KR20170077044A - Resin composition - Google Patents

Abstract

[PROBLEMS] To provide a resin composition which can lower the surface roughness of the insulating layer and is excellent in the peel strength of the insulating layer and the conductor layer after the roughening treatment, the plating infiltration depth, the parts filling property, and the flame retardancy; A printed wiring board comprising the resin composition and a sheet-like laminate material, an insulating layer formed by the cured product of the resin composition, and a semiconductor device.
[Solution] A resin composition containing (A) an epoxy resin, (B) a curing agent, (C) a fluorine atom-containing alkoxysilane compound, and (D) an inorganic filler.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition. The present invention also relates to a printed wiring board comprising a sheet-like laminated material containing the resin composition, an insulating layer formed by the cured product of the resin composition, and a semiconductor device.

As a manufacturing technique of a printed wiring board, there is known a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately laminated on an inner layer substrate. The insulating layer is generally formed by curing the resin composition.

For example, Patent Document 1 discloses a resin composition containing an inorganic filler surface-treated with an epoxy resin, a curing agent and an alkoxysilane compound, wherein the inorganic filler has an average particle diameter of 0.01 탆 to 5 탆, And the content of the inorganic filler is 30% by mass to 90% by mass when the component is 100% by mass.

Patent Document 2 discloses a resin composition containing an epoxy resin, a curing agent and an inorganic filler, wherein when the inorganic filler is surface-treated with aminoalkylsilane and the nonvolatile component in the resin composition is 100 mass% And a filler content of 55 to 90 mass%.

Japanese Laid-Open Patent Publication No. 2014-12763 Japanese Laid-Open Patent Publication No. 2014-28880

2. Description of the Related Art In recent years, miniaturization and high performance of electronic devices have progressed, and in a printed wiring board, buildup layers are layered, and micro wiring and high density are demanded. The use of the resin composition disclosed in the reference 1 and the reference 2 can reduce the arithmetic average roughness of the surface of the insulating layer in the wet roughening step and can form a conductor layer having sufficient fill strength, (plating diving) depth, component landfillability, flame retardancy, and the like.

Disclosure of the Invention Problems to be Solved by the Invention A resin composition which can lower the roughness of the surface of an insulating layer and is excellent in peel strength, depth of plating penetration, parts filling property, and flame retardancy of an insulating layer and a conductor layer after roughening treatment; A printed wiring board comprising a sheet-like laminate material containing the resin composition, an insulating layer formed of a cured product of the resin composition, and a semiconductor device.

DISCLOSURE OF THE INVENTION The present inventors have intensively studied the above problems and found that the above problems can be solved by using a fluorine atom-containing alkoxysilane compound, and the present invention has been accomplished.

That is, the present invention includes the following contents.

[1] A resin composition comprising (A) an epoxy resin, (B) a curing agent, (C) a fluorine atom-containing alkoxysilane compound, and (D) an inorganic filler.

[2] The resin composition according to [1], wherein the content of the component (D) is 60% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.

[3] The resin composition according to [1] or [2], wherein the component (D) has an average particle diameter of 0.01 탆 to 2 탆.

[4] The resin composition according to any one of [1] to [3], wherein the component (D) is silica or alumina.

[5] The resin composition according to any one of [1] to [4], wherein the number of fluorine atoms in one molecule of the component (C) is 1 to 10.

[6] The resin composition according to any one of [1] to [5], wherein the number of alkoxy groups in one molecule of the component (C) is 1 to 5.

[7] The resin composition according to any one of [1] to [6], wherein the component (C) is 3,3,3-trifluoropropyltrimethoxysilane.

[8] The resin composition according to any one of [1] to [7], wherein the component (D) is surface-treated with the component (C).

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

[10] The resin composition according to any one of [1] to [9], which is used for a buildup layer of a printed wiring board.

[11] A sheet-like laminated material containing the resin composition according to any one of [1] to [10].

[12] A sheet-stacked material comprising a resin composition layer formed from the resin composition according to any one of [1] to [10].

[13] The sheet-laminated material according to [12], wherein the thickness of the resin composition layer is 10 μm or less.

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

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

According to the present invention, it is possible to lower the roughness of the surface of the insulating layer, and to provide a resin composition having satisfactory peel strength, depth of plating penetration, parts embedding property, and flame retardancy of the insulating layer and conductor layer after roughening treatment; It has become possible to provide a printed wiring board comprising a sheet-like laminate material containing the resin composition, an insulating layer formed by the cured product of the resin composition, and a semiconductor device.

1 is a schematic diagram showing an example of a cross-section of an inner substrate with an attached part.

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

[Resin composition]

The resin composition of the present invention contains (A) an epoxy resin, (B) a curing agent, (C) a fluorine atom-containing alkoxysilane compound, and (D) an inorganic filler.

Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

≪ (A) Epoxy resin >

Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, dicyclopentadiene epoxy resin, trisphenol epoxy resin, naphthol novolak type epoxy resin, 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, glycidyl ester type epoxy resin, Cresol novolak type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spirocyclic epoxy resins, cyclohexanedimethanol type epoxy resins, Tylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane type epoxy resin , The beak nolhyeong silane, an epoxy resin or the like. The epoxy resin may be used singly or in combination of two or more kinds. The component (A) is preferably at least one selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, and biphenyl type epoxy resin.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, it is preferable that at least 50% by mass or more of the epoxy resin is an epoxy resin having two or more epoxy groups in one molecule. Among them, epoxy resins having two or more epoxy groups in one molecule and having a liquid phase at 20 占 폚 (hereinafter referred to as " liquid epoxy resin ") and three or more epoxy groups in one molecule, It is preferable to contain an epoxy resin (hereinafter referred to as " solid epoxy resin "). When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, a resin composition having excellent flexibility can be obtained. Further, the fracture strength of the cured product of the resin composition is also improved.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolak type epoxy resin , An alicyclic epoxy resin having an ester skeleton, a cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a glycidylamine type epoxy resin, a bisphenol A type epoxy resin , Bisphenol F type epoxy resin, bisphenol AF type epoxy resin and naphthalene type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin), "828US" and "jER828EL" (bisphenol A type epoxy resin manufactured by Mitsubishi Kagaku Co., (Epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "630", "630LSD" (glycidyl amine type epoxy resin), Shinnitetsu Sumikin EX-721 " (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Co., Ltd., and ZX1059 (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) (Cycloaliphatic epoxy resin having an ester skeleton), " PB-3600 " (epoxy resin having a butadiene structure), " ZX1658 ", " ZX1658GS " (Liquid 1,4-glycidylcyclohexane), 630LSD (glycidylamine type, manufactured by Mitsubishi Chemical Corporation) Epoxy resin) and the like. These may be used singly or in combination of two or more kinds.

Examples of the solid epoxy resin include naphthalene type tetrafunctional epoxy resins, cresol novolak type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins , An anthracene epoxy resin, a bisphenol A epoxy resin and a tetraphenyl ethane epoxy resin are preferable, and a naphthalene type tetrafunctional epoxy resin, a naphthol type epoxy resin and a biphenyl type epoxy resin are more preferable. Specific examples of the solid epoxy resin include HP4032H (naphthalene type epoxy resin), HP-4700, HP-4710 (naphthalene type tetrafunctional epoxy resin), N-690 HP-7200H "," HP-7200H "," EXA (epoxy resin) ", EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(naphthylene ether type epoxy resin)," EPPN Quot; NC3000H ", " NC3000L ", " NC3100 " (biphenyl type epoxy resin), Shinnitetsu Sumikin "ESN475V" (naphthalene type epoxy resin), "ESN485" (naphthol novolak type epoxy resin), "YX4000H" and "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Kagaku Co., , "YX4000HK" (VIK "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF manufactured by Mitsubishi Chemical Corp.) (Solid epoxy resin), "YL7800" (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1031S" (tetraphenyl ethane type epoxy resin) . These may be used singly or in combination of two or more kinds.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, their ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1: 0.1 to 1:15 in terms of the mass ratio. By setting the proportions of the liquid epoxy resin and the solid epoxy resin in this range, suitable adhesiveness is obtained when i) is used in the form of a resin sheet, ii) sufficient flexibility is obtained in the case of using in the form of a resin sheet, The handling property is improved, and (iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii), the ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably in the range of 1: 0.3 to 1:10, : 0.6 to 1: 8 is more preferable.

The content of the epoxy resin in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability . The upper limit of the content of the epoxy resin is not particularly limited insofar as the effect of the present invention is exhibited, but is preferably 50 mass% or less, more preferably 30 mass% or less, further preferably 20 mass% or less.

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

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

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

<(B) Hardener>

The curing agent is not particularly limited as long as it has a function of curing an epoxy resin, and examples thereof include phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents, benzoxazine- based curing agents, cyanate ester- And a hardening agent. The curing agent may be used singly or in combination of two or more kinds. The component (B) is preferably at least one selected from phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents and cyanate ester-based curing agents.

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

Specific examples of the phenol-based curing agent and naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN375", and "SN375" manufactured by Shinnetsu Tetsu Sumikin Co., LA-7054 "," LA-1356 "," LA-3018-50P ", and" EXB-9500 "manufactured by DIC Corporation have.

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

Specifically, there can be mentioned an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, an ester compound containing a phenol novolak benzoylate Of these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene type diphenol structure" refers to a divalent structural unit comprising phenylene-dicyclopentylene-phenylene.

EXB9451 "," EXB9460 "," EXB9460S "," HPC-8000-65T "," HPC-8000H-65TM "as active ester compounds containing a dicyclopentadiene type diphenol structure as commercial products of active ester- EXB9416-70BK "(manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, an active ester containing an acetylated product of phenol novolac (manufactured by DIC Corporation)," EXB-8000L-65TM " YLH1026 &quot; (manufactured by Mitsubishi Chemical) as an active ester compound containing a benzoylate of phenol novolac, an active ester which is an acetylated product of phenol novolac (manufactured by Mitsubishi Chemical Co., Ltd.) YLH1026 &quot; (manufactured by Mitsubishi Chemical Corp.), and &quot; YLH1030 &quot; (manufactured by Mitsubishi Chemical Corp.) as a curing agent for the epoxy resin (trade name: DC808 manufactured by Mitsubishi Chemical Corp.) ), &Quot; YLH1048 &quot; (manufactured by Mitsubishi Kagaku Co., Division), and the like.

Specific examples of the benzoxazine type curing agent include "HFB2006M" manufactured by Shawako Co., Ltd., "P-d" and "F-a" manufactured by Shikoku Kasei Corporation.

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'- Dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1- Cyanate phenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis Bifunctional cyanate resins derived from phenolic novolacs and cresol novolacs such as bis (4-cyanophenyl) thioether and bis (4-cyanate phenyl) ether, and polyfunctional cyanate resins derived from these cyanate resins, And prepolymers. Specific examples of the cyanate ester curing agent include &quot; PT30 &quot; and &quot; PT60 &quot; (all phenol novolak type polyfunctional cyanate ester resins), &quot; BA230 &quot;, &quot; BA230S75 &quot; (bisphenol A dicyanate Or a prepolymer in which a part or all of the triazine is trimellated), and the like.

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

The ratio of the epoxy resin to the curing agent is preferably from 1: 0.01 to 1: 2, more preferably from 1: 0.015 to 1: 1.5, in terms of the ratio of [the total number of epoxy groups of epoxy resin]: [the total number of reactors of the curing agent] More preferably 1: 0.02 to 1: 1. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like and varies depending on the kind of the curing agent. The total number of epoxy groups in the epoxy resin refers to a value obtained by dividing the solid component mass of each epoxy resin by the epoxy equivalent in terms of all epoxy resins and the total number of reactors in the curing agent means that the solid mass of each curing agent is equivalent to the reactor Of the total amount of the curing agent. By setting the ratio of the epoxy resin and the curing agent to this range, the heat resistance of the cured product of the resin composition is further improved.

In one embodiment, the resin composition contains the above-mentioned (A) epoxy resin and (B) a curing agent. The resin composition preferably contains (A) a mixture of a liquid epoxy resin and a solid epoxy resin as the epoxy resin (the mass ratio of the liquid epoxy resin: solid epoxy resin is preferably from 1: 0.1 to 1:15, more preferably from 1: 0.3 to 1 (B) at least one member selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent and a cyanate ester-based curing agent as the curing agent Preferably one or more selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent and an active ester-based curing agent).

The content of the curing agent in the resin composition is not particularly limited, but is preferably 30 mass% or less, more preferably 25 mass% or less, further preferably 20 mass% or less, further preferably 10 mass% or less. The lower limit is not particularly limited, but is preferably 0.5% by mass or more.

&Lt; (C) Fluorine atom-containing alkoxysilane compound >

The resin composition of the present invention contains component (C). As a result of studies by the inventors of the present invention, it has been found that by containing the component (C), the surface roughness of the insulating layer can be lowered and a conductor layer having sufficient fill strength can be formed. And the flame retardancy is improved. The component (C) is chemically stable. As a result, the resistance to the oxidizing agent (desmear liquid) is high, and the illuminance and the plating immersion depth can be reduced, thereby improving the peel strength. Further, since the component (C) is flame retardant, flame retardancy can be imparted even if the flame retardant described later is not contained.

The component (C) preferably has 1 to 10 fluorine atoms in one molecule of the component (C) and has a fluorine atom number of 1 to 5, more preferably 1 to 5, in view of lowering the resistance to the oxidizing agent used in the roughening treatment and the plating- More preferably 1 to 3 fluorine atoms.

The component (C) preferably has an alkyl fluoride group from the viewpoint of lowering the resistance to the oxidizing agent used in the roughening treatment and the plating immersion depth, and the fluorinated alkyl group preferably has a fluorine atom at the terminal. The fluorinated alkyl group is preferably a fluorinated alkyl group having 1 to 20 carbon atoms, more preferably a fluorinated alkyl group having 1 to 10 carbon atoms, and more preferably a fluorinated alkyl group having 1 to 6 carbon atoms. Examples of such fluorinated alkyl groups include -CF ₃ , -CH ₂ CF ₃ , -CF ₂ CF ₃ , -CH ₂ CH ₂ CF ₃ , -CH (CF ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ CF ₃ , a _{-CH 2 CH (CF 3) 2} , and the like _{-C (CF 3) 3, -CH} 2 CH 2 CF 3 is preferred.

From the viewpoint of improving the reactivity, the component (C) preferably has 1 to 5 alkoxy groups in one molecule of the component (C), more preferably 1 to 3 alkoxy groups, 3 is more preferable.

The alkoxy group in the component (C) is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms Is more preferable. Examples of such alkoxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, s-butoxy, isobutoxy, An octyloxy group, a nonyloxy group, and a decyloxy group, and a methoxy group is preferable.

The alkoxy group may have a substituent. As a substituent, it is not particularly limited, for example, a halogen atom, -OH, -OC _1-6 alkyl, -N (C _1-6 alkyl) _2, C _1-6 alkyl, C _6-10 aryl, - NH ₂ , -CN, -C (O) OC _1-6 alkyl group, -COOH, -C (O) H, -NO ₂ and the like.

Here, the term &quot; C _pq &quot; (p and q are positive integers and p &lt; q is satisfied) indicates that the number of carbon atoms of the organic group described immediately after this term is p to q. For example, the expression &quot; C _1-6 alkyl group &quot; represents an alkyl group having 1 to 6 carbon atoms.

The above substituent may also have a substituent (hereinafter sometimes referred to as &quot; secondary substituent &quot;). As the secondary substituent, the same substituents as those described above may be used, unless otherwise specified.

The molecular weight of the component (C) is preferably from 50 to 2000, more preferably from 75 to 100, and still more preferably from 100 to 500, from the viewpoint of improving the compatibility.

Among them, examples of the component (C) include 3,3,3-trifluoropropyltrimethoxysilane, and a perfluoro (poly) ether group-containing alkoxysilane compound. These may be used singly or in combination of two or more kinds. Among them, 3,3,3-trifluoropropyltrimethoxysilane is preferable as the component (C). As the component (C), a commercially available product may be used, and for example, "KBM-7103" manufactured by Shin-Etsu Chemical Co., Ltd. and "Off-tool DSX"

The form of the component (C) contained in the resin composition of the present invention is not particularly limited, but is preferably contained in the resin composition in the form of the following (i) to (iii) More preferably contained in the resin composition, more preferably in the form of (i). That is, the component (C) is preferably contained in the resin composition as the surface treating agent for the component (D).

(i) the component (C) is contained as the surface treatment agent of the component (D)

(ii) the component (C) is contained alone in the resin composition

(iii) the component (C) is contained as the surface treating agent of the component (D), and the component (C)

The phrase "the component (C) contains the component (D) as a surface treatment agent" means that the component (D) is surface-treated with the component (C). In this case, the component (C) is usually present on the surface of the component (D). Incidentally, "(C) component alone in resin composition" means that component (C) is not contained as the surface treatment agent of component (D). When the component (C) is not contained as the surface treatment agent for the component (D), the component (D) is advantageous in the resin composition and is effective for lowering the surface of the insulating layer.

When the component (C) is contained in the resin composition alone, the content of the component (C) is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and still more preferably 0.2% by mass or more. The upper limit is not particularly limited, but is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 6% by mass or less.

When the component (C) is contained as the surface treatment agent of the component (D), the degree of surface treatment with the component (C) is preferably from 100 parts by mass to 100 parts by mass from the viewpoint of lowering the surface roughness of the insulating layer, Is preferably surface-treated with 0.2 to 5 parts by mass of the component (C), more preferably 0.3 to 3 parts by mass of the component (C), more preferably 0.5 to 2.5 parts by mass And more preferably the surface treated with the component (C) in the mass part.

<(D) Inorganic filler>

The material of the inorganic filler is not particularly limited and may be, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Aluminum hydroxide, aluminum hydroxide, magnesium hydroxide, 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 zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica and alumina are particularly suitable. As the silica, spherical silica is preferable. The inorganic fillers may be used singly or in combination of two or more kinds.

The average particle diameter of the inorganic filler is not particularly limited, but is preferably 2 탆 or less, more preferably 1.5 탆 or less in view of obtaining an insulating layer having a small surface roughness and improvement in fine wiring formation property, 1 mu m or less. The lower limit of the average particle diameter is not particularly limited, but is preferably 0.01 占 퐉 or more, more preferably 0.1 占 퐉 or more, and still more preferably 0.3 占 퐉 or more. Examples of commercially available inorganic fillers having such an average particle diameter include "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Adomex Corporation, "YA010C" manufactured by Denki Kagaku Kogyo Co., 4 "," Seal Pill NSS-5N "," SO-C4 "and" SO-C2 "manufactured by Adomex Co., , &Quot; SO-C1 &quot;, and the like.

The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured with a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter is determined as the average particle diameter. The measurement sample can be preferably those in which an inorganic filler is dispersed in water by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring apparatus, "LA-500" manufactured by Horiba Seisakusho Co., Ltd. and the like can be used.

The inorganic filler is preferably surface-treated with a surface treatment agent. As the surface treatment agent, there may be mentioned a surface treatment agent (hereinafter also referred to as "other surface treatment agent") other than the component (C) and the component (C). The inorganic filler may be surface-treated with the component (C), or may be surface-treated with other surface-treating agent. It is preferable that the surface treatment is performed with the component (C) in view of increasing the moisture resistance and dispersibility and lowering the roughness of the surface of the insulating layer and the depth of penetration of the plating. In addition to the component (C) There may be.

Examples of other surface treating agents include amino silane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, alkoxysilane compounds, organosilazane compounds and titanate coupling agents. These may be used singly or in combination of two or more kinds. Examples of commercially available products of such other surface treatment agents include "KBM-403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-803 KBE-903 "(3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.," KBM-573 "manufactured by Shin-Etsu Chemical Co., (N-phenyl-3-aminopropyltrimethoxysilane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-103" Phenyltrimethoxysilane), KBM-4803 (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

The degree of the surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The carbon content per unit surface area of the inorganic filler is preferably 0.05 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and still more preferably 0.2 mg / m 2 or more from the viewpoint of improving the dispersibility of the inorganic filler. On the other hand, it is preferably 1 mg / m 2 or less, more preferably 0.8 mg / m 2 or less, still more preferably 0.5 mg / m 2 or less from the viewpoint of preventing the melt viscosity of the resin varnish or the melt viscosity in the sheet form from rising . The amount of carbon per unit surface area of the inorganic filler can be measured according to the method described in &quot; Calculation of carbon amount per unit surface area &quot;

The content of the inorganic filler in the resin composition is preferably 60% by mass or more, more preferably 65% by mass or more, and even more preferably 70% by mass or more from the viewpoint of obtaining an insulating layer having a low thermal expansion coefficient. The upper limit of the content of the inorganic filler in the resin composition is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less from the viewpoint of the mechanical strength of the insulating layer. When the component (D) is surface-treated with the component (C), the content of the inorganic filler is the content containing the component (C).

&Lt; (E) Thermoplastic resin >

The resin composition of the present invention may contain (E) a thermoplastic resin in addition to the components (A) to (D).

Examples of the thermoplastic resin include thermoplastic resins such as phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyether sulfone resin, Ether resins, polycarbonate resins, polyether ether ketone resins, and polyester resins. Phenoxy resins are preferred. The thermoplastic resin may be used singly or in combination of two or more kinds.

The weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. The weight average molecular weight of the thermoplastic resin in terms of polystyrene is measured by a gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight of the thermoplastic resin in terms of polystyrene was measured using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K (manufactured by Showa Denko K.K. -804L / K-804L as a mobile phase, chloroform at a column temperature of 40 占 폚, and using a standard polystyrene calibration curve.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, A phenoxy resin having at least one skeleton selected from the group consisting of a skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethyl cyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used singly or in combination of two or more kinds. Specific examples of the phenoxy resin include "1256" and "4250" (both phenol resins containing a bisphenol A skeleton), "YX8100BH30" (phenoxy resin containing a bisphenol S skeleton), and "YX6954BH30" (Phenoxy resin containing a bisphenylacetophenone skeleton). In addition, "FX280" and "FX293" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., "YX6954BH30" and "YX7553BH30" manufactured by Mitsubishi Kagaku Co., , "YL7769BH30", "YL6794BH30", "YL7213BH30", "YL7290BH30", and "YL7482BH30"

Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include "DENKA BUTYLAL 4000-2", "DENKA BUTYLAL 5000-A", "DENKA BUTYLAL 6000-C" and "DENKA BUTYLAL 6000-C" manufactured by Denki Kagaku Kogyo Co., (Eg, BX-5Z), KS series (eg KS-1), BL series, BM series, etc., manufactured by Sekisui Chemical Co., .

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

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

Specific examples of the polyether sulfone resin include "PES 5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Specific examples of the polyphenylene ether resin include an oligophenylene ether styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Kagaku Co., Ltd., and the like.

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

Among them, a phenoxy resin and a polyvinyl acetal resin are preferable as the thermoplastic resin. Accordingly, in a preferred embodiment, the thermoplastic resin contains at least one member selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin.

When the resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 0.5% by mass to 10% by mass, more preferably 0.6% by mass to 5% by mass, still more preferably 0.7% by mass to 3% to be.

<(F) Curing accelerator>

The resin composition of the present invention may contain a curing accelerator (F) in addition to the components (A) to (D).

Examples of the curing accelerator include phosphorus hardening accelerators, amine hardening accelerators, imidazole hardening accelerators, guanidine hardening accelerators and metal hardening accelerators. Phosphorus hardening accelerators, amine hardening accelerators, imidazole hardening accelerators, Accelerators and metal curing accelerators are preferable, and amine curing accelerators, imidazole curing accelerators and metal curing accelerators are more preferable. The curing accelerator may be used singly or in combination of two or more kinds.

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

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) -Diazabicyclo (5,4,0) undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferred.

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

As the imidazole-based curing accelerator, a commercially available product may be used, and for example, "P200-H50" manufactured by Mitsubishi Kagaku Co., Ltd. and the like can be mentioned.

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

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

Although the content of the curing accelerator in the resin composition is not particularly limited, it is preferably 0.01% by mass to 9% by mass based on 100% by mass of the nonvolatile component of the epoxy resin and the curing agent.

<(G) Flame Retardant>

The resin composition of the present invention is excellent in flame retardancy even if it does not contain a flame retardant, but may contain a flame retardant (G). Examples of the flame retardant include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, metal hydroxides, and the like. The flame retardant may be used alone, or two or more flame retardants may be used in combination.

As the flame retardant, a commercially available product may be used, for example, "HCA-HQ" manufactured by Sanko Co., Ltd., "PX-200" manufactured by Ohachi Kagaku Kogyo Co.,

When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, further preferably 0.5% by mass to 10% % By mass is more preferable.

<(H) Organic filler>

The resin composition may contain (H) an organic filler in order to improve stretching. As the organic filler, any organic filler that can be used in forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicon particles.

As the rubber particles, a commercially available product may be used, for example, "EXL2655" manufactured by Dow Chemical Co., Ltd., "AC3816N" manufactured by Gansu Kasei Co., Ltd., and the like.

When the resin composition contains an organic filler, the content of the organic filler is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass, still more preferably 0.3% by mass to 5% , Or 0.5% by mass to 3% by mass.

&Lt; (I) Optional additives >

The resin composition may further contain other additives as required. Examples of such other additives include organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds, and thickeners, defoaming agents, leveling agents An adhesion promoter, and a resin additive such as a colorant.

From the viewpoint of producing a flexible printed wiring board, it is preferable that the resin composition further contains a polybutadiene structure, a urethane structure, an imide structure, and a polyimide resin having a phenol structure at the molecular terminals in the molecule. When the polyimide resin is contained, the content is preferably 10% by mass to 85% by mass, more preferably 15% by mass to 50% by mass, and still more preferably 20% by mass to 30% by mass.

The details of the polyimide may be taken into account in the description of WO 2008/153208, the contents of which are incorporated herein.

INDUSTRIAL APPLICABILITY The resin composition of the present invention results in an insulating layer having good surface roughness, fill strength, plating immersion depth, parts embedding property, and flame retardancy of the thermosetting resin. Therefore, the resin composition of the present invention can be suitably used as a resin composition (resin composition for an insulating layer of a printed wiring board) for forming an insulating layer of a printed wiring board, and can be used as a resin composition for forming an interlayer insulating layer of a printed wiring board (For example, a resin composition for an interlaminar insulating layer). Further, the resin composition of the present invention can be suitably used even in the case where the printed wiring board is a component built-in circuit board, because it results in an insulating layer having a good part filling property.

[Sheet-like laminated material]

The resin composition of the present invention can be applied in the form of a varnish, and is industrially generally used in the form of a sheet-like laminate material containing the resin composition.

As the sheet-like laminated material, the following resin sheet and prepreg are preferable.

In one embodiment, the resin sheet comprises a support and a resin composition layer bonded to the support, wherein the resin composition layer is formed from the resin composition of the present invention.

The thickness of the resin composition layer is preferably 900 占 퐉 or less, more preferably 800 占 퐉 or less, further preferably 700 占 퐉 or less, and still more preferably 600 占 퐉 or less. Particularly, in the present invention, it is preferable that the depth is less than 30 占 퐉, more preferably not more than 20 占 퐉, and further preferably not more than 10 占 퐉. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 1 占 퐉 or more, 1.5 占 퐉 or more, 2 占 퐉 or more, and the like.

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

In the case of using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter abbreviated as "PET"), polyethylene naphthalate (hereinafter abbreviated as "PEN" (Hereinafter sometimes abbreviated as "PC") and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

In the case of using a metal foil as a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, or a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, It is also good.

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

As the support, a support having a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the release agent used for the release layer of the release layer-adhered support include at least one release agent selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin. The release layer-adhered support may be a commercially available product, and examples thereof include "SK-1", "AL-5" and "AL-5", each of which is a PET film having a release layer composed mainly of an alkyd resin- AL-7 &quot; manufactured by Toray Industries, Inc., and &quot; LUMIRA T6AM &quot;

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

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

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

Drying may be carried out by a known method such as heating, hot air blowing, or the like. The drying conditions are not particularly limited, but the drying is carried out so that the content of the organic solvent in the resin composition layer is 10 mass% or less, preferably 5 mass% or less. When a resin varnish containing, for example, 30% by mass to 60% by mass of an organic solvent is used, it is dried at 50 ° C to 150 ° C for 3 minutes to 10 minutes, A resin composition layer can be formed.

In the resin sheet, a protective film according to the support may be further laminated on the surface of the resin composition layer not bonded to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 m to 40 m. By laminating a protective film, it is possible to prevent adhesion and scratching of dust or the like to the surface of the resin composition layer. The resin sheet can be rolled up and stored. When the resin sheet has a protective film, it can be used by peeling the protective film.

In one embodiment, the prepreg is formed by impregnating a sheet-like fibrous substrate with the resin composition of the present invention.

The sheet-like fibrous substrate used in the prepreg is not particularly limited, and those commonly used as prepreg substrates such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-like fibrous base material is preferably 900 占 퐉 or less, more preferably 800 占 퐉 or less, further preferably 700 占 퐉 or less, still more preferably 600 占 퐉 or less. Particularly, in the present invention, it is preferable that the depth is less than 30 占 퐉, more preferably not more than 20 占 퐉, and further preferably not more than 10 占 퐉. The lower limit of the thickness of the sheet-like fibrous base material is not particularly limited, but may be usually 1 占 퐉 or more, 1.5 占 퐉 or more, 2 占 퐉 or more, or the like.

The prepreg can be produced by a known method such as a hot melt method or a solvent method.

The thickness of the prepreg can be the same as that of the resin composition layer in the above resin sheet.

The minimum melt viscosity of the resin composition layer in the sheet-like laminated material (in the case of the prepreg, the resin composition impregnated into the sheet-like fiber substrate) is preferably 12000 poise (1200 Pa · s) More preferably not more than 10000 poise (1000 Pa · s), even more preferably not more than 8000 poise (800 Pa · s), not more than 5000 poise (500 Pa · s), or not more than 4000 poise (400 Pa · s). The lower limit of the lowest melt viscosity is preferably 100 poise (10 Pa · s) or higher, more preferably 200 poise (20 Pa · s) or higher, and more preferably 250 poise (25 Pa · s) s) or more is more preferable.

The lowest melt viscosity of the resin composition layer means the lowest viscosity exhibited by the resin composition layer when the resin of the resin composition layer is melted. Specifically, when the resin composition is heated by heating at a constant heating rate to melt the resin, the melt viscosity of the resin is lowered along with the temperature rise in the initial stage, and thereafter, the melt viscosity increases with the temperature rise. The lowest melt viscosity refers to the melt viscosity of such a minimum point. The minimum melt viscosity of the resin composition layer can be measured by a dynamic viscoelasticity method and can be measured, for example, by the method described in &quot; Measurement of Minimum Melting Viscosity of Resin Composition Layer &quot;

The cured product of the resin composition (or the resin composition layer) of the present invention (for example, thermosetting the resin composition at 190 캜 for 90 minutes) exhibits excellent flame retardancy. The flame retardancy is preferably V-0 based on the UL-94V standard or better. The evaluation of the flame retardancy can be carried out according to the method described in &quot; evaluation of flame retardancy &quot;

[Printed circuit board]

The printed wiring board of the present invention includes an insulating layer formed by a cured product of the resin composition of the present invention.

For example, the printed wiring board of the present invention can be produced by a method including the following steps (I) and (II) using the above resin sheet.

(I) Step of laminating a resin sheet on the inner layer substrate and the resin composition layer of the resin sheet to be bonded to the inner layer substrate

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

The term &quot; inner layer substrate &quot; used in the step (I) mainly refers to a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, Or circuit boards (circuits) patterned on both sides are formed. Further, when manufacturing a printed wiring board, an inner layer circuit board of an intermediate product in which an insulating layer and / or a conductor layer is to be formed is also included in the &quot; inner layer board &quot; When the printed wiring board is a component built-in circuit board, an inner-layer board containing the components may be used (the conductor layer is also referred to as a wiring layer).

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet to the inner layer substrate on the support side. Examples of the member for heating and pressing the resin sheet to the inner layer substrate (hereinafter also referred to as &quot; hot pressing member &quot;) include a heated metal plate (SUS hard plate) or a metal roll (SUS roll). It is also preferable to press the heat-press member through an elastic material such as heat-resistant rubber so that the resin sheet is sufficiently harvested on the surface unevenness of the inner layer substrate without directly pressing the heat-press member on the resin sheet.

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

The lamination can be performed by a commercial vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressurized laminator manufactured by Meikishesakusho Co., Ltd., a vacuum applicator manufactured by Nichigo Morton Co., Ltd., and the like can be given.

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

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

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

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

For example, the thermosetting condition of the resin composition layer varies depending on the kind of the resin composition and the like, but the curing temperature is in the range of 120 캜 to 240 캜 (preferably in the range of 150 캜 to 220 캜, more preferably 170 ° C to 200 ° C), and the curing time is in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

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

In the production of the printed wiring board, (III) a step of punching the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used in the production of printed wiring boards. When the support is removed after the step (II), the removal of the support is carried out between the step (II) and the step (III), between the step (III) and the step (IV) ).

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

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

Step (V) is a step of forming a conductor layer.

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

The conductor layer may have a single-layer structure or a multi-layer structure in which two or more single-metal layers or alloy layers made of different kinds of metals or alloys are stacked. When the conductor layer 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.

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-custom method or a pull-on-wet method. Hereinafter, an example in which the conductor layer is formed by the semi-

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

The resin composition of the present invention can be suitably used even in the case where the printed wiring board is a component built-in circuit board, because it results in an insulating layer having a good part embedding property.

As such a method for manufacturing the component built-in circuit board,

(i) an inner layer substrate having opposing first and second main surfaces, the inner layer substrate having a cavity formed therebetween, and a bonding material bonded to a second major surface of the inner layer substrate, A step of preparing an inner layer substrate to which the component is attached, the inner layer substrate including a component adhered to the inner surface of the cavity by a bonding material,

(ii) a step of laminating the resin sheet of the present invention such that the resin composition layer is bonded to the first main surface of the inner layer substrate,

(iii) a step of peeling the attachment material from the second main surface of the inner layer substrate,

(iv) laminating the resin sheet so that the resin composition layer is bonded to the second main surface of the inner layer substrate, and

(v) thermally curing the resin composition layer.

As shown in Fig. 1, an inner-layer substrate 100 (also referred to as a &quot; cavity substrate &quot;) having parts has first and second opposed main surfaces 11 and 12, An inner layer substrate 1 on which a cavity 1a penetrating between main surfaces is formed, a bonding material 2 bonded to the second main surface 12 of the inner layer substrate 1, (1a, 1b) includes a part (3) attached by a bonding material (2). The inner layer substrate 1 may be provided with circuit wiring 4 such as via wiring, surface wiring, and the like.

The cavity formed in the inner layer substrate can be formed by a known method using, for example, a drill, a laser, a plasma, an etching medium or the like in consideration of the characteristics of the inner layer substrate. A plurality of cavities may be formed at predetermined intervals, and the shape of the opening of the cavity is not particularly limited, and may be any shape such as a rectangle, a circle, a substantially rectangular shape, and a substantially circular shape.

Is not particularly limited as long as it has an adhesive surface exhibiting sufficient tackiness for attaching the component, and any conventionally known adhesive material may be used in manufacturing the component built-in circuit board. Examples of the adhesive material include PFDKE-1525TT (a pressure-sensitive adhesive-imparted polyimide film) manufactured by ARISA and CERASAKO Co., Ltd. and UC series (UV tape for wafer dicing) manufactured by FURUKAWA DENKI KOGYO Co., .

The component is attached to the adhesive surface of the exposed adhesive material exposed through the cavity. As the component, an appropriate electric component may be selected according to a desired characteristic. For example, the component may be a passive component such as a capacitor, an inductor, a resistor, a multilayer ceramic capacitor, or an active component such as a semiconductor bare chip. The same parts may be used for all the cavities, or different parts may be used for each cavity.

Step (ii) is a step of laminating the resin sheet of the present invention so that the resin composition layer is bonded to the first main surface of the inner layer substrate. The lamination conditions of the first main surface and the resin sheet are the same as those of the above-mentioned step (I), and the preferable range is also the same.

The resin composition layer may be laminated on the first main surface of the inner layer substrate, and then the resin composition layer may be thermally cured. The conditions for thermally curing the resin composition layer are the same as those of the above-mentioned step (II), and the preferable range is also the same.

Step (iii) is a step of peeling the attachment material from the second main surface of the inner layer substrate. The peeling of the attachment material may be carried out according to a conventionally known method depending on the kind of the attachment material.

Step (iv) is a step of laminating the resin sheet so that the resin composition layer is bonded to the second main surface of the inner layer substrate. The lamination conditions of the second main surface and the resin sheet are the same as those of the above-mentioned step (I), and the preferable range is also the same. The resin composition layer in the step (iv) may be the same resin composition layer as the resin composition layer in the step (ii) or may be a different resin composition layer.

Step (v) is a step of thermally curing the resin composition layer. The conditions for thermally curing the resin composition layer are the same as those of the above-mentioned step (II), and the preferable range is also the same.

The manufacturing method of the component built-in circuit board may further include a step of piercing the insulating layer (perforating step), a step of roughening the surface of the insulating layer, and a step of forming a conductive layer on the surface of the roughened insulating layer . These processes are as described above.

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

As a method for producing such a printed wiring board,

(1) a step of preparing an inner layer substrate and a wiring layer-attached substrate having a wiring layer provided on at least one side of the substrate,

(2) a step of laminating the resin sheet of the present invention on a substrate with a wiring layer so that the wiring layer is embedded in the resin composition layer, and thermally curing the resin sheet to form an insulating layer;

(3) a step of interconnecting the wiring layers, and

(4) removing the substrate.

It is preferable that the inner layer substrate used in this manufacturing method has a metal layer made of copper foil or the like on both sides thereof, and more preferably two or more metal layers are laminated on the metal layer. The details of the step (1) are as follows. A dry film (photosensitive resist film) is laminated on an inner layer substrate, and exposed and developed under a predetermined condition using a photomask to form a patterned dry film. Using the developed pattern dry film as a plating mask, an interconnection layer is formed by an electric field plating method, and then the pattern dry film is peeled off.

The lamination conditions of the inner layer substrate and the dry film are the same as those of the above-mentioned process (II), and the preferable range is also the same.

After the dry film is laminated on the inner layer substrate, exposure and development are performed under a predetermined condition using a photomask to form a desired pattern on the dry film.

The ratio of the line (circuit width) / space (width between circuits) of the wiring layer is not particularly limited, but is preferably 20/20 m or less (i.e., pitch is 40 m or less), more preferably 18 / Mu m or less), and more preferably 15/15 mu m or less (pitch is 30 mu m or less). The lower limit of the line / space ratio of the wiring layer is not particularly limited, but is preferably 0.5 / 0.5 占 퐉 or more, and more preferably 1/1 占 퐉 or more. The pitch does not have to be the same throughout the wiring layer.

After the pattern of the dry film is formed, a wiring layer is formed and the dry film is peeled off. Here, the wiring layer can be formed by a plating method using a dry film having a desired pattern formed thereon as a plating mask.

The conductor material used for the wiring layer is not particularly limited. In a preferred embodiment, the wiring layer contains at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium . The wiring layer may be a single metal layer or an alloy layer. Examples of the alloy layer include alloys of two or more metals (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) .

The thickness of the wiring layer varies depending on the design of the desired printed wiring board, but is preferably 3 mu m to 35 mu m, more preferably 5 mu m to 30 mu m, further preferably 10 mu m to 20 mu m, or 15 mu m.

After forming the wiring layer, the dry film is peeled off. The delamination of the dry film can be carried out by a known method. If desired, an unnecessary wiring pattern may be removed by etching or the like to form a desired wiring pattern.

Step (2) is a step of laminating the resin sheet on the substrate with the wiring layer so that the wiring layer is embedded in the resin composition layer, and thermally curing to form the insulating layer. The lamination conditions of the wiring layer-adhered base material and the resin sheet are the same as those in the above-mentioned step (II), and the preferable range is also the same.

The step (3) is not particularly limited as long as the interconnection layers can be interlayer-connected. However, the step (3) may include a step of forming a via hole in the insulating layer to form a conductor layer, and a step of polishing or grinding the insulating layer to expose the interconnection layer . The steps of forming a via hole in the insulating layer and forming the conductor layer are as described above.

As the polishing method or the grinding method of the insulating layer, it is possible to expose the printed wiring layer, and if the polishing or grinding surface is horizontal, a conventionally known polishing method or a grinding method can be applied. For example, A chemical mechanical polishing method using a polishing apparatus, a mechanical polishing method such as a buff, and a planar grinding method using a grinding wheel.

Step (4) is a step of removing the inner layer substrate and forming the printed wiring board of the present invention. The method of removing the inner layer substrate is not particularly limited. In a preferred embodiment, the inner layer substrate is peeled from the printed wiring board at the interface of the metal layer on the inner layer substrate, and the metal layer is removed by etching with, for example, a copper chloride aqueous solution.

In another embodiment, the printed wiring board of the present invention can be produced by using the above prepreg. The manufacturing method is basically the same as the case of using a resin sheet.

The printed wiring board of the present invention includes an insulating layer formed by a cured product of the resin composition of the present invention. As a result, it shows a characteristic of being excellent in part embedding property. That is, in the component built-in circuit board manufactured by using the sheet-like laminated material of the present invention, in all the cavities, the outer peripheral portion of the component may be covered with the resin composition. The evaluation of the part embeddability can be carried out according to the method described in < Evaluation of part embeddability > described later.

Since the printed wiring board of the present invention includes the insulating layer formed by the cured product of the resin composition of the present invention, the illuminance can be lowered. Specifically, the arithmetic mean roughness (Ra) and the square root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment show good results. The arithmetic mean roughness (Ra) is preferably 500 nm or less, more preferably 450 nm or less, and further preferably 400 nm or less. The lower limit is not particularly limited, but may be 100 nm or less. The square root mean square roughness (Rq) of the surface of the insulating layer is preferably 600 nm or less, more preferably 550 nm or less, and further preferably 530 nm or less. The lower limit is not particularly limited, but may be 100 nm or more. The evaluation of the arithmetic mean roughness Ra and the square root mean square roughness Rq can be performed using a commercially available non-contact surface roughing machine. For example, the arithmetic mean roughness Ra, Measurement of surface roughness (Rq)).

The printed wiring board of the present invention includes an insulating layer formed by a cured product of the resin composition of the present invention. As a result, the peel strength (peel strength) between the insulating layer and the conductor layer after the roughening treatment shows good results. The fill strength is preferably 0.3 kgf / cm or more, more preferably 0.40 kgf / cm or more, and still more preferably 0.45 kgf / cm or more. The upper limit is not particularly limited, but may be 1.2 kgf / cm or less, 0.9 kgf / cm or less, and the like. In the present invention, since the conductor layer exhibiting such a high fill strength can be formed despite the low arithmetic mean roughness (Ra) and square root mean square roughness (Rq) of the insulating layer after the roughening treatment, Thereby significantly contributing to the fine wiring. The evaluation of the peel strength can be carried out according to the method described later (measurement of the peel strength).

The insulating layer formed by the resin composition (or resin composition layer) of the present invention exhibits a good plating penetration depth. The plating penetration depth is preferably 3.0 占 퐉 or less, more preferably 2.5 占 퐉 or less, and more preferably 2.0 占 퐉 or less. The lower limit is not particularly limited, but may be 0.1 탆 or more. In an embodiment of the present invention, since the depth of plating is low, even an insulating layer made of a resin composition layer having a thickness of 10 m or less has insulation property, thereby remarkably reducing the wiring and thinning of the printed wiring board Contributing. The plating penetration depth can be evaluated according to the method described later (measurement of plating penetration depth).

[Semiconductor device]

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

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

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) to a conductive portion of a printed wiring board. The &quot; conduction point &quot; is a &quot; point giving electrical signals in the printed wiring board &quot;, and the position may be a surface or a buried point. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor material.

The method of mounting the semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip effectively functions. Specifically, the semiconductor chip mounting method, the flip chip mounting method, the bump- (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), and the like. Here, the "mounting method using the bumpless buildup layer (BBUL)" is a "mounting method in which the semiconductor chip is directly buried in the concave portion of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board".

[Example]

Hereinafter, the present invention will be described concretely with reference to examples, but the present invention is not limited to these examples. In the following description, &quot; part &quot; and &quot;% &quot; mean &quot; part by mass &quot; and &quot;% by mass &quot;, respectively, unless otherwise specified.

<Calculation of carbon amount per unit surface area>

3 g each of the following inorganic fillers was used as a sample. The sample and 30 g of MEK (methyl ethyl ketone) were placed in a centrifuge tube of a centrifugal separator and stirred to suspend the solid content, and ultrasonic waves of 500 W were irradiated at 25 캜 for 5 minutes. Thereafter, solid-liquid separation was carried out by centrifugation, and 20 g of the supernatant was removed. Further, 20 g of MEK was filled and stirred to suspend the solid content, and ultrasonic waves of 500 W were irradiated at 25 캜 for 5 minutes. Thereafter, solid-liquid separation was carried out by centrifugation, and 26 g of the supernatant was removed. The remaining suspension was dried at 160 DEG C for 30 minutes. 0.3 g of the dried sample was precisely weighed and placed in a crucible for measurement. Then, a baking agent (3.0 g of tungsten and 0.3 g of tin) was added to the crucible for measurement. The crucible for measurement was set in a carbon analyzer (&quot; EMIA-321V2 &quot;, manufactured by Horiba Seisakusho Co., Ltd.) and the amount of carbon was measured. The carbon amount per unit surface area was calculated by dividing the measured value of the amount of carbon by the specific surface area of the inorganic filler used.

<Used inorganic filler>

Inorganic filler 1: 100 parts of spherical silica ("SO-C4" manufactured by Adomex Co., Ltd., surface treatment with hexamethyldisilazane, average particle size of about 1 μm on a maker base) And surface-treated with 1 part of 3-trifluoropropyltrimethoxysilane (KBM-7103, Shin-Etsu Chemical Co., Ltd.). The amount of carbon per unit surface area was 0.25 mg / m 2.

Inorganic filler 2: 100 parts of spherical silica ("SO-C1" manufactured by Adomex Co., Ltd., surface treatment with hexamethyldisilazane, average particle size of about 0.3 μm on a maker base) - Surface treated with 2 parts of trifluoropropyltrimethoxysilane (KBM-7103, Shin-Etsu Chemical Co., Ltd.). The amount of carbon per unit surface area was 0.16 mg / m 2.

Inorganic filler 3: 100 parts of spherical alumina ("DAW-01" manufactured by DENKA CO., LTD., Manufacturer base average particle diameter: about 1.5 μm), 3,3,3-trifluoropropyltrimethoxysilane (KBM-7103, manufactured by Kogyo Co., Ltd.). The amount of carbon per unit surface area was 0.12 mg / m 2.

Inorganic filler 4: 100 parts of spherical silica ("SO-C4" manufactured by Adomex Co., Ltd., surface treatment with hexamethyldisilazane, average particle size of about 1 μm on a maker base) And surface-treated with 1 part of propyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of carbon per unit surface area was 0.31 mg / m 2.

Inorganic filler 5: 100 parts of spherical silica ("SO-C1" manufactured by Adomex Co., Ltd., surface treatment with hexamethyldisilazane, average particle size of about 0.3 μm on a maker base) And surface-treated with 2 parts of methoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of carbon per unit surface area was 0.23 mg / m 2.

Inorganic filler 6: 100 parts of spherical alumina ("DAW-01" manufactured by Denka Co., Ltd., manufacturer base average particle diameter: about 1.5 μm) was added with acetalkoxy aluminum diisopropylate (manufactured by Ajinomoto Fine Techno Co., Quot; AKTO AL-M &quot;). The amount of carbon per unit surface area was 0.15 mg / m 2.

Inorganic filler 7: 100 parts of spherical silica (manufactured by Adomex Co., Ltd., "SO-C4" surface-treated with hexamethyldisilazane, and having an average particle diameter of about 1 μm on a maker base) (KBM-103, manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of carbon per unit surface area was 0.30 mg / m 2.

[Production of Resin Sheet]

Using the resin varnish (resin composition) prepared in the following procedure, resin sheets of Examples and Comparative Examples were prepared.

<Preparation of resin varnish 1>

, 4 parts of a bisphenol type liquid epoxy resin ("ZX1059" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., an epoxy equivalent weight of about 169, and a 1: 1 mixture of bisphenol A type and bisphenol F type), 4 parts of a biscylenol type epoxy resin (Manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight: about 272) in an amount of 15 parts by weight of solvent naphtha and 10 parts by weight of cyclohexanone 10 (trade name: "YX4000HK" In a mixed solvent while stirring. After cooling to room temperature, a triazine skeleton-containing cresol novolac curing agent ("LA-3018-50P" manufactured by DIC Corporation, hydroxyl group equivalent of about 151, 2-methoxypropanol solution of 50% , 4 parts of phenol novolak type curing agent ("LA-7054" manufactured by DIC Corporation, hydroxyl equivalent weight of about 125, solid content of 60%), 4 parts of triazine skeleton-containing phenol novolak type curing agent (Nippon Tetsu Sumikin Kagaku Co., 1 part of amine curing accelerator (4-dimethylaminopyridine (DMAP), 5% by mass of solid content of MEK solution), 10 parts of rubber particles (&quot; SN-495V &quot;, hydroxyl group equivalent of about 231, (EXL2655, manufactured by Dow Chemical Co., Ltd.) and 190 parts of inorganic filler 1 were mixed and uniformly dispersed with a high-speed rotary mixer, followed by filtration with a cartridge filter (SHP050, manufactured by ROKITECHNO) Lt; / RTI &gt;

&Lt; Preparation of resin varnish 2 >

4 parts of cyclohexane dimethanol type liquid epoxy resin ("ZX1658GS" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent weight: about 135), 4 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, 15 parts of a naphthalene type epoxy resin ("ESN475V" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent weight 330), 15 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, (1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK)) in 10 parts of a solvent mixture of 15 parts of solvent naphtha and 5 parts of cyclohexanone while stirring. After cooling to room temperature, a triazine skeleton-containing cresol novolac curing agent ("LA-3018-50P" manufactured by DIC Corporation, hydroxyl group equivalent of about 151, 2-methoxypropanol solution of 50% , 12 parts of an active ester curing agent ("EXB-8000L-65M" manufactured by DIC Corporation, active group equivalent of about 220, and a nonvolatile component of 65% by mass of MEK solution), 12 parts of amine curing accelerator (4-dimethylaminopyridine ), 1.5 parts of a solid content of 5% by mass (MEK solution) and 125 parts of inorganic filler 2 were uniformly dispersed with a high-speed rotary mixer and then filtered through a cartridge filter (SHP030, manufactured by ROKITECHNO) to prepare resin varnish 2 Respectively.

<Preparation of resin varnish 3>

, 50 parts of the component (i) prepared as described below, 2 parts of naphthylene ether type epoxy resin ("EXA-7311-G4" manufactured by DIC Corporation, epoxy equivalent weight of about 213), bisphenol AF type epoxy resin 4 parts of a flame retardant ("YL7760" manufactured by Nippon Shokubai Co., Ltd., epoxy equivalent: about 238) and 2 parts of a flame retardant ("PX-200" manufactured by Ohashi Chemical Industry Co., Ltd.) were mixed with 10 parts of solvent naphtha and 5 parts of cyclohexanone And dissolved by heating. 2 parts of an active ester type curing agent ("EXB-8000L-65M" manufactured by DIC Corporation, an activating group equivalent of about 220, and a nonvolatile component of 65 mass% of MEK solution), 2 parts of an imidazole type curing accelerator 1 part of 1B2PZ "1-benzyl-2-phenylimidazole, MEK solution of solid content 5%) and 125 parts of inorganic filler 3 were uniformly dispersed in a high-speed rotary mixer, and the mixture was filtered through a cartridge filter ROKITECHNO Ltd., &quot; SHP050 &quot;) to prepare a resin varnish 3.

(Preparation of (i) component)

50 g of G-3000 (bifunctional hydroxyl group terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl group equivalent = 1798 g / eq, solid content of 100% by mass, manufactured by Nippon Soda Co., Ltd.) , 23.5 g of solvent naphtha ("Ipe Sol 150" manufactured by Idemitsu Sekiyu Kagaku Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. After the temperature became uniform, the temperature was raised to 50 占 폚, and 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g / eq.) Was added while stirring again to carry out the reaction for about 3 hours. Subsequently, the reaction product was cooled to room temperature, and then 8.96 g of benzophenone tetracarboxylic acid dianhydride (acid anhydride equivalent = 161.1 g / eq.), 0.07 g of triethylenediamine, 0.09 g of ethyldiglycol acetate Cell preparation) was added, the temperature was raised to 130 캜 with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ^-1 was confirmed by FT-IR. The reaction product was cooled to room temperature and then filtered through a 100-mesh follicle to obtain a polymer resin (component (i)) having an imide skeleton, a urethane skeleton, and a butadiene skeleton. The analysis results of this polymer resin (component (i)) are as follows.

Viscosity: 7.5 Pa · s (25 ° C, E type viscometer)

Acid value: 16.9 mg KOH / g

Solid content: 50 mass%

Number average molecular weight: 13723

Glass transition temperature: -10 ° C

Content ratio of polybutadiene structural part: 50 / (50 + 4.8 + 8.96) x 100 = 78.4 mass%

<Preparation of resin varnish 4>

In the preparation of resin varnish 1, 190 parts of inorganic filler 1 was changed to 190 parts of inorganic filler 4, and 15 parts of solvent naphtha was changed to 20 parts. Resin varnish 4 was prepared in the same manner as resin varnish 1 except for the above.

<Preparation of resin varnish 5>

In the preparation of resin varnish 2, 125 parts of inorganic filler 2 was changed to 125 parts of inorganic filler 5, and 15 parts of solvent naphtha was changed to 20 parts. Resin varnish 5 was prepared in the same manner as resin varnish 2 except for the above.

<Preparation of resin varnish 6>

In the preparation of the resin varnish 3, 125 parts of the inorganic filler 3 was changed to 125 parts of the inorganic filler 6. Resin varnish 6 was prepared in the same manner as resin varnish 3 except for the above.

<Preparation of resin varnish 7>

In the preparation of the resin varnish 1, 190 parts of the inorganic filler 1 was changed to 190 parts of the inorganic filler 7. Resin varnish 7 was prepared in the same manner as resin varnish 1 except for the above.

The materials used for the production of each resin varnish and the amount thereof (parts by mass of the nonvolatile component) are shown in the following table. (% By mass) in the non-volatile components of the liquid epoxy resin and the inorganic filler (C) are also shown.

&Lt; Examples 1 to 3 and Comparative Examples 1 to 4: Production of resin sheet >

(Lumirra T6AM manufactured by Toray Co., Ltd., thickness 38 탆, softening point 130 캜, "release PET") which had been subjected to release treatment with an alkyd resin releasing agent (AL-5, Prepared.

Each of the resin varnishes was uniformly coated on the release PET with a die coater so that the thickness of the resin composition layer after drying was 25 占 퐉 and dried at 80 占 폚 to 110 占 폚 for 4 minutes to obtain a resin composition layer on the releasing PET. Subsequently, a polypropylene film ("ALPAN MA-430" manufactured by OUFAFEX Co., Ltd., thickness 20 μm) was laminated as a protective film on the surface of the resin composition layer not bonded to the mold releasing PET to laminate with the resin composition layer Respectively. As a result, a resin sheet comprising the release PET, the resin composition layer, and the protective film in this order was obtained.

&Lt; Measurement of Minimum Melting Viscosity of Resin Composition Layer >

Only the resin composition layer was peeled off from the mold releasing PET and compressed by a mold to prepare pellets for measurement (diameter 18 mm, 1.2 g to 1.3 g). Using a paralle plate having a diameter of 18 mm, 1 g of the sample resin composition layer was measured with a dynamic viscoelasticity measuring apparatus ("Rheosol-G3000" available from Yu-Bi Co., Ltd.) The temperature was raised from 60 ° C to 200 ° C at a heating rate of 5 ° C / min. The dynamic viscoelasticity was measured under measurement conditions of a measurement temperature interval of 2.5 ° C, a frequency of 1Hz and an elasticity of 1deg, and the lowest melt viscosity poise was calculated. Are shown in the following table.

&Lt; Evaluation of Part Fillability &

Using the resin sheets prepared in the examples and the comparative examples, a component-adhered circuit board was manufactured in accordance with the following procedure, and the component's landability was evaluated.

(1) Preparation of circuit board (cavity substrate) with components attached

On a glass forging substrate BT resin double-sided copper-clad laminate (thickness of copper foil of 18 탆, substrate thickness of 0.15 mm, "HL832NSF LCA" manufactured by Mitsubishi Gas Kagaku Co., Ltd.) of 255 mm x 340 mm, The cavity was formed at a pitch of 3 mm. Then, the surface of the copper surface was subjected to a roughening treatment, followed by rust-proofing treatment (&quot; CL8300 &quot;, manufactured by MEC Corporation) Lt; / RTI &gt;

(2) Fabrication of circuit board with components attached

(Polyimide 38 占 퐉 thickness, "PFDKE-1525TT", manufactured by Arima Seisakusho Co., Ltd.) with a thickness of 25 占 퐉 was placed on one surface of the substrate obtained in the above-mentioned (1) by using a batch type vacuum laminator A two-stage build-up laminator &quot; CVP700 &quot; manufactured by Morton Co., Ltd.), and the pressure-sensitive adhesive was laminated on one side. The lamination was carried out by reducing the pressure for 30 seconds to bring the air pressure to 13 hPa or less, followed by compression at 80 DEG C and a pressure of 0.74 MPa for 30 seconds. Subsequently, a multilayer ceramic capacitor component (1005 = 1 x 0.5 mm in size, 0.14 mm in thickness) was attached one by one in the cavity to manufacture a component circuit board (cavity substrate).

(3) Evaluation test of the parts filling property

A resin composition layer in which protective films were peeled and exposed from resin sheets prepared in Examples and Comparative Examples using a batch type vacuum pressure laminator (CVP700, 2 stage build-up laminator manufactured by Nichigo Morton Co., Ltd.) (2) were stacked so that the surface of the mounting circuit board (cavity substrate) opposite to the adhesive-attached polyimide film placement surface was bonded. The lamination was carried out by reducing the pressure for 30 seconds to bring the air pressure to 13 hPa or less, followed by compression at 120 DEG C and a pressure of 0.74 MPa for 30 seconds. Subsequently, the laminated resin sheet was subjected to heat pressing under atmospheric pressure at 120 DEG C and a pressure of 0.5 MPa for 60 seconds to be smoothed. The parts cooled to room temperature were peeled off the adhesive-coated polyimide film from the adhesive circuit board to prepare the evaluation board A for evaluation. From the surface of the evaluation substrate A on which the polyimide film was peeled off, the resin flow in the cavity was observed with an optical microscope (150 times) (10 cavities were performed) Are shown in the following table.

(Evaluation standard)

A: In all the cavities, the outer peripheral portion of the multilayer ceramic capacitor component is covered with resin.

C: Even one of the cavities may be voided or the resin may not be embedded in the outer peripheral portion of the multilayer ceramic capacitor component.

.

&Lt; Evaluation of Peel Strength (Peel Strength), Roughness (Arithmetic Mean Roughness (Ra), Square Average Square Root Roughness (Rq)

Using the resin sheets prepared in Examples and Comparative Examples, substrates for measurement B and C were manufactured according to the following procedure, and the peel strength, roughness and plating penetration depth were evaluated.

(1) Foundation treatment of laminates

Both surfaces of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil depth 18 탆, substrate thickness 0.3 mm, R5715ES manufactured by Matsushita Electric Industrial Co., Ltd.) were etched with a co-treatment agent (CZ8100) Surface roughening treatment was carried out.

(2) Laminate of resin sheet

The resin composition layer in which the protective film was peeled from the resin sheet prepared in the examples and the comparative example and exposed was then laminated using a batch type vacuum laminator (CVP700, 2 stage build-up laminator manufactured by Nichigo Morton Co., Ltd.) The resin composition layer was laminated on both sides of the substrate so as to be bonded to the substrate. The lamination was carried out by reducing the pressure for 30 seconds to bring the air pressure to 13 hPa or less, followed by compression at 120 DEG C and a pressure of 0.74 MPa for 30 seconds. Subsequently, the laminated resin sheet was subjected to heat pressing under atmospheric pressure at 120 DEG C and a pressure of 0.5 MPa for 60 seconds to be smoothed.

(3) Thermal curing of the resin composition layer

After laminating the resin sheets, the resin composition layer was thermally cured (at 100 占 폚 for 30 minutes and then at 175 占 폚 for 30 minutes) to form an insulating layer on both sides of the substrate. Thereafter, for Examples 1 and 2 and Comparative Examples 1, 2 and 4, the resin composition layer was heat-cured in the state that the releasing PET as a support was adhered. As for Example 3 and Comparative Example 3, the release layer PET was peeled off and the resin composition layer was thermally cured.

(4) Harmonization processing

The laminate having the insulating layer formed thereon was immersed in a Swelling Dip Sekurigans P (glycol ether, an aqueous solution of sodium hydroxide) containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd., which is a swelling liquid, at 60 ° C And immersed for 5 minutes. Subsequently, the solution was immersed in a Concentrate Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) of Atotech Japan Co., Ltd. for 15 minutes at 80 캜 as a roughening solution (Example 2, 2 was immersed at 80 DEG C for 20 minutes). Finally, the solution was immersed in a Reducing Soluble Sucrine · Sucuregent P (aqueous solution of sulfuric acid) of Atotech Japan Co., Ltd. at 40 ° C for 5 minutes as a neutralizing solution. After drying at 80 DEG C for 30 minutes, this substrate was used as evaluation substrate B.

(5) Plating by semi-permanent method

The evaluation substrate B prepared in (4) was immersed in a solution for electroless plating containing PdCl ₂ at 40 ° C for 5 minutes and then immersed in electroless copper plating solution at 25 ° C for 20 minutes. After heating at 150 占 폚 for 30 minutes to carry out an annealing process, an etching resist was formed, and after forming a pattern by etching, copper sulfate electroplating was performed to form a conductor layer having a thickness of 30 占 퐉. Next, the substrate obtained by performing annealing at 190 캜 for 60 minutes was used as evaluation substrate C.

(Measurement of arithmetic mean roughness (Ra), square root mean square roughness (Rq)) [

The evaluation board B was evaluated by using a non-contact surface roughness machine (WYKO NT3300, manufactured by Vico Instruments Inc.), the Ra value, Rq Respectively. The average value of 10 points was calculated, and the results are shown in the following table.

(Measurement of Peel Strength)

A partial notch having a width of 10 mm and a length of 100 mm was placed in the conductor layer of the evaluation substrate C and one end of the notch was peeled off and picked up with a gripper (T. S .; autocompar tester AC-50C-SL) The load (kgf / cm (N / cm)) at the time of holding 35 mm in the vertical direction at a rate of 50 mm / min at room temperature (25 ° C) was measured.

(Measurement of plating penetration depth)

The substrate for evaluation C was subjected to cross-sectional observation using an FIB-SEM composite device ("SMI3050SE" manufactured by SII Nanotechnology Co., Ltd.). In detail, a cross section in the direction perpendicular to the surface of the evaluation substrate C was cut out by a FIB (focused ion beam), and a cross-sectional SEM image (observation width 7.5 mu m, Observation magnification x 36000) was obtained. Regarding each sample, 10 cross-sectional SEM images were randomly selected, and the maximum value (탆) of the copper plating depth was measured.

&Lt; Evaluation of flame retardancy &

(1) Laminate of resin sheet

The resin composition layer in which the protective film was peeled from the resin sheet prepared in the examples and the comparative example and exposed was then laminated using a batch type vacuum laminator (CVP700, 2 stage build-up laminator manufactured by Nichigo Morton Co., Ltd.) The resin composition layer was laminated on both sides of the laminate so that the resin composition layer was bonded to the laminate (no copper foil, substrate thickness 0.2 mm, 679FG manufactured by Hitachi Chemical Co., Ltd.). The lamination was carried out by reducing the pressure for 30 seconds to bring the air pressure to 13 hPa or less, followed by compression at 100 deg. C and a pressure of 0.74 MPa for 30 seconds. Subsequently, the laminated resin sheet was subjected to heat pressing under atmospheric pressure at 120 DEG C and a pressure of 0.5 MPa for 60 seconds to be smoothed.

(2) Curing of the resin composition layer

After the lamination of the resin sheets, the releasing PET, which is a support, was peeled off and the resin composition layer was thermally cured (at 190 캜 for 90 minutes) to form a cured product on both sides of the laminate.

(3) Flame retardancy test

UL-94V. The resulting laminate (thickness of about 380 탆) was cut to have a size of 12.7 mm × 127 mm and an edge of 1.27 mm, treated in an oven at 70 ± 1 ° C. for 168 hours, and then cooled with a desiccator for at least 4 hours. .

The burner was moved right under the obtained test piece, and the flame was brought into contact with the lower center of the test piece for 10 seconds, and the burning time thereafter was measured. Again for 10 seconds, and the subsequent burning time was measured. These were repeated five times and evaluated based on the following criteria.

(Evaluation standard)

V-0: No drop of combustible material, no burning of test specimen, and burning time of test specimen of 50 seconds or less

V-1: No drop of combustible material, no burning of test specimen, and burning time of test specimen exceeding 50 sec.

Note: Burning drops, burning of test specimens, or burning times of specimens exceed 250 s.

Examples 1 to 3 using the resin composition containing the component (C) were found to have excellent parts embeddability, arithmetic mean roughness (Ra), square root mean square roughness (Rq), fill strength, plating penetration depth, .

Comparative Example 1 using an epoxy silane coupling agent (KBM-403) instead of the component (C) tends to aggregate as compared with Examples 1 to 3, and as a result, the lowest melt viscosity is lowered, In addition, it can be seen that the arithmetic mean roughness (Ra), square root mean square roughness (Rq), plating penetration depth, and flame retardancy are also inferior.

(KBM-903) was used instead of the component (C), coupling depth of the amino group with a resin such as the component (A) lowered the plating immersion depth. However, since the lowest melt viscosity was high, It can be seen that the sex is falling. In addition, it can be seen that the flame retardancy is lower than those of Examples 1 to 3.

Comparative Example 3 using an aluminum-based coupling agent (Prenalact AL-M) instead of the component (C) had a low minimum melt viscosity and therefore good component embeddability. However, the arithmetic average roughness (Ra) , The penetration depth of plating, and the flame retardancy are inferior.

With respect to Comparative Example 4 in which the silane compound (KBM-103) was used in place of the component (C), the silane compound had no reactor and therefore the depth of plating penetration was increased without coupling with a resin such as the component (A) have. Also, it can be seen that the arithmetic mean roughness (Ra), square root mean square roughness (Rq), plating penetration depth, and flame retardancy are lower than those of Examples 1 to 3.

100 parts are attached Inner layer substrate (cavity substrate)
1 inner layer substrate
1a cavity
11 First week
12 Second week
Two-valent attachment material
3 parts
4 circuit wiring

Claims (15)

(A) an epoxy resin, (B) a curing agent, (C) a fluorine atom-containing alkoxysilane compound, and (D) an inorganic filler. The resin composition according to claim 1, wherein the content of the component (D) is 60% by mass or more when the content of the nonvolatile component in the resin composition is 100% by mass. The resin composition according to claim 1, wherein the component (D) has an average particle diameter of 0.01 탆 to 2 탆. The resin composition according to claim 1, wherein the component (D) is silica or alumina. The resin composition according to claim 1, wherein the number of fluorine atoms in one molecule of the component (C) is 1 to 10. The resin composition according to claim 1, wherein the number of alkoxy groups in one molecule of the component (C) is 1 to 5. The resin composition according to claim 1, wherein the component (C) is 3,3,3-trifluoropropyltrimethoxysilane. The resin composition according to claim 1, wherein component (D) is surface-treated with component (C). The resin composition according to claim 1, which is used for forming an insulating layer of a printed wiring board. The resin composition according to claim 1, which is for a build-up layer of a printed wiring board. A sheet-like laminated material containing the resin composition according to any one of claims 1 to 10. A sheet-stacked material comprising a resin composition layer formed from the resin composition according to any one of claims 1 to 10. The sheet-on-laminate material according to claim 12, wherein the thickness of the resin composition layer is 10 占 퐉 or less. A printed wiring board comprising an insulating layer formed by a cured product of the resin composition according to any one of claims 1 to 10. A semiconductor device comprising the printed wiring board according to claim 14.

Images