TW202222934A - 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 DEG C.

Description

Manufacturing method of prepreg, prepreg, laminate, printed wiring board, and semiconductor package

The present invention relates to a method for manufacturing a prepreg, a prepreg, a laminate, a printed circuit board and a semiconductor package.

In recent years, the miniaturization, weight reduction, and multi-functionalization of electronic equipment have progressed. With this situation, large-scale integrated circuits (LSI), chip parts, etc. have been highly integrated, and their forms have also increased in number of pins. and rapid changes in miniaturization. Therefore, in order to increase the packing density of electronic components, the development of fine wiring of multilayer printed wiring boards has continued to progress. As a method of manufacturing multilayer printed wiring boards that meet these requirements, for example, a build-up method using a prepreg is becoming mainstream as a method suitable for weight reduction, miniaturization, and micro-circuits. It is used as an insulating layer, and a wiring layer is formed while connecting only a required portion, for example, a through hole (hereinafter, also referred to as a "laser through hole") formed by irradiating a laser.

The main point of the multilayer printed wiring board is to have high electrical connection reliability and excellent high-frequency characteristics between wiring patterns formed by a plurality of layers with fine wiring pitches, and it is required to have reliable connection with semiconductor chips. Sex is high. In particular, in recent years, in the motherboards of multifunctional mobile phone terminals, there are high-speed communication, high circuit density, extremely thin circuit boards, and the circuit width (L) and spacing (S) of the circuit boards (hereinafter, In some cases, the line width and the space are combined and indicated as [L/S]), which tends to be narrowed. With such narrowing of L/S, it has become difficult to stably produce circuit boards with good yields. In addition, in the design of a conventional circuit board, a layer with no circuit pattern called a "skip layer" is provided in some layers in consideration of communication obstacles and the like. Electronic equipment is gradually becoming more functional, and the number of circuit designs and the number of layers of the circuit board is gradually increased. However, due to the provision of the skip layer, the thickness of the motherboard is further increased. As a method to improve these problems, a more effective method is to reduce the relative permittivity of the insulating material used in the circuit board. Since it is easy to control the resistance of L/S by lowering the relative permittivity of the insulating material, it is possible to stably manufacture with a shape of L/S close to the current design, and it is possible to reduce the number of layers by reducing the number of jumping layers. Therefore, for insulating materials used in wiring boards, material properties with a relatively small relative permittivity are currently being sought.

In recent years, in motherboards of mobile phones, etc., which are being thinned and reduced in price with the increase in density of electronic devices, materials with a low relative permittivity are also being sought in order to cope with the thinning. In addition, in the equipment of communication systems represented by servers, routers, mobile base stations, etc., they have been gradually used in higher frequency bands, and lead-free solders with high melting point have been gradually used for soldering electronic parts. Therefore, As the material of the substrate used among these, there is a tendency to obtain a material having a low dielectric constant, a high glass transition temperature (high Tg), and excellent reflow heat resistance.

In addition, in a motherboard used in a multi-function mobile phone terminal or the like, as the line density increases and the pattern width becomes narrower, it is required to connect the layers through laser vias having a small diameter. From the viewpoint of connection reliability, there are many examples using field plating, and the connectivity of the interface between the inner layer copper and the copper plating is very important. Therefore, there are also attempts to improve the lightning protection of the base material. Tendency to shot machinability. Generally, after the laser processing of the substrate, a step of partially removing resin residues (desmear treatment step) is performed. Since the bottom surface and wall surface of the laser through hole will be subjected to desmear treatment, when the resin component of the base material is dissolved in a large amount due to the desmear treatment, there is a possibility that the shape of the laser through hole will be significantly deformed due to the dissolution of the resin. , and the following various problems may arise: unevenness of throwing and the like due to unevenness of the wall surface. Therefore, the following quantity is calculated|required as the quantity which melt|dissolved the resin component of a base material by performing desmear processing to an appropriate value, that is, the so-called desmear-dissolved quantity.

Among the various properties sought for insulating materials used in wiring boards, the following methods have been used for the purpose of lowering the relative permittivity: a method of incorporating an epoxy resin with a low relative permittivity, a method of introducing cyanide The method of acid group, the method of containing polyphenylene ether, etc. For example, a resin composition containing epoxy resin (refer to Patent Document 1); a resin composition containing polyphenylene ether and bismaleimide (refer to Patent Document 2); a resin composition containing polyphenylene ether and cyanate ester have been proposed resin composition (refer to Patent Document 3); resin composition containing at least one of styrene-based thermoplastic elastomers, etc. and/or triallyl cyanurate, etc. (refer to Patent Document 4); containing polybutylene Diene resin composition (refer to Patent Document 5); obtained by preliminarily reacting polyphenylene ether-based resin with polyfunctional maleimide and/or polyfunctional cyanate resin and liquid polybutadiene resin composition (refer to Patent Document 6); containing polyphenylene ether obtained by supplying or grafting a compound having an unsaturated double bond group, and triallyl cyanurate and/or triallyl Resin compositions such as isocyanurate (refer to Patent Document 7); resin compositions containing polyphenylene ether, unsaturated carboxylic acid or unsaturated acid anhydride reaction product, and polyfunctional maleimide (refer to Patent Document 8) and so on. [Prior Art Literature] (patent literature)

Patent Document 1: Japanese Patent Laid-Open No. 58-69046 Patent Document 2: Japanese Patent Laid-Open No. 56-133355 Patent Document 3: Japanese Patent Publication No. 61-18937 Patent Document 4: Japanese Patent Laid-Open No. 61-286130 Patent Document 5: Japanese Patent Laid-Open No. 62-148512 Patent Document 6: Japanese Patent Laid-Open No. 58-164638 Patent Document 7: Japanese Patent Application Laid-Open No. 2-208355 Patent Document 8: Japanese Patent Application Laid-Open No. 6-179734

[Problems to be Solved by Invention] As mentioned above, there is a tendency to reduce the relative permittivity and other properties of the insulating material used in the wiring board, but one of the most important properties for interlayer connection by small-diameter laser vias may be For example, the variation in the amount of dimensional change of the prepreg is small. As the thickness of the main board is reduced, a multi-stage lamination method is required as a prepreg lamination method, and the prepreg is subjected to a plurality of times of heating and a plurality of times of pressure during lamination. Therefore, when the variation in the amount of dimensional change of the prepreg (meaning the variation in the amount of thermal shrinkage) is large, the position of the through hole for connecting the layers is inconveniently shifted every time the layers are stacked. Therefore, it is desired to stabilize the variation in the amount of thermal shrinkage of the prepreg. However, according to the study of the present inventors, it was found that the prepreg containing the conventional resin composition cannot sufficiently suppress the variation in the dimensional change, and there is still room for further improvement in this regard.

Therefore, the problem to be solved by the present invention is to provide a method for manufacturing a prepreg, the deviation of the dimensional change of the prepreg is small, and the problem to be solved by the present invention is to provide a prepreg, a laminate, a For printed wiring boards and semiconductor packages, the variation in the dimensional variation of the prepreg is small. In addition, the problem to be solved by the present invention is to provide a prepreg, a laminated board, a printed wiring board and a semiconductor package, in which the positional deviation of the through holes is less likely to occur. [Technical means to solve the problem]

The inventors of the present invention have made studies to solve the above-mentioned problems, and as a result, they have found a prepreg that can solve the above-mentioned problems, and completed the present invention. The prepreg is obtained by going through the following steps. : After the thermosetting resin composition is impregnated into the base material, the thermosetting resin composition is B-staged to obtain a prepreg precursor, and then the surface of the prepreg precursor is heated at a predetermined heat source temperature. Heat treatment is performed to obtain surface heat treatment of the prepreg. The present invention has been accomplished based on such a technical idea.

通式(a2-1)中，R ^A4表示從羥基、羧基及磺酸基之中選出的酸性取代基，R ^A5表示碳數1～5的烷基或鹵素原子，t為1～5的整數，u為0～4的整數且滿足1≦t＋u≦5，其中，當t為2～5的整數時，複數個R ^A4可相同且亦可不同，此外，當u為2～4的整數時，複數個R ^A5可相同且亦可不同；

通式(a3-1)中，X ^A2表示碳數1～3的脂肪族烴基或－O－，R ^A6及R ^A7各自獨立地表示碳數1～5的烷基、鹵素原子、羥基、羧基或磺酸基，v及w各自獨立地為0～4的整數。 [7]如上述[5]或[6]所述之預浸體的製造方法，其中，前述熱硬化性樹脂組成物進一步含有： (B)環氧樹脂； (C)共聚樹脂，其具有源自經取代的乙烯系化合物的結構單元與源自馬來酸酐的結構單元；及， (D)以胺基矽烷系耦合劑進行處理後的氧化矽。 [8]如上述[7]所述之預浸體的製造方法，其中，前述(B)成分為從由雙酚F型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、萘型環氧樹脂、蒽型環氧樹脂、聯苯型環氧樹脂、聯苯芳烷基酚醛清漆型環氧樹脂、及雙環戊二烯型環氧樹脂所組成之群組中選出的至少1種。 [9]如上述[7]或[8]所述之預浸體的製造方法，其中，前述(C)成分為具有由下述通式(C-i)表示的結構單元與由下述通式(C-ii)表示的結構單元之共聚樹脂：

式(C-i)中，R ^C1為氫原子或碳數1～5的烷基，R ^C2為碳數1～5的烷基、碳數2～5的烯基、碳數6～20的芳基、羥基、或(甲基)丙烯醯基，x為0～3的整數，其中，當x為2或3時，複數個R ^C2可相同且亦可不同。 [10]一種預浸體，其是包含基材及熱硬化性樹脂組成物而成，且依照下述方法來求出的標準偏差σ為0.012％以下， 標準偏差σ的算出方法： 將厚度18 μm的銅箔重疊在1片預浸體的雙面上，並以190℃、2.45 MPa的條件進行90分鐘的加熱加壓成形，來製作厚度0.1 mm的雙面覆銅積層板；對於以上述方式獲得的雙面覆銅積層板，在該雙面覆銅積層板的面內的在第1圖中所記載的1～8處實施直徑1.0 mm的開孔；對在第1圖中所記載的縱線方向也就是1-7、2-6、3-5的方向及橫線方向也就是1-3、8-4、7-5的方向的各3點，使用影像測定機來對各3點之間的距離進行測定後，將各測定距離設為初期值；然後，將外層銅箔去除，並利用乾燥機以185℃加熱60分鐘；冷卻後，以與初期值的測定方法相同之方式，來對縱線方向也就是1-7、2-6、3-5的方向及橫線方向也就是1-3、8-4、7-5的方向的各3點之間的距離進行測定；根據相對於各測定距離的初期值的變化率來求出該等變化率的平均值，並算出相對於該平均值的標準偏差σ。 [11]如上述[10]所述之預浸體，其是藉由上述[1]至[9]中任一項所述之預浸體的製造方法來獲得。 [12]如上述[10]所述之預浸體，其中，前述熱硬化性樹脂組成物含有(A)馬來醯亞胺化合物。 [13]如上述[10]或[12]所述之預浸體，其中，前述熱硬化性樹脂組成物進一步含有： (B)環氧樹脂； (C)共聚樹脂，其具有源自經取代的乙烯系化合物的結構單元與源自馬來酸酐的結構單元；及， (D)以胺基矽烷系耦合劑進行處理後的氧化矽。 [14]如上述[10]所述之預浸體，其中，前述熱硬化性樹脂組成物含有(G)環氧樹脂及(H)環氧樹脂硬化劑。 [15]如上述[10]所述之預浸體，其中，前述熱硬化性樹脂組成物含有(K)矽氧改質馬來醯亞胺化合物及(L)咪唑化合物。 [16]一種積層板，其是包含上述[10]至[15]中任一項所述之預浸體與金屬箔而成。 [17]一種印刷線路板，其是包含上述[10]至[15]中任一項所述之預浸體或上述[16]所述之積層板而成。 [18]一種半導體封裝體，其是將半導體元件安裝在上述[17]所述之印刷線路板上而成。 [19]如上述[1]至[4]中任一項所述之預浸體的製造方法，其中，前述熱硬化性樹脂組成物含有(G)環氧樹脂及(H)環氧樹脂硬化劑。 [20]如上述[1]至[4]中任一項所述之預浸體的製造方法，其中，前述熱硬化性樹脂組成物含有(K)矽氧改質馬來醯亞胺化合物及(L)咪唑化合物。 [功效] The present invention relates to the techniques of the following [1] to [20]. [1] A method for producing a prepreg, comprising: after impregnating a base material with a thermosetting resin composition, the thermosetting resin composition is B-staged to obtain a prepreg precursor and, a surface heating treatment step performed after the aforementioned step of obtaining a prepreg precursor; and, the aforementioned surface heating treatment step is a step of heating the surface of the prepreg precursor at a heat source temperature of 200 to 700°C . [2] A method for producing a prepreg, comprising: after impregnating a base material with a thermosetting resin composition, the thermosetting resin composition is B-staged to obtain a prepreg precursor and, a surface heat treatment step performed after the aforementioned step of obtaining a prepreg precursor; and, the aforementioned surface heat treatment step is to heat the prepreg in such a way that the surface temperature of the prepreg precursor becomes 40-130°C The step of heating the surface of the precursor. [3] The method for producing a prepreg according to the above [1] or [2], wherein after the step of obtaining the prepreg precursor and before the surface heat treatment step, the prepreg precursor is The step of cooling the material to 5-60 °C. [4] The method for producing a prepreg according to any one of the above [1] to [3], 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 the above [1] to [4], wherein the thermosetting resin composition contains (A) a maleimide compound. [6] The method for producing a prepreg according to the above [5], wherein the component (A) is a maleimide compound having an N-substituted maleimide group, wherein (a1) Maleimide compounds having at least 2 N-substituted maleimide groups, (a2) monoamine compounds represented by the following general formula (a2-1), and (a3) by the following general formula (a3) -1) The diamine compound represented by the reaction is obtained;

In the general formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group and a sulfonic acid group, R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, and t is an integer of 1 to 5 , u is an integer from 0 to 4 and satisfies 1≦t+u≦5, where, when t is an integer from 2 to 5, a plurality of R ^A4 may be the same or different, and in addition, when u is an integer from 2 to 4 , a plurality of R ^A5 can 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-, and R ^A6 and R ^A7 each independently represent an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, and a carboxyl group. or a sulfonic acid group, v and w are each independently an integer of 0-4. [7] The method for producing a prepreg according to the above [5] or [6], wherein the thermosetting resin composition further contains: (B) an epoxy resin; (C) a copolymer resin having a source A structural unit derived from a substituted vinyl compound and a structural unit derived from maleic anhydride; and, (D) silicon oxide treated with an aminosilane-based coupling agent. [8] The method for producing a prepreg according to the above [7], wherein the component (B) is composed of a bisphenol F epoxy resin, a phenol novolak epoxy resin, and a cresol novolak ring. Selected from the group consisting of oxygen resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl novolac type epoxy resin, and dicyclopentadiene type epoxy resin of at least 1 species. [9] The method for producing a prepreg according to the above [7] or [8], wherein the component (C) has a structural unit represented by the following general formula (Ci) and a structural unit represented by the following general formula ( The copolymer resin of the structural unit represented by C-ii):

In formula (Ci), 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, and an aryl group having 6 to 20 carbon atoms. , a hydroxyl group, or a (meth)acryloyl group, and x is an integer of 0 to 3, wherein when x is 2 or 3, a plurality of R ^C2 may be the same or different. [10] A prepreg comprising a base material and a thermosetting resin composition, and the standard deviation σ obtained by the following method is 0.012% or less, and the calculation method of the standard deviation σ: The copper foil of μm is superimposed on both sides of a prepreg, and heat-pressed at 190°C and 2.45 MPa for 90 minutes to produce a double-sided copper-clad laminate with a thickness of 0.1 mm; For the double-sided copper-clad laminate obtained by the method, holes with a diameter of 1.0 mm are implemented in 1 to 8 places in the surface of the double-sided copper-clad laminate as described in Fig. 1; The vertical line direction is the direction of 1-7, 2-6, 3-5 and the horizontal line direction is the direction of 1-3, 8-4, 7-5. After the distance between the three points was measured, each measurement distance was set as the initial value; then, the outer layer copper foil was removed, and heated at 185°C for 60 minutes in a dryer; after cooling, the same as the initial value measurement method. method, to measure the distance between the three points in the direction of the vertical line, that is, the direction of 1-7, 2-6, 3-5, and the direction of the horizontal line, that is, the direction of 1-3, 8-4, and 7-5. Measurement: From the rate of change with respect to the initial value of each measurement distance, the average value of the rate of change is obtained, and the standard deviation σ with respect to the average value is calculated. [11] The prepreg according to the above [10], which is obtained by the method for producing a prepreg according to any one of the above [1] to [9]. [12] The prepreg according to the above [10], wherein the thermosetting resin composition contains (A) a maleimide compound. [13] The prepreg according to the above [10] or [12], wherein the thermosetting resin composition further contains: (B) an epoxy resin; (C) a copolymer resin having a resin derived from substituted and, (D) silicon oxide treated with an aminosilane-based coupling agent. [14] The prepreg according to the above [10], wherein the thermosetting resin composition contains (G) an epoxy resin and (H) an epoxy resin curing agent. [15] The prepreg according to the above [10], wherein the thermosetting resin composition contains (K) a siloxane-modified maleimide compound and (L) an imidazole compound. [16] A laminate comprising the prepreg according to any one of the above [10] to [15] and a metal foil. [17] A printed wiring board comprising the prepreg according to any one of the above [10] to [15] or the laminate according to the above [16]. [18] A semiconductor package obtained by mounting a semiconductor element on the printed wiring board according to the above [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) epoxy resin and (H) 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 siloxane-modified maleimide compound and (L) Imidazole compound. [effect]

According to the present invention, it is possible to provide a method for manufacturing a prepreg, the variation of the dimensional change of the prepreg is small, and a prepreg, a laminated board, a printed wiring board, and a semiconductor package can be provided. The deviation of the dimensional change is small. In addition, the present invention can also provide a prepreg, a laminate, a printed wiring board, and a semiconductor package, in which the positional displacement of the through holes is less likely to occur.

In the numerical range described in this specification, the upper limit or the lower limit of the numerical range can be replaced with the value disclosed in the Example. In addition, 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 the other numerical range, respectively. In addition, each component and material illustrated in this specification may be used individually by 1 type unless otherwise specified, or may use 2 or more types together. In the present specification, when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified, the total amount of the plurality of substances present in the composition is meant. The present invention also includes aspects in which the matters described in this specification are arbitrarily combined.

[Manufacturing method of prepreg] The present invention is a manufacturing method of a prepreg, which has: After impregnating the base material with the thermosetting resin composition, the step of B-staging the thermosetting resin composition to obtain a prepreg precursor (step 1); and, The surface heating treatment step (step 3) is performed after the aforementioned step of obtaining the prepreg precursor; and, the aforementioned step 3 is to heat the surface of the prepreg precursor at a heat source temperature of 200 to 700°C to obtain the prepreg precursor. body immersion steps. The aforementioned step 3 can also be referred to as a surface heating treatment step, which is after the aforementioned step of obtaining the prepreg precursor, in such a way that the surface temperature of the prepreg precursor becomes 40-130° C. to the prepreg precursor. The surface of the prepreg is heat-treated to obtain a prepreg. Furthermore, it is generally preferred that after the aforementioned step of obtaining the prepreg precursor (step 1) and before the aforementioned surface heat treatment step (step 3), there is a cooling method for cooling the prepreg precursor to 5 to 35°C. step (step 2). Hereinafter, steps 1 to 3 will be described in order, and then, the base material and the thermosetting resin composition for constituting the prepreg will be described.

<Step 1> Step 1 is a step of obtaining a prepreg precursor by B-staging the thermosetting resin composition after impregnating the base material with the thermosetting resin composition. The method of impregnating the base material with the thermosetting resin composition is not particularly limited, and examples thereof include a hot-melt method, a solvent method, and the like. 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. A method of laminating on a substrate after forming a resin film with cloth paper or the like; a method of directly applying a thermosetting resin composition on a substrate using a die coater or the like. The solvent method is a method of impregnating a substrate in a state where the thermosetting resin composition contains an organic solvent to prepare a resin varnish, and examples thereof include a method of dipping the substrate in the resin varnish and drying.

A prepreg precursor in which the thermosetting resin composition is B-staged can be obtained by performing heat treatment after impregnating the base material with the thermosetting resin composition. Here, when the above-mentioned hot-melt method is applied, the B-staging can be performed simultaneously with the heating at the time of laminating the above-mentioned resin film on the base material. In other words, the thermosetting resin composition can be B-staged to obtain a prepreg precursor by heating one side of the resin film and layering it on the base material, and continuing the heating while maintaining this state. At this time, the heating temperature at the time of lamination may be the same or different from the heating temperature at the time of B-staging. When the above-mentioned resin film is laminated on the base material, the heating temperature is not particularly limited, but is preferably 15 to 150°C, and may be 20 to 130°C or 20 to 100°C. Further, when the aforementioned solvent method is applied, the B-staging can be performed simultaneously with the heating at the time of drying the aforementioned resin varnish. In other words, the thermosetting resin composition can be B-staged to obtain a prepreg precursor by dipping the base material in the resin varnish, and then drying the organic solvent by heating while maintaining this state. continue to heat up. At this time, the heating temperature at the time of lamination may be the same or different from the heating temperature at the time of B-staging. When drying the resin varnish, the heating temperature is not particularly limited, but is preferably 10 to 190°C, and may be 15 to 180°C or 15 to 170°C.

In this step 1, the conditions for B-staging are not particularly limited as long as the thermosetting resin composition can be B-staging, and may be appropriately determined according to the type of the thermosetting resin and the like. As heating temperature, 70-190 degreeC is preferable, for example, 80-180 degreeC may be sufficient, 120-180 degreeC may be sufficient, and 140-180 degreeC may be sufficient. The heating method is not particularly limited, and examples thereof include a heating method using a flat plate heater, a heating method by hot air, a heating method by a high frequency, a heating method by magnetic lines of force, a heating method by a laser, The heating method etc. which combine these. Among these, the heating method using a flat heater and the heating method by hot air are simpler and more preferable. Moreover, as a heating time, for example, it may be 1 to 30 minutes, may be 2 to 20 minutes, may be 2 to 10 minutes, or may be 2 to 6 minutes.

<Step 2> Step 2 is a step of cooling the prepreg precursor obtained in Step 1. In other words, step 2 is for the prepreg precursor obtained by subjecting the prepreg precursor to heat treatment in step 1 for B-staging, and cooling the prepreg precursor at least to a level lower than that in the step 1. A step of heat treatment at a lower temperature. By carrying out step 2, the thermal history that is generally applied in the production of prepregs, such as B-staging and cooling of the thermosetting resin composition, is received, and the obtained prepreg precursor may have some problems in its prepreg. There is a tendency for strain or the like to occur in a conventional prepreg inside, and this strain becomes a factor of dimensional change. As described above, it is preferable that the following can be easily and effectively achieved by allowing the strain and the like generated by the thermal history such as heating (step 1) and cooling (step 2) to exist in the interior before step 3 to be described later. : By step 3, the above-mentioned strain and the like are eliminated and the amount of dimensional change is made uniform. Furthermore, since the strain due to the thermal history such as heating (step 1) and cooling (step 2) has been eliminated by step 3, even if the same thermal history is applied after step 3, the strain does not occur, or even if it occurs Since the strain is also very small, the prepreg obtained by the present invention tends to have very little variation in the amount of dimensional change.

The cooling of the prepreg precursor may be performed by natural standing cooling, or may be performed using a cooling device such as an air blower or a cooling roll. Furthermore, from the viewpoint of productivity, cooling by an air blower is preferable. In this step, the surface temperature of the cooled prepreg precursor is usually 5-60°C, preferably 10-45°C, preferably 10-30°C, and more preferably room temperature. In addition, in this specification, the so-called room temperature refers to the ambient temperature without temperature control such as heating and cooling. Generally, it is about 15 to 25°C. However, since it may change due to weather, season, etc. within the above range.

<Step 3> Step 3 is a surface heating treatment step, which is to heat-treat the surface of the prepreg precursor obtained in the aforementioned step 1 or the aforementioned step 2 at a heat source temperature of 200-700° C. to obtain a prepreg It can also be referred to as a surface heating treatment step, which heat-treats the surface of the prepreg precursor in such a way that the surface temperature of the prepreg precursor becomes 40-130° C. to obtain a prepreg. By this step 3, the deviation of the dimensional change amount of the prepreg will be small. The exact reason for this is not clear, but it is considered that by this step 3, the strain of the base material in the prepreg precursor obtained in step 1 or step 2 can be eliminated, and the strain derived from the strain can be reduced. Dimensional change during hardening can therefore reduce variation in the amount of dimensional change. By reducing the variation in the amount of dimensional change, it is possible to reduce the inconvenience of positional displacement of the through hole.

In step 3, the heating method for the surface heating treatment is not particularly limited, for example, a heating method using a flat heater, a heating method by hot air, a heating method by high frequency, a heating method by magnetic lines of force, A heating method by a laser, a heating method combining these, and the like. Among these, from the viewpoint of the ease of controlling the surface temperature, a heating method using a flat heater and a heating method by hot air are preferred. In one aspect of the present invention, the surface heat treatment is performed at a heat source temperature of 200 to 700° C. from the viewpoint of keeping the productivity of the prepreg more favorable and while maintaining the prepreg in the B-stage state. From the viewpoint of reducing the variation in the amount of dimensional change while maintaining good formability, the surface heat treatment is preferably carried out at a higher temperature and in a shorter time than the heat treatment at the time of B-staging in step 1. From this viewpoint, the heat source temperature when performing the surface heat treatment is preferably 250 to 700°C, more preferably 300 to 600°C, and more preferably 350 to 550°C. In particular, when a heating method using a flat heater or a heating method by hot air is performed, it is preferable to perform the surface heating treatment within the aforementioned temperature range. Furthermore, in one aspect of the present invention, the surface heat treatment is performed so that the surface temperature of the prepreg precursor becomes, eg It is implemented in the form of the following temperature: Preferably it is 40-130 degreeC, More preferably, it is 40-110 degreeC, More preferably, it is 60-90 degreeC. It is preferable to set the surface temperature of the prepreg precursor in this range by the above-mentioned heat source temperature. The heating time of the surface heat treatment is not particularly limited, from the viewpoint of keeping the productivity of the prepreg good, and from the viewpoint of keeping the prepreg in the B-stage state and keeping the formability good while reducing the variation in the amount of dimensional change In view of this, 1.0 to 10.0 seconds is preferable, 1.5 to 6.0 seconds is more preferable, and 2.0 to 4.0 seconds is more preferable. From the viewpoint of reducing the variation in the amount of dimensional change while maintaining good formability of the prepreg, the value of the increase in the surface temperature of the prepreg precursor due to the surface heat treatment (that is, before the surface heat treatment The absolute value of the difference between the surface temperature and the highest surface temperature reached in the surface heat treatment) is preferably 5 to 110°C, more preferably 20 to 90°C, and more preferably 40 to 70°C. Here, the detailed heating conditions for the surface heat treatment may be conditions that can increase the surface temperature of the prepreg precursor more than the surface temperature before the surface heat treatment by setting the heat source temperature in the aforementioned range, and the There is no particular limitation as long as it does not significantly affect various properties (for example, fluidity) of the obtained prepreg, and it may be appropriately determined according to the type of thermosetting resin and the like.

From the viewpoints of the handleability and adhesion of the prepreg, the prepreg obtained in step 3 is preferably used in a cooling step in which the prepreg is cooled. The cooling of the prepreg may be performed by natural standing cooling, or may be performed using a cooling device such as an air blower or a cooling roll. The temperature of the cooled prepreg is usually 5 to 80°C, preferably 8 to 50°C, preferably 10 to 30°C, and more preferably room temperature.

In the prepreg of the present invention obtained as described above, the content of the thermosetting resin composition in terms of solid content is preferably 20 to 90 mass %, more preferably 30 to 85 mass %, and 50 to 80 mass % % is better. The thickness of the prepreg of the present invention is, for example, 0.01 to 0.5 mm, preferably 0.02 to 0.3 mm, and more preferably 0.05 to 0.2 mm, from the viewpoint of formability and high-density wiring.

Hereinafter, the base material and the thermosetting resin composition used for producing the prepreg of the present invention will be described in detail in order. [Substrate] As a base material for constituting the prepreg of the present invention, a sheet-like reinforcing base material is used, and a conventional base material used for a laminate for various electrical insulating materials can be used. Examples of the material of the base material include: natural fibers such as paper and cotton wool; inorganic fibers such as glass fibers and asbestos; aramid, polyimide, polyvinyl alcohol, polyester, tetrafluoroethylene, and acrylic Force and other organic fibers; mixtures of these, etc. Among these, from the viewpoint of flame retardancy, glass fiber is preferable. As the glass fiber substrate, for example, a woven fabric obtained by using E glass, C glass, D glass, S glass, etc., or a glass woven fabric obtained by bonding short fibers with an organic binder; Substrates made of mixed cellulose fibers, etc. The glass woven fabric obtained by using E glass is preferable. These substrates have, for example, woven fabrics, non-woven fabrics, yarn bundles, strand mats, surface mats, and the like. In addition, the material and shape are selected according to the intended use and performance of the molded product, and one type may be used alone, or two or more types of materials and shapes may be combined as required. The thickness of the base material is, for example, 0.01 to 0.5 mm, preferably 0.015 to 0.2 mm, and more preferably 0.02 to 0.15 mm, from the viewpoints of formability and high-density wiring. From the viewpoints of heat resistance, moisture resistance, workability, etc., these substrates are preferably those subjected to surface treatment with a silane coupling agent or the like, or those subjected to mechanical fiber opening treatment. .

However, although the prepregs described in the above-mentioned Patent Documents 1 to 8 show relatively good relative permittivity, there are increasing cases in which the prepregs cannot meet the stringent requirements of the market in recent years. In addition, not only the variation in the amount of dimensional change cannot be sufficiently suppressed, but also there are often high heat resistance, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing properties (laser workability). Either one is insufficient, and there is room for further improvement in this regard. In addition, the actual situation is that materials have not been sufficiently developed from the viewpoint of satisfying all the aforementioned properties. However, in the present invention, the components of the thermosetting resin composition are set to the following components while using the above-mentioned method for producing a prepreg of the present invention, so that in addition to sufficiently suppressing variations in the amount of dimensional change, it is possible to make high Heat resistance, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability and throwability (laser workability) are all satisfactory. 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, and in addition to sufficiently suppressing variation in the amount of dimensional change, high heat resistance, high metal foil adhesion, high glass transition temperature, low thermal expansion, molding From the viewpoint of satisfactory properties and throwing properties (laser workability), preferably a thermosetting resin composition (hereinafter referred to as thermosetting resin composition [I]) containing (A) Maleimide compound. From the same viewpoint, the thermosetting resin composition [I] more preferably further contains: (B) an epoxy resin; (C) a copolymer resin having a structural unit derived from a substituted vinyl compound and a source A structural unit derived from maleic anhydride; and, (D) silicon oxide treated with an aminosilane-based coupling agent. From the same viewpoint, the thermosetting resin composition [I] preferably contains (E) a curing agent, and preferably contains (F) a flame retardant from the viewpoint of flame retardancy. In addition, from the viewpoint of sufficiently suppressing the variation in the amount of dimensional change, an epoxy resin composition [II] containing (G) an epoxy resin and (H) an epoxy resin hardener, and ( I) Hardening accelerator and (J) Inorganic filler, or thermosetting resin composition [III], which contains (K) siloxane-modified maleimide compound and (L) imidazole compound, and corresponding Required (M) inorganic filler material.

通式(a2-1)中，R ^A4表示從羥基、羧基及磺酸基之中選出的酸性取代基，R ^A5表示碳數1～5的烷基或鹵素原子，t為1～5的整數，u為0～4的整數，且滿足1≦t＋u≦5，其中，當t為2～5的整數時，複數個R ^A4可相同且亦可不同，此外，當u為2～4的整數時，複數個R ^A5可相同且亦可不同；

通式(a3-1)中，X ^A2表示碳數1～3的脂肪族烴基或－O－，R ^A6及R ^A7各自獨立地表示碳數1～5的烷基、鹵素原子、羥基、羧基、或磺酸基，v及w各自獨立地為0～4的整數。 以下，關於馬來醯亞胺化合物(A)的記載，亦能夠解讀為上述具有N-取代馬來醯亞胺基之馬來醯亞胺化合物的記載。 First, each component contained in the thermosetting resin composition [I] will be described in detail. <(A) Maleimide compound> (A) component is a maleimide compound (hereinafter, sometimes referred to as a maleimide compound (A)), and has an N-substituted maleimide The maleimide compound of the group is preferably, preferably a maleimide compound having an N-substituted maleimide group, which is such that (a1) has at least 2 N-substituted maleimide groups Maleimide compound of amine group [hereinafter, abbreviated as maleimide compound (a1)], (a2) Monoamine compound represented by the following general formula (a2-1) [hereinafter, abbreviated as monoamine Compounds (a2)] and (a3) are obtained by reacting a diamine compound [hereinafter abbreviated as diamine compound (a3)] represented by the following general formula (a3-1).

In the general formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group and a sulfonic acid group, R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, and t is an integer of 1 to 5 , u is an integer from 0 to 4, and satisfies 1≦t+u≦5, where, when t is an integer from 2 to 5, a plurality of R ^A4 can be the same or different, in addition, when u is an integer from 2 to 4 When , the plurality of R ^A5 can 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-, and R ^A6 and R ^A7 each independently represent an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, and a carboxyl group. , or a sulfonic acid group, and v and w are each independently an integer of 0 to 4. Hereinafter, the description of the maleimide compound (A) can also be interpreted as the description of the above-mentioned maleimide compound having an N-substituted maleimide group.

The weight average molecular weight (Mw) of the maleimide compound (A) is preferably from 400 to 3,500, preferably from 400 to 2,300, and preferably from 800 to 800 from the viewpoint of solubility in organic solvents and mechanical strength. 2,000 is better. In addition, in this specification, the weight average molecular weight is a value measured by a gel permeation chromatography (GPC) method (in terms of standard polystyrene) using tetrahydrofuran as an eluent, and more specifically, it is The value measured by the method described in the Example.

(maleimide compound (a1)) The maleimide compound (a1) is a maleimide compound having at least two N-substituted maleimide groups in one molecule. The maleimide compound (a1) includes, for example, an aliphatic hydrocarbon group (wherein no aromatic hydrocarbon group is present between any two maleimide groups among a plurality of maleimide groups). ) maleimide compound [hereinafter, referred to as aliphatic hydrocarbon group-containing maleimide], or an aromatic group between any two maleimide groups among a plurality of maleimide groups The maleimide compound of the aromatic hydrocarbon group [hereinafter, referred to as the aromatic hydrocarbon group-containing maleimide]. Among them, from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability and throwing properties, aromatic hydrocarbon group-containing maleic Imines are preferred. The aromatic hydrocarbon group-containing maleimide may contain an aromatic hydrocarbon group between any combination of any two maleimide groups selected arbitrarily, and may have both an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The maleimide compound (a1) is preferably a Maleimide compounds having 2 to 5 N-substituted maleimide groups in the molecule, more preferably maleimide compounds having 2 N-substituted maleimide groups in one molecule . In addition, the maleimide compound (a1) is preferred from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability and throwing properties is an aromatic hydrocarbon group-containing maleimide represented by any one of the following general formulae (a1-1) to (a1-4), more preferably by the following general formulae (a1-1), (a1-4) The aromatic hydrocarbon group-containing maleimide represented by -2) or (a1-4) is particularly preferably an aromatic hydrocarbon group-containing maleimide represented by the following general formula (a1-2).

In the above formulae (a1-1) to (a1-3), R ^A1 to R ^A3 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms; X ^A1 represents an alkylene group having 1 to 5 carbon atoms, a carbon number of 2 ~5 alkylene, -O-, -C(=O)-, -S-, -S-S-, or sulfonyl; p, q and r are each independently an integer from 0 to 4; s is an integer from 0 to 10. Examples of the aliphatic hydrocarbon groups having 1 to 5 carbon atoms represented by R ^A1 to R ^A3 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-butyl Amyl etc. From the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing properties, the aliphatic hydrocarbon group has a carbon number of 1 to 3. Aliphatic hydrocarbon groups are preferred, and methyl and ethyl groups are preferred.

Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^A1 include methylene, 1,2-dimethylene, 1,3-trimethylene, 1,4-tetramethylene, 1 , 5-pentamethylene and so on. From the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing properties, as the alkylene group, those having 1 to 3 carbon atoms are used. Alkylene is preferred, and methylene is preferred. As a C2-C5 alkylene group represented by X ^A1 , an ethylene group, a propylene group, an isopropylidene group, a butylene group, an isobutylene group, a pentylene group, an isopentylene group, etc. are mentioned, for example. Among these, from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing properties, as the alkylene group, the Isopropyl is preferred. Among the above options, X ^A1 is preferably an alkylene group having 1 to 5 carbon atoms or an alkylene group having 2 to 5 carbon atoms. The preferred example is as described above. p, q and r are each independently an integer of 0 to 4, from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing properties It can be seen that any one is preferably 0 to 2, preferably 0 or 1, and more preferably 0. s is an integer of 0 to 10, and 0 to 5 are preferable, and 0 to 3 are more preferable from the viewpoint of easiness of acquisition. 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.

The maleimide compound (a1) specifically includes, for example, N,N'-ethylidenebismaleimide, N,N'-hexamethylenebismaleimide, bis(4 - Maleimidocyclohexyl)methane, 1,4-bis(maleimidomethyl)cyclohexane, etc. containing aliphatic hydrocarbyl 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 bis Maleimide, bis(4-maleimidophenyl) ether, bis(4-maleimidophenyl) sulfide, bis(4-maleimidophenyl) sulfide ether, bis(4-maleimidophenyl)ketone, 1,4-bis(4-maleimidophenyl)cyclohexane, 1,4-bis(maleimidophenyl) Methyl)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-(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)benzene yl]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-maleimide phenylphenoxy) biphenyl, 4,4-bis(4-maleimidophenoxy)biphenyl, bis[4-(3-maleimidophenoxy)phenyl]ketone , bis[4-(4-maleimidophenoxy)phenyl]ketone, 2,2'-bis(4-maleimidophenyl) disulfide, bis(4-maleimidophenyl)disulfide Lysimidophenyl) disulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfide, bis[4-(4-maleimidophenoxy) base) phenyl] sulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfene, bis[4-(4-maleimidophenoxy)phenyl ] bisulfite, bis[4-(3-maleimidophenoxy)phenyl] bis[4-(4 -Maleimidophenoxy)phenyl] bis[4-(3-maleimidophenoxy)phenyl]ether, bis[4-(4-maleimide) phenoxy)phenyl] ether, 1,4-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis [4-(4-Maleiminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy) )-α,α-dimethylbenzyl]benzene, 1,3-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-maleinyl] iminophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy) -3,5-dimethyl-α,α-dimethylbenzyl]benzene, polyphenylmethane maleimide, etc. containing aromatic hydrocarbon group maleimide.

Among these, bis(4-maleimidophenyl)methane, bis(4-maleimidophenyl), and bis(4-maleimidophenyl) are preferred from the viewpoints of high reaction rate and higher heat resistance. Phenyl) bisulfite, bis(4-maleimidophenyl) sulfide, bis(4-maleimidophenyl) disulfide, N,N'-(1,3-phenylene) base) bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, from the viewpoint of low cost, bis(4 -maleimidophenyl)methane, N,N'-(1,3-phenylene)bismaleimide, and bis(4) is particularly preferred from the viewpoint of solubility in solvents -maleimidophenyl)methane. The maleimide compound (a1) may be used alone or in combination of two or more.

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

In the above general formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group and a sulfonic acid group, R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, and t is a group of 1 to 5 carbon atoms. Integer, u is an integer of 0 to 4, and satisfies 1≦t+u≦5, wherein, when t is an integer of 2 to 5, a plurality of R ^A4 may be the same or different, and in addition, when u is an integer of 2 to 4 In the case of an integer, a plurality of R ^A5 may be the same or different. From the viewpoints of solubility and reactivity, as the acidic substituent represented by R ^A4 , a hydroxyl group and a carboxyl group are preferable, and when heat resistance is also considered, a hydroxyl group is preferable. t is an integer from 1 to 5, and from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability and throwing property, t is 1 to 3. is preferably an integer, preferably 1 or 2, more preferably 1. Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^A5 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, and n-pentyl. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. As a halogen atom represented by R ^A5 , a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example. u is an integer from 0 to 4, and from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing properties, 0 to 3 An integer is preferable, an integer of 0-2 is preferable, 0 or 1 is more preferable, and 0 is especially preferable. From the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability and throwing properties, the monoamine compound (a2) is preferably the following The monoamine compound represented by the general formula (a2-2) or (a2-3) is more preferably a monoamine compound represented by the following general formula (a2-2). Among them, in the general formulas (a2-2) and (a2-3), R ^A4 , R ^A5 and u are the same as R ^A4 , R ^A5 and u in the general formula (a2-1), and the preferred examples are also the same.

As the monoamine compound (a2), for example: o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-aminobenzenesulfonic acid Acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and other monoamine compounds with acidic substituents. Among these, m-aminophenol, p-aminophenol, p-aminobenzoic acid, and 3,5-dihydroxyaniline are preferred from the viewpoint of solubility and reactivity, and from the viewpoint of heat resistance , preferably o-aminophenol, m-aminophenol, p-aminophenol, and also considering dielectric properties, low thermal expansion and manufacturing cost, more preferably is p-aminophenol. A monoamine compound (a2) may be used individually by 1 type, and may use 2 or more types together.

通式(a3-1)中，X ^A2表示碳數1～3的脂肪族烴基或－O－，R ^A6及R ^A7各自獨立地表示碳數1～5的烷基、鹵素原子、羥基、羧基、或磺酸基，v及w各自獨立地為0～4的整數。 (Diamine Compound (a3)) The diamine compound (a3) is a diamine compound represented by 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-, and R ^A6 and R ^A7 each independently represent an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, and a carboxyl group. , or a sulfonic acid group, and v and w are each independently an integer of 0 to 4.

As a C1-C3 aliphatic hydrocarbon group represented by X ^A2 , a methylene group, an ethylidene group, a propylene group, a propylene group, etc. are mentioned, for example. As X ^A2 , a methylene group is preferable. Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^A6 and R ^A7 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl Base et al. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. v and w are preferably an integer of 0 to 2, preferably 0 or 1, more preferably 0.

通式(a3-1’)中，X ^A2、R ^A6、R ^A7、v及w與前述通式(a3-1)中的X ^A2、R ^A6、R ^A7、v及w相同，較佳態樣亦相同。 As the diamine compound (a3), a diamine compound represented by the following general formula (a3-1') is preferable.

In the general formula (a3-1'), X ^A2 , R ^A6 , R ^A7 , v and w are the same as X ^A2 , R ^A6 , R ^A7 , v and w in the aforementioned general formula (a3-1), preferably The same is true.

Specific examples of the diamine compound (a3) include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, and 4,4'-diamine diphenylpropane, 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'-diaminodiphenylethane Ethyl-4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,3'-diphenyl ether Hydroxy-4,4'-diaminodiphenylmethane, 2,2',6,6'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro- 4,4'-Diaminodiphenylmethane, 3,3'-dibromo-4,4'-diaminodiphenylmethane, 2,2',6,6'-tetramethylchloro-4 ,4'-diaminodiphenylmethane, 2,2',6,6'-tetrabromo-4,4'-diaminodiphenylmethane, etc. Among these, from the viewpoint of low cost, 4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenyl Methane is more preferably 4,4'-diaminodiphenylmethane from the viewpoint of solubility in a solvent.

The reaction of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3) is preferably carried out in the following manner: preferably in the presence of an organic solvent, at a reaction temperature of 70 ℃ The reaction is allowed to proceed at ~200°C for 0.1 to 10 hours. The reaction temperature is preferably 70-160°C, more preferably 70-130°C, and particularly preferably 80-120°C. The reaction time is preferably 1 to 6 hours, more preferably 1 to 4 hours.

(Amounts of maleimide compound (a1), monoamine compound (a2), and diamine compound (a3) used) Maleimide compound (a1), monoamine compound (a2), and diamine compound (a3) ) in the reaction of ), the usage amount of the three is preferably the sum of the primary amine group equivalents [recorded as -NH ₂ group equivalents] possessed by the monoamine compound (a2) and the diamine compound (a3) and the maleimide The relationship between the maleimide group equivalents of the compound (a1) satisfies the following formula. 0.1≦[Maleimide group equivalents]/[total of—NH ₂ group equivalents]≦10 By setting [maleimide group equivalents]/[total—NH ₂ group equivalents] to 0.1 or more, It is possible to prevent gelation and heat resistance from decreasing, and by setting [maleimide group equivalent]/[-NH ₂ group equivalent total] to 10 or less, the solubility in organic solvents can be prevented from decreasing. , Metal foil adhesion and heat resistance, it is better. From the same viewpoint, it is more preferable to satisfy the following formula. 1≦[maleimide group equivalent]/[total of —NH ₂ group equivalent]≦9 More preferably, the following formula is satisfied. 2≦[Maleimide group equivalent]/[-NH ₂ group equivalent total]≦8

(Organic solvents) As described above, the reaction of the maleimide compound (a1), the monoamine compound (a2), and the diamine compound (a3) is preferably carried out in an organic solvent. The organic solvent is not particularly limited as long as it does not adversely affect the reaction. Examples include: alcohol-based solvents such as ethanol, propanol, butanol, methyl cellulose, butyl cellulose, and propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane Ketone-based solvents such as ketones; ether-based solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and mesitylene; including amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone Nitrogen-atom-containing solvents including sulfite-based solvents; sulfur-atom-containing solvents including sulfite-based solvents such as dimethyl sulfoxide; ester-based solvents such as ethyl acetate and γ-butyrolactone, and the like. Among them, from the viewpoint of solubility, alcohol-based solvents, ketone-based solvents, and ester-based solvents are preferable, and from the viewpoint of low toxicity, cyclohexanone, propylene glycol monomethyl ether, Methylcellulose and γ-butyrolactone are also considered to be highly volatile, and when the prepreg is not easily retained as a residual solvent, cyclohexanone, propylene glycol monomethyl ether, dimethyl ethyl ether are more preferable. Acetamide, particularly preferably dimethylacetamide. An organic solvent may be used individually by 1 type, and may use 2 or more types together. The amount of the organic solvent to be used is not particularly limited, but from the viewpoint of solubility and reaction efficiency, it is based on 100 parts by mass of the total of the maleimide compound (a1), the monoamine compound (a2), and the diamine compound (a3) , as long as the usage-amount of an organic solvent becomes the following amount: Preferably it is 25-1,000 mass parts, More preferably, it is 40-700 mass parts, More preferably, it is 60-250 mass parts. Solubility can be easily ensured by setting the usage amount of the organic solvent to 25 parts by mass with respect to 100 parts by mass in total of the maleimide compound (a1), the monoamine compound (a2), and the diamine compound (a3). , by setting the usage amount of the organic solvent to 1,000 parts by mass or less with respect to the total of 100 parts by mass of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3), it is easy to suppress The reaction efficiency is greatly reduced.

(reaction catalyst) The reaction of the maleimide compound (a1), the monoamine compound (a2), and the diamine compound (a3) can be carried out in the presence of a reaction catalyst as necessary. Examples of the reaction catalyst include amine-based catalysts such as triethylamine, pyridine, and tributylamine; imidazole-based catalysts such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine. A reaction catalyst may be used individually by 1 type, and may use 2 or more types together. The usage-amount of a reaction catalyst is not specifically limited, It is preferable that it is 0.001-5 mass parts with respect to a total of 100 mass parts 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 epoxy resin (B)), and preferably an epoxy resin having at least two epoxy groups in one molecule. As an epoxy resin which has at least two epoxy groups in one molecule, a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, etc. are mentioned, for example. Among these, glycidyl ether type epoxy resins are preferred. Epoxy resins can also be classified into various epoxy resins according to different main skeletons. Among the above types of epoxy resins, they can be further classified into: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol F type epoxy resin. Bisphenol type epoxy resin such as S type epoxy resin; biphenyl aralkyl novolac type epoxy resin, phenol novolak type epoxy resin, alkylphenol novolac type epoxy resin, cresol novolac type epoxy resin Resin, naphthol alkyl phenol copolyphenol novolak epoxy resin, naphthol aralkyl cresol copolymer novolak epoxy resin, bisphenol A novolak epoxy resin, bisphenol F novolak epoxy resin, etc. Novolak type epoxy resin; stilbene type epoxy resin; triazine skeleton epoxy resin; stilbene skeleton epoxy resin; naphthalene type epoxy resin; ; Biphenyl type epoxy resin; Xylene type epoxy resin; Alicyclic epoxy resin such as dicyclopentadiene type epoxy resin, etc. Among them, from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability and throwing properties, it is preferable to use 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 ring At least one kind selected from the group consisting of oxygen resins and dicyclopentadiene epoxy resins, from the viewpoints of low thermal expansion and high glass transition temperature, more preferably a cresol novolac epoxy resin , at least one selected from the group consisting of naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl novolac type epoxy resin and phenol novolac type epoxy resin , more preferably a cresol novolac 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 100-500 g/eq, preferably 120-400 g/eq, more preferably 140-300 g/eq, and particularly preferably 170-240 g/eq. Here, the epoxy equivalent is the equivalent weight (g/eq) of the resin per epoxy group, and can be measured in accordance with the method prescribed in JIS K 7236 (2001). Specifically, it can be obtained by using an automatic titration device "GT-200 type" manufactured by Mitsubishi Chemical Analytech Co., Ltd., and after weighing 2 g of epoxy resin into a 200 mL beaker, dropwise added 90 mL of methyl ethyl ketone was dissolved with an ultrasonic cleaner, 10 mL of glacial acetic acid and 1.5 g of cetyltrimethylammonium bromide were added, and a 0.1 mol/L perchloric acid/acetic acid solution was added. to titrate. As a commercial product of epoxy resin (B), for example, a cresol novolak type epoxy resin "EPICLON (registered trademark) N-673" (manufactured by DIC Co., Ltd., epoxy equivalent: 205 to 215 g/ eq), naphthalene type epoxy resin "HP-4032" (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 152 g/eq), biphenyl type epoxy resin "YX-4000" (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 186 g/eq), dicyclopentadiene-type epoxy resin "HP-7200H" (manufactured by DIC Co., Ltd., epoxy equivalent: 280 g/eq), and the like. In addition, the epoxy equivalent is the value described in the catalog of the manufacturing company of this product.

<(C) Specific copolymer resin> The component (C) is a copolymer resin (hereinafter, sometimes referred to as a copolymer resin (C)), which has a structural unit derived from a substituted vinyl compound and a structural unit derived from maleic anhydride. As the substituted vinyl compound, an aromatic vinyl compound, an aliphatic vinyl compound, a functional group-substituted vinyl compound, etc. are mentioned, for example. As an aromatic vinyl compound, styrene, 1-methylstyrene, vinyltoluene, dimethylstyrene, etc. are mentioned, for example. As an aliphatic vinyl compound, propylene, butadiene, isobutylene, etc. are mentioned, for example. As the vinyl-based compound substituted by a functional group, acrylonitrile; a compound having a (meth)acryloyl group such as methyl acrylate and methyl methacrylate, etc. may be mentioned, for example. Among these, as the substituted vinyl compound, an aromatic vinyl compound is preferable, and styrene is preferable. As the component (C), a copolymer resin having a structural unit represented by the following general formula (C-i) and a structural unit represented by the following general formula (C-ii) is preferable.

式(C-i)中，R ^C1為氫原子或碳數1～5的烷基，R ^C2為碳數1～5的烷基、碳數2～5的烯基、碳數6～20的芳基、羥基、或(甲基)丙烯醯基；x為0～3的整數；其中，當x為2或3時，複數個R ^C2可相同且亦可不同。

In formula (Ci), 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, and an aryl group having 6 to 20 carbon atoms. , hydroxyl, or (meth)acryloyl; x is an integer from 0 to 3; wherein, when x is 2 or 3, a plurality of R ^C2 may be the same or different.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^C1 and R ^C2 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl Base et al. 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, a crotyl group, and the like. The alkenyl group is preferably an alkenyl group having 3 to 5 carbon atoms, and preferably an alkenyl group having 3 or 4 carbon atoms. As a C6-C20 aryl group represented by R ^C2 , a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, etc. are mentioned, for example. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and preferably an aryl group having 6 to 10 carbon atoms. x is preferably 0 or 1, preferably 0. Among the structural units represented by the general formula (Ci), a structural unit represented by the following general formula (Ci-1) in which R ^C1 is a hydrogen atom and x is 0 is preferably a structural unit derived from styrene.

In the copolymer resin (C), the content ratio of the structural unit derived from the substituted vinyl compound and the structural unit derived from maleic anhydride is the structural unit derived from the substituted vinyl compound/the one derived from maleic anhydride. The mol ratio of the structural unit is preferably 1-9, more preferably 2-9, more preferably 3-8, and particularly preferably 3-7. In addition, the content ratio of the structural unit represented by the aforementioned general formula (C-i) to the structural unit represented by the aforementioned general formula (C-ii), that is, the mol ratio of (C-i)/(C-ii), is similarly expressed as 1 to 9 are preferred, 2 to 9 are more preferred, 3 to 8 are more preferred, and 3 to 7 are particularly preferred. When these mol ratios are 1 or more, preferably 2 or more, the effect of improving the dielectric properties tends to be more sufficient, and when these mol ratios are 9 or less, compatibility tends to be good. In the copolymer resin (C), the total content of the structural unit derived from the substituted vinyl compound and the structural unit derived from maleic anhydride, and the structural unit represented by the general formula (C-i) and the structural unit represented by the formula (C-ii) The total content of the indicated structural units is preferably 50% by mass or more, more preferably 70% by mass or more, 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 4,500-18,000, preferably 5,000-18,000, more preferably 6,000-17,000, more preferably 8,000-16,000, particularly preferably 8,000-15,000, and more preferably 9,000 ~13,000 Best.

Furthermore, the method of lowering the dielectric constant of the epoxy resin by using the copolymer resin of styrene and maleic anhydride, when applied to the material for printed wiring boards, the impregnation of the base material and the peeling strength of the copper foil will be reduced. will be insufficient, so there is a tendency to generally avoid the above methods. Therefore, there is a tendency to generally avoid the use of the aforementioned copolymer resin (C), but the present invention was accomplished by knowing the fact that although the aforementioned copolymer resin (C) was used, by containing the aforementioned components (A) and (B) ) component, it will become a thermosetting resin composition, which has high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature and low thermal expansion, and is excellent in formability and throwing properties.

(Manufacturing method of copolymer resin (C)) The copolymer resin (C) can be produced by copolymerizing a substituted vinyl compound and maleic anhydride. The substituted vinyl compounds are as described above. A substituted vinyl compound may be used individually by 1 type, and may use 2 or more types together. Furthermore, in addition to the aforementioned substituted vinyl compound and maleic anhydride, various polymerizable components may be copolymerized. In addition, substituents such as allyl, methacryloyl, acryl, and hydroxyl groups can be introduced into the substituted vinyl compound, especially the aromatic vinyl compound, by the following reaction: Friedel-Crafts ( Friedel-Crafts) reaction; or a reaction using a metal-based catalyst such as lithium.

As a copolymer resin (C), a commercial item can also be used. As a commercial product, "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) [the above are manufactured by CRAY VALLEY Corporation], etc.

<(D) Silicon oxide treated with an aminosilane-based coupling agent> In the case of silicon oxide treated with an aminosilane-based coupling agent (hereinafter, sometimes referred to as silicon oxide treated with an aminosilane-based coupling agent (D)) as ( D) component, in addition to the effect of improving the low thermal expansion property, since the peeling of silicon oxide can be suppressed by improving the adhesiveness with the above-mentioned components (A) to (C), it is also possible to obtain the effect of suppressing the The effects such as the shape deformation of the laser via caused by the excess amount of desmear are preferable.

式(D-1)，R ^D1為碳數1～3的烷基或碳數2～4的醯基，y為0～3的整數。 Specifically, as the aminosilane-based coupling agent, a silane coupling agent having a silicon group and an amino group represented by the following general formula (D-1) is preferable.

In formula (D-1), R ^D1 is an alkyl group having 1 to 3 carbon atoms or an acyl group having 2 to 4 carbon atoms, and y is an integer of 0 to 3.

As a C1-C3 alkyl group represented by R ^D1 , a methyl group, an ethyl group, a n-propyl group, and an isopropyl group are mentioned, for example. Among these, a methyl group is preferable. Examples of the acyl group having 2 to 4 carbon atoms represented by R ^D1 include an acetyl group, a propionyl group, and an acryl group. Among these, acetyl group is preferred.

The amino silane-based coupling agent may have one amino group, may have two amino groups, and may have three or more amino groups, and usually has one or two amino groups. Examples of aminosilane-based coupling agents having one amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-amino Propyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, [3-(trimethoxysilyl)propyl]carbamic acid 2- Propargyl esters and the like, but are not particularly limited thereto. Examples of the aminosilane-based coupling agent having two amino groups include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl) Ethyl)-3-aminopropyltrimethoxysilane, 1-[3-(trimethoxysilyl)propyl]urea, 1-[3-(triethoxysilyl)propyl]urea, etc. , but are not particularly limited by these.

Although it is also possible to use a specific silicon oxide as an inorganic filler other than the component (D) in place of the silicon oxide (D) treated with an aminosilane-based coupling agent, it is preferable from the viewpoint of the aforementioned effect. Silicon oxide (D) treated with an aminosilane-based coupling agent is used, such as silicon oxide treated with a specific coupling agent, silicon oxide without surface treatment, etc. Specific coupling agents are: epoxysilane-based coupling agent, phenylsilane-based coupling agent, alkylsilane-based coupling agent, alkenylsilane-based coupling agent, alkynylsilane-based coupling agent, haloalkylsilane-based coupling agent, silicon Oxane-based coupling agent, hydrosilane-based coupling agent, silazane-based coupling agent, alkoxysilane-based coupling agent, chlorosilane-based coupling agent, (meth)acrylic-based silane-based coupling agent, aminosilane-based coupling agent , Isocyanurate silane coupling agent, ureido silane coupling agent, mercapto silane coupling agent, thioether silane coupling agent, or isocyanato silane coupling agent, etc. Moreover, the silicon oxide (D) processed with the aminosilane type coupling agent can be used together with the silicon oxide processed with the other coupling agent mentioned above. In this case, the amount of the silicon oxide treated with the other coupling agent is preferably 50 parts by mass or less, and 30 parts by mass relative to 100 parts by mass of the silicon oxide (D) treated with the aminosilane-based coupling agent. The content is preferably not more than 15 parts by mass, more preferably not more than 10 parts by mass, and most preferably not more than 5 parts by mass, but is not particularly limited.

Examples of the above-mentioned silicon oxide include: deposited silicon oxide produced by a wet method and has a high water content; and dry method silicon oxide produced by a dry method and hardly contains bound water or the like. As dry-process silicon oxide, according to different manufacturing methods, for example, pulverized silicon oxide, fumed silicon oxide, fused silicon oxide (fused spherical silicon oxide), and the like can be used. Among these, fused silica is preferable from the viewpoint of low thermal expansion and high fluidity when filled in resin. The average particle size of the silicon oxide is not particularly limited, and is preferably 0.1-10 μm, preferably 0.1-6 μm, more preferably 0.1-3 μm, and particularly preferably 1-3 μm. When the average particle size of silicon oxide is 0.1 μm or more, the fluidity at high filling can be kept good, and when the average particle size of silicon oxide is 10 μm or less, the mixing probability of coarse particles can be reduced and suppressed Malfunctions due to coarse particles occur. Here, the average particle size refers to the particle size at a point corresponding to 50% of the volume when the cumulative particle size distribution curve is obtained from the particle size, taking the total volume of the particles as 100%, and can be obtained by using laser diffraction The particle size distribution measuring apparatus of the scattering method or the like is used for measurement. In addition, the specific surface area of the silicon oxide is preferably 4 cm ² /g or more, preferably 4-9 cm ² /g, more preferably 5-7 cm ² /g.

<(E) Hardener> The thermosetting resin composition [I] may further contain a hardener as the component (E) (hereinafter, sometimes referred to as a hardener (E)). As the hardening agent (E), for example, dicyandiamide; ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, diethylaminopropyl Chain aliphatic amines other than dicyandiamide, such as amine, tetramethylguanidine, triethanolamine; isophorone diamine, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, bis(4 -amino-3-methyldicyclohexyl)methane, N-aminoethylpiperazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[ 5.5] Cyclic aliphatic amines such as undecane; aromatic amines such as xylylenediamine, phenylenediamine, diaminodiphenylmethane, diaminodiphenyl amine, and the like. Among these, dicyandiamide is preferable from the viewpoint 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 the melting point of dicyandiamide with higher purity is 207 to 212° C. Dicyandiamide is a crystalline substance, which can be orthorhombic or lamellar. The purity of dicyandiamide is preferably above 98%, preferably above 99%, more preferably above 99.4%. Commercially available dicyandiamide can be used, and for example, commercially available products such as Nippon Carbide 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 as a component (F) (hereinafter sometimes referred to as a flame retardant (F)). Here, dicyandiamide and the like among the above-mentioned curing agents also have the effect of a flame retardant, but in the present invention, a substance capable of producing the function of a curing agent is classified as a curing agent, and it is not included in ( F) in the ingredients. Examples of the flame retardant include halogen-containing flame retardants containing bromine and chlorine; phosphorus-based flame retardants; nitrogen-based flame retardants such as guanidine sulfonate, melamine sulfate, melamine polyphosphate, and melamine cyanurate. ; Phosphazene flame retardants such as cyclophosphazene and polyphosphazene; inorganic flame retardants such as antimony trioxide. Among these, phosphorus-based flame retardants are preferred. As the phosphorus-based flame retardant, there are inorganic phosphorus-based flame retardants and organic phosphorus-based flame retardants. Examples of inorganic phosphorus-based flame retardants include ammonium phosphates such as red phosphorus, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphamide; phosphoric acid; Phosphine oxide, etc. Examples of organic phosphorus-based flame retardants include aromatic phosphoric acid esters, monosubstituted phosphonic acid diesters, disubstituted phosphinic acid esters, metal salts of disubstituted phosphinic acids, organic nitrogen-containing phosphorus compounds, cyclic Organic phosphorus compounds, phosphorus-containing phenol resins, etc. Among these, aromatic phosphoric acid esters and metal salts of disubstituted phosphinic acids are preferred. Here, the metal salt is preferably any 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 more preferably an aluminum salt. Among the organic phosphorus-based flame retardants, aromatic phosphates are preferred.

Examples of aromatic phosphoric acid esters include triphenyl phosphate, tris(cresyl phosphate), tris(xylyl phosphate), cresyl diphenyl phosphate, and bis(2,6-xylyl phosphate) cresyl phosphate. , Resorcinol bis(diphenyl phosphate), 1,3-phenylene bis(bis(2,6-xylylene phosphate)), bisphenol A bis(diphenyl phosphate), 1,3- phenylene bis(diphenyl phosphate), etc. As a monosubstituted phosphonic acid diester, divinyl phenylphosphonate, diallyl phenylphosphonate, bis(1-butenyl phenylphosphonate), etc. are mentioned, for example. As a disubstituted phosphinate, phenyl diphenylphosphinate, methyl diphenylphosphinate, etc. are mentioned, for example. Examples of the metal salt of disubstituted phosphinic acid include metal salts of dialkylphosphinic acid, metal salts of diallylphosphinic acid, metal salts of divinylphosphinic acid, and diarylphosphines. Acid metal salts, etc. These metal salts are as described above, preferably any of lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, and zinc salts. Examples of the organic nitrogen-containing phosphorus compound include phosphazene compounds such as bis(2-allylphenoxy)phosphazene and bis(tolyl)phosphazene; melamine phosphate, melamine pyrophosphate, melamine polyphosphate, polyphosphate Melam Phosphate, etc. Examples of the cyclic organic phosphorus compound include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10 -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc. Among these, at least one selected from the group consisting of aromatic phosphoric acid esters, metal salts of disubstituted phosphinic acids, and cyclic organic phosphorus compounds is preferred, and aromatic phosphoric acid esters are more preferred.

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

In formulas (F-1) to (F-3), R ^F1 to R ^F5 are each independently an alkyl group with 1 to 5 carbon atoms or a halogen atom; e and F are each independently an integer of 0 to 5, g, h and i are each independently an integer of 0 to 4. 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, Zinc atom; j is an integer of 1-4.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^F1 to R ^F5 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl Base et al. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. As a halogen atom represented by R ^F1 - R ^F5 , a fluorine atom etc. are mentioned, for example. e and f are preferably an integer of 0 to 2, more preferably 2. g, h and i are preferably an integer of 0 to 2, preferably 0 or 1, 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 the case of R ^F1 to R ^F5 . As a C6-C14 aryl group represented by R ^F6 and R ^F7 , a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, etc. are mentioned, for example. 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, it varies in the range of 1 to 4 according to the type of M. As M, an aluminum atom is preferable. Furthermore, when M is an aluminum atom, j is 3.

(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 the content of the components (A) to (C) is preferably 100 parts by mass of the total of the components (A) to (C). It is 15-65 mass parts, (B) component is 15-50 mass parts, (C) component is 10-45 mass parts, (D) component is 30-70 mass parts. High heat resistance, low relative permittivity, high glass transition temperature, and low thermal expansion can be obtained by containing 15 parts by mass or more of (A) component with respect to 100 parts by mass of the total of (A) to (C) components. Propensity. On the other hand, when the (A) component is 65 parts by mass or less with respect to the total of 100 parts by mass of the components (A) to (C), the fluidity and formability of the thermosetting resin composition [I] are good. Propensity. When the (B) component is 15 parts by mass or more with respect to the total of 100 parts by mass 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 the component (B) is 50 parts by mass or less with respect to the total of 100 parts by mass of the components (A) to (C), high heat resistance, low relative permittivity, and high glass transition temperature may occur. and the tendency for low thermal expansion. When the (C) component is 10 parts by mass or more with respect to the total of 100 parts by mass of the components (A) to (C), high heat resistance and low relative permittivity tend to be obtained. On the other hand, when the component (C) is 45 parts by mass or less with respect to the total of 100 parts by mass of the components (A) to (C), high heat resistance, high metal foil adhesion, and low thermal expansion can be obtained. tendency. When the (D) component is 30 parts by mass or more with respect to the total of 100 parts by mass of the components (A) to (C), there is a tendency that excellent low thermal expansion properties can be obtained. On the other hand, when the component (D) is 70 parts by mass or less with respect to the total of 100 parts by mass of the components (A) to (C), heat resistance can be obtained and the flow of the thermosetting resin composition [I] can be obtained. The property and formability tend to be good.

In addition, when the thermosetting resin composition [I] contains the (E) component, the content of the (E) component is preferably 0.5 to 6 parts by mass relative to 100 parts by mass of the total of the (A) to (C) components . When the (E) component is 0.5 parts by mass or more with respect to the total of 100 parts by mass of the components (A) to (C), high metal foil adhesion and excellent low thermal expansion tend to be obtained. On the other hand, when (E) component is 6 mass parts or less with respect to a total of 100 mass parts of (A)-(C) components, there exists a tendency for high heat resistance to be acquired.

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

(other ingredients) Other components, such as an additive and an organic solvent, can be contained in the thermosetting resin composition [I] as needed in the range which does not impair the effect of this invention. These may be contained individually by 1 type, and may contain 2 or more types.

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

(Organic solvents) The thermosetting resin composition [I] may contain an organic solvent from the viewpoint of easy handling by dilution and from the viewpoint of easy production of a prepreg to be described later. In this specification, the thermosetting resin composition containing an organic solvent may be called resin varnish. The organic solvent is not particularly limited, and examples thereof include methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, and triethylene glycol monomethyl ether. , triethylene glycol monoethyl ether, triethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether and other alcohol solvents; acetone, methyl ethyl ether ketone-based solvents such as methyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and trimethylbenzene; including formamide, N-methylformamide, Nitrogen-containing solvents including amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; Sulfur atom-containing solvents including sulfite-based solvents; ester-based solvents such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, and the like. Among them, from the viewpoint of solubility, alcohol-based solvents, ketone-based solvents, and nitrogen-atom-containing solvents are preferred, and methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl ethyl ketone, methyl ethyl ketone, methyl ethyl ketone, methyl ethyl ketone, methyl ethyl ketone, methyl ethyl ketone, methyl Cellulose and propylene glycol monomethyl ether, more preferably methyl ethyl ketone and methyl isobutyl ketone, and particularly preferably methyl ethyl ketone. An organic solvent may be used individually by 1 type, and may use 2 or more types together.

In the thermosetting resin composition [I] (resin varnish), the content of the organic solvent may be appropriately adjusted to such an extent that the thermosetting resin composition [I] can be easily handled, and the content of the organic solvent may be adjusted appropriately in the coating of the resin varnish. There is no particular limitation as long as the cloth properties are within a good range, but the solid content concentration (the concentration of components other than the organic solvent) derived from the thermosetting resin composition [I] is preferably 30 to 90% by mass, more preferably It is 40-80 mass %, More preferably, it is 50-80 mass %.

Next, each component contained in the epoxy resin composition [II] will be described in detail. Furthermore, in order to avoid duplication with the aforementioned thermosetting resin composition [I], the epoxy resin composition [II] may not contain the (A) maleimide compound contained in the thermosetting resin composition [I], but The above-mentioned (A) maleimide compound may be contained without being particularly limited to this aspect.

<(G) Epoxy resin> As (G) epoxy resin contained in epoxy resin composition [II], the same epoxy resin as (B) epoxy resin in said thermosetting resin composition [I] is mentioned, for example, and the description is also same. Among these, preferred are epoxy resins made of bisphenol F type, phenol novolac type epoxy resin, cresol novolak type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin At least one selected from the group consisting of epoxy resins, biphenyl aralkyl novolac-type epoxy resins, and dicyclopentadiene-type epoxy resins, from the viewpoints of low thermal expansion and high glass transition temperature, More preferably, it is composed of 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 novolak type epoxy resin. At least one kind selected from the group consisting of oxygen resins, more preferably biphenyl aralkyl novolak type epoxy resin.

<(H) Epoxy resin hardener> As an epoxy resin hardening|curing agent, various phenol resin compounds, acid anhydride compounds, amine compounds, hydrazine compounds, etc. are mentioned, for example. As the phenolic resin compound, for example, novolak-type phenolic resin, resol-type phenolic resin, etc. are mentioned; as the acid anhydride compound, for example, phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl Nadic Acid et al. Moreover, as an amine compound, dicyandiamide, diaminodiphenylmethane, guancarbazide, etc. are mentioned, for example. Among these epoxy resin hardeners, from the viewpoint of improving reliability, novolak-type phenol resins are preferred, and cresol novolak resins are preferred.

Commercially available novolak-type phenol resins can be used, and examples thereof include phenol novolak resins such as "TD2090" (manufactured by DIC Co., Ltd., trade name); "KA-1165" (manufactured by DIC Corporation, trade name), etc. Cresol novolac resin, etc. In addition, commercially available products such as "PHENOLITE LA-1356" (manufactured by DIC Co., Ltd., trade name) and "PHENOLITE LA7050 series" (manufactured by DIC Co., Ltd., trade name) such as triazine ring-containing novolak-type phenol resins can be mentioned. For example, a triazine cresol-containing novolak resin such as "PHENOLITE LA-3018" (manufactured by DIC Co., Ltd., trade name) is commercially available.

The epoxy resin composition [II] may contain (I) a hardening accelerator and (J) an inorganic filler as needed. <(I) Hardening accelerator> The epoxy resin composition [II] preferably contains (I) a curing accelerator from the viewpoint of promoting the reaction of the (G) epoxy resin and the (H) epoxy resin hardener. As (I) hardening accelerators, for example, imidazole compounds such as 2-phenylimidazole, 2-ethyl-4-methylimidazole, and 1-cyanoethyl-2-phenylimidazolium trimellitic acid; Organophosphorus compounds such as triphenylphosphine; onium salts such as phosphonium borate; amines such as 1,8-diazabicycloundecene; 3-(3,4-dichlorophenyl)-1,1-dimethylurea Wait. These may be used individually by 1 type, and may use 2 or more types together. Among these, an imidazole compound is preferable, and 2-ethyl-4-methylimidazole is preferable.

<(J) Inorganic Filler> From the viewpoint of reducing thermal expansion, the epoxy resin composition [II] preferably contains (J) an inorganic filler. (J) Inorganic fillers include, for example, silicon oxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, boric acid Aluminum, barium titanate, strontium titanate, calcium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, etc. These may be used individually by 1 type, and may use 2 or more types together. Among them, silicon oxide 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 more preferably 0.3 μm or more. The inorganic filler material may be subjected to surface treatment. For example, when silicon oxide is used as an inorganic filler, a silane coupling agent treatment can be performed as a surface treatment. As a silane coupling agent, an amino silane coupling agent, a vinyl silane coupling agent, an epoxy silane coupling agent, etc. are mentioned, for example. Among these, silicon oxide after 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 the content of the components (G) is preferably 100 parts by mass of the total of the components (G) to (J). 5-50 mass parts, (H) component is 5-50 mass parts, (I) component is 0.001-1 mass part, (J) component is 20-80 mass parts. More preferably, the (G) component is 5 to 35 parts by mass, the (H) component is 5 to 40 parts by mass, and the (I) component is 0.001 to 1 with respect to 100 parts by mass of the total of the (G) to (J) components. The mass parts and (J) component are 35-80 mass parts.

(other ingredients) The epoxy resin composition [II] can contain other components such as additives and organic solvents as necessary within a range that does not impair the effects of the present invention. These may be contained individually by 1 type, and may contain 2 or more types.

(additive) Examples of additives include colorants, antioxidants, reducing agents, ultraviolet absorbers, optical brighteners, adhesion improvers, organic fillers, and the like. These may be used individually by 1 type, and may use 2 or more types together.

(Organic solvents) The description of the organic solvent is the same as the description of the organic solvent in the thermosetting resin composition [I].

Next, each component contained in the thermosetting resin composition [III] will be described in detail. ＜(K) Siloxane-modified maleimide compound＞ (K) The siloxane-modified maleimide compound is not particularly limited as long as it is a maleimide compound having a siloxane skeleton. Preferably, for example: a maleimide compound (k-1) having at least two N-substituted maleimide groups in one molecule [hereinafter, also referred to as a maleimide compound (k-1) )] and a siloxane compound (k-2) [hereinafter, also referred to as siloxane compound (k-2)] having at least two primary amine groups in one molecule, etc., preferably a horse An addition reaction product of a lyimide compound (k-1), a siloxane compound (k-2) and a monoamine compound [hereinafter also referred to as a monoamine compound (k-3)]. As the maleimide compound (k-1), the same as the maleimide compound (a1) in the description of the (A) maleimide compound in the thermosetting resin composition [I] can be used compound of. The siloxane compound (k-2) preferably contains a structural unit represented by the following general formula (k-2-1).

通式(k-2-1)中，R ^k1及R ^k2各自獨立地表示碳數1～5的烷基、苯基、或具有取代基之苯基。

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

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^k1 and R ^k2 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl Base et al. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, preferably a methyl group. In the "substituted phenyl group", examples of the substituent which the phenyl group has 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 include the same alkyl groups as described above. Examples of the alkenyl group having 2 to 5 carbon atoms include a vinyl group, an allyl group, and the like. Examples of the alkynyl group having 2 to 5 carbon atoms include an ethynyl group, a propargyl group, and the like. Both R ^k1 and R ^k2 are preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group.

The siloxane compound (k-2) is preferably a siloxanediamine represented by the following general formula (k-2-2).

通式(k-2-2)中，R ^k1及R ^k2與通式(k-2-1)中的R ^k1及R ^k2相同；R ^k3及R ^k4各自獨立地表示碳數1～5的烷基、苯基、或具有取代基之苯基；R ^k5及R ^k6各自獨立地表示2價有機基，m為2～100的整數。

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

The description of the alkyl group having 1 to 5 carbon atoms, the phenyl group, and the substituted phenyl group represented by R ^k3 and R ^k4 are the same as those of R ^k1 and R ^k2 . R ^k3 and R ^k4 are preferably methyl groups. Examples of the divalent organic group represented by R ^k5 and R ^k6 include an alkylene group, an alkenylene group, an alkynylene group, an arylidene group, -O-, a divalent linking group formed by combining these, and the like. . Examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms such as a methylene group, an ethylidene group, and a propylidene group. As the alkenylene group, for example, an alkenylene group having 2 to 10 carbon atoms is mentioned. Examples of the alkynylene group include alkynylene groups having 2 to 10 carbon atoms. Examples of the arylidene group include arylidene groups having 6 to 20 carbon atoms, such as a phenylene group and a naphthylene group. Among these, R ^k5 and R ^k6 are preferably an alkylene group or an aryl group. m is preferably an integer of 2-50, more preferably an integer of 3-40, more preferably an integer of 5-30, still more preferably an integer of 7-30.

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

As a siloxane compound (k-2), a commercial item can be used. Commercially available products include, for example: "KF-8010" (the functional group equivalent of the amine group is 430 g/mol), "X-22-161A" (the functional group equivalent of the amine group is 800 g/mol), "X- 22-161B” (the functional group equivalent of the amine group is 1,500 g/mol), “KF-8012” (the functional group equivalent of the amine group is 2,200 g/mol), “KF-8008” (the functional group equivalent of the amine group is 5,700 g/mol), "X-22-9409" (the functional group equivalent of the amine group is 700 g/mol), "X-22-1660B-3" (the functional group equivalent of the amine group is 2,200 g/mol) ( The above are manufactured by Shin-Etsu Chemical Co., Ltd.); "BY-16-853U" (the functional group equivalent of the amine group is 460 g/mol), "BY-16-853" (the functional group equivalent of the amine group is 650 g/mol) mol), "BY-16-853B" (the functional group equivalent of the amine group is 2,200 g/mol) (the above are manufactured by Dow Corning Toray Co., Ltd.); "XF42-C5742" (the functional group equivalent of the amine group is 1,280 g) /mol), "XF42-C6252" (the functional group equivalent of the amine group is 1,255 g/mol), "XF42-C5379" (the functional group equivalent of the amine group is 745 g/mol) (the above are Momentive Performance Materials Japan Co., Ltd. system) etc. 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 above-mentioned thermosetting resin composition [I] can be used, and the preferred examples are also the same.

As described above, one aspect of the (K) siloxane-modified maleimide compound can be produced by using the maleimide compound (k-1) and the siloxane compound described above. (k-2) is reacted with the monoamine compound (k-3) according to need. From the viewpoints of preventing gelation and heat resistance, in this reaction, the maleimide compound (k-1), the siloxane compound (k-2), and the monoamine compound (k- 3) The respective usage ratios, preferably: the maleimide group equivalent of the maleimide compound (k-1) exceeds the siloxane compound (k-2) and the monoamine compound (k-3) The sum of the equivalents of the primary amine groups of the The ratio of the sum of the equivalents of the amine groups, that is, (k-1)/[(k-2)+(k-3)] is preferably 1 to 15, more preferably 2 to 10, and more preferably 3 to 10. From the viewpoint of productivity and uniform reaction, the reaction temperature is preferably 70 to 150°C, and more preferably 90 to 130°C. In addition, the reaction time is not particularly limited, but is preferably 0.1 to 10 hours, more preferably 1 to 6 hours.

<(L) Imidazole compound> As the (L) imidazole compound, for example, 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1,2-diazole Methylimidazole, 2-ethyl-1-methylimidazole, 1,2-diethylimidazole, 1-ethyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl -2-methylimidazole, 1-isobutyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2- Methylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl- 4,5-Dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 2 ,4-Diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazole yl-(1')]ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyl-s- Imidazole compounds such as triazine; modified imidazole compounds such as isocyanato-shielded imidazole and epoxy-shielded imidazole; the aforementioned imidazole compounds such as trimellitic acid 1-cyanoethyl-2-phenylimidazolium salt and trimellitic acid salts of the aforementioned imidazole compounds; salts of the aforementioned imidazole compounds and isocyanuric acid; salts of the aforementioned imidazole compounds and hydrobromic acid, etc. Among these, a modified imidazole compound is preferable, and an isocyanate group-shielded imidazole is preferable. An imidazole compound may be used individually by 1 type, and may use 2 or more types together.

<(M) Inorganic Filler> The description of the (M) inorganic filler is the same as the description of the (J) inorganic filler in the aforementioned 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 the content of the components (K) is preferably 100 parts by mass of the total of the components (K) to (M). It is 15-80 mass parts, (L) component is 0.01-5 mass parts, (M) component is 15-80 mass parts. More preferably, the (K) component is 30 to 65 parts by mass, the (L) component is 0.01 to 3 parts by mass, and the (M) component is 30 to 65 parts by mass relative to 100 parts by mass of the total of the (K) to (M) components. parts by mass.

(other ingredients) The thermosetting resin composition [III] can contain other components such as additives and organic solvents as necessary within a range that does not impair the effects of the present invention. These may be contained individually by 1 type, and may contain 2 or more types.

(additive) Examples of additives include colorants, antioxidants, reducing agents, ultraviolet absorbers, optical brighteners, adhesion improvers, organic fillers, and the like. These may be used individually by 1 type, and may use 2 or more types together.

(Organic solvents) The description of the organic solvent is the same as the description of the organic solvent in the thermosetting resin composition [I].

[prepreg] The prepreg obtained by the production method of the present invention has a small variation in the amount of dimensional change, and when the above-mentioned thermosetting resin composition is used, high heat resistance, high metal foil adhesion, high glass transition temperature, and low glass transition temperature are obtained. It is also excellent in thermal expansion property, formability, and throwing property (laser workability).

Further, according to the present invention, the following prepreg can be provided. The prepreg obtained by the manufacturing method of this 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 wherein the standard deviation σ obtained by the following method is 0.012% or less, How to calculate the standard deviation σ: A copper foil with a thickness of 18 μm is superimposed on both sides of a prepreg, and heated and pressed for 90 minutes under the conditions of 190°C and 2.45 MPa to produce a double-sided copper-clad laminate with a thickness of 0.1 mm; For the double-sided copper-clad laminate obtained in the above-mentioned manner, holes with a diameter of 1.0 mm were implemented at 1 to 8 points in the surface of the double-sided copper-clad laminate as described in Fig. 1; The vertical line direction, which is the direction of 1-7, 2-6, and 3-5, and the horizontal line direction, which is the direction of 1-3, 8-4, and 7-5, are three points each, using an image measuring machine. After measuring the distance between each 3 points, each measurement distance was set as an initial value; then, the outer layer copper foil was removed, and heated at 185°C for 60 minutes in a dryer; after cooling, the initial value was measured with The direction of the method is the same, to the direction of the vertical line, that is, the direction of 1-7, 2-6, 3-5, and the direction of the horizontal line, that is, the direction of 1-3, 8-4, 7-5. The distance is measured; the average value of these rates of change is calculated based on the rate of change with respect to the initial value of each measurement distance [(measured value after heat treatment - initial value) × 100/initial value], and calculated relative to The standard deviation σ of this mean. The image measuring machine is not particularly limited, and for example, "QV-A808P1L-D" (manufactured by Mitutoyo Corporation) can be used.

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

[laminated board] The laminate of the present invention includes the aforementioned prepreg and metal foil. It can be produced, for example, by using one sheet of the prepreg, or by stacking 2 to 20 sheets of the prepreg according to need, and laminating and molding the metal foil on one or both sides of the prepreg. . In addition, the laminated board in which the metal foil is arrange|positioned may be called a metal-clad laminated board. The metal of the metal foil is not particularly limited as long as it is a metal used for an electrical insulating material. From the viewpoint of electrical conductivity, the metal of the metal foil is preferably copper, gold, silver, nickel, platinum, molybdenum, and ruthenium. , aluminum, tungsten, iron, titanium, chromium, or an alloy containing at least one of these metal elements, more preferably copper, aluminum, and still more preferably copper. The forming conditions of the laminate can be applied to the conventional forming methods of laminates and multilayer boards for electrical insulating materials. For example, multi-stage pressing, multi-stage vacuum pressing, continuous forming, autoclave forming machine, etc. , the pressure is 0.2 to 10 MPa, and the heating time is 0.1 to 5 hours to form. Moreover, a multilayer board can also be manufactured by combining the prepreg of the present invention and the printed wiring board for inner layers, laminating and molding. The thickness of the metal foil is not particularly limited, and may be appropriately selected according to the application of the printed wiring board and the like. The thickness of the metal foil is preferably 0.5 to 150 μm, preferably 1 to 100 μm, more preferably 5 to 50 μm, and particularly preferably 5 to 30 μm.

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

[Printed Wiring Board] The present invention also provides a printed wiring board comprising the prepreg or the laminate. The printed wiring board of the present invention can be produced by subjecting the metal foil of the metal-clad laminate to circuit processing. Circuit processing can be performed by, for example, the following methods: after forming a resist pattern on the surface of the metal foil, the excess metal foil is removed by etching, and after peeling off the resist pattern, a drill is used to form the required penetrations. After forming a hole and forming a resist pattern again, plating for conduction is performed on the through hole, and finally the resist pattern is peeled off. A multilayer printed wiring board can be produced by further laminating the above metal-clad laminate on the surface of the printed wiring board obtained above under the same conditions as above, and further performing circuit processing in the same manner as above. At this time, it is not necessary to form a through hole, a through hole may be formed, and both of them may be formed. Such multi-layering is the number of sheets required to perform.

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

Next, the present invention is described in more detail by the following examples, but these examples are not intended to limit the present invention in any sense. The thermosetting resin composition of the present invention is used to produce: a resin varnish, a prepreg precursor obtained by using the resin varnish, and a prepreg obtained by subjecting the prepreg precursor to surface heat treatment, and further produced After the copper clad laminate, the prepared copper clad laminate was evaluated. The evaluation method is as follows.

[assessment method] <1. Heat resistance (reflow heat resistance)> Using the four-layer copper clad laminate obtained in each example, and setting the maximum temperature at 266°C, the four-layer copper-clad laminate was allowed to flow in a constant temperature bath environment of 260°C or higher for 30 seconds to set one cycle, and the number of cycles until the expansion of the substrate can be visually confirmed was obtained. The higher the number of cycles, the better the heat resistance.

<2. Relative permittivity (Dk)> Using a network analyzer "8722C" (manufactured by HP), the relative permittivity of a 1 GHz double-sided copper-clad laminate was measured by a three-plate structure linear line resonator method. The size of the test piece is 200 mm × 50 mm × thickness 0.8 mm, and a straight line (line length 200 mm) with a width of 1.0 mm is formed in the center of one side of a double-sided copper-clad laminate by etching, and copper remains The entire rear surface is set as a ground layer. For another double-sided copper-clad laminate, etch the entire surface of one side, and set the back side as the ground layer. These two double-sided copper-clad laminates were superimposed so that the ground layer was outside, and a strip line was produced. Measurements are performed at 25°C. The smaller the relative permittivity, the better.

<3. Metal foil adhesion (copper foil peel strength)> Metal foil adhesion was evaluated by copper foil peel strength. An evaluation board was produced by immersing the double-sided copper-clad laminate obtained in each example in a copper etching solution "ammonium persulfate (APS)" (manufactured by ADEKA Co., Ltd.) to form a copper foil with a width of 3 mm. , and used the autoclave "AG-100C" (manufactured by Shimadzu Corporation) to measure the peel strength of the copper foil. The larger the value, the more excellent the metal foil adhesiveness is.

<4. Glass transition temperature (Tg)> By immersing the double-sided copper-clad laminate obtained in each example in a copper etching solution "ammonium persulfate (APS)" (manufactured by ADEKA Co., Ltd.), the copper foil was removed, and an evaluation of 5 mm square was produced. The substrate was used to observe and evaluate the thermal expansion characteristics of the substrate in the plane direction (Z direction) at 30 to 260°C using a thermomechanical analysis (TMA) test apparatus "Q400EM" (manufactured by TA instruments), and the inverse inflection point of the amount of expansion was calculated. Set to glass transition temperature.

<5. Low thermal expansion> The copper foil was removed by immersing the double-sided copper-clad laminate obtained in each example in a copper etching solution "ammonium persulfate (APS)" (manufactured by ADEKA Co., Ltd.), Then, an evaluation substrate of 5 mm square was produced, and the thermal expansion coefficient (linear expansion coefficient) in the plane direction of the evaluation substrate was measured using a TMA test apparatus "Q400EM" (manufactured by TA instruments). In addition, in order to remove the influence of the thermal strain possessed by the sample, after repeating the heating-cooling cycle twice, the thermal expansion coefficient [ppm/°C] from 30°C to 260°C in the temperature shift chart for the second time was measured, and set as It is an indicator of low thermal expansion. The smaller the value, the more excellent the low thermal expansion property. In addition, in the table, the thermal expansion coefficient when Tg is not reached (indicated as "<Tg") and the thermal expansion coefficient in excess of Tg (indicated as ">Tg") are separately described. Measurement conditions ^1st Run: Room temperature→210°C (heating rate 10°C/min) ^2nd Run: 0°C→270°C (heating rate 10°C/min) Copper clad laminates are expected to be further thinned, and this is also the case It is desired and research is being conducted to reduce the thickness of a prepreg for forming a copper-clad laminate. Since the thinned prepreg tends to warp, it is desirable that the warpage of the prepreg during heat treatment is small. In order to reduce warpage, it is effective to make the thermal expansion coefficient of the base material in the plane direction small.

<6. Throwing property (laser workability)> For the four-layer copper-clad laminates obtained in each example, a laser machine "LC-2F21B/2C" (manufactured by Hitachi Via Mechanics Co., Ltd.) was used. Laser drilling was performed by the copper direct method with a target aperture of 80 μm, Gaussian, and cyclic mode, a pulse width of 15 μs×1 time, and 7 μs×4 times. For the obtained laser holed substrate, a swelling liquid "Swelling Dip Securiganth P" (manufactured by Atotech Japan Co., Ltd.) was used at 70°C for 5 minutes, and a roughening liquid "Dosing" was used at 70°C for 9 minutes. Securiganth P500J" (manufactured by Atotech Japan Co., Ltd.) was subjected to desmear treatment using a neutralizing solution "Reduction Conditioner Securiganth P500" (manufactured by Atotech Japan Co., Ltd.) at 40°C for 5 minutes. Then, the electroless plating solution "Priganth MSK-DK" (manufactured by Atotech Japan Co., Ltd.) was used for 20 minutes at 30°C, and the plating solution "Cupracid HL" (Atotech Japan Co., Ltd.) was used at 24°C and 2 A/dm ² Co., Ltd.) for 2 hours to perform plating on the laser-processed substrate. Cross-sectional observation of the obtained laser holed substrate was carried out, and the throwing property was confirmed. As a method for evaluating the leveling property, the leveling property is preferably that the difference between the thickness of the coating on the upper part of the laser hole and the thickness of the coating on the bottom of the laser hole is within 10% of the thickness of the coating on the upper part of the laser hole. Therefore, The presence ratio (%) of pores included in this range in 100 pores was determined.

<7. Formability> For the four-layer copper-clad laminates obtained in each example, after removing the outer layer copper, the presence or absence of holes and scratches in a surface of 340 mm × 500 mm was visually confirmed, and the formability was used as an index. "Good" was indicated when there were no holes and scratches, and the situation was indicated when there were holes or scratches. It can be said that the formability is good when there are no holes or scratches.

<8. Evaluation of Variation in Dimensional Change> For the double-sided copper-clad laminates obtained in each example, a hole having a diameter of 1.0 mm was implemented as shown in FIG. 1 . As described in Figure 1, the vertical direction of the glass cloth is the direction of 1-7, 2-6, 3-5 and the horizontal direction is the direction of 1-3, 8-4, 7-5. At each of three points, the distance between each of the three points was measured using a video measuring machine "QV-A808P1L-D" (manufactured by Mitutoyo Co., Ltd.), and each measured distance was set as an initial value. Then, the outer layer copper foil was removed and heated at 185° C. for 60 minutes with a dryer. After cooling, in the same manner as the measurement method of the initial value, the vertical line directions, that is, the directions of 1-7, 2-6, and 3-5, and the horizontal line directions, that is, 1-3, 8-4, and 7- The distance between each 3 points in the 5 directions was measured. The average value of these rates of change is obtained from the rate of change with respect to the initial value of each measurement distance [(measured value - initial value) × 100/initial value], and the standard deviation σ from the average value is calculated. The standard deviation σ is used as an index of the variation in the amount of dimensional change. A smaller value of the standard deviation σ means that the variation in the amount of dimensional change is smaller, which is preferable.

Hereinafter, each component used in an Example and a comparative example is demonstrated.

(A) component: The solution of the maleimide compound (A) produced in the following production example 1 was used. [Production Example 1] In a reaction vessel with a volume of 1 L equipped with a thermometer, a stirring device, and a moisture analyzer equipped with a reflux cooling tube, 19.2 g of 4,4'-diaminodiphenylmethane, bis(4-maleimide) were added. 174.0 g of phenyl)methane, 6.6 g of p-aminophenol, and 330.0 g of dimethylacetamide were reacted at 100° C. for 2 hours to obtain an acidic substituent and N-substituted maleimide The dimethylacetamide solution of the maleimide compound (A) (Mw=1,370) of the base was used as the (A) component. In addition, the said weight average molecular weight (Mw) was converted from the calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve is using standard polystyrene: TSK standard POLYSTYRENE (Model: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [Tosoh Co., Ltd.] is approximated by a cubic equation. The conditions of GPC are as follows. Device: (Pump: Model L-6200 [manufactured by Hitachi High-Technologies Co., Ltd.]), (Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Co., Ltd.]), (Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Co., Ltd.]) Column: TSKgel SuperHZ2000 + TSKgel SuperHZ2300 (both are manufactured by Tosoh Corporation) String size: 6.0×40 mm (protection string), 7.8×300 mm (string) Elution solution: tetrahydrofuran Sample concentration: 20 mg/5 mL Injection volume: 10 μL Flow: 0.5 mL/min Measurement temperature: 40℃

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

(D) Component: fused silica (average particle size: 1.9 μm, specific surface area: 5.8 m ² /g) treated with an aminosilane-based coupling agent Other inorganic fillers: “F05-30” (not Processed pulverized silica, average particle size: 4.2 μm, specific surface area 5.8 m ² /g, manufactured by Fukushima Kiln Co., Ltd.)

(E) Component: Dicyandiamide (manufactured by Nippon Carbide Industrial Co., Ltd.) (F) Component: "PX-200" (aromatic phosphate ester (refer to the following structural formula), manufactured by Daihachi Chemical Industry Co., Ltd.)

[Examples 1 to 13, Comparative Examples 1 to 4] Each component shown above is prepared like the following Tables 1 to 4 (wherein, in the case of a solution, it represents the amount in terms of solid content), and additionally added so that the nonvolatile content of the solution becomes 65 to 75% by mass methyl ethyl ketone, and resin varnishes were prepared for the thermosetting resin compositions of the respective Examples and Comparative Examples. Each obtained resin varnish was impregnated into a glass cloth (0.1 mm) of IPC specification #3313, dried for 4 minutes using a flat heater set at a temperature of 160° C. to perform B-staging (step 1), and then placed in a room. The temperature (about 20°C) was left to cool (step 2) to obtain a prepreg precursor. In addition, in the comparative example, it used as a prepreg as it is while maintaining the state of the prepreg precursor. In each example, the obtained prepreg precursor was subjected to surface heat treatment (product surface temperature of 70°C) for 3 seconds using a plate heater with the surface heating temperature set at 500°C, and then cooled until room temperature (approximately 70°C). 20°C) to prepare a prepreg (step 3).

(Fabrication and performance evaluation of double-sided copper-clad laminate) After stacking 8 pieces of the aforementioned prepreg, copper foil "3EC-VLP-18" (manufactured by Mitsui Metals Co., Ltd.) with a thickness of 18 μm was stacked on both sides of the prepreg. , and heated and pressed for 90 minutes at a temperature of 190°C and a pressure of 25 kgf/cm ² (2.45 MPa) to produce a double-sided copper-clad laminate with a thickness of 0.8 mm (8 pieces of prepreg), using the copper-clad laminate. The laminates were measured and evaluated for relative permittivity, metal foil adhesion, glass transition temperature (Tg), and low thermal expansion according to the aforementioned methods. In addition, copper foil "3EC-VLP-18" (manufactured by Mitsui Metals Co., Ltd.) with a thickness of 18 μm was superimposed on both sides of a prepreg, and was heated at 190°C and a pressure of 25 kgf/cm ² (2.45 MPa). ) for 90 minutes by heating and pressing to form a double-sided copper-clad laminate with a thickness of 0.1 mm (1 prepreg), and then using the double-sided copper-clad laminate to measure and evaluate the dimensional change according to the method described above. deviation.

(Production and performance evaluation of four-layer copper-clad laminate) On the other hand, using one sheet of the prepreg described above, copper foil "YGP-18" (manufactured by Nippon Electron Co., Ltd.) with a thickness of 18 μm was laminated on both sides of the prepreg. , and heated and pressed for 90 minutes at a temperature of 190°C and a pressure of 25 kgf/cm ² (2.45 MPa) to produce a double-sided copper-clad laminate with a thickness of 0.1 mm (1 piece of prepreg). The surface was subjected to inner layer adhesion treatment (using "BF treatment liquid" (manufactured by Hitachi Chemical Co., Ltd.)), and the copper foil "YGP- 18" (manufactured by Nippon Electron Co., Ltd.) was superimposed on both sides, and heated and press-molded for 90 minutes at a temperature of 190°C and a pressure of 25 kgf/cm ² (2.45 MPa) to produce a four-layer copper-clad laminate. Using this four-layer copper-clad laminate, the evaluation of heat resistance, throwing property, and formability was carried out according to the aforementioned method. The results are shown in Tables 1-4.

[Table 1]

[Table 2]

[table 3]

[Table 4]

[Example 14] Instead of preparing a resin varnish in Example 1, a resin varnish was prepared using the following components. 19 parts by mass of biphenyl aralkyl novolak epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-3000, epoxy equivalent: 280 to 300 g/eq), cresol novolak resin (DIC Co., Ltd., trade name: KA-1165, hydroxyl equivalent: 119 g/eq) 16 parts by mass, 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd.) 0.02 parts by mass, molten oxidation Silicon (Admatechs Co., Ltd., fused silica treated with an aminosilane coupling agent, average particle size: 2 μm) was mixed with 65 parts by mass, and diluted with a solvent (methyl ethyl ketone), thereby A resin varnish (solid content concentration: 70 mass %) was prepared. The other steps were carried out in the same manner as in Example 1, whereby a prepreg was obtained. Using the obtained prepreg, a double-sided copper-clad laminate was produced by the same method as in Example 1. After measuring and evaluating the deviation of the dimensional change using the double-sided copper-clad laminate, the standard deviation of the result was σ. The value is 0.010%.

[Example 15] Instead of preparing resin varnish in Example 1, resin varnish was prepared using the following components. KF-8010 (two-terminal amine-modified silicone oil, Shin-Etsu Chemical Industry Co., Ltd.) was added to a 2 L reaction vessel equipped with a stirring device, a moisture metering device equipped with a reflux cooling tube, and capable of heating and cooling. made) 75.7 g, bis(4-maleimidophenyl)methane (manufactured by Yamato Chemical Industry Co., Ltd., trade name: BMI-1000) 168.0 g, p-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) 6.4 g and 250.0 g of a solvent (methyl ethyl ketone) were reacted at 100° C. for 3 hours to obtain a siloxane-modified maleimide compound. 49.5 parts by mass of the siloxane-modified maleimide compound, 50 parts by mass of fused silica (made by Admatechs Co., Ltd., fused silica treated with an aminosilane coupling agent), and an isocyanato group A resin varnish (solid content concentration: 70% by mass) was prepared by mixing 0.5 parts by mass of masking imidazole (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., trade name: G-8009L) and diluting it with a solvent (methyl ethyl ketone). ). The other steps were carried out in the same manner as in Example 1, whereby a prepreg was obtained. Using the obtained prepreg, a double-sided copper-clad laminate was produced by the same method as in Example 1. After measuring and evaluating the deviation of the dimensional change using the double-sided copper-clad laminate, the standard deviation of the result was σ. The value is 0.009%.

From the above-mentioned results, the following facts are known. In the examples, since the surface heat treatment was performed on the prepreg precursor, the standard deviation σ was reduced more than that of the comparative example in which the surface heat treatment was not performed, and the variation in the dimensional change amount could be sufficiently suppressed. In addition, in Examples 1 to 13, the reflow heat resistance reached 10 cycles or more of the heat resistance requirement level or more, low relative permittivity, high metal foil adhesion, and high glass transition temperature were obtained, and low thermal expansion was exhibited. In addition, since the glass cloth protruded from the wall surface and had a moderately roughened shape, it was confirmed that it had good throwing properties. In terms of formability, the embedding property of the resin was also good, and abnormalities such as scratches and holes could not be confirmed. Among them, compared with Examples 11 to 13, in Examples 1 to 10, the relative permittivity and metal foil adhesion were more favorable, and other characteristics were also stably exhibited. [Industrial Availability]

The prepreg obtained by the present invention and the laminate including the prepreg have small variation in the amount of dimensional change, and thus are useful as printed wiring boards for electronic equipment.

FIG. 1 is a schematic diagram of an evaluation substrate used for measuring the variation of the dimensional change in the Example.

Domestic storage information (please note in the order of storage institution, date and number) none

Foreign deposit information (please mark in the order of deposit country, institution, date and number) none

Claims (20)

A method of manufacturing a prepreg, comprising: After impregnating the base material with the thermosetting resin composition, the thermosetting resin composition is B-staged to obtain a prepreg precursor; and, a surface heat treatment step performed after the aforementioned step of obtaining the prepreg precursor; In addition, 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 of manufacturing a prepreg, comprising: After impregnating the base material with the thermosetting resin composition, the thermosetting resin composition is B-staged to obtain a prepreg precursor; and, a surface heat treatment step performed after the aforementioned step of obtaining the prepreg precursor; Moreover, the said surface heat processing process is a process of heat-processing the surface of a prepreg precursor so that the surface temperature of a prepreg precursor may become 40-130 degreeC. The method for manufacturing a prepreg according to claim 1 or 2, wherein after the step of obtaining the prepreg precursor and before the surface heat treatment step, the prepreg precursor is cooled to 5-60°C °C steps. The method for producing a prepreg according to any one of claims 1 to 3, wherein the time for 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 method for producing a prepreg according to claim 5, wherein the component (A) is a maleimide compound having an N-substituted maleimide group, wherein (a1) has at least two N-substituted maleimide group maleimide compound, (a2) monoamine compound represented by following general formula (a2-1) and (a3) represented by following general formula (a3-1) The diamine compound is reacted to obtain;

In the general formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group and a sulfonic acid group, R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, and t is an integer of 1 to 5 , u is an integer from 0 to 4 and satisfies 1≦t+u≦5, where, when t is an integer from 2 to 5, a plurality of R ^A4 may be the same or different, and in addition, when u is an integer from 2 to 4 , a plurality of R ^A5 can 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-, and R ^A6 and R ^A7 each independently represent an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, and a carboxyl group. or a sulfonic acid group, v and w are each independently an integer of 0-4. The method for producing a prepreg according to claim 5 or 6, wherein the thermosetting resin composition further contains: (B) 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) Silicon oxide treated with an aminosilane-based coupling agent. The method for producing a prepreg according to claim 7, wherein the component (B) is made from bisphenol F epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, naphthalene At least one selected from the group consisting of epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl novolac type epoxy resin, and dicyclopentadiene type epoxy resin . The method for producing a prepreg according to claim 7 or 8, wherein the component (C) has a structural unit represented by the following general formula (Ci) and a structural unit represented by the following general formula (C-ii) Copolymer resin of structural unit:

In formula (Ci), 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, and an aryl group having 6 to 20 carbon atoms. , a hydroxyl group, or a (meth)acryloyl group, and x is an integer of 0 to 3, wherein when x is 2 or 3, a plurality of R ^C2 may be the same or different. A prepreg comprising a base material and a thermosetting resin composition, and wherein the standard deviation σ obtained by the following method is 0.012% or less, How to calculate the standard deviation σ: A copper foil with a thickness of 18 μm is superimposed on both sides of a prepreg, and heated and pressed for 90 minutes under the conditions of 190°C and 2.45 MPa to produce a double-sided copper-clad laminate with a thickness of 0.1 mm; For the double-sided copper-clad laminate obtained in the above-mentioned manner, holes with a diameter of 1.0 mm were implemented at 1 to 8 points in the surface of the double-sided copper-clad laminate as described in Fig. 1; The vertical line direction, which is the direction of 1-7, 2-6, and 3-5, and the horizontal line direction, which is the direction of 1-3, 8-4, and 7-5, are three points each, using an image measuring machine. After measuring the distance between each 3 points, each measurement distance was set as an initial value; then, the outer layer copper foil was removed, and heated at 185°C for 60 minutes in a dryer; after cooling, the initial value was measured with In the same way, the vertical line direction is the direction of 1-7, 2-6, 3-5 and the horizontal line direction is the direction of 1-3, 8-4, 7-5. The distance is measured; the average value of the change rates is obtained from the change rate relative to the initial value of each measurement distance, and the standard deviation σ with respect to the average value is calculated. The prepreg according to claim 10, which is obtained by the manufacturing method of the prepreg 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 prepreg according to claim 10 or 12, wherein the thermosetting resin composition further contains: (B) 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) Silicon oxide treated with an aminosilane-based coupling agent. 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 contains (K) a siloxane-modified maleimide compound and (L) an imidazole compound. A laminate comprising the prepreg described in any one of claims 10 to 15 and a metal foil. A printed wiring board comprising the prepreg described in any one of claims 10 to 15 or the laminate described in claim 16. A semiconductor package is formed by mounting a semiconductor element on the printed wiring board described in 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 siloxane-modified maleimide compound and (L) an imidazole compound.

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