Laminate, printed wiring board, semiconductor package, and method for manufacturing laminate

Abstract

Provided are a laminate that has a high elastic modulus and low thermal expansion while also having excellent connection reliability, a printed wiring board and a semiconductor package that use the laminate, and a method for producing the laminate. [Solution] A laminate containing two or more composite layers each containing a fiber base material and a cured product of a thermosetting resin composition, wherein the two or more composite layers contain one or more composite layers (X) and one or more composite layers (Y), wherein the composite layer (X) is a layer containing a first fiber base material composed of a first glass fiber, and the composite layer (Y) is a layer containing a second fiber base material composed of a second glass fiber, and the first glass fiber has a higher tensile modulus at 25°C than the second glass fiber. The laminate, printed wiring boards and semiconductor packages using the laminate, and a method for producing the laminate are also provided.

Description

[Technical Field]

[0001] The present embodiment relates to a laminate, a printed wiring board, a semiconductor package, and a method for manufacturing the laminate. [Background technology]

[0002] In recent years, the miniaturization and high performance of electronic devices have led to advances in the wiring density and integration of printed wiring boards, which has led to increased demand for improved reliability of printed wiring boards. In particular, with semiconductor packages becoming smaller and thinner, warpage occurring during component mounting and package assembly has become a major issue.

[0003] One of the factors that causes semiconductor package warpage is the difference in the thermal expansion coefficient between the semiconductor element and the printed wiring board on which the semiconductor element is mounted. Generally, the thermal expansion coefficient of the printed wiring board is greater than that of the semiconductor element. Therefore, warpage stress due to the difference in the thermal expansion coefficient occurs in the package that is subjected to thermal history, such as heating during mounting of the semiconductor element. Therefore, effective methods for suppressing warpage of semiconductor packages include reducing the thermal expansion coefficient of the printed wiring board to reduce the difference with the thermal expansion coefficient of the semiconductor element, and increasing the elastic modulus of the printed wiring board to increase its rigidity.

[0004] Laminates for printed wiring boards are generally made by laminating prepregs obtained by impregnating or coating a fiber substrate such as glass cloth with a thermosetting resin composition, and then heat-curing the prepregs. The resin components contained in prepregs have a high coefficient of thermal expansion and a low modulus of elasticity among the materials that make up prepregs, so by increasing the loading of inorganic fillers such as silica, a high modulus of elasticity and a low thermal expansion are achieved (see, for example, Patent Document 1). However, increasing the inorganic filler content may reduce insulation reliability, adhesion to copper foil, press workability, etc., and therefore, from the viewpoint of ensuring these performance properties, there is a limit to how much the elastic modulus and thermal expansion of a laminate can be increased and reduced by increasing the inorganic filler content alone. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 5-148343 Summary of the Invention [Problem to be solved by the invention]

[0006] Another method for increasing the elastic modulus and decreasing the thermal expansion of a laminate is to use a fiber base material with a lower thermal expansion coefficient and a higher elastic modulus. However, according to the investigations of the present inventors, it has been found that when the thermal expansion coefficient of the fiber base material is reduced and the elastic modulus is increased, the resulting laminate tends to have poor connection reliability. Therefore, simply adjusting the coefficient of thermal expansion and modulus of elasticity of the fiber base material is not enough to achieve a high modulus of elasticity and low thermal expansion of the laminate while maintaining good connection reliability.

[0007] The present embodiment has been made in consideration of the above circumstances, and aims to provide a laminate having a high elastic modulus and low thermal expansion while also having excellent connection reliability, a printed wiring board and a semiconductor package using the laminate, and a method for manufacturing the laminate. [Means for solving the problem]

[0008] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by the present embodiment described below. That is, this embodiment relates to the following [1] to

[14] . [1] A laminate comprising two or more composite layers containing a fiber substrate and a cured product of a thermosetting resin composition, The two or more composite layers include one or more composite layers (X) and one or more composite layers (Y), The composite layer (X) is a layer containing a first fiber substrate composed of a first glass fiber, The composite layer (Y) is a layer containing a second fiber substrate composed of a second glass fiber, A laminate wherein the first glass fibers have a higher tensile modulus at 25°C than the second glass fibers. [2] The first glass fiber has a tensile modulus of elasticity of 80 GPa or more at 25°C, The laminate according to [1], wherein the second glass fiber has a tensile modulus at 25°C of less than 80 GPa. [3] The laminate according to [1] or [2], wherein the difference in tensile modulus at 25°C between the first glass fiber and the second glass fiber is 10 GPa or more. [4] A laminate comprising two or more composite layers containing a fiber substrate and a cured product of a thermosetting resin composition, The two or more composite layers include one or more composite layers (X) and one or more composite layers (Y), The composite layer (X) is a layer containing a first fiber substrate composed of a first glass fiber, The composite layer (Y) is a layer containing a second fiber substrate composed of a second glass fiber, A laminate, wherein the total content of SiO2 and Al2O3 in the first glass fibers is higher than the total content of SiO2 and Al2O3 in the second glass fibers. [5] The laminate according to any one of [1] to [4], wherein the first glass fiber is S-glass. [6] The laminate according to any one of [1] to [5], wherein the second glass fiber is E-glass. [7] The laminate according to any one of [1] to [6], wherein the number of layers of the composite layer (X) is greater than the number of layers of the composite layer (Y). [8] A laminate comprising one or more composite layers (X) and two or more composite layers (Y), The laminate according to any one of [1] to [7], wherein at least one composite layer (X) is disposed between two composite layers (Y). [9] A laminate comprising one or more composite layers (X) and two or more composite layers (Y), The laminate according to any one of [1] to [8], wherein the composite layer (Y) is the outermost layer on both sides of the laminate.

[10] The laminate according to [9], which comprises one or more composite layers (X) and two composite layers (Y), and the outermost layers on both sides of the laminate are the composite layers (Y).

[11] The laminate according to [9] or

[10] , which contains two or more composite layers (X).

[12] A printed wiring board comprising the laminate according to any one of [1] to

[11] .

[13] A semiconductor package comprising a semiconductor element mounted on the printed wiring board described in

[12] .

[14] A method for producing the laminate according to any one of [1] to

[11] , A prepreg (a) obtained by impregnating a first fiber base material composed of the first glass fiber with a thermosetting resin composition; a prepreg (b) obtained by impregnating a second fiber base material composed of the second glass fiber with a thermosetting resin composition; A method for manufacturing a laminated plate, comprising laminating and molding the above. [Effects of the Invention]

[0009] According to the present embodiment, it is possible to provide a laminate having a high elastic modulus and low thermal expansion while also having excellent connection reliability, a printed wiring board and a semiconductor package using the laminate, and a method for manufacturing the laminate. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 2 is a schematic diagram showing a cross section of a composite layer. [Figure 2] 1A and 1B are schematic diagrams illustrating examples of sandwich laminates. [Figure 3] FIG. 10 is a schematic diagram showing another example of a sandwich laminate. [Figure 4] 1 is a schematic diagram illustrating an example of a laminated plate according to an embodiment of the present invention. [Figure 5] FIG. 2 is a schematic diagram showing another example of the laminated plate of the present embodiment. [Figure 6]FIG. 2 is a schematic diagram showing another example of the laminated plate of the present embodiment. [Figure 7] FIG. 2 is a schematic diagram showing another example of the laminated plate of the present embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0011] Numerical ranges indicated using "to" in this specification indicate a numerical range that includes the numerical value before "to" as the minimum value and the numerical value after "to" as the maximum value. For example, a numerical range "X to Y" (X and Y are real numbers) means a numerical range that is equal to or greater than X and equal to or less than Y. In this specification, the expression "equal to or greater than X" means X and a numerical value that exceeds X. In addition, the expression "equal to or less than Y" means Y and a numerical value that is less than Y. In the numerical ranges described herein, the upper or lower limit of the numerical range may be replaced with the values ​​shown in the examples. In addition, the lower and upper limit of a numerical range may be arbitrarily combined with the lower or upper limit of another numerical range. Furthermore, unless otherwise specified, each component and material exemplified in this specification may be used alone or in combination of two or more. In this specification, the content of each component in a composition means the total amount of the multiple substances present in the composition when multiple substances corresponding to each component are present in the composition, unless otherwise specified. Any combination of the features described in this specification is also included in this embodiment. The mechanism of action described in this specification is speculation and does not limit the mechanism by which the resin composition according to this embodiment exhibits its effects.

[0012] [Laminate] This embodiment provides a laminate of the first embodiment shown in [1] below (hereinafter also referred to as "laminate (1)"), and a laminate of the second embodiment shown in [2] below (hereinafter also referred to as "laminate (2)").

[0013] [1] A laminate comprising two or more composite layers containing a fiber substrate and a cured product of a thermosetting resin composition, The two or more composite layers include one or more composite layers (X) and one or more composite layers (Y), The composite layer (X) is a layer containing a first fiber substrate composed of a first glass fiber, The composite layer (Y) is a layer containing a second fiber substrate composed of a second glass fiber, A laminate wherein the first glass fibers have a higher tensile modulus at 25°C than the second glass fibers.

[0014] [2] A laminate comprising two or more composite layers containing a fiber substrate and a cured product of a thermosetting resin composition, The two or more composite layers include one or more composite layers (X) and one or more composite layers (Y), The composite layer (X) is a layer containing a first fiber substrate composed of a first glass fiber, The composite layer (Y) is a layer containing a second fiber substrate composed of a second glass fiber, A laminate, wherein the total content of SiO2 and Al2O3 in the first glass fibers is higher than the total content of SiO2 and Al2O3 in the second glass fibers.

[0015] Unless otherwise specified, the following explanation applies to both the laminate (1) and the laminate (2) of this embodiment, and when simply referring to a "laminate," it refers to both the laminate (1) and the laminate (2) of this embodiment.

[0016] The reason why the laminate of this embodiment has a high elastic modulus and low thermal expansion and yet excellent connection reliability is not clear, but is presumed to be as follows. The elastic modulus of the glass fiber or the SiO2 and Al2O3 content is one of the factors that determine the elastic modulus and thermal expansion coefficient of the fiber substrate made of the glass fiber. Specifically, a fiber substrate made of a second glass fiber with a low elastic modulus or a low SiO2 content provides a composite layer (Y) with a low elastic modulus. The composite layer (Y) with a low elastic modulus has a significant impact on the connection reliability of a package using a laminate with a motherboard, and the application of the composite layer (Y) effectively improves the connection reliability of the laminate compared to the case of only the composite layer (X). On the other hand, the warpage of the laminate during curing improves depending on the number of composite layers (X) with a high elastic modulus and / or a high total content of SiO2 and Al2O3. As a result, it is thought that the connection reliability of a laminate containing composite layers (X) and composite layers (Y) is close to that of composite layer (Y), and the elastic modulus and thermal expansion coefficient improve depending on the number of composite layers (X). Each member of the laminated plate of this embodiment will be described below.

[0017] <Composite layer> The laminate of this embodiment contains two or more composite layers each containing a fiber base material and a cured product of a thermosetting resin composition. In this embodiment, the number of composite layers is an integer. Therefore, for example, 2 to 16 composite layers is an integer value within the range of 2 to 16, and in this case, the lower and upper limits of the number of composite layers can be arbitrarily combined using integer values ​​within the range. Furthermore, in this embodiment, one composite layer refers to a composite layer made up of one layer of fiber base material and a cured product of a thermosetting resin composition contained in the fiber base material. Furthermore, a single-layer fiber substrate is one that can be handled as a single sheet before being combined with a thermosetting resin composition, and is a sheet-like substrate having gaps in which the fibers are united by entanglement of the fibers, a fiber binder, etc. The laminate (1) of this embodiment includes a composite layer (X) containing a first fiber base material made of first glass fibers and a composite layer (Y) containing a second fiber base material made of second glass fibers. In the laminate (1) of this embodiment, the first glass fibers have a higher tensile modulus at 25°C than the second glass fibers. The laminate (2) of this embodiment includes a composite layer (X) containing a first fiber base material composed of first glass fibers and a composite layer (Y) containing a second fiber base material composed of second glass fibers. In the laminate (2) of this embodiment, the total content of SiO2 and Al2O3 in the first glass fibers is higher than the total content of SiO2 and Al2O3 in the second glass fibers. FIG. 1 shows a schematic cross-sectional view of an example of a composite layer contained in the laminate of this embodiment. As shown in FIG. 1, the composite layer 1 contains a fiber base material 2 and a cured product 3 of a thermosetting resin composition. In the composite layer 1, the fiber base material 2 is a glass cloth obtained by interweaving yarns, which are warp threads 2a and weft threads 2b, each of which is made by twisting strands of glass fibers, which are monofilaments. Suitable embodiments of the fiber substrate and the thermosetting resin composition will be described later.

[0018] <Laminate structure> The total number of composite layers contained in the laminate of this embodiment may be adjusted appropriately depending on the application of the laminate, but from the viewpoint of improving the mechanical strength of the laminate, it is preferably 3 or more layers, more preferably 4 or more layers, and even more preferably 5 or more layers. Furthermore, from the viewpoints of miniaturization of the printed wiring board and processability of the laminate, the total number of composite layers is preferably 20 or less layers, more preferably 18 or less layers, and even more preferably 16 or less layers.

[0019] The number of composite layers (X) contained in the laminate of this embodiment is not particularly limited, but from the viewpoint of improving warpage, it is preferably 2 or more. Furthermore, from the viewpoints of miniaturization of the printed wiring board and processability of the laminate, the number of composite layers (X) is preferably 16 or less, more preferably 15 or less, and even more preferably 14 or less. The volume ratio of the composite layer (X) in the laminate of this embodiment is not particularly limited, but from the viewpoint of improving warpage, it is preferably 50% by volume or more, more preferably 55% by volume or more, and even more preferably 60% by volume or more. Furthermore, from the viewpoints of miniaturization of printed wiring boards and processability of the laminate, the volume ratio of the composite layer (X) is preferably 95% by volume or less, more preferably 90% by volume or less, and even more preferably 88% by volume or less.

[0020] The number of composite layers (Y) contained in the laminate of this embodiment is not particularly limited, but from the viewpoint of connection reliability, it is preferably 1 or more, more preferably 2 or more. Moreover, from the viewpoint of increasing the elastic modulus and decreasing the thermal expansion of the laminate, the number of composite layers (Y) is preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less. The volume ratio of the composite layer (Y) in the laminate of this embodiment is not particularly limited, but from the viewpoint of connection reliability of the laminate, it is preferably 5% by volume or more, more preferably 10% by volume or more, and even more preferably 12% by volume or more. Moreover, from the viewpoint of improving warpage, the volume ratio of the composite layer (Y) is preferably 50% by volume or less, more preferably 45% by volume or less, and even more preferably 40% by volume or less.

[0021] From the viewpoint of improving warpage, the number of composite layers (X) contained in the laminate of this embodiment is preferably greater than the number of composite layers (Y). The difference between the number of layers of the composite layer (X) and the number of layers of the composite layer (Y) [composite layer (X) - composite layer (Y)] is not particularly limited, but from the viewpoint of improving warpage, it is preferably 1 layer or more, more preferably 2 layers or more, and even more preferably 3 layers or more. Furthermore, from the viewpoint of miniaturization of the printed wiring board and processability of the laminate, the difference in the number of layers is preferably 15 layers or less, more preferably 14 layers or less, and even more preferably 13 layers or less.

[0022] The thickness of each composite layer contained in the laminate of this embodiment is not particularly limited, but is preferably 0.01 mm or more, more preferably 0.02 mm or more, and even more preferably 0.025 mm or more from the viewpoints of insulation reliability, processability, etc. Furthermore, the thickness of each composite layer is preferably 0.5 mm or less, more preferably 0.3 mm or less, and even more preferably 0.2 mm or less from the viewpoint of thinning the printed wiring board.

[0023] The thickness of the laminate of this embodiment is not particularly limited, but is preferably 0.3 mm or more, more preferably 0.4 mm or more, and even more preferably 0.5 mm or more from the viewpoint of the mechanical strength, processability, etc. of the laminate. Furthermore, from the viewpoint of thinning the printed wiring board, the thickness of the laminate is preferably 5 mm or less, more preferably 3 mm or less, even more preferably 2 mm or less, and particularly preferably 1.6 mm or less. The thickness of the laminate does not include the thickness of an outer layer such as a metal foil, which may be optionally provided as described below.

[0024] The laminate of this embodiment preferably contains one or more composite layers (X) and two or more composite layers (Y), and has at least a laminate portion (hereinafter also referred to as a "sandwich laminate portion") in which at least one composite layer (X) is disposed between two composite layers (Y).

[0025] 2 and 3 show an example of a sandwich laminate. The sandwich laminated section 4A shown in FIG. 2 has a configuration in which one composite layer (X) is disposed between two composite layers (Y). The sandwich laminated section 4B shown in FIG. 3 has a configuration in which ten composite layers (X) are arranged between two composite layers (Y).

[0026] In the sandwich laminate, the number of composite layers (X) disposed between the two composite layers (Y) on both sides is not particularly limited, but from the viewpoint of improving warpage, it is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. In addition, the number of composite layers (X) disposed between the two composite layers (Y) on both sides is not particularly limited, but from the viewpoint of miniaturization of the printed wiring board and processability of the laminate, it is preferably 16 or less, more preferably 15 or less, and even more preferably 14 or less.

[0027] The laminate of this embodiment preferably has a sandwich laminate portion in at least a part of the laminate, and may be composed only of a sandwich laminate portion. Examples of laminates having a sandwich laminate portion in at least a portion thereof include laminates having one or more layers selected from the group consisting of composite layer (X) and composite layer (Y) on the outside of the composite layer (Y) on both or one side of the sandwich laminate portion. 4 and 5 show an example of a laminate having a sandwich laminated portion as a part of the laminate plate. FIG. 4 shows a laminate 10 having one composite layer (Y) on each of the outer sides of the composite layers (Y) on both sides that make up the sandwich laminated portion 4B. FIG. 5 shows a laminate 11 having one composite layer (X) on each side of the composite layers (Y) that make up the sandwich laminate 4B. An example of a laminate consisting of only sandwich laminated portions is a laminate plate consisting of only sandwich laminated portions 4A or 4B shown in FIGS.

[0028] The laminate of this embodiment is a laminate containing two or more composite layers (Y), and it is preferable that the outermost layers on both sides of the laminate are composite layers (Y). In this case, the composite layer disposed between the outermost composite layers (Y) on both sides may contain at least one composite layer (X), and may be a combination of one or more composite layers (X) and one or more composite layers (Y), but it is preferable that it contains only one or more composite layers (X). That is, the laminate of this embodiment is a laminate containing one or more composite layers (X) and only two composite layers (Y), and it is preferable that the outermost layers on both sides of the laminate are composite layers (Y) (hereinafter, this embodiment will also be referred to as a "sandwich laminate." A sandwich laminate corresponds to a laminate composed only of the above-mentioned sandwich laminate portion).

[0029] In the sandwich laminate, the number of composite layers (X) disposed between the two composite layers (Y) on both sides is the same as the preferred range in the sandwich laminate portion described above. The volume ratio of the outermost composite layer (Y) in the laminate of this embodiment is not particularly limited, but from the viewpoint of connection reliability, it is preferably 3 volume % or more, more preferably 5 volume % or more, and even more preferably 6 volume % or more. The volume ratio of the outermost composite layer (Y) in the laminate of this embodiment is not particularly limited, but from the viewpoint of improving warpage, it is preferably 25 volume % or less.

[0030] FIG. 6 shows an example of a sandwich laminate. The sandwich laminate 12 shown in FIG. 6 has a structure in which 12 composite layers (X) are arranged between two composite layers (Y) on both sides.

[0031] When the laminate of this embodiment contains two or more composite layers (X), the two or more composite layers (X) may be the same or different. Furthermore, when the laminate of this embodiment contains two or more composite layers (Y), the two or more composite layers (Y) may be the same or different. For example, in the sandwich laminate 4A shown in Fig. 3 and the sandwich laminate 12 shown in Fig. 6, the two composite layers (Y) on both sides may be the same or different in structure such as thickness, physical properties such as elastic modulus, composition, etc. Similarly, the two or more composite layers (X) disposed between the two composite layers (Y) on both sides may be the same or different in structure such as thickness, physical properties such as elastic modulus, composition, etc.

[0032] The above-described configuration of the laminated plate is one example of the laminated plate of this embodiment, and this embodiment is not limited to laminated plates having these configurations. Next, preferred embodiments of materials constituting the composite layer of this embodiment will be described.

[0033] <Fiber base material> The shape of the fiber substrate can be any well-known shape used in various laminates for electrical insulating materials, such as a woven fabric formed by interweaving warp and weft yarns (i.e., glass cloth), a nonwoven fabric, roving, a chopped strand mat, a surfacing mat, etc. Among these, the fiber substrate is preferably a glass cloth. The fiber substrate is preferably one that has been surface-treated with a silane coupling agent or the like, or one that has been mechanically opened, from the viewpoints of heat resistance, moisture resistance, processability, and the like.

[0034] The thickness of the fiber substrate is not particularly limited, but is preferably 0.01 mm or more, more preferably 0.02 mm or more, and even more preferably 0.025 mm or more from the viewpoints of insulation reliability, processability, etc. Furthermore, the thickness of the fiber substrate is preferably 0.5 mm or less, more preferably 0.3 mm or less, and even more preferably 0.2 mm or less from the viewpoint of thinning the printed wiring board.

[0035] <Glass fiber> Next, the glass fibers constituting the fiber substrate will be described. Unless otherwise specified, the following explanation applies to both the first glass fiber and the second glass fiber, and when simply referring to "glass fiber," it refers to both the first glass fiber and the second glass fiber.

[0036] The glass fiber is not particularly limited, but is preferably used, for example, as a strand consisting of tens to hundreds of fibers bundled together or as a yarn formed by twisting strands, and the fiber substrate used in this embodiment is preferably a glass cloth woven with the above-mentioned yarns as warp and weft. The single fiber diameter of the glass fiber is not particularly limited, but is preferably 2 to 12 μm, more preferably 3 to 11 μm, and even more preferably 4 to 10 μm. The number of fibers in the bundle of glass fibers is not particularly limited, but is preferably 40 to 1,000, more preferably 45 to 700, and even more preferably 50 to 400.

[0037] (Tensile modulus of glass fiber) In the laminate (1) of this embodiment, the first glass fiber has a higher tensile modulus at 25°C (hereinafter, when simply referred to as "tensile modulus" it refers to the tensile modulus at 25°C) than the second glass fiber, and in the laminate (2) of this embodiment as well, it is preferable that the first glass fiber has a higher tensile modulus than the second glass fiber.

[0038] The tensile modulus of the glass fibers is not particularly limited, but the tensile modulus of the first glass fiber is preferably 80 GPa or more, and the tensile modulus of the second glass fiber is preferably less than 80 GPa. When the tensile modulus of the first and second glass fibers is within the above range, the obtained laminate exhibits even more excellent effects of the invention.

[0039] From the same viewpoint as above, the tensile modulus of the first glass fiber is more preferably 82 GPa or more, further preferably 84 GPa or more, and particularly preferably 85 GPa or more. Also, from the viewpoint of maintaining good drilling processability and insulation reliability, the tensile modulus of the first glass fiber is preferably 110 GPa or less, more preferably 100 GPa or less, and further preferably 90 GPa or less. From the same viewpoint as above, the tensile modulus of the second glass fiber is more preferably less than 79 GPa, even more preferably less than 78 GPa, and particularly preferably less than 75 GPa. From the viewpoint of maintaining good drilling processability and insulation reliability, the tensile modulus of the second glass fiber is preferably 53 GPa or more, more preferably 69 GPa or more, and even more preferably 70 GPa or more. The tensile modulus of the glass fiber at 25° C. can be measured by a known method for measuring the tensile modulus using, for example, a Tensilon with a monofilament as the measurement object.

[0040] From the same viewpoint as above, the difference in tensile modulus at 25° C. between the first glass fiber and the second glass fiber is preferably 10 GPa or more, more preferably 11 GPa or more, and even more preferably 12 GPa or more.

[0041] (Glass fiber composition) The ratio of the Al2O3 content to the SiO2 content in the second glass fiber [Al2O3 content / SiO2 content] (by mass) is preferably 0.35 or less, more preferably 0.32 or less, and even more preferably 0.30 or less. If the ratio of the Al2O3 content to the SiO2 content is within this range, a laminate with better connection reliability can be obtained.

[0042] The total content of SiO2 and Al2O3 in the first glass fiber is not particularly limited, but is preferably 80 mass% or more, and the total content of SiO2 and Al2O3 in the second glass fiber is not particularly limited, but is preferably less than 80 mass%. When the total content of SiO2 and Al2O3 in the first and second glass fibers is within the above range, the resulting laminate has even better connection reliability and warpage resistance.

[0043] From the same viewpoint as above, the total content of SiO2 and Al2O3 in the first glass fiber is more preferably 81 mass% or more, and even more preferably 82 mass% or more. Furthermore, from the viewpoint of maintaining good drilling processability and insulation reliability, the total content of SiO2 and Al2O3 in the first glass fiber is preferably 96 mass% or less, more preferably 94 mass% or less, even more preferably 92 mass% or less, and particularly preferably 90 mass% or less. From the same viewpoint as above, the total content of SiO2 and Al2O3 in the second glass fiber is more preferably less than 78 mass%, further preferably less than 76 mass%, and particularly preferably less than 74 mass%. From the viewpoint of increasing the elastic modulus and decreasing the thermal expansion of the laminate, the total content of SiO2 and Al2O3 in the second glass fiber is preferably 50 mass% or more, more preferably 55 mass% or more, and even more preferably 60 mass% or more.

[0044] The first glass fibers satisfy the above total content of SiO2 and Al2O3, and the Al2O3 content is preferably 20 mass % or more, more preferably 20 to 30 mass %, and even more preferably 20 to 25 mass %. The second glass fibers satisfy the above total content of SiO2 and Al2O3, and the Al2O3 content is preferably less than 24 mass%, more preferably less than 22 mass%, and even more preferably less than 20 mass%.

[0045] In addition to SiO2 and Al2O3, the glass fiber may contain other components such as Fe2O3, B2O3, CaO, MgO, Na2O, K2O, Li2O, TiO2, ZnO, ZrO2, and F2. The component other than SiO2 and Al2O3 contained in the glass fiber is preferably one or more of the above other components. Among these, the first glass fibers satisfy the above total content of SiO2 and Al2O3, and the MgO content is preferably 8 mass% or more, more preferably 9 mass% or more, and even more preferably 10 mass% or more. The second glass fibers satisfy the above total content of SiO2 and Al2O3, and the MgO content is preferably less than 8 mass%, and more preferably less than 7 mass%.

[0046] (Thermal expansion coefficient of glass fiber) The thermal expansion coefficient of the glass fiber is not particularly limited, but the thermal expansion coefficient of the first glass fiber is preferably less than 4.0 ppm / °C. When the thermal expansion coefficient of the first glass fiber is within the above range, the resulting laminate has even lower thermal expansion and higher elastic modulus. From the same viewpoint, the thermal expansion coefficient of the first glass fiber is preferably less than 3.8 ppm / °C, more preferably less than 3.5 ppm / °C, and even more preferably less than 3.0 ppm / °C. Furthermore, taking into consideration the balance with other physical properties, the thermal expansion coefficient of the first glass fiber may be 2.0 ppm / °C or more, 2.3 ppm / °C or more, or 2.5 ppm / °C or more.

[0047] The thermal expansion coefficient of the second glass fiber is preferably as small as possible to reduce the thermal expansion coefficient of the laminate. From the same viewpoint, the thermal expansion coefficient of the second glass fiber is preferably less than 6.5 ppm / °C, more preferably less than 6.0 ppm / °C, and even more preferably less than 5.7 ppm / °C. On the other hand, the thermal expansion coefficient of the second glass fiber tends to be higher than that of the first glass fiber, taking into consideration the balance between its composition and other physical properties. From such a viewpoint, the thermal expansion coefficient of the second glass fiber may be 4.0 ppm / °C or more, 4.5 ppm / °C or more, 5.0 ppm / °C or more, or 5.3 ppm / °C or more.

[0048] (Type of glass fiber) Examples of glass fibers constituting the fiber substrate include E glass, S glass, C glass, D glass, T glass, NE glass, A glass, H glass, and quartz glass. From these, an appropriate glass fiber may be selected in consideration of the preferred physical properties, composition, and the like of the first glass fiber and the second glass fiber described above.

[0049] Representative compositions of E glass, S glass, C glass, D glass, T glass, and NE glass are as follows: E glass: SiO2 (52-56 mass%), Al2O3 (12-16 mass%), Fe2O3 (0-0.8 mass%), B2O3 (5-10 mass%), CaO (16-25 mass%), MgO (0-6 mass%), Na2O+K2O (0-2 mass%), TiO2 (0-1.5 mass%), F2 (0-1 mass%) S-glass: SiO2 (62 to 65 mass%), Al2O3 (20 to 25 mass%), CaO (0 to 0.01 mass%), MgO (10 to 15 mass%), B2O3 (0 to 0.01 mass%), Na2O, and K2O (0 to 1 mass%) C glass: SiO2 (65 mass%), Al2O3 (4 mass%), B2O3 (5 mass%), CaO (7 mass%), MgO (3 mass%), Na2O (11 mass%), K2O (1 mass%), Li2O (0.5 mass%), ZnO (3.5 mass%) D glass: SiO2 (74 mass%), Al2O3 (0.5 mass%), B2O3 (22 mass%), CaO (0.5 mass%), Na2O (1 mass%), K2O (1.5 mass%), Li2O (0.5 mass%), T glass: SiO2 (64~66% by mass), Al2O3 (24~26% by mass), MgO (9~11% by mass) NE glass: SiO2 (52-56 mass%), CaO (0-10 mass%), Al2O3 (10-15 mass%), B2O3 (15-20 mass%), MgO (0-5 mass%), Na2O+K2O (0-1 mass%), TiO2 (0.5-5 mass%)

[0050] Among the glass fibers having these materials, the first glass fiber is preferably S-glass, and the second glass fiber is preferably E-glass. That is, the first fiber base material used in the laminate of this embodiment is preferably a fiber base material made of S-glass fiber, and the second fiber base material is preferably a fiber base material made of E-glass fiber. Furthermore, it is more preferable that the first fiber base material is a glass cloth made of S-glass fibers (hereinafter also referred to as "S-glass cloth"), and it is more preferable that the second fiber base material is a glass cloth made of E-glass fibers (hereinafter also referred to as "E-glass cloth"). The S-glass cloth and the E-glass cloth may each contain glass fibers other than the S-glass fiber and the E-glass fiber, but the content thereof is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and particularly preferably zero.

[0051] <Thermosetting resin composition> The thermosetting resin composition used to form the composite layer is not particularly limited as long as it contains a thermosetting resin, and may contain, as necessary, a curing agent, a curing accelerator, an inorganic filler, etc. Hereinafter, each component contained in the thermosetting resin composition will be described.

[0052] (thermosetting resin) Examples of thermosetting resins include epoxy resins, phenolic resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, modified silicone resins, triazine resins, melamine resins, urea resins, furan resins, etc. Among these, modified silicone resins and epoxy resins are preferred. The thermosetting resin may be used alone or in combination of two or more kinds.

[0053] [Modified silicone resin] The modified silicone resin is preferably one obtained by reacting a siloxane compound (A) having a primary amino group (hereinafter also referred to as "siloxane compound (A)") with a maleimide compound (B) having at least two N-substituted maleimide groups in one molecule (hereinafter also referred to as "maleimide compound (B)"), and more preferably one obtained by further reacting one or more compounds selected from the group consisting of an amine compound (C) having an acidic substituent and an amine compound (D) having at least two primary amino groups in one molecule (hereinafter also referred to as "amine compound (D)").

[0054] -Siloxane compound (A)- The siloxane compound (A) is a siloxane compound having a primary amino group, and is preferably a compound represented by the following general formula (A-1).

[0055] [ka] (In the formula, R 1 ~R 4 each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group; X 1 and X 2 each independently represents a divalent organic group, and n represents an integer of 2 to 100.

[0056] In the above general formula (A-1), R 1 ~R 4 Examples of the alkyl group having 1 to 5 carbon atoms represented by include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc. Among these, a methyl group is preferred. R 1 ~R 4 Examples of the substituent of the substituted phenyl group represented by the formula include an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, an amino group, a vinyl group, and a carboxy group. X 1 and X 2 Examples of the divalent organic group represented by the formula (I) include alkylene groups having 1 to 5 carbon atoms. Examples of the alkylene group include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group. Among these, a 1,3-trimethylene group is preferred. The amine equivalent of the siloxane compound (A) is preferably from 500 to 3,000 g / mol, more preferably from 600 to 2,000 g / mol, and even more preferably from 700 to 1,500 g / mol.

[0057] -Maleimide compound (B)- The maleimide compound (B) is a maleimide compound having at least two N-substituted maleimide groups in one molecule, and is preferably a compound represented by any one of the following general formulae (B-1) to (B-4).

[0058] [ka] (In the formula, R 11 ~R 13 Each of X independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms. 11 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O-, or a sulfonyl group. p, q, and r each independently represent an integer of 0 to 4. m represents an integer of 0 to 10.

[0059] In the above general formulas (B-1) to (B-4), R 11 ~R 13 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R in the above general formula (A-1) is 1 The same can be mentioned. X 11 The alkylene group having 1 to 5 carbon atoms represented by X in the above general formula (A-1) is 1 The same can be mentioned. X 11 Examples of the alkylidene group having 2 to 5 carbon atoms represented by the formula include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group.

[0060] Examples of the maleimide compound (B) include bis(4-maleimidophenyl)methane, polyphenylmethane maleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, m-phenylene bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, etc. Among these, bis(4-maleimidophenyl)methane is preferred.

[0061] -Amine compound (C) having an acidic substituent- The amine compound (C) having an acidic substituent is preferably an amine compound represented by the following general formula (C-1).

[0062] [ka] (In the formula, R 21 R each independently represents a hydroxyl group, a carboxyl group, or a sulfonic acid group. 22 each independently represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, and x is an integer of 1 to 5. , y is an integer of 0 to 4, and satisfies 1≦x+y≦5.

[0063] In the above general formula (C-1), R 21 The alkyl group having 1 to 5 carbon atoms represented by R in the above general formula (A-1) is 1 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0064] Examples of the amine compound (C) having an acidic substituent include o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, etc. Among these, m-aminophenol and p-aminophenol are preferred from the viewpoints of solubility and reactivity.

[0065] -Amine compound (D)- The amine compound (D) is an amine compound (D) having at least two primary amino groups in one molecule, and is preferably a compound represented by any one of the following general formulas (D-1) to (D-3).

[0066] [ka] (In the formula, X 13 represents a single bond, an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O-, a sulfonyl group, a keto group, a fluorenediyl group, or a phenylenedioxy group. 14 and R 15 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a methoxy group, or a hydroxyl group. s and t each independently represent an integer of 0 to 4. X 14 ~X 16 each independently represents a single bond, an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O-, or a sulfonyl group.

[0067] X 13 ~X 16 The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by the formula (B-1) are, for example, X 11 The same can be mentioned. R 14 and R 15 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R in the above general formula (A-1) is 1 Among these, a methyl group and an ethyl group are preferred.

[0068] Examples of the amine compound (D) include m-phenylenediamine, p-phenylenediamine, 1,4-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, benzidine, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diaminodiphenyl sulfide, 4,4'-diamino-3,3'-biphenyldiol, and benzoguanamine. Of these, 3,3'-diethyl-4,4'-diaminodiphenylmethane is preferred.

[0069] The modified silicone resin can be prepared by reacting the above components (A) to (D), for example, at a temperature of 70 to 150°C. During the reaction, an organic solvent such as propylene glycol monomethyl ether or cyclohexanone; a reaction catalyst, etc. may be used as needed.

[0070] (Amount of each ingredient used) Regarding the amounts of each component used in the reaction of components (A) to (D), the equivalent ratio (C=C groups / NH2 groups) of the sum of the primary amino groups in components (A), (C), and (D) to the sum of the carbon-carbon double bond groups in the maleimide groups of component (B) is preferably 0.1 to 10, more preferably 1 to 9, and even more preferably 2 to 5. An equivalent ratio of 0.1 or more can suppress gelation and a decrease in heat resistance, while an equivalent ratio of 10 or less can suppress a decrease in solubility in organic solvents and a decrease in heat resistance. The amount of component (D) used is preferably 20 to 500 parts by mass, more preferably 30 to 200 parts by mass, and even more preferably 40 to 100 parts by mass per 100 parts by mass of component (A), while satisfying the above relational expression. The amount of component (C) used is preferably 1 to 500 parts by mass, more preferably 4 to 200 parts by mass, even more preferably 7 to 100 parts by mass, and particularly preferably 10 to 50 parts by mass, per 100 parts by mass of component (A), while satisfying the above relational formula.

[0071] From the viewpoints of heat resistance, low water absorption, and thermal expansion coefficient, the content of the modified silicone resin in the thermosetting resin composition is preferably 5 to 80 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 40 parts by mass, per 100 parts by mass of the solid content of the thermosetting resin composition. In this specification, the term "solid content" refers to the non-volatile content excluding volatile substances such as solvents, and refers to the components that remain without volatilization when the resin composition is dried, including those that are liquid, syrup-like, or wax-like at room temperature. Here, in this specification, room temperature refers to 25°C.

[0072] [Epoxy resin] Examples of epoxy resins include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol A novolac epoxy resins, bisphenol F novolac epoxy resins, stilbene epoxy resins, triazine skeleton-containing epoxy resins, fluorene skeleton-containing epoxy resins, triphenolmethane epoxy resins, biphenyl epoxy resins, xylylene epoxy resins, biphenylaralkyl epoxy resins, naphthalene epoxy resins, dicyclopentadiene epoxy resins, alicyclic epoxy resins, diglycidyl ether compounds of polyfunctional phenols and polycyclic aromatics such as anthracene, and phosphorus-containing epoxy resins in which a phosphorus compound has been introduced into these. Among these, biphenylaralkyl epoxy resins are preferred from the viewpoints of heat resistance and flame retardancy.

[0073] When the thermosetting resin composition contains an epoxy resin, the content thereof is preferably 2 to 60 parts by mass, more preferably 5 to 40 parts by mass, and even more preferably 8 to 20 parts by mass, relative to 100 parts by mass of the solid content of the thermosetting resin composition, from the viewpoints of heat resistance, low water absorption, and thermal expansion coefficient.

[0074] [Acrylic polymer] The thermosetting resin composition may be a resin composition containing an acrylic polymer and a thermosetting resin, in which case the thermosetting resin composition may form a phase-separated structure of a first phase containing the acrylic polymer and a second phase containing the thermosetting resin. An acrylic polymer is usually a polymer containing a (meth)acrylic acid ester as a monomer. The acrylic polymers may be used alone or in combination of two or more.

[0075] The acrylic polymer is preferably an acrylic polymer containing a structural unit derived from a (meth)acrylic acid ester represented by the following general formula (1). In this embodiment, "(meth)acrylic acid" refers to both "acrylic acid" and "methacrylic acid", and the same applies to other similar terms.

[0076] [ka] (In formula (1), R 32 represents an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an aryl group, or an aralkyl group. 31 represents a hydrogen atom or a methyl group.

[0077] R 32The number of carbon atoms in the alkyl group represented by the formula (I) is preferably 1 to 20, more preferably 1 to 15, and even more preferably 2 to 10. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a 2-ethylhexyl group. These alkyl groups may have a substituent. Examples of the substituent on the alkyl group include an alicyclic hydrocarbon group, a hydroxyl group, a halogen atom, an oxygen-containing hydrocarbon group, and a nitrogen-containing cyclic group. R 32 The number of carbon atoms in the cycloalkyl group represented by the formula (I) is preferably 6 to 13, more preferably 6 to 12, and still more preferably 7 to 10. Examples of the cycloalkyl group include a cyclohexyl group, a norbornyl group, a tricyclodecanyl group, an isobornyl group, and an adamantyl group, and among these, a norbornyl group, a tricyclodecanyl group, and an isobornyl group are preferred. R 32 The number of carbon atoms in the cycloalkylalkyl group represented by the following formula is preferably 6 to 13, more preferably 6 to 12, and further preferably 7 to 10. Examples of the cycloalkylalkyl group include a norbornylmethyl group and a tricyclodecylethyl group. R 32 The number of carbon atoms in the aryl group represented by the formula is preferably 6 to 13, more preferably 6 to 12, and even more preferably 6 to 10. Examples of the aryl group include a phenyl group and a nonylphenyl group. R 32 The number of carbon atoms in the aralkyl group represented by the formula (I) is preferably 7 to 15, more preferably 7 to 13, and even more preferably 7 to 11. Examples of the aralkyl group include a benzyl group and a 4-methylbenzyl group.

[0078] Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobutyl (meth)acrylate, ethylene glycol methyl ether (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1,0(2,6)]dec-8yl (meth)acrylate, isodecyl (meth)acrylate, octadecyl (meth)acrylate, lauryl (meth)acrylate, allyl (meth)acrylate, norbornylmethyl (meth)acrylate, tricyclodecylethyl (meth)acrylate, phenyl (meth)acrylate, nonylphenyl (meth)acrylate, benzyl (meth)acrylate, and 4-methylbenzyl (meth)acrylate. These may be used alone or in combination of two or more.

[0079] (Inorganic filler) Examples of inorganic fillers include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, aluminum borate, potassium titanate, short glass fibers, fine glass powder, hollow glass, etc. Among these, from the viewpoints of heat resistance and flame retardancy, silica is preferred, and fused silica such as fused spherical silica is more preferred. The average particle size of the inorganic filler is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and even more preferably 0.2 to 1 μm. An average particle size of 0.1 μm or more can maintain good fluidity, while an average particle size of 10 μm or less can prevent defects caused by coarse particles. Here, the average particle size refers to the particle size at the point corresponding to 50% volume when a cumulative frequency distribution curve of particle sizes is calculated, assuming the total volume of particles to be 100%, and can be measured using a particle size distribution analyzer using a laser diffraction scattering method. The inorganic filler may be used alone or in combination of two or more kinds.

[0080] When the thermosetting resin composition contains an inorganic filler, the content thereof is preferably 10 to 80 parts by mass, more preferably 30 to 75 parts by mass, and even more preferably 50 to 70 parts by mass, relative to 100 parts by mass of the solid content of the thermosetting resin composition, from the viewpoints of reducing the coefficient of thermal expansion and increasing the modulus of elasticity.

[0081] (curing accelerator) Examples of the curing accelerator include organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octoate, cobalt octoate, bisacetylacetonate cobalt(II), and trisacetylacetonate cobalt(III); imidazole compounds and derivatives thereof; organic phosphorus compounds; secondary amines, tertiary amines, and quaternary ammonium salts. Among these, imidazole compounds and derivatives thereof are preferred from the viewpoints of heat resistance and flame retardancy. The curing accelerator may be used alone or in combination of two or more kinds. When the thermosetting resin composition contains a curing accelerator, the content thereof is, from the viewpoint of heat resistance and flame retardancy, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, and is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less, per 100 parts by mass of the solid content of the thermosetting resin composition.

[0082] The thermosetting resin composition may or may not contain, as necessary, one or more selected from the group consisting of a flame retardant, a functional resin, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent brightening agent, an adhesion improver, and an organic solvent.

[0083] The thermosetting resin composition may be in the form of a varnish in which each component is dissolved or dispersed in an organic solvent, so as to facilitate use in the production of prepregs and the like. Examples of the organic solvent include alcohol-based solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as butyl acetate and propylene glycol monomethyl ether acetate; ether-based solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; and sulfur-containing solvents such as dimethyl sulfoxide. These may be used alone or in combination of two or more. The solid content of the varnish is preferably 40 to 90 mass%, more preferably 45 to 85 mass%, and even more preferably 50 to 80 mass%. When the solid content of the varnish is within this range, good coatability can be maintained and a prepreg with an appropriate content of the thermosetting resin composition can be obtained.

[0084] [Laminate manufacturing method] The method for manufacturing a laminated board of this embodiment is as follows: A prepreg (a) obtained by impregnating a fiber base material composed of a first glass fiber with a thermosetting resin composition; A prepreg (b) obtained by impregnating a fiber base material composed of second glass fibers with a thermosetting resin composition; This is a method for manufacturing a laminated plate, in which the above is laminated and molded. The glass fiber, fiber base material, thermosetting resin composition, and the like used in the method for producing a laminated board of this embodiment are as described above.

[0085] The prepregs (a) and (b) used in the manufacturing method of this embodiment are obtained by impregnating a fiber substrate with a thermosetting resin composition, and can be manufactured, for example, by impregnating a fiber substrate with a varnish-like thermosetting resin composition and then semi-curing (B-stage) the composition by heating and drying at a temperature of 100 to 200°C for 1 to 30 minutes. The content of solids derived from the thermosetting resin composition in the prepregs (a) and (b) is preferably 20 to 90 mass %, more preferably 30 to 70 mass %, and even more preferably 40 to 60 mass %.

[0086] Next, the obtained prepreg (a) and prepreg (b) are appropriately stacked to form the desired laminate configuration, and metal foil such as copper or aluminum is arranged on one or both sides as needed, thereby manufacturing the laminate of this embodiment. The metal foil is not particularly limited as long as it is used for laminates for electrical insulating materials. Note that a laminate of this embodiment having metal foil arranged on one or both sides is called a metal-clad laminate, and among these, a laminate having copper foil arranged on one or both sides is called a copper-clad laminate. The molding conditions for producing the laminated board can be the same as those for laminated boards and multilayer boards for electrical insulating materials, and can be, for example, a temperature of 100 to 250°C, a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours, using a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc.

[0087] [Printed wiring board] The printed wiring board of this embodiment is a printed wiring board that includes the laminate of this embodiment. The printed wiring board of this embodiment can be manufactured, for example, by forming a circuit on the surface of the laminate of this embodiment. Alternatively, the conductor layer of the laminate of this embodiment can be processed for wiring by a conventional etching method, and then multiple laminates with prepregs interposed therebetween can be stacked together and hot-pressed to form a multilayer structure. The printed wiring board can then be manufactured by forming through-holes or blind via holes by drilling or laser processing and forming interlayer wiring using plating or a conductive paste.

[0088] [Semiconductor Package] The semiconductor package of this embodiment is formed by mounting a semiconductor on the printed wiring board of this embodiment. The semiconductor package of this embodiment can be manufactured by mounting a semiconductor chip, memory, etc. on the printed wiring board of this embodiment. [Example]

[0089] Next, the present embodiment will be described in more detail with reference to the following examples, but these examples do not limit the present embodiment. The performance of the prepreg and copper-clad laminate obtained in each example was measured and evaluated by the following methods.

[0090] [Evaluation method] (1) Thermal expansion coefficient The copper foil was removed from the copper-clad laminate obtained in each example by immersing it in a copper etching solution to prepare an evaluation board measuring 5 mm in length (X direction) × 5 mm in width (Y direction). The evaluation board was used as the measurement object for thermomechanical analysis using a compression method using a TMA tester (manufactured by DuPont, product name: TMA2940). After mounting the evaluation board in the X direction, measurements were performed twice consecutively under the measurement conditions of a load of 5 g and a heating rate of 10°C / min. The average thermal expansion coefficient from 30°C to 100°C in the second measurement was calculated, and this was used as the thermal expansion coefficient value.

[0091] (2) Flexural modulus The copper foil was removed from the copper-clad laminate obtained in each example by immersing it in a copper etching solution to prepare a 50 mm × 25 mm evaluation board. The flexural modulus of the evaluation board was measured using a 5-ton Tensilon manufactured by Orientec Co., Ltd. at a crosshead speed of 1 mm / min and a span distance of 20 mm.

[0092] (3) Connection reliability To evaluate the reliability of the connection with the motherboard, a circuit-formed package substrate and a motherboard were fabricated using the copper-clad laminate obtained in each example. The package substrate and the motherboard were then electrically connected using solder balls. The resulting structure was then placed in a temperature cycle tester (-55 to 125°C), and the connection resistance was measured every specified number of cycles. The number of cycles until solder ball fracture was determined as the resistance value fluctuating by 20% or more. The connection reliability was evaluated based on the number of cycles at a 20% cumulative failure rate in a Weibull plot.

[0093] <Manufacturing of copper clad laminates> [Example 1] (Copper clad laminate 1: A copper clad laminate with copper foil on both sides of the laminate shown in Figure 6) (1) Preparation of varnish A 1-liter reactor equipped with a thermometer, stirrer, and reflux condenser and capable of heating and cooling was charged with 19.4 g of siloxane diamine (Dow Corning Toray Co., Ltd., trade name: X-22-161A, amino functional group equivalent weight: 800 g / mol), 13.0 g of 3,3'-diethyl-4,4'-diaminodiphenylmethane, 122.9 g of N,N'-(4,4'-diphenylmethane)bismaleimide, 4.7 g of p-aminophenol, and 240.0 g of propylene glycol monomethyl ether. After reacting these components at 115°C, the mixture was concentrated under atmospheric pressure until the resin concentration reached 60% by mass. Furthermore, 53.3 g of cyclohexanone was added at 90°C and stirred for 30 minutes to obtain an intermediate varnish. 303.5 g of this intermediate varnish was mixed with 601.0 g of a silica methyl isobutyl ketone solution (prepared by adding 700 g of spherical silica with an average particle size of 0.25 μm to 300 g of methyl isobutyl ketone solution containing 7 g of 3-aminopropyltrimethoxysilane while stirring), 1.2 g of a curing accelerator (manufactured by Shikoku Chemicals Corporation, product name: C17Z), and 65.6 g of a biphenylaralkyl novolac epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product name: NC-3000-H). Further addition of methyl ethyl ketone as a dilution solvent yielded a uniform varnish with a solids concentration of 65% by mass.

[0094] (2) Prepreg fabrication Next, the varnish was applied to 0.1 mm S-glass cloth (tensile modulus at 25°C: 85.3 GPa, total SiO2 and Al2O3 content: 82-90% by mass, thermal expansion coefficient: 2.9 ppm / °C) and 0.1 mm E-glass (tensile modulus at 25°C: 73 GPa, total SiO2 and Al2O3 content: 64-72% by mass, ratio of Al2O3 content to SiO2 content (by mass): 0.28, thermal expansion coefficient: 5.5 ppm / °C), respectively, by impregnation, and then heated and dried at 130°C for 3 minutes. This resulted in prepregs containing S-glass cloth and E-glass cloth, each with a solid content derived from the thermosetting resin composition of 48% by mass. Furthermore, the number of prepregs required for the production of the laminates described below was produced using the same procedure.

[0095] (3) Fabrication of laminated plates Next, the prepregs prepared above were laminated so that the outermost layers on each side were prepregs containing E-glass cloth, and the inner 12 layers were prepregs containing S-glass cloth. Electrodeposited copper foils with a thickness of 12 μm were then placed on both sides, and the laminate was pressed at a pressure of 2.5 MPa and a temperature of 240°C for 60 minutes to obtain copper-clad laminate 1.

[0096] [Example 2] (Copper clad laminate 2: A copper clad laminate with copper foil on both sides of the laminate shown in Figure 4) A copper-clad laminate 2 was obtained in the same manner as in Example 1, except that the prepreg lamination structure was such that the two outermost layers on each side were prepregs containing E-glass cloth, and the inner 10 layers were prepregs containing S-glass cloth.

[0097] [Example 3] (Copper clad laminate 3: A copper clad laminate with copper foil on both sides of the laminate shown in Figure 7) A copper-clad laminate 3 was obtained in the same manner as in Example 1, except that the prepreg lamination structure was changed to a structure in which the order was 6 layers of prepreg containing S-glass cloth, 2 layers of prepreg containing E-glass cloth, and 6 layers of prepreg containing S-glass cloth.

[0098] [Comparative Example 1] (Copper clad laminate 4: Copper clad laminate containing only S-glass cloth as the fiber substrate) A copper-clad laminate 4 was obtained in the same manner as in Example 1, except that the prepreg lamination structure was changed to 14 layers of prepreg containing S-glass cloth.

[0099] Comparative Example 2 (Copper clad laminate 5: Copper clad laminate containing only E-glass cloth as the fiber substrate) A copper-clad laminate 5 was obtained in the same manner as in Example 1, except that the prepreg lamination structure was changed to 14 layers of prepreg containing E-glass cloth.

[0100] The evaluation results of the laminated plate prepared above are shown in Table 1.

[0101] [Table 1]

[0102] As shown in Table 1, it was confirmed that the laminates of Examples 1 to 3 of this embodiment had high elastic modulus and low thermal expansion, and also had excellent connection reliability. [Explanation of symbols]

[0103] (X) Composite layer (X) (Y) Composite layer (Y) 1 composite layer 2. Fiber base material 2a warp thread 2b weft 3. Cured product of thermosetting resin composition 4A, 4B sandwich laminate 10~13 Laminated board

Claims

1. A laminate comprising 4 to 20 composite layers each containing a fiber base material and a cured product of a thermosetting resin composition, The four or more composite layers include two or more composite layers (X) and two or more composite layers (Y), The outermost layers on both surfaces of the laminate are composite layers (X), the content of the cured product of the thermosetting resin composition in the composite layer (X) which is the outermost layer on both surfaces is 20 to 60 mass %, the content of the inorganic filler in the cured product of the thermosetting resin composition contained in the composite layer (X) that is the outermost layer on both surfaces is 50 parts by mass or more per 100 parts by mass of the cured product of the thermosetting resin composition; The composite layer (X) is a layer containing a first fiber base material composed of a first glass fiber (excluding T-glass), the composite layer (Y) is a layer containing a second fiber base material composed of a second glass fiber, the first glass fiber (excluding T-glass) has a higher tensile modulus at 25°C than the second glass fiber; A laminate, wherein the cured product of the thermosetting resin composition contained in the composite layer (Y) contains an inorganic filler.

2. the first glass fiber (excluding T-glass) has a tensile modulus at 25°C of 80 GPa or more; 2. The laminate of claim 1, wherein the second glass fibers have a tensile modulus at 25°C of less than 80 GPa.

3. 3. The laminate according to claim 1, wherein the difference in tensile modulus at 25°C between the first glass fiber (excluding T-glass) and the second glass fiber is 10 GPa or more.

4. A laminate comprising 4 to 20 composite layers each containing a fiber base material and a cured product of a thermosetting resin composition, The four or more composite layers include two or more composite layers (X) and two or more composite layers (Y), The outermost layers on both surfaces of the laminate are composite layers (X), the content of the cured product of the thermosetting resin composition in the composite layer (X) which is the outermost layer on both surfaces is 20 to 60 mass %, the content of the inorganic filler in the cured product of the thermosetting resin composition contained in the composite layer (X) that is the outermost layer on both surfaces is 50 parts by mass or more per 100 parts by mass of the cured product of the thermosetting resin composition; The composite layer (X) is a layer containing a first fiber base material composed of a first glass fiber (excluding T-glass), the composite layer (Y) is a layer containing a second fiber base material composed of a second glass fiber, SiO in the first glass fiber (excluding T-glass) ２ and Al ２ O ３ The total content of SiO in the second glass fiber ２ and Al ２ O ３ is higher than the total content of A laminate, wherein the cured product of the thermosetting resin composition contained in the composite layer (Y) contains an inorganic filler.

5. The cured product of the thermosetting resin composition contained in the composite layer (Y) is a cured product of a thermosetting resin composition containing 10 to 80 parts by mass of an inorganic filler in 100 parts by mass of the thermosetting resin composition. The laminate according to any one of claims 1 to 4.

6. The cured product of the thermosetting resin composition contained in the composite layer (Y) is a cured product of a thermosetting resin composition containing 30 to 80 parts by mass of an inorganic filler in 100 parts by mass of the thermosetting resin composition. The laminate according to any one of claims 1 to 5.

7. The laminate according to any one of claims 1 to 6, wherein the inorganic filler is silica.

8. The laminate according to any one of claims 1 to 7, wherein the inorganic filler has an average particle size of 0.1 to 1 µm.

9. The laminate according to any one of claims 1 to 8, comprising five or more composite layers containing the fiber base material and a cured product of a thermosetting resin composition.

10. The laminate according to any one of claims 1 to 9, wherein the number of layers of the composite layer (X) is two.

11. The laminate according to any one of claims 1 to 10, which is for use in a printed wiring board.

12. A printed wiring board comprising the laminate according to any one of claims 1 to 11.

13. A semiconductor package comprising a semiconductor element mounted on the printed wiring board according to claim 12.

14. A method for producing the laminate according to any one of claims 1 to 11, comprising: a prepreg (a) obtained by impregnating a first fiber base material composed of the first glass fiber (excluding T-glass) with a thermosetting resin composition; a prepreg (b) obtained by impregnating a second fiber base material composed of the second glass fiber with a thermosetting resin composition; A method for manufacturing a laminated plate, comprising laminating and molding the above.

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