TW201840664A - 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, laminated board, printed wiring board and semiconductor package

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

In recent years, miniaturization, weight reduction, and multifunctionalization of electronic devices have progressed. With this situation, large-scale integrated circuits (LSI), chip parts, and the like have been increasingly integrated, and their forms are also becoming multi-pin. And rapid changes in miniaturization. Therefore, in order to increase the mounting density of electronic parts, the development of fine wiring of multilayer printed wiring boards has continued to progress. As a manufacturing method of a multilayer printed wiring board that meets these requirements, for example, a multi-layer printed wiring board of an extension method is gradually becoming mainstream as a method suitable for weight reduction, miniaturization, and micro-wiring. The expansion method is to use a prepreg. The circuit layer is formed by waiting as an insulating layer and connecting only a required portion. The required portion is, for example, a via hole (hereinafter, also referred to as a “laser via hole”) formed by irradiating a laser.

The important point of a multilayer printed wiring board is to have high electrical connection reliability and excellent high-frequency characteristics between a plurality of layers of circuit patterns formed at a fine line pitch, and reliable connection to a semiconductor wafer is required. High sex. In particular, in recent years, motherboards such as multifunctional mobile phone terminals include high-speed communication, high-density lines, extremely thin circuit boards, and line widths (L) and spaces (S) (hereinafter, In some cases, the line width and interval are combined and marked as [L / S]), which tends to narrow. With the narrowing of such L / S, it becomes difficult to stabilize the production of circuit boards with good yield. In addition, in the design of the conventional circuit board, a layer of a wireless circuit pattern called a "skip layer" is provided in a part of the layers in consideration of communication obstacles and the like. Electronic devices have gradually become highly functional and the amount of circuit design has gradually increased and the number of layers of the circuit board has gradually increased. However, the aforementioned skip layer is provided, which causes a problem that the thickness of the motherboard is further increased. As a method to improve these problems, a more effective method is to reduce the relative dielectric constant of the insulating material used in the circuit board. Because it is easy to control the impedance of L / S by reducing the relative dielectric constant of the insulating material, it is possible to stabilize production with a shape where L / S is close to the current design, and it is possible to reduce the number of layers by skipping layers. Therefore, with regard to insulating materials used in wiring boards, material characteristics with relatively low relative permittivity are currently being sought.

In recent years, motherboards such as mobile phones, which are becoming thinner and cheaper as electronic devices become denser, are also seeking materials with a lower relative permittivity in order to cope with the reduction in thickness. In addition, communication system devices such as servers, routers, and mobile base stations have gradually been used in higher frequency bands, and high-melting lead-free solders have been gradually used for soldering electronic parts. As a material of the substrate used among these, there is a tendency for a material having a low dielectric constant, a high glass transition temperature (high Tg), and excellent reflow heat resistance.

In addition, as motherboards used in multifunctional mobile phone terminals and the like increase in line density and narrow pattern widths, connection between layers is required to be connected through laser vias with small diameters. From the point of view of connection reliability, there are many examples where field plating is used, and the connectivity at the interface between the inner layer copper and the copper plating is very important. Therefore, there are also attempts to improve the lightning resistance of the substrate. Tendency to processability. Generally, after the substrate is subjected to laser processing, a step (desmear processing step) of removing the residue of the resin is performed. Because the slag removal treatment is performed on the bottom and wall surfaces of the laser through hole, when the resin component of the substrate is largely dissolved due to the slag removal treatment, the shape of the laser through hole may be significantly deformed due to the resin dissolution. In addition, there may be various problems such as unevenness of uniform plating due to variations in unevenness of the wall surface. Therefore, it is desirable to make the amount which is the amount by which the resin component of a base material melt | dissolves by performing a desmear process, and is what is called a desmear dissolve amount.

Among the various characteristics sought for insulating materials used in circuit boards, the following methods have been used so far for the purpose of reducing the relative dielectric constant: a method containing an epoxy resin with a small relative dielectric constant, and introduction of cyanide Acid group method, polyphenylene ether-containing method, and the like. For example, a resin composition containing an epoxy resin (see Patent Document 1), a resin composition containing polyphenylene ether and bismaleimide (see Patent Document 2), and a resin containing polyphenylene ether and a cyanate ester have been proposed. Resin composition (see Patent Document 3); resin composition containing at least one of a styrene-based thermoplastic elastomer and the like and / or triallyl cyanurate (see Patent Document 4); polybutylene Resin composition of diene (see Patent Document 5); formed by reacting a polyphenylene ether resin with a polyfunctional maleimide and / or a polyfunctional cyanate resin and a liquid polybutadiene in advance Resin composition (refer to Patent Document 6); polyphenylene ether obtained by supplying or grafting a compound having an unsaturated double bond group, and triallyl cyanurate and / or triallyl Resin composition such as isocyanurate (see Patent Document 7); resin composition containing polyphenylene ether and unsaturated carboxylic acid or unsaturated acid anhydride reaction product, and polyfunctional maleimide etc. (see Patent Document 8) and the like. [Prior Art Literature] (Patent Literature)

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

[Problems to be Solved by the Invention] As mentioned above, there is a tendency to reduce the relative dielectric constant and other characteristics of the insulating materials used in circuit boards. However, interlayer connection is achieved by a laser via having a small diameter. One of the most important characteristics is, for example, that the variation in the dimensional change of the prepreg is small. With the thinning of the motherboard, as a prepreg lamination method, a multi-stage lamination method is required, and the prepreg is subjected to multiple heating and pressure during lamination. Therefore, when the variation in the dimensional change amount of the prepreg (meaning the variation in the amount of thermal shrinkage) is large, the position of the through-hole used to connect the layers is deviated every time it is laminated. Therefore, it is desired to stabilize variations in the amount of thermal shrinkage of the prepreg. However, according to the research by the present inventors, it is known that the prepreg made of the conventional resin composition cannot sufficiently suppress the variation in the dimensional change, so there is still room for improvement in this regard.

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

The present inventors made efforts to solve the above-mentioned problem, and found that a prepreg can solve the above-mentioned problem, and then completed the present invention. The prepreg is obtained by going through the following steps. : After impregnating a thermosetting resin composition in a base material, performing B-stage conversion on the thermosetting resin composition to obtain a prepreg precursor, and then applying a predetermined heat source temperature to the surface of the prepreg precursor A heat treatment is performed to obtain a surface heat treatment of the prepreg. The present invention is completed based on such a technical idea.

The present invention relates to the following techniques [1] to [20]. [1] A method for producing a prepreg, the method comprising: after impregnating a thermosetting resin composition in a base material, performing a B-stage process on the thermosetting resin composition to obtain a prepreg precursor; And, a surface heating treatment step performed after the foregoing step of obtaining a prepreg precursor; and, the foregoing surface heating treatment step is a step of heating the surface of the prepreg precursor with a heat source temperature of 200 to 700 ° C; . [2] A method for producing a prepreg, the method comprising: after impregnating a thermosetting resin composition in a base material, performing a step B of the thermosetting resin composition to obtain a prepreg precursor And, a surface heating treatment step performed after the step of obtaining the prepreg precursor; and the surface heating treatment step is performed on the prepreg so that the surface temperature of the prepreg precursor is 40 to 130 ° C. The surface of the precursor is subjected to a heat treatment step. [3] The method for producing a prepreg according to the above [1] or [2], wherein after the step of obtaining a prepreg precursor and before the surface heating treatment step, the method includes: A step of cooling the product to 5 to 60 ° C. [4] The method for producing a prepreg according to any one of the above [1] to [3], wherein a time of 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, and (a1) A maleimide compound having at least two N-substituted maleimide groups, (a2) a monoamine compound represented by the following general formula (a2-1), and (a3) by the following general formula (a3 -1) obtained by reacting a diamine compound; 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 or a halogen atom having 1 to 5 carbon atoms, and t is an integer of 1 to 5 , U is an integer of 0 to 4 and satisfies 1 ≦ t + u ≦ 5, where when t is an integer of 2 to 5, the plurality of R ^A4 may be the same or different, and when u is an integer of 2 to 4 , The plurality of R ^A5 may be the same or different; In the general formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or -O-, 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 sulfonic acid groups, v and w are each independently an integer of 0 to 4. [7] The method for producing a prepreg according to the above [5] or [6], wherein the thermosetting resin composition further comprises: (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-type epoxy resin, a phenol novolac-type epoxy resin, and a cresol novolac-type ring. Selected from the group consisting of oxygen resin, naphthalene-type epoxy resin, anthracene-type epoxy resin, biphenyl-type epoxy resin, biphenylaralkyl novolac-type epoxy resin, and dicyclopentadiene-type epoxy resin 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 formula (Ci) C-ii) copolymer resin of structural unit: In the formula (Ci), R ^C1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, 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. , Hydroxy, or (meth) acrylfluorenyl, 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. [10] A prepreg comprising a base material and a thermosetting resin composition, and a standard deviation σ obtained in accordance with the following method is 0.012% or less, and a method of calculating the standard deviation σ: The thickness is 18 A copper foil of μm was superposed on both sides of a prepreg, and subjected to heat and pressure molding at 190 ° C and 2.45 MPa for 90 minutes to produce a double-sided copper-clad laminate having a thickness of 0.1 mm. The double-sided copper-clad laminated board obtained in the above manner is provided with openings having a diameter of 1.0 mm at 1 to 8 places described in FIG. 1 in the plane of the double-sided copper-clad laminated board; Each of the three points of 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 measuring the distance between 3 points, set each measurement distance to the initial value; then, remove the outer layer of copper foil and heat it at 185 ° C for 60 minutes with a dryer; after cooling, use the same method as the initial value measurement method Way, to each of the vertical direction is 1-7, 2-6, 3-5 and the horizontal direction is 1-3, 8-4, 7-5. The distance between the measuring; the rate of change with respect to the initial values of the distance measurement to an average value of such rate of change, and calculates the average value of the relative standard deviation of σ. [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 substitution derived from a substituted resin A structural unit of a vinyl compound and a structural unit derived from maleic anhydride; and (D) a 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 hardener. [15] The prepreg according to the above [10], wherein the thermosetting resin composition contains (K) a silicone modified maleimide compound and (L) an imidazole compound. [16] A laminated board comprising the prepreg according to any one of [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 laminated board according to the above [16]. [18] A semiconductor package obtained by mounting a semiconductor element on the printed wiring board described in [17] above. [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 hardening 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 silicon modified maleimide compound and (L) an imidazole compound. [efficacy]

According to the present invention, a method for manufacturing a prepreg can be provided, and the variation in 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 laminated board, a printed wiring board, and a semiconductor package, and the disadvantages of the positional deviation of the through holes rarely occur.

In the numerical range described in this specification, the upper limit value or lower limit value of the numerical range may be replaced with the value disclosed in the embodiment. 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 other numerical ranges, respectively. In addition, each component and material exemplified in the present specification may be used alone or in combination of two or more unless otherwise specified. In the present specification, when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified, it means the total amount of the plurality of substances present in the composition. The present invention also includes an aspect in which the matters described in this specification are arbitrarily combined.

[Manufacturing method of prepreg] The present invention is a method for manufacturing a prepreg, which comprises: 之后 impregnating a thermosetting resin composition in a base material, and then performing B-stage conversion on the thermosetting resin composition. A step of obtaining a prepreg precursor (step 1); and a surface heating treatment step (step 3) performed after the foregoing step of obtaining a prepreg precursor; and the foregoing step 3 is a heat source at 200 to 700 ° C A step of obtaining a prepreg by heating the surface of a prepreg precursor at a temperature. The foregoing step 3 can also be referred to as a surface heating treatment step, which is performed on the prepreg precursor so that the surface temperature of the prepreg precursor becomes 40 to 130 ° C. after the foregoing step of obtaining the prepreg precursor. The surface was heated to obtain a prepreg. Furthermore, it is generally preferred that after the step (step 1) of obtaining the prepreg precursor and before the step of surface heating treatment (step 3), the method has a method of cooling the prepreg precursor to 5 to 35 ° C. Step (step 2). Hereinafter, steps 1 to 3 will be described in order, and then a base material and a thermosetting resin composition for forming a prepreg will be described.

<Step 1> (1) Step 1 is a step of obtaining a prepreg precursor by impregnating a thermosetting resin composition into a base material and then subjecting the thermosetting resin composition to B-stage. The method of impregnating a thermosetting resin composition in a base material is not specifically limited, For example, a hot-melt method, a solvent method, etc. are mentioned. The hot-melt method is a method of directly impregnating a thermosetting resin composition that is reduced in viscosity by heating into a substrate. For example, the thermosetting resin composition is temporarily applied to a coating having excellent peelability. A method in which a resin film is formed by cloth or the like and then laminated on a substrate; a method in which a thermosetting resin composition is directly applied to the substrate using a die coater or the like. The solvent method is a method of impregnating a base material with a thermosetting resin composition containing an organic solvent to prepare a resin varnish, and for example, a method of immersing the base material in the resin varnish and then drying it.

By immersing a thermosetting resin composition in a base material and performing a heat treatment, it is possible to obtain a prepreg precursor in which the thermosetting resin composition is B-staged. Here, when the aforementioned hot-melt method is applied, the B-stage conversion can be performed simultaneously with heating when the aforementioned resin film is laminated on a substrate. In other words, the prepreg precursor can be obtained by performing the B-stage conversion of the thermosetting resin composition in such a manner that the resin film is heated on one side and an area layer on the substrate, and the heating is continued while maintaining this state. In this case, the heating temperature during the lamination may be the same as or different from the heating temperature during the B-stage conversion. When the resin film is laminated on a substrate, the heating temperature is not particularly limited, but is preferably 15 to 150 ° C, may be 20 to 130 ° C, or may be 20 to 100 ° C. In addition, when the aforementioned solvent method is applied, the B-stage conversion can be performed simultaneously with heating when the aforementioned resin varnish is dried. In other words, it is possible to obtain a prepreg precursor by performing B-stage conversion of the thermosetting resin composition in the following manner: After the base material is immersed in the resin varnish, the organic solvent is dried by heating while maintaining the state Under continuous heating. In this case, the heating temperature during the lamination may be the same as or different from the heating temperature during the B-stage conversion. When the resin varnish is dried, the heating temperature is not particularly limited, but is preferably 10 to 190 ° C, may be 15 to 180 ° C, or may be 15 to 170 ° C.

In this step 1, the conditions for the B-stage conversion are not particularly limited as long as they are capable of B-stage conversion of the thermosetting resin composition, and may be appropriately determined depending on the type of the thermosetting resin and the like. The heating temperature is preferably 70 to 190 ° C, for example, 80 to 180 ° C, 120 to 180 ° C, or 140 to 180 ° C. The heating method is not particularly limited, and examples thereof include a heating method using a flat plate heater, a heating method using hot air, a heating method using high frequency, a heating method using magnetic field lines, a heating method using laser, A heating method or the like combined with these. Among these, a heating method using a flat plate heater and a heating method using hot air are simple and preferable. The heating time is, for example, 1 to 30 minutes, 2 to 20 minutes, 2 to 10 minutes, or 2 to 6 minutes.

<Step 2> Step 2 is a step of cooling the prepreg precursor obtained in step 1. In other words, step 2 is directed to the prepreg precursor obtained by subjecting the prepreg precursor to a B-stage heating treatment in step 1, and cooling the prepreg precursor to at least A step of lowering the temperature of the heat treatment. By performing step 2, the thermal history generally applied when manufacturing a prepreg, such as B-stage conversion and cooling of a thermosetting resin composition, is received, and the obtained prepreg precursor may Inside, there is a tendency that strain and the like occur in a conventional prepreg, and this strain becomes a main cause of dimensional change. As described above, it is easy to effectively implement the following, because the strain and the like caused by the thermal history such as heating (step 1) and cooling (step 2) are stored in advance before step 3 to be described later. : Eliminate the above-mentioned strains and make the amount of dimensional change uniform by step 3. Further, since the strain caused by thermal history such as heating (step 1) and cooling (step 2) has been eliminated by step 3, after step 3, even if the same thermal history is applied, no strain occurs or even occurs The strain is also very small, so 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 can be performed by natural cooling, or a cooling device such as a blower or a cooling roller can be used. Furthermore, from the viewpoint of productivity, it is preferable to perform cooling by a blower. In this step, the surface temperature of the cooled prepreg precursor is usually 5 to 60 ° C, preferably 10 to 45 ° C, more preferably 10 to 30 ° C, and more preferably room temperature. In addition, in this specification, the room temperature refers to an ambient temperature without temperature control such as heating and cooling, and is generally about 15 to 25 ° C. However, since it may change due to weather, season, etc., it is not limited to Within the above range.

<Step 3> Step 3 is a surface heating treatment step, which heat-treats the surface of the prepreg precursor at a heat source temperature of 200 to 700 ° C. to the prepreg precursor obtained in the foregoing step 1 or step 2. A prepreg is obtained; and it can also be referred to as a surface heating treatment step, in which the surface of the prepreg precursor is heated to obtain a prepreg so that the surface temperature of the prepreg precursor becomes 40 to 130 ° C. body.本 With this step 3, the deviation of the dimensional change of the prepreg will be small. Although the correct reason is not clear, it is thought that by this step 3, the strain of the substrate in the prepreg precursor obtained in step 1 or step 2 can be eliminated, and the strain derived from the strain can be reduced. The dimensional change during curing can reduce the variation in the amount of dimensional change. By reducing the variation in the amount of dimensional change, it is possible to reduce the problem of positional deviation of the through hole.

In step 3, the heating method as the surface heating treatment is not particularly limited, and examples thereof include a heating method using a flat plate heater, a heating method using hot air, a heating method using high frequency, a heating method using magnetic field lines, A heating method by 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 plate heater or a heating method using hot air is preferred. In one aspect of the present invention, the surface heating treatment is performed at a heat source temperature of 200 to 700 ° C. From the viewpoint of maintaining the productivity of the prepreg better, and 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 performed at a higher temperature and in a shorter time than the heat treatment when the B-stage conversion is performed in step 1. From this point of view, the heat source temperature during the surface heating treatment is preferably 250 to 700 ° C, more preferably 300 to 600 ° C, and even more preferably 350 to 550 ° C. In particular, when a heating method using a flat plate heater or a heating method by hot air is performed, it is preferable to perform a surface heating treatment within the aforementioned temperature range. Furthermore, in one aspect of the present invention, from the viewpoint of reducing the variation in the amount of dimensional change while maintaining the formability of the prepreg, the surface heating treatment is performed such that the surface temperature of the prepreg precursor becomes, for example, The following temperature mode is implemented: preferably 40 to 130 ° C, more preferably 40 to 110 ° C, and still more preferably 60 to 90 ° C. It is preferable to set the surface temperature of the prepreg precursor to this range by the aforementioned heat source temperature. The heating time of the surface heating treatment is not particularly limited, and from the viewpoint of maintaining good productivity of the prepreg and the viewpoint of keeping the prepreg in a B-stage state while maintaining good formability while reducing 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 the formability of the prepreg, the value of the rise in the surface temperature of the prepreg precursor caused by the surface heating treatment (that is, the value before the surface heating treatment) The absolute value of the difference between the surface temperature and the highest surface temperature reached during the surface heating treatment is preferably 5 to 110 ° C, more preferably 20 to 90 ° C, and even more preferably 40 to 70 ° C. The detailed heating conditions for the surface heating treatment may be conditions that can increase the surface temperature of the prepreg precursor more than the surface temperature before the surface heating treatment by setting the heat source temperature to the aforementioned range, and only The range which does not significantly influence various characteristics (for example, fluidity) of the obtained prepreg is not specifically limited, What is necessary is just to determine suitably according to the kind of thermosetting resin, etc.

From the viewpoints of handleability and stickiness of the prepreg, the prepreg obtained in step 3 is preferably provided to a cooling step of cooling the prepreg. The cooling of the prepreg may be performed by natural cooling, or a cooling device such as a blower or a cooling roll may be used. The temperature of the prepreg after cooling is usually 5 to 80 ° C, preferably 8 to 50 ° C, more preferably 10 to 30 ° C, and even 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% by mass, more preferably 30 to 85% by mass, and 50 to 80% by mass. % Is better.的 The thickness of the prepreg of the present invention is, for example, 0.01 to 0.5 mm, and from the viewpoint of moldability and high-density wiring, it is preferably 0.02 to 0.3 mm, and more preferably 0.05 to 0.2 mm.

Hereinafter, the base material and the thermosetting resin composition used in the production of the prepreg of the present invention will be described in detail in order. [Substrate] As a substrate for constituting the prepreg of the present invention, a sheet-like reinforcing substrate is used, and a conventional substrate used in a laminated board 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 fiber and asbestos; aramide, polyimide, polyvinyl alcohol, polyester, tetrafluoroethylene, and acrylic Organic fibers; such mixtures and the like. Among these, glass fiber is preferred from the viewpoint of flame retardancy. As the glass fiber substrate, for example, a woven fabric obtained by using E glass, C glass, D glass, S glass or the like, or a glass woven fabric obtained by adhering short fibers with an organic binder; Base material made of cellulose fibers. A glass woven fabric obtained by using E glass is preferred. These substrates have shapes such as woven fabrics, non-woven fabrics, yarn bundles, cut felts, and surface felts. In addition, the material and shape are selected according to the intended use and performance of the molded product, and one kind can be used alone, and two or more kinds of materials and shapes can be combined as needed. The thickness of the base material is, for example, 0.01 to 0.5 mm. From the viewpoint of moldability and high-density wiring, it is preferably 0.015 to 0.2 mm, and more preferably 0.02 to 0.15 mm. From the viewpoints of heat resistance, moisture resistance, processability, etc., these substrates are preferably: a substrate subjected to a surface treatment with a silane coupling agent or the like, and a substrate subjected to a mechanical fiber opening treatment .

However, although the prepregs described in the aforementioned Patent Documents 1 to 8 show relatively good relative dielectric constants, examples that fail to meet the stringent requirements of the market in recent years are increasing. In addition, not only the variation in the amount of dimensional change cannot be sufficiently suppressed, but also often has high heat resistance, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and uniform plating (laser processability). Either is insufficient, and there is still room for further improvement in this regard. In addition, in reality, materials have not been sufficiently developed from the viewpoint of satisfying all the aforementioned characteristics. However, in the present invention, the components of the thermosetting resin composition are set to the following components while using the method for producing a prepreg of the present invention as described below. In addition to sufficiently suppressing variations in the amount of dimensional change, it is possible to increase the Heat resistance, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and uniformity (laser processability) 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. In addition to sufficiently suppressing variations in the amount of dimensional change, it can also achieve high heat resistance, high metal foil adhesion, and high glass. From the viewpoints that the transition temperature, low thermal expansion, moldability, and uniform plating (laser processability) are satisfactory, a thermosetting resin composition (hereinafter referred to as a thermosetting resin composition [I ]), Which contains (A) a maleimide compound. From the same viewpoint, the thermosetting resin composition [I] preferably further contains: (B) an epoxy resin; (C) a copolymer resin having a structural unit and a source derived from a substituted vinyl compound A structural unit derived from maleic anhydride; and (D) silicon oxide treated with an aminosilane-based coupling agent. From the same viewpoint, it is preferable that the thermosetting resin composition [I] contains (E) a hardener, and from the viewpoint of flame retardancy, it is preferable to contain (F) a flame retarder. In addition, from the viewpoint of sufficiently suppressing the variation in the amount of dimensional change, it may be an epoxy resin composition [II] containing (G) an epoxy resin and (H) an epoxy resin hardener, and ( I) A hardening accelerator and (J) an inorganic filler, or a thermosetting resin composition [III], which contains (K) a silicone modified maleimide compound and (L) an imidazole compound, and responds (M) Inorganic filler required.

First, each component contained in the thermosetting resin composition [I] will be described in detail. <(A) Maleimide compound> (A) The component is a maleimide compound (hereinafter, sometimes referred to as a maleimide compound (A)) so as to have N-substituted maleimide A maleimide compound based on methyl is preferred, and a maleimide compound having N-substituted maleimide is preferred, and (a1) has at least two N-substituted maleimides Amine-based maleimide compounds [hereinafter, abbreviated as maleimide compounds (a1)], (a2) monoamine compounds represented by the following general formula (a2-1) [hereinafter, abbreviated as monoamines The compounds (a2)] and (a3) are obtained by reacting a diamine compound [hereinafter, simply referred to as a 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 or a halogen atom having 1 to 5 carbon atoms, and t is an integer of 1 to 5 , U is an integer of 0 to 4, and satisfies 1 ≦ t + u ≦ 5, where when t is an integer of 2 to 5, the plural R ^A4 may be the same or different, and in addition, when u is an integer of 2 to 4 , The plurality of R ^A5 may be the same or different; In the general formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or -O-, 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 sulfonic acid groups, 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 maleimide compound having an N-substituted maleimide group.

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

(Maleimide compound (a1)) The maleimide compound (a1) is a maleimide compound having at least two N-substituted maleimide groups in one molecule. Examples of the maleimide compound (a1) include an aliphatic hydrocarbon group between any two maleimide groups (there is no aromatic hydrocarbon group). ), A maleimide compound [hereinafter, referred to as an aliphatic hydrocarbon-containing maleimide], or an aromatic compound between any two maleimide groups among a plurality of maleimide groups Maleimide compound of the group hydrocarbon group [hereinafter, referred to as aromatic hydrocarbon group-containing maleimide compound]. Among these, from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and uniform plating, the aromatic hydrocarbon group-containing maleic acid is used. Imines are preferred. The aromatic hydrocarbon group-containing maleimide may contain an aromatic hydrocarbon group between any combination of two maleimide groups arbitrarily selected, and may have both an aliphatic hydrocarbon group and an aromatic hydrocarbon group. From the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and uniform plating, the maleimidine imine compound (a1) is preferably one. A maleimide compound having 2 to 5 N-substituted maleimide imino groups in the molecule, more preferably a maleimide compound having 2 N-substituted maleimide imino groups in one molecule . In addition, from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and uniform plating, the maleimide imine compound (a1) is preferred. It is an aromatic hydrocarbon group-containing maleimidine imide represented by any one of the following general formulae (a1-1) to (a1-4), and more preferably is represented by the following general formulae (a1-1), (a1) -2) or (a1-4) The aromatic hydrocarbon group-containing maleimide imide represented by the following formula (a1-2) is particularly preferred.

In the 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 and 2 carbon atoms ~ 5 alkylene, -O-, -C (= O)-, -S-, -S-S-, or sulfonyl; p, q, and r are each independently an integer of 0 to 4; s It is an integer from 0 to 10. Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^A1 to R ^A3 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, and n-butyl. Amyl and others. From the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and uniform plating property, as the aliphatic hydrocarbon group, a carbon number of 1 to 3 Aliphatic hydrocarbon groups are preferred, with methyl and ethyl being 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, and 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, moldability, and uniform plating, as the alkylene group, a carbon number of 1 to 3 Alkylene is preferred, and methylene is more preferred. Examples of the alkylene group having 2 to 5 carbon atoms represented by X ^A1 include ethylene, propylene, isopropylidene, butylene, isobutylene, pentylene, and isopentylene. Among these, from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and uniform plating, 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 and an alkylene group having 2 to 5 carbon atoms. The preferred examples are 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 dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and uniform plating See, any one is preferably 0 to 2, more preferably 0 or 1, more preferably 0. s is an integer of 0 to 10, and from the viewpoint of easiness of acquisition, 0 to 5 is preferable, and 0 to 3 is more preferable. In particular, the aromatic hydrocarbon group-containing maleimide imide compound represented by the general formula (a1-3) is preferably a mixture of s of 0 to 3.

Specific examples of the maleimidine compound (a1) include: N, N'-ethylidenebismaleimide, N, N'-hexamethylenebismaleimide, and bis (4 -Aliphatic hydrocarbon-containing maleimide imide such as maleimide iminocyclohexyl) methane, 1,4-bis (maleimideiminomethyl) cyclohexane; N, N '-(1,3 -Phenylene) bismaleimide, N, N '-[1,3- (2-methylphenylene)] bismaleimide, N, N'-[1,3- ( 4-methylphenylene)] bismaleimide, N, N '-(1,4-phenylene) bismaleimide, bis (4-maleimidophenyl) Methane, bis (3-methyl-4-maleiminophenylphenyl) methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bis Maleimide, bis (4-maleimideiminophenyl) ether, bis (4-maleimideiminophenyl) fluorene, bis (4-maleimideiminophenyl) sulfide Ether, bis (4-maleimidoiminophenyl) ketone, 1,4-bis (4-maleimidoiminophenyl) cyclohexane, 1,4-bis (maleimidoimino) (Methyl) cyclohexane, 1,3-bis (4-maleimidophenoxy) benzene, 1,3-bis (3-maleimidophenoxy) benzene, bis [4 -(3-maleimidoiminophenoxy) phenyl] methane, [4- (4-maleimidoiminophenoxy) phenyl] methane, 1,1-bis [4- (3-maleimidoimidophenoxy) phenyl] ethane, 1, 1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimidophenoxy) phenyl] ethyl Alkane, 1,2-bis [4- (4-maleimidoimidophenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimidoimidophenoxy) Phenyl] propane, 2,2-bis [4- (4-maleimidoimidophenoxy) phenyl] propane, 2,2-bis [4- (3-maleimidoimidophenoxy) Phenyl) phenyl] butane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidine Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-maleiminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3-maleimidoimidophenoxy) biphenyl, 4,4-bis (4-maleimidine Aminophenoxy) biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (4-maleimidophenoxy) phenyl ] Ketone, 2,2'-bis (4-maleimidoimidophenyl) disulfide, bis (4-maleimidoimidophenyl) disulfide, bis [4- (3-Ma Lyme iminophenoxy) phenyl] sulfide, [4- (4-maleimidoiminophenoxy) phenyl] sulfide, bis [4- (3-maleimidoimidophenoxy) phenyl] sulfinium, bis [4- ( 4-maleimidoiminophenoxy) phenyl] fluorene, bis [4- (3-maleimidoiminophenoxy) phenyl] fluorene, bis [4- (4-maleimidine Iminophenoxy) phenyl] fluorene, bis [4- (3-maleimidoiminophenoxy) phenyl] ether, bis [4- (4-maleimidoiminophenoxy) ) Phenyl] ether, 1,4-bis [4- (4-maleimidoiminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- ( 4-maleimidoimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidoimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidoiminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4- Bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4- Maleimidoiminophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidoiminobenzene) (Oxy))-3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -3,5 -Dimethyl-α, α-dimethylbenzyl] benzene, Diphenylmethane maleic acyl imine (PEI) containing maleic aromatic hydrocarbon.

Among these, bis (4-maleimidoiminophenyl) methane and bis (4-maleimidoimino) are preferred from the viewpoint of high reaction rate and higher heat resistance. Phenyl) fluorene, bis (4-maleiminoiminophenyl) sulfide, bis (4-maleiminoiminophenyl) disulfide, N, N '-(1,3-phenylene Group) bismaleimide and 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane, and from the viewpoint of low cost, bis (4 -Maleimidoiminophenyl) methane, N, N '-(1,3-phenylene) bismaleimidoimine, from the viewpoint of solubility in a solvent, bis (4 -Maleimidoiminophenyl) methane. The maleimide imine compound (a1) may be used alone or in combination of two or more.

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

In the general formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group, and a sulfonic acid group, R ^A5 represents an alkyl group or a halogen atom having 1 to 5 carbon atoms, and t is 1 to 5 Integer, u is an integer from 0 to 4, and satisfies 1 ≦ t + u ≦ 5, where when t is an integer from 2 to 5, the plurality of R ^A4 may be the same or different. In addition, when u is 2 to 4 For integers, the 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 preferred, and when heat resistance is also considered, a hydroxyl group is preferred. t is an integer of 1 to 5, and from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and uniform plating, t ranges from 1 to 3 An integer of 1 is preferred, 1 or 2 is preferred, and 1 is more preferred. 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. Examples of the halogen atom represented by R ^A5 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. u is an integer of 0 to 4, and from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and uniform plating, An integer is preferred, an integer of 0 to 2 is preferred, 0 or 1 is more preferred, and 0 is particularly preferred. From the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and uniform plating properties, the monoamine compound (a2) is preferably as follows 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). Wherein in the general formula (A2-2) and ^{(a2-3), R A4, R} A5 , and u is the formula (A2-1) in R ^A4, R ^A5, and the same u, preferred embodiments are also the same.

Examples of the monoamine compound (a2) include o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, and o-aminobenzenesulfonic acid. Monoamine compounds having acidic substituents such as acids, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, and 3,5-dicarboxyaniline. Among these, m-aminophenol, p-aminophenol, p-aminobenzoic acid, and 3,5-dihydroxyaniline are preferred from the viewpoint of solubility and reactivity, and from the viewpoint of heat resistance Preferably, o-aminophenol, m-aminophenol, and p-aminophenol are used. When considering the dielectric characteristics, low thermal expansion, and manufacturing cost, p-aminophenol is more preferred. The monoamine compound (a2) may be used individually by 1 type, and may use 2 or more types together.

(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 sulfonic acid groups, v and w are each independently an integer of 0 to 4.

Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms represented by X ^A2 include methylene, ethylene, propylene, and propylene. X ^{A2 is} preferably a methylene group. Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^A6 and R ^A7 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, and n-pentyl. Base etc. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. v and w are preferably integers of 0 to 2, 0 or 1 is more preferred, and 0 is more preferred.

The diamine compound (a3) is preferably a diamine compound represented by the following general formula (a3-1 '). In the general formula ^{(a3-1 '), X A2,} R A6, R A7, v and w and the general formula (A3-1) in the ^{X A2, R A6, R A7} , and the same v w, preferred state 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'-di Ethyl-4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfide, 3,3'-di 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'-tetramethyl chloride-4 , 4'-diaminodiphenylmethane, 2,2 ', 6,6'-tetrabromo-4,4'-diaminodiphenylmethane and the like. Among these, 4,4'-diaminodiphenylmethane and 3,3'-diethyl-4,4'-diaminodiphenyl are preferred from the viewpoint of low cost. 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 performed by the following method: preferably in the presence of an organic solvent at a reaction temperature of 70 The reaction is carried out at -200 ° C for 0.1 to 10 hours. The reaction temperature is preferably 70 to 160 ° C, more preferably 70 to 130 ° C, and particularly preferably 80 to 120 ° C. The reaction time is preferably 1 to 6 hours, and more preferably 1 to 4 hours.

(Use amounts of maleimide imine compound (a1), monoamine compound (a2), and diamine compound (a3)) Maleimide imine compound (a1), monoamine compound (a2), and diamine compound (a3) In the reaction of (3), the amount of the three is preferably: the total of the primary amine equivalents (described as -NH ₂ group equivalents) of the monoamine compound (a2) and the diamine compound (a3) and maleimide The relationship between the maleimidine imide equivalents of the compound (a1) satisfies the following formula. 0.1 ≦ [maleimide imide equivalent] / [-total of NH ₂ radical equivalent] ≦ 10 By setting [maleimide imide equivalent] / [— NH ₂ radical equivalent] to 0.1 or more, It is possible not to reduce gelation and heat resistance, and by setting [maleimide imide equivalent] / [-NH ₂ group equivalent] to 10 or less, it is possible to prevent the solubility in organic solvents from being reduced. , Metal foil adhesion and heat resistance, so it is better. From the same viewpoint, it is more preferable to satisfy the following formula. 1 ≦ [maleimide imide equivalent] / [-total of NH ₂ group equivalent] ≦ 9 is more preferable to satisfy the following formula. 2 ≦ [maleimide imide equivalent] / [-total of NH ₂ group equivalent] ≦ 8

(Organic solvent) As described above, the reaction of the maleimide imine compound (a1), the monoamine compound (a2), and the diamine compound (a3) is preferably performed in an organic solvent. As an organic solvent, as long as it does not adversely affect the reaction, it is not particularly limited. Examples include alcohol solvents such as ethanol, propanol, butanol, methylcellulose, butylcellulose, propylene glycol monomethyl ether, and the like; acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexane Ketone solvents such as ketones; Ether solvents such as tetrahydrofuran; Aromatic solvents such as toluene, xylene, and xylene; fluorene amines such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone Nitrogen atom-containing solvents, including solvents; sulfur atom-containing solvents, including fluorene-based solvents such as dimethyl fluorene; ester solvents, such as ethyl acetate and γ-butyrolactone. Among these, alcohol solvents, ketone solvents, and ester solvents are preferred from the viewpoint of solubility, and cyclohexanone, propylene glycol monomethyl ether, and Methylcellulose and γ-butyrolactone are also considered to be highly volatile and difficult to remain as residual solvents in the production of prepregs. Cyclohexanone, propylene glycol monomethyl ether, and dimethyl ethyl are more preferred. Phenamine, particularly preferably dimethylacetamide. Organic solvents can be used alone or in combination of two or more. The amount of the organic solvent used is not particularly limited. From the viewpoints 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 use amount of the organic solvent is the following amount, it is preferably 25 to 1,000 parts by mass, more preferably 40 to 700 parts by mass, and still more preferably 60 to 250 parts by mass. By using 100 parts by mass of the total amount of the maleimide imine compound (a1), the monoamine compound (a2), and the diamine compound (a3), the use amount of the organic solvent is set to 25 parts by mass, and the solubility is easily ensured. With 100 parts by mass of the total of the maleimide imine compound (a1), the monoamine compound (a2), and the diamine compound (a3), the use amount of the organic solvent is set to 1,000 parts by mass or less, which is easily suppressed. The reaction efficiency is greatly reduced.

(Reaction catalyst) The reaction of the maleimide imine 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; phosphorus-based catalysts such as triphenylphosphine and the like. The hafnium reaction catalyst may be used singly or in combination of two or more kinds. The amount of the amidine reaction catalyst used is not particularly limited, and it is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of the maleimide imine compound (a1) and the monoamine compound (a2).

<(B) Epoxy resin> The component (B) is an epoxy resin (hereinafter sometimes referred to as an epoxy resin (B)), and an epoxy resin having at least two epoxy groups in one molecule is preferred. As an epoxy resin having at least two epoxy groups in one molecule, for example, a glycidyl ether epoxy resin, a glycidylamine epoxy resin, a glycidyl ester epoxy resin, and the like can be mentioned. Among these, a glycidyl ether type epoxy resin is preferable. Epoxy resins can also be classified into various epoxy resins according to the main skeleton. Among the above types of epoxy resins, they can be further classified into: bisphenol A epoxy resin, bisphenol F epoxy resin, and bisphenol. S-type epoxy resin and other bisphenol epoxy resins; biphenylaralkyl novolac epoxy resin, phenol novolac epoxy resin, alkylphenol novolac epoxy resin, cresol novolac epoxy Resin, naphthol alkylphenol copolymer novolac epoxy resin, naphthol aralkyl cresol copolymer novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, etc. Novolac epoxy resin; stilbene epoxy resin; triazine skeleton epoxy resin; fluorene skeleton epoxy resin; naphthalene epoxy resin; anthracene epoxy resin; triphenylmethane epoxy resin ; Biphenyl epoxy resin; xylene epoxy resin; alicyclic epoxy resin such as dicyclopentadiene epoxy resin. Among these, from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and uniform plating property, it is preferably from bisphenol F Type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenylaralkyl novolac type ring At least one selected from the group consisting of an oxyresin and a dicyclopentadiene-type epoxy resin is more preferably a cresol novolac-type epoxy resin from the viewpoint of low thermal expansion and high glass transition temperature. At least one selected from the group consisting of naphthalene-type epoxy resin, anthracene-type epoxy resin, biphenyl-type epoxy resin, biphenylaralkyl novolac-type epoxy resin, and phenol novolac-type epoxy resin More preferably, it is a cresol novolac epoxy resin. Epoxy resin (B) may be used alone or in combination of two or more.

The epoxy equivalent of the epoxy resin (B) is preferably 100 to 500 g / eq, more preferably 120 to 400 g / eq, more preferably 140 to 300 g / eq, and particularly preferably 170 to 240 g / eq. Here, the epoxy equivalent is the equivalent (g / eq) of the resin per epoxy group, and it can be measured according to the method prescribed by JIS K 7236 (2001). Specifically, it can be obtained by measuring an automatic titration device "GT-200" manufactured by Mitsubishi Chemical Analytech Co., Ltd., and measuring 2 g of epoxy resin into a 200 mL beaker, and then dripping the solution. 90 mL of methyl ethyl ketone was dissolved in 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 item of an epoxy resin (B), a cresol novolak-type epoxy resin "EPICLON (registered trademark) N-673" (made by DIC Corporation, epoxy equivalent weight: 205-215 g / eq), naphthalene epoxy resin "HP-4032" (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 152 g / eq), biphenyl epoxy resin "YX-4000" (manufactured by Mitsubishi Chemical Corporation, Epoxy equivalent: 186 g / eq), dicyclopentadiene epoxy resin "HP-7200H" (manufactured by DIC Corporation, epoxy equivalent: 280 g / eq), and the like. The epoxy equivalent is a value described in a catalog of a manufacturing company of the product.

<(C) Specific copolymer resin> (C) The component 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. . Examples of the substituted vinyl compound include an aromatic vinyl compound, an aliphatic vinyl compound, and a vinyl compound substituted with a functional group. Examples of the aromatic vinyl compound include styrene, 1-methylstyrene, vinyltoluene, and dimethylstyrene. Examples of the aliphatic ethylene-based compound include propylene, butadiene, and isobutylene. Examples of the vinyl compound substituted with a functional group include acrylonitrile; compounds having a (meth) acrylfluorenyl group such as methyl acrylate and methyl methacrylate; and the like. Among these, as the substituted vinyl compound, an aromatic vinyl compound is preferable, and styrene is more preferable. As the component (C), a copolymer resin having a structural unit represented by the following general formula (C-i) and a structural unit represented by the following general formula (C-ii) is preferred.

In the formula (Ci), R ^C1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, 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. , Hydroxy, or (meth) acrylfluorenyl; 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, and n-pentyl. Base etc. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. Examples of the alkenyl group having 2 to 5 carbon atoms represented by R ^C2 include an allyl group and a crotonyl group. The alkenyl group is preferably an alkenyl group having 3 to 5 carbon atoms, and more preferably an alkenyl group having 3 or 4 carbon atoms. Examples of the aryl group having 6 to 20 carbon atoms represented by R ^C2 include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. x is preferably 0 or 1, more preferably 0. Among the structural units represented by the general formula (Ci), the structural unit represented by the following general formula (Ci-1) in which R ^C1 is a hydrogen atom and x is 0, that is, a structural unit derived from styrene is preferable.

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 also the structural unit derived from the substituted vinyl compound. The mol ratio of the structural unit is preferably from 1 to 9, more preferably from 2 to 9, more preferably from 3 to 8, and particularly preferably from 3 to 7. In addition, the content ratio of the structural unit represented by the general formula (Ci) to the structural unit represented by the general formula (C-ii), that is, the mol ratio of (Ci) / (C-ii) is the same as 1 to 9 is preferable, 2 to 9 is preferable, 3 to 8 is more preferable, and 3 to 7 is particularly preferable. If these mol ratios are 1 or more, preferably 2 or more, the effect of improving the dielectric properties tends to be more sufficient, and if these mol ratios are 9 or less, the 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 (Ci) and the structural unit represented by the formula (C-ii) The total content of the structural units shown is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass. The weight average molecular weight (Mw) of the copolymer resin (C) is preferably 4,500 to 18,000, more preferably 5,000 to 18,000, even more preferably 6,000 to 17,000, more preferably 8,000 to 16,000, particularly preferably 8,000 to 15,000, and preferably 9,000. ~ 13,000 is the best.

In addition, by using a copolymer resin of styrene and maleic anhydride to reduce the dielectric constant of the epoxy resin, if it is applied to a material for a printed wiring board, the impregnation property to the substrate and the copper foil peeling strength It is not sufficient, so there is a tendency to generally avoid the above-mentioned methods. Therefore, there is a tendency that the use of the aforementioned copolymer resin (C) is generally avoided, but the present invention has been accomplished by knowing the following facts: Although the aforementioned copolymer resin (C) is used, the use of the above-mentioned (A) component and (B) ) Component, which will become a thermosetting resin composition, which has high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, and excellent moldability and uniformity.

(Manufacturing method of copolymer resin (C)) The copolymer resin (C) can be produced by copolymerizing a substituted ethylene-based compound and maleic anhydride.取代 Substituted vinyl compounds are as described above. The substituted vinyl compounds may be used alone or in combination of two or more. Further, in addition to the substituted vinyl compound and maleic anhydride, various components capable of being polymerized may be copolymerized. In addition, substituents such as allyl, methacryl group, acryl group, and hydroxyl group can be introduced into the substituted ethylene-based compound, particularly an aromatic vinyl-based compound through the following reaction: Fu-gram ( Friedel-Crafts) reaction; or a reaction using a metal catalyst such as lithium.

As the copolymer resin (C), a commercially available product can also be used. Examples of commercially available products include: "SMA (registered trademark) 1000" (styrene / maleic anhydride = 1, Mw = 5,000), "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 is made by CRAY VALLEY] and the like.

<(D) Silicon oxide treated with amine-based silane coupling agent> If silicon oxide treated with amine-based silane-based coupling agent (hereinafter, sometimes referred to as The silicon oxide (D) after being treated with an aminosilane-based coupling agent as the component (D), in addition to the effect of improving the low thermal expansion property, it is possible to improve the effect with (A) to (C) ) It is preferable because the adhesion between the components can suppress the silicon oxide from falling off. Therefore, the effect of suppressing the deformation of the shape of the laser through hole caused by the excess amount of the slag removal can be obtained.

As the amine-based silane coupling agent, specifically, a silane-based and amine-containing silane coupling agent represented by the following general formula (D-1) is preferred. In the formula (D-1), R ^D1 is an alkyl group having 1 to 3 carbon atoms or a fluorenyl group having 2 to 4 carbon atoms, and y is an integer of 0 to 3.

Examples of the alkyl group having 1 to 3 carbon atoms represented by R ^D1 include methyl, ethyl, n-propyl, and isopropyl. Of these, methyl is preferred. Examples of the fluorenyl group having 2 to 4 carbon atoms represented by R ^D1 include an ethylfluorenyl group, a propylfluorenyl group, and an acrylic fluorenyl group. Of these, ethenyl is preferred.

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

It is also possible to use a specific silicon oxide as an inorganic filler other than the component (D) instead of the silicon oxide (D) treated with an amine silane-based coupling agent, but it is preferable from the viewpoint of the aforementioned effects. A silicon oxide (D) treated with an amine silane-based coupling agent is used. The specific silicon oxide is, for example, silicon oxide treated with a specific coupling agent, or silicon oxide without surface treatment. Specific coupling agents are: epoxy silane-based coupling agents, phenyl silane-based coupling agents, alkyl silane-based coupling agents, alkenyl silane-based coupling agents, alkynyl silane-based coupling agents, haloalkyl silane-based coupling agents, silicon Oxygen-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, Amine silane-based coupling agent , Isocyanurate-based coupling agent, urea-based silane-based coupling agent, mercaptosilane-based coupling agent, thioether silane-based coupling agent, or isocyanatosilane-based coupling agent. In addition, the silicon oxide (D) treated with an aminosilane-based coupling agent and the silicon oxide treated with another coupling agent may be used in combination. At this time, it is preferable that the silicon oxide (D) treated with another coupling agent be 50 parts by mass or less, and 30 parts by weight, with respect 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 15 parts by mass, particularly preferably not more than 10 parts by mass, and most preferably not more than 5 parts by mass, but there is no particular limitation.

Examples of the silicon oxide include: deposited silicon oxide produced by a wet method and having a high moisture content; and dry process silicon oxide produced by a dry method with almost no bonding water or the like. The dry-type silicon oxide can be further classified according to different manufacturing methods, such as pulverized silicon oxide, fumed silicon oxide, fused silica (fused spherical silica), and the like. Among these, fused silica is preferable from the viewpoints of low thermal expansion and high fluidity when filled in a resin. The average particle diameter of the silicon oxide is not particularly limited, but it is preferably 0.1 to 10 μm, more preferably 0.1 to 6 μm, more preferably 0.1 to 3 μm, and particularly preferably 1 to 3 μm. When the average particle diameter of the silicon oxide is 0.1 μm or more, the fluidity at the time of high filling can be maintained, and when the average particle diameter of the silicon oxide is 10 μm or less, the mixing probability of coarse particles can be reduced and suppressed. Defects due to coarse particles occur. Here, the average particle diameter refers to a particle diameter of a point corresponding to 50% of the volume when the total particle size is 100% and the cumulative particle size distribution curve is obtained from the particle diameter. Laser diffraction can be used. The measurement is performed by a particle size distribution measuring device such as a scattering method. The specific surface area of the silicon oxide is preferably 4 cm ² / g or more, more preferably 4 to 9 cm ² / g, and even more preferably 5 to 7 cm ² / g.

<(E) Hardener> The thermosetting resin composition [I] may further contain a hardener as a component (E) (hereinafter, sometimes referred to as a hardener (E)). Examples of the hardening agent (E) include dicyandiamide, ethylenediamine, ethylenediamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, and diethylaminopropyl. Chain aliphatic amines other than dicyandiamide such as amine, tetramethylguanidine, triethanolamine; isophoronediamine, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, bis (4 -Amino-3-methyldicyclohexyl) methane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [ 5.5] Cyclic aliphatic amines such as undecane; aromatic amines such as xylylenediamine, phenylenediamine, diaminodiphenylmethane, and diaminodiphenylphosphonium. Among these, dicyandiamide is preferred from the viewpoints of metal foil adhesiveness and low thermal expansion. The dicyandiamide has a melting point of 205 to 215 ° C, as shown by H ₂ N-C (= NH) -NH-CN, and a higher purity dicyandiamide has a melting point of 207 to 212 ° C. Dicyandiamide is a crystalline substance, which may be orthorhombic, and may also be flaky. Dicyandiamide is preferably at least 98% pure, more preferably at least 99% pure, and even more preferably at least 99.4% pure. As the dicyandiamide, a commercially available product can be used. For example, a commercially available product manufactured by CARBIDE Industrial 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, although dicyandiamide and the like among the aforementioned hardeners also have the effect of a flame retardant, in the present invention, a substance capable of generating a function of a hardener is classified as a hardener, and is not included in ( F) in the ingredients. Examples of the flame retardant include: halogen-based flame retardants containing bromine and chlorine; phosphorus-based flame retardants; guanidine sulfamate, melamine sulfate, melamine polyphosphate, and melamine cyanurate ; Phosphazene flame retardants such as cyclophosphazene and polyphosphazene; inorganic flame retardants such as antimony trioxide. Among these, a phosphorus-based flame retardant is preferred. As phosphorus-based flame retardants, there are inorganic phosphorus-based flame retardants and organic phosphorus-based flame retardants. Examples of inorganic phosphorus-based flame retardants include: red phosphorus, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, ammonium polyphosphate and other ammonium phosphates; inorganic nitrogen-containing phosphorus compounds such as phosphatidamine; phosphoric acid; Phosphine oxide, etc. Examples of the organic phosphorus-based flame retardant include aromatic phosphates, mono-substituted phosphonic acid diesters, di-substituted phosphinates, metal salts of di-substituted phosphinic acids, organic nitrogen-containing phosphorus compounds, and cyclic compounds. Organic phosphorus compounds, phosphorus-containing phenol resins, etc. Among these, an aromatic phosphate and a metal salt of a disubstituted phosphinic acid 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, an aromatic phosphate is preferred.

Examples of the aromatic phosphate include triphenyl phosphate, tri (toluyl phosphate), tri (xylyl phosphate), tolyl phosphate diphenyl, and tolyl phosphate bis (2,6-xylyl). Resorcinol bis (diphenyl phosphate), 1,3-phenylene bis (bis (2,6-xylyl phosphate)), bisphenol A bis (diphenyl phosphate), 1,3- Phenylbis (diphenyl phosphate) and the like. As the monosubstituted phosphonic acid diester, for example, divinyl phenylphosphonate, diallyl phenylphosphonate, bis (1-butenyl) phenylphosphonate, and the like can be mentioned. As the disubstituted phosphinate, for example, phenyl diphenyl phosphinate, methyl diphenyl phosphinate, and the like can be mentioned. Examples of the metal salt of the disubstituted phosphinic acid include a metal salt of a dialkyl phosphinic acid, a metal salt of a diallyl phosphinic acid, a metal salt of a divinyl phosphinic acid, and a diaryl phosphinic acid. Acid metal salts and the like. As mentioned above, these metal salts are preferably any of lithium, sodium, potassium, calcium, magnesium, aluminum, titanium, and zinc salts. Examples of organic nitrogen-containing phosphorus compounds include phosphazene compounds such as bis (2-allylphenoxy) phosphazene and bis (tolyl) phosphazene; melamine phosphate, melamine pyrophosphate, melamine polyphosphate, poly Melamine phosphate and so on. 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 and the like. Among these, at least one selected from an aromatic phosphate, a metal salt of a disubstituted phosphinic acid, and a cyclic organic phosphorus compound is preferable, and an aromatic phosphate is more preferable.

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

In formulae (F-1) to (F-3), R ^F1 to R ^F5 are each independently an alkyl or halogen atom having 1 to 5 carbon atoms; 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 to 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, and n-pentyl. Base etc. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. Examples of the halogen atom represented by R ^F1 to R ^F5 include a fluorine atom and the like. e and f are preferably integers of 0 to 2, and more preferably 2. g, h, and i are preferably integers of 0 to 2, more preferably 0 or 1, and even 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 those in the case of R ^F1 to R ^F5 . Examples of the aryl group having 6 to 14 carbon atoms represented by R ^F6 and R ^F7 include a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group. The aromatic hydrocarbon group is preferably an aryl group having 6 to 10 carbon atoms. The valence of j is the same as that of the metal ion, that is, it changes within the range of 1 to 4 depending on the type of M. As M, an aluminum atom is preferred. When M is an aluminum atom, j is 3.

(Content of each component of the thermosetting resin composition [I]) The content of the components (A) to (D) in the thermosetting resin composition [I] is not particularly limited, and it is preferably: ) To (C) 100 parts by mass in total, (A) component is 15 to 65 parts by mass, (B) component is 15 to 50 parts by mass, (C) component is 10 to 45 parts by mass, and (D) component is 30 to 70 parts by mass. With respect to 100 parts by mass of the total of the components (A) to (C) and 15 parts by mass or more of the component (A), high heat resistance, low relative permittivity, high glass transition temperature, and low thermal expansion can be obtained. Propensity. On the other hand, since 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 moldability of the thermosetting resin composition [I] are good. Propensity. The component (B) is 15 parts by mass or more relative to 100 parts by mass of the total of the components (A) to (C), so that high heat resistance, high glass transition temperature, and low thermal expansion tend to be obtained. On the other hand, 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), and may have high heat resistance, low relative permittivity, and high glass transition temperature. And the tendency of low thermal expansion. The component (C) is 10 parts by mass or more relative to 100 parts by mass of the total of the components (A) to (C), so that high heat resistance and low relative permittivity tend to be obtained. On the other hand, the (C) component is 45 parts by mass or less with respect to 100 parts by mass of the total of the components (A) to (C), and there are those which can obtain high heat resistance, high metal foil adhesion, and low thermal expansion. tendency. The component (D) is 30 parts by mass or more with respect to the total of 100 parts by mass of the components (A) to (C), and thus tends to be able to obtain excellent low thermal expansion properties. On the other hand, since the (D) component is 70 parts by mass or less with respect to 100 parts by mass of the total of the components (A) to (C), the heat-resistant and thermosetting resin composition [I] flows. It tends to have good properties and moldability.

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

In addition, when the (F) component is contained in the thermosetting resin composition [I], from the viewpoint of flame retardancy, the content of the (F) component is 100 parts by mass with respect to the total of the (A) to (C) components. The content is preferably from 0.1 to 20 parts by mass, and more preferably from 0.5 to 10 parts by mass. In particular, when a phosphorus-based flame retardant is used as the (F) component, from the viewpoint of flame retardancy, the phosphorus atom content rate is set to 100 parts by mass based on the total of the components (A) to (C). An amount of 0.1 to 3 parts by mass is preferable, an amount such that the phosphorus atom content rate is 0.2 to 3 parts by mass is more preferable, and an amount such that the phosphorus atom content rate is 0.5 to 3 parts by mass is more preferable.

(Other components) (1) The thermosetting resin composition [I] can contain other components such as additives and organic solvents as needed, as long as the effects of the present invention are not impaired. These may be contained individually by 1 type, and may contain 2 or more types.

(Additives) As additives, for example, inorganic fillers other than the component (D), hardening accelerators, colorants, antioxidants, reducing agents, ultraviolet absorbers, fluorescent whitening agents, adhesion improvers, Organic fillers and more. These may be used individually by 1 type, and may use 2 or more types together.

(Organic Solvent) 热 The thermosetting resin composition [I] may contain an organic solvent from the viewpoint that processing can be easily performed by dilution and the viewpoint that it is easy to produce a prepreg described later. In this specification, a thermosetting resin composition containing an organic solvent may be referred to as a 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-based solvents; acetone, methyl ethyl Ketone solvents such as methyl ketone, methyl isobutyl ketone, cyclohexanone; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and xylene; including methylformamide, N-methylformamide, Nitrogen atom solvents including N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone, etc. Sulfur atom-containing solvents including fluorene-based solvents; methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, propylene glycol monomethyl ether acetate, and ethyl ester solvents such as ethyl acetate. Among these, 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, and methyl formaldehyde are more preferred. Kiselosu and propylene glycol monomethyl ether are more preferably methyl ethyl ketone and methyl isobutyl ketone, and particularly preferably methyl ethyl ketone. Organic solvents can be used alone or in combination of two or more.

The content of the organic solvent in the thermosetting resin composition [I] (resin varnish) may be appropriately adjusted to such an extent that the thermosetting resin composition [I] can be easily processed. There is no particular limitation on the range of good cloth properties, and it is preferred that the solid content concentration (concentration of components other than the organic solvent) derived from the thermosetting resin composition [I] is 30 to 90% by mass, more preferably It is 40 to 80% by mass, and more preferably 50 to 80% by mass.

Next, each component contained in the epoxy resin composition [II] will be described in detail. Furthermore, in order to avoid duplication with the thermosetting resin composition [I], the epoxy resin composition [II] may not contain the (A) maleimide compound contained in the thermosetting resin composition [I], but It is not particularly limited to this aspect, and may contain the (A) maleimide compound.

<(G) Epoxy resin>) The (G) epoxy resin contained in the epoxy resin composition [II] is, for example, the same as the (B) epoxy resin in the thermosetting resin composition [I]. Epoxy resin, and its description is the same. Among these, bisphenol F-type epoxy resin, phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, naphthalene-type epoxy resin, anthracene-type epoxy resin, and biphenyl type are preferred. At least one selected from the group consisting of epoxy resin, biphenylaralkyl novolac epoxy resin, and dicyclopentadiene epoxy resin. From the viewpoint of low thermal expansion and high glass transition temperature, More preferred are from cresol novolac epoxy resin, naphthalene epoxy resin, anthracene epoxy resin, biphenyl epoxy resin, biphenylaralkyl novolac epoxy resin and phenol novolac ring At least one selected from the group consisting of oxygen resins, and more preferably biphenylaralkyl novolac-type epoxy resins.

<(H) Epoxy Resin Hardener> As the epoxy resin hardener, for example, various phenol resin compounds, acid anhydride compounds, amine compounds, and hydrazine compounds can be mentioned. Examples of the phenol resin compound include novolac phenol resin and resol type phenol resin. Examples of the acid anhydride compound include phthalic anhydride, benzophenonetetracarboxylic dianhydride, and methyl group. Nadic acid. Examples of the amine compound include dicyandiamide, diaminodiphenylmethane, and guanyl urea. Among these epoxy resin hardeners, from the viewpoint of improving reliability, novolac-type phenol resins are preferred, and cresol novolac resins are more preferred.

Commercial products such as "TD2090" (manufactured by DIC Corporation, trade name) can be used as the novolac phenol resin; for example, "KA-1165" (manufactured by DIC Corporation, trade name), etc. Cresol novolac resin, etc. In addition, for example, cities such as "PHENOLITE LA-1356" (manufactured by DIC Corporation, trade name), "PHENOLITE LA7050 series" (manufactured by DIC Corporation, trade name), and other cities containing triazine ring novolac-type phenol resins For example, a triazine cresol novolac resin such as "PHENOLITE LA-3018" (manufactured by DIC Corporation, trade name) can be mentioned.

The epoxy resin composition [II] may contain (I) a hardening accelerator and (J) an inorganic filler as needed. <(I) hardening accelerator> From the viewpoint of accelerating the reaction between (G) epoxy resin and (H) epoxy resin hardener, the epoxy resin composition [II] preferably contains (I) a hardening accelerator. . Examples of the (I) hardening accelerator include imidazole compounds such as 2-phenylimidazole, 2-ethyl-4-methylimidazole, and trimellitic acid 1-cyanoethyl-2-phenylimidazolium salt; Organophosphorus compounds such as triphenylphosphine; Onium salts such as osmium 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> 的 From the viewpoint of low thermal expansion, the epoxy resin composition [II] preferably contains (J) an inorganic filler. Examples of the (J) inorganic filler include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, and boric acid. Aluminum, barium titanate, strontium titanate, calcium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. These may be used individually by 1 type, and may use 2 or more types together. Among these, silicon oxide is preferred from the viewpoint of a low thermal expansion coefficient. The average particle diameter of the inorganic filler is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more. Inorganic filler can be surface-treated. For example, when using silicon oxide as an inorganic filler, a silane coupling agent treatment may be performed as a surface treatment. Examples of the silane coupling agent include an amino silane coupling agent, a vinyl silane coupling agent, and an epoxy silane coupling agent. Among these, silicon oxide which has been surface-treated with an amine silane coupling agent is preferred.

(Contents of each component of the epoxy resin composition [II]) 中 The content of the (G) to (J) components in the epoxy resin composition [II] is not particularly limited, and is preferably relative to (G) to (J) A total of 100 parts by mass of components, (G) a component of 5 to 50 parts by mass, (H) a component of 5 to 50 parts by mass, (I) a component of 0.001 to 1 part by mass, and (J) a component of 20 to 80 parts by mass. More preferably, the component (G) is 5 to 35 parts by mass, the component (H) is 5 to 40 parts by mass, and the component (I) is 0.001 to 1 with respect to 100 parts by mass of the total of the components (G) to (J). The mass part and (J) component are 35-80 mass parts.

(Other components) 环氧树脂 The epoxy resin composition [II] can contain other components such as an additive and an organic solvent as needed, as long as the effect of the present invention is not impaired. These may be contained individually by 1 type, and may contain 2 or more types.

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

(Organic solvent) The description of the organic solvent is the same as that 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) Siloxane-modified maleimide compound is not particularly limited as long as it is a maleimide compound having a siloxane skeleton. Preferred examples include: a maleimide compound (k-1) having at least two N-substituted maleimide imino groups in one molecule [hereinafter, also referred to as a maleimide compound (k-1 )] An addition reaction product with a siloxane compound (k-2) [hereinafter, also referred to as a siloxane compound (k-2)] having at least two primary amine groups in one molecule, preferably horse Addition reactants of a lyme imine 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 imine compound (k-1), the same as the maleimide compound (a1) in the description of the (A) maleimide imine compound in the thermosetting resin composition [I] can be used. compound of. As the siloxane compound (k-2), it is preferable to contain a structural unit represented by the following general formula (k-2-1).

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 phenyl group having a substituent.

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, and n-pentyl. Base etc. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. In the "phenyl group having a substituent", examples of the substituent included in the phenyl group 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 and an allyl group. Examples of the alkynyl group having 2 to 5 carbon atoms include ethynyl and propargyl. R ^k1 and R ^{k2 are each} preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group.

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

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

The description of the alkyl group having 1 to 5 carbon atoms, the phenyl group, and the phenyl group having a substituent represented by R ^k3 and R ^k4 is the same as the description of R ^k1 and R ^k2 . R ^k3 and R ^k4 are preferably methyl. Examples of the divalent organic group represented by R ^k5 and R ^k6 include an alkylene group, an alkenyl group, an alkynyl group, an arylene group, -O-, or a divalent linking group composed of these. . Examples of the alkylene group include an alkylene group having 1 to 10 carbon atoms, such as methylene, ethylidene, and propylidene. Examples of the alkenyl group include an alkenyl group having 2 to 10 carbon atoms. Examples of the alkynyl group include an alkynyl group having 2 to 10 carbon atoms. Examples of the arylene group include an arylene group having 6 to 20 carbon atoms such as a phenylene group and a naphthyl group. Among these, R ^k5 and R ^k6 are preferably an alkylene group and an alkylene group. m is preferably an integer of 2 to 50, more preferably an integer of 3 to 40, more preferably an integer of 5 to 30, and even more preferably an integer of 7 to 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 the siloxane compound (k-2), a commercially available product can be used. Commercial products include, for example, "KF-8010" (functional group equivalent of amine group is 430 g / mol), "X-22-161A" (functional group equivalent of amine group is 800 g / mol), "X- 22-161B "(functional group equivalent of amine group is 1,500 g / mol)," KF-8012 "(functional group equivalent of amine group is 2,200 g / mol)," KF-8008 "(functional group equivalent of amine group is 5,700 g / mol), "X-22-9409" (functional group equivalent of amine group is 700 g / mol), "X-22-1660B-3" (functional group equivalent of amine group is 2,200 g / mol) ( The above is manufactured by Shin-Etsu Chemical Industry Co., Ltd.); "BY-16-853U" (functional group equivalent of amine group is 460 g / mol), "BY-16-853" (functional group equivalent of amine group is 650 g / mol), "BY-16-853B" (the functional group equivalent of an amine group is 2,200 g / mol) (the above is made by Dow Corning Toray Co., Ltd.); "XF42-C5742" (the functional group equivalent of an amine group is 1,280 g / mol), "XF42-C6252" (functional group equivalent of amine group is 1,255 g / mol), "XF42-C5379" (functional group equivalent of amine group is 745 g / mol) (The above is Momentive Performance Materials Japan Co., Ltd.制) and so on. These may be used individually by 1 type, and may use 2 or more types together.

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

As described above, one aspect of the (K) siloxane-modified maleimide compound can be produced by making the maleimide compound (k-1) and the silicone compound (k-2) and the monoamine compound (k-3) as required. From the viewpoint 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 use ratios, preferably: the equivalent of the maleimide group of the maleimide compound (k-1) exceeds the siloxane compound (k-2) and the monoamine compound (k-3) The total of the equivalents of the primary amine groups, the equivalents of the maleimide group of the maleimide compound (k-1), and the primary order of the siloxane compound (k-2) and the monoamine compound (k-3). The total ratio of the equivalent of the amine group, that is, (k-1) / [(k-2) + (k-3)] is preferably 1 to 15, more preferably 2 to 10, and even more preferably 3 to 10.反应 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, and 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-phenyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-1-methylimidazole, 1,2-diethylimidazole, 1-ethyl-2-methylimidazole, 2-ethyl-4-methyl Imidazole, 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-methyl Imidazole, 2-phenyl-4,5-dimethylol imidazole, 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 '-Undecyl imidazolyl- (1')] ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ' )] Imidazole compounds such as ethyl-s-triazine; modified imidazole compounds such as isocyanate-masked imidazole and epoxy-masked imidazole; trimellitic acid 1-cyanoethyl-2-phenylimidazolium salt and the like Salts of imidazole compounds and trimellitic acid; salts of the aforementioned imidazole compounds and isocyanuric acid; salts of the aforementioned imidazole compounds and hydrobromic acid, and the like. Among these, a modified imidazole compound is preferable, and an imidazole is preferably masked by an isocyanate group. The imidazole compounds may be used alone or in combination of two or more.

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

(Contents of each component of the thermosetting resin composition [III]) The content of the (K) to (M) components in the thermosetting resin composition [III] is not particularly limited, and it is preferable to be relative to (K A total of 100 parts by mass of the components) to (M), 15 to 80 parts by mass of the (K) component, 0.01 to 5 parts by mass of the (L) component, and 15 to 80 parts by mass of the (M) component. More preferably, the component (K) is 30 to 65 parts by mass, the component (L) is 0.01 to 3 parts by mass, and the component (M) is 30 to 65 parts with respect to 100 parts by mass of the total of the components (K) to (M). Parts by mass.

(Other components) 热 The thermosetting resin composition [III] can contain other components such as an additive and an organic solvent as needed, as long as the effect of the present invention is not impaired. These may be contained individually by 1 type, and may contain 2 or more types.

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

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

[Prepreg] The variation in the dimensional change of the prepreg obtained by the production method of the present invention is small, and when the aforementioned thermosetting resin composition is used, it has high heat resistance, high metal foil adhesion, and high It also has excellent glass transition temperature, low thermal expansion, moldability, and uniform plating properties (laser processability).

Moreover, according to this invention, the following prepregs can be provided. The prepreg obtained by the manufacturing method of this invention is also equivalent to the following prepreg. In other words, the following prepreg can be manufactured by the manufacturing method of this invention. A prepreg comprising a base material and a thermosetting resin composition, and having a standard deviation σ determined in accordance with the following method of 0.012% or less, a method of calculating the standard deviation σ: copper having a thickness of 18 μm The foil was superimposed on both sides of a prepreg and subjected to heat and pressure molding at 190 ° C and 2.45 MPa for 90 minutes to produce a double-sided copper-clad laminate having a thickness of 0.1 mm; The double-sided copper-clad laminated board is provided with openings having a diameter of 1.0 mm at 1 to 8 locations shown in the first figure in the plane of the double-sided copper-clad laminated board; The directions are 1-7, 2-6, 3-5, and the horizontal line directions are 1-3, 8-4, and 7-5. Each of the 3 points is measured using an image measuring machine. After measuring the distance between them, set each measurement distance to the initial value; then, remove the outer layer of copper foil and heat it at 185 ° C for 60 minutes with a dryer; after cooling, follow the same direction as the initial value measurement method. The direction of the vertical line is 1-7, 2-6, 3-5 and the direction of the horizontal line is 1-3, 8-4, 7-5 The distance between each three points is measured; the average value of these rates of change is obtained from the rate of change [(measured value after heat treatment-initial value) × 100 / initial value] relative to the initial value of each measured distance And calculate the standard deviation σ from the average. The aforementioned video measuring machine is not particularly limited, and for example, "QV-A808P1L-D" (manufactured by Mitutoyo) can be used.

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

[Laminated Sheet] 的 The laminated sheet of the present invention includes the aforementioned prepreg and a metal foil. It can be manufactured, for example, by laminating and forming the prepreg by using one piece of the prepreg or by stacking the prepreg by 2 to 20 pieces as required, and arranging metal foil on one or both sides thereof. . In addition, a laminated board in which a metal foil is arranged may be referred to as a metal-clad laminated board. The metal of the metal foil is not particularly limited as long as it is a metal used for electrical insulation materials. From the viewpoint of 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 even more preferably copper. The forming conditions of the laminated board can be applied to the conventional forming method of laminated board for electric insulation material and multilayer board. For example, it can use multi-stage pressure, multi-stage vacuum pressure, continuous forming, autoclave forming machine, etc., at a temperature of 100 to 250 ° C. , Forming at a pressure of 0.2 to 10 MPa and a heating time of 0.1 to 5 hours. In addition, the prepreg of the present invention and a printed wiring board for an inner layer can be combined and laminated to form a multilayer board.的 The thickness of the metal foil is not particularly limited as long as it is appropriately selected depending on the use of the printed wiring board and the like. The thickness of the metal foil is preferably 0.5 to 150 μm, more preferably 1 to 100 μm, more preferably 5 to 50 μm, and particularly preferably 5 to 30 μm.

Moreover, it is also preferable to form a plating layer by plating metal foil. The metal of the hafnium plating layer is not particularly limited as long as it can be used for plating. The metal of the plating layer is preferably selected from copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and an alloy containing at least one of these metal elements. . As the plating method, there is no particular limitation, and conventional methods such as electrolytic plating method and electroless plating method can be used.

[Printed wiring board] The present invention also provides a printed wiring board comprising the aforementioned prepreg or the aforementioned laminated board.印刷 The printed wiring board of the present invention can be manufactured by performing circuit processing on a metal foil of a metal-clad laminate. The circuit processing can be performed, for example, by forming a resist pattern on the surface of the metal foil, removing the unnecessary portion of the metal foil by etching, and peeling off the resist pattern, and then forming a required penetration with a drill. After forming the resist pattern again, the through-hole is plated for conduction, and the resist pattern is finally peeled off. The multilayer printed wiring board can be produced by further laminating the metal-clad laminated board on the surface of the printed wiring board obtained as described above under the same conditions as described above, and further performing circuit processing in the same manner as described above. In this case, 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 performed for the required number of sheets.

[Semiconductor Package] The semiconductor package of the present invention is obtained by mounting a semiconductor element on the printed wiring board of the present invention.半导体 The semiconductor package of the present invention can be manufactured by mounting a semiconductor wafer, a memory, and 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 prepared using the resin varnish, a prepreg obtained by subjecting the prepreg precursor to a surface heating treatment, and further manufacturing the prepreg. After the copper-clad laminated board was evaluated, the obtained copper-clad laminated board was evaluated. The evaluation method is shown below.

[Evaluation method] <1. Heat resistance (reflow heat resistance)> Using the four-layer copper-clad laminates prepared in each example, and setting the maximum temperature to 266 ° C, the four-layer copper-clad laminates were placed at One cycle is set to flow for 30 seconds in a constant temperature bath environment at 260 ° C or higher, and the number of cycles until the expansion of the substrate can be confirmed with the naked eye is determined. The greater the number of cycles, the better the heat resistance.

<2. Relative permittivity (Dk)> Use a network analyzer "8722C" (manufactured by HP) to implement a 1 GHz double-sided copper clad laminate with a relative dielectric using a three-plate structure linear line resonator method. Determination of constants. The size of the test piece was 200 mm × 50 mm × thickness 0.8 mm, and a 1.0-mm-wide straight line (200 mm in length) was formed at the center of one side of a double-sided copper-clad laminate by etching, and copper remained. A ground layer is provided on the entire back surface. For another double-sided copper-clad laminated board, the entire surface of one side was etched, and the back side was set as a ground layer. These two double-sided copper-clad laminated boards are laminated so that the ground layer is outside, and a strip line is produced. The measurement was performed at 25 ° C. The smaller the relative dielectric constant, the better.

<3. Metal foil adhesiveness (copper foil peeling strength)> 箔 Metal foil adhesiveness is evaluated by copper foil peeling strength. A 3 mm-wide copper foil was formed by immersing the double-sided copper-clad laminated board prepared in each example in a copper etching solution "ammonium persulfate (APS)" (manufactured by ADEKA Co., Ltd.) to prepare an evaluation substrate. The peel strength of the copper foil was measured using an autoclave "AG-100C" (manufactured by Shimadzu Corporation). The larger the value, the more excellent the metal foil adhesion is.

<4. Glass transition temperature (Tg)> 铜 Copper was immersed in a copper etching solution "ammonium persulfate (APS)" (manufactured by ADEKA Co., Ltd.) by immersing the double-sided copper-clad laminates prepared in each example. The foil was removed, and a 5 mm square evaluation substrate was produced, and a thermal mechanical analysis (TMA) test device "Q400EM" (manufactured by TA Instruments) was used to observe the thermal expansion of the evaluation substrate in the plane direction (Z direction) at 30 to 260 ° C. Characteristics, and the inflection point of the amount of expansion is the glass transition temperature.

<5. Low thermal expansion property> The copper foil was removed by immersing the double-sided copper clad laminate prepared in each example in a copper etching solution "ammonium persulfate (APS)" (made by ADEKA Corporation), A 5 mm square evaluation substrate was produced, and a 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 of the sample, the heating and cooling cycle was repeated twice, and the thermal expansion coefficient [ppm / ° C] of 30 ° C to 260 ° C in the second temperature shift graph was measured and set. It is an index of low thermal expansion. The smaller the value, the better the low thermal expansion property. In addition, in the table, the thermal expansion coefficient when Tg is not reached (labeled as "<Tg") and the thermal expansion coefficient when Tg (labeled as ">Tg") is described separately. Measurement conditions 1 ^st Run: room temperature → 210 ° C (temperature rise rate 10 ° C / min) 2 ^nd Run: 0 ° C → 270 ° C (temperature rise rate 10 ° C / min) Copper-clad laminated board is expected to be further thinned, and it is also compatible with this Expectations are being made to reduce the thickness of the prepreg used to form a copper-clad laminate. Since the thinned prepreg is easily warped, it is desirable that the prepreg at the time of heat treatment has a small warpage. In order to reduce warpage, it is more effective to make the thermal expansion coefficient of the substrate in the plane direction smaller.

<6. Uniformity (laser processability)> For the four-layer copper-clad laminates prepared in each example, a laser machine "LC-2F21B / 2C" (manufactured by Hitachi Via Mechanics Co., Ltd.) was used. The laser aperture was performed by performing a 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 aperture 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 used at 40 ° C for 5 minutes to use a neutralizing solution "Reduction Conditioner Securiganth P500" (manufactured by Atotech Japan Co., Ltd.) to perform the desmearing process. Then, electroless plating using the plating solution "Priganth MSK-DK" (Atotech Japan Co., Ltd.) for 20 minutes at 30 ℃, and 24 ℃, ² A / dm 2 using a plating solution "Cupracid HL" (Atotech Japan Co., Co., Ltd.) for 2 hours to plate the laser-processed substrate. A cross-sectional observation was performed on the obtained laser perforated substrate, and uniform plating properties were confirmed. As a method for evaluating the uniform plating property, since the uniform plating property is better, the difference between the thickness of the plating layer above the laser hole and the plating thickness at the bottom of the laser hole is within 10% of the thickness of the plating layer above the laser hole. The existence ratio (%) of the pores included in this range among 100 pores was determined.

<7. Formability> After removing the outer layer of copper from the four-layer copper-clad laminates prepared in each example, confirm the presence or absence of holes and abrasions in the surface of 340 mm × 500 mm with the naked eye, and make it formable. index. When there are no holes or abrasions, it is indicated as "good", and when there are holes or abrasions, it is indicated. When there are no holes or abrasions, it can be said that the formability is good.

<8. Evaluation of variation of dimensional change amount> (1) The double-sided copper-clad laminates prepared in each example were opened as shown in FIG. 1 with a diameter of 1.0 mm. As shown in Figure 1, the vertical direction of the glass cloth is 1-7, 2-6, 3-5, and the horizontal direction is 1-3, 8-4, 7-5. After measuring the distance between the three points at each of three points using an image measuring machine "QV-A808P1L-D" (manufactured by Mitutoyo Co., Ltd.), each measurement distance was set to an initial value. Then, the outer-layer copper foil was removed, and it heated at 185 degreeC for 60 minutes with the dryer. After cooling, it is performed in the same manner as the initial value measurement method. The vertical direction is 1-7, 2-6, 3-5, and the horizontal direction is 1-3, 8-4, 7-. The distance between each of the three points in the 5 direction was measured. Based on the change rate [(measurement value-initial value) × 100 / initial value] from the initial value of each measurement distance, an average value of the change rates is obtained, and a standard deviation σ relative to the average value is calculated. This standard deviation σ is set as an index of the variation in the amount of dimensional change. A smaller value of the standard deviation σ indicates that the deviation of the dimensional change amount is smaller and better.

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

(A) Component: The solution of the maleimide compound (A) obtained by the following manufacture example 1 was used. [Manufacturing Example 1] (1) A reaction vessel having a volume of 1 L having a thermometer, a stirring device, and a moisture meter equipped with a reflux cooling pipe was charged with 19.2 g of 4,4'-diaminodiphenylmethane and bis (4- 174.0 g of maleimidoiminophenyl) methane, 6.6 g of p-aminophenol and 330.0 g of dimethylacetamide, and reacted at 100 ° C for 2 hours to obtain an acidic substituent and N-substitution. A solution of the maleimidine imine compound (A) (Mw = 1,370) in dimethylacetamide is used as the component (A). Furthermore, the weight average molecular weight (Mw) is converted from a 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) [东 曹Co., Ltd.] is approximated by a cubic equation. The conditions of GPC are as follows. Device: (pump: L-6200 [Hitachi High-Technologies Co., Ltd.]), (detector: L-3300 RI [Hitachi High-Technologies Co., Ltd.]), (column oven: L- 655A-52 [manufactured by Hitachi High-Technologies Co., Ltd.]) column: TSKgel SuperHZ2000 + TSKgel SuperHZ2300 (both manufactured by Tosoh Corporation) 大小 column size: 6.0 × 40 mm (protective column), 7.8 × 300 mm (tube Column) Eluent: Tetrahydrofuran Sample concentration: 20 mg / 5 mL Injection volume: 10 μL Flow rate: 0.5 mL / min Measurement temperature: 40 ° C

(B) Ingredient: Cresol novolac epoxy resin "EPICLON (registered trademark) N-673" (manufactured by DIC Corporation) (C-1) Ingredient: "SMA (registered trademark) EF40" (styrene / horse (Anhydride = 4, Mw = 11,000, manufactured by Cray Valley Co., Ltd.) (C-2) component: "SMA (registered trademark) 3000" (styrene / maleic anhydride = 2, Mw = 7,500, manufactured by Cray Valley Co., Ltd.) (C) -3) Ingredient: "SMA (registered trademark) EF80" (styrene / maleic anhydride = 8, Mw = 14,400, manufactured by Cray Valley Co., Ltd.) (C-4) Ingredient: "SMA (registered trademark) 1000" (styrene / Maleic anhydride = 1, Mw = 5,000, manufactured by Cray Valley Co., Ltd.)

(D) Component: Fused silica (average particle diameter: 1.9 μm, specific surface area: 5.8 m ² / g) after treatment with an aminosilane-based coupling agent. Other inorganic fillers: "F05-30" (unknown Processed pulverized silica, average particle size: 4.2 μm, specific surface area 5.8 m ² / g, manufactured by Fukushima Kiln Co., Ltd.)

(E) Ingredient: Dicyandiamide (manufactured by CARBIDE Industrial Co., Ltd.) (F) Ingredient: "PX-200" (aromatic phosphate ester (refer to the following structural formula), manufactured by Big Eight Chemical Industry Co., Ltd.)

[Examples 1 to 13, Comparative Examples 1 to 4] (1) Each component shown above was prepared as shown in the following Tables 1 to 4 (wherein, when it is a solution, it means the amount converted by the solid content), and Methyl ethyl ketone was additionally added so that the non-volatile content became 65 to 75% by mass, and a resin varnish was prepared for each of the thermosetting resin compositions of the examples and comparative examples. Each of the obtained resin varnishes was impregnated in glass cloth (0.1 mm) of IPC standard # 3313, and dried using a flat-plate heater set at a temperature of 160 ° C for 4 minutes to perform B-stage conversion (step 1). It was left to cool (step 2) at a warm temperature (about 20 ° C) to obtain a prepreg precursor. In the comparative example, the prepreg was used as it was while maintaining the prepreg precursor. In each example, the obtained prepreg precursor was subjected to a surface heating treatment (product surface temperature of 70 ° C) for 3 seconds using a flat plate heater having a surface heating temperature set at 500 ° C, and then cooled until room temperature (about 20 ° C) to prepare a prepreg (step 3).

(Production and performance evaluation of double-sided copper-clad laminated board) After stacking the aforementioned prepregs by 8 pieces, a copper foil "3EC-VLP-18" (manufactured by Mitsui Metals Co., Ltd.) with a thickness of 18 μm was laminated on both sides And heat-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 laminated board having a thickness of 0.8 mm (8 prepregs), and then used the copper-clad laminate According to the foregoing method, the laminated board measures and evaluates the relative permittivity, metal foil adhesion, glass transition temperature (Tg), and low thermal expansion. In addition, a copper foil "3EC-VLP-18" (manufactured by Mitsui Metals Co., Ltd.) having a thickness of 18 μm was laminated on both sides of a single prepreg, and the pressure was 190 ° C and a pressure of 25 kgf / cm ² (2.45 MPa ) Heating and press molding for 90 minutes to produce a double-sided copper-clad laminate with a thickness of 0.1 mm (1 prepreg), and use the double-sided copper-clad laminate to measure and evaluate the dimensional change in accordance with the method described above. The deviation.

(Production and performance evaluation of four-layer copper-clad laminated board) On the other hand, using one piece of the aforementioned prepreg, a copper foil "YGP-18" (manufactured by Japan Electrolytic Co., Ltd.) with a thickness of 18 μm was laminated on both sides , And heated and pressed at a temperature of 190 ° C. and a pressure of 25 kgf / cm ² (2.45 MPa) for 90 minutes to produce a double-sided copper-clad laminate having a thickness of 0.1 mm (1 piece of prepreg), and then two copper foils An inner layer was adhered to the surface (using a "BF treatment solution" (manufactured by Hitachi Chemical Co., Ltd.)), and a copper foil having a thickness of 18 μm "YGP- 18 "(manufactured by Japan Electrolytic Co., Ltd.) was laminated on both sides, and heated and pressed at a temperature of 190 ° C and a pressure of 25 kgf / cm ² (2.45 MPa) for 90 minutes to produce a four-layer copper-clad laminate. Using this four-layer copper-clad laminate, evaluation of heat resistance, uniform plating property, and formability was performed in accordance with the aforementioned method. The results are shown in Tables 1 to 4.

[Table 1]

[Table 2]

[table 3]

[Table 4]

[Example 14] 取代 Instead of preparing a resin varnish in Example 1, a resin varnish was prepared using the following ingredients. 19 parts by mass of a biphenylaralkyl novolac epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-3000, epoxy equivalent weight: 280 to 300 g / eq), and cresol novolac 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, melt oxidation 65 parts by mass of silicon (fused silica produced by Admatechs Co., Ltd., treated with an amine silane coupling agent, average particle diameter: 2 μm), and diluted with a solvent (methyl ethyl ketone) A resin varnish (solid content concentration: 70% by mass) was prepared. Other steps were performed in the same manner as in Example 1 to obtain a prepreg. Using the obtained prepreg, a double-sided copper-clad laminated board was produced by the same method as in Example 1. After using this double-sided copper-clad laminated board to measure and evaluate the deviation of the dimensional change, the standard deviation σ The value is 0.010%.

[Example 15] Instead of preparing a resin varnish in Example 1, a resin varnish was prepared using the following ingredients. Add KF-8010 (both terminal amine modified silicone oil, Shin-Etsu Chemical Industry Co., Ltd.) to a reaction vessel with a volume of 2 L that can be heated and cooled with a stirring device and a moisture meter equipped with a reflux cooling pipe. (Manufactured) 75.7 g, bis (4-maleimidoiminophenyl) methane (manufactured by Daiwa Chemical Industry Co., Ltd., trade name: BMI-1000) 168.0 g, p-aminophenol (manufactured by Tokyo Chemical 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 silicon modified maleimide compound. 49.5 parts by mass of this silicon modified maleimide compound, 50 parts by mass of fused silica (fused silica produced by Admatechs Co., Ltd. and treated with an amine silane coupling agent), and an isocyanate group 0.5 parts by mass of masking imidazole (manufactured by Daiichi Kogyo Co., Ltd., trade name: G-8009L) was mixed and diluted with a solvent (methyl ethyl ketone) to prepare a resin varnish (solid content concentration: 70% by mass) ). Other steps were performed in the same manner as in Example 1 to obtain a prepreg. Using the obtained prepreg, a double-sided copper-clad laminated board was produced by the same method as in Example 1. After using this double-sided copper-clad laminated board to measure and evaluate the deviation of the dimensional change, the standard deviation σ The value is 0.009%.

From the above results, the following facts are known. In the embodiment, since the prepreg precursor is subjected to surface heating treatment, the standard deviation σ is smaller than that in the comparative example without surface heating treatment, and the variation in the amount of dimensional change can be sufficiently suppressed. In addition, in Examples 1 to 13, the reflow heat resistance reached 10 or more cycles with a heat resistance requirement level or higher, and obtained a low relative dielectric constant, high metal foil adhesion, and high glass transition temperature, and exhibited low thermal expansion. In addition, since it has a glass cloth protruding from the wall surface and a moderately roughened shape, it has been confirmed that it has good uniform plating properties. In terms of moldability, the resin has good landfill properties, and abnormalities such as scratches and holes cannot be confirmed. Among these, compared to Examples 11 to 13, Examples 1 to 10 have better relative permittivity and metal foil adhesion, and also exhibit other characteristics stably. [Industrial availability]

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

FIG. 1 is a schematic diagram of an evaluation substrate used when measuring the variation in the amount of dimensional change in the examples.

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Claims (20)

A method for producing a prepreg, comprising: (i) immersing a thermosetting resin composition in a substrate, and then performing a B-stage process on the thermosetting resin composition to obtain a prepreg precursor; and, A surface heating treatment step performed after the foregoing step of obtaining a prepreg precursor; and the foregoing 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. A method for producing a prepreg, comprising: (i) immersing a thermosetting resin composition in a substrate, and then performing a B-stage process on the thermosetting resin composition to obtain a prepreg precursor; and, A surface heating treatment step performed after the step of obtaining the prepreg precursor; and the surface heating treatment step is performed on the prepreg precursor so that the surface temperature of the prepreg precursor becomes 40 to 130 ° C. The surface is subjected to a heat treatment step. The method for producing a prepreg according to claim 1 or 2, further comprising cooling the prepreg precursor to 5 to 60 after the step of obtaining the prepreg precursor and before the surface heating treatment step. ° C steps. The method for producing a prepreg according to any one of claims 1 to 3, wherein the time of the surface heat treatment is 1.0 to 10.0 seconds. The method for producing a prepreg according to any one of claims 1 to 4, wherein the thermosetting resin composition contains (A) a maleimide compound. The method for producing a prepreg according to claim 5, wherein the component (A) is a maleimide compound having an N-substituted maleimide group, and (a1) has at least two N-substituted maleimide imide-based maleimide compounds, (a2) a monoamine compound represented by the following general formula (a2-1), and (a3) represented by the following general formula (a3-1) To obtain a diamine compound; 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 or a halogen atom having 1 to 5 carbon atoms, and t is an integer of 1 to 5 , U is an integer of 0 to 4 and satisfies 1 ≦ t + u ≦ 5, where when t is an integer of 2 to 5, the plurality of R ^A4 may be the same or different, and when u is an integer of 2 to 4 , The plurality of R ^A5 may be the same or different; In the general formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or -O-, 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 sulfonic acid groups, v and w are each independently an integer of 0 to 4. The method for producing a prepreg according to claim 5 or 6, wherein the thermosetting resin composition further comprises: (B) an epoxy resin; (C) a copolymer resin having a substituted vinyl-based resin The structural unit of the compound and the structural unit derived from maleic anhydride; and silicon oxide in which fluorene (D) is treated with an aminosilane-based coupling agent. The method for producing a prepreg according to claim 7, wherein the component (B) is selected from the group consisting of bisphenol F-type epoxy resin, phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, and naphthalene At least one selected from the group consisting of epoxy resin, anthracene epoxy resin, biphenyl epoxy resin, biphenylaralkyl novolac epoxy resin, and dicyclopentadiene 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 component represented by the following general formula (C-ii) Copolymer resin of structural unit: In the formula (Ci), R ^C1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, 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. , Hydroxy, or (meth) acrylfluorenyl, 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. A prepreg comprising a base material and a thermosetting resin composition, and having a standard deviation σ determined in accordance with the following method of 0.012% or less, a method of calculating the standard deviation σ: copper having a thickness of 18 μm The foil was superimposed on both sides of a prepreg and subjected to heat and pressure molding at 190 ° C and 2.45 MPa for 90 minutes to produce a double-sided copper-clad laminate having a thickness of 0.1 mm; The double-sided copper-clad laminated board is provided with openings having a diameter of 1.0 mm at 1 to 8 locations shown in the first figure in the plane of the double-sided copper-clad laminated board; The directions are 1-7, 2-6, 3-5, and the horizontal line directions are 1-3, 8-4, and 7-5. Each of the 3 points is measured using an image measuring machine. After measuring the distance between them, the respective measurement distances are set to initial values. Then, the outer layer of copper foil is removed and heated at 185 ° C. for 60 minutes with a dryer. After cooling, the same method as the initial value measurement method is used. Each of the vertical direction is the direction of 1-7, 2-6, 3-5 and the horizontal direction is the direction of 1-3, 8-4, 7-5. The distance between the points is measured; an average value of the change rates is obtained from the change rates of the initial values of the respective measurement distances, and a standard deviation σ relative to the average value is calculated. The prepreg according to claim 10 is obtained by the method for producing a 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 comprises: (B) an epoxy resin; (C) a copolymer resin having a structure derived from a substituted vinyl compound Unit and a structural unit derived from maleic anhydride; and silicon oxide in which fluorene (D) is 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 hardener. The prepreg according to claim 10, wherein the thermosetting resin composition contains (K) a silicone modified maleimide compound and (L) an imidazole compound. A laminated board comprising the prepreg according to any one of claims 10 to 15 and a metal foil. A printed wiring board comprising a prepreg according to any one of claims 10 to 15 or a laminated board according to claim 16. A semiconductor package comprising a semiconductor element mounted on a printed wiring board according to claim 17. The method for producing a prepreg according to any one of claims 1 to 4, wherein the thermosetting resin composition contains (G) an epoxy resin and (H) an epoxy resin hardener. The method for producing a prepreg according to any one of claims 1 to 4, wherein the thermosetting resin composition contains (K) a silicon modified maleimide compound and (L) an imidazole compound.