CN117903563A

CN117903563A - Resin composition

Info

Publication number: CN117903563A
Application number: CN202311333817.6A
Authority: CN
Inventors: 藤岛祥平
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2022-10-17
Filing date: 2023-10-16
Publication date: 2024-04-19
Also published as: KR20240053541A; JP2024059029A

Abstract

Disclosed is a resin composition which can give a cured product having excellent mechanical strength and a low relative dielectric constant. A resin composition comprising an inorganic filler (A), wherein the component (A) comprises a hollow inorganic filler (A-1) having an average circularity of 0.6 or more and an average particle diameter of 5 [ mu ] m or less, the resin composition has a dielectric loss tangent (Df) of 0.010 or less when measured at 5.8GHz and 23 ℃, and the resin composition has a relative dielectric constant (Dk) of 3.0 or less when measured at 5.8GHz and 23 ℃.

Description

Resin composition

Technical Field

The present invention relates to a resin composition. Further, the present invention relates to a cured product, a sheet-like laminate, a resin sheet, a printed wiring board, and a semiconductor device, each obtained using the resin composition.

Background

As a technique for manufacturing a printed wiring board, a build-up method is known, which is based on alternating layers of insulating layers and conductor layers. In the build-up method, the insulating layer in a typical printed wiring board is formed by curing a resin composition. In recent years, in order to improve the performance of electronic components, it has been demanded to suppress the relative dielectric constant of the insulating layer to a lower level than heretofore. As one of the methods of suppressing the relative dielectric constant low, the use of hollow inorganic filler particles has been attempted (patent document 1 or 2).

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 2020-83966

Patent document 2: japanese patent No. 5864299

Disclosure of Invention

Problems to be solved by the invention

It has been known that the use of hollow inorganic filler particles having a small diameter of 5 μm or less can reduce the relative dielectric constant, but the use of hollow inorganic filler particles having a small diameter has a problem of reduced mechanical strength.

The invention provides a resin composition which can obtain a cured product having excellent mechanical strength and a low relative dielectric constant.

Means for solving the problems

The inventors have found out to date that: when conventional hollow inorganic particles (hollow inorganic filler) having an average particle diameter of 5 μm or less and a low average circularity are used in a resin composition, pressure locally exists at convex portions of the particles in a kneading step for dispersing the resin composition before curing, and thus the hollow inorganic particles are broken, fragments of the hollow inorganic particles thus generated become starting points of the breakage, and the mechanical strength of the cured product is lowered. Accordingly, the present inventors have succeeded in obtaining a cured product excellent in mechanical strength and suppressed in relative permittivity by producing (a-1) a hollow inorganic filler having an average circularity of 0.6 or more and an average particle diameter of 5 μm or less and using the hollow inorganic filler as (a) an inorganic filler in a resin composition to achieve the object of the present invention, and have completed the present invention.

Namely, the present invention includes the following.

[1] A resin composition comprising (A) an inorganic filler, wherein,

(A) The component (A-1) comprises a hollow inorganic filler having an average circularity of 0.6 or more and an average particle diameter of 5 μm or less,

The cured product of the resin composition has a dielectric loss tangent (Df) of 0.010 or less when measured at 5.8GHz and 23 ℃, and

The relative dielectric constant (Dk) of the cured product of the resin composition is 3.0 or less when measured at 5.8GHz and 23 ℃.

[2] The resin composition according to the above [1], wherein the content of the component (A) is 40% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.

[3] The resin composition according to the above [1] or [2], wherein the average particle diameter of the component (A-1) is 0.3 μm or more.

[4] The resin composition according to any one of the above [1] to [3], wherein the porosity of the component (A-1) is 15% by volume or more.

[5] The resin composition according to any one of the above [1] to [4], wherein the material forming the component (A-1) is silica.

[6] The resin composition according to any one of the above [1] to [5], wherein the content of the component (A-1) is 30% by mass or more, based on 100% by mass of the total component (A) in the resin composition.

[7] The resin composition according to any one of the above [1] to [6], which further comprises (B) an epoxy resin.

[8] The resin composition according to any one of the above [1] to [7], which further comprises (C) a curing agent.

[9] The resin composition according to the above [8], wherein the component (C) contains an active ester-based curing agent.

[10] The resin composition according to the above [8] or [9], wherein the component (C) contains a naphthalene-type active ester-based curing agent.

[11] The resin composition according to any one of the above [8] to [10], wherein the component (C) contains a phenol-based curing agent.

[12] The resin composition according to any one of the above [1] to [11], which further comprises (D) a thermoplastic resin.

[13] The resin composition according to the above [12], wherein the component (D) comprises a phenoxy resin.

[14] The resin composition according to any one of the above [1] to [13], wherein an elongation at break of a cured product of the resin composition is 1.0% or more when measured at 23 ℃.

[15] The resin composition according to any one of the above [1] to [14], wherein a linear thermal expansion coefficient of a cured product of the resin composition is 30 ppm/. Degree.C.or less.

[16] A cured product of the resin composition according to any one of the above [1] to [15 ].

[17] A sheet-like laminate comprising the resin composition according to any one of [1] to [15 ].

[18] A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of [1] to [15] above provided on the support.

[19] A printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of [1] to [15 ].

[20] A semiconductor device comprising the printed wiring board according to [19 ].

Effects of the invention

According to the resin composition of the present invention, a cured product having excellent mechanical strength and a low relative dielectric constant can be obtained.

Detailed Description

The present invention will be described in detail below with reference to preferred embodiments thereof. The present invention is not limited to the following embodiments and examples, and may be implemented with any modifications within the scope of the claims and their equivalents.

< Resin composition >

The resin composition of the present invention comprises (A) an inorganic filler, wherein (A) the inorganic filler comprises (A-1) a hollow inorganic filler having an average circularity of 0.6 or more and an average particle diameter of 5 [ mu ] m or less. By using such a resin composition, a cured product having excellent mechanical strength and a low relative dielectric constant can be obtained. The dielectric loss tangent (Df) of the cured product of the resin composition was 0.010 or less when measured at 5.8GHz and 23 ℃, and the relative dielectric constant (Dk) of the cured product of the resin composition was 3.0 or less when measured at 5.8GHz and 23 ℃.

The resin composition of the present invention may be a composition further comprising an optional resin component on the basis of the inorganic filler (a). The resin component is not particularly limited, and examples thereof include (B) epoxy resin, (C) curing agent, (D) thermoplastic resin, (E) curing accelerator, (F) other additives, and (G) organic solvent. Hereinafter, each component that can be contained in the resin composition will be described in detail.

In the present invention, unless otherwise explicitly indicated, the content of each component in the resin composition is a value obtained when the nonvolatile component in the resin composition is set to 100 mass%, and the nonvolatile component is the entire nonvolatile component excluding the solvent in the resin composition.

Inorganic filler (A)

The resin composition of the present invention contains (A) an inorganic filler. (A) The inorganic filler is contained in the resin composition in a particulate state. As the inorganic filler (a), there are exemplified a hollow inorganic filler having a void inside the particle (void content >0 vol%) and a non-hollow inorganic filler having no void inside the particle (void content=0 vol%).

In the resin composition of the present invention, the inorganic filler (A) contains (A-1) a hollow inorganic filler (hereinafter, sometimes referred to as "specific hollow inorganic filler") having an average circularity of 0.6 or more and an average particle diameter of 5 μm or less. The specific hollow inorganic filler (A-1) may be used alone or in combination of at least 2 kinds in any ratio.

Examples of the material forming the specific hollow inorganic filler (A-1) include silica, alumina, and aluminosilicate, and among them, silica is preferable.

The average circularity of the specific hollow inorganic filler (A-1) is 0.6 or more, preferably 0.65 or more, and more preferably 0.68 or more. The upper limit of the average circularity of the specific hollow inorganic filler (A-1) may be, for example, 1 or less. (A-1) the average circularity of the specific hollow inorganic filler is (A-1) the circularity of the particles of the specific hollow inorganic fillerAverage value of (2). Circularity/>Is defined as: the ratio of the circumference of a perfect circle having an area equal to the projected area of the particle in the shape image analysis of the particle to the actual circumference of the particle (the circumference of a perfect circle equal to the area of the particle/the actual circumference of the particle) is calculated using, for example, the projected area S (m ²) of the particle in the image obtained by the shape image analysis of the particle and the circumference L (m) of the particle in the image, and using the following formula (1).

[ Mathematics 1]

From the viewpoint of obtaining the desired effect of the present invention more remarkably, the average particle diameter of the (a-1) specific hollow inorganic filler is 5.0 μm or less, preferably 4.0 μm or less, more preferably 3.0 μm or less, still more preferably 2.5 μm or less, and particularly preferably 2.2 μm or less. The lower limit of the average particle diameter of the specific hollow inorganic filler (A-1) is preferably 0.3 μm or more, more preferably 0.5 μm or more. The average particle size of the inorganic filler material can be determined by laser diffraction/scattering methods based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be produced on a volume basis by using a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size can be measured as the average particle size. The measurement sample may be prepared as follows: a sample was taken, in which 100mg of the inorganic filler and 10g of methyl ethyl ketone were placed in a vial, and the mixture was dispersed by ultrasonic waves for 10 minutes. For the measurement sample, a laser diffraction type particle size distribution measuring apparatus was used, the wavelength of the used light source was set to blue and red, the volume-based particle size distribution of the inorganic filler was measured by a flow cell (flow cell) system, and the average particle size was calculated as the median particle size from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, inc.

The specific surface area of the specific hollow inorganic filler (A-1) is not particularly limited, but is preferably 60m ²/g or less, more preferably 40m ²/g or less, still more preferably 20m ²/g or less, and particularly preferably 15m ²/g or less. The lower limit of the specific surface area of the specific hollow inorganic filler (A-1) is not particularly limited, and is, for example, 1m ²/g or more. The specific surface area of the inorganic filler was obtained by adsorbing nitrogen gas onto the sample surface by the BET method using a specific surface area measuring device (Macsorb HM-1210 manufactured by makron, inc.) and calculating the specific surface area by the BET multipoint method.

(A-1) the specific hollow inorganic filler material has voids inside the particles. The specific hollow inorganic filler (A-1) may be a single hollow particle having only 1 hollow hole in the interior of the particle, a multi-hollow particle having 2 or more hollow holes in the interior of the particle, or a mixture thereof.

The porosity of the specific hollow inorganic filler (a-1) is preferably 15% by volume or more, more preferably 30% by volume or more, still more preferably 45% by volume or more, still more preferably 60% by volume or more, particularly preferably 75% by volume or more, from the viewpoint of further improving the mechanical strength, and the upper limit thereof is preferably 90% by volume or less, more preferably 85% by volume or less. The porosity P (volume%) of the inorganic filler is defined as: the volume reference ratio (total volume of voids/volume of particles) of the total volume of 1 or more voids present inside the particles to the total volume of the particles based on the outer surface of the particles, for example, a measured value D _M(g/cm³ of the actual density of the inorganic filler material and a theoretical value D _T(g/cm³ of the mass density of the material forming the inorganic filler material) is calculated using the following formula (2).

[ Math figure 2]

The specific hollow inorganic filler (A-1) may be commercially available ones, or may be produced by a known method or a method based on a known method. Examples of the commercial products of the specific hollow inorganic filler (A-1) include "setafm", "MGH-005", "MG-005" manufactured by Pacific Cement Co; and "eyese" made by solar volatile catalyst formation company, such as "eyese", "BA-1", etc. Specific examples of the method for producing the hollow inorganic filler include, but are not particularly limited to, the following methods: an aqueous solution containing a substance capable of forming voids and a basic compound is prepared, the aqueous solution is mixed with an alkoxysilane and stirred to precipitate silica particles, the substance capable of forming voids is removed from the silica particles to obtain a hollow silica precursor, and the obtained hollow silica precursor is fired.

(A-1) the specific hollow inorganic filler is preferably surface-heat-treated. The conditions for the heat treatment of the surface are not particularly limited, and the treatment temperature is, for example, in the range of 50 to 100 ℃, preferably 70 to 80 ℃, and the treatment time is, for example, in the range of 0.5 to 3 hours, preferably 1 to 3 hours, from the viewpoint of suppressing breakage (cleavage) caused by the impact of the particles with each other.

From the viewpoint of improving moisture resistance and dispersibility, (a-1) the specific hollow inorganic filler is preferably treated with a surface treating agent. The treatment with the surface treating agent is preferably performed simultaneously with the above-described heat treatment. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, alkoxysilanes, organosilane-nitrogen compounds, titanate coupling agents, and the like. The surface treatment agent may be used alone or in combination of 1 or more than 2 kinds.

Examples of the commercial products of the surface treatment agent include "KBM403" (3-glycidoxypropyl trimethoxysilane) by Xinshi chemical industry Co., ltd., "KBM803" (3-mercaptopropyl trimethoxysilane) by Xinshi chemical industry Co., ltd., KBE903 "(3-aminopropyl triethoxysilane) by Xinshi chemical industry Co., ltd., KBM573" (N-phenyl-3-aminopropyl trimethoxysilane) by Xinshi chemical industry Co., ltd., SZ-31 "(hexamethyldisilazane) by Xinshi chemical industry Co., ltd., KBM103" (phenyl trimethoxysilane) by Xinshi chemical industry Co., KBM-4803) by Xinshi chemical industry Co., ltd., long-chain epoxy silane coupling agent, and "KBM-7103" (3, 3-trifluoropropyl trimethoxysilane) by Xinshi chemical industry Co., ltd.

From the viewpoint of improving the dispersibility of the specific hollow inorganic filler of (a-1), the degree of surface treatment by the surface treatment agent preferably falls within a prescribed range. Specifically, the surface treatment is preferably performed with 0.2 to 5 mass% of a surface treatment agent, more preferably 0.2 to 3 mass% of a surface treatment agent, and even more preferably 0.3 to 2 mass% of a surface treatment agent, based on 100 mass% of the specific hollow inorganic filler (A-1).

The degree of surface treatment based on the surface treatment agent can be evaluated by using the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, (A-1) the carbon amount per unit surface area of the specific hollow inorganic filler is preferably 0.02mg/m ² or more, more preferably 0.1mg/m ² or more, and still more preferably 0.2mg/m ² or more. On the other hand, from the viewpoint of preventing an increase in melt viscosity of the resin composition or in melt viscosity in the form of a sheet, the content is preferably 1.0mg/m ² or less, more preferably 0.8mg/m ² or less, and still more preferably 0.5mg/m ² or less. The carbon amount per unit surface area of the inorganic filler may be measured after the surface-treated inorganic filler is subjected to a cleaning treatment with a solvent (for example, methyl Ethyl Ketone (MEK)). Specifically, MEK in an amount sufficient as a solvent was added to the inorganic filler surface-treated with the surface treating agent, and the mixture was ultrasonically cleaned at 25 ℃ for 5 minutes. The carbon amount per unit surface area of the inorganic filler material can be measured using a carbon analyzer after removing the supernatant and drying the solid component. As the carbon analyzer, EMIA-320V manufactured by horiba, inc. can be used.

The content of the specific hollow inorganic filler (a-1) in the resin composition is not particularly limited, but is preferably 90 mass% or less, more preferably 85 mass% or less, and particularly preferably 80 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. The lower limit of the content of the specific hollow inorganic filler (a-1) in the resin composition is not particularly limited, but is preferably 5 mass% or more, more preferably 10 mass% or more, particularly preferably 15 mass% or more, from the viewpoint of suppressing the dielectric loss tangent of the cured product to be low, more particularly preferably 20 mass% or more, still more particularly preferably 30 mass% or more, and most preferably 40 mass% or more, when the nonvolatile component in the resin composition is 100 mass% or more, from the viewpoint of obtaining the desired effect of the present invention more remarkably.

The content of the specific hollow inorganic filler (a-1) is not particularly limited, but from the viewpoint of obtaining the desired effect of the present invention more remarkably, the content of the specific hollow inorganic filler (a) in the resin composition is preferably 10 mass% or more, more preferably 20 mass% or more, particularly preferably 30 mass% or more, and from the viewpoint of suppressing the dielectric loss tangent of the cured product to be lower, more particularly preferably 40 mass% or more, still more particularly preferably 50 mass% or more, most preferably 60 mass% or more, and the upper limit is not particularly limited, and may be 99 mass% or less, 95 mass% or less, 90 mass% or less, 80 mass% or less.

In the resin composition of the present invention, (A) the inorganic filler may further contain (A-2) a non-hollow inorganic filler as an optional component. When the non-hollow inorganic filler (A-2) is contained, 1 kind of the non-hollow inorganic filler (A-2) may be used alone, or 2 or more kinds may be used in combination at an arbitrary ratio.

As the material of the non-hollow inorganic filler (A-2), an inorganic compound is used. Examples of the material of the non-hollow inorganic filler (A-2) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate. Among these, silica is particularly suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, and synthetic silica. In addition, (A-2) the non-hollow inorganic filler material is preferably spherical silica.

Examples of the commercially available non-hollow inorganic filler (A-2) include "SP60-05" and "SP507-05" manufactured by Nitro chemical company; the "YC100C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by the mountain company; "UFP-30", "DAW-03", "FB-105FD" manufactured by Duhong; and "charging NSS-3N", "charging NSS-4N", "charging NSS-5N" manufactured by charging corporation.

The average particle diameter of the non-hollow inorganic filler (A-2) is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, further preferably 3 μm or less, further preferably 2 μm or less, particularly preferably 1.5 μm or less. The lower limit of the average particle diameter of the non-hollow inorganic filler (A-2) is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more.

The specific surface area of the non-hollow inorganic filler (A-2) is not particularly limited, but is preferably 0.1m ²/g or more, more preferably 0.5m ²/g or more, still more preferably 1m ²/g or more, and particularly preferably 3m ²/g or more. The upper limit of the specific surface area of the non-hollow inorganic filler (A-2) is not particularly limited, but is preferably 100m ²/g or less, more preferably 70m ²/g or less, still more preferably 50m ²/g or less, still more preferably 30m ²/g or less, and particularly preferably 10m ²/g or less.

The average circularity of the non-hollow inorganic filler (A-2) is preferably 0.4 or more, preferably 0.5 or more, preferably 0.6 or more, preferably 0.65 or more. The upper limit of the average circularity of the non-hollow inorganic filler (A-2) may be, for example, 1 or less.

From the viewpoint of improving moisture resistance and dispersibility, (a-2) the non-hollow inorganic filler is preferably treated with a surface treating agent. As the surface treating agent, those listed above can be used in the same manner as the specific hollow inorganic filler (A-1). The degree of surface treatment based on the surface treatment agent and the amount of carbon per unit surface area may be the same as (a-1) the specific hollow inorganic filler material.

The content of the non-hollow inorganic filler (a-2) in the resin composition is not particularly limited, but is preferably 80 mass% or less, more preferably 70 mass% or less, still more preferably 60 mass% or less, still more preferably 50 mass% or less, particularly preferably 40 mass% or less, based on 100 mass% of the non-volatile component in the resin composition, and is more particularly preferably 30 mass% or less, from the viewpoint of suppressing the dielectric loss tangent of the cured product to be lower. The lower limit of the content of the non-hollow inorganic filler (a-2) in the resin composition is not particularly limited, but is, for example, 0 mass% or more, 1 mass% or more, preferably 5 mass% or more, and more preferably 10 mass% or more, based on 100 mass% of the non-volatile component in the resin composition.

The content of the non-hollow inorganic filler (a-2) relative to the total inorganic filler (a) is not particularly limited, but from the viewpoint of obtaining the desired effect of the present invention more remarkably, the total inorganic filler (a) in the resin composition is preferably 90 mass% or less, more preferably 80 mass% or less, particularly preferably 70 mass% or less, and from the viewpoint of suppressing the dielectric loss tangent of the cured product to be lower, more particularly preferably 60 mass% or less, still more particularly preferably 50 mass% or less, most preferably 40 mass% or less, and the lower limit is not particularly limited, and may be 1 mass% or more, 5 mass% or more, 10 mass% or more, 20 mass% or more, or the like.

The content of the inorganic filler (a) in the resin composition is not particularly limited, but is preferably 90 mass% or less, more preferably 80 mass% or less, still more preferably 75 mass% or less, and particularly preferably 70 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. The lower limit of the content of the inorganic filler (a) in the resin composition is not particularly limited, but is preferably 30 mass% or more, more preferably 40 mass% or more, still more preferably 50 mass% or more, and particularly preferably 60 mass% or more, when the nonvolatile component in the resin composition is 100 mass% from the viewpoint of suppressing the dielectric loss tangent and the relative dielectric constant to be lower.

Epoxy resin (B)

The resin composition of the present invention may further contain (B) an epoxy resin as an optional component. (B) The epoxy resin is a curable resin having an epoxy group and having an epoxy equivalent weight of 5,000g/eq.

Examples of the epoxy resin (B) include a binaphthol-type epoxy resin, a bisphenol a-type epoxy resin, a bisphenol F-type epoxy resin, a bisphenol S-type epoxy resin, a bisphenol AF-type epoxy resin, a dicyclopentadiene-type epoxy resin, a triphenol-type epoxy resin, a naphthol novolac-type epoxy resin, a phenol novolac-type epoxy resin, a tert-butyl-catechol-type epoxy resin, a naphthalene-type epoxy resin, a naphthol-type epoxy resin, an anthracene-type epoxy resin, a glycidol-amine-type epoxy resin, a glycidylester-type epoxy resin, a cresol novolac-type epoxy resin, a phenol aralkyl-type epoxy resin, a biphenyl-type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, an alicyclic epoxy resin, a heterocyclic epoxy resin, a spiro-containing epoxy resin, a cyclohexane-type epoxy resin, a cyclohexanedimethanol-type epoxy resin, a naphthalene ether-type epoxy resin, a trimethylol-type epoxy resin, a tetraphenyl ethane-type epoxy resin, an isocyanurate-type epoxy resin, and a phenol benzopyrrolone-type epoxy resin. (B) The epoxy resin may be used alone or in combination of 1 or more than 2.

The resin composition preferably contains (B) an epoxy resin having 2 or more epoxy groups in 1 molecule. The proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, based on 100% by mass of the nonvolatile component of the (B) epoxy resin.

The epoxy resin includes an epoxy resin that is liquid at a temperature of 20 ℃ (hereinafter, sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20 ℃ (hereinafter, sometimes referred to as "solid epoxy resin"). The resin composition of the present invention may contain only a liquid epoxy resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin, and preferably contains a combination of a liquid epoxy resin and a solid epoxy resin as the epoxy resin.

The liquid epoxy resin is preferably a liquid epoxy resin having 2 or more epoxy groups in 1 molecule.

The liquid epoxy resin is preferably a glycyrrhizic alcohol type epoxy resin, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexanedimethanol type epoxy resin, a cyclic aliphatic glycidyl ether, or an epoxy resin having a butadiene structure.

Specific examples of the liquid epoxy resin include EX-992L of the back case, EX-yo 7400 of mitsubishi chemical company, HP4032D, HP4032SS (naphthalene type epoxy resin); "828US", "828EL", "825", "コ" made by Mitsubishi chemical corporation (bisphenol A type epoxy resin); "jER807", "1750" manufactured by mitsubishi chemical company (bisphenol F type epoxy resin); "jER152" (phenol novolac type epoxy resin) manufactured by mitsubishi chemical company; "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi chemical corporation; "ED-523T" (glycyrrhizic alcohol type epoxy resin) manufactured by ADEKA Co., ltd; "EP-3950L", "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA Co; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA Co., ltd; "ZX1059" manufactured by Nitro chemical company (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by the Uk company; "EX-991L" (epoxy resin containing alkyleneoxy skeleton and butadiene skeleton) manufactured by Uk company; a "cartridge 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by cartridge company; "PB-3600" by Waxwall corporation, and "JP-100", "JP-200", and "JP-400" by Nippon Caddha corporation (epoxy resin having butadiene structure); "ZX1658", "ZX1658GS" (liquid 1, 4-glycidic cyclohexane type epoxy resin) manufactured by Nitro chemical company; "EG-280" manufactured by Osaka gas chemical Co., ltd. (epoxy resin containing a fluorene structure); and "EX-201" (cyclic aliphatic glycidyl ether) manufactured by the Uk company.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.

The solid epoxy resin is preferably a binaphthol-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a naphthol novolac-type epoxy resin, a cresol novolac-type epoxy resin, a dicyclopentadiene-type epoxy resin, a triphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthalene-ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol a-type epoxy resin, a bisphenol AF-type epoxy resin, a phenol aralkyl-type epoxy resin, a tetraphenyl ethane-type epoxy resin, or a phenol benzopyrrolone-type epoxy resin.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC corporation; "HP-4700", "HP-4710" manufactured by DIC corporation (naphthalene type tetrafunctional epoxy resin); "N-690" (cresol novolac type epoxy resin) manufactured by DIC Co., ltd; "N-695" manufactured by DIC Co., ltd. (cresol novolak type epoxy resin); "HP-7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene type epoxy resin) manufactured by DIC Co; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4S", "HP6000L" manufactured by DIC; "EPPN-502H" (triphenol epoxy resin) manufactured by Japanese chemical Co., ltd; "NC7000L" manufactured by Japanese chemical Co., ltd. (naphthol novolac type epoxy resin); "NC3000H", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by japan chemical pharmaceutical company; "ESN475V" and "ESN4100V" manufactured by Nitro chemical company; "ESN485" (naphthol type epoxy resin) manufactured by solar iron chemistry company; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by solar iron chemistry company; "YX4000H", "YX4000HK", "YL7890" (Bixylenol type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical corporation; "YX8800" (anthracene-type epoxy resin) manufactured by mitsubishi chemical company; "YX7700" manufactured by Mitsubishi chemical corporation (phenol aralkyl type epoxy resin); "PG-100", "CG-500" manufactured by Osaka gas chemical Co., ltd; "YX7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER1010" (bisphenol a type epoxy resin) manufactured by mitsubishi chemical company; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by mitsubishi chemical company; "WHR991S" (phenol benzopyrrolidone type epoxy resin) manufactured by Japanese chemical Co., ltd. The number of these may be 1 alone or 2 or more.

When the solid epoxy resin and the liquid epoxy resin are used in combination, the mass ratio of the solid epoxy resin to the liquid epoxy resin is preferably 10:1 to 1:50, more preferably 2:1 to 1:20, and particularly preferably 1.5:1 to 1:10.

(B) The epoxy equivalent of the epoxy resin is preferably 50g/eq to 5,000g/eq, more preferably 60g/eq to 2,000g/eq, still more preferably 70g/eq to 1,000g/eq, still more preferably 80g/eq to 500g/eq. The epoxy equivalent is the mass of the resin per 1 equivalent of epoxy group. The epoxy equivalent can be measured in accordance with JIS K7236.

(B) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a polystyrene equivalent by Gel Permeation Chromatography (GPC).

The content of the epoxy resin (B) in the resin composition is not particularly limited, but is preferably 50 mass% or less, more preferably 45 mass% or less, still more preferably 40 mass% or less, still more preferably 35 mass% or less, and particularly preferably 30 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. The lower limit of the content of the epoxy resin (B) in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is set to 100% by mass, for example, 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, still more preferably 10% by mass or more, and particularly preferably 15% by mass or more.

The mass ratio of the inorganic filler (a) to the epoxy resin (B) (component (a)/component (B)) in the resin composition is not particularly limited, but is preferably 0.1 or more, more preferably 0.5 or more, and still more preferably 1 or more from the viewpoint of obtaining the desired effect of the present invention more remarkably. The upper limit of the mass ratio of the inorganic filler (a) to the epoxy resin (B) (component (a)/component (B)) in the resin composition is not particularly limited, but is more preferably 50 or less, still more preferably 10 or less, and particularly preferably 5 or less.

(C) curing agent ]

The resin composition of the present invention may further contain (C) a curing agent as an optional component. (C) The curing agent may be used alone or in combination of at least 2 kinds. (C) The curing agent has a function of reacting with the (B) epoxy resin to cure it.

The curing agent (C) is not particularly limited, and examples thereof include an active ester curing agent, a phenol curing agent, a carbodiimide curing agent, an acid anhydride curing agent, an amine curing agent, a benzoxazine curing agent, a cyanate curing agent, a thiol curing agent, and the like. (C) The curing agent preferably contains 1 or more curing agents selected from the group consisting of active ester curing agents and phenol curing agents. From the viewpoint of suppressing the dielectric loss tangent to be lower, the curing agent (C) particularly preferably contains an active ester-based curing agent. In addition, from the viewpoint of further improving curability, the (C) curing agent particularly preferably contains a phenol curing agent.

As the active ester-based curing agent, compounds having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters, thiophene esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds, are generally preferably used. The active ester compound is preferably obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester compound 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 the naphthol compound include hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, trihydroxybenzene, dicyclopentadiene type diphenol compound, phenol novolac, and the like. The "dicyclopentadiene type diphenol compound" herein means a diphenol compound obtained by condensing a phenol 2 molecule with a dicyclopentadiene 1 molecule.

The active ester-based curing agent is preferably a dicyclopentadiene-type active ester-based curing agent (an active ester compound containing a dicyclopentadiene-type diphenol structure), a naphthalene-type active ester-based curing agent (an active ester compound containing a naphthalene structure), or a phenol novolac-type active ester-based curing agent (an active ester compound (an acetyl or benzoyl compound) containing a phenol novolac structure), and more preferably at least 1 selected from the dicyclopentadiene-type active ester-based curing agent and naphthalene-type active ester-based curing agent, and further preferably a naphthalene-type active ester-based curing agent from the viewpoint of suppressing the dielectric tangent of the cured product to be lower. As an embodiment of the present invention, a combination of a dicyclopentadiene type active ester curing agent and a naphthalene type active ester curing agent is also preferable.

Examples of the commercially available active ester compounds containing a dicyclopentadiene type diphenol structure include "EXB9451", "EXB9460S", "HPC-8000L-65TM", "HPC-8000-65T", "HPC-8000H-65TM" (manufactured by DIC); examples of the active ester compound having a naphthalene structure include "HP-B-8151-62T", "EXB-8100L-65T", "EXB-9416-70BK", "HPC-8150-62T", "EXB-8" (manufactured by DIC Co.); examples of the phosphorus-containing active ester compound include "EXB9401" (manufactured by DIC Co., ltd.); examples of the active ester compound belonging to the phenol novolac type of acetylated compounds include "DC808" (manufactured by mitsubishi chemical company); examples of the active ester compound belonging to the class of phenol novolacs as the benzoyl compound include "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi chemical corporation); examples of the active ester compound containing a styryl group and a naphthalene structure include "PC1300-02-65MA" (manufactured by the company d. O., ltd.).

The phenol curing agent is preferably a phenol curing agent having a novolak structure from the viewpoints of heat resistance and water resistance. In addition, from the viewpoint of adhesion to an adherend, a nitrogen-containing phenol-based curing agent is preferable, and a phenol-based curing agent containing a triazine skeleton is more preferable. Among them, a phenol novolac resin containing a triazine skeleton is preferable from the viewpoint of satisfying heat resistance, water resistance and adhesion to a high degree. Specific examples of the phenol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851", manufactured by Ming and Chemicals; "NHN", "CBN", "GPH" manufactured by Japanese chemical Co., ltd; "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395" manufactured by Nitro chemical company; "LA-7052", "LA-7054", "LA-3018-50P", "LA-1356", "TD2090", "KA-1160" manufactured by DIC.

Examples of the carbodiimide-based curing agent include curing agents having 1 or more, preferably 2 or more carbodiimide structures in 1 molecule, and examples thereof include aliphatic biscarbodiimides such as tetramethylene-bis (t-butylcarbodiimide) and cyclohexanedis (methylene-t-butylcarbodiimide); an aromatic dicarboximide such as phenylene-bis (xylyl carbodiimide); aliphatic polycarbodiimides such as polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, polycyclohexylene carbodiimide, poly (methylene dicyclohexyl carbodiimide) and poly (isophorone carbodiimide); poly (carbodiimides) such as poly (phenylene carbodiimides), poly (naphthylene carbodiimides), poly (toluene carbodiimides), poly (methyl diisopropylphenylene carbodiimides), poly (triethyl phenylene carbodiimides), poly (diethyl phenylene carbodiimides), poly (triisopropyl phenylene carbodiimides), poly (xylylene carbodiimides), poly (tetramethyl xylylene carbodiimides), poly (methylene diphenylene carbodiimides), poly [ methylene bis (methyl phenylene) carbodiimides ], and other aromatic polycarbodiimides.

Examples of the commercial products of the carbodiimide-based curing agent include "bil V-02B", "bil V-03", "bil V-04K", "bil V-07" and "bil V-09" manufactured by the japanese spinning chemical company; the "oven P", "oven P400" and "oven 510" manufactured by the company of the oven.

The acid anhydride-based curing agent may be a curing agent having 1 or more acid anhydride groups in 1 molecule, and preferably a curing agent having 2 or more acid anhydride groups in 1 molecule. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5- (2, 5-dioxotetrahydro-3-furyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3'-4,4' -diphenyl sulfone tetracarboxylic dianhydride, 1, 3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphtho [1,2-C ] furan-1, 3-dione, ethylene glycol bis (trimellitate), and styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid. Examples of the commercial products of the acid anhydride-based curing agent include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by New Japan physical and chemical Co., ltd; "YH-306", "YH-307" manufactured by Mitsubishi chemical corporation; "HN-2200", "HN-5500" manufactured by Hitachi chemical Co., ltd; "EF-30", "EF-40", "EF-60", "EF-80", etc. made by the company of the UK.

Examples of the amine-based curing agent include curing agents having 1 or more, preferably 2 or more amino groups in 1 molecule, and examples thereof include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, and among these, aromatic amines are preferable from the viewpoint of exhibiting the desired effects of the present invention. The amine-based curing agent is preferably a primary amine or a secondary amine, more preferably a primary amine. As a specific example of the amine-based curing agent, examples thereof include 4,4' -methylenebis (2, 6-dimethylaniline), 4' -diaminodiphenylmethane, 4' -diaminodiphenylsulfone, 3' -diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine 4,4' -diaminodiphenyl ether, 3' -dimethyl-4, 4' -diaminobiphenyl, 2' -dimethyl-4, 4' -diaminobiphenyl, 3' -dihydroxybenzidine, 2-bis (3-amino-4-hydroxyphenyl) propane 3, 3-dimethyl-5, 5-diethyl-4, 4-diphenyl methane diamine, 2-bis (4-aminophenoxy) phenyl) propane, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, and the like. As the amine-based curing agent, commercially available ones can be used, and examples thereof include "SEIKACURE-S" manufactured by Searche; "KAYABOND C-200S", "KAYABOND C-100", "mountain A-A", "mountain A-B", "mountain A-S" by Kagaku corporation; and "d" by mitsubishi chemical company.

Specific examples of the benzoxazine-based curing agent include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE chemical company; "HFB2006M" manufactured by Showa Polymer Co., ltd; "P-d", "F-a", etc. manufactured by the chemical industry Co., ltd.

Examples of the cyanate-based curing agent include difunctional cyanate resins such as bisphenol a dicyanate, polyphenol cyanate (oligo (3-methylene-1, 5-phenylene cyanate)), 4 '-methylenebis (2, 6-dimethylphenyl cyanate), 4' -ethylenediphenyl dicyanate, hexafluorobisphenol a dicyanate, 2-bis (4-cyanate) phenylpropane, 1-bis (4-cyanate phenylmethane), bis (4-cyanate-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate phenyl-1- (methylethylene)) benzene, bis (4-cyanate phenyl) sulfide and bis (4-cyanate phenyl) ether; polyfunctional cyanate resins derived from phenol novolacs, cresol novolacs, and the like, partially triazinized prepolymers of these cyanate resins, and the like. Specific examples of the cyanate ester curing agent include "PT30" and "PT60" manufactured by eun corporation (both of which are phenol novolac type polyfunctional cyanate ester resins), "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol a dicyanate is triazinized into a trimer).

Examples of the thiol curing agent include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), and tris (3-mercaptopropyl) isocyanurate.

(C) The equivalent weight of the reaction group of the curing agent is preferably 50g/eq to 3000g/eq, more preferably 100g/eq to 1000g/eq, still more preferably 100g/eq to 500g/eq, particularly preferably 100g/eq to 300g/eq. The equivalent of reactive groups is the mass of the (C) curing agent per 1 equivalent of reactive groups.

The molar ratio of the total of the epoxy groups of the (B) epoxy resin to the total of the reactive groups of the (C) curing agent (the molar number of the epoxy groups: the molar number of the reactive groups) in the resin composition is preferably in the range of 1:0.2 to 1:2, more preferably in the range of 1:0.3 to 1:1.5, still more preferably in the range of 1:0.4 to 1:1.

The content of the curing agent (C) in the resin composition is not particularly limited, but is preferably 40 mass% or less, more preferably 30 mass% or less, further preferably 25 mass% or less, and particularly preferably 20 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. The lower limit of the content of the curing agent (C) in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is set to 100 mass%, it may be, for example, 0 mass% or more, 0.1 mass% or more, 1 mass% or more, preferably 5 mass% or more, more preferably 8 mass% or more, and particularly preferably 10 mass% or more.

When the active ester-based curing agent is contained in the curing agent (C), the content of the active ester-based curing agent in the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and particularly preferably 7% by mass or more, from the viewpoint of suppressing the dielectric loss tangent to be lower when the nonvolatile component in the resin composition is 100% by mass. When the amount of the curing agent (C) in the resin composition is 100% by mass, the content of the active ester-based curing agent in the resin composition is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and particularly preferably 50% by mass or more, from the viewpoint of suppressing the dielectric loss tangent to be lower.

When the phenol-based curing agent is contained in the curing agent (C), the content of the phenol-based curing agent in the resin composition is preferably 0.5 mass% or more, more preferably 1 mass% or more, particularly preferably 2 mass% or more, and the upper limit may be 10 mass% or less, 5 mass% or less, from the viewpoint of further improving the curability, when the nonvolatile component in the resin composition is 100 mass%.

Thermoplastic resin (D)

The resin composition of the present invention may further contain (D) a thermoplastic resin as an optional component. (D) The thermoplastic resin is a component of the epoxy resin (B) which does not meet the above description.

Examples of the thermoplastic resin (D) include polyimide resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins. In one embodiment, (D) the thermoplastic resin preferably comprises a thermoplastic resin selected from polyimide resins and phenoxy resins, more preferably comprises a phenoxy resin. In addition, the thermoplastic resin may be used alone or in combination of 1 or more than 2.

Specific examples of the polyimide resin include "SLK-6100" manufactured by the company Chemie Co., ltd; and "brush コ and" brush コ "manufactured by new japan physicochemical company, PN 20.

Examples of the phenoxy resin include phenoxy resins having 1 or more kinds of skeletons selected from bisphenol a skeletons, bisphenol F skeletons, bisphenol S skeletons, bisphenol acetophenone skeletons, novolak skeletons, biphenyl skeletons, fluorene skeletons, dicyclopentadiene skeletons, norbornene skeletons, naphthalene skeletons, anthracene skeletons, adamantane skeletons, terpene skeletons, and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

Specific examples of the phenoxy resin include "1256" and "4250" manufactured by mitsubishi chemical company (both are phenoxy resins having bisphenol a skeleton); "YX8100" manufactured by Mitsubishi chemical corporation (phenoxy resin containing bisphenol S skeleton); "YX6954" manufactured by Mitsubishi chemical corporation (phenoxy resin containing bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nile chemical company; "YX7200B35", "YL7500BH30", "YX6954BH30", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482", etc. manufactured by Mitsubishi chemical corporation.

Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include "electrochemical drive 4000-2", "electrochemical drive 5000-a", "electrochemical drive 6000-C", "electrochemical drive 6000-EP" manufactured by electrochemical industries; the inox series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, BM series, etc. manufactured by the Water chemical industry Co.

Examples of the polyolefin resin include ethylene-based copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; polyolefin polymers such as polypropylene and ethylene-propylene block copolymers.

Examples of the polybutadiene resin include a hydrogenated polybutadiene skeleton-containing resin, a hydroxyl-containing polybutadiene resin, a phenolic hydroxyl-containing polybutadiene resin, a carboxyl-containing polybutadiene resin, an acid anhydride-containing polybutadiene resin, an epoxy-containing polybutadiene resin, an isocyanate-containing polybutadiene resin, a urethane-containing polybutadiene resin, and a polyphenylene ether-polybutadiene resin.

Specific examples of the polyamideimide resin include "headstock HR11NN" and "headstock HR16NN" manufactured by eastern spinning corporation. Specific examples of the polyamide-imide resin include modified polyamide-imides such as "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane skeleton) manufactured by hitachi chemical company.

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by sumitomo chemical company.

Specific examples of polysulfone resins include a solver, a polysulfone "P1700" and a polysulfone "P3500" manufactured by the company of the matrixing.

Specific examples of the polyphenylene ether resin include "NORYL SA90" manufactured by SABIC corporation. Specific examples of the polyetherimide resin include "clo tower" manufactured by GE corporation.

Examples of the polycarbonate resin include a hydroxyl group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxyl group-containing carbonate resin, an acid anhydride group-containing carbonate resin, an isocyanate group-containing carbonate resin, and a urethane group-containing carbonate resin. Specific examples of the polycarbonate resin include "FPC0220" manufactured by mitsubishi gas chemical company; "T6002", "T6001" (polycarbonate diol) manufactured by Asahi chemical Co., ltd; "C-1090", "C-2090", "C-3090" (polycarbonate diol) made by the company Larray. Specific examples of the polyether-ether-ketone resin include "su-i-K" manufactured by sumitomo chemical company.

Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, 1, 3-propanediol terephthalate resin, 1, 3-propanediol naphthalate resin, and cyclohexanedimethanol terephthalate resin.

From the viewpoint of further improving the film formability, the weight average molecular weight (Mw) of the thermoplastic resin (D) is preferably 5,000 or more, more preferably 8,000 or more, still more preferably 10,000 or more, particularly preferably 20,000 or more, and is preferably 100,000 or less, more preferably 70,000 or less, still more preferably 60,000 or less, particularly preferably 50,000 or less.

The content of the thermoplastic resin (D) in the resin composition is not particularly limited, but is preferably 20 mass% or less, more preferably 15 mass% or less, still more preferably 10 mass% or less, still more preferably 5 mass% or less, and particularly preferably 3 mass% or less, based on 100 mass% of the nonvolatile components in the resin composition. (D) The lower limit of the content of the thermoplastic resin relative to the total nonvolatile components is not particularly limited, but is, for example, 0 mass% or more, 0.01 mass% or more, 0.1 mass% or more, preferably 0.5 mass% or more, and more preferably 1 mass% or more, based on 100 mass% of the nonvolatile components in the resin composition.

Curing accelerator (E)

The resin composition of the present invention further comprises (E) a curing accelerator as an optional component. (E) The curing accelerator has a function as a curing catalyst for accelerating the curing of the (B) epoxy resin.

Examples of the curing accelerator (E) include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. (E) The curing accelerator preferably contains a curing accelerator selected from imidazole-based curing accelerators and amine-based curing accelerators, and particularly preferably contains an amine-based curing accelerator. (E) The curing accelerator may be used alone or in combination of 1 or more than 2.

Examples of the phosphorus-based curing accelerator include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis (tetrabutylphosphonium) pyromellitic acid, tetrabutylphosphonium hexahydrophthalate, tetrabutylphosphonium-2, 6-bis [ (2-hydroxy-5-methylphenyl) methyl ] -4-methylphenoxide, and di-t-butylmethylphosphonium tetraphenylborate; aromatic phosphonium salts such as methyltriphenyl phosphonium bromide, ethyltriphenyl phosphonium bromide, propyltriphenyl phosphonium bromide, butyltriphenyl phosphonium bromide, benzyltriphenyl phosphonium chloride, tetraphenyl phosphonium bromide, p-tolyltrimethyl phosphonium tetra-p-tolylborate, tetraphenyl phosphonium tetraphenyl borate, tetraphenyl phosphonium tetra-p-tolylborate, triphenylethyl phosphonium tetraphenyl borate, tris (3-methylphenyl) ethylphosphinium tetraphenyl borate, tris (2-methoxyphenyl) ethylphosphinium tetraphenyl borate, (4-methylphenyl) triphenylphosphine thiocyanate, tetraphenyl phosphonium thiocyanate, butyltriphenyl phosphonium thiocyanate, and the like; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactant; aliphatic phosphines such as tributylphosphine, tri-t-butylphosphine, trioctylphosphine, di-t-butyl (2-butenyl) phosphine, di-t-butyl (3-methyl-2-butenyl) phosphine, and tricyclohexylphosphine; dibutyl phenyl phosphine, di-tert-butyl phenyl phosphine, methyl diphenyl phosphine, ethyl diphenyl phosphine, butyl diphenyl phosphine, diphenyl cyclohexyl phosphine, triphenyl phosphine, tri-o-tolyl phosphine, tri-m-tolyl phosphine, tri-p-tolyl phosphine, tri (4-ethylphenyl) phosphine, tri (4-propylphenyl) phosphine, tri (4-isopropylphenyl) phosphine, tri (4-butylphenyl) phosphine, tri (4-tert-butylphenyl) phosphine, tri (2, 4-dimethylphenyl) phosphine, tri (2, 5-dimethylphenyl) phosphine, tri (2, 6-dimethylphenyl) phosphine, tri (3, 5-dimethylphenyl) phosphine, tri (2, 4, 6-trimethylphenyl) phosphine, tri (2, 6-dimethyl-4-ethoxyphenyl) phosphine, tri (2-methoxyphenyl) phosphine, tri (4-ethoxyphenyl) phosphine, tri (4-tert-butoxyphenyl) phosphine, diphenyl-2-pyridylphosphine, 1, 2-bis (diphenyl) phosphino-ethane, 1, 3-bis (diphenyl) phosphine, 2 '-diphenyl) phosphine, bis (2, 2' -diphenyl) phosphine, bis (2, 2-diphenyl) phosphine, etc.

Examples of the urea-based curing accelerator include 1, 1-dimethylurea; aliphatic dimethylureas such as 1, 3-trimethylurea, 3-ethyl-1, 1-dimethylurea, 3-cyclohexyl-1, 1-dimethylurea, and 3-cyclooctyl-1, 1-dimethylurea; 3-phenyl-1, 1-dimethylurea, 3- (4-chlorophenyl) -1, 1-dimethylurea, 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea, 3- (3-chloro-4-methylphenyl) -1, 1-dimethylurea, 3- (2-methylphenyl) -1, 1-dimethylurea, 3- (4-methylphenyl) -1, 1-dimethylurea, 3- (3, 4-dimethylphenyl) -1, 1-dimethylurea, 3- (4-isopropylphenyl) -1, 1-dimethylurea, 3- (4-methoxyphenyl) -1, 1-dimethylurea, 3- (4-nitrophenyl) -1, 1-dimethylurea, 3- [4- (4-methoxyphenoxy) phenyl ] -1, 1-dimethylurea, 3- [4- (4-chlorophenoxy) phenyl ] -1, 1-dimethylurea, N- (1, 4-phenylene) bis (N ', N ' -dimethylurea, N- (4-dimethylphenyl) bis (N, N ' -dimethyltoluene) urea, etc.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolylguanidine), dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1-dimethylbiguanide, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1- (o-tolylguanide).

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2' -methylimidazole- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -undecylimidazole ] -ethyl-s-triazine, and 2, 4-diamino-6- [2' -methyl-4 ' -imidazolyl ] -s-triazine Imidazole compounds such as 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline; and adducts of imidazole compounds with epoxy resins.

As the imidazole-based curing accelerator, commercially available products may be used, and examples thereof include "1B2PZ", "2MZA-PW", "2PHZ-PW" and "C11Z-A" manufactured by four-national chemical industry Co., ltd; "P200-H50" manufactured by Mitsubishi chemical corporation, etc.

Examples of the metal curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate; organic copper complexes such as copper (II) acetylacetonate; organic zinc complexes such as zinc acetylacetonate (II); organic iron complexes such as iron (III) acetylacetonate; organonickel complexes such as nickel (II) acetylacetonate; organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine; 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1, 8-diazabicyclo (5, 4, 0) -undecene, and the like.

Examples of the amine-based curing accelerator include commercially available products such as "MY-25" manufactured by rufin corporation.

The content of the (E) curing accelerator in the resin composition is not particularly limited, but is preferably 5 mass% or less, more preferably 1 mass% or less, further preferably 0.5 mass% or less, particularly preferably 0.3 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. The lower limit of the content of the (E) curing accelerator in the resin composition is not particularly limited, and the content of the nonvolatile component in the resin composition may be, for example, 0 mass% or more, 0.001 mass% or more, 0.01 mass% or more, or the like, based on 100 mass%.

(F) other additives ]

The resin composition of the present invention may further contain (F) an optional other additive as a nonvolatile component. Examples of such an additive include radical polymerizable compounds having a vinylphenyl group, (meth) acryl group, maleimide group, and the like; radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; thermosetting resins other than epoxy resins, such as epoxy acrylate resins, urethane resins, cyanate resins, benzoxazine resins, unsaturated polyester resins, melamine resins, and silicone resins; organocopper compounds, organozinc compounds, organocobalt compounds, and other organometallic compounds; coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, phenothiazine, etc.; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; thickeners such as BENTON and montmorillonite; an antifoaming agent such as an organosilicon antifoaming agent, an acrylic antifoaming agent, a fluorine antifoaming agent, and a vinyl resin antifoaming agent; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as ureidosilane; adhesion-imparting agents such as triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, and triazine-based adhesion-imparting agents; antioxidants such as hindered phenol antioxidants; fluorescent whitening agents such as stilbene derivatives; a surfactant such as a fluorine-based surfactant and an organosilicon-based surfactant; flame retardants such as phosphorus flame retardants (for example, phosphate compounds, phosphazene compounds, phosphinic acid compounds, and red phosphorus), nitrogen flame retardants (for example, melamine sulfate), halogen flame retardants, and inorganic flame retardants (for example, antimony trioxide); a dispersant such as a phosphate dispersant, a polyoxyalkylene dispersant, an acetylene dispersant, a silicone dispersant, an anionic dispersant, and a cationic dispersant; borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, carboxylic anhydride-based stabilizers, and the like. (F) The other additives may be used alone in 1 kind, or may be used in combination in an arbitrary ratio of 2 or more kinds. The content of the other additive (F) may be appropriately set by those skilled in the art.

(G) organic solvent ]

In addition to the above-mentioned nonvolatile components, the resin composition of the present invention may further contain an optional organic solvent as a volatile component. As the organic solvent (G), a known solvent may be suitably used, and the kind thereof is not particularly limited. Examples of the organic solvent (G) include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ -butyrolactone; ether solvents such as tetrahydrofuran, 1, 4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyldiglycol acetate, γ -butyrolactone, methyl methoxypropionate, and the like; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (G) The organic solvents may be used alone or in combination of 2 or more kinds in any ratio.

The content of the organic solvent (G) in the varnish-like resin composition before drying is not particularly limited, and is, for example, preferably 40 mass% or less, more preferably 30 mass% or less, further preferably 20 mass% or less, and particularly preferably 10 mass% or less, based on 100 mass% of the total components in the resin composition. The content of the organic solvent (G) in the resin composition forming the dried resin composition layer in the resin sheet is not particularly limited, but is preferably 5 mass% or less, more preferably 3 mass% or less, further preferably 2 mass% or less, and particularly preferably 1 mass% or less, based on 100 mass% of the total components in the resin composition.

< Method for producing resin composition >

The resin composition of the present invention can be produced, for example, by adding (A) an inorganic filler, (B) an epoxy resin, optionally, (C) a curing agent, optionally, (D) a thermoplastic resin, optionally, (E) a curing accelerator, optionally, (F) other additives, and optionally, (G) an organic solvent to an optional production vessel in any order and/or partially or all at the same time and kneading them. The inventors found that: the fracture of the hollow inorganic filler particles, which is a cause of the decrease in mechanical strength, which is one of the problems of the present invention, occurs due to kneading of the resin composition.

As the kneading method, a method using a kneader is exemplified. As the kneading machine, an open-type kneading machine such as a two-roll mill, a three-roll mill, or the like can be used; an internal mixer such as a high-speed rotary mixer.

In one embodiment, when the resin composition of the present invention further comprises (B) an epoxy resin and (C) a curing agent in addition to (a) an inorganic filler, it is preferable to produce the resin composition by the following operations, for the purpose of suppressing as much as possible an undesired reaction between (B) an epoxy resin and (C) a curing agent: adding (A) an inorganic filler, (B) an epoxy resin, optionally (F) other additives and optionally (G) an organic solvent to an arbitrary preparation vessel in an arbitrary order and/or partially or completely at the same time, kneading with a first kneader (hereinafter referred to as "first kneading") before adding (C) a curing agent, further adding (C) a curing agent, optionally (D) a thermoplastic resin, optionally (E) a curing accelerator, optionally (F) other additives and optionally (G) an organic solvent in an arbitrary order and/or partially or completely at the same time after kneading, and kneading with a second kneader (hereinafter referred to as "second kneading").

As the first mixer and the second mixer, the above-mentioned mixers can be used, respectively, and the first mixer is preferably an open mixer, more preferably a three-roll mill, and the second mixer is preferably an internal mixer, more preferably a high-speed rotary mixer.

The resin composition may be defoamed under low pressure conditions such as vacuum after kneading or while kneading.

< Properties of resin composition >

To date it has been found that: when conventional hollow inorganic particles (hollow inorganic filler) having a small average particle diameter of 5 μm or less and a low average circularity are used in the resin composition, the hollow inorganic particles are broken due to the local presence of pressure in the convex portions of the particles in the kneading step for dispersing the resin composition before curing, and fragments of the hollow inorganic particles become the starting points of the breakage, and the mechanical strength of the cured product is lowered.

In addition, in one embodiment, as described above, it is sometimes preferable to perform the "first mixing" first using an open mixer having a very high shear stress such as a two-roll mill or a three-roll mill as the first mixer, and thereafter to perform the "second mixing" using an internal mixer having a small shear stress such as a high-speed rotary mixer as the second mixer, but it is found that: in this case, when conventional hollow inorganic particles are used, breakage is likely to occur during "first kneading" in which the shear stress is large, as compared with "second kneading".

The resin composition of the present invention is a resin composition containing (A) an inorganic filler, and (A) the inorganic filler contains (A-1) a hollow inorganic filler having an average circularity of 0.6 or more and an average particle diameter of 5 [ mu ] m or less, and therefore breakage of the hollow inorganic filler is less likely to occur during kneading, and a cured product having excellent mechanical strength and a low relative dielectric constant can be obtained.

The cured product of the resin composition of the present invention has a dielectric loss tangent (Df) of 0.010 or less, preferably 0.0090 or less, more preferably 0.0085 or less, still more preferably 0.0080 or less, still more preferably 0.0075 or less, and particularly preferably 0.0070 or less, when measured at 5.8GHz and 23 ℃ as in test example 2 described below.

The cured product of the resin composition of the present invention has a relative dielectric constant (Dk) of 3.0 or less, preferably 2.9 or less, more preferably 2.8 or less, still more preferably 2.7 or less, particularly preferably 2.6 or less, or 2.5 or less, when measured at 5.8GHz and 23 ℃ as in test example 2.

The cured product of the resin composition of the present invention has a characteristic of excellent mechanical strength. Therefore, in one embodiment, the elongation at break of the cured product measured as in test example 3 below is preferably 0.5% or more, more preferably 1.0% or more, still more preferably 1.3% or more, still more preferably 1.5% or more, and particularly preferably 1.7% or more, as measured at 23 ℃. The upper limit of the elongation at break is not particularly limited, and is usually 10% or less and 5% or less.

In one embodiment, the cured product of the resin composition of the present invention has a characteristic of low coefficient of linear thermal expansion (CTE). Therefore, in one embodiment, the coefficient of linear thermal expansion (CTE) of the cured product measured as in test example 1 below is preferably 40 ppm/DEG C or less, more preferably 35 ppm/DEG C or less, still more preferably 30 ppm/DEG C or less, and particularly preferably 25 ppm/DEG C or less. The lower limit of the coefficient of linear thermal expansion (CTE) is not particularly limited, but is set to 1 ppm/DEG C or more.

< Use of resin composition >

The resin composition of the present invention can be suitably used as a resin composition for insulation use, and can be particularly suitably used as a resin composition for forming an insulation layer. Specifically, it can be suitably used as a resin composition for forming an insulating layer (a resin composition for forming an insulating layer for forming a conductor layer) for forming a conductor layer (including a rewiring layer) formed on an insulating layer. In addition, in a printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of the printed wiring board (a resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention can be widely used in applications requiring a resin composition, such as resin sheets, sheet-like laminates such as prepregs, solder resists, underfills, die attach materials, semiconductor sealing materials, hole-filling resins, and component embedding resins.

In addition, for example, in the case of manufacturing a semiconductor chip package through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for a rewiring formation layer (a resin composition for a rewiring formation layer formation) and a resin composition for sealing a semiconductor chip (a resin composition for a semiconductor chip sealing), which are insulating layers for forming a rewiring layer. In manufacturing the semiconductor chip package, a rewiring layer may be further formed on the sealing layer.

(1) A step of laminating a temporary fixing film on a base material;

(2) A step of temporarily fixing the semiconductor chip to the temporary fixing film;

(3) Forming a sealing layer on the semiconductor chip;

(4) A step of peeling the base material and the temporary fixing film from the semiconductor chip;

(5) Forming a rewiring forming layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film are peeled off; and

(6) And forming a rewiring layer as a conductor layer on the rewiring layer.

Further, the resin composition of the present invention can realize an insulating layer excellent in component embedding property, and therefore, can be suitably used even when the printed wiring board is a component-embedded wiring board.

< Sheet-like laminate >

The resin composition of the present invention can be used in the form of a varnish by coating, and is industrially generally suitable for use in the form of a sheet-like laminate containing the resin composition.

The sheet-like laminate is preferably a resin sheet or prepreg shown below.

In one embodiment, a resin sheet includes a support, and a resin composition layer provided on the support, the resin composition layer being formed from the resin composition of the present invention.

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of thinning of the printed wiring board and providing a cured product excellent in insulation even if the cured product of the resin composition is a film. The lower limit of the thickness of the resin composition layer is not particularly limited, and is usually 5 μm or more and 10 μm or more.

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

When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter, abbreviated as "PET") and polyethylene naphthalate (hereinafter, abbreviated as "PEN"), polycarbonates (hereinafter, abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyether sulfides (PES), polyether ketones, polyimide, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

The support may be subjected to matting treatment, corona treatment, antistatic treatment, or the like on the surface to be joined to the resin composition layer.

As the support, a support with a release layer having a release layer on a surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the support with a release layer includes, for example, 1 or more release agents selected from alkyd resins, polyolefin resins, urethane resins, and silicone resins. Examples of the support having a release layer include PET films having a release layer containing an alkyd-based release agent as a main component, namely, "SK-1", "AL-5", "AL-7" manufactured by the company of Koku; "LumirrorT 60" manufactured by Toli corporation; a "heart" manufactured by diner corporation; and "a" made by the company of rattle.

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

In one embodiment, the resin sheet may further include an optional layer as needed. Examples of the optional layer include a support-based protective film provided on a surface of the resin composition layer that is not bonded to the support (i.e., a surface on the opposite side of the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust and the like to the surface of the resin composition layer can be suppressed.

The resin sheet can be produced by, for example, applying a liquid resin composition or a resin varnish to a support using a die coater or the like, and drying the same to form a resin composition layer.

The organic solvent may be the same as the organic solvent described as a component of the resin composition. The organic solvent may be used alone or in combination of at least 2 kinds.

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

The resin sheet may be rolled into a roll shape for storage. In the case where the resin sheet has a protective film, the protective film can be peeled off for use.

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

The sheet-like fibrous base material used in the prepreg is not particularly limited, and glass cloth, aramid nonwoven fabric, liquid crystal polymer nonwoven fabric, or the like can be used as a base material for the prepreg, which is commonly used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-like fibrous base material is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fibrous base material is not particularly limited. Typically 10 μm or more.

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

The thickness of the prepreg may be set in the same range as the resin composition layer in the resin sheet.

The sheet-like laminate of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for insulating layer use of a printed wiring board), and can be more suitably used for forming an interlayer insulating layer of a printed wiring board (for insulating layer use of a printed wiring board).

< Printed wiring Board >

The printed wiring board of the present invention comprises an insulating layer formed from a cured product obtained by curing the resin composition of the present invention.

The printed wiring board can be manufactured using, for example, the above resin sheet and by a method including the following steps (I) and (II).

(I) Laminating the resin sheet on the inner substrate so that the resin composition layer of the resin sheet is bonded to the inner substrate;

(II) a step of forming an insulating layer by curing (e.g., thermally curing) the resin composition layer.

The "inner layer substrate" used in the step (I) is a member to be a substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be subjected to patterning. An inner layer substrate having a conductor layer (circuit) formed on one or both surfaces of the substrate is sometimes referred to as an "inner layer circuit substrate". In addition, intermediate products, in which an insulating layer and/or a conductor layer should be further formed in manufacturing a printed wiring board, are also included in the "inner layer substrate" mentioned in the present invention. In the case where the printed wiring board is a component-embedded wiring board, an inner layer substrate having a component embedded therein may be used.

Lamination of the inner layer substrate and the resin sheet can be performed by, for example, thermocompression bonding the resin sheet to the inner layer substrate from the support side. As a member for thermocompression bonding the fat sheet to the inner substrate (hereinafter, also referred to as "thermocompression bonding member"), for example, a heated metal plate (SUS end plate or the like), a metal roller (SUS roller) or the like can be cited. It is preferable that the heat pressure bonding member is not directly pressed against the resin sheet, but is pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably 60 to 160 ℃, more preferably 80 to 140 ℃, and the thermocompression bonding pressure is preferably 0.098 to 1.77MPa, more preferably 0.29 to 1.47MPa, and the thermocompression bonding time is preferably 20 to 400 seconds, more preferably 30 to 300 seconds. The lamination is preferably performed under reduced pressure of 26.7hPa or less.

Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressure laminators manufactured by Ming machine manufacturing company, vacuum applicators manufactured by Nikko-Materials company, batch vacuum pressure laminators, and the like.

After lamination, the laminated resin sheets can be smoothed by pressurizing the thermocompression bonding member at normal pressure (atmospheric pressure), for example, from the support body side. The pressurizing conditions for the smoothing treatment may be the same as the above-described lamination thermocompression bonding conditions. The smoothing treatment may be performed by a commercially available laminator. The lamination and smoothing treatment may be continuously performed using the commercially available vacuum laminator.

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 cured (for example, thermally cured) to form an insulating layer composed of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and conditions generally employed in forming an insulating layer of a printed wiring board can be used.

For example, the heat curing conditions of the resin composition layer may vary depending on the type of the resin composition, and in one embodiment, the curing temperature is preferably 120 to 240 ℃, more preferably 150 to 220 ℃, and even more preferably 170 to 210 ℃. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and still more preferably 15 minutes to 100 minutes.

The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature of 50 to 120 ℃, preferably 60 to 115 ℃, more preferably 70 to 110 ℃ for 5 minutes or more, preferably 5 to 150 minutes, more preferably 15 to 120 minutes, and still more preferably 15 to 100 minutes.

In the case of manufacturing a printed wiring board, (III) a step of forming a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further performed. These steps (III) to (V) may be performed according to various methods known to those skilled in the art for manufacturing a printed wiring board. In the case where the support is removed after the step (II), the removal of the support may be performed between the step (II) and the step (III), between the step (III) and the step (IV), or between the step (IV) and the step (V). The insulating layer and the conductor layer of the steps (II) to (V) may be repeatedly formed as necessary to form a multilayer wiring board.

In other embodiments, the printed wiring board of the present invention may be manufactured using the above prepreg. The manufacturing method is basically the same as in the case of using a resin sheet.

The step (III) is a step of forming a hole in the insulating layer, whereby a via hole, a through hole, or the like can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer, or the like. The size and shape of the holes can be appropriately determined according to the design of the printed wiring board.

The step (IV) is a step of roughening the insulating layer. In this step (IV), generally, the dirt is removed. The step and condition of the roughening treatment are not particularly limited, and known steps and conditions generally used in forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer may be roughened by sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralization liquid.

The swelling liquid used in the roughening treatment is not particularly limited, and examples thereof include an alkali solution, a surfactant solution, and the like, preferably an alkali solution, and more preferably a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include parts by parts, and the like. The swelling treatment with the swelling solution is not particularly limited, and the swelling treatment may be performed by immersing the insulating layer in the swelling solution at 30 to 90 ℃ for 1 to 20 minutes, for example. From the viewpoint of suppressing swelling of the resin of the insulating layer to a proper level, it is preferable to impregnate the insulating layer in a swelling liquid at 40 to 80 ℃ for 5 to 15 minutes.

The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 100 ℃ for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10 mass%. Examples of the commercially available oxidizing agent include alkaline permanganate solutions such as "コ fluke, by the company of maycross, maybush, コ fluke, maybush CP", "maybush, and the like.

The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and is commercially available, examples of the polymer include "parts of the polymer" by the company of je, i.e., parts of the polymer "by the company of je.

The treatment with the neutralizing solution may be performed by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30 to 80 ℃ for 5 to 30 minutes. From the viewpoint of handling, the object roughened with the oxidizing agent is preferably immersed in the neutralization solution at 40 to 70 ℃ for 5 to 20 minutes.

In one embodiment, the arithmetic average roughness (Ra) of the surface of the insulating layer after the roughening treatment is not particularly limited, and is preferably 500nm or less, more preferably 400nm or less, and still more preferably 300nm or less. The lower limit is not particularly limited, and may be, for example, 1nm or more, 2nm or more, or the like. The root mean square roughness (Rq) of the roughened insulating layer surface is preferably 500nm or less, more preferably 400nm or less, and still more preferably 300nm or less. The lower limit is not particularly limited, and may be, for example, 1nm or more, 2nm or more, or the like. The arithmetic average roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

The step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises 1 or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer, and examples of the alloy layer include a layer formed of an alloy of 2 or more metals selected from the above (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, from the viewpoints of versatility, cost, ease of patterning, and the like of the conductor layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, and still more preferably a single metal layer of copper is preferable.

The conductor layer may have a single-layer structure or a multilayer structure in which 2 or more single metal layers or alloy layers made of different types 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 nickel-chromium alloy.

The thickness of the conductor layer is usually 3 μm to 35 μm, preferably 5 μm to 30 μm, depending on the design of the desired printed wiring board.

In one embodiment, the conductor layer may be formed by plating. For example, the surface of the insulating layer can be plated by a conventionally known technique such as a half-addition method or a full-addition method to form a conductor layer having a desired wiring pattern, and it is preferable to form the conductor layer by the half-addition method from the viewpoint of ease of production. Hereinafter, an example in which a conductor layer is formed by a half-addition method is shown.

First, a plating seed layer is formed on the surface of an insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer, which exposes a portion of the plating seed layer in accordance with a desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like, whereby a conductor layer having a desired wiring pattern can be formed.

In other embodiments, the conductor layer may be formed using a metal foil. When the conductor layer is formed using a metal foil, the step (V) is preferably performed between the steps (I) and (II). For example, after the step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. Lamination of the resin composition layer and the metal foil may be performed by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Thereafter, a conductor layer having a desired wiring pattern can be formed by using a metal foil on the insulating layer and conventional known techniques such as a subtractive process and a modified semi-additive process.

The metal foil can be produced by a known method such as electrolysis or rolling. Examples of the commercial products of the metal foil include HLP foil manufactured by JX rikenite metal company and JXUT-III foil; 3EC-III foil, TP-III foil, etc. manufactured by Mitsui Metal mine Co.

< Semiconductor device >

The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

As the semiconductor device, various semiconductor devices used for electric products (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, motorcycles, automobiles, electric trains, ships, aircraft, and the like) are exemplified.

Examples

Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to these examples. The terms "part(s)" and "%" used in the following expression means "part(s) by mass" and "% by mass", respectively, unless otherwise explicitly stated. In the following description, the temperature condition, particularly when the temperature is not specified, is set at normal temperature (25 ℃) and the pressure condition, particularly when the pressure is not specified, is set at normal pressure (1 atm).

Example 1]

30 Parts of bisphenol A type epoxy resin (828 US made by Mitsubishi chemical corporation, epoxy equivalent of about 180 g/eq.) and 30 parts of biphenyl type epoxy resin (NC 3000H made by Japanese chemical corporation, epoxy equivalent of about 269 g/eq.) were heated and dissolved in 55 parts of solvent naphtha while stirring, and then cooled to room temperature. To this mixed solution, 144 parts of hollow silica particles 1 (average particle diameter of 2.0 μm, average circularity of 0.7, and porosity of 20 vol%) surface-treated with an aminosilane-based coupling agent (KBM 573 made by Xinyue chemical industry Co.) and 80 parts of non-hollow silica particles (SO-C2 made by Santa Clay Co., ltd., average particle diameter of 0.5 μm, average circularity of 0.9) surface-treated with an aminosilane-based coupling agent (KBM 573 made by Xinyue chemical industry Co.) were added, and kneaded by a three-roll mill to uniformly disperse the particles. To this roll dispersion were mixed 14 parts of a triazine skeleton-containing phenol-based curing agent ("LA-3018-50P" manufactured by DIC Co., ltd., a 2-methoxypropanol solution having a hydroxyl equivalent weight of about 151 and a solid content of 50%), 40 parts of a dicyclopentadiene-type active ester compound (HPC-8000-65T "manufactured by DIC Co., ltd., an active group equivalent weight of about 223, a toluene solution having a nonvolatile content of 65 mass%), 20 parts of a phenoxy resin (YX 6954BH30 manufactured by Mitsubishi chemical Co., ltd., a 1:1 mixed solution of MEK having a solid content of 30% and cyclohexanone), 6 parts of a curing accelerator (DMAP", 4-dimethylaminopyridine, a MEK solution having a solid content of 5 mass%) and uniformly dispersed by a high-speed rotary stirrer, to prepare a varnish-like resin composition.

Example 2 ]

A varnish-like resin composition was prepared in the same manner as in example 1 except that the amount of the surface-treated hollow silica particles 1 (average particle diameter: 2.0 μm, average circularity: 0.7, and porosity: 20% by volume) was changed from 144 parts to 208 parts, and 80 parts of the surface-treated non-hollow silica particles (SO-C2, average particle diameter: 0.5 μm, and average circularity: 0.9) were not used.

Example 3]

A varnish-like resin composition was prepared in the same manner as in example 1 except that 144 parts of hollow silica particles 1 (average particle diameter: 2.0 μm, average circularity: 0.7, and porosity: 20% by volume) subjected to surface treatment were replaced with 36 parts of hollow aluminosilicate particles (MG-005, average particle diameter: 1.6 μm, and porosity: 80% by volume) manufactured by pacific cement corporation.

Example 4]

A varnish-like resin composition was prepared in the same manner as in example 1 except that 30 parts of a naphthol-type epoxy resin (ESN 475V, epoxy equivalent 332g/eq, manufactured by daycare chemical company) was used instead of 30 parts of a biphenyl-type epoxy resin (NC 3000H, epoxy equivalent 269g/eq, manufactured by daycare chemical company).

Example 5 ]

A varnish-like resin composition was prepared in the same manner as in example 1 except that 30 parts of a biphenyl type epoxy resin (NC 3000H, epoxy equivalent: about 269g/eq. Manufactured by japan chemical company) was used instead of 30 parts of a biscresol type epoxy resin (YX 4000HK, epoxy equivalent: about 185g/eq. Manufactured by mitsubishi chemical company).

Example 6 ]

A varnish-like resin composition was prepared in the same manner as in example 1 except that 40 parts of a dicyclopentadiene-type active ester compound (HPC-8000-65T, available from DIC Co., ltd., an active group equivalent of about 223, and a toluene solution having a nonvolatile content of 65% by mass) was used instead of 40 parts of the dicyclopentadiene-type active ester compound (HPC-8150-62T, available from DIC Co., ltd., an active group equivalent of about 229, and a toluene solution having a nonvolatile content of 62% by mass), and 42 parts of a naphthalene-type active ester compound was used.

Example 7 ]

A varnish-like resin composition was prepared in the same manner as in example 1 except that the amount of dicyclopentadiene-type active ester compound (HPC-8000-65T, available from DIC Co., ltd.) used was changed from 40 parts to 20 parts, and 21 parts of naphthalene-type active ester compound (HPC-8150-62T, available from DIC Co., ltd.), available from active group equivalent weight of 229 and available from non-volatile component was used as a toluene solution having a non-volatile component of 65 mass%.

Comparative example 1 ]

A varnish-like resin composition was prepared in the same manner as in example 1 except that 144 parts of surface-treated hollow silica particles 1 (average particle diameter: 2.0 μm, average circularity: 0.7, and porosity: 20% by volume) were not used, and the amount of surface-treated non-hollow silica particles "SO-C2", average particle diameter: 0.5 μm, and average circularity: 0.9 "manufactured by the company of tikokusu was changed from 80 parts to 260 parts.

Comparative example 2]

A varnish-like resin composition was prepared in the same manner as in example 1 except that 144 parts of surface-treated hollow silica particles 1 (average particle diameter: 2.0 μm, average circularity: 0.7, and porosity: 20% by volume) were not used, and instead of 80 parts of surface-treated non-hollow silica particles (SO-C2, average particle diameter: 0.5 μm, average circularity: 0.9) 80 parts of surface-treated non-hollow silica particles (IMSILA-8, average particle diameter: 2.2 μm, and average circularity: 0.5) were used, each of which was surface-treated with an aminosilane-based coupling agent (KBM 573, believed to be the same manner as in example 1).

Comparative example 3 ]

A varnish-like resin composition was prepared in the same manner as in example 1 except that, instead of 144 parts of the hollow silica particles 1 (average particle diameter: 2.0 μm, average circularity: 0.7 and porosity: 20% by volume) subjected to the surface treatment, 135 parts of hollow silica particles 2 (average particle diameter: 2.6 μm, average circularity: 0.5 and porosity: 25% by volume) subjected to the surface treatment with an aminosilane-based coupling agent (KBM 573, made by the company of the shiny-chemical industry) were used.

< Test example a: determination of the average particle size of the inorganic filler particles-

100Mg of the inorganic filler particles used in each of examples and comparative examples and 10g of methyl ethyl ketone were weighed and placed in a vial, and dispersed by ultrasonic waves for 10 minutes. The particle size distribution of the inorganic particles was measured by a flow cell method using a laser diffraction type particle size distribution measuring apparatus ("LA-960" manufactured by horiba, ltd.) with the wavelength of the light source used being blue and red, based on volume. From the resulting particle size distribution, the average particle size of the inorganic particles is calculated as the median particle size.

< Test example B: calculation of the porosity of the inorganic filler particles-

The densities of the inorganic filler particles used in each of the examples and comparative examples were measured using a true density measuring apparatus ("ULTRAPYCNOMETER 1000" manufactured by quanthactome corporation). In this measurement, nitrogen was used as the measurement gas. Thereafter, the measured value D _M of the density of the inorganic filler and the theoretical value D _T of the mass density of the material forming the inorganic filler particles are substituted into the above-described formula (2), and the porosity P of the inorganic filler particles is calculated. The theoretical value D _T of the mass density of silica was set to 2.2g/cm ³.

< Test example C: calculation of the average circularity of the inorganic filler particles-

The inorganic filler particles used in each of examples and comparative examples were subjected to image analysis using a particle shape image analysis apparatus (PITA-04, manufactured by setafung corporation). Silica particles dispersed in methyl ethyl ketone (hereinafter abbreviated as "MEK") as a diluting solvent were injected into an analyzer, and data of projection area S and circumference L of particles in an image were counted for 1000 or more particles per sample using a 20-fold optical lens, and substituted into the above-described formula (1), and circularity was calculatedThe average circularity is calculated from the calculated circularities.

< Test example 1: measurement of linear thermal expansion coefficient of cured product ]

As a support, a PET film (AL 5, thickness 38 μm, manufactured by doctor blade corporation) with an alkyd resin-based release layer was prepared. The varnish-like resin compositions prepared in examples and comparative examples were uniformly applied to the release layer of the support so that the thickness of the dried resin composition layer became 40. Mu.m, and dried at 80 to 120℃for 5 minutes (average 100 ℃) to prepare a resin sheet.

The resin sheet having a thickness of 40 μm of the prepared resin composition layer was heated at 200℃for 90 minutes to thermally cure the resin composition layer, and then the support was peeled off to obtain a cured product for evaluation. The cured product for evaluation was cut into test pieces having a width of 5mm and a length of 15 mm. The test piece was subjected to thermomechanical analysis by a tensile load method using a thermomechanical analysis device (Thermo Plus TMA 8310) manufactured by the company of the rakuck. Specifically, after the test piece was mounted on the thermal mechanical analyzer, the test piece was continuously measured 2 times under a measurement condition of a load of 1g and a temperature rise rate of 5 ℃/min. In addition, in 2 measurements, the linear thermal expansion coefficient (ppm/. Degree. C.) in the plane direction was calculated in the range of 25℃to 150 ℃.

< Test example 2: determination of relative permittivity and dielectric loss tangent of cured product >

The cured product for evaluation obtained by the same method as in test example 1 was cut into test pieces having a width of 2mm and a length of 80 mm. The test piece was subjected to a cavity resonance perturbation method using "HP8362B" manufactured by AgilentTechnologies, whereby the relative permittivity and dielectric loss tangent were measured at a measurement frequency of 5.8GHz and a measurement temperature of 23 ℃. The measurement was performed on 2 test pieces, and an average value was calculated.

< Test example 3: determination of elongation at Break of cured product ]

The tensile test was performed on the cured product for evaluation obtained in the same manner as in test example 1 by using TENSILON universal tester (RTC-1250A manufactured by ORIENTEC Co.) according to Japanese Industrial Standard (JIS K7127), and the elongation at break (%) was measured.

The content of the nonvolatile components of the resin compositions of examples and comparative examples, the calculation results of the test examples, and the measurement results are shown in table 1 below.

As shown in the table, it can be seen that: by using a resin composition containing (A) an inorganic filler, wherein (A) the inorganic filler contains (A-1) a hollow inorganic filler having an average circularity of 0.6 or more and an average particle diameter of 5 μm or less, a cured product having excellent mechanical strength and a low relative dielectric constant can be obtained.

Claims

1. A resin composition comprising (A) an inorganic filler, wherein,

2. The resin composition according to claim 1, wherein the content of the component (A) is 40% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.

3. The resin composition according to claim 1, wherein the average particle diameter of the component (A-1) is 0.3 μm or more.

4. The resin composition according to claim 1, wherein the porosity of the component (A-1) is 15% by volume or more.

5. The resin composition according to claim 1, wherein the component (A-1) is formed of silica.

6. The resin composition according to claim 1, wherein the content of the component (A-1) is 30% by mass or more based on 100% by mass of the total component (A) in the resin composition.

7. The resin composition of claim 1, further comprising (B) an epoxy resin.

8. The resin composition according to claim 1, further comprising (C) a curing agent.

9. The resin composition according to claim 8, wherein component (C) comprises an active ester-based curing agent.

10. The resin composition according to claim 8, wherein component (C) comprises a naphthalene-type active ester-based curing agent.

11. The resin composition according to claim 8, wherein component (C) comprises a phenol-based curing agent.

12. The resin composition of claim 1, further comprising (D) a thermoplastic resin.

13. The resin composition according to claim 12, wherein component (D) comprises a phenoxy resin.

14. The resin composition according to claim 1, wherein the elongation at break of the cured product of the resin composition is 1.0% or more when measured at 23 ℃.

15. The resin composition according to claim 1, wherein a linear thermal expansion coefficient of a cured product of the resin composition is 30ppm/°c or less.

16. A cured product of the resin composition according to any one of claims 1 to 15.

17. A sheet-like laminate comprising the resin composition according to any one of claims 1 to 15.

18. A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of claims 1 to 15 provided on the support.

19. A printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 15.

20. A semiconductor device comprising the printed wiring board according to claim 19.