamine and having the cyclohexane ring is different from dimerdiamine and contains the cyclohexane ring. The average ratio of the first skeleton derived from the aliphatic diamine compound having a cyclohexane ring is 50 mol% or more and 85 mol% or less in 100 mol% of the total structural units of the skeleton derived from the diamine compound contained in the compound. Provided is a resin material in which the average ratio of the second skeleton derived from the dimerdiamine is 15 mol% or more and less than 50 mol% in 100 mol% of the total structural units of the skeleton derived from the diamine compound contained in the cyclohexane ring-containing compound. Will be done.

In certain aspects of the resin material according to the present invention, the cyclohexane ring-containing compound has a third skeleton derived from a diamine compound different from the aliphatic diamine compound having a cyclohexane ring, and the fat having the cyclohexane ring. A diamine compound different from the group diamine compound is different from the diamine diamine.

In certain aspects of the resin material according to the present invention, a third skeleton derived from a diamine compound different from the aliphatic diamine compound having a cyclohexane ring has an aromatic ring.

In certain aspects of the resin material according to the present invention, the third skeleton derived from a diamine compound different from the aliphatic diamine compound having a cyclohexane ring has a fluorine atom.

In a specific aspect of the resin material according to the present invention, in the first skeleton derived from the aliphatic diamine compound having a cyclohexane ring, a nitrogen atom constituting the first amino group and a carbon atom constituting the cyclohexane ring Is directly bonded or is bonded via two or less atoms.

In a particular aspect of the resin material according to the present invention, a nitrogen atom constituting a second amino group different from the first amino group in the first skeleton derived from the aliphatic diamine compound having a cyclohexane ring. And the carbon atoms constituting the cyclohexane ring are directly bonded or bonded via three or less atoms.

In certain aspects of the resin material according to the present invention, the aliphatic diamine compound having a cyclohexane ring is tricyclodecanediamine, norbornanediamine, or isophoronediamine.

In a specific aspect of the resin material according to the present invention, the glass transition temperature of the cyclohexane ring-containing compound is 80 ° C. or higher and 250 ° C. or lower.

In a specific aspect of the resin material according to the present invention, the weight average molecular weight of the cyclohexane ring-containing compound is 2000 or more and 100,000 or less.

In a specific aspect of the resin material according to the present invention, a thermosetting compound different from the cyclohexane ring-containing compound and a curing agent are included.

In certain aspects of the resin material according to the present invention, the cyclohexane ring-containing compound is a maleimide compound having the cyclohexane ring, and the thermosetting compound contains a maleimide compound.

In certain aspects of the resin material according to the invention, the maleimide compound is a maleimide compound that does not have a skeleton derived from diaminediamine, or the maleimide compound has a skeleton derived from diaminediamine. Moreover, it is a maleimide compound in which the average ratio of the skeleton derived from dimerdiamine is 50 mol% or more in 100 mol% of the total structural units of the skeleton derived from the diamine compound contained in the maleimide compound.

In certain aspects of the resin material according to the present invention, the thermosetting compound comprises an epoxy compound.

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

In certain aspects of the resin material according to the present invention, the thermosetting compound comprises a radical curable compound.

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

In a specific aspect of the resin material according to the present invention, the content of the inorganic filler is 50% by weight or more in 100% by weight of the components excluding the solvent in the resin material.

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

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

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

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

The resin material according to the present invention includes at least one cyclohexane ring-containing compound among the maleimide compound having a cyclohexane ring and the benzoxazine compound having a cyclohexane ring, and a curing accelerator. In the resin material according to the present invention, the cyclohexane ring-containing compound has a first skeleton derived from an aliphatic diamine compound having a cyclohexane ring and a second skeleton derived from a diamine diamine, and the cyclohexane ring is used. The aliphatic diamine compound it has is different from diamine diamine. In the resin material according to the present invention, the average ratio of the first skeleton derived from the aliphatic diamine compound having the cyclohexane ring is the average ratio of 100 mol% of the total structural units of the skeleton derived from the diamine compound contained in the cyclohexane ring-containing compound. It is 50 mol% or more and 85 mol% or less. In the resin material according to the present invention, the average ratio of the second skeleton derived from the dimer diamine is 15 mol% or more and 50 mol% of the total structural unit of the skeleton derived from the diamine compound contained in the cyclohexane ring-containing compound. Less than%. Since the resin material according to the present invention has the above-mentioned structure, 1) the dielectric loss tangent of the cured product can be lowered, 2) the thermal dimensional stability of the cured product can be improved, and 3) desmear. Smear can be effectively removed by the treatment, 4) the surface roughness after etching can be reduced, and 5) the plating peel strength can be increased.

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

Hereinafter, the present invention will be described in detail.

The resin material according to the present invention includes at least one cyclohexane ring-containing compound among the maleimide compound having a cyclohexane ring and the benzoxazine compound having a cyclohexane ring, and a curing accelerator.

In the resin material according to the present invention, the cyclohexane ring-containing compound has a first skeleton derived from an aliphatic diamine compound having a cyclohexane ring, and the aliphatic diamine compound having a cyclohexane ring is different from dimer diamine.

In the resin material according to the present invention, the cyclohexane ring-containing compound has a second skeleton derived from dimer diamine.

In the resin material according to the present invention, the average ratio of the first skeleton derived from the aliphatic diamine compound having the cyclohexane ring is the average ratio of 100 mol% of the total structural units of the skeleton derived from the diamine compound contained in the cyclohexane ring-containing compound. It is 50 mol% or more and 85 mol% or less.

In the resin material according to the present invention, the average ratio of the second skeleton derived from the dimer diamine is 15 mol% or more and 50 mol% of the total structural unit of the skeleton derived from the diamine compound contained in the cyclohexane ring-containing compound. Less than%.

Since the resin material according to the present invention has the above-mentioned structure, 1) the dielectric loss tangent of the cured product can be lowered, 2) the thermal dimensional stability of the cured product can be improved, and 3) desmear. Smear can be effectively removed by the treatment, 4) the surface roughness after etching can be reduced, and 5) the plating peel strength can be increased. With the resin material according to the present invention, all the effects of 1) -5) can be exhibited.

Since the resin material according to the present invention has the above structure, it is possible to enhance the compatibility between the cyclohexane ring-containing compound and a thermosetting compound different from the cyclohexane ring-containing compound. As a result, the occurrence of excessive phase separation can be suppressed, and the surface uniformity can be improved.

Further, since the resin material according to the present invention has the above-mentioned structure, the flexibility of the B stage film can be increased.

Further, since the resin material according to the present invention has the above-mentioned structure, the elongation characteristics of the cured product can be improved. Therefore, for example, the connection reliability can be improved even in a place where stress is likely to be concentrated, such as a multi-stage via stack portion.

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

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

Hereinafter, the details of each component used in the resin material according to the present invention, the use of the resin material according to the present invention, and the like will be described. In addition, a preferable structure and the like capable of exerting the effect of the present invention more effectively will be specifically described below.

[Cyclohexane ring-containing compound]
The resin material according to the present invention contains a cyclohexane ring-containing compound. The cyclohexane ring-containing compound is at least one of a maleimide compound having a cyclohexane ring and a benzoxazine compound having a cyclohexane ring. In the present specification, the above-mentioned "maleimide compound having a cyclohexane ring" may be described as "a cyclohexane ring-containing maleimide compound", and the above "benzoxazine compound having a cyclohexane ring" may be described as "a cyclohexane ring-containing benzoxazine compound". There is something to do. Therefore, the cyclohexane ring-containing compound is at least one of the cyclohexane ring-containing maleimide compound and the cyclohexane ring-containing benzoxazine compound. Only one kind of the cyclohexane ring-containing compound may be used, or two or more kinds may be used in combination.

The cyclohexane ring-containing maleimide compound preferably has a maleimide skeleton at the terminal. The cyclohexane ring-containing maleimide compound may have a maleimide skeleton at a portion other than the terminal. As the cyclohexane ring-containing maleimide compound, only one type may be used, or two or more types may be used in combination.

The cyclohexane ring-containing benzoxazine compound has a benzoxazine skeleton. As the cyclohexane ring-containing benzoxazine compound, only one type may be used, or two or more types may be used in combination.

As used herein, the cyclohexane ring means an alicyclic structure of a six-membered ring in which six carbon atoms are cyclically bonded. The carbon atom constituting the cyclohexane ring may be bonded to a hydrocarbon group having 1 or more and 20 or less carbon atoms, or may be bonded to a hydrocarbon group having 1 or more and 4 or less carbon atoms. In addition, the cyclohexane ring-containing compound may have a cyclohexane ring as a ring constituting a tricyclodecane ring, a norbornane ring, an adamantane skeleton, or the like. Further, the cyclohexane ring-containing compound may have a structure in which a plurality of cyclohexane rings are connected via a hydrocarbon group such as an alkyl group.

Examples of the cyclohexane ring include rings represented by the following formula (X1), the following formula (X2), the following formula (X3), the following formula (X4), the following formula (X5), and the like.

In the above formula (X1), R1 to R10 each represent a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms. In the above formula (X1), R1 to R10 are preferably hydrogen atoms or methyl groups, respectively. In the above formula (X1), R1 to R10 may be the same or different.

In the above formula (X2), R1 to R10 each represent a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms. In the above formula (X2), R1 to R10 are preferably hydrogen atoms or methyl groups, respectively. In the above formula (X2), R1 to R10 may be the same or different.

In the above formula (X3), R1 to R18 each represent a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms, and Q represents an arbitrary group. In the above formula (X3), R1 to R18 are preferably hydrogen atoms or methyl groups, respectively. In the above formula (X3), Q is preferably a hydrocarbon group having 1 to 4 carbon atoms or a group having an aromatic ring, more preferably an alkylene group, and even more preferably a methylene group. .. In the above formula (X3), when Q is a group having an aromatic ring, Q may be a group in which aromatic rings are bonded to each other via an ester bond. In the above formula (X3), R1 to R18 may be the same or different.

In the above formula (X4), R1 to R8 each represent a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms. The ring represented by the above formula (X4) is a norbornane ring. In the above formula (X4), R1 to R8 are preferably hydrogen atoms or methyl groups, respectively. In the above formula (X4), R1 to R8 may be the same or different.

The cyclohexane ring may be a ring represented by the following formula (X4-1).

In the above formula (X4-1), R1 to R10 each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and two of R1 to R10 are with a nitrogen atom constituting an imide skeleton. Represents a group that is bound. In the above formula (X4-1), the case where R9 and R10 represent a group bonded to a nitrogen atom constituting an imide skeleton corresponds to the above formula (X4).

In the above formula (X5), R1 to R12 each represent a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms. The ring represented by the above formula (X5) is a tricyclodecane ring. In the above formula (X5), R1 to R12 are preferably hydrogen atoms or methyl groups, respectively. In the above formula (X5), R1 to R12 may be the same or different.

The cyclohexane ring may be a ring represented by the following formula (X5-1).

In the above formula (X5-1), R1 to R14 each represent a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms, and two of R1 to R14 are a nitrogen atom constituting an imide skeleton. Represents a group that is bound. In the above formula (X5-1), the case where R13 and R14 represent a group bonded to a nitrogen atom constituting an imide skeleton corresponds to the above formula (X5).

The cyclohexane ring-containing compound has a first skeleton derived from an aliphatic diamine compound having a cyclohexane ring, and the aliphatic diamine compound having a cyclohexane ring is different from dimer diamine. Therefore, the aliphatic diamine compound is different from the dimer diamine and is an aliphatic diamine compound having a cyclohexane ring. The first skeleton has a cyclohexane ring.

In the present specification, "an aliphatic diamine compound different from dimer diamine and having a cyclohexane ring" may be referred to as "aliphatic diamine compound A".

The cyclohexane ring-containing compound has a second skeleton derived from dimer diamine. Dimer diamine is a diamine compound. The second skeleton is different from the first skeleton.

The cyclohexane ring-containing compound may or may not have a third skeleton derived from a diamine compound different from the aliphatic diamine compound having a cyclohexane ring. However, with respect to the third skeleton, the aliphatic diamine compound having a cyclohexane ring (diamine compound constituting the third skeleton) is different from dimer diamine. Therefore, the diamine compound constituting the third skeleton is a diamine compound different from dimer diamine and different from the aliphatic diamine compound having a cyclohexane ring (aliphatic diamine compound A). The third skeleton is different from the first skeleton. The third skeleton is different from the second skeleton. The third skeleton may or may not have a cyclohexane ring.

In the present specification, "a diamine compound different from a dimer diamine and different from an aliphatic diamine compound having a cyclohexane ring" may be referred to as "diamine compound B".

Hereinafter, the skeleton of the cyclohexane ring-containing compound and other details will be described in more detail. In addition, a preferable structure and the like capable of exerting the effect of the present invention more effectively will be specifically described below.

<First skeleton derived from aliphatic diamine compound A>
The cyclohexane ring-containing compound has a first skeleton derived from the aliphatic diamine compound A. The cyclohexane ring-containing compound has the cyclohexane ring by having at least the first skeleton derived from the aliphatic diamine compound A. The first skeleton derived from the aliphatic diamine compound A exists as a partial skeleton in the cyclohexane ring-containing compound.

The aliphatic diamine compound A is an aliphatic diamine compound different from the dimer diamine. The aliphatic diamine compound A has a cyclohexane ring. The aliphatic diamine compound A has a first amino group and a second amino group.

The number of carbon atoms of the aliphatic diamine compound A is preferably less than the number of carbon atoms of the dimer diamine (36). That is, the aliphatic diamine compound A preferably has less than 36 carbon atoms.

The aliphatic diamine compound A may have one cyclohexane ring, two cyclohexane rings, or three or more cyclohexane rings.

The carbon atom constituting the cyclohexane ring of the aliphatic diamine compound A may be bonded to a hydrocarbon group having 1 or more and 20 or less carbon atoms. Further, the aliphatic diamine compound A may have a cyclohexane ring as a ring constituting a tricyclodecane ring, a norbornane ring, an adamantane skeleton and the like.

Examples of the cyclohexane ring contained in the aliphatic diamine compound A include rings represented by the above formula (X1), the above formula (X2), the above formula (X3), the above formula (X4), the above formula (X5) and the like. Be done.

From the viewpoint of exerting the effects of the present invention even more effectively, in the first skeleton derived from the aliphatic diamine compound A, the nitrogen atom constituting the first amino group and the carbon atom constituting the cyclohexane ring are used. However, it is preferable that they are directly bonded or are bonded via two or less atoms. The atom is preferably a carbon atom.

From the viewpoint of exerting the effect of the present invention even more effectively, in the first skeleton derived from the aliphatic diamine compound A, a nitrogen atom constituting a second amino group and a carbon atom constituting a cyclohexane ring are used. However, it is preferable that they are directly bonded or are bonded via 3 or less atoms. The atom is preferably a carbon atom.

When the aliphatic diamine compound A has the tricyclodecane ring as the cyclohexane ring, the nitrogen atom constituting the first amino group and the tricyclodecane in the first skeleton derived from the aliphatic diamine compound A It is preferable that the carbon atoms constituting the ring are directly bonded or are bonded via two or less atoms. The atom is preferably a carbon atom. In this case, the effect of the present invention can be exhibited even more effectively.

When the aliphatic diamine compound A has the tricyclodecane ring as the cyclohexane ring, the nitrogen atom constituting the second amino group and the tricyclodecane in the first skeleton derived from the aliphatic diamine compound A It is preferable that the carbon atoms constituting the ring are directly bonded or are bonded via two or less atoms. In this case, the effect of the present invention can be exhibited even more effectively. The atom is preferably a carbon atom.

The first skeleton derived from the aliphatic diamine compound A includes the following formula (A1), the following formula (A2), the following formula (A3), the following formula (A4), the following formula (A5), and the following formula (A6). ) Etc. can be mentioned.

In the above formula (A1), R1 to R10 each represent a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms, and R11 and R12 each represent a group forming a heterocycle together with a nitrogen atom. In the above formula (A1), R1 to R10 are preferably hydrogen atoms or methyl groups, respectively. In the above formula (A1), R1 to R10 may be the same or different. In the above formula (A1), R11 and R12 may be the same or different.

In the skeleton represented by the above formula (A1), the nitrogen atom constituting the first amino group (amino group on the left side) and the atom constituting the cyclohexane ring are bonded via one carbon atom. The nitrogen atom constituting the second amino group (amino group on the right side) and the atom constituting the cyclohexane ring are bonded via one carbon atom.

In the above formula (A2), R1 to R10 each represent a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms, and R11 and R12 each represent a group constituting a heterocycle together with a nitrogen atom. In the above formula (A2), R1 to R10 are preferably hydrogen atoms or methyl groups, respectively. In the above formula (A2), R1 to R10 may be the same or different. In the above formula (A2), R11 and R12 may be the same or different.

In the skeleton represented by the above formula (A2), the nitrogen atom constituting the first amino group (amino group on the left side) and the atom constituting the cyclohexane ring are directly bonded and the second atom is bonded. The nitrogen atom constituting the amino group (amino group on the right side) and the atom constituting the cyclohexane ring are bonded via one carbon atom.

In the above formula (A3), R1 to R10 each represent a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms, and R11 and R12 each represent a group constituting a heterocycle together with a nitrogen atom. In the above formula (A3), R1 to R10 are preferably hydrogen atoms or methyl groups, respectively. In the above formula (A3), R1 to R10 may be the same or different. In the above formula (A3), R11 and R12 may be the same or different.

In the skeleton represented by the above formula (A3), the nitrogen atom constituting the first amino group (amino group on the left side) and the atom constituting the cyclohexane ring are bonded via two carbon atoms. The nitrogen atom that constitutes the second amino group (amino group on the right side) and the atom that constitutes the cyclohexane ring are directly bonded.

In the above formula (A4), R1 to R18 each represent a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms, R19 and R20 each represent a group forming a heterocycle together with a nitrogen atom, and Q is , Represents any group. In the above formula (A4), R1 to R18 are preferably hydrogen atoms or methyl groups, respectively. In the above formula (A4), Q is preferably a hydrocarbon group having 1 to 4 carbon atoms or a group having an aromatic ring, more preferably an alkylene group, and even more preferably a methylene group. .. In the above formula (A4), when Q is a group having an aromatic ring, Q may be a group in which aromatic rings are bonded to each other via an ester bond. In the above formula (A4), R1 to R18 may be the same or different. In the above formula (A4), R19 and R20 may be the same or different.

In the skeleton represented by the above formula (A4), the nitrogen atom constituting the first amino group (amino group on the left side) and the atom constituting the cyclohexane ring are directly bonded and the second atom is bonded. The nitrogen atom constituting the amino group (amino group on the right side) and the atom constituting the cyclohexane ring are directly bonded.

In the above formula (A5), R1 to R8 each represent a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms, and R9 and R10 each represent a group forming a heterocycle together with a nitrogen atom. In the above formula (A5), R1 to R8 are preferably hydrogen atoms or methyl groups, respectively. In the above formula (A5), R1 to R8 may be the same or different. In the above formula (A5), R9 and R10 may be the same or different.

In the skeleton represented by the above formula (A5), the nitrogen atom constituting the first amino group (amino group on the left side) and the atom constituting the cyclohexane ring are bonded via one carbon atom. The nitrogen atom constituting the second amino group (amino group on the right side) and the atom constituting the cyclohexane ring are bonded via one carbon atom.

The first skeleton derived from the aliphatic diamine compound A may be a skeleton represented by the following formula (A5-1).

In the above formula (A5-1), R1 to R8, R11 and R12 each represent a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms, and two of R1 to R8, R11 and R12 are imides. Represents a group bonded to a nitrogen atom constituting the skeleton, and R9 and R10 each represent a group forming a heterocycle together with the nitrogen atom. In the above formula (A5-1), the case where R11 and R12 represent a group bonded to a nitrogen atom constituting an imide skeleton corresponds to the above formula (A5). In the above formula (A5-1), R1 to R8, R11 and R12 are preferably hydrogen atoms or methyl groups, respectively. In the above formula (A5-1), R1 to R8, R11 and R12 may be the same or different from each other. In the above formula (A5-1), R9 and R10 may be the same or different.

In the above formula (A6), R1 to R12 each represent a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms, and R13 and R14 each represent a group forming a heterocycle together with a nitrogen atom. In the above formula (A6), R1 to R12 are preferably hydrogen atoms or methyl groups, respectively. In the above formula (A6), R1 to R12 may be the same or different. In the above formula (A6), R13 and R14 may be the same or different.

In the skeleton represented by the above formula (A6), the nitrogen atom constituting the first amino group (amino group on the left side) and the atom constituting the cyclohexane ring are bonded via one carbon atom. The nitrogen atom constituting the second amino group (amino group on the right side) and the atom constituting the cyclohexane ring are bonded to each other via two carbon atoms. In the skeleton represented by the above formula (A6), the nitrogen atom constituting the second amino group and the carbon atom constituting the tricyclodecane ring are bonded via one carbon atom. ..

The first skeleton derived from the aliphatic diamine compound A may be a skeleton represented by the following formula (A6-1).

In the above formula (A6-1), R1 to R12, R15 and R16 each represent a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms, and two of R1 to R12, R15 and R16 are imides. Represents a group bonded to a nitrogen atom constituting the skeleton, and R13 and R14 each represent a group forming a heterocycle together with the nitrogen atom. In the above formula (A6-1), the case where R15 and R16 represent a group bonded to a nitrogen atom constituting an imide skeleton corresponds to the above formula (A6). In the above formula (A6-1), R1 to R12, R15 and R16 are preferably hydrogen atoms or methyl groups, respectively. In the above formula (A6-1), R1 to R12, R15 and R16 may be the same or different from each other. In the above formula (A6-1), R13 and R14 may be the same or different.

The above formula (A1), the above formula (A2), the above formula (A3), the above formula (A4), the above formula (A5), the above formula (A5-1), the above formula (A6) and the above formula (A6-1). ), Examples of the group forming a hetero ring together with the nitrogen atom include a group represented by the following formula (A11), the following formula (A12), or the following formula (A13).

Hereinafter, compounds capable of forming the skeletons of the above formulas (A1), (A2), (A3), (A4), (A5) and (A6), and the above formulas (A1), (A2), (A3) ), (A4), (A5) and (A6), a compound capable of forming a skeleton derived from an aliphatic diamine compound having a cyclohexane ring and the like will be further described.

Examples of the aliphatic diamine compound A include tricyclodecanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, and bis (aminomethyl) norbornan, 3 (4), 8 (9). ) -Bis (aminomethyl) tricyclo [5.2.1.02,6] decane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, isophoronediamine, 4,4'-methylenebis (cyclohexylamine), and Examples thereof include 4,4'-methylenebis (2-methylcyclohexylamine). Only one type of the aliphatic diamine compound A may be used, or two or more types may be used in combination.

From the viewpoint of exerting the effects of the present invention more effectively, the aliphatic diamine compound A is preferably tricyclodecanediamine, norbornanediamine, or isophoronediamine, and more preferably tricyclodecanediamine. .. When the aliphatic diamine compound A is tricyclodecanediamine, the cyclohexane ring-containing compound has, for example, a skeleton represented by the above formula (A6). When the aliphatic diamine compound A is norbornane diamine (bis (aminomethyl) norbornane), the cyclohexane ring-containing compound has, for example, a skeleton represented by the above formula (A5). When the aliphatic diamine compound A is isophorone diamine, the cyclohexane ring-containing compound has, for example, a skeleton represented by the above formula (A2).

The first skeleton derived from the aliphatic diamine compound A is preferably a skeleton derived from a reaction product of the aliphatic diamine compound A and the acid dianhydride. The skeleton derived from the reaction product of the aliphatic diamine compound A and the acid dianhydride has a first skeleton derived from the aliphatic diamine compound A.

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

Examples of the tetracarboxylic acid dianhydride include pyromellitic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-biphenylsulfonetetra. Carboxyl dianhydride, 1,4,5,8-naphthalenetetracarboxylic hydride, 2,3,6,7-naphthalenetetracarboxylic hydride, 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-Frantetracarboxylic acid dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl Symphonic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3', 4,4'-perfluoroisopropyridene diphthalic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid 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'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, 4,4'-(hexa) Fluoroisopropylidene) diphthalic anhydride, bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic hydride, and 5- (2,5-dioxotetrahydrofuryl) ) -3-Methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride and the like.

From the viewpoint of further enhancing the thermal dimensional stability of the cured product and enhancing the compatibility with other resins, the aliphatic diamine in 100 mol% of the total structural unit of the skeleton derived from the diamine compound contained in the cyclohexane ring-containing compound. The average proportion of the first skeleton derived from compound A is 50 mol% or more and 85 mol% or less.

The average ratio of the first skeleton derived from the aliphatic diamine compound A is preferably 60 mol% or more, more preferably 65, among 100 mol% of the total structural units of the skeleton derived from the diamine compound contained in the cyclohexane ring-containing compound. It is mol% or more, more preferably 70 mol% or more, preferably 80 mol% or less, and more preferably 75 mol% or less. When the average ratio of the first skeleton derived from the aliphatic diamine compound A is not more than the above lower limit, the effect of the present invention can be exhibited even more effectively. Further, when the average ratio of the first skeleton derived from the aliphatic diamine compound A is at least the above lower limit, the glass transition temperature of the resin material can be further increased. When the average ratio of the first skeleton derived from the aliphatic diamine compound A is not more than the above upper limit, the compatibility between the cyclohexane ring-containing compound and the thermosetting compound different from the cyclohexane ring-containing compound is further enhanced. It is possible to further improve the surface uniformity after laminating and after precure. Moreover, since the concentration of the imide skeleton can be increased, the desmear property can be improved.

<Second skeleton derived from dimer diamine>
The cyclohexane ring-containing compound has a second skeleton derived from dimer diamine. The cyclohexane ring-containing compound has the cyclohexane ring by having a second skeleton derived from dimer diamine. The second skeleton derived from the dimer diamine exists as a partial skeleton in the cyclohexane ring-containing compound. However, since the dimer diamine is, for example, a mixture (natural product), it may be difficult to define the structure of the dimer diamine as one structure. Therefore, the dimer diamine may contain, for example, a dimer diamine having a cyclohexene ring.

Since the cyclohexane ring-containing compound has a second skeleton derived from dimer diamine, the dielectric loss tangent of the cured product can be lowered, and smear can be effectively removed by desmear treatment. The second skeleton derived from the dimer diamine is a flexible skeleton. Therefore, when the cyclohexane ring-containing compound has a second skeleton derived from the dimer diamine, the sheet property of a resin film such as a B stage film can be improved. Further, since the elongation characteristics and stress relaxation properties of the cured product can be improved, the occurrence of warping can be effectively suppressed, and the reliability of the multilayer printed wiring board or the like can be improved. In addition, the embedding property at the time of laminating can be improved.

The second skeleton derived from the dimer diamine is preferably a skeleton derived from a reaction product of dimer diamine and acid dianhydride. The skeleton derived from the reaction product of the dimer diamine and the acid dianhydride has a second skeleton derived from the dimer diamine.

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

Examples of the acid dianhydride include the above-mentioned tetracarboxylic dianhydride and the like.

From the viewpoint of lowering the dielectric loss tangent of the cured product, reducing the surface roughness after etching, and increasing the plating peel strength, the total structural unit of the skeleton derived from the diamine compound contained in the cyclohexane ring-containing compound is 100 mol%. , The average proportion of the second skeleton derived from the diamine diamine is 15 mol% or more and less than 50 mol%.

The average proportion of the second skeleton derived from the dimer diamine is preferably 18 mol% or more, more preferably 20 mol%, based on 100 mol% of the total structural units of the skeleton derived from the diamine compound contained in the cyclohexane ring-containing compound. As mentioned above, it is preferably 40 mol% or less, and more preferably 30 mol% or less. When the average ratio of the second skeleton derived from the dimer diamine is not more than the above upper limit, the effect of the present invention can be exhibited even more effectively. Further, when the average ratio of the second skeleton derived from the dimer diamine is equal to or higher than the above lower limit, smear can be removed more effectively by the desmear treatment, and the resin film (B stage film) is flexible. The properties and elongation characteristics of the cured product can be further enhanced. In addition, it is possible to improve the embedding property in the uneven surface at the time of laminating.

<Third skeleton derived from diamine compound B>
The cyclohexane ring-containing compound does not have a third skeleton derived from diamine compound B, or has a third skeleton derived from diamine compound B. When the cyclohexane ring-containing compound has a third skeleton derived from the diamine compound B, the third skeleton derived from the diamine compound B exists as a partial skeleton in the cyclohexane ring-containing compound.

The diamine compound B is a diamine compound different from both the aliphatic diamine compound A and the dimer diamine. Diamine compound B has or does not have an aromatic ring. The diamine compound B may or may not have an aromatic ring. Diamine compound B has or does not have an aliphatic ring. The diamine compound B may or may not have an aliphatic ring.

The diamine compound B may or may not have a fluorine atom. Further, the diamine compound B may or may not have a phenolic hydroxyl group. When the diamine compound B is an aromatic diamine compound having a phenolic hydroxyl group, the coefficient of linear expansion can be further reduced.

Examples of the diamine compound B include an aliphatic diamine compound having no cyclohexane skeleton, a diamine compound having a cyclohexane skeleton and not having an aliphatic skeleton, and an aliphatic skeleton having no cyclohexane skeleton and having an aliphatic skeleton. Examples include diamine compounds that do not. The diamine compound B may be an aliphatic diamine compound having no cyclohexane skeleton, may be a diamine compound having a cyclohexane skeleton and not having an aliphatic skeleton, and may not have a cyclohexane skeleton. And it may be a diamine compound having no aliphatic skeleton. When the diamine compound B is a diamine compound having an aromatic ring, the diamine compound B may or may not have a carbon chain between the aromatic ring and the amino group. ..

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

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

From the viewpoint of further enhancing the thermal dimensional stability of the cured product, the cyclohexane ring-containing compound preferably has a third skeleton derived from the diamine compound B having an aromatic ring. From the viewpoint of further enhancing the thermal dimensional stability of the cured product, the third skeleton derived from the diamine compound B preferably has an aromatic ring.

The third skeleton derived from the diamine compound B is preferably a skeleton derived from a reaction product of the diamine compound B and the acid dianhydride. The skeleton derived from the reaction product of the diamine compound B and the acid dianhydride has a third skeleton derived from the diamine compound B. From the viewpoint of reducing the dielectric loss tangent and the dielectric constant of the cured product, the third skeleton derived from the diamine compound B preferably has a fluorine atom.

Examples of the diamine compound B include 1,1-bis (4-aminophenyl) cyclohexane, 2,7-diaminofluorene, 4,4'-ethylenedianiline, and 4,4'-methylenebis (2,6-diethylaniline). 4,4'-Methylenebis (2-ethyl-6-methylaniline), 1,4-diaminobutane, 1,10-diaminodecane, 1,12-diaminododecane, 1,7-diaminoheptane, 1,6-diamino Hexane, 1,5-diaminopentane, 1,8-diaminooctane, 1,3-diaminopropane, 1,11-diaminoundecane, 2-methyl-1,5-diaminopentane, 4,4'-isopropyridenebis ( 2-Aminophenol), 4,4'-(hexafluoroisopropyridene) bis (2-aminophenol), 4,4'-(hexafluoroisopropyridene) dianiline and the like. As the diamine compound B, only one type may be used, or two or more types may be used in combination.

Examples of the acid dianhydride include the above-mentioned tetracarboxylic dianhydride and the like.

From the viewpoint of enhancing the thermal dimensional stability of the cured product, the average ratio of the third skeleton derived from the diamine compound B is 35 mol in 100 mol% of the total structural units of the skeleton derived from the diamine compound contained in the cyclohexane ring-containing compound. Less than%.

The average proportion of the third skeleton derived from diamine compound B is preferably 0 mol% or more, more preferably 5 mol%, out of 100 mol% of the total structural units of the skeleton derived from the diamine compound contained in the cyclohexane ring-containing compound. As mentioned above, it is preferably 20 mol% or less, more preferably 10 mol% or less. When the average ratio of the third skeleton derived from the diamine compound B is not less than the above lower limit and not more than the above upper limit, the effect of the present invention can be exhibited even more effectively. The average proportion of the third skeleton derived from the diamine compound B may be 0 mol%, and exceeds 0 mol%, out of 100 mol% of the total structural units of the skeleton derived from the diamine compound contained in the cyclohexane ring-containing compound. May be. In particular, when a diamine compound having an aromatic skeleton is used as the diamine compound B, it is preferable to satisfy the above-mentioned preferable range from the viewpoint of solubility. Further, when a diamine compound having a hetero element other than the amine moiety is used as the diamine compound B, when the average ratio of the third skeleton derived from the diamine compound B is equal to or more than the above lower limit and below the above upper limit, copper and copper are used. Adhesion can be further improved.

The average ratio of the first skeleton derived from the aliphatic diamine compound A and the average ratio of the second skeleton derived from dimerdiamine in 100 mol% of the total structural units of the skeleton derived from the diamine compound contained in the cyclohexane ring-containing compound. , And the average proportion of the third skeleton derived from the diamine compound B can be calculated from, for example, the peak area of ^{1 H-NMR.}

The cyclohexane ring-containing compound may or may not have a branched structure.

The weight average molecular weight of the cyclohexane ring-containing compound is preferably 1000 or more, more preferably 2000 or more, still more preferably 3500 or more, particularly preferably 4000 or more, preferably 100,000 or less, more preferably 70,000 or less, still more preferably 25,000. Below, it is more preferably 18,000 or less, and particularly preferably 15,000 or less. When the weight average molecular weight is at least the above lower limit, the coefficient of linear expansion can be kept low. Further, when the weight average molecular weight exceeds 25,000, the melt viscosity of the resin material becomes higher and the embedding property in the uneven surface may decrease as compared with the case where the weight average molecular weight is 25,000 or less.

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

From the viewpoint of further enhancing the thermal dimensional stability of the cured product and further enhancing the adhesion between the insulating layer and the metal layer, the glass transition temperature of the cyclohexane ring-containing compound preferably exceeds 75 ° C., more preferably. It is 80 ° C. or higher, more preferably 85 ° C. or higher, particularly preferably 90 ° C. or higher, and preferably 250 ° C. or lower.

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

The content of the cyclohexane ring-containing compound is preferably 3% by weight or more, more preferably 5% by weight or more, still more preferably 10% by weight or more in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. , Especially preferably 15% by weight or more, preferably 80% by weight or less, and more preferably 70% by weight or less. When the content of the cyclohexane ring-containing compound is at least the above lower limit, the dielectric loss tangent of the cured product can be further lowered and the coefficient of linear expansion can be further reduced. When the content of the cyclohexane ring-containing compound is not more than the above upper limit, the uniformity of the surface roughness after etching can be enhanced.

The cyclohexane ring-containing maleimide compound can be produced, for example, as follows. The aliphatic diamine compound A is reacted with an acid dianhydride to obtain a first reaction product. The obtained first reactant is reacted with a dimer diamine to obtain a second reactant. The obtained second reactant is reacted with maleic anhydride.

The number of the maleimide skeletons in the cyclohexane ring-containing maleimide compound is preferably 2 or more, more preferably 3 or more, preferably 10 or less, and more preferably 5 or less. When the number of the maleimide skeletons is at least the above lower limit and at least the above upper limit, the effect of the present invention can be more effectively exhibited.

The cyclohexane ring-containing maleimide compound preferably has an imide skeleton. The number of imide skeletons in the cyclohexane ring-containing maleimide compound is preferably 1 or more, more preferably 2 or more, preferably 15 or less, and more preferably 10 or less.

The cyclohexane ring-containing compound may have an even number of imide skeletons, may have an odd number of imide skeletons, and may have an even number of imide skeletons and an odd number of imide skeletons. It may be a mixture with.

The cyclohexane ring-containing benzoxazine compound can be produced, for example, as follows. The aliphatic diamine compound A is reacted with an acid dianhydride to obtain a first reactant having amino groups at both ends. The first reactant obtained is reacted with paraform and phenol.

[Thermosetting compound]
The resin material preferably contains a thermosetting compound different from the cyclohexane ring-containing compound. The thermosetting compound may have a skeleton derived from a dimer diamine. The thermosetting compound preferably contains a thermosetting compound different from the maleimide compound having a skeleton derived from an aliphatic diamine compound having a cyclohexane ring. Only one type of the thermosetting compound may be used, or two or more types may be used in combination.

Examples of the thermosetting compound include maleimide compounds, epoxy compounds, cyanate compounds, vinyl compounds, phenoxy compounds, oxetane compounds, polyarylate compounds, diallylphthalate compounds, episulfide compounds, (meth) acrylic compounds, amino compounds, and unsaturated polyester compounds. , Polyurethane compounds, silicone compounds and the like.

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

<Maleimide compound>
The maleimide compound is a maleimide compound different from the cyclohexane ring-containing maleimide compound (hereinafter, may be referred to as "maleimide compound X"). Only one type of the maleimide compound X may be used, or two or more types may be used in combination.

The maleimide compound X may be a bismaleimide compound.

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

The maleimide compound X may or may not have a skeleton derived from a dimer diamine.

When the cyclohexane ring-containing compound is the cyclohexane ring-containing maleimide compound, the resin material preferably contains the maleimide compound X. In this case, the maleimide compound X is preferably a maleimide compound that satisfies the following (1) or the following (2). (1) A maleimide compound having no skeleton derived from a dimer diamine. (2) Maleimide having a skeleton derived from diaminediamine and having an average ratio of skeleton derived from dimerdiamine of 50 mol% or more in 100 mol% of all structural units of the skeleton derived from the diamine compound possessed by the maleimide compound. It is a compound.

The maleimide compound X preferably has an aromatic ring.

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

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

The content of the maleimide compound X is preferably 2% by weight or more, more preferably 5% by weight or more, preferably 50% by weight or less, based on 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. It is preferably 35% by weight or less, more preferably 20% by weight or less. When the content of the maleimide compound X is at least the above lower limit and at least the above upper limit, the thermal dimensional stability of the cured product can be further enhanced.

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

The molecular weight of the maleimide compound X means a molecular weight that can be calculated from the structural formula when the maleimide compound X is not a polymer and when the structural formula of the maleimide compound X can be specified. In addition, the molecular weight of the maleimide compound X indicates the 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 products of the maleimide compound X include "BMI-4000" and "BMI-5100" manufactured by Daiwa Kasei Kogyo Co., Ltd., "MIR-3000" manufactured by Nippon Kayaku Co., Ltd., and Designer Moleculars Inc. Examples thereof include "BMI-3000" and "BMI-689" manufactured by Japan.

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

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

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

From the viewpoint of further lowering the dielectric loss tangent of the cured product, the epoxy compound preferably contains an epoxy compound having a fluorine atom.

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

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

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

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

The molecular weight of the epoxy compound is more preferably 1000 or less. In this case, even if the content of the inorganic filler is 50% by weight or more in 100% by weight of the component excluding the solvent in the resin material, a resin material having high fluidity at the time of forming the insulating layer can be obtained. Therefore, when the uncured resin material or the B-staged product is laminated on the circuit board, the inorganic filler can be uniformly present.

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

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

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

Weight ratio of the content of the epoxy compound to the total content of the cyclohexane ring-containing compound and the curing agent described later (content of the epoxy compound / total content of the cyclohexane ring-containing compound and the curing agent described later) The amount) is preferably 0.2 or more, more preferably 0.3 or more, preferably 1 or less, and more preferably 0.8 or less. When the weight ratio is at least the above lower limit and at least the above upper limit, the dielectric loss tangent can be further lowered and the thermal dimensional stability can be further improved.

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

Examples of the vinyl compound include styrene compounds, acrylate compounds, and divinyl compounds. Examples of the divinyl compound include a divinylbenzyl ether compound. The vinyl compound may be a divinyl compound having an aliphatic skeleton or a divinyl ether compound.

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

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

The vinyl compounds such as the styrene compound and the acrylate compound also correspond to radical curable compounds. Therefore, the thermosetting compound preferably contains a radical curable compound. The thermosetting compound preferably contains a radical curable compound other than the maleimide compound. The resin material preferably contains a radical curable compound.

The content of the vinyl compound in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 20% by weight or more. Is 80% by weight or less, more preferably 70% by weight or less. When the content of the vinyl compound is not less than the above lower limit and not more than the above upper limit, the dielectric loss tangent of the cured product can be further lowered and the thermal dimensional stability can be further improved.

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

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

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

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

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

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

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

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

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

The inorganic filler is preferably surface-treated, more preferably a surface-treated product with a coupling agent, and even more preferably a surface-treated product with a silane coupling agent. By surface-treating the inorganic filler, the surface roughness of the surface of the roughened cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased. Further, since the inorganic filler is surface-treated, finer wiring can be formed on the surface of the cured product, and even better inter-wiring insulation reliability and interlayer insulation reliability can be obtained in the cured product. Can be granted.

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

The content of the inorganic filler in 100% by weight of the component excluding the solvent in the resin material is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 65% by weight or more, and particularly preferably 68% by weight. % Or more, preferably 90% by weight or less, more preferably 85% by weight or less, still more preferably 80% by weight or less, and particularly preferably 75% by weight or less. When the content of the inorganic filler is at least the above lower limit, the dielectric loss tangent is effectively lowered. When the content of the inorganic filler is not more than the above upper limit, the thermal dimensional stability can be improved and the warpage of the cured product can be effectively suppressed. When the content of the inorganic filler is at least the above lower limit and at least the above upper limit, the surface roughness of the surface of the cured product can be further reduced, and finer wiring can be formed on the surface of the cured product. Can be done. Further, the content of this inorganic filler makes it possible to reduce the coefficient of thermal expansion of the cured product and at the same time improve the smear removability.

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

Examples of the curing agent include a phenol compound (phenol curing agent), an active ester compound, a cyanate ester compound (cyanate ester curing agent), a benzoxazine compound having no cyclohexane ring (benzoxazine curing agent), and a carbodiimide compound (carbodiimide curing agent). ), Amine compound (amine curing agent), thiol compound (thiol curing agent), phosphine compound, dicyandiamide, acid anhydride and the like. The curing agent preferably has a functional group capable of reacting with the epoxy group of the epoxy compound.

From the viewpoint of further lowering the dielectric adjacency of the cured product and further enhancing the thermal dimensional stability of the cured product, the curing agent is a phenol compound, an active ester compound, a cyanate ester compound, or a benzoxazine compound having no cyclohexane ring. , Carbodiimide compound and acid anhydride preferably contain at least one component. From the viewpoint of further lowering the dielectric tangent and further enhancing the thermal dimensional stability, the curing agent is one of the phenol compound, the active ester compound, the cyanate ester compound, the benzoxazine compound having no cyclohexane ring, and the carbodiimide compound. It is more preferable to contain at least one component of the above, and it is further preferable to contain an active ester compound.

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

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

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

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

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

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

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

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

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

Examples of the cyanate ester compound include a novolak type cyanate ester resin, a bisphenol type cyanate ester resin, and a prepolymer in which these are partially triquantized. Examples of the novolak type cyanate ester resin include phenol novolac type cyanate ester resin and alkylphenol type cyanate ester resin. Examples of the bisphenol type cyanate ester resin include bisphenol A type cyanate ester resin, bisphenol E type cyanate ester resin, and tetramethyl bisphenol F type cyanate ester resin.

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

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

Examples of the benzoxazine compound having no cyclohexane ring include Pd-type benzoxazine and Fa-type benzoxazine.

Examples of commercially available products of the benzoxazine compound having no cyclohexane ring include "P-d type" manufactured by Shikoku Chemicals Corporation and "ODA-BOZ" manufactured by JFE Chemicals Corporation.

The content of the benzoxazine compound having no cyclohexane ring is preferably 1% by weight or more, more preferably 5% by weight or more, still more preferably 5% by weight or more, based on 100% by weight of the components excluding the inorganic filler and the solvent in the resin material. Is 10% by weight or more, preferably 70% by weight or less, and more preferably 60% by weight or less. When the content of the benzoxazine compound having no cyclohexane ring is at least the above lower limit and at least the above upper limit, the dielectric loss tangent of the cured product can be lowered and the thermal dimensional stability of the cured product can be further improved.

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

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

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

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

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

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

The content of the curing agent with respect to 100 parts by weight of the epoxy compound is preferably 70 parts by weight or more, more preferably 85 parts by weight or more, preferably 150 parts by weight or less, and more preferably 120 parts by weight or less. When the content of the curing agent is not less than the above lower limit and not more than the above upper limit, the curability is further improved, the thermal dimensional stability is further enhanced, and the volatilization of the residual unreacted component can be further suppressed.

The total content of the cyclohexane ring-containing compound, the thermosetting compound, and the curing agent in 100% by weight of the components excluding the inorganic filler and the solvent in the resin material is preferably 50% by weight or more, more preferably. Is 60% by weight or more, preferably 98% by weight or less, and more preferably 95% 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 further improved and the thermal dimensional stability can be further improved.

[Curing accelerator]
The resin material contains a curing accelerator. By using the above-mentioned curing accelerator, the curing rate becomes even faster. By rapidly curing the resin material, the crosslinked structure in the cured product becomes uniform, the number of unreacted functional groups decreases, and as a result, the crosslinked density increases. The curing accelerator is not particularly limited, and conventionally known curing accelerators can be used. Only one type of the curing accelerator may be used, or two or more types may be used in combination.

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

Examples of the imidazole compound include 2-undecyl imidazole, 2-heptadecyl imidazole, 2-methyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 2-phenyl-4-methyl imidazole and 1-benzyl-. 2-Methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-un Decylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimerite, 1-cyanoethyl-2-phenylimidazolium trimerite, 2,4-diamino-6- [2' -Methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino- 6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s -Triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-dihydroxymethylimidazole And so on.

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

Examples of the phosphorus compound include triphenylphosphine compounds.

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

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

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

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

When the thermosetting compound contains a radical curable compound such as the vinyl compound, the acrylate compound, and the styrene compound, radical curing proceeds. Therefore, the curing accelerator may contain the radical curing accelerator. It is preferable to include a radical curing accelerator having a one-minute half-life temperature of 170 ° C. or higher and 200 ° C. or lower. Examples of commercially available products of radical curing accelerators having a one-minute half-life temperature of 170 ° C. or higher and 200 ° C. or lower include "Perhexin 25B" manufactured by NOF CORPORATION.

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

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

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

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

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

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

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

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

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

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

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

From the viewpoint of obtaining a resin material having more excellent storage stability, the weight average molecular weights of the thermoplastic resin, the polyimide resin and the phenoxy resin are preferably 10,000 or more, more preferably 15,000 or more, preferably 100,000 or less. It is preferably 50,000 or less.

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

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

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

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

Most of the solvent is preferably removed when the resin composition is formed into a film. Therefore, the boiling point of the solvent is preferably 200 ° C. or lower, more preferably 180 ° C. or lower. The content of the solvent in the resin composition is not particularly limited. The content of the solvent can be appropriately changed in consideration of the coatability of the resin composition and the like.

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

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

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

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

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

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

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

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

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

The resin film does not have to be a prepreg. When the resin film is not a prepreg, migration does not occur along the glass cloth or the like. Further, when the resin film is laminated or pre-cured, unevenness due to the glass cloth does not occur on the surface.

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

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

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

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

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

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

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

The material of the metal layer is preferably copper.

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

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

The thickness of the copper foil of the copper-clad laminate is not particularly limited. The thickness of the copper foil is preferably in the range of 1 μm to 50 μm. Further, in order to increase the adhesive strength between the cured product of the resin material and the copper foil, it is preferable that the copper foil has fine irregularities on the surface. The method of forming the unevenness is not particularly limited. Examples of the method for forming the unevenness include a method for forming the unevenness by a treatment using a known chemical solution.

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

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

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

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

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

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

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

Among the multilayer boards, the multilayer printed wiring board is required to have a low dielectric loss tangent and high insulation reliability due to the insulating layer. Therefore, the resin material according to the present invention is suitably used for forming an insulating layer in a multilayer printed wiring board.

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

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

In the multilayer printed wiring board 11 shown in FIG. 1, a plurality of insulating layers 13 to 16 are laminated on the upper surface 12a of the circuit board 12. The insulating layers 13 to 16 are cured product layers. A metal layer 17 is formed in a part of the upper surface 12a of the circuit board 12. Of the plurality of insulating layers 13 to 16, the metal layer 17 is formed in a part of the upper surface of the insulating layers 13 to 15 other than the insulating layer 16 located on the outer surface opposite to the circuit board 12 side. ing. The metal layer 17 is a circuit. A metal layer 17 is arranged between the circuit board 12 and the insulating layer 13 and between the layers of the laminated insulating layers 13 to 16, respectively. The lower metal layer 17 and the upper metal layer 17 are connected to each other by at least one of a via hole connection and a through hole connection (not shown).

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

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

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

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

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

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

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

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

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

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

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

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

The following materials were prepared.

(Cyclohexane ring-containing compound)
Cyclohexane ring-containing maleimide compound 1:
According to the following Synthesis Example 1, a cyclohexane ring-containing maleimide compound 1 (molecular weight 4500) represented by the following formula (1A) was synthesized. However, the structure of the cyclohexane ring-containing maleimide compound 1 represented by the following formula (1A) is an example, and the cyclohexane ring-containing maleimide compound 1 is, for example, a compound represented by the following formula (1A), and the compound is an amine. It is a mixture with compounds in different positions. In the obtained cyclohexane ring-containing maleimide compound 1, the average ratio of the first skeleton derived from the aliphatic diamine compound A was 72 mol% in 100 mol% of the total structural units of the skeleton derived from the diamine compound, which was derived from diamine diamine. The average proportion of the second skeleton was 28 mol%.

<Synthesis example 1>
Tricyclodecanediamine was used as the aliphatic diamine compound A.

In a 500 mL eggplant flask, 100 g of toluene, 36 g of N-methyl-2-pyrrolidone (NMP), and 6 g of methanesulfonic acid were placed. Then, 6.6 g (16 mmol) of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) and 12.5 g (64 mmol) of tricyclodecane diamine were added. Then, 17.7 g (60 mmol) of biphenylic dianhydride was added little by little. An eggplant flask was attached to the Dean-Stark apparatus and heated to reflux for 3.5 hours. In this way, a compound having amines at both ends and having a plurality of imide skeletons was obtained. After removing the water discharged during the condensation and returning to room temperature, 4.42 g (45 mmol) of maleic anhydride was added, the mixture was stirred, and the mixture was similarly heated and reacted. In this way, a compound having a maleimide skeleton at both ends was obtained. The organic layer was washed with a mixed solvent of water and ethanol, and then the mixed solvent was removed to obtain a toluene solution. Isopropanol was then added to the toluene solution to reprecipitate the product. Then, it was dried in a vacuum oven to obtain a cyclohexane ring-containing maleimide compound 1.

Cyclohexane ring-containing maleimide compound 2:
According to the following Synthesis Example 2, a cyclohexane ring-containing maleimide compound 2 (molecular weight 12000) represented by the following formula (2A) was synthesized. However, the structure of the cyclohexane ring-containing maleimide compound 2 represented by the following formula (2A) is an example, and the cyclohexane ring-containing maleimide compound 2 is, for example, a compound represented by the following formula (2A) and the compound being an amine. It is a mixture with compounds in different positions. In the obtained cyclohexane ring-containing maleimide compound 2, the average ratio of the first skeleton derived from the aliphatic diamine compound A was 65 mol% in 100 mol% of the total structural units of the skeleton derived from the diamine compound, which was derived from diamine diamine. The average proportion of the second skeleton was 35 mol%.

<Synthesis example 2>
Tricyclodecanediamine was used as the aliphatic diamine compound A.

105 g of toluene, 41 g of N-methyl-2-pyrrolidone (NMP) and 7 g of methanesulfonic acid were placed in a 500 mL eggplant flask. Then, 9.3 g (23 mmol) of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) and 10.2 g (53 mmol) of tricyclodecane diamine were added. Then, 13.1 g (60 mmol) of pyromellitic dianhydride was added little by little. An eggplant flask was attached to the Dean-Stark apparatus and heated to reflux for 3.5 hours. In this way, a compound having amines at both ends and having a plurality of imide skeletons was obtained. After removing the water discharged during the condensation and returning to room temperature, 4.42 g (45 mmol) of maleic anhydride was added, the mixture was stirred, and the mixture was similarly heated and reacted. In this way, a compound having a maleimide skeleton at both ends was obtained. The organic layer was washed with a mixed solvent of water and ethanol, and then the mixed solvent was removed to obtain a toluene solution. Isopropanol was then added to the toluene solution to reprecipitate the product. Then, it was dried in a vacuum oven to obtain a cyclohexane ring-containing maleimide compound 2.

Cyclohexane ring-containing maleimide compound 3:
A cyclohexane ring-containing maleimide compound 3 (molecular weight 4300) was synthesized according to the following Synthesis Example 3. In the obtained cyclohexane ring-containing maleimide compound 3, the average ratio of the first skeleton derived from the aliphatic diamine compound A was 66 mol% in 100 mol% of the total structural units of the skeleton derived from the diamine compound, which was derived from diamine diamine. The average proportion of the second skeleton was 34 mol%.

<Synthesis example 3>
In a 500 mL eggplant flask, 105 g of toluene, 41 g of N-methyl-2-pyrrolidone (NMP), and 7 g of methanesulfonic acid were placed. Then, 9.9 g (24.2 mmol) of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) and 8.6 g (55.8 mmol) of norbornane diamine (“Pro-NBDA” manufactured by Mitsui Kagaku Fine Co., Ltd.) were added. Then, 15.9 g (54 mmol) of biphenylic acid dianhydride and 1.5 g (6 mmol) of bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic dianhydride were added. Was mixed and then added little by little. An eggplant flask was attached to the Dean-Stark apparatus and heated to reflux for 3.5 hours. In this way, a compound having amines at both ends and having a plurality of imide skeletons was obtained. After removing the water discharged during the condensation and returning to room temperature, 4.42 g (45 mmol) of maleic anhydride was added, the mixture was stirred, and the mixture was similarly heated and reacted. In this way, a compound having a maleimide skeleton at both ends was obtained. The organic layer was washed with a mixed solvent of water and ethanol, and then the mixed solvent was removed to obtain a toluene solution. Isopropanol was then added to the toluene solution to reprecipitate the product. Then, it was dried in a vacuum oven to obtain a cyclohexane ring-containing maleimide compound 3.

Cyclohexane ring-containing maleimide compound 4:
A cyclohexane ring-containing maleimide compound 4 (molecular weight 4400) was synthesized according to the following Synthesis Example 4. In the obtained cyclohexane ring-containing maleimide compound 4, the average ratio of the first skeleton derived from the aliphatic diamine compound A was 63 mol% in 100 mol% of the total structural units of the skeleton derived from the diamine compound, which was derived from diamine diamine. The average proportion of the second skeleton was 29 mol%, and the average proportion of the third skeleton derived from the diamine compound B was 8 mol%.

<Synthesis example 4>
90 g of toluene, 46 g of N-methyl-2-pyrrolidone (NMP) and 7 g of methanesulfonic acid were placed in a 500 mL eggplant flask. Then, 9.0 g (22 mmol) of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) and 7.4 g (52 mmol) of norbornane diamine (“Pro-NBDA” manufactured by Mitsui Kagaku Fine Co., Ltd.) were added. Then, 2.0 g (6 mmol) of 4,4'-(hexafluoroisopropyridene) dianiline was added. Then, 15.9 g (54 mmol) of biphenylic acid dianhydride and 1.5 g (6 mmol) of bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic dianhydride were added. Was mixed and then added little by little. An eggplant flask was attached to the Dean-Stark apparatus and heated to reflux for 3.5 hours. In this way, a compound having amines at both ends and having a plurality of imide skeletons was obtained. After removing the water discharged during the condensation and returning to room temperature, 4.42 g (45 mmol) of maleic anhydride was added, the mixture was stirred, and the mixture was similarly heated and reacted. In this way, a compound having a maleimide skeleton at both ends was obtained. The organic layer was washed with a mixed solvent of water and ethanol, and then the mixed solvent was removed with an evaporator to obtain a toluene solution. Isopropanol was then added to the toluene solution to reprecipitate the product. Then, it was dried in a vacuum oven to obtain a cyclohexane ring-containing maleimide compound 4.

The molecular weight of the cyclohexane ring-containing maleimide compound synthesized in Synthesis Examples 1 to 4 was determined as follows.

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

The average ratio of each skeleton of the cyclohexane ring-containing maleimide compound synthesized in Synthesis Examples 1 to 4 is the signal of the hydrogen atom bonded to the carbon atom bonded to the nitrogen atom constituting each diamine skeleton by ^{1 H-NMR measurement.} Calculated from the area ratio.

(Thermosetting compound)
Biphenyl type epoxy compound ("NC-3000" manufactured by Nippon Kayaku Co., Ltd.)
Naphthalene type epoxy compound ("ESN-475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
Resorcinol diglycidyl ether (“EX-201” manufactured by Nagase ChemteX Corporation)
Epoxy compound having a glycidylamine skeleton ("630" manufactured by Mitsubishi Chemical Corporation)
Epoxy compound having a polybutadiene skeleton ("PB3600" manufactured by Daicel Corporation)
Epoxy compound with amide skeleton (Nippon Kayaku Co., Ltd. "WHR-991S")
Multi-branched aliphatic epoxy compound (Nissan Chemical Industries, Ltd. "Foldi E101")
Maleimide compound 1 (N-alkylbismaleimide compound, "BMI-1500" manufactured by Designer Moleculars Inc.)
Maleimide compound 2 (N-alkylbismaleimide compound, "BMI-1700" manufactured by Designer Moleculars Inc.)
Maleimide compound 3 ("BMI-4100" manufactured by Daiwa Kasei Co., Ltd.)
Maleimide compound 4 ("MIR-3000" manufactured by Nippon Kayaku Co., Ltd.)
Styrene compound ("OPE-2St-1200" manufactured by Mitsubishi Gas Chemical Company, radical curable compound, styrene compound having a phenylene ether skeleton)
Acrylate compound (“Light acrylate DCP-A” manufactured by Kyoeisha Chemical Co., Ltd., radical curable compound, abbreviated as “DCP-A” in the table)

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

(Hardener)
Liquid containing 1 active ester compound (“EXB-9416-70BK” manufactured by DIC Corporation, solid content 70% by weight)
Active ester compound 2 containing liquid (DIC Corporation "HPC-8150-62T", solid content 62% by weight)
Active ester compound 3 containing liquid (DIC Corporation "HPC-8000L-65T", solid content 65% by weight)
Active ester compound 4 (“EXB-8” manufactured by DIC Corporation, solid content 100% by weight)
Carbodiimide compound ("Carbodilite V-03" manufactured by Nisshinbo Chemical Co., Ltd., abbreviated as "V-03" in the table)
Phenol compound-containing liquid ("LA-1356" manufactured by DIC Corporation, solid content 60% by weight)

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

(Thermoplastic resin)
Styrene-butadiene resin (Asahi Kasei's "Tough Tech H1043", abbreviated as "H1043" in the table)
Alicyclic thermoplastic resin ("Neoresin EP-140" manufactured by JXTG, abbreviated as "EP-140" in the table)
Polyimide compound (polyimide resin):
A polyimide compound-containing solution (nonvolatile content 26.8% by weight), which is a reaction product of tetracarboxylic dianhydride and dimer diamine, was synthesized according to the following Synthesis Example 5.

<Synthesis example 5>
300.0 g of tetracarboxylic dianhydride (“BisDA-1000” manufactured by SABIC Japan GK) and 665.5 g of cyclohexanone were placed in a reaction vessel equipped with a stirrer, a water divider, a thermometer and a nitrogen gas introduction tube. And the solution in the reaction vessel was heated to 60 ° C. Next, 89.0 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) and 54.7 g of 1,3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Company) were added dropwise to the reaction vessel. Next, 121.0 g of methylcyclohexane and 423.5 g of ethylene glycol dimethyl ether were added to the reaction vessel, and an imidization reaction was carried out at 140 ° C. for 10 hours. In this way, a polyimide compound-containing solution (nonvolatile content 26.8% by weight) was obtained. The molecular weight (weight average molecular weight) of the obtained polyimide compound was 20000. The molar ratio of the acid component / amine component was 1.04.

The molecular weight of the polyimide compound synthesized in Synthesis Example 5 was determined as follows.

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

(Examples 1 to 10 and Comparative Examples 1 to 3)
The components shown in Tables 1 to 3 below were blended in the blending amounts shown in Tables 1 to 3 below (unit: parts by weight of solid content) and stirred at room temperature until a uniform solution was obtained to obtain a resin material.

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

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

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

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

[Criteria for determining the coefficient of linear expansion]
○ ○: Average coefficient of linear expansion is 25 ppm / ° C or less ○: Average coefficient of linear expansion exceeds 25 ppm / ° C and is 29 ppm / ° C or less ×: Average coefficient of linear expansion exceeds 29 ppm / ° C

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

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

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

(B) Permanganate treatment (roughening treatment and desmear treatment)
The swelling-treated laminate B was placed in a crude aqueous solution of potassium permanganate (“Concentrate Compact CP” manufactured by Atotech Japan) at 80 ° C. and shaken for 30 minutes. Next, after treating for 2 minutes with a cleaning solution at 25 ° C. (“Reduction Securigant P” manufactured by Atotech Japan), cleaning with pure water was performed to obtain evaluation sample 1.

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

[Criteria for removing residue on the bottom of vias]
○ ○: Maximum smear length is less than 2 μm ○: Maximum smear length is 2 μm or more and less than 4 μm ×: Maximum smear length is 4 μm or more

(4) Surface Roughness (Surface Roughness) After Etching and Uniformity of Surface Roughness Laminating process and semi-hardening treatment:
A double-sided copper-clad laminate (CCL substrate) (“E679FG” manufactured by Hitachi Kasei Co., Ltd.) was prepared. Both sides of the copper foil surface of this double-sided copper-clad laminate were immersed in "Cz8101" manufactured by MEC to roughen the surface of the copper foil. Using "Batch type vacuum laminator MVLP-500-IIA" manufactured by Meiki Co., Ltd. on both sides of the roughened copper-clad laminate, the resin film (B stage film) side of the laminate is placed on the copper-clad laminate. It was laminated on top of each other to obtain a laminated structure. The laminating conditions were such that the pressure was reduced for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then the pressure was pressed at 100 ° C. and a pressure of 0.4 MPa for 30 seconds. Then, the resin film was semi-cured by heating at 180 ° C. for 30 minutes. In this way, a laminated body in which a semi-cured resin film was laminated on the CCL substrate was obtained.

Roughening process:
(A) Swelling treatment:
The obtained laminate was placed in a swelling solution at 60 ° C. (“Swelling Dip Securigant P” manufactured by Atotech Japan) and shaken for 10 minutes. Then, it was washed with pure water.

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

Measurement of surface roughness:
On the surface of the evaluation sample (roughened cured product), 10 regions of 94 μm × 123 μm were arbitrarily selected. Arithmetic mean roughness Ra was measured for each of these 10 regions using a non-contact three-dimensional surface shape measuring device (“WYKO NT1100” manufactured by Veeco). The following surface roughness is evaluated from the average value of the measured arithmetic average roughness Ra at 10 points, and the following from the absolute value of the difference between the maximum value and the minimum value of the measured arithmetic average roughness Ra at 10 points. The uniformity of surface roughness was evaluated. The arithmetic mean roughness Ra was measured according to JIS B0601: 1994.

[Criteria for determining surface roughness after etching]
○○: The average value of the arithmetic average roughness Ra is less than 50 nm ○: The average value of the arithmetic average roughness Ra is 50 nm or more and less than 80 nm ×: The average value of the arithmetic average roughness Ra is 80 nm or more

[Criteria for determining the uniformity of surface roughness (surface roughness) after etching]
◯: Absolute value of the difference between the maximum value and the minimum value of the arithmetic mean roughness Ra is less than 10 nm Δ: Absolute value of the difference between the maximum value and the minimum value of the arithmetic average roughness Ra is 10 nm or more and less than 20 nm ×: Arithmetic mean The absolute value of the difference between the maximum and minimum values of roughness Ra is 20 nm or more.

(5) Plating peel strength Laminating process and semi-hardening process:
A 100 mm square double-sided copper-clad laminate (CCL substrate) (“E679FG” manufactured by Hitachi Kasei Co., Ltd.) was prepared. Both sides of the copper foil surface of this double-sided copper-clad laminate were immersed in "Cz8101" manufactured by MEC to roughen the surface of the copper foil. Using "Batch type vacuum laminator MVLP-500-IIA" manufactured by Meiki Co., Ltd., the resin film (B stage film) side of the laminated film is placed on the copper-clad laminate on both sides of the roughened copper-clad laminate. It was laminated on top of each other to obtain a laminated structure. The laminating conditions were such that the pressure was reduced for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, then laminating at 100 ° C. and pressure 0.7 MPa for 30 seconds, and further pressing at a press pressure of 0.8 MPa and a press temperature of 100 ° C. for 60 seconds. Then, the resin film in the laminated structure was heated at 100 ° C. for 30 minutes with the PET film attached, and then further heated at 180 ° C. for 30 minutes to semi-cure the resin film. Then, the PET film was peeled off to obtain a laminated body in which a semi-cured product of the resin film was laminated on the CCL substrate.

Roughening process:
(A) Swelling treatment:
The obtained laminate was placed in a swelling solution at 60 ° C. (“Swelling Dip Securigant P” manufactured by Atotech Japan) and shaken for 10 minutes. Then, it was washed with pure water.

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

Electroless plating:
The surface of the obtained roughened cured product was treated with an alkaline cleaner at 60 ° C. (“Cleaner Securigant 902” manufactured by Atotech Japan Co., Ltd.) for 5 minutes, and degreased and washed. After washing, the cured product was treated with a predip solution at 25 ° C. (“Pridip Neogant B” manufactured by Atotech Japan) for 2 minutes. Then, the cured product was treated with an activator solution at 40 ° C. (“Activator Neogant 834” manufactured by Atotech Japan Co., Ltd.) for 5 minutes, and a palladium catalyst was attached. Next, the cured product was treated with a reducing solution at 30 ° C. (“Reducer Neogant WA” manufactured by Atotech Japan) for 5 minutes.

Next, the cured product was placed in a chemical copper solution (Atotech Japan's "Basic Print Gantt MSK-DK", "Copper Print Gantt MSK", "Stabilizer Print Gantt MSK", and "Reducer Cu") for electroless plating. Was carried out until the plating thickness became about 0.5 μm. After electroless plating, annealing treatment was performed at a temperature of 120 ° C. for 30 minutes in order to remove residual hydrogen gas. All the steps up to the electroless plating step were carried out with a beaker scale containing 2 L of the treatment liquid and shaking the cured product.

Electroplating:
Next, the cured product subjected to the electroless plating treatment was subjected to electrolytic plating until the plating thickness became 25 μm. Copper sulfate solution for electrolytic copper plating ("Copper sulfate pentahydrate" manufactured by Wako Pure Chemical Industries, Ltd., "Sulfate" manufactured by Wako Pure Chemical Industries, Ltd., "Basic leveler capallaside HL" manufactured by Atotech Japan, "Basic leveler capallaside HL" manufactured by Atotech Japan. Using the corrective agent Capalacid GS ”), ^{electrolytic plating was carried out by passing a current of 0.6 A / cm 2} until the plating thickness became about 25 μm. After the copper plating treatment, the cured product was heated at 200 ° C. for 60 minutes to further cure the cured product. In this way, a cured product in which the copper plating layer was laminated on the upper surface was obtained.

Measurement of plating peel strength:
A total of 6 strip-shaped cuts having a width of 10 mm were made at 5 mm intervals on the surface of the cured copper plating layer on which the obtained copper plating layer was laminated on the upper surface. Set the cured product with the copper plating layer laminated on the upper surface in a 90 ° peeling tester (“TE-3001” manufactured by Tester Sangyo Co., Ltd.), pick up the end of the notched copper plating layer with a grip, and copper. The plating layer was peeled off by 20 mm and the peeling strength (plating peel strength) was measured. The peeling strength (plating peel strength) was measured at each of the six notches, and the average value of the plating peel strength was obtained. The plating peel strength was judged according to the following criteria.

[Criteria for plating peel strength]
○ ○: The average value of the plating peel strength is 0.5 kgf / cm or more ○: The average value of the plating peel strength is 0.45 kgf / cm or more and less than 0.5 kgf / cm Δ: The average value of the plating peel strength is 0.35 kgf / Cm or more and less than 0.45 kgf / cm ×: The average value of plating peel strength is less than 0.35 kgf / cm

(6) Glass transition temperature Tg
The obtained resin film (B stage film) having a thickness of 40 μm was heated at 190 ° C. for 90 minutes, and the obtained cured product was cut into a size of 5 mm × 50 mm. Using a thermomechanical analyzer (“DMS6100” manufactured by SII Nanotechnology Co., Ltd.), the distance between chucks is 20 mm, the amplitude is 10 μm, the initial tension amplitude is 400 mN, and the temperature rise rate is from 50 ° C to 330 ° C at 5 ° C / min. The measurement was carried out under the condition of raising the temperature and the condition of the frequency of 10 Hz. In the obtained measurement results, the peak temperature of the tangent loss was defined as the glass transition temperature Tg (° C.).

[Criteria for determining glass transition temperature Tg]
○○: Tg is 180 ° C or higher ○: Tg is 175 ° C or higher and lower than 180 ° C ×: Tg is lower than 175 ° C

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

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

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

[Criteria for embedding on uneven surfaces]
◯: Number ratio of dents in which voids were observed 0%
Δ: Number ratio of dents in which voids were observed Exceeded from 0% and less than 5% ×: Number ratio of dents in which voids were observed 5% or more

(8) Flexibility of B Stage Film The obtained resin film (B stage film) was bent at different positions at 180 degrees for a total of 10 times. The number of times the resin film cracked or cracked was observed during 10 times.

[Criteria for determining the flexibility of B stage film]
○○: The number of times cracks or cracks occur in 10 times is less than 3 times ○: The number of times cracks or cracks occur in 10 times is 3 times or more and less than 6 times ×: Cracks or cracks occur in 10 times Occurs 6 times or more

(9) Elongation characteristics of cured product The obtained cured resin film (B stage film) having a thickness of 40 μm was heated at 130 ° C. for 60 minutes and then heated at 190 ° C. for 90 minutes to obtain a cured product having a size of 10 mm × 100 mm. I cut it. Using a tensile tester (“AGS-J 100N” manufactured by SHIMADZU), measurements were made under the conditions of a distance between chucks of 60 mm and a tensile speed of 5 mm / min, and the maximum elongation was measured. The initial tension was 0.35 N. The measurement was repeated 5 times, and the average value of the elongation at break (average elongation at break) was calculated.

[Criteria for determining the elongation characteristics of cured products]
○○: Average breaking elongation is 1.8% or more ○: Average breaking elongation is 1.5% or more and less than 1.8% ×: Average breaking elongation is less than 1.5%

The composition and results are shown in Tables 1 to 3 below.

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

Claims (21)

A cyclohexane ring-containing compound of at least one of a maleimide compound having a cyclohexane ring and a benzoxazine compound having a cyclohexane ring,
Contains curing accelerators
The cyclohexane ring-containing compound has a first skeleton derived from an aliphatic diamine compound having a cyclohexane ring and a second skeleton derived from dimerdiamine, and the aliphatic diamine compound having a cyclohexane ring is dimerdiamine. Unlike,
The average ratio of the first skeleton derived from the aliphatic diamine compound having a cyclohexane ring is 50 mol% or more and 85 mol% or less in 100 mol% of the total structural units of the skeleton derived from the diamine compound contained in the cyclohexane ring-containing compound. And
A resin material in which the average proportion of the second skeleton derived from the dimer diamine is 15 mol% or more and less than 50 mol% in 100 mol% of the total structural units of the skeleton derived from the diamine compound contained in the cyclohexane ring-containing compound. The cyclohexane ring-containing compound has a third skeleton derived from a diamine compound different from the aliphatic diamine compound having a cyclohexane ring, and the diamine compound different from the aliphatic diamine compound having the cyclohexane ring is a diamine diamine. The different resin material according to claim 1. The resin material according to claim 2, wherein the third skeleton derived from a diamine compound different from the aliphatic diamine compound having a cyclohexane ring has an aromatic ring. The resin material according to claim 2 or 3, wherein the third skeleton derived from a diamine compound different from the aliphatic diamine compound having a cyclohexane ring has a fluorine atom. In the first skeleton derived from the aliphatic diamine compound having a cyclohexane ring, the nitrogen atom constituting the first amino group and the carbon atom constituting the cyclohexane ring are directly bonded or two. The resin material according to any one of claims 1 to 4, which is bonded via the following atoms. In the first skeleton derived from the aliphatic diamine compound having a cyclohexane ring, the nitrogen atom constituting the second amino group different from the first amino group and the carbon atom constituting the cyclohexane ring are directly linked. The resin material according to claim 5, which is bonded or bonded via 3 or less atoms. The resin material according to any one of claims 1 to 6, wherein the aliphatic diamine compound having a cyclohexane ring is tricyclodecanediamine, norbornanediamine, or isophoronediamine. The resin material according to any one of claims 1 to 7, wherein the cyclohexane ring-containing compound has a glass transition temperature of 80 ° C. or higher and 250 ° C. or lower. The resin material according to any one of claims 1 to 8, wherein the cyclohexane ring-containing compound has a weight average molecular weight of 2000 or more and 100,000 or less. A thermosetting compound different from the cyclohexane ring-containing compound,
The resin material according to any one of claims 1 to 9, which comprises a curing agent. The cyclohexane ring-containing compound is a maleimide compound having the cyclohexane ring.
The resin material according to claim 10, wherein the thermosetting compound contains a maleimide compound. The maleimide compound is a maleimide compound having no skeleton derived from a dimer diamine, or
The maleimide compound has a skeleton derived from diaminediamine, and the average ratio of the skeleton derived from dimerdiamine is 50 mol% or more in 100 mol% of the total structural units of the skeleton derived from the diamine compound contained in the maleimide compound. The resin material according to claim 11, which is a maleimide compound. The resin material according to any one of claims 10 to 12, wherein the thermosetting compound contains an epoxy compound. The resin material according to any one of claims 10 to 13, wherein the curing agent contains an active ester compound. The resin material according to any one of claims 10 to 14, wherein the thermosetting compound contains a radical curable compound. The resin material according to any one of claims 1 to 15, which comprises an inorganic filler. The resin material according to claim 16, wherein the content of the inorganic filler is 50% by weight or more in 100% by weight of the component excluding the solvent in the resin material. The resin material according to claim 16 or 17, wherein the inorganic filler is silica. The resin material according to any one of claims 1 to 18, which is a resin film. The resin material according to any one of claims 1 to 19, which is used for forming an insulating layer in a multilayer printed wiring board. With the circuit board
A plurality of insulating layers arranged on the surface of the circuit board,
With a plurality of metal layers arranged between the insulating layers,
A multilayer printed wiring board in which at least one of the plurality of insulating layers is a cured product of the resin material according to any one of claims 1 to 20.

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