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

Abstract

The present invention provides a laminate that has a high modulus of elasticity and low thermal expansion while also exhibiting excellent connection reliability, a printed circuit board and a semiconductor package using the laminate, and a method for manufacturing the laminate. [Solution] A laminate containing two or more composite layers containing a fiber substrate 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 composite layer (X) is a layer containing a first fiber substrate made of first glass fibers, and composite layer (Y) is a layer containing a second fiber substrate made of second glass fibers, wherein the first glass fibers have a higher tensile modulus of elasticity at 25°C than the second glass fibers, a laminate, a printed wiring board and a semiconductor package using the laminate, and a method for manufacturing the laminate.

Description

[Technical Field]

[0001] This embodiment relates to laminates, printed circuit boards, semiconductor packages, and methods for manufacturing laminates. [Background technology]

[0002] In recent years, the miniaturization and increased performance of electronic devices have led to advancements in the wiring density and integration of printed circuit boards (PCBs), and consequently, the demand for improved reliability of PCBs has been strengthening. In particular, with the miniaturization and thinning of semiconductor packages, the occurrence of warping during component mounting and package assembly has become a major challenge.

[0003] One of the factors causing semiconductor packages to warp is the difference in thermal expansion coefficients between the semiconductor element and the printed circuit board on which it is mounted. Generally, the thermal expansion coefficient of the printed circuit board is greater than that of the semiconductor element. Therefore, packages subjected to thermal history such as heating during semiconductor element mounting experience warping stress due to this difference in thermal expansion coefficients. Effective methods to suppress semiconductor package warping include reducing the thermal expansion coefficient of the printed circuit board to minimize the difference with that of the semiconductor element, and increasing the rigidity of the printed circuit board by increasing its modulus of elasticity.

[0004] As laminates for printed circuit boards, prepregs obtained by impregnating or coating a fibrous substrate such as glass cloth with a thermosetting resin composition are generally used, and then laminated and heat-cured. The resin component contained in the prepreg has a high coefficient of thermal expansion and a low modulus of elasticity among the materials that make up the prepreg, so efforts are made to increase the modulus of elasticity and decrease the thermal expansion by increasing the density of inorganic fillers such as silica (see, for example, Patent Document 1). However, increasing the density of inorganic fillers may reduce insulation reliability, adhesion to copper foil, and press-workability. Therefore, from the perspective of ensuring these performance characteristics, there are limitations to increasing the elastic modulus and reducing thermal expansion of laminates solely through increasing the density of inorganic fillers. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 5-148343 [Overview of the project] [Problems that the invention aims to solve]

[0006] Another method for increasing the elastic modulus and reducing the thermal expansion of laminates is to use a fiber base material that has a lower thermal expansion coefficient and a higher elastic modulus. However, our research has shown that when the thermal expansion coefficient of the fiber substrate is lowered and the elastic modulus is increased, the resulting laminate tends to have poor connection reliability. Therefore, simply adjusting the thermal expansion coefficient and elastic modulus of the fibrous substrate is not sufficient to increase the elastic modulus and decrease the thermal expansion of the laminate while maintaining good connection reliability.

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

[0008] The inventors have conducted extensive research to solve the above problems and have found that the above problems can be solved by the following embodiment. In other words, this embodiment relates to the following [1] to

[14] . [1] A laminate containing two or more composite layers containing a fiber base material and a cured product of a thermosetting resin composition, The aforementioned 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 fibrous substrate composed of first glass fibers, The composite layer (Y) is a layer containing a second fiber base material composed of second glass fibers, A laminate, wherein the first glass fibers have a higher tensile elastic modulus at 25°C than the second glass fibers. [2] The tensile elastic modulus of the first glass fibers at 25°C is 80 GPa or more, The laminate according to [1], wherein the tensile elastic modulus of the second glass fibers at 25°C is less than 80 GPa. [3] The laminate according to [1] or [2], wherein the difference in the tensile elastic modulus at 25°C between the first glass fibers and the second glass fibers is 10 GPa or more. [4] 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), the composite layer (X) is a layer containing a first fiber base material composed of first glass fibers, the composite layer (Y) is a layer containing a second fiber base material composed of second glass fibers, 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 fibers are S glass. [6] The laminate according to any one of [1] to [5], wherein the second glass fibers are 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 containing 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 containing 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 outermost layer on both sides of the laminate is the composite layer (Y).

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

[11] The laminate according to [9] or

[10] , comprising two or more composite layers (X). A printed circuit board comprising a laminate described in any one of items

[12] [1] to

[11] .

[13] A semiconductor package comprising semiconductor elements mounted on a printed circuit board as described in

[12] . A method for manufacturing a laminate according to any one of items

[14] [1] to

[11] , A prepreg (a) is formed by impregnating a thermosetting resin composition with a first fibrous substrate composed of the first glass fibers, A prepreg (b) is formed by impregnating a thermosetting resin composition into a second fibrous base material composed of the second glass fiber, A method for manufacturing laminated boards by laminating and molding them. [Effects of the Invention]

[0009] According to this embodiment, it is possible to provide a laminate that has a high modulus of elasticity and low thermal expansion while also having excellent connection reliability, a printed circuit board and a semiconductor package using the laminate, and a method for manufacturing the laminate. [Brief explanation of the drawing]

[0010] [Figure 1] This is a schematic diagram showing a cross-section of a composite layer. [Figure 2] This is a schematic diagram showing an example of a sandwich-type laminated structure. [Figure 3] This is a schematic diagram showing another example of a sandwich-type laminate. [Figure 4] This is a schematic diagram showing an example of a laminate according to this embodiment. [Figure 5] This is a schematic diagram showing another example of the laminate of this embodiment. [Figure 6]This is a schematic diagram showing another example of the laminate of this embodiment. [Figure 7] This is a schematic diagram showing another example of the laminate of this embodiment. [Modes for carrying out the invention]

[0011] Numerical ranges indicated using "~" in this specification include the number before "~" as the minimum value and the number after "~" as the maximum value. For example, the notation "X~Y" (where X and Y are real numbers) means the numerical range that is greater than or equal to X and less than or equal to Y. Furthermore, the notation "greater than or equal to X" in this specification means X and numbers greater than X. Also, the notation "less than or equal to Y" in this specification means Y and numbers less than Y. Within the numerical ranges described herein, the upper or lower limits of those ranges may be replaced with the values ​​shown in the examples. Furthermore, the lower and upper limits of the numerical ranges may be arbitrarily combined with the lower or upper limits of other numerical ranges. Furthermore, unless otherwise specified, each component and material exemplified herein 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 multiple substances present in the composition, unless otherwise specified, if multiple substances corresponding to each component are present in the composition. Embodiments that combine any combination of the information described herein are also included. The mechanism of action described herein is speculative and does not limit the mechanism by which the resin composition according to this embodiment exerts its effects.

[0012] [Laminated board] This embodiment provides a laminate according to the first embodiment shown in [1] below (hereinafter also referred to as "laminated board (1)") and a laminate according to the second embodiment shown in [2] below (hereinafter also referred to as "laminated board (2)").

[0013] [1] A laminate containing two or more composite layers containing a fiber base material and a cured product of a thermosetting resin composition, The aforementioned 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 fibrous substrate composed of first glass fibers, The composite layer (Y) is a layer containing a second fibrous substrate composed of second glass fibers, A laminate in which the first glass fiber has a higher tensile modulus at 25°C than the second glass fiber.

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

[0015] The following description applies to both laminate (1) and laminate (2) of this embodiment unless otherwise specified, and when simply referred to as "laminated board," it refers to both laminate (1) and laminate (2) of this embodiment.

[0016] The reason why the laminate in this embodiment has a high modulus of elasticity and low thermal expansion while also exhibiting excellent connection reliability is not entirely clear, but it can be inferred as follows. The elastic modulus of glass fibers, or their SiO2 and Al2O3 content, is one of the factors that determine the elastic modulus and thermal expansion coefficient of the fibrous substrate composed of these glass fibers. Specifically, a fibrous substrate composed of a second glass fiber with a low elastic modulus or low SiO2 content yields a composite layer (Y) with a low elastic modulus. The connection reliability of a package using laminates to a motherboard is greatly influenced by the composite layer (Y) with a low elastic modulus, and the application of composite layer (Y) effectively improves the connection reliability of the laminate compared to the case with composite layer (X) alone. On the other hand, the warping of the laminate during curing improves with increasing elastic modulus and / or total SiO2 and Al2O3 content of composite layer (X). As a result, it is considered that laminates containing composite layer (X) and composite layer (Y) have connection reliability close to that of composite layer (Y), and that their elastic modulus and thermal expansion coefficient improve with increasing composite layer (X) content. The following describes each component of the laminated board of this embodiment.

[0017] <Composite layer> The laminate of this embodiment contains two or more composite layers, each containing a fibrous substrate and a cured product of a thermosetting resin composition. In this embodiment, the number of composite layers is an integer value. Therefore, for example, a composite layer of 2 to 16 layers is an integer value within the numerical 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 numerical range. Furthermore, in this embodiment, the single-layer composite layer refers to a composite layer consisting of a single fibrous substrate and a cured product of a thermosetting resin composition contained in the fibrous substrate. Furthermore, a single-layer fibrous substrate is a material that can be handled as a single sheet before being compounded with a thermosetting resin composition. It is a sheet-like substrate with gaps between the fibers, where the fibers are intertwined and bonded together by a fiber binder. The laminate (1) of this embodiment contains a composite layer (X) containing a first fibrous base material composed of first glass fibers, and a composite layer (Y) containing a second fibrous base material composed 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 contains a composite layer (X) containing a first fibrous substrate composed of first glass fibers and a composite layer (Y) containing a second fibrous substrate 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. Figure 1 shows a schematic cross-sectional view of an example of a composite layer contained in the laminate of this embodiment. As shown in Figure 1, the composite layer 1 contains a fibrous base material 2 and a cured product 3 of a thermosetting resin composition. In the composite layer 1, the fibrous base material 2 is a glass cloth made by interweaving yarn, which is made by twisting strands of glass fibers (single fibers) together, as the warp threads 2a and the weft threads 2b. Preferred embodiments of the fiber substrate and thermosetting resin composition are as described later.

[0018] <Laminate structure> The total number of composite layers contained in the laminate of this embodiment can be adjusted as appropriate depending on the application of the laminate, but from the viewpoint of improving the mechanical strength of the laminate, 3 or more layers are preferable, 4 or more layers are more preferable, and 5 or more layers are even preferable. Furthermore, from the viewpoint of miniaturizing the printed circuit board and the processability of the laminate, the total number of composite layers is preferably 20 or less, more preferably 18 or less, and even more preferably 16 or less.

[0019] The number of composite layers (X) contained in the laminate of this embodiment is not particularly limited, but from the viewpoint of improving warping, two or more layers are preferred. Furthermore, from the viewpoint of miniaturizing the printed circuit board and the 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 volume% or more, more preferably 55 volume% or more, and even more preferably 60 volume% or more. Furthermore, from the viewpoint of miniaturizing the printed circuit board and the processability of the laminate, the volume ratio of the composite layer (X) is preferably 95 volume% or less, more preferably 90 volume% or less, and even more preferably 88 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, one or more layers are preferred, and two or more layers are more preferred. Furthermore, from the viewpoint of increasing the elastic modulus and reducing thermal expansion of the laminate, the number of composite layers (Y) is preferably six or fewer, more preferably five or fewer, and even more preferably four or fewer. 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 volume% or more, more preferably 10 volume% or more, and even more preferably 12 volume% or more. Furthermore, from the viewpoint of improving warpage, the volume ratio of the composite layer (Y) is preferably 50 volume% or less, more preferably 45 volume% or less, and even more preferably 40 volume% or less.

[0021] From the viewpoint of improving warp resistance, it is preferable that the number of composite layers (X) contained in the laminate of this embodiment is greater than the number of composite layers (Y). The difference between the number of layers of composite layer (X) and the number of layers of composite layer (Y) [composite layer (X) - composite layer (Y)] is not particularly limited, but from the viewpoint of improving warpage, one or more layers are preferable, two or more layers are more preferable, and three or more layers are even preferable. Furthermore, from the viewpoint of miniaturizing the printed circuit board and the 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 layer of the composite layer contained in the laminate of this embodiment is not particularly limited, but from the viewpoint of insulation reliability, processability, etc., it is preferably 0.01 mm or more, more preferably 0.02 mm or more, and even more preferably 0.025 mm or more. Furthermore, from the viewpoint of thinning the printed circuit board, the thickness of each layer of the 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.

[0023] The thickness of the laminate in this embodiment is not particularly limited, but from the viewpoint of mechanical strength and processability of the laminate, it is preferably 0.3 mm or more, more preferably 0.4 mm or more, and even more preferably 0.5 mm or more. Furthermore, from the viewpoint of thinning the printed circuit 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 laminated board mentioned above does not include the thickness of the outer layer, such as metal foil, which may be optionally provided as described later.

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

[0025] Figures 2 and 3 show an example of a sandwich-type laminated section. The sandwich laminated section 4A shown in Figure 2 has a configuration in which one composite layer (X) is placed between two composite layers (Y). The sandwich laminated section 4B shown in Figure 3 has a configuration in which 10 composite layers (X) are arranged between 2 composite layers (Y).

[0026] In the sandwich laminate section, the number of composite layers (X) arranged between the two composite layers (Y) on both sides is not particularly limited, but from the viewpoint of improving warpage, two or more layers are preferable, three or more layers are more preferable, and four or more layers are even preferable. Furthermore, although the number of composite layers (X) arranged between the two composite layers (Y) on both sides is not particularly limited, from the viewpoint of miniaturizing the printed circuit board and the processability of the laminate, 16 layers or less is preferable, 15 layers or less is more preferable, and 14 layers or less is even preferable.

[0027] The laminate of this embodiment preferably has a sandwich laminate portion in at least a part of the laminate, and may also consist only of the sandwich laminate portion. An example of a laminate having a sandwich laminate portion in at least a part of it is one in which there is one or more layers selected from the group consisting of composite layers (X) and composite layers (Y) on the outside of the composite layers (Y) on both sides or one side that constitute the sandwich laminate portion. Figures 4 and 5 show an example of a laminate having a sandwich laminate portion in part of the laminate. Figure 4 shows a laminated board 10 having one composite layer (Y) on each side outside of the composite layers (Y) that constitute the sandwich laminated section 4B. Figure 5 shows a laminated board 11 having one composite layer (X) on each side of the composite layers (Y) that constitute the sandwich laminated section 4B. An example of a structure consisting solely of sandwich laminated sections is a laminated board composed only of sandwich laminated sections 4A or 4B, as shown in Figures 2 and 3.

[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 placed between the outermost composite layers (Y) on both sides only needs to 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 consists of only one or more composite layers (X). In other words, 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-described sandwich laminate portion).

[0029] In a sandwich laminate, the number of composite layers (X) placed between the two composite layers (Y) on both sides is the same as the preferred range in the sandwich laminate described above. Furthermore, 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. Furthermore, 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] Figure 6 shows an example of a sandwich laminate. The sandwich laminate 12 shown in Figure 6 has a configuration in which 12 composite layers (X) are arranged between two composite layers (Y) on both sides.

[0031] In the laminate of this embodiment, if it contains two or more composite layers (X), the two or more composite layers (X) may be the same or different. Furthermore, in the laminate of this embodiment, if it contains two or more composite layers (Y), the two or more composite layers (Y) may be the same or different. For example, in the case of the sandwich laminate section 4A shown in Figure 3 and the sandwich laminate board 12 shown in Figure 6, the two composite layers (Y) on both sides may be identical or different in terms of their structure, such as thickness, physical properties, such as elastic modulus, and composition. Similarly, the two or more composite layers (X) placed between the two composite layers (Y) on both sides may be identical or different in terms of their structure, such as thickness, physical properties, such as elastic modulus, and composition.

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

[0033] <Textile base material> As for the shape of the fibrous base material, well-known shapes used in various types of laminates for electrical insulation materials can be used, such as woven fabrics (i.e., glass cloth) formed by interweaving warp and weft threads, nonwoven fabrics, robbing, chopped strand mats, and surfacing mats. Among these, glass cloth is preferred as the fibrous base material. Fiber base materials that have been surface-treated with a silane coupling agent or the like, or that have been mechanically opened, are preferable in terms of heat resistance, moisture resistance, and processability.

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

[0035] <Glass fiber> Next, we will explain the glass fibers that make up the fibrous substrate. The following explanation applies to both the first and second glass fibers unless otherwise specified, and the term "glass fiber" refers to both the first and second glass fibers.

[0036] The glass fibers are not particularly limited, but are preferably used as strands of several tens to several hundred fibers bundled together, or as yarn made by twisting strands. The fiber base material used in this embodiment is preferably a glass cloth made by weaving the above-mentioned yarn as warp and weft threads. The 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 bundled glass fibers is not particularly limited, but is preferably 40 to 1000, 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 than the second glass fiber (hereinafter, when simply referred to as "tensile modulus," it refers to the tensile modulus at 25°C). In the laminate (2) of this embodiment, it is also 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 higher, and the tensile modulus of the second glass fiber is preferably less than 80 GPa. When the tensile moduli of the first and second glass fibers are within the above range, the resulting laminate exhibits even greater effectiveness of the invention.

[0039] From the same viewpoint as above, the tensile modulus of the first glass fiber is more preferably 82 GPa or higher, even more preferably 84 GPa or higher, and particularly preferably 85 GPa or higher. Furthermore, from the viewpoint of maintaining good drillability and insulation reliability, the tensile modulus of the first glass fiber is preferably 110 GPa or lower, more preferably 100 GPa or lower, and even more preferably 90 GPa or lower. Furthermore, 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. In addition, from the viewpoint of maintaining good drillability and insulation reliability, the tensile modulus of the second glass fiber is preferably 53 GPa or higher, more preferably 69 GPa or higher, and even more preferably 70 GPa or higher. The tensile modulus of glass fiber at 25°C can be measured, for example, using a monofilament and a Tensilon, according to known methods for measuring tensile modulus.

[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] (Composition of glass fibers) The ratio of Al2O3 content to 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 Al2O3 content to SiO2 content is within this range, a laminate with superior 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% by 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% by mass. When the total content of SiO2 and Al2O3 in the first and second glass fibers is within the above range, the resulting laminate will have even better connection reliability and warp resistance.

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

[0044] The first glass fiber satisfies the total content of SiO2 and Al2O3 as described above, and the Al2O3 content is preferably 20% by mass or more, more preferably 20-30% by mass, and even more preferably 20-25% by mass. The second glass fiber satisfies the total content of SiO2 and Al2O3 as described above, and the Al2O3 content is preferably less than 24% by mass, more preferably less than 22% by mass, and even more preferably less than 20% by mass.

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

[0046] (Thermal expansion coefficient of glass fiber) The thermal expansion coefficient of the glass fibers is not particularly limited, but it is preferable that the thermal expansion coefficient of the first glass fibers be less than 4.0 ppm / °C. When the thermal expansion coefficient of the first glass fibers is within the above range, the resulting laminate has even lower thermal expansion and higher modulus of elasticity. From a similar viewpoint, the thermal expansion coefficient of the first glass fibers 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, considering the balance with other physical properties, the thermal expansion coefficient of the first glass fibers may be 2.0 ppm / °C or higher, 2.3 ppm / °C or higher, or 2.5 ppm / °C or higher.

[0047] The thermal expansion coefficient of the second glass fiber is also preferable to be small from the viewpoint of lowering the thermal expansion coefficient of the laminate. From a similar 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, considering the balance between its composition and other physical properties, the thermal expansion coefficient of the second glass fiber tends to be larger than that of the first glass fiber. From such a viewpoint, the thermal expansion coefficient of the second glass fiber may be 4.0 ppm / °C or higher, 4.5 ppm / °C or higher, 5.0 ppm / °C or higher, or 5.3 ppm / °C or higher.

[0048] (Types of glass fiber) Examples of glass fibers constituting the fibrous base material include E glass, S glass, C glass, D glass, T glass, NE glass, A glass, H glass, quartz glass, etc. From these, appropriate selections can be made considering the preferred physical properties and composition for the first and second glass fibers as described above.

[0049] The typical 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 (62-65% by mass), Al2O3 (20-25% by mass), CaO (0-0.01% by mass), MgO (10-15% by mass), B2O3 (0-0.01% by mass), Na2O and K2O (0-1% by 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. In other words, the first fiber substrate used in the laminate of this embodiment is preferably a fiber substrate made of S glass fibers, and the second fiber substrate is preferably a fiber substrate made of E glass fibers. Furthermore, the first fiber base material is more preferably a glass cloth made of S glass fibers (hereinafter also referred to as "S glass cloth"), and the second fiber base material is more preferably a glass cloth made of E glass fibers (hereinafter also referred to as "E glass cloth"). S glass cloth and E glass cloth may each contain glass fibers other than S glass fibers and E glass fibers, but the content 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 none.

[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 a curing agent, a curing accelerator, an inorganic filler, etc., as needed. The components contained in the thermosetting resin composition will be described below.

[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, and furan resins. Among these, modified silicone resins and epoxy resins are preferred. Thermosetting resins may be used individually or in combination of two or more types.

[0053] [Modified silicone resin] The modified silicone resin is preferably 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 by 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 a compound represented by the following general formula (A-1) is preferred.

[0055] [Chemical formula] (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, and X 1 and X 2 each independently represents a divalent organic group. n represents an integer of 2 to 100.)

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

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

[0058] [ka] (In the formula, R 11 ~R 13 Each of these independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms. 11 (This represents an alkylene group with 1 to 5 carbon atoms, an alkylidene group with 2 to 5 carbon atoms, an -O- group, or a sulfonyl group. p, q, and r are each independently integers from 0 to 4. m is an integer from 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 shown is R in the general formula (A-1) above. 1 The same things can be cited. X 11 The alkylene group with 1 to 5 carbon atoms shown is X in the general formula (A-1) above. 1 The same things can be cited. X 11 Examples of alkylidene groups with 2 to 5 carbon atoms include ethylidene, propyridene, isopropylidene, butylidene, isobutylidene, pentylidene, and isopentylidene.

[0060] Examples of maleimide compounds (B) include bis(4-maleimidophenyl)methane, polyphenylmethanemaleimide, bis(4-maleimidophenyl) ether, bis(4-maleimidophenyl) sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane. Among these, bis(4-maleimidophenyl)methane is preferred.

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

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

[0063] In the above general formula (C-1), R 21 The alkyl group having 1 to 5 carbon atoms shown is R in the above general formula (A-1). 1 The same can be said for halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0064] Examples of amine compounds (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, and 3,5-dicarboxyaniline. Among these, m-aminophenol and p-aminophenol are preferred from the viewpoint 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 of the following general formulas (D-1) to (D-3).

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

[0067] X 13 ~X 16 The alkylene group with 1 to 5 carbon atoms and the alkylidene group with 2 to 5 carbon atoms shown are X of the general formula (B-2) above. 11 The same things can be cited. R 14 and R 15 The aliphatic hydrocarbon group having 1 to 5 carbon atoms shown is R in the general formula (A-1) above. 1 The same can be said for the above. Among these, methyl groups and ethyl groups are preferred.

[0068] Examples of amine compounds (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'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 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. Among these, 3,3'-diethyl-4,4'-diaminodiphenylmethane is preferred.

[0069] Modified silicone resin can be prepared by reacting components (A) to (D) above, for example, at 70 to 150°C. During the reaction, organic solvents such as propylene glycol monomethyl ether and cyclohexanone, or reaction catalysts may be used as needed.

[0070] (Amount of each ingredient used) In the reaction of components (A) to (D), the equivalent ratio [C=C group / NH2 group] 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 group of component (B) is preferably 0.1 to 10, more preferably 1 to 9, and even more preferably 2 to 5. If the equivalent ratio is 0.1 or higher, gelation and a decrease in heat resistance can be suppressed, and if it is 10 or lower, a decrease in solubility in organic solvents and a decrease in heat resistance can be suppressed. 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 relationship. 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 relationship.

[0071] From the viewpoint of heat resistance, low water absorption, and thermal expansion coefficient, the content of 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 solid content of the thermosetting resin composition. In this specification, "solids" refers to the non-volatile components excluding volatile substances such as solvents, and includes components that remain without volatilization when the resin composition is dried, including liquid, syrup-like, and waxy substances at room temperature. Here, room temperature is defined as 25°C.

[0072] [Epoxy resin] Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, stilbene type epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, triphenolmethane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, diglycidyl ether compounds of polycyclic aromatics such as polyfunctional phenols and anthracenes, and phosphorus-containing epoxy resins obtained by introducing phosphorus compounds into these. Among these, biphenyl aralkyl type epoxy resin is preferred from the viewpoint of heat resistance and flame retardancy.

[0073] If the thermosetting resin composition contains epoxy resin, the amount of epoxy resin 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, based on the solid content of 100 parts by mass of the thermosetting resin composition, from the viewpoint of heat resistance, low water absorption, and coefficient of thermal expansion.

[0074] [Acrylic polymer] The thermosetting resin composition may be a resin composition comprising an acrylic polymer and a thermosetting resin. In this case, the thermosetting resin composition may be a resin composition that forms a phase separation structure between a first phase comprising an acrylic polymer and a second phase comprising a thermosetting resin. Acrylic polymers are typically polymers that use (meth)acrylic acid esters as monomers. Acrylic polymers may be used individually or in combination of two or more types.

[0075] The acrylic polymer is preferably an acrylic polymer that contains constituent units derived from (meth)acrylic acid esters 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 R represents an alkyl group, cycloalkyl group, cycloalkylalkyl group, aryl group, or aralkyl group. 31 (This represents a hydrogen atom or a methyl group.)

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

[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)]deca-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 individually or in combination of two or more types.

[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, glass short fibers, glass fine powder, and hollow glass. Among these, silica is preferred from the viewpoint of heat resistance and flame retardancy, and fused silica such as molten 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. When the average particle size is 0.1 μm or larger, good fluidity can be maintained, and when it is 10 μm or smaller, the occurrence of defects caused by coarse particles can be suppressed. Here, the average particle size is the particle size at the point corresponding to 50% of the volume when the cumulative frequency distribution curve by particle size is calculated with the total volume of particles as 100%, and can be measured using a particle size distribution analyzer that uses laser diffraction scattering or the like. Inorganic fillers may be used individually or in combination of two or more types.

[0080] When a thermosetting resin composition contains an inorganic filler, the amount of the filler 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, per 100 parts by mass of solid content of the thermosetting resin composition, from the viewpoint of reducing the coefficient of thermal expansion and increasing the modulus of elasticity.

[0081] (Curing accelerator) Examples of curing accelerators include organometallic salts such as zinc naphthenate, cobalt naphthenate, tin octoate, cobalt octoate, bisacetylacetonate cobalt(II), and trisacetylacetonate cobalt(III); imidazole compounds and their derivatives; organophosphorus compounds; and secondary amines, tertiary amines, and quaternary ammonium salts. Among these, imidazole compounds and their derivatives are preferred from the viewpoint of heat resistance and flame retardancy. The hardening accelerator may be used alone or in combination of two or more types. If the thermosetting resin composition contains a curing accelerator, the amount of the accelerator is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, and even more 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, from the viewpoint of heat resistance and flame retardancy.

[0082] The thermosetting resin composition may optionally contain one or more substances selected from the group consisting of flame retardants, functional resins, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, adhesion enhancers, and organic solvents, or it may not contain them.

[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, in order to facilitate its use in the manufacture of prepregs and the like. Examples of organic solvents include alcoholic solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as butyl acetate and propylene glycol monomethyl ether acetate; ether 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 individually or in combination of two or more. The solid content concentration of the varnish is preferably 40 to 90% by mass, more preferably 45 to 85% by mass, and even more preferably 50 to 80% by mass. When the solid content concentration of the varnish is within the above range, a prepreg with appropriate content of thermosetting resin composition can be obtained while maintaining good coatability.

[0084] [Manufacturing method for laminated boards] The method for manufacturing the laminated board in this embodiment is: A prepreg (a) is formed by impregnating a thermosetting resin composition with a fibrous base material composed of first glass fibers, A prepreg (b) is made by impregnating a thermosetting resin composition with a fibrous base material composed of a second glass fiber, This is a method for manufacturing laminated boards by laminating and molding them. The embodiments of the glass fibers, fiber substrate, thermosetting resin composition, etc., used in the manufacturing method of the laminate 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 fibrous substrate with a thermosetting resin composition. For example, they can be manufactured by impregnating a fibrous substrate with a varnish-like thermosetting resin composition, and then partially curing (stage B) them by heating and drying them at a temperature of 100 to 200°C for 1 to 30 minutes. The solid content derived from the thermosetting resin composition in prepregs (a) and (b) is preferably 20 to 90% by mass, more preferably 30 to 70% by mass, and even more preferably 40 to 60% by mass.

[0086] Next, the obtained prepreg (a) and prepreg (b) are stacked as appropriate to form the desired laminate, and the laminate of this embodiment can be manufactured by laminating them with metal foil such as copper or aluminum placed on one or both sides as needed. The metal foil is not particularly limited as long as it is used for laminates for electrical insulating materials. Laminates of this embodiment with metal foil placed on one or both sides are called metal-clad laminates, and among these, those with copper foil are called copper-clad laminates. The molding conditions for manufacturing laminates can be those used for electrical insulating laminates and multilayer boards, and can be achieved using multi-stage presses, multi-stage vacuum presses, continuous molding machines, autoclave molding machines, etc. For example, the conditions can be 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.

[0087] [Printed wiring board] The printed circuit board of this embodiment is a printed circuit board that includes the laminate of this embodiment. The printed circuit board of this embodiment can be manufactured, for example, by forming circuits on the surface of the laminate of this embodiment. Alternatively, the conductive layer of the laminate of this embodiment can be wired using a conventional etching method, and then multiple laminates with the wired layers stacked together with prepregs in between, and finally heat-pressed to create a multilayer structure. After that, the printed circuit board can be manufactured by forming through-holes or blind via holes by drilling or laser cutting, and forming interlayer wiring by plating or conductive paste.

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

[0089] Next, this embodiment will be described in more detail by the following examples, but these examples are not intended to limit this embodiment. The prepregs and copper-clad laminates obtained in each example were measured and evaluated for performance using the following methods.

[0090] [Evaluation Method] (1) Thermal expansion coefficient The copper foil was removed from the copper-clad laminates obtained in each example by immersion in a copper etching solution to create evaluation substrates measuring 5 mm in length (X direction) x 5 mm in width (Y direction). Thermomechanical analysis was performed on these evaluation substrates using a TMA test apparatus (DuPont, product name: TMA2940) by compression. After mounting the evaluation substrate in the X direction in the apparatus, measurements were taken twice consecutively under 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 taken as the value of the thermal expansion coefficient.

[0091] (2) Flexural modulus For each example, a 50mm x 25mm evaluation substrate was prepared by removing the copper foil from the copper-clad laminate obtained by immersing it in a copper etching solution. The bending modulus of elasticity was measured using this evaluation substrate as the measurement target, with a 5-ton Tensilon manufactured by Orientec Co., Ltd., at a crosshead speed of 1mm / min and a span distance of 20mm.

[0092] (3) Connection reliability Using the copper-clad laminates obtained in each example, package boards and motherboard boards were fabricated with circuits formed on them to evaluate the connection reliability with the motherboard. These package boards and motherboard boards were then electrically connected using solder balls. Next, they were placed in a temperature cycling tester (-55 to 125°C), and the connection resistance was measured at predetermined cycle intervals. The number of solder ball fractures was defined as the number of cycles at which the resistance value fluctuated by 20% or more, and the connection reliability was evaluated from the number of cycles at which the cumulative failure rate reached 20% using a Weibull plot.

[0093] <Manufacturing of copper-clad laminates> [Example 1] (Copper-clad laminate 1: A copper-clad laminate with copper foil placed on both sides of the laminate shown in Figure 6) (1) Preparation of varnish In a 1-liter reaction vessel equipped with a thermometer, stirrer, and reflux condenser, 19.4 g of siloxanediamine (manufactured by Toray Dow Corning Co., Ltd., trade name: X-22-161A, amino group functional equivalent: 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 were added. After reacting these at 115°C, the mixture was concentrated under atmospheric pressure until the resin concentration reached 60% by mass. Further, 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 a methyl isobutyl ketone solution containing 7 g of 3-aminopropyltrimethoxysilane while stirring), 1.2 g of a curing accelerator (manufactured by Shikoku Chemicals, Ltd., product name: C17Z), and 65.6 g of a biphenyl aralkyl novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product name: NC-3000-H). Furthermore, by adding methyl ethyl ketone as a diluent, a uniform varnish with a solid content concentration of 65% by mass was obtained.

[0094] (2) Preparation of prepregs Next, the above varnish was impregnated onto 0.1 mm S glass cloth (tensile modulus of elasticity at 25°C: 85.3 GPa, total content of SiO2 and Al2O3: 82-90% by mass, thermal expansion coefficient: 2.9 ppm / °C) and 0.1 mm E glass (tensile modulus of elasticity at 25°C: 73 GPa, total content of SiO2 and Al2O3: 64-72% by mass, ratio of Al2O3 content to SiO2 content (by mass): 0.28, thermal expansion coefficient: 5.5 ppm / °C), respectively, and then heated and dried at 130°C for 3 minutes. This yielded prepregs containing S glass cloth and E glass cloth, respectively, with a solid content of 48% by mass derived from the thermosetting resin composition. Furthermore, the same procedure was used to produce the number of prepregs necessary for the production of the laminate described later.

[0095] (3) Fabrication of laminated boards Next, the prepregs prepared above were laminated in such a configuration that the outermost layer on each side contained E glass cloth, and the inner 12 layers contained S glass cloth. Furthermore, electrolytic copper foil with a thickness of 12 μm was placed on both sides, and then 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 placed on both sides of the laminate shown in Figure 4) In Example 1, 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 top two layers on each side were prepregs containing E-glass cloth, and the inner ten layers were prepregs containing S-glass cloth.

[0097] [Example 3] (Copper-clad laminate 3: A copper-clad laminate with copper foil placed 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 lamination configuration of the prepreg was changed to a configuration of 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 base material) 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 base material) 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] Table 1 shows the evaluation results of the laminates prepared as described above.

[0101] [Table 1]

[0102] As shown in Table 1, the laminates of Examples 1 to 3 of this embodiment were confirmed to have excellent connection reliability while possessing high modulus of elasticity and low thermal expansion. [Explanation of Symbols]

[0103] (X) Composite layer (X) (Y) Composite layer (Y) 1 composite layer 2. Fiber base material 2a Warp 2b Weft 3. Cured product of thermosetting resin composition 4A, 4B Sandwich Laminate 10-13 laminated board

Claims

1. A laminate containing two or more composite layers containing a fiber base material and a cured product of a thermosetting resin composition, The aforementioned 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 fibrous substrate composed of first glass fibers, The composite layer (Y) is a layer containing a second fibrous substrate composed of second glass fibers, A laminate in which the first glass fiber has a higher tensile modulus at 25°C than the second glass fiber.

2. The tensile modulus of the first glass fiber at 25°C is 80 GPa or more. The laminate according to claim 1, wherein the tensile modulus of the second glass fiber at 25°C is less than 80 GPa.

3. The laminate according to claim 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 containing two or more composite layers containing a fiber base material and a cured product of a thermosetting resin composition, The aforementioned 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 fibrous substrate composed of first glass fibers, The composite layer (Y) is a layer containing a second fibrous substrate composed of second glass fibers, SiO in the first glass fiber ２ and Al ２ O ３ The total content of SiO in the second glass fiber ２ and Al ２ O ３ A laminated board that has a higher content than the total content of [the substance].

5. The laminate according to any one of claims 1 to 4, wherein the first glass fiber is S glass.

6. The laminate according to any one of claims 1 to 5, wherein the second glass fiber is E-glass.

7. The laminate according to any one of claims 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 containing one or more layers of the composite layer (X) and two or more layers of the composite layer (Y), A laminate according to any one of claims 1 to 7, wherein at least one composite layer (X) is disposed between two composite layers (Y).

9. A laminate containing one or more layers of the composite layer (X) and two or more layers of the composite layer (Y), The laminate according to any one of claims 1 to 8, wherein the outermost layer on both sides of the laminate is the composite layer (Y).

10. A laminate containing one or more layers of the composite layer (X) and two layers of the composite layer (Y), The laminate according to claim 9, wherein the outermost layer on both sides of the laminate is the composite layer (Y).

11. The laminate according to claim 9 or 10, comprising two or more of the composite layers (X).

12. A printed circuit board comprising a laminate according to any one of claims 1 to 11.

13. A semiconductor package comprising a semiconductor element mounted on a printed circuit board as described in claim 12.

14. A method for manufacturing a laminate according to any one of claims 1 to 11, A prepreg (a) is formed by impregnating a thermosetting resin composition into a first fibrous substrate composed of the first glass fibers, A prepreg (b) is formed by impregnating a thermosetting resin composition into a second fibrous substrate composed of the second glass fiber, A method for manufacturing laminated boards by laminating and molding them.

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