WO2019146797A1

WO2019146797A1 - Thermosetting resin composition, resin film for interlayer insulation, composite film, printed wiring board, and semiconductor package

Info

Publication number: WO2019146797A1
Application number: PCT/JP2019/002962
Authority: WO
Inventors: 彩笠原; 哲郎岩倉; 由佳子庄子; 信次土川
Original assignee: 日立化成株式会社
Priority date: 2018-01-29
Filing date: 2019-01-29
Publication date: 2019-08-01
Also published as: TW201936786A; JP7251482B2; JPWO2019146797A1

Abstract

Provided is a thermosetting resin composition which, as a thermosetting resin composition that can be used as a composite film for electronic devices using high frequency band signals, has a high glass transition temperature, excellent embedding properties with respect to unevenness in a circuit, etc., excellent dielectric characteristics as well as low thermal expansion, and also has good handling properties (that is, when the thermosetting resin composition has been B staged, said thermosetting resin composition is flexible, and in addition, when said thermosetting resin composition is made into a film, cracks do not easily occur even if the same is bent, and the thermosetting resin composition is easy to peel from a protective film.) Further provided is a resin film for interlayer insulation in which the thermosetting resin composition is used, a composite film, a printed wiring board, and a semiconductor package. Specifically, the thermosetting resin composition comprises a polyimide compound (A) which has: a structural unit derived from a maleimide compound (a1) having at least two N-substituted maleimide groups; and a structural unit derived from an amine compound (a2) having a total carbon number of 3-13.

Description

Thermosetting resin composition, resin film for interlayer insulation, composite film, printed wiring board and semiconductor package

The present invention relates to a thermosetting resin composition, an interlayer insulating resin film, a composite film, a printed wiring board, and a semiconductor package.

In recent years, miniaturization, weight reduction, multi-functionalization, and the like of electronic devices have further progressed, and along with this, high integration of LSI (Large Scale Integration), chip parts, etc. has progressed, and the form thereof is also multi-pin and compact. Is rapidly changing. For this reason, in order to improve the mounting density of electronic components, development of micro wiring of a multilayer printed wiring board is advanced. As a multilayer printed wiring board meeting these requirements, a multilayer printed wiring board of a buildup structure in which an insulating resin film not containing glass cloth is used as an insulating layer (hereinafter also referred to as a "buildup layer") instead of a prepreg. However, it is becoming mainstream as a printed wiring board suitable for weight reduction, miniaturization and miniaturization.

When producing a film for forming a buildup layer, it is required to have good handling properties, that is, to have flexibility when the thermosetting resin composition is B-staged, and when it is formed into a film Properties (generally referred to as handling properties) are also required, such as being resistant to cracking even when bent and easily peeling off from the protective film. Conventionally, a thermosetting resin composition containing a liquid epoxy resin has been adopted as a material of the film in order to obtain a film having a good handling property (see, for example, Patent Document 1). However, a film obtained from a thermosetting resin composition containing a liquid epoxy resin usually has a problem that the dielectric loss tangent is large.
On the other hand, a polyimide compound having a structural unit derived from a maleimide compound (a1) having at least two N-substituted maleimide groups and a structural unit derived from a diamine compound (a2) as a material of a film capable of obtaining a low dielectric loss tangent The thermosetting resin composition to contain is known (for example, refer to patent documents 2).

Patent No. 5504553 International Publication No. 2016/114030

However, since the polyimide compound is generally rigid, it is not easy to improve the handling property. In this respect, in Patent Document 2, a bending test is conducted to evaluate the handling property of the film, and it is successful to obtain a film having a good handling property from this point of view. However, as for the handling property, as described above, the thermosetting resin composition has flexibility when it is B-staged, and when it is formed into a film, it easily peels off from the protective film (tackiness is not too strong, so much The property of good) is also important industrially. That is, the handling property is good from the viewpoints of flexibility when the thermosetting resin composition is B-staged, that a crack does not easily occur during bending, and that it is easily peeled off from a protective film. desired.
In addition, the buildup layer is required to have a high glass transition temperature (Tg) from the viewpoint of reliability, and an embeddability to irregularities of a circuit or the like (hereinafter, may be simply referred to as "embeddability"). Ru. Furthermore, low thermal expansion is also required in order to improve processing dimensional stability and reduce the amount of warpage after semiconductor mounting.
Under such circumstances, in recent years, computers and information communication devices have become increasingly sophisticated and sophisticated, and in order to process a large amount of data at a high speed, signals to be handled tend to have high frequencies. In particular, the frequency range of radio waves used for mobile phones and satellite broadcasting is in the high frequency range of GHz band, and in order to suppress the transmission loss due to high frequency, the relative dielectric constant as an organic material used in the high frequency range And materials with low dielectric loss tangent are desired.

Therefore, the subject of the present invention is a high glass transition temperature as a thermosetting resin composition that can be used as a composite film for electronic devices using signals in a high frequency band, and it is excellent in embedding property to irregularities of a circuit etc. It has both dielectric properties and low thermal expansion, and also has good handling properties (that is, it has flexibility when B-staging the thermosetting resin composition, and along with that, it has cracks even when it is bent into a film To provide a thermosetting resin composition which is less likely to form and easily peel from a protective film, and an interlayer insulating resin film, a composite film, a printed wiring board and a semiconductor package using the thermosetting resin composition To provide.

As a result of intensive studies to solve the above problems, the present inventors have found that a structural unit derived from a structural unit derived from a maleimide compound having at least two N-substituted maleimide groups and an amine compound having a predetermined total carbon number It has been found that a thermosetting resin composition containing a polyimide compound (A) having a unit can solve the above problems, and the present invention has been completed.

That is, the present invention relates to the following [1] to [14].
[1] A polyimide compound (A) having a structural unit derived from a maleimide compound (a1) having at least two N-substituted maleimide groups and a structural unit derived from an amine compound (a2) having a total of 3 to 13 carbon atoms A thermosetting resin composition containing
[2] The thermosetting resin composition according to the above [1], wherein the amine compound (a2) is liquid at normal temperature.
[3] The thermosetting resin composition according to the above [1] or [2], wherein the amine compound (a2) is an aliphatic amine.
[4] The thermosetting resin composition according to [3] above, wherein the aliphatic amine is at least one selected from the group consisting of aliphatic monoamines, aliphatic diamines and alicyclic diamines.
[5] A group derived from a maleimide group derived from a maleimide compound (a1) (including a maleimide group) with respect to the total equivalent (Ta2) of groups derived from the amino group of the amine compound (a2) in the polyimide compound (A) The thermosetting resin composition according to any one of the above [1] to [4], wherein an equivalent ratio [Ta1 / Ta2] to a total equivalent (Ta1) of is from 1.0 to 50.
[6] The thermosetting resin composition according to any one of the above [1] to [5], wherein the polyimide compound (A) further has a structural unit derived from a polyamine compound (a3).
[7] Sum of the total equivalent (Ta2) of the amino group-derived group of the amine compound (a2) and the amino group-derived group (including the amino group) of the polyamine compound (a3) in the polyimide compound (A) The equivalent ratio [Ta1 / (Ta2 + Ta3)] to the total equivalent (Ta1) of the group derived from the maleimide group (including the maleimide group) derived from the maleimide compound (a1) relative to the total amount with the equivalent (Ta3) is 1.0 The thermosetting resin composition according to the above [6], which is -10.
[8] The total number of moles of the amino group-derived group (Ma2) of the amine compound (a2) and the total number of moles (Ma3) of the amino group-derived group (including the amino group) of the polyamine compound (a3) The thermosetting resin composition according to the above [6] or [7], wherein the ratio [Ma2 / Ma3] is 0.01 to 10.
[9] Furthermore, it contains at least 1 sort (s) selected from the group consisting of an elastomer (B), an inorganic filler (C), and a hardening accelerator (D) in any one of said [1]-[8] Thermosetting resin composition.
[10] The thermosetting resin composition according to the above [9], wherein the curing accelerator (D) contains a peroxide.
[11] A resin film for interlayer insulation, which comprises the thermosetting resin composition according to any one of the above [1] to [10].
[12] A composite film comprising a first resin layer containing the thermosetting resin composition according to any one of the above [1] to [10] and a second resin layer.
[13] A printed wiring board comprising the cured product of the resin film for interlayer insulation according to the above [11] or the cured product of the composite film according to the above [12].
[14] A semiconductor package comprising the printed wiring board according to the above [13].

According to the present invention, as a thermosetting resin composition that can be used as a composite film for an electronic device using a signal in a high frequency band, it has a high glass transition temperature, is excellent in embeddability with respect to irregularities of circuits and the like, and has excellent dielectric properties. It has both properties and low thermal expansion, and also has good handling when made into a film (that is, it has flexibility when the thermosetting resin composition is B-staged, and when it is made into a film, it is bent as well) However, the thermosetting resin composition can be provided which can be less likely to be cracked and easily peeled off from the protective film. And the resin film for interlayer insulation using this thermosetting resin composition, a composite film, a printed wiring board, and a semiconductor package can be provided.

It is the figure which showed typically the one aspect | mode of the composite film of this embodiment. FIG. 6 is a graph showing a temperature-melt viscosity curve of the resin film for interlayer insulation manufactured in Example 4 and Comparative Example 1. FIG.

Hereinafter, embodiments of the present invention will be described in detail. In the present specification, a numerical range (X, Y is a real number) which is X or more and Y or less may be expressed as “X to Y”. For example, the description “0.1 to 2” indicates a numerical range which is 0.1 or more and 2 or less, and the numerical range includes 0.1, 0.34, 1.03, 2 and the like.

In the present specification, the films such as “interlayer insulating resin film” and “composite film” are films in which the thermosetting resin composition contained is uncured and semi-cured thermosetting resin composition contained. Includes both films (in a so-called B-stage).
The "composite" of the composite film means that the film is formed of a plurality of resin layers, and if the embodiment is included, it further has another layer comprising a support, a protective film, etc. May be

Further, in the present specification, the “interlayer insulating layer” is a layer which is located between two conductor layers and insulates the conductor layers. The “interlayer insulating layer” in the present specification includes, for example, a cured product of a composite film. In the present specification, the term "layer" includes those which are partially missing and those where vias or patterns are formed.
Further, in this specification, the dielectric constant and dielectric loss tangent in the high frequency band may be referred to as dielectric characteristics or high frequency characteristics, and the fact that the dielectric constant and dielectric loss tangent in the high frequency band are low is expressed as excellent high frequency characteristics. Sometimes.
In addition, the aspect which combined the description item in this specification arbitrarily is also contained in this invention in all.

[Thermosetting resin composition]
The thermosetting resin composition of the present embodiment has a structural unit derived from a maleimide compound (a1) having at least two N-substituted maleimide groups, and a structure derived from an amine compound (a2) having a total of 3 to 13 carbon atoms. It is a thermosetting resin composition containing the polyimide compound (A) which has a unit and.
The polyimide compound (A) will be described in detail below.

<Polyimide compound (A)>
The polyimide compound (A) has a structural unit derived from a maleimide compound (a1) having at least two N-substituted maleimide groups and a structural unit derived from an amine compound (a2) having a total of 3 to 13 carbon atoms It is. The polyimide compound (A) may further contain other structural units.

(Maleimide compound (a1) having at least two N-substituted maleimide groups)
The maleimide compound (a1) having at least two N-substituted maleimide groups (hereinafter also referred to as "component (a1)") is not particularly limited as long as it is a maleimide compound having two or more N-substituted maleimide groups.
As the component (a1), for example, bis (4-maleimidophenyl) methane, polyphenylmethane maleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3′-dimethyl-5, 5'-Diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane and the like Can be mentioned. These may be used alone or in combination of two or more.
The component (a1) may be a maleimide compound containing an aromatic hydrocarbon group somewhere in the molecule, that is, an aromatic maleimide compound, or a so-called aliphatic maleimide having only an aliphatic hydrocarbon group. It may be a compound, but is preferably an aromatic maleimide compound.
Component (a1) is preferably bis (4-maleimidophenyl) methane from the viewpoint of being inexpensive, and is excellent in dielectric properties and low in water absorption, so 3,3'-dimethyl-5,5'-diethyl- 4,4'-Diphenylmethane bismaleimide is preferred, and 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane is preferred from the viewpoint of excellent mechanical properties such as high adhesion to a conductor, elongation, and breaking strength. .

Examples of the structural unit derived from the component (a1) include a group represented by the following general formula (1-1), a group represented by the following general formula (1-2), and the like.

In the general formulas (1-1) and (1-2), A ¹ represents a residue of the component (a1), and * represents a bond. Although A ¹ is not particularly limited, for example, the same residues as A ³ described later are preferable.
In addition, a residue means the structure of the part except the functional group (The maleimide group in component (a1)) provided to coupling | bonding from a raw material component.

(Amine compound (a2) having a total of 3 to 13 carbon atoms)
The amine compound (a2) having a total carbon number of 3 to 13 (hereinafter also referred to as "component (a2)") is not particularly limited as long as the total carbon number is 3 to 13, and aliphatic amines (alicyclic Or an aromatic amine, may be a monoamine compound, or may be a diamine compound. Among these, aliphatic amines are preferable as the component (a2).
The said component (a2) used by this embodiment is an amine compound liquid at normal temperature, and when B-staging a thermosetting resin composition, a softness becomes favorable, ie, it is excellent in handling property. Here, when a general liquid amine compound is used, when the carbon number of the amine compound is increased, the embedding property to irregularities of a circuit or the like is deteriorated at low Tg with respect to the characteristics of the cured product of the polyimide compound, and thermal The expansion coefficient also increases. However, in the present embodiment, although it is an amine compound having a small total number of carbon atoms as described above, by using a liquid compound at normal temperature, it has a high Tg and is excellent in the burying property to irregularities of a circuit etc. Dielectric property and low thermal expansion, and also good handling when used as a film (that is, it has flexibility when the thermosetting resin composition is B-staged, and when it is used as a film Even if it is bent, it is hard to form a crack and it is easy to peel from a protective film. It is possible that the amino groups in the amine compound (a2) Michael-added to the component (a1) are stacked (stacked) due to substitution of a group having a small carbon number with a nitrogen atom, such as improvement of Tg and low thermal expansion coefficient I guess that it was connected.

Among the above, at least one selected from the group consisting of aliphatic monoamines, aliphatic diamines and alicyclic diamines is preferable as the aliphatic amine, and aliphatic monoamines are more preferable.
Examples of aliphatic monoamines include allylamine and diallylamine. Among these, diallylamine is preferred.
Examples of aliphatic diamines include ethylene diamine and the like.
Examples of alicyclic diamines include norbornane diamine, norbornene diamine, 4,4′-diaminodicyclohexylmethane and the like.

Sum of maleimide group-derived groups (including maleimide group) derived from maleimide compound (a1) relative to the total equivalent (Ta2) of amino group-derived groups of the amine compound (a2) in the polyimide compound (A) The equivalent ratio [Ta1 / Ta2] to the equivalent (Ta1) is preferably 1.0 to 50, and more preferably 1.0 to 30. When the content is in the above range, better heat resistance and glass transition temperature tend to be obtained.

The polyimide compound (A) may further have a structural unit derived from a polyamine compound (a3) (hereinafter, also referred to as “component (a3)”. However, the above-mentioned amine compound (a2) is not included). Moreover, it is preferable to have.

Component (a3) is not particularly limited as long as it is a compound having two or more amino groups. The component (a3) is preferably a compound having two amino groups, that is, a diamine compound.
As the component (a3), for example, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, 4,4 '-Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4 '-Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3'- Dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-) 4-Aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4, 4'-bis (4-aminophenoxy) biphenyl, 1,3-bis (1- (4- (4-aminophenoxy) phenyl) -1-methylethyl) benzene, 1,4-bis (1- (4- (4-amino-4-phenoxy) phenyl) benzene (4-Aminophenoxy) phenyl) -1-methylethyl) benzene, 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 4,4 ′-[1,4-phenylenebis ( 1-Methylethylidene)] bisaniline, 3,3 '-[1,3-phenylenebis (1-methylethylidene)] bisaniline, bis (4- (4-aminophenoxy) phenyl Sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 9,9-bis (4-aminophenyl) fluorene, and the like. These may be used alone or in combination of two or more.

The component (a3) is 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, from the viewpoint of excellent solubility in organic solvents, reactivity during synthesis, and heat resistance. 4,4'-Diamino-3,3'-diethyldiphenylmethane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 4,4 '-[1,3-phenylenebis (1-methylethylidene) ]] Bisaniline and 4,4 '-[1,4-phenylenebis (1-methylethylidene)] bisaniline are preferred. Component (a3) is preferably 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane from the viewpoint of excellent dielectric properties and low water absorption. Component (a3) is preferably 2,2-bis (4- (4-aminophenoxy) phenyl) propane, from the viewpoint of excellent mechanical properties such as high adhesion to a conductor, elongation, and breaking strength. Furthermore, in addition to the above-mentioned solubility in organic solvents, reactivity during synthesis, heat resistance, and high adhesion with a conductor, the component (a3) can exhibit excellent high-frequency characteristics and low hygroscopicity. 4) is preferably 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bisaniline or 4,4'-[1,4-phenylenebis (1-methylethylidene)] bisaniline. These may be used alone or in combination of two or more depending on the purpose, application and the like.

Examples of the structural unit derived from the component (a3) include a group represented by the following general formula (3-1), a group represented by the following general formula (3-2), and the like.

In the general formulas (3-1) and (3-2), A ² represents a residue of component (a3), and * represents a binding site. A ² is not particularly limited, but is preferably a group represented by the following general formula (4).

(Wherein, R ¹ and R ² each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom. A ³ represents carbon An alkylene group of 1 to 5 carbon atoms, an alkylidene group of 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a ketone group, a fluorenylene group, a single bond, the following general formula (4-1) It is a residue represented by formula (4-2).)

(Wherein, R ³ and R ⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom. A ⁴ represents an alkylene group having 1 to 5 carbon atoms, 2 carbon atoms. And an alkylidene group, an m- or p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a ketone group, or a single bond.

(Wherein each R ⁵ independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom. A ⁵ and A ^{6 each} represent an alkylene group having 1 to 5 carbon atoms, 2 carbon atoms An alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a ketone group, or a single bond of to 5

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ¹ to R ⁵ include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl and n-. A pentyl group etc. are mentioned.
Examples of the halogen atom represented by R ¹ to R ⁵ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkylene group of 1 to 5 carbon atoms represented by A ³ to A ⁶ include a methylene group, a dimethylene group, a trimethylene group, a tetramethylene group and a pentamethylene group.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by A ³ to A ⁶ include an ethylidene group, a propylidene group, an isopropylidene group, an isobutylidene group and the like. The alkylidene group having 2 to 5 carbon atoms is preferably an isopropylidene group.

In the general formula (4), R ¹ and R ² are preferably hydrogen atoms. A ³ is preferably a residue represented by General Formula (4-2). A ⁵ and A ⁶ in the general formula (4-2) are preferably isopropylidene groups, and R ⁵ is preferably a hydrogen atom. Moreover, the aspect which combined these is also more preferable.

With respect to the total amount of the total equivalent (Ta2) of groups derived from the amino group of the amine compound (a2) and the total equivalent (Ta3) of groups derived from the amino group of the amine compound (a3) in the polyimide compound (A) The equivalent ratio [Ta1 / (Ta2 + Ta3)] to the total equivalent (Ta1) of the group derived from the maleimide group (including the maleimide group) derived from the maleimide compound (a1) is preferably 1.0 to 10, More preferably, it is in the range of from 0 to 5.0. By setting the content in the above range, better high frequency characteristics, heat resistance, flame retardancy, and glass transition temperature tend to be obtained.

Further, the ratio of the total number of moles of the amino group-derived group (Ma2) of the amine compound (a2) and the total number of moles of the amino group-derived group (including the amino group) of the polyamine compound (a3) (Ma3) [Ma2 / Ma3] is preferably 0.01 to 10, more preferably 0.05 to 5, and even more preferably 0.1 to 4, 0.1 to 3. Is more preferable, and 0.3 to 1.5 is particularly preferable. By being in the above-mentioned range, the glass transition temperature is high, the burying property to irregularities of a circuit or the like is excellent, both the excellent dielectric property and the low thermal expansion are compatible, and the handling property when made into a film is also good ( It has flexibility when B-staged the thermosetting resin composition, and along with it, when it is made into a film, it becomes a thermosetting resin composition which hardly cracks and easily peels off from the protective film even when bent. It tends to be easy.

(Method for producing polyimide compound (A))
The polyimide compound (A) can be produced, for example, by reacting the component (a1), the component (a2), and, if necessary, the component (a3) and other components in an organic solvent.
The organic solvent used when manufacturing a polyimide compound (A) does not have a restriction | limiting in particular, A well-known solvent can be used. The organic solvent may be an organic solvent used for producing a varnish for a resin film for interlayer insulation described later.

When manufacturing a polyimide compound (A), a reaction catalyst can also be used as needed. The reaction catalyst is not limited, but is, for example, an acidic catalyst such as p-toluenesulfonic acid; amines such as triethylamine, pyridine and tributylamine; imidazoles such as methylimidazole and phenylimidazole; phosphorus catalysts such as triphenylphosphine Can be mentioned. These may be used alone or in combination of two or more.
The amount of the reaction catalyst used is not particularly limited, but, for example, it is 0 based on the total amount of 100 parts by mass of the component (a1), the component (a2), and the component (a3) used as needed and other components. It can be used in the range of .01 to 5.0 parts by mass.

Component (a1), component (a2), optionally component (a3) and other components are charged into the reactor in predetermined amounts, component (a1), component (a2) and optionally component (a3) and other components The polyimide compound (A) is obtained by the Michael addition reaction. The reaction conditions in this step are not particularly limited, but for example, the reaction temperature is preferably 50 to 160 ° C., and the reaction time is preferably 1 to 10 hours, from the viewpoint of workability such as reaction rate, gelation suppression, etc. .
In this step, the above-mentioned organic solvent can be added or concentrated to adjust the solid content concentration and solution viscosity of the reaction raw material. The solid content concentration of the reaction raw material is not particularly limited, but is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass. When the solid content concentration of the reaction raw material is 10% by mass or more, the reaction rate does not become too slow, which is advantageous in terms of production cost. In addition, when the solid content concentration of the reaction raw material is 90% by mass or less, better solubility is obtained, the stirring efficiency is good, and gelation is less.
In addition, after manufacture of a polyimide compound (A), according to the objective, some or all of an organic solvent may be removed and it may concentrate, and an organic solvent may be added and diluted. As an organic solvent used additionally, the organic solvent illustrated by the manufacturing process of a polyimide compound (A) is applicable. These may be used alone or in combination of two or more. Further, from the viewpoint of solubility, the organic solvent to be used is preferably methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, more preferably propylene glycol monomethyl ether.

The weight average molecular weight (Mw) of the polyimide compound (A) is not particularly limited, but for example, a range of 800 to 1,500 is preferable, a range of 800 to 1,300 is more preferable, and 1,000 to 1,300 A range is more preferred. The weight average molecular weight of the polyimide compound (A) can be determined by the method described in the examples.

(Content of Polyimide Compound (A))
The content of the polyimide compound (A) in the thermosetting resin composition of the present embodiment is not particularly limited, but it is 50 in the total mass of all the resin components contained in the thermosetting resin composition of the present embodiment. -95% by mass is preferable, 60-90% by mass is more preferable, and 70-85% by mass is more preferable. By making content of a polyimide compound (A) into the said range, it exists in the tendency for a dielectric characteristic to become more favorable.

The thermosetting resin composition of the present embodiment may further contain at least one selected from the group consisting of an elastomer (B), an inorganic filler (C), and a curing accelerator (D). Moreover, it is preferable to contain. Hereinafter, these components will be described in order.
<Elastomer (B)>
The elastomer (B) is not particularly limited, and examples thereof include polybutadiene-based elastomers, styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, silicone-based elastomers, and the like. Derivatives and the like can be mentioned. One of these may be used alone, or two or more may be used in combination.

As the elastomer (B), one having a reactive functional group in the molecular terminal or in the molecular chain can be used. The reactive functional group is, for example, one or more selected from the group consisting of a maleic anhydride group, an epoxy group, a hydroxyl group, a carboxy group, an amino group, an amido group, an isocyanato group, an acrylic group, a methacrylic group and a vinyl group. It is preferably at least one selected from the group consisting of a maleic anhydride group, an epoxy group, a hydroxyl group, a carboxy group, an amino group and an amide group, from the viewpoint of adhesion to a metal foil. From the viewpoint of dielectric properties, maleic anhydride is more preferred. By having these reactive functional groups, compatibility with the resin is improved, and separation of the inorganic filler (C) and the resin component when forming the interlayer insulating layer tends to be suppressed. From the same viewpoint, the elastomer (B) is preferably an elastomer modified by maleic anhydride.

As the polybutadiene-based elastomer, one comprising a structure of a 1,4-trans body and a 1,4-cis body containing a 1,2-vinyl group is preferably mentioned.
As a polybutadiene-based elastomer, one having a reactive functional group from the viewpoint of improving the compatibility with the resin and suppressing the separation of the inorganic filler (C) and the resin component when the interlayer insulating layer is formed. In particular, polybutadiene-based elastomers which are modified with acid anhydrides are preferred. The acid anhydride is not particularly limited, and examples thereof include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, Glutaric anhydride, dimethyl glutaric anhydride, diethyl glutaric anhydride, succinic anhydride, methyl hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride and the like can be mentioned. Among these, maleic anhydride is preferred.
When the elastomer (B) is modified with an acid anhydride, the number of acid anhydride-derived groups (hereinafter also referred to as "acid anhydride group") contained in one molecule of the elastomer (B) is 1 to 10 Is preferable, 1 to 6 is more preferable, and 2 to 5 is more preferable. When the number of acid anhydride groups is 1 or more in one molecule, the separation of the inorganic filler (C) and the resin component tends to be further suppressed when the interlayer insulating layer is formed. When the number of acid anhydride groups is 10 or less in one molecule, the relative dielectric constant and the dielectric loss tangent of the thermosetting resin composition tend to be lower. When the elastomer (B) is modified with maleic anhydride, from the same viewpoint as above, a group derived from maleic anhydride contained in one molecule of the elastomer (B) (hereinafter, also referred to as "maleic anhydride group") 1 to 10 is preferable, 1 to 6 is more preferable, and 2 to 5 is more preferable.

Preferred examples of the styrene-based elastomer include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, and styrene-ethylene-propylene-styrene block copolymer. As components constituting the styrene-based elastomer, besides styrene, styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene and the like can be mentioned.

Examples of the olefin elastomer include copolymers of α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-pentene and the like, and examples thereof include ethylene-propylene co-polymers. Polymers (EPR), ethylene-propylene-diene copolymers (EPDM) and the like are preferably mentioned. Also, copolymers of the above-mentioned α-olefins and non-conjugated dienes having 2 to 20 carbon atoms such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene, isoprene and the like can be mentioned. . Furthermore, carboxy modified NBR etc. which copolymerized methacrylic acid to the butadiene-acrylonitrile copolymer etc. are mentioned.

The urethane-based elastomer preferably includes, for example, a hard segment composed of a short chain diol and a diisocyanate, and a soft segment composed of a high molecular (long chain) diol and a diisocyanate.
Examples of high molecular (long chain) diols include polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene-1,4-butylene adipate), polycaprolactone, and poly (1,6-hexane). Xylene carbonate), poly (1,6-hexylene neopentylene adipate) and the like. The number average molecular weight of the high molecular (long chain) diol is preferably 500 to 10,000.
Examples of short chain diols include ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A. The number average molecular weight of the short chain diol is preferably 48 to 500.

Examples of polyester-based elastomers include those obtained by polycondensation of a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof.
Specific examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid, and aromatic dicarboxylic acids in which the hydrogen atom of their aromatic nucleus is substituted with a methyl group, an ethyl group, a phenyl group or the like; Aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid and dodecanedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. One of these compounds may be used alone, or two or more thereof may be used in combination.
Specific examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and 1,10-decanediol; 1,4-cyclohexanediol And alicyclic diols such as bisphenol A, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) propane, and resorcin. One of these compounds may be used alone, or two or more thereof may be used in combination.

In addition, as a polyester elastomer, a multi-block copolymer having an aromatic polyester (for example, polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (for example, polytetramethylene glycol) portion as a soft segment component is preferable. It can be mentioned. Multiblock copolymers are of various grades depending on the type, ratio, and molecular weight of the hard segment and the soft segment. As a specific example, "Hytrel (registered trademark)" (made by Toray DuPont Co., Ltd.), "Perprene (registered trademark)" (made by Toyobo Co., Ltd.), "Espel (registered trademark)" (made by Hitachi Chemical Co., Ltd.) Etc.

Examples of polyamide-based elastomers include a hard segment component of polyamide, polybutadiene, butadiene-acrylonitrile copolymer, styrene-butadiene copolymer, polyisoprene, ethylene propylene copolymer, polyether, polyester, polybutadiene, polycarbonate, polyacrylate And block copolymers containing polymethacrylates, polyurethanes, silicone rubbers, etc. as soft segment components.

As an acryl-type elastomer, the polymer of the raw material monomer which has an acrylic ester as a main component is mentioned, for example. Preferred acrylic esters include ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate and the like. Further, as the crosslinking point monomer, glycidyl methacrylate, allyl glycidyl ether or the like may be copolymerized, or acrylonitrile, ethylene or the like may be copolymerized. Specifically, acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer and the like can be mentioned.

The silicone-based elastomer is an elastomer containing organopolysiloxane as a main component, and is classified into, for example, polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane.

Among these elastomers, styrene-based elastomers, polybutadiene-based elastomers, olefin-based elastomers, polyamide-based elastomers and silicone-based elastomers are preferable from the viewpoint of heat resistance and insulation reliability, and from the viewpoint of dielectric characteristics, polybutadiene-based elastomers and styrene-based elastomers Elastomers are more preferred, and polybutadiene based elastomers are even more preferred.

The weight average molecular weight (Mw) of the elastomer (B) is preferably 500 to 50,000, and more preferably 1,000 to 30,000. If the weight average molecular weight of the elastomer (B) is 500 or more, the curing properties of the thermosetting resin composition and the dielectric properties of the cured product tend to be better. When the weight average molecular weight of the elastomer (B) is 50,000 or less, the separation of the inorganic filler (C) and the resin component tends to be suppressed when the interlayer insulating layer is formed. In addition, the weight average molecular weight of an elastomer (B) can apply the measuring method of the weight average molecular weight of the polyimide compound (A) as described in an Example.

When the thermosetting resin composition contains the elastomer (B), the content thereof is preferably 1 to 70% by mass, and 5 to 50% by mass with respect to the total resin component contained in the thermosetting resin composition. More preferably, 10 to 30% by mass is more preferable. By setting the content of the elastomer (B) within the above range, the relative dielectric constant and the dielectric loss tangent are low, the handling property when formed into a film is excellent, and the inorganic filler (C) when forming the interlayer insulating layer There is a tendency that the separation between the resin and the resin component is suppressed.

<Inorganic filler (C)>
Examples of the inorganic filler (C) include, but are not limited to, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, Aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate and the like can be mentioned. These may be used alone or in combination of two or more. Among these, silica is preferable from the viewpoint of further reducing thermal expansion.

The shape of the inorganic filler (C) is not particularly limited, and may be, for example, spherical, crushed, needle-like or plate-like, but it is possible to improve the dispersibility in the thermosetting resin composition, organic solvent Improvement of dispersibility in resin varnish in which thermosetting resin composition is dissolved or dispersed, flowability improvement by viscosity reduction of resin varnish, increase suppression of surface roughness of insulating layer formed of thermosetting resin composition, etc. It is preferable that it is spherical shape from a viewpoint of these.

The volume average particle size of the inorganic filler (C) is not particularly limited, but is preferably 0.05 to 5 μm, more preferably 0.1 to 3 μm, and still more preferably 0.2 to 1 μm. If the volume average particle diameter of the inorganic filler (C) is 5 μm or less, it tends to be possible to more stably form the fine pattern when forming the circuit pattern on the interlayer insulating layer. If the volume average particle size of the inorganic filler (C) is 0.1 μm or more, the heat resistance tends to be better.
The volume average particle diameter is the particle diameter of a point corresponding to 50% of the volume when the cumulative frequency distribution curve according to particle diameter is determined with the total volume of particles as 100%, and the laser diffraction scattering method It can measure with the particle size distribution measuring apparatus etc. which were used.

In addition, in order to improve the dispersibility of the inorganic filler (C) and the adhesion between the inorganic filler (C) and the organic component in the thermosetting resin composition, a coupling agent may be used in combination, as necessary. It is also good. The coupling agent is not particularly limited, and, for example, various silane coupling agents, titanate coupling agents and the like can be used. These may be used alone or in combination of two or more. Among these, silane coupling agents are preferred. As a silane coupling agent, an aminosilane type coupling agent, an epoxysilane type coupling agent, a phenylsilane type coupling agent, an alkylsilane type coupling agent, an alkenylsilane type coupling agent, a mercaptosilane type coupling agent, etc. are mentioned. Be Among these, an aminosilane coupling agent is preferable from the viewpoint of the improvement of the dispersibility of the inorganic filler (C) and the improvement of the adhesion between the inorganic filler (C) and the organic component.
Moreover, when using a coupling agent, although the usage-amount is not specifically limited, 0.1-5 mass parts is preferable with respect to 100 mass parts of inorganic fillers (C), 0.5-3 mass parts is more preferable preferable. If it is this range, the feature by use of an inorganic filler (C) can be exhibited more effectively.
When a coupling agent is used, the addition method may be a so-called integral blend processing method in which a coupling agent is added after the inorganic filler (C) is blended in the thermosetting resin composition. From the viewpoint of expressing the characteristics of the inorganic filler (C) more effectively, the coupling agent may be surface-treated in advance with the dry type or the wet type with respect to the inorganic filler before blending.

The inorganic filler (C) is preferably used in the form of a slurry dispersed in advance in an organic solvent, from the viewpoint of enhancing the dispersibility in the thermosetting resin composition. Although there is no restriction | limiting in particular in the organic solvent used for the slurry of an inorganic filler (C), For example, the organic solvent illustrated at the manufacturing process of the polyimide compound (A) mentioned above is applicable. These may be used alone or in combination of two or more. Among these organic solvents, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone are preferable from the viewpoint of further improving the dispersibility.
The solid content concentration of the slurry of the inorganic filler (C) is not particularly limited. For example, from the viewpoint of the sedimentation and dispersibility of the inorganic filler (C), 50 to 80% by mass is preferable, and 60 to 80% by mass Is more preferable, and 60 to 75% by mass is more preferable.

When the thermosetting resin composition contains the inorganic filler (C), the content thereof can be appropriately selected depending on the properties and functions to be obtained, but is 55% by volume or more based on the solid content of the thermosetting resin composition Is preferable, 55 to 85% by volume is more preferable, 55 to 80% by volume is more preferable, and 55 to 75% by volume is particularly preferable. By making content of an inorganic filler (C) into such a range, it can have a low thermal expansion coefficient.
In addition, in this specification, the solid content contained in a thermosetting resin composition means the remainder which remove | eliminated the volatile component from the component which comprises a thermosetting resin composition.

<Hardening accelerator (D)>
By incorporating the curing accelerator (D) into the thermosetting resin composition of the present embodiment, the curability of the thermosetting resin composition is improved, and dielectric characteristics, heat resistance, elastic modulus, glass transition temperature, etc. It can be improved more.
The curing accelerator (D) is not particularly limited, but, for example, various imidazole compounds and derivatives thereof; various tertiary amine compounds; various quaternary ammonium compounds; various phosphorus compounds such as triphenylphosphine; peroxides Etc. Among these, various imidazole compounds and derivatives thereof and peroxides are preferable.
In particular, when the amine compound (a2) used for the production of the polyimide compound (A) has a carbon-carbon double bond, the curing accelerator (D) contains a peroxide, whereby the polyimide compound (A) is contained. The carbon-carbon double bond possessed by) causes radical polymerization, which is preferable because the effects of the present invention can be easily obtained. From the same viewpoint, the curing accelerator (D) preferably contains a peroxide together with various imidazole compounds and their derivatives.

As various imidazole compounds and derivatives thereof, for example, 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-1 -Methylimidazole, 1,2-diethylimidazole, 1-ethyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, 2-phenyl -4-Methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethylimidazole -Methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 2 , 4-Diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)] ethyl-s- Imidazole compounds such as triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)] ethyl-s-triazine; 1-cyanoethyl-2-phenylimidazolium trimellitate etc An addition reaction product of the imidazole compound and trimellitic acid; an addition reaction product of the imidazole compound and isocyanuric acid; the imidazo And the addition reaction product of hydrobromic acid and the like.

As a peroxide, for example, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexine, dicumyl peroxide Organic peroxides such as di (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di-t-hexyl peroxide, and t-butylcumyl peroxide Can be mentioned. The peroxide may be used alone or in combination of two or more.

When the thermosetting resin composition contains a curing accelerator (D), the content thereof can be appropriately selected depending on the properties and functions to be determined, but the content of the curing accelerator is 0. 0 to the entire resin component contained in the thermosetting resin composition. The content is more preferably 01 to 10% by mass, still more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 3% by mass. By making content of a hardening accelerator (D) into such a range, it exists in the tendency for hardenability and storage stability to become favorable.
In particular, when the curing accelerator (D) contains the peroxide, the content of the peroxide is preferably 30 to 95% by mass, more preferably 50 to 95% by mass, in the curing accelerator (D). Preferably, 60 to 90% by mass is more preferable, and 70 to 90% by mass is particularly preferable. The same applies to the case where the curing accelerator (D) contains a peroxide together with various imidazole compounds and their derivatives.

<Other ingredients>
The thermosetting resin composition of the present embodiment may, if necessary, contain additives such as a flame retardant, an antioxidant, a UV absorber, and a flow control agent.
Although it does not specifically limit as a flame retardant, For example, a chlorine system flame retardant, a bromine system flame retardant, a phosphorus system flame retardant, a metal hydrate system flame retardant etc. are mentioned. Phosphorus flame retardants and metal hydrate flame retardants are preferred from the viewpoint of environmental compatibility.
The antioxidant is not particularly limited, and examples thereof include phenol-based antioxidants such as hindered phenol-based antioxidants and styrenated phenol-based antioxidants.
The ultraviolet absorber is not particularly limited, and examples thereof include benzotriazole-based ultraviolet absorbers and the like.

[Resin film for interlayer insulation]
The resin film for interlayer insulation of this embodiment contains the thermosetting resin composition of this embodiment.
The interlayer insulating resin film of this embodiment may be provided with a support on any one of the surfaces.
Examples of the support include films of polyolefins such as polyethylene, polypropylene and polyvinyl chloride; films of polyesters such as polyethylene terephthalate (hereinafter, also referred to as "PET") and polyethylene naphthalate; various plastics such as polycarbonate film and polyimide film A film etc. are mentioned. Moreover, you may use metal foil, such as copper foil and aluminum foil, mold release paper, etc. The support and a protective film described later may be subjected to surface treatment such as matting treatment or corona treatment. In addition, the support and the protective film described later may be subjected to a release treatment with a silicone resin release agent, an alkyd resin release agent, a fluorine resin release agent, or the like.
The thickness of the support is not particularly limited, but is preferably 10 to 150 μm, and more preferably 25 to 50 μm.

Although the application of the resin film for interlayer insulation of this embodiment is not particularly limited, insulating resin sheets such as adhesive films and prepregs, circuit boards, solder resists, underfills, die bonding materials, semiconductor sealing materials, hole filling resins, parts It can be used in a wide range of applications where interlayer insulating layers such as embedded resins are required. Especially, it can be suitably used in order to form an interlayer insulation layer in manufacture of a printed wiring board.
Next, the manufacturing method of the resin film for interlayer insulation of this embodiment is demonstrated.

<Method of manufacturing resin film for interlayer insulation>
The interlayer insulating resin film of the present embodiment can be used as a first resin layer described later, and can be manufactured, for example, as follows.
When manufacturing the resin film for interlayer insulations, first, said each component is mixed and a thermosetting resin composition is manufactured. At this time, the thermosetting resin composition is preferably brought into the state of a resin varnish dissolved or dispersed in an organic solvent (hereinafter, also referred to as "varnish for resin film for interlayer insulation"). The said resin varnish is also a category of the thermosetting resin composition of this invention.
Examples of organic solvents used for the production of varnishes for resin films for interlayer insulation include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether, carbitol acetate Acetic esters such as: carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. These organic solvents may be used alone or in combination of two or more.
The blending amount of the organic solvent is preferably 10 to 50 parts by mass, and more preferably 20 to 40 parts by mass with respect to 100 parts by mass of the total mass of the varnish for resin film for interlayer insulation.

The varnish for a resin film for interlayer insulation produced in this manner is coated on the support and then dried by heating to obtain a resin film for interlayer insulation.
As a method of applying the varnish for resin films for interlayer insulation to a support body, coating apparatuses, such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, a die coater, can be used, for example. It is preferable that these coating apparatuses be appropriately selected depending on the film thickness.
The drying conditions after coating are not particularly limited and may be suitably determined in accordance with the type of solvent. For example, the drying temperature is preferably 50 to 150 ° C., and more preferably 70 to 120 ° C. The drying time can be, for example, 2 to 10 minutes.

The thickness of the resin film for interlayer insulation of the present embodiment is preferably equal to or greater than the thickness of the conductor layer of the circuit board from the viewpoint of embedding the conductor layer of the circuit board when it is disposed on the conductor layer. Specifically, since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the interlayer insulating resin film is preferably 5 to 100 μm, and is 5 to 60 μm. Is more preferable, and 10 to 60 μm is more preferable.

A protective film may be provided on the surface of the interlayer insulating resin film formed on the support, on the side opposite to the support. The thickness of the protective film is not particularly limited, and is, for example, 1 to 40 μm. By laminating the protective film, it is possible to prevent adhesion and scratching of dust and the like on the surface of the interlayer insulating resin film. The interlayer insulating resin film can be wound and stored in a roll.

Composite film
A composite film can be formed using the thermosetting resin composition of the present embodiment. The composite film of the present embodiment is a composite film including a first resin layer containing the thermosetting resin composition of the present embodiment and a second resin layer. The composite film of the present embodiment is useful as a composite film for an electronic device using a signal in a high frequency band.

For example, in the case of producing a printed wiring board using the composite film of the present embodiment, the first resin layer is provided between the circuit board and the adhesion auxiliary layer, and the conductor layer of the circuit board and the layer thereon And are used to insulate. In addition, when the through hole, the via hole and the like exist in the circuit board, the first resin layer also plays a role of flowing into them and filling the inside of the hole.

The second resin layer is provided between the first resin layer and the conductor layer in the printed wiring board of the present embodiment described later, and is provided for the purpose of improving the adhesion to the conductor layer. is there. By providing the second resin layer, a smooth surface can be obtained, and a better adhesion strength with the conductor layer formed by plating can be obtained.
The component of the second resin layer is not particularly limited as long as it improves adhesion to the conductor layer, but it is preferable that the first resin layer and the first resin layer do not become the same. For example, from the viewpoint of obtaining an interlayer insulating layer having excellent adhesion to plated copper and excellent dielectric properties even if the surface roughness is small, a polyfunctional epoxy resin (b1), and a phenolic hydroxyl group-containing polybutadiene-modified polyamide resin ( A thermosetting resin composition containing b2) is preferably mentioned. The component of the second resin layer is more preferably a thermosetting resin composition further containing an active ester curing agent (b3) in addition to the components (b1) and (b2). For details of the components (b1) to (b3), the description of the second resin layer described in WO 2016/11404 can be referred to, and the second resin layer described in the document is adopted as it is. May be

The composite film of the present embodiment has the first resin layer and the second resin layer, and a support is provided on the surface of the second resin layer opposite to the first resin layer. Good. In this case, the structure is: first resin layer / second resin layer / support. Examples of the support include films of polyolefins such as polyethylene, polypropylene and polyvinyl chloride; films of polyesters such as polyethylene terephthalate (hereinafter, also referred to as "PET") and polyethylene naphthalate; various plastics such as polycarbonate film and polyimide film A film etc. are mentioned. Moreover, you may use metal foil, such as copper foil and aluminum foil, mold release paper, etc. The support and a protective film described later may be subjected to surface treatment such as matting treatment or corona treatment. In addition, the support may be subjected to release treatment with a silicone resin release agent, an alkyd resin release agent, a fluorine resin release agent, or the like.
The thickness of the support is not particularly limited, but is preferably 10 to 150 μm, and more preferably 25 to 50 μm.

The composite film of the present embodiment may be provided with a protective film. For example, the aspect which provides a protective film in the surface on the opposite side to a 2nd resin layer in a 1st resin layer is mentioned. In this case, for example, the structure is as follows: protective film / first resin layer / second resin layer, protective film / first resin layer / second resin layer / support, and the like.
As a protective film, plastic films, such as a polytetrafluoroethylene film, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polymethyl pentene film, a polyimide film, etc. are mentioned, for example. In addition, the protective film may be subjected to surface treatment such as primer coating, UV treatment, corona discharge treatment, polishing treatment, etching treatment, release treatment, and the like, as necessary.
In addition, you may use the said support body as a protective film.

In the composite film of the present embodiment, for example, a second resin layer is formed on the support, and a first resin layer is formed on the second resin layer. It can manufacture by the method of forming a protective layer on a resin layer. For forming the second resin layer, the varnish for the second resin layer to be described later is applied to the support and then dried by heating, and further, the varnish for the first resin layer to be described later is applied thereon It can be formed by heating and drying. As a method of coating a resin varnish, coating apparatuses, such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, a die coater, can be used, for example. It is preferable that these coating apparatuses be appropriately selected depending on the film thickness.
The drying conditions after coating are not particularly limited, and may be appropriately determined according to the type of solvent. For example, when forming the first resin layer, the drying temperature is preferably 50 to 130 ° C., and more preferably 70 to 110 ° C. The drying time can be, for example, 1 to 10 minutes when forming the first resin layer. For example, when forming the second resin layer, the drying temperature is preferably 50 to 150 ° C., and more preferably 100 to 145 ° C. The drying time can be, for example, 1 to 10 minutes when forming the second resin layer.
In the above drying, the content of the volatile component (mainly organic solvent) in the first resin layer or the second resin layer after drying is preferably 10% by mass or less, preferably 6% It is more preferable to dry so that it becomes% or less.

The composite film of the present embodiment can also be produced by preparing a film of the first resin layer and a film of the second resin layer, respectively, and bonding them by thermocompression bonding or a laminator at a temperature higher than the softening temperature.

In the composite film of the present embodiment, in order to embed the unevenness height c of the circuit, the thickness of the first resin layer is preferably 1c to 3c, more preferably 1c to 2c, and 1.1c More preferably, it is -1.5c. When the thickness of the first resin layer is 1 c or more, sufficient embeddability can be secured when embedding the unevenness of the circuit, and the surface layer of the composite film after embedding tends to be kept flat. On the other hand, if it is 3 c or less, thinning of the substrate is facilitated and warpage tends to be reduced, which is preferable.
Specifically, in order to embed the uneven height of the circuit, the thickness of the first resin layer is preferably 5 to 60 μm, for example. The thickness of the first resin layer is more preferably 7 to 50 μm, further preferably 10 to 40 μm.

On the other hand, the second resin layer is a layer adaptable to the semi-additive method. The thickness of the second resin layer is preferably 1 to 10 μm, more preferably 1 to 7 μm, and 1 to 5 μm in order to ensure surface flatness and high adhesion to plated copper. It is more preferable that If the thickness of the second resin layer is 1 μm or more, it is easy to avoid that the second resin layer is broken and the first resin layer is exposed to the surface at the time of embedding in the unevenness of the circuit, and desmear There is little risk of the second resin layer eluting and disappearing in the process. On the other hand, if it is 10 micrometers or less, while it is easy to suppress the fall of surface flatness and a substrate can be made thin, it is preferable.

Assuming that the thickness of the first resin layer is a (μm), the thickness of the second resin layer is b (μm), and the height of the circuit is c (μm), c ≦ a ≦ 3c, c ≦ a ≦ It is preferable to set it as the composite film which satisfy | fills the relationship of 2c, or c <= a <= 1.5c, 1 <= b <= 10, or 1 <= b <= 5. If the film satisfies this relationship, it is possible to simultaneously achieve sufficient embedding and fine circuit formation.

The first resin layer preferably has a minimum melt viscosity at 80 to 150 ° C. of 100 to 4,000 Pa · s. Within this range, the first resin layer can be made to flow at 80 to 150 ° C., which is preferable from the viewpoint of embeddability. Here, the minimum melt viscosity is the viscosity when the thermosetting resin composition is melted before the start of curing.
When the minimum melt viscosity at 80 to 150 ° C. is 100 Pa · s or more, the flowability of the film does not become too large, the surface flatness of the composite film after embedding becomes easy to be maintained, and the thickness of the substrate varies. Tend to be able to Moreover, by being 4,000 Pa · s or less, the fluidity becomes good, and it tends to be easy to embed the unevenness of the wiring.

On the other hand, the second resin layer has a minimum melt viscosity at 80 to 150 ° C. of 50,000 Pa · s or more. The second resin layer makes it easy to maintain the surface flatness of the composite film after embedding, while the second resin layer maintains a certain thickness when embedding the composite film in a circuit. From the same viewpoint, the minimum melt viscosity at 80 to 150 ° C. of the second resin layer is preferably 50,000 to 100,000 Pa · s, and more preferably 50,000 to 75,000 Pa · s. preferable.

The composite film of the present embodiment can be cured by heat or active energy rays. Examples of the active energy ray include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays and X-rays; and particle rays such as α-rays, γ-rays and electron beams. Among these, ultraviolet light is preferred.

An example of the composite film of this embodiment is shown in FIG. 1 as a schematic cross-sectional view. The composite film which concerns on this embodiment is equipped with the 1st resin layer 1 and the 2nd resin layer 2, and the support body 3 and / or the protective film 4 as needed.
There is no clear interface between the first resin layer 1 and the second resin layer 2. For example, part of the components of the first resin layer 1 and the second resin layer Some of the two components may be in a state of being compatible and / or mixed.

[Printed wiring board and its manufacturing method]
The printed wiring board of the present embodiment contains a cured product of the interlayer insulating resin film or a cured product of the composite film. In other words, the printed wiring board (multilayer printed wiring board) of the present embodiment has an interlayer insulating layer, and at least one of the interlayer insulating layers contains the thermosetting resin composition of the present embodiment.
Below, the composite film of this embodiment is laminated to a circuit board, and the method to manufacture a printed wiring board is demonstrated.

The method for manufacturing a printed wiring board of the present embodiment includes the following step (1). More specifically, the method for manufacturing a printed wiring board of the present embodiment includes the following steps (1) to (5), and after the step (1), the step (2) or the step (3), The support may be peeled off or removed.
Step (1): Step of laminating the composite film of the present embodiment on one side or both sides of the circuit board Step (2): Step of curing the composite film to form an interlayer insulating layer Step (3): interlayer insulating layer Step of drilling holes in the formed circuit board Step (4): Step of roughening the surface of the interlayer insulating layer Step (5): step of plating the surface of the roughened interlayer insulating layer

<Step (1)>
Step (1) is a step of laminating the composite film of the present embodiment on one side or both sides of the circuit board. As an apparatus which laminates a composite film, vacuum laminators, such as a vacuum applicator made from Nikko Materials, Inc., are mentioned, for example.

In the laminate, when the composite film has a protective film, after removing the protective film, the composite film is crimped to the circuit board while pressing and / or heating.
When using a composite film, it arrange | positions so that a 1st resin layer may face the surface in which the circuit of the circuit board is formed.
Laminating conditions include preheating the composite film and the circuit board as required, a pressure bonding temperature (lamination temperature) of 60 to 140 ° C., and a pressure bonding pressure of 0.1 to 1.1 MPa (9.8 × 10 ⁴ to 107 .9 × 10 ⁴ N / m ² ), air pressure 20 mmHg (26.7 hPa) or less may be laminated under reduced pressure. Also, the method of lamination may be a batch system or a continuous system with a roll.
The substrate usually has a step due to a circuit or component, but after the composite film of the present embodiment is laminated to the substrate, the step can be sufficiently filled with the first resin layer of the composite film. The lamination temperature is preferably 70 to 130.degree. C. from the viewpoint of sufficient degree of filling.

<Step (2)>
The step (2) is a step of curing the composite film to form an interlayer insulating layer. Curing may be heat curing or curing by active energy rays. The conditions of the heat curing are not particularly limited, but can be selected, for example, in the range of 20 to 80 minutes at 170 to 220 ° C. The active energy ray is as described above.
In addition, after curing, the support may be peeled off.

<Step (3)>
The step (3) is a step of forming a hole in the circuit board on which the interlayer insulating layer is formed. In this step, holes are formed in the interlayer insulating layer and the circuit board by a method such as drilling, laser, plasma, or a combination thereof to form via holes, through holes, and the like. As a laser, a carbon dioxide gas laser, a YAG laser, a UV laser, an excimer laser or the like is generally used.

<Step (4)>
The step (4) is a step of roughening the surface of the interlayer insulating layer. In this step, when the surface of the interlayer insulating layer formed in step (2) is roughened with an oxidizing agent and at the same time a via hole, a through hole, etc. are formed, they occur when these are formed. Removal of "smear" can also be performed.
The oxidizing agent is not particularly limited, and examples thereof include permanganate (potassium permanganate, sodium permanganate), dichromate, ozone, hydrogen peroxide, sulfuric acid, nitric acid and the like. Among these, alkaline permanganate solution (for example, potassium permanganate, sodium permanganate solution), which is an oxidizing agent generally used for roughening an interlayer insulating layer in manufacturing a multilayer printed wiring board by a build-up method Roughening and smear removal may be performed.

<Step (5)>
Step (5) is a step of plating the surface of the roughened interlayer insulating layer. The second resin layer of the composite film is a layer adaptable to the semi-additive process. Therefore, in this process, a feed layer is formed on the surface of the interlayer insulating layer by electroless plating, and then a plating resist having a pattern reverse to that of the conductor layer is formed, and a conductor layer (circuit) is formed by electrolytic plating. Additive methods can be used.
After forming the conductor layer, annealing treatment may be performed at 150 to 200 ° C. for 20 to 120 minutes, for example, to improve and stabilize the adhesive strength between the interlayer insulating layer and the conductor layer.

Furthermore, it may have the process of roughening the surface of the conductor layer produced in this way. Roughening of the surface of the conductor layer has the effect of enhancing the adhesion to the resin in contact with the conductor layer. The treating agent for roughening the conductor layer is not particularly limited, and, for example, MEC etch bond CZ-8100, MEC etch bond CZ-8101, MEC etch bond CZ-5480 (organic acid microetching agents) Mec Co., Ltd., trade name), and the like.

Among the above manufacturing methods, the following method for manufacturing a printed wiring board can be mentioned as an example of a preferable embodiment.
Bonding the first resin layer side of the composite film to a substrate having a step due to a circuit or a component on the surface using the composite film, and filling the step;
Curing the first resin layer and the second resin layer of the composite film,
Forming a circuit by a semi-additive method on the surface on the second resin layer side of the composite film;
A method of manufacturing a printed wiring board, comprising:

The composite film and printed wiring board of the present embodiment can be particularly suitably used for electronic devices that handle high frequency signals of 1 GHz or more, and in particular, handle high frequency signals of 5 GHz or more, high frequency signals of 10 GHz or more, or high frequency signals of 30 GHz or more. It can be suitably used for electronic devices. That is, the composite film of the present embodiment is useful as a composite film for an electronic device using a signal in a high frequency band.

[Semiconductor package]
The present invention also provides a semiconductor package comprising the printed wiring board, more specifically, a semiconductor package comprising a semiconductor element mounted on the printed wiring board. The semiconductor package of the present embodiment can be manufactured by mounting a semiconductor element such as a semiconductor chip or a memory at a predetermined position of the printed wiring board and sealing the semiconductor element with a sealing resin or the like.

The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, which has substantially the same configuration as the technical idea described in the claims of the present invention, and exhibits the same function and effect as that of the present invention. It is included in the technical scope.

EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

Production Examples 1 to 4 (Production of Polyimide Compounds (A-1) to (A-4))
A 2-liter [4- (4-maleimidophenoxy) phenyl] propane (manufactured by Yamato Kasei Kogyo Co., Ltd.) in a 1-liter glass flask container capable of heating and cooling and equipped with a thermometer, a reflux condenser, and a stirrer. Product name: BMI-4000), 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bisaniline (manufactured by Mitsui Chemicals Fine Inc., trade name: Bisaniline M) 70 parts by mass, diallylamine (Tokyo) Chemical conversion industrial Co., Ltd.) and propylene glycol monomethyl ether are added in the amounts listed in Table 1 below (unit: parts by mass unless otherwise specified. However, the unit of the numerical value in parentheses is mmol). The mixture was reacted at a liquid temperature of 120 ° C. for 3 hours while refluxing.
Thereafter, the resultant was cooled and subjected to 200 mesh filtration to produce polyimide compounds (A-1) to (A-4) (solid content concentration: 65% by mass) having a weight average molecular weight (Mw) of 1,200.

Comparative Production Example 1 (Production of Polyimide Compound (A'-5))
A reaction was carried out in the same manner as in Production Example 1 except that the amount of each component used was changed as described in Table 1, and a polyimide compound (A'-5) having a weight average molecular weight (Mw) of 1,200 was obtained. Manufactured.

<Method of measuring weight average molecular weight>
The weight average molecular weight of the obtained polyimide compound (A) was converted from the calibration curve using standard polystyrene by gel permeation chromatography (GPC). Standard curve: Standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) (manufactured by Tosoh Corporation) It is approximated by a cubic expression using a trade name]]. The conditions of GPC are shown below.
Device: Pump: L-6200 (manufactured by Hitachi High-Technologies Corporation)
Detector: L-3300 RI [manufactured by Hitachi High-Technologies Corporation]
Column oven: L-655A-52 [made by Hitachi High-Technologies Corporation]
Column: Guard column; TSK Guardcolumn HHR-L + column; TSK gel-G4000 HHR + TSK gel-G 2000 HHR (all manufactured by Tosoh Corporation, trade name)
Column size: 6.0 x 40 mm (guard column), 7.8 x 300 mm (column)
Eluent: Tetrahydrofuran Sample concentration: 30 mg / 5 mL
Injection volume: 20 μL
Flow rate: 1.00 mL / min Measurement temperature: 40 ° C

<Method for producing thermosetting resin composition (resin varnish) and resin film for interlayer insulation>
Example 1 (Manufacture of resin varnish 1 and resin film 1 for interlayer insulation)
20% by mass of a polybutadiene-based elastomer (trade name: POLYVEST 75 MA, manufactured by Evonik Co., Ltd.) as the elastomer (B) (that is, based on all resin components, that is, all components including no inorganic filler and organic solvent) 65% by volume (relative to the total volume not containing an organic solvent) of an silica treated with aminosilane coupling agent as an inorganic filler (C) (Admatex Co., Ltd., dispersion of 70% by mass methyl isobutyl ketone dispersion) Mixed with
A ratio in which the content of the polyimide compound (A-1) obtained in Production Example 1 is 80% by mass with respect to the total resin component contained in the thermosetting resin composition. And allowed to dissolve at room temperature with a high speed rotary mixer.
After visually confirming that the polyimide compound (A-1) was dissolved, an organic peroxide (manufactured by NOF Corporation, trade name: Perbutyl P) was used as a curing accelerator, as a polyimide compound (A-1). The raw material (maleimide compound) and the elastomer (B), which are converted from the preparation amount, 1.0 phr, isocyanate mask imidazole (Daiichi Kogyo Seiyaku Co., Ltd., trade name: G8009 L), a polyimide compound (A-1) It mixed with 0.5 phr with respect to the maleimide compound of the raw material converted from preparation amount. Then, they were dispersed by nanomizer treatment to obtain a resin varnish 1.
The obtained resin varnish 1 is coated on a release-treated support (PET film) using a comma coater so that the thickness of the layer after drying is 40 μm, and dried at 90 ° C. for 3 minutes. Then, a first resin layer was formed on the support to obtain an interlayer insulating resin film.
Furthermore, it wound up in roll shape, bonding a 15-micrometer-thick polypropylene film as a protective film on the surface of this 1st resin layer, and obtained the resin film 1 for interlayer insulation which has a support body and a protective film.
Each characteristic was measured or evaluated according to the method described later using the interlayer insulating resin film. The results are shown in Table 2.

Examples 2 to 4 (Production of resin varnishes 2 to 4 and resin films 2 to 4 for interlayer insulation)
The same as Example 1, except that the polyimide compounds (A-2) to (A-4) obtained in Production Examples 2 to 4 were used instead of the polyimide compound (A-1) obtained in Production Example 1 The resin varnishes 2 to 4 were obtained, and further, resin films 2 to 4 for interlayer insulation were obtained.
Each characteristic was measured or evaluated according to the method described later using the obtained resin films 2 to 4 for interlayer insulation. The results are shown in Table 2.

Comparative Example 1 (Production of Resin Varnish 5 for Comparison and Resin Film 5 for Interlayer Insulation)
The same procedure as in Example 1 was repeated except that the polyimide compound (A'-5) obtained in Comparative Production Example 1 was used instead of the polyimide compound (A-1) obtained in Production Example 1. The resin varnish 5 was obtained, and further, the interlayer insulating resin film 5 was obtained.
Each characteristic was measured or evaluated according to the method of the below-mentioned using resin film 5 for interlayer insulation obtained. The results are shown in Table 2.

The resin board was produced according to the following method for measurement or evaluation of a characteristic.
(I) After peeling a protective film from the resin film for interlayer insulation which has a support body and a protective film obtained in each case, it dried at 120 degreeC for 5 minutes.
Next, using a vacuum pressure type laminator (trade name: MVLP-500 / 600-II, manufactured by Meieki Co., Ltd.), a resin film for interlayer insulation having a support after drying is used as a copper foil (electric field copper foil) On a shiny surface of 35 μm in thickness so that the resin layer of the interlayer insulating resin film and the copper foil are in contact with each other, and the copper foil, the interlayer insulating resin film and the support are laminated in this order I got the body (P). The lamination was performed by reducing the pressure for 30 seconds to 0.5 MPa and then pressing at 120 ° C. for 30 seconds with a pressure bonding pressure of 0.5 MPa. Thereafter, the support was peeled off from the laminate (P).
(II) Next, another resin film for interlayer insulation having a PET film as a support and a polypropylene film as a protective film was prepared, and after peeling off the protective film, drying was performed at 120 ° C. for 5 minutes.
(III) Next, a laminate (P) obtained by peeling the support obtained in the above (I), and a resin film for interlayer insulation having the dried support obtained in the above (II), Lamination is performed under the same conditions as in the above (I) so that the layers are in contact with each other to obtain a laminate (Q) in which a copper foil, a layer consisting of two resin films for interlayer insulation, and a support are laminated in this order. The Thereafter, the support was peeled off from the laminate (Q).
(IV) Next, an interlayer insulating resin film having a laminate (Q) obtained by peeling the support obtained in the above (III) and a support after drying obtained by the same method as the above (II) Such that the resin layers are in contact with each other under the same conditions as in (I) above, and a laminate comprising a copper foil, a layer consisting of three resin films for interlayer insulation, and a support laminated in this order ( R) got.
(V) A laminate (Q) was produced by the same method as in (I) to (III).
(VI) The laminate (Q) obtained in the above (V) and the support of the laminate (R) obtained in the above (IV) are respectively peeled off, and the laminate (Q) and the laminate (R) The resin layers of the above were bonded to each other, and press molding was performed using a vacuum press at 190 ° C. for 60 minutes under a pressure bonding pressure of 10.0 MPa. After curing the obtained resin plate with double-sided copper foil at 190 ° C. for 2 hours, the copper foil was etched with ammonium persulfate to obtain a resin plate.

[1. Measuring method of dielectric constant and dielectric loss tangent-high frequency characteristics]
The resin plate prepared above is cut into a test piece of 2 mm in width and 70 mm in length, and a network analyzer (manufactured by Agilent Technologies, Inc., trade name: E8364B) and a cavity resonator for 5 GHz (manufactured by Kanto Electronics Application Development Co., Ltd.) The relative dielectric constant and the dielectric loss tangent were measured. The measurement temperature was 25 ° C. The lower the relative dielectric constant and the dielectric loss tangent obtained according to the measurement method, the better the high frequency characteristics.

[2. Method of measuring thermal expansion coefficient and glass transition temperature]
The resin plate produced above was cut into a test piece having a width of 4 mm and a length of 15 mm, and the coefficient of thermal expansion was measured using a thermal stress strain measuring device (manufactured by Seiko Instruments Inc., model: TMA / SS6100). The coefficient of thermal expansion is heated from room temperature to 260 ° C. (1st) at a heating rate of 10 ° C./min under a load of 0.05 N, then cooled to 260 ° C. to -30 ° C., and then -30 ° C. to 300 ° C. Values of average thermal expansion coefficient (ppm / ° C) in the range of 30 ° C to 120 ° C of 2nd and values of average thermal expansion coefficient (ppm / ° C) in the range of 250 ° C to 300 ° C when heated up to 2nd Was determined as the coefficient of thermal expansion. Also, the inflection point of the amount of expansion was determined as the glass transition temperature.

[3. Method of measuring storage modulus]
The resin plate prepared above is cut into a test piece with a width of 5 mm and a length of 30 mm, and the storage elastic modulus (E ') is measured using a wide area dynamic viscoelasticity measuring device (manufactured by Rheology Co., Ltd., trade name: DVE-V4) did. The measurement temperature range was 40 to 300 ° C., the temperature rise rate was 5 ° C./min, the excitation frequency was 10 Hz, and the storage elastic modulus (E ′) at 40 ° C. was determined. When the storage elastic modulus (E ′) is high, warpage of the substrate at the time of mounting can be reduced.

The following is a test method for the interlayer insulating resin film.
[4. Evaluation method of embeddability]
The protective film of the resin film for interlayer insulation obtained in Example 4 or Comparative Example 1 was peeled off and overlapped so as to be 1.0 mm, and the melt viscosity was measured using a sample punched to φ 8 mm. The viscosity was measured using a rheometer (trade name: ARESG2, manufactured by TA Instruments Japan Co., Ltd.) at a temperature rising rate of 5 ° C./min, a φ 8 mm jig, a frequency of 1.0 Hz, and a strain of 1%. When the melt viscosity is low, the embeddability is excellent. The temperature-melt viscosity curve obtained by the measurement is shown in FIG.

[5. Bending test]
The protective film of the resin film for interlayer insulation obtained in each example was peeled off, and the resin film for interlayer insulation having a support was bent 180 degrees so that the resin surface was on the outside. Thereafter, the state of the film resin surface was visually observed and evaluated according to the following evaluation criteria.
A: There was no abnormality in the resin surface.
B: A slight crack was observed on the resin surface.
C: The resin surface was cracked and peeled off from the support.

[6. Peeling test of protective film]
Peeling of the protective film was attempted from the resin film for interlayer insulation having the support and the protective film obtained in each example. The state of the interlayer insulating resin film was visually observed and evaluated according to the following evaluation criteria.
A: There was no abnormality in the interlayer insulating resin film.
B: A part of the resin film for interlayer insulation did not peel from the protective film, but peeled from the support.
C: The protective film could not be peeled off.

[7. Method of measuring surface roughness]
<Method of producing substrate for measuring surface roughness>
A substrate for measuring surface roughness was produced by the following procedure.
The interlayer insulating resin film having the support and the protective film obtained in each example was cut into a size of 240 mm × 240 mm, and then the protective film was peeled off.
The resin film for interlayer insulation having the obtained support was treated with a first resin layer and a printed wiring board on a printed wiring board (manufactured by Hitachi Chemical Co., Ltd., trade name: E-700GR) subjected to CZ treatment. Laminated so as to abut. Lamination was performed by a method of vacuuming at 100 ° C. for 30 seconds in a first step, pressing for 30 seconds under pressure, and pressure 0.5 MPa, and flattening in a second step 120 ° C. for 60 seconds at a pressure 0.5 MPa.
Then, it cooled to room temperature and obtained the printed wiring board which distribute | arranged the resin film for interlayer insulation. Next, the printed wiring board on which the interlayer insulating resin film is disposed is cured in an explosion-proof dryer at 130 ° C. for 20 minutes as the first stage curing with the support attached, and then the second stage Curing was performed in an explosion-proof dryer at 190 ° C. for 40 minutes as curing of the eyes. Thereafter, the support was peeled off to obtain a printed wiring board on which an interlayer insulating layer was formed.

(Roughening treatment method)
Swelling solution (made by Atotech Japan Co., Ltd., trade name: SWELLING DEP Securityant (registered trademark) P) in which the printed wiring board obtained by the method for producing a substrate for measuring surface roughness described above was heated to 60 ° C. Soaked for a minute. Next, it was subjected to immersion treatment for 15 minutes in a roughening solution (manufactured by Atotech Japan Co., Ltd., trade name: Consulate Compact CP) heated to 80 ° C. Subsequently, it was neutralized by soaking for 5 minutes in a neutralization solution (manufactured by Atotech Japan Co., Ltd., trade name: Reduction Solution Security Gant (registered trademark) P500) heated to 40 ° C. In this manner, the surface of the interlayer insulating layer which was roughened was used as a substrate for measuring surface roughness.

The surface roughness of the substrate for surface roughness measurement obtained above was measured using a non-contact surface roughness tester (manufactured by Bruker AXS Co., Ltd., trade name: WykoNT 9100), 1 × internal lens, 50 × external lens To determine the arithmetic mean roughness (Ra).

The details of each component in Table 2 are as follows.
A-1: Polyimide compound produced in Production Example 1 (A-1)
A-2: Polyimide compound produced in Production Example 2 (A-2)
A-3: Polyimide compound produced in Production Example 3 (A-3)
A-4: Polyimide compound produced in Production Example 4 (A-4)
A'-5: Polyimide compound produced in Comparative Preparation Example 1 (A'-5)
・ POLYVEST (registered trademark) 75MA: Polybutadiene based elastomer (manufactured by Evonik Co., Ltd.)
Inorganic filler (C): silica (Admatex Co., Ltd., dispersion of methyl isobutyl ketone having a solid content concentration of 70% by mass)
Perbutyl P: α, α′-bis (t-butylperoxy) diisopropylbenzene (manufactured by NOF Corporation)
G8009L: isocyanate mask imidazole (made by Daiichi Kogyo Seiyaku Co., Ltd.)

From Table 2, it is a high glass transition temperature in the Example using the thermosetting resin composition containing a polyimide compound (A), It is excellent in the embeddability with respect to unevenness | corrugation, such as a circuit, and excellent dielectric property and low thermal expansion And the handling property is also good.
On the other hand, in the comparative example, the thermal expansion coefficient in the range of 250 to 300 ° C. increased, the storage elastic modulus decreased, the bending test result was not excellent, and the surface roughness increased.

INDUSTRIAL APPLICABILITY The composite film and printed wiring board of the present invention are useful for vehicles such as computers, mobile phones, digital cameras, electric appliances such as digital cameras, televisions, motorcycles, automobiles, trains, ships, and aircraft.

1 first resin layer 2 second resin layer 3 support 4 protective film

Claims

It contains a polyimide compound (A) having a structural unit derived from a maleimide compound (a1) having at least two N-substituted maleimide groups and a structural unit derived from an amine compound (a2) having a total of 3 to 13 carbon atoms. Thermosetting resin composition.
The thermosetting resin composition according to claim 1, wherein the amine compound (a2) is liquid at normal temperature.
The thermosetting resin composition according to claim 1 or 2, wherein the amine compound (a2) is an aliphatic amine.
The thermosetting resin composition according to claim 3, wherein the aliphatic amine is at least one selected from the group consisting of aliphatic monoamines, aliphatic diamines and alicyclic diamines.
Total equivalent of maleimide group-derived group (including maleimide group) derived from maleimide compound (a1) relative to the total equivalent (Ta2) of amino group-derived groups of the amine compound (a2) in the polyimide compound (A) The thermosetting resin composition according to any one of claims 1 to 4, wherein the equivalent ratio [Ta1 / Ta2] to (Ta1) is 1.0 to 50.
The thermosetting resin composition according to any one of claims 1 to 5, wherein the polyimide compound (A) further has a structural unit derived from a polyamine compound (a3).
The total equivalent (Ta3) of the total equivalent (Ta2) of the amino group-derived group of the amine compound (a2) and the amino group-derived group (including the amino group) of the polyamine compound (a3) in the polyimide compound (A) The equivalent ratio [Ta1 / (Ta2 + Ta3)] to the total equivalent (Ta1) of the group derived from the maleimide group (including the maleimide group) derived from the maleimide compound (a1) relative to the total amount of The thermosetting resin composition according to claim 6.
Ratio [Ma2] of the total number of moles of the group derived from the amino group of the amine compound (a2) (Ma2) and the total number of moles of the group derived from the amino group of the polyamine compound (a3) (including the amino group) (Ma3) The thermosetting resin composition according to claim 6 or 7, wherein / Ma3] is 0.01 to 10.
The thermosetting resin according to any one of claims 1 to 8, further comprising at least one selected from the group consisting of an elastomer (B), an inorganic filler (C) and a curing accelerator (D). Resin composition.
The thermosetting resin composition according to claim 9, wherein the curing accelerator (D) contains a peroxide.
An interlayer insulating resin film comprising the thermosetting resin composition according to any one of claims 1 to 10.
A composite film comprising a first resin layer comprising the thermosetting resin composition according to any one of claims 1 to 10, and a second resin layer.
A printed wiring board comprising the cured product of the interlayer insulating resin film according to claim 11 or the cured product of the composite film according to claim 12.
A semiconductor package comprising the printed wiring board according to claim 13.