TWI824422B - Prepreg manufacturing method, prepreg, laminated board, printed wiring board and semiconductor package - Google Patents

Abstract

The present invention provides a method for manufacturing a prepreg. The dimensional variation of the prepreg is small. The invention also provides a prepreg, a laminate, a printed wiring board and a semiconductor package. The prepreg has a dimensional variation of The deviation in the amount of change is small. Furthermore, the present invention provides a prepreg, a laminate, a printed wiring board, and a semiconductor package in which the problem of positional deviation of through holes is less likely to occur. The above-mentioned manufacturing method of a prepreg is specifically a method of manufacturing a prepreg, which includes: after impregnating a base material with a thermosetting resin composition, the thermosetting resin composition is subjected to a B-stage The step of obtaining a prepreg precursor; and, the surface heating step performed after the aforementioned step of obtaining a prepreg precursor; and, the aforementioned surface heating step is to treat the prepreg with a heat source temperature of 200 to 700°C. The step of performing heat treatment on the surface of the precursor.

Description

Prepreg manufacturing method, 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 circuit board and a semiconductor package.

In recent years, electronic equipment has become more compact, lightweight, and multi-functional. With this situation, large-scale integrated circuits (LSI), chip components, etc. are becoming highly integrated, and their forms are also becoming multi-pin. and rapid changes in miniaturization. Therefore, in order to increase the packaging density of electronic components, development of multilayer printed wiring boards with finer circuits continues. As a manufacturing method for multilayer printed wiring boards that meets these requirements, the build-up method of multilayer printed wiring boards, which uses prepregs, is gradually becoming mainstream as a method suitable for lightweighting, miniaturization, and fine wiring. As an insulating layer, a wiring layer is formed while connecting only necessary parts, such as through holes formed by irradiating laser (hereinafter also referred to as "laser through holes").

The key point of a multilayer printed circuit board is to have high electrical connection reliability between multiple layers of circuit patterns formed with fine circuit pitches and excellent high-frequency characteristics. In addition, reliable connection to the semiconductor chip is required. High sex. In particular, in recent years, motherboards for multifunctional mobile phone terminals and the like have been subject to high-speed communications, high-density circuits, extremely thin circuit boards, and the circuit width (L) and spacing (S) of the circuit board (hereinafter, The line width and spacing are sometimes combined and denoted as [L/S]), which also tends to become narrower. As L/S becomes narrower, it becomes increasingly difficult to stably produce circuit boards with good yield. In addition, in the design of conventional circuit boards, a wireless circuit pattern layer called a "skip layer" is provided on some layers in consideration of communication obstacles. As electronic devices become more highly functional, the amount of circuit design is gradually increasing, and the number of circuit board layers is gradually increasing. However, the thickness of the motherboard is further increased due to the provision of the aforementioned jump layer. 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 the impedance of L/S can be easily controlled by lowering the relative dielectric constant of the insulating material, stable production can be achieved with L/S having a shape close to the current design, and the number of layers can be reduced by reducing the number of jump layers. Therefore, for insulating materials used in circuit boards, material properties with a smaller relative dielectric constant are currently being sought.

In recent years, in motherboards such as mobile phones, which are becoming thinner and cheaper as electronic devices become more dense, materials with a lower relative dielectric constant are being sought to cope with the thinning. In addition, communication system machines represented by servers, routers, mobile base stations, etc. have gradually been used in higher frequency bands, and high melting point lead-free solder has been gradually used to solder electronic parts. Therefore, As a material for the substrate used among these, there is a tendency to require a material with a low dielectric constant, a high glass transition temperature (high Tg), and excellent reflow heat resistance.

In addition, motherboards used in multi-function mobile phone terminals and the like require laser vias with small diameters to connect layers as circuit density increases and pattern widths narrow. From the perspective of connection reliability, there are many examples of using field plating, and the connectivity of the interface between the inner copper layer and the copper plating is very important. Therefore, there are also attempts to improve the lightning resistance of the base material. Processability tendency. Generally, after laser processing of the base material, a step of partially removing the resin residue (desmear treatment step) is performed. Since desmear processing will be carried out on the bottom and wall of the laser through hole, when the resin component of the base material is dissolved in large quantities due to the desmear treatment, there is a risk that the shape of the laser through hole will be significantly deformed due to the dissolution of the resin. , and various problems such as the unevenness of throwing plating due to the unevenness of the wall surface may occur. Therefore, it is desired that the amount of the resin component of the base material dissolved by the desmear treatment, that is, the so-called desmear dissolution amount, be an appropriate value.

Among the various characteristics sought for insulating materials used in circuit boards, the following methods have been used for the purpose of lowering the relative dielectric constant: the method of containing epoxy resin with a small relative dielectric constant, the method of introducing cyanide Acid-based methods, polyphenylene ether-containing methods, etc. For example, resin compositions containing epoxy resin (see Patent Document 1); resin compositions containing polyphenylene ether and bismaleimide (see Patent Document 2); and resin compositions containing polyphenylene ether and cyanate ester have been proposed. A resin composition (refer to Patent Document 3); a resin composition containing at least one of styrenic thermoplastic elastomers and/or triallyl cyanurate, etc. (Refer to Patent Document 4); containing polybutyl Diene resin composition (see Patent Document 5); prepared by reacting polyphenylene ether resin and polyfunctional maleimide and/or polyfunctional cyanate ester resin and liquid polybutadiene in advance A resin composition (see Patent Document 6); containing polyphenylene ether obtained by supplying or grafting a compound having an unsaturated double bond group, and triallyl cyanurate and/or triallyl Resin compositions such as isocyanurate (refer to Patent Document 7); resin compositions containing reaction products of polyphenylene ether and unsaturated carboxylic acid or unsaturated acid anhydride, and polyfunctional maleimide (refer to Patent document 8) etc. [Prior technical literature] (patent document)

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

[Problem to be solved by the invention] As mentioned above, insulating materials used in circuit boards tend to have various characteristics such as lowering the relative dielectric constant. However, one of the most important characteristics for interlayer connection through small-diameter laser vias is For example, the variation in dimensional change of prepregs is small. As motherboards become thinner, a multi-stage lamination method is required as a prepreg lamination method, which requires multiple times of heating and multiple times of pressure during lamination. Therefore, when the variation in the amount of dimensional change of the prepreg (meaning the variation in the amount of thermal shrinkage) is large, the position of the through hole used to connect the layers will shift each time the layers are laminated. Therefore, it is attempted to stabilize the variation in the amount of thermal shrinkage of the prepreg. However, according to studies by the present inventors, it was found that prepregs containing conventional resin compositions cannot sufficiently suppress the variation in dimensional change, so there is still room for further improvement in this regard.

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

After the inventor devoted himself to research in order to solve the above-mentioned problems, he found that a prepreg can solve the above-mentioned problems and completed the present invention. The prepreg is obtained through the following steps. : After the thermosetting resin composition is impregnated into the base material, the thermosetting resin composition is B-staged to obtain a prepreg precursor, and then the surface of the prepreg precursor is treated at a predetermined heat source temperature. Heat treatment is performed to obtain surface heat treatment of the prepreg. The present invention is completed based on such technical ideas.

The present invention relates to the following technologies [1] to [20]. [1] A method for manufacturing a prepreg, comprising: impregnating a base material with a thermosetting resin composition, and then B-staged the thermosetting resin composition to obtain a prepreg precursor. ; and, a surface heating treatment step performed after the aforementioned step of obtaining a prepreg precursor; and, the aforementioned surface heating treatment step is a step of heating the surface of the prepreg precursor at a heat source temperature of 200 to 700°C . [2] A method for manufacturing a prepreg, comprising: impregnating a base material with a thermosetting resin composition, and then B-staged the thermosetting resin composition to obtain a prepreg precursor. ; and, a surface heating treatment step performed after the aforementioned step of obtaining a prepreg precursor; and, the aforementioned surface heating treatment step is to treat the prepreg in such a manner that the surface temperature of the prepreg precursor becomes 40 to 130°C. The step of heat treating the surface of the precursor. [3] The method for manufacturing a prepreg according to the above [1] or [2], wherein after the step of obtaining the prepreg precursor and before the step of surface heating treatment, there is a step of converting the prepreg precursor into The step of cooling the material to 5~60℃. [4] The method for manufacturing a prepreg according to any one of the above [1] to [3], wherein the 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 [1] to [4] above, 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 maleimine compound having at least 2 N-substituted maleimide groups, (a2) a monoamine compound represented by the following general formula (a2-1), and (a3) represented by the following general formula (a3) The diamine compound represented by -1) is obtained by reacting; In the general formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group and a sulfonic acid group, R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, and t is an integer of 1 to 5. , u is an integer from 0 to 4 and satisfies 1≦t+u≦5, where, when t is an integer from 2 to 5, the plural R ^A4 can be the same or different, in addition, when u is an integer from 2 to 4 , plural RA ^A5 can be the same or different; In General Formula ⁽ a3-1 ^{) ,} or a sulfonic acid group, v and w are each independently an integer of 0 to 4. [7] The method for manufacturing a prepreg according to the above [5] or [6], wherein the thermosetting resin composition further contains: (B) epoxy resin; (C) copolymer resin having 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 coupling agent. [8] The method for manufacturing a prepreg according to the above [7], wherein the component (B) is selected from the group consisting of bisphenol F-type epoxy resin, phenol novolak-type epoxy resin, and cresol novolak-type epoxy resin. Selected from the group consisting of oxy resin, naphthalene-type epoxy resin, anthracene-type epoxy resin, biphenyl-type epoxy resin, biphenyl aralkyl novolac-type epoxy resin, and dicyclopentadiene-type epoxy resin of at least 1 species. [9] The method for producing a prepreg according to the above [7] or [8], wherein the component (C) has a structural unit represented by the following general formula (Ci) and a structural unit represented by the following general formula (Ci) Copolymer resin of structural unit represented by C-ii): In formula (Ci), R ^C1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ^C2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms. , hydroxyl group, or (meth)acrylyl group, x is an integer from 0 to 3, where, when x is 2 or 3, the plurality of R ^C2 may be the same or different. [10] A prepreg including a base material and a thermosetting resin composition, and having a standard deviation σ calculated according to the following method of 0.012% or less. The method for calculating the standard deviation σ is: Divide thickness 18 μm copper foil is overlapped on both sides of a prepreg, and heat and pressure molding is performed at 190°C and 2.45 MPa for 90 minutes to produce a double-sided copper-clad laminate with a thickness of 0.1 mm; for the above The double-sided copper-clad laminated board obtained by the method is provided with openings with a diameter of 1.0 mm at locations 1 to 8 described in Figure 1 on the surface of the double-sided copper-clad laminated board; The vertical direction is the direction of 1-7, 2-6, 3-5 and the horizontal direction is 3 points of the direction of 1-3, 8-4, 7-5. Use the image measuring machine to measure each After measuring the distance between the three points, set each measured distance as an initial value. Then, remove the outer copper foil and heat it with a dryer at 185°C for 60 minutes. After cooling, measure the initial value using the same method. method, to measure the distance between each three points in the vertical direction, that is, the direction of 1-7, 2-6, 3-5, and the horizontal direction, that is, in the direction of 1-3, 8-4, and 7-5. Measurement: Find the average value of the change rates from the initial value of each measured distance, and calculate the standard deviation σ relative to the average value. [11] The prepreg according to the above [10], which is obtained by the prepreg manufacturing method 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) epoxy resin; (C) copolymer resin having a substituted a structural unit of a vinyl compound and a structural unit derived from maleic anhydride; and (D) silica treated with an aminosilane coupling agent. [14] The prepreg according to the above [10], wherein the thermosetting resin composition contains (G) epoxy resin and (H) 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 including the prepreg according to any one of the above [10] to [15] and a metal foil. [17] A printed wiring board including the prepreg according to any one of the above [10] to [15] or the laminate according to the above [16]. [18] A semiconductor package in which a semiconductor element is mounted on the printed wiring board described in [17]. [19] The method for manufacturing 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 cured agent. [20] The method for producing a prepreg according to any one of the above [1] to [4], wherein the thermosetting resin composition contains (K) a silicone-modified maleimide compound and (L) Imidazole compound. [effect]

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

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

[Prepreg manufacturing method] The invention is a method for manufacturing prepregs, which has: A step (step 1) of impregnating a base material with a thermosetting resin composition and then B-stage the thermosetting resin composition to obtain a prepreg precursor; and, The surface heating treatment step (step 3) is performed after the aforementioned step of obtaining the prepreg precursor; and the aforementioned step 3 is to heat the surface of the prepreg precursor at a heat source temperature of 200 to 700°C to obtain the prepreg precursor. Soaking steps. The aforementioned step 3 can also be called a surface heating treatment step, which is to treat the prepreg precursor so that the surface temperature of the prepreg precursor becomes 40 to 130°C after the aforementioned step of obtaining the prepreg precursor. The surface is heated to obtain a prepreg. Furthermore, it is generally preferred to have a method of cooling the prepreg precursor to 5 to 35°C after the aforementioned step of obtaining the prepreg precursor (step 1) and before the aforementioned surface heating treatment step (step 3). step (step 2). Hereinafter, steps 1 to 3 will be described in order, and then the base material and thermosetting resin composition constituting the prepreg will be described.

＜Step 1＞ Step 1 is a step in which a base material is impregnated with a thermosetting resin composition, and then the thermosetting resin composition is B-staged to obtain a prepreg precursor. The method of impregnating the base material with the thermosetting resin composition is not particularly limited, and examples include a hot melt method, a solvent method, and the like. The hot melt method is a method of directly impregnating a base material with a thermosetting resin composition whose viscosity is reduced by heating. For example, the thermosetting resin composition is temporarily applied to a coating with excellent releasability. A method of forming a resin film on cloth paper, etc. and then laminating it on a base material; a method of directly applying a thermosetting resin composition to a base material using a die coater, etc. The solvent method is a method in which a thermosetting resin composition contains an organic solvent and is impregnated into a base material in a state of preparing a resin varnish. Examples thereof include a method in which the base material is immersed in the resin varnish and then dried.

By impregnating the base material with the thermosetting resin composition and then 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, B-stage formation may be performed simultaneously with heating when the aforementioned resin film is laminated on the base material. In other words, a thermosetting resin composition can be B-staged to obtain a prepreg precursor by laminating the aforementioned resin film on a base material while heating, and continuing to heat while maintaining this state. At this time, the heating temperature during lamination and the heating temperature during B-stage formation may be the same or different. When the aforementioned resin film is laminated on a base material, 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, B-stage formation may be performed simultaneously with heating when drying the aforementioned resin varnish. In other words, the thermosetting resin composition can be B-staged to obtain a prepreg precursor by immersing the base material in the resin varnish and then drying the organic solvent by heating while maintaining this state. Continue heating. At this time, the heating temperature during lamination and the heating temperature during B-stage formation may be the same or different. When drying the resin varnish, the heating temperature is not particularly limited, but is preferably 10 to 190°C, and may be 15 to 180°C, or 15 to 170°C.

In this step 1, the B-stage conditions are not particularly limited as long as the thermosetting resin composition can be B-staged, and may be appropriately determined according to the type of thermosetting resin and the like. As the heating temperature, for example, 70 to 190°C is preferred, and it may be 80 to 180°C, 120 to 180°C, or 140 to 180°C. The heating method is not particularly limited, and examples include a heating method using a flat heater, a heating method using hot air, a heating method using high frequency, a heating method using magnetic lines of force, and a heating method using a laser. Heating methods that combine these, etc. Among these, the heating method using a flat heater and the heating method using hot air are simpler and more preferable. In addition, the heating time may be, 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 to cool the prepreg precursor obtained by subjecting the prepreg precursor to a B-stage by heat treatment in step 1 and cooling the prepreg precursor to at least a lower temperature than that in which the prepreg precursor is B-staged. The temperature of the heat treatment is a lower temperature step. By implementing step 2, the thermosetting resin composition undergoes a heat history that is generally applied when manufacturing a prepreg, such as B-stage formation and cooling, and the prepreg precursor obtained may be Internally, there is a tendency for strain, etc., which is known to occur in prepregs, and this strain may become the main cause of dimensional changes. As mentioned above, it is preferable to allow the strain etc. caused by thermal history such as heating (step 1) and cooling (step 2) to exist inside before step 3 to be described later. This makes it easier to effectively achieve the following. : Use step 3 to eliminate the above-mentioned strains and make the dimensional changes uniform. Furthermore, since the strain caused by the thermal history of heating (step 1) and cooling (step 2) has been eliminated by step 3, even if the same thermal history is applied after step 3, no strain will occur, or even if it does The strain is also very small, so the prepreg obtained by the present invention tends to have extremely small variation in the amount of dimensional change.

The prepreg precursor can be cooled by leaving it to cool naturally, or by using cooling devices such as air blowers and cooling rollers. Furthermore, from the viewpoint of productivity, cooling is preferably performed by an air blower. In this step, the surface temperature of the cooled prepreg precursor is usually 5-60°C, preferably 10-45°C, preferably 10-30°C, and more preferably room temperature. In addition, in this specification, the so-called room temperature refers to the ambient temperature without temperature control such as heating and cooling. It is generally about 15 to 25°C, but it may change due to weather, season, etc., so it is not limited to within the above range.

＜Step 3＞ Step 3 is a surface heating treatment step, which heats the surface of the prepreg precursor obtained in the aforementioned step 1 or the aforementioned step 2 at a heat source temperature of 200 to 700°C to obtain a prepreg. It can also be called a surface heating treatment step, which heats the surface of the prepreg precursor so that the surface temperature of the prepreg precursor becomes 40 to 130°C to obtain a prepreg. Through this step 3, the deviation of the dimensional change amount of the prepreg will be smaller. The correct reason for this is not yet clear, but it is thought that through this step 3, the strain of the base material in the prepreg precursor obtained in step 1 or step 2 can be eliminated, and the strain caused by the strain can be reduced. Dimensional changes during hardening, therefore, the variation in dimensional changes can be reduced. By reducing the variation in the dimensional change amount, the problem of positional deviation of the through holes can be reduced.

In step 3, the heating method of the surface heat treatment is not particularly limited, and examples thereof include: a heating method using a flat heater, a heating method using hot air, a heating method using high frequency, and a heating method using magnetic lines of force. Heating methods by laser, heating methods combining these, etc. Among these, from the viewpoint of ease of controlling the surface temperature, the heating method using a flat heater and the heating method using hot air are 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 better productivity of the prepreg and maintaining the prepreg in the B-stage state while using it. From the viewpoint of reducing variation in 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 performing B-stage formation in step 1. From this point of view, the heat source temperature when performing surface heating treatment is preferably 250 to 700°C, more preferably 300 to 600°C, and more preferably 350 to 550°C. In particular, when performing a heating method using a flat heater or a heating method using hot air, it is preferable to perform surface heating treatment within the aforementioned temperature range. Furthermore, in one aspect of the present invention, from the viewpoint of reducing variation in dimensional change while maintaining good formability of the prepreg, the surface heating treatment is performed such that the surface temperature of the prepreg precursor becomes, for example, It is carried out at the following temperature: preferably 40 to 130°C, more preferably 40 to 110°C, still more preferably 60 to 90°C. It is preferable to set the surface temperature of the prepreg precursor to this range based on the aforementioned heat source temperature. The heating time of the surface heat treatment is not particularly limited, from the viewpoint of maintaining good productivity of the prepreg, and from the viewpoint of maintaining the prepreg in the B-stage state and reducing the variation in dimensional change while maintaining good formability. It seems that 1.0 to 10.0 seconds is better, 1.5 to 6.0 seconds is better, and 2.0 to 4.0 seconds is better. From the viewpoint of reducing the variation in dimensional change while maintaining good formability of the prepreg, the increase in the surface temperature of the prepreg precursor caused by the surface heat treatment (that is, the increase in the surface temperature of the prepreg precursor before the surface heat treatment) The absolute value of the difference between the surface temperature and the maximum surface temperature reached during the surface heating treatment) is preferably 5 to 110°C, more preferably 20 to 90°C, and more preferably 40 to 70°C. The detailed heating conditions of the surface heating treatment only need to be conditions that can raise the surface temperature of the prepreg precursor higher than the surface temperature before the surface heating treatment by setting the heat source temperature to the aforementioned range, and as long as the surface temperature is There is no particular limitation within the range that the various properties (such as fluidity) of the obtained prepreg are not significantly affected, and it may be appropriately determined according to the type of thermosetting resin, etc.

From the viewpoint of the handleability and adhesion of the prepreg, the prepreg obtained in step 3 is preferably provided to a cooling step of cooling the prepreg. The prepreg can be cooled by natural cooling, or by using cooling devices such as air blowers and cooling rollers. The temperature of the prepreg after cooling is usually 5 to 80°C, preferably 8 to 50°C, preferably 10 to 30°C, and more preferably room temperature.

In the prepreg of the present invention obtained in the above manner, the content of the thermosetting resin composition in terms of solid content is preferably 20 to 90 mass%, preferably 30 to 85 mass%, and 50 to 80 mass%. % better. The thickness of the prepreg of the present invention is, for example, 0.01 to 0.5 mm. From the viewpoint of formability 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 manufacturing the prepreg of the present invention will be described in detail in order. [Substrate] As the base material constituting the prepreg of the present invention, a sheet-shaped reinforced base material is used, and conventional base materials used in various laminates for electrically insulating materials can be used. Examples of the base material include natural fibers such as paper and cotton lint; inorganic fibers such as glass fiber and asbestos; arylamide, polyimide, polyvinyl alcohol, polyester, tetrafluoroethylene, and acrylic. organic fibers such as force; mixtures thereof, etc. Among these, glass fiber is preferred from the viewpoint of flame retardancy. Examples of the glass fiber base material include: woven fabrics using E glass, C glass, D glass, S glass, etc.; or glass woven fabrics in which short fibers are bonded with an organic binder; glass fibers and Base materials made of mixed cellulose fibers, etc. Glass fabric using E glass is preferred. These substrates have shapes such as woven fabrics, non-woven fabrics, yarn bundles, cut-strand felts, surface felts, etc. Furthermore, the material and shape are selected according to the intended use and performance of the molded article. One type can be used alone, and two or more 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 formability and high-density wiring, 0.015 to 0.2 mm is preferable, and 0.02 to 0.15 mm is more preferable. From the viewpoints of heat resistance, moisture resistance, processability, etc., these substrates are preferably surface-treated with a silane coupling agent or the like, or mechanically opened. .

However, although the prepregs described in the aforementioned Patent Documents 1 to 8 show relatively good relative dielectric constants, there are an increasing number of examples in which they cannot meet the stringent requirements of the market in recent years. In addition, not only cannot the variation in dimensional change be sufficiently suppressed, but there are also often problems in high heat resistance, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing properties (laser processability). Neither is adequate, and there is room for further improvement at this point. In addition, the actual situation is that materials have not been fully developed from the perspective of satisfying all the aforementioned characteristics. However, in the present invention, by using the prepreg manufacturing method of the present invention described above and setting the components of the thermosetting resin composition to the following components, it is possible to fully suppress the variation in the amount of dimensional change and to achieve a high temperature. Heat resistance, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability and throwing properties (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. It can achieve high heat resistance, high metal foil adhesion, high glass transition temperature, low thermal expansion, and moldability in addition to fully suppressing the variation in dimensional change. From the viewpoint of satisfactory properties and throwing properties (laser processability), a thermosetting resin composition (hereinafter referred to as thermosetting resin composition [I]) containing (A) is preferred Maleimide compounds. From the same viewpoint, the thermosetting resin composition [I] preferably further contains: (B) epoxy resin; (C) copolymer resin having a structural unit and source derived from a substituted vinyl compound A structural unit derived from maleic anhydride; and (D) silica treated with an aminosilane coupling agent. From the same viewpoint, the thermosetting resin composition [I] preferably contains the (E) curing agent, and from the viewpoint of flame retardancy, it is preferable to contain the (F) flame retardant. In addition, from the viewpoint of fully suppressing variation in the amount of dimensional change, an epoxy resin composition [II] containing (G) epoxy resin and (H) epoxy resin hardener, and (if necessary) may be used. I) hardening accelerator and (J) inorganic filler material, which can also be a thermosetting resin composition [III], which contains (K) silicone modified maleimide compound and (L) imidazole compound, and Required (M) Inorganic filler material.

First, each component contained in the thermosetting resin composition [I] will be described in detail. <(A) Maleimine Compound> The component (A) is a maleimine compound (hereinafter, sometimes referred to as a maleimide compound (A)) having an N-substituted maleimine compound. It is preferably a maleimide compound having an N-substituted maleimide group, preferably a maleimide compound having an N-substituted maleimide group, wherein (a1) has at least 2 N-substituted maleimide groups. Amine-based maleimine compound [hereinafter, abbreviated to maleimine compound (a1)], (a2) a monoamine compound represented by the following general formula (a2-1) [hereinafter, abbreviated to monoamine Compounds (a2)] and (a3) are obtained by reacting a diamine compound represented by the following general formula (a3-1) [hereinafter simply referred to as a diamine compound (a3)]. In the general formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group and a sulfonic acid group, R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, and t is an integer of 1 to 5. , u is an integer from 0 to 4, and satisfies 1≦t+u≦5, where, when t is an integer from 2 to 5, the plural R ^A4 can be the same or different, in addition, when u is an integer from 2 to 4 When , a plurality of R ^A5 can be the same or different; In General Formula ⁽ a3-1 ^{) ,} , or a sulfonic acid group, v and w are each independently an integer from 0 to 4. The following 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 organic solvents and 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 800. 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 (converted to standard polystyrene) using tetrahydrofuran as a solution. More specifically, it is Values 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 maleimine compound (a1) include an aliphatic hydrocarbon group between any two maleimide groups among a plurality of maleimine groups (where no aromatic hydrocarbon group is present). ) of a maleimine compound [hereinafter, referred to as aliphatic hydrocarbon group-containing maleimide], or an aromatic aromatic compound between any two maleimine groups among a plurality of maleimine groups. A maleimide compound containing an aromatic hydrocarbon group [hereinafter referred to as an aromatic hydrocarbon group-containing maleimide compound]. Among them, aromatic hydrocarbon-containing maleyl is the most popular from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing properties. Imine is preferred. The aromatic hydrocarbon group-containing maleimine only needs to contain an aromatic hydrocarbon group between any combination of two arbitrarily selected maleimine groups, and may have both an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The maleimide compound (a1) is preferred from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability and throwing properties. A maleimine compound having 2 to 5 N-substituted maleimide groups in the molecule, more preferably a maleimine compound having 2 N-substituted maleimide groups in the molecule . In addition, the maleimide compound (a1) is preferable from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing properties. It is an aromatic hydrocarbon group-containing maleimide represented by any one of the following general formulas (a1-1) to (a1-4), more preferably, it is represented by the following general formulas (a1-1), (a1 The aromatic hydrocarbon group-containing maleimide represented by -2) or (a1-4) is particularly preferably the aromatic hydrocarbon group-containing maleimide represented by the following general formula (a1-2).

In the above formulas (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 or 2 carbon atoms. ~5 alkylene group, -O-, -C(=O)-, -S-, -S-S-, or sulfonyl group; p, q and r are each independently an integer from 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, n- Pentyl etc. From the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability and throwing properties, as the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is used. Aliphatic hydrocarbon groups are preferred, and methyl and ethyl groups are preferred.

Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^A1 include methylene, 1,2-dimethylene, 1,3-trimethylene, 1,4-tetramethylene, 1 ,5-pentamethylene, etc. From the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing properties, the alkylene group has 1 to 3 carbon atoms. An alkylene group is preferred, and a methylene group is preferred. Examples of the alkylene group having 2 to 5 carbon atoms represented by X ^A1 include ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, isopentylene group, and the like. Among them, as the alkylene group, from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing properties, alkylene groups are Isopropyl is preferred. Among the above options, X ^A1 is preferably an alkylene group having 1 to 5 carbon atoms or an alkylene group having 2 to 5 carbon atoms. The preferred example is as mentioned above. p, q and r are each independently an integer from 0 to 4, from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability and throwing properties. Look, in any case, 0 to 2 is better, 0 or 1 is better, and 0 is better. s is an integer of 0 to 10, and from the viewpoint of ease of acquisition, 0 to 5 is preferred, and 0 to 3 is more preferred. In particular, the aromatic hydrocarbon group-containing maleimide compound represented by the general formula (a1-3) is preferably a mixture in which s is 0 to 3.

Specific examples of the maleimide compound (a1) include N,N'-ethylidenebismaleimide, N,N'-hexamethylenebismaleimide, bis(4 -Maleiminocyclohexyl)methane, 1,4-bis(maleiminomethyl)cyclohexane and other aliphatic hydrocarbon-containing maleimide; N,N'-(1,3 -phenylene) bismaleimide, N,N'-[1,3-(2-methylphenylene)]bismaleimide, N,N'-[1,3-( 4-methylphenylene)]bismaleimide, N,N'-(1,4-phenylene)bismaleimide, bis(4-maleimidophenyl) Methane, bis(3-methyl-4-maleimidophenyl)methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bis Maleimide, bis(4-maleimidophenyl) ether, bis(4-maleimidophenyl)sulfide, bis(4-maleimidophenyl)sulfide Ether, bis(4-maleimidophenyl)ketone, 1,4-bis(4-maleimidophenyl)cyclohexane, 1,4-bis(maleimidophenyl) Methyl)cyclohexane, 1,3-bis(4-maleiminophenoxy)benzene, 1,3-bis(3-maleiminophenoxy)benzene, bis[4 -(3-maleimidophenoxy)phenyl]methane, bis[4-(4-maleimidophenoxy)phenyl]methane, 1,1-bis[4-( 3-Maleimidophenoxy)phenyl]ethane, 1,1-bis[4-(4-maleimidophenoxy)phenyl]ethane, 1,2-bis [4-(3-maleiminophenoxy)phenyl]ethane, 1,2-bis[4-(4-maleimidophenoxy)phenyl]ethane, 2 ,2-bis[4-(3-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane , 2,2-bis[4-(3-maleiminophenoxy)phenyl]butane, 2,2-bis[4-(4-maleimidophenoxy)benzene yl]butane, 2,2-bis[4-(3-maleiminophenoxy)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-maleimide phenyloxy)biphenyl, 4,4-bis(4-maleiminophenoxy)biphenyl, bis[4-(3-maleiminophenoxy)phenyl]one , bis[4-(4-maleiminophenoxy)phenyl]one, 2,2'-bis(4-maleimidophenyl) disulfide, bis(4-maleiminophenyl) Leimidophenoxy) disulfide, bis[4-(3-maleiminophenoxy)phenyl] sulfide, bis[4-(4-maleiminophenoxy) base)phenyl] sulfide, bis[4-(3-maleiminophenoxy)phenyl]sulfoxide, bis[4-(4-maleiminophenoxy)phenyl ]Shenyl, bis[4-(3-maleiminophenoxy)phenyl]sine, bis[4-(4-maleiminophenoxy)phenyl]sine, bis[ 4-(3-maleiminophenoxy)phenyl] ether, bis[4-(4-maleimidophenoxy)phenyl] ether, 1,4-bis[4- (4-maleiminophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-maleimidophenoxy)-α ,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleiminophenoxy)-α,α-dimethylbenzyl]benzene, 1,3 -Bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene Oxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-maleiminophenoxy)-3,5 -Dimethyl-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleiminophenoxy)-3,5-dimethyl-α, α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleiminophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl base] benzene, polyphenylmethane maleimide and other aromatic hydrocarbon-containing maleimide.

Among these, bis(4-maleimidophenyl)methane and bis(4-maleimidophenyl)methane are preferred from the viewpoint of high reaction rate and the ability to achieve higher heat resistance. Phenyl)sulfide, bis(4-maleimidophenyl) sulfide, bis(4-maleimidophenyl) disulfide, N,N'-(1,3-phenylene) base) bismaleimide and 2,2-bis[4-(4-maleiminophenoxy)phenyl]propane. From the viewpoint of low cost, bis(4 -Maleimidophenyl)methane, N,N'-(1,3-phenylene)bismaleimide, particularly preferably bis(4) from the viewpoint of solubility in solvents -Maleimidophenyl)methane. One type of maleimide compound (a1) may be used alone, or two or more types may be used in combination.

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

In the above general formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group and a sulfonic acid group, R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, and t is 1 to 5. Integer, u is an integer from 0 to 4, and satisfies 1≦t+u≦5. When t is an integer from 2 to 5, the plural R ^A4 can be the same or different. In addition, when u is an integer from 2 to 4, When it is an integer, the plural RA ^A5 may be the same or different. From the viewpoint of solubility and reactivity, the acidic substituent represented by R ^A4 is preferably a hydroxyl group or a carboxyl group, and when heat resistance is also taken into consideration, a hydroxyl group is preferably used. t is an integer from 1 to 5. From the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability and throwing properties, t is 1 to 3 The integer is better, 1 or 2 is better, 1 is better. 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, n-pentyl, and the like. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. Examples of the halogen atom represented by R ^A5 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. u is an integer from 0 to 4. From the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability and throwing properties, u is an integer from 0 to 3. An integer is preferred, an integer from 0 to 2 is preferred, 0 or 1 is more preferred, and 0 is particularly preferred. From the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing properties, the following is preferred as the monoamine compound (a2): The monoamine compound represented by the general formula (a2-2) or (a2-3) is more preferably a monoamine compound represented by the following general formula (a2-2). Among them, R ^A4 , R ^A5 and u in the general formula (a2-2) and (a2-3) are the same as R ^A4 , R ^A5 and u in the general formula (a2-1), and the preferred examples are also the same.

Examples of the monoamine compound (a2) include o-aminophenol, m-aminophenol, p-aminophenol, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, and o-aminobenzene sulfonate. Acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and other monoamine compounds with acidic substituents. Among these, m-aminophenol, p-aminophenol, p-aminobenzoic acid, and 3,5-dihydroxyaniline are preferred from the viewpoint of solubility and reactivity, and from the viewpoint of heat resistance , o-aminophenol, meta-aminophenol, and p-aminophenol are preferred, and p-aminophenol is more preferred when considering dielectric properties, low thermal expansion and manufacturing cost. 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 General Formula ⁽ a3-1 ^{) ,} , or a sulfonic acid group, v and w are each independently an integer from 0 to 4.

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

As the diamine compound (a3), a diamine compound represented by the following general formula (a3-1') is preferred. In the general formula (a3-1'), X ^A2 , R ^A6 , R ^A7 , v and w are the same as X ^A2 , R ^A6 , R ^A7 , v and w in the aforementioned general formula (a3-1), and the preferred state is Same thing.

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'-diaminodiphenyl sulfide, 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'-Tetramethylchloride-4 ,4'-diaminodiphenylmethane, 2,2',6,6'-tetrabromo-4,4'-diaminodiphenylmethane, etc. Among these, from the viewpoint of low cost, 4,4'-diaminodiphenylmethane and 3,3'-diethyl-4,4'-diaminodiphenyl are preferred. From the viewpoint of solubility in solvents, methane is more preferably 4,4'-diaminodiphenylmethane.

The reaction of the maleimine compound (a1), the monoamine compound (a2) and the diamine compound (a3) is preferably carried out in the following manner: preferably in the presence of an organic solvent, at a reaction temperature of 70 The reaction is 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.

(Amounts of maleimine compound (a1), monoamine compound (a2), and diamine compound (a3) used) Maleimine compound (a1), monoamine compound (a2), and diamine compound (a3) ), the preferred usage amounts of the three are: the sum of the primary amine group equivalents [recorded as -NH ₂ group equivalents] of the monoamine compound (a2) and the diamine compound (a3) and the maleimine The relationship between the maleimide group equivalents of the compound (a1) satisfies the following formula. 0.1≦[maleimide group equivalent]/[total amount of −NH ₂ group equivalent]≦10 By setting [maleimide group equivalent]/[total amount of −NH ₂ group equivalent] to 0.1 or more, It is possible to prevent gelation and heat resistance from being reduced, and by setting [maleimide group equivalent]/[total -NH ₂ group equivalent] to 10 or less, it is possible to prevent 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 group equivalent]/[total of −NH ₂ group equivalents]≦9 More preferably, the following formula is satisfied. 2≦[Maleimide group equivalent]/[Total of -NH ₂ group equivalents]≦8

(organic solvent) As mentioned above, the reaction of the maleimine compound (a1), the monoamine compound (a2) and the diamine compound (a3) is preferably carried out in an organic solvent. The organic solvent is not particularly limited as long as it does not adversely affect the reaction. Examples include: alcohol solvents such as ethanol, propanol, butanol, methylcellulose, butylcellulose, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane Ketone solvents such as ketones; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and trimethylbenzene; including amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone Nitrogen atom-containing solvents including dimethyl tyrosine-based solvents; sulfur atom-containing solvents including dimethyl tyrosine-based solvents; ester-based solvents such as ethyl acetate and γ-butyrolactone, etc. Among these, from the viewpoint of solubility, alcohol-based solvents, ketone-based solvents, and ester-based solvents are preferred, and from the viewpoint of low toxicity, cyclohexanone, propylene glycol monomethyl ether, and Methylcellulose and γ-butyrolactone are also more preferred when considering their high volatility and not being easily left as residual solvents when manufacturing prepregs, cyclohexanone, propylene glycol monomethyl ether, and dimethyl ethyl ether. Amide, particularly dimethylacetamide. One type of organic solvent may be used alone, or two or more types may be used in combination. The usage amount of the organic solvent is not particularly limited. From the viewpoint of solubility and reaction efficiency, the amount is 100 parts by mass in total of the maleimine compound (a1), the monoamine compound (a2), and the diamine compound (a3). , as long as the usage amount of the organic solvent is the following amount: preferably 25 to 1,000 parts by mass, more preferably 40 to 700 parts by mass, still more preferably 60 to 250 parts by mass. By setting the usage amount of the organic solvent to 25 parts by mass relative to a total of 100 parts by mass of the maleimine compound (a1), the monoamine compound (a2), and the diamine compound (a3), it is easy to ensure solubility. , it can be easily suppressed by setting the usage amount of the organic solvent to 1,000 parts by mass or less based on a total of 100 parts by mass of the maleimine compound (a1), the monoamine compound (a2), and the diamine compound (a3). Reaction efficiency is greatly reduced.

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

＜(B) Epoxy resin＞ Component (B) is an epoxy resin (hereinafter sometimes referred to as epoxy resin (B)), and an epoxy resin having at least two epoxy groups in one molecule is preferred. Examples of the epoxy resin having at least two epoxy groups in one molecule include glycidyl ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, and the like. Among these, glycidyl ether type epoxy resin is preferred. Epoxy resins can also be classified into various epoxy resins based on different main skeletons. Among the above types of epoxy resins, they can be further classified into: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S-type epoxy resin and other bisphenol-type epoxy resins; biphenyl aralkyl novolak-type epoxy resin, phenol novolac-type epoxy resin, alkylphenol novolak-type epoxy resin, cresol novolak-type epoxy resin Resin, naphthol alkylphenol copolymer novolak type epoxy resin, naphthol aralkyl cresol copolymer novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, etc. Novolac type epoxy resin; stilbene type epoxy resin; triazine skeleton-containing epoxy resin; fluorine skeleton-containing epoxy resin; naphthalene-type epoxy resin; anthracene-type epoxy resin; triphenylmethane-type epoxy resin ; Biphenyl-type epoxy resin; xylene-type epoxy resin; dicyclopentadiene-type epoxy resin and other alicyclic epoxy resins, etc. Among these, from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing properties, those made of bisphenol F are preferred. type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl novolac type ring At least one selected from the group consisting of oxy resin and dicyclopentadiene-type epoxy resin, preferably from the viewpoint of low thermal expansion and high glass transition temperature, a cresol novolac-type epoxy resin At least 1 selected from the group consisting of, naphthalene-type epoxy resin, anthracene-type epoxy resin, biphenyl-type epoxy resin, biphenyl aralkyl novolac-type epoxy resin and phenol novolak-type epoxy resin , preferably cresol novolak type epoxy resin. Epoxy resin (B) may be used individually by 1 type, and may use 2 or more types together.

The epoxy equivalent of the epoxy resin (B) is preferably 100 to 500 g/eq, more preferably 120 to 400 g/eq, more preferably 140 to 300 g/eq, and particularly preferably 170 to 240 g/eq. Here, the epoxy equivalent is the resin equivalent per epoxy group (g/eq), and can be measured according to the method specified in JIS K 7236 (2001). Specifically, it can be determined by using the automatic titration device "GT-200 type" manufactured by Mitsubishi Chemical Analytech Co., Ltd., weighing 2 g of epoxy resin into a 200 mL beaker, and then dripping After dissolving 90 mL of methyl ethyl ketone with an ultrasonic cleaner, add 10 mL of glacial acetic acid and 1.5 g of cetyltrimethylammonium bromide, and add 0.1 mol/L perchloric acid/acetic acid solution. to titrate. Examples of commercially available epoxy resins (B) include cresol novolak type epoxy resin "EPICLON (registered trademark) N-673" (manufactured by DIC Co., Ltd., epoxy equivalent: 205 to 215 g/ eq), naphthalene-type epoxy resin "HP-4032" (manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 152 g/eq), biphenyl-type epoxy resin "YX-4000" (manufactured by Mitsubishi Chemical Co., Ltd., Epoxy equivalent: 186 g/eq), dicyclopentadiene epoxy resin "HP-7200H" (manufactured by DIC Co., Ltd., epoxy equivalent: 280 g/eq), etc. In addition, the epoxy equivalent is the value described in the catalog of the manufacturing company of the product.

＜(C) Specific copolymer resin＞ Component (C) is a copolymerized resin (hereinafter sometimes referred to as copolymerized resin (C)) having a structural unit derived from a substituted vinyl compound and a structural unit derived from maleic anhydride. Examples of substituted vinyl compounds include aromatic vinyl compounds, aliphatic vinyl compounds, vinyl compounds substituted with functional groups, and the like. Examples of the aromatic vinyl compound include styrene, 1-methylstyrene, vinyltoluene, dimethylstyrene, and the like. Examples of aliphatic vinyl compounds include propylene, butadiene, isobutylene, and the like. Examples of vinyl compounds substituted with functional groups include acrylonitrile; compounds having (meth)acrylyl groups such as methyl acrylate and methyl methacrylate. Among these, as the substituted vinyl compound, an aromatic vinyl compound is preferred, and styrene is preferred. As 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 formula (Ci), R ^C1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ^C2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms. , hydroxyl group, or (meth)acrylyl group; x is an integer from 0 to 3; where, when x is 2 or 3, the plurality of R ^C2 may be the same or different.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^C1 and R ^C2 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl Key et al. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. Examples of the alkenyl group having 2 to 5 carbon atoms represented by R ^C2 include allyl group, crotyl group, and the like. The alkenyl group is preferably an alkenyl group having 3 to 5 carbon atoms, and more preferably an alkenyl group having 3 or 4 carbon atoms. Examples of the aryl group having 6 to 20 carbon atoms represented by R ^C2 include phenyl group, naphthyl group, anthracenyl group, biphenyl group, and the like. 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, and 0 is better. Among the structural units represented by the general formula (Ci), a structural unit represented by the following general formula (Ci-1) in which R ^C1 is a hydrogen atom and x is 0, that is, a structural unit derived from styrene, is preferred.

In the copolymer resin (C), the content ratio of the structural units derived from the substituted vinyl compound and the structural units derived from maleic anhydride is the structural unit derived from the substituted vinyl compound/the structural units derived from maleic anhydride. The molar ratio of the structural units is preferably 1 to 9, more preferably 2 to 9, more preferably 3 to 8, and particularly preferably 3 to 7. In addition, the content ratio of the structural unit represented by the aforementioned general formula (C-i) to the structural unit represented by the aforementioned general formula (C-ii), that is, the molar ratio of (C-i)/(C-ii), is also expressed as 1 to 9 is preferred, 2 to 9 is more preferred, 3 to 8 is more preferred, and 3 to 7 is particularly preferred. If the molar ratio is 1 or more, preferably 2 or more, the dielectric properties improvement effect tends to be more sufficient, and if the molar ratio is 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 (C-i) and the structural unit represented by the formula (C-ii) The total content of the structural units represented is preferably 50 mass% or more, more preferably 70 mass% or more, more preferably 90 mass% or more, and substantially 100 mass% is particularly preferred. The weight average molecular weight (Mw) of the copolymer resin (C) is preferably 4,500 to 18,000, more preferably 5,000 to 18,000, more preferably 6,000 to 17,000, more preferably 8,000 to 16,000, particularly preferably 8,000 to 15,000, and 9,000 ~13,000 best.

Furthermore, by using a copolymer resin of styrene and maleic anhydride to lower the dielectric constant of the epoxy resin, if it is applied to printed wiring board materials, the impregnation of the base material and the copper foil peeling strength will be improved. will be insufficient, so there is a general tendency to avoid the above methods. Therefore, there is a general tendency to avoid the use of the aforementioned copolymer resin (C). However, the present invention was accomplished by finding out that although the aforementioned copolymer resin (C) is used, by containing the aforementioned components (A) and (B) ) component, it becomes a thermosetting resin composition with high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, and excellent formability and throwing properties.

(Production method of copolymer resin (C)) The copolymer resin (C) can be produced by copolymerizing a substituted vinyl compound and maleic anhydride. The substituted vinyl compound is as described above. One type of substituted vinyl compound may be used alone, or two or more types may be used in combination. Furthermore, in addition to the aforementioned substituted vinyl compound and maleic anhydride, various polymerizable components can also be copolymerized. In addition, substituents such as allyl, methacryloyl, acryloyl, and hydroxyl can be introduced into the substituted vinyl compound, especially the aromatic vinyl compound, through the following reaction: Friedel-Crafts ( 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) and "SMA (registered trademark) EF30" (styrene/maleic anhydride = 3, Mw＝9,500), "SMA(registered trademark) EF40" (styrene/maleic anhydride＝4, Mw＝11,000), "SMA(registered trademark) EF60" (styrene/maleic anhydride＝6, Mw＝11,500) , "SMA (registered trademark) EF80" (styrene/maleic anhydride = 8, Mw = 14,400) [the above is made by CRAY VALLEY Co., Ltd.], etc.

<(D) Silicon oxide treated with aminosilane coupling agent> If silicon oxide treated with an aminosilane coupling agent among silicon oxides (hereinafter, sometimes referred to as silicon oxide (D) treated with an aminosilane coupling agent) is used as ( D) component, in addition to the effect of improving low thermal expansion, it is also possible to suppress silicon oxide from falling off by improving the adhesion with the components (A) to (C). It is better to reduce the deformation of the shape of the laser through hole caused by the excessive amount of desmear.

As the aminosilane-based coupling agent, specifically, a silane coupling agent having a silicon group and an amino group represented by the following general formula (D-1) is preferred. In formula (D-1), R ^D1 is an alkyl group having 1 to 3 carbon atoms or a hydroxyl 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 ^RD1 include methyl, ethyl, n-propyl and isopropyl. Among these, methyl is preferred. Examples of the C2-C4 acyl group represented by ^RD1 include an acetyl group, a propyl group, and an acryl group. Among these, the acetyl group is preferred.

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

Although specific silicon oxide as an inorganic filler other than component (D) can be used instead of silicon oxide (D) treated with an aminosilane-based coupling agent, from the viewpoint of the above-mentioned effects, it is preferable. Silicon oxide (D) treated with an aminosilane coupling agent is used. The specific silicon oxide is, for example, silicon oxide treated with a specific coupling agent, silicon oxide without surface treatment, etc. Specific coupling agents are: epoxy silane coupling agent, phenyl silane coupling agent, alkyl silane coupling agent, alkenyl silane coupling agent, alkynyl silane coupling agent, haloalkyl silane coupling agent, silicon Oxane-based coupling agent, hydrogen silane-based coupling agent, silazane-based coupling agent, alkoxysilane-based coupling agent, chlorosilane-based coupling agent, (meth)acrylic-based silane-based coupling agent, aminosilane-based coupling agent , Isocyanurate silane coupling agent, ureido silane coupling agent, mercapto silane coupling agent, thioether silane coupling agent, or isocyanato silane coupling agent, etc. In addition, silicon oxide (D) treated with an aminosilane coupling agent may be used in combination with the silicon oxide treated with another coupling agent. At this time, relative to 100 parts by mass of silicon oxide (D) treated with an aminosilane coupling agent, the silicon oxide treated with other coupling agents is preferably 50 parts by mass or less, and 30 parts by mass or less. The amount is preferably not more than 15 parts by mass, more preferably not more than 10 parts by mass, and most preferably not more than 5 parts by mass, but is not particularly limited.

Examples of the silicon oxide include deposited silicon oxide produced by a wet process and having a high moisture content, and dry process silicon oxide produced by a dry process and containing almost no bonded water or the like. Examples of dry process silicon oxide include, depending on the production method, grinded silicon oxide, fumed silicon oxide, fused silicon oxide (molten spherical silicon oxide), and the like. Among these, molten silicon oxide is preferred from the viewpoint of low thermal expansion and high fluidity when filled in resin. The average particle size of the silicon oxide is not particularly limited, but 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. By setting the average particle size of silicon oxide to 0.1 μm or more, it is possible to maintain good fluidity during high filling, and by setting the average particle size of silicon oxide to 10 μm or less, it is possible to reduce the probability of mixing coarse particles and suppress Undesirable situations caused by coarse particles occur. Here, the average particle diameter refers to the particle diameter corresponding to the point corresponding to 50% of the volume when the cumulative particle size distribution curve is calculated using the particle diameter, assuming that the total volume of the particles is 100%. It can be determined using laser diffraction. The particle size distribution measuring device of the scattering method can be used for measurement. In addition, the specific surface area of the silicon oxide is preferably 4 cm ² /g or more, preferably 4 to 9 cm ² /g, and more preferably 5 to 7 cm ² /g.

<(E) Curing Agent> The thermosetting resin composition [I] may further contain a curing agent as the (E) component (hereinafter, may be referred to as a curing agent (E)). Examples of the hardener (E) include: dicyandiamide; ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, and diethylaminopropyl Amine, tetramethylguanidine, triethanolamine and other chain aliphatic amines other than dicyandiamide; isophorone diamine, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, bis(4) -Amino-3-methyldicyclohexyl)methane, N-aminoethylpiperazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraxaspiro[ 5.5] cyclic aliphatic amines such as undecane; aromatic amines such as xylylenediamine, phenylenediamine, diaminodiphenylmethane, and diaminodiphenylthione. Among these, dicyandiamide is preferred from the viewpoint of metal foil adhesion and low thermal expansion. This dicyandiamide is represented by H ₂ N-C (=NH)-NH-CN, and its melting point is usually 205 to 215°C. The melting point of dicyandiamide with higher purity is 207 to 212°C. Dicyandiamide is a crystalline substance, which can be orthorhombic crystals or flaky crystals. The purity of dicyandiamide is preferably at least 98%, more preferably at least 99%, and even more preferably at least 99.4%. Commercially available dicyandiamide can be used, and for example, commercially available products manufactured by Japan 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 component (F) (hereinafter, it may be referred to as a flame retardant (F)). Here, although dicyandiamide and the like in the above-mentioned hardener also have the effect of a flame retardant, in the present invention, substances that can exert the function of a hardener are classified as hardeners and are not included in ( F) Ingredients. Examples of the flame retardant include halogen-containing flame retardants containing bromine and chlorine; phosphorus-based flame retardants; and nitrogen-based flame retardants such as guanidine sulfonate, melamine sulfate, melamine polyphosphate, and melamine cyanurate. ; Phosphazene flame retardants such as cyclophosphazene and polyphosphazene; inorganic flame retardants such as antimony trioxide, etc. Among these, phosphorus-based flame retardants are 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 ammonium phosphates such as red phosphorus, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphorus amide; and phosphoric acid; Phosphine oxide, etc. Examples of organic phosphorus-based flame retardants include aromatic phosphates, monosubstituted phosphonic acid diesters, disubstituted phosphinic acid esters, metal salts of disubstituted phosphinic acid, organic nitrogen-containing phosphorus compounds, cyclic Organophosphorus compounds, phosphorus-containing phenolic resins, etc. Among these, aromatic phosphates and metal salts of disubstituted phosphinic acids are preferred. Here, the metal salt is preferably any one of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt, and zinc salt, and is more preferably an aluminum salt. Among organic phosphorus-based flame retardants, aromatic phosphates are preferred.

Examples of aromatic phosphates include triphenyl phosphate, tris(tolyl) phosphate, tris(xylyl) phosphate, diphenyl cresyl phosphate, and bis(2,6-xylyl) cresyl phosphate. , Resorcinol bis(diphenyl phosphate), 1,3-phenylene bis(bis(2,6-xylyl phosphate)), bisphenol A bis(diphenyl phosphate), 1,3- Phenylene bis(diphenyl phosphate), etc. Examples of the monosubstituted phosphonic acid diester include divinyl benzene phosphonate, diallyl benzene phosphonate, bis(1-butenyl benzene phosphonate), and the like. Examples of the disubstituted phosphinate include phenyl diphenylphosphinate, methyl diphenylphosphinate, and the like. Examples of metal salts of disubstituted phosphinic acids include metal salts of dialkylphosphinic acid, metal salts of diallylphosphinic acid, metal salts of divinylphosphinic acid, and diarylphosphinic acids. Metal salts of acids, etc. As mentioned above, these metal salts are preferably any one of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt and zinc salt. Examples of organic nitrogen-containing phosphorus compounds include phosphazene compounds such as bis(2-allylphenoxy)phosphazene and bis(tolyl)phosphazene; melamine phosphate, melamine pyrophosphate, melamine polyphosphate, polyphosphate, etc. Melamine phosphate, etc. Examples of cyclic organophosphorus compounds include: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10 -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc. Among these, at least one selected from aromatic phosphates, metal salts of disubstituted phosphinic acids, and cyclic organophosphorus compounds is preferred, and aromatic phosphates are more preferred.

Furthermore, the aromatic phosphate ester 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) Metal salt of disubstituted phosphinic acid.

In the formulas (F-1) to (F-3), R ^F1 to R ^F5 are each independently an alkyl group or a halogen atom having 1 to 5 carbon atoms; e and F are each independently an integer of 0 to 5, and g, h and i are each independently an integer from 0 to 4. R ^F6 and R ^F7 are each independently an alkyl group with 1 to 5 carbon atoms or an aryl group with 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 from 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, n-pentyl Key et al. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. Examples of the halogen atoms represented by ^RF1 to ^RF5 include fluorine atoms and the like. It is preferable that e and f are integers from 0 to 2, and 2 is more preferable. g, h and i are preferably integers from 0 to 2, preferably 0 or 1, and more preferably 0. Examples of the alkyl group having 1 to 5 carbon atoms represented by ^RF6 and ^RF7 include the same groups as in the case of ^RF1 to ^RF5 . Examples of the aryl group having 6 to 14 carbon atoms represented by ^RF6 and ^RF7 include phenyl group, naphthyl group, biphenyl group, anthracenyl group, and the like. The aromatic hydrocarbon group is preferably an aryl group having 6 to 10 carbon atoms. j is equal to the valence of the metal ion, that is, it changes in the range of 1 to 4 according to the type of M. As M, an aluminum atom is preferred. Furthermore, when M is an aluminum atom, j is 3.

(Content of each component of thermosetting resin composition [I]) In the thermosetting resin composition [I], the content of components (A) to (D) is not particularly limited. Preferably, the content of component (A) is 100 parts by mass in total of components (A) to (C). It is 15-65 parts by mass, the component (B) is 15-50 parts by mass, the component (C) is 10-45 parts by mass, and the component (D) is 30-70 parts by mass. When the component (A) is 15 parts by mass or more based on 100 parts by mass of the components (A) to (C) in total, it is possible to obtain high heat resistance, low relative dielectric constant, high glass transition temperature and low thermal expansion. tendency. On the other hand, when the component (A) is 65 parts by mass or less based on 100 parts by mass of the components (A) to (C) in total, the thermosetting resin composition [I] has good fluidity and moldability. tendency. When the component (B) is 15 parts by mass or more based on 100 parts by mass of the components (A) to (C) in total, high heat resistance, high glass transition temperature, and low thermal expansion tend to be obtained. On the other hand, when the component (B) is 50 parts by mass or less based on 100 parts by mass of the components (A) to (C) in total, it may result in high heat resistance, low relative dielectric constant, and high glass transition temperature. and low thermal expansion tendency. When the component (C) is 10 parts by mass or more relative to 100 parts by mass of the components (A) to (C) in total, high heat resistance and a low relative dielectric constant tend to be obtained. On the other hand, it is possible to obtain high heat resistance, high metal foil adhesion and low thermal expansion by containing 45 parts by mass or less of the component (C) with respect to 100 parts by mass of the components (A) to (C) in total. tendency. When the component (D) is 30 parts by mass or more relative to 100 parts by mass of the components (A) to (C) in total, there is a tendency that excellent low thermal expansion properties can be obtained. On the other hand, when the component (D) is 70 parts by mass or less based on 100 parts by mass of the components (A) to (C) in total, it is possible to obtain heat resistance and flow of the thermosetting resin composition [I] Tendency to have good properties and formability.

In addition, 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 relative to 100 parts by mass of the components (A) to (C) in total. . When the component (E) is 0.5 parts by mass or more relative to 100 parts by mass of the components (A) to (C) in total, high metal foil adhesion and excellent low thermal expansion tend to be obtained. On the other hand, when the component (E) is 6 parts by mass or less based on 100 parts by mass of the components (A) to (C) in total, there is a tendency that high heat resistance can be obtained.

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

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

(additive) Examples of additives include inorganic fillers other than the aforementioned component (D), hardening accelerators, colorants, antioxidants, reducing agents, ultraviolet absorbers, fluorescent whitening agents, adhesion improving agents, and organic fillers. wait. One type of these may be used alone, or two or more types may be used in combination.

(organic solvent) The thermosetting resin composition [I] may contain an organic solvent from the viewpoint of easy handling by dilution and the viewpoint of easy production of a prepreg to be described later. In this specification, the thermosetting resin composition containing an organic solvent may be called resin varnish. The organic solvent is not particularly limited, and examples thereof include methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, and triethylene glycol monomethyl ether. , triethylene glycol monoethyl ether, triethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether and other alcohol solvents; acetone, methyl ethyl ether, etc. Ketone solvents such as ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and trimethylbenzene; including formamide, N-methylformamide, Nitrogen atom-containing solvents including amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; including dimethyl terine and other amide solvents Sulfur atom-containing solvents including sulfur-based solvents; ester-based solvents such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, propylene glycol monomethyl ether acetate, and 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 methane are more preferred. Kitaselusu, propylene glycol monomethyl ether, more preferably methyl ethyl ketone, methyl isobutyl ketone, particularly preferably methyl ethyl ketone. One type of organic solvent may be used alone, or two or more types may be used in combination.

In the thermosetting resin composition [I] (resin varnish), the content of the organic solvent may be appropriately adjusted to a level that facilitates handling of the thermosetting resin composition [I], and the content of the organic solvent in the resin varnish shall be There is no particular restriction within the range in which the cloth properties are good, but the solid content concentration (concentration of components other than organic solvents) derived from the thermosetting resin composition [I] is preferably 30 to 90 mass %, more preferably The content is 40 to 80% by mass, more preferably 50 to 80% by mass.

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

＜(G)Epoxy resin＞ Examples of the (G) epoxy resin contained in the epoxy resin composition [II] include the same epoxy resin as the (B) epoxy resin in the aforementioned thermosetting resin composition [I], and the description thereof is also same. Among these, preferred ones are selected from the group consisting of bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, and biphenyl type epoxy resin. At least one selected from the group consisting of epoxy resin, biphenyl aralkyl novolak type epoxy resin and dicyclopentadiene type epoxy resin, from the viewpoint of low thermal expansion and high glass transition temperature, More preferably, the resin is made from cresol novolak type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl novolak type epoxy resin and phenol novolac type epoxy resin. At least one selected from the group consisting of oxy resins, more preferably a biphenyl aralkyl novolak type epoxy resin.

＜(H) Epoxy resin hardener＞ Examples of the epoxy resin hardener include various phenol resin compounds, acid anhydride compounds, amine compounds, and hydrazine compounds. Examples of the phenol resin compound include novolak type phenol resin, resol type phenol resin, etc. Examples of the acid anhydride compound include phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl Nadic acid etc. In addition, examples of the amine compound include dicyandiamide, diaminodiphenylmethane, guanidine urea, and the like. Among these epoxy resin hardeners, from the viewpoint of improving reliability, novolak type phenol resin is preferred, and cresol novolak resin is preferred.

Commercially available novolak-type phenol resins can be used, and examples include phenol novolak resins such as "TD2090" (trade name, manufactured by DIC Co., Ltd.); "KA-1165" (trade name, manufactured by DIC Co., Ltd.), etc. Cresol novolac resin, etc. In addition, commercially available triazine ring-containing novolac varnish-type phenolic resins such as "PHENOLITE LA-1356" (trade name, manufactured by DIC Co., Ltd.) and "PHENOLITE LA7050 Series" (trade name, manufactured by DIC Co., Ltd.) can be cited. For example, triazinecresol novolak resins such as "PHENOLITE LA-3018" (trade name, manufactured by DIC Co., Ltd.) can be used.

The epoxy resin composition [II] may contain (I) a hardening accelerator and (J) an inorganic filler material as needed. ＜(I) Hardening accelerator＞ From the viewpoint of accelerating the reaction between the (G) epoxy resin and the (H) epoxy resin hardener, the epoxy resin composition [II] preferably contains the (I) hardening accelerator. Examples of (I) hardening accelerators include imidazole compounds such as 2-phenylimidazole, 2-ethyl-4-methylimidazole, and 1-cyanoethyl-2-phenylimidazolium trimellitate; Organophosphorus compounds such as triphenylphosphine; onium salts such as phosphonium borate; amines such as 1,8-diazabicycloundecene; 3-(3,4-dichlorophenyl)-1,1-dimethylurea wait. One type of these may be used alone, or two or more types may be used in combination. Among these, imidazole compounds are preferred, and 2-ethyl-4-methylimidazole is preferred.

＜(J) Inorganic filler＞ 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 silicon oxide, aluminum oxide, 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, etc. One type of these may be used alone, or two or more types may be used in combination. Among these, silicon oxide is preferred from the viewpoint of low thermal expansion coefficient. The average particle size of the inorganic filler is preferably 0.1 μm or more, more preferably 0.2 μm or more, and more preferably 0.3 μm or more. The inorganic filler material can be surface treated. For example: when using silica as the inorganic filler material, a silane coupling agent treatment can be implemented as a surface treatment. Examples of the silane coupling agent include an aminosilane coupling agent, a vinylsilane coupling agent, an epoxysilane coupling agent, and the like. Among these, silicon oxide surface-treated with an aminosilane coupling agent is preferred.

(Content of each component of the epoxy resin composition [II]) In the epoxy resin composition [II], the content of components (G) to (J) is not particularly limited. Preferably, the component (G) is: 5 to 50 parts by mass, component (H) is 5 to 50 parts by mass, component (I) is 0.001 to 1 part by mass, and component (J) is 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, based on 100 parts by mass of the components (G) to (J) in total. Parts by mass, (J) component are 35 to 80 parts by mass.

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

(additive) Examples of additives include colorants, antioxidants, reducing agents, ultraviolet absorbers, fluorescent whitening agents, adhesion improving agents, organic fillers, and the like. One type of these may be used alone, or two or more types may be used in combination.

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

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

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, n-pentyl Key et al. As the alkyl group, an alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group is preferred. In the "substituted phenyl group", examples of the substituent of 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 vinyl, allyl, and the like. Examples of the alkynyl group having 2 to 5 carbon atoms include ethynyl group, propargyl group, and the like. R ^k1 and R ^k2 are preferably both alkyl groups having 1 to 5 carbon atoms, and more preferably are methyl groups.

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 are the same as R ^k1 and R ^k2 in the general formula (k-2-1); R ^k3 and R ^k4 each independently represent a carbon number of 1 to 5 an alkyl group, a phenyl group, or a phenyl group having a substituent; R ^k5 and R ^k6 each independently represent a divalent organic group, and m is an integer from 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 alkenylene group, an alkynylene group, an aryl group, -O-, or a divalent linking group obtained by combining these groups. . Examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms such as methylene, ethylene, and propylene. Examples of the alkenylene group include alkenylene groups having 2 to 10 carbon atoms. Examples of the alkynylene group include an alkynylene group having 2 to 10 carbon atoms. Examples of the aryl group include aryl groups having 6 to 20 carbon atoms, such as a phenyl group and a naphthylene group. Among these, R ^k5 and R ^k6 are preferably an alkylene group or an aryl group. m is preferably an integer of 2 to 50, more preferably an integer of 3 to 40, more preferably an integer of 5 to 30, and still more preferably an integer of 7 to 30.

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

As the siloxane compound (k-2), a commercially available product can be used. Examples of commercially available products include: "KF-8010" (the functional group equivalent of the amine group is 430 g/mol), "X-22-161A" (the functional group equivalent of the amine group is 800 g/mol), "X- 22-161B" (the functional group equivalent of the amine group is 1,500 g/mol), "KF-8012" (the functional group equivalent of the amine group is 2,200 g/mol), "KF-8008" (the functional group equivalent of the amine group is 5,700 g/mol), "X-22-9409" (the functional group equivalent of the amine group is 700 g/mol), "X-22-1660B-3" (the functional group equivalent of the amine group is 2,200 g/mol) ( The above are manufactured by Shin-Etsu Chemical Industry Co., Ltd.); "BY-16-853U" (the functional group equivalent of the amine group is 460 g/mol), "BY-16-853" (the functional group equivalent of the amine group is 650 g/mol) mol), "BY-16-853B" (the functional group equivalent of the amine group is 2,200 g/mol) (the above is manufactured by Dow Corning Toray Co., Ltd.); "XF42-C5742" (the functional group equivalent of the amine group is 1,280 g /mol), "XF42-C6252" (the functional group equivalent of the amine group is 1,255 g/mol), "XF42-C5379" (the functional group equivalent of the amine group is 745 g/mol) (the above is Momentive Performance Materials Japan Co., Ltd. system), etc. One type of these may be used alone, or two or more types may be used in combination.

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

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

＜(L)imidazole compound＞ Examples of the (L) imidazole compound include 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1,2-di Methylimidazole, 2-ethyl-1-methylimidazole, 1,2-diethylimidazole, 1-ethyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl -2-methylimidazole, 1-isobutyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 1-phenylmethyl-2-phenylimidazole, 1-cyanoethyl-2- Methylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl- 4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 2 ,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazole Triazine-(1')]ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyl-s- Imidazole compounds such as triazine; modified imidazole compounds such as isocyanate masked imidazole and epoxy masked imidazole; trimellitic acid 1-cyanoethyl-2-phenylimidazolium salt and other aforementioned imidazole compounds and trimellitic acid The salt of the aforementioned imidazole compound and isocyanuric acid; the salt of the aforementioned imidazole compound and hydrobromic acid, etc. Among these, a modified imidazole compound is preferred, and an isocyanate group-shielded imidazole is preferred. One type of imidazole compound may be used alone, or two or more types may be used in combination.

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

(Content of each component of the thermosetting resin composition [III]) In the thermosetting resin composition [III], the content of components (K) to (M) is not particularly limited. Preferably, the content of component (K) is 100 parts by mass in total of components (K) to (M). The amount is 15 to 80 parts by mass, the component (L) is 0.01 to 5 parts by mass, and the component (M) is 15 to 80 parts by mass. 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 by mass based on 100 parts by mass of the components (K) to (M) in total. parts by mass.

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

(additive) Examples of additives include colorants, antioxidants, reducing agents, ultraviolet absorbers, fluorescent whitening agents, adhesion improving agents, organic fillers, and the like. One type of these may be used alone, or two or more types may be used in combination.

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

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

Furthermore, according to the present invention, the following prepreg can be provided. The prepreg obtained by the manufacturing method of the present invention also corresponds to the following prepreg. In other words, the following prepreg can be produced by the production method of the present invention. A prepreg consisting of a base material and a thermosetting resin composition and having a standard deviation σ of 0.012% or less as determined by the following method, How to calculate standard deviation σ: Copper foil with a thickness of 18 μm is overlapped on both sides of a prepreg, and heat and pressure molding is performed at 190°C and 2.45 MPa for 90 minutes to produce a double-sided copper-clad laminate with a thickness of 0.1 mm; For the double-sided copper-clad laminated board obtained in the above manner, holes with a diameter of 1.0 mm are made at locations 1 to 8 described in Figure 1 on the surface of the double-sided copper-clad laminated board; The vertical direction, which is the direction of 1-7, 2-6, and 3-5, and the transverse direction, which are the directions of 1-3, 8-4, and 7-5, are three points each. Use an image measuring machine. After measuring the distance between each three points, set each measured distance as the initial value; then, remove the outer copper foil and heat it with a dryer at 185°C for 60 minutes; after cooling, use the same measured distance as the initial value. In the same direction, use the vertical direction, which is the direction of 1-7, 2-6, 3-5, and the horizontal direction, which is between 3 points in the direction of 1-3, 8-4, and 7-5. The distance is measured; the average value of the change rates is calculated based on the change rate relative to the initial value of each measured distance [(measured value after heat treatment - initial value) × 100/initial value], and calculated relative to The standard deviation σ of this mean. The aforementioned image measuring machine is not particularly limited, and for example, “QV-A808P1L-D” (manufactured by Mitutoyo Corporation) can be used.

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

[Laminated board] The laminated board of the present invention contains the prepreg and metal foil. It can be produced, for example, by laminating and molding a structure in which one sheet of the above-mentioned prepreg is used or 2 to 20 sheets of the above-mentioned prepreg are stacked as necessary and a metal foil is arranged on one or both sides of the prepreg. . In addition, a laminated board on which metal foil is arranged may be called a metal-clad laminated board. The metal of the metal foil is not particularly limited as long as it is a metal used for electrical insulating materials. From the viewpoint of electrical conductivity, the metal of the metal foil is preferably copper, gold, silver, nickel, platinum, molybdenum, or 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 based on conventional forming techniques of laminated boards and multi-layer boards for electrically insulating materials. For example, multi-stage pressurization, multi-stage vacuum pressurization, continuous forming, autoclave forming machines, etc. can be used at a temperature of 100 to 250°C. , pressure 0.2 ~ 10 MPa, heating time 0.1 ~ 5 hours to form. Furthermore, a multilayer board can also be produced by combining the prepreg of the present invention with an inner layer printed wiring board, laminating them, and molding them. The thickness of the metal foil is not particularly limited and may be appropriately selected depending on the use of the printed wiring board. The thickness of the metal foil is preferably 0.5 to 150 μm, preferably 1 to 100 μm, more preferably 5 to 50 μm, and particularly preferably 5 to 30 μm.

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

[Printed circuit board] The present invention also provides a printed wiring board, which includes the aforementioned prepreg or the aforementioned laminated board. The printed wiring board of the present invention can be produced by subjecting the metal foil of the metal-clad laminate to circuit processing. Circuit processing can be performed by, for example, the following method: after forming a resist pattern on the surface of the metal foil, removing the excess metal foil by etching, peeling off the resist pattern, and then using a drill to form the required penetration. After forming the hole and forming the resist pattern again, the through hole is plated for conduction, and finally the resist pattern is peeled off. A 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 above under the same conditions as above, and further performing circuit processing in the same manner as above. At this time, it is not necessary to form a through hole, a through hole may be formed, and both of these may be formed. Such multi-layering is required for the number of slices required.

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

Next, the present invention is described in more detail through 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 produced using the resin varnish, a prepreg obtained by subjecting the prepreg precursor to surface heat treatment, and further produce After cladding the copper-clad laminated board, the obtained copper-clad laminated board was evaluated. The evaluation method is as follows.

[Evaluation method] ＜1. Heat resistance (reflow heat resistance)＞ Using the four-layer copper-clad laminate prepared in each example, and setting the maximum reaching temperature to 266°C, the four-layer copper-clad laminate will flow in a constant temperature bath environment above 260°C for 30 seconds. Cycles were performed to determine the number of cycles until expansion of the substrate could be visually confirmed. The greater the number of cycles, the better the heat resistance.

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

＜3.Metal foil adhesion (copper foil peeling strength)＞ Metal foil adhesion is evaluated by copper foil peel strength. The double-sided copper-clad laminate prepared in each example was immersed in the copper etching solution "Ammonium Persulfate (APS)" (manufactured by ADEKA Co., Ltd.) to form a 3 mm wide copper foil, and an evaluation substrate was produced. , and the peel strength of the copper foil was measured using an autoclave "AG-100C" (manufactured by Shimadzu Corporation). The larger the value, the better the metal foil adhesion is.

＜4. Glass transition temperature (Tg)＞ The double-sided copper-clad laminates produced in each example were immersed in the copper etching solution "Ammonium Persulfate (APS)" (manufactured by ADEKA Co., Ltd.) to remove the copper foil and produce a 5 mm square evaluation The thermal expansion characteristics of the substrate in the surface direction (Z direction) of the substrate at 30 to 260°C are observed and evaluated using a thermomechanical analysis (TMA) test device "Q400EM" (manufactured by TA Instruments), and the inflection point of the expansion amount is Set to glass transition temperature.

<5. Low thermal expansion> The copper foil was removed by immersing the double-sided copper-clad laminate produced in each example in the copper etching solution "ammonium persulfate (APS)" (manufactured by ADEKA Co., Ltd.). A 5 mm square evaluation substrate was produced, and the thermal expansion coefficient (linear expansion coefficient) in the surface direction of the evaluation substrate was measured using the TMA test device "Q400EM" (manufactured by TA Instruments). In addition, in order to remove the influence of thermal strain of the sample, after repeating the heating-cooling cycle twice, the thermal expansion coefficient [ppm/°C] of 30°C to 260°C in the second temperature displacement graph was measured, and set An indicator of low thermal expansion. The smaller the value, the more excellent the low thermal expansion property. In addition, the thermal expansion coefficient when Tg is not reached (marked as "<Tg") and the thermal expansion coefficient when it exceeds Tg (marked as ">Tg") are separately described in the table. Measurement conditions ^1st Run: Room temperature → 210°C (heating rate 10°C/min) ^2nd Run: 0°C → 270°C (heating rate 10°C/min) Copper-clad laminated boards are expected to be further thinned, and this is also in line with this Desirably, thinning of prepregs constituting copper-clad laminates is being studied. Since a thinned prepreg is prone to warpage, it is desired that the prepreg has less warpage during heat treatment. In order to reduce warpage, a more effective method is to make the thermal expansion coefficient in the surface direction of the base material smaller.

<6. Throwing property (laser processability)> For the four-layer copper-clad laminate produced in each example, a laser machine "LC-2F21B/2C" (manufactured by Hitachi Via Mechanics Co., Ltd.) was used. Laser drilling was performed using the copper direct method with a target aperture of 80 μm, Gaussian, and cyclic mode, with a pulse width of 15 μs × 1 time and 7 μs × 4 times. For the obtained laser-opened 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.), and perform desmear treatment using a neutralizing liquid "Reduction Conditioner Securiganth P500" (manufactured by Atotech Japan Co., Ltd.) at 40°C for 5 minutes. Then, an electroless plating solution "Priganth MSK-DK" (manufactured by Atotech Japan Co., Ltd.) was used at 30°C for 20 minutes, and a plating solution "Cupracid HL" (manufactured by Atotech Japan Co., Ltd.) was used at 24°C and 2 A/ ^dm2 . Company-made) 2 hours to perform plating on the laser processing substrate. A cross-section of the obtained laser-opened substrate was observed to confirm the throwability. As an evaluation method of throwing property, because the throwing property is better when the difference between the coating thickness at the top of the laser hole and the coating thickness at the bottom of the laser hole is within 10% of the coating thickness at the top of the laser hole, therefore, Find the ratio (%) of pores included in this range among 100 pores.

＜7. Formability＞ For the four-layer copper-clad laminated board produced in each example, after removing the outer copper layer, the presence or absence of holes and scratches in the 340 mm × 500 mm surface was visually confirmed, and this was used as an indicator of formability. When there are no holes or scratches, it is indicated as "good". When there are holes or scratches, this condition is indicated. When there are no holes or scratches, it can be said to have good formability.

＜8. Evaluation of deviations in dimensional change＞ For the double-sided copper-clad laminate produced in each example, holes with a diameter of 1.0 mm were made as shown in Figure 1. As recorded in Figure 1, the vertical direction of the glass cloth is the direction of 1-7, 2-6, 3-5 and the horizontal direction is the direction of 1-3, 8-4, 7-5. After measuring the distance between each of the three points using an image measuring machine "QV-A808P1L-D" (manufactured by Mitutoyo Co., Ltd.), each measured distance is set as an initial value. Then, the outer copper foil was removed and heated at 185° C. for 60 minutes using a dryer. After cooling, proceed in the same manner as the initial value measurement method to measure the longitudinal direction, that is, the direction of 1-7, 2-6, 3-5, and the transverse direction, that is, 1-3, 8-4, 7- The distance between each three points in the direction of 5 is measured. The average value of the change rates with respect to the initial value of each measured distance is calculated [(measured value - initial value) × 100/initial value], and the standard deviation σ with respect to the average value is calculated. This standard deviation σ is an index of the variation in the amount of dimensional change. A smaller value of the standard deviation σ means that the variation in the dimensional change amount is smaller and is preferable.

Each component used in Examples and Comparative Examples will be described below.

(A) Component: The solution of the maleimide compound (A) prepared in the following Production Example 1 was used. [Manufacturing Example 1] In a reaction vessel with a volume of 1 L equipped with a thermometer, a stirring device and a moisture meter equipped with a reflux cooling tube, add 19.2 g of 4,4'-diaminodiphenylmethane and bis(4-maleimide) 174.0 g of phenyl)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-substituted maleimide. A dimethylacetamide solution of a maleimide compound (A) (Mw=1,370) was used as component (A). In addition, the above-mentioned weight average molecular weight (Mw) is converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve uses standard polystyrene: TSK standard POLYSTYRENE (model: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [Tosoh Limited company] is approximated by a cubic equation. The conditions for GPC are as follows. Device: (Pump: Model L-6200 [manufactured by Hitachi High-Technologies Co., Ltd.]), (Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Co., Ltd.]), (Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Co., Ltd.]) Column: TSKgel SuperHZ2000 + TSKgel SuperHZ2300 (both manufactured by Tosoh Co., Ltd.) Column size: 6.0×40 mm (protection column), 7.8×300 mm (column) Eluate: Tetrahydrofuran Sample concentration: 20 mg/5 mL Injection volume: 10 μL Flow: 0.5 mL/min Measuring temperature: 40℃

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

(D) Component: Fused silica treated with an aminosilane coupling agent (average particle size: 1.9 μm, specific surface area 5.8 m ² /g) Other inorganic filler materials: "F05-30" (not yet available) Processed pulverized silica, average particle diameter: 4.2 μm, specific surface area 5.8 m ² /g, manufactured by Fukushima Kiln Co., Ltd.)

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

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

(Preparation and performance evaluation of double-sided copper-clad laminates) After stacking eight pieces of the aforementioned prepregs, 18 μm-thick copper foil "3EC-VLP-18" (manufactured by Mitsui Metals Co., Ltd.) was stacked on both sides. , and heat and press mold 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 with a thickness of 0.8 mm (prepreg 8 pieces), and then use the copper-clad laminate For laminates, the relative dielectric constant, metal foil adhesion, glass transition temperature (Tg) and low thermal expansion are measured and evaluated according to the aforementioned methods. In addition, a copper foil "3EC-VLP-18" (manufactured by Mitsui Metals Co., Ltd.) with a thickness of 18 μm was laminated on both sides of one prepreg, and the temperature was maintained at 190°C and a pressure of 25 kgf/cm ² (2.45 MPa). ) is heated and pressurized for 90 minutes to produce a double-sided copper-clad laminated board with a thickness of 0.1 mm (1 piece of prepreg). The double-sided copper-clad laminated board is used to measure and evaluate the dimensional change according to the above method. deviation.

(Production and performance evaluation of a four-layer copper-clad laminate) On the other hand, one piece of the above-mentioned prepreg was used, and a copper foil "YGP-18" (manufactured by Nippon Electrolytic Co., Ltd.) with a thickness of 18 μm was laminated on both sides of the prepreg. , and heat and press it for 90 minutes at a temperature of 190°C and a pressure of 25 kgf/cm ² (2.45 MPa) to produce a double-sided copper-clad laminate with a thickness of 0.1 mm (1 piece of prepreg). The inner layer adhesion treatment (using "BF treatment liquid" (manufactured by Hitachi Chemical Co., Ltd.)) was performed on the surface, and the 18 μm-thick copper foil "YGP- 18" (manufactured by Nippon Electrolytic Co., Ltd.) was stacked on both sides, and heated and pressurized 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 laminated board, heat resistance, throwing properties, and formability were evaluated according to the method described above. The results are shown in Tables 1 to 4.

[Table 1]

[Table 2]

[table 3]

[Table 4]

[Example 14] The following components were used to prepare a resin varnish instead of preparing the resin varnish in Example 1. 19 parts by mass of biphenyl aralkyl novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-3000, epoxy equivalent: 280 to 300 g/eq), cresol novolak resin (DIC Co., Ltd., trade name: KA-1165, hydroxyl equivalent: 119 g/eq) 16 parts by mass, 0.02 parts by mass of 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd.), melt oxidation 65 parts by mass of silicon (manufactured by Admatechs Co., Ltd., fused silicon oxide treated with an aminosilane coupling agent, average particle size: 2 μm) was mixed and diluted with a solvent (methyl ethyl ketone), thereby A resin varnish (solid content concentration: 70% by mass) was prepared. Other steps were performed in the same manner as in Example 1, thereby obtaining a prepreg. Using the obtained prepreg, a double-sided copper-clad laminated board was produced in the same manner as in Example 1. The deviation of the dimensional change amount was measured and evaluated using the double-sided copper-clad laminated board. As a result, the standard deviation σ was The value is 0.010%.

[Example 15] The following components were used to prepare a resin varnish instead of preparing the resin varnish in Example 1. In a 2 L reaction vessel equipped with a stirring device and a moisture meter equipped with a reflux cooling tube, which can be heated and cooled, add KF-8010 (both terminal amine modified silicone oil, Shin-Etsu Chemical Industry Co., Ltd. (manufactured by Yamato Chemical Industry Co., Ltd., trade name: BMI-1000) 75.7 g, 168.0 g of bis(4-maleimidophenyl)methane (manufactured by Yamato Chemical Industry Co., Ltd., trade name: BMI-1000), p-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) 6.4 g, and 250.0 g of solvent (methyl ethyl ketone), and reacted at 100°C for 3 hours, thereby obtaining a silicone-modified maleimide compound. 49.5 parts by mass of this silica-modified maleimine compound, 50 parts by mass of fused silica (manufactured by Admatechs Co., Ltd., fused silica treated with an aminosilane coupling agent), and isocyanate 0.5 parts by mass of masking imidazole (trade name: G-8009L, manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.) was mixed and diluted with a solvent (methyl ethyl ketone) to prepare a resin varnish (solid content concentration: 70 mass% ). Other steps were performed in the same manner as in Example 1, thereby obtaining a prepreg. Using the obtained prepreg, a double-sided copper-clad laminated board was produced in the same manner as in Example 1. The deviation of the dimensional change amount was measured and evaluated using the double-sided copper-clad laminated board. As a result, the standard deviation σ was The value is 0.009%.

From the above results, the following facts are known. In the Examples, since the prepreg precursor was subjected to surface heat treatment, the standard deviation σ was reduced compared with the comparative example in which the surface heat treatment was not carried out, and the variation in the dimensional change amount could be sufficiently suppressed. In addition, in Examples 1 to 13, the reflow heat resistance reached more than 10 cycles above the required heat resistance level, and low relative dielectric constant, high metal foil adhesion and high glass transition temperature were obtained, and low thermal expansion was exhibited. In addition, since the glass cloth protruded from the wall surface and had a moderately roughened shape, it was confirmed that it had good throw plating properties. In terms of formability, the filling properties of the resin were also good, and no abnormalities such as scratches or holes were observed. Among them, in Examples 1 to 10, compared with Examples 11 to 13, the relative dielectric constant and metal foil adhesion are better, and other characteristics are also stably exhibited. [Industrial availability]

Since the prepreg obtained by the present invention and the laminate containing the prepreg have small variation in dimensional change, they are useful as printed wiring boards for electronic devices.

Fig. 1 is a schematic diagram of an evaluation substrate used when measuring variation in dimensional change amounts in Examples.

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Claims (19)

A method for manufacturing a prepreg, which includes the step of: impregnating a thermosetting resin composition into a glass fiber base material, and then B-stepping the thermosetting resin composition to obtain a prepreg precursor; and, a surface heating treatment step performed after the aforementioned step of obtaining a prepreg precursor; and, the aforementioned surface heating treatment step is to heat the surface of the prepreg precursor by a heating method with a heat source temperature of 200 to 700°C The step of processing for 1.0~6.0 seconds, the heating method is the heating method using a flat heater, the heating method by hot air, the heating method by high frequency, the heating method by magnetic lines of force, the heating method by laser, Or a heating method that combines these. A method for manufacturing a prepreg, which includes the step of: impregnating a thermosetting resin composition into a glass fiber base material, and then B-stepping the thermosetting resin composition to obtain a prepreg precursor; And, the surface heating treatment step is performed after the aforementioned step of obtaining the prepreg precursor; and, the aforementioned surface heating treatment step is performed by heating the surface temperature of the prepreg precursor to 40 to 130°C. The surface of the prepreg precursor is heated for 1.0 to 6.0 seconds. The heating method is a heating method using a flat heater, a heating method by hot air, a heating method by high frequency, a heating method by magnetic lines of force, a heating method by laser, or a combination of these. method. The manufacturing method of prepreg according to claim 1 or 2, wherein, after the aforementioned step of obtaining the prepreg precursor and before the aforementioned surface heating treatment step, the prepreg precursor is cooled to 5 to 60° C. ℃ steps. The manufacturing method of prepreg according to claim 1 or 2, wherein the time of the aforementioned surface heating treatment is 1.0 to 4.0 seconds. The method for manufacturing a prepreg according to claim 1 or 2, wherein the thermosetting resin composition contains (A) a maleimide compound. The method for manufacturing 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 2 A maleimide compound of an N-substituted maleimide group, (a2) a monoamine compound represented by the following general formula (a2-1), and (a3) represented by the following general formula (a3-1) Obtained by reacting diamine compounds;

In the general formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group and a sulfonic acid group, R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, and t is an integer of 1 to 5. , u is an integer from 0 to 4 and satisfies 1<t+u≦5, where, when t is an integer from 2 to 5, the plural R ^A4 can be the same or different, in addition, when u is an integer from 2 to 4 When it is an integer, the plural R ^A5 can be the same or different;

In the general formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or -O-, and R ^A6 and R ^A7 each independently represent an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, or a carboxyl group. or a sulfonic acid group, v and w are each independently an integer from 0 to 4. The method for manufacturing a prepreg according to claim 5, wherein the thermosetting resin composition further contains: (B) epoxy resin; (C) copolymer resin having a content derived from a substituted vinyl compound a structural unit and a structural unit derived from maleic anhydride; and (D) silicon oxide treated with an aminosilane coupling agent. The method for manufacturing a prepreg according to claim 7, wherein the component (B) is selected from the group consisting of bisphenol F epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkylphenol At least one selected from the group consisting of aldehyde varnish type epoxy resin and dicyclopentadiene type epoxy resin. The method for manufacturing a prepreg according to claim 7, wherein the component (C) has a structural unit represented by the following general formula (Ci) and a structural unit represented by the following general formula (C-ii) Copolymer resin:

In formula (Ci), R ^C1 is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and R ^C2 is an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an aryl group with 6 to 20 carbon atoms. , hydroxyl group, or (meth)acrylyl group, x is an integer from 0 to 3, where, when x is 2 or 3, the plurality of R ^C2 may be the same or different. A prepreg that includes a base material and a thermosetting resin composition and has a standard deviation σ calculated according to the following method of 0.009% or less. The method for calculating the standard deviation σ is: a copper foil with a thickness of 18 μm Overlap on both sides of a piece of prepreg, And perform heating and pressure molding at 190°C and 2.45MPa for 90 minutes to produce a double-sided copper-clad laminate with a thickness of 0.1mm; for the double-sided copper-clad laminate obtained in the above manner, the double-sided copper-clad laminate is Holes with a diameter of 1.0 mm are made at locations 1 to 8 on the surface of the laminate board as shown in Figure 1; the longitudinal directions as shown in Figure 1 are 1-7, 2-6, and 3- The distance between each of the three points in the direction of 5 and the transverse direction, that is, the direction of 1-3, 8-4, and 7-5, is measured using an image measuring machine, and each measured distance is set to Initial value; then, remove the outer copper foil and heat it with a dryer at 185°C for 60 minutes; after cooling, measure the longitudinal direction in the same way as the initial value, that is, 1-7, 2-6 , the direction of 3-5 and the transverse direction, that is, the distance between three points in the direction of 1-3, 8-4, and 7-5 is measured; it is calculated based on the change rate relative to the initial value of each measured distance. Find the average of these rates of change, and calculate the standard deviation σ relative to the average. The prepreg according to claim 10, wherein the thermosetting resin composition contains (A) a maleimide compound. The prepreg according to claim 10 or 11, wherein the thermosetting resin composition further contains: (B) epoxy resin; (C) copolymer resin having a structure derived from a substituted vinyl compound unit and a structural unit derived from maleic anhydride; and (D) silicon oxide treated with an aminosilane coupling agent. The prepreg according to claim 10, wherein the thermosetting resin composition contains (G) epoxy resin and (H) 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 including the prepreg according to any one of claims 10 to 14 and a metal foil. A printed wiring board including the prepreg according to any one of claims 10 to 14 or the laminate according to claim 15. A semiconductor package in which a semiconductor element is mounted on the printed circuit board according to claim 16. The method for manufacturing a prepreg according to claim 1 or 2, wherein the thermosetting resin composition contains (G) epoxy resin and (H) epoxy resin hardener. The method for manufacturing a prepreg according to claim 1 or 2, wherein the thermosetting resin composition contains (K) a silicone-modified maleimide compound and (L) an imidazole compound.