JP2019157027A - Thermosetting resin composition, resin film for interlayer insulation, composite film, printed wiring board and method for producing the same - Google Patents

Abstract

To provide a thermosetting resin composition that, when made into a film, prevents the occurrence of whitening in wiring pattern embedding; and a resin film for interlayer insulation, a composite film, a printed wiring board and a method of producing the same, using the thermosetting resin composition.SOLUTION: A thermosetting resin composition contains an epoxy resin (A), an active ester curing agent (B), a phosphorous curing accelerator (C) and a pyridine compound having a tertiary amino group (D). There are also provided a resin film for interlayer insulation, a composite film, a printed wiring board and a method of producing the same, using the thermosetting resin composition.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, and with this, LSI (Large Scale Integration), chip parts, etc. have become more highly integrated, and their forms are also multi-pin and miniaturized. It is changing rapidly. For this reason, in order to improve the mounting density of electronic components, development of micro wiring of a multilayer printed wiring board has been advanced. As a multilayer printed wiring board meeting these requirements, a multilayer printed wiring board having a build-up structure in which an insulating resin film not containing glass cloth is used 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.

  The build-up layer is required to have a low thermal expansion in order to improve the processing dimension stability and reduce the amount of warpage after semiconductor mounting. One method for reducing the thermal expansion of the build-up layer is a method of highly filling the filler. For example, low thermal expansion of the buildup layer is achieved by using 40% by mass or more of the buildup layer as a silica filler (Patent Documents 1 to 3).

  On the other hand, in recent years, computers, information communication devices, and the like have become higher performance and higher functionality, and in order to process a large amount of data at a high speed, signals to be handled tend to be high-frequency. 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. In order to suppress transmission loss due to higher frequencies, a material having a low relative dielectric constant and dielectric loss tangent is desired as an organic material used in the high frequency region. Various efforts have been made to meet such demands. For example, Patent Document 4 discloses a resin composition containing a cyanate resin.

In addition, in order to satisfy the various requirements described above, a composite film for an insulating layer composed of two layers having different functions has been studied. Here, the first resin layer has a role of improving the adhesion between the second resin layer and the conductor layer, and the second resin layer functions as a build-up layer such as insulation and wiring pattern embedding. There is a role to express.
For example, Patent Document 5 discloses a resin film for interlayer insulation with an adhesion auxiliary layer and a printed wiring board using the film.

JP 2007-87982 A JP 2009-280758 A JP 2005-39247 A Japanese Unexamined Patent Publication No. 2014-136791 Japanese Patent Laid-Open No. 2006-135859

  However, according to the study by the present inventors, when the wiring pattern is embedded with the two-layer composite film for insulating layer, the first resin layer breaks when the wiring board pattern is embedded, and the second resin layer May be exposed and whitening may occur. This is presumed to be caused by insufficient curing of the adhesion auxiliary layer which is the first resin layer. Whitening causes poor appearance of the obtained printed wiring board, and there is a concern about the influence on the plating peel strength and the like.

  The present invention has been made in view of such a situation, a thermosetting resin composition in which the occurrence of whitening at the time of embedding a wiring pattern in a film is suppressed, a resin film for interlayer insulation using the same, It aims at providing a composite film, a printed wiring board, and its manufacturing method.

As a result of investigations to solve the above problems, the present inventors have found that a thermosetting resin composition having a specific composition can solve the problems.
That is, the present invention provides the following [1] to [16].
[1] A thermosetting resin composition containing an epoxy resin (A), an active ester curing agent (B), a phosphorus-based curing accelerator (C), and a pyridine compound (D) having a tertiary amino group.
[2] The equivalent ratio (ester group / epoxy group) of the ester group of the active ester curing agent (B) to the epoxy group of the epoxy resin (A) contained in the thermosetting resin composition is 0.3 to 1. The thermosetting resin composition according to the above [1], which is 0.5.
[3] The thermosetting resin composition according to [1] or [2], further including a phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (E).
[4] The thermosetting resin composition according to [3], wherein the content of the component (E) is 1 to 20 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting resin composition. object.
[5] The thermosetting resin composition according to any one of [1] to [4], wherein the phosphorus curing accelerator (C) is an adduct of a tertiary phosphine and a quinone.
[6] The above [1] to [5], wherein the content of the phosphorus-based curing accelerator (C) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting resin composition. ] The thermosetting resin composition in any one of.
[7] The thermosetting resin composition according to any one of [1] to [6], wherein the pyridine compound (D) having a tertiary amino group is 4-dimethylaminopyridine.
[8] The above [1], wherein the content of the pyridine compound (D) having a tertiary amino group is 0.1 to 20 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting resin composition. ] The thermosetting resin composition in any one of [7].
[9] A resin film for interlayer insulation containing the thermosetting resin composition according to any one of [1] to [8].
[10] A composite film comprising a first resin composition layer containing the thermosetting resin composition according to any one of [1] to [8] and a second resin composition layer.
[11] The polyimide compound (F), the modified polybutadiene (G), and the inorganic filler (H) in which the second resin composition layer has a structural unit derived from an aliphatic maleimide compound and a structural unit derived from a diamine compound. The composite film as described in [10] above, comprising a second thermosetting resin composition containing
[12] The composite film according to [10] or [11] above, wherein the cured product has a dielectric loss tangent of 5 GHz of 0.005 or less.
[13] A printed wiring board comprising a cured product of the interlayer insulating resin film according to [9] or a cured product of the composite film according to any of [10] to [12].
[14] A printed wiring comprising a step of laminating the interlayer insulating resin film according to [9] or the composite film according to any one of [10] to [12] on one side or both sides of a substrate. A manufacturing method of a board.
[15] A resin composition layer (I) containing a thermosetting resin composition (I);
A resin composition layer (II) containing a thermosetting resin composition (II);
A composite film having
The resin composition layer (II) is a layer that embeds the inner layer circuit to form an interlayer insulating layer,
The resin composition layer (I) is a layer that forms an adhesion auxiliary layer with a conductor layer on the surface opposite to the inner layer circuit of the interlayer insulating layer,
The composite film whose reaction start temperature of a thermosetting resin composition (I) is 140 degrees C or less.
[16] The reaction start temperature of the thermosetting resin composition (II) is higher than the reaction start temperature of the thermosetting resin composition (I), and the temperature difference is 5 to 50 ° C. The composite film according to [15] above.

  According to the present invention, a thermosetting resin composition in which the occurrence of whitening at the time of embedding a wiring pattern in a film is suppressed, a resin film for interlayer insulation using the same, a composite film, a printed wiring board, and a method for producing the same Can be provided.

It is a schematic cross section which shows the composite film of this embodiment.

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

  In the present specification, the “resin composition” refers to a mixture of components described later, a product obtained by semi-curing the mixture (so-called B-stage shape) and a product obtained by curing (so-called C-stage shape). including.

  In this specification, the “interlayer insulating layer” is a layer that is located between two conductor layers and insulates the conductor layer. Examples of the “interlayer insulating 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. Note that in this specification, the “layer” includes a part in which a part is missing and a part in which a via or a pattern is formed.

[Thermosetting resin composition]
The thermosetting resin composition of the present embodiment includes an epoxy resin (A) (hereinafter also referred to as “component (A)”), an active ester curing agent (B) (hereinafter also referred to as “component (B)”), It contains a phosphorus-based curing accelerator (C) (hereinafter also referred to as “component (C)”) and a pyridine compound (D) having a tertiary amino group (hereinafter also referred to as “component (D)”). is there.

<Epoxy resin (A)>
Although it does not specifically limit as an epoxy resin (A), The polyfunctional epoxy resin which has 2 or more of epoxy groups is preferable, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, cresol novolak 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, aralkyl novolac type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, etc. Is mentioned. Among these, from the viewpoint of adhesiveness with plated copper, an epoxy resin having a biphenyl structure or a naphthalene structure is preferable, a polyfunctional epoxy resin having a biphenyl structure or a naphthalene structure, an aralkyl novolac type epoxy resin having a biphenyl structure or a naphthalene structure Is more preferable.

  Although the epoxy equivalent of an epoxy resin (A) is not specifically limited, From an adhesive viewpoint with plated copper, 150-450 g / eq is preferable, 200-400 g / eq is more preferable, 250-350 g / eq is further more preferable. .

  An epoxy resin (A) may be used individually by 1 type, and may be used in combination of 2 or more type.

Although content of the epoxy resin (A) in the thermosetting resin composition of this embodiment is not specifically limited, 10-90 mass parts is preferable with respect to 100 mass parts of solid content of a thermosetting resin composition. 20-80 mass parts is more preferable, and 30-70 mass parts is further more preferable. When the content of the epoxy resin (A) is 10 parts by mass or more, better adhesive strength with the plated copper can be obtained, and when it is 90 parts by mass or less, a lower dielectric loss tangent tends to be obtained.
In addition, in this specification, solid content of a thermosetting resin composition means the residue which excluded volatile components, such as an organic solvent, from the component which comprises a thermosetting resin composition, and room temperature (25 ℃) including liquid, water tank and wax.

<Active ester curing agent (B)>
The active ester curing agent (B) has one or more ester groups in one molecule and has a curing action of the epoxy resin (A).
Although it does not specifically limit as an active ester hardening | curing agent (B), The ester compound etc. which are obtained from an aliphatic or aromatic carboxylic acid and an aliphatic or aromatic hydroxy compound are mentioned.
Among these, ester compounds obtained from aliphatic carboxylic acids, aliphatic hydroxy compounds, and the like tend to have high solubility in organic solvents and compatibility with epoxy resins by including aliphatic chains.
Moreover, the ester compound obtained from aromatic carboxylic acid, an aromatic hydroxy compound, etc. exists in the tendency for heat resistance to be improved by having an aromatic ring.

Examples of the active ester curing agent (B) include phenol ester compounds, thiophenol ester compounds, N-hydroxyamine ester compounds, and esterified compounds of heterocyclic hydroxy compounds.
More specifically, for example, aromatic esters 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, diphenylsulfonic acid and the like can be mentioned. Aromatic carboxylic acid components selected from those in which 2 to 4 hydrogen atoms in the ring are substituted with carboxy groups, monovalent phenols in which one of the hydrogen atoms in the aromatic ring is substituted with a hydroxyl group, and hydrogen atoms in the aromatic ring Aromatic esters obtained by a condensation reaction of an aromatic carboxylic acid and a phenolic hydroxyl group using a mixture of 2 to 4 of the above with a polyhydric phenol substituted with a hydroxyl group is preferred. That is, an aromatic ester having a structural unit derived from the aromatic carboxylic acid component, a structural unit derived from the monohydric phenol, and a structural unit derived from the polyhydric phenol is preferable.

  A commercially available product may be used as the active ester curing agent (B). As a commercial item of the active ester curing agent (B), for example, as an active ester compound containing a dicyclopentadiene type diphenol structure, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T” (DIC) Co., Ltd.), “EXB9416-70BK” (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, “DC808” (manufactured by Mitsubishi Chemical) as an active ester compound containing an acetylated product of phenol novolac, and phenol novolak Examples of the active ester compound containing a benzoylated product of “YLH1026” (manufactured by Mitsubishi Chemical Corporation) and the like.

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

  An active ester hardening agent (B) may be used individually by 1 type, and may be used in combination of 2 or more type.

  Although content of the active ester hardening | curing agent (B) in the thermosetting resin composition of this embodiment is not specifically limited, The ester group of the active ester hardening | curing agent (B) with respect to the epoxy group of an epoxy resin (A) is not limited. The amount that the equivalent ratio (ester group / epoxy group) is 0.3 to 1.5 is preferable, the amount that becomes 0.4 to 1.3 is more preferable, and the amount that becomes 0.5 to 1.0 is further increased. preferable. When the content of the active ester curing agent (B) is within the above range, the adhesive strength with the plated copper can be further increased, and a lower dielectric loss tangent and a smooth surface can be obtained. It is.

<Phosphorus curing accelerator (C)>
The phosphorus curing accelerator (C) can be used without particular limitation as long as it is a curing accelerator containing a phosphorus atom and accelerating the reaction between the epoxy resin (A) and the active ester curing agent (B). .
The thermosetting resin composition of the present embodiment can further promote the curing reaction by containing the phosphorus-based curing accelerator (C). The reason for this is that by using the phosphorus-based curing accelerator (C), the electron withdrawing property of the carbonyl group in the active ester curing agent (B) can be increased, whereby the active ester curing agent (B) and the epoxy are cured. It is assumed that the reaction with the resin (A) is promoted.
As described above, the thermosetting resin composition of the present embodiment contains the phosphorus-based curing accelerator (C), so that the epoxy resin (A) and the active ester curing agent are used more than when other curing accelerators are used. Since the curing reaction with (B) proceeds more sufficiently, it is considered that a low dielectric loss tangent can be obtained when combined with the second thermosetting resin composition layer described later.

Although it does not specifically limit as a phosphorus hardening accelerator (C), A triphenylphosphine, a diphenyl (alkylphenyl) phosphine, a tris (alkylphenyl) phosphine, a tris (alkoxyphenyl) phosphine, a tris (alkyl alkoxyphenyl) phosphine, a tris (Dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, Organic phosphines such as dialkylarylphosphine and alkyldiarylphosphine; complexes of organic phosphines and organic borons; tertiary phosphines and quino And addition products of class thereof. Among these, an adduct of a tertiary phosphine and a quinone is preferable from the viewpoint that the curing reaction proceeds more sufficiently and can exhibit high adhesion to plated copper.
Although it does not specifically limit as a tertiary phosphine, Tri-normal butyl phosphine, dibutyl phenyl phosphine, butyl diphenyl phosphine, ethyl diphenyl phosphine, triphenyl phosphine, tris (4-methylphenyl) phosphine, tris (4-methoxyphenyl) phosphine, etc. Is mentioned. The quinones are not particularly limited, and examples include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, and anthraquinone. Among these, an adduct of trinormal butylphosphine and p-benzoquinone is more preferable from the viewpoints of adhesion to plated copper, heat resistance, and a smooth surface.

  A phosphorus hardening accelerator (C) may be used individually by 1 type, and may be used in combination of 2 or more type.

Although content of the phosphorus hardening accelerator (C) in the thermosetting resin composition of this embodiment is not specifically limited, It is 0.1 with respect to 100 mass parts of solid content of a thermosetting resin composition. 20 mass parts is preferable, 0.2-15 mass parts is more preferable, 0.4-10 mass parts is further more preferable. When the content of the phosphorus curing accelerator (C) is 0.1 part by mass or more, the curing reaction can be sufficiently advanced, and when it is 20 parts by mass or less, the homogeneity of the cured product can be maintained. .
Further, the content of the phosphorus-based curing accelerator (C) in the thermosetting resin composition of the present embodiment based on the epoxy resin (A) is based on 100 parts by mass of the epoxy resin (A). 0.25-20 mass parts is preferable, 0.5-10 mass parts is more preferable, and 0.8-5 mass parts is still more preferable. When the content of the phosphorus-based curing accelerator (C) is 0.2 parts by mass or more with respect to 100 parts by mass of the epoxy resin (A), the curing reaction can be sufficiently advanced and is 20 parts by mass or less. And the homogeneity of the cured product can be maintained.

<Pyridine compound having a tertiary amino group (D)>
The thermosetting resin composition of this embodiment can further promote the curing reaction by containing the pyridine compound (D) having a tertiary amino group. This is because the reaction between the active ester curing agent (B) and the epoxy resin (A) is promoted by using the component (D) having a reaction initiation temperature lower than that of the phosphorus-based curing accelerator (C). Inferred. That is, the thermosetting resin composition of the present embodiment contains the component (D), so that the epoxy resin (A) and the active ester curing agent (C) are used more than when only the phosphorus-based curing accelerator (C) is used. Since the curing reaction with B) proceeds more sufficiently, when combined with the second thermosetting resin composition layer described below, whitening at the time of pattern embedding due to insufficient curing of the interlayer insulating layer is suppressed. Conceivable.

  Examples of the pyridine compound (D) having a tertiary amino group include compounds in which one or two or more hydrogen atoms are substituted with a tertiary amino group among the hydrogen atoms of the heterocyclic ring constituting the pyridine. Such a component (D) is preferably a compound represented by the following general formula (1).

(Wherein, ^{R 1} and ^{R 2} each independently represents a hydrocarbon group having 1 to 10 carbon atoms, n represents if .n represents an integer of 1 to 5 is 2 or more, plural ^{R 1} each other Or a plurality of R ² may be the same or different from each other.)

Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by R ¹ and R ² in the general formula (D-1) include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. Among these, an alkyl group is preferable. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, hexyl group, octyl group, nonyl group, and decyl group. Can be mentioned. Among these, a methyl group is preferable.
The hydrocarbon groups R ¹ and ^{R 2} represents the 1 to 5 preferably 1 to 3 is more preferable.
n is an integer of 1 to 5, an integer of 1 to 3 is preferable, and 1 is more preferable.
Among the above components (D), a compound represented by the following general formula (D-2) is more preferable.

(Wherein R ¹ and R ² are as described above.)

  Examples of the component (D) include 2-dimethylaminopyridine, 3-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 3-diethylaminopyridine, 4-diethylaminopyridine and the like. Among these, 4-dimethylaminopyridine is preferable from the viewpoint that the curing reaction can be further sufficiently advanced.

  A component (D) may be used individually by 1 type, and may be used in combination of 2 or more type.

Although content of the component (D) in the thermosetting resin composition of this embodiment is not specifically limited, 0.1-20 mass parts is with respect to 100 mass parts of solid content of a thermosetting resin composition. Preferably, 0.15-15 mass parts is more preferable, and 0.2-10 mass parts is further more preferable. When the content of the component (D) is 0.1 parts by mass or more, the curing reaction can be sufficiently advanced, and when it is 20 parts by mass or less, the homogeneity of the cured product can be maintained.
In addition, the content of the component (D) in the thermosetting resin composition of the present embodiment based on the epoxy resin (A) is 0.2 with respect to 100 parts by mass of the epoxy resin (A). -20 mass parts is preferable, 0.5-10 mass parts is more preferable, 0.8-5 mass parts is further more preferable. When the content of the component (D) is 0.2 parts by mass or more with respect to 100 parts by mass of the epoxy resin (A), the curing reaction can be sufficiently advanced, and when it is 20 parts by mass or less, the cured product. Can maintain homogeneity.

  The mass ratio of the component (C) and the component (D) in the thermosetting resin composition of the present embodiment [component (C) / component (D)] is preferably 0.1 to 10, 0.2-8 are more preferable, 0.3-6 are more preferable, and 0.5-5 are especially preferable. When the content ratio is within the above range, whitening at the time of pattern embedding due to insufficient curing of the interlayer insulating layer is more effectively suppressed.

<Phenolic hydroxyl group-containing polybutadiene modified polyamide resin (E)>
The component (E) is not particularly limited as long as it is a polybutadiene-modified polyamide resin having a phenolic hydroxyl group, but is not limited to a structural unit derived from a diamine, a structural unit derived from a dicarboxylic acid containing a phenolic hydroxyl group, and a phenolic hydroxyl group. Those having a structural unit derived from dicarboxylic acid containing no carboxylic acid and a structural unit derived from polybutadiene having carboxy groups at both ends are preferred. Specifically, preferred are 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). It is done.

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 Y + z = 2 to 300 ((y + z) / x) for ˜30, x = 1, and z ≧ 20 (z / y) for y = 1.
In the general formulas (i) to (iii), R ′ each independently represents a divalent group derived from an aromatic diamine or an aliphatic diamine, and in the general formula (iii), R ″ represents an aromatic dicarboxylic acid. , A divalent group derived from an aliphatic dicarboxylic acid or an oligomer having a carboxy group at both ends.
A plurality of R ′ contained in the general formulas (i) to (iii) may be the same or different. When z is an integer of 2 or more, the plurality of R ″ 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 described later. It is preferably a divalent group derived from dicarboxylic acid, aliphatic dicarboxylic acid or an oligomer having a carboxy group at both ends.

Examples of diamines include aromatic diamines and aliphatic diamines.
Examples of the aromatic diamine include diaminobenzene, diaminotoluene, diaminophenol, diaminodimethylbenzene, diaminomesitylene, diaminonitrobenzene, diaminodiazobenzene, diaminonaphthalene, diaminobiphenyl, diaminodimethoxybiphenyl, diaminodiphenyl ether, diaminodimethyldiphenyl ether, methylenediamine, Methylenebis (dimethylaniline), methylenebis (methoxyaniline), methylenebis (dimethoxyaniline), methylenebis (ethylaniline), methylenebis (diethylaniline), methylenebis (ethoxyaniline), methylenebis (diethoxyaniline), isopropylidenedianiline, diaminobenzophenone , Diaminodimethylbenzophenone, diaminoan Rakinon, diaminodiphenyl thioether, diaminodiphenyl dimethyl diphenyl thioether, diaminodiphenyl sulfone, diaminodiphenyl sulfoxide, diaminofluorene and the like.
Examples of the aliphatic diamine include ethylenediamine, propanediamine, hydroxypropanediamine, butanediamine, heptanediamine, hexanediamine, cyclopentanediamine, cyclohexanediamine, azapentanediamine, and triazaundecadiamine.

Examples of the dicarboxylic acid containing a phenolic hydroxyl group include hydroxyisophthalic acid, hydroxyphthalic acid, hydroxyterephthalic acid, dihydroxyisophthalic acid, and dihydroxyterephthalic acid.
Examples of the dicarboxylic acid not containing a phenolic hydroxyl group include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and oligomers having carboxy groups at both ends.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, biphenyl dicarboxylic acid, methylene dibenzoic acid, thiodibenzoic acid, carbonyl dibenzoic acid, sulfonylbenzoic acid, and naphthalenedicarboxylic acid.
Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, methylmalonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, malic acid, tartaric acid, (meth) acryloyloxysuccinic acid, di (meta) ) Acryloyloxysuccinic acid, (meth) acryloyloxymalic acid, (meth) acrylamide succinic acid, (meth) acrylamide malic acid and the like.

  Although the weight average molecular weight of a component (E) is not specifically limited, 60,000-250,000 are preferable and 80,000-200,000 are more preferable. The weight average molecular weight of a component (E) can be calculated | required by the method similar to the weight average molecular weight of the below-mentioned polyimide compound (F).

  The active hydroxyl equivalent of the component (E) 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. Further preferred.

  Component (E) is, for example, a diamine, a dicarboxylic acid containing a phenolic hydroxyl group, a dicarboxylic acid not containing a phenolic hydroxyl group, and a polybutadiene having a carboxy group at both ends in an organic solvent such as dimethylacetamide. And synthesized by polycondensation of a carboxy group and an amino group by reacting in the presence of a phosphite ester and a pyridine derivative as a catalyst. Examples of the compounds that can be used for the production include those described above.

  For example, the polybutadiene having a carboxy group at both ends used for the production of the component (E) 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. It is more preferable.

  Commercially available products can be used as the component (E), and examples of the commercially available component (E) include BPAM-155 manufactured by Nippon Kayaku Co., Ltd.

  A component (E) may be used individually by 1 type, and may be used in combination of 2 or more type.

  When the thermosetting resin composition of this embodiment contains a component (E), the content is not specifically limited, 1-20 with respect to 100 mass parts of solid content of a thermosetting resin composition. Mass parts are preferred, 2-15 parts by mass are more preferred, and 3-10 parts by mass are even more preferred. When the content of the component (E) is 1 part by mass or more, the toughness of the resin composition can be increased, a dense roughened shape can be obtained, and the adhesive strength with the plated copper can be increased. . Moreover, when it is 20 parts by mass or less, there is no decrease in heat resistance, and it is possible to prevent a decrease in resistance to chemicals during the roughening step. Moreover, sufficient adhesiveness with plated copper can be ensured.

<Filler (J)>
The thermosetting resin composition of the present embodiment may further contain a filler (J). Examples of the filler (J) include inorganic fillers and organic fillers.
By containing the filler (J), the thermosetting resin composition of this embodiment can further reduce resin scattering when laser processing the obtained insulating layer.

  The inorganic filler is not particularly limited, but silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, titanium Examples thereof include barium acid, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate.

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, from the viewpoint of forming fine wiring on the resin layer of the present embodiment. Although there is no restriction | limiting in particular in the upper limit of a specific surface area, 500 m < ² > / g or less is preferable from a viewpoint of availability, and 200 m < ² > / g or less is more preferable. The specific surface area can be determined by a BET method by low-temperature low-humidity physical adsorption of an inert gas. Specifically, molecules having a known adsorption occupation area such as nitrogen are adsorbed on the surface of the powder particles at the liquid nitrogen temperature, and the specific surface area of the powder particles can be determined from the amount of adsorption.

As the inorganic filler having a specific surface area of 20 m ² / g or more, a commercially available product may be used. Examples of commercially available products include AEROSIL R972 (trade name, specific surface area 110 ± 20 m ² / g, manufactured by Nippon Aerosil Co., Ltd.), which is fumed silica, and AEROSIL R202 (trade name, specific surface area 100, manufactured by Nippon Aerosil Co., Ltd.). ^{± 20m 2 / g), PL} -1 ( Fuso chemical Co., Ltd. is a colloidal silica, trade name, specific surface area ^{181m 2 / g), PL-} 7 ( Fuso chemical Co., Ltd., trade name, specific surface area 36m ² / g). Further, from the viewpoint of improving moisture resistance, an inorganic filler surface-treated with a surface treatment agent such as a silane coupling agent is preferable.

  When the thermosetting resin composition of this embodiment contains an inorganic filler, the content is 1-30 mass parts with respect to 100 mass parts of solid content of the resin component in a thermosetting resin composition. Preferably, 2-25 mass parts is more preferable, 3-20 mass parts is more preferable, and 5-18 mass parts is especially preferable. When the content of the inorganic filler is 1 part by mass or more, better laser processability tends to be obtained, and when it is 30 parts by mass or less, the second thermosetting resin composition layer described later There exists a tendency which the adhesive strength with a conductor layer improves more.

  The organic filler is not particularly limited, but as a copolymer of acrylonitrile butadiene, a crosslinked NBR particle obtained by copolymerizing acrylonitrile and butadiene, a copolymer of acrylonitrile, butadiene and carboxylic acid such as acrylic acid, polybutadiene, Examples include so-called core-shell rubber particles having NBR, silicone rubber as a core, and acrylic acid derivative as a shell. By containing the organic filler, the extensibility of the resin layer is further improved.

<Other ingredients>
The thermosetting resin composition of the present embodiment includes, in addition to the above-described components, a thermosetting resin, a thermoplastic resin, and the like other than the above-described components, as long as the effects of the present invention are not impaired. Other resin components; antioxidants, flow regulators, additives such as curing accelerators other than the above components (C) and (D); flame retardants described later; organic solvents and the like may be included. As for the other components, one kind may be used alone, or two or more kinds may be used in combination.

(Other resin components)
Examples of other resin components include phenoxy resins.
Here, the “phenoxy resin” is a general term for polymers whose main chain is a polyaddition structure of an aromatic diol and an aromatic diglycidyl ether. In the present specification, the weight average molecular weight is 10,000 or more. Refers to things. In addition, when the polymer whose main chain is a polyaddition structure of aromatic diol and aromatic diglycidyl ether has an epoxy group, those having a weight average molecular weight of 10,000 or more are classified as phenoxy resins, and the weight average molecular weight is Those less than 10,000 are classified as epoxy resin (A).

  Examples of the phenoxy resin include a phenoxy resin containing a cyclohexane structure, a phenoxy resin containing a trimethylcyclohexane structure, and a phenoxy resin containing a terpene structure. Among these, from the viewpoint of improving the handleability of the resin film, a phenoxy resin containing one or more selected from a terpene structure and a trimethylcyclohexane structure is preferable, and a phenoxy resin containing a trimethylcyclohexane (TMC) structure is more preferable. More preferred is a phenoxy resin containing a skeleton derived from a biphenyl type epoxy resin and a bisphenol compound containing a trimethylcyclohexane structure (1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane). .

  When the thermosetting resin composition of this embodiment contains a phenoxy resin, the content is not particularly limited, but is 2 to 30 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting resin composition. Preferably, 5-25 mass parts is more preferable, and 10-20 mass parts is further more preferable. When the content of the phenoxy resin is 2 parts by mass or more, the flexibility and handleability are excellent, and the peel strength of the conductor layer tends to be excellent. When the content is 30 parts by mass or less, storage stability and fluidity are obtained. And an appropriate roughness tends to be obtained.

(Antioxidant)
Examples of the antioxidant include phenolic antioxidants such as hindered phenolic antioxidants and styrenated phenolic antioxidants.
In the case where the thermosetting resin composition of the present embodiment contains an antioxidant, the content is improved from the viewpoint of improving the antioxidant properties without impairing the adhesion, heat resistance and dielectric properties with the conductor layer. 0.001-5 mass parts is preferable with respect to 100 mass parts of solid content of a thermosetting resin composition, 0.01-3 mass parts is more preferable, 0.1-0.5 mass part is further more preferable.

(Flow control agent)
Examples of the flow control agent include silicone, vinyl, acrylic, and fluorine flow control agents. Among these, a silicone type flow regulator is preferable.
In the case where the thermosetting resin composition of the present embodiment contains a flow regulator, the content is improved from the viewpoint of improving repellency without impairing the adhesion, heat resistance and dielectric properties with the conductor layer. 0.001-5 mass parts is preferable with respect to 100 mass parts of solid content of a thermosetting resin composition, 0.01-3 mass parts is more preferable, 0.1-0.5 mass part is further more preferable.

(Organic solvent)
The thermosetting resin composition of the present embodiment is in a varnish state (hereinafter also referred to as “resin varnish”) in which each component is dissolved and / or dispersed in an organic solvent in order to facilitate the production of a resin film. Also good.
Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methyl cellosolve; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and mesitylene. . Among these, from the viewpoint of solubility and the like, a ketone solvent is preferable, and methyl ethyl ketone is more preferable.
The total solid content of the thermosetting resin composition in the resin varnish is preferably 5 to 50% by mass and more preferably 10 to 30% by mass from the viewpoint of ease of application.

  100-140 degreeC is preferable, as for the reaction start temperature of the thermosetting resin composition of this embodiment, 105-130 degreeC is more preferable, 110-125 degreeC is further more preferable, and 110-120 degreeC is especially preferable. When the reaction start temperature is within the above range, whitening during pattern embedding due to insufficient curing of the interlayer insulating layer is more effectively suppressed. In addition, reaction start temperature is the value measured by the method as described in an Example.

  120-180 J / g is preferable, the reaction heat at the time of hardening of the thermosetting resin composition of this embodiment is more preferable, 130-170 J / g is more preferable, and 140-160 J / g is further more preferable. When the reaction heat is within the above range, whitening during pattern embedding due to insufficient curing of the interlayer insulating layer is more effectively suppressed. In addition, reaction heat is the value measured by the method as described in an Example.

[Composite film, resin film for interlayer insulation]
The composite film of this embodiment includes a first resin composition layer (hereinafter, also referred to as “first resin layer”) containing the thermosetting resin composition of this embodiment, and a second resin composition layer ( Hereinafter, it is also referred to as “second resin layer”).
Moreover, the resin film for interlayer insulation of this embodiment is a resin film for interlayer insulation containing the thermosetting resin composition of this embodiment.

An example of the composite film of this 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 2 and a second resin layer 1, and a support 3 and / or a protective film 4 as necessary.
In addition, there is no clear interface between the first resin layer and the second insulating layer, for example, a part of the constituent components of the first resin layer and the constituent components of the second insulating layer. May be in a state of being compatible and / or mixed.

<First resin layer>
The first resin layer includes the thermosetting resin composition of the present embodiment (herein also referred to as “first thermosetting resin composition”). In the printed wiring board of the present embodiment, the first resin layer will be described later. It is located between the cured product of the second resin layer containing the thermosetting resin composition and the conductor layer, and is provided for the purpose of improving the adhesion to the conductor layer. By providing the first resin layer, a smooth surface can be obtained, and better adhesive strength can be obtained with a conductor layer formed by plating. Therefore, it is preferable to provide the first resin layer from the viewpoint of forming fine wiring.

<Second resin layer>
For example, in the case of manufacturing a multilayer printed wiring board using the composite film of the present embodiment, the second resin layer is provided between the circuit board and the adhesion auxiliary layer, and the conductor layer of the circuit board and the top thereof Used to insulate the layers. In addition, when the through hole, the via hole, or the like exists in the circuit board, the second resin layer also flows in the circuit board and fills the inside of the hole.

The second resin layer is not particularly limited as long as it insulates the conductor layer of the circuit board from the layer above it. For example, maleimide compound (f1) (hereinafter also referred to as “component (f1)”) ) Derived structural unit and a diamine compound (f2) (hereinafter also referred to as “component (f2)”), a polyimide compound (F), (hereinafter referred to as “polyimide compound (F)” or “component ( F) ”, modified polybutadiene (G) (hereinafter also referred to as“ component (G) ”), and inorganic filler (H) (hereinafter also referred to as“ component (H) ”), It is preferable that the thermosetting resin composition is included.
With regard to each of the components (F) to (H), one type may be used alone, or two or more types may be used in combination.

<Polyimide compound (F)>
The polyimide compound (F) has a structural unit derived from the maleimide compound (f1) and a structural unit derived from the diamine compound (f2).
In addition, component (f1) and (f2) may be used individually by 1 type, respectively, and may be used in combination of 2 or more type, respectively.

As the component (f1), an aliphatic maleimide compound is preferable.
The aliphatic maleimide compound is preferably a maleimide compound having 6 to 40 carbon atoms between imide groups and having two or more N-substituted maleimide groups.
Examples of the aliphatic maleimide compound include 1,6-bismaleimide- (2,2,4-trimethyl) hexane, pyrroluronic acid binder type long chain alkyl bismaleimide and the like. Among these, 1,6-bismaleimide- (2,2,4-trimethyl) hexane is preferable from the viewpoint that the coefficient of thermal expansion is low and the glass transition temperature is excellent.

Component (f1) may contain a structural unit derived from a maleimide compound other than the aliphatic maleimide compound (hereinafter also referred to as “other maleimide compounds”) together with or in place of the aliphatic maleimide compound. Good.
Other maleimide compounds are not particularly limited as long as they are maleimide compounds having two or more N-substituted maleimide groups. For example, bis (4-maleimidophenyl) methane, polyphenylmethanemaleimide, bis (4-maleimidophenyl) Ether, bis (4-maleimidophenyl) sulfone, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebis And maleimide and 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane. Among these, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane is preferable from the viewpoint of excellent mechanical properties such as high adhesion to a conductor, elongation, and breaking strength.

  Examples of the structural unit derived from the component (f1) include a group represented by the following general formula (F-1) and a group represented by the following general formula (F-2).

(In the formula, A ¹ represents a residue of the component (f1), and * represents a bonding portion. The residue of the component (f1) is a functional group (maleimide) provided from the component (f1) for bonding. (The structure of the part excluding the group).)

  5-95 mass% is preferable, as for the total content of the structural unit derived from a component (f1) in a polyimide compound (F), 30-93 mass% is more preferable, and 60-90 mass% is further more preferable. When the content of the structural unit derived from the component (f1) is within the above range, in the thermosetting resin composition of the present embodiment, better high-frequency characteristics and film handling properties tend to be obtained.

The component (f2) is not particularly limited as long as it is a compound having two amino groups.
As the component (f2), 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, 4,4′- Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'- Diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dihydroxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3′-dimethyl- 5,5′-diethyl-4,4′-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 2,2-bis [4- (4-a Nophenoxy) 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] sulfo , Bis [4- (3-aminophenoxy) phenyl] sulfone, 9,9-bis (4-aminophenyl) fluorene, and the like.
Among these, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4 from the viewpoint of excellent solubility in organic solvents, reactivity during synthesis, and heat resistance. , 4′-diamino-3,3′-diethyldiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4 ′-[1,3-phenylenebis (1-methylethylidene) Bisaniline and 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline are preferred. Component (f2) is preferably 3,3′-dimethyl-5,5′-diethyl-4,4′-diaminodiphenylmethane from the viewpoint of excellent dielectric properties and low water absorption. The component (f2) is preferably 2,2-bis [4- (4-aminophenoxy) phenyl] propane from the viewpoint of excellent mechanical properties such as high adhesion to the conductor, elongation, and breaking strength. Furthermore, in addition to excellent solubility in the organic solvent, reactivity during synthesis, heat resistance, and high adhesion to the conductor, the component (f2 ) Is preferably 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisaniline and 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline.

  Examples of the structural unit derived from the component (f2) include a group represented by the following general formula (F-3), a group represented by the following general formula (F-4), and the like.

(In the formula, A ² represents a residue of the component (f2), and * represents a bonding part. The residue of the component (f2) is a functional group (amino) provided for bonding from the component (f2). (The structure of the part excluding the group).)

  5-95 mass% is preferable, as for the total content of the structural unit derived from a component (f2) in a polyimide compound (F), 7-70 mass% is more preferable, and 10-40 mass% is further more preferable. When the content of the structural unit derived from the component (f2) is within the above range, in the thermosetting resin composition of the present embodiment, better high-frequency characteristics, heat resistance, flame retardancy, and glass transition temperature are obtained. It tends to be.

The content ratio of the structural unit derived from the component (f1) in the polyimide compound (F) and the structural unit derived from the component (f2) is derived from the —NH ₂ group of the component (f2) in the polyimide compound (F). the total equivalents of groups (-NH ₂ including) (Ta2), component (f1) derived from a maleimide group derived from group equivalent ratio (Ta2 / Ta1) of the total equivalents of (maleimido group containing) (Ta1) is 0.05 to 10.0, and more preferably 1.0 to 5.0. When the equivalent ratio (Ta2 / Ta1) is within the above range, the thermosetting resin composition of the present embodiment tends to obtain better high-frequency characteristics, heat resistance, flame retardancy, and glass transition temperature.

  The polyimide compound (F) is a polyamino bismaleimide compound represented by the following general formula (F-5) from the viewpoints of solubility in an organic solvent, high frequency characteristics, high adhesion to a conductor, film formability, and the like. It is preferable to include.

(In the formula, A ¹ and A ² are as described above.)

The polyimide compound (F) can be produced, for example, by reacting the component (f1) and the component (f2) in an organic solvent.
When manufacturing a polyimide compound (F) by making a component (f1) and a component (f2) react, a reaction catalyst can also be used as needed. Although it does not restrict | limit as a reaction catalyst, For example, Acid catalysts, such as p-toluenesulfonic acid; Amines, such as a triethylamine, a pyridine, and a tributylamine; Imidazoles, such as a methylimidazole and a phenylimidazole; Phosphorus catalysts, such as a triphenylphosphine Etc. You may use these individually or in mixture of 2 or more types. Moreover, the compounding quantity of a reaction catalyst is although it does not specifically limit, For example, it is used in 0.01-5.0 mass parts with respect to 100 mass parts of total amounts of a component (f1) and a component (f2). it can.

A predetermined amount of the component (f1), the component (f2), and other components as needed is charged into the synthesis kettle, and the component (f1) and the component (f2) are subjected to a Michael addition reaction to obtain the polyimide compound (F). The reaction conditions in this step are not particularly limited. For example, the reaction temperature is preferably 50 to 160 ° C. and the reaction time is preferably 1 to 10 hours from the viewpoints of workability such as reaction rate and suppression of gelation. .
In this step, an organic solvent can be added or concentrated to adjust the solid content concentration of the reaction raw material and the solution viscosity. Although the solid content density | concentration of a reaction raw material is not specifically limited, For example, 10-90 mass% is preferable and 20-80 mass% is more preferable. 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. Moreover, when the solid content concentration of the reaction raw material is 90% by mass or less, better solubility is obtained, the stirring efficiency is good, and gelation is less likely.

  Although the weight average molecular weight of a polyimide compound (F) is not specifically limited, 800-10,000 are preferable, 900-5,000 are more preferable, 1,000-3,000 are more preferable. The weight average molecular weight of a polyimide compound (F) can be calculated | required by the method as described in an Example.

  Although content of the polyimide compound (F) in a 2nd thermosetting resin composition is not specifically limited, 50-95 mass% in the total mass of all the resin components in a 2nd thermosetting resin composition. Is preferable, and 60 to 90 mass% is more preferable. When the content of the polyimide compound (F) is within the above range, the insulation reliability is excellent, and a low thermal expansion coefficient, a high glass transition temperature, and a good dielectric loss tangent tend to be obtained.

<Modified polybutadiene (G)>
The modified polybutadiene (G) is preferably a chemically modified polybutadiene. When the modified polybutadiene (G) is used, separation between the inorganic filler (H) and the resin component, uneven gloss, and the like can be reduced in the obtained interlayer insulating layer. In the present specification, the chemically modified polybutadiene means that 1,2-vinyl group and / or one or both ends of the side chain in the molecule are acid anhydrided, epoxidized, glycolated, phenolated, maleated. Chemically modified such as chemical, (meth) acrylated, urethanized.
The modified polybutadiene (G) preferably contains 1,2-butadiene units having a 1,2-vinyl group in the side chain in the molecule, and contains 40% by mass or more of the 1,2-butadiene units. More preferred.

From the viewpoint of obtaining a thermosetting resin composition having a lower dielectric loss tangent, the modified polybutadiene (G) is preferably a polybutadiene modified with an acid anhydride. The acid anhydride is not particularly limited, but phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, glutaric anhydride Acid, dimethyl glutaric anhydride, diethyl glutaric anhydride, succinic anhydride, methyl hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, etc., including phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride Any of hexahydrophthalic anhydride and tetrahydrophthalic anhydride is preferred, and maleic anhydride is more preferred.
When the modified polybutadiene (G) is modified with an acid anhydride, the number of groups derived from an acid anhydride (hereinafter also referred to as “acid anhydride groups”) contained in one molecule of the modified polybutadiene (G) is 1 -10 are preferable, 1-6 are more preferable, and 2-5 are more preferable. When the number of acid anhydride groups is 1 or more per molecule, the separation between the inorganic filler (H) and the resin component when the interlayer insulating layer is formed tends to be further suppressed. Moreover, when the number of acid anhydride groups is 10 or less per molecule, the dielectric loss tangent of the resulting thermosetting resin composition tends to be lower.
That is, when the modified polybutadiene (G) is modified with maleic anhydride, from the same viewpoint as described above, the number of groups derived from maleic anhydride contained in one molecule of the modified polybutadiene (G) is 1-10. 1-6 are more preferable, and 2-5 are more preferable.

  The weight average molecular weight of the modified polybutadiene (G) is preferably 500 to 25,000, more preferably 1,000 to 20,000, still more preferably 2,000 to 13,000, and particularly preferably 3,000 to 10,000. preferable. When the weight average molecular weight of the modified polybutadiene (G) 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 is 25,000 or less, in the obtained interlayer insulating layer, separation between the inorganic filler (H) and the resin component and gloss unevenness tend to be further suppressed. In addition, the measuring method of the weight average molecular weight of the polyimide compound (F) in the Example of this specification can be applied to the weight average molecular weight of the modified polybutadiene (G).

  A commercially available product may be used as the modified polybutadiene (G). Examples of commercially available modified polybutadiene (G) include POLYVEST MA75, POLYVEST EP MA120 (trade name, manufactured by Evonik), Ricon 130MA8, Ricon 131MA5, and Ricon 184MA6 (trade name, manufactured by Clay Valley).

  The content of the modified polybutadiene (G) in the second thermosetting resin composition is not particularly limited, but 1 to 50% by mass is 1% by mass in the total mass of all resin components in the second thermosetting resin composition. Preferably, 5-40 mass% is more preferable, and 10-30 mass% is further more preferable. When the content of the modified polybutadiene (G) is within the above range, there is a tendency that resin separation and gloss unevenness can be further reduced.

  The total content of the polyimide compound (F) and the modified polybutadiene (G) in the second thermosetting resin composition is not particularly limited, but is 5 to 50 in the total mass of the second thermosetting resin composition. % By mass is preferable, 10 to 40% by mass is more preferable, and 15 to 30% by mass is further preferable.

<Inorganic filler (H)>
It does not specifically limit as an inorganic filler (H), For example, the thing similar to what was illustrated as a filler (J) is mentioned. Among these, silica is preferable from the viewpoint of lowering the thermal expansion of the obtained interlayer insulating layer.
Although the volume average particle diameter of an inorganic filler (H) is not specifically limited, 0.05-5 micrometers is preferable, 0.1-3 micrometers is more preferable, 0.2-1 micrometer is further more preferable. When the volume average particle size is 5 μm or less, the fine pattern tends to be formed more stably when the circuit pattern is formed on the interlayer insulating layer. Further, when the volume average particle size is 0.1 μm or more, the heat resistance tends to be better. The volume average particle diameter is a particle diameter at a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle diameter is obtained with the total volume of the particles being 100%, and the laser diffraction scattering method is used. It can be measured with the used particle size distribution measuring device or the like.

In order to improve the dispersibility of the inorganic filler (H) and the adhesion between the inorganic filler (H) and the organic component in the resin composition, a coupling agent may be used in combination as necessary. As the coupling agent, various silane coupling agents, titanate coupling agents and the like can be used. Moreover, the usage-amount is not specifically limited, For example, 0.1-5 mass parts is preferable with respect to 100 mass parts of inorganic fillers (H) to be used, and 0.5-3 mass parts is more preferable. Within this range, the advantages of using the inorganic filler (H) can be more effectively exhibited.
When a coupling agent is used, the addition method is a so-called integral blend treatment method in which an inorganic filler (H) is added to the second thermosetting resin composition and then the coupling agent is added. However, from the viewpoint of expressing the characteristics of the inorganic filler (H) more effectively, a method may be used in which an inorganic filler obtained by subjecting the inorganic filler to a dry or wet surface treatment with a coupling agent in advance is used. .

From the viewpoint of dispersibility of the inorganic filler (H) in the thermosetting resin composition, it is preferable to use the inorganic filler (H) as a slurry in which the inorganic filler (H) is previously dispersed in an organic solvent, if necessary. As the organic solvent used when slurrying the inorganic filler (H), the above-described organic solvents can be applied. These may be used alone or in combination of two or more. Among these organic solvents, methyl isobutyl ketone is preferable from the viewpoint of higher dispersibility.
Moreover, the non-volatile content density | concentration of the slurry of an inorganic filler (H) is although it does not specifically limit, For example, 50-80 mass% is preferable from a sedimentation property and dispersibility viewpoint of an inorganic filler (H), and 60-80 The mass% is more preferable.

  The content of the inorganic filler (H) in the second thermosetting resin composition can be appropriately selected depending on the characteristics and functions required of the second thermosetting resin composition, but the second thermosetting resin composition 80-600 mass parts is preferable with respect to 100 mass parts of total mass of all the resin components in a thing, 100-500 mass parts is more preferable, 200-400 mass parts is more preferable. When the content of the inorganic filler (H) is within the above range, it can have a low coefficient of thermal expansion.

<Other ingredients>
In the second thermosetting resin composition, in addition to the above-described components, other resin components such as other thermosetting resins and thermoplastic resins as necessary, within a range not inhibiting the effects of the present invention; It can contain additives such as inhibitors, flow regulators, curing accelerators; flame retardants; organic solvents and the like.
Examples of these other components include the same as those described in the thermosetting resin composition of the present embodiment, and each of them may be used alone or in combination of two or more. May be used.

(Flame retardants)
By including a flame retardant in the second thermosetting resin composition, better flame retardancy can be imparted. Although it does not specifically limit as a flame retardant, A chlorine flame retardant, a bromine flame retardant, a phosphorus flame retardant, a metal hydrate flame retardant, etc. are mentioned. Among these, a phosphorus flame retardant or a metal hydrate flame retardant is preferable from the viewpoint of compatibility with the environment.

(Curing accelerator)
By including an appropriate curing accelerator in the second thermosetting resin composition, the curability of the thermosetting resin composition is improved, and the dielectric properties, heat resistance, high elastic modulus, glass of the interlayer insulating layer The transition temperature and the like 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.

(Organic solvent)
The second thermosetting resin composition may be in the form of a varnish in which each component is dissolved and / or dispersed in an organic solvent in order to facilitate the production of a resin film.
As an organic solvent, the same thing as the organic solvent which the thermosetting resin composition of the said embodiment may contain is mentioned.

<Support and protective film>
Examples of the support include polyolefin films such as polyethylene, polypropylene and polyvinyl chloride; polyester films such as polyethylene terephthalate (hereinafter also referred to as “PET”) and polyethylene naphthalate; various plastics such as polycarbonate films and polyimide films. A film etc. are mentioned. Moreover, you may use metal foil, release paper, etc., such as copper foil and aluminum foil. The support and the protective film described later may be subjected to surface treatment such as mat treatment or corona treatment. In addition, the support and the protective film described later may be subjected to a release treatment with a silicone resin release agent, an alkyd resin release agent, a fluororesin release agent, or the like.
Although the thickness of a support body is not specifically limited, 10-150 micrometers is preferable and 25-50 micrometers is more preferable.

  A protective film may be provided on the surface of the first resin layer opposite to the support. Although the thickness of a protective film is not specifically limited, For example, 1-40 micrometers may be sufficient. By providing the protective film, it is possible to prevent adhesion of dust and the like to the surface of the first resin layer and scratches. The composite film can also be stored in a roll form.

  In addition, the resin film for interlayer insulation of this embodiment may not have a 2nd resin layer in the composite film demonstrated above.

<Production method of composite film and resin film for interlayer insulation>
The composite film of this embodiment can be manufactured by the method of forming a 1st resin layer on a support body and forming a 2nd resin layer on it, for example.
For the formation of the first resin layer, the thermosetting resin composition of the present embodiment or the resin varnish of the thermosetting resin composition of the present embodiment (herein also referred to as “first varnish for the resin layer”) Is preferably used.
For the formation of the second resin layer, a second thermosetting resin composition or a resin varnish of the second thermosetting resin composition (hereinafter, also referred to as “second resin layer varnish”) is used. Is preferred.
As a method for applying the resin varnish 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. These coating apparatuses are preferably selected as appropriate depending on the film thickness.

As drying conditions after coating the first varnish for the resin layer on the support, for example, the drying temperature is preferably 50 to 150 ° C, more preferably 100 to 150 ° C, and still more preferably 120 to 150 ° C. The drying time is preferably 1 to 10 minutes, more preferably 2 to 5 minutes.
As drying conditions after coating the 2nd varnish for resin layers on the 1st resin layer, for example, drying temperature becomes like this. Preferably it is 50-150 degreeC, More preferably, it is 60-130 degreeC, More preferably, it is 80- The drying time is preferably 1 to 10 minutes, more preferably 2 to 5 minutes.
In addition, it is preferable to dry so that content of the volatile component (mainly organic solvent) in the composite film after drying may be 10 mass% or less, and it is more preferable to dry so that it may be 6 mass% or less. .

The thickness of the first resin layer formed in the composite film of this embodiment is preferably from 1 to 15 μm, more preferably from 2 to 10 μm, and even more preferably from 4 to 7 μm, from the viewpoint of high frequency characteristics and fine wiring formation.
The thickness of the second resin layer may be appropriately determined according to the required performance, but is preferably equal to or greater than the thickness of the conductor layer of the circuit board from the viewpoint of embedding the conductor layer of the circuit board. 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 second resin layer is preferably 10 to 100 μm, more preferably 15 to 80 μm. 50 μm is more preferable.

  In addition, the resin film for interlayer insulation of this embodiment can be manufactured by the method which does not form a 2nd resin layer in the manufacturing method of the composite film demonstrated above, Other preferable conditions were demonstrated above. The same as the composite film.

<Physical properties of composite film>
The dielectric loss tangent at 5 GHz of the cured product of the composite film of this embodiment is preferably 0.010 or less, more preferably 0.008 or less, and further preferably 0.005 or less. In addition, the dielectric loss tangent of hardened | cured material can be calculated | required by the method as described in an Example.

  The peel strength of the cured product of the composite film of the present embodiment is preferably 0.5 kgf / cm or more, more preferably 0.6 kgf / cm or more, and further 0.65 kgf / cm or more from the viewpoint of adhesion to the conductor layer. preferable. Although there is no restriction | limiting in the upper limit of peel strength, For example, it is 15 kgf / cm or less. The peel strength is a value measured by the method described in the examples.

  From the viewpoint of fine wiring formation, the surface roughness Ra of the cured product of the composite film of the present embodiment is preferably 250 nm or less, more preferably 240 nm or less, and further preferably 180 nm or less. Further, the surface roughness Ra is preferably 1 nm or more from the viewpoint of further increasing the peel strength. The surface roughness is a value measured by the method described in the examples.

120-160 degreeC is preferable, the reaction start temperature of the composite film of this embodiment has more preferable 125-150 degreeC, and 130-140 degreeC is further more preferable. Whitening during pattern embedding due to insufficient curing of the interlayer insulating layer is more effectively suppressed. In addition, reaction start temperature is the value measured by the method as described in an Example.
The reaction start temperature of the second thermosetting resin composition is preferably higher than the reaction start temperature of the first thermosetting resin composition, and the temperature difference is 5 to 50 ° C. Preferably, 10-30 degreeC is more preferable. When the temperature difference is 5 ° C. or more, the first resin layer and the second resin layer can be prevented from reacting simultaneously without causing the whitening, and when it is 50 ° C. or less, the set curing temperature is reached. Since the curing reaction proceeds, the desired cured physical properties can be obtained.

  50-120 J / g is preferable, as for the heat of reaction of the composite film of this embodiment, 60-100 J / g is more preferable, and 70-90 J / g is further more preferable. When the reaction heat at the time of curing of the composite film is within the above range, whitening at the time of pattern embedding due to insufficient curing of the interlayer insulating layer is more effectively suppressed. In addition, reaction heat is the value measured by the method as described in an Example.

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

The multilayer printed wiring board according to this embodiment includes the following steps (1) to (5), and the support is peeled off or removed after the step (1), the step (2) or the step (3). May be.
Step (1): Step of laminating the composite film of this embodiment on one or both sides of the circuit board Step (2): Step of thermosetting the composite film to form an interlayer insulating layer Step (3): Interlayer insulating layer Step (4): Step of roughening the surface of the interlayer insulating layer Step (5): Step of plating on the surface of the roughened interlayer insulating layer

<Step (1)>
Step (1) is a step of laminating the composite film of the present embodiment on one or both sides of the circuit board. Examples of the apparatus for laminating the composite film include a vacuum laminator. Commercially available products can be used as the vacuum laminator. Examples of commercially available vacuum laminators include a vacuum applicator manufactured by Nichigo-Morton, a vacuum pressure laminator manufactured by Meiki Seisakusho, and a Hitachi Industries, Ltd. And a roll laminator manufactured by Hitachi AIC Co., Ltd.

In the lamination, when the composite film has a protective film, after removing the protective film, the composite film is pressure-bonded to the circuit board while being pressurized and / or heated.
When using a composite film, it arrange | positions so that a 2nd resin layer may oppose the surface in which the circuit of the circuit board is formed.
The lamination conditions are as follows. The composite film and the circuit board are preheated as necessary, the pressure bonding temperature (laminating temperature) is 60 to 140 ° C., and the pressure bonding pressure is 0.1 to 1.1 MPa (9.8 × 10 ^{4 to} 107 9.9 × 10 ⁴ N / m ² ) and air pressure of 20 mmHg (26.7 hPa) or less may be laminated. The laminating method may be a batch method or a continuous method using a roll.

<Step (2)>
Step (2) is a step of thermosetting the 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. You may peel a support body, after making it thermoset.

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

<Process (4)>
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 these are formed. “Smear” removal can also be performed.
Although it does not specifically limit as an oxidizing agent, For example, permanganate (potassium permanganate, sodium permanganate), dichromate, ozone, hydrogen peroxide, sulfuric acid, nitric acid, etc. are mentioned. Among these, alkaline permanganate solutions (for example, potassium permanganate and sodium permanganate solutions), which are oxidizers commonly used for roughening interlayer insulation layers in the production of multilayer printed wiring boards by the build-up method, are used. It may be used for roughening and smear removal.

<Step (5)>
Step (5) is a step of plating the surface of the roughened interlayer insulating layer. In this process, a power 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 conductive layer is formed, and a conductive layer (circuit) is formed by electrolytic plating. Can be used. In addition, after forming a conductor layer, the adhesive strength of an interlayer insulation layer and a conductor layer can be improved and stabilized by performing an annealing process at 150 to 200 ° C. for 20 to 120 minutes, for example.

  Furthermore, you may have the process of roughening the surface of the conductor layer produced in this way. The roughening of the surface of the conductor layer has the effect of improving the adhesion with the resin in contact with the conductor layer. The treatment agent for roughening the conductor layer is not particularly limited. For example, MEC etch bond CZ-8100, MEC etch bond CZ-8101, and MEC etch bond CZ-5480 (which are organic acid microetching agents) MEC Co., Ltd. product name).

  The thermosetting resin composition, the composite film, and the printed wiring board of the present embodiment can be particularly suitably used for electronic devices that handle high-frequency signals of 1 GHz or higher, particularly high-frequency signals of 5 GHz or higher, and high-frequency signals of 10 GHz or higher. Or it can use suitably for the electronic device which handles the high frequency signal of 30 GHz or more.

[Second composite film]
Moreover, according to the present invention,
A resin composition layer (I) containing a thermosetting resin composition (I);
A resin composition layer (II) containing a thermosetting resin composition (II);
A composite film having
The resin composition layer (II) is a layer that embeds the inner layer circuit to form an interlayer insulating layer,
The resin composition layer (I) is a layer that forms an adhesion auxiliary layer with a conductor layer on the surface opposite to the inner layer circuit of the interlayer insulating layer,
The 2nd composite film whose reaction start temperature of thermosetting resin composition (I) is 140 degrees C or less is also provided.

The thermosetting resin composition (I) is not particularly limited as long as the resin composition layer (I) can be formed and the reaction start temperature is 140 ° C. or lower, but the thermosetting resin of the present embodiment is not limited thereto. A composition is preferred. The reaction start temperature of the resin composition layer (I) can be measured by the method described in Examples.
The reaction start temperature of the thermosetting resin composition (I) is 140 ° C. or lower, preferably 95 to 130 ° C., more preferably 100 to 120 ° C.

  The thermosetting resin composition (II) is not particularly limited as long as it can form the resin composition layer (II), but is preferably the second thermosetting resin composition.

  The reaction initiation temperature of the thermosetting resin composition (II) is preferably higher than the reaction initiation temperature of the thermosetting resin composition (I), and the temperature difference is preferably 5 to 50 ° C. 10-30 are more preferable. When the temperature difference is 5 ° C. or more, the resin composition layer (I) and the resin composition layer (II) can be prevented from reacting simultaneously without reacting, and the temperature difference is set to 50 ° C. or less. Since the curing reaction proceeds at the cured temperature, the desired cured physical properties can be obtained.

  The preferable manufacturing method, form, physical properties, etc. of the second composite film are the same as those of the composite film of the present embodiment described above.

  In addition, this invention is not limited to the said embodiment. The above-described embodiment is an exemplification, and any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and has the same function and effect can be used. Included in the technical scope.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In addition, the room temperature in a present Example is 25 degreeC.

[Production of first resin composition]
Example 1
(First resin composition A)
The 1st resin composition A was prepared with the following method so that it might become a compounding composition shown in Table 1. FIG.
As component (A), naphthalene type epoxy resin (manufactured by DIC Corporation, trade name: HP-5000, epoxy equivalent 252 g / mol), and as component (B), active ester curing agent (manufactured by DIC Corporation, trade name: HPC). -8000-65T, toluene diluted product (65 mass%), active ester compound containing dicyclopentadiene type diphenol structure, ester group equivalent 223 g / eq), component (C), phosphorus-based curing accelerator (tri-normal butyl 4-dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed as an adduct of phosphine and p-benzoquinone) and component (D) to obtain a first resin composition A.

Examples 2-3 and Comparative Example 1
(First resin composition B to D)
First resin compositions B to D were obtained in the same manner as the first resin composition A except that each component and the blending amount thereof were changed to the blending shown in Table 1.

[Measurement of reaction start temperature and reaction heat]
The first resin composition obtained above is powdered and heated at a rate of temperature increase of 10 using a differential calorimeter (TA Instruments, trade name: Q200 type differential calorimeter) under a nitrogen atmosphere. The reaction start temperature and reaction heat when measuring between 50 and 350 ° C. at a rate of ° C./min were measured.
The reaction start temperature is the temperature at the intersection of the tangent of the maximum slope of the curing exothermic peak and the baseline in the DSC curve obtained above, and the reaction heat is the above-mentioned curing in the DSC curve obtained above. The amount of heat determined from the area of the exothermic peak was used. The evaluation results are shown in Table 1.

*: In the table, the unit of the blending amount of each component that does not have a unit is “part by mass”.
* 1: Means blending amount (phr) with respect to 100 parts by mass of epoxy resin (A).

From Table 1, in Examples 1 to 3 using the thermosetting resin composition of the present embodiment, the reaction start temperature was lower than that of Comparative Example 1, and the reaction heat was increased.
That is, the thermosetting resin composition of the present embodiment is likely to be hardened at the time of drying after varnish coating, and it is presumed that the degree of hardening becomes a film.

  Next, the composite film of this embodiment was manufactured and its physical properties were evaluated.

[Production of polyimide compound (F)]
Production Example 1
1,6-bismaleimide- (2,2,4-trimethyl) hexane (Daiwa Kasei Kogyo Co., Ltd.) was added to a glass flask container having a thermometer, a reflux condenser, and a stirrer and capable of heating and cooling. Manufactured, trade name: BMI-TMH) (component (f1)) 330 g, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000)) 1381 g (component (f1)), 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisaniline (Mitsui Chemical Fine Co., Ltd., trade name: Bisaniline M) (component (f2)) 238 g and 1050 g of propylene glycol monomethyl ether was added, and the mixture was allowed to react for 2.5 hours with stirring at a liquid temperature of 120 ° C. while refluxing. Thereafter, the reaction product is confirmed to have a weight average molecular weight of 1,500 by gel permeation chromatography (GPC), and cooled and filtered through 200 mesh to obtain a polyimide compound (F) (solid content concentration 65 mass%). Manufactured.

The weight average molecular weight of the obtained polyimide compound (F) was converted from a calibration curve using standard polystyrene by GPC. The calibration curve is standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, Product name]) and approximated by a cubic equation. The GPC conditions are shown below.
Apparatus: (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 Guardcolumn HHR-L + column; TSK gel-G4000HHR + TSK gel-G2000HHR (all trade names, manufactured by Tosoh Corporation)
Column size: 6.0 × 40 mm (guard column), 7.8 × 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

[Production of second resin composition for forming composite film]
Production Example 2
A second resin composition was prepared by the following method so as to have the composition shown in Table 2.
As component (H), silica treated with an aminosilane coupling agent (manufactured by Admatechs Co., Ltd., trade name: SC-2050-KNK, methyl isobutyl ketone dispersion with a solid content concentration of 70% by mass), and component (G) As a mixture, a polybutadiene elastomer (manufactured by Evonik, trade name: POLYVEST 75MA) was mixed.
The polyimide compound (F) produced in Production Example 1 was mixed therewith and dissolved at room temperature using a high-speed rotary mixer.
After visually confirming that the polyimide compound (F) was dissolved, 1,3-phenylenebis (di-2,6-xylenyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd., trade name: PX) was used as a flame retardant. -200), 4,4′-butylidenebis- (6-tert-butyl-3-methylphenol) (manufactured by Mitsubishi Chemical Co., Ltd., trade name: Yoshinox BB), a flow regulator (Big Chemie Japan Co., Ltd.) Company name, BYK-310, xylene solution having a solid concentration of 25% by mass) were mixed.
Thereafter, an organic peroxide (manufactured by NOF Corporation, trade name: Perbutyl P) is used as the curing accelerator 1, and an isocyanate mask imidazole (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: G8009L) is used as the curing accelerator 2. Mixed. Subsequently, it disperse | distributed by the nanomizer process and the varnish-like 2nd resin composition for producing a composite film was obtained.

[Production of first resin composition for composite film]
Production Example 3
(Production of first resin composition E)
The 1st resin composition E was prepared with the following method so that it might become a compounding composition shown in Table 2.
A phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (manufactured by Nippon Kayaku Co., Ltd., trade name: BPAM-155) was mixed with dimethylacetamide and cyclohexanone (dimethylacetamide: cyclohexanone) so that the mass% was 2.1%. (Mixed solvent having a mass ratio of 7: 3). After dissolution, as component (A), naphthalene type epoxy resin (manufactured by DIC Corporation, trade name: HP-5000, epoxy equivalent 252 g / mol), as component (J), inorganic filler (manufactured by Nippon Aerosil Co., Ltd., product) Name: Aerosil R972, specific surface area 110 ± 20 m ² / g), antioxidant (manufactured by API Corporation, trade name: Yoshinox BB), phenoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: YX7200, methyl ethyl ketone diluted product) (35 mass%)), active ingredient curing agent (manufactured by DIC Corporation, trade name: HPC-8000-65T, toluene diluted product (65 mass%), dicyclopentadiene type diphenol structure as component (B) Active ester compound, ester group equivalent 223 g / eq), flow modifier (Big Chemie) Made by Japan Co., Ltd., trade name: BYK-310), component (C) as phosphorus curing accelerator (adduct of tri-normal butylphosphine and p-benzoquinone), component (D) as 4-dimethylaminopyridine ( Wako Pure Chemical Industries, Ltd.) was mixed and dissolved, and the varnish was diluted with methyl ethyl ketone so that the solid content concentration was 18% by mass. Then, it disperse | distributed by the nanomizer process and the varnish-like 1st resin composition E was obtained.

Production Examples 4-5
(Production of first resin compositions F and G)
First resin compositions F and G were obtained in the same manner as the first resin composition E, except that each component and the blending amount thereof were changed to the blending shown in Table 2.

[Manufacture of composite film]
Example 4
(Composite film 1)
The first resin composition E obtained above was dried on a release-treated support (PET film, manufactured by Toray Film Processing Co., Ltd., trade name: Therapy SY (01) (thickness 38 μm)). The first resin layer was applied using a comma coater so that the thickness of the first resin layer became 4.5 μm, and dried at 140 ° C. for 3 minutes to form the first resin layer on the support.
Next, on the formed first resin layer, the second resin composition was applied using a comma coater so that the thickness of the second resin layer after drying was 35.5 μm, and at 95 ° C. Dried for 2 minutes. Next, a 15 μm-thick polypropylene film was wound as a protective film on the surface of the second resin layer while being rolled up to obtain a composite film 1 having a support and a protective film.

Comparative Examples 2-3
(Composite film 2-3)
In Example 4, composite films 2 to 3 were obtained in the same manner as in Example 4 except that the first resin composition E was changed to the first resin compositions F and G.

[Evaluation of composite film]
The composite film obtained above was evaluated by the following method. The results are shown in Table 2.

[Reaction start temperature and reaction heat]
The protective film was peeled off from the composite film, and the resin layer was scraped off. Using the scraped resin composition, the reaction start temperature and reaction heat of the composite film were measured by the same method as the measurement method of the reaction start temperature and reaction heat of the first resin composition described above.

[Surface roughness Ra after roughening treatment]
A substrate for evaluating the surface roughness was prepared by the following procedure.
(Test piece preparation method)
The composite film obtained in each example was cut into a size of 240 mm × 240 mm, and then the protective film was peeled off.
The second resin layer and the printed wiring board come into contact with the obtained composite film having the support on the printed wiring board (trade name: E-700GR, manufactured by Hitachi Chemical Co., Ltd.) subjected to CZ treatment. Was laminated as follows. Lamination was performed by a method in which pressure was reduced to 0.5 MPa by reducing the pressure at 100 ° C. for 45 seconds, and then pressing was performed at 110 ° C. for 60 seconds at a pressure of 0.5 MPa.
Then, it cooled to room temperature and obtained the printed wiring board which distribute | arranged the composite film. Next, the printed wiring board on which the composite film is arranged is cured in an explosion-proof dryer at 130 ° C. for 20 minutes as the first stage curing with the support attached, and then the second stage curing. Curing was performed in an explosion-proof dryer at 190 ° C. for 40 minutes to obtain a printed wiring board on which an interlayer insulating layer was formed. Then, the printed wiring board obtained by peeling a support body was made into the test piece.

(Roughening method of test piece)
Next, the test piece obtained above was subjected to roughening treatment by the following method.
The test piece was dipped in a swelling liquid heated to 60 ° C. (Rohm and Haas Electronic Materials Co., Ltd., trade name: CIRCUPOSIT MLB CONDITIONER 211) for 10 minutes. Next, it was immersed in a roughening liquid (Rohm and Haas Electronic Materials Co., Ltd., trade name: CIRCUPOSIT MLB PROMOTER213) heated to 80 ° C. for 15 minutes. Subsequently, the mixture was neutralized by immersion for 5 minutes in a neutralizing solution heated to 45 ° C. (Rohm and Haas Electronic Materials Co., Ltd., trade name: CIRCUPOSIT MLB NEUTRALIZER MLB216). Thus, what roughened the surface of the interlayer insulation layer of the said test piece was used as a substrate for surface roughness measurement.

(Surface roughness measurement method for substrate for surface roughness measurement)
Next, the surface roughness of the surface roughness measurement substrate obtained above was measured by the following method.
The surface roughness of the substrate for measuring the surface roughness is measured using a specific contact surface roughness meter (Bruker AXS Co., Ltd., trade name: wykoNT9100), using an internal lens 1 × and an external lens 50 ×. The arithmetic average roughness (Ra) was obtained, and this was defined as the surface roughness Ra. From the gist of the present invention, Ra is preferably smaller, and if it is less than 250 nm, it is suitable for forming fine wiring.

[Plating peel strength]
A substrate for plating peel strength measurement was produced by the following procedure.
(Preparation method of plating peel strength measurement substrate)
First, a printed wiring board with a composite film produced by the same method as in [Surface roughness Ra after roughening treatment] was cut into 40 mm × 60 mm, and used as a test piece. After roughening the test piece in the same manner as the substrate for measuring the surface roughness, the test piece was treated with an alkali cleaner (manufactured by Atotech Japan Co., Ltd., trade name: Cleaner Securigant 902) for 5 minutes, and degreased and washed. did. After washing, it was treated with a 23 ° C. pre-dip solution (manufactured by Atotech Japan Co., Ltd., trade name: Pre-dip Neo Gant B) for 2 minutes. Then, it processed for 5 minutes with the 40 degreeC activator liquid (Atotech Japan Co., Ltd. make, brand name: Activator Neogant 834), and the palladium catalyst was made to adhere. Next, it processed for 5 minutes with a 30 degreeC reducing liquid (Atotech Japan Co., Ltd. make, brand name: Reducer Neogant WA).
The test piece subjected to the above treatment is put in a chemical copper solution (manufactured by Atotech Japan Co., Ltd., trade name: Basic Print Gantt MSK-DK), and until the plating thickness on the interlayer insulating layer reaches 0.5 μm Electroplating was performed. After the electroless plating, a 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, electrolytic plating was performed on the test piece subjected to the electroless plating treatment until the plating thickness on the interlayer insulating layer became 35 μm, and a copper layer was formed as a conductor layer. After the electrolytic plating, the substrate was heated and cured at 190 ° C. for 120 minutes to obtain a measurement substrate before production of the adhesive strength measurement part.
A 10 mm wide resist was formed on the copper layer, and the copper layer was etched with ammonium persulfate to obtain a plating peel strength measurement substrate having a 10 mm wide copper layer as an adhesive strength measurement part.

(Measurement method of plating peel strength)
Using the plating peel strength measurement substrate obtained as described above, the adhesion strength between the interlayer insulating layer and the copper layer was measured by the following method.
One end of the copper layer of the adhesive strength measuring section is peeled off at the interface between the copper layer and the interlayer insulating layer and is gripped with a gripper, and vertically using a small tabletop testing machine (manufactured by Shimadzu Corporation, trade name: EZT Test). The load when it was peeled off at room temperature at a pulling speed of 50 mm / min in the direction was measured.

[Presence or absence of whitening on the surface of the interlayer insulating layer]
The composite film obtained in each example was cut into a size of 240 mm × 240 mm, and then the protective film was peeled off.
The second resin layer and the printed wiring board come into contact with the composite film having the obtained support on the printed wiring board (trade name: E-700GR, manufactured by Hitachi Chemical Co., Ltd.) on which the wiring pattern has been applied. Was laminated as follows. Lamination was performed by a method in which pressure was reduced to 0.5 MPa by reducing the pressure at 100 ° C. for 45 seconds, and then pressing was performed at 110 ° C. for 60 seconds at a pressure of 0.5 MPa.
Then, it cooled to room temperature and obtained the printed wiring board which distribute | arranged the composite film. Next, the printed wiring board on which the composite film is disposed is cured in an explosion-proof dryer at 130 ° C. for 20 minutes as the first stage curing with the support attached, and then 190 ° C. as the second stage curing. Was cured in an explosion-proof dryer for 40 minutes to obtain a printed wiring board on which an interlayer insulating layer was formed. Thereafter, the support was peeled off to obtain a printed wiring board.
The presence or absence of whitening is observed by visually observing the surface of the interlayer insulating layer of the obtained printed wiring board, and no whitening occurs on the surface of the interlayer insulating layer. The thing is “Yes”. In the evaluation of whitening, “none” is preferable.

[Dielectric loss tangent]
The resin plate used for the measurement of dielectric loss tangent was produced by the following procedure.
(Production method of resin plate)
(I) After the protective film was peeled off from the composite film obtained in each example, it was dried at 120 ° C. for 3 minutes.
Next, the composite film having the support after drying is subjected to copper foil (electrolytic copper foil, thickness) using a vacuum pressure laminator (manufactured by Meiki Seisakusho Co., Ltd., trade name: MVLP-500 / 600-II). On the glossy surface of 35 μm), the second resin layer and the copper foil were laminated so that they contacted to obtain a laminate (P) in which the copper foil, the composite film, and the support were laminated in this order. Lamination was performed by reducing pressure for 30 seconds to a pressure of 0.5 MPa, and then pressing at 120 ° C. for 30 seconds with a pressure of 0.5 MPa. Then, the support body was peeled from the laminated body (P).
(II) Next, another composite film was prepared and the protective film was peeled off, followed by drying at 110 ° C. for 3 minutes.
(III) Next, the laminate (P) from which the support obtained in (I) above was peeled off, and the composite film having the dried support obtained in (II) above, Lamination was performed under the same conditions as in (I) above to obtain a laminate (Q) in which a copper foil, a layer composed of two composite films, and a support were laminated in this order. Thereafter, the support was peeled from the laminate (Q).
(IV) Next, a laminate (Q) from which the support obtained in (III) was peeled, and a composite film having a dried support obtained by the same method as in (II) above, Lamination was performed under the same conditions as in the above (I) so that the composite films were in contact with each other, thereby obtaining a laminate (R) in which a copper foil, a layer composed of three composite films, and a support were laminated in this order.
(V) A laminate (Q) was produced by the same method as in the above (I) to (III).
(VI) The laminate (Q) obtained in the above (V) and the support of the laminate (R) obtained in the above (I) to (IV) are peeled off, and the laminate (Q) and the laminate are laminated. The composite films of the body (R) were bonded together, and press-molded using a vacuum press at 190 ° C. for 60 minutes at a pressure of 3.0 MPa. After the obtained resin plate with double-sided copper foil was cured at 190 ° C. for 2 hours, the copper foil was etched with ammonium persulfate to obtain a resin plate.

(Measurement method of dielectric loss tangent)
The resin plate produced above is cut into a test piece having a width of 2 mm and a length of 70 mm, and a network analyzer (manufactured by Agilent Technologies, trade name: E8364B) and a cavity resonator for 5 GHz (manufactured by Kanto Electronics Application Development Co., Ltd.) Was used to measure the dielectric loss tangent. The measurement temperature was 25 ° C. A lower dielectric loss tangent indicates better dielectric properties.

*: In the table, the unit of the blending amount of each component that does not have a unit is “part by mass”.
* 1: Means the amount of component (C) or component (D) to 100 parts by mass of component (A).
* 2: It means the blending amount with respect to 100 parts by mass in total of the raw material (bismaleimide) and the modified polybutadiene (G) converted from the charged amount of the polyimide compound (F).
* 3: It means the blending amount with respect to the raw material (bismaleimide) converted from the charged amount of the polyimide compound (F).

From Table 2, the printed wiring board of Example 4 using the composite film of the present embodiment is not whitened during pattern embedding, and has a smooth surface (low surface roughness (Ra)) and adhesive strength between plated copper. It had an excellent interlayer insulating layer. On the other hand, it turns out that the interlayer insulation layer of Comparative Examples 2-3 is inferior to Example 4 by either characteristic. Moreover, since the composite film of Example 4 has a smaller reaction heat than the composite films of Comparative Examples 2 and 3, the curing reaction of the first resin layer proceeds during drying when the composite film is produced. This suggests that the occurrence of whitening is suppressed.
As described above, the composite film of the present embodiment does not whiten during pattern embedding, can form a smooth surface and an interlayer insulating layer excellent in adhesive strength with plated copper, and is suitable for forming fine wiring. I understand that.

  The composite film for interlayer insulation of the present invention does not cause whitening during pattern embedding, and has a smooth surface and an interlayer insulating layer excellent in adhesive strength between plated copper. Therefore, the thermosetting resin composition, the resin film for interlayer insulation, the composite film, and the printed wiring board of the present invention are used for electrical products such as computers, mobile phones, digital cameras, and televisions; motorcycles, automobiles, trains, ships, Useful for vehicles such as aircraft.

DESCRIPTION OF SYMBOLS 1 2nd resin layer 2 1st resin layer 3 Support body 4 Protective film

Claims (16)

  A thermosetting resin composition comprising an epoxy resin (A), an active ester curing agent (B), a phosphorus curing accelerator (C) and a pyridine compound (D) having a tertiary amino group.   The equivalent ratio (ester group / epoxy group) of the ester group of the active ester curing agent (B) to the epoxy group of the epoxy resin (A) contained in the thermosetting resin composition is 0.3 to 1.5. The thermosetting resin composition according to claim 1.   The thermosetting resin composition according to claim 1 or 2, further comprising a phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (E).   The thermosetting resin composition of Claim 3 whose content of the said component (E) is 1-20 mass parts with respect to 100 mass parts of solid content of the said thermosetting resin composition.   The thermosetting resin composition according to any one of claims 1 to 4, wherein the phosphorus-based curing accelerator (C) is an adduct of a tertiary phosphine and a quinone.   The content of the phosphorus-based curing accelerator (C) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting resin composition. The thermosetting resin composition described in 1.   The thermosetting resin composition according to any one of claims 1 to 6, wherein the pyridine compound (D) having a tertiary amino group is 4-dimethylaminopyridine.   The content of the pyridine compound (D) having a tertiary amino group is 0.1 to 20 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting resin composition. The thermosetting resin composition according to any one of the above.   The resin film for interlayer insulation containing the thermosetting resin composition of any one of Claims 1-8.   The composite film containing the 1st resin composition layer containing the thermosetting resin composition of any one of Claims 1-8, and the 2nd resin composition layer.   The second resin composition layer contains a polyimide compound (F) having a structural unit derived from an aliphatic maleimide compound and a structural unit derived from a diamine compound, a modified polybutadiene (G), and an inorganic filler (H). The composite film according to claim 10, comprising a second thermosetting resin composition.   The composite film according to claim 10 or 11, wherein the cured product has a dielectric loss tangent of 5 GHz of 0.005 or less.   The printed wiring board containing the hardened | cured material of the resin film for interlayer insulation of Claim 9, or the hardened | cured material of the composite film of any one of Claims 10-12.   The manufacturing method of a printed wiring board provided with the process of laminating the resin film for interlayer insulation of Claim 9, or the composite film of any one of Claims 10-12 on the single side | surface or both surfaces of a base material. A resin composition layer (I) containing a thermosetting resin composition (I);
A resin composition layer (II) containing a thermosetting resin composition (II);
A composite film having
The resin composition layer (II) is a layer that embeds the inner layer circuit to form an interlayer insulating layer,
The resin composition layer (I) is a layer that forms an adhesion auxiliary layer with a conductor layer on the surface opposite to the inner layer circuit of the interlayer insulating layer,
The composite film whose reaction start temperature of a thermosetting resin composition (I) is 140 degrees C or less.   The reaction start temperature of the thermosetting resin composition (II) is higher than the reaction start temperature of the thermosetting resin composition (I), and the temperature difference is 5 to 50 ° C. 15. The composite film according to 15.