TWI804597B - Resin materials and multilayer printed wiring boards - Google Patents

Abstract

The present invention provides a resin material, which can 1) reduce the dielectric loss tangent of the hardened product, 2) improve the adhesion between the insulating layer and the metal layer, 3) improve the peeling strength of the plating layer, 4) improve the flame retardancy of the hardened product, and 5) Keep the hardening temperature low. The resin material of the present invention comprises: an N-alkylbismaleimide compound having a skeleton derived from dimer diamine or an N-alkylbenzoxene compound having a skeleton derived from dimer diamine A thiol compound, an epoxy compound, an inorganic filler, and a curing agent containing specific components, and the content of the N-alkylbismaleimide compound having a skeleton derived from dimer diamine or the above-mentioned The weight ratio of the N-alkylbenzo(a) compound derived from the skeleton of the dimer diamine to the total content of the epoxy compound and the curing agent is 0.05 to 0.75.

Description

Resin materials and multilayer printed wiring boards

The invention relates to a resin material including epoxy compound, inorganic filler and hardener. Also, the present invention relates to a multilayer printed wiring board using the above-mentioned resin material.

Conventionally, various resin materials have been used to obtain electronic components such as semiconductor devices, laminated boards, and printed wiring boards. For example, in a multilayer printed wiring board, a resin material is used to form an insulating layer for insulating internal layers or to form an insulating layer located on a surface layer. On the surface of the above-mentioned insulating layer, a layer is generally laminated as a metal wiring. Moreover, in order to form the said insulating layer, the resin film which made the said resin material into a film may be used. The above-mentioned resin material and the above-mentioned resin film are used as an insulating material for a multilayer printed wiring board including a buildup film, and the like.

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

[Patent Document 1] WO2016/114286A1

[Problem to be solved by the invention]

In order to improve the electrical characteristics of the cured product (insulating layer), there are cases where a compound with low polarity is blended into the resin material (resin composition). However, when the insulating layer is formed using a resin material prepared with a relatively small polar compound, the adhesiveness between the insulating layer and wiring (metal layer) may not be sufficiently high. Therefore, the metal layer may peel off from the insulating layer. In addition, conventional resin materials may have large thickness or insufficient plating peel strength.

Moreover, the flame retardancy of the conventional resin material which mix|blended the maleimide compound which has an aliphatic skeleton as described in patent document 1 may fall. On the other hand, conventional resin materials containing a maleimide compound having an aromatic skeleton are difficult to lower the curing temperature (for example, 200° C. or less) because the Tg of the maleimide compound is relatively high. ). Also, when the curing temperature is lowered, it is difficult to generate sufficient molecular motion, and thus poor curing may occur. Also, when the hardening temperature is lowered, the resin material of the initial layer is heated more times and for a longer time than the resin material of the later layer when manufacturing a multilayer printed wiring board, so there is an insulating layer. Changes in electrical characteristics or physical properties. In addition, conventional resin materials that harden by radical reaction react quickly, so it is difficult to control the degree of hardening before etching, and anchors cannot be formed sufficiently. As a result, the peeling strength of the plating layer may not be sufficiently high.

Thus, there is a current situation in which it is extremely difficult to obtain a resin material that exhibits all the effects of 1) to 5), that is, 1) reducing the dielectric loss tangent of the cured product, 2) improving the adhesion between the insulating layer and the metal layer, 3) Improve the peeling strength of the coating, 4) improve the flame retardancy of the hardened product, and 5) suppress the hardening temperature to a low level.

The object of the present invention is to provide a resin material, which can 1) reduce the dielectric loss tangent of the hardened product, 2) improve the adhesion between the insulating layer and the metal layer, 3) improve the peeling strength of the coating, and 4) improve the flame retardancy of the hardened product , and 5) suppress the hardening temperature lower. Moreover, the object of this invention is to provide the multilayer printed wiring board which used the said resin material. [Technical means to solve the problem]

According to a broad aspect of the present invention, there is provided a resin material comprising: an N-alkyl bismaleimide compound having a skeleton derived from dimer diamine or a compound having a skeleton derived from dimer diamine N-alkyl benzo 㗁 𠯤 compounds of the skeleton; epoxy compounds; inorganic fillers; and containing phenolic compounds, cyanate compounds, acid anhydrides, active ester compounds, carbodiimide compounds, and A hardener for at least one component of a benzodiazepine compound having a skeleton derived from a diamine; in the case of containing the above-mentioned N-alkylbismaleimide compound having a skeleton derived from a dimer diamine In this case, the weight ratio of the content of the above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine to the total content of the above-mentioned epoxy compound and the above-mentioned hardening agent is 0.05 to 0.75 , and in the case of including the above-mentioned N-alkylbenzo 㗁 だ は compound having a skeleton derived from dimer diamine, the above N-alkyl benzo 㗁 だ は compound having a skeleton derived from dimer diamine The weight ratio of the content to the total content of the said epoxy compound and the said hardening agent is 0.05-0.75.

In a specific aspect of the resin material of the present invention, the above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine has a structure represented by the following formula (X) , or the above-mentioned N-alkylbenzoxamethonium compound having a skeleton derived from dimer diamine has a structure represented by the following formula (X).

[chemical 1]

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

In a specific aspect of the resin material of the present invention, the above-mentioned epoxy compound is an epoxy compound having an aromatic skeleton, and the above-mentioned component is a component having an aromatic skeleton.

In a specific aspect of the resin material of the present invention, the hardener includes an active ester compound having two or more aromatic skeletons.

In a certain aspect of the resin material of this invention, the said resin material contains a hardening accelerator.

In a certain aspect of the resin material of this invention, the said hardening accelerator contains an anionic hardening accelerator.

In a specific aspect of the resin material of the present invention, the content of the above-mentioned anionic hardening accelerator is 50% by weight or more in 100% by weight of the above-mentioned hardening accelerator.

In a specific aspect of the resin material of the present invention, the above-mentioned anionic hardening accelerator is an imidazole compound.

In a specific aspect of the resin material of the present invention, the hardening accelerator includes a radical hardening accelerator and an imidazole compound, or includes a radical hardening accelerator and a phosphorus compound.

In a specific aspect of the resin material of the present invention, the above-mentioned inorganic filler has an average particle diameter of 1 μm or less.

In a specific aspect of the resin material of the present invention, it comprises the above-mentioned N-alkylbismaleimide compound having a skeleton derived from a dimer diamine, and the above-mentioned compound having a skeleton derived from a dimer The molecular weight of the N-alkylbismaleimide compound having a diamine skeleton is less than 15,000.

In a specific aspect of the resin material of the present invention, it includes the above-mentioned N-alkylbenzoxamethonium compound having a skeleton derived from dimer diamine, and the above-mentioned N-alkylbenzoxo compound having a skeleton derived from dimer diamine The molecular weight of the N-alkyl benzo 㗁 𠯤 compound is less than 15,000.

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 to form an insulating layer in a multilayer printed wiring board.

According to a broad 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 above-mentioned resin material. [Effect of Invention]

The resin material of the present invention comprises: an N-alkylbismaleimide compound having a skeleton derived from dimer diamine or an N-alkylbenzoxene compound having a skeleton derived from dimer diamine 𠯤 compounds, epoxy compounds, and inorganic fillers. The resin material of the present invention includes a hardener containing a phenolic compound, a cyanate compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a benzophenone that does not have a skeleton derived from a dimer diamine At least one component of the compound. In the resin material of the present invention, when the above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine is included, the above-mentioned having a skeleton derived from dimer diamine The weight ratio of the content of the N-alkylbismaleimide compound to the total content of the epoxy compound and the curing agent is 0.05 to 0.75. In the resin material of the present invention, in the case of including the above-mentioned N-alkylbenzoxene compound having a skeleton derived from dimer diamine, the above-mentioned N-alkyl compound having a skeleton derived from dimer diamine The weight ratio of the content of the benzobenzoyl compound to the total content of the epoxy compound and the curing agent is not less than 0.05 and not more than 0.75. Since the resin material of the present invention has the above structure, it can exert all the effects of the following 1)-5): 1) reduce the dielectric loss tangent of the cured product, 2) improve the adhesion between the insulating layer and the metal layer, 3) improve the Plating peel strength, 4) improve the flame retardancy of the hardened product, and 5) suppress the hardening temperature lower.

Hereinafter, the present invention will be described in detail.

The resin material of the present invention comprises an N-alkylbismaleimide compound having a skeleton derived from dimer diamine or an N-alkylbenzoxadiamide compound having a skeleton derived from dimer diamine compound.

The resin material of the present invention contains an epoxy compound.

The resin material of the present invention contains an inorganic filler.

The resin material of the present invention includes a hardener containing a phenolic compound, a cyanate compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a benzophenone that does not have a skeleton derived from a dimer diamine At least one component of the compound.

In this specification, sometimes at least one of "phenol compound, cyanate compound, acid anhydride, active ester compound, carbodiimide compound, and benzodiazepine compound not having a skeleton derived from dimer diamine A component" is described as "ingredient X".

Therefore, the resin material of the present invention comprises: an N-alkylbismaleimide compound having a skeleton derived from dimer diamine or an N-alkylbenzene compound having a skeleton derived from dimer diamine And 㗁𠯤 compounds, epoxy compounds, inorganic fillers, and hardeners containing component X.

In the resin material of the present invention, when the resin material includes the above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine, the above-mentioned compound having a skeleton derived from dimer diamine The weight ratio of the content of the N-alkylbismaleimide compound in the backbone to the total content of the epoxy compound and the hardener is 0.05 to 0.75.

In the resin material of the present invention, in the case where the resin material contains the above-mentioned N-alkylbenzoxazine compound having a skeleton derived from dimer diamine, the above-mentioned N compound having a skeleton derived from dimer diamine - The weight ratio of the content of the alkyl benzo α - compound to the total content of the epoxy compound and the curing agent is not less than 0.05 and not more than 0.75.

Since the resin material of the present invention has the above structure, it can exert all the effects of the following 1)-5): 1) reduce the dielectric loss tangent of the cured product, 2) improve the adhesion between the insulating layer and the metal layer, 3) improve the Plating peel strength, 4) improve the flame retardancy of the hardened product, and 5) suppress the hardening temperature lower. For example, 2) The peel strength between the insulating layer and the metal layer in the temperature range from room temperature to high temperature (for example, 260° C.), which is the adhesion between the insulating layer and the metal layer, can be improved. Also, 3) The peel strength between the roughened cured product (insulating layer) and the metal layer laminated by plating on the surface of the insulating layer can be improved. In the above roughened cured product (insulating layer), fine recesses are formed on the surface. The resin portion present near the opening of the recess exhibits an anchoring effect on the metal layer. The resin material of the present invention can improve the peeling strength of the plating because the resin that contributes to the anchoring effect can be suppressed from locally becoming too fine due to the roughening of the cured product (insulating layer) that has been roughened. In addition, the resin material of the present invention can prevent anchorage from becoming too small due to the roughened cured product (insulation layer), thereby improving the peel strength of the plating layer.

Furthermore, since the resin material of the present invention has the above-mentioned constitution, it is possible to improve the coverage of the uneven surface.

The resin material of the present invention may be a resin composition or a resin film. The aforementioned resin composition has fluidity. The aforementioned resin composition may be in a paste form. The above-mentioned pasty form includes liquid form. The resin material of the present invention is preferably a resin film in terms of excellent handleability.

When the resin material of the present invention is a resin film, the flexibility of the resin film can be improved. Regarding the resin film (resin material) of the present invention, when the resin film is handled, the resin film is less likely to be cracked or broken. That is, when the resin material of the present invention is a resin film, in addition to the above-mentioned effects of 1) to 5), 6) can also improve the flexibility of the resin film.

The resin material of the present invention is preferably a thermosetting material. When the above-mentioned resin material is a resin film, the resin film is preferably a thermosetting resin film.

Hereinafter, details of each component used for the resin material of the present invention, uses of the resin material of the present invention, and the like will be described.

[Compound having a skeleton derived from dimer diamine] The resin material of the present invention includes an N-alkylbismaleimide compound having a skeleton derived from dimer diamine or a compound having a skeleton derived from dimer diamine. N-alkyl benzo 㗁 𠯤 compound with the skeleton of diamine. The resin material of the present invention may only contain the N-alkylbismaleimide compound, may only contain the N-alkylbenzozil compound, or may contain the N-alkylbismaleimide compound. Both of the imide compound and the N-alkylbenzo 㗁 𠯤 compound.

<N-Alkyl bismaleimide compound having a skeleton derived from dimer diamine> The resin material of the present invention preferably contains an N-alkyl group having a skeleton derived from dimer diamine Bismaleimide compound. The above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine has a maleimide group. By using the above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine, the dielectric loss tangent can be reduced, and the adhesion between the insulating layer and the metal layer and the peeling strength of the plating layer can be improved. Moreover, etching performance can be improved by using the said N-alkyl bismaleimide compound which has the skeleton derived from the dimer diamine. Furthermore, by using the above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine, the curing temperature can be kept low. The aforementioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine may also be in the state of an oligomer. The aforementioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine may also have a molecular weight distribution. The N-alkylbismaleimide compound which has the said skeleton derived from dimer diamine may use only 1 type, and may use 2 or more types together.

In the N-alkylbismaleimide compound having the skeleton derived from dimer diamine, the skeleton derived from dimer diamine exists as a partial skeleton. The N-alkylbismaleimide compound having a skeleton derived from dimer diamine preferably has a structure in which an aliphatic skeleton is bonded to a nitrogen atom in a maleimide group .

The N-alkylbismaleimide compound having a skeleton derived from dimer diamine of the present invention may also be a citraconimide compound. The aforementioned citraconimide compound refers to a compound in which a methyl group is bonded to one of the carbon atoms constituting the double bond between carbon atoms in the maleimide group. The reactivity of the above-mentioned citraconimide compound is slightly lower than that of the maleimide compound, so the storage stability can be improved.

The above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine preferably has a skeleton derived from a reactant of tetracarboxylic dianhydride and dimer diamine. The reactant of the above-mentioned tetracarboxylic dianhydride and the above-mentioned dimer diamine is preferably a compound having amino groups at both ends.

The above-mentioned N-alkyl bismaleimide compound having a skeleton derived from dimer diamine, for example, can be used to obtain the reactant of tetracarboxylic dianhydride and dimer diamine (preferably two ends are Amino compound) and reacting the reactant with maleic anhydride.

Examples of the tetracarboxylic dianhydride include: pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'- Benzene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-biphenyl 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)diphenylsulfide dianhydride, 4,4'-bis(3,4- Dicarboxyphenoxy)diphenyldiphenyldianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropanedianhydride, 3,3',4,4'-perfluoro Isopropyl diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenyl phthalic acid) dianhydride, m-benzene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylether dianhydride, and bis (Triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, etc.

Examples of commercially available dimer diamines include Versamine 551 (trade name, manufactured by BASF Japan, 3,4-bis(1-aminoheptyl)-6-hexyl-5-(1- octenyl) cyclohexene), Versamine 552 (trade name, manufactured by Cognis Japan, hydride of Versamine 551), PRIAMINE 1075, PRIAMINE 1074, and PRIAMINE 1071 (trade name, all manufactured by Croda Japan), etc. In addition, dimer diamine may have an unsaturated hydrocarbon as a partial frame|skeleton, and may not have it.

Examples of commercially available N-alkylbismaleimide compounds having a skeleton derived from dimer diamine include "BMI-1500" and "BMI-1500" manufactured by Designer Molecules Inc. 1700", and "BMI-3000", etc.

From the viewpoint of exerting the effect of the present invention more effectively, the above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine is preferably represented by the following formula (X): representation structure.

[Chem 2]

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

As R1 in said formula (X), the group which has an aromatic ring, the group which has a biphenyl ether skeleton, etc. are mentioned. As a group which has the said aromatic ring, the group which has a skeleton derived from pyromellitic anhydride, etc. are mentioned. As the group having the above-mentioned biphenyl ether skeleton, a group having a skeleton derived from 4,4'-oxydiphthalic anhydride, etc. are mentioned.

The above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine may have one structure represented by the above formula (X), may have two structures, or may have two or more structures .

The weight ratio of the content of the above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine to the total content of the above-mentioned epoxy compound and the above-mentioned hardening agent is called "weight ratio ( Content of N-alkylbismaleimide compound having a skeleton derived from dimer diamine/total content of epoxy compound and hardener)". In the case where the above-mentioned resin material contains the above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine, the above weight ratio (N having a skeleton derived from dimer diamine - The content of the alkylbismaleimide compound/the total content of the epoxy compound and the curing agent) is not less than 0.05 and not more than 0.75. If the above weight ratio (content of N-alkylbismaleimide compound having a skeleton derived from dimer diamine/total content of epoxy compound and hardener) is less than 0.05 or exceeds 0.75, then It is difficult to exert all the effects of the present invention of the above-mentioned 1)-5) and the effects of 1)-6).

The above weight ratio (content of N-alkylbismaleimide compound having a skeleton derived from dimer diamine/total content of epoxy compound and hardener) is preferably 0.15 or more, and preferably 0.5 or less. When the said weight ratio is more than the said minimum and below the said upper limit, the effect of this invention of said 1)-5) and the effect of 1)-6) can be exhibited more effectively.

The content of the N-alkylbismaleimide compound having a skeleton derived from a dimer diamine in 100% by weight of the components other than the inorganic filler and the solvent in the resin material is preferably 5 wt% or more, more preferably 10 wt% or more, further preferably 15 wt% or more. The content of the N-alkylbismaleimide compound having a skeleton derived from a dimer diamine in 100% by weight of the components other than the inorganic filler and the solvent in the resin material is preferably 65%. % by weight or less, more preferably less than 60% by weight, further preferably less than 55% by weight, especially preferably less than 50% by weight. If the content of the above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine is more than the above-mentioned lower limit, the dielectric loss tangent can be reduced, and the distance between the insulating layer and the metal layer can be further improved. Adhesiveness, plating peel strength, etching performance and flexibility of resin film. If the content of the above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine is below the above-mentioned upper limit, the flame retardancy can be further improved, and the coefficient of linear expansion can be suppressed even lower. Further improve the peel strength of the coating.

The molecular weight of the above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine is preferably 500 or more, more preferably 600 or more, and is preferably less than 15,000, more preferably It is less than 11000, more preferably less than 8000. When the above-mentioned molecular weight is more than the above-mentioned lower limit and below the above-mentioned upper limit, the adhesion between the insulating layer and the metal layer can be further improved, and the melt viscosity can be reduced to improve the coverage of the resin material (resin film) on the circuit board.

The molecular weight of the above-mentioned N-alkylbismaleimide compound having a skeleton derived from a dimer diamine is in the case where the N-alkylbismaleimide compound is not a polymer, and may be When specifying the structural formula of the N-alkylbismaleimide compound, it means a molecular weight that can be calculated from the structural formula. In addition, the molecular weight of the above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine is when the N-alkylbismaleimide compound is a polymer. , represents the weight average molecular weight in terms of polystyrene as measured by gel permeation chromatography (GPC).

<N-Alkylbenzophenone compound having a skeleton derived from dimer diamine> The resin material of the present invention preferably contains the above-mentioned N-alkylbenzophenone compound having a skeleton derived from dimer diamine 𠯤 compounds. The above-mentioned N-alkylbenzophenone compound having a skeleton derived from dimer diamine is preferably one of the above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine. A compound in which the maleimide skeleton is substituted with a benzo㗁𠯤 skeleton. The dielectric loss tangent can be reduced, and the adhesion between the insulating layer and the metal layer and the peeling strength of the plating layer can be improved by using the above-mentioned N-alkylbenzoxalgae compound having a skeleton derived from dimer diamine. In addition, etching performance can be improved by using the above-mentioned N-alkylbenzoxazine compound having a skeleton derived from dimer diamine. In addition, the curing temperature can be kept low by using the above-mentioned N-alkylbenzoxazine compound having a skeleton derived from dimer diamine. The above-mentioned N-alkylbenzo(a)benzo(a) compound having a skeleton derived from dimer diamine may also be in the state of an oligomer. The above-mentioned N-alkylbenzo[rho]yl compound having a skeleton derived from dimer diamine may also have a molecular weight distribution. The above-mentioned N-alkylbenzo(a)benzo(a) compounds having a skeleton derived from dimer diamine may be used alone or in combination of two or more.

The skeleton derived from dimer diamine exists as a part of the skeleton in the N-alkylbenzoxazine compound having the skeleton derived from dimer diamine. It is preferable that the N-alkyl benzo 㗁 𠯤 compound having a skeleton derived from a dimer diamine has a structure in which an aliphatic skeleton is bonded to a nitrogen atom in a benzo 㗁 𠯤 group.

It is preferable that the above-mentioned N-alkylbenzoxazolium compound having a skeleton derived from dimer diamine is an N-alkylbisbenzoxazolium compound having a skeleton derived from dimer diamine.

It is preferable that the above-mentioned N-alkylbenzoxamethonium compound having a skeleton derived from dimer diamine has a skeleton derived from a reactant of tetracarboxylic dianhydride and dimer diamine. The reactant of the above-mentioned tetracarboxylic dianhydride and the above-mentioned dimer diamine is preferably a compound having amino groups at both ends.

The above-mentioned N-alkylbenzophenone compound having a skeleton derived from dimer diamine, for example, can be used to obtain the reactant of tetracarboxylic dianhydride and dimer diamine (preferably a compound with amino groups at both ends) ) After, make this reactant, phenol and paraformaldehyde react and obtain.

As said tetracarboxylic dianhydride, the said tetracarboxylic dianhydride is mentioned.

As a commercial item of the said dimer diamine, the said commercial item is mentioned.

From the viewpoint of more effectively exerting the effects of the present invention, the N-alkylbenzoxamethonium compound having a skeleton derived from dimer diamine preferably has a structure represented by the following formula (X).

[Chem 3]

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

As R1 in said formula (X), the group which has an aromatic ring, the group which has a biphenyl ether skeleton, etc. are mentioned. As a group which has the said aromatic ring, the group which has a skeleton derived from pyromellitic anhydride, etc. are mentioned. As the group having the above-mentioned biphenyl ether skeleton, a group having a skeleton derived from 4,4'-oxydiphthalic anhydride, etc. are mentioned.

The above-mentioned N-alkylbenzoxamethonium compound having a skeleton derived from dimer diamine may have one structure represented by the above formula (X), may have two structures, or may have two or more structures.

The weight ratio of the content of the above-mentioned N-alkylbenzoxazine compound having a skeleton derived from dimer diamine to the total content of the above-mentioned epoxy compound and the above-mentioned hardener is referred to as "weight ratio (with diamine-derived The content of N-alkyl benzo 㗁 𠯤 compound in the backbone of polymer diamine/total content of epoxy compound and hardener)". In the case where the above-mentioned resin material contains the above-mentioned N-alkylbenzophenone compound having a skeleton derived from dimer diamine, the above weight ratio (N-alkylbenzene having a skeleton derived from dimer diamine And 㗁𠯤 compound content/total content of epoxy compound and hardener) is 0.05 to 0.75. If the above-mentioned weight ratio (content of N-alkyl benzo-a-methan compound having a skeleton derived from dimer diamine/total content of epoxy compound and hardener) is less than 0.05 or exceeds 0.75, it is difficult to exert the above-mentioned 1 )-5) of the effects of the present invention and all of the effects of 1)-6).

The above-mentioned weight ratio (content of N-alkylbenzoxamethene compound having a skeleton derived from dimer diamine/total content of epoxy compound and hardener) is preferably 0.15 or more and preferably 0.5 or less. When the said weight ratio is more than the said minimum and below the said upper limit, the effect of this invention of said 1)-5) and the effect of 1)-6) can be exhibited more effectively.

It is preferable that the content of the above-mentioned N-alkylbenzoxamethan compound having a skeleton derived from a dimer diamine is 5% by weight or more in 100% by weight of the components other than the inorganic filler and the solvent in the above-mentioned resin material, More preferably, it is 10 weight% or more, More preferably, it is 15 weight% or more. It is preferable that the content of the above-mentioned N-alkylbenzo(o)sulfone compound having a skeleton derived from dimer diamine is not more than 65% by weight in 100% by weight of the components other than the inorganic filler and the solvent in the above-mentioned resin material, More preferably, it is 60 weight% or less, More preferably, it is 55 weight% or less, Especially preferably, it is 50 weight% or less. If the content of the above-mentioned N-alkylbenzo-a-methan compound having a skeleton derived from dimer diamine is more than the above-mentioned lower limit, the dielectric loss tangent can be reduced, and the adhesion between the insulating layer and the metal layer can be further improved, and the plating layer can be peeled off. Strength, etching performance and flexibility of resin film. If the content of the above-mentioned N-alkylbenzoxamethene compound having a skeleton derived from dimer diamine is below the above-mentioned upper limit, the flame retardancy can be further improved, the coefficient of linear expansion can be suppressed even lower, and the peeling of the plating layer can be further improved. strength.

The molecular weight of the above-mentioned N-alkylbenzoxamethan compound having a skeleton derived from dimer diamine is preferably 500 or more, more preferably 600 or more, and is preferably less than 15,000, more preferably less than 11,000, Furthermore, it is more preferable that it is less than 8000. When the above-mentioned molecular weight is more than the above-mentioned lower limit and below the above-mentioned upper limit, the adhesion between the insulating layer and the metal layer can be further improved, and the melt viscosity can be reduced to improve the coverage of the resin material (resin film) on the circuit board.

The molecular weight of the above-mentioned N-alkylbenzoxazine compound having a skeleton derived from dimer diamine can be specified in the case where the N-alkylbenzoxazolium compound is not a polymer, and the N-alkylbenzene In the case of a structural formula of a 㗁𠯤 compound, it means a molecular weight that can be calculated from the structural formula. In addition, the molecular weight of the above-mentioned N-alkylbenzoxazine compound having a skeleton derived from a dimer diamine indicates that the molecular weight of the N-alkylbenzoxazolium compound passed through the gel permeation layer when the N-alkylbenzoxazolium compound is a polymer The weight average molecular weight in terms of polystyrene conversion measured by analytical method (GPC).

[Epoxy Compound] The resin material described above contains an epoxy compound. As the epoxy compound, a conventionally known epoxy compound can be used. The above-mentioned epoxy compound refers to an organic compound having at least one epoxy group. The said epoxy compound may use only 1 type, and may use 2 or more types together.

Examples of the above-mentioned epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenolic novolak type epoxy compounds, biphenyl type epoxy compounds, bisphenol type epoxy compounds, and bisphenol type epoxy compounds. Phenol novolak type epoxy compound, biphenol type epoxy compound, naphthalene type epoxy compound, fennel type epoxy compound, phenol aralkyl type epoxy compound, naphthol aralkyl type epoxy compound, dicyclopentadiene Alkene-type epoxy compounds, anthracene-type epoxy compounds, epoxy compounds having an adamantane skeleton, epoxy compounds having a tricyclodecane skeleton, naphthyl ether-type epoxy compounds, and rings having a tricyclodecane skeleton as a skeleton Oxygen compounds, etc.

The above-mentioned epoxy compound is preferably an epoxy compound with an aromatic skeleton, more preferably an epoxy compound with a naphthalene skeleton or a phenyl skeleton, more preferably an epoxy compound with an aromatic skeleton, especially an epoxy compound with Epoxy compound with naphthalene skeleton. In this case, the dielectric loss tangent can be further reduced, the flame retardancy can be improved, and the linear expansion coefficient can be reduced.

From the viewpoint of further reducing the dielectric loss tangent and improving the coefficient of linear expansion (CTE) of the cured product, the above-mentioned epoxy compound is preferably a liquid epoxy compound at 25°C and an epoxy compound at 25°C. The following is a solid epoxy compound.

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

When measuring the viscosity of the said epoxy compound, the dynamic viscoelasticity measuring apparatus ("VAR-100" by Reologica Instruments company) etc. can be used, for example.

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

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

From the viewpoint of further improving the adhesive strength between the hardened product and the metal layer, the content of the above-mentioned epoxy compound is preferably at least 15% by weight, more preferably 20% by weight, in 100% by weight of the components in the resin material except the solvent. above, and preferably less than 50% by weight, more preferably less than 40% by weight.

The weight ratio of the content of the above-mentioned epoxy compound to the total content of the above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine and the above-mentioned curing agent (the content of the above-mentioned epoxy compound /The total content of the above-mentioned N-alkylbismaleimide compound and the above-mentioned curing agent) is preferably 0.2 or more, more preferably 0.25 or more. The weight ratio of the content of the above-mentioned epoxy compound to the total content of the above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine and the above-mentioned curing agent (the content of the above-mentioned epoxy compound /The total content of the above-mentioned N-alkylbismaleimide compound and the above-mentioned curing agent) is preferably 0.9 or less, more preferably 0.8 or less. When the above weight ratio (content of the above epoxy compound/total content of the above N-alkylbismaleimide compound and the above curing agent) is more than the above lower limit and below the above upper limit, the dielectric loss tangent can be reduced. , to further improve the adhesion between the insulating layer and the metal layer, the peeling strength of the coating, the flame retardancy and the flexibility of the resin film, and reduce the roughness.

The weight ratio of the content of the above-mentioned epoxy compound to the total content of the above-mentioned N-alkylbenzoxamethene compound having a skeleton derived from dimer diamine and the above-mentioned curing agent (content of the above-mentioned epoxy compound/the above-mentioned N- The total content of the alkyl benzo (a) compound and the aforementioned curing agent) is preferably 0.2 or more, more preferably 0.25 or more. The weight ratio of the content of the above-mentioned epoxy compound to the total content of the above-mentioned N-alkylbenzoxamethene compound having a skeleton derived from dimer diamine and the above-mentioned curing agent (content of the above-mentioned epoxy compound/the above-mentioned N- The total content of the alkyl benzo (a) compound and the curing agent) is preferably 0.9 or less, more preferably 0.8 or less. If the above weight ratio (the content of the above-mentioned epoxy compound/the total content of the above-mentioned N-alkyl benzo α ◁ ? The adhesion between the layer and the metal layer, the peeling strength of the coating, the flame retardancy and the flexibility of the resin film can reduce the roughness.

[Inorganic Filler] The above resin material includes an inorganic filler. By using the above-mentioned inorganic filler, the dielectric loss tangent of the cured product can be further reduced. In addition, by using the above-mentioned inorganic filler, the dimensional change due to the heat of the cured product is further reduced. The said inorganic filler may use only 1 type, and may use 2 or more types together.

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

In terms of reducing the surface roughness of the hardened product, further improving the bonding strength between the hardened product and the metal layer, and forming finer wiring on the surface of the hardened product, and giving good insulation reliability by the cured product , the above-mentioned inorganic filler is preferably silicon dioxide or aluminum oxide, more preferably silicon dioxide, and further preferably fused silicon dioxide. By using silicon dioxide, the thermal expansion coefficient of the cured product is further lowered, and the dielectric loss tangent of the cured product is further lowered. In addition, by using silicon dioxide, the surface roughness of the surface of the hardened product is effectively reduced, and the bonding strength between the hardened product and the metal layer is effectively improved. The shape of silicon dioxide is preferably spherical.

From the standpoint of curing the resin regardless of the curing environment, effectively increasing the glass transition temperature of the cured product, and effectively reducing the thermal expansion coefficient of the cured product, the above-mentioned inorganic filler is preferably spherical silica.

The average particle size of the inorganic filler is preferably more than 50 nm, more preferably more than 100 nm, more preferably more than 500 nm, and preferably less than 5 μm, more preferably less than 3 μm, and more preferably 2 μm or less. μm or less. If the average particle size of the above-mentioned inorganic filler is more than the above-mentioned lower limit and below the above-mentioned upper limit, the thickness can be reduced, and the adhesion between the insulating layer and the metal layer and the peeling strength of the plating layer can be further improved.

As the average particle diameter of the said inorganic filler, the value which becomes a 50% median diameter (d50) is employ|adopted. The said average particle diameter can be measured using the particle size distribution measuring apparatus of a laser diffraction scattering method.

The aforementioned inorganic filler is preferably spherical, more preferably spherical silica. In this case, the surface roughness of the surface of the hardened product is effectively reduced, and the bonding strength between the hardened product and the metal layer is effectively improved. When the above-mentioned inorganic filler is spherical, the aspect ratio of the above-mentioned 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 obtained by using a coupling agent, and still more preferably a surface-treated product obtained by using a silane coupling agent. By performing surface treatment on the above-mentioned inorganic filler, the surface roughness of the surface of the roughened hardened product is further reduced, and the adhesive strength between the hardened product and the metal layer is further improved. Moreover, by surface-treating the above-mentioned inorganic filler, finer wiring can be formed on the surface of the cured product, and better inter-wiring insulation reliability and interlayer insulation reliability can be imparted to the cured 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 methacrylsilane, acrylsilane, aminosilane, imidazolesilane, vinylsilane, and epoxysilane.

The content of the above-mentioned inorganic filler is preferably at least 50% by weight, more preferably at least 60% by weight, further preferably at least 65% by weight, and most preferably at least 68% by weight, based on 100% by weight of the components other than the solvent in the resin material. % or more, and preferably less than 90% by weight, more preferably less than 85% by weight, further preferably less than 80% by weight, especially preferably less than 75% by weight. The dielectric loss tangent will be reduced effectively that content of the said inorganic filler is more than the said minimum. Etching performance can be improved as content of the said inorganic filler is below the said upper limit. When the content of the above-mentioned inorganic filler is more than the above-mentioned lower limit and below the above-mentioned upper limit, the surface roughness of the surface of the cured product can be further reduced, and finer wiring can be formed on the surface of the cured product. Furthermore, if the amount of the inorganic filler is such that the thermal expansion coefficient of the cured product is lowered, the decontamination property can also be improved.

[Hardener] The above-mentioned resin material includes a hardener containing a phenolic compound, a cyanate compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a benzo that does not have a skeleton derived from a dimer diamine. At least one component of the 㗁𠯤 compound. That is, the above-mentioned resin material contains a curing agent containing component X. It is preferable that the above-mentioned benzodiazepine compound does not have a skeleton derived from a diamine compound other than dimer diamine. The above curing agents may be used alone or in combination of two or more.

Component X: Component X is a phenolic compound (phenol hardener), a cyanate compound (cyanate hardener), an anhydride, an active ester compound, a carbodiimide compound (carbodiimide hardener), and no source At least one component of a benzo㗁𠯤 compound derived from a dimer diamine skeleton (benzo㗁𠯤 hardening agent). That is, the above-mentioned resin material contains a curing agent containing component X. The said component X may use only 1 type, and may use 2 or more types together.

From the viewpoint of further improving the flame retardancy and reducing the coefficient of linear expansion, the above-mentioned component X is preferably a component having an aromatic skeleton, and more preferably contains at least a phenolic compound. Also, from the viewpoint of further improving the flame retardancy and further reducing the coefficient of linear expansion, it is preferable that the above-mentioned epoxy compound is an epoxy compound having an aromatic skeleton, and that the above-mentioned component X is a component having an aromatic skeleton. .

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

Examples of commercially available phenolic compounds include novolak-type phenols ("TD-2091" manufactured by DIC Corporation), biphenyl novolak-type phenols ("MEH-7851" manufactured by Meiwa Kasei Co., Ltd.), aralkyl Type phenolic compounds ("MEH-7800" manufactured by Meiwa Kasei Co., Ltd.), and phenols having an amino trisulfone skeleton ("LA1356" and "LA3018-50P" manufactured by DIC Corporation) and the like.

Examples of the cyanate compound include novolak-type cyanate resins, bisphenol-type cyanate resins, and prepolymers obtained by partial trimerization of these. As said novolac type cyanate resin, a phenolic 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, tetramethylbisphenol F type cyanate resin, etc. are mentioned.

Examples of commercially available cyanate compounds include phenolic novolak-type cyanate resins ("PT-30" and "PT-60" manufactured by Lonza Japan Co., Ltd.), and bisphenol-type cyanate resins. Prepolymers obtained by trimerization ("BA-230S", "BA-3000S", "BTP-1000S" and "BTP-6020S" manufactured by Lonza Japan Co., Ltd.), etc.

Tetrahydrophthalic anhydride, an alkylstyrene-maleic anhydride copolymer, etc. are mentioned as said acid anhydride.

As a commercial item of the said acid anhydride, "RIKACID TDA-100" by the Nippon Physical and Chemical Co., Ltd. etc. are mentioned.

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

[chemical 4]

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 said aromatic ring containing group, the benzene ring which may have a substituent, the naphthalene ring which may have a substituent, etc. are mentioned. A hydrocarbon group is mentioned as said substituent. The carbon number of the hydrocarbon group is preferably 12 or less, more preferably 6 or less, still more preferably 4 or less.

Examples of the combination of X1 and X2 include a combination of an optionally substituted benzene ring and an optionally substituted benzene ring, and a combination of an optionally substituted benzene ring and an optionally substituted naphthalene ring. Furthermore, as a combination of X1 and X2, the combination of the naphthalene ring which may have a substituent, and the naphthalene ring which may have a substituent is mentioned.

The above-mentioned active ester compound is not particularly limited. From the viewpoint of further improving the flame retardancy and reducing the coefficient of linear expansion, the above-mentioned active ester is preferably an active ester compound having two or more aromatic skeletons. Therefore, it is preferable that the said hardening|curing agent contains the active ester compound which has 2 or more aromatic skeletons. From the viewpoint of reducing the dielectric loss tangent of the cured product and improving the thermal dimensional stability of the cured product, it is more preferable to have a naphthalene ring in the main chain skeleton of the active ester.

As a commercial item of the said active ester compound, "HPC-8000-65T", "EXB9416-70BK", "EXB8100-65T", "HPC-8150-60T" by DIC Corporation etc. are mentioned.

The above-mentioned carbodiimide compound has a structural unit represented by the following formula (2). In the following formula (2), the right end and the left end are bonding sites with other groups. The said carbodiimide compound may use only 1 type, and may use 2 or more types together.

[chemical 5]

In the above formula (2), X represents an alkylene group, a group having a substituent bonded to the alkylene group, a cycloalkylene group, a group having a substituent bonded to the cycloalkylene group, an aryl group, or In the group having a substituent bonded to the aryl group, p represents an integer of 1-5. When there are plural Xs, the plural Xs may be the same or different.

In a preferred embodiment, at least one X is an alkylene group, a group having a substituent bonded to the alkylene group, a cycloalkylene group, or a group having a substituent bonded to the cycloalkylene group.

Commercially available products of the aforementioned carbodiimide compounds include "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", "Carbodilite V-09", "Carbodilite 10M-SP", and "Carbodilite 10M-SP (modified)", "Stabaxol P", "Stabaxol P400", and "Hycasyl 510" manufactured by Rhein Chemie Co., Ltd., etc.

Examples of the benzophenone compound not having a skeleton derived from dimer diamine include P-d type benzophenone, F-a type benzophenone, and the like.

As a commercially available product of the above-mentioned benzoglyceride compound not having a skeleton derived from dimer diamine, "P-d type" manufactured by Shikoku Chemical Industry Co., Ltd. and the like are exemplified.

The content of the component X is preferably at least 50 parts by weight, more preferably at least 85 parts by weight, and preferably at most 150 parts by weight, more preferably at most 120 parts by weight, based on 100 parts by weight of the epoxy compound. When the content of the above-mentioned component X is more than the above-mentioned lower limit and below the above-mentioned upper limit, the curability is more excellent, and the dimensional change of the cured product caused by heat or the volatilization of remaining unreacted components can be further suppressed.

The total content of the above-mentioned epoxy compound and the above-mentioned component X is preferably at least 40% by weight, more preferably at least 60% by weight, and is preferably 90% by weight or less, more preferably 85% by weight or less. When the total content of the above-mentioned epoxy compound and the above-mentioned component X is more than the above-mentioned minimum and below the above-mentioned upper limit, a better cured product can be obtained, and the dimensional change of the cured product due to heat can be further suppressed.

The above-mentioned resin material may contain a curing agent different from the above-mentioned curing agent containing the above-mentioned component X. Examples of hardeners that are different from the above-mentioned hardeners containing the above-mentioned component X include amine compounds (amine hardeners), thiol compounds (thiol hardeners), phosphine compounds, dicyandiamide, and maleimide Amine compound (maleimide hardener), etc.

[Hardening accelerator] The resin material described above preferably contains a hardening accelerator. By using the above-mentioned hardening accelerator, the hardening rate is further increased. By rapidly hardening the resin material, the cross-linked structure of the hardened product becomes uniform, and the number of unreacted functional groups decreases, resulting in an increase in cross-link density. When the curing of the resin material is not sufficiently advanced, the dielectric loss tangent becomes high and the coefficient of linear expansion may become large. By using a hardening accelerator, the effect of the resin material can be fully performed. The above-mentioned hardening accelerator is not particularly limited, and a previously known hardening accelerator can be used. The said hardening accelerator may use only 1 type, and may use 2 or more types together.

Examples of the 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 Base-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methyl Imidazole, 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 '-Methylimidazolyl-(1')]-Ethyl-S-trimethazolium, 2,4-Diamino-6-[2'-Undecylimidazolyl-(1')]-Ethyl- S-Trisone, 2,4-Diamino-6-[2'-Ethyl-4'-methylimidazolyl-(1')]-Ethyl-S-Trisone, 2,4-Diamino- 6-[2'-Methylimidazolyl-(1')]-Ethyl-S-tri-isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methyl Imidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-dihydroxymethylimidazole, etc.

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

As said phosphorus compound, a triphenylphosphine compound etc. are mentioned.

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

As said peroxide, dicumyl peroxide, PERHEXYL 25B, etc. are mentioned.

From the viewpoint of suppressing the curing temperature lower, the above-mentioned curing accelerator preferably contains the above-mentioned anionic curing accelerator, and more preferably contains the above-mentioned imidazole compound.

From the viewpoint of keeping the curing temperature lower, the content of the anionic curing accelerator in 100% by weight of the curing accelerator is preferably at least 50% by weight, more preferably at least 70% by weight, and still more preferably at least 70% by weight. More than 80% by weight, preferably 100% by weight (full amount).

The above-mentioned hardening accelerator preferably contains at least one of an anionic hardening accelerator and a radical hardening accelerator. The anionic hardening accelerator is preferably an imidazole compound. The above-mentioned hardening accelerator may also contain the above-mentioned radical hardening accelerator and the above-mentioned imidazole compound. The above-mentioned radical hardening accelerator is preferably a radical hardening accelerator whose reaction temperature in the presence of the above-mentioned radical hardening accelerator is higher than the hardening temperature before etching and lower than the full-scale hardening temperature after etching. In the case of using a radical hardening accelerator, by using PERHEXYL 25B as a radical hardening accelerator, the above effects can be more effectively exhibited.

Moreover, it is preferable that the said hardening accelerator contains a radical hardening accelerator and an imidazole compound, or contains a radical hardening accelerator and a phosphorus compound. In this case, hardening of the said resin material can be made to progress favorably, and a more favorable cured product can be obtained.

The above-mentioned hardening accelerator may contain a radical hardening accelerator and at least one compound selected from dimethylaminopyridine, imidazole compound, and phosphorus compound.

The content of the above-mentioned hardening accelerator is not particularly limited. The content of the hardening accelerator is preferably at least 0.01% by weight, more preferably at least 0.05% by weight, and more preferably at most 5% by weight, in 100% by weight of components other than inorganic fillers and solvents in the resin material, and more preferably at most 5% by weight. Preferably, it is 3% by weight or less. The resin material will be hardened efficiently as content of the said hardening accelerator is more than the said minimum and below the said upper limit. If the content of the above-mentioned hardening accelerator is in a more preferable range, the storage stability of the resin material is further improved, and a better hardened product can be obtained.

[Thermoplastic Resin] The resin material described above preferably contains a thermoplastic resin. As said thermoplastic resin, a polyvinyl acetal resin, a polyimide resin, a phenoxy resin, etc. are mentioned. The said thermoplastic resin may use only 1 type, and may use 2 or more types together.

The above-mentioned thermoplastic resin is preferably a phenoxy resin from the viewpoint of effectively reducing the dielectric loss tangent regardless of the curing environment and effectively improving the adhesion of metal wiring. By using a phenoxy resin, deterioration of coverage of holes or unevenness of a circuit board by a resin film and unevenness of an inorganic filler can be suppressed. In addition, by using phenoxy resin, the melt viscosity can be adjusted, so the dispersibility of the inorganic filler becomes good, and the resin composition or B-staged product becomes less prone to wetting and spreading in unintended areas during the curing process. .

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

Examples of the above-mentioned phenoxy resins include phenoxy resins having a bisphenol A-type skeleton, a bisphenol F-type skeleton, a bisphenol S-type skeleton, a biphenyl skeleton, a novolac skeleton, a naphthalene skeleton, and an imide skeleton. base resin etc.

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

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

From the viewpoint of improving solubility, the above-mentioned polyimide compound is preferably a polyimide compound obtained by a method of making tetracarboxylic dianhydride and dimer diamine react.

As said tetracarboxylic dianhydride, the said tetracarboxylic dianhydride is mentioned.

As a commercial item of the said dimer diamine, the said commercial item is mentioned.

From the viewpoint of obtaining a resin material more excellent in storage stability, the weight average molecular weight of the above-mentioned thermoplastic resin, the above-mentioned polyimide resin and the above-mentioned phenoxy resin is preferably 5000 or more, more preferably 10000 or more, and preferably It is 100000 or less, more preferably 50000 or less.

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

The content of the above-mentioned thermoplastic resin, the above-mentioned polyimide resin and the above-mentioned phenoxy resin is not particularly limited. The content of the above-mentioned thermoplastic resin in 100% by weight of the components other than the above-mentioned inorganic filler and the above-mentioned solvent in the resin material (when the above-mentioned thermoplastic resin is a polyimide resin or a phenoxy resin, it is a polyimide resin or phenoxy resin content) is preferably at least 1% by weight, more preferably at least 2% by weight, and is preferably at most 30% by weight, more preferably at most 20% by weight. When content of the said thermoplastic resin is more than the said minimum and below the said upper limit, the coverage property of a resin material with respect to the hole of a circuit board, or uneven|corrugated becomes favorable. Formation of a resin film will become easier as content of the said thermoplastic resin is more than the said minimum, and a more favorable insulating layer can be obtained. When content of the said thermoplastic resin is below the said upper limit, the thermal expansion coefficient of hardened|cured material will fall further. 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 will be further reduced, and the bonding strength between the cured product and the metal layer will be further improved.

[Solvent] The above-mentioned resin material does not contain a solvent or contains a solvent. By using the above-mentioned solvent, the viscosity of the resin material can be controlled in a preferable range, and the coatability of the resin material can be improved. Moreover, the said solvent can also be used to obtain the slurry containing the said inorganic filler. The said solvent may use only 1 type, and may use 2 or more types together.

Examples of the solvent include: acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-acetyl 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 molding the above-mentioned resin composition into a film. Therefore, the boiling point of the above-mentioned solvent is preferably below 200°C, more preferably below 180°C. The content of the above-mentioned solvent in the above-mentioned resin composition is not particularly limited. The content of the above-mentioned solvent may be appropriately changed in consideration of the coatability of the above-mentioned resin composition and the like.

When the above-mentioned resin material is a B-stage film, the content of the above-mentioned solvent in 100% by weight of the above-mentioned 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 weight% or less.

[Other components] For the purpose of improving impact resistance, heat resistance, resin compatibility and workability, etc., the above resin materials may also contain leveling agents, flame retardants, coupling agents, colorants, antioxidants, and UV degradation prevention Agents, defoamers, tackifiers, thixotropy imparting agents, and other thermosetting resins other than epoxy compounds.

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.

Examples of the above-mentioned other thermosetting resins include polyphenylene ether resins, divinylbenzyl ether resins, polyarylate resins, diallyl phthalate resins, benzoxazole resins, and benzoxazole resins. , bismaleimide resin and acrylate resin, etc.

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

The aforementioned resin material is preferably a thermosetting material.

As a method of molding a resin composition into a film shape and obtaining a resin film, the following methods are mentioned. An extrusion molding method in which a resin composition is melted and kneaded using an extruder, and then extruded into a film shape using a T-die or a circular die. A tape casting method in which a resin composition containing a solvent is cast to form a film. Other previously known film forming methods. Extrusion molding method or tape casting method is preferable at the point which can cope with thinning. Films comprise sheets.

A resin film as a B-stage film can be obtained by molding the resin composition into a film, and heating and drying at, for example, 50° C. to 150° C. for 1 minute to 10 minutes so as not to excessively harden by heat.

The film-like resin composition obtainable through the drying step as described above is called a B-stage film. The B-staged film described above is in a semi-cured state. The semi-hardened material is not fully hardened and can be further hardened.

The said resin film does not need to be a prepreg. When the above-mentioned resin film is not a prepreg, migration along glass cloth or the like does not occur. In addition, when the resin film is laminated or pre-cured, unevenness due to the glass cloth will not be generated on the surface. The above-mentioned resin film can be used in the form of a laminated film comprising a metal foil or a base material and a resin film laminated on the surface of the metal foil or base material. The aforementioned metal foil is preferably copper foil.

Examples of the base material 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, etc. The surface of the above-mentioned substrate may also be subjected to mold release treatment as required.

From the viewpoint of controlling the degree of curing of the resin film more uniformly, the thickness of the resin film is preferably 5 μm or more and preferably 200 μm or less. When using the above-mentioned resin film as an insulating layer of a circuit, the thickness of the insulating layer formed by the above-mentioned resin film is preferably greater than or equal to the thickness of a conductor layer (metal layer) forming a circuit. The thickness of the insulating layer is preferably not less than 5 μm, and is preferably not more than 200 μm.

(Semiconductor Device, Printed Wiring Board, Copper Clad Laminated Board, and Multilayer Printed Wiring Board) The resin material described above can be suitably used as a molding resin for forming a semiconductor chip embedded in a semiconductor device.

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

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

For the above resin film, metal foil can be laminated on one or both sides. The method of laminating the above-mentioned resin film and metal foil is not particularly limited, and a known method can be used. For example, the above-mentioned resin film can be laminated on the metal foil while heating or applying pressure without heating using an apparatus such as a parallel plate press or a roll laminator.

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

The thickness of the said copper foil of the said copper clad 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, it is preferable that the copper foil has fine unevenness on the surface. The method of forming the unevenness is not particularly limited. As a method of forming the above-mentioned unevenness, a method of forming by treatment using a known chemical liquid, etc. may be mentioned.

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

As an example of the said multilayer board|substrate, the multilayer board|substrate provided with the circuit board and the insulating layer laminated|stacked on this circuit board is mentioned. The insulating layer of the multi-layer substrate is formed of the above-mentioned resin material. In addition, a laminated film may be used, and the insulating layer of the multilayer substrate may be formed using the above-mentioned resin film of the above-mentioned laminated film. The above insulating layer is preferably laminated on the surface of the circuit board on which the circuit is provided. A part of the insulating layer is preferably buried between the circuits.

In the above-mentioned multilayer substrate, it is preferable to roughen the surface of the above-mentioned insulating layer opposite to the surface on which the above-mentioned circuit board is laminated.

As the roughening treatment method, a previously known roughening treatment method can be used, and it is not particularly limited. The surface of the insulating layer can also be subjected to swelling treatment before the roughening treatment.

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

Also, as another example of the above-mentioned multilayer substrate, a multilayer substrate including a circuit substrate, an insulating layer laminated on the surface of the circuit substrate, and a surface opposite to the surface on which the circuit substrate is laminated on the insulating layer can be cited. Copper foil on the surface of the side. The insulating layer is preferably formed by using a copper-clad laminate including a copper foil and a resin film laminated on one surface of the copper foil, and curing the resin film. Furthermore, the above-mentioned copper foil is etched, and is preferably a copper circuit.

Another example of the above-mentioned multilayer substrate includes a multilayer substrate including a circuit substrate and a plurality of insulating layers laminated on the surface of the circuit substrate. At least one of the plurality of insulating layers disposed on the circuit board is formed using the resin material described above. It is preferable that the said multilayer board|substrate is further equipped with the circuit laminated|stacked on at least one surface of the said insulating layer formed using the said resin film.

Regarding multilayer printed wiring boards among multilayer substrates, a lower dielectric loss tangent is required, and higher insulation reliability obtained by insulating layers is required. The resin material of the present invention can effectively improve the insulation reliability by reducing the dielectric loss tangent and improving the adhesion and etching performance between the insulating layer and the metal layer. Therefore, the resin material of the present invention can be suitably used to form 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 to 16 are cured material layers. A metal layer 17 is formed on a part of the upper surface 12 a of the circuit substrate 12 . Among the plurality of insulating layers 13-16, except for the insulating layer 16 on the surface opposite to the circuit board 12, the insulating layers 13-15 have a metal layer 17 formed on a part of the upper surface. The metal layer 17 is a circuit. Metal layers 17 are disposed between the circuit board 12 and the insulating layer 13 and between the laminated insulating layers 13 to 16 . The lower metal layer 17 and the upper metal layer 17 are connected to each other by at least one of a via connection and a via connection not shown.

In the multilayer printed wiring board 11, the insulating layers 13-16 are formed of the hardened|cured material of the said resin material. In this embodiment, since the surfaces of the insulating layers 13 to 16 are roughened, fine pores not shown are formed on the surfaces of the insulating layers 13 to 16 . Also, the metal layer 17 reaches inside the fine holes. Moreover, in the multilayer printed wiring board 11, the width direction dimension (L) of the metal layer 17 and the width direction dimension (S) of the part where the metal layer 17 is not formed can be made small. In addition, in the multilayer printed wiring board 11 , good insulation reliability is provided between the upper metal layer and the lower metal layer that are not connected by via connection and via connection not shown.

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

In order to form fine unevenness on the surface of the cured product obtained by precuring the resin material, it is preferable to roughen the cured product. Before roughening treatment, swelling treatment is preferably performed on the cured product. The cured product is preferably subjected to swelling treatment after pre-hardening and before roughening treatment, and then hardened after roughening treatment. However, the swelling treatment may not necessarily be performed on the cured product.

As the method of the above-mentioned swelling treatment, for example, a method of treating a cured product with an aqueous solution of a compound containing ethylene glycol or the like as a main component, an organic solvent dispersion solution, or the like can be used. The swelling solution used for swelling treatment generally contains alkali as a pH value adjusting agent and the like. The swelling liquid preferably contains sodium hydroxide. Specifically, for example, the above-mentioned swelling treatment is performed by 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 aqueous solution of ethylene glycol 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, it will take a long time for the swelling treatment, and the adhesive strength between the cured product and the metal layer will tend to decrease.

The aforementioned roughening treatment uses, for example, a chemical acidifier such as a manganese compound, a chromium compound, or a persulfate compound. These chemical acidifying agents are used in the form of aqueous solution or organic solvent dispersion solution after adding water or organic solvent. The roughening solution used for roughening generally contains alkali as a pH adjuster and the like. It is preferable that a roughening liquid contains sodium hydroxide.

Potassium permanganate, sodium permanganate, etc. are mentioned as said manganese compound. Potassium dichromate, anhydrous potassium chromate, etc. are mentioned as said chromium compound. Sodium persulfate, potassium persulfate, ammonium persulfate, etc. are mentioned as said persulfate compound.

The arithmetic mean roughness Ra of the surface of the cured product is preferably at least 10 nm, 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 cured product and the metal layer is improved, 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 said arithmetic mean roughness Ra is measured based on JISB0601:1994.

(Desmearing treatment) There are cases where through-holes are formed in a cured product obtained by pre-hardening the above-mentioned resin material. In the multilayer substrate and the like described above, a via hole, a via hole, or the like is formed as the through hole. For example, a via hole can be formed by irradiation of a laser such as a CO ₂ laser. The diameter of the via hole is about 60 μm to 80 μm, but it is not particularly limited. In many cases, due to the formation of the above-mentioned through-holes, residues of the resin derived from the resin components contained in the cured product, that is, stains, are formed on the bottom of the via-holes.

In order to remove the above-mentioned stains, the surface of the cured product is preferably subjected to desmear treatment. There are also situations where decontamination treatment is also used as roughening treatment.

The desmutting treatment uses, for example, a chemical acidifying agent such as a manganese compound, a chromium compound, or a persulfate compound in the same manner as the above-mentioned roughening treatment. These chemical acidifying agents are used in the form of aqueous solution or organic solvent dispersion solution after adding water or organic solvent. Decontamination treatment liquids used for decontamination generally contain alkali. The decontamination treatment liquid preferably contains sodium hydroxide.

By using the above-mentioned resin material, the surface roughness of the surface of the desmear-treated cured product becomes sufficiently small.

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

(N-Alkylbismaleimide compound having a skeleton derived from dimer diamine) N-Alkylbismaleimide compound 1 ("BMI" manufactured by Designer Molecules Inc. -1500", number average molecular weight 1500) N-alkylbismaleimide compound 2 ("BMI-1700" manufactured by Designer Molecules Inc., number average molecular weight 1700) N-alkylbismaleimide Diamide imide compound 3 ("BMI-3000" manufactured by Designer Molecules Inc., number average molecular weight 3000) N-alkylbismaleimide compound 4 ("BMI-3000" manufactured by Designer Molecules Inc. 3000J", number average molecular weight 5100) N-alkylbismaleimide compound 5 (after dissolving "BMI-3000J" manufactured by Designer Molecules Inc. in toluene solution, adding isopropanol, and then The compound obtained by recovering the precipitated polymer components (recorded as BMI-3000J treated product in the table), weight average molecular weight 15000)

(N-Alkyl benzo 㗁 𠯤 compound having a skeleton derived from dimer diamine) N-Alkyl benzo 㗁 𠯤 compound (synthesized according to Synthesis Example 1 below)

(Synthesis Example 1) 65 g of pyromellitic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 218.12) and 500 mL of cyclohexanone were added to a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube, and then 164 g of dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan Co., Ltd.) was dissolved in cyclohexanone and added dropwise. Thereafter, a Dean-Stark separator and a condenser were installed in the flask, and the mixture was heated under reflux for 2 hours to obtain an imide compound having amine structures at both ends. The obtained imide compound, 38 g of phenol (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 94.11) and 12 g of paraformaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and the obtained mixture was further refluxed for 12 hours to perform Benzoization. Thereafter, reprecipitation was carried out with isopropanol, thereby obtaining an N-alkylbenzo[url] compound (weight average molecular weight: 7,700).

(Others) N-phenylmaleimide compound ("BMI-2300" manufactured by Daiwa Chemical Industry Co., Ltd.) N-phenylmaleimide compound ("BMI-2300" manufactured by Daiwa Chemical Industry Co., Ltd.) 4000")

(Epoxy compound) Biphenyl type epoxy compound ("NC-3000" manufactured by Nippon Kayaku Co., Ltd.) Naphthalene type epoxy compound ("HP-4032D" manufactured by DIC Corporation) Resorcinol diglycidyl ether (Nagase "EX-201" manufactured by chemteX Corporation) dicyclopentadiene type epoxy compound ("EP4088S" manufactured by ADEKA Corporation) naphthol aralkyl type epoxy compound ("ESN-475V" manufactured by Nippon Steel Sumikin Chemical Co., Ltd.) 」)

(Inorganic filler) Slurry containing silica (75% by weight of silica: “SC4050-HOA” manufactured by Admatechs, average particle size 1.0 μm, treated with aminosilane, 25% by weight of cyclohexanone)

(Curing agent) Component X: Liquid containing cyanate compound ("BA-3000S" manufactured by Lonza Japan Co., Ltd., solid content 75% by weight) Liquid containing active ester compound 1 ("EXB-9416-70BK" manufactured by DIC Corporation) , solid content 70% by weight) active ester compound 2 containing liquid ("HPC-8000L" manufactured by DIC Corporation, solid content 65% by weight) active ester compound 3 containing liquid ("HPC-8150" manufactured by DIC Corporation, solid 62% by weight) Phenolic compound-containing liquid ("LA-1356" manufactured by DIC Corporation, solid content 60% by weight) Carbodiimide compound-containing liquid ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., solid content 50% by weight)

(Hardening accelerator) Dimethylaminopyridine (“DMAP” manufactured by Wako Pure Chemical Industries, Ltd. 2-Phenyl-4-methylimidazole (“2P4MZ” manufactured by Shikoku Chemical Industry Co., Ltd.) 2-Ethyl-4 -Methylimidazole ("2E4MZ" manufactured by Shikoku Chemical Industry Co., Ltd.) Percumyl D (manufactured by NOF Corporation)

(thermoplastic resin) polyimide compound (polyimide resin) (according to the following Synthesis Example 2 to synthesize the reaction product of tetracarboxylic dianhydride and dimer diamine, that is, a solution containing polyimide compound (non-volatile 26.8% by weight)) Phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Corporation)

(Synthesis Example 2) 300.0 g of tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan Co., Ltd.) and 665.5 g of cyclohexanone were added to a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube. g. Heat the solution in the reaction vessel to 60°C. Then, 89.0 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan Co., Ltd.) and 54.7 g of 1,3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd.) were added dropwise to the reaction vessel. . Next, 121.0 g of methylcyclohexane and 423.5 g of ethylene glycol dimethyl ether were added to the reaction container, and an imidization reaction was performed at 140° C. for 10 hours. In this way, a solution (26.8% by weight of non-volatile matter) containing a polyimide compound was obtained. The molecular weight (weight average molecular weight) of the obtained polyimide compound was 20,000. In addition, the molar ratio of acid component/amine component was 1.04.

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

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

(Examples 1-15 and Comparative Examples 1-3) The ingredients shown in the following Tables 1-3 were prepared in the amounts shown in the following Tables 1-3, and stirred at room temperature until a uniform solution was obtained to obtain a resin material.

Manufacture of the resin film: Apply the obtained resin material on the release-treated surface of the release-treated PET film ("XG284" manufactured by Toray Co., Ltd., thickness 25 μm) using an applicator, and heat it in a 100°C Gil oven (Geer oven) for 2 minutes and 30 seconds to evaporate the solvent. In this way, a laminated film (laminated film of a PET film and a resin film) in which a resin film (B-stage film) with a thickness of 40 μm was laminated on the PET film was obtained.

(Evaluation) (1) Dielectric loss tangent The obtained resin film was cut into a size of 2 mm in width and 80 mm in length, and five sheets were stacked to obtain a laminate with a thickness of 200 μm. The obtained laminate was heated at 190° C. for 90 minutes to obtain a hardened body. For the hardened body obtained, the "Cavity Resonance Perturbation Method Dielectric Constant Measuring Device CP521" manufactured by Kanto Electronics Application Development Co., Ltd. and the "Network Analyzer N5224A PNA" manufactured by Keysight Technologie were used in the cavity resonance method. At room temperature (23°C), the dielectric loss tangent was measured at a frequency of 1.0 GHz.

(2) Adhesion (peel strength) between the insulating layer and the metal layer Lamination steps: Prepare double-sided copper-clad laminates (the thickness of the copper foil on each side is 18 μm, the thickness of the substrate is 0.7 mm, and the substrate size is 100 mm×100 mm , "MCL-E679FG" manufactured by Hitachi Chemical Co., Ltd.). Both sides of the copper foil surface of this double-sided copper-clad laminate were dipped in "Cz8101" manufactured by MEC Corporation, and the surface of the copper foil was roughened. On both sides of the roughened copper-clad laminate, use the "batch type vacuum laminator MVLP-500-IIA" manufactured by Meiki Co., Ltd. to overlap the resin film (B-stage film) side of the laminate film on the Copper-clad laminates are laminated to obtain a laminated structure. The lamination conditions were depressurized for 30 seconds so that the air pressure became 13 hPa or less, and then pressurized at 100° C. and a pressure of 0.4 MPa for 30 seconds.

Film peeling step: In the obtained laminated structure, the PET films on both sides were peeled off.

Copper foil attachment step: Cz treatment ("Cz8101" manufactured by MEC Co., Ltd.) is performed on the smooth surface of the copper foil (thickness 35 μm, manufactured by Mitsui Kinzoku Co., Ltd.), and the surface of the copper foil is etched by about 1 μm. The etched copper foil was bonded to the laminated structure in which the PET film was peeled off to obtain a copper foil-attached substrate. The obtained substrate with copper foil was heat-treated at 190° C. for 90 minutes in a Jill oven to obtain an evaluation sample.

(2-1) Measurement of peel strength at room temperature: A short strip-shaped incision with a width of 1 cm was cut on the surface of the copper foil of the evaluation sample. An evaluation sample was installed in a 90° peel tester ("TE-3001" manufactured by TESTER SANGYO Co., Ltd.), the end of the copper foil having a notch was clamped with a jig, and the copper foil was peeled off by 20 mm to measure the peel strength (peel strength).

[Criteria for judging peel strength at room temperature] ○○: Peel strength is 0.6 kgf or more ○: Peel strength is 0.4 kgf or more and less than 0.6 kgf ×: Peel strength is less than 0.4 kgf

(2-2) Measurement of peel strength under high temperature (260°C) environment: A short strip-shaped incision with a width of 1 cm was cut on the surface of the copper foil of the evaluation sample. After installing the heating unit at the position where the evaluation sample was installed in the 90° peel tester ("TE-3001" manufactured by Tester Sangyo Co., Ltd.), the evaluation sample was installed, and the heating unit was set at 260°C. Then, the edge part of the copper foil which has a notch was clamped with the jig, and the copper foil was peeled off 20 mm, and the peel strength (peel strength) was measured.

[Criteria for judging peel strength under high temperature (260°C) environment] ○○: Peel strength is 0.1 kgf or more ○: Peel strength is 0.05 kgf or more and less than 0.1 kgf ×: Peel strength is less than 0.05 kgf

(3) Flame retardancy Lamination process: Prepare a double-sided copper-clad laminate (thickness 0.2 mm, "MCL-E-679FGR" manufactured by Hitachi Chemical Co., Ltd.). On both sides of the double-sided copper-clad laminate, use the "batch type vacuum laminator MVLP-500-IIA" manufactured by Meiji Co., Ltd. to overlap the resin film (B-stage film) side of the laminate film on the copper-clad The laminated sheets are laminated to obtain a laminated structure. The lamination conditions were depressurized for 30 seconds so that the air pressure became 13 hPa or less, and then pressurized at 100° C. and a pressure of 0.4 MPa for 30 seconds.

Film peeling step: In the obtained laminated structure, the PET films on both sides were peeled off.

Lamination process: The obtained resin film with a thickness of 40 μm is attached twice on both sides of the above-mentioned laminate structure, and a resin film with a total thickness of 120 μm is layered on each single area of a double-sided copper-clad laminate Laminated samples.

Hardening step: The obtained laminated sample was heat-treated in a Gil oven at 190°C for 90 minutes to obtain an evaluation sample.

Evaluation of Flame Retardancy: The obtained evaluation sample was cut into length 135 mm x width 13 mm. Next, the cut out evaluation sample was fixed with a splint, the flame of the gas burner was placed under the evaluation sample, and the resin film was burned. The time until the flame spreading to the resin film is extinguished was measured.

[Criteria for Flame Retardancy] ○○: The time until the flame is extinguished is less than 7 seconds ○: The time until the flame is extinguished is more than 7 seconds and less than 10 seconds ×: The time until the flame is extinguished is more than 10 seconds

(4) Surface roughness (surface roughness after roughening treatment) Lamination step and semi-hardening treatment: A double-sided copper-clad laminate (CCL substrate) ("E679FG" manufactured by Hitachi Chemical Co., Ltd.) was prepared. Both sides of the copper foil surface of this double-sided copper-clad laminate were dipped in "Cz8101" manufactured by MEC Corporation, and the surface of the copper foil was roughened. On both sides of the roughened copper-clad laminate, use the "batch type vacuum laminator MVLP-500-IIA" manufactured by Meiki Co., Ltd. to overlap the resin film (B-stage film) side of the laminate film on the Copper-clad laminates are laminated to obtain a laminated structure. The lamination conditions were depressurized for 30 seconds so that the air pressure became 13 hPa or less, and then pressurized at 100° C. and a pressure of 0.4 MPa for 30 seconds. Thereafter, heating was performed at 180° C. for 30 minutes to semi-harden the resin film. In this way, a laminate in which the semi-cured material of the resin film was laminated on the CCL substrate was obtained.

Coarsening treatment: (a) Swelling treatment: The obtained laminate was placed in an 80°C swelling solution ("Swelling Dip Securigant P" manufactured by Atotech Japan Co., Ltd.), and shaken for 10 minutes. Thereafter, it was washed with pure water.

(b) Permanganate treatment (coarsening treatment and decontamination treatment): Put the laminate after swelling treatment in a coarsening aqueous solution of potassium permanganate ("Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd.) at 60°C , shake for 30 minutes. Next, after treating for 2 minutes with a cleaning solution ("Reduction Securigant P" manufactured by Atotech Japan Co., Ltd.) at 25° C., it was washed with pure water to obtain an evaluation sample.

Measurement of surface roughness: For the surface of the evaluation sample (roughened hardened product), use a non-contact three-dimensional surface shape measurement device ("WYKO NT1100" manufactured by Veeco Corporation) to measure in a measurement area of 94 μm×123 μm Arithmetic mean roughness Ra. In addition, the said arithmetic mean roughness Ra is measured based on JISB0601:1994. The surface roughness was judged according to the following criteria.

[Criteria for judging surface roughness] ○○: Ra is less than 50 nm ○: Ra is more than 50 nm and less than 200 nm ×: Ra is more than 200 nm

(5) Plating peeling strength Electroless plating treatment: Hardening after roughening treatment obtained in (4) Evaluation of surface roughness using an alkaline cleaning solution at 60°C ("Cleaner Securigant 902" manufactured by Atotech Japan Co., Ltd.) The surface of the object is treated for 5 minutes, and degreased and washed. After washing, the cured product was treated with a 25°C pre-dip solution ("Pre-dip Neogant B" manufactured by Atotech Japan Co., Ltd.) for 2 minutes. Thereafter, the cured product was treated with an activator ("Activator Neogant 834" manufactured by Atotech Japan Co., Ltd.) at 40° C. for 5 minutes, and a palladium catalyst was added. Next, the cured product was treated with a reducing solution ("Reducer Neogant WA" manufactured by Atotech Japan Co., Ltd.) at 30° C. for 5 minutes.

Next, add the above-mentioned cured product to chemical copper solution ("Basic Printganth MSK-DK", "Copper Printganth MSK", "Stabilizer Printganth MSK" and "Reducer Cu" manufactured by Atotech Japan Co., Ltd.), and perform electroless plating to The plating thickness is about 0.5 μm. After electroless plating, in order to remove residual hydrogen, an annealing treatment was performed at a temperature of 120° C. for 30 minutes. In addition, all the steps up to the step of electroless plating were carried out while shaking the cured product while setting the treatment solution to 2 L with the scale of the beaker.

Electrolytic plating treatment: Next, electrolytic plating was performed on the hardened product subjected to the electroless plating treatment until the plating thickness became 25 μm. As electrolytic copper plating, a copper sulfate solution ("copper sulfate pentahydrate" manufactured by Wako Pure Chemical Industries, Ltd., "sulfuric acid" manufactured by Ko Pure Chemical Industries, Ltd., "Basic Leveler Cupracid HL" manufactured by Atotech Japan Co., Ltd., Atotech Japan Co., Ltd. Manufactured "correction agent Cupracid GS"), flow a current of 0.6 A/cm ² , and perform electrolytic plating until the plating thickness becomes about 25 μm. After the copper plating treatment, the cured product was heated at 190° C. for 90 minutes to further harden the cured product. In this way, a hardened product having a copper-plated layer on the upper surface was obtained.

Determination of peeling strength of the plating layer: A short strip-shaped incision with a width of 0.5 cm was cut on the surface of the copper plating layer of the obtained hardened product with a copper plating layer layered on the upper surface. In a 90° peel tester ("TE-3001" manufactured by TESTER SANGYO Co., Ltd.), set a hardened object with a copper plating layer on the upper surface, clamp the end of the copper plating layer with a notch with a jig, and peel the copper plating layer 15 mm to measure the peel strength (coating peel strength).

[Judgement criteria for plating peel strength] ○○: Plating peel strength is 0.5 kgf or more ○: Plating peel strength is 0.3 kgf or more and less than 0.5 kgf ×: Plating peel strength is less than 0.3 kgf

(6) Curing temperature The exothermic peak accompanying the hardening of the obtained resin film (B-stage film) was evaluated using a differential scanning calorimeter ("Q2000" manufactured by TA Instruments). Take 8 mg of the resin film in a special aluminum pot and cover it with a special jig. Set the special aluminum pot and the empty aluminum pot (reference) in the heating unit, and heat it from -30°C to 250°C at a heating rate of 3°C/min under a nitrogen atmosphere to observe reverse heat flow and non-reverse heat flow. Confirm the hardening temperature according to the exothermic peak observed in the non-reverse heat flow.

[Criteria for hardening temperature] ○: All exothermic peaks are present below 200°C X: At least one exothermic peak is present at a temperature higher than 200°C (including exothermic peaks at temperatures higher than 200°C and at 200°C The following also have exothermic peaks)

(7) Flexibility of resin film The obtained resin film (B-stage film) was bent at 180 degrees 10 times. Observe the number of times that the resin film is chapped or broken out of 10 times.

[Criteria for Judgment of Flexibility of Resin Film] ○: The number of cracks or cracks was less than 3 times out of 10 times. The number of cracks or ruptures is more than 6 times

(8) Coverage of concave-convex surface Only the copper foil of a 100 mm square copper-clad laminate (a laminate of a glass epoxy substrate with a thickness of 400 μm and a copper foil with a thickness of 25 μm) is etched, and the center of the substrate is 30 In the mm square area, recesses (openings) with a diameter of 100 μm and a depth of 25 μm were formed such that the distance between the centers of adjacent holes was 900 μm on a straight line. In this way, an evaluation substrate having a total of 900 wells of depressions was prepared.

The resin film side of the obtained laminated film was overlaid on the evaluation substrate, and the "batch type vacuum laminator MVLP-500-IIA" manufactured by Meiki Co., Ltd. was used to perform lamination at a pressure of 0.4 MPa for 20 seconds. Press at 0.8 MPa for 20 seconds, heat and press at a temperature of 90°C for lamination and press. After cooling at normal temperature, the PET film was peeled off. Thus, the evaluation sample in which the resin film was laminated|stacked on the evaluation board|substrate was obtained.

For the obtained evaluation samples, voids were observed in the depressions using an optical microscope. By evaluating the ratio of dents where voids were observed, the coverage on the uneven surface was judged according to the following criteria.

[Criteria for judging the coverage of uneven surfaces] ○: The ratio of voids and depressions is 0% △: The ratio of voids and depressions is more than 0% and less than 5% ×: The ratio of voids and depressions is observed 5% or more

The compositions and results are shown in Tables 1 to 3 below. In addition, in Tables 1-3, content of each component is described as a pure amount (solid content weight part).

[Table 1]

[Table 2]

[table 3]

11‧‧‧multilayer printed wiring board 12‧‧‧circuit substrate 12a‧‧‧top surface 13～16‧‧‧insulating 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 (14)

A resin material comprising: an N-alkylbismaleimide compound having a skeleton derived from dimer diamine or an N-alkylbenzo compound having a skeleton derived from dimer diamine

Compound; Epoxy compound; Inorganic filler; In the case of the maleimide compound, the content of the above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine is relative to the content of the above-mentioned epoxy compound and the above-mentioned hardener. The weight ratio of the total content is not less than 0.05 and not more than 0.75, and in the above-mentioned N-alkylbenzone having a skeleton derived from dimer diamine

In the case of compounds, the above-mentioned N-alkylbenzos having a skeleton derived from dimer diamine

The weight ratio of content of the compound with respect to the total content of the said epoxy compound and the said hardening|curing agent is 0.05-0.75. The resin material according to claim 1, wherein the above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine has a structure represented by the following formula (X), or the above-mentioned N-alkylbismaleimide compound having a N-Alkylbenzos from the backbone of dimer diamines

The compound has a structure represented by the following formula (X),

In the above formula (X), R1 represents a tetravalent organic group. The resin material according to claim 1 or 2, wherein the above-mentioned epoxy compound is an epoxy compound having an aromatic skeleton, and the above-mentioned component is a component having an aromatic skeleton. The resin material according to claim 1 or 2, which contains a hardening accelerator. The resin material according to claim 4, wherein the hardening accelerator includes an anionic hardening accelerator. The resin material according to claim 5, wherein the content of the above-mentioned anionic hardening accelerator is 50% by weight or more in 100% by weight of the above-mentioned hardening accelerator. The resin material according to claim 5, wherein the anionic hardening accelerator is an imidazole compound. The resin material according to claim 4, wherein the hardening accelerator comprises a radical hardening accelerator and an imidazole compound, or a radical hardening accelerator and a phosphorus compound. The resin material according to claim 1 or 2, wherein the average particle diameter of the above-mentioned inorganic filler is 1 μm or less. The resin material according to claim 1 or 2, which comprises the above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine, and the above-mentioned N-alkylbismaleimide compound having a skeleton derived from dimer diamine The molecular weight of the N-alkylbismaleimide compound is less than 15,000, and the above-mentioned molecular weight of the N-alkylbismaleimide compound having a skeleton derived from dimer diamine is less than the above-mentioned molecular weight. When the N-alkylbismaleimide compound is not a polymer, and when the structural formula of the above-mentioned N-alkylbismaleimide compound can be specified, it means that the structural formula can be obtained The calculated molecular weight represents the weight average in terms of polystyrene measured by gel permeation chromatography (GPC) when the above-mentioned N-alkylbismaleimide compound is a polymer. molecular weight. The resin material as claimed in claim 1 or 2, which comprises the above-mentioned N-alkylbenzo with a skeleton derived from dimer diamine

Compounds, the above-mentioned N-alkylbenzos having a skeleton derived from dimer diamine

The molecular weight of the compound is less than 15000, and the above-mentioned N-alkylbenzos having a skeleton derived from dimer diamine

The above-mentioned molecular weight of the compound is lower than the above-mentioned N-alkylbenzo

The case where the compound is not a polymer, and the above-mentioned N-alkylbenzo

In the case of the structural formula of a compound, it means the molecular weight that can be calculated from the structural formula, and in the case of the above-mentioned N-alkylbenzo

When the compound is a polymer, it shows the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC). The resin material according to claim 1 or 2, which is a resin film. The resin material according to claim 1 or 2, which is used to form an insulating layer in a multilayer printed wiring board. A multilayer printed wiring board comprising: a circuit substrate; a plurality of insulating layers disposed on the surface of the circuit substrate; and a metal layer disposed between the plurality of insulating layers; and at least one of the plurality of insulating layers The first layer is a cured product of the resin material according to any one of claims 1 to 13.

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