JP7136389B2 - Laminate, printed wiring board, semiconductor package, and method for manufacturing laminate - Google Patents

Description

The present embodiment relates to a laminate, a printed wiring board, a semiconductor package, and a method for manufacturing a laminate.

In recent years, due to the miniaturization and high performance of electronic devices, the wiring density and integration of printed wiring boards have been increasing. . In semiconductor packages, in particular, warping during component mounting and package assembly has become a major issue as the size and thickness of semiconductor packages have been reduced.

One factor that causes the semiconductor package to warp is the difference in coefficient of thermal expansion between the semiconductor element and the printed wiring board on which the semiconductor element is mounted. Generally, the coefficient of thermal expansion of a printed wiring board is larger than that of a semiconductor element. Warp stress occurs. Therefore, as a method of suppressing the warp of the semiconductor package, a method of reducing the thermal expansion coefficient of the printed wiring board to reduce the difference from the thermal expansion coefficient of the semiconductor element, and a method of increasing the elastic modulus of the printed wiring board to increase the rigidity. methods are effective.

As laminates for printed wiring boards, prepregs obtained by impregnating or coating a fiber base material such as glass cloth with a thermosetting resin composition are generally 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. (See, for example, Patent Document 1).
However, high filling of inorganic fillers may reduce insulation reliability, adhesion with copper foil, press workability, etc. Therefore, from the viewpoint of ensuring these performances, high filling of inorganic fillers There is a limit to increasing the modulus of elasticity and decreasing the thermal expansion of a laminate only by curing.

JP-A-5-148343

As another method for increasing the modulus of elasticity and reducing the thermal expansion of the laminate, it is conceivable to use a material having a lower coefficient of thermal expansion and a higher modulus of elasticity for the fiber base material.
However, according to studies by the present inventors, it has been found that when the coefficient of thermal expansion of the fiber base material is decreased and the modulus of elasticity is increased, the resulting laminate tends to have poor connection reliability. .
Therefore, simply adjusting the coefficient of thermal expansion and the modulus of elasticity of the fiber base material cannot increase the modulus of elasticity and reduce the thermal expansion of the laminate while maintaining good connection reliability.

This embodiment has been made in view of the above circumstances, a laminate having excellent connection reliability while having a high elastic modulus and low thermal expansion, a printed wiring board and a semiconductor package using the laminate, and a laminate It is an object of the present invention to provide a method for manufacturing a plate.

The present inventors have made intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by the present embodiment described below.
That is, the present 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 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 the first fiber base material composed of the first glass fiber,
The composite layer (Y) is a layer containing a second fiber base material composed of a second glass fiber,
The laminate, wherein the first glass fiber has a higher tensile modulus at 25° C. than the second glass fiber.
[2] the first glass fiber has a tensile modulus at 25° C. of 80 GPa or more;
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 elastic 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 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 the first fiber base material composed of the first glass fiber,
The composite layer (Y) is a layer containing a second fiber base material 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 composite layer (X) has a greater number of layers than 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 arranged 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] A laminate containing one or more layers of the composite layer (X) and two layers of the composite layer (Y), and the outermost layer on both sides of the laminate is the composite layer (Y). ] The laminate according to .
[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 obtained by mounting a semiconductor element on the printed wiring board according to [12].
[14] A method for producing a laminate according to any one of [1] to [11],
A prepreg (a) obtained by impregnating a thermosetting resin composition into a first fiber base material composed of the first glass fiber;
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 producing a laminate, comprising laminating and molding.

According to the present embodiment, it is possible to provide a laminate having excellent connection reliability while having a high elastic modulus and low thermal expansion, a printed wiring board and a semiconductor package using the laminate, and a method for manufacturing the laminate. can.

It is a schematic diagram which shows the cross section of a composite layer. FIG. 4 is a schematic diagram showing an example of a sandwich laminate. FIG. 4 is a schematic diagram showing another example of a sandwich laminate; BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows an example of the laminated board of this embodiment. It is a schematic diagram which shows another example of the laminated board of this embodiment. It is a schematic diagram which shows another example of the laminated board of this embodiment. It is a schematic diagram which shows another example of the laminated board of this embodiment.

The numerical range indicated using "to" described in this specification includes the numerical value described before "to" as the minimum value and the numerical value described after "to" as the maximum value. Indicates a numeric range. For example, the notation of a numerical range “X to Y” (where X and Y are real numbers) means a numerical range that is greater than or equal to X and less than or equal to Y. And the description "X or more" in this specification means X and a numerical value exceeding X. In addition, the description “Y or less” in this specification means Y and a numerical value less than Y.
In the numerical ranges described herein, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples. Also, the lower and upper limits of a numerical range can be arbitrarily combined with the lower and upper limits of other numerical ranges, respectively.
In addition, each component and material exemplified in this specification may be used alone or in combination of two or more unless otherwise specified. As used herein, the content of each component in the composition refers to the total amount of the multiple substances present in the composition when there are multiple substances corresponding to each component in the composition, unless otherwise specified. means
Aspects in which the items described in this specification are arbitrarily combined are also included in this embodiment.
The mechanism of action described in this specification is an assumption, and does not limit the mechanism of the effect of the resin composition according to the present embodiment.

[Laminate]
This embodiment includes the laminate of the first embodiment shown in [1] below (hereinafter also referred to as "laminate (1)"), and the laminate according to the second embodiment shown in [2] below (hereinafter, A "laminate (2)") is provided.

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

[2] A laminate containing two or more composite layers containing a fiber base material and a cured product of a thermosetting resin composition,
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 the first fiber base material composed of the first glass fiber,
The composite layer (Y) is a layer containing a second fiber base material 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.

Unless otherwise specified, the following description is common to the laminate (1) and laminate (2) of the present embodiment, and when simply referred to as "laminate", the laminate ( 1) and laminate (2).

Although the reason why the laminate of the present embodiment has excellent connection reliability while having a high elastic modulus and a low thermal expansion property is not clear, it is presumed as follows.
The elastic modulus of the glass fiber or the content of SiO ₂ and Al ₂ O ₃ is one of the factors that determine the elastic modulus and thermal expansion coefficient of the fiber base material composed of the glass fiber. Specifically, a fibrous substrate composed of second glass fibers with a low modulus or a low SiO ₂ content gives a composite layer (Y) with a low modulus. The connection reliability of a package using a laminate with a motherboard is greatly affected by the composite layer (Y) having a low elastic modulus. The laminate effectively improves connection reliability.
On the other hand, the warpage of the laminate during curing becomes better depending on the number of composite layers (X) with a high modulus of elasticity and/or a high total content of SiO ₂ and Al ₂ O ₃ . As a result, the laminate containing the composite layer (X) and the composite layer (Y) has a connection reliability close to that of the composite layer (Y), and an elastic modulus and a thermal expansion coefficient that are equal to the number of the composite layers (X). It is thought that it will be a good one depending on the situation.
Each member included in the laminate of the present embodiment will be described below.

<Composite layer>
The laminate of the present embodiment contains two or more composite layers containing a fiber base material and a cured product of a thermosetting resin composition.
Note that the number of composite layers in this embodiment is an integer value. Therefore, for example, a composite layer of 2 to 16 layers is an integer value included in the numerical range of 2 to 16. In this case, the lower limit and upper limit of the number of composite layers are included in the numerical range. Arbitrarily combined using integer values.
In addition, the one-layer composite layer in the present embodiment means a composite layer composed of one fiber base material and a cured product of the thermosetting resin composition contained in the fiber base material.
In addition, the one-layer fiber base material is one that can be handled as a single sheet before being combined with the thermosetting resin composition, and the fibers are integrated by the entanglement of the fibers, the binder for the fibers, etc. It is a sheet-like substrate having a gap.
The laminate (1) of the present embodiment comprises a composite layer (X) containing a first fiber base made of first glass fibers and a second fiber base made of second glass fibers. It contains a composite layer (Y) containing a material. In the laminate (1) of the present embodiment, the first glass fibers have a higher tensile modulus at 25°C than the second glass fibers.
The laminate (2) of the present embodiment comprises a composite layer (X) containing a first fiber base made of first glass fibers and a second fiber base made of second glass fibers. It contains a composite layer (Y) containing a material. In the laminate (2) of the present embodiment, the total content of SiO ₂ and Al ₂ O ₃ in the first glass fibers is the total content of SiO ₂ and Al ₂ O ₃ in the second glass fibers. is higher than quantity,
FIG. 1 shows a schematic cross-sectional view of an example of the composite layer contained in the laminate of the present 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 obtained by twisting strands of glass fibers, which are monofilaments, as warp yarns 2a and weft yarns 2b.
Preferred aspects of the fiber base material and the thermosetting resin composition are as described below.

<Structure of laminate>
The total number of composite layers contained in the laminate of the present embodiment may be appropriately adjusted according to 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 layers or more, more preferably 5 layers or more. The total number of composite layers is preferably 20 layers or less, more preferably 18 layers or less, and even more preferably 16 layers or less, from the viewpoints of miniaturization of the printed wiring board and workability of the laminate.

The number of layers of the composite layer (X) contained in the laminate of the present embodiment is not particularly limited, but from the viewpoint of improving warpage, two or more layers are preferable. The number of layers of the composite layer (X) is preferably 16 layers or less, more preferably 15 layers or less, and even more preferably 14 layers or less, from the viewpoints of miniaturization of the printed wiring board and workability of the laminate.
The volume ratio of the composite layer (X) in the laminate of the present 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 60% by volume. % or more is more preferable. In addition, the volume ratio of the composite layer (X) is preferably 95% by volume or less, more preferably 90% by volume or less, and 88% by volume or less from the viewpoint of miniaturization of the printed wiring board and workability of the laminate. More preferred.

The number of composite layers (Y) contained in the laminate of the present embodiment is not particularly limited, but from the viewpoint of connection reliability, it is preferably one or more, more preferably two or more. The number of layers of the composite layer (Y) is preferably 6 or less, more preferably 5 or less, and still more preferably 4 or less, from the viewpoint of increasing the modulus of elasticity and reducing the thermal expansion of the laminate.
The volume ratio of the composite layer (Y) in the laminate of the present embodiment is not particularly limited, but from the viewpoint of the connection reliability of the laminate, it is preferably 5% by volume or more, more preferably 10% by volume or more. 12% by volume or more is more preferable. Moreover, 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, from the viewpoint of improving warpage.

The number of layers of the composite layer (X) contained in the laminate of the present embodiment is preferably larger than the number of layers of the composite layer (Y) from the viewpoint of improving warpage.
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, One or more layers are preferred, two or more layers are more preferred, and three or more layers are even more preferred. 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, from the viewpoint of miniaturization of the printed wiring board, workability of the laminate, and the like.

The thickness of each composite layer contained in the laminate of the present embodiment is not particularly limited, but from the viewpoint of insulation reliability, workability, etc., it is preferably 0.01 mm or more, more preferably 0.02 mm or more. , more preferably 0.025 mm or more. In addition, 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.

The thickness of the laminate of the present embodiment is not particularly limited, but from the viewpoint of mechanical strength, workability, etc. of the laminate, it is preferably 0.3 mm or more, more preferably 0.4 mm or more, and 0.5 mm or more. More preferred. Moreover, 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, from the viewpoint of thinning the printed wiring board.
It should be noted that the thickness of the laminated plate does not include the thickness of the metal foil or the like of the outer layer, which may be provided arbitrarily, as described later.

The laminate of the present embodiment contains one or more composite layers (X) and two or more composite layers (Y), and at least one composite layer (X) is composed of two composite layers (Y). It is preferable to have at least a part of the laminated portion (hereinafter, also referred to as a “sandwich laminated portion”) interposed therebetween.

2 and 3 show an example of a sandwich laminate.
The sandwich laminated part 4A shown in FIG. 2 has a structure in which one composite layer (X) is arranged between two composite layers (Y).
The sandwich laminated portion 4B shown in FIG. 3 has a structure in which ten composite layers (X) are arranged between two composite layers (Y).

In the sandwich laminate, the number of layers of the composite layer (X) arranged between the two layers of the composite layer (Y) on both sides is not particularly limited, but from the viewpoint of improving the warp, two or more layers are preferable. Three or more layers are more preferred, and four or more layers are even more preferred. In addition, the number of layers of the composite layer (X) arranged between the two composite layers (Y) on both sides is not particularly limited. 16 layers or less are preferable, 15 layers or less are more preferable, and 14 layers or less are even more preferable.

The laminated plate of the present embodiment preferably has a sandwich laminated portion in at least a portion of the laminated plate, and may be composed only of the sandwich laminated portion.
Examples of those having a sandwich laminated portion in at least a part of a laminated plate include, for example, a composite layer (X) and a composite layer (Y ) having one or more layers selected from the group consisting of
4 and 5 show an example of a laminate having a sandwich laminate as a part of the laminate.
FIG. 4 shows a laminated plate 10 having one composite layer (Y) outside the composite layers (Y) on both sides constituting the sandwich laminate portion 4B.
FIG. 5 shows a laminated plate 11 having one composite layer (X) outside the composite layers (Y) on both sides constituting the sandwich laminate portion 4B.
As an example of the one composed only of the sandwich laminate portion, there is a laminated plate composed only of the sandwich laminate portion 4A or 4B shown in FIGS. 2 and 3, for example.

The laminate of the present embodiment is a laminate containing two or more composite layers (Y), and the outermost layer on both sides of the laminate is preferably the composite layer (Y).
At this time, the composite layer disposed between the outermost composite layers (Y) on both sides may contain at least one composite layer (X), and one or more composite layers (X) and one or more composite layers (Y), but preferably one or more composite layers (X) alone.
That is, the laminate of the present embodiment is a laminate containing only one or more composite layers (X) and two composite layers (Y), and the outermost layer on both sides of the laminate is the composite layer (Y). (This aspect is hereinafter also referred to as a "sandwich laminate". A sandwich laminate corresponds to a laminate composed only of the sandwich laminate portion described above).

In the sandwich laminate, the number of composite layers (X) arranged between the two composite layers (Y) on both sides is the same as the preferred range for the above-described sandwich laminate.
In addition, the volume ratio of the outermost composite layer (Y) in the laminate of the present embodiment is not particularly limited, but from the viewpoint of connection reliability, it is preferably 3% by volume or more, and 5% by volume. The above is more preferable, and 6% by volume or more is even more preferable. The volume ratio of the composite layer (Y), which is the outermost layer, in the laminate of the present embodiment is not particularly limited, but is preferably 25% by volume or less from the viewpoint of improving warpage.

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

When the laminate of the present embodiment contains two or more composite layers (X), the two or more composite layers (X) may be the same or different.
When the laminate of the present 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 case of the sandwich laminate portion 4A shown in FIG. 3 and the sandwich laminate plate 12 shown in FIG. etc. may be the same or different. Similarly, the two or more composite layers (X) disposed between the two composite layers (Y) on both sides are identical in structure such as thickness, physical properties such as elastic modulus, and composition. may also be different.

The configuration of the laminate described above is an example of the laminate of this embodiment, and this embodiment is not limited to laminates having these configurations.
Next, preferred aspects of the material that constitutes the composite layer of this embodiment will be described.

<Fibrous base material>
As the shape of the fiber base material, well-known shapes used for various laminates for electrical insulating materials can be used. , chopped strand mat, surfacing mat and the like. Among these, the fiber base material is preferably glass cloth.
The fiber substrate is preferably surface-treated with a silane coupling agent or the like or mechanically fiber-opened from the standpoint of heat resistance, moisture resistance, processability, and the like.

Although the thickness of the fiber base material is not particularly limited, it 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 viewpoint of insulation reliability, processability, and the like. Moreover, 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, from the viewpoint of thinning the printed wiring board.

<Glass fiber>
Next, the glass fibers constituting the fiber base material will be described.
In addition, unless otherwise specified, the following description is common to the first glass fiber and the second glass fiber. shall refer to both

The glass fiber is not particularly limited, but for example, it is preferably used as a strand in which several tens to several hundreds are bundled or as a yarn twisted to the strand. A glass cloth obtained by interweaving the above yarns as warp and weft is preferable.
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 bundled 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.

(tensile modulus of glass fiber)
In the laminate (1) of the present embodiment, the first glass fiber has a higher tensile modulus at 25°C than the second glass fiber (hereinafter simply referred to as "tensile modulus" at 25°C). ) is high, and also in the laminate (2) of the present embodiment, the first glass fiber preferably has a higher tensile modulus than the second glass fiber.

The tensile modulus of the glass fiber 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 elasticity of the first and second glass fibers is within the above range, the resulting laminated board is even more excellent in the effects of the invention.

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. In addition, the tensile modulus of the first glass fiber is preferably 110 GPa or less, more preferably 100 GPa or less, and even more preferably 90 GPa or less, from the viewpoint of maintaining good drillability and insulation reliability.
From the same viewpoint as above, the tensile modulus of the second glass fiber is more preferably less than 79 GPa, still more preferably less than 78 GPa, and particularly preferably less than 75 GPa. In addition, 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, from the viewpoint of keeping good drillability and insulation reliability.
The tensile elastic modulus of glass fiber at 25° C. can be measured by a known tensile elastic modulus measuring method using Tensilon, for example, using a monofilament as an object to be measured.

From the same viewpoint as above, the difference in tensile elastic 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.

(Composition of glass fiber)
The ratio of the content of Al ₂ O ₃ to the content of SiO ₂ in the second glass fiber [content of Al ₂ O ₃ /content of SiO ₂ ] (based on mass) is 0.35 or less. is preferred, 0.32 or less is more preferred, and 0.30 or less is even more preferred. If the ratio of the content of Al ₂ O ₃ to the content of SiO ₂ is within this range, a laminate with more excellent connection reliability can be obtained.

The total content of SiO ₂ and Al ₂ O ₃ in the first glass fiber is not particularly limited, but is preferably 80% by mass or more, and the total content of SiO ₂ and Al ₂ O ₃ in the second glass fiber is not particularly limited, but is preferably less than 80% by mass. When the total content of SiO ₂ and Al ₂ O ₃ in the first and second glass fibers is within the above range, the resulting laminate will be even more excellent in connection reliability and warpage.

From the same viewpoint as above, the total content of SiO ₂ and Al ₂ O ₃ in the first glass fiber is more preferably 81% by mass or more, and even more preferably 82% by mass or more. In addition, the total content of SiO ₂ and Al ₂ O ₃ in the first glass fiber is preferably 96% by mass or less, more preferably 94% by mass or less, from the viewpoint of maintaining good drillability and insulation reliability. It is preferably 92 mass % or less, more preferably 90 mass % or less.
Also, from the same viewpoint as above, the total content of SiO ₂ and Al ₂ O ₃ in the second glass fiber is more preferably less than 78% by mass, still more preferably less than 76% by mass, and less than 74% by mass. Especially preferred. Further, the total content of SiO ₂ and Al ₂ O ₃ in the second glass fiber is preferably 50% by mass or more, more preferably 55% by mass or more, from the viewpoint of increasing the elastic modulus and decreasing the thermal expansion of the laminate. More preferably, 60% by mass or more is even more preferable.

The first glass fiber satisfies the total content of SiO ₂ and Al ₂ O ₃ , and the content of Al ₂ O ₃ is preferably 20% by mass or more, and 20 to 30% by mass. More preferably, 20 to 25% by mass is even more preferable.
The second glass fiber satisfies the total content of SiO ₂ and Al ₂ O ₃ , and the content of Al ₂ O ₃ is preferably less than 24% by mass, more preferably less than 22% by mass. Preferably, less than 20% by mass is more preferable.

Glass fibers include _{Fe2O3 , B2O3 ,} CaO, MgO, _Na2O , _K2O , _Li2O , _TiO2 , _ZnO , _ZrO2 , F, in addition to _SiO2 and _Al2O3 . ₂ or the like may be contained. Components other than SiO ₂ and Al ₂ O ₃ contained in the glass fiber are preferably one or more of the above other components.
Among these, the first glass fiber satisfies the total content of SiO ₂ and Al ₂ O ₃ , and the content of MgO is preferably 8% by mass or more, and 9% by mass or more. More preferably, 10% by mass or more is even more preferable. In addition, the second glass fiber satisfies the total content of SiO ₂ and Al ₂ O ₃ , and the content of MgO is preferably less than 8% by mass, more preferably less than 7% by mass. .

(Thermal expansion coefficient of glass fiber)
The coefficient of thermal expansion of the glass fiber is not particularly limited, but the coefficient of thermal expansion of the first glass fiber is preferably less than 4.0 ppm/°C. When the coefficient of thermal expansion of the first glass fiber is within the above range, the laminate obtained has even lower thermal expansion and a higher elastic modulus. From the same point of view, the coefficient of thermal expansion 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. In addition, the coefficient of thermal expansion of the first glass fiber may be 2.0 ppm/° C. or more, or 2.3 ppm/° C. or more, in consideration of the balance with other physical properties. It may be 5 ppm/°C or more.

The thermal expansion coefficient of the second glass fiber is also preferably as small as possible from the viewpoint of lowering the thermal expansion coefficient of the laminate. From the same point of view, the coefficient of thermal expansion 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 coefficient of thermal expansion of the second glass fiber tends to be higher than that of the first glass fiber, considering its composition and balance with other physical properties. From such a point of view, the coefficient of thermal expansion of the second glass fiber may be 4.0 ppm/°C or higher, 4.5 ppm/°C or higher, or 5.0 ppm/°C or higher. may be 5.3 ppm/° C. or higher.

(type of glass fiber)
Examples of the glass fiber constituting the fiber base material include E glass, S glass, C glass, D glass, T glass, NE glass, A glass, H glass, quartz glass, and the like. The material may be appropriately selected in consideration of the physical properties, composition, etc., that are preferable for the first glass fiber and the second glass fiber.

Typical compositions of E-glass, S-glass, C-glass, D-glass, T-glass and NE-glass are as follows.
E glass: SiO ₂ (52 to 56% by mass), Al ₂ O ₃ (12 to 16% by mass), Fe ₂ O ₃ (0 to 0.8% by mass), B ₂ O ₃ (5 to 10% by mass) , CaO (16-25% by mass), MgO (0-6% by mass), Na ₂ O + K ₂ O (0-2% by mass), TiO ₂ (0-1.5% by mass), F ₂ (0-1 mass%)
S glass: SiO ₂ (62 to 65% by mass), Al ₂ O ₃ (20 to 25% by mass), CaO (0 to 0.01% by mass), MgO (10 to 15% by mass), B ₂ O ₃ ( 0-0.01% by weight), Na ₂ O and K ₂ O (0-1% by weight)
C glass: SiO ₂ (65% by mass), Al ₂ O ₃ (4% by mass), B ₂ O ₃ (5% by mass), CaO (7% by mass), MgO (3% by mass), Na ₂ O (11% by mass) % by mass), K ₂ O (1% by mass), Li ₂ O (0.5% by mass), ZnO (3.5% by mass)
D glass: _SiO2 (74% by mass), _{Al2O3 (} 0.5% by mass) _, B2O3 ₍ 22% by mass), CaO (0.5% by mass), _Na2O (1% by mass) , K2O ₍ 1.5% by weight), Li2O ₍ 0.5% by weight),
T glass: SiO ₂ (64-66% by mass), Al ₂ O ₃ (24-26% by mass), MgO (9-11% by mass)
NE glass: SiO ₂ (52-56% by mass), CaO (0-10% by mass), Al ₂ O ₃ (10-15% by mass), B ₂ O ₃ (15-20% by mass), MgO (0- 5% by mass), Na ₂ O + K ₂ O (0 to 1% by mass), TiO ₂ (0.5 to 5% by mass)

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 the present embodiment is preferably a fiber base material made of S glass fiber, and the second fiber base material is a fiber made of E glass fiber. It is preferably a substrate.
Further, it is more preferable that the first fiber base material is glass cloth made of S glass fiber (hereinafter also referred to as "S glass cloth"), and the second fiber base material is made of E glass fiber. It is more preferable that the glass cloth (hereinafter also referred to as “E glass cloth”) is used.
The S glass cloth and the E glass cloth may contain glass fibers other than the S glass fiber and the E glass fiber, respectively, but the content thereof is preferably 10% by mass or less, more preferably 5% by mass or less. , 1% by mass or less is more preferable, and it is particularly preferable not to contain.

<Thermosetting resin composition>
The thermosetting resin composition used for forming the composite layer is not particularly limited as long as it contains a thermosetting resin, and if necessary, it contains a curing agent, a curing accelerator, an inorganic filler, etc. You may have Each component contained in the thermosetting resin composition will be described below.

(Thermosetting resin)
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, and modified silicone resins. , triazine resin, melamine resin, urea resin, furan resin and the like. Among these, modified silicone resins and epoxy resins are preferred.
Thermosetting resins may be used alone or in combination of two or more.

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

- 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).

（式中、Ｒ^１～Ｒ^４は、各々独立に、炭素数１～５のアルキル基、フェニル基又は置換フェニル基を示し、Ｘ^１及びＸ^２は、各々独立に、２価の有機基を示す。ｎは、２～１００の整数を示す。）

(In the formula, R ¹ to R ⁴ each independently represent 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 represent a divalent organic group. , and n is an integer of 2 to 100.)

In general formula (A-1) above, the alkyl group having 1 to 5 carbon atoms represented by R ¹ to R ⁴ includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group and the like. Among these, a methyl group is preferred.
Substituents of the substituted phenyl group represented by R ¹ to R ⁴ include alkyl groups having 1 to 5 carbon atoms, hydroxyl groups, amino groups, vinyl groups, carboxy groups and the like.
Examples of the divalent organic group represented by X ¹ and X ² include an alkylene group having 1 to 5 carbon atoms. Examples of the alkylene group include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group and 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, even more preferably from 700 to 1,500 g/mol.

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

（式中、Ｒ^１１～Ｒ^１３は、各々独立に、炭素数１～５の脂肪族炭化水素基を示す。Ｘ^１１は、炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、－Ｏ－又はスルホニル基を示す。ｐ、ｑ及びｒは、各々独立に、０～４の整数である。ｍは、０～１０の整数である。）

(wherein R ¹¹ to R ¹³ each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms; X ¹¹ is 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 are each independently an integer of 0 to 4. m is an integer of 0 to 10.)

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

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'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, etc. mentioned. Among these, bis(4-maleimidophenyl)methane is preferred.

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

（式中、Ｒ^２１は、各々独立に、水酸基、カルボキシ基又はスルホン酸基を示す。Ｒ^２２は、各々独立に、炭素数１～５のアルキル基又はハロゲン原子を示す。ｘは１～５の整数
、ｙは０～４の整数であり、且つ、１≦ｘ＋ｙ≦５を満たす。）

(wherein each R ²¹ independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group; each R ²² independently represents an alkyl group having 1 to 5 carbon atoms or a halogen atom; x represents 1 to 5 and y is an integer of 0 to 4, and satisfies 1 ≤ x + y ≤ 5.)

In general formula (C-1) above, examples of the alkyl group having 1 to 5 carbon atoms represented by R ²¹ include the same groups as those for R ¹ in general formula (A-1) above. Halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

Amine compounds (C) having an acidic substituent include o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, and o-aminobenzene. sulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like. Among these, m-aminophenol and p-aminophenol are preferred from the viewpoint of solubility and reactivity.

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

（式中、Ｘ^１３は、単結合、炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、－Ｏ－、スルホニル基、ケト基、フルオレンジイル基又はフェニレンジオキシ基を示す。Ｒ^１４及びＲ^１５は、各々独立に、炭素数１～５の脂肪族炭化水素基、メトキシ基又は水酸基を示す。ｓ及びｔは、各々独立に、０～４の整数である。Ｘ^１４～Ｘ^１６は、各々独立に、単結合、炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、－Ｏ－又はスルホニル基を示す。）

(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. R ¹⁴ and R ¹⁵ each independently represent 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 ~X16 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.)

Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X ¹³ to X ¹⁶ include the same groups as X ¹¹ in general formula (B-2) above.
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ¹⁴ and R ¹⁵ include the same groups as those for R ¹ in general formula (A-1) above. Among these, a methyl group and an ethyl group are preferable.

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'-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, benzoguanamine and the like. Among these, 3,3'-diethyl-4,4'-diaminodiphenylmethane is preferred.

The modified silicone resin can be prepared by reacting the components (A) to (D) above at, for example, 70 to 150°C. Organic solvent; reaction catalyst and the like may be used.

(Use amount of each component)
The amount of each component used in the reaction of components (A) to (D) is the sum of the primary amino groups of component (A), component (C) and component (D), and the maleimide group of component (B). The equivalent ratio [C═C group/NH ₂ group] to the total sum of carbon-carbon double bond groups in the group is preferably 0.1-10, more preferably 1-9, even more preferably 2-5. When the equivalent ratio is 0.1 or more, gelation and deterioration of heat resistance can be suppressed, and when it is 10 or less, deterioration of solubility in an organic solvent and 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, more preferably 40 to 100 parts by mass with respect to 100 parts by mass of component (A) while satisfying the above relational expression. More preferred.
The amount of component (C) used is preferably 1 to 500 parts by mass, more preferably 4 to 200 parts by mass, more preferably 7 to 100 parts by mass, relative to 100 parts by mass of component (A) while satisfying the above relational expression. More preferably, 10 to 50 parts by mass is particularly preferable.

The content of the modified silicone resin in the thermosetting resin composition is 5 to 80 parts by mass based on 100 parts by mass of the solid content of the thermosetting resin composition from the viewpoint of heat resistance, low water absorption and thermal expansion coefficient. It is preferably 10 to 60 parts by mass, even more preferably 20 to 40 parts by mass.
In the present specification, the term "solid content" refers to the non-volatile content excluding volatile substances such as solvents. Also includes liquid, starch syrup and wax. Here, room temperature indicates 25° C. in this specification.

〔Epoxy resin〕
Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak 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, biphenylaralkyl-type epoxy resin, naphthalene-type epoxy resin, dicyclopentadiene-type epoxy resin , alicyclic epoxy resins, diglycidyl ether compounds of polyfunctional phenols and polycyclic aromatics such as anthracene, and phosphorus-containing epoxy resins obtained by introducing phosphorus compounds into these compounds. Among these, biphenyl aralkyl type epoxy resins are preferred from the viewpoint of heat resistance and flame retardancy.

When the thermosetting resin composition contains an epoxy resin, its content is 2 to 60 in 100 parts by mass of the solid content of the thermosetting resin composition from the viewpoint of heat resistance, low water absorption and thermal expansion coefficient. Parts by weight are preferred, 5 to 40 parts by weight are more preferred, and 8 to 20 parts by weight are even more preferred.

[Acrylic polymer]
The thermosetting resin composition may be a resin composition containing an acrylic polymer and a thermosetting resin. In that case, the thermosetting resin composition may be a resin composition forming a phase-separated structure of a first phase containing an acrylic polymer and a second phase containing a thermosetting resin.
Acrylic polymers are usually polymers containing (meth)acrylic acid esters as monomers.
One type of acrylic polymer may be used alone, or two or more types may be used in combination.

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 addition, in this embodiment, "(meth)acrylic acid" indicates both "acrylic acid" and "methacrylic acid", and the same applies to other similar terms.

（式（１）中、Ｒ^３２はアルキル基、シクロアルキル基、シクロアルキルアルキル基、アリール基又はアラルキル基を示す。Ｒ^３１は水素原子又はメチル基を示す。）

(In formula (1), ^R32 represents an alkyl group, cycloalkyl group, cycloalkylalkyl group, aryl group or aralkyl group. ^R31 represents a hydrogen atom or a methyl group.)

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

(Meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, and (meth)acrylic acid 2 - Ethylhexyl, isobutyl (meth)acrylate, ethylene glycol methyl ether (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylate isobornyl acrylate, tricyclo[5.2.1,0(2,6)]dec-8yl (meth)acrylate, isodecyl (meth)acrylate, octadecyl (meth)acrylate, lauryl (meth)acrylate, (meth)allyl 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 by 1 type, and may use 2 or more types together.

(Inorganic filler)
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, boron Examples include aluminum oxide, potassium titanate, short glass fibers, fine glass powder, hollow glass, and the like. Among these, from the viewpoint of heat resistance and flame retardancy, silica is preferable, and fused silica such as fused spherical silica is more preferable.
The average particle size of the inorganic filler is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, even more preferably 0.2 to 1 μm. When the average particle size is 0.1 µm or more, good fluidity can be maintained, and when it is 10 µm or less, 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% volume when the cumulative frequency distribution curve by particle size is obtained with the total volume of the particles being 100%, and the laser diffraction scattering method is used. It can be measured with a particle size distribution measuring device or the like.
An inorganic filler may be used individually by 1 type, and may use 2 or more types together.

When the thermosetting resin composition contains an inorganic filler, its content is 10 in 100 parts by mass of the solid content of the thermosetting resin composition from the viewpoint of reducing the coefficient of thermal expansion and increasing the elastic modulus. 80 parts by mass is preferable, 30 to 75 parts by mass is more preferable, and 50 to 70 parts by mass is even more preferable.

(Curing accelerator)
Curing accelerators include organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, 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 viewpoint of heat resistance and flame retardancy.
A hardening accelerator may be used individually by 1 type, and may use 2 or more types together.
When the thermosetting resin composition contains a curing accelerator, its content is 0.01 parts by mass or more in 100 parts by mass of the solid content of the thermosetting resin composition from the viewpoint of heat resistance and flame retardancy. is preferred, 0.05 parts by mass or more is more preferred, 0.1 parts by mass or more is even more preferred, 5 parts by mass or less is preferred, 3 parts by mass or less is more preferred, and 1 part by mass or less is even more preferred.

The thermosetting resin composition is optionally selected from the group consisting of flame retardants, functional resins, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, adhesion improvers and organic solvents. may or may not contain one or more of the

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 production of prepregs and the like.
Examples of the organic solvent include alcohol 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; butyl acetate and propylene glycol monomethyl. ester solvents such as ether acetate; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfur atoms such as dimethyl sulfoxide Contained solvent etc. are mentioned. These may be used individually by 1 type, and may use 2 or more types together.
The solid content concentration of the varnish is preferably 40 to 90% by mass, more preferably 45 to 85% by mass, even more preferably 50 to 80% by mass. When the solid content concentration of the varnish is within the above range, good coatability can be maintained, and a prepreg having an appropriate content of the thermosetting resin composition can be obtained.

[Method for producing laminate]
The method for manufacturing the laminate of this embodiment includes:
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 a second glass fiber with a thermosetting resin composition;
is a method for manufacturing a laminate, in which
Aspects of the glass fiber, the fiber base material, the thermosetting resin composition, and the like used in the method for manufacturing the laminate of the present embodiment are as described above.

The prepregs (a) and (b) used in the production method of the present embodiment are obtained by impregnating a fiber base material with a thermosetting resin composition. After impregnating the substrate, it is semi-cured (B-staged) 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% by mass, more preferably 30 to 70% by mass, and even more preferably 40 to 60% by mass.

Next, the obtained prepreg (a) and prepreg (b) are appropriately stacked so as to form a desired laminate structure, and if necessary, a metal foil such as copper or aluminum is arranged on one or both sides. The laminate of the present embodiment can be manufactured by lamination molding. The metal foil is not particularly limited as long as it is used for laminates for electrical insulating materials. In addition, the laminate of the present embodiment in which metal foil is applied on one side or both sides is called a metal-clad laminate, and among these, a laminate in which copper foil is applied is called a copper-clad laminate.
As for the molding conditions for manufacturing the laminate, the technique for laminates for electrical insulating materials and multilayer boards can be applied, and multi-stage press, multi-stage vacuum press, continuous molding, autoclave molding machine, etc. are used, and the temperature is, for example, 100 to 250. C., pressure of 0.2 to 10 MPa, and heating time of 0.1 to 5 hours.

[Printed wiring board]
The printed wiring board of this embodiment is a printed wiring board containing the laminate of this embodiment.
The printed wiring board of this embodiment can be manufactured by forming a circuit on the surface of the laminate of this embodiment, for example. In addition, after wiring the conductor layer of the laminate of the present embodiment by a normal etching method, a plurality of the wiring-processed laminates are laminated with prepreg interposed therebetween, and then hot-pressed. Multilayering can also be performed collectively. After that, a printed wiring board can be manufactured through the formation of through holes or blind via holes by drilling or laser processing and the formation of interlayer wiring by plating or conductive paste.

[Semiconductor package]
The semiconductor package of this embodiment is obtained 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.

Next, the present embodiment will be described in more detail by the following examples, but these examples are not intended to 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.

[Evaluation method]
(1) Coefficient of Thermal Expansion The copper-clad laminate obtained in each example was immersed in a copper etchant to remove the copper foil to prepare an evaluation board of 5 mm length (X direction)×5 mm width (Y direction). Thermomechanical analysis was performed by a compression method using a TMA testing device (manufactured by DuPont, trade name: TMA2940) using the evaluation substrate as a measurement object. After the evaluation substrate was mounted on the apparatus in the X direction, the measurement was continuously performed twice under the measurement conditions of a load of 5 g and a temperature increase rate of 10° C./min. The average coefficient of thermal expansion from 30° C. to 100° C. in the second measurement was calculated and used as the coefficient of thermal expansion.

(2) Flexural modulus The copper-clad laminate obtained in each example was immersed in a copper etchant to remove the copper foil to prepare an evaluation board of 50 mm x 25 mm. The flexural modulus of elasticity of the evaluation substrate 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.

(3) Connection Reliability Using the copper-clad laminate obtained in each example, a circuit-formed package board and a motherboard board were prepared to evaluate the connection reliability with the motherboard, and then the package board and the motherboard board were soldered. An electrical connection was made using a ball. Next, after putting this into a temperature cycle tester (-55 to 125°C), the connection resistance value was measured for each predetermined number of cycles. When the resistance value fluctuated by 20% or more, the number of solder ball breakage cycles was defined, and connection reliability was evaluated from the number of cycles at 20% cumulative failure rate by Weibull plot.

<Production of copper-clad laminate>
[Example 1]
(Copper clad laminate 1: copper clad laminate in which copper foil is arranged on both sides of the laminate shown in FIG. 6)
(1) Preparation of varnish A siloxane diamine (manufactured by Dow Corning Toray Co., Ltd., trade name: X-22-161A, manufactured by Dow Corning Toray Co., Ltd., trade name: X-22-161A , Functional group equivalent of amino group: 800 g / mol) 19.4 g, 3,3'-diethyl-4,4'-diaminodiphenylmethane 13.0 g, N,N'-(4,4'-diphenylmethane) bis 122.9 g of maleimide, 4.7 g of p-aminophenol and 240.0 g of propylene glycol monomethyl ether were added. After reacting these at 115 ° C., atmospheric concentration is performed until the resin concentration reaches 60% by mass, and 53.3 g of cyclohexanone is added at 90 ° C. and stirred for 30 minutes to obtain an intermediate varnish. rice field.
303.5 g of this intermediate varnish and a silica methyl isobutyl ketone solution (700 g of spherical silica having an average particle size of 0.25 μm were added to 300 g of methyl isobutyl ketone solution containing 7 g of 3-aminopropyltrimethoxysilane while stirring. Additionally prepared) 601.0 g, a curing accelerator (manufactured by Shikoku Kasei Co., Ltd., trade name: C17Z) 1.2 g, and a biphenyl aralkyl novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC -3000-H) and 65.6 g were mixed. Furthermore, by adding methyl ethyl ketone as a diluting solvent, a uniform varnish having a solid content concentration of 65% by mass was obtained.

_{( 2} ) _Prepreg production thermal expansion coefficient of 2.9 ppm / ° C.) and 0.1 mm E glass (tensile modulus at 25 ° C. of 73 GPa, total content of SiO ₂ and Al ₂ O ₃ is 64 to 72% by mass, SiO ₂ content Al ₂ O ₃ content ratio (mass basis) to the amount of Al 2 O 3 was 0.28, thermal expansion coefficient was 5.5 ppm/°C), and then impregnated and coated, and then dried by heating at 130°C for 3 minutes. As a result, a prepreg containing S glass cloth and a prepreg containing E glass cloth having a thermosetting resin composition-derived solid content of 48% by mass were obtained. Further, the same number of prepregs as required for manufacturing a laminated plate, which will be described later, were manufactured.

(3) Production of Laminate Next, the prepregs produced above were laminated in such a manner that the outermost layer on each side was a prepreg containing E glass cloth, and the inner 12 layers were prepreg containing S glass cloth. Further, an electrolytic copper foil having a thickness of 12 μm was placed on both sides of the plate, and then pressed at a pressure of 2.5 MPa and a temperature of 240° C. for 60 minutes to obtain a copper-clad laminate 1 .

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

[Example 3]
(Copper clad laminate 3: copper clad laminate in which copper foil is arranged on both sides of the laminate shown in FIG. 7)
Except that in Example 1, the laminated structure of the prepreg was changed to a structure in which 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 were arranged in this order. obtained a copper-clad laminate 3 in the same manner as in Example 1.

[Comparative Example 1]
(Copper-clad laminate 4: Copper-clad laminate containing only S glass cloth as a 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.

[Comparative Example 2]
(Copper-clad laminate 5: Copper-clad laminate containing only E-glass cloth as a 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.

Table 1 shows the evaluation results of the laminates produced above.

As shown in Table 1, it was confirmed that the laminates of Examples 1 to 3 of the present embodiment had excellent connection reliability while having a high elastic modulus and a low thermal expansion property.

(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 Laminate

Claims (14)

A laminate containing a composite layer (X) and a composite layer (Y) containing a fiber base material and a cured product of a thermosetting resin composition,
At least one composite layer (X) is arranged between two 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 6 or more,
The composite layer (X) is a layer containing the first fiber base material composed of the first glass fiber,
The composite layer (Y) is a layer containing a second fiber base material composed of a second glass fiber,
The laminate, wherein the first glass fiber has a higher tensile modulus at 25° C. than the second glass fiber. The first glass fiber has a tensile modulus at 25° C. of 80 GPa or more,
2. The laminate according to claim 1, wherein the second glass fiber has a tensile modulus at 25[deg.]C of less than 80 GPa. 3. The laminate according to claim 1, wherein a difference in tensile elastic modulus at 25[deg.] C. between said first glass fiber and said second glass fiber is 10 GPa or more. A laminate containing a composite layer (X) and a composite layer (Y) containing a fiber base material and a cured product of a thermosetting resin composition,
At least one composite layer (X) is arranged between two 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 6 or more,
The composite layer (X) is a layer containing the first fiber base material composed of the first glass fiber,
The composite layer (Y) is a layer containing a second fiber base material 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. The laminate according to any one of claims 1 to 4, wherein said first glass fibers are S-glass. A laminate according to any one of claims 1 to 5, wherein said second glass fibers are E-glass. Any one of claims 1 to 6, wherein the difference between the number of composite layers (X) and the number of composite layers (Y) [composite layer (X) - composite layer (Y)] is 15 or less. A laminate according to any one of the preceding paragraphs. The laminate according to any one of claims 1 to 7, wherein the outermost layer on both sides of said laminate is a composite layer (Y). The laminate according to any one of claims 1 to 8, wherein the composite layer (Y) has two layers. The laminate according to any one of claims 1 to 9, wherein the thermosetting resin composition contains an inorganic filler. The laminate according to any one of claims 1 to 10, which is for printed wiring boards. A printed wiring board comprising the laminate according to any one of claims 1 to 11. A semiconductor package comprising the printed wiring board according to claim 12 and a semiconductor element mounted thereon. A method for producing a laminate according to any one of claims 1 to 11,
A prepreg (a) obtained by impregnating a thermosetting resin composition into a first fiber base material composed of the first glass fiber;
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 producing a laminate, comprising laminating and molding.

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