JP2016069401A - Prepreg, resin board, metal-clad laminate, printed wiring board, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a prepreg capable of realizing a printed wiring board having fine circuit dimensions and also excellent insulation reliability under high temperature-high moisture, a resin board, a printed wiring board, and a semiconductor device.SOLUTION: Provided is a prepreg provided with: a fiber base material layer 101 including a sheet-shaped surface-treated glass fiber woven fabric treated with a coupling agent; and a resin layer 103 including an epoxy resin and an inorganic filler, in which provided that the brightness in the surface part in the film thickness direction of the surface-treated glass fiber woven fabric is defined as Xand the brightness in the central part of the glass fiber bundle in the film thickness direction of the surface-treated glass fiber woven fabric is defined as X, X/Xbeing 0.8 to 1.3, the coating weight of the coupling agent in the surface-treated glass fiber woven fabric being 0.07 to 0.50 mass% to 100 mass% of the surface-treated glass fiber woven fabric. In the prepreg, the glass transition temperature of the cured matter obtained by being subjected to hot molding at 220°C for 120 min under 4 MPa being 180°C or higher.SELECTED DRAWING: Figure 1

Description

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

In recent years, along with the demand for higher functionality of electronic devices, the integration of electronic components and the mounting of high-density packaging have progressed, and the miniaturization of semiconductor devices used in these electronic devices has rapidly progressed. ing. A printed wiring board used for a semiconductor device is required to have a high-density and fine circuit.
As a method for forming a fine circuit, an SAP (semi-additive process) method has been proposed.
In the SAP method, first, a roughening treatment is performed on the surface of the insulating layer, and an electroless metal plating film serving as a base is formed on the surface of the insulating layer. Next, the non-circuit forming portion is protected by the plating resist, and the copper thickness of the circuit forming portion is thickened by electrolytic plating. Thereafter, the plating resist is removed, and the electroless metal plating film other than the circuit forming portion is removed by flash etching, thereby forming a circuit on the insulating layer. In the SAP method, since the metal layer laminated on the insulating layer can be thinned, finer circuit wiring is possible.

  The semiconductor device is formed, for example, by mounting a semiconductor element on a printed wiring board. As a technique related to such a printed wiring board, for example, one described in Patent Document 1 below can be cited. Patent Document 1 describes a prepreg and a laminate using a thermosetting resin composition containing a curing agent having an N-substituted maleimide group and an acidic substituent, and a bisphenol F-type phenol novolac-type epoxy resin. .

JP2012-21098A

  A semiconductor device formed by mounting a semiconductor element on a printed wiring board is required to have excellent insulation reliability between wirings. Such a requirement is particularly noticeable with the recent increase in wiring density of printed wiring boards. However, according to the study by the present inventors, it has been clarified that it is difficult to obtain sufficient insulation reliability of the printed wiring board under high temperature and high humidity with the technique described in Patent Document 1.

According to the present invention,
A prepreg used for forming an insulating layer of a printed wiring board,
A fiber base layer comprising a sheet-like surface-treated glass fiber woven fabric treated with a coupling agent;
A resin layer provided on both sides of the fiber base layer and containing an epoxy resin and an inorganic filler;
With
When the surface-treated glass fiber woven fabric is treated with a fluorescent labeling agent that reacts with the coupling agent, and a cross-section of the surface-treated glass fiber woven fabric is observed with a confocal laser fluorescence microscope,
The luminance of the surface portion of the thickness direction of the surface-treated glass fiber woven fabric and X _1,
When the luminance at the center of the glass fiber bundles in the thickness direction of the surface-treated glass fiber woven fabric was X _2,
X ₁ / _{X 2} is 0.8 to 1.3,
The amount of the coupling agent in the surface-treated glass fiber woven fabric is 0.07% by mass to 0.50% by mass with respect to 100% by mass of the surface-treated glass fiber woven fabric,
The glass transition temperature of a cured product obtained by heating and pressing the prepreg at a pressure of 4 MPa and a temperature of 220 ° C. for 120 minutes, measured by dynamic viscoelasticity measurement under conditions of a heating rate of 5 ° C./min and a frequency of 1 Hz. A prepreg having a temperature of 180 ° C. or higher is provided.

  Furthermore, according to this invention, the resin substrate containing the hardened | cured material of the said prepreg is provided.

  Furthermore, according to the present invention, there is provided a metal-clad laminate in which a metal foil is provided on one or both sides of the resin substrate or a laminate in which two or more resin substrates are stacked.

  Furthermore, according to the present invention, there is provided a printed wiring board in which one or two or more circuit layers are provided on one or both sides of the resin substrate or a laminate in which two or more resin substrates are stacked. Is done.

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

  According to the present invention, a prepreg and a resin substrate that can realize a printed wiring board having fine circuit dimensions and excellent insulation reliability under high temperature and high humidity, and a print excellent in insulation reliability under high temperature and high humidity. A wiring board and a semiconductor device can be provided.

It is sectional drawing which shows an example of a structure of the prepreg in this embodiment. 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 a structure of the metal-clad laminated board 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 printed wiring board in this embodiment. It is sectional drawing which shows an example of a structure of the printed wiring board in this embodiment. It is sectional drawing which shows an example of a structure of the semiconductor device 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. Unless otherwise specified, “to” in the numerical value range represents the following.

  First, the prepreg 100 in this embodiment is demonstrated. FIG. 1 is a cross-sectional view showing an example of the configuration of the prepreg 100 in the present embodiment. FIG. 2 is a cross-sectional view showing an example of the configuration of the resin substrate 150 in the present embodiment.

The prepreg 100 is used to form an insulating layer of a printed wiring board, and includes a fiber base layer 101 including a sheet-like surface-treated glass fiber woven fabric treated with a coupling agent, and a fiber base layer. 101, and a resin layer 103 including an epoxy resin (A) and an inorganic filler (B).
Then, the surface-treated glass fiber woven fabric is treated with a fluorescent labeling agent that reacts with the coupling agent, and the cross-section of the glass fiber woven fabric is observed with a confocal laser fluorescence microscope. when the luminance of the surface portion of the thickness of the fabric and X _1, and the brightness at the center of the glass fiber bundles in the thickness direction of the surface-treated glass fiber woven fabric and X _2, X 1 _/ X ₂ are 0. It is 8 or more and 1.3 or less, preferably 0.9 or more and 1.2 or less.
The amount of the coupling agent in the surface-treated glass fiber woven fabric is 0.07% by mass to 0.50% by mass with respect to 100% by mass of the surface-treated glass fiber woven fabric, preferably It is 0.08 mass% or more and 0.30 mass% or less, Most preferably, it is 0.09 mass% or more and 0.20 mass% or less.

The resin substrate 150 is used for forming an insulating layer of a printed wiring board.
Here, the resin substrate 150 includes a cured product of the prepreg 100, and can be obtained, for example, by heat curing the prepreg 100.

The luminance of the surface-treated glass fiber woven fabric can be measured by analyzing an image obtained with a confocal laser fluorescence microscope. For example, measurement is performed according to the following procedure.
First, the surface-treated glass fiber woven fabric is treated with a fluorescent labeling agent that reacts with the coupling agent. Next, the surface-treated glass fiber woven fabric is washed with a solvent such as acetone to remove the unreacted fluorescent labeling agent. Next, a cross section of the surface-treated glass fiber woven fabric is photographed with a confocal laser fluorescence microscope. From the obtained observation image, the luminance (X ₁ ) at the surface portion in the film thickness direction of the surface-treated glass fiber woven fabric and the luminance at the center portion of the glass fiber bundle in the film thickness direction of the surface-treated glass fiber woven fabric ( X ₂ ) is digitized according to the value of the G element in the RGB color system, and X ₁ / X ₂ is calculated from the obtained value.

  The adhesion amount of the coupling agent in the surface-treated glass fiber woven fabric can be measured by the ignition loss method of the glass fiber substrate in JIS R3420.

According to the inventor's study, in a sheet-like surface-treated glass fiber woven fabric treated with a coupling agent, a luminance ratio (X ₁ / X) representing an index of uniformity of the amount of coupling agent attached in the film thickness direction. X ₂ ) and the glass fiber and epoxy resin composition (A) constituting the surface-treated glass fiber woven fabric by setting the adhesion amount of the coupling agent in the surface-treated glass fiber woven fabric within the above ranges, respectively. ) Is improved, and the generation of voids between the glass fiber and the resin is suppressed. As a result, the insulation reliability of the resulting printed wiring board under high temperature and high humidity is improved. Clarified what to do.

In this embodiment, the type of glass fiber woven fabric constituting the surface-treated glass fiber woven fabric, the concentration of the coupling agent in the treatment liquid containing the coupling agent, the pH, the treatment temperature, the treatment time, etc. (X ₁ / X ₂ ) and a factor for controlling the amount of the coupling agent attached to the above range.

The prepreg 100 can be used, for example, to form an insulating layer in a buildup layer or an insulating layer in a core layer in a printed wiring board.
When the prepreg 100 is used to form an insulating layer in the core layer of the printed wiring board, for example, two or more prepregs 100 are stacked, and the obtained laminate is heat-cured to heat and cure the core layer. It can also be.

Further, from the viewpoint of improving the rigidity and heat resistance of the printed wiring board obtained using the prepreg 100, the prepreg 100 measured by dynamic viscoelasticity measurement under conditions of a temperature rising rate of 5 ° C./min and a frequency of 1 Hz is used. The glass transition temperature of the cured product or resin substrate 150 obtained by heating and pressing at a pressure of 4 MPa and a temperature of 220 ° C. for 120 minutes is 180 ° C. or higher, preferably 190 ° C. or higher, more preferably 200 ° C. or higher. is there. About an upper limit, 400 degrees C or less is preferable, for example. The glass transition temperature can be measured using a dynamic viscoelasticity analyzer (DMA).
Further, in the cured product or the resin substrate 150, when the glass transition temperature by dynamic viscoelasticity measurement satisfies the above range, the rigidity of the obtained printed wiring board is increased, and the warpage of the printed wiring board during mounting can be further reduced. . As a result, in the obtained semiconductor device, the positional deviation of the semiconductor element with respect to the printed wiring board can be further suppressed, and the connection reliability between the semiconductor element and the printed wiring board can be further enhanced.
In order to achieve such a glass transition temperature, as will be described later, epoxy resin (A), inorganic filler (B), bismaleimide compound (C), cyanate resin (D), glass fiber woven fabric, etc. It is important to select an appropriate material and appropriately adjust the cross-linking density of the resin and the like, and appropriately adjust the blending amount of each material.

Further, from the viewpoint of further improving the rigidity and heat resistance of a printed wiring board obtained using the prepreg 100, a cured product or a resin substrate obtained by heating and pressing the prepreg 100 at a pressure of 4 MPa and a temperature of 220 ° C. for 120 minutes. The storage elastic modulus E ′ of 150 at 25 ° C. is preferably 5 GPa or more, and more preferably 10 GPa or more. Although it does not specifically limit about an upper limit, For example, it can be 40 GPa or less.
Further, in the cured product or the resin substrate 150, when the storage elastic modulus E ′ at 25 ° C. satisfies the above range, the rigidity of the obtained printed wiring board is increased, and the warpage of the printed wiring board during mounting can be further reduced. . As a result, in the obtained semiconductor device, the positional deviation of the semiconductor element with respect to the printed wiring board can be further suppressed, and the connection reliability between the semiconductor element and the printed wiring board can be further enhanced.
In order to achieve such storage elastic modulus E ′, as will be described later, epoxy resin (A), inorganic filler (B), bismaleimide compound (C), cyanate resin (D), glass fiber woven fabric It is important to select appropriate ones for the resin, etc., and adjust the crosslinking density of the resin as appropriate, and adjust the blending amount of each material as appropriate.

Further, from the viewpoint of further improving the connection reliability between the semiconductor element and the printed wiring board, the surface of the cured product or the resin substrate 150 obtained by heating and pressing the prepreg 100 at a pressure of 4 MPa and a temperature of 220 ° C. for 120 minutes. The average linear expansion coefficient α ₁ in the range from 25 ° C. to 150 ° C. in the inward direction is preferably 20.0 ppm / ° C. or less, more preferably 15.0 ppm / ° C. or less. Although it does not specifically limit about a lower limit, For example, it can be set as 0.1 ppm / degrees C or more.
In the present embodiment, the average linear expansion coefficient α ₁ is a temperature range of 25 ° C. to 150 ° C. and a temperature increase rate of 10 ° C./min using a TMA (thermomechanical analysis) apparatus (TA Instruments, Q400). The average value of the coefficient of linear expansion (CTE) in the plane direction (XY direction), measured under conditions of a load of 5 g and a tensile mode.
Further, in the above cured product or resin substrate 150, the average linear expansion coefficient alpha ₁ satisfies the above range, the linear expansion between the semiconductor device obtained, a printed wiring board and the semiconductor element when exposed to high temperatures The stress generated due to the coefficient difference can be reduced. As a result, the positional deviation of the semiconductor element with respect to the printed wiring board can be further suppressed, and the connection reliability at high temperatures and the temperature cycle reliability between the semiconductor element and the printed wiring board can be further enhanced.
To achieve such an average coefficient of linear expansion alpha _1, as described later, the epoxy resin (A), the inorganic filler (B), a bismaleimide compound (C), cyanate resin (D), a glass fiber woven It is important to select an appropriate cloth or the like, and appropriately adjust the cross-linking density of the resin, or adjust the blending amount of each material as appropriate.

Moreover, in the prepreg 100, it is preferable that the surface-treated glass fiber woven fabric is composed of strands, and some silica particles described later are present in the strands.
When the prepreg 100 is formed so that silica particles are present in the strand, the impregnation property of the epoxy resin composition (A) into the surface-treated glass fiber woven fabric can be improved while maintaining the various properties of the prepreg 100. it can. Here, the various characteristics include, for example, insulation reliability of the printed wiring board, laser processability of the prepreg 100, low thermal expansion of the prepreg 100, and the like.
When the impregnation property of the epoxy resin composition (A) to the surface-treated glass fiber woven fabric is good, generation of voids in the obtained prepreg 100 can be suppressed. Thereby, in the printed wiring board using the prepreg 100 as an insulating layer, the insulation reliability can be improved.
Further, even when a high-density surface-treated glass fiber woven fabric is used, a high impregnation property can be obtained. For this reason, the prepreg 100 excellent in laser workability can be formed using a high-density surface-treated glass fiber woven fabric.
Furthermore, by improving the impregnation property of the epoxy resin composition (A) into the surface-treated glass fiber woven fabric, the surface-treated glass fiber woven fabric can be highly filled with the inorganic filler (B). For this reason, the low thermal expansion of the prepreg 100 can be achieved. Thereby, it can suppress that the printed wiring board which used the said prepreg 100 for the insulating layer generate | occur | produces curvature. Therefore, connection reliability in the semiconductor device can be improved.

  The thickness of the prepreg 100 is, for example, 30 μm or more and 220 μm or less. When the thickness of the prepreg 100 is within the above range, the balance of mechanical strength and productivity is particularly excellent, and a resin substrate 150 suitable for a thin printed wiring board can be obtained.

  FIG. 3 is a cross-sectional view showing an example of the configuration of the metal-clad laminate 200 in the present embodiment. The metal-clad plate 200 is provided with a metal foil 105 on one side or both sides of a resin substrate 150 (insulating layer 301) or a laminate (insulating layer 301) in which two or more resin substrates 150 are stacked. The metal-clad laminate 200 can be used for forming an insulating layer of a printed wiring board.

It continues and the manufacturing method of the prepreg 100 is demonstrated. FIG. 4 is a cross-sectional view showing an example of a method for manufacturing the prepreg 100 in the present embodiment.
The prepreg 100 in this embodiment is a sheet-like material obtained by impregnating the surface-treated glass fiber woven fabric 11 with the epoxy resin composition (P) and then semi-curing it. The sheet-like material having such a structure is excellent in various properties such as dielectric properties, mechanical and electrical connection reliability under high temperature and high humidity, and is suitable for manufacturing an insulating layer of a printed wiring board.
Here, in the present embodiment, in the prepreg 100, the layer including the surface-treated glass fiber woven fabric 11 is the fiber base layer 101, and the other layer not including the fiber base is the resin layer 103.

The method for impregnating the surface-treated glass fiber woven fabric 11 with the epoxy resin composition (P) is not particularly limited. For example, the resin-varnish is prepared by dissolving the epoxy resin composition (P) in a solvent, and the surface-treated glass. A method of immersing the fiber woven fabric 11 in the resin varnish, a method of applying the resin varnish to the surface-treated glass fiber woven fabric 11 with various coaters, a method of spraying the resin varnish on the surface-treated glass fiber woven fabric 11 by spraying, a surface A method of laminating the surface-treated glass fiber woven fabric 11 with the resin layer (P) made of the epoxy resin composition (P) from both sides of the treated glass fiber woven fabric 11 is exemplified.
Among these, the method of laminating the surface-treated glass fiber woven fabric 11 with the resin layer (P) made of the epoxy resin composition (P) from both surfaces of the surface-treated glass fiber woven fabric 11 is preferable. Thereby, the amount of the epoxy resin composition (P) impregnated into the surface-treated glass fiber woven fabric 11 can be freely adjusted, and the moldability of the prepreg 100 can be improved. In addition, when laminating the resin layer (P) made of the epoxy resin composition (P), it is more preferable to use a vacuum laminating apparatus or the like.

  In this embodiment, for example, the epoxy resin composition (P) is obtained by laminating the surface-treated glass fiber woven fabric 11 from both sides of the sheet-like surface-treated glass fiber woven fabric 11 with a resin layer (P) with a supporting substrate. The surface-treated glass fiber woven fabric 11 is impregnated with a resin layer (P) made of

  The manufacturing process of the prepreg 100 using the method of laminating the surface-treated glass fiber woven fabric 11 with the resin layer (P) with the supporting substrate from both surfaces of the sheet-like surface-treated glass fiber woven fabric 11 will be described with reference to FIG. To do.

  First, carrier materials 5a and 5b and a surface-treated glass fiber woven fabric 11 are prepared as materials. Further, a vacuum laminating device 60 and a hot air drying device 62 are prepared as devices. Carrier material 5a, 5b is comprised by the resin layer (P) which consists of an epoxy resin composition (P). The carrier materials 5a and 5b can be obtained, for example, by a method of applying a resin varnish of the epoxy resin composition (P) to a carrier film.

  Next, a bonded body is formed by bonding the carrier material 5a, the surface-treated glass fiber woven fabric 11 and the carrier material 5b in this order using the vacuum laminating apparatus 60. The vacuum laminating apparatus 60 includes a roll around which the carrier material 5 a is wound, a roll around which the carrier material 5 b is wound, a roll around which the surface-treated glass fiber woven fabric 11 is wound, and a laminating roll 61. Under reduced pressure, the carrier material 5a and the carrier material 5b fed from each roll are superimposed on both surfaces of the surface-treated glass fiber woven fabric 11. Then, for example, the stacked laminates are joined by the laminate roll 61 in a vacuum at a temperature of 60 ° C. or higher and 150 ° C. or lower. Thereby, the joined body comprised from the carrier material 5a, the surface treatment glass fiber woven fabric 11, and the carrier material 5b is obtained.

  In such a joining process, other devices such as a vacuum box device and a vacuum becquerel device can also be used.

  Next, heat treatment is performed using a hot air drying device 62 at a temperature equal to or higher than the melting temperature of the epoxy resin composition (P) constituting each of the carrier materials 5a and 5b constituting the joined body. Other methods of heat treatment can be carried out using, for example, an infrared heating device, a heating roll device, a flat platen hot platen press device, or the like.

  After laminating the carrier materials 5a and 5b on the surface-treated glass fiber woven fabric 11, the carrier film is peeled off. By this method, the epoxy resin composition (P) is supported on the surface-treated glass fiber woven fabric 11, and the prepreg 100 including the epoxy resin composition (P) and the surface-treated glass fiber woven fabric 11 is obtained.

Next, a method for manufacturing the metal-clad laminate 200 and the resin substrate 150 using the prepreg 100 obtained above will be described. A method for manufacturing the metal-clad laminate 200 and the resin substrate 150 using the prepreg 100 is, for example, as follows.
The metal foils 105 are stacked on the upper and lower surfaces or one surface of the outer side of the prepreg 100 or a laminate obtained by superimposing two or more prepregs 100, and these are joined under a high vacuum condition using a laminator device or a becquerel device, or the prepreg 100 is used as it is. The metal foil 105 is overlapped on the upper and lower sides or one side of the outer side. When two or more prepregs 100 are stacked, the metal foil 105 is stacked on the outermost upper and lower surfaces or one surface of the stacked prepregs 100.
Subsequently, the metal-clad laminate 200 can be obtained by heat-pressing the laminate in which the prepreg 100 and the metal foil 105 are stacked. Here, it is preferable to continue the pressurization until the end of cooling at the time of heat-pressure molding.

The heating temperature at the time of the above-described heating and pressing is preferably 120 ° C. or higher and 250 ° C. or lower, and more preferably 150 ° C. or higher and 240 ° C. or lower.
Moreover, the pressure at the time of the above-described heat and pressure molding is preferably 0.5 MPa or more and 5 MPa or less, and more preferably a high pressure of 2.5 MPa or more and 5 MPa or less.

  Further, after the heat and pressure molding, if necessary, post-curing may be performed in a thermostatic bath or the like. The post-curing temperature is preferably 150 ° C. or higher and 300 ° C. or lower, more preferably 250 ° C. or higher and 300 ° C. or lower.

  The resin substrate 150 can be obtained by removing the metal foil 105 from the metal-clad laminate 200.

  Moreover, a printed wiring board can be obtained using the metal-clad laminate 200 or the resin substrate 150 as a core substrate.

  Hereinafter, each material used when manufacturing the prepreg 100, the metal-clad laminate 200, and the resin substrate 150 will be described in detail.

Examples of the metal constituting the metal foil 105 include copper, a copper alloy, aluminum, an aluminum alloy, silver, a silver alloy, gold, a gold alloy, zinc, a zinc alloy, nickel, a nickel alloy, tin, Examples thereof include tin-based alloy, iron, iron-based alloy, Kovar (trade name), 42 alloy, Fe-Ni based alloy such as Invar, Super Invar, W, Mo, and the like. Among these, the metal constituting the metal foil 105 is preferably copper or a copper alloy because of its excellent conductivity, easy circuit formation by etching, and low cost. That is, the metal foil 105 is preferably a copper foil.
Further, as the metal foil 105, a metal foil with a carrier or the like can also be used.
The thickness of the metal foil 105 is preferably 0.5 μm or more and 20 μm or less, and more preferably 1.5 μm or more and 18 μm or less.

  The epoxy resin composition (P) includes an epoxy resin (A) and an inorganic filler (B).

  Examples of the epoxy resin (A) 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 (4,4 ′-(1,3- Phenylenediisopridiene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4 '-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4' -Cyclohexidiene bisphenol type epoxy resin), etc .; phenol novolac type epoxy resin, cresol novolac type epoxy resin, tetraphenol group ethane type novolac type epoxy resin, condensed ring aromatic hydrocarbon structure Novolak-type epoxy resins such as volac-type epoxy resins; biphenyl-type epoxy resins; aralkyl-type epoxy resins such as xylylene-type epoxy resins and biphenyl-aralkyl-type epoxy resins; naphthylene ether-type epoxy resins, naphthol-type epoxy resins, naphthalenediol-type epoxy resins Naphthalene type epoxy resins such as bifunctional to tetrafunctional epoxy type naphthalene resins, binaphthyl type epoxy resins, naphthalene aralkyl type epoxy resins; anthracene type epoxy resins; phenoxy type epoxy resins; dicyclopentadiene type epoxy resins; norbornene type epoxy resins; Examples thereof include adamantane type epoxy resins and fluorene type epoxy resins.

  As the epoxy resin (A), one of these may be used alone, two or more may be used in combination, and one or two or more thereof and a prepolymer thereof may be used in combination. .

  Among epoxy resins (A), bisphenol type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, naphthalene type from the viewpoint of further improving the heat resistance and insulation reliability of the obtained printed wiring board One or more selected from the group consisting of epoxy resins, anthracene type epoxy resins and dicyclopentadiene type epoxy resins are preferred, aralkyl type epoxy resins, novolak type epoxy resins having a condensed ring aromatic hydrocarbon structure and naphthalene types One or more selected from the group consisting of epoxy resins are more preferred.

  As the bisphenol A type epoxy resin, “Epicoat 828EL” and “YL980” manufactured by Mitsubishi Chemical Corporation can be used. As the bisphenol F type epoxy resin, “jER806H” and “YL983U” manufactured by Mitsubishi Chemical Corporation, “EPICLON 830S” manufactured by DIC Corporation, and the like can be used. As the bifunctional naphthalene type epoxy resin, “HP4032”, “HP4032D”, “HP4032SS” manufactured by DIC, and the like can be used. As the tetrafunctional naphthalene type epoxy resin, “HP4700” and “HP4710” manufactured by DIC, etc. can be used. As the naphthol type epoxy resin, “ESN-475V” manufactured by Nippon Steel Chemical Co., Ltd., “NC7000L” manufactured by Nippon Kayaku Co., Ltd. and the like can be used. As the aralkyl type epoxy resin, “NC3000”, “NC3000H”, “NC3000L”, “NC3000S”, “NC3000S-H”, “NC3100” manufactured by Nippon Kayaku Co., Ltd., “ESN-170” manufactured by Nippon Steel Chemical Co., Ltd. And “ESN-480” can be used. As the biphenyl type epoxy resin, “YX4000”, “YX4000H”, “YX4000HK”, “YL6121” and the like manufactured by Mitsubishi Chemical Corporation can be used. As the anthracene type epoxy resin, “YX8800” manufactured by Mitsubishi Chemical Corporation can be used. As the naphthylene ether type epoxy resin, “HP6000”, “EXA-7310”, “EXA-7311”, “EXA-7311L”, “EXA7311-G3” and the like manufactured by DIC can be used.

  As the epoxy resin (A), one of these may be used alone, or two or more having different weight average molecular weights may be used in combination, and one or two or more prepolymers thereof. And may be used in combination.

Among these epoxy resins (A), an aralkyl type epoxy resin is particularly preferable. Thereby, the moisture absorption solder heat resistance and flame retardance of the resin substrate 150 can be further improved.
The aralkyl type epoxy resin is represented by the following formula (1), for example.

ここで、ＡおよびＢは、ベンゼン環、ビフェニル構造などの芳香族環を表す。またＡおよびＢの芳香族環の水素が置換されていてもよい。置換基としては、例えば、メチル基、エチル基、プロピル基、フェニル基などが挙げられる。ｎは繰返し単位を表し、例えば、１〜１０の整数である。

Here, A and B represent aromatic rings such as a benzene ring and a biphenyl structure. Moreover, the hydrogen of the aromatic ring of A and B may be substituted. Examples of the substituent include a methyl group, an ethyl group, a propyl group, and a phenyl group. n represents a repeating unit, for example, an integer of 1 to 10.

  Specific examples of the aralkyl type epoxy resin include the following (1a) and (1b).

（式中、ｎは、１〜５の整数を示す。）

(In the formula, n represents an integer of 1 to 5.)

（式中、ｎは、１〜５の整数を示す。）

(In the formula, n represents an integer of 1 to 5.)

  The epoxy resin (A) other than the above is preferably a novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure. 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, 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, the flame retardancy is excellent as compared with the conventional novolac type epoxy resin.

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

  The phenol compound is not particularly limited, and examples thereof include phenol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2, Xylenols such as 6-xylenol, 3,4-xylenol, 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 and t-butylphenol; phenylphenols such as o-phenylphenol, m-phenylphenol and p-phenylphenol; 1,5-dihydroxynaphthalene and 1,6-dihydro Naphthalenediols such as cinaphthalene and 2,7-dihydroxynaphthalene; polyhydric phenols such as resorcin, catechol, hydroquinone, pyrogallol, and fluoroglucin; and alkyl polyhydric phenols such as alkylresorcin, alkylcatechol, and alkylhydroquinone It is done. Of these, phenol is preferable from the viewpoint of cost and the effect on the decomposition reaction.

  The aldehyde compound is not particularly limited, for example, 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.

  The condensed ring aromatic hydrocarbon compound is not particularly limited, but 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; A triphenylene derivative; a tetraphen derivative and the like.

  The novolak-type epoxy resin having a condensed ring aromatic hydrocarbon structure is not particularly limited. For example, methoxynaphthalene-modified orthocresol 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, and R may be the same or different from each other; a hydrogen atom; a hydrocarbon group having 1 to 10 carbon atoms; a halogen element; a phenyl group; An aryl group such as a benzyl group; and a group selected from organic groups including glycidyl ether, wherein n, p, and q are integers of 1 or more, and the values of p and q may be the same or different for each repeating unit. May be.)

(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 hydrogen atom; a hydrocarbon group having 1 to 10 carbon atoms; a halogen element; an aryl group such as a phenyl group or a benzyl group; and an organic group including a glycidyl ether.)

Further, as the epoxy resin (A) other than the above, naphthalene type epoxy resins such as naphthol type epoxy resin, naphthalene diol type epoxy resin, bifunctional to tetrafunctional epoxy type naphthalene resin, naphthylene ether type epoxy resin and the like are preferable. Thereby, the heat resistance and low thermal expansibility of the printed wiring board to be obtained can be further improved. Here, the naphthalene type epoxy resin refers to one having a naphthalene ring skeleton and having two or more glycidyl groups.
Further, since the π-π stacking effect of the naphthalene ring is higher than that of the benzene ring, the naphthalene type epoxy resin is particularly excellent in low thermal expansion and low thermal shrinkage. Further, 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.

（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の何れか一方は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.)

  Although the minimum of the weight average molecular weight (Mw) of an epoxy resin (A) is not specifically limited, Mw300 or more is preferable and especially Mw800 or more is preferable. It can suppress that tackiness arises in the prepreg 100 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 into the surface-treated glass fiber woven fabric is improved when the prepreg 100 is produced, and a more uniform prepreg 100 can be obtained. The Mw of the epoxy resin can be measured by GPC, for example.

  The content of the epoxy resin (A) contained in the epoxy resin composition (P) is not particularly limited as long as it is appropriately adjusted according to the purpose, but the total solid content of the epoxy resin composition (P) (that is, , The component excluding the solvent) is 100% by mass, preferably 7.0% by mass to 30.0% by mass, and more preferably 8.0% by mass to 28.0% by mass. When the content of the epoxy resin (A) is not less than the above lower limit value, the handling property is improved and the prepreg 100 can be easily formed. When the content of the epoxy resin (A) is less than or equal to the above upper limit, the strength and flame retardancy of the obtained printed wiring board are improved, the linear expansion coefficient of the printed wiring board is lowered, and the effect of reducing warpage is improved. There is a case to do.

  The epoxy resin composition (P) according to this embodiment preferably further includes one or more selected from the group consisting of a bismaleimide compound (C) and a cyanate resin (D).

  The maleimide group of the bismaleimide compound has a five-membered planar structure, and since the double bond of the maleimide group easily interacts between molecules and has high polarity, the compound has a maleimide group, a benzene ring, and other planar structures. It shows strong intermolecular interactions and can suppress molecular motion. Therefore, the epoxy resin composition (P) can reduce the linear expansion coefficient of the cured product of the prepreg 100 and the resin substrate 150 obtained by including the bismaleimide compound (C), and can improve the glass transition temperature. Furthermore, heat resistance can be improved.

As the bismaleimide compound (C), a bismaleimide compound (C-1) having at least two maleimide groups in the molecule is preferable.
Examples of the bismaleimide compound (C-1) include 4,4′-diphenylmethane bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, and 2,2-bis [4- (4-maleimidophenoxy) phenyl]. Propane, bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane, 4-methyl-1,3-phenylenebismaleimide, N, N′-ethylenedimaleimide, N, N′-hexamethylenedimaleimide , Bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, etc., compounds having two maleimide groups in the molecule 3 or more maleimide groups in the molecule such as polyphenylmethanemaleimide Such compounds, and the like.
One of these can be used alone, or two or more can be used in combination. Among these bismaleimide compounds (C-1), 4,4′-diphenylmethane bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis, etc. because of its low water absorption. -(3-Ethyl-5-methyl-4-maleimidophenyl) methane and polyphenylmethanemaleimide are preferred.

  Moreover, as a bismaleimide compound (C), the reaction material of a bismaleimide compound (C-1) and an amine compound can also be used. As the amine compound, at least one selected from an aromatic diamine compound and a monoamine compound can be used.

  Examples of the aromatic diamine compound include o-dianisidine, o-tolidine, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, and 2,2 ′. -Dimethyl-4,4'-diaminobiphenyl, m-phenylenediamine, p-phenylenediamine, o-xylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 1,5-diaminonaphthalene, 4,4 ′-(p-phenylenediisopropylidene) dianiline, 2,2- [4- (4 -Aminophenoxy) phenyl] propane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, Examples thereof include bis (4- (4-aminophenoxy) phenyl) sulfone.

  Examples of the monoamine compound include o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-aminobenzenesulfonic acid, m-amino. Benzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, o-aniline, m-aniline, p-aniline, o-methylaniline, m-methylaniline, p- Examples include methylaniline, o-ethylaniline, m-ethylaniline, p-ethylaniline, o-vinylaniline, m-vinylaniline, p-vinylaniline, o-allylaniline, m-allylaniline, p-allylaniline, and the like. It is done.

  Reaction of a bismaleimide compound (C-1) and an amine compound can be made to react in an organic solvent. The reaction temperature is, for example, 70 to 200 ° C., and the reaction time is, for example, 0.1 to 10 hours.

  The content of the bismaleimide compound (C) contained in the epoxy resin composition (P) is not particularly limited, but the total solid content (that is, the component excluding the solvent) of the epoxy resin composition (P) is 100% by mass. Is preferably 1.0% by mass or more and 25.0% by mass or less, and more preferably 5.0% by mass or more and 20.0% by mass or less. When the content of the bismaleimide compound (C) is within the above range, the cured product of the obtained prepreg 100 and the elastic modulus of the resin substrate 150 can be further improved.

Although the said cyanate resin (D) is not specifically limited, For example, it can obtain by making a halogenated cyanide compound, phenols, and naphthol react, and prepolymerizing by methods, such as a heating, as needed. Moreover, the commercial item prepared in this way can also be used.
The epoxy resin composition (P) can further reduce the linear expansion coefficient of the cured product of the prepreg 100 and the resin substrate 150 by further including the cyanate resin (D) as a thermosetting resin. Furthermore, by using the cyanate resin (D), the cured product of the obtained prepreg 100, the electrical properties (low dielectric constant, low dielectric loss tangent) of the resin substrate 150, mechanical strength, and the like can be improved.

  Examples of the cyanate resin (D) include novolak type cyanate resins; bisphenol A type cyanate resins, bisphenol E type cyanate resins, tetramethylbisphenol F type cyanate resins, and the like; naphthol aralkyl type phenol resins, and cyanogen halides. Naphthol aralkyl type cyanate resin obtained by the reaction with; dicyclopentadiene type cyanate resin; biphenylalkyl type cyanate resin. Among these, novolak type cyanate resins and naphthol aralkyl type cyanate resins are preferable, and novolak type cyanate resins are more preferable. By using the novolac-type cyanate resin, the cured product of the obtained prepreg 100 and the crosslinking density of the resin substrate 150 are increased, and the heat resistance is 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. Moreover, the insulating layer containing a novolac type cyanate resin has excellent rigidity. Therefore, the heat resistance of the cured product of the obtained prepreg 100 and the resin substrate 150 can be further improved.
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 average repeating unit n is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. When the average repeating unit n is not less than the above lower limit, the heat resistance of the novolak cyanate resin is improved, and it is possible to suppress the demerization and volatilization of the low mer during heating. The average repeating unit n is not particularly limited, but is preferably 10 or less, more preferably 7 or less. It can suppress that melt viscosity becomes it high that n is below the said upper limit, and the moldability of the prepreg 100 can be improved.

  As the cyanate resin (D), a naphthol aralkyl type cyanate resin represented by the following general formula (II) is also preferably used. The naphthol aralkyl type cyanate resin represented by the following general formula (II) includes, for example, naphthols such as α-naphthol or β-naphthol, p-xylylene glycol, α, α′-dimethoxy-p-xylene, 1,4 -It is obtained by condensing a naphthol aralkyl type phenol resin obtained by reaction with di (2-hydroxy-2-propyl) benzene and cyanogen halide. The repeating unit n of the general formula (II) is preferably an integer of 10 or less. When the repeating unit n is 10 or less, a more uniform resin layer can be obtained. 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はそれぞれ独立に水素原子またはメチル基を示し、ｎは１以上１０以下の整数を示す。）

(In the formula, each R independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more and 10 or less.)

  Moreover, cyanate resin (D) may be used individually by 1 type, may use 2 or more types together, and may use 1 type, 2 or more types, and those prepolymers together.

  Although content of cyanate resin (D) contained in an epoxy resin composition (P) is not specifically limited, The total solid content (namely, component except a solvent) of an epoxy resin composition (P) is 100 mass%. 1.0 mass% or more and 25.0 mass% or less is preferable, and 3.0 mass% or more and 20.0 mass% or less are more preferable. When the content of the cyanate resin (D) is within the above range, the cured product of the obtained prepreg 100 and the storage elastic modulus E ′ of the resin substrate 150 can be further improved.

  The epoxy resin composition (P) according to this embodiment contains an inorganic filler (B) as an essential component. Thereby, the hardened | cured material of the obtained prepreg 100 and the storage elastic modulus E 'of the resin substrate 150 can be improved. Furthermore, the linear expansion coefficient of the insulating layer 301 obtained can be reduced.

Examples of the inorganic filler (B) include silicates such as talc, fired clay, unfired clay, mica and glass; oxides such as titanium oxide, alumina, boehmite, silica and fused silica; calcium carbonate and magnesium carbonate Carbonates such as hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide; sulfates or sulfites such as barium sulfate, calcium sulfate and calcium sulfite; zinc borate, barium metaborate, Borates such as aluminum borate, calcium borate and sodium borate; nitrides such as aluminum nitride, boron nitride, silicon nitride and carbon nitride; titanates such as strontium titanate and barium titanate it can.
Among these, talc, alumina, glass, silica, mica, aluminum hydroxide, and magnesium hydroxide are preferable, and silica is particularly preferable. As the inorganic filler (B), one of these may be used alone, or two or more may be used in combination.

Although the average particle diameter of an inorganic filler (B) is not specifically limited, 0.01 micrometer or more is preferable and 0.05 micrometer or more is more preferable. When the average particle diameter of the inorganic filler (B) is not less than the above lower limit value, it is possible to suppress the viscosity of the varnish from being increased, and workability at the time of producing the prepreg 100 can be improved. The average particle diameter of the inorganic filler (B) is not particularly limited, but is preferably 5.0 μm or less, more preferably 2.0 μm or less, and further preferably 1.0 μm or less. When the average particle size of the inorganic filler (B) is not more than the above upper limit, phenomena such as sedimentation of the inorganic filler (B) in the varnish can be suppressed, and a more uniform resin layer can be obtained. Further, when the circuit dimension L / S of the printed wiring board 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 inorganic filler (B) is measured, for example, by measuring the particle size distribution on a volume basis using a laser diffraction particle size distribution measuring device (LA-500, manufactured by HORIBA), and the median diameter (D ₅₀ ). Can be the average particle size.

  In addition, the inorganic filler (B) is not particularly limited, but an inorganic filler having a monodispersed average particle diameter may be used, or an inorganic filler having a polydispersed average particle diameter may be used. Furthermore, one type or two or more types of inorganic fillers having an average particle size of monodispersed and / or polydispersed may be used in combination.

  The inorganic filler (B) is preferably silica particles, preferably silica particles having an average particle size of 5.0 μm or less, more preferably silica particles having an average particle size of 0.1 μm to 4.0 μm, and 0.2 μm to 2.0 μm. The following silica particles are particularly preferred. Thereby, the filling property of an inorganic filler (B) can further be improved.

  The content of the inorganic filler (B) is not particularly limited, but is 50.0% by mass or more and 90% by mass when the total solid content of the epoxy resin composition (P) (that is, the component excluding the solvent) is 100% by mass. 0.0 mass% or less is preferable, and 55.0 mass% or more and 80.0 mass% or less is more preferable. When the content of the inorganic filler (B) is within the above range, the resulting cured product of the prepreg 100 and the resin substrate 150 can have particularly low thermal expansion and low water absorption.

The inorganic filler (B) preferably further contains silica nanoparticles.
The average particle diameter of the silica nanoparticles is preferably 1 nm or more and less than 100 nm, more preferably 10 nm or more and less than 100 nm, and particularly preferably 10 nm or more and 70 nm or less from the viewpoint of impregnation. When the average particle diameter of the silica nanoparticles is equal to or more than the above lower limit, the distance between the fibers of the surface-treated glass fiber woven fabric can be further expanded. Further, when the average particle diameter of the silica nanoparticles is less than or less than the above upper limit value, the silica nanoparticles can sufficiently enter between the fibers of the surface-treated glass fiber woven fabric.
In particular, it is preferably used in combination with silica particles having an average particle size of 0.1 μm or more and 5.0 μm or less. Thereby, silica can be uniformly contained in the epoxy resin composition (P) at a high concentration.
The average particle diameter of the silica nanoparticles can be measured by, for example, a dynamic light scattering method. Particles are dispersed in water with ultrasonic waves, and the particle size distribution of the particles is measured on a volume basis using a dynamic light scattering particle size distribution analyzer (manufactured by HORIBA, LB-550). The median diameter (D ₅₀ ) is the average particle diameter. And

Moreover, 1.0 mass% or more and 20.0 mass% or less are preferable with respect to 100 mass% of inorganic fillers (B), and content of the said silica nanoparticle is 3.0 mass% or more and 18.0 mass% or less. More preferred.
When the content of the silica nanoparticles is within the above range, a prepreg 100 obtained by impregnating a high-density surface-treated glass fiber woven fabric with an epoxy resin composition (A) containing a large amount of an inorganic filler (B). Even so, the impregnation property of the surface-treated glass fiber woven fabric of the epoxy resin composition (A) becomes good. This is because the silica nanoparticles enter between the fibers of the surface-treated glass fiber woven fabric, that is, into the strands to widen the fibers, so that the inorganic filler (B) other than the silica nanoparticles can also enter the fiber woven fabric. This is considered to be. Thus, the prepreg 100 which has a silica particle in a strand can be obtained by using the said silica nanoparticle as an inorganic filler (B).

The method for producing the silica particles is not particularly limited. For example, a combustion method such as a VMC (Vaporized Metal Combustion) method, a PVS (Physical Vapor Synthesis) method, a melting method in which crushed silica is melted by flame, a precipitation method, a gel method, etc. Among these, the VMC method is particularly preferable.
The VMC method is a method in which silica particles are formed by putting silicon powder into a chemical flame formed in an oxygen-containing gas, burning it, and cooling it. In the VMC method, since the particle diameter of the silica particles to be obtained can be adjusted by adjusting the particle diameter of the silicon powder to be input, the input amount, the flame temperature, and the like, silica particles having different particle diameters can be produced.
Commercially available products such as NSS-5N (manufactured by Tokuyama) and Sicastar 43-00-501 (manufactured by Micromod) can also be used as the silica nanoparticles.

  In addition, a curing agent and a coupling agent can be appropriately blended in the epoxy resin composition (P) as necessary.

Examples of the curing agent include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole, 2-ethyl-4-methylimidazole (EMI24), 2-phenyl-4-methylimidazole (2P4MZ), 2-phenylimidazole (2PZ), 2-phenyl-4-methyl-5-hydroxyimidazole (2P4MHZ), 1-benzyl-2-phenylimidazole (1B2PZ) ) And the like; and catalyst-type curing agents such as Lewis acids such as BF ₃ complexes.
In addition, for example, aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylenediamine (MXDA), m-phenylenediamine, p-phenylenediamine, o-xylenediamine, 4,4′- Diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 1,5-diaminonaphthalene, 4,4′- (P-phenylenediisopropylidene) dianiline, 2,2- [4- (4-aminophenoxy) phenyl] propane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3 , 3′-diethyl-5,5′-dimethyldiphenylmethane, 3 In addition to aromatic polyamines such as 3′-diethyl-4,4′-diaminodiphenylmethane, polyamine compounds including dicyandiamide (DICY), organic acid dihydrazide, etc .; hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA) Acid anhydrides including aromatic acid anhydrides such as alicyclic acid anhydrides such as, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA); polysulfide, thioester, Polymercaptan compounds such as thioethers; Isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; polyaddition type curing agents such as organic acids such as carboxylic acid-containing polyester resins; 2,2′-methylenebis (4-ethyl-6- t ert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3- Methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butylhydroquinone, 1,3,5-tris (3,5-di-tert) Phenolic compounds such as -butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) trione can also be used.

Furthermore, for example, phenolic resin-based curing agents such as novolak-type phenolic resins and resol-type phenolic resins; urea resins such as methylol group-containing urea resins; and condensation-type curing agents such as melamine resins such as methylol group-containing melamine resins It may be used.
The phenol resin-based curing agent is a monomer, oligomer, or polymer in general having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, phenol novolak resin, cresol novolak Resins, naphthol novolak resins and other novolac phenol resins; trifunctional methane type phenol resins and other polyfunctional phenol resins; terpene modified phenol resins and dicyclopentadiene modified phenol resins and other modified phenol resins; phenylene skeleton and / or biphenylene skeleton Aralkyl-type resins such as phenol aralkyl resins having phenylene and / or naphthol aralkyl resins having a biphenylene skeleton; bisphenols such as bisphenol A and bisphenol F Is like compounds, they may be used in combination of two or more be used one kind alone. Among these, the hydroxyl equivalent is preferably 90 g / eq or more and 250 g / eq or less from the viewpoint of curability.
The weight average molecular weight of the phenol resin is not particularly limited, but is preferably 4 × 10 ^{2 to} 1.8 × 10 ^{3 and} more preferably 5 × 10 ^{2 to} 1.5 × 10 ³ . By making the weight average molecular weight equal to or higher than the lower limit, problems such as tackiness occurring in the prepreg are less likely to occur. By making the weight average molecular weight or lower the impregnation into the surface-treated glass fiber woven fabric when the prepreg 100 is manufactured. The properties are improved and a more uniform product can be obtained.

  In the epoxy resin composition (P), the content of the curing agent is not particularly limited, but is 0 when the total solid content of the epoxy resin composition (P) (that is, the component excluding the solvent) is 100% by mass. 0.01 mass% or more and 15.0 mass% or less is preferable, and 0.1 mass% or more and 10.0 mass% or less is more preferable. When the content of the curing agent is not less than the above lower limit, the effect of promoting curing can be sufficiently exhibited. When the content of the curing agent is not more than the above upper limit value, the storability of the prepreg 100 can be further improved.

  Furthermore, the epoxy resin composition (P) may contain a coupling agent. By using the coupling agent, the wettability of the interface between the surface-treated glass fiber woven fabric or the inorganic filler (B) and each resin can be improved. Therefore, it is preferable to use a coupling agent, and the heat resistance of the cured product of the obtained prepreg 100 and the resin substrate 150 can be improved.

Examples of the coupling agent include silane coupling agents such as epoxy silane coupling agents, cationic silane coupling agents, and amino silane coupling agents, titanate coupling agents, and silicone oil type coupling agents. A coupling agent may be used individually by 1 type, and may use 2 or more types together.
Thereby, the wettability of the interface between the surface-treated glass fiber woven fabric or the inorganic filler (B) and each resin can be increased, and the cured product of the obtained prepreg 100 and the heat resistance of the resin substrate 150 are further improved. be able to.

The addition amount of the coupling agent is not particularly limited because it depends on the specific surface area of the inorganic filler (B), but the total solid content of the epoxy resin composition (P) (that is, the component excluding the solvent) is 100% by mass. When it is, 0.01 mass% or more and 1 mass% or less are preferable, and 0.05 mass% or more and 0.5 mass% or less are more preferable.
When the content of the coupling agent is not less than the above lower limit value, the inorganic filler (B) can be sufficiently covered, and the cured product of the obtained prepreg 100 and the heat resistance of the resin substrate 150 can be improved. . Moreover, when content of a coupling agent is below the said upper limit, it can suppress affecting reaction, and can suppress the fall of the cured | curing material of the obtained prepreg 100, the bending strength of the resin substrate 150, etc. .

  Furthermore, the epoxy resin composition (P) includes a curing accelerator, a pigment, a dye, an antifoaming agent, a leveling agent, an ultraviolet absorber, a foaming agent, an antioxidant, and a flame retardant, as long as the object of the present invention is not impaired. In addition, additives other than the above components such as an ion scavenger may be added.

  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, azomethine and the like.

The epoxy resin composition (P) is acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve, carbitol In organic solvents such as anisole and N-methylpyrrolidone, various mixing machines such as ultrasonic dispersion method, high-pressure collision dispersion method, high-speed rotation dispersion method, bead mill method, high-speed shear dispersion method, rotation and revolution dispersion method are used. The resin varnish (I) can be obtained by dissolving, mixing and stirring.
The solid content of the resin varnish (I) is not particularly limited, but is preferably 40% by mass or more and 80% by mass or less, and particularly preferably 50% by mass or more and 70% by mass or less. Thereby, the impregnation property to the surface treatment glass fiber woven fabric of resin varnish (I) can further be improved.

In the above epoxy resin composition (P), the ratio of each component is as follows, for example.
When the total solid content of the epoxy resin composition (P) (that is, the component excluding the solvent) is 100% by mass, the proportion of the epoxy resin (A) is preferably 7.0% by mass or more and 30.0% by mass or less. The ratio of one or more selected from the bismaleimide compound (C) and the cyanate resin (D) is 1.0% by mass or more and 25.0% by mass or less, and the ratio of the inorganic filler (B) Is 50.0 mass% or more and 90.0 mass% or less.
More preferably, the proportion of the epoxy resin (A) is 8.0% by mass or more and 28.0% by mass or less, and the proportion of one or more selected from the bismaleimide compound (C) and the cyanate resin (D) Is 3.0 mass% or more and 20.0 mass% or less, and the ratio of an inorganic filler (B) is 55.0 mass% or more and 80.0 mass% or less.

Next, the surface-treated glass fiber woven fabric used in this embodiment will be described.
The thickness of the glass fiber woven fabric constituting the surface-treated glass fiber woven fabric is not particularly limited, but is preferably 5 μm or more and 150 μm or less, more preferably 10 μm or more and 140 μm or less, and further preferably 12 μm or more and 130 μm or less. . By using the glass fiber woven fabric having such a thickness, the handling property at the time of manufacturing the prepreg 100 can be further improved.
Further, when the thickness of the glass fiber woven fabric is not more than the above upper limit value, the impregnation property of the coupling agent to the glass fiber woven fabric becomes good, and the luminance ratio (X ₁ / X ₂ ) is in the above range. An inner surface-treated glass fiber woven fabric can be obtained.
Furthermore, when the thickness of the glass fiber woven fabric is not more than the above upper limit value, the impregnation property of the epoxy resin composition (P) into the surface-treated glass fiber woven fabric is improved, and the occurrence of a decrease in strand void and insulation reliability is caused. It can be suppressed more. In addition, it is possible to easily form a through hole by a laser such as carbon dioxide, UV, or excimer. Further, when the thickness of the glass fiber woven fabric is equal to or more than the above lower limit value, the mechanical strength of the surface-treated glass fiber woven fabric, a cured product of the obtained prepreg 100, the resin substrate 150, and the like can be improved. As a result, handling properties can be improved, production of the prepreg 100 can be facilitated, and warpage of the obtained printed wiring board can be suppressed.

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

The glass fiber woven fabric used in the present embodiment preferably has a basis weight (weight of fiber substrate per 1 m ² ) of 4 g / m ² or more and 200 g / m ² or less, and 8 g / m ² or more and 180 g / m. It is more preferably ² or less, and further preferably 12 g / m ² or more and 160 g / m ² or less.

When the basis weight of the glass fiber woven fabric is not more than the above upper limit value, the impregnation property of the coupling agent to the glass fiber woven fabric becomes good, and the luminance ratio (X ₁ / X ₂ ) is within the above range. A surface-treated glass fiber woven fabric can be obtained.
Further, when the basis weight is not more than the above upper limit value, the impregnation property of the epoxy resin composition (P) into the glass fiber woven fabric is improved, and the occurrence of strand voids and a decrease in insulation reliability can be further suppressed. . In addition, it is possible to easily form a through hole by a laser such as carbon dioxide, UV, or excimer. Moreover, mechanical strength of surface-treated glass fiber woven fabric, the hardened | cured material of the obtained prepreg 100, the resin substrate 150, etc. can be improved as basic weight is more than the said lower limit. As a result, handling properties can be improved, production of the prepreg 100 can be facilitated, and warpage of the obtained printed wiring board can be suppressed.

The bulk density of the glass fiber woven fabric used in the present embodiment is preferably 0.5 g / cm ³ or more and 1.5 g / cm ³ or less, particularly 0.8 g / cm ³ or more and 1.3 g / cm ³ or less. Preferably there is.
When the bulk density of the glass fiber woven fabric is not less than the above lower limit value, the laser processability of the insulating layer is excellent.
When the bulk density of the glass fiber woven fabric is not more than the above upper limit value, the impregnation property of the coupling agent to the glass fiber woven fabric is improved, and the luminance ratio (X ₁ / X ₂ ) is within the above range. A surface-treated glass fiber woven fabric can be obtained.
Moreover, the impregnation property of the epoxy resin composition (P) with respect to a glass fiber woven fabric improves that the bulk density of a glass fiber woven fabric is below the said upper limit. The bulk density of the glass fiber woven fabric can be adjusted, for example, by adjusting the number of warps and wefts to be driven and the thickness of the fiber that has been opened and flattened.

The glass fiber woven fabric used in the present embodiment is not particularly limited, but the air permeability is preferably 1 cc / cm ² / sec or more and 100 cc / cm ² / sec or less, preferably 3 cc / cm ² / sec or more and 80 cc / cm ^2. / Sec or less is particularly preferable. When the air permeability is equal to or higher than the above lower limit value, the surface treated glass in which the impregnation property of the coupling agent to the glass fiber woven fabric is improved and the luminance ratio (X ₁ / X ₂ ) is within the above range. A fiber woven fabric can be obtained. When the air permeability is equal to or higher than the lower limit, the impregnation property of the epoxy resin composition (P) with respect to the glass fiber woven fabric is improved. The air permeability can be measured according to JIS R3420.
When the air permeability is not more than the above upper limit value, the insulating layer is more excellent in laser processability.

  The glass fiber woven fabric is preferably made of a strand composed of a plurality of fibrillar glass fibers. Thereby, the glass fiber woven fabric becomes rigid, and the rigidity and dimensional stability of the prepreg 100 can be improved. At this time, the glass fiber used as the fibrillar glass fiber is preferably cylindrical, and the average diameter of the glass fiber is preferably 1 μm or more and 12 μm or less, particularly preferably 4 μm or more and 9 μm or less. By being in the said range, the rigidity of a glass fiber woven fabric can be improved.

  As the glass fiber woven fabric constituting the surface-treated glass fiber woven fabric, for example, glass fibers made of E glass, S glass, D glass, T glass, NE glass, UT glass, L glass, HP glass, quartz glass and the like are used. Are preferably used.

  Although the said glass fiber is not specifically limited, It is preferable that the thermal expansion coefficient of the warp direction measured based on JISR3102 is 10 ppm / degrees C or less, and it is especially preferable that it is 3 ppm / degrees C or less. Thereby, the curvature by the thermal expansion of a printed wiring board can be made small.

  In addition, the woven structure of the glass fiber woven fabric is not particularly limited, and examples thereof include plain weave, nanako weave, satin weave, twill weave, etc. Among them, laser workability, strength, interlayer insulation of via holes, among others. From the viewpoint of excellent reliability, a plain weave structure is preferable.

Next, a method for producing the surface-treated glass fiber woven fabric will be described.
The surface-treated glass fiber woven fabric in the present embodiment can be produced by impregnating the glass fiber woven fabric with a treatment liquid containing a coupling agent.

The content of the coupling agent in the treatment liquid containing the coupling agent is preferably 2.2% by mass or more and 10.0% by mass or less, more preferably 3.0% by mass or more and 5.0% by mass or less. .
Further, from the viewpoint of improving the impregnation property of the coupling agent into the glass fiber woven fabric, the time for impregnating the glass fiber woven fabric with the treatment liquid containing the coupling agent is preferably 0.01 minutes or more and 10 minutes or less. The impregnation temperature is preferably 10 ° C. or more and 40 ° C. or less, and the pH of the treatment liquid containing the coupling agent is preferably 4 or more and 10 or less.
With such treatment conditions, the luminance ratio (X ₁ / X ₂ ) of the sheet-like surface-treated glass fiber woven fabric treated with the coupling agent and the coupling agent in the surface-treated glass fiber woven fabric A surface-treated glass fiber woven fabric having an adhesion amount within the above range can be obtained more efficiently.

Examples of the coupling agent include epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, styrylsilane, methacryloxysilane, acryloxysilane, mercaptosilane, N-butylaminopropyltrimethoxysilane, and N-ethylamino. Isobutyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3- (N-allylamino) propyltrimethoxysilane, (cyclohexylaminomethyl) triethoxysilane, N-cyclohexyl Aminopropyltrimethoxysilane, N-ethylaminoisobutylmethoxyldiethoxysilane, (phenylaminomethyl) methyldimethoxysilane, N-phenylaminomethyltriethoxysilane, N-methyl Ruaminopropylmethyldimethoxysilane, vinylsilane, isocyanate silane, sulfide silane, chloropropylsilane, ureidosilane, hexamethyldisilazane (HMDS), 1,3-divinyl-1,1,3,3-tetramethyldisilazane, octa One type or two or more types selected from methyltrisilazane, hexamethylcyclotrisilazane compound, N- (vinylbenzyl) -2-aminoethyl-3-aminopropylmethoxysilane and the like can be mentioned.
Among these, γ-glycidoxypropyltrimethoxysilane, N-butylaminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxy Silane, 3- (N-allylamino) propyltrimethoxysilane, (cyclohexylaminomethyl) triethoxysilane, N-cyclohexylaminopropyltrimethoxysilane, N-ethylaminoisobutylmethoxyldiethoxysilane, (phenylaminomethyl) methyldimethoxysilane N-phenylaminomethyltriethoxysilane, N-methylaminopropylmethyldimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropylmethoxysilane One or more selected from the preferred.

  As the solvent of the treatment liquid, either water or an organic solvent can be used, but water is preferable from the viewpoint of improving the reactivity between the coupling agent and the glass fiber woven fabric.

  Next, the printed wiring board 300 according to the present embodiment will be described. 5 and 6 are cross-sectional views showing an example of the configuration of the printed wiring board 300 in the present embodiment.

  The printed wiring board 300 includes at least an insulating layer 301 provided with a via hole 307 and a metal layer 303 provided on at least one surface of the insulating layer 301. In the present embodiment, the via hole 307 is a hole for electrically connecting the layers, and may be either a through hole or a non-through hole.

As shown in FIG. 5, the printed wiring board 300 according to the present embodiment may be a single-sided printed wiring board, a double-sided printed wiring board, or a multilayer printed wiring board. A double-sided printed wiring board is a printed wiring board in which a metal layer 303 is laminated on both sides of an insulating layer 301. The multilayer printed wiring board is a print in which two or more metal layers 303 are stacked on an insulating layer 301 via an interlayer insulating layer (also referred to as a build-up layer) by a plated through hole method, a build-up method, or the like. It is a wiring board.
Here, in the printed wiring board 300 according to the present embodiment, the insulating layer 301 corresponds to the insulating layer 301 of the resin substrate 150 or the metal-clad laminate 200 according to the present embodiment.

  The metal layer 303 is, for example, a circuit layer, and includes an electroless metal plating film 308 and an electrolytic metal plating layer 309.

  When the printed wiring board 300 is a multilayer printed wiring board as shown in FIG. 6, the metal layer 303 is a circuit layer in the core layer 311 or the buildup layer 317.

  The metal layer 303 is formed by, for example, the SAP (semi-additive process) method on the surface of the insulating layer 301 that has been subjected to chemical treatment or plasma treatment. After the electroless plating film 308 is applied on the insulating layer 301, the non-circuit forming portion is protected by a plating resist, the electrolytic metal plating layer 309 is applied by electrolytic plating, and the electroless metal plating is removed by removing the plating resist and flash etching. The metal layer 303 is formed over the insulating layer 301 by removing the film 308.

  The circuit dimension of the metal layer 303 can be 25 μm / 25 μm or less, particularly 15 μm / 15 μm or less, when expressed in line and space (L / S). If the circuit dimensions are reduced and the wiring is made fine, the insulation reliability between the wirings decreases. However, the printed wiring board 300 according to the present embodiment is capable of fine wiring with a line and space (L / S) of 15 μm / 15 μm or less, and the line and space (L / S) can be refined to about 10 μm / 10 μm. Can be achieved.

  The thickness of the metal layer 303 is not particularly limited, but is usually 5 μm or more and 25 μm or less.

The insulating layer 305 in the buildup layer 317 is not particularly limited as long as it is made of an insulating material, but can be made of, for example, a resin film or a prepreg. Among these, the prepreg is a sheet-like material and has excellent dielectric properties, various properties such as mechanical and electrical connection reliability under high temperature and high humidity, and is suitable for manufacturing a build-up layer 317 for a printed wiring board. preferable.
As the prepreg, the prepreg 100 described above is particularly preferable.

  The thickness of the insulating layer 301 in the core layer 311 (including the insulating layer 301 in the printed wiring board 300 not including the build-up layer 317) is preferably 0.025 mm or more and 0.3 mm or less. When the thickness of the insulating layer 301 is within the above range, the balance between mechanical strength and productivity is particularly excellent, and the insulating layer 301 suitable for a thin printed wiring board can be obtained.

  The thickness of the insulating layer 305 in the buildup layer 317 is preferably 0.015 mm or more and 0.05 mm or less. When the thickness of the insulating layer 305 is within the above range, the balance between mechanical strength and productivity is particularly excellent, and the insulating layer 305 suitable for a thin printed wiring board can be obtained.

  Next, an example of a method for manufacturing the printed wiring board 300 will be described. However, the method for manufacturing the printed wiring board 300 according to the present embodiment is not limited to the following example.

First, the metal-clad laminate 200 is prepared.
Next, the metal foil 105 is removed by etching.

Next, a via hole 307 is formed in the insulating layer 301. The via hole 307 can be formed using, for example, a drilling machine or laser irradiation. Examples of the laser used for laser irradiation include an excimer laser, a UV laser, and a carbon dioxide gas laser. Resin residues after forming the via hole 307 may be removed by an oxidizing agent such as permanganate or dichromate.
Note that the via hole 307 may be formed in the insulating layer 301 before the metal foil 105 is removed by the etching treatment.

Next, a chemical treatment or a plasma treatment is performed on the surface of the insulating layer 301.
The chemical treatment is not particularly limited, and examples thereof include a method using an oxidant solution having an organic substance decomposing action. Examples of the plasma treatment include a method of removing organic residue by irradiating a target with an active species (plasma, radical, etc.) having a strong oxidizing action directly.

  Next, the metal layer 303 is formed. The metal layer 303 can be formed by, for example, a semi-additive process. This will be specifically described below.

  First, an electroless metal plating film 308 is formed on the surface of the insulating layer 301 and the via hole 307 by using an electroless plating method, so that both sides of the printed wiring board 300 are electrically connected. The via hole 307 can be appropriately filled with a conductor paste or a resin paste. An example of the electroless plating method will be described. For example, first, catalyst nuclei are provided on the surface of the insulating layer 301. The catalyst nucleus is not particularly limited. For example, a noble metal ion or palladium colloid can be used. Subsequently, an electroless metal plating film 308 is formed by electroless plating using the catalyst nucleus as a nucleus. For the electroless plating treatment, for example, one containing copper sulfate, formalin, complexing agent, sodium hydroxide, or the like can be used. In addition, it is preferable to heat-process 100-250 degreeC after electroless plating, and to stabilize a plating film. A heat treatment at 120 to 180 ° C. is particularly preferable in that a film capable of suppressing oxidation can be formed. Moreover, the average thickness of the electroless metal plating film 308 is, for example, about 0.1 to 2 μm.

  Next, a plating resist having a predetermined opening pattern is formed on the electroless metal plating film 308. This opening pattern corresponds to, for example, a circuit pattern. The plating resist is not particularly limited, and known materials can be used, but liquid and dry films can be used. In the case of forming fine wiring, it is preferable to use a photosensitive dry film or the like as the plating resist. An example using a photosensitive dry film will be described. For example, a photosensitive dry film is laminated on the electroless metal plating film 308, the non-circuit formation region is exposed and photocured, and the unexposed portion is dissolved and removed with a developer. A plating resist is formed by leaving the cured photosensitive dry film.

  Next, an electrolytic metal plating layer 309 is formed by electroplating at least inside the opening pattern of the plating resist and on the electroless metal plating film 308. The electroplating treatment is not particularly limited, but a known method used for ordinary printed wiring boards can be used. For example, in a state where the plating solution is immersed in a plating solution such as copper sulfate, an electric current is supplied to the plating solution. A method such as flowing can be used. The electrolytic metal plating layer 309 may be a single layer or may have a multilayer structure. The material of the electrolytic metal plating layer 309 is not particularly limited, and for example, any one or more of copper, copper alloy, 42 alloy, nickel, iron, chromium, tungsten, gold, and solder can be used.

  Next, the plating resist is removed using an alkaline stripping solution, sulfuric acid, or a commercially available resist stripping solution.

  Next, the electroless metal plating film 308 other than the region where the electrolytic metal plating layer 309 is formed is removed. For example, the electroless metal plating film 308 can be removed by using soft etching (flash etching) or the like. Here, the soft etching treatment can be performed, for example, by etching using an etchant containing sulfuric acid and hydrogen peroxide. Thereby, the metal layer 303 can be formed. The metal layer 303 is composed of an electroless metal plating film 308 and an electrolytic metal plating layer 309.

  Furthermore, a build-up layer 317 can be stacked on the printed wiring board 300 as necessary, and the steps of interlayer connection and circuit formation by a semi-additive process can be repeated to form a multilayer.

  The printed wiring board 300 of this embodiment is obtained by the above.

  Next, the semiconductor device 400 according to the present embodiment will be described. 7 and 8 are cross-sectional views showing an example of the configuration of the semiconductor device 400 in the present embodiment. The printed wiring board 300 can be used in a semiconductor device 400 as shown in FIGS. A method for manufacturing the semiconductor device 400 is not particularly limited, and examples thereof include the following method.

  First, a build-up layer is laminated on the metal layer 303 (circuit layer) as necessary, and the steps of interlayer connection and circuit formation by a semi-additive process are repeated. And the soldering resist layer 401 is laminated | stacked on the both surfaces or single side | surface of the printed wiring board 300 as needed.

  The method of forming the solder resist layer 401 is not particularly limited. For example, a method of forming by laminating, exposing and developing a dry film type solder resist, or exposing and developing a liquid resist printed This is done by the forming method.

  Subsequently, by performing a reflow process, the semiconductor element 407 is fixed to the connection terminal which is a part of the circuit layer via the solder bump 410. Thereafter, the semiconductor device 400 as shown in FIGS. 7 and 8 is obtained by sealing the semiconductor element 407, the solder bump 410, and the like with the sealing material 413.

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 100 is one layer is shown, but an insulating layer may be manufactured using a laminate of two or more prepregs 100.
Moreover, in the said embodiment, although the semiconductor element 407 and the circuit layer of the printed wiring board 300 were connected by the solder bump 410, it is not restricted to this. For example, the semiconductor element 407 and the circuit layer of the printed wiring board 300 may be connected by a bonding wire.

  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: Aralkyl-type epoxy resin (Nippon Kayaku Co., Ltd., NC3000H)
Epoxy resin B: naphthylene ether type epoxy resin (manufactured by DIC, HP6000)

Cyanate resin A: Novolac-type cyanate resin (Lonza Japan, Primaset PT-30)
Cyanate resin B: naphthol aralkyl type cyanate resin (synthesized by the method described in Synthesis Example 1 of paragraph 0026 of JP-A-2009-35728)

  Bismaleimide Compound B: Polyphenylmethane maleimide (manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-2300)

  Phenoxy resin: Phenoxy resin containing a bisphenolacetophenone structure (YX-6900BH45, manufactured by Mitsubishi Chemical Corporation)

Filler B: Spherical silica (manufactured by Admatechs, SO-31R, average particle size 1.0 μm)
Filler C: Spherical silica (manufactured by Denki Kagaku Kogyo, SFP-130MC, average particle size 0.7 μm)
Filler D: Nanosilica (manufactured by Admatechs, Admanano, γ-glycidoxypropyltrimethoxysilane (KBM403E) surface-treated product, average particle size 65 nm)

Coupling agent A: γ-glycidoxypropyltrimethoxysilane (manufactured by Momentive Performance Materials, A-187)
Curing accelerator A: Phosphorus catalyst of onium salt compound (Sumitomo Bakelite Co., Ltd., C05-MB)

Surface-treated glass fiber woven fabric A: Glass woven fabric (T glass woven fabric manufactured by Nitto Boseki Co., Ltd., WTX1035-X133, IPC standard 1035, linear expansion coefficient in warp direction: 2.8 ppm / ° C., thickness: 30 μm, basis weight: 30 g / M ² , average diameter of glass fiber: 5 μm, bulk density: 1.0 g / cm ³ , air permeability: 40 cc / cm ² / sec), 1.5% by mass of N- (vinylbenzyl) -2-amino After immersing in an aqueous solution of ethyl-3-aminopropylmethoxysilane (pH 6) at 30 ° C. for 0.1 minute to attach N- (vinylbenzyl) -2-aminoethyl-3-aminopropylmethoxysilane to a glass woven fabric It was produced by drying at 110 ° C. for 2 minutes in a drying furnace.

  Surface-treated glass fiber woven fabric B: produced by increasing the concentration of the N- (vinylbenzyl) -2-aminoethyl-3-aminopropylmethoxysilane aqueous solution at the time of production of the surface-treated glass fiber woven fabric A by 1.5 times.

  Surface-treated glass fiber woven fabric C: produced by doubling the concentration of the N- (vinylbenzyl) -2-aminoethyl-3-aminopropylmethoxysilane aqueous solution in the production of the surface-treated glass fiber woven fabric A.

  Surface-treated glass fiber woven fabric D: The surface-treated glass fiber woven fabric A was prepared by increasing the concentration of the N- (vinylbenzyl) -2-aminoethyl-3-aminopropylmethoxysilane aqueous solution three times during the production of the surface-treated glass fiber woven fabric A.

Surface-treated glass fiber woven fabric E: Glass woven fabric (T glass woven fabric manufactured by Nittobo, WTX-116E-X133, IPC standard 2116, linear expansion coefficient in warp direction: 2.8 ppm / ° C., thickness: 89 μm, basis weight : 104 g / m ² , average diameter of glass fiber: 7 μm, bulk density: 1.2 g / cm ³ , air permeability: 7 cc / cm ² / sec) Produced.

Surface treated glass fiber woven fabric F: Glass woven fabric (T glass woven fabric manufactured by Nittobo Co., Ltd., WTX-116E-X137, IPC standard 2116, linear expansion coefficient in the warp direction: 2.8 ppm / ° C., thickness: 89 μm, basis weight : 104 g / m ² , average diameter of glass fiber: 7 μm, bulk density: 1.2 g / cm ³ , air permeability: 7 cc / cm ² / sec) Produced.

Surface-treated glass fiber woven fabric G: Glass woven fabric (T glass woven fabric manufactured by Nittobo Co., Ltd., WTX1302-X133, no IPC standard, linear expansion coefficient in warp direction: 2.8 ppm / ° C., thickness: 128 μm, basis weight: 154 g / M ² , average diameter of glass fiber: 7 μm, bulk density: 1.2 g / cm ³ , air permeability: 3 cc / cm ² / sec) .

Surface-treated glass fiber woven fabric H: Glass woven fabric (T glass woven fabric manufactured by Nitto Boseki Co., Ltd., WTX1302-X137, no IPC standard, linear expansion coefficient in warp direction: 2.8 ppm / ° C., thickness: 128 μm, basis weight: 154 g / M ² , average diameter of glass fiber: 7 μm, bulk density: 1.2 g / cm ³ , air permeability: 3 cc / cm ² / sec) .

(Examples and comparative examples)
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 11 are shown in Table 2. In addition, P1 to P11 described in Tables 2 and 3 mean prepreg 1 to prepreg 11.

[1] Prepreg 1
1. Preparation of Varnish 1 of Resin Material 23 parts by mass of aralkyl type epoxy resin (Nippon Kayaku Co., Ltd., NC3000H) as epoxy resin A, 11 mass of novolak type cyanate resin (Lonza Japan Co., Ltd., Primaset PT-30) as cyanate resin A 2 parts by mass of a phenoxy resin (manufactured by Mitsubishi Chemical Corporation, YX-6900BH45) containing a bisphenolacetophenone structure as a phenoxy resin was dissolved and dispersed in methyl ethyl ketone. Furthermore, 58.0 parts by mass of spherical silica (manufactured by Admatechs, SO-31R, average particle size 1.0 μm) as filler B and nanosilica (manufactured by Admatechs, Admanano, KBM403E surface treated product, average) Particle size 65 nm) 5.0 parts by mass, γ-glycidoxypropyltrimethoxysilane (Momentive Performance Materials, A-187) 0.5 part by mass as coupling agent A, onium as curing accelerator Phosphorus catalyst of a salt compound (Sumitomo Bakelite Co., Ltd., C05-MB) 0.5 part by mass was added, and the mixture was stirred for 30 minutes using a high-speed stirrer to adjust the nonvolatile content to 70% by mass, A resin material varnish 1 (resin varnish 1) was prepared.

2. Manufacture of prepreg (prepreg 1)
The surface-treated glass fiber woven fabric D was impregnated with the resin varnish 1 with a coating device and dried in a heating furnace at 180 ° C. for 2 minutes to obtain a prepreg 1 (P1) having a thickness of 50 μm.

(Prepreg 3-11)
Prepregs 3 to 11 were produced in the same manner as prepreg 1 except that the types of resin varnish and surface-treated glass fiber woven fabric were changed as shown in Tables 1 and 2.

Example 1
1. Manufacture of resin substrate Two prepregs 1 are stacked, and ultra-thin copper foil (Mitsui Metal Mining Co., Ltd., Micro-Sin Ex, 1.5 μm) is stacked on both sides, followed by heat-pressure molding at a pressure of 4 MPa and a temperature of 220 ° C. for 120 minutes. 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 0.1 mm.

2. Production of Printed Wiring Substrate After the electrolytic copper foil layer on the surface of the resin substrate with metal foil obtained in the previous section was subjected to blackening treatment, a through hole of φ80 μm for interlayer connection was formed with a carbon dioxide laser. Next, it is immersed for 5 minutes in a swelling liquid at 70 ° C. (Swelling Dip Securigant P, manufactured by Atotech Japan), and further immersed for 5 minutes in an aqueous solution of potassium permanganate at 80 ° C. (Concentrate Compact CP, manufactured by Atotech Japan). Then, it neutralized and the desmear process in a through hole was performed. Next, after the surface of the electrolytic copper foil layer is etched by about 1 μm by flash etching, electroless copper plating is performed with a thickness of 0.5 μm, a resist layer for electrolytic copper plating is formed with a thickness of 18 μm, and pattern copper plating is performed. The film was post-cured by heating at 200 ° C. for 60 minutes. Next, the plating resist was removed and the entire surface was flash etched to form a pattern of L / S = 15/15 μm.

(Examples 2-6 and Comparative Examples 1-4)
A resin substrate and a printed wiring board were produced in the same manner as in Example 1 except that the resin substrate configuration shown in Tables 3 and 4 was used.

  In addition, the following evaluations were performed on the resin substrates obtained in the examples and comparative examples. The evaluation results are shown in Tables 3 and 4.

(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 the copper foil was removed with an etching solution (ferric chloride solution, 35 ° C.). Subsequently, measurement was performed at a temperature rising rate of 5 ° C./min and a frequency of 1 Hz using DMA 2980 manufactured by TA Instruments. The glass transition temperature was a temperature at which tan δ had a maximum value at a frequency of 1 Hz.

(2) Storage elastic modulus E '
The storage elastic modulus E ′ was measured by dynamic viscoelasticity measurement (DMA).
A test piece of 8 mm × 40 mm was cut out from the obtained resin substrate, and the copper foil was removed with an etching solution (ferric chloride solution, 35 ° C.). Next, storage elastic modulus was measured at 25 ° C. using a TA instrument DMA 2980 at a heating rate of 5 ° C./min and a frequency of 1 Hz.

(3) Linear expansion coefficient A test piece of 4 mm x 15 mm was cut out from the obtained resin substrate, and the copper foil was removed with an etching solution (ferric chloride solution, 35 ° C). Next, a planar direction (XY direction) in the range of 25 ° C. to 150 ° C. using a thermomechanical analyzer TMA (manufactured by TA Instruments, Q400) under conditions of a heating rate of 10 ° C./min, a load of 5 g, and a tensile mode. ) Of the linear expansion coefficient.

(4) Presence / absence of silica particles in the strand The cross-section perpendicular to the thickness direction of the obtained resin substrate was observed with SEM (50000 times magnification), and the silica particles as a filler inside the strand of the surface-treated glass fiber woven fabric The presence or absence of was evaluated.

(5) Insulation reliability evaluation A fine circuit pattern portion having a distance of 100 μm between two through holes in a printed wiring board is coated with an insulating resin sheet (BLA-3700GS, manufactured by Sumitomo Bakelite Co., Ltd.) at a temperature of 200 ° C. after lamination. Hardened) to produce a test sample. With respect to this test sample, the insulation resistance in continuous humidity was evaluated under the conditions of a temperature of 130 ° C., a humidity of 85%, and an applied voltage of 3.3 V. A resistance value of 10 ⁶ Ω or less was regarded as a failure. Evaluation was made according to the following criteria.
◎: No failure for 300 hours or more ○: Failure in 200 to less than 300 hours △: Failure in 100 to less than 200 hours ×: Failure in less than 100 hours

(6) Luminance ratio between the surface of the glass woven fabric and the inside of the fiber bundle The surface-treated glass fiber woven fabric is treated with a fluorescent labeling agent (A5593 manufactured by Tokyo Chemical Industry Co., Ltd.) that reacts with the coupling agent attached to the glass woven fabric. Processed. Next, the surface-treated glass fiber woven fabric was washed with acetone to remove the unreacted fluorescent labeling agent. Next, a cross section of the surface-treated glass fiber woven fabric was photographed with a confocal laser fluorescence microscope (magnification 50 times). From the obtained observation image, the luminance (X ₁ ) at the surface portion in the film thickness direction of the surface-treated glass fiber woven fabric and the luminance at the center portion of the glass fiber bundle in the film thickness direction of the surface-treated glass fiber woven fabric ( The luminance ratio X ₁ / X ₂ was calculated using the value of the G element in the RGB color system as X ₂ ).

(7) Coupling agent adhesion amount of surface-treated glass fiber woven fabric The coupling agent adhesion amount of surface-treated glass fiber woven fabric was measured by measuring the loss on ignition of the surface-treated glass fiber woven fabric in JIS R3420.

(8) Air permeability of glass fiber woven fabric The air permeability of glass fiber woven fabric was measured by measuring the air permeability of the cloth in JIS R3420.

(9) Bulk density of glass fiber woven cloth Measure the thickness of the cloth and mat in JIS R3420 and the thickness of the cloth and mat in JIS R3420, and divide the thickness of the cloth from the mass per unit area obtained. Then, the bulk density of the glass fiber woven fabric was calculated.

5a Carrier material 5b Carrier material 11 Surface-treated glass fiber woven fabric 100 Prepreg 101 Fiber substrate layer 103 Resin layer 105 Metal foil 150 Resin substrate 60 Vacuum laminating device 61 Laminating roll 62 Hot air drying device 200 Metal-clad laminate 300 Printed wiring substrate 301 Insulating layer 303 Metal layer 305 Insulating layer 307 Via hole 308 Electroless metal plating film 309 Electrolytic metal plating layer 311 Core layer 317 Build-up layer 400 Semiconductor device 401 Solder resist layer 407 Semiconductor element 410 Solder bump 413 Sealant

Claims (15)

A prepreg used for forming an insulating layer of a printed wiring board,
A fiber base layer comprising a sheet-like surface-treated glass fiber woven fabric treated with a coupling agent;
A resin layer provided on both surfaces of the fiber base layer and containing an epoxy resin and an inorganic filler;
With
When the surface-treated glass fiber woven fabric is treated with a fluorescent labeling agent that reacts with the coupling agent, and a cross-section of the surface-treated glass fiber woven fabric is observed with a confocal laser fluorescence microscope,
The luminance of the surface portion of the thickness direction of the surface-treated glass fiber woven fabric and X _1,
When the luminance at the center of the glass fiber bundles in the thickness direction of the surface-treated glass fiber woven fabric was X _2,
X ₁ / _{X 2} is 0.8 to 1.3,
The amount of the coupling agent in the surface-treated glass fiber woven fabric is 0.07% by mass to 0.50% by mass with respect to 100% by mass of the surface-treated glass fiber woven fabric,
The glass transition temperature of a cured product obtained by heating and pressing the prepreg at a pressure of 4 MPa and a temperature of 220 ° C. for 120 minutes, measured by dynamic viscoelasticity measurement under conditions of a heating rate of 5 ° C./min and a frequency of 1 Hz. A prepreg having a temperature of 180 ° C. or higher. The prepreg according to claim 1,
A prepreg in which the resin layer further contains one or more selected from the group consisting of a bismaleimide compound and a cyanate resin. The prepreg according to claim 1 or 2,
A prepreg in which the glass fiber woven fabric constituting the surface-treated glass fiber woven fabric has an air permeability of 1 cc / cm ² / sec to 100 cc / cm ² / sec. In the prepreg as described in any one of Claims 1 thru | or 3,
The glass fiber woven fabric constituting the surface-treated glass fiber woven fabric is one or two selected from E glass, S glass, D glass, T glass, NE glass, UT glass, L glass, HP glass, and quartz glass. A prepreg using the above glass fiber. In the prepreg as described in any one of Claims 1 thru | or 4,
A prepreg having a bulk density of 0.5 g / cm ³ or more and 1.5 g / cm ³ or less of the glass fiber woven fabric constituting the surface-treated glass fiber woven fabric. In the prepreg as described in any one of Claims 1 thru | or 5,
A prepreg in which the inorganic filler contains silica particles. The prepreg according to claim 6,
The surface-treated glass fiber woven fabric is composed of strands,
A prepreg in which a part of the silica particles is present in the strand. In the prepreg as described in any one of Claims 1 thru | or 7,
A cured product obtained by heating and pressing the prepreg at a pressure of 4 MPa and a temperature of 220 ° C. for 120 minutes, measured using a thermomechanical analyzer under conditions of a temperature rising rate of 10 ° C./min, a load of 5 g, and a tensile mode. A prepreg having an average linear expansion coefficient α ₁ in the range of 25 ° C. to 150 ° C. in the in-plane direction of 20.0 ppm / ° C. or less. In the prepreg as described in any one of Claims 1 thru | or 8,
A prepreg having a storage elastic modulus E ′ at 25 ° C. of 5 GPa or more of a cured product obtained by heating and pressing the prepreg at a pressure of 4 MPa and a temperature of 220 ° C. for 120 minutes. In the prepreg as described in any one of Claims 1 thru | or 9,
A prepreg containing a naphthalene type epoxy resin in which the epoxy resin has a naphthalene ring skeleton and has two or more glycidyl groups. In the prepreg as described in any one of Claims 1 thru | or 10,
A prepreg having a thickness of 30 μm or more and 220 μm or less.   The resin substrate containing the hardened | cured material of the prepreg as described in any one of Claims 1 thru | or 11.   The metal-clad laminated board by which the metal foil is provided in the single side | surface or both surfaces of the laminated body which laminated | stacked the resin substrate of Claim 12, or the said resin substrate 2 or more.   A printed wiring board, wherein one or two or more circuit layers are provided on one or both sides of the resin substrate according to claim 12 or a laminate in which two or more of the resin substrates are stacked.   The semiconductor device which mounted the semiconductor element on the said circuit layer of the printed wiring board of Claim 14.

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