KR20210110212A - Resin composition - Google Patents

Abstract

Provided is a resin composition capable of suppressing curvature during curing and obtaining a cured product having excellent adhesion strength. The resin composition includes: (A) a condensed ring structure-containing epoxy resin; (B) an alkoxy group-containing naphthol aralkyl resin; and (C) an inorganic filler, wherein the content of the (C) component is 70 mass% or more when the content of a non-volatile component in the resin composition is 100 mass%.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition comprising an epoxy resin. Moreover, it is related with the hardened|cured material obtained using the said resin composition, a sheet-like laminated material, a resin sheet, a printed wiring board, and a semiconductor device.

As a manufacturing technique of a printed wiring board, the manufacturing method by the build-up method which piles up an insulating layer and a conductor layer alternately is known. In the manufacturing method by the build-up method, in general, the insulating layer is formed by curing the resin composition.

In general, printed wiring boards are exposed to a wide temperature environment from a low temperature environment such as room temperature to a high temperature environment such as reflow. Repeatedly, cracks occur due to the deformation.

As a method of suppressing the coefficient of linear thermal expansion low, the method of making a resin material highly fill an inorganic filler (patent document 1) is known. However, when an inorganic filler is highly filled in a resin material, the elasticity modulus at the time of hardening will become high, and it will become difficult to suppress curvature.

Moreover, high adhesive strength is calculated|required by an insulating layer.

Japanese Patent Laid-Open No. 2016-27097

The subject of this invention is providing the resin composition which can suppress the curvature at the time of hardening and can obtain the hardened|cured material which has the outstanding adhesive strength.

In order to achieve the subject of this invention, as a result of earnest examination of the present inventors, even if it is a resin composition containing 70 mass % or more (C) inorganic filler, (A) condensed ring structure containing epoxy resin, and (B) alkoxy group containing naphthol By containing an aralkyl resin, it discovered that the curvature at the time of hardening can be suppressed and the hardened|cured material which has the outstanding adhesive strength can be obtained, and came to complete this invention.

That is, the present invention includes the following contents.

[1] A resin composition comprising (A) a condensed ring structure-containing epoxy resin, (B) an alkoxy group-containing naphthol aralkyl resin, and (C) an inorganic filler,

(C) When content of a component makes the non-volatile component in a resin composition 100 mass %, the resin composition of 70 mass % or more.

[2] The component (B) has the following formula (2):

[Formula (2)]

[wherein, each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, at least one R is an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 2 to 20]

The resin composition according to the above [1], which is a naphthol aralkyl resin represented by .

[3] The resin composition according to [1] or [2], wherein the component (A) contains (A-1) a monomer-type condensed ring structure-containing epoxy resin.

[4] The epoxy equivalent of the component (A-1) was 120 g/eq. more than 200g/eq. The resin composition as described in said [3] which is the following.

[5] The resin composition according to the above [3] or [4], wherein the molecular weight of the component (A-1) is 500 or less.

[6] The resin composition according to any one of [1] to [5], wherein the component (A) contains (A-2) a condensed ring structure-containing epoxy resin of a repeating structure type.

[7] The epoxy equivalent of the component (A-2) is 250 g/eq. more than 400g/eq. The resin composition as described in said [6] which is the following.

[8] The resin composition according to [6] or [7], wherein the component (A-2) is a naphthol aralkyl-type epoxy resin.

[9] the above [3] to [8], wherein the component (A) contains both (A-1) a monomeric type condensed ring structure-containing epoxy resin and (A-2) a repeating structure type condensed ring structure-containing epoxy resin ] The resin composition as described in any one of.

[10] The resin composition according to the above [9], wherein the mass ratio (monomer type/repeating structure type) of the component (A-1) to the component (A-2) is 1 or more and 5 or less.

[11] The resin composition according to any one of [1] to [10], wherein the content of the component (A) is 90% by mass or more when the total epoxy resin in the resin composition is 100% by mass.

[12] The resin according to any one of [1] to [11], wherein the content of the component (A) is 50% by mass or more when the nonvolatile components other than the component (C) in the resin composition are 100% by mass. composition.

[13] (D) The resin composition according to any one of [1] to [12], further comprising an organic filler.

[14] The resin composition according to the above [13], wherein the component (D) is a core-shell rubber particle.

[15] The resin composition according to any one of [1] to [14], wherein the content of the component (C) is 80% by mass or more when the nonvolatile component in the resin composition is 100% by mass.

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

[17] A sheet-like laminated material containing the resin composition according to any one of [1] to [15].

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

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

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

ADVANTAGE OF THE INVENTION According to the resin composition of this invention, the curvature at the time of hardening can be suppressed and the hardened|cured material which has the outstanding adhesive strength can be obtained.

Hereinafter, the present invention will be described in detail based on preferred embodiments thereof. However, the present invention is not limited to the following embodiments and examples, and may be arbitrarily changed and implemented without departing from the scope of the claims of the present invention and its equivalents.

<Resin composition>

The resin composition of this invention contains (A) condensed ring structure containing epoxy resin, (B) alkoxy group containing naphthol aralkyl resin, and (C) inorganic filler, Content of (C)component is non-volatile in a resin composition When a component is 100 mass %, it is 70 mass % or more. By using such a resin composition, the curvature at the time of hardening can be suppressed and the hardened|cured material which has the outstanding adhesive strength can be obtained.

The resin composition of this invention may further contain arbitrary components other than (A) condensed ring structure containing epoxy resin, (B) alkoxy group containing naphthol aralkyl resin, and (C) inorganic filler. As optional components, for example, (D) organic filler, (E) curing agent, (F) curing accelerator, (G) radically polymerizable compound, (H) radical polymerization initiator, (I) other additives, (J) and organic solvents. Hereinafter, each component contained in a resin composition is demonstrated in detail.

<(A) Condensed ring structure-containing epoxy resin>

The resin composition of this invention contains the (A) condensed-ring structure containing epoxy resin. (A) Condensed ring structure-containing epoxy resin means a resin having one or more condensed rings and one or more (preferably two or more) epoxy groups in one molecule. (A) Condensed ring structure-containing epoxy resin is an epoxy resin prepolymer that can be crosslinked through an epoxy group. (A) Condensed ring structure containing epoxy resin may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

(A) It is preferable that the condensed ring contained in the condensed-ring structure containing epoxy resin is a condensed aromatic hydrocarbon ring. The condensed aromatic hydrocarbon ring is a bicyclic or more aromatic hydrocarbon ring obtained by condensing two or more benzene rings, preferably having 10 to 18 carbon atoms, more preferably 10 to 14 carbon atoms, for example, a naphthalene ring, an anthracene ring, A phenanthrene ring etc. are mentioned, Especially preferably, it is a naphthalene ring.

(A) Condensed ring structure-containing epoxy resin may be any of glycidyl ether type, glycidyl amine type, glycidyl ester type, and olefin oxidation (alicyclic) type, but among them, glycidyl ether type it is preferable

(A) Condensed ring structure containing epoxy resin may be a monomer type or a repeating structure type may be sufficient as it. Here, the repeating structural type refers to a resin having a polymer structure having 3 or more repeating units containing 1 or 2 or more condensed rings, and the monomeric type refers to other resins. In one embodiment, (A) Condensed ring structure containing epoxy resin contains (A-1) monomeric type Condensed ring structure containing epoxy resin. In one embodiment, (A) Condensed ring structure containing epoxy resin contains (A-2) Condensed ring structure containing epoxy resin of a repeating structure type. In one embodiment, (A) the condensed ring structure-containing epoxy resin comprises both (A-1) a monomeric condensed ring structure-containing epoxy resin and (A-2) a repeating structure type condensed ring structure-containing epoxy resin it is preferable

(A-1) Examples of the monomer-type condensed ring structure-containing epoxy resin include 1,6-bis(glycidyloxy)naphthalene, 1,5-bis(glycidyloxy)naphthalene, 2,7- Monomeric type condensed ring structure containing epoxy resin which has one condensed ring in 1 molecule, such as bis (glycidyloxy) naphthalene and 2, 6-bis (glycidyloxy) naphthalene; Bis[2-(glycidyloxy)-1-naphthyl]methane, 2,2-bis[2-(glycidyloxy)-1-naphthyl]propane, bis[2,7-bis(glycy Dyloxy)-1-naphthyl]methane, 2,2-bis[2,7-bis(glycidyloxy)-1-naphthyl]propane, [2,7-bis(glycidyloxy)-1 -naphthyl][2-(glycidyloxy)-1-naphthyl]methane, 2-[2,7-bis(glycidyloxy)-1-naphthyl]-2-[2-(glycy and monomeric condensed ring structure-containing epoxy resins having two condensed rings in one molecule, such as diloxy)-1-naphthyl]propane.

(A-1) The monomeric condensed ring structure-containing epoxy resin is preferably a monomeric condensed ring structure-containing epoxy resin having one condensed ring in one molecule, particularly preferably 1,6-bis (glycidyloxy)naphthalene.

(A-1) The monomer-type condensed ring structure-containing epoxy resin is preferably a bifunctional to tetrafunctional epoxy resin, more preferably a bifunctional or trifunctional epoxy resin, and a bifunctional epoxy resin Especially preferred.

(A-1) Although the epoxy equivalent of a monomeric condensed-ring structure containing epoxy resin is not specifically limited, Preferably 50 g/eq. above, more preferably 80 g/eq. or more, more preferably 100 g/eq. or more, more preferably 120 g/eq. or more, particularly preferably 130 g/eq. More than that. (A-1) Although the upper limit of the epoxy equivalent of a monomeric condensed-ring structure containing epoxy resin is not specifically limited, Preferably 1,000 g/eq. Hereinafter, more preferably 500 g/eq. Hereinafter, more preferably 300 g/eq. Hereinafter, more preferably 200 g/eq. Below, particularly preferably 160 g/eq. is below.

(A-1) The molecular weight of the monomeric condensed ring structure-containing epoxy resin is not particularly limited, but preferably 2,000 or less, more preferably 1,000 or less, still more preferably 700 or less, still more preferably 600 or less. or less, particularly preferably 500 or less.

(A-1) As a commercial item of monomeric condensed-ring structure containing epoxy resin, For example, "HP-4032D", "HP-4032SS" by DIC Corporation (epoxy resin which has one naphthalene ring in 1 molecule) ; "EXA-4750", "HP-4770", "HP-4700", "HP-4710" (epoxy resin which has two naphthalene rings in 1 molecule) etc. by DIC company are mentioned.

(A-2) As the condensed ring structure-containing epoxy resin of the repeating structure type, for example, a naphthol novolak-type epoxy resin, a naphthol-phenol co-condensed novolac-type epoxy resin, a naphthol-cresol co-condensed novolac-type epoxy resin, and a naphthol aralkyl and epoxy resins containing a condensed ring structure of a repeating structure containing molecules having three or more condensed rings in one molecule, such as a type epoxy resin, a naphthalenediol aralkyl type epoxy resin, and a naphthylene ether type epoxy resin. Especially, a naphthol aralkyl type epoxy resin is especially preferable. In addition, a naphthol aralkyl type epoxy resin means the epoxy resin which has a molecular structure in which the naphthylene unit and aralkylene unit which have an epoxy group are repeated alternately.

(A-2) Although the epoxy equivalent of the condensed-ring structure containing epoxy resin of a repeating structure type is not specifically limited, Preferably 50 g/eq. or more, more preferably 100 g/eq. or more, more preferably 200 g/eq. or more, more preferably 250 g/eq. or more, particularly preferably 300 g/eq. More than that. (A-2) Although the upper limit of the epoxy equivalent of the condensed-ring structure containing epoxy resin of a repeating structure type is not specifically limited, Preferably 2,000 g/eq. Hereinafter, more preferably 1,000 g/eq. Hereinafter, more preferably 500 g/eq. Hereinafter, more preferably 400 g/eq. is below.

(A-2) As a commercial item of the condensed-ring structure containing epoxy resin of a repeating structure type, "ESN-155", "ESN-185V", "ESN-175", "ESN" by Nittetsu Chemical & Materials, for example. -475V", "ESN-485", "TX-1507B" (naphthol aralkyl type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP-6000", "HP-6000-L" (naphthylene) manufactured by DIC Corporation ether-type epoxy resin); "NC7000L" (naphthol novolak-type epoxy resin) by a Nippon Kayaku company, etc. are mentioned.

(A) When the condensed ring structure-containing epoxy resin contains both (A-1) a monomeric condensed ring structure-containing epoxy resin and (A-2) a repeating structure type condensed ring structure-containing epoxy resin, (A-1 ) The mass ratio (monomer type/repeating structure type) of the monomeric condensed ring structure-containing epoxy resin and (A-2) repeating structure type condensed ring structure-containing epoxy resin is not particularly limited, but preferably 0.1 or more, more preferably Preferably it is 0.5 or more, More preferably, it is 1 or more, Especially preferably, it is 1.2 or more. Although the upper limit of the said mass ratio is not specifically limited, Preferably it is 10 or less, More preferably, it is 5 or less.

The resin composition may contain other epoxy resins in addition to the (A) condensed ring structure-containing epoxy resin, but the content of the (A) condensed ring structure-containing epoxy resin in the resin composition is 100% by mass of all the epoxy resins in the resin composition. %, preferably 50 mass % or more, 60 mass % or more, more preferably 70 mass % or more, 80 mass % or more, still more preferably 90 mass % or more, from the viewpoint of significantly obtaining the desired effect of the present invention. or more, 95 mass % or more, More preferably, it is 98 mass % or more, 99 mass % or more, Especially preferably, it is 100 mass %.

Although content of (A) condensed-ring structure containing epoxy resin in a resin composition is not specifically limited, When making non-volatile components other than (C) inorganic filler in a resin composition 100 mass %, from a viewpoint of improving adhesive strength , Preferably it is 10 mass % or more, More preferably, it is 30 mass % or more, More preferably, it is 40 mass % or more, More preferably, it is 50 mass % or more, Especially preferably, it is 55 mass % or more or 60 mass % or more. am. Although the upper limit of content of (A) condensed-ring structure containing epoxy resin in a resin composition is not specifically limited, When making non-volatile components other than (C) inorganic filler in a resin composition 100 mass %, Preferably it is 90 mass % or less, more preferably 80 mass% or less, still more preferably 75 mass% or less, still more preferably 70 mass% or less, particularly preferably 65 mass% or less.

<(B) Alkoxy group-containing naphthol aralkyl resin>

The resin composition of the present invention contains (B) an alkoxy group-containing naphthol aralkyl resin. (B) Alkoxy group-containing naphthol aralkyl resin means a resin having a molecular structure in which naphthylene units having a hydroxyl group and/or an alkoxy group and aralkylene units are alternately repeated. Each unit may further have arbitrary substituents. In addition, (B) alkoxy group containing naphthol aralkyl resin demonstrated below is resin which does not contain an epoxy group, and does not contain the thing corresponding to (A) component. (B) Alkoxy group containing naphthol aralkyl resin may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

(B) In the naphthol aralkyl resin containing an alkoxy group, the alkoxy group is preferably directly bonded to the naphthalene ring, and particularly preferably directly bonded to the α-position of the naphthalene ring. The alkoxy group refers to a monovalent group to which a linear, branched and/or cyclic monovalent aliphatic saturated hydrocarbon group is bonded through an oxygen atom. (B) A C1-C6 alkoxy group is preferable and, as for the alkoxy group contained in naphthol aralkyl resin containing an alkoxy group, a C1-C3 alkoxy group is more preferable. As an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group etc. are mentioned, for example, Especially, a methoxy group is especially preferable.

In one embodiment, (B) the alkoxy group-containing naphthol aralkyl resin further contains a hydroxyl group (preferably a phenolic hydroxyl group directly bonded to a naphthalene ring (particularly preferably directly bonded to the α-position)) desirable. Therefore, in the said embodiment, (B) alkoxy group containing naphthol aralkyl resin may have a function as a hardening|curing agent which hardens the epoxy resin containing (A) component. In the above embodiment, the equivalent ratio (hydroxyl group/alkoxy group) of the hydroxyl group and the alkoxy group may be preferably 0.1 or more, more preferably 1 or more, still more preferably 2 or more, particularly preferably 3 or more.

(B) Alkoxy group-containing naphthol aralkyl resin is not particularly limited, but preferably, the following formula (1):

[Formula (1)]

[wherein, each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, at least one R is an alkyl group having 1 to 6 carbon atoms, n represents an integer of 2 to 20, and X is each independently is a naphthol aralkyl resin represented by an alkylene group having 1 to 6 carbon atoms, and rings A, B and C may each independently have a substituent;

More preferably, the formula (2):

[Formula (2)]

Naphthol represented by [wherein, each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, at least one R is an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 2 to 20] It is an aralkyl resin.

In formulas (1) and (2), R each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and at least one R is an alkyl group having 1 to 6 carbon atoms. The alkyl group refers to a linear, branched and/or cyclic monovalent aliphatic saturated hydrocarbon group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a sec-pentyl group. , a tert-pentyl group, a cyclopentyl group, a cyclohexyl group, and the like. R each preferably independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and at least one R is an alkyl group having 1 to 3 carbon atoms; More preferably, each independently represents a hydrogen atom or a methyl group, and at least one R is a methyl group. In one embodiment, it is preferred that at least one R is a hydrogen atom. In the above embodiment, the proportion of R which is a hydrogen atom is preferably 50% or more, more preferably 60% or more, when all Rs are 100%.

In general formulas (1) and (2), n represents the integer of 2-20. n is preferably an integer of 2 to 10, more preferably an integer of 2 to 8, still more preferably an integer of 3 to 6, particularly preferably 4 or 5.

In general formula (1), each X independently represents a C1-C6 alkylene group. The alkylene group means a linear, branched or cyclic divalent aliphatic saturated hydrocarbon group. Examples of the alkylene group include -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH(CH ₃ )- , -CH(CH ₃ )-CH ₂ -, -C(CH ₃ ) ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH(CH ₃ )-, - CH ₂ -CH(CH ₃ )-CH ₂ -, -CH(CH ₃ )-CH ₂ -CH ₂ -, -CH ₂ -C(CH ₃ ) ₂ -, -C(CH ₃ ) ₂ -CH ₂ - and the like. X is preferably, each independently an alkylene group having 1 to 3 carbon atoms, more preferably -CH ₂ -.

In the formula (1), each of the rings A, B, and C independently may further have a substituent. Additional substituents in Rings A, B and C are not particularly limited, For example, hydrocarbon groups such as an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aralkyl group having 7 to 15 carbon atoms can An aryl group means a monovalent|monohydric aromatic hydrocarbon group. As an aryl group, a phenyl group, 1-naphthyl group, 2-naphthyl group etc. are mentioned, for example. The aralkyl group refers to an alkyl group substituted with one or two or more aryl groups. As an aralkyl group, a benzyl group, a phenethyl group, 2-naphthylmethyl group, etc. are mentioned, for example. It is preferable that the number of additional substituents of rings A, B and C is 0-2, and it is especially preferable that rings A, B and C do not have a substituent further. It is preferable that the ring C is couple|bonded with two X at the para position.

(B) Although the number average molecular weight of an alkoxy group containing naphthol aralkyl resin is not specifically limited, Preferably it is 400-5,000, More preferably, it is 600-3,000, More preferably, it is 800-2,000. The number average molecular weight may be, for example, what was measured as a value in terms of polystyrene by a gel permeation chromatography (GPC) method.

Although content of (B) alkoxy group containing naphthol aralkyl resin in a resin composition is not specifically limited, When making non-volatile components other than (C) inorganic filler in a resin composition 100 mass %, Preferably it is 0.1 mass % More preferably, it is 1 mass % or more, More preferably, it is 2 mass % or more. Although the upper limit of content of (B) alkoxy group containing naphthol aralkyl resin in a resin composition is not specifically limited, When making non-volatile components other than (C) inorganic filler in a resin composition 100 mass %, Preferably 40 It is mass % or less, More preferably, it is 30 mass % or less, More preferably, it is 25 mass % or less, More preferably, it is 20 mass % or less, Especially preferably, it is 15 mass % or less.

<(C) Inorganic filler>

The resin composition of this invention contains (C) an inorganic filler. (C) The inorganic filler is contained in the resin composition in the state of particle|grains.

(C) An inorganic compound is used as a material of an inorganic filler. (C) As the material of the inorganic filler, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, hydroxide Aluminum, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, Barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphate tungstate, etc. are mentioned. Among these, silica is particularly suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as a silica, spherical silica is preferable. (C) An inorganic filler may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

(C) As a commercial item of an inorganic filler, For example, "UFP-30" by Denka Chemical Co., Ltd.; "SP60-05", "SP507-05" by the Shin-Nitetsu Sumikin Materials company; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Adomatex Corporation; "UFP-30" by Denka Corporation; "Silly writing NSS-3N", "Silly writing NSS-4N", "Silly writing NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" by Adomatex Corporation; "DAW-03" by Denka Corporation, "FB-105FD", etc. are mentioned.

(C) The average particle diameter of the inorganic filler is not particularly limited, but preferably 20 µm or less, more preferably 10 µm or less, still more preferably 5 µm or less, still more preferably 3 µm or less, particularly Preferably it is 1 micrometer or less. (C) The lower limit of the average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.01 µm or more, more preferably 0.05 µm or more, still more preferably 0.1 µm or more, particularly preferably 0.2 µm or more. . (C) The average particle diameter of an inorganic filler can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, it can measure by creating the particle diameter distribution of an inorganic filler on a volume basis with a laser diffraction scattering type particle diameter distribution measuring apparatus, and making the intermediate diameter into an average particle diameter. As the measurement sample, 100 mg of inorganic filler and 10 g of methyl ethyl ketone were weighed in a vial bottle, and what was dispersed by ultrasonic waves for 10 minutes can be used. Using a laser diffraction particle size distribution measuring device, the measurement sample was measured for the volume-based particle size distribution of the inorganic filler by a flow cell method using a light source wavelength of blue and red, and the median diameter from the obtained particle size distribution The average particle diameter was calculated as As a laser diffraction type particle size distribution measuring apparatus, "LA-960" by Horiba Corporation, etc. are mentioned, for example.

(C) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m 2 /g or more, more preferably 0.5 m 2 /g or more, still more preferably 1 m 2 /g or more, particularly preferably 3 m2/g or more. (C) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but preferably 50 m 2 /g or less, more preferably 30 m 2 /g or less, still more preferably 20 m 2 /g or less, particularly preferably is 10 m 2 /g or less. The specific surface area of the inorganic filler is obtained by adsorbing nitrogen gas to the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec) according to the BET method, and calculating the specific surface area using the BET multi-point method. .

(C) It is preferable that the inorganic filler is surface-treated with the appropriate surface treating agent. By surface-treating, the moisture resistance and dispersibility of (C) inorganic filler can be improved. As a surface treatment agent, For example, vinyl-type silane coupling agents, such as vinyl trimethoxysilane and vinyl triethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, epoxy-based silane coupling agents such as 3-glycidoxypropyltriethoxysilane; styryl-based silane coupling agents such as p-styryltrimethoxysilane; Methacryl silane couples such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane ringer; acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltri Ethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrime amino-based silane coupling agents such as oxysilane and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; isocyanurate-based silane coupling agents such as tris-(trimethoxysilylpropyl)isocyanurate; urea-based silane coupling agents such as 3-ureidepropyltrialkoxysilane; mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatepropyltriethoxysilane; silane coupling agents such as acid anhydride-based silane coupling agents such as 3-trimethoxysilylpropyl succinic anhydride; Methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, Non-silane couplings such as hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, and trifluoropropyltrimethoxysilane - Alkoxysilane, etc. are mentioned. In addition, a surface treating agent may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

As a commercial item of a surface treatment agent, For example, "KBM-1003" by a Shin-Etsu Chemical Co., Ltd. product, "KBE-1003" (vinyl-type silane coupling agent); "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403" (epoxy silane coupling agent); "KBM-1403" (styryl-based silane coupling agent); "KBM-502", "KBM-503", "KBE-502", "KBE-503" (methacrylic silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM-603", "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-575" (amino silane coupling agent); "KBM-9659" (isocyanurate-based silane coupling agent); "KBE-585" (urea-based silane coupling agent); "KBM-802", "KBM-803" (mercapto-based silane coupling agent); "KBE-9007N" (isocyanate-based silane coupling agent); "X-12-967C" (acid anhydride-based silane coupling agent); 「KBM-13」, 「KBM-22」, 「KBM-103」, 「KBE-13」, 「KBE-22」, 「KBE-103」, 「KBM-3033」, 「KBE-3033」, 「KBM -3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" (non-silane coupling-alkoxysilane compound), etc. are mentioned.

It is preferable that the grade of the surface treatment by a surface treating agent falls within a predetermined range from a viewpoint of the dispersibility improvement of an inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with a surface treatment agent of 0.2% by mass to 5% by mass, more preferably surface-treated at 0.2% by mass to 3% by mass, 0.3% by mass It is more preferable that it is surface-treated at -2 mass %.

The grade of the surface treatment by a surface treating agent can be evaluated by the amount of carbon per unit surface area of an inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and still more preferably 0.2 mg/m 2 or more. In addition, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or melt viscosity in the form of a sheet, 1.0 mg/m 2 or less is preferable, 0.8 mg/m 2 or less is more preferable, and 0.5 mg/m 2 or less is still more preferable. .

(C) The amount of carbon per unit surface area of an inorganic filler can be measured, after washing-processing the inorganic filler after surface treatment with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, MEK in a sufficient amount as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, followed by ultrasonic cleaning at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" by Horiba Corporation, etc. can be used.

The content of the (C) inorganic filler in the resin composition is 70% by mass or more, preferably 75% by mass or more, more preferably 78% by mass or more, when the nonvolatile component in the resin composition is 100% by mass. Preferably it is 80 mass % or more, Especially preferably, it is 82 mass % or more. Although the upper limit of content of (C) inorganic filler in a resin composition is not specifically limited, When making the non-volatile component in a resin composition 100 mass %, For example, 98 mass % or less, 95 mass % or less, 90 mass % or less, or 85% by mass or less.

<(D) organic filler>

The resin composition of the present invention may further contain (D) an organic filler as an optional component. (D) An organic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

(D) The organic filler is present in the resin composition in particulate form. (D) Examples of the organic filler include rubber particles, polyamide fine particles, and silicone particles. In the present invention, it is preferable to use rubber particles from the viewpoint of significantly obtaining the desired effect of the present invention. .

Examples of the rubber component contained in the rubber particles include polybutadiene, polyisoprene, polychlorobutadiene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutylene copolymer, olefinic thermoplastic elastomers such as acrylonitrile-butadiene copolymer, isoprene-isobutylene copolymer, isobutylene-butadiene copolymer, ethylene-propylene-diene terpolymer, and ethylene-propylene-butene terpolymer; and thermoplastic elastomers such as acrylic thermoplastic elastomers such as poly(meth)acrylic acid propyl, poly(meth)acrylic acid butyl, poly(meth)acrylic acid cyclohexyl, and poly(meth)acrylic acid octyl, Preferably, olefinic thermoplastic elastomer and, more preferably, a styrene-butadiene copolymer. Moreover, you may mix silicone type rubber, such as polyorganosiloxane rubber, with a rubber component. The glass transition temperature of the rubber component contained in the rubber particles is, for example, 0°C or less, preferably -10°C or less, more preferably -20°C or less, and still more preferably -30°C or less.

(D) It is preferable that an organic filler is a core-shell type rubber particle from a viewpoint of acquiring the desired effect of this invention remarkably. The core-shell type rubber particle is a particulate organic filler composed of a core particle containing a rubber component as exemplified above and a shell portion of one or more layers covering the core particle. In addition, the core-shell type particle is a core-shell type graft copolymer rubber particle comprising a core particle containing a rubber component as exemplified above, and a shell portion obtained by graft copolymerizing a monomer component copolymerizable with the rubber component contained in the core particle. it is preferable The core-shell type as used herein does not necessarily refer only to those in which the core particle and the shell part can be clearly distinguished, but also includes those in which the boundary between the core particle and the shell part is unclear, and the core particle may not be completely covered with the shell part.

It is preferable to contain 40 mass % or more in core-shell type rubber particle, as for a rubber component, it is more preferable to contain 50 mass % or more, It is still more preferable to contain 60 mass % or more. The upper limit of the content of the rubber component in the core-shell rubber particles is not particularly limited, but is preferably 95% by mass or less and 90% by mass or less from the viewpoint of sufficiently covering the core particles with the shell portion.

The monomer component forming the shell part of the core-shell type rubber particle is, for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, (meth)acrylate ) (meth)acrylic acid esters such as glycidyl acrylate; (meth)acrylic acid; N-substituted maleimides, such as N-methylmaleimide and N-phenylmaleimide; maleimide; α,β-unsaturated carboxylic acids such as maleic acid and itaconic acid; aromatic vinyl compounds such as styrene, 4-vinyltoluene and α-methylstyrene; (meth)acrylonitrile etc. are included, Especially, it is preferable that (meth)acrylic acid ester is included, and it is more preferable that methyl (meth)acrylate is included.

As a commercial item of a core-shell type rubber particle, For example, "CHT" by the Cheil Industries; "B602" manufactured by UMGABS; "Pararoid EXL-2602", "Paraloid EXL-2603", "Pararoid EXL-2655", "Pararoid EXL-2311", "Pararoid EXL2313", "Pararoid EXL-2315" manufactured by Dow Chemical Nippon Corporation ', "Pararoid KM-330", "Pararoid KM-336P", "Pararoid KCZ-201", "Metablen C-223A" manufactured by Mitsubishi Rayon, "Metablen E-901", "Metablen" S-2001", "Metablen W-450A", "Metablen SRK-200", "Kaneace M-511", "Kaneace M-600", "Kaneace M-400", Carneace M-580", "Carneace MR-01", etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

(D) The average particle diameter (average primary particle diameter) of the organic filler is not particularly limited, but is preferably 20 nm or more, more preferably 50 nm or more, still more preferably 80 nm or more, particularly preferably 100 nm or more. . (D) The upper limit of the average particle diameter (average primary particle diameter) of the organic filler is not particularly limited, but is preferably 5,000 nm or less, more preferably 2,000 nm or less, still more preferably 1,000 nm or less, particularly preferably It is usually less than 500 nm. (D) The average particle diameter (average primary particle diameter) of the organic filler can be measured using a zeta potential particle size distribution analyzer or the like.

Although content of (D) organic filler in a resin composition is not specifically limited, When making non-volatile components other than (C) inorganic filler in a resin composition 100 mass %, Preferably it is 40 mass % or less, More preferably is 30% by mass or less, more preferably 20% by mass or less, particularly preferably 15% by mass or less. Although the lower limit of content of (D) organic filler in a resin composition is not specifically limited, When making non-volatile components other than (C) inorganic filler in a resin composition 100 mass %, Preferably it is 0.1 mass % or more, More Preferably it is 1 mass % or more, More preferably, it is 5 mass % or more, Especially preferably, it is 10 mass % or more.

<(E) curing agent>

The resin composition of the present invention may further contain (E) a curing agent as an optional component. (E) A hardening|curing agent has a function which hardens the epoxy resin containing (A) component. (E) hardening|curing agent here is a component which does not correspond to (B) component.

(E) The curing agent is not particularly limited, but for example, a phenol-based curing agent, a naphthol-based curing agent, an acid anhydride-based curing agent, an amine-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, A bodyimide-type hardening|curing agent etc. are mentioned. (E) A hardening|curing agent may be used individually by 1 type, and may be used in combination of 2 or more type.

As the phenol-based curing agent and the naphthol-based curing agent, from the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable. Further, from the viewpoint of adhesion to an adherend, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. Among them, a triazine skeleton-containing phenol novolak resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance and adhesiveness. As a specific example of a phenolic hardening|curing agent and a naphthol type hardening|curing agent, For example, "MEH-7700", "MEH-7810", "MEH-7851" by Meiwa Kasei Corporation, "NHN" by Nippon Kayaku Corporation, "CBN" ”, “GPH”, “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485”, “SN-495” manufactured by Nittetsu Chemical & Materials Co., Ltd. "SN-375", "SN-395", "LA-7052" manufactured by DIC, "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090" ', "TD-2090-60M", etc. are mentioned.

Examples of the acid anhydride curing agent include curing agents having one or more acid anhydride groups in one molecule, and curing agents having two or more acid anhydride groups in one molecule are preferable. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride , dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trimellitic anhydride, pyromelli anhydride Tonic acid, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3, 3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis (anhydrotrimellitate) and polymer type acid anhydrides, such as styrene maleic acid resin which copolymerized styrene and maleic acid, etc. are mentioned. As a commercial item of an acid anhydride type hardening|curing agent, "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" by Shin-Nippon Rika Corporation, "YH-306" by Mitsubishi Chemical Corporation , "YH-307", "HN-2200" by Hitachi Kasei Corporation, "HN-5500", etc. are mentioned.

Examples of the amine-based curing agent include curing agents having one or more, preferably two or more amino groups in one molecule, for example, aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, and the like. Among them, aromatic amines are preferable from the viewpoint of exhibiting the desired effect of the present invention. Primary amine or secondary amine is preferable and, as for an amine type hardening|curing agent, primary amine is more preferable. Specific examples of the amine curing agent include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'- Diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobi Phenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3 -Dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane , 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis( 4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. are mentioned. A commercial item may be used for an amine-type hardening|curing agent, For example, "SEIKACURE-S" by Seika Corporation, "KAYABOND C-200S" by Nippon Kayaku Corporation, "KAYABOND C-100", "Kayahard AA", "Kaya Hard AB", "Kayahard AS", "Epicure W" by Mitsubishi Chemical, etc. are mentioned.

Although there is no restriction|limiting in particular as an active ester type hardening|curing agent, Generally, ester groups with high reaction activity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compound esters, are 2 in 1 molecule. Compounds having at least one compound are preferably used. It is preferable that the said active ester type hardening|curing agent is obtained by the condensation reaction of 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, 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, etc. are mentioned. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol to one molecule of dicyclopentadiene.

Specifically, an active ester-based curing agent containing a dicyclopentadiene-type diphenol structure, an active ester-based curing agent containing a naphthalene structure, an active ester-based curing agent containing an acetylated product of phenol novolac, and a benzoyl product of phenol novolac An active ester-based curing agent containing The "dicyclopentadiene type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Commercially available products of the active ester-based curing agent include “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000”, “HPC-8000H”, “ HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM" (manufactured by DIC); As an active ester curing agent containing a naphthalene structure, "EXB-9416-70BK", "EXB-8150-65T", "EXB-8100L-65T", "EXB-8150L-65T", "EXB-8150-62T" ( manufactured by DIC); As an active ester curing agent which is an acetylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical); Examples of the active ester curing agent that is a benzoyl product of phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation).

As a specific example of a benzoxazine type hardening|curing agent, "JBZ-OP100D" by JFE Chemicals, "ODA-BOZ"; "HFB2006M" by Showa Kobunshi Corporation; "P-d", "F-a" manufactured by Shikoku Kaseiko Co., Ltd., etc. are mentioned.

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'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4- Cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cya Bifunctional cyanate resins such as natephenyl)thioether and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolac and cresol novolac, etc., and prepolymers in which these cyanate resins are partially triazined and the like. As a specific example of a cyanate ester type hardening|curing agent, "PT30" and "PT60" (all are phenol novolak-type polyfunctional cyanate ester resin), "BA230", "BA230S75" (a part of bisphenol A dicyanate by Ronza Japan) Or the prepolymer which all was triazine-ized and became a trimer) etc. are mentioned.

As a specific example of a carbodiimide-type hardening|curing agent, "V-03", "V-07" by a Nisshinbo Chemical company, etc. are mentioned.

When the resin composition contains the (E) curing agent, the ratio of the epoxy resin to the (B) component and the (E) curing agent is [the number of epoxy groups in the epoxy resin]: [the number of hydroxyl groups in the component (B) and the (E) curing agent of the total number of reactors], 1:0.2 to 1:2 are preferable, 1:0.3 to 1:1.5 are more preferable, and 1:0.4 to 1:1.4 are still more preferable. Here, (E) the reactive group of the curing agent is, for example, an aromatic hydroxyl group in the case of a phenol-based curing agent and a naphthol curing agent, and an active ester group in the case of an active ester-based curing agent, depending on the type of the curing agent.

(E) The reactive weight of the curing agent is preferably 50 g/eq. to 3,000 g/eq., more preferably 100 g/eq. to 1,000 g/eq., more preferably 100 g/eq. to 500 g/eq., particularly preferably 100 g/eq. to 300 g/eq. The reactor equivalent is the mass of the curing agent per equivalent of the reactor.

Although content of (E) hardening|curing agent in a resin composition is not specifically limited, When making non-volatile components other than (C) inorganic filler in a resin composition 100 mass %, Preferably it is 50 mass % or less, More preferably 30 mass % or less, More preferably, it is 20 mass % or less, Especially preferably, it is 10 mass % or less. Although the lower limit of content of (E) hardening|curing agent in a resin composition is not specifically limited, When making non-volatile components other than (C) inorganic filler in a resin composition 100 mass %, For example, 0 mass % or more, 0.01 They are mass % or more, 0.1 mass % or more, 1 mass % or more, 3 mass % or more, and 5 mass % or more.

<(F) curing accelerator>

The resin composition of this invention may contain (F) hardening accelerator as an arbitrary component. (F) A hardening accelerator has a function which accelerates|stimulates hardening of the epoxy resin containing (A) component.

(F) Examples of the curing accelerator include, but are not particularly limited to, phosphorus curing accelerators, urea curing accelerators, amine curing accelerators, imidazole curing accelerators, guanidine curing accelerators, metal curing accelerators, and the like. . Especially, a phosphorus type hardening accelerator, an amine type hardening accelerator, an imidazole type hardening accelerator, and a metal type hardening accelerator are preferable, and an imidazole type hardening accelerator is especially preferable. (F) A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the phosphorus-based curing accelerator include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphoniumdecanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyro aliphatic phosphonium salts such as melitate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium cresol novolac trimer salt, and di-tert-butylmethylphosphonium tetraphenylborate; Methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra- p-tolyl borate, tetraphenylphosphonium tetraphenyl borate, tetraphenylphosphonium tetrap-tolyl borate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphoniumtetraphenylborate, tris(2-methyl aromatic phosphonium salts such as oxyphenyl)ethylphosphoniumtetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; aromatic phosphine-quinone addition products such as triphenylphosphine/p-benzoquinone addition products; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl-2-butenyl) phosphine, aliphatic phosphines such as tricyclohexylphosphine; Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolyl Phosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, Tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2, 6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine , tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl- 2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2- Aromatic phosphines, such as bis (diphenyl phosphino) acetylene and 2,2'- bis (diphenyl phosphino) diphenyl ether, etc. are mentioned.

Examples of the urea-based curing accelerator include 1,1-dimethyl urea; aliphatic dimethylureas such as 1,1,3-trimethyl urea, 3-ethyl-1,1-dimethyl urea, 3-cyclohexyl-1,1-dimethyl urea, 3-cyclooctyl-1,1-dimethyl urea; 3-phenyl-1,1-dimethyl urea, 3-(4-chlorophenyl)-1,1-dimethyl urea, 3-(3,4-dichlorophenyl)-1,1-dimethyl urea, 3-(3- Chloro-4-methylphenyl)-1,1-dimethyl urea, 3-(2-methylphenyl)-1,1-dimethyl urea, 3-(4-methylphenyl)-1,1-dimethyl urea, 3-(3,4 -Dimethylphenyl)-1,1-dimethyl urea, 3-(4-isopropylphenyl)-1,1-dimethyl urea, 3-(4-methoxyphenyl)-1,1-dimethyl urea, 3-(4 -Nitrophenyl)-1,1-dimethyl urea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethyl urea, 3-[4-(4-chlorophenoxy)phenyl]- 1,1-dimethyl urea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethyl urea, N,N-(1,4-phenylene)bis(N',N'-dimethyl urea ), an aromatic dimethyl urea such as N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea], and the like.

Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene etc. are mentioned, 4-dimethylaminopyridine is preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 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-phenylimida Zolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-unde Silimidazolyl-(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-triazineisocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1, 2-a] imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline, imidazole compounds and epoxy resins and an adduct body with

As an imidazole-type hardening accelerator, you may use a commercial item, for example, "P200-H50" by Mitsubishi Chemical, etc. are mentioned.

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

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

Although content of (F) hardening accelerator in a resin composition is not specifically limited, When making non-volatile components other than (C) inorganic filler in a resin composition 100 mass %, Preferably it is 5 mass % or less, More preferably is 2 mass% or less, more preferably 1 mass% or less, still more preferably 0.5 mass% or less, particularly preferably 0.2 mass% or less. Although the lower limit of content of (F) hardening accelerator in a resin composition is not specifically limited, When making non-volatile components other than (C) inorganic filler in a resin composition 100 mass %, For example, 0 mass % or more, It can be set as 0.0001 mass % or more, 0.001 mass % or more, 0.01 mass % or more, 0.05 mass % or more, 0.1 mass % or more.

<(G) radically polymerizable compound>

The resin composition of this invention may further contain (G) a radically polymerizable compound as an arbitrary component. (G) A radically polymerizable compound may be used individually by 1 type, and may be used in combination of 2 or more types arbitrarily.

(G) A radically polymerizable compound may be a compound which has a radically polymerizable unsaturated group, for example. The radically polymerizable unsaturated group is not particularly limited as long as it can be radically polymerized, but may be an ethylenically unsaturated group having a carbon-carbon double bond at the terminal or inside. Specifically, unsaturated groups such as allyl group and 3-cyclohexenyl group aliphatic group; unsaturated aliphatic group-containing aromatic groups such as p-vinylphenyl group, m-vinylphenyl group, and styryl group; α,β-unsaturated carbonyl groups such as acryloyl group, methacryloyl group, maleoyl group, and fumaroyl group. (G) It is preferable to have one or more radically polymerizable unsaturated groups, and, as for a radically polymerizable compound, it is more preferable to have two or more.

As a compound which has a radically polymerizable unsaturated group, For example, the maleimide-type radically polymerizable compound which has a maleimide group; a vinylphenyl radical polymerizable compound having a vinylphenyl group such as a p-vinylphenyl group and an m-vinylphenyl group; (meth)acrylic radically polymerizable compound having an acryloyl group and/or a methacryloyl group (hereinafter, collectively referred to as “(meth)acryloyl group”); an allyl radical polymerizable compound having an allyl group; and a polybutadiene radical polymerizable compound having a polybutadiene skeleton, and more preferably any one of a maleimide radical polymerizable compound and a vinylphenyl radical polymerizable compound.

A maleimide-type radically polymerizable compound is a compound which has a maleimide group in a molecule|numerator. The number of maleimide groups per molecule of the maleimide radical polymerizable compound is preferably two or more.

In the first embodiment, the maleimide radical polymerizable compound is preferably a polymaleimide compound having a repeating unit, more preferably an aromatic polymaleimide compound having a repeating unit, particularly preferably , the formula (3):

[Formula (3)]

[Wherein, X ¹ and X ² are each independently a single bond, an alkylene group having 1 to 6 carbon atoms, -O-, -CO-, -S-, -SO-, or -SO ₂ - (preferably represents an alkylene group having 1 to 6 carbon atoms, more preferably -CH ₂ -), and Ar is an arylene group having 6 to 14 carbon atoms which may have an alkyl group having 1 to 6 carbon atoms (preferably a 4,4'-biphenyl group) ), n1 each independently represents 0 or 1, n2 represents an integer of 1 to 100 (preferably 1 to 50, more preferably 1 to 20, still more preferably 1 to 5)] It is an aromatic polymaleimide compound represented by .

The arylene group means a divalent aromatic hydrocarbon group, and even if a plurality of aromatic rings are condensed, they may be directly connected. Examples of the arylene group include 1,3-phenylene group, 1,4-phenylene group, 1,5-naphthylene group, 1,8-naphthylene group, 2,6-naphthylene group, 4,4' -biphenyl group, 3,4'-biphenyl group, etc. are mentioned.

In the second embodiment, the maleimide radical polymerizable compound is preferably imidized with a polyamine compound (particularly a diamine compound), maleic anhydride, and optionally polycarboxylic acid anhydride (particularly tetracarboxylic dianhydride) It is a bismaleimide compound obtained by reacting, and particularly preferably, the following formula (4):

[Formula (4)]

[wherein, Y ¹ and Y ³ _{each independently represent a divalent group obtained by removing two —NH 2 s} from a diamine compound, for example, at least two selected from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom. It may be a divalent organic group consisting of (eg, 2 to 3,000, 2 to 1,000, 2 to 100, 2 to 50) skeletal atoms. Y ² represents a tetravalent group obtained by removing two -CO-O-CO- from tetracarboxylic dianhydride, for example, two or more selected from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom (for example, 2 to 3,000, 2 to 1,000, 2 to 100, 2 to 50) of skeletal atoms) may be a tetravalent organic group. m represents 0 or an integer of 1 or more].

Although it does not specifically limit as a diamine compound for preparing a maleimide-type radically polymerizable compound, For example, an aliphatic diamine compound and an aromatic diamine compound are mentioned.

Examples of the aliphatic diamine compound include 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1, straight-chain aliphatic diamine compounds such as 6-diaminohexane and 1,10-diaminodecane; branched aliphatic diamine compounds such as 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butane and 2-methyl-1,5-diaminopentane; 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis( alicyclic diamine compounds such as cyclohexylamine); Dimer acid type diamine etc. are mentioned.

The dimer acid-type diamine means a diamine compound obtained by substituting two terminal carboxyl groups (-COOH) of a dimer acid with an aminomethyl group (-CH ₂ -NH ₂ ) or an amino group (-NH _{2 ).} A dimer acid is a known compound obtained by dimerizing an unsaturated fatty acid (preferably having 11 to 22 carbon atoms, particularly preferably having 18 carbon atoms), and its industrial production process is almost standardized in the industry. The dimer acid can easily obtain what has a C36 dimer acid as a main component obtained by dimerizing C18 unsaturated fatty acids, such as oleic acid and linoleic acid which are cheap and easy to obtain especially. In addition, the dimer acid may contain arbitrary amounts of a monomeric acid, a trimer acid, other polymeric fatty acid, etc. depending on a manufacturing method, the grade of refinement|purification, etc. In addition, although a double bond remains after the polymerization reaction of an unsaturated fatty acid, in this specification, the hydrogenated substance which further reduced the degree of unsaturation by hydrogenation reaction shall also be included in dimer acid. As for dimer acid type diamine, a commercial item can be obtained, For example, "PRIAMINE1073", "PRIAMINE1074", "PRIAMINE1075" by Croda Japan, "Vasamine 551" by Cognis Japan, "vasamine 552" etc. can be heard

Examples of the aromatic diamine compound include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3 phenylenediamine compounds such as ,5-diaminobiphenyl and 2,4,5,6-tetrafluoro-1,3-phenylenediamine; naphthalenediamine compounds such as 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, and 2,3-diaminonaphthalene; 4,4'-diamino-2,2'-ditrifluoromethyl-1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3 ,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4-aminophenyl4-aminobenzoate, 1,3-bis(3- Aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 4,4 '-hexafluoroisopropylidene) dianiline, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoro lopropane, α,α-bis[4-(4-aminophenoxy)phenyl]-1,3-diisopropylbenzene, α,α-bis[4-(4-aminophenoxy)phenyl]-1, 4-Diisopropylbenzene, 4,4'-9-fluorenylidene)dianiline, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-methyl-4 -Aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl-1,1'-biphenyl, 4,4'-diamino-2,2'-dimethyl-1,1'-bi Phenyl, 9,9'-bis(3-methyl-4-aminophenyl)fluorene, 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1, Dianiline compounds, such as 3-trimethylindane and 4-aminobenzoic acid 5-amino-1,1'- biphenyl-2-yl, etc. are mentioned.

A commercially available thing may be used for a diamine compound, and what was synthesize|combined by a well-known method may be used for it. A diamine compound may be used individually by 1 type, and may be used in combination of 2 or more type.

Although it does not specifically limit as tetracarboxylic acid anhydride for preparing a maleimide-type radically polymerizable compound, For example, aliphatic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride are mentioned.

Specifically as aliphatic tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane -1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-di Carboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl- 4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride etc. are mentioned.

As aromatic tetracarboxylic dianhydride, For example, benzenetetracarboxylic dianhydride, such as pyromellitic dianhydride and a 1,2,3,4- benzenetetracarboxylic dianhydride; naphthalenetetracarboxylic dianhydride such as 1,4,5,8-naphthalenetetracarboxylic dianhydride and 2,3,6,7-naphthalenetetracarboxylic dianhydride; anthracene tetracarboxylic dianhydride such as 2,3,6,7-anthracenetetracarboxylic dianhydride; 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetra Carboxylic acid dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-di Phenylsulfonetetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, methylene-4,4'-diphthalic acid dianhydride, 1,1-ethynylidene-4, 4'-diphthalic dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4, 4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 1,3-bis(3, 4-dicarboxyphenyl)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4 -bis(3,4-dicarboxyphenoxy)benzene dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane 2 Diphthalic acid dianhydride, such as an anhydride and 4,4'- (4,4'- isopropylidene diphenoxy) bisphthalic acid dianhydride, etc. are mentioned.

The maleimide-type radically polymerizable compound may contain both the maleimide-type radically polymerizable compound in 1st Embodiment, and the maleimide-type radically polymerizable compound in 2nd Embodiment.

As a commercial item of a maleimide type radically polymerizable compound, For example, "MIR-3000-70MT" by the Nippon Kayaku company; "BMI-689", "BMI-1500", "BMI-1700", "BMI-3000" by Designer Molecules Corporation, etc. are mentioned.

A vinylphenyl-type radically polymerizable compound is a radically polymerizable compound which has a vinylphenyl group. It is preferable that a vinylphenyl type radically polymerizable compound has two or more vinylphenyl groups per molecule.

The vinylphenyl-based radically polymerizable compound is preferably a vinylbenzyl-modified polyphenylene ether having a vinylbenzyl group and a polyphenylene ether skeleton, and the following formula (5):

[Formula (5)]

[Wherein, R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms (preferably a methyl group), and Z ¹ , Z ² and Z ³ are each independently a single bond, a C 1 to C 6 alkyl group. represents an alkylene group, -O-, -CO-, -S-, -SO-, or -SO ₂ - (Z ¹ and Z ³ are preferably -O-, Z ² is preferably a single bond), a1 and a2 each independently represent an integer of 1 to 300 (preferably 1 to 100, more preferably 1 to 50), and b1 and b2 each independently represent an integer of 0 to 4] It is especially preferable that it is resin used.

As a commercial item of a vinylphenyl type radically polymerizable compound, "OPE-2St" (vinylbenzyl-modified polyphenylene ether) manufactured by Mitsubishi Gas Chemical Co., Ltd. etc. is mentioned, for example.

A (meth)acrylic-type radically polymerizable compound is a compound which has a (meth)acryloyl group. As a (meth)acrylic-type radically polymerizable compound, what has 2 or more (meth)acryloyl groups per molecule is preferable. A (meth)acrylic radically polymerizable compound may use a commercial item, for example, "A-DOG" by Shin-Nakamura Chemical Co., Ltd., "DCP-A" by Kyoeisha Chemical Company, Nippon Kayaku Co., Ltd. “NPDGA”, “FM-400”, “R-687”, “THE-330”, “PET-30”, “DPHA”, and “NK Ester DCP” manufactured by Shin-Nakamura Kagakuko Co., Ltd. have.

The allyl radical polymerizable compound having an allyl group is a compound having an allyl group in the molecule. It is preferable that an allyl-type radically polymerizable compound has two or more allyl groups. A commercial item can be used for an allyl-type radically polymerizable compound. As a commercial item, For example, the Meiwa Kasei company make "MEH-8000H", "MEH-8005" (Allyl-type radically polymerizable compound which has a phenol structure); "RE-810NM" manufactured by Nippon Kayaku (allyl radical polymerizable compound having an epoxy group); "ALP-d" manufactured by Shikoku Chemical Co., Ltd. (allyl radical polymerizable compound having a benzoxazine ring); "L-DAIC" manufactured by Shikoku Chemical Co., Ltd. (allyl radical polymerizable compound having an isocyanuric ring); "TAIC" by Nippon Kasei Co., Ltd. (allyl-type radically polymerizable compound which has an isocyanuric ring); "MDAC" by Osaka Soda (allyl radical polymerizable compound having a cyclohexanedicarboxylic acid derivative); "DAD" manufactured by Nisshoku Techno Fine Chemicals (diphenate diallyl); Osaka Soda Co., Ltd. "Daisodap Monomer" (ortho diallyl phthalate) etc. are mentioned.

The polybutadiene-based radically polymerizable compound is a compound having a polybutadiene skeleton. In addition, a part of polybutadiene skeleton may be hydrogenated. Examples of the polybutadiene radical polymerizable compound include hydroxyl group-containing butadiene resin, phenolic hydroxyl group-containing butadiene resin, carboxyl group-containing butadiene resin, acid anhydride group-containing butadiene resin, epoxy group-containing butadiene resin, isocyanate group-containing butadiene resin and urethane group-containing At least one resin selected from the group consisting of butadiene resins is more preferable. As a specific example of a polybutadiene radical polymerizable compound, "JP-100" by Nippon Soda Corporation, "Ricon100" by CRAY VALLEY, "Ricon150", "Ricon130MA8", "Ricon130MA13", "Ricon130MA20", "Ricon131MA5" , "Ricon131MA10", "Ricon131MA17", "Ricon131MA20", "Ricon 184MA6", etc. are mentioned.

Although content of (G) radically polymerizable compound in a resin composition is not specifically limited, When making non-volatile components other than (C) inorganic filler in a resin composition 100 mass %, Preferably it is 50 mass % or less, More Preferably it is 40 mass % or less, More preferably, it is 30 mass % or less, More preferably, it is 20 mass % or less, Especially preferably, it is 10 mass % or less. Although the minimum of content of (G) radically polymerizable compound in a resin composition is not specifically limited, When making non-volatile components other than (C) inorganic filler in a resin composition 100 mass %, for example, 0 mass % or more, 0.001 mass % or more, 0.01 mass % or more, 0.1 mass % or more, 0.5 mass % or more, 1 mass % or more, etc. can be set as.

<(H) radical polymerization initiator>

The resin composition of the present invention may further contain (H) a radical polymerization initiator as an optional component. (H) The radical polymerization initiator may be, for example, a thermal polymerization initiator that generates free radicals upon heating. (H) A radical polymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more types arbitrarily.

(H) As a radical polymerization initiator, a peroxide type radical polymerization initiator, an azo radical polymerization initiator, etc. are mentioned, for example. Especially, a peroxide type radical polymerization initiator is preferable.

As a peroxide radical polymerization initiator, For example, Hydroperoxide compounds, such as 1,1,3,3-tetramethylbutyl hydroperoxide; tert-butylcumyl peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, dicumyl peroxide, 1,4-bis(1-tert-butylperoxy-1-methylethyl)benzene, 2, dialkyl peroxide compounds such as 5-dimethyl-2,5-bis(tert-butylperoxy)hexane; diacyl peroxide compounds such as dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl peroxydicarbonate, and bis(4-tert-butylcyclohexyl)peroxydicarbonate; tert-butylperoxyacetate, tert-butylperoxybenzoate, tert-butylperoxyisopropylmonocarbonate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyneodecanoate, tert- Hexyl peroxyisopropyl monocarbonate, tert-butyl peroxy laurate, (1,1-dimethylpropyl) 2-ethyl perhexanoate, tert-butyl 2-ethyl perhexanoate, tert-butyl 3,5, Peroxyester compounds, such as 5-trimethyl perhexanoate, tert- butyl peroxy 2-ethylhexyl monocarbonate, and tert- butyl peroxy maleic acid, etc. are mentioned.

As the azo radical polymerization initiator, for example, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile) ), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 1-[ azonitrile compounds such as (1-cyano-1-methylethyl)azo]formamide and 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile; 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], 2,2'-azobis[2-methyl-N- [1,1-bis(hydroxymethyl)ethyl]propionamide], 2,2'-azobis[2-methyl-N-[2-(1-hydroxybutyl)]-propionamide], 2,2 '-Azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2'-azobis(2-methylpropionamide)dihydrate, 2,2'-azobis[N- (2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide) azoamide compounds such as amide); and alkylazo compounds such as 2,2'-azobis(2,4,4-trimethylpentane) and 2,2'-azobis(2-methylpropane).

(H) As a commercial item of a radical polymerization initiator, "perbutyl C", "perbutyl A", "perbutyl P", "perbutyl L", "perbutyl O", "per Butyl ND”, “Perbutyl Z”, “Perbutyl I”, “Percumyl P”, “Percumyl D”, “Perhexyl D”, “Perhexyl A”, “Perhexyl I”, “Perhexyl Z” ', "perhexyl ND", "perhexyl O", "perhexyl PV", "perhexyl O", etc. are mentioned.

Although content of (H) radical polymerization initiator in a resin composition is not specifically limited, When making non-volatile components other than (C) inorganic filler in a resin composition 100 mass %, Preferably it is 5 mass % or less, More preferably Preferably it is 1 mass % or less, More preferably, it is 0.5 mass % or less, More preferably, it is 0.3 mass % or less, Especially preferably, it is 0.2 mass % or less. Although the minimum of content of (H) radical polymerization initiator in a resin composition is not specifically limited, When making non-volatile components other than (C) inorganic filler in a resin composition 100 mass %, For example, 0 mass % or more , 0.001 mass % or more, 0.01 mass % or more, 0.05 mass % or more, 0.1 mass % or more, and the like.

<(I) Other additives>

The resin composition of this invention may further contain arbitrary additives as a nonvolatile component. As such an additive, for example, bisphenol A epoxy resin, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, phenol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy Epoxy resins other than (A) component, such as resin; thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentone and montmorillonite; Antifoaming agent of silicone type antifoaming agent, acrylic type antifoaming agent, fluorine type antifoaming agent, and vinyl resin type antifoaming agent; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion-imparting agents such as triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, and triazine-based adhesion-imparting agents; antioxidants such as hindered phenol antioxidants and hindered amine antioxidants; optical brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; Flame retardants such as phosphorus-based flame retardants (for example, phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red), nitrogen-based flame retardants (for example, melamine sulfate), halogen-based flame retardants, inorganic flame retardants (for example, antimony trioxide) can be heard An additive may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios. (I) Content of other additives can be suitably set if it is a person skilled in the art.

<(J) organic solvent>

The resin composition of this invention may further contain arbitrary organic solvents as a volatile component other than said nonvolatile component. (J) As an organic solvent, a well-known thing can be used suitably, The kind is not specifically limited. (J) As an organic solvent, For example, Ketone solvents, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene and trimethylbenzene. (J) The organic solvent may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

In one embodiment, (J) organic solvent, when all components in the resin composition are 100 mass %, for example, 60 mass % or less, 40 mass % or less, 20 mass % or less, 15 mass % or less, 10 mass % or less may be sufficient.

<Method for producing resin composition>

The resin composition of the present invention is, for example, in an arbitrary reaction vessel, (A) a condensed ring structure-containing epoxy resin, (B) an alkoxy group-containing naphthol aralkyl resin, (C) an inorganic filler, and optionally (D) organic a filler, optionally (E) a curing agent, optionally (F) a curing accelerator, optionally (G) a radically polymerizable compound, optionally (H) a radical polymerization initiator, optionally (I) other additives, and If necessary, it can manufacture by adding (J) organic solvent in arbitrary order and/or adding and mixing partly or all simultaneously. In addition, in the process of adding and mixing each component, the temperature can be set suitably, and you may heat and/or cool over temporarily or continuously. In addition, in the process of adding and mixing each component, you may perform stirring or shaking. In addition, when adding and mixing, you may stir and disperse|distribute a resin composition uniformly using stirring apparatuses, such as a mixer, for example, after or after.

<Characteristics of the resin composition>

The resin composition of this invention contains (A) condensed ring structure containing epoxy resin, (B) alkoxy group containing naphthol aralkyl resin, and (C) inorganic filler, Content of (C)component is non-volatile in a resin composition When a component is 100 mass %, since it is 70 mass % or more, the curvature at the time of hardening can be suppressed and the hardened|cured material which has the outstanding adhesive strength can be obtained. Moreover, in one Embodiment, the hardened|cured material of the resin composition of this invention can have the outstanding electrical property.

In one embodiment, since the resin composition of the present invention can suppress warpage during curing, for example, as in Test Example 1 below, in accordance with JEITA EDX-7311-24, which is a standard of the Electronic Information Technology Industry Association, warpage When measured, the amount of deflection may be preferably less than 10 mm, more preferably less than 5 mm, still more preferably less than 3 mm, particularly preferably less than 2 mm.

In one embodiment, since the resin composition of the present invention can obtain a cured product having excellent adhesion strength, for example, as in Test Example 2 below, peel strength (adhesion) by a stud pull peel strength test. strength), the peel strength (adhesion strength) is preferably 100 kgf/cm 3 or more, more preferably 200 kgf/cm 3 or more, still more preferably 230 kgf/cm 3 or more, particularly preferably 250 kgf/cm 3 or more. can be

In one embodiment, since the cured product of the resin composition of the present invention can also have excellent electrical properties, the dielectric loss tangent of the cured product of the resin composition when measured at 5.8 GHz and 23° C. as in Test Example 3 below is preferably Preferably, it may be 0.030 or less, 0.020 or less, more preferably 0.015 or less, 0.012 or less, still more preferably 0.010 or less, 0.009 or less, particularly preferably 0.008 or less, 0.007 or less.

<Use of the resin composition>

The resin composition of this invention can be used suitably as a resin composition for insulating uses, especially a resin composition for forming an insulating layer. Specifically, it can be suitably used as a resin composition (resin composition for forming an insulating layer for forming a conductor layer) for forming the insulating layer for forming a conductor layer (including a rewiring layer) formed on the insulating layer. have. Moreover, the printed wiring board mentioned later WHEREIN: It can use suitably as a resin composition for forming the insulating layer of a printed wiring board (resin composition for insulating layer formation of a printed wiring board). The resin composition of the present invention can also be widely used in applications requiring a resin composition, such as a resin sheet, a sheet-like laminated material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, a component embedding resin, etc. can

For example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention is a resin composition for a redistribution forming layer as an insulating layer for forming a redistribution layer (cultivation). It can be used suitably also as resin composition for line forming layer formation) and the resin composition for sealing a semiconductor chip (resin composition for semiconductor chip sealing). When the semiconductor chip package is manufactured, a redistribution layer may be additionally formed on the sealing layer.

(1) the step of laminating a temporarily fixed film on the substrate,

(2) the step of temporarily fixing the semiconductor chip on the temporarily fixing film,

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

(4) the step of peeling the substrate and the temporarily fixed film from the semiconductor chip,

(5) a step of forming a rewiring forming layer as an insulating layer on the surface where the substrate and the temporarily fixed film of the semiconductor chip are peeled; and

(6) Step of forming a redistribution layer as a conductor layer on the redistribution forming layer

Moreover, since the resin composition of this invention forms an insulating layer with good component embedding property, when a printed wiring board is a component built-in circuit board, it can be used suitably.

<Sheet-like laminated material>

Although the resin composition of the present invention may be applied and used in a varnish state, it is generally suitable for use in the form of a sheet-like laminated material containing the resin composition industrially.

As a sheet-like laminated material, the resin sheet and prepreg shown below are preferable.

In one embodiment, the resin sheet comprises a support body and a resin composition layer provided on the support body, and the resin composition layer is formed of the resin composition of the present invention.

The thickness of the resin composition layer is preferably 50 µm or less, more preferably 40 µm or less, from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product excellent in insulation even if the cured product of the resin composition is a thin film. . Although the lower limit of the thickness of a resin composition layer is not specifically limited, Usually, it can be 5 micrometers or more, 10 micrometers or more, etc.

As a support body, the film which consists of a plastics material, metal foil, and a release paper are mentioned, for example, The film which consists of a plastics material, and metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material is, for example, polyethylene terephthalate (hereinafter, may be abbreviated as "PET"), polyethylene naphthalate (hereinafter abbreviated as "PEN"). Polyester such as ), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide ( PES), polyether ketone, polyimide, etc. are mentioned. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When using metal foil as a support body, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, Copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, or a foil made of an alloy of copper and another metal (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. good.

A support body may give a mat treatment, a corona treatment, and an antistatic treatment to the surface to join with the resin composition layer.

Moreover, as a support body, you may use the support body with a mold release layer which has a mold release layer on the surface to join with the resin composition layer. As a mold release agent used for the mold release layer of a support body with a mold release layer, 1 or more types of mold release agents are mentioned from the group which consists of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin, for example. The support with a release layer may use a commercial item, for example, "SK-1", "AL-5", "AL-" manufactured by Lintec which is a PET film which has a release layer which has an alkyd resin type mold release agent as a main component. 7", "Lumira T60" by Tore Corporation, "Purex" by Teijin Corporation, "Uni-pil" by Unichika Corporation, etc. are mentioned.

Although the thickness of a support body is not specifically limited, The range of 5 micrometers - 75 micrometers is preferable, and the range of 10 micrometers - 60 micrometers is more preferable. Moreover, when using a support body with a mold release layer, it is preferable that the thickness of the whole support body with a mold release layer is the said range.

In one embodiment, the resin sheet may further contain arbitrary layers as needed. As such an arbitrary layer, the protective film according to the support body etc. which were provided on the surface (that is, the surface on the opposite side to the support body) which are not joined to the support body of a resin composition layer, for example are mentioned, for example. Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer - 40 micrometers. By laminating|stacking a protective film, adhesion of dust, etc. to the surface of a resin composition layer, and a flaw can be suppressed.

For the resin sheet, for example, a liquid resin composition as it is or a resin varnish obtained by dissolving the resin composition in an organic solvent is prepared, this is applied on a support using a die coater or the like, and further dried to form a resin composition layer It can be manufactured by

As an organic solvent, the thing similar to the organic solvent demonstrated as a component of a resin composition is mentioned. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

You may perform drying by well-known methods, such as a heating and hot-air spraying. Although drying conditions are not specifically limited, Content of the organic solvent in a resin composition layer is 10 mass % or less, Preferably it is made to dry so that it may become 5 mass % or less. Depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when using a resin composition or resin varnish containing 30% by mass to 60% by mass of an organic solvent, 50°C to 150°C for 3 minutes By drying for 10 minutes, a resin composition layer can be formed.

The resin sheet can be wound and stored in a roll shape. When a resin sheet has a protective film, it becomes usable by peeling off a protective film.

In one Embodiment, a prepreg makes a sheet-like fiber base material impregnate the resin composition of this invention, and is formed.

The sheet-like fiber base material used for a prepreg is not specifically limited, What is commonly used as a base material for prepregs, such as glass cloth, an aramid nonwoven fabric, and a liquid crystal polymer nonwoven fabric, can be used. From a viewpoint of thickness reduction of a printed wiring board, the thickness of a sheet-like fiber base material becomes like this. Preferably it is 50 micrometers or less, More preferably, it is 40 micrometers or less, More preferably, it is 30 micrometers or less, Especially preferably, it is 20 micrometers or less. The lower limit of the thickness of a sheet-like fiber base material is not specifically limited. Usually, it is 10 micrometers or more.

A prepreg can be manufactured by well-known methods, such as a hot melt method and a solvent method.

The thickness of a prepreg can be made into the range similar to the resin composition layer in the said resin sheet.

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

<Printed wiring board>

The printed wiring board of this invention contains the insulating layer which consists of hardened|cured material obtained by hardening|curing the resin composition of this invention.

A printed wiring board can be manufactured by the method including the process of following (I) and (II) using the said resin sheet, for example.

(I) Step of laminating a resin sheet on the inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate

(II) Step of curing (eg, thermosetting) the resin composition layer to form an insulating layer

The "inner-layer substrate" used in step (I) is a member used as a substrate for a printed wiring board, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene. An ether substrate etc. are mentioned. Moreover, the said board|substrate may have a conductor layer on one side or both surfaces thereof, and this conductor layer may be pattern-processed. An inner-layer substrate in which a conductor layer (circuit) is formed on one or both surfaces of the substrate is sometimes referred to as an "inner-layer circuit board". Moreover, when manufacturing a printed wiring board, the intermediate product in which an insulating layer and/or a conductor layer should be further formed is also included in the "inner-layer board|substrate" referred to in this invention. When a printed wiring board is a component-embedded circuit board, you may use the inner-layer board which incorporated components.

Lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. As a member (hereinafter also referred to as "thermal compression member") for heat-bonding the resin sheet to the inner layer substrate, a heated metal plate (such as a SUS head plate) or a metal roll (such as a SUS roll) is exemplified. In addition, it is preferable not to press the thermocompression-bonding member directly to the resin sheet, but to press through an elastic material, such as a heat-resistant rubber, so that the resin sheet may fully follow the surface unevenness|corrugation of an inner-layer board|substrate.

You may perform lamination|stacking of an inner-layer board|substrate and a resin sheet by the vacuum lamination method. In the vacuum lamination method, the thermocompression compression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, and the thermocompression compression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably is in the range of 0.29 MPa to 1.47 MPa, and the heat compression time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. The lamination may be preferably carried out under reduced pressure conditions of a pressure of 26.7 hPa or less.

Lamination can be performed with a commercially available vacuum laminator. As a commercially available vacuum laminator, the vacuum pressure laminator by the Meiki Sesakusho company, the vacuum applicator by the Nikko Materials company, a batch type vacuum pressure laminator etc. are mentioned, for example.

After lamination, the laminated resin sheet may be smoothed under normal pressure (under atmospheric pressure), for example, by pressing the thermocompression-bonding member from the support side. The press conditions of the smoothing process can be made into the same conditions as the thermocompression-bonding conditions of the said lamination|stacking. A smoothing process can be performed with a commercially available laminator. In addition, you may perform lamination|stacking and a smoothing process continuously using the said commercially available vacuum laminator.

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

Step (II) WHEREIN: The resin composition layer is hardened (for example, thermosetting), and the insulating layer which consists of a hardened|cured material of a resin composition is formed. The curing conditions of the resin composition layer are not particularly limited, and when forming the insulating layer of a printed wiring board, you may use the conditions normally employ|adopted.

For example, although the thermosetting conditions of the resin composition layer also vary depending on the kind of resin composition, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, still more preferably 170°C. to 210°C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, still more preferably 15 minutes to 100 minutes.

Before thermosetting a resin composition layer, you may preheat a resin composition layer at temperature lower than hardening temperature. For example, prior to thermosetting the resin composition layer, at a temperature of 50 ° C. to 120 ° C., preferably 60 ° C. to 115 ° C., more preferably 70 ° C. to 110 ° C., for 5 minutes or more, Preferably, you may preheat for 5 minutes - 150 minutes, More preferably, it is 15 minutes - 120 minutes, More preferably, it is 15 minutes - 100 minutes.

When manufacturing a printed wiring board, you may further perform the process of (III) the process of drilling in an insulating layer, the process of (IV) roughening an insulating layer, and the process of (V) forming a conductor layer. You may implement these process (III) - process (V) according to various methods well-known to those skilled in the art used for manufacture of a printed wiring board. In addition, when the support is removed after step (II), the removal of the support is performed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). ) may be performed between If necessary, the formation of the insulating layer and the conductor layer in the steps (II) to (V) may be repeated to form a multilayer wiring board.

In another embodiment, the printed wiring board of this invention can be manufactured using the said prepreg. The manufacturing method is basically the same as in the case of using a resin sheet.

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

Process (IV) is a process of roughening an insulating layer. Usually, smear removal is also performed in this process (IV). The procedure and conditions of a roughening process are not specifically limited, When forming the insulating layer of a printed wiring board, the well-known procedure and conditions normally used are employable. For example, the insulating layer can be roughened by performing the swelling process by a swelling liquid, the roughening process by an oxidizing agent, and the neutralization process by a neutralizing liquid in this order.

Although it does not specifically limit as a swelling liquid used for a roughening process, An alkali solution, surfactant solution, etc. are mentioned, Preferably it is an alkali solution, As said alkali solution, sodium hydroxide solution and potassium hydroxide solution are more preferable. As a commercially available swelling liquid, "Swelling Deep Security P", "Swelling Deep Security SBU" by Atotech Japan, etc. are mentioned, for example. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer in a 30 degreeC-90 degreeC swelling liquid for 1 minute - 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes.

Although it does not specifically limit as an oxidizing agent used for a roughening process, For example, the alkaline permanganic acid solution which melt|dissolved potassium permanganate or sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. It is preferable to perform the roughening process by oxidizing agents, such as an alkaline permanganic acid solution, by making the insulating layer immerse for 10 minutes - 30 minutes in the oxidizing agent solution heated to 60 degreeC - 100 degreeC. Moreover, as for the density|concentration of the permanganate in an alkaline permanganic acid solution, 5 mass % - 10 mass % are preferable. As a commercially available oxidizing agent, alkaline permanganic acid solutions, such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" by Atotech Japan, are mentioned, for example.

Moreover, as a neutralization liquid used for a roughening process, acidic aqueous solution is preferable, and as a commercial item, "reduction solution securigant P" by Atotech Japan company is mentioned, for example.

The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in a neutralizing solution at 30°C to 80°C for 5 minutes to 30 minutes. The method of immersing the target object roughened by the oxidizing agent from points, such as workability|operativity, in the neutralization liquid of 40 degreeC - 70 degreeC for 5 minutes - 20 minutes is preferable.

In one embodiment, although the arithmetic mean roughness Ra of the insulating layer surface after a roughening process is not specifically limited, Preferably it is 500 nm or less, More preferably, it is 400 nm or less, More preferably, it is 300 nm or less. It does not specifically limit about a minimum, For example, it can be set as 1 nm or more, 2 nm or more, etc. Moreover, the root mean square roughness (Rq) of the insulating layer surface after a roughening process becomes like this. Preferably it is 500 nm or less, More preferably, it is 400 nm or less, More preferably, it is 300 nm or less. It does not specifically limit about a minimum, For example, it can be set as 1 nm or more, 2 nm or more, etc. The arithmetic mean roughness (Ra) and the root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact type surface roughness meter.

A process (V) is a process of forming a conductor layer, and forms a conductor layer on an insulating layer. The conductor material used for a conductor layer is not specifically limited. In a suitable embodiment, the conductor layer comprises at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. do. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer is, for example, an alloy of two or more metals selected from the group described above (eg, a nickel/chromium alloy, a copper/nickel alloy, and a copper/titanium alloy). ) can be mentioned. Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, a copper-nickel alloy , a copper/titanium alloy alloy layer is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel/chromium alloy is more preferable, and a single metal layer of copper This is more preferable.

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

Although the thickness of a conductor layer depends on the design of a desired printed wiring board, it is 3 micrometers - 35 micrometers generally, Preferably it is 5 micrometers - 30 micrometers.

In one embodiment, the conductor layer may be formed by plating. For example, by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full additive method, a conductor layer having a desired wiring pattern can be formed, and from the viewpoint of simplicity of manufacture, a semi-additive method It is preferable to form by the additive method. Hereinafter, the example in which a conductor layer is formed by the semiadditive method is shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Then, on the formed plating seed layer, a mask pattern for exposing a part of the plating seed layer corresponding to the desired wiring pattern is formed. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

In another embodiment, you may form a conductor layer using metal foil. When forming a conductor layer using metal foil, it is suitable to implement a process (V) between a process (I) and a process (II). For example, after a process (I), a support body is removed and metal foil is laminated|stacked on the surface of the exposed resin composition layer. You may perform lamination|stacking of a resin composition layer and metal foil by the vacuum lamination method. The lamination conditions may be the same as those described for the step (I). Then, step (II) is performed to form an insulating layer. Then, the conductor layer which has a desired wiring pattern can be formed by conventionally well-known techniques, such as a subtractive method and a modified semiadditive method, using the metal foil on an insulating layer.

Metal foil can be manufactured by well-known methods, such as an electrolytic method and a rolling method, for example. As a commercial item of metal foil, HLP foil, JXUT-III foil, 3EC-III foil by the Mitsui Kinzoku Kozan company, TP-III foil etc. are mentioned, for example by JX Nikko Nisseki Kinzoku.

<Semiconductor device>

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

Examples of the semiconductor device include various semiconductor devices provided for electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trams, ships and aircraft). have.

[Example]

Hereinafter, the present invention will be specifically described by way of Examples. The present invention is not limited to these examples. In addition, in the following, "part" and "%" which show quantity means a "mass part" and "mass %", respectively, unless otherwise indicated.

<Example 1>

30 parts of naphthalene type epoxy resin ("HP-4032-SS" manufactured by DIC, 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent about 145 g/eq.), naphthol aralkyl type epoxy resin (Nitetsu Chemical) & Materials, "ESN-475V", epoxy equivalent: about 332 g/eq.) 20 parts, naphthol aralkyl resin (Nitetsu Chemical & Materials, "SN-4110V", partially containing a methoxy group) 20 parts, spherical silica ( "SO-C2" manufactured by Adomatex, average particle diameter of 0.5 µm, specific surface area of 5.8 m 2 /g) 400 parts, core-shell type graft copolymer rubber particles ("EXL-2655" manufactured by Dow Chemical Nippon Corporation) 12 parts, already 0.1 parts of a dazole-type hardening accelerator ("1B2PZ" by Shikoku Chemical Co., Ltd., 1-benzyl-2-phenylimidazole) was disperse|distributed uniformly using the mixer, and the resin composition was prepared.

<Example 2>

The amount of naphthol aralkyl resin (“SN-4110V” manufactured by Nittetsu Chemical & Materials, containing some methoxy groups) was changed from 20 parts to 15 parts, triazine-containing cresol novolac resin (“LA-3018” manufactured by DIC) A resin composition was prepared in the same manner as in Example 1 except that 10 parts of -50P” and a propylene glycol monomethyl ether solution having a solid content of 50% by mass) were further used.

<Example 3>

What changed the usage-amount of spherical silica ("SO-C2" manufactured by Adomatex Co., Ltd., 0.5 μm, average particle diameter, specific surface area 5.8 m 2 /g) from 400 parts to 430 parts, a vinylphenyl radical polymerizable compound (Mitsubishi Gas Kaga) A resin composition was prepared in the same manner as in Example 2, except that 5 parts of "OPE-2St" manufactured by Kusa Corporation and 0.1 parts of a radical polymerization initiator ("Perbutyl C" manufactured by Nichi Industries, Ltd.) were further used.

<Example 4>

What changed the usage-amount of spherical silica ("SO-C2" manufactured by Adomatex Co., Ltd., 0.5 µm, average particle diameter, specific surface area: 5.8 m 2 /g) from 430 parts to 410 parts, a vinylphenyl radical polymerizable compound (Mitsubishi Gas Kaga) A resin composition was prepared in the same manner as in Example 3 except that 2 parts of a maleimide radical polymerizable compound (“BMI-689” manufactured by Designer Molecules) was used instead of 5 parts of "OPE-2St" by Kusa Co., Ltd.).

<Example 5>

In place of 5 parts of a vinylphenyl radical polymerizable compound (“OPE-2St” manufactured by Mitsubishi Gas Chemical Co., Ltd.), a maleimide radical polymerizable compound (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd., MEK/ with a solid content of 70% A resin composition was prepared in the same manner as in Example 3 except that 7.1 parts of toluene mixed solution) was used.

<Example 6>

What changed the amount of spherical silica (“SO-C2” manufactured by Adomatex Co., Ltd. “SO-C2”, average particle diameter 0.5 μm, specific surface area 5.8 m 2 /g) from 400 parts to 430 parts, an active ester curing agent (“EXB-” manufactured by DIC) 8150-62T", an active group equivalent of about 230 g/eq., a resin composition was prepared in the same manner as in Example 2 except that 8.1 parts of a toluene solution having a solid content of 62% by mass) was further used.

<Comparative Example 1>

Instead of 20 parts of naphthol aralkyl resin (“SN-4110V” manufactured by Nittetsu Chemical & Materials, containing a part of methoxy group), naphthol aralkyl resin (“SN-485” manufactured by Nittetsu Chemical & Materials, without methoxy group) A resin composition was prepared in the same manner as in Example 1 except that 20 parts were used.

<Comparative Example 2>

30 parts of naphthalene type epoxy resin ("HP-4032-SS" manufactured by DIC, 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent about 145 g/eq.) and naphthol aralkyl type epoxy resin (Nitetsu Chemical) & Materials Co., Ltd. "ESN-475V", epoxy equivalent about 332 g/eq.) Instead of 20 parts, bisphenol-type epoxy resin ("ZX-1059" manufactured by Nittetsu Chemical & Materials, epoxy equivalent about 165 g/eq.) 50 A resin composition was prepared in the same manner as in Example 1 except that parts were used.

<Production Example 1: Resin sheet having a thickness of the resin composition layer of 165 µm>

As a support body, the polyethylene terephthalate film ("AL5" by Lintec company, 38 micrometers in thickness) which has a mold release layer was prepared. On the release layer of this support body, the resin composition obtained by the Example and the comparative example was apply|coated uniformly so that the thickness of the resin composition layer after drying might be set to 165 micrometers. Then, the resin composition was dried at 80 degreeC - 120 degreeC (average of 100 degreeC) for 10 minutes, and the resin sheet containing a support body and a resin composition layer was obtained.

<Production Example 2: Resin sheet in which the thickness of the resin composition layer is 70 µm>

As a support body, the polyethylene terephthalate film ("AL5" by Lintec company, 38 micrometers in thickness) which has a mold release layer was prepared. On the release layer of this support body, the resin composition obtained by the Example and the comparative example was apply|coated uniformly so that the thickness of the resin composition layer after drying might be set to 70 micrometers. Then, the resin composition was dried at 80 degreeC - 100 degreeC (average 90 degreeC) for 5 minutes, and the resin sheet containing a support body and a resin composition layer was obtained.

<Test Example 1: Measurement and evaluation of warpage>

On a 12-inch silicon wafer, the resin sheet prepared in Production Example 1 was peeled off the protective film from the resin sheet to expose the resin composition layer, and a batch type vacuum pressurized laminator (manufactured by Nikko Materials Co., Ltd., two-stage build-up laminator "CVP700") ) was laminated on one side of the inner layer substrate so that the resin composition layer was in contact with the inner layer substrate. After lamination was pressure-reduced for 30 second and air pressure was adjusted to 13 hPa or less, it performed by crimping|bonding at 100 degreeC and pressure 0.74 MPa for 30 second. Thereafter, hot pressing was performed at 100°C and a pressure of 0.5 MPa for 60 seconds.

Thereafter, the support is peeled, and the wafer on which the resin sheet is laminated is put into an oven at 130° C. and heated for 30 minutes, then transferred to an oven at 200° C. and heated for 90 minutes to thermoset the resin composition layer to form an insulating layer. did.

Using a shadow moire measuring device ("ThermoireAXP" manufactured by Akormetrix), the amount of warpage at 25°C of the sample substrate was measured. The measurement was performed based on JEITA EDX-7311-24 which is a standard of the Electronic Information Technology Industry Association. Specifically, the virtual plane calculated by the least squares method of all data on the substrate surface of the measurement region was used as the reference plane, and the difference between the minimum and maximum values in the vertical direction from the reference plane was calculated as the amount of deflection. Less than 2 mm of curvature was judged as "circle" and 2 mm or more as "x".

<Test Example 2: Evaluation of adhesion strength by stud pull test>

(1) Preparation of the inner layer substrate

Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness of 18 µm, substrate thickness of 0.4 mm, "R1515A" manufactured by Panasonic Corporation) on which an inner-layer circuit was formed were coated with a micro-etching agent ("CZ8101" manufactured by Mack Corporation) 1 µm It etched and roughened the copper surface.

(2) Lamination of resin sheets

The protective film was peeled off from the resin sheet manufactured in Production Example 2, and the resin composition layer was exposed. Using a batch-type vacuum pressurization laminator (manufactured by Nikko Materials, a two-stage build-up laminator "CVP700"), the resin composition layer was laminated on both surfaces of the inner layer substrate so that it was in contact with the inner layer substrate. After lamination was pressure-reduced for 30 second and air pressure was adjusted to 13 hPa or less, it performed by crimping|bonding at 100 degreeC and pressure 0.74 MPa for 30 second. Thereafter, hot pressing was performed at 100°C and a pressure of 0.5 MPa for 60 seconds.

(3) Thermosetting of the resin composition layer

Thereafter, the support is peeled off, and the inner layer substrate on which the resin sheet is laminated is put into an oven at 130° C. and heated for 30 minutes, then transferred to an oven at 200° C. and heated for 90 minutes to thermoset the resin composition layer for insulation layer was formed. A cured substrate A having an insulating layer, an inner layer substrate and an insulating layer in this order was obtained.

(4) stud pull peel strength test

After cutting the said cured substrate A into 1 cm square, 2.7 mm diameter stud pins with an epoxy adhesive were adhere|attached, and it hardened|cured at 150 degreeC for 1 hour, and made it adhere|attach. This was subjected to a stud pull peel strength test with a thin film adhesion strength measuring instrument Romulus manufactured by Quad Group. The case where peeling strength was 250 kgf/cm<3> or more was judged as "(circle)", and the case where it was less than that was determined as "x".

<Test Example 3: Measurement of dielectric loss tangent (Df)>

The resin sheet manufactured in Production Example 2 was cured in an oven at 190°C for 90 minutes, and further peeled off from the support to obtain a cured product. The hardened|cured material was cut out to 80 mm in length and 2 mm in width, and it was set as the evaluation sample. About this evaluation sample, the dielectric loss tangent was measured at the measurement frequency of 5.8 GHz, and the measurement temperature of 23 degreeC by the cavity resonance perturbation method using the HP8362B apparatus manufactured by Agilent Technologies. It measured about two test pieces, and computed the average value.

The usage-amount of the nonvolatile component of the resin composition of an Example and a comparative example, the evaluation result of a test example, etc. are shown in Table 1 below.

(A) Condensed ring structure-containing epoxy resin, (B) alkoxy group-containing naphthol aralkyl resin, and (C) inorganic filler, the content of (C) component is 100% by mass of the nonvolatile component in the resin composition In this case, it turned out that the curvature at the time of hardening can be suppressed and the hardened|cured material which has the outstanding adhesive strength can be obtained by using the resin composition of 70 mass % or more.

Claims (20)

A resin composition comprising (A) a condensed ring structure-containing epoxy resin, (B) an alkoxy group-containing naphthol aralkyl resin, and (C) an inorganic filler,
(C) When content of a component makes the non-volatile component in a resin composition 100 mass %, the resin composition of 70 mass % or more. The method according to claim 1, wherein the component (B) is represented by the following formula (2):
[Formula (2)]

[wherein, each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, at least one R is an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 2 to 20]
A naphthol aralkyl resin represented by a resin composition. The resin composition according to claim 1, wherein the component (A) contains a (A-1) monomer-type condensed ring structure-containing epoxy resin. The epoxy equivalent of the component (A-1) according to claim 3, 120 g/eq. more than 200g/eq. Below, the resin composition. The resin composition according to claim 3, wherein the molecular weight of component (A-1) is 500 or less. The resin composition according to claim 1, wherein the component (A) contains (A-2) a condensed ring structure-containing epoxy resin of a repeating structure type. The epoxy equivalent of the component (A-2) according to claim 6, 250 g/eq. more than 400g/eq. Below, the resin composition. The resin composition according to claim 6, wherein the component (A-2) is a naphthol aralkyl type epoxy resin. The resin composition according to claim 3, wherein the component (A) contains both (A-1) a monomeric fused-ring structure-containing epoxy resin and (A-2) a repeating structural-type fused-ring structure-containing epoxy resin. The resin composition according to claim 9, wherein the mass ratio (monomer type/repeating structure type) of component (A-1) to component (A-2) is 1 or more and 5 or less. The resin composition of Claim 1 whose content of (A) component makes all the epoxy resins in a resin composition 100 mass %, 90 mass % or more. The resin composition of Claim 1 whose content of (A) component is 50 mass % or more, when content of non-volatile components other than (C) component in a resin composition makes 100 mass %. The resin composition according to claim 1, further comprising (D) an organic filler. The resin composition according to claim 13, wherein the component (D) is a core-shell type rubber particle. The resin composition of Claim 1 whose content of (C)component is 80 mass % or more, when content of the non-volatile component in a resin composition makes 100 mass %. A cured product of the resin composition according to any one of claims 1 to 15. The sheet-like laminated material containing the resin composition in any one of Claims 1-15. A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of claims 1 to 15 provided on the support. A printed wiring board provided with the insulating layer which consists of hardened|cured material of the resin composition in any one of Claims 1-15. A semiconductor device comprising the printed wiring board according to claim 19 .