JP2015211086A - Resin composition for insulator layer of printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for an insulator layer of a printed wiring board, which has good dispersion stability, shows an adequate melt viscosity, and enables the suppression of warp in the step of mounting a part.SOLUTION: A resin composition for an insulator layer of a printed wiring board comprises: a nonvolatile component; and an inorganic filler of which the content is 40-75 vol.% to 100 vol.% of the nonvolatile component in the resin composition, and the geometric parameter A satisfies the following condition: 20≤6A≤40, where A=SRρ/6. [In the formula, S represents a specific surface area (m/g) of the inorganic filler; R represents an average particle diameter (μm) of the inorganic filler; and ρ represents a density (g/cm) of the inorganic filler.]

Description

  The present invention relates to a resin composition for an insulating layer of a printed wiring board.

  As a manufacturing technique of a printed wiring board, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately stacked on an inner layer substrate is known. In the manufacturing method by the build-up method, the insulating layer is formed by, for example, laminating the resin composition layer on the inner substrate using an adhesive film including the resin composition layer and curing the resin composition layer. From the viewpoint of reducing the thermal expansion coefficient of the resulting insulating layer and preventing the occurrence of cracks and circuit distortion due to the difference in thermal expansion between the insulating layer and the conductor layer, the resin composition used for forming the insulating layer, In general, it contains an inorganic filler. As the inorganic filler, a spherical inorganic filler is preferably used (Patent Document 1).

JP 2010-238667 A

  With the recent replacement from lead-containing solder to lead-free solder, the solder reflow temperature in the component mounting process is increasing. In recent years, printed wiring boards have been further reduced in thickness in order to achieve miniaturization of electronic devices.

  As the printed wiring board becomes thinner, the printed wiring board is warped in the component mounting process, which may cause problems such as circuit distortion and component contact failure. The present inventors have found that warpage in a component mounting process can be suppressed by using a crushed inorganic filler instead of a spherical inorganic filler. However, a resin composition containing a crushed inorganic filler is inferior in dispersion stability and tends to result in a high melt viscosity, resulting in poor lamination.

  The subject of this invention is providing the resin composition for insulating layers of a printed wiring board which can suppress the curvature in the mounting process of components while showing favorable dispersion stability and moderate melt viscosity.

  As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by using a predetermined amount of an inorganic filler having a specific shape, and have completed the present invention.

That is, the present invention includes the following contents.
[1] A resin composition for an insulating layer of a printed wiring board,
When the non-volatile component in the resin composition is 100% by volume, the content of the inorganic filler is 40 to 75% by volume,
Formula: A = SRρ / 6 [wherein S is the specific surface area of the inorganic filler (m ² / g), R is the average particle diameter (μm) of the inorganic filler, and ρ is the density of the inorganic filler (g / cm ³ ). ] The resin composition in which the shape parameter A of the inorganic filler represented by 20 satisfies 20 ≦ 6A ≦ 40.
[2] A resin composition for an insulating layer of a printed wiring board,
When the non-volatile component in the resin composition is 100% by volume, the content of the inorganic filler is 40 to 75% by volume,
Formula: B = Lc / L [wherein L is the perimeter of the inorganic filler in a predetermined cross section (μm), Lc is the perimeter of a perfect circle of the same area as the cross section of the inorganic filler in the cross section (μm) Represents. ] The resin composition whose average value of the shape parameter B of the inorganic filler represented by this is 0.8 or more and 0.9 or less.
[3] The resin composition according to [1] or [2], wherein the average crystallite size of the inorganic filler is 1800 angstroms or less.
[4] The resin composition according to any one of [1] to [3], wherein the inorganic filler has a specific surface area of 3 to 10 m ² / g.
[5] The resin composition according to any one of [1] to [4], wherein the inorganic filler has an average particle size of 4 μm or less.
[6] The resin composition according to any one of [1] to [5], wherein the inorganic filler has an average particle size of 3 μm or less.
[7] The inorganic filler is obtained by dispersing tufted aggregates of microcrystalline particles having an average crystallite diameter of 1800 angstroms or less, and the maximum particle size of the tufted aggregates is 20 μm or less. [6] The resin composition according to any one of [6].
[8] The content of the crystalline inorganic filler in the inorganic filler is any one of [1] to [7], which is 50% by mass or more when the entire inorganic filler is 100% by mass. Resin composition.
[9] The resin composition according to [8], wherein the crystalline inorganic filler is crystalline silica.
[10] The resin composition according to any one of [1] to [9], further comprising an epoxy resin and a curing agent.
[11] The resin composition according to any one of [1] to [10], which is a resin composition for an interlayer insulating layer.
[12] A sheet-shaped laminated material including a resin composition layer formed of the resin composition according to any one of [1] to [11].
[13] A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [11].
[14] A semiconductor device including the printed wiring board according to [13].

  ADVANTAGE OF THE INVENTION According to this invention, while showing favorable dispersion stability and moderate melt viscosity, the curvature in the mounting process of components can be suppressed, The resin composition for insulating layers of a printed wiring board can be provided.

[Resin composition for insulating layer of printed wiring board]
The resin composition for an insulating layer of a printed wiring board of the present invention (hereinafter also simply referred to as “the resin composition of the present invention”) has a shape different from a conventionally known spherical inorganic filler and crushed inorganic filler. It contains an inorganic filler having a predetermined amount.

  Unlike the spherical inorganic filler, the inorganic filler used in the present invention has an angular shape. In this respect, the crushed inorganic filler has a sharp and square shape, and the inorganic filler used in the present invention is slightly rounded and has a shape different from the crushed inorganic filler.

  Compared with the projected shape on a plane, unlike the spherical inorganic filler whose corners are not clearly recognized, the inorganic filler used in the present invention can clearly recognize the corners. Here, “the angle can be recognized in the projected shape on the plane” means that in the projected shape on the plane, a certain straight line or substantially straight line, and the straight line or substantially straight line and a certain angle θ (inside the projected shape) It is possible to recognize a straight line or a substantially straight line that touches at an angle. And about the inorganic filler used by this invention, the average value of this angle (theta) is large compared with the crushed inorganic filler. For example, the inorganic filler used in the present invention has an average value of the angle θ of preferably 5 °, more preferably 7.5 °, still more preferably 10 °, and 12 °, compared to the crushed inorganic filler. 5 °, 15 °, 17.5 °, or 20 ° larger.

  Hereinafter, the shape of the inorganic filler used in the present invention will be described using two shape parameters, that is, the shape parameter A and the shape parameter B. Although the shape parameter A and the shape parameter B are different in whether they are parameters derived by a three-dimensional approach or parameters derived by a two-dimensional approach, both are related to the shape of the inorganic filler. This parameter represents the degree of deformation from a true sphere.

<Shape parameter A>
The shape parameter A is represented by the following formula (1).

Formula (1): A = SRρ / 6
[Where:
S represents the specific surface area (m ² / g) of the inorganic filler,
R represents the average particle size (μm) of the inorganic filler,
ρ represents the density (g / cm ³ ) of the inorganic filler. ]

Consider a system in which a plurality of true spheres exist (hereinafter also referred to as “true sphere model system”). When the average particle diameter of a sphere (diameter) is R, the average surface area of the plurality of sphericity present within a sphere model system is represented by .pi.R ^2, the average volume is represented by .pi.R ^3/6. Further, when the density of a true sphere is [rho, the average mass of the plurality of sphericity present within a sphere model system is represented by πρR ^3/6.

Next, an inorganic filler system having the same average volume and density as the true sphere model system is considered. Based on the fact that a true sphere has the smallest surface area in an object of the same volume, the average surface area of multiple inorganic fillers present in such an inorganic filler system can be expressed as AπR ² . Here, A is the shape parameter of the inorganic filler, and its lower limit is 1 (when the inorganic filler is a true sphere). Further, based on the condition that the equal average volume and density to the true sphere model system, the average mass of the plurality of inorganic filler present in the system of the inorganic filler can be represented by πρR ^3/6. In the inorganic filler system, the specific surface area S of the inorganic filler is [average surface area (AπR ² ) of a plurality of inorganic fillers present in the inorganic filler system] / [inorganic filler system] average mass of the plurality of the inorganic filler is present can be represented by (πρR ^3/6)], which becomes 6A / (Rρ). That is, the relational expression of S = 6A / (Rρ) is established, and when the expression is transformed with respect to the shape parameter A, the above expression (1) is obtained.

  The inorganic filler used in the present invention is characterized in that the shape parameter A represented by the above formula (1) satisfies 20 ≦ 6A ≦ 40. A suitable range of the shape parameter A will be described later.

  The specific surface area S of the inorganic filler necessary for obtaining the shape parameter A can be measured by the BET method. Specifically, a molecule having a known adsorption occupation area is adsorbed on the inorganic filler sample at the temperature of liquid nitrogen, and the specific surface area of the inorganic filler sample can be obtained from the amount of adsorption. As a molecule having a known adsorption-occupied area, an inert gas such as nitrogen or helium is preferably used. The specific surface area S of the inorganic filler can be measured using an automatic specific surface area measuring device, and examples of the automatic specific surface area measuring device include “Macsorb HM-1210” manufactured by Mountec Co., Ltd.

  The average particle diameter R of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis with a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. Examples of the laser diffraction type particle size distribution measuring apparatus include “SALD2200” manufactured by Shimadzu Corporation and “LA-500”, “LA-750”, and “LA-950” manufactured by Horiba, Ltd.

<Shape parameter B>
The shape parameter B is represented by the following formula (2).

Formula (2): B = Lc / L
[Where:
L represents the peripheral length (μm) of the inorganic filler in a predetermined cross section
Lc represents the circumference (μm) of a perfect circle having the same area as the cross-sectional area of the inorganic filler in the cross section. ]

  The shape parameter B is a parameter derived based on the fact that a perfect circle has the smallest perimeter in figures of the same area, and its upper limit is 1 (the cross-sectional shape of the inorganic filler is a perfect circle in a predetermined cross section) If).

  The shape parameter B is a parameter established for each particle of the inorganic filler, and by obtaining the shape parameter B for a sufficient number of particles constituting the inorganic filler, the overall characteristics regarding the shape of the inorganic filler can be obtained. It is possible to grasp. In one embodiment of the present invention, the shape parameter B is obtained for a sufficient number of particles constituting the inorganic filler, and the shape of the inorganic filler is characterized by the average value. In such an embodiment, the inorganic filler used in the present invention is characterized in that the average value of the shape parameter B represented by the above formula (2) is 0.8 or more and 0.9 or less. A suitable range of the average value of the shape parameter B will be described later.

  Alternatively, the shape parameter B can be obtained for a sufficient number of particles constituting the inorganic filler, and the shape distribution of the particles constituting the inorganic filler can be grasped based on the value of the obtained shape parameter B. . In the inorganic filler used in the present invention, the content of particles whose shape parameter B represented by the above formula (2) is less than 0.8 is usually 50% by number or less. In the inorganic filler used in the present invention, the content of particles having a shape parameter B represented by the above formula (2) greater than 0.9 is usually 30% by number or less. Suitable ranges for these contents will be described later.

  The peripheral length L of the inorganic filler in a predetermined cross section and the cross sectional area of the inorganic filler in the cross section necessary for obtaining the shape parameter B are the cross-sectional observations for the layer formed using the resin composition of the present invention. Can be measured. For cross-sectional observation, a FIB-SEM composite apparatus is preferably used. From the obtained FIB-SEM image, the peripheral length and area (cross-sectional area) of the inorganic filler present in the layer can be obtained using image processing software such as “QWin V3” manufactured by Leica Co., Ltd. . An example of the FIB-SEM composite device is “SMI3050SE” manufactured by SII Nanotechnology.

  Lc may be calculated by calculating the circumference (circumference) of a perfect circle having the same area as the cross-sectional area of the obtained inorganic filler.

  In one embodiment, the resin composition of the present invention has an inorganic filler content of 40 to 75% by volume when the nonvolatile component in the resin composition is 100% by volume, and is represented by the above formula (1). The shape parameter A of the inorganic filler to be satisfied satisfies 20 ≦ 6A ≦ 40 (hereinafter, also referred to as “resin composition of the first embodiment”).

  From the viewpoint of obtaining a resin composition exhibiting good dispersion stability and moderate melt viscosity, it is important that the value of 6A is 40 or less. Further, from the viewpoint of obtaining a resin composition exhibiting good dispersion stability and melt viscosity, the value of 6A is 39.8 or less, 39.6 or less, 39.4 or less, 39.2 or less, 39 or less, 38 or less. 37 or less, 36 or less, 35 or less, 34 or less, 33 or less, 32 or less, 31 or less, or 30 or less. The lower limit of 6A is important to be 20 or more from the viewpoint of sufficiently suppressing warpage in the component mounting process. From the viewpoint of further suppressing warpage in the component mounting process, the lower limit of 6A is preferably 21 or more, 22 or more, or 23 or more.

  In another embodiment, the resin composition of the present invention has an inorganic filler content of 40 to 75% by volume when the nonvolatile component in the resin composition is 100% by volume. The average value of the shape parameter B of the inorganic filler represented is 0.8 or more and 0.9 or less (hereinafter also referred to as “resin composition of the second embodiment”).

  From the viewpoint of obtaining a resin composition exhibiting good dispersion stability and moderate melt viscosity, it is important that the average value of the shape parameter B is 0.8 or more. Further, from the viewpoint of obtaining a resin composition exhibiting good dispersion stability and melt viscosity, the average value of the shape parameter B is preferably 0.81 or more, or 0.82 or more. The upper limit of the average value of the shape parameter B is important to be 0.9 or less from the viewpoint of sufficiently suppressing warpage in the component mounting process. From the viewpoint of further suppressing warpage in the component mounting process, the upper limit of the average value of the shape parameter B is 0.89 or less, 0.88 or less, 0.87 or less, 0.86 or less, or 0.85 or less. Preferably there is.

  Regardless of whether the first embodiment or the second embodiment is different, when the content of the inorganic filler is 100% by volume of the nonvolatile component in the resin composition, the viewpoint of sufficiently suppressing warpage in the component mounting process. From the viewpoint of sufficiently reducing the coefficient of thermal expansion of the resulting insulating layer, it is 40% by volume or more, preferably 42% by volume or more, more preferably 44% by volume or more, still more preferably 46% by volume or more, and even more preferably. Is 48% by volume or more, particularly preferably 50% by volume or more, 52% by volume or more, 54% by volume or more, 56% by volume or more, 58% by volume or more, or 60% by volume or more. When a crushed inorganic filler is used, the melt viscosity tends to increase excessively as the content of the inorganic filler increases. On the other hand, regarding the inorganic filler that satisfies the specific shape parameter condition used in the present invention, the content can be further increased while realizing a good melt viscosity. For example, in the resin composition of the present invention, the content of the inorganic filler may be increased to 62% by volume or more, 64% by volume or more, 66% by volume or more, or 68% by volume or more. The upper limit of the content of the inorganic filler is 75 from the viewpoint of obtaining a resin composition exhibiting an appropriate melt viscosity, and from the viewpoint of obtaining an insulating layer having a small surface roughness and excellent adhesion strength (peel strength) with a conductor layer. It is not more than volume%, preferably not more than 74 volume%, more preferably not more than 73 volume%, still more preferably not more than 72 volume%, still more preferably not more than 71 volume%, particularly preferably not more than 70 volume%. In particular, in the production of a printed wiring board, when laminating the resin composition layer and the inner layer substrate by a vacuum laminating method, the upper limit of the content of the inorganic filler is preferably 70% by volume or less. . The content (volume%) of the inorganic filler is based on the mass and density of the inorganic filler used for preparing the resin composition and the mass and density of the non-volatile components other than the inorganic filler used for preparing the resin composition. Can be calculated.

  Regardless of whether the first embodiment or the second embodiment, the shape parameter represented by the above formula (2) in the inorganic filler from the viewpoint of obtaining a resin composition exhibiting good dispersion stability and melt viscosity. The content of particles having a B value of less than 0.8 is preferably low. In the resin composition of the present invention, the content of particles in which the value of the shape parameter B represented by the above formula (2) in the inorganic filler is less than 0.8 is usually 50% by number or less, preferably Is 48% by number or less, more preferably 46% by number or less, still more preferably 44% by number or less, still more preferably 42% by number or less, or 40% by number or less. In particular, the content of particles having a shape parameter B value of 0.75 or less is preferably 20% by number or less, 18% by number or less, or 16% by number or less.

  Regardless of whether the first embodiment or the second embodiment is different, the value of the shape parameter B represented by the above formula (2) in the inorganic filler is sufficiently reduced from the viewpoint of sufficiently suppressing warpage in the component mounting process. The content of particles greater than 0.9 is preferably low. In the resin composition of the present invention, the content of particles having a shape parameter B value represented by the above formula (2) of greater than 0.9 in the inorganic filler is usually 30% by number or less, preferably It is 28% by number or less, more preferably 26% by number or less, further preferably 24% by number or less, still more preferably 22% by number or less, or 20% by number or less. In particular, the content of particles having a shape parameter B value of 0.94 or more is 6% or less, 4% or less, 2% or less, 1% or less, 0.8% or less, 0.6% or less. % Or less, 0.4 number% or less, and 0.2 number% or less are preferable.

  In the resin composition of the present invention, the material of the inorganic filler is not particularly limited. For example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide , Hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, titanate Magnesium, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate Gerare, silica is particularly preferred. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

  The average particle diameter (R) of the inorganic filler is preferably 4 μm or less, more preferably 3.5 μm or less, and even more preferably 3 μm or less, from the viewpoint of circuit wiring miniaturization. The lower limit of the average particle diameter of the inorganic filler is preferably 0.01 μm or more from the viewpoint of obtaining a resin varnish having an appropriate viscosity and good handleability when forming a resin varnish using the resin composition, 0.03 μm or more is more preferable, 0.05 μm or more is further preferable, 0.07 μm or more is even more preferable, and 0.1 μm or more is particularly preferable.

The specific surface area (S) of the inorganic filler is not particularly limited as long as the above shape parameter condition is satisfied in relation to the average particle diameter (R) and the density (ρ). The specific surface area of the inorganic filler, for example, may range from 3 to 10 m ² / g, it is preferably in the range of 3 to 8 m ² / g.

  The inorganic filler may be either amorphous or crystalline as long as the above shape parameter condition is satisfied. In one embodiment, the resin composition of the present invention contains a crystalline inorganic filler. The content of the crystalline inorganic filler in the inorganic filler is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more, when the total amount of the inorganic filler is 100% by mass. Even more preferably, it is 80% by mass or more, particularly preferably 90% by mass or more, 92% by mass or more, 94% by mass or more, 96% by mass or more, 98% by mass or more, or 99% by mass or more. The inorganic filler may be substantially composed of a crystalline inorganic filler except for impurities inevitably contained. In such an embodiment, the average crystallite diameter of the inorganic filler is preferably 1800 angstroms (Å) or less, more preferably 1600 Å or less, and even more preferably 1400 Å or less. Although the lower limit of the average crystallite diameter is not particularly limited, it can be usually 100 mm or more, 200 mm or more, and the like. The crystallite diameter of the inorganic filler can be measured using an X-ray diffraction (XRD) apparatus. Examples of the XRD apparatus include “Multi FLEX” manufactured by Rigaku Corporation.

  Among them, it is preferable to use crystalline silica as the crystalline inorganic filler.

  The inorganic filler satisfying the above-mentioned shape parameter is slightly rounded by, for example, a method of physically and / or chemically polishing the surface of a crushed inorganic filler having a sharp and angular shape, a method of heat treatment, and the like. It may be prepared by applying. The method of physical polishing and chemical polishing is not particularly limited, and any conventionally known method may be used. Examples of commercially available crushed silica include “VX-SR” manufactured by Tatsumori Co., Ltd.

  In addition, among the inorganic oxides that are naturally produced, there are inorganic oxides that suitably satisfy the above shape parameter conditions. For example, natural silica produced as tufted aggregates of microcrystalline particles having an average crystallite size of 1800 mm or less (especially when the maximum particle size of tufted aggregates is 20 μm or less) is dispersed during the preparation of the resin composition. As a result, the tufted aggregates are unraveled and the shape parameter condition is satisfied. Therefore, in one embodiment, the inorganic filler contained in the resin composition of the present invention is obtained by dispersing tufted aggregates of microcrystalline particles having an average crystallite diameter of 1800 mm or less, and the maximum of the tufted aggregates The particle diameter is 20 μm or less. Examples of such natural silica commercial products include “IMSIL A-8”, “IMSIL A-10”, “IMSIL A-15”, and “IMSIL A-25” manufactured by Unimin.

  The inorganic filler used in the resin composition of the present invention is preferably surface-treated with a surface treatment agent from the viewpoint of improving dispersibility and moisture resistance. Examples of the surface treatment agent include an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an organosilazane compound, and a titanate coupling agent. A surface treating agent may be used individually by 1 type, and may be used in combination of 2 or more type. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM803” (3-mercaptopropyltrimethoxy manufactured by Shin-Etsu Chemical Co., Ltd.). Silane), Shin-Etsu Chemical "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical "SZ-31" (Hexamethyldisilazane) manufactured by Co., Ltd.

After the surface treatment of the inorganic filler, the amount of carbon per unit surface area bonded to the surface of the inorganic filler is preferably 0.05 mg / m ² or more, more preferably 0.08 mg / m ² or more, more preferably 0.11 mg / ^{m 2} or more, even more preferably 0.14 mg / ^{m 2} or more, particularly preferably 0.17 mg / ^{m 2} or more, 0.20 mg / ^{m 2} or more, 0.23 mg / ^{m 2} or more, or 0. 26 mg / m ² or more. The upper limit of the carbon content is preferably 1.00 mg / ^{m 2} or less, more preferably 0.75 mg / ^{m 2} or less, more preferably 0.70 mg / ^{m 2} or less, even more preferably 0.65 mg / ^{m 2} or less , 0.60 mg / ^{m 2} or less, 0.55 mg / ^{m 2} or less, 0.50 mg / ^{m 2} or less.

  The amount of carbon per unit area bonded to the surface of the inorganic filler can be calculated by the following procedure. A sufficient amount of methyl ethyl ketone (MEK) as a solvent is added to the inorganic filler after the surface treatment, followed by ultrasonic cleaning. After removing the supernatant and drying the solid content, the amount of carbon bonded to the surface of the inorganic filler is measured using a carbon analyzer. By dividing the obtained amount of carbon by the specific surface area of the inorganic filler, the amount of carbon per unit surface area bonded to the inorganic filler is calculated. Examples of the carbon analyzer include “EMIA-320V” manufactured by Horiba, Ltd.

  The resin composition of the present invention preferably further contains a thermosetting resin and a curing agent. As the thermosetting resin, an epoxy resin is preferable. Therefore, in one embodiment, the resin composition of the present invention contains an epoxy resin and a curing agent in addition to the inorganic filler.

-Epoxy resin-
Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, Phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type Epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing ester Carboxymethyl resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, it has two or more epoxy groups in one molecule, and has a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and three or more epoxy groups in one molecule, It is preferable to contain a solid epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 20 ° C. By using a liquid epoxy resin and a solid epoxy resin in combination as an epoxy resin, a resin composition having excellent flexibility can be obtained. Moreover, the breaking strength of the cured product of the resin composition is also improved.

  As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, phenol novolac type epoxy resin, and epoxy resin having a butadiene structure are preferable, and bisphenol A type epoxy resin Bisphenol F type epoxy resin and naphthalene type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032H”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, and “jER828EL” (bisphenol A) manufactured by Mitsubishi Chemical Corporation. Type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "ZX1059" (bisphenol A type epoxy resin and bisphenol F type epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) ), “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, and “PB-3600” (epoxy resin having a butadiene structure) manufactured by Daicel Chemical Industries, Ltd. . These may be used alone or in combination of two or more.

  Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin, tetraphenylethane type epoxy resin are preferable, naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, bisphenol A type epoxy resin, Tetraphenylethane type epoxy resin is more preferable. Specific examples of the solid epoxy resin include “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” (cresol novolac type epoxy resin) manufactured by DIC Corporation, “ N-695 ”(cresol novolac type epoxy resin),“ HP-7200 ”(dicyclopentadiene type epoxy resin),“ EXA7311 ”,“ EXA7311-G3 ”,“ EXA7311-G4 ”,“ EXA7311-G4S ”,“ HP6000 ” ”(Naphthylene ether type epoxy resin),“ EPPN-502H ”(trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.,“ NC7000L ”(naphthol novolac type epoxy resin),“ NC3000H ”,“ NC3000 ”, “NC3000L”, “NC3100” (biphenyl) Epoxy resin), “ESN475V” (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “ESN485” (naphthol novolac type epoxy resin), “YX4000H”, “YL6121” (biphenyl type) manufactured by Mitsubishi Chemical Corporation Epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., Mitsubishi Chemical Corporation “YL7800” (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. “jER1010” (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “jER1031S” (tetraphenylethane type epoxy resin), and the like.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1: 4 in terms of mass ratio. preferable. By setting the quantitative ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is obtained when used in the form of a sheet-like laminated material, ii) the form of the sheet-like laminated material When used in the above, sufficient flexibility is obtained, handling properties are improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii) above, the quantitative ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is from 1: 0.3 to 1: 3.5 in mass ratio. Is more preferable, and a range of 1: 0.6 to 1: 3 is more preferable.

  The content of the epoxy resin in the resin composition is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 35% by mass, and even more preferably when the nonvolatile component in the resin composition is 100% by mass. Is 10% by mass to 30% by mass.

  The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By becoming this range, the crosslinked density of hardened | cured material becomes sufficient and it can bring about an insulating layer with small surface roughness. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

-Curing agent-
The curing agent is not particularly limited as long as it has a function of curing the epoxy resin. For example, a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, and a cyanate ester curing agent are included. Can be mentioned. A hardening | curing agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion strength with the conductor layer, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. Among these, a triazine skeleton-containing phenol novolac resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion strength with the conductor layer. These may be used alone or in combination of two or more.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "SN-495", "SN-375", "SN-395", "LA-7052," "LA-7054," "LA-3018," "LA-1356," "TD2090" manufactured by DIC Corporation Or the like.

  Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule. A compound having two or more in the above is preferably used. The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, and m-cresol. P-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzene Examples include triol, dicyclopentadiene type diphenol compound, phenol novolac and the like. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  The active ester type curing agent includes an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. These may be used alone or in combination of two or more. The “dicyclopentadiene-type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentalene-phenylene.

  As a commercial product of an active ester type curing agent, as an active ester compound containing a dicyclopentadiene type diphenol structure, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T” (manufactured by DIC Corporation) ), “EXB9416-70BK” (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, “DC808” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac, and benzoyl of phenol novolac Examples of the active ester compound containing a compound include “YLH1026” (manufactured by Mitsubishi Chemical Corporation).

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd., “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Although it does not specifically limit as a cyanate ester type hardening | curing agent, For example, novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardening agent, dicyclopentadiene type cyanate ester type hardening agent, bisphenol type (bisphenol A type, And bisphenol F type, bisphenol S type, and the like) and cyanate ester-based curing agents, and prepolymers in which these are partially triazines. Specific examples include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4′-ethylidene diphenyl diester. Cyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, , 3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bifunctional cyanate resins such as bis (4-cyanatephenyl) ether, phenol novolac and cresol novolac Derived from Polyfunctional cyanate resins, prepolymers in which these cyanate resins are partially triazine-modified, etc. Commercial products of cyanate ester-based curing agents include “PT30” and “PT60” manufactured by Lonza Japan K.K. Phenol novolac type polyfunctional cyanate ester resin), “BA230” (a prepolymer in which a part or all of bisphenol A dicyanate is triazine-modified into a trimer), and the like.

  From the viewpoint of improving the mechanical strength and water resistance of the resulting insulating layer, the amount ratio of the epoxy resin and the curing agent is a ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of curing agent]. The range of 1: 0.2 to 1: 2 is preferable, the range of 1: 0.3 to 1: 1.5 is more preferable, and the range of 1: 0.4 to 1: 1 is more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like, and varies depending on the type of the curing agent. Moreover, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the value obtained by dividing the solid mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is: The value obtained by dividing the solid mass of each curing agent by the reactive group equivalent is the total value for all curing agents.

  In one embodiment, the resin composition of the present invention contains the above-described inorganic filler, epoxy resin, and curing agent. Among them, the resin composition includes crystalline silica as an inorganic filler, and a mixture of a liquid epoxy resin and a solid epoxy resin as an epoxy resin (the mass ratio of liquid epoxy resin: solid epoxy resin is preferably 1: 0.1 to 0.15). 1: 4, more preferably 1: 0.3-1: 3.5, more preferably 1: 0.6-1: 3) as a curing agent, a phenolic curing agent, a naphthol curing agent, an active ester It is preferable that each contains at least one selected from the group consisting of a curing agent and a cyanate ester curing agent. Also regarding the resin composition layer containing a combination of such specific components, suitable contents of the inorganic filler, the epoxy resin, and the curing agent are as described above.

  The resin composition of the present invention may further contain one or more additives selected from the group consisting of a thermoplastic resin, a curing accelerator, a flame retardant, and an organic filler, if necessary.

-Thermoplastic resin-
Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, and polyether. Examples include ether ketone resins and polyester resins. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

  The weight average molecular weight in terms of polystyrene of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-reduced weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). In addition, “FX280” and “FX293” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “YL7553”, “YL6794”, “YL7213” manufactured by Mitsubishi Chemical Corporation, “YL7290”, “YL7482” and the like can be mentioned.

  Specific examples of the polyvinyl acetal resin include electric butyral 4000-2, 5000-A, 6000-C, and 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., and ESREC BH series and BX series manufactured by Sekisui Chemical Co., Ltd. KS series, BL series, BM series, etc. are mentioned.

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (described in JP-A No. 2002-12667 and JP-A No. 2000-319386).

  Specific examples of the polyamide-imide resin include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd.

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.

  The content of the thermoplastic resin in the resin composition is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, when the nonvolatile component in the resin composition is 100% by mass. It is 1 mass%, More preferably, it is 1 mass%-5 mass%.

-Curing accelerator-
Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, phosphorus-based curing accelerators, amine-based curing accelerators, and imidazole-based accelerators. A curing accelerator is preferred. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type. The content of the curing accelerator is preferably used in the range of 0.05% by mass to 3% by mass when the total of the nonvolatile components of the epoxy resin and the curing agent is 100% by mass.

-Flame retardant-
Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. A flame retardant may be used individually by 1 type, or may be used in combination of 2 or more type. The content of the flame retardant in the resin composition is not particularly limited, but is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass when the nonvolatile component in the resin composition is 100% by mass. -9 mass%.

-Organic filler-
As the organic filler, any organic filler that can be used for forming an insulating layer of a printed wiring board may be used. Examples thereof include rubber particles, polyamide fine particles, and silicone particles, and rubber particles are preferable.

  The rubber particle is not particularly limited as long as it is a fine particle of a resin that has been subjected to a chemical crosslinking treatment on a resin exhibiting rubber elasticity and is insoluble and infusible in an organic solvent. For example, acrylonitrile butadiene rubber particles, butadiene rubber particles, Examples include acrylic rubber particles. Specific examples of rubber particles include XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Staphyloid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (above, manufactured by Aika Industry Co., Ltd.) Paraloid EXL2655. , EXL2602 (manufactured by Kureha Chemical Industry Co., Ltd.) and the like.

  The average particle diameter of the organic filler is preferably in the range of 0.005 μm to 1 μm, more preferably in the range of 0.2 μm to 0.6 μm. The average particle diameter of the rubber particles can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and the particle size distribution of the rubber particles is measured on a mass basis using a concentrated particle size analyzer (“FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.). The median diameter can be measured by making the average particle diameter. The content of the rubber particles in the resin composition is preferably 1% by mass to 10% by mass, more preferably 2% by mass to 5% by mass.

-Other ingredients-
The resin composition of the present invention may contain other components as necessary. Such other components include, for example, organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds, as well as thickeners, antifoaming agents, leveling agents, adhesion imparting agents, colorants, and curable resins. And the like, and the like.

  The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which the compounding components are mixed and dispersed using a rotary mixer or the like after adding a solvent or the like as necessary.

  The resin composition of the present invention exhibits good dispersion stability and moderate melt viscosity, and can suppress warpage in the component mounting process. The resin composition of the present invention can be suitably used as a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for an interlayer insulating layer of a printed wiring board), and by plating thereon It can be more suitably used as a resin composition for forming an interlayer insulating layer on which a conductor layer is formed (a resin composition for an interlayer insulating layer of a printed wiring board on which a conductor layer is formed by plating). The resin composition of the present invention also requires a resin composition such as an adhesive film, a sheet-like laminated material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a hole-filling resin, and a component-filling resin. Can be used in a wide range of applications.

[Sheet laminated material]
The resin composition of the present invention can be used by being applied in a varnish state, but industrially generally, it is used in the form of a sheet-like laminate material including a resin composition layer formed of the resin composition. Is preferred.

  As the sheet-like laminated material, the following adhesive films and prepregs are preferable.

  In one embodiment, the adhesive film includes a support and a resin composition layer (adhesive layer) bonded to the support, and the resin composition layer (adhesive layer) is the resin composition of the present invention. Formed from.

  The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, and even more preferably 50 μm or less or 40 μm or less, from the viewpoint of reducing the thickness of the printed wiring board. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, it is 10 micrometers or more.

  Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). .) Polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), polymethyl methacrylate (PMMA) and other acrylics, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When using metal foil as a support body, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, Copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.). It may be used.

  The support may be subjected to a mat treatment or a corona treatment on the surface to be joined to the resin composition layer. Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resins, olefin resins, urethane resins, and silicone resins. . Examples of commercially available release agents include “SK-1”, “AL-5”, and “AL-7” manufactured by Lintec Corporation, which are alkyd resin release agents.

  Although the thickness of a support body is not specifically limited, The range of 5-75 micrometers is preferable and the range of 10-60 micrometers is more preferable. In addition, when a support body is a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  For the adhesive film, for example, a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and this resin varnish is applied on a support using a die coater or the like and further dried to form a resin composition layer. Can be manufactured.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol, etc. Carbitols, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

  Drying may be performed by a known method such as heating or hot air blowing. The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of the organic solvent is used, the resin composition layer is dried at 50 to 150 ° C. for 3 to 10 minutes. Can be formed.

  In the adhesive film, a protective film according to the support can be further laminated on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support). Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can be stored in a roll. When an adhesive film has a protective film, it can be used by peeling off the protective film.

  In one embodiment, the prepreg is formed by impregnating the sheet-like fiber base material with the resin composition of the present invention.

  The sheet-like fiber base material used for a prepreg is not specifically limited, What is used normally as base materials for prepregs, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and even more preferably 20 μm or less. Although the minimum of the thickness of a sheet-like fiber base material is not specifically limited, Usually, it is 10 micrometers or more.

  The prepreg can be produced by a known method such as a hot melt method or a solvent method.

  The thickness of the prepreg can be in the same range as the resin composition layer in the adhesive film described above.

  In the sheet-like laminated material, the minimum melt viscosity of the resin composition layer is preferably 300 poise or more, more preferably 500 poise or more, and still more preferably 700 poise, from the viewpoint of suppressing the seepage of the resin during the production of the printed wiring board. Above, it is 900 poise or more, or 1000 poise or more. The upper limit of the minimum melt viscosity of the resin composition layer is preferably 30000 poise or less, more preferably 25000 poise or less, and further preferably 20000 from the viewpoint of achieving good lamination properties (circuit embedding properties) in the production of a printed wiring board. Below poise, below 15000 poise, below 10,000 poise, below 5000 poise, or below 3500 poise. In particular, when laminating a resin composition layer and an inner layer substrate by vacuum laminating in the production of a printed wiring board, the upper limit of the minimum melt viscosity of the resin composition layer is 5000 poise or less, or 3500 poise or less. Is preferred. Here, the “minimum melt viscosity” of the resin composition layer refers to the lowest viscosity exhibited by the resin composition layer when the resin of the resin composition layer is melted. Specifically, when the resin composition layer is heated at a constant temperature increase rate to melt the resin, the initial stage of the melt viscosity decreases with increasing temperature, and then, when the temperature exceeds a certain temperature, the melt viscosity decreases with increasing temperature. To rise. “Minimum melt viscosity” refers to the melt viscosity at such a minimum point. The minimum melt viscosity of the resin composition layer can be measured by a dynamic viscoelastic method, and can be measured, for example, according to the method described in <Measurement of minimum melt viscosity> described later.

  In the present invention in which a predetermined amount of an inorganic filler that satisfies a specific shape parameter condition is used, a resin composition layer exhibiting a minimum melt viscosity within the above-mentioned preferred range can be advantageously formed, which is favorable when manufacturing a printed wiring board. A sheet-like laminate material exhibiting excellent laminate properties can be provided. Moreover, since the resin composition of this invention shows favorable dispersion stability, it can suppress that a coarse aggregated particle precipitates in a resin composition layer in the sheet-like laminated material obtained.

  The sheet-like laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (printing) Resin composition for forming an interlayer insulation layer on which a conductor layer can be formed by plating (printed wiring board on which a conductor layer is formed by plating). For the interlayer insulating layer).

[Printed wiring board]
The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.

In one Embodiment, the printed wiring board of this invention can be manufactured by the method including the process of following (I) and (II) using the above-mentioned adhesive film.
(I) A step of laminating an adhesive film on an inner layer substrate so that the resin composition layer of the adhesive film is bonded to the inner layer substrate (II) A step of thermosetting the resin composition layer to form an insulating layer

  The “inner layer substrate” used in step (I) is mainly a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or one or both surfaces of the substrate. A circuit board on which a patterned conductor layer (circuit) is formed. Further, when the printed wiring board is manufactured, an inner layer circuit board of an intermediate product in which an insulating layer and / or a conductor layer is further formed is also included in the “inner layer board” in the present invention.

  The thickness of the inner layer substrate is preferably 800 μm or less, more preferably 400 μm or less, and even more preferably 200 μm or less, from the viewpoint of reducing the thickness of the printed wiring board. According to the present invention, even when a thinner inner layer substrate is used, warpage of the printed wiring board in the mounting process can be suppressed. For example, even when an inner substrate having a thickness of 190 μm or less, 180 μm or less, 170 μm or less, 160 μm or less, 150 μm or less, 140 μm or less, 130 μm or less, 120 μm or less, 110 μm or less, or 100 μm or less is used, warpage in the mounting process Can be suppressed. The lower limit of the thickness of the inner layer substrate is not particularly limited, but is preferably 10 μm or more, more preferably 20 μm or more from the viewpoint of improving the handleability during the production of the printed wiring board.

  The bending elastic modulus of the inner layer substrate is not particularly limited. In the present invention, it is possible to suppress warpage in the component mounting process regardless of the flexural modulus of the inner layer substrate.

  Lamination | stacking of an inner layer board | substrate and an adhesive film can be performed by heat-pressing an adhesive film to an inner layer board | substrate from the support body side, for example. Examples of the member that heat-presses the adhesive film to the inner layer substrate (hereinafter also referred to as “heat-pressing member”) include a heated metal plate (SUS end plate, etc.) or a metal roll (SUS roll). In addition, it is preferable not to press the thermocompression bonding member directly on the adhesive film but to press it through an elastic material such as heat resistant rubber so that the adhesive film sufficiently follows the surface irregularities of the inner layer substrate.

  Lamination of the inner layer substrate and the adhesive film may be performed by a vacuum laminating method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C, and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

  Lamination can be performed with a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nichigo Morton, and the like.

  After lamination, the laminated adhesive film may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same conditions as the thermocompression bonding conditions for the laminate. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform lamination | stacking and a smoothing process continuously using said commercially available vacuum laminator.

Lamination of the inner layer substrate and the adhesive film may also be performed using a vacuum hot press. By using a vacuum hot press machine, even when a resin composition having a high inorganic filler content is used, good laminating properties (circuit embedding properties) can be achieved. Although heating and pressurization may be performed in one stage, it is preferable to perform the conditions separately in two or more stages from the viewpoint of suppressing resin oozing. For example, the first stage press has a temperature in the range of 70 to 150 ° C. and the pressure in the range of 0.098 MPa to 1.77 MPa. The second stage press has a temperature of 150 to 200 ° C. and the pressure in the range of 0.098 MPa to 3. It is preferable to carry out in the range of 92 MPa. The time for each stage is preferably 30 to 120 minutes. The pressing is usually performed under a reduced pressure of 1 × 10 ⁻² MPa or less, preferably 1 × 10 ⁻³ MPa or less. Examples of commercially available vacuum hot press machines include “MNPC-V-750-5-200” manufactured by Meiki Seisakusho, “VH1-1603” manufactured by Kitagawa Seiki Co., Ltd., and the like. When implementing a process (I) using a vacuum hot press machine, this process may serve as thermosetting (namely, process (II)) of a resin composition layer.

  The support may be removed between step (I) and step (II), or may be removed after step (II).

  In step (II), the resin composition layer is thermally cured to form an insulating layer.

  The thermosetting conditions for the resin composition layer are not particularly limited, and the conditions normally employed when forming the insulating layer of the printed wiring board may be used.

  For example, the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition, but the curing temperature is in the range of 120 to 240 ° C (preferably in the range of 150 to 210 ° C, more preferably in the range of 170 to 190 ° C. Range), the curing time can be in the range of 5 to 90 minutes (preferably 10 to 75 minutes, more preferably 15 to 60 minutes).

  Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is formed at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). Preheating may be performed for 5 minutes or more (preferably 5 to 150 minutes, more preferably 15 to 120 minutes).

  The insulating layer formed of the cured product of the resin composition of the present invention exhibits a low coefficient of thermal expansion. In one embodiment, the insulating layer formed of the cured product of the resin composition of the present invention preferably has a linear thermal expansion coefficient of 30 ppm / ° C. or lower, more preferably 28 ppm / ° C. or lower. The lower limit of the linear thermal expansion coefficient of the insulating layer is not particularly limited, but is usually 1 ppm / ° C. or higher. The linear thermal expansion coefficient of the insulating layer can be measured by a known method such as thermomechanical analysis. Examples of the thermomechanical analyzer include “Thermo Plus TMA8310” manufactured by Rigaku Corporation. In the present invention, the linear thermal expansion coefficient of the insulating layer is a linear thermal expansion coefficient of 25 to 150 ° C. in the planar direction when thermomechanical analysis is performed by a tensile load method.

  When manufacturing a printed wiring board, (III) a step of drilling an insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer on the surface of the insulating layer may be further performed. Good. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used in the production of printed wiring boards. In addition, when removing a support body after process (II), removal of this support body is performed between process (II) and process (III), between process (III) and process (IV), or process ( It may be carried out between IV) and step (V).

  Step (III) is a step of making a hole in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, laser, plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board. As described above, since the resin composition of the present invention exhibits good dispersion stability, it is possible to suppress the precipitation of coarse aggregated particles in the resin composition layer and thus in the insulating layer. In the insulating layer having such a uniform composition, holes having a desired cross-sectional shape can be formed in the step (III). Therefore, even when a hole is filled with a conductive metal to form a filled via, the inside of the hole can be filled with the conductive metal smoothly. In this regard, when the inorganic filler having sharp corners or coarse aggregated particles thereof are present on the wall surface of the hole as in the case of using a crushed inorganic filler, the inorganic filler or coarse aggregated particles are used as a starting point. In some cases, voids are generated in the filled via due to the elongation of the plating. In the present invention using an inorganic filler that satisfies a specific shape parameter condition, it is possible to suppress the presence of such agglomerated particles and the like on the wall surface of the hole, so that the plating extends uniformly over the entire wall surface of the hole, The generation of voids in the filled via can be advantageously suppressed.

  Step (IV) is a step of roughening the insulating layer. The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. Although it does not specifically limit as a swelling liquid, An alkaline solution, surfactant solution, etc. are mentioned, Preferably it is an alkaline solution, As this alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include Swelling Dip Securigans P and Swelling Dip Securigans SBU manufactured by Atotech Japan. Although the swelling process by a swelling liquid is not specifically limited, For example, it can carry out by immersing an insulating layer for 1 minute-20 minutes in 30-90 degreeC swelling liquid. Although it does not specifically limit as an oxidizing agent, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as concentrate compact CP and dosing solution securigans P manufactured by Atotech Japan. Moreover, as a neutralization liquid, acidic aqueous solution is preferable, As a commercial item, the reduction solution securigant P by Atotech Japan Co., Ltd. is mentioned, for example. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidant solution in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes.

  The insulating layer formed using the resin composition of the present invention exhibits low surface roughness after the roughening treatment. In one embodiment, the arithmetic average roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 480 nm or less, further preferably 450 nm or less, still more preferably 400 nm or less, 360 nm or less, or 320 nm or less. It is. The insulating layer formed using the resin composition of the present invention exhibits excellent adhesion strength to the conductor layer even when Ra is small as described above. Although the lower limit of Ra value is not specifically limited, 0.5 nm or more is preferable and 1 nm or more is more preferable. The arithmetic average roughness Ra of the insulating layer surface can be measured using a non-contact type surface roughness meter. As a specific example of the non-contact type surface roughness meter, “WYKO NT3300” manufactured by Becoins Instruments is cited.

  Step (V) is a step of forming a conductor layer on the surface of the insulating layer.

  The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A layer formed from a nickel alloy and a copper / titanium alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel / chromium alloy, copper / An alloy layer of nickel alloy or copper / titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel / chromium alloy is more preferable, and a single layer of copper is preferable. A metal layer is more preferred.

  The conductor layer may have a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel / chromium alloy.

  Although the thickness of a conductor layer is based on the design of a desired printed wiring board, generally it is 3 micrometers-35 micrometers, Preferably it is 5 micrometers-30 micrometers.

  The conductor layer may be formed by plating. For example, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern. Hereinafter, an example in which the conductor layer is formed by a semi-additive method will be described.

  First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. A metal layer is formed by electrolytic plating on the exposed plating seed layer, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

  The insulating layer formed using the resin composition of the present invention exhibits sufficient adhesion strength to the conductor layer. In one embodiment, the adhesion strength between the insulating layer and the conductor layer is preferably 0.50 kgf / cm or more, more preferably 0.55 kgf / cm or more, and further preferably 0.60 kgf / cm or more. The upper limit value of the adhesion strength is not particularly limited, but is 1.2 kgf / cm or less, 0.90 kgf / cm or less, and the like. In the present invention, since the insulating layer exhibiting such high adhesion strength can be formed even though the surface roughness Ra of the insulating layer after the roughening treatment is small, it contributes significantly to miniaturization of circuit wiring. Is. In the present invention, the adhesion strength between the insulating layer and the conductor layer refers to a peel strength (90-degree peel strength) when the conductor layer is peeled in a direction perpendicular to the insulating layer (90-degree direction). The peel strength when the layer is peeled in the direction perpendicular to the insulating layer (90-degree direction) can be determined by measuring with a tensile tester. Examples of the tensile tester include “AC-50C-SL” manufactured by TSE Corporation.

  In another embodiment, the printed wiring board of the present invention can be manufactured using the prepreg described above. The manufacturing method is basically the same as when an adhesive film is used.

[Semiconductor device]
A semiconductor device can be manufactured using the printed wiring board of the present invention. Even though the printed wiring board of the present invention is thin, it can suppress warpage even in the component mounting process that uses a high solder reflow temperature, and advantageously reduces problems such as circuit distortion and poor component contact. Can do.

  In one embodiment, the printed wiring board of the present invention can suppress warpage of the printed wiring board to less than 40 μm in a mounting process that employs a solder reflow temperature having a peak temperature as high as 260 ° C. In the present invention, the warpage of the printed wiring board is a value of the difference between the maximum height and the minimum height of the displacement data when the warping behavior of the 10 mm square portion at the center of the printed wiring board is observed with a shadow moire device. In the measurement, a reflow temperature profile described in IPC / JEDEC J-STD-020C (“Moisture / Reflow Sensitivity Classification For Nonhermetic Solid State Surface Devices”, July 2002, Reflow Profile Temperature) The printed wiring board is passed once through a reflow apparatus that reproduces the temperature of [° C.], and then one side of the printed wiring board is heat-treated with a reflow temperature profile in accordance with the IPC / JEDEC J-STD-020C. Displacement data was obtained for the grid lines provided on the other surface. An example of the reflow apparatus is “HAS-6116” manufactured by Nippon Antom Co., Ltd., and an example of the shadow moire apparatus is “Thermoire AXP” manufactured by Akrometrix. Even if the printed wiring board of the present invention including an insulating layer formed of a cured product of a resin composition containing a predetermined amount of an inorganic filler satisfying a specific shape parameter condition is advantageous in warping in the mounting process. Can be suppressed.

  Examples of the semiconductor device include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

  The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) at a conduction point of the printed wiring board of the present invention. The “conduction location” is a “location where an electrical signal is transmitted on a printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, “a mounting method using a build-up layer without a bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. It is.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following, “part” and “%” mean “part by mass” and “% by mass”, respectively, unless otherwise specified.

  First, various measurement methods and evaluation methods will be described.

[Preparation of Evaluation Substrate 1]
(1) Preparation of inner layer circuit board Glass cloth base epoxy resin double-sided copper-clad laminate with inner layer circuit (copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Works, Ltd. “R5715ES”) The copper surface was roughened by 1 μm etching with “CZ8100” manufactured by MEC Co., Ltd.

(2) Lamination of adhesive film The adhesive film produced in the examples and comparative examples was obtained by using a batch type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.) and the resin composition layer was an inner layer circuit. It laminated | stacked on both surfaces of the inner-layer circuit board so that it might join with a board | substrate. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Curing of resin composition layer After lamination, the support was peeled from both sides of the substrate. Next, the resin composition layer was thermally cured under a curing condition of 100 ° C. for 30 minutes and further at 170 ° C. for 30 minutes to form an insulating layer.

(4) Roughening treatment After forming the insulating layer, the substrate is placed in a swelling liquid (an aqueous solution containing “Swelling Dip Securigant P” manufactured by Atotech Japan Co., Ltd., diethylene glycol monobutyl ether and sodium hydroxide) at 80 ° C. For 10 minutes in an oxidizing agent (“Concentrate Compact CP” manufactured by Atotech Japan Co., Ltd., KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 10 minutes, and finally a neutralizing solution (Atotech Japan ( It was immersed for 5 minutes at 40 ° C. in “Reduction Solution Securigant P” manufactured by the same company, hydroxylamine sulfate aqueous solution). Subsequently, it was dried at 80 ° C. for 30 minutes. The obtained substrate is referred to as “substrate 1a”.

For Example 6 and Comparative Example 5, the operations (2) to (4) were performed as follows to obtain a substrate 1a.
Using the vacuum press apparatus ("VH1-1603" manufactured by Kitagawa Seiki Co., Ltd.), the adhesive film produced in the examples and comparative examples was bonded to the inner circuit board so that the resin composition layer was bonded to the inner circuit board. Laminated on both sides. The lamination is pressure-bonded at 100 ° C. and a pressure of 1.0 MPa for 30 minutes under a reduced pressure of 1 × 10 ⁻³ MPa, then heated to 180 ° C. over 10 minutes, and then pressure-bonded at 180 ° C. and a pressure of 1.0 MPa for 30 minutes. Was done. Thereby, the resin composition layer was thermoset to form an insulating layer. The roughening treatment was carried out in the same manner as (4) above except that it was immersed in the swelling solution at 60 ° C. for 5 minutes and in the oxidizing agent at 80 ° C. for 5 minutes.

(5) Formation of conductor layer According to the semi-additive method, a conductor layer was formed on the surface of the insulating layer as described below.
The substrate 1a was immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C. for 20 minutes. Next, after annealing at 150 ° C. for 30 minutes, an etching resist was formed, and a pattern was formed by etching. Thereafter, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 25 μm, and annealing treatment was performed at 180 ° C. for 30 minutes. The obtained substrate is referred to as “substrate 1b”.

[Preparation of evaluation substrate 2]
(1) Preparation of Inner Layer Substrate An unclad plate (thickness: 100 μm) from which all the double-sided copper foil of the glass cloth base epoxy resin double-sided copper-clad laminate was removed was prepared as the inner layer substrate. As the glass cloth base epoxy resin double-sided copper-clad laminate, “HL832NSF-LCA” manufactured by Mitsubishi Gas Chemical Co., Ltd. (size 100 mm × 150 mm, base base material thickness 100 μm, thermal expansion coefficient 4 ppm / ° C., flexural modulus) 34 GPa, surface copper circuit thickness 16 μm).

(2) Lamination of adhesive film The adhesive film produced in the examples and comparative examples was obtained by using a batch type vacuum pressure laminator (a two-stage build-up laminator “CVP700” manufactured by Nichigo Morton Co., Ltd.) and a resin composition. The inner layer substrate was laminated on both sides so that the layer was in contact with the inner layer substrate. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less and then pressing the film at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. Next, hot pressing was performed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Curing of resin composition layer After lamination, the support was peeled from the substrate. Next, the resin composition layer was thermally cured at 190 ° C. for 90 minutes to form an insulating layer. The obtained substrate is referred to as “substrate 2a”.

<Measurement of specific surface area (S) of inorganic filler>
The specific surface area of the inorganic filler was determined by a nitrogen BET method using an automatic specific surface area measuring device ("Macsorb HM-1210" manufactured by Mountec Co., Ltd.).

<Measurement of average particle diameter (R) of inorganic filler>
To a 20 ml vial, add 0.01 g of an inorganic filler, 0.2 g of a nonionic dispersant (“T208.5” manufactured by NOF Corporation) and 10 g of pure water, and ultrasonicate for 10 minutes with an ultrasonic cleaner. Dispersion was performed to prepare a sample. Next, the sample was put into a laser diffraction particle size distribution measuring apparatus (“SALD2200” manufactured by Shimadzu Corporation) and irradiated with ultrasonic waves for 10 minutes while being circulated. Thereafter, the ultrasonic wave was stopped, the particle size distribution was measured while maintaining the circulation of the sample, and the average particle diameter (R) of the inorganic filler was determined. The refractive index at the time of measurement was set to 1.45 to 0.001i.

<Calculation of shape parameter A>
The shape parameter A was calculated by substituting the values of the specific surface area (S), average particle diameter (R), and density (ρ) of the inorganic filler into the following formula (1).
Formula (1): A = SRρ / 6

<Calculation of shape parameter B>
About the insulating layer laminated | stacked on the single side | surface of the board | substrate 1a, cross-sectional observation was performed by 14,000 times of observation magnification using the FIB-SEM composite apparatus ("SMI3050SE" by SII nanotechnology Co., Ltd.). From the obtained FIB-SEM image, the peripheral length (L) and area of the inorganic filler particles present in the insulating layer were measured using image processing software (“QWin V3” manufactured by Leica Co., Ltd.). In addition, the measurement was performed about arbitrary 50 inorganic filler particles per sample, avoiding the inorganic filler particle with an unknown whole image, or the inorganic filler particle with a blurred outline. From the area of the obtained inorganic filler particles, the perimeter of a perfect circle (circumference; Lc) of the same area as that was calculated. And the value of L and Lc was substituted into following formula (2), shape parameter B was computed about each inorganic filler particle, and the average value of shape parameter B and its distribution were obtained.
Formula (2): B = Lc / L

<Measurement of average crystallite diameter of inorganic filler>
The average crystallite size of the inorganic filler was determined according to the following procedure. First, a sample plate was prepared by fixing an inorganic filler to a glass sample plate. The sample plate was set in a wide-angle X-ray diffractometer (“Multi FLEX” manufactured by Rigaku Corporation), and a diffraction profile was measured by a wide-angle X-ray diffraction reflection method. The X-ray source was CuKα, the detector was a scintillation counter, and the output was 40 kV, 40 mA. From the diffraction line based on the SiO ₂ Quarts (101) plane of the obtained diffraction profile, the crystallite diameter was calculated using the Scherrer equation.

<Evaluation of dispersion stability>
About the adhesive film produced by the Example and the comparative example, the aggregated particle in a resin composition layer was observed with the observation magnification | multiplying_factor 1000 times using the microscope ("VH-2250" by Corporation | KK KEYENCE). The dispersion stability of the resin composition was evaluated according to the following criteria.
Evaluation criteria:
○: Less than 2 aggregated particles of 10 μm or more in 10 fields of view X: 2 or more aggregated particles of 10 μm or more in 10 fields of view

<Measurement of minimum melt viscosity>
About the resin composition layer of the adhesive film produced in the Example and the comparative example, the melt viscosity was measured using the dynamic viscoelasticity measuring apparatus ("Rhesol-G3000" by UBM). About 1 g of the sample resin composition, using a parallel plate with a diameter of 18 mm, the temperature was increased from a starting temperature of 60 ° C. to 200 ° C. at a heating rate of 5 ° C./min, a measurement temperature interval of 2.5 ° C., vibration of 1 Hz, and strain The dynamic viscoelastic modulus was measured under a measurement condition of 1 deg, and the minimum melt viscosity was measured. The stackability was evaluated according to the following criteria.
Evaluation criteria:
○: Minimum melt viscosity is 30000 poise or less X: Minimum melt viscosity is higher than 30000 poise

<Evaluation of warpage>
The substrate 2a (n = 5) was passed once through a reflow apparatus (“HAS-6116” manufactured by Nippon Antom Co., Ltd.) that reproduces the solder reflow temperature at a peak temperature of 260 ° C. (reflow temperature profile is IPC / JEDEC J- Conforms to STD-020C). Next, the lower surface of the substrate is heated with a reflow temperature profile conforming to IPC / JEDEC J-STD-020C (peak temperature 260 ° C.) using a shadow moire device (“Thermoire AXP” manufactured by Akrometrix), and is disposed on the upper surface of the substrate. The displacement of the 10 mm square portion at the center of the substrate was measured based on the lattice lines. The warpage was evaluated according to the following evaluation criteria.
Evaluation criteria:
○: For all five samples, the difference between the maximum height and the minimum height of the displacement data in the entire temperature range is less than 40 μm. ×: For at least one sample, the difference between the maximum height and the minimum height of the displacement data in the entire temperature range is 40 μm or more.

<Measurement of arithmetic average roughness (Ra)>
With respect to the substrate 1a, the Ra value was determined by using a non-contact type surface roughness meter ("WYKO NT3300" manufactured by BEIKO INSTRUMENTS Co., Ltd.) and a numerical value obtained by setting the measurement range to 121 μm × 92 μm with a VSI contact mode and a 50 × lens. A measurement value was obtained by calculating an average value of 10 points selected at random.

<Measurement of adhesion strength of conductor layer>
The adhesion strength between the insulating layer and the conductor layer was measured according to JIS C6481 for the evaluation substrate 1b. Specifically, the conductor layer of the substrate 1b is cut into a portion having a width of 10 mm and a length of 100 mm, this one end is peeled off and grasped with a gripping tool, and at a room temperature, the vertical direction is 35 mm at a speed of 50 mm / min. The load (kgf / cm) when the film was peeled off was measured to determine the adhesion strength.

<Measurement of linear thermal expansion coefficient>
The adhesive films prepared in Examples and Comparative Examples were heated at 190 ° C. for 90 minutes to thermally cure the resin composition layer. Subsequently, the support was peeled off to obtain a sheet-like cured product. The obtained sheet-like cured product was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and subjected to a tensile load method using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Corporation). Thermomechanical analysis was performed. Specifically, after the test piece was mounted on the thermomechanical analyzer, the test piece was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. In the second measurement, an average linear thermal expansion coefficient in a range from 25 ° C. to 150 ° C. was calculated.

<Evaluation of filled via voids>
Evaluation of voids in filled vias was performed according to the following procedure.
(1) Formation of via hole Using a carbon dioxide gas laser processing machine ("LC-2E21B / 1C" manufactured by Hitachi, Ltd.), an insulating layer laminated on one side of the substrate 1a has a top diameter of 60 μm and a bottom diameter of 50 μm. The via hole was formed.
(2) Formation of filled vias After forming via holes, the insulating layer was roughened to form conductor layers. The roughening treatment and the formation of the conductor layer were carried out in the same manner as in [Preparation of evaluation substrate 1]. Thereby, the inside of the via hole was filled with the conductive metal, and a filled via was obtained.
(3) Evaluation of voids The formed filled vias were cross-sectionally observed using a scanning electron microscope (SEM) (manufactured by Hitachi High-Technologies Corporation, model “SU-1500”). And the case where the number of voids in 10 filled vias is less than 2 is “◯”, and the case where it is 2 or more is “x”.

  Table 1 summarizes the physical properties and shape parameters A and B of the inorganic fillers used in the examples and comparative examples.

  For IMSIL A-8, the content of particles having a shape parameter B of less than 0.8 is 36% by number, particularly the content of particles having a shape parameter B of 0.75 or less is 16% by number, and the shape parameter B The content of particles having a particle size greater than 0.9 was 12% by number, and in particular, the content of particles having a shape parameter B of 0.94 or more was 0% by number. For IMSIL A-25, the content of particles having a shape parameter B of less than 0.8 is 26% by number, and in particular, the content of particles having a shape parameter B of 0.75 or less is 20% by number. The content of particles having a particle size greater than 0.9 was 14 number%, and in particular, the content of particles having a shape parameter B of 0.94 or more was 0 number%.

<Example 1>
(1) Preparation of resin varnish 20 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 187, “jER828EL” manufactured by Mitsubishi Chemical Corporation), biphenyl type epoxy resin (epoxy equivalent 276, “NC3000” manufactured by Nippon Kayaku Co., Ltd.) ) 30 parts, 5 parts of tetraphenylethane type epoxy resin (epoxy equivalent 198, “jER1031S” manufactured by Mitsubishi Chemical Corporation), solid bisphenol A type epoxy resin (epoxy equivalent of about 3000 to 5000, manufactured by Mitsubishi Chemical Corporation) jER1010 ") in a mixed solvent of methyl ethyl ketone (MEK) and cyclohexanone in a mass ratio of 1: 1, 5 parts of a resin solution of 50% by mass of a non-volatile component is heated and dissolved in a mixed solvent of 20 parts of MEK and 10 parts of cyclohexanone with stirring. I let you. Thereto, 10 parts of a triazine skeleton-containing phenol novolac curing agent (hydroxyl equivalent 125, “LA-7054” manufactured by DIC Corporation, MEK solution having a solid content of 60%), phenol novolac curing agent (hydroxyl equivalent 105, DIC ( "TD2090"), 6 parts, amine curing accelerator (4-dimethylaminopyridine (DMAP), 5 mass% MEK solution), 3 parts, N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu) Crystalline silica ("IMSIL A-8" manufactured by Unimin Co., Ltd.), average particle size 1.38 [mu] m, maximum particle size 20 [mu] m, specific surface area 6.54 m < ² > / g, density 2. 65 g / cm ^3, an average crystallite size 1000 Å) 180 parts, made of a flame retardant (Sanko Co. "HCA-HQ", 10- (2,5-dihydroxy Phenyl) -10-hydro-9-oxa-10-phosphatonin phenanthrene-10-oxide, a mixture of average particle diameter 2 [mu] m) 5 parts were uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish. The overall density of the nonvolatile components other than the inorganic filler used for preparing the resin varnish was about 1.2 g / cm ³ .
(2) Production of Adhesive Film A polyethylene terephthalate film with an alkyd resin release layer (thickness 38 μm, manufactured by Lintec Corporation, “AL5”) was prepared as a support. The resin varnish prepared above was uniformly coated on the support with a die coater and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes to form a resin composition layer. The thickness of the resin composition layer was 40 μm, and the amount of residual solvent in the resin composition was about 2% by mass. Next, a polypropylene film (manufactured by Oji Specialty Paper Co., Ltd., “Alphan MA-411”, smooth surface side, 15 μm in thickness) was bonded to the surface of the resin composition layer as a protective film, and wound into a roll. The adhesive film was slit to a width of 507 mm to obtain an adhesive film having a size of 507 mm × 336 mm.

<Example 2>
Instead of 30 parts of biphenyl type epoxy resin (epoxy equivalent 276, “NC3000” manufactured by Nippon Kayaku Co., Ltd.), 10 parts of biphenyl type epoxy resin (epoxy equivalent 276, “NC3000” manufactured by Nippon Kayaku Co., Ltd.) and naphthi A resin varnish was prepared in the same manner as in Example 1 except that 18 parts of a renether type epoxy resin (epoxy equivalent 250, “HP6000” manufactured by DIC Corporation) was used, and an adhesive film was prepared.

<Example 3>
Instead of 6 parts of a phenol novolac-based curing agent (hydroxyl equivalent 105, “TD2090” manufactured by DIC Corporation), 12 parts of a naphthol novolak-based curing agent (hydroxyl equivalent 215, “SN485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) was used. And the amount of crystalline silica ("IMSIL A-8" manufactured by Unimin) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) to 210 parts. Except for the changed points, a resin varnish was prepared in the same manner as in Example 1 to produce an adhesive film.

<Example 4>
Instead of solid bisphenol A type epoxy resin (epoxy equivalent of about 3000 to 5000, “jER1010” manufactured by Mitsubishi Chemical Corporation), phenoxy resin (“YL7553BH30 manufactured by Mitsubishi Chemical Corporation), MEK / A resin varnish was prepared in the same manner as in Example 1 except that 8 parts of (cyclohexanone = 1/1 solution) was used, and an adhesive film was prepared.

<Example 5>
Instead of 180 parts of crystalline silica ("IMSIL A-8" manufactured by Unimin) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), N-phenyl-3 -Crystalline silica treated with aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("IMSIL A-25" manufactured by Unimin), average particle size 2.55 [mu] m, maximum particle size 20 [mu] m, specific surface area 5. A resin varnish was prepared in the same manner as in Example 1 except that 87 m ² / g, density 2.65 g / cm ³ , average crystallite diameter 1400 Å) was used, and an adhesive film was produced.

<Example 6>
Crystalline silica surface treated with N-phenyl-3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“IMSIL A-8” manufactured by Unimin, average particle size 1.38 μm, maximum particle size 20 μm) The resin varnish was prepared and bonded in the same manner as in Example 1 except that the specific surface area 6.54 m ² / g, density 2.65 g / cm ³ , average crystallite diameter 1000 mm) was changed to 400 parts. A film was prepared.

<Comparative Example 1>
Instead of 180 parts of crystalline silica ("IMSIL A-8" manufactured by Unimin) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), N-phenyl-3 -Spherical silica surfaced with aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C2” manufactured by Admatechs Co., Ltd.), average particle size 0.90 μm, specific surface area 5.75 m ² / g, density 2.2 g / cm ³ ) A resin varnish was prepared in the same manner as in Example 1 except that 150 parts were used, and an adhesive film was produced.

<Comparative Example 2>
Instead of 180 parts of crystalline silica ("IMSIL A-8" manufactured by Unimin) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), N-phenyl-3 -Spherical silica surfaced with aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C6” manufactured by Admatechs Co., Ltd.), average particle size 2.06 μm, specific surface area 2.15 m ² / g, density 2.2 g / cm ³ ) A resin varnish was prepared in the same manner as in Example 1 except that 150 parts were used, and an adhesive film was produced.

<Comparative Example 3>
Instead of 180 parts of crystalline silica ("IMSIL A-8" manufactured by Unimin) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), N-phenyl-3 -Crushed silica ("VX-SR" manufactured by Tatsumori Co., Ltd.), surface treated with aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 1.30 [mu] m, specific surface area 11.94 m < ² > / G, density 2.65 g / cm ³ , average crystallite diameter 1900 mm) except that 180 parts were used, a resin varnish was prepared in the same manner as in Example 1 to prepare an adhesive film.

<Comparative Example 4>
Other than changing the usage amount of crystalline silica ("IMSIL A-8" manufactured by Unimin) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) to 80 parts Prepared the resin varnish like Example 1, and produced the adhesive film.

<Comparative Example 5>
Other than changing the usage amount of crystalline silica ("IMSIL A-8" manufactured by Unimin) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) to 480 parts Prepared the resin varnish like Example 1, and produced the adhesive film.

Claims (14)

A resin composition for an insulating layer of a printed wiring board,
When the non-volatile component in the resin composition is 100% by volume, the content of the inorganic filler is 40 to 75% by volume,
Formula: A = SRρ / 6 [wherein S is the specific surface area of the inorganic filler (m ² / g), R is the average particle diameter (μm) of the inorganic filler, and ρ is the density of the inorganic filler (g / cm ³ ). ] The resin composition in which the shape parameter A of the inorganic filler represented by 20 satisfies 20 ≦ 6A ≦ 40. A resin composition for an insulating layer of a printed wiring board,
When the non-volatile component in the resin composition is 100% by volume, the content of the inorganic filler is 40 to 75% by volume,
Formula: B = Lc / L [wherein L is the perimeter of the inorganic filler in a predetermined cross section (μm), Lc is the perimeter of a perfect circle of the same area as the cross section of the inorganic filler in the cross section (μm) Represents. ] The resin composition whose average value of the shape parameter B of the inorganic filler represented by this is 0.8 or more and 0.9 or less.   The resin composition according to claim 1 or 2, wherein the inorganic filler has an average crystallite diameter of 1800 angstroms or less. The resin composition of any one of Claims 1-3 whose specific surface area of an inorganic filler is 3-10 m < ² > / g.   The resin composition of any one of Claims 1-4 whose average particle diameter of an inorganic filler is 4 micrometers or less.   The resin composition according to any one of claims 1 to 5, wherein the average particle size of the inorganic filler is 3 µm or less.   The inorganic filler is obtained by dispersing tufted aggregates of microcrystalline particles having an average crystallite diameter of 1800 angstroms or less, and the maximum particle size of the tufted aggregates is 20 μm or less. 2. The resin composition according to item 1.   The resin composition according to any one of claims 1 to 7, wherein the content of the crystalline inorganic filler in the inorganic filler is 50% by mass or more when the entire inorganic filler is 100% by mass. object.   The resin composition according to claim 8, wherein the crystalline inorganic filler is crystalline silica.   Furthermore, the resin composition of any one of Claims 1-9 containing an epoxy resin and a hardening | curing agent.   The resin composition according to any one of claims 1 to 10, which is a resin composition for an interlayer insulating layer.   The sheet-like laminated material containing the resin composition layer formed with the resin composition of any one of Claims 1-11.   The printed wiring board containing the insulating layer formed with the hardened | cured material of the resin composition of any one of Claims 1-11.   A semiconductor device comprising the printed wiring board according to claim 13.