KR102293385B1 - Resin composition for insulating layer of printed wiring board - Google Patents

Abstract

PROBLEM To provide the resin composition for insulating layers of a printed wiring board which can suppress the curvature in the mounting process of a component while exhibiting favorable dispersion stability and moderate melt viscosity.
[Solution] As a resin composition for an insulating layer of a printed wiring board, when the nonvolatile component in the resin composition is 100% by volume, the content of the inorganic filler is 40 to 75% by volume, and the formula: A = SRρ/6 [where S is the specific surface area (m2/g) of the inorganic filler, R is the average particle diameter (μm) of the inorganic filler, and ρ is the density (g/cm3) of the inorganic filler.] satisfies 20≤6A≤40.

Description

The resin composition for the insulating layer of a printed wiring board TECHNICAL FIELD

This invention relates to the resin composition for insulating layers of a printed wiring board.

As a manufacturing technique of a printed wiring board, the manufacturing method by the build-up system which laminates|stacks an insulating layer and a conductor layer alternately on an inner-layer board|substrate is known. In the manufacturing method by a build-up method, an insulating layer is formed by laminating|stacking a resin composition layer on an inner-layer substrate using the adhesive film etc. containing a resin composition layer, for example, and hardening the resin composition layer. The resin composition used for the formation of the insulating layer reduces the thermal expansion coefficient of the insulating layer obtained, and from the viewpoint of preventing the occurrence of cracks or circuit deformation due to the difference in thermal expansion between the insulating layer and the conductor layer, in general, inorganic fillers contains As the said inorganic filler, a spherical inorganic filler is used suitably (patent document 1).

Japanese Patent Laid-Open No. 2010-238667

As lead-containing solders are replaced with lead-free solders in recent years, the solder reflow temperature in the component mounting process is rising. Moreover, in order to achieve size reduction of an electronic device, thickness reduction of a printed wiring board is progressing further in recent years.

As the thickness of the printed wiring board progresses, warpage may occur in the printed wiring board in the component mounting process, and problems such as circuit deformation and poor contact of components may occur. The present inventors discovered that the curvature in the mounting process of a component could be suppressed by using a crushed inorganic filler instead of a spherical inorganic filler. However, while a resin composition containing a crushed inorganic filler is inferior to dispersion stability, it is easy to result in a high melt viscosity, and may cause lamination|stacking defect.

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 a component while showing favorable dispersion stability and moderate melt viscosity.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the said subject, the present inventors discovered that the said subject was solvable by using the predetermined amount of the inorganic filler which has a specific shape, and came to complete this invention.

That is, the present invention includes the following contents.

[1] A resin composition for an insulating layer of a printed wiring board, comprising:

When the nonvolatile component in the resin composition is 100% by volume, the content of the inorganic filler is 40 to 75% by volume,

Equation: A = SRρ/6 [where S is the specific surface area (m2/g) of the inorganic filler, R is the average particle diameter (㎛) of the inorganic filler, and ρ is the density (g/cm3) of the inorganic filler The resin composition, wherein the shape parameter A of the inorganic filler represented by ] satisfies 20≤6A≤40.

[2] A resin composition for an insulating layer of a printed wiring board, comprising:

When the nonvolatile component in the resin composition is 100% by volume, the content of the inorganic filler is 40 to 75% by volume,

Equation: B = Lc/L [where L is the peripheral length (μm) of the inorganic filler in a predetermined cross-section, and Lc is the cross-sectional area of the inorganic filler in the cross-section and the equal area It is the peripheral length (micrometer) of a perfect circle.] The average value of the shape parameter B of the inorganic filler represented by 0.8 or more and 0.9 or less, The resin composition.

[3] The resin composition according to [1] or [2], wherein the inorganic filler has an average crystallite diameter of 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 diameter 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 diameter of 3 µm or less.

[7] The inorganic filler is obtained by dispersing a cluster-like aggregate of microcrystalline particles having an average crystallite diameter of 1800 Å or less, and the maximum particle diameter of the cluster-like aggregate is 20 µm or less, [1] to The resin composition according to any one of [6].

[8] In any one of [1] to [7], wherein the inorganic filler contains a crystalline inorganic filler, and the content of the crystalline inorganic filler is 50% by mass or more when the total inorganic filler is 100% by mass. The described 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-like laminated material comprising a resin composition layer formed of the resin composition according to any one of [1] to [11].

[13] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [11].

[14] A semiconductor device comprising 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 resin composition for insulating layers of a printed wiring board which can suppress the curvature in the mounting process of a component 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") contains a predetermined amount of an inorganic filler having a shape different from that of a conventionally known spherical inorganic filler and crushed inorganic filler. characterized in that it contains

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

Compared with the projection shape to a plane, unlike the spherical inorganic filler in which an angle is not recognized clearly, the inorganic filler used by this invention can recognize an angle clearly. Here, "an angle can be recognized in the projection shape on a plane" means a certain straight line or substantially straight line and a certain straight line or substantially straight line and a constant angle θ (inside the projection shape) in the projection shape onto a plane. It means that a straight line tangent with an angle or an approximate straight line can be recognized. And about the inorganic filler used by this invention, the average value of the said angle (theta) is large compared with the crushed inorganic filler. For example, as for the inorganic filler used by this invention, compared with the crushed inorganic filler, Preferably the average value of the said angle (θ) is 5°, more preferably 7.5°, still more preferably 10°, 12.5° , 15°, 17.5°, or 20° greater.

Hereinafter, the shape of the inorganic filler used by this invention is demonstrated using two shape parameters, ie, shape parameter A and shape parameter B. In addition, although there is a difference in whether the shape parameter A and the shape parameter B are a parameter derived by a three-dimensional approach or a parameter derived by a two-dimensional approach, in either case, regarding the shape of the inorganic filler, ) is a parameter indicating the degree of deformation from

<Shape parameter A>

The shape parameter A is expressed by the following formula (1).

[Equation 1]

Ａ＝SRSρ／６

In Equation 1,

S is the specific surface area (m2 / g) of the inorganic filler,

R is the average particle diameter (㎛) of the inorganic filler,

ρ is the density (g/cm 3 ) of the inorganic filler.

A system in which a plurality of true spheres exist (hereinafter also referred to as a "real sphere model system") is considered. When the average particle diameter (diameter) of these true spheres is R, the average surface area of a plurality of true spheres existing in the true sphere model system is ^{expressed by πR 2} , and the average volume is expressed by πR ³ /6. In addition, when the density of a true sphere is ρ, the average mass of a plurality of true spheres existing in the true sphere model system is ^{expressed as πρR 3} /6.

Next, consider a system of an inorganic filler having the same average volume and density as that of a true sphere model system. 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 a plurality of inorganic fillers present in this system of inorganic fillers 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). In addition, based on the condition that the average volume and density are the same as those of the true sphere model system, the average mass of the plurality of inorganic fillers present in the system of the inorganic filler can be expressed as ^{πρR 3 /6.} And, in the system of the inorganic filler, the specific surface area S of the inorganic filler is [average surface area (AπR ² ) of a plurality of inorganic fillers present in the system of the inorganic filler]/[a plurality of inorganic fillers present in the system of the inorganic filler] The average mass of the inorganic filler (πρR ³ /6)], which becomes 6A/(Rρ). That is, when the relational expression of S = 6A/(Rρ) is established and the expression is transformed with respect to the parameter A, the above expression (1) is obtained.

The inorganic filler used in the present invention is characterized in that the shape parameter A expressed 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 required to obtain the shape parameter A can be measured by the BET method. Specifically, molecules having a known adsorption occupied area are adsorbed to 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 adsorption amount thereof. As the 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 measurement device, and examples of the automatic specific surface area measurement device include “Macsorb HM-1210” manufactured by Mountec Co., Ltd. have.

In addition, the average particle diameter (R) of an inorganic filler can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, it can measure by creating the particle size distribution of an inorganic filler on a volume basis with a laser diffraction type particle size distribution measuring apparatus, and making this median diameter into an average particle diameter. As a measurement sample, what disperse|distributed the inorganic filler in water by ultrasonic wave can be used preferably. As a laser diffraction type particle size distribution measuring apparatus, For example, Shimadzu Corporation make "SALD2200", Horibase Corporation make "LA-500", "LA-750", "LA-950" can be heard

<Shape parameter B>

The shape parameter B is expressed by the following formula (2).

[Equation 2]

B = Lc/L

In Equation 2,

L is the peripheral length (μm) of the inorganic filler in a given cross section,

Lc is the perimeter length (μm) of the perfect circle equal to 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 peripheral length in a figure of the same area, and its upper limit is 1 (when the cross-sectional shape of the inorganic filler is a perfect circle in a given cross section) .

The shape parameter B is a parameter established for individual particles of the inorganic filler, and by obtaining the shape parameter B for a sufficient number of particles constituting the inorganic filler, it is possible to grasp the overall characteristics regarding the shape of the inorganic filler. . 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 thereof. Such an embodiment WHEREIN: The inorganic filler used by this invention is characterized by the average value of the shape parameter B represented by said Formula (2) being 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, it is also possible to obtain the shape parameter B with respect to a sufficient number of particles constituting the inorganic filler, and grasp the shape distribution of the particles constituting the inorganic filler based on the obtained value of the shape parameter B. The inorganic filler used by this invention WHEREIN: Content of the particle|grains whose value of the shape parameter B represented by said Formula (2) is less than 0.8 is 50 number% or less normally. Moreover, the inorganic filler used by this invention WHEREIN: Content of the particle|grains whose value of the shape parameter B represented by said Formula (2) is larger than 0.9 is 30 number% or less normally. The suitable range of these content is mentioned later.

The circumferential length (L) of the inorganic filler in a given cross section and the cross-sectional area of the inorganic filler in the cross section, which are necessary when obtaining the shape parameter B, are the cross-sectional observations of the layer formed using the resin composition of the present invention. It can be measured by carrying out. For cross-sectional observation, a FIB-SEM composite apparatus is suitably used. From the obtained FIB-SEM image, the peripheral length and area (cross-sectional area) of the inorganic filler existing in the layer can be calculated|required using image processing software, such as "QWin V3" by Leica Corporation. As an FIB-SEM composite apparatus, "SMI3050SE" manufactured by SII Nanotechnology Co., Ltd. is mentioned, for example.

Lc may be calculated by calculating the circumferential length (circumference) of the perfect circle of the cross-sectional area and the equal area of the obtained inorganic filler.

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

From the viewpoint of obtaining a resin composition exhibiting good dispersion stability and suitable melt viscosity, it is important that the value of 6A is 40 or less. From the viewpoint of obtaining a resin composition exhibiting better 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, It is preferably 34 or less, 33 or less, 32 or less, 31 or less, or 30 or less. It is important that the lower limit of 6A is 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, in the resin composition of the present invention, when the nonvolatile component in the resin composition is 100% by volume, the content of the inorganic filler is 40 to 75% by volume, and the shape of the inorganic filler represented by the above formula (2) The average value of the parameter B is 0.8 or more and 0.9 or less, It is characterized by the above-mentioned (henceforth, it is also called "resin composition of 2nd 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. From the viewpoint of obtaining a resin composition exhibiting better dispersion stability and melt viscosity, the average value of the shape parameter B is preferably 0.81 or more, or 0.82 or more. It is important that the upper limit of the average value of the shape parameter B is 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 preferably 0.89 or less, 0.88 or less, 0.87 or less, 0.86 or less, or 0.85 or less.

Regardless of the first embodiment and the second embodiment, the content of the inorganic filler is, when the non-volatile component in the resin composition is 100% by volume, from the viewpoint of sufficiently suppressing warpage in the component mounting process, the insulation obtained From the viewpoint of sufficiently reducing the thermal expansion coefficient of the layer, it is 40 vol% or more, preferably 42 vol% or more, more preferably 44 vol% or more, still more preferably 46 vol% or more, still more preferably 48 vol% or more. % 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 using a crushed inorganic filler, there exists a tendency for melt viscosity to rise excessively as content of the said inorganic filler becomes high. On the other hand, regarding the inorganic filler used by this invention which satisfy|fills specific shape parameter conditions, while realizing a favorable melt viscosity, content can be raised further. For example, the resin composition of this invention WHEREIN: You may raise content of the said inorganic filler to 62 volume% or more, 64 volume% or more, 66 volume% or more, or 68 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 obtaining an insulating layer having a small surface roughness and excellent adhesion strength (peel strength) with the conductor layer, 75 vol% or less, preferably 74 vol% or less, more preferably 73 vol% or less, still more preferably 72 vol% or less, still more preferably 71 vol% or less, particularly preferably 70 vol% or less. . In particular, when laminating|stacking a resin composition layer and an inner-layer board|substrate by the vacuum lamination method in manufacture of a printed wiring board, it is suitable that the upper limit of content of the said inorganic filler is 70 volume% or less. The content (vol%) of the inorganic filler can be calculated based on the mass and density of the inorganic filler used for preparation of the resin composition, and the mass and density of nonvolatile components other than the inorganic filler used for preparation of the resin composition. .

Regardless of the first embodiment and the second embodiment, from the viewpoint of obtaining a resin composition exhibiting good dispersion stability and melt viscosity, in the inorganic filler, the value of the shape parameter B represented by the above formula (2) is less than 0.8. It is preferable that content is low. In the resin composition of the present invention, the content of particles having a shape parameter B of less than 0.8 in the inorganic filler is usually 50% by number or less, preferably 48% by number or less, more preferably is 46% by number or less, 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 the particles having the shape parameter B 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 the first embodiment and the second embodiment, from the viewpoint of sufficiently suppressing warpage in the component mounting process, the value of the shape parameter B expressed by the above formula (2) in the inorganic filler is larger than 0.9. It is preferable that content is low. In the resin composition of the present invention, in the inorganic filler, the content of particles having a value of the shape parameter B expressed by the above formula (2) greater than 0.9 is usually 30% by number or less, preferably 28% by number or less, more preferably Preferably, it is 26 % by number or less, more preferably 24 % or less, and 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 of 0.94 or more is 6% by number, 4% or less, 2% or less, 1% or less, 0.8% or less, 0.6% or less, 0.4% or less, 0.2 It is preferable that it is number % or less.

In the resin composition of the present invention, the material of the inorganic filler is not particularly limited, and 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, magnesium titanate, bismuth titanate, Titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphate tungsten, etc. are mentioned, Silica is especially suitable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type. When two or more inorganic fillers are used in combination, the average particle diameter (R), specific surface area (S) and density (ρ) required to obtain the shape parameter A are, respectively, the average particles of the obtained inorganic filler mixture. Diameter, specific surface area, and density may be used.

From a viewpoint of refinement|miniaturization of circuit wiring, 4 micrometers or less are preferable, as for the average particle diameter R of an inorganic filler, 3.5 micrometers or less are more preferable, and its 3 micrometers or less are still more preferable. The lower limit of the average particle diameter of the inorganic filler is preferably 0.01 µm or more, and more preferably 0.03 µm or more, from the viewpoint of obtaining a resin varnish having a suitable viscosity and good handleability when forming a resin varnish using the resin composition. and more preferably 0.05 µm or more, still more preferably 0.07 µm or more, and particularly preferably 0.1 µm or more.

The specific surface area (S) of the inorganic filler is not particularly limited as long as the above shape parameter conditions are satisfied in relation to the average particle diameter (R) and the density (ρ). The range of 3-10 m<2>/g may be sufficient as the specific surface area of an inorganic filler, for example, and it is preferable that it is the range of 3-8 m<2>/g.

The inorganic filler may be either amorphous or crystalline as long as the above shape parameter conditions are satisfied. In one embodiment, the resin composition of this invention contains a crystalline inorganic filler. When content of the crystalline inorganic filler in an inorganic filler makes the whole inorganic filler 100 mass %, Preferably it is 50 mass % or more, More preferably, it is 60 mass % or more, More preferably, it is 70 mass % or more. Preferably it is 80 mass % or more, Especially preferably, it is 90 mass % or more, 92 mass % or more, 94 mass % or more, 96 mass % or more, 98 mass % or more, or 99 mass % or more. An inorganic filler may remove the impurity contained inevitably, and may consist of a crystalline inorganic filler substantially. In this embodiment, the average crystallite diameter of the inorganic filler is preferably 1800 angstroms or less, more preferably 1600 angstroms or less, still more preferably 1400 angstroms or less. Although the lower limit of the said average crystallite diameter is not specifically limited, Usually, it can be 100 angstrom or more, 200 angstrom or more, etc. The crystallite diameter of the inorganic filler can be measured using an X-ray diffraction (XRD) apparatus. As an XRD apparatus, "Multi FLEX" by Rigaku Co., Ltd. is mentioned, for example.

Among these, it is preferable to use crystalline silica as a crystalline inorganic filler.

The inorganic filler satisfying the above shape parameter conditions is prepared by, for example, slightly rounding the surface of the crushed inorganic filler having a sharp angular shape by a method of physically and/or chemically polishing, a method of heat treatment, etc. Do it. The methods of physical polishing and chemical polishing are not particularly limited, and any conventionally known method may be used. As a commercial item of crushed silica, Tatsumori Co., Ltd. product "VX-SR" etc. are mentioned, for example.

In addition, among the naturally occurring inorganic oxides, there exist inorganic oxides that suitably satisfy the above shape parameter conditions. For example, natural silica (especially when the maximum particle diameter of the cluster-like aggregate is 20 µm or less) is produced as a cluster-like aggregate of microcrystalline particles with an average crystallite diameter of 1800 Å or less by passing through a dispersion operation at the time of preparation of the resin composition, The pine-like agglomerates are released to satisfy the above shape parameter conditions. Therefore, in one embodiment, the inorganic filler contained in the resin composition of the present invention is obtained by dispersing a cluster-like aggregate of microcrystalline particles having an average crystallite diameter of 1800 Å or less, and the maximum particle diameter of the cluster-like aggregate is 20 µm or less. characterized. As a commercial item of such natural silica, "IMSIL A-8" by Unimin, "IMSIL A-10", "IMSIL A-15", "IMSIL A-25" etc. are mentioned, for example.

It is preferable that the inorganic filler used for the resin composition of this invention is surface-treated with the surface treating agent from a viewpoint of improving dispersibility and moisture resistance. Examples of the surface treatment agent include an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an organosilazane compound, and a titanate-based coupling agent. A surface treating agent may be used individually by 1 type, and may be used in combination of 2 or more type. As a commercial item of a surface treatment agent, For example, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyl trimethoxysilane), Shin-Etsu Chemical Co., Ltd. product "KBM803" (3-mercapto) propyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltri methoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), etc. are mentioned.

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/m2 or more, more preferably 0.08 mg/m2 or more, still more preferably 0.11 mg/m2 or more. , still 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 amount of carbon is preferably 1.00 mg/m2 or less, more preferably 0.75 mg/m2 or less, still more preferably 0.70 mg/m2 or less, still more preferably 0.65 mg/m2 or less, 0.60 mg/m2 or less. m 2 or less, 0.55 mg/m 2 or less, and 0.50 mg/m 2 or less.

The amount of carbon per unit area couple|bonded with the surface of an inorganic filler is computable with the following procedure. A sufficient amount of methyl ethyl ketone (MEK) as a solvent is added to the inorganic filler after 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 carbon amount by the specific surface area of an inorganic filler, the carbon amount per unit surface area couple|bonded with the inorganic filler is computed. As a carbon analyzer, "EMIA-320V" by Horibase Corporation, etc. is mentioned, for example.

It is preferable that the resin composition of this invention contains a thermosetting resin and a hardening|curing agent further. As a thermosetting resin, an epoxy resin is preferable. Therefore, in one Embodiment, the resin composition of this invention contains an epoxy resin and a hardening|curing agent in addition to an inorganic filler.

-Epoxy resin-

Examples of the epoxy resin include bisphenol A 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 novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, Cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, butadiene structure epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, naph A thylene ether type epoxy resin, a trimethylol type epoxy resin, a tetraphenylethane type epoxy resin, etc. are mentioned. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

It is preferable that an epoxy resin contains the epoxy resin which has two or more epoxy groups in 1 molecule. When the nonvolatile component of an epoxy resin is 100 mass %, it is preferable that at least 50 mass % or more is an epoxy resin which has two or more epoxy groups in 1 molecule. Among them, an epoxy resin that has two or more epoxy groups in one molecule and is liquid at a temperature of 20°C (hereinafter referred to as “liquid epoxy resin”), and three or more epoxy groups in one molecule, which are solid at a temperature of 20°C It is preferable to contain an epoxy resin (hereinafter referred to as "solid epoxy resin"). As the epoxy resin, a resin composition having excellent flexibility is obtained by using a liquid epoxy resin and a solid epoxy resin together. Moreover, the breaking strength of the hardened|cured material of a resin composition also improves.

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 novolak type epoxy resin, and epoxy resin having a butadiene structure are preferable, and bisphenol A A type epoxy resin, a bisphenol F type epoxy resin, and a 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, "jER828EL" manufactured by Mitsubishi Chemical Co., Ltd. (bisphenol A type) Epoxy resin), "jER807" (bisphenol F-type epoxy resin), "jER152" (phenol novolak-type epoxy resin), "ZX1059" (bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Shin-Nittetsu Chemical Co., Ltd. mixture of resin), "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Co., Ltd., "PB-3600" manufactured by Daicel Chemicals Co., Ltd. (epoxy resin having a butadiene structure) ) can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the solid-state epoxy resin include a naphthalene-type tetrafunctional epoxy resin, a cresol novolak-type epoxy resin, a dicyclopentadiene-type epoxy resin, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, and a 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 An epoxy resin and a tetraphenylethane type epoxy resin are more preferable. As a specific example of a solid-state epoxy resin, "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Corporation, "N-690" (cresol novolak type epoxy resin), "N- 695” (cresol novolak 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 Nihon Kayaku Co., Ltd., “NC7000L” (naphthol novolak type epoxy resin), “NC3000H”, “NC3000” , "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthol type epoxy resin) manufactured by Shin-Nittetsu Chemical Co., Ltd., "ESN485" (naphthol novolac type epoxy resin), Mitsubishi "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" manufactured by Kaku Corporation (Anthracene type epoxy resin), Osaka Chemical Co., Ltd. "PG-100", "CG-500", Mitsubishi Chemical Co., Ltd. "YL7800" (fluorene type epoxy resin), Mitsubishi Chemical ( "jER1010" (solid bisphenol A type epoxy resin) manufactured by Note), "jER1031S" (tetraphenylethane type epoxy resin), etc. are mentioned.

As an epoxy resin, when using a liquid epoxy resin and a solid epoxy resin together, these ratios (liquid epoxy resin:solid epoxy resin) are mass ratio, and the range of 1:0.1 - 1:4 is preferable. By setting the ratio of the liquid epoxy resin to the solid epoxy resin in such a range, i) proper tackiness is brought about when used in the form of a sheet-like laminated material, and ii) sufficient flexibility is obtained when used in the form of a sheet-like laminated material. This is obtained, and effects such as improved handling properties and iii) being able to obtain a cured product having sufficient breaking strength are obtained. From the viewpoint of the effects of i) to iii) above, the amount ratio of the liquid epoxy resin and the solid epoxy resin (liquid epoxy resin:solid epoxy resin) is, in terms of mass ratio, more preferably in the range of 1:0.3 to 1:3.5, 1 The range of :0.6 to 1:3 is more preferable.

When content of the epoxy resin in a resin composition makes the non-volatile component in a resin composition 100 mass %, Preferably it is 3-40 mass %, More preferably, it is 5-35 mass %, More preferably, it is 10-30 mass %. %am.

The epoxy equivalent of an epoxy resin becomes like this. Preferably it is 50-5000, More preferably, it is 50-3000, More preferably, it is 80-2000, More preferably, it is 110-1000. By being in this range, the crosslinking density of hardened|cured material becomes sufficient, and the insulating layer with a small surface roughness can be brought about. In addition, an epoxy equivalent can be measured according to JISK7236, and is the mass of resin containing 1 equivalent of an epoxy group.

The weight average molecular weight of an epoxy resin becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. Here, the weight average molecular weight of an epoxy resin is the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) method.

-hardener-

The curing agent is not particularly limited as long as it has a function of curing the epoxy resin, and examples thereof include a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, and a cyanate ester-based curing agent. 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, from the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable. 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 novolak resin is preferable from a viewpoint of highly satisfying heat resistance, water resistance, and adhesive strength with a conductor layer. These may be used individually by 1 type, and may be used in combination of 2 or more type.

As a specific example of a phenol type hardening|curing agent and a naphthol type hardening|curing agent, For example, Meiwa Chemical Co., Ltd. product "MEH-7700", "MEH-7810", "MEH-7851", Nihon Kayaku Co., Ltd. product “NHN”, “CBN”, “GPH”, “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485” manufactured by Shin-Nittetsu Sumi-King Chemical Co., Ltd. ”, “SN-495”, “SN-375”, “SN-395”, “LA-7052”, “LA-7054”, “LA-3018”, “LA-1356” manufactured by DIC Co., Ltd. "TD2090" etc. are mentioned.

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 esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compound esters, are 2 in 1 molecule. Compounds having at least one compound are preferably used. It is preferable that the said active ester type hardening|curing agent is obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound, and 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, tri Hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolak, etc. are mentioned. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol to one molecule of dicyclopentadiene.

Examples of the active ester curing agent include 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 a benzoyl product of phenol novolac. The active ester compound contained is preferable, and among these, the active ester compound containing a naphthalene structure and the active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. These may be used individually by 1 type, and may be used in combination of 2 or more type. In addition, "dicyclopentadiene type diphenol structure" represents the divalent structural unit which consists of phenylene-dicyclopentalene-phenylene.

Commercially available active ester curing agents are active ester compounds containing a dicyclopentadiene type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", and "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 Co., Ltd.) as an active ester compound containing an acetylated product of phenol novolac, phenol "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) etc. are mentioned as an active ester compound containing a novolak benzoyl compound.

As a specific example of a benzoxazine type hardening|curing agent, "HFB2006M" by Showa Kofunshi Co., Ltd., "P-d" by Shikoku Chemical Industry Co., Ltd. product, and "F-a" are mentioned.

Although it does not specifically limit as a cyanate ester type hardening|curing agent, For example, a novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardening|curing agent, a dicyclopentadiene type cyanate ester type hardening|curing agent, bisphenol type (bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate ester curing agent, and a prepolymer in which these are partially triazined. Specific examples include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenyl cyanate), 4, 4'-ethylidenediphenyldisinate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis( 4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis bifunctional cyanate resins such as (4-cyanate phenyl) ether, polyfunctional cyanate resins derived from phenol novolac and cresol novolak, etc., and prepolymers in which these cyanate resins are partially triazined; and the like. As a commercial item of a cyanate ester type hardening|curing agent, "PT30" and "PT60" (both phenol novolak-type polyfunctional cyanate ester resin) manufactured by Ronjapan Co., Ltd., "BA230" (part of bisphenol A dicyanate or prepolymers in which all were triazineized and trimer); and the like.

The amount ratio of the epoxy resin and the curing agent is from the viewpoint of improving the mechanical strength and water resistance of the obtained insulating layer, [the total number of epoxy groups of the epoxy resin]: [the total number of reactive groups of the curing agent] in a ratio of 1:0.2 to 1 The range of :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 still more preferable. Here, a reactive group of a hardening|curing agent is an active hydroxyl group, an active ester group, etc., and it changes with the kind of hardening|curing agent. In addition, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the solid content 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 solid content mass of each curing agent equal to the reactor equivalent. It is a value obtained by dividing the value obtained by dividing by the sum of all curing agents.

In one embodiment, the resin composition of this invention contains said inorganic filler, an epoxy resin, and a hardening|curing agent. Among these, the resin composition uses 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 1:4, more preferably preferably 1:0.3 to 1:3.5, more preferably 1:0.6 to 1:3) as a curing agent, selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and a cyanate ester-based curing agent. It is preferable to contain 1 or more types, respectively. Also regarding the resin composition layer containing these specific components in combination, suitable content of an inorganic filler, an epoxy resin, and a hardening|curing agent is as above-mentioned.

The resin composition of this invention may further contain 1 or more types of additives selected from the group which consists of a thermoplastic resin, a hardening accelerator, a flame retardant, and an organic filler as needed.

-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, polyether ether ketone resin, and polyester resin are mentioned. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

The range of 8,000-70,000 is preferable, as for the polystyrene conversion weight average molecular weight of a thermoplastic resin, the range of 10,000-60,000 is more preferable, The range of 20,000-60,000 is still more preferable. The weight average molecular weight of a thermoplastic resin in terms of polystyrene is measured by a gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight in terms of polystyrene 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 Corporation as a column. -804L/K-804L can be calculated by using chloroform or the like as a mobile phase and measuring at a column temperature of 40°C using a standard polystyrene calibration curve.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetphenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene. and phenoxy resins having at least one skeleton selected from the group consisting of skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. Any functional group, such as a phenolic hydroxyl group and an epoxy group, may be sufficient as the terminal of a phenoxy resin. 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 resins) manufactured by Mitsubishi Chemical Co., Ltd., "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" (Bisphenolacetphenone skeleton-containing phenoxy resin), in addition, "FX280" and "FX293" manufactured by Shin-Nittetsu Chemical Co., Ltd., "YL7553" and "YL6794" manufactured by Mitsubishi Chemical Co., Ltd. ', "YL7213", "YL7290" and "YL7482".

Specific examples of polyvinyl acetal resin include Denkabutyral 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Denki Chemical Co., Ltd., S-Rec BH series manufactured by Sekisui Chemical Co., Ltd. , BX series, KS series, BL series, BM series, and the like.

As a specific example of polyimide resin, "Ricacoat SN20" and "Ricacoat PN20" by Shin-Nippon Rica Co., Ltd. are mentioned. As specific examples of the polyimide resin, furthermore, a linear polyimide obtained by reacting a difunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (the one described in Japanese Patent Application Laid-Open No. 2006-37083), polysiloxane and modified polyimides such as skeleton-containing polyimides (things described in JP-A-2002-12667 and JP-A-2000-319386).

Specific examples of the polyamideimide resin include "Hiromax HR11NN" and "Hiromax HR16NN" manufactured by Toyobo Seki Co., Ltd. Specific examples of the polyamideimide resin include modified polyamideimides such as polyamideimides containing polysiloxane skeleton manufactured by Hitachi Chemical Industry Co., Ltd. "KS9100" and "KS9300".

As a specific example of polyether sulfone resin, Sumitomo Chemical Co., Ltd. product "PES5003P" etc. are mentioned.

As a specific example of polysulfone resin, Solvay Advanced Polymers Co., Ltd. product polysulfone "P1700", "P3500", etc. are mentioned.

When content of the thermoplastic resin in a resin composition makes the non-volatile component in a resin composition 100 mass %, Preferably it is 0.1-20 mass %, More preferably, it is 0.5-10 mass %, More preferably, it is 1-5 mass %. %am.

-curing accelerator-

Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and guanidine-based curing accelerators, and phosphorus-based curing accelerators, amine-based curing accelerators and imidazole-based curing accelerators are preferable. . A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type. When content of a hardening accelerator makes the sum total of an epoxy resin and the nonvolatile component of a hardening|curing agent 100 mass %, it is preferable to use it in 0.05-3 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. Although content in particular of the flame retardant in a resin composition is not limited, When the nonvolatile component in a resin composition is 100 mass %, Preferably it is 0.5-10 mass %, More preferably, it is 1-9 mass %.

-Organic Fillings-

As the organic filler, any organic filler that can be used when forming the insulating layer of the printed wiring board may be used. Examples of the organic filler include rubber particles, polyamide fine particles and silicon particles, and rubber particles are preferable.

The rubber particles are not particularly limited as long as they are fine particles of a resin that is chemically crosslinked to a resin exhibiting rubber elasticity and made insoluble and infusible in an organic solvent, for example, acrylonitrile butadiene rubber particles, butadiene rubber particles, acrylic a rubber particle etc. are mentioned. Specifically as rubber particles, XER-91 (manufactured by Nippon Kosei Rubber Co., Ltd.), Staphyloid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (above, manufactured by Aika Kogyo Co., Ltd.), Paraloid EXL2655 and EXL2602 (above, Kureha Chemical Co., Ltd. make) etc. are mentioned.

The average particle diameter of the organic filler is preferably in the range of 0.005 to 1 µm, more preferably in the range of 0.2 to 0.6 µm. The average particle diameter of rubber particles can be measured using a dynamic light scattering method. For example, the rubber particles are uniformly dispersed in a suitable organic solvent by ultrasonic waves or the like, and the particle size distribution of the rubber particles is determined by mass using a thick particle size analyzer (“FPAR-1000” manufactured by Otsuka Denshi Co., Ltd.). It can measure by creating and making this median diameter into an average particle diameter. Content of the rubber particle in a resin composition becomes like this. Preferably it is 1-10 mass %, More preferably, it is 2-5 mass %.

-Other Ingredients-

The resin composition of this invention may contain other components as needed. Examples of such other components include organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds, and resin additives such as thickeners, defoamers, leveling agents, adhesion imparting agents, colorants and curable resins. have.

The preparation method of the resin composition of this invention is not specifically limited, For example, the method of adding a solvent etc. to a compounding component as needed, mixing and dispersing using a rotary mixer etc. are mentioned.

While the resin composition of this invention shows favorable dispersion stability and moderate melt viscosity, the curvature in the mounting process of a component can be suppressed. 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 further forms an interlayer insulating layer in which a conductor layer is formed by plating It can be used further suitably as a resin composition (resin composition for interlayer insulating layers of a printed wiring board which forms a conductor layer by plating) for following. The resin composition of the present invention is further used in applications requiring 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 encapsulant, a hole filling resin, a component filling resin, etc. can be used extensively in

[Sheet-like laminated material]

Although the resin composition of this invention can also be apply|coated and used in a varnish state, it is industrially generally suitable to use it in the form of the sheet-like laminated material containing the resin composition layer formed from the said resin composition.

As a sheet-like laminated material, the adhesive film and prepreg shown below are preferable.

In one embodiment, the adhesive film contains a support body and the resin composition layer (adhesive layer) bonded to the said support body, The resin composition layer (adhesive layer) is formed from the resin composition of this invention.

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

As a support body, the film which consists of a plastic material, metal foil, and a release paper is mentioned, for example, The film which consists of a plastic material, and metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material is, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”). .) polyester, polycarbonate (hereinafter, may be abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES) ), polyether ketone, polyimide, and the like. 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, or a foil made of an alloy of copper and other metals (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) is used. also good

As for a support body, mat treatment and corona treatment may be given to the surface of the side joined with the resin composition layer. Moreover, as a support body, you may use the support body with a mold release layer which has a mold release layer on the surface of the side joined with a resin composition layer. As a mold release agent used for the mold release layer of a support body with a mold release layer, 1 or more types of mold release agents are mentioned from the group which consists of an alkyd resin, an olefin resin, a urethane resin, and a silicone resin, for example. As a commercial item of a mold release agent, "SK-1", "AL-5", "AL-7" etc. which are alkyd resin mold release agents manufactured by Lintec Co., Ltd. are mentioned, for example.

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. On the other hand, when a support body is a support body with a mold release layer, it is preferable that the total thickness of a support body with a mold release layer is the said range.

The adhesive film can be produced by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying this resin varnish to a support using a die coater, etc., and drying it to form a resin composition layer. .

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitols such as cellosolve and butylcarbitol; aromatic hydrocarbons such as toluene and xylene; and 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.

What is necessary is just to perform drying by well-known methods, such as heating and hot-air spraying. Although drying conditions are not specifically limited, Content of the organic solvent in a resin composition layer is 10 mass % or less, Preferably it is made to dry so that it may become 5 mass % or less. Although it changes also with the boiling point of the organic solvent in a resin varnish, when using the resin varnish containing 30-60 mass % of organic solvents, for example, by drying at 50-150 degreeC for 3-10 minutes, the resin composition layer is can be formed

An adhesive film WHEREIN: On the surface which is not joined to the support body of a resin composition layer (that is, the surface on the opposite side to a support body), the protective film according to a support body can be laminated|stacked further. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating|stacking a protective film, adhesion of dust, etc. to the surface of a resin composition layer, and a flaw can be prevented. The adhesive film can be wound and stored in roll shape. When an adhesive film has a protective film, it becomes usable by peeling a protective film.

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

The sheet-like fiber base material used for the prepreg is not particularly limited, and those commonly used as the base material for prepregs, such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric, can be used. From a viewpoint of thickness reduction of a printed wiring board, the thickness of a sheet-like fiber base material becomes like this. Preferably it is 50 micrometers or less, More preferably, it is 40 micrometers or less, More preferably, it is 30 micrometers or less, More preferably, it is 20 micrometers 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.

A prepreg can be manufactured by well-known methods, such as a hot melt method and a solvent method.

The thickness of a prepreg can be made into the range similar to the resin composition layer in said adhesive film.

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, still more preferably from the viewpoint of suppressing the exuding of the resin during production of the printed wiring board. is 700 poise or more, 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, still more preferably from the viewpoint of achieving good lamination properties (circuit embedding property) at the time of manufacturing a printed wiring board. 20000 poise or less, 15000 poise or less, 10000 poise or less, 5000 poise or less, or 3500 poise or less. In particular, when laminating the resin composition layer and the inner layer substrate by the vacuum lamination method in the production of a printed wiring board, the upper limit of the minimum melt viscosity of the resin composition layer is preferably 5000 poise or less or 3500 poise or less. Here, the "minimum melt viscosity" of a resin composition layer means the minimum viscosity which a resin composition layer shows when resin of a resin composition layer melt|dissolves. Specifically, when the resin composition layer is heated at a constant temperature increase rate to melt the resin, in the initial stage, the melt viscosity decreases as the temperature rises, and then, when the temperature exceeds a certain temperature, the melt viscosity increases with the temperature rise. "Minimum melt viscosity" means the melt viscosity of such a minimum point. The minimum melt viscosity of the resin composition layer can be measured by a dynamic viscoelasticity method, for example, according to the method described in <Measurement of minimum melt viscosity> mentioned later.

In the present invention, in which a predetermined amount of an inorganic filler satisfying specific shape parameter conditions is used, a resin composition layer exhibiting the lowest melt viscosity in the above suitable range can be advantageously formed, and exhibiting good lamination properties in the production of a printed wiring board. may result in a sheet-like laminated material. Moreover, since the resin composition of this invention shows favorable dispersion stability, in the sheet-like laminated material obtained WHEREIN: It can suppress that coarse aggregated particle precipitates in a resin composition layer.

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 (for an interlayer insulating layer of a printed wiring board). It can be used suitably, and can be used further suitably for the resin composition (for the interlayer insulating layer of a printed wiring board which forms a conductor layer by plating) for forming the interlayer insulating layer in which the conductor layer is formed by plating.

[Printed wiring board]

The printed wiring board of this invention contains the insulating layer formed with the hardened|cured material of the resin composition of this 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 said adhesive film.

(I) a step of laminating an adhesive film on the inner layer substrate so that the resin composition layer of the adhesive film is bonded to the inner layer substrate

(II) Step of thermosetting the resin composition layer to form an insulating layer

The "inner layer substrate" used in the step (I) is mainly a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or one side of the substrate Or it refers to a circuit board on which a patterned conductor layer (circuit) is formed on both sides. In addition, when manufacturing a printed wiring board, an inner-layer circuit board of an intermediate product on which an insulating layer and/or a conductor layer is to be formed is also included in the "inner-layer board" referred to in the present invention.

From a viewpoint of thickness reduction of a printed wiring board, the thickness of an inner-layer board becomes like this. Preferably it is 800 micrometers or less, More preferably, it is 400 micrometers or less, More preferably, it is 200 micrometers or less. ADVANTAGE OF THE INVENTION According to this invention, even when using a thinner inner-layer board, the curvature of the printed wiring board in a mounting process can be suppressed. For example, use an inner-layer 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. Even in the case of doing so, the curvature in the mounting process can be suppressed. Although the lower limit of the thickness of an inner-layer substrate is not specifically limited, From a viewpoint of the handleability improvement at the time of printed wiring board manufacture, Preferably it is 10 micrometers or more, More preferably, it is 20 micrometers or more.

The flexural modulus of the inner layer substrate is not particularly limited. In the present invention, the curvature in the component mounting step can be suppressed regardless of the flexural modulus of the inner layer substrate.

Lamination of the inner layer substrate and the adhesive film can be performed, for example, by thermocompression bonding the adhesive film to the inner layer substrate from the support side. As a member (hereinafter also referred to as "thermal compression member") which heat-compresses an adhesive film to an inner-layer board|substrate, a heated metal plate (SUS mirror plate etc.), a metal roll (SUS roll), etc. are mentioned, for example. On the other hand, it is preferable to press through an elastic material, such as a heat-resistant rubber, so that the adhesive film can fully harvest the surface unevenness|corrugation of an inner-layer board|substrate, without directly pressing a heat-compression-compression-compression-bonding member to an adhesive film.

What is necessary is just to perform lamination|stacking of an inner-layer board|substrate and an adhesive film by the vacuum lamination method. In the vacuum lamination method, the thermocompression compression temperature is preferably in the range of 60 to 160°C, more preferably 80 to 140°C, and the thermocompression compression pressure is preferably 0.098 to 1.77 MPa, more preferably 0.29 to It is the range of 1.47 MPa, and thermocompression bonding time becomes like this. Preferably it is for 20 to 400 second, More preferably, it is the range for 30 to 300 second. Lamination is preferably carried out under reduced pressure conditions of a pressure of 26.7 hPa or less.

Lamination can be performed with a commercially available vacuum laminator. As a commercially available vacuum laminator, the vacuum pressurization type laminator by the Meiki Sesakusho Co., Ltd. product, the vacuum applicator by the Nichigo Morton Co., Ltd. product, etc. are mentioned, for example.

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

You may also perform lamination|stacking of an inner-layer board|substrate and an adhesive film using a vacuum hot press machine. By using a vacuum hot press machine, even when using a resin composition with high inorganic filler content, favorable lamination property (circuit embedding property) can be achieved. Although heating and pressurization may be performed in one step, it is preferable to carry out by dividing conditions into two or more steps from a viewpoint of suppressing that resin seeps. For example, in the first stage press, the temperature is in the range of 70 to 150°C and the pressure is in the range of 0.098 to 1.77 MPa, and in the second stage press, the temperature is in the range of 150 to 200°C and the pressure is in the range of 0.098 to 3.92 MPa. It is preferable to carry out It is preferable that the time of each step is 30 to 120 minutes. Pressing is usually performed under reduced pressure of ^{1×10 -2} MPa or less, preferably 1×10 ^{-3 MPa or less.} As a commercially available vacuum hot press machine, "MNPC-V-750-5-200" by Meiki Sesakusho Co., Ltd., "VH1-1603" by Kitagawa Seiki Co., Ltd. etc. are mentioned, for example. When performing the step (I) using a vacuum hot press machine, the step may also serve as thermosetting of the resin composition layer (ie, step (II)).

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

In the process (II), the resin composition layer is thermosetted to form an insulating layer.

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

For example, although the thermosetting conditions of the resin composition layer also differ depending on the type of resin composition, etc., the curing temperature is in the range of 120 to 240°C (preferably in the range of 150 to 210°C, more preferably 170 to 190°C). ℃) and curing time in the range of 5 to 90 minutes (preferably 10 to 75 minutes, more preferably 15 to 60 minutes).

Before thermosetting a resin composition layer, you may preheat a resin composition layer at temperature lower than hardening temperature. For example, prior to thermosetting the resin composition layer, at a temperature of 50°C or more and less than 120°C (preferably 60°C or more and 110°C or less, more preferably 70°C or more and 100°C or less), the resin composition layer is 5 You may preheat for more than a minute (preferably for 5 to 150 minutes, More preferably, for 15 to 120 minutes).

The insulating layer formed of the hardened|cured material of the resin composition of this invention shows a low coefficient of thermal expansion. In one embodiment, the insulating layer formed of the hardened|cured material of the resin composition of this invention becomes like this. Preferably it is 30 ppm/degreeC or less, More preferably, it has a coefficient of linear thermal expansion of 28 ppm/degreeC or less. Although the lower limit in particular of the coefficient of linear thermal expansion of an insulating layer is not restrict|limited, Usually, it is 1 ppm/degreeC or more. The linear thermal expansion coefficient of an insulating layer can be measured by well-known methods, such as a thermomechanical analysis, for example. As a thermomechanical analyzer, "Thermo Plus TMA8310" by Rigaku Co., Ltd. is mentioned, for example. In the present invention, the coefficient of linear thermal expansion of the insulating layer is a coefficient of linear thermal expansion of 25 to 150°C in the planar direction when thermomechanical analysis is performed by the tensile weighting method.

When manufacturing a printed wiring board, (III) the step of drilling the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming a conductor layer on the surface of the insulating layer may be additionally performed. good. What is necessary is just to implement these processes (III)-(V) according to various methods well-known to those skilled in the art used for manufacture of a printed wiring board. On the other hand, when the support is removed after the step (II), the removal of the support is carried out between the steps (II) and (III), between the steps (III) and (IV), or between the steps (IV) and the step (V). ) can be done between

Step (III) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. The step (III) may be performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer and the like. What is necessary is just to determine the dimension and shape of a hole suitably according to the design of a printed wiring board. As mentioned above, since the resin composition of this invention shows favorable dispersion stability, it can suppress that coarse aggregated particle precipitates in a resin composition layer by extension, and also in an insulating layer. In the insulating layer having such a uniform composition, a hole having a desired cross-sectional shape can be formed in the step (III). Accordingly, even when a filled via is formed by filling the hole with the conductor metal, the inside of the hole can be smoothly filled with the conductor metal. In this regard, if sharply angled inorganic fillers or coarse aggregates thereof exist on the wall surface of the hole, such as in the case of using crushed inorganic fillers, the plating will preferentially elongate with the inorganic filler or coarse aggregates thereof as a starting point. Voids may occur during field vias. In the present invention using an inorganic filler that satisfies specific shape parameter conditions, it is possible to suppress the presence of such aggregated particles on the wall surface of the hole, so that the plating is uniformly extended over the entire wall surface of the hole, and voids in the filled via can be advantageously suppressed.

Process (IV) is a process of roughening an insulating layer. The procedure and conditions of a roughening process are not specifically limited, When forming the insulating layer of a printed wiring board, the well-known procedure and conditions normally used are employable. For example, the insulating layer can be roughened by performing the swelling process by a swelling liquid, the roughening process by an oxidizing agent, and the neutralization process by a neutralizing liquid in this order. Although it does not specifically limit as a swelling liquid, An alkali solution, surfactant solution, etc. are mentioned, Preferably it is an alkali solution, As said alkali solution, sodium hydroxide solution and potassium hydroxide solution are more preferable. As a commercially available swelling liquid, Swelling Deep Securigant P, Swelling Deep Securigant SBU, etc. manufactured by Atotech Japan Co., Ltd. are mentioned, for example. Although the swelling process by a swelling liquid is not specifically limited, For example, it can implement by immersing an insulating layer in a 30-90 degreeC swelling liquid for 1 to 20 minutes. Although it does not specifically limit as an oxidizing agent, For example, the alkaline permanganic acid solution which melt|dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. It is preferable to perform the roughening process by oxidizing agents, such as alkaline permanganic acid solution, by making the insulating layer immerse for 10 to 30 minutes in the oxidizing agent solution heated to 60-80 degreeC. Moreover, as for the density|concentration of the permanganate in an alkaline permanganic acid solution, 5-10 mass % is preferable. As a commercially available oxidizing agent, alkaline permanganic acid solutions, such as Atotech Japan Co., Ltd.|KK Concentrate Compact CP and Dosing Solution Securigant P, are mentioned, for example. Moreover, as a neutralizing liquid, acidic aqueous solution is preferable, As a commercial item, Atotech Japan Co., Ltd. product reduction solution Securigant P 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 oxidizing agent solution in a neutralizing solution at 30 to 80° C. for 5 to 30 minutes.

The insulating layer formed using the resin composition of this invention shows low surface roughness after a roughening process. In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening is preferably 500 nm or less, more preferably 480 nm or less, still more preferably 450 nm or less, still more preferably 400 nm or less, 360 nm or less. or less or 320 nm or less. Even when Ra is small in this way, the insulating layer formed using the resin composition of this invention shows the adhesive strength excellent with respect to a conductor layer. Although limitation in particular is not carried out as for the minimum of Ra value, 0.5 nm or more is preferable and 1 nm or more is more preferable. The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact type surface roughness meter. As a specific example of a non-contact type surface roughness meter, "WYKO NT3300" by a BCoin Instruments company is mentioned.

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

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

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, it is preferable that the layer in contact with the insulating layer is a single metal layer of chromium, zinc or titanium, or an alloy layer of a nickel-chromium alloy.

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

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

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Then, on the formed plating seed layer, a mask pattern for exposing a portion of the plating seed layer corresponding to a desired wiring pattern is formed. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is 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 this invention shows sufficient adhesive strength with respect to a conductor layer. In one embodiment, the adhesive strength of an insulating layer and a conductor layer becomes like this. Preferably it is 0.50 kgf/cm or more, More preferably, it is 0.55 kgf/cm or more, More preferably, it is 0.60 kgf/cm or more. Although the upper limit of adhesion strength is not specifically limited, It becomes 1.2 kgf/cm or less, 0.90 kgf/cm or less, etc. In this invention, although the surface roughness Ra of the insulating layer after a roughening process is small, since the insulating layer which shows such high adhesion strength can be formed, it contributes remarkably to refinement|miniaturization of circuit wiring. In addition, in this invention, the adhesive strength of an insulating layer and a conductor layer means the peeling strength (90 degree|times peeling strength) when a conductor layer is peeled in the perpendicular|vertical direction (90 degree|times direction) with respect to an insulating layer, and insulating a conductor layer. It can obtain|require by measuring the peeling strength at the time of peeling in the perpendicular|vertical direction (90 degree|times direction) with respect to a layer with a tensile tester. As a tensile tester, "AC-50C-SL" by TES Co., Ltd. etc. is mentioned, for example.

In another embodiment, the printed wiring board of this invention can be manufactured using said prepreg. The manufacturing method is basically the same as in the case of using an adhesive film.

[Semiconductor device]

A semiconductor device can be manufactured using the printed wiring board of this invention. Although the printed wiring board of the present invention is thin, it can suppress warpage even in the mounting process of components employing a high solder reflow temperature, and problems such as circuit deformation and poor contact of components can be advantageously reduced.

In one embodiment, the printed wiring board of this invention can suppress the curvature of a printed wiring board to less than 40 micrometers in the mounting process employ|adopting the solder reflow temperature as high as 260 degreeC of peak temperature. In the present invention, the warpage of the printed wiring board is the value of the difference between the maximum height and the minimum height of the displacement data when the warpage behavior of each 10 mm portion in the center of the printed wiring board is observed with a shadow moiré device. During measurement, the reflow temperature profile (profile for lead-free assembly; peak temperature 260) described in IPC/JEDEC J-STD-020C (“Moisture/Reflow Sensitivity Classification For Nonhermetic Solid State Surface Mount Devices”, July 2004) ℃), after passing the printed wiring board once through a reflow device that reproduces the Displacement data were obtained for the grid lines formed in . On the other hand, as a reflow apparatus, "HAS-6116" manufactured by Nippon Antom Co., Ltd. is mentioned, for example, As a shadow moire apparatus, "TherMoire AXP" by Akrometrix is mentioned, for example. The printed wiring board of the present invention comprising an insulating layer formed of a cured product of a resin composition containing a predetermined amount of an inorganic filler satisfying specific shape parameter conditions, even if thin, can advantageously suppress warpage in the mounting process .

Examples of the semiconductor device include various semiconductor devices provided for electric products (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trams, ships, aircraft, etc.) can

The semiconductor device of this invention can be manufactured by mounting a component (semiconductor chip) in the conduction|electrical_connection location of the printed wiring board of this invention. A "conduction location" is "a location through which an electric signal is transmitted in a printed wiring board", and the location may be a surface, a buried location, or any. In addition, a semiconductor chip will not be specifically limited if it is an electric circuit element which uses a semiconductor as a material.

Although the semiconductor chip mounting method at the time of manufacturing the semiconductor device of this invention is not specifically limited as long as the semiconductor chip functions effectively, Specifically, a wire bonding mounting method, a flip chip mounting method, a bumpless build-up layer The mounting method by (BBUL), the mounting method by an anisotropic conductive film (ACF), the mounting method by a nonelectroconductive film (NCF), etc. are mentioned. Here, "a mounting method using a bumpless build-up layer (BBUL)" refers to a "mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board, and the semiconductor chip and the wiring on the printed wiring board are connected" .

[Example]

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In addition, in the following, "part" and "%" mean "part by mass" and "mass %", respectively, unless otherwise indicated.

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

[Preparation of substrate 1 for evaluation]

(1) Preparation of inner-layer circuit board

Both sides of the glass cloth base epoxy resin double-sided copper clad laminate (copper foil thickness 18㎛, substrate thickness 0.3mm, Matsushita Denko Co., Ltd. "R5715ES") on which the inner-layer circuit was formed were coated with "CZ8100" manufactured by Meg Co., Ltd. 1 It etched micrometer and performed the roughening process of the copper surface.

(2) Lamination of the adhesive film

The adhesive films produced in Examples and Comparative Examples were bonded to the inner circuit board by using a batch vacuum pressurized laminator (“MVLP-500” manufactured by Meiki Sesakusho Co., Ltd.) so that the resin composition layer was bonded to the inner circuit board. was laminated on both sides of the Lamination|stacking was performed by pressure-reducing for 30 second and making atmospheric|air pressure 13 hPa or less, and then crimping|bonding at 100 degreeC and pressure 0.74 MPa for 30 second.

(3) Hardening of the resin composition layer

After lamination, the support was peeled from both surfaces of the substrate. Next, the resin composition layer was thermosetted under curing conditions at 100°C for 30 minutes and at 170°C for 30 minutes to form an insulating layer.

(4) Harmonization processing

After the formation of the insulating layer, the substrate was placed in a swelling solution (Atotech Japan Co., Ltd. “Swelling Dip Securigant P”, an aqueous solution containing diethylene glycol monobutyl ether and sodium hydroxide) at 80° C. for 5 minutes, followed by an oxidizing agent (Atotech Japan Co., Ltd. “Concentrate Compact CP”, KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) at 80° C. for 10 minutes, and finally a neutralizing solution (Atotech Japan Co., Ltd.) It was immersed at 40 degreeC for 5 minutes in "reduction solution securigant P", aqueous hydroxylamine sulfate aqueous solution). Then, it dried at 80 degreeC for 30 minutes. The obtained board|substrate is called "substrate 1a".

On the other hand, with respect to Example 6 and Comparative Example 5, the operations (2) to (4) were performed as follows to obtain a substrate 1a.

The adhesive films produced in Examples and Comparative Examples were applied to both sides of the inner circuit board using a vacuum press device (“VH1-1603” manufactured by Kitagawa Seiki Co., Ltd.) so that the resin composition layer was bonded to the inner circuit board. laminated. Lamination was carried out by ^{pressing under a reduced pressure of 1×10 -3} MPa at 100° C. and a pressure of 1.0 MPa for 30 minutes, then raising the temperature to 180° C. over 10 minutes, and then pressing at 180° C. and a pressure of 1.0 MPa for 30 minutes. . Thereby, the resin composition layer was thermosetted and the insulating layer was formed. The roughening process was carried out like said (4) except having immersed in the swelling liquid at 60 degreeC for 5 minutes, and 80 degreeC for 5 minutes in the oxidizing agent.

(5) Formation of conductor layer

According to the semiadditive method, a conductor layer was formed on the surface of the insulating layer as follows.

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. Then, after heating at 150 degreeC for 30 minutes and performing annealing process, the etching resist was formed and it pattern-formed by etching. Then, copper sulfate electroplating was performed, the 25-micrometer-thick conductor layer was formed, and the annealing process was performed at 180 degreeC for 30 minute(s). The obtained substrate is called &quot;substrate 1b&quot;.

[Preparation of substrate 2 for evaluation]

(1) Preparation of the inner layer substrate

As the inner layer substrate, an unclad plate (thickness of 100 µm) from which the copper foil on both sides of the glass cloth base epoxy resin double-sided copper clad laminate was removed was prepared. As a glass cloth base epoxy resin double-sided copper clad laminate, Mitsubishi Gas Chemical Co., Ltd. "HL832NSF-LCA" (size 100mm x 150mm, base base material thickness 100㎛, thermal expansion rate 4ppm/°C, flexural modulus 34GPa, surface copper circuit thickness of 16 μm) was used.

(2) Lamination of the adhesive film

The adhesive films produced in Examples and Comparative Examples were subjected to a batch-type vacuum pressurization laminator (two-stage build-up laminator "CVP700" manufactured by Richigo Morton Co., Ltd.) so that the resin composition layer was in contact with the inner layer substrate, It was laminated on both sides of the inner layer substrate. Lamination|stacking was performed by pressure-reducing for 30 second and making atmospheric|air pressure 13 hPa or less, and then crimping|bonding at 100 degreeC and pressure 0.74 MPa for 30 second. Then, it hot-pressed for 60 second at 100 degreeC and the pressure of 0.5 MPa.

(3) Hardening of the resin composition layer

After lamination, the support was peeled from the substrate. Next, the resin composition layer was thermosetted under curing conditions at 190°C for 90 minutes to form an insulating layer. The obtained board|substrate is called "substrate 2a".

<Measurement of specific surface area (S) of inorganic filler>

The specific surface area of the inorganic filler was calculated|required by nitrogen BET method using the automatic specific surface area measuring apparatus ("Macsorb HM-1210" manufactured by Mountec Co., Ltd.).

<Measurement of average particle diameter (R) of inorganic filler>

To a 20 ml vial, 0.01 g of inorganic filler, 0.2 g of a nonionic dispersant (“T208.5” manufactured by Nihon Yushi Co., Ltd.), and 10 g of pure water were added, followed by ultrasonic dispersion for 10 minutes with an ultrasonic cleaner to prepare a sample did. Next, the sample was put into a laser diffraction particle size distribution analyzer ("SALD2200" manufactured by Shimadzu Corporation), and ultrasonic waves were irradiated for 10 minutes while being circulated. Then, the ultrasonic wave was stopped, the particle size distribution was measured while the circulation of the sample was maintained, and the average particle diameter (R) of the inorganic filler was calculated|required. On the other hand, the refractive index at the time of measurement was set to 1.45-0.001i.

<Calculation of shape parameter A>

The shape parameter A was calculated by substituting the values of the specific surface area (S), the average particle diameter (R), and the density (ρ) of the inorganic filler into the following formula (1).

[Equation 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 using the FIB-SEM composite apparatus ("SMI3050SE" manufactured by SII Nanotechnology Co., Ltd.) at an observation magnification of 14,000 times. 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 Corporation). On the other hand, the measurement was performed with respect to arbitrary 50 inorganic filler particles per sample, avoiding the inorganic filler particle which is not clear on the whole image, or the inorganic filler particle whose outline is not clear. From the area of the obtained inorganic filler particles, the perimeter length (circumference; Lc) of a perfect circle equal to it was calculated. Then, by substituting the values of L and Lc into Equation 2 below, the shape parameter B was calculated for each inorganic filler particle, and the average value of the shape parameter B and its distribution were obtained.

[Equation 2]

B = Lc/L

<Measurement of average crystallite diameter of inorganic filler>

The average crystallite diameter of the inorganic filler was calculated|required according to the following procedure. First, the inorganic filler was fixed to a glass test plate, and the sample plate was prepared. The sample plate was set in a wide-angle X-ray diffraction apparatus ("Multi FLEX" manufactured by Rigaku Co., Ltd.), and the diffraction profile was measured by a wide-angle X-ray diffraction and 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 Scherrer's formula.

<Evaluation of dispersion stability>

About the adhesive film produced by the Example and the comparative example, the flock|aggregate in the resin composition layer was observed using the microscope ("VH-2250" manufactured by KEYENCE Corporation) at an observation magnification of 1000 times. The dispersion stability of the resin composition was evaluated according to the following criteria.

Evaluation standard:

(circle): 10 micrometers or more aggregation particle is less than 2 out of 10 fields of view

x: 2 or more 10 micrometers or more aggregated particles 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, melt viscosity was measured using the dynamic viscoelasticity measuring apparatus ("Rheosol-G3000" manufactured by UBM Co., Ltd.). With respect to 1 g of the sample resin composition, using a parallel plate having a diameter of 18 mm, the temperature was raised from the starting temperature of 60°C to 200°C at a temperature increase rate of 5°C/min, and dynamic with measurement conditions of 2.5°C, measurement temperature interval, 1 Hz intensity, and 1deg deformation. The viscoelastic modulus was measured and the lowest melt viscosity was determined. Laminability was averaged according to the following criteria.

Evaluation standard:

○: Minimum melt viscosity of 30000 poise or less

x: The minimum melt viscosity is higher than 30000 poise

<Evaluation of warpage>

The substrate 2a (n = 5) was passed once through a reflow device (“HAS-6116” manufactured by Nippon Antom Co., Ltd.) that reproduces the solder reflow temperature of a peak temperature of 260°C (the reflow temperature profile is Conforms to IPC/JEDEC J-STD-020C). Next, using a shadow moire apparatus (“TherMoire AXP” manufactured by Akrometrix), the lower surface of the substrate is heated with a reflow temperature profile conforming to IPC/JEDEC J-STD-020C (peak temperature 260°C), and placed on the upper surface of the substrate Based on one grid line, the displacement of each part of 10 mm in the center of the substrate was measured. The curvature was evaluated according to the following evaluation criteria.

Evaluation standard:

○: For all 5 samples, the difference between the maximum height and the minimum height of the displacement data in the entire temperature range was less than 40 µm

x: 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 mean roughness (Ra)>

Regarding the substrate 1a, using a non-contact type surface roughness meter ("WYKO NT3300" manufactured by BCoin Instruments), Ra by the numerical value obtained by setting the measurement range to 121 탆 x 92 탆 with a 50x lens in VSI contact mode. value was obtained. It was set as the measured value by calculating|requiring the average value of 10 randomly selected points|pieces.

<Measurement of adhesion strength of conductor layer>

The measurement of the adhesive strength of an insulating layer and a conductor layer was performed based on JISC6481 about the evaluation board|substrate 1b. Specifically, when a notch having a width of 10 mm and a length of 100 mm is put in the conductor layer of the substrate 1b, this end is peeled off and picked up with tongs, and 35 mm is peeled off in the vertical direction at a rate of 50 mm/min at room temperature. The load (kgf/cm) of was measured, and the adhesion strength was calculated|required.

<Measurement of coefficient of linear thermal expansion>

The adhesive films prepared in Examples and Comparative Examples were heated at 190° C. for 90 minutes to thermoset the resin composition layer. Then, the support was peeled off to obtain a sheet-like cured product. The obtained sheet-like cured product was cut into test pieces having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was performed by a tensile weighting method using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Co., Ltd.). carried out. In detail, after the test piece was mounted on the said thermomechanical analysis apparatus, it measured twice continuously under the measurement conditions of 1 g of load and 5 degreeC/min of temperature increase rate. And the 2nd measurement WHEREIN: The average coefficient of linear thermal expansion in the range from 25 degreeC to 150 degreeC was computed.

<Evaluation of Void of Field Via>

Evaluation of the void of a field via was performed according to the following procedure.

(1) Formation of via hole

Using a carbon dioxide laser processing machine (“LC-2E21B/1C” manufactured by Hitachi Chemical Corporation), a via hole having a top diameter of 60 µm and a void diameter of 50 µm was formed in the insulating layer laminated on one side of the substrate 1a. formed.

(2) Formation of filled vias

After the via hole was formed, the insulating layer was roughened to form a conductor layer. The roughening process and formation of a conductor layer were performed like [Preparation of the board|substrate 1 for evaluation]. Thereby, the conductor metal was also filled in the inside of the via hole, and a filled via was obtained.

(3) evaluation of voids

The formed field via was cross-sectionally observed using a scanning electron microscope (SEM) (made by Hitachi High-Technologies Corporation, model "SU-1500"). In addition, the case where the number of voids was less than 2 among 10 filled vias was made into "circle", and the case where 2 or more was made into "x".

Table 1 lists the physical properties and shape parameters A and B of the inorganic fillers used in Examples and Comparative Examples together.

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

<Example 1>

(1) Preparation of resin varnish

20 parts of liquid bisphenol A epoxy resin (epoxy equivalent 187, "jER828EL" manufactured by Mitsubishi Chemical Co., Ltd.), 30 parts of biphenyl type epoxy resin (epoxy equivalent 276, "NC3000" manufactured by Nihon Kayaku Co., Ltd.) 30 parts, tetra 5 parts of phenylethane type epoxy resin (epoxy equivalent 198, manufactured by Mitsubishi Chemical Co., Ltd. "jER1031S"), solid bisphenol A type epoxy resin (epoxy equivalent approximately 3000 to 5000, manufactured by Mitsubishi Chemical Co., Ltd. "jER1010") 5 parts of a 50 mass % nonvolatile component resin solution dissolved in a mixed solvent having a mass ratio of methyl ethyl ketone (MEK) and cyclohexanone of 1:1 in a mixed solvent of 20 parts of MEK and 10 parts of cyclohexanone was dissolved by heating while stirring. . In addition, 10 parts of triazine skeleton-containing phenol novolac curing agent (hydroxyl equivalent 125, DIC Co., Ltd. “LA-7054”, MEK solution having a solid content of 60%), phenol novolac curing agent (hydroxyl equivalent 105, DIC ( 6 parts of "TD2090" manufactured by Co., Ltd.), 3 parts of an amine-based curing accelerator (4-dimethylaminopyridine (DMAP), a MEK solution having a solid content of 5% by mass), N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Co., Ltd.) Crystalline silica surface-treated ("KBM573" manufactured by Kaku Corporation) ("IMSIL A-8" manufactured by Unimin, average particle diameter 1.38 μm, maximum particle diameter 20 μm, specific surface area 6.54 m 2 /g, density 2.65 g/cm 3 , average crystallite diameter of 1000 Å) 180 parts, flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene- 10-oxide, average particle diameter 2 µm) 5 parts were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. On the other hand, the total density of nonvolatile components other than the inorganic filler used for preparation of the resin varnish was about 1.2 g/cm<3>.

(2) Preparation of adhesive film

As a support body, the polyethylene terephthalate film (38 micrometers in thickness, Lintech Co., Ltd. product, "AL5") with an alkyd resin type mold release layer was prepared. The resin varnish prepared above was uniformly applied 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 micrometers, and the amount of residual solvent in the resin composition was about 2 mass %. Next, on the surface of the resin composition layer, as a protective film, a polypropylene film (manufactured by Oshitoku Shushi Co., Ltd., on the smooth surface side of "Alpan MA-411", 15 µm in thickness) was applied and wound in roll shape. It was slitted to 507 mm, and the adhesive film of the size of 507 mm x 336 mm was obtained.

<Example 2>

Instead of 30 parts of a biphenyl type epoxy resin (epoxy equivalent 276, manufactured by Nihon Kayaku Co., Ltd. "NC3000"), 10 parts of a biphenyl type epoxy resin (epoxy equivalent 276, manufactured by Nippon Gayaku Co., Ltd. "NC3000") 10 parts and naphtha A resin varnish was prepared in the same manner as in Example 1 except that 18 parts of a thylene ether type epoxy resin (epoxy equivalent 250, "HP6000" manufactured by DIC Corporation) was used to prepare an adhesive film.

<Example 3>

12 parts of a naphthol novolac hardener (hydroxyl equivalent: 215, "SN485" manufactured by Shin-Nittetsu Sumikingaku Co., Ltd.) was used instead of 6 parts of a phenol novolak-based curing agent (hydroxyl equivalent: 105, manufactured by DIC Co., Ltd. “TD2090”); and N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) The amount of crystalline silica surface-treated ("IMSIL A-8" manufactured by Unimin) was changed to 210 parts Other than that, it carried out similarly to Example 1, the resin varnish was prepared, and the adhesive film was produced.

<Example 4>

In place of the solid bisphenol A epoxy resin (epoxy equivalent of about 3000 to 5000, manufactured by Mitsubishi Chemical Co., Ltd. "jER1010"), phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Co., Ltd.), MEK/cyclo with a solid content of 30% by mass Except having used 8 parts of hexanone = 1/1 solution), the resin varnish was prepared like Example 1, and the adhesive film was produced.

<Example 5>

Instead of 180 parts of crystalline silica surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("IMSIL A-8" manufactured by Unimin), N-phenyl-3 -Crystallized silica surface-treated with aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("IMSIL A-25" manufactured by Unimin, average particle diameter 2.55 μm, maximum particle diameter 20 μm, specific surface area A resin varnish was prepared in the same manner as in Example 1, except that 5.87 m 2 /g, a density of 2.65 g/cm 3 , and an average crystallite diameter of 1400 Å) was used to prepare an adhesive film.

<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 diameter 1.38 µm, maximum particle diameter) 20 μm, specific surface area 6.54 m 2 / g, density 2.65 g/cm 3 , average crystallite diameter of 1000 Å) was changed to 400 parts, except that a resin varnish was prepared in the same manner as in Example 1 to prepare an adhesive film.

<Comparative Example 1>

Instead of 180 parts of crystalline silica surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("IMSIL A-8" manufactured by Unimin), N-phenyl-3 -Spherical silica surface-treated with aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C2” manufactured by Adomatex Co., Ltd., average particle diameter 0.90 μm, specific surface area 5.75 m 2 / g, density 2.2 g/cm 3 ) Except having used 150 parts, a resin varnish was prepared like Example 1, and the adhesive film was produced.

<Comparative Example 2>

Instead of 180 parts of crystalline silica surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("IMSIL A-8" manufactured by Unimin), N-phenyl-3 -Spherical silica surface-treated with aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C6” manufactured by Adomatex Co., Ltd., average particle diameter 2.06 μm, specific surface area 2.15 m 2 / g, density 2.2 g/cm 3 ) Except having used 150 parts, a resin varnish was prepared like Example 1, and the adhesive film was produced.

<Comparative Example 3>

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

<Comparative Example 4>

Except that the amount of crystalline silica surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“IMSIL A-8” manufactured by Unimin) was changed to 80 parts. , A resin varnish was prepared in the same manner as in Example 1, and an adhesive film was produced.

<Comparative Example 5>

Except that the amount of crystalline silica surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“IMSIL A-8” manufactured by Unimin) was changed to 480 parts. , A resin varnish was prepared in the same manner as in Example 1, and an adhesive film was produced.

Claims (14)

A resin composition for an insulating layer of a printed wiring board, comprising:
When the nonvolatile component in the resin composition is 100% by volume, the content of the inorganic filler is 40 to 75% by volume,
Equation: A = SRρ/6 [where S is the specific surface area (m2/g) of the inorganic filler, R is the average particle diameter (㎛) of the inorganic filler, and ρ is the density (g/cm3) of the inorganic filler The resin composition, wherein the shape parameter A of the inorganic filler represented by ] satisfies 20≤6A≤40. A resin composition for an insulating layer of a printed wiring board, comprising:
When the nonvolatile component in the resin composition is 100% by volume, the content of the inorganic filler is 40 to 75% by volume,
Equation: B = Lc/L [where L is the peripheral length (μm) of the inorganic filler in a predetermined cross-section, and Lc is the cross-sectional area of the inorganic filler in the cross-section and the equal area It is the peripheral length (micrometer) of a perfect circle.] The average value of the shape parameter B of the inorganic filler represented by 0.8 or more and 0.9 or less, The resin composition. 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 according to claim 1 or 2, wherein the inorganic filler has a specific surface area of 3 to 10 m 2 /g. The resin composition of Claim 1 or 2 whose average particle diameter of an inorganic filler is 4 micrometers or less. The resin composition of Claim 1 or 2 whose average particle diameter of an inorganic filler is 3 micrometers or less. The inorganic filler according to claim 1 or 2, wherein the inorganic filler is obtained by dispersing a grape cluster agglomerate of microcrystalline particles having an average crystallite diameter of 1800 Å or less, and the maximum particle diameter of the grape cluster agglomerate. The resin composition which is 20 micrometers or less. The resin composition according to claim 1 or 2, wherein the inorganic filler contains a crystalline inorganic filler, and the content of the crystalline inorganic filler is 50% by mass or more when the total amount of the inorganic filler is 100% by mass. The resin composition according to claim 8, wherein the crystalline inorganic filler is crystalline silica. The resin composition according to claim 1 or 2, further comprising an epoxy resin and a curing agent. The resin composition according to claim 1 or 2, which is a resin composition for an interlayer insulating layer. A sheet-like laminated material comprising a resin composition layer formed of the resin composition according to claim 1 or 2. The printed wiring board containing the insulating layer formed with the hardened|cured material of the resin composition of Claim 1 or 2. A semiconductor device comprising the printed wiring board according to claim 13 .