JP2014032979A - Resin substrate, prepreg, printed wiring board, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin substrate having an excellent lead-free solder reflow property and reduced warpage at mounting.SOLUTION: A resin substrate 100 comprises a fiber base material 101 and an insulation resin layer 103, and is obtained by impregnating the fiber base material 101 with a resin material. The 1%-weight reduction temperature of the resin substrate 100 is 350°C or more and 500°C or less.

Description

  The present invention relates to a resin substrate, a prepreg, a printed wiring board, and a semiconductor device.

In recent years, with the demand for higher functionality and lighter, thinner and smaller electronic devices, high-density integration and further high-density mounting of electronic components have been promoted. The miniaturization of semiconductor devices used in these electronic devices The process is progressing rapidly.
For this reason, printed wiring boards on which electronic components including semiconductor elements are mounted tend to be thinned, and a resin board used for the printed wiring board has a thickness of about 0.8 mm.
More recently, a package-on-package (hereinafter referred to as POP) in which semiconductor devices using resin substrates of 0.4 mm or less are stacked is mounted on mobile devices (for example, mobile phones, smartphones, tablet PCs, etc.). Has been.

JP 2006-203142 A

  As the semiconductor device is miniaturized in this way, the thickness of the semiconductor element and the sealing material, which conventionally has been responsible for most of the rigidity of the semiconductor device, becomes extremely thin, and the warp of the semiconductor device is likely to occur. In addition, since the proportion of the resin substrate as a constituent member increases, the physical properties and behavior of the resin substrate have a great influence on the warpage of the semiconductor device.

On the other hand, as lead-free soldering progresses from the viewpoint of protecting the global environment, the maximum temperature in the reflow process that is experienced when solder balls are mounted on a printed wiring board or mounted on a mother board has become very high. Since the melting point of commonly used lead-free solder is about 210 degrees, the maximum temperature during the reflow process is a level exceeding 260 degrees.
For this reason, the semiconductor devices above and below the POP at the time of heating may be greatly warped because the difference in thermal expansion between the semiconductor element and the printed wiring board on which the semiconductor element is mounted is very large. In addition, large semiconductor packages such as FCBGA used for CPUs, etc. go through a reflow process of 260 degrees, and also through a reflow process for repairing and remounting from a defective substrate, resulting in high thermal stability. Is needed. Further, when volatile gas such as outgas generated from the resin substrate is generated, the conductor wiring layer and the buildup insulating layer may be peeled off.

As means for solving such problems, for example, there are means described in the following documents.
In Patent Document 1 (Japanese Patent Laid-Open No. 2006-203142), a woven fabric made of organic fibers having a negative coefficient of thermal expansion is used as the base material of the prepreg, so that the heat of the multilayer printed wiring board for semiconductor packages can be obtained. It is described that the expansion coefficient can be made close to the thermal expansion coefficient of the silicon chip, and the connection reliability when the silicon chip is mounted can be improved.

  However, like patent document 1, when the organic fiber base material which shows a negative thermal expansion is used as a fiber base material used for a prepreg, the glass transition temperature of the resin substrate obtained from the value expected from the used material As a result, the elastic modulus of the resin substrate may be lowered. Therefore, the obtained resin substrate has insufficient rigidity, and the effect of suppressing warping after heating such as reflow is not sufficiently satisfactory. Further, when the reflow process is repeated, a large amount of outgas (volatile matter) is generated from the resin substrate, volume shrinkage occurs due to a decrease in resin weight, and warpage may be worsened.

  Then, this invention makes it a subject to provide the resin substrate which was excellent in the lead-free solder reflow property, and the curvature at the time of mounting was reduced.

  The present inventors diligently studied about design guidelines for solving the above problems. As a result, the inventors have found that the scale of 1% weight loss temperature of the resin substrate is effective as such a design guideline, and have reached the present invention.

According to the present invention,
A resin substrate obtained by impregnating a fiber base material with a resin material,
A resin substrate having a 1% weight reduction temperature of 350 ° C. or more and 500 ° C. or less is provided.

According to the present invention,
A prepreg formed by impregnating a fiber base material with a resin material,
There is provided a prepreg in which a 1% weight reduction temperature of a cured product obtained by curing the prepreg at 200 ° C. for 1 hour is from 350 ° C. to 500 ° C.

  Furthermore, according to this invention, the printed wiring board formed by carrying out circuit processing of the said resin substrate is provided.

  Furthermore, according to the present invention, there is provided a semiconductor device in which a semiconductor element is mounted on the printed wiring board.

  ADVANTAGE OF THE INVENTION According to this invention, the resin board which was excellent in the lead-free solder reflow property and the curvature at the time of mounting was reduced can be provided.

It is sectional drawing which shows an example of a structure of the resin substrate in this embodiment. It is sectional drawing which shows an example of the manufacturing method of the prepreg in this embodiment. It is the schematic which shows the form example of each width direction dimension about the support base material, the insulating resin layer, and the fiber base material which are used for the manufacturing method of the prepreg in this embodiment. It is sectional drawing which shows an example of the manufacturing method of the prepreg in this embodiment. It is sectional drawing which shows an example of the manufacturing method of the prepreg in this embodiment. It is sectional drawing which shows an example of the manufacturing method of the prepreg in this embodiment. It is sectional drawing which shows an example of a structure of the semiconductor package in this embodiment. It is sectional drawing which shows an example of a structure of the semiconductor device in this embodiment.

  Embodiments of the present invention will be described below with reference to the drawings. In all the drawings, similar constituent elements are denoted by common reference numerals, and description thereof is omitted as appropriate. Moreover, the figure is a schematic diagram and does not necessarily match the actual dimensional ratio.

(Resin substrate)
First, the structure of the resin substrate in this embodiment is demonstrated. FIG. 1 is a cross-sectional view showing an example of the configuration of the resin substrate 100 in the present embodiment.
The resin substrate 100 includes a fiber base material 101 and an insulating resin layer 103, and is obtained by impregnating the fiber base material 101 with a resin material. And the 1% weight reduction | decrease temperature of the resin substrate 100 is 350 degreeC or more, Preferably it is 360 degreeC or more, More preferably, it is 370 degreeC or more. The 1% weight loss temperature of the resin substrate 100 is 500 ° C. or lower, and is usually 400 ° C. or lower. Here, the 1% weight loss temperature can be measured by, for example, a thermogravimetry apparatus.

Resin substrate 100 having a 1% weight reduction temperature within the above range can reduce warpage of resin substrate 100 during heat treatment such as reflow.
Further, as a result, warpage of the semiconductor package 200 and the semiconductor device 300 including the resin substrate 100 can be reduced.

In the resin substrate 100 in the present embodiment, the linear expansion coefficient in the in-plane direction of the substrate calculated in the range of 25 ° C. to 150 ° C. is preferably −10 ppm / ° C. to 10 ppm / ° C., more preferably −5 ppm. / ° C. or more and 7 ppm / ° C. or less, particularly preferably 0 ppm / ° C. or more and 4 ppm / ° C. or less. In addition, the linear expansion coefficient of this embodiment is an average value in the said temperature range.
When the linear expansion coefficient of the resin substrate 100 is within the above range, the printed circuit board on which the wiring pattern is formed and the semiconductor package 200 on which the semiconductor element is mounted can be more effectively suppressed in warpage and improved in temperature cycle reliability. . Furthermore, the temperature cycle reliability with the mother board of the semiconductor device 300 on which the semiconductor package 200 is secondarily mounted can be improved more effectively.

Moreover, in order to obtain the effect of preventing the warp of the resin substrate 100 more effectively, it is not particularly limited, but the glass transition temperature by the dynamic viscoelasticity measurement of the resin substrate 100 is preferably 250 ° C. or more, more preferably. Is 260 ° C. or higher, more preferably 270 ° C. or higher. About an upper limit, 350 degrees C or less is preferable, for example.
When the glass transition temperature by the dynamic viscoelasticity measurement satisfies the above range, the resin substrate 100 increases the rigidity of the resin substrate 100 and can further reduce the warp of the resin substrate 100 during mounting.

Further, in order to more effectively obtain the effect of preventing warpage of the resin substrate 100, the storage elastic modulus E ′ at 250 ° C. of the resin substrate 100 is preferably 15 GPa or more, more preferably. 25 GPa or more. Although it does not specifically limit about an upper limit, For example, it can be 50 GPa or less.
When the storage elastic modulus E ′ at 250 ° C. satisfies the above range, the resin substrate 100 increases the rigidity of the resin substrate 100 and can further reduce the warp of the resin substrate 100 during mounting.

  The thickness of the resin substrate 100 in this embodiment is preferably 0.025 mm or more and 0.6 mm or less. More preferably, it is 0.04 mm or more and 0.4 mm or less, More preferably, it is 0.04 mm or more and 0.3 mm or less, More preferably, it is 0.05 mm or more and 0.2 mm or less. When the thickness of the resin substrate 100 is within the above range, the balance of mechanical strength and productivity is particularly excellent, and the resin substrate 100 suitable for a thin printed wiring board can be obtained.

(Manufacturing method of the resin substrate 100)
It continues and demonstrates the manufacturing method of the resin substrate 100 in this embodiment. The resin substrate 100 is obtained by, for example, heat curing a prepreg. The prepreg used here is a sheet-like material, which is excellent in various properties such as dielectric properties, mechanical and electrical connection reliability under high temperature and high humidity, and is suitable for the production of the resin substrate 100 for a printed wiring board.

The prepreg in the present embodiment is not particularly limited. For example, the prepreg is obtained by impregnating a fiber base material with a resin material containing one or two or more thermosetting resins and a filler, and then semi-curing.
In the present embodiment, the method of impregnating the fiber base material with the resin material is not particularly limited. For example, (1) a method of laminating a resin layer with a support base material on a fiber base material, and (2) a resin material as a solvent And a method of preparing a resin varnish by dissolving the resin varnish and applying the resin varnish to a fiber substrate.

  Among these, (1) a method of laminating a resin layer with a supporting substrate on a fiber substrate is particularly preferable. The method of laminating the resin layer with a supporting substrate on the fiber substrate is easy to adjust the tension applied to the fiber substrate to a low pressure.

  In particular, when the thickness of the fiber substrate is 0.2 mm or less, (1) a method of laminating a resin layer with a supporting substrate on the fiber substrate is preferable. According to this method, the amount of the resin material impregnated into the fiber base can be freely adjusted, and the moldability of the prepreg can be further improved. In addition, when laminating the resin layer with a supporting base material on a fiber base material, it is more preferable to use a vacuum laminating apparatus or the like.

Below, (1) The manufacturing method of the prepreg using the method of laminating the resin layer with a support base material on a fiber base material is demonstrated, and the constituent material of the resin substrate 100 is also demonstrated each time. FIG. 2 is a cross-sectional view showing a method for producing a prepreg in the present embodiment. FIG. 3 is a schematic view showing an example of the width-direction dimensions of the support base material 13, the resin layers 15 a and 15 b, and the fiber base material 11 used in the prepreg manufacturing method of the present embodiment.
(1) A method for producing a prepreg using a method of laminating a resin layer with a supporting substrate is as follows. (A) First carrier material 5a in which resin layers 15a and 15b made of a resin material are formed on one side of a supporting substrate 13. And a step of preparing each of the second carrier materials 5b, and a step (B) of superimposing the resin layers of the carrier materials 5a and 5b on both surfaces of the fiber base material 11 and laminating them under reduced pressure conditions. It is out.

First, the step (A) will be described.
In the step (A), the first carrier material 5a and the second carrier material 5b in which the resin layers 15a and 15b are formed on one side of the support base 13 are respectively prepared and prepared. The carrier materials 5 a and 5 b are obtained by forming resin layers 15 a and 15 b in a thin layer on one side of the support base 13. The resin layers 15 a and 15 b can be formed on one side of the support base 13 with a predetermined thickness.

The method for producing the carrier materials 5a and 5b is not particularly limited. For example, using various coater apparatuses such as a comma coater, a knife coater, and a die coater, a method of applying a resin material to the support base 13, a spray nozzle, and the like. Examples thereof include a method of applying a resin material to the support base 13 using various spray devices.
Among these, the method of applying the resin material to the support base 13 using various coater apparatuses is preferable. Thereby, the resin layers 15a and 15b excellent in thickness accuracy can be formed with a simple apparatus.

After the resin material is applied to the support base 13, it can be dried at room temperature or under heating as necessary. Thereby, when an organic solvent or a dispersion medium is used when preparing the resin material, these are substantially removed to eliminate the tackiness of the resin layer surface, and the carrier materials 5a and 5b having excellent handling properties. It can be.
Moreover, the hardening reaction of a thermosetting resin can be advanced to the middle, and the fluidity | liquidity of the resin layers 15a and 15b in the (B) process or (C) process mentioned later can also be adjusted.
Although it does not specifically limit as a method to dry under the said heating, The method of processing continuously using a hot air drying apparatus, an infrared heating apparatus, etc. can be applied preferably.

In the carrier materials 5a and 5b in the present embodiment, the thicknesses of the resin layers 15a and 15b can be appropriately set according to the thickness of the fiber base 11 used. For example, it can be 1 μm or more and 100 μm or less.
The resin layers 15a and 15b may be formed by one or a plurality of coatings using the same resin material, or may be formed by a plurality of coatings using different resin materials. May be.

  After the carrier materials 5a and 5b are manufactured in this way, a protective film is overlaid on the upper surface side where the resin layers 15a and 15b are formed, that is, on the side opposite to the support base material 13 in order to protect the resin layer surface. May be.

As the support substrate 13, for example, a long sheet can be suitably used. The material of the support base 13 is not particularly limited. For example, a thermoplastic resin film formed from a thermoplastic resin such as polyethylene terephthalate, polyethylene, or polyimide, or copper or copper alloy, aluminum or aluminum alloy, silver or silver A metal foil formed from a metal such as an alloy can be suitably used.
Among these, as the thermoplastic resin for forming the thermoplastic resin film, polyethylene terephthalate is preferable because it is excellent in heat resistance and inexpensive.
Moreover, as a metal which forms metal foil, it is excellent in electroconductivity, the circuit formation by an etching is easy, and since it is cheap, copper or a copper alloy is preferable.

  When a thermoplastic resin film is used as the support substrate 13, it is preferable that the surface on which the resin layers 15a and 15b are formed is subjected to a peelable process. Thereby, resin layer 15a, 15b and the support base material 13 can be isolate | separated easily at the time of manufacture of a prepreg or after manufacture.

As the thickness of the thermoplastic resin film, for example, a film having a thickness of 15 μm or more and 75 μm or less can be used. In this case, the workability at the time of manufacturing the carrier materials 5a and 5b can be improved.
When the thickness of the thermoplastic resin film is not less than the above lower limit value, sufficient mechanical strength can be ensured when the carrier materials 5a and 5b are manufactured. Moreover, productivity of carrier material 5a, 5b can be improved as thickness is below the said upper limit.

  When a metal foil is used as the support base material 13, a surface on which the resin layers 15 a and 15 b are formed may be subjected to a detachable process, or such a process is not performed. What gave the process which improves adhesiveness with resin layer 15a, 15b can also be used.

When a metal foil having a peelable treatment applied to the surface on which the resin layers 15a and 15b are formed is used as the support substrate 13, the same effect as that obtained when the thermoplastic resin film is used is expressed. Can do.
As the thickness of this metal foil, for example, a thickness of 1 μm or more and 70 μm or less can be used. Thereby, workability | operativity at the time of manufacturing carrier material 5a, 5b can be made favorable.
When the thickness of the metal foil is equal to or more than the above lower limit value, sufficient mechanical strength can be ensured when the carrier materials 5a and 5b are manufactured. Moreover, productivity of carrier material 5a, 5b can be improved as thickness is below the said upper limit.

  In the case where a thermoplastic resin film or a metal foil having a peelable treatment applied to the surface on which the resin layers 15a and 15b are formed is used as the support substrate, the support on the side on which the resin layers 15a and 15b are formed is used. The unevenness on the surface of the base material 13 is preferably as small as possible. Thereby, when the resin substrate 100 is manufactured, the surface smoothness of the resin substrate 100 can be improved. Therefore, when a new conductor layer is formed by metal plating or the like after the surface of the resin substrate 100 is roughened, A fine circuit can be processed and formed more easily.

On the other hand, when a metal foil that has not been subjected to a detachable treatment or has been subjected to a treatment that improves the adhesion to the resin layer is used as the support substrate, Can be used as it is as a conductor layer for circuit formation.
At this time, the unevenness of the surface of the support base on the side where the resin layers 15a and 15b are formed is not particularly limited, but for example, Ra: 0.1 μm or more and 1.5 μm or less can be used.

In this case, sufficient adhesion between the resin layer and the metal foil can be ensured, and a fine circuit can be easily formed by performing an etching process or the like on the metal foil.
Moreover, as thickness of this metal foil, what is 1 micrometer or more and 35 micrometers or less can be used suitably, for example. When the thickness of the metal foil is equal to or greater than the lower limit, sufficient mechanical strength can be ensured when the carrier materials 5a and 5b are manufactured. Further, if the thickness is not more than the above upper limit value, a fine circuit may be more easily formed by processing.
This metal foil can be used for manufacturing the prepreg by using it for at least one support base material 13 of the carrier materials 5a and 5b used for manufacturing the prepreg.
In addition, as metal foil used for this use, metal foil formed from one layer can also be used, and metal foil comprised from two or more layers which metal foil can peel can also be used. . For example, a first metal foil on the side to be in close contact with the resin layer and a second metal foil that can support the first metal foil on the side opposite to the side to be in close contact with the resin layer are joined in a peelable manner 2 A layered metal foil can be used.

Next, the step (B) will be described.
In the step (B), the resin layer side of the carrier material 5a, 5b in which the resin layer is formed on one side of the support base material is overlapped on both sides of the fiber base material 11, and these are laminated under reduced pressure conditions. . FIG. 2 shows an example when the carrier materials 5a and 5b and the fiber base material 11 are overlapped.

The carrier material 5a in which the first resin material is applied to the base material in advance and the carrier material 5b in which the second resin material is applied to the base material are manufactured. Next, using the vacuum laminating apparatus 60, the carrier materials 5a and 5b are overlapped from both surfaces of the fiber base material 11 under reduced pressure, and bonded with a laminating roll 61 heated to a temperature at which the resin material melts as necessary. The fiber base material 11 is impregnated with the resin material applied on the base material.
Here, when the resin layers of the carrier materials 5a and 5b and the fiber substrate 11 are bonded by bonding under reduced pressure, the inside of the fiber substrate 11 or the resin layers and fibers of the carrier materials 5a and 5b are bonded. Even if there is an unfilled portion at the joint portion with the base material 11, it can be a reduced-pressure void or a substantial vacuum void. The decompression condition is preferably 7000 Pa or less. More preferably, it is 3000 Pa or less. Thereby, the said effect can be expressed highly.
As another device for joining the fiber base material 11 and the carrier materials 5a and 5b under such a reduced pressure, for example, a vacuum box device, a vacuum becquerel device, or the like can be used.

  The fiber base material 11 can be continuously supplied and transported in the same direction as the transport direction of the carrier materials 5a and 5b, and has dimensions in the width direction. Here, the dimension in the width direction refers to the dimension of the fiber base material 11 in the direction orthogonal to the transport direction of the fiber base material 11. As such a fiber base material 11, the thing of a long sheet form can be used suitably, for example.

When laminating the carrier materials 5a and 5b and the fiber base material 11, it is preferable to heat to a temperature at which the resin layer can be melted. Thereby, carrier material 5a, 5b and the fiber base material 11 can be joined easily. Moreover, when at least a part of the resin layer is melted and impregnated into the fiber base material 11, it becomes easy to obtain the prepreg 21 with good impregnation properties.
Although it does not specifically limit as a method to heat here, For example, the method of using the laminate roll heated to predetermined temperature at the time of joining etc. can be used suitably.
The temperature to be heated (hereinafter also referred to as “laminate temperature”) is not particularly limited because it varies depending on the type and composition of the resin forming the resin layer, but is not lower than the softening point of the resin forming the resin layer + 10 ° C. or higher. The temperature is preferred, and the softening point + 30 ° C. or more is more preferred. Thereby, the fiber base material 11 and the resin layer can be easily joined. Further, the productivity of the resin substrate 100 can be further improved by increasing the laminating speed. For example, it can be carried out at 60 ° C. or higher and 150 ° C. or lower. The softening point can be defined by a peak temperature of G ′ / G ″ in a dynamic viscoelasticity test, for example.

  The laminating speed during lamination is preferably 0.5 m / min or more and 10 m / min or less, and more preferably 1.0 m / min or more and 10 m / min or less. If it is 0.5 m / min or more, sufficient lamination becomes possible, and if it is 1.0 m / min or more, productivity can be further improved.

In addition, other methods for applying pressure during lamination are not particularly limited, and conventionally known methods that can apply a predetermined pressure, such as a hydraulic method, a pneumatic method, and a gap pressure method, can be employed.
Among these, the method of carrying out without substantially applying pressure to the above-mentioned joined one is preferable. According to this method, since the resin component does not flow excessively in the step (B), the prepreg 21 having a desired insulating layer thickness and high uniformity in the insulating layer thickness is efficiently obtained. Can be manufactured well.
Moreover, since the stress which acts on the fiber base material 11 with the flow of the resin component can be minimized, the internal strain can be extremely reduced. Furthermore, since the pressure is not substantially applied when the resin component is melted, it is possible to substantially eliminate the occurrence of a dent in this step.

Therefore, the lamination pressure is not particularly limited, but is preferably in the range of 15 N / cm ² or more and 250 N / cm ² or less, and more preferably in the range of 20 N / cm ² or more and 100 N / cm ² or less. Within this range, productivity can be further improved.

Further, at the time of lamination, it is preferable that the tension applied to the fiber base material 11 is as small as possible without causing a problem in appearance such as wrinkles. Specifically, it is preferably in the range of 10 N / m to 350 N / m, more preferably in the range of 15 N / m to 250 N / m, and in the range of 18 N / m to 150 N / m. It is particularly preferred that By setting the tension within the above range, strain generated in the prepreg 21 is relieved, and as a result, the resin substrate 100 having excellent stress relieving ability can be obtained.

  Moreover, in this embodiment, it is preferable that the process of performing the tension | tensile_strength cut of the tension concerning the fiber base material 11 is included before the process of laminating. Thereby, it is possible to eliminate defects in appearance such as wrinkles that occur when laminating at a low tension.

  The tension cutting method is not particularly limited, and for example, a known tension cutting method such as a nip roll or an S-shaped nip roll can be used. Further, the tension cut can be achieved by introducing a tension cut device before the lamination. By performing the tension cut by the method as exemplified above, the tension can be reduced as much as possible without impairing the transportability of the fiber base material 11. Therefore, the occurrence of distortion that occurs during lamination and causes warping can be further suppressed.

  Furthermore, in this embodiment, the specific configuration of the means for carrying out the lamination is not particularly limited, but in order to improve the appearance of the resulting resin substrate 100, it is between the pressing surface and the support base material 13. A protective film may be arranged.

Next, the relationship between the dimensions in the width direction will be described with reference to FIGS. FIG. 3 is a schematic view showing an example of the width dimension of each of the support base material, the resin layer, and the fiber base material used in the prepreg manufacturing method of the present embodiment.
3 (1) to 3 (3), the carrier materials 5a and 5b have a support base 13 having a width dimension larger than that of the fiber base 11 and a resin having a width dimension larger than that of the fiber base 11. What has the layer 15 is used. Here, FIG. 3A shows the relationship among the width direction dimensions of the support base 13, the resin layers 15a and 15b, and the fiber cloth.
In this embodiment, in the step (B), the resin layer 15a of the carrier material 5a and the fiber base material in the inner region of the width direction dimension of the fiber base material 11, that is, in the region where the fiber base material 11 exists in the width direction. 11 and the resin layer 15b of the carrier material 5b and the fiber base material 11 can be bonded to each other.
Further, in the outer region of the width direction of the fiber base material 11, that is, the region where the fiber base material 11 does not exist, the resin layer 15a surface of the carrier material 5b and the resin layer 15b surface of the carrier material 5b are directly connected. Can be joined. This state is shown in FIG.
And since these joining is implemented under reduced pressure, an unfilled part remains in the inside of the fiber base 11 or the joint surface between the resin layers 15a and 15b of the carrier materials 5a and 5b and the fiber base 11 and the like. However, since these can be reduced pressure voids or substantial vacuum voids, this can be easily performed when heat treatment is performed in a temperature range equal to or higher than the melting temperature of the resin in step (C) after step (B). Can be eliminated. In the step (C), it is possible to prevent air from entering from the peripheral portion in the width direction and forming a new void. This state is shown in FIG.

  Moreover, while having the support base material 13 whose width direction dimension is larger than the fiber base material 11 as carrier material 5a, 5b, one of the carrier materials 5a, 5b, for example, as the carrier material 5a, rather than the fiber base material 11 What has the resin layer 15a with a large width direction dimension may be used, and what has the resin layer 15b with the same width direction dimension as the fiber base material 11 may be used as the carrier material 5b.

  Moreover, you may use as the carrier material 5a, 5b what has the resin layers 15a and 15b whose width direction dimension is the same as the fiber base material 11. FIG.

After the step (B), a step (C) in which heat treatment is performed at a temperature equal to or higher than the melting temperature of the insulating resin using the hot air drying device 62 may be performed. Thereby, the decompression void etc. which have occurred in the joining process under reduced pressure can be almost eliminated.
Other methods for the heat treatment are not particularly limited, but conventionally known methods that can be heated at a predetermined temperature such as an infrared heating device, a heating roll device, a flat platen hot plate press device, a heat circulation heating device, an induction heating device, etc. It can be carried out using a heating device. Among these, the method of carrying out without substantially applying pressure to the above-mentioned joined one is preferable.
In the case of using a hot air drying device or an infrared heating device, it can be carried out without substantially applying pressure to the joined one. According to this method, since the resin component does not flow excessively, a prepreg having a desired insulating layer thickness and high uniformity in the insulating layer thickness can be manufactured more efficiently. Can do.
Moreover, when using a heating roll apparatus and a flat hot disk press apparatus, it can implement by making a predetermined pressure act on the said joined thing. Further, since the stress acting on the fiber base material along with the flow of the resin component can be minimized, the internal strain can be extremely reduced.
Furthermore, since the pressure is not substantially applied when the resin component is melted, it is possible to substantially eliminate the occurrence of a dent in this step.
The heating temperature is not particularly limited because it varies depending on the type and composition of the resin forming the resin layer, but the temperature range is such that the thermosetting resin used melts and the curing reaction of the thermosetting resin does not proceed rapidly. It is preferable to do.
In addition, the time for the heat treatment is not particularly limited because it varies depending on the type of thermosetting resin to be used, but for example, it can be carried out by treating for 1 to 10 minutes.

  In the manufacturing method of the prepreg in this embodiment, after the said (B) process or (C) process, it can have the process of winding up the prepreg obtained above continuously as needed. Thereby, a prepreg can be made into a roll form and the handling workability | operativity at the time of manufacturing the resin substrate 100 etc. can be improved using a prepreg.

  Moreover, the manufacturing method of the prepreg in this embodiment other than said method includes (2) a method in which a resin varnish is prepared by dissolving a resin material in a solvent, and the resin varnish is applied to a fiber substrate. For example, the method is described in paragraphs 0022 to 0041 of Reference Document 1 (Japanese Patent Laid-Open No. 2010-275337). Hereinafter, a specific description will be given with reference to FIG.

  The fiber base material 3 is conveyed so as to pass between the two die coaters to a coating machine provided with the first coating device 1a and the second coating device 1b, which are two die coaters, on both sides thereof. The resin varnish 4 is applied on each side. The first coating apparatus 1a and the second coating apparatus 1b may use the same die coater or different ones. Moreover, as shown in FIG. 5, the 1st coating apparatus 1a and the 2nd coating apparatus 1b may use a roll coater. Further, the coating distance L and the tip overlap distance D preferably have a constant distance as shown in FIGS. 4 and 5, but may not have a constant distance as shown in FIG. .

  Each of the first coating device 1 a and the second coating device 1 b has a coating tip 2, and each coating tip 2 is elongated in the width direction of the fiber substrate 3. And the 1st coating front-end | tip part 2a which is a coating front-end | tip part of the 1st coating apparatus 1a protrudes toward one surface of the fiber base material 3, and is the coating front-end | tip part of the 2nd coating apparatus 1b. The 2 coating front-end | tip part 2b protrudes toward the other surface of the fiber base material 3. FIG. Thereby, when the resin varnish 4 is applied, the first coating tip 2a is in contact with one surface of the fiber substrate 3 via the resin varnish 4, and the second coating tip 2b is a fiber base. The other surface of the material 3 comes into contact with the resin varnish 4.

The discharge amount per unit time of the resin varnish 4 discharged from the first coating device 1a and the second coating device 1b may be the same or different. By varying the discharge amount per unit time of the resin varnish 4, the thickness of the resin varnish 4 to be applied can be individually controlled on one side and the other side of the fiber substrate 3, and the resin layer It is possible to easily adjust the layer thickness.
A prepreg is manufactured by heating at a predetermined temperature in a dryer to volatilize the solvent of the applied resin varnish 4 and to semi-cure the resin material. In this way, by supplying only the necessary resin amount to the fiber base material 11, the stress acting on the fiber base material 11 can be minimized, and the strain generated inside the prepreg is alleviated.
In the method of (2) preparing a resin varnish by dissolving a resin material in a solvent and applying the resin varnish to a fiber substrate, the materials and processing conditions to be used are the above-mentioned (1) resin layer with a supporting substrate. It is desirable to use materials and processing conditions according to the prepreg manufacturing method using the method of laminating on a fiber substrate.

  Moreover, although the solvent used for the resin varnish 4 preferably exhibits good solubility with respect to the resin component in the resin material, a poor solvent may be used as long as it does not have an adverse effect. Examples of the solvent exhibiting good solubility include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve and carbitol.

  The solid content of the resin varnish 4 is not particularly limited, but is preferably 40% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass. Thereby, the impregnation property to the fiber base material of the resin varnish 4 can further be improved. A prepreg can be obtained by impregnating a fiber base material with a resin material and drying at a predetermined temperature, for example, 80 ° C. or more and 200 ° C. or less.

  In the prepreg of this embodiment, the 1% weight loss temperature of a cured product obtained by curing the prepreg at 200 ° C. for 1 hour is 350 ° C. or higher, preferably 360 ° C. or higher, more preferably 370 ° C. or higher. is there. In the prepreg of this embodiment, the 1% weight reduction temperature of a cured product obtained by curing the prepreg at 200 ° C. for 1 hour is 500 ° C. or less, and usually 400 ° C. or less. Here, the 1% weight loss temperature can be measured by, for example, a thermogravimetry apparatus.

The resin substrate 100 using the prepreg whose 1% weight reduction temperature is within the above range can reduce the warpage of the resin substrate 100 during heat treatment such as reflow.
Further, as a result, warpage of the semiconductor package 200 and the semiconductor device 300 including the resin substrate 100 can be reduced.

Then, the manufacturing method of the resin substrate 100 using the prepreg obtained above is demonstrated. Although the manufacturing method of the resin substrate 100 using a prepreg is not specifically limited, For example, it is as follows.
After peeling the supporting base material from the obtained prepreg, metal foils are stacked on the upper and lower surfaces or one side of the outer side of the prepreg, and these are joined under a high vacuum condition using a laminator device or a becquerel device, or directly outside the prepreg. Stack metal foil on top and bottom or one side.
Next, what laminated | stacked metal foil on the prepreg is heated and pressurized with a vacuum press, or it heats with a dryer, and the resin substrate 100 can be obtained.
The thickness of the metal foil is, for example, 1 μm or more and 35 μm or less. When the thickness of the metal foil is equal to or greater than the lower limit, sufficient mechanical strength can be ensured when the carrier materials 5a and 5b are manufactured. Further, if the thickness is not more than the above upper limit value, it may be easy to process and form a fine circuit.
In addition, when metal foil is used as a support base material, it can be used as it is without peeling the support base material.

  Examples of the metal constituting the metal foil include copper and copper alloys, aluminum and aluminum alloys, silver and silver alloys, gold and gold alloys, zinc and zinc alloys, nickel and nickel alloys, tin and tin alloys. Alloys, iron and iron-based alloys, Kovar (trade name), 42 alloys, Fe-Ni alloys such as Invar or Super Invar, W or Mo, and the like can be given. Also, an electrolytic copper foil with a carrier can be used.

(Constituent material of resin substrate)
Hereinafter, each material used when manufacturing the resin substrate 100 will be described in detail.

(Thermosetting resin)
Although it does not specifically limit as a thermosetting resin, It is preferable that it has a low linear expansion coefficient and a high elasticity modulus, and is excellent in the reliability of thermal shock property.
The glass transition temperature of the thermosetting resin is preferably 160 ° C. or higher and 350 ° C. or lower, more preferably 180 ° C. or higher and 300 ° C. or lower. By using a thermosetting resin having such a glass transition temperature, the effect of further improving the lead-free solder reflow heat resistance can be obtained.

Specific thermosetting resins include, for example, novolac type phenolic resins such as phenol novolak resin, cresol novolac resin, bisphenol A novolak resin, unmodified resole phenolic resin, oil modified resole modified with tung oil, linseed oil, walnut oil, etc. Phenol resin such as phenolic resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol Bisphenol type epoxy resin such as Z type epoxy resin, novolak type epoxy resin such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, biffe Type epoxy resin, biphenyl aralkyl type epoxy resin, aryl alkylene type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene Type epoxy resin, epoxy resin, urea (urea) resin, resin having triazine ring such as melamine resin, unsaturated polyester resin, bismaleimide resin, polyurethane resin, diallyl phthalate resin, silicone resin, resin having benzoxazine ring, Examples include cyanate resin, polyimide resin, polyamideimide resin, and benzocyclobutene resin.
One of these may be used alone, two or more having different weight average molecular weights may be used in combination, and one or two or more thereof and a prepolymer thereof may be used in combination.

  Among these, cyanate resins (including prepolymers of cyanate resins) are preferable. By using cyanate resin, the linear expansion coefficient of the resin substrate 100 can be reduced. Further, the cyanate resin is excellent in electrical characteristics (low dielectric constant, low dielectric loss tangent), mechanical strength, and the like.

  Examples of the cyanate resin that can be used include those obtained by reacting a cyanogen halide compound with phenols, and those obtained by prepolymerization by a method such as heating as required. Specifically, bisphenol cyanate resins such as novolac type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, tetramethylbisphenol F type cyanate resin, naphthol aralkyl type polyvalent naphthols, and cyanogen halides Cyanate resin, dicyclopentadiene-type cyanate resin, biphenylalkyl-type cyanate resin, and the like obtained by the above reaction. Among these, novolac type cyanate resin is preferable. By using the novolac type cyanate resin, the crosslink density is increased and the heat resistance is improved. Therefore, the flame retardance of the resin substrate 100 and the like can be improved.

The reason for this is that the novolak cyanate resin forms a triazine ring after the curing reaction. Furthermore, it is considered that novolak-type cyanate resin has a high benzene ring ratio due to its structure and is easily carbonized. Furthermore, even when the thickness of the insulating resin layer is 0.6 mm or less, the resin substrate 100 manufactured by curing the novolac-type cyanate resin has excellent rigidity. In particular, since such a resin substrate 100 is excellent in rigidity during heating, it is also excellent in reliability when mounting a semiconductor element.
As a novolak-type cyanate resin, what is shown by the following general formula (I) can be used, for example.

  The average repeating unit n of the novolak type cyanate resin represented by the general formula (I) is an arbitrary integer. The lower limit of n is not particularly limited, but is preferably 1 or more, and particularly preferably 2 or more. When n is not less than the above lower limit, the heat resistance of the novolak-type cyanate resin is improved, and it is possible to suppress desorption and volatilization of the low monomer during heating. The upper limit of n is not particularly limited, but is preferably 10 or less, particularly preferably 7 or less. It can suppress that a melt viscosity becomes it high that n is below the said upper limit, and can suppress that the moldability of an insulating resin layer falls.

  As the cyanate resin, a naphthol type cyanate resin represented by the following general formula (II) is also preferably used. The naphthol type cyanate resin represented by the following general formula (II) includes naphthols such as α-naphthol or β-naphthol, p-xylylene glycol, α, α′-dimethoxy-p-xylene, 1,4-di ( It is obtained by condensing naphthol aralkyl resin obtained by reaction with 2-hydroxy-2-propyl) benzene and cyanic acid. In the general formula (II), n is more preferably 10 or less. When n is 10 or less, the resin viscosity does not increase, the impregnation property to the fiber base material is good, and the performance as the resin substrate 100 tends not to deteriorate. In addition, intramolecular polymerization hardly occurs at the time of synthesis, the liquid separation property at the time of washing with water tends to be improved, and the decrease in yield tends to be prevented.

（式中、Ｒは水素原子またはメチル基を示し、ｎは１以上の整数を示す。）

(In the formula, R represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more.)

  As the cyanate resin, a dicyclopentadiene type cyanate resin represented by the following general formula (III) is also preferably used. In the dicyclopentadiene type cyanate resin represented by the following general formula (III), n in the following general formula (III) is more preferably 0 or more and 8 or less. When n is 8 or less, the resin viscosity is not high, the impregnation property to the fiber base material is good, and the performance as the resin substrate 100 can be prevented from being lowered. Moreover, by using a dicyclopentadiene type cyanate resin, it is excellent in low hygroscopicity and chemical resistance.

（ｎは０以上８以下の整数を示す。）

(N represents an integer of 0 or more and 8 or less.)

Although the minimum of the weight average molecular weight (Mw) of cyanate resin is not specifically limited, Mw500 or more is preferable and especially Mw600 or more is preferable. When Mw is equal to or more than the above lower limit value, it is possible to suppress the occurrence of tackiness when the insulating resin layer is produced, and to suppress the adhesion of the insulating resin layers to each other or the transfer of the resin. be able to. The upper limit of Mw is not particularly limited, but is preferably Mw 4,500 or less, and particularly preferably Mw 3,000 or less. Moreover, when Mw is equal to or less than the above upper limit value, it is possible to suppress the reaction from being accelerated, and it is possible to suppress the occurrence of molding defects and the decrease in interlayer peel strength when the printed wiring board is used.
Mw such as cyanate resin can be measured by, for example, GPC (gel permeation chromatography, standard substance: converted to polystyrene).

  Moreover, although it does not specifically limit, cyanate resin may be used individually by 1 type, may use together 2 or more types which have different Mw, and uses 1 type or 2 types and those prepolymers together. May be.

  The content of the thermosetting resin contained in the resin material is not particularly limited as long as it is appropriately adjusted according to the purpose, but is preferably 5% by mass or more and 90% by mass or less based on the entire resin material, and further 10 The mass% is preferably 80% by mass or less, and particularly preferably 20% by mass or more and 50% by mass or less. When the content of the thermosetting resin is not less than the above lower limit value, handling properties are improved, and it becomes easy to form an insulating resin layer. When the content of the thermosetting resin is not more than the above upper limit, the strength and flame retardancy of the insulating resin layer are improved, the linear expansion coefficient of the insulating resin layer is reduced, and the warping reduction effect of the semiconductor device is improved. Sometimes.

  In addition to using cyanate resin (particularly novolak-type cyanate resin, naphthol-type cyanate resin, dicyclopentadiene-type cyanate resin) as a thermosetting resin, an epoxy resin (substantially free of halogen atoms) may be used, You may use together. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol Z type epoxy resin and the like. Type epoxy resin, phenol novolac type epoxy resin, novolac type epoxy resin such as cresol novolac type epoxy resin, arylphenyl type epoxy resin such as biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol type epoxy resin, Naphthalenediol type epoxy resin, bifunctional or tetrafunctional epoxy type naphthalene resin, naphthylene ether type epoxy resin, binaphthyl type epoxy resin Naphthalene type epoxy resins such as xylic resin, naphthalene aralkyl type epoxy resin, anthracene type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, etc. .

  As an epoxy resin, one of these may be used alone, or two or more having different weight average molecular weights may be used in combination, or one or two or more and those prepolymers may be used in combination. May be.

  Among these epoxy resins, naphthalene type epoxy resins are particularly preferable. Thereby, moisture-absorbing solder heat resistance and flame retardance can be further improved.

  Examples of naphthalene type epoxy resins include naphthol type epoxy resins, naphthalene diol type epoxy resins, bifunctional to tetrafunctional epoxy type naphthalene resins, and naphthylene ether type epoxy resins. Thereby, heat resistance and low thermal expansibility can further be improved. In addition, since the naphthalene ring has a higher π-π stacking effect than a benzene ring, it is particularly excellent in low thermal expansion and low thermal shrinkage. Furthermore, since the polycyclic structure has a high rigidity effect and the glass transition temperature is particularly high, the change in heat shrinkage before and after reflow is small. As a naphthol type epoxy resin, for example, the following general formula (VII-1), as a naphthalene diol type epoxy resin, the following formula (VII-2), as a bifunctional or tetrafunctional epoxy type naphthalene resin, the following formula (VII-3): As (VII-4) (VII-5) and a naphthylene ether type epoxy resin, it can show by the following general formula (VII-6), for example. Among these, naphthylene ether type epoxy resins are particularly preferable from the viewpoints of flame retardancy, heat resistance, high glass transition temperature, and low thermal expansion.

（ｎは平均１以上６以下の数を示し、Ｒはグリシジル基または炭素数１以上１０以下の炭化水素基を示す。）

(N represents an average number of 1 to 6, and R represents a glycidyl group or a hydrocarbon group having 1 to 10 carbon atoms.)

（式中、Ｒ^１は水素原子またはメチル基を表し、Ｒ^２はそれぞれ独立的に水素原子、炭素原子数１〜４のアルキル基、アラルキル基、ナフタレン基、またはグリシジルエーテル基含有ナフタレン基を表し、ｏおよびｍはそれぞれ０〜２の整数であって、かつｏまたはｍのいずれか一方は１以上である。）

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aralkyl group, a naphthalene group, or a glycidyl ether group-containing naphthalene group. , O and m are each an integer of 0 to 2, and either o or m is 1 or more.)

Furthermore, as an epoxy resin other than the above, an aryl alkylene type epoxy resin is preferable.
The aryl alkylene type epoxy resin refers to an epoxy resin having one or more aryl alkylene groups in a repeating unit. For example, a xylylene type epoxy resin, a biphenyl dimethylene type epoxy resin, etc. are mentioned. Among these, a biphenyl dimethylene type epoxy resin is preferable. A biphenyl dimethylene type | mold epoxy resin can be shown, for example with the following general formula (IV).

  The average repeating unit n of the biphenyl dimethylene type epoxy resin represented by the general formula (IV) is an arbitrary integer. The lower limit of n is not particularly limited, but is preferably 1 or more, and particularly preferably 2 or more. When n is not less than the above lower limit, crystallization of the biphenyldimethylene type epoxy resin can be suppressed and the solubility in a general-purpose solvent is improved, so that handling becomes easy. The upper limit of n is not particularly limited, but is preferably 10 or less, and particularly preferably 5 or less. When n is less than or equal to the above upper limit, the fluidity of the resin is improved and the occurrence of molding defects and the like can be suppressed.

  As the epoxy resin other than the above, a novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure is preferable. Thereby, heat resistance and low thermal expansibility can further be improved.

  The novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure is a novolak type epoxy resin having a naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, triphenylene, and tetraphen or other condensed ring aromatic hydrocarbon structure. . The novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure is excellent in low thermal expansion because a plurality of aromatic rings can be regularly arranged. Moreover, since the glass transition temperature is also high, it is excellent in heat resistance. Furthermore, since the molecular weight of the repeating structure is large, it is superior in flame retardancy as compared with conventional novolac type epoxy resins, and the weakness of the weakness of the cyanate resin can be improved by combining with the cyanate resin. Therefore, when used in combination with a cyanate resin, the glass transition temperature is further increased, so that the lead-free compatible mounting reliability is excellent.

  The novolak-type epoxy resin having a condensed ring aromatic hydrocarbon structure is obtained by epoxidizing a novolak-type phenol resin synthesized from a phenol compound, a formaldehyde compound, and a condensed ring aromatic hydrocarbon compound.

  The phenol compound is not particularly limited, but examples thereof include cresols such as phenol, o-cresol, m-cresol, and p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2, 6-xylenol, 3,4-xylenol, xylenols such as 3,5-xylenol, trimethylphenols such as 2,3,5 trimethylphenol, ethyl such as o-ethylphenol, m-ethylphenol, p-ethylphenol Phenols, alkylphenols such as isopropylphenol, butylphenol, t-butylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene , 2,7-naphthalene diols such as dihydroxynaphthalene, resorcinol, catechol, hydroquinone, pyrogallol, polyhydric phenols such as fluoro Guru Singh, alkyl resorcinol, alkyl catechol, alkyl polyhydric phenols such as alkyl hydroquinone. Of these, phenol is preferable from the viewpoint of cost and the effect on the decomposition reaction.

  The aldehyde compound is not particularly limited, and examples thereof include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, Examples include benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, dihydroxybenzaldehyde, trihydroxybenzaldehyde, 4-hydroxy-3-methoxyaldehyde paraformaldehyde and the like.

  Although the condensed ring aromatic hydrocarbon compound is not particularly limited, for example, naphthalene derivatives such as methoxynaphthalene and butoxynaphthalene, anthracene derivatives such as methoxyanthracene, phenanthrene derivatives such as methoxyphenanthrene, other tetracene derivatives, chrysene derivatives, pyrene derivatives, Derivatives such as triphenylene and tetraphen derivatives are mentioned.

  The novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure is not particularly limited. For example, methoxynaphthalene-modified ortho-cresol novolak epoxy resin, butoxynaphthalene-modified meta (para) cresol novolak epoxy resin, and methoxynaphthalene-modified novolak epoxy resin Etc. Among these, a novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure represented by the following formula (V) is preferable.

(In the formula, Ar is a condensed ring aromatic hydrocarbon group, R may be the same or different from each other, and is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen element, a phenyl group, A group selected from an aryl group such as a benzyl group and an organic group containing a glycidyl ether, n, p and q are integers of 1 or more, and the values of p and q may be the same for each repeating unit, May be different.)

(Ar in the formula (V) is a structure represented by (Ar1) to (Ar4) in the formula (VI), and Rs in the formula (VI) may be the same or different from each other. It is often a group selected from a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogen element, an aryl group such as a phenyl group and a benzyl group, and an organic group including glycidyl ether.)

  Although the minimum of content of an epoxy resin is not specifically limited, 1 mass% or more is preferable in the whole resin material, and 2 mass% or more is especially preferable. When the content is not less than the above lower limit, the reactivity with the cyanate resin is improved, and the moisture resistance of the resulting product can be improved. Although the upper limit of content of an epoxy resin is not specifically limited, 55 mass% or less is preferable and especially 40 mass% or less is preferable. Heat resistance can be improved more as content is below the said upper limit.

  Although the minimum of the weight average molecular weight (Mw) of an epoxy resin is not specifically limited, Mw500 or more is preferable and especially Mw800 or more is preferable. It can suppress that tackiness arises in a resin layer as Mw is more than the said lower limit. The upper limit of Mw is not particularly limited, but is preferably Mw 20,000 or less, and particularly preferably Mw 15,000 or less. When the Mw is not more than the above upper limit value, the impregnation property to the fiber base material is improved during the production of the insulating resin layer, and a more uniform product can be obtained. The Mw of the epoxy resin can be measured by GPC, for example.

  Cyanate resins (especially novolak-type cyanate resins, naphthol-type cyanate resins, dicyclopentadiene-type cyanate resins) and epoxy resins (naphthalene-type epoxy resins, arylalkylene-type epoxy resins, biphenyldimethylene-type epoxy resins, condensed rings) as thermosetting resins In the case of using a novolac type epoxy resin having an aromatic hydrocarbon structure (particularly a naphthylene ether type epoxy resin), it is preferable to use a phenol resin. Examples of the phenol resin include novolac type phenol resins, resol type phenol resins, aryl alkylene type phenol resins, and the like. As a phenol resin, one of these may be used alone, two or more having different weight average molecular weights may be used in combination, and one or two or more thereof and a prepolymer thereof may be used in combination. May be. Among these, aryl alkylene type phenol resins are particularly preferable. Thereby, moisture absorption solder heat resistance can be improved further.

  Examples of the aryl alkylene type phenol resin include a xylylene type phenol resin and a biphenyl dimethylene type phenol resin. A biphenyl dimethylene type phenol resin can be shown by the following general formula (VIII), for example.

  The repeating unit n of the biphenyldimethylene type phenol resin represented by the general formula (VIII) is an arbitrary integer. The lower limit of n is not particularly limited, but is preferably 1 or more, and particularly preferably 2 or more. Heat resistance can be improved more as n is more than the said lower limit. Further, the upper limit of the repeating unit n is not particularly limited, but is preferably 12 or less, particularly preferably 8 or less. Moreover, compatibility with other resin improves that n is below the said upper limit, and workability | operativity can be improved.

  Cyanate resin (especially novolak-type cyanate resin, naphthol-type cyanate resin, dicyclopentadiene-type cyanate resin) and epoxy resin (naphthalene-type epoxy resin, arylalkylene-type epoxy resin, biphenyldimethylene-type epoxy resin, condensed ring aromatic carbonization) The combination of a novolak type epoxy resin having a hydrogen structure, particularly a naphthylene ether type epoxy resin) and an arylalkylene type phenol resin can control the crosslinking density and easily control the reactivity.

  Although the minimum of content of a phenol resin is not specifically limited, 1 mass% or more is preferable in the whole resin material, and 5 mass% or more is especially preferable. Heat resistance can be improved as content of a phenol resin is more than the said lower limit. Moreover, the upper limit of content of a phenol resin is not specifically limited, However, 55 mass% or less is preferable in the whole resin material, and 40 mass% or less is especially preferable. When the content of the phenol resin is not more than the above upper limit value, the characteristics of low thermal expansion can be improved.

  Although the minimum of the weight average molecular weight (Mw) of a phenol resin is not specifically limited, Mw400 or more is preferable and especially Mw500 or more is preferable. It can suppress that tackiness arises in a resin layer as Mw is more than the said minimum. Moreover, the upper limit of Mw of the phenol resin is not particularly limited, but Mw is preferably 18,000 or less, and particularly preferably Mw 15,000 or less. When the Mw is not more than the above upper limit, the impregnation property to the fiber base material is improved during the production of the resin layer, and a more uniform product can be obtained. The Mw of the phenol resin can be measured by GPC, for example.

  Furthermore, cyanate resins (especially novolac-type cyanate resins, naphthol-type cyanate resins, dicyclopentadiene-type cyanate resins) and phenol resins (arylalkylene-type phenol resins, especially biphenyldimethylene-type phenol resins) and epoxy resins (naphthalene-type epoxy resins, Fabrication of substrates (especially printed wiring boards) using combinations of aryl alkylene type epoxy resins, biphenyl dimethylene type epoxy resins, novolac type epoxy resins having a condensed ring aromatic hydrocarbon structure, especially naphthylene ether type epoxy resins) In particular, excellent dimensional stability can be obtained.

  The resin material may further include a filler. Thereby, even if the resin substrate 100 is thinned, it is possible to impart even more excellent mechanical strength. Furthermore, the low thermal expansion of the resin substrate 100 can be further improved.

(Filler)
Examples of fillers include silicates such as talc, calcined clay, unfired clay, mica and glass, oxides such as titanium oxide, alumina, silica and fused silica, and carbonates such as calcium carbonate, magnesium carbonate and hydrotalcite. Salts, hydroxides such as aluminum hydroxide, magnesium hydroxide, boehmite, calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite, zinc borate, barium metaborate, aluminum borate, boron Examples thereof include borates such as calcium oxide and sodium borate, nitrides such as aluminum nitride, boron nitride, silicon nitride, and carbon nitride, and titanates such as strontium titanate and barium titanate.

  As the filler, one of these may be used alone, or two or more may be used in combination. Among these, those with a small amount of generated gas (gas) are preferable. For example, talc, boehmite, and silica are preferable, and fused silica (especially spherical fused silica) is particularly preferable in terms of excellent low thermal expansion. The fused silica has a crushed shape and a spherical shape. In order to ensure the impregnation property to the fiber base material, it is possible to adopt a usage method suitable for the purpose, such as using spherical silica to lower the melt viscosity of the resin material.

  Although the minimum of the average particle diameter of a filler is not specifically limited, 0.01 micrometer or more is preferable and especially 0.1 micrometer or more is preferable. It can suppress that the viscosity of a varnish becomes high as the particle size of a filler is the said lower limit or more, and the workability | operativity at the time of prepreg preparation can be improved. The upper limit of the average particle size is not particularly limited, but is preferably 5.0 μm or less, and particularly preferably 2.0 μm or less. When the particle size of the filler is not more than the above upper limit, phenomena such as sedimentation of the filler in the varnish can be suppressed, and a more uniform resin layer can be obtained. In addition, when the L / S of the conductor circuit of the inner layer substrate is less than 20/20 μm, it is possible to suppress the influence on the insulation between the wirings.

The average particle size of the filler is measured, for example, by measuring the particle size distribution of the particles on a volume basis using a laser diffraction particle size distribution measuring device (manufactured by HORIBA, LA-500), and the median diameter (D ₅₀ ) is defined as the average particle size. To do.

  Further, the filler is not particularly limited, but a monodisperse filler having an average particle diameter may be used, or a polydisperse filler having an average particle diameter may be used. Furthermore, a monodispersed and / or polydispersed filler having an average particle size may be used alone or in combination of two or more.

The resin material of the present embodiment preferably includes a nanosilica less than the median diameter d ₅₀ of 100 nm (particularly spherical nanosilica) a volume-based particle size distribution by a laser diffraction scattering particle size distribution measuring method. Since the said nano silica can exist in the clearance gap of a filler with a large particle size, or the strand of a fiber base material, the filling property of a filler can further be improved by containing nano silica.

  Although content of a filler is not specifically limited, 20 mass% or more and 80 mass% or less are preferable in the whole resin material, and 30 mass% or more and 75 mass% or less are especially preferable. When the content is within the above range, particularly low thermal expansion and low water absorption can be achieved.

  Moreover, the resin material used for this Embodiment can also mix | blend a rubber component, for example, a rubber particle can be used. Preferable examples of the rubber particles include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles, and silicone particles.

  The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, a two-layer structure in which an outer shell layer is formed of a glassy polymer and an inner core layer is formed of a rubbery polymer, or Examples include a three-layer structure in which the outer shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer. The glassy polymer layer is made of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber). Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N (trade names, manufactured by Ganz Kasei Co., Ltd.), and Metabrene KW-4426 (trade names, manufactured by Mitsubishi Rayon Co., Ltd.). Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle size: 0.5 μm, manufactured by JSR).

  Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 (average particle size 0.5 μm, manufactured by JSR). Specific examples of the acrylic rubber particles include methabrene W300A (average particle size 0.1 μm), W450A (average particle size 0.2 μm) (manufactured by Mitsubishi Rayon Co., Ltd.), and the like.

  The silicone particles are not particularly limited as long as they are rubber elastic fine particles formed of organopolysiloxane. For example, fine particles made of silicone rubber (organopolysiloxane crosslinked elastomer) itself and a core portion made of silicone mainly composed of two-dimensional crosslinks. Examples thereof include core-shell structure particles coated with silicone mainly composed of a three-dimensional crosslinking type. As silicone rubber fine particles, commercially available products such as KMP-605, KMP-600, KMP-597, KMP-594 (manufactured by Shin-Etsu Chemical Co., Ltd.), Trefil E-500, Trefil E-600 (manufactured by Toray Dow Corning) Can be used.

  Although the content of the rubber particles is not particularly limited, it is preferably 20% by mass or more and 80% by mass or less, and particularly preferably 30% by mass or more and 75% by mass or less based on the entire resin material including the above fillers. When the content is within the range, particularly low water absorption can be achieved.

(Other additives)
In addition, additives such as a coupling agent, a curing accelerator, a curing agent, a thermoplastic resin, and an organic filler can be appropriately blended in the resin material as necessary. The resin material used in the present embodiment can be suitably used in a liquid form in which the above components are dissolved and / or dispersed with an organic solvent or the like.

  By using the coupling agent, the wettability of the interface between the thermosetting resin and the filler is improved, and the resin material can be uniformly fixed to the fiber base material. Therefore, it is preferable to use a coupling agent, and heat resistance, particularly solder heat resistance after moisture absorption can be improved.

  As the coupling agent, any of those usually used as a coupling agent can be used. Specifically, an epoxy silane coupling agent, a cationic silane coupling agent, an aminosilane coupling agent, a titanate coupling agent, and silicone. It is preferable to use one or more coupling agents selected from oil-type coupling agents. Thereby, the wettability with the interface of a filler can be made high, and thereby heat resistance can be improved more.

  The lower limit of the addition amount of the coupling agent is not particularly limited because it depends on the specific surface area of the filler, but is preferably 0.05 parts by mass or more, particularly 0.1 parts by mass or more with respect to 100 parts by mass of the filler. A filler can fully be coat | covered as content of a coupling agent is more than the said lower limit, and heat resistance can be improved. The upper limit of the amount added is not particularly limited, but is preferably 3 parts by mass or less, and particularly preferably 2 parts by mass or less. When the content is not more than the above upper limit value, it is possible to suppress the influence on the reaction, and it is possible to suppress a decrease in bending strength and the like.

A well-known thing can be used as a hardening accelerator. For example, organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, zinc octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III), triethylamine, tributylamine, Tertiary amines such as diazabicyclo [2,2,2] octane, 2-phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, 2-phenyl-4-ethylimidazole, 2-phenyl-4-methyl Imidazoles such as -5-hydroxyimidazole and 2-phenyl-4,5-dihydroxyimidazole, phenolic compounds such as phenol, bisphenol A and nonylphenol, organic acids such as acetic acid, benzoic acid, salicylic acid and paratoluenesulfonic acid, oni A salt compound, or a mixture thereof. As the curing accelerator, one kind including these derivatives may be used alone, or two or more kinds including these derivatives may be used in combination.
The onium salt compound is not particularly limited, and for example, an onium salt compound represented by the following general formula (IX) can be used.

(In the formula, P represents a phosphorus atom, R ¹ , R ² , R ³ and R ⁴ each represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. A ⁻ may be the same as or different from each other, and A ⁻ is an anion of an n (n ≧ 1) -valent proton donor having at least one proton that can be released to the outside of the molecule, or a complex anion thereof. Is shown.)

  Although the minimum of content of a hardening accelerator is not specifically limited, 0.005 mass% or more of the whole resin material is preferable, and 0.008 mass% or more is especially preferable. When the content is not less than the above lower limit, the effect of promoting curing can be sufficiently exerted. The upper limit of the content is not particularly limited, but is preferably 5% by mass or less, and particularly preferably 2% by mass or less, based on the entire resin material. The preservability of a prepreg can be improved more as content is below the said upper limit.

  Resin materials include phenoxy resin, polyimide resin, polyamideimide resin, polyphenylene oxide resin, polyethersulfone resin, polyester resin, polyethylene resin, polystyrene resin and other thermoplastic resins, styrene-butadiene copolymer, styrene-isoprene copolymer. In addition, thermoplastic elastomers such as polystyrene-based thermoplastic elastomers, polyolefin-based thermoplastic elastomers, polyamide-based elastomers, and polyester-based elastomers, and diene-based elastomers such as polybutadiene, epoxy-modified polybutadiene, acrylic-modified polybutadiene, and methacryl-modified polybutadiene are used in combination. May be.

  Examples of the phenoxy resin include a phenoxy resin having a bisphenol skeleton, a phenoxy resin having a naphthalene skeleton, a phenoxy resin having an anthracene skeleton, and a phenoxy resin having a biphenyl skeleton. A phenoxy resin having a structure having a plurality of these skeletons can also be used.

Among these, it is preferable to use a phenoxy resin having a biphenyl skeleton and a bisphenol S skeleton as the phenoxy resin. Thereby, the glass transition temperature of the phenoxy resin can be increased due to the rigidity of the biphenyl skeleton, and the adhesion between the phenoxy resin and the metal can be improved due to the presence of the bisphenol S skeleton. As a result, the heat resistance of the resin substrate can be improved, and the adhesion of the wiring layer to the resin substrate can be improved when the printed wiring board is manufactured. It is also preferable to use a phenoxy resin having a bisphenol A skeleton and a bisphenol F skeleton as the phenoxy resin. Thereby, the adhesiveness to the resin substrate of a wiring layer can be further improved at the time of manufacture of a printed wiring board.
It is also preferable to use a phenoxy resin having a bisphenolacetophenone structure represented by the following general formula (X).

(Wherein R ₁ may be the same or different from each other, and is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a group selected from halogen elements, and R ₂ is a hydrogen atom, carbon It is a group selected from a hydrocarbon group having a number of 1 or more and 10 or less, or a halogen element, R ₃ is a hydrogen atom or a hydrocarbon group having a carbon number of 1 or more and 10 or less, and m is an integer of 0 or more and 5 or less. )

  Since the phenoxy resin containing a bisphenol acetophenone structure has a bulky structure, it is excellent in solvent solubility and compatibility with the thermosetting resin component to be blended. Moreover, since a uniform rough surface can be formed with low roughness, the fine wiring formability is excellent.

  The phenoxy resin having a bisphenol acetophenone structure can be synthesized by a known method such as a method in which an epoxy resin and a phenol resin are polymerized with a catalyst.

  The phenoxy resin having a bisphenol acetophenone structure may contain a structure other than the bisphenol acetophenone structure of the general formula (X), and the structure is not particularly limited, but bisphenol A type, bisphenol F type, bisphenol S type, biphenyl Type, phenol novolac type, cresol novolac type structure and the like. Among them, those containing a biphenyl structure are preferable because of their high glass transition temperature.

  The content of the bisphenol acetophenone structure of the general formula (X) in the phenoxy resin containing a bisphenol acetophenone structure is not particularly limited, but is preferably 5 mol% to 95 mol%, more preferably 10 mol% to 85 mol%. Or less, more preferably 15 mol% or more and 75 mol% or less. The effect which improves heat resistance and moisture-proof reliability can fully be exhibited as content is more than the said lower limit. Moreover, solvent solubility can be improved as content is below the said upper limit.

  The weight average molecular weight (Mw) of the phenoxy resin is not particularly limited, but is preferably from 5,000 to 100,000, more preferably from 10,000 to 70,000, particularly preferably from 20,000 to 50,000. . When Mw is not more than the above upper limit, compatibility with other resins and solubility in a solvent can be improved. When it is at least the above lower limit, the film-forming property is improved, and it is possible to suppress the occurrence of problems when used for the production of a printed wiring board.

  The content of the phenoxy resin is not particularly limited, but is preferably 0.5% by mass or more and 40% by mass or less, and particularly preferably 1% by mass or more and 20% by mass or less of the resin material excluding the filler. When the content is equal to or higher than the lower limit, it is possible to suppress a decrease in mechanical strength of the insulating resin layer and a decrease in plating adhesion with the conductor circuit. When it is not more than the above upper limit, an increase in the coefficient of thermal expansion of the resin substrate 100 can be suppressed, and the heat resistance can be lowered.

  In addition, additives other than the above components such as pigments, dyes, antifoaming agents, leveling agents, UV absorbers, foaming agents, antioxidants, flame retardants, and ion scavengers are added to the resin material as necessary. May be.

  Examples of pigments include kaolin, synthetic iron oxide red, cadmium yellow, nickel titanium yellow, strontium yellow, hydrous chromium oxide, chromium oxide, cobalt aluminate, synthetic ultramarine blue and other inorganic pigments, phthalocyanine polycyclic pigments, azo pigments, etc. Etc.

  Examples of the dye include isoindolinone, isoindoline, quinophthalone, xanthene, diketopyrrolopyrrole, perylene, perinone, anthraquinone, indigoid, oxazine, quinacridone, benzimidazolone, violanthrone, phthalocyanine, and azomethine.

(Fiber base)
Although it does not specifically limit as a fiber base material, Polyamide-type resin fiber base materials, such as glass fiber base materials, such as a glass cloth, polybenzoxazole resin fiber, a polyamide resin fiber, an aromatic polyamide resin fiber, a wholly aromatic polyamide resin fiber Polyester resin fiber base materials such as polyester resin fibers, aromatic polyester resin fibers, wholly aromatic polyester resin fibers, synthetic fiber base materials composed mainly of polyimide resin fibers, fluororesin fibers, kraft paper, cotton Examples thereof include organic fiber base materials such as linter paper and paper base materials mainly composed of linter paper and kraft pulp mixed paper. Among these, a glass fiber substrate is particularly preferable from the viewpoint of strength and water absorption. Moreover, the linear expansion coefficient of the resin substrate 100 can be further reduced by using a glass fiber base material.

The glass fiber substrate used in the present embodiment preferably has a basis weight (weight of the fiber substrate per 1 m ² ) of 4 g / m ² or more and 150 g / m ² or less, and 8 g / m ² or more and 110 g / m. ² or less, more preferably 12 g / m ² or more and 60 g / m ² or less, further preferably 12 g / m ² or more and 30 g / m ² or less, and further preferably 12 g / m ² or more and 24 g / m ² or less. it is particularly preferable that m ² or less.

  When the basis weight is less than or equal to the above upper limit, the impregnation property of the resin material in the glass fiber substrate is improved, and the occurrence of strand voids and a decrease in insulation reliability can be suppressed. In addition, it is possible to easily form a through hole by a laser such as carbon dioxide, UV, or excimer. Moreover, the intensity | strength of a glass fiber base material or a prepreg can be improved as basic weight is more than the said lower limit. As a result, handling properties can be improved, prepreg can be easily produced, and reduction in the warpage reduction effect of the substrate can be suppressed.

  Among the above fiber base materials, it is particularly preferable that the fiber base material has a linear expansion coefficient of −7 ppm / ° C. or more and 10 ppm / ° C. or less calculated in the range of 25 ° C. to 150 ° C., − A fiber base material of 5 ppm / ° C. to 7 ppm / ° C. is more preferable, and a fiber base material of −3 ppm / ° C. to 3 ppm / ° C. is particularly preferable. By using a fiber base material having such a linear expansion coefficient, it is possible to further suppress warping of the resin substrate 100 of the present embodiment.

  Furthermore, the tensile modulus of the material constituting the glass fiber substrate used in the present embodiment is preferably 60 GPa or more and 100 GPa or less, more preferably 65 GPa or more and 95 GPa or less, and particularly preferably 85 GPa or more and 95 GPa or less. preferable. By using a glass fiber base material having such a tensile elastic modulus, for example, deformation of the wiring board due to reflow heat during semiconductor mounting can be effectively suppressed, so that the connection reliability of electronic components is further improved. .

  The glass fiber substrate used in the present embodiment preferably has a dielectric constant at 1 GHz of 3.8 or more and 7.0 or less, more preferably 3.8 or more and 6.8 or less. It is particularly preferably 8 or more and 5.5 or less. By using a glass fiber base material having such a dielectric constant, the dielectric constant of the resin substrate 100 can be further reduced, which is suitable for a semiconductor device using a high-speed signal.

  Glass containing at least one selected from the group consisting of T glass, S glass, E glass, NE glass, and quartz glass, for example, as the glass fiber substrate having the above-described linear expansion coefficient, tensile elastic modulus, and dielectric constant A fiber base material is preferably used.

  Although the thickness of a fiber base material is not specifically limited, Preferably it is 5 micrometers or more and 150 micrometers or less, More preferably, they are 10 micrometers or more and 100 micrometers or less, More preferably, they are 12 micrometers or more and 60 micrometers or less. By using the fiber base material having such a thickness, the handling property at the time of manufacturing the prepreg is further improved, and the warp reduction effect is particularly remarkable.

  When the thickness of the fiber base material is not more than the above upper limit value, the impregnation property of the resin material in the fiber base material is improved, and the occurrence of strand voids and a decrease in insulation reliability can be suppressed. In addition, it is possible to easily form a through hole by a laser such as carbon dioxide, UV, or excimer. Moreover, the intensity | strength of a fiber base material or a prepreg can be improved as the thickness of a fiber base material is more than the said lower limit. As a result, handling properties can be improved, prepreg can be easily produced, and reduction in the warpage reduction effect of the substrate can be suppressed.

  Further, the number of fiber base materials used is not limited to one, and a plurality of thin fiber base materials can be used in a stacked manner. In addition, when using a plurality of fiber base materials in piles, the total thickness only needs to satisfy the above range.

  Moreover, it is preferable that the sum total of the fiber base material and filler contained in the resin substrate 100 in this embodiment is 55 mass% or more and 90 mass% or less, and it is more preferable that it is 70 mass% or more and 85 mass% or less. preferable. When the total of the fiber base material and the filler satisfies the above range, the rigidity of the resin substrate 100 increases while balancing the impregnation property and moldability of the resin material into the fiber base material, and the semiconductor device warps during mounting. Can be further reduced.

  In order to obtain the resin substrate of the present embodiment, it is important to appropriately select each material described above and appropriately adjust the blending amount of each material. However, the resin substrate of this embodiment is not limited to each material mentioned above, The resin substrate of this embodiment can be obtained by adjusting various conditions appropriately.

(Semiconductor package)
Next, the semiconductor package 200 in the present embodiment will be described.
The resin substrate 100 (213) can be used in a semiconductor package 200 as shown in FIG. A method for manufacturing the semiconductor package 200 is not particularly limited, and examples thereof include the following methods.
A through hole 215 for interlayer connection is formed in the resin substrate with metal foil 100 (213), and a wiring layer is manufactured by a subtractive method, a semi-additive method, or the like. Thereafter, build-up layers (not shown in FIG. 7) are stacked as necessary, and the steps of interlayer connection and circuit formation by the additive method are repeated. Then, if necessary, a solder resist layer 201 is laminated and a circuit is formed by a method according to the above, whereby a printed wiring board is obtained. Here, a part or all of the buildup layer and the solder resist layer may or may not include a fiber base material.

  Next, after a photoresist is applied to the entire surface of the solder resist layer 201, a part of the photoresist is removed to expose a part of the solder resist layer 201. Note that a resist having a photoresist function may be used for the solder resist layer 201. In this case, the step of applying a photoresist can be omitted. Next, the exposed solder resist layer is removed to form the opening 209.

  Subsequently, by performing a reflow process, the semiconductor element 203 is fixed to the connection terminal 205 which is a part of the wiring pattern via the solder bump 207. Thereafter, the semiconductor element 203, the solder bump 207, and the like are sealed with a sealing material 211, whereby the semiconductor package 200 as shown in FIG. 7 is obtained.

(Semiconductor device)
Next, the semiconductor device 300 in this embodiment will be described.
The semiconductor package 200 can be used in a semiconductor device 300 as shown in FIG. A method for manufacturing the semiconductor device 300 is not particularly limited, and examples thereof include the following methods.
First, the solder bump 301 is formed by supplying a solder paste to the opening 209 of the solder resist layer 201 of the obtained semiconductor package 200 and performing a reflow process. The solder bump 301 can also be formed by attaching a solder ball prepared in advance to the opening 209.

  Next, the semiconductor package 200 is mounted on the mounting substrate 303 by bonding the connection terminals 305 and the solder bumps 301 of the mounting substrate 303, and the semiconductor device 300 shown in FIG. 8 is obtained.

  As described above, according to the present embodiment, the resin substrate 100 (213) capable of obtaining a semiconductor device with reduced warpage during mounting is provided. In particular, even when the resin substrate 100 (213) is thin, the occurrence of warpage can be effectively suppressed. And the printed wiring board using the resin board | substrate 100 (213) in this embodiment is excellent in mechanical characteristics, such as curvature and dimensional stability, and a moldability. Therefore, the resin substrate 100 (213) in the present embodiment can be suitably used for applications that require reliability, such as a printed wiring board that requires high density and high multilayer.

  In the resin substrate 100 (213) in this embodiment, the occurrence of warpage is reduced in the above-described circuit processing and the subsequent processes. Further, the semiconductor package 200 in the present embodiment is less likely to warp and crack, and can be thinned. Therefore, the semiconductor device 300 including the semiconductor package 200 can improve connection reliability.

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable. For example, in the present embodiment, the case where the prepreg has one layer is shown, but the resin substrate 100 may be manufactured using a laminate of two or more prepregs.
A configuration in which a build-up layer is further laminated on the resin substrate 100 (213) in the present embodiment may be employed.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these. In addition, in an Example, unless otherwise specified, a part represents a mass part. Moreover, each thickness is represented by the average film thickness.

In the examples and comparative examples, the following raw materials were used.
Epoxy resin A: biphenyl aralkyl type novolak epoxy resin (Nippon Kayaku Co., Ltd., NC-3000)
Epoxy resin B: naphthalenediol diglycidyl ether (manufactured by DIC, Epicron HP-4032D)
Epoxy resin C: naphthylene ether type epoxy resin (manufactured by DIC, Epicron HP-6000)
Epoxy resin D: Phosphorus-modified epoxy resin (manufactured by Tohto Kasei Co., Ltd., FX-305EK70, solid content 70% by mass)

Cyanate resin A: Novolac-type cyanate resin (Lonza Japan, Primaset PT-30)
Cyanate resin B: p-xylene-modified naphthol aralkyl type cyanate resin represented by the general formula (II) (naphthol aralkyl type phenol resin (manufactured by Toto Kasei Co., Ltd., “SN-485 derivative”) and cyan chloride)

Phenol resin: Biphenyl dimethylene type phenol resin (manufactured by Nippon Kayaku Co., Ltd., GPH-103)
Amine compound: 4,4′-diaminodiphenylmethane bismaleimide compound (KMI Kasei Kogyo Co., Ltd., BMI-70)

  Phenoxy resin: Phenoxy resin containing a bisphenolacetophenone structure (manufactured by Mitsubishi Chemical Corporation, YX-6594BH30, solid content 30% by weight)

Filler A: Spherical silica (manufactured by Admatechs, SO-25R, average particle size 0.5 μm)
Filler B: Spherical silica (manufactured by Admatechs, SO-31R, average particle size 1.0 μm)
Filler C: Nanosilica (manufactured by Admatechs, Admanano, KBM403E surface treated product, average particle size 65 nm)
Filler D: Boehmite (Navaltech AOH-30)
Filler E: Aluminum hydroxide (Nippon Light Metal Co., Ltd., BE033)
Filler F: Silicone particles (Momentive Performance Materials Japan, Tospearl 120, average particle size 2 μm)

Flame retardant A: Aluminum salt of dialkylphosphinic acid (manufactured by Clariant, OP-930)
Flame retardant B: Aromatic phosphate ester flame retardant (Daihachi Chemical Co., Ltd., PX-200)

Coupling agent A: γ-glycidoxypropyltrimethoxysilane (manufactured by Momentive Performance Materials, A-187)
Coupling agent B: N-phenyl-γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-573)
Curing accelerator A: phosphorus-based catalyst of an onium salt compound corresponding to the above general formula (IX) (C05-MB, manufactured by Sumitomo Bakelite Co., Ltd.)
Curing accelerator B: Zinc octylate

(Example)
The resin substrate in this embodiment was produced using the following procedure.
First, production of a prepreg will be described. The composition of the resin varnish used is shown in Table 1 (solid substance amount%), and the thicknesses and the like of the obtained prepregs 1 to 12 are shown in Table 2. In addition, P1 to P12 described in Tables 2 and 3 mean prepreg 1 to prepreg 12, Unitika described in Table 2 is manufactured by Unitika Glass Fiber, Nittobo is manufactured by Nittobo, and Asahi Kasei is Asahi Kasei. E-materials, Shin-Etsu quartz means Shin-Etsu quartz.

(Prepreg 1)
1. Preparation of resin material varnish 1 As epoxy resin C, naphthylene ether type epoxy resin (manufactured by DIC, Epicron HP-6000) 9.0 parts by mass, amine compound 4,4′-diaminodiphenylmethane 3.0 parts by mass, bis As a maleimide compound, 17.5 parts by mass of bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane (manufactured by Keiai Chemical Industry Co., Ltd., BMI-70) was dissolved and dispersed in methyl ethyl ketone. Further, spherical silica (manufactured by Admatechs, SO-31R, average particle size 1.0 μm) 63.0 parts by mass as filler B, and nanosilica (manufactured by Admatechs, Admanano, KBM403E surface-treated product, average) as filler C Particle size 65 nm) 2.0 parts by weight, filler D as boehmite (Navaltech, AOH-30) 5.0 parts by weight and coupling agent A as γ-glycidoxypropyltrimethoxysilane (momentive performance) -Materials Co., Ltd., A-187) 0.5 mass part was added, it stirred for 30 minutes using a high-speed stirring apparatus, and it adjusted so that it might become 70 mass% of non-volatile matters, and varnish 1 ( Resin varnish 1) was prepared.

2. Manufacture of prepreg (prepreg 1)
A glass fiber substrate (91 μm thick, E glass woven fabric manufactured by Unitika, E10C, IPC standard 2118, linear expansion coefficient: 5.8 ppm / ° C.) is impregnated with resin varnish 1 using a coating apparatus, and a heating furnace at 180 ° C. And dried for 2 minutes to obtain 100 μm of prepreg 1 (P1).

(Prepreg 2-12)
Prepregs 2 to 12 were produced in the same manner as prepreg 1 except that the type of resin varnish and the type of fiber substrate were changed as shown in Tables 1 and 2.

Example 1
1. Production of Resin Substrate Ultra-thin copper foil (Mitsui Metal Mining Co., Ltd., Micro Thin Ex, 1.5 μm) is superimposed on both surfaces of four prepregs 1 and heated and pressed at 220 ° C. and 3.0 MPa for 2 hours. As a result, a resin substrate was obtained. The thickness of the core layer (part consisting of the resin substrate) of the obtained resin substrate with metal foil was 0.40 mm.

2. Manufacture of printed wiring board Inner layer circuit using the resin substrate with metal foil obtained above as a core substrate, and forming a fine circuit pattern on both sides by a semi-additive method (residual copper ratio 70%, L / S = 25/25 μm) A substrate was produced. A buildup material (BLA-3700GS manufactured by Sumitomo Bakelite Co., Ltd.) was laminated on both surfaces by vacuum lamination, and then heat-cured at 175 ° C. for 60 minutes with a hot air drying apparatus. Next, after peeling off the supporting substrate, blind via holes (non-through holes) were formed by a carbonic acid laser. Next, the inside of the via is immersed in a 60 ° C. swelling liquid (Atotech Japan Co., Swelling Dip Securigant P) for 5 minutes, and further an 80 ° C. potassium permanganate aqueous solution (Atotech Japan Co., Concentrate Compact CP). After 20 minutes of soaking, it was neutralized and roughened.

  After passing through the steps of degreasing, applying a catalyst, and activating this, an electroless copper plating film is formed to a thickness of about 0.5 μm, a plating resist is formed, and electroless copper plating film is used as a power supply layer to form a pattern electroplated copper of 20 μm , L / S = 15/15 μm fine circuit processing was performed. Next, after performing an annealing process at 200 ° C. for 60 minutes with a hot air drying apparatus, the power feeding layer was removed by flash etching.

  Next, the solder resist layer was laminated | stacked, and it exposed so that a semiconductor element mounting pad etc. might be exposed then. Then it was developed and opened.

  Finally, on the circuit layer exposed from the solder resist layer, the electroless nickel plating layer 3 μm, and further, the electroless gold plating layer 0.1 μm and then the solder plating layer 5 μm are formed, The obtained board | substrate was cut | disconnected to 50 mm x 50 mm size, and the printed wiring board for semiconductor packages was obtained.

3. Production of Semiconductor Package On the obtained printed wiring board, a semiconductor element (TEG chip, size 15 mm × 15 mm, thickness 300 μm) having solder bumps was mounted by thermocompression bonding using a flip chip bonder device. Next, after melt-bonding the solder bumps in an IR reflow furnace, a liquid sealing resin (manufactured by Sumitomo Bakelite Co., Ltd., CRP-X4800B) was filled and the liquid sealing resin was cured to obtain a semiconductor package. The liquid sealing resin was cured at a temperature of 150 ° C. for 120 minutes. Moreover, the solder bump of the semiconductor element used what was formed with the lead free solder of Sn / Ag / Cu composition.

(Examples 2-8, Comparative Examples 1-4)
Resin substrates and semiconductor packages were produced in the same manner as in Example 1 except that the type of prepreg was changed.

  The following evaluations were performed on the resin substrates and semiconductor packages obtained in the examples and comparative examples. Each evaluation is shown below together with the evaluation method. The obtained results are shown in Table 3.

(1) Glass transition temperature The glass transition temperature was measured by dynamic viscoelasticity measurement (DMA).
A test piece of 8 mm × 40 mm was cut out from the obtained resin substrate, and measured using a DMA 2980 manufactured by TA Instruments at a heating rate of 5 ° C./min and a frequency of 1 Hz. The glass transition temperature was a temperature at which tan δ had a maximum value at a frequency of 1 Hz.

(2) Linear expansion coefficient The test piece of 4 mm x 15 mm resin substrate produced in the Example was cut out, and the copper foil was removed with an etching solution (ferric chloride solution, 35 ° C). Subsequently, the linear expansion coefficient in the range of 25 ° C. to 150 ° C. was calculated under a pulling condition of 10 ° C./min using a thermomechanical analyzer TMA (manufactured by TA Instruments, Q400).

(3) 1% weight reduction temperature of resin substrate Using a differential thermothermal gravimetric simultaneous measurement device (Seiko Instruments Inc., TG / DTA6200 type), under a dry nitrogen stream under a temperature rising rate of 10 ° C / min, The temperature at which the resin substrate was reduced by 1% was calculated by raising the temperature of the resin substrates prepared in the examples and comparative examples from 30 ° C. to 650 ° C. In addition, the sample used what dried for 1 hour at 110 degreeC before the measurement.

(4) Multi-Reflow of Printed Wiring Board The printed wiring board obtained above is repeatedly passed through a 260 ° C. reflow furnace in accordance with IPC / JEDEC J-STD-20, and is visually or ultrasonically removed every 5 times. Peeling and cracking of the insulating layer of the printed wiring board were evaluated with a scratch inspection apparatus.
Each code is as follows.
A: There is no peeling of the insulating layer 15 times or more, or copper penetration failure.
○: Exfoliation of the insulating layer or the like or copper penetration failure occurred 5 times or more and less than 15 times.
X: Less than 5 times Insulation layer peeling or copper defect occurred.

(5) Warpage amount of the semiconductor package The warpage amount of the semiconductor package is placed on the substrate (size: 50 mm × 50 mm) from the BGA surface in an atmosphere of 25 ° C. and 260 ° C. with the chip surface placed in a chamber that can be heated and cooled. The change in the amount of warpage in the 48 mm × 48 mm portion of was measured. In addition, the semiconductor package produced by the said Example and the comparative example was used for the sample. Each code is as follows.
(Double-circle): The change of the curvature amount was less than 250 micrometers (good).
◯: The change in warpage amount was 250 μm or more and less than 300 μm (substantially no problem).
X The amount of warpage was 300 μm or more (problematic).

(6) Continuity test Circuit terminals that pass between the semiconductor element and the printed wiring board through solder bumps using the flying checker (1116X-YC Hitester: manufactured by Hioki Electric Co., Ltd.) for the three semiconductor packages produced in the examples and comparative examples. The continuity was measured and set as the initial value. Next, after treatment for 40 hours at 60 ° C. and 60% moisture absorption, treatment was performed three times in an IR reflow furnace (peak temperature: 260 ° C.), and the continuity was measured in the same manner, and the resistance value was 5% or more from the initial value. The rise was determined to be a disconnection during mounting. Here, when the disconnection has occurred at the initial value, it is determined that it is a malfunction in circuit fabrication and is not counted. In addition, the measurement location was 61 locations per semiconductor package, and a total of 183 locations were measured.
Each code is as follows.
(Double-circle): There was no disconnection location.
○: The disconnection portion was 1% or more and less than 11%.
(Triangle | delta): The disconnection location was 11% or more and less than 51%.
X: The disconnection location was 51% or more.

(7) Temperature cycle (TC) test Four semiconductor packages produced in the examples and comparative examples were treated for 40 hours under conditions of 60 ° C and 60%, and then treated three times in an IR reflow furnace (peak temperature: 260 ° C). And 500 cycles at −55 ° C. (15 minutes) and 125 ° C. (15 minutes) in the atmosphere. Next, using an ultrasonic imaging apparatus (manufactured by Hitachi Construction Machinery Finetech Co., Ltd., FS300), the semiconductor element and the solder bump were observed for abnormalities.
A: No abnormality in both semiconductor element and solder bump.
○: Cracks are seen in a part of the semiconductor element and / or solder bump, but there is no practical problem.
(Triangle | delta): A crack is seen in a part of semiconductor element and / or a solder bump, and there is a problem in practical use.
X: Both the semiconductor element and the solder bump are cracked and cannot be used.

DESCRIPTION OF SYMBOLS 100 Resin substrate 101 Fiber base material 103 Insulating resin layer 5a Carrier material 5b Carrier material 11 Fiber base material 21 Prepreg 60 Vacuum laminating device 61 Laminating roll 62 Hot air drying device 13 Support base material 15a Resin layer 15b Resin layer 1 Coating device 1a First 1 coating device 1b second coating device 2 coating tip 2a first coating tip 2b second coating tip 3 fiber substrate 4 resin varnish 200 semiconductor package 201 solder resist layer 203 semiconductor element 205 connection terminal 207 Solder bump 209 Opening 211 Sealing material 213 Resin substrate 215 Through hole 300 Semiconductor device 301 Solder bump 303 Mounting substrate 305 Connection terminal

Claims (18)

A resin substrate obtained by impregnating a fiber base material with a resin material,
A resin substrate having a 1% weight loss temperature of 350 ° C. or more and 500 ° C. or less of the resin substrate. The resin substrate according to claim 1,
The resin substrate whose said fiber base material is a glass fiber base material. The resin substrate according to claim 2,
The resin substrate in which the said glass fiber base material contains at least 1 type chosen from the group which consists of T glass, S glass, E glass, NE glass, and quartz glass. In the resin substrate as described in any one of Claims 1 thru | or 3,
The resin substrate whose linear expansion coefficient in the substrate in-plane direction of the said fiber base material computed in the range of 25 to 150 degreeC is 10 ppm / degrees C or less. In the resin substrate as described in any one of Claims 1 thru | or 4,
A resin substrate in which nano silica is present in the strand of the fiber base material. In the resin substrate as described in any one of Claims 1 thru | or 5,
The resin material is a resin substrate containing a naphthylene ether type epoxy resin. The resin substrate according to claim 6,
The resin material further includes a cyanate resin. In the resin substrate according to claim 6 or 7,
The resin material further includes nano silica,
Median diameter d ₅₀ of less than 100nm in volume-based particle size distribution by a laser diffraction scattering particle size distribution measuring method of the nanosilica, the resin substrate. The resin substrate according to any one of claims 1 to 8,
The resin substrate whose linear expansion coefficient in the substrate surface direction of the said resin substrate computed in the range of 25 to 150 degreeC is 10 ppm / degrees C or less. In the resin substrate as described in any one of Claims 1 thru | or 9,
The resin substrate whose glass transition temperature by the dynamic viscoelasticity measurement of the said resin substrate is 250 degreeC or more. In the resin substrate as described in any one of Claims 1 thru | or 10,
The resin substrate whose thickness of the said resin substrate is 0.6 mm or less. A prepreg formed by impregnating a fiber base material with a resin material,
A prepreg in which a 1% weight reduction temperature of a cured product obtained by curing the prepreg at 200 ° C. for 1 hour is from 350 ° C. to 500 ° C. The prepreg according to claim 12, wherein
A prepreg, wherein the fiber base material is a glass fiber base material. The prepreg according to claim 12 or 13,
The resin material is a prepreg containing a naphthylene ether type epoxy resin. The prepreg according to claim 14, wherein
The resin material further includes a cyanate resin. The prepreg according to any one of claims 12 to 15,
The resin material further includes nano silica,
Median diameter d ₅₀ of less than 100nm in volume-based particle size distribution by a laser diffraction scattering particle size distribution measuring method of the nanosilica, prepreg.   The printed wiring board formed by carrying out circuit processing of the resin substrate as described in any one of Claims 1 thru | or 11.   A semiconductor device comprising a semiconductor element mounted on the printed wiring board according to claim 17.

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