TW201912713A - Resin composition - Google Patents

Abstract

An object of the present invention is to provide a resin composition which is low in dielectric constant, provided with an insulating layer excellent in adhesion to a conductor layer and a fluorine-based filling material, and excellent in dispersibility. The solution of the present invention is a resin composition which comprises (A) an epoxy resin containing a fluorine atom in its molecule, (B) a curing agent, and (C) a fluorine-based filling material, wherein the epoxy resin containing fluorine atom is a bisphenol AF epoxy resin, the curing agent is an active ester curing agent, and the average particle diameter of the fluorine-based filling material is from 0.05 [mu]m to 5 [mu]m.

Description

Resin composition

The present invention relates to a resin composition. Furthermore, the present invention relates to a sheet-like laminated material including the resin composition, a circuit board including a resin layer formed of a cured material of the resin composition, and a semiconductor device.

In recent years, requests for miniaturization of electronic equipment, high-speed signals, and high-density wiring have sought to reduce the thickness of the insulating layer. In order to reduce the thickness of the insulating layer, it is desirable to reduce the dielectric constant by controlling the impedance. It is known that in order to reduce the dielectric constant of the insulating layer, it is preferable to use a filler having a lower specific dielectric constant, for example, a fluororesin powder such as polytetrafluoroethylene (see Patent Document 1). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 11-269530

[Questions to be Solved by the Invention]

However, a fluorine-based filler such as polytetrafluoroethylene particles is highly hydrophobic, and when mixed with a resin component such as an epoxy resin to obtain a resin composition, the dispersibility is insufficient. Furthermore, the insulating layer formed using a resin composition containing a fluorine-based filler has insufficient adhesiveness with a conductor layer formed on the insulating layer.

The present invention has been made by the inventors in view of the foregoing problems, and provides a resin composition which can obtain an insulating layer having a low dielectric constant and excellent adhesion to a conductor layer, and further having excellent dispersibility of a fluorine-based filler; A sheet-like laminated material of a resin composition; a circuit board and a semiconductor device including an insulating layer composed of a hardened body of the resin composition are for the purpose. [Means to solve the problem]

As a result of diligent research in order to solve the aforementioned problems, the present inventors have found that a resin composition containing (A) an epoxy resin containing a fluorine atom in a molecule, (B) a hardener, and (C) a fluorine-based filler may be combined. The present invention has been achieved by solving the aforementioned problems. That is, the present invention includes the following.

[1] A resin composition comprising (A) an epoxy resin containing a fluorine atom in a molecule, (B) a hardener, and (C) a fluorine-based filler. [2] The resin composition according to [1], wherein the component (A) is a bisphenol AF epoxy resin. [3] The resin composition according to [1] or [2], wherein the average particle diameter of the component (C) is 0.05 μm to 5 μm. [4] The resin composition according to any one of [1] to [3], wherein the component (B) contains an active ester-based hardener. [5] The resin composition according to any one of [1] to [4], which contains (D) an inorganic filler. [6] The resin composition according to [5], wherein the amount of the component (C) is 20% to 80% by mass based on 100% by mass of the total amount of the (C) component and the (D) component. [7] The resin composition according to any one of [1] to [6], which is used for forming an insulating layer of a circuit board. [8] A sheet-like laminated material comprising the resin composition according to any one of [1] to [7]. [9] A sheet-like laminate comprising a resin composition layer formed of the resin composition according to any one of [1] to [7]. [10] The sheet-like laminated body according to [9], wherein the thickness of the resin composition layer is 30 μm or less. [11] A circuit board comprising an insulating layer composed of a hardened body of the resin composition according to any one of [1] to [7]. [12] A semiconductor device including the circuit board according to [11]. [Effect of the invention]

According to the present invention, it is possible to provide a resin composition capable of obtaining an insulating layer having a low dielectric constant and excellent adhesion to a conductor layer, and further having excellent dispersibility of a fluorine-based filler; and a sheet-like layer including the foregoing resin composition. Composite material; a circuit board and a semiconductor device including an insulating layer composed of a hardened body of the aforementioned resin composition.

Hereinafter, embodiments and exemplified objects will be described, and the present invention will be described in detail. However, the present invention is not limited to the embodiments and examples shown below, and can be arbitrarily changed and implemented without departing from the scope of the patent application of the present invention and its equivalent range.

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

In the following description, the term "dielectric constant" means the specific dielectric constant unless otherwise specified.

[1. Overview of resin composition] The resin composition of the present invention includes (A) an epoxy resin containing a fluorine atom in a molecule, (B) a hardener, and (C) a fluorine-based filler. In the following description, an epoxy resin containing a fluorine atom in a molecule as the component (A) may be referred to as a "fluorine-based epoxy resin". The term "fluorine-based" refers to a fluorine atom. The term "fluorine-based filler" refers to a filler containing a compound containing a fluorine atom as a material. With such a resin composition, an insulating layer having a low dielectric constant and excellent adhesion to a conductor layer can be obtained, and further, the so-called desired effect of the present invention having excellent dispersibility of a fluorine-based filler can be obtained.

[2. (A) Fluorine-based Epoxy Resin] 氟 The fluorine-based epoxy resin as the component (A) is an epoxy resin containing a fluorine atom in the molecule. (A) The number of fluorine atoms per molecule of the fluorine-based epoxy resin is usually 1 or more, preferably 2 or more, usually 30 or less, preferably 25 or less, and more preferably 20 or less. When the number of fluorine atoms per molecule of (A) fluorine-based epoxy resin is in the aforementioned range, the desired effect of the present invention can be significantly obtained.

(A) Since the fluorine-based epoxy resin is an epoxy resin, an epoxy group is contained in the molecule. (A) The number of epoxy groups per molecule of the fluorine-based epoxy resin is usually 1 or more, and preferably 2 or more. In addition, the proportion of the (A) fluorine-based epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more with respect to 100% by mass of the non-volatile component of the (A) fluorine-based epoxy resin. It is more preferably 60% by mass or more, and particularly preferably 70% by mass or more. Since the ratio of the (A) fluorine-based epoxy resin having two or more epoxy groups in one molecule is as described above, the desired effect of the present invention can be significantly obtained. Moreover, the crosslinked density of the hardened | cured material of a resin composition becomes sufficient normally, and the insulating layer with small surface roughness can be obtained.

The (A) fluorine-based epoxy resin is preferably an aromatic epoxy resin from the viewpoint of reducing the average linear thermal expansion coefficient of the insulating layer. Here, the so-called aromatic epoxy resin refers to an epoxy resin in which the molecule contains an aromatic skeleton. The so-called aromatic skeleton is generally defined as an aromatic chemical structure, 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.

As an example of a preferable (A) fluorine-type epoxy resin, the bisphenol AF epoxy resin represented by following formula (1) is mentioned.

In Formula (1), R ¹ to R ⁸ each independently represent a group selected from the group consisting of a hydrogen atom, a fluorine atom, and an alkyl group. The number of carbon atoms of the aforementioned alkyl group is usually 1 or more, preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. Among them, R ¹ to R ^{8 are} preferably a hydrogen atom.

Among the bisphenol AF epoxy resins represented by formula (1), the (A) fluorine-based epoxy resin is particularly preferably 4,4 '-[2,2,2-trifluoro-1- (trifluoromethyl) ) Ethylene] bisphenol type epoxy resin. As described above, according to the preferred (A) fluorine-based epoxy resin, the desired effect of the present invention can be significantly obtained.

Specific examples of the (A) fluorine-based epoxy resin include "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and the like. In addition, (A) a fluorine-based epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

(A) The epoxy equivalent of the fluorine-based epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, even more preferably 80 to 2000, and particularly preferably 110 to 1,000. When the epoxy equivalent of the (A) fluorine-based epoxy resin is in the aforementioned 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 refers to the mass of a resin containing 1 equivalent of an epoxy group, and can be measured in accordance with JIS K7236.

(A) The weight-average molecular weight of the fluorine-based epoxy resin is preferably from 100 to 5,000, more preferably from 250 to 3,000, and even more preferably from 400 to 1500, from the viewpoint of remarkably obtaining 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 (A) fluorine-based epoxy resin in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1.0% with respect to 100% by mass of the nonvolatile matter in the resin composition. At least mass%, preferably at most 50 mass%, more preferably at most 40 mass%, and particularly preferably at most 20 mass%. When the amount of the (A) fluorine-based epoxy resin is in the aforementioned range, the desired effect of the present invention can be significantly obtained. Furthermore, an insulating layer that generally exhibits good mechanical strength and insulation reliability can be obtained.

The amount of (A) fluorine-based epoxy resin in the resin composition is preferably 100% by mass or more, more preferably 5% by mass or more, relative to 100% by mass of the (C) fluorine-based filler in the resin composition. Particularly preferred is 10% by mass or more, preferably 80% by mass or less, more preferably 50% by mass or less, and particularly preferably 30% by mass or less. When the amount of the (A) fluorine-based epoxy resin is in the aforementioned range, the desired effect of the present invention can be significantly obtained, and in particular, the dispersibility of the (C) fluorine-based filler can be effectively improved.

[3. (B) Hardener] As a hardener of (B) component, it usually has a function of reacting with (A) a fluorine-based epoxy resin to harden a resin composition. Examples of the (B) curing agent include an active ester curing agent, a phenol curing agent, a naphthol curing agent, a benzoxazine curing agent, a cyanate curing agent, and a carbodiimide curing agent. Agent. In addition, one type of hardener may be used alone, or two or more types may be used in combination.

As an active ester hardener, it can be used for a compound having one or more active ester groups in one molecule. Among them, as the active ester-based hardener, phenolic esters, thiophenolic esters, N-hydroxyamine esters, heterocyclic hydroxy compound esters, and the like are preferred. The ester group has two or more highly reactive ester groups in the molecule. compound of. The active ester-based hardener is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based hardener obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based hardener obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. hardener.

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, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, and methylol Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, resorcinol, benzenetriol, dicyclopentadiene type diphenol compound , Phenol novolac, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol into one molecule of dicyclopentadiene.

Preferred specific examples of the active ester-based hardener include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetic acid compound of a novolac, and An active ester compound of benzamidine of phenol novolac. Among these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit composed of phenylene-bicyclopentyl-phenylene.

As commercially available products of the active ester-based hardener, for example, as an active ester compound containing a dicyclopentadiene-type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", " "HPC-8000H-65TM", "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC Corporation); as an active ester compound containing a naphthalene structure, "EXB9416-70BK" (manufactured by DIC Corporation); As an active ester compound containing an acetic acid compound of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.); as an active ester compound containing an anilide compound of phenol novolac, "YLH1026" (Mitsubishi Chemical (Manufactured by the company); as the active ester-based hardener for the acetic acid compound of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation); as the active ester-based hardener for the benzoyl compound of phenol novolac, "YLH1026" (Mitsubishi Chemical Corporation), "YLH1030" (Mitsubishi Chemical Corporation), "YLH1048" (Mitsubishi Chemical Corporation); etc.

As a phenol-type hardener and a naphthol-type hardener, it is preferable that it has a novolak structure from a viewpoint of heat resistance and water resistance. From the standpoint of adhesion between the insulating layer and the conductor layer, a nitrogen-containing phenol-based hardener is preferred, and a phenol-based hardener containing a triazine skeleton is more preferred. Among these, a phenol novolak hardener containing a triazine skeleton is preferred from the viewpoint of satisfying high heat resistance, water resistance, and adhesion between the insulating layer and the conductor layer.

Specific examples of the phenol-based hardener and naphthol-based hardener include, for example, "MEH-7700", "MEH-7810", "MEH-7851", and "NHN" manufactured by Nippon Kayakusei Corporation. , "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V" "SN375" manufactured by Nippon Steel & Sumitomo Chemical Corporation; "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500") manufactured by DIC; etc.

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

Examples of the cyanate-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), and 4,4 ' -Methylenebis (2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2- Bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1, 3-bis (4-cyanatephenyl-1- (methylethylene)) benzene, bis (4-cyanatephenyl) sulfide, and bis (4-cyanatephenyl) ether 2-functional cyanate resins; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; etc .; part of these cyanate resins are triazinated prepolymers; etc. Specific examples of the cyanate-based curing agent include "PT30" and "PT60" (phenol novolac-type polyfunctional cyanate resin) and "ULL-950S" (polyfunctional cyanate resin) manufactured by Lonza Japan. ), "BA230", "BA230S75" (prepolymers in which part or all of the bisphenol A dicyanate becomes a triazinated terpolymer) and the like.

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

Among the above, from the viewpoint of significantly obtaining the desired effect of the present invention, the (B) hardener is preferably selected from the group consisting of an active ester hardener, a phenol hardener, and a naphthol hardener. One or more types of hardener. Furthermore, from the viewpoint of effectively improving the dispersibility of the (C) fluorine-based filler, an active ester-based hardener is particularly preferred. Therefore, it is preferable that the (B) hardener used in the resin composition contains an active ester-based hardener.

When using an active ester-based hardener, the amount of the active ester-based hardener based on 100% by mass of the (B) hardener is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. It is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. When the amount of the active ester-based hardener is in the aforementioned range, the desired effect of the present invention can be significantly obtained, and in particular, the dispersibility of the (C) fluorine-based filler can be effectively improved.

The amount of the (B) hardener in the resin composition is preferably 0.1% by mass or more with respect to 100% by mass of the nonvolatile matter in the resin composition, from the viewpoint that the desired effect of the present invention is significantly obtained. It is more preferably 0.5% by mass or more, even more preferably 1% by mass or more, more preferably 40% by mass or less, even more preferably 30% by mass or less, still more preferably 20% by mass or less.

When the epoxy group number of the entire epoxy resin containing (A) a fluorine-based epoxy resin and (E) a fluorine-free epoxy resin ((E) non-fluorine-based epoxy resin) described later is set to 1, ( B) The active group number of the hardener is preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.3 or more, more preferably 1.5 or less, even more preferably 1.2 or less, even more preferably 1 or less, and particularly preferably 0.8 or less. . Here, the "epoxy number of the entire epoxy resin" refers to the epoxy resins such as (A) fluorine-based epoxy resins and (E) non-fluorine-based epoxy resins present in all resin compositions. The value of the mass of the non-volatile component divided by the epoxy equivalent is the total value. The "number of active groups of (B) hardener" refers to a value obtained by dividing the mass of the nonvolatile component of (B) hardener present in all resin compositions by the value of the equivalent of the active group. When the epoxy group number of the epoxy resin as a whole is set to 1 and the active group number of the (B) hardener is in the aforementioned range, the desired effect of the present invention can be significantly obtained, and the heat resistance of the hardened product of the resin composition is generally further improved. Sex.

[4. (C) Fluorine Filler] The fluorine-based filler as the component (C) is a filler containing a compound containing a fluorine atom as a material. The fluorine-based filler is generally particles. Therefore, as the (C) fluorine-based filler, particles containing a compound containing a fluorine atom as a material are generally used.

Examples of the material of the (C) fluorine-based filler include a fluorine-based polymer and a fluorine-based rubber. Among them, from the viewpoint of reducing the dielectric constant of the insulating layer, a fluorine-based polymer is preferred. Therefore, as the (C) fluorine-based filler, fluorine-based polymer particles are preferred.

Examples of the fluorine-based polymer include polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene propylene copolymer (FEP), ethylene / tetrafluoroethylene copolymer (ETFE), and tetrafluoro Ethylene-perfluorodioxole copolymer (TFE / PDD), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE) Polyvinyl fluoride (PVF). These can be used alone or in combination of two or more.

Among these, from the viewpoint of particularly reducing the dielectric constant of the insulating layer, as the fluorine-based polymer, polytetrafluoroethylene is preferred. Therefore, the (C) fluorine-based filler is preferably polytetrafluoroethylene particles containing particles of polytetrafluoroethylene.

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 remarkably obtaining the desired effect of the present invention.

(C) The average particle diameter of the fluorine-based filler is preferably 0.05 μm or more, more preferably 0.08 μm or more, particularly preferably 0.10 μm or more, more preferably 5 μm or less, even more preferably 4.5 μm or less, and particularly preferably 4 μm. the following. When the average particle diameter of the (C) fluorine-based filler is in the aforementioned range, the desired effect of the present invention can be significantly obtained, and further, the dispersibility of the (C) fluorine-based filler in the resin composition can generally be improved. .

(C) The average particle diameter of particles such as a fluorine-based filler can be measured by a laser diffraction chirped scattering method based on the Mie scattering theory. Specifically, a laser diffraction scattering type particle size distribution measuring device can be used to measure the particle size distribution of particles on a volume basis, and the average particle size can be obtained from the particle size distribution as the median diameter. As the measurement sample, those in which the particles are dispersed in a solvent by ultrasound are preferably used. As the laser diffraction scattering type particle size distribution measuring device, "LA-500" manufactured by Horiba, Ltd. can be used.

Examples of commercially available (C) fluorine-based fillers include "LUBRON L-2", "LUBRON L-5", and "LUBRON L-5F" manufactured by Daikin Industries; and "FluonPTFE L" manufactured by Asahi Glass Co., Ltd. -170JE "," FluonPTFEL-172JE "," FluonPTFE L-173JE ";" KTL-500F "," KTL-2N "," KTL-1N "manufactured by Kitamura;" TLP10F- "manufactured by Mitsui DuPont Fluorochemical Company 1 "; etc.

(C) The fluorine-based filler can be surface-treated. For example, (C) a fluorine-based filler may be surface-treated with any surface-treating 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. In addition, as the fluorine-based surfactant, non-particulate appropriate fluorine-based polymers and fluorine-based oligomers can be used. Specific examples of the fluorine-based surfactant include "SURFLON S-243" (perfluoroalkyl ethylene oxide adduct) manufactured by AGC Seimi Chemical; "MEGAFAC F-251" and "MEGAFAC" manufactured by DIC. "F-477", "MEGAFAC F-553", "MEGAFAC R-40", "MEGAFAC R-43", "MEGAFAC R-94"; "FTX-218" and "FTERGENT 610FM" manufactured by NEOS Corporation.

The amount of the (C) fluorine-based filler in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass relative to 100% by mass of the nonvolatile components in the resin composition. % Or more, preferably 80% by mass or less, more preferably 60% by mass or less, and particularly preferably 40% by mass or less. When the amount of the (C) fluorine-based filler is in the aforementioned range, the desired effect of the present invention can be significantly obtained, and in particular, the dielectric constant of the hardened material of the resin composition can be effectively reduced.

Moreover, especially when the resin composition contains (D) an inorganic filler, the amount of the (C) fluorine-based filler in the resin composition is 100 mass relative to the total of (C) the fluorine-based filler and (D) the inorganic filler. %, Preferably 20% by mass or more, more preferably 30% by mass or more, 35% by mass or more, 80% by mass or less, 75% by mass or less, and 70% by mass or less is particularly preferred. When the amount of the (C) fluorine-based filler is in the aforementioned range, the desired effect of the present invention can be significantly obtained, and in particular, the dielectric constant of the hardened material of the resin composition can be effectively reduced.

[5. (D) Inorganic Filler] The resin composition may contain (D) an inorganic filler as an optional component in addition to the components described above. Examples of the material of the inorganic filler of the component (D) include silicon dioxide, aluminum oxide, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Gibbsite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate , Bismuth titanate, titanium oxide, zirconia, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium phosphate tungstate. Among them, it is particularly suitable for silicon dioxide from the viewpoint of remarkably obtaining the desired effect of the present invention. Examples of the silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. Among them, spherical silica is preferred. (D) The inorganic filler may be used alone or in combination of two or more kinds.

In general, (D) the inorganic filler is contained in the resin composition in a state of particles. (D) The average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and more preferably from the viewpoint of remarkably obtaining the desired effect of the present invention. 5.0 μm or less, more preferably 2.0 μm or less, and even more preferably 1.0 μm or less. In addition, when the average particle diameter of the (D) inorganic filler is in the aforementioned range, the circuit embedding property of the resin composition layer can be generally improved or the surface roughness of the insulating layer can be reduced.

Examples of commercially available (D) inorganic fillers include "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials; "YC100C", "YA050C", and "YA050C-" manufactured by Admatechs "MJE", "YA010C"; "UFP-30" manufactured by Denki Chemical Industries; "SILFIL NSS-3N", "SILFIL NSS-4N", "SILFIL NSS-5N" manufactured by Tokuyama; "Admatechs" SC2500SQ "," SO-C4 "," SO-C2 "," SO-C1 "; etc. The average particle diameter of the (D) inorganic filler is the same as that of the (C) fluorine-based filler, and can be measured by the laser diffraction chirped scattering method based on the Mie scattering theory.

The specific surface area (D) of an inorganic filler, to obtain the desired effect of the present invention is significant from the point of view, is preferably 1m ² / g or more, more preferably 2m ² / g or more, particularly preferably 3m ² / g or more . Although the upper limit is not particularly limited, it 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 is obtained by using a specific surface area measuring device (Macsorb HM-1210, manufactured by Mountech) to adsorb a nitrogen gas on the surface of a sample according to the BET method, and calculate the specific surface area by a BET multipoint method.

(D) The inorganic filler may be surface-treated with any surface-treating agent. Examples of the surface treatment agent include coupling agents such as amine-based silane coupling agents, epoxy silane-based coupling agents, mercapto silane-based coupling agents, titanate-based coupling agents, and the like; alkoxysilane compounds, organic silazane compounds ;Wait. Surface treatment with such a surface treatment agent can improve the moisture resistance and dispersibility of the (D) inorganic filler.

Examples of commercially available surface treatment agents include "KBM403" (3-glycidyloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd. and "KBM803" (3-mercaptopropyltrimethyl) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Oxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxy) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Silane), Shin-Etsu Chemical Industry Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Industry Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Industry Co., Ltd. "KBM-4803" (Long-chain epoxy-type silane coupling agent) and the like. The surface treatment agents may be used singly or in combination of two or more kinds.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the (D) inorganic filler. (D) The carbon content per unit surface area of the inorganic filler is preferably 0.02 mg / m ² or more, and more preferably 0.1 mg / m ² or more, from the viewpoint of improving the dispersibility of the inorganic filler. Particularly preferred is 0.2 mg / m ² or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, the aforementioned carbon content is preferably 1 mg / m ² or less, more preferably 0.8 mg / m ² or less, and particularly preferably It is 0.5 mg / m ² or less.

(D) The amount of carbon per unit surface area of the inorganic filler. The surface treated (D) inorganic filler can be washed with a solvent (such as methyl ethyl ketone (hereinafter sometimes referred to as "MEK")). Determined after net treatment. Specifically, a sufficient amount of MEK and an inorganic filler (D) surface-treated with a surface treatment agent were mixed, and ultrasonic cleaning was performed at 25 ° C for 5 minutes. Secondly, after removing the supernatant so as not to volatilize to dryness, a carbon analyzer can be used to measure the carbon content of each unit surface area of the (D) inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

The amount of the (D) inorganic filler in the resin composition is preferably 100% by mass or more, more preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass relative to the nonvolatile content in the resin composition. % Or more, particularly preferably 20% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less. When the amount of the (D) inorganic filler is equal to or more than the lower limit of the aforementioned range, the thermal expansion rate of the hardened material of the resin composition can be reduced, and the warpage of the insulating layer can be suppressed. In addition, when the amount of the (D) inorganic filler is equal to or less than the upper limit of the aforementioned range, the mechanical strength of the hardened material of the resin composition can be improved, and particularly the resistance to elongation can be improved.

[6. (E) Epoxy resin not containing a fluorine atom] The resin composition may contain (E) a non-fluorine-based epoxy resin as an optional component in addition to the components described above. The (E) non-fluorine-based epoxy resin refers to an epoxy resin that does not contain a fluorine atom in the molecule. Examples of the (E) non-fluorine-based epoxy resin include xylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and dicyclopentadiene. Epoxy resin, phenol novolac epoxy resin, naphthol novolac epoxy resin, novolac epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthalene Phenolic epoxy resin, onion epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, linear aliphatic Epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiral ring, cyclohexane epoxy resin, cyclohexanedimethanol type Epoxy resin, naphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin. One type of epoxy resin can be used alone, or two or more types can be used in combination.

As the (E) non-fluorine-based epoxy resin, an aromatic epoxy resin is preferred from the viewpoint of reducing the average linear thermal expansion coefficient of the insulating layer. Among them, (E) the non-fluorine-based epoxy resin is preferably selected from the group consisting of bisphenol A-type epoxy resin, xylenol-type epoxy resin, and biphenyl from the viewpoint that the desired effect of the present invention is significantly obtained. One or more types of epoxy resins in the group consisting of aralkyl-type epoxy resin, naphthyl ether-type epoxy resin, naphthalene-type 4-functional epoxy resin, and naphthol-type epoxy resin, particularly preferably double Phenol A type epoxy resin, xylenol type epoxy resin and naphthol type epoxy resin.

As the (E) non-fluorine-based epoxy resin, the resin composition is preferably an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of significantly obtaining the desired effect of the present invention, the epoxy resin having two or more epoxy groups in one molecule is 100% by mass of the non-volatile content of the (E) non-fluorine-based epoxy resin. The proportion is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

Among the epoxy resins, there are epoxy resins that are liquid at 20 ° C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at 20 ° C (hereinafter sometimes referred to as "liquid epoxy resins"). "Solid epoxy resin"). As the (E) non-fluorine-based epoxy resin, the resin composition may include only a liquid epoxy resin, and may include only a solid epoxy resin, but preferably includes a combination of a liquid epoxy resin and a solid epoxy resin. Epoxy. As the (E) non-fluorine-based epoxy resin, by combining a liquid epoxy resin and a solid epoxy resin, the flexibility of the resin composition layer can be improved, or the hardened material of the resin composition can be broken. strength.

The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule, and more preferably an aromatic liquid epoxy resin having two or more epoxy groups in one molecule. Resin.

The liquid epoxy resin is preferably a bisphenol A epoxy resin, a bisphenol F epoxy resin, a naphthalene epoxy resin, a glycidyl ester epoxy resin, a glycidylamine epoxy resin, Novolac epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane epoxy resin, cyclohexanedimethanol epoxy resin, glycidylamine epoxy resin, and butadiene The structured epoxy resin is more preferably a glycidylamine epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, and a naphthalene epoxy resin, and particularly preferably a bisphenol A epoxy resin. .

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC; "828US", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation "," EPIKOTE 828EL "(bisphenol A type epoxy resin);" jER807 "," 1750 "(bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation;" jER152 "(phenol novolak) manufactured by Mitsubishi Chemical Corporation Type epoxy resin); "630" and "630LSD" (glycidylamine type epoxy resin) made by Mitsubishi Chemical Corporation; "ZX1059" (bisphenol A type epoxy resin and Mixture of phenol F-type epoxy resins; "EX-721" (glycidyl ester epoxy resin) manufactured by Nagase ChemteX, "CELLOXIDE 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel Resin); "PB-3600" (an epoxy resin with a butadiene structure) manufactured by Daicel; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidyl ring) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. Hexane type epoxy resin); etc. These can be used alone or in combination of two or more.

The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule. Resin.

The solid epoxy resin is preferably a cresol-type epoxy resin, a biphenylaralkyl-type epoxy resin, a naphthalene-type epoxy resin, a naphthalene-type 4-functional epoxy resin, and a cresol novolac-type epoxy resin. , Dicyclopentadiene epoxy resin, ginseng phenol epoxy resin, naphthol epoxy resin, biphenyl epoxy resin, naphthyl ether epoxy resin, onion epoxy resin, bisphenol A type Epoxy resin, tetraphenylethane type epoxy resin, more preferably xylenol type epoxy resin, biphenylaralkyl type epoxy resin, naphthyl ether type epoxy resin, naphthalene type 4-functional epoxy resin Resin and naphthol type epoxy resin.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene-type 4-functional epoxy resin) manufactured by DIC ); "N-690" (cresol novolac epoxy resin) manufactured by DIC; "N-695" (cresol novolac epoxy resin) manufactured by DIC; "HP-7200" manufactured by DIC "(Dicyclopentadiene epoxy resin);" HP-7200HH "," HP-7200H "," EXA-7311 "," EXA-7311-G3 "," EXA-7311-G4 ", "EXA-7311-G4S", "HP6000" (Dnaphthyl Ether Type Epoxy Resin); "EPPN-502H" (Shen Phenol Type Epoxy Resin) made by Nippon Kayaku Co .; "NC7000L" made by Nippon Kayaku Co. "(Naphthol novolac epoxy resin);" NC3000H "," NC3000 "," NC3000L "," NC3100 "(biphenylaralkyl type epoxy resin) made by Nippon Kayaku Co., Ltd .; Nippon Steel & Sumitomo Chemical "ESN475V" (naphthol type epoxy resin) made by the company; "ESN485" (naphthol novolac type epoxy resin) made by Nippon Steel & Sumitomo Chemical Corporation; "YX4000H", "YX400" made by Mitsubishi Chemical Corporation 0 "," YL6121 "(biphenyl type epoxy resin);" YX4000HK "(xylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation;" YX8800 "(onion type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi "YL7800" (茀 -type epoxy resin) manufactured by Chemical Corporation; "jER1010" (solid bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type) manufactured by Mitsubishi Chemical Corporation Epoxy). These can be used alone or in combination of two or more.

When (E) a non-fluorine-based epoxy resin is used in combination of a liquid epoxy resin and a solid epoxy resin, the mass ratio of these (liquid epoxy resin: solid epoxy resin) is preferably 1: 0.1 to 1:15, more preferably 1: 0.5 to 1:10, and particularly preferably 1: 1 to 1: 8. When the mass ratio of the liquid epoxy resin to the solid epoxy resin is in the aforementioned range, when used in the form of a film, better adhesion can be obtained. In addition, when used in the form of a film, sufficient flexibility is obtained, and operability can be improved. Furthermore, the breaking strength of the hardened | cured material of a resin composition can be improved effectively.

The range of the epoxy equivalent of the (E) non-fluorine-based epoxy resin is preferably the same range as the range of the epoxy equivalent of the (A) fluorine-based epoxy resin. Thereby, the same advantages as those described in the item (A) of the fluorine-based epoxy resin can be obtained.

The range of the weight average molecular weight of the (E) non-fluorine-based epoxy resin is preferably the same as that described as the range of the weight average molecular weight of the (A) fluorine-based epoxy resin. Thereby, the same advantages as those described in the item (A) of the fluorine-based epoxy resin can be obtained.

The amount of the (E) non-fluorine-based epoxy resin in the resin composition is 100% by mass based on the non-volatile content in the resin composition from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability. It is preferably 5 mass% or more, more preferably 8 mass% or more, particularly preferably 10 mass% or more, more preferably 70 mass% or less, more preferably 50 mass% or less, and particularly preferably 40 mass% or less.

[7. (F) Thermoplastic resin] The resin composition may contain (F) a thermoplastic resin as an optional component in addition to the components described above. Examples of the thermoplastic resin as the (F) component include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyimide resin, polyetherimide Imine resin, polyfluorene resin, polyetherfluorene resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin. Among these, a phenoxy resin is preferable from the viewpoint that the desired effect of the present invention is significantly obtained. The thermoplastic resin may be used alone or in combination of two or more kinds.

Examples of the phenoxy resin include those selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorene skeleton, and a dicyclopentadiene skeleton. 1 or more types of phenoxy resins in the group consisting of norbornene skeleton, naphthalene skeleton, onion skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

Specific examples of the phenoxy resin include "1256" and "4250" (both are phenoxy resins containing a bisphenol A skeleton) manufactured by Mitsubishi Chemical Corporation; and "YX8100" (containing bisphenols) manufactured by Mitsubishi Chemical Corporation S-frame phenoxy resin); "YX6954" (phenoxy resin containing bisphenolacetophenone skeleton) manufactured by Mitsubishi Chemical Corporation; "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Chemical Corporation; Mitsubishi Chemical Company-made "YX6954BH30", "YX7553", "YX7553BH30", "YL7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7891BH30" and "YL7482".

(F) The weight average molecular weight in terms of polystyrene of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, particularly preferably 20,000 or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. It is 70,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less. (F) The polystyrene-equivalent weight average molecular weight of the thermoplastic resin can be measured by a gel permeation chromatography (GPC) method.

When (F) a thermoplastic resin is used, the amount of the (F) thermoplastic resin in the resin composition is preferably 0.5% by mass or more, more preferably 0.6% by mass or more, based on 100% by mass of the nonvolatile matter in the resin composition. It is more preferably 0.7 mass% or more, more preferably 15 mass% or less, even more preferably 12 mass% or less, and still more preferably 10 mass% or less.

[8. (G) Hardening Accelerator] The resin composition may contain (G) a hardening accelerator as an optional component in addition to the components described above. By using (G) a hardening accelerator, hardening can be accelerated | stimulated when hardening a resin composition.

Examples of the (G) hardening accelerator include a phosphorus-based hardening accelerator, an amine-based hardening accelerator, an imidazole-based hardening accelerator, a guanidine-based hardening accelerator, a metal-based hardening accelerator, and a peroxide-based hardening accelerator. Among them, preferred are phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators, and more preferred are amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators. Particularly preferred is an amine-based hardening accelerator. (G) A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the phosphorus-based hardening accelerator include triphenylphosphine, osmium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate. Among them, triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine, tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6-ginseng ( Dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) -undecene. Among them, 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferred.

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl 4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2- Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamine -6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methyl Imidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine Cyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl Imidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzo Imidazole compounds such as azole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline; and the addition of imidazole compounds and epoxy resins Adult. Among these, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

Commercially available products can be used as the imidazole-based hardening accelerator, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine-based hardening accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, and dimethyl Guanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1 , 5,7-triazabicyclo [4.4.0] dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1- (o-tolyl) biguanide. Among them, dicyandiamide and 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

Examples of the metal-based hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organocobalt complexes such as cobalt (II) acetopyruvate, cobalt (III) ethidium pyruvate, and organocopper complexes such as copper (II) acetopyruvate. Compounds, organic zinc complexes such as zinc (II) acetonate, organic iron complexes such as iron (III) acetonate, nickel organic complexes of nickel (II) acetonate Organomanganese complexes such as manganese (II) acetamidine pyruvate. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

Examples of the peroxide-based hardening accelerator include cyclohexanone peroxide, tert-butylperoxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, and tert-butyl Cumene peroxide, di-tert-butyl peroxide, dicumyl hydrogen peroxide, cumene hydrogen peroxide, tert-butyl hydrogen peroxide.

As the peroxide-based hardening accelerator, a commercially available product can be used, and examples thereof include "PERCUMYL D" manufactured by Nippon Oil Corporation.

When the (G) hardening accelerator is used, the amount of the (G) hardening accelerator in the resin composition is from the viewpoint of remarkably obtaining the desired effect of the present invention, relative to 100 mass of the non-volatile component in the resin composition. %, Preferably 0.01 mass% or more, more preferably 0.03 mass% or more, particularly preferably 0.05 mass% or more, more preferably 3 mass% or less, more preferably 2 mass% or less, and particularly preferably 1 mass% or less.

[9. (H) Coupling agent] The resin composition may contain (H) a coupling agent as an optional component in addition to the components described above. Since the dispersibility of the (D) inorganic filler can be improved by using the (H) coupling agent, the surface roughness of the insulating layer after the roughening treatment can be reduced.

Examples of the (H) coupling agent include the same as those exemplified as the surface treatment agent for the (D) inorganic filler. The (H) coupling agent may be used alone or in combination of two or more kinds.

When the (H) coupling agent is used, the amount of the (H) coupling agent in the resin composition is preferably 0.1% by mass or more, and more preferably 0.2% by mass or more, based on 100% by mass of the nonvolatile matter in the resin composition. Particularly preferred is 0.5 mass% or more, preferably 5 mass% or less, more preferably 3 mass% or less, and particularly preferred 1 mass% or less. When the amount of the (H) coupling agent is in the aforementioned range, the surface roughness of the insulating layer after the roughening treatment can be reduced.

[10. (I) Additives] The fluorene resin composition may further contain additives as optional components in addition to the components described above. Examples of such additives include organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; thickeners, defoamers, leveling agents, adhesion-imparting agents; colorants; flame retardants; Wait. The additives may be used singly or in combination of two kinds.

[11. Production method of resin composition] (2) The resin composition can be produced, for example, by mixing the blended component with a solvent as necessary, and using a stirring device such as a rotary mixer.

[12. Characteristics of resin composition] (1) The above-mentioned hardened product of the resin composition can reduce its dielectric constant. Therefore, an insulating layer having a low dielectric constant can be obtained from the cured product of the resin composition. For example, when the resin composition is cured by the method described in the examples to obtain a cured product, the dielectric constant of the cured product is preferably 3.00 or less, more preferably 2.98 or less, and particularly preferably It is 2.97 or less. Here, the dielectric constant of the hardened material can be measured by the method described in the examples.

When the conductor layer is formed on the layer of the hardened material of the resin composition described above, the adhesion between the layer of the hardened material and the conductor layer can be improved. Thereby, the hardened | cured material of the said resin composition can obtain the insulating layer with high adhesiveness with respect to a conductor layer. For example, in the method described in the examples, when the insulating layer is formed of a cured product of a resin composition, and the conductive layer is formed on the insulating layer by plating, the peeling strength can be increased. Specifically, the aforementioned peel strength may be preferably set to 0.2 kgf / cm or more, more preferably set to 0.3 kgf / cm or more, and particularly preferably set to 0.4 kgf / cm or more. The aforementioned peel strength can be measured by the method described in the examples.

The resin composition containing (A) a fluorine-based epoxy resin can achieve high adhesiveness to the conductor layer as described above, and it is surprising to consider from the common sense of a person having ordinary knowledge in the field of the present invention. In general, since a material containing fluorine has a low affinity for a conductor, the adhesion tends to be low. The above-mentioned tendency can also be understood from the conventional insulation layer obtained from the resin composition containing the (C) fluorine-based filler material from the deterioration of the adhesion of the conductor layer. Therefore, if a person with ordinary knowledge in the field of the present invention knows that when (C) a fluorine-based filler is used in combination with (A) a fluorine-based epoxy resin, the amount of fluorine-containing materials is increased, and the adhesiveness is expected to further decrease. However, in the resin composition described above, high adhesion can be achieved by a combination of (C) a fluorine-based filler and (A) a fluorine-based epoxy resin.

The resin composition-based (C) fluorine-based filler is excellent in dispersibility. Therefore, (C) aggregation of the fluorine-based filler can be suppressed in the resin composition. For example, when a resin composition layer having a thickness described in the examples is formed, and the resin composition layer is observed at a magnification of 1000 times by the method described in the examples, the number of aggregates observed can be reduced. Specifically, the number of aggregates having a diameter of 50 μm or more can be set to 0 per 10 fields of view, and the number of aggregates having a diameter of 10 μm or more can be set to less than 10 per 10 fields of view.

Based on the resin composition described above, the inventors have speculated as follows on how to obtain the effect mechanism of the aforementioned effects. However, the technical scope of the present invention is not limited by the action mechanism described below.组合 When (C) a fluorine-based filler is combined with an epoxy resin and (B) a hardener, it has the effect of reducing the dielectric constant of the hardened material of the resin composition. However, (C) the fluorine-based filler has low affinity with general epoxy resins. Therefore, when the (C) fluorine-based filler is combined with a general epoxy resin to be included in the resin composition, the (C) fluorine-based filler is low in dispersibility and easily aggregates. On the other hand, since (A) fluorine-based epoxy resin contains a fluorine atom, it has high affinity with (C) fluorine-based filler and is a resin having an epoxy group. Other ingredients also have high affinity. Therefore, by combining the (C) fluorine-based filler with (A) the fluorine-based epoxy resin, the aggregation of the (C) fluorine-based filler is suppressed, so that the dispersibility of the (C) fluorine-based filler can be improved. Further, when the aggregation of the fluorine-based filler (C) is suppressed as described above, the resin composition suppresses compositional shift. Therefore, when the resin composition is thermally cured, it is difficult to cause stress concentration due to expansion and contraction of each component. Therefore, it is difficult for the hardened material of the resin composition to generate a starting point of destruction due to stress concentration. In addition, in general, (C) the periphery of the agglomerates of the fluorine-based filler is easily immersed in a chemical solution for roughening treatment. When voids are generated in the hardened material due to the immersion of the chemical solution, the mechanical strength of the hardened material may be reduced, and swelling due to annealing may occur. On the other hand, when the aggregation of the (C) fluorine-based filler is suppressed, the infiltration of the chemical solution as described above can be suppressed. Accordingly, the combination of (A) a fluorine-based epoxy resin, (B) a hardener, and (C) a fluorine-based filler can suppress the peeling of the conductor layer accompanying the destruction of the hardened material of the insulating layer. The conductive layer exhibits high adhesion.

In general, when a hardened product of a resin composition containing a filler material includes agglomerates of the filler material, during the roughening treatment, it is easy to immerse the chemical solution around the agglomerates, which may increase the surface of the roughened surface. Ten-point average roughness Rz tendency. Therefore, the ten-point average roughness Rz is generally related to the dispersibility of the (C) fluorine-based filler in the hardened material. The greater the degree of aggregation of the (C) fluorine-based filler, the ten-point average roughness Rz has The greater the tendency. As described above, since the dispersibility of the (C) fluorine-based filler is good, when the hardened material of the resin composition is subjected to roughening treatment, the ten-point average roughness Rz can usually be reduced. For example, in the method described in the examples, an insulating layer is formed from a hardened product of a resin composition. When the insulating layer is roughened, the ten-point average roughness Rz of the roughened insulating layer can be reduced. Specifically, the ten-point average roughness Rz is preferably 4.5 μm or less, more preferably 4.0 μm or less, and particularly preferably 3.0 μm or less.

When the hardened material of the resin composition is subjected to roughening treatment, the surface roughness after the roughening treatment can generally be reduced. According to this, the hardened | cured material of the said resin composition can obtain the insulating layer with small surface roughness normally. For example, in the method described in the example, an insulating layer is formed by a hardened product of a resin composition. When the insulating layer is roughened, the arithmetic average roughness Ra of the roughened insulating layer can be set to a specified value. range. Specifically, the aforementioned arithmetic average roughness Ra is preferably 400 nm or less, more preferably 300 nm or less, and particularly preferably 250 nm or less.

[13. Use of resin composition] The resin composition of the present invention can be used as a resin composition for forming an insulating layer of a circuit board such as a printed circuit board. The aforementioned insulating layer is an insulating layer formed on the insulating layer to form a conductor layer (including a redistribution layer). Therefore, the resin composition can 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 manufacture of a circuit board by a build-up method.

In particular, the advantage of using an insulating layer with a low dielectric constant is obtained. This resin composition is suitable as a resin composition for forming an insulating layer of a high-frequency circuit board (a resin composition for forming an insulating layer of a high-frequency circuit board). )use. Among them, this resin composition can be suitably used as a resin composition for forming an interlayer insulating layer of a high-frequency circuit board (a resin composition for forming an interlayer insulating layer of a high-frequency circuit board). Here, the "high-frequency circuit board" means a circuit board that can operate even with electrical signals in a high-frequency region. The "high-frequency region" means a region that is usually 1 GHz or more, and the above-mentioned resin composition is effective particularly in a region from 28 GHz to 80 GHz.

In addition, an insulating layer having a low dielectric constant contributes to the reduction of the circuit substrate, and is therefore suitable for applications in which a thin circuit substrate is sought. Furthermore, an insulating layer having a low dielectric constant is suitable because it makes it easier to control the impedance of the circuit board and improves the degree of freedom in designing the circuit board. From such a point of view, when a suitable application of the resin composition is enumerated, for example, a circuit board such as a motherboard, an IC package substrate, a camera module substrate, and a fingerprint authentication sensor substrate used in a mobile device can be cited. In specific examples, the fingerprint authentication sensor may be provided in the order of an insulating layer included in a circuit board, a plurality of electrodes formed on the aforementioned insulating layer, and an insulating film. In this fingerprint authentication sensor, the capacitance value of the capacitor formed by the fingers and electrodes placed on the insulating film and the insulating film is different from the convex part and the concave part of the fingerprint to authenticate the fingerprint. When such a fingerprint authentication sensor can reduce the thickness of the insulation layer, miniaturization of the sensor itself becomes possible.

In addition, the resin composition of the present invention can be used as a sheet-like laminated material such as a film, a prepreg, a solder resist, an underfill material, a wafer bonding material, a semiconductor sealing material, a filling resin, a component embedding resin, etc., A wide range of uses for resin compositions.

[14. Sheet-like laminated material] The above-mentioned resin composition is applied in a varnish state, and can be used for the formation of an insulating layer. However, industrially, it is preferably used in the form of a sheet-like laminated material containing this resin composition. Preferable examples of the laminar laminate include adhesive films and prepregs.

In one embodiment, the thin film includes a support and a resin composition layer provided on the support. The resin composition layer is a layer formed of the resin composition described above, and is sometimes referred to as a "adhesive layer".

From the viewpoint of thinning, the thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, and still more preferably 60 μm or less. Among them, 50 μm or less is particularly preferred, and 30 μm or less is particularly preferred. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be, for example, 1 μm or more, 5 μm or more, 10 μm or more.

Examples of the support include a film made of a plastic material, a metal foil, and a release paper. As the support, a film or metal foil made of a plastic material is preferred.

When a film made of a plastic material is used as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter referred to as " Polyester (such as "PEN"); polycarbonate (hereinafter sometimes referred to as "PC"); acrylic methyl polymers such as polymethyl methacrylate (hereinafter sometimes referred to as PMMA); cyclic Polyolefin; triethylfluorene cellulose (hereinafter sometimes referred to as TAC), polyether sulfide (hereinafter sometimes referred to as PES); polyetherketone; polyfluorene. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and polyethylene terephthalate is particularly preferred because it is inexpensive and has excellent availability.

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

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

Moreover, as a support body, the support body with a mold release layer which has a mold release layer can be used for the surface joined to a resin composition layer. As a mold release agent which can be used for the mold release layer of the support provided with a mold release layer, for example, it can be selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. One or more types of release agent. Examples of commercially available mold release agents include "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, which are alkyd resin-based release agents. Examples of the support with a release layer include "Lumirror T60" manufactured by Toray, "Purex" manufactured by Teijin; "Unipiel" manufactured by Unitika; and the like.

The thickness of the support is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

Next, for example, a thin film of a resin varnish containing an organic solvent and a resin composition is prepared. This resin varnish can be applied to a support using a coating device such as a die coater, and then dried to form a resin composition layer. .

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and Acetate solvents such as carbitol acetate; Cellulose solvents and carbitol solvents such as butyl carbitol; Aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide and dimethyl Amidamine-based solvents such as acetylacetamide (DMAc) and N-methylpyrrolidone. The organic solvents may be used singly or in combination of two or more kinds.

Drying can be performed by a known method such as heating or hot air blowing. The drying conditions are set such that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, and preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing an organic solvent of 30% to 60% by mass is used, the resin can be formed by drying at 50 ° C to 150 ° C for 3 to 10 minutes. Composition layer. The resin composition layer is generally obtained by using a coating film of a resin varnish as a semi-hardened film.

The film may include any layer other than the support and the resin composition layer if necessary. For example, a protective film according to the support may be provided on the surface of the adhesive film that 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 μm to 40 μm. By the protective film, adhesion or scratches to the dust or the like on the surface of the resin composition layer can be suppressed. When the adhesive film has a protective film, the adhesive film is usually made usable by peeling the protective film. The film can then be rolled into a roll and stored.

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

The sheet-like fibrous substrate used for the prepreg is not particularly limited. As the sheet-like fibrous substrate, for example, an arbitrary fibrous substrate used as a substrate 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 substrate is preferably 900 μm or less, more preferably 800 μm or less, even more preferably 700 μm or less, and particularly preferably 600 μm or less. From the viewpoint of suppressing the immersion depth of the plating concerning the formation of the conductor layer, the thickness of the sheet-like fiber substrate is preferably 30 μm or less, more preferably 20 μm or less, and particularly preferably 10 μm or less. The lower limit of the thickness of the sheet-like fiber substrate is usually 1 μm or more, and may be 1.5 μm or more or 2 μm or more.

The prepreg can be produced by a method such as a hot melt method, a solvent method, and the like. The thickness of the prepreg may be in the same range as the resin composition layer of the above-mentioned adhesive film.

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

The "inner substrate" refers to a member that becomes a substrate of a circuit substrate. Examples of the inner layer substrate include those including 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. In addition, the inner substrate generally includes a conductor layer formed directly or indirectly on one or both surfaces of the core substrate. This conductor layer can be patterned in order to function as an electrical circuit, for example. A conductor layer formed on one or both sides of a core substrate substrate as an inner layer substrate of a circuit is sometimes referred to as an "inner layer circuit substrate." In addition, in order to manufacture a printed circuit board, at least one of an insulating layer and a conductor layer is an intermediate manufactured product to be formed, and is also included in the term "inner substrate". When the circuit board is a built-in part, an inner substrate of the built-in part can be used.

The thickness of the inner layer substrate is usually 50 μm to 4000 μm, and from the viewpoint of improving the mechanical strength of the circuit substrate and low backing (reduction in thickness), it is preferably 200 μm to 3200 μm.

In the inner substrate, in order to electrically connect the conductor layers on both sides thereof, one or more through holes may be provided from one surface to the other surface. The inner substrate may include other components such as a passive element.

The insulating layer is a layer of a cured product of a resin composition. The insulating layer formed from this hardened material is particularly suitable for motherboards, IC package substrates, camera module substrates, and fingerprint authentication for circuit boards for stacked circuits, high-frequency circuit boards, and mobile devices. An insulating layer for a circuit substrate such as a sensor substrate.

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

The thickness of the insulating layer is usually 1 μm to 200 μm, and from the viewpoint of improving electrical characteristics and lowering of the circuit substrate, it is preferably 1 μm to 30 μm.

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

Since the aforementioned insulating layer is a layer formed from the cured product of the above-mentioned resin composition, the excellent characteristics of the aforementioned cured product of the resin composition can be exhibited. Therefore, the insulating layer of the circuit substrate is preferably the surface roughness such as the dielectric constant of the insulating layer, the peel strength of the insulating layer and the conductor layer, the ten-point average roughness Rz and the arithmetic average roughness Ra after the roughening treatment. The characteristics of the resin composition are adjusted to the same ranges as those described in the item of the characteristics of the resin composition. These characteristics can be measured by the methods described in the examples.

The circuit substrate can be manufactured by a manufacturing method including the following steps (I) and (II), for example, using an adhesive film. (I) A step of laminating an adhesive film on the inner substrate such that the resin composition layer of the adhesive film is bonded to the inner substrate. (II) A step of forming the insulating layer by the thermosetting resin composition layer.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by a heat-pressing step of pressing the adhesive film from the support side and heating the inner layer substrate. Examples of the member for heating and pressing step (also referred to as "heating and pressing member") include a heated metal plate (SUS mirror plate, etc.), a metal roller (SUS roller), and the like. Still, it is preferable that the heat-pressing member is not directly pressed to the support of the bonding film, but that the unevenness on the surface of the inner layer substrate is pressed through the elastic material such as heat-resistant rubber to sufficiently follow the bonding film.

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

Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressure laminators made by Meiki Seisakusho, vacuum applicators made by Nikko Materials Co., Ltd., and batch vacuum pressure laminators.

After lamination, the laminated resin composition layer can be smoothed under normal pressure (under atmospheric pressure), for example, by pressing a heated and pressed member from the support side. The pressing conditions for the smoothing treatment can be set to the same conditions as the heat-pressing conditions for the above-mentioned lamination. The smoothing treatment can be performed by a commercially available laminator. The lamination and smoothing treatment can be continuously performed using the above-mentioned commercially available vacuum laminator.

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

In step (II), the resin composition layer is thermally hardened to form an insulating layer. The conditions for thermal curing of the resin composition layer are not particularly limited, and the conditions used when forming the insulating layer of the circuit board can be arbitrarily adopted.

The thermosetting conditions of the resin composition layer differ 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 ° C to 240 ° C (preferably in the range of 150 ° C to 220 ° C, more preferably in the range of 170 ° C to 200 ° C). The curing time is usually in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, and more preferably 15 minutes to 90 minutes).

Before the resin composition layer is thermally cured, the resin composition layer may be pre-heated at a temperature lower than the curing temperature. For example, before the thermosetting resin composition layer, the resin composition layer can usually be preheated at a temperature of 50 ° C to 120 ° C (preferably 60 ° C to 110 ° C, more preferably 70 ° C to 100 ° C). Usually 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

The method of manufacturing a circuit substrate may further include (III) a step of drilling into the insulating layer, (IV) a step of performing a roughening treatment on the insulating layer, and (V) a step of forming a conductor layer. These steps (III) to (V) can be performed in accordance with an appropriate method used for manufacturing a circuit board. Moreover, when the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or step (IV). And at any point in time between step (V).

Step (III) is a step of drilling holes in the insulating layer. By drilling, holes such as through holes and through holes can be formed in the insulating layer. Step (III) can be carried out according to the composition of the resin composition used for forming the insulating layer, for example, using a drill, a laser, a plasma, or the like. The size or shape of the hole can be appropriately determined according to the design of the printed circuit board.

Step (IV) is a step of performing a roughening treatment on the insulating layer. The order and conditions of the roughening treatment are not particularly limited, and any order and conditions used when forming the insulating layer of the circuit substrate can be adopted. For example, the insulating layer can be roughened by sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing solution.

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

Examples of the oxidizing agent include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The oxidant may be used alone or in combination of two or more kinds. The roughening treatment of an oxidant such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in the oxidant solution heated to 60 ° C to 80 ° C for 10 to 30 minutes. The concentration of the permanganate in the alkaline permanganate solution is preferably 5 to 10% by mass. Examples of commercially available oxidants include alkaline permanganic acid solutions such as "Concentrate (R) Compact CP" and "Dosing solution" (Securiganth P) manufactured by Atotech Japan.

The neutralizing solution is preferably an acidic aqueous solution. As a commercially available product of the neutralizing solution, for example, "Reduction solution Securigant P" manufactured by Atotech Japan is mentioned. The neutralizing solution may be used singly or in combination of two or more kinds. The treatment with the neutralizing solution can be performed by immersing the treated surface of the insulating layer subjected to the roughening treatment with an oxidizing agent at a neutralizing solution at 30 ° C to 80 ° C for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing the insulating layer subjected to the roughening treatment with an oxidizing agent at a neutralizing solution at 40 ° C to 70 ° C for 5 to 20 minutes is preferred.

Step (V) is a step of forming a conductor layer. The material used for the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer includes one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Above the metal. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include a layer selected from an alloy of two or more metals (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy) selected from the above group. Among them, from the viewpoints of versatility of forming the conductor layer, cost, and ease of patterning, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or nickel is preferred. ･ Cr alloy, Cu ･ Ni alloy, Cu ･ Ti alloy alloy layer. Further, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper; or an alloy layer of a nickel-chromium alloy, and even more preferably a single metal layer of copper.

The conductor layer may have a single-layer structure, or a multi-layer structure including two or more single metal layers or alloy layers composed of different kinds of metals or alloys. When the conductor layer has a multi-layer structure, the layer bonded to the insulating layer is preferably a single metal layer of chromium, zinc, or titanium or an alloy layer of a nickel-chromium alloy.

The thickness of the conductive layer is 3 μm to 200 μm, and preferably 10 μm to 100 μm.

The conductive layer can be formed by directly patterning the metal foil used as a support for a thin film, for example. The conductive layer can be formed by, for example, plating. As a formation method by plating, for example, the surface of the insulating layer can be plated by a method such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern. Among them, from the standpoint of simplicity of production, it is preferably formed by a semi-additive method.

Hereinafter, an example in which a conductive layer is formed by a semi-additive method will be described. First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern that exposes a part of the plating seed layer is formed in a manner corresponding to a desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Then, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

The conductive layer can be formed using, for example, a metal foil. When a metal foil is used to form the conductor layer, step (V) is preferably performed between step (I) and step (II). For example, after step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. Lamination of the resin composition layer and the metal foil can be performed by a vacuum lamination method. The conditions for lamination may be the same as the conditions for lamination of the inner substrate and the adhesive film in step (I). Next, step (II) is performed to form an insulating layer. Then, using a metal foil on the insulating layer, a conductive layer having a desired wiring pattern can be formed by a subtractive method, a modified semi-additive method, or the like. The metal foil can be produced by, for example, an electrolytic method or a rolling method. Examples of commercially available metal foils include HLP foil manufactured by JX Nippon Nissei Metal Co., Ltd., JXUT-III foil, 3EC-III foil manufactured by Mitsui Metal Mining Corporation, and TP-III foil.

When the circuit board includes two or more insulating layers and conductive layers (stacked layers), the above-mentioned steps of forming the insulating layer and the steps of forming the conductive layer are repeated one or more times, and it is possible to manufacture multiple layers that can be used as circuits. Circuit board with wiring structure.

In other embodiments, the circuit substrate may be replaced by a prepreg instead of a film. The manufacturing method using a prepreg is basically the same as that in the case of using an adhesive film.

[16. Semiconductor device] (1) The semiconductor device includes the circuit board described above. This semiconductor device can be manufactured using a circuit board.

Examples of the semiconductor device include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trains, ships, and aircraft).

The semiconductor device can be manufactured, for example, by mounting a component (semiconductor wafer) on a conductive substrate. The so-called "conducting place" means "a place where an electric signal can be transmitted on a circuit board". This place can be the surface of the circuit board, or it can be any place embedded in the circuit board. In addition, as the semiconductor wafer, an electric circuit element using a semiconductor as a material can be arbitrarily used.

As a method for mounting a semiconductor wafer during the manufacture of a semiconductor device, any method for effectively performing the function of the semiconductor wafer can be adopted. Examples of the mounting method of a semiconductor wafer include a wire bonding mounting method, a flip chip mounting method, a mounting method by a bumpless layer (BBUL), and a mounting method by an anisotropic conductive film (ACF). Mounting method, mounting method by non-conductive film (NCF). Here, the "mounting method by a bumpless layer (BBUL)" means a "mounting method of directly embedding a semiconductor wafer into a circuit board and connecting the wiring between the semiconductor wafer and the circuit board". [Example]

Hereinafter, although the present invention will be specifically described by way of examples, the present invention is not limited to these examples. In the following description, "parts" and "%" mean "mass parts" and "mass%", respectively, unless explicitly stated otherwise.

[Example 1] 12 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828US" manufactured by Mitsubishi Chemical Corporation), xylenol type epoxy resin (epoxy equivalent 190, manufactured by Mitsubishi Chemical Corporation " YX4000HK '') 10 parts, biphenyl aralkyl epoxy resin (epoxy equivalent 276, NC3000 manufactured by Nippon Kayaku Co., Ltd.) 30 parts, naphthol epoxy resin (epoxy equivalent 332, Nippon Steel & Sumitomo Chemical) 10 parts of "ESN475V" made by the company, 10 parts of bisphenol AF epoxy resin (epoxy equivalent 235, "YL7760" made by Mitsubishi Chemical Corporation), phenoxy resin (30% by mass of methyl ethyl ketone / Cyclohexanone = 1/1 solution, 20 parts of "YL7553BH30" manufactured by Mitsubishi Chemical Corporation, were heated and dissolved while stirring 60 parts of methyl ethyl ketone and 20 parts of cyclohexanone to obtain a resin solution.

For this resin solution, 15 parts of an active ester-based hardener (active group equivalent 223, toluene solution of 65% by mass of non-volatile content, "HPC8000-65T" manufactured by DIC Corporation) was mixed, and a cresol novolac type hardener containing a triazine skeleton Agent (151 phenol equivalents, 2-methoxypropanol solution with 50% by mass of solid content, "LA3018-50P" manufactured by DIC Corporation), hardening accelerator (4-dimethylaminopyridine (DMAP), solid 5 parts by weight of methyl ethyl ketone solution) 4 parts, spherical silica (Admatechs) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 100 parts of "SO-C2" manufactured by the company, average particle diameter of 0.5 μm, specific surface area of 5.9 m ² / g) and 80 parts of polytetrafluoroethylene particles ("LUBRON L-2" manufactured by Daikin Industries, average particle diameter of 3 μm) The resin varnish is obtained by uniformly dispersing with a high-speed rotary mixer.

As a support, a polyethylene terephthalate film (thickness: 38 μm, manufactured by Lintec Corporation) having an alkyd resin-based release layer on the surface was prepared. The aforementioned resin varnish was uniformly applied on this support using a die coater. The coated resin varnish was dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 6 minutes to form a resin composition layer, and an adhesive film having a support and a resin composition layer was obtained. The thickness of the resin composition layer was 50 μm, and the amount of residual solvent in the resin composition was about 2% by mass.

Next, a 15 μm-thick polypropylene film was bonded to the surface of the resin composition layer, and the subsequent film was wound into a roll shape. The rolled adhesive film was cut into a width of 507 mm to obtain a sheet-shaped adhesive film having a size of 507 mm × 336 mm.

[Example 2] 变更 80 parts of polytetrafluoroethylene particles ("LUBRON L-2" manufactured by Daikin Industries, Ltd.) were changed to polytetrafluoroethylene particles ("KTL-500F" manufactured by Kitamura, average particle diameter 0.3 μm) 80 Serving. Except the above matters, it carried out similarly to Example 1, and produced the resin varnish and the adhesive film.

[Example 3] The amount of bisphenol AF-type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation) was changed from 10 parts to 25 parts. Furthermore, 170 parts of polytetrafluoroethylene particles ("LUBRON L-2" manufactured by Daikin Industries, Ltd.) were changed to 170 parts of polytetrafluoroethylene particles ("KTL-500F" manufactured by Kitamura Corporation, with an average particle diameter of 0.3 µm). Furthermore, spherical silica ("SO-C2" manufactured by Admatechs) was surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of the liquid bisphenol A epoxy resin ("jER828US" manufactured by Mitsubishi Chemical Corporation) was changed from 12 parts to 5 parts. Furthermore, the amount of xylenol-type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation) was changed from 10 parts to 5 parts. Except the above matters, it carried out similarly to Example 1, and produced the resin varnish and the adhesive film.

[Example 4] 变更 30 parts of biphenylaralkyl-type epoxy resin ("NC3000" manufactured by Nippon Kayaku Co., Ltd.) was changed to a naphthyl ether-type epoxy resin (epoxy equivalent 260, "HP6000" manufactured by DIC Corporation) 27 servings. Except the above matters, it carried out similarly to Example 1, and produced the resin varnish and the adhesive film.

[Example 5] 变更 30 parts of biphenylaralkyl-type epoxy resin ("NC3000" manufactured by Nippon Kayaku Co., Ltd.) was changed to a naphthyl ether-type epoxy resin (epoxy equivalent 260, "HP6000" manufactured by DIC Corporation) 20 parts and 5 parts of naphthalene-type 4-functional epoxy resin (epoxy equivalent 163, "HP4700" manufactured by DIC Corporation). Except the above matters, it carried out similarly to Example 1, and produced the resin varnish and the adhesive film.

[Example 6] 份 15 parts of an active ester-based hardener (a toluene solution of 65% by mass of nonvolatile matter, "HPC8000-65T" manufactured by DIC Corporation), and a cresol novolac-type hardener containing a triazine skeleton (solid content 50 25 parts by mass of 2-methoxypropanol solution, "LA3018-50P" manufactured by DIC, changed to 15 parts of naphthol-based hardener (hydroxyl equivalent 215, "SN485" manufactured by Nippon Steel Chemical Co., Ltd.) and contained 12 parts of a triazine phenol novolac resin (a hydroxyl equivalent of 125, a methyl ethyl ketone solution with a solid content of 60%, "LA7054" manufactured by DIC Corporation). Except the above matters, it carried out similarly to Example 1, and produced the resin varnish and the adhesive film.

[Example 7] N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was further added to the resin varnish. Except the above matters, it carried out similarly to Example 1, and produced the resin varnish and the adhesive film.

[Example 8] Spherical silicon dioxide ("SO-C2" manufactured by Admatechs) was surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 100 Parts, changed to spherical silica ("SO-C1" manufactured by Admatechs Corporation) with a surface diameter of N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle diameter 0.3 μm, specific surface area 10 m ² / g) 100 parts. Except the above matters, it carried out similarly to Example 1, and produced the resin varnish and the adhesive film.

[Example 9] Spherical silica ("SO-C2" manufactured by Admatechs) was surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) The amount was changed from 100 to 50. In addition, a spherical silica ("SO-C1" manufactured by Admatechs Co., Ltd.) with a surface treatment of N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the resin varnish. Particle size 0.3 μm) 50 parts. Except the above matters, it carried out similarly to Example 1, and produced the resin varnish and the adhesive film.

[Example 10] Spherical silica ("SO-C2" manufactured by Admatechs) was surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.). The amount was changed from 100 to 50. In addition, the amount of polytetrafluoroethylene particles ("LUBRON L-2" manufactured by Daikin Industries, Ltd.) was changed from 80 parts to 40 parts. Furthermore, to the resin varnish, spherical silica ("SO-C1" manufactured by Admatechs Co., Ltd.) with a surface treatment of N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was added. 50 parts of particle diameter) and 40 parts of polytetrafluoroethylene particles ("KTL-500F" manufactured by Kitamura Corporation, average particle diameter of 0.3 µm). Except the above matters, it carried out similarly to Example 1, and produced the resin varnish and the adhesive film.

[Example 11] The thickness of the resin composition layer of the adhesive film was changed from 50 μm to 15 μm. Except the above matters, it carried out similarly to Example 1, and produced the resin varnish and the adhesive film.

[Comparative Example 1] 双 Bisphenol AF epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation) was not used. The amount of the liquid bisphenol A epoxy resin ("jER828US" manufactured by Mitsubishi Chemical Corporation) was changed from 12 parts to 20 parts. Except the above matters, it carried out similarly to Example 1, and produced the resin varnish and the adhesive film.

[Comparative Example 2] Bisphenol AF-type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation) was not used. The amount of the liquid bisphenol A epoxy resin ("jER828US" manufactured by Mitsubishi Chemical Corporation) was changed from 12 parts to 20 parts. Furthermore, 4 parts of a fluorine-based surfactant ("SURFLONS-243" manufactured by AGC Seimi Chemical) was added to the resin varnish. Except the above matters, it carried out similarly to Example 1, and produced the resin varnish and the adhesive film.

[Comparative Example 3] Bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation) was not used. The amount of the liquid bisphenol A epoxy resin ("jER828US" manufactured by Mitsubishi Chemical Corporation) was changed from 12 parts to 20 parts. Furthermore, 2 parts of N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the resin varnish. Except the above matters, it carried out similarly to Example 1, and produced the resin varnish and the adhesive film.

[Measurement of Dielectric Rate] A polyethylene terephthalate film ("PET501010" manufactured by Lintec) was prepared on the surface to be subjected to a mold release treatment. On this polyethylene terephthalate film, the resin varnishes obtained in the examples and comparative examples were uniformly coated with a die coater so that the thickness of the dried resin composition layer became 50 μm. The coated resin varnish was dried at 80 ° C to 110 ° C (average 95 ° C) for 6 minutes to obtain a resin composition layer. Then, the resin composition layer was heat-treated at 200 ° C. for 90 minutes to harden it, and the support was peeled off to obtain a cured product film formed of a cured product of the resin composition. The hardened film was cut out to a length of 80 mm and a width of 2 mm to obtain an evaluation sample.

With regard to this evaluation sample, the dielectric constant of the hardened material of the resin composition was measured by a cavity resonance perturbation method using an analysis device ("HP8362B" manufactured by Agilent Technologies) at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. The measurement was performed on two test pieces, and the average value was calculated.

[Dispersion Evaluation of Filler] 接着 The adhesive films obtained in the examples and comparative examples were observed at a magnification of 1000 times using a microscope ("VH-2250" manufactured by KEYENCE Corporation). When the number of aggregates having a diameter of 50 μm or more is 0 per 10 fields of view and the number of aggregates having a diameter of 10 μm or more is less than 10 per 10 fields of view, the dispersibility of the filler is judged to be “good”. When the number of aggregates having a diameter of 50 μm or more is one or more per 10 fields of view, or the number of aggregates having a diameter of 10 μm or more is 10 or more per 10 fields of view, the dispersibility of the filler is judged to be “bad”.

[Measurement of peeling strength] (1) Base treatment of inner layer substrate: Prepare a copper-clad laminate with epoxy resin on both sides of the glass cloth base material forming the inner layer circuit (thickness of copper foil 18 μm, substrate thickness 0.8 mm, Panasonic Corporation) "R5715ES") as the inner substrate. Both sides of this inner layer substrate were etched with an etchant ("CZ8100" manufactured by MEC Corporation) for 1 µm, and the copper surfaces of both inner layer substrates were roughened.

(2) Lamination of the adhesive film: The adhesive films produced in the examples and comparative examples were produced using a batch type vacuum pressure laminator (a two-stage stacking laminator "CVP700" manufactured by Nichigo Morton Co., Ltd.) with a resin composition. The layer is bonded to the inner circuit board, and the two sides of the inner circuit board are laminated. The lamination was performed by depressurizing for 30 seconds to reduce the air pressure to 13 hPa or less, and then pressing at 100 ° C and a pressure of 0.74 MPa for 30 seconds. Next, hot stamping was performed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Hardening of the resin composition: The adhesive film laminated on the inner substrate is heated at 100 ° C for 30 minutes, and then 180 ° C for 30 minutes to heat cure the resin composition layer to form an insulating layer. Then, the polyethylene terephthalate film as a support was peeled. Thereby, a sample substrate having the order of the insulating layer, the inner substrate, and the insulating layer is obtained.

(4) Roughening process: The aforementioned sample substrate was immersed in a swelling liquid ("Swelling dip Securigant P" manufactured by Atotech Japan Co., containing diethylene glycol monobutyl ether) at 60 ° C for 10 minutes. Next, the sample substrate was immersed in a roughening solution ("Concentrate (R) Compact P" KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution manufactured by Atotech Japan) at 20 ° C for 20 minutes. Next, the sample substrate was immersed in a neutralizing solution ("Reduction solution Securigant P" manufactured by Atotech Japan) at 40 ° C for 5 minutes. Then, the sample substrate was dried at 80 ° C. for 30 minutes to obtain a roughened substrate. The arithmetic average roughness (Ra value) and ten-point average roughness (Rz value) of the surface of the insulating layer of the roughened substrate were measured by a method described later.

(5) Plating by the semi-additive method: The roughened substrate is immersed in a solution for electroless plating containing PdCl ₂ at 40 ° C for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C for 20 minutes . Then, the roughened substrate was annealed at 150 ° C for 30 minutes. An etching resist is formed on the roughened substrate after the annealing treatment, and patterning is performed by etching. Then, copper sulfate electrolytic plating was performed, and a conductor layer was formed on the surface of the insulating layer to a thickness of 25 μm. Next, an annealing treatment was performed by heating at 180 ° C for 30 minutes to obtain a circuit board having a conductor layer on the insulating layer.

(6) Measurement of peeling strength (peeling strength) of the plated conductor layer: Put on a conductor layer of a circuit board, and place it into a cut piece so as to surround a rectangular portion having a width of 10 mm and a length of 100 mm. One end of this rectangular portion in the longitudinal direction is peeled off and clamped with a jig (Autocom-type testing machine "AC-50CSL" manufactured by T · S · E). Further, at a room temperature, a peeling test was performed at a speed of 50 mm / minute with respect to the surface of the circuit substrate, and a peeling strength (kgf / cm) at a peeling length of 35 mm was measured as a peeling strength. In addition, in the case where the insulating layer is swollen, the peel strength is deteriorated without actual measurement, so the measurement is not performed.

[Measurement of arithmetic average roughness (Ra) and ten-point average roughness (Rz)] The arithmetic average roughness Ra and ten-point average roughness Rz of the surface of the insulating layer of the substrate are roughened, and a non-contact surface roughness is used. The meter ("WYKO NT3300" manufactured by VICO Instruments) was obtained by a value obtained by setting the measurement range to 121 μm × 92 μm using a VSI contact mode and a 50x lens. An average value of 10 points was randomly selected as a measurement value by finding.

[Results] (1) The results of the above examples and comparative examples are shown in the following table. In the following table, the amount of each component represents a mass part of a non-volatile component.

[Study] 即可 It is clear from Table 1 that in the examples, a low dielectric constant is obtained. In addition, in Examples, high dispersibility of a filler such as a fluorine-based filler (C) was obtained. Furthermore, in Example, the peeling strength which shows the height of the adhesiveness of an insulating layer and a conductor layer is large. Therefore, from this result, it was confirmed that according to the present invention, a resin composition having a low dielectric constant and excellent adhesion to the conductor layer can be obtained, and further, a resin composition having excellent dispersibility of the (C) fluorine-based filler can be achieved.

On the other hand, in Comparative Examples 1 to 3 in which the (A) fluorine-based epoxy resin was not used, expansion occurred in the insulating layer, and the adhesion with the conductor layer could not be improved. The expansion of the insulating layer is considered to be caused by agglomeration of the (C) fluorine-based filler. In particular, Comparative Example 2 improved the dispersibility of the (C) fluorine-based filler by using a fluorine-based surfactant, but the degree of improvement was insufficient from the viewpoint of improving the adhesiveness of the conductive layer. When comparing these comparative examples with the examples, it is understood that in order to obtain the desired effect of the present invention, it is particularly desirable to combine (A) a fluorine-based epoxy resin containing a fluorine atom and (C) a fluorine-based filler.

In the aforementioned examples, it was confirmed that even when the components (D) to (H) were not used, the results were the same as those of the above-mentioned examples, although there was a difference in degree.

Claims (12)

A resin composition comprising (A) an epoxy resin containing a fluorine atom in a molecule, (B) a hardener, and (C) a fluorine-based filler. The resin composition according to claim 1, wherein the component (A) is a bisphenol AF epoxy resin. The resin composition according to claim 1, wherein the average particle diameter of the component (C) is 0.05 µm to 5 µm. The resin composition according to claim 1, wherein the component (B) contains an active ester-based hardener. The resin composition according to claim 1, which comprises (D) an inorganic filler. The resin composition according to claim 5, wherein the amount of the (C) component is 20 to 80% by mass based on 100% by mass of the total amount of the (C) and (D) components. The resin composition of claim 1 is for forming an insulating layer of a circuit board. A sheet-like laminated material comprising the resin composition according to any one of claims 1 to 7. A sheet-like laminate comprising a resin composition layer formed of the resin composition according to any one of claims 1 to 7. The sheet-like laminated body according to claim 9, wherein the thickness of the resin composition layer is 30 μm or less. A circuit board comprising an insulating layer composed of a hardened body of the resin composition according to any one of claims 1 to 7. A semiconductor device includes the circuit board according to claim 11.