TWI666268B - Resin composition for insulating layer of printed circuit board - Google Patents

Abstract

An object of the present invention is to provide a resin composition for an insulating layer of a printed circuit board that exhibits good dispersion stability and moderate melt viscosity, and can suppress warpage in a part packaging step.

The solution is a resin composition, which is a resin composition for an insulating layer of a printed circuit board. If the non-volatile content in the resin composition is 100% by volume, the content of the inorganic filler is 40 to 75% by volume. : A = SRρ / 6 [where S is the specific surface area of the inorganic filler (m ² / g), R is the average particle diameter of the inorganic filler (μm), and ρ is the density of the inorganic filler (g / cm ³ The shape parameter A of the inorganic filler shown in the figure) satisfies 20 ≦ 6A ≦ 40.

Description

Resin composition for insulating layer of printed circuit board

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

As a manufacturing technology of a printed circuit board, a manufacturing method is known that employs a build-up method in which an insulating layer and a conductive layer are alternately overlapped on an inner substrate. In the manufacturing method using the build-up method, the insulating layer is formed by, for example, laminating a resin composition layer on an inner substrate by using an adhesive film including a resin composition layer, and then curing the resin composition layer. The resin composition used for the formation of the insulating layer is generally based on the viewpoint of reducing the thermal expansion coefficient of the obtained insulating layer and preventing the occurrence of cracks or circuit distortion caused by the difference in thermal expansion between the insulating layer and the conductor layer. material. As this inorganic filler, a spherical inorganic filler is suitably used (Patent Document 1).

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2010-238667

With the replacement of lead-free solder to lead-free solder in recent years, the reflow temperature in the component packaging step has also increased. Furthermore, in recent years, in order to reduce the size of electronic equipment, further reductions in the thickness of printed circuit boards have been continuously promoted.

With the progress of thinning the printed circuit board, the printed circuit board may warp during the packaging step of the part, which may cause problems such as circuit distortion or poor contact of the part. The inventors of the present invention have found that by using a crushed inorganic filler instead of a spherical inorganic filler, it is possible to suppress warpage in the packaging step of the part. However, a resin composition containing a crushed inorganic filler has poor dispersion stability, and may easily become a high melt viscosity and cause poor lamination.

An object of the present invention is to provide a resin composition for an insulating layer of a printed circuit board that exhibits good dispersion stability and moderate melt viscosity, and can suppress warpage in a part packaging step.

As a result of intensive research on the above-mentioned problems, the inventors of the present case have found that the above-mentioned problems can be solved by using an existing amount of an inorganic filler having a specific shape, and the present invention has finally been completed.

That is, the present invention includes the following:

[1] A resin composition, which is a resin composition for an insulating layer of a printed circuit board. When the non-volatile content in the resin composition is 100% by volume, the content of the inorganic filler is 40 to 75% by volume. : A = SRρ / 6 [where S is the specific surface area of the inorganic filler (m ² / g), R is the average particle diameter of the inorganic filler (μm), and ρ is the density of the inorganic filler (g / cm ³ The shape parameter A of the inorganic filler shown in the figure) satisfies 20 ≦ 6A ≦ 40.

[2] A resin composition, which is a resin composition for an insulating layer of a printed circuit board. If the non-volatile content in the resin composition is 100% by volume, the content of the inorganic filler is 40 to 75% by volume. : B = Lc / L [where L is the perimeter (μm) of the inorganic filler of a predetermined cross section, and Lc is the perimeter (μm) of a perfect circle having the same area as the cross section of the inorganic filler of the aforementioned cross section] The average value of the shape parameter B of the inorganic filler shown is 0.8 or more and 0.9 or less.

[3] The resin composition according to [1] or [2], wherein the average crystallite diameter of the inorganic filler is 1800 angstroms or less.

[4] The resin composition according to any one of [1] to [3], wherein the specific surface area of the inorganic filler is 3 to 10 m ² / g.

[5] The resin composition according to any one of [1] to [4], wherein the average particle diameter of the inorganic filler is 4 μm or less.

[6] The resin composition according to any one of [1] to [5], wherein the average particle diameter of the inorganic filler is 3 μm or less.

[7] The resin composition according to any one of [1] to [6], wherein the inorganic filler It is obtained by dispersing fine granular aggregates of microcrystalline particles having an average crystallite diameter of 1800 angstroms or less, and the maximum particle diameter of the fine granular aggregates is 20 μm or less.

[8] The resin composition according to any one of [1] to [7], wherein the inorganic filler material includes a crystalline inorganic filler material, and the content of the crystalline inorganic filler material is set to 100 mass as a whole of the inorganic filler material. At%, it is 50% by mass or more.

[9] The resin composition according to [8], wherein the crystalline inorganic filler is crystalline silicon dioxide.

[10] The resin composition according to any one of [1] to [9], further comprising an epoxy resin and a hardener.

[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 circuit board comprising an insulating layer formed of a cured product of a resin composition according to any one of [1] to [11].

[14] A semiconductor device comprising a printed circuit board as in [13].

According to the present invention, it is possible to provide a resin composition for an insulating layer of a printed circuit board that exhibits good dispersion stability and moderate melt viscosity, and can suppress warpage in a part packaging step.

[Resin composition for insulating layer of printed circuit board]

The resin composition for an insulating layer of a printed circuit board of the present invention (hereinafter also simply referred to as "the resin composition of the present invention") contains a predetermined amount of inorganic filler having a spherical shape and a conventionally known inorganic filler, and a broken inorganic material. Inorganic fillers with different shapes are featured.

The inorganic filler used in the present invention is different from the spherical inorganic filler, and has an angular shape, and the broken inorganic filler has an acute angle shape; and the inorganic filler used in the present invention is slightly rounded. ; In these two points, it has a shape different from the crushed inorganic filler.

If the projected shape on a plane is compared with a spherical inorganic filler that cannot clearly identify edges and corners, the inorganic filler used in the present invention can clearly identify edges and corners. Here, the term "identifiable edges and corners of a projected shape on a plane" refers to a projected shape on a plane that can be identified as a straight line or a substantially straight line, and at a certain angle θ (projected shape) with the straight line or a substantially straight line. Inside angle) straight or slightly straight. In addition, in the inorganic filler used in the present invention, the average value of the angle θ is larger than that of the crushed inorganic filler system. For example, compared to the broken inorganic filler, the average value of the angle θ of the inorganic filler used in the present invention is preferably 5 ° larger, more preferably 7.5 ° larger, and even more preferably 10 °, 12.5 ° larger. , 15 °, 17.5 °, or 20 °.

Hereinafter, the shape of the inorganic filler used in the present invention will be described using two shape parameters, that is, shape parameter A and shape parameter B. In addition, although shape parameter A and shape parameter B The difference between the parameters derived from the two-dimensional method or the parameters derived from the two-dimensional method, but either one is a parameter that indicates the degree of deformation of the true sphere from the shape of the inorganic filler.

<Shape parameter A>

The shape parameter A is expressed by the following formula (1): Formula (1): A = SRρ / 6 In the formula, S is the specific surface area of the inorganic filler (m ² / g), and R is the average particle diameter of the inorganic filler ( μm), and ρ represents the density (g / cm ³ ) of the inorganic filler.

It is assumed that a system having a plurality of true balls (hereinafter also referred to as a "true ball model system") is assumed. When the average surface area-based average particle diameter of such a true sphere (diameter) of R, present on a plurality of balls within the true model of the system to true sphere πR ² represents the average volume of places πR ^3/6 FIG. Further, when the sphere is really a density [rho], the average mass present in the plurality of true spherical balls within the true model of the system is represented by an πρR ^3/6.

Secondly, an imaginary average volume and density of an inorganic filler system equal to the true sphere model system. Based on the fact that a true sphere has the smallest surface area for an object of the same volume, the average surface area of the plurality of inorganic fillers existing in the inorganic filler system can be represented by AπR ² . Here, A is a shape parameter of the inorganic filler, and the lower limit thereof is 1 (when the inorganic filler is a true sphere). Further, when a condition based on volume and the average density equal to the true sphere model system, the average mass present in the plurality of the inorganic filler of inorganic filler within the system may πρR ^3/6 FIG. Moreover, in the inorganic filler material system, the specific surface area S of the inorganic filler material can be [the average surface area of the plurality of inorganic filler materials existing in the inorganic filler material system (AπR ² )] / [the plural number existing in the inorganic filler material system the average mass of an inorganic filler (πρR ^3/6)] indicates, it becomes 6A / (Rρ). That is, when the relational expression of S = 6A / (Rρ) holds, and the expression is transformed with respect to the shape parameter A, the above-mentioned expression (1) can be obtained.

The inorganic filler used in the present invention is characterized in that the shape parameter A shown in the above formula (1) satisfies 20 ≦ 6A ≦ 40. A preferable 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, a molecule having a known adsorption area can be adsorbed on an inorganic filler sample at a temperature of liquid nitrogen, and the specific surface area of the inorganic filler sample can be determined from the amount of the adsorbed amount. As a molecule whose adsorption area is known, 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. Examples of the automatic specific surface area measurement device include "Macsorb HM-1210" manufactured by Mountain Tech.

The average particle diameter R of the inorganic filler can be measured by a laser diffraction · scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler based on volume can be prepared by using a laser diffraction particle size distribution measuring device, and the median diameter can be used as the average particle diameter for measurement. The measurement sample can be preferably used: the inorganic filler Ultrasonic waves are dispersed in water. Examples of the laser diffraction type particle size distribution measurement device include "SALD2200" manufactured by Shimadzu Corporation, "LA-500", "LA-750", and "LA-950" manufactured by Horiba Corporation.

<Shape parameter B>

The shape parameter B is expressed by the following formula (2): Formula (2): B = Lc / L where L is the perimeter (μm) of the inorganic filler with a predetermined cross section, and Lc is the same as the inorganic filler with the aforementioned cross section. The perimeter (μm) of a perfect circle with a cross-sectional area of equal area.

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

The shape parameter B is a parameter established for each particle of the inorganic filler. By obtaining the shape parameter B for a sufficient number of particles constituting the inorganic filler, it is possible to grasp the overall characteristics related to 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 average value is used to identify the shape of the inorganic filler. In the said embodiment, the inorganic filler used by this invention is characterized by the average value of the shape parameter B shown by said Formula (2) being 0.8 or more and 0.9 or less. A better range for the average value of the shape parameter B Will be described later.

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

In order to obtain the perimeter L of the inorganic filler of a predetermined cross-section and the cross-sectional area of the inorganic filler of the cross-section required to obtain the shape parameter B, the cross-sectional observation of a layer formed using the resin composition of the present invention can be used to measure . Section observation is more suitable for using FIB-SEM composite device. From the obtained FIB-SEM image, the perimeter and area (cross-sectional area) of the inorganic filler existing in the layer can be determined by using image processing software such as "QWin V3" manufactured by Leica Corporation. An example of the FIB-SEM composite device is "SMI3050SE" manufactured by SII Nanotechnology.

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

In one embodiment, the resin composition of the present invention is such that if the non-volatile content in the resin composition is 100% by volume, the content of the inorganic filler is 40 to 75% by volume, as shown in the above formula (1) The shape parameter A of the inorganic filler is characterized by satisfying 20 ≦ 6A ≦ 40 (hereinafter also referred to as “the resin composition of the first embodiment”).

From the viewpoint of obtaining a resin composition that exhibits good dispersion stability and moderate 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 preferably 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 Below, below 34, below 33, below 32, below 31, or below 30. From the viewpoint of sufficiently suppressing warpage in the packaging step of the part, it is important that the lower limit of the above 6A is 20 or more. From the viewpoint of further suppressing warpage in the packaging step of the part, the lower limit value of the above 6A is preferably 21 or more, 22 or more, or 23 or more.

In another embodiment, the resin composition of the present invention is such that if the non-volatile content in the resin composition is 100% by volume, the content of the inorganic filler is 40 to 75% by volume. It is characteristic that the average value of the shape parameter B of the inorganic filler shown is 0.8 or more and 0.9 or less (hereinafter also referred to as "the resin composition of the second embodiment").

From the viewpoint of obtaining a resin composition showing 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. From the viewpoint of sufficiently suppressing warpage in the packaging step of the part, 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 further suppressing warpage in the packaging step of the part, 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 difference between the first embodiment and the second embodiment, if the non-volatile content in the resin composition is set to 100% by volume, based on the viewpoint of sufficiently suppressing warpage in the part packaging step, the thermal expansion coefficient of the obtained insulating layer is sufficiently reduced. From a viewpoint, the content of the inorganic filler is 40% by volume or more, preferably 42% by volume or more, more preferably 44% by volume or more, still more preferably 46% by volume or more, still more preferably 48% by volume or more, particularly preferably 50% by volume, 52% by volume, 54% by volume, 56% by volume, 58% by volume, or 60% by volume. When a crushed inorganic filler is used, the melt viscosity tends to increase excessively as the content of the inorganic filler increases. In contrast, for the inorganic filler used in the present invention that satisfies specific shape parameter conditions, a good melt viscosity can be achieved, and the content can be further increased. For example, in the resin composition of the present invention, the content of the inorganic filler can be increased to 62% by volume or more, 64% by volume or more, 66% by volume or more, or 68% by volume or more. The upper limit of the content of the inorganic filler is 75% by volume or less from the viewpoint of obtaining a resin composition exhibiting a moderate melt viscosity and an insulating layer having a small surface roughness and excellent adhesion strength (peel strength) to the conductor layer. It is preferably 74% by volume or less, more preferably 73% by volume or less, even more preferably 72% by volume or less, still more preferably 71% by volume or less, and particularly preferably 70% by volume or less. In particular, when the resin composition layer and the inner layer substrate are laminated by a vacuum lamination method during the manufacture of a printed wiring board, the upper limit of the content of the inorganic filler is preferably 70% by volume or less. The content (vol%) of the inorganic filler can be based on the mass and density of the inorganic filler used for the preparation of the resin composition, and the non-volatile components other than the inorganic filler used for the preparation of the resin composition. Calculate mass and density.

Regardless of the difference between the first embodiment and the second embodiment, from the viewpoint of obtaining a resin composition that exhibits good dispersion stability and melt viscosity, the value of the shape parameter B shown in the above formula (2) in the inorganic filler has not reached The lower the particle content of 0.8, the better. In the resin composition of the present invention, the content of particles having a shape parameter B represented by the above formula (2) of less than 0.8 in the inorganic filler is usually 50% or less, preferably 48% or less. It is more preferably 46% or less, even more preferably 44% or less, even more preferably 42% or less, or 40% or less. In particular, the content of particles having a value of the shape parameter B of 0.75 or less is preferably 20% or less, 18% or less, or 16% or less.

Regardless of the difference between the first embodiment and the second embodiment, based on the viewpoint of sufficiently suppressing warpage in the packaging step of the part, the content of the particles in the inorganic filler having a value of the shape parameter B represented by the above formula (2) greater than 0.9 is greater than 0.9. The lower the line, the better. In the resin composition of the present invention, the content of the particles having a value of the shape parameter B represented by the above formula (2) in the inorganic filler greater than 0.9 is usually 30% or less, preferably 28% or less, more It is preferably 26 or less%, even more preferably 24 or less%, and even more preferably 22 or less or 20 or less. In particular, the content of particles having a value of the shape parameter B of 0.94 or more is preferably 6% or less, 4% or less, 2% or less, 1% or less, 0.8% or less, 0.6 Several percent or less, 0.4 percent or less, 0.2 percent or less.

In the resin composition of the present invention, the material of the inorganic filler is not particularly limited, and examples thereof include silica, alumina, glass, and cordierite. Stone, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, gibbsite, 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, zirconia, barium titanate, barium zirconate titanate, barium zirconate, Calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate are particularly preferred as silicon dioxide. The inorganic fillers may be used alone or in combination of two or more. When two or more types of 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 can be achieved by using the obtained inorganic filler mixture separately. The average particle diameter, specific surface area, and density are sufficient.

From the viewpoint of miniaturization of circuit wiring, the average particle diameter (R) of the inorganic filler is preferably 4 μm or less, more preferably 3.5 μm or less, and even more preferably 3 μm or less. From the viewpoint of obtaining a resin varnish with a moderate viscosity and good handling properties when forming a resin varnish using a resin composition, the lower limit of the average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.03 μm or more, and even more preferably It is 0.05 μm or more, 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-mentioned shape parameter conditions are satisfied in the relationship between the average particle diameter (R) and the density (ρ). The specific surface area of the inorganic filler may be, for example, in a range of 3 to 10 m ² / g, and preferably in a range of 3 to 8 m ² / g.

The inorganic filler may be either amorphous or crystalline as long as it satisfies the aforementioned shape parameter conditions. In one embodiment, the resin composition of the present invention contains a crystalline inorganic filler. If you set inorganic filler When the total amount of the filler is 100% by mass, the content of the crystalline inorganic filler in the inorganic filler is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more, particularly preferably 90% by mass or more, 92% by mass or more, 94% by mass or more, 96% by mass or more, 98% by mass or more, or 99% by mass or more. The inorganic filler may be substantially composed of a crystalline inorganic filler, with the exception of impurities that cannot be avoided. In the embodiment, the average crystallite diameter of the inorganic filler is preferably 1800 Å or less, more preferably 1600 Å or less, and even more preferably 1400 Å or less. The lower limit of the average crystallite diameter is not particularly limited, but it is usually preferably 100 Å or more, 200 Å or more. The crystallite diameter of the inorganic filler can be measured using an X-ray diffraction (XRD) device. Examples of the XRD device include "Multi FLEX" manufactured by Rigaku.

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

The inorganic filler that satisfies the above-mentioned conditions of the shape parameter can be made slightly smaller by, for example, physically and / or chemically grinding the surface of the broken inorganic filler having an acute-angled shape by a method of physical and / or chemical polishing, Modulated with a circle. The method of physical polishing and chemical polishing is not particularly limited, and any conventionally known method can be used. Examples of commercially available products of crushed silica include "VX-SR" manufactured by Ronson Corporation.

In addition, among the naturally produced inorganic oxides, there are inorganic oxides that ideally satisfy the aforementioned shape parameter conditions. For example, natural silicon dioxide produced from fine-grained aggregates of microcrystalline particles with an average crystallite diameter of less than 1800Å In the following case), through the dispersion operation during the preparation of the resin composition, the fine-grained aggregates disintegrate to satisfy the aforementioned shape parameter conditions. Therefore, in one embodiment, the inorganic filler contained in the resin composition of the present invention is obtained by dispersing fine-grained aggregates of microcrystalline particles having an average crystallite diameter of 1800 Å or less. It is characterized by a maximum particle diameter of 20 μm or less. Examples of commercially available products of the natural silicon dioxide include, for example, "IMSIL A-8", "IMSIL A-10", "IMSIL A-15", "IMSIL A-25", and the like manufactured by Unimin Corporation.

The inorganic filler used in the resin composition of the present invention is preferably surface-treated with a surface-treating agent from the 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 organic silazane compound, and a titanate (salt) -based coupling agent. The surface treatment agents may be used singly or in combination of two or more kinds. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and "KBM803" (3) manufactured by Shin-Etsu Chemical Industry Co., Ltd. -Mercaptopropyltrimethoxysilane), "KBE903" (3-Aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM573" (N-phenyl- 3-aminopropyltrimethoxysilane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and the like.

After the surface treatment of the inorganic filler, the amount of carbon per unit surface area bonded to the surface of the inorganic filler is preferably 0.05 mg / m ² or more, more preferably 0.08 mg / m ² or more, and even more preferably 0.11 mg / m. ² or more, still more preferably 0.14mg / m ² or more, particularly preferably 0.17mg / m ² or more, 0.20mg / m ² or more, 0.23mg / m ² or more, or 0.26mg / m ² or more. The upper limit of the carbon content is preferably 1.00mg / m ² or less, more preferably 0.75mg / m ² or less, and then the best of 0.70mg / m ² or less, and still more preferably 0.65mg / m ² or less, 0.60mg / m ² or less, 0.55mg / m ² or less, ² or less 0.50mg / m.

The amount of carbon per unit surface area bonded to the surface of the inorganic filler can be calculated by the following procedure. A sufficient amount of methyl ethyl ketone (MEK) as a solvent was added to the inorganic filler after the surface treatment, and ultrasonic cleaning was performed. After removing the upper solution and drying the solid content, the amount of carbon bonded to the surface of the inorganic filler was measured with a carbon analyzer. The obtained carbon content was divided by the specific surface area of the inorganic filler to calculate the amount of carbon per unit surface area bonded to the inorganic filler. Examples of the carbon analyzer include "EMIA-320V" manufactured by Horiba Ltd.

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

-Epoxy resin-

Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, and dicyclopentadiene epoxy resin. Ginseng phenol epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tertiary butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene Epoxy Resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure , Alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexanedimethanol epoxy resin, naphthyl ester epoxy resin, trimethylol epoxy resin, four Phenylethane type epoxy resin and the like. One type of epoxy resin may be used alone, or two or more types may be used in combination.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile content of the epoxy resin is 100% by mass, it is preferable that at least 50% by mass or more be an epoxy resin having two or more epoxy groups in one molecule. Among them, an epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C. (hereinafter referred to as a “liquid epoxy resin”) is preferred, and three in one molecule are included. The epoxy resin having the above epoxy group and having a solid state at a temperature of 20 ° C (hereinafter referred to as "solid epoxy resin"). As the epoxy resin, a liquid epoxy resin and a solid epoxy resin are used in combination to obtain a resin composition having excellent flexibility. Moreover, the fracture strength of the hardened | cured material of a resin composition is also improved.

The liquid epoxy resin is preferably a bisphenol A epoxy resin, a bisphenol F epoxy resin, a naphthalene epoxy resin, a glycidyl ester epoxy resin, a phenol novolac epoxy resin, and a butyl epoxy resin. Diene-structured epoxy resins are more preferably bisphenol A epoxy resin, bisphenol F epoxy resin, and naphthalene epoxy resin. Specific examples of the liquid epoxy resin include "HP4032", "HP4032H", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin), and "jER828EL" manufactured by Mitsubishi Chemical Corporation. (Bisphenol A ring Oxygen resin), "jER807" (bisphenol F-type epoxy resin), "jER152" (phenol-phenol novolac-type epoxy resin), "ZX1059" (bisphenol A-type epoxy resin and Mixture of bisphenol F-type epoxy resin), "EX-721" (glycidyl-type epoxy resin) made by Nagase ChemteX (stock), "PB-3600" (with butadiene) made by DAICEL Chemical Industry (stock) Structure of epoxy resin). These may be used individually by 1 type, and may use 2 or more types together.

The solid epoxy resin is preferably a naphthalene-type tetrafunctional epoxy resin, a cresol novolac-type epoxy resin, a dicyclopentadiene-type epoxy resin, a phenol-type epoxy resin, a naphthol-type epoxy resin, Biphenyl epoxy resin, naphthalene ether epoxy resin, anthracene epoxy resin, bisphenol A epoxy resin, tetraphenylethane epoxy resin, more preferably naphthalene tetrafunctional epoxy resin, naphthalene Phenol type epoxy resin, biphenyl type epoxy resin, naphthalene ether type epoxy resin, bisphenol A type epoxy resin, tetraphenylethane type epoxy resin. Specific examples of the solid epoxy resin include "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin), and "N-690" (cresol novolac ring) Oxygen resin), "N-695" (cresol novolac epoxy resin), "HP-7200" (dicyclopentadiene epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4 "," EXA7311-G4S "," HP6000 "(naphthalene ether type epoxy resin)," EPPN-502H "(reference phenol type epoxy resin) made by Nippon Kayaku Co., Ltd., and" NC7000L "(naphthol phenol type ring) Oxygen resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthol type epoxy resin) made by Nippon Steel & Sumitomo Chemical Co., Ltd., " "ESN485" (naphthol novolac epoxy resin), "YX4000H" made by Mitsubishi Chemical Corporation, "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), Osaka Gas Chemicals (stock), PG-100, "CG-500", Mitsubishi Chemical Corporation's "YL7800" (茀 -type epoxy resin), Mitsubishi Chemical Corporation's "jER1010" (solid bisphenol A-type epoxy resin), "jER1031S" (tetrabenzene Ethane type epoxy resin) and the like.

As the epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used in combination, their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1: 0.1 to 1 in terms of mass ratio. : 4 range. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within the above range, the following effects can be obtained: i) moderate adhesion when used in the form of a sheet-like laminated material; ii) sheet When the shape of the layered material is used, sufficient flexibility can be obtained to improve handling properties; and iii) a hardened material having sufficient fracture strength can be obtained. From the viewpoint of the effects of i) to iii) above, the amount ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably 1: 0.3 by mass ratio. The range is from ~ 1: 3.5, and even more preferably from 1: 0.6 to 1: 3.

When the non-volatile content in the resin composition is 100% by mass, the content of the epoxy resin in the resin composition is preferably 3% to 40% by mass, more preferably 5% to 35% by mass, and even more preferably It is 10% to 30% by mass.

The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, even more preferably 80 to 2000, and even more preferably 110 to 1,000. By adopting this range, the crosslinking density of the hardened material is more sufficient, and the rough surface can be provided. Insulation with less roughness. The epoxy equivalent can be measured in accordance with JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. Herein, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

-hardener-

The hardener is not particularly limited as long as it has a function of hardening the epoxy resin, and examples thereof include a phenol-based hardener, a naphthol-based hardener, an active ester-based hardener, a benzoxazine-based hardener, and cyanic acid. Ester-based hardener. The hardener may be used alone or in combination of two or more.

As the phenol-based hardener and the naphthol-based hardener, from the viewpoints of heat resistance and water resistance, a phenol-based hardener having a phenolic structure or a naphthol-based hardener having a phenolic structure is preferred. From the viewpoint of adhesion strength with the conductor layer, a nitrogen-containing phenol-based hardener or a nitrogen-containing naphthol-based hardener is preferable, and a triazine skeleton-containing phenol-based hardener or a triazine-based naphthol-based hardener is more preferable. hardener. Among them, a phenol novolac resin containing a triazine skeleton is preferred from the viewpoints that heat resistance, water resistance, and adhesion strength with a conductor layer can be highly satisfied. These may be used individually by 1 type, and may use 2 or more types together.

Specific examples of the phenol-based hardener and the naphthol-based hardener include, for example, "MEH-7700", "MEH-7810", "MEH-7851", manufactured by Meiwa Kasei Co., Ltd., and manufactured by Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", Nippon Steel & Sumitomo Chemical Co., Ltd.'s "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", " "SN-375", "SN-395", DIC (shares) system "LA-7052", "LA-7054", "LA-3018", "LA-1356", "TD2090", etc.

The active ester-based hardener is not particularly limited. Generally, it is preferable to use two or more reactions in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxyl compounds. Highly active ester-based compounds. The active ester-based hardener is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. Especially from the viewpoint of improving heat resistance, an active ester-based hardener obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based hardener 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, pyromellitic acid, and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, reduced phenolphthalein, methylated bisphenol A, and methylation. Bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6 -Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, resorcinol, pyrol, dicyclopentadiene type di Phenol compounds, phenol novolacs, etc. Here, "dicyclopentadiene-type diphenol compound" means that one molecule of dicyclopentadiene and two molecules of phenol are condensed. The resulting diphenol compound.

The active ester-based hardener is preferably an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetaldehyde compound containing phenol novolac, and an active ester compound containing phenol novolac. Among the active ester compounds of benzamidine, more preferred are active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure. These may be used individually by 1 type, and may use 2 or more types together. The "dicyclopentadiene-type diphenol structure" means a divalent structural unit composed of phenylene-dicyclopentadiene-phenylene.

As commercially available products of the active ester-based hardener, examples of the active ester compound containing a dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" ( DIC (made by DIC); for active ester compounds containing naphthalene structure, "EXB9416-70BK" (made by DIC (stock)); for active ester compounds containing phenolic aldehyde ethylacetate, " "DC808" (manufactured by Mitsubishi Chemical Corporation); for the active ester compound of a benzamidine compound containing phenol novolac, "YLH1026" (manufactured by Mitsubishi Chemical Corporation) and the like.

Specific examples of the benzoxazine-based hardener include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industry Co., Ltd.

The cyanate-based hardener is not particularly limited, and examples thereof include phenol-based (phenol-phenol-based, alkylphenol-phenol-based) cyanate-based hardeners, dicyclopentadiene-based cyanate-based hardeners, Bisphenol type (bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate ester-based hardeners, and the like Some prepolymers are triazinated. Specific examples include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis ( 2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanooxy ) Phenylpropane, 1,1-bis (4-cyanooxyphenylmethane), bis (4-cyanooxy-3,5-dimethylphenyl) methane, 1,3-bis (4-cyano Bifunctional cyanate ester resins such as oxyphenyl-1- (methylethylene)) benzene, bis (4-cyanoxyphenyl) sulfide, and bis (4-cyanoxyphenyl) ether, Polyfunctional cyanate resins derived from phenol novolac and cresol novolac, and prepolymers obtained by triazinating a part of these cyanate resins. As a commercially available product of a cyanate-based hardener, Examples include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate resins) and "BA230" (part or all of bisphenol A dicyanate) made by LONZA Japan Co., Ltd. Trimer prepolymers) and the like.

From the viewpoint of improving the mechanical strength and water resistance of the obtained insulating layer, the ratio of the epoxy resin to the hardener is calculated by the ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of hardener]. The range is preferably 1: 0.2 ~ 1: 2, more preferably 1: 0.3 ~ 1: 1.5, and even more preferably 1: 0.4 ~ 1: 1. Here, the reactive group of the hardener refers to an active hydroxyl group, an active ester group, and the like, and it depends on the type of the hardener. In addition, the total number of epoxy groups of epoxy resin refers to a value obtained by dividing the solid content mass of each epoxy resin by the value of epoxy equivalent for all epoxy resins; The total count means a value obtained by dividing the solid content mass of each hardener by the value of the reactive group equivalent for all the hardeners.

In one embodiment, the resin composition of the present invention contains the above-mentioned inorganic filler, epoxy resin, and hardener. Among them, the resin composition uses crystalline silicon dioxide as an inorganic filler, and contains a mixture of a liquid epoxy resin and a solid epoxy resin (liquid epoxy resin: solid epoxy resin has a better quality of 1: 0.1 ~ 1: 4, more preferably 1: 0.3 ~ 1: 3.5, even more preferably 1: 0.6 ~ 1: 3) as epoxy resin, containing phenol-based hardener, naphthol-based hardener, and active ester-based hardener One or more selected from the group consisting of a curing agent and a cyanate-based curing agent are preferred as the curing agent. The preferable content of the inorganic filler, the epoxy resin, and the hardener for the resin composition layer including the specific component in combination is as described above.

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

-Thermoplastic resin-

Examples of the thermoplastic resin include a phenoxy resin, a polyvinyl acetal resin, a polyolefin resin, a polybutadiene resin, a polyimide resin, a polyimide resin, a polyetherimide resin, and a polyimide resin.碸 resin, polyether 碸 resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin. The thermoplastic resin may be used singly or in combination of two or more kinds.

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

Examples of the phenoxy resin include a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a phenolic skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, One or more phenoxy resins selected from the group consisting of a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" made by Mitsubishi Chemical Corporation (both phenoxy resins containing a bisphenol A skeleton), and "YX8100" (phenoxy resins containing a bisphenol S skeleton) Resin), and "YX6954" (phenoxy resin containing bisphenol acetophenone skeleton); in addition, examples include "FX280" and "FX293" made by Nippon Steel & Sumikin Chemical Co., Ltd. ) To make "YL7553", "YL6794", "YL7213", "YL7290", "YL7482", etc.

Specific examples of the polyvinyl acetal resin include DENKA BUTYRAL 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Electrochemical Industry Co., Ltd., SLEC BH series manufactured by Sekisui Chemical Industry Co., Ltd., and BX Series, KS series, BL series, BM series, etc.

Specific examples of the polyimide resin include "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Nippon Rika Co., Ltd. Specific examples of the polyfluorene imide resin include linear polyfluorene imide obtained by reacting a difunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a quaternary acid anhydride (Japanese Patent Laid-Open No. 2006-37083). Those disclosed in the Gazette), modified polyimines containing a polysiloxane skeleton (as described in Japanese Patent Application Laid-Open No. 2002-12667 and Japanese Patent Application Laid-Open No. 2000-319386), and the like.

Specific examples of the polyamidamine / imide resin include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Corporation. As specific examples of the polyamidoamine imine resin, modified polyamidoamines such as polyamidoamine imines "KS9100" and "KS9300" containing a polysiloxane skeleton manufactured by Hitachi Chemical Industries, Ltd. can also be mentioned.醯 imine.

Specific examples of the polyether fluorene resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. and the like.

Specific examples of the polyfluorene resin include polyfluorene "P1700" and "P3500" made by Solvay Advanced Polymers.

When the non-volatile content in the resin composition is 100% by mass, the content of the thermoplastic resin in the resin composition is preferably 0.1% to 20% by mass, more preferably 0.5% to 10% by mass, and even more preferably 1% to 5% by mass.

-Hardening accelerator-

Examples of the hardening accelerator include a phosphorus-based hardening accelerator, an amine-based hardening accelerator, an imidazole-based hardening accelerator, and a guanidine-based hardening accelerator. Preferred are phosphorus-based hardening accelerators, amine-based hardening accelerators, and imidazole-based hardening accelerators. A hardening accelerator may be used individually by 1 type, and may use 2 or more types together. When the total amount of the nonvolatile components of the epoxy resin and the curing agent is 100% by mass, the content of the curing accelerator is preferably used in a range of 0.05% to 3% by mass.

-Flame retardant-

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

-Organic Filler-

As the organic filler, any organic filler that can be used when forming an insulating layer of a printed circuit board can be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles, and rubber particles are preferred.

The rubber particles are not particularly limited as long as they are chemically cross-linked to a resin exhibiting rubber elasticity, and the microparticles of the resin are insoluble and insoluble to organic solvents. Diene rubber particles, acrylic rubber particles, etc. Specific examples of the rubber particles include XER-91 (made by Japan Synthetic Rubber Co., Ltd.), STAFYROID AC3355, AC3816, AC3816N, AC3832 AC4030, AC3364, IM101 (the above is made by Aica Industrial Co., Ltd.) PARALOID EXL2655, EXL2602 (the above is made by Wu Yu Chemical Industry Co., Ltd.) and so on.

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

-Other ingredients-

The resin composition of the present invention may include other components as required. Examples of the other components include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; and thickeners, defoamers, leveling agents, adhesion-imparting agents, colorants, and hardening agents. Resin additives such as flexible resins.

The method of preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method of mixing and dispersing a blended component, adding a solvent, etc. as required, and using a rotary mixer or the like.

The resin composition of the present invention can exhibit good dispersion stability and moderate melt viscosity, and can suppress warpage in the packaging step of parts. The resin composition of the present invention can be suitably used as a resin composition for forming an interlayer insulation layer of a printed circuit board (interlayer insulation layer of a printed circuit board). Resin composition), and can be further suitable as a resin composition for forming: an interlayer insulating layer on which a conductor layer is formed by plating (interlayer of a printed circuit board with a conductor layer formed by plating) Resin composition for insulating layer). The resin composition of the present invention can also be used in the sheet-like laminated material, such as a film, a prepreg, a solder resist, an underfill, a die bonding material, a semiconductor sealing material, a hole filling resin, a part landfill resin, etc. The resin composition is used in a wide range of applications.

[Laminated sheet material]

The resin composition of the present invention can also be applied in the form of a varnish. However, in general, it is preferably used in the form of a sheet-like laminated material including a resin composition layer formed of the resin composition.

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

In one embodiment, the subsequent film comprises a support and a resin composition layer (adhesive layer) bonded to the support, and the resin composition layer (adhesive layer) is formed of the resin composition of the present invention.

From the viewpoint of reducing the thickness of the printed circuit board, the thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, even more preferably 60 μm or less, even more preferably 50 μm or less or 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but is usually 10 μm or more.

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

When a film made of a plastic material is used as a support, examples of the plastic material include polyethylene terephthalate (hereinafter referred to as "PET"), polyethylene naphthalate (hereinafter referred to as "PET") "PEN") and other polyesters, polycarbonate (hereinafter abbreviated as "PC"), acrylates such as polymethyl methacrylate (PMMA), cyclic polyolefins, and triethyl cellulose (TAC) , Polyethersulfur (PES), polyetherketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and low-cost polyethylene terephthalate is particularly preferred.

When a metal foil is used as a support, examples of the metal foil include copper foil, aluminum foil, and the like, and copper foil is preferred. As the copper foil, a foil composed of a single metal of copper may be used, or a foil composed of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

As for the support, the surface on one side to which the resin composition layer is bonded may be subjected to a matte treatment or a corona treatment. Moreover, as a support body, the support body with a mold release layer which has a mold release layer on the surface on the side to which a resin composition layer is joined can also be used. Examples of the release agent used as the release layer of the support provided with a release layer include a group selected from an alkyd resin, an olefin resin, a urethane resin, and a silicone resin. More than 1 release agent. Examples of commercially available mold release agents include "SK-1", "AL-5", and "AL-7" made by LINTEC Corporation, which are alkyd resin-based release agents.

The thickness of the support is not particularly limited, but is preferably in the range of 5 to 75 μm, and more preferably in the range of 10 to 60 μm. In addition, when the support is attached When the support having a release layer is used, the thickness of the entire support having the release layer is preferably in the above range.

Next, the film can be produced, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish to a support using a die coater, and then drying the resin varnish to form a resin composition layer. .

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; ethyl acetate, butyl acetate, celex acetate, propylene glycol monomethyl ether acetate, and Acetates such as carbitol acetate, carbitols such as cyrus and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamidine Ammonium solvents such as amines (DMAc) and N-methylpyrrolidone. The organic solvents may be used alone or in combination of two or more.

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

In the adhesive film, the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support) may be further laminated with a support-based protective film. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. Prevents dust by laminating protective film Adhesion or damage to the surface of the resin composition layer. The film can then be rolled into a roll and stored. When the adhesive film has a protective film, it can be used by peeling off the protective film.

In one embodiment, the prepreg system is formed by impregnating the sheet-like fibrous substrate with the resin composition of the present invention.

The sheet-like fibrous substrate used for the prepreg is not particularly limited, and a substrate for prepregs such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of reducing the thickness of the printed circuit board, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less, and still more preferably 20 μm or less. The lower limit of the thickness of the sheet-like fibrous substrate is not particularly limited, but is usually 10 μm or more.

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

The thickness of the prepreg may be in the same range as the resin composition layer in the above-mentioned adhesive film.

In the sheet-like laminated material, from the viewpoint of suppressing resin bleeding during the manufacture of printed circuit boards, the minimum melt viscosity of the resin composition layer is preferably 300 poise or more, more preferably 500 poise or more, and even more preferably 700 poise or more , Above 900 poises, or above 1000 poises. From the viewpoint of achieving good lamination properties (circuit filling properties) during the manufacture of printed circuit boards, the upper limit of the minimum melt viscosity of the resin composition layer is preferably 30,000 poise or less, more preferably 25,000 poise or less, and even more preferably Below 20000 poises, below 15,000 poises, below 10,000 poises, below 5000 poises or below 3500 poises. Especially in the manufacture of printed circuit boards, the resin composition layer and the inner layer are implemented by a vacuum lamination method. When laminating substrates, the upper limit of the minimum melt viscosity of the resin composition layer is preferably 5,000 poise or less, or 3500 poise or less. Here, the "minimum melt viscosity" of the resin composition layer means the lowest viscosity exhibited by the resin composition layer when the resin of the resin composition layer is melted. In detail, when the resin composition layer is heated at a certain heating rate to melt the resin, the melt viscosity will decrease with the increase in temperature in the initial stage, and then, the melt viscosity will increase with the increase in temperature after exceeding a certain temperature. . "Minimum melt viscosity" refers to the melt viscosity of the minimum point. The minimum melt viscosity of the resin composition layer can be measured by a dynamic viscoelasticity method, and can be measured according to a method described in <Measurement of minimum melt viscosity> described later, for example.

In the present invention using a predetermined amount of an inorganic filler that satisfies a specific shape parameter condition, a resin composition layer showing the lowest melt viscosity in the above-mentioned preferable range can be favorably formed, and it can provide a display during the manufacture of a printed circuit board Laminated sheet material with good lamination. Moreover, since the resin composition of the present invention exhibits good dispersion stability, in the obtained sheet-like laminated material, it is possible to suppress the precipitation of a large volume of aggregated particles in the resin composition layer.

The sheet-like laminated material of the present invention can be used for forming an insulating layer of a printed circuit board (for an insulating layer of a printed circuit board), and can further be used for forming an interlayer insulating layer of a printed circuit board (for an interlayer insulating layer of a printed circuit board). It can be further applied to a resin composition for forming: an interlayer insulating layer on which a conductor layer is formed by plating (for an interlayer insulating layer of a printed circuit board having a conductor layer formed by plating).

[A printed circuit board]

The printed circuit board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.

In one embodiment, the printed circuit board of the present invention can be manufactured by a method including the following steps (I) and (II) using the above-mentioned adhesive film.

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

(II) a step of thermally curing the resin composition layer to form an insulating layer

The "inner substrate" used in step (I) mainly refers to 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 A circuit board having a patterned conductive layer (circuit) formed on one or both sides of the substrate. In addition, when manufacturing a printed circuit board, an inner-layer circuit substrate to be further formed with an intermediate layer of an insulating layer and / or a conductor layer is also included in the "inner-layer substrate" referred to in the present invention.

From the viewpoint of reducing the thickness of the printed circuit board, the thickness of the inner layer substrate is preferably 800 μm or less, more preferably 400 μm or less, and even more preferably 200 μm or less. According to the present invention, even when a thinner inner layer substrate is used, warpage of the printed circuit board in the packaging step can be suppressed. Even when 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 is used, warpage in the packaging step can be suppressed . The lower limit of the thickness of the inner substrate is not special Limitation is preferably from 10 μm or more, and more preferably from 20 μm or more, from the viewpoint of improving handling properties at the time of manufacturing a printed circuit board.

The bending modulus of the inner layer substrate is not particularly limited. In the present invention, regardless of the bending modulus of the inner substrate, warpage in the packaging step of the part can be suppressed.

The lamination of the inner substrate and the adhesive film can be performed, for example, by heat-pressing the inner substrate with the adhesive film from the support side. Examples of a member (hereinafter, also referred to as a "heat-compression-bonding member") for heat-compression-bonding an inner-layer substrate to a film include a heated metal plate (SUS mirror plate, etc.), a metal roller (SUS roller), and the like. In addition, it is preferable to press through an elastic material such as heat-resistant rubber, so that the adhesive film sufficiently follows the surface unevenness of the inner layer substrate, instead of directly pressing the heat-compression bonding member against the adhesive film.

The lamination of the inner substrate and the adhesive film can be performed by a vacuum lamination method. In the vacuum lamination method, the heating and compression bonding temperature is preferably in the range of 60 ° C to 160 ° C, more preferably in the range of 80 ° C to 140 ° C; the heating and compression bonding pressure is preferably 0.098MPa to 1.77MPa, and more preferably 0.29MPa to The range of 1.47 MPa; the heating and crimping time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably performed under a reduced pressure of a pressure of 26.7 hPa or less.

Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressure laminators made by Meiki Seisakusho, and vacuum applicators made by Nichigo-Morton.

After lamination, the film can also be laminated under normal pressure (atmospheric pressure), for example, by pressing the heat-compression bonding member from the support side. Smoothing process. As the pressing condition of the smoothing treatment, the same conditions as those of the above-mentioned laminated heat-pressing conditions can be used. The smoothing process can be performed using a commercially available laminator. The lamination and trimming treatment can be continuously performed by using the above-mentioned commercially available vacuum laminator.

The lamination of the inner substrate and the adhesive film can be performed by a vacuum hot press. By using a vacuum hot press, even when a resin composition having a relatively high content of inorganic fillers is used, good lamination properties (circuit burial properties) can be achieved. Heating and pressurization can be performed in one stage, but from the viewpoint of suppressing resin bleeding, it is preferred to perform the conditions in two or more stages. For example, it is preferable to perform the first stage of pressing at a temperature of 70 to 150 ° C and a pressure of 0.098 MPa to 1.77 MPa, and to perform the second stage of pressing at a temperature of 150 to 200 ° C and a pressure of 0.098 MPa to 3.92 MPa. Press. The time of each stage is preferably 30 to 120 minutes. The pressing is performed under a reduced pressure of generally 1 × 10 ^-2 MPa or less, preferably 1 × 10 ^-3 MPa or less. Examples of commercially available vacuum hot presses include "MNPC-V-750-5-200" manufactured by Meiji Seisakusho Co., Ltd., and "VH1-1603" manufactured by Kitagawa Seiki Co., Ltd. When the step (I) is carried out by using a vacuum hot press, this step can also serve as a heat-curing member of the resin composition layer (that is, step (II)).

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

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

The conditions for the thermosetting of the resin composition layer are not particularly limited, and conditions generally used when forming an insulating layer of a printed wiring board can be used.

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

Before the resin composition layer is thermally hardened, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before the resin composition layer is thermally cured, the temperature may be 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 pre-heated for more than 5 minutes (preferably 5 to 150 minutes, more preferably 15 to 120 minutes).

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

When manufacturing a printed circuit board, (III) a step of opening the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer on the surface of the insulating layer may be further performed. These steps (III) to (V) can be implemented in accordance with various methods known to those skilled in the art used in the manufacture of printed circuit boards. In addition, when the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and Implemented between steps (V).

Step (III) is a step of making holes in the insulating layer, thereby forming holes such as through holes, through holes, and the like in the insulating layer. Step (III) can be performed using, for example, a drill, a laser, a plasma, or the like depending on the composition of the resin composition used for the formation of the insulating layer. The size or shape of the hole can be appropriately determined according to the design of the printed circuit board. As described above, since the resin composition of the present invention exhibits good dispersion stability, in the resin composition layer, it is possible to further suppress the precipitation of a large volume of aggregated particles in the insulating layer layer. In the insulating layer having a uniform composition, a hole having a desired cross-sectional shape may be formed in step (III). therefore. When a hole is filled with a conductive metal to form a filled guide hole, the inside of the hole may be smoothly filled with a conductive metal. In this way, for example, in the case of using a broken inorganic filler, if an inorganic filler having an acute angle or a large volume of aggregated particles is present on the wall surface of the hole, there is a reason for using the inorganic filler or its large volume. The agglomerated particles preferentially stretch the plating layer as a starting point to generate voids in the filled vias. In the present invention using an inorganic filler that satisfies a specific shape parameter condition, the presence of the agglomerated particles and the like on the wall surface of the hole can be suppressed, and the plating layer can be uniformly stretched throughout the entire wall surface of the hole, which can advantageously suppress filling of the guide hole The generation of voids.

Step (IV) is a step of roughening the insulating layer. The procedure and conditions for the roughening process are not particularly limited, and a printed circuit board can be formed. The well-known procedures and conditions usually used for the insulation layer. For example, a roughening treatment using a swelling liquid, a roughening treatment using an oxidizing agent, and a neutralizing treatment using a neutralizing solution may be sequentially performed. The swelling liquid is not particularly limited, and examples thereof include an alkali solution and a surfactant solution, and an alkali solution is preferred. As the alkali solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferred. Examples of commercially available swelling liquids include Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, etc., manufactured by Atotech Japan. The swelling treatment using a swelling liquid is not particularly limited, and can be performed, for example, by immersing the insulating layer in a swelling liquid at 30 to 90 ° C. for 1 to 20 minutes. The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidant such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidant solution heated to 60 ° C to 80 ° C for 10 minutes to 30 minutes. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by mass. Examples of commercially available oxidants include alkaline permanganic acid solutions such as Concentrate Compact CP and Dozing Solution Securiganth P manufactured by Atotech Japan. The neutralizing solution is preferably an acidic aqueous solution. Examples of commercially available products include Reduction Solution Securiganth P manufactured by Atotech Japan. The treatment using the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment using the oxidant solution in a neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes.

The insulating layer formed using the resin composition of the present invention shows a low surface roughness after the roughening treatment. In one embodiment, the The arithmetic average roughness Ra of the surface of the insulating layer after the chemical treatment is preferably 500 nm or less, more preferably 480 nm or less, even more preferably 450 nm or less, even more preferably 400 nm or less, 360 nm or less, or 320 nm or less. The insulating layer formed using the resin composition of the present invention exhibits excellent adhesion strength to the conductor layer even when Ra is small. The lower limit of the Ra value is not particularly limited, but is preferably 0.5 nm or more, and more preferably 1 nm or more. The arithmetic average roughness Ra of the surface of the insulating layer can be measured by a non-contact surface roughness meter. A specific example of the non-contact type surface roughness meter is "WYKO NT3300" manufactured by Veeco Instruments.

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

The conductive material used for the conductive layer is not particularly limited. In a preferred embodiment, the conductor layer includes one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Above the metal. The conductor layer may be a single metal layer or an alloy layer, and examples of the alloy layer include an alloy of two or more metals selected from the group (for example, nickel, chromium alloy, copper, nickel alloy, and copper, titanium alloy). ). Among these, from the viewpoints of versatility, cost, and ease of patterning of the conductor layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or nickel and chromium are preferred. Alloy, copper‧nickel alloy, copper‧titanium alloy, preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel‧chrome alloy, and It is preferably a single metal layer of copper.

The conductor layer can be a single layer structure, or a single metal layer or an alloy layer composed of different kinds of metals or alloys can be laminated in two or more layers. Made of a multilayer structure. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of a nickel-chromium alloy.

The thickness of the conductive layer depends on the desired design of the printed circuit board, and is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

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

First, a seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed seed layer, a mask pattern is formed in which a part of the seed layer is exposed in accordance with a desired wiring pattern. After the metal layer is formed on the exposed plating layer by electrolytic plating, the mask pattern is removed. Thereafter, the excess plating 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 the present invention exhibits sufficient adhesion strength to a conductor layer. In one embodiment, the adhesion strength between the insulating layer and the conductor layer is preferably 0.50 kgf / cm or more, more preferably 0.55 kgf / cm or more, and still more preferably 0.60 kgf / cm or more. The upper limit value of the adhesion strength is not particularly limited, and is taken as 1.2 kgf / cm or less, 0.90 kgf / cm or less. In the present invention, the surface roughness Ra of the insulation layer after the roughening treatment is relatively small, but since an insulation layer exhibiting such high adhesion strength can be formed, it is obviously beneficial to the miniaturization of circuit wiring. In addition, in the present invention, the adhesion strength between the insulating layer and the conductor layer means that the conductor layer is directed toward The peeling strength (90-degree peeling strength) when peeled in the direction (90-degree direction) can be measured by using a tensile tester to measure the peeling strength when the conductor layer is peeled in a direction perpendicular to the insulating layer (90-degree direction). Find it. Examples of the tensile testing machine include "AC-50C-SL" manufactured by TSE Corporation.

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

[Semiconductor device]

Using the printed circuit board of the present invention, a semiconductor device can be manufactured. The printed circuit board of the present invention is thin in length, and can still suppress warpage in the packaging step of parts using high reflow temperature, and can advantageously reduce problems such as circuit distortion or poor contact of parts.

In one embodiment, the printed circuit board of the present invention can reduce the warpage of the printed circuit board to less than 40 μm in a packaging step using a reflow temperature with a peak temperature of up to 260 ° C. In the present invention, the warpage of the printed circuit board is a value of the difference between the maximum height and the minimum height of the displacement data when the warpage behavior of a 10 mm square portion in the center of the printed circuit board is observed with a shading device. During the measurement, the printed circuit board passed the reflow temperature curve described in IPC / JEDEC J-STD-020C ("Moisture / Reflow Sensitivity Classification For Nonhermetic Solid State Surface Mount Devices", July 2004). (Curve for lead-free components; peak temperature: 260 ° C) After the reflow device once, the printed circuit board is printed according to the reflow temperature curve of IPC / JEDEC J-STD-020C. One side is heated, and displacement data is obtained based on a ruled line provided on the other side of the printed circuit board. Examples of the reflow device include "HAS-6116" manufactured by Japan's ANTOM Co., Ltd .; and "TherMoire AXP" manufactured by Akrometrix can be cited as a shadow moire device. The printed circuit board of the present invention, which includes an insulating layer formed of a cured product of a resin composition containing an inorganic filler that satisfies a specific shape parameter condition in a predetermined amount, is thin and can suppress the warpage in the packaging step.

Examples of the semiconductor device include various semiconductor devices used in power supply products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, locomotives, automobiles, trams, ships, and aircraft).

The semiconductor device of the present invention can be manufactured by encapsulating a component (semiconductor wafer) at a conductive portion of the printed circuit board of the present invention. The "conducting part" means "a part for transmitting electric signals in a printed circuit board", and the place may be either a surface or a landfilled part. The semiconductor wafer is not particularly limited as long as it is a circuit element made of a semiconductor.

The method for packaging a semiconductor wafer when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor wafer can effectively perform its functions. Specific examples include a wire bonding packaging method, a flip-chip packaging method, and bumpless increase. Layer-by-layer (BBUL) packaging method, anisotropic conductive film (ACF) packaging method, non-conductive film (NCF) packaging method, etc. Here, the term "package method using bumpless layer (BBUL)" refers to a "package method in which a semiconductor wafer is directly buried in a recess of a printed circuit board and the semiconductor wafer is connected to the wiring on the printed circuit board. ".

[Example]

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited by these examples. In addition, the following “parts” and “%” mean “mass parts” and “mass%”, respectively, unless expressly stated otherwise.

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

[Preparation of Evaluation Board 1] (1) Preparation of the inner circuit board

The MEC (strand) is used on both sides of the copper-clad laminate with glass cloth substrate epoxy resin on both sides where the inner-layer circuit is formed (the thickness of the copper foil is 18 μm; the thickness of the substrate is 0.3 mm; "R5715ES" manufactured by Panasonic Corporation "CZ8100" was etched to 1 μm to perform a roughening treatment on the copper surface.

(2) Laminating the film

The adhesive films produced in the examples and comparative examples were bonded to the inner circuit board with a resin composition layer using a batch vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.). The method is laminated on both sides of the inner-layer circuit board. The lamination system was performed by reducing the pressure for 30 seconds so that the pressure became 13 hPa or less, and then performing pressure bonding at 100 ° C and a pressure of 0.74 MPa for 30 seconds.

(3) Hardening of the resin composition layer

After lamination, the support is peeled from both sides of the substrate. Next, the resin composition layer was thermally hardened at 100 ° C. for 30 minutes, and then at 170 ° C. for 30 minutes to form an insulating layer.

(4) Roughening

After the insulating layer was formed, the substrate was immersed in a swelling liquid ("Swelling Dip Securiganth P" manufactured by Atotech Japan Co., Ltd .; an aqueous solution containing diethylene glycol monobutyl ether and sodium hydroxide) at 80 ° C for 5 minutes at 80 ° C. Immersed in an oxidant ("Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd .; KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) for 10 minutes, and finally immersed in a neutralizing solution (Atotech Japan (stock) ) "Reduction Solution Securiganth P"; hydroxylamine sulfate aqueous solution) for 5 minutes. Then, it dried at 80 degreeC for 30 minutes. The obtained substrate is referred to as "substrate 1a".

In addition, in Example 6 and Comparative Example 5, the substrate 1a was obtained by performing the operations (2) to (4) as described below.

The adhesive films produced in the examples and comparative examples were laminated on the inner layer circuit using a vacuum pressing device ("VH1-1603" manufactured by Kitagawa Seiki Co., Ltd.) so that the resin composition layer and the inner layer circuit board were bonded together. Both sides of the substrate. The lamination system was carried out under a reduced pressure of 1 × 10 ^-3 MPa at 100 ° C. and a pressure of 1.0 MPa for 30 minutes, and then took 10 minutes to increase the temperature to 180 ° C. Then, the pressure was applied at 180 ° C. and 1.0 MPa. Take it for 30 minutes. Thereby, the resin composition layer is thermally cured to form an insulating layer. The roughening treatment was carried out in the same manner as in (4) above except that it was immersed in a swelling liquid at 60 ° C for 5 minutes and immersed in an oxidant at 80 ° C for 5 minutes.

(5) Formation of the conductor layer

According to the semi-additive method, as described below, a conductor layer is formed on the surface of the insulating layer.

The substrate 1a was immersed in an electroless plating solution containing PdCl ₂ at 40 ° C for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C for 20 minutes. Next, after annealing at 150 ° C. for 30 minutes, an etching protection film is formed, and patterning is performed by etching. Thereafter, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 25 μm, and an annealing treatment was performed at 180 ° C. for 30 minutes. The obtained substrate is referred to as "substrate 1b".

[Preparation of Evaluation Board 2] (1) Preparation of the inner substrate

As the inner layer substrate, an uncoated copper plate (thickness: 100 μm) in which copper foil on both sides of a copper-clad laminate with a glass cloth substrate epoxy resin on both sides was removed was prepared. As a copper-clad laminate with glass cloth substrate epoxy resin on both sides, "HL832NSF-LCA" (size 100mm × 150mm, thickness of the underlying substrate 100μm, thermal expansion coefficient 4ppm / ° C, bending) The modulus is 34 GPa and the thickness of the surface copper circuit is 16 μm).

(2) Laminating the film

The adhesive films produced in the examples and comparative examples were subjected to a batch-type vacuum pressure laminator (a two-stage build-up laminator manufactured by Nichigo-Morton Co., Ltd.). "CVP700") is laminated on both sides of the inner circuit board so that the resin composition layer is bonded to the inner circuit board. The lamination system was implemented by reducing the pressure for 30 seconds so that the air pressure became 13 hPa or less, and then performing pressure bonding at 100 ° C and a pressure of 0.74 MPa for 30 seconds. Next, hot pressing was performed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Hardening of the resin composition layer

After lamination, the support was peeled from the substrate. Next, the resin composition layer was thermally cured under a curing condition of 190 ° C and 90 minutes to form an insulating layer. The obtained substrate is referred to as "substrate 2a".

<Measurement of Specific Surface Area (S) of Inorganic Filler>

The specific surface area of the inorganic filler was obtained by an automatic specific surface area measuring device ("Macsorb HM-1210" manufactured by Mountun Co., Ltd.) by a nitrogen BET method.

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

To a 20 ml vial, 0.01 g of an inorganic filler, 0.2 g of a non-ionic dispersant ("T208.5" manufactured by Nippon Oil & Fat Co., Ltd.) and 10 g of pure water were added, and ultrasonic dispersion was performed with an ultrasonic cleaner for 10 minutes. Prepare into samples. Next, the sample was put into a laser diffraction type particle size distribution measuring device ("SALD2200" manufactured by Shimadzu Corporation) and irradiated with ultrasound for 10 minutes while circulating it. Thereafter, the ultrasonic wave was stopped, and the particle size distribution was measured while maintaining the cycle of the sample, and the average particle diameter (R) of the inorganic filler was determined. In addition, The refractive index at the time of measurement was set to 1.45-0.001i.

<Calculation of Shape Parameter A>

The value of the specific surface area (S), average particle diameter (R), and density (ρ) of the inorganic filler was substituted into the following formula (1) to calculate the shape parameter A.

Equation (1): A = SRρ / 6

<Calculation of Shape Parameter B>

The insulating layer laminated on one side of the substrate 1a was subjected to cross-sectional observation at an observation magnification of 14,000 times using a FIB-SEM composite device ("SMI3050SE" manufactured by SII Nanotechnology (KK)). From the obtained FIB-SEM image, the perimeter (L) and area of the inorganic filler particles existing in the insulating layer were measured using image processing software ("QWin V3" manufactured by Leica Co., Ltd.). In addition, the measurement was performed by excluding any inorganic filler particles having an unclear overall image or inorganic filler particles having an inconspicuous outline, and arbitrarily selecting 50 inorganic filler particles per sample. From the area of the obtained inorganic filler particles, the perimeter (circumference; Lc) of a perfect circle of the same area is calculated. Then, the values of L and Lc were substituted into the following formula (2), and 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 is obtained by the following procedure. First, an inorganic filler is fixed to a glass sample plate to prepare a sample piece. This sample piece was installed in a wide-angle X-ray diffraction device ("Multi FLEX" manufactured by Rigaku Co., Ltd.), and the diffraction curve was measured by a wide-angle X-ray diffraction reflection method. The X-ray source is CuKα, the detector is a scintillation counter, and the output is 40kV, 40mA. From the obtained diffraction curve based on the diffraction curve of the SiO ₂ Quarts (101) plane, the crystallite diameter was calculated using the Scherrer formula.

<Evaluation of dispersion stability>

Regarding the adhesive films produced in the examples and comparative examples, the aggregated particles in the resin composition layer were observed with a 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 criteria:

○: Condensed particles of 10 μm or more did not reach 2 in 10 fields of view

×: Two or more aggregated particles of 10 μm or more in 10 fields of view

<Determination of minimum melt viscosity>

The melt-viscosity was measured about the resin composition layer of the adhesive film produced in the Example and the comparative example using the dynamic viscoelasticity measuring device ("Rheosol-G3000" made by UBM). A 1 g sample resin composition was heated from a starting temperature of 60 ° C. to 200 ° C. at a heating rate of 5 ° C./min using a parallel plate having a diameter of 18 mm, and the dynamics were measured under measurement conditions at a measurement temperature interval of 2.5 ° C., vibration of 1 Hz, and strain of 1 deg. Viscoelastic modulus, determine the lowest melt viscosity. Laminarity was evaluated according to the following criteria.

Evaluation criteria:

○: The minimum melt viscosity is 30,000 poise or less

×: The lowest melt viscosity is higher than 30,000 poise

<Evaluation of warpage>

The substrate 2a (n = 5) was passed through a reflow device ("HAS-6116" manufactured by Japan's ANTOM Corporation) to reproduce the reflow temperature at a peak temperature of 260 ° C (the reflow temperature curve is based on IPC / JEDEC J- STD-020C). Next, a shadow moire device ("TherMoire AXP" manufactured by Akrometrix) was used to heat the lower surface of the substrate according to the reflow temperature curve of IPC / JEDEC J-STD-020C (peak temperature 260 ° C), based on the placement on the upper surface of the substrate Measure the displacement of the 10mm square part of the center of the substrate with a ruled line. Warpage is evaluated according to the following evaluation criteria.

Evaluation criteria:

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

×: For at least one sample, the difference between the maximum and minimum heights of the displacement data over the entire temperature range is 40 μm or more

<Measurement of Arithmetic Mean Roughness (Ra)>

The Ra value was obtained for the substrate 1a by using a non-contact surface roughness meter ("WYKO NT3300" manufactured by Veeco Instruments) in a VSI contact mode with a 50-times lens and a measurement range of 121 μm × 92 μm. Calculate the average of 10 randomly selected points, and use this as the measured value.

<Measurement of Adhesive Strength of Conductor Layer>

The measurement of the adhesion strength between the insulating layer and the conductor layer is performed on the evaluation substrate 1b in accordance with JIS C6481. Specifically, a cut of a portion having a width of 10 mm and a length of 100 mm is made on the conductor layer of the substrate 1b, and this end is peeled off and held with a gripper, and measured at room temperature in a vertical direction at a speed of 50 mm / min The load (kgf / cm) at 35 mm was peeled to obtain the adhesion strength.

<Measurement of linear thermal expansion coefficient>

The adhesive films produced in the examples and comparative examples were heated at 190 ° C for 90 minutes to thermally harden the resin composition layer. Next, the support was peeled 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 a thermo-mechanical analysis was performed by a tensile load method using a thermo-mechanical analysis device ("Thermo Plus TMA8310" manufactured by Rigaku Co., Ltd.). Specifically, after the test piece was installed in the thermo-mechanical analysis device, the measurement was performed twice under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. Thereafter, in the second measurement, an average linear thermal expansion coefficient in a range of 25 ° C to 150 ° C was calculated.

<Assessment of Filled Voids>

The filling of the voids in the pilot holes was evaluated according to the following procedure.

(1) Formation of through holes

A carbon dioxide laser processing machine ("LC-2E21B / 1C" manufactured by Hitachi, Ltd.) was used to form through holes having a top diameter of 60 μm and a bottom diameter of 50 μm for the insulating layer laminated on one side of the substrate 1 a.

(2) Formation of filled guide holes

After the through-holes are formed, the insulating layer is roughened to form a conductor layer. The roughening treatment and the formation of the conductor layer are performed in the same manner as in [Preparation of the substrate for evaluation 1]. Thereby, the inside of the through hole is filled with a conductive metal to obtain a filled via hole.

(3) Evaluation of voids

The formed filled vias were observed with a scanning electron microscope (SEM) (manufactured by Hitachi High-Technologies (KK); type "SU-1500"). Further, a case where the number of voids in the ten filled guide holes was less than two was rated as "○", and a case where there were two or more were rated as "x".

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

In addition, for IMSIL A-8, the content of particles with a shape parameter B of less than 0.8 is 36%, especially the shape parameter B is 0.75 or more. The content of the particles below is 16%; the content of particles with a shape parameter B greater than 0.9 is 12%, and the content of particles with a shape parameter B of 0.94 or more is 0%. For IMSIL A-25, the content of particles with a shape parameter B less than 0.8 is 26%, especially the content of particles with a shape parameter B of 0.75 or less is 20%. For particles with a shape parameter B greater than 0.9, The content is 14%, and in particular, the content of particles having a shape parameter B of 0.94 or more is 0%.

<Example 1> (1) Preparation of resin varnish

While stirring, 20 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 187; "jER828EL" manufactured by Mitsubishi Chemical Corporation), 30 parts of biphenyl epoxy resin (epoxy equivalent 276; Japanese chemical medicine ( "NC3000"), 5 parts of tetraphenylethane type epoxy resin (epoxy equivalent 198; "jER1031S" manufactured by Mitsubishi Chemical Corporation), 5 parts of bisphenol A type epoxy resin (ring Oxygen equivalent is about 3000 ~ 5000; 50% by mass of non-volatile components made from a mixed solvent in which the mass ratio of methyl ethyl ketone (MEK) and cyclohexanone is 1: 1, which is "jER1010" manufactured by Mitsubishi Chemical Corporation. The resin solution was heated and dissolved in a mixed solvent of 20 parts of MEK and 10 parts of cyclohexanone. To this was mixed 10 parts of a phenol novolac-based hardener containing a triazine skeleton (hydroxyl equivalent weight 125; "LA-7054" manufactured by DIC Corporation; solid content 60% MEK solution), and 6 parts of a phenol novolac-based hardener (hydroxy equivalent 105; "TD2090" manufactured by DIC (stock), 3 parts of amine hardening accelerator (4-dimethylaminopyridine (DMAP); MEK solution with a solid content of 5% by mass), 180 parts of N-phenyl-3 -Aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) is a crystalline silicon dioxide ("IMSIL A-8" manufactured by Unimin Corporation); the average particle diameter is 1.38 μm; the maximum particle diameter is 20 μm; Specific surface area 6.54m ² / g; density 2.65g / cm ³ ; average crystallite diameter 1000Å), 5 parts flame retardant ("HCA-HQ" made by Sanguang Co., Ltd.); 10- (2,5-dihydroxyphenyl) ) -10-Hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide; average particle diameter: 2 μm), uniformly dispersed with a high-speed rotating mixer to prepare a resin varnish. The total density of non-volatile components other than the inorganic filler used for the preparation of the resin varnish was about 1.2 g / cm ³ .

(2) Production of Adhesive Film

As a support, a polyethylene terephthalate film (thickness: 38 μm; LINTEC (AL5)) made of an alkyd resin-based release layer was prepared. The prepared resin varnish was uniformly coated on the support with a die coater, and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes to form a resin composition layer. The thickness of the resin composition layer was 40 μm, and the amount of residual solvent in the resin composition was about 2% by mass. Next, a polypropylene film (made by Oji Special Paper Co., Ltd .; smooth surface side of "ALPHAN MA-411"; thickness 15 μm) was wound into a roll shape while facing the surface of the resin composition layer. . The roll-shaped adhesive film was cut into a width of 507 mm to obtain an adhesive film having a size of 507 mm × 336 mm.

<Example 2>

Except using 10 parts of biphenyl type epoxy resin (epoxy equivalent 276; "NC3000" manufactured by Nippon Kayaku Co., Ltd.) and 18 parts of naphthalene ether type epoxy resin (epoxy equivalent 250; DIC (HP6000) made by DIC (stock) instead of 30 parts of biphenyl epoxy resin (epoxy equivalent 276; NC3000 made by Nippon Kayaku Co., Ltd.), prepared in the same manner as in Example 1. Resin varnish to make an adhesive film.

<Example 3>

In addition to using 12 parts of naphthol phenolic hardener (hydroxyl equivalent 215; Nippon Steel & Sumikin Chemical Co., Ltd. "SN485") instead of 6 parts of phenol phenolic hardener (hydroxyl equivalent 105; DIC (TD) 90TD) ), And crystalline silicon dioxide ("IMSIL A-8", manufactured by Unimin Corporation), which is surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573", manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of varnish was changed to 210 parts, and a resin varnish was prepared in the same manner as in Example 1 to prepare an adhesive film.

<Example 4>

In addition to using 8 parts of phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation; 30% by mass of MEK / cyclohexanone = 1/1 solution) to replace solid bisphenol A epoxy resin (epoxy equivalent) About 3000 to 5000; except for "jER1010" manufactured by Mitsubishi Chemical Corporation, a resin varnish was prepared in the same manner as in Example 1 to prepare an adhesive film.

<Example 5>

In addition, N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was used for surface treatment of crystalline silicon dioxide ("IMSIL A-25" manufactured by Unimin Corporation; average particle size) Diameter 2.55μm; maximum particle size 20 μm; specific surface area 5.87m ² / g; density 2.65g / cm ³ ; average crystallite diameter 1400Å) to replace 180 parts of N-phenyl-3-aminopropyltrimethoxy Except for silane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) and surface-treated crystalline silicon dioxide ("IMSIL A-8" manufactured by Unimin Corporation), a resin varnish was prepared in the same manner as in Example 1 to form an adhesive film .

<Example 6>

In addition to N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), a surface-treated crystalline silicon dioxide ("IMSIL A-8" manufactured by Unimin Corporation; Diameter 1.38μm; maximum particle diameter 20μm; specific surface area 6.54m ² / g; density 2.65g / cm ³ ; average crystallite diameter 1000Å) The dosage was changed to 400 parts except that the resin varnish was prepared in the same manner as in Example 1. , Made of adhesive film.

<Comparative example 1>

In addition, 150 parts of spherical silicon dioxide ("SO-C2" manufactured by Admatechs Corporation) was surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.). ”; Average particle diameter 0.90 μm; specific surface area 5.75 m ² / g; density 2.2 g / cm ³ ) instead of 180 parts of N-phenyl-3-aminopropyltrimethoxysilane (made by Shin-Etsu Chemical Co., Ltd.) "KBM573"), except for crystalline silicon dioxide ("IMSIL A-8", manufactured by Unimin), was prepared in the same manner as in Example 1 to prepare an adhesive film.

<Comparative example 2>

In addition, 150 parts of spherical silicon dioxide ("SO-C6" manufactured by Admatechs Corporation) was surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.). ”; Average particle diameter 2.06 μm; specific surface area 2.15 m ² / g; density 2.2 g / cm ³ ) instead of 180 parts of N-phenyl-3-aminopropyltrimethoxysilane (made by Shin-Etsu Chemical Co., Ltd.) "KBM573"), except for crystalline silicon dioxide ("IMSIL A-8", manufactured by Unimin), was prepared in the same manner as in Example 1 to prepare an adhesive film.

<Comparative example 3>

In addition to using 180 parts of N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) for surface treatment, crushed silicon dioxide ("VX- SR "; average particle size 1.30μm; specific surface area 11.94m ² / g; density 2.65g / cm ³ ; average crystallite diameter 1900Å) to replace 180 parts of N-phenyl-3-aminopropyltrimethoxysilane Except for (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) surface-treated crystalline silicon dioxide ("IMSIL A-8" manufactured by Unimin), a resin varnish was prepared in the same manner as in Example 1 to prepare an adhesive film.

<Comparative Example 4>

In addition to the amount of N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) surface-treated crystalline silicon dioxide ("IMSIL A-8" manufactured by Unimin) Change to something other than 80. In the same manner as in Example 1, a resin varnish was prepared to prepare an adhesive film.

<Comparative example 5>

In addition to the amount of N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) surface-treated crystalline silicon dioxide ("IMSIL A-8" manufactured by Unimin) Resin varnish was prepared in the same manner as in Example 1 except that it was changed to 480 parts to prepare an adhesive film.

Claims (14)

A resin composition is a resin composition for an insulating layer of a printed circuit board. If the non-volatile content in the resin composition is 100% by volume, the content of the inorganic filler is 40 to 75% by volume, formula: A = SRρ / 6 [where S is the specific surface area of the inorganic filler (m ² / g), R is the average particle diameter of the inorganic filler (μm), and ρ is the density of the inorganic filler (g / cm ³ )] The shape parameter A of the inorganic filler is shown to satisfy 20 ≦ 6A ≦ 40. A resin composition is a resin composition for an insulating layer of a printed circuit board. If the non-volatile content in the resin composition is 100% by volume, the content of the inorganic filler is 40 to 75% by volume. Formula: B = Lc / L [In the formula, L represents the perimeter (μm) of the inorganic filler with a predetermined cross section, and Lc represents the perimeter (μm) of a circle with the same area as the cross section of the inorganic filler with the aforementioned cross section] The average value of the shape parameter B of the filler is 0.8 or more and 0.9 or less. For example, the resin composition of claim 1 or 2, wherein the average crystallite diameter of the inorganic filler is 1800 angstroms or less. For example, the resin composition of claim 1 or 2, wherein the specific surface area of the inorganic filler is 3 to 10 m ² / g. For example, the resin composition of claim 1 or 2, wherein the average particle diameter of the inorganic filler is 4 μm or less. For example, the resin composition of claim 1 or 2, wherein the average particle diameter of the inorganic filler is 3 μm or less. For example, the resin composition of claim 1 or 2, wherein the inorganic filler is obtained by dispersing fine granular aggregates of microcrystalline particles having an average crystallite diameter of 1800 angstroms or less. The maximum particle size of the fine granular aggregates is 20 μm. the following. For example, the resin composition of claim 1 or 2, wherein the inorganic filler includes a crystalline inorganic filler, and the content of the crystalline inorganic filler is 50% by mass or more if the entire inorganic filler is 100% by mass. The resin composition according to claim 8, wherein the crystalline inorganic filler is crystalline silicon dioxide. The resin composition according to claim 1 or 2, further comprising an epoxy resin and a hardener. The resin composition of claim 1 or 2 is a resin composition for an interlayer insulating layer. A sheet-like laminated material comprising a resin composition layer formed with the resin composition as claimed in claim 1 or 2. A printed circuit board comprising an insulating layer formed of a cured product of a resin composition as claimed in claim 1 or 2. A semiconductor device comprising a printed circuit board as claimed in claim 13.