JPWO2019146105A1 - Thermosetting resin composition, resin film for interlayer insulation, composite film, printed wiring board and semiconductor package - Google Patents

Abstract

As a thermosetting resin composition that can be used as a composite film for electronic devices that uses signals in the high frequency band, it has a high glass transition temperature, excellent embedding property in irregularities such as circuits, excellent dielectric properties and low thermal expansion. (That is, it has flexibility when the thermosetting resin composition is B-staged, and at the same time, cracks are unlikely to occur even if it is bent when it is made into a film, and it is peeled off from the cover film. To provide a thermosetting resin composition that can easily be used, and to provide a resin film for interlayer insulation, a composite film, a printed wiring board, and a semiconductor package using the thermosetting resin composition. More specifically, the thermosetting resin composition is derived from a structural unit derived from a maleimide compound (a1) having at least two N-substituted maleimide groups and an amine compound (a2) having a carbon-carbon double bond. It is a thermosetting resin composition containing a polyimide compound (A) having the structural unit of.

Description

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

In recent years, electronic devices have become smaller, lighter, more multifunctional, etc., and along with this, LSI (Large Scale Integration), chip parts, etc. have become more integrated, and their forms have also become multi-pin and miniaturized. Is changing rapidly. Therefore, in order to improve the mounting density of electronic components, the development of fine wiring of multilayer printed wiring boards is underway. As a multilayer printed wiring board that meets these requirements, a multilayer printed wiring board with a build-up structure that uses an insulating resin film that does not contain glass cloth as an insulating layer (hereinafter, also referred to as “build-up 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 build-up layer, it is required to have good handleability, that is, to have flexibility when the thermosetting resin composition is B-staged, and at the same time, when it is made into a film. Properties such as less cracking even when bent and easy peeling from the cover film (generally referred to as handleability) are also required. In order to obtain a film having good handleability, a thermosetting resin composition containing a liquid epoxy resin has been conventionally used as a film material (see, for example, Patent Document 1). However, a film obtained from a thermosetting resin composition containing a liquid epoxy resin usually has a problem of having a large dielectric loss tangent.
On the other hand, as a film material capable of obtaining a low dielectric positive contact, 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) is used. The thermosetting resin composition contained is known (see, for example, Patent Document 2).

Japanese Patent No. 5504553 International Publication No. 2016/11430

However, since the polyimide compound is generally rigid, it is not easy to improve the handleability. In this respect, Patent Document 2 conducts a bending test as an evaluation of the handleability of the film, and has succeeded in obtaining a film having good handleability from this viewpoint. However, as described above, the thermosetting resin composition has flexibility when it is B-staged, and it is easily peeled off from the cover film when it is made into a film (the tackiness is not too strong, and the handling property is not so high. The property of (good) is also industrially important. That is, the handleability is good from the viewpoints of having flexibility when the thermosetting resin composition is B-staged, being less likely to crack during bending, and being easily peeled off from the protective film. desired.
Further, the build-up layer is required to have a high glass transition temperature (Tg) from the viewpoint of reliability, and to have embedding property in irregularities of circuits and the like (hereinafter, may be simply referred to as "embedding property"). To. Further, low thermal expansion is also required in order to improve the processing dimensional stability and reduce the amount of warpage after mounting the semiconductor.
Under such circumstances, computers and information and communication devices have become more sophisticated and sophisticated in recent years, and in order to process a large amount of data at high speed, the signals to be handled tend to have higher frequencies. In particular, the frequency range of radio waves used for mobile phones and satellite broadcasting is in the high frequency range of the GHz band, and in order to suppress transmission loss due to high frequency, the relative permittivity is used as an organic material used in the high frequency range. And a material having a low dielectric loss tangent is desired.

Therefore, the subject of the present invention is that the thermosetting resin composition that can be used as a composite film for electronic devices that uses signals in the high frequency band has a high glass transition temperature and is excellent in embedding property in irregularities of circuits and the like. It has both dielectric properties and low thermal expansion, and also has good handleability (that is, it has flexibility when the thermosetting resin composition is B-staged, and at the same time, cracks occur even when bent as a film. To provide a thermosetting resin composition that is unlikely to occur and easily peels off from the cover film), and a resin film for interlayer insulation, a composite film, a printed wiring board, and a semiconductor package using the thermosetting resin composition. Is to provide.

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

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 carbon-carbon double bond. A thermosetting resin composition containing.
[2] The thermosetting resin composition according to the above [1], wherein the amine compound (a2) has two or more carbon-carbon double bonds.
[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 the above [3], wherein the aliphatic amine is at least one selected from the group consisting of an aliphatic monoamine and an alicyclic diamine.
[5] A maleimide group-derived group (including a maleimide group) derived from the maleimide compound (a1) with respect to the total equivalent (Ta2) of the amino group-derived groups 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 the equivalent ratio [Ta1 / Ta2] with the total equivalent (Ta1) of the above is 1.0 to 30.
[6] The thermosetting resin composition according to any one of [1] to [5] above, wherein the polyimide compound (A) further has a structural unit derived from the polyamine compound (a3).
[7] In the polyimide compound (A), the total equivalent of the amino group-derived groups (Ta2) of the amine compound (a2) and the amino group-derived groups (including amino groups) of the polyamine compound (a3). The equivalent ratio [Ta1 / (Ta2 + Ta3)] to the total equivalent (Ta1) of the maleimide group-derived group (including the maleimide group) derived from the maleimide compound (a1) to the total amount with the equivalent (Ta3) is 1.0. 10. The thermocurable resin composition according to the above [6].
[8] The total number of moles (Ma2) of the amino group-derived groups of the amine compound (a2) and the total number of moles (Ma3) of the amino group-derived groups (including amino groups) 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] Further, according to any one of the above [1] to [8], which contains at least one selected from the group consisting of an elastomer (B), an inorganic filler (C) and a curing accelerator (D). 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 an interlayer insulating layer containing the thermosetting resin composition according to any one of the above [1] to [10].
[12] A composite film containing 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 containing a cured product of the resin film for interlayer insulation according to the above [11] or a 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 electronic devices using signals in a high frequency band, it has a high glass transition temperature, is excellent in embedding property in irregularities of circuits and the like, and is excellent in dielectric. It has both characteristics and low thermal expansion, and has good handleability when made into a film (that is, it has flexibility when the thermosetting resin composition is B-staged, and at the same time, it is bent when made into a film. However, it is possible to provide a thermosetting resin composition that is less likely to cause cracks and is easily peeled off from the cover film). Then, it is possible to provide a resin film for interlayer insulation, a composite film, a printed wiring board, and a semiconductor package using the thermosetting resin composition.

It is a figure which showed typically one aspect of the composite film of this embodiment. It is a graph which shows the temperature-melt viscosity curve about the resin film for interlayer insulation produced in Example 4 and Comparative Example 1.

Hereinafter, embodiments of the present invention will be described in detail. In this specification, a numerical range (X and Y are real numbers) that are greater than or equal to X and less than or equal to Y may be expressed as "X to Y". For example, the description "0.1 to 2" indicates a numerical range of 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 "composite film" is a composite film in which the contained thermosetting resin composition is uncured, and a composite film in which the contained thermosetting resin composition is semi-cured (so-called B-stage shape). Including both.
The "composite" of a 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 composed of a support, a protective film, and the like. You may.

Further, in the present specification, the "interlayer insulating layer" is a layer located between two conductor layers and for insulating the conductor layer. Examples of the "interlayer insulating layer" in the present specification include a cured product of a composite film. In addition, in this specification, a "layer" also includes a layer in which a part is missing, a via or a pattern is formed.
Further, in the present specification, the relative permittivity and dielectric loss tangent in the high frequency band may be referred to as dielectric characteristics or high frequency characteristics, and low relative permittivity and dielectric loss tangent in the high frequency band are expressed as excellent high frequency characteristics. Sometimes.
It should be noted that the present invention also includes all aspects in which the items described in the present specification are arbitrarily combined.

[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 structural unit derived from an amine compound (a2) having a carbon-carbon double bond. It is a thermosetting resin composition containing the polyimide compound (A) having.
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 carbon-carbon double bond. is there. 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.
Examples of the component (a1) include bis (4-maleimidephenyl) methane, polyphenylmethanemaleimide, bis (4-maleimidephenyl) ether, bis (4-maleimidephenyl) sulfone, 3,3'-dimethyl-5, 5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane, etc. 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. Although it may be a compound, it is preferably an aromatic maleimide compound.
As the component (a1), bis (4-maleimidephenyl) methane is preferable from the viewpoint of low cost, and 3,3'-dimethyl-5,5'-diethyl- from the viewpoint of excellent dielectric properties and low water absorption. 4,4'-Diphenylmethanebismaleimide is preferable, and 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane is preferable because it has 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 indicates the residue of the component (a1), and * indicates the binding portion. A ¹ is not particularly limited, but for example, a residue similar to A ³ described later is preferable.
The residue refers to the structure of a portion of the raw material component excluding the functional group (maleimide group in the component (a1)) provided for bonding.

(Amine compound having a carbon-carbon double bond (a2))
The amine compound (a2) having a carbon-carbon double bond (hereinafter, also referred to as “component (a2)”) is not particularly limited as long as it has a carbon-carbon double bond, and is an aliphatic amine (alicyclic). The formula amine is included.), It may be an aromatic amine, it may be a monoamine compound, or it may be a diamine compound. Among these, an aliphatic amine is preferable as the component (a2).
The number of carbon-carbon double bonds contained in the component (a2) may be one or two or more. The number of carbon-carbon double bonds of the component (a2) may be one or two from the viewpoints of high glass transition temperature, embedding property in unevenness of circuits, dielectric properties, low thermal expansion property, and handleability. Preferably, it is more preferably two. When the number of carbon-carbon double bonds of the component (a2) is two, nitrogen is used from the viewpoints of high glass transition temperature, embedding property in irregularities such as circuits, dielectric property, low thermal expansion property, and handleability. It is preferably present one at a time on another group attached to the atom. When the number of carbon-carbon double bonds of the component (a2) is two or more, at least one is obtained from the viewpoints of high glass transition temperature, embedding property in irregularities such as circuits, dielectric property, low thermal expansion property, and handleability. It is preferred that one carbon-carbon double bond is not conjugated to another carbon-carbon double bond.
Further, the amino group contained in the component (a2) may be a primary amino group or a secondary amino group. From the viewpoints of high glass transition temperature, embedding property in irregularities such as circuits, dielectric property, low thermal expansion property and handleability, the amino group contained in the component (a2) is preferably a secondary amino group, and is preferably a secondary amino group. More preferably, it is a group monoamine.

The component (a2) used in the present embodiment is an amine compound that is liquid at room temperature, and when the thermosetting resin composition is B-staged, it has good flexibility, that is, excellent handleability. In the present embodiment, by using the amine compound (a2) having a carbon-carbon double bond, it has a high Tg, is excellent in embedding property in irregularities of circuits and the like, and has both excellent dielectric properties and low thermal expansion property. Furthermore, the handleability when made into a film is also good (that is, it has flexibility when the thermosetting resin composition is B-staged, and at the same time, when it is made into a film, cracks are unlikely to occur and the cover film It is easy to peel off). By substituting the group having a carbon-carbon double bond with a nitrogen atom, the amino groups having a carbon-carbon double bond in the amine compound (a2) Michael added to the component (a1) are stacked (stacked). This, and the fact that the component (a1) and the component (a2) react in a complicated manner with a cross-linking reaction due to radical polymerization by a carbon-carbon double bond at the time of curing leads to an improvement in Tg and a low thermal expansion rate. I guess it was.
The molecular weight of the component (a2) is preferably 50 to 400, more preferably 50 to 300, still more preferably 50 to 200, particularly preferably 50 to 150, from the viewpoint of ease of stacking and handleability. Most preferably, it is 70 to 120.

Among the above, the aliphatic monoamine is preferably at least one selected from the group consisting of an aliphatic monoamine and an alicyclic diamine, and an aliphatic monoamine is more preferable.
Examples of the aliphatic monoamine having a carbon-carbon double bond include allylamine and diallylamine. Of these, diallylamine is preferable. Examples of the alicyclic diamine having a carbon-carbon double bond include norbornene diamine.

The total number of maleimide group-derived groups (including maleimide groups) derived from the maleimide compound (a1) with respect to the total equivalent (Ta2) of the 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 to 50, and more preferably 1 to 30. Within 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 the polyamine compound (a3) (hereinafter, also referred to as “component (a3)”, but the amine compound (a2) is not included). Also, it is preferable to have it.

The 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.
Examples of the component (a3) include 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4. '-Diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylketone, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4 '-Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzene, 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-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- Examples thereof include bis (4-aminophenyl) fluorene. 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, because it is excellent in solubility in an organic solvent, 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. The component (a3) is preferably 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane from the viewpoint of excellent dielectric properties and low water absorption. The component (a3) is preferably 2,2-bis (4- (4-aminophenoxy) phenyl) propane from the viewpoint of excellent mechanical properties such as high adhesiveness to a conductor, elongation, and breaking strength. Further, in addition to being excellent in solubility in the above-mentioned organic solvent, reactivity at the time of synthesis, heat resistance, and high adhesion to a conductor, the component (a3) can exhibit excellent high frequency characteristics and low hygroscopicity. ) Are preferably 4,4'-[1,3-phenylenebis (1-methylethylidene)] bisaniline and 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.

（式中、Ｒ^１及びＲ^２は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基、炭素数１〜５のアルコキシ基、水酸基、又はハロゲン原子を示す。Ａ^３は炭素数１〜５のアルキレン基、アルキリデン基、エーテル基、スルフィド基、スルフォニル基、カルボニルオキシ基、ケトン基、フルオレニレン基、単結合、下記一般式（４−１）、又は下記一般式（４−２）で表される残基である。）

（式中、Ｒ^３及びＲ^４は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基、又はハロゲン原子を示す。Ａ^４は炭素数１〜５のアルキレン基、イソプロピリデン基、ｍ−又はｐ−フェニレンジイソプロピリデン基、エーテル基、スルフィド基、スルフォニル基、カルボニルオキシ基、ケトン基、又は単結合である。）

（式中、Ｒ^５は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基、又はハロゲン原子を示す。Ａ^５及びＡ^６は炭素数１〜５のアルキレン基、イソプロピリデン基、エーテル基、スルフィド基、スルフォニル基、カルボニルオキシ基、ケトン基、又は単結合である。）In the general formulas (3-1) and (3-2), A ² indicates the residue of the component (a3), and * indicates the binding portion. A ² is not particularly limited, but is preferably a group represented by the following general formula (4).

(In the formula, 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 is carbon. Numbers 1 to 5 of alkylene group, alkylidene group, ether group, sulfide group, sulfonyl group, carbonyloxy group, ketone group, fluorenylene group, single bond, the following general formula (4-1), or the following general formula (4-2) ) Is a residue.)

(In the formula, R ³ and R ⁴ independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom. A ⁴ is an alkylene group having 1 to 5 carbon atoms and an isopropylidene group. , M- or p-phenylenediisopropylidene group, ether group, sulfide group, sulfonyl group, carbonyloxy group, ketone group, or single bond.)

(In the formula, 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 are an alkylene group having 1 to 5 carbon atoms and an isopropylidene group. , Ether group, sulfide group, sulfonyl group, carbonyloxy group, ketone group, or single bond.)

With respect to the total equivalent of the amino group-derived groups (Ta2) of the amine compound (a2) and the total equivalent (Ta3) of the amino group-derived groups of the amine compound (a3) in the polyimide compound (A). The equivalent ratio [Ta1 / (Ta2 + Ta3)] to the total equivalent (Ta1) of the maleimide group-derived group (including the maleimide group) derived from the maleimide compound (a1) is preferably 1.0 to 10 and 1 More preferably, it is 0 to 5.0. Within 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 (Ma2) of the amino group-derived groups of the amine compound (a2) to the total number of moles (Ma3) of the amino group-derived groups (including amino groups) of the polyamine compound (a3). [Ma2 / Ma3] is preferably 0.01 to 10, more preferably 0.05 to 5, further preferably 0.1 to 3, and 0.3 to 1.5. It is particularly preferable to have. Within the above range, the glass transition temperature is high, the embedding property in irregularities of circuits, etc. is excellent, both excellent dielectric properties and low thermal expansion are achieved, and the handling property when made into a film is also good (that is,). The thermosetting resin composition has flexibility when it is B-staged, and at the same time, it is a thermosetting resin composition that is less likely to crack even when bent and easily peeled off from the cover film). 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 for producing the polyimide compound (A) is not particularly limited, and a 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, which will be described later.

When producing the polyimide compound (A), a reaction catalyst can be used if necessary. The reaction catalyst is not limited, but for example, acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine and tributylamine; imidazoles such as methylimidazole and phenylimidazole; phosphorus catalysts such as triphenylphosphine and the like. 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 is 0, for example, with respect to 100 parts by mass of the total amount of the component (a1), the component (a2), the component (a3) used as needed, and other components. It can be used in the range of 0.01 to 5.0 parts by mass.

A predetermined amount of the component (a1), the component (a2), the component (a3) and other components are charged into the reactor, and the component (a1), the component (a2) and, if necessary, the component (a3) and other components are charged. The polyimide compound (A) is obtained by carrying out 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 and suppression of gelation. ..
Further, in this step, the solid content concentration and the solution viscosity of the reaction raw material can be adjusted by adding or concentrating the above-mentioned organic solvent. The solid content concentration of the reaction raw material is not particularly limited, but is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, for example. 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. Further, when the solid content concentration of the reaction raw material is 90% by mass or less, better solubility can be obtained, stirring efficiency is good, and gelation is less likely to occur.
After the production of the polyimide compound (A), a part or all of the organic solvent may be removed and concentrated according to the purpose, or the organic solvent may be added and diluted. As the organic solvent additionally used, the organic solvent exemplified in the production process of the polyimide compound (A) can be applied. These may be used alone or in combination of two or more. From the viewpoint of solubility, the organic solvent used is preferably methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, and more preferably propylene glycol monomethyl ether.

The weight average molecular weight (Mw) of the polyimide compound (A) is not particularly limited, but is preferably in the range of 800 to 1,500, more preferably in the range of 800 to 1,300, and is preferably in the range of 1,000 to 1,300. The range is even more preferred. The weight average molecular weight of the polyimide compound (A) can be determined by the method described in 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 is 50 in the total mass of all the resin components contained in the thermosetting resin composition of the present embodiment. It is preferably ~ 95% by mass, more preferably 60 to 90% by mass, still more preferably 70 to 85% by mass. By setting the content of the polyimide compound (A) within the above range, the dielectric properties tend to be better.

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 that it is contained. Hereinafter, these components will be described in order.
<Elastomer (B)>
The elastomer (B) is not particularly limited, and for example, 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 these elastomers. Examples include derivatives. These may be used alone or in combination of two or more.

As the elastomer (B), one having a reactive functional group at the molecular terminal or in the molecular chain can be used. As the reactive functional group, 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 amide group, an isocyanato group, an acrylic group, a methacryl group and a vinyl group. It is more preferable that there is 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, a maleic anhydride group is more preferable. By having these reactive functional groups, the compatibility with the resin is improved, and the separation of the inorganic filler (C) and the resin component when the interlayer insulating layer is formed tends to be suppressed. From the same viewpoint, the elastomer (B) is preferably an elastomer modified with maleic anhydride.

The polybutadiene-based elastomer preferably includes a structure consisting of a 1,4-trans form and a 1,4-cis form containing a 1,2-vinyl group.
As the polybutadiene-based elastomer, one having a reactive functional group is used from the viewpoint of improving compatibility with the resin and suppressing separation of the inorganic filler (C) and the resin component when the interlayer insulating layer is formed. Preferably, a polybutadiene-based elastomer modified with an acid anhydride is particularly preferable. The acid anhydride is not particularly limited, and for example, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadicic anhydride, Phthalic anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride and the like can be mentioned. Of these, maleic anhydride is preferred.
When the elastoma (B) is modified with an acid anhydride, the number of acid anhydride-derived groups (hereinafter, also referred to as "acid anhydride groups") contained in one molecule of the elastoma (B) is 1 to 10. Is preferable, 1 to 6 are more preferable, and 2 to 5 are even more preferable. When the number of acid anhydride groups is 1 or more in one molecule, the separation between the inorganic filler (C) and the resin component when the interlayer insulating layer is formed tends to be further suppressed. Further, when the number of acid anhydride groups is 10 or less in one molecule, the relative permittivity and the dielectric loss tangent of the thermosetting resin composition tend to be lower. When the elastomer (B) is modified with maleic anhydride, a group derived from maleic anhydride contained in one molecule of the elastomer (B) (hereinafter, also referred to as "maleic anhydride group") from the same viewpoint as above. The number of is preferably 1 to 10, more preferably 1 to 6, and even more preferably 2 to 5.

Preferable examples of the styrene-based elastoma include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, and styrene-ethylene-propylene-styrene block copolymer. Examples of the components constituting the styrene-based elastomer include styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene, in addition to styrene.

Examples of the olefin-based elastoma include copolymers of α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene and 4-methyl-pentene, and examples thereof include ethylene-propylene. Preferable examples include a polymer (EPR) and an ethylene-propylene-diene copolymer (EPDM). Examples thereof include a copolymer of the α-olefin with a non-conjugated diene having 2 to 20 carbon atoms such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, etylidene norbornene, butadiene, and isoprene. .. Further, carboxy-modified NBR obtained by copolymerizing methacrylic acid with a butadiene-acnillonitrile copolymer can be mentioned.

The urethane-based elastomer preferably contains, for example, a hard segment composed of a short-chain diol and a diisocyanate, and a soft segment composed of a polymer (long-chain) diol and a diisocyanate.
Examples of the polymer (long chain) diol include polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene-1,4-butylene adipate), polycaprolactone, and poly (1,6-he). Xylene carbonate), poly (1,6-hexylene / neopentylene adipate) and the like. The number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000.
Examples of the short chain diol 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 the polyester-based elastomer include those obtained by polycondensing 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 naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which the hydrogen atom of these aromatic nuclei is substituted with a methyl group, an ethyl group, a phenyl group, or the like; Examples thereof include 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 of these compounds 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. Aliphatic diols such as bisphenol A, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) propane, aromatic diols such as resorcin and the like. One of these compounds may be used alone, or two or more of these compounds may be used in combination.

Further, as the polyester-based 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. Can be mentioned. There are various grades of multi-block copolymers depending on the types, ratios, and molecular weights of hard segments and soft segments. Specific examples are "Hitrel (registered trademark)" (manufactured by Toray DuPont Co., Ltd.), "Perprene (registered trademark)" (manufactured by Toyobo Co., Ltd.), and "Esper (registered trademark)" (manufactured by Hitachi Kasei Co., Ltd.). And so on.

As the polyamide-based elastoma, for example, polyamide is a hard segment component, polybutadiene, butadiene-acrylonitrile copolymer, styrene-butadiene copolymer, polyisoprene, ethylene propylene copolymer, polyether, polyester, polybutadiene, polycarbonate, polyacrylate. , Polymethacrylate, polyurethane, silicone rubber and the like as soft segment components.

Examples of the acrylic elastomer include a polymer of a raw material monomer containing an acrylic ester as a main component. Preferable examples of the acrylate ester include ethyl acrylate, butyl acrylate, methoxyethyl acrylate, and ethoxyethyl acrylate. Further, as the cross-linking point monomer, glycidyl methacrylate, allyl glycidyl ether and the like may be copolymerized, and further, acrylonitrile, ethylene and the like may be copolymerized. Specific examples thereof include an acrylonitrile-butyl acrylate copolymer, an acrylonitrile-butyl acrylate-ethyl acrylate copolymer, and an acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer.

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

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 polybutadiene-based elastomers and styrene-based elastomers are preferable from the viewpoint of dielectric properties. 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, more preferably 1,000 to 30,000. When the weight average molecular weight of the elastomer (B) is 500 or more, the curability of the thermosetting resin composition and the dielectric properties of the cured product tend to be better. Further, 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 when the interlayer insulating layer is formed tends to be suppressed. As the weight average molecular weight of the elastomer (B), the method for measuring the weight average molecular weight of the polyimide compound (A) described in Examples can be applied.

When the thermosetting resin composition contains an elastomer (B), the content thereof is preferably 1 to 70% by mass, preferably 5 to 50% by mass, based on the total resin components contained in the thermosetting resin composition. More preferably, 10 to 30% by mass is further preferable. By keeping the content of the elastomer (B) within the above range, the relative permittivity and the dielectric loss tangent are low, the handleability when formed into a film is excellent, and the inorganic filler (C) when the interlayer insulating layer is formed. The separation between the resin component and the resin component tends to be suppressed.

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

The shape of the inorganic filler (C) is not particularly limited, and may be, for example, spherical, crushed, needle-shaped or plate-shaped, but can be used as an organic solvent for improving dispersibility in a thermosetting resin composition. Improvement of dispersibility in the resin varnish in which the thermosetting resin composition is dissolved or dispersed, improvement of fluidity by reducing the viscosity of the resin varnish, suppression of increase in surface roughness of the insulating layer formed from the thermosetting resin composition, etc. From the viewpoint of, it is preferable that it is spherical.

The volume average particle diameter of the inorganic filler (C) is not particularly limited, but is preferably, for example, 0.05 to 5 μm, more preferably 0.1 to 3 μm, and even more preferably 0.2 to 1 μm. When the volume average particle diameter of the inorganic filler (C) is 5 μm or less, the fine pattern tends to be formed more stably when the circuit pattern is formed on the interlayer insulating layer. Further, when the volume average particle diameter of the inorganic filler (C) is 0.1 μm or more, the heat resistance tends to be better.
The volume average particle size is the particle size of a point corresponding to 50% of the volume when the cumulative frequency distribution curve based on the particle size is obtained with the total volume of the particles as 100%. It can be measured with the particle size distribution measuring device or the like used.

Further, for the purpose of improving the dispersibility of the inorganic filler (C) and the adhesiveness between the inorganic filler (C) and the organic component in the thermosetting resin composition, a coupling agent is used in combination as necessary. May be 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, a silane coupling agent is preferable. Examples of the silane coupling agent include aminosilane-based coupling agents, epoxysilane-based coupling agents, phenylsilane-based coupling agents, alkylsilane-based coupling agents, alkenylsilane-based coupling agents, and mercaptosilane-based coupling agents. Be done. Among these, an aminosilane-based coupling agent is preferable from the viewpoint of improving the dispersibility of the inorganic filler (C) and improving the adhesiveness between the inorganic filler (C) and the organic component.
When a coupling agent is used, the amount used is not particularly limited, but is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the inorganic filler (C). preferable. Within this range, the features of using the inorganic filler (C) can be exhibited more effectively.
When a coupling agent is used, the addition method may be a so-called integral blend treatment method in which the inorganic filler (C) is added to the thermosetting resin composition and then the coupling agent is added. From the viewpoint of more effectively expressing the features of the inorganic filler (C), a method of surface-treating the coupling agent in advance with the inorganic filler before compounding may be used.

The inorganic filler (C) is preferably used in the form of a slurry previously dispersed in an organic solvent from the viewpoint of enhancing dispersibility in the thermosetting resin composition. The organic solvent used in the slurry of the inorganic filler (C) is not particularly limited, and for example, the organic solvent exemplified in the above-mentioned production step of the polyimide compound (A) can be applied. 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 enhancing dispersibility.
The solid content concentration of the slurry of the inorganic filler (C) is not particularly limited, but for example, from the viewpoint of sedimentation and dispersibility of the inorganic filler (C), 50 to 80% by mass is preferable, and 60 to 80% by mass is preferable. Is more preferable, and 60 to 75% by mass is further preferable.

When the thermosetting resin composition contains the inorganic filler (C), the content thereof can be appropriately selected depending on the desired properties and functions, but is 55% by volume or more with respect to the solid content of the thermosetting resin composition. Is preferable, 55 to 85% by volume is more preferable, 55 to 80% by volume is further preferable, and 55 to 75% by volume is particularly preferable. By setting the content of the inorganic filler (C) in such a range, a low coefficient of thermal expansion can be obtained.
In the present specification, the solid content contained in the thermosetting resin composition means a residue obtained by excluding volatile components from the components constituting the thermosetting resin composition.

<Curing accelerator (D)>
By containing the curing accelerator (D) in the thermosetting resin composition of the present embodiment, the curability of the thermosetting resin composition is improved, and the dielectric properties, heat resistance, elastic modulus, glass transition temperature, etc. are improved. It can be improved further.
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. And so on. Among these, various imidazole compounds, derivatives thereof, and peroxides are preferable.
In particular, from the viewpoint of obtaining the effect of the present invention by radical polymerization of the carbon-carbon double bond of the amine compound (a2) used for producing the polyimide compound (A), the curing accelerator (D) contains a peroxide. It is preferable to contain it. From the same viewpoint, the curing accelerator (D) preferably contains a peroxide together with various imidazole compounds and derivatives thereof.

Examples of various imidazole compounds and derivatives thereof include 2-methylimidazole, 2-ethylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenyl imidazole, 1,2-dimethyl imidazole and 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-ethyl- 4-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 -Triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')] imidazole compounds such as ethyl-s-triazine; 1-cyanoethyl-2-phenylimidazolium trimerite Examples thereof include an addition reaction product of the imidazole compound and trimellitic acid; an addition reaction product of the imidazole compound and isocyanuric acid; and an addition reaction product of the imidazole compound and hydrobromic acid.

Examples of the peroxide include t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexine, and dicumyl peroxide. , Di (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di-t-hexyl peroxide, t-butyl cumyl peroxide and other organic peroxides Can be mentioned. One type of peroxide may be used alone, or two or more types may be used in combination.

When the thermosetting resin composition contains the curing accelerator (D), the content thereof can be appropriately selected depending on the desired properties and functions, but is 0. For all the resin components contained in the thermosetting resin composition. 01 to 10% by mass is more preferable, 0.1 to 5% by mass is further preferable, and 0.1 to 3% by mass is particularly preferable. By setting the content of the curing accelerator (D) in such a range, the curability and storage stability tend to be good.
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, based on the curing accelerator (D). Preferably, 60 to 90% by mass is more preferable, and 70 to 90% by mass is particularly preferable. This also applies when the curing accelerator (D) contains a peroxide together with various imidazole compounds and their derivatives.

<Other ingredients>
If necessary, the thermosetting resin composition of the present embodiment may contain additives such as a flame retardant, an antioxidant, an ultraviolet absorber, and a flow conditioner.
The flame retardant is not particularly limited, and examples thereof include chlorine-based flame retardants, bromine-based flame retardants, phosphorus-based flame retardants, and metal hydrate-based flame retardants. Phosphorus-based flame retardants and metal hydrate-based flame retardants are preferable from the viewpoint of compatibility with the environment.
The antioxidant is not particularly limited, and examples thereof include phenolic antioxidants such as hindered phenolic antioxidants and styrenated phenolic antioxidants.
The ultraviolet absorber is not particularly limited, and examples thereof include a benzotriazole-based ultraviolet absorber.

[Resin film for interlayer insulation]
The interlayer insulating resin film of the present embodiment contains the thermosetting resin composition of the present embodiment.
The interlayer insulating resin film of the present embodiment may have a support provided on one of the surfaces thereof.
Examples of the support include a polyolefin film such as polyethylene, polypropylene, and polyvinyl chloride; a polyester film such as polyethylene terephthalate (hereinafter, also referred to as “PET”) and polyethylene naphthalate; various plastics such as a polycarbonate film and a polyimide film. Examples include film. Further, a metal foil such as a copper foil or an aluminum foil, a paper pattern, or the like may be used. The support and the protective film described later may be subjected to surface treatment such as matte treatment and corona treatment. Further, the support and the protective film described later may be subjected to a mold release treatment with a silicone resin-based mold release agent, an alkyd resin-based mold release agent, a fluororesin-based mold release agent, or the like.
The thickness of the support is not particularly limited, but is preferably 10 to 150 μm, more preferably 25 to 50 μm.

The use of the interlayer insulating resin film of the present embodiment is not particularly limited, but an adhesive film, an insulating resin sheet such as a prepreg, a circuit board, a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, and a component. It can be used in a wide range of applications where an interlayer insulating layer such as an embedded resin is required. Among them, it can be suitably used for forming an interlayer insulating layer in the production of a printed wiring board.
Next, a method for producing the interlayer insulating resin film of the present embodiment will be described.

<Manufacturing method of resin film for interlayer insulation>
The interlayer insulating resin film of the present embodiment can be used as the first resin layer described later, and can be produced, for example, as follows.
When producing a resin film for interlayer insulation, first, each of the above components is mixed to produce a thermosetting resin composition. At this time, the thermosetting resin composition is preferably in a 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 resin varnish is also in the category of the thermosetting resin composition of the present invention.
Examples of the organic solvent used for producing the varnish for the resin film 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 and carbitol acetate. Acetic acid esters such as; carbitols such as cellosolve and butylcarbitol; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. One type of these organic solvents may be used alone, or two or more types may be used in combination.
The amount of the organic solvent blended is preferably 10 to 50 parts by mass, more preferably 20 to 40 parts by mass, based on 100 parts by mass of the total mass of the varnish for the resin film for interlayer insulation.

The interlayer insulating resin film varnish produced in this manner is applied to the support and then heat-dried to obtain an interlayer insulating resin film.
As a method of applying the varnish for the resin film for interlayer insulation to the support, for example, a coating device such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, or a die coater can be used. It is preferable that these coating devices are appropriately selected depending on the film thickness.
The drying conditions after coating are not particularly limited and may be appropriately determined depending on the type of solvent. For example, the drying temperature is preferably 50 to 150 ° C, more preferably 100 to 145 ° C. The drying time can be, for example, 2 to 10 minutes.

When the resin film for interlayer insulation of the present embodiment is used by arranging it on the conductor layer, it is preferably equal to or more than the thickness of the conductor layer of the circuit board from the viewpoint of embedding the conductor layer of the circuit board. 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, preferably 5 to 60 μm. More preferably, it is more preferably 10 to 60 μm.

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, but is, for example, 1 to 40 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to the surface of the interlayer insulating resin film and scratches. The interlayer insulating resin film can be rolled up and stored.

[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 containing 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 electronic devices that uses signals in a high frequency band.

The first resin layer is provided between the circuit board and the adhesion auxiliary layer in the case of manufacturing a printed wiring board using the composite film of the present embodiment, for example, and is provided between the conductor layer of the circuit board and the layer above it. It is used to insulate and. Further, when the circuit board has through holes, via holes, etc., the first resin layer flows into them and also plays a role of filling the holes.

The second resin layer is located 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 adhesiveness with the conductor layer. is there. By providing the second resin layer, a smooth surface can be obtained, and better adhesive strength can be obtained with the conductor layer formed by plating.
The component of the second resin layer is not particularly limited as long as it improves the adhesiveness with the conductor layer. For example, a polyfunctional epoxy resin (b1) and a phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (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 thermosetting resin composition containing b2) is preferably mentioned. The component of the second resin layer is more preferably a thermosetting resin composition containing the 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 International Publication No. 2016/11404 can be referred to, and the second resin layer described in the document is adopted as it is. You may.

Even if the composite film of the present embodiment has the first resin layer and the second resin layer, and the support is provided on the surface of the second resin layer opposite to the first resin layer. Good. In this case, the configuration is a first resin layer / a second resin layer / a support. Examples of the support include a polyolefin film such as polyethylene, polypropylene, and polyvinyl chloride; a polyester film such as polyethylene terephthalate (hereinafter, also referred to as “PET”) and polyethylene naphthalate; various plastics such as a polycarbonate film and a polyimide film. Examples include film. Further, a metal foil such as a copper foil or an aluminum foil, a paper pattern, or the like may be used. The support and the protective film described later may be subjected to surface treatment such as matte treatment and corona treatment. Further, the support may be subjected to a mold release treatment with a silicone resin-based mold release agent, an alkyd resin-based mold release agent, a fluororesin-based mold release agent, or the like.
The thickness of the support is not particularly limited, but is preferably 10 to 150 μm, more preferably 25 to 50 μm.

The composite film of the present embodiment may be provided with a protective film. For example, an embodiment in which a protective film is provided on the surface of the first resin layer opposite to the second resin layer can be mentioned. In this case, for example, the configuration is a protective film / first resin layer / second resin layer, protective film / first resin layer / second resin layer / support, and the like.
Examples of the protective film include plastic films such as polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, and polyimide film. Further, the protective film may be subjected to surface treatment such as primer coating, UV treatment, corona discharge treatment, polishing treatment, etching treatment, and mold release treatment, if necessary.
The support may be used as a protective film.

In the composite film of the present embodiment, for example, a second resin layer is formed on the support, a first resin layer is formed on the second resin layer, and a first resin layer is formed if necessary. It can be produced by a method of forming a protective layer on a resin layer. To form the second resin layer, a varnish for the second resin layer, which will be described later, is applied to the support, dried by heating, and then a varnish for the first resin layer, which will be described later, is applied onto the support. , Can be formed by heating and drying. As a method of applying the resin varnish, for example, a coating device such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, or a die coater can be used. It is preferable that these coating devices are 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, the drying temperature is preferably 50 to 130 ° C., more preferably 70 to 110 ° C. when forming the first resin layer. When forming the first resin layer, the drying time can be, for example, 1 to 10 minutes. For example, the drying temperature is preferably 50 to 150 ° C., more preferably 100 to 145 ° C. when forming the second resin layer. When forming the second resin layer, the drying time can be, for example, 1 to 10 minutes.
In the above drying, it is preferable to dry so that the content of the volatile component (mainly an organic solvent) in the first resin layer or the second resin layer after drying is 10% by mass or less, preferably 6% by mass. It is more preferable to dry it so that it becomes% or less.

Further, 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 or the like at a softening temperature or higher.

In the composite film of the present embodiment, the thickness of the first resin layer is preferably 1c to 3c, more preferably 1c to 2c, and 1.1c in order to embed the uneven height c of the circuit. It is more preferably ~ 1.5c. When the thickness of the first resin layer is 1c or more, sufficient embedding property can be ensured when the unevenness of the circuit is embedded, and the surface layer of the composite film after embedding tends to be easily kept flat. On the other hand, when it is 3c or less, the thickness of the substrate tends to be easy and the warpage tends to be low, which is preferable.
Specifically, the thickness of the first resin layer is preferably, for example, 10 to 40 μm in order to embed the uneven height of the circuit. The thickness of the first resin layer is more preferably 15 to 35 μm, and even more preferably 20 to 35 μm.

On the other hand, the second resin layer is a layer that can be applied to the semi-additive method. In order to ensure surface flatness and high adhesiveness to plated copper, the thickness of the second resin layer is preferably 1 to 10 μm, more preferably 1 to 7 μm, and 1 to 5 μm. It is more preferably 1 to 3 μm, and further preferably 1.5 to 3 μm. When the thickness of the second resin layer is 1 μm or more, it is easy to prevent the second resin layer from breaking and exposing the first resin layer to the surface when embedding in the unevenness of the circuit, and the desmear There is little risk that the second resin layer will elute and disappear during the process. On the other hand, when it is 10 μm or less, it is easy to suppress a decrease in surface flatness and it is preferable because the substrate can be made thinner.

When 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 and c ≦ a ≦ It is preferable that the composite film satisfies the relationship of 2c or c ≦ a ≦ 1.5c and 1 ≦ b ≦ 10 or 1 ≦ b ≦ 5. A film that satisfies this relationship can achieve both sufficient embedding property and fine circuit forming property.

The first resin layer has a minimum melt viscosity at 80 to 150 ° C., preferably 100 to 4,000 Pa · s. Within this range, the first resin layer can be flowed at 80 to 150 ° C., which is preferable from the viewpoint of embedding property. 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 fluidity of the film does not become too large, it becomes easy to maintain the surface flatness of the composite film after embedding, and the thickness of the substrate varies. Tends to be able to suppress. Further, when it is 4,000 Pa · s or less, the fluidity becomes good and the unevenness of the wiring tends to be easily embedded.

On the other hand, the second resin layer has a minimum melt viscosity of 50,000 Pa · s or more at 80 to 150 ° C. In the second resin layer, when the composite film is embedded in the circuit, the second resin layer maintains a constant thickness, and the surface flatness of the composite film after embedding can be easily maintained. From the same viewpoint, the minimum melt viscosity of the second resin layer at 80 to 150 ° C. is preferably 50,000 to 100,000 Pa · s, and more preferably 50,000 to 75,000 Pa · s. preferable.

The composite film of this 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 beams such as α-rays, γ-rays, and electron beams. Among these, ultraviolet rays are preferable.

An example of the composite film of the present embodiment is shown in FIG. 1 as a schematic cross-sectional view. The composite film according to the present embodiment includes a first resin layer 1 and a second resin layer 2, and if necessary, a support 3 and / or a protective film 4.
There is no clear interface between the first resin layer 1 and the second resin layer 2. For example, a part of the constituent components of the first resin layer 1 and the second resin layer A part of the constituents of 2 may be in a compatible and / or mixed state.

[Printed wiring board and its manufacturing method]
The printed wiring board of the present embodiment contains a cured product of the resin film for interlayer insulation 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.
Hereinafter, a method of manufacturing a printed wiring board by laminating the composite film of the present embodiment on a circuit board will be described.

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): Laminating the composite film of the present embodiment on one side or both sides of the circuit board Step (2): Curing the composite film to form an interlayer insulating layer Step (3): Layering the 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

<Process (1)>
The step (1) is a step of laminating the composite film of the present embodiment on one side or both sides of the circuit board. Examples of the apparatus for laminating the composite film include a vacuum laminator such as a vacuum applicator manufactured by Nikko Materials Co., Ltd.

In the lamination, when the composite film has a protective film, after removing the protective film, the composite film is pressure-bonded to the circuit board while being pressurized and / or heated.
When a composite film is used, the first resin layer is arranged so as to face the surface of the circuit board on which the circuit is formed.
As for the laminating conditions, the composite film and the circuit board are preheated as necessary, the crimping temperature (lamination temperature) is 60 to 140 ° C., and the crimping pressure is 0.1 to 1.1 MPa (9.8 × 10 ^{4 to} 107). It may be laminated under a reduced pressure of .9 × 10 ⁴ N / m ² ) and an air pressure of 20 mmHg (26.7 hPa) or less. Further, the laminating method may be a batch method or a continuous method using a roll.
The substrate usually has a step due to a circuit or a component, but after laminating the composite film of the present embodiment on the substrate, the step can be sufficiently filled with the first resin layer of the composite film. From the viewpoint of ensuring a sufficient degree of filling, the lamination temperature is particularly preferably 70 to 130 ° C.

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

<Process (3)>
The step (3) is a step of drilling a hole in the circuit board on which the interlayer insulating layer is formed. In this step, holes are drilled 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 the laser, a carbon dioxide gas laser, a YAG laser, a UV laser, an excimer laser and the like are generally used.

<Process (4)>
The step (4) is a step of roughening the surface of the interlayer insulating layer. In this step, the surface of the interlayer insulating layer formed in step (2) is roughened with an oxidizing agent, and at the same time, if via holes, through holes, etc. are formed, they are generated when they are formed. It is also possible to remove "smear".
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 commonly used for roughening the interlayer insulating layer in the production of a multilayer printed wiring board by the build-up method, is used. It may be used to roughen and remove smear.

<Process (5)>
The 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 that can be applied to the semi-additive method. Therefore, in this step, a feeding layer is formed on the surface of the interlayer insulating layer by electroless plating, then a plating resist having a pattern opposite to that of the conductor layer is formed, and a conductor layer (circuit) is formed by electrolytic plating. The additive method can be used.
After forming the conductor layer, for example, by performing an annealing treatment at 150 to 200 ° C. for 20 to 120 minutes, the adhesive strength between the interlayer insulating layer and the conductor layer can be improved and stabilized.

Further, it may have a step of roughening the surface of the conductor layer thus produced. Roughening the surface of the conductor layer has the effect of enhancing the adhesiveness with the resin in contact with the conductor layer. The treatment agent for roughening the conductor layer is not particularly limited, but for example, MEC Etch Bond CZ-8100, MEC Etch Bond CZ-8101, and MEC Etch Bond CZ-5480, which are organic acid-based micro-etching agents, are used. MEC Co., Ltd., trade name) and the like.

Among the above manufacturing methods, the following manufacturing method of the printed wiring board is given as an example of a preferable embodiment.
A step of using the composite film to attach 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 and filling the step.
A step of curing the first resin layer and the second resin layer of the composite film,
A step of forming a circuit on the surface of the composite film on the second resin layer side by a semi-additive method.
A method for manufacturing a printed wiring board.

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

[Semiconductor package]
The present invention also provides a semiconductor package in which a semiconductor element is 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 on 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 example, and any object having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect and effect is the present invention. Included in the technical scope.

Hereinafter, the present invention will be specifically described with reference to 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))
2,2-Bis [4- (4-maleimidephenoxy) phenyl] propane (manufactured by Daiwa Kasei Kogyo Co., Ltd.) in a 1 L volume glass flask container equipped with a thermometer, a reflux condenser, and a stirrer. , Product name: BMI-4000), 4,4'-[1,3-Phenylylene bis (1-methylethylidene)] Bisaniline (manufactured by Mitsui Kagaku Fine Co., Ltd., Product name: Bisaniline M) 70 parts by mass, diallylamine (Tokyo) (Manufactured by Kasei Kogyo Co., Ltd.) and propylene glycol monomethyl ether are added in the blending amounts shown in Table 1 below (unit: parts by mass unless otherwise specified. However, the unit of the numerical value in parentheses is mmol). The reaction was carried out at a liquid temperature of 120 ° C. for 3 hours while refluxing.
Then, it was cooled and filtered by 200 meshes to produce polyimide compounds (A-1) to (A-4) having a weight average molecular weight (Mw) of 1,200 (solid content concentration: 65% by mass).

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

<Measurement method of weight average molecular weight>
The weight average molecular weight of the obtained polyimide compound (A) was converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve is 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, Product name]) was used for approximation by a cubic equation. The conditions for GPC are shown below.
Equipment: Pump: L-6200 type [manufactured by Hitachi High-Technologies Corporation]
Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Corporation]
Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation]
Column: Guard column; TSK Guardcolum HHR-L + Column; TSK gel-G4000HHR + TSK gel-G2000HHR (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

<Manufacturing method of thermosetting resin composition (resin varnish)>
Example 1 (Production of Resin Varnish 1)
As the elastomer (B), 20% by mass of a polybutadiene-based elastomer (manufactured by Ebonic, trade name: POLYVEST 75MA) (for all resin components, that is, for all components not containing inorganic fillers and organic solvents), As the inorganic filler (C), silica (manufactured by Admatex Co., Ltd., methyl isobutyl ketone dispersion having a solid content concentration of 70% by mass) treated with an aminosilane coupling agent 65% by mass (relative to the total volume not containing an organic solvent) ) And mixed.
The ratio of the polyimide compound (A-1) obtained in Production Example 1 to such that the content of the polyimide compound (A-1) is 80% by mass with respect to the total resin components contained in the thermosetting resin composition. And dissolved 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 Nichiyu Co., Ltd., trade name: Perbutyl P) was used as a curing accelerator for the polyimide compound (A-1). 1.0 phr for the raw material (maleimide compound) and elastoma (B) converted from the amount charged, isocyanate mask imidazole (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: G8009L), and the polyimide compound (A-1). 0.5 phr was mixed with the raw material maleimide compound converted from the charged amount. Then, it was dispersed by nanomizer treatment to obtain a resin varnish 1.
The obtained resin varnish 1 is applied to 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. A first resin layer was formed on the support to obtain a resin film for interlayer insulation.
Further, a polypropylene film having a thickness of 15 μm was attached to the surface of the first resin layer and wound into a roll to obtain a resin film 1 for interlayer insulation having a support 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 2-4 (Production of resin varnishes 2-4)
The same applies to 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. To obtain resin varnishes 2 to 4 and further to obtain resin films 2 to 4 for interlayer insulation.
Using the obtained resin films 2 to 4 for interlayer insulation, each characteristic was measured or evaluated according to the method described later. The results are shown in Table 2.

Comparative Example 1 (Manufacturing of Comparative Resin Varnish 5)
In Example 1, the same operation was performed 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 for comparison. A resin varnish 5 for interlayer production was obtained, and a resin film 5 for interlayer insulation was further obtained.
Using the obtained resin film 5 for interlayer insulation, each characteristic was measured or evaluated according to the method described later. The results are shown in Table 2.

A resin plate was prepared according to the following method for measuring or evaluating the characteristics.
(I) The protective film was peeled off from the interlayer insulating resin film having the support and the protective film obtained in each example, and then dried at 120 ° C. for 5 minutes.
Next, a resin film for interlayer insulation having a support after drying is subjected to a copper foil (electric field copper foil) using a vacuum pressure type laminator (manufactured by Meiki Co., Ltd., trade name: MVLP-500 / 600-II). , 35 μm thick), laminated 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. Body (P) was obtained. The laminating was carried out by a method in which the pressure was reduced to 0.5 MPa for 30 seconds and then pressed at 120 ° C. for 30 seconds at a crimping pressure of 0.5 MPa. Then, the support was peeled off from the laminated body (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, the protective film was peeled off, and then the film was dried at 110 ° C. for 3 minutes.
(III) Next, the laminate (P) from which the support obtained in (I) above has been peeled off, and the resin film for interlayer insulation having the support after drying obtained in (II) above are resinated. Laminating under the same conditions as in (I) above so that the layers are in contact with each other, a laminated body (Q) in which a copper foil, a layer composed of two layers of an interlayer insulating resin film, and a support are laminated in this order is obtained. It was. Then, the support was peeled off from the laminated body (Q).
(IV) Next, a resin film for interlayer insulation having a laminate (Q) from which the support obtained in (III) above has been peeled off and a support after drying obtained by the same method as in (II) above. And are laminated under the same conditions as in (I) above so that the resin layers come into contact with each other, and a layer composed of a copper foil, three layers of resin film for interlayer insulation, and a support are laminated in this order ( R) was obtained.
(V) A laminated body (Q) was prepared by the same method as in (I) to (III) above.
(VI) The support of the laminated body (Q) obtained in the above (V) and the support of the laminated body (R) obtained in the above (I) to (IV) are peeled off, and laminated with the laminated body (Q). The resin layers of the body (R) were bonded to each other, and press molding was performed at 190 ° C. for 60 minutes at a crimping pressure of 3.0 MPa using a vacuum press. The obtained resin plate with double-sided copper foil was cured at 190 ° C. for 2 hours, and then the copper foil was etched with ammonium persulfate to obtain a resin plate.

[1. Relative permittivity and dielectric loss tangent measurement method]
Cut out the resin plate produced above into a test piece with a width of 2 mm and a length of 70 mm, and use a network analyzer (manufactured by Agilent Technologies, Inc., trade name: E8364B) and a 5 GHz compatible cavity resonator (manufactured by Kanto Electronics Applied Development Co., Ltd.). The relative permittivity and dielectric loss tangent were measured using. The measurement temperature was 25 ° C. The lower the relative permittivity and the dielectric loss tangent obtained according to the measurement method, the better the high frequency characteristics.

[2. Method for measuring thermal expansion rate 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 Co., Ltd., model: TMA / SS6100 type). The coefficient of thermal expansion is such that the coefficient of thermal expansion is 10 ° C./min and a load of 0.05 N, and after heating (1st) from room temperature to 260 ° C., cooling from 260 ° C. to -30 ° C., and then from -30 ° C to 300 ° C. The value of the average coefficient of thermal expansion (ppm / ° C) in the range of 30 ° C to 120 ° C and the value of the average coefficient of thermal expansion (ppm / ° C) in the range of 250 ° C to 300 ° C when heated to (2nd). Was calculated as the coefficient of thermal expansion. In addition, the inflection point of the expansion amount was determined as the glass transition temperature.

[3. Method for measuring storage elastic modulus]
The resin plate produced above is cut into a test piece having 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, trade name: DVE-V4). did. The measurement temperature range was 40 to 300 ° C., the temperature rising rate was 5 ° C./min, and 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 at the time of mounting can be suppressed.

The following is a test method for a resin film for interlayer insulation.
[4. Evaluation method of embedding property]
The protective film of the resin film for interlayer insulation obtained in Example 4 or Comparative Example 1 was peeled off, stacked so as to have a thickness of 1.0 mm, and the melt viscosity was measured using a sample punched to φ8 mm. The viscosity was measured using a rheometer (trade name: ARESG2, manufactured by TA Instruments Japan Co., Ltd.) at a heating rate of 5 ° C./min, a φ8 mm jig, a frequency of 1.0 Hz, and a strain of 1%. When the melt viscosity is low, the embedding property is excellent. The temperature-melt viscosity curve obtained by the measurement is shown in FIG.

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

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

[7. Surface roughness measurement method]
<Method of manufacturing substrate for surface roughness measurement>
A substrate for measuring surface roughness was prepared 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.
A resin film for interlayer insulation having the obtained support is placed on a CZ-treated printed wiring board (manufactured by Hitachi Kasei Co., Ltd., trade name: E-700GR) with a first resin layer and a printed wiring board. Laminated so that they abut. Lamination was carried out by a method of vacuuming at 100 ° C. for 30 seconds in the first step, crimping for 30 seconds, pressing at a pressure of 0.5 MPa, and flattening at 120 ° C. for 60 seconds at a pressure of 0.5 MPa in the second step.
Then, it cooled to room temperature, and the printed wiring board which arranged the resin film for interlayer insulation was obtained. Next, the printed wiring board on which the resin film for interlayer insulation is arranged 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 is cured. The eyes were cured at 190 ° C. for 40 minutes in an explosion-proof dryer. Then, the support was peeled off to obtain a printed wiring board on which an interlayer insulating layer was formed.

(Roughening treatment method)
The printed wiring board obtained by the above method for manufacturing a substrate for surface roughness measurement is mixed with a swelling solution (manufactured by Attec Japan Co., Ltd., trade name: Swelling Dep Securigant (registered trademark) P) heated to 60 ° C. Immersion treatment for minutes. Next, it was immersed in a roughened solution heated to 80 ° C. (manufactured by Atotech Japan Co., Ltd., trade name: Consate Rate Compact CP) for 15 minutes. Subsequently, it was neutralized by immersing it in a neutralizing solution heated to 40 ° C. (manufactured by Atotech Japan Co., Ltd., trade name: Reduction Solution Security Gant (registered trademark) P500) for 5 minutes. The surface of the interlayer insulating layer roughened in this way was used as a substrate for surface roughness measurement.

Using a specific contact type surface roughness meter (manufactured by Bruker AXS Co., Ltd., trade name: WykoNT9100), the surface roughness of the surface roughness measurement substrate obtained above was measured with an internal lens of 1x and an external lens of 50x. The arithmetic average roughness (Ra) was determined by measurement using.

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

From Table 2, in the examples using the thermosetting resin composition containing the polyimide compound (A), the glass transition temperature was high, the embedding property in irregularities of circuits and the like was excellent, and excellent dielectric properties and low thermal expansion properties were obtained. In addition, the handling performance has been improved.
On the other hand, in the comparative example using the polyimide compound formed without using the amine compound (a2) having a carbon-carbon double bond, the coefficient of thermal expansion in the range of 250 to 300 ° C. increases and the storage elastic modulus decreases. , The bending test result was not excellent, and the surface roughness became large.

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

1 1st resin layer 2 2nd resin layer 3 Support 4 Protective film

Claims (14)

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 carbon-carbon double bond. Thermosetting resin composition. The thermosetting resin composition according to claim 1, wherein the amine compound (a2) has two or more carbon-carbon double bonds. 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 an aliphatic monoamine and an alicyclic diamine. The total equivalent of the maleimide group-derived groups (including the maleimide group) derived from the maleimide compound (a1) to the total equivalent (Ta2) of the 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] with (Ta1) is 1.0 to 30. 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 the polyamine compound (a3). In the polyimide compound (A), the total equivalent (Ta2) of the amino group-derived groups of the amine compound (a2) and the total equivalent (Ta3) of the amino group-derived groups (including the amino group) of the polyamine compound (a3). The equivalent ratio [Ta1 / (Ta2 + Ta3)] to the total equivalent (Ta1) of the maleimide group-derived group (including the maleimide group) derived from the maleimide compound (a1) to the total amount with) is 1.0 to 10. The thermocurable resin composition according to claim 6. The ratio of the total number of moles of amino group-derived groups (Ma2) of the amine compound (a2) to the total number of moles (Ma3) of amino group-derived groups (including amino groups) of the polyamine compound (a3) [Ma2]. / Ma3] is 0.01 to 10, the thermosetting resin composition according to claim 6 or 7. The thermosetting property 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. A resin film for an interlayer insulating layer, which comprises the thermosetting resin composition according to any one of claims 1 to 10. A composite film comprising a first resin layer containing the thermosetting resin composition according to any one of claims 1 to 10 and a second resin layer. A printed wiring board containing a cured product of the resin film for interlayer insulation according to claim 11 or a cured product of the composite film according to claim 12. A semiconductor package comprising the printed wiring board according to claim 13.

Images