JP6885001B2 - Prepreg, laminated board and printed wiring board - Google Patents

Description

The present invention relates to a prepreg, a laminated board and a printed wiring board suitable as materials for electronic devices and the like.

In recent years, in motherboards such as multifunctional mobile phone terminals, the ratio of the wiring width (L) to the interval (S) of the wiring board [L / S] has been increased along with high-speed communication, high-density wiring, and ultra-thin wiring board. ] Also tends to narrow. With such narrowing of L / S, it is becoming difficult to stably produce wiring boards with good yield. Further, in the conventional design of the wiring board, in consideration of communication failure and the like, a layer without a wiring pattern called a "skip layer" is provided in some layers. As electronic devices become more sophisticated, the amount of wiring design increases, and the number of layers of wiring boards increases. However, by providing the skip layer, there is a problem that the thickness of the motherboard is further increased.
As a method of improving these problems, it is effective to reduce the relative permittivity of the insulating material used for the wiring board. By lowering the relative permittivity of the insulating material, it becomes easier to control the impedance of the L / S, so stable production of the L / S can be achieved with a shape close to the current design, and the number of layers can be reduced by reducing the number of skip layers. Become. Therefore, the insulating material used for the wiring board is required to have a material property with a small relative permittivity.

In recent years, as the density of electronic devices has increased, the thickness and price of motherboards such as mobile phones have been reduced, and materials having a low relative permittivity are required in order to cope with the reduction in thickness. In addition, communication equipment such as servers, routers, and mobile base stations are also being used in the higher frequency band region, and high melting point lead-free soldering is used for soldering electronic components. As the material of the substrate used for these, a material having a low dielectric constant, a high glass transition temperature (high Tg), and excellent reflow heat resistance is required. It has come to be.
Further, in a motherboard used for a multifunctional mobile phone terminal or the like, as the wiring density increases and the pattern width becomes narrower, a small-diameter laser via is required to connect the layers. From the viewpoint of connection reliability, filled plating is often used, and since the connectivity at the interface between the inner layer copper and the plated copper is very important, improvement of the laser workability of the base material is required.

After laser processing of the base material, a step of removing the residual component of the resin (desmear treatment step) is generally performed. Since the desmear treatment is performed on the bottom surface and the wall surface of the laser via, if a large amount of the resin component of the base material is dissolved by the desmear treatment, the shape of the laser via may be significantly deformed due to the dissolution of the resin, and the unevenness of the wall surface may vary. Various problems can occur, such as non-uniformity around the plating. From this, it is required that the amount of the resin component of the base material dissolved by the desmear treatment, that is, the so-called desmear dissolution amount, becomes an appropriate value.

So far, in order to obtain a thermosetting resin composition having a small relative permittivity, a method of containing an epoxy resin having a small relative permittivity, a method of introducing a cyanate group, a method of containing a polyphenylene ether, and the like have been used. It was. However, it has been difficult to satisfy various requirements such as reduction of relative permittivity, high heat resistance, reliability, and halogen-free by simply combining these methods. For example, a resin composition containing an epoxy resin (see Patent Document 1), a resin composition containing a polyphenylene ether and bismaleimide (see Patent Document 2), and a resin composition containing a polyphenylene ether and a cyanate resin (Patent). (Refer to Document 3), a resin composition containing at least one of a styrene-based thermoplastic elastomer and / or triallyl cyanurate (see Patent Document 4), a resin composition containing polybutadiene (see Patent Document 5), and polyphenylene. A resin composition obtained by pre-reacting an ether resin, a polyfunctional maleimide and / or a polyfunctional cyanate resin, and a liquid polybutadiene (see Patent Document 6), a compound having an unsaturated double bond group is added or added. Resin composition containing grafted polyphenylene ether and triallyl cyanurate and / or triallyl isocyanurate (see Patent Document 7), reaction formation between polyphenylene ether and unsaturated carboxylic acid or unsaturated acid anhydride A resin composition containing a product and a polyfunctional maleimide or the like (see Patent Document 8) and the like have been proposed.

Japanese Unexamined Patent Publication No. 58-69046 Japanese Unexamined Patent Publication No. 56-133355 Special Publication No. 61-18937 Japanese Unexamined Patent Publication No. 61-286130 Japanese Unexamined Patent Publication No. 62-148512 Japanese Unexamined Patent Publication No. 58-164638 Japanese Unexamined Patent Publication No. 2-208355 Japanese Unexamined Patent Publication No. 6-179734

The prepreg containing the resin compositions described in Patent Documents 1 to 8 exhibits a relatively good relative permittivity, but there have been many cases in which the strict requirements of the market in recent years cannot be satisfied. In addition, any of high heat resistance, high metal leaf adhesiveness, high glass transition temperature, low thermal expansion, moldability and plating turnability (laser workability) is often insufficient, and there is room for further improvement. is there. Further, in the past, the actual situation is that material development has not been sufficiently carried out from the viewpoint of being suitable for plating turnability.
Therefore, the subject of the present invention is a prepreg, a laminated board, which has high heat resistance, low relative permittivity, high metal leaf adhesiveness, high glass transition temperature and low thermal expansion, and excellent moldability and plating turnability. The purpose is to provide a printed wiring board.

As a result of diligent research to solve the above problems, the present inventors have "(A) maleimide compound", "(B) epoxy resin", and "(C) copolymer resin having a specific structural unit". The present invention has been completed by finding that a prepreg containing a thermosetting resin composition containing "(D) silica treated with an aminosilane-based coupling agent" can solve the above-mentioned problems. I came to do it. The present invention has been completed based on such findings.

（一般式（ａ２−１）中、Ｒ^Ａ４は、水酸基、カルボキシ基及びスルホン酸基から選択される酸性置換基を示す。Ｒ^Ａ５は、炭素数１〜５のアルキル基又はハロゲン原子を示す。ｔは１〜５の整数、ｕは０〜４の整数であり、且つ、１≦ｔ＋ｕ≦５を満たす。但し、ｔが２〜５の整数の場合、複数のＲ^Ａ４は同一であってもよいし、異なっていてもよい。また、ｕが２〜４の整数の場合、複数のＲ^Ａ５は同一であってもよいし、異なっていてもよい。）

（一般式（ａ３−１）中、Ｘ^Ａ２は、炭素数１〜３の脂肪族炭化水素基又は−Ｏ−を示す。Ｒ^Ａ６及びＲ^Ａ７は、各々独立に、炭素数１〜５のアルキル基、ハロゲン原子、水酸基、カルボキシ基又はスルホン酸基を示す。ｖ及びｗは、各々独立に、０〜４の整数である。）
［３］前記（Ｃ）成分が、下記一般式（Ｃ−ｉ）で表される構造単位と下記式（Ｃ−ii）で表される構造単位とを有する共重合樹脂である、上記［１］又は［２］に記載のプリプレグ。

（式中、Ｒ^Ｃ１は、水素原子又は炭素数１〜５のアルキル基であり、Ｒ^Ｃ２は、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基、炭素数６〜２０のアリール基、水酸基又は（メタ）アクリロイル基である。ｘは、０〜３の整数である。但し、ｘが２又は３である場合、複数のＲ^Ｃ２は同一であってもよいし、異なっていてもよい。）
［４］前記一般式（Ｃ−ｉ）中、Ｒ^Ｃ１が水素原子であり、且つｘが０である、上記［３］に記載のプリプレグ。
［５］前記（Ｃ）成分において、芳香族ビニル化合物に由来する構造単位と無水マレイン酸に由来する構造単位の含有比率［芳香族ビニル化合物に由来する構造単位／無水マレイン酸に由来する構造単位］（モル比）が２〜９である、上記［１］又は［２］に記載のプリプレグ。
［６］前記（Ｃ）成分において、芳香族ビニル化合物に由来する構造単位と無水マレイン酸に由来する構造単位の含有比率［芳香族ビニル化合物に由来する構造単位／無水マレイン酸に由来する構造単位］（モル比）が３〜７である、上記［１］又は［２］に記載のプリプレグ。
［７］前記（Ｃ）成分の重量平均分子量が４，５００〜１８，０００である、上記［１］〜［６］のいずれかに記載のプリプレグ。
［８］前記（Ｃ）成分の重量平均分子量が９，０００〜１３，０００である、上記［１］〜［７］のいずれかに記載のプリプレグ。
［９］前記（Ｂ）成分が、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ナフタレン型エポキシ樹脂、アントラセン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂又はジシクロペンタジエン型エポキシ樹脂である、上記［１］〜［８］のいずれかに記載のプリプレグ。
［１０］前記熱硬化性樹脂組成物がさらに（Ｅ）硬化剤を含有する、上記［１］〜［９］のいずれかに記載のプリプレグ。
［１１］前記熱硬化性樹脂組成物がさらに（Ｆ）難燃剤を含有する、上記［１］〜［１０］のいずれかに記載のプリプレグ。
［１２］上記［１］〜［１１］のいずれかに記載のプリプレグと金属箔とを含有してなる積層板。
［１３］上記［１］〜［１１］のいずれかに記載のプリプレグ又は上記［１２］に記載の積層板を含有してなるプリント配線板。 The present invention relates to the following [1] to [13].
[1] (A) Maleimide compound,
(B) An epoxy resin having at least two epoxy groups in one molecule,
A thermosetting resin composition containing (C) a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride, and (D) silica treated with an aminosilane-based coupling agent. A prepreg containing a substance.
[2] The component (A) includes a maleimide compound having at least two N-substituted maleimide groups in one molecule (a1), and (a2) a monoamine compound represented by the following general formula (a2-1). (A3) The prepreg according to the above [1], which is a maleimide compound having an N-substituted maleimide group obtained by reacting with a diamine compound represented by the following general formula (a3-1).

(In the general formula ^{(a2-1), R A4} represents a hydroxyl group, ^{.R A5} is showing an acidic substituent group selected from a carboxy group and a sulfonic acid group, an alkyl group or a halogen atom having 1 to 5 carbon atoms. t is an integer of 1 to 5, u is an integer of 0 to 4, and satisfies 1 ≦ t + u ≦ 5. However, when t is an integer of 2 to 5, a plurality of ^RA4s may be the same. It may be different, and when u is an integer of 2 to 4, a plurality of ^RA5s may be the same or different.)

(In the general formula ^{(a3-1), X A2} is ^{.R A6} and ^{R A7} represents an aliphatic hydrocarbon group or an -O- of 1 to 3 carbon atoms are each independently alkyl having 1 to 5 carbon atoms Indicates a group, a halogen atom, a hydroxyl group, a carboxy group or a sulfonic acid group. V and w are independently integers of 0 to 4).
[3] The component (C) is a copolymer resin having a structural unit represented by the following general formula (C-i) and a structural unit represented by the following formula (C-ii). ] Or [2].

(In the formula, ^RC1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and ^RC2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and 6 to 20 carbon atoms. It is an aryl group, a hydroxyl group or a (meth) acryloyl group. X is an integer of 0 to 3. However, when x is 2 or 3, a plurality of ^RC2s may be the same or different. May be.)
[4] The prepreg according to the above [3], wherein ^RC1 is a hydrogen atom and x is 0 in the general formula (C-i).
[5] In the component (C), the content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from maleic anhydride [Structural unit derived from the aromatic vinyl compound / structural unit derived from maleic anhydride ] (Mole ratio) is 2-9, the prepreg according to the above [1] or [2].
[6] In the component (C), the content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from maleic anhydride [Structural unit derived from the aromatic vinyl compound / structural unit derived from maleic anhydride ] (Mole ratio) is 3 to 7, the prepreg according to the above [1] or [2].
[7] The prepreg according to any one of the above [1] to [6], wherein the weight average molecular weight of the component (C) is 4,500 to 18,000.
[8] The prepreg according to any one of the above [1] to [7], wherein the weight average molecular weight of the component (C) is 9,000 to 13,000.
[9] The component (B) is a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthalene type epoxy resin, an anthracene type epoxy resin, a biphenyl type epoxy resin, a biphenyl aralkyl type epoxy resin or a diphenyl. The prepreg according to any one of the above [1] to [8], which is a cyclopentadiene type epoxy resin.
[10] The prepreg according to any one of [1] to [9] above, wherein the thermosetting resin composition further contains (E) a curing agent.
[11] The prepreg according to any one of the above [1] to [10], wherein the thermosetting resin composition further contains (F) a flame retardant.
[12] A laminated board containing the prepreg according to any one of the above [1] to [11] and a metal foil.
[13] A printed wiring board containing the prepreg according to any one of the above [1] to [11] or the laminated board according to the above [12].

According to the present invention, a prepreg, a laminated board and a printed wiring board having high heat resistance, low relative permittivity, high metal leaf adhesiveness, high glass transition temperature and low thermal expansion property, and excellent moldability and plating turnability can be obtained. can get.

Hereinafter, the present invention will be described in detail.
The present invention provides a prepreg containing the following thermosetting resin composition.
[Thermosetting resin composition]
The thermosetting resin composition is
(A) Maleimide compound,
(B) Epoxy resin,
A thermosetting resin composition containing (C) a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride, and (D) silica treated with an aminosilane-based coupling agent. It is a prepreg containing a substance.

（一般式（ａ２−１）中、Ｒ^Ａ４は、水酸基、カルボキシ基及びスルホン酸基から選択される酸性置換基を示す。Ｒ^Ａ５は、炭素数１〜５のアルキル基又はハロゲン原子を示す。ｔは１〜５の整数、ｕは０〜４の整数であり、且つ、１≦ｔ＋ｕ≦５を満たす。但し、ｔが２〜５の整数の場合、複数のＲ^Ａ４は同一であってもよいし、異なっていてもよい。また、ｕが２〜４の整数の場合、複数のＲ^Ａ５は同一であってもよいし、異なっていてもよい。）
で示されるモノアミン化合物［以下、モノアミン化合物（ａ２）と略称する］と、（ａ３）下記一般式（ａ３−１）

（一般式（ａ３−１）中、Ｘ^Ａ２は、炭素数１〜３の脂肪族炭化水素基又は−Ｏ−を示す。Ｒ^Ａ６及びＲ^Ａ７は、各々独立に、炭素数１〜５のアルキル基、ハロゲン原子、水酸基、カルボキシ基又はスルホン酸基を示す。ｖ及びｗは、各々独立に、０〜４の整数である。）
で示されるジアミン化合物［以下、ジアミン化合物（ａ３）と略称する］とを反応させて得られる、Ｎ−置換マレイミド基を有するマレイミド化合物である。
以下、マレイミド化合物（Ａ）に関する記載は、上記のＮ−置換マレイミド基を有するマレイミド化合物の記載として読むこともできる。 Hereinafter, each component contained in the thermosetting resin composition will be described in detail.
<(A) Maleimide compound>
The component (A) is a maleimide compound (hereinafter, may be referred to as a maleimide compound (A)), preferably a maleimide compound having an N-substituted maleimide group, and more preferably (a1) at least in one molecule. A maleimide compound having two N-substituted maleimide groups [hereinafter abbreviated as maleimide compound (a1)] and (a2) the following general formula (a2-1)

(In the general formula ^{(a2-1), R A4} represents a hydroxyl group, ^{.R A5} is showing an acidic substituent group selected from a carboxy group and a sulfonic acid group, an alkyl group or a halogen atom having 1 to 5 carbon atoms. t is an integer of 1 to 5, u is an integer of 0 to 4, and satisfies 1 ≦ t + u ≦ 5. However, when t is an integer of 2 to 5, a plurality of ^RA4s may be the same. It may be different, and when u is an integer of 2 to 4, a plurality of ^RA5s may be the same or different.)
[Hereinafter, abbreviated as monoamine compound (a2)] and (a3) the following general formula (a3-1).

(In the general formula ^{(a3-1), X A2} is ^{.R A6} and ^{R A7} represents an aliphatic hydrocarbon group or an -O- of 1 to 3 carbon atoms are each independently alkyl having 1 to 5 carbon atoms Indicates a group, a halogen atom, a hydroxyl group, a carboxy group or a sulfonic acid group. V and w are independently integers of 0 to 4).
It is a maleimide compound having an N-substituted maleimide group obtained by reacting with the diamine compound represented by (hereinafter, abbreviated as diamine compound (a3)].
Hereinafter, the description regarding the maleimide compound (A) can also be read as the description of the above-mentioned maleimide compound having an N-substituted maleimide group.

The weight average molecular weight (Mw) of the maleimide compound (A) is preferably 400 to 3,500, more preferably 400 to 2,300, still more preferably 800, from the viewpoint of solubility in an organic solvent and mechanical strength. ~ 2,000. The weight average molecular weight in the present specification is a value measured by a gel permeation chromatography (GPC) method (standard polystyrene conversion) using tetrahydrofuran as an eluent, and more specifically described in Examples. It is a value measured by the method.

(Maleimide compound (a1))
The maleimide compound (a1) is a maleimide compound having at least two N-substituted maleimide groups in one molecule.
Is the maleimide compound (a1) a maleimide compound having an aliphatic hydrocarbon group between any two maleimide groups among a plurality of maleimide groups [hereinafter, referred to as an aliphatic hydrocarbon group-containing maleimide]? Alternatively, a maleimide compound containing an aromatic hydrocarbon group between any two maleimide groups among the plurality of maleimide groups [hereinafter, referred to as an aromatic hydrocarbon group-containing maleimide] can be mentioned. Among these, aromatic hydrocarbon group-containing maleimides are preferable from the viewpoints of high heat resistance, low relative permittivity, high metal leaf adhesiveness, high glass transition temperature, low thermal expansion, moldability and plating turnability. The aromatic hydrocarbon group-containing maleimide may contain an aromatic hydrocarbon group between any combination of two optionally selected maleimide groups.
As the maleimide compound (a1), 2 to 2 per molecule from the viewpoints of high heat resistance, low specific dielectric constant, high metal foil adhesiveness, high glass transition temperature, low thermal expansion, moldability and turnability with plating. A maleimide compound having 5 N-substituted maleimide groups is preferable, and a maleimide compound having 2 N-substituted maleimide groups in one molecule is more preferable. The maleimide compound (a1) has the following general formula (a1) from the viewpoints of high heat resistance, low specific dielectric constant, high metal foil adhesiveness, high glass transition temperature, low thermal expansion, moldability and turnability with plating. It is more preferable that it is an aromatic hydrocarbon group-containing maleimide represented by any one of -1) to (a1-4), and the following general formulas (a1-1), (a1-2) or (a1-4). It is more preferable that it is an aromatic hydrocarbon group-containing maleimide represented by, and it is particularly preferable that it is an aromatic hydrocarbon group-containing maleimide represented by the following general formula (a1-2).

In the above ^formulas, R A1 ^{to R A3} each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms. X ^A1 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O -, - C (= O) -, - S -, - shows the S-S- or a sulfonyl group. p, q and r are each independently an integer of 0-4. s is an integer from 0 to 10.
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^A1 to R ^A3, for example, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, t- butyl group, Examples thereof include an n-pentyl group. The aliphatic hydrocarbon group preferably has 1 to 1 carbon atoms from the viewpoints of high heat resistance, low specific dielectric constant, high metal foil adhesiveness, high glass transition temperature, low thermal expansion, moldability and turnability. 3 is an aliphatic hydrocarbon group, more preferably a methyl group or an ethyl group.

As the alkylene group having 1 to 5 carbon atoms represented by X ^A1, for example, methylene, 1,2-dimethylene group, a 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group Can be mentioned. The alkylene group is preferably an alkylene having 1 to 3 carbon atoms from the viewpoints of high heat resistance, low relative permittivity, high metal leaf adhesiveness, high glass transition temperature, low thermal expansion, moldability and plating turnability. It is a group, more preferably a methylene group.
The alkylidene group having 2 to 5 carbon atoms represented by X ^A1, for example, ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group, and the like. Among these, an isopropylidene group is preferable from the viewpoints of high heat resistance, low relative permittivity, high metal leaf adhesiveness, high glass transition temperature, low thermal expansion, moldability and plating turnability.
Among the above options, the X ^A1 is preferably an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms. More preferred are as described above.
p, q and r are each independently an integer of 0 to 4, and have high heat resistance, low relative permittivity, high metal foil adhesiveness, high glass transition temperature, low thermal expansion, moldability and plating turnability. From this point of view, all of them are preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
s is an integer of 0 to 10, preferably 0 to 5, and more preferably 0 to 3 from the viewpoint of availability. In particular, the aromatic hydrocarbon group-containing maleimide compound represented by the general formula (a1-3) is preferably a mixture having s of 0 to 3.

Specific examples of the maleimide compound (a1) include N, N'-ethylene bismaleimide, N, N'-hexamethylene bismaleimide, bis (4-maleimide cyclohexyl) methane, and 1,4-bis (maleimide). Maleimide containing an aliphatic hydrocarbon group such as methyl) cyclohexane; N, N'-(1,3-phenylene) bismaleimide, N, N'-[1,3- (2-methylphenylene)] bismaleimide, N, N'-[1,3- (4-methylphenylene)] bismaleimide, N, N'-(1,4-phenylene) bismaleimide, bis (4-maleimidephenyl) methane, bis (3-methyl-4- Maleimide phenyl) methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, bis (4-maleimidephenyl) ether, bis (4-maleimidephenyl) sulfone, bis (4-) Maleimide phenyl) sulfide, bis (4-maleimide phenyl) ketone, 1,4-bis (4-maleimidephenyl) cyclohexane, 1,4-bis (maleimidemethyl) cyclohexane, 1,3-bis (4-maleimidephenoxy) benzene , 1,3-bis (3-maleimide phenoxy) benzene, bis [4- (3-maleimide phenoxy) phenyl] methane, bis [4- (4-maleimide phenoxy) phenyl] methane, 1,1-bis [4- (3-Maleimide phenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimide phenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimide phenoxy) phenyl] ethane, 1,2- Bis [4- (4-maleimide phenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimide phenoxy) phenyl] propane, 2,2-bis [4- (4-maleimide phenoxy) phenyl] propane, 2,2-bis [4- (3-maleimide phenoxy) phenyl] butane, 2,2-bis [4- (4-maleimide phenoxy) phenyl] butane, 2,2-bis [4- (3-maleimide phenoxy)) Phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-maleimidephenoxy) phenyl] -1,1,1,3,3,3-hexafluoro Propane, 4,4-bis (3-maleimide phenoxy) biphenyl, 4,4-bis (4-maleimide phenoxy) biphenyl, bis [4- (3-maleimide phenoxy) phenyl] Ton, bis [4- (4-maleimidephenoxy) phenyl] ketone, 2,2'-bis (4-maleimidephenyl) disulfide, bis (4-maleimidephenyl) disulfide, bis [4- (3-maleimidephenoxy) phenyl ] Sulfate, bis [4- (4-maleimide phenoxy) phenyl] sulfide, bis [4- (3-maleimide phenoxy) phenyl] sulfoxide, bis [4- (4-maleimide phenoxy) phenyl] sulfoxide, bis [4- ( 3-Maleimide phenoxy) phenyl] sulfone, bis [4- (4-maleimide phenoxy) phenyl] sulfone, bis [4- (3-maleimide phenoxy) phenyl] ether, bis [4- (4-maleimide phenoxy) phenyl] ether , 1,4-bis [4- (4-maleimide phenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimide phenoxy) -α, α-dimethylbenzyl] benzene, 1, , 4-bis [4- (3-maleimide phenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimide phenoxy) -α, α-dimethylbenzyl] benzene, 1,4 -Bis [4- (4-maleimide phenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimide phenoxy) -3,5-dimethyl-α, α-Dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimide phenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimide phenoxy) ) -3,5-dimethyl-α, α-dimethylbenzyl] Examples thereof include aromatic hydrocarbon group-containing maleimides such as benzene and polyphenylmethane maleimide.
Among these, bis (4-maleimidephenyl) methane, bis (4-maleimidephenyl) sulfone, bis (4-maleimidephenyl) sulfide, and bis (4) from the viewpoint of high reaction rate and higher heat resistance. -Maleimidephenyl) disulfide, N, N'-(1,3-phenylene) bismaleimide, 2,2-bis [4- (4-maleimide phenyloxy) phenyl] propane are preferable, and bis from the viewpoint of low cost. (4-Maleimidephenyl) methane, N, N'-(1,3-phenylene) bismaleimide is preferable, and bis (4-maleimidephenyl) methane is particularly preferable from the viewpoint of solubility in a solvent.
The maleimide compound (a1) may be used alone or in combination of two or more.

(Monoamine compound (a2))
The monoamine compound (a2) is a monoamine compound represented by the following general formula (a2-1).

In the general formula ^{(a2-1), R A4} represents a hydroxyl group, an acidic substituent selected from a carboxy group and sulfonic acid groups. ^RA5 represents an alkyl group or a halogen atom having 1 to 5 carbon atoms. t is an integer of 1 to 5, u is an integer of 0 to 4, and 1 ≦ t + u ≦ 5 is satisfied. However, when t is an integer of 2 to 5, a plurality of ^RA4s may be the same or different. Further, when u is an integer of 2 to 4, a plurality of ^RA5s may be the same or different.
The ^{acidic substituent indicated by RA4} is preferably a hydroxyl group or a carboxy group from the viewpoint of solubility and reactivity, and more preferably a hydroxyl group in consideration of heat resistance.
t is an integer of 1 to 5, and is preferably 1 to 3 from the viewpoints of high heat resistance, low relative permittivity, high metal leaf adhesiveness, high glass transition temperature, low thermal expansion, moldability, and plating turnability. Is an integer of, more preferably 1 or 2, and even more preferably 1.
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^A5, for example, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, t- butyl group, n- pentyl group, and the Can be mentioned. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
As the halogen atom represented by R ^A5, fluorine atom, chlorine atom, bromine atom, and an iodine atom.
u is an integer of 0 to 4, and is preferably 0 to 3 from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesiveness, high glass transition temperature, low thermal expansion, moldability, and turnability with plating. , More preferably an integer of 0-2, even more preferably 0 or 1, and particularly preferably 0.
The monoamine compound (a2) is more preferably represented by the following general formula (a2) from the viewpoints of high heat resistance, low relative permittivity, high metal leaf adhesiveness, high glass transition temperature, low thermal expansion, moldability and plating turnability. It is a monoamine compound represented by a2-2) or (a2-3), and more preferably a monoamine compound represented by the following general formula (a2-2). However, ^{R A4, R A5} and u in the general formula (a2-2) and (a2-3) are the same as those of the general formula (a2-1), and preferred ones are also the same.

Examples of the monoamine compound (a2) include o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, and o-aminobenzenesulfonic acid. Examples thereof include monoamine compounds having an acidic substituent such as m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, and 3,5-dicarboxyaniline.
Among these, m-aminophenol, p-aminophenol, p-aminobenzoic acid, and 3,5-dihydroxyaniline are preferable from the viewpoint of solubility and reactivity, and o-aminophenol is preferable from the viewpoint of heat resistance. , M-Aminophenol and p-Aminophenol are preferable, and p-Aminophenol is more preferable in consideration of dielectric properties, low thermal expansion property and manufacturing cost.
One type of monoamine compound (a2) may be used alone, or two or more types may be used in combination.

（式中、Ｘ^Ａ２は、炭素数１〜３の脂肪族炭化水素基又は−Ｏ−を示す。Ｒ^Ａ６及びＲ^Ａ７は、各々独立に、炭素数１〜５のアルキル基、ハロゲン原子、水酸基、カルボキシ基又はスルホン酸基を示す。ｖ及びｗは、各々独立に、０〜４の整数である。） (Diamine compound (a3))
The diamine compound (a3) is a diamine compound represented by the following general formula (a3-1).

^{(Wherein, X A2} is ^{.R A6} and ^{R A7} represents an aliphatic hydrocarbon group or an -O- of 1 to 3 carbon atoms are each independently an alkyl group of 1 to 5 carbon atoms, a halogen atom, a hydroxyl group , Carboxy group or sulfonic acid group. V and w are independently integers from 0 to 4.)

Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms represented by X ^A2, for example, methylene group, ethylene group, propylene group, propylidene group, and the like.
As X ^A2 , a methylene group is preferable.
^{Examples of the alkyl group having 1 to 5 carbon atoms indicated by RA6} and ^RA7 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. Group etc. can be mentioned. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
v and w are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0.

Specific examples of the diamine compound (a3) include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylpropane, and 2,2'-bis [4. 4'-Diaminodiphenyl] Propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'- Diaminodiphenylethane, 3,3'-diethyl-4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylthioether, 3,3'-dihydroxy-4,4'-diamino Diphenylmethane, 2,2', 6,6'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dibromo-4,4'- Examples thereof include diaminodiphenylmethane, 2,2', 6,6'-tetramethylchloro-4,4'-diaminodiphenylmethane, 2,2', 6,6'-tetrabromo-4,4'-diaminodiphenylmethane and the like. Among these, 4,4'-diaminodiphenylmethane and 3,3'-diethyl-4,4'-diaminodiphenylmethane are preferable from the viewpoint of low cost, and 4,4'-from the viewpoint of solubility in a solvent. Diaminodiphenylmethane is more preferred.

The reaction of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3) can be carried out by reacting them at a reaction temperature of 70 to 200 ° C. for 0.1 to 10 hours, preferably in the presence of an organic solvent. preferable.
The reaction temperature is more preferably 70 to 160 ° C, still more preferably 70 to 130 ° C, and particularly preferably 80 to 120 ° C.
The reaction time is more preferably 1 to 6 hours, still more preferably 1 to 4 hours.

(Amount of Maleimide Compound (a1), Monoamine Compound (a2) and Diamine Compound (a3) Used)
In the reaction of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3), the amounts of the three used are the primary amino group equivalents [-NH] of the monoamine compound (a2) and the diamine compound (a3). _{It is preferable that the relationship between the sum of [2} group equivalents] and the maleimide group equivalent of the maleimide compound (a1) satisfies the following formula.
0.1 ≤ [maleimide group equivalent] / [-NH _{total of 2} group equivalents] ≤ 10
By setting [maleimide group equivalent] / [ _{sum of -NH 2} group equivalents] to 0.1 or more, gelation and heat resistance do not decrease, and by setting it to 10 or less, it becomes an organic solvent. It is preferable because the solubility, the adhesiveness to the metal foil and the heat resistance are not deteriorated.
From the same point of view, more preferably
1 ≤ [maleimide group equivalent] / [-NH _{total of 2} group equivalents] ≤ 9 is satisfied, and more preferably.
2 ≦ [maleimide group equivalent] / [-NH _{total of 2} group equivalents] ≦ 8 is satisfied.

(Organic solvent)
As described above, the reaction of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3) is preferably carried out in an organic solvent.
The organic solvent is not particularly limited as long as it does not adversely affect the reaction. For example, alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as tetrahydrofuran; toluene, xylene, and mesityrene. Aromatic solvents such as; nitrogen atom-containing solvents including amide-based solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; sulfur atom-containing solvents including sulfoxide-based solvents such as dimethylsulfoxide; ethyl acetate, γ- Examples thereof include ester solvents such as butyrolactone. Among these, alcohol solvents, ketone solvents, and ester solvents are preferable from the viewpoint of solubility, and cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are more preferable from the viewpoint of low toxicity, and they are volatile. Considering that the properties are high and it is difficult to remain as a residual solvent during the production of prepreg, cyclohexanone, propylene glycol monomethyl ether, and dimethylacetamide are more preferable, and dimethylacetamide is particularly preferable.
As the organic solvent, one type may be used alone, or two or more types may be used in combination.
The amount of the organic solvent used is not particularly limited, but from the viewpoint of solubility and reaction efficiency, it is preferably 25 with respect to a total of 100 parts by mass of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3). The amount may be ~ 1,000 parts by mass, more preferably 40 to 700 parts by mass, and even more preferably 60 to 250 parts by mass. By making the total of 100 parts by mass or more of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3) 25 parts by mass or more, it becomes easy to secure the solubility, and the solubility should be 1,000 parts by mass or less. Therefore, it is easy to suppress a significant decrease in reaction efficiency.

(Reaction catalyst)
The reaction of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3) may be carried out in the presence of a reaction catalyst, if necessary. Examples of the reaction catalyst include amine-based catalysts such as triethylamine, pyridine and tributylamine; imidazole-based catalysts such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine.
One type of reaction catalyst may be used alone, or two or more types may be used in combination.
The amount of the reaction catalyst used is not particularly limited, but is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total mass of the maleimide compound (a1) and the monoamine compound (a2).

<(B) Epoxy resin>
The component (B) is an epoxy resin (hereinafter, may be referred to as an epoxy resin (B)), preferably an epoxy resin having at least two epoxy groups in one molecule.
Examples of the epoxy resin having at least two epoxy groups in one molecule include a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, and a glycidyl ester type epoxy resin. Among these, a glycidyl ether type epoxy resin is preferable.
The epoxy resin (B) is classified into various epoxy resins according to the difference in the main skeleton, and in each of the above types of epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and the like are further classified. Bisphenol type epoxy resin; biphenyl aralkylphenol type epoxy resin; phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol alkylphenol copolymer novolak type epoxy resin, naphthol aralkyl cresol copolymer novolac type epoxy resin, Novolak type epoxy resin such as bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin; stillben type epoxy resin; triazine skeleton-containing epoxy resin; fluorene skeleton-containing epoxy resin; naphthalene type epoxy resin; anthracene type epoxy resin; triphenylmethane Type epoxy resin; biphenyl type epoxy resin; biphenyl aralkyl type epoxy resin; xylylene type epoxy resin; alicyclic epoxy resin such as dicyclopentadiene type epoxy resin.
Among these, bisphenol F type epoxy resin and phenol novolac type epoxy resin from the viewpoints of high heat resistance, low specific dielectric constant, high metal foil adhesiveness, high glass transition temperature, low thermal expansion, moldability and turnability with plating. , Cresol novolac type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, dicyclopentadiene type epoxy resin are preferable, and cresol from the viewpoint of low thermal expansion and high glass transition temperature. Novolak type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, phenol novolac type epoxy resin are more preferable, and cresol novolac type epoxy resin is further preferable.
As the epoxy resin (B), one type may be used alone, or two or more types may be used in combination.

The epoxy equivalent of the epoxy resin (B) is preferably 100 to 500 g / eq, more preferably 120 to 400 g / eq, still more preferably 140 to 300 g / eq, and particularly preferably 170 to 240 g / eq.
Here, the epoxy equivalent is the mass (g / eq) of the resin per epoxy group, and can be measured according to the method specified in JIS K 7236 (2001). Specifically, using an automatic titrator "GT-200 type" manufactured by Mitsubishi Chemical Analytech Co., Ltd., 2 g of epoxy resin was weighed in a 200 ml beaker, 90 ml of methyl ethyl ketone was added dropwise, and after melting with an ultrasonic washer, ice was added. It is obtained by adding 10 ml of acetic acid and 1.5 g of cetyltrimethylammonium bromide and titrating with a 0.1 mol / L perchloric acid / acetic acid solution.
Commercially available epoxy resin (B) includes cresol novolac type epoxy resin "EPICLON (registered trademark) N-673" (manufactured by DIC Corporation, epoxy equivalent; 205-215 g / eq) and naphthalene type epoxy resin "HP-4032". (Made by Mitsubishi Chemical Co., Ltd., epoxy equivalent; 152 g / eq), biphenyl type epoxy resin "YX-4000" (manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent; 186 g / eq), dicyclopentadiene type epoxy resin "HP-7200H" (Manufactured by DIC Corporation, epoxy equivalent; 280 g / eq) and the like. The epoxy equivalent is a value described in the catalog of the manufacturer of the product.

<(C) Specific copolymer resin>
The component (C) is a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride (hereinafter, may be referred to as a copolymer resin (C)). Examples of the aromatic vinyl compound include styrene, 1-methylstyrene, vinyltoluene, dimethylstyrene and the like. Of these, styrene is preferable.
As the component (C), a copolymer resin having a structural unit represented by the following general formula (C-i) and a structural unit represented by the following formula (C-ii) is preferable.

（式中、Ｒ^Ｃ１は、水素原子又は炭素数１〜５のアルキル基であり、Ｒ^Ｃ２は、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基、炭素数６〜２０のアリール基、水酸基又は（メタ）アクリロイル基である。ｘは、０〜３の整数である。但し、ｘが２又は３である場合、複数のＲ^Ｃ２は同一であってもよいし、異なっていてもよい。）

(In the formula, ^RC1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and ^RC2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and 6 to 20 carbon atoms. It is an aryl group, a hydroxyl group or a (meth) acryloyl group. X is an integer of 0 to 3. However, when x is 2 or 3, a plurality of ^RC2s may be the same or different. May be.)

The alkyl group of 1 to 5 carbon atoms which R ^C1 and ^{R C2} are represented, for example, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, t- butyl group, n- pentyl Group etc. can be mentioned. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
The alkenyl group having 2 to 5 carbon atoms which R ^C2 is represented, for example, allyl, crotyl and the like. The alkenyl group is preferably an alkenyl group having 3 to 5 carbon atoms, and more preferably an alkenyl group having 3 or 4 carbon atoms.
Examples of the aryl group having 6 to 20 carbon atoms R ^C2 represents, for example, a phenyl group, a naphthyl group, an anthryl group, etc. biphenylyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms.
x is preferably 0 or 1, more preferably 0.
In the structural unit represented by the general formula (C-i), ^RC1 is a hydrogen atom and x is 0, which is derived from the structural unit represented by the following general formula (C-i-1), that is, styrene. The structural unit to be used is preferable.

Content ratio of structural unit derived from aromatic vinyl compound and structural unit derived from maleic anhydride in the copolymer resin (C) [Structural unit derived from aromatic vinyl compound / structural unit derived from maleic anhydride] The (molar ratio) is preferably 1 to 9, more preferably 2 to 9, still more preferably 3 to 8, and particularly preferably 3 to 7. Further, the content ratio of the structural unit represented by the general formula (C-i) to the structural unit represented by the formula (C-ii) [(C-i) / (C-ii)] (molar ratio). Similarly, it is preferably 1 to 9, more preferably 2 to 9, still more preferably 3 to 8, and particularly preferably 3 to 7. When these molar ratios are 1 or more, preferably 2 or more, the effect of improving the dielectric properties tends to be sufficient, and when these molar ratios are 9 or less, the compatibility tends to be good.
The total content of the structural unit derived from the aromatic vinyl compound and the structural unit derived from maleic anhydride in the copolymer resin (C), and the structural unit and formula represented by the general formula (C-i). The total content with the structural unit represented by (C-ii) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably substantially 100. It is mass%.
The weight average molecular weight (Mw) of the copolymerized resin (C) is preferably 4,500 to 18,000, more preferably 5,000 to 18,000, more preferably 6,000 to 17,000, and even more preferably 6,000 to 17,000. It is 8,000 to 16,000, particularly preferably 8,000 to 15,000, and most preferably 9,000 to 13,000.

When the method of lowering the dielectric constant of the epoxy resin by using a copolymer resin of styrene and maleic anhydride is applied to a material for a printed wiring board, the impregnation property to the base material and the copper foil peel strength become insufficient. Therefore, it generally tends to be avoided. Therefore, the use of the copolymer resin (C) tends to be generally avoided, but in the present invention, the components (A) and (B) are used while using the copolymer resin (C). With a thermosetting resin composition having high heat resistance, low relative permittivity, high metal foil adhesiveness, high glass transition temperature and low thermal expansion property, and excellent moldability and plating turnability. It turned out to be and was achieved.

(Manufacturing method of copolymer resin (C))
The copolymerized resin (C) can be produced by copolymerizing an aromatic vinyl compound and maleic anhydride.
Examples of the aromatic vinyl compound include styrene, 1-methylstyrene, vinyltoluene, dimethylstyrene and the like, as described above. These may be used alone or in combination of two or more.
Further, in addition to the aromatic vinyl compound and maleic anhydride, various polymerizable components may be copolymerized. Examples of various polymerizable components include vinyl compounds such as ethylene, propylene, butadiene, isobutylene and acrylonitrile; and compounds having a (meth) acryloyl group such as methyl acrylate and methyl methacrylate.
Further, a substituent such as an allyl group, a methacryloyl group, an acryloyl group or a hydroxy group may be introduced into the aromatic vinyl compound through a Friedel-Crafts reaction or a reaction using a metal catalyst such as lithium.

As the copolymerization resin (C), a commercially available product can also be used. Examples of commercially available products include "SMA (registered trademark) 1000" (styrene / maleic anhydride = 1, Mw = 5,000) and "SMA (registered trademark) EF30" (styrene / maleic anhydride = 3, Mw = 9). , 500), "SMA (registered trademark) EF40" (styrene / maleic anhydride = 4, Mw = 11,000), "SMA (registered trademark) EF60" (styrene / maleic anhydride = 6, Mw = 11,500) ), "SMA (registered trademark) EF80" (styrene / maleic anhydride = 8, Mw = 14,400) [above, manufactured by CRAY VALLEY] and the like.

<Silica treated with (D) aminosilane coupling agent>
The thermosetting resin composition contains an inorganic filler in order to reduce the coefficient of thermal expansion of the insulating resin layer. In the present invention, the component (D) is an aminosilane type among silicas. Silica treated with a coupling agent (hereinafter, may be referred to as silica (D) treated with an aminosilane-based coupling agent) is used. By incorporating silica (D) treated with an aminosilane-based coupling agent into the thermosetting resin composition, in addition to the effect of improving low thermal expansion, adhesion with the above-mentioned components (A) to (C) Since the removal of silica is suppressed by the improvement of the above, the effect of suppressing the deformation of the laser via shape due to excessive desmear can be obtained.

（式中、Ｒ^Ｄ１は、炭素数１〜３のアルキル基又は炭素数２〜４のアシル基である。ｙは、０〜３の整数である。） Specifically, as the aminosilane-based coupling agent, a silane coupling agent having a silicon-containing group represented by the following general formula (D-1) and an amino group is preferable.

(In the formula, ^RD1 is an alkyl group having 1 to 3 carbon atoms or an acyl group having 2 to 4 carbon atoms. Y is an integer of 0 to 3.)

The alkyl group having 1 to 3 carbon atoms R ^D1 represents a methyl group, an ethyl group, n- propyl group, an isopropyl group. Of these, a methyl group is preferred.
The acyl group having 2 to 4 carbon atoms R ^D1 represents an acetyl group, a propionyl group, and acrylic group. Of these, an acetyl group is preferable.

The aminosilane-based coupling agent may have one amino group, two amino groups, or three or more amino groups, but usually has one amino group or one amino group or more. I have two.
Examples of the aminosilane-based coupling agent having one amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and 3-triethoxysilyl-. Examples thereof include N- (1,3-dimethyl-butylidene) propylamine and 2-propynyl [3- (trimethoxysilyl) propyl] carbamate, but the present invention is not particularly limited thereto.
Examples of the aminosilane-based coupling agent having two amino groups include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and the like. Examples thereof include 1- [3- (trimethoxysilyl) propyl] urea and 1- [3- (triethoxysilyl) propyl] urea, but the present invention is not particularly limited thereto.

Instead of silica (D) treated with an aminosilane-based coupling agent, for example, an epoxysilane-based coupling agent, a phenylsilane-based coupling agent, an alkylsilane-based coupling agent, an alkenylsilane-based coupling agent, an alkynylsilane-based agent. Coupling agent, haloalkylsilane-based coupling agent, siloxane-based coupling agent, hydrosilane-based coupling agent, silazane-based coupling agent, alkoxysilane-based coupling agent, chlorosilane-based coupling agent, (meth) acrylic silane-based coupling Agents, aminosilane-based coupling agents, isocyanuratesilane-based coupling agents, ureidosilane-based coupling agents, mercaptosilane-based coupling agents, sulfidesilane-based coupling agents, isocyanate-silane-based coupling agents, and the like. When used, the adhesion to the components (A) to (C) is lowered and the silica tends to fall off easily, and the effect of suppressing deformation of the laser via shape due to excessive desmear is poor.
As long as silica (D) treated with an aminosilane-based coupling agent is used, silica treated with the other coupling agents described above may be used in combination as long as the effects of the present invention are not impaired. When silica treated with the above-mentioned other coupling agent is used in combination, silica treated with another coupling agent is preferably used with respect to 100 parts by mass of silica (D) treated with the aminosilane-based coupling agent. It is 50 parts by mass or less, more preferably 30 parts by mass or less, further preferably 15 parts by mass or less, particularly preferably 10 parts by mass or less, and most preferably 5 parts by mass or less.

Examples of silica used for silica (D) treated with an aminosilane-based coupling agent include precipitated silica manufactured by a wet method and having a high water content, and dry silica manufactured by a dry method and containing almost no bound water or the like. Can be mentioned. Further, examples of the dry silica include crushed silica, fumed silica, and fused silica (molten spherical silica) depending on the manufacturing method. As the silica, molten silica is preferable from the viewpoint of low thermal expansion and high fluidity when filled in a resin.
The average particle size of the silica is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.1 to 6 μm, further preferably 0.1 to 3 μm, and particularly preferably 1 to 3 μm. By setting the average particle size of silica to 0.1 μm or more, the fluidity at the time of high filling can be maintained well, and by setting it to 10 μm or less, the mixing probability of coarse particles is reduced to make coarse particles. It is possible to suppress the occurrence of defects caused by it. Here, the average particle size is the particle size of a point corresponding to exactly 50% of the volume when the cumulative frequency distribution curve by the particle size is obtained with the total volume of the particles as 100%. It can be measured with the particle size distribution measuring device or the like used.
The specific surface area of the silica is preferably 4 cm ² / g or more, more preferably ^{4 to 9 cm 2} / g, and further preferably 5 to 7 cm ² / g.

<(E) Hardener>
The thermosetting resin composition may further contain a curing agent (hereinafter, may be referred to as a curing agent (E)) as the component (E). The curing agent (E) includes dicyandiamide; a chain aliphatic amine excluding dicyandiamide such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, diethylaminopropylamine, tetramethylguanidine, and triethanolamine; Isophoronediamine, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, bis (4-amino-3-methyldicyclohexyl) methane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8 , 10-Tetraoxaspiro [5.5] Cyclic aliphatic amines such as undecane; aromatic amines such as xylene diamine, phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and the like. Among these, dicyandiamide is preferable from the viewpoint of metal leaf adhesiveness and low thermal expansion.
The dicyandiamide _is represented by H 2 N-C (= NH ) -NH-CN, melting point typically, 205-215 ° C., than more high purity is 207 to 212 ° C.. The dicyandiamide is a crystalline substance and may be an orthorhombic crystal or a plate crystal. The dicyandiamide preferably has a purity of 98% or more, more preferably 99% or more, and further preferably 99.4% or more. As the dicyandiamide, a commercially available product can be used. For example, a commercially available product such as Nippon Carbide Industry Co., Ltd., Tokyo Chemical Industry Co., Ltd., Kishida Chemical Co., Ltd., Nacalai Tesque Co., Ltd., etc. can be used. ..

<(F) Flame Retardant>
The thermosetting resin composition of the present invention may further contain a flame retardant (hereinafter, may be referred to as a flame retardant (F)) as a component (F). Here, among the above-mentioned curing agents, dicyandiamide and the like also have an effect as a flame retardant, but in the present invention, those capable of functioning as a curing agent are classified as curing agents and are not included in the component (F). ..
Examples of the flame retardant include halogen-containing flame retardants containing bromine and chlorine; phosphorus-based flame retardants; nitrogen-based flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate, and melamine cyanurate; cyclophosphazene and polyphosphazene. Phosphazene-based flame retardants such as; and inorganic flame retardants such as antimony trioxide. Among these, phosphorus-based flame retardants are preferable.
Phosphorus-based flame retardants include inorganic phosphorus-based flame retardants and organic phosphorus-based flame retardants.
Examples of the inorganic phosphorus-based flame retardant include red phosphorus; ammonium phosphate such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amide. Phosphoric acid; phosphine oxide and the like.
Examples of the organic phosphorus-based flame retardant include aromatic phosphoric acid ester, mono-substituted phosphonic acid diester, 2-substituted phosphinic acid ester, metal salt of 2-substituted phosphinic acid, organic nitrogen-containing phosphorus compound, and cyclic organic phosphorus compound. Phosphorus-containing phenolic resin and the like can be mentioned. Among these, a metal salt of an aromatic phosphoric acid ester and a disubstituted phosphinic acid is preferable. Here, the metal salt is preferably any one of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt and zinc salt, and is preferably an aluminum salt. Further, among the organic phosphorus-based flame retardants, aromatic phosphoric acid esters are more preferable.

Examples of the aromatic phosphate ester include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresildiphenyl phosphate, cresildi-2,6-xylenyl phosphate, resorcinol bis (diphenyl phosphate), 1,3. -Phenylene bis (di-2,6-xylenyl phosphate), bisphenol A-bis (diphenyl phosphate), 1,3-phenylene bis (diphenyl phosphate) and the like can be mentioned.
Examples of the mono-substituted phosphonic acid diester include divinyl phenylphosphonate, diallyl phenylphosphonate, and bis (1-butenyl) phenylphosphonate.
Examples of the disubstituted phosphinic acid ester include phenyl diphenylphosphinate and methyl diphenylphosphinate.
Examples of the metal salt of disubstituted phosphinic acid include a metal salt of dialkylphosphinic acid, a metal salt of diallylphosphinic acid, a metal salt of divinylphosphinic acid, and a metal salt of diarylphosphinic acid. As described above, these metal salts are preferably any one of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt and zinc salt.
Examples of the organic nitrogen-containing phosphorus compound include phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicredylphosphazene; melamine phosphate, melamine pyrophosphate, melamine polyphosphate, and melam polyphosphate.
Examples of the cyclic organophosphorus compound include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-. Examples thereof include 10-phosphaphenanthrene-10-oxide.
Among these, at least one selected from an aromatic phosphoric acid ester, a metal salt of disubstituted phosphinic acid and a cyclic organic phosphorus compound is preferable, and an aromatic phosphoric acid ester is more preferable.

The aromatic phosphoric acid ester is preferably an aromatic phosphoric acid ester represented by the following general formula (F-1) or (F-2), and the metal salt of the disubstituted phosphinic acid is described below. It is preferably a metal salt of disubstituted phosphinic acid represented by the general formula (F-3).

(In the formula, R ^{F1 to} R ^F5 are independently alkyl groups or halogen atoms having 1 to 5 carbon atoms. E and f are independently integers of 0 to 5, and g, h and i are respectively. It is an integer from 0 to 4 independently.
^RF6 and ^RF7 are independently alkyl groups having 1 to 5 carbon atoms or aryl groups having 6 to 14 carbon atoms. M is a lithium atom, a sodium atom, a potassium atom, a calcium atom, a magnesium atom, an aluminum atom, a titanium atom, and a zinc atom. j is an integer of 1 to 4. )

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^F1 to R ^F5, for example, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, t- butyl group, n- pentyl Group etc. can be mentioned. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. The halogen atom represented by R ^F1 to R ^F5, and a fluorine atom.
e and f are preferably integers of 0 to 2, more preferably 2. g, h and i are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0.
Examples of the alkyl group having 1 to 5 carbon atoms R ^F6 and ^{R F7} represent ^include the same ones as for R F1 ^{to R F5.}
The aryl group having 6 to 14 carbon atoms R ^F6 and ^{R F7} represented, for example, a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group. As the aromatic hydrocarbon group, an aryl group having 6 to 10 carbon atoms is preferable.
j is equal to the valence of the metal ion, that is, varies within the range of 1-4 depending on the type of M.
As M, an aluminum atom is preferable. When M is an aluminum atom, j is 3.

(Content of each component)
The content of the components (A) to (D) in the thermosetting resin composition is not particularly limited, but (A) is based on 100 parts by mass of the total of the components (A) to (C). It is preferable that the component is 15 to 65 parts by mass, the component (B) is 15 to 50 parts by mass, the component (C) is 10 to 45 parts by mass, and the component (D) is 30 to 70 parts by mass.
By having 15 parts by mass or more of the component (A) with respect to 100 parts by mass of the total of the components (A) to (C), high heat resistance, low relative permittivity, high glass transition temperature and low thermal expansion can be obtained. There is a tendency. On the other hand, when it is 65 parts by mass or less, the fluidity and moldability of the thermosetting resin composition tend to be good.
When the component (B) is 15 parts by mass or more with respect to 100 parts by mass of the total of the components (A) to (C), high heat resistance, high glass transition temperature and low thermal expansion tend to be obtained. On the other hand, when it is 50 parts by mass or less, it tends to have high heat resistance, low relative permittivity, high glass transition temperature and low thermal expansion.
When the component (C) is 10 parts by mass or more with respect to 100 parts by mass of the total of the components (A) to (C), high heat resistance and low relative permittivity tend to be obtained. On the other hand, when it is 45 parts by mass or less, high heat resistance, high metal leaf adhesiveness and low thermal expansion tend to be obtained.
When the component (D) is 30 parts by mass or more with respect to 100 parts by mass of the total of the components (A) to (C), excellent low thermal expansion tends to be obtained, while it is 70 parts by mass or less. As a result, heat resistance tends to be obtained, and the fluidity and moldability of the thermosetting resin composition tend to be good.

When the thermosetting resin composition of the present invention contains the component (E), the content thereof is 0.5 to 6 parts by mass with respect to 100 parts by mass of the total of the components (A) to (C). Is preferable.
When the component (E) is 0.5 parts by mass or more with respect to 100 parts by mass of the total of the components (A) to (C), high metal leaf adhesiveness and excellent low thermal expansion tend to be obtained. On the other hand, when the amount is 6 parts by mass or less, high heat resistance tends to be obtained.

When the thermosetting resin composition of the present invention contains the component (F), the content thereof is based on 100 parts by mass of the total of the components (A) to (C) from the viewpoint of flame retardancy. It is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass. In particular, when a phosphorus-based flame retardant is used as the component (F), the phosphorus atom content is 0.1 to 3% by mass with respect to 100 parts by mass of the total of the components (A) to (C) from the viewpoint of flame retardancy. The amount of parts is preferable, the amount of 0.2 to 3 parts by mass is more preferable, and the amount of 0.5 to 3 parts by mass is further preferable.

(Other ingredients)
The thermosetting resin composition of the present invention may contain other components such as additives and organic solvents, if necessary, as long as the effects of the present invention are not impaired. These may contain one kind alone or two or more kinds.

(Additive)
Examples of the additive include a curing agent, a curing accelerator, a coloring agent, an antioxidant, a reducing agent, an ultraviolet absorber, a fluorescent whitening agent, an adhesion improver, an organic filler and the like. These may be used alone or in combination of two or more.

(Organic solvent)
The thermosetting resin composition may contain an organic solvent from the viewpoint of facilitating handling by diluting and from the viewpoint of facilitating the production of a prepreg described later. In the present specification, the thermosetting resin composition containing an organic solvent may be referred to as a resin varnish.
The organic solvent is not particularly limited, and for example, methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol, and the like. Alcohol-based solvents such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether and dipropylene glycol monopropyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ether solvents such as tetrahydrofuran Aromatic solvents such as toluene, xylene, mesitylen; nitrogen atom-containing solvents including amide solvents such as formamide, N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone. Sulfur atom-containing solvent containing a sulfoxide solvent such as dimethyl sulfoxide; ester solvents such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate and the like can be mentioned.
Among these, alcohol solvents, ketone solvents, and nitrogen atom-containing solvents are preferable from the viewpoint of solubility, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are more preferable, and methyl ethyl ketone and methyl isobutyl ketone are more preferable. More preferably, methyl ethyl ketone is particularly preferable.
As the organic solvent, one type may be used alone, or two or more types may be used in combination.
The content of the organic solvent in the thermosetting resin composition may be appropriately adjusted to such an extent that the thermosetting resin composition can be easily handled, and as long as the coatability of the resin varnish is good. Although not particularly limited, the solid content concentration (concentration of components other than the organic solvent) derived from the thermosetting resin composition is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and further preferably 50 to 80. Make it mass%.

[Prepreg]
The prepreg of the present invention contains the thermosetting resin composition, and the method for producing the prepreg is not particularly limited. For example, the prepreg of the present invention is impregnated or coated on a sheet-shaped reinforcing base material, and semi-finished by heating or the like. It can be manufactured by curing (B-stage).
As the sheet-shaped reinforcing base material of the prepreg, well-known materials used for various laminated plates for electrical insulating materials can be used. As the material of the sheet-like reinforcing base material, natural fibers such as paper and cotton linter; inorganic fibers such as glass fiber and asbestos; organic fibers such as aramid, polyimide, polyvinyl alcohol, polyester, tetrafluoroethylene and acrylic; these Examples include mixtures. Among these, glass fiber is preferable from the viewpoint of flame retardancy. As the glass fiber base material, a woven cloth using E glass, C glass, D glass, S glass, etc. or a glass woven cloth in which short fibers are bonded with an organic binder; a mixture of glass fibers and cellulose fibers, etc. Can be mentioned. More preferably, it is a glass woven fabric using E glass.
These sheet-shaped reinforcing base materials have a shape such as a woven fabric, a non-woven fabric, a robink, a chopped strand mat or a surfaced mat. The material and shape are selected according to the intended use and performance of the molded product, and one type may be used alone, or two or more types of materials and shapes may be combined as required.

The following hot melt method or solvent method is preferable as a method for impregnating or coating the sheet-shaped reinforcing base material with the thermosetting resin composition.
The hot melt method is a method in which the thermosetting resin composition does not contain an organic solvent, and (1) is once coated on coated paper having good peelability from the composition and then laminated on a sheet-like reinforcing base material. Or (2) A method of directly coating the sheet-shaped reinforcing base material with a die coater.
On the other hand, in the solvent method, a varnish is prepared by impregnating a thermosetting resin composition with an organic solvent, a sheet-shaped reinforcing base material is immersed in the varnish, the varnish is impregnated in the sheet-shaped reinforcing base material, and then the varnish is impregnated. It is a method of drying.

The thickness of the sheet-shaped reinforcing base material is not particularly limited, and for example, about 0.03 to 0.5 mm can be used, and the sheet-like reinforcing base material is surface-treated with a silane coupling agent or the like or mechanically opened. The applied one is preferable from the viewpoint of heat resistance, moisture resistance and processability. After impregnating or coating a base material with a thermosetting resin composition, the substrate is usually semi-cured (B-staged) by heating and drying at a temperature of 100 to 200 ° C. for 1 to 30 minutes. You can get a prepreg.
One prepreg may be used, or preferably 2 to 20 prepregs may be stacked as required.

[Laminated board]
The laminated board of the present invention contains the prepreg. For example, it can be produced by using one of the prepregs or, if necessary, stacking 2 to 20 sheets and laminating and molding the prepreg in a configuration in which metal foils are arranged on one side or both sides thereof. The laminated board on which the metal foil is arranged may be referred to as a metal-clad laminated board.
The metal of the metal foil is not particularly limited as long as it is used for electrical insulating material applications, but from the viewpoint of conductivity, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, etc. are preferable. It is preferably an alloy containing iron, titanium, chromium, or at least one of these metal elements, more preferably copper, amyrnium, and even more preferably copper.
As the molding conditions for the laminated board, a known molding method for a laminated board for an electrically insulating material and a multi-layer board can be applied. For example, a multi-stage press, a multi-stage vacuum press, continuous molding, an autoclave molding machine or the like is used, and the temperature is adjusted. It can be molded at 100 to 250 ° C., a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours.
Further, the prepreg of the present invention and the printed wiring board for the inner layer can be combined and laminated to produce a multilayer board.
The thickness of the metal foil is not particularly limited and can be appropriately selected depending on the application of the printed wiring board and the like. The thickness of the metal foil is preferably 0.5 to 150 μm, more preferably 1 to 100 μm, still more preferably 5 to 50 μm, and particularly preferably 5 to 30 μm.

It is also preferable to form a plating layer by plating a metal foil.
The metal of the plating layer is not particularly limited as long as it is a metal that can be used for plating. The metal of the plating layer is preferably from among alloys containing copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and at least one of these metal elements. It is preferably selected.
The plating method is not particularly limited, and known methods such as an electrolytic plating method and an electroless plating method can be used.

[Printed circuit board]
The present invention also provides a printed wiring board containing the prepreg or the laminated board.
The printed wiring board of the present invention can be manufactured by applying circuit processing to the metal foil of the metal-clad laminate. In the circuit processing, for example, after forming a resist pattern on the surface of the metal foil, removing the unnecessary metal foil by etching, peeling the resist pattern, forming a necessary through hole by a drill, and forming the resist pattern again, the resist pattern is formed. This can be done by plating the through holes to make them conductive, and finally peeling off the resist pattern. The above-mentioned metal-clad laminate is further laminated on the surface of the printed wiring board thus obtained under the same conditions as described above, and further circuit-processed in the same manner as described above to obtain a multilayer printed wiring board. Can be done. In this case, it is not always necessary to form through holes, and via holes may be formed, or both can be formed. Such multi-layering is performed in the required number of sheets.

Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention in any sense. Using the thermosetting resin composition according to the present invention, a prepreg and a copper-clad laminate were prepared, and the prepared copper-clad laminate was evaluated. The evaluation method is shown below.

[Evaluation method]
<1. Heat resistance (reflow solder heat resistance)>
Using the 4-layer copper-clad laminate prepared in each example, the maximum temperature reached was 266 ° C, and the 4-layer copper-clad laminate was flown for 30 seconds in a constant temperature bath environment of 260 ° C or higher as one cycle, visually. The number of cycles until it was confirmed that the substrate had swelled was calculated. The larger the number of cycles, the better the heat resistance.

<2. Relative permittivity (Dk)>
Using a network analyzer "8722C" (manufactured by Hewlett-Packard Co., Ltd.), the relative permittivity of the double-sided copper-clad laminate at 1 GHz was measured by the triplate structure linear line resonator method. The size of the test piece is 200 mm x 50 mm x 0.8 mm thickness, and a straight line (line length 200 mm) with a width of 1.0 mm is formed by etching at the center of one side of one double-sided copper-clad laminate, and the back side is Copper was left on the entire surface to form a ground layer. One side of the other double-sided copper-clad laminate was etched on one side, and the back side was used as a ground layer. These two double-sided copper-clad laminates were laminated with the ground layer on the outside to form a strip line. The measurement was performed at 25 ° C.
The smaller the relative permittivity, the more preferable.

<3. Metal leaf adhesiveness (copper foil peel strength)>
The metal leaf adhesiveness was evaluated by the copper foil peel strength. By immersing the double-sided copper-clad laminate prepared in each example in a copper etching solution "ammonium persulfate (APS)" (manufactured by ADEKA Co., Ltd.), a copper foil having a width of 3 mm was formed to prepare an evaluation substrate, and an autograph " The peel strength of the copper foil was measured using "AG-100C" (manufactured by Shimadzu Corporation). The larger the value, the better the metal leaf adhesiveness.

<4. Glass transition temperature (Tg)>
By immersing the double-sided copper-clad laminate prepared in each example in the copper etching solution "ammonium persulfate (APS)" (manufactured by ADEKA Co., Ltd.), a 5 mm square evaluation substrate from which the copper foil was removed was prepared, and the TMA test apparatus " Using "Q400EM" (manufactured by TA Instruments), the thermal expansion characteristics in the plane direction (Z direction) of the evaluation substrate at 30 to 260 ° C. were observed, and the change point of the expansion amount was defined as the glass transition temperature.

<5. Low thermal expansion>
A 5 mm square evaluation substrate from which the copper foil was removed was prepared by immersing the double-sided copper-clad laminate prepared in each example in a copper etching solution "ammonium persulfate (APS)" (manufactured by ADEKA Corporation), and the TMA test apparatus " The coefficient of thermal expansion (linear expansion rate) in the plane direction of the evaluation substrate was measured using "Q400EM" (manufactured by TA Instruments). In order to remove the influence of the thermal strain of the sample, the temperature raising-cooling cycle was repeated twice, and the coefficient of thermal expansion [ppm / ° C.] of 30 ° C. to 260 ° C. on the second temperature displacement chart was measured. It was used as an index of low thermal expansion. The smaller the value, the better the low thermal expansion. In the table, the coefficient of thermal expansion below Tg (denoted as "<Tg") and the coefficient of thermal expansion above Tg (denoted as ">Tg") are described separately.
Measurement conditions 1 ^st Run: Room temperature → 210 ° C (heating rate 10 ° C / min)
^{2 nd Run: 0 ℃ → 270} ℃ ( heating rate 10 ° C. / min)
Further thinning of the copper-clad laminate is desired, and at the same time, thinning of the prepreg constituting the copper-clad laminate is also being studied. Since the thinned prepreg tends to warp, it is desired that the warp of the prepreg during heat treatment is small. In order to reduce the warpage, it is effective that the coefficient of thermal expansion in the surface direction of the base material is small.

<6. Rotation with plating (laser workability)>
For the 4-layer copper-clad laminate produced in each example, a laser machine "LC-2F21B / 2C" (manufactured by Hitachi Via Mechanics, Ltd.) was used, and a target hole diameter of 80 μm, Gaussian, and a copper direct method were used in a cycle mode. , The pulse width was 15 μs × 1 time and 7 μs × 4 times, and laser drilling was performed.
For the obtained laser perforated substrate, apply the swelling solution "Swelling Dip Securigant P" (manufactured by Atotech Japan Co., Ltd.) at 70 ° C for 5 minutes, and the roughening solution "Dosing Securigant P500J" (manufactured by Atotech Japan Co., Ltd.) Desmear treatment was carried out at 70 ° C. for 9 minutes using a neutralizing solution "Reduction Conditioner Securigant P500" (manufactured by Atotech Japan Co., Ltd.) at 40 ° C. for 5 minutes. After this, the electroless plating solution "Puriganto MSK-DK" (manufactured by Atotech Japan Co., Ltd.) to 30 ℃, 20 minutes, electroplating solution "Cupracid HL" (manufactured by Atotech Japan Co., ^{Ltd.) 24 ℃, 2A / dm 2} , The process was carried out for 2 hours, and the laser-processed substrate was plated.
The cross-sectional observation of the obtained laser-drilled substrate was carried out, and the turning property of the plating was confirmed. As a method for evaluating the turnability of plating, it is preferable that the difference between the plating thickness at the top of the laser hole and the plating thickness at the bottom of the laser hole is within 10% of the plating thickness at the top of the laser hole. The abundance ratio (%) of holes included in this range in the holes was determined.

<7. Moldability>
For the 4-layer copper-clad laminates produced in each example, after removing the outer layer copper, the presence or absence of voids and faintness in the in-plane of 340 x 500 mm was visually confirmed as the resin embedding property, and an index of moldability was obtained. And said. The absence of voids and scratches indicates that the moldability is good.

Hereinafter, each component used in Examples and Comparative Examples will be described.

Component (A): A solution of the maleimide compound (A) produced in Production Example 1 below was used.
[Manufacturing Example 1]
19.2 g of 4,4'-diaminodiphenylmethane, 174.0 g of bis (4-maleimidephenyl) methane, p-aminophenol in a 1 L volume reaction vessel equipped with a thermometer, a stirrer and a moisture quantifier with a reflux condenser. Add 6.6 g and 330.0 g of dimethylacetamide and react at 100 ° C. for 2 hours to prepare a dimethylacetamide solution of the maleimide compound (A) (Mw = 1,370) having an acidic substituent and an N-substituted maleimide group. Obtained and used as the component (A).
The weight average molecular weight (Mw) was converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve is standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation] Was approximated by a cubic equation. The conditions for GPC are shown below.
Equipment: (Pump: L-6200 type [manufactured by Hitachi High-Technologies Corporation]),
(Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Corporation]),
(Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation])
Column: TSKgel SuperHZ2000 + TSKgel SuperHZ2300 (all manufactured by Tosoh Corporation)
Column size: 6.0 x 40 mm (guard column), 7.8 x 300 mm (column)
Eluent: tetrahydrofuran Sample concentration: 20 mg / 5 mL
Injection volume: 10 μL
Flow rate: 0.5 mL / min Measurement temperature: 40 ° C

(B) Ingredient: Cresol novolac type epoxy resin "EPICLON (registered trademark) N-673" (manufactured by DIC Corporation)
(C-1) Ingredient: "SMA (registered trademark) EF40" (styrene / maleic anhydride = 4, Mw = 11,000, manufactured by CRAY VALLEY)
(C-2) Ingredient: "SMA (registered trademark) 3000" (styrene / maleic anhydride = 2, Mw = 7,500, manufactured by CRAY VALLEY)
(C-3) Ingredient: "SMA (registered trademark) EF80" (styrene / maleic anhydride = 8, Mw = 14,400, manufactured by CRAY VALLEY)
(C-4) Ingredient: SMA (registered trademark) 1000 "(styrene / maleic anhydride = 1, Mw = 5,000, manufactured by CRAY VALLEY)

(D) Ingredient: "Megasil 525 ARI" (molten silica treated with an aminosilane coupling agent, average particle size: 1.9 μm, specific surface area 5.8 m ² / g, manufactured by Sibelco Japan Co., Ltd.)
Inorganic filler: "F05-30" (untreated crushed silica, average particle size: 4.2 μm, specific surface area 5.8 m ² / g, manufactured by Fukushima Ceramics Co., Ltd.)

(E) Ingredient: dicyandiamide (manufactured by Nippon Carbide Industry Co., Ltd.)
(F) Ingredient: "PX-200" (aromatic phosphate ester (see structural formula below), manufactured by Daihachi Chemical Industry Co., Ltd.)

[Examples 1 to 13, Comparative Example 1]
Each component shown above is blended as shown in Tables 1 to 4 below (however, in the case of a solution, the solid content conversion amount is shown), and methyl ethyl ketone is further added so that the non-volatile content of the solution is 65 to 75% by mass. In addition, thermosetting resin compositions of each Example and each Comparative Example were prepared.
Each of the obtained thermosetting resin compositions was impregnated with a glass cloth (0.1 mm) of IPC standard # 3313 and dried at 160 ° C. for 4 minutes to obtain a prepreg.
18 μm copper foil “3EC-VLP-18” (manufactured by Mitsui Kinzoku Co., Ltd.) was layered on both sides of a stack of eight prepregs, and ^{heated at a temperature of 190 ° C. and a pressure of 25 kgf / cm 2} (2.45 MPa) for 90 minutes. Pressure molding is performed to prepare a double-sided copper-clad laminate having a thickness of 0.8 mm (for eight prepregs), and the copper-clad laminate is used to obtain relative permittivity, metal leaf adhesiveness, and glass transition according to the above method. Temperature (Tg) and low thermal expansion were measured and evaluated.
On the other hand, using one of the prepregs, 18 μm copper foil “YGP-18” (manufactured by Nippon Denki Co., Ltd.) was layered on both sides, and the temperature was 190 ° C. and the pressure was 25 kgf / cm ² (2.45 MPa) for 90 minutes. After heat-press molding to prepare a double-sided copper-clad laminate with a thickness of 0.1 mm (for one prepreg), inner layer adhesion treatment ("BF treatment liquid" (manufactured by Hitachi Kasei Co., Ltd.)) is applied to both copper foil surfaces. Prepreg with a thickness of 0.05 mm is layered one by one, and 18 μm copper foil “YGP-18” (manufactured by Nippon Denki Co., Ltd.) is layered on both sides, and the temperature is 190 ° C. and the pressure is 25 kgf / cm ² (2). A 4-layer copper-clad laminate was produced by heat-press molding at .45 MPa) for 90 minutes. Using the 4-layer copper-clad laminate, heat resistance, plating turnability, and moldability were evaluated according to the above method.
The results are shown in Tables 1-4.

In the examples, the reflow solder heat resistance achieved 10 cycles or more, which is higher than the heat resistance requirement level, low relative permittivity, high metal leaf adhesiveness, high glass transition temperature were obtained, and low thermal expansion was exhibited. In addition, it was confirmed that the glass cloth had a good turning property with plating because the glass cloth protruded from the wall surface and had an appropriate roughened shape. In terms of moldability, the resin was well embedded, and no abnormalities such as fading and voids were confirmed. Among them, in Examples 1 to 10, the relative permittivity and the metal leaf adhesiveness were better than those in Examples 11 to 13, and other characteristics were stably exhibited.
On the other hand, in Comparative Example 1 in which silica not treated with an aminosilane-based coupling agent is used as the inorganic filler, the amount of desmear dissolved becomes large, and the unevenness of the laser hole wall surface and the protrusion of the glass cloth tend to be large. In, the turnability with plating was significantly reduced.

The prepreg of the present invention and the laminated board containing the prepreg have high heat resistance, low relative permittivity, high metal leaf adhesiveness, high glass transition temperature and low thermal expansion, and have moldability and plating. It is useful as a printed wiring board for electronic devices because of its excellent properties.

Claims (15)

(A) Maleimide compound,
(B) An epoxy resin having at least two epoxy groups in one molecule,
A thermosetting resin composition containing (C) a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride, and (D) silica treated with an aminosilane-based coupling agent. A prepreg formed by impregnating or coating a glass fiber base material with a material and semi-curing it.
A prepreg having an average particle size of the component (D) of 0.1 to 10 μm . The component (A) is (a1) a maleimide compound having at least two N-substituted maleimide groups in one molecule, (a2) a monoamine compound represented by the following general formula (a2-1), and (a3). The prepreg according to claim 1, which is a maleimide compound having an N-substituted maleimide group, which is obtained by reacting with a diamine compound represented by the following general formula (a3-1).

(In the general formula ^{(a2-1), R A4} represents a hydroxyl group, ^{.R A5} is showing an acidic substituent group selected from a carboxy group and a sulfonic acid group, an alkyl group or a halogen atom having 1 to 5 carbon atoms. t is an integer of 1 to 5, u is an integer of 0 to 4, and satisfies 1 ≦ t + u ≦ 5. However, when t is an integer of 2 to 5, a plurality of ^RA4s may be the same. It may be different, and when u is an integer of 2 to 4, a plurality of ^RA5s may be the same or different.)

(In the general formula ^{(a3-1), X A2} is ^{.R A6} and ^{R A7} represents an aliphatic hydrocarbon group or an -O- of 1 to 3 carbon atoms are each independently alkyl having 1 to 5 carbon atoms Indicates a group, a halogen atom, a hydroxyl group, a carboxy group or a sulfonic acid group. V and w are independently integers of 0 to 4). According to claim 1 or 2, the component (C) is a copolymer resin having a structural unit represented by the following general formula (C-i) and a structural unit represented by the following formula (C-ii). The listed prepreg.

(In the formula, ^RC1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and ^RC2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and 6 to 20 carbon atoms. It is an aryl group, a hydroxyl group or a (meth) acryloyl group. X is an integer of 0 to 3. However, when x is 2 or 3, a plurality of ^RC2s may be the same or different. May be.) The prepreg according to claim 3, wherein in the general formula (C-i), ^RC1 is a hydrogen atom and x is 0. In the component (C), the content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from maleic anhydride [structural unit derived from the aromatic vinyl compound / structural unit derived from maleic anhydride] (mol). The prepreg according to claim 1 or 2, wherein the ratio) is 2-9. In the component (C), the content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from maleic anhydride [structural unit derived from the aromatic vinyl compound / structural unit derived from maleic anhydride] (mol). The prepreg according to claim 1 or 2, wherein the ratio) is 3 to 7. The prepreg according to any one of claims 1 to 6, wherein the weight average molecular weight of the component (C) is 4,500 to 18,000. The prepreg according to any one of claims 1 to 7, wherein the weight average molecular weight of the component (C) is 9,000 to 13,000. The component (B) is a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthalene type epoxy resin, an anthracene type epoxy resin, a biphenyl type epoxy resin, a biphenyl aralkyl type epoxy resin or a dicyclopentadiene type. The prepreg according to any one of claims 1 to 8, which is an epoxy resin. The prepreg according to any one of claims 1 to 9, wherein the thermosetting resin composition further contains (E) a curing agent. The prepreg according to any one of claims 1 to 10, wherein the thermosetting resin composition further contains (F) a flame retardant. The prepreg according to any one of claims 1 to 11 , wherein the average particle size of the component (D) is 0.1 to 6 μm. The prepreg according to any one of claims 1 to 12 , wherein the specific surface area of the component (D) is 4 cm ² / g or more. A laminated board containing the prepreg according to any one of claims 1 to 13 and a metal foil. A printed wiring board comprising the prepreg according to any one of claims 1 to 13 or the laminated board according to claim 14.