JP2021175795A - Thermosetting resin composition, resin film for interlayer insulation, composite film, printed wiring board and production method of the same - Google Patents

Abstract

To provide a thermosetting resin composition that gives a cured product having a low dielectric loss tangent and high elasticity, and a resin film for interlayer insulation, a composite film, a printed wiring board and a production method of the printed wiring board using the above composition.SOLUTION: The thermosetting resin composition comprises an inorganic filler (A), a polyimide compound (B) having a structural unit derived from a maleimide compound (b1) having at least two N-substituted maleimide groups and a structural unit derived from a diamine compound (b2), and an elastomer (C); and a cured product of the composition has an elastic modulus of 8.0 to 12.0 GPa. The present invention discloses, by using the above composition, a resin film for interlayer insulation, a composite film, a printed wiring board and a production method of the printed wiring board.SELECTED DRAWING: None

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 method for producing the same.

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.

In addition, computers, information and communication equipment, etc. 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 it is required to suppress transmission loss due to high frequency. Therefore, as an organic material used in a high frequency region, a material having a low relative permittivity and a dielectric loss tangent is desired.
In order to meet such demands, various efforts have been made for the build-up layer, and for example, Patent Document 1 discloses a resin composition containing a cyanate resin.

On the other hand, the build-up layer is required to have low thermal expansion and high elasticity in order to improve the processing dimensional stability and reduce the amount of warpage after semiconductor mounting. As one of the methods for lowering the thermal expansion and increasing the elasticity of the build-up layer, there is a method of highly filling the filler. For example, by using silica filler for 40% by mass or more of the build-up layer, studies are underway to reduce thermal expansion and elasticity of the build-up layer and reduce warpage during mounting (for example, Patent Documents 2 and 2). 4).

Japanese Unexamined Patent Publication No. 2014-136779 JP-A-2007-87982 Japanese Unexamined Patent Publication No. 2009-280758 Japanese Unexamined Patent Publication No. 2005-39247

However, with the increase in performance and functionality of electronic devices as described above, as a next-generation material, a material having lower thermal expansion and higher elasticity than the resin composition disclosed in Patent Documents 2 to 4 is used. Demand is increasing.
The present invention has been made in view of such a situation, and a thermosetting resin composition in which the cured product has low dielectric loss tangent and high elasticity, a resin film for interlayer insulation using the same, a composite film, and a printed wiring board. And its manufacturing method.

As a result of studying to solve the above-mentioned problems, the present inventors have found that the following problems can be solved by the present invention. That is, the present invention provides the following [1] to [12].
[1] Inorganic filler (A), polyimide compound (B) having a structural unit derived from a maleimide compound (b1) having at least two N-substituted maleimide groups and a structural unit derived from a diamine compound (b2), and elastoma ( A thermosetting resin composition containing C) and having an elastic coefficient of a cured product of 8.0 to 12.0 GPa.
[2] The thermosetting resin composition according to the above [1], wherein the inorganic filler (A) is silica.
[3] The thermosetting resin composition according to the above [1] or [2], wherein the elastomer (C) has a weight average molecular weight of 500 to 50,000.
[4] The thermosetting resin composition according to any one of the above [1] to [3], wherein the elastomer (C) is an elastomer modified with maleic anhydride.
[5] A resin film for interlayer insulation containing the thermosetting resin composition according to any one of the above [1] to [4].
[6] A composite film containing a first resin layer containing the thermosetting resin composition according to any one of the above [1] to [4] and a second resin layer.
[7] A second thermosetting resin composition in which the second resin layer contains a polyfunctional epoxy resin (D), an active ester curing agent (E), and a phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (F). The composite film according to the above [6].
[8] The equivalent ratio (ester group / epoxy group) of the ester group of the active ester curing agent (E) to the epoxy group of the polycyclic epoxy resin (D) in the second thermosetting resin composition is determined. The composite film according to the above [7], which is 0.05 to 1.5.
[9] The composite film according to the above [7] or [8], wherein the second thermosetting resin composition further contains a phosphorus-based curing accelerator (G).
[10] The composite film according to any one of [7] to [9] above, wherein the cured product has a 5 GHz dielectric loss tangent of 0.005 or less.
[11] A printed wiring board containing a cured product of the resin film for interlayer insulation according to the above [5] or a cured product of the composite film according to any one of the above [6] to [10].
[12] A printed wiring board comprising a step of laminating the resin film for interlayer insulation according to the above [5] or the composite film according to any one of the above [6] to [10] on one or both sides of a base material. Manufacturing method.

According to the present invention, it is possible to provide a thermosetting resin composition in which the cured product has low dielectric loss tangent and high elasticity, a resin film for interlayer insulation using the same, a composite film, a printed wiring board, and a method for producing the same. ..

It is a figure which showed typically the composite film of this embodiment.

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.

Further, in the present specification, the "resin composition" includes a mixture of each component described later and a semi-cured (so-called B-stage) mixture of the mixture.

Further, in the present specification, the "interlayer insulation layer" is a layer located between two conductor layers and for insulating the conductor layer. Examples of the "interlayer insulation layer" in the present specification include a cured product of a resin film for interlayer insulation, a cured product of a composite film, and the like. In addition, in this specification, a "layer" includes a layer which is partially missing, and a layer in which a via or a pattern is formed.

[Thermosetting resin composition]
The thermosetting resin composition of the present embodiment contains an inorganic filler (A), a structural unit derived from a maleimide compound (b1) having at least two N-substituted maleimide groups, and a structural unit derived from a diamine compound (b2). It contains the polyimide compound (B) and the elastoma (C), and has an elastic coefficient of 8.0 to 12.0 GPa.
The thermosetting resin composition of the present embodiment not only contains the above-mentioned components, but also can significantly reduce the dielectric loss tangent by adjusting the elastic modulus within a specific range, resulting in a low dielectric loss tangent. It is possible to achieve both dielectric loss tangent and high elasticity at a high level. Therefore, the cured product obtained from the thermosetting resin composition has excellent high-frequency characteristics and can suppress the occurrence of warpage and cracks.

<Inorganic filler (A)>
The inorganic filler (A) 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 further reducing the coefficient of thermal expansion. Examples of silica include spherical silica, amorphous silica, fused silica, crystalline silica, synthetic silica and the like.

The shape of the inorganic filler (A) may be spherical, crushed, needle-shaped or plate-shaped, but the dispersibility in the thermosetting resin composition is improved, and the thermosetting resin composition is used in an organic solvent. Spherical from the viewpoints of improving dispersibility in the resin varnish in which the resin varnish is dissolved or dispersed, improving the fluidity by reducing the viscosity of the resin varnish, and suppressing the increase in surface roughness of the insulating layer formed from the thermosetting resin composition. It is preferable to have.

The average particle size of the inorganic filler (A) is preferably 1.0 μm or less, more preferably 0.8 μm or less. When the average particle size is 1.0 μm or less, the adhesive layer of the insulating layer formed from the thermosetting resin composition tends to have excellent adhesiveness to the plated copper. The average particle size of the inorganic filler (A) is preferably 0.01 μm or more, more preferably 0.05 μm or more, and even more preferably 0.1 μm or more. When the average particle size is 0.01 μm or more, the increase in viscosity when the thermosetting resin composition is used as a resin varnish is suppressed, and the handleability tends to be excellent.
The 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%, and the laser diffraction scattering method is used. It can be measured with the particle size distribution measuring device or the like.

If necessary, a coupling agent may be used for the purpose of improving the dispersibility of the inorganic filler (A) and the adhesiveness between the inorganic filler (A) and the organic component in the thermosetting resin composition. good. Examples of the coupling agent include a silane coupling agent, a titanate coupling agent and the like. 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 (A) and improving the adhesiveness between the inorganic filler (A) and the organic component. These may be used alone or in combination of two or more.
When a coupling agent is used, the amount used is not particularly limited, but from the viewpoint of more effectively exerting the features of the inorganic filler (A), 0. 1 to 5 parts by mass is preferable, and 0.5 to 3 parts by mass is more preferable.
When a coupling agent is used, the addition method may be a so-called integral blend treatment method in which the inorganic filler (A) is added to the thermosetting resin composition and then the coupling agent is added. However, from the viewpoint of more effectively expressing the features of the inorganic filler (A), a method of surface-treating the coupling agent in advance with respect to the inorganic filler before compounding is preferable.

The inorganic filler (A) is preferably used in the state of a slurry previously dispersed in an organic solvent from the viewpoint of enhancing the dispersibility in the thermosetting resin composition. The organic solvent used in the slurry of the inorganic filler (A) is not particularly limited, but for example, the organic solvent exemplified in the production of the polyimide compound (B) described later 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 higher dispersibility.
The solid content concentration of the slurry of the inorganic filler (A) is not particularly limited, but is preferably 50 to 80% by mass, preferably 60 to 75% by mass, for example, from the viewpoint of sedimentation and dispersibility of the inorganic filler (A). Is more preferable.

The content of the inorganic filler (A) in the thermosetting resin composition of the present embodiment can be appropriately selected depending on the desired properties and functions, but is 40 to 90 mass by mass with respect to the solid content of the thermosetting resin composition. % Is preferable, 60 to 85% by mass is more preferable, and 65 to 80% by mass is further preferable. When the content of the inorganic filler (A) is 40% by mass or more, both a low coefficient of thermal expansion and a high elastic modulus can be achieved at the same time, and the amount of warpage during mounting can be reduced. Further, when it is 90% by mass or less, the viscosity of the resin varnish can be kept good.
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.

<Polyimide compound (B)>
The polyimide compound (B) is a structural unit derived from a maleimide compound (b1) having at least two N-substituted maleimide groups (hereinafter, also referred to as “component (b1)”) and a diamine compound (b2) (hereinafter, “component (b1)”. It has a structural unit derived from b2) ”).

(Maleimide compound having at least two N-substituted maleimide groups (b1))
The component (b1) is not particularly limited, and is, for example, bis (4-maleimidephenyl) methane, polyphenylmethane maleimide, 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-maleimide) Phenoxy) phenyl] propane, 1,6-bismaleimide- (2,2,4-trimethyl) hexane and the like. These may be used alone or in combination of two or more. Among these, bis (4-maleimidephenyl) methane is preferable because it is inexpensive, and it has excellent dielectric properties and low water absorption. Therefore, 3,3'-dimethyl-5,5'-diethyl-4, 4'-Diphenylmethane bismaleimide is preferable, and 2,2-bis [4- (4-maleimide) is excellent in mechanical properties such as high adhesion to a conductor, elongation of cured product, breaking strength, elastic modulus, and dielectric property. Phenoxy) phenyl] propane and 1,6-bismaleimide- (2,2,4-trimethyl) hexane are preferred.

Examples of the structural unit derived from the component (b1) 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 (b1), and * indicates the binding part.
The residue refers to the structure of a portion of the raw material component excluding the functional group (maleimide group in the component (b1)) provided for bonding.

The ^{residue represented by A 1} is preferably a divalent group represented by the following general formulas (2), (3), (4) or (5).

（式中、Ｒ^１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。）

(In the formula, R ¹ independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom.)

（式中、Ｒ^２及びＲ^３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し、Ａ^２は炭素数１〜５のアルキレン基若しくはアルキリデン基、エーテル基、スルフィド基、スルフォニル基、カルボオキシ基、ケトン基、単結合又は下記一般式（３−１）で表される基である。）

(In the formula, R ² and R ³ independently represent a hydrogen atom, an aliphatic hydrocarbon group ^{having 1 to 5 carbon atoms or a halogen atom, and A 2} is an alkylene group or an alkylidene group having 1 to 5 carbon atoms and an ether. A group, a sulfide group, a sulfonyl group, a carbooxy group, a ketone group, a single bond or a group represented by the following general formula (3-1).)

（式中、Ｒ^４及び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し、Ａ^３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、カルボオキシ基、ケトン基又は単結合である。）

(In the formula, R ⁴ and R ⁵ each independently represent a hydrogen atom, an aliphatic hydrocarbon group ^{having 1 to 5 carbon atoms or a halogen atom, and A 3} is an alkylene group having 1 to 5 carbon atoms and an isopropylidene group. It is an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a ketone group or a single bond.)

（式中、ｉは１〜１０の整数である。）

(In the formula, i is an integer from 1 to 10.)

（式中、Ｒ^６及びＲ^７は各々独立に、水素原子又は炭素数１〜５の脂肪族炭化水素基を示し、ｊは１〜８の整数である。）

(In the formula, R ⁶ and R ⁷ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and j is an integer of 1 to 8.)

R ^{1 in} the general formula ( ² ), R 2 and R ^{3 in the general formula (3), R 4} and R ⁵ in the general formula (3-1) ^{, R 6} and R ^{7 in the} general formula (5). Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms shown in the above include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group and the like. Can be mentioned. The aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms or a methyl group.
The general formula (3) A ² and general formula (3-1) alkylene group of 1 to 5 carbon atoms represented by A ³ in in, methylene group, ethylene group, propylene group, butylene group, pentylene group and the like Can be mentioned.
^{Examples of the alkylidene group having 1 to 5 carbon atoms represented by A 2} in the general formula (3) include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, and a pentylidene group.

(Diamine compound (b2))
The component (b2) is not particularly limited as long as it is a compound having two amino groups, and is, for example, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4. '-Diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-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'-diphenylmethanediamine, 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-bis (4-aminophenyl) fluorene and the like can be mentioned. These may be used alone or in combination of two or more.
Among these, 4,4'-diaminodiphenylmethane and 4,4'-diamino-3,3'are highly soluble in organic solvents, have a high reaction rate during synthesis, and can have high heat resistance. -Dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4'-[1,3-phenylenebis ( 1-Methylethylidene)] bisaniline, 4,4'-[1,4-phenylenebis (1-methylethylidene)] bisaniline is preferable, and from the viewpoint of excellent dielectric properties and low water absorption, 3,3'- Didimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide is preferable, and 2,2-bis [4] is excellent in mechanical properties such as high adhesion to a conductor, elongation of a cured product, and breaking strength. -(4-Maleimidephenoxy) phenyl] propane is preferred. Further, in addition to the above-mentioned excellent solubility, reaction rate, heat resistance, and high adhesiveness to a conductor, excellent high-frequency characteristics and low hygroscopicity can be exhibited, which is 4,4'-[1,3. -Phenylenebis (1-methylethylidene)] bisaniline and 4,4'-[1,4-phenylenebis (1-methylethylidene)] bisaniline are more preferred.

Examples of the structural unit derived from the component (b2) include a group represented by the following general formula (6-1), a group represented by the following general formula (6-2), and the like.

In the general formula (6-1) and (6-2), ^{A 4} represents a residue of component (b2), * represents a bonding unit.

The residue A ⁴ is shown, is preferably a divalent group represented by the following general formula (7).

（式中、Ｒ^８及びＲ^９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し、Ａ^５は炭素数１〜５のアルキレン基若しくはアルキリデン基、エーテル基、スルフィド基、スルフォニル基、カルボオキシ基、ケトン基、フルオレニレン基、単結合、下記一般式（７−１）又は下記一般式（７−２）で表される基である。）

(In the formula, R ⁸ and R ⁹ 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, and A ⁵ has a carbon number of carbon atoms. 1 to 5 alkylene group or alkylidene group, ether group, sulfide group, sulfonyl group, carbooxy group, ketone group, fluorenylene group, single bond, represented by the following general formula (7-1) or the following general formula (7-2) It is the group to be done.)

（式中、Ｒ^１０及びＲ^１１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し、Ａ^６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、カルボオキシ基、ケトン基又は単結合である。）

(In the formula, R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an aliphatic hydrocarbon group ^{having 1 to 5 carbon atoms or a halogen atom, and A 6} is an alkylene group having 1 to 5 carbon atoms and an isopropylidene group. It is an m- or p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a ketone group or a single bond).

（式中、Ｒ^１２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し、Ａ^７及びＡ^８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、カルボオキシ基、ケトン基又は単結合である。）

(In the formula, R ¹² independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and A ⁷ and A ⁸ are an alkylene group having 1 to 5 carbon atoms and an isopropylidene group. It is an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a ketone group or a single bond.)

Aliphatic hydrocarbons having 1 to 5 carbon atoms represented by R ⁸ and R ^{9 in} the general formula (7), R ¹⁰ and R ^{11 in} the general formula (7-1), and R ^{12 in the general formula (7-2).} The hydrogen group is described in the same manner as the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by ^{R 1} in the general formula (2).
The alkylene groups having 1 to 5 carbon atoms represented by A ^{5 in} the general formula (7), A ^{6 in} the general formula (7-1), and A ⁷ and A ^{8 in the general formula (7-2) are described above.} It will be described in the same manner as the alkylene group having 1 to 5 carbon atoms represented by ^{A 2} in the general formula (3).
The alkylidene group having 1 to 5 carbon atoms represented by A ⁵ in formula (7), is described as with an alkylidene group having 1 to 5 carbon atoms A ² represents in the general formula (3).

The polyimide compound (B) contains a polyaminobismaleimide compound represented by the following general formula (8) from the viewpoints of solubility in an organic solvent, high frequency characteristics, high adhesiveness to a conductor, moldability of a film, and the like. Is preferable.

（式中、Ａ^９は前記一般式（１−１）のＡ^１と同様に説明され、Ａ^１０は前記一般式（６−１）のＡ^４と同様に説明される。）

(In the formula, A ⁹ is described in the same manner as ^{A 1 in the} general formula (1-1) ^{, and A 10} is described in the same manner as ^{A 4 in the} general formula (6-1).)

(Method for producing polyimide compound (B))
The polyimide compound (B) can be produced, for example, by reacting the component (b1) with the component (b2).
The reaction between the component (b1) and the component (b2) is preferably carried out in an organic solvent. The organic solvent is not particularly limited, and for example, alcohols such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; toluene, Aromatic hydrocarbons such as xylene and mesitylen; esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate and ethyl acetate; N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2- Examples thereof include nitrogen-containing substances such as pyrrolidone. These may be used alone or in combination of two or more. Among these organic solvents, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N, N-dimethylformamide, and N, N-dimethylacetamide are preferable from the viewpoint of solubility.

Polyimide compound in the preparation of (B), the equivalent ratio (Tb2 / Tb1) of the -NH ₂ group of the maleimide group equivalent (Tb1) and component (b2) equivalents of component (b1) (Tb2), 0.05 ~ 1.0 is preferable, and 0.1 to 0.8 is more preferable. By reacting the component (b1) and the component (b2) within the above range, good high frequency characteristics, heat resistance, flame retardancy and glass transition temperature can be obtained.

When the component (b1) and the component (b2) are reacted, a reaction catalyst can be used if necessary. The reaction catalyst is not particularly limited, but for example, an acidic catalyst such as p-toluenesulfonic acid; amines such as triethylamine, pyridine and tributylamine; imidazoles such as methylimidazole and phenylimidazole; phosphorus-based such as triphenylphosphine. Examples include catalysts. These may be used alone or in combination of two or more. When the reaction catalyst is used, the amount used is not particularly limited, but for example, it is used in the range of 0.01 to 5.0 parts by mass with respect to 100 parts by mass in total of the component (b1) and the component (b2). can do.

A polyimide compound (B) is obtained by charging a predetermined amount of the component (b1), the component (b2), an organic solvent and, if necessary, a reaction catalyst and the like into a synthesis kettle and causing a Michael addition reaction. The reaction conditions in this step are not particularly limited, but from the viewpoint of workability such as reaction rate and suppression of gelation, for example, the reaction temperature is preferably 50 to 160 ° C. and the reaction time is preferably 1 to 10 hours. ..
In this step, the above-mentioned organic solvent may be added or concentrated to adjust the solid content concentration and solution viscosity of the reaction raw material. The solid content concentration of the reaction raw material is not particularly limited, but is preferably 10 to 90% by mass, 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, good solubility is obtained, stirring efficiency is good, and gelation is less likely to occur.
Further, after the production of the polyimide compound (B), 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.

The weight average molecular weight of the polyimide compound (B) is not particularly limited, but is preferably 500 to 6,000, more preferably 1,000 to 5,000, and even more preferably 1,500 to 4,000, for example. The weight average molecular weight of the polyimide compound (B) can be measured by the method described in Examples.

The content of the polyimide compound (B) in the thermosetting resin composition of the present embodiment is 20 to 95% by mass based on the total mass of all the resin components contained in the thermosetting resin composition of the present embodiment. Preferably, 40 to 90% by mass is more preferable, and 65 to 85% by mass is further preferable.

<Elastomer (C)>
The elastomer (C) is not particularly limited, and for example, polybutadiene-based elastomer, styrene-based elastomer, olefin-based elastomer, urethane-based elastomer, polyester-based elastomer, polyamide-based elastomer, acrylic-based elastomer, silicone-based elastomer, and these elastomers. Derivatives and the like can be mentioned. These may be used alone or in combination of two or more.

As the elastomer (C), one having a reactive functional group at the molecular terminal or in the molecular chain can be used. The reactive functional group is, for example, one or more selected from the group consisting of a maleic anhydride group, an epoxy group, a hydroxyl group, a carboxy group, an amino group, an 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 between the inorganic filler (A) and the resin component when the interlayer insulating layer is formed tends to be suppressed. From the same viewpoint, the elastomer (C) 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, those having a reactive functional group are used from the viewpoint of improving the compatibility with the resin and suppressing the separation of the inorganic filler (A) 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, Examples thereof include glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, and among these, maleic anhydride is preferable.
When the elastoma (C) 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 (C) 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 (A) 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 dielectric loss tangent of the thermosetting resin composition tends to be lower. When the elastomer (C) is modified with maleic anhydride, a group derived from maleic anhydride contained in one molecule of the elastomer (C) (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.
Polybutadiene-based elastomers are available as commercial products, and specific examples thereof include "POLYVEST (registered trademark) MA75" and "POLYVEST (registered trademark) EP MA120" (all manufactured by Evonik Industries, Inc., trade name). Examples thereof include "Ricon (registered trademark) 130MA8", "Ricon (registered trademark) 131MA5", and "Ricon (registered trademark) 184MA6" (all manufactured by Clay Valley Co., Ltd., trade name).

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 elastoma include styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene, in addition to styrene. Styrene-based elastoma is available as a commercial product, and specific examples thereof include "Toughprene (registered trademark)", "Asaprene (registered trademark) T", "Toughtech (registered trademark) H", and "Toughtech (registered trademark)". ) MP10 ”,“ Tough Tech (registered trademark) M1911 ”,“ Tough Tech (registered trademark) M1913 ”(above, manufactured by Asahi Kasei Chemicals Co., Ltd.),“ Epofriend (registered trademark) AT501 ”,“ Epofriend (registered trademark) CT310 ” (The above is manufactured by Daicel Co., Ltd.) and the like.

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. Polymers (EPR), ethylene-propylene-diene copolymers (EPDM) and the like are preferably mentioned. 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, methylenenorbornene, etylidenenorbornene, butadiene, and isoprene. .. Further, carboxy-modified NBR obtained by copolymerizing methacrylic acid with a butadiene-acnillonitrile copolymer can be mentioned. Olefin-based elastomas are available as commercial products, and specific examples thereof include "PB3600", "PB4700" (all manufactured by Daicel Corporation), "G-1000", "G-2000", and "G-". 3000 ”,“ JP-100 ”,“ JP-100 ”,“ BN-1015 ”,“ TP-1001 ”,“ TEA-1000 ”,“ EA-3000 ”,“ TE-2000 ”,“ EMA-3000 ” (The above is manufactured by Nippon Soda Co., Ltd.), "Denalex (registered trademark) R45" (manufactured by Nagase ChemteX Corporation), and the like.

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 high molecular weight (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.
Urethane-based elastomers are available as commercial products, and specific examples thereof include "PANDEX (registered trademark) T-2185" and "PANDEX (registered trademark) T-2983N" (all manufactured by DIC Corporation). Can be mentioned.

Examples of the polyester-based elastoma 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. These may be used alone or in combination of two or more.
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. Alicyclic diols such as bisphenol A, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) propane, aromatic diols such as resorcin and the like. These may be used alone or in combination of two or more.

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 include "Hitrel (registered trademark)" (Dupont Toray Co., Ltd.), "Perprene (registered trademark)" (Toyo Spinning Co., Ltd.), and "Esper (registered trademark)" (Hitachi Kasei Co., Ltd.). ) Etc. can be mentioned.

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.
Polyamide-based elastoma is available as a commercial product, and specific examples thereof include "UBE Polyamide Elastoma" (manufactured by Ube Industries, Ltd.), "Dyamide (registered trademark)" (manufactured by Daicel Evonik Co., Ltd.), and "PEBAX". (Registered Trademark) ”(Toray Co., Ltd.),“ Grillon (Registered Trademark) ELY ”(M.Schemy Japan Co., Ltd.),“ Novamid (Registered Trademark) ”(Mitsubishi Chemical Co., Ltd.) ) ”(Manufactured by DIC Co., Ltd.),“ BPAM-01 ”,“ BPAM-155 ”(all manufactured by Nippon Kayaku Co., Ltd.) and the like.

Examples of the acrylic elastomer include a polymer of a raw material monomer containing an acrylic acid ester as a main component. Preferable examples of the acrylic acid 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.

Silicone-based elastomers are elastomers containing organopolysiloxane as a main component, and are classified into, for example, polydimethylsiloxane-based, polymethylphenylsiloxane-based, polydiphenylsiloxane-based, and the like. Silicone-based elastomas are available as commercial products, and specific examples thereof include "X-22-163B", "X-22-163C", "X-22-1821", and "X-22-162C". (Shin-Etsu Chemical Co., Ltd.), Core-shell type silicone rubber "SY series" (Asahi Kasei Wacker Silicone Co., Ltd.), "SE series", "CY series", "SH series" (Toray Dow Corning Co., Ltd.) (Made by company), etc.

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.

The weight average molecular weight of the elastomer (C) is preferably 500 to 50,000, more preferably 1,000 to 30,000. When the weight average molecular weight of the elastomer (C) 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 (C) is 50,000 or less, the separation of the inorganic filler (A) and the resin component when the interlayer insulating layer is formed tends to be suppressed. As the weight average molecular weight of the elastomer (C), the method for measuring the weight average molecular weight of the polyimide compound (B) described in Examples can be applied.

The content of the elastomer (C) component in the thermosetting resin composition of the present embodiment is 1 to 70% by mass based on the total mass of all the resin components contained in the thermosetting resin composition of the present embodiment. Preferably, 5 to 50% by mass is more preferable, and 10 to 30% by mass is further preferable. By setting the content of the elastomer (C) within the above range, the dielectric loss tangent is low, the handleability when formed into a film is excellent, and the inorganic filler (A) and the resin component when the interlayer insulating layer is formed Separation tends to be suppressed.

The total content of the polyimide compound (B) and the elastomer (C) in the thermosetting resin composition of the present embodiment is not particularly limited, but is 5% by mass or more with respect to the solid content of the thermosetting resin composition. Is preferable, 10% by mass or more is more preferable, and 15% by mass or more is further preferable. The upper limit of the content is not particularly limited, and may be 50% by mass or less, or 40% by mass or less.

<Other ingredients>
The thermosetting resin composition of the present embodiment may contain a flame retardant, a curing accelerator, or the like, if necessary.
By incorporating a flame retardant into the thermosetting resin composition of the present embodiment, better flame retardancy can be imparted. The flame retardant is not particularly limited, and examples thereof include a chlorine-based flame retardant, a bromine-based flame retardant, a phosphorus-based flame retardant, and a metal hydrate-based flame retardant. From the viewpoint of environmental compatibility, phosphorus-based flame retardants or metal hydrate-based flame retardants are preferable.
By including an appropriate curing accelerator in the thermosetting resin composition of the present embodiment, the curability of the thermosetting resin composition is improved, and the dielectric property, heat resistance, high elastic modulus, glass transition temperature, etc. Can be further improved. The curing accelerator is not particularly limited, and examples thereof include various imidazole compounds and derivatives thereof; various tertiary amine compounds; various quaternary ammonium compounds; and various phosphorus compounds such as triphenylphosphine.
In addition to the above, the thermosetting resin composition of the present embodiment may contain additives such as an antioxidant and a flow conditioner.

<Elastic modulus>
The elastic modulus of the cured product of the thermosetting resin composition of the present embodiment is 8.0 to 12.0 GPa, preferably 8.0 to 11.5 GPa, preferably 8 from the viewpoint of reducing the amount of warpage during mounting. .0 to 11.0 GPa is more preferable.
The elastic modulus of the cured product was measured using a wide-area dynamic viscoelasticity measuring device (manufactured by Rheology, trade name: DVE-V4) in a measurement temperature range of 40 to 300 ° C., a heating rate of 5 ° C./min, and vibration. It is a value of 40 ° C. of the storage elastic modulus (E') measured under the condition of a frequency of 10 Hz.
Further, the cured product used for the measurement of the elastic modulus is the thermosetting resin composition of the present embodiment in air, preferably 160 to 220 ° C, more preferably 170 to 210 ° C, still more preferably. It is cured at 180 to 200 ° C., preferably for 60 to 300 minutes, more preferably for 120 to 240 minutes, and even more preferably for 150 to 210 minutes.

[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; and 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 is limited to adhesive films, insulating resin sheets such as prepregs, circuit boards, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, fill-in-the-blank resins, and parts. It can be used in a wide range of applications that require an interlayer insulating layer such as an embedded resin. 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 produced, for example, as follows.
When producing a resin film for interlayer insulation, first, an inorganic filler (A), a polyimide compound (B), an elastoma (C), and other components used as necessary are dissolved or dispersed in an organic solvent. It is preferable to use a resin varnish (hereinafter, also referred to as “varnish for resin film for interlayer insulation”).

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; and acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate and carbitol acetate. (Di) ethylene glycol monoalkyl ether or propylene glycol monoalkyl ether such as cellosolve, butylcarbitol, propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Examples thereof include amide-based solvents. These organic solvents may be used alone or in combination of two or more.
The blending amount of the organic solvent is preferably 10 to 60% by mass, more preferably 10 to 35% by mass, based on the total mass of the varnish for the resin film for interlayer insulation.

The interlayer insulating resin film varnish thus produced 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, but for example, in the case of a varnish for an interlayer insulating resin film containing 10 to 35% by mass of an organic solvent, the varnish is dried at 50 to 150 ° C. for about 2 to 10 minutes. , A resin film for interlayer insulation can be preferably formed. It is preferable to dry the resin film for interlayer insulation after drying so that the content of the volatile component (mainly an organic solvent) is 10% by mass or less, and it is dried so that it is 5.0% by mass or less. Is more preferable.

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 larger 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.

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]
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.

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.

<First resin layer>
The first resin layer contains the thermosetting resin composition of the present embodiment. The first resin layer is provided between the circuit board and the adhesion auxiliary layer in the case of manufacturing a multilayer printed wiring board using the composite film of the present embodiment, for example, and is provided on the conductor layer of the circuit board and above it. It is used to insulate the layer. 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.

<Second resin layer>
The second resin layer is located between the cured product of the first resin layer containing the thermosetting resin composition of the present embodiment and the conductor layer in the printed wiring board of the present embodiment described later. It is provided for the purpose of improving the adhesiveness with the conductor layer. 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. Therefore, from the viewpoint of forming fine wiring, it is preferable to provide the second resin layer.

The second resin layer is not particularly limited as long as it improves the adhesiveness with the conductor layer, but for example, even if the surface roughness is small, the adhesiveness with the plated copper is excellent and the dielectric positive contact is low. From the viewpoint of obtaining an interlayer insulating layer, it contains a polyfunctional epoxy resin (D), an active ester curing agent (E), and a phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (F) (hereinafter, also referred to as “component (F)”). , It is preferable to contain a second thermosetting resin composition.

<Multifunctional epoxy resin (D)>
The polyfunctional epoxy resin (D) is not particularly limited as long as it is a resin having two or more epoxy groups, and is, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, and a cresol novolac type epoxy. Resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, aralkylnovolac type epoxy resin, fluorene type epoxy resin, xantene type epoxy resin And so on. From the viewpoint of adhesiveness to plated copper, it is preferable to have a biphenyl structure, and a polyfunctional epoxy resin having a biphenyl structure or an aralkyl novolac type epoxy resin having a biphenyl structure is more preferable.
As the polyfunctional epoxy resin (D), a commercially available product may be used. Commercially available polyfunctional epoxy resins (D) include "NC-3000-H", "NC-3000-L", and "NC" manufactured by Nippon Kayaku Co., Ltd., which are aralkyl novolac type epoxy resins having a biphenyl structure. -3100 ”,“ NC-3000 ”and the like.
The polyfunctional epoxy resin (D) may be used alone or in combination of two or more.

The epoxy equivalent of the polyfunctional epoxy resin (D) is not particularly limited, but is preferably 150 to 450 g / mol, more preferably 200 to 400 g / mol, and even more preferably 250 to 350 g / mol from the viewpoint of adhesiveness.

The content of the polyfunctional epoxy resin (D) in the second thermosetting resin composition is not particularly limited, but is 10 to 10 in the total mass of all the resin components contained in the second thermosetting resin composition. 90% by mass is preferable, 20 to 80% by mass is more preferable, and 30 to 70% by mass is further preferable. When the content of the polyfunctional epoxy resin (D) is 10% by mass or more, better adhesive strength with plated copper is obtained, and when it is 90% by mass or less, lower dielectric loss tangent tends to be obtained. be.

<Active ester curing agent (E)>
The active ester curing agent (E) has one or more ester groups in one molecule and has a curing action of an epoxy resin.
The active ester curing agent (E) is not particularly limited, and examples thereof include an ester compound obtained from an aliphatic or aromatic carboxylic acid and an aliphatic or aromatic hydroxy compound.
Among these, ester compounds obtained from aliphatic carboxylic acids, aliphatic hydroxy compounds and the like tend to be soluble in organic solvents and highly compatible with epoxy resins by containing aliphatic chains.
Further, an ester compound obtained from an aromatic carboxylic acid, an aromatic hydroxy compound or the like tends to have an aromatic ring to enhance heat resistance.
Examples of the active ester curing agent (E) include a phenol ester compound, a thiophenol ester compound, an N-hydroxyamine ester compound, and an esterified compound of a heterocyclic hydroxy compound.
More specifically, for example, an aromatic ester obtained by a condensation reaction of an aromatic carboxylic acid and a phenolic hydroxyl group can be mentioned, and aromatics such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, and diphenylsulfonic acid can be mentioned. An aromatic carboxylic acid component selected from those in which 2 to 4 hydrogen atoms in the ring are substituted with a carboxy group, a monovalent phenol in which one of the hydrogen atoms in the aromatic ring is substituted with a hydroxyl group, and a hydrogen atom in the aromatic ring. Aromatic esters obtained by a condensation reaction between an aromatic carboxylic acid and a phenolic hydroxyl group are preferable, using a mixture of 2 to 4 of the above with a polyvalent phenol substituted with a hydroxyl group as a raw material. That is, an aromatic ester having a structural unit derived from the aromatic carboxylic acid component, a structural unit derived from the monovalent phenol, and a structural unit derived from the polyhydric phenol is preferable.
As the active ester curing agent (E), a commercially available product may be used. Commercially available products of the active ester curing agent (E) include, for example, "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" (DIC) as active ester compounds containing a dicyclopentadiene type diphenol structure. (Manufactured by Co., Ltd.), "EXB9416-70BK" (manufactured by DIC Co., Ltd.) as an active ester compound containing a naphthalene structure, "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing an acetylated product of phenol novolac, Examples of the active ester compound containing a benzoyl compound include "YLH1026" (manufactured by Mitsubishi Chemical Corporation).
The active ester curing agent (E) may be used alone or in combination of two or more.

The ester equivalent of the active ester curing agent (E) is not particularly limited, but is preferably 150 to 400 g / mol, more preferably 170 to 300 g / mol, and even more preferably 200 to 250 g / mol.

The equivalent ratio (ester group / epoxy group) of the ester group of the active ester curing agent (E) to the epoxy group of the polyfunctional epoxy resin (D) in the second thermosetting resin composition is 0.05 to 1. .5 is preferable, 0.1 to 1.3 is more preferable, and 0.2 to 1.0 is further preferable. When the equivalent ratio (ester group / epoxy group) is within the above range, the adhesive strength with the plated copper is further increased, and a lower dielectric loss tangent and a smooth surface can be obtained, which is preferable from the viewpoint of forming fine wiring. be.

<Phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (F)>
The component (F) is not particularly limited as long as it is a polybutadiene-modified polyamide resin having a phenolic hydroxyl group, but is a diamine-derived structural unit, a dicarboxylic acid-derived structural unit containing a phenolic hydroxyl group, and a phenolic hydroxyl group. It is preferable to have a structural unit derived from a dicarboxylic acid that does not contain the above and a structural unit derived from polybutadiene having a carboxy group at both ends. Specifically, those having a structural unit represented by the following general formula (i), a structural unit represented by the following general formula (ii), and a structural unit represented by the following general formula (iii) are preferably mentioned. ..

In the general formulas (i) to (iii), a, b, c, x, y and z are integers indicating the average degree of polymerization, respectively, and a = 2 to 10, b = 0 to 3, c = 3. ~ 30, y + z = 2 to 300 ((y + z) / x) for x = 1, and z ≧ 20 (z / y) for y = 1.
In the general formulas (i) to (iii), R'independently represents a divalent group derived from an aromatic diamine or an aliphatic diamine, and in the general formula (iii), R'' is an aromatic dicarboxylic acid. , An aliphatic dicarboxylic acid or a divalent group derived from an oligomer having a carboxy group at both ends.
The plurality of R'included in the general formulas (i) to (iii) may be the same or different. Further, when z is an integer of 2 or more, a plurality of R''s may be the same or different.
In the general formulas (i) to (iii), R'is specifically a divalent group derived from an aromatic diamine or an aliphatic diamine described later, and R'' is an aromatic group described later. It is preferably a divalent group derived from a dicarboxylic acid, an aliphatic dicarboxylic acid or an oligomer having a carboxy group at both ends.

Examples of the diamine used for forming the structural unit derived from diamine in the component (F) include aromatic diamines and aliphatic diamines.
Examples of the aromatic diamine include diaminobenzene, diaminotoluene, diaminophenol, diaminodimethylbenzene, diaminomethicylene, diaminonitrobenzene, diaminodiazobenzene, diaminonaphthalene, diaminobiphenyl, diaminodimethoxybiphenyl, diaminodiphenyl ether, diaminodimethyldiphenyl ether, and methylene. Diamine, methylenebis (dimethylaniline), methylenebis (methoxyaniline), methylenebis (dimethoxyaniline), methylenebis (ethylaniline), methylenebis (diethylaniline), methylenebis (ethoxyaniline), methylenebis (diethoxyaniline), isopropyridendianiline, Examples thereof include diaminobenzophenone, diaminodimethylbenzophenone, diaminoanthraquinone, diaminodiphenylthioether, diaminodimethyldiphenylthioether, diaminodiphenylsulfone, diaminodiphenylsulfooxide, diaminofluorene and the like.

Examples of the aliphatic diamine include ethylenediamine, propanediamine, hydroxypropanediamine, butanediamine, heptanediamine, hexanediamine, cyclopentanediamine, cyclohexanediamine, azapentanediamine, triazaundecadiamine and the like.

Examples of the dicarboxylic acid containing a phenolic hydroxyl acid used for forming a structural unit derived from a dicarboxylic acid containing a phenolic hydroxyl acid in the component (F) include hydroxyisophthalic acid, hydroxyphthalic acid, hydroxyterephthalic acid, and dihydroxy. Examples thereof include isophthalic acid and dihydroxyterephthalic acid.

Examples of the phenolic hydroxyl group-free dicarboxylic acid used to form a structural unit derived from a dicarboxylic acid that does not contain a phenolic hydroxyl group in the component (F) include aromatic dicarboxylic acid and aliphatic dicarboxylic acid at both ends. Examples thereof include an oligomer having a carboxy group.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, biphenyldicarboxylic acid, methylenedibenzoic acid, thiodibenzoic acid, carbonyldibenzoic acid, sulfonylbenzoic acid, naphthalenedicarboxylic acid and the like.
Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, methylmalonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, apple acid, tartaric acid, (meth) acryloyloxysuccinic acid, and di (meth). ) Acryloyloxysuccinic acid, (meth) acryloyloxysuccinic acid, (meth) acrylamide succinic acid, (meth) acrylamide malonic acid and the like can be mentioned.

The weight average molecular weight of the component (F) is not particularly limited, but is preferably 60,000 to 250,000, more preferably 80,000 to 200,000, for example. The weight average molecular weight of the component (F) can be determined by the same method as the weight average molecular weight of the polyimide compound (B).

The active hydroxyl group equivalent of the component (F) is not particularly limited, but is preferably 1,500 to 7,000 g / mol, more preferably 2,000 to 6,000 g / mol, and 3,000 to 5,000 g / mol. More preferred.

The component (F) contains, for example, a diamine, a dicarboxylic acid containing a phenolic hydroxyl group, a dicarboxylic acid not containing a phenolic hydroxyl group, and polybutadiene having a carboxy group at both ends in an organic solvent such as dimethylacetamide. , It is synthesized by reacting a carboxylic acid ester as a catalyst in the presence of a pyridine derivative and polycondensing a carboxy group and an amino group. Examples of each compound that can be used in the production include those described above.
The polybutadiene having carboxy groups at both ends used in the production of the component (F) is preferably an oligomer having a number average molecular weight of 200 to 10,000 and a number average molecular weight of 500 to 5,000, for example. Is more preferable.

As the component (F), a commercially available product can be used, and examples of the component (F) of the commercially available product include "BPAM-155" manufactured by Nippon Kayaku Co., Ltd.

The content of the component (F) in the second thermosetting resin composition is not particularly limited, but is 1 to 20% by mass in the total mass of all the resin components contained in the second thermosetting resin composition. Is preferable, 2 to 15% by mass is more preferable, and 3 to 10% by mass is further preferable. When the content of the component (F) is 1% by mass or more, the toughness of the thermosetting resin composition can be increased, a fine roughened shape can be obtained, and the adhesive strength with the plated copper can be enhanced. be able to. Further, when it is 20% by mass or less, the heat resistance does not decrease, and the decrease in resistance to the chemical solution during the roughening step can be prevented. In addition, sufficient adhesiveness with plated copper can be ensured.

<Phosphorus-based curing accelerator (G)>
The second thermosetting resin composition preferably further contains a phosphorus-based curing accelerator (G).
The phosphorus-based curing accelerator (G) is not particularly limited as long as it contains a phosphorus atom and promotes the reaction between the polyfunctional epoxy resin (D) and the active ester curing agent (E). Can be done.
By containing the phosphorus-based curing accelerator (G) in the second thermosetting resin composition, the curing reaction can be further sufficiently promoted. The reason for this is that by using the phosphorus-based curing accelerator (G), the electron-attracting property of the carbonyl group in the active ester curing agent (E) can be enhanced, which is more than that of the active ester curing agent (E). It is presumed that this is because the reaction with the functional epoxy resin (D) is promoted.
As described above, by containing the phosphorus-based curing accelerator (G), the second thermosetting resin composition cures the polyfunctional epoxy resin (D) and the active ester more than when other curing accelerators are used. Since the curing reaction with the agent (E) proceeds more sufficiently, it is considered that a low dielectric loss tangent can be obtained when combined with the first resin layer.

Examples of the phosphorus-based curing accelerator (G) include triphenylphosphine, diphenyl (alkylphenyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, and tris (dialkylphenyl). ) Phosphine, Tris (trialkylphenyl) phosphine, Tris (tetraalkylphenyl) phosphine, Tris (dialkoxyphenyl) phosphine, Tris (trialkoxyphenyl) phosphine, Tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine , Organic phosphines such as alkyldiarylphosphine; complexes of organic phosphines and organic borons; adjuncts of tertiary phosphines and quinones. An adduct of tertiary phosphine and quinones is preferable from the viewpoint that the curing reaction proceeds more sufficiently and high adhesiveness to plated copper can be exhibited.
The third phosphine is not particularly limited, and is, for example, tri-n-butylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-methoxy). Phosphine) phosphine and the like. Examples of quinones include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, anthraquinone and the like. An adduct of tri-n-butylphosphine and p-benzoquinone is more preferable from the viewpoint of obtaining adhesiveness to plated copper, heat resistance and a smooth surface.

As a method for producing an adduct of the tertiary phosphine and quinones, for example, a method of stirring and mixing the three phosphine and quinones as raw materials in a solvent in which both of them are dissolved, subjecting them to an addition reaction, and then isolating them. And so on. In this case, for example, the tertiary phosphine and quinones are stirred in a solvent such as methyl isobutyl ketone, methyl ethyl ketone, and ketones such as acetone in the range of 20 to 80 ° C. for 1 to 12 hours. , It is preferable to carry out an addition reaction.

One type of phosphorus-based curing accelerator (G) may be used alone, or two or more types may be used in combination. In addition, one or more curing accelerators other than the phosphorus-based curing accelerator (G) may be used in combination.

The content of the phosphorus-based curing accelerator (G) in the second thermosetting resin composition is not particularly limited, but is 0 in the total mass of all the resin components contained in the second thermosetting resin composition. .1 to 20% by mass is preferable, 0.2 to 15% by mass is more preferable, and 0.4 to 10% by mass is further preferable. When the content of the phosphorus-based curing accelerator (G) is 0.1% by mass or more, the curing reaction can be sufficiently advanced, and when it is 20% by mass or less, the homogeneity of the cured product can be maintained. ..

<Filler (H)>
The second thermosetting resin composition may contain a filler (H). Examples of the filler (H) include an inorganic filler and an organic filler.
By containing the filler (H), the scattering of the resin can be further reduced when the second resin layer is laser-processed.

The inorganic filler is not particularly limited, but for example, the same one as that exemplified as the inorganic filler (A) can be used.
The particle size of the inorganic filler is preferably small from the viewpoint of forming fine wiring on the second resin layer. From the same viewpoint, the specific surface area of the inorganic filler ^{is preferably 20 m 2} / g or more, and more preferably 50 m ² / g or more. There is no particular limitation on the upper limit of the specific surface area, from the viewpoint of easy availability, preferably 500 meters ² / g or less, 200 meters ² / g or less is more preferable.
The specific surface area can be determined by the BET method by low-temperature, low-humidity physical adsorption of an inert gas. Specifically, a molecule having a known adsorption area such as nitrogen is adsorbed on the surface of the powder particles at the temperature of liquid nitrogen, and the specific surface area of the powder particles can be obtained from the adsorption amount.
As the inorganic filler having a specific surface area of 20 m ² / g or more, a commercially available product may be used. Commercially available products include, for example, fumed silica "AEROSIL (registered trademark) R972" (manufactured by Nippon Aerosil Co., Ltd., trade name, specific surface area 110 ± 20 m ² / g), "AEROSIL (registered trademark) R202" (Japan). Aerosil Co., Ltd., trade name, specific surface area 100 ± 20 m ² / g), colloidal silica "PL-1" (Fuso Chemical Industry Co., Ltd., trade name, specific surface area 181 m ² / g), "PL-7" (Manufactured by Fuso Chemical Industry Co., Ltd., trade name, specific surface area 36 m ² / g) and the like. Further, from the viewpoint of improving the moisture resistance, it is preferable that the inorganic filler is surface-treated with a surface treatment agent such as a silane coupling agent.

The content of the inorganic filler in the second thermosetting resin composition is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, based on the solid content of the second thermosetting resin composition. Preferably, 3 to 20% by mass is more preferable, and 5 to 20% by mass is particularly preferable. When the content of the inorganic filler is 1% by mass or more, better laser workability tends to be obtained, and when it is 30% by mass or less, the adhesiveness between the second resin layer and the conductor layer becomes poor. It tends to improve.

The organic filler is not particularly limited, and is, for example, a crosslinked NBR particle obtained by copolymerizing acrylonitrile and butadiene, a copolymer of acrylonitrile butadiene such as a copolymer of acrylonitrile and butadiene and a carboxylic acid such as acrylic acid; and polybutadiene; , NBR, silicone rubber and the like as a core, and an acrylic acid derivative as a shell, so-called core-shell rubber particles and the like can be mentioned. By containing the organic filler, the extensibility of the resin layer tends to be further improved.

<Other ingredients>
In addition to the above components, the second thermosetting resin composition includes other thermosetting resins, thermoplastic resins, flame retardants, and antioxidants as necessary, as long as the effects of the present invention are not impaired. , Additives such as flow conditioner and curing accelerator can be contained.

<Support>
In the composite film of the present embodiment, a support may be further provided on the surface of the second resin layer opposite to the first resin layer.
Examples of the support include the same supports that can be used for the interlayer insulating resin film of the present embodiment.

<Manufacturing method of composite film>
The composite film of the present embodiment can be produced, for example, by a method of forming a second resin layer on the support and forming a first resin layer on the second resin layer.
For the formation of the first resin layer, the above-mentioned varnish for the resin film for interlayer insulation (here, also referred to as “varnish for the first resin layer”) can be used.
In order to form the second resin layer, a resin varnish in which the second thermosetting resin composition is dissolved or dispersed in an organic solvent (hereinafter, also referred to as “varnish for the second resin layer”) may be formed. preferable.
Examples of the method for producing the varnish for the second resin layer and the organic solvent used for producing the varnish for the second resin layer include the same organic solvents as those that can be used for the varnish for the resin film for interlayer insulation.
The blending amount of the organic solvent is preferably 70 to 95% by mass, more preferably 80 to 90% by mass, based on the total mass of the varnish for the second resin layer.

The second resin layer varnish produced in this manner is applied to the support and then heat-dried, and then the first resin layer varnish is further applied and then heat-dried. , Composite film can be formed.
The coating method of the varnish for the second resin layer or the varnish for the first resin layer and the drying conditions after coating the varnish are the coating method and the drying in the method for producing the resin film for interlayer insulation of the present embodiment. Same as the conditions.

The thickness of the first resin layer formed in the composite film of the present embodiment may be appropriately determined according to the required performance, but from the viewpoint of embedding the conductor layer of the circuit board, the thickness of the conductor layer of the circuit board. The above is preferable. 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 first resin layer is preferably 10 to 100 μm. The thickness of the second resin layer is preferably 1 to 15 μm.

A protective film may be provided on the surface of the first resin layer on which the second resin layer is not provided. The thickness of the protective film is not particularly limited, but may be, for example, 1 to 40 μm. By providing the protective film, it is possible to prevent dust and the like from adhering to the surface of the first resin layer and scratches. The composite film can also be rolled up and stored.

In the composite film of the present embodiment, the dielectric loss tangent of the cured product at 5 GHz is preferably 0.010 or less, more preferably 0.008 or less, further preferably 0.006 or less, and 0. It is particularly preferable that it is 005 or less. The dielectric loss tangent of the cured product of the composite film of the present embodiment can be obtained by the method described in the examples. Further, the curing conditions of the cured product used for measuring the dielectric loss tangent are the same as the curing conditions of the cured product used for measuring the elastic modulus of the thermosetting resin composition of the present embodiment.

[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 of the present embodiment or a cured product of the composite film of the present embodiment. In other words, the printed wiring board of the present embodiment has an interlayer insulating layer, and at least one of the interlayer insulating layers contains a cured product of the thermosetting resin composition of the present embodiment.
Hereinafter, a method of manufacturing a multilayer printed wiring board by laminating a resin film for interlayer insulation or a composite film of the present embodiment on a circuit board will be described.

The method for manufacturing a multilayer printed wiring board according to the present embodiment includes the following steps (1) to (5), and after the step (1), the step (2) or the step (3), the support is attached. It may be peeled off or removed.
Step (1): Laminating the interlayer insulating resin film or composite film of the present embodiment on one side or both sides of the circuit board Step (2): Heat-curing the interlayer insulating resin film or composite film to form an interlayer insulating layer. Step (3): Drilling a hole in the circuit board on which the interlayer insulating layer is formed Step (4): Roughening the surface of the interlayer insulating layer Step (5): Roughening the interlayer insulating layer The process of plating on the surface

<Process (1)>
The step (1) is a step of laminating the interlayer insulating resin film or composite film of the present embodiment on one side or both sides of the circuit board. Examples of the device for laminating the resin film for interlayer insulation or the composite film include a vacuum laminator. A commercially available product can be used as the vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum applicator manufactured by Nichigo Morton Co., Ltd., a vacuum pressurized laminator manufactured by Meiki Seisakusho Co., Ltd., and a vacuum pressurizing laminator manufactured by Hitachi Industries, Ltd. Roll type dry coater, vacuum laminator manufactured by Hitachi AIC Co., Ltd., etc. can be mentioned.

In the lamination, when the interlayer insulating resin film or composite film has a protective film, after removing the protective film, the interlayer insulating resin film or composite film is pressed and / or heated on the circuit board. Crimping.
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.
The conditions for laminating are that the interlayer insulating resin film or 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. It may be laminated under a reduced pressure of 8 × 10 ^{4 to} 107.9 × 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.

<Process (2)>
The step (2) is a step of thermosetting the interlayer insulating resin film or composite film to form an interlayer insulating layer. The conditions for heat curing are not particularly limited, but can be selected, for example, at 170 to 220 ° C. for 20 to 80 minutes. After the thermosetting, 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 a drill, a laser, a 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. In this step, a semi-additive method in which 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. 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, "Mech Etch Bond (registered trademark) CZ-8100" and "Mech Etch Bond (registered trademark) CZ-" which are organic acid-based microetching agents. 8101 ”,“ MEC Etch Bond (registered trademark) CZ-5480 ”(above, manufactured by MEC Co., Ltd., trade name) and the like can be mentioned.

The thermosetting resin composition, the resin film for interlayer insulation, the composite film, and the printed wiring board of the present embodiment can be particularly preferably used for electronic devices that handle high frequency signals of 1 GHz or higher, and particularly high frequency signals of 5 GHz or higher. It can be suitably used for electronic devices that handle high-frequency signals of 10 GHz or higher or high-frequency signals of 30 GHz or higher.

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 of 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.

Manufacturing example 1
<Manufacturing of polyimide compound (B)>
1,6-Bismaleimide- (2,2,4-trimethyl) hexane (Daiwa Kasei Kogyo Co., Ltd.) in a glass flask container with a volume of 1 liter that can be heated and cooled equipped with a thermometer, a reflux condenser, and a stirrer. Manufactured by, trade name: BMI-TMH) 385.377 g, 2,2-bis [4- (4-maleimide phenoxy) phenyl] propane (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000) 1611.619 g, 4 , 4'-[1,3-phenylenebis (1-methylethylidene)] bisaniline (manufactured by Mitsui Kagaku Fine Co., Ltd., trade name: bisaniline M) 278.004 g and propylene glycol monomethyl ether 3500 g were added, and the liquid temperature was 120 ° C. The reaction was carried out under stirring for 3 hours while refluxing with. Then, by gel permeation chromatography (GPC), it was confirmed that the weight average molecular weight of the reaction product was 3,000, and the polyimide compound (B) (solid content concentration 65% by mass) was cooled and filtered by 200 mesh. Manufactured.

<Measurement method of weight average molecular weight>
The weight average molecular weight of the obtained polyimide compound (B) was converted by GPC from a calibration curve using standard polystyrene. 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 to approximate with 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 of varnish for second resin layer>
Manufacturing example 2
After blending and mixing the compositions according to the compounding composition shown in Table 1 (the content in the table is the content of the resin composition with respect to the solid content, and in the case of a solution or dispersion, it is the solid content equivalent amount). It was diluted with methyl ethyl ketone so that the solid content concentration became 18% by mass. Then, it was dispersed by the nanomizer treatment to obtain a varnish for the second resin layer.

The details of each component shown in Table 1 are as follows.
NC-3000-H: Aralkyl novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name, epoxy equivalent 289 g / mol)
HPC-8000-65T: Active ester curing agent (manufactured by DIC Corporation, trade name, ester equivalent: 223 g / mol, diluted toluene, solid content concentration: 65% by mass)
BPAM-155: A mixed solvent (dimethyl) of dimethylacetamide and cyclohexanone of phenolic hydroxyl group-containing polybutadiene-modified polyamide resin "BPAM-155" manufactured by Nippon Kayaku Co., Ltd. so that the solid content concentration is 1.6% by mass. Acetamide: Cyclohexanone dissolved in 7: 3) ・ Addition of tri-n-butylphosphine and p-benzoquinone: manufactured by Kurokin Kasei Co., Ltd., trade name "TBP2"
Aerosil (registered trademark) R972: Fumed silica (manufactured by Nippon Aerosil Co., Ltd., trade name, specific surface area 110 ± 20 m ² / g)
-Yoshinox (registered trademark) BB: 4,4'-butylidenebis- (6-t-butyl-3-methylphenol) (manufactured by Mitsubishi Chemical Corporation, trade name)
-BYK-310: Silicon-based surface conditioner (manufactured by Big Chemie Japan Co., Ltd., product name)
-YX7200: Phenoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name, diluted methyl ethyl ketone, solid content concentration 35% by mass)

[Manufacturing of varnish for first resin layer]
Manufacturing example 3
(Manufacturing of varnish A for the first resin layer)
Inorganic filling so as to have the compounding composition shown in Table 2 (the content (% by mass) in the table is the content of the resin composition with respect to the solid content, and in the case of a solution or dispersion, it is the solid content equivalent amount). The material (A) and the elastoma (C) were mixed. The polyimide compound (B) produced in Production Example 1 was mixed therewith and dissolved at room temperature with a high-speed rotary mixer. After visually confirming that the polyimide compound (B) was dissolved, a flame retardant, an antioxidant, a flow conditioner, and a curing accelerator were mixed so as to have the composition shown in Table 2. Then, it was dispersed by nanomizer treatment to obtain a first resin layer varnish A.

Production Examples 4 to 6
(Manufacture of varnishes B to D for the first resin layer)
Varnishes B to D for the first resin layer were obtained in the same manner as the varnish A for the first resin layer except that the compounding composition was changed as shown in Table 2.

[Manufacturing of composite film]
Example 1
The second resin layer varnish obtained above is applied to a release-treated support (PET film, manufactured by Toray Film Processing Co., Ltd., trade name: Therapy (registered trademark) SY (RX), thickness 38 μm). The film was applied using a comma coater so that the thickness after drying was 2.7 μm, and dried at 140 ° C. for 3 minutes to form a second resin layer on the support. Next, the varnish A for the first resin layer is applied onto the second resin layer using a comma coater so that the thickness of the first resin layer after drying is 27.3 μm, and 90 It was dried at ° C. for 2 minutes. Next, 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 composite film 1 having a support and a protective film.

Examples 2-3, Comparative Example 1
Using the first resin layer varnishes B to D, composite films 2 to 4 were obtained in the same manner as in Example 1.

[Manufacturing of resin plate]
The resin plate used for the dielectric loss tangent and the measurement of the elastic modulus was produced by the following procedure.
(I) The protective film was peeled off from the composite film having the support and the protective film obtained in each example, and then dried at 120 ° C. for 5 minutes.
Next, a composite film having a support after drying is subjected to a copper foil (electroelectric copper foil, thickness) using a vacuum pressurizing laminator (manufactured by Meiki Seisakusho Co., Ltd., trade name: MVLP-500 / 600-II). The resin layer and the copper foil were laminated on the glossy surface of 35 μm) so as to be in contact with each other to obtain a laminated body (P) in which the copper foil, the composite film, and the support were laminated in this order. 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, a composite film having another support and a protective film was prepared, the protective film was peeled off, and then dried at 110 ° C. for 3 minutes.
(III) Next, the resin layers of the laminated body (P) obtained by peeling off the support obtained in the above (I) and the composite film having the dried support obtained in the above (II) are formed by the resin layers. By laminating under the same conditions as in (I) above so as to abut, a laminated body (Q) in which a copper foil, a layer composed of two layers of composite films, and a support were laminated in this order was obtained. Then, the support was peeled off from the laminated body (Q).
(IV) Next, the laminated body (Q) obtained by peeling off the support obtained in (III) above and the composite film having the support after drying obtained by the same method as in (II) above are obtained. The resin layers were laminated under the same conditions as in (I) so that the resin layers were in contact with each other to obtain a laminated body (R) in which a copper foil, a layer composed of three composite film layers, and a support were laminated in this order.
(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 from each other 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.

[Measurement method of dielectric loss tangent]
The resin plate produced above was cut into test pieces with a width of 2 mm and a length of 70 mm, and 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.) Was used to measure the dielectric loss tangent. The measurement temperature was 25 ° C. The evaluation results are shown in Table 2. The lower the dielectric loss tangent, the better the dielectric properties.

[Measurement method of 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). The measurement was performed, and the value at 40 ° C. was taken as the elastic modulus. The measurement was performed at a measurement temperature range of 40 to 300 ° C., a temperature rising rate of 5 ° C./min, and a vibration frequency of 10 Hz. The evaluation results are shown in Table 2.

[Measurement method of surface roughness]
(1) Method for manufacturing a substrate for surface roughness measurement A substrate for surface roughness measurement was prepared by the following procedure.
The composite film having the support and the protective film obtained in each example was cut into a size of 240 mm × 240 mm, and then the protective film was peeled off.
The first resin layer and the printed wiring board come into contact with the obtained composite film having the support on a printed wiring board (manufactured by Hitachi Kasei Co., Ltd., trade name: E-700GR) that has been subjected to CZ treatment. Laminated as. Lamination was carried out by a method of reducing the pressure for 15 seconds, pressurizing at 100 ° C. and a crimping pressure of 0.5 MPa for 45 seconds, and then pressing at 120 ° C. for 60 seconds at a crimping pressure of 0.5 MPa.
Then, it cooled to room temperature, and the printed wiring board which arranged the composite film was obtained. Next, the printed wiring board on which the composite film was arranged was cured in an explosion-proof dryer at 130 ° C. for 20 minutes as the first-stage curing with the support attached, and then 190 as the second-stage curing. Curing was performed in an explosion-proof dryer at ° C. for 40 minutes. After curing, the support was peeled off to obtain a printed wiring board on which an interlayer insulating layer was formed.

The printed wiring board obtained above was immersed in a swelling solution heated to 60 ° C. (manufactured by Atotech Japan Co., Ltd., trade name: Swelling Dep Securigant (registered trademark) P) for 10 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 measuring surface roughness.

(2) Surface Roughness Measurement Conditions The surface roughness of the surface roughness measurement substrate obtained above was measured using a specific contact type surface roughness meter (manufactured by Bruker AXS Co., Ltd., trade name: wykoNT9100). Arithmetic mean roughness (Ra) was obtained by measurement using an internal lens 1x and an external lens 50x. The evaluation results are shown in Table 2. From the gist of the present invention, Ra is preferably as small as possible, and less than 200 nm is suitable for forming fine wiring.

[Measurement method of adhesive strength with plated copper]
(1) Method for manufacturing a substrate for measuring adhesive strength (plating peel strength) with plated copper First, a printed wiring board with a composite film manufactured by the same method as the substrate for measuring surface roughness was cut out to a size of 40 mm × 60 mm and tested. It was a piece.
The test piece is roughened under the same conditions as the surface roughness measuring substrate, and then treated with an alkaline cleaner at 60 ° C. (manufactured by Atotech Japan Co., Ltd., trade name: Cleaner Security Gant (registered trademark) 902) for 5 minutes. And degreased and washed. After washing, it was treated with a predip solution at 23 ° C. (manufactured by Atotech Japan Co., Ltd., trade name: Predip Neogant (registered trademark) B) for 2 minutes. Then, it was treated with an activator solution at 40 ° C. (manufactured by Atotech Japan Co., Ltd., trade name: Activator Neogant (registered trademark) 834) for 5 minutes to attach a palladium catalyst. Next, it was treated with a reducing solution at 30 ° C. (manufactured by Atotech Japan Co., Ltd., trade name: Reducer Neogant (registered trademark) WA) for 5 minutes.
The test piece subjected to the above treatment was placed in a chemical copper solution (manufactured by Atotech Japan Co., Ltd., trade name: Basic Print Gantt (registered trademark) MSK-DK) to bring the plating thickness on the interlayer insulating layer to 0.5 μm. Electroless plating was performed until it became. After electroless plating, baking treatment was performed at 120 ° C. for 15 minutes in order to relieve the stress remaining in the plating film and remove the remaining hydrogen gas.
Next, the test piece subjected to the electroless plating treatment was further electroplated until the plating thickness on the interlayer insulating layer became 35 μm to form a copper layer as a conductor layer. After electrolytic plating, annealing treatment was performed at 190 ° C. for 120 minutes to obtain a measurement substrate before manufacturing the adhesive strength measuring section.
By forming a resist having a width of 10 mm on the copper layer of the obtained measurement substrate and etching the copper layer with ammonium persulfate, a substrate for measuring the adhesive strength with plated copper having a copper layer having a width of 10 mm as an adhesive strength measuring part. Got

(2) Measurement conditions for adhesive strength with plated copper One end of the copper layer of the adhesive strength measuring part formed on the substrate for measuring adhesive strength is peeled off at the interface between the copper layer and the interlayer insulating layer and grasped with a gripper, and a small desktop is used. Using a testing machine (manufactured by Shimadzu Corporation, trade name: EZT Test), the pulling speed in the vertical direction was 50 mm / min, and the load when peeled off at room temperature was measured. The evaluation results are shown in Table 2.

＊１：ポリイミド化合物（Ｂ）の仕込み量から換算される原料成分（ｂ１）及びエラストマ（Ｃ）の総量１００質量部に対する仕込み量（ｐｈｒ）
＊２：ポリイミド化合物（Ｂ）の仕込み量から換算される原料成分（ｂ１）１００質量部に対する仕込み量（ｐｈｒ）

* 1: Charged amount (phr) with respect to 100 parts by mass of the total amount of the raw material component (b1) and the elastomer (C) converted from the charged amount of the polyimide compound (B).
* 2: Charged amount (phr) with respect to 100 parts by mass of the raw material component (b1) converted from the charged amount of the polyimide compound (B).

Details of each component shown in Table 2 are as follows.
-SC-2050-KNK: Silica treated with an aminosilane coupling agent (manufactured by Admatex Co., Ltd., trade name, methyl isobutyl ketone dispersion having a solid content concentration of 70% by mass, average particle size of 0.5 μm)
-Elastomer (C): Maleic anhydride-modified polybutadiene-based elastomer "POLYVEST (registered trademark) MA75" (manufactured by Evonik, trade name)
-Polyimide compound (B): The polyimide compound (B) produced in Production Example 1.
-PX-200: 1,3-phenylenebis (di-2,6-xylenyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd., trade name)
-Yoshinox (registered trademark) BB: 4,4'-butylidenebis- (6-t-butyl-3-methylphenol) (manufactured by Mitsubishi Chemical Corporation, trade name)
BYK310: Silicon-based surface conditioner (manufactured by Big Chemie Japan Co., Ltd., trade name, xylene solution with a solid content concentration of 25% by mass)
-Perbutyl P: α, α'-di (tert-butylperoxy) diisopropylbenzene (manufactured by NOF CORPORATION, trade name)
-G8009L: Isocyanate mask imidazole (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name)

From Table 2, it can be seen that the resin plates obtained by using the composite films of Examples 1 to 3 have a small dielectric loss tangent and high elasticity. Further, the printed wiring board obtained by using the composite films of Examples 1 to 3 has a smooth surface (low surface roughness (Ra)) by providing a second resin layer which is an adhesive layer. However, it has an interlayer insulating layer having excellent adhesive strength with plated copper, and it can be seen that it is suitable for forming fine wiring.

In the thermosetting resin composition of the present invention, the cured product has low dielectric loss tangent and high elasticity. Therefore, the thermosetting resin composition of the present invention, the resin film for interlayer insulation using the same, the composite film and the printed wiring board are electric products such as computers, mobile phones, digital cameras and televisions; motorcycles, automobiles and trains. It is useful for vehicles such as ships and aircraft.

1 First resin layer 2 Second resin layer 3 Support 4 Protective film

Claims (12)

Inorganic filler (A), polyimide compound (B) and elastoma (C) having a structural unit derived from a maleimide compound (b1) having at least two N-substituted maleimide groups and a structural unit derived from a diamine compound (b2). A thermosetting resin composition containing and having an elastic coefficient of a cured product of 8.0 to 12.0 GPa. The thermosetting resin composition according to claim 1, wherein the inorganic filler (A) is silica. The thermosetting resin composition according to claim 1 or 2, wherein the elastomer (C) has a weight average molecular weight of 500 to 50,000. The thermosetting resin composition according to any one of claims 1 to 3, wherein the elastomer (C) is an elastomer modified with maleic anhydride. A resin film for interlayer insulation containing the thermosetting resin composition according to any one of claims 1 to 4. A composite film containing a first resin layer containing the thermosetting resin composition according to any one of claims 1 to 4 and a second resin layer. The second resin layer contains a second thermosetting resin composition containing a polyfunctional epoxy resin (D), an active ester curing agent (E), and a phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (F). , The composite film according to claim 6. The equivalent ratio (ester group / epoxy group) of the ester group of the active ester curing agent (E) to the epoxy group of the polycyclic epoxy resin (D) in the second thermosetting resin composition is 0.05. The composite film according to claim 7, which is ~ 1.5. The composite film according to claim 7 or 8, wherein the second thermosetting resin composition further contains a phosphorus-based curing accelerator (G). The composite film according to any one of claims 7 to 9, wherein the cured product has a 5 GHz dielectric loss tangent of 0.005 or less. A printed wiring board containing a cured product of the resin film for interlayer insulation according to claim 5 or a cured product of the composite film according to any one of claims 6 to 10. A method for producing a printed wiring board, comprising a step of laminating the resin film for interlayer insulation according to claim 5 or the composite film according to any one of claims 6 to 10 on one side or both sides of a base material.

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