WO2018181286A1 - Method for producing prepreg, prepreg, laminate, printed wiring board and semiconductor package - Google Patents

Abstract

The present invention provides: a method for producing a prepreg which has small variation in the amount of dimensional change; a prepreg which has small variation in the amount of dimensional change; a laminate; a printed wiring board; and a semiconductor package. The present invention additionally provides: a prepreg which is suppressed in the occurrence of a positional shift of a via; a laminate; a printed wiring board; and a semiconductor package. The method for producing a prepreg specifically comprises: a step for obtaining a prepreg precursor by impregnating a base material with a thermosetting resin composition and subsequently converting the thermosetting resin composition into a B-stage state; and a surface heat treatment step that is carried out after the step for obtaining a prepreg precursor. In the surface heat treatment step, the surface of the prepreg precursor is subjected to a heat treatment with a heat source temperature of 200-700°C.

Description

Prepreg manufacturing method, prepreg, laminate, printed wiring board, and semiconductor package

The present invention relates to a prepreg manufacturing method, a prepreg, a laminated board, a printed wiring board, and a semiconductor package.

In recent years, electronic devices have become smaller, lighter, and more multifunctional, and as a result, LSI (Large Scale Integration), chip components, etc. have become more highly integrated, and their form has also increased in number and size. 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 method for manufacturing a multilayer printed wiring board meeting these requirements, for example, using a prepreg as an insulating layer, only necessary portions are connected, for example, via holes formed by laser irradiation (hereinafter also referred to as “laser vias”). Build-up multilayer printed wiring boards for forming wiring layers are becoming mainstream as methods suitable for weight reduction, miniaturization, and fine wiring.

In multilayer printed wiring boards, it is important to have high electrical connection reliability and excellent high-frequency characteristics between multiple layers of wiring patterns formed with fine wiring pitch, and high connection reliability with semiconductor chips. Sex is required. In particular, in recent years, in a mother board such as a multi-function mobile phone terminal, the wiring board has a wiring width (L) and a spacing (S) (hereinafter referred to as wiring) along with high-speed communication, high wiring density, and extremely thin wiring board. In some cases, the width and the interval are combined to be expressed as [L / S]). With such narrowing of L / S, it is becoming difficult to stably produce a wiring board with a high yield. In the conventional wiring board design, a layer without a wiring pattern called a “skip layer” is provided in a part of the layers in consideration of a communication failure or the like. As electronic devices become highly functional, the amount of wiring design increases and the number of layers of the wiring board increases. However, the provision of the skip layer causes a problem that the thickness of the motherboard further increases.
As a method for improving these problems, it is effective to lower the dielectric constant of the insulating material used for the wiring board. L / S impedance can be easily controlled by lowering the dielectric constant of the insulating material, so L / S can be stably produced in a shape close to the current design, and the number of layers can be reduced by reducing skip layers. Become. For this reason, the insulating material used for the wiring board is required to have a material characteristic with a small relative dielectric constant.

In recent years, as the density of electronic devices has been increased, even for motherboards such as cellular phones, which are becoming thinner and lower in price, a material having a low relative dielectric constant is required in order to cope with the reduction in thickness. In addition, communication devices represented by servers, routers, mobile base stations, etc. are also used in higher frequency bands, and high melting point lead-free solder is used for soldering electronic components. Therefore, materials for substrates used for these materials are required to have a low dielectric constant, a high glass transition temperature (high Tg), and excellent reflow heat resistance. There is a tendency.

In addition, a mother board used for a multifunctional mobile phone terminal or the like is required to be connected by a small-diameter laser via when connecting between layers as the wiring density increases and the pattern width narrows. From the viewpoint of connection reliability, filled plating is often used, and the connectivity at the interface between inner layer copper and plated copper is very important, so there is a tendency to improve the laser workability of the base material. .
Generally, after laser processing of the substrate, a step of removing resin residual components (desmear treatment step) is performed. Since the desmear treatment is performed on the bottom surface and the wall surface of the laser via, when the resin component of the base material is dissolved in a large amount by the desmear treatment, the shape of the laser via may be remarkably deformed due to the dissolution of the resin. Various problems such as non-uniformity around the plating may occur. For this reason, 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 is an appropriate value.

Among various properties required for insulating materials used for wiring boards, for the purpose of reducing the relative dielectric constant, a method of containing an epoxy resin having a low relative dielectric constant, a method of introducing a cyanate group, a polyphenylene ether Methods of inclusion have been used. For example, a resin composition containing an epoxy resin (see Patent Document 1), a resin composition containing polyphenylene ether and bismaleimide (see Patent Document 2), and a resin composition containing polyphenylene ether and a cyanate resin (patent Reference 3), a resin composition containing at least one of styrene-based thermoplastic elastomers and / or triallyl cyanurate (see Patent Document 4), a resin composition containing polybutadiene (see Patent Document 5), polyphenylene A resin composition obtained by pre-reacting an ether resin, a polyfunctional maleimide and / or polyfunctional cyanate resin, and liquid polybutadiene (see Patent Document 6), and a compound having an unsaturated double bond group are provided. Or grafted polyphenylene ether and triallyl cyanurate and / or Resin composition containing lyaryl isocyanurate and the like (see Patent Document 7), reaction product of polyphenylene ether and unsaturated carboxylic acid or unsaturated acid anhydride, and polyfunctional maleimide and the like A thing (refer patent document 8) etc. are proposed.

JP 58-69046 A JP-A-56-133355 Japanese Patent Publication No. 61-18937 JP-A-61-286130 JP-A-62-148512 JP 58-164638 A Japanese Patent Laid-Open No. 2-208355 JP-A-6-179734

As described above, insulating materials used for wiring boards tend to require various characteristics such as reducing the relative dielectric constant. However, the dimensional variation of the prepreg varies with respect to interlayer connection by small diameter laser vias. Is also one of the most important characteristics. As the mother board becomes thinner, a multi-step lamination method is required as a method for laminating the prepreg, and the prepreg is subjected to a plurality of heat amounts and stress during lamination. For this reason, when the variation in the dimensional change of the prepreg is large (meaning the variation in the amount of heat shrinkage), a misalignment of vias connecting the layers may occur each time the layers are stacked. For this reason, it is required to stabilize the variation in the amount of heat shrinkage of the prepreg.
However, according to the study by the present inventors, it was found that the prepreg containing the conventional resin composition does not sufficiently suppress the variation in the dimensional change, and there is room for further improvement in this respect. .

Accordingly, an object of the present invention is to provide a method for manufacturing a prepreg with a small variation in dimensional change, and to provide a prepreg, a laminate, a printed wiring board, and a semiconductor package with a small variation in dimensional change. .
Another object of the present invention is to provide a prepreg, a laminated board, a printed wiring board, and a semiconductor package that are less likely to cause misalignment of vias.

As a result of diligent research to solve the above-mentioned problems, the present inventors impregnated a thermosetting resin composition into a substrate, and then B-staged the thermosetting resin composition to obtain a prepreg precursor. After obtaining the prepreg, the surface of the prepreg precursor is heat-treated at a predetermined heat source temperature to obtain a prepreg. It came to do. The present invention has been completed based on such knowledge.

（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。）
［７］前記熱硬化性樹脂組成物が、さらに
（Ｂ）エポキシ樹脂、
（Ｃ）置換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とを有する共重合樹脂、及び
（Ｄ）アミノシラン系カップリング剤で処理されたシリカ
を含有する、上記［５］又は［６］に記載のプリプレグの製造方法。
［８］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ノボラック型エポキシ樹脂及びジシクロペンタジエン型エポキシ樹脂からなる群から選択される少なくとも１種である、上記［７］に記載のプリプレグの製造方法。
［９］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［７］又は［８］に記載のプリプレグの製造方法。

（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。）
［１０］基材及び熱硬化性樹脂組成物を含有してなり、下記方法に従って求める標準偏差σが０．０１２％以下であるプリプレグ。
標準偏差σの算出方法：
　プリプレグ１枚の両面に厚さ１８μｍの銅箔を重ね、１９０℃、２．４５ＭＰａにて９０分間加熱加圧成形し、厚さ０．１ｍｍの両面銅張積層板を作製する。こうして得られた両面銅張積層板について、面内に直径１．０ｍｍの穴開けを図１に記載の１～８の場所に実施する。図１に記載のたて糸方向（１－７、２－６、３－５）及びよこ糸方向（１－３、８－４、７－５）の各３点ずつの距離を画像測定機を使用して測定し、各測定距離を初期値とする。その後、外層銅箔を除去し、乾燥機にて１８５℃で６０分間加熱する。冷却後、初期値の測定方法と同様にして、たて糸方向（１－７、２－６、３－５）及びよこ糸方向（１－３、８－４、７－５）の各３点ずつの距離を測定する。各測定距離の初期値に対する変化率からそれらの変化率の平均値を求め、該平均値に対する標準偏差σを算出する。
［１１］上記［１］～［９］のいずれかに記載の製造方法により得られた、上記［１０］に記載のプリプレグ。
［１２］前記熱硬化性樹脂組成物が（Ａ）マレイミド化合物を含有する、上記［１０］に記載のプリプレグ。
［１３］前記熱硬化性樹脂組成物が、さらに
（Ｂ）エポキシ樹脂、
（Ｃ）置換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とを有する共重合樹脂、及び
（Ｄ）アミノシラン系カップリング剤で処理されたシリカ
を含有する、上記［１０］又は［１２］に記載のプリプレグ。
［１４］前記熱硬化性樹脂組成物が、（Ｇ）エポキシ樹脂及び（Ｈ）エポキシ樹脂硬化剤を含有する、上記［１０］に記載のプリプレグ。
［１５］前記熱硬化性樹脂組成物が、（Ｋ）シリコーン変性マレイミド化合物及び（Ｌ）イミダゾール化合物を含有する、上記［１０］に記載のプリプレグ。
［１６］上記［１０］～［１５］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。
［１７］上記［１０］～［１５］のいずれかに記載のプリプレグ又は上記［１６］に記載の積層板を含有してなるプリント配線板。
［１８］上記［１７］に記載のプリント配線板に半導体素子を搭載してなる半導体パッケージ。
［１９］前記熱硬化性樹脂組成物が、（Ｇ）エポキシ樹脂及び（Ｈ）エポキシ樹脂硬化剤を含有する、上記［１］～［４］のいずれかに記載のプリプレグの製造方法。
［２０］前記熱硬化性樹脂組成物が、（Ｋ）シリコーン変性マレイミド化合物及び（Ｌ）イミダゾール化合物を含有する、上記［１］～［４］のいずれかに記載のプリプレグの製造方法。 The present invention relates to the following [1] to [20].
[1] After impregnating a base material with a thermosetting resin composition, B-stage the thermosetting resin composition to obtain a prepreg precursor, and after obtaining the prepreg precursor, a surface Having a heat treatment step,
The surface heat treatment step is a step of heat-treating the surface of the prepreg precursor at a heat source temperature of 200 to 700 ° C.
A method for producing a prepreg.
[2] After impregnating the base material with the thermosetting resin composition, B-stage the thermosetting resin composition to obtain a prepreg precursor, and after obtaining the prepreg precursor, Having a heat treatment step,
The surface heat treatment step is a step of heat-treating the surface of the prepreg precursor so that the surface temperature of the prepreg precursor is 40 to 130 ° C.
A method for producing a prepreg.
[3] The prepreg according to [1] or [2], further including a step of cooling the prepreg precursor to 5 to 60 ° C. after the step of obtaining the prepreg precursor and before the surface heat treatment step. Manufacturing method.
[4] The method for producing a prepreg according to any one of [1] to [3] above, wherein the time for the surface heat treatment is 1.0 to 10.0 seconds.
[5] The method for producing a prepreg according to any one of [1] to [4] above, wherein the thermosetting resin composition contains (A) a maleimide compound.
[6] The component (A) includes (a1) a maleimide compound having at least two N-substituted maleimide groups, (a2) a monoamine compound represented by the following general formula (a2-1), and (a3) The method for producing a prepreg according to the above [5], which is a maleimide compound having an N-substituted maleimide group obtained by reacting with a diamine compound represented by the general formula (a3-1).

(In General Formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group, and R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom. t is an integer of 1 to 5, u is an integer of 0 to 4, and 1 ≦ t + u ≦ 5, provided that when t is an integer of 2 to 5, a plurality of R ^A4 may be the same And when u is an integer of 2 to 4, a plurality of R ^A5 may be the same or different.)

(In the general formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or —O—. R ^A6 and R ^A7 each independently represents an alkyl having 1 to 5 carbon atoms. A group, a halogen atom, a hydroxyl group, a carboxy group, or a sulfonic acid group, and v and w are each independently an integer of 0 to 4.)
[7] The thermosetting resin composition further comprises (B) an epoxy resin,
The above [5] or (C) containing a copolymer resin having a structural unit derived from a substituted vinyl compound and a structural unit derived from maleic anhydride, and (D) silica treated with an aminosilane coupling agent. The method for producing a prepreg according to [6].
[8] The component (B) is a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a naphthalene type epoxy resin, an anthracene type epoxy resin, a biphenyl type epoxy resin, a biphenyl aralkyl novolak type epoxy resin, and The method for producing a prepreg according to the above [7], which is at least one selected from the group consisting of dicyclopentadiene type epoxy resins.
[9] The above-mentioned [7], wherein the component (C) is a copolymer resin having a structural unit represented by the following general formula (Ci) and a structural unit represented by the following formula (C-ii) ] Or the manufacturing method of the prepreg as described in [8].

(Wherein R ^C1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ^C2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkyl group having 6 to 20 carbon atoms) An aryl group, a hydroxyl group, or a (meth) acryloyl group, where x is an integer of 0 to 3, provided that when x is 2 or 3, a plurality of R ^C2 may be the same or different. May be.)
[10] A prepreg comprising a base material and a thermosetting resin composition and having a standard deviation σ of 0.012% or less determined according to the following method.
Standard deviation σ calculation method:
A copper foil having a thickness of 18 μm is stacked on both surfaces of one prepreg, and heat-press molding is performed at 190 ° C. and 2.45 MPa for 90 minutes, thereby producing a double-sided copper-clad laminate having a thickness of 0.1 mm. With respect to the double-sided copper clad laminate thus obtained, a hole having a diameter of 1.0 mm is formed in the plane at the locations 1 to 8 shown in FIG. Use an image measuring machine to determine the distance between each of the three points in the warp direction (1-7, 2-6, 3-5) and weft direction (1-3, 8-4, 7-5) shown in FIG. And measure each distance as the initial value. Thereafter, the outer layer copper foil is removed and heated at 185 ° C. for 60 minutes in a dryer. After cooling, in the same manner as the initial value measurement method, three points each in the warp direction (1-7, 2-6, 3-5) and the weft direction (1-3, 8-4, 7-5) Measure distance. An average value of the change rates is obtained from the change rate with respect to the initial value of each measurement distance, and a standard deviation σ with respect to the average value is calculated.
[11] The prepreg according to [10] obtained by the production method according to any one of [1] to [9].
[12] The prepreg according to [10] above, wherein the thermosetting resin composition contains (A) a maleimide compound.
[13] The thermosetting resin composition further comprises (B) an epoxy resin,
The above [10] or (C) containing a copolymer resin having a structural unit derived from a substituted vinyl compound and a structural unit derived from maleic anhydride, and (D) silica treated with an aminosilane coupling agent. The prepreg according to [12].
[14] The prepreg according to [10] above, wherein the thermosetting resin composition contains (G) an epoxy resin and (H) an epoxy resin curing agent.
[15] The prepreg according to [10] above, wherein the thermosetting resin composition contains (K) a silicone-modified maleimide compound and (L) an imidazole compound.
[16] A laminate comprising the prepreg according to any one of [10] to [15] above and a metal foil.
[17] A printed wiring board comprising the prepreg according to any one of [10] to [15] or the laminated board according to [16].
[18] A semiconductor package comprising a semiconductor element mounted on the printed wiring board according to [17].
[19] The method for producing a prepreg according to any one of the above [1] to [4], wherein the thermosetting resin composition contains (G) an epoxy resin and (H) an epoxy resin curing agent.
[20] The method for producing a prepreg according to any one of the above [1] to [4], wherein the thermosetting resin composition contains (K) a silicone-modified maleimide compound and (L) an imidazole compound.

According to the present invention, it is possible to provide a method for producing a prepreg with a small variation in dimensional change, and to provide a prepreg, a laminate, a printed wiring board, and a semiconductor package with a small variation in dimensional change. The present invention can also provide a prepreg, a laminated board, a printed wiring board, and a semiconductor package that are less likely to cause misalignment of vias.

It is a schematic diagram of the evaluation board | substrate used for the measurement of the variation in the dimensional change amount in an Example.

In the numerical range described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples. Further, the lower limit value and the upper limit value of the numerical range can be arbitrarily combined with the lower limit value and the upper limit value of other numerical ranges, respectively.
Moreover, unless otherwise indicated, each component and material illustrated in this specification may be used individually by 1 type, and may use 2 or more types together. In the present specification, the content of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. Means.
Embodiments in which the items described in this specification are arbitrarily combined are also included in the present invention.

[Prepreg production method]
The present invention includes a step (step 1) of obtaining a prepreg precursor by impregnating a base material with a thermosetting resin composition and then B-staging the thermosetting resin composition to obtain the prepreg precursor. A method for producing a prepreg having a surface heat treatment step (step 3) after the step, wherein the step 3 is a step of obtaining a prepreg by heat-treating the surface of the prepreg precursor at a heat source temperature of 200 to 700 ° C.
The step 3 is a surface heat treatment step of obtaining a prepreg by heat-treating the surface of the prepreg precursor so that the surface temperature of the prepreg precursor becomes 40 to 130 ° C. after the step of obtaining the prepreg precursor. it can.
Usually, after the step of obtaining the prepreg precursor (step 1) and before the surface heat treatment step (step 3), the step of cooling the prepreg precursor to 5 to 35 ° C. (step 2) is included. It is preferable.
Hereinafter, Steps 1 to 3 will be described in order, and then the base material and the thermosetting resin composition constituting the prepreg will be described.

<Step 1>
Step 1 is a step of impregnating a base material with a thermosetting resin composition, and then B-staging the thermosetting resin composition to obtain a prepreg precursor.
Although it does not specifically limit as a method of impregnating a base material with a thermosetting resin composition, A hot-melt method, a solvent method, etc. are mentioned.
The hot melt method is a method of directly impregnating a base material with a thermosetting resin composition whose viscosity has been reduced by heating. For example, the thermosetting resin composition is once applied to coated paper having excellent peelability. And a method of laminating the resin film on the substrate, a method of directly applying the thermosetting resin composition to the substrate with a die coater, and the like.
The solvent method is a method of impregnating a base material in a state where a thermosetting resin composition contains an organic solvent to form a resin varnish. Can be mentioned.

A prepreg precursor in which the thermosetting resin composition is B-staged can be obtained by impregnating the base material with the thermosetting resin composition and then performing a heat treatment.
Here, when the hot melt method is applied, the B-staging may be performed simultaneously with the heating in laminating the resin film on the substrate. That is, the resin film may be laminated to the substrate while being heated, and the heating may be continued as it is to obtain a prepreg precursor by B-staging the thermosetting resin composition. In that case, the heating temperature at the time of lamination and the heating temperature at the B-stage may be the same or different. The heating temperature when laminating the resin film on the substrate is not particularly limited, but is preferably 15 to 150 ° C, 20 to 130 ° C, or 20 to 100 ° C.
Further, when the solvent method is applied, the B-staging may be performed simultaneously with the heating for drying the resin varnish. That is, after the base material is immersed in the resin varnish, the organic solvent is dried by heating, and the heating is continued as it is, so that the thermosetting resin composition is B-staged to obtain a prepreg precursor. In that case, the heating temperature at the time of lamination and the heating temperature at the B-stage may be the same or different. The heating temperature for drying the resin varnish is not particularly limited, but is preferably 10 to 190 ° C., 15 to 180 ° C., or 15 to 170 ° C.

The conditions for B-staging in this step 1 are not particularly limited as long as the thermosetting resin composition can be B-staged, and may be appropriately determined according to the type of the thermosetting resin. The heating temperature is, for example, preferably 70 to 190 ° C., 80 to 180 ° C., 120 to 180 ° C., or 140 to 180 ° C. The heating method is not particularly limited, and examples thereof include a heating method using a panel heater, a heating method using hot air, a heating method using high frequency, a heating method using magnetic lines, a heating method using a laser, and a heating method combining these. Among these, a heating method using a panel heater and a heating method using hot air are simple and preferable. The heating time is, for example, 1 to 30 minutes, 2 to 20 minutes, 2 to 10 minutes, or 2 to 6 minutes.

<Process 2>
Step 2 is a step of cooling the prepreg precursor obtained in Step 1. That is, in step 2, the prepreg precursor obtained by subjecting the thermosetting resin composition to B-stage by performing heat treatment in step 1 is cooled to at least a temperature lower than the temperature at which the heat treatment was performed. It is a process.
By performing step 2, the thermosetting resin composition is subjected to a thermal history that is generally imparted when producing a prepreg, such as B-staging and cooling, and the obtained prepreg precursor is There is a tendency to inherently cause strains and the like that cause dimensional changes in the prepreg.
In this way, by eliminating the strain caused by the thermal history of heating (step 1) and cooling (step 2) before the step 3 to be described later, the above-described strain and the like are eliminated by the step 3 and the dimensional change. This is preferable because it is easy to effectively achieve uniform amount. Furthermore, the strain caused by the thermal history of heating (step 1) and cooling (step 2) once eliminated by step 3 does not occur even if the same thermal history is applied after step 3, Or even if it occurs, it becomes very small, and the prepreg obtained by the present invention tends to have very little variation in dimensional change.

The prepreg precursor may be cooled by natural cooling or may be performed using a cooling device such as a blower or a cooling roll. In addition, it is preferable to perform cooling with a blower from the viewpoint of productivity. The surface temperature of the prepreg precursor after cooling in this step is usually 5 to 60 ° C., preferably 10 to 45 ° C., more preferably 10 to 30 ° C., and even more preferably room temperature.
In this specification, room temperature refers to an ambient temperature without temperature control such as heating and cooling, and is generally about 15 to 25 ° C., but may vary depending on the weather, season, etc. It is not limited.

<Step 3>
Step 3 is a surface heat treatment step for obtaining a prepreg by heat-treating the surface of the prepreg precursor at a heat source temperature of 200 to 700 ° C. with respect to the prepreg precursor obtained in the step 1 or the step 2. It can also be referred to as a surface heat treatment step in which the surface of the prepreg precursor is heat-treated so that the surface temperature of the body becomes 40 to 130 ° C. to obtain a prepreg.
By this step 3, a prepreg having a small variation in the dimensional change amount is obtained. Although the exact reason is not clear, this step 3 eliminates the distortion of the base material in the prepreg precursor obtained in step 1 or 2, and reduces the dimensional change during curing due to the distortion. Therefore, it is considered that the variation in the dimensional change amount is reduced. By reducing the variation in the dimensional change amount, the occurrence of via misalignment is reduced.

The heating method of the surface heat treatment in step 3 is not particularly limited, and is a heating method using a panel heater, a heating method using hot air, a heating method using high frequency, a heating method using magnetic lines, a heating method using a laser, a heating method combining these, and the like. Is mentioned. Among these, from the viewpoint of easy control of the surface temperature, a heating method using a panel heater and a heating method using hot air are preferable.
In one embodiment of the present invention, the surface heat treatment is carried out at a heat source temperature of 200 to 700 ° C., but from the viewpoint of keeping the prepreg productivity better, and keeping the prepreg in the B-stage state, the moldability is kept good. However, from the viewpoint of reducing the variation in the amount of dimensional change, it is preferable to perform the heat treatment at a higher temperature and in a shorter time than the heat treatment for forming the B-stage in step 1. From this viewpoint, the heat source temperature in the surface heat treatment is preferably 250 to 700 ° C., more preferably 300 to 600 ° C., and further preferably 350 to 550 ° C. In particular, when a heating method using a panel heater or hot air is performed, it is preferable to perform the surface heat treatment in the temperature range.
In one embodiment of the present invention, the surface heat treatment is performed at a surface temperature of the prepreg precursor of, for example, preferably 40 to 40 from the viewpoint of reducing variation in dimensional change while maintaining good prepreg moldability. It is carried out so that the temperature is 130 ° C., more preferably 40 to 110 ° C., still more preferably 60 to 90 ° C. It is preferable that the surface temperature of the prepreg precursor is within the above range at the heat source temperature.
The heating time of the surface heat treatment is not particularly limited, but the viewpoint of keeping the prepreg productivity good, and maintaining the prepreg in the B-stage state, the dimensional change varies while keeping the moldability good. From the viewpoint of reduction, 1.0 to 10.0 seconds are preferred, 1.5 to 6.0 seconds are more preferred, and 2.0 to 4.0 seconds are even more preferred.
Increase in surface temperature of prepreg precursor due to surface heat treatment (that is, absolute value of difference between surface temperature before surface heat treatment and maximum surface temperature reached during surface heat treatment) has good moldability of prepreg From the viewpoint of reducing the variation in the amount of dimensional change while maintaining the temperature, it is preferably 5 to 110 ° C, more preferably 20 to 90 ° C, and further preferably 40 to 70 ° C.
However, the detailed heating conditions of the surface heat treatment may be obtained as long as the surface temperature of the prepreg precursor is higher than the surface temperature before the surface heat treatment is performed by setting the heat source temperature in the above-described range. It is not particularly limited as long as it does not significantly affect various properties (for example, fluidity) of the prepreg, and may be appropriately determined according to the type of the thermosetting resin.

The prepreg obtained in step 3 is preferably subjected to a cooling step for cooling the prepreg from the viewpoints of prepreg handling and tackiness. The prepreg may be cooled by natural cooling or using a cooling device such as a blower or a cooling roll. The temperature of the prepreg after cooling is usually 5 to 80 ° C., preferably 8 to 50 ° C., more preferably 10 to 30 ° C., and further preferably room temperature.

The content in terms of solid content of the thermosetting resin composition in the prepreg of the present invention obtained as described above is preferably 20 to 90% by mass, more preferably 30 to 85% by mass, and 50 to 80% by mass. Is more preferable.
The thickness of the prepreg of the present invention is, for example, 0.01 to 0.5 mm, and is preferably 0.02 to 0.3 mm from the viewpoint of enabling moldability and high-density wiring, and 0.05 to 0.00 mm. 2 mm is more preferable.

Hereinafter, the base material and thermosetting resin composition used for the production of the prepreg of the present invention will be described in detail.
〔Base material〕
As a base material which comprises the prepreg of this invention, a sheet-like reinforcement base material is used, The well-known thing used for the laminated board for various electrical insulation materials can be used. Examples of the material of the base material include 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; and mixtures thereof. Can be mentioned. Among these, glass fiber is preferable from the viewpoint of flame retardancy. Glass fiber base materials include woven fabrics using E glass, C glass, D glass, S glass, etc., or glass woven fabrics in which short fibers are bonded with an organic binder; Can be mentioned. More preferably, it is a glass woven fabric using E glass.
These base materials have shapes, such as a woven fabric, a nonwoven fabric, a robink, a chopped strand mat, or a surfacing mat, for example. In addition, a material and a shape are selected by the use and performance of the target molding, and 1 type may be used independently and 2 or more types of materials and shapes can also be combined as needed.
The thickness of the substrate is, for example, 0.01 to 0.5 mm, and is preferably 0.015 to 0.2 mm, and preferably 0.02 to 0.15 mm from the viewpoint of enabling moldability and high-density wiring. More preferred. From the viewpoint of heat resistance, moisture resistance, workability, and the like, these substrates are preferably those that have been surface-treated with a silane coupling agent or the like, or those that have been mechanically subjected to fiber opening treatment.

By the way, the prepregs described in Patent Documents 1 to 8 show a relatively good relative dielectric constant, but there are many cases where the strict demands of the market in recent years cannot be satisfied. In addition, the variation in the amount of dimensional change is not sufficiently suppressed, but it is also one of high heat resistance, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and plating rotation (laser processability). In many cases, there is room for further improvement. In the past, material development from the viewpoint of satisfying all of the above characteristics has not been made.
However, in the present invention, in addition to sufficiently suppressing the variation in dimensional change by using the following components of the thermosetting resin composition while utilizing the method for producing the prepreg of the present invention, High heat resistance, high metal foil adhesiveness, high glass transition temperature, low thermal expansion, moldability, and plating wraparound (laser processability) can be satisfied. From this viewpoint, it is preferable to use the following thermosetting resin composition.

[Thermosetting resin composition]
The thermosetting resin composition that can be used in the present invention is not particularly limited, but in addition to sufficiently suppressing variation in dimensional change, it has high heat resistance, high metal foil adhesion, and high glass. From the viewpoint of satisfying the transition temperature, low thermal expansibility, moldability, and plating rotability (laser processability), (A) a thermosetting resin composition containing a maleimide compound (hereinafter, thermosetting resin composition [I ] Is preferred. From the same viewpoint, the thermosetting resin composition [I] further comprises (B) an epoxy resin, (C) a copolymer resin having a structural unit derived from a substituted vinyl compound and a structural unit derived from maleic anhydride. And (D) silica treated with an aminosilane coupling agent is more preferable. From the same viewpoint, the thermosetting resin composition [I] preferably contains (E) a curing agent, and from the viewpoint of flame retardancy, (F) preferably contains a flame retardant.
In addition, from the viewpoint of sufficiently suppressing the variation in dimensional change, (G) an epoxy resin and (H) an epoxy resin curing agent, and, if necessary, (I) a curing accelerator and (J) an inorganic filler Or (K) a silicone-modified maleimide compound and (L) an imidazole compound, and (M) a thermosetting resin composition containing an inorganic filler, if necessary. III].

（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。 First, each component contained in the thermosetting resin composition [I] will be described in detail.
<(A) Maleimide compound>
Component (A) is a maleimide compound (hereinafter sometimes referred to as maleimide compound (A)), preferably a maleimide compound having an N-substituted maleimide group, and more preferably (a1) at least two N A maleimide compound having a substituted maleimide group [hereinafter abbreviated as maleimide compound (a1)], (a2) the following general formula (a2-1)

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

(In the general formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or —O—. R ^A6 and R ^A7 each independently represents an alkyl having 1 to 5 carbon atoms. A group, a halogen atom, a hydroxyl group, a carboxy group, or a sulfonic acid group, and v and w are each independently an integer of 0 to 4.)
A maleimide compound having an N-substituted maleimide group, obtained by reacting with a diamine compound represented by the following [hereinafter abbreviated as diamine compound (a3)].
Hereinafter, the description regarding the maleimide compound (A) can also be read as the description of the 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, and still more preferably 800 from the viewpoints of solubility in organic solvents and mechanical strength. ~ 2,000. In addition, the weight average molecular weight in this specification is a value measured by 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.
As the maleimide compound (a1), a maleimide compound having an aliphatic hydrocarbon group (but no aromatic hydrocarbon group is present) between any two maleimide groups among a plurality of maleimide groups [hereinafter referred to as fat Or a maleimide compound containing an aromatic hydrocarbon group between any two maleimide groups of the plurality of maleimide groups [hereinafter referred to as aromatic hydrocarbon group] Referred to as a containing maleimide]. Among these, an aromatic hydrocarbon group-containing maleimide is preferable from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating revolving property. The aromatic hydrocarbon group-containing maleimide only needs to contain an aromatic hydrocarbon group between any combination of two maleimide groups selected arbitrarily, and is also an aliphatic hydrocarbon together with the aromatic hydrocarbon group. It may have a group.
As maleimide compound (a1), from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesiveness, high glass transition temperature, low thermal expansion, moldability, and plating rotation, two or more per molecule Maleimide compounds having 5 N-substituted maleimide groups are preferred, and maleimide compounds having 2 N-substituted maleimide groups in one molecule are more preferred. Moreover, as a maleimide compound (a1), following general formula (a1) from a viewpoint of high heat resistance, a low dielectric constant, high metal foil adhesiveness, high glass transition temperature, low thermal expansion property, moldability, and plating revolving property. -1) to (a1-4), and more preferably an aromatic hydrocarbon group-containing maleimide represented by any of the following general formulas (a1-1), (a1-2) or (a1-4) The aromatic hydrocarbon group-containing maleimide represented by general formula (a1-2) is more preferred, and the aromatic hydrocarbon group-containing maleimide represented by the following general formula (a1-2) is particularly preferred.

In the above formula, R ^A1 to R ^A3 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms. X ^A1 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, —O—, —C (═O) —, —S—, —SS— or a sulfonyl group. p, q, and r are each independently an integer of 0-4. s is an integer of 0 to 10.
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^A1 to R ^A3 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 n-pentyl group. The aliphatic hydrocarbon group is preferably 1 to 1 carbon atoms from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating swirlability. 3 is an aliphatic hydrocarbon group, more preferably a methyl group or an ethyl group.

Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^A1 include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group. Is mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating rotation. Group, more preferably a methylene group.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X ^A1 include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group. Among these, an isopropylidene group is preferable from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesiveness, high glass transition temperature, low thermal expansion, moldability, and plating rotation.
X ^A1 is preferably an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms among the above options. 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 dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and roundness with plating. In view of the above, each is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
s is an integer of 0 to 10, and is preferably 0 to 5, 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 in which s is 0 to 3.

Specific examples of the maleimide compound (a1) include N, N′-ethylene bismaleimide, N, N′-hexamethylene bismaleimide, bis (4-maleimidocyclohexyl) methane, and 1,4-bis (maleimide). Methyl) cyclohexane or other aliphatic hydrocarbon group-containing maleimide; 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-maleimidophenyl) methane, bis (3-methyl-4- Maleimidophenyl) methane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, bis (4-maleimide) Phenyl) ether, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ketone, 1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis ( Maleimidomethyl) cyclohexane, 1,3-bis (4-maleimidophenoxy) benzene, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, bis [4- ( 4-maleimidophenoxy) phenyl] methane, 1,1-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (3-Maleimidophenoxy) phenyl] ethane, 1,2-bis [4- ( -Maleimidophenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [ 4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1 , 1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4- Bis (3-maleimidophenoxy) biphenyl, 4,4-bis (4-maleimidophenoxy) biphenyl, bis [4- (3-maleimidophenoxy) phenyl] Ketone, bis [4- (4-maleimidophenoxy) phenyl] ketone, bis (4-maleimidophenyl) disulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfide, bis [4- (4-maleimidophenoxy) phenyl ] Sulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- ( 4-maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] ether, 1,4-bis [4- (4-maleimidophenoxy) ) -Α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 3-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] Benzene, 1,3-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -3,5 -Dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, polyphenylmeta And an aromatic hydrocarbon group-containing maleimide such as Nmaleimide.

Among these, from the viewpoint of high reaction rate and higher heat resistance, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4 -Maleimidophenyl) disulfide, N, N ′-(1,3-phenylene) bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane are preferred, and bis (4-Maleimidophenyl) methane and N, N ′-(1,3-phenylene) bismaleimide are preferred, and bis (4-maleimidophenyl) methane is particularly preferred from the viewpoint of solubility in a solvent.
As the maleimide compound (a1), one type may be used alone, or two or more types may be used in combination.

(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 an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group. R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom. 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 R ^A4 may be the same or different. When u is an integer of 2 to 4, a plurality of R ^A5 may be the same or different.
The acidic substituent represented by R ^A4 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 preferably 1 to 3 from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and plating-around properties. An integer of 1, more preferably 1 or 2, and still more preferably 1.
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^A5 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. Can be mentioned. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
Examples of the halogen atom represented by R ^A5 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
u is an integer of 0 to 4, and preferably 0 to 3 from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and plating rotation. An integer of 0, more preferably an integer of 0 to 2, still more preferably 0 or 1, and particularly preferably 0.
As the monoamine compound (a2), from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesiveness, high glass transition temperature, low thermal expansion, moldability, and plating revolving property, the following general formula ( a monoamine compound represented by a2-2) or (a2-3), more preferably a monoamine compound represented by the following general formula (a2-2). However, R ^A4 , R ^A5 and u in the general formulas (a2-2) and (a2-3) are the same as those in 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, 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 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 expansibility and production cost.
A monoamine compound (a2) may be used individually by 1 type, and may use 2 or more types together.

（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 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or —O—. R ^A6 and R ^A7 each independently represents an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a hydroxyl group. Represents a carboxy group or a sulfonic acid group, and v and w are each independently an integer of 0 to 4.)

Examples of the aliphatic hydrocarbon group of X ^A2 carbon number of 1 to 3 shown, for example, methylene group, ethylene group, propylene group, propylidene group, and the like.
X ^A2 is preferably a methylene group.
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^A6 and R ^A7 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. Groups and the like. 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 still more preferably 0.

（式中、Ｘ^Ａ２、Ｒ^Ａ６、Ｒ^Ａ７、ｖ及びｗは、前記一般式（ａ３－１）中のものと同じであり、好ましい態様も同じである。） The diamine compound (a3) is preferably a diamine compound represented by the following general formula (a3-1 ′).

(In the formula, X ^A2 , R ^A6 , R ^A7 , v and w are the same as those in the general formula (a3-1), and preferred embodiments are also the same.)

Specific examples of the diamine compound (a3) include 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenylpropane, 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'-di Loro-4,4′-diaminodiphenylmethane, 3,3′-dibromo-4,4′-diaminodiphenylmethane, 2,2 ′, 6,6′-tetramethylchloro-4,4′-diaminodiphenylmethane, 2,2 Examples include ', 6,6'-tetrabromo-4,4'-diaminodiphenylmethane. Among these, 4,4′-diaminodiphenylmethane and 3,3′-diethyl-4,4′-diaminodiphenylmethane are preferable from the viewpoint of inexpensiveness, and 4,4′- from the viewpoint of solubility in a solvent. Diaminodiphenylmethane is more preferred.

The reaction of the maleimide compound (a1), monoamine compound (a2) and diamine compound (a3) is preferably carried out by reacting at a reaction temperature of 70 to 200 ° C. for 0.1 to 10 hours in the presence of an organic solvent. preferable.
The reaction temperature is more preferably 70 to 160 ° C., further 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.

(Use amount of maleimide compound (a1), monoamine compound (a2) and diamine compound (a3))
In the reaction of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3), the three amounts used are equivalent to the primary amino group equivalent [—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 ₂ group equivalent] ≦ 10
By setting [maleimide group equivalent] / [-NH ₂ group equivalent total] to 0.1 or more, gelation and heat resistance do not decrease, and by setting it to 10 or less, Since solubility, metal foil adhesiveness, and heat resistance do not fall, it is preferable.
From the same viewpoint, more preferably,
1 ≦ [maleimide group equivalent] / [total sum of —NH ₂ group equivalents] ≦ 9, more preferably
2 ≦ [maleimide group equivalent] / [total of —NH ₂ group equivalent] ≦ 8.

(Organic solvent)
As described above, the reaction of the maleimide compound (a1), the monoamine compound (a2), and the diamine compound (a3) is preferably performed 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, propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ether solvents such as tetrahydrofuran; toluene, xylene, mesitylene Aromatic solvents such as dimethylformamide, dimethylacetamide, nitrogen atom-containing solvents including amide solvents such as N-methylpyrrolidone; sulfur atom-containing solvents including sulfoxide solvents such as dimethylsulfoxide; ethyl acetate, γ- Examples thereof include ester solvents such as butyrolactone. Of 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. In view of the fact that it is highly soluble and hardly remains as a residual solvent during the production of the prepreg, cyclohexanone, propylene glycol monomethyl ether, and dimethylacetamide are more preferable, and dimethylacetamide is particularly preferable.
An organic solvent may be used individually by 1 type, and may use 2 or more types together.
Although there is no restriction | limiting in particular in the usage-amount of an organic solvent, Preferably it is 25 with respect to a total of 100 mass parts of a maleimide compound (a1), a monoamine compound (a2), and a diamine compound (a3) from a viewpoint of solubility and reaction efficiency. The amount may be ˜1,000 parts by mass, more preferably 40 to 700 parts by mass, and still more preferably 60 to 250 parts by mass. By making it 25 parts by mass or more with respect to a total of 100 parts by mass of the maleimide compound (a1), monoamine compound (a2) and diamine compound (a3), it becomes easy to ensure solubility, and it should be 1,000 parts by mass or less. Therefore, it is easy to suppress a significant decrease in reaction efficiency.

(Reaction catalyst)
You may implement reaction of a maleimide compound (a1), a monoamine compound (a2), and a diamine compound (a3) in presence of a reaction catalyst as needed. 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.
A reaction catalyst may be used individually by 1 type, and may use 2 or more types together.
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 sometimes 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 glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, and glycidyl ester type epoxy resins. Among these, a glycidyl ether type epoxy resin is preferable.
The epoxy resin (B) is classified into various epoxy resins depending on the main skeleton, and in each of the above-mentioned types of epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, etc. Bisphenol type epoxy resin; biphenylaralkyl novolak type epoxy resin, phenol novolak type epoxy resin, alkylphenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthol alkylphenol copolymer novolak type epoxy resin, naphthol aralkyl cresol copolymer novolak type epoxy resin, Bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin and other novolac epoxy resins; stilbene 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; Xylylene-type epoxy resin; Dicyclopentadiene-type epoxy resin It is classified into alicyclic epoxy resin.
Among these, from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesiveness, high glass transition temperature, low thermal expansion, moldability and plating rotation, bisphenol F type epoxy resin, phenol novolac type epoxy resin Preferably, at least one selected from the group consisting of cresol novolac type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenylaralkyl novolak type epoxy resin and dicyclopentadiene type epoxy resin, and low thermal expansion Cresol novolac type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl novolak type epoxy resin and phenol novolac type More preferably at least one selected from the group consisting of epoxy resin, more preferably a cresol novolak type epoxy resin.
An epoxy resin (B) may be used individually by 1 type, and may use 2 or more types together.

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 of the resin per epoxy group (g / eq), and can be measured according to the method defined in JIS K 7236 (2001). Specifically, using an automatic titrator “GT-200 type” manufactured by Mitsubishi Chemical Analytech Co., Ltd., weigh 2 g of epoxy resin in a 200 ml beaker, drop 90 ml of methyl ethyl ketone, dissolve in an ultrasonic cleaner, 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.
As a commercially available product of the epoxy resin (B), a cresol novolac type epoxy resin “EPICLON (registered trademark) N-673” (manufactured by DIC Corporation, epoxy equivalent: 205 to 215 g / eq), a naphthalene type epoxy resin “HP-4032” (Mitsubishi Chemical Corporation, epoxy equivalent: 152 g / eq), biphenyl type epoxy resin “YX-4000” (Mitsubishi Chemical Corporation, epoxy equivalent: 186 g / eq), dicyclopentadiene type epoxy resin “HP-7200H” (DIC Corporation, epoxy equivalent; 280 g / eq) and the like. The epoxy equivalent is a value described in the catalog of the product manufacturer.

<(C) Specific copolymer resin>
Component (C) is a copolymer resin having a structural unit derived from a substituted vinyl compound and a structural unit derived from maleic anhydride (hereinafter sometimes referred to as copolymer resin (C)). Examples of the substituted vinyl compound include aromatic vinyl compounds, aliphatic vinyl compounds, and functional group-substituted vinyl compounds. Examples of the aromatic vinyl compound include styrene, 1-methylstyrene, vinyltoluene, dimethylstyrene and the like. Examples of the aliphatic vinyl compound include propylene, butadiene, isobutylene and the like. Examples of the functional group-substituted vinyl compound include acrylonitrile; a compound having a (meth) acryloyl group such as methyl acrylate and methyl methacrylate.
Among these, as the substituted vinyl compound, an aromatic vinyl compound is preferable, and styrene is more preferable.
As the component (C), a copolymer resin having a structural unit represented by the following general formula (Ci) 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。）

(Wherein R ^C1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ^C2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkyl group having 6 to 20 carbon atoms) An aryl group, a hydroxyl group, or a (meth) acryloyl group, where x is an integer of 0 to 3, provided that when x is 2 or 3, a plurality of R ^C2 may be the same or different. May be.)

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^C1 and R ^C2 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. Groups and the like. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
Examples of the alkenyl group having 2 to 5 carbon atoms represented by R ^C2 include an allyl group and a crotyl group. The alkenyl group is preferably an alkenyl group having 3 to 5 carbon atoms, more preferably an alkenyl group having 3 or 4 carbon atoms.
Examples of the aryl group having 6 to 20 carbon atoms represented by R ^C2 include a phenyl group, a naphthyl group, an anthryl group, and a biphenylyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, 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 (Ci), R ^C1 is a hydrogen atom and x is 0, derived from the structural unit represented by the following general formula (Ci-1), that is, styrene The structural unit is preferred.

Content ratio of the structural unit derived from the substituted vinyl compound and the structural unit derived from maleic anhydride in the copolymer resin (C) [structural unit derived from the substituted vinyl compound / structural unit derived from maleic anhydride] (mol) The ratio is preferably from 1 to 9, more preferably from 2 to 9, even more preferably from 3 to 8, particularly preferably from 3 to 7. The content ratio of the structural unit represented by the general formula (Ci) to the structural unit represented by the formula (C-ii) [(Ci) / (Cii)] (molar ratio) Similarly, it is preferably 1 to 9, more preferably 2 to 9, further preferably 3 to 8, and particularly preferably 3 to 7. If the molar ratio is 1 or more, preferably 2 or more, the effect of improving the dielectric properties tends to be sufficient, and if it is 9 or less, the compatibility tends to be good.
The total content of the structural unit derived from the substituted vinyl compound and the structural unit derived from maleic anhydride in the copolymer resin (C), and the structural unit represented by the general formula (Ci) and the formula ( The total content of 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% by mass. %.
The weight average molecular weight (Mw) of the copolymer resin (C) is preferably 4,500 to 18,000, more preferably 5,000 to 18,000, more preferably 6,000 to 17,000, still more preferably. It is 8,000 to 16,000, particularly preferably 8,000 to 15,000, most preferably 9,000 to 13,000.

In addition, the technique for lowering the dielectric constant of an epoxy resin by using a copolymer resin of styrene and maleic anhydride, when applied to a printed wiring board material, results in insufficient impregnation into the substrate and copper foil peel strength. Therefore, it generally tends to be avoided. For this reason, the use of the copolymer resin (C) generally tends to be avoided, but the present invention uses the copolymer resin (C) while the components (A) and (B). And a thermosetting resin composition having high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature and low thermal expansion, and excellent moldability and plating-around properties. It was discovered and accomplished.

(Method for producing copolymer resin (C))
The copolymer resin (C) can be produced by copolymerizing a substituted vinyl compound and maleic anhydride.
The substituted vinyl compound is as described above. A substituted vinyl compound may be used individually by 1 type, and may use 2 or more types together. In addition to the substituted vinyl compound and maleic anhydride, various polymerizable components may be copolymerized.
In addition, substituents such as allyl groups, methacryloyl groups, acryloyl groups, and hydroxy groups are introduced into the substituted vinyl compounds, particularly aromatic vinyl compounds, through Friedel-Crafts reactions or reactions using metal catalysts such as lithium. May be.

Commercial products can also be used as the copolymer resin (C). Examples of commercially available products include “SMA (registered trademark) 1000” (styrene / maleic anhydride = 1, Mw = 5,000), “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 Co., Ltd.].

<(D) Silica Treated with Aminosilane Coupling Agent>
As the component (D), among silicas, when silica treated with an aminosilane coupling agent (hereinafter, sometimes referred to as silica (D) treated with an aminosilane coupling agent) is used, low thermal expansibility is obtained. In addition to the effect of improving, since the drop-off of silica is suppressed by improving the adhesion with the components (A) to (C), the effect of suppressing deformation of the laser via shape due to excessive desmear can be obtained. Therefore, it is preferable.

（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, the aminosilane coupling agent is preferably a silane coupling agent having a silicon-containing group represented by the following general formula (D-1) and an amino group.

(Wherein R ^D1 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)

^Examples of the alkyl group having 1 to 3 carbon atoms represented by R ^D1 include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Among these, a methyl group is preferable.
^Examples of the acyl group having 2 to 4 carbon atoms represented by RD1 include an acetyl group, a propionyl group, and an acrylic group. Among these, an acetyl group is preferable.

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

Instead of silica (D) treated with an aminosilane coupling agent, as an inorganic filler other than the component (D), for example, an epoxysilane coupling agent, a phenylsilane coupling agent, an alkylsilane coupling agent Alkenyl silane coupling agents, alkynyl silane coupling agents, haloalkyl silane coupling agents, siloxane coupling agents, hydrosilane coupling agents, silazane coupling agents, alkoxy silane coupling agents, chlorosilane cups Ring agent, (meth) acryl silane coupling agent, amino silane coupling agent, isocyanurate silane coupling agent, ureido silane coupling agent, mercapto silane coupling agent, sulfide silane coupling agent or Silica treated with a socyanate silane coupling agent or the like; Silica that has not been surface-treated can be used, but from the viewpoint of the above effect, silica (D) treated with an aminosilane coupling agent is used. Is preferred.
Moreover, you may use together the silica (D) processed with the aminosilane type coupling agent, and the silica processed with the above-mentioned other coupling agent. In this case, although not particularly limited, the content of silica treated with another coupling agent is preferably 50 with respect to 100 parts by mass of silica (D) treated with an aminosilane coupling agent. It is at most 30 parts by mass, more preferably at most 15 parts by mass, particularly preferably at most 10 parts by mass, most preferably at most 5 parts by mass.

Examples of the silica include precipitated silica produced by a wet method and having a high water content, and dry method silica produced by a dry method and containing almost no bound water or the like. Examples of the dry process silica include crushed silica, fumed silica, and fused silica (fused spherical silica) depending on the production method. Silica is preferably fused silica from the viewpoint of low thermal expansibility and high fluidity when filled in a resin.
The average particle diameter of the silica is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.1 to 6 μm, still more preferably 0.1 to 3 μm, and particularly preferably 1 to 3 μm. By making the average particle diameter of silica 0.1 μm or more, the fluidity at the time of high filling can be kept good, and by making it 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 due to it. Here, the 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 a laser diffraction scattering method is used. It can be measured with a particle size distribution measuring device.
The specific surface area of the silica is preferably 4 cm ² / g or more, more preferably 4 to 9 cm ² / g, still more preferably 5 to 7 cm ² / g.

<(E) Curing agent>
The thermosetting resin composition [I] may further contain a curing agent (hereinafter sometimes referred to as a curing agent (E)) as the component (E). Examples of the curing agent (E) include dicyandiamide; chain aliphatic amines other than 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] undecane and other cyclic aliphatic amines; xylenediamine, phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and other aromatic amines And the like. Among these, dicyandiamide is preferable from the viewpoints of metal foil adhesion and low thermal expansion.
The dicyandiamide is represented by H ₂ N—C (═NH) —NH—CN, and the melting point is usually 205 to 215 ° C., and higher purity is 207 to 212 ° C. Dicyandiamide is a crystalline substance and may be orthorhombic or plate-like. Dicyandiamide preferably has a purity of 98% or more, more preferably has a purity of 99% or more, and still more preferably has a purity of 99.4% or more. As dicyandiamide, commercially available products can be used. For example, commercially available products such as those manufactured by Nippon Carbide Industries Co., Ltd., Tokyo Chemical Industry Co., Ltd., Kishida Chemical Co., Ltd., and Nacalai Tesque Co., Ltd. can be used. .

<(F) Flame retardant>
The thermosetting resin composition [I] may further contain a flame retardant (hereinafter sometimes referred to as a flame retardant (F)) as the component (F). Here, among the curing agents, dicyandiamide and the like also have an effect as a flame retardant, but in the present invention, those that can function 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 flame retardants; nitrogen flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate and melamine cyanurate; cyclophosphazene and polyphosphazene And phosphazene flame retardants such as inorganic flame retardants such as antimony trioxide. Among these, a phosphorus flame retardant is preferable.
Examples of the phosphorus flame retardant include an inorganic phosphorus flame retardant and an organic phosphorus flame retardant.
Examples of inorganic phosphorus flame retardants include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphate amides Phosphoric acid; phosphine oxide and the like.
Examples of organic phosphorus flame retardants include aromatic phosphate esters, monosubstituted phosphonic acid diesters, disubstituted phosphinic acid esters, disubstituted phosphinic acid metal salts, organic nitrogen-containing phosphorus compounds, cyclic organophosphorus compounds, Examples thereof include phosphorus-containing phenol resins. Among these, aromatic phosphate esters and metal salts of disubstituted phosphinic acids are preferred. Here, the metal salt is preferably any one of a lithium salt, a sodium salt, a potassium salt, a calcium salt, a magnesium salt, an aluminum salt, a titanium salt, and a zinc salt, and preferably an aluminum salt. Among organic phosphorus flame retardants, aromatic phosphates are more preferable.

Examples of the aromatic phosphate ester include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis (diphenyl phosphate), 1,3 -Phenylenebis (di-2,6-xylenyl phosphate), bisphenol A-bis (diphenyl phosphate), 1,3-phenylenebis (diphenyl phosphate) and the like.
Examples of monosubstituted phosphonic acid diesters 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, a metal salt of diarylphosphinic acid, and the like. As described above, these metal salts are preferably any 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 dicresyl phosphazene; melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, and the like.
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- And 10-phosphaphenanthrene-10-oxide.
Among these, at least one selected from an aromatic phosphate ester, a metal salt of a disubstituted phosphinic acid and a cyclic organic phosphorus compound is preferable, and an aromatic phosphate ester is more preferable.

The aromatic phosphate is preferably an aromatic phosphate represented by the following general formula (F-1) or (F-2), and the metal salt of the disubstituted phosphinic acid is: A metal salt of a disubstituted phosphinic acid represented by the general formula (F-3) is preferable.

(Wherein R ^F1 to R ^F5 are each independently an alkyl group having 1 to 5 carbon atoms or a halogen atom. E and f are each independently an integer of 0 to 5, and g, h and i are each It is an integer of 0 to 4 independently.
R ^F6 and R ^F7 are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group 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, or 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 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. Groups and the like. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. Examples of the halogen atom represented by R ^F1 to R ^F5 include a fluorine atom.
e and f are preferably integers of 0 to 2, and more preferably 2. g, h and i are preferably integers of 0 to 2, more preferably 0 or 1, and still more preferably 0.
^Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^F6 and R ^F7 include the same groups as in R ^F1 to R ^F5 .
Examples of the aryl group having 6 to 14 carbon atoms represented by R ^F6 and R ^F7 include a phenyl group, a naphthyl group, a biphenylyl group, and an anthryl group. The aromatic hydrocarbon group is preferably an aryl group having 6 to 10 carbon atoms.
j is equal to the valence of the metal ion, that is, varies within the range of 1 to 4 corresponding to the type of M.
M is preferably an aluminum atom. In addition, j is 3 when M is an aluminum atom.

(Content of each component of thermosetting resin composition [I])
In the thermosetting resin composition [I], the content of the components (A) to (D) is not particularly limited, but with respect to 100 parts by mass of the sum of the components (A) to (C), The component (A) is preferably 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 preferably 30 to 70 parts by mass.
When the component (A) is 15 parts by mass or more with respect to 100 parts by mass of the sum of the components (A) to (C), high heat resistance, low relative dielectric constant, 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 [I] 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 be high heat resistance, low relative dielectric constant, 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 sum of the components (A) to (C), high heat resistance and a low relative dielectric constant tend to be obtained. On the other hand, when the amount is 45 parts by mass or less, high heat resistance, high metal foil adhesion, and low thermal expansion tend to be obtained.
When component (D) is 30 parts by mass or more with respect to 100 parts by mass of the total of components (A) to (C), excellent low thermal expansion tends to be obtained. On the other hand, when it is 70 parts by mass or less, heat resistance is obtained, and the fluidity and moldability of the thermosetting resin composition [I] tend to be good.

Further, when the component (E) is contained in the thermosetting resin composition [I], 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). It is preferable that
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 foil adhesion and excellent low thermal expansion tend to be obtained. On the other hand, when it is 6 parts by mass or less, high heat resistance tends to be obtained.

In addition, when the component (F) is contained in the thermosetting resin composition [I], the content is from the viewpoint of flame retardancy, with respect to 100 parts by mass of the sum of the components (A) to (C). The amount 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), from the viewpoint of flame retardancy, the phosphorus atom content is 0.1 to 3 masses per 100 mass parts of the total of the components (A) to (C). Is preferably 0.2 to 3 parts by mass, more preferably 0.5 to 3 parts by mass.

(Other ingredients)
The thermosetting resin composition [I] can contain other components such as an additive and an organic solvent as needed within a range not impairing the effects of the present invention. These may contain 1 type independently, and may contain 2 or more types.

(Additive)
Examples of additives include inorganic fillers other than the component (D), curing accelerators, colorants, antioxidants, reducing agents, ultraviolet absorbers, fluorescent brighteners, adhesion improvers, organic fillers, and the like. Is mentioned. These may be used individually by 1 type and may use 2 or more types together.

(Organic solvent)
The thermosetting resin composition [I] may contain an organic solvent from the viewpoint of facilitating handling by dilution and easy manufacture of a prepreg described later. In this specification, the thermosetting resin composition containing an organic solvent may be referred to as a resin varnish.
The organic solvent is not particularly limited. 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, Alcohol solvents such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ether solvents such as tetrahydrofuran ; Aromatic solvents such as toluene, xylene, mesitylene; Form Nitrogen-containing solvents including amide solvents such as amide, N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; sulfur atoms including sulfoxide solvents such as dimethyl sulfoxide Solvent; ester solvents such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate and the like.
Among these, from the viewpoint of solubility, alcohol solvents, ketone solvents, and nitrogen atom-containing solvents are preferable, 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 preferable. More preferred is methyl ethyl ketone.
An organic solvent may be used individually by 1 type, and may use 2 or more types together.

The content of the organic solvent in the thermosetting resin composition [I] (resin varnish) may be appropriately adjusted to such an extent that the thermosetting resin composition [I] can be easily handled. The solid content concentration (concentration of components other than the organic solvent) derived from the thermosetting resin composition [I] is preferably 30 to 90% by mass, and more preferably, as long as the workability is in the range. Is 40 to 80% by mass, more preferably 50 to 80% by mass.

Next, each component contained in the epoxy resin composition [II] will be described in detail. In order to avoid duplication with the thermosetting resin composition [I], the epoxy resin composition [II] contains the (A) maleimide compound contained in the thermosetting resin composition [I]. However, the present invention is not particularly limited to this embodiment, and may contain the (A) maleimide compound.

<(G) Epoxy resin>
As (G) epoxy resin which epoxy resin composition [II] contains, the same thing as (B) epoxy resin in the said thermosetting resin composition [I] is mentioned, It demonstrates similarly. Among them, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl novolak type epoxy resin and dicyclopentadiene type epoxy resin At least one selected from the group consisting of: cresol novolak type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl novolak type from the viewpoint of low thermal expansion and high glass transition temperature More preferably, at least one selected from the group consisting of epoxy resins and phenol novolac type epoxy resins, biphenylaralkyl novolac type epoxy Fat is more preferable.

<(H) Epoxy resin curing agent>
Examples of the epoxy resin curing agent include various phenol resin compounds, acid anhydride compounds, amine compounds, hydragit compounds, and the like. Examples of the phenol resin compound include novolak type phenol resins and resol type phenol resins. Examples of the acid anhydride compound include phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl hymic acid, and the like. It is done. Examples of the amine compound include dicyandiamide, diaminodiphenylmethane, and guanylurea.
Among these epoxy resin curing agents, from the viewpoint of improving reliability, a novolac type phenol resin is preferable, and a cresol novolac resin is more preferable.

As the novolac type phenol resin, a commercially available product may be used, for example, a phenol novolac resin such as “TD2090” (trade name, manufactured by DIC Corporation), or a cresol such as “KA-1165” (trade name, manufactured by DIC Corporation). Examples thereof include novolac resin. Further, for example, commercially available products of triazine ring-containing novolac type phenol resins such as “Phenolite LA-1356” (trade name, manufactured by DIC Corporation), “Phenolite LA7050 series” (trade name, manufactured by DIC Corporation), and the like. Examples thereof include triazine-containing cresol novolak resins such as “Phenolite LA-3018” (trade name, manufactured by DIC Corporation).

The epoxy resin composition [II] may contain (I) a curing accelerator and (J) an inorganic filler, if necessary.
<(I) Curing accelerator>
The epoxy resin composition [II] preferably contains (I) a curing accelerator from the viewpoint of promoting the reaction between the (G) epoxy resin and the (H) epoxy resin curing agent. (I) Curing accelerators include, for example, imidazole compounds such as 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate; organophosphorus compounds such as triphenylphosphine Onium salts such as phosphonium borate; amines such as 1,8-diazabicycloundecene; 3- (3,4-dichlorophenyl) -1,1-dimethylurea and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, imidazole compounds are preferable, and 2-ethyl-4-methylimidazole is more preferable.

<(J) Inorganic filler>
The epoxy resin composition [II] preferably contains an inorganic filler (J) from the viewpoint of low thermal expansion. (J) As the inorganic filler, for example, 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, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. These may be used individually by 1 type and may use 2 or more types together. Among these, silica is preferable from the viewpoint of a low thermal expansion coefficient.
The average particle size of the inorganic filler is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.
The inorganic filler may be subjected to a surface treatment. For example, when silica is used as the inorganic filler, a silane coupling agent treatment may be performed as the surface treatment. Examples of the silane coupling agent include amino silane coupling agents, vinyl silane coupling agents, and epoxy silane coupling agents. Among these, silica subjected to surface treatment with an aminosilane coupling agent is preferable.

(Content of each component of epoxy resin composition [II])
In the epoxy resin composition [II], the content of the components (G) to (J) is not particularly limited, but with respect to 100 parts by mass of the sum of the components (G) to (J), (G 5) to 50 parts by weight of component (H), 5 to 50 parts by weight of component (H), 0.001 to 1 part by weight of component (I), and 20 to 80 parts by weight of component (J). More preferably, (G) component is 5 to 35 parts by mass, (H) component is 5 to 40 parts by mass, and (I) component is 0.1 parts by mass with respect to 100 parts by mass of the sum of components (G) to (J). 001 to 1 part by mass, component (J) is 35 to 80 parts by mass.

(Other ingredients)
The epoxy resin composition [II] can contain other components such as an additive and an organic solvent as necessary within a range not impairing the effects of the present invention. These may contain 1 type independently, and may contain 2 or more types.

(Additive)
Examples of the additive include a colorant, an antioxidant, a reducing agent, an ultraviolet absorber, a fluorescent brightener, an adhesion improver, and an organic filler. These may be used individually by 1 type and may use 2 or more types together.

(Organic solvent)
About an organic solvent, it is demonstrated similarly to description of the organic solvent in the said thermosetting resin composition [I].

Next, each component contained in the thermosetting resin composition [III] will be described in detail.
<(K) Silicone-modified maleimide compound>
(K) The silicone-modified maleimide compound is not particularly limited as long as it is a maleimide compound having a siloxane skeleton. For example, a maleimide compound (k-1) having at least two N-substituted maleimide groups in one molecule [hereinafter also referred to as “maleimide compound (k-1)”] and at least two second maleimide groups in one molecule. Preferred examples include addition reaction products with a siloxane compound (k-2) having a primary amino group [hereinafter also referred to as “siloxane compound (k-2)”], and maleimide compound (k-1) and siloxane compound ( More preferred is an addition reaction product of k-2) and a monoamine compound [hereinafter also referred to as “monoamine compound (k-3)”].
As the maleimide compound (k-1), the same compounds as the maleimide compound (a1) in the description of the (A) maleimide compound in the thermosetting resin composition [I] can be used.
The siloxane compound (k-2) preferably contains a structural unit represented by the following general formula (k-2-1).

（一般式（ｋ－２－１）中、Ｒ^ｋ１及びＲ^ｋ２は各々独立に、炭素数１～５のアルキル基、フェニル基、又は置換基を有するフェニル基を示す。）

(In general formula (k-2-1), R ^k1 and R ^k2 each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a phenyl group having a substituent.)

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^k1 and R ^k2 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. Groups and the like. As the alkyl group, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
Examples of the substituent of the phenyl group in the “phenyl group having a substituent” include an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and an alkynyl group having 2 to 5 carbon atoms. . Examples of the alkyl group having 1 to 5 carbon atoms are the same as those described above. Examples of the alkenyl group having 2 to 5 carbon atoms include a vinyl group and an allyl group. Examples of the alkynyl group having 2 to 5 carbon atoms include ethynyl group and propargyl group.
R ^k1 and R ^k2 are each preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group.

As the siloxane compound (k-2), a siloxane diamine represented by the following general formula (k-2-2) is more preferable.

（一般式（ｋ－２－２）中、Ｒ^ｋ１及びＲ^ｋ２は、一般式（ｋ－２－１）中のものと同じである。Ｒ^ｋ３及びＲ^ｋ４は各々独立に、炭素数１～５のアルキル基、フェニル基、又は置換基を有するフェニル基を示す。Ｒ^ｋ５及びＲ^ｋ６は各々独立に、２価の有機基を表し、ｍは２～１００の整数である。）

(In general formula (k-2-2), R ^k1 and R ^k2 are the same as those in general formula (k-2-1). R ^k3 and R ^k4 each independently represent 1 to 5 represents an alkyl group, a phenyl group, or a phenyl group having a substituent, wherein R ^k5 and R ^k6 each independently represents a divalent organic group, and m is an integer of 2 to 100.)

The alkyl group having 1 to 5 carbon atoms, the phenyl group, and the phenyl group having a substituent represented by R ^k3 and R ^k4 are described in the same manner as described for R ^k1 and R ^k2 . As R ^k3 and R ^k4 , a methyl group is preferable.
^Examples of the divalent organic group represented by R ^k5 and R ^k6 include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O—, or a divalent linking group in which these are combined. Examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms such as a methylene group, an ethylene group, and a propylene group. Examples of the alkenylene group include alkenylene groups having 2 to 10 carbon atoms. Examples of the alkynylene group include alkynylene groups having 2 to 10 carbon atoms. Examples of the arylene group include arylene groups having 6 to 20 carbon atoms such as a phenylene group and a naphthylene group.
Among these, as R ^k5 and R ^k6 , an alkylene group and an arylene group are preferable.
m is preferably an integer of 2 to 50, more preferably an integer of 3 to 40, still more preferably an integer of 5 to 30, and further preferably an integer of 7 to 30.

The functional group equivalent of the siloxane compound (k-2) is not particularly limited, but is preferably 300 to 3,000 g / mol, more preferably 300 to 2,000 g / mol, and still more preferably 300 to 1,500 g / mol. is there.

A commercially available product can be used as the siloxane compound (k-2). Examples of commercially available products include “KF-8010” (functional group equivalent of amino group: 430 g / mol), “X-22-161A” (functional group equivalent of amino group: 800 g / mol), “X-22- 161B "(functional group equivalent of amino group: 1,500 g / mol)," KF-8012 "(functional group equivalent of amino group: 2,200 g / mol)," KF-8008 "(functional group equivalent of amino group: 5,700 g / mol), “X-22-9409” (functional group equivalent of amino group: 700 g / mol), “X-22-1660B-3” (functional group equivalent of amino group: 2,200 g / mol) (Above, manufactured by Shin-Etsu Chemical Co., Ltd.), “BY-16-853U” (functional group equivalent of amino group: 460 g / mol), “BY-16-853” (functional group equivalent of amino group: 650 g / mol) , "B -16-853B "(functional group equivalent of amino group: 2,200 g / mol) (above, manufactured by Toray Dow Corning Co., Ltd.)," XF42-C5742 "(functional group equivalent of amino group: 1,280 g / mol) "XF42-C6252" (amino group functional group equivalent: 1,255 g / mol), "XF42-C5379" (amino group functional group equivalent: 745 g / mol) (above, Momentive Performance Materials Japan Joint Company-made). These may be used individually by 1 type and may use 2 or more types together.

As the monoamine compound (k-3), the same compounds as the monoamine compound (a2) in the thermosetting resin composition [I] can be used, and preferable ones are also the same.

As described above, one embodiment of the (K) silicone-modified maleimide compound is a reaction between the maleimide compound (k-1), the siloxane compound (k-2), and, if necessary, the monoamine compound (k-3). Can be manufactured.
In the reaction, the respective use ratios of the maleimide compound (k-1), the siloxane compound (k-2) and the monoamine compound (k-3) used as necessary are from the viewpoint of prevention of gelation and heat resistance. The maleimide group equivalent of the maleimide compound (k-1) preferably exceeds the sum of the equivalents of primary amino groups of the siloxane compound (k-2) and the monoamine compound (k-3), and the maleimide compound (k- The ratio of the equivalent of the maleimide group of 1) to the sum of the equivalents of primary amino groups of the siloxane compound (k-2) and the monoamine compound (k-3) [(k-1) / [(k-2) + (K−3)] is preferably from 1 to 15, more preferably from 2 to 10, and even more preferably from 3 to 10.
The reaction temperature is preferably 70 to 150 ° C., more preferably 90 to 130 ° C. from the viewpoint of productivity and uniform reaction. The reaction time is not particularly limited, but is preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.

<(L) Imidazole compound>
Examples of the (L) imidazole compound include 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-1- Methylimidazole, 1,2-diethylimidazole, 1-ethyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, 2-phenyl- 4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4 -Methylimi Sol, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 2,4 -Diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')] ethyl-s-triazine, Imidazole compounds such as 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)] ethyl-s-triazine; modified imidazole compounds such as isocyanate mask imidazole and epoxy mask imidazole; A salt of the imidazole compound and trimellitic acid, such as cyanoethyl-2-phenylimidazolium trimellitate; Salts with tetrazole compound and isocyanuric acid; and salts with the imidazole compound and hydrobromic acid. Among these, a modified imidazole compound is preferable, and an isocyanate mask imidazole is more preferable. An imidazole compound may be used individually by 1 type, and may use 2 or more types together.

<(M) Inorganic filler>
(M) The inorganic filler is described in the same manner as the description of (J) inorganic filler in the epoxy resin composition [II].

(Content of each component of thermosetting resin composition [III])
In the thermosetting resin composition [III], the content of the components (K) to (M) is not particularly limited, but with respect to 100 parts by mass of the sum of the components (K) to (M), The component (K) is preferably 15 to 80 parts by mass, the component (L) is 0.01 to 5 parts by mass, and the component (M) is preferably 15 to 80 parts by mass. More preferably, for 100 parts by mass of the sum of the components (K) to (M), the component (K) is 30 to 65 parts by mass, the component (L) is 0.01 to 3 parts by mass, and the component (M) is 30 to 65 parts by mass.

(Other ingredients)
The thermosetting resin composition [III] can contain other components such as an additive and an organic solvent as necessary within the range not impairing the effects of the present invention. These may contain 1 type independently, and may contain 2 or more types.

(Additive)
Examples of the additive include a colorant, an antioxidant, a reducing agent, an ultraviolet absorber, a fluorescent brightener, an adhesion improver, and an organic filler. These may be used individually by 1 type and may use 2 or more types together.

(Organic solvent)
About an organic solvent, it is demonstrated similarly to description of the organic solvent in the said thermosetting resin composition [I].

[Prepreg]
The prepreg obtained by the production method of the present invention has little variation in the amount of dimensional change. Further, if the thermosetting resin composition is used, the prepreg has high heat resistance, high metal foil adhesion, and high glass transition temperature. Also, it has excellent low thermal expansibility, formability, and wraparound (laser processability).

Moreover, according to this invention, the following prepregs can be provided. The prepreg obtained by the production method of the present invention also corresponds to the following prepreg. In other words, the following prepreg can be produced by the production method of the present invention.
A prepreg comprising a base material and a thermosetting resin composition and having a standard deviation σ of 0.012% or less determined according to the following method.
Standard deviation σ calculation method:
A copper foil having a thickness of 18 μm is stacked on both surfaces of one prepreg, and heat-press molding is performed at 190 ° C. and 2.45 MPa for 90 minutes, thereby producing a double-sided copper-clad laminate having a thickness of 0.1 mm. With respect to the double-sided copper clad laminate thus obtained, a hole having a diameter of 1.0 mm is formed in the plane at the locations 1 to 8 shown in FIG. Use an image measuring machine to determine the distance between each of the three points in the warp direction (1-7, 2-6, 3-5) and weft direction (1-3, 8-4, 7-5) shown in FIG. And measure each distance as the initial value. Thereafter, the outer layer copper foil is removed and heated at 185 ° C. for 60 minutes in a dryer. After cooling, in the same manner as the initial value measurement method, three points each in the warp direction (1-7, 2-6, 3-5) and the weft direction (1-3, 8-4, 7-5) Measure distance. An average value of the change rates is obtained from the change rate [(measured value after heat treatment−initial value) × 100 / initial value] with respect to the initial value of each measurement distance, and the standard deviation σ with respect to the average value is calculated.
The image measuring machine is not particularly limited, but for example, “QV-A808P1L-D” (manufactured by Mitutoyo) can be used.

The standard deviation σ is preferably 0.011% or less, more preferably 0.010% or less, and further preferably 0.009% or less. The lower limit value of the standard deviation σ is not particularly limited, but is usually 0.003% or more, 0.005% or more, 0.006% or more, 0.007 % Or more.

[Laminated board]
The laminated board of this invention contains the said prepreg and metal foil. For example, it can be manufactured by using one sheet of the prepreg or stacking 2 to 20 sheets as necessary, and arranging metal foil on one side or both sides thereof, preferably by heating and laminate molding. In addition, the laminated board which has arrange | positioned metal foil may be called a metal-clad laminated board.
The metal of the metal foil is not particularly limited as long as it is used for electrical insulating materials, but from the viewpoint of conductivity, preferably copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, Iron, titanium, chromium, or an alloy containing at least one of these metal elements is preferable, copper and amylnium are more preferable, and copper is more preferable.
As the molding conditions of the laminated plate, a known molding method of a laminated plate for an electrical insulating material and a multilayer plate can be applied, for example, using a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc. Molding can be performed at 100 to 250 ° C., a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours.
Moreover, the prepreg of the present invention and the printed wiring board for inner layer can be combined and laminated to produce a multilayer board.
There is no restriction | limiting in particular in the thickness of metal foil, According to the use etc. of a printed wiring board, it can select suitably. 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.

In addition, it is also preferable to form a plating layer by plating metal foil.
The metal of the plating layer is not particularly limited as long as it can be used for plating. The metal of the plating layer is preferably made of copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and an alloy containing at least one of these metal elements. Preferably it is selected.
There is no restriction | limiting in particular as a plating method, For example, a well-known method, for example, the electroplating method and the electroless-plating method, can be utilized.

[Printed wiring board]
The present invention also provides a printed wiring board comprising the prepreg or the laminated board.
The printed wiring board of the present invention can be produced by subjecting a metal foil of a metal-clad laminate to circuit processing. For example, after forming a resist pattern on the surface of the metal foil, the unnecessary portion of the metal foil is removed by etching, the resist pattern is peeled off, a necessary through hole is formed by a drill, and a resist pattern is formed again. It can be performed by plating for conducting through holes and finally peeling off the resist pattern. The above-described 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, the circuit is processed in the same manner as described above to obtain a multilayer printed wiring board. Can do. In this case, it is not always necessary to form a through hole, a via hole may be formed, and both can be formed. Such multi-layering is performed as many times as necessary.

[Semiconductor package]
The semiconductor package of the present invention is obtained by mounting a semiconductor on the printed wiring board of the present invention. The semiconductor package of the present invention can be manufactured by mounting a semiconductor chip, a memory or the like at a predetermined position of the printed wiring board of the present invention.

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 way. Using the thermosetting resin composition according to the present invention, a resin varnish, a prepreg precursor produced using a resin varnish, a prepreg obtained by subjecting the prepreg precursor to surface heat treatment, and a copper-clad laminate are produced, The produced copper clad laminate was evaluated. The evaluation method is shown below.

[Evaluation methods]
<1. Heat resistance (Reflow soldering heat resistance)>
Using the four-layer copper-clad laminate produced in each example, the maximum temperature reached 266 ° C., and flowing the four-layer copper-clad laminate for 30 seconds in a thermostatic bath environment of 260 ° C. or higher was regarded as one cycle. Thus, the number of cycles until it was confirmed that the substrate was swollen was obtained. The greater the number of cycles, the better the heat resistance.

<2. Relative permittivity (Dk)>
Using a network analyzer “8722C” (manufactured by Hewlett-Packard Company), the relative dielectric constant of the double-sided copper-clad laminate at 1 GHz was measured by a triplate structure linear line resonator method. The test piece size is 200 mm x 50 mm x thickness 0.8 mm. 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 A ground layer was formed by leaving copper on the entire surface. For the other double-sided copper-clad laminate, one side was etched entirely and the back side was a ground layer. These two double-sided copper-clad laminates were stacked with the ground layer on the outside to form a strip line. The measurement was performed at 25 ° C.
The smaller the relative dielectric constant, the better.

<3. Metal foil adhesion (copper foil peel strength)>
Metal foil adhesion was evaluated by copper foil peel strength. The double-sided copper-clad laminate produced in each example was immersed in a copper etching solution “ammonium persulfate (APS)” (manufactured by ADEKA) to form a copper foil having a width of 3 mm to produce an evaluation board. The peel strength of the copper foil was measured using “AG-100C” (manufactured by Shimadzu Corporation). It shows that it is excellent in metal foil adhesiveness, so that a value is large.

<4. Glass transition temperature (Tg)>
The double-sided copper-clad laminate produced in each example was immersed in a copper etching solution “Ammonium Persulfate (APS)” (manufactured by ADEKA Corporation) to produce a 5 mm square evaluation substrate from which the copper foil was removed. Q400EM "(manufactured by TA Instruments) was used to observe the thermal expansion characteristics at 30 to 260 ° C. in the plane direction (Z direction) of the evaluation substrate, and the inflection point of the expansion amount was defined as the glass transition temperature.

<5. Low thermal expansion>
The double-sided copper-clad laminate produced in each example was immersed in a copper etching solution “Ammonium Persulfate (APS)” (manufactured by ADEKA Corporation) to produce a 5 mm square evaluation substrate from which the copper foil was removed. The thermal expansion coefficient (linear expansion coefficient) in the surface 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 rising / cooling cycle was repeated twice, and the coefficient of thermal expansion [ppm / ° C.] of 30 ° C. to 260 ° C. in the second temperature displacement chart was measured. An index of low thermal expansion was used. The smaller the value, the better the low thermal expansion. In the table, the thermal expansion coefficient below Tg (denoted as “<Tg”) and the thermal expansion coefficient above Tg (denoted as “> Tg”) are shown separately.
Measurement conditions 1 ^st Run: room temperature → 210 ° C. (temperature increase rate 10 ° C./min)
2 ^nd Run: 0 ° C. → 270 ° C. (temperature increase rate 10 ° C./min)
The copper-clad laminate is desired to be further reduced in thickness, and in conjunction with this, the prepreg constituting the copper-clad laminate is also being considered to be thinner. Since the thinned prepreg is likely to warp, it is desired that the prepreg warp during heat treatment be small. In order to reduce the warpage, it is effective that the coefficient of thermal expansion in the surface direction of the substrate is small.

<6. Plating rotation (Laser workability)>
Using the laser machine “LC-2F21B / 2C” (manufactured by Hitachi Via Mechanics Co., Ltd.) with the target hole diameter of 80 μm, Gaussian, and cycle mode for the 4-layer copper-clad laminate produced in each example, the copper direct method The laser was drilled with a pulse width of 15 μs × 1 and 7 μs × 4.
Regarding the obtained laser drilled substrate, the swelling liquid “Swelling Dip Securigant P” (manufactured by Atotech Japan Co., Ltd.) is 70 ° C. for 5 minutes, and the roughening liquid “Dosing Securigant P500J” (manufactured by Atotech Japan Co., Ltd.) is used. The desmear treatment was carried out at 70 ° C. for 9 minutes using the neutralizing solution “Reduction Conditioner Securigant P500” (manufactured by Atotech Japan Co., Ltd.) at 40 ° C. for 5 minutes. Thereafter, electroless plating solution “Prigant MSK-DK” (manufactured by Atotech Japan Co., Ltd.) at 30 ° C. for 20 minutes, electroplating solution “Kaparaside HL” (manufactured by Atotech Japan Co., Ltd.) at 24 ° C., 2 A / dm ² After 2 hours, the laser-processed substrate was plated.
The cross section of the obtained laser drilled substrate was observed, and the plating coverage was confirmed. As a method for evaluating the throwing power of plating, 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 preferably within 10% of the plating thickness at the top of the laser hole. The existence ratio (%) of holes included in this range in the hole was determined.

<7. Formability>
For the four-layer copper-clad laminate produced in each example, after removing the outer layer copper, the presence or absence of voids and blurring in the in-plane of 340 mm × 500 mm was visually confirmed as resin embedding ability, and an index of formability It was. When there is no void or blur, it is indicated as “good”, and when there is a void or blur, this is indicated. When there is no void and blur, it can be said that the moldability is good.

<8. Evaluation of variation in dimensional change>
About the double-sided copper clad laminated board produced in each example, the hole with a diameter of 1.0 mm was implemented in the surface as FIG. As shown in FIG. 1, the distance between three points in the warp direction (1-7, 2-6, 3-5) and the weft direction (1-3, 8-4, 7-5) of the glass cloth is shown in the image. Measurement was performed using a measuring instrument “QV-A808P1L-D” (manufactured by Mitutoyo), and each measurement distance was set as an initial value. Thereafter, the outer layer copper foil was removed and heated at 185 ° C. for 60 minutes in a dryer. After cooling, in the same manner as the initial value measurement method, three points each in the warp direction (1-7, 2-6, 3-5) and the weft direction (1-3, 8-4, 7-5) The distance was measured. The average value of the rate of change is obtained from the rate of change of each measurement distance with respect to the initial value [(measured value−initial value) × 100 / initial value], and the standard deviation σ with respect to the average value is calculated. It was used as an index of variation in dimensional change. A small value of the standard deviation σ indicates that the variation in dimensional change is small and preferable.

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

(A) component: The solution of the maleimide compound (A) manufactured by the following manufacture example 1 was used.
[Production Example 1]
In a reaction vessel having a volume of 1 L equipped with a thermometer, a stirrer and a moisture meter with a reflux condenser, 19.2 g of 4,4′-diaminodiphenylmethane, 174.0 g of bis (4-maleimidophenyl) methane, p-aminophenol 6.6 g and dimethylacetamide 330.0 g were added and reacted at 100 ° C. for 2 hours to obtain a dimethylacetamide solution of maleimide compound (A) (Mw = 1,370) having an acidic substituent and an N-substituted maleimide group. And used as 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 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: TSKgel SuperHZ2000 + TSKgel SuperHZ2300 (all manufactured by Tosoh Corporation)
Column size: 6.0 mm × 40 mm (guard column), 7.8 mm × 300 mm (column)
Eluent: Tetrahydrofuran Sample concentration: 20mg / 5mL
Injection volume: 10 μL
Flow rate: 0.5 mL / min Measurement temperature: 40 ° C

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

Component (D): fused silica treated with an aminosilane coupling agent (average particle size: 1.9 μm, specific surface area 5.8 m ² / g)
Other 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) component: Dicyandiamide (Nippon Carbide Industries Co., Ltd.)
Component (F): “PX-200” (aromatic phosphate ester (see structural formula below), manufactured by Daihachi Chemical Industry Co., Ltd.)

[Examples 1 to 13, Comparative Examples 1 to 4]
Each component shown above was blended as shown in Tables 1 to 4 below (however, in the case of a solution, the solid content is shown), and methyl ethyl ketone was added so that the nonvolatile content of the solution was 65 to 75% by mass. In addition, resin varnishes were prepared for the thermosetting resin compositions of each Example and each Comparative Example.
Each resin varnish obtained was impregnated with IPC standard # 3313 glass cloth (0.1 mm), dried with a panel heater set at a temperature of 160 ° C. for 4 minutes to be B-staged (step 1), and then at room temperature (step 1). The mixture was allowed to cool to about 20 ° C. (step 2) to obtain a prepreg precursor. In the comparative example, the prepreg was used as it was.
In each example, the obtained prepreg precursor was subjected to surface heat treatment (product surface temperature 70 ° C.) for 3 seconds with a panel heater whose surface heat treatment was set to a temperature of 500 ° C. A prepreg was produced by cooling to 20 ° C. (step 3).

(Production and performance evaluation of double-sided copper-clad laminates)
Copper foil “3EC-VLP-18” (manufactured by Mitsui Kinzoku Co., Ltd.) having a thickness of 18 μm is layered on both sides of the above-described eight prepregs, and the temperature is 190 ° C. and the pressure is 25 kgf / cm ² (2.45 MPa). Heat-press molding for a minute to prepare a double-sided copper-clad laminate with a thickness of 0.8 mm (equivalent to 8 prepregs), and using the copper-clad laminate, according to the above methods, relative dielectric constant, metal foil adhesion, Glass transition temperature (Tg) and low thermal expansion were measured and evaluated.
Also, a 18 μm thick copper foil “3EC-VLP-18” (manufactured by Mitsui Kinzoku Co., Ltd.) is stacked on both sides of one prepreg, and heated for 90 minutes at a temperature of 190 ° C. and a pressure of 25 kgf / cm ² (2.45 MPa). A double-sided copper-clad laminate having a thickness of 0.1 mm (for one prepreg) was prepared, and the dimensional variation was measured and evaluated using the double-sided copper-clad laminate according to the above-described method.

(Production and performance evaluation of 4-layer copper-clad laminate)
On the other hand, one prepreg was used, and a copper foil “YGP-18” (manufactured by Nippon Electrolytic Co., Ltd.) having a thickness of 18 μm was stacked on both sides at a temperature of 190 ° C. and a pressure of 25 kgf / cm ² (2.45 MPa). After heat-press molding for 90 minutes to produce a double-sided copper-clad laminate with a thickness of 0.1 mm (one prepreg), inner layer adhesion treatment (“BF treatment solution” (manufactured by Hitachi Chemical Co., Ltd.) on both copper foil surfaces ), And prepregs with a thickness of 0.05 mm are stacked one by one, and a copper foil “YGP-18” (manufactured by Nippon Electrolytic Co., Ltd.) with a thickness of 18 μm is stacked on both sides, and the temperature is 190 ° C. and the pressure is 25 kgf / A four-layer copper-clad laminate was produced by heating and pressing at cm ² (2.45 MPa) for 90 minutes. Using the four-layer copper-clad laminate, heat resistance, plating-around property and formability were evaluated according to the above methods.
The results are shown in Tables 1 to 4.

 

 

 

 

 

 

 

 

[Example 14]
Instead of preparing the resin varnish in Example 1, a resin varnish was prepared using the following components.
19 parts by mass of biphenylaralkyl novolac type epoxy resin (Nippon Kayaku Co., Ltd., trade name: NC-3000, epoxy equivalent: 280 to 300 g / eq), cresol novolac resin (manufactured by DIC Corporation, trade name: KA-1165), Hydroxyl equivalent: 119 g / eq) 16 parts by mass, 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd.) 0.02 parts by mass, fused silica (manufactured by Admatechs Co., Ltd., treated with an aminosilane coupling agent) A resin varnish (solid content concentration: 70% by mass) was prepared by mixing 65 parts by mass of silica (average particle size: 2 μm) and diluting with a solvent (methyl ethyl ketone).
Other steps were performed in the same manner as in Example 1 to obtain a prepreg. Using the obtained prepreg, a double-sided copper-clad laminate was prepared by the same method as in Example 1, and when the dimensional variation was measured and evaluated using the double-sided copper-clad laminate, the standard deviation σ The value was 0.010%.

[Example 15]
Instead of preparing the resin varnish in Example 1, a resin varnish was prepared using the following components.
In a reaction vessel with a volume of 2 L that can be heated and cooled, equipped with a stirrer and a moisture quantifier with a reflux condenser, 75.7 g of KF-8010 (both end amine-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.) and bis ( 4-maleimidophenyl) methane (trade name: BMI-1000, manufactured by Daiwa Kasei Kogyo Co., Ltd.) 168.0 g, p-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) 6.4 g, and solvent (methyl ethyl ketone) 250.0 g And reacted at 100 ° C. for 3 hours to obtain a silicone-modified maleimide compound. 49.5 parts by mass of the silicone-modified maleimide compound, 50 parts by mass of fused silica (manufactured by Admatex Co., Ltd., fused silica treated with an aminosilane coupling agent) and 0.5 parts by mass of an isocyanate mask imidazole (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) , Trade name: G-809L) was mixed and diluted with a solvent (methyl ethyl ketone) to prepare a resin varnish (solid content concentration: 70% by mass).
Other steps were performed in the same manner as in Example 1 to obtain a prepreg. Using the obtained prepreg, a double-sided copper-clad laminate was prepared by the same method as in Example 1, and when the dimensional variation was measured and evaluated using the double-sided copper-clad laminate, the standard deviation σ The value was 0.009%.

From the above results, the following was found.
In the examples, since the surface heat treatment was performed on the prepreg precursor, the standard deviation σ was smaller than that of the comparative example in which the surface heat treatment was not performed, and the variation in the dimensional change was sufficiently suppressed.
In Examples 1 to 13, the heat resistance of the reflow solder is 10 cycles or more, which is higher than the required heat resistance level, low dielectric constant, high metal foil adhesion and high glass transition temperature are obtained, and low thermal expansion is achieved. Indicated. Moreover, since it jumped out of the glass cloth from the wall surface and had an appropriate roughened shape, it was confirmed that it has good plating revolving property. Also in the moldability, the embedding property of the resin was good, and abnormalities such as blurring and voids were not confirmed. Among them, in Examples 1 to 10, the specific permittivity and the metal foil adhesion were better than those in Examples 11 to 13, and other characteristics were stably expressed.

The prepreg obtained by the present invention and a laminate comprising the prepreg are useful as printed wiring boards for electronic devices because of little variation in dimensional change.

Claims (20)

After impregnating the base material with a thermosetting resin composition, B-stage the thermosetting resin composition to obtain a prepreg precursor, and a surface heat treatment step after obtaining the prepreg precursor. Have
The surface heat treatment step is a step of heat-treating the surface of the prepreg precursor at a heat source temperature of 200 to 700 ° C.
A method for producing a prepreg. After impregnating the base material with a thermosetting resin composition, B-stage the thermosetting resin composition to obtain a prepreg precursor, and a surface heat treatment step after obtaining the prepreg precursor. Have
The surface heat treatment step is a step of heat-treating the surface of the prepreg precursor so that the surface temperature of the prepreg precursor is 40 to 130 ° C.
A method for producing a prepreg. The method for producing a prepreg according to claim 1 or 2, further comprising a step of cooling the prepreg precursor to 5 to 60 ° C after the step of obtaining the prepreg precursor and before the surface heat treatment step. The method for producing a prepreg according to any one of claims 1 to 3, wherein the time of the surface heat treatment is 1.0 to 10.0 seconds. The method for producing a prepreg according to any one of claims 1 to 4, wherein the thermosetting resin composition contains (A) a maleimide compound. The component (A) comprises (a1) a maleimide compound having at least two N-substituted maleimide groups, (a2) a monoamine compound represented by the following general formula (a2-1), and (a3) the following general formula ( 6. The method for producing a prepreg according to claim 5, which is a maleimide compound having an N-substituted maleimide group obtained by reacting with a diamine compound represented by a3-1).

(In General Formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group, and R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom. t is an integer of 1 to 5, u is an integer of 0 to 4, and 1 ≦ t + u ≦ 5, provided that when t is an integer of 2 to 5, a plurality of R ^A4 may be the same And when u is an integer of 2 to 4, a plurality of R ^A5 may be the same or different.)

(In the general formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or —O—. R ^A6 and R ^A7 each independently represents an alkyl having 1 to 5 carbon atoms. A group, a halogen atom, a hydroxyl group, a carboxy group, or a sulfonic acid group, and v and w are each independently an integer of 0 to 4.) The thermosetting resin composition further comprises (B) an epoxy resin,
(C) A copolymer resin having a structural unit derived from a substituted vinyl compound and a structural unit derived from maleic anhydride, and (D) silica treated with an aminosilane coupling agent. The method for producing a prepreg according to 1. The component (B) is bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl novolak type epoxy resin and dicyclopentadiene. The manufacturing method of the prepreg of Claim 7 which is at least 1 sort (s) selected from the group which consists of a type | mold epoxy resin. The component (C) is a copolymer resin having a structural unit represented by the following general formula (Ci) and a structural unit represented by the following formula (C-ii): The manufacturing method of prepreg of description.

(Wherein R ^C1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ^C2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkyl group having 6 to 20 carbon atoms) An aryl group, a hydroxyl group, or a (meth) acryloyl group, where x is an integer of 0 to 3, provided that when x is 2 or 3, a plurality of R ^C2 may be the same or different. May be.) A prepreg comprising a base material and a thermosetting resin composition and having a standard deviation σ of 0.012% or less determined according to the following method.
Standard deviation σ calculation method:
A copper foil having a thickness of 18 μm is stacked on both surfaces of one prepreg, and heat-press molding is performed at 190 ° C. and 2.45 MPa for 90 minutes, thereby producing a double-sided copper-clad laminate having a thickness of 0.1 mm. With respect to the double-sided copper clad laminate thus obtained, a hole having a diameter of 1.0 mm is formed in the plane at the locations 1 to 8 shown in FIG. Use an image measuring machine to determine the distance between each of the three points in the warp direction (1-7, 2-6, 3-5) and weft direction (1-3, 8-4, 7-5) shown in FIG. And measure each distance as the initial value. Thereafter, the outer layer copper foil is removed and heated at 185 ° C. for 60 minutes in a dryer. After cooling, in the same manner as the initial value measurement method, three points each in the warp direction (1-7, 2-6, 3-5) and the weft direction (1-3, 8-4, 7-5) Measure distance. An average value of the change rates is obtained from the change rate with respect to the initial value of each measurement distance, and a standard deviation σ with respect to the average value is calculated. The prepreg according to claim 10, obtained by the production method according to any one of claims 1 to 9. The prepreg according to claim 10, wherein the thermosetting resin composition contains (A) a maleimide compound. The thermosetting resin composition further comprises (B) an epoxy resin,
(C) A copolymer resin having a structural unit derived from a substituted vinyl compound and a structural unit derived from maleic anhydride, and (D) silica treated with an aminosilane coupling agent. The prepreg described in 1. The prepreg according to claim 10, wherein the thermosetting resin composition contains (G) an epoxy resin and (H) an epoxy resin curing agent. The prepreg according to claim 10, wherein the thermosetting resin composition comprises (K) a silicone-modified maleimide compound and (L) an imidazole compound. A laminate comprising the prepreg according to any one of claims 10 to 15 and a metal foil. A printed wiring board comprising the prepreg according to any one of claims 10 to 15 or the laminated board according to claim 16. A semiconductor package comprising a semiconductor element mounted on the printed wiring board according to claim 17. The method for producing a prepreg according to any one of claims 1 to 4, wherein the thermosetting resin composition contains (G) an epoxy resin and (H) an epoxy resin curing agent. The method for producing a prepreg according to any one of claims 1 to 4, wherein the thermosetting resin composition contains (K) a silicone-modified maleimide compound and (L) an imidazole compound.

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