KR20190020623A - Resin composition - Google Patents

Abstract

Provided is a resin composition capable of obtaining an insulating layer having a low dielectric constant and excellent temperature stability of a dielectric tangent. The resin composition comprises: (A) an epoxy resin; (B) a maleimide compound; (C) an inorganic filler; and (D) a fluorine-based filler, wherein the amount of the component (B) is 10-70 mass% relative to 100 mass% of the component (A).

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition, a sheet-like laminated material, a circuit board and a semiconductor device.

BACKGROUND ART [0002] As a manufacturing technique of a circuit board, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately laminated on an inner layer substrate is known. The insulating layer is generally formed by obtaining a resin composition layer as a coating film of a resin varnish containing a resin composition and curing the resin composition layer. For example, Patent Document 1 discloses a resin composition containing an epoxy resin, a curing agent, and a fluorine resin filler, wherein the content of the fluorine resin filler is 50 to 85% by mass with respect to the solid content of the resin composition A resin composition is described.

Japanese Laid-Open Patent Publication No. 2016-166347

The resin composition for forming the insulating layer generally contains a large amount of thermosetting resin from the viewpoint of achieving high insulation performance. As this thermosetting resin, an epoxy resin was generally used. On the contrary, the present inventors studied the application of a fluorine-based filler to a resin composition containing an epoxy resin in order to develop an insulating layer having a low dielectric constant.

The present inventor has also attempted to apply a resin composition containing an epoxy resin and a fluorine-based filler to an insulating layer of an antenna circuit board of a radar as described above. It has been found that the range of detectability of the radar equipped with this antenna circuit board varies depending on the temperature. For example, even if the detectable range at a certain temperature is as wide as 20 m, the detectable range at a different temperature may be narrowed to 5 m.

SUMMARY OF THE INVENTION The present invention has been devised in view of the above problems, and it is an object of the present invention to provide a resin composition capable of suppressing a change in the detectable range of a radar by temperature when installed on an antenna circuit board of a radar, A sheet-like laminate material comprising the resin composition; And a circuit board and a semiconductor device including an insulating layer made of a cured product of the resin composition.

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems. As a result, the inventor of the present invention has obtained the knowledge that the cause of the change in temperature of the radar detectable range is the temperature stability of the dielectric tangent of the insulating layer. Specifically, when the dielectric loss tangent of the insulating layer of the antenna circuit board of the radar is changed by the temperature, the loss magnitude of the antenna circuit board is changed by the temperature, so that the sensitivity of the antenna circuit board is changed by temperature, As a result, a change was caused by the temperature of the detectable range. Therefore, the present inventors have found that the above problems can be solved by a resin composition capable of obtaining an insulating layer having excellent dielectric stability of dielectric loss tangent, and completed the present invention.

That is, the present invention includes the following.

[1] A resin composition comprising (A) an epoxy resin, (B) a maleimide compound, (C) an inorganic filler, and (D) a fluorine-based filler, wherein the amount of the component (B) By mass to 10% by mass to 70% by mass.

(2) A resin composition comprising (A) an epoxy resin and (D) a fluorine-based filler, wherein the dielectric tangent at -10 ° C, 25 ° C and 100 ° C of the cured product obtained by heat- (-10 ° C) / Df (25 ° C) of Df (-10 ° C) relative to Df (25 ° C) when Df (-10 ° C), Df Is 85% to 115%, and the ratio Df (100 占 폚) / Df (25 占 폚) of Df (100 占 폚) to Df (25 占 폚) is 85% to 115%.

[3] The resin composition according to [2], which comprises (B) a maleimide compound.

[4] The resin composition according to any one of [1] to [3], wherein the component (D) is a fluorine-based polymer particle.

[5] The resin composition according to any one of [1] to [4], wherein the component (D) is a polytetrafluoroethylene particle.

[6] A resin composition according to any one of [1] to [5], which comprises a resin having (E) an unsaturated hydrocarbon group.

[7] The resin composition according to [6], wherein the component (E) has at least one unsaturated hydrocarbon group selected from the group consisting of an acrylic group, a methacrylic group, a styryl group, an allyl group, a vinyl group and a propenyl group.

[8] The resin composition according to [6] or [7], wherein the component (E) has a vinyl group and has a cyclic ether structure having five or more ring members.

[9] The resin composition according to any one of [1] to [8], which is for forming an insulating layer of a circuit board.

[10] A sheet-like laminated material comprising the resin composition according to any one of [1] to [9].

[11] A circuit board comprising an insulating layer made of a cured product of the resin composition according to any one of [1] to [9].

[12] A semiconductor device comprising the circuit board according to [11].

According to the present invention, there is provided a resin composition capable of suppressing changes in the detectable range of a radar due to temperature when installed on an antenna circuit board of a radar and obtaining an insulating layer with a low dielectric constant; A sheet-like laminate material comprising the resin composition; A circuit board and a semiconductor device including the insulating layer made of the cured product of the resin composition can be provided.

Hereinafter, the present invention will be described in detail with reference to embodiments and examples. It should be noted, however, that the present invention is not limited to the embodiments and examples described below, and can be arbitrarily changed without departing from the scope of the present invention and its equivalent scope.

In the following description, the amount of each component in the resin composition is a value relative to 100 mass% of the nonvolatile component in the resin composition unless otherwise specified.

In the following description, the term " dielectric constant " refers to a dielectric constant unless otherwise specified.

[One. Resin composition according to the first embodiment]

[1.1. Outline of resin composition]

The resin composition according to the first embodiment of the present invention comprises (A) an epoxy resin, (B) a maleimide compound, (C) an inorganic filler, and (D) a fluorine-based filler. Here, the term " fluorine-based " means a fluorine-containing one. The term " fluorine-based filler " refers to a filler containing a fluorine-containing compound as a material. Further, in this resin composition, the amount of the maleimide compound (B) is within a predetermined range.

The cured product of such a resin composition has a low dielectric constant. Further, the cured product of such a resin composition has excellent temperature stability of dielectric tangent. Therefore, by using the above resin composition, it is possible to obtain an insulating layer having a low dielectric constant, which is excellent in temperature stability of dielectric loss tangent and can suppress changes in temperature of the radar detectable range in the case where it is provided on an antenna circuit board of a radar, A desired effect of the present invention can be obtained.

[1.2. (A) epoxy resin]

Examples of the epoxy resin as the component (A) include epoxy resins such as a bicyclanol 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 , Trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type Epoxy resins, glycidyl ester type epoxy resins, cresol novolak type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, A resin, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a naphthylene ether Epoxy resins, there may be mentioned trimethyl olhyeong epoxy resin, tetraphenyl ethane epoxy resin. The epoxy resin may be used singly or in combination of two or more kinds.

As the epoxy resin (A), an epoxy resin having a cyclic structure such as an alicyclic structure and an aromatic cyclic structure in addition to an epoxy group is preferable because a change in characteristics due to temperature is small. Among them, an aromatic epoxy resin is preferable from the viewpoint of lowering the average linear thermal expansion coefficient of the insulating layer. Here, the aromatic epoxy resin refers to an epoxy resin whose molecule contains an aromatic skeleton. The aromatic skeleton is a chemical structure generally defined as an aromatic group, and includes not only a monocyclic structure such as a benzene ring, but also a polycyclic aromatic structure such as a naphthalene ring and an aromatic heterocyclic structure. Among them, the epoxy resin (A) is preferably a bisphenol A type epoxy resin, a biquilene type epoxy resin, a biphenyl aralkyl type epoxy resin, a naphthylene ether type epoxy resin, a naphthalene type 4 Functional epoxy resin and naphthol-type epoxy resin, and a biscylenol-type epoxy resin is particularly preferable.

The resin composition preferably contains, as the epoxy resin (A), an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of obtaining a desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule to (A) 100% by mass of the nonvolatile component of the epoxy resin is preferably 50% by mass or more, More preferably not less than 60% by mass, particularly preferably not less than 70% by mass.

As the epoxy resin, a liquid epoxy resin (hereinafter sometimes referred to as " liquid epoxy resin ") and a solid epoxy resin (hereinafter sometimes referred to as " solid epoxy resin " have. As the resin composition (A), an epoxy resin may contain only liquid epoxy resin, may contain only solid epoxy resin, and may contain a combination of liquid epoxy resin and solid epoxy resin. (A) By using a combination of a liquid epoxy resin and a solid epoxy resin as the epoxy resin, it is possible to improve the flexibility of the resin composition layer or to improve the fracture strength of the cured product of the resin composition.

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable, and an aromatic liquid epoxy resin having two or more epoxy groups in one molecule is more preferable.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolak type epoxy resin , An alicyclic epoxy resin having an ester skeleton, a cyclohexane-type epoxy resin, a cyclohexane dimethanol-type epoxy resin, a glycidylamine-type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a glycidylamine type epoxy resin , A bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin and a naphthalene type epoxy resin are more preferable, and a bisphenol A type epoxy resin is particularly preferable.

Specific examples of the liquid epoxy resin include " HP4032 ", " HP4032D ", " HP4032SS " (naphthalene type epoxy resin) manufactured by DIC Corporation; "828US", "jER828US", "jER828EL", "825", "Epikote 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "JER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; &Quot; jER152 " (phenol novolak type epoxy resin) manufactured by Mitsubishi Chemical Corporation; 630 ", " 630LSD " (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; ZX1059 " (a mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin) manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.; EX-721 " (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation; &Quot; Celloxide 2021P " (an alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Company; &Quot; PB-3600 " (epoxy resin having a butadiene structure) manufactured by Daicel Company; ZX1658 " and " ZX1658GS " (liquid 1,4-glycidyl cyclohexane type epoxy resin) manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., and the like. These may be used singly or in combination of two or more.

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

Examples of the solid epoxy resin include a biscylenol type epoxy resin, a biphenyl aralkyl type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin , Naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin and tetraphenylethane type epoxy resin are preferable, A naphthalene ether type epoxy resin, a naphthalene type tetrafunctional epoxy resin and a naphthol type epoxy resin are more preferable, and a biscylenol type epoxy resin is particularly preferable.

Specific examples of the solid epoxy resin include " HP4032H " (naphthalene type epoxy resin) manufactured by DIC Corporation; HP-4700 ", " HP-4710 " (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; HP-7200 " (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; EXA-7311-G4 "," EXA-7311-G4S ", and" HP6000 "(manufactured by DIC Corporation," HP-7200HH "," HP-7200H "," EXA-7311 " Naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; NC7000L " (naphthol novolak type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; Quot; NC3000H ", " NC3000 ", " NC3000L ", and " NC3100 " (biphenyl aralkyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; &Quot; ESN475V " (naphthol type epoxy resin) manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.; ESN485 " (naphthol novolac type epoxy resin) manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.; YX4000H ", " YX4000 ", and " YL6121 " (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; &Quot; YX4000HK " (biquileneol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; &Quot; PG-100 ", " CG-500 " (Bisphenol AF type epoxy resin) manufactured by Osaka Gas Chemical Co., Ltd.; &Quot; YL7760 " (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; &Quot; YL7800 " (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; &Quot; jER1010 " (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Quot; jER1031S " (tetraphenyl ethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used singly or in combination of two or more.

(A) When the liquid epoxy resin and the solid epoxy resin are used in combination as the epoxy resin, their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1: 0.1 to 1:15, more preferably 1 : 0.5 to 1:10, particularly preferably 1: 1 to 1: 8. When the mass ratio of the liquid epoxy resin to the solid epoxy resin is in the above range, favorable tackiness can be obtained when used in the form of an adhesive film. In addition, when used in the form of an adhesive film, sufficient flexibility can be obtained and handling properties can be improved. Further, the breaking strength of the cured product of the resin composition can be effectively increased.

The epoxy equivalent of the epoxy resin (A) is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, still more preferably 110 to 1000. When the epoxy equivalent of the epoxy resin (A) is in the above range, the crosslinked density of the cured product of the resin composition becomes sufficient, and an insulating layer having a small surface roughness can be obtained. The epoxy equivalent is a mass of a resin containing one equivalent of an epoxy group and can be measured in accordance with JIS K7236D.

The weight-average molecular weight of the epoxy resin (A) is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500, from the viewpoint of achieving the desired effect of the present invention. The weight average molecular weight of a resin such as an epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

The amount of the epoxy resin (A) in the resin composition is preferably 3% by mass or more, more preferably 3% by mass or more, more preferably 100% by mass or less, Is not less than 5% by mass, particularly preferably not less than 9% by mass, preferably not more than 70% by mass, more preferably not more than 50% by mass, particularly preferably not more than 30% by mass.

[1.3. (B) maleimide compound]

The maleimide compound as the component (B) is a compound containing a maleimide group represented by the following formula (B1) in the molecule.

(B1)

The number of maleimide groups per molecule of the maleimide compound (B) may be one, but is preferably 2 or more, preferably 10 or less, more preferably 6 or less, particularly preferably 3 or less to be. By using the maleimide compound (B) having two or more maleimide groups per molecule, the desired effect of the present invention can be remarkably obtained, and in particular, the temperature stability of the dielectric tangent of the cured product can be effectively improved.

The maleimide compound (B) preferably contains an aromatic skeleton in combination with a maleimide group. By using the maleimide compound (B) containing an aromatic skeleton, the desired effect of the present invention can be remarkably obtained, and in particular, the temperature stability of the dielectric tangent of the cured product can be effectively improved. In particular, the maleimide compound (B) preferably contains a benzene ring as an aromatic skeleton.

Examples of the maleimide compound (B) include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'- Diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide- (2,2,2- 4-trimethylhexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, (4-maleimidophenoxy) benzene, and the like.

As the maleimide compound (B), polyphenylmethane maleimide represented by the formula (B2) and phenylenebismaleimide represented by the formula (B3) are particularly preferable from the viewpoint of obtaining the desired effect of the present invention remarkably . In the formula (B2), n represents an integer of 0 or more.

(B2)

(B3)

Specific examples of the (B) maleimide compound include "BMI-1000" manufactured by Daisuke Seiko Co., "BMI" (4,4'-diphenylmethane bismaleimide) manufactured by K. &Quot; BMI-2000 " (polyphenylmethane maleimide) manufactured by Daiwa Kasei Kogyo Co., Ltd.; &Quot; BMI-3000 " (m-phenylenebismaleimide) manufactured by Daiwa Kasei Kogyo Co., Ltd.; BMI-4000 " manufactured by Daiwa Kasei Kogyo Co., Ltd., " BMI-80 " (bisphenol A diphenyl ether bismaleimide) BMI-5100 "manufactured by Daiwa Kasei Kogyo Co., Ltd.," BMI-70 "(3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide) ; BMI-7000 " (4-methyl-1,3-phenylenebismaleimide) manufactured by Daikin Industries, Ltd.; &Quot; BMI-TMH " (1,6'-bismaleimide (2,2,4-trimethyl) hexane) manufactured by Daiwa Kasei Corporation; &Quot; BMI-6000 " (4,4'-diphenyl ether bismaleimide) manufactured by Daikin Industries, Ltd.; &Quot; BMI-8000 " (4,4'-diphenyl sulfone bismaleimide) manufactured by Daiwa Kasei Kogyo Co., Ltd.; 1,3-bis (3-maleimidophenoxy) benzene manufactured by Daiwa Kasei Kogyo Co., Ltd.; 1,3-bis (4-maleimidophenoxy) benzene manufactured by Daiwa Kasei Kogyo Co., Ltd.; &Quot; ANILIX-MI " manufactured by Mitsui Kagaku Co., Ltd., and the like. The maleimide compound (B) may be used singly or in combination of two or more.

The maleimide compound (B) can be prepared, for example, by reacting maleic anhydride with a suitable amine compound.

The amount of the maleimide compound (B) in the resin composition is preferably 10% by mass or more, more preferably 11% by mass or more, particularly preferably 12% by mass or more, relative to 100% by mass of the epoxy resin (A) Preferably 70 mass% or less, more preferably 69 mass% or less, and particularly preferably 68 mass% or less. When the amount of the (B) maleimide compound is in the above range, the temperature stability of the dielectric loss tangent of the cured product of the resin composition can be improved.

The amount of the maleimide compound (B) in the resin composition is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, particularly preferably 1.0% by mass or more based on 100% by mass of the nonvolatile component in the resin composition , Preferably 7.0 mass% or less, more preferably 6.7 mass% or less, particularly preferably 6.2 mass% or less. When the amount of the (B) maleimide compound is in the above range, the desired effect of the present invention can be obtained remarkably, and the temperature stability of the dielectric loss tangent of the cured product can be effectively improved.

[1.4. (C) inorganic filler]

As the material of the inorganic filler as the component (C), for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, , Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, Barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly suitable from the viewpoint of obtaining a desired effect of the present invention remarkably. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Among them, spherical silica is preferable. The inorganic filler (C) may be used singly or in combination of two or more kinds.

Usually, the inorganic filler (C) is contained in the resin composition in the form of particles. The average particle diameter of the inorganic filler (C) is preferably 0.01 占 퐉 or more, more preferably 0.05 占 퐉 or more, particularly preferably 0.1 占 퐉 or more, and preferably 5.0 占 or more, from the viewpoint of achieving a desired effect of the present invention remarkably. Mu m or less, more preferably 2.0 mu m or less, and further preferably 1.0 mu m or less. When the average particle diameter of the inorganic filler (C) is in the above range, the circuit filling property of the resin composition layer can be improved or the surface roughness of the insulating layer can be reduced.

(C) Examples of commercially available inorganic fillers include " SP60-05 " and " SP507-05 " manufactured by Shinnitetsu Sumikin Materials Company; "YC100C", "YA050C", "YA050C-MJE" and "YA010C" manufactured by Adomatex Co., "UFP-30" manufactured by Denka Corporation; Quot; NSS-3N ", " NSS-4N ", and " NSS-5N " manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2" and "SO-C1" manufactured by Adomatex Co., Ltd.

(C) The average particle diameter of particles such as inorganic fillers can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the particles can be measured on the volume basis using a laser diffraction scattering particle size distribution measuring apparatus, and the average particle diameter can be obtained as the median diameter from the particle size distribution. The sample to be measured can be preferably those obtained by dispersing particles in a solvent such as water by ultrasonic waves. As the laser diffraction scattering type particle diameter distribution measuring apparatus, "LA-500" manufactured by Horiba Seisakusho Co., Ltd. and the like can be used.

The specific surface area of the inorganic filler (C) is preferably not less than 1 m 2 / g, more preferably not less than 2 m 2 / g, particularly preferably not less than 3 m 2 / g, from the viewpoint of achieving a desired effect of the present invention . The upper limit is not particularly limited, but is preferably 60 m 2 / g or less, 50 m 2 / g or less, or 40 m 2 / g or less. The specific surface area can be obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring apparatus (Macsorb HM-1210, manufactured by Mountain Tex) according to the BET method, and calculating the specific surface area using the BET multi-point method.

(C) The inorganic filler may be surface-treated with any surface-treating agent. Examples of the surface treatment agent include coupling agents such as amino silane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents and titanate coupling agents; Alkoxysilane compounds; Organosilazane compounds, and the like. The surface treatment with these surface treatment agents can improve the moisture resistance and dispersibility of the inorganic filler (C).

Examples of commercial products of surface treatment agents include KBM403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM803 (3-mercaptopropyltrimethoxy Silane), KBE903 (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM573 (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin- KBM-4803 " manufactured by Shin-Etsu Chemical Co., Ltd. (manufactured by Shin-Etsu Chemical Co., Ltd.) (long-chain epoxy type Silane coupling agents). The surface treatment agent may be used singly or in combination of two or more kinds.

The degree of the surface treatment by the surface treatment agent can be evaluated by the carbon amount per unit surface area (C) of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler (C), the carbon content per unit surface area of the inorganic filler (C) is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / Or more, particularly preferably 0.2 mg / m 2 or more. On the other hand, the amount of carbon is preferably 1 mg / m 2 or less, more preferably 0.8 mg / m 2 or less from the viewpoint of suppressing the melt viscosity of the resin varnish and the increase of the melt viscosity in the sheet form, And not more than 0.5 mg / m 2.

The amount of carbon per unit surface area of the inorganic filler (C) can be measured by washing the surface-treated inorganic filler (C) with a solvent (for example, methyl ethyl ketone (hereinafter may be abbreviated as "MEK" can do. Specifically, a sufficient amount of MEK and inorganic filler (C) surface-treated with a surface treatment agent are mixed and ultrasonically cleaned at 25 占 폚 for 5 minutes. Subsequently, the supernatant liquid is removed and the nonvolatile component is dried, and then the amount of carbon per unit surface area (C) of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba Seisakusho Co., Ltd. can be used.

The amount of the inorganic filler (C) in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and particularly preferably 10% by mass or more based on 100% by mass of the non- Preferably 20 mass% or more, preferably 80 mass% or less, more preferably 70 mass% or less, further preferably 60 mass% or less, particularly preferably 50 mass% or less. (C) Since the amount of the inorganic filler is the lower limit value or more of the above range, the thermal expansion rate of the cured product of the resin composition can be lowered, and warping of the insulating layer can be suppressed. Further, when the amount of the inorganic filler (C) is not more than the upper limit of the above range, the mechanical strength of the cured product of the resin composition can be improved, and the resistance to elongation can be increased.

[1.5. (D) Fluorine-based filler]

The fluorine-based filler as the component (D) is a filler containing a compound containing a fluorine atom as a material. The fluorine-based filler is generally in the form of particles. Therefore, as the fluorine-based filler (D), particles containing a compound containing a fluorine atom as a material are generally used.

Examples of the material of the fluorine-based filler (D) include a fluorine-based polymer and a fluorine-based rubber. Of these, a fluorine-based polymer is preferable from the viewpoint of reducing the dielectric constant of the insulating layer. Therefore, fluorine-based polymer particles are preferable as the fluorine-based filler (D).

Examples of the fluorine-based polymer include polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene propene copolymer (FEP), ethylene / tetrafluoroethylene copolymer (ETFE) (TFE / PDD), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyfluorinated Vinyl (PVF). These may be used singly or in combination of two or more.

Of these, polytetrafluoroethylene is preferable as the fluorine-based polymer from the viewpoint of particularly reducing the dielectric constant of the insulating layer. Therefore, as the fluorine-based filler (D), polytetrafluoroethylene particles as particles containing polytetrafluoroethylene are preferable.

The weight average molecular weight of the fluorine-based polymer is preferably 5,000,000 or less, more preferably 4,000,000 or less, and particularly preferably 3,000,000 or less, from the viewpoint of achieving the desired effect of the present invention.

The average particle diameter of the fluorine-based filler (D) is preferably 0.05 μm or more, more preferably 0.08 μm or more, particularly preferably 0.10 μm or more, preferably 10 μm or less, more preferably 5 μm or less, And particularly preferably 4 mu m or less. When the average particle diameter of the fluorine-based filler (D) is in the above range, the desired effect of the present invention can be obtained remarkably and the dispersibility of the fluorine-based filler (D) in the resin composition can be improved. The average particle diameter of the fluorine-containing filler (D) can be measured by a laser diffraction / scattering method based on the (Mie) scattering theory, similarly to (C) inorganic filler.

Examples of commercially available products of the fluorine-based filler (D) include "Lubron L-2", "Lubron L-5", "Lubron L-5F" manufactured by Daikenko; "FluonPTFE L-170JE", "FluonPTFEL-172JE" and "FluonPTFE L-173JE" manufactured by Asahi Glass Co., Ltd.; "KTL-500F", "KTL-2N" and "KTL-1N" manufactured by Kitamura Co., Ltd.; And " TLP10F-1 " manufactured by Mitsui-DuPont Fluorochemicals.

The fluorine-based filler (D) may be surface-treated. For example, the fluorine-based filler (D) may be surface-treated with an optional surface treatment agent. Examples of the surface treatment agent include surfactants such as nonionic surfactants, amphoteric surfactants, cationic surfactants and anionic surfactants; Inorganic fine particles, and the like. From the viewpoint of affinity, it is preferable to use a fluorine-based surfactant as the surface treatment agent. Specific examples of the fluorine-based surfactant include "Surflon S-243" (perfluoroalkyl ethylene oxide adduct) manufactured by AGC Seiyam Chemical Co., Ltd.; Megapak F-251 "," Megapack F-477 "," Megapack F-553 "," Megapark R-40 "," Megapark R-43 " "; FTX-218 " and " Futagent 610FM " manufactured by NEOS.

The amount of the fluorine-based filler (D) in the resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, and particularly preferably 20% by mass or more based on 100% by mass of the nonvolatile component in the resin composition, Preferably 80 mass% or less, more preferably 60 mass% or less, particularly preferably 40 mass% or less. When the amount of the fluorine-based filler (D) is in the above range, the desired effect of the present invention can be obtained remarkably, and the dielectric constant of the cured product of the resin composition can be effectively reduced.

The amount of the fluorine-based filler (D) in the resin composition is preferably 20% by mass or more, more preferably 30% by mass or more, particularly preferably 100% by mass or more, based on the total 100% by mass of the inorganic filler (D) Is not less than 35 mass%, preferably not more than 90 mass%, more preferably not more than 70 mass%, particularly preferably not more than 50 mass%. When the amount of the fluorine-based filler (D) is in the above range, the desired effect of the present invention can be obtained remarkably, and the dielectric constant of the cured product of the resin composition can be effectively reduced.

[1.6. (E) Resin Having an Unsaturated Hydrocarbon Group]

The resin composition may contain, as optional components, a resin having an unsaturated hydrocarbon group (E) in addition to the above components. In the following description, the "resin having an unsaturated hydrocarbon group" as the component (E) is sometimes referred to as "unsaturated resin". The carbon-carbon unsaturated bond may be contained in only one molecule of the unsaturated resin (E), or a plurality of carbon-carbon unsaturated bonds may be contained. The cured product of the resin composition comprising (E) the unsaturated resin usually includes a molecular structure moiety in which the unsaturated bond of the unsaturated resin (E) is formed by the reaction. Thereby, the polarity of the cured product becomes small, and the value of the dielectric loss tangent can be reduced. In addition, the dispersibility of the fluorine-based filler (D) can be improved by the unsaturated resin (E). Therefore, since the uniformity of the composition of the resin composition is improved, the adhesion of the cured product to the conductor layer can be further improved.

The unsaturated (E) resin contains an unsaturated hydrocarbon group in the molecule of the (E) unsaturated resin. The unsaturated hydrocarbon group is preferably at least one group selected from the group consisting of an acrylic group, a methacrylic group, a styryl group and an olefin group. Here, the "olefin group" refers to an aliphatic hydrocarbon group having a carbon-carbon double bond in the molecule. Preferable examples of the olefin group include an allyl group, a vinyl group, and a propenyl group. Accordingly, it is preferable that the unsaturated resin (E) has at least one unsaturated hydrocarbon group selected from the group consisting of an acryl group, a methacryl group, a styryl group, an allyl group, a vinyl group and a propenyl group.

The unsaturated resin (E) is preferably a compound having a cyclic ether structure having five or more ring members. In the following description, the "compound having a cyclic ether structure having five or more ring members" is sometimes referred to as "unsaturated cyclic ether compound". The unsaturated cyclic ether compound usually has a limited movement of molecules, so that the dielectric tangent can be effectively lowered.

The unsaturated cyclic ether compound may contain a carbon-carbon unsaturated bond in the cyclic ether structure or may include a cyclic ether structure.

The unsaturated cyclic ether compound may contain only one cyclic ether structure or a plurality of unsaturated cyclic ether compounds.

The cyclic ether structure may have a monocyclic structure containing only one ring, a polycyclic structure containing two or more rings, or a condensed ring structure containing a condensed ring.

The number of oxygen atoms contained in one cyclic ether structure is preferably 1 or more, more preferably 2 or more, preferably 5 or less, more preferably 4 or less, from the viewpoint of obtaining a desired effect of the present invention remarkably. , And more preferably 3 or less.

The cyclic ether structure is preferably a 5- to 10-membered ring, more preferably a 5- to 8-membered ring, and even more preferably a 5- to 6-membered ring. Specific examples of the cyclic ether structure having five or more ring members include a furan structure, a tetrahydrofuran structure, a dioxolane structure, a pyran structure, a dihydropyran structure, a tetrahydropyran structure, and a dioxane structure. Among them, a dioxane structure is preferable from the viewpoint of improving compatibility. The dioxane structure includes a 1,2-dioxane structure, a 1,3-dioxane structure and a 1,4-dioxane structure, and a 1,3-dioxane structure is preferable.

A substituent such as an alkyl group or an alkoxy group may be bonded to the cyclic ether structure. The number of carbon atoms of such a substituent is usually 1 to 6, preferably 1 to 3.

Among the above-mentioned unsaturated cyclic ether compounds, those having a vinyl group are preferable. By using an unsaturated cyclic ether compound having a vinyl group (that is, a compound having a vinyl group and having a cyclic ether structure having five or more rings) as the unsaturated resin (E), the desired effect of the present invention can be obtained remarkably. In addition, dielectric tangent of the resin composition can be effectively lowered.

Preferable examples of the unsaturated (E) unsaturated resin include a compound represented by the following formula (E1), a compound represented by the following formula (E6), and a compound represented by the following formula (E7). Among them, the compound represented by the formula (E7) is preferably an unsaturated cyclic ether compound.

(E1)

In the formula (E1), each of R ¹ to R ⁶ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. In the formula (E1), A represents a bivalent group represented by the following formula (E2) or the following formula (E3).

(E2)

In the formula (E2), B represents a divalent group represented by the following formula (E2-1), (E2-2) or (E2-3).

(E2-1)

(E2-2)

(E2-3)

In formula (E2-1), R ¹⁵ to R ¹⁸ each independently represents a hydrogen atom, an alkyl group or a phenyl group of 6 or less carbon atoms, preferably a hydrogen atom or a methyl group.

In formula (E2-2), R ¹⁹ to R ²⁶ each independently represents an alkyl group or a phenyl group of a hydrogen atom, the number of carbon atoms not more than 6, and preferably represents a hydrogen atom or a methyl group.

In the formula (E2-3), R ²⁷ to R ³⁴ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, preferably a hydrogen atom or a methyl group. In the formula (E2-3), E represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

(E3)

In the formula (E3), D represents a divalent group represented by the following formula (E4).

(E4)

In the formula (E4), each of R ⁷ to R ¹⁴ independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, preferably a hydrogen atom or a methyl group. In particular, R ⁷ , R ⁸ , R ¹³ and R ¹⁴ more preferably represent a methyl group. In the formula (E4), a and b are integers of not less than 0 but not more than 100, at least one of which is not 0. In the formula (E4), B represents a divalent group represented by the above formula (E2-1), (E2-2) or (E2-3).

The compound represented by the above formula (E1) is preferably a compound represented by the following formula (E5).

(E5)

And in the formula (E5), R ¹ to R ⁶ denotes the same as R ¹ to R ⁶ in the formula (E1), B is the same meaning as B in the formula (E2), a and b have the above formula (E4 Quot; a " and " b "

(E6)

(E7)

In the formula (E7), the ring F represents a divalent group having a cyclic ether structure having five or more ring members. The range of the cyclic ether structure is as described above. The cyclic ether structure may have a substituent bonded thereto as described above.

Examples of the divalent group having a cyclic ether structure having five or more ring members include a furan-2,5-diyl group, a tetrahydrofuran-2,5-diyl group, a dioxolane-2,5-diyl group, A dihydropyran-2,5-diyl group, a tetrahydropyran-2,5-diyl group, a 1,2-dioxane-3,6-diyl group, a 1,3- A 2,5-diyl group, a 1,4-dioxane-2,5-diyl group, and a 5-ethyl-1,3-dioxane-2,5-diyl group. Among them, 5-ethyl-1,3-dioxane-2,5-diyl group is preferable.

In the formula (E7), B ¹ and B ² each independently represent a single bond or a divalent linking group. B ¹ and B ² are preferably divalent linking groups. Examples of the divalent linking group include an alkylene group which may have a substituent, an alkynylene group which may have a substituent, an arylene group which may have a substituent, a heteroarylene group which may have a substituent, a group represented by -COO- , A group represented by -CO-, a group represented by -CONH-, a group represented by -NHCONH-, a group represented by -NHCOO-, a group represented by -C (= O) -, a group represented by -S- , A group represented by -SO-, a group represented by -NH-, and a group obtained by combining a plurality of these groups.

Examples of the substituent include a halogen atom, -OH, -OC _1-6 alkyl group, -N (C _1-6 alkyl group) ₂ , C _1-6 alkyl group, C _6-10 aryl group, -NH ₂ , -CN , -C (O) OC _1-6 alkyl group, -COOH, -C (O) H, -NO ₂ and the like. Here, the term " C _pq " (p and q are positive integers and satisfying p < q) indicates that the number of carbon atoms of the organic group described immediately after this term is p to q. For example, the expression " C _1-6 alkyl group " represents an alkyl group having 1 to 6 carbon atoms.

The substituent may further have a substituent (hereinafter may be referred to as " secondary substituent "). As the secondary substituent, for example, there can be mentioned a group such as the substituent already described.

Among them, B ¹ and B ² are selected from two or more groups selected from the group consisting of an alkylene group which may have a substituent, an alkynylene group which may have a substituent, a group represented by -COO-, and a group represented by -O- Is preferable. In particular, B ¹ and B ² are more preferably a group in which two or more groups are selected from the group consisting of an alkylene group which may have a substituent and a group represented by -COO-.

In the formula (E7), C ¹ and C ² each independently represent a functional group. Examples of the functional group include a vinyl group, a methacrylic group, an acrylic group, an allyl group, a styryl group, a propenyl group, and an epoxy group. The functional group is preferably a vinyl group.

Specific examples of the compound represented by the formula (E7) include a compound represented by the following formula (E8).

(E8)

Examples of the unsaturated (E) unsaturated resin include "OPE-2St 1200" (styrene-modified polyphenylene ether resin, number average molecular weight: 1200, equivalent to the above formula (E5)) manufactured by Mitsubishi Gas Chemical Co., Quot; A-DOG " (dioxane acrylic monomer glycol diacrylate, number average molecular weight: 326, manufactured by Shin Nakamura Kagaku Ko), YL7776 (biquilene diallyl ether resin, number average molecular weight: 331, (Corresponding to the above formula (E8)) and "KAYARAD R-604" (corresponding to the above formula (E8)) manufactured by Nippon Kayaku Co., The unsaturated resin (E) may be used singly or in combination of two or more kinds.

The number average molecular weight of the unsaturated (E) unsaturated resin is preferably 100 or more, more preferably 200 or more, preferably 10000 or less, more preferably 3000 or less. When the number average molecular weight of the unsaturated (E) unsaturated resin falls within the above range, it is possible to suppress the volatilization of the resin varnish during drying or to prevent the resin composition from having an excessive melt viscosity. The number average molecular weight can be measured by a gel permeation chromatography (GPC) method in terms of polystyrene conversion. The measurement of the number average molecular weight by the GPC method can be carried out by, for example, using "LC-9A / RID-6A" manufactured by Shimadzu Corporation as a measuring apparatus and "Shodex K-800P / K -804L / K-804L " and using chloroform as the mobile phase at a column temperature of 40 占 폚.

The amount of the unsaturated resin (E) in the resin composition is preferably not less than 1% by mass, more preferably not less than 3% by mass, and preferably not more than 15% by mass with respect to 100% by mass of the nonvolatile component in the resin composition. Preferably 10 mass% or less. The amount of the unsaturated resin (E) is at least the lower limit of the above range, the dielectric tangent of the cured product of the resin composition can be effectively lowered, and the compatibility of the resin varnish can be improved.

The mass ratio of the epoxy resin (A) and the unsaturated resin (E) (the mass of the epoxy resin (A) to the mass of the unsaturated resin (E)) is preferably in the range of 1: 0.01 to 1: 100, : 90, and more preferably in the range of 1: 0.2 to 1: 80. When the mass ratio of the epoxy resin (A) and the unsaturated resin (E) is in the above range, the compatibility of the resin composition can be improved.

[1.7. (F) Curing agent]

The resin composition may contain (F) a curing agent as an optional component in addition to the above components. The curing agent as the component (F) generally has a function of reacting with the epoxy resin (A) to cure the resin composition. Examples of such a (C) curing agent include an active ester type curing agent, a phenol type curing agent, a naphthol type curing agent, a benzoxazine type curing agent, a cyanate ester type curing agent, and a carbodiimide type curing agent. The curing agent may be used singly or in combination of two or more kinds.

As the active ester type curing agent, a compound having at least one active ester group in one molecule can be used. Among them, examples of the active ester curing agent include compounds having two or more ester groups having high reactivity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, . It is preferable that the active ester-based curing agent is obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. Particularly, from the viewpoint of improving the heat resistance, active ester type curing agents obtained from carboxylic acid compounds and hydroxy compounds are preferable, and active ester type curing agents obtained from carboxylic acid compounds and phenol compounds and / or naphthol compounds are more preferable.

Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid.

Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o- Cresol, catechol, alpha -naphthol, beta -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzene triol, dicyclopentadiene type diphenol compounds, phenol novolak, and the like. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol in one dicyclopentadiene molecule.

Specific preferred examples of the active ester-based curing agent include active ester compounds containing a dicyclopentadiene type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated phenol novolac, And an active ester compound including a benzoylate. Of these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

EXB9451 "," EXB9460 "," EXB9460S "," HPC-8000-65T "," HPC-8000-65T ", and" HPC-8000-65T "as active ester compounds containing a dicyclopentadiene type diphenol structure as commercial products of the active ester- -8000H-65TM, EXB-8000L-65TM and EXB-8150-65T (manufactured by DIC); EXB9416-70BK " (manufactured by DIC) as an active ester compound containing a naphthalene structure; &Quot; DC808 " (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing acetylated phenol novolak; &Quot; YLH1026 " (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylate of phenol novolak; &Quot; DC808 " (manufactured by Mitsubishi Chemical Corporation) as an active ester-based curing agent which is acetylated phenol novolak; YLH1026 " (manufactured by Mitsubishi Chemical Corporation), " YLH1030 " (manufactured by Mitsubishi Chemical Corp.), and YLH1048 (manufactured by Mitsubishi Chemical Corporation) as the benzoylates of phenol novolak.

As the phenol-based curing agent and naphthol-based curing agent, those having a novolak structure are preferable from the viewpoints of heat resistance and water resistance. From the viewpoint of adhesion between the insulating layer and the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a phenazine-based curing agent containing a triazine skeleton is more preferable.

Specific examples of the phenol-based curing agent and naphthol-based curing agent include "MEH-7700", "MEH-7810" and "MEH-7851" manufactured by Meiwa Kasei; NHN ", " CBN ", " GPH ", manufactured by Nippon Kayaku Co., "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V" and "SN375" manufactured by Shinnitetsu Sumi- TD-2090 "," LA-7052 "," LA-7054 "," LA-1356 "," LA-3018-50P "and" EXB-9500 "manufactured by DIC Corporation.

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

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'- Dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1- Cyanate phenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis Naphthyl phenyl) thioether, and bis (4-cyanate phenyl) ether; Polyfunctional cyanate resins derived from phenol novolak and cresol novolak; And prepolymerized prepolymers of these cyanate resins. Specific examples of the cyanate ester curing agent include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resin), "ULL-950S" (multifunctional cyanate ester resin), "BA230 BA230S75 " (a prepolymer obtained by trimerizing a part or all of bisphenol A dicyanate to form a trimer), and the like.

Specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co.,

Among the above, as the curing agent (F), an active ester curing agent is preferable from the viewpoint of obtaining a desired effect of the present invention remarkably. When the active ester type curing agent is used, the amount of the active ester type curing agent relative to 100 mass% of the (C) curing agent is preferably 10 mass% or more, more preferably 20 mass% or more, still more preferably 30 mass% , And preferably not more than 100 mass%. When the amount of the active ester type curing agent is in the above range, the desired effect of the present invention can be obtained remarkably, and the dielectric constant of the cured product of the resin composition can be effectively reduced.

The amount of the curing agent (F) in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on 100% by mass of the nonvolatile component in the resin composition, , More preferably not less than 1% by mass, preferably not more than 40% by mass, more preferably not more than 30% by mass, further preferably not more than 20% by mass.

When the epoxy group number of the epoxy resin (A) is 1, the number of active groups of the (F) curing agent is preferably 0.1 or more, more preferably 0.2 or more, further preferably 0.3 or more, preferably 1.5 or less, More preferably 1.2 or less, and further preferably 1 or less. Here, the "epoxy group number of the epoxy resin (A)" is a value obtained by adding up the values obtained by dividing the mass of the nonvolatile component (A) of the epoxy resin present in the resin composition by the epoxy equivalent. The "number of active groups of the (F) curing agent" is a value obtained by summing the values obtained by dividing the mass of the nonvolatile component of the (C) curing agent present in the resin composition by the equivalent weight of the active agent. When the number of epoxy groups in the epoxy resin (A) is 1 and the number of active groups of the (F) curing agent is in the above range, the desired effect of the present invention can be remarkably obtained and the heat resistance of the cured product do.

[1.8. (G) Curing accelerator]

The resin composition may contain a curing accelerator (G) as an optional component in addition to the above components. By using the (G) curing accelerator, curing can be promoted when the resin composition is cured.

Examples of the (G) curing accelerator include phosphorus hardening accelerators, amine hardening accelerators, imidazole hardening accelerators, guanidine hardening accelerators, metal hardening accelerators and peroxide hardening accelerators. Among them, an amine-based curing accelerator and a peroxide-based curing accelerator are particularly preferable. The (G) curing accelerator may be used singly or in combination of two or more kinds.

Examples of phosphorus hardening accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenyl Phosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. Among them, triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine; amines such as 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 8-diazabicyclo (5,4,0) -undecene. Among them, 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl- Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] -ethyl-s-triazine, 2,4- diamino-6- [ Imidazolyl- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- Triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl- , 2-phenylimidazole isocyanuric acid 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 Imidazole compounds; And adducts of an imidazole compound and an epoxy resin. Among them, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As the imidazole-based curing accelerator, a commercially available product may be used, and for example, " P200-H50 " manufactured by Mitsubishi Chemical Corporation may be mentioned.

Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, , Trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [ 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1- (o-tolyl) biguanide. Among them, dicyandiamide and 1,5,7-triazabicyclo [4.4.0] deca-5-ene are preferable.

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

Examples of the peroxide-based curing accelerator include cyclohexanone peroxide, tert-butylperoxy benzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, di- Propylbenzene hydroperoxide, cumene hydroperoxide, and tert-butyl hydroperoxide.

As the peroxide-based curing accelerator, a commercially available product can be used, and for example, " PERCUMIL D "

When the (G) curing accelerator is used, the amount of the (C) curing accelerator in the resin composition is preferably 0.01 mass% or more, more preferably 0.01 mass% or less More preferably not less than 0.02% by mass, particularly preferably not less than 0.03% by mass, preferably not more than 3% by mass, more preferably not more than 2% by mass, particularly preferably not more than 1% by mass.

[1.9. (H) Additive]

In addition to the above-mentioned components, the resin composition may further contain additives as optional components. Examples of such additives include organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds; Thickener; Defoamer; Leveling agents; An adhesion imparting agent; coloring agent; Flame retardant; Thermoplastic resins and the like. The additives may be used singly or in combination of two or more kinds.

[1.10. Method of producing resin composition]

The resin composition can be produced, for example, by mixing a compounding component with a solvent as required and stirring by using a stirring device such as a rotary mixer.

[1.11. Characteristics of Resin Composition]

The cured product of the above resin composition can lower its dielectric constant. Therefore, an insulating layer having a low dielectric constant can be obtained by the cured product of the resin composition. For example, when a cured product is obtained by curing the resin composition by the method described in the examples, the dielectric constant of the cured product is preferably 3.0 or less, more preferably 2.9 or less. Here, the dielectric constant of the cured product can be measured by the method described in the embodiment.

The above cured product of the resin composition is excellent in the temperature stability of the dielectric loss tangent. Specifically, the cured product of the resin composition can reduce the difference between the value of the dielectric loss tangent at room temperature and the value of dielectric loss tangent at high temperature, and the value of the dielectric loss tangent at room temperature and the dielectric loss tangent Can be made small.

Therefore, an insulating layer excellent in the temperature stability of the dielectric loss tangent can be obtained by the cured product of the resin composition. Specifically, the dielectric loss tangent at -10 ° C, 25 ° C and 100 ° C of the cured product obtained by heat-treating the resin composition at 200 ° C for 90 minutes is Df (-10 ° C), Df (25 ° C) and Df The ratio Df (-10 ° C) to Df (25 ° C) of Df (-10 ° C) relative to Df (25 ° C) (100 deg. C) / Df (25 deg. C) is in the following range.

That is, the ratio of dielectric loss tangent Df (-10 ° C) / Df (25 ° C) is usually 85% or more, preferably 87% or more, particularly preferably 90% or more, Or less, particularly preferably 113% or less.

The ratio of dielectric loss tangent Df (100 占 폚) / Df (25 占 폚) is usually 85% or more, preferably 90% or more, more preferably 95% or more and usually 115% or less, preferably 114% , Particularly preferably not more than 113%.

The dielectric loss tangent Df (-10 ° C), Df (25 ° C) and Df (100 ° C) can be measured by the methods described in the examples.

As described above, the inventor of the present invention conjectures that the structure exhibiting excellent temperature stability of dielectric tangent is as follows. However, the technical scope of the present invention is not limited by the structure described below.

According to the study by the present inventors, the dielectric loss tangent of the cured product of the resin composition containing the epoxy resin (A) and the fluorine-containing filler (D) is lower in a practical temperature range from -10 ° C to 100 ° C, It turned out to be a big trend. On the other hand, the dielectric tangent of the polymer of the maleimide compound (B) tends to be larger at lower temperatures and smaller at higher temperatures due to the action of the maleimide group in the practical temperature range of the extruder. Thus, the temperature dependence of the dielectric loss tangent of the cured product of the resin composition containing the epoxy resin (A) and the fluorine-containing filler (D) and the temperature dependence of the dielectric tangent of the polymer of the maleimide compound (B) are opposite. Therefore, when the epoxy resin (A), the fluorine-containing filler (D) and the maleimide compound (B) are combined, the temperature dependency of the dielectric tangent of the two is canceled each other, and the dielectric tangent Df Can be obtained. Therefore, the dielectric loss tangent of the cured product of the resin composition containing the epoxy resin (A), the (B) maleimide compound and the (D) fluorine-based filler has good temperature stability.

The cured product of the above resin composition usually has a small dielectric loss tangent at 25 占 폚. For example, the dielectric loss tangent Df (25 DEG C) at 25 DEG C of the cured product obtained by heat-treating the resin composition at 200 DEG C for 90 minutes is preferably 0.020 or less, more preferably 0.010 or less, more preferably 0.009 or less, Particularly preferably 0.008 or less, 0.007 or less, or 0.006 or less. The lower limit is not particularly limited, but is usually 0.001 or more.

[2. Resin composition according to the second embodiment]

The resin composition according to the second embodiment of the present invention comprises (A) an epoxy resin and (D) a fluorine-based filler. The dielectric loss tangent at -10 占 폚, 25 占 폚 and 100 占 폚 of the cured product obtained by heat-treating the resin composition according to the second embodiment at 200 占 폚 for 90 minutes is Df (-10 占 폚), Df (25 占 폚) (-10 ° C) / Df (25 ° C) of Df (-10 ° C) relative to Df (25 ° C) is 85% to 115%, and Df (100 deg. C) / Df (25 deg. C) of Df (100 deg. C) to 85 deg.

The cured product of such a resin composition has a low dielectric constant due to the action of the (D) fluorine-based filler. Further, since the ratio of dielectric loss tangent Df (-10 ° C) / Df (25 ° C) and Df (100 ° C) / Df (25 ° C) fall within a predetermined range of 85% to 115% Cargo has excellent temperature stability of dielectric tangent. Therefore, according to the resin composition of the second embodiment, the temperature stability of the dielectric loss tangent is excellent, so that it is possible to suppress the change in temperature of the radar detectable range when it is provided on the antenna circuit board of the radar, It is possible to realize a resin composition capable of obtaining an insulating layer, and the desired effect of the present invention can be obtained. Further, according to the resin composition of the second embodiment, the same advantages as those of the resin composition of the first embodiment can be obtained.

With respect to the epoxy resin (A) and the fluorine-based filler (D) of the resin composition according to the second embodiment, the matters described in the first embodiment can be applied as in the first embodiment.

The resin composition according to the second embodiment is preferably such that the ratio of the dielectric loss tangent Df (-10 DEG C) / Df (25 DEG C) and Df (100 DEG C) / Df (25 DEG C) ) Maleimide compounds. Usually, the ratio Df (-10 캜) / Df (25 캜) and Df (100 캜) / Df (25 캜) can be set within a predetermined range by adjusting the amount of the maleimide compound (B). With respect to the maleimide compound (B) of the resin composition according to the second embodiment, the matters described in the first embodiment can be applied as in the first embodiment.

The resin composition according to the second embodiment may contain, as optional components, at least one of (C) an inorganic filler, (E) an unsaturated resin, (F) a curing agent, (G) a curing accelerator, and Two or more of them may be included. Regarding the inorganic filler (C), the unsaturated resin (E), the curing agent (G), the curing accelerator and the additive (H) in the resin composition according to the second embodiment, The present invention is not limited thereto.

The resin composition according to the second embodiment can be usually produced by the same production method as the resin composition according to the first embodiment.

The resin composition according to the second embodiment usually has the same properties as the resin composition according to the first embodiment. Therefore, the cured product of the resin composition according to the second embodiment has a low dielectric constant, excellent temperature stability of dielectric tangent, and a small dielectric loss tangent at 25 占 폚.

[3. Use of Resin Composition]

The above-mentioned resin composition can be used as a resin composition for forming an insulating layer of a circuit board such as a printed circuit board. The insulating layer includes an insulating layer for forming a conductor layer (including a rewiring layer) on the insulating layer. Therefore, the resin composition may be used as a resin composition for forming an insulating layer for forming a conductor layer. Among them, the resin composition is preferably used as a resin composition for forming a build-up insulating layer for forming an insulating layer in the production of a circuit board by a build-up method.

In particular, taking advantage of the fact that an insulating layer with a low dielectric constant can be obtained, the resin composition is preferably used as a resin composition (resin composition for forming an insulating layer of a high-frequency circuit substrate) for forming an insulating layer of a high- . Among them, the resin composition can be more suitably used as a resin composition (a resin composition for forming an interlayer insulating layer of a high-frequency circuit substrate) for forming an interlayer insulating layer of a high-frequency circuit board. Here, the " high frequency circuit board " means a circuit board capable of operating even an electric signal of a high frequency band. The term " high-frequency band " means a band of 1 GHz or higher, and the resin composition is particularly effective in a band of 28 GHz to 150 GHz.

Further, taking advantage of the excellent temperature stability of dielectric loss tangent, the resin composition is preferably used as a resin composition for an insulating layer of an antenna circuit board for radar. As the insulating layer of the antenna circuit board, for example, a wiring forming layer and the like can be given. As described above, by using the cured product having good dielectric stability and temperature stability as the material of the insulating layer, it is possible to reduce the change in the size of the loss in the antenna circuit board due to the temperature, Can be realized.

In addition, the insulating layer having a low dielectric constant contributes to lowering the height of the circuit board, which is suitable for applications requiring a thin circuit board. Further, the insulating layer having a low dielectric constant facilitates impedance control of the circuit board, which is suitable for increasing the degree of freedom in designing the circuit board. From such a viewpoint, a suitable use of the resin composition is, for example, a circuit board such as a mother board, an IC package substrate, a camera module substrate, and a substrate for a fingerprint authentication sensor used in portable equipment. Specifically, for example, the fingerprint authentication sensor may include an insulating layer included in a circuit board, a plurality of electrodes formed on the insulating layer, and an insulating film in this order. In this fingerprint authentication sensor, the authentication of the fingerprint is performed by using the capacitance value of the capacitors formed by the finger, the electrode, and the insulating film on the insulating film different from the concave portion and the convex portion of the fingerprint. In such a fingerprint authentication sensor, if the insulating layer can be made thinner, the size of the sensor itself can be reduced.

In addition, the above-mentioned resin composition can be used for a wide range of applications in which a resin composition such as a sheet-like laminate material such as an adhesive film and a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a hole filling resin, .

[4. Sheet laminated material]

The above-mentioned resin composition can be applied in the form of a varnish to form an insulating layer. However, it is industrially preferable to use it in the form of a sheet-like laminate material containing the resin composition. Preferable examples of the sheet-like laminated material include an adhesive film and a prepreg.

In one embodiment, the adhesive film comprises a support and a resin composition layer disposed on the support. The resin composition layer is a layer formed of the resin composition described above and may be referred to as an " adhesive layer ".

The thickness of the resin composition layer is preferably 100 占 퐉 or less, more preferably 80 占 퐉 or less, still more preferably 60 占 퐉 or less, and most preferably 50 占 퐉 or less, from the viewpoint of thinning. The lower limit of the thickness of the resin composition layer is not particularly limited and may be, for example, 1 占 퐉 or more, 5 占 퐉 or more, 10 占 퐉 or more and the like.

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

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter sometimes referred to as "PEN") Of polyester; Polycarbonate (hereinafter sometimes referred to as " PC "); Acrylic polymers such as polymethyl methacrylate (hereinafter sometimes referred to as " PMMA "); Cyclic polyolefin; Triacetyl cellulose (hereinafter sometimes referred to as " TAC "); Polyether sulfide (hereinafter sometimes referred to as " PES "); Polyether ketones; Polyimide. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and polyethylene terephthalate is particularly preferable because it is inexpensive and excellent in availability.

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

The support may be subjected to a treatment such as a mat treatment, a corona treatment, and an antistatic treatment on the surface to be bonded to the resin composition layer.

As the support, a support having a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the release agent that can be used for the release layer of the release layer-adhered support include one or more types of release agents selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin. Examples of commercially available products of the release agent include "SK-1", "AL-5", and "AL-7" manufactured by Lin Tec Corporation, an alkyd resin type release agent. As the release layer-adhered support, for example, " Lumirror T60 " "Purex" manufactured by Dejin Corporation; And " Unipyl " manufactured by Uni-Chika Corporation.

The thickness of the support is preferably in the range of 5 탆 to 75 탆, more preferably in the range of 10 탆 to 60 탆. When a release layer-adhered support is used, it is preferable that the thickness of the entirety of the release layer-adhered support is in the above range.

The adhesive film can be formed, for example, by preparing a resin varnish containing an organic solvent and a resin composition, applying the resin varnish to a support using a coating apparatus such as a die coater, and further drying the resin varnish to form a resin composition layer Can be manufactured.

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; Acetic acid ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; Carbitol solvents such as cellosolve and butyl carbitol; Aromatic hydrocarbon solvents such as toluene and xylene; And amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used singly or in combination of two or more kinds.

The drying can be carried out by a known method such as heating or hot air spraying. The drying conditions are set so that the content of the organic solvent in the resin composition layer is usually 10 mass% or less, preferably 5 mass% or less. When a resin varnish containing an organic solvent of 30% by mass to 60% by mass, for example, is used, it is dried at 50 to 150 ° C for 3 minutes to 10 minutes to obtain a resin A composition layer can be formed. Usually, the resin composition layer is obtained as a film obtained by partially curing the coating film of the resin varnish.

The adhesive film may optionally include a layer other than the support and the resin composition layer. For example, a protective film according to a support may be provided on the surface of the adhesive film which is not bonded to the support of the resin composition layer (that is, the surface opposite to the support). The thickness of the protective film is, for example, 1 占 퐉 to 40 占 퐉. By the protective film, adhesion and scratches of dust or the like to the surface of the resin composition layer can be suppressed. When the adhesive film has a protective film, the adhesive film is usually usable by peeling the protective film. Further, the adhesive film can be rolled and stored.

In one embodiment, the prepreg can be formed by impregnating a sheet-like fibrous substrate with a resin composition.

The sheet-like fibrous substrate used in the prepreg is not particularly limited. As the sheet-like fiber base material, any fiber base material used as a base material for a prepreg, such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of thinning, the thickness of the sheet-like fiber base material is preferably 900 占 퐉 or less, more preferably 800 占 퐉 or less, further preferably 700 占 퐉 or less, particularly preferably 600 占 퐉 or less. The thickness of the sheet-like fiber base material is preferably 30 占 퐉 or less, more preferably 20 占 퐉 or less, and particularly preferably 10 占 퐉 or less from the viewpoint of suppressing the depth of immersion of the plating in forming the conductor layer. The lower limit of the thickness of the sheet-like fibrous base material is usually 1 占 퐉 or more, 1.5 占 퐉 or more, or 2 占 퐉 or more.

The prepreg can be produced by a method such as a hot melt method or a solvent method. The thickness of the prepreg may be the same as that of the resin composition layer in the adhesive film.

[5. Circuit board]

The circuit board of the present invention includes an insulating layer formed of a cured product of the above resin composition. In one embodiment, the circuit board includes an inner layer substrate and an insulating layer provided on the inner layer substrate.

The " inner layer substrate " is a member serving as a substrate of a circuit substrate. Examples of the inner-layer substrate include a core substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. Further, usually, the inner layer substrate has a conductor layer formed directly or indirectly on one or both surfaces of the core substrate. The conductor layer may be patterned to function as, for example, an electric circuit. An inner layer substrate on which a conductor layer is formed as a circuit on one side or both sides of the core substrate is sometimes referred to as an " inner layer circuit substrate ". Further, an intermediate product to which at least one of the insulating layer and the conductor layer is to be further formed for manufacturing a circuit board is also included in the term "inner layer substrate". In the case where the circuit board incorporates a component, an inner-layer board containing components may be used.

The thickness of the inner layer substrate is usually from 50 mu m to 4000 mu m and preferably from 200 mu m to 3200 mu m from the standpoint of improvement of the mechanical strength of the circuit board and reduction in thickness (reduction in thickness).

The inner layer substrate may be provided with one or more through holes extending from one surface to the other surface in order to electrically connect the conductor layers on both sides thereof. Further, the inner-layer substrate may have additional components such as passive elements.

The insulating layer is a layer of a cured product of the resin composition. The insulating layer formed of the cured product is particularly suitable for use in a build-up type circuit board, a high frequency circuit board, a radar antenna circuit board, and a mother board, an IC package substrate, a camera module substrate, It can be suitably applied to an insulating layer for a circuit board such as a substrate for a sensor.

The circuit board may have only one insulating layer or two or more insulating layers. When the circuit board has an insulating layer having two or more layers, it can be provided as a build-up layer in which a conductor layer and an insulating layer are alternately stacked.

The thickness of the insulating layer is usually 20 占 퐉 to 200 占 퐉, preferably 50 占 퐉 to 150 占 퐉, from the viewpoints of improvement of electrical characteristics and lowering of the circuit board.

The insulating layer may be provided with one or more via holes for electrically connecting the conductor layers of the circuit board to each other.

Since the insulating layer is a layer formed by the cured product of the resin composition described above, the cured product of the resin composition can exert excellent properties. Therefore, the dielectric layer of the circuit board preferably has a dielectric constant, a dielectric loss tangent Df (-10 캜) / Df (25 캜), a dielectric loss tangent Df (100 캜) / Df (25 캜) And the dielectric loss tangent Df (25 占 폚) at 25 占 폚 can be adjusted to the range as described in the section of the resin composition. These properties can also be measured by the methods described in the examples.

The circuit board can be manufactured by a manufacturing method including the following steps (I) and (II) using, for example, an adhesive film.

(I) A step of laminating an adhesive film on the inner layer substrate and a resin composition layer of the adhesive film to be bonded to the inner layer substrate.

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

The lamination of the inner layer substrate and the adhesive film can be performed, for example, by a heat pressing process in which the adhesive film is heated while being pressed against the inner layer substrate from the support side. Examples of members (also referred to as " hot pressed members ") for a hot pressing process include a heated metal plate (SUS hard plate) or a metal roll (SUS roll). Further, it is preferable to press the hot pressing member through an elastic material such as heat-resistant rubber so that the adhesive film sufficiently follows the unevenness of the surface of the inner layer substrate, instead of directly pressing the hot pressing member against the support of the adhesive film.

The lamination of the inner layer substrate and the adhesive film can be carried out, for example, by a vacuum laminating method. The temperature of the hot pressing in the vacuum laminating method is preferably 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C. The pressure of the hot pressing is preferably 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa. The time for hot pressing is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably performed under a reduced pressure of 26.7 hPa or less.

The lamination can be performed by a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressurized laminator manufactured by Meiji Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Material Co., Ltd., and a batch type vacuum pressure laminator can be given.

After lamination, the laminated resin composition layer may be subjected to smoothing treatment by pressing under atmospheric pressure (at atmospheric pressure), for example, from a support side by a hot pressing member. The pressing condition of the smoothing process can be the same as the condition of the hot pressing of the lamination. The smoothing process can be performed by a commercially available laminator. The lamination and smoothing process may be performed continuously using the commercially available vacuum laminator described above.

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

In the step (II), the resin composition layer is thermally cured to form an insulating layer. The conditions of the thermosetting of the resin composition layer are not particularly limited, and the conditions employed in forming the insulating layer of the circuit board can be arbitrarily adopted.

The thermosetting condition of the resin composition layer varies depending on, for example, the type of the resin composition. The curing temperature of the resin composition layer is usually in the range of 120 캜 to 240 캜 (preferably in the range of 150 캜 to 220 캜, more preferably in the range of 170 캜 to 200 캜). The curing time is usually in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

The resin composition layer may be preheated to a temperature lower than the curing temperature before thermosetting the resin composition layer. For example, before the resin composition layer is thermally cured, the resin composition layer is heated to a temperature of generally 50 ° C or more and less than 120 ° C (preferably 60 ° C or more and 110 ° C or less, more preferably 70 ° C or more and 100 ° C or less) May be preliminarily heated for usually 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

The manufacturing method of the circuit board may further include (III) a step of piercing the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer. These steps (III) to (V) may be carried out according to a suitable method used in the production of a circuit board. When the support is removed after the step (II), the removal of the support is carried out between the steps (II) and (III), between the steps (III) and (IV) May be performed at any point in time.

Step (III) is a step of perforating the insulating layer. Through holes, holes such as via holes and through holes can be formed in the insulating layer. The step (III) can be carried out by, for example, a method such as drilling, laser or plasma, depending on the composition of the resin composition used for forming the insulating layer. The dimensions and shape of the holes can be determined appropriately according to the design of the circuit board.

Step (IV) is a step of applying a roughening treatment to the insulating layer. The order and conditions of the harmonic treatment are not particularly limited, and any order and conditions used in forming the insulating layer of the circuit board can be employed. For example, swelling treatment with a swollen liquid, coarsening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid can be carried out in this order to roughen the insulating layer.

The swelling liquid includes, for example, an alkali solution and a surfactant solution, and preferably an alkali solution. As the alkali solution, a sodium hydroxide solution or a potassium hydroxide solution is more preferable. Examples of commercially available swelling liquids include Swelling Dip Siculgans P and Swelling Dip Siculgans SBU manufactured by Atotech Japan Co., Ltd. The swelling liquid may be used alone or in combination of two or more. The swelling treatment by the swelling liquid is not particularly limited. The swelling treatment can be performed, for example, by immersing the insulating layer in a swelling solution at 30 캜 to 90 캜 for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in the swelling liquid at 40 占 폚 to 80 占 폚 for 5 minutes to 15 minutes.

As the oxidizing agent, there can be mentioned, for example, an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The oxidizing agent may be used singly or in combination of two or more kinds. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated at 60 캜 to 80 캜 for 10 minutes to 30 minutes. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd. and "Dozing Solution · Securigans P".

As the neutralizing solution, an acidic aqueous solution is preferable. As a commercial product of the neutralization liquid, for example, "Reduction Solution · Securigans P" manufactured by Atotech Japan Co., Ltd. can be mentioned. The neutralizing liquid may be used singly or in combination of two or more kinds. The treatment with the neutralizing liquid can be performed by immersing the treated surface of the insulating layer subjected to the roughening treatment with an oxidizing agent in a neutralizing solution at 30 ° C to 80 ° C for 5 minutes to 30 minutes. It is preferable to immerse the insulating layer subjected to the roughening treatment with an oxidizing agent in a neutralizing solution at 40 캜 to 70 캜 for 5 minutes to 20 minutes in terms of workability and the like.

Step (V) is a step of forming a conductor layer. The material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises at least one metal selected from the group consisting of 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. Examples of the alloy layer include a layer formed of an alloy of two or more metals selected from the above-mentioned group (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or a copper single metal layer is preferable from the viewpoints of versatility, cost and ease of patterning of the conductor layer. Or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy. In addition, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal layers; Alternatively, an alloy layer of nickel-chromium alloy is more preferable, and a metal layer of copper is more preferable.

The conductor layer may have a single-layer structure or may have a multi-layer structure including two or more single metal layers or alloy layers made of different kinds of metals or alloys. When the conductor layer is 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 from 3 to 200 mu m, preferably from 10 to 100 mu m.

The conductor layer can be formed, for example, by directly patterning it using a metal foil used as a support for an adhesive film. The conductor layer can be formed by, for example, plating. As a forming method by plating, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a method such as a semiadditive method or a pull additive method. Above all, from the viewpoint of simplicity of production, it is preferable to form it by the semi-additive method.

Hereinafter, an example of forming the conductor layer by the semi-additive method will be described. First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Subsequently, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer so as to correspond to the desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

The conductor layer may be formed using, for example, a metal foil. In the case of forming the conductor layer using a metal foil, it is preferable that the step (V) is carried out between the step (I) and the step (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. The lamination of the resin composition layer and the metal foil can be carried out by a vacuum laminating method. The lamination conditions may be the same as the lamination conditions of the inner layer substrate and the adhesive film in the step (I). Subsequently, an insulating layer is formed by carrying out the step (II). Thereafter, the metal layer on the insulating layer can be used to form a conductor layer having a desired wiring pattern by a subtractive method, a modified semi-additive method or the like. The metal foil can be produced by, for example, an electrolytic method, a rolling method, or the like. Examples of commercial products of metal foil include HLP foil, JXUT-III foil, 3EC-III foil, and TP-III foil manufactured by JX Nikkosuke Kikuchi Kogyo Co., Ltd., and the like.

When the circuit board has two or more insulating layers and a conductor layer (build-up layer), the above-described step of forming the insulating layer and the step of forming the conductor layer are repeated one or more times, A circuit board having a multilayer wiring structure can be manufactured.

In another embodiment, the circuit board can be made using a prepreg instead of an adhesive film. The manufacturing method using the prepreg is basically the same as the case of using the adhesive film.

[6. Semiconductor device]

The semiconductor device includes the circuit board. This semiconductor device can be manufactured by using a circuit board.

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

The semiconductor device can be manufactured, for example, by mounting a component (semiconductor chip) in a conductive portion of a circuit board. The " conduction point " is a " position for transmitting an electrical signal on a circuit board ", and the position may be a surface of the circuit board or a portion embedded in the circuit board. Further, the semiconductor chip can be arbitrarily used as an electric circuit element made of a semiconductor.

The semiconductor chip mounting method in manufacturing the semiconductor device can employ any method in which the semiconductor chip effectively functions. Examples of the semiconductor chip mounting method include a wire bonding mounting method, a flip chip mounting method, a mounting method using a bumpless buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF) As shown in Fig. Here, the " mounting method using the bumpless buildup layer (BBUL) " means a mounting method in which " the semiconductor chip is directly buried in the circuit board to connect the semiconductor chip and the circuit board wiring.

Example

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

[Example 1]

, 20 parts of biscylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: about 185) and 2.5 parts of phenylmethanemaleimide resin ("BMI-2000" manufactured by Daikase Seiko) were added to 20 parts of solvent naphtha The solution was heated and dissolved, and then cooled to room temperature to obtain a resin solution.

100 parts of an inorganic filler (" SO-C2 " manufactured by Adomex Co., Ltd., average particle diameter 0.5 占 퐉, specific surface area 5.9 m2 / g, carbon amount per unit surface area 0.38 mg / m2) and polytetrafluoro And 55 parts of ethylene particles ("Lubron L-2" manufactured by Daikin Industries, Ltd., average particle diameter 3 μm) were mixed and kneaded by a three-roll mill and dispersed.

31 parts of an active ester type curing agent (" HPC-8000-65T ", manufactured by DIC Co., Ltd., a toluene solution of 65% of nonvolatile matter having an equivalent weight of about 223 as an activating group equivalent), 30 parts of an acrylic resin (Shin Nakamura Kagakuko Co., , 2 parts of a hardening accelerator (5% methyl ethyl ketone solution of 4-dimethylaminopyridine (DMAP)) and 0.13 parts of a curing accelerator (Dicumylperoxide "Percumyl D" And uniformly dispersed in a rotary mixer to prepare a resin varnish 1.

[Example 2]

Phenylmethane maleimide resin (" BMI-2000 ", manufactured by TAIWA SEIKO CO., LTD.) Was changed to 10 parts. In addition, acrylic resin ("A-DOG" manufactured by Shin Nakamura Kagakuko Co., Ltd.) and dicumyl peroxide ("Percumyl D" manufactured by Nichi- The resin varnish 2 was produced in the same manner as in Example 1 except for the above.

[Example 3]

Phenylmethane maleimide resin (" BMI-2000 " manufactured by Daicel Chemical Industries Ltd.) was changed to 13.5 parts. A resin varnish 3 was produced in the same manner as in Example 1 except for the above.

[Example 4]

2.5 parts of phenylmethane maleimide resin ("BMI-2000" manufactured by Daicel Chemical Industries Ltd.) was changed to 2.5 parts of m-phenylene bismaleimide resin ("BMI-3000" manufactured by Daikase Seiko). The resin varnish 4 was produced in the same manner as in Example 1 except for the above.

[Example 5]

2.5 parts of phenylmethane maleimide resin ("BMI-2000" manufactured by Daicel Chemical Industries Ltd.) was changed to 10 parts of m-phenylene bismaleimide resin ("BMI-3000" manufactured by TAIWA SEIKO CO., LTD.). In addition, acrylic resin ("A-DOG" manufactured by Shin Nakamura Kagakuko Co., Ltd.) and dicumyl peroxide ("Percumyl D" manufactured by Nichi- A resin varnish 5 was produced in the same manner as in Example 1 except for the above.

[Example 6]

2.5 parts of phenylmethane maleimide resin ("BMI-2000" manufactured by Daicel Chemical Industries Ltd.) was changed to 13.5 parts of m-phenylene bismaleimide resin ("BMI-3000" manufactured by Daikase Seiko). The resin varnish 6 was produced in the same manner as in Example 1 except for the above.

[Comparative Example 1]

Phenylmethane maleimide resin (" BMI-2000 " manufactured by Daicel Chemical Industries Ltd.) was changed to 1 part. A resin varnish 7 was produced in the same manner as in Example 1 except for the above.

[Comparative Example 2]

Phenylmethane maleimide resin (" BMI-2000 ", manufactured by TAIWA SEIKO CO., LTD.) Was changed to 16 parts. The resin varnish 8 was produced in the same manner as in Example 1 except for the above.

[Comparative Example 3]

2.5 parts of phenylmethanemaleimide resin ("BMI-2000" manufactured by Daicel Chemical Industries Ltd.) was changed to 1 part of m-phenylene bismaleimide resin ("BMI-3000" manufactured by Daikase Seiko). A resin varnish 9 was produced in the same manner as in Example 1 except for the above.

[Comparative Example 4]

2.5 parts of phenylmethane maleimide resin ("BMI-2000" manufactured by Daicel Chemical Industries Ltd.) was changed to 16 parts of m-phenylene bismaleimide resin ("BMI-3000" manufactured by Daikase Seiko). The resin varnish 10 was produced in the same manner as in Example 1 except for the above.

[Assessment Methods]

(Preparation of Evaluation Sample of Cured Product)

A polyethylene terephthalate film ("PET501010" manufactured by Lynchtech Co., Ltd.) having a surface subjected to release treatment was prepared as a support. On this support, resin varnishes obtained in Examples and Comparative Examples were uniformly coated using a die coater so that the thickness of the resin composition layer after drying was 40 占 퐉. The applied resin varnish was dried at 80 ° C to 110 ° C (average 95 ° C) for 6 minutes to obtain a resin composition layer. Thereafter, the resin composition layer was heat-treated at 200 캜 for 90 minutes to cure, and the support was peeled off to obtain a cured film formed of the cured product of the resin composition. This cured film was cut into a length of 80 mm and a width of 2 mm to obtain an evaluation sample.

(Measurement of dielectric constant (Dk) and dielectric tangent (Df)

The dielectric loss tangent and dielectric constant of the evaluation sample were measured at a measurement frequency of 10 GHz by a cavity resonance perturbation method using a measuring device ("HP8362B" manufactured by Agilent Technologies). The dielectric loss tangent was measured at -10 캜, 25 캜 and 100 캜. The measurement of the dielectric constant was carried out at 25 占 폚.

(Evaluation of dielectric constant (Dk)) [

And a case where the dielectric constant Dk was 3.0 or less was evaluated as " good ". The case where the dielectric constant Dk exceeded 3.0 was evaluated as " defective ".

(Evaluation of Temperature Stability of Dielectric Tangent)

The ratio Df (-10 캜) / Df (25 캜) of the dielectric loss tangent (Df) (-10 캜) at -10 캜 to the dielectric loss tangent (Df) at 25 캜 at 25 캜 was calculated. When the ratio Df (-10 DEG C) / Df (25 DEG C) was in the range of 85% to 115%, the temperature stability at low temperature was judged as " good ". Further, when the ratio Df (-10 ° C) / Df (25 ° C) was not within the range of 85% to 115%, the temperature stability at low temperature was judged as "poor".

A ratio Df (100 占 폚) / Df (25 占 폚) of the dielectric loss tangent (Df) (100 占 폚) at 100 占 폚 to the dielectric loss tangent (Df) at 25 占 폚 at 25 占 폚 was calculated. When the ratio Df (100 占 폚) / Df (25 占 폚) was in the range of 85% to 115%, the temperature stability at high temperature was judged as "positive". Further, when the ratio Df (100 deg. C) / Df (25 deg. C) was not within the range of 85% to 115%, the temperature stability at high temperature was judged as " defective ".

[result]

The results of the above-described examples and comparative examples are shown in the following table. In the following table, the amount of each component represents the mass part of the non-volatile component. In the following table, the abbreviations have the following meanings.

(B) / (A): the mass ratio of the component (B) to the component (A) of 100 mass%.

[Review]

As can be seen from Table 1, low dielectric constant is obtained in the examples. Further, in the examples, the ratio of the dielectric loss tangent Df (100 ° C) / Df (25 ° C) falls within a predetermined range (100% ± 15%) close to 100% and the temperature stability of the dielectric loss tangent at a high temperature is satisfactory Do. Further, in the examples, the temperature dependency of the dielectric loss tangent at low temperature is within a predetermined range (100% ± 15%) in which the ratio of dielectric loss tangent Df (-10 ° C) / Df Good. As a result, it has been confirmed that the present invention can realize a resin composition capable of obtaining an insulating layer having a low dielectric constant and excellent temperature stability of dielectric tangent. It is also understood by those skilled in the art that when an insulation layer having excellent dielectric stability of dielectric loss tangent is applied to an antenna circuit board of a radar device, a change in temperature of the radar detectable range can be suppressed.

In the above examples, even when the components (E) to (G) were not used, it was confirmed that the results were the same as those of the above-mentioned examples although there were differences in the degree.

Claims (12)

A resin composition comprising (A) an epoxy resin, (B) a maleimide compound, (C) an inorganic filler, and (D) a fluorine-based filler, wherein the amount of the component (B) % To 70% by mass. (A) an epoxy resin and (D) a fluorine-based filler, the dielectric loss tangent at -10 ° C, 25 ° C and 100 ° C of the cured product obtained by heat-treating the resin composition at 200 ° C for 90 minutes is represented by Df (-10 占 폚) / Df (25 占 폚) ratio of Df (-10 占 폚) to Df (25 占 폚) is 85% when Df And the ratio Df (100 DEG C) / Df (25 DEG C) of Df (100 DEG C) to Df (25 DEG C) is 85% to 115%. The resin composition according to claim 2, which comprises (B) a maleimide compound. The resin composition according to claim 1 or 2, wherein the component (D) is a fluorine-based polymer particle. The resin composition according to claim 1 or 2, wherein the component (D) is polytetrafluoroethylene particles. The resin composition according to claim 1 or 2, wherein the resin composition comprises (E) a resin having an unsaturated hydrocarbon group. The resin composition according to claim 6, wherein the component (E) has at least one unsaturated hydrocarbon group selected from the group consisting of an acryl group, a methacryl group, a styryl group, an allyl group, a vinyl group and a propenyl group. The resin composition according to claim 6, wherein the component (E) has a vinyl group and further has a cyclic ether structure having five or more ring members. The resin composition according to claim 1 or 2, which is used for forming an insulating layer of a circuit board. 10. A sheet-like laminated material comprising the resin composition according to any one of claims 1 to 9. A circuit board comprising an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 9. A semiconductor device comprising the circuit board according to claim 11.