TW201945469A - Resin material and multilayer printed wiring board - Google Patents

Abstract

A resin material is provided which can (1) reduce the dielectric loss tangent of a cured product, (2) increase adhesion between an insulation layer and a metal layer, (3) increase the plated peel strength, (4) increase flame retardancy of the cured product and (5) keep the curing temperature low. This resin material contains an N-alkyl bismaleimide compound having a skeleton derived from dimer diamines or an N-alkyl benzoxazine compound having a skeleton derived from dimer diamines, an epoxy compound, an inorganic filler material, and a curing agent containing a specific component, wherein the weight ratio of the content of the N-alkyl bismaleimide compound having a skeleton derived from dimer diamines or the N-alkyl benzoxazine compound having a skeleton derived from dimer diamines to the total content of the epoxy compound and the curing agent is 0.05-0.75.

Description

Resin material and multilayer printed wiring board

The present invention relates to a resin material containing an epoxy compound, an inorganic filler, and a hardener. Moreover, this invention relates to the multilayer printed wiring board using the said resin material.

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

The following Patent Document 1 discloses a resin composition containing a compound having a cis-butene diamidino group and a divalent group having at least two fluorene imine bonds and a saturated or unsaturated divalent hydrocarbon group. Patent Document 1 describes that a cured product of the resin composition can be used as an insulating layer of a multilayer printed wiring board or the like. [Prior Art Literature] [Patent Literature]

[Patent Document 1] WO2016 / 114286A1

[Problems to be solved by the invention]

In order to improve the electrical characteristics of the hardened material (insulating layer), a compound with a relatively low polarity may be blended in the resin material (resin composition). However, in the case where an insulating layer is formed using a resin material prepared with a compound having a lower polarity, the adhesion between the insulating layer and the wiring (metal layer) may not be sufficiently high. Therefore, the metal layer may be peeled from the insulating layer. In addition, the conventional resin materials may have increased roughness or the peeling strength of the plating layer may not be sufficiently increased.

In addition, as described in Patent Document 1, a conventional resin material prepared with a cis-butene diimine compound having an aliphatic skeleton may have reduced flame retardancy. On the other hand, a conventional resin material prepared with a maleimide compound having an aromatic skeleton has a high Tg of the maleimide compound, which makes it difficult to lower the curing temperature (for example, 200 ° C or lower). ). In addition, when the curing temperature is lowered, it is difficult to generate sufficient molecular motion, so that there is a case where a poor curing occurs. In addition, when the curing temperature is reduced, when manufacturing a multilayer printed wiring board, the resin material laminated in the initial stage is heated more times and longer than the resin material laminated in the later stage. Changes in electrical characteristics or physical properties. In addition, since the conventional resin material hardened by the radical reaction reacts quickly, 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 increased.

As such, there is a current situation in which it is extremely difficult to obtain a resin material exhibiting all of the following effects 1) -5), that is, 1) reduce the dielectric loss tangent of the hardened material, 2) improve 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 material, 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 material, 2) improve the adhesion between the insulating layer and the metal layer, 3) increase the peeling strength of the plating layer, and 4) improve the flame retardance of the hardened material And 5) suppress the hardening temperature to be low. Another object of the present invention is to provide a multilayer printed wiring board using the resin material. [Technical means to solve the problem]

According to a broad aspect of the present invention, there is provided a resin material including: an N-alkylbiscisbutenedifluorene imine compound having a skeleton derived from a dimer diamine or a diamine derived from a dimer N-alkylbenzopyrene compound of a skeleton; epoxy compound; inorganic filler; and containing a phenol compound, a cyanate compound, an acid anhydride, an active ester compound, a carbodiimide compound, and does not have a dimer-derived compound A hardener of at least one component in a benzofluorene compound of a diamine skeleton; when the above-mentioned N-alkylbiscis-butenedifluorene imine compound having a skeleton derived from a dimer diamine is used, The weight ratio of the content of the N-alkylbiscisbutenedifluorene imine compound having a skeleton derived from a dimer diamine to the total content of the epoxy compound and the hardener is 0.05 or more and 0.75 or less, and When the above-mentioned N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine is included, the content of the above-mentioned N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine is relative to The epoxy compound and the hardener The weight ratio of the total content is 0.05 or more 0.75 or less.

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

[Chemical 1]

In the 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 specific aspect of the resin material of the present invention, the resin material contains a hardening accelerator.

In a specific aspect of the resin material of the present invention, the hardening accelerator includes an anionic hardening accelerator.

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

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

In a specific aspect of the resin material of the present invention, the average particle diameter of the inorganic filler is 1 μm or less.

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

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

In a specific aspect of the resin material of the present invention, the 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 wide aspect of the present invention, there is provided a multilayer printed wiring board including: 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 is a hardened product of the resin material. [Effect of the invention]

The resin material of the present invention comprises: an N-alkylbiscisbutenedifluorene imine compound having a skeleton derived from a dimer diamine or an N-alkylbenzofluorene having a skeleton derived from a dimer diamine Compounds, epoxy compounds, and inorganic fillers. The resin material of the present invention contains a hardener containing a phenol compound, a cyanate ester compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a benzofluorene compound having no skeleton derived from a dimer diamine. At least one of the ingredients. In the resin material of the present invention, when the above-mentioned N-alkylbiscis-butenedifluorene imine compound having a skeleton derived from a dimer diamine is included, the above-mentioned skeleton having a dimer derived diamine The weight ratio of the content of the N-alkylbiscis-butenedifluorene imide compound to the total content of the epoxy compound and the hardener is 0.05 or more and 0.75 or less. In the resin material of the present invention, when the above-mentioned N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine is included, the above-mentioned N-alkyl having a skeleton derived from a dimer diamine The weight ratio of the content of the benzofluorene compound to the total content of the epoxy compound and the hardener is 0.05 or more and 0.75 or less. Since the resin material of the present invention has the above-mentioned structure, it can exhibit all the effects of 1) -5): 1) it can reduce the dielectric loss tangent of the hardened material, 2) it can improve the adhesion between the insulating layer and the metal layer, and 3) it can improve The peeling strength of the plating layer, 4) improves the flame retardancy of the cured product, and 5) suppresses the curing temperature to a low level.

Hereinafter, the present invention will be described in detail.

The resin material of the present invention contains an N-alkylbiscis-butenedifluorene imine compound having a skeleton derived from a dimer diamine or an N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine .

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

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

The resin material of the present invention contains a hardener containing a phenol compound, a cyanate ester compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a benzofluorene compound having no skeleton derived from a dimer diamine. At least one of the ingredients.

In this specification, at least one of a phenol compound, a cyanate compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a benzofluorene compound which does not have a skeleton derived from a dimer diamine may be used. "Component" is described as "component X".

Therefore, the resin material of the present invention includes: an N-alkylbiscis-butenedifluorene imine compound having a skeleton derived from a dimer diamine or an N-alkylbenzene having a skeleton derived from a dimer diamine Pyrene compound, epoxy compound, inorganic filler, and hardener containing component X.

In the resin material of the present invention, in a case where the resin material includes the above-mentioned N-alkylbiscis-butenediamidoimine compound having a skeleton derived from a dimer diamine, the above-mentioned resin having a dimer derived diamine The weight ratio of the content of the N-alkylbiscis-butenedifluorene imine compound of the skeleton to the total content of the epoxy compound and the hardener is 0.05 or more and 0.75 or less.

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

Since the resin material of the present invention has the above-mentioned structure, all the effects of 1) -5) can be exhibited: 1) it can reduce the dielectric loss tangent of the hardened material, 2) it can improve the adhesion between the insulating layer and the metal layer, and 3) it can improve The peeling strength of the plating layer, 4) improves the flame retardancy of the cured product, and 5) suppresses the curing temperature to a low level. For example, 2) The peeling strength of the insulating layer and the metal layer can be improved in a temperature range from room temperature to high temperature (for example, 260 ° C.) as the adhesion between the insulating layer and the metal layer. In addition, 3) the peeling strength of the hardened material (insulating layer) subjected to the roughening treatment as the peeling strength of the plating layer and the metal layer laminated by performing a plating treatment on the surface of the insulating layer can be improved. In the above-mentioned roughened hardened material (insulating layer), fine concave portions are formed on the surface. The resin portion existing near the opening of the recessed portion exhibits an anchoring effect on the metal layer. The resin material of the present invention can suppress the resin that contributes to the anchoring effect from being locally thin because the thickness of the roughened hardened material (insulating layer) becomes excessively large, so that the peeling strength of the plating layer can be improved. In addition, the resin material of the present invention can prevent the anchorage from being formed because the thickness of the roughened hardened material (insulating layer) becomes too small, so that the peeling strength of the plating layer can be improved.

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

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 unlikely to be cracked or cracked. That is, when the resin material of the present invention is a resin film, in addition to the effects 1) to 5) above, 6) can also improve the flexibility of the resin film.

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

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

[Compound having a skeleton derived from a dimer diamine] The resin material of the present invention contains an N-alkylbiscisbutene difluorene imine compound having a skeleton derived from a dimer diamine or has a dimer derived N-alkylbenzofluorene compounds of the structure of diamine. The resin material of the present invention may include only the N-alkylbiscisbutenedifluorene imine compound, may include only the N-alkylbenzocenefluorene compound, and may also include the N-alkylbiscisbutenedifluorene compound. Both an imine compound and the N-alkylbenzofluorene compound.

<N-alkylbiscis-butenediamidoimine compound having a skeleton derived from a dimer diamine> The resin material of the present invention preferably contains an N-alkyl having a skeleton derived from a dimer diamine Dicis-butene difluorene imine compound. The above-mentioned N-alkylbis-cis-butene-diimide compound having a skeleton derived from a dimer diamine has a cis-butene-diimide group. By using the above-mentioned N-alkylbiscis-butenediamidoimine 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. In addition, by using the above-mentioned N-alkylbiscis-butenedifluorene imine compound having a skeleton derived from a dimer diamine, the etching performance can be improved. Furthermore, by using the above-mentioned N-alkylbiscis-butenedifluorene imine compound having a skeleton derived from a dimer diamine, it is possible to suppress the curing temperature to be low. The above-mentioned N-alkylbiscis-butenedifluorene imine compound having a skeleton derived from a dimer diamine may be in an oligomer state. The above-mentioned N-alkylbiscis-butenedifluorene imine compound having a skeleton derived from a dimer diamine may also have a molecular weight distribution. The N-alkylbiscis-butenedifluorene imine compound having a skeleton derived from a dimer diamine may be used alone or in combination of two or more.

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

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

The above-mentioned N-alkylbiscis-butenedifluorene imine compound having a skeleton derived from a dimer diamine is preferably a skeleton having a reactant derived from a tetracarboxylic dianhydride and a dimer diamine. The reactant of the tetracarboxylic dianhydride and the dimer diamine is preferably a compound having amine groups at both ends.

The above-mentioned N-alkylbiscis-butenediamidoimine compound having a skeleton derived from a dimer diamine can be obtained, for example, from a reaction product of a tetracarboxylic dianhydride and a dimer diamine (preferably at both ends is An amine compound) is obtained by reacting the reactant with maleic anhydride.

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, and 3,3', 4,4'-dicarboxylic acid. Benzenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl Ether tetracarboxylic dianhydride, 3,3 ', 4,4'-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) diphenylfluorene dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroimide Isopropyl diphthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-benzene-bis (triphenyl) Phthalic acid) dianhydride, m-benzene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, and bis (Triphenylphthalic acid) -4,4'-diphenylmethane dianhydride and the like.

As a commercially available product of the dimer diamine, for example, 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), and PRIAMINE 1075, PRIAMINE 1074, and PRIAMINE 1071 (trade names, all manufactured by Croda Japan) and the like. The dimer diamine may or may not have an unsaturated hydrocarbon as a partial skeleton.

Examples of the commercially available N-alkylbiscis-butenediamidoimide compound having a skeleton derived from a dimer diamine include "BMI-1500" and "BMI-1500" manufactured by Designer Molecules Inc. 1700 "and" BMI-3000 ".

From the viewpoint of more effectively exerting the effects of the present invention, the N-alkylbiscisbutenediamidine imine compound having a skeleton derived from a dimer diamine is preferably one having the following formula (X): The structure of the representation.

[Chemical 2]

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

Examples of R1 in the formula (X) include a group having an aromatic ring and a group having a diphenyl ether skeleton. Examples of the group having an aromatic ring include a group having a skeleton derived from pyromellitic anhydride. Examples of the above-mentioned group having a diphenyl ether skeleton include a group having a skeleton derived from 4,4′-oxydiphthalic anhydride.

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

The weight ratio of the content of the N-alkylbiscis-butenedifluorene imine compound having a skeleton derived from dimer diamine to the total content of the epoxy compound and the hardener is referred to as "weight ratio ( Content of N-alkylbiscisbutenediamidoimide compound having a skeleton derived from dimer diamine / total content of epoxy compound and hardener) ". In the case where the resin material includes the N-alkylbiscis-butenedifluorene imine compound having a skeleton derived from a dimer diamine, the above-mentioned weight ratio (N having a skeleton derived from a dimer diamine -The content of the alkylbiscis-butenedifluorene imine compound / the total content of the epoxy compound and the hardener) is 0.05 or more and 0.75 or less. If the above weight ratio (content of N-alkylbiscisbutenediamidine imide compound with a skeleton derived from dimer diamine / total content of epoxy compound and hardener) is less than 0.05 or more than 0.75, then It is difficult to bring out the effects of the present invention 1) -5) and the effects of 1) -6) above.

The aforementioned weight ratio (content of N-alkylbiscisbutenediamidine imide compound having a skeleton derived from dimer diamine / total content of epoxy compound and hardener) is preferably 0.15 or more, and more preferably It is 0.5 or less. If the weight ratio is greater than or equal to the above lower limit and less than or equal to the above upper limit, the effects of the present invention 1) -5) and the effects of 1) -6) can be more effectively exhibited.

The content of the N-alkylbiscis-butenedifluorene imine 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 At least 10% by weight or more, more preferably at least 15% by weight. The content of the N-alkylbiscis-butenedifluorene imine 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. It is preferably 60% by weight or less, more preferably 55% by weight or less, and even more preferably 50% by weight or less. If the content of the N-alkylbiscis-butenedifluorene imine compound having a skeleton derived from dimer diamine is above the lower limit described above, the dielectric loss tangent can be reduced, and the insulation layer and the metal layer can be further improved. Adhesiveness, peeling strength of plating, etching performance and softness of resin film. If the content of the N-alkylbiscis-butenedifluorene imine compound having a skeleton derived from dimer diamine is below the above upper limit, the flame retardancy can be further improved, and the linear expansion coefficient can be suppressed to be lower. Further increase the plating peel strength.

The molecular weight of the N-alkylbiscisbutenedifluorene imine compound having a skeleton derived from a dimer diamine is preferably 500 or more, more preferably 600 or more, and preferably less than 15,000, and more preferably It is less than 11,000, and more preferably less than 8,000. If the molecular weight is above the lower limit and below the upper limit, the adhesion between the insulating layer and the metal layer can be further improved, the melt viscosity can be reduced, and the coverage of the circuit board by the resin material (resin film) can be improved.

The molecular weight of the N-alkylbiscisbutenedifluorene imine compound having a skeleton derived from a dimer diamine is higher than the case where the N-alkylbiscisbutadiene diimine compound is not a polymer, and When specifying the structural formula of the N-alkylbiscis-butenediamidine imine compound, it means the molecular weight calculated from the structural formula. In addition, the molecular weight of the N-alkylbiscisbutenedifluorene imine compound having a skeleton derived from a dimer diamine is when the N-alkylbiscisbutadiene diimine compound is a polymer. , Represents the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

<N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine> The resin material of the present invention preferably contains the above-mentioned N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine. . The above-mentioned N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine is preferably a cis of the above-mentioned N-alkylbiscisbutene difluorene imide compound having a skeleton derived from a dimer diamine. A compound having a butene difluorene imine skeleton replaced with a benzofluorene skeleton. By using the above-mentioned N-alkylbenzopyrene 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. In addition, by using the above-mentioned N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine, the etching performance can be improved. In addition, by using the N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine, the curing temperature can be suppressed to be low. The above-mentioned N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine may be in an oligomer state. The aforementioned N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine may also have a molecular weight distribution. The N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine may be used alone or in combination of two or more.

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

The N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine is preferably an N-alkylbisbenzofluorene compound having a skeleton derived from a dimer diamine.

The aforementioned N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine is preferably a skeleton derived from a reactant of a tetracarboxylic dianhydride and a dimer diamine. The reactant of the tetracarboxylic dianhydride and the dimer diamine is preferably a compound having amine groups at both ends.

The above-mentioned N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine can be obtained, for example, as a reactant of a tetracarboxylic dianhydride and a dimer diamine (preferably, a compound having amine groups at both ends). Then, this reactant, phenol, and paraformaldehyde were reacted and obtained.

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-alkylbenzofluorene compound having a skeleton derived from a dimer diamine preferably has a structure represented by the following formula (X).

[Chemical 3]

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

Examples of R1 in the formula (X) include a group having an aromatic ring and a group having a diphenyl ether skeleton. Examples of the group having an aromatic ring include a group having a skeleton derived from pyromellitic anhydride. Examples of the above-mentioned group having a diphenyl ether skeleton include a group having a skeleton derived from 4,4′-oxydiphthalic anhydride.

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

The weight ratio of the content of the N-alkylbenzofluorene compound having a skeleton derived from dimer diamine to the total content of the epoxy compound and the hardener is referred to as "weight ratio (having dimerization Content of N-alkylbenzopyrene compounds of the compound diamine / total content of epoxy compound and hardener) ". When the resin material includes the above-mentioned N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine, the above-mentioned weight ratio (the N-alkylbenzo compound having a skeleton derived from a dimer diamine) The content of rhenium compound / total content of epoxy compound and hardener) is 0.05 or more and 0.75 or less. If the above weight ratio (content of N-alkylbenzofluorene compound having a skeleton derived from dimer diamine / total content of epoxy compound and hardener) is less than 0.05 or more than 0.75, it is difficult to exert the above 1) -5) the effects of the present invention and 1) -6).

The aforementioned weight ratio (content of N-alkylbenzofluorene compound having a skeleton derived from dimer diamine / total content of epoxy compound and hardener) is preferably 0.15 or more, and more preferably 0.5 or less. If the weight ratio is greater than or equal to the above lower limit and less than or equal to the above upper limit, the effects of the present invention 1) -5) and the effects of 1) -6) can be more effectively exhibited.

The content of the N-alkylbenzofluorene 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% by weight or more, more It is preferably 10% by weight or more, and further preferably 15% by weight or more. The content of the N-alkylbenzofluorene 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 It is preferably 60% by weight or less, more preferably 55% by weight or less, and even more preferably 50% by weight or less. If the content of the N-alkylbenzopyrene compound having a skeleton derived from dimer diamine is above the lower limit, the tangent of dielectric loss 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. , Etching performance and softness of resin film. If the content of the N-alkylbenzopyrene compound having a skeleton derived from dimer diamine is below the upper limit described above, the flame retardancy can be further improved, the linear expansion coefficient can be suppressed to be lower, and the peeling strength of the plating layer can be further improved. .

The molecular weight of the N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine is preferably 500 or more, more preferably 600 or more, and preferably less than 15,000, more preferably less than 11,000, and furthermore It is preferably less than 8000. If the molecular weight is above the lower limit and below the upper limit, the adhesion between the insulating layer and the metal layer can be further improved, the melt viscosity can be reduced, and the coverage of the circuit board by the resin material (resin film) can be improved.

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

[Epoxy Compound] The resin material contains an epoxy compound. As the epoxy compound, a conventionally known epoxy compound can be used. The epoxy compound refers to an organic compound having at least one epoxy group. These epoxy compounds may be used alone or in combination of two or more.

Examples of the epoxy compound include a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, a phenol novolac epoxy compound, a biphenyl epoxy compound, and a biphenyl epoxy compound. Novolac epoxy compounds, biphenol epoxy compounds, naphthalene epoxy compounds, fluorene epoxy compounds, phenol aralkyl epoxy compounds, naphthol aralkyl epoxy compounds, dicyclopentadiene Ethylene type epoxy compound, anthracene type epoxy compound, epoxy compound having adamantane skeleton, epoxy compound having tricyclodecane skeleton, dnaphthyl ether type epoxy compound, and epoxy having trinuclear as a skeleton Compounds etc.

The epoxy compound is preferably an epoxy compound having an aromatic skeleton, more preferably an epoxy compound having a naphthalene skeleton or a phenyl skeleton, and further preferably an epoxy compound having an aromatic skeleton, particularly preferably an epoxy compound having an aromatic skeleton. Epoxy compound of 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 linear expansion coefficient (CTE) of the hardened material, the epoxy compound is preferably comprised of an epoxy compound that is liquid at 25 ° C and 25 ° C. Below is a solid epoxy compound.

The viscosity of the above-mentioned epoxy compound which is liquid at 25 ° C at 25 ° C is preferably 1,000 mPa · s or less, and more preferably 500 mPa · s or less.

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

The molecular weight of the epoxy compound is more preferably 1,000 or less. In this case, even if the content of the inorganic filler in 100% by weight of the components other than the solvent in the resin material is 50% by weight or more, a resin material having high fluidity when forming the insulating layer can be obtained. Therefore, when an uncured material or a B-staged material of a resin material is laminated on a circuit board, an inorganic filler can be made to exist uniformly.

The molecular weight of the said epoxy compound is the case where 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 calculated from the structural formula. When the epoxy compound is a polymer, it means a weight average molecular weight.

From the viewpoint of further improving the bonding strength between the cured material and the metal layer, the content of the epoxy compound in 100% by weight of the components other than the solvent in the resin material is preferably 15% by weight or more, and more preferably 20% by weight. The above is preferably 50% by weight or less, and more preferably 40% by weight or less.

The weight ratio of the content of the above-mentioned epoxy compound to the total content of the above-mentioned N-alkylbiscis-butenedifluorene imide compound having a skeleton derived from a dimer diamine and the above-mentioned hardener (the content of the above-mentioned epoxy compound / The total content of the N-alkylbiscis-butenediamidine imine compound and the hardener) is preferably 0.2 or more, and 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-alkylbiscis-butenedifluorene imide compound having a skeleton derived from dimer diamine and the above-mentioned hardener / The total content of the N-alkylbiscis-butenedifluorene imine compound and the curing agent) is preferably 0.9 or less, and more preferably 0.8 or less. If the weight ratio (the content of the epoxy compound / the total content of the N-alkylbiscis-butenediimine compound and the hardener) is at least 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 plating layer, the flame retardancy and the softness of the resin film, and reduce the thickness.

The weight ratio of the content of the epoxy compound to the total content of the N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine and the hardener (the content of the epoxy compound / the N-alkane The total content of the benzobenzofluorene compound and the hardener is preferably 0.2 or more, and more preferably 0.25 or more. The weight ratio of the content of the epoxy compound to the total content of the N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine and the hardener (the content of the epoxy compound / the N-alkane The total content of the benzobenzofluorene compound and the hardener is preferably 0.9 or less, and more preferably 0.8 or less. If the weight ratio (the content of the epoxy compound / the total content of the N-alkylbenzopyrene compound and the hardener) is above the lower limit and lower than the upper limit, the dielectric loss tangent can be reduced, and the insulating layer can be further improved. Adhesiveness to metal layer, peeling strength of coating, flame retardancy and softness of resin film, reduce the thickness.

[Inorganic Filler] The resin material includes an inorganic filler. By using the inorganic filler, the dielectric loss tangent of the hardened material can be further reduced. Moreover, by using the said inorganic filler, the dimensional change by the heat of a hardened | cured material becomes further smaller. These inorganic fillers may be used alone or in combination of two or more.

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

From the viewpoint of reducing the surface roughness of the surface of the hardened object, further improving the bonding strength between the hardened object and the metal layer, and forming finer wiring on the surface of the hardened object, and imparting good insulation reliability to the hardened object The above-mentioned inorganic filler is preferably silicon dioxide or aluminum oxide, more preferably silicon dioxide, and even more preferably fused silicon dioxide. By using silicon dioxide, the thermal expansion rate of the hardened material is further reduced, and the dielectric loss tangent of the hardened material is further reduced. In addition, by using silicon dioxide, the surface roughness of the surface of the hardened material is effectively reduced, and the bonding strength between the hardened material and the metal layer is effectively improved. The shape of the silicon dioxide is preferably spherical.

Regardless of the viewpoint of hardening the resin regardless of the hardening environment, effectively increasing the glass transition temperature of the hardened material and effectively reducing the coefficient of thermal expansion of the hardened material, the inorganic filler is preferably spherical silica.

The average particle diameter of the inorganic filler is preferably 50 nm or more, more preferably 100 nm or more, still more preferably 500 nm or more, and more preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 2 μm or less. If the average particle diameter of the inorganic filler is at least the above lower limit and at most the above 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 an average particle diameter of the said inorganic filler, the value which becomes 50% median diameter (d50) is used. The average particle diameter can be measured using a particle size distribution measuring device of a laser diffraction scattering method.

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

The above-mentioned inorganic filler is preferably subjected to a surface treatment, more preferably a surface-treated product obtained using a coupling agent, and still more preferably a surface-treated product obtained using a silane coupling agent. By subjecting the inorganic filler to surface treatment, the surface roughness of the surface of the roughened hardened material is further reduced, and the bonding strength between the hardened material and the metal layer is further improved. In addition, by subjecting the inorganic filler to surface treatment, finer wiring can be formed on the surface of the cured product, and the cured product can be provided with better inter-wiring insulation reliability and inter-layer insulation reliability.

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

The content of the inorganic filler in 100% by weight of the components other than the solvent in the resin material is preferably 50% by weight or more, more preferably 60% by weight or more, more preferably 65% by weight or more, and most preferably 68% by weight. % Or more, and preferably 90% by weight or less, more preferably 85% by weight or less, still more preferably 80% by weight or less, and even more preferably 75% by weight or less. When the content of the inorganic filler is greater than or equal to the above lower limit, the dielectric loss tangent is effectively reduced. When the content of the inorganic filler is equal to or less than the above upper limit, the etching performance can be improved. If the content of the inorganic filler is at least the above lower limit and below the above upper limit, the surface roughness of the surface of the hardened material can be further reduced, and finer wiring can be formed on the surface of the hardened material. Furthermore, if it is the amount of this inorganic filler, the thermal expansion coefficient of a hardened | cured material can be reduced, and detergency can also be made favorable.

[Hardener] The resin material contains a hardener containing a phenol compound, a cyanate ester compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a benzo compound which does not have a skeleton derived from a dimer diamine. At least one component of the hydrazone compound. That is, the resin material contains a curing agent containing component X. The benzofluorene compound preferably has no skeleton derived from a diamine compound other than the dimer diamine. These hardeners may be used alone or in combination of two or more.

Component X: Component X is a phenol compound (phenol hardener), a cyanate compound (cyanate hardener), an acid anhydride, an active ester compound, a carbodiimide compound (carbodiimide hardener), and has no source At least one component of a benzofluorene compound (benzofluorene hardener) from the skeleton of a dimer diamine. That is, the resin material contains a curing agent containing component X. The component X may be used alone or in combination of two or more.

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

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

Examples of the commercially available phenol compound include novolac phenol ("TD-2091" manufactured by DIC Corporation), biphenol novolac phenol ("MEH-7851" manufactured by Meiwa Chemical Co., Ltd.), and aralkyl Type phenolic compounds ("MEH-7800" manufactured by Meiwa Chemical Co., Ltd.), and phenols having an amine triple skeleton ("LA1356" and "LA3018-50P" manufactured by DIC Corporation) and the like.

Examples of the cyanate ester compound include a novolac-type cyanate resin, a bisphenol-type cyanate resin, and a prepolymer obtained by partial trimerization thereof. Examples of the novolac-type cyanate resin include a phenol-based novolac-type cyanate resin and an alkylphenol-type cyanate resin. Examples of the bisphenol type cyanate resin include a bisphenol A type cyanate resin, a bisphenol E type cyanate resin, and a tetramethylbisphenol F type cyanate resin.

Examples of commercially available products of the cyanate ester compounds include phenol-based novolac-type cyanate resins ("PT-30" and "PT-60" manufactured by Lonza Japan), and bisphenol-type cyanate resins. Prepolymers ("BA-230S", "BA-3000S", "BTP-1000S", "BTP-6020S", etc.) manufactured by trimerization, and others.

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

As a commercially available product of the said acid anhydride, the "RIKACID TDA-100" manufactured by Shin Nihon Chemical Co., Ltd., etc. are mentioned.

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

[Chemical 4]

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

Examples of the combination of X1 and X2 include a combination of a benzene ring which may have a substituent and a benzene ring which may have a substituent, and a combination of a benzene ring which may have a substituent and a naphthalene ring which may have a substituent. Further, examples of the combination of X1 and X2 include a combination of a naphthalene ring which may have a substituent and a naphthalene ring which may have a substituent.

The active ester compound is not particularly limited. From the viewpoint of further improving the flame retardancy and reducing the coefficient of linear expansion, the 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 two or more aromatic skeletons. From the viewpoint of reducing the tangent of the dielectric loss 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.

Examples of the commercially available active ester compound include "HPC-8000-65T", "EXB9416-70BK", "EXB8100-65T", and "HPC-8150-60T" manufactured by DIC Corporation.

The carbodiimide compound has a structural unit represented by the following formula (2). In the following formula (2), the right end portion and the left end portion are bonded portions with other bases. These carbodiimide compounds may be used alone or in combination of two or more.

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

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

Examples of commercially available carbodiimide compounds include "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", and "Carbodilite" manufactured by Nisshinbo Chemical Company. V-09 "," Carbodilite 10M-SP ", and" Carbodilite 10M-SP (modified) ", and" Stabaxol P "," Stabaxol P400 ", and" Hycasyl 510 "manufactured by Rhein Chemie.

Examples of the benzofluorene compound that does not have a skeleton derived from a dimer diamine include P-d type benzofluorene and F-a type benzofluorene.

Examples of commercially available benzopyrene compounds which do not have a skeleton derived from dimer diamine include "P-d type" manufactured by Shikoku Chemical Industry Co., Ltd. and the like.

The content of the component X with respect to 100 parts by weight of the epoxy compound is preferably 50 parts by weight or more, more preferably 85 parts by weight or more, and preferably 150 parts by weight or less, and more preferably 120 parts by weight or less. When the content of the component X is at least the above lower limit and below the above upper limit, the hardenability is more excellent, and the dimensional change of the hardened material due to heat or the volatilization of the remaining unreacted components can be further suppressed.

In 100% by weight of the components other than the inorganic filler and the solvent in the resin material, the total content of the epoxy compound and the component X is preferably 40% by weight or more, more preferably 60% by weight or more, and more preferably 90% by weight or less, more preferably 85% by weight or less. If the total content of the epoxy compound and the component X is greater than or equal to the above lower limit and less than or equal to the above 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 resin material may contain a hardener different from the hardener containing the component X. Examples of the hardener different from the hardener containing the component X include amine compounds (amine hardeners), thiol compounds (thiol hardeners), phosphine compounds, dicyandiamide, and maleimide Amine compounds (cis butylene diimide hardener) and the like.

[Hardening Accelerator] The resin material preferably contains a hardening accelerator. By using the above-mentioned hardening accelerator, the hardening speed is further increased. By rapidly curing the resin material, the crosslinked structure of the hardened material becomes uniform, and the number of unreacted functional groups decreases, resulting in an increase in the crosslink density. When the hardening of the resin material is not sufficiently performed, the dielectric loss tangent may become high and the linear expansion coefficient may become large. By using a hardening accelerator, the effect of a resin material can fully be advanced. The hardening accelerator is not particularly limited, and a conventionally known hardening accelerator can be used. These hardening accelerators may be used alone or in combination of two or more.

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 Free radical hardening accelerators such as peroxides.

Examples of the imidazole compound include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-benzene 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-mesytri, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-homo Tris, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-tris, 2,4-diamino-6- [ 2'-methylimidazolyl- (1 ')]-ethyl-tristriisocyanuric acid adduct, 2-phenylimidazole isotrimeric cyanic acid adduct, 2-methylimidazole isotrimeric Cyanate adducts, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-dihydroxymethylimidazole.

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

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

Examples of the organometallic compound include zinc naphthenate, cobalt naphthenate, tin octoate, cobalt octoate, cobalt (II) acetoacetone, cobalt (III) acetoacetate, and the like.

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

From the viewpoint of suppressing the hardening temperature to be lower, the hardening accelerator preferably contains the anionic hardening accelerator, and more preferably contains the imidazole compound.

From the viewpoint of suppressing the hardening temperature to be lower, the content of the anionic hardening accelerator in 100% by weight of the hardening accelerator is preferably 50% by weight or more, more preferably 70% by weight or more, and even more preferably 80% by weight or more, preferably 100% by weight (whole amount).

The 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 hardening accelerator may include the radical hardening accelerator and the imidazole compound. The radical hardening accelerator is preferably a radical hardening accelerator whose reaction temperature in the presence of the radical hardening accelerator is higher than the hardening temperature before etching and lower than the formal hardening temperature after etching. When a radical hardening accelerator is used, by using PERHEXYL 25B as a radical hardening accelerator, the above effects can be further 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, the hardening of the resin material can be performed well, and a better cured product can be obtained.

The hardening accelerator may include at least one of a radical hardening accelerator, dimethylaminopyridine, an imidazole compound, and a phosphorus compound.

The content of the hardening accelerator is not particularly limited. The content of the above-mentioned hardening accelerator in 100% by weight of the components other than the inorganic filler and the solvent in the resin material is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and more preferably 5% by weight or less. It is preferably 3% by weight or less. When the content of the hardening accelerator is at least the above lower limit and at most the above upper limit, the resin material is hardened efficiently. When the content of the hardening accelerator is in a more preferable range, the storage stability of the resin material is further improved, and a better cured product can be obtained.

[Thermoplastic resin] The resin material preferably contains a thermoplastic resin. Examples of the thermoplastic resin include a polyvinyl acetal resin, a polyimide resin, and a phenoxy resin. These thermoplastic resins may be used alone or in combination of two or more.

From the viewpoint of effectively reducing the dielectric loss tangent and effectively improving the adhesion of the metal wiring regardless of the hardening environment, the thermoplastic resin is preferably a phenoxy resin. By using a phenoxy resin, it is possible to suppress deterioration of the coverage of the holes or irregularities of the resin film on the circuit board and unevenness of the inorganic filler. In addition, by using a phenoxy resin, the melt viscosity can be adjusted, so the dispersibility of the inorganic filler becomes good, and during the hardening process, the resin composition or the B-staged compound becomes less prone to wetting and diffusion in unexpected regions .

The phenoxy resin contained in the resin material is not particularly limited. As the phenoxy resin, a conventionally known phenoxy resin can be used. These phenoxy resins may be used alone or in combination of two or more.

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

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

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

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

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 having more excellent storage stability, the weight average molecular weight of the thermoplastic resin, the polyimide resin, and the phenoxy resin is preferably 5,000 or more, more preferably 10,000 or more, and more preferably It is 100,000 or less, and more preferably 50,000 or less.

The weight average molecular weight of the thermoplastic resin, the polyfluorene imide resin, and the phenoxy resin represents a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The content of the thermoplastic resin, the polyfluorene imine resin, and the phenoxy resin is not particularly limited. The content of the thermoplastic resin in 100% by weight of components other than the inorganic filler and the solvent in the resin material (in the case where the thermoplastic resin is a polyimide resin or a phenoxy resin, it is a polyimide resin Or the content of the phenoxy resin) is preferably 1% by weight or more, more preferably 2% by weight or more, and preferably 30% by weight or less, and more preferably 20% by weight or less. When the content of the thermoplastic resin is greater than or equal to the above lower limit and less than or equal to the above upper limit, the coverage of holes or irregularities of the circuit board by the resin material becomes good. When the content of the thermoplastic resin is greater than or equal to the above lower limit, the formation of a resin film becomes easier, and a more favorable insulating layer can be obtained. When the content of the thermoplastic resin is equal to or less than the above upper limit, the thermal expansion coefficient of the cured product is further reduced. When the content of the thermoplastic resin is equal to or less than the above upper limit, the surface roughness of the surface of the hardened material is further reduced, and the bonding strength between the hardened material and the metal layer is further improved.

[Solvent] The above-mentioned resin material contains no solvent or contains a solvent. By using the solvent, the viscosity of the resin material can be controlled to a preferable range, and the coating property of the resin material can be improved. Moreover, the said solvent can also be used to obtain the slurry containing the said inorganic filler. These solvents may be used alone or in combination of two or more.

Examples of the solvent include acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, and 2-acetamidine. 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 solvent is preferably removed when the resin composition is formed into a film. Therefore, the boiling point of the solvent is preferably 200 ° C or lower, and more preferably 180 ° C or lower. The content of the solvent in the resin composition is not particularly limited. In consideration of the applicability of the resin composition and the like, the content of the solvent may be appropriately changed.

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

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

Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent. Examples of the silane coupling agent include vinyl silane, amine silane, imidazole silane, and epoxy silane.

Examples of the other thermosetting resin include polyphenylene ether resin, divinyl benzyl ether resin, polyarylate resin, diallyl phthalate resin, benzofluorene resin, benzoxazole resin, Biscis butylene diimide resin and acrylic resin.

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

The resin material is preferably a thermosetting material.

As a method of forming a resin composition into a film shape, and obtaining a resin film, the following method is mentioned. The resin composition is melt-kneaded using an extruder, and after extrusion, it is formed into a film-like extrusion molding method using a T-die or a round die. A casting method in which a solvent-containing resin composition is cast to form a film. Other previously known film forming methods. In terms of being able to cope with the reduction in thickness, an extrusion molding method or a cast molding method is preferred. The film contains a sheet.

The resin composition can be obtained as a B-stage film by molding the resin composition into a film shape and curing it with heat so as not to be excessive, for example, by heating and drying at 50 ° C to 150 ° C for 1 minute to 10 minutes.

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

The resin film may not be a prepreg. When the resin film is not a prepreg, migration does not occur along glass cloth or the like. In addition, when the resin film is laminated or pre-cured, unevenness due to glass cloth does not occur on the surface. The resin film may be used in the form of a laminated film including a metal foil or a substrate and a resin film laminated on the surface of the metal foil or the substrate. The metal foil is preferably a copper foil.

Examples of the base material of the laminated film include polyester resin films such as polyethylene terephthalate film and polybutylene terephthalate film, olefin resin films such as polyethylene film and polypropylene film, and Polyimide resin film, etc. The surface of the above substrate may also be subjected to a demolding treatment as required.

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

(Semiconductor device, printed wiring board, copper clad laminate, and multilayer printed wiring board) The above-mentioned resin material can be suitably used to form a mold resin embedded in a semiconductor wafer in a semiconductor device.

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

The printed wiring board is obtained, for example, by subjecting the resin material to heat and pressure molding.

The resin film may be a single-sided or double-area metal foil. The method for laminating the resin film and the metal foil is not particularly limited, and a known method can be used. For example, a device such as a parallel flat plate press or a roll laminator can be used to laminate the resin film to a metal foil while heating or pressing without heating.

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

The thickness of the copper foil of the copper-clad laminated board is not particularly limited. The thickness of the copper foil is preferably within a range of 1 μm to 50 μm. In addition, in order to improve the bonding strength between the cured material of the resin material and the copper foil, the copper foil preferably has fine unevenness on the surface. The method for forming the unevenness is not particularly limited. Examples of the method of forming the unevenness include a method of forming the unevenness by a treatment using a known chemical liquid.

The above-mentioned resin material can be suitably used for obtaining a multilayer substrate.

As an example of the multilayer substrate, a multilayer substrate including a circuit substrate and an insulating layer laminated on the circuit substrate may be mentioned. The insulating layer of the multilayer substrate is formed of the resin material. Alternatively, a laminated film may be used, and the insulating film of a multilayer substrate may be formed using the resin film of the laminated film. The above-mentioned insulating layer is preferably laminated on the surface of the circuit substrate on which the circuit is provided. A part of the insulating layer is preferably buried between the circuits.

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

The roughening processing method can use a conventionally well-known roughening processing method, and it does not specifically limit. The surface of the insulating layer may be subjected to a swelling treatment before the roughening treatment.

The multilayer substrate is preferably further provided with a copper plating layer laminated on the roughened surface of the insulating layer.

In addition, 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 of the insulating layer laminated on the insulating layer opposite to the surface on which the circuit substrate is laminated may be cited Copper foil on the side surface. The insulating layer is preferably formed by using a copper-clad laminated board including a copper foil and a resin film laminated on one surface of the copper foil to harden the resin film. Furthermore, the copper foil is preferably a copper circuit after being etched.

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

Regarding the multilayer printed wiring board in the multilayer substrate, a lower dielectric loss tangent is required, and a higher insulation reliability obtained from the insulating layer 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 between the insulating layer and the metal layer and the etching performance. 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 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. 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 substrate 12. The insulating layers 13 to 16 are hardened 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 to 16, the insulating layer 13 to 15 other than the insulating layer 16 on the surface opposite to the circuit substrate 12 side is formed with a metal layer 17 on a part of the upper surface. The metal layer 17 is a circuit. A metal layer 17 is disposed between the circuit substrate 12 and the insulating layer 13 and between the layers of the laminated insulating layers 13 to 16, respectively. The lower metal layer 17 and the upper metal layer 17 are connected to each other by at least one of via connection and via connection (not shown).

In the multilayer printed wiring board 11, the insulating layers 13 to 16 are formed of a cured product of the resin material described above. In this embodiment, since the surfaces of the insulating layers 13 to 16 are roughened, fine holes (not shown) are formed on the surfaces of the insulating layers 13 to 16. The metal layer 17 reaches the inside of the fine holes. Further, in the multilayer printed wiring board 11, the widthwise dimension (L) of the metal layer 17 and the widthwise dimension (S) of a portion where the metal layer 17 is not formed can be reduced. Moreover, in the multilayer printed wiring board 11, good insulation reliability is provided between the upper metal layer and the lower metal layer which are not connected by via connections and via connections (not shown).

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

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

As a method of the said swelling process, the method of processing a hardened | cured material, for example with the aqueous solution of an compound which has ethylene glycol etc. as a main component, an organic solvent dispersion solution, etc. can be used. The swelling liquid used for swelling treatment generally contains alkali as a pH adjuster and the like. The swelling liquid preferably contains sodium hydroxide. Specifically, for example, the above swelling treatment is performed by using a 40% by weight ethylene glycol aqueous solution or the like, and curing the cured product at a processing temperature of 30 ° C to 85 ° C for 1 minute to 30 minutes. The temperature of the swelling treatment is preferably within a range of 50 ° C to 85 ° C. If the temperature of the above swelling treatment is too low, the swelling treatment takes a long time, and the bonding strength between the hardened material and the metal layer tends to decrease.

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

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

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

(Decontamination treatment) In some cases, a hardened material obtained by pre-hardening the resin material may form a through hole. In the above-mentioned multilayer substrate and the like, via holes, via holes, and the like are formed as through holes. For example, the via 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 hole, a residue, that is, a residue of a resin derived from a resin component contained in the hardened substance, is formed on the bottom of the through hole.

In order to remove the stain, the surface of the hardened material is preferably subjected to a decontamination treatment. There are also cases where the decontamination treatment is also used as the roughening treatment.

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

By using the above-mentioned resin material, the surface roughness of the surface of the hardened material subjected to the decontamination treatment becomes sufficiently small.

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

(N-alkylbis-cis-butenedifluorene imine compound having a skeleton derived from a dimer diamine) N-alkylbis-cis-butenedifluorene imine compound 1 ("BMI" manufactured by Designer Molecules Inc. -1500 ", number average molecular weight 1500) N-alkylbiscisbutenediamidoimine compound 2 (" BMI-1700 "manufactured by Designer Molecules Inc., number average molecular weight 1700) N-alkylbiscisbutene Diamidoimine compound 3 ("BMI-3000" manufactured by Designer Molecules Inc., number average molecular weight 3000) N-alkylbiscisbutene diamidoimine compound 4 ("BMI-3000" manufactured by Designer Molecules Inc. 3000J ", number-average molecular weight 5100) N-alkylbiscis-butenediamidoimine compound 5 (" BMI-3000J "manufactured by Designer Molecules Inc. was dissolved in a toluene solution, and isopropanol was added. A compound obtained by recovering the precipitated polymer component (denoted as BMI-3000J treated product in the table) (weight average molecular weight 15000)

(N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine) N-alkylbenzofluorene compound (synthesized according to Synthesis Example 1 below)

(Synthesis example 1) In a reaction vessel provided with a stirrer, a water separator, a thermometer, and a nitrogen introduction tube, 65 g of pyromellitic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 218.12) and 500 mL of cyclohexanone were added. 164 g of a dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan) was dissolved in cyclohexanone and added dropwise. Thereafter, a Dean-Stark separator and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to be heated to obtain a pyrimide compound having an amine structure at both ends. 38 g of the obtained stilbeneimine compound, 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 Benzopyrene. Thereafter, reprecipitation was performed with isopropyl alcohol, whereby an N-alkylbenzofluorene compound (weight average molecular weight 7700) was obtained.

(Others) N-phenyl-cis-butene-diimide compound ("BMI-2300" manufactured by Yamato Chemical Industry Co., Ltd.) N-phenyl-cis-butene-di-imide compound ("BMI-" 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 company) Dicyclopentadiene type epoxy compound ("EP4088S" manufactured by ADEKA company) Naphthol aralkyl type epoxy compound ("ESN-475V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. ")

(Inorganic filler) Silicon dioxide-containing slurry (75% by weight of silicon dioxide: "SC4050-HOA" manufactured by Admatechs, average particle size 1.0 μm, amine silane treatment, cyclohexanone 25% by weight)

(Hardener) Component X: Cyanate compound containing liquid ("BA-3000S" manufactured by Lonza Japan, 75% by weight of solid content) Active ester compound 1 containing liquid ("EXB-9416-70BK" manufactured by DIC) , 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) phenol compound-containing liquid ("LA-1356" manufactured by DIC Corporation, solid content 60% by weight) Carbodiimide compound-containing liquid ("V-03" manufactured by Nisshinbo Chemical Corporation, solid content 50% by weight)

(Hardening accelerator) dimethylaminopyridine ("DMAP" 2-phenyl-4-methylimidazole ("2P4MZ" manufactured by Shikoku Chemical Industry Co., Ltd.) manufactured by Wako Pure Chemical Industries, Ltd.) 2-ethyl-4 -Methylimidazole ("2E4MZ" manufactured by Shikoku Chemical Industry Co., Ltd.) Percumyl D (manufactured by Nippon Oil Corporation)

(Thermoplastic resin) Polyimide compound (Polyimide resin) (According to Synthesis Example 2 below, a reaction product of tetracarboxylic dianhydride and dimer diamine is synthesized, which is a solution containing polyimide compound (non-volatile) 26.8% by weight)) Phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Corporation)

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

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

GPC (gel permeation chromatography) measurement: A high-performance liquid chromatography system manufactured by Shimadzu Corporation was used, and tetrahydrofuran (THF) was used 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 a string system was used in which two "KF-804L" (excluded the limiting molecular weight 400,000) manufactured by Shodex Corporation were connected in series. As the standard polystyrene, a calibration curve was prepared by using "TSK standard polystyrene" manufactured by Tosoh Corporation, and using 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 Calculate the molecular weight.

(Examples 1 to 15 and Comparative Examples 1 to 3) The components shown in the following Tables 1 to 3 were blended at the blending amounts shown in the following Tables 1 to 3, and stirred at normal temperature until a uniform solution was obtained to obtain a resin material.

Production of resin film: Using the applicator, apply the obtained resin material to the release-treated PET film ("XG284", manufactured by Toray, thickness 25 μm), and apply the obtained resin material to a 100 ° C Gil oven (Geer oven) Dry for 2 minutes and 30 seconds to evaporate the solvent. In this way, a laminated film (a laminated film of a PET film and a resin film) having a resin film (B-stage film) having a thickness of 40 μm was laminated on the PET film.

(Evaluation) (1) Dielectric loss tangent The obtained resin film was cut into a width of 2 mm and a length of 80 mm, and five sheets were stacked to obtain a laminated body having a thickness of 200 μm. The obtained laminated body was heated at 190 ° C for 90 minutes to obtain a hardened body. For the obtained hardened body, a "cavity resonance perturbation dielectric constant measuring device CP521" manufactured by Kanto Electronics Application Development Corporation and a "network analyzer N5224A PNA" manufactured by Keysight Technologie were used. The dielectric loss tangent was measured at room temperature (23 ° C) at a frequency of 1.0 GHz.

(2) Adhesiveness (peeling strength) of the insulating layer and the metal layer Laminating steps: Prepare a double-sided copper-clad laminated board (thickness of copper foil on each side of 18 μm, thickness of the substrate 0.7 mm, substrate size 100 mm × 100 mm "MCL-E679FG" manufactured by Hitachi Chemical Co., Ltd.). Both sides of the copper foil surface of the double-sided copper-clad laminated board were immersed in "Cz8101" manufactured by MEC, and the surface of the copper foil was roughened. On both sides of the roughened copper-clad laminated board, the "batch vacuum laminator MVLP-500-IIA" manufactured by Meiko Seisakusho was used to overlap the resin film (B-stage film) side of the laminated film on A copper-clad laminated board was laminated and laminated to obtain a laminated structure. The conditions for lamination are 30 seconds, and the pressure is reduced to 13 hPa or less, and then the pressure is applied at 30 seconds, 100 ° C, and 0.4 MPa.

Film peeling step: In the obtained laminated structure, a double-sided PET film is peeled.

Copper foil attaching step: Cz processing ("Cz8101" manufactured by MEC Corporation) is performed on the smooth surface of a copper foil (thickness: 35 μm, manufactured by Mitsui Metals Co., Ltd.), and the surface of the copper foil is etched by about 1 μm. The copper foil subjected to the etching treatment was bonded to the laminated structure obtained by peeling the PET film to obtain a copper-clad substrate. The obtained copper-clad substrate was heat-treated at 190 ° C for 90 minutes in a Gil oven to obtain an evaluation sample.

(2-1) Measurement of peel strength under room temperature environment: A short strip-shaped incision with a width of 1 cm was cut into the surface of the copper foil of the evaluation sample. An evaluation sample was set on a 90 ° peel tester ("TE-3001" manufactured by TESTER SANGYO), and the end of the copper foil with a cut was clamped by a jig, and the copper foil was peeled off by 20 mm, and the peel strength was measured.

[Judgment Criteria for Peel Strength in Room Temperature Environment] ○: 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 into the surface of the copper foil of the evaluation sample. A heating unit was set in a 90 ° peel tester ("TE-3001" manufactured by TESTER SANGYO) where the evaluation sample was installed, and then the evaluation sample was set and the heating unit was set to 260 ° C. Then, the edge part of the copper foil which has a notch was clamped by the jig | tool, the copper foil was peeled by 20 mm, and 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 retardance Lamination step: Prepare a double-sided copper-clad laminated board (0.2 mm thick, "MCL-E-679FGR" manufactured by Hitachi Chemical Co., Ltd.). On both sides of the double-sided copper-clad laminated board, a "batch vacuum laminator MVLP-500-IIA" manufactured by Mingji Seisakusho was used to overlap the resin film (B-stage film) side of the laminated film on the copper-clad The laminate is laminated and laminated to obtain a laminate structure. The conditions for lamination are 30 seconds, and the pressure is reduced to 13 hPa or less, and then the pressure is applied at 30 seconds, 100 ° C, and 0.4 MPa.

Film peeling step: In the obtained laminated structure, a double-sided PET film is peeled.

Lamination step: The obtained resin film with a thickness of 40 μm is further pasted twice on the double-sided surface of the above-mentioned laminated structure, and each single-area layer on a double-sided copper-clad laminated board is produced with a resin film with a total thickness of 120 μm. Laminated samples.

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

Evaluation of flame retardancy: The obtained evaluation samples were cut into 135 mm in length × 13 mm in width. Then, the cut-out evaluation sample was fixed with a splint, and a flame of a gas burner was placed under the evaluation sample to burn the resin film. The time until the flame spread out of the resin film was measured.

[Judgment criteria for flame retardancy] ○ ○: The time until the flame goes out is less than 7 seconds ○: The time until the flame goes out is 7 seconds or more and less than 10 seconds ×: The time until the flame goes out is 10 seconds or more

(4) Surface roughness (surface roughness after roughening treatment) Lamination step and semi-hardening treatment: Prepare a double-sided copper clad laminate (CCL substrate) ("E679FG" manufactured by Hitachi Chemical Co., Ltd.). Both sides of the copper foil surface of the double-sided copper-clad laminated board were immersed in "Cz8101" manufactured by MEC, and the surface of the copper foil was roughened. On both sides of the roughened copper-clad laminated board, the "batch vacuum laminator MVLP-500-IIA" manufactured by Meiko Seisakusho was used to overlap the resin film (B-stage film) side of the laminated film on A copper-clad laminated board was laminated and laminated to obtain a laminated structure. The conditions for lamination are 30 seconds, and the pressure is reduced to 13 hPa or less, and then the pressure is applied at 30 seconds, 100 ° C, and 0.4 MPa. Then, it heated at 180 degreeC for 30 minutes, and hardened the resin film. In this way, a laminated body of a semi-hardened material having a resin film laminated on a CCL substrate was obtained.

Roughening treatment: (a) Swelling treatment: The obtained laminate was put into a swelling liquid ("Swelling Dip Securigant P" manufactured by Atotech Japan) at 80 ° C, and shaken for 10 minutes. Thereafter, it was washed with pure water.

(b) Permanganate treatment (roughening treatment and decontamination treatment): The laminated body after the swelling treatment is placed in a roughened aqueous solution of potassium permanganate ("Concentrate Compact CP" manufactured by Atotech Japan) at 60 ° C. , Shake for 30 minutes. Next, a 25 ° C washing solution ("Reduction Securigant P" manufactured by Atotech Japan) was used for 2 minutes, and then washed with pure water to obtain an evaluation sample.

Measurement of surface roughness: The surface of the evaluation sample (roughened hardened material) was measured in a measurement area of 94 μm × 123 μm using a non-contact three-dimensional surface shape measuring device ("WYKO NT1100" manufactured by Veeco). Arithmetic average roughness Ra. The arithmetic mean roughness Ra is measured in accordance with JIS B0601: 1994. The surface roughness was determined based on the following criteria.

[Judgment Criteria for Surface Roughness] ○: Ra is less than 50 nm ○: Ra is 50 nm or more and less than 200 nm ×: Ra is 200 nm or more

(5) Electrolytic plating treatment for peeling strength of the coating layer: Roughened hardening obtained in the evaluation of (4) surface roughness using an alkaline cleaning solution ("Cleaner Securigant 902" manufactured by Atotech Japan) at 60 ° C The surface of the object was treated for 5 minutes, and then degreased and washed. After washing, the cured product was treated with a 25 ° C prepreg ("Pre-dip Neogant B" manufactured by Atotech Japan) for 2 minutes. 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 at 30 ° C ("Reducer Neogant WA" manufactured by Atotech Japan) for 5 minutes.

Next, the hardened material was added to a chemical copper solution ("Basic Printganth MSK-DK", "Copper Printganth MSK", "Stabilizer Printganth MSK", and "Reducer Cu") manufactured by Atotech Japan, and electroless plating was performed 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 steps up to the step of electroless plating are performed by setting the treatment liquid to 2 L with a beaker scale while shaking the hardened material.

Electrolytic plating treatment: Next, the hardened material subjected to the electroless plating treatment is subjected to electrolytic plating until the plating thickness becomes 25 μm. For electrolytic copper plating, copper sulfate solution ("copper sulfate pentahydrate" manufactured by Wako Pure Chemical Industries, "sulfuric acid" manufactured by Ko Pure Chemical Industries, "Basic Leveller Cupracid HL" manufactured by Atotech Japan, and Atotech Japan "Cupracid GS" (manufactured by the company), a current of 0.6 A / cm ^{2 was} passed, and electrolytic plating was performed until the plating thickness became 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 plating layer on the upper surface area was obtained.

Measurement of the peeling strength of the plating layer: A short strip-shaped notch having a width of 0.5 cm was cut into the surface of the copper-plated layer of the hardened product having the copper-plated layer on the upper surface area. A 90 ° peel tester ("TE-3001" manufactured by TESTER SANGYO Co., Ltd.) was installed on a hardened object having a copper plating layer on its upper surface area. The end of the copper plating layer with a cut was clamped by a jig to peel the copper plating layer. 15 mm, and measured peel strength (plating peel strength).

[Criteria for judging the peeling strength of the plating layer] ○ ○: The peeling strength of the coating is 0.5 kgf or more ○: The peeling strength of the coating is 0.3 kgf or more and less than 0.5 kgf ×: The peeling strength of the coating is less than 0.3 kgf

(6) Hardening temperature A differential scanning calorimeter ("Q2000" manufactured by TA Instruments) was used to evaluate the exothermic peak accompanying the hardening of the obtained resin film (B-stage film). Take 8 mg of resin film in a special aluminum pan and cover it with a special jig. This special aluminum pan and empty aluminum pan (for reference) are set in a heating unit, and heated from -30 ° C to 250 ° C at a heating rate of 3 ° C / min under a nitrogen environment, and observed the reverse heat flow and non-reverse heat flow. From the exothermic peak observed in the non-reverse heat flow, the hardening temperature was confirmed.

[Criterion Criteria for Hardening Temperature] ○: All exothermic peaks below 200 ° C ×: At least one exothermic peak at temperatures above 200 ° C (including exothermic peaks at temperatures above 200 ° C and 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 cracks or cracks in the resin film in 10 times.

[Criteria for judging the flexibility of the resin film] ○: The number of occurrences of cracks or cracks in 10 times has not reached 3 times △: The number of occurrences of cracks or cracks in 10 times is 3 or more and less than 6 times ×: 10 times Occurrence of cracks or ruptures more than 6 times

(8) The coverage of the uneven surface is only for 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), and the center of the substrate is 30 In the area of mm square, a depression (opening) with a diameter of 100 μm and a depth of 25 μm is opened so that the interval between the centers of adjacent holes located on a straight line is 900 μm. In this manner, an evaluation substrate having a total of 900 pits was prepared.

The resin film side of the obtained laminated film was superimposed on the evaluation substrate, and a "batch vacuum laminator MVLP-500-IIA" manufactured by Meiki Seisakusho was used, and the lamination pressure was 0.4 MPa for 20 seconds. The pressing pressure was 0.8 MPa for 20 seconds, and the heating and pressing were performed at a lamination and pressing temperature of 90 ° C. After cooling at normal temperature, the PET film was peeled. In this way, an evaluation sample having a resin film laminated on the evaluation substrate was obtained.

With respect to the obtained evaluation samples, voids were observed in the depressions using an optical microscope. By evaluating the ratio of the depressions in which voids were observed, the coverage on the uneven surface was determined based on the following criteria.

[Criteria for determining the coverage of uneven surfaces] ○: The ratio of voids in which voids are observed is 0% △: The ratio of voids in which voids are observed exceeds 0% to less than 5% ×: The ratio of voids in which voids are observed is 5% or more

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

[Table 1]

[Table 2]

[table 3]

11‧‧‧Multilayer printed wiring board

12‧‧‧circuit board

12a‧‧‧upper surface

13 ～ 16‧‧‧ Insulation layer

17‧‧‧ metal layer

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

Claims (15)

A resin material comprising: an N-alkylbiscisbutenedifluorene imine compound having a skeleton derived from a dimer diamine or an N-alkylbenzofluorene having a skeleton derived from a dimer diamine Compounds; epoxy compounds; inorganic fillers; and benzopyrene compounds containing a phenol compound, a cyanate compound, an acid anhydride, an active ester compound, a carbodiimide compound, and a skeleton derived from a dimer diamine At least one component of a hardener; when the above-mentioned N-alkylbiscis-butenedifluorene imine compound having a skeleton derived from a dimer diamine is included, the above-mentioned compound having a dimer derived diamine The weight ratio of the content of the N-alkylbiscis-butenedifluorene imine compound of the skeleton to the total content of the epoxy compound and the hardener is 0.05 or more and 0.75 or less. In the case of an N-alkylbenzofluorene compound having an amine skeleton, the content of the N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine is relative to the total of the epoxy compound and the hardener. The weight ratio of content is 0.05 On 0.75. The resin material according to claim 1, wherein the N-alkylbiscis-butenediamidine imine compound having a skeleton derived from a dimer diamine has a structure represented by the following formula (X), The N-alkylbenzofluorene compound of the skeleton of a dimer diamine has a structure represented by the following formula (X), In the formula (X), R1 represents a tetravalent organic group. The resin material according to claim 1 or 2, wherein the epoxy compound is an epoxy compound having an aromatic skeleton, and the component is a component having an aromatic skeleton. The resin material according to claim 1 or 2, wherein the hardener comprises an active ester compound having two or more aromatic skeletons. The resin material as claimed in claim 1 or 2, which contains a hardening accelerator. The resin material according to claim 5, wherein the hardening accelerator comprises an anionic hardening accelerator. The resin material according to claim 6, wherein the content of the anionic hardening accelerator in 100% by weight of the hardening accelerator is 50% by weight or more. The resin material according to claim 6, wherein the anionic hardening accelerator is an imidazole compound. The resin material according to claim 5, 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 inorganic filler is 1 μm or less. The resin material according to claim 1 or 2, comprising the above-mentioned N-alkylbiscis-butenediamidoimine compound having a skeleton derived from a dimer diamine, and the above having a skeleton derived from a dimer diamine The molecular weight of the N-alkylbiscis-butenedifluorene imine compound is less than 15,000. The resin material according to claim 1 or 2, comprising the above-mentioned N-alkylbenzofluorene compound having a skeleton derived from a dimer diamine, and the above-mentioned N-alkyl compound having a skeleton derived from a dimer diamine The molecular weight of the benzofluorene compound is less than 15,000. If the resin material of claim 1 or 2 is a resin film. The resin material of claim 1 or 2 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 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. The first layer is a hardened material of the resin material according to any one of claims 1 to 14.