TW202112904A - Resin material and multilayer printed wiring board - Google Patents

Abstract

Provided is a resin material whereby (1) the dielectric dissipation factor of a cured article thereof can be lowered, (2) the thermal dimensional stability of the cured article can be increased, (3) resin smear can be effectively removed by desmearing, (4) variation in surface roughness after etching can be suppressed, and (5) plating peel strength can be increased. The resin material pertaining to the present invention includes a compound having a structure represented by formula (X), and a curing accelerator. In formula (X), R represents an organic group, and n ≥ 1.

Description

Resin materials and multilayer printed wiring boards

The present invention relates to a resin material containing a compound having an imine skeleton. In addition, the present invention relates to a multilayer printed wiring board using the above-mentioned resin material.

In the past, various resin materials have been used to obtain electronic components such as semiconductor devices, build-up boards, and printed wiring boards. For example, in a multilayer printed wiring board, a resin material is used in order to form an insulating layer to insulate the internal interlayers, or to form an insulating layer located on the surface part. The surface of the above-mentioned insulating layer is usually laminated as a metal wiring. Moreover, in order to form the said insulating layer, the resin film which formed the said resin material into a film may be used. The above-mentioned resin material and the above-mentioned resin film are used as insulating materials for multilayer printed wiring boards including build-up films.

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

The following Patent Document 2 discloses a resin composition comprising (A) an epoxy resin and (B) a maleimide compound, and the (B) component contains an alkyl group having 5 or more carbon atoms And at least any one of alkylene groups having 5 or more carbon atoms.

The following Patent Document 3 discloses a resin composition for electronic materials, which contains a bismaleimide compound having two maleimide groups, And more than one polyimide group with specific structure. In the above-mentioned bismaleimide compound, two of the above-mentioned maleimide groups are each independently bonded to each other via a first linking group formed by at least 8 or more atoms in a straight chain. Both ends of the above-mentioned polyimide group.

The following Patent Document 4 discloses a resin composition for a printed wiring board, which is a thermosetting resin composition for forming an insulating layer in a printed wiring board, and contains a maleimide compound (A) , The maleimide compound (A) includes at least a bismaleimide compound (A1) having a specific structure. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] WO2016/114286A1 [Patent Document 2] Japanese Patent Laid-Open No. 2019-44128 [Patent Document 3] Japanese Patent Laid-Open No. 2018-90728 [Patent Document 4] Japanese Patent Laid-Open No. 2016-196549

[The problem to be solved by the invention]

In the case of forming an insulating layer using the previous resin material as described in Patent Document 1, the thermal dimensional stability of the cured product may not become sufficiently high. In addition, when the insulating layer is formed using the previous resin material as described in Patent Document 2, the dielectric loss factor of the cured product may not become sufficiently low. As described in Patent Documents 3 and 4, if a resin material containing a maleimide compound having a specific structure is used, the dielectric loss factor and thermal dimensional stability can be improved to a certain extent, but further improvement is expected .

In addition, with regard to the previous resin materials described in Patent Documents 1-4, the scum in the through holes may not be sufficiently removed by the desmear treatment when forming the insulating layer.

Furthermore, when the insulating layer is formed using the previous resin material, the surface roughness after etching may be uneven, or the plating peel strength of the metal layer deposited by the plating treatment on the surface of the insulating layer may be different. The situation becomes high enough.

The purpose of the present invention is to provide a resin material, which 1) can reduce the dielectric loss factor of the hardened object, 2) can improve the thermal dimensional stability of the hardened object, and 3) can effectively remove the scum by desmear treatment, 4) It can suppress the unevenness of the surface roughness after etching, and 5) it can improve the peeling strength of the plating. Moreover, the object of the present invention is also to provide a multilayer printed wiring board using the above-mentioned resin material. [Technical means to solve the problem]

According to a broader aspect of the present invention, a resin material is provided, which includes a compound having a structure represented by the following formula (X) and a hardening accelerator.

[化1]

In the above formula (X), R represents an organic group, and n represents a number of 1 or more.

In a specific aspect of the resin material of the present invention, in the above formula (X), n represents a number of 2 or more.

In a specific aspect of the resin material of the present invention, in the above formula (X), R is an aliphatic ring group.

In a specific aspect of the resin material of the present invention, in the above formula (X), R has a partial skeleton derived from the skeleton of dimer diamine.

In a specific aspect of the resin material of the present invention, in the above formula (X), R has a partial skeleton derived from the skeleton of a diamine compound other than dimer diamine.

In a specific aspect of the resin material of the present invention, in the above-mentioned compound, the nitrogen atom constituting the imine skeleton is only bonded to the carbon atom constituting the aliphatic skeleton.

In a specific aspect of the resin material of the present invention, the above-mentioned compound is a compound having a maleimide skeleton.

In a specific aspect of the resin material of the present invention, the above-mentioned compound is a compound having a maleimide skeleton at both ends.

In a specific aspect of the resin material of the present invention, the weight average molecular weight of the above-mentioned compound is 1,000 or more and 100,000 or less.

In a specific aspect of the resin material of the present invention, the compound has a structure represented by the following formula (Y), and the number of repetitions of the structure represented by the above formula (X) is the same as that represented by the following formula (Y) In 100% of the total number of repetitions of the structure, the number of repetitions of the structure represented by the above formula (X) is 10% or more and 90% or less. [化2]

In the above formula (Y), R1 represents a tetravalent organic group, R2 represents an organic group, and m represents a number of 1 or more.

In a specific aspect of the resin material of the present invention, in the above formula (Y), R1 does not have a skeleton derived from phthalimide, and in the above formula (Y), R2 does not have a skeleton derived from phthalimide The skeleton of dimethyl imide.

In a specific aspect of the resin material of the present invention, in the above formula (Y), R1 does not have an aromatic skeleton.

In a specific aspect of the resin material of the present invention, a thermosetting compound and a curing agent are included, and the thermosetting compound includes an epoxy compound.

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

In a specific aspect of the resin material of the present invention, at least one of the epoxy compound and the active ester compound has an amide skeleton or an amide skeleton.

In a specific aspect of the resin material of the present invention, the thermosetting compound includes a radical curing compound.

In a specific aspect of the resin material of the present invention, the above-mentioned resin material includes an inorganic filler.

In a specific aspect of the resin material of the present invention, in 100% by weight of the components other than the solvent in the resin material, the content of the above-mentioned inorganic filler is 50% by weight or more.

In a specific aspect of the resin material of the present invention, the above-mentioned inorganic filler is silica.

In a specific aspect of the resin material of the present invention, the above-mentioned resin material is a resin film.

The resin material of the present invention can be suitably used for forming an insulating layer in a multilayer printed wiring board.

According to a broader aspect of the present invention, there is provided a multilayer printed wiring board comprising: a circuit substrate, a plurality of insulating layers arranged on the surface of the circuit substrate, and a metal layer arranged between the plurality of insulating layers, and At least one of the plurality of insulating layers is a cured product of the resin material. [Effects of Invention]

The resin material of the present invention includes a compound having a structure represented by formula (X) and a hardening accelerator. Regarding the resin material of the present invention, due to the above-mentioned structure, 1) the dielectric loss factor of the hardened material can be reduced, 2) the thermal dimensional stability of the hardened material can be improved, and 3) the glue can be effectively removed by desmear treatment Dross, 4) can suppress uneven surface roughness after etching, and 5) can improve plating peel strength.

Hereinafter, the present invention will be explained in detail.

The resin material of the present invention includes a compound having a structure represented by the following formula (X) (hereinafter, sometimes referred to as compound X), and a curing accelerator.

[化3]

In the above formula (X), R represents an organic group, and n represents a number of 1 or more.

Regarding the resin material of the present invention, due to the above-mentioned structure, 1) the dielectric loss factor of the hardened material can be reduced, 2) the thermal dimensional stability of the hardened material can be improved, and 3) the glue can be effectively removed by desmear treatment Dross, 4) can suppress uneven surface roughness after etching, and 5) can improve plating peel strength. The resin material of the present invention can exert all the effects of 1)-5).

In addition, since the resin material of the present invention has the above-mentioned structure, the compatibility of the resin material can be improved. Furthermore, since the resin material of the present invention has the above-mentioned structure, the elongation characteristic of the cured resin material can be improved.

The resin material of the present invention may be a resin composition or a resin film. The above-mentioned resin composition has fluidity. The above-mentioned resin composition may be in a paste form. The above-mentioned paste state includes a liquid state. In terms of excellent handling properties, the resin material of the present invention is preferably a resin film.

The resin material of the present invention is preferably a thermosetting resin material. When the above-mentioned 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 of the present invention and the use of the resin material of the present invention will be described.

[Compound X] The resin material of the present invention includes a compound X having a structure represented by the following formula (X). The structure represented by the following formula (X) has a skeleton derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride. The structure represented by the following formula (X) has an imine skeleton. Therefore, compound X has an imine skeleton. The compound X is preferably a thermosetting compound. Compound X may use only one type, or two or more types may be used in combination. Hereinafter, the preferable structure etc. which can exhibit the effect of this invention more effectively are demonstrated concretely.

[化4]

In the above formula (X), R represents an organic group, and n represents a number of 1 or more.

In the above formula (X), n preferably represents a number of 2 or more, and preferably represents a number of 20 or less, and more preferably represents a number of 10 or less.

In the above formula (X), as R, a group having an aliphatic ring and the like can be mentioned. Examples of the group having an aliphatic ring include a group having a cyclohexane ring, a group forming a part of the skeleton derived from dimer diamine, and the like.

From the viewpoint of further effectively exerting the effects of the present invention, in the above formula (X), R is preferably a group having an aliphatic ring, and more preferably a group having a cyclohexane ring.

Furthermore, in this specification, the so-called cyclohexane ring refers to an alicyclic structure of a six-membered ring formed by cyclic bonding of six carbon atoms. The carbon atoms constituting the cyclohexane ring may be bonded to a hydrocarbon group having a carbon number of 1 or more and 20 or less, or may be bonded to a hydrocarbon group having a carbon number of 1 or more and 4 or less. In addition, the above-mentioned compound X may have a tricyclodecane ring, a nordecane ring, and a cyclohexane ring as a ring constituting the adamantane skeleton and the like. In addition, the aforementioned compound X may have a structure in which a plurality of cyclohexane rings are connected via a hydrocarbon group such as an alkyl group.

In the case where R in the above formula (X) has a cyclohexane ring group, it is preferable that the carbon atoms constituting the cyclohexane ring be derived from 3,3',4,4'-biphenyltetracarboxylic acid The nitrogen atoms in the skeleton of the acid dianhydride are directly bonded or bonded via 3 or less atoms. The atom is preferably a carbon atom.

When R in the above formula (X) has the above tricyclodecane ring as the cyclohexane ring, it is preferable that the carbon atoms constituting the tricyclodecane ring are derived from 3,3',4,4' -The nitrogen atom in the skeleton of biphenyltetracarboxylic dianhydride is directly bonded or bonded via 2 or less atoms. The atom is preferably a carbon atom.

From the viewpoint of further effectively exerting the effects of the present invention, in the above formula (X), R is preferably the following formula (A1), the following formula (A2), the following formula (A3), and the following A group represented by the formula (A4), the following formula (A5), the following formula (A6), or the following formula (A7).

[化5]

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. In the above formula (A1), R1 to R10 are each preferably a hydrogen atom or a methyl group. In the above formula (A1), R1 to R10 may be the same or different.

The group represented by the above formula (A1) has a cyclohexane ring.

In the structure represented by the above formula (X) having the group represented by the above formula (A1), the carbon atoms constituting the cyclohexane ring are derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride The nitrogen atom in the skeleton is bonded via a carbon atom.

[化6]

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. In the above formula (A2), R1 to R10 are each preferably a hydrogen atom or a methyl group. In the above formula (A2), R1 to R10 may be the same or different.

The group represented by the above formula (A2) has a cyclohexane ring.

In the structure represented by the above formula (X) having the group represented by the above formula (A2), the first carbon atom (the carbon atom on the left side) constituting the cyclohexane ring is derived from 3,3',4,4' -The nitrogen atom in the skeleton of biphenyltetracarboxylic dianhydride is directly bonded. In the structure represented by the above formula (X) having the group represented by the above formula (A2), the second carbon atom (the carbon atom on the right side) constituting the cyclohexane ring is derived from 3,3',4,4' -The nitrogen atom in the skeleton of biphenyltetracarboxylic dianhydride is bonded via one carbon atom.

[化7]

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. In the above formula (A3), R1 to R10 are each preferably a hydrogen atom or a methyl group. In the above formula (A3), R1 to R10 may be the same or different.

The group represented by the above formula (A3) has a cyclohexane ring.

In the structure represented by the above formula (X) having the group represented by the above formula (A3), the first carbon atom (the carbon atom on the left side) constituting the cyclohexane ring is derived from 3,3',4,4' -The nitrogen atom in the skeleton of biphenyltetracarboxylic dianhydride is bonded via 2 carbon atoms. In the structure represented by the above formula (X) having the group represented by the above formula (A3), the second carbon atom (the carbon atom on the right side) constituting the cyclohexane ring is derived from 3,3',4,4 The nitrogen atom in the skeleton of'-biphenyltetracarboxylic dianhydride is directly bonded.

[化8]

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, and Q represents an arbitrary group. In the above formula (A4), R1 to R18 are each preferably a hydrogen atom or a methyl group. In the above formula (A4), Q is preferably a hydrocarbon group having a carbon number of 1 or more and 4 or less, or a group having an aromatic ring, more preferably an alkylene group, and still more preferably a methylene group. In the above formula (A4), when Q is a group having an aromatic ring, Q may also 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.

The group represented by the above formula (A4) has a cyclohexane ring.

In the structure represented by the above formula (X) having the group represented by the above formula (A4), the first carbon atom (the carbon atom on the left side) constituting the cyclohexane ring is derived from 3,3',4,4' -The nitrogen atom in the skeleton of biphenyltetracarboxylic dianhydride is directly bonded. In the structure represented by the above formula (X) having the group represented by the above formula (A4), the second carbon atom (the carbon atom on the right side) constituting the cyclohexane ring is derived from 3,3',4,4' -The nitrogen atom in the skeleton of biphenyltetracarboxylic dianhydride is directly bonded.

[化9]

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. In the above formula (A5), R1 to R8 are each preferably a hydrogen atom or a methyl group. In the above formula (A5), R1 to R8 may be the same or different.

Furthermore, in the above formula (X), R may be a group represented by the following formula (A5-1).

[化10]

In the above formula (A5-1), R1 to R10 each represent a hydrogen atom or a hydrocarbon group having a carbon number of 1 or more and 20 or less, and two of R1 to R10 represent a group that is bonded to the nitrogen atom constituting the imine skeleton. In the above formula (A5-1), the case where R9 and R10 represent a group bonded to the nitrogen atom constituting the imidine skeleton corresponds to the above formula (A5).

The group represented by the above formula (A5) and the above formula (A5-1) has a nordane ring.

In the structure represented by the above formula (X) having the group represented by the above formula (A5) and the above formula (A5-1), the carbon atoms constituting the cyclohexane ring are derived from 3,3',4,4' -The nitrogen atom in the skeleton of biphenyltetracarboxylic dianhydride is bonded via one carbon atom.

[化11]

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. In the above formula (A6), R1 to R12 are each preferably a hydrogen atom or a methyl group. In the above formula (A6), R1 to R12 may be the same or different.

Furthermore, in the above formula (X), R may be a group represented by the following formula (A6-1).

[化12]

In the above formula (A6-1), R1 to R14 each represent a hydrogen atom or a hydrocarbon group having a carbon number of 1 or more and 20 or less, and two of R1 to R14 represent a group that is bonded to the nitrogen atom constituting the imine skeleton. In the above formula (A6-1), the case where R13 and R14 represent a group bonded to the nitrogen atom constituting the amide skeleton corresponds to the above formula (A6).

The group represented by the above formula (A6) and the above formula (A6-1) has a tricyclodecane ring.

In the structure represented by the above formula (X) having the group represented by the above formula (A6) and the above formula (A6-1), the first carbon atom (the carbon atom on the left side) constituting the cyclohexane ring is derived from 3 The nitrogen atom in the skeleton of ,3',4,4'-biphenyltetracarboxylic dianhydride is bonded via 1 carbon atom. In the structure represented by the above formula (X) having the group represented by the above formula (A6) and the above formula (A6-1), the second carbon atom (the carbon atom on the right side) constituting the cyclohexane ring is derived from 3 The nitrogen atom in the skeleton of ,3',4,4'-biphenyltetracarboxylic dianhydride is bonded via 2 carbon atoms. In the structure represented by the above formula (X) having the group represented by the above formula (A6) and the above formula (A6-1), the second carbon atom (the carbon atom on the right side) constituting the tricyclodecane ring is derived from The nitrogen atom in the skeleton of 3,3',4,4'-biphenyltetracarboxylic dianhydride is bonded via 1 carbon atom.

[化13]

The group represented by the above formula (A7) has a cyclohexane ring. The group represented by the above formula (A7) is a group derived from dimer diamine. When synthesizing the compound X having the group represented by the above formula (A7), dimer diamine is used as a raw material. However, since dimer diamine is a natural product (mixture), it is difficult to define the structure of the dimer diamine as a structure. Therefore, in the obtained compound X, in addition to the group represented by the above formula (A7), there may be, for example, a compound having a group having a double bond in the above formula (A7).

From the viewpoint of further effectively exerting the effects of the present invention, with regard to the above compound X, in the above formula (X), R preferably has a partial skeleton derived from a dimer diamine skeleton, and preferably has Part of the skeleton derived from the skeleton of a diamine compound other than dimer diamine.

From the viewpoint of further effectively exerting the effects of the present invention, it is preferable that in the above formula (X), the nitrogen atom constituting the imine skeleton is only bonded to the carbon atom constituting the aliphatic skeleton. From the viewpoint of further effectively exerting the effects of the present invention, it is preferable that in the above compound X, the nitrogen atom constituting the imine skeleton is only bonded to the carbon atom constituting the aliphatic skeleton.

From the viewpoint of further effectively exerting the effects of the present invention, regarding the compound X, in the formula (X), as R, it is preferable to have the formula (A5), the formula (A6), or the formula (A7). The group represented by) more preferably has the group represented by the above formula (A6) or the above (A7).

From the viewpoint of further improving the desmear property and the viewpoint of further improving the thermal dimensional stability, with respect to the above-mentioned compound X, in the above-mentioned formula (X), R preferably has the above-mentioned formula (A5) or the above-mentioned formula (A6) represents the base. The reason is that the compound X having the group represented by the above formula (A5) or the above formula (A6) has a shorter distance between the imine skeletons than the compound X having the group represented by the above formula (A7), Therefore, it can increase the concentration of the imine skeleton in the molecule.

The compound X may have two structures represented by the above formula (X), two or more structures represented by the above formula (X), or three or more structures represented by the above formula (X).

For example, the aforementioned compound X may have a structure represented by the following formula (X1) as the structure represented by the aforementioned formula (X). The two skeletons of the structure represented by the following formula (X1) (the skeleton A on the left and the skeleton B on the right) can be randomly arranged (for example...A/B/A/B... etc.).

[化14]

In the above formula (X1), R1 and R2 each represent an organic group, and p and q each represent a number of 1 or more.

In the above formula (X1), p and q each preferably represent a number of 2 or more, and preferably represent a number of 10 or less, and more preferably represent a number of 7 or less.

In the above formula (X1), the combination of R1 and R2 is preferably the following first combination, and more preferably the following second combination.

The first combination: R1 is the above-mentioned formula (A1), the above-mentioned formula (A2), the above-mentioned formula (A3), the above-mentioned formula (A4), the above-mentioned formula (A5), or the above-mentioned formula (A6), and R2 is the above-mentioned formula (A7) .

The second combination: R1 is the above-mentioned formula (A6), and R2 is the above-mentioned formula (A7).

When the above formula (X1) is the above first combination, in the above formula (X1), p preferably represents a number of 1 or more, more preferably represents a number of 3 or more, and preferably represents a number of 18 or less , More preferably represents a number of 12 or less. When the above formula (X1) is the above first combination, in the above formula (X1), q more preferably represents a number of 1 or more, and preferably represents a number of 10 or less, and more preferably represents a number of 8 or less .

When the above formula (X1) is the above second combination, in the above formula (X1), p preferably represents a number of 2 or more, more preferably represents a number of 3 or more, and preferably represents a number of 18 or less , More preferably represents a number of 12 or less. When the above formula (X1) is the above second combination, in the above formula (X1), q preferably represents a number of 1 or more, more preferably represents a number of 2 or more, and preferably represents a number of 10 or less , More preferably represents a number of 8 or less.

Hereinafter, for the skeleton represented by the above formula (X) which can form the base represented by the above formula (A1), (A2), (A3), (A4), (A5), (A6) and (A7) The compound is further explained. Furthermore, it is possible to form a base different from the base represented by the above formula (A1), (A2), (A3), (A4), (A5), (A6), and (A7) as expressed by the above formula (X) The compound etc. of the skeleton shown are further explained.

The structure represented by the above formula (X) can be obtained, for example, by reacting a diamine compound with 3,3',4,4'-biphenyltetracarboxylic dianhydride.

The above-mentioned diamine compound may be an aliphatic diamine compound or a diamine compound different from the aliphatic diamine compound.

Examples of aliphatic diamine compounds include dimer diamine, tricyclodecane diamine, 1,3-bis(aminomethyl)cyclohexane, and 1,4-bis(aminomethyl)cyclohexane Alkane, bis(aminomethyl)nor ethane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.02,6]decane, 1,3-cyclohexanedi Amine, 1,4-cyclohexanediamine, isophoronediamine, 4,4'-methylenebis(cyclohexylamine), and 4,4'-methylenebis(2-methyl ring Hexylamine) and so on. Only one type of aliphatic diamine compound may be used, or two or more types may be used in combination.

Examples of the dimer diamine include: VERSAMINE 551 (trade name, 3,4-bis(1-aminoheptyl)-6-hexyl-5-(1-octenyl) ring manufactured by BASF Japan Hexene), VERSAMINE 552 (trade name, hydride of VERSAMINE 551 manufactured by Cognis Japan), PRIAMINE 1075, and PRIAMINE 1074 (trade name, all manufactured by Croda Japan), etc.

From the viewpoint of further reducing the dielectric loss factor of the hardened material, the above-mentioned dimer diamine is preferably the dimer diamine of "PRIAMINE 1075" manufactured by Croda Japan.

From the viewpoint of further improving the scum removal performance, the above-mentioned dimer diamine is preferably the dimer diamine of "PRIAMINE 1074" manufactured by Croda Japan.

From the viewpoint of further effectively exerting the effects of the present invention, the aliphatic diamine compound is preferably a compound having 36 carbon atoms or less.

From the viewpoint of further effectively exerting the effects of the present invention, the above-mentioned aliphatic diamine compound is preferably dimer diamine, tricyclodecane diamine, bis(aminomethyl)nordecane, isophor Ketone diamine or 4,4'-methylene bis(2-methylcyclohexylamine). From the viewpoint of further effectively exerting the effects of the present invention, the aliphatic diamine compound is more preferably dimer diamine, tricyclodecane diamine, or bis(aminomethyl)norcarne. When the aliphatic diamine compound is bis(aminomethyl)norethane, the compound X has, for example, a group represented by the formula (A5). When the aliphatic diamine compound is tricyclodecane diamine, the compound X has, for example, a group represented by the formula (A6). When the aliphatic diamine compound is a dimer diamine, the compound X has, for example, a group represented by the formula (A7).

Examples of diamine compounds that are different from the above-mentioned aliphatic diamine compounds include: 1,1-bis(4-aminophenyl)cyclohexane, 2,7-diaminopyridine, and 4,4'-ethylene ethylene Diphenylamine, 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(2-ethyl-6-methylaniline), 1,4- Diaminobutane, 1,10-diaminodecane, 1,12-diaminododecane, 1,7-diaminoheptane, 1,6-diaminohexane, 1,5 -Diaminopentane, 1,8-diaminooctane, 1,3-diaminopropane, 1,11-diaminoundecane, 2-methyl-1,5-diaminopentan Alkane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, etc. The diamine compound different from the above-mentioned aliphatic diamine compound may use only 1 type, and may use 2 or more types together.

The diamine compound different from the above-mentioned aliphatic diamine compound may also be an aromatic diamine having a phenolic hydroxyl group. In this case, the coefficient of linear expansion can be further reduced.

The above compound X may have a skeleton derived from a reactant of a diamine compound and an acid dianhydride other than 3,3',4,4'-biphenyltetracarboxylic dianhydride.

Examples of acid dianhydrides other than the aforementioned 3,3',4,4'-biphenyltetracarboxylic dianhydride include tetracarboxylic dianhydride and the like. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-di Phenyl tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-linked Phenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride , 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4 -Dicarboxyphenoxy)diphenyl dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoro Isopropylidene diphthalic dianhydride, bis(phthalic acid) phenyl phosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis (Triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'- Diphenylmethane dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid Anhydride, and 5-(2,5-dioxatetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, etc.

From the viewpoint of reducing the dielectric loss factor of the cured product and the viewpoint of improving the thermal dimensional stability of the cured product, the above-mentioned compound X preferably has a maleimide skeleton.

The number of maleimide skeletons in the compound X is preferably 2 or more, more preferably 3 or more, and preferably 10 or less, more preferably 5 or less. If the number of the maleimide skeleton is more than the aforementioned lower limit and less than the aforementioned upper limit, the effects of the present invention can be more effectively exhibited.

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

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

From the viewpoint of further effectively exerting the effects of the present invention, the compound X preferably has a structure represented by the following formula (Y). [化15]

In the above formula (Y), R1 represents a tetravalent organic group, R2 represents an organic group, and m represents a number of 1 or more.

In the above formula (Y), m preferably represents a number of 2 or more, and preferably represents a number of 20 or less, and more preferably represents a number of 10 or less.

In the above formula (Y), as R1, a skeleton having no biphenyl skeleton can be mentioned, for example, skeletons derived from acid dianhydrides other than the above 3,3',4,4'-biphenyltetracarboxylic dianhydride can be mentioned . In the above-mentioned formula (Y), as R2, the same organic group as the organic group of R in the above-mentioned formula (X) can be exemplified.

From the viewpoint of further effectively exerting the effects of the present invention, in the above formula (Y), R1 preferably does not have a skeleton derived from phthalimide. From the viewpoint of further effectively exerting the effects of the present invention, in the above formula (Y), R1 preferably does not have an aromatic skeleton.

From the viewpoint of further effectively exerting the effects of the present invention, in the above formula (Y), R2 preferably does not have a skeleton derived from phthalimide.

In the above compound X, 100% of the total of the repetition number (n) of the structure represented by the above formula (X) and the repetition number (m) of the structure represented by the above formula (Y) is represented by the above formula (X) The number of repetitions (n) of the structure is preferably 10% or more, more preferably 20% or more, and preferably 90% or less, more preferably 75% or less, and more preferably 60% or less. In this case, the effect of the present invention can be more effectively exhibited.

The above compound X may have an even number of amide skeletons, an odd number of amide skeletons, or a mixture of a compound having an even number of amide skeletons and a compound having an odd number of amide skeletons.

The above-mentioned compound X can be synthesized in the following manner, for example. The diamine compound, dimer diamine, and 3,3',4,4'-biphenyltetracarboxylic dianhydride are reacted to obtain a first reactant. The obtained first reactant is reacted with maleic anhydride.

In addition, the compound X having a dimer diamine skeleton at the terminal can be synthesized as follows, for example. The diamine compound is reacted with 3,3',4,4'-biphenyltetracarboxylic dianhydride to obtain a first reactant having an acid anhydride structure at both ends. The obtained first compound is reacted with dimer diamine to obtain a second reactant. The obtained second reactant is reacted with maleic anhydride.

The weight average molecular weight of the compound X is preferably 1,000 or more, more preferably 3100 or more, still more preferably 4,500 or more, and preferably 100,000 or less, more preferably 70,000 or less, still more preferably 25,000 or less, particularly preferably 18,000 Below, the best is 15000 or less. If the weight average molecular weight is greater than or equal to the lower limit, the coefficient of linear expansion can be further reduced. In addition, if the weight average molecular weight exceeds 25,000, the melt viscosity of the resin material may increase compared with the case where the weight average molecular weight is 25,000 or less, and the embedding property on the uneven surface may decrease.

The weight average molecular weight of the above compound X represents the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

From the viewpoint of further improving the thermal dimensional stability of the cured product and the viewpoint of further improving the adhesion between the insulating layer and the metal layer, the glass transition temperature of the compound X is preferably 70°C or higher, more preferably 85°C or higher .

The above-mentioned glass transition temperature can be measured using a differential scanning calorimetry device (such as "Q2000" manufactured by TA Instruments), heated from -30°C to 260°C in a nitrogen atmosphere at a heating rate of 3°C/min, and according to the reverse of the reverse heat flow Find the curve point.

In 100% by weight of the components other than inorganic fillers and solvents in the resin material, the content of the compound X is preferably 3% by weight or more, more preferably 5% by weight or more, and still more preferably 10% by weight or more, and It is preferably 80% by weight or less, more preferably 70% by weight or less, and still more preferably 50% by weight or less. If the content of the above-mentioned compound X is above the above-mentioned lower limit, the dielectric loss factor of the hardened product can be further reduced, and the scum removal performance can be further improved. If the content of the above-mentioned compound X is below the above-mentioned upper limit, the surface roughness of the resin material after desmearing treatment can be reduced, and the embedding property for the unevenness of the substrate and the like can be improved.

[Thermosetting compound] The above-mentioned resin material preferably contains a thermosetting compound that does not have a structure represented by the following formula (100). The above-mentioned thermosetting compound is a thermosetting compound different from the above-mentioned compound X. Only one kind of the above-mentioned thermosetting compound may be used, or two or more kinds may be used in combination.

[化16]

In the above formula (100), R represents an organic group, and n represents a number of 1 or more.

Examples of the above-mentioned thermosetting compounds include: phenoxy compounds, oxetane compounds, maleimide compounds, epoxy compounds, cyanate compounds, vinyl compounds, polyarylate compounds, ortho Diallyl phthalate compounds, episulfide compounds, (meth)acrylic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, polysiloxane compounds, etc.

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 still more preferably contains an epoxy compound. The above-mentioned vinyl compound preferably contains a styrene compound or an acrylate compound, and preferably contains a styrene compound. In this case, the dielectric loss factor of the cured product can be further reduced, and the thermal dimensional stability of the cured product can be further improved.

＜Maleimide compound＞ The maleimide compound is a maleimide compound that does not have the structure represented by the above formula (100). The maleimide compound is different from the maleimide compound X described above. The maleimide compound mentioned above may be a citraconimine compound. Only one type of the maleimide compound may be used, or two or more types may be used in combination.

The above maleimide compound may be a bismaleimide compound.

As said maleimide compound, N-phenyl maleimide, N-alkyl bismaleimide, etc. are mentioned.

The maleimide compound may have a skeleton derived from a diamine compound other than dimer diamine or a triamine compound other than trimer triamine, or not.

The maleimide compound preferably has an aromatic skeleton.

Among the above maleimide compounds, it is preferable that the nitrogen atom in the maleimide skeleton is bonded to the aromatic ring.

From the viewpoint of further improving the thermal dimensional stability of the cured product, the content of the maleimide compound is preferably 0.5% by weight or more in 100% by weight of the components other than the solvent in the resin material. It is preferably 1% by weight or more, preferably 15% by weight or less, and more preferably 10% by weight or less.

The content of the maleimide compound in 100% by weight of the components other than the inorganic filler and solvent in the resin material is preferably 2.5% by weight or more, more preferably 5% by weight or more, and more preferably 50% by weight or less, more preferably 35% by weight or less, and still more preferably 20% by weight or less. If the content of the maleimide compound is above the above lower limit and below the above upper limit, the thermal dimensional stability of the cured product can be further improved.

From the viewpoint of effectively exerting the effects of the present invention, the molecular weight of the maleimide compound is preferably 500 or more, more preferably 1,000 or more, and preferably less than 30,000, more preferably less than 20000.

Regarding the molecular weight of the maleimide compound, when the maleimide compound is not a polymer, and when the structural formula of the maleimide compound can be specified, Refers to the molecular weight that can be calculated according to the structural formula. In addition, regarding the molecular weight of the maleimide compound, when the maleimide compound is a polymer, it means that it is measured by gel permeation chromatography (GPC) with polystyrene Converted weight average molecular weight.

Examples of commercially available products of the maleimide compound include: "BMI4000" and "BMI5100" manufactured by Daiwa Chemical Industry Co., Ltd., "MIR-3000" manufactured by Nippon Kayaku Co., Ltd., and Designer Molecules Inc. Manufactured "BMI-3000" and "BMI-689", etc.

＜Epoxy compound＞ As the above-mentioned epoxy compound, a conventionally known epoxy compound can be used. The epoxy compound is an organic compound having at least one epoxy group. As for the said epoxy compound, only 1 type may be used, and 2 or more types may be used together.

Examples of the epoxy compound include: bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, phenol novolak type epoxy compound, biphenyl type epoxy compound, and biphenol Aldehyde type epoxy compound, biphenol type epoxy compound, naphthalene type epoxy compound, sulphur type epoxy compound, phenol aralkyl type epoxy compound, naphthol aralkyl type epoxy compound, dicyclopentadiene Type epoxy compounds, anthracene type epoxy compounds, epoxy compounds with adamantane skeleton, epoxy compounds with tricyclodecane skeleton, naphthyl ether type epoxy compounds, and epoxy compounds with three nuclei on the skeleton, etc. .

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

The above-mentioned epoxy compound may be an epoxy compound having a fluorine atom.

From the viewpoint of further reducing the dielectric loss factor of the cured product and improving the thermal dimensional stability and flame retardancy, the above-mentioned epoxy compound preferably includes an epoxy compound having an aromatic skeleton, and preferably includes a naphthalene The epoxy compound having a skeleton or a phenyl skeleton is more preferably an epoxy compound having an aromatic skeleton.

From the viewpoint of further reducing the dielectric loss factor and improving the coefficient of linear expansion (CTE) of the cured product, the epoxy compound preferably includes a liquid epoxy compound at 25°C and a solid form at 25°C. The epoxy compound.

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

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

The molecular weight of the above-mentioned epoxy compound is more preferably 1000 or less. In this case, in 100% by weight of the components other than the solvent in the resin material, even if the content of the inorganic filler is 50% by weight or more, a resin material with higher fluidity can be obtained when the insulating layer is formed. Therefore, when the uncured resin material or the B-staged compound is laminated on the circuit board, the inorganic filler can be uniformly present.

Regarding the molecular weight of the epoxy compound, when the epoxy compound is not a polymer, and when the structural formula of the epoxy compound can be specified, it means the molecular weight that can be calculated from the structural formula. In addition, when the above-mentioned epoxy compound is a polymer, it means a weight average molecular weight.

From the viewpoint of further improving the thermal dimensional stability of the cured product, the content of the epoxy compound in 100% by weight of the components other than the solvent in the resin material is preferably 4% by weight or more, more preferably 7% by weight Above, 15% by weight or less is preferable, and 12% by weight or less is more preferable.

The content of the epoxy compound is preferably 15% by weight or more, more preferably 25% by weight or more, and preferably 50% by weight or less in 100% by weight of the components other than inorganic fillers and solvents in the resin material. More preferably, it is 40% by weight or less. If the content of the epoxy compound is above the above lower limit and below the above upper limit, the thermal dimensional stability of the cured product can be further improved.

The weight ratio of the content of the epoxy compound to the total content of the compound X and the following curing agent (the content of the epoxy compound/the total content of the compound X and the curing agent) is preferably 0.2 or more, more preferably Is 0.3 or more. The weight ratio of the content of the epoxy compound to the total content of the compound X and the following curing agent (the content of the epoxy compound/the total content of the compound X and the curing agent) is preferably 1 or less, more preferably It is 0.8 or less. If the weight ratio is greater than or equal to the aforementioned lower limit and less than or equal to the aforementioned upper limit, the dielectric loss factor can be further reduced, and the thermal dimensional stability can be further improved.

＜Ethylene compounds＞ As the above-mentioned ethylene-based compound, a conventionally known ethylene-based compound can be used. The above-mentioned vinyl compound is an organic compound having at least one vinyl group. Only one type of the above-mentioned vinyl compound may be used, or two or more types may be used in combination.

As said vinyl compound, a styrene compound, an acrylate compound, a divinyl compound, etc. are mentioned. As said divinyl compound, a divinyl benzyl ether compound is mentioned. The above-mentioned vinyl compound may be a divinyl compound having an aliphatic skeleton, or may be a divinyl ether compound.

Examples of the above-mentioned styrene compounds include terminal styrene-modified phenylene ether compounds. Only one kind of the above-mentioned styrene compound may be used, or two or more kinds may be used in combination.

As a commercially available product of the styrene compound, for example, "OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd. can be cited.

In addition, vinyl compounds such as the above-mentioned styrene compound and the above-mentioned acrylate compound also correspond to a radical curable compound. Therefore, it is preferable that the said thermosetting compound contains a radical-hardening compound. The above-mentioned resin material preferably contains a radical curable compound.

In 100% by weight of the components other than inorganic fillers and solvents in the resin material, the content of the ethylene compound is preferably 5% by weight or more, more preferably 10% by weight or more, and still more preferably 20% by weight or more, And it is preferably 80% by weight or less, more preferably 70% by weight or less. If the content of the ethylene-based compound is more than the aforementioned lower limit and less than the aforementioned upper limit, the thermal dimensional stability of the cured product can be further improved.

[Inorganic Filler] The above-mentioned resin material preferably contains an inorganic filler. By using the above-mentioned inorganic filler, the dielectric loss factor of the hardened material can be further reduced. In addition, by using the above-mentioned inorganic filler, the dimensional change caused by the heat of the hardened product is further reduced. Only one kind of the above-mentioned inorganic filler may be used, or two or more kinds may be used in combination.

Examples of the above-mentioned inorganic fillers include silica, talc, clay, mica, hydrotalcite, alumina, magnesia, aluminum hydroxide, diamond, aluminum nitride, and boron nitride.

The above-mentioned 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.

From the viewpoint of reducing the surface roughness of the hardened object, further improving the bonding strength between the hardened object and the metal layer, and forming finer wiring on the surface of the hardened object, and using the hardened object to provide good insulation reliability, The above-mentioned inorganic filler is preferably silica or alumina, more preferably silica, and still more preferably fused silica. The above-mentioned silicon dioxide may be hollow silicon dioxide. By using silicon dioxide, the thermal expansion rate of the hardened material is further reduced, and the dielectric loss factor of the hardened material is further reduced. In addition, by using silicon dioxide, the surface roughness of the hardened object surface is effectively reduced, and the bonding strength between the hardened object and the metal layer is effectively increased. The shape of silicon dioxide is preferably spherical.

From the viewpoint of curing the resin without depending on the curing environment, effectively increasing the glass transition temperature of the cured product, and effectively reducing the thermal linear expansion coefficient of the cured product, the above-mentioned inorganic filler is preferably spherical silica.

From the viewpoint of improving thermal conductivity and improving insulation, the above-mentioned inorganic filler is preferably alumina or boron nitride. In particular, because boron nitride has anisotropy, it can further reduce the thermal linear expansion coefficient.

The average particle diameter of the above-mentioned inorganic filler is preferably 50 nm or more, more preferably 100 nm or more, still more preferably 500 nm or more, and preferably 5 μm or less, more preferably 3 μm or less, and still more preferably 1 Below μm. If the average particle size of the above-mentioned inorganic filler is above the above lower limit and below the above upper limit, the surface roughness after etching can be reduced, the peeling strength of plating can be improved, and the adhesion between the insulating layer and the metal layer can be further improved .

As the average particle diameter of the above-mentioned inorganic filler, a value that becomes 50% of the median diameter (d50) is adopted. The above-mentioned average particle size can be measured using a particle size distribution measuring device of a laser diffraction scattering method. Furthermore, when the inorganic filler is agglomerated particles, the average particle diameter of the inorganic filler refers to the primary particle diameter.

The above-mentioned inorganic filler is preferably spherical, more preferably spherical silica. In this case, the surface roughness of the surface of the hardened object is effectively reduced, and the bonding strength between the hardened object 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 above-mentioned inorganic filler is preferably surface-treated, more preferably a surface-treated product using a coupling agent, and still more preferably a surface-treated product using a silane coupling agent. With the above-mentioned inorganic filler undergoing surface treatment, the surface roughness of the surface of the roughened hardened product is further reduced, and the bonding strength between the hardened product and the metal layer becomes higher. In addition, by surface treatment of the above-mentioned inorganic filler, finer wiring can be formed on the surface of the hardened product, and better inter-wiring insulation reliability and interlayer insulation reliability can be imparted to the hardened product.

As said coupling agent, a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, etc. are mentioned. Examples of the silane coupling agent include methacrylic silane, acrylic silane, amino silane, imidazole silane, vinyl silane, epoxy silane, and the like.

In 100% by weight of the components other than the solvent in the resin material, the content of the above-mentioned inorganic filler 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, and 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. If the content of the above-mentioned inorganic filler is more than the above-mentioned lower limit, the dielectric loss factor is effectively reduced. If the content of the above-mentioned inorganic filler is not more than the above-mentioned upper limit, the thermal dimensional stability can be improved and the warpage of the cured product can be effectively suppressed. If the content of the inorganic filler is above the above lower limit and below the above upper limit, the surface roughness of the surface of the hardened product can be further reduced, and finer wiring can be formed on the surface of the hardened product. Furthermore, if it is the content of the inorganic filler, the thermal expansion rate of the hardened product can also be reduced, and the sludge removability can be improved at the same time.

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

Examples of the above-mentioned hardener include: phenol compounds (phenol hardeners), active ester compounds, cyanate ester compounds (cyanate ester hardeners), and benzo ketone compounds (benzo ketone hardeners) that do not have an imine bond. Agents), carbodiimide compounds (carbodiimide hardeners), amine compounds (amine hardeners), thiol compounds (thiol hardeners), phosphine compounds, dicyandiamide, and acid anhydrides. The curing agent preferably has a functional group capable of reacting with the epoxy group of the epoxy compound.

From the viewpoint of further improving the thermal dimensional stability and the viewpoint of further reducing the dielectric loss factor, the above-mentioned hardener preferably includes a phenol compound, an active ester compound, a cyanate ester compound, and a benzoic acid compound without an imine bond. At least one component of 㗁𠯤 compound, carbodiimide compound and acid anhydride. From the viewpoint of further improving the thermal dimensional stability and the viewpoint of further reducing the dielectric loss factor, the above-mentioned hardener is more preferably composed of a phenol compound, an active ester compound, a cyanate ester compound, and a benzoyl compound without an imine bond. At least one of the 㗁𠯤 compound and the carbodiimide compound further preferably contains an active ester compound.

From the viewpoint of further improving the thermal dimensional stability and the viewpoint of further reducing the dielectric loss factor, the thermosetting compound includes an epoxy compound, and the hardener preferably includes both a phenol compound and an active ester compound.

As said phenol compound, a novolak type phenol, a biphenol type phenol, a naphthalene type phenol, a dicyclopentadiene type phenol, an aralkyl type phenol, a dicyclopentadiene type phenol, etc. are mentioned.

Commercial products of the above-mentioned phenol compounds include: novolac type phenol ("TD-2091" manufactured by DIC Corporation), biphenol novolac type phenol ("MEH-7851" manufactured by Meiwa Chemical Co., Ltd.), and aralkyl groups Type phenolic compound ("MEH-7800" manufactured by Meiwa Chemical Co., Ltd.), and phenol with an amino tris-frame ("LA-1356" and "LA-3018-50P" manufactured by DIC Company), etc.

The above-mentioned active ester compound refers to a compound containing at least one ester bond in the structure, and an aliphatic chain, aliphatic ring, or aromatic ring is bonded to both sides of the ester bond. The active ester compound is obtained, for example, by the condensation reaction of a carboxylic acid compound or a thiocarboxylic acid compound and a hydroxyl compound or a thiol compound. As an example of an active ester compound, the compound represented by following formula (1) can be mentioned.

[化17]

In the above formula (1), X1 represents an aliphatic chain-containing group, an aliphatic ring-containing group, or an aromatic ring-containing group, and X2 represents an aromatic ring-containing group. As a preferable example of the group containing an aromatic ring mentioned above, the benzene ring which may have a substituent, the naphthalene ring which may have a substituent, etc. are mentioned. As said substituent, a hydrocarbon group can be mentioned. The carbon number of the hydrocarbon group is preferably 12 or less, more preferably 6 or less, and still more preferably 4 or less.

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, a benzene ring which may have a substituent and a naphthalene ring which may have a substituent的组合。 The combination. Furthermore, in the above formula (1), the combination of X1 and X2 includes a combination of a naphthalene ring which may have a substituent and a naphthalene ring which may have a substituent.

The above-mentioned active ester compound is not particularly limited. From the viewpoint of further improving thermal dimensional stability and flame retardancy, the above-mentioned active ester compound is preferably an active ester compound having two or more aromatic skeletons. From the viewpoint of reducing the dielectric loss factor of the cured product and improving the thermal dimensional stability of the cured product, the active ester compound preferably has a naphthalene ring or a dicyclopentadiene skeleton in the main chain skeleton.

When the resin material includes the epoxy compound and the active ester compound, it is preferable that at least one of the epoxy compound and the active ester compound has an amide skeleton or an amide skeleton. In this case, the effect of the present invention can be more effectively exhibited.

Commercial products of the above-mentioned active ester compounds include: "HPC-8000-65T", "EXB9416-70BK", "EXB8100-65T", "HPC-8150-62T" and "EXB-8" manufactured by DIC Corporation Wait.

From the viewpoint of reducing the melt viscosity of the resin material, shortening the distance between cross-linking points, and further reducing the linear expansion coefficient of the cured product, the above-mentioned 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 "EXB-8" manufactured by the aforementioned DIC company.

As said cyanate ester compound, a novolak type cyanate ester resin, a bisphenol type cyanate ester resin, and these prepolymers etc. which were partially trimerized are mentioned. As said novolak type cyanate resin, a phenol novolak type cyanate resin, an alkylphenol type cyanate resin, etc. are mentioned. As said bisphenol type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, tetramethyl bisphenol F type cyanate resin, etc. are mentioned.

Commercial products of the above-mentioned cyanate ester compounds include: phenol novolac type cyanate ester resins ("PT-30" and "PT-60" manufactured by Lonza Japan), and bisphenol type cyanate ester resins Prepolymers made by trimerization ("BA-230S", "BA-3000S", "BTP-1000S" and "BTP-6020S" manufactured by Lonza Japan), etc.

The content of the cyanate ester compound is preferably 10% by weight or more, more preferably 15% by weight or more, and still more preferably 20% by weight or more in 100% by weight of the components other than the inorganic filler and solvent in the resin material , And preferably 85% by weight or less, more preferably 75% by weight or less. If the content of the cyanate ester compound is greater than or equal to the aforementioned lower limit and less than the aforementioned upper limit, the thermal dimensional stability of the cured product can be further improved.

As the above-mentioned benzodiazepine compound which does not have an imine bond, P-d type benzodiazepine, F-a type benzodiazepine, and the like can be cited.

Examples of commercially available products of the above-mentioned benzoxa compound without an imine bond include "P-d type" manufactured by Shikoku Kasei Kogyo Co., Ltd., "ODA-BOZ" manufactured by JFE Chemical Co., Ltd., and the like.

In 100% by weight of the components other than inorganic fillers and solvents in the above resin material, the content of the above-mentioned benzophenone compound without an imine bond is preferably 1% by weight or more, more preferably 5% by weight or more, It is more preferably 10% by weight or more, more preferably 70% by weight or less, and more preferably 60% by weight or less. If the content of the above-mentioned benzophenone compound without an imine bond is above the above lower limit and below the above upper limit, the dielectric loss factor of the hardened product can be reduced, and the thermal dimensional stability can be further improved.

The above-mentioned 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 the bonding sites with other bases. As for the said carbodiimide compound, only 1 type may be used, and 2 or more types may be used together.

[化18]

In the above formula (2), X represents an alkylene group, a group formed by bonding a substituent to an alkylene group, a cycloalkylene group, a group formed by bonding a substituent to a cycloalkylene group, an aryl group , Or a group formed by bonding a substituent to an aryl group, p represents an integer of 1 to 5. When there are a plurality of Xs, the plurality of Xs may be the same or different.

In a suitable form, at least one X is an alkylene group, a group formed by bonding a substituent to an alkylene group, a cycloalkylene group, or a group formed by bonding a substituent to a cycloalkylene group .

Commercial products of the above-mentioned carbodiimide compounds include: "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", and "Carbodilite V-02B" manufactured by Nisshinbo Chemical Co., Ltd. "Carbodilite V-09", "Carbodilite 10M-SP", and "Carbodilite 10M-SP (modified)", as well as "Stabaxol P", "Stabaxol P400", and "Hycasyl 510" manufactured by Rhein Chemie.

Examples of the acid anhydride include tetrahydrophthalic anhydride and alkylstyrene-maleic anhydride copolymers.

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

The content of the curing agent relative 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, and preferably 150 parts by weight or less, and more preferably 120 parts by weight or less. If the content of the curing agent is more than the aforementioned lower limit and less than the aforementioned upper limit, the curability is more excellent, the thermal dimensional stability can be further improved, and the volatilization of remaining unreacted components can be further suppressed.

The total content of the above-mentioned compound X, the above-mentioned thermosetting compound, and the above-mentioned hardener in 100% by weight of the components other than the inorganic filler and the solvent in the above-mentioned resin material is preferably 40% by weight or more, more preferably 60% by weight or more , And preferably 98% by weight or less, more preferably 95% by weight or less. If the total content of the compound X, the thermosetting compound, and the curing agent is greater than or equal to the aforementioned lower limit and less than or equal to the aforementioned upper limit, the curability is more excellent, and the thermal dimensional stability can be further improved.

[Hardening accelerator] The above-mentioned resin material contains a hardening accelerator. By using the above-mentioned hardening accelerator, the hardening speed becomes faster. By using the resin material to harden quickly, the cross-linked structure in the hardened product becomes uniform, and the number of unreacted functional groups is reduced, resulting in an increase in the cross-linking density. The above-mentioned hardening accelerator is not particularly limited, and conventionally known hardening accelerators can be used. Only one kind of the above-mentioned hardening accelerator may be used, or two or more kinds may be used in combination.

Examples of the above-mentioned hardening accelerator include anionic hardening accelerators such as imidazole compounds, cationic hardening accelerators such as amine compounds, hardening accelerators other than anionic and cationic hardening accelerators such as phosphorus compounds and organometallic compounds, and Radical hardening accelerators such as peroxides, etc.

Examples of the imidazole compound include: 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-benzene 4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole , 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl- 2-Undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methyl Imidazolyl-(1')]-ethyl-symmetric tris, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-symmetric tris, 2,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-symmetric tris, 2,4-diamino-6-[2 '-Methylimidazolyl-(1')]-Ethyl-symmetric triisocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isotrimer Cyanate adducts, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-dihydroxymethylimidazole, etc.

As said amine compound, diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, 4, 4- dimethylamino pyridine, etc. are mentioned.

As said phosphorus compound, a triphenyl phosphine compound etc. are mentioned.

As said organometallic compound, zinc naphthenate, cobalt naphthenate, tin octoate, cobalt octoate, cobalt diacetone (II), cobalt triacetone (III), etc. are mentioned.

As said peroxide, dicumyl peroxide, PERHEXYL25B, etc. are mentioned.

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

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

In the case where the thermosetting compound contains a radical curable compound such as the vinyl compound, the acrylate compound, and the styrene compound, radical curing is performed. Therefore, the curing accelerator preferably contains the radical curing compound. Accelerator.

The content of the above-mentioned hardening accelerator is not particularly limited. In 100% by weight of the components other than the inorganic filler and solvent in the resin material, the content of the hardening accelerator is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and preferably 5% by weight or less, and more It is preferably 3% by weight or less. If the content of the hardening accelerator is greater than or equal to the aforementioned lower limit and less than or equal to the aforementioned upper limit, the resin material is cured efficiently. If the content of the above-mentioned hardening accelerator is in a better range, the storage stability of the resin material becomes higher, and a better hardened product can be obtained.

[Thermoplastic resin] The above-mentioned resin material preferably contains a thermoplastic resin. As said thermoplastic resin, polyvinyl acetal resin, polyimide resin, phenoxy resin, styrene butadiene resin, etc. are mentioned. As for the said thermoplastic resin, only 1 type may be used, and 2 or more types may be used together.

From the viewpoint of effectively reducing the dielectric loss factor without depending on the curing environment, and effectively improving the adhesion of the metal wiring, the above-mentioned thermoplastic resin is preferably a phenoxy resin. By using phenoxy resin, it is possible to suppress the deterioration of the embedding property of the resin film into the holes or unevenness of the circuit board and the unevenness of the inorganic filler. In addition, by using phenoxy resin, the melt viscosity can be adjusted, so the dispersibility of the inorganic filler becomes good, and during the curing process, the resin composition or the B-stage compound is difficult to wet and spread in undesired areas.

The phenoxy resin contained in the above resin material is not particularly limited. As the above-mentioned phenoxy resin, a conventionally known phenoxy resin can be used. As for the said phenoxy resin, only 1 type may be used, and 2 or more types may be used together.

Examples of the above-mentioned phenoxy resin include those having a bisphenol A type skeleton, a bisphenol F type skeleton, a bisphenol S type skeleton, a biphenyl skeleton, a novolak skeleton, a naphthalene skeleton, and an amide skeleton. Phenoxy resin etc.

Examples of commercially available products of the above-mentioned phenoxy resin include: "YP50", "YP55" and "YP70" manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation, and "1256B40", "4250", and "Mitsubishi Chemical Corporation" manufactured by Mitsubishi Chemical Corporation. 4256H40", "4275", "YX6954BH30" and "YX8100BH30" etc.

From the viewpoints of improving handleability, plating peel strength at low thickness, and adhesion between the insulating layer and the metal layer, the above-mentioned thermoplastic resin is preferably a polyimide resin (polyimide compound).

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

Examples of the tetracarboxylic dianhydride include: pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-di Phenyl tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-linked Phenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride , 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4 -Dicarboxyphenoxy)diphenyl dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoro Isopropylidene diphthalic acid dianhydride, bis(phthalic acid) phenyl phosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis (Triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, and bis(triphenylphthalic acid)-4,4' -Diphenylmethane dianhydride, etc.

As said aliphatic diamine, dimer diamine etc. are mentioned. As the dimer diamine, for example, VERSAMINE 551 (trade name 3,4-bis(1-aminoheptyl)-6-hexyl-5-(1-octenyl)cyclohexyl) manufactured by BASF Japan Ene), VERSAMINE 552 (trade name, hydride of VERSAMINE 551 manufactured by Coconic Japan), PRIAMINE 1075, PRIAMINE 1074 (trade name, all manufactured by Croda Japan), etc.

Furthermore, the above-mentioned polyimide compound may have an acid anhydride structure, a maleimide structure, and a citraconic imine structure at the end. In this case, the above-mentioned polyimide compound and epoxy compound can be reacted. By reacting the above-mentioned polyimide compound with an epoxy compound, the thermal dimensional stability of the cured product can be improved.

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

The weight average molecular weight of the thermoplastic resin, the polyimide resin, and the phenoxy resin means the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The content of the thermoplastic resin, the polyimide resin, and the phenoxy resin is not particularly limited. The content of the above-mentioned thermoplastic resin in 100% by weight of the above-mentioned inorganic filler and the above-mentioned solvent in the resin material (when the thermoplastic resin is polyimide resin or phenoxy resin, polyimide resin or benzene The content of the oxy resin is preferably 1% by weight or more, more preferably 2% by weight or more, and preferably 30% by weight or less, and more preferably 20% by weight or less. If the content of the thermoplastic resin is greater than or equal to the aforementioned lower limit and less than or equal to the aforementioned upper limit, the embedding properties of the holes or irregularities of the resin material circuit board become good. If the content of the thermoplastic resin is greater than or equal to the lower limit, it becomes easier to form a resin film, and a better insulating layer can be obtained. If the content of the thermoplastic resin is less than or equal to the upper limit, the thermal expansion coefficient of the cured product is further reduced. If the content of the above-mentioned thermoplastic resin is below the above-mentioned upper limit, the surface roughness of the surface of the cured product is further reduced, and the bonding strength between the cured product and the metal layer becomes higher.

[Solvent] The above-mentioned resin material does not contain or contains a solvent. By using the above-mentioned solvent, the viscosity of the resin material can be controlled within an appropriate range, and the coating property of the resin material can be improved. In addition, the above-mentioned solvent can be used to obtain a slurry containing the above-mentioned inorganic filler. Only one kind of the above-mentioned solvent may be used, or two or more kinds may be used in combination.

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

Most of the above-mentioned solvents are preferably removed when the above-mentioned resin composition is formed into a film shape. Therefore, the boiling point of the above-mentioned 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 coating properties 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, it is 5 wt% or less.

[Other ingredients] In order to improve impact resistance, heat resistance, resin compatibility and workability, the above resin materials may also include organic fillers, leveling agents, flame retardants, coupling agents, colorants, antioxidants, anti-ultraviolet degradation agents, Antifoaming agent, tackifier, and denaturation imparting agent, etc.

Examples of the above-mentioned organic filler include particulate matter containing benzoxazole resin, benzoxazole resin, fluororesin, acrylic resin, and styrene resin. As said fluororesin, polytetrafluoroethylene (PTFE) etc. are mentioned. By using fluororesin particles as the above-mentioned organic filler, the relative dielectric constant of the cured product can be further reduced. The average particle diameter of the organic filler is preferably 1 μm or less. If the average particle size of the organic filler is below the above upper limit, the surface roughness after etching can be reduced, the plating peel strength can be improved, and the adhesion between the insulating layer and the metal layer can be further improved. The average particle size of the organic filler may be 50 nm or more.

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

As said coupling agent, a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, etc. are mentioned. As said silane coupling agent, vinyl silane, amino silane, imidazole silane, epoxy silane, etc. are mentioned.

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

As a method of forming a resin composition into a film shape to obtain a resin film, the following methods can be cited. An extrusion molding method in which the resin composition is melted and kneaded using an extruder, and after extrusion, it is molded into a film shape using a T-die or a circular die. A casting method of casting a resin composition containing a solvent into a film shape. Previously known other film forming methods. In terms of being able to cope with thinning, an extrusion molding method or a cast molding method is preferable. The film contains a sheet.

The resin composition is formed into a film shape so that the hardening caused by heat does not proceed excessively, for example, by heating and drying at 50°C to 150°C for 1 minute to 10 minutes, thereby obtaining a resin film as a B-stage film.

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

The above-mentioned resin film may not be a prepreg. When the above-mentioned resin film is not a prepreg, no electron migration occurs along glass cloth or the like. In addition, when the resin film is laminated or pre-cured, the surface does not have unevenness caused by the glass cloth.

The above-mentioned resin film can be used in the form of a laminated film provided with a metal foil or a base film, and a resin film laminated on the surface of the metal foil or the base. The above-mentioned metal foil is preferably copper foil.

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

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

(Semiconductor devices, printed wiring boards, copper foil laminates and multilayer printed wiring boards) The above-mentioned resin material can be suitably used to form a mold resin for embedding a semiconductor chip in a semiconductor device.

The above-mentioned resin material can be suitably used as an insulating material. The above-mentioned resin material can be suitably used to form an insulating layer in a printed wiring board.

The printed wiring board can be obtained, for example, by heating and pressing the resin material.

The above-mentioned resin film may be a laminate target member having a metal layer on the surface of a single-sided or double-area layer. A laminated structure comprising: a member to be laminated having a metal layer on the surface; and a resin film laminated on the surface of the metal layer, wherein the resin film is the resin material, can be suitably 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, an apparatus such as a parallel plate press or a roll laminator can be used to laminate the above-mentioned resin film on a laminate target member having a metal layer on the surface while heating or pressing without heating.

The material of the metal layer is preferably copper.

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

The above-mentioned resin material can be suitably used for obtaining a copper foil laminated board. As an example of the said copper foil laminated board, the copper foil laminated board provided with the resin film laminated|stacked on one surface of the copper foil and this copper foil is mentioned.

The thickness of the said copper foil of the said copper foil laminated board is not specifically limited. The thickness of the above-mentioned copper foil is preferably in the range of 1 μm to 50 μm. In addition, in order to increase the bonding strength between the cured product of the resin material and the copper foil, the copper foil preferably has fine irregularities on the surface. The method of forming the unevenness is not particularly limited. As a method of forming the above-mentioned concavities and convexities, a method of forming using a treatment using a known chemical solution, etc., can be cited.

The above-mentioned resin materials can be suitably used to obtain a multilayer substrate.

As an example of the above-mentioned multilayer substrate, a multilayer substrate including a circuit substrate and an insulating layer laminated on the circuit substrate can be cited. The insulating layer of the multilayer substrate is formed using the above-mentioned resin material. In addition, the insulating layer of the multilayer substrate may also be a laminate film, and it may be formed using the above-mentioned resin film of the above-mentioned laminate film. The above-mentioned insulating layer is preferably laminated on the surface of the circuit board where the circuit is provided. A part of the above-mentioned insulating layer is preferably embedded between the above-mentioned circuits.

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

The roughening treatment method can use a previously known roughening treatment method, and it is not particularly limited. The surface of the above-mentioned insulating layer may also be subjected to swelling treatment before roughening treatment.

Moreover, it is preferable that the said multilayer board|substrate is further provided with the copper plating layer laminated|stacked on the roughened surface of the said insulating layer.

In addition, as another example of the above-mentioned multilayer substrate, the following multilayer substrate may be cited, which includes: a circuit substrate, an insulating layer laminated on the surface of the circuit substrate, and the insulating layer laminated on the surface opposite to the surface on which the circuit substrate is laminated The copper foil on the side of the surface. It is preferable that the said insulating layer is formed by hardening the said resin film using the copper foil laminated board provided with the copper foil and the resin film laminated|stacked on one surface of this copper foil. Furthermore, it is preferable that the said copper foil is etched, and it is a copper circuit.

As another example of the above-mentioned multilayer substrate, a multilayer substrate provided with a circuit substrate and a plurality of insulating layers laminated on the surface of the circuit substrate can be cited. At least one of the plurality of insulating layers arranged on the circuit board is formed using the resin material. The multilayer substrate preferably further includes a circuit laminated on at least one surface of the insulating layer formed using the resin film.

In a multilayer printed wiring board in a multilayer substrate, a lower dielectric loss factor is required, and a higher insulation reliability of the insulating layer is required. In the resin material of the present invention, by reducing the dielectric loss factor, and improving the adhesion and etching performance between the insulating layer and the metal layer, the insulation reliability can be effectively improved. Therefore, the resin material of the present invention can be 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 12 a of the circuit board 12. The insulating layers 13-16 are hardened layers. A metal layer 17 is formed in the area of a part of the upper surface 12a of the circuit board 12. Among the plurality of insulating layers 13-16, the insulating layers 13-15 other than the insulating layer 16 on the outer side opposite to the circuit board 12 side have a metal layer 17 formed in a part of the upper surface area. 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 13-16, respectively. The lower metal layer 17 and the upper metal layer 17 are connected to each other by at least one of via connection and through-hole connection not shown.

In the multilayer printed wiring board 11, the insulating layers 13-16 are formed using the hardened|cured material of the said resin material. In this embodiment, the surfaces of the insulating layers 13-16 are roughened, so that the surfaces of the insulating layers 13-16 are formed with fine holes (not shown). In addition, the metal layer 17 reaches the inside of the fine hole. In addition, in the multilayer printed wiring board 11, the widthwise dimension (L) of the metal layer 17 and the widthwise dimension (S) of the portion where the metal layer 17 is not formed can be reduced. Moreover, in the multilayer printed wiring board 11, good insulation reliability is provided between the upper metal layer and the lower metal layer which are not connected by via connection and through-hole connection which are not shown in figure.

(Roughening treatment and swelling treatment) The above-mentioned resin material is preferably used to obtain a hardened product that has undergone roughening treatment or desmearing treatment. The above-mentioned hardened material further includes a pre-hardened material that can be hardened.

In order to form fine concavities and convexities on the surface of the cured product obtained by pre-curing the above resin material, the cured product is preferably roughened. Before the roughening treatment, the hardened product is preferably subjected to swelling treatment. The hardened product is preferably subjected to swelling treatment after pre-hardening and before roughening treatment, and then hardening after roughening treatment. Among them, the hardened product may not necessarily undergo swelling treatment.

As the method of the above-mentioned swelling treatment, for example, a method of treating the hardened product with an aqueous solution of a compound mainly composed of ethylene glycol or the like or an organic solvent dispersion solution or the like can be used. The swelling liquid used in the swelling treatment usually contains an alkali as a pH adjuster or the like. The swelling liquid preferably contains sodium hydroxide. Specifically, for example, the above-mentioned swelling treatment is performed by a method of treating the cured product at a treatment temperature of 30°C to 85°C for 1 minute to 30 minutes using a 40% by weight ethylene glycol aqueous solution or the like. The temperature of the above-mentioned swelling treatment is preferably in the range of 50°C to 85°C. If the temperature of the above-mentioned swelling treatment is too low, the swelling treatment may take a long time, and the adhesive strength between the hardened product and the metal layer tends to decrease.

For the roughening treatment, for example, chemical oxidizing agents such as manganese compounds, chromium compounds, or persulfuric acid compounds can be used. These chemical oxidants can be used as aqueous solutions or organic solvent dispersion solutions after adding water or organic solvents. The roughening liquid used in the roughening treatment usually contains an alkali as a pH adjuster or the like. The roughening liquid preferably contains sodium hydroxide.

As said manganese compound, potassium permanganate, sodium permanganate, etc. are mentioned. As said chromium compound, potassium dichromate, anhydrous potassium chromate, etc. are mentioned. As said persulfuric acid compound, sodium persulfate, potassium persulfate, ammonium persulfate, etc. are mentioned.

The arithmetic average roughness Ra of the surface of the hardened object is preferably 10 nm or more, preferably less than 300 nm, more preferably less than 200 nm, and still more preferably less than 150 nm. In this case, the bonding strength between the hardened product and the metal layer is increased, and finer wiring is formed on the surface of the insulating layer. Furthermore, conductor loss can be suppressed, and signal loss can be suppressed low. The above-mentioned arithmetic average roughness Ra is measured in accordance with JIS B0601:1994.

(Desmear treatment) There are cases where through holes are formed in the cured product obtained by pre-curing the above-mentioned resin material. In the above-mentioned multilayer substrate or the like, as a through hole, a through hole, a through hole, or the like is formed. For example, the through hole can be formed by irradiating a laser such as a _{CO 2 laser.} The diameter of the through hole is not particularly limited, but is about 60 μm to 80 μm. By forming the above-mentioned through hole, in most cases, a scum, which is a residue of resin derived from the resin component contained in the hardened substance, is formed at the bottom of the through hole.

In order to remove the above-mentioned scum, the surface of the hardened object is preferably treated with scum removal. Desmear treatment is sometimes also used as a roughening treatment.

In the aforementioned desmear treatment, similar to the aforementioned roughening treatment, for example, chemical oxidizing agents such as manganese compounds, chromium compounds, or persulfuric acid compounds can be used. These chemical oxidants can be used as aqueous solutions or organic solvent dispersion solutions after adding water or organic solvents. The desmear treatment liquid used in the desmear treatment usually contains an alkali. The desmear treatment liquid preferably contains sodium hydroxide.

By using the above-mentioned resin material, the surface roughness of the surface of the hardened object after desmearing treatment becomes sufficiently small.

Hereinafter, the present invention will be explained concretely by way of examples and comparative examples. The present invention is not limited to the following examples.

Prepare the following materials.

(Compound X) Compound X-1: According to the following synthesis example 1, compound X-1 (molecular weight 4000) represented by the following formula (X-1) was synthesized.

＜Synthesis example 1＞ A 500 mL round bottom flask was charged with 90 g of toluene, 46 g of N-methyl-2-pyrrolidone (NMP), and 9 g of methanesulfonic acid. Then, 15.6 g (80 mmol) of tricyclodecane diamine was added. Then, 17.7 g (60 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride was gradually added in small amounts. Then, a round-bottomed flask was installed on the Dean-Stark device, and heating and refluxing were performed for 3.5 hours. In this way, a compound having an acid anhydride structure at the end and a plurality of imine skeletons is obtained. The water discharged during the condensation was removed, and after returning to room temperature, 4.42 g (45 mmol) of maleic anhydride was added and stirred, and the mixture was heated and reacted in the same manner. After washing the organic layer with a mixed solvent of water and ethanol, the mixed solvent is removed to obtain a toluene solution. Then, isopropanol was added to the toluene solution to perform reprecipitation of the product. Then, it was dried in a vacuum oven to obtain compound X-1.

[化19]

Compound X-2: According to the following synthesis example 2, compound X-2 (molecular weight 4500) represented by the following formula (X-2) was synthesized. In the obtained compound X-2, in 100 mol% of all structural units derived from the skeleton of the diamine compound, the average ratio of the first skeleton derived from tricyclodecane diamine was 72 mol%, which was derived from The average ratio of the second skeleton of dimer diamine is 28 mol%. Furthermore, the following formula (X-2) is an example of the compound X-2 obtained in Synthesis Example 2. The compound X-2 is obtained as a mixture of compounds with different positions of each amine.

＜Synthesis example 2＞ A 500 mL round bottom flask was charged with 90 g of toluene, 46 g of N-methyl-2-pyrrolidone (NMP), and 7 g of methanesulfonic acid. Next, 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 3,3',4,4'-biphenyltetracarboxylic dianhydride was gradually added in small amounts. A round-bottomed flask was installed on the Dean-Stark device and heated to reflux for 3.5 hours. In this way, a compound having an amine at both ends and a plurality of imidine skeletons is obtained. The water discharged during the condensation was removed, and after returning to room temperature, 4.42 g (45 mmol) of maleic anhydride was added and stirred, and the mixture was heated and reacted in the same manner. In this way, a compound having a maleimide skeleton at both ends is obtained. After washing the organic layer with a mixed solvent of water and ethanol, the mixed solvent is removed to obtain a toluene solution. Then, isopropanol was added to the toluene solution to perform reprecipitation of the product. Then, it was dried in a vacuum oven to obtain compound X-2.

[化20]

Compound X-3: According to the following synthesis example 3, compound X-3 (molecular weight 4200) represented by the following formula (X-3) was synthesized. In the obtained compound X-3, in 100 mol% of all structural units derived from the skeleton of the diamine compound, the average ratio of the first skeleton derived from tricyclodecane diamine is 75 mol%, which is derived from The average ratio of the second skeleton of dimer diamine is 25 mol%. Furthermore, the following formula (X-3) is an example of the compound X-3 obtained in Synthesis Example 3. The compound X-3 is obtained as a mixture of compounds having different positions of each amine.

＜Synthesis example 3＞ A 500 mL round bottom flask was charged with 90 g of toluene, 46 g of N-methyl-2-pyrrolidone (NMP), and 7 g of methanesulfonic acid. Then, 6.6 g (16 mmol) of dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan) and 9.9 g (64 mmol) of noralane diamine ("Pro-NBDA" manufactured by Mitsui Fine Chemicals) were added. , Mix 3,3',4,4'-biphenyltetracarboxylic dianhydride 15.9 g (54 mmol), and bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid After 1.5 g (6 mmol) of dianhydride, a small amount was added gradually. A round-bottom flask was installed on the Dean-Stark apparatus and heated to reflux for 3.5 hours. In this way, a product with an amine at both ends and a plurality of imine skeletons was obtained. Compound. After removing the water discharged during the condensation and returning to room temperature, 4.42 g (45 mmol) of maleic anhydride was added and stirred, and heated in the same way to react. In this way, the maleic acid at both ends was obtained. A compound of imine skeleton. After washing the organic layer with a mixed solvent of water and ethanol, the mixed solvent is removed to obtain a toluene solution of compound X-3.

[化21]

(Compounds not equivalent to compound X (compound Y)) Compound Y-1: According to Synthesis Example 4 below, compound Y-1 (molecular weight 3300) was synthesized.

＜Synthesis example 4＞ A 500 mL round bottom flask was charged with 90 g of toluene, 46 g of N-methyl-2-pyrrolidone (NMP), and 9 g of methanesulfonic acid. Then, 15.6 g (80 mmol) of tricyclodecane diamine was added. Then, 13.1 g (60 mmol) of pyromellitic dianhydride was gradually added in small amounts. Then, a round-bottomed flask was installed on the Dean-Stark device, and heating and refluxing were performed for 3.5 hours. In this way, a compound having an acid anhydride structure at the end and a plurality of imine skeletons is obtained. The water discharged during the condensation was removed, and after returning to room temperature, 4.42 g (45 mmol) of maleic anhydride was added and stirred, and the reaction was carried out by heating in the same manner. After washing the organic layer with a mixed solvent of water and ethanol, the mixed solvent is removed to obtain a toluene solution. Then, isopropanol was added to the toluene solution to perform reprecipitation of the product. After that, it was dried in a vacuum oven to obtain compound Y-1.

Compound Y-2: According to Synthesis Example 5 below, compound Y-2 (molecular weight 5100) was synthesized.

＜Synthesis example 5＞ A 500 mL round bottom flask was charged with 90 g of toluene, 46 g of N-methyl-2-pyrrolidone (NMP), and 7 g of methanesulfonic acid. Next, 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, 31.3 g (60 mmol) of BisA type acid dianhydride was gradually added in small amounts. A round-bottomed flask was installed on the Dean-Stark device and heated to reflux for 3.5 hours. In this way, a compound having an amine at both ends and a plurality of imidine skeletons is obtained. The water discharged during the condensation was removed, and after returning to room temperature, 4.42 g (45 mmol) of maleic anhydride was added and stirred, and the reaction was performed by heating in the same manner. In this way, a compound having a maleimide skeleton at both ends is obtained. After washing the organic layer with a mixed solvent of water and ethanol, the mixed solvent is removed to obtain a toluene solution. Then, isopropanol was added to the toluene solution to perform reprecipitation of the product. After that, it was dried in a vacuum oven to obtain compound Y-2.

The molecular weights of compound X and compound Y synthesized in Synthesis Example 1-5 were determined as follows.

GPC (Gel Permeation Chromatography) measurement: Using a high-speed liquid chromatograph system manufactured by Shimadzu Corporation, using tetrahydrofuran (THF) as a developing solvent, the measurement was performed at a column temperature of 40°C and a flow rate of 1.0 ml/min. Use "SPD-10A" as a detector, and use two columns of "KF-804L" (excluded limit molecular weight 400,000) manufactured by Shodex Corporation in series. Use "TSK Standard Polystyrene" manufactured by Tosoh Corporation as the standard polystyrene, and use the weight average molecular weight Mw=354,000, 189,000, 98,900, 37,200, 17,100, 9,830, 5,870, 2,500, 1,050, 500 to create the calibration curve. And calculate the molecular weight.

The average ratios of the skeletons of the compounds X-2 and X-3 synthesized in Synthesis Examples 2 and 3 were determined by ¹ H-NMR (Nuclear Magnetic Resonance, nuclear magnetic resonance) and based on the bond to the structure of the respective diamine skeletons. Calculate the area ratio of the signal of the hydrogen atom bonded to the carbon atom of the nitrogen atom.

(Thermosetting compound) Biphenyl type epoxy compound ("NC-3000" manufactured by Nippon Kayaku Co., Ltd.) Naphthalene epoxy compound ("ESN-475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Resorcinol diglycidyl ether ("EX-201" manufactured by Nagase chemtex) Epoxy compound with glycidylamine skeleton ("630" manufactured by Mitsubishi Chemical Corporation) Epoxy compound with polybutadiene skeleton ("PB3600" manufactured by Daicel) Epoxy compound with amide skeleton ("WHR-991S" manufactured by Nippon Kayaku Co., Ltd.) Multi-branched aliphatic epoxy compound ("FoldiE101" manufactured by Nissan Chemical Co., Ltd.) Maleimide compound 1 ("BMI-689" manufactured by Designer Molecules Inc.) Maleimide compound 2 (N-alkyl bismaleimide compound, "BMI-1500" manufactured by Designer Molecules Inc.) Maleimide compound 3 (N-alkyl bismaleimide compound, "BMI-1700" manufactured by Designer Molecules Inc.) Maleimide compound 4 (“BMI-4100” manufactured by Daiwa Chemical Co., Ltd.) Maleimide compound 5 ("MIR-3000" manufactured by Nippon Kayaku Co., Ltd.) Styrene compounds (Mitsubishi Gas Chemical "OPE-2St-1200", radical curable compounds, styrene compounds with phenyl ether skeleton) Acrylate compound ("Light Acrylate DCP-A" manufactured by Kyoeisha Chemical Co., Ltd., free radical hardening compound, abbreviated as "DCP-A" in the table)

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

(hardener) Solution containing active ester compound 1 ("EXB-9416-70BK" manufactured by DIC Corporation, 70% by weight of solid content) Solution containing active ester compound 2 ("HPC-8150-62T" manufactured by DIC Corporation, 62% by weight of solid content) Solution containing active ester compound 3 ("HPC-8000L-65T" manufactured by DIC Corporation, 65% by weight of solid content) Active ester compound 4 ("EXB-8" manufactured by DIC, 100% by weight of solid content) Carbodilite imide compound ("Carbodilite V-03" manufactured by Nisshinbo Chemical Co., Ltd., abbreviated as "V-03" in the table) Phenolic compound-containing solution ("LA-1356" manufactured by DIC, 60% by weight solid content, phenolic compound with an amino tri-skeleton)

(Hardening accelerator) Dimethylaminopyridine ("DMAP" manufactured by Wako Pure Chemical Industries, Ltd.) 2-Phenyl-4-methylimidazole ("2P4MZ", anionic hardening accelerator manufactured by Shikoku Chemical Industry Co., Ltd.) Dicumyl peroxide

(Thermoplastic resin) Styrene butadiene resin ("Tuftec H1043" manufactured by Asahi Kasei Co., Ltd., abbreviated as "H1043" in the table) Unhydrogenated alicyclic/aromatic hydrocarbon resin ("Neo Resin EP-140" manufactured by JXTG, abbreviated as "EP-140" in the table) Polyimide compound (polyimide resin): According to Synthesis Example 6 below, a solution containing a polyimide compound (non-volatile content 26.8% by weight) as a reactant of tetracarboxylic dianhydride and dimerdiamine was synthesized.

＜Synthesis example 6＞ Add 300.0 g of tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC JAPAN LLC) and 665.5 g of cyclohexanone to a reaction vessel equipped with a stirrer, a water trap, a thermometer, and a nitrogen introduction tube, and put it in the reaction vessel. The solution was heated to 60°C. Then, 89.0 g of dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan) and 54.7 g of 1,3-diaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd.) were dropped into the reaction vessel. Then, 121.0 g of methylcyclohexane and 423.5 g of ethylene glycol dimethyl ether were added to the reaction vessel, and the imidization reaction was performed at 140° C. for 10 hours. In this way, a solution containing a polyimide compound (non-volatile content 26.8% by weight) was obtained. The molecular weight (weight average molecular weight) of the obtained polyimide compound was 20,000. Furthermore, the molar ratio of acid component/amine component was 1.04.

The molecular weight of the polyimide compound synthesized in Synthesis Example 6 was determined as follows.

GPC (Gel Permeation Chromatography) measurement: Using a high-speed liquid chromatograph system manufactured by Shimadzu Corporation, using tetrahydrofuran (THF) as a developing solvent, the measurement was performed at a column temperature of 40°C and a flow rate of 1.0 ml/min. Use "SPD-10A" as a detector, and use two columns of "KF-804L" manufactured by Shodex (excluding 400,000 limit molecular weight) in series. Use "TSK Standard Polystyrene" manufactured by Tosoh Corporation as the standard polystyrene, and use the weight average molecular weight Mw=354,000, 189,000, 98,900, 37,200, 17,100, 9,830, 5,870, 2,500, 1,050, 500 to create the calibration curve. And calculate the molecular weight.

(Examples 1 to 9 and Comparative Examples 1 to 5) The ingredients shown in the following Tables 1 to 3 were blended in the blending amounts shown in the following Tables 1 to 3 (units are parts by weight of the solid content), and stirred at room temperature until it becomes a uniform solution to obtain a resin material.

Production of resin film: Using an applicator, apply the obtained resin material on the demolding surface of a PET (Polyethylene Terephthalate) film ("XG284" manufactured by Toray, thickness 25 μm) that has been demolded After that, it was dried in a gear oven at 100°C for 2 minutes and 30 seconds to volatilize the solvent. In this way, a laminate film (a laminate film of a PET film and a resin film) in which a resin film (B-stage film) having a thickness of 40 μm was laminated on the PET film was obtained.

(Evaluation) (1) Dielectric loss factor The obtained resin film was heated at 190°C for 90 minutes to obtain a cured product. The obtained hardened material was cut into a size of 2 mm in width and 80 mm in length, and 10 pieces were superimposed, using the "cavity resonance perturbation method dielectric constant measuring device CP521" manufactured by Kanto Electronics Application Development Co., Ltd. and manufactured by Keysight Technologies. The "Network Analyzer N5224A PNA" uses the cavity resonance method to measure the dielectric loss factor at room temperature (23°C) at a frequency of 5.8 GHz.

[Criteria for the determination of dielectric loss factor] ○: The dielectric loss factor is less than 2.9×10 ^-3 ×: The dielectric loss factor is 2.9×10 ^-3 or more

(2) Thermal dimensional stability (average coefficient of linear expansion (CTE)) The obtained resin film (B-stage film) with 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 analysis device ("EXSTAR TMA/SS6100" manufactured by SII NanoTechnology), under the conditions of a tensile load of 33 mN and a heating rate of 5°C/min, calculate the average of the cut hardened material at 25°C to 150°C Coefficient of linear expansion (ppm/°C).

[Judgment criteria for average linear expansion coefficient] ○ ○: The average linear expansion coefficient is 25 ppm/℃ or less ○: The average linear expansion coefficient exceeds 25 ppm/℃ and is below 29 ppm/℃ ×: The average linear expansion coefficient exceeds 29 ppm/℃

(3) Desmear property (removability of residue at the bottom of the through hole) Laminated and semi-hardened treatment: Vacuum lamination was performed on the obtained resin film CCL (Copper Clad Laminate) substrate ("E679FG" manufactured by Hitachi Chemical Co., Ltd.), and heated at 180°C for 30 minutes to semi-cured. In this way, a laminate A in which a semi-cured resin film is laminated on a CCL substrate is obtained.

_{Through hole (through hole) formation: Use CO 2} laser (manufactured by Hitachi Via Mechanics) on the semi-cured material of the resin film of the laminate A, formed at the upper end with a diameter of 60 μm and at the lower end (bottom) The diameter is 40 μm through holes (through holes). In this way, a laminate B in which a semi-cured resin film is laminated on the CCL substrate, and a through hole (through hole) is formed in the semi-cured resin film is obtained.

Removal of the residue at the bottom of the through hole: (a) Swelling treatment To a swelling liquid ("Swelling Dip Securigant P" manufactured by Atotech Japan Co., Ltd.) at 60°C, the obtained laminate B was added, and the mixture was shaken for 10 minutes. After that, it was washed with pure water.

(b) Permanganate treatment (roughening treatment and desmear treatment) To a roughening aqueous solution of potassium permanganate ("Concentrate Compact CP" manufactured by Atotech Japan) at 80°C, the layered body B after swelling treatment was added, and the mixture was shaken for 30 minutes. Next, a 25°C washing solution ("Reduction Securigant P" manufactured by Atotech Japan) was treated for 2 minutes, and then washed with pure water to obtain evaluation sample 1.

The bottom of the through hole of the evaluation sample 1 was observed with a scanning electron microscope (SEM), and the maximum scum length from the wall surface of the bottom of the through hole was determined. Use the following criteria to determine the removability of the residue at the bottom of the through hole.

[Judgment criteria for the removal of residues at the bottom of the through hole] ○○: The maximum glue residue length is less than 2 μm ○: The maximum glue residue length is 2 μm or more and less than 5 μm ×: The maximum slag length is 5 μm or more

(4) Surface roughness (surface roughness) and uniformity of surface roughness after etching Laminating steps and semi-hardening treatment: Prepare a double-sided copper-clad laminate (CCL substrate) ("E679FG" manufactured by Hitachi Chemical Co., Ltd.). The both sides of the copper foil surface of this double-sided copper foil laminated board were immersed in "Cz8101" manufactured by MEC Corporation, and the surface of the copper foil was roughened. On both sides of the copper foil laminated board that has been roughened, use the "Batch Vacuum Laminator MVLP-500-IIA" manufactured by Meike Manufacturing Co., Ltd. to overlap the resin film (B-stage film) side of the laminated film on the The copper foil laminated board is laminated to obtain a laminated structure. The conditions of lamination were as follows: pressure was reduced for 30 seconds, the air pressure was set to 13 hPa or less, and then pressure was applied at 100°C and 0.4 MPa for 30 seconds. After that, it was heated at 180°C for 30 minutes to semi-harden the resin film. In this way, a laminate in which a semi-cured resin film is laminated on a CCL substrate is obtained.

Coarse treatment: (a) Swelling treatment: The obtained laminate was added to a swelling liquid ("Swelling Dip Securigant P" manufactured by Atotech Japan) at 60°C, and shaken for 10 minutes. After that, it was washed with pure water.

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

Measurement of surface roughness: On the surface of the evaluation sample (hardened product after roughening treatment), select any 10 locations in the area of 94 μm×123 μm. A non-contact three-dimensional surface profile measuring device ("WYKO NT1100" manufactured by Veeco Corporation) was used to measure the arithmetic average roughness Ra for each area of the 10 locations. Evaluate the following surface roughness based on the average value of the arithmetic average roughness Ra of the 10 measured locations, and evaluate the following surface roughness based on the absolute value of the difference between the maximum and minimum values of the arithmetic average roughness Ra of the 10 measured locations Uniformity of surface roughness. In addition, the above-mentioned arithmetic average roughness Ra is measured in accordance with JIS B0601:1994.

[Criteria for judging 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

[Judgement criteria for uniformity of surface roughness (surface roughness) after etching] ○: The absolute value of the difference between the maximum and minimum arithmetic mean roughness Ra is less than 10 nm △: The absolute value of the difference between the maximum and minimum arithmetic mean roughness Ra is 10 nm or more and less than 20 nm ×: The absolute value of the difference between the maximum and minimum arithmetic average roughness Ra is 20 nm or more

(5) Plating peel strength Laminating steps and semi-hardening treatment: Prepare a 100 mm square double-sided copper-clad laminate (CCL substrate) (“E679FG” manufactured by Hitachi Chemical Co., Ltd.). The both sides of the copper foil surface of this double-sided copper foil laminated board were immersed in "Cz8101" manufactured by MEC Corporation, and the surface of the copper foil was roughened. Using the "Batch Type Vacuum Laminator MVLP-500-IIA" manufactured by Meiji Manufacturing Co., Ltd., overlap the resin film (B-stage film) side of the laminated film on both sides of the roughened copper foil laminated board The copper foil laminated board is laminated to obtain a laminated structure. The lamination conditions are set to reduce pressure for 30 seconds, set the air pressure to 13 hPa or less, and then perform lamination at 100°C and 0.7 MPa for 30 seconds, and then at a pressure of 0.8 MPa and a pressure of 100 Press at ℃ for 60 seconds. Thereafter, with the PET film mounted, the resin film in the laminated structure was heated at 100°C for 30 minutes, and then further heated at 180°C for 30 minutes to semi-harden the resin film. Thereafter, by peeling off the PET film, a laminate in which a semi-cured resin film was laminated on the CCL substrate was obtained.

Coarse treatment: (a) Swelling treatment: The obtained laminate was added to a swelling liquid ("Swelling Dip Securigant P" manufactured by Atotech Japan) at 60°C, and shaken for 10 minutes. After that, it was washed with pure water.

(b) Permanganate treatment (roughening treatment and desmear treatment): The swelling-treated laminate was added to the roughening aqueous solution of potassium permanganate ("Concentrate Compact CP" manufactured by Atotech Japan) at 80°C and shaken for 30 minutes. Next, a 25°C washing solution ("Reduction Securigant P" manufactured by Atotech Japan Co., Ltd.) was used for 2 minutes of treatment, then washed with pure water, and subjected to roughening treatment.

Electroless plating treatment: The surface of the obtained roughened hardened product was treated with an alkaline cleaning solution ("Cleaner Securigant 902" manufactured by Atotech Japan Co., Ltd.) for 5 minutes at 60°C, and then degreased and washed. After washing, the cured product was treated with a 25°C prepreg ("Pre-dip Neogant B" manufactured by Atotech Japan) for 2 minutes. After that, the cured product was treated with an activator liquid ("Activator Neogant 834" manufactured by Atotech Japan Co., Ltd.) at 40°C for 5 minutes, and a palladium catalyst was added. Next, a 30°C reducing solution ("Reducer Neogant WA" manufactured by Atotech Japan) was used to process the hardened product for 5 minutes.

Next, add the above-mentioned hardened material to the chemical copper solution ("Basic Printganth MSK-DK", "Copper Printganth MSK", "Stabilizer Printganth MSK", and "Reducer Cu" manufactured by Atotech Japan), and perform electroless plating Until the plating thickness becomes about 0.5 μm. After electroless plating, the residual hydrogen is removed, so an annealing treatment is carried out at a temperature of 120°C for 30 minutes. In addition, all the steps up to the step of electroless plating were performed with the treatment liquid set to 2 L with the scale of the beaker, and the hardened product was shaken.

Electrolytic plating treatment: Secondly, electrolytic plating is performed on the hardened product after electroless plating treatment until the plating thickness becomes 25 μm. For electrolytic copper plating, copper sulfate solution ("copper sulfate pentahydrate" manufactured by Wako Pure Chemical Industries, Ltd., "sulfuric acid" manufactured by Wako Pure Chemical Industries, Ltd., "Basic Leveller Cupracid HL" manufactured by Atotech Japan, and Atotech Japan The "Correction Agent Cupracid GS" manufactured by the company) is supplied with a current of 0.6 A/cm ² and electrolytic plating is performed until the plating thickness becomes about 25 μm. After the copper plating treatment, the hardened product is heated at 200°C for 60 minutes to further harden the hardened product. In this way, a hardened product in which a copper plating layer is laminated on the upper surface is obtained.

Measurement of plating peel strength: A total of 6 short 10 mm wide slits are placed at 5 mm intervals on the surface of the hardened copper plating layer of the obtained copper plating layer laminated on the upper surface. Set up a hardened product made of copper plating layer on the upper surface on a 90° peeling tester ("TE-3001" manufactured by TESTER SANGYO), and use a jig to pick up the end of the cut copper plating layer , The copper plating layer was peeled off by 20 mm, and the peel strength (plating peel strength) was measured. The peeling strength (plating peeling strength) was measured for each of the 6 cut portions, and the average value of the plating peeling strength was determined. The plating peel strength was judged based on the following criteria.

[Criteria for determination of plating peel strength] ○ ○: The average value of plating peel strength is 0.5 kgf/cm or more ○: The average value of plating peel strength is 0.45 kgf/cm or more and less than 0.5 kgf/cm △: The average peel strength of the coating 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

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

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Compound X Compound X-1 Synthesis example 1 Parts by weight 4.5 Compound X-2 Synthesis Example 2 Parts by weight 4.5 Compound X-3 Synthesis Example 3 Parts by weight 4.5 4.4 5.4 Compound Y (compound not equivalent to compound X) Compound Y-1 Synthesis Example 4 Parts by weight Compound Y-2 Synthesis Example 5 Parts by weight Thermosetting compound Biphenyl type epoxy compound NC-3000 Parts by weight 4.1 4.1 4.1 5.0 3.4 Naphthalene type epoxy compound ESN-475V Parts by weight 4.1 4.1 4.1 4.5 4.0 Resorcinol diglycidyl ether EX-201 Parts by weight 1.6 1.6 1.6 0.8 0.8 Epoxy compound with glycidylamine skeleton 630 Parts by weight 0.2 Epoxy compound with polybutadiene skeleton PB3600 Parts by weight 0.5 Epoxy compound with amide skeleton WHR-991S Parts by weight 1.2 Multi-branched aliphatic epoxy compound FoldiE101 Parts by weight 1.8 1.8 1.8 2.2 1.8 Maleimide compound 1 BM1-689 Parts by weight 0.3 Maleic imide compound 2 BMI-1500 Parts by weight Maleimide compound 3 BMI-1700 Parts by weight Maleimide compound 4 BM1-4100 Parts by weight Maleimide compound 5 MIR-3000 Parts by weight 0.3 Styrene compound (free radical hardening compound) 0PE-2St-1200 Parts by weight Acrylate compound (radical hardenable compound) DCP-A Parts by weight Inorganic filler Silicon dioxide SC4050-H0A Parts by weight 70 70 70 70 70 hardener Active ester compound 1 EXB-9416-70BK Parts by weight 4.9 4.9 4.9 Active ester compound 2 HPC-8150-62T Parts by weight 5.2 5.2 5.2 4.8 5.0 Active ester compound 3 HPC-8000L-65T Parts by weight 1.7 1.8 Active ester compound 4 EXB-8 Parts by weight 2.9 2.9 Carbodiimide compound V-03 Parts by weight 0.4 Phenol compound LA-1356 Parts by weight 0.6 0.6 0.6 0.5 0.3 Hardening accelerator Dimethylaminopyridine DMAP Parts by weight 0.03 0.03 0.03 0.03 0.03 2-phenyl-4-methylimidazole 2P4MZ Parts by weight 0.28 0.28 0.28 0.26 0.26 Dicumyl peroxide Parts by weight Thermoplastic resin Polyimide compound Synthesis Example 6 Parts by weight 2.7 2.7 2.7 2.0 2.0 Styrene butadiene resin H1043 Parts by weight Unhydrogenated alicyclic/aromatic hydrocarbon resin EP140 Parts by weight 0.4 The content of compound X in 100% by weight of components other than inorganic fillers and solvents in the resin material weight% 15 15 15 15 18 The content of inorganic fillers in 100% by weight of the components other than the solvent in the resin material weight% 70 70 70 70 70 Evaluation Dielectric loss factor ×10 ^-3 2.85 2.70 2.65 2.50 2.80 determination ○ ○ ○ ○ ○ Thermal dimensional stability (average coefficient of linear expansion (CTE)) ppm/℃ 19 twenty four 25 twenty four twenty four determination ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Desmear determination ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Surface roughness after etching (surface roughness) Average value of Ra nm 32 48 45 40 48 Surface roughness determination ○ ○ ○ ○ ○ Maximum value of Ra nm 35 51 49 44 52 Minimum value of Ra nm 28 45 41 37 44 Uniformity determination ○ ○ ○ ○ ○ Plating peel strength determination ○ ○ ○ ○ ○ ○ ○ ○

[Table 2] Example 6 Example 7 Example 8 Example 9 Compound X Compound X-1 Synthesis example 1 Parts by weight Compound X-2 Synthesis Example 2 Parts by weight 2.8 Compound X-3 Synthesis Example 3 Parts by weight 3.5 4.7 3.5 4.9 Compound Y (compound not equivalent to compound X) Compound Y-1 Synthesis Example 4 Parts by weight Compound Y-2 Synthesis Example 5 Parts by weight Thermosetting compound Bisphenol type epoxy compound NC-3000 Parts by weight 3.7 4.0 4.0 3.6 Naphthalene type epoxy compound ESN-475V Parts by weight 4.4 4.7 4.4 4.2 Resorcinol diglycidyl ether EX-201 Parts by weight 0.8 0.8 0.7 0.7 Epoxy compound with glycidylamine skeleton 630 Parts by weight Epoxy compound with polybutadiene skeleton PB3600 Parts by weight Epoxy compound with amide skeleton WHR-991S Parts by weight 1.1 1.2 1.1 Multi-branched aliphatic epoxy compound FoldiE101 Parts by weight 1.6 1.7 1.9 1.6 Maleimide compound 1 BM1-689 Parts by weight 0.3 Maleic imide compound 2 BM1-1500 Parts by weight Maleimide compound 3 BM1-1700 Parts by weight Maleimide compound 4 BM1-4100 Parts by weight Maleimide compound 5 MIR-3000 Parts by weight 0.2 0.3 Styrene compound (free radical hardening compound) 0PE-2St-1200 Parts by weight 2.5 Acrylate compound (radical hardenable compound) DCP-A Parts by weight 2.0 Inorganic filler Silicon dioxide SC4050-H0A Parts by weight 70 70 70 73 hardener Active ester compound 1 EXB-9416-70BK Parts by weight Active ester compound 2 HPC-8150-62T Parts by weight 4.6 4.8 4.2 4.3 Active ester compound 3 HPC-8000L-65T Parts by weight 1.6 1.7 1.5 1.6 Active ester compound 4 EXB-8 Parts by weight 2.7 2.9 2.5 2.6 Carbodiimide compound V-03 Parts by weight Phenol compound LA-1356 Parts by weight 0.5 0.5 0.5 0.5 Hardening accelerator Dimethylaminopyridine DMAP Parts by weight 0.03 0.03 0.03 2-phenyl-4-methylimidazole 2P4MZ Parts by weight 0.24 0.26 0.23 0.23 Dicumyl peroxide Parts by weight 0.05 Thermoplastic resin Polyimide compound Synthesis Example 6 Parts by weight 1.9 2.0 0.9 1.8 Styrene butadiene resin H1043 Parts by weight 0.9 Unhydrogenated alicyclic/aromatic hydrocarbon resin EP140 Parts by weight The content of compound X in 100% by weight of components other than inorganic fillers and solvents in the resin material weight% twenty one 16 12 18 The content of inorganic fillers in 100% by weight of the components other than the solvent in the resin material weight% 70 70 70 73 Evaluation Dielectric loss factor ×10 ^-3 2.60 2.50 2.45 2.30 determination ○ ○ ○ ○ Thermal dimensional stability (average coefficient of linear expansion (CTE)) ppm/℃ twenty two twenty three twenty one twenty one determination ○ ○ ○ ○ ○ ○ ○ ○ Desmear determination ○ ○ ○ ○ ○ ○ ○ ○ Surface roughness after etching (surface roughness) Average value of Ra nm 45 46 49 52 Surface roughness determination ○ ○ ○ △ Maximum value of Ra nm 49 49 53 56 Minimum value of Ra nm 41 42 44 47 Uniformity determination ○ ○ ○ ○ Plating peel strength determination ○ ○ ○ ○ ○ ○ ○

[table 3] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Compound X Compound X-1 Synthesis example 1 Parts by weight Compound X-2 Synthesis Example 2 Parts by weight Compound X-3 Synthesis Example 3 Parts by weight Compound Y (compound not equivalent to compound X) Compound Y-1 Synthesis Example 4 Parts by weight 4.5 Compound Y-2 Synthesis Example 5 Parts by weight 4.5 Thermosetting compound Bisphenol type epoxy compound NC-3000 Parts by weight 4.1 4.1 4.2 4.6 Naphthalene type epoxy compound ESN-475V Parts by weight 4.1 4.1 5.5 4.6 Resorcinol diglycidyl ether EX-201 Parts by weight 1.6 1.6 1.8 1.8 Epoxy compound with glycidylamine skeleton 630 Parts by weight Epoxy compound with polybutadiene skeleton PB3600 Parts by weight Epoxy compound with amide skeleton WHR-991S Parts by weight Multi-branched aliphatic epoxy compound FoldiE101 Parts by weight 1.8 1.8 2.0 Maleimide compound 1 BM1-689 Parts by weight Maleic imide compound 2 BMI-1500 Parts by weight 3.0 Maleimide compound 3 BMI-1700 Parts by weight 24.5 Maleimide compound 4 BM1-4100 Parts by weight 4.9 Maleimide compound 5 MIR-3000 Parts by weight Styrene compound (free radical hardening compound) 0PE-2St-1200 Parts by weight Acrylate compound (radical hardenable compound) DCP-A Parts by weight Inorganic filler Silicon dioxide SC4050-H0A Parts by weight 70 70 70 70 70 hardener Active ester compound 1 EXB-9416-70BK Parts by weight 4.9 4.9 4.9 5.5 Active ester compound 2 HPC-8150-62T Parts by weight 5.2 5.2 5.3 5.8 Active ester compound 3 HPC-8000L-65T Parts by weight Active ester compound 4 EXB-8 Parts by weight Carbodiimide compound V-03 Parts by weight Phenol compound LA-1356 Parts by weight 0.6 0.6 0.6 0.7 Hardening accelerator Dimethylaminopyridine DMAP Parts by weight 0.03 0.03 0.03 0.06 2-phenyl-4-methylimidazole 2P4MZ Parts by weight 0.28 0.28 0.35 0.31 Dicumyl peroxide Parts by weight 0.5882 Thermoplastic resin Polyimide compound Synthesis Example 6 Parts by weight 2.7 2.7 2.7 5.1 Styrene butadiene resin H1043 Parts by weight Unhydrogenated alicyclic/aromatic hydrocarbon resin EP140 Parts by weight The content of compound X in 100% by weight of components other than inorganic fillers and solvents in the resin material weight% 0 0 0 0 0 The content of inorganic fillers in 100% by weight of the components other than the solvent in the resin material weight% 70 70 70 71 70 Evaluation Dielectric loss factor ×10 ^-3 2.94 2.80 2.75 2.82 2.70 determination X ○ ○ ○ ○ Thermal dimensional stability (average coefficient of linear expansion (CTE)) ppm/℃ twenty two 35 40 29 30 determination ○ ○ X X ○ X Desmear determination ○ ○ ○ ○ X Surface roughness after etching (surface roughness) Average value of Ra nm 28 45 210 81 57 Surface roughness determination ○ ○ X X △ Maximum value of Ra nm 31 48 225 88 62 Minimum value of Ra nm 26 40 203 76 54 Uniformity determination ○ ○ X △ ○ Plating peel strength determination X ○ X X ○

11: Multilayer printed wiring board 12: Circuit board 12a: upper surface 13: Insulation layer 14: Insulation layer 15: Insulation layer 16: insulation layer 17: Metal layer

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.

Claims (22)

A resin material comprising a compound having a structure represented by the following formula (X) and a hardening accelerator, [化1]

In the above formula (X), R represents an organic group, and n represents a number of 1 or more. Such as the resin material of claim 1, wherein in the above formula (X), n represents a number of 2 or more. The resin material of claim 1 or 2, wherein in the above formula (X), R is a group having an aliphatic ring. The resin material of claim 1 or 2, wherein in the above formula (X), R has a partial skeleton derived from the skeleton of dimer diamine. The resin material of claim 1 or 2, wherein in the above formula (X), R has a partial skeleton derived from the skeleton of a diamine compound other than dimer diamine. The resin material of claim 1 or 2, wherein in the above-mentioned compound, the nitrogen atom constituting the imine skeleton is only bonded to the carbon atom constituting the aliphatic skeleton. The resin material of claim 1 or 2, wherein the above-mentioned compound is a compound having a maleimide skeleton. The resin material of claim 1 or 2, wherein the above-mentioned compound is a compound having a maleimide skeleton at both ends. The resin material of claim 1 or 2, wherein the weight average molecular weight of the above-mentioned compound is 1,000 or more and 100,000 or less. The resin material of claim 1 or 2, wherein the above compound has a structure represented by the following formula (Y), and the number of repetitions of the structure represented by the above formula (X) and the structure represented by the following formula (Y) In 100% of the total number of repetitions, the number of repetitions of the structure represented by the above formula (X) is 10% or more and 90% or less, [Chemical 2]

In the above formula (Y), R1 represents a tetravalent organic group, R2 represents an organic group, and m represents a number of 1 or more. The resin material of claim 10, wherein in the above formula (Y), R1 does not have a skeleton derived from phthalimide, In the above formula (Y), R2 does not have a skeleton derived from phthalimide. The resin material of claim 10, wherein in the above formula (Y), R1 does not have an aromatic skeleton. Such as the resin material of claim 1 or 2, which contains a thermosetting compound and a hardener, and The said thermosetting compound contains an epoxy compound. The resin material according to claim 13, wherein the hardener includes an active ester compound. The resin material of claim 14, wherein at least one of the epoxy compound and the active ester compound has an amide skeleton or an amide skeleton. The resin material according to claim 13, wherein the thermosetting compound includes a radical curing compound. Such as the resin material of claim 1 or 2, which contains an inorganic filler. Such as the resin material of claim 17, wherein the content of the above-mentioned inorganic filler in 100% by weight of the components other than the solvent in the resin material is 50% by weight or more. The resin material of claim 17, wherein the above-mentioned inorganic filler is silicon dioxide. Such as the resin material of claim 1 or 2, which is a resin film. The resin material of claim 1 or 2, which is used to form an insulating layer in a multilayer printed wiring board. A multilayer printed wiring board is provided with: Circuit board, A plurality of insulating layers arranged on the surface of the above-mentioned circuit substrate, and A metal layer arranged between the plurality of insulating layers, and At least one of the plurality of insulating layers is a cured product of a resin material according to any one of claims 1 to 20.

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