KR20150123179A - Resin composition for insulating layer of printed wiring board - Google Patents

Abstract

[PROBLEMS] To provide a resin composition for an insulating layer of a printed wiring board which exhibits good dispersion stability and an appropriate melt viscosity, and which can suppress warping in a component mounting step.
[MEANS FOR SOLVING PROBLEMS] A resin composition for an insulating layer of a printed wiring board, wherein the content of the inorganic filler is 40 to 75% by volume and the formula: A = SRρ / 6, where 100% by volume of the non- S is the specific surface area (m 2 / g) of the inorganic filler, R is the average particle diameter (탆) of the inorganic filler and ρ is the density (g / Satisfies 20? 6A? 40.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a resin composition for an insulating layer of a printed wiring board,

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

As a manufacturing technique of a printed wiring board, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately laminated on an inner layer substrate is known. In the manufacturing method according to the build-up method, the insulating layer is formed by laminating a resin composition layer on an inner layer substrate using, for example, an adhesive film containing a resin composition layer, and curing the resin composition layer. From the viewpoint of reducing the coefficient of thermal expansion of the obtained insulating layer and preventing the occurrence of cracks and circuit deformation due to the difference in thermal expansion between the insulating layer and the conductor layer, the resin composition used for forming the insulating layer generally has, Lt; / RTI > As the inorganic filler, a spherical inorganic filler is suitably used (Patent Document 1).

Japanese Unexamined Patent Application Publication No. 2010-238667

In recent years, the solder reflow temperature in the mounting process of parts has been rising as the lead-free solder is replaced by lead-free solder. In addition, in recent years, in order to achieve miniaturization of electronic devices, printed wiring boards have been further thinned.

As the printed wiring board is made thinner, warping occurs in the printed wiring board in the process of mounting the components, and problems such as circuit deformation and poor contact of components may occur. The inventors of the present invention have found that use of a crushing inorganic filler in place of a spherical inorganic filler makes it possible to suppress warping in a component mounting process. However, the resin composition containing the inorganic filler on the fracture tends to have a low dispersion stability and a high melt viscosity, resulting in poor lamination.

An object of the present invention is to provide a resin composition for an insulating layer of a printed wiring board which exhibits good dispersion stability and an appropriate melt viscosity and can suppress warping in a component mounting process.

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

That is, the present invention includes the following contents.

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

Wherein the content of the inorganic filler in the resin composition is 40 to 75% by volume,

Wherein S is the specific surface area (m 2 / g) of the inorganic filler, R is the average particle diameter (탆) of the inorganic filler and ρ is the density (g / cm 3) of the inorganic filler Wherein the shape parameter A of the inorganic filler satisfies 20? 6A? 40.

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

Wherein the content of the inorganic filler in the resin composition is 40 to 75% by volume,

Where L is the peripheral length (mu m) of the inorganic filler in a predetermined cross-section, Lc is the cross-sectional area of the inorganic filler in the cross section, Wherein the average value of the shape parameter B of the inorganic filler represented by the following formula is a peripheral length (탆) of a true circle of 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 Å or less.

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

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

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

[7] The method according to any one of [1] to [6], wherein the inorganic filler is obtained by dispersing monolithic aggregates of microcrystalline particles having an average crystallite diameter of 1800 Å or less and the maximum particle diameter of the monolith aggregates is 20 탆 or less. [6] The resin composition according to any one of [1] to [6].

[8] The method for producing a magnetic recording medium according to any one of [1] to [7], wherein the inorganic filler contains a crystalline inorganic filler and the content of the crystalline inorganic filler is 50% by mass or more based on 100% ≪ / RTI >

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

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

[11] The resin composition according to any one of [1] to [10], which is a resin composition for an interlayer insulating layer.

[12] A sheet-stacked material comprising a resin composition layer formed from the resin composition according to any one of [1] to [11].

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

[14] A semiconductor device comprising the printed wiring board according to [13].

According to the present invention, it is possible to provide a resin composition for an insulating layer of a printed wiring board, which exhibits good dispersion stability and an appropriate melt viscosity, and which can suppress warping in a component mounting step.

[Resin composition for insulating layer of printed wiring board]

The resin composition for insulating layer of the printed wiring board of the present invention (hereinafter, simply referred to as " resin composition of the present invention ") may be prepared by mixing conventionally known spherical inorganic fillers, inorganic fillers having a shape different from that of crushed- .

Unlike the spherical inorganic filler, the inorganic filler used in the present invention has an angular shape. In this respect, the inorganic filler on the fracture has a sharp angled shape, and the inorganic filler used in the present invention has a shape that is different from that of the crushing inorganic filler in that it is somewhat rounded.

Unlike the spherical inorganic filler in which the angle is not clearly recognized, the inorganic filler used in the present invention can clearly recognize the angle when compared with the projected shape on the plane. Here, " an angle can be recognized in a projection shape in a plane " means that, in a projected shape in a plane, a certain straight line or a substantially straight line and a straight line or a substantially straight line Angle), which is capable of recognizing a straight line or an approximate straight line. With respect to the inorganic filler used in the present invention, the average value of the angle? Is larger than that of the inorganic filler on the fracture surface. For example, the inorganic filler used in the present invention is preferably such that the average value of the angle? Is preferably 5 °, more preferably 7.5 °, more preferably 10 °, 12.5 ° , 15 [deg.], 17.5 [deg.], Or 20 [deg.].

Hereinafter, the shape of the inorganic filler used in the present invention will be described using two shape parameters, that is, a shape parameter A and a shape parameter B. In addition, the shape parameter A and the shape parameter B differ from each other depending on whether the parameter is derived from a three-dimensional approach or a two-dimensional approach. However, in both cases, In the case of the second embodiment.

<Configuration parameter A>

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

[Equation 1]

A = SR? / 6

In Equation (1) above,

S is the specific surface area (m 2 / g) of the inorganic filler,

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

and rho is the density (g / cm &lt; 3 &gt;) of the inorganic filler.

(Hereinafter, also referred to as &quot; jingu model system &quot;) in which a plurality of jinguids exist. The average particle size (diameter) of the average surface area of the plurality of sphericity present in, Jingu modelgye when the R of sphericity thereof is represented by πR ^2, an average volume is represented by the πR ^3/6. In addition, when the density ρ of the sphericity, the average mass of the plurality of sphericity present in modelgye sphericity is represented by πρR ^3/6.

Next, a system of an inorganic filler having the same average volume and density as the sphericity model system is considered. Based on the fact that the sieve has the smallest surface area in an object of the same volume, the average surface area of a plurality of inorganic fillers present in the system of such an inorganic filler can be expressed as AπR ² . Here, A is a shape parameter of the inorganic filler, and the lower limit thereof is 1 (when the inorganic filler is spheric). In addition, Based on modelgye sphericity and average volume, and a density equal to that condition, the average mass of the plurality of the inorganic filler present in the system of the inorganic filler can be represented by πρR ^3/6. In the system of the inorganic filler, the specific surface area S of the inorganic filler is defined as the average surface area (AπR ² ) of the plurality of inorganic fillers existing in the system of the inorganic filler / It can be represented by the average mass of the inorganic filler (πρR ^3/6)], which is a 6A / (Rρ). That is, a relation of S = 6A / (Rρ) holds, and when this equation is modified with respect to the parameter A, the above formula (1) is obtained.

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

The specific surface area S of the inorganic filler required for obtaining the shape parameter A can be measured by the BET method. Specifically, the specific surface area of the inorganic filler sample can be determined from the adsorption amount of the inorganic filler sample by adsorbing the known molecules having the adsorption occupied area at the temperature of the liquid nitrogen. An inert gas such as nitrogen or helium is suitably used as a molecule having an adsorption occupying area. The specific surface area S of the inorganic filler can be measured using an automatic specific surface area measuring apparatus. Examples of the automatic specific surface area measuring apparatus include "Macsorb HM-1210" manufactured by Moon Tec Co., have.

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 can be measured by using a laser diffraction particle size distribution measuring apparatus, and the median diameter of the inorganic filler is determined as the average particle diameter. The measurement sample can be preferably those in which an inorganic filler is dispersed in water by ultrasonic waves. Examples of the laser diffraction particle size distribution measuring apparatus include "SALD2200" manufactured by Shimadzu Corporation, "LA-500", "LA-750", and "LA-950" manufactured by Horiba Seisakusho Co., .

&Lt; Configuration parameter B &

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

&Quot; (2) &quot;

B = Lc / L

In Equation (2) above,

L is a circumferential length (mu m) of the inorganic filler at a predetermined cross section,

Lc is the cross-sectional area of the inorganic filler in the cross-section and the circumferential length (탆) of the center of the equal area.

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

The shape parameter B is a parameter that is established with respect to individual particles of the inorganic filler and it is possible to grasp the overall characteristics of the shape of the inorganic filler by obtaining the shape parameter B with respect to a sufficient number of particles constituting the inorganic filler . In one embodiment of the present invention, the shape parameter B is determined for a sufficient number of particles constituting the inorganic filler, and the shape of the inorganic filler is characterized by the average value thereof. In this embodiment, the inorganic filler used in the present invention is characterized in that the average value of the shape parameter B represented by the formula (2) is 0.8 or more and 0.9 or less. A suitable range of the average value of the shape parameter B will be described later.

Alternatively, the shape parameter B may be determined for a sufficient number of particles constituting the inorganic filler, and the shape distribution of 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 the particles having a value of the shape parameter B represented by the formula (2) below 0.8 is usually 50% by number or less. Further, in the inorganic filler used in the present invention, the content of the particles having a value of the shape parameter B expressed by the above-mentioned formula (2) larger than 0.9 is usually 30% by number or less. A suitable range of these contents will be described later.

The peripheral length (L) of the inorganic filler at a predetermined cross section required for obtaining the shape parameter B and the cross-sectional area of the inorganic filler at the cross section of the cross section of the cross section of the cross section of the layer formed using the resin composition of the present invention Can be measured. For the cross-sectional observation, an FIB-SEM hybrid apparatus is suitably used. From the obtained FIB-SEM image, the peripheral length and area (cross-sectional area) of the inorganic filler existing in the layer can be obtained by using image processing software such as &quot; QWin V3 &quot; As the FIB-SEM hybrid device, for example, "SMI3050SE" manufactured by SII Nanotechnology Co., Ltd. can be mentioned.

Lc can be obtained by calculating the circumferential length (circumference) of the cross section of the cross-sectional area and the equivalent area of the obtained inorganic filler.

In one embodiment, the resin composition of the present invention contains 40 to 75% by volume of an inorganic filler when the nonvolatile component in the resin composition is 100% by volume, and the shape of the inorganic filler represented by the formula And the parameter A satisfies 20? 6A? 40 (hereinafter, also referred to as &quot; resin composition of the first embodiment &quot;).

From the viewpoint of obtaining a resin composition exhibiting good dispersion stability and an appropriate melt viscosity, it is important that the value of 6A is 40 or less. 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 or less, 34 or less, 33 or less, 32 or less, 31 or less, or 30 or less. It is important that the lower limit of 6A is 20 or more from the viewpoint of sufficiently suppressing the warping in the component mounting process. From the viewpoint of further suppressing the warping in the mounting process of the component, the lower limit value of 6A is preferably 21 or more, 22 or more, or 23 or more.

In another embodiment, the resin composition of the present invention is characterized in that the content of the inorganic filler is 40 to 75% by volume when the nonvolatile component in the resin composition is taken as 100% by volume, the shape of the inorganic filler represented by the formula And the average value of the parameter B is 0.8 or more and 0.9 or less (hereinafter, also referred to as &quot; resin composition of the second embodiment &quot;).

From the viewpoint of obtaining a resin composition exhibiting good dispersion stability and an appropriate melt viscosity, it is important that the average value of the shape parameter B is 0.8 or more. From the viewpoint of obtaining a resin composition exhibiting better dispersion stability and melt viscosity, the average value of the shape parameter B is preferably 0.81 or more, or 0.82 or more. It is important that the upper limit of the average value of the shape parameter B is 0.9 or less from the viewpoint of sufficiently suppressing the warping in the component mounting process. It is preferable that the upper limit of the average value of the shape parameter B is 0.89 or less, 0.88 or less, 0.87 or less, 0.86 or less, or 0.85 or less from the viewpoint that the warpage in the mounting process of the component can be further suppressed.

Regardless of the first embodiment and the second embodiment, the content of the inorganic filler is preferably from 100% by volume to 100% by volume, from the viewpoint of sufficiently suppressing warping in the component mounting step, Is preferably 40 vol% or more, preferably 42 vol% or more, more preferably 44 vol% or more, further preferably 46 vol% or more, still more preferably 48 vol% or more, in view of sufficiently lowering the thermal expansion coefficient of the layer More preferably 50 vol.% Or more, 52 vol.% Or more, 54 vol.% Or more, 56 vol.% Or more, 58 vol.% Or more, or 60 vol.% Or more. In the case of using a crushing inorganic filler, the melt viscosity tends to increase excessively as the content of the inorganic filler increases. On the other hand, with respect to the inorganic filler satisfying the specific shape parameter conditions used in the present invention, the content can be further increased while realizing a good melt viscosity. For example, in the resin composition of the present invention, the content of the inorganic filler may be increased to 62 vol% or more, 64 vol% or more, 66 vol% or 68 vol% or more. From the viewpoint of obtaining a resin composition exhibiting an appropriate melt viscosity, an insulating layer having a small surface roughness and excellent adhesion strength (fill strength) to the conductor layer, the upper limit of the content of the inorganic filler is preferably 75 , Preferably not more than 74 vol.%, More preferably not more than 73 vol.%, Further preferably not more than 72 vol.%, Still more preferably not more than 71 vol.%, Particularly preferably not more than 70 vol.% . Particularly in the production of a printed wiring board, when the resin composition layer and the inner layer substrate are laminated by a vacuum laminating method, the upper limit of the content of the inorganic filler is preferably 70 vol% or less. The content (volume%) of the inorganic filler can be calculated based on the mass and density of the inorganic filler used for preparing the resin composition and the mass and density of the nonvolatile component other than the inorganic filler used for preparing the resin composition .

From the viewpoint of obtaining a resin composition exhibiting good dispersion stability and melt viscosity regardless of the first embodiment and the second embodiment, it is preferable that the ratio of the particle diameter of particles having a value of the shape parameter B represented by the formula (2) The content is preferably low. In the resin composition of the present invention, the content of particles having a value of the shape parameter B represented by the formula (2) below 0.8 in the inorganic filler is usually 50% by number or less, preferably 48% by number or less, Is preferably 46% by number or less, more preferably 44% by number or less, still more preferably 42% by number or less, or 40% by number or less. Particularly, the content of the particles having the value of the shape parameter B of 0.75 or less is preferably 20% by number or less, 18% by number or less, or 16% by number or less.

From the viewpoint of sufficiently suppressing the warping in the component mounting step regardless of the first embodiment and the second embodiment, it is preferable that the value of the shape parameter B represented by the formula (2) in the inorganic filler is larger than 0.9 The content is preferably low. In the resin composition of the present invention, the content of the particles having a value of the shape parameter B represented by the formula (2) in the inorganic filler of more than 0.9 is usually 30% by number or less, preferably 28% by number or less, more preferably , Preferably not more than 26%, more preferably not more than 24%, still more preferably not more than 22%, or not more than 20%. In particular, the content of the particles having the value of the shape parameter B of 0.94 or more is 6% or less, 4% or less, 2% or less, 1% or less, 0.8% or less, 0.6% or less, 0.4% or less, 0.2% % 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, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide Magnesium hydroxide, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, Titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, and silica is particularly suitable. The inorganic fillers may be used singly or in combination of two or more kinds. When two or more inorganic fillers are used in combination, the average particle diameter (R), the specific surface area (S) and the density (rho) required to obtain the shape parameter A are preferably the average particle size Diameter, specific surface area and density may be used.

The average particle diameter R of the inorganic filler is preferably 4 mu m or less, more preferably 3.5 mu m or less, and further preferably 3 mu m or less from the viewpoint of refinement of the circuit wiring. The lower limit of the average particle diameter of the inorganic filler is preferably 0.01 탆 or more, more preferably 0.03 탆 or more from the viewpoint of obtaining a resin varnish having a suitable viscosity at the time of forming a resin varnish by using the resin composition and having good handling properties More preferably at least 0.05 탆, even more preferably at least 0.07 탆, and particularly preferably at least 0.1 탆.

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

The inorganic filler may be amorphous or crystalline insofar as the above shape parameter conditions are satisfied. In one embodiment, the resin composition of the present invention contains a crystalline inorganic filler. The content of the crystalline inorganic filler in the inorganic filler is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, more preferably 70% by mass or more, Preferably 90 mass% or more, 92 mass% or more, 94 mass% or more, 96 mass% or more, 98 mass% or more, or 99 mass% or more. The inorganic filler may be made of a substantially crystalline inorganic filler by removing impurities inevitably contained therein. In this embodiment, the average crystallite diameter of the inorganic filler is preferably 1800 ANGSTROM or less, more preferably 1600 ANGSTROM or less, and further preferably 1400 ANGSTROM or less. The lower limit of the average crystallite diameter is not particularly limited, but it is usually 100 angstroms or more, 200 angstroms or more. The crystallite diameter of the inorganic filler can be measured using an X-ray diffraction (XRD) apparatus. As the XRD apparatus, for example, "Multi FLEX" manufactured by Rigaku Corporation can be mentioned.

Of these, crystalline silica is preferably used as the crystalline inorganic filler.

The inorganic filler satisfying the above-mentioned shape parameter condition is slightly rounded by, for example, a method of physically and / or chemically polishing the surface of the fractured inorganic filler having a sharp-angled shape and a heat treatment method, . The method of physical polishing and chemical polishing is not particularly limited, and any conventionally known method may be used. Commercially available products of the crushed silica include, for example, &quot; VX-SR &quot; manufactured by Tatsumori Co., Ltd. and the like.

Further, among the inorganic oxides which are naturally produced, inorganic oxides that suitably satisfy the above shape parameter conditions exist. For example, when the natural silica (in particular, the maximum particle diameter of the agglomerates having a maximum particle size of 20 mu m or less) calculated as agglomerates of fine crystalline particles having an average crystallite diameter of 1800 ANGSTROM or less is dispersed during the preparation of the resin composition, The agglomerates are released and the above shape parameter condition is satisfied. Accordingly, in one embodiment, the inorganic filler contained in the resin composition of the present invention is obtained by dispersing the fine aggregate of microcrystalline particles having an average crystallite diameter of 1800 Å or less and the maximum particle diameter of the aggregate of the microcrystalline particles is 20 μm or less . Examples of commercially available natural silica include "IMSIL A-8", "IMSIL A-10", "IMSIL A-15" and "IMSIL A-25" manufactured by Unimin Corporation.

The inorganic filler to be used in the resin composition of the present invention is preferably surface-treated with a surface treatment agent from the viewpoint of improving dispersibility and moisture resistance. Examples of the surface treatment agent include an amino silane coupling agent, an epoxy silane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an organosilazane compound and a titanate coupling agent. The surface treatment agent may be used singly or in combination of two or more kinds. As commercially available products of the surface treatment agent, for example, KBM403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM803 (3-mercapto KBE903 "(3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.," KBM573 "(manufactured by Shin-Etsu Chemical Co., Methoxysilane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

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

The amount of carbon per unit area bonded to the surface of the inorganic filler can be calculated by the following procedure. A sufficient amount of methyl ethyl ketone (MEK) as a solvent is added to the inorganic filler after the surface treatment, followed by ultrasonic cleaning. After the supernatant is removed and the solid content is dried, the amount of carbon bonded to the surface of the inorganic filler is measured using a carbon analyzer. By dividing the obtained amount of carbon by the specific surface area of the inorganic filler, the amount of carbon per unit surface area bonded to the inorganic filler is calculated. As the carbon analyzer, for example, "EMIA-320V" manufactured by Horiba Seisakusho Co., Ltd. and the like can be mentioned.

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

- Epoxy resin -

Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, dicyclopentadiene epoxy resin, trisphenol epoxy resin, naphthol novolak type epoxy resin, Epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, Cresol novolak type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spirocyclic epoxy resins, cyclohexanedimethanol type epoxy resins, Tylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane type epoxy resin And the like. The epoxy resin may be used singly or in combination of two or more kinds.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, it is preferable that at least 50% by mass or more of the epoxy resin is an epoxy resin having two or more epoxy groups in one molecule. Among them, epoxy resins having two or more epoxy groups in one molecule and having a liquid phase at 20 占 폚 (hereinafter referred to as &quot; liquid epoxy resin &quot;) and three or more epoxy groups in one molecule, It is preferable to contain an epoxy resin (hereinafter referred to as &quot; solid epoxy resin &quot;). When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, a resin composition having excellent flexibility is obtained. Further, the fracture strength of the cured product of the resin composition is also improved.

The liquid epoxy resin is preferably a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a phenol novolak type epoxy resin, and an epoxy resin having a butadiene structure. Type epoxy resin, a bisphenol F type epoxy resin, and a naphthalene type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032H", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation, "jER828EL" manufactured by Mitsubishi Chemical Corporation (bisphenol A type (Epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "ZX1059" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd. (bisphenol A type epoxy resin and bisphenol F type epoxy EX-721 &quot; (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Co., Ltd., &quot; PB-3600 &quot; (epoxy resin having a butadiene structure ). These may be used singly or in combination of two or more kinds.

Examples of the solid epoxy resin include naphthalene type tetrafunctional epoxy resins, cresol novolak type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins Naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, bisphenol A type epoxy resin, bisphenol A type epoxy resin, An epoxy resin, and a tetraphenyl ethane type epoxy resin are more preferable. Specific examples of the solid epoxy resin include "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolak type epoxy resin) EXA7311-G3 "," EXA7311-G4 "," EXA7311-G4S "," HP6000 "(dicyclopentadiene type epoxy resin) (Naphthylene ether type epoxy resin), "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolak type epoxy resin), "NC3000H", "NC3000" manufactured by Nippon Kayaku Co., , "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthol type epoxy resin), "ESN485" (naphthol novolak type epoxy resin) manufactured by Shinnetsu Tatsu Sumika Kagaku Co., YX4000H "," YL6121 "(biphenyl type epoxy resin)," YX4000H "," YL6121 "(biphenyl type epoxy resin)," YX4000HK " "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7800" manufactured by Mitsubishi Chemical Corporation (fluorene type epoxy resin "JER1010" (solid bisphenol A type epoxy resin) and "jER1031S" (tetraphenyl ethane type epoxy resin) manufactured by Mitsubishi Kagaku Co., Ltd., and the like.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the amount ratio (liquid epoxy resin: solid epoxy resin) thereof is preferably in the range of 1: 0.1 to 1: 4 by mass ratio. By setting the proportions of the liquid epoxy resin and the solid epoxy resin in this range, suitable adhesiveness is obtained in the case of using in the form of a sheet-like laminate material, and ii) sufficient flexibility in the case of using in the form of a sheet- Is obtained, handling is improved, and (iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii), the ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably in the range of 1: 0.3 to 1: 3.5, : 0.6 to 1: 3.

The content of the epoxy resin in the resin composition is preferably 3 to 40% by mass, more preferably 5 to 35% by mass, further preferably 10 to 30% by mass, based on 100% by mass of the nonvolatile component in the resin composition %to be.

The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, still more preferably 110 to 1000. With this range, the cross-linking density of the cured product becomes sufficient, resulting in an insulating layer having a small surface roughness. The epoxy equivalent can be measured in accordance with JIS K7236, and is the mass of the resin containing one 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 still more preferably 400 to 1500. Here, 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 curing agent is not particularly limited as long as it has a function of curing the epoxy resin, and examples thereof include a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent and a cyanate ester-based curing agent. The curing agent may be used singly or in combination of two or more kinds.

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

Specific examples of the phenol-based curing agent and naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., SN-170 "," SN-180 "," SN-190 "," SN-475 "and" SN-485 "manufactured by Shinnetsu Tsushin Kagaku Co., LA-7054 "," LA-3018 "," LA-1356 "," SN-395 " &Quot; TD2090 &quot;, and the like.

The active ester-based curing agent is not particularly limited, but generally includes ester groups having high reactivity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, Are preferably used. It is preferable that the active ester-based curing agent is obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. From the viewpoint of heat resistance improvement, an active ester type curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester type curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenol phthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o- , p-cresol, catechol, alpha -naphthol, beta -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, tri Hydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzenetriol, dicyclopentadiene type diphenol compounds, phenol novolak, and the like. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol in one dicyclopentadiene molecule.

Examples of the active ester curing agent include active ester compounds containing a dicyclopentadiene type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated phenol novolak, benzoylated phenol novolacs Among these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferable. These may be used singly or in combination of two or more kinds. On the other hand, the "dicyclopentadiene type diphenol structure" refers to a divalent structural unit comprising phenylene-dicyclopentalene-phenylene.

EXB9451 "," EXB9460 "," EXB9460S "," HPC-8000-65T "(manufactured by DIC Corporation) as the active ester compound containing a dicyclopentadiene type diphenol structure as a commercially available product of the active ester type curing agent, , "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, "DC808" (manufactured by Mitsubishi Chemical Corp.) as an active ester compound containing acetylated phenol novolak, phenol And YLH1026 (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing benzoylated novolak.

Specific examples of the benzoxazine type curing agent include "HFB2006M" manufactured by Shawako Co., Ltd., "P-d" and "F-a" manufactured by Shikoku Kasei Corporation.

Examples of the cyanate ester curing agent include, but are not limited to, cyanate ester curing agents such as novolak type (phenol novolac type, alkylphenol novolak type and the like), dicyclopentadiene type cyanate ester type curing agents, (Bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate ester type curing agents, and partially triarylated prepolymers thereof. Specific examples thereof include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylene bis (2,6-dimethyl phenyl cyanate) Bis (4-cyanate phenylmethane), bis (4-cyanate) phenylpropane, 4,4'-diphenylmethane diisocyanate, Benzene, bis (4-cyanate phenyl) thioether, and bis (4-cyanate-3,5-dimethylphenyl) (4-cyanate phenyl) ether, polyfunctional cyanate resins derived from phenol novolak and cresol novolak, and prepolymers in which these cyanate resins are partly triarized As commercially available products of the cyanate ester curing agent, "PT30" and "PT60" (both of phenol novolak type polyfunctional epoxy resin Sites ester resin), "BA230" (a part or the whole of bisphenol A dish ah carbonate triazol evolution of prepolymer trimer), and the like.

The ratio of the epoxy resin to the curing agent is preferably from 1: 0.2 to 1: 1 in terms of the ratio of [the total number of epoxy groups of the epoxy resin]: [the total number of the reactors of the curing agent] from the viewpoint of improving the mechanical strength and water resistance of the resulting insulating layer. : 2, more preferably in the range of 1: 0.3 to 1: 1.5, further preferably in the range of 1: 0.4 to 1: 1. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like and varies depending on the kind of the curing agent. The total number of epoxy groups in the epoxy resin refers to a value obtained by dividing the solid component mass of each epoxy resin by the epoxy equivalent in terms of all epoxy resins and the total number of reactors in the curing agent means that the solid mass of each curing agent is equivalent to the reactor Of the total amount of the curing agent.

In one embodiment, the resin composition of the present invention contains the inorganic filler, the epoxy resin and the curing agent. Among them, the resin composition preferably contains crystalline silica as an inorganic filler, a mixture of a liquid epoxy resin and a solid epoxy resin as an epoxy resin (a mass ratio of liquid epoxy resin: solid epoxy resin is preferably 1: 0.1 to 1: 4, (1: 0.3 to 1: 3.5, more preferably 1: 0.6 to 1: 3) is used as the curing agent, and a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent and a cyanate ester- It is preferable to contain at least one of them. As for the resin composition layer containing these specific components in combination, the preferable contents of the inorganic filler, the epoxy resin and the curing agent are as described above.

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

- Thermoplastic resin -

Examples of the thermoplastic resin include thermoplastic resins such as phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyether sulfone resin, Ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins. The thermoplastic resin may be used singly or in combination of two or more kinds.

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

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, A phenoxy resin having at least one skeleton selected from the group consisting of a skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethyl cyclohexane 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 singly or in combination of two or more kinds. Specific examples of the phenoxy resin include "1256" and "4250" (both phenol resins containing a bisphenol A skeleton), "YX8100" (phenoxy resin containing a bisphenol S skeleton), and "YX6954" (Phenoxy resin containing a bisphenol acetophenone skeleton), and "FX280" and "FX293" manufactured by Shin Nitetsu Sumikin Kagaku Co., Ltd., "YL7553" and "YL6794" manufactured by Mitsubishi Kagaku Co., YL7213 &quot;, &quot; YL7290 &quot;, and &quot; YL7482 &quot;.

Specific examples of the polyvinyl acetal resin include DENKA BUTYRAL 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Denki Kagaku Kogyo K.K., , BX series, KS series, BL series, BM series and the like.

Specific examples of the polyimide resin include "Rika Coat SN20" and "Rika Coat PN20" manufactured by Shin-Nihon Rika K.K. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (described in JP-A 2006-37083), a polysiloxane And modified polyimides such as skeleton-containing polyimide (JP-A-2002-12667 and JP-A-2000-319386).

Specific examples of the polyamide-imide resin include "Hiromax HR11NN" and "Hiromax HR16NN" manufactured by Toyo Boseki K.K. Specific examples of the polyamideimide resin include modified polyamideimide such as polyamideimide "KS9100" and "KS9300" containing polysiloxane skeleton manufactured by Hitachi Chemical Co., Ltd.

Specific examples of the polyether sulfone resin include "PES 5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

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

The content of the thermoplastic resin in the resin composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 to 5% by mass based on 100% by mass of the nonvolatile component in the resin composition %to be.

- Curing accelerator -

Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators and guanidine-based curing accelerators, and phosphorus-based curing accelerators, amine-based curing accelerators and imidazole- . The curing accelerator may be used singly or in combination of two or more kinds. The content of the curing accelerator is preferably in the range of 0.05 to 3% by mass based on 100% by mass of the total of the nonvolatile component of the epoxy resin and the curing agent.

- Flame retardant -

Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicon-based flame retardant, a metal hydroxide, and the like. The flame retardant may be used singly or in combination of two or more kinds. The content of the flame retardant in the resin composition is not particularly limited, but is preferably 0.5 to 10 mass%, more preferably 1 to 9 mass%, based on 100 mass% of the nonvolatile component in the resin composition.

- Organic filler -

As the organic filler, any organic filler that can be used in forming the insulating layer of the printed wiring board may be used. Examples thereof include rubber particles, polyamide fine particles, and silicone particles. Rubber particles are preferred.

The rubber particles are not particularly limited as long as they are fine particles of a resin which is chemically crosslinked to a rubber elasticity and rendered insoluble or non-soluble in an organic solvent. Examples thereof include acrylonitrile butadiene rubber particles, butadiene rubber particles, Rubber particles and the like. Specific examples of the rubber particles include XER-91 (manufactured by Nihon Gosei Rubber Co., Ltd.), Stypylloid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (manufactured by Aika Kogyo Co., EXL2655, and EXL2602 (manufactured by Kureha Chemical Industry Co., Ltd.).

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

- Other ingredients -

The resin composition of the present invention may contain other components as required. Examples of such other components include organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds, and resin additives such as thickeners, defoaming agents, leveling agents, adhesion promoters, colorants and curable resins. have.

The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method of mixing and dispersing the compounding ingredients with a solvent or the like, if necessary, using a rotary mixer or the like.

INDUSTRIAL APPLICABILITY The resin composition of the present invention exhibits good dispersion stability and appropriate melt viscosity, and can suppress warpage in the component mounting process. The resin composition of the present invention can be suitably used as a resin composition (a resin composition for an interlayer insulating layer of a printed wiring board) for forming an interlayer insulating layer of a printed wiring board and further forms an interlayer insulating layer in which a conductor layer is formed by plating (A resin composition for an interlayer insulating layer of a printed wiring board on which a conductor layer is formed by plating). The resin composition of the present invention can also be applied to various uses such as a sheet-like laminated material such as an adhesive film and a prepreg, a resin composition such as a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, Can be widely used.

[Sheet-like laminated material]

The resin composition of the present invention may be applied in a varnish state, but it is industrially generally used in the form of a sheet-like laminate material including a resin composition layer formed of the resin composition.

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

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

The thickness of the resin composition layer is preferably 100 占 퐉 or less, more preferably 80 占 퐉 or less, still more preferably 60 占 퐉 or less, still more preferably 50 占 퐉 or less or 40 占 퐉 or less to be. The lower limit of the thickness of the resin composition layer is not particularly limited, but is usually 10 占 퐉 or more.

As the support, for example, a film made of a plastic material, a metal foil and a release paper can be mentioned, and a film or a metal foil made of a plastic material is preferable.

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter may be abbreviated as "PET"), polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN" (TAC), polyether sulfide (PES), and the like, such as polyesters, polycarbonates (hereinafter, sometimes abbreviated as PC) and polymethylmethacrylate ), Polyether ketone, polyimide and the like. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

In the case of using a metal foil as a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used or a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) It is also good.

The support may be subjected to a mat treatment or a corona treatment on the surface of the support on the side to be bonded with the resin composition layer. As the support, a release layer-adhered support having a release layer on the surface to be bonded to the resin composition layer may be used. As the releasing agent to be used for the release layer of the release layer-adhered support, for example, one or more release agents selected from the group consisting of an alkyd resin, an olefin resin, a urethane resin, and a silicone resin can be mentioned. Examples of commercially available products of the release agent include SK-1, AL-5, and AL-7 manufactured 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 탆, more preferably in the range of 10 to 60 탆. On the other hand, when the support is a release layer-attached support, it is preferable that the total thickness of the release layer-adhered support is in the above range.

The adhesive film can be produced, for example, by preparing a resin varnish obtained by dissolving a resin composition in an organic solvent, coating the resin varnish on a support using a die coater or the like, and 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, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, Carbitol such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used singly or in combination of two or more kinds.

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

In the adhesive film, a protective film conforming to the support may be further laminated on the surface of the resin composition layer not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 to 40 탆. By laminating a protective film, it is possible to prevent adhesion and scratching of dust or the like to the surface of the resin composition layer. The adhesive film can be rolled up and stored. When the adhesive film has a protective film, it can be used by peeling the protective film.

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

The sheet-like fibrous substrate used in the prepreg is not particularly limited, and those commonly used as prepreg substrates such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. The thickness of the sheet-like fiber base material is preferably 50 占 퐉 or less, more preferably 40 占 퐉 or less, further preferably 30 占 퐉 or less, still more preferably 20 占 퐉 or less, from the viewpoint of reducing the thickness of the printed wiring board. The lower limit of the thickness of the sheet-like fibrous substrate is not particularly limited, but is usually 10 占 퐉 or more.

And can be produced by a known method such as prepreg, hot melt method, solvent method and the like.

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

In the sheet-like laminated material, the minimum melt viscosity of the resin composition layer is preferably 300 poise or more, more preferably 500 poise or more, and still more preferably 500 poise or more from the viewpoint of suppressing resin seeping during production of the printed wiring board Is at least 700 poise, at least 900 poise, or at least 1000 poise. The upper limit of the lowest melt viscosity of the resin composition layer is preferably 30,000 poise or less, more preferably 25000 poise or less, still more preferably 25000 poise or less, and still more preferably 25000 poise or less, from the viewpoint of achieving good lamination 20,000 poise or less, 15000 poise or less, 10000 poise or less, 5000 poise or less or 3500 poise or less. Particularly in the production of a printed wiring board, when the resin composition layer and the inner layer substrate are laminated by a vacuum laminating method, 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 &quot; minimum melt viscosity &quot; 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. Specifically, when the resin composition is heated by heating at a constant heating rate to melt the resin, the melt viscosity of the resin is lowered at the initial stage as the temperature rises. Thereafter, when the temperature exceeds the predetermined temperature, the melt viscosity increases with the temperature rise. The "minimum melt viscosity" refers to the melt viscosity of such a minimum point. The lowest melt viscosity of the resin composition layer can be measured by a dynamic viscoelasticity method, and can be measured, for example, by the method described in &quot; Measurement of Minimum Melting Viscosity &quot;

In the present invention using a predetermined amount of an inorganic filler satisfying a specific shape parameter condition, it is possible to advantageously form a resin composition layer exhibiting the lowest melt viscosity in the above-mentioned preferable range and to exhibit a good lamination property at the time of production of a printed wiring board Resulting in sheet-over-stack material. Further, since the resin composition of the present invention exhibits good dispersion stability, precipitation of coarse aggregated particles in the resin composition layer can be suppressed in the obtained sheet-like laminated material.

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

[Printed circuit board]

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

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

(I) Step of laminating an adhesive film on the inner layer substrate and bonding the resin composition layer of the adhesive film to the inner layer substrate

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

The term &quot; inner layer substrate &quot; used in the 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 circuit boards (circuits) patterned on both sides are formed. Further, when manufacturing a printed wiring board, an inner layer circuit board of an intermediate product in which an insulating layer and / or a conductor layer is to be formed is also included in the &quot; inner layer board &quot;

The thickness of the inner layer substrate is preferably 800 占 퐉 or less, more preferably 400 占 퐉 or less, and still more preferably 200 占 퐉 or less, from the viewpoint of reducing the thickness of the printed wiring board. According to the present invention, even when a thinner inner-layer substrate is used, the warp of the printed wiring board in the mounting process can be suppressed. An inner layer substrate having a thickness of, for example, 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, It is possible to suppress the warping in the mounting process. The lower limit of the thickness of the inner layer substrate is not particularly limited, but is preferably 10 占 퐉 or more, and more preferably 20 占 퐉 or more, from the viewpoint of improvement in handling during production of a printed wiring board.

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

The lamination of the inner layer substrate and the adhesive film can be carried out, for example, by thermally bonding an adhesive film to the inner layer substrate on the support side. Examples of the member for heating and pressing the adhesive film to the inner layer substrate (hereinafter also referred to as &quot; hot pressing member &quot;) include a heated metal plate (SUS hard plate) or a metal roll (SUS roll). On the other hand, it is preferable to press the heat-press member through an elastic material such as heat-resistant rubber so that the adhesive film sufficiently sucks the surface unevenness of the surface of the inner layer substrate without directly pressing the adhesive member.

The lamination of the inner layer substrate and the adhesive film may be carried out by a vacuum lamination method. In the vacuum laminating method, the heat pressing temperature is preferably in the range of 60 to 160 占 폚, more preferably 80 to 140 占 폚, and the heat pressing pressure is preferably 0.098 to 1.77 MPa, 1.47 MPa, and the heat pressing time is preferably in the range of 20 to 400 seconds, and more preferably 30 to 300 seconds. The lamination is preferably performed under a reduced pressure of 26.7 hPa or less.

The lamination can be performed by a commercial vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressurized laminator manufactured by Meikishesakusho Co., Ltd., a vacuum applicator manufactured by Nichigo Morton Co., Ltd., and the like can be given.

After lamination, the laminated adhesive film may be subjected to smoothing treatment under atmospheric pressure (at atmospheric pressure), for example, by pressing the hot press member on the support side. The pressing condition of the smoothing treatment can be set to the same conditions as the hot pressing conditions of the lamination. The smoothing process can be performed by a commercial laminator. On the other hand, the lamination and smoothing process may be carried out continuously using the above-mentioned commercial vacuum laminator.

The lamination of the inner layer substrate and the adhesive film may also be carried out using a vacuum hot press. By using a vacuum hot press machine, even when a resin composition having a high content of inorganic filler is used, good lamination performance (circuit embedding property) can be achieved. The heating and pressurization may be carried out in one step, but it is preferable to carry out the heating and pressurization in two or more stages from the viewpoint of inhibiting the resin from leaching out. For example, the first-stage press is carried out at a temperature of 70 to 150 DEG C, a pressure of 0.098 to 1.77 MPa, and a second-stage press at a temperature of 150 to 200 DEG C and a pressure of 0.098 to 3.92 MPa . The time for each step is preferably 30 to 120 minutes. Presses, of usually 1 × 10 ^-2 MPa or less, and preferably is carried out under a reduced pressure of less than 1 × 10 ^-3 MPa. As a commercially available vacuum hot press, for example, "MNPC-V-750-5-200" manufactured by Meikishesakusho Co., Ltd. and "VH1-1603" manufactured by Kitagawa Seiki Co., Ltd. can be mentioned. When the step (I) is carried out using a vacuum hot press, the step may also serve as a thermosetting (i.e., step (II)) of the resin composition layer.

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

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

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

For example, the thermosetting condition of the resin composition layer varies depending on the kind of the resin composition and the like, but the curing temperature is in the range of 120 to 240 캜 (preferably in the range of 150 to 210 캜, more preferably in the range of 170 to 190 ° C.), and the curing time is in the range of 5 to 90 minutes (preferably 10 to 75 minutes, and more preferably 15 to 60 minutes).

The resin composition layer may be preheated at a temperature lower than the curing temperature before thermosetting the resin composition layer. For example, before the resin composition layer is thermally cured, the resin composition layer is heated to a temperature of not less than 50 ° C and not more than 120 ° C (preferably not less than 60 ° C and not more than 110 ° C, more preferably not less than 70 ° C and not more than 100 ° C) (Preferably 5 to 150 minutes, more preferably 15 to 120 minutes).

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

(III) the step of piercing the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming the conductor layer on the surface of the insulating layer. good. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used in the production of printed wiring boards. On the other hand, when the support is removed after the step (II), the removal of the support is carried out between the step (II) and the step (III), between the step (III) ).

The step (III) is a step of perforating the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. The step (III) may be carried out using, for example, a drill, a laser or a plasma, depending on the composition of the resin composition used for forming the insulating layer. The dimensions and shape of the holes may be suitably determined in accordance with the design of the printed wiring board. As described above, since the resin composition of the present invention exhibits good dispersion stability, precipitation of coarse aggregated particles in the resin composition layer and further in the insulating layer can be suppressed. In the insulating layer having such a uniform composition, a hole having a desired cross-sectional shape in the step (III) can be formed. Therefore, even when the holes are filled with the conductor metal to form the field via, the holes can be smoothly filled with the conductor metal. On the other hand, when sharpened angular inorganic fillers or coarsely agglomerated particles thereof exist on the wall surface of the hole as in the case of using the inorganic filler on the fracture surface, the plating is preferentially stretched from the inorganic filler or its coarse agglomerated particle as a starting point Voids may be generated in the field vias. In the present invention using an inorganic filler satisfying a specific shape parameter condition, it is possible to suppress the presence of such aggregated particles on the wall surface of the hole, so that the plating is uniformly extended over the entire wall surface of the hole, Can be advantageously suppressed.

Step (IV) is a step of roughening the insulating layer. The procedure and condition of the roughening treatment are not particularly limited, and a known procedure and condition commonly used in forming the insulating layer of the printed wiring board can be adopted. For example, the swelling treatment with a swelling liquid, the harmonization treatment with an oxidizing agent, and the neutralization treatment with a neutralizing liquid can be carried out in this order to roughen the insulating layer. The swelling liquid is not particularly limited, but an alkaline solution, a surfactant solution and the like can be mentioned, and an alkaline solution is preferable, and a sodium hydroxide solution and a potassium hydroxide solution are more preferable as the alkaline solution. Examples of commercially available swelling liquids include Swelling Dip · Sucrygant P, Swelling Dip · Sucrygant SBU manufactured by Atotech Japan Co., Ltd., and the like. The swelling treatment with the swelling liquid is not particularly limited, and can be carried out, for example, by immersing the insulating layer in a swelling solution at 30 to 90 캜 for 1 to 20 minutes. The oxidizing agent is not particularly limited, and for example, an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide may be mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 캜 for 10 to 30 minutes. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by mass. Examples of the commercially available oxidizing agent include alkaline permanganic acid solutions such as Concentrate Compact CP manufactured by Atotech Japan Co., Ltd., and Dozing Solution · Sucry Gent P (trade name). As the neutralization solution, an acidic aqueous solution is preferable, and as a commercial product, for example, Reduction Solution · Sucrygant P manufactured by Atotech Japan Co., Ltd. may be mentioned. The treatment with the neutralizing liquid can be carried out by immersing the treated surface subjected to the roughening treatment with the oxidizing agent solution in a neutralizing solution at 30 to 80 캜 for 5 to 30 minutes.

The insulating layer formed using the resin composition of the present invention exhibits a low surface roughness after the roughening treatment. In one embodiment, the arithmetic average roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 480 nm or less, still more preferably 450 nm or less, still more preferably 400 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 the Ra is small. The lower limit of the Ra value is not particularly limited, but is preferably 0.5 nm or more, more preferably 1 nm or more. The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact surface roughness meter. As a specific example of the non-contact type surface roughness meter, "WYKO NT3300" manufactured by Vico Instruments Inc. can be mentioned.

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

The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, do. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include alloys of two or more metals selected from the above-mentioned group (for example, nickel-chromium alloy, copper-nickel alloy, Alloy). Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, a copper-nickel alloy And an alloy layer of a copper-titanium alloy is preferable and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper or an alloy layer of a nickel- chromium alloy is more preferable, Is more preferable.

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

The thickness of the conductor layer depends on the design of the desired printed wiring board, but is generally from 3 to 35 mu m, preferably from 5 to 30 mu m.

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

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

The insulating layer formed using the resin composition of the present invention exhibits sufficient adhesion strength to the conductor layer. In one embodiment, the adhesion strength between the insulating layer and the conductor layer is preferably 0.50 kgf / cm or more, more preferably 0.55 kgf / cm or more, and still more preferably 0.60 kgf / cm or more. The upper limit value of the adhesion strength is not particularly limited, but is 1.2 kgf / cm or less and 0.90 kgf / cm or less. In the present invention, since the insulating layer exhibiting such high adhesion strength can be formed even though the surface roughness (Ra) of the insulating layer after the roughening treatment is small, it contributes significantly to miniaturization of the circuit wiring. In the present invention, the adhesion strength between the insulating layer and the conductor layer refers to the peel strength (90 degree fill strength) when the conductor layer is peeled in the direction perpendicular to the insulating layer (90 degrees direction) And the peel strength when peeling in the direction perpendicular to the layer (in the direction of 90 degrees) is measured by a tensile tester. As the tensile tester, for example, "AC-50C-SL" manufactured by TES Co., Ltd. and the like can be mentioned.

In another embodiment, the printed wiring board of the present invention can be produced by using the above prepreg. The manufacturing method is basically the same as the case of using an adhesive film.

[Semiconductor device]

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

In one embodiment, the printed wiring board of the present invention can suppress the warpage of the printed wiring board to less than 40 mu m in a mounting process employing a solder reflow temperature which has a peak temperature as high as 260 deg. In the present invention, the warp of the printed wiring board is a value of the difference between the maximum height and the minimum height of the displacement data when the warping behavior of each 10 mm portion in the center of the printed wiring board is observed with a shadow moire apparatus. For the measurement, the reflow temperature profile (profile for lead-free assembly, peak temperature 260 (as described in IPC / JEDEC J-STD-020C (Moisture / Reflow Sensitivity Classification for Nonhermetic Solid State Surface Mount Devices, ° C.), and one side of the printed wiring board was subjected to a heat treatment with a reflow temperature profile conforming to IPC / JEDEC J-STD-020C, and the other side of the printed wiring board The displacement data was obtained with respect to the lattice lines formed on the substrate. On the other hand, as the reflow apparatus, for example, "HAS-6116" manufactured by Nihon Anthom Co., Ltd. can be mentioned, and as the shadow moiré apparatus, for example, TherMoire AXP manufactured by Akrometrix. The printed wiring board of the present invention including the insulating layer formed by the cured product of the resin composition containing a predetermined amount of the inorganic filler satisfying the specific shape parameter condition can advantageously suppress the warping in the mounting step even if it is thin .

Examples of the semiconductor device include various semiconductor devices provided in electrical products (such as a computer, a mobile phone, a digital camera, and a television) and a vehicle (such as a motorcycle, a car, a train, .

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion (conductive portion) of the printed wiring board of the present invention. The &quot; conduction site &quot; is a &quot; location for transmitting electrical signals in a printed wiring board &quot;, and may be a surface or a buried site. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor material.

The method of mounting the semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip effectively functions. Specifically, the semiconductor chip mounting method, the flip chip mounting method, the bump- (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), and the like. Here, the "mounting method using the bumpless buildup layer (BBUL)" refers to a mounting method in which "the semiconductor chip is directly buried in the concave portion of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board" .

[Example]

Hereinafter, the present invention will be described concretely with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" mean "part by mass" and "% by mass", respectively, unless otherwise specified.

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

[Preparation of evaluation substrate 1]

(1) Preparation of inner layer circuit board

Both surfaces of a glass cloth base epoxy resin double-sided copper clad laminate (thickness of copper foil of 18 탆, thickness of the substrate of 0.3 mm, "R5715ES" manufactured by Matsushita Electric Industrial Co., Ltd.) Mu] m to conduct coarsening treatment of the copper surface.

(2) lamination of an adhesive film

The adhesive films produced in the examples and the comparative examples were laminated on the inner layer circuit board such that the resin composition layer was bonded to the innerlayer circuit board using a batch type vacuum laminator ("MVLP-500" manufactured by Meikisha Sakusho Co., Ltd.) Respectively. The lamination was carried out by reducing the pressure for 30 seconds to bring the air pressure to 13 hPa or less, followed by pressing at 100 DEG C and a pressure of 0.74 MPa for 30 seconds.

(3) Curing of the resin composition layer

After lamination, the support was peeled from both sides of the substrate. Subsequently, the resin composition layer was thermally cured at 100 占 폚 for 30 minutes and at 170 占 폚 for 30 minutes to form an insulating layer.

(4) Harmonization processing

After the formation of the insulating layer, the substrate was immersed in a swelling liquid (aqueous solution containing "Swelling Dip · Sucuregent P", diethylene glycol monobutyl ether and sodium hydroxide manufactured by Atotech Japan Co., Ltd.) at 80 ° C for 5 minutes, (Aqueous solution of KMnO ₄ : 60 g / L, NaOH: 40 g / L) at 80 ° C for 10 minutes, and finally with a neutralizing solution (manufactured by Atotech Japan K.K. &Quot; Reduction Solution · Sucuregent P &quot;, aqueous solution of hydroxylamine sulfate) at 40 ° C for 5 minutes. Then, it was dried at 80 DEG C for 30 minutes. The resulting substrate is referred to as &quot; substrate 1a &quot;.

On the other hand, regarding the example 6 and the comparative example 5, the operations (2) to (4) were carried out as described below to obtain the substrate 1a.

The adhesive films produced in Examples and Comparative Examples were laminated on both surfaces of the inner layer circuit board so that the resin composition layer was bonded to the inner layer circuit board using a vacuum press apparatus ("VH1-1603" manufactured by Kitagawa Seiki Co., Ltd.) Respectively. The lamination was performed by pressing the laminate at a reduced pressure of 1 x 10 ^-3 MPa at 100 캜 and a pressure of 1.0 MPa for 30 minutes, then heating the laminate to 180 캜 for 10 minutes, and then pressing the laminate at 180 캜 and a pressure of 1.0 MPa for 30 minutes . Thus, the resin composition layer was thermally cured to form an insulating layer. The roughening treatment was carried out in the same manner as in the above (4) except that the roughening treatment was carried out at 60 캜 for 5 minutes and at 80 캜 for 5 minutes in an oxidizing agent.

(5) Formation of conductor layer

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

The substrate 1a was immersed in an electroless plating solution containing PdCl ₂ at 40 ° C for 5 minutes and immersed in an electroless copper plating solution at 25 ° C for 20 minutes. Subsequently, annealing was performed by heating at 150 占 폚 for 30 minutes, etching resist was formed, and a pattern was formed by etching. Thereafter, copper sulfate electroplating was performed to form a conductor layer having a thickness of 25 mu m, and annealing was performed at 180 DEG C for 30 minutes. The resulting substrate is referred to as &quot; substrate 1b &quot;.

[Preparation of Evaluation Substrate 2]

(1) Preparation of inner layer substrate

As an inner layer substrate, an unclad plate (thickness 100 탆) was prepared by removing all the copper foils on both sides of a copper clad epoxy resin double-sided copper clad laminate. As the glass cloth epoxy resin double-sided copper-clad laminate, "HL832NSF-LCA" (size: 100 mm × 150 mm, thickness of base substrate: 100 μm, coefficient of thermal expansion: 4 ppm / ° C., flexural modulus: 34 GPa, manufactured by Mitsubishi Gas Kagaku Co., Thickness 16 mu m) was used.

(2) lamination of an adhesive film

The adhesive films prepared in Examples and Comparative Examples were laminated by using a batch type vacuum laminator (CVP700, two-stage build-up laminator manufactured by Ricoh Morton Co., Ltd.) And laminated on both surfaces of the inner layer substrate. The lamination was carried out by reducing the pressure for 30 seconds to bring the air pressure to 13 hPa or less, followed by compression at 100 DEG C and a pressure of 0.74 MPa for 30 seconds. Then, hot pressing was performed at 100 占 폚 and a pressure of 0.5 MPa for 60 seconds.

(3) Curing of the resin composition layer

After lamination, the support was peeled from the substrate. Subsequently, the resin composition layer was thermally cured at 190 占 폚 for 90 minutes to form an insulating layer. The resulting substrate is referred to as &quot; substrate 2a &quot;.

&Lt; Measurement of specific surface area (S) of inorganic filler &

The specific surface area of the inorganic filler was determined by the nitrogen BET method using an automatic specific surface area measuring apparatus (Macsorb HM-1210 manufactured by Moon Tec Co., Ltd.).

&Lt; Measurement of average particle diameter (R) of inorganic filler >

0.2 g of a nonionic dispersant ("T208.5" manufactured by Nippon Oil Co., Ltd.) and 10 g of pure water were added to a vial bottle of 20 ml, and ultrasonic dispersion was performed for 10 minutes using an ultrasonic cleaner to prepare a sample Respectively. Subsequently, the sample was introduced into a laser diffraction particle size distribution analyzer ("SALD2200" manufactured by Shimadzu Corporation) and subjected to ultrasonic irradiation for 10 minutes while circulating the sample. Thereafter, the ultrasonic wave was stopped, and the particle size distribution was measured while the circulation of the sample was maintained to obtain the average particle diameter (R) of the inorganic filler. On the other hand, the refractive index at the time of measurement was set to 1.45-0.001i.

<Calculation of Form Parameter A>

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

[Equation 1]

A = SR? / 6

&Lt; Calculation of shape parameter B >

Sections were observed at an observation magnification of 14,000 times using an FIB-SEM composite device (&quot; SMI3050SE &quot;, manufactured by SII Nanotechnology) with respect to the insulating layer laminated on one surface of the substrate 1a. From the obtained FIB-SEM image, the peripheral length (L) and area of the inorganic filler particles existing in the insulating layer were measured using image processing software ("QWin V3" manufactured by Leica). On the other hand, the measurement was carried out with respect to any 50 inorganic filler particles per one sample, avoiding unrecognized inorganic filler particles or unsharp inorganic filler particles as a whole. The circumferential length (circumference; Lc) of a circle of the same area as that of the obtained inorganic filler particle was calculated. Then, the values of L and Lc were substituted into the following equation (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.

&Quot; (2) &quot;

B = Lc / L

&Lt; Measurement of average crystallite diameter of inorganic filler &

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

&Lt; Evaluation of dispersion stability &

With regard to the adhesive films produced in Examples and Comparative Examples, the aggregated particles in the resin composition layer were observed at a magnification of 1000 times using a microscope ("VH-2250" manufactured by KEYENCE Co., Ltd.). The dispersion stability of the resin composition was evaluated according to the following criteria.

Evaluation standard:

○: agglomerated particles having a size of 10 μm or more were less than 2 in 10 visual fields

X: Cohesive particles having a size of 10 탆 or more were observed at 2 or more out of 10 fields

<Measurement of Minimum Melting Viscosity>

The melt viscosity of the resin composition layer of the adhesive film prepared in the examples and comparative examples was measured using a dynamic viscoelasticity measuring apparatus ("Rheosol-G3000" manufactured by Yu-Bu Co., Ltd.). With respect to 1 g of the sample resin composition, a parallel plate having a diameter of 18 mm was used to raise the temperature from a starting temperature of 60 ° C to 200 ° C at a temperature raising rate of 5 ° C / min, and a dynamic temperature of 2.5 ° C, The modulus of viscoelasticity was measured and the lowest melt viscosity was measured. The lamination properties were averaged according to the following criteria.

Evaluation standard:

?: The lowest melt viscosity was 30000 poise or less

X: Minimum melt viscosity is higher than 30000 poise

<Evaluation of warpage>

The substrate 2a (n = 5) was passed once through a reflow apparatus ("HAS-6116" manufactured by Nihon Anthom Co., Ltd.) for reproducing the solder reflow temperature at a peak temperature of 260 ° C IPC / JEDEC J-STD-020C). Subsequently, the substrate was heated with a reflow temperature profile conforming to IPC / JEDEC J-STD-020C (peak temperature 260 ° C) using a shadow moire apparatus ("TherMoire AXP" manufactured by Akrometrix) Based on one grating line, the displacement of each 10 mm square at the center of the substrate was measured. The warpage was evaluated according to the following evaluation criteria.

Evaluation standard:

?: With respect to all 5 samples, the difference between the maximum height and the minimum height of the displacement data in the entire temperature range was less than 40 占 퐉

X: With respect to at least one sample, if the difference between the maximum height and the minimum height of the displacement data in the entire temperature range is 40 占 퐉 or more

&Lt; Measurement of arithmetic mean roughness (Ra) >

With respect to the substrate 1a, a value obtained by setting the measurement range to 121 占 퐉 92 占 퐉 by using a VSI contact mode and a 50x lens using a non-contact surface roughness meter ("WYKO NT3300" manufactured by Vico Instruments Inc.) Respectively. The average value of 10 randomly selected points was obtained as a measurement value.

&Lt; Measurement of adhesion strength of conductor layer >

The adhesion strength between the insulating layer and the conductor layer was measured according to JIS C6481 with respect to the evaluation board 1b. Specifically, a notch in a portion of a width of 10 mm and a length of 100 mm was inserted into the conductor layer of the substrate 1b, the one end was peeled off and picked up by a forceps, and 35 mm was peeled in a vertical direction at a rate of 50 mm / (Kgf / cm) was measured, and the adhesion strength was determined.

<Measurement of Linear Thermal Expansion Coefficient>

The adhesive films prepared in Examples and Comparative Examples were heated at 190 占 폚 for 90 minutes to thermally cure the resin composition layer. Then, the support was peeled off to obtain a sheet-like cured product. The obtained sheet-like cured product was cut into test pieces each having a width of about 5 mm and a length of about 15 mm and subjected to thermomechanical analysis by the tensile weighting method using a thermomechanical analyzer ("Thermo Plus TMA8310" manufactured by Rigaku Corporation) Respectively. Specifically, after the test piece was mounted on the thermomechanical analyzer, the test piece was continuously measured twice under the measurement conditions of a load of 1 g and a temperature raising rate of 5 캜 / minute. Then, in the second measurement, the average linear thermal expansion coefficient in a range from 25 ° C to 150 ° C was calculated.

&Lt; Evaluation of voids of field vias &

The evaluation of the voids of the via vias was carried out according to the following procedure.

(1) Formation of via hole

A via hole having a top diameter of 60 占 퐉 and a void diameter of 50 占 퐉 was formed in an insulating layer laminated on one surface of the substrate 1a using a carbon dioxide gas laser processing machine ("LC-2E21B / 1C" manufactured by Hitachi, .

(2) Formation of field vias

After the formation of the via hole, the insulating layer was roughened to form a conductor layer. The roughening treatment and the formation of the conductor layer were carried out in the same manner as in [Preparation of evaluation substrate 1]. Thereby, the conductor metal was also filled in the via hole, and a field via was obtained.

(3) Evaluation of void

The formed field vias were observed with a scanning electron microscope (SEM) (model "SU-1500", manufactured by Hitachi High-Technologies Corporation). The case where the number of voids was less than 2 was defined as &quot; &quot;, and the case where the number of voids was 2 or more was defined as &quot; x &quot;.

Table 1 shows physical properties and shape parameters A and B of the inorganic filler used in Examples and Comparative Examples.

With respect to IMSIL A-8, the content of particles having a shape parameter B of less than 0.8 is 36% by number, particularly the content of particles having a shape parameter B of 0.75 or less is 16% 12% by number, particularly, the content of particles having the shape parameter B of 0.94 or more was 0% by number. With respect to IMSIL A-25, the content of particles having a shape parameter B of less than 0.8 is 26% by number, particularly the content of particles having a shape parameter B of 0.75 or less is 20% 14% by number, particularly, the content of particles having the shape parameter B of 0.94 or more was 0% by number.

&Lt; Example 1 >

(1) Preparation of resin varnishes

20 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828EL" manufactured by Mitsubishi Chemical Corporation), 30 parts of biphenyl type epoxy resin (epoxy equivalent 276, "NC3000" manufactured by Nippon Kayaku Co., Ltd.) , 5 parts of a phenol ethane type epoxy resin (epoxy equivalent 198, "jER1031S" manufactured by Mitsubishi Chemical Corporation), 5 parts of a solid bisphenol A type epoxy resin (epoxy equivalent weight about 3000 to 5000, "jER1010" manufactured by Mitsubishi Chemical Corporation) 5 parts of a 50% by mass resin solution of a nonvolatile component dissolved in a mixed solvent of methyl ethyl ketone (MEK) and cyclohexanone in a mass ratio of 1: 1 was dissolved by heating in a mixed solvent of 20 parts of MEK and 10 parts of cyclohexanone with stirring . 10 parts of a phenol novolak type curing agent containing a triazine skeleton (hydroxyl equivalent 125, "LA-7054" manufactured by DIC Corporation, MEK solution having a solid content of 60%), 10 parts of phenol novolak type curing agent (hydroxyl equivalent 105, DIC , 3 parts of an amine-based curing accelerator (4-dimethylaminopyridine (DMAP), 5% by mass of a solid content of MEK solution), 3 parts of N-phenyl-3-aminopropyltrimethoxysilane (IMSIL A-8, manufactured by Unimin Co., Ltd.) having an average particle diameter of 1.38 mu m, a maximum particle diameter of 20 mu m, a specific surface area of 6.54 m2 / g and a density of 2.65 g / , 180 parts of an average crystallite diameter of 1000 Å), 180 parts of a flame retardant ("HCA-HQ" manufactured by Sanko Corporation, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene- 10-oxide, average particle diameter 2 占 퐉) were mixed and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish. On the other hand, the total density of the nonvolatile component other than the inorganic filler used for preparing the resin varnish was about 1.2 g / cm 3.

(2) Production of adhesive film

As the support, a polyethylene terephthalate film (thickness 38 mu m, "AL5", manufactured by Lintec Corporation) having an alkyd resin-based release layer was prepared. The resin varnish prepared above was uniformly coated on the support by a die coater and dried at 80 to 120 캜 (average 100 캜) for 6 minutes to form a resin composition layer. The thickness of the resin composition layer was 40 占 퐉, and the residual solvent amount in the resin composition was about 2% by mass. Next, a roll of a polypropylene film ("ALPAN MA-411", manufactured by Oshitoku Shusho Co., Ltd.) was wound on the surface of the resin composition layer in a rolled state while sticking a thickness of 15 μm on the smooth surface side. Slit to 507 mm, and an adhesive film having a size of 507 mm x 336 mm was obtained.

&Lt; Example 2 >

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

&Lt; Example 3 >

12 parts of a naphthol novolak type curing agent (hydroxyl equivalent number 215, "SN485" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.) was used in place of 6 parts of phenol novolac type curing agent (hydroxyl equivalent 105, "TD2090" ("IMSIL A-8" manufactured by Unimin Co., Ltd.) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) A resin varnish was prepared in the same manner as in Example 1 except for that, and an adhesive film was produced.

<Example 4>

(YL7553BH30 manufactured by Mitsubishi Kagaku Co., Ltd .; MEK / cyclohexane having a solid content of 30% by mass) in place of the solid bisphenol A type epoxy resin (epoxy equivalent weight about 3000 to 5000, "jER1010" manufactured by Mitsubishi Chemical Corporation) Hexane = 1/1 solution) was used in place of the resin varnish prepared in Example 1, and an adhesive film was prepared.

&Lt; Example 5 >

Instead of 180 parts of crystalline silica ("IMSIL A-8" manufactured by Unimin Co., Ltd.) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (KBM573 manufactured by Shin- (IMSIL A-25, manufactured by Unimin Co., Ltd.) having an average particle diameter of 2.55 占 퐉, a maximum particle diameter of 20 占 퐉, a specific surface area 5.87 m &lt; 2 &gt; / g, density: 2.65 g / cm &lt; 3 &gt;, average crystallite diameter: 1400 ANGSTROM) was used to prepare an adhesive film.

&Lt; Example 6 >

("IMSIL A-8" manufactured by Unimin Co., Ltd.) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (KBM573 manufactured by Shin-Etsu Chemical Co., 20 mu m, specific surface area of 6.54 m &lt; 2 &gt; / g, density of 2.65 g / cm3, average crystallite diameter of 1000 angstroms) was changed to 400 parts.

&Lt; Comparative Example 1 &

Instead of 180 parts of crystalline silica ("IMSIL A-8" manufactured by Unimin Co., Ltd.) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (KBM573 manufactured by Shin- ("SO-C2" manufactured by Adomatex Co., Ltd.) having an average particle diameter of 0.90 탆 and a specific surface area of 5.75 m 2 / g, which had been surface-treated with aminopropyltrimethoxysilane (KBM573 manufactured by Shin- g and a density of 2.2 g / cm 3) were used in place of the resin varnish prepared in Example 1, to prepare an adhesive film.

&Lt; Comparative Example 2 &

Instead of 180 parts of crystalline silica ("IMSIL A-8" manufactured by Unimin Co., Ltd.) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (KBM573 manufactured by Shin- ("SO-C6" manufactured by Adomatex KK) having an average particle diameter of 2.06 mu m and a specific surface area of 2.15 m &lt; 2 &gt; / g, which had been surface-treated with aminopropyltrimethoxysilane (KBM573 manufactured by Shin- g and a density of 2.2 g / cm 3) were used in place of the resin varnish prepared in Example 1, to prepare an adhesive film.

&Lt; Comparative Example 3 &

Instead of 180 parts of crystalline silica ("IMSIL A-8" manufactured by Unimin Co., Ltd.) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (KBM573 manufactured by Shin- (VX-SR, manufactured by Tatsumori KK) having an average particle diameter of 1.30 mu m and a specific surface area of 11.94 m &lt; 2 &gt;, which was surface-treated with aminopropyltrimethoxysilane (KBM573 manufactured by Shin- g, density: 2.65 g / cm &lt; 3 &gt;, average crystallite diameter: 1900 angstroms) was used as a binder resin.

&Lt; Comparative Example 4 &

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

&Lt; Comparative Example 5 &

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

Claims (14)

A resin composition for an insulating layer of a printed wiring board,
Wherein the content of the inorganic filler in the resin composition is 40 to 75% by volume,
Wherein S is the specific surface area (m 2 / g) of the inorganic filler, R is the average particle diameter (탆) of the inorganic filler and ρ is the density (g / cm 3) of the inorganic filler Wherein the shape parameter A of the inorganic filler satisfies 20? 6A? 40. A resin composition for an insulating layer of a printed wiring board,
Wherein the content of the inorganic filler in the resin composition is 40 to 75% by volume,
Where L is the peripheral length (mu m) of the inorganic filler in a predetermined cross-section, Lc is the cross-sectional area of the inorganic filler in the cross section, Wherein the average value of the shape parameter B of the inorganic filler represented by the following formula is a peripheral length (탆) of a true circle of 0.8 or more and 0.9 or less. 3. The resin composition according to claim 1 or 2, wherein the average crystallite diameter of the inorganic filler is 1800A or less. The resin composition according to claim 1 or 2, wherein the inorganic filler has a specific surface area of 3 to 10 m 2 / g. The resin composition according to claim 1 or 2, wherein the inorganic filler has an average particle diameter of 4 탆 or less. 3. The resin composition according to claim 1 or 2, wherein the inorganic filler has an average particle diameter of 3 m or less. The method according to claim 1 or 2, wherein the inorganic filler is obtained by dispersing monolithic aggregates of microcrystalline particles having an average crystallite diameter of 1800 ANGSTROM or less, and the maximum particle diameter of the monolith aggregates is 20 Mu m or less. The resin composition according to Claim 1 or 2, wherein the inorganic filler contains a crystalline inorganic filler and the content of the crystalline inorganic filler is 50% by mass or more based on 100% by mass of the entire inorganic filler. The resin composition according to claim 8, wherein the crystalline inorganic filler is crystalline silica. The resin composition according to claim 1 or 2, further comprising an epoxy resin and a curing agent. The resin composition according to claim 1 or 2, which is a resin composition for an interlayer insulating layer. A sheet-like laminated material comprising a resin composition layer formed from the resin composition according to any one of claims 1 to 3. A printed wiring board comprising an insulating layer formed by a cured product of the resin composition according to claim 1 or 2. A semiconductor device comprising the printed wiring board according to claim 13.