TWI609917B - Resin composition - Google Patents

Abstract

The present invention provides a resin composition which maintains glass transition temperature and thermal expansion rate, and has a small arithmetic mean roughness and a square root mean square roughness on the surface of an insulating layer in a wet roughening step, and can be formed thereon. Plating conductor layer with sufficient peel strength.

The present invention is completed by a resin composition containing an epoxy resin, a specific alkoxysilane modified resin, and an inorganic filler.

Description

Resin composition

The present invention relates to a resin composition. The present invention also relates to an adhesive film, a prepreg, a multilayer printed wiring board, and a semiconductor device containing the resin composition.

In recent years, with the progress of miniaturization and high performance of electronic equipment, multilayer printed wiring boards have been required to increase the number of layers, finer wiring and higher density.

In contrast, there are various combinations. For example, Patent Document 1 discloses a resin composition containing an alkoxysilane modified resin. It is described that the insulating material formed of these compositions has heat resistance, low thermal expansion, and flame resistance. However, its performance is not necessarily satisfactory.

[Prior technical literature] [Patent Literature]

[Patent Document 1] JP 2001-261776

The problem to be solved by the present invention is to provide a method that maintains the glass transition temperature and the thermal expansion rate, and at the same time has a small arithmetic mean roughness and a square root roughness of the surface of the insulating layer in the wet roughening step, and can be formed thereon with sufficient peeling. A resin composition having a strong plating conductor layer.

As a result of an intensive review by the present inventors in order to solve the above-mentioned problems, the present inventors have found a resin composition characterized by containing an epoxy resin, a specific alkoxysilane modified resin, and an inorganic filler, and completed the present invention.

That is, the present invention includes the following.

[1] A resin composition comprising (A) an epoxy resin, (B) a trifunctional alkoxysilane modified resin, and (C) an inorganic filler.

[2] The resin composition according to the above [1], wherein (B) at least a part of the trifunctional alkoxysilane modified resin is reacted with (C) an inorganic filler to form a reactant.

[3] The resin composition according to the above item [2], which is obtained by reacting (B) a trifunctional alkoxysilane modified resin with (C) an inorganic filler in advance, and then adding it to (A) an epoxy resin. In resin.

[4] The resin composition according to any one of the above [1] to [3], in which (C) the inorganic filler is 100% by mass, (B) the trifunctional alkoxysilane modified resin is 0.1 to 5 mass%.

[5] The resin composition according to any one of the above [1] to [4], wherein (B) the trifunctional alkoxysilane modified resin is a hydroxyl group in an epoxy resin containing a hydroxyl group via a silane Modified trifunctional alkoxysilane modified epoxy resin and / or phenolic phenolic hydroxyl group of phenol resin modified by silane modified trifunctional alkoxysilane modified phenol resin.

式(1)中，R₃為碳數1~10之直鏈或分支鏈之烷基，或烯丙基，R₄、R₅各獨立為氫、碳數1~10之直鏈或分支鏈烷基，式(1)中，m表示1~10，式(1)中，X係選自環氧樹脂或酚樹脂。 [6] The resin composition according to any one of the above [1] to [5], wherein the (B) trifunctional alkoxysilane modified resin is the following formula (1):

In formula (1), R ₃ is a straight or branched alkyl group having 1 to 10 carbon atoms, or an allyl group, and R ₄ and R _{5 are} each independently hydrogen and a straight or branched chain having 1 to 10 carbon atoms. Alkyl group, in the formula (1), m represents 1 to 10, and in the formula (1), X is selected from an epoxy resin or a phenol resin.

式(1)中，R₃為碳數1~10之直鏈或分支鏈之烷基，或烯丙基，R₄、R₅各獨立為氫、碳數1~10之直鏈或分支鏈烷基，式(1)中，m表示1~10，式(1)中，X係選自雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚AF型環氧樹脂、雙酚S型環氧樹脂、酚醛清漆酚樹脂。 [7] The resin composition according to any one of the above [1] to [6], wherein (B) the trifunctional alkoxysilane modified resin is the following formula (1):

In formula (1), R ₃ is a straight or branched alkyl group having 1 to 10 carbon atoms, or an allyl group, and R ₄ and R _{5 are} each independently hydrogen and a straight or branched chain having 1 to 10 carbon atoms. Alkyl, in formula (1), m represents 1 to 10, and in formula (1), X is selected from bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AF epoxy resin, bis Phenolic S-type epoxy resin, novolac phenol resin.

[8] The resin composition according to any one of the above [1] to [7], wherein the resin composition is hardened to form an insulating layer, and the surface of the insulating layer is subjected to The peeling strength of the conductor layer and the insulating layer obtained by the roughening treatment and the plating is 0.43 kgf / cm ~ 1.0 kgf / cm. The resin composition is hardened to form an insulating layer, and the surface of the insulating layer is subjected to roughening treatment. The arithmetic average roughness is 10nm ~ 300nm, and the square root roughness is 10nm ~ 520nm.

[9] An adhesive film formed by forming the resin composition according to any one of [1] to [8] above on a support.

[10] A prepreg obtained by impregnating the resinous composition as described in any one of the above [1] to [8] in a sheet-like reinforcing substrate.

[11] A multilayer printed wiring board formed by forming an insulating layer from a cured product of the resin composition according to any one of the items [1] to [8].

[12] A semiconductor device characterized by using the multilayer printed wiring board according to the item [11].

By using a resin composition containing an epoxy resin, a specific alkoxysilane modified resin, and an inorganic filler, the arithmetic of the surface of the insulating layer in the wet roughening step can be provided while maintaining the glass transition temperature and thermal expansion rate. The average roughness and the square root roughness are small, and a resin composition having a plated conductor layer having sufficient peeling strength can be formed thereon.

The present invention is a resin composition characterized by containing (A) an epoxy resin, (B) a trifunctional alkoxysilane modified resin, and (C) an inorganic filler. The so-called "trifunctional alkoxysilane" used in the present invention means "at least Silane compounds that are tri-substituted with alkyl and alkoxy-containing oxy groups on one silicon atom. "

〈(A) Epoxy resin〉

The epoxy resin used in the present invention is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, and phenol novolac. Lacquer type epoxy resin, third butyl catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthalene ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester Epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic Epoxy resin, epoxy resin containing a spiro ring, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, etc. These may be used singly or in combination of two or more.

Among these, bisphenol A type epoxy resin, naphthol type epoxy resin, and naphthalene type epoxy resin are preferred from the viewpoints of improving heat resistance, improving insulation reliability, and improving adhesion to metal foil. 2, biphenyl epoxy resin, naphthalene ether epoxy resin, epoxy resin with butadiene structure. Specifically, for example, bisphenol A type epoxy resin ("Epicoat 828EL" and "YL980" manufactured by Mitsubishi Chemical Corporation), and bisphenol F type epoxy resin ("jER806H" manufactured by Mitsubishi Chemical Corporation) , "YL983U"), naphthalene-type bifunctional epoxy resin ("HP4032", "HP4032D", "HP4032SS", "EXA4032SS") manufactured by DIC (share) "HP4700", "HP4710"), Naphthol-type epoxy resin (Toto Kasei ( `` ESN-475V ''), epoxy resin with butadiene structure (`` PB-3600 '' by Daicel Chemical Industry Co., Ltd.), epoxy resin with biphenyl structure (Nippon Kayaku Co., Ltd. ) "NC3000H", "NC3000L", "NC3100", "YX4000", "YX4000H", "YX4000HK", "YL6121") manufactured by Mitsubishi Chemical Co., Ltd., anthracene epoxy resin (Mitsubishi Chemical Co., Ltd. "YX8800"), naphthalene ether type epoxy resin ("EXA-7310", "EXA-7311", "EXA-7311L", "EXA7311-G3") manufactured by DIC Corporation.

The epoxy resin may be used in combination of two or more kinds, but it is preferable to contain an epoxy resin having two or more epoxy groups in one molecule. Furthermore, an epoxy resin containing an aromatic epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C., and an epoxy resin having three or more molecules in one molecule are more preferable. It is a solid aromatic epoxy resin at a temperature of 20 ° C. The term "aromatic epoxy resin" as used in the present invention means an epoxy resin having an aromatic ring structure in its molecule. When a liquid epoxy resin and a solid epoxy resin are used as the epoxy resin, the resin composition has a moderate flexibility when the resin composition is used in the form of a continuous film, or a hardened product of the resin composition has a moderate fracture strength. , Its blending ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1: 0.1 ~ 2, more preferably in the range of 1: 0.3 ~ 1.8, and more preferably 1: The range is 0.6 ~ 1.5.

In the resin composition of the present invention, from the viewpoint of improving the mechanical strength or water resistance of the hardened material of the resin composition, when the nonvolatile content in the resin composition is 100% by mass, the content of the epoxy resin is preferably 3 to 40% by mass, more preferably 5 to 35% by mass, and even more preferably 10 to 30% by mass.

<(B) Trifunctional alkoxysilane modified resin>

In the (B) trifunctional alkoxysilane modified resin used in the present invention, as long as the "trifunctional alkoxysilane" is "a trisubstituted alkyl group on at least one silicon atom, and an alkoxy group-containing The "oxysilane compound" is not particularly limited. Specifically, it is represented by R ₁ -Si- (OR ₂ ) ₃ . Here R ₁ is a lower alkyl group (preferably a straight or branched alkyl group having 1 to 10 carbon atoms, more preferably a straight or branched alkyl group having 1 to 8 carbon atoms, and more preferably A straight or branched alkyl group having 1 to 6 carbon atoms, more preferably a straight or branched alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl, ethyl, or propyl group, most preferably Is methyl), or allyl. R ₂ is hydrogen, lower alkyl (preferably a straight or branched alkyl group having 1 to 10 carbons, more preferably a straight or branched alkyl group having 1 to 8 carbons, and more preferably carbon A straight or branched alkyl group of 1 to 6 is more preferably a straight or branched alkyl group of 1 to 4 carbons, and even more preferably a methyl, ethyl, or propyl group, and most preferably Methyl), allyl, or silane. According to this, the (B) trifunctional alkoxysilane modified resin is not particularly limited, but it is preferred that the silane compound is substituted with an alkyl group and an alkoxy group-containing oxy group on at least one silicon atom. Modified resin. Therefore, a trifunctional alkoxysilane modified epoxy resin in which the hydroxyl group of the epoxy resin containing the hydroxyl group is modified by silane, or a trifunctional alkoxy group modified by the phenolic hydroxyl group of the phenol resin in the silane Silane modified phenol resin.

As the epoxy resin containing a hydroxyl group, various bisphenol-type epoxy resins can be used. The bisphenol type epoxy resin is obtained by the reaction of bisphenols with a halogen epoxide such as epichlorohydrin or β-methylepichlorohydrin. As for the bisphenols listed as phenol or 2,6- Dihalophenol reacts with formaldehyde, acetaldehyde, acetone, acetophenone, cyclohexanone, benzophenone and other aldehydes or ketones, as well as oxidation using dioxyphenyl sulfide peroxygen, by hydrogen Those obtained by etherification reaction of quinones, or hydrogenated bisphenols obtained by hydrogenation of these. The bisphenols may be 4,4'-dihydroxybiphenyl, trihydroxydiphenyldimethylethane, long-chain bisphenols, resorcinol, or salicin. Partially replaced by others. Among these bisphenol-type epoxy resins, a bisphenol A-type epoxy resin is preferred from the viewpoint of improving compatibility.

The aforementioned phenol resin is preferably a novolac phenol resin obtained by reacting phenols with aldehydes in the presence of an acid catalyst. As the phenols, for example, phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6 -Xylenol, 3,4-xylenol, 3,5-xylenol, p-ethylphenol, p-isopropylphenol, p-third butylphenol, p-chlorophenol, p-bromo Phenol and others. As for the aldehydes, in addition to formalin, paraformaldehyde, trioxane, tetraoxane and other formaldehyde generating source materials can also be used.

(B) Trifunctional alkoxysilane modified resin is a trifunctional alkoxysilane modified epoxy resin modified by silane in the above-mentioned hydroxyl-containing epoxy resin, or a phenolic hydroxyl group of phenol resin In the case of a phenol resin modified by a silane modified trifunctional alkoxysilane, the functional group equivalent (epoxy equivalent or phenolic hydroxyl equivalent) is preferably 150 to 350.

More specifically, the (B) trifunctional alkoxysilane modified resin can be represented by the structure of the following general formula (1).

In formula (1), R ₃ is a linear or branched alkyl group having 1 to 10 carbon atoms, or an allyl group, preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably A linear or branched alkyl group having 1 to 4 carbon atoms is more preferably methyl, ethyl, propyl, allyl, and more preferably methyl. R ₄ and R _{5 are} each independently hydrogen, a straight or branched alkyl group having 1 to 10 carbon atoms, preferably a straight or branched alkyl group having 1 to 5 carbon atoms, and more preferably 1 to 6 carbon atoms The straight or branched chain of 4 is more preferably methyl, ethyl, propyl, allyl, and even more preferably methyl.

In Formula (1), m represents 1-10.

In formula (1), X is selected from epoxy resin or phenol resin, and more preferably selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, and bisphenol S type epoxy resin. Resin, novolac phenol resin. When X is more specifically expressed, it is enumerated by the following formula (2) or (3).

(式中，n表示1~10，R₆各獨立表示氫、甲基、苯基、三氟甲基，^＊部與O原子鍵結)。

(In the formula, n represents 1 to 10, and R ₆ each independently represents hydrogen, methyl, phenyl, and trifluoromethyl, and the ^* part is bonded to an O atom).

(式中，^＊部與O原子鍵結)。

(In the formula, the ^* part is bonded to an O atom).

Commercially available trifunctional alkoxysilane modified resins are listed as "E201" (manufactured by Arakawa Chemical Industries, Ltd., epoxy equivalent 285) represented by the following formula (4), and "P501" represented by the following formula (5) ( Manufactured by Arakawa Chemical Industries, Ltd., phenolic hydroxyl equivalent 275).

(式中，n表示1~10，m表示1~10)。

(In the formula, n represents 1 to 10, and m represents 1 to 10).

(式中，m表示1~10)。

(In the formula, m represents 1 to 10).

<(C) Inorganic Filler>

The (C) inorganic filler used in the present invention is not particularly limited, and examples thereof include silicon dioxide, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, Magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. Among them, silicon dioxide is preferred. In addition, preferred is silicon dioxide such as amorphous silicon dioxide, pulverized silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide, and more preferably fused silicon dioxide. The silica is preferably spherical. These may be used singly or in combination of two or more kinds. Commercially available spherical fused silica is listed as "SOC2" and "SOC1" manufactured by Advantex.

The average particle diameter of the inorganic filler is not particularly limited, but the upper limit of the average particle diameter of the inorganic filler is formed by fine wiring on the insulating layer. From a viewpoint, it is preferably 5 μm or less, more preferably 3 μm or less, still more preferably 1 μm or less, still more preferably 0.7 μm or less, still more preferably 0.5 μm or less, most preferably 0.4 μm or less, and most preferably It is 0.3 m or less. On the other hand, when the lower limit of the average particle diameter of the inorganic filler is used, when epoxy resin composition is used as the resin composition paint, it is preferable from the viewpoint of preventing increase in paint viscosity and reducing workability. It is 0.01 μm or more, more preferably 0.03 μm or more, still more preferably 0.05 μm or more, still more preferably 0.07 μm or more, and most preferably 0.1 μm or more. The average particle diameter of the inorganic filler can be diffracted by laser according to Mie scattering theory. Determination by scattering method. Specifically, a laser diffraction type particle size distribution measuring device can be used to prepare a particle size distribution of an inorganic filler on a volume basis, and use the median diameter as the average particle diameter to measure. As the measurement sample, an inorganic filler is dispersed in water by ultrasonic waves. As the laser diffraction type particle size distribution measuring device, LA-500, 750, 950, etc. manufactured by Horiba, Ltd. can be used. The present invention uses LA-750.

When the content of the inorganic filler is formulated, and the non-volatile content in the resin composition is taken as 100% by mass, although it depends on the characteristics required of the resin composition, it is preferably 20 to 85% by mass, more preferably 30 to 80% by mass, more preferably 40 to 75% by mass, and even more preferably 50 to 70% by mass. When the content of the inorganic filler is too small, the thermal expansion rate of the cured product tends to be high, and when the content is too large, the cured product tends to become brittle or the peel strength tends to decrease.

In the resin composition of the present invention, at least a part of the (B) trifunctional alkoxysilane modified resin may also react with the (C) inorganic filler to form a reaction. Thing.

The so-called "reaction" of (B) trifunctional alkoxysilane modified resin and (C) inorganic filler in this specification means (B) the alkoxy group of (B) trifunctional alkoxysilane modified resin and ( C) The condensation reaction between the hydroxyl groups on the surface of the inorganic filler, specifically the hydrolysis. Dehydration condensation reaction and dealcoholization condensation reaction. Accordingly, the so-called "reactant" formed by the reaction between (B) trifunctional alkoxysilane modified resin and (C) inorganic filler means (B) trifunctional alkoxysilane modified resin and (C) Condensate of inorganic filler. In this condensate, (B) a trifunctional alkoxysilane modified resin is covalently bonded to the surface of (C) an inorganic filler.

The (C) inorganic filler of the present invention, or the (C) inorganic filler which reacts with at least a part of the (B) trifunctional alkoxysilane modified resin to form a reactant, does not impair the effect of the present invention. It is preferable that the surface is treated with a surface treating agent such as an epoxy silane-based coupling agent, an amino silane-based coupling agent, a mercapto silane-based coupling agent, a silane-based coupling agent, an organic silazane compound, or a titanate-based coupling agent. Treated to improve its moisture resistance. These can be used singly or in combination of two or more kinds. Specific surface treatment agents include aminopropylmethoxysilane, aminopropyltriethoxysilane, ureapropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N -2 (aminoethyl) aminopropyltrimethoxysilane and other aminosilane-based coupling agents, glycidyloxypropyltrimethoxysilane, glycidyloxypropyltriethoxysilane, glycidyloxy Epoxysilane coupling agents such as propylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, mercaptopropyl Trimethoxysilane, mercaptopropyltris Mercaptosilane coupling agents such as ethoxysilane, methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazolylsilane Silane coupling agents such as triazine silane, hexamethyldisilazane, hexaphenyldisilazane, trisilazane, cyclotrisilazane, 1,1,3,3,5,5-hexa Organosilazane compounds such as methylcyclotrisilazane, butyl titanate dimer, titanium octanoate, titanium diisopropoxy bis (triethanolvalerate), titanium dihydroxylactate, Hydroxy bis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tri-n-butoxy monostearate Titanate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropylbis (dioctyl phosphate) titanate, tetraoctylbis (di-tridecyl phosphate) (Ester) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphate titanate, isopropyltrioctylfluorenyl titanate, isopropyl Propyltricumylphenyl titanate, isopropyltriisostearylfluorenyl titanate, isopropyl Stearyl fluorenyl dipropenyl fluorenyl titanate, isopropyl methacryl fluorenyl isostearyl fluorenyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tri- Dodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tris (N-fluorenylaminoethyl.aminoethyl) titanate, etc. Titanate silicon coupling agent.

Among these, when the (C) inorganic filler is surface-treated with an organic silazane compound, the dispersibility of the resin paint is improved, and the inorganic filler is modified with a trifunctional alkoxysilane modified resin. From the viewpoint of coverage, it is more favorable. In particular, hexamethyldisilazane is preferred. When (C) an inorganic filler treated with a surface treatment agent is used, (B) a trifunctional alkoxysilane modified resin can also be covalently bonded to (C) without passing through the surface treatment agent. The surface of the machine filling material.

In the resin composition of the present invention, (B) a trifunctional alkoxysilane modified resin and (C) an inorganic filler can be directly added to the resin composition, or (B) a trifunctional alkoxysilane can be added. The modified resin is reacted with the inorganic filler (C) in advance and added. From the viewpoint of improving the dispersibility in the resin composition, it is preferable that the (B) trifunctional alkoxysilane modified resin is reacted with the (C) inorganic filler in advance and then added to the resin composition. The (B) trifunctional alkoxysilane modified resin is reacted with the (C) inorganic filler in advance and added to the resin composition, so that the (B) trifunctional alkoxy group can be appropriately obtained as described above. A resin composition in which at least a part of the silane-modified modified resin reacts with (C) an inorganic filler to form a reactant. The method in which (B) a trifunctional alkoxysilane modified resin and (C) an inorganic filler are reacted in advance is, for example, the following method.

Put the (C) inorganic filler into the rotary kneader, and while mixing the (B) trifunctional alkoxysilane modified resin with MEK in advance, spray the (C) inorganic filler for 5 to 30 minutes Then, it is stirred at 50 to 150 ° C for 0.5 to 3 hours to perform a preliminary reaction. It is better to stir at 55 ~ 130 ° C for 0.5 ~ 3 hours, more preferably at 60 ~ 110 ° C for 0.5 ~ 3 hours, and even more preferably at 70 ~ 80 ° C for 1 ~ 3 hours. Subsequently, a method for distilling off volatile components is listed. In addition to the rotary kneader, a drum-type kneader, a rock kneader, a vibrating fluidized bed, a powder dryer, etc. may be used, but a rotary kneader is preferred in terms of simplicity. Rotary kneaders are listed as Henschel powder mixers.

(B) Trifunctional alkoxysilane modified resin content prevents melting From the viewpoint of an increase in melt viscosity, it is preferably 5 mass% or less, more preferably 4 mass% or less, and still more preferably 3 mass% or less with respect to 100 mass% of the (C) inorganic filler. From the viewpoint of improving the dispersibility of the resin paint, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more.

The resin composition of the present invention is hardened to form an insulating layer. The surface of the insulating layer is roughened, and the peeling strength of the conductor layer and the insulating layer obtained by plating can be used. The measurement method described in (Measurement of Peel Strength) is grasped.

The upper limit of the peel strength is preferably 0.7 kgf / cm or less, more preferably 0.8 kgf / cm or less, still more preferably 0.9 kgf / cm or less, and still more preferably 1.0 kgf / cm or less. The lower limit of the peel strength is preferably 0.43 kgf / cm or more, more preferably 0.48 kgf / cm or more, and still more preferably 0.53 kgf / cm or more.

The resin composition of the present invention is hardened to form an insulating layer, and the arithmetic average roughness (Ra value) and square root mean square roughness (Rq value) of the surface of the insulating layer after roughening treatment can be used as described below. The measurement methods described in "Measurement of Arithmetic Mean Roughness (Ra Value) and Mean Square Square Root Roughness (Rq Value)" are mastered.

The upper limit of the arithmetic average roughness (Ra value) is preferably 300 nm or less, more preferably 250 nm or less, still more preferably 220 nm or less, still more preferably 200 nm or less, still more preferably 190 nm or less, and most preferably 170 nm. Hereinafter, it is more preferably 150 nm or less. The lower limit of the arithmetic average roughness (Ra value) is preferably 50 nm or more, more preferably 30 nm or more, and even more preferably 10 nm or more.

The upper limit of the square root roughness (Rq value) is preferably 520 nm or less, more preferably 450 nm or less, still more preferably 400 nm or less, still more preferably 380 nm or less, and still more preferably 350 nm or less, and most preferably 330 nm or less, preferably 300 nm or less, and 250 nm or less is more preferable. The lower limit of the root mean square roughness (Rq value) is preferably 90 nm or more, more preferably 70 nm or more, more preferably 50 nm or more, still more preferably 30 nm or more, and still more preferably 10 nm or more.

〈(D) Hardening accelerator〉

By further containing a hardening accelerator, the resin composition of the present invention can effectively harden an epoxy resin and a hardener. The hardening accelerator is not particularly limited, and examples thereof include amine-based hardening accelerators, guanidine-based hardening accelerators, imidazole-based hardening accelerators, fluorene-based hardening accelerators, and metal-based hardening accelerators. These may be used singly or in combination of two or more kinds.

The amine-based hardening accelerator is not particularly limited, and examples thereof include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6-ginseng ( Amine compounds such as dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU), and the like. These may be used singly or in combination of two or more kinds.

The guanidine-based hardening accelerator is not particularly limited, and examples thereof include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, and 1- (o-tolyl group). ) Guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7 -Methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, 1-methyl biguanide, 1-ethylbis Guanidine, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1 -Phenyl biguanide, 1- (o-tolyl) biguanide and the like. These may be used singly or in combination of two or more kinds.

The imidazole-based hardening accelerator is not particularly limited, and examples thereof include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl- 4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2- Methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl 4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenyl Imidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6 -[2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl -(1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid Adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a] benzimidazole 2-methyl-1-dodecyl benzimidazolium chloride, 2-imidazoline, 2-phenyl imidazole and imidazoline compounds, and adducts of an imidazole compound with an epoxy resin. These can be used singly or in combination of two or more kinds.

The fluorene-based hardening accelerator is not particularly limited, and examples thereof include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, ( 4-methylphenyl) triphenylphosphonium thiocyanate Salt, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like. These can be used singly or in combination of two or more kinds.

In the resin composition of the present invention, when the content of the hardening accelerator (excluding the metal-based oxidation accelerator) is 100% by mass of the nonvolatile component in the resin composition, it is preferably in the range of 0.005 to 1% by mass, and more preferably 0.01 to 0.5% by mass. If it is less than 0.005 mass%, the curing tends to be slow and the heat-curing time is prolonged. If it exceeds 1 mass%, the storage stability of the resin composition tends to decrease.

The metal-based hardening accelerator is not particularly limited, and examples thereof include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organocobalt complexes such as cobalt (II) ethionylpyruvate and cobalt (III) ethidiumpyruvate, and complexes of organic copper such as copper (II) ethyruvate Compounds, organic zinc complexes such as zinc (II) acetonylpyruvate, organic iron complexes such as iron (III) acetonylpyruvate, organic nickel complexes such as nickel (II) acetonylpyruvate, Organomanganese complexes such as manganese (II) acetamidinate and the like. As the organic metal salt, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like are listed. These can be used singly or in combination of two or more kinds.

In the resin composition of the present invention, when the amount of the metal-based hardening accelerator is taken as 100% by mass of the non-volatile component in the resin composition, the metal content based on the amount of the metal-based hardening catalyst is preferably in the range of 25 to 500 ppm. , Better in the range of 40 ~ 200ppm. When it is less than 25 ppm, it is difficult to form a conductive layer having excellent adhesion to the surface of the insulating layer having a low arithmetic average roughness. When it exceeds 500 ppm, the resin composition may be stored. Tendency to decrease stability and insulation.

<(E) Hardener>

By further containing a hardener, the resin composition of the present invention can improve insulation properties or mechanical properties. The (E) hardener is not particularly limited, and examples thereof include a phenol-based hardener, a naphthol-based hardener, an active ester-based hardener, a benzoxazine-based hardener, a cyanate-based hardener, and an anhydride-based hardener. From the viewpoint of further reducing the arithmetic average roughness (Ra value), a phenol-based hardener, a naphthol-based hardener, and an active ester-based hardener are preferred. These can be used singly or in combination of two or more kinds.

The phenol-based hardener and the naphthol-based hardener are not particularly limited, and examples thereof include a phenol-based hardener having a novolac structure or a naphthol-based hardener having a novolac structure, preferably a phenol novolac resin and a triazine skeleton Phenol novolac resin, naphthol novolac resin, naphthol aralkyl resin, naphthol resin containing a triazine skeleton, and biphenylaralkyl phenol resin. As for commercially available products, examples of biphenylaralkyl phenol resins include "MEH-7700", "MEH-7810", and "MEH-7851"; "MEH-7851-4H" (made by Meiwa Chemical Co., Ltd.), "GPH" (manufactured by Nippon Kayaku Co., Ltd.) is listed as "naphthol novolac resin" as "NHN", "CBN" (manufactured by Nippon Kayaku Co., Ltd.), and "naphthol aralkyl resin" is listed as " "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN395", "SN375" (manufactured by Totsuka Kasei Co., Ltd.) are listed as "TD2090" ( (Manufactured by DIC), and phenol novolak resins containing a triazine skeleton are listed as "LA3018", "LA7052", " LA7054 "," LA1356 "(DIC (shares) system), etc. These may be used singly or in combination of two or more.

The active ester-based hardener is not particularly limited. Generally, it is preferable to use a phenolic ester, a thiophene ester, an N-hydroxyamine ester, a heterocyclic hydroxy compound ester or the like having two or more highly reactive esters in the molecule. Of the compound. The active ester-based hardener is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. Especially from the viewpoint of improving heat resistance, an active ester-based hardener obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based hardener obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Agent. As the carboxylic acid compound, for example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like are listed. As for the phenol compound or naphthol compound, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenylphthalin, methylated bisphenol A, methylated bisphenol F, Methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene Diphenol, phenol novolac resin, etc. As the active ester-based hardener, one kind or two or more kinds can be used. As the active ester-based hardener, the active ester-based hardener disclosed in Japanese Patent Application Laid-Open No. 2004-277460 can also be used, and a commercially available one can also be used. Commercially available active ester-based hardeners are preferably those containing a dicyclopentadiene diphenol structure, an acetonide of a phenol novolac resin, a benzyl compound of a phenol novolac resin, and the like. in particular, Dicyclopentadienyl diphenol-containing structures are listed as EXB9451, EXB9460, EXB9460S-65T, HPC-8000-65T (manufactured by DIC (shares), active group equivalent of about 223), and ethyl acetate of novolac resins are listed as DC808 (made by Japan Epoxy Resin Co., Ltd., with an active group equivalent of about 149), benzoic acid compounds of phenol novolac resin are listed as YLH1026 (made by Japan Epoxy Resin Co., Ltd., with an active group equivalent of about 200), YLH1030 (Japan Made of epoxy resin (share), active group equivalent of about 201), YLH1048 (made of Japan epoxy resin (share), active group equivalent of about 245), etc., among them, the viewpoints of storage stability of paint and thermal expansion rate of hardened materials In terms of EXB9460S.

More specifically, the active ester hardener containing a dicyclopentadienyl diphenol structure is a compound of the following formula (6).

(式中，R為苯基、萘基，k表示0或1，n為重複單位之平均，為0.05~2.5)。

(In the formula, R is a phenyl group, a naphthyl group, k is 0 or 1, and n is an average of repeating units, and is 0.05 to 2.5).

From the viewpoint of reducing the dielectric tangent and improving the heat resistance, R is preferably a naphthyl group, on the other hand, k is preferably 0, and n is preferably 0.25 to 1.5.

The benzoxazine-based hardener is not particularly limited, and specific examples include F-a, P-d (manufactured by Shikoku Kasei Co., Ltd.), HFB2006M (manufactured by Showa Polymer Co., Ltd.), and the like.

The cyanate-based curing agent is not particularly limited, and examples thereof include novolac type ( (Phenol novolac type, alkylphenol novolac type, etc.) cyanate type hardener, dicyclopentadiene type cyanate type hardener, bisphenol type (bisphenol A type, bisphenol F type, bisphenol S Type, etc.) cyanate ester-based hardeners, and prepolymers in which some of them are triazinated. The weight average molecular weight of the cyanate-based hardener is not particularly limited, but is preferably 500 to 4500, and more preferably 600 to 3000. Specific examples of the cyanate-based curing agent include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4 '-Methylenebis (2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2 -Bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylphenylmethane), bis (4-cyanate-3,5-dimethylphenyl) Methane, 1,3-bis (4-cyanatephenyl-1- (methylethylene)) benzene, bis (4-cyanatephenyl) sulfide, bis (4-cyanate Difunctional cyanate resins such as phenyl phenyl ether, polyfunctional cyanate resins derived from phenol novolacs, cresol novolacs, phenol resins containing a dicyclopentadiene structure, etc., part of these cyanate resins Triazinated prepolymers, etc. These can be used singly or in combination of two or more. Commercially available cyanate resins are listed as phenol novolac-type polyfunctional cyanate resins represented by the following formula (7) (Japan LON30 (PT), PT30, cyanate equivalent 124), a part or all of a prepolymer of a bisphenol A dicyanate represented by the following formula (8) (Japanese) LONZA (stock), BA230, cyanate equivalent 232), a cyanate resin containing a dicyclopentadiene structure represented by the following formula (9) (Japanese LONZA (stock), DT-4000, DT-7000) Wait.

[式中，n表示平均值而為任意數(較好為0~20)]。

[In the formula, n represents an average value and is an arbitrary number (preferably 0 to 20)].

(式中，n表示平均值而為0~5之數)。

(In the formula, n represents an average value and is a number from 0 to 5.)

The acid anhydride-based hardener is not particularly limited, and examples thereof include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, Methyl nadic acid anhydride, hydrogenated methyl natic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5- (2,5-dioxotetrahydro-3 -Furyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalene Tetracarboxylic dianhydride, oxydiphthalic anhydride, 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 -(Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione, ethylene glycol bis (trimellitic anhydride), styrene and malay Acid copolymerized styrene. Polymeric acid anhydrides such as maleic resin.

In the resin composition of the present invention, from the viewpoint of improving the mechanical strength or water resistance of the cured product of the resin composition, the total of (A) the epoxy group of the epoxy resin and (E) the total of the reactive groups of the curing agent. The number ratio is preferably 1: 0.2 ~ 2, more preferably 1: 0.3 ~ 1.5, and even more preferably 1: 0.4 ~ 1. The total number of epoxy groups of epoxy resins present in the resin composition is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent value for all epoxy resins. The total number of reaction groups is a value obtained by dividing the solid content mass of each hardener by the value of the reaction group equivalents for all the hardeners.

<(F) Thermoplastic resin>

The resin composition of the present invention may further contain (F) thermoplastic resin. This resin improves the mechanical strength of the cured product, and also improves the film forming performance when used in the form of a film. Examples of the thermoplastic resin include phenoxy resin, polyimide resin, polyimide resin, polyether imide resin, polyfluorene resin, polyether resin, polyphenylene ether resin, and polycarbonate. Resin, polyetheretherketone resin, polyester resin. These thermoplastic resins can be used individually or in combination of two or more. The weight average molecular weight of the thermoplastic resin is preferably in the range of 5000 to 200,000. If it is smaller than this range, the film forming ability or the effect of improving the mechanical strength cannot be fully exerted. When it is larger than this range, the compatibility of the cyanate resin and the naphthol type epoxy resin is insufficient, and the surface unevenness after hardening becomes large, making it difficult. A tendency to form high-density fine wiring. The weight average molecular weight in the present invention is measured by a gel permeation chromatography (GPC) method (equivalent to polystyrene). Specifically, the weight-average molecular weight measured by the GPC method can use LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko Corporation -804L was used as a column, and chloroform was used as a mobile phase. The column temperature was measured at 40 ° C, and calculated using a calibration line of standard polystyrene.

When the (F) thermoplastic resin is blended in the resin composition of the present invention, the content of the thermoplastic resin in the resin composition is not particularly limited, but it is preferably 0.1% by mass with respect to 100% by mass of the nonvolatile matter in the resin composition. ~ 10 mass%, more preferably 1 to 5 mass%. When the content of the thermoplastic resin is too small, the film forming ability or the effect of improving the mechanical strength tends to be insufficient. When the content of the thermoplastic resin is too high, the arithmetic average roughness of the surface of the insulating layer after the wet roughening step increases. Great tendency.

<(G) Rubber particles>

The resin composition of the present invention can further improve the plating peeling strength by further containing (G) rubber particles, and can also improve the drilling processability, reduce the dielectric tangent, and reduce the stress. The rubber particles that can be used in the present invention are, for example, those which are insoluble in an organic solvent used when preparing a paint for the resin composition, and are incompatible with cyanate resin or epoxy resin, which are essential components. Accordingly, the rubber particles are present in a dispersed state in the paint of the resin composition of the present invention. The rubber particles are generally prepared by making the molecular weight of the rubber component so large that it cannot be dissolved in an organic solvent or resin, and the particles are in the form of particles.

Preferable examples of the rubber particles usable in the present invention include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles, and the like. Core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, the shell layer of the outer layer is composed of a glass-like polymer, the core layer of the inner layer is a two-layer structure composed of a rubber-like polymer, or the shell of the outer layer The layer is composed of a glass-like polymer, the intermediate layer is composed of a rubber-like polymer, and the core layer is composed of a three-layer structure composed of a glass-like polymer. The glassy polymer layer is formed of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is formed of, for example, butyl acrylate polymer (butyl rubber). The rubber particles may be used in combination of two or more. Specific examples of the core-shell type rubber particles are STAFILOID AC3832, AC3816N, IM-401 to 1, IM-401 to 7-17 (trade name, manufactured by GANTZ Kasei Co., Ltd.), and METAPLENE KW-4426 (trade name, Mitsubishi Corporation萦 (shares) system). Specific examples of crosslinked acrylonitrile butadiene rubber (NBR) particles XER-91 (average particle diameter: 0.5 μm, manufactured by JSR (strand)) and the like. Specific examples of the cross-linked styrene butadiene rubber (SBR) particles include XSK-500 (average particle diameter: 0.5 μm, manufactured by JSR). Specific examples of the acrylic rubber particles include METAPLENE W300A (average particle diameter of 0.1 μm) and W450A (average particle diameter of 0.2 μm) (manufactured by Mitsubishi Chemical Corporation).

The average particle diameter of the prepared rubber particles is preferably in the range of 0.005 to 1 μm, and more preferably in the range of 0.2 to 0.6 μm. The average particle diameter of the rubber particles used in the present invention can be measured using a dynamic light scattering method. For example, the rubber particles are uniformly dispersed in an appropriate organic solvent by using ultrasonic waves, etc., and the particle size distribution of the rubber particles is prepared on a mass basis using a thick particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.), and The value diameter is measured as an average particle diameter.

The content of the rubber particles is preferably 1 to 10% by mass, and more preferably 2 to 5% by mass based on 100% by mass of the nonvolatile matter in the resin composition.

<(H) flame retardant>

The resin composition of the present invention can impart flame retardancy by further containing (H) a flame retarder. Examples of the flame retardant include organic phosphorus-based flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicon-based flame retardants, metal oxides, and the like. Organophosphorus-based flame retardants include phenanthrene phosphorus compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko, and phosphorus-containing benzoxazine compounds such as HFB-2006M manufactured by Showa High Polymers. REOFOS 30, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP manufactured by Ajinomoto Precision Technology Co., Ltd. Phosphate compounds such as TPPO and PPQ manufactured by Gakuin Industry Co., Ltd., OP930 manufactured by CLARIANT Co., Ltd., PX200 manufactured by Da Yah Chemical Co., Ltd., and phosphorus-containing compounds such as FX289, FX305, TX0712 manufactured by Todo Chemical Co., Ltd. Epoxy resin, phosphorus-containing phenoxy resins such as ERF001 manufactured by Totsu Kasei Co., Ltd., and phosphorus-containing epoxy resins such as YL7613 manufactured by Japan Epoxy Resins Co., Ltd. Organic nitrogen-containing phosphorus compounds are listed as phosphate ester compounds such as SP670 and SP703 manufactured by Shikoku Chemical Industries, Ltd., SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd., and FP- manufactured by Fushimi Pharmaceutical Co., Ltd. Series of phosphazene compounds and the like. The metal hydroxides are listed as magnesium hydroxides such as UD65, UD650, and UD653 manufactured by Utsu Materials, and B-30, B-325, B-315, B-308, and B- 303, UFH-20, etc.

The content of the flame retardant is based on 100% by mass of the nonvolatile matter in the resin composition, preferably 0.5 to 10% by mass, and more preferably 1 to 5% by mass.

〈Other ingredients〉

The resin composition of the present invention may be blended with other components as long as the effect of the present invention is not hindered. As for the other components, there can be mentioned thermosetting resins such as vinylbenzene compounds, acrylic compounds, maleimide compounds, and block isocyanate compounds, organic fillers such as silicon powder, nylon powder, and fluorine powder. Oluben, Benton, etc. Adhesive, polysiloxane-based, fluorine-based, polymer-based defoamer or advection agent, imidazole-based, thiazole-based, triazole-based, silane-based coupling agents and other adhesion-imparting agents, phthalocyanine. Blue, phthalocyanine. Green and iodine. Colorants such as green, cis azo yellow, and carbon black.

The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method of adding a component to be prepared, a solvent as required, and the like, and mixing using a rotary kneader or the like.

The use of the resin composition of the present invention is not particularly limited, but it can be used for insulating resin sheets such as films, prepregs, circuit boards (laminates, multilayer printed wiring boards, etc.), solder resist, underfill materials, adhesives, etc. Crystal materials, semiconductor packaging materials, buried-hole resins, and embedded resins are used in a wide range of applications where a resin composition is necessary. Among them, in the manufacture of a multilayer printed wiring board, a resin composition for forming an insulating layer (resin composition for an insulating layer of a multilayer printed wiring board) can be preferably used, and it can be suitably used as The resin composition for forming a conductor layer by plating (the resin composition for an insulating layer of a multilayer printed wiring board by which the conductor layer is formed by plating) can be better used as a resin composition for forming an additional layer (multilayer printed wiring) Resin composition for buildup of boards). The resin composition of the present invention can also be coated on a circuit board to form an insulating layer in a paint state, but it is generally preferred to use it in the form of a sheet-like laminated material such as a film and a prepreg in the industry. The softening point of the resin composition is preferably from 40 to 150 ° C from the viewpoint of the lamination property of the sheet-like laminate.

<Adhesive film>

The adhesive film of the present invention can be prepared by a method known to those skilled in the art, for example, the resin composition is dissolved in an organic solvent to prepare a resin varnish, and the resin varnish is applied to a support using a die applicator, etc. It is then prepared by heating or drying the organic solvent with hot air to form a resin composition layer. Made.

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Acetates, carbitols such as lyocells, butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. Amine-based solvents. The organic solvent may be used in combination of two or more.

The drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent to the resin composition layer becomes 10% by mass or less, and preferably 5% by mass or less. Although the amount of organic solvent in the paint varies depending on the boiling point of the organic solvent, for example, by drying a paint containing 30 to 60% by mass of an organic solvent at 50 to 150 ° C for about 3 to 10 minutes, a resin composition can be formed. Physical layer.

The thickness of the resin composition layer formed in the next film is preferably equal to or greater than the thickness of the conductor layer. The thickness of the conductor layer of the circuit substrate is usually in the range of 5 to 70 μm, so the resin composition layer preferably has a thickness of 10 to 100 μm.

Examples of the support include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes referred to as "PET"), and polyesters such as polyethylene naphthalate. Film, polycarbonate film, polyimide film and other plastic films. In addition, release foil, metal foil such as copper foil, aluminum foil, etc. can also be used. The support and a protective film described later may be subjected to surface treatments such as matting treatment and corona treatment. In addition, a release treatment may be performed using a release agent such as a silicone resin-based release agent, an alkyd resin-based release agent, or a fluororesin-based release agent.

The thickness of the support is not particularly limited, but is preferably 10 to 150 μm, and more preferably 25 to 50 μm.

The surface of the resin composition layer that is not in contact with the support may be laminated with a protective film according to the support. The thickness of the protective film is not particularly limited, but may be, for example, 1 to 40 μm. By laminating the protective film, dust or scratches can be prevented from adhering to the surface of the resin composition layer. The film can then be rolled into a roll and stored.

〈Multilayer printed wiring board using film bonding〉

Next, an example of a method for manufacturing a multilayer printed wiring board using the adhesive film manufactured as described above will be described.

First, using a vacuum laminator, the adhesive film was laminated on one or both sides of a circuit board. Examples of the substrate used on the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. The term "circuit board" as used herein means a patterned conductor layer (circuit) formed on one or both sides of the substrate as described above. And in a multilayer printed wiring board that alternately laminates a conductor layer and an insulating layer, one or both sides of the outermost layer of the multilayer printed wiring board can also be patterned into a conductor layer (circuit), and is included herein as referred to herein Circuit board. The surface of the conductor layer may be pre-roughened by blackening treatment, copper etching treatment, or the like.

In the above-mentioned lamination, when the adhesive film has a protective film, after removing the protective film, the adhesive film and the circuit substrate may be preheated as necessary, and the circuit substrate may be pressed while pressing and heating the adhesive film. In the adhesive film of the present invention, a method in which a vacuum lamination method is used to laminate a circuit substrate under reduced pressure is preferably used. The lamination conditions are not particularly limited, for example, the pressing temperature (laminating temperature) is preferably 70 to 140 ° C, and the pressing pressure is preferably 1 to 11 kgf / cm ² (9.8 × 10 ⁴ to 107.9 × 10 ⁴ N / m ² ), and preferably laminated under a reduced pressure of an air pressure of 20 mmHg (26.7 hPa) or less. The lamination method may be a batch method or a continuous method of a roll. For vacuum lamination, a commercially available vacuum laminator can be used. Commercially available vacuum laminators include, for example, a vacuum coater made by NICHIGO MORTON, a vacuum pressurized laminator made by Meiji Seisakusho, and a roll dry coating made by Hitachi Kogyo. Fabrics, vacuum laminators manufactured by Hitachi AIC, etc.

The laminating step of heating and pressing under reduced pressure can also be performed using a general vacuum hot press. For example, it can be performed by pressing a heated metal plate such as SUS from the support layer side. The pressing conditions are such that the degree of reduced pressure is usually 1 × 10 ^-2 MPa or less, and preferably 1 × 10 ^-3 MPa or less. The heating and pressing may be performed in one stage, but from the viewpoint of controlling resin penetration, it is preferably performed in two or more stages. For example, in the first stage of pressing at a temperature of 70 to 150 ° C, the pressure is in the range of 1 to 15 kgf / cm ² , and in the second stage of pressing at a temperature of 150 to 200 ° C, the pressure is in the range of 1 to 40 kgf / cm ² good. The time of each stage is preferably 30 ~ 120 minutes. Commercially available vacuum hot presses include, for example, MNPC-V-750-5-200 (made by Meiki Seisakusho Co., Ltd.), VH1-1603 (made by Kitagawa Seiki Co., Ltd.), and the like.

After the adhesive film is laminated on the circuit substrate, and after cooling to a temperature near room temperature, when the support is peeled off, an insulating layer can be formed on the circuit substrate by peeling and thermal curing. The conditions for heat curing may be appropriately selected according to the type and content of the resin component in the resin composition, but it is preferably 20 minutes to 180 minutes at 150 ° C to 220 ° C, and more preferably 30 to 160 ° C to 210 ° C. Choose within 120 minutes.

After the insulating layer is formed, if the support is not peeled before curing, it is peeled at this time. Then, if necessary, a hole is formed in the insulating layer formed on the circuit substrate to form a through hole and a through hole. The drilling can be performed by conventional methods such as drilling, laser, plasma, etc., and can be combined according to the needs, but the most common method is to use carbon dioxide gas laser, YAG laser and other lasers for drilling.

Next, a conductive layer is formed on the insulating layer by dry plating or wet plating. For the dry plating, conventional methods such as vapor deposition, sputtering, and ion plating can be used. In the case of wet plating, the surface of the insulating layer is sequentially subjected to a swelling treatment with a swelling solution, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution to form an uneven anchor. The swelling treatment with a swelling liquid is performed by immersing the insulating layer in a swelling liquid at 50 to 80 ° C. for 5 to 20 minutes. The swelling liquid is exemplified by an alkaline solution, a surfactant solution, and the like, preferably an alkaline solution, and the alkaline solution is exemplified by a sodium hydroxide solution, a potassium hydroxide solution, and the like. Examples of commercially available swelling liquids include Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, etc. manufactured by ATOTECH Japan. The roughening treatment by the oxidant is performed by immersing the insulating layer in an oxidant solution at 60 to 80 ° C for 10 to 30 minutes. Examples of the oxidizing agent include an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, and the like. In addition, the permanganate concentration in the alkaline permanganic acid solution is preferably 5 to 10% by weight. Commercially available oxidants are listed as, for example, CONCENTRATE manufactured by ATOTECH Japan. COMPACT CP, DOSING SOLUTION SECURIGANTH P and other alkaline permanganic acid solutions. Neutralization treatment with a neutralizing solution is performed by immersing in a neutralizing solution at 30 to 50 ° C for 3 to 10 minutes. As for the neutralization solution, an acidic aqueous solution is preferred, and commercially available products are REDUCTION SOLUTION SECURIGANTH P manufactured by ATOTECH Japan.

Next, the electroless plating and electrolytic plating are combined to form a conductor layer. In addition, a plating resist having a pattern opposite to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. As for the subsequent pattern formation method, for example, a reduction method, a semi-addition method, and the like known to those skilled in the art can be used.

<Prepreg sheet>

The prepreg sheet of the present invention can be produced by impregnating the resin composition of the present invention in a sheet-like reinforcing substrate composed of fibers by a hot melt method or a solvent method, and heating and semi-hardening it. That is, it is a prepreg in a state where the resin composition of the present invention is impregnated in a sheet-like reinforcing substrate composed of fibers. As the sheet-like reinforcing substrate composed of fibers, for example, a fiber commonly used as a fiber for prepregs such as glass cloth or aramide fiber can be used.

The hot-melt method does not dissolve the resin in an organic solvent, but temporarily coats the coated paper with good releasability from the resin, and laminates it on a sheet-like reinforcing substrate, or does not dissolve the resin in an organic solvent. The method of manufacturing a prepreg by directly coating a thin-shaped reinforcing substrate with a die applicator. And the solvent method is the same as that of the film, the resin is dissolved in an organic solvent, the resin paint is prepared, the sheet-like reinforcing substrate is immersed in the paint, the resin paint is impregnated in the sheet-like reinforcing substrate, and then dried Method.

〈Multilayer printed wiring board using prepregs〉

Next, an example of a method for manufacturing a multilayer printed wiring board using the prepreg manufactured as described above will be described. One piece or as many pieces of the prepreg according to the present invention are superimposed on a circuit substrate, held by a metal plate through a release film, and laminated under vacuum under pressure and heating. Pressure. The heating conditions are preferably a pressure of 5 to 40 kgf / cm ² (49 × 10 ⁴ to 392 × 10 ⁴ N / m ² ), and a temperature of 120 to 200 ° C. for 20 to 100 minutes. And like the adhesive film, the prepreg can be laminated on the circuit substrate by vacuum lamination, and then heat-hardened. Subsequently, in the same manner as described above, the surface of the cured prepreg is roughened, and then a conductor layer is formed by plating to manufacture a multilayer printed wiring board.

<Semiconductor device>

A semiconductor device can be manufactured by using the multilayer printed wiring board of the present invention. A semiconductor device can be manufactured by mounting a semiconductor die on a conducting portion of the multilayer printed wiring board of the present invention. The so-called "conducting part" is "a part that conducts electric signals in a multilayer printed wiring board", and the position may be either a surface or an embedded part. In addition, the semiconductor crystal grain is not particularly limited as long as it is an electrical circuit element using a semiconductor as a material.

The mounting method of the semiconductor die when the semiconductor device of the present invention is manufactured is not particularly limited as long as the semiconductor die performs an effective function. Specifically, it is a wire bonding installation method, a flip chip installation method, an installation method using a bumpless build up layer (BBUL), an installation method using an anisotropic conductive film (ACF), and a non-conductive method. Sex film (NCF) installation method.

The so-called "mounting method using bumpless build-up (BBUL)" is "mounting method of directly embedding semiconductor die in recesses of a multilayer printed wiring board and connecting semiconductor die to wiring on the printed wiring board" Furthermore, it can be roughly divided into the following BBUL method 1) and BBUL method 2) installation methods.

BBUL method 1) A mounting method for mounting a semiconductor die in a recess of a multilayer printed wiring board using an underfill.

BBUL method 2) A mounting method in which a semiconductor die is mounted in a recess of a multilayer printed wiring board using an adhesive film or a prepreg.

The BBUL method 1) specifically includes the following steps.

Step 1) A person who removes the conductor layer from both sides of the multilayer printed wiring board is provided, and a through hole is formed by laser and mechanical drilling.

Step 2) Adhere the adhesive tape on one side of the multilayer printed wiring board, and arrange it so that the bottom surface of the semiconductor die is fixed to the adhesive tape in the through hole. The semiconductor crystal grains at this time are preferably lower than the height of the through holes.

Step 3) An underfill is injected and filled in the gap between the through hole and the semiconductor die, and the semiconductor die is fixed in the through hole.

Step 4) Then peel the adhesive tape to expose the bottom surface of the semiconductor die.

Step 5) The adhesive film or prepreg of the present invention is laminated on the bottom side of the semiconductor die to cover the semiconductor die.

Step 6) After the adhesive film or prepreg is hardened, perforation is performed by laser to expose the bonding pad on the bottom surface of the semiconductor die, and roughened as shown above. Treatment, electroless plating, electrolytic plating, and connection to wiring. If necessary, further laminating the film or prepreg.

The BBUL method 2) specifically includes the following steps.

Step 1) A photoresist film is formed on the conductor layers on both sides of the multilayer printed wiring board, and an opening portion is formed only on one side of the photoresist film by a photolithography method.

Step 2) The conductive layer exposed at the opening is removed with an etchant to expose the insulating layer, and then the photoresist films on both sides are removed.

Step 3) Use a laser or drilling machine to completely remove the exposed insulating layer and make a hole to form a recess. It is preferable that the laser energy can adjust the laser energy in such a manner that the laser absorption rate of copper can be reduced and the laser absorption rate of the insulation layer can be increased, and more preferably a carbon dioxide laser. By using such a laser, it is possible to prevent the laser from penetrating the conductor layer opposite to the opening portion of the conductor layer, and only remove the insulating layer.

Step 4) The bottom surface of the semiconductor crystal grains is arranged in the recessed portion toward the opening portion side, and the adhesive film or prepreg of the present invention is laminated from the opening portion side to cover the semiconductor crystal grains and embed the gap between the semiconductor crystal grains and the recessed portions. The semiconductor crystal grains at this time are preferably lower than the height of the concave portion.

Step 5) After the adhesive film or prepreg is hardened, a laser is used to make holes to expose the bonding pads on the bottom surface of the semiconductor die.

Step 6) Connect the wiring by performing the roughening treatment, electroless plating, and electrolytic plating described above, and then laminate the film or prepreg as necessary.

In the method of mounting a semiconductor die, from the viewpoint of miniaturization of a semiconductor device and reduction of transmission loss, or because no solder is used, the semiconductor is not required. From the viewpoint of applying thermal history to the die, so that solder and resin deformation will not occur in the future, it is better to use the bumpless build-up (BBUL) installation method, more preferably BBUL method 1), BBUL method 2), and Better for BBUL method 2).

[Example]

Hereinafter, the present invention will be specifically described with examples, but the present invention is not limited to these examples.

<test methods. Evaluation method>

First of all, for various determination methods. The evaluation method is explained.

<Preparation of samples for measurement of peel strength, arithmetic average roughness (Ra value), and root mean square square root roughness (Rq value)> (1) Bottom layer processing of inner circuit board

CZ8100 made of MEC (copper) will etch 1 μm on both sides of a copper laminated board (copper foil thickness of 18 μm, substrate thickness of 0.3 mm, and Matsushita Electric Works Co., Ltd. R5715ES) on both sides of the glass cloth substrate epoxy resin that forms the inner circuit , Roughening the copper surface.

(2) Laminating the film

Using the batch-type vacuum pressure laminator MVLP-500 (trade name manufactured by Meiki Co., Ltd.), the adhesive films produced in the examples and comparative examples were laminated on both sides of the inner-layer circuit board. Laminated system is decompressed for 30 seconds to make the air pressure 13 hPa Hereinafter, it was carried out by pressing at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Roughening of resin composition

After laminating the adhesive film, the PET film was peeled off in Examples 1 to 4, and then the resin composition was cured at 100 ° C for 30 minutes, and then at 180 ° C for 30 minutes. After thermal curing under the same conditions, the PET film was peeled to form an insulating layer.

(4) Roughening

The inner circuit board forming the insulating layer was immersed in Swelling Dip Securiganth P (glycol ether, aqueous sodium hydroxide solution) containing diethylene glycol monobutyl ether manufactured by Japan ATOTECH Co., Ltd. in a swelling liquid. Examples 1 to 4 were immersed at 60 ° C for 5 minutes, Example 5 was immersed at 60 ° C for 10 minutes, and then immersed in CONCENTRATE COMPACT P (KMnO ₄ : 60g / L) of Japan ATOTECH Co., Ltd. as a roughening solution. NaOH: 40g / L aqueous solution), immersed at 80 ° C for 15 minutes in Examples 1 to 4, immersed at 80 ° C for 20 minutes, and finally immersed in Japan as a neutralizing solution at 40 ° C REDUCTION SOLUTION SECURIGANTH P (glutaraldehyde, aqueous solution of sulfuric acid) manufactured by ATOTECH Co., Ltd. for 5 minutes. After drying at 80 ° C for 30 minutes, the surface of the insulating layer after the roughening treatment was measured for arithmetic mean roughness (Ra value) and mean square root roughness (Rq value).

(5) Plating by semi-additive process

To form a circuit on the surface of the insulating layer, the inner circuit board was immersed in an electroless plating solution containing PdCl ₂ at 40 ° C for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C for 20 minutes. . After annealing at 150 ° C. for 30 minutes, an etching resist is formed, and a pattern is formed by etching, and then copper sulfate electrolytic plating is performed to form a conductor layer having a thickness of 35 ± 5 μm. Then, annealing treatment was performed at 200 ° C for 60 minutes. The circuit board was measured for the tensile peel strength (peel strength) of the plated conductor layer.

<Measurement of the tensile peel strength (peel strength) of the plated conductor layer>

Cut out a cut of 10mm in width and 100mm in length in the conductor layer of the circuit board, peel off one end and clamp it with a jig (TSE Co., Ltd., AUTOCOM-type testing machine AC-50C-SL), at room temperature , The load (kgf / cm) was measured at a speed of 50 mm / minute when 35 mm was peeled in the vertical direction.

〈Measurement of arithmetic mean roughness (Ra value) and mean square square root roughness (Rq value) after roughening〉

Using a non-contact type surface roughness meter (WYKO NT3300 manufactured by VEECO Instruments Co., Ltd.), a VSI contact mode, a 50-times lens, and a measurement range of 121 μm × 92 μm were used to obtain Ra and Rq values. Next, an average value of 10 points was measured.

<Measurement of average thermal expansion coefficient and glass transition temperature>

The adhesive films obtained in Examples and Comparative Examples were heated at 200 ° C. for 90 minutes for thermal curing, and the PET film was peeled to obtain a sheet-like cured product. This cured product was cut into test pieces having a width of about 5 mm and a length of about 15 mm. The thermo-mechanical analysis was performed using a thermo-mechanical analyzer Thermo Plus TMA8310 (manufactured by Rigaku Co., Ltd.) by a tensile weight method. After the test piece was mounted on the aforementioned device, the measurement was performed twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./minute. Calculate the average thermal expansion rate (ppm) from 25 ° C to 150 ° C for the second measurement. The glass transition temperature (° C) was calculated from the point where the slope of the dimensional change signal was changed for the second measurement.

<Manufacturing Example 1>

100 parts by mass of spherical silicon dioxide ("SOC2" manufactured by ADMATECHS Co., Ltd., with an average particle diameter of 0.5 µm) was put into a Henschel mixer, and the trifunctional alkoxysilane modified resin ( A solution of 1.8 parts by mass of "E201" manufactured by Arakawa Chemical Industries, Ltd. (epoxy equivalent: 285) and 1.8 parts by mass of MEK was stirred with spherical silica for 10 minutes, and then stirred at 75 ° C for 1 hour. The volatile components were distilled off to prepare a manufactured product 1.

<Manufacturing Example 2>

100 parts by mass of spherical silicon dioxide ("SOC2" manufactured by ADMATECHS Co., Ltd., with an average particle diameter of 0.5 µm) was put into a Henschel mixer, and the trifunctional alkoxysilane modified resin ( "P501" manufactured by Arakawa Chemical Industries, Ltd., 275 phenolic hydroxyl equivalents (1.8) parts by mass and 1.8 parts by mass of MEK were mixed in advance while stirring the spherical silica for 10 minutes. After stirring at 75 ° C. for 1 hour, the volatile components were distilled off to prepare a product 2.

<Manufacturing Example 3>

100 parts by mass of spherical silicon dioxide ("SOC2" manufactured by ADMATECHS Co., Ltd., with an average particle diameter of 0.5 µm) was put into a Henschel mixer, and the 4-functional alkoxysilane modified resin ( 1.8 parts by mass of "E202C" (Equation (10)) manufactured by Arakawa Chemical Industries, Ltd. (epoxy equivalent: 285) and 1.8 parts by mass of MEK were mixed in advance while stirring the spherical silica for 10 minutes. After stirring at 75 ° C. for 1 hour, the volatile components were distilled off to produce a product 3.

(式中，n表示1~10，m表示1~10)。

(In the formula, n represents 1 to 10, and m represents 1 to 10).

<Manufacturing Example 4>

100 parts by mass of spherical silicon dioxide ("SOC2" manufactured by ADMATECHS Co., Ltd., with an average particle diameter of 0.5 µm) was put into a Henschel mixer, and the 4-functional alkoxysilane modified resin ( 1.8 parts by mass of "P502" (formula (11)) manufactured by Arakawa Chemical Industries, Ltd. (300 phenolic hydroxyl equivalents) and 1.8 parts by mass of MEK are mixed in advance while stirring spherical silica 10 After being stirred at 75 ° C. for 1 hour, the volatile components were distilled off to prepare a product 4.

(式中，m表示1~10)。

(In the formula, m represents 1 to 10).

<Example 1>

5 parts by mass of naphthalene-type epoxy resin (epoxy equivalent 144, "HP4700" manufactured by DIC Corporation), liquid bisphenol A-type epoxy resin (epoxy equivalent 180, manufactured by Mitsubishi Chemical Corporation) jER828EL ") 14 parts by mass, 14 parts by mass of biphenyl epoxy resin (epoxy equivalent 269," NC3000H "manufactured by Nippon Kayaku Co., Ltd.) was dissolved in 30 parts by mass of solvent petroleum naphthalene, heated to dissolve, and then cooled to At room temperature, mixture 1 was prepared. Next, 1.5 parts by mass of rubber particles (STAFILOID AC3816N manufactured by GANTZ Kasei Co., Ltd.) were allowed to stand and swell in 6 parts by mass of solvent naphtha at room temperature for 12 hours to prepare a mixture 2. Add Mixture 2 and Spherical Silicon Dioxide ("SOC2" made by ADMATECHS Co., Ltd.) directly to Mixture 1. Average particle size 0.5 μm) 100 parts by mass of a trifunctional alkoxysilane modified resin ("E201" manufactured by Arakawa Chemical Industries, Ltd., epoxy equivalent 285) 1.8 parts by mass, followed by the addition of a flame retardant (manufactured by Mitsuko Corporation) "HCA-HQ", 5 parts by mass of 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, with an average particle size of 1 μm. Three rollers are kneaded and dispersed. Next, a phenol novolac-based hardener ("LA-7054" manufactured by DIC Corporation), and a 60% by mass non-volatile methyl ethyl ketone (hereinafter referred to as "MEK") solution of phenolic hydroxyl equivalent 124 were mixed. 10 parts by mass, naphthalene-based phenol resin (phenolic hydroxyl equivalent 215, "SN485" manufactured by Nippon Steel Chemical Co., Ltd., non-volatile 60% by mass MEK solution), 10 parts by mass, phenoxy resin (weight average molecular weight 35000 , 7 parts by mass of a non-volatile MEK and cyclohexanone 1: 1 solution of 30% by mass of "YL7553" manufactured by Mitsubishi Chemical Corporation, and 5% by mass of 4-dimethylaminopyridine as a hardening accelerator 2 parts by mass of the solution and 4 parts by mass of methyl ethyl ketone (MEK) were uniformly dispersed with a rotary kneader to prepare a resin paint. Next, the resin varnish was uniformly applied to a polyethylene terephthalate film (thickness) to which an alkyd-based mold release treatment was applied with a die applicator so that the thickness of the dried resin composition layer became 40 μm. 38 μm) on the release surface, and then dried at 80 to 110 ° C. (average 95 ° C.) for 5 minutes (the amount of residual solvent in the resin composition layer: about 2% by mass). Next, a 15 μm-thick polypropylene film was bonded to the surface of the resin composition layer and rolled into a roll shape. The roll-shaped adhesive film was cut into a width of 507 mm to obtain a sheet-shaped adhesive film having a size of 507 × 336 mm.

<Example 2>

Except changing 1.8 parts by mass of the trifunctional alkoxysilane modified resin ("E201" manufactured by Arakawa Chemical Industries, Ltd., epoxy equivalent 285) of Example 1 to the trifunctional alkoxysilane modified resin ( 1.8 parts by mass of "P501" manufactured by Arakawa Chemical Industry Co., Ltd., phenolic hydroxyl equivalent 275), the rest are the same, and resin varnish is produced. Next, using this resin paint, it carried out similarly to Example 1, and obtained the adhesive film.

<Example 3>

In addition to adding product 1, instead of directly adding 100 parts by mass of spherical silicon dioxide ("SOC2" manufactured by ADMATECHS Co., Ltd., with an average particle diameter of 0.5 µm) and trifunctional alkoxysilane modified resin (Arakawa Except for 1.8 parts by mass of "E201" (epoxy equivalent 285) manufactured by Chemical Industry Co., Ltd., the rest are the same, and resin paint is produced. Next, using this resin paint, it carried out similarly to Example 1, and obtained the adhesive film.

<Example 4>

In addition to adding product 2 instead of directly adding 100 parts by mass of spherical silicon dioxide ("SOC2" manufactured by ADMATECHS Co., Ltd., with an average particle diameter of 0.5 µm) of Example 1 and a trifunctional alkoxysilane modified resin (Arakawa Except for "E201" manufactured by Chemical Industry Co., Ltd., which has an epoxy equivalent of 285) and 1.8 parts by mass, the rest are the same, and resin paint is produced. Next, using this resin paint, it carried out similarly to Example 1, and obtained the adhesive film.

<Example 5>

8 parts by mass of naphthalene-type epoxy resin (epoxy equivalent 144, "EXA4032SS" manufactured by DIC Corporation), bixylenol-type epoxy resin (epoxy equivalent 190, Mitsubishi Chemical Corporation "" YX4000HK " ") 10 parts by mass of modified naphthalene-type epoxy resin (epoxy equivalent of about 330," ESN-475V "manufactured by Nippon Steel Chemical Co., Ltd.) 9 parts by mass was dissolved in 33 parts by mass of solvent petroleum naphtha while heating and dissolving. . After cooling to room temperature, next, 1.5 mass parts of STAFILOID (GANTZ Kasei Co., Ltd., AC3816N) as rubber particles was added and left to swell in 6 mass parts of solvent petroleum naphtha at room temperature for 12 hours, and 140 parts by mass of spherical silicon dioxide ("SOC2" manufactured by ADMATECHS Co., Ltd., with an average particle diameter of 0.5 μm), and 1.4 parts by mass of a trifunctional alkoxysilane modified resin (manufactured by Arakawa Chemical Industries, Ltd.) "P501", phenolic hydroxyl equivalent 275), kneaded and dispersed with three rollers. Next, 45 parts by mass of an active ester hardener ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution of 65% by mass of a nonvolatile matter with an active group equivalent of about 223), and a phenoxy resin (weight average molecular weight 35000) , 5 parts by mass of MEK and 1: 1 solution of cyclohexanone with 30% by mass of "YL7553" made by Mitsubishi Chemical Corporation, and 5% by mass of MEK with 4-dimethylaminopyridine as a hardening accelerator 4 parts by mass of the solution and 4 parts by mass of methyl ethyl ketone (MEK) were uniformly dispersed with a rotary kneader to prepare a resin paint. This resin paint was then used in exactly the same manner as in Example 1 to obtain an adhesive film.

<Comparative Example 1>

Except that the 3-functional alkoxysilane modified resin of Example 1 ("E201" manufactured by Arakawa Chemical Industries, Ltd., epoxy equivalent 285) was not added, the rest All are the same, and a resin paint is made. This resin paint was then used in exactly the same manner as in Example 1 to obtain an adhesive film.

<Comparative Example 2>

Except changing 1.8 parts by mass of the trifunctional alkoxysilane modified resin ("E201" manufactured by Arakawa Chemical Industries, Ltd., epoxy equivalent 285) of Example 1 to a 4-functional alkoxysilane modified resin (Arakawa Except for 1.8 parts by mass of "E202C" (Equation (10)), epoxy equivalent 285) manufactured by Chemical Industry Co., Ltd., the rest are the same, and resin paint is produced. This resin paint was then used in exactly the same manner as in Example 1 to obtain an adhesive film.

<Comparative Example 3>

Except changing 1.8 parts by mass of the trifunctional alkoxysilane modified resin of Example 1 (epoxy equivalent 285, E201 manufactured by Arakawa Chemical Industries, Ltd.) to a 4-functional alkoxysilane modified resin (Arakawa Chemical Industries) Except for 1.8 parts by mass of "P502" (the above formula (11)) made by (stock), the phenolic hydroxyl equivalent is 300), and the rest are the same, and a resin paint is produced. This resin paint was then used in exactly the same manner as in Example 1 to obtain an adhesive film.

<Comparative Example 4>

In addition to adding product 3 instead of directly adding 100 parts by mass of spherical silicon dioxide ("SOC2" manufactured by ADMATECHS Co., Ltd., with an average particle diameter of 0.5 μm) and trifunctional alkoxysilane modified resin (Arakawa Except for "E201" manufactured by Chemical Industry Co., Ltd., epoxy equivalent 285) 1.8 parts by mass, the rest are the same , Making resin paint. Next, using this resin paint, it carried out similarly to Example 1, and obtained the adhesive film.

<Comparative Example 5>

In addition to adding the product 4, instead of directly adding 100 parts by mass of spherical silicon dioxide ("SOC2" manufactured by ADMATECHS Co., Ltd., with an average particle diameter of 0.5 m) and a trifunctional alkoxysilane modified resin (Arakawa Except for "E201" manufactured by Chemical Industry Co., Ltd., which has an epoxy equivalent of 285) and 1.8 parts by mass, the rest are the same, and resin paint is produced. Next, using this resin paint, it carried out similarly to Example 1, and obtained the adhesive film.

<Comparative Example 6>

Except changing 1.8 parts by mass of the trifunctional alkoxysilane modified resin ("E201" manufactured by Arakawa Chemical Industries, Ltd., epoxy equivalent 285) of Example 1 to an epoxy-based silane coupling agent (Shin-Etsu Chemical Industry ( "KBM403" (manufactured in stock) except 0.6 parts by mass, the rest are the same, and resin paint is made. This resin paint was then used in exactly the same manner as in Example 1 to obtain an adhesive film.

The results are shown in Table 1.

From the results in Table 1, it can be seen that the resin compositions of Examples 1 to 5 have low arithmetic mean roughness, low mean square root roughness, and can obtain values with sufficient peel strength. On the other hand, since Comparative Example 1 does not contain the component (B), the arithmetic average roughness and the square root roughness increase, and the peel strength is also low. In Comparative Examples 2 to 6, the component (B) was not included, and the arithmetic average roughness and the square root roughness increased, and they bulged during plating to make the peeling strength significantly smaller.

[Possibility of industrial use]

The invention can provide a glass transition temperature and a thermal expansion rate on the one hand, and the arithmetic mean roughness and the root mean square root roughness of the insulating layer surface in the wet roughening step on the other hand can be made small, and can be formed thereon with sufficient strength. A resin composition for plating a conductor layer. Furthermore, using such an adhesive film, a prepreg, a multilayer printed wiring board, and a semiconductor device can be provided. Furthermore, electrical appliances such as computers, mobile phones, digital cameras, televisions, or electric bicycles, automobiles, trams, ships, and airplanes can be provided.

Claims (13)

A resin composition characterized by a resin composition containing (A) an epoxy resin, (B) a trifunctional alkoxysilane modified resin, and (C) an inorganic filler, wherein (A) the epoxy resin is contained at a temperature The liquid epoxy resin at 20 ° C and the solid epoxy resin at a temperature of 20 ° C, the blending ratio (liquid epoxy resin: solid epoxy resin) is 1: 0.1 ~ 2, of which When the non-volatile content in the resin composition is 100% by mass, the content of the (C) inorganic filler is 20 to 85% by mass. For example, the resin composition of the first patent application range, wherein (B) at least a part of the trifunctional alkoxysilane modified resin is reacted with (C) an inorganic filler to form a reactant. For example, the resin composition of the second patent application range is formed by reacting (B) a trifunctional alkoxysilane modified resin with (C) an inorganic filler in advance and adding it to (A) an epoxy resin. . For example, if the resin composition of the first patent application range is (C) the inorganic filler is 100% by mass, the (B) trifunctional alkoxysilane modified resin is 0.1 to 5% by mass. For example, the resin composition of item 1 of the patent application range, wherein (B) the trifunctional alkoxysilane modified resin is a trifunctional alkoxysilane modified by a silane in a hydroxyl group-containing epoxy resin. Modified epoxy resin and / or phenolic phenolic hydroxyl group modified by silane trifunctional alkoxysilane modified phenol resin. For example, the resin composition of the first patent application range, wherein the (B) trifunctional alkoxysilane modified resin is the following formula (1):

In formula (1), R ₃ is a straight or branched alkyl group having 1 to 10 carbon atoms, or an allyl group, and R ₄ and R _{5 are} each independently hydrogen and a straight or branched chain having 1 to 10 carbon atoms. Alkyl group, in the formula (1), m represents 1 to 10, and in the formula (1), X is selected from an epoxy resin or a phenol resin. For example, the resin composition of the first patent application range, wherein the (B) trifunctional alkoxysilane modified resin is the following formula (1):

In formula (1), R ₃ is a straight or branched alkyl group having 1 to 10 carbon atoms, or an allyl group, and R ₄ and R _{5 are} each independently hydrogen and a straight or branched chain having 1 to 10 carbon atoms. Alkyl, in formula (1), m represents 1 to 10, and in formula (1), X is selected from bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AF epoxy resin, bis Phenolic S-type epoxy resin, novolac phenol resin. For example, the resin composition of the scope of patent application, wherein the resin composition is hardened to form an insulating layer, and the surface of the insulating layer is roughened. And the peeling strength of the conductor layer and the insulating layer obtained by plating is 0.43kgf / cm ~ 1.0kgf / cm, the resin composition is hardened to form an insulating layer, and the arithmetic average roughness of the surface of the insulating layer after roughening treatment The degree is 10nm ~ 300nm, and the square root roughness is 10nm ~ 520nm. For example, the resin composition of the scope of application for patent No. 1 is for forming an insulating layer of a multilayer printed wiring board. An adhesive film is formed by forming a resin composition as described in any one of claims 1 to 9 on an upper layer of a support. A prepreg sheet is prepared by impregnating a resin composition as described in any one of claims 1 to 9 in a sheet-like reinforcing substrate. A multilayer printed wiring board is formed of a hardened product of a resin composition as described in any one of claims 1 to 9 of the patent application scope to form an insulating layer. A semiconductor device characterized by using a multilayer printed wiring board such as the item 12 in the patent application scope.