KR20190026615A - Resin compositions - Google Patents

Abstract

A purpose of the presentation is to provide a resin composition and the like, wherein the resin composition is excellent in thin film insulating properties even when an inorganic filler having a small average particle diameter is used and is able to obtain a balanced cured product which can maintain adhesiveness between conductor layers after an environmental test under a high temperature and high humidity environment. The resin composition comprises: (A) an epoxy resin; (B) a benzoxazine compound; and (C) the inorganic filler having an average particle diameter of 100 nm or less, wherein the content of the component (C) is 40 mass% or more when the content of non-volatile components in the resin composition is 100 mass%.

Description

RESIN COMPOSITIONS [0001]

The present invention relates to a resin composition. Further, the present invention relates to a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition.

BACKGROUND ART [0002] As a manufacturing technique of a printed wiring board, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately stacked is known. In the build-up method, generally, the insulating layer is formed by curing the resin composition. For example, Patent Document 1 discloses an epoxy resin composition comprising an epoxy resin, an active ester compound, a carbodiimide compound, a thermoplastic resin and an inorganic filler, wherein when the content of the inorganic filler is 100 mass% By mass or more and 40% by mass or more.

Patent Document 1: JP-A-2016-27097

Generally, when the thickness of the insulating layer is reduced, it is conceivable to use an inorganic filler having a small average particle diameter or a large specific surface area from the viewpoint of ensuring insulation reliability. However, the present inventors have found that it is difficult to maintain the adhesion between the conductor layer and the insulating layer after the environmental test under a high-temperature and high-humidity environment when the resin composition contains an inorganic filler having a small average particle size or a large specific surface area I got it. Particularly, in order to solve the mismatch of the thermal expansion coefficient between the conductor layer and the insulating layer, it is sometimes required to blend more inorganic fillers. When a large amount of inorganic filler is used, it becomes more difficult to maintain the adhesion. In order to meet the demand of the fine wiring in the future, it is required to maintain the adhesion after the environmental test even if an inorganic filler having a small average particle diameter or a large specific surface area is used.

However, among the constraints of using an inorganic filler having a small average particle diameter or a large specific surface area, a technique for increasing the adhesion after environmental testing has not been developed.

Disclosure of Invention An object of the present invention is to provide a resin composition which is excellent in thin film insulation even when an inorganic filler having a small average particle size or a large specific surface area is used and which can maintain adhesion between conductor layers after environmental testing under a high temperature and high humidity environment, A resin composition capable of obtaining a cargo; A resin sheet containing the resin composition; A printed wiring board having an insulating layer formed using the resin composition, and a semiconductor device.

In order to achieve the object of the present invention, the present inventors have intensively studied and, as a result, have found that even when an inorganic filler having a small average particle size or a large specific surface is used, a benzoxazine compound is contained in the resin composition, The adhesion between the layers can be maintained, and the present invention has been accomplished.

That is, the present invention includes the following contents.

[1] A resin composition comprising (A) an epoxy resin, (B) a benzoxazine compound, and (C) an inorganic filler having an average particle diameter of 100 nm or less,

And the content of the component (C) is 40% by mass or more when the content of the nonvolatile component in the resin composition is 100% by mass.

[2] A resin composition comprising (A) an epoxy resin, (B) a benzoxazine compound, and (C) an inorganic filler having a specific surface area of 15 m ² /

And the content of the component (C) is 40% by mass or more when the content of the nonvolatile component in the resin composition is 100% by mass.

[3] The resin composition according to [1] or [2], further comprising (D) a curing agent.

[4] The resin composition according to [3], wherein the component (D) comprises at least one of a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a cyanate ester-based curing agent and a carbodiimide-based curing agent.

[5] The resin composition according to any one of [1] to [4], wherein the content of the component (B) is 0.1% by mass or more and 30% by mass or less based on 100% by mass of the nonvolatile component in the resin composition.

[6] The resin composition according to any one of [1] to [5], wherein the component (B) is represented by the following formula (B-1).

The formula (B-1)

In the above formula (B-1)

R ¹ represents an n-valent group, and each R ² independently represents a halogen atom, an alkyl group, or an aryl group. n represents an integer of 2 to 4, and m represents an integer of 0 to 4.

[7] The resin composition according to [6], wherein in the formula (1), R ¹ is an n-valent group consisting of an arylene group, an alkylene group, an oxygen atom or a combination of two or more thereof.

[8] The resin composition according to [6] or [7], wherein in the formula (1), m represents 0.

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

[10] The resin composition according to any one of [1] to [9], which is for forming an interlayer insulating layer of a printed wiring board.

[11] A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of [1] to [10], which is provided on the support.

[12] The resin sheet according to [11], wherein the resin composition layer has a thickness of 15 μm or less.

[13] A printed circuit board comprising a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer, wherein the first conductor layer and the second conductor layer have an interval of 6 [ The resin sheet according to [11] or [12], wherein the resin sheet is for forming the insulating layer.

[14] A printed wiring board comprising a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,

The insulating layer is a cured product of the resin composition according to any one of [1] to [10].

[15] The printed wiring board according to [14], wherein the interval between the first conductor layer and the second conductor layer is 6 μm or less.

[16] A semiconductor device comprising the printed wiring board according to [14] or [15].

According to the present invention, even when an inorganic filler having a small average particle size or a large specific surface area is used, it is possible to maintain a good balance between the conductor layers after the environmental test under a high temperature and high humidity environment, Can be obtained; A resin sheet containing the resin composition; A printed wiring board having an insulating layer formed using the resin composition, and a semiconductor device.

1 is a partial cross-sectional view schematically showing an example of a printed wiring board.

Hereinafter, the resin composition, resin sheet, printed wiring board, and semiconductor device of the present invention will be described in detail.

[Resin composition]

The first resin composition of the present invention is a resin composition comprising (A) an epoxy resin, (B) a benzoxazine compound, and (C) an inorganic filler having an average particle diameter of 100 nm or less, wherein the content of the component Is not less than 40% by mass, based on 100% by mass of the nonvolatile component. The second resin composition of the present invention is a resin composition comprising (A) an epoxy resin, (B) a benzoxazine compound, (C) an inorganic filler having a specific surface area of 15 m ² / g or more, Is not less than 40% by mass based on 100% by mass of the nonvolatile component in the resin composition. The resin composition of the first and second embodiments contains (B) a benzoxazine compound, so that even when an inorganic filler having a small average particle diameter or a large specific surface area is used, the resin composition of the first and second embodiments has excellent thin film insulation properties, It is possible to obtain a cured product capable of maintaining the adhesion between the posterior conductor layers. In general, a cured product capable of maintaining high adhesiveness even after an environmental test under such a high temperature and high humidity environment can exhibit high adhesiveness over a long period of time.

Conventionally, (B) benzoxazine compounds are known to function as curing agents for epoxy resins. However, when the inorganic filler having an average particle diameter of 100 nm or less or an inorganic filler having a specific surface area of 15 m ² / g or more and a benzoxazine compound are contained in combination, the inventors of the present invention have found that, even after the environmental test under a high- It was found that adhesion can be maintained. As long as the present inventors know, the technical idea of maintaining a high adhesion even after an environmental test under a high temperature and high humidity environment by containing a benzoxazine compound is not proposed at all in the past.

The resin composition contains, in addition to the components (A) to (C), a curing agent, (E) a curing accelerator, (F) a thermoplastic resin, (G) a flame retardant, and (H) good. Hereinafter, each component contained in the resin composition of the first and second embodiments of the present invention will be described in detail. Here, the resin composition of the first embodiment and the resin composition of the second embodiment may be collectively referred to as " resin composition ".

≪ (A) Epoxy resin >

The resin composition comprises (A) an epoxy resin. Examples of the epoxy resin (A) include epoxy resins such as a biscylenol type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, Phenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tertiary-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy A cresol novolak type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, an alicyclic epoxy resin, a heterocyclic epoxy resin, a spirocyclic epoxy resin , Cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, naphthylene ether type epoxy resin Trimethylol type epoxy resin, tetraphenylethan type epoxy resin, and the like. The epoxy resins may be used alone or in combination of two or more.

The epoxy resin (A) is preferably an aromatic epoxy resin from the viewpoint of obtaining a cured product capable of maintaining high adhesiveness even after an environmental test under a high temperature and high humidity environment, and is preferably a bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, It is preferable to use any one of biphenyl type epoxy resins.

The epoxy resin (A) preferably has two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100 mass%, it is preferable that at least 50 mass% or more is an epoxy resin having two or more epoxy groups in one molecule. Among them, the resin composition preferably includes a combination of an epoxy resin (hereinafter also referred to as a " liquid epoxy resin ") that is liquid at 20 ° C and an epoxy resin (also referred to as a "solid epoxy resin") that is solid at 20 ° C Do. As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable, and an aromatic liquid epoxy resin having two or more epoxy groups in one molecule is more preferable. As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable. In the present invention, an aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolak type epoxy resin , An alicyclic epoxy resin having an ester skeleton, a cyclohexane-type epoxy resin, a cyclohexane dimethanol-type epoxy resin, a glycidylamine-type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a bisphenol A- desirable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC, "828US", "jER828EL", "825", "Epikote 828EL (Bisphenol A type epoxy resin), "jER807", "1750" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin) "630" ZX1059 " (a mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin) manufactured by Shinnitetsu Sumikinka Chemical Co., and EX-721 (a glycidyl ester type epoxy resin (Alicyclic epoxy resin having an ester skeleton), " PB-3600 " (epoxy resin having a butadiene structure), " ZX1658 ", " ZX1658GS (Liquid 1,4-glycidyl cyclohexane type epoxy resin ), "630LSD" (glycidyl amine-type epoxy resin manufactured by Mitsubishi Chemical Co., Ltd.) and the like. These may be used alone, or two or more kinds may be used in combination.

Examples of the solid epoxy resin include epoxy resins such as bicalcylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, cresol novolak type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, Epoxy type epoxy resins, phenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins and tetraphenyl ethane type epoxy resins are preferable. Vicillanol type epoxy resins and bisphenol AF type epoxy The resin is more preferable. Specific examples of the solid epoxy resin include HP4032H (naphthalene type epoxy resin), HP-4700, HP-4710 (naphthalene type tetrafunctional epoxy resin), N-690 HP-7200H "," HP-7200H "," EXA-7311 "(dicyclopentadiene type epoxy resin)," N-695 "(cresol novolak type epoxy resin) EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(naphthylene ether type epoxy resin)" EPPN-502H "(manufactured by Nippon Kayaku Co., Quot; NC3000L ", " NC3100L ", " NC3100 " (biphenyl type epoxy resin), " NC7000L " (naphthol novolak type epoxy resin) ESN475V "(naphthalene type epoxy resin)," ESN485 "(naphthol novolak type epoxy resin)," YX4000H "," YX4000 "and" YL6121 "manufactured by Mitsubishi Chemical Co., , "YX4000HK" (biquileneol type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" manufactured by Mitsubishi Chemical Corporation Quot; jER1010 " (solid bisphenol A type epoxy resin) and " jER1031S " (tetraphenyl ethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. have. These may be used alone, or two or more kinds may be used in combination.

When the liquid epoxy resin and the solid epoxy resin are used in combination as the component (A), their ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1: 1 to 1:20 in terms of the mass ratio. By setting the proportions of the liquid epoxy resin and the solid epoxy resin within this range, it is possible to obtain an appropriate tackiness when i) the resin sheet is used in the form of a resin sheet, ii) sufficient flexibility can be obtained when used in the form of a resin sheet, And (iii) a cured product having sufficient breaking strength can be obtained. In view of the effects of i) to iii), the ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably in the range of 1: 1 to 1: 5, 1 to 1: 3 is more preferable.

From the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability, the content of the component (A) in the resin composition is preferably 10% by mass or more, more preferably 10% by mass or more when the nonvolatile component in the resin composition is 100% By mass or more, and more preferably 20% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited insofar as the effects of the present invention are exhibited, but is preferably 40 mass% or less, more preferably 35 mass% or less, further preferably 30 mass% or less.

In the present invention, the content of each component in the resin composition is a value obtained by assuming that the nonvolatile component in the resin composition is 100% by mass, unless otherwise specified.

The epoxy equivalent of the component (A) is preferably 50 to 5000, more preferably 50 to 3000, even more preferably 80 to 2000, still more preferably 110 to 1000. With this range, the cross-linking density of the cured product becomes sufficient, resulting in an insulating layer having a small surface roughness. The epoxy equivalent can be measured in accordance with JIS K7236, and is the mass of the resin containing one equivalent of epoxy group.

The weight average molecular weight of the component (A) is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

≪ (B) benzoxazine compound >

The resin composition contains (B) a benzoxazine compound. The benzoxazine photographic compound (B) is a compound having in its molecule a benzoxazine ring represented by the following formula (B-2).

(B-2)

The number of benzoxazine rings per molecule of the benzoxazine compound (B) is preferably 1 or more, more preferably 2 or more, and more preferably 2 or more, from the viewpoint of improving the high adhesion property even after the environmental test under a high- Is 10 or less, more preferably 5 or less.

The (B) benzoxazine compound preferably has an aromatic ring in addition to the benzoxazine ring. By having an aromatic ring in addition to the benzoxazine ring, it is possible to maintain high adhesiveness even after the environmental test under a high temperature and high humidity environment. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring and a biphenyl ring, and a benzene ring is preferable. The number of aromatic rings is preferably 1 or more, more preferably 2 or more, preferably 10 or less, more preferably 5 or less, from the viewpoint of improving the adhesion.

As the benzooxazine compound (B), a benzoxazine compound represented by the following formula (B-1) is preferable.

The formula (B-1)

In the above formula (B-1)

R ¹ represents an n-valent group, and each R ² independently represents a halogen atom, an alkyl group, or an aryl group. n represents an integer of 2 to 4, and m represents an integer of 0 to 4.

R ¹ represents an n-valent group. These groups are preferably an arylene group, an alkylene group, an oxygen atom, or an n-valent group composed of a combination of two or more thereof, more preferably an arylene group or an n-valent group consisting of a combination of two or more, Is more preferable.

The arylene group is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 15 carbon atoms, and still more preferably an arylene group having 6 to 12 carbon atoms. Specific examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group and a biphenylene group, and a phenylene group is preferable.

The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 3 carbon atoms. Specific examples of the alkylene group include a methylene group, an ethylene group and a propylene group, and a methylene group is preferable.

Examples of the group formed by combining two or more groups include a group in which at least one arylene group is bonded to at least one oxygen atom, a group in which at least one arylene group and at least one alkylene group are bonded, a group in which at least one alkylene group is bonded with at least one oxygen atom, A group in which at least one arylene group and at least one oxygen atom are bonded, and a group in which at least one arylene group and at least one alkylene group are bonded is preferable. Specific examples of the groups formed by combining two or more groups include the following groups. In the formula, " * " represents the number of bonds (bonds).

The arylene group and the alkylene group may have a substituent. Substituent is not particularly limited, for example, a halogen atom, -OH, -OC _1-6 alkyl, -N (C _1-6 alkyl) _2, C _1-6 alkyl, C _6-10 aryl groups, -NH ₂ , -CN, -C (O) OC _1-6 alkyl group, -COOH, -C (O) H, -NO ₂ and the like. Here, the term " C _pq " (p and q are positive integers and satisfying p < q) indicates that the number of carbon atoms of the organic group described immediately after this term is p to q. For example, the expression " C _1-6 alkyl group " represents an alkyl group having 1 to 6 carbon atoms.

The above substituent may further have a substituent (hereinafter may be referred to as " secondary substituent "). As the secondary substituent, the same substituents as those described above may be used, unless otherwise specified.

R ² each independently represents a halogen atom, an alkyl group, or an aryl group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms. The halogen atom represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The alkyl group and the aryl group may have a substituent. The substituent is the same as the substituent which the arylene group may have.

n represents an integer of 2 to 4, preferably an integer of 2 to 3, and more preferably 2. m represents an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably 0.

The benzoxazine photographic compound represented by the general formula (B-1) is preferably at least one of the benzoxazine photographic compounds represented by the following general formulas (B-3) and (B-4) .

(B-3)

The compound represented by the formula (B-4)

The benzoxazine compound represented by the formula (B-3) is preferably at least any one of the benzoxazine compounds represented by the formula (B-5) and the formula (B-6) Is preferably a benzoxazine compound represented by the formula (B-7).

The compound of formula (B-5)

The formula (B-6)

The compound of formula (B-7)

The benzoxazine compound represented by the formula (B-1) may be used singly or as a mixture of two or more thereof. For example, when the benzoxazine compound represented by the formula (B-5) and the benzoxazine compound represented by the formula (B-6) are used as a mixture, the mass mixing ratio (formula (B-5) B-6) is preferably 1:10 to 10: 1, more preferably 1: 5 to 5: 1, and even more preferably 1: 3 to 3: 1. By setting the mass mixing ratio within this range, the adhesion with the conductor layer after the environmental test can be improved.

Specific examples of the benzooxazine compound (B) include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., "P-d" and "F-a" manufactured by Shikoku Seiko Co., &Quot; HFB2006M " manufactured by Shawako Bunshi Co., Ltd., and the like.

The molecular weight of the (B) benzoxazine compound is preferably 200 or more, more preferably 300 or more, further preferably 400 or more, preferably 1000 or less, more preferably 800 or less, from the viewpoint of improving the adhesion property , More preferably 500 or less.

The content of the (B) benzoxazine compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 1% by mass or more, based on 100% by mass of the nonvolatile component in the resin composition . The upper limit is preferably 30 mass% or less, more preferably 10 mass% or less, further preferably 5 mass% or less or 3 mass% or less. By making the content of the component (B) fall within this range, adhesion with the conductor layer after the environmental test can be improved.

<(C) Inorganic filler>

The first resin composition (C) contains an inorganic filler having an average particle diameter of 100 nm or less. The resin composition of the second embodiment contains (C) an inorganic filler having a specific surface area of 15 m ² / g or more. These inorganic fillers may be simply referred to as &quot; (C) inorganic fillers &quot;.

The material of the inorganic filler (C) is not particularly limited as long as it is an inorganic compound, and examples thereof include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, Aluminum oxide, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium titanate, zirconium titanate, zirconium titanate, zirconium titanate , Zirconium oxide, barium titanate, barium titanate-barium zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. As the silica, spherical silica is preferable. The inorganic fillers may be used singly or in combination of two or more kinds.

The average particle diameter of the inorganic filler (C) in the first embodiment is 100 nm or less, preferably 90 nm or less, more preferably 80 nm or less from the viewpoint of thin film insulation. The lower limit of the average particle diameter is not particularly limited, but is preferably 1 nm or more, more preferably 5 nm or more, and further preferably 10 nm or more.

The average particle diameter of the inorganic filler in the second embodiment is preferably 100 nm or less, more preferably 90 nm or less, and still more preferably 80 nm or less, from the viewpoint of thin film insulation. The lower limit of the average particle diameter is not particularly limited, but is preferably 1 nm or more, more preferably 5 nm or more, and further preferably 10 nm or more.

Examples of commercial products of the inorganic filler (C) having such an average particle size include &quot; UFP-30 &quot; manufactured by Denki Kagaku Ko Corporation.

(C) The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler (C) can be measured by using a laser diffraction scattering particle size distribution measuring apparatus, and the median diameter is determined as the average particle diameter. The sample to be measured is preferably (C) an inorganic filler dispersed in methyl ethyl ketone by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring apparatus, "LA-500" manufactured by Horiba Seisakusho Co., Ltd., "SALD-2200" manufactured by Shimadzu Corporation can be used.

The specific surface area of the inorganic filler in the second embodiment is preferably 15 m ² / g or more, more preferably 20 m ² / g or more, and still more preferably 30 m ² / g or more, from the viewpoint of thin film insulation. The upper limit is not particularly limited, but is preferably 60 m ² / g or less, more preferably 50 m ² / g or less, and still more preferably 40 m ² / g or less.

The specific surface area of the inorganic filler in the first embodiment is preferably 15 m ² / g or more, more preferably 20 ^{m 2} / g or more, still more preferably 30 m ² / g or more from the viewpoint of thin film insulation. The upper limit is not particularly limited, but is preferably 60 m ² / g or less, more preferably 50 m ² / g or less, and still more preferably 40 m ² / g or less.

The specific surface area is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring apparatus (Macsorb HM-1210, manufactured by Mountain Tex) according to the BET method and calculating the specific surface area using the BET multi-point method.

The inorganic filler (C) may be surface-treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include an amino silane coupling agent, an epoxy silane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an alkoxysilane, an organosilazane compound, and a titanate coupling agent . Examples of commercial products of surface treatment agents include KBM403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM803 (3-mercaptopropyltrimethoxy Silane), KBE903 (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM573 (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin- KBM103 "(phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.," KBM-4803 "manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy-type silane couples , KBM-7103 (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like. The surface treatment agent may be used alone, or two or more kinds may be used in combination.

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

The amount of carbon per unit surface area of the inorganic filler (C) can be measured after the inorganic filler (C) after the surface treatment is cleaned with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler (C) surface-treated with a surface treatment agent, and ultrasonically cleaned at 25 캜 for 5 minutes. After the supernatant is removed and the solid content is dried, the amount of carbon per unit surface area of inorganic filler (C) can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba Seisakusho Co., Ltd. and the like can be used.

The content of the inorganic filler (C) is preferably not less than 40% by mass, more preferably not less than 45% by mass, more preferably not less than 50% by mass based on 100% by mass of the nonvolatile component in the resin composition, %. The upper limit is preferably 80 mass% or less, more preferably 70 mass% or less, further preferably 65 mass% or less. In the present invention, since the benzoxazine compound (B) is contained, it is possible to maintain the adhesiveness after the HAST test even if the inorganic filler (C) is contained in an amount of 40 mass% or more.

&Lt; (D) Curing agent >

In one embodiment, the resin composition may contain (D) a curing agent. The (D) curing agent is not particularly limited as long as it has a function of curing the component (A), and examples thereof include phenol series curing agents, naphthol series curing agents, active ester series curing agents, cyanate ester series curing agents, and carbodiimide series And a hardening agent. Among them, from the viewpoint of improving insulation reliability, (D) the curing agent is preferably at least one of a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a cyanate ester-based curing agent and a carbodiimide- It is more preferable to include a phenol-based curing agent. The curing agent may be used alone or in combination of two or more.

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

Specific examples of the phenol-based curing agent and naphthol-based curing agent include MEH-7700, MEH-7810 and MEH-7851 manufactured by Meiwa Kasei Co., Ltd., NHN manufactured by Nippon Kayaku Co., SN375 "," SN-495V "," SN375 "," SN395 "," SN375 "," TD-2090 "," LA-7052 "," LA-7054 "," LA-1356 "," LA-3018-50P "and" EXB-9500 "manufactured by DIC Corporation.

The active ester-based curing agent is not particularly limited, but generally, an ester group having high reactivity such as esters of phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compounds is used in an amount of 2 Are preferably used. It is preferable that the active ester-based curing agent is obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. From the viewpoint of heat resistance improvement, an active ester type curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester type curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o- Cresol, catechol, alpha -naphthol, beta -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzene triol, dicyclopentadiene type diphenol compounds, phenol novolak, and the like. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol in one dicyclopentadiene molecule.

Specifically, there can be mentioned an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated phenol novolac, a benzoyl compound of phenol novolac Active ester compounds are preferable, and active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

EXB9451 "," EXB9460 "," EXB9460S "," HPC-8000-65T "," HPC-8000H-65TM ", and the like are available as commercial products of the active ester- , EXB8000L-65TM, EXB8150-65T (manufactured by DIC), EXB9416-70BK (manufactured by DIC) as an active ester compound containing a naphthalene structure, active ester containing phenol novolac acetylate "DC808" (manufactured by Mitsubishi Chemical Corporation), "YLH1026" (manufactured by Mitsubishi Chemical Corp.) as an active ester compound containing benzoylated phenol novolac, "DC808" as an active ester- YLH1026 &quot; (manufactured by Mitsubishi Chemical Corporation), &quot; YLH1030 &quot; (manufactured by Mitsubishi Chemical Corp.), and &quot; YLH1048 &quot; (manufactured by Mitsubishi Chemical Corporation) as a benzoylate of phenol novolac, Manufactured by Chemical Co., Ltd.).

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

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

The proportion of the epoxy resin and the curing agent is preferably in the range of 1: 0.01 to 1: 2, more preferably 1: 0.05 to 1: 3, in the ratio of [the total number of epoxy groups of epoxy resin]: [the total number of reactors of the curing agent] , More preferably from 1: 0.1 to 1: 1.5. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, and the like, depending on the kind of the curing agent. The total number of epoxy groups in the epoxy resin refers to a value obtained by dividing the solid content of each epoxy resin by the epoxy equivalent in terms of the total epoxy resin and the total number of reactors in the curing agent means the total mass of the solid components in the curing agent Divided by the total amount of the curing agent. By setting the ratio of the epoxy resin and the curing agent to this range, the heat resistance of the cured product of the resin composition is further improved.

When the (D) curing agent is contained, the content of the (D) curing agent is preferably 1% by mass or more, more preferably 3% by mass or more, more preferably 3% Is not less than 5% by mass. The upper limit is preferably 30 mass% or less, more preferably 25 mass% or less, further preferably 20 mass% or less. When the content of the (D) curing agent is within this range, the adhesion with the conductor layer can be improved.

<(E) Curing accelerator>

In one embodiment, the resin composition may contain (E) a curing accelerator. Examples of the curing accelerator include phosphorus hardening accelerators, amine hardening accelerators, imidazole hardening accelerators, guanidine hardening accelerators and metal hardening accelerators. Phosphorus hardening accelerators, amine hardening accelerators, imidazole hardening accelerators, Accelerators and metal-based curing accelerators are preferable, and amine-based curing accelerators are more preferable. The curing accelerator may be used singly or in combination of two or more.

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

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl- Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] -ethyl-s-triazine, 2,4- diamino-6- [ Imidazolyl- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- Triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl- , 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3- Dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline An imidazole compound and an adduct of an imidazole compound and an epoxy resin, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As the imidazole-based curing accelerator, a commercially available product may be used. Examples thereof include &quot; P200-H50 &quot; manufactured by Mitsubishi Chemical Corporation.

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

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

When the resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, more preferably 0.03% by mass or more, 0.05% by mass or more. The upper limit is preferably 3 mass% or less, more preferably 2 mass% or less, further preferably 1 mass% or less. By setting the content of the curing accelerator within this range, it is possible to obtain a cured product having excellent adhesion after environmental testing under a high temperature and high humidity environment even when an inorganic filler having a small average particle diameter or a large specific surface area is used.

&Lt; (F) Thermoplastic resin >

In one embodiment, the resin composition may contain (F) a thermoplastic resin. Examples of the thermoplastic resin (F) include thermoplastic resins such as phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, Polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, and polyester resins. Phenoxy resins are preferred. The thermoplastic resins may be used alone or in combination of two or more.

The weight average molecular weight of the thermoplastic resin (F) in terms of polystyrene is preferably 38,000 or more, more preferably 40,000 or more, and still more preferably 42,000 or more. The upper limit is preferably not more than 100000, more preferably not more than 70000, still more preferably not more than 60,000. (F) The weight average molecular weight of the thermoplastic resin in terms of polystyrene is measured by gel permeation chromatography (GPC). Specifically, the weight average molecular weight of the thermoplastic resin (F) in terms of polystyrene was measured using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L / K-804L as a mobile phase, chloroform at a column temperature of 40 占 폚, and using a standard polystyrene calibration curve.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, A phenoxy resin having at least one skeleton selected from the group consisting of a skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethyl cyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resins may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (both phenol resins containing a bisphenol A skeleton), "YX8100" (phenoxy resin containing a bisphenol S skeleton), and "YX6954" Phenone skeleton-containing phenoxy resin). In addition, "FX280" and "FX293" manufactured by Shinnetsu Tsushiminka Chemical Co., Ltd., "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30 YL7769BH30 "," YL6794 "," YL7213 "," YL7290 ", and" YL7482 ".

Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, "Denkabutilal 4000-2", "Denkabutilal 5000-A", "Denkabutilal 6000-C", "Denkabutiral (For example, KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd., and the like.

Specific examples of the polyimide resin include "Rika coat SN20" and "Rika coat PN20" manufactured by Shin-Nihon Rika Co., Ltd. Specific examples of the polyimide resin include a linear polyimide (polyimide described in JP-A 2006-37083) obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride, Modified polyimides such as polysiloxane skeleton-containing polyimide (Japanese Patent Application Laid-Open No. 2002-12667 and Japanese Patent Application Laid-Open No. 2000-319386, etc.).

Specific examples of the polyamide-imide resin include "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyo Boseki Company. Specific examples of the polyamideimide resin include modified polyamideimides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamideimide) produced by Hitachi Kasei Corporation.

Specific examples of the polyether sulfone resin include "PES 5003P" manufactured by Sumitomo Chemical Co., Ltd. Specific examples of the polyphenylene ether resin include an oligophenylene ether styrene resin &quot; OPE-2St 1200 &quot; manufactured by Mitsubishi Gas Sukagaku Co., Ltd. and the like.

Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd.

Among them, as the thermoplastic resin (F), a phenoxy resin and a polyvinyl acetal resin are preferable. Accordingly, in a preferred embodiment, the thermoplastic resin includes at least one selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin. Among them, a phenoxy resin is preferable as the thermoplastic resin, and a phenoxy resin having a weight average molecular weight of 40,000 or more is particularly preferable.

When the resin composition contains (F) a thermoplastic resin, the content of the thermoplastic resin (F) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, Or more, and more preferably 1 mass% or more. The upper limit is preferably 5 mass% or less, more preferably 3 mass% or less, further preferably 2 mass% or less. (F) By setting the content of the thermoplastic resin within this range, it is possible to obtain a cured product having excellent adhesion after environmental testing under a high temperature and high humidity environment even when an inorganic filler having a small average particle diameter or a large specific surface area is used.

<(G) Flame Retardant>

In one embodiment, the resin composition may contain (G) a flame retardant. Examples of the flame retardant (G) include phosphazene compounds, organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicon-based flame retardants and metal hydroxides. Phosphazene compounds are preferred. The flame retardant may be used alone, or two or more thereof may be used in combination.

The phosphazene compound is not particularly limited as long as it is a cyclic compound containing nitrogen and phosphorus as constituent elements, but the phosphazene compound is preferably a phosphazene compound having a phenolic hydroxyl group.

Specific examples of the phosphazene compound include "SPH-100", "SPS-100", "SPB-100" and "SPE-100" manufactured by Otsuka Chemical Co., FP-110 "," FP-300 "and" FP-400 ", and" SPH-100 "manufactured by Otsuka Kagaku Co., Ltd. is preferable.

As the flame retardant other than the phosphazene compound, a commercially available product may be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd., and "PX-200" manufactured by Daihachi Chikakaku Corporation. As the flame retardant, it is preferable that hydrolysis is difficult, and for example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like are preferable.

When the resin composition contains the flame retardant (G), the content of the flame retardant (G) in the resin composition is preferably at least 0.3 mass%, more preferably at least 0.5 mass%, more preferably at least 0.5 mass% More preferably, it is 0.7% by mass or more. The upper limit is preferably 5 mass% or less, more preferably 4 mass% or less, further preferably 3 mass% or less.

&Lt; (H) Optional additives >

In one embodiment, the resin composition may further contain other additives, if necessary. Examples of such other additives include organic metal compounds such as organic fillers, organic copper compounds, organic zinc compounds and organic cobalt compounds , And a resin additive such as a thickener, a defoaming agent, a leveling agent, an adhesion-imparting agent, and a colorant.

As the organic filler, any organic filler that can be used in forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicon particles. As the rubber particles, a commercially available product may be used, for example, "EXL2655" manufactured by Dow Chemical Co., Ltd., "AC3401N" manufactured by Aikoko Co., Ltd., and "AC3816N".

&Lt; Physical properties and uses of resin composition >

The cured product obtained by thermosetting the resin composition at 100 占 폚 for 30 minutes and then at 180 占 폚 for 30 minutes usually has an excellent insulation property even if the thickness thereof is 5.0 占 0.5 占, (Thin film insulation property). The insulation resistance value of the cured product having a thickness of 5 占 0 占 퐉 is preferably 1 占⁰⁷ or more, more preferably 1 占⁰⁸ or more, and still more preferably 1 占⁰⁹ or more. The upper limit is not particularly limited, but may be 100 x 10 &lt; ¹² &gt; The measurement of the insulation resistance value can be performed by the method described in the following embodiments. When the component (B) is reacted with the component (A), a phenolic hydroxyl group is generated from the component (B), and the phenolic hydroxyl group inhibits the oxidation of metals such as copper during the environmental test. As a result, it can be considered that the cured product of the resin composition of the present invention improves the adhesion after the environmental test.

The cured product obtained by thermosetting the resin composition at 190 占 폚 for 90 minutes generally exhibits excellent peel strength (adhesion) before the environmental test. In other words, this results in an insulating layer having excellent adhesion before the environmental test. The peel strength of the copper foil before the environmental test is preferably 0.45 kgf / cm or more, more preferably 0.50 kgf / cm or more, and still more preferably 0.55 kgf / cm or more. The upper limit is not particularly limited, but may be 10 kgf / cm or less. The peeling strength of the copper foil before the environmental test can be measured by the method described in Examples to be described later.

The cured product obtained by thermosetting the resin composition at 190 占 폚 for 90 minutes generally exhibits excellent peel strength (adhesion) after the environmental test. In other words, it results in an insulating layer which is excellent in adhesion after environmental testing and can exhibit high adhesiveness over a long period of time. The copper foil peel strength after the environmental test is preferably 0.20 kgf / cm or more, more preferably 0.21 kgf / cm or more, and further preferably 0.25 kgf / cm or more. The upper limit is not particularly limited, but may be 10 kgf / cm or less. The peeling strength of the copper foil after the environmental test can be measured by the method described in the following Examples.

The resin composition of the present invention has an excellent thin film insulation property and can result in an insulating layer capable of maintaining adhesiveness between conductor layers after an environmental test under a high temperature and high humidity environment. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulation purposes. Specifically, there are 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, (A resin composition for an insulating layer of a printed wiring board) which can be suitably used as a resin composition (resin composition for an insulating layer of a printed wiring board) for forming an interlayer insulating layer of a printed wiring board . In addition, the resin composition of the present invention can be suitably used even in the case where the printed wiring board is a component built-in circuit board, because it results in an insulating layer having a good part filling property.

When the semiconductor chip package is manufactured through the following steps (1) to (6), for example, the resin composition of the present invention is a resin composition for rewiring layer A resin composition for forming a rewiring film forming layer), and a resin composition (a resin composition for sealing a semiconductor chip) for sealing a semiconductor chip. When the semiconductor chip package is manufactured, a redistribution layer may be further formed on the sealing layer.

(1) a step of laminating a temporary fixing film on a substrate,

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

(3) a step of forming a sealing layer on the semiconductor chip,

(4) a step of peeling the base material and the temporary film from the semiconductor chip,

(5) a step of forming a rewiring layer as an insulating layer on a surface of the base material and the temporary fixing film of the semiconductor chip,

(6) A step of forming a re-wiring layer as a conductor layer on the rewiring film forming layer

[Resin sheet]

The resin sheet of the present invention comprises a support and a resin composition layer formed on the support and formed from the resin composition of the present invention.

The thickness of the resin composition layer is preferably 15 占 퐉 or less, more preferably 13 占 퐉 or less, further preferably 10 占 퐉 or less, more preferably 10 占 퐉 or less, from the viewpoint of thinning of the printed wiring board and providing a cured product, Or 8 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 1 占 퐉 or more, 1.5 占 퐉 or more, 2 占 퐉 or more, or the like.

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

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN" (TAC), polyether sulfide (PES), poly (methyl methacrylate), poly (methyl methacrylate), poly Ether ketone, and polyimide. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, and 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 (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) .

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

As the support, a support having a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the release agent used for the release layer of the release layer-adherend support include at least one release agent selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin. SK-1 &quot;, &quot; AL-5 &quot;, and &quot; AL-5 &quot;, manufactured by Lintec Corporation, which is a PET film having a release layer composed mainly of an alkyd resin releasing agent as a main component, 7, &quot; Lumirror T60 &quot; manufactured by Toray Industries, Inc., &quot; Purex &quot; manufactured by Dejin Corporation, and Unipyl manufactured by Uniqica Corporation.

The thickness of the support is not particularly limited, but is preferably in the range of 5 탆 to 75 탆, more preferably in the range of 10 탆 to 60 탆. When the release layer-adhered support is used, it is preferable that the thickness of the entirety of the release layer-adhered support is in the above range.

In one embodiment, the resin sheet may further include other layers as required. Examples of such other layers include a protective film based on a support provided on a surface of the resin composition layer not bonded to a support (that is, a surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 m to 40 m. By laminating a protective film, adhesion and scratches of dust or the like to the surface of the resin composition layer can be suppressed.

The resin sheet can be produced, for example, by preparing a resin varnish obtained by dissolving a resin composition in an organic solvent, coating the resin varnish on a support using a die coater or the like, and drying the resin varnish to form a resin composition layer .

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

The drying may be carried out by a known method such as heating or hot air spraying. The drying conditions are not particularly limited, but the drying is carried out so that the content of the organic solvent in the resin composition layer is 10 mass% or less, preferably 5 mass% or less. For example, 30 to 60% by mass, is used, the resin varnish is dried at 50 to 150 DEG C for 3 minutes to 10 minutes to form a resin composition layer Can be formed.

The resin sheet can be rolled and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

Even if the resin sheet of the present invention is thin, it leads to an insulating layer (cured resin composition layer) capable of maintaining the adhesiveness between the conductor layers after the environmental test under the thin film insulation property and the high temperature and high humidity environment. Therefore, the resin sheet of the present invention can be suitably used as a resin sheet (for forming an insulating layer of a printed wiring board) for forming an insulating layer of a printed wiring board, and can be suitably used as a resin sheet for forming an interlayer insulating layer of a printed wiring board A resin sheet for an interlayer insulating layer of a wiring board). In addition, for example, in a printed wiring board comprising a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer, (Preferably, the thickness of the insulating layer between the first and second conductor layers) of the first and second conductor layers is set to 6 탆 or less (preferably 5.5 탆 or less, more preferably 5 탆 or less) Can be made excellent.

[Printed circuit board]

The printed wiring board of the present invention comprises an insulating layer, a first conductor layer, and a second conductor layer formed by a cured product of the resin composition of the present invention. The insulating layer is provided between the first conductor layer and the second conductor layer to insulate the first conductor layer from the second conductor layer (the conductor layer may be referred to as a wiring layer).

Since the insulating layer is formed by the cured product of the resin composition of the present invention, the insulating property of the thin film is excellent. Therefore, the thickness of the insulating layer between the first and second conductor layers is preferably 6 占 퐉 or less, more preferably 5.5 占 퐉 or less, and still more preferably 5 占 퐉 or less. The lower limit is not particularly limited, but may be 0.1 탆 or more. The distance between the first conductor layer and the second conductor layer (the thickness of the insulating layer between the first and second conductor layers) is, as shown in an example in Fig. 1, the distance between the major surface 11 of the first conductor layer 1 Refers to the thickness t1 of the insulating layer 3 between the main surfaces 21 of the second conductor layer 2. [ The first and second conductor layers are adjacent conductor layers through the insulating layer, and the main surface 11 and the main surface 21 are opposed to each other.

The total thickness t2 of the insulating layer is preferably 15 mu m or less, more preferably 13 mu m or less, and further preferably 10 mu m or less. The lower limit is not particularly limited, but may be usually 1 占 퐉 or more, 1.5 占 퐉 or more, 2 占 퐉 or more, or the like.

The printed wiring board can be produced by a method including the following steps (I) and (II) using the resin sheet described above.

(I) a step of laminating a resin composition layer of a resin sheet to be laminated on an inner layer substrate on an inner layer substrate

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

The &quot; inner layer substrate &quot; used in the step (I) is a member which becomes a substrate of a printed wiring board, and examples thereof include glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, Ether substrates and the like. The substrate may have a conductor layer on one side or both sides thereof, and the conductor layer may be patterned. An inner-layer substrate on which a conductor layer (circuit) is formed on one or both surfaces of the substrate is sometimes referred to as an &quot; inner-layer circuit substrate &quot;. Further, in manufacturing a printed wiring board, an intermediate product in which an insulating layer and / or a conductor layer is to be further formed is also included in the &quot; inner layer substrate &quot; When the printed wiring board is a component built-in circuit board, an inner-layer board containing components can be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet from the support side to the inner layer substrate. Examples of the member for heating and pressing the resin sheet to the inner layer substrate (hereinafter also referred to as "hot pressing member") include a heated metal plate (SUS hard plate) or a metal roll (SUS roll). Further, it is preferable to press the heat-press member through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface unevenness of the inner layer substrate, not directly press the resin sheet.

The lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. The hot-pressing temperature in the vacuum laminating method is preferably in the range of 60 占 폚 to 160 占 폚, more preferably 80 占 폚 to 140 占 폚, and the hot pressing pressure is preferably 0.098 MPa to 1.77 MPa, Preferably 0.29 MPa to 1.47 MPa, and the heat pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably performed under a reduced pressure of 26.7 hPa or less.

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

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

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

In the step (II), the resin composition layer is thermally cured to form an insulating layer.

The thermosetting conditions of the resin composition layer are not particularly limited, and conditions generally employed in forming the insulating layer of the printed wiring board may be used.

For example, the thermosetting condition of the resin composition layer varies depending on the type of the resin composition and the like, but the curing temperature is preferably 120 deg. C to 240 deg. C, more preferably 150 deg. C to 220 deg. C, 200 ° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and further preferably 15 minutes to 90 minutes.

The resin composition layer may be preheated to a temperature lower than the curing temperature before thermosetting the resin composition layer. For example, before the resin composition layer is thermally cured, the resin composition layer is heated to a temperature of 50 占 폚 or more and less than 120 占 폚 (preferably 60 占 폚 or more and 115 占 폚 or less, more preferably 70 占 폚 or more and 110 占 폚 or less) It may be preheated for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, more preferably 15 minutes to 100 minutes).

In the production of the printed wiring board, (III) a step of piercing the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further performed. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used in the production of printed wiring boards. When the support is removed after the step (II), the removal of the support is carried out between the steps (II) and (III), between the steps (III) and (IV) Or the like. Furthermore, if necessary, the formation of the insulating layer and the conductor layer in the process (II) to the process (V) may be repeated to form a multilayer wiring board. In this case, it is preferable that the thickness of the insulating layer (t1 in Fig. 1) between the respective conductor layers is within the above range.

Step (III) is a step of perforating the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. The step (III) may be carried out using, for example, a drill, a laser, a plasma or the like depending on the composition of the resin composition used for forming the insulating layer. The dimensions and shape of the holes may be appropriately determined in accordance with the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. The order and condition of the harmonization treatment are not particularly limited, and a well-known sequence and conditions commonly used in forming the insulating layer of the printed wiring board can be adopted. For example, the swelling treatment with a swelling liquid, the harmonization treatment with an oxidizing agent, and the neutralization treatment with a neutralizing liquid can be carried out in this order to roughen the insulating layer. The swelling liquid used for the harmonic treatment is not particularly limited, but examples thereof include an alkali solution and a surfactant solution, preferably an alkali solution, and more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Siculiganth P, Swelling Dip Sicurgis SBU manufactured by Atotech Japan Co., Ltd., and the like. The swelling treatment by the swelling liquid is not particularly limited, but can be carried out, for example, by immersing the swelling liquid at 30 占 폚 to 90 占 폚 for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in the swelling liquid at 40 占 폚 to 80 占 폚 for 5 minutes to 15 minutes. The oxidizing agent used for the harmonic treatment is not particularly limited, and for example, an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated at 60 ° C to 80 ° C for 10 minutes to 30 minutes. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd. and "Dozing Solution · Securigans P". An acidic aqueous solution is preferable as the neutralization solution used in the harmonization treatment, and commercially available products include, for example, "Reduction Solution · Securigant P" manufactured by Atotech Japan Co., The treatment with the neutralizing liquid can be carried out 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. From the standpoint of workability and the like, it is preferable to immerse the object subjected to the roughening treatment with an oxidizing agent in a neutralizing solution at 40 to 70 캜 for 5 to 20 minutes.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, further preferably 300 nm or less. The lower limit is not particularly limited, but is preferably 0.5 nm or more, more preferably 1 nm or more. The square root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, still more preferably 300 nm or less. The lower limit is not particularly limited, but is preferably 0.5 nm or more, more preferably 1 nm or more. The arithmetic mean roughness (Ra) and square-root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness machine.

Step (V) is a step of forming a conductor layer. Step (V) is a step of forming the first conductor layer when the conductor layer is not formed on the inner layer substrate, and when the conductor layer is formed on the inner layer substrate, the conductor layer is the first conductor layer, V) is a step of forming the second conductor layer.

The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium . The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include alloys of two or more metals selected from the above-mentioned group (for example, nickel-chromium alloy, copper-nickel alloy and copper- ). &Lt; / RTI &gt; Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper or a nickel-chromium alloy, a copper-nickel alloy And an alloy layer of a copper-titanium alloy 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, Is more preferable.

The conductor layer may have a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are stacked. When the conductor layer is a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

The thickness of the conductor layer depends on the design of the desired printed wiring board, but is generally from 3 탆 to 35 탆, preferably from 5 탆 to 30 탆.

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

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Subsequently, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to the desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

The resin sheet of the present invention can be suitably used even in the case where the printed wiring board is a component built-in circuit board, because it leads to a good insulating layer in terms of part embedding property. The component built-in circuit board can be manufactured by a known manufacturing method.

The printed wiring board manufactured using the resin sheet of the present invention may be provided with an insulating layer which is a cured product of the resin composition layer of the resin sheet and a buried wiring layer embedded in the insulating layer.

[Semiconductor device]

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

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

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) in a conductive portion of a printed wiring board. The "conduction point" is a "point for transmitting an electrical signal on the printed wiring board", and may be a surface or a buried point. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor material.

The method of mounting the semiconductor chip at the time of manufacturing the semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. Specifically, the semiconductor chip is manufactured by a wire bonding mounting method, a flip chip mounting method, a bump- A mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), and the like. Here, the "mounting method using the bumpless buildup layer (BBUL)" is a "mounting method in which the semiconductor chip is directly embedded in the concave portion of the printed wiring board to connect the wiring on the semiconductor chip and the printed wiring board".

[Example]

Hereinafter, the present invention will be described more specifically with reference to Examples. The present invention is not limited to these examples. In the following description, &quot; part (s) &quot; and &quot;% &quot; for quantities mean &quot; part by mass &quot; and &quot;% by mass &quot;

[Production of resin composition]

&Lt; Example 1: Production of Resin Composition 1 >

, 10 parts of bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 180), 20 parts of biphenyl type epoxy resin ("YX4000H" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight of about 190), and bisphenol AF type epoxy resin (Manufactured by Mitsubishi Chemical Co., Ltd., "YL7553BH30", solid content 30% by mass), 10 parts of an epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238), 3 parts of phosphazene resin ("SPH- Of 1: 1 solution of MEK and cyclohexanone) was heated and dissolved in 60 parts of MEK with stirring.

After cooling to room temperature, 30 parts of an active ester type curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 223, a toluene solution of a solid content of 65% by mass), 30 parts of a phenolic curing agent ("LA- 16 parts of a benzooxazine compound ("ODA-BOZ" manufactured by JFE Chemical Co., Ltd.), 3 parts of a curing accelerator (4-dimethylaminopyridine (DMAP ), 4 parts of a solid content 5% by mass of MEK solution), spherical silica ("UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd.) surface-treated with an amine-based silane coupling agent (KBM573 manufactured by Shin- 0.078 mu m, specific surface area 30.7 m &lt; ² &gt; / g) were mixed and homogeneously dispersed with a high-speed rotary mixer, followed by filtration through a cartridge filter (SHP020, manufactured by ROKITECHNO) to prepare Resin Composition 1.

&Lt; Example 2: Production of Resin Composition 2 >

In Example 1, the amount of the benzoxazine compound ("ODA-BOZ" manufactured by JFE Chemical Co., Ltd.) was changed from 3 parts to 15 parts. Resin composition 2 was prepared in the same manner as in Example 1 except for the above.

&Lt; Example 3: Production of resin composition 3 >

In Example 1, 3 parts of benzoxazine compound ("ODA-BOZ" manufactured by JFE Chemical Co., Ltd.) was changed to 3 parts of benzoxazine compound ("P-d" manufactured by Shikoku Chemicals Corporation). Resin composition 3 was prepared in the same manner as in Example 1 except for the above.

&Lt; Example 4: Production of Resin Composition 4 >

In Example 1, 30 parts of an active ester type curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active equivalent weight of about 223 and a solid content of 65% by weight of toluene solution) were mixed with an active ester type curing agent ("EXB9416-70BK" , An activating group equivalent of about 274, and a solid content of 70% by mass of MIBK (methyl isobutyl ketone) solution). Resin composition 4 was produced in the same manner as in Example 1 except for the above.

&Lt; Example 5: Production of Resin Composition 5 >

In Example 1, 10 parts of a carbodiimide-based curing agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., active agent equivalent weight about 216, toluene solution having a solid content of 50 mass%) was added. Resin composition 5 was produced in the same manner as in Example 1 except for the above.

&Lt; Example 6: Production of Resin Composition 6 >

In Example 1, 30 parts of an active ester type curing agent (&quot; HPC-8000-65T &quot;, manufactured by DIC Corporation, active equivalent weight of about 223 and a solid content of 65% by weight of toluene solution) was mixed with a naphthol curing agent (SN485, manufactured by Shinnitetsu Sumikin Chemical Co., ) And 16 parts of a phenolic curing agent (&quot; LA-3018-50P &quot;, manufactured by DIC Corporation, active agent equivalent weight: about 151 and a solid content of 50%, 2-methoxypropanol solution) (MEK solution having an active equivalent weight of about 124 and a solid content of 60%) was changed to 12 parts, and a spherical silica surface-treated with an amine-based silane coupling agent (KBM573, manufactured by Shin-Etsu Chemical Co., UFP-30 "manufactured by Kakuko Co., Ltd., average particle diameter 0.078 mu m, specific surface area 30.7 m &lt; ² &gt; / g) was changed to 100 parts. Resin composition 6 was produced in the same manner as in Example 1 except for the above.

&Lt; Example 7: Production of Resin Composition 7 >

In Example 6, the amount of the benzoxazine compound ("ODA-BOZ" manufactured by JFE Chemical Co., Ltd.) was changed from 3 parts to 15 parts. Resin composition 7 was produced in the same manner as in Example 6 except for the above.

&Lt; Example 8: Production of Resin Composition 8 >

In Example 6, 3 parts of a benzoxazine compound ("ODA-BOZ" manufactured by JFE Chemical Co., Ltd.) was changed to 3 parts of a benzoxazine compound ("P-d" manufactured by Shikoku Chemicals Inc.). Resin composition 8 was produced in the same manner as in Example 6 except for the above.

&Lt; Comparative Example 1: Production of Resin Composition 9 >

(UFP-30, manufactured by Denki Kagaku Ko Corporation) surface-treated with an amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd., average particle diameter: 0.078 μm, specific surface area: 30.7 m ² / g) was subjected to surface treatment with spherical silica (average particle diameter 0.77 mu m, specific surface area 5.9 m &lt; ² &gt; / g, manufactured by Adomex Co., C2 &quot;) 110 parts. A resin composition 9 was prepared in the same manner as in Example 1 except for the above.

&Lt; Comparative Example 2: Production of Resin Composition 10 >

In Example 6, spherical silica ("UFP-30" manufactured by Denki Kagaku Ko Corporation) surface-treated with an amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd., average particle diameter: 0.078 μm, specific surface area: 30.7 m ² / g) 100 parts of an amine-based silane coupling agent (Shin-Etsu Kagaku Kogyo Preparation "KBM573") surface-treated spherical silica (average particle diameter in 0.77㎛, a specific surface area of 5.9m ² / g, Thomas O-Tex Co., Ltd. "SO- C2 &quot;). A resin composition 10 was produced in the same manner as in Example 6 except for the above.

&Lt; Comparative Example 3: Production of Resin Composition 11 >

In Example 1, 3 parts of the benzoxazine compound ("ODA-BOZ" manufactured by JFE Chemical Co., Ltd.) was not added. In the same manner as in Example 1 except for the above, resin composition 11 was produced.

&Lt; Comparative Example 4: Production of Resin Composition 12 >

In Example 6, 3 parts of the benzoxazine compound ("ODA-BOZ" manufactured by JFE Chemical Co., Ltd.) was not added. Resin composition 12 was produced in the same manner as in Example 6 except for the above.

&Lt; Measurement of average particle diameter of inorganic filler &

, 0.1 g of a dispersing agent (&quot; SN9228 &quot; manufactured by Sanofocus Corporation) and 10 g of methyl ethyl ketone were placed in a vial bottle and dispersed by ultrasonic wave for 20 minutes. The particle diameter distribution was measured in a batch cell system using a laser diffraction particle size distribution measuring apparatus ("SALD-2200" manufactured by Shimadzu Seisakusho Co., Ltd.), and the average particle diameter was calculated as a median diameter.

[Production of Resin Sheet]

As a support, a PET film ("Lumirror R80" manufactured by Doreya Co., Ltd., thickness 38 탆, softening point 130 캜, hereinafter also referred to as "release PET") having been subjected to release treatment with an alkyd resin releasing agent ).

&Lt; Production of Resin Sheet A &

Each of the resin compositions was uniformly coated on the mold-releasing PET with a die coater so that the thickness of the resin composition layer after drying was 15 占 퐉 and dried at 80 占 폚 for 3 minutes to obtain a resin composition layer on the releasing PET. Subsequently, a roughened surface of a polypropylene film ("ALPAN MA-411" manufactured by Oji-Fetex Co., Ltd., thickness 15 μm) as a protective film was laminated on the surface of the resin composition layer not bonded to the mold- Respectively. Thus, a resin sheet A was obtained in the order of a release PET (support), a resin composition layer, and a protective film.

&Lt; Production of Resin Sheet B &

Each of the resin compositions was uniformly coated on the mold releasing PET with a die coater so that the thickness of the resin composition layer after drying was 6 占 퐉 and dried at 80 占 폚 for 1 minute to obtain a resin composition layer on the releasing PET. Subsequently, a roughened surface of a polypropylene film ("ALPAN MA-411" manufactured by Oji-Fetex Co., Ltd., thickness 15 μm) as a protective film was laminated on the surface of the resin composition layer not bonded to the support to be laminated with the resin composition layer . Thus, a resin sheet B made up of a release PET (support), a resin composition layer, and a protective film in this order was obtained.

[Measurement of peeling strength of copper foil]

<Production of sample>

(1) Treatment of copper foil

(Ra value = 1 mu m) was applied to the copper surface by immersing the glossy surface of "3EC-III" (electric field copper foil, 35 mu m) manufactured by Mitsugi-owned Jokkozzu Co., Ltd. into a McKess et al. And rust-proofing treatment (CL8300) was carried out. This copper foil is called a CZ copper foil. Further, it was heat-treated in an oven at 130 캜 for 30 minutes.

(2) Lamination of copper foil and formation of insulating layer

The protective film was peeled off from each resin sheet A previously prepared, and a glass cloth-base epoxy resin double-sided copper clad laminate (hereinafter referred to as &quot; glass cloth substrate epoxy resin double-sided copper clad laminate &quot; (The thickness of the copper foil was 18 mu m, the thickness of the substrate was 0.4 mm, "R1515A" manufactured by Panasonic Corporation). The lamination treatment was carried out by reducing the pressure for 30 seconds to bring the air pressure to 13 hPa or less, followed by pressing at 100 DEG C and a pressure of 0.74 MPa for 30 seconds. The release PET was peeled from the laminated resin sheet. The treated surface of the CZ copper foil was laminated on the resin composition layer under the same conditions as above. Then, the resin composition layer was cured at 190 DEG C for 90 minutes under a curing condition to form an insulating layer, thereby preparing a sample.

&Lt; Measurement of peel strength (adhesion 1)

The prepared sample was cut into small pieces of 150 x 30 mm. (10 mm in width and 100 mm in length) was cut into a small piece of copper foil using a cutter and the copper foil was peeled off and held with a holding tool (automobile tester "AC-50C-SL" The load at the time of peeling 35 mm in the vertical direction at a rate of 50 mm / min at room temperature using a Tron universal testing machine was measured according to JIS C6481.

&Lt; Measurement of copper foil peel strength (adhesion property 2) after environmental test (HAST) >

The produced sample was subjected to an accelerated environmental test (environmental test) for 100 hours under the conditions of 130 占 폚 and 85% RH using an advanced accelerated life test apparatus ("PM422" manufactured by Gusumoto Chemical Industry Co., Ltd.). Thereafter, one end of the copper foil was peeled off and held with a gripping tool (manufactured by TSE, automobile type tester, "AC-50C-SL") in the same manner as in the measurement of the adhesion property 1, Minute, the load at the time of peeling 35 mm in the vertical direction was measured according to JIS C6481.

In addition, a case where the measurement result at the adhesion 2 was less than 0.20 kgf / cm was evaluated as &quot; X &quot;, and a case where the measurement result was 0.20 kgf / cm or more was evaluated as &quot;

[Measurement of thickness of insulating layer between conductor layers and insulation reliability of insulating layer]

(Preparation of substrate for evaluation)

(1) ground treatment of inner layer circuit board

A copper clad epoxy resin double-sided copper clad laminate (copper foil having a thickness of 3 mu m and a thickness of 3 mu m) having circuit conductors (copper) formed on both surfaces thereof with wiring patterns of L / S (line / space) = 2 mu m / 0.15 mm, &quot; HL832NSF LCA &quot; manufactured by Mitsubishi Chemical Corporation, size 255 x 340 mm) was prepared. Both surfaces of the laminate were subjected to organic film treatment of the copper surface with &quot; FlatBOND-FT &quot;

(2) Laminate of resin sheet

The protective film was peeled off from each resin sheet B prepared in advance, and the resin composition layer was laminated on both sides of the laminate so that the resin composition layer was in contact with the laminate by using a batch type vacuum pressure laminator (Niko Material Stamp, 2 stage built-up laminator, CVP700) Lt; / RTI &gt; The laminate was decompressed for 30 seconds to adjust the air pressure to 13 hPa or less, and compression was performed at 130 캜 under a pressure of 0.74 MPa for 45 seconds. Then, hot pressing was performed at 120 DEG C and a pressure of 0.5 MPa for 75 seconds.

(3) Thermal curing of the resin composition layer

The laminate laminated with the resin sheet was placed in an oven at 100 캜, transferred to an oven at 180 캜 for 30 minutes, and thermally cured for 30 minutes to form an insulating layer having a thickness of 5 탆, and the releasing PET was peeled off. This is referred to as substrate A.

(4) Step of performing harmonic treatment

The insulating layer of the substrate A was subjected to a desmear treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was carried out.

Wet desmear treatment:

Was added to a swelling liquid (aqueous solution of "Swelling Dip · Securigant P", manufactured by Atotech Japan Co., Ltd., diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C for 5 minutes and then with an oxidizing agent solution (Concentrate Compact CP ", an aqueous potassium permanganate concentration of about 6%, and a sodium hydroxide concentration of about 4%) at 80 ° C. for 10 minutes, and finally with a neutralizing solution (" Reduction Solution · Securigant P ", aqueous sulfuric acid solution manufactured by Atotech Japan) After immersing at 40 DEG C for 5 minutes, drying was carried out at 80 DEG C for 15 minutes. This is referred to as a coarse substrate A.

(5) Step of forming conductor layer

(5-1) Electroless plating process

In order to form a conductor layer on the surface of the insulating layer of the coarse substrate A, a plating process (a copper plating process using a chemical solution manufactured by Atotech Japan) including the following steps 1 to 6 was performed to form a conductor layer .

1. Alkali cleaning (cleaning and charge control of the surface of insulating layer with via hole)

The surface of the coarsened substrate A was cleaned using a Cleaning cleaner Securiganth 902 (trade name) at 60 ° C for 5 minutes.

2. Soft etching (cleaning in via hole)

The surface of the coarsened substrate A was treated with an aqueous solution of sulfuric acid-oxidized peroxodisulfate sodium at 30 DEG C for 1 minute.

3. Pre-dip (adjustment of charge on the insulating layer surface for Pd application)

The surface of the coarsened substrate A was treated with Pre.Dip Neoganth B (trade name) at room temperature for 1 minute.

4. Providing an activator (imparting Pd to the surface of the insulating layer)

The surface of the coarsened substrate A was treated with Activator Neoganth 834 (trade name) at 35 DEG C for 5 minutes.

5. Reduction (reduction of Pd given to insulating layer)

The surface of the harmonic substrate A was treated with a mixture solution of Reducer Neoganth WA (trade name) and Reducer Accelerator 810 mod. (Trade name) at 30 ° C for 5 minutes.

6. Electroless copper plating process (depositing Cu on the surface of the insulating layer (Pd surface))

The surface of the harmony substrate A was treated with a mixture solution of Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name) and Reducer Cu For 20 minutes. The thickness of the formed electroless copper plating layer was 0.8 mu m.

(5-2) Electroplating process

Subsequently, an electrolytic copper plating process was performed under the condition that copper was filled in the via hole by using a chemical solution manufactured by Atotech Japan. Thereafter, as a resist pattern for patterning by etching, a land pattern of 1 mm in diameter, which was conducted to a via hole, and a circular conductor pattern of 10 mm in diameter, which was not connected to the lower layer conductor, A conductor layer having a land and a conductor pattern was formed. Next, the annealing was performed at 200 캜 for 90 minutes. This substrate was referred to as &quot; evaluation substrate B &quot;.

&Lt; Measurement of thickness of insulating layer between conductor layers >

The evaluation substrate B was subjected to cross-sectional observation using an FIB-SEM composite device ("SMI3050SE" manufactured by SII Nanotechnology Co., Ltd.). Specifically, the cross section in the direction perpendicular to the surface of the conductor layer was cut off by FIB (focused ion beam), and the thickness of the insulation layer between the conductor layers was measured from the cross-sectional SEM image. For each sample, five randomly selected sections of SEM images were observed, and the average value thereof was shown in the following table as the thickness (mu m) of the insulating layer between the conductor layers.

&Lt; Evaluation of Insulation Reliability of Insulating Layer &

The side of the circular conductor with a diameter of 10 mm of the evaluation substrate B obtained above was used as a positive electrode and the side of the laminate lattice conductor (copper) connected to a land having a diameter of 1 mm as a negative electrode was subjected to an advanced acceleration lifetime tester Quot; ECM-100 &quot; manufactured by J-RAS Co., Ltd.), and the insulation resistance value at 200 deg. C under the conditions of 130 deg. C, 85% relative humidity and 3.3V DC voltage was measured using an electrochemical migration tester ). If performed six times with the measurement, and that the resistance in both of the six-point test piece 10 ⁷ Ω the "○" La, and less than 1 even 10 ⁷ Ω or more is to to as "×", and when the result and isolated The resistance values are shown in the following table. The insulation resistance values shown in the following table are the lowest values of the insulation resistance values of the six test pieces.

The components used in the preparation of Resin Compositions 1 to 12 and their blending amounts (in terms of nonvolatile content) are shown in the following table.

In Examples 1 to 8, even when the components (D) to (G) were not contained, it was confirmed that the results were the same as those of the above-mentioned Examples although there were differences in the degree.

1: first conductor layer
11: Main surface of first conductor layer
2: second conductor layer
21: Main surface of second conductor layer
3: Insulating layer
t1: the distance between the first conductor layer and the second conductor layer (the thickness of the insulating layer between the first and second conductor layers)
t2: thickness of the entire insulating layer

Claims (16)

(A) an epoxy resin, (B) a benzoxazine compound, and (C) an inorganic filler having an average particle diameter of 100 nm or less,
And the content of the component (C) is 40% by mass or more when the content of the nonvolatile component in the resin composition is 100% by mass. (A) an epoxy resin, (B) a benzoxazine compound, (C) an inorganic filler having a specific surface area of 15 m ² / g or more,
And the content of the component (C) is 40% by mass or more when the content of the nonvolatile component in the resin composition is 100% by mass. The resin composition according to claim 1 or 2, further comprising (D) a curing agent. The resin composition according to claim 3, wherein the component (D) comprises at least one of a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a cyanate ester-based curing agent and a carbodiimide-based curing agent. 3. The resin composition according to claim 1 or 2, wherein the content of the component (B) is 0.1% by mass or more and 30% by mass or less based on 100% by mass of the nonvolatile component in the resin composition. The resin composition according to claim 1 or 2, wherein the component (B) is represented by the following formula (B-1).
The formula (B-1)

In the above formula (B-1)
R ¹ represents an n-valent group, and each R ² independently represents a halogen atom, an alkyl group, or an aryl group. n represents an integer of 2 to 4, and m represents an integer of 0 to 4. The resin composition according to claim 6, wherein in the formula (B-1), R ¹ is an n-valent group consisting of an arylene group, an alkylene group, an oxygen atom or a combination of two or more thereof. The resin composition according to claim 6, wherein in the formula (B-1), m represents 0. The resin composition according to claim 1 or 2, which is for forming an insulating layer of a printed wiring board. The resin composition according to claim 1 or 2, which is used for forming an interlayer insulating layer of a printed wiring board. A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 10 provided on the support. 12. The resin sheet according to claim 11, wherein the thickness of the resin composition layer is 15 占 퐉 or less. 12. The semiconductor device according to claim 11, further comprising a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer, wherein an interval between the first conductor layer and the second conductor layer is 6 mu m Or less, of the resin sheet for forming the insulating layer. A printed wiring board comprising a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,
Wherein the insulating layer is a cured product of the resin composition according to any one of claims 1 to 10. 15. The printed wiring board according to claim 14, wherein a distance between the first conductor layer and the second conductor layer is 6 mu m or less. A semiconductor device comprising the printed wiring board according to claim 14.

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