KR20210109462A - Resin composition - Google Patents

Abstract

Provided are a resin composition capable of obtaining a cured product in which occurrence of warpage is suppressed, a resin sheet including the resin composition, a printed wiring board provided with an insulating layer formed using the resin composition, and a semiconductor device. Provided is a resin composition including (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, wherein the (A) component contains an epoxy resin having a hyperbranched structure.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition. Moreover, it is related with the resin sheet obtained using the said resin composition, a printed wiring board, and a semiconductor device.

As a manufacturing technique of a printed wiring board, the manufacturing method by the buildup system which piles up an insulating layer and a conductor layer alternately is known.

As an insulating material of the printed wiring board used for such an insulating layer, the resin composition is disclosed by patent document 1, for example.

[Patent Document 1] Japanese Patent Laid-Open No. 2019-53092

By the way, in recent years, suppression of the curvature which arises when forming an insulating layer is calculated|required by the insulating layer used for the wiring board provided with a buried type wiring layer, for example.

The subject of this invention is the resin composition which can obtain the hardened|cured material by which generation|occurrence|production of curvature was suppressed; a resin sheet containing the resin composition; It is providing the printed wiring board provided with the insulating layer formed using the said resin composition, and a semiconductor device.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the said subject, the present inventors discovered that the said subject was solvable by containing the epoxy resin which has a hyperbranched structure as an epoxy resin, and came to complete this invention.

That is, the present invention includes the following contents.

[1] (A) an epoxy resin,

(B) a curing agent, and

(C) a resin composition comprising an inorganic filler,

(A) The resin composition in which a component contains the epoxy resin which has a hyperbranched structure.

[2] The resin composition according to [1], wherein the epoxy resin having a hyperbranched structure has a molecular weight of 1000 or more and 10000 or less.

[3] The epoxy equivalent of the epoxy resin having a hyperbranched structure, 250 g/eq. more than 700g/eq. The resin composition as described in [1] or [2] which is the following.

[4] The resin according to any one of [1] to [3], wherein the epoxy resin having a hyperbranched structure has a multi-branched structure in which a structure derived from a trifunctional compound or more and a structure derived from a bifunctional compound are alternately bonded. composition.

[5] The resin composition according to any one of [1] to [4], wherein the epoxy resin having a hyperbranched structure contains a cyclic structure.

[6] The resin composition according to [4], wherein the structure derived from the bifunctional compound includes a cyclic structure.

[7] The resin according to any one of [1] to [6], wherein the content of the epoxy resin having a hyperbranched structure is 3% by mass or more and 10% by mass or less when the nonvolatile component in the resin composition is 100% by mass. composition.

[8] The resin composition according to any one of [1] to [7], wherein the content of the epoxy resin having a hyperbranched structure is 20% by mass or more and 50% by mass or less when the entire component (A) is 100% by mass. .

[9] The resin composition according to any one of [1] to [8], wherein the component (B) contains any one of an active ester curing agent, a phenol curing agent, a benzoxazine curing agent, and a carbodiimide curing agent. .

[10] The resin composition according to any one of [1] to [9], further comprising (D) a thermoplastic resin.

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

[12] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [10].

[13] A semiconductor device comprising the printed wiring board according to [12].

ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can obtain the hardened|cured material by which generation|occurrence|production of curvature was suppressed; a resin sheet containing the resin composition; A printed wiring board provided with the insulating layer formed using the said resin composition, and a semiconductor device can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on the suitable embodiment. However, the present invention is not limited to the following embodiments and examples, and may be arbitrarily changed and implemented without departing from the scope of the claims of the present invention and their equivalents.

[resin composition]

The resin composition of this invention is a resin composition containing (A) epoxy resin, (B) hardening|curing agent, and (C) inorganic filler, Comprising: (A) component contains the epoxy resin which has a hyperbranched structure. In this invention, the hardened|cured material by which generation|occurrence|production of curvature was suppressed can be obtained by containing the epoxy resin which has a hyperbranched structure as (A) component. Moreover, in this invention, it is excellent also normally in plating adhesiveness and the plating adhesiveness after a reliability test, and also can obtain the hardened|cured material with a low coefficient of linear thermal expansion (CTE).

The resin composition may further contain optional components in combination with the components (A) to (C). As arbitrary components, (D) thermoplastic resin, (E) hardening accelerator, (F) flame retardant, (G) other additives, etc. are mentioned, for example. Hereinafter, each component contained in a resin composition is demonstrated in detail.

<(A) Epoxy resin>

The resin composition contains (A) epoxy resin as (A) component, (A) component contains the epoxy resin which has a hyperbranched structure. (A) By containing a component in a resin composition, it becomes possible to obtain the hardened|cured material by which generation|occurrence|production of curvature was suppressed.

The epoxy resin having a hyperbranched structure refers to an epoxy resin having a multi-branched structure having a plurality of branches and having an epoxy group at the terminal. The epoxy resin having a hyperbranched structure preferably has an epoxy group at the terminal of the branched chain of 4 or more (preferably 6 or more, more preferably 8 or more), and having an epoxy group at all ends of the branched chain It is particularly preferred. Among them, preferably, the epoxy resin having a hyperbranched structure refers to an epoxy resin having a multi-branched structure in which a structure derived from a trifunctional or higher compound and a structure derived from a bifunctional compound are alternately bonded, and having an epoxy group at the terminal. . An epoxy resin having such a preferable hyperbranched structure can be obtained by reacting a trifunctional or higher functional compound as the center of a molecular structure with a bifunctional compound. The epoxy resin having a hyperbranched structure may have a free space around the branching portion in that it has a multi-branched structure. By having free space, even if a resin composition hardens|cures, it becomes difficult to shrink|contract, and since it is hard to generate|occur|produce a stress, it is thought that generation|occurrence|production of curvature is suppressed as a result.

It is preferable that a cyclic structure is included from a viewpoint of acquiring the effect of this invention remarkably, and, as for the epoxy resin which has a hyperbranched structure, it is more preferable that an aromatic structure is included. An aromatic structure is a chemical structure generally defined as aromatic, and polycyclic aromatic and aromatic heterocyclic ring are also included. As a cyclic structure, a bisphenol skeleton, a phenylene skeleton, a naphthylene skeleton, a dimethylmethylene biscyclohexylene skeleton, anthracene skeleton, etc. are mentioned, for example, A bisphenol skeleton is preferable. As the bisphenol skeleton, bisphenol A skeleton, bisphenol F skeleton, bisphenol AP skeleton, bisphenol AF skeleton, bisphenol B skeleton, bisphenol BP skeleton, bisphenol S skeleton, bisphenol Z skeleton, bisphenol C skeleton, bisphenol TMC skeleton, bisphenol AF skeleton, bisphenol E skeleton Skeleton, bisphenol G skeleton, bisphenol M skeleton, bisphenol PH skeleton, etc. are mentioned, Bisphenol A skeleton is preferable.

The cyclic structure preferably has either a structure derived from a trifunctional or higher functional compound and a structure derived from a bifunctional compound, and more preferably a structure derived from a bifunctional compound.

The ring in the cyclic structure may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an arylalkyl group having 7 to 12 carbon atoms, a silyl group, an acyl group, an acyloxy group, a carboxy group, A sulfo group, a cyano group, a nitro group, a hydroxyl group, a mercapto group, an oxo group, etc. are mentioned.

The trifunctional or higher compound is a compound capable of becoming a core of a hyperbranched structure, and has a functional group capable of reacting with a bifunctional compound. The trifunctional or higher compound has a structure derived from the trifunctional or higher functional compound in the hyperbranched structure. As a trifunctional or more than trifunctional compound, it is preferable that they are a trifunctional compound and a tetrafunctional compound, and a tetrafunctional compound is more preferable.

As a functional group which a trifunctional or more than trifunctional compound has, an OH group (including a phenolic hydroxyl group), an amino group, an epoxy group, a glycidyl ether group etc. are mentioned, for example, OH group is preferable.

Specific examples of the trifunctional or higher compound include pentaerythritol, glycerin, and compounds represented by the following formulas (1) to (12). Especially, as a trifunctional or more than trifunctional compound, pentaerythritol is preferable.

A bifunctional compound is a compound which can couple|bond with the functional group of a trifunctional or more than trifunctional compound, and has a functional group which can react with the functional group of a trifunctional or more than trifunctional compound. The bifunctional compound becomes a structure derived from the bifunctional compound in the hyperbranched structure.

As a functional group which a bifunctional compound has, an epoxy group, a glycidyl ether group, OH group (including phenolic hydroxyl group), an amino group etc. are mentioned, for example, An epoxy group and a glycidyl ether group are preferable, and glycidyl ether group is preferable. A dilether group is more preferable.

From a viewpoint of being excellent in heat resistance, it is preferable that a bifunctional compound contains a cyclic structure, and, especially, it is more preferable that an aromatic structure is included.

Specific examples of the bifunctional compound include compounds represented by the following formulas (13) to (41). Among them, the compound represented by the general formula (13) is preferable.

The epoxy resin which has a hyperbranched structure can be prepared by making a trifunctional or more than trifunctional compound, a bifunctional compound, and an epoxy compound react.

An epoxy compound is a compound which introduce|transduces an epoxy group at the terminal. As an epoxy compound, epichlorohydrin is mentioned, for example, Epichlorohydrin is preferable.

The reaction temperature is preferably 90°C or higher, more preferably 100°C or higher, still more preferably 110°C or higher, preferably 200°C or lower, more preferably 150°C or lower, still more preferably 120°C or lower. am.

The reaction time is preferably 2 hours or more, more preferably 3 hours or more, still more preferably 4 hours or more, preferably 7 hours or less, more preferably 6 hours or less, still more preferably 5 hours or less. am.

The molecular weight of the epoxy resin having a hyperbranched structure is preferably 1000 or more, more preferably 1200 or more, still more preferably 1400 or more, preferably 10000 or less, more Preferably it is 7500 or less, More preferably, it is 5000 or less. Molecular weight can be measured with a mass spectrometer.

As a weight molecular weight of the epoxy resin having a hyperbranched structure, from the viewpoint of significantly obtaining the effect of the present invention, preferably 1000 or more, more preferably 1200 or more, still more preferably 1400 or more, preferably 10000 or less, More preferably, it is 7500 or less, More preferably, it is 5000 or less.

The weight average molecular weight of resin can be measured as a polystyrene conversion value by the gel permeation chromatography (GPC) method.

The epoxy equivalent of the epoxy resin having a hyperbranched structure is preferably 250 g/eq. above, more preferably 300 g/eq. or more, more preferably 350 g/eq. or more, preferably 700 g/eq. Hereinafter, more preferably 500 g/eq. Hereinafter, more preferably 450 g/eq. Below, 400 g/eq. is below. Epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of an epoxy group. This epoxy equivalent can be measured according to JISK7236.

As a specific example of the epoxy resin which has a hyperbranched structure, "PHE4h", "PHE5", "PHE15" etc. of RSC Adv., 2015, 5, 35080-35088 are mentioned, for example.

As the component (A), an epoxy resin other than an epoxy resin having a hyperbranched structure (hereinafter, an epoxy resin other than an epoxy resin having a hyperbranched structure may be simply referred to as “component (A-1)” in some cases.) it's fine to do Examples of such an epoxy resin include a bixylenol-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, and a trisphenol-type epoxy resin. Epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidylamine type epoxy resin Cydyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, butadiene structure epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane A type epoxy resin, a cyclohexane dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, a tetraphenylethane type epoxy resin, etc. are mentioned. (A-1) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

(A-1) It is preferable that a component is an epoxy resin which has two or more epoxy groups in 1 molecule. From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the nonvolatile component of the component (A-1) is preferably 50% by mass or more. , More preferably, it is 60 mass % or more, Especially preferably, it is 70 mass % or more.

The component (A-1) includes a component (A-1) that is liquid at a temperature of 20°C and a component (A-1) that is solid at a temperature of 20°C. (A-1) component may contain only liquid (A-1) component, may contain only solid (A-1) component, liquid (A-1) component and solid (A-) 1) Although it may contain in combination, it is preferable to include solid (A-1) component and liquid (A-1) component in combination from a viewpoint of acquiring the desired effect of this invention remarkably.

The solid (A-1) component is preferably a solid (A-1) component having three or more epoxy groups in one molecule, and an aromatic solid (A-1) having three or more epoxy groups in one molecule. A component is more preferable.

As a solid component (A-1), a bixylenol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, naphthol Preferred epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, and tetraphenylethane type epoxy resins, biphenyl type epoxy resins more preferably.

Specific examples of the solid component (A-1) include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700", "HP-4710" by DIC company (naphthalene type tetrafunctional epoxy resin); "N-690" by DIC (cresol novolak type epoxy resin); "N-695" by DIC (cresol novolak type epoxy resin); "HP-7200", "HP-7200HH", and "HP-7200H" (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" by DIC company (naphthylene ether type epoxy resin); "EPPN-502H" by a Nippon Kayaku company (trisphenol type epoxy resin); "NC7000L" by a Nippon Kayaku company (naphthol novolak type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) by a Nippon Kayaku company; "ESN475V" (naphthol type epoxy resin) by the Nitetsu Chemical & Materials company; "ESN485" (naphthol novolak-type epoxy resin) by the Nitetsu Chemical & Materials company; "YX4000H", "YX4000", "YL6121" by Mitsubishi Chemical Corporation (biphenyl type epoxy resin); "YX4000HK" by Mitsubishi Chemical (bixylenol type epoxy resin); "YX8800" by Mitsubishi Chemical (anthracene type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" by a Mitsubishi Chemical company (bisphenol AF type|mold epoxy resin); "YL7800" by Mitsubishi Chemical (fluorene type epoxy resin); "jER1010" manufactured by Mitsubishi Chemical Corporation (solid bisphenol A epoxy resin); "jER1031S" (tetraphenylethane type epoxy resin) by a Mitsubishi Chemical company, etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

As a liquid (A-1) component, the liquid (A-1) component which has two or more epoxy groups in 1 molecule is preferable.

As the liquid component (A-1), 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 A novolak-type epoxy resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexane-type epoxy resin, a cyclohexanedimethanol-type epoxy resin, a glycidylamine-type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and bisphenol A A type epoxy resin is more preferable.

As a specific example of liquid (A-1) component, "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) by DIC Corporation; "828US", "jER828EL", "825", "Epicoat 828EL" by Mitsubishi Chemical Corporation (bisphenol A epoxy resin); "jER807", "1750" by Mitsubishi Chemical Corporation (bisphenol F-type epoxy resin); "jER152" (phenol novolak-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" and "630LSD" by Mitsubishi Chemical (glycidylamine type epoxy resin); "ZX1059" (mixture of a bisphenol A epoxy resin and a bisphenol F type epoxy resin) by the Nitetsu Chemical & Materials company; "EX-721" by the Nagase Chemtex company (glycidyl ester type epoxy resin); "Celoxide 2021P" by Daicel (alicyclic epoxy resin which has ester skeleton); "PB-3600" by Daicel (epoxy resin which has a butadiene structure); "ZX1658", "ZX1658GS" (liquid 1, 4- glycidyl cyclohexane type epoxy resin), etc. by the Nitetsu Chemical & Materials company are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

When the liquid (A-1) component and the solid (A-1) component are used in combination, their quantity ratio (liquid (A-1) component: solid (A-1) component) is a mass ratio, Preferably 1:1 to 1:20, more preferably 1:1.5 to 1:15, particularly preferably 1:2 to 1:10. When the amount ratio of the liquid component (A-1) and the solid component (A-1) is within such a range, the desired effect of the present invention can be obtained remarkably. Moreover, when using in the form of a resin sheet normally, moderate adhesiveness is formed. Moreover, when using in the form of a resin sheet normally, sufficient flexibility is acquired and handling property improves. In addition, usually, a cured product having sufficient breaking strength can be obtained.

(A-1) The epoxy equivalent of a component becomes like this. Preferably it is 50 g/eq. to 5000 g/eq., more preferably 50 g/eq. to 3000 g/eq., more preferably 80 g/eq. to 2000 g/eq., even more preferably 110 g/eq. to 1000 g/eq. By setting it as this range, the crosslinking density of the hardened|cured material of a resin composition becomes enough, and the insulating layer with small surface roughness can be formed.

(A-1) The weight average molecular weight (Mw) of the component is preferably 100 to 5000, more preferably 250 to 3000, still more preferably 400 to 1500 from the viewpoint of remarkably obtaining the desired effect of the present invention. .

Content of the epoxy resin which has a hyperbranched structure, from a viewpoint of acquiring the effect of this invention remarkably, when the non-volatile component in a resin composition is 100 mass %, Preferably it is 3 mass % or more, More preferably, it is 4 mass %. % or more, more preferably 5 mass% or more. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and particularly preferably 7% by mass or less from the viewpoint of remarkably obtaining the desired effect of the present invention.

In addition, in this invention, unless otherwise indicated, content of each component in a resin composition is a value when the non-volatile component in a resin composition is 100 mass %.

(A-1) When content of component makes 100 mass % of non-volatile components in a resin composition from a viewpoint of obtaining the insulating layer which shows favorable mechanical strength and insulation reliability, Preferably it is 1 mass % or more, More preferably Preferably it is 5 mass % or more, More preferably, it is 8 mass % or more. The upper limit of the content of the epoxy resin is preferably 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less from the viewpoint of remarkably obtaining the desired effect of the present invention.

(A) When content of the whole component makes the non-volatile component in a resin composition 100 mass % from a viewpoint of acquiring the effect of this invention remarkably, Preferably it is 1 mass % or more, More preferably, it is 5 mass % or more. , More preferably, it is 10 mass % or more. The upper limit of the content of the epoxy resin is preferably 35% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less from the viewpoint of remarkably obtaining the desired effect of the present invention.

Content of the epoxy resin which has a hyperbranched structure, from a viewpoint of acquiring the effect of this invention remarkably, when (A) the whole component is 100 mass %, Preferably it is 20 mass % or more, More preferably, it is 25 mass %. More preferably, it is 30 mass % or more. The upper limit is preferably 50 mass % or less, more preferably 45 mass % or less, particularly preferably 40 mass % or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.

The content when the nonvolatile component in the resin composition of the epoxy resin having a hyperbranched structure is 100% by mass is h (mass%), and the nonvolatile component in the resin composition of the component (A-1) is 100% by mass. From the viewpoint of remarkably obtaining the effect of the present invention, h/(h+e) is preferably 0.1 or more, more preferably 0.2 or more, further preferably is 0.3 or more, preferably 5 or less, more preferably 3 or less, still more preferably 1 or less.

<(B) curing agent>

A resin composition contains a hardening|curing agent as (B) component. (B) A hardening|curing agent has a function which reacts with (A) component normally, and hardens a resin composition. (B) A hardening|curing agent may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

(B) As the curing agent, a compound capable of curing the resin composition by reacting with the component (A) can be used, for example, an active ester curing agent, a phenol curing agent, a benzoxazine curing agent, a carbodiimide curing agent, and an acid anhydride curing agent, an amine curing agent, and a cyanate ester curing agent. Among them, any one of an active ester-based curing agent, a phenol-based curing agent, a benzoxazine-based curing agent, and a carbodiimide-based curing agent is preferable from the viewpoint of significantly obtaining the effects of the present invention, and an active ester-based curing agent and a phenol-based curing agent Either one is more preferable.

Examples of the active ester curing agent include curing agents having one or more active ester groups in one molecule. Among them, as the active ester-based curing agent, phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. having two or more ester groups with high reaction activity in one molecule compounds are preferred. It is preferable that the said active ester type hardening|curing agent is obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound, and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is more preferable.

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

Examples of the phenolic compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac, etc. are mentioned. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol to one molecule of dicyclopentadiene.

Preferred specific examples of the active ester curing agent include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and phenol novolac and active ester compounds containing benzoylate. Especially, the active ester compound containing a naphthalene structure and the active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene type diphenol structure" represents a divalent structure consisting of phenylene-dicyclopentylene-phenylene.

Commercially available active ester curing agents are active ester compounds containing a dicyclopentadiene type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC" -8000-65T", "HPC-8000H-65TM", "HPC-8150-62T", "EXB-8000L", "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC); As an active ester compound containing a naphthalene structure, "EXB-8100L-65T", "EXB-8150L-65T", "EXB9416-70BK" (made by DIC); "DC808" (made by Mitsubishi Chemical) as an active ester compound containing the acetylated product of phenol novolak; "YLH1026" (made by Mitsubishi Chemical) as an active ester compound containing the benzoyl compound of phenol novolak; As an active ester curing agent which is an acetylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical); "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent that is a benzoyl product of phenol novolac; and the like.

As a phenolic hardening|curing agent, the hardening|curing agent which has 1 or more, Preferably it has 2 or more hydroxyl groups couple|bonded with the aromatic ring (a benzene ring, a naphthalene ring, etc.) in 1 molecule is mentioned. Especially, the compound which has the hydroxyl group couple|bonded with the benzene ring is preferable. Moreover, from a viewpoint of heat resistance and water resistance, the phenolic hardening|curing agent which has a novolak structure is preferable. Furthermore, from an adhesive viewpoint, a nitrogen-containing phenolic hardening|curing agent is preferable, and a triazine skeleton containing phenolic hardening|curing agent is more preferable. In particular, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion.

As a specific example of a phenol type hardening|curing agent and a naphthol type hardening|curing agent, Meiwa Kasei Corporation make "MEH-7700", "MEH-7810", "MEH-7851", "MEH-8000H"; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-495V" manufactured by Nittetsu Chemical & Materials , "SN-375", "SN-395"; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1365", "LA-3018", "LA-3018-50P" manufactured by DIC Corporation, "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165"; "GDP-6115L", "GDP-6115H", "ELPC75", etc. made from Gunei Chemical Co., Ltd. are mentioned.

As a specific example of a benzoxazine type hardening|curing agent, "HFB2006M" by a Showa Kobunshi company, "P-d" by a Shikoku Kasei Co., Ltd. product, and "F-a" are mentioned.

Specific examples of the carbodiimide-based curing agent include "V-03", "V-05", "V-07" manufactured by Nisshinbo Chemical; Stavaxol (registered trademark) P manufactured by Rhein Chemie Co., Ltd., etc. are mentioned.

As an acid anhydride type hardening|curing agent, the hardening|curing agent which has one or more acid anhydride groups in 1 molecule is mentioned. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic acid. Anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, anhydride Trimellitic acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl)-naphtho [1,2-C] furan-1, Polymeric acid anhydrides, such as 3-dione, ethylene glycol bis (anhydro trimellitate), and styrene maleic acid resin which copolymerized styrene and maleic acid, etc. are mentioned. A commercial item may be used for an acid anhydride type hardening|curing agent, For example, "MH-700" by a Shin-Nippon Rika company, etc. are mentioned.

Examples of the amine-based curing agent include curing agents having at least one amino group in one molecule, for example, aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, and the like. From the viewpoint of exhibiting a desired effect, aromatic amines are preferable. Primary amine or secondary amine is preferable and, as for an amine type hardening|curing agent, primary amine is more preferable. Specific examples of the amine curing agent include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone , 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4, 4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl ) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4- (4-amino) Phenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4 ,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. are mentioned. . Commercially available amine curing agents may be used, for example, "KAYABOND C-200S", "KAYABOND C-100", "Kayahard AA", "Kayahard AB", "Kayahard AS" manufactured by Nippon Kayaku Co., Ltd. , "Epicure W" manufactured by Mitsubishi Chemical, etc. are mentioned.

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6- Dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4- Cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cya bifunctional cyanate resins such as natephenyl)thioether and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; Prepolymers in which these cyanate resins are partially triazinated; and the like. As a specific example of a cyanate ester type hardening|curing agent, "PT30" and "PT60" by Ronza Japan (both are phenol novolak-type polyfunctional cyanate ester resin); "ULL-950S" (polyfunctional cyanate ester resin); "BA230", "BA230S75" (a prepolymer in which a part or all of bisphenol A dicyanate was triazined and trimerized); and the like.

(B) The content of the curing agent is preferably 1% by mass or more, more preferably 5% by mass or more, when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of significantly obtaining the effect of the present invention. Preferably it is 10 mass % or more, Preferably it is 25 mass % or less, More preferably, it is 20 mass % or less, More preferably, it is 15 mass % or less.

When the number of epoxy groups in the component (A) is 1, the number of active groups in the (B) curing agent is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, preferably 2 or less, more Preferably it is 1.8 or less, More preferably, it is 1.6 or less, Especially preferably, it is 1.4 or less. Here, "the number of epoxy groups of (A) component" is the value which summed up all the values obtained by dividing the mass of the nonvolatile component of (A) component present in the resin composition by the epoxy equivalent. In addition, "the number of active groups of (B) hardening|curing agent" is the sum total of the value which divided the mass of the nonvolatile component of (B) hardening|curing agent which exists in a resin composition by the active group equivalent. When the number of active groups of the (B) curing agent in the case where the number of epoxy groups in the component (A) is 1 is in the above range, the desired effect of the present invention can be obtained remarkably.

<(C) Inorganic filler>

A resin composition contains an inorganic filler as (C)component. (C) By containing an inorganic filler in a resin composition, it becomes possible to obtain hardened|cured material with a low linear thermal expansion coefficient.

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

(C) As a commercial item of an inorganic filler, For example, "UFP-30" by Denki Chemical Industries; "SP60-05", "SP507-05" by the Shin-Nitetsu Sumikin Materials company; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Adomatex Corporation; "UFP-30" by Denka Corporation; "Silly writing NSS-3N", "Silly writing NSS-4N", "Silly writing NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "SC2050-SXF" manufactured by Adomatex Corporation; and the like.

(C) The average particle diameter of the inorganic filler is preferably 0.01 µm or more, more preferably 0.05 µm or more, particularly preferably 0.1 µm or more, from the viewpoint of remarkably obtaining the desired effect of the present invention, preferably It is 5 micrometers or less, More preferably, it is 2 micrometers or less, More preferably, it is 1 micrometer or less.

(C) The average particle diameter of an inorganic filler can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, it can measure by creating the particle diameter distribution of an inorganic filler on a volume basis with a laser diffraction scattering type particle diameter distribution measuring apparatus, and making the median diameter into an average particle diameter. As the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone were measured and placed in a vial bottle and dispersed by ultrasonic waves for 10 minutes can be used. Using a laser diffraction particle size distribution measuring device, the measurement sample was measured for the volume-based particle size distribution of the inorganic filler by a flow cell method using a light source wavelength of blue and red, and the median diameter from the obtained particle size distribution The average particle diameter is calculated as As a laser diffraction type particle size distribution measuring apparatus, "LA-960" by Horiba Corporation, etc. are mentioned, for example.

(C) a specific surface area of the inorganic filler is, in terms remarkably obtain the desired effect of the present invention, preferably 1m ² / g or more, more preferably 2m ² / g or more, and particularly preferably from 3m ² / g or more am. Although there is no particular limitation on the upper limit, it is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area was determined by adsorbing nitrogen gas to the sample surface using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec), and calculating the specific surface area using the BET multi-point method to determine the specific surface area of the inorganic filler. It is obtained by measuring.

(C) It is preferable that the inorganic filler is treated with the surface treating agent from a viewpoint of improving moisture resistance and dispersibility. As the surface treatment agent, for example, a fluorine-containing silane coupling agent, an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an alkoxysilane, an organosilazane compound, a titanate-based coupler A ring agent etc. are mentioned. In addition, a surface treatment agent may be used individually by 1 type, and may be used combining two or more types arbitrarily.

As a commercial item of a surface treatment agent, Shin-Etsu Chemical Co., Ltd. make "KBM403" (3-glycidoxypropyl trimethoxysilane), Shin-Etsu Chemical Co., Ltd. make "KBM803" (3-mercaptopropyltrimethoxy), for example, silane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane) manufactured by Kogyo Co., Ltd. "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type silane coupler) ring agent), Shin-Etsu Chemical Co., Ltd. "KBM-7103" (3,3,3-trifluoropropyl trimethoxysilane), etc. are mentioned.

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

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Of suitable unit surface of the inorganic filler of carbon amount, in terms of improving dispersibility of the inorganic filler, 0.02mg / m ² or more is preferable, and, 0.1mg / m ² or more is more preferable, 0.2mg / m ² or more is more preferred do. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin varnish and the melt viscosity of the sheet form, 1mg / m ² or less are preferred, 0.8mg / m ² or less, more preferably, 0.5mg / m ² or less, more desirable.

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

(C) As content of an inorganic filler, when the nonvolatile component in a resin composition is 100 mass % from a viewpoint of acquiring the effect of this invention remarkably, Preferably it is 50 mass % or more, More preferably, it is 60 mass % or more. , More preferably, it is 65 mass % or more, Preferably it is 90 mass % or less, More preferably, it is 80 mass % or less, More preferably, it is 75 mass % or less.

<(D) Thermoplastic resin>

The resin composition may further contain (D) a thermoplastic resin as an arbitrary component other than the component mentioned above.

(D) Examples of the thermoplastic resin as the component include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone. Resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc. are mentioned. Especially, a phenoxy resin is preferable from a viewpoint of acquiring the desired effect of this invention remarkably. In addition, a thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton , an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a phenoxy resin having at least one skeleton selected from the group consisting of trimethylcyclohexane skeleton. Any functional group in a phenolic hydroxyl group, an epoxy group, etc. may be sufficient as the terminal of a phenoxy resin.

Specific examples of the phenoxy resin include "1256" and "4250" manufactured by Mitsubishi Chemical (both are bisphenol A skeleton-containing phenoxy resins); "YX8100" by a Mitsubishi Chemical company (bisphenol S skeleton containing phenoxy resin); "YX6954" by Mitsubishi Chemical (bisphenolacetophenone skeleton-containing phenoxy resin); "FX280" and "FX293" manufactured by Nittetsu Chemical &Materials; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482" manufactured by Mitsubishi Chemical Corporation; and the like.

As polyvinyl acetal resin, polyvinyl formal resin and polyvinyl butyral resin are mentioned, for example, Polyvinyl butyral resin is preferable. As a specific example of polyvinyl acetal resin, "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", "Denka Butyral 6000-EP" manufactured by Denki Chemical Co., Ltd. ; S-rec BH series, BX series (eg BX-5Z), KS series (eg KS-1), BL series, BM series manufactured by Sekisui Kagaku Co., Ltd.; and the like.

As a specific example of polyimide resin, "Ricacoat SN20" and "Ricacoat PN20" by a Shin-Nippon Rica company are mentioned. Specific examples of the polyimide resin include a linear polyimide obtained by reacting a difunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (a polyimide described in Japanese Patent Application Laid-Open No. 2006-37083), polysiloxane Modified polyimides, such as skeleton containing polyimide (the polyimide described in Unexamined-Japanese-Patent No. 2002-12667, Unexamined-Japanese-Patent No. 2000-319386, etc.) are mentioned.

Specific examples of the polyamideimide resin include "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo Corporation. Specific examples of the polyamideimide resin include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing polysiloxane skeleton) manufactured by Hitachi Chemical.

As a specific example of polyether sulfone resin, "PES5003P" by Sumitomo Chemical Co., Ltd., etc. are mentioned.

As a specific example of polyphenylene ether resin, the oligophenylene ether styrene resin "OPE-2St1200" by a Mitsubishi Gas Chemical company, etc. are mentioned.

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

(D) The weight average molecular weight (Mw) of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, particularly preferably 20,000 or more, from the viewpoint of remarkably obtaining the desired effect of the present invention, preferably It is 70,000 or less, More preferably, it is 60,000 or less, Especially preferably, it is 50,000 or less.

(D) the content of the thermoplastic resin is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, when the nonvolatile component in the resin composition is 100 mass% from the viewpoint of significantly obtaining the desired effect of the present invention; More preferably, it is 0.3 mass % or more, Preferably it is 5 mass % or less, More preferably, it is 3 mass % or less, More preferably, it is 1 mass % or less.

<(E) curing accelerator>

The resin composition may contain the hardening accelerator as (E) component further as arbitrary components other than the component mentioned above.

(E) As a component, a phosphorus type hardening accelerator, an amine type hardening accelerator, an imidazole type hardening accelerator, a guanidine type hardening accelerator, a metal type hardening accelerator, etc. are mentioned, for example. (E) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphoniumdecanoate, (4-methylphenyl)triphenyl Phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc. are mentioned, Triphenyl phosphine and tetrabutyl phosphonium decanoate are preferable.

Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8 -diazabicyclo(5,4,0)-undecene etc. are mentioned, 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, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl Imidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s- Triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazineisocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid adduct Water, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2 -a] an imidazole compound such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, an imidazole compound, and an epoxy resin; of adducts, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

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

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

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

(E) When content of component makes the nonvolatile component in a resin composition 100 mass % from a viewpoint of acquiring the desired effect of this invention remarkably, Preferably it is 0.01 mass % or more, More preferably, it is 0.05 mass % or more. , More preferably, it is 0.1 mass % or more, Preferably it is 3 mass % or less, More preferably, it is 1.5 mass % or less, More preferably, it is 1 mass % or less.

<(F) Flame Retardant>

The resin composition may contain the flame retardant as (F) component further as arbitrary components other than the component mentioned above.

(F) Examples of the flame retardant include a phosphazene compound, an organophosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide, and a phosphazene compound is preferred. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

Although a phosphazene compound will not be specifically limited if it is a cyclic compound which has nitrogen and phosphorus as structural elements, It is preferable that a phosphazene compound is a phosphazene compound which has a phenolic hydroxyl group.

Specific examples of the phosphazene compound include "SPH-100", "SPS-100", "SPB-100", "SPE-100" manufactured by Otsuka Chemical, "FP-" manufactured by Fushimi Chemical Corporation. 100", "FP-110", "FP-300", "FP-400", etc. are mentioned, "SPH-100" by the Otsuka Chemical Company is preferable.

As a flame retardant other than a phosphazene compound, you may use a commercial item, For example, "HCA-HQ" by Sankosha, "PX-200" by a Daihachi Chemical Industry, etc. are mentioned. The flame retardant is preferably one that is difficult to hydrolyze, and for example, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like are preferable.

(F) the content of the flame retardant, from the viewpoint of significantly obtaining the effect of the present invention, when the nonvolatile component in the resin composition is 100% by mass, preferably 0.1% by mass or more, more preferably 0.3% by mass or more, More preferably, it is 0.5 mass % or more. An upper limit becomes like this. Preferably it is 5 mass % or less, More preferably, it is 3 mass % or less, More preferably, it is 1 mass % or less.

<(G) Other additives>

The resin composition may further contain other additives as arbitrary components other than the component mentioned above. As such an additive, resin additives, such as a thickener, an antifoamer, a leveling agent, and an adhesion-imparting agent, etc. are mentioned, for example. These additives may be used individually by 1 type, and may be used in combination of 2 or more types. Each content can be suitably set by a person skilled in the art.

The preparation method of the resin composition of this invention is not specifically limited, For example, the method of adding a solvent etc. to a compounding component as needed, and mixing and dispersing using a rotary mixer etc. are mentioned.

<Physical properties and uses of the resin composition>

Since the resin composition contains the epoxy resin which has a hyperbranched structure as (A) component, the hardened|cured material by which generation|occurrence|production of curvature was suppressed can be obtained. Moreover, normally, a resin composition is excellent also in plating adhesiveness and the plating adhesiveness after a reliability test, and can obtain hardened|cured material with a low linear thermal expansion coefficient.

A resin composition shows the characteristic that generation|occurrence|production of curvature can be suppressed. Specifically, it is carried out according to the method described in Examples to be described later. At this time, the curvature is reduced, specifically, the size of the curvature is less than 1 cm. The detail of evaluation of curvature can be measured according to the method as described in the Example mentioned later.

A cured product obtained by thermosetting the resin composition at 130°C for 30 minutes, then at 170°C for 30 minutes, usually exhibits excellent plating adhesion (peel strength) with a conductor layer (plated conductor layer) formed by plating. indicates. Therefore, the said hardened|cured material forms the insulating layer excellent in the plating adhesiveness between a plating conductor layer. Plating adhesiveness becomes like this. Preferably it is 0.35 kgf/cm or more, More preferably, it is 0.40 kgf/cm or more, More preferably, it is 0.45 kgf/cm or more. The upper limit of peeling strength can be 10 kgf/cm or less, etc. The measurement of plating adhesion can be measured according to the method as described in the Example mentioned later.

The cured product obtained by thermosetting the resin composition at 130° C. for 30 minutes, then at 170° C. for 30 minutes is usually a conductor layer (plated conductor layer) formed by plating after a reliability test (130° C., humidity 85% RH, 200 hours). It shows the characteristic that it is excellent in the plating adhesiveness (peel strength) between fruit. Therefore, the said hardened|cured material forms the insulating layer excellent in the plating adhesiveness between the plating conductor layers after a reliability test. The plating adhesion after a reliability test becomes like this. Preferably it is 0.25 kgf/cm or more, More preferably, it is 0.3 kgf/cm or more, More preferably, it is 0.35 kgf/cm or more. The upper limit of plating adhesion after a reliability test can be made into 10 kgf/cm or less, etc. The measurement of plating adhesion after a reliability test can be measured according to the method as described in the Example mentioned later.

The hardened|cured material which thermosetted the resin composition at 190 degreeC for 90 minute(s) usually shows the characteristic that a linear thermal expansion coefficient is low. Accordingly, the cured product forms an insulating layer having a low coefficient of linear thermal expansion. A coefficient of linear thermal expansion becomes like this. Preferably it is 30 ppm or less, More preferably, it is 25 ppm or less, More preferably, it is 22 ppm or less. On the other hand, the lower limit of the coefficient of linear thermal expansion can be 1 ppm or more. The measurement of the coefficient of linear thermal expansion can be measured according to the method described in Examples described later.

The resin composition can obtain the hardened|cured material by which generation|occurrence|production of curvature was suppressed. Moreover, a resin composition is excellent in plating adhesiveness and the plating adhesiveness after a reliability test normally, and can obtain hardened|cured material with a low linear thermal expansion coefficient. Therefore, the resin composition of this invention can be used suitably as a resin composition for an insulation use. Specifically, it can be suitably used as a resin composition (resin composition for forming an insulating layer for forming a conductor layer) for forming the insulating layer for forming a conductor layer (including a rewiring layer) formed on the insulating layer. have.

In the multilayer printed wiring board described later, a resin composition for forming an insulating layer of a multilayer printed wiring board (resin composition for forming an insulating layer of a multilayer printed wiring board), and a resin composition for forming an interlayer insulating layer of a printed wiring board (printed wiring board) resin composition for forming an interlayer insulating layer of

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

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

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

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

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

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

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

[Resin Sheet]

The resin sheet of this invention contains a support body and the resin composition layer provided on the said support body and formed from the resin composition of this invention.

The thickness of the resin composition layer is preferably 50 µm or less, more preferably 40 µm or less, still more preferably from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product excellent in insulation even if the cured product of the resin composition is a thin film. It is preferably less than 30 μm. Although the lower limit of the thickness of a resin composition layer is not specifically limited, Usually, it can be 5 micrometers or more, etc.

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

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

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

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

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

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

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

A resin sheet can be produced by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying this resin varnish on a support using a die coater or the like, and further drying to form a resin composition layer. have.

As an organic solvent, For example, ketones, such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

[Printed wiring board]

The printed wiring board of this invention contains the insulating layer formed with the hardened|cured material of the resin composition of this invention.

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

(I) Step of laminating the resin composition layer of the resin sheet on the inner-layer substrate so as to be bonded to the inner-layer substrate

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

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

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

You may perform lamination|stacking of an inner-layer board|substrate and a resin sheet by the vacuum lamination method. In the vacuum lamination method, the thermocompression compression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, and the thermocompression compression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably It is the range of 0.29 MPa - 1.47 MPa, and the thermocompression bonding time becomes like this. Preferably it is 20 second - 400 second, More preferably, it is the range of 30 second - 300 second. Lamination|stacking is preferably performed under reduced pressure conditions of pressure 26.7 hPa or less.

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

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

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

In step (II), the resin composition layer is thermosetted to form an insulating layer. The thermosetting conditions of a resin composition layer are not specifically limited, When forming the insulating layer of a printed wiring board, you may use the conditions normally employ|adopted.

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

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

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

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

Process (IV) is a process of roughening an insulating layer. Usually, in this step (IV), smear removal is also performed. The procedure and conditions of a roughening process are not specifically limited, When forming the insulating layer of a printed wiring board, the well-known procedure and conditions normally used are employable. For example, the insulating layer can be roughened by performing the swelling process by a swelling liquid, the roughening process by an oxidizing agent, and the neutralization process by a neutralizing liquid in this order. Although it does not specifically limit as a swelling liquid used for a roughening process, An alkali solution, surfactant solution, etc. are mentioned, Preferably it is an alkali solution, As said alkali solution, sodium hydroxide solution and potassium hydroxide solution are more preferable. As a commercially available swelling liquid, "Swelling Deep Securiganth P", "Swelling Deep Securiganth SBU", "Swelling Deep Securigant P" manufactured by Atotech Japan, etc. are mentioned, for example. have. The swelling treatment by the swelling liquid is not particularly limited, and for example, it can be performed by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent used for a roughening process, For example, the alkaline permanganic acid solution which melt|dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. Moreover, as for the density|concentration of the permanganate in an alkaline permanganic acid solution, 5 mass % - 10 mass % are preferable. As a commercially available oxidizing agent, alkaline permanganic acid solutions, such as "Concentrate Compact CP" and "Dosing Solution Securigans P" by Atotech Japan, are mentioned, for example. Moreover, as a neutralization liquid used for a roughening process, an acidic aqueous solution is preferable, and as a commercial item, "reduction solution securigant P" by Atotech Japan company is mentioned, for example. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in a neutralizing solution at 30°C to 80°C for 1 minute to 30 minutes. The method of immersing the target object in which the roughening process by an oxidizing agent was made|formed from points, such as workability|operativity, in the neutralization liquid of 40 degreeC - 70 degreeC for 5 minutes - 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 300 nm or less, more preferably 250 nm or less, still more preferably 200 nm or less. Although it does not specifically limit about a minimum, Preferably it is 30 nm or more, More preferably, it is 40 nm or more, More preferably, it is 50 nm or more. The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact type surface roughness meter.

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

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

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

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

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

[Semiconductor device]

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

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

The semiconductor device of this invention can be manufactured by mounting a component (semiconductor chip) in the conduction|electrical_connection location of a printed wiring board. A "conduction location" is "a location through which an electric signal is transmitted on a printed wiring board", and the location may be on the surface, at a buried location, or anywhere. In addition, a semiconductor chip will not be specifically limited if it is an electric circuit element which uses a semiconductor as a material.

The semiconductor chip mounting method at the time of manufacturing a semiconductor device is not specifically limited as long as the semiconductor chip functions effectively, Specifically, a wire bonding mounting method, a flip chip mounting method, a bumpless build-up layer (BBUL) The mounting method by , the mounting method by the anisotropic conductive film (ACF), the mounting method by the non-conductive film (NCF), etc. are mentioned. Here, "a mounting method using a bumpless build-up layer (BBUL)" is "a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board to connect a semiconductor chip and wiring on a printed wiring board".

[Example]

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Synthesis Example 1: Synthesis of an epoxy resin having a hyperbranched structure>

The epoxy resin which has a hyperbranched structure was synthesize|combined by polycondensation. Into a reaction vessel were put 1.0 g of pentaerythritol (aqueous solution having a solid content of 10%), 10 g of bisphenol A, and 21.64 g of epichlorohydrin, and reacted at 110°C for 4 hours. Then, 4.67 g of sodium hydroxide 5N aqueous solution was dripped, it heated up from 60 degreeC to 110 degreeC, and was made to react for 30 minutes. After completion of the reaction, 100 ml of the reactant and toluene were placed in a separatory funnel and separated, and the aqueous layer was separated from the desired organic layer. Next, the organic layer was washed twice with 15% aqueous sodium hydroxide solution, and then dried at 70° C. under vacuum to obtain PHE4h (epoxy equivalent: about 394 g/eq., molecular weight 1430).

<Example 1: Preparation of resin composition 1>

20 parts of an epoxy resin having a hyperbranched structure synthesized in Synthesis Example 1 (“PHE4h”, epoxy equivalent 394 g/eq., molecular weight 1430), bisphenol A epoxy resin (“828US”, manufactured by Mitsubishi Chemicals, epoxy equivalent about 180 g/eq.) 5 parts, bisphenol AF type epoxy resin (“NC-3000L”, manufactured by Nippon Kayaku, epoxy equivalent about 271 g/eq.) 15 parts, and bixylenol type epoxy resin (“YX4000H”, Mitsubishi Chemical Company) production, epoxy equivalent 190 g/eq.) 15 parts were dissolved by heating while stirring in 60 parts of MEK.

After cooling to room temperature, 70 parts of an active ester curing agent (“HPC-8000-65T” manufactured by DIC, about 223 g/eq. of active group equivalent, a toluene solution having a solid content of 65% by mass), a phenol curing agent (“LA” manufactured by DIC) -3018-50P", active group equivalent of about 151 g/eq., 2-methoxypropanol solution with a solid content of 50%) 6 parts, a curing accelerator (4-dimethylaminopyridine (DMAP), a MEK solution with a solid content of 5 mass%) 10 parts , spherical silica surface-treated with N-phenyl-8-aminooctyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 325.2) (“SC2050-SXF” manufactured by Adomatex Co., Ltd., specific surface area 5.9 m ² /g , average particle diameter 0.77 µm) 245 parts were mixed and uniformly dispersed with a high-speed rotary mixer, followed by filtration with a cartridge filter ("SHP020" manufactured by ROKITECHNO) to prepare a resin composition 1.

<Example 2: Preparation of resin composition 2>

In Example 1,

1) Spherical silica surface-treated with N-phenyl-8-aminooctyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 325.2) (“SC2050-SXF”, manufactured by Adomatex, specific surface area 5.9 m ² /g, average particle diameter 0.77 μm) is changed from 245 parts to 260 parts,

2) 9 parts of thermoplastic resin (“YX7553BH30”, manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK having a solid content of 30% by mass and cyclohexanone) is added,

3) 3 parts of a flame retardant (PX-200, manufactured by Daihachi Chemical Industry Co., Ltd.) was further added.

Except for the above, it carried out similarly to Example 1, and produced the resin composition 2.

<Comparative Example 1: Preparation of resin composition 3>

In Example 1, 20 parts of an epoxy resin having a hyperbranched structure (“PHE4h”, epoxy equivalent 394 g/eq., molecular weight 1430) was mixed with a naphthol aralkyl type epoxy resin (“ESN-4100VEK75”, manufactured by Nittetsu Chemical & Materials Co., Ltd.) , epoxy equivalent 363 g/eq.) was changed to 20 parts. Except for the above, it carried out similarly to Example 1, and produced the resin composition 3.

<Comparative Example 2: Preparation of resin composition 4>

In Example 2, 20 parts of an epoxy resin having a hyperbranched structure (“PHE4h”, epoxy equivalent 394 g/eq., molecular weight 1430) was mixed with a naphthol aralkyl type epoxy resin (“ESN-4100VEK75”, manufactured by Nittetsu Chemical & Materials Co., Ltd.) , epoxy equivalent 363 g/eq.) was changed to 20 parts. Except for the above, it carried out similarly to Example 1, and produced the resin composition 4.

<Production of resin sheet>

As a support, PET film ("Lumira R80" manufactured by Tore Corporation, 38 μm thick, softening point 130° C., hereinafter referred to as “release PET”) subjected to release treatment with an alkyd resin mold release agent (“AL-5” manufactured by Lintec Co., Ltd.). ) was prepared.

Each resin composition was uniformly apply|coated with the die coater on mold release PET so that the thickness of the resin composition layer after drying might be set to 25 micrometers, and by drying at 80 degreeC for 1 minute, the resin composition layer was obtained on mold release PET. Next, a rough surface of a polypropylene film ("Alpan MA-411" manufactured by Ouji Ftex Corporation, 15 µm in thickness) as a protective film on the surface that is not bonded to the support of the resin composition layer, the resin composition layer and laminated to bond. Thereby, the resin sheet which consists of mold release PET (support body), a resin composition layer, and a protective film in order was obtained.

<Measurement of plating adhesion>

(Production of sample for measurement)

(1) Underlying treatment of inner-layer circuit board

The copper surface was roughened by etching both sides of the glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic R1515A manufactured by Panasonic) to 1 μm with “CZ8101” manufactured by Meg Co., Ltd. on which the inner-layer circuit was formed.

(2) Lamination of a resin sheet with a support body

The protective film was peeled off from each produced resin sheet, and it laminated|stacked on both surfaces of the inner-layer circuit board using the batch type vacuum pressure laminator (The Nikko Materials Co., Ltd. make, two-stage build-up laminator, CVP700). Lamination was performed by pressure-reducing for 30 second, making atmospheric pressure 13 hPa or less, and crimping|bonding at 130 degreeC and pressure 0.74 MPa for 45 second. Then, hot pressing was performed at 120° C. and a pressure of 0.5 MPa for 75 seconds.

(3) curing of the resin composition

The laminated resin sheet was cured at 130° C. for 30 minutes, and then the resin composition was cured under curing conditions at 170° C. for 30 minutes to form an insulating layer.

(4) Harmonization processing

The inner circuit board with the insulating layer was placed in a swelling solution, Swelling Dip Securigant P (glycol ether, aqueous sodium hydroxide solution) containing diethylene glycol monobutyl ether manufactured by Atotech Japan at 60° C. for 10 minutes. After immersion, as a roughening solution, Atotech Japan Co., Ltd. Concentrate Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) was immersed at 80° C. for 20 minutes, and finally, as a neutralizing solution, Atotech It was immersed in the reduction solution Securigant P (aqueous solution of sulfuric acid) manufactured by Japan at 40 degreeC for 5 minutes, and dried at 80 degreeC after that for 30 minutes. This board|substrate was made into "evaluation board|substrate A".

(5) Plating by semi-additive method

The evaluation substrate A was _{immersed in a solution for electroless plating containing PdCl 2} at 40° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25° C. for 20 minutes. After performing annealing treatment by heating at 150 DEG C for 30 minutes, an etching resist was formed, and after pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer to a thickness of 20 mu m. Next, annealing treatment was performed at 200 DEG C for 60 minutes. This board|substrate was made into "evaluation board|substrate B".

(Measurement of plating adhesion)

In the conductor layer of the evaluation board B, an incision was made at a portion with a width of 10 mm and a length of 100 mm, and this end was peeled off and picked up with a clipper (manufactured by TS Corporation, Autocom-type testing machine AC-50C-SL) at room temperature at 50 mm/min. The load (kgf/cm) when 35 mm was removed in the vertical direction at a speed of was measured.

(Measurement of plating adhesion after reliability test)

The produced sample was made to elapse for 200 hours under the conditions of 130 degreeC, 85% relative humidity, and 3.3V DC voltage application using the highly accelerated life test apparatus ("PM422" by ETAC). Thereafter, one end of the copper foil was peeled off and picked up with a clipper (manufactured by T.S., Autocom-type testing machine "AC-50C-SL"), using an Instron universal testing machine, in the vertical direction at a speed of 50 mm/min at room temperature. The load at the time of peeling off 35 mm was measured based on JIS C6481.

In addition, the following references|standards evaluated plating adhesiveness and the plating adhesiveness after a reliability test.

○: 0.35kgf/cm or more

×: less than 0.30 kgf/cm

<Evaluation of warpage>

(1) Lamination of resin sheets

The resin sheets produced in Examples and Comparative Examples were cut to a size of 9.5 cm × 9.5 cm, and using a batch vacuum pressurized laminator (manufactured by Nikko Materials, two-stage build-up laminator, CVP700), to 10 cm × 10 cm It laminated on the roughened surface of the cut out Mitsui Kinzoku Kogyo copper foil "3EC-III (thickness 35 micrometers)". After lamination was pressure-reduced for 30 second and atmospheric pressure was 13 hPa or less, the metal foil with a resin composition layer was produced by crimping|bonding at 120 degreeC for 30 second, and the pressure of 0.74 MPa, and the PET film which is a support body was peeled after that.

(2) Hardening of the resin composition layer

The four sides of the metal foil with a resin composition layer obtained in (1) were pasted with polyimide tape to a 1 mm thick SUS plate so that the resin composition layer became the upper surface, and the resin composition layer was cured under curing conditions at 190 ° C. for 90 minutes. .

(3) Measurement of warpage

Of the four sides of the metal foil with a resin composition layer obtained in the above (2), the polyimide tape on three sides was peeled off, and the curvature value was calculated|required by calculating|requiring the height of the highest point from the SUS board, and the following reference|standard evaluated.

○: The size of the curvature is less than 1 cm.

(triangle|delta): The magnitude|size of the curvature is 1 cm or more and less than 3 cm.

x: The size of the curvature is 3 cm or more.

<Measurement of coefficient of linear thermal expansion>

The resin sheet obtained by the Example and the comparative example was thermosetted by heating at 190 degreeC for 90 minute(s), and the sheet-like hardened|cured material was obtained by peeling from the PET film which is a support body. The cured product was cut into test pieces having a width of 5 mm, a length of 15 mm, and a thickness of 30 mm, and thermomechanical analysis was performed by a tensile weighting method using a thermomechanical analyzer (Rigaku Co., Ltd., Thermo Plus TMA8310). After attaching the test piece to the said apparatus, it measured twice continuously under the measurement conditions of 1 g of load and 5 degreeC/min of temperature increase rate. The average coefficient of linear thermal expansion (ppm) from 25°C to 150°C in the second measurement was calculated.

* Content (mass %) of the epoxy resin which has a hyperbranched structure is content of the epoxy resin which has a hyperbranched structure when the non-volatile component in a resin composition is 100 mass %.

Content (mass %) of the epoxy resin which has a hyperbranched structure in (A) component is content of the epoxy resin which has a hyperbranched structure when the whole (A) component is 100 mass %.

In Examples 1 and 2, even when component (D) - component (F) is not contained, although there is a difference in degree, it is confirmed that it leads to the result similar to the said Example.

Claims (13)

(A) an epoxy resin;
(B) a curing agent, and
(C) a resin composition comprising an inorganic filler,
(A) The resin composition in which a component contains the epoxy resin which has a hyperbranched structure. The resin composition according to claim 1, wherein the epoxy resin having a hyperbranched structure has a molecular weight of 1000 or more and 10000 or less. The epoxy equivalent of the epoxy resin having a hyperbranched structure according to claim 1, 250 g/eq. more than 700g/eq. Below, the resin composition. The resin composition according to claim 1, wherein the epoxy resin having a hyperbranched structure has a multi-branched structure in which a structure derived from a trifunctional compound or more and a structure derived from a bifunctional compound are alternately bonded. The resin composition according to claim 1, wherein the epoxy resin having a hyperbranched structure includes a cyclic structure. The resin composition according to claim 4, wherein the structure derived from the bifunctional compound includes a cyclic structure. The resin composition according to claim 1, wherein the content of the epoxy resin having a hyperbranched structure is 3% by mass or more and 10% by mass or less when the nonvolatile component in the resin composition is 100% by mass. The resin composition of Claim 1 whose content of the epoxy resin which has a hyperbranched structure is 20 mass % or more and 50 mass % or less when the whole (A) component is 100 mass %. The resin composition according to claim 1, wherein the component (B) contains any one of an active ester curing agent, a phenol curing agent, a benzoxazine curing agent, and a carbodiimide curing agent. The resin composition according to claim 1, further comprising (D) a thermoplastic resin. A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of claims 1 to 10 provided on the support. The printed wiring board containing the insulating layer formed with the hardened|cured material of the resin composition in any one of Claims 1-10. A semiconductor device comprising the printed wiring board according to claim 12 .