JP2019035050A - Resin composition - Google Patents

Abstract

To provide a resin composition that makes it possible to obtain an insulating layer having a low dielectric constant and excellent adhesion to a conductor layer, and is also characterized by excellent dispersibility of a fluorine-based filler.SOLUTION: A resin composition contains (A) an epoxy resin containing a fluorine atom in the molecule, (B) a curing agent, and (C) a fluorine-based filler.SELECTED DRAWING: None

Description

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

  In recent years, there has been a demand for thinner insulating layers because of demands for smaller electronic devices, higher signal speeds, and higher wiring density. In order to reduce the thickness of the insulating layer, it is desired to reduce the dielectric constant in order to control impedance. In order to reduce the dielectric constant of the insulating layer, it is preferable to use a filler having a low relative dielectric constant. For example, it is known to use a fluororesin powder such as polytetrafluoroethylene (see Patent Document 1). .

JP-A-11-269530

  However, fluorine-based fillers such as polytetrafluoroethylene particles have strong hydrophobicity, and dispersibility is insufficient when a resin composition is obtained by mixing with a resin component such as an epoxy resin. Furthermore, the insulating layer formed using the resin composition containing the fluorine-based filler has insufficient adhesion to the conductor layer formed on the insulating layer.

  The present invention was devised in view of the above problems, and can provide 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. An object of the present invention is to provide a sheet-shaped laminated material containing the resin composition; a circuit board and a semiconductor device including an insulating layer made of a cured product of the resin composition.

As a result of intensive studies to solve the above problems, the present inventor has (A) an epoxy resin containing a fluorine atom in the molecule, (B) a curing agent, and (C) a resin containing a combination of fluorine-based fillers. The present inventors have found that the composition can solve the above-mentioned problems and have completed the present invention.
That is, the present invention includes the following.

[1] A resin composition comprising (A) an epoxy resin containing a fluorine atom in the molecule, (B) a curing agent, and (C) a fluorine-based filler.
[2] The resin composition according to [1], wherein the component (A) is a bisphenol AF type epoxy resin.
[3] The resin composition according to [1] or [2], wherein the average particle size 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) includes an active ester curing agent.
[5] The resin composition according to any one of [1] to [4], comprising (D) an inorganic filler.
[6] The resin composition according to [5], wherein the amount of the component (C) is 20% by mass to 80% by mass with respect to 100% by mass of the total amount of the component (C) and the component (D).
[7] The resin composition according to any one of [1] to [6], which is 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 including a resin composition layer formed of the resin composition according to any one of [1] to [7].
[10] The sheet-like laminate according to [9], wherein the resin composition layer has a thickness of 30 μm or less.
[11] A circuit board including an insulating layer made of a cured product of the resin composition according to any one of [1] to [7].
[12] A semiconductor device including the circuit board according to [11].

  According to the present invention, an insulating layer having a low dielectric constant and excellent adhesion to a conductor layer can be obtained, and furthermore, a resin composition excellent in dispersibility of a fluorine-based filler; a sheet containing the resin composition A circuit board and a semiconductor device including an insulating layer made of a cured product of the resin composition.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and exemplifications, and can be implemented with any modifications without departing from the scope of the claims of the present invention and the equivalents thereof.

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

  In the following description, the term “dielectric constant” indicates a relative dielectric constant unless otherwise specified.

[1. Outline of Resin Composition]
The resin composition of the present invention includes (A) an epoxy resin containing fluorine atoms in the molecule, (B) a curing agent, and (C) a fluorine-based filler. In the following description, an epoxy resin containing a fluorine atom in the molecule as the component (A) may be referred to as a “fluorine-based epoxy resin”. The term “fluorine-based” means containing a fluorine atom. The term “fluorine-based filler” refers to a filler that contains 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 the conductor layer can be obtained, and further, the desired effect of the present invention that the dispersibility of the fluorine-based filler is excellent can be obtained. be able to.

[2. (A) Fluorine-based epoxy resin]
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 fluorine-based epoxy resin is usually 1 or more, preferably 2 or more, and usually 30 or less, preferably 25 or less, more preferably 20 or less. (A) When the number of fluorine atoms per molecule of the fluorine-based epoxy resin is in the above range, the desired effect of the present invention can be remarkably obtained.

  (A) Since the fluorine-based epoxy resin is an epoxy resin, it contains an epoxy group in its molecule. (A) The number of epoxy groups per molecule of fluorine-based epoxy resin is usually 1 or more, preferably 2 or more. The proportion of (A) fluorine-based epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, based on 100% by mass of the nonvolatile component of (A) fluorine-based epoxy resin. Preferably it is 60 mass% or more, Most preferably, it is 70 mass% or more. Since the ratio of the (A) fluorine-based epoxy resin having two or more epoxy groups in one molecule is large as described above, the desired effect of the present invention can be remarkably obtained. Moreover, normally, the crosslinked density of the hardened | cured material of a resin composition becomes sufficient, and an insulating layer with small surface roughness can be obtained.

  (A) As a fluorine-type epoxy resin, an aromatic epoxy resin is preferable from a viewpoint of reducing the average linear thermal expansion coefficient of an insulating layer. Here, the aromatic epoxy resin refers to an epoxy resin whose molecule contains an aromatic skeleton. The aromatic skeleton is a chemical structure generally defined as aromatic, 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 preferable (A) fluorine-type epoxy resin, the bisphenol AF type | mold 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 alkyl group is usually 1 or more, preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. Among ^them, R 1 to R ⁸ is preferably a hydrogen atom.

  Among the bisphenol AF type epoxy resins represented by the formula (1), (A) fluorinated epoxy resin includes 4,4 ′-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene]. Bisphenol type epoxy resins are particularly preferred. Thus, according to the preferable (A) fluorine-based epoxy resin, the desired effect of the present invention can be remarkably obtained.

(A) As a specific example of a fluorine-type epoxy resin, Mitsubishi Chemical Corporation "YL7760" (bisphenol AF type epoxy resin); etc. are mentioned.
Moreover, (A) a fluorine-type 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 a fluorine-type epoxy resin becomes like this. Preferably it is 50-5000, More preferably, it is 50-3000, More preferably, it is 80-2000, Most preferably, it is 110-1000. (A) When the epoxy equivalent of a fluorine-type epoxy resin exists in the said range, the crosslinked density of the hardened | cured material of a resin composition becomes sufficient, and an insulating layer with small surface roughness can be obtained. The epoxy equivalent is the mass of a resin containing 1 equivalent of an epoxy group, and can be measured according to JIS K7236.

  The weight average molecular weight of the (A) fluorine-based epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500 from the viewpoint of remarkably obtaining the desired effect of the present invention. is there. 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, particularly preferably 100% by mass of the nonvolatile component in the resin composition. Is 1.0% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 20% by mass or less. (A) When the quantity of a fluorine-type epoxy resin exists in the said range, the desired effect of this invention can be acquired notably. Furthermore, it is possible to obtain an insulating layer that normally exhibits good mechanical strength and insulation reliability.

  The amount of (A) fluorine-based epoxy resin in the resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, particularly preferably 100% by mass of (C) fluorine-based filler in the resin composition. Preferably it is 10 mass% or more, Preferably it is 80 mass% or less, More preferably, it is 50 mass% or less, Most preferably, it is 30 mass% or less. When the amount of the (A) fluorine-based epoxy resin is in the above range, the desired effect of the present invention can be remarkably obtained, and in particular, the dispersibility of the (C) fluorine-based filler is effectively enhanced. be able to.

[3. (B) Curing agent]
The curing agent as the component (B) usually has a function of reacting with the (A) fluorine-based epoxy resin to cure the 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 ester curing agent, and a carbodiimide curing agent. . Moreover, a hardening | curing agent may be used individually by 1 type, or may use 2 or more types together.

  As the active ester curing agent, a compound having one or more active ester groups in one molecule can be used. Among them, as the active ester curing agent, two or more ester groups having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compound esters in one molecule are used. The compound which has is preferable. The active ester curing agent 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 curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. .

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

  Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac and the like can be mentioned. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  Preferable specific examples of the active ester curing agent include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoylated product of phenol novolac. The active ester compound containing is mentioned. Of these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure are more preferred. The “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

  As a commercial product of an active ester type curing agent, 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);" EXB9416-70BK "(manufactured by DIC) as an active ester compound containing a naphthalene structure; Phenol novolac acetylated product "DC808" (manufactured by Mitsubishi Chemical Corp.) as an active ester compound containing: YLH1026 (manufactured by Mitsubishi Chemical Corp.) as an active ester compound containing a benzoylated phenol novolac; an active ester which is an acetylated phenol novolac “DC808” (manufactured by Mitsubishi Chemical Corporation) as a curing agent; “YLH1026” (manufactured by Mitsubishi Chemical Corporation), “YLH1030” (manufactured by Mitsubishi Chemical Corporation), “YLH1048” (manufactured by Mitsubishi Chemical Corporation) as benzoylated phenol novolac Mitsubishi Chemical Co., Ltd.);

  As a phenol type hardening | curing agent and a naphthol type | system | group hardening | curing agent, what has a novolak structure from a heat resistant and water-resistant viewpoint is preferable. Further, from the viewpoint of adhesion between the insulating layer and the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Among these, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion between the insulating layer and the conductor layer.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd .; “NHN” manufactured by Nippon Kayaku Co., Ltd. “CBN”, “GPH”: “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN-495V”, “SN375” manufactured by Nippon Steel & Sumikin Chemical; “TD-2090”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018-50P”, “EXB-9500”;

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd. and “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether; Phenol novolac and Polyfunctional cyanate resin derived from resol novolac; prepolymer these cyanate resin is partially triazine of; and the like. Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (phenol novolac type polyfunctional cyanate ester resin), “ULL-950S” (polyfunctional cyanate ester resin), and “BA230” manufactured by Lonza Japan. , “BA230S75” (a prepolymer in which part or all of bisphenol A dicyanate is triazine-modified into a trimer), and the like.

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

  Among the above, from the viewpoint of remarkably obtaining the desired effect of the present invention, (B) the curing agent is one or more selected from the group consisting of an active ester curing agent, a phenol curing agent and a naphthol curing agent. A curing agent is preferred. Furthermore, from the viewpoint of effectively increasing the dispersibility of the (C) fluorine-based filler, an active ester curing agent is particularly preferable. Therefore, it is preferable that the (B) curing agent used for the resin composition includes an active ester curing agent.

  When using an active ester type curing agent, the amount of the active ester type curing agent with respect to 100% by mass of the (B) curing agent is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more. Yes, preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less. When the amount of the active ester curing agent is in the above range, the desired effect of the present invention can be remarkably obtained, and in particular, the dispersibility of the (C) fluorine-based filler can be effectively enhanced.

  The amount of the (B) curing agent in the resin composition is preferably 0.1% by mass or more with respect to 100% by mass of the nonvolatile component in the resin composition, from the viewpoint of remarkably obtaining the desired effect of the present invention. Preferably it is 0.5 mass% or more, More preferably, it is 1 mass% or more, Preferably it is 40 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less.

  When the number of epoxy groups of the entire epoxy resin including (A) a fluorine-based epoxy resin and (E) a fluorine atom-free epoxy resin ((E) non-fluorine-based epoxy resin) described later is 1, (B) the curing agent The number of active groups is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, preferably 1.5 or less, more preferably 1.2 or less, still more preferably 1 or less, Especially preferably, it is 0.8 or less. Here, “the number of epoxy groups in the entire epoxy resin” means the mass of nonvolatile components of epoxy resin such as (A) fluorine-based epoxy resin and (E) non-fluorine-based epoxy resin present in the resin composition in terms of epoxy equivalent. This is the sum of all the divided values. Further, “(B) the number of active groups of the curing agent” is a value obtained by adding up all values obtained by dividing the mass of the non-volatile component of the (B) curing agent present in the resin composition by the active group equivalent. When the number of active groups of the (B) curing agent when the number of epoxy groups of the entire epoxy resin is 1, the desired effect of the present invention can be remarkably obtained. The heat resistance of the cured product is further improved.

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

  (C) As a material of a fluorine-type filler, fluorine-type polymer, fluorine-type rubber, etc. are mentioned, for example. Among these, a fluoropolymer is preferable from the viewpoint of reducing the dielectric constant of the insulating layer. Therefore, as the (C) fluorine-based filler, fluorine-based polymer particles are preferable.

  Examples of the fluoropolymer include polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene propene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-perfluorodiode. Xol copolymer (TFE / PDD), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride (PVF). These may 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, polytetrafluoroethylene is preferable as the fluoropolymer. Therefore, as the fluorine-containing filler (C), polytetrafluoroethylene particles as particles containing polytetrafluoroethylene are preferable.

  The weight average molecular weight of the fluoropolymer is preferably 5000000 or less, more preferably 4000000 or less, and particularly preferably 3000000 or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.

  (C) The average particle size 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, preferably 5 μm or less, more preferably 4.5 μm or less. Particularly preferably, it is 4 μm or less. When the average particle diameter of the (C) fluorine-based filler is in the above range, the desired effect of the present invention can be remarkably obtained, and more usually (C) the fluorine-based filler in the resin composition. The dispersibility can be improved.

  (C) The average particle diameter of particles such as fluorine-based fillers can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the particles is measured on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the average particle size can be obtained as the median diameter from the particle size distribution. As the measurement sample, one in which particles are dispersed in a solvent by ultrasonic waves can be preferably used. As the laser diffraction / scattering particle size distribution measuring apparatus, “LA-500” manufactured by Horiba, Ltd. or the like can be used.

  (C) Examples of commercially available fluorine-based fillers include “Lublon L-2”, “Lublon L-5” and “Lublon L-5F” manufactured by Daikin Industries, Ltd .; “Fluon PTFE L-170JE” manufactured by Asahi Glass Co., Ltd. ”,“ FluonPTFEEL-172JE ”,“ FluonPTFE L-173JE ”;“ KTL-500F ”,“ KTL-2N ”,“ KTL-1N ”manufactured by Kitamura Co., Ltd .;“ TLP10F-1 ”manufactured by Mitsui DuPont Fluorochemical Co., Ltd. And the like.

  (C) The fluorine-containing filler may be surface-treated. For example, (C) the fluorine-based filler may be surface-treated with an arbitrary surface treatment agent. Examples of the surface treatment agent include surfactants such as nonionic surfactants, amphoteric surfactants, cationic surfactants and anionic surfactants; inorganic fine particles. From the viewpoint of affinity, it is preferable to use a fluorosurfactant as the surface treatment agent. Further, as the above-mentioned fluorine-based surfactant, a suitable non-particulate fluorine-based polymer or fluorine-based oligomer may be used. Specific examples of the fluorosurfactant include “Surflon S-243” (perfluoroalkyl ethylene oxide adduct) manufactured by AGC Seimi Chemical Co .; “Megafac F-251” and “Megafac F-” manufactured by DIC "477", "Megafuck F-553", "Megafuck R-40", "Megafuck R-43", "Megafuck R-94"; "FTX-218", "Futgent 610FM" manufactured by Neos ;

  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 with respect to 100% by mass of the nonvolatile component in the resin composition. It is above, Preferably it is 80 mass% or less, More preferably, it is 60 mass% or less, Most preferably, it is 40 mass% or less. (C) When the amount of the fluorine-based filler is in the above range, the desired effect of the present invention can be remarkably obtained, and in particular, the dielectric constant of the cured product of the resin composition can be effectively reduced. it can.

  In particular, when the resin composition includes (D) an inorganic filler, the amount of (C) fluorine-based filler in the resin composition is 100 mass in total of (C) fluorine-based filler and (D) inorganic filler. % Is preferably 20% by mass or more, more preferably 30% by mass or more, particularly preferably 35% by mass or more, preferably 80% by mass or less, more preferably 75% by mass or less, and particularly preferably 70% by mass. % Or less. (C) When the amount of the fluorine-based filler is in the above range, the desired effect of the present invention can be remarkably obtained, and in particular, the dielectric constant of the cured product of the resin composition can be effectively reduced. it can.

[5. (D) Inorganic filler]
The resin composition may include (D) an inorganic filler as an optional component in addition to the components described above. Examples of the inorganic filler material as the component (D) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate , Titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferable from the viewpoint of remarkably obtaining the desired effect of the present invention. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Among these, spherical silica is preferable. (D) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types.

  Usually, the (D) inorganic filler is contained in the resin composition in the form 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, from the viewpoint of remarkably obtaining the desired effect of the present invention. Preferably it is 5.0 micrometers or less, More preferably, it is 2.0 micrometers or less, More preferably, it is 1.0 micrometers or less. Moreover, (D) When the average particle diameter of the inorganic filler is in the above range, normally, the circuit embedding property of the resin composition layer can be improved, or the surface roughness of the insulating layer can be reduced.

  (D) Examples of commercially available inorganic fillers include “SP60-05” and “SP507-05” manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; “YC100C”, “YA050C” and “YA050C-MJE” manufactured by Admatex. "YA010C"; Denka's "UFP-30"; Tokuyama's "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N"; Admatechs' "SC2500SQ" “SO-C4”, “SO-C2”, “SO-C1”; and the like. (D) The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory, as in the (C) fluorine-based filler.

  (D) The inorganic filler may be surface-treated with an arbitrary surface treatment agent. Examples of the surface treatment agent include coupling agents such as aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, titanate coupling agents; alkoxysilane compounds; organosilazane compounds; It is done. By performing the surface treatment with these surface treatment agents, the moisture resistance and dispersibility of the inorganic filler (D) can be enhanced.

  Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu. “KBE903” (3-aminopropyltriethoxysilane) manufactured by Chemical Industry Co., Ltd. “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “SZ-31” manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), “KBM-103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-4803” (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and the like. Moreover, a surface treating agent may be used individually by 1 type, and may be used in combination of 2 or more types.

The degree of the surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the (D) inorganic filler. Carbon content per unit surface area of the inorganic filler (D) is, (D) from the viewpoint of the dispersibility of the inorganic filler improved, preferably 0.02 mg / ^{m 2} or more, more preferably 0.1 mg / ^{m 2} or more, Particularly preferably, it 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 sheet form, the carbon amount is preferably 1 mg / m ² or less, more preferably 0.8 mg / m ² or less, particularly preferably. 0.5 mg / m ² or less.

  (D) The amount of carbon per unit surface area of the inorganic filler is determined by washing the surface-treated (D) inorganic filler with a solvent (for example, methyl ethyl ketone (hereinafter sometimes referred to as “MEK”)). Can be measured. Specifically, a sufficient amount of MEK and (D) inorganic filler surface-treated with a surface treatment agent are mixed and ultrasonically cleaned at 25 ° C. for 5 minutes. Subsequently, after removing a supernatant liquid and drying a non-volatile component, the carbon amount per unit surface area of (D) inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. can be used.

  The amount of the (D) inorganic filler in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more with respect to 100% by mass of the nonvolatile component in the resin composition. Especially preferably, it is 20 mass% or more, Preferably it is 70 mass% or less, More preferably, it is 60 mass% or less, More preferably, it is 50 mass% or less, Most preferably, it is 40 mass% or less. (D) Since the thermal expansion coefficient of the hardened | cured material of a resin composition can be made low because the quantity of an inorganic filler is more than the lower limit of the said range, the curvature of an insulating layer can be suppressed. Moreover, when the amount of the (D) inorganic filler is not more than the upper limit of the above range, the mechanical strength of the cured product of the resin composition can be improved, and particularly the resistance to elongation can be increased.

[6. (E) Epoxy resin containing no fluorine atom]
In addition to the components described above, the resin composition may contain (E) a non-fluorine epoxy resin as an optional component. (E) A non-fluorine type epoxy resin means an epoxy resin which does not contain a fluorine atom in the molecule. (E) Non-fluorinated epoxy resins include, for example, bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, Naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin, cresol novolac Type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, Pyro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

  (E) As a non-fluorine-type epoxy resin, an aromatic epoxy resin is preferable from a viewpoint of reducing the average linear thermal expansion coefficient of an insulating layer. Among these, from the viewpoint of remarkably obtaining the desired effect of the present invention, (E) non-fluorine type epoxy resin is bisphenol A type epoxy resin, bixylenol type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, One or more epoxy resins selected from the group consisting of naphthalene-type tetrafunctional epoxy resins and naphthol-type epoxy resins are preferable, and bisphenol A-type epoxy resins, bixylenol-type epoxy resins and naphthol-type epoxy resins are particularly preferable.

  It is preferable that a resin composition contains the epoxy resin which has a 2 or more epoxy group in 1 molecule as (E) non-fluorine-type epoxy resin. From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably (E) with respect to 100% by mass of the nonvolatile component of the non-fluorinated epoxy resin. Is 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

  As the epoxy resin, an epoxy resin that is liquid at a temperature of 20 ° C. (hereinafter sometimes referred to as “liquid epoxy resin”) and an epoxy resin that is a solid at a temperature of 20 ° C. (sometimes referred to as “solid epoxy resin”). There is. The resin composition (E) may contain only a liquid epoxy resin or a solid epoxy resin as a non-fluorine-based epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin. It is preferable to include. (E) By using a combination of a liquid epoxy resin and a solid epoxy resin as a non-fluorine-based epoxy resin, the flexibility of the resin composition layer is improved, or the breaking strength of the cured product of the resin composition is improved. You can make it.

  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.

  Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, and alicyclic epoxy resins having an ester skeleton. , Cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having a butadiene structure are preferred, glycidylamine type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin and naphthalene type epoxy A resin is more preferable, and a bisphenol A type epoxy resin is particularly preferable.

  Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC; “828US”, “jER828US”, “jER828EL”, “825” manufactured by Mitsubishi Chemical Corporation. "Epicoat 828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical; “630”, “630LSD” (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “ZX1059” (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; Nagase ChemteX Corporation "EX" made “721” (glycidyl ester type epoxy resin); “Celoxide 2021P” (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel; “PB-3600” (epoxy resin having a butadiene structure) manufactured by Daicel; “ZX1658”, “ZX1658GS” (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Kagaku Co., Ltd .; These may be used alone or in combination of two or more.

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

  Solid epoxy resins include bixylenol type epoxy resins, biphenyl aralkyl type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, Naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, tetraphenylethane type epoxy resin are preferable, bixylenol type epoxy resin, biphenyl aralkyl type epoxy resin, naphthy Ren ether type epoxy resins, naphthalene type tetrafunctional epoxy resins and naphthol type epoxy resins are more preferred.

  Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin) manufactured by DIC; “HP-4700” and “HP-4710” (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200" (dicyclopentadiene type epoxy resin) manufactured by DIC; “HP-7200HH”, “HP-7200H”, “EXA-7311”, “EXA-7311-G3”, “EXA-7311-G4”, “EXA-7311-G4S”, “HP6000” (manufactured by DIC) Naphthylene ether type epoxy resin) “EPPN-502H” (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Resin); “NC7000L” (naphthol novolak type epoxy resin) manufactured by Nippon Kayaku; “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenylaralkyl type epoxy resin) manufactured by Nippon Kayaku; Nippon Steel “ESN475V” (naphthol type epoxy resin) manufactured by Sumikin Chemical Co., Ltd .; “ESN485” (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; “YX4000H”, “YX4000”, “YL6121” (biphenyl) manufactured by Mitsubishi Chemical Corporation Type epoxy resin); "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical ; Mitsubishi Chemi Le manufactured by "jER1010" (solid bisphenol A epoxy resin); Mitsubishi Chemical Co. "jER1031S" (tetraphenyl ethane epoxy resin); and the like. These may be used alone or in combination of two or more.

  (E) When a liquid epoxy resin and a solid epoxy resin are used in combination as a non-fluorine-based epoxy resin, their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1: 0.1 to 1 : 15, more preferably 1: 0.5 to 1:10, particularly preferably 1: 1 to 1: 8. When the mass ratio between the liquid epoxy resin and the solid epoxy resin is in the above range, preferable adhesiveness can be obtained when the adhesive is used in the form of an adhesive film. Moreover, when using it with the form of an adhesive film, sufficient flexibility is acquired and a handleability can be improved. Furthermore, the breaking strength of the cured product of the resin composition can be effectively increased.

  (E) The range of the epoxy equivalent of the non-fluorinated epoxy resin is preferably the same range as described as the range of the epoxy equivalent of (A) the fluorine-based epoxy resin. Thereby, the same advantage as that described in the section of (A) fluorinated epoxy resin can be obtained.

  (E) The range of the weight average molecular weight of the non-fluorinated 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 advantage as that described in the section of (A) fluorinated epoxy resin can be obtained.

  The amount of the (E) non-fluorinated epoxy resin in the resin composition is preferably 5 with respect to 100% by mass of the nonvolatile component in the resin composition from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. It is at least 8 mass%, more preferably at least 8 mass%, particularly preferably at least 10 mass%, preferably at most 70 mass%, more preferably at most 50 mass%, particularly preferably at most 40 mass%.

[7. (F) Thermoplastic resin]
In addition to the components described above, the resin composition may contain (F) a thermoplastic resin as an optional component. Examples of the thermoplastic resin as the component (F) include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, and polyphenylene ether resin. , Polycarbonate resin, polyether ether ketone resin, and polyester resin. Among these, phenoxy resin is preferable from the viewpoint of remarkably obtaining the desired effect of the present invention. A thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more types.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include a phenoxy resin having one or more skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

  Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resins) manufactured by Mitsubishi Chemical; “YX8100” (bisphenol S skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical; "YX6954" (bisphenol acetophenone skeleton-containing phenoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; “YL7769BH30”, “YL6794”, “YL7213”, “YL7290”, “YL7891BH30” and “YL7482” may be mentioned.

  (F) The polystyrene-reduced weight average molecular weight of the thermoplastic resin is preferably 8000 or more, more preferably 10,000 or more, particularly preferably 20000 or more, preferably 70000 from the viewpoint of remarkably obtaining the desired effect of the present invention. Below, more preferably 60000 or less, particularly preferably 50000 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, 100% by mass of the non-volatile component in the resin composition. It is 0.6 mass% or more, More preferably, it is 0.7 mass% or more, Preferably it is 15 mass% or less, More preferably, it is 12 mass% or less, More preferably, it is 10 mass% or less.

[8. (G) Curing accelerator]
In addition to the components described above, the resin composition may contain (G) a curing accelerator as an optional component. (G) By using a curing accelerator, curing can be accelerated when the resin composition is cured.

  (G) As a hardening accelerator, a phosphorus hardening accelerator, an amine hardening accelerator, an imidazole hardening accelerator, a guanidine hardening accelerator, a metal hardening accelerator, a peroxide hardening accelerator is mentioned, for example. It is done. Among these, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable, amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are more preferable. A system curing accelerator is particularly preferred. (G) A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

  Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. Of these, triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

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

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 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-diamino-6- [2'-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-me Le benzyl-imidazolium chloride, 2-methyl-imidazoline, 2-phenyl imidazole compounds of imidazoline and the like; and, adducts of imidazole compounds and epoxy resin; and the like. Of these, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

  A commercial item may be used as an imidazole series hardening accelerator, for example, "P200-H50" by Mitsubishi Chemical Corporation is mentioned.

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-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- ( - tolyl), and the biguanide. Of these, dicyandiamide and 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned, for example. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

  Examples of the peroxide curing accelerator include cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydro Examples thereof include peroxide, cumene hydroperoxide, and tert-butyl hydroperoxide.

  A commercially available product can be used as the peroxide curing accelerator, and examples thereof include “Park Mill D” manufactured by NOF Corporation.

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

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

  (H) As a coupling agent, the same thing as the example quoted as the surface treating agent of (D) inorganic filler is mentioned, for example. Moreover, (H) coupling agent may be used individually by 1 type, and may be used in combination of 2 or more types.

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

[10. (I) Additive]
The resin composition may further contain an additive as an optional component in addition to the components described above. Examples of such additives include organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds; thickeners; antifoaming agents; leveling agents; adhesion-imparting agents; colorants; Is mentioned. Moreover, an additive may be used individually by 1 type and may be used combining two types of arbitrary forms.

[11. Method for producing resin composition]
The resin composition can be produced, for example, by a method in which the compounding components are mixed with a solvent as necessary and stirred using a stirring device such as a rotary mixer.

[12. Characteristics of resin composition]
The hardened | cured material of the resin composition mentioned above can make the dielectric constant low. Therefore, an insulating layer having a low dielectric constant can be obtained from the cured product of the resin composition. For example, when a cured product is obtained by curing the resin composition by the method described in Examples, the dielectric constant of the cured product is preferably 3.00 or less, more preferably 2.98 or less, and particularly preferably 2 97 or less. Here, the dielectric constant of the cured product can be measured by the method described in Examples.

  When the conductor layer is formed on the cured product layer of the resin composition described above, the adhesion between the cured product layer and the conductor layer can be increased. Therefore, according to the hardened | cured material of the resin composition mentioned above, an insulating layer with high adhesiveness with respect to a conductor layer can be obtained. For example, when an insulating layer is formed by a cured product of the resin composition and a conductor layer is formed on the insulating layer by plating according to the method described in the examples, the peel strength can be increased. Specifically, the peel strength can be preferably 0.2 kgf / cm or more, more preferably 0.3 kgf / cm or more, and particularly preferably 0.4 kgf / cm or more. The peel strength can be measured by the method described in Examples.

  (A) It is surprising from the common sense of those skilled in the art that high adhesiveness to the conductor layer can be realized by the resin composition containing the fluorine-based epoxy resin as described above. In general, since a material containing fluorine has a low affinity for a conductor, the adhesion tends to be low. (C) The said tendency can also be understood from the fact that a conventional insulating layer obtained from a resin composition containing a fluorine-based filler is inferior in adhesion to a conductor layer. Therefore, according to common knowledge of those skilled in the art, when (A) a fluorine-based epoxy resin is combined with (C) a fluorine-based filler, the amount of fluorine-containing material is increased, and thus the adhesion is expected to be further lowered. 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 mentioned above is excellent in the dispersibility of the (C) fluorine-based filler. Therefore, in the resin composition, aggregation of the (C) fluorine-based filler can be suppressed. For example, when the resin composition layer having the thickness described in the example is formed and the resin composition layer is observed at an observation magnification of 1000 times by the method described in the example, the number of aggregates observed can be reduced. Specifically, the number of aggregates having a diameter of 50 μm or more can be 0 per 10 fields, and the number of aggregates having a diameter of 10 μm or more can be less than 10 per 10 fields.

The inventor presumes the mechanism by which the above-described effect can be obtained by the resin composition described above as follows. However, the technical scope of the present invention is not limited by the mechanism described below.
(C) The fluorine-based filler has an effect of lowering the dielectric constant of the cured product of the resin composition when combined with an epoxy resin and (B) a curing agent.
However, (C) the fluorine-based filler has a low affinity with a general epoxy resin. Therefore, when the (C) fluorine-based filler is contained in the resin composition in combination with a general epoxy resin, the dispersibility of the (C) fluorine-based filler is low, and aggregation tends to occur. On the other hand, since (A) fluorine-based epoxy resin has a high affinity with (C) fluorine-based filler by containing fluorine atoms and is a resin having an epoxy group, (C) fluorine-based filling It has high affinity with components other than materials. Therefore, by combining the (C) fluorine-based filler with the (A) fluorine-based epoxy resin, the aggregation of the (C) fluorine-based filler is suppressed, so that the dispersibility of the (C) fluorine-based filler is increased. Can do.
Furthermore, as described above, when aggregation of the (C) fluorine-based filler is suppressed, compositional deviation in the resin composition is suppressed. Therefore, stress concentration due to expansion and contraction of each component hardly occurs during the thermosetting of the resin composition. Therefore, it is difficult for the cured product of the resin composition to have a starting point of breakage due to stress concentration. In general, the chemical solution for roughening treatment is likely to enter the periphery of the aggregate of (C) fluorine-based filler. When voids are generated in the cured product due to the penetration of the chemical solution, phenomena such as a decrease in mechanical strength of the cured product and expansion due to the annealing treatment 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. Therefore, the combination of (A) fluorine-based epoxy resin, (B) curing agent, and (C) fluorine-based filler can suppress the peeling of the conductor layer accompanied by the destruction of the cured product of the insulating layer. High adhesion can be demonstrated.

  In general, if the cured product of the resin composition containing a filler contains agglomerates of the filler, the chemical solution can easily enter the periphery of the agglomerates during the roughening treatment. Ten-point average roughness Rz tends to increase. Therefore, the ten-point average roughness Rz generally has a correlation with the dispersibility of the (C) fluorine-based filler in the cured product, and the ten-point average roughness RC increases as the degree of aggregation of the (C) fluorine-based filler increases. Rz tends to be large. Since the dispersibility of the (C) fluorine-based filler is good as described above, the cured product of the resin composition usually has a ten-point average roughness Rz when subjected to a roughening treatment. Can be small. For example, when an insulating layer is formed with a cured product of the resin composition by the method described in the Examples, and the insulating layer is subjected to a roughening treatment, the ten-point average roughness Rz of the insulating layer after the roughening treatment is set to Can be small. 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 cured product of the resin composition is subjected to a roughening treatment, the surface roughness after the roughening treatment can usually be reduced. Therefore, according to the hardened | cured material of the resin composition mentioned above, an insulating layer with small surface roughness can be normally obtained. For example, when the insulating layer is formed from the cured product of the resin composition by the method described in the Examples and the insulating layer is subjected to a roughening treatment, the arithmetic average roughness of the insulating layer after the roughening treatment is set to a predetermined value. Can be in range. Specifically, the arithmetic average roughness Ra is preferably 400 nm or less, more preferably 300 nm or less, and particularly preferably 250 nm or less.

[13. Application 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, and in particular, build-up for forming an insulating layer in manufacturing a circuit board by a build-up method. It is preferably used as a resin composition for forming an insulating layer.

  In particular, taking advantage of the fact that an insulating layer having a low dielectric constant can be obtained, this resin composition is a resin composition for forming an insulating layer of a high-frequency circuit board (for forming an insulating layer of a high-frequency circuit board). Resin composition) can be suitably used. Especially, this resin composition can be more suitably used as a resin composition (resin composition for forming an interlayer insulating layer of a high frequency circuit board) for forming an interlayer insulating layer of a high frequency circuit board. Here, the “high frequency circuit board” means a circuit board that can be operated even with an electric signal in a high frequency band. The “high frequency band” usually means a band of 1 GHz or more, and the above resin composition is particularly effective in a band of 28 GHz to 80 GHz.

  In addition, since the insulating layer having a low dielectric constant can contribute to a reduction in the height of the circuit board, it is suitable for applications requiring a thin circuit board. Furthermore, an insulating layer having a low dielectric constant facilitates impedance control of the circuit board, and thus is suitable for increasing the degree of design freedom of the circuit board. From this point of view, examples of suitable applications of the resin composition include circuit boards such as a mother board, an IC package board, a camera module board, and a fingerprint authentication sensor board used for portable devices. As a specific example, the fingerprint authentication sensor may include an insulating layer included in a circuit board, a plurality of electrodes formed on the insulating layer, and an insulating film in this order. In this fingerprint authentication sensor, fingerprint authentication is performed by utilizing the fact that the capacitance value of the capacitor formed by the finger, electrode and insulating film placed on the insulating film differs between the concave and convex parts of the fingerprint. Is called. In such a fingerprint authentication sensor, if the insulating layer can be made thin, the sensor itself can be miniaturized.

  The resin composition of the present invention uses a resin composition such as an adhesive film, a sheet-like laminated material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a hole-filling resin, a component-filling resin, etc. Can be used in a wide range of applications.

[14. Sheet-like laminated material]
The resin composition described above can be applied in a varnish state and used for forming 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 sheet-like laminated material include an adhesive film and a prepreg.

  In one embodiment, the adhesive film includes a support and a resin composition layer provided on the support. The resin composition layer is a layer formed of the above-described resin composition and may be referred to as an “adhesion layer”.

  The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, particularly preferably 50 μm or less, and particularly preferably 30 μm or less from the viewpoint of thinning. The minimum of the thickness of a resin composition layer is not specifically limited, For example, it may be 1 micrometer or more, 5 micrometers or more, 10 micrometers or more.

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

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as “PET”) and polyethylene naphthalate (hereinafter sometimes referred to as “PEN”). Polyester; Polycarbonate (hereinafter sometimes referred to as “PC”); Acrylic polymer such as polymethyl methacrylate (hereinafter sometimes referred to as “PMMA”); Cyclic polyolefin; Triacetylcellulose (hereinafter sometimes referred to as “TAC”). ); Polyether sulfide (hereinafter sometimes referred to as “PES”); polyether ketone; polyimide; Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and polyethylene terephthalate is particularly preferable because it is inexpensive and excellent in availability.

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

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

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. Examples of the release agent that can be used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . Examples of commercially available release agents include “SK-1”, “AL-5”, and “AL-7” manufactured by Lintec Corporation, which are alkyd resin release agents. In addition, examples of the support with a release layer include “Lumirror T60” manufactured by Toray Industries, Inc., “Purex” manufactured by Teijin Limited, “Unipeel” manufactured by Unitika, and the like.

  The thickness of the support is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. In addition, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  For the adhesive film, for example, a resin varnish containing an organic solvent and a resin composition is prepared, and this resin varnish is applied to a support using a coating device such as a die coater and further dried to form a resin composition layer. By making it, it can manufacture.

  Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; cellosolve and butyl carbitol Carbitol solvents of the following: aromatic hydrocarbon solvents such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone; One organic solvent may be used alone, or two or more organic solvents may be used in combination.

  Drying can be carried out by a known method such as heating or hot air blowing. The drying conditions are set so that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the resin composition is dried at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes. A physical layer can be formed. Usually, the resin composition layer is obtained as a film obtained by semi-curing a coating film of a resin varnish.

  The adhesive film may contain arbitrary layers other than a support body and a resin composition layer as needed. For example, a protective film according to the support may be provided on the surface of the adhesive film that is not joined 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, it is possible to suppress the adhesion and scratches of dust and the like to the surface of the resin composition layer. When the adhesive film has a protective film, the adhesive film can usually be used by peeling off the protective film. The adhesive film can be stored in a roll.

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

  The sheet-like fiber base material used for the prepreg is not particularly limited. As a sheet-like fiber base material, arbitrary fiber base materials used as a base material for prepregs, such as a glass cloth, an aramid nonwoven fabric, and a liquid crystal polymer nonwoven fabric, can be used, for example. From the viewpoint of thinning, the thickness of the sheet-like fiber base material is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, and particularly preferably 600 μm or less. From the viewpoint of reducing the depth of plating for forming the conductor layer, the thickness of the sheet-like fiber base material 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 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 or a solvent method.
The thickness of the prepreg may be in the same range as the resin composition layer in the adhesive film described above.

[15. Circuit board]
The circuit board of this invention contains the insulating layer formed with the hardened | cured material of the resin composition mentioned above. In one embodiment, the circuit board includes an inner layer substrate and an insulating layer provided on the inner layer substrate.

  The “inner layer substrate” is a member that becomes a base material of the circuit board. 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 general, the inner layer substrate includes a conductor layer formed directly or indirectly on one side or both sides of the core base material. This conductor layer may be patterned so as to function as an electrical circuit, for example. An inner layer substrate in which a conductor layer is formed as a circuit on one side or both sides of the core substrate may be referred to as an “inner layer circuit board”. Further, an intermediate product in which at least one of an insulating layer and a conductor layer is to be formed for manufacturing a circuit board is also included in the term “inner layer board”. When the circuit board incorporates components, an inner layer substrate incorporating the components may be used.

  The thickness of the inner layer substrate is usually from 50 μm to 4000 μm, and preferably from 200 μm to 3200 μm from the viewpoint of improving the mechanical strength and reducing the height (reducing thickness) of the circuit board.

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

  The insulating layer is a layer of a cured product of the resin composition. The insulating layer formed of the cured product is a circuit for a build-up circuit board, a high-frequency circuit board, a mother board, an IC package board, a camera module board, and a fingerprint authentication sensor board used for portable devices. It can be suitably applied to an insulating layer for a substrate.

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

  The thickness of the insulating layer is usually 1 μm to 200 μm, and preferably 1 μm to 30 μm from the viewpoint of improving electrical characteristics and reducing the height of the circuit board.

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

  Since the said insulating layer is a layer formed with the hardened | cured material of the resin composition mentioned above, the outstanding characteristic of the hardened | cured material of the resin composition mentioned above can be exhibited. Therefore, the insulating layer of the circuit board preferably has a surface roughness such as a dielectric constant of the insulating layer, a peel strength between the insulating layer and the conductor layer, a ten-point average roughness Rz and an arithmetic average roughness Ra after the roughening treatment. These characteristics can be adjusted within the same range as described in the section of the characteristics of the resin composition. These characteristics can be measured by the methods described in the examples.

A circuit board can be manufactured by the manufacturing method including the following process (I) and process (II), for example using an adhesive film.
(I) The process of laminating | stacking an adhesive film on an inner layer board | substrate so that the resin composition layer of this adhesive film may join an inner layer board | substrate.
(II) A step of thermosetting the resin composition layer to form an insulating layer.

  Lamination | stacking with an inner layer board | substrate and an adhesive film can be performed by the thermocompression bonding process heated, for example, pressing an adhesive film to an inner layer board | substrate from the support body side. Examples of the member for the thermocompression bonding process (also referred to as “thermocompression bonding member”) include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). In addition, the thermocompression bonding member is not directly pressed against the support of the adhesive film and pressed, but through an elastic material such as heat-resistant rubber so that the adhesive film sufficiently follows the unevenness of the surface of the inner layer substrate. It is preferable to press.

  Lamination | stacking with an inner layer board | substrate and an adhesive film can be implemented by the vacuum laminating method, for example. In the vacuum laminating method, the temperature for thermocompression bonding is preferably 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C. The pressure for thermocompression bonding is preferably 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa. The time for thermocompression bonding is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

  Lamination can be performed with a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressurizing laminator.

  After the lamination, the laminated resin composition layer may be smoothed by pressing from the support side under normal pressure (under atmospheric pressure), for example, with a thermocompression bonding member. The pressing conditions for the smoothing treatment can be the same as the conditions for the thermocompression bonding of the laminate. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform a lamination | stacking and smoothing process continuously using said 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 cured to form an insulating layer. The conditions for thermosetting the resin composition layer are not particularly limited, and the conditions employed when forming the insulating layer of the circuit board can be arbitrarily employed.

  The thermosetting conditions of the resin composition layer vary depending on, for example, the type of 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, more preferably 15 minutes to 90 minutes).

  Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is usually at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). May be preheated for usually 5 minutes or longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

  The method for manufacturing a circuit board may further include (III) a step of drilling the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer. These steps (III) to (V) can be performed according to an appropriate method used for manufacturing a circuit board. When the support is removed after step (II), the support is removed between step (II) and step (III), between step (III) and step (IV), or step You may implement at any time between (IV) and process (V).

  Step (III) is a step of making a hole in the insulating layer. By drilling, holes such as via holes and through holes can be formed in the insulating layer. Step (III) can be performed, for example, by a method such as drilling, lasering, or plasma depending on the composition of the resin composition used for forming the insulating layer. The size and shape of the hole can be appropriately determined according to the design of the circuit board.

  Step (IV) is a step of subjecting the insulating layer to a roughening treatment. The procedure and conditions of the roughening treatment are not particularly limited, and any procedure and conditions used when forming the insulating layer of the circuit board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

  Examples of the swelling liquid include an alkaline solution and a surfactant solution, and preferably an alkaline solution. As an alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan. Moreover, a swelling liquid may be used individually by 1 type, and may be used in combination of 2 or more types. The swelling treatment with the swelling liquid is not particularly limited. The swelling treatment can be performed, for example, by immersing the insulating layer in a swelling liquid at 30 ° C. to 90 ° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes 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. Moreover, an oxidizing agent may be used individually by 1 type, and may be used in combination of 2 or more types. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizers include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan.

  As the neutralizing solution, an acidic aqueous solution is preferable. As a commercial item of the neutralization liquid, for example, “Reduction Solution Securigans P” manufactured by Atotech Japan Co., Ltd. may be mentioned. Moreover, a neutralization liquid may be used individually by 1 type, and may be used in combination of 2 or more types. The treatment with the neutralizing solution can be performed by immersing the treated surface of the insulating layer subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 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 the oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

  Step (V) is a step of forming a conductor layer. The material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include a layer formed of an alloy of two or more kinds of metals selected from the above group (for example, a nickel / chromium alloy, a copper / nickel alloy, and a copper / titanium alloy). Among them, from the viewpoint of versatility of forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; or nickel / chromium alloy, copper -An alloy layer of nickel alloy or copper / titanium alloy is preferable. Further, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; or an alloy layer of nickel / chromium alloy is more preferable, and a single metal layer of copper is still more preferable.

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

  The thickness of the conductor layer is usually 3 μm to 200 μm, preferably 10 μm to 100 μm.

  The conductor layer can be formed by, for example, directly patterning a metal foil used as a support for the adhesive film. The conductor layer can be formed by plating, for example. 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. Especially, it is preferable to form by a semi-additive method from a viewpoint of the simplicity of manufacture.

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

  The conductor layer may be formed using a metal foil, for example. When forming a conductor layer using metal foil, it is preferable to implement process (V) between process (I) and process (II). For example, after the step (I), the support is removed, and a metal foil is laminated on the exposed surface of the resin composition layer. Lamination of the resin composition layer and the metal foil can be performed by a vacuum laminating method. The lamination conditions may be the same as the lamination conditions of the inner layer substrate and the adhesive film in step (I). Next, step (II) is performed to form an insulating layer. Thereafter, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by a method such as a subtractive method or a modified semi-additive method. A metal foil can be manufactured by methods, such as an electrolytic method and a rolling method, for example. Examples of commercially available metal foil include HLP foil manufactured by JX Nippon Mining & Metals, JXUT-III foil, 3EC-III foil, TP-III foil manufactured by Mitsui Metal Mining.

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

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

[16. Semiconductor device]
A semiconductor device includes the circuit board. This semiconductor device can be manufactured using a circuit board.

  Examples of the semiconductor device include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

  The semiconductor device can be manufactured, for example, by mounting a component (semiconductor chip) on a conductive portion of a circuit board. The “conducting part” is “a part where an electric signal can be transmitted on the circuit board”, and the part may be a surface of the circuit board or a part embedded in the circuit board. Absent. In addition, an electric circuit element made of a semiconductor can be arbitrarily used for the semiconductor chip.

  As a method for mounting a semiconductor chip when manufacturing a semiconductor device, any method in which the semiconductor chip functions effectively can be adopted. As a semiconductor chip mounting method, for example, a wire bonding mounting method, a flip chip mounting method, a mounting method using a bumpless buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a non-conductive film (NCF) ) Mounting method. Here, the “mounting method using a build-up layer without bumps (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a circuit board and the semiconductor chip and wiring of the circuit board are connected”.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, “parts” and “%” mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.

[Example 1]
12 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 187, “jER828US” manufactured by Mitsubishi Chemical Corporation), 10 parts of bixylenol type epoxy resin (epoxy equivalent 190, “YX4000HK” manufactured by Mitsubishi Chemical Corporation), biphenylaralkyl type epoxy resin (epoxy) Equivalent 276, Nippon Kayaku “NC3000” 30 parts, naphthol type epoxy resin (epoxy equivalent 332, Nippon Steel & Sumikin Chemical “ESN475V”) 10 parts, bisphenol AF type epoxy resin (epoxy equivalent 235, manufactured by Mitsubishi Chemical Corporation) 10 parts of "YL7760") and 20 parts of phenoxy resin (methyl ethyl ketone / cyclohexanone = 1/1 solution having a solid content of 30% by mass, "YL7553BH30" manufactured by Mitsubishi Chemical Corporation) are added to 60 parts of methyl ethyl ketone and 20 parts of cyclohexanone with stirring. Dissolved, to obtain a resin solution.

  To this resin solution, 15 parts of active ester type curing agent (active group equivalent 223, non-volatile component 65% by mass toluene solution, “DIC” HPC8000-65T ”), triazine skeleton-containing cresol novolac type curing agent (phenol equivalent 151, 25 parts by mass of a 2-methoxypropanol solution having a solid content of 50% by mass, “LA3018-50P” manufactured by DIC, 4 parts of a curing accelerator (4-dimethylaminopyridine (DMAP), methyl ethyl ketone solution having a solid content of 5% by mass), N -100 parts of spherical silica ("SO-C2" manufactured by Admatechs, average particle size of 0.5 [mu] m) surface-treated with phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), and polytetra Fluoroethylene particles (“Lublon L-2” manufactured by Daikin Industries, Ltd., average particle size 3 μm) 80 The parts were mixed and dispersed uniformly with a high-speed rotary mixer to obtain a resin varnish.

  As a support, a polyethylene terephthalate film (thickness 38 μm, “AL5” manufactured by Lintec) having an alkyd resin release layer on the surface was prepared. On this support body, the said resin varnish was apply | coated uniformly using the die-coater. The applied 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, the adhesive film was wound up in a roll shape while a 15 μm-thick polypropylene film was bonded to the surface of the resin composition layer. The wound adhesive film was slit to a width of 507 mm to obtain a sheet-like adhesive film having a size of 507 mm × 336 mm.

[Example 2]
80 parts of polytetrafluoroethylene particles (“Lublon L-2” manufactured by Daikin Industries, Ltd.) were changed to 80 parts of polytetrafluoroethylene particles (“KTL-500F” manufactured by Kitamura Co., Ltd., average particle size: 0.3 μm). Except for the above, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Example 3]
The amount of bisphenol AF type epoxy resin (“YL7760” manufactured by Mitsubishi Chemical Corporation) was changed from 10 parts to 25 parts. In addition, 80 parts of polytetrafluoroethylene particles (“Lublon L-2” manufactured by Daikin Industries, Ltd.) were changed to 170 parts of polytetrafluoroethylene particles (“KTL-500F” manufactured by Kitamura Co., Ltd., average particle size 0.3 μm). . Further, spherical silica (“SO-C2” manufactured by Admatechs) that was surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) was not used. Further, the amount of liquid bisphenol A type epoxy resin (“jER828US” manufactured by Mitsubishi Chemical Corporation) was changed from 12 parts to 5 parts. Further, the amount of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation) was changed from 10 parts to 5 parts. Except for the above, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Example 4]
30 parts of biphenyl aralkyl type epoxy resin (“NC3000” manufactured by Nippon Kayaku Co., Ltd.) was changed to 27 parts of naphthylene ether type epoxy resin (epoxy equivalent 260, “HP6000” manufactured by DIC). Except for the above, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Example 5]
30 parts of biphenyl aralkyl type epoxy resin (“NC3000” manufactured by Nippon Kayaku Co., Ltd.), 20 parts of naphthylene ether type epoxy resin (epoxy equivalent 260, “HP6000” manufactured by DIC) and naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163) , “HP4700” manufactured by DIC Corporation). Except for the above, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Example 6]
15 parts of active ester-based curing agent (toluene solution with 65% by mass of non-volatile component, “HPC8000-65T” manufactured by DIC) and triazine skeleton-containing cresol novolac type curing agent (2-methoxypropanol solution with a solid content of 50% by mass, DIC) 25 parts of “LA3018-50P”), 15 parts of naphthol-based curing agent (hydroxyl equivalent 215, “SN485” manufactured by Nippon Steel Chemical Co., Ltd.) and triazine-containing phenol novolac resin (hydroxyl equivalent 125, methyl ethyl ketone solution having a solid content of 60%) , "LA7054" manufactured by DIC Corporation). Except for the above, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Example 7]
To the resin varnish, 2 parts of N-phenyl-3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) was further added. Except for the above, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Example 8]
100 parts of spherical silica ("SO-C2" manufactured by Admatechs) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was added to N-phenyl-3-aminopropyltrimethoxysilane. The amount was changed to 100 parts of spherical silica (“SO-C1” manufactured by Admatechs, average particle size of 0.3 μm) surface-treated with methoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.). Except for the above, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Example 9]
The amount of spherical silica ("SO-C2" manufactured by Admatechs) that was surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 100 parts to 50 parts. In addition, spherical silica (“SO-C1” manufactured by Admatechs, average particle size of 0.3 μm) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) on the resin varnish. 50 parts were added. Except for the above, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Example 10]
The amount of spherical silica ("SO-C2" manufactured by Admatechs) that was surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 100 parts to 50 parts. In addition, the amount of polytetrafluoroethylene particles (“Lublon L-2” manufactured by Daikin Industries, Ltd.) was changed from 80 parts to 40 parts. Furthermore, spherical silica (“SO-C1” manufactured by Admatechs, average particle size of 0.3 μm) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) on the resin varnish. 50 parts and 40 parts of polytetrafluoroethylene particles (“KTL-500F” manufactured by Kitamura Co., Ltd., average particle diameter: 0.3 μm) were added. Except for the above, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Example 11]
The thickness of the resin composition layer of the adhesive film was changed from 50 μm to 15 μm. Except for the above, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Comparative Example 1]
A bisphenol AF type epoxy resin (“YL7760” manufactured by Mitsubishi Chemical Corporation) was not used. Further, the amount of liquid bisphenol A type epoxy resin (“jER828US” manufactured by Mitsubishi Chemical Corporation) was changed from 12 parts to 20 parts. Except for the above, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Comparative Example 2]
A bisphenol AF type epoxy resin (“YL7760” manufactured by Mitsubishi Chemical Corporation) was not used. Further, the amount of liquid bisphenol A type epoxy resin (“jER828US” manufactured by Mitsubishi Chemical Corporation) was changed from 12 parts to 20 parts. Further, 4 parts of a fluorosurfactant (“Surflon S-243” manufactured by AGC Seimi Chemical Co., Ltd.) was added to the resin varnish. Except for the above, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Comparative Example 3]
A bisphenol AF type epoxy resin (“YL7760” manufactured by Mitsubishi Chemical Corporation) was not used. Further, the amount of liquid bisphenol A type epoxy resin (“jER828US” manufactured by Mitsubishi Chemical Corporation) was changed from 12 parts to 20 parts. Further, 2 parts of N-phenyl-3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the resin varnish. Except for the above, a resin varnish and an adhesive film were produced in exactly the same manner as in Example 1.

[Measurement of dielectric constant]
A polyethylene terephthalate film ("PET501010" manufactured by Lintec Corporation) having a release treatment on the surface was prepared. On this polyethylene terephthalate film, the resin varnish obtained in the Examples and Comparative Examples was uniformly applied using a die coater so that the thickness of the resin composition layer after drying was 50 μm. The applied resin varnish was dried at 80 ° C. to 110 ° C. (average 95 ° C.) for 6 minutes to obtain a resin composition layer. Thereafter, the resin composition layer was cured by heat treatment at 200 ° C. for 90 minutes, and the support was peeled off to obtain a cured film formed of a cured product of the resin composition. The cured product film was cut into a length of 80 mm and a width of 2 mm to obtain an evaluation sample.

  With respect to this evaluation sample, by a cavity resonance perturbation method using an analyzer (“HP 8362B” manufactured by Agilent Technologies) at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C., the dielectric of the cured product of the resin composition The rate was measured. The measurement was performed on two test pieces, and the average value was calculated.

[Evaluation of dispersibility of filler]
The adhesive films obtained in Examples and Comparative Examples were observed at a magnification of 1000 times using a microscope (“VH-2250” manufactured by KEYENCE). When the number of aggregates having a diameter of 50 μm or more was 0 per 10 fields and the number of aggregates having a diameter of 10 μm or more was less than 10 per 10 fields, the dispersibility of the filler was determined as “◯”. When the number of aggregates having a diameter of 50 μm or more was 1 or more per 10 fields, or when the number of aggregates having a diameter of 10 μm or more was 10 or more per 10 fields, the dispersibility of the filler was determined as “x”.

[Measurement of peel strength]
(1) Inner layer substrate surface treatment:
A glass cloth base epoxy resin double-sided copper-clad laminate (with a copper foil thickness of 18 μm, a substrate thickness of 0.8 mm, “R5715ES” manufactured by Matsushita Electric Works, Ltd.) on which an inner layer circuit was formed was prepared as an inner layer substrate. Both surfaces of this inner layer substrate were etched by 1 μm with an etching agent (“CZ8100” manufactured by MEC Co., Ltd.) to roughen both copper surfaces of the inner layer substrate.

(2) Lamination of adhesive film:
Using the batch type vacuum pressure laminator (two-stage build-up laminator “CVP700” manufactured by Nichigo Morton Co., Ltd.), the adhesive film produced in Examples and Comparative Examples was used so that the resin composition layer was in contact with the inner layer substrate. Lamination was performed on both sides of the inner layer substrate. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing the film at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. Next, hot pressing was performed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Curing of resin composition:
The adhesive film laminated on the inner layer substrate was heated at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes to cure the resin composition layer, thereby forming an insulating layer. Thereafter, the polyethylene terephthalate film as a support was peeled off. Thus, a sample substrate having an insulating layer, an inner layer substrate, and an insulating layer in this order was obtained.

(4) Roughening treatment:
The sample substrate was immersed in a swelling liquid (including “Swelling Dip Securigant P” manufactured by Atotech Japan, diethylene glycol monobutyl ether) at 60 ° C. for 10 minutes. Next, the sample substrate was immersed for 20 minutes at 80 ° C. in a roughening solution (“Concentrate Compact P” KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution manufactured by Atotech Japan). Next, the sample substrate was immersed for 5 minutes at 40 ° C. in a neutralizing solution (“Reduction Sholycine Securigant P” manufactured by Atotech Japan). Thereafter, 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 the methods described later.

(5) Plating by semi-additive method:
The roughened substrate was immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C. for 20 minutes. Thereafter, the roughened substrate was subjected to an annealing process of heating at 150 ° C. for 30 minutes. An etching resist was formed on the roughened substrate after the annealing treatment, and a pattern was formed by etching. Thereafter, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 25 μm on the surface of the insulating layer. Next, annealing 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 peel strength (peel strength) of plated conductor layer:
A cut was made in the conductor layer of the circuit board so as to surround a rectangular portion having a width of 10 mm and a length of 100 mm. One end of the rectangular portion in the length direction was peeled off and grasped with a gripping tool (Autocom type tester “AC-50CSL” manufactured by TS E). Then, at room temperature, a peeling test is conducted to peel off the conductor layer in the direction perpendicular to the surface of the circuit board at a speed of 50 mm / min, and the load (kgf / cm) when peeling the length of 35 mm is peeled off. Measured as strength. In addition, the case where the insulating layer was swollen was not measured because it was inferior in peel strength without actual measurement.

[Measurement of arithmetic average roughness (Ra) and ten-point average roughness (Rz)]
Arithmetic average surface roughness Ra and ten-point average surface roughness Rz of the insulating layer of the roughened substrate were measured using a non-contact type surface roughness meter ("WYKO NT3300" manufactured by BEIKO INSTRUMENTS), VSI contact mode, 50 times. Using a lens, the measurement range was 121 μm × 92 μm. A measurement value was obtained by obtaining an average value of 10 points selected at random.

[result]
The results of the above-described examples and comparative examples are shown in the following table. In the following table, the amount of each component represents parts by mass of the non-volatile component. In the table below, the meanings of the abbreviations are as follows.
YL7760: Bisphenol AF type epoxy resin (epoxy equivalent 235, “YL7760” manufactured by Mitsubishi Chemical Corporation).
HPC8000-65T: active ester-based curing agent (active group equivalent 223, non-volatile component 65% by weight toluene solution, DIC Corporation “HPC8000-65T”).
SN485: a naphthol-based curing agent (hydroxyl group equivalent 215, “SN485” manufactured by Nippon Steel Chemical Co., Ltd.).
LA3018-50P: Triazine skeleton-containing cresol novolac type curing agent (phenol equivalent 151, 2-methoxypropanol solution having a solid content of 50% by mass, “LA3018-50P” manufactured by DIC).
LA7054: Triazine-containing phenol novolak resin (methylethylketone solution having a hydroxyl group equivalent of 125 and a solid content of 60%, "LA7054" manufactured by DIC).
Lubron L-2: polytetrafluoroethylene particles (“Lublon L-2” manufactured by Daikin Industries, Ltd., average particle diameter: 3 μm).
KTL-500F: polytetrafluoroethylene particles (“KTL-500F” manufactured by Kitamura Co., Ltd., average particle size: 0.3 μm).
SO-C1: Spherical silica surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C1” manufactured by Admatechs, average particle size: 0.3 μm).
SO-C2: Spherical silica surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C2” manufactured by Admatechs, average particle size of 0.5 μm).
828US: Liquid bisphenol A type epoxy resin (epoxy equivalent 187, “jER828US” manufactured by Mitsubishi Chemical Corporation).
YX4000HK: Boxylenol type epoxy resin (epoxy equivalent 190, “YX4000HK” manufactured by Mitsubishi Chemical Corporation).
NC3000: biphenyl aralkyl type epoxy resin (epoxy equivalent 276, “NC3000” manufactured by Nippon Kayaku Co., Ltd.).
HP6000: A naphthylene ether type epoxy resin (epoxy equivalent 260, “HP6000” manufactured by DIC).
HP4700: Naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, “HP4700” manufactured by DIC Corporation).
ESN475V: naphthol type epoxy resin (epoxy equivalent 332, “ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
YL7553BH30: Phenoxy resin (methyl ethyl ketone / cyclohexanone = 1/1 solution having a solid content of 30% by mass, “YL7553BH30” manufactured by Mitsubishi Chemical Corporation).
DMAP: curing accelerator (4-dimethylaminopyridine, methyl ethyl ketone solution having a solid content of 5% by mass).
KBM573: N-phenyl-3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.).
S-243: Fluorine-based surfactant (“Surflon S-243” manufactured by AGC Seimi Chemical Co., Ltd.).

[Consideration]
As can be seen from Table 1, in the examples, a low dielectric constant is obtained. Moreover, in the Example, (C) High dispersibility of fillers, such as a fluorine-type filler, is acquired. Furthermore, in an Example, the peel strength which shows the high adhesiveness of an insulating layer and a conductor layer is large. Therefore, from this result, according to the present invention, an insulating layer having a low dielectric constant and excellent adhesion to the conductor layer can be obtained, and further, (C) a resin composition excellent in dispersibility of the fluorine-based filler is realized. It was confirmed that it was possible.

  On the other hand, in (A) Comparative Examples 1 to 3 in which no fluorine-based epoxy resin is used, the insulating layer is swollen and the adhesion to the conductor layer cannot be improved. The swelling of the insulating layer is considered to be caused by aggregation of (C) fluorine-based filler. In particular, Comparative Example 2 was able to improve the dispersibility of the (C) fluorine-based filler by using the fluorine-based surfactant, but the degree of improvement was from the viewpoint of increasing the adhesion of the conductor layer. It was insufficient. When these comparative examples are compared with the examples, in order to obtain the desired effect of the present invention, it is particularly desirable to combine (A) a fluorine-based epoxy resin containing fluorine atoms with (C) a fluorine-based filler. I understand.

  In the above examples, it was confirmed that even if the components (D) to (H) were not used, the results were the same as in the above examples, although there were differences in the degree.

Claims (12)

  (A) A resin composition comprising an epoxy resin containing fluorine atoms in the molecule, (B) a curing agent, and (C) a fluorine-based filler.   The resin composition according to claim 1, wherein the component (A) is a bisphenol AF type epoxy resin.   (C) The resin composition of Claim 1 or 2 whose average particle diameter of a component is 0.05 micrometer-5 micrometers.   The resin composition according to any one of claims 1 to 3, wherein the component (B) contains an active ester curing agent.   (D) The resin composition of any one of Claims 1-4 containing an inorganic filler.   The resin composition of Claim 5 whose quantity of (C) component is 20 mass%-80 mass% with respect to 100 mass% of total amounts of (C) component and (D) component.   The resin composition according to claim 1, which is used for forming an insulating layer on a circuit board.   A sheet-like laminate material comprising the resin composition according to claim 1.   The sheet-like laminated body containing the resin composition layer formed with the resin composition of any one of Claims 1-7.   The sheet-like laminated body of Claim 9 whose thickness of a resin composition layer is 30 micrometers or less.   The circuit board containing the insulating layer which consists of a hardened | cured material of the resin composition of any one of Claims 1-7.   A semiconductor device comprising the circuit board according to claim 11.